CN101193943B - Films and/or sheets comprising certain bonded polyester compositions comprising cyclobutanediol and having an inherent viscosity and a moderate glass transition temperature - Google Patents

Abstract

Translated fromChinese

描述了薄膜和/或薄板，其包含聚酯，该聚酯包含(a)二羧酸组分，其具有对苯二甲酸残基；任选地，芳族二羧酸残基或脂族二羧酸残基；2，2，4，4-四甲基-1，3-环丁二醇残基；和1，4-环己烷二甲醇残基。

Films and/or sheets are described that comprise polyesters comprising (a) a dicarboxylic acid component having terephthalic acid residues; optionally, aromatic dicarboxylic acid residues or aliphatic dicarboxylic acid residues; 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and 1,4-cyclohexanedimethanol residues.

Description

Translated fromChinese

包含含有环丁二醇且具有比浓对数粘度和适度的玻璃化转变温度的某种结合的聚酯组合物的薄膜和/或薄板Films and/or sheets comprising certain bonded polyester compositions comprising cyclobutanediol and having an inherent viscosity and a moderate glass transition temperature

相关申请的交叉引用Cross References to Related Applications

本申请根据35 U.S.C.§119(e)要求以下申请的优先权：美国临时申请60/691,567(申请日为2005年6月17日)、美国临时申请60/731,454(申请日为2005年10月28日)、美国临时申请60/731,389(申请日为2005年10月28日)、美国临时申请60/739,058(申请日为2005年11月22日)、美国临时申请60/738,869(申请日为2005年11月22日)、美国临时申请60/750,692(申请日为2005年12月15日)、美国临时申请60/750,693(申请日为2005年12月15日)、美国临时申请60/750,682(申请日为2005年12月15日)和美国临时申请60/750,547(申请日为2005年12月15日)，所有这些文献以其全部内容引入本文作为参考。This application claims priority under 35 U.S.C. §119(e): U.S. Provisional Application 60/691,567 (filed June 17, 2005), U.S. Provisional Application 60/731,454 (filed October 28, 2005) date), U.S. provisional application 60/731,389 (filed October 28, 2005), U.S. provisional application 60/739,058 (filed November 22, 2005), U.S. provisional application 60/738,869 (filed 2005 November 22, 2005), U.S. Provisional Application 60/750,692 (filed December 15, 2005), U.S. Provisional Application 60/750,693 (filed December 15, 2005), U.S. Provisional Application 60/750,682 ( filed December 15, 2005) and US Provisional Application 60/750,547 (filed December 15, 2005), all of which are incorporated herein by reference in their entirety.

技术领域technical field

本发明一般地涉及包含聚酯组合物的薄膜和/或薄板，该聚酯组合物包含至少一种聚酯，其由对苯二甲酸、其酯或其混合物；2，2，4，4-四甲基-1，3-环丁二醇；和1，4-环己烷二甲醇制成，并且具有比浓对数粘度和玻璃化转变温度(Tg)的某种结合。这些薄膜和/或薄板具有以下性能中的至少两种的独特结合：高冲击强度、适度的玻璃化转变温度(Tg)、韧性、某一比浓对数粘度、低韧脆性转变温度、良好的颜色和透明性、低密度和长结晶半衰期，这使得其易于成形为薄膜和/或薄板。The present invention generally relates to films and/or sheets comprising polyester compositions comprising at least one polyester consisting of terephthalic acid, its esters or mixtures thereof; 2,2,4,4- Tetramethyl-1,3-cyclobutanediol; and 1,4-cyclohexanedimethanol, and has some combination of inherent viscosity and glass transition temperature (Tg). These films and/or sheets have a unique combination of at least two of the following properties: high impact strength, moderate glass transition temperature (Tg), toughness, a certain inherent viscosity, low ductile-brittle transition temperature, good Color and clarity, low density and long crystallization half-life, which make it easy to form into films and/or sheets.

背景技术Background technique

聚对苯二甲酸1，4-环己二亚甲酯(PCT)，一种仅仅基于对苯二甲酸和1，4-环己烷二甲醇的聚酯，是本领域已知的并且是市售可得的。这种聚酯当冷却时从熔体中迅速地结晶，这使得通过本领域已知的方法如挤出、注塑和类似方法很难形成无定形制品。为了使PCT的结晶速率变慢，可以制备含有另外的二羧酸或二醇如间苯二甲酸或乙二醇的共聚酯。这些乙二醇或者问苯二甲酸改性的PCT也是本领域已知的和是市售可得的。Polyethylene terephthalate (PCT), a polyester based solely on terephthalic acid and 1,4-cyclohexanedimethanol, is known in the art and is commercially available available for sale. Such polyesters crystallize rapidly from the melt when cooled, making it difficult to form amorphous articles by methods known in the art such as extrusion, injection molding, and the like. To slow the crystallization rate of PCT, copolyesters can be prepared containing additional dicarboxylic acids or diols such as isophthalic acid or ethylene glycol. These glycol or phthalic acid modified PCTs are also known in the art and are commercially available.

一种用于生产薄膜、薄板和模制品的常用的共聚酯由对苯二甲酸、1，4-环己烷二甲醇和乙二醇制成。虽然这些共聚酯可用于许多终端使用的应用中，但是当充足的改性乙二醇含于制剂中以便提供长结晶半衰期时，它们在如玻璃化转变温度和冲击强度等的性能方面显示出不足。例如，具有足够长结晶半衰期的由对苯二甲酸、1，4-环己烷二甲醇和乙二醇制成的共聚酯提供了无定形产品，相比于本文中公开的组合物，这些产品显示出较高的韧脆性转变温度和较低的玻璃化转变温度。A common copolyester used in the production of films, sheets and moldings is made from terephthalic acid, 1,4-cyclohexanedimethanol and ethylene glycol. While these copolyesters are useful in many end-use applications, they exhibit poor performance in properties such as glass transition temperature and impact strength when sufficient modifying glycols are included in the formulation to provide long crystallization half-life. insufficient. For example, copolyesters made from terephthalic acid, 1,4-cyclohexanedimethanol, and ethylene glycol with sufficiently long crystallization half-lives provide amorphous products that are less complex than the compositions disclosed herein. The product shows a higher ductile-brittle transition temperature and a lower glass transition temperature.

4，4′-亚异丙基二苯酚的聚碳酸酯(双酚A聚碳酸酯)已被用作本领域已知的聚酯的替换物并且是众所周知的工程模塑塑料。双酚A聚碳酸酯是一种具有良好的物理性能如形稳性、高耐热性和良好的冲击强度的透明的高性能塑料。虽然双酚A聚碳酸酯具有许多良好的物理性能，但是其较高熔体粘度导致差的熔体加工性能并且聚碳酸酯显示出差的耐化学性。此外其还难以热成形。Polycarbonate of 4,4'-isopropylidene diphenol (bisphenol A polycarbonate) has been used as an alternative to polyester known in the art and is a well known engineering molding plastic. Bisphenol A polycarbonate is a transparent high-performance plastic with good physical properties such as dimensional stability, high heat resistance and good impact strength. Although bisphenol A polycarbonate has many good physical properties, its high melt viscosity results in poor melt processability and polycarbonate exhibits poor chemical resistance. Furthermore it is difficult to thermoform.

在本领域中通常还已经描述了含有2，2，4，4-四甲基-1，3-环丁二醇的聚合物。然而通常，这些聚合物显示出高比浓对数粘度、高熔体粘度和高玻璃化转变温度，使得工业中所用的设备不能胜任制造或后聚合加工这些材料。Polymers containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol have also generally been described in the art. Typically, however, these polymers exhibit high inherent viscosities, high melt viscosities, and high glass transition temperatures, making the equipment used in the industry inadequate for the manufacture or post-polymerization processing of these materials.

因而，在本领域中需要包含聚酯组合物的薄膜和/或薄板，所述聚酯组合物包含至少一种聚酯，其具有选自以下至少一种的两种或更多种性能的结合：韧性、适度的玻璃化转变温度、良好的冲击强度、水解稳定性、耐化学性、长结晶半衰期、低韧脆性转变温度、良好的颜色和透明性、较低的密度和/或聚酯的热成形性，同时在工业中所用的标准设备上保持加工性能。Thus, there is a need in the art for films and/or sheets comprising polyester compositions comprising at least one polyester having a combination of two or more properties selected from at least one of : Toughness, moderate glass transition temperature, good impact strength, hydrolytic stability, chemical resistance, long crystallization half-life, low ductile-brittle transition temperature, good color and transparency, low density and/or polyester Thermoformability while maintaining processability on standard equipment used in industry.

发明内容Contents of the invention

据信，具有比浓对数粘度和/或玻璃化转变温度的某种结合、包含聚酯组合物(其又包含对苯二甲酸、其酯或其混合物；1，4-环己烷二甲醇；和2，2，4，4-四甲基-1，3-环丁二醇)的某些薄膜和/或薄板，在以下至少一个方面优于由本领域已知的聚酯和聚碳酸酯制成的薄膜和薄板：水解稳定性、韧性、耐化学性、较低的比重和热成形性。这些薄膜和/或薄板据信在耐热性方面类似于由聚碳酸酯制备的那些，并且在标准工业设备上仍可加工。It is believed that some combination of inherent viscosity and/or glass transition temperature, comprising a polyester composition (which in turn comprises terephthalic acid, its esters, or mixtures thereof; 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol) certain films and/or sheets are superior to polyesters and polycarbonates known in the art in at least one of the following aspects Produced films and sheets: hydrolytic stability, toughness, chemical resistance, low specific gravity and thermoformability. These films and/or sheets are believed to be similar in heat resistance to those made from polycarbonate and are still processable on standard industrial equipment.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，所述聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)1-99mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 1-99 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)1-99mol％的1，4-环己烷二甲醇残基，ii) 1-99 mol % of 1,4-cyclohexanedimethanol residues,

其中二羧酸组分的总摩尔百分数是100mol％，和wherein the total mole percent of the dicarboxylic acid component is 100 mole percent, and

二醇组分的总摩尔百分数是100mol％；和The total mole percent of the diol component is 100 mole percent; and

其中比浓对数粘度是0.10-小于1.0dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和wherein the inherent viscosity is from 0.10 to less than 1.0 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C; and

其中聚酯的Tg为85-120℃。The Tg of the polyester is 85-120°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，所述聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)1-99mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 1-99 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)1-99mol％的1，4-环己烷二甲醇残基，ii) 1-99 mol % of 1,4-cyclohexanedimethanol residues,

其中二羧酸组分的总摩尔百分数是100mol％，和wherein the total mole percent of the dicarboxylic acid component is 100 mole percent, and

二醇组分的总摩尔百分数是100mol％；和The total mole percent of the diol component is 100 mole percent; and

其中比浓对数粘度是0.35-小于1.0dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和wherein the inherent viscosity is from 0.35 to less than 1.0 dL/g, as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C; and

其中聚酯的Tg为85-120℃。The Tg of the polyester is 85-120°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，所述聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)5-小于50mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 5 - less than 50 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)大于50-95mol％的1，4-环己烷二甲醇残基，ii) greater than 50-95 mol % of 1,4-cyclohexanedimethanol residues,

其中所述二羧酸组分的总摩尔百分数是100mol％，而所述二醇组分的总摩尔百分数是100mol％；和wherein the total mole percent of the dicarboxylic acid component is 100 mol%, and the total mole percent of the diol component is 100 mol%; and

其中聚酯的比浓对数粘度为0.50-1.2dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和wherein the polyester has an inherent viscosity of 0.50 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C; and

其中聚酯的Tg为85-120℃。The Tg of the polyester is 85-120°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，所述聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)10-30mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 10-30 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)70-90mol％的1，4-环己烷二甲醇残基，ii) 70-90 mol % of 1,4-cyclohexanedimethanol residues,

其中所述二羧酸组分的总摩尔百分数是100mol％，而所述二醇组分的总摩尔百分数是100mol％；和wherein the total mole percent of the dicarboxylic acid component is 100 mol%, and the total mole percent of the diol component is 100 mol%; and

其中聚酯的比浓对数粘度为0.50-1.2dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和wherein the polyester has an inherent viscosity of 0.50 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C; and

其中所述聚酯的Tg为85-120℃。Wherein the Tg of the polyester is 85-120°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，所述聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)15-25mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 15-25 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)75-85mol％的1，4-环己烷二甲醇残基，ii) 75-85 mol % of 1,4-cyclohexanedimethanol residues,

其中所述二羧酸组分的总摩尔百分数是100mol％，而所述二醇组分的总摩尔百分数是100mol％；和wherein the total mole percent of the dicarboxylic acid component is 100 mol%, and the total mole percent of the diol component is 100 mol%; and

其中比浓对数粘度为0.50-1.2dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和wherein the inherent viscosity is from 0.50 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C; and

其中聚酯的Tg为85-120℃。The Tg of the polyester is 85-120°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，该聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)5-小于50mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 5 - less than 50 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)大于50-95mol％的1，4-环己烷二甲醇残基，ii) greater than 50-95 mol % of 1,4-cyclohexanedimethanol residues,

其中所述二羧酸组分的总摩尔百分数是100mol％，而所述二醇组分的总摩尔百分数是100mol％；和wherein the total mole percent of the dicarboxylic acid component is 100 mol%, and the total mole percent of the diol component is 100 mol%; and

其中聚酯的比浓对数粘度为0.50-1.2dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和其中聚酯的Tg为95-115℃。wherein the polyester has an inherent viscosity of 0.50-1.2 dL/g, as determined at 25°C at a concentration of 0.5g/100ml in 60/40 (wt/wt) phenol/tetrachloroethane; and wherein the poly The Tg of the ester is 95-115°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，所述聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)10-30mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 10-30 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)70-90mol％的1，4-环己烷二甲醇残基，ii) 70-90 mol % of 1,4-cyclohexanedimethanol residues,

其中所述二羧酸组分的总摩尔百分数是100mol％，而所述二醇组分的总摩尔百分数是100mol％；和wherein the total mole percent of the dicarboxylic acid component is 100 mol%, and the total mole percent of the diol component is 100 mol%; and

其中聚酯的比浓对数粘度为0.50-1.2dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和其中聚酯的Tg为95-115℃。wherein the polyester has an inherent viscosity of 0.50-1.2 dL/g, as determined at 25°C at a concentration of 0.5g/100ml in 60/40 (wt/wt) phenol/tetrachloroethane; and wherein the poly The Tg of the ester is 95-115°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，所述聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)15-25mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 15-25 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)75-85mol％的1，4-环己烷二甲醇残基，ii) 75-85 mol % of 1,4-cyclohexanedimethanol residues,

其中所述二羧酸组分的总摩尔百分数是100mol％，而所述二醇组分的总摩尔百分数是100mol％；和wherein the total mole percent of the dicarboxylic acid component is 100 mol%, and the total mole percent of the diol component is 100 mol%; and

其中，所述聚酯的比浓对数粘度是0.50-1.2dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和其中聚酯的Tg为95-115℃。Wherein, the inherent viscosity of the polyester is 0.50-1.2dL/g, as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25°C; And wherein the Tg of the polyester is 95-115°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，该聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)5-小于50mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 5 - less than 50 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)大于50-95mol％的1，4-环己烷二甲醇残基，ii) greater than 50-95 mol % of 1,4-cyclohexanedimethanol residues,

其中所述二羧酸组分的总摩尔百分数是100mol％，而所述二醇组分的总摩尔百分数是100mol％；和wherein the total mole percent of the dicarboxylic acid component is 100 mol%, and the total mole percent of the diol component is 100 mol%; and

其中，所述聚酯的比浓对数粘度是0.50-小于0.75dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和其中聚酯的Tg为85-120℃。wherein said polyester has an inherent viscosity of 0.50 to less than 0.75 dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C and wherein the Tg of the polyester is 85-120°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，该聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)10-30mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 10-30 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)70-90mol％的1，4-环己烷二甲醇残基，ii) 70-90 mol % of 1,4-cyclohexanedimethanol residues,

其中所述二羧酸组分的总摩尔百分数是100mol％，而所述二醇组分的总摩尔百分数是100mol％；和wherein the total mole percent of the dicarboxylic acid component is 100 mol%, and the total mole percent of the diol component is 100 mol%; and

其中，所述聚酯的比浓对数粘度是0.50-小于0.75dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和其中聚酯的Tg为85-120℃。wherein said polyester has an inherent viscosity of 0.50 to less than 0.75 dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C and wherein the Tg of the polyester is 85-120°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，所述聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)15-25mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 15-25 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)75-85mol％的1，4-环己烷二甲醇残基，ii) 75-85 mol % of 1,4-cyclohexanedimethanol residues,

其中所述二羧酸组分的总摩尔百分数是100mol％，而所述二醇组分的总摩尔百分数是100mol％；和wherein the total mole percent of the dicarboxylic acid component is 100 mol%, and the total mole percent of the diol component is 100 mol%; and

其中，所述聚酯的比浓对数粘度是0.50-小于0.75dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和其中聚酯的Tg为85-120℃。wherein said polyester has an inherent viscosity of 0.50 to less than 0.75 dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C and wherein the Tg of the polyester is 85-120°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，所述聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)5-小于50mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 5 - less than 50 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)大于50-95mol％的1，4-环己烷二甲醇残基，ii) greater than 50-95 mol % of 1,4-cyclohexanedimethanol residues,

其中所述二羧酸组分的总摩尔百分数是100mol％，而所述二醇组分的总摩尔百分数是100mol％；和wherein the total mole percent of the dicarboxylic acid component is 100 mol%, and the total mole percent of the diol component is 100 mol%; and

其中，所述聚酯的比浓对数粘度是0.50-小于0.75dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和其中聚酯的Tg为95-115℃。wherein said polyester has an inherent viscosity of 0.50 to less than 0.75 dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C and wherein the Tg of the polyester is 95-115°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，该聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)10-30mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 10-30 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)70-90mol％的1，4-环己烷二甲醇残基，ii) 70-90 mol % of 1,4-cyclohexanedimethanol residues,

其中所述二羧酸组分的总摩尔百分数是100mol％，而所述二醇组分的总摩尔百分数是100mol％；和wherein the total mole percent of the dicarboxylic acid component is 100 mol%, and the total mole percent of the diol component is 100 mol%; and

其中，所述聚酯的比浓对数粘度是0.50-小于0.75dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和其中聚酯的Tg为95-115℃。wherein said polyester has an inherent viscosity of 0.50 to less than 0.75 dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C and wherein the Tg of the polyester is 95-115°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，该聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)15-25mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 15-25 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)75-85mol％的1，4-环己烷二甲醇残基，ii) 75-85 mol % of 1,4-cyclohexanedimethanol residues,

其中所述二羧酸组分的总摩尔百分数是100mol％，而所述二醇组分的总摩尔百分数是100mol％；和wherein the total mole percent of the dicarboxylic acid component is 100 mol%, and the total mole percent of the diol component is 100 mol%; and

其中，所述聚酯的比浓对数粘度是0.50-小于0.75dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和其中聚酯的Tg为95-115℃。wherein said polyester has an inherent viscosity of 0.50 to less than 0.75 dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C and wherein the Tg of the polyester is 95-115°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，所述聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)15-25mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 15-25 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)75-85mol％的1，4-环己烷二甲醇残基，ii) 75-85 mol % of 1,4-cyclohexanedimethanol residues,

其中所述二羧酸组分的总摩尔百分数是100mol％，而所述二醇组分的总摩尔百分数是100mol％；和wherein the total mole percent of the dicarboxylic acid component is 100 mol%, and the total mole percent of the diol component is 100 mol%; and

其中，所述聚酯的比浓对数粘度是0.60-0.72dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和其中聚酯的Tg为95-115℃。Wherein, the inherent viscosity of the polyester is 0.60-0.72dL/g, as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25°C; And wherein the Tg of the polyester is 95-115°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，所述聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)1-99mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 1-99 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)1-98.99mol％的1，4-环己烷二甲醇残基，ii) 1-98.99 mol % of 1,4-cyclohexanedimethanol residues,

iii)0.01-小于15mol％乙二醇；iii) 0.01-less than 15mol% ethylene glycol;

其中二羧酸组分的总摩尔百分数是100mol％，和wherein the total mole percent of the dicarboxylic acid component is 100 mole percent, and

二醇组分的总摩尔百分数是100mol％；和The total mole percent of the diol component is 100 mole percent; and

其中比浓对数粘度是0.35-1.2dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和wherein the inherent viscosity is from 0.35 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C; and

其中聚酯的Tg为85-120℃。The Tg of the polyester is 85-120°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，所述聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)1-99mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 1-99 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)1-99mol％的1，4-环己烷二甲醇残基，ii) 1-99 mol % of 1,4-cyclohexanedimethanol residues,

其中二羧酸组分的总摩尔百分数是100mol％，和wherein the total mole percent of the dicarboxylic acid component is 100 mole percent, and

二醇组分的总摩尔百分数是100mol％；和The total mole percent of the diol component is 100 mole percent; and

其中比浓对数粘度是0.35-1.2dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和wherein the inherent viscosity is from 0.35 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C; and

其中聚酯的Tg为85-120℃；和任选地，其中在所述聚酯聚合之前或期间添加一种或多种支化剂。wherein the polyester has a Tg of 85-120°C; and optionally, wherein one or more branching agents are added before or during polymerization of said polyester.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，所述聚酯包含：In one aspect, the present invention relates to a film or sheet comprising a polyester composition comprising at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms;

(b)二醇组分，其包含：(b) a diol component comprising:

i)1-99mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 1-99 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)1-99mol％的1，4-环己烷二甲醇残基；和ii) 1-99 mol% of 1,4-cyclohexanedimethanol residues; and

(c)来自至少一种支化剂的残基；(c) residues from at least one branching agent;

其中二羧酸组分的总摩尔百分数是100mol％，和wherein the total mole percent of the dicarboxylic acid component is 100 mole percent, and

二醇组分的总摩尔百分数是100mol％；和The total mole percent of the diol component is 100 mole percent; and

其中比浓对数粘度是0.35-1.2dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和wherein the inherent viscosity is from 0.35 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C; and

其中聚酯的Tg为85-120℃。The Tg of the polyester is 85-120°C.

在一个方面中，本发明涉及一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含：In one aspect, the invention relates to a film or sheet comprising a polyester composition comprising:

至少一种聚酯，其包含：at least one polyester comprising:

(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:

i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;

ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b)二醇组分，其包含：(b) a diol component comprising:

i)1-99mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 1-99 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii)1-99mol％的1，4-环己烷二甲醇残基；和ii) 1-99 mol% of 1,4-cyclohexanedimethanol residues; and

至少一种热稳定剂或其反应产物；at least one heat stabilizer or reaction product thereof;

其中二羧酸组分的总摩尔百分数是100mol％，和wherein the total mole percent of the dicarboxylic acid component is 100 mole percent, and

二醇组分的总摩尔百分数是100mol％；和The total mole percent of the diol component is 100 mole percent; and

其中聚酯的比浓对数粘度为0.35-1.2dL/g，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的；和其中聚酯的Tg为85-135℃。wherein the polyester has an inherent viscosity of 0.35-1.2 dL/g, as determined at 25°C at a concentration of 0.5 g/100 ml in 60/40 (wt/wt) phenol/tetrachloroethane; and wherein the poly The Tg of the ester is 85-135°C.

在一个方面中，包含对本发明有用的聚酯组合物的薄膜和/或薄板包含至少一种聚碳酸酯。In one aspect, films and/or sheets comprising polyester compositions useful in the present invention comprise at least one polycarbonate.

在一个方面中，可用于本发明的薄膜和/或薄板的聚酯组合物不包含聚碳酸酯。In one aspect, polyester compositions useful in the films and/or sheets of the present invention do not comprise polycarbonate.

在一个方面中，可用于本发明的薄膜和/或薄板的聚酯包含小于15mol％乙二醇残基，例如0.01-小于15mol％乙二醇残基。In one aspect, the polyesters useful in the films and/or sheets of the invention comprise less than 15 mol% ethylene glycol residues, eg, from 0.01 to less than 15 mol% ethylene glycol residues.

在一个方面中，可用于本发明薄膜或者薄板的聚酯不包含乙二醇残基。In one aspect, the polyesters useful in the films or sheets of the present invention do not contain ethylene glycol residues.

在一个方面中，可用于本发明的薄膜或者薄板的聚酯组合物包含至少一种热稳定剂或其反应产物。In one aspect, the polyester composition useful in the film or sheet of the present invention comprises at least one thermal stabilizer or a reaction product thereof.

在一个方面中，可用于本发明薄膜或者薄板的聚酯组合物不包含支化剂，或者，在聚酯的聚合之前或者期间添加至少一种支化剂。In one aspect, the polyester compositions useful in the films or sheets of the present invention do not contain a branching agent, or, alternatively, at least one branching agent is added before or during the polymerization of the polyester.

在一个方面中，可用于本发明薄膜或者薄板的聚酯包含至少一种支化剂，而这与其中添加其的方法或顺序无关。In one aspect, the polyesters useful in the films or sheets of the present invention comprise at least one branching agent, regardless of the method or order in which they are added.

在一个方面中，可用于本发明薄膜或者薄板的聚酯组合物已经借助至少一种支化剂来制备，而这与其中添加其的方法或顺序无关。In one aspect, the polyester compositions useful in the films or sheets of the present invention have been prepared with at least one branching agent, regardless of the method or order in which they are added.

在一个方面中，可用于本发明薄膜或者薄板的聚酯不是由单独或者以组合形式的1，3-丙二醇或者1，4-丁二醇制成。在其它方面中，1，3-丙二醇或1，4-丁二醇，单独或者以组合形式地，可被用于制备本发明的聚酯。在本发明的一个方面中，可用于对本发明有用的某些聚酯中的顺-2，2，4，4-四甲基-1，3-环丁二醇的摩尔百分数是大于50mol％或者大于55mol％的顺-2，2，4，4-四甲基-1，3-环丁二醇或者大于70mol％的顺-2，2，4，4-四甲基-1，3-环丁二醇；其中顺-2，2，4，4-四甲基-1，3-环丁二醇和反-2，2，4，4-四甲基-1，3-环丁二醇的总摩尔百分数总共等于100mol％。In one aspect, the polyesters useful in the films or sheets of the present invention are not made from 1,3-propanediol or 1,4-butanediol alone or in combination. In other aspects, 1,3-propanediol or 1,4-butanediol, alone or in combination, can be used to prepare the polyesters of the invention. In one aspect of the invention, the mole percent of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol useful in certain polyesters useful in the invention is greater than 50 mole percent or More than 55 mol% of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or more than 70 mol% of cis-2,2,4,4-tetramethyl-1,3-cyclo Butanediol; of which cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol The total mole percentages equal 100 mol% in total.

在本发明的一个方面中，可用于对本发明有用的某些聚酯中的2，2，4，4-四甲基-1，3-环丁二醇的异构体的摩尔百分数为30-70mol％的顺-2，2，4，4-四甲基-1，3-环丁二醇或者30-70mol％的反-2，2，4，4-四甲基-1，3-环丁二醇，或者40-60mol％的顺-2，2，4，4-四甲基-1，3-环丁二醇或者40-60mol％的反-2，2，4，4-四甲基-1，3-环丁二醇，其中顺-2，2，4，4-四甲基-1，3-环丁二醇和反-2，2，4，4-四甲基-1，3-环丁二醇的总摩尔百分数总共等于100mol％。In one aspect of the invention, the mole percent of isomers of 2,2,4,4-tetramethyl-1,3-cyclobutanediol that can be used in certain polyesters useful for the invention ranges from 30 to 70mol% cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or 30-70mol% trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol Butanediol, or 40-60mol% cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or 40-60mol% trans-2,2,4,4-tetramethyl Base-1,3-cyclobutanediol, wherein cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1, The total mole percent of 3-cyclobutanediol amounts to 100 mole percent.

此外，在一个方面中，在某些本发明的薄膜或者薄板中使用这些特定的聚酯组合物最小化和/或消除了在熔融加工和/或热成形之前的干燥步骤。Additionally, in one aspect, use of these specific polyester compositions in certain inventive films or sheets minimizes and/or eliminates drying steps prior to melt processing and/or thermoforming.

在一个方面中，可用于本发明的薄膜或者薄板的聚酯组合物可以以薄膜和/或薄板的各种型式使用，包括但不限于挤塑薄膜和/或薄板、压延薄膜和/或薄板、压塑薄膜和/或薄板、溶液铸塑薄膜和/或薄板。制造薄膜和/或薄板的方法包括但不限于挤塑、压延、压塑和溶液铸塑。In one aspect, the polyester compositions useful in the films or sheets of the present invention can be used in various forms of film and/or sheet, including but not limited to extruded film and/or sheet, calendered film and/or sheet, Compression molded film and/or sheet, solution cast film and/or sheet. Methods of making films and/or sheets include, but are not limited to, extrusion, calendering, compression molding, and solution casting.

在一个方面中，可用于本发明薄膜或者薄板的聚酯可以是无定形的或半结晶的。在一个方面中，对本发明有用的某些聚酯可能具有较低的结晶度。对本发明有用的某些聚酯因而可能具有基本上无定形的形态，意味着聚酯包括聚合物的基本上无序区域。In one aspect, the polyesters useful in the films or sheets of the present invention can be amorphous or semi-crystalline. In one aspect, certain polyesters useful in the present invention may have lower crystallinity. Certain polyesters useful in the present invention may thus have a substantially amorphous morphology, meaning that the polyester comprises substantially disordered regions of the polymer.

附图说明Description of drawings

图1是显示共聚单体对改性PCT共聚酯的最快结晶半衰期的影响的图。Figure 1 is a graph showing the effect of comonomers on the fastest crystallization half-life of modified PCT copolyesters.

图2是显示在缺口冲击试验(ASTM D256，1/8英寸厚，10密耳切口)中共聚单体对韧脆性转变温度(T_bd)的影响的图。Figure 2 is a graph showing the effect of comonomer on the ductile-brittle transition temperature (T_bd ) in a notched impact test (ASTM D256, 1/8 inch thick, 10 mil notch).

图3是显示2，2，4，4-四甲基-1，3-环丁二醇组成对共聚酯的玻璃化转变温度(Tg)的影响的图。Figure 3 is a graph showing the effect of 2,2,4,4-tetramethyl-1,3-cyclobutanediol composition on the glass transition temperature (Tg) of copolyesters.

发明的详细说明Detailed Description of the Invention

通过参考下面本发明的某些实施方案的详细说明和工作实施例可以更容易地理解本发明。根据本发明的目的，本发明的某些实施方案描述于发明内容中并且进一步在下文中进行描述。同样，本文中描述了本发明的其它实施方案。The present invention may be understood more readily by reference to the following detailed description and working examples of certain embodiments of the invention. For purposes of the present invention, certain embodiments of the invention are described in the Summary of the Invention and further described below. Likewise, other embodiments of the invention are described herein.

据信本文中所述的可用于本发明薄膜或者薄板的聚酯可以具有例如以下的两种或更多种物理性能的结合：高冲击强度、适度的玻璃化转变温度、耐化学性、水解稳定性、韧性、低韧脆性转变温度、良好的颜色和透明性、低密度、长结晶半衰期和良好的加工性能，由此使其易于成形为薄膜或者薄板。在对本发明有用的一些实施方案中，聚酯具有良好的冲击强度、耐热性、耐化学性、密度的独特的性能的组合和/或良好的冲击强度、耐热性和加工性能的性能的组合和/或所述性能的两种或多种的组合，这些以前未被考虑存在于包含至少一种聚酯的薄膜或者薄板中。It is believed that the polyesters described herein useful in the films or sheets of the present invention may have a combination of two or more of the following physical properties, for example: high impact strength, moderate glass transition temperature, chemical resistance, hydrolytic stability properties, toughness, low ductile-brittle transition temperature, good color and transparency, low density, long crystallization half-life and good processability, thus making it easy to form into film or sheet. In some embodiments useful for the present invention, the polyester has a unique combination of properties of good impact strength, heat resistance, chemical resistance, density and/or the properties of good impact strength, heat resistance and processability Combinations and/or combinations of two or more of said properties, which have not been considered before in films or sheets comprising at least one polyester.

如本文中使用的，术语“聚酯”意图包括“共聚酯”并且应理解为是指通过一种或多种双官能羧酸和/或多官能羧酸与一种或多种双官能羟基化合物和/或多官能羟基化合物的反应而制备的合成聚合物。通常，双官能羧酸可以是二羧酸，而双官能羟基化合物可以是二元醇，例如二醇(glycol)和二醇(diol)。如本申请中使用的，术语“二醇”包括但不限于二醇、二醇和/或多官能羟基化合物，例如支化剂。或者，双官能羧酸可以是羟基羧酸，例如对羟基苯甲酸，而双官能羟基化合物可能是带有2个羟基取代基的芳基核，例如氢醌。如本文中使用的，术语“残基”是指由相应单体通过缩聚和/或酯化反应引入到聚合物的任何有机结构。如本文中使用的，术语“重复单元”是指具有通过羰氧基基团键合的二羧酸残基和二醇残基的有机结构。因此，例如，二羧酸残基可以衍生自二羧酸单体或其相关的酰卤、酯、盐、酸酐或其混合物。因此，如本文中使用的，术语二羧酸意图包括二羧酸和二羧酸的任何衍生物，包括其相关的酰卤、酯、半酯、盐、半盐、酸酐、混合酸酐或其混合物，它们可用于与二醇的反应过程以制备聚酯。此外，如本申请中使用的，术语“二酸”包括多官能酸，如支化剂。如本文中使用的，术语“对苯二甲酸”意图包括对苯二甲酸本身和其残基以及对苯二甲酸的任何衍生物，包括其相关的酰卤、酯、半酯、盐、半盐、酸酐、混合酸酐或其混合物或其残基，它们可用于与二醇的反应过程以制备聚酯。As used herein, the term "polyester" is intended to include "copolyesters" and is understood to mean that the polyfunctional carboxylic acid(s) formed by one or more difunctional carboxylic acids and/or polyfunctional carboxylic acids with one or more difunctional hydroxyl groups Synthetic polymers prepared by the reaction of compounds and/or polyfunctional hydroxyl compounds. Generally, the difunctional carboxylic acid may be a dicarboxylic acid, and the difunctional hydroxy compound may be a dihydric alcohol, such as glycol and diol. As used in this application, the term "diol" includes, but is not limited to, diols, diols, and/or polyfunctional hydroxyl compounds, such as branching agents. Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid, such as p-hydroxybenzoic acid, and the difunctional hydroxy compound may be an aryl core with 2 hydroxyl substituents, such as hydroquinone. As used herein, the term "residue" refers to any organic structure introduced into a polymer by polycondensation and/or esterification reactions from corresponding monomers. As used herein, the term "repeating unit" refers to an organic structure having a dicarboxylic acid residue and a diol residue bonded through a carbonyloxy group. Thus, for example, a dicarboxylic acid residue may be derived from a dicarboxylic acid monomer or its related halides, esters, salts, anhydrides or mixtures thereof. Thus, as used herein, the term dicarboxylic acid is intended to include dicarboxylic acids and any derivatives of dicarboxylic acids, including their related halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof , they can be used in the reaction process with diols to prepare polyesters. Furthermore, as used in this application, the term "diacid" includes polyfunctional acids, such as branching agents. As used herein, the term "terephthalic acid" is intended to include terephthalic acid itself and its residues as well as any derivatives of terephthalic acid, including its related halides, esters, half-esters, salts, half-salts , anhydrides, mixed anhydrides or mixtures thereof or their residues, which can be used in the reaction process with diols to prepare polyesters.

在一种实施方案中，对苯二甲酸可以用作起始材料。在另一实施方案中，对苯二甲酸二甲酯可以用作起始材料。在又一实施方案中，对苯二甲酸和对苯二甲酸二甲酯的混合物可以用作起始材料和/或中间材料。In one embodiment, terephthalic acid can be used as a starting material. In another embodiment, dimethyl terephthalate can be used as a starting material. In yet another embodiment, a mixture of terephthalic acid and dimethyl terephthalate can be used as starting material and/or intermediate material.

用于本发明的薄膜或者薄板中的聚酯通常可以由基本上等比例反应并且引入到聚酯聚合物中作为它们的相应残基的二羧酸和二醇制备。因此，可用于本发明的聚酯可以包含基本上等摩尔比的酸残基(100mol％)和二醇(和/或多官能羟基混合物)残基(100mol％)，使得重复单元的总摩尔数等于100mol％。因此，本公开内容中提供的摩尔百分比可以基于酸残基的总摩尔数、二醇残基的总摩尔数或重复单元的总摩尔数。例如，基于总酸残基，含30mol％间苯二甲酸的聚酯，是指在总共100mol％酸残基中，聚酯包含30mol％间苯二甲酸残基。因此，在每100mol酸残基中，存在30mol间苯二甲酸残基。在另一实例中，基于总二醇残基，含30mol％2，2，4，4-四甲基-1，3-环丁二醇的聚酯，是指在总共100mol％二醇残基中，聚酯包含30mol％2，2，4，4-四甲基-1，3-环丁二醇残基。因此，在每100mol二醇残基中，存在30mol的2，2，4，4-四甲基-1，3-环丁二醇残基。The polyesters used in the films or sheets of the present invention can generally be prepared from dicarboxylic acids and diols reacted in substantially equal proportions and incorporated into the polyester polymer as their corresponding residues. Accordingly, polyesters useful in the present invention may comprise substantially equimolar ratios of acid residues (100 mol%) and diol (and/or polyfunctional hydroxyl mixture) residues (100 mol%) such that the total number of moles of repeating units Equal to 100 mol%. Accordingly, the mole percentages provided in this disclosure may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeat units. For example, a polyester containing 30 mole percent isophthalic acid based on total acid residues means that the polyester contains 30 mole percent isophthalic acid residues out of a total of 100 mole percent acid residues. Thus, for every 100 moles of acid residues, there are 30 moles of isophthalic acid residues. In another example, a polyester containing 30 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol, based on total diol residues, means that in a total of 100 mol% diol residues In, the polyester contains 30 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. Thus, for every 100 mol of diol residues, there are 30 mol of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

在本发明的其它方面中，可用于本发明薄膜或者薄板的聚酯的Tg可以是以下范围中的至少一个：85-200℃；85-190℃；85-180℃；85-170℃；85-160℃；85-155℃；85-150℃；85-145℃；85-140℃；85-138℃；85-135℃；85-130℃；85-125℃；85-120℃；85-115℃；85-110℃；85-105℃；85-100℃；85-95℃；85-90℃；90-200℃；90-190℃；90-180℃；90-170℃；90-160℃；90-155℃；90-150℃；90-145℃；90-140℃；90-138℃；90-135℃；90-130℃；90-125℃；90-120℃；90-115℃；90-110℃；90-105℃；90-100℃；90-95℃；95-200℃；95-190℃；95-180℃；95-170℃；95-160℃；95-155℃；95-150℃；95-145℃；95-140℃；95-138℃；95-135℃；95-130℃；95-125℃；95-120℃；95-115℃；95-110℃；95-105℃；95-小于105℃；95-100℃；100-200℃；100-190℃；100-180℃；100-170℃；100-160℃；100-155℃；100-150℃；100-145℃；100-140℃；100-138℃；100-135℃；100-130℃；100-125℃；100-120℃；100-115℃；100-110℃；105-200℃；105-190℃；105-180℃；105-170℃；105-160℃；105-155℃；105-150℃；105-145℃；105-140℃；105-138℃；105-135℃；105-130℃；105-125℃；105-120℃；105-115℃；105-110℃；大于105-125℃；大于105-120℃；大于105-115℃；大于105-110℃；110-200℃；110-190℃；110-180℃；110-170℃；110-160℃；110-155℃；110-150℃；110-145℃；110-140℃；110-138℃；110-135℃；110-130℃；110-125℃；110-120℃；110-115℃；115-200℃；115-190℃；115-180℃；115-170℃；115-160℃；115-155℃；115-150℃；115-145℃；115-140℃；115-138℃；115-135℃；110-130℃；115-125℃；115-120℃；120-200℃；120-190℃；120-180℃；120-170℃；120-160℃；120-155℃；120-150℃；120-145℃；120-140℃；120-138℃；120-135℃；120-130℃；125-200℃；125-190℃；125-180℃；125-170℃；125-160℃；125-155℃；125-150℃；125-145℃；125-140℃；125-138℃；125-135℃；127-200℃；127-190℃；127-180℃；127-170℃；127-160℃；127-150℃；127-145℃；127-140℃；127-138℃；127-135℃；130-200℃；130-190℃；130-180℃；130-170℃；130-160℃；130-155℃；130-150℃；130-145℃；130-140℃；130-138℃；130-135℃；135-200℃；135-190℃；135-180℃；135-170℃；135-160℃；135-155℃；135-150℃；135-145℃；135-140℃；140-200℃；140-190℃；140-180℃；140-170℃；140-160℃；140-155℃；140-150℃；140-145℃；148-200℃；148-190℃；148-180℃；148-170℃；148-160℃；148-155℃；148-150℃；150-200℃；150-190℃；150-180℃；150-170℃；150-160；155-190℃；155-180℃；155-170℃；和155-165℃。In other aspects of the present invention, the Tg of the polyester useful in the film or sheet of the present invention may be at least one of the following ranges: 85-200°C; 85-190°C; 85-180°C; 85-170°C; 85 -160°C; 85-155°C; 85-150°C; 85-145°C; 85-140°C; 85-138°C; 85-135°C; -115°C; 85-110°C; 85-105°C; 85-100°C; 85-95°C; 85-90°C; 90-200°C; 90-190°C; -160°C; 90-155°C; 90-150°C; 90-145°C; 90-140°C; 90-138°C; 90-135°C; -115°C; 90-110°C; 90-105°C; 90-100°C; 90-95°C; 95-200°C; 95-190°C; 95-180°C; -155°C; 95-150°C; 95-145°C; 95-140°C; 95-138°C; 95-135°C; 95-130°C; -110°C; 95-105°C; 95-less than 105°C; 95-100°C; 100-200°C; 100-190°C; 100-180°C; 100-170°C; 100-150℃; 100-145℃; 100-140℃; 100-138℃; 100-135℃; 100-130℃; 100-125℃; 100-120℃; 105-200℃; 105-190℃; 105-180℃; 105-170℃; 105-160℃; 105-155℃; 105-150℃; 105-145℃; 105-135°C; 105-130°C; 105-125°C; 105-120°C; 105-115°C; -110℃; 110-200℃; 110-190℃; 110-180℃; 110-170℃; 110-160℃; 110-155℃; 110-150℃; -138°C; 110-135°C; 110-130°C; 110-125°C; 110-120°C; 110-115°C; 115-200°C; 115-170℃; 115-160℃; 115-155℃; 115-150℃; 115-145℃; 115-140℃; 115-138℃; 115-135℃; 115-120℃; 120-200℃; 120-190℃; 120-180℃; 120-170℃; 120-160℃; 120-155℃; 120-150℃; 120-138℃; 120-135℃; 120-130℃; 125-200℃; 125-190℃; 125-180℃; 125-170℃; 125-160℃; 125-145℃; 125-140℃; 125-138℃; 125-135℃; 127-200℃; 127-190℃; 127-180℃; 127-170℃; 127-145℃; 127-140℃; 127-138℃; 127-135℃; 130-200℃; 130-190℃; 130-180℃; 130-170℃; 130-150℃; 130-145℃; 130-140℃; 130-138℃; 130-135℃; 135-200℃; 135-190℃; 135-180℃; 135-155℃; 135-150℃; 135-145℃; 135-140℃; 140-200℃; 140-190℃; 140-180℃; 140-170℃; 140-150℃; 140-145℃; 148-200℃; 148-190℃; 148-180℃; 148-170℃; 148-160℃; 148-155℃; 150-190°C; 150-180°C; 150-170°C; 150-160; 155-190°C; 155-180°C;

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：1-99mol％2，2，4，4-四甲基-1，3-环丁二醇和1-99mol％1，4-环己烷二甲醇；1-95mol％2，2，4，4-四甲基-1，3-环丁二醇和5-99mol％1，4-环己烷二甲醇；1-90mol％2，2，4，4-四甲基-1，3-环丁二醇和10-99mol％1，4-环己烷二甲醇；1-85mol％2，2，4，4-四甲基-1，3-环丁二醇和15-99mol％1，4-环己烷二甲醇；1-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-99mol％1，4-环己烷二甲醇，1-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-99mol％1，4-环己烷二甲醇；1-70mol％2，2，4，4-四甲基-1，3-环丁二醇和30-99mol％1，4-环己烷二甲醇；1-65mol％2，2，4，4-四甲基-1，3-环丁二醇和35-99mol％1，4-环己烷二甲醇；1-60mol％2，2，4，4-四甲基-1，3-环丁二醇和40-99mol％1，4-环己烷二甲醇；1-55mol％2，2，4，4-四甲基-1，3-环丁二醇和45-99mol％1，4-环己烷二甲醇；1-50mol％2，2，4，4-四甲基-1，3-环丁二醇和50-99mol％1，4-环己烷二甲醇；1-45mol％2，2，4，4-四甲基-1，3-环丁二醇和55-99mol％1，4-环己烷二甲醇；1-40mol％2，2，4，4-四甲基-1，3-环丁二醇和60-99mol％1，4-环己烷二甲醇；1-35mol％2，2，4，4-四甲基-1，3-环丁二醇和65-99mol％1，4-环己烷二甲醇；1-30mol％2，2，4，4-四甲基-1，3-环丁二醇和70-99mol％1，4-环己烷二甲醇；1-25mol％2，2，4，4-四甲基-1，3-环丁二醇和75-99mol％1，4-环己烷二甲醇；1-20mol％2，2，4，4-四甲基-1，3-环丁二醇和80-99mol％1，4-环己烷二甲醇；1-15mol％2，2，4，4-四甲基-1，3-环丁二醇和85-99mol％1，4-环己烷二甲醇；1-10mol％2，2，4，4-四甲基-1，3-环丁二醇和90-99mol％1，4-环己烷二甲醇；1-小于10mol％2，2，4，4-四甲基-1，3-环丁二醇和大于90-99mol％1，4-环己烷二甲醇；1-9mol％2，2，4，4-四甲基-1，3-环丁二醇和91-99mol％1，4-环己烷二甲醇；1-8mol％2，2，4，4-四甲基-1，3-环丁二醇和92-99mol％1，4-环己烷二甲醇；1-7mol％2，2，4，4-四甲基-1，3-环丁二醇和93-99mol％1，4-环己烷二甲醇；1-6mol％2，2，4，4-四甲基-1，3-环丁二醇和94-99mol％1，4-环己烷二甲醇；和1-5mol％2，2，4，4-四甲基-1，3-环丁二醇和95-99mol％1，4-环己烷二甲醇；1-小于5mol％2，2，4，4-四甲基-1，3-环丁二醇和大于90-99mol％1，4-环己烷二甲醇；大于0.01-10mol％2，2，4，4-四甲基-1，3-环丁二醇和90-小于99.99mol％1，4-环己烷二甲醇；和大于0.01-5mol％2，2，4，4-四甲基-1，3-环丁二醇和95-小于99.99mol％1，4-环己烷二甲醇。In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 1-99mol% 2,2,4,4-Tetra Methyl-1,3-cyclobutanediol and 1-99mol% 1,4-cyclohexanedimethanol; 1-95mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 -99mol% 1,4-cyclohexanedimethanol; 1-90mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-99mol% 1,4-cyclohexanedimethanol ; 1-85mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-99mol% 1,4-cyclohexanedimethanol; 1-80mol% 2,2,4,4 -Tetramethyl-1,3-cyclobutanediol and 20-99mol% 1,4-cyclohexanedimethanol, 1-75mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol Alcohol and 25-99mol% 1,4-cyclohexanedimethanol; 1-70mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-99mol% 1,4-cyclohexane Dimethanol; 1-65mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-99mol% 1,4-cyclohexanedimethanol; 1-60mol% 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol and 40-99mol% 1,4-cyclohexanedimethanol; 1-55mol% 2,2,4,4-tetramethyl-1,3-cyclo Butanediol and 45-99mol% 1,4-cyclohexanedimethanol; 1-50mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-99mol% 1,4-cyclohexane Hexanedimethanol; 1-45mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-99mol% 1,4-cyclohexanedimethanol; 1-40mol% 2,2 , 4,4-tetramethyl-1,3-cyclobutanediol and 60-99mol% 1,4-cyclohexanedimethanol; 1-35mol% 2,2,4,4-tetramethyl-1,3 - cyclobutanediol and 65-99mol% 1,4-cyclohexanedimethanol; 1-30mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-99mol% 1,4 - cyclohexanedimethanol; 1-25mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-99mol% 1,4-cyclohexanedimethanol; 1-20mol% 2 , 2,4,4-tetramethyl-1,3-cyclobutanediol and 80-99mol% 1,4-cyclohexanedimethanol; 1-15mol% 2,2,4,4-tetramethyl-1 , 3-cyclobutanediol and 85-99mol% 1,4-cyclohexanedimethanol; 1-10mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 90-99mol% 1 , 4-cyclohexanedimethanol; 1-less than 10mol% 2,2,4,4-tetra Methyl-1,3-cyclobutanediol and greater than 90-99mol% 1,4-cyclohexanedimethanol; 1-9mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 91-99mol% 1,4-cyclohexanedimethanol; 1-8mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 92-99mol% 1,4-cyclohexanedimethanol Methanol; 1-7mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 93-99mol% 1,4-cyclohexanedimethanol; 1-6mol% 2,2,4, 4-tetramethyl-1,3-cyclobutanediol and 94-99 mol% 1,4-cyclohexanedimethanol; and 1-5 mol% 2,2,4,4-tetramethyl-1,3-cyclo Butanediol and 95-99mol% 1,4-cyclohexanedimethanol; 1-less than 5mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 90-99mol% 1,4 - cyclohexanedimethanol; greater than 0.01-10 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 90-less than 99.99 mol% 1,4-cyclohexanedimethanol; and greater than 0.01-5 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 95-less than 99.99 mol% 1,4-cyclohexanedimethanol.

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：5-小于50mol％2，2，4，4-四甲基-1，3-环丁二醇和大于50-95mol％1，4-环己烷二甲醇；5-45mol％2，2，4，4-四甲基-1，3-环丁二醇和55-95mol％1，4-环己烷二甲醇；5-40mol％2，2，4，4-四甲基-1，3-环丁二醇和60-95mol％1，4-环己烷二甲醇；5-35mol％2，2，4，4-四甲基-1，3-环丁二醇和65-95mol％1，4-环己烷二甲醇；5-小于35mol％2，2，4，4-四甲基-1，3-环丁二醇和大于65-95mol％1，4-环己烷二甲醇；5-30mol％2，2，4，4-四甲基-1，3-环丁二醇和70-95mol％1，4-环己烷二甲醇；5-25mol％2，2，4，4-四甲基-1，3-环丁二醇和75-95mol％1，4-环己烷二甲醇；5-20mol％2，2，4，4-四甲基-1，3-环丁二醇和80-95mol％1，4-环己烷二甲醇；5-15mol％2，2，4，4-四甲基-1，3-环丁二醇和85-95mol％1，4-环己烷二甲醇；5-10mol％2，2，4，4-四甲基-1，3-环丁二醇和75-90mol％1，4-环己烷二甲醇；10-小于50mol％2，2，4，4-四甲基-1，3-环丁二醇和大于50-90mol％1，4-环己烷二甲醇；10-45mol％2，2，4，4-四甲基-1，3-环丁二醇和55-90mol％1，4-环己烷二甲醇；10-40mol％2，2，4，4-四甲基-1，3-环丁二醇和60-90mol％1，4-环己烷二甲醇；10-35mol％2，2，4，4-四甲基-1，3-环丁二醇和65-90mol％1，4-环己烷二甲醇；10-小于35mol％2，2，4，4-四甲基-1，3-环丁二醇和大于65-至多90mol％1，4-环己烷二甲醇；10-30mol％2，2，4，4-四甲基-1，3-环丁二醇和70-90mol％1，4-环己烷二甲醇；10-25mol％2，2，4，4-四甲基-1，3-环丁二醇和大于75-90mol％1，4-环己烷二甲醇；14-小于50mol％2，2，4，4-四甲基-1，3-环丁二醇和大于50-至多86mol％1，4-环己烷二甲醇；14-45mol％2，2，4，4-四甲基-1，3-环丁二醇和55-86mol％1，4-环己烷二甲醇；14-40mol％2，2，4，4-四甲基-1，3-环丁二醇和60-86mol％1，4-环己烷二甲醇；14-35mol％2，2，4，4-四甲基-1，3-环丁二醇和65-86mol％1，4-环己烷二甲醇；14-30mol％2，2，4，4-四甲基-1，3-环丁二醇和70-86mol％1，4-环己烷二甲醇；14-25mol％2，2，4，4-四甲基-1，3-环丁二醇和75-86mol％1，4-环己烷二甲醇；1 5-小于50mol％2，2，4，4-四甲基-1，3-环丁二醇和大于50-至多85mol％1，4-环己烷二甲醇；15-45mol％2，2，4，4-四甲基-1，3-环丁二醇和55-85mol％1，4-环己烷二甲醇；15-40mol％2，2，4，4-四甲基-1，3-环丁二醇和60-85mol％1，4-环己烷二甲醇；15-35mol％2，2，4，4-四甲基-1，3-环丁二醇和65-85mol％1，4-环己烷二甲醇；15-30mol％2，2，4，4-四甲基-1，3-环丁二醇和70-85mol％1，4-环己烷二甲醇；15-25mol％2，2，4，4-四甲基-1，3-环丁二醇和75-85mol％1，4-环己烷二甲醇；和17-23mol％2，2，4，4-四甲基-1，3-环丁二醇和77-83mol％1，4-环己烷二甲醇。In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 5-less than 50mol% 2,2,4,4- Tetramethyl-1,3-cyclobutanediol and greater than 50-95mol% 1,4-cyclohexanedimethanol; 5-45mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol Alcohol and 55-95mol% 1,4-cyclohexanedimethanol; 5-40mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-95mol% 1,4-cyclohexane Dimethanol; 5-35mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-95mol% 1,4-cyclohexanedimethanol; 5-less than 35mol% 2,2, 4,4-tetramethyl-1,3-cyclobutanediol and greater than 65-95mol% 1,4-cyclohexanedimethanol; 5-30mol% 2,2,4,4-tetramethyl-1,3 - cyclobutanediol and 70-95mol% 1,4-cyclohexanedimethanol; 5-25mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-95mol% 1,4 - cyclohexanedimethanol; 5-20mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-95mol% 1,4-cyclohexanedimethanol; 5-15mol% 2 , 2,4,4-tetramethyl-1,3-cyclobutanediol and 85-95mol% 1,4-cyclohexanedimethanol; 5-10mol% 2,2,4,4-tetramethyl-1 , 3-cyclobutanediol and 75-90mol% 1,4-cyclohexanedimethanol; 10-less than 50mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-90mol % 1,4-cyclohexanedimethanol; 10-45mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-90mol% 1,4-cyclohexanedimethanol; 10 -40mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-90mol% 1,4-cyclohexanedimethanol; 10-35mol% 2,2,4,4-tetramethyl Methyl-1,3-cyclobutanediol and 65-90mol% 1,4-cyclohexanedimethanol; 10-less than 35mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and Greater than 65-up to 90 mol% 1,4-cyclohexanedimethanol; 10-30 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-90 mol% 1,4-cyclohexane Alkanedimethanol; 10-25mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 75-90mol% 1,4-cyclohexanedimethanol; 14-less than 50mol% 2, 2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-up to 86 mol% 1,4-cyclohexanedimethanol; 14-45 mol% 2,2,4,4-tetramethyl- 1,3-Cyclobutanediol and 55 -86mol% 1,4-cyclohexanedimethanol; 14-40mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-86mol% 1,4-cyclohexanedimethanol ; 14-35mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-86mol% 1,4-cyclohexanedimethanol; 14-30mol% 2,2,4,4 -Tetramethyl-1,3-cyclobutanediol and 70-86mol% 1,4-cyclohexanedimethanol; 14-25mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol Alcohol and 75-86mol% 1,4-cyclohexanedimethanol; 1 5-less than 50mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-up to 85mol% 1,4 - Cyclohexanedimethanol; 15-45mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-85mol% 1,4-cyclohexanedimethanol; 15-40mol% 2 , 2,4,4-tetramethyl-1,3-cyclobutanediol and 60-85mol% 1,4-cyclohexanedimethanol; 15-35mol% 2,2,4,4-tetramethyl-1 , 3-cyclobutanediol and 65-85mol% 1,4-cyclohexanedimethanol; 15-30mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-85mol% 1 , 4-cyclohexanedimethanol; 15-25mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-85mol% 1,4-cyclohexanedimethanol; and 17- 23 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 77-83 mol% 1,4-cyclohexanedimethanol.

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：11-99mol％2，2，4，4-四甲基-1，3-环丁二醇和1-89mol％1，4-环己烷二甲醇；11-95mol％2，2，4，4-四甲基-1，3-环丁二醇和5-89mol％1，4-环己烷二甲醇；11-90mol％2，2，4，4-四甲基-1，3-环丁二醇和10-89mol％1，4-环己烷二甲醇；11-85mol％2，2，4，4-四甲基-1，3-环丁二醇和15-89mol％1，4-环己烷二甲醇；11-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-89mol％1，4-环己烷二甲醇，11-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-89mol％1，4-环己烷二甲醇；11-70mol％2，2，4，4-四甲基-1，3-环丁二醇和30-89mol％1，4-环己烷二甲醇；11-65mol％2，2，4，4-四甲基-1，3-环丁二醇和35-89mol％1，4-环己烷二甲醇；11-60mol％2，2，4，4-四甲基-1，3-环丁二醇和40-89mol％1，4-环己烷二甲醇；11-55mol％2，2，4，4-四甲基-1，3-环丁二醇和45-89mol％1，4-环己烷二甲醇；和11-50mol％2，2，4，4-四甲基-1，3-环丁二醇和50-89mol％1，4-环己烷二甲醇。In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 11-99mol% 2,2,4,4-Tetra Methyl-1,3-cyclobutanediol and 1-89mol% 1,4-cyclohexanedimethanol; 11-95mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 -89mol% 1,4-cyclohexanedimethanol; 11-90mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-89mol% 1,4-cyclohexanedimethanol ; 11-85mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-89mol% 1,4-cyclohexanedimethanol; 11-80mol% 2,2,4,4 -Tetramethyl-1,3-cyclobutanediol and 20-89mol% 1,4-cyclohexanedimethanol, 11-75mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol Alcohol and 25-89mol% 1,4-cyclohexanedimethanol; 11-70mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-89mol% 1,4-cyclohexane Dimethanol; 11-65mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-89mol% 1,4-cyclohexanedimethanol; 11-60mol% 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol and 40-89mol% 1,4-cyclohexanedimethanol; 11-55mol% 2,2,4,4-tetramethyl-1,3-cyclo Butanediol and 45-89mol% 1,4-cyclohexanedimethanol; and 11-50mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-89mol% 1,4- Cyclohexanedimethanol.

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：11-小于50mol％2，2，4，4-四甲基-1，3-环丁二醇和大于50-至多89mol％1，4-环己烷二甲醇；11-45mol％2，2，4，4-四甲基-1，3-环丁二醇和55-89mol％1，4-环己烷二甲醇；11-40mol％2，2，4，4-四甲基-1，3-环丁二醇和60-89mol％1，4-环己烷二甲醇；11-35mol％2，2，4，4-四甲基-1，3-环丁二醇和65-89mol％1，4-环己烷二甲醇；11-30mol％2，2，4，4-四甲基-1，3-环丁二醇和70-89mol％1，4-环己烷二甲醇；11-25mol％2，2，4，4-四甲基-1，3-环丁二醇和75-89mol％1，4-环己烷二甲醇；11-20mol％2，2，4，4-四甲基-1，3-环丁二醇和80-89mol％1，4-环己烷二甲醇，和11-15mol％2，2，4，4-四甲基-1，3-环丁二醇和80-85mol％1，4-环己烷二甲醇。In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 11-less than 50mol% 2,2,4,4- Tetramethyl-1,3-cyclobutanediol and greater than 50-up to 89 mol% 1,4-cyclohexanedimethanol; 11-45 mol% 2,2,4,4-tetramethyl-1,3-cyclobutane Diol and 55-89mol% 1,4-cyclohexanedimethanol; 11-40mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-89mol% 1,4-cyclohexane Alkanedimethanol; 11-35mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-89mol% 1,4-cyclohexanedimethanol; 11-30mol% 2,2, 4,4-tetramethyl-1,3-cyclobutanediol and 70-89mol% 1,4-cyclohexanedimethanol; 11-25mol% 2,2,4,4-tetramethyl-1,3- Cyclobutanediol and 75-89mol% 1,4-cyclohexanedimethanol; 11-20mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-89mol% 1,4- Cyclohexanedimethanol, and 11-15 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-85 mol% 1,4-cyclohexanedimethanol.

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：12-99mol％2，2，4，4-四甲基-1，3-环丁二醇和1-86mol％1，4-环己烷二甲醇；12-95mol％2，2，4，4-四甲基-1，3-环丁二醇和5-88mol％1，4-环己烷二甲醇；12-90mol％2，2，4，4-四甲基-1，3-环丁二醇和10-88mol％1，4-环己烷二甲醇；12-85mol％2，2，4，4-四甲基-1，3-环丁二醇和15-88mol％1，4-环己烷二甲醇；12-86mol％2，2，4，4-四甲基-1，3-环丁二醇和14-88mol％1，4-环己烷二甲醇，12-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-88mol％1，4-环己烷二甲醇；12-70mol％2，2，4，4-四甲基-1，3-环丁二醇和30-88mol％1，4-环己烷二甲醇；12-65mol％2，2，4，4-四甲基-1，3-环丁二醇和35-88mol％1，4-环己烷二甲醇；12-60mol％2，2，4，4-四甲基-1，3-环丁二醇和40-88mol％1，4-环己烷二甲醇；12-55mol％2，2，4，4-四甲基-1，3-环丁二醇和45-88mol％1，4-环己烷二甲醇；和12-50mol％2，2，4，4-四甲基-1，3-环丁二醇和50-88mol％1，4-环己烷二甲醇；In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 12-99mol% 2,2,4,4-Tetra Methyl-1,3-cyclobutanediol and 1-86mol% 1,4-cyclohexanedimethanol; 12-95mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 -88mol% 1,4-cyclohexanedimethanol; 12-90mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-88mol% 1,4-cyclohexanedimethanol ; 12-85mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-88mol% 1,4-cyclohexanedimethanol; 12-86mol% 2,2,4,4 -Tetramethyl-1,3-cyclobutanediol and 14-88mol% 1,4-cyclohexanedimethanol, 12-75mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol Alcohol and 25-88mol% 1,4-cyclohexanedimethanol; 12-70mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-88mol% 1,4-cyclohexane Dimethanol; 12-65mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-88mol% 1,4-cyclohexanedimethanol; 12-60mol% 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol and 40-88mol% 1,4-cyclohexanedimethanol; 12-55mol% 2,2,4,4-tetramethyl-1,3-cyclo Butanediol and 45-88mol% 1,4-cyclohexanedimethanol; and 12-50mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-88mol% 1,4- Cyclohexanedimethanol;

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：12-小于50mol％2，2，4，4-四甲基-1，3-环丁二醇和大于50-至多88mol％1，4-环己烷二甲醇；12-45mol％2，2，4，4-四甲基-1，3-环丁二醇和55-88mol％1，4-环己烷二甲醇；12-40mol％2，2，4，4-四甲基-1，3-环丁二醇和60-88mol％1，4-环己烷二甲醇；12-35mol％2，2，4，4-四甲基-1，3-环丁二醇和65-88mol％1，4-环己烷二甲醇；12-30mol％2，2，4，4-四甲基-1，3-环丁二醇和70-88mol％1，4-环己烷二甲醇；12-25mol％2，2，4，4-四甲基-1，3-环丁二醇和75-88mol％1，4-环己烷二甲醇；12-20mol％2，2，4，4-四甲基-1，3-环丁二醇和80-88mol％1，4-环己烷二甲醇，和12-15mol％2，2，4，4-四甲基-1，3-环丁二醇；和85-88mol％1，4-环己烷二甲醇。In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 12-less than 50mol% 2,2,4,4- Tetramethyl-1,3-cyclobutanediol and greater than 50-up to 88 mol% 1,4-cyclohexanedimethanol; 12-45 mol% 2,2,4,4-tetramethyl-1,3-cyclobutane Diol and 55-88mol% 1,4-cyclohexanedimethanol; 12-40mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-88mol% 1,4-cyclohexane Alkanedimethanol; 12-35mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-88mol% 1,4-cyclohexanedimethanol; 12-30mol% 2,2, 4,4-tetramethyl-1,3-cyclobutanediol and 70-88mol% 1,4-cyclohexanedimethanol; 12-25mol% 2,2,4,4-tetramethyl-1,3- Cyclobutanediol and 75-88mol% 1,4-cyclohexanedimethanol; 12-20mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-88mol% 1,4- cyclohexanedimethanol, and 12-15 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol; and 85-88 mol% 1,4-cyclohexanedimethanol.

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：13-99mol％2，2，4，4-四甲基-1，3-环丁二醇和1-87mol％1，4-环己烷二甲醇；13-95mol％2，2，4，4-四甲基-1，3-环丁二醇和5-87mol％1，4-环己烷二甲醇；13-90mol％2，2，4，4-四甲基-1，3-环丁二醇和10-87mol％1，4-环己烷二甲醇；13-85mol％2，2，4，4-四甲基-1，3-环丁二醇和15-87mol％1，4-环己烷二甲醇；13-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-87mol％1，4-环己烷二甲醇，13-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-87mol％1，4-环己烷二甲醇；13-70mol％2，2，4，4-四甲基-1，3-环丁二醇和30-87mol％1，4-环己烷二甲醇；13-65mol％2，2，4，4-四甲基-1，3-环丁二醇和35-87mol％1，4-环己烷二甲醇；13-60mol％2，2，4，4-四甲基-1，3-环丁二醇和40-87mol％1，4-环己烷二甲醇；13-55mol％2，2，4，4-四甲基-1，3-环丁二醇和45-87mol％1，4-环己烷二甲醇；和13-50mol％2，2，4，4-四甲基-1，3-环丁二醇和50-87mol％1，4-环己烷二甲醇。In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 13-99mol% 2,2,4,4-Tetra Methyl-1,3-cyclobutanediol and 1-87mol% 1,4-cyclohexanedimethanol; 13-95mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 -87mol% 1,4-cyclohexanedimethanol; 13-90mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-87mol% 1,4-cyclohexanedimethanol ; 13-85mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-87mol% 1,4-cyclohexanedimethanol; 13-80mol% 2,2,4,4 -Tetramethyl-1,3-cyclobutanediol and 20-87mol% 1,4-cyclohexanedimethanol, 13-75mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol Alcohol and 25-87mol% 1,4-cyclohexanedimethanol; 13-70mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-87mol% 1,4-cyclohexane Dimethanol; 13-65mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-87mol% 1,4-cyclohexanedimethanol; 13-60mol% 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol and 40-87mol% 1,4-cyclohexanedimethanol; 13-55mol% 2,2,4,4-tetramethyl-1,3-cyclo Butanediol and 45-87mol% 1,4-cyclohexanedimethanol; and 13-50mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-87mol% 1,4- Cyclohexanedimethanol.

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：13-小于50mol％2，2，4，4-四甲基-1，3-环丁二醇和大于50-至多87mol％1，4-环己烷二甲醇；13-45mol％2，2，4，4-四甲基-1，3-环丁二醇和55-87mol％1，4-环己烷二甲醇；13-40mol％2，2，4，4-四甲基-1，3-环丁二醇和60-87mol％1，4-环己烷二甲醇；13-35mol％2，2，4，4-四甲基-1，3-环丁二醇和65-87mol％1，4-环己烷二甲醇；13-30mol％2，2，4，4-四甲基-1，3-环丁二醇和70-87mol％1，4-环己烷二甲醇；13-25mol％2，2，4，4-四甲基-1，3-环丁二醇和75-87mol％1，4-环己烷二甲醇；13-20mol％2，2，4，4-四甲基-1，3-环丁二醇和80-87mol％1，4-环己烷二甲醇，和13-15mol％2，2，4，4-四甲基-1，3-环丁二醇；和85-87mol％1，4-环己烷二甲醇。In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 13-less than 50mol% 2,2,4,4- Tetramethyl-1,3-cyclobutanediol and greater than 50-up to 87 mol% 1,4-cyclohexanedimethanol; 13-45 mol% 2,2,4,4-tetramethyl-1,3-cyclobutane Diol and 55-87mol% 1,4-cyclohexanedimethanol; 13-40mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-87mol% 1,4-cyclohexane Alkanedimethanol; 13-35mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-87mol% 1,4-cyclohexanedimethanol; 13-30mol% 2,2, 4,4-tetramethyl-1,3-cyclobutanediol and 70-87mol% 1,4-cyclohexanedimethanol; 13-25mol% 2,2,4,4-tetramethyl-1,3- Cyclobutanediol and 75-87mol% 1,4-cyclohexanedimethanol; 13-20mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-87mol% 1,4- Cyclohexanedimethanol, and 13-15 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol; and 85-87 mol% 1,4-cyclohexanedimethanol.

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：14-99mol％2，2，4，4-四甲基-1，3-环丁二醇和1-86mol％1，4-环己烷二甲醇；14-95mol％2，2，4，4-四甲基-1，3-环丁二醇和5-86mol％1，4-环己烷二甲醇；14-90mol％2，2，4，4-四甲基-1，3-环丁二醇和10-86mol％1，4-环己烷二甲醇；14-85mol％2，2，4，4-四甲基-1，3-环丁二醇和15-86mol％1，4-环己烷二甲醇；14-86mol％2，2，4，4-四甲基-1，3-环丁二醇和14-86mol％1，4-环己烷二甲醇，14-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-86mol％1，4-环己烷二甲醇；14-70mol％2，2，4，4-四甲基-1，3-环丁二醇和30-86mol％1，4-环己烷二甲醇；14-65mol％2，2，4，4-四甲基-1，3-环丁二醇和35-86mol％1，4-环己烷二甲醇；14-60mol％2，2，4，4-四甲基-1，3-环丁二醇和40-86mol％1，4-环己烷二甲醇；14-55mol％2，2，4，4-四甲基-1，3-环丁二醇和45-86mol％1，4-环己烷二甲醇；和14-50mol％2，2，4，4-四甲基-1，3-环丁二醇和50-86mol％1，4-环己烷二甲醇；In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 14-99mol% 2,2,4,4-Tetra Methyl-1,3-cyclobutanediol and 1-86mol% 1,4-cyclohexanedimethanol; 14-95mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 -86mol% 1,4-cyclohexanedimethanol; 14-90mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-86mol% 1,4-cyclohexanedimethanol ; 14-85mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-86mol% 1,4-cyclohexanedimethanol; 14-86mol% 2,2,4,4 -Tetramethyl-1,3-cyclobutanediol and 14-86mol% 1,4-cyclohexanedimethanol, 14-75mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol Alcohol and 25-86mol% 1,4-cyclohexanedimethanol; 14-70mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-86mol% 1,4-cyclohexane Dimethanol; 14-65mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-86mol% 1,4-cyclohexanedimethanol; 14-60mol% 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol and 40-86mol% 1,4-cyclohexanedimethanol; 14-55mol% 2,2,4,4-tetramethyl-1,3-cyclo Butanediol and 45-86mol% 1,4-cyclohexanedimethanol; and 14-50mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-86mol% 1,4- Cyclohexanedimethanol;

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：14-小于50mol％2，2，4，4-四甲基-1，3-环丁二醇和大于50-至多86mol％1，4-环己烷二甲醇；14-45mol％2，2，4，4-四甲基-1，3-环丁二醇和55-86mol％1，4-环己烷二甲醇；14-40mol％2，2，4，4-四甲基-1，3-环丁二醇和60-86mol％1，4-环己烷二甲醇；14-35mol％2，2，4，4-四甲基-1，3-环丁二醇和65-86mol％1，4-环己烷二甲醇；14-30mol％2，2，4，4-四甲基-1，3-环丁二醇和70-86mol％1，4-环己烷二甲醇；14-25mol％2，2，4，4-四甲基-1，3-环丁二醇和75-86mol％1，4-环己烷二甲醇；和14-20mol％2，2，4，4-四甲基-1，3-环丁二醇和80-86mol％1，4-环己烷二甲醇。In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 14-less than 50mol% 2,2,4,4- Tetramethyl-1,3-cyclobutanediol and greater than 50-up to 86 mol% 1,4-cyclohexanedimethanol; 14-45 mol% 2,2,4,4-tetramethyl-1,3-cyclobutane Diol and 55-86mol% 1,4-cyclohexanedimethanol; 14-40mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-86mol% 1,4-cyclohexane Alkanedimethanol; 14-35mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-86mol% 1,4-cyclohexanedimethanol; 14-30mol% 2,2, 4,4-tetramethyl-1,3-cyclobutanediol and 70-86mol% 1,4-cyclohexanedimethanol; 14-25mol% 2,2,4,4-tetramethyl-1,3- Cyclobutanediol and 75-86mol% 1,4-cyclohexanedimethanol; and 14-20mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-86mol% 1,4 - Cyclohexanedimethanol.

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：15-99mol％2，2，4，4-四甲基-1，3-环丁二醇和1-85mol％1，4-环己烷二甲醇；15-95mol％2，2，4，4-四甲基-1，3-环丁二醇和5-85mol％1，4-环己烷二甲醇；15-90mol％2，2，4，4-四甲基-1，3-环丁二醇和10-85mol％1，4-环己烷二甲醇；15-85mol％2，2，4，4-四甲基-1，3-环丁二醇和15-85mol％1，4-环己烷二甲醇；15-85mol％2，2，4，4-四甲基-1，3-环丁二醇和15-85mol％1，4-环己烷二甲醇，15-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-85mol％1，4-环己烷二甲醇；15-70mol％2，2，4，4-四甲基-1，3-环丁二醇和30-85mol％1，4-环己烷二甲醇；15-65mol％2，2，4，4-四甲基-1，3-环丁二醇和35-85mol％1，4-环己烷二甲醇；15-60mol％2，2，4，4-四甲基-1，3-环丁二醇和40-85mol％1，4-环己烷二甲醇；15-55mol％2，2，4，4-四甲基-1，3-环丁二醇和45-85mol％1，4-环己烷二甲醇；和15-50mol％2，2，4，4-四甲基-1，3-环丁二醇和50-85mol％1，4-环己烷二甲醇。In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 15-99mol% 2,2,4,4-Tetra Methyl-1,3-cyclobutanediol and 1-85mol% 1,4-cyclohexanedimethanol; 15-95mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 -85mol% 1,4-cyclohexanedimethanol; 15-90mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-85mol% 1,4-cyclohexanedimethanol ; 15-85mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-85mol% 1,4-cyclohexanedimethanol; 15-85mol% 2,2,4,4 -Tetramethyl-1,3-cyclobutanediol and 15-85mol% 1,4-cyclohexanedimethanol, 15-75mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol Alcohol and 25-85mol% 1,4-cyclohexanedimethanol; 15-70mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-85mol% 1,4-cyclohexane Dimethanol; 15-65mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-85mol% 1,4-cyclohexanedimethanol; 15-60mol% 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol and 40-85mol% 1,4-cyclohexanedimethanol; 15-55mol% 2,2,4,4-tetramethyl-1,3-cyclo Butanediol and 45-85mol% 1,4-cyclohexanedimethanol; and 15-50mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-85mol% 1,4- Cyclohexanedimethanol.

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：15-小于50mol％2，2，4，4-四甲基-1，3-环丁二醇和大于50-至多85mol％1，4-环己烷二甲醇；15-45mol％2，2，4，4-四甲基-1，3-环丁二醇和55-85mol％1，4-环己烷二甲醇；15-40mol％2，2，4，4-四甲基-1，3-环丁二醇和60-85mol％1，4-环己烷二甲醇；15-35mol％2，2，4，4-四甲基-1，3-环丁二醇和65-85mol％1，4-环己烷二甲醇；15-30mol％2，2，4，4-四甲基-1，3-环丁二醇和70-85mol％1，4-环己烷二甲醇；15-25mol％2，2，4，4-四甲基-1，3-环丁二醇和75-85mol％1，4-环己烷二甲醇；和15-20mol％2，2，4，4-四甲基-1，3-环丁二醇和80-85mol％1，4-环己烷二甲醇。In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 15-less than 50mol% 2,2,4,4- Tetramethyl-1,3-cyclobutanediol and greater than 50-up to 85 mol% 1,4-cyclohexanedimethanol; 15-45 mol% 2,2,4,4-tetramethyl-1,3-cyclobutane Diol and 55-85mol% 1,4-cyclohexanedimethanol; 15-40mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-85mol% 1,4-cyclohexane Alkanedimethanol; 15-35mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-85mol% 1,4-cyclohexanedimethanol; 15-30mol% 2,2, 4,4-tetramethyl-1,3-cyclobutanediol and 70-85mol% 1,4-cyclohexanedimethanol; 15-25mol% 2,2,4,4-tetramethyl-1,3- Cyclobutanediol and 75-85mol% 1,4-cyclohexanedimethanol; and 15-20mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-85mol% 1,4 - Cyclohexanedimethanol.

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：20-99mol％2，2，4，4-四甲基-1，3-环丁二醇和1-80mol％1，4-环己烷二甲醇；20-95mol％2，2，4，4-四甲基-1，3-环丁二醇和5-80mol％1，4-环己烷二甲醇；20-90mol％2，2，4，4-四甲基-1，3-环丁二醇和10-80mol％1，4-环己烷二甲醇；20-85mol％2，2，4，4-四甲基-1，3-环丁二醇和15-80mol％1，4-环己烷二甲醇；20-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-80mol％1，4-环己烷二甲醇，20-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-80mol％1，4-环己烷二甲醇；20-70mol％2，2，4，4-四甲基-1，3-环丁二醇和30-80mol％1，4-环己烷二甲醇；20-65mol％2，2，4，4-四甲基-1，3-环丁二醇和35-80mol％1，4-环己烷二甲醇；20-60mol％2，2，4，4-四甲基-1，3-环丁二醇和40-80mol％1，4-环己烷二甲醇；20-55mol％2，2，4，4-四甲基-1，3-环丁二醇和45-80mol％1，4-环己烷二甲醇；20-50mol％2，2，4，4-四甲基-1，3-环丁二醇和50-80mol％1，4-环己烷二甲醇；20-45mol％2，2，4，4-四甲基-1，3-环丁二醇和55-80mol％1，4-环己烷二甲醇；20-40mol％2，2，4，4-四甲基-1，3-环丁二醇和60-80mol％1，4-环己烷二甲醇；20-35mol％2，2，4，4-四甲基-1，3-环丁二醇和65-80mol％1，4-环己烷二甲醇；20-30mol％2，2，4，4-四甲基-1，3-环丁二醇和70-80mol％1，4-环己烷二甲醇；和20-25mol％2，2，4，4-四甲基-1，3-环丁二醇和75-80mol％1，4-环己烷二甲醇。In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 20-99mol% 2,2,4,4-Tetra Methyl-1,3-cyclobutanediol and 1-80mol% 1,4-cyclohexanedimethanol; 20-95mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 -80mol% 1,4-cyclohexanedimethanol; 20-90mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-80mol% 1,4-cyclohexanedimethanol ; 20-85mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-80mol% 1,4-cyclohexanedimethanol; 20-80mol% 2,2,4,4 -Tetramethyl-1,3-cyclobutanediol and 20-80mol% 1,4-cyclohexanedimethanol, 20-75mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol Alcohol and 25-80mol% 1,4-cyclohexanedimethanol; 20-70mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-80mol% 1,4-cyclohexane Dimethanol; 20-65mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-80mol% 1,4-cyclohexanedimethanol; 20-60mol% 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol and 40-80mol% 1,4-cyclohexanedimethanol; 20-55mol% 2,2,4,4-tetramethyl-1,3-cyclo Butanediol and 45-80mol% 1,4-cyclohexanedimethanol; 20-50mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-80mol% 1,4-cyclohexane Hexanedimethanol; 20-45mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-80mol% 1,4-cyclohexanedimethanol; 20-40mol% 2,2 , 4,4-tetramethyl-1,3-cyclobutanediol and 60-80mol% 1,4-cyclohexanedimethanol; 20-35mol% 2,2,4,4-tetramethyl-1,3 - cyclobutanediol and 65-80mol% 1,4-cyclohexanedimethanol; 20-30mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-80mol% 1,4 - cyclohexanedimethanol; and 20-25 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-80 mol% 1,4-cyclohexanedimethanol.

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：25-99mol％2，2，4，4-四甲基-1，3-环丁二醇和1-75mol％1，4-环己烷二甲醇；25-90mol％2，2，4，4-四甲基-1，3-环丁二醇和10-75mol％1，4-环己烷二甲醇；25-85mol％2，2，4，4-四甲基-1，3-环丁二醇和15-75mol％1，4-环己烷二甲醇；25-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-75mol％1，4-环己烷二甲醇，25-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-75mol％1，4-环己烷二甲醇；25-70mol％2，2，4，4-四甲基-1，3-环丁二醇和30-75mol％1，4-环己烷二甲醇；25-65mol％2，2，4，4-四甲基-1，3-环丁二醇和35-75mol％1，4-环己烷二甲醇；25-60mol％2，2，4，4-四甲基-1，3-环丁二醇和40-75mol％1，4-环己烷二甲醇；25-55mol％2，2，4，4-四甲基-1，3-环丁二醇和45-75mol％1，4-环己烷二甲醇；25-50mol％2，2，4，4-四甲基-1，3-环丁二醇和50-75mol％1，4-环己烷二甲醇；25-45mol％2，2，4，4-四甲基-1，3-环丁二醇和55-75mol％1，4-环己烷二甲醇；25-40mol％2，2，4，4-四甲基-1，3-环丁二醇和60-75mol％1，4-环己烷二甲醇；25-35mol％2，2，4，4-四甲基-1，3-环丁二醇和65-75mol％1，4-环己烷二甲醇；25-30mol％2，2，4，4-四甲基-1，3-环丁二醇和70-75mol％1，4-环己烷二甲醇。In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 25-99mol% 2,2,4,4-Tetra Methyl-1,3-cyclobutanediol and 1-75mol% 1,4-cyclohexanedimethanol; 25-90mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 -75mol% 1,4-cyclohexanedimethanol; 25-85mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-75mol% 1,4-cyclohexanedimethanol ; 25-80mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-75mol% 1,4-cyclohexanedimethanol, 25-75mol% 2,2,4,4 -Tetramethyl-1,3-cyclobutanediol and 25-75mol% 1,4-cyclohexanedimethanol; 25-70mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol Alcohol and 30-75mol% 1,4-cyclohexanedimethanol; 25-65mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-75mol% 1,4-cyclohexane Dimethanol; 25-60mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-75mol% 1,4-cyclohexanedimethanol; 25-55mol% 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol and 45-75mol% 1,4-cyclohexanedimethanol; 25-50mol% 2,2,4,4-tetramethyl-1,3-cyclo Butanediol and 50-75mol% 1,4-cyclohexanedimethanol; 25-45mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-75mol% 1,4-cyclohexane Hexanedimethanol; 25-40mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-75mol% 1,4-cyclohexanedimethanol; 25-35mol% 2,2 , 4,4-tetramethyl-1,3-cyclobutanediol and 65-75mol% 1,4-cyclohexanedimethanol; 25-30mol% 2,2,4,4-tetramethyl-1,3 - Cyclobutanediol and 70-75 mol% 1,4-cyclohexanedimethanol.

在本发明的其它方面中，对于可用于本发明薄膜或者薄板的聚酯的二醇组分包括但不限于以下范围组合中的至少一种：35-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-65mol％1，4-环己烷二甲醇；37-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-63mol％1，4-环己烷二甲醇；40-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-60mol％1，4-环己烷二甲醇；45-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-55mol％1，4-环己烷二甲醇；50-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-50mol％1，4-环己烷二甲醇；大于50-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-小于50mol％1，4-环己烷二甲醇；55-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-45mol％1，4-环己烷二甲醇；60-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-40mol％1，4-环己烷二甲醇；65-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-35mol％1，4-环己烷二甲醇；70-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-30mol％1，4-环己烷二甲醇；40-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-60mol％1，4-环己烷二甲醇；45-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-55mol％1，4-环己烷二甲醇；50-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-50mol％1，4-环己烷二甲醇；55-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-45mol％1，4-环己烷二甲醇；60-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-40mol％1，4-环己烷二甲醇；65-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-35mol％1，4-环己烷二甲醇；40-70mol％2，2，4，4-四甲基-1，3-环丁二醇和30-60mol％1，4-环己烷二甲醇；45-70mol％2，2，4，4-四甲基-1，3-环丁二醇和30-55mol％1，4-环己烷二甲醇；50-70mol％2，2，4，4-四甲基-1，3-环丁二醇和30-50mol％1，4-环己烷二甲醇；大于50-99mol％2，2，4，4-四甲基-1，3-环丁二醇和1-小于50mol％1，4-环己烷二甲醇；大于50-80mol％2，2，4，4-四甲基-1，3-环丁二醇和20-小于50mol％1，4-环己烷二甲醇；大于50-75mol％2，2，4，4-四甲基-1，3-环丁二醇和25-小于50mol％1，4-环己烷二甲醇；大于50-70mol％2，2，4，4-四甲基-1，3-环丁二醇和30-小于50mol％1，4-环己烷二甲醇；55-70mol％2，2，4，4-四甲基-1，3-环丁二醇和30-45mol％1，4-环己烷二甲醇；60-70mol％2，2，4，4-四甲基-1，3-环丁二醇和30-40mol％1，4-环己烷二甲醇；40-65mol％2，2，4，4-四甲基-1，3-环丁二醇和35-60mol％1，4-环己烷二甲醇；40-55mol％2，2，4，4-四甲基-1，3-环丁二醇和45-60mol％1，4-环己烷二甲醇；40-小于45mol％2，2，4，4-四甲基-1，3-环丁二醇和大于55-60mol％1，4-环己烷二甲醇；45-65mol％2，2，4，4-四甲基-1，3-环丁二醇和35-55mol％1，4-环己烷二甲醇；大于50-65mol％2，2，4，4-四甲基-1，3-环丁二醇和35-小于50mol％1，4-环己烷二甲醇；50-65mol％2，2，4，4-四甲基-1，3-环丁二醇和35-50mol％1，4-环己烷二甲醇；55-65mol％2，2，4，4-四甲基-1，3-环丁二醇和35-45mol％1，4-环己烷二甲醇；40-60mol％2，2，4，4-四甲基-1，3-环丁二醇和40-60mol％1，4-环己烷二甲醇；45-60mol％2，2，4，4-四甲基-1，3-环丁二醇和40-55mol％1，4-环己烷二甲醇；45-55mol％2，2，4，4-四甲基-1，3-环丁二醇和45-55mol％1，4-环己烷二甲醇；大于45-55mol％2，2，4，4-四甲基-1，3-环丁二醇，45-小于55mol％1，4-环己烷二甲醇；和46-55mol％2，2，4，4-四甲基-1，3-环丁二醇和45-54mol％1，4-环己烷二甲醇；和46-65mol％2，2，4，4-四甲基-1，3-环丁二醇和35-54mol％1，4-环己烷二甲醇。In other aspects of the present invention, the diol component of the polyester that can be used in the film or sheet of the present invention includes but is not limited to at least one of the following range combinations: 35-80mol% 2,2,4,4-Tetra Methyl-1,3-cyclobutanediol and 20-65mol% 1,4-cyclohexanedimethanol; 37-80mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 -63mol% 1,4-cyclohexanedimethanol; 40-80mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-60mol% 1,4-cyclohexanedimethanol ; 45-80mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-55mol% 1,4-cyclohexanedimethanol; 50-80mol% 2,2,4,4 -Tetramethyl-1,3-cyclobutanediol and 20-50 mol% 1,4-cyclohexanedimethanol; greater than 50-80 mol% 2,2,4,4-tetramethyl-1,3-cyclobutane Diol and 20-less than 50mol% 1,4-cyclohexanedimethanol; 55-80mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-45mol% 1,4-cyclohexane Hexanedimethanol; 60-80mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-40mol% 1,4-cyclohexanedimethanol; 65-80mol% 2,2 , 4,4-tetramethyl-1,3-cyclobutanediol and 20-35mol% 1,4-cyclohexanedimethanol; 70-80mol% 2,2,4,4-tetramethyl-1,3 - cyclobutanediol and 20-30mol% 1,4-cyclohexanedimethanol; 40-75mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-60mol% 1,4 - Cyclohexanedimethanol; 45-75mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-55mol% 1,4-cyclohexanedimethanol; 50-75mol% 2 , 2,4,4-tetramethyl-1,3-cyclobutanediol and 25-50mol% 1,4-cyclohexanedimethanol; 55-75mol% 2,2,4,4-tetramethyl-1 , 3-cyclobutanediol and 25-45mol% 1,4-cyclohexanedimethanol; 60-75mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-40mol% 1 , 4-cyclohexanedimethanol; 65-75mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-35mol% 1,4-cyclohexanedimethanol; 40-70mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-60mol% 1,4-cyclohexanedimethanol; 45-70mol% 2,2,4,4-tetramethyl -1,3-cyclobutanediol and 30-55mol% 1,4-cyclohexanedimethanol; 50-70mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-50mol% %1,4-ring Hexanedimethanol; greater than 50-99mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-less than 50mol% 1,4-cyclohexanedimethanol; greater than 50-80mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-less than 50mol% 1,4-cyclohexanedimethanol; more than 50-75mol% 2,2,4,4-tetramethyl Base-1,3-cyclobutanediol and 25-less than 50mol% 1,4-cyclohexanedimethanol; more than 50-70mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-less than 50mol% 1,4-cyclohexanedimethanol; 55-70mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-45mol% 1,4-cyclohexane Dimethanol; 60-70mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-40mol% 1,4-cyclohexanedimethanol; 40-65mol% 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol and 35-60mol% 1,4-cyclohexanedimethanol; 40-55mol% 2,2,4,4-tetramethyl-1,3-cyclo Butanediol and 45-60mol% 1,4-cyclohexanedimethanol; 40-less than 45mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 55-60mol% 1,4 - Cyclohexanedimethanol; 45-65 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-55 mol% 1,4-cyclohexanedimethanol; greater than 50-65 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-less than 50mol% 1,4-cyclohexanedimethanol; 50-65mol% 2,2,4,4-tetramethyl -1,3-cyclobutanediol and 35-50mol% 1,4-cyclohexanedimethanol; 55-65mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-45mol% % 1,4-cyclohexanedimethanol; 40-60mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-60mol% 1,4-cyclohexanedimethanol; 45 -60mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-55mol% 1,4-cyclohexanedimethanol; 45-55mol% 2,2,4,4-tetra Methyl-1,3-cyclobutanediol and 45-55mol% 1,4-cyclohexanedimethanol; greater than 45-55mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol , 45-less than 55mol% 1,4-cyclohexanedimethanol; and 46-55mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-54mol% 1,4-cyclohexane hexanedimethanol; and 46-65 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-54 mol% 1,4-cyclohexanedimethanol.

除了上述所列二醇，可用于本发明薄膜或者薄板的聚酯组合物的聚酯还可由1，3-丙二醇、1，4-丁二醇或其混合物制备。In addition to the diols listed above, the polyesters useful in the polyester compositions of the films or sheets of the present invention can also be prepared from 1,3-propanediol, 1,4-butanediol or mixtures thereof.

除了上述所列二醇，可用于本发明薄膜或者薄板的聚酯组合物的聚酯还可由1，3-丙二醇、1，4-丁二醇或其混合物制备，可以具有本文所述Tg的范围中的至少一个、本文所述比浓对数粘度的范围中的至少一个和/或本文所述二醇或二酸的范围中的至少一个。此外或备选地，可用于本发明薄膜或者薄板的聚酯可由1，3-丙二醇或1，4-丁二醇或其混合物制备，还可由1，4-环己烷二甲醇以至少一种下述的量来制备：0.1-99mol％；0.1-95mol％；0.1-90mol％；0.1-85mol％；0.1-80mol％；0.1-70mol％；0.1-60mol％；0.1-50mol％；0.1-40mol％；0.1-35mol％；0.1-30mol％；0.1-25mol％；0.1-20mol％；0.1-15mol％；0.1-10mol％；0.1-5mol％；1-99mol％；1-95mol％；1-90mol％；1-85mol％；1-80mol％；1-70mol％；1-60mol％；1-50mol％；1-40mol％；1-35mol％；1-30mol％；1-25mol％；1-20mol％；1-15mol％；1-10mol％；1-5mol％；5-99mol％；5-95mol％；5-90mol％；5-85mol％；5-80mol％；5-70mol％；5-60mol％；5-50mol％；5-40mol％；5-35mol％；5-30mol％；5-25mol％；5-20mol％；and5-15mol％；5-10mol％；10-99mol％；10-95mol％；10-90mol％；10-85mol％；10-80mol％；10-70mol％；10-60mol％；10-50mol％；10-40mol％；10-35mol％；10-30mol％；10-25mol％；10-20mol％；10-15mol％；20-99mol％；20-95mol％；20-90mol％；20-85mol％；20-80mol％；20-70mol％；20-60mol％；20-50mol％；20-40mol％；20-35mol％；20-30mol％；和20-25mol％。In addition to the diols listed above, the polyesters useful in the polyester compositions of the films or sheets of the present invention may also be prepared from 1,3-propanediol, 1,4-butanediol, or mixtures thereof, and may have a Tg in the range described herein at least one of the ranges for inherent viscosities described herein, and/or at least one of the ranges for diols or diacids described herein. Additionally or alternatively, the polyesters useful in the films or sheets of the present invention may be prepared from 1,3-propanediol or 1,4-butanediol or mixtures thereof, and from 1,4-cyclohexanedimethanol in at least one 0.1-99mol%; 0.1-95mol%; 0.1-90mol%; 0.1-85mol%; 0.1-80mol%; 0.1-70mol%; 0.1-60mol%; %; 0.1-35mol%; 0.1-30mol%; 0.1-25mol%; 0.1-20mol%; 0.1-15mol%; 0.1-10mol%; 0.1-5mol%; %;1-85mol%;1-80mol%;1-70mol%;1-60mol%;1-50mol%;1-40mol%;1-35mol%;1-30mol%;1-25mol%;1-20mol 5-99mol%; 5-95mol%; 5-90mol%; 5-85mol%; 5-80mol%; 5-70mol%; 5-60mol% 5-50mol%; 5-40mol%; 5-35mol%; 5-30mol%; 5-25mol%; 5-20mol%; and5-15mol%; 5-10mol%; %;10-90mol%;10-85mol%;10-80mol%;10-70mol%;10-60mol%;10-50mol%;10-40mol%;10-35mol%;10-30mol%;10-25mol% 10-20mol%; 10-15mol%; 20-99mol%; 20-95mol%; 20-90mol%; 20-85mol%; 20-80mol%; 20-70mol%; 20-40 mol%; 20-35 mol%; 20-30 mol%; and 20-25 mol%.

对于本发明某些实施方案来说，可用于本发明薄膜或者薄板的聚酯可显示以下比浓对数粘度中的至少一个，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的：0.10-1.2dL/g；0.10-1.1dL/g；0.10-1dL/g；；0.10-小于1dL/g；0.10-0.98dL/g；0.10-0.95dL/g；0.10-0.90dL/g；0.10-0.85dL/g；0.10-0.80dL/g；0.10-0.75dL/g；0.10-小于0.75dL/g；0.10-0.72dL/g；0.10-0.70dL/g；0.10-小于0.70dL/g；0.10-0.68dL/g；0.10-小于0.68dL/g；0.10-0.65dL/g；0.20-1.2dL/g；0.20-1.1dL/g；0.20-1dL/g；0.20-小于1dL/g；0.20-0.98dL/g；0.20-0.95dL/g；0.20-0.90dL/g；0.20-0.85dL/g；0.20-0.80dL/g；0.20-0.75dL/g；0.20-小于0.75dL/g；0.20-0.72dL/g；0.20-0.70dL/g；0.20-小于0.70dL/g；0.20-0.68dL/g；0.20-小于0.68dL/g；0.20-0.65dL/g；0.35-1.2dL/g；0.35-1.1dL/g；0.35-1dL/g；0.35-小于1dL/g；0.35-0.98dL/g；0.35-0.95dL/g；0.35-0.90dL/g；0.35-0.85dL/g；0.35-0.80dL/g；0.35-0.75dL/g；0.35-小于0.75dL/g；0.35-0.72dL/g；0.35-0.70dL/g；0.35-小于0.70dL/g；0.35-0.68dL/g；0.35-小于0.68dL/g；0.35-0.65dL/g；0.40-1.2dL/g；0.40-1.1dL/g；0.40-1dL/g；0.40-小于1dL/g；0.40-0.98dL/g；0.40-0.95dL/g；0.40-0.90dL/g；0.40-0.85dL/g；0.40-0.80dL/g；0.40-0.75dL/g；0.40-小于0.75dL/g；0.40-0.72dL/g；0.40-0.70dL/g；0.40-小于0.70dL/g；0.40-0.68dL/g；0.40-小于0.68dL/g；0.40-0.65dL/g；大于0.42-1.2dL/g；大于0.42-1.1dL/g；大于0.42-1dL/g；大于0.42-小于1dL/g；大于0.42-0.98dL/g；大于0.42-0.95dL/g；大于0.42-0.90dL/g；大于0.42-0.85dL/g；大于0.42-0.80dL/g；大于0.42-0.75dL/g；大于0.42-小于0.75dL/g；大于0.42-0.72dL/g；大于0.42-小于0.70dL/g；大于0.42-0.68dL/g；大于0.42-小于0.68dL/g；和大于0.42-0.65dL/g。For certain embodiments of the present invention, the polyesters useful in the films or sheets of the present invention may exhibit at least one of the following inherent viscosities, such as 60/40 (wt) at a concentration of 0.5 g/100 ml at 25° C. 0.10-1.1dL/g; 0.10-1dL/g; 0.10-less than 1dL/g; 0.10-0.98dL/g; 0.10- 0.95dL/g; 0.10-0.90dL/g; 0.10-0.85dL/g; 0.10-0.80dL/g; 0.10-0.75dL/g; 0.10-less than 0.75dL/g; 0.70dL/g; 0.10-less than 0.70dL/g; 0.10-0.68dL/g; 0.10-less than 0.68dL/g; 0.10-0.65dL/g; 0.20-1.2dL/g; -1dL/g; 0.20-less than 1dL/g; 0.20-0.98dL/g; 0.20-0.95dL/g; 0.20-0.90dL/g; 0.20-0.85dL/g; dL/g; 0.20-less than 0.75dL/g; 0.20-0.72dL/g; 0.20-0.70dL/g; 0.20-less than 0.70dL/g; 0.20-0.68dL/g; -0.65dL/g; 0.35-1.2dL/g; 0.35-1.1dL/g; 0.35-1dL/g; 0.35-less than 1dL/g; dL/g; 0.35-0.85dL/g; 0.35-0.80dL/g; 0.35-0.75dL/g; 0.35-less than 0.75dL/g; 0.70dL/g; 0.35-0.68dL/g; 0.35-less than 0.68dL/g; 0.35-0.65dL/g; 0.40-1.2dL/g; 0.40-1.1dL/g; 1dL/g; 0.40-0.98dL/g; 0.40-0.95dL/g; 0.40-0.90dL/g; 0.40-0.85dL/g; dL/g; 0.40-0.72dL/g; 0.40-0.70dL/g; 0.40-less than 0.70dL/g; 0.40-0.68dL/g; 0.40-less than 0.68dL/g; 0.40-0.65dL/g; greater than 0.42-1.2dL/g; greater than 0.42-1.1dL/g; greater than 0.42-1dL/g; greater than 0.42-less than 1dL /g; greater than 0.42-0.98dL/g; greater than 0.42-0.95dL/g; greater than 0.42-0.90dL/g; greater than 0.42-0.85dL/g; greater than 0.42-0.80dL/g; greater than 0.42-0.75dL/g ; greater than 0.42-less than 0.75dL/g; greater than 0.42-0.72dL/g; greater than 0.42-less than 0.70dL/g; greater than 0.42-0.68dL/g; greater than 0.42-less than 0.68dL/g; /g.

对于本发明某些实施方案来说，可用于本发明薄膜或者薄板的聚酯可显示以下比浓对数粘度中的至少一个，如在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的：0.45-1.2dL/g；0.45-1.1dL/g；0.45-1dL/g；0.45-0.98dL/g；0.45-0.95dL/g；0.45-0.90dL/g；0.45-0.85dL/g；0.45-0.80dL/g；0.45-0.75dL/g；0.45-小于0.75dL/g；0.45-0.72dL/g；0.45-0.70dL/g；0.45-小于0.70dL/g；0.45-0.68dL/g；0.45-小于0.68dL/g；0.45-0.65dL/g；0.50-1.2dL/g；0.50-1.1dL/g；0.50-1dL/g；0.50-小于1dL/g；0.50-0.98dL/g；0.50-0.95dL/g；0.50-0.90dL/g；0.50-0.85dL/g；0.50-0.80dL/g；0.50-0.75dL/g；0.50-小于0.75dL/g；0.50-0.72dL/g；0.50-0.70dL/g；0.50-小于0.70dL/g；0.50-0.68dL/g；0.50-小于0.68dL/g；0.50-0.65dL/g；0.55-1.2dL/g；0.55-11dL/g；0.55-1dL/g；0.55-小于1dL/g；0.55-0.98dL/g；0.55-0.95dL/g；0.55-0.90dL/g；0.55-0.85dL/g；0.55-0.80dL/g；0.55-0.75dL/g；0.55-小于0.75dL/g；0.55-0.72dL/g；0.55-0.70dL/g；0.55-小于0.70dL/g；0.55-0.68dL/g；0.55-小于0.68dL/g；0.55-0.65dL/g；0.58-1.2dL/g；0.5 8-1.1dL/g；0.58-1dL/g；0.58-小于1dL/g；0.58-0.98dL/g；0.58-0.95dL/g；0.58-0.90dL/g；0.58-0.85dL/g；0.58-0.80dL/g；0.58-0.75dL/g；0.58-小于0.75dL/g；0.58-0.72dL/g；0.58-0.70dL/g；0.58-小于0.70dL/g；0.58-0.68dL/g；0.58-小于0.68dL/g；0.58-0.65dL/g；0.60-1.2dL/g；0.60-1.1dL/g；0.60-1dL/g；0.60-小于1dL/g；0.60-0.98dL/g；0.60-0.95dL/g；0.60-0.90dL/g；0.60-0.85dL/g；0.60-0.80dL/g；0.60-0.75dL/g；0.60-小于0.75dL/g；0.60-0.72dL/g；0.60-0.70dL/g；0.60-小于0.70dL/g；0.60-0.68dL/g；0.60-小于0.68dL/g；0.60-0.65dL/g；0.65-1.2dL/g；0.65-1.1dL/g；0.65-1dL/g；0.65-小于1dL/g；0.65-0.98dL/g；0.65-0.95dL/g；0.65-0.90dL/g；0.65-0.85dL/g；0.65-0.80dL/g；0.65-0.75dL/g；0.65-小于0.75dL/g；0.65-0.72dL/g；0.65-0.70dL/g；0.65-小于0.70dL/g；0.68-1.2dL/g；0.68-1.1dL/g；0.68-1dL/g；0.68-小于1dL/g；0.68-0.98dL/g；0.68-0.95dL/g；0.68-0.90dL/g；0.68-0.85dL/g；0.68-0.80dL/g；0.68-0.75dL/g；0.68-小于0.75dL/g；0.68-0.72dL/g；大于0.76dL/g-1.2dL/g；大于0.76dL/g-1.1dL/g；大于0.76dL/g-1dL/g；大于0.76dL/g-小于1dL/g；大于0.76dL/g-0.98dL/g；大于0.76dL/g-0.95dL/g；大于0.76dL/g-0.90dL/g；大于0.80dL/g-1.2dL/g；大于0.80dL/g-1.1dL/g；大于0.80dL/g-1dL/g；大于0.80dL/g-小于1dL/g；大于0.80dL/g-1.2dL/g；大于0.80dL/g-0.98dL/g；大于0.80dL/g-0.95dL/g；大于0.80dL/g-0.90dL/g。For certain embodiments of the present invention, the polyesters useful in the films or sheets of the present invention may exhibit at least one of the following inherent viscosities, such as 60/40 (wt) at a concentration of 0.5 g/100 ml at 25° C. /wt) determined in phenol/tetrachloroethane: 0.45-1.2dL/g; 0.45-1.1dL/g; 0.45-1dL/g; 0.45-0.98dL/g; dL/g; 0.45-0.85dL/g; 0.45-0.80dL/g; 0.45-0.75dL/g; 0.45-less than 0.75dL/g; 0.70dL/g; 0.45-0.68dL/g; 0.45-less than 0.68dL/g; 0.45-0.65dL/g; 0.50-1.2dL/g; 0.50-1.1dL/g; 1dL/g; 0.50-0.98dL/g; 0.50-0.95dL/g; 0.50-0.90dL/g; 0.50-0.85dL/g; dL/g; 0.50-0.72dL/g; 0.50-0.70dL/g; 0.50-less than 0.70dL/g; 0.50-0.68dL/g; 1.2dL/g; 0.55-11dL/g; 0.55-1dL/g; 0.55-less than 1dL/g; 0.55-0.98dL/g; g; 0.55-0.80dL/g; 0.55-0.75dL/g; 0.55-less than 0.75dL/g; 0.55-0.72dL/g; /g; 0.55-less than 0.68dL/g; 0.55-0.65dL/g; 0.58-1.2dL/g; 0.5 8-1.1dL/g; 0.58-1dL/g; /g; 0.58-0.95dL/g; 0.58-0.90dL/g; 0.58-0.85dL/g; 0.58-0.80dL/g; /g; 0.58-0.70dL/g; 0.58-less than 0.70dL/g; 0.58-0.68dL/g; 0.58-less than 0.68dL/g; 0.58-0.65dL/g; 0.60-1.2dL/g; 0.60-1.1dL/g; 0.60-1dL/g; 0.60-less than 1dL/g; -0.95dL/g; 0.60-0.90dL/g; 0.60-0.85dL/g; 0.60-0.80dL/g; 0.60-0.75dL/g; 0.60-less than 0.75dL/g; -0.70dL/g; 0.60-less than 0.70dL/g; 0.60-0.68dL/g; 0.60-less than 0.68dL/g; 0.60-0.65dL/g; 0.65-1.2dL/g; 0.65-1dL/g; 0.65-less than 1dL/g; 0.65-0.98dL/g; 0.65-0.95dL/g; 0.65-0.90dL/g; 0.65-0.85dL/g; 0.75dL/g; 0.65-less than 0.75dL/g; 0.65-0.72dL/g; 0.65-0.70dL/g; 0.65-less than 0.70dL/g; 0.68-1.2dL/g; -1dL/g; 0.68-less than 1dL/g; 0.68-0.98dL/g; 0.68-0.95dL/g; 0.68-0.90dL/g; 0.68-0.85dL/g; dL/g; 0.68-less than 0.75dL/g; 0.68-0.72dL/g; greater than 0.76dL/g-1.2dL/g; greater than 0.76dL/g-1.1dL/g; greater than 0.76dL/g-1dL/g ; greater than 0.76dL/g-less than 1dL/g; greater than 0.76dL/g-0.98dL/g; greater than 0.76dL/g-0.95dL/g; greater than 0.76dL/g-0.90dL/g; greater than 0.80dL/g -1.2dL/g; greater than 0.80dL/g-1.1dL/g; greater than 0.80dL/g-1dL/g; greater than 0.80dL/g-less than 1dL/g; greater than 0.80dL/g-1.2dL/g; 0.80dL/g-0.98dL/g; greater than 0.80dL/g-0.95dL/g; greater than 0.80dL/g-0.90dL/g.

预期可用于本发明薄膜或者薄板的聚酯组合物可以具有本文所述比浓对数粘度的范围中的至少一个和本文中所述的用于组合物的单体的范围中的至少一个，除非另有说明。还预期可用于本发明薄膜或者薄板的聚酯组合物可以具有本文所述Tg的范围中的至少一个和本文中所述的用于组合物的单体的范围中的至少一个，除非另有说明。还预期可用于本发明薄膜或者薄板的聚酯组合物可以具有本文所述Tg的范围中的至少一个、本文所述比浓对数粘度的范围中的至少一个和本文中所述的用于组合物的单体的范围中的至少一个，除非另有说明。Polyester compositions contemplated for use in the films or sheets of the present invention may have at least one of the ranges for inherent viscosities described herein and at least one of the ranges described herein for the monomers of the composition, unless otherwise stated. It is also contemplated that the polyester compositions useful in the films or sheets of the present invention may have at least one of the Tg ranges described herein and at least one of the monomer ranges described herein for the composition, unless otherwise stated . It is also contemplated that the polyester compositions useful in the films or sheets of the present invention may have at least one of the Tg ranges described herein, at least one of the inherent viscosity ranges described herein, and combinations of the Tg ranges described herein. at least one of the monomeric ranges of the compounds, unless otherwise stated.

对于期望的可用于本发明薄膜或者薄板的聚酯，顺式/反式2，2，4，4-四甲基-1，3-环丁二醇的摩尔比由于各自的纯形式或其混合物可变化。在某些实施方案中，顺式和/或反式2，2，4，4-四甲基-1，3-环丁二醇的摩尔百分数是大于50mol％顺式和小于50mol％反式；或者大于55mol％ 顺式和小于45mol％反式；或者30-70mol％顺式和70-30％反式；或者40-60mol％顺式和60-40mol％反式；或者50-70mol％反式和50-30mol％顺式；或者50-70mol％顺式和50-30％反式或者60-70mol％顺式和30-40mol％反式；或者大于70mol％顺式和小于30mol％反式；其中顺式和反式-2，2，4，4-四甲基-1，3-环丁二醇的摩尔百分数的总和等于100mol％。顺式/反式1，4-环己烷二甲醇的摩尔比可在以下范围变化：50/50-0/100，例如，40/60-20/80。The molar ratio of cis/trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol for the desired polyesters useful in the film or sheet of the present invention is due to the respective pure forms or mixtures thereof subject to change. In certain embodiments, the molar percentage of cis and/or trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol is greater than 50 mol% cis and less than 50 mol% trans; Or greater than 55mol% cis and less than 45mol% trans; or 30-70mol% cis and 70-30% trans; or 40-60mol% cis and 60-40mol% trans; or 50-70mol% trans and 50-30mol% cis; or 50-70mol% cis and 50-30% trans or 60-70mol% cis and 30-40mol% trans; or greater than 70mol% cis and less than 30mol% trans; Wherein the sum of the mole percentages of cis and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to 100 mol%. The molar ratio of cis/trans 1,4-cyclohexanedimethanol can vary in the following range: 50/50-0/100, for example, 40/60-20/80.

在某些实施方案中，对苯二甲酸或其酯，例如对苯二甲酸二甲酯，或者对苯二甲酸和其酯的混合物，构成了用于形成可用于本发明薄膜或者薄板的聚酯的二羧酸组分的大部分或者全部。在某些实施方案中，对苯二甲酸残基可以构成一部分或者全部的用于形成本发明的聚酯的二羧酸组分，其浓度为至少70mol％，如至少80mol％，至少90mol％，至少95mol％，至少99mol％或100mol％。在某些实施方案中，可以使用具有较高量的对苯二甲酸的聚酯以便获得较高的冲击强度性能。就本公开内容的目的而言，术语“对苯二甲酸”和“对苯二甲酸二甲酯”在本文中可互换使用。在一个实施方案中，对苯二甲酸二甲酯是用于制备对本发明有用的聚酯的二羧酸组分的一部分或全部。在所有的实施方案中，可以使用70-100mol％；或80-100mol％；或90-100mol％；或99-100mol％；或100mol％的对苯二甲酸和/或对苯二甲酸二甲酯和/或其混合物。In certain embodiments, terephthalic acid or its esters, such as dimethyl terephthalate, or mixtures of terephthalic acid and its esters, constitute the polyesters used to form films or sheets useful in the present invention. Most or all of the dicarboxylic acid components. In certain embodiments, the terephthalic acid residues may constitute part or all of the dicarboxylic acid component used to form the polyesters of the present invention at a concentration of at least 70 mol%, such as at least 80 mol%, at least 90 mol%, At least 95 mol%, at least 99 mol% or 100 mol%. In certain embodiments, polyesters with higher amounts of terephthalic acid may be used in order to obtain higher impact strength properties. For the purposes of this disclosure, the terms "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein. In one embodiment, dimethyl terephthalate is part or all of the dicarboxylic acid component used to prepare the polyesters useful in this invention. In all embodiments, 70-100 mol %; or 80-100 mol %; or 90-100 mol %; or 99-100 mol %; or 100 mol % of terephthalic acid and/or dimethyl terephthalate may be used and/or mixtures thereof.

除了对苯二甲酸残基，可用于本发明薄膜或者薄板的聚酯的二羧酸组分可包含至多30mol％、至多20mol％、至多10mol％、至多5mol％、或至多1mol％的一种或多种改性芳族二羧酸。又一个实施方案包含0mol％改性芳族二羧酸。因此，如果存在的话，预期一种或多种改性芳族二羧酸的量可以从任何这些上述端点值延伸，包括例如0.01-30mol％、0.01-20mol％、0.01-10mol％、0.01-5mol％、或者0.01-1mol％的一种或多种改性芳族二羧酸。在一种实施方案中，可用于本发明的改性芳族二羧酸包括但不限于具有至多20个碳原子的那些，并且它们可以是线性的、对位取向的或对称的。可用于本发明的改性芳族二羧酸的实例包括但不限于间苯二甲酸、4，4′-联苯二甲酸、1，4-，1，5-，2，6-，2，7-萘二甲酸和反-4，4′-均二苯代乙烯二甲酸及其酯。在一种实施方案中，间苯二甲酸是该改性芳族二羧酸。In addition to terephthalic acid residues, the dicarboxylic acid component of the polyester useful in the film or sheet of the present invention may contain up to 30 mol%, up to 20 mol%, up to 10 mol%, up to 5 mol%, or up to 1 mol% of one or more A variety of modified aromatic dicarboxylic acids. Yet another embodiment comprises 0 mol% modified aromatic dicarboxylic acid. Accordingly, it is contemplated that the amount of one or more modified aromatic dicarboxylic acids, if present, may extend from any of these above-mentioned endpoints, including for example 0.01-30 mol%, 0.01-20 mol%, 0.01-10 mol%, 0.01-5 mol% %, or 0.01-1 mol% of one or more modified aromatic dicarboxylic acids. In one embodiment, modified aromatic dicarboxylic acids useful in the present invention include, but are not limited to, those having up to 20 carbon atoms, and they may be linear, para-oriented, or symmetrical. Examples of modified aromatic dicarboxylic acids useful in the present invention include, but are not limited to, isophthalic acid, 4,4'-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2, 7-naphthalene dicarboxylic acid and trans-4,4'-stilbene dicarboxylic acid and esters thereof. In one embodiment, isophthalic acid is the modified aromatic dicarboxylic acid.

可用于本发明薄膜或者薄板的聚酯的羧酸组分可进一步用至多10mol％，例如至多5mol％或至多1mol％的一种或多种含有2-16个碳原子的脂族二羧酸，例如丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸和十二烷二酸来改性。某些实施方案也可包含0.01mol％或更多，如0.1mol％或更多，1mol％或更多，5mol％或更多，或者10mol％或更多的一种或多种改性脂族二羧酸。又一个实施方案包含0mol％改性脂族二羧酸。因此，如果存在的话，预期一种或多种改性脂族二羧酸的量可以从任何这些上述端点值延伸，包括例如0.01-10mol％和0.1-10mol％。二羧酸组分的总摩尔百分数为100mol％。The carboxylic acid component of the polyester that can be used in the film or sheet of the present invention can further use up to 10 mol%, for example up to 5 mol% or up to 1 mol% of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms, Such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and dodecanedioic acid to modify. Certain embodiments may also comprise 0.01 mol% or more, such as 0.1 mol% or more, 1 mol% or more, 5 mol% or more, or 10 mol% or more of one or more modified aliphatic dicarboxylic acid. Yet another embodiment comprises 0 mol% modified aliphatic dicarboxylic acid. Thus, it is contemplated that the amount of one or more modified aliphatic dicarboxylic acids, if present, can extend from any of these above-mentioned endpoints, including, for example, 0.01-10 mole percent and 0.1-10 mole percent. The total mole percentage of dicarboxylic acid components is 100 mole%.

可以使用对苯二甲酸的酯和其它改性二羧酸或它们相应的酯和/或盐来代替二羧酸。二羧酸酯的合适的实例包括但不限于二甲基、二乙基、二丙基、二异丙基、二丁基和二苯基的酯。在一种实施方案中，所述酯选自以下中的至少一种：甲基、乙基、丙基、异丙基和苯基酯。Esters of terephthalic acid and other modified dicarboxylic acids or their corresponding esters and/or salts may be used instead of dicarboxylic acids. Suitable examples of dicarboxylates include, but are not limited to, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the ester is at least one selected from the group consisting of methyl, ethyl, propyl, isopropyl and phenyl esters.

1，4-环己烷二甲醇可以是顺式、反式或其混合物，例如顺式/反式比例为60∶40-40∶60。在另一实施方案中，反式-1，4-环己烷二甲醇的存在量可以为60-80mol％。1,4-Cyclohexanedimethanol can be in cis form, trans form or a mixture thereof, for example the cis/trans form ratio is 60:40-40:60. In another embodiment, trans-1,4-cyclohexanedimethanol may be present in an amount of 60-80 mole percent.

可用于本发明薄膜或者薄板的聚酯组合物的聚酯部分的二醇组分可以包含25mol％或更少的一种或多种并非2，2，4，4-四甲基-1，3-环丁二醇或1，4-环己烷二甲醇的改性二醇；在一种实施方案中，可用于本发明薄膜或者薄板的聚酯可以包含小于15mol％的一种或多种改性二醇。在另一实施方案中，可用于本发明薄膜或者薄板的聚酯可以包含10mol％或更少的一种或多种改性二醇。在另一实施方案中，可用于本发明薄膜或者薄板的聚酯可以包含5mol％或更少的一种或多种改性二醇。在另一实施方案中，可用于本发明薄膜或者薄板的聚酯可以包含3mol％或更少的一种或多种改性二醇。在另一实施方案中，可用于本发明薄膜或者薄板的聚酯可以包含0mol％的改性二醇。某些实施方案也可包含0.01mol％或更多，如0.1mol％或更多，1mol％或更多，5mol％或更多，或者10mol％或更多的一种或多种改性二醇。因此，如果存在的话，预期一种或多种改性二醇的量可以从任何这些上述端点值延伸，包括例如0.01-15mol％和0.1-10mol％。The diol component of the polyester portion of the polyester composition usable in the film or sheet of the present invention may contain 25 mol% or less of one or more compounds other than 2,2,4,4-tetramethyl-1,3 - modified diols of cyclobutanediol or 1,4-cyclohexanedimethanol; in one embodiment, the polyesters useful in the films or sheets of the present invention may contain less than 15 mol% of one or more modified sexual diol. In another embodiment, the polyesters useful in the films or sheets of the present invention may contain 10 mole percent or less of one or more modifying diols. In another embodiment, the polyesters useful in the films or sheets of the present invention may contain 5 mole percent or less of one or more modifying diols. In another embodiment, the polyesters useful in the films or sheets of the present invention may contain 3 mole percent or less of one or more modifying diols. In another embodiment, the polyesters useful in the films or sheets of the present invention may contain 0 mole percent modifying diol. Certain embodiments may also comprise 0.01 mol% or more, such as 0.1 mol% or more, 1 mol% or more, 5 mol% or more, or 10 mol% or more of one or more modifying diols . Thus, it is contemplated that the amount of one or more modifying diols, if present, can extend from any of these aforementioned endpoints, including, for example, 0.01-15 mole percent and 0.1-10 mole percent.

对可用于本发明薄膜或者薄板的聚酯有用的改性二醇是指除2，2，4，4-四甲基-1，3-环丁二醇和1，4-环己烷二甲醇之外的二醇，并且可以包含2-16个碳原子。合适的改性二醇的实例包括但不局限于乙二醇、二甘醇、1，2-丙二醇、1，3-丙二醇、新戊二醇、1，4-丁二醇、1，5-戊二醇、1，6-己二醇、对二甲苯二醇或其混合物。在一个实施方案中，改性二醇为乙二醇。在另一实施方案中，改性二醇包括但不限于1，3-丙二醇和/或1，4-丁二醇。在另一实施方案中，排除乙二醇作为改性二醇。在另一实施方案中，排除1，3-丙二醇和1，4-丁二醇作为改性二醇。在另一实施方案中，排除2，2-二甲基-1，3-丙二醇作为改性二醇。对本发明薄膜或者薄板的聚酯组合物有用的聚酯和/或聚碳酸酯，分别基于二醇或二酸残基的总摩尔百分数，可以包含0-10mol％，例如0.01-5mol％、0.01-1mol％、0.05-5mol％、0.05-1mol％、或者0.1-0.7mol％、或者0.1-0.5mol％的一种或多种支化单体的残基，其在本文中也称作支化剂，具有3个或更多个羧基取代基、羟基取代基或其组合。在某些实施方案中，可以在聚酯聚合之前和/或期间和/或之后添加支化单体或支化剂。因此，可用于本发明薄膜或者薄板的聚酯可以是线性或分枝的。聚碳酸酯还可能是线性或分枝的。在某些实施方案中，可以在聚碳酸酯聚合之前和/或期间和/或之后添加支化单体或支化剂。Useful modifying diols for polyesters that can be used in the film or sheet of the present invention are those other than 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol and can contain 2-16 carbon atoms. Examples of suitable modifying diols include, but are not limited to, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5- Pentylene glycol, 1,6-hexanediol, p-xylylene glycol or mixtures thereof. In one embodiment, the modifying diol is ethylene glycol. In another embodiment, modifying diols include, but are not limited to, 1,3-propanediol and/or 1,4-butanediol. In another embodiment, ethylene glycol is excluded as the modifying diol. In another embodiment, 1,3-propanediol and 1,4-butanediol are excluded as modifying diols. In another embodiment, 2,2-dimethyl-1,3-propanediol is excluded as modifying diol. The polyester and/or polycarbonate useful for the polyester composition of the film or sheet of the present invention, based on the total mole percentage of diol or diacid residues, respectively, may comprise 0-10 mol%, for example 0.01-5 mol%, 0.01- 1 mol%, 0.05-5 mol%, 0.05-1 mol%, or 0.1-0.7 mol%, or 0.1-0.5 mol% residues of one or more branching monomers, also referred to herein as branching agents , having 3 or more carboxy substituents, hydroxy substituents, or combinations thereof. In certain embodiments, branching monomers or branching agents may be added before and/or during and/or after polyester polymerization. Thus, the polyesters useful in the films or sheets of the present invention may be linear or branched. Polycarbonates may also be linear or branched. In certain embodiments, branching monomers or branching agents may be added before and/or during and/or after polycarbonate polymerization.

支化单体的实例包括但不限于多官能酸或多官能醇，例如偏苯三酸、偏苯三酸酐、均苯四酸二酐、三羟甲基丙烷、甘油、季戊四醇、柠檬酸、酒石酸、3-羟基戊二酸等。在一种实施方案中，支化单体残基可以包含0.1-0.7mol％的一种或多种选自下列至少一种的残基：偏苯三酸酐、均苯四酸二酐、甘油、山梨糖醇、1，2，6-己三醇、季戊四醇、三羟甲基乙烷和/或苯均三酸。可以将支化单体加到聚酯反应混合物中，或者以浓缩物形式与聚酯共混，如例如美国专利5,654,347和5,696,176中所述，其关于支化单体的公开内容引入本文作为参考。Examples of branching monomers include, but are not limited to, polyfunctional acids or alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3- Hydroxyglutaric acid, etc. In one embodiment, the branched monomer residues may comprise 0.1-0.7 mol% of one or more residues selected from at least one of the following: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol , 1,2,6-hexanetriol, pentaerythritol, trimethylolethane and/or trimesic acid. Branching monomers can be added to the polyester reaction mixture or blended with the polyester as a concentrate as described, for example, in US Patent Nos. 5,654,347 and 5,696,176, the disclosures of which are incorporated herein by reference for branching monomers.

可用于本发明薄膜或者薄板的聚酯的玻璃化转变温度(Tg)是使用Thermal Analyst Instruments的TA DSC 2920以20℃/min的扫描速率测定的。The glass transition temperature (Tg) of the polyesters useful in the films or sheets of the present invention was determined using a TA DSC 2920 from Thermal Analyst Instruments at a scan rate of 20°C/min.

对本发明有用的聚酯可以是无定形的或半结晶的。在一种实施方案中，“无定形”聚酯可以具有在170℃大于5分钟或在170℃大于10分钟或在170℃大于50分钟或在170℃大于100分钟的结晶半衰期。本发明的一种实施方案中，结晶半衰期在170℃大于1000分钟。在本发明的另一实施方案中，对本发明有用的聚酯的结晶半衰期在170℃大于10,000分钟。如本文中使用的，聚酯的结晶半衰期可以使用本领域技术人员众所周知的方法来测量。例如，聚酯的结晶半衰期，t1/2，可以通过在温控热台上随着时间经激光器和光电检测器测量样品的透光率来测定。这种测量可以是这样进行的：通过将聚合物暴露于温度T_max，并随后将其冷却到期望的温度。随后可以通过热台将样品保持在期望的温度，同时测量透光率随时间的变化。最初，样品可以是视觉上透明的，具有高透光率，且随着样品结晶而变得不透明。结晶半衰期是透光率在初始透光率与最终透光率之间一半时的时间。T_max定义为熔融样品晶畴所需的温度(如果存在晶畴的话)。可以在结晶半衰期测量之前将样品加热到T_max以调理该样品。对于每一种组合物，绝对T_max温度是不同的。例如可以将PCT加热到高于290℃的某温度以熔融晶畴。Polyesters useful in the present invention can be amorphous or semicrystalline. In one embodiment, an "amorphous" polyester may have a crystallization half-life of greater than 5 minutes at 170°C, or greater than 10 minutes at 170°C, or greater than 50 minutes at 170°C, or greater than 100 minutes at 170°C. In one embodiment of the invention, the crystallization half-life is greater than 1000 minutes at 170°C. In another embodiment of the present invention, the polyesters useful in the present invention have a crystallization half-life of greater than 10,000 minutes at 170°C. As used herein, the crystallization half-life of a polyester can be measured using methods well known to those skilled in the art. For example, the crystallization half-life of polyesters, t1/2, can be determined by measuring the transmittance of a sample over time on a temperature-controlled hot-stage via a laser and a photodetector. This measurement can be carried out by exposing the polymer to the temperature_Tmax and subsequently cooling it to the desired temperature. The sample can then be maintained at the desired temperature by means of a hot stage while the transmittance is measured over time. Initially, the sample may be visually transparent with high light transmission and become opaque as the sample crystallizes. The crystallization half-life is the time at which the transmittance is halfway between the initial transmittance and the final transmittance. T_max is defined as the temperature required to melt the crystal domains of the sample (if domains exist). The sample can be conditioned by heating it to_Tmax prior to crystallization half-life measurements. The absolute_Tmax temperature is different for each composition. For example the PCT can be heated to a temperature above 290°C to melt the domains.

如实施例的表1和图1所示，在提高结晶半衰期(即聚合物达到其最大结晶度一半所需的时间)方面，2，2，4，4-四甲基-1，3-环丁二醇比其它共聚单体，如乙二醇和间苯二甲酸更有效。通过降低PCT的结晶速率，即提高结晶半衰期，可以通过本领域已知的方法如挤出、注塑等制造基于改性PCT的无定形制品。如表1所示，这些材料可以显示比其它改性PCT共聚酯更高的玻璃化转变温度和更低的密度。As shown in Table 1 and Figure 1 of the Examples, 2,2,4,4-tetramethyl-1,3-cyclo Butanediol is more effective than other comonomers such as ethylene glycol and isophthalic acid. By reducing the crystallization rate of PCT, that is, increasing the half-life of crystallization, amorphous articles based on modified PCT can be produced by methods known in the art, such as extrusion, injection molding, and the like. As shown in Table 1, these materials can exhibit higher glass transition temperatures and lower densities than other modified PCT copolyesters.

对于某些本发明的实施方案，本发明薄膜或者薄板的聚酯可以显示出韧性与加工性能结合的改进。例如，出人意料的是稍微降低可用于本发明薄膜或者薄板的聚酯的比浓对数粘度导致更易加工的熔体粘度，同时保持聚酯的良好的物理性能，例如韧性和耐热性。For certain embodiments of the present invention, the polyesters of the films or sheets of the present invention may exhibit an improved combination of toughness and processability. For example, it was surprising that slightly lowering the inherent viscosity of the polyesters useful in the films or sheets of the present invention results in more processable melt viscosities while maintaining the good physical properties of the polyesters, such as toughness and heat resistance.

在基于对苯二甲酸、乙二醇和1，4-环己烷二甲醇的共聚酯中提高1，4-环己烷二甲醇的含量可以改进韧性，所述韧性可以在如由ASTM D256测量的切口伊佐德冲击强度测试中通过韧脆性转变温度来测定。据信，通过用1，4-环己烷二甲醇降低韧脆性转变温度，这种韧性改进是由于共聚酯中1，4-环己烷二甲醇的挠性和构象性能而发生的。据信，将2，2，4，4-四甲基-1，3-环丁二醇引入到PCT中，通过降低韧脆性转变温度改进了韧性，如实施例的表2和图2所示。Increasing the content of 1,4-cyclohexanedimethanol in copolyesters based on terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol improves toughness as measured by ASTM D256 The notched Izod impact strength test is determined by the ductile-brittle transition temperature. It is believed that this toughness improvement occurs due to the flexibility and conformational properties of 1,4-cyclohexanedimethanol in the copolyester by lowering the ductile-brittle transition temperature with 1,4-cyclohexanedimethanol. It is believed that incorporation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol into PCT improves toughness by lowering the ductile-brittle transition temperature, as shown in Table 2 and Figure 2 of the Examples .

在一种实施方案中，对本发明薄膜或者薄板有用的聚酯的熔体粘度小于30,000泊，如在290℃在旋转熔体流变仪上在1弧度/秒测量的。在另一实施方案中，对本发明薄膜或者薄板有用的聚酯的熔体粘度小于20,000泊，如在290℃在旋转熔体流变仪上在1弧度/秒测量的。In one embodiment, polyesters useful for films or sheets of the present invention have a melt viscosity of less than 30,000 poise as measured at 290°C on a rotational melt rheometer at 1 rad/sec. In another embodiment, polyesters useful for the films or sheets of the present invention have a melt viscosity of less than 20,000 poise, as measured at 290°C on a rotational melt rheometer at 1 rad/sec.

在一种实施方案中，对本发明薄膜或者薄板有用的聚酯的熔体粘度小于15,000泊，如在旋转熔体流变仪上在290℃以1弧度/秒测量的。在一种实施方案中，对本发明薄膜或者薄板有用的聚酯的熔体粘度小于10,000泊，如在旋转熔体流变仪上在290℃以1弧度/秒测量的。在另一实施方案中，对本发明薄膜或者薄板有用的聚酯的熔体粘度小于6,000泊，如在290℃在旋转熔体流变仪上在1弧度/秒测量的。以弧度/秒为单位的粘度与加工性能有关。当在其加工温度测量时，典型聚合物具有小于10000泊的粘度，如在1弧度/秒测量的。一般不在290℃以上加工聚酯。一般在290℃加工聚碳酸酯。在290℃，典型的12熔体流动速率聚碳酸酯在1弧度/秒下的粘度为7000泊。In one embodiment, polyesters useful for films or sheets of the present invention have a melt viscosity of less than 15,000 poise, as measured on a rotational melt rheometer at 290°C at 1 rad/sec. In one embodiment, polyesters useful for films or sheets of the present invention have a melt viscosity of less than 10,000 poise as measured on a rotational melt rheometer at 290°C at 1 rad/sec. In another embodiment, the polyesters useful for the films or sheets of the present invention have a melt viscosity of less than 6,000 poise, as measured at 290°C on a rotational melt rheometer at 1 rad/sec. Viscosity in rad/s is related to processability. Typical polymers have a viscosity of less than 10,000 poise, as measured at 1 rad/sec, when measured at their processing temperature. Polyester is generally not processed above 290°C. Polycarbonate is generally processed at 290°C. A typical 12 melt flow rate polycarbonate has a viscosity of 7000 poise at 1 rad/sec at 290°C.

在一种实施方案中，本发明薄膜或者薄板的聚酯显示出优良的在厚度截面上的切口韧性。ASTM D256所述的切口伊佐德冲击强度是测量韧性的一种常用方法。在一种实施方案中，可用于本发明薄膜或者薄板的聚酯显示出在23℃以10-密耳切口在3.2mm(1/8-英寸)厚试条中的至少150J/m(3ft-lb/in)的冲击强度，本发明的薄膜或者薄板显示出在23℃以10-密耳切口在3.2mm(1/8-英寸)厚试条中根据ASTM D256测定的至少(400J/m)7.5ft-lb/in的切口伊佐德冲击强度；在一种实施方案中，可用于本发明薄膜或者薄板的聚酯显示出在23℃以10-密耳切口在3.2mm(1/8-英寸)厚试条中根据ASTM D256测定的至少1000J/m(18ft-lb/in)的切口伊佐德冲击强度。在一种实施方案中，可用于本发明薄膜或者薄板的聚酯显示出在23℃以10-密耳切口在6.4mm(1/4-in)厚试条中根据ASTM D256测定的至少150J/m(3ft-lb/in)的切口伊佐德冲击强度；在一种实施方案中，可用于本发明薄膜或者薄板的聚酯显示出在23℃以10-密耳切口在6.4mm(1/4-in)厚试条中根据ASTM D256测定的至少(400J/m)7.5ft-lb/in的切口伊佐德冲击强度；在一种实施方案中，可用于本发明薄膜或者薄板的聚酯显示出在23℃以10-密耳切口在6.4mm(1/4-in)厚试条中根据ASTM D256测定的至少1000J/m(18ft-lb/in)的切口伊佐德冲击强度。In one embodiment, the polyesters of the films or sheets of the invention exhibit excellent notch toughness in the thickness section. Notched Izod impact strength as described in ASTM D256 is a common method of measuring toughness. In one embodiment, the polyesters useful in the films or sheets of the present invention exhibit at least 150 J/m (3 ft- lb/in) of impact strength, the film or sheet of the present invention exhibits at least (400 J/m) as determined in accordance with ASTM D256 with a 10-mil notch at 23°C in a 3.2 mm (1/8-inch) thick test bar Notched Izod impact strength of 7.5 ft-lb/in; In one embodiment, polyesters useful in the films or sheets of the present invention exhibit ) notched Izod impact strength of at least 1000 J/m (18 ft-lb/in) as determined in accordance with ASTM D256 in thick bars. In one embodiment, the polyesters useful in the films or sheets of the present invention exhibit at least 150 J/L measured in accordance with ASTM D256 with a 10-mil notch at 23°C in a 6.4 mm (1/4-in) thick test bar. Notched Izod impact strength in m (3 ft-lb/in); in one embodiment, polyesters useful in the films or sheets of the present invention exhibit - in) a notched Izod impact strength of at least (400 J/m) 7.5 ft-lb/in as determined according to ASTM D256 in thick bars; in one embodiment, the polyesters useful in the films or sheets of the present invention exhibit A notched Izod impact strength of at least 1000 J/m (18 ft-lb/in) measured according to ASTM D256 with a 10-mil notch at 23°C in 6.4 mm (1/4-in) thick bars.

在另一实施方案中，对本发明薄膜或者薄板有用的某些聚酯，与在-5℃测量时以10-密耳切口在1/8-in厚试条中根据ASTM D256测定的切口伊佐德冲击强度相比，可以显示出在0℃测量时的切口伊佐德冲击强度增加了至少3％或者至少5％或者至少10％或者至少15％。另外，本发明的某些其它聚酯还可以显示出根据ASTM D256在1/8-in厚试条中以10-密耳切口测定的在0℃-30℃测量时的在正或负5％以内的切口伊佐德冲击强度的保持。In another embodiment, certain polyesters useful in the films or sheets of the present invention are compared to the Notch Izod measured at -5°C with a 10-mil notch in 1/8-in thick test strips according to ASTM D256. It may be shown that the notched Izod impact strength when measured at 0° C. is increased by at least 3%, or at least 5%, or at least 10%, or at least 15% compared to the impact strength. In addition, certain other polyesters of the present invention may also exhibit a 0°C to 30°C measurement in accordance with ASTM D256 with a 10-mil notch in 1/8-in. Retention of Izod impact strength within the cut.

在又一实施方案中，对本发明薄膜或者薄板有用的某些聚酯可以显示出根据ASTM D256在1/8-in厚试条中以10-密耳切口测定的在23℃测量时的切口伊佐德冲击强度的保持的损失不大于70％，相比于根据ASTM D256在1/8-in厚试条中以10-密耳切口测定的在相同温度测量时的相同聚酯的切口伊佐德冲击强度来说。In yet another embodiment, certain polyesters useful for the films or sheets of the present invention may exhibit a Notch IZO when measured at 23°C according to ASTM D256 as determined with a 10-mil notch in 1/8-in thick test strips. Retained Izod impact strength with no more than a 70% loss compared to the notched Izod impact of the same polyester when measured at the same temperature as determined with a 10-mil notch in 1/8-in thick bars according to ASTM D256 In terms of strength.

在一种实施方案中，可用于本发明薄膜或者薄板的聚酯可以显示出小于0℃的韧脆性转变温度，基于10-密耳切口在1/8-in厚试条中正如ASTM D256所定义的。In one embodiment, the polyesters useful in the films or sheets of the present invention may exhibit a ductile-brittle transition temperature of less than 0°C, based on a 10-mil notch in a 1/8-in thick test bar as defined by ASTM D256 of.

在一种实施方案中，在23℃使用梯度密度柱，可用于本发明薄膜或者薄板的聚酯可以显示出至少一种以下密度：在23℃小于1.2g/ml的密度；在23℃小于1.18g/ml的密度；在23℃ 0.8-1.3g/ml的密度；在23℃ 0.80-1.2g/ml的密度；在23℃ 0.80-小于1.2g/ml的密度；在23℃ 1.0-1.3g/ml的密度；在23℃ 1.0-1.2g/ml的密度；在23℃ 1.0-1.1g/ml的密度；在23℃ 1.13-1.3g/ml的密度；在23℃ 1.13-1.2g/ml的密度。In one embodiment, using a gradient density column at 23°C, polyesters useful in the films or sheets of the present invention may exhibit at least one of the following densities: a density of less than 1.2 g/ml at 23°C; a density of less than 1.18 g/ml at 23°C; Density in g/ml; density at 23°C 0.8-1.3g/ml; density at 23°C 0.80-1.2g/ml; density at 23°C 0.80-less than 1.2g/ml; density at 23°C 1.0-1.3g Density per ml; density at 23°C 1.0-1.2g/ml; density at 23°C 1.0-1.1g/ml; density at 23°C 1.13-1.3g/ml; density at 23°C 1.13-1.2g/ml Density.

在一种实施方案中，本发明薄膜或者薄板的聚酯可以是视觉上透明的。术语“视觉上透明的”在本文中定义为当目视检测时明显没有浑浊、朦胧和/或污浊。在另一实施方案中，当可用于本发明薄膜或者薄板的聚酯与聚碳酸酯(包括但不限于双酚A聚碳酸酯)共混时，则共混物可以是视觉上透明的。In one embodiment, the polyester of the film or sheet of the present invention may be visually clear. The term "visually clear" is defined herein as being visibly free from cloudiness, haze, and/or smudging when inspected visually. In another embodiment, when the polyesters useful in the films or sheets of the present invention are blended with polycarbonates, including but not limited to bisphenol A polycarbonates, then the blends may be visually clear.

可用于本发明薄膜或者薄板的聚酯具有一种或多种下列性能。在其它实施方案中，可用于本发明薄膜或者薄板的聚酯可以具有小于50或小于20的黄度指数(ASTM D-1925)。Polyesters useful in the films or sheets of the present invention have one or more of the following properties. In other embodiments, the polyesters useful in the films or sheets of the present invention may have a yellowness index (ASTM D-1925) of less than 50 or less than 20.

在一种实施方案中，可用于本发明薄膜或者薄板的聚酯和/或本发明薄膜或者薄板的聚酯组合物，含或不含调色剂，可以具有色值L^*、a^*和b^*，其可以是使用由Hunter Associates Lab Inc.，Reston，Va制造的Hunter Lab Ultrascan Spectra Colorimeter测定的。颜色测定值是在聚酯粒料或由其注塑或挤出的板或其它物件上测量的值的平均值。它们是由CIE(国际照明委员会)(译)的L^*a^*b^*色系测定的，其中L^*表示光亮度坐标，a^*表示红/绿坐标，b^*表示黄/蓝坐标。在某些实施方案中，可用于本发明薄膜或者薄板的聚酯的b^*值可以为-10至小于10，而L^*值可以为50至90。在其它实施方案中，可用于本发明薄膜或者薄板的聚酯的b^*值可以存在于下述范围之一：-10至9；-10至8；-10至7；-10至6；-10至5；-10至4；-10至3；-10至2；-5至9；-5至8；-5至7；-5至6；-5至5；-5至4；-5至3；-5至2；0至9；0至8；0至7；0至6；0至5；0至4；0至3；0至2；1至10；1至9；1至8；1至7；1至6；1至5；1至4；1至3；和1至2。在其它实施方案中，可用于本发明薄膜或者薄板的聚酯的L^*值可以存在于下述范围之一：50-60；50-70；50-80；50-90；60-70；60-80；60-90；70-80；79-90。In one embodiment, the polyesters useful in the films or sheets of the invention and/or the polyester compositions of the films or sheets of the invention, with or without toners, can have color values L^* , a^* and b^* , which can be determined using a Hunter Lab Ultrascan Spectra Colorimeter manufactured by Hunter Associates Lab Inc., Reston, Va. The color determination is the average of the values measured on polyester pellets or sheets or other objects injected or extruded therefrom. They are determined by the L^* a^* b^* color system of the CIE (International Commission on Illumination) (translation), where L^* indicates the luminance coordinate, a^* indicates the red/green coordinate, and b^* indicates the yellow/blue coordinate. In certain embodiments, the polyesters useful in the films or sheets of the present invention can have a b^* value of -10 to less than 10, and an L^* value of 50 to 90. In other embodiments, the b^* value of the polyesters useful in the films or sheets of the present invention may exist in one of the following ranges: -10 to 9; -10 to 8; -10 to 7; -10 to 6; - 10 to 5; -10 to 4; -10 to 3; -10 to 2; -5 to 9; -5 to 8; -5 to 7; -5 to 6; -5 to 5; -5 to 4; - 5 to 3; -5 to 2; 0 to 9; 0 to 8; 0 to 7; 0 to 6; 0 to 5; 0 to 4; 0 to 3; 0 to 2; 1 to 10; 1 to 9; 1 to 8; 1 to 7; 1 to 6; 1 to 5; 1 to 4; 1 to 3; and 1 to 2. In other embodiments, the L^* value of the polyesters useful in the films or sheets of the present invention may exist in one of the following ranges: 50-60; 50-70; 50-80; 50-90; 60-70; 60 -80; 60-90; 70-80; 79-90.

在一些实施方案中，使用可用于本发明薄膜或者薄板的聚酯组合物最小化和/或消除了在熔融加工和/或热成形之前的干燥步骤。In some embodiments, use of the polyester compositions useful in the films or sheets of the present invention minimizes and/or eliminates drying steps prior to melt processing and/or thermoforming.

虽然可用于本发明薄膜或者薄板的聚酯可以具有任何水分含量，在一种实施方案中，它们的水分含量可以为0.02-1.0wt％的熔融加工前的聚酯的总重量。While the polyesters useful in the films or sheets of the present invention can have any moisture content, in one embodiment they can have a moisture content of from 0.02 to 1.0 wt% of the total weight of the polyester prior to melt processing.

在某些实施方案中，在熔融加工前通过常规方法在60℃-100℃干燥可用于本发明薄膜或者薄板的聚酯小于2小时。In certain embodiments, polyesters useful in films or sheets of the present invention are dried by conventional methods at 60°C to 100°C for less than 2 hours prior to melt processing.

可用于本发明薄膜或者薄板的聚酯可以通过文献中已知工艺制备，例如通过在均质溶液中的工艺、通过熔体中的酯交换工艺和通过双相界面工艺。合适的方法包括但不限于使一种或多种二羧酸与一种或多种二醇在100℃-315℃的温度和0.1-760mmHg的压力下反应足以形成聚酯的时间的步骤。对于生产聚酯的方法，参见美国专利3,772,405，这种方法的公开内容引入本文作为参考。The polyesters which can be used in the films or sheets according to the invention can be prepared by processes known in the literature, for example by processes in homogeneous solutions, by transesterification processes in the melt and by two-phase interface processes. Suitable methods include, but are not limited to, the step of reacting one or more dicarboxylic acids with one or more diols at a temperature of 100°C to 315°C and a pressure of 0.1 to 760 mmHg for a time sufficient to form a polyester. For methods of producing polyesters, see US Patent 3,772,405, the disclosure of which is incorporated herein by reference.

在另一方面中，本发明涉及用于生产对本发明薄膜或者薄板有用的聚酯的方法。所述方法包括：(I)在催化剂存在下在150-240℃加热包含可用于任何对本发明有用的聚酯的单体的混合物足以产生初始聚酯的时间；(II)在240-320℃温度下加热步骤(I)的初始聚酯达1-4小时；和(III)除去任何未反应的二醇。In another aspect, the invention relates to a process for producing polyesters useful for the films or sheets of the invention. The process comprises: (I) heating a mixture comprising monomers useful in any polyester useful in the present invention at 150-240°C in the presence of a catalyst for a time sufficient to produce the initial polyester; (II) at a temperature of 240-320°C The initial polyester of step (I) is heated for 1-4 hours; and (III) any unreacted diol is removed.

用于该方法的合适的催化剂包括但不局限于有机锌或锡化合物。使用这种类型的催化剂在本领域中是众所周知的。可用于本发明的催化剂的实例包括但不限于乙酸锌、三(2-乙基己酸)丁基锡、二乙酸二丁基锡和/或氧化二丁锡。其它催化剂可包括但不限于基于钛、锌、锰、锂、锗和钴的那些。催化剂数量可以为10ppm-20,000ppm或者10-10,000ppm，或者10-5000ppm或者10-1000ppm或者10-500ppm，或者10-300ppm或者10-250，基于催化剂金属和基于最终聚合物的重量。该方法可以以间歇过程或连续过程的方式进行。Suitable catalysts for this process include, but are not limited to, organozinc or tin compounds. The use of catalysts of this type is well known in the art. Examples of catalysts useful in the present invention include, but are not limited to, zinc acetate, butyltin tris(2-ethylhexanoate), dibutyltin diacetate, and/or dibutyltin oxide. Other catalysts may include, but are not limited to, those based on titanium, zinc, manganese, lithium, germanium, and cobalt. Catalyst amounts can range from 10 ppm to 20,000 ppm or 10-10,000 ppm, or 10-5000 ppm or 10-1000 ppm or 10-500 ppm, or 10-300 ppm or 10-250, based on catalyst metal and based on the weight of the final polymer. The method can be carried out as a batch process or as a continuous process.

一般地，步骤(I)可以进行直到50wt％或更多的2，2，4，4-四甲基-1，3-环丁二醇已经反应。步骤(I)可以在压力下进行，压力范围为大气压力至100psig。如与任何对可用于本发明薄膜或者薄板的聚酯有用的催化剂相结合使用的术语“反应产物”是指使用催化剂和用于制备聚酯的任何单体的缩聚或者酯化反应的任何产物以及催化剂和任何其它类型的添加剂间的缩聚或者酯化反应的产物。Generally, step (I) can be carried out until 50 wt% or more of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol has reacted. Step (I) can be performed under pressure ranging from atmospheric pressure to 100 psig. The term "reaction product" as used in connection with any catalyst useful for the polyesters useful in the films or sheets of the present invention means any product of a polycondensation or esterification reaction using the catalyst and any monomers used to make the polyester and The product of a polycondensation or esterification reaction between a catalyst and any other type of additive.

一般地，步骤(II)和步骤(III)可以同时进行。这些步骤可以通过本领域已知的方法进行，例如通过将反应混合物置于压力下，压力范围为0.002psig至低于大气压力，或者通过在混合物上吹入热氮气。Generally, step (II) and step (III) can be carried out simultaneously. These steps can be performed by methods known in the art, such as by placing the reaction mixture under pressure, ranging from 0.002 psig to subatmospheric pressure, or by blowing hot nitrogen over the mixture.

本发明还涉及对本发明薄膜或者薄板有用的聚合物的共混物。所述共混物包含：(a)5-95wt％的至少一种的上述聚酯；和(b)5-95wt％的至少一种的聚合物组分。The invention also relates to blends of polymers useful for the films or sheets of the invention. The blend comprises: (a) 5-95 wt% of at least one polyester described above; and (b) 5-95 wt% of at least one polymer component.

聚合物组分的合适的实例包括但不限于，尼龙，不同于本文中所述的那些的其它聚酯，尼龙，聚酰胺如来自DuPont的ZYTEL

；不同于本文中所述的那些的聚酯；聚苯乙烯，聚苯乙烯生聚物，苯乙烯丙烯腈共聚物，丙烯腈-丁二烯-苯乙烯共聚物，聚甲基丙烯酸甲酯，丙烯酸系共聚物，聚(醚-酰亚胺)如ULTEM

(聚(醚-酰亚胺)，获自GeneralElectric)；聚苯醚如聚(2，6-二甲基苯醚)或者聚苯醚/聚苯乙烯共混物如NORYL 1000

(聚(2，6-二甲基苯醚)和聚苯乙烯树脂的共混物，获自General Electric)；聚苯硫醚；聚苯硫醚/砜；聚(酯-碳酸酯)；聚碳酸酯如LEXAN(聚碳酸酯，获自General Electric)；聚砜；聚砜醚；和芳族二羟基化合物的聚(醚-酮)或任何其它在前聚合物的混合物。共混物可以通过本领域已知的常规处理工艺制备，如熔融共混或溶液共混。在一种实施方案中，聚碳酸酯不存在于可用于本发明薄膜或者薄板的聚酯组合物中。如果聚碳酸酯用于可用于本发明薄膜或者薄板的聚酯组合物的共混物中，则共混物可以是视觉上透明的。然而，可用于本发明薄膜或者薄板的聚酯组合物也预期了聚碳酸酯的排除以及包括聚碳酸酯。Suitable examples of polymer components include, but are not limited to, nylon, other polyesters than those described herein, nylon, polyamides such as ZYTEL from DuPont

; polyesters other than those described herein; polystyrene, polystyrene biopolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polymethylmethacrylate, Acrylic copolymers, poly(ether-imide) such as ULTEM

(poly(ether-imide), available from General Electric); polyphenylene ethers such as poly(2,6-dimethylphenylene ether) or polyphenylene ether/polystyrene blends such as NORYL 1000

(blend of poly(2,6-dimethylphenylene ether) and polystyrene resin, available from General Electric); polyphenylene sulfide; polyphenylene sulfide/sulfone; poly(ester-carbonate); poly(ester-carbonate); Carbonate such as LEXAN (polycarbonate, available from General Electric); polysulfone; polysulfone ether; and poly(ether-ketone) of aromatic dihydroxy compounds or any other mixture of the preceding polymers. Blends can be prepared by conventional processing techniques known in the art, such as melt blending or solution blending. In one embodiment, polycarbonate is absent from the polyester compositions useful in the films or sheets of the present invention. If polycarbonates are used in blends of polyester compositions useful in the films or sheets of the present invention, the blends may be visually clear. However, the exclusion of and inclusion of polycarbonate is also contemplated by the polyester compositions useful in the films or sheets of the present invention.

对本发明薄膜或者薄板有用的聚碳酸酯可以根据已知方法制备，例如通过使二羟基芳族化合物与碳酸酯前体如光气、卤代甲酸酯或碳酸酯、分子量调节剂、受酸体和催化剂反应。用于制备聚碳酸酯的方法是本领域已知的并且例如描述于美国专利4,452,933中，其中关于聚碳酸酯制备的公开内容在此引入本文作为参考。Polycarbonates useful for films or sheets according to the invention can be prepared according to known methods, for example by reacting dihydroxyaromatic compounds with carbonate precursors such as phosgene, haloformates or carbonates, molecular weight regulators, acid acceptors react with the catalyst. Methods for preparing polycarbonates are known in the art and are described, for example, in US Pat. No. 4,452,933, the disclosure of which with respect to the preparation of polycarbonates is incorporated herein by reference.

合适的碳酸酯前体的实例包括但不局限于，碳酰溴、碳酰氯或其混合物；碳酸二苯酯；碳酸二(卤代苯基)酯，例如，碳酸二(三氯苯基)酯，碳酸二(三溴苯基)酯等；碳酸二(烷基苯基)酯，例如，碳酸二(甲苯基)酯；碳酸二(萘基)酯；碳酸二(氯萘基)酯或其混合物；和二元酚的二卤代甲酸酯。Examples of suitable carbonate precursors include, but are not limited to, carbonyl bromide, carbonyl chloride, or mixtures thereof; diphenyl carbonate; bis(halophenyl)carbonate, e.g., bis(trichlorophenyl)carbonate , bis(tribromophenyl)carbonate, etc.; bis(alkylphenyl)carbonate, for example, bis(cresyl)carbonate; bis(naphthyl)carbonate; bis(chloronaphthyl)carbonate or mixtures; and dihaloformates of dihydric phenols.

合适的分子量调节剂的实例包括但不限于，苯酚、环己醇、甲醇、烷基化苯酚如辛基苯酚、对叔丁基苯酚等。在一种实施方案中，分子量调节剂是苯酚或者烷基化苯酚。Examples of suitable molecular weight regulators include, but are not limited to, phenol, cyclohexanol, methanol, alkylated phenols such as octylphenol, p-tert-butylphenol, and the like. In one embodiment, the molecular weight regulator is phenol or alkylated phenols.

酸受体可能是有机或者无机酸受体。合适的有机酸受体可以是叔胺并且包括但不局限于，诸如吡啶、三乙胺、二甲苯胺、三丁胺等材料。无机酸受体可以是碱金属或碱土金属的氢氧化物、碳酸盐、碳酸氢盐或磷酸盐。Acid acceptors may be organic or inorganic acid acceptors. Suitable organic acid acceptors may be tertiary amines and include, but are not limited to, materials such as pyridine, triethylamine, xylidine, tributylamine, and the like. The inorganic acid acceptor may be an alkali metal or alkaline earth metal hydroxide, carbonate, bicarbonate or phosphate.

可以使用的催化剂包括但不局限于，通常有助于单体与光气聚合的那些。合适的催化剂包括但不限于，叔胺如三乙胺、三丙胺、N，N-二甲苯胺，季铵化合物如四乙基溴化铵、十六烷基三乙基溴化铵、四正庚基碘化铵、四正丙基溴化铵、四甲基氯化铵、四甲基氢氧化铵、四正丁基碘化铵、苄基三甲基氯化胺以及季鏻化合物如正丁基三苯基溴化鏻和甲基三苯基溴化鏻。Catalysts that may be used include, but are not limited to, those that generally facilitate the polymerization of monomers and phosgene. Suitable catalysts include, but are not limited to, tertiary amines such as triethylamine, tripropylamine, N,N-xylaniline, quaternary ammonium compounds such as tetraethylammonium bromide, cetyltriethylammonium bromide, tetra-n- Heptylammonium iodide, tetra-n-propylammonium bromide, tetramethylammonium chloride, tetramethylammonium hydroxide, tetra-n-butylammonium iodide, benzyltrimethylammonium chloride and quaternary phosphonium compounds such as Butyltriphenylphosphonium bromide and methyltriphenylphosphonium bromide.

对本发明薄膜或者薄板的聚酯组合物有用的聚碳酸酯还可能是共聚酯碳酸酯，如描述于以下美国专利中的那些：3,169,121；3,207,814；4,194,038；4,156,069；4,430,484、4,465,820和4,981,898；其中各篇美国专利有关共聚酯碳酸酯的公开内容引入本文作为参考。Polycarbonates useful for the polyester compositions of the films or sheets of the present invention may also be copolyestercarbonates such as those described in the following U.S. Patents: 3,169,121; 3,207,814; 4,194,038; 4,156,069; The disclosures of this US patent relating to copolyestercarbonates are incorporated herein by reference.

对本发明薄膜或者薄板有用的共聚酯碳酸酯可以是市售可得的和/或可以通过本领域中已知的方法制备。例如，它们可以一般通过使至少一种二羟基芳族化合物与光气和至少一种二酰氯(特别是间苯二酰氯、对苯二酰氯或两者)的混合物反应而获得。Copolyestercarbonates useful for the films or sheets of the present invention may be commercially available and/or may be prepared by methods known in the art. For example, they can generally be obtained by reacting at least one dihydroxyaromatic compound with a mixture of phosgene and at least one diacid chloride, in particular isophthaloyl dichloride, terephthaloyl dichloride or both.

另外，包含可用于本发明薄膜或者薄板的聚酯的聚酯组合物和聚合物共混物组合物还可包含聚酯组合物总重量的0.01-25wt％或0.01-20wt％或0.01-15wt％或0.01-10wt％或0.01-5wt％的常用添加剂如着色剂、染料、脱模剂、阻燃剂、增塑剂、成核剂、稳定剂(包括但不限于紫外稳定剂、热稳定剂和/或其反应产物)、填料和耐冲击性改进剂。本领域众所周知的且可用于本发明的典型的市售可得的耐冲击性改进剂的实例包括但不局限于，乙烯/丙烯三元共聚物；官能化聚烯烃，如包含丙烯酸甲酯和/或甲基丙烯酸缩水甘油酯的那些；基于苯乙烯的嵌段共聚物耐冲击性改进剂；和各种丙烯酸系的核/壳型耐冲击性改进剂。例如，通过经施加硬膜或者经共挤压盖层而添加到本体中，可以将UV添加剂结合到制品中。也预期将这种添加剂的残余物作为对本发明薄膜或者薄板有用的聚酯组合物的一部分。In addition, polyester compositions and polymer blend compositions comprising polyesters useful in the films or sheets of the present invention may further comprise 0.01-25 wt % or 0.01-20 wt % or 0.01-15 wt % of the total weight of the polyester composition Or 0.01-10wt% or 0.01-5wt% of commonly used additives such as colorants, dyes, release agents, flame retardants, plasticizers, nucleating agents, stabilizers (including but not limited to UV stabilizers, heat stabilizers and / or its reaction products), fillers and impact modifiers. Examples of typical commercially available impact modifiers well known in the art and useful in the present invention include, but are not limited to, ethylene/propylene terpolymers; functionalized polyolefins, such as those containing methyl acrylate and/or or glycidyl methacrylate; styrene-based block copolymer impact modifiers; and various acrylic core/shell impact modifiers. For example, UV additives can be incorporated into the article by adding to the body via application of a hard film or via a coextruded cover layer. Residues of such additives are also contemplated as part of the polyester composition useful for the films or sheets of the present invention.

可用于本发明薄膜或者薄板的聚酯可以包括至少一种增链剂。合适的增链剂包括但不局限于，多官能(包括但不限于双官能)异氰酸酯，多官能环氧化物，包括例如环氧(线型)酚醛清漆，和苯氧基树脂。在某些实施方案中，增链剂可以在聚合过程的末尾或在聚合过程之后添加。如果在聚合过程之后添加，可以通过在转化过程如注塑或挤出期间配混或添加而引入增链剂。增链剂的用量可以取决于所用具体单体的组成和所期望的物理性能而变化，但一般为约0.1wt％-约10wt％，优选地约0.1-约5wt％，基于对本发明薄膜或者薄板有用的聚酯的总重量。The polyesters useful in the films or sheets of the present invention may include at least one chain extender. Suitable chain extenders include, but are not limited to, multifunctional (including but not limited to difunctional) isocyanates, multifunctional epoxides, including, for example, epoxy (novolacs), and phenoxy resins. In certain embodiments, the chain extender can be added at the end of or after the polymerization process. If added after the polymerization process, the chain extender can be introduced by compounding or addition during a conversion process such as injection molding or extrusion. The amount of chain extender used may vary depending on the composition of the particular monomers used and the desired physical properties, but generally ranges from about 0.1 wt% to about 10 wt%, preferably from about 0.1 wt% to about The total weight of polyester available.

热稳定剂是在聚酯制造和/或后聚合期间稳定对本发明薄膜或者薄板有用的聚酯的化合物，包括但不限于含磷化合物，其包括但不限于磷酸、亚磷酸、膦酸、次膦酸、亚膦酸以及其各种酯和盐。这些可以存在于可用于本发明薄膜或者薄板的聚酯组合物中。酯可以是烷基、支链烷基、取代烷基、二官能烷基、烷基醚、芳基和取代芳基的(酯)。在一种实施方案中，存在于特定含磷化合物中的酯基的数目可以从零变化到至多基于存在于所用热稳定剂中的羟基的数目所允许的最大值。术语”热稳定剂”意图包括其反应产物。如与对可用于本发明薄膜或者薄板的聚酯组合物有用的热稳定剂相结合使用的术语“反应产物”是指热稳定剂和用于制备聚酯的任何单体间的缩聚或者酯化反应的任何产物以及催化剂和任何其它类型的添加剂间的缩聚或者酯化反应的产物。Thermal stabilizers are compounds that stabilize the polyesters useful for the films or sheets of the present invention during polyester manufacture and/or post-polymerization, including but not limited to phosphorus-containing compounds including but not limited to phosphoric acid, phosphorous acid, phosphonic acid, phosphine Acids, phosphonous acids and their various esters and salts. These may be present in the polyester compositions useful in the films or sheets of the present invention. Esters can be (esters) of alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ether, aryl, and substituted aryl. In one embodiment, the number of ester groups present in a particular phosphorus-containing compound can vary from zero to up to the maximum allowed based on the number of hydroxyl groups present in the heat stabilizer used. The term "thermal stabilizer" is intended to include reaction products thereof. The term "reaction product" as used in connection with a heat stabilizer useful in the polyester compositions useful in the film or sheet of the present invention refers to the polycondensation or esterification between the heat stabilizer and any monomers used to make the polyester Any product of the reaction as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive.

增强材料可用于对本发明有用的组合物中。增强材料可包括但不限于碳灯丝、硅酸盐、云母、粘土、滑石、二氧化钛、硅灰石、玻璃片、玻璃珠和纤维和聚合物纤维和其组合。在一种实施方案中，增强材料是玻璃如纤维玻璃长丝，玻璃和滑石、玻璃和云母以及玻璃和聚合物纤维的混合物。Reinforcing materials may be used in compositions useful with the present invention. Reinforcing materials may include, but are not limited to, carbon filaments, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers and polymeric fibers and combinations thereof. In one embodiment, the reinforcing material is glass such as fiberglass filaments, mixtures of glass and steatite, glass and mica, and glass and polymer fibers.

在另一实施方案中，本发明还涉及制品，其包含薄膜和/或薄板，该薄膜和/或薄板包含本文中所述的聚酯组合物。In another embodiment, the present invention also relates to articles comprising films and/or sheets comprising the polyester compositions described herein.

可用于本发明的薄膜和/或薄板可以具有任何会对本领域技术人员显而易见的厚度。在一种实施方案中，本发明的薄膜的厚度为不大于40mil。在一种实施方案中，本发明的薄膜的厚度为不大于35mil。在一种实施方案中，本发明的薄膜的厚度为不大于30mil。在一种实施方案中，本发明的薄膜的厚度为不大于25mil。在一种实施方案中，本发明的薄膜的厚度为不大于20mil。Films and/or sheets useful in the present invention can have any thickness that will be apparent to those skilled in the art. In one embodiment, the films of the present invention have a thickness of no greater than 40 mils. In one embodiment, the films of the present invention have a thickness of no greater than 35 mils. In one embodiment, the films of the present invention have a thickness of no greater than 30 mils. In one embodiment, the films of the present invention have a thickness of no greater than 25 mils. In one embodiment, the thickness of the films of the present invention is no greater than 20 mils.

在一种实施方案中，本发明的薄板的厚度为不小于20mil。在另一实施方案中，本发明的薄板的厚度为不小于25mil。在另一实施方案中，本发明的薄板的厚度为不小于30mil。在另一实施方案中，本发明的薄板的厚度为不小于35mil。在另一实施方案中，本发明的薄板的厚度为不小于40mil。In one embodiment, the sheet of the present invention has a thickness of not less than 20 mils. In another embodiment, the sheet of the present invention has a thickness of not less than 25 mils. In another embodiment, the sheet of the present invention has a thickness of not less than 30 mils. In another embodiment, the sheet of the present invention has a thickness of not less than 35 mils. In another embodiment, the sheet of the present invention has a thickness of not less than 40 mils.

将聚酯成形为薄膜和/或薄板的方法在本领域中是众所周知的。本发明的薄膜和/或薄板的实例包括但不限于挤塑薄膜和/或薄板、压延薄膜和/或薄板、压塑薄膜和/或薄板、溶液铸塑薄膜和/或薄板。制造薄膜和/或薄板的方法包括但不限于挤塑、压延、压塑和溶液铸塑。Methods of forming polyesters into films and/or sheets are well known in the art. Examples of films and/or sheets of the present invention include, but are not limited to, extruded films and/or sheets, calendered films and/or sheets, compression molded films and/or sheets, solution cast films and/or sheets. Methods of making films and/or sheets include, but are not limited to, extrusion, calendering, compression molding, and solution casting.

由薄膜和/或薄板制备的潜在制品的实例包括但不限于单向拉伸薄膜、双向拉伸薄膜、收缩薄膜(无论是单向还是双向拉伸的)、液晶显示器薄膜(包括但不限于漫射体薄板、补偿薄膜和保护薄膜)、热成形的薄板、图版工艺薄膜(graphic arts film)、室外标志、天窗、涂层、涂层制品、涂漆制品、层合物、层压制品和/或多层薄膜或者薄板。Examples of potential articles made from film and/or sheet include, but are not limited to, uniaxially oriented films, biaxially oriented films, shrink films (whether unidirectionally or biaxially oriented), liquid crystal display films (including but not limited to diffuse film, compensating film and protective film), thermoformed sheet, graphic arts film, exterior signs, skylights, coatings, coated products, painted products, laminates, laminated products and/or Or multilayer film or sheet.

图版工艺薄膜的实例包括但不局限于铭牌、膜开关饰面；购买点显示器；洗衣机上的平面或模内装饰面板；冰箱上的平面触板；炉上的平板；汽车内饰；汽车仪表组；手机盖；加热和通风控制显示器；汽车控制板；汽车齿轮变速机构面板；汽车仪表板的控制显示器或报警信号；家庭用具上的饰面、表盘或显示器；洗衣机上的饰面、表盘或显示器；洗碗机上的饰面、表盘或显示器；电子设备的小键盘；移动电话、PDA(手提电脑)或远程控制器的小键盘；电子设备的显示器；手提电子设备如电话和PDA的显示器；移动或标准电话的面板和外壳；电子设备上的徽标；和手提电话的徽标。Examples of graphic arts films include, but are not limited to, nameplates, membrane switch finishes; point-of-purchase displays; flat or in-mold decorative panels on washing machines; flat touch panels on refrigerators; flat panels on stoves; automotive interiors; automotive clusters Cell phone covers; Heating and ventilation control displays; Automotive control panels; Automotive gear shifting mechanism panels; Control displays or alarm signals on automotive dashboards; Finishes, dials or displays on household appliances; Finishes, dials or displays on washing machines ; finishes, dials or displays on dishwashers; keypads for electronic devices; keypads for mobile phones, PDAs (laptop computers) or remote controls; displays for electronic devices; displays for portable electronic devices such as telephones and PDAs; mobile Or the panels and casings of standard telephones; the logos on electronic devices; and the logos of mobile phones.

多层薄膜或者薄板是指挤出成由彼此借助竖直肋连接的多个层组成的剖面的薄板。多层薄膜或者薄板的实例包括但不限于温室和商业伞盖。A multilayer film or sheet refers to a sheet extruded into a profile consisting of a plurality of layers connected to each other by vertical ribs. Examples of multilayer films or sheets include, but are not limited to, greenhouses and commercial canopies.

包含对本发明有用的聚酯的挤塑制品的实例包括但不局限于用于图版工艺应用的薄膜、室外标志、天窗、多层薄膜、用于塑料玻璃层合物的塑料薄膜和液晶显示器(LCD)薄膜，液晶显示器(LCD)薄膜包括但不限于用于LCD的漫射体薄板、补偿薄膜和保护薄膜。Examples of extruded articles comprising polyesters useful in the present invention include, but are not limited to, films for graphic arts applications, exterior signs, skylights, multilayer films, plastic films for plastic glass laminates, and liquid crystal displays (LCDs). ) films, liquid crystal display (LCD) films include, but are not limited to, diffuser sheets, compensation films, and protective films for LCDs.

如本文中使用的，缩写“wt”是指“重量”。As used herein, the abbreviation "wt" means "weight."

以下实施例进一步举例说明如何聚酯组合物可用于薄膜和/或薄板和制造聚酯组合物的方法以及其的评估，并且意图是纯粹举例说明本发明而不意图限制其范围。除非另外说明，份数为重量份，温度为摄氏度或处于室温，压力为或接近大气气压。The following examples further illustrate how polyester compositions can be used in films and/or sheets and methods of making polyester compositions and their evaluation, and are intended to be purely illustrative of the invention and not intended to limit the scope thereof. Unless indicated otherwise, parts are parts by weight, temperature is in degrees Celsius or is at ambient temperature, and pressure is at or near atmospheric.

实施例Example

测量方法Measurement methods

聚酯的比浓对数粘度是在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定的。The inherent viscosity of the polyesters is determined at 25°C at a concentration of 0.5 g/100 ml in 60/40 (wt/wt) phenol/tetrachloroethane.

除非另有说明，否则玻璃化转变温度(Tg)是根据ASTMD3418使用Thermal Analyst Instruments的TA DSC 2920仪器以20℃/min的扫描速率测定的。Unless otherwise stated, glass transition temperatures (Tg) are determined according to ASTM D3418 using a TA DSC 2920 instrument from Thermal Analyst Instruments at a scan rate of 20°C/min.

组合物的二醇含量和顺式/反式比例是通过质子核磁共振(NMR)谱测定的。所有NMR谱都记录在JEOL Eclipse Plus 600MHz核磁共振光谱仪上，对于聚合物，使用氯仿-三氟乙酸(70-30体积/体积)，或者对于低聚物样品，使用60/40(wt/wt)苯酚/四氯乙烷，以及为锁峰而添加的氘化氯仿。通过与模型2，2，4，4-四甲基-1，3-环丁二醇的单和二苯甲酸酯进行对比，进行2，2，4，4-四甲基-1，3-环丁二醇共振的峰指认。这些模型化合物非常接近在聚合物和低聚物中存在的共振位置。The diol content and cis/trans ratio of the compositions were determined by proton nuclear magnetic resonance (NMR) spectroscopy. All NMR spectra were recorded on a JEOL Eclipse Plus 600MHz NMR spectrometer using chloroform-trifluoroacetic acid (70-30 v/v) for polymers or 60/40 (wt/wt) for oligomer samples Phenol/tetrachloroethane with deuterated chloroform added for peak locking. 2,2,4,4-Tetramethyl-1,3 - Peak assignment of the cyclobutanediol resonance. These model compounds are in close proximity to resonance positions that exist in polymers and oligomers.

结晶半衰期，t1/2，是通过在温控热台上随着时间经激光器和光电检测器测量样品的透光率来测定。这种测量是这样进行的：将聚合物暴露于温度T_max，并随后将其冷却到期望的温度。随后通过热台将样品保持在期望的温度，同时测量透光率随时间的变化。最初，样品在视觉上是透明的，具有高透光率，且随着样品结晶而变得不透明。结晶半衰期记录为透光率是初始透光率与最终透光率之间一半时的时间。T_max定义为熔融样品晶畴所需的温度(如果存在晶畴的话)。以下实施例中报道的T_max代表在结晶半衰期测量之前将每种样品加热以调理该样品的温度。T_max温度依赖于组成并且对于每种聚酯一般是不同的。例如，可能需要将PCT加热到高于290℃的某温度以熔融晶畴。The crystallization half-life, t1/2, was determined by measuring the light transmittance of the sample over time on a temperature-controlled hot-stage through a laser and a photodetector. This measurement is carried out by exposing the polymer to the temperature_Tmax and subsequently cooling it down to the desired temperature. The samples were then kept at the desired temperature by means of a hot stage while the transmittance was measured as a function of time. Initially, the sample is visually transparent with high light transmission and becomes opaque as the sample crystallizes. The crystallization half-life is recorded as the time at which the transmittance is halfway between the initial transmittance and the final transmittance. T_max is defined as the temperature required to melt the crystal domains of the sample (if domains exist). The_Tmax reported in the Examples below represents the temperature at which each sample was heated to condition the sample prior to crystallization half-life measurements. The_Tmax temperature is composition dependent and generally different for each polyester. For example, it may be necessary to heat the PCT to some temperature above 290°C to melt the domains.

密度是使用梯度密度柱在23℃测定的。Densities were determined at 23°C using gradient density columns.

本文中报道的熔体粘度是通过使用Rheometrics DynamicAnalyzer(RDA II)测量的。在所报道的温度，以1-400弧度/秒的频率测量熔体粘度随剪切速率的变化。零剪切熔体粘度(η₀)是通过本领域已知模型由外推数据而估算的零剪切速率下的熔体粘度。该步骤由RheometricsDynamic Analyzer(RDA II)软件自动实现。Melt viscosities reported herein are measured by using a Rheometrics Dynamic Analyzer (RDA II). Melt viscosity was measured as a function of shear rate at the reported temperature at a frequency of 1-400 rad/sec. Zero shear melt viscosity (η₀ ) is the melt viscosity at zero shear rate estimated from extrapolated data by models known in the art. This step is automatically implemented by Rheometrics Dynamic Analyzer (RDA II) software.

聚合物在80-100℃在真空烘箱中干燥24小时并在Boy 22S模塑机上注塑而得到1/8×1/2×5-英寸和1/4×1/2×5-英寸挠曲试条。根据ASTM D256，将这些试条切成长度为2.5英寸并沿着该1/2英寸宽度进行切口而得到10-mil切口。由5个样条的测量值来测定23℃的平均伊佐德冲击强度。The polymers were dried in a vacuum oven at 80-100°C for 24 hours and injection molded on a Boy 22S molding machine to give 1/8 x 1/2 x 5-inch and 1/4 x 1/2 x 5-inch flex tests. strip. The bars were cut to a length of 2.5 inches and notched along the 1/2 inch width to make 10-mil cuts according to ASTM D256. The average Izod impact strength at 23° C. was determined from the measurements of 5 specimens.

另外，在不同温度使用5℃增量测试5个样条以测定脆韧转变温度。韧脆性转变温度定义为50％样条在由ASTM D256表示的脆性方式中失效时的温度。Additionally, five specimens were tested at different temperatures using 5°C increments to determine the brittle-ductile transition temperature. The ductile-brittle transition temperature is defined as the temperature at which 50% of the bar fails in the brittle mode indicated by ASTM D256.

本文中报道的色值是使用由Hunter Associates Lab Inc.，Reston，Va制造的Hunter Lab Ultrascan Spectra Colorimeter测定的。颜色测定值是在聚酯粒料或由其注塑或挤出的板或其它物件上测量的值的平均值。它们由CIE(国际照明委员会)(译)的L^*a^*b^*色系确定，其中L^*表示光亮度坐标，a^*表示红/绿坐标，b^*表示黄/蓝坐标。Color values reported herein were determined using a Hunter Lab Ultrascan Spectra Colorimeter manufactured by Hunter Associates Lab Inc., Reston, Va. The color determination is the average of the values measured on polyester pellets or sheets or other objects injected or extruded therefrom. They are determined by the L^* a^* b^* color system of CIE (International Commission on Illumination) (translation), where L^* indicates the luminance coordinate, a^* indicates the red/green coordinate, and b^* indicates the yellow/blue coordinate.

另外，使用Carver压机在240℃压塑10-密耳膜。Additionally, 10-mil films were compression molded using a Carver press at 240°C.

除非另作说明，否则用于以下实施例的1，4-环己烷二甲醇的顺式/反式比例约为30/70，并且可以为35/65-25/75。除非另作说明，否则用于以下实施例的2，2，4，4-四甲基-1，3-环丁二醇的顺式/反式比例约为50/50。Unless otherwise stated, the cis/trans ratio of 1,4-cyclohexanedimethanol used in the following examples is about 30/70 and can range from 35/65 to 25/75. Unless otherwise stated, the cis/trans ratio of 2,2,4,4-tetramethyl-1,3-cyclobutanediol used in the following examples was approximately 50/50.

以下缩写适用于全部工作实施例和附图：The following abbreviations apply to all working examples and figures:

实施例1Example 1

本实施例举例说明2，2，4，4-四甲基-1，3-环丁二醇在降低PCT的结晶速率方面比乙二醇或间苯二甲酸更有效。另外，本实施例举例说明2，2，4，4-四甲基-1，3-环丁二醇在玻璃化转变温度和密度方面的益处。This example illustrates that 2,2,4,4-tetramethyl-1,3-cyclobutanediol is more effective than ethylene glycol or isophthalic acid in reducing the crystallization rate of PCT. Additionally, this example illustrates the benefits of 2,2,4,4-tetramethyl-1,3-cyclobutanediol in terms of glass transition temperature and density.

如下所述，制备多种共聚酯。这些共聚酯均采用200ppm氧化二丁锡作为催化剂制备，以最小化催化剂类型和浓度对结晶研究期间成核作用的影响。1，4-环己烷二甲醇的顺式/反式比例为31/69，而2，2，4，4-四甲基-1，3-环丁二醇的顺式/反式比例记录在表1中。A variety of copolyesters were prepared as described below. These copolyesters were prepared using 200 ppm dibutyltin oxide as catalyst to minimize the effect of catalyst type and concentration on nucleation during crystallization studies. 1,4-Cyclohexanedimethanol has a cis/trans ratio of 31/69, while 2,2,4,4-tetramethyl-1,3-cyclobutanediol has a record cis/trans ratio of in Table 1.

对本实施例而言，各样品具有足够相似的比浓对数粘度，因而在结晶速率测量中实际上排除此作为变量。For this example, the samples had sufficiently similar inherent viscosities that this was practically excluded as a variable in the crystallization rate measurements.

在140-200℃以10℃为增量，进行自熔体的结晶半衰期的测量，并将测量结果记录在表1中。每种样品的最快结晶半衰期作为随温度变化的结晶半衰期的最小值，一般出现在大约170-180℃。将样品的最快结晶半衰期作为对PCT改性的共聚单体的mol％的函数绘制在图1中。Measurements of the crystallization half-life from the melt were performed at 140-200°C in 10°C increments and are reported in Table 1. The fastest crystallization half-life for each sample generally occurs at about 170-180°C as a minimum of crystallization half-life as a function of temperature. The fastest crystallization half-life of the samples is plotted in Figure 1 as a function of mol % of PCT-modified comonomer.

数据显示，2，2，4，4-四甲基-1，3-环丁二醇在降低结晶速率(即提高结晶半衰期)方面比乙二醇和间苯二甲酸更有效。另外，2，2，4，4-四甲基-1，3-环丁二醇提高了Tg并降低了密度。The data show that 2,2,4,4-tetramethyl-1,3-cyclobutanediol is more effective than ethylene glycol and isophthalic acid in reducing the crystallization rate (ie, increasing the crystallization half-life). Additionally, 2,2,4,4-tetramethyl-1,3-cyclobutanediol increases Tg and decreases density.

表1Table 1

结晶半衰期(分钟)Crystallization half-life (minutes)

1  表1中聚酯的二醇组分的剩余部分为1，4-环己烷二甲醇；并且表1中聚酯的二羧酸组分的剩余部分为对苯二甲酸二甲酯；如果未描述二羧酸，则其为100mol％对苯二甲酸二甲酯。1 The remainder of the diol component of the polyester in Table 1 is 1,4-cyclohexanedimethanol; and the remainder of the dicarboxylic acid component of the polyester in Table 1 is dimethyl terephthalate; if Where no dicarboxylic acid is described, it is 100 mol% dimethyl terephthalate.

2  100mol％1，4-环己烷二甲醇。2 100mol% 1,4-cyclohexanedimethanol.

3  在240℃由实施例1G的研磨聚酯压制薄膜。所得薄膜具有0.575dL/g的比浓对数粘度值。3 Films were pressed from the milled polyester of Example 1G at 240°C. The resulting film had an inherent viscosity value of 0.575 dL/g.

4  在240℃由实施例1H的研磨聚酯压制薄膜。所得薄膜具有0.0.652dL/g的比浓对数粘度值。4 Films were pressed from the milled polyester of Example 1H at 240°C. The resulting film had an inherent viscosity value of 0.0.652 dL/g.

其中：in:

A为间苯二甲酸A is isophthalic acid

B为乙二醇B is ethylene glycol

C为2，2，4，4-四甲基-1，3-环丁二醇(约50/50顺式/反式)C is 2,2,4,4-tetramethyl-1,3-cyclobutanediol (about 50/50 cis/trans)

D为2，2，4，4-四甲基-1，3-环丁二醇(98/2顺式/反式)D is 2,2,4,4-tetramethyl-1,3-cyclobutanediol (98/2 cis/trans)

E为2，2，4，4-四甲基-1，3-环丁二醇(5/95顺式/反式)E is 2,2,4,4-tetramethyl-1,3-cyclobutanediol (5/95 cis/trans)

如表1和图1所示，在提高结晶半衰期(即聚合物达到其最大结晶度一半所需的时间)方面，2，2，4，4-四甲基-1，3-环丁二醇比其它共聚单体如乙二醇和间苯二甲酸更有效。通过降低PCT的结晶速率(提高结晶半衰期)，可以通过本领域已知的方法制造基于如本文所述的2，2，4，4-四甲基-1，3-环丁二醇改性的PCT的无定形制品。如表1所示，这些材料可以显示出比其它改性PCT共聚酯更高的玻璃化转变温度和更低的密度。As shown in Table 1 and Figure 1, 2,2,4,4-tetramethyl-1,3-cyclobutanediol is more effective at increasing the crystallization half-life (i.e., the time required for a polymer to reach half of its maximum crystallinity). More effective than other comonomers such as ethylene glycol and isophthalic acid. By reducing the crystallization rate of PCT (increasing the crystallization half-life), 2,2,4,4-tetramethyl-1,3-cyclobutanediol-modified based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol as described herein can be produced by methods known in the art. Amorphous articles of PCT. As shown in Table 1, these materials can exhibit higher glass transition temperatures and lower densities than other modified PCT copolyesters.

下面描述表1所示的聚酯的制备。The preparation of the polyesters shown in Table 1 is described below.

实施例1AExample 1A

本实施例举例说明目标的组成为80mol％对苯二甲酸二甲酯残基、20mol％间苯二甲酸二甲酯残基和100mol％1，4-环己烷二甲醇残基(28/72顺式/反式)的共聚酯的制备。This example illustrates that the target composition is 80 mol% dimethyl terephthalate residues, 20 mol% dimethyl isophthalate residues and 100 mol% 1,4-cyclohexanedimethanol residues (28/72 cis/trans) copolyester preparation.

将56.63g对苯二甲酸二甲酯、55.2g 1，4-环己烷二甲醇、14.16g间苯二甲酸二甲酯和0.0419g氧化二丁锡的混合物置于装配有氮气进气口、金属搅拌器和短蒸馏柱的500毫升烧瓶中。将烧瓶置于已经加热到210℃的伍德合金浴(Wood′s metal bath)中。在整个实验过程中搅拌速度设定为200RPM。将烧瓶中的内容物在210℃加热5分钟并随后在30分钟内逐渐将温度升高到290℃。反应混合物在290℃保持60分钟，然后在接下来的5分钟内逐渐施加真空直到烧瓶内压力达到100mmHg。在接下来的5分钟内再将烧瓶内压力降低到0.3mmHg。保持0.3mmHg的压力总共90分钟以除去过量未反应的二醇。得到高熔体粘度、视觉上透明且无色的聚合物，玻璃化转变温度为87.5℃，比浓对数粘度为0.63dl/g。NMR分析表明聚合物包含100mol％1，4-环己烷二甲醇残基和20.2mol％间苯二甲酸二甲酯残基。A mixture of 56.63 g dimethyl terephthalate, 55.2 g 1,4-cyclohexanedimethanol, 14.16 g dimethyl isophthalate and 0.0419 g dibutyltin oxide was placed in a 500 mL flask with metal stirrer and short distillation column. The flask was placed in a Wood's metal bath which had been heated to 210°C. The stirring speed was set at 200 RPM throughout the experiment. The contents of the flask were heated at 210°C for 5 minutes and then the temperature was gradually increased to 290°C over 30 minutes. The reaction mixture was held at 290°C for 60 minutes, then vacuum was gradually applied over the next 5 minutes until the pressure in the flask reached 100 mmHg. The pressure in the flask was then reduced to 0.3 mmHg over the next 5 minutes. A pressure of 0.3 mmHg was maintained for a total of 90 minutes to remove excess unreacted diol. A high melt viscosity, visually clear and colorless polymer with a glass transition temperature of 87.5° C. and an inherent viscosity of 0.63 dl/g was obtained. NMR analysis indicated that the polymer contained 100 mol% 1,4-cyclohexanedimethanol residues and 20.2 mol% dimethyl isophthalate residues.

实施例1BExample 1B

本实施例举例说明目标的组成为100mol％对苯二甲酸二甲酯残基、20mol％乙二醇残基和80mol％1，4-环己烷二甲醇残基(32/68顺式/反式)的共聚酯的制备。This example illustrates the target composition as 100 mol% dimethyl terephthalate residues, 20 mol% ethylene glycol residues, and 80 mol% 1,4-cyclohexanedimethanol residues (32/68 cis/trans Preparation of copolyesters of formula).

将77.68g对苯二甲酸二甲酯、50.77g 1，4-环己烷二甲醇、27.81g乙二醇和0.0433g氧化二丁锡的混合物置于装配有氮气进气口、金属搅拌器和短蒸馏柱的500毫升烧瓶中。将烧瓶置于已经加热到200℃的伍德合金浴中。在整个实验过程中搅拌速度设定为200RPM。将烧瓶中的内容物在200℃加热60分钟并随后在5分钟内逐渐将温度升高到210℃。反应混合物在210℃保持120分钟并随后在30分钟内加热到280℃。一旦处于280℃，在接下来的5分钟内逐渐施加真空直到烧瓶内压力达到100mmHg。在接下来的10分钟内再将烧瓶内压力降低到0.3mmHg。保持0.3mmHg的压力总共90分钟以除去过量未反应的二醇。得到高熔体粘度、视觉上透明且无色的聚合物，玻璃化转变温度为87.7℃，比浓对数粘度为0.71dl/g。NMR分析表明聚合物包含19.8mol％乙二醇残基。A mixture of 77.68 g of dimethyl terephthalate, 50.77 g of 1,4-cyclohexanedimethanol, 27.81 g of ethylene glycol and 0.0433 g of dibutyltin oxide was placed in a Distillation column in a 500 ml flask. The flask was placed in a Wood's metal bath that had been heated to 200°C. The stirring speed was set at 200 RPM throughout the experiment. The contents of the flask were heated at 200°C for 60 minutes and then the temperature was gradually increased to 210°C over 5 minutes. The reaction mixture was maintained at 210°C for 120 minutes and then heated to 280°C within 30 minutes. Once at 280°C, vacuum was gradually applied over the next 5 minutes until the pressure in the flask reached 100 mmHg. The pressure in the flask was then reduced to 0.3 mmHg over the next 10 minutes. A pressure of 0.3 mmHg was maintained for a total of 90 minutes to remove excess unreacted diol. A high melt viscosity, visually clear and colorless polymer with a glass transition temperature of 87.7° C. and an inherent viscosity of 0.71 dl/g was obtained. NMR analysis indicated that the polymer contained 19.8 mol% ethylene glycol residues.

实施例1CExample 1C

本实施例举例说明目标的组成为100mol％对苯二甲酸二甲酯残基、20mol％2，2，4，4-四甲基-1，3-环丁二醇残基和80mol％1，4-环己烷二甲醇残基(31/69顺式/反式)的共聚酯的制备。This example illustrates the target composition as 100 mol% dimethyl terephthalate residues, 20 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 80 mol% 1, Preparation of copolyesters of 4-cyclohexanedimethanol residues (31/69 cis/trans).

将77.68g对苯二甲酸二甲酯、48.46g 1，4-环己烷二甲醇、17.86g2，2，4，4-四甲基-1，3-环丁二醇和0.046g氧化二丁锡的混合物置于装配有氮气进气口、金属搅拌器和短蒸馏柱的500毫升烧瓶中。该聚酯以与实施例1A所述相似的方式制备。得到高熔体粘度、视觉上透明且无色的聚合物，玻璃化转变温度为100.5℃，比浓对数粘度为0.73dl/g。NMR分析表明聚合物包含80.5mol％1，4-环己烷二甲醇残基和19.5mol％2，2，4，4-四甲基-1，3-环丁二醇残基。77.68g dimethyl terephthalate, 48.46g 1,4-cyclohexanedimethanol, 17.86g2,2,4,4-tetramethyl-1,3-cyclobutanediol and 0.046g dibutyltin oxide The mixture was placed in a 500 mL flask equipped with a nitrogen gas inlet, a metal stirrer and a short distillation column. The polyester was prepared in a manner similar to that described in Example 1A. A high melt viscosity, visually clear and colorless polymer with a glass transition temperature of 100.5° C. and an inherent viscosity of 0.73 dl/g was obtained. NMR analysis indicated that the polymer contained 80.5 mol% 1,4-cyclohexanedimethanol residues and 19.5 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

实施例1DExample 1D

本实施例举例说明目标的组成为100mol％对苯二甲酸二甲酯残基、40mol％间苯二甲酸二甲酯残基和100mol％1，4-环己烷二甲醇残基(28/72顺式/反式)的共聚酯的制备。This example illustrates that the target composition is 100 mol% dimethyl terephthalate residues, 40 mol% dimethyl isophthalate residues and 100 mol% 1,4-cyclohexanedimethanol residues (28/72 cis/trans) copolyester preparation.

将42.83g对苯二甲酸二甲酯、55.26g 1，4-环己烷二甲醇、28.45g间苯二甲酸二甲酯和0.0419g氧化二丁锡的混合物置于装配有氮气进气口、金属搅拌器和短蒸馏柱的500毫升烧瓶中。将烧瓶置于已经加热到210℃的伍德合金浴(Wood′s metal bath)中。在整个实验过程中搅拌速度设定为200RPM。将烧瓶中的内容物在210℃加热5分钟并随后在30分钟内逐渐将温度升高到290℃。反应混合物在290℃保持60分钟，然后在接下来的5分钟内逐渐施加真空直到烧瓶内压力达到100mmHg。在接下来的5分钟内再将烧瓶内压力降低到0.3mmHg。保持0.3mmHg的压力总共90分钟以除去过量未反应的二醇。得到高熔体粘度、视觉上透明且无色的聚合物，玻璃化转变温度为81.2℃，比浓对数粘度为0.67dL/g。NMR分析表明聚合物包含100mol％1，4-环己烷二甲醇残基和40.2mol％间苯二甲酸二甲酯残基。A mixture of 42.83 g dimethyl terephthalate, 55.26 g 1,4-cyclohexanedimethanol, 28.45 g dimethyl isophthalate and 0.0419 g dibutyltin oxide was placed in a 500 mL flask with metal stirrer and short distillation column. The flask was placed in a Wood's metal bath which had been heated to 210°C. The stirring speed was set at 200 RPM throughout the experiment. The contents of the flask were heated at 210°C for 5 minutes and then the temperature was gradually increased to 290°C over 30 minutes. The reaction mixture was held at 290°C for 60 minutes, then vacuum was gradually applied over the next 5 minutes until the pressure in the flask reached 100 mmHg. The pressure in the flask was then reduced to 0.3 mmHg over the next 5 minutes. A pressure of 0.3 mmHg was maintained for a total of 90 minutes to remove excess unreacted diol. A high melt viscosity, visually clear and colorless polymer with a glass transition temperature of 81.2° C. and an inherent viscosity of 0.67 dL/g was obtained. NMR analysis indicated that the polymer contained 100 mol% 1,4-cyclohexanedimethanol residues and 40.2 mol% dimethyl isophthalate residues.

实施例1EExample 1E

本实施例举例说明目标的组成为100mol％对苯二甲酸二甲酯残基、40mol％乙二醇残基和60mol％1，4-环己烷二甲醇残基(31/69顺式/反式)的共聚酯的制备。This example illustrates the target composition as 100 mol% dimethyl terephthalate residues, 40 mol% ethylene glycol residues and 60 mol% 1,4-cyclohexanedimethanol residues (31/69 cis/trans Preparation of copolyesters of formula).

将81.3g对苯二甲酸二甲酯、42.85g 1，4-环己烷二甲醇、34.44g乙二醇和0.0419g氧化二丁锡的混合物置于装配有氮气进气口、金属搅拌器和短蒸馏柱的500毫升烧瓶中。将烧瓶置于已经加热到200℃的伍德合金浴中。在整个实验过程中搅拌速度设定为200RPM。将烧瓶中的内容物在200℃加热60分钟并随后在5分钟内逐渐将温度升高到210℃。反应混合物在210℃保持120分钟并随后在30分钟内加热到280℃。一旦处于280℃，在接下来的5分钟内逐渐施加真空直到烧瓶内压力达到100mmHg。在接下来的10分钟内再将烧瓶内压力降低到0.3mmHg。保持0.3mmHg的压力总共90分钟以除去过量未反应的二醇。得到高熔体粘度、视觉上透明且无色的聚合物，玻璃化转变温度为82.1℃，比浓对数粘度为0.64dl/g。NMR分析表明聚合物包含34.5mol％乙二醇残基。A mixture of 81.3 g dimethyl terephthalate, 42.85 g 1,4-cyclohexanedimethanol, 34.44 g ethylene glycol, and 0.0419 g dibutyltin oxide was placed in a device equipped with a nitrogen gas inlet, a metal stirrer, and a short Distillation column in a 500 ml flask. The flask was placed in a Wood's metal bath that had been heated to 200°C. The stirring speed was set at 200 RPM throughout the experiment. The contents of the flask were heated at 200°C for 60 minutes and then the temperature was gradually increased to 210°C over 5 minutes. The reaction mixture was maintained at 210°C for 120 minutes and then heated to 280°C within 30 minutes. Once at 280°C, vacuum was gradually applied over the next 5 minutes until the pressure in the flask reached 100 mmHg. The pressure in the flask was then reduced to 0.3 mmHg over the next 10 minutes. A pressure of 0.3 mmHg was maintained for a total of 90 minutes to remove excess unreacted diol. A high melt viscosity, visually clear and colorless polymer with a glass transition temperature of 82.1° C. and an inherent viscosity of 0.64 dl/g was obtained. NMR analysis indicated that the polymer contained 34.5 mol% ethylene glycol residues.

实施例1FExample 1F

本实施例举例说明目标的组成为100mol％对苯二甲酸二甲酯残基、40mol％2，2，4，4-四甲基-1，3-环丁二醇残基和60mol％1，4-环己烷二甲醇残基(31/69顺式/反式)的共聚酯的制备。This example illustrates the target composition as 100 mol% dimethyl terephthalate residues, 40 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 mol% 1, Preparation of copolyesters of 4-cyclohexanedimethanol residues (31/69 cis/trans).

将77.4g对苯二甲酸二甲酯、36.9g 1，4-环己烷二甲醇、32.5g2，2，4，4-四甲基-1，3-环丁二醇和0.046g氧化二丁锡的混合物置于装配有氮气进气口、金属搅拌器和短蒸馏柱的500毫升烧瓶中。将烧瓶置于已经加热到210℃的伍德合金浴(Wood′s metal bath)中。在整个实验过程中搅拌速度设定为200RPM。将烧瓶的内容物在210℃加热3分钟并随后在30分钟内逐渐将温度升高到260℃。反应混合物在260℃保持120分钟并随后在30分钟内加热到290℃。一旦处于290℃，在接下来的5分钟内逐渐施加真空直到烧瓶内压力达到100mmHg。在接下来的5分钟内再将烧瓶内压力降低到0.3mmHg。保持0.3mmHg的压力总共90分钟以除去过量未反应的二醇。得到高熔体粘度、视觉上透明且无色的聚合物，玻璃化转变温度为122℃，比浓对数粘度为0.65dl/g。NMR分析表明聚合物包含59.9mol％1，4-环己烷二甲醇残基和40.1mol％2，2，4，4-四甲基-1，3-环丁二醇残基。77.4g dimethyl terephthalate, 36.9g 1,4-cyclohexanedimethanol, 32.5g2,2,4,4-tetramethyl-1,3-cyclobutanediol and 0.046g dibutyltin oxide The mixture was placed in a 500 mL flask equipped with a nitrogen gas inlet, a metal stirrer and a short distillation column. The flask was placed in a Wood's metal bath which had been heated to 210°C. The stirring speed was set at 200 RPM throughout the experiment. The contents of the flask were heated at 210°C for 3 minutes and then the temperature was gradually increased to 260°C over 30 minutes. The reaction mixture was maintained at 260°C for 120 minutes and then heated to 290°C within 30 minutes. Once at 290°C, vacuum was gradually applied over the next 5 minutes until the pressure in the flask reached 100 mmHg. The pressure in the flask was then reduced to 0.3 mmHg over the next 5 minutes. A pressure of 0.3 mmHg was maintained for a total of 90 minutes to remove excess unreacted diol. A high melt viscosity, visually clear and colorless polymer with a glass transition temperature of 122° C. and an inherent viscosity of 0.65 dl/g was obtained. NMR analysis indicated that the polymer contained 59.9 mol% 1,4-cyclohexanedimethanol residues and 40.1 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

实施例1GExample 1G

本实施例举例说明目标的组成为100mol％对苯二甲酸二甲酯残基、20mol％2，2，4，4-四甲基-1，3-环丁二醇残基(98/2顺式/反式)和80mol％1，4-环己烷二甲醇残基(31/69顺式/反式)的共聚酯的制备。This example illustrates that the target composition is 100 mol% dimethyl terephthalate residues, 20 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues (98/2 cis Preparation of a copolyester of 1,4-cyclohexanedimethanol residues (31/69 cis/trans) and 80 mol % 1,4-cyclohexanedimethanol residues.

将77，68g对苯二甲酸二甲酯、48.46g 1，4-环己烷二甲醇、20.77g2，2，4，4-四甲基-1，3-环丁二醇和0.046g氧化二丁锡的混合物置于装配有氮气进气口、金属搅拌器和短蒸馏柱的500毫升烧瓶中。将烧瓶置于已经加热到210℃的伍德合金浴(Wood′s metal bath)中。在整个实验过程中搅拌速度设定为200RPM。将烧瓶的内容物在210℃加热3分钟并随后在30分钟内逐渐将温度升高到260℃。反应混合物在260℃保持120分钟并随后在30分钟内加热到290℃。一旦处于290℃，在接下来的5分钟内逐渐施加真空直到烧瓶内压力达到100mmHg，并也将搅拌速度降到100RPM。在接下来的5分钟内再将烧瓶内压降低到0.3mmHg，并且将搅拌速度降到50RPM。保持0.3mmHg的压力总共60分钟以除去过量未反应的二醇。得到高熔体粘度、视觉上透明且无色的聚合物，玻璃化转变温度为103℃，比浓对数粘度为0.65dl/g。NMR分析表明聚合物包含85.7mol％1，4-环己烷二甲醇残基和14.3mol％2，2，4，4-四甲基-1，3-环丁二醇残基。77,68g of dimethyl terephthalate, 48.46g of 1,4-cyclohexanedimethanol, 20.77g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 0.046g of dibutyl oxide The tin mixture was placed in a 500 mL flask equipped with a nitrogen gas inlet, a metal stirrer and a short distillation column. The flask was placed in a Wood's metal bath which had been heated to 210°C. The stirring speed was set at 200 RPM throughout the experiment. The contents of the flask were heated at 210°C for 3 minutes and then the temperature was gradually increased to 260°C over 30 minutes. The reaction mixture was maintained at 260°C for 120 minutes and then heated to 290°C within 30 minutes. Once at 290°C, gradually apply vacuum over the next 5 minutes until the pressure in the flask reaches 100 mmHg and also reduce the stirring speed to 100 RPM. The internal pressure of the flask was reduced to 0.3 mmHg again and the stirring speed was reduced to 50 RPM over the next 5 minutes. A pressure of 0.3 mmHg was maintained for a total of 60 minutes to remove excess unreacted diol. A high melt viscosity, visually clear and colorless polymer with a glass transition temperature of 103° C. and an inherent viscosity of 0.65 dl/g was obtained. NMR analysis indicated that the polymer contained 85.7 mol% 1,4-cyclohexanedimethanol residues and 14.3 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

实施例1HExample 1H

本实施例举例说明目标的组成为100mol％对苯二甲酸二甲酯残基、20mol％2，2，4，4-四甲基-1，3-环丁二醇残基(5/95顺式/反式)和80mol％1，4-环己烷二甲醇残基(31/69顺式/反式)的共聚酯的制备。This example illustrates that the target composition is 100 mol% dimethyl terephthalate residues, 20 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues (5/95 cis Preparation of a copolyester of 1,4-cyclohexanedimethanol residues (31/69 cis/trans) and 80 mol % 1,4-cyclohexanedimethanol residues.

将77.68g对苯二甲酸二甲酯、48.46g 1，4-环己烷二甲醇、20.77g2，2，4，4-四甲基-1，3-环丁二醇和0.046g氧化二丁锡的混合物置于装配有氮气进气口、金属搅拌器和短蒸馏柱的500毫升烧瓶中。将烧瓶置于已经加热到210℃的伍德合金浴(Wood′s metal bath)中。在实验开始时，搅拌速度设定为200RPM。将烧瓶的内容物在210℃加热3分钟并随后在30分钟内逐渐将温度升高到260℃。反应混合物在260℃保持120分钟并随后在30分钟内加热到290℃。一旦处于290℃，在接下来的5分钟内逐渐施加真空，设定点为100mmHg，并也将搅拌速度降到100RPM。在接下来的5分钟内再将烧瓶内压力降低到设定点0.3mmHg，并且将搅拌速度降到50RPM。保持该压力总共60分钟以除去过量未反应的二醇。注意到真空系统没有达到上述设定点，但产生了足够的真空以制备高熔体粘度、视觉上透明且无色的聚合物，玻璃化转变温度为99℃，比浓对数粘度为0.73dl/g。NMR分析表明聚合物包含85mol％1，4-环己烷二甲醇残基和15mol％2，2，4，4-四甲基-1，3-环丁二醇残基。77.68g dimethyl terephthalate, 48.46g 1,4-cyclohexanedimethanol, 20.77g2,2,4,4-tetramethyl-1,3-cyclobutanediol and 0.046g dibutyltin oxide The mixture was placed in a 500 mL flask equipped with a nitrogen gas inlet, a metal stirrer and a short distillation column. The flask was placed in a Wood's metal bath which had been heated to 210°C. At the beginning of the experiment, the stirring speed was set at 200 RPM. The contents of the flask were heated at 210°C for 3 minutes and then the temperature was gradually increased to 260°C over 30 minutes. The reaction mixture was maintained at 260°C for 120 minutes and then heated to 290°C within 30 minutes. Once at 290°C, gradually apply vacuum over the next 5 minutes with a set point of 100 mmHg and also reduce the stirring speed to 100 RPM. The pressure in the flask was then reduced to the set point of 0.3 mmHg over the next 5 minutes and the stirring speed was reduced to 50 RPM. This pressure was maintained for a total of 60 minutes to remove excess unreacted diol. Note that the vacuum system did not reach the above set point, but produced sufficient vacuum to produce a high melt viscosity, visually clear and colorless polymer with a glass transition temperature of 99°C and an inherent viscosity of 0.73dl /g. NMR analysis indicated that the polymer contained 85 mol% 1,4-cyclohexanedimethanol residues and 15 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

实施例2Example 2

本实施例举例说明2，2，4，4-四甲基-1，3-环丁二醇改善了基于PCT的共聚酯(包含对苯二甲酸和1，4-环己烷二甲醇的聚酯)的韧性。This example illustrates that 2,2,4,4-tetramethyl-1,3-cyclobutanediol improves PCT-based copolyesters (containing terephthalic acid and 1,4-cyclohexanedimethanol) Polyester) toughness.

如下所述，制备基于2，2，4，4-四甲基-1，3-环丁二醇的共聚酯。对于所有样品，1，4-环己烷二甲醇的顺式/反式比例约为31/69。基于乙二醇和1，4-环己烷二甲醇的共聚酯是商品化聚酯。实施例2A的共聚酯(Eastar PCTG5445)从Eastman Chemical Co.获得。实施例2B的共聚酯从Eastman Chemical Co.以商品名Spectar获得。实施例2C和实施例2D以中试规模(各为15-lb批次)适应实施例1A所述过程制备，并且具有下表2中所述的比浓对数粘度和玻璃化转变温度。以目标锡数量为300ppm(氧化二丁锡)来制备实施例2C。最终产物包含295ppm锡。实施例2C的聚酯的色值为L^*＝77.11；a^*＝-1.50；和b^*＝5.79。以目标锡数量为300ppm(氧化二丁锡)来制备实施例2D。最终产物包含307ppm锡。实施例2D的聚酯的色值为L^*＝66.72；a^*＝-1.22；和b^*＝16.28。Copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol were prepared as described below. The cis/trans ratio for 1,4-cyclohexanedimethanol was approximately 31/69 for all samples. Copolyesters based on ethylene glycol and 1,4-cyclohexanedimethanol are commercial polyesters. The copolyester of Example 2A (Eastar PCTG5445) was obtained from Eastman Chemical Co. The copolyester of Example 2B was obtained from Eastman Chemical Co. under the Spectar trade name. Example 2C and Example 2D were prepared at pilot scale (15-lb batches each) adapting the procedure described in Example 1A and had inherent viscosities and glass transition temperatures described in Table 2 below. Example 2C was prepared with a target tin amount of 300 ppm (dibutyltin oxide). The final product contained 295 ppm tin. The color values of the polyester of Example 2C are L^* = 77.11; a^* = -1.50; and b^* = 5.79. Example 2D was prepared with a target tin amount of 300 ppm (dibutyltin oxide). The final product contained 307 ppm tin. The color values of the polyester of Example 2D were L^* = 66.72; a^* = -1.22; and b^* = 16.28.

将材料注塑成试条并随后切口进行伊佐德测试。随温度变化获得切口伊佐德冲击强度，同样将其报道在表2中。The material was injection molded into test bars and then notched for Izod testing. Notched Izod impact strength was obtained as a function of temperature, which is also reported in Table 2.

对于给定样品，伊佐德冲击强度在小温度范围内经历大转变(major transition)。例如，基于38mol％乙二醇的共聚酯的伊佐德冲击强度在15-20℃经历这种转变。该转变温度与失效模式的变化有关；脆性/低能量在较低温度失效，而韧性/高能量在较高温度失效。该转变温度表示为韧脆性转变温度T_bd，其是韧性的量度。T_bd报道在表2中并在图2中相对于共聚单体mol％作图。For a given sample, the Izod impact strength undergoes a major transition over a small temperature range. For example, the Izod impact strength of a copolyester based on 38 mol% ethylene glycol undergoes this transition at 15-20°C. This transition temperature is related to a change in failure mode; brittle/low energy failure at lower temperatures and ductile/high energy failure at higher temperatures. This transition temperature is denoted as the ductile-brittle transition temperature T_bd , which is a measure of toughness. T_bd is reported in Table 2 and plotted against comonomer mol % in Figure 2 .

数据表明，与提高PCT的T_bd的乙二醇相比，向PCT中加入2，2，4，4-四甲基-1，3-环丁二醇降低了T_bd并且改善了韧性。The data show that the addition of 2,2,4,4-tetramethyl-1,3-_{cyclobutanediol} to PCT lowers_Tbd and improves toughness compared to ethylene glycol which increases the Tbd of PCT.

表2Table 2

切口伊佐德冲击能量(ft-lb/in)Notched Izod Impact Energy (ft-lb/in)

1.表中聚酯的二醇组分的剩余部分为1，4-环己烷二甲醇。所有聚合物均由100mol％对苯二甲酸二甲酯制备。NA＝不可得到的。其中：B为乙二醇C为2，2，4，4-四甲基-1，3-环丁二醇(50/50顺式/反式)1. The remainder of the diol component of the polyesters in the table is 1,4-cyclohexanedimethanol. All polymers were prepared from 100 mol% dimethyl terephthalate. NA = not available. Among them: B is ethylene glycol C is 2,2,4,4-tetramethyl-1,3-cyclobutanediol (50/50 cis/trans)

实施例3Example 3

本实施例举例说明2，2，4，4-四甲基-1，3-环丁二醇能够改善基于PCT的共聚酯(包含对苯二甲酸和1，4-环己烷二甲醇的聚酯)的韧性。在本实施例中制备的聚酯包含15-25mol％的2，2，4，4-四甲基-1，3-环丁二醇残基。This example illustrates the ability of 2,2,4,4-tetramethyl-1,3-cyclobutanediol to improve PCT-based copolyesters (containing terephthalic acid and 1,4-cyclohexanedimethanol) Polyester) toughness. The polyesters prepared in this example contained 15-25 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

如下所述，制备基于对苯二甲酸二甲酯、2，2，4，4-四甲基-1，3-环丁二醇和1，4-环己烷二甲醇的共聚酯，其具有表3所示的组成和性能。表3中至多100mol％的聚酯的二醇组分的剩余部分为1，4-环己烷二甲醇(31/69顺式/反式)。Copolyesters based on dimethyl terephthalate, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol were prepared as follows, having Composition and properties shown in Table 3. The remainder of the diol component up to 100 mol% of the polyesters in Table 3 is 1,4-cyclohexanedimethanol (31/69 cis/trans).

将材料注塑成3.2mm和6.4mm厚的试条并随后切口进行伊佐德冲击测试。在23℃获得切口伊佐德冲击强度并报道在表3中。测量模塑试条的密度、Tg和结晶半衰期。在290℃测量粒料的熔体粘度。The material was injection molded into 3.2 mm and 6.4 mm thick bars and then notched for Izod impact testing. Notched Izod impact strengths were obtained at 23°C and are reported in Table 3. The density, Tg and crystallization half-life of the molded bars were measured. The melt viscosity of the pellets was measured at 290°C.

表3table 3

对本发明有用的某些聚酯的各种性能汇编Compilation of various properties of certain polyesters useful in the present invention

NA＝不可得到的。NA = not available.

实施例3AExample 3A

在200ppm催化剂三(2-乙基己酸)丁基锡存在下，使21.241b(49.71gram-mol)对苯二甲酸二甲酯、14.34lb(45.21gram-mol)1，4-环己烷二甲醇和4.58lb(14.44gram-mol)2，2，4，4-四甲基-1，3-环丁二醇一起反应。反应在氮气吹扫下在配有冷凝柱、真空系统和HELICONE型搅拌器的18加仑不锈钢压力容器中进行。随着搅拌器以25RPM运转，反应混合物温度升高到250℃，压力升高到20psig。反应混合物在250℃和20psig压力下保持2小时。然后以3psig/min的速率将压力降至0psig。然后将反应混合物的温度升至270℃并将压力降至90mmHg。在270℃和90mmHg下的1小时的保持时间后，将搅拌器速度降至15RPM，反应混合物温度升高到290℃和将压力降至＜1mmHg。将反应混合物保持在290℃和＜1mmHg的压力下直到搅拌器的功率不再升高(70分钟)。然后使用氮气将压力容器的压力升高到1个大气压。随后从压力容器中挤出熔融聚合物。研磨冷却的、挤出的聚合物以便通过6-mm筛。聚合物的比浓对数粘度为0.736dL/g，Tg为104℃。NMR分析表明聚合物包含85.4mol％1，4-环己烷二甲醇残基和14.6mol％2，2，4，4-四甲基-1，3-环丁二醇残基。聚合物的色值为L^*＝78.20，a^*＝-1.62，和b^*＝6.23。In the presence of 200 ppm catalyst tris(2-ethylhexanoate) butyltin, 21.241b (49.71gram-mol) dimethyl terephthalate, 14.34lb (45.21gram-mol) 1,4-cyclohexanedimethanol Reaction with 4.58 lb (14.44 gram-mol) of 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Reactions were performed under a nitrogen purge in an 18 gallon stainless steel pressure vessel equipped with a condensation column, vacuum system and HELICONE type stirrer. With the agitator running at 25 RPM, the temperature of the reaction mixture was raised to 250°C and the pressure to 20 psig. The reaction mixture was maintained at 250°C and 20 psig pressure for 2 hours. The pressure was then reduced to 0 psig at a rate of 3 psig/min. The temperature of the reaction mixture was then raised to 270°C and the pressure was lowered to 90 mmHg. After a 1 hour hold time at 270°C and 90 mmHg, the stirrer speed was reduced to 15 RPM, the temperature of the reaction mixture was raised to 290°C and the pressure was reduced to <1 mmHg. The reaction mixture was maintained at 290°C and a pressure <1 mmHg until the power of the stirrer was no longer increased (70 minutes). The pressure of the pressure vessel was then raised to 1 atmosphere using nitrogen. The molten polymer is then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass through a 6-mm sieve. The polymer had an inherent viscosity of 0.736 dL/g and a Tg of 104°C. NMR analysis indicated that the polymer contained 85.4 mol% 1,4-cyclohexanedimethanol residues and 14.6 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The color values of the polymer were L^* = 78.20, a^* = -1.62, and b^* = 6.23.

实施例3B-实施例3DExample 3B-Example 3D

实施例3B-实施例3D中所述的聚酯按照与实施例3A所述程序的相似程序制备。这种聚酯的组成和性能示于表3中。The polyesters described in Example 3B-Example 3D were prepared following a procedure similar to that described in Example 3A. The composition and properties of this polyester are shown in Table 3.

实施例3EExample 3E

在200ppm催化剂三(2-乙基己酸)丁基锡存在下，使21.24lb(49.71gram-mol)对苯二甲酸二甲酯、12.61lb(39.77gram-mol)1，4-环己烷二甲醇、6.30lb(19.88gram-mol)2，2，4，4-四甲基-1，3-环丁二醇一起反应。反应在氮气吹扫下在配有冷凝柱、真空系统和HELICONE型搅拌器的18加仑不锈钢压力容器中进行。随着搅拌器以25RPM运转，反应混合物温度升高到250℃，压力升高到20psig。反应混合物在250℃和20psig压力下保持2小时。然后以3psig/min的速率将压力降至0psig。然后将反应混合物的温度升至270℃并将压力降至90mmHg。在270℃和90mmHg下的1小时的保持时间后，将搅拌器速度降至15RPM，反应混合物温度升高到290℃和将压力降至＜1mmHg。反应混合物在290℃和＜1mmHg的压力下保持60分钟。然后使用氮气将压力容器的压力升高到1个大气压。随后从压力容器中挤出熔融聚合物。研磨冷却的、挤出的聚合物以便通过6-mm筛。聚合物的比浓对数粘度为0.715dL/g，Tg为110℃。X射线分析表明聚酯具有223ppm锡。NMR分析表明聚合物包含78.6mol％1，4-环己烷二甲醇残基和21.4mol％2，2，4，4-四甲基-1，3-环丁二醇残基。聚合物的色值为L^*＝76.45；a^*＝-1.65；和b^*＝6.47。In the presence of 200 ppm catalyst tris(2-ethylhexanoate) butyltin, 21.24 lb (49.71 gram-mol) dimethyl terephthalate, 12.61 lb (39.77 gram-mol) 1,4-cyclohexanedimethanol , 6.30lb (19.88gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together. Reactions were performed under a nitrogen purge in an 18 gallon stainless steel pressure vessel equipped with a condensation column, vacuum system and HELICONE type stirrer. With the agitator running at 25 RPM, the temperature of the reaction mixture was raised to 250°C and the pressure to 20 psig. The reaction mixture was maintained at 250°C and 20 psig pressure for 2 hours. The pressure was then reduced to 0 psig at a rate of 3 psig/min. The temperature of the reaction mixture was then raised to 270°C and the pressure was lowered to 90 mmHg. After a 1 hour hold time at 270°C and 90 mmHg, the stirrer speed was reduced to 15 RPM, the temperature of the reaction mixture was raised to 290°C and the pressure was reduced to <1 mmHg. The reaction mixture was maintained at 290°C and a pressure of <1 mmHg for 60 minutes. The pressure of the pressure vessel was then raised to 1 atmosphere using nitrogen. The molten polymer is then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass through a 6-mm sieve. The polymer had an inherent viscosity of 0.715 dL/g and a Tg of 110°C. X-ray analysis indicated that the polyester had 223 ppm tin. NMR analysis indicated that the polymer contained 78.6 mol% 1,4-cyclohexanedimethanol residues and 21.4 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The color values of the polymer were L^* = 76.45; a^* = -1.65; and b^* = 6.47.

实施例3FExample 3F

实施例3F中所述的聚酯按照与实施例3A所述程序的相似程序制备。这种聚酯的组成和性能示于表3中。The polyester described in Example 3F was prepared following a procedure similar to that described in Example 3A. The composition and properties of this polyester are shown in Table 3.

实施例3HExample 3H

在200ppm催化剂三(2-乙基己酸)丁基锡存在下，使21.24lb(49.71gram-mol)对苯二甲酸二甲酯、12.61lb(39.77gram-mol)1，4-环己烷二甲醇、6.30lb(19.88gram-mol)2，2，4，4-四甲基-1，3-环丁二醇一起反应。反应在氮气吹扫下在配有冷凝柱、真空系统和HELICONE型搅拌器的18加仑不锈钢压力容器中进行。随着搅拌器以25RPM运转，反应混合物温度升高到250℃，压力升高到20psig。反应混合物在250℃和20psig压力下保持2小时。然后以3psig/min的速率将压力降至0psig。然后将反应混合物的温度升至270℃并将压力降至90mmHg。在270℃和90mmHg下的1小时的保持时间后，将搅拌器速度降至15RPM，反应混合物温度升高到290℃和将压力降至＜1mmHg。反应混合物在290℃和＜1mmHg的压力下保持12分钟。然后使用氮气将压力容器的压力升高到1个大气压。随后从压力容器中挤出熔融聚合物。研磨冷却的、挤出的聚合物以便通过6-mm筛。聚合物的比浓对数粘度为0.590dL/g，Tg为106℃。NMR分析表明聚合物包含77.1mol％1，4-环己烷二甲醇残基和22.9mol％2，2，4，4-四甲基-1，3-环丁二醇残基。聚合物的色值为L^*＝83.27；a^*＝-1.34；和b^*＝5.08。In the presence of 200 ppm catalyst tris(2-ethylhexanoate) butyltin, 21.24 lb (49.71 gram-mol) dimethyl terephthalate, 12.61 lb (39.77 gram-mol) 1,4-cyclohexanedimethanol , 6.30lb (19.88gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together. Reactions were performed under a nitrogen purge in an 18 gallon stainless steel pressure vessel equipped with a condensation column, vacuum system and HELICONE type stirrer. With the agitator running at 25 RPM, the temperature of the reaction mixture was raised to 250°C and the pressure to 20 psig. The reaction mixture was maintained at 250°C and 20 psig pressure for 2 hours. The pressure was then reduced to 0 psig at a rate of 3 psig/min. The temperature of the reaction mixture was then raised to 270°C and the pressure was lowered to 90 mmHg. After a 1 hour hold time at 270°C and 90 mmHg, the stirrer speed was reduced to 15 RPM, the temperature of the reaction mixture was raised to 290°C and the pressure was reduced to <1 mmHg. The reaction mixture was maintained at 290°C and a pressure of <1 mmHg for 12 minutes. The pressure of the pressure vessel was then raised to 1 atmosphere using nitrogen. The molten polymer is then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass through a 6-mm sieve. The polymer had an inherent viscosity of 0.590 dL/g and a Tg of 106°C. NMR analysis indicated that the polymer contained 77.1 mol% 1,4-cyclohexanedimethanol residues and 22.9 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The color values of the polymer were L^* = 83.27; a^* = -1.34; and b^* = 5.08.

实施例3IExample 3I

在200ppm催化剂三(2-乙基己酸)丁基锡存在下，使21.24lb(49.71gram-mol)对苯二甲酸二甲酯、12.61lb(39.77gram-mol)1，4-环己烷二甲醇、6.30lb(19.88gram-mol)2，2，4，4-四甲基-1，3-环丁二醇一起反应。反应在氮气吹扫下在配有冷凝柱、真空系统和HELICONE型搅拌器的18加仑不锈钢压力容器中进行。随着搅拌器以25RPM运转，反应混合物温度升高到250℃，压力升高到20psig。反应混合物在250℃和20psig压力下保持2小时。然后以3psig/min的速率将压力降至0psig。然后将反应混合物的温度升至270℃并将压力降至90mmHg。在270℃和90mmHg下的1小时的保持时间后，将搅拌器速度降至15RPM，反应混合物温度升高到290℃，和将压力降至4mmHg。反应混合物在290℃和4mmHg的压力下保持30分钟。然后使用氮气将压力容器的压力升高到1个大气压。随后从压力容器中挤出熔融聚合物。研磨冷却的、挤出的聚合物以便通过6-mm筛。聚合物的比浓对数粘度为0.531dL/g，Tg为105℃。NMR分析表明聚合物包含76.9mol％1，4-环己烷二甲醇残基和23.1mol％2，2，4，4-四甲基-1，3-环丁二醇残基。聚合物的色值为L^*＝80.42，a^*＝-1.28，和b^*＝5.13。In the presence of 200 ppm catalyst tris(2-ethylhexanoate) butyltin, 21.24 lb (49.71 gram-mol) dimethyl terephthalate, 12.61 lb (39.77 gram-mol) 1,4-cyclohexanedimethanol , 6.30lb (19.88gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together. Reactions were performed under a nitrogen purge in an 18 gallon stainless steel pressure vessel equipped with a condensation column, vacuum system and HELICONE type stirrer. With the agitator running at 25 RPM, the temperature of the reaction mixture was raised to 250°C and the pressure to 20 psig. The reaction mixture was maintained at 250°C and 20 psig pressure for 2 hours. The pressure was then reduced to 0 psig at a rate of 3 psig/min. The temperature of the reaction mixture was then raised to 270°C and the pressure was lowered to 90 mmHg. After a hold time of 1 hour at 270°C and 90 mmHg, the stirrer speed was reduced to 15 RPM, the temperature of the reaction mixture was raised to 290°C, and the pressure was reduced to 4 mmHg. The reaction mixture was maintained at 290°C and a pressure of 4 mmHg for 30 minutes. The pressure of the pressure vessel was then raised to 1 atmosphere using nitrogen. The molten polymer is then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass through a 6-mm sieve. The polymer had an inherent viscosity of 0.531 dL/g and a Tg of 105°C. NMR analysis indicated that the polymer contained 76.9 mol% 1,4-cyclohexanedimethanol residues and 23.1 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The color values of the polymer were L^* = 80.42, a^* = -1.28, and b^* = 5.13.

实施例3JExample 3J

在200ppm催化剂三(2-乙基己酸)丁基锡存在下，使21.24lb(49.71gram-mol)对苯二甲酸二甲酯、12.61lb(39.77gram-mol)1，4-环己烷二甲醇、6.30lb(19.88gram-mol)2，2，4，4-四甲基-1，3-环丁二醇一起反应。反应在氮气吹扫下在配有冷凝柱、真空系统和HELICONE型搅拌器的18加仑不锈钢压力容器中进行。随着搅拌器以25RPM运转，反应混合物温度升高到250℃，压力升高到20psig。反应混合物在250℃和20psig压力下保持2小时。然后以3psig/min的速率将压力降至0psig。然后将反应混合物的温度升至270℃并将压力降至90mmHg。在270℃和90mmHg下的1小时的保持时间后，将搅拌器速度降至15RPM，反应混合物温度升高到290℃，和将压力降至4mmHg。当反应混合物温度是290℃并且压力是4mmHg时，使用氮气立即将压力容器的压力增加到1个大气压。随后从压力容器中挤出熔融聚合物。研磨冷却的、挤出的聚合物以便通过6-mm筛。聚合物的比浓对数粘度为0.364dL/g，Tg为98℃。NMR分析表明聚合物包含77.5mol％1，4-环己烷二甲醇残基和22.5mol％2，2，4，4-四甲基-1，3-环丁二醇残基。聚合物的色值为L^*＝77.20，a^*＝-1.47，和b^*＝4.62。In the presence of 200 ppm catalyst tris(2-ethylhexanoate) butyltin, 21.24 lb (49.71 gram-mol) dimethyl terephthalate, 12.61 lb (39.77 gram-mol) 1,4-cyclohexanedimethanol , 6.30lb (19.88gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together. Reactions were performed under a nitrogen purge in an 18 gallon stainless steel pressure vessel equipped with a condensation column, vacuum system and HELICONE type stirrer. With the agitator running at 25 RPM, the temperature of the reaction mixture was raised to 250°C and the pressure to 20 psig. The reaction mixture was maintained at 250°C and 20 psig pressure for 2 hours. The pressure was then reduced to 0 psig at a rate of 3 psig/min. The temperature of the reaction mixture was then raised to 270°C and the pressure was lowered to 90 mmHg. After a hold time of 1 hour at 270°C and 90 mmHg, the stirrer speed was reduced to 15 RPM, the temperature of the reaction mixture was raised to 290°C, and the pressure was reduced to 4 mmHg. When the temperature of the reaction mixture was 290° C. and the pressure was 4 mmHg, the pressure of the pressure vessel was immediately increased to 1 atmosphere using nitrogen. The molten polymer is then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass through a 6-mm sieve. The polymer had an inherent viscosity of 0.364 dL/g and a Tg of 98°C. NMR analysis indicated that the polymer contained 77.5 mol% 1,4-cyclohexanedimethanol residues and 22.5 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The color values of the polymer were L^* = 77.20, a^* = -1.47, and b^* = 4.62.

实施例4Example 4

本实施例举例说明2，2，4，4-四甲基-1，3-环丁二醇能够改善基于PCT的共聚酯(包含对苯二甲酸和1，4-环己烷二甲醇的聚酯)的韧性。在本实施例中制备的聚酯包含大于25-小于40mol％的2，2，4，4-四甲基-1，3-环丁二醇残基。This example illustrates the ability of 2,2,4,4-tetramethyl-1,3-cyclobutanediol to improve PCT-based copolyesters (containing terephthalic acid and 1,4-cyclohexanedimethanol) Polyester) toughness. The polyesters prepared in this example contained greater than 25 to less than 40 mole percent 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

如下所述，制备基于对苯二甲酸二甲酯、2，2，4，4-四甲基-1，3-环丁二醇和1，4-环己烷二甲醇(3 1/69顺式/反式)的共聚酯，其具有表4所示的组成和性能。表4中至多100mol％的聚酯的二醇组分的剩余部分为1，4-环己烷二甲醇(31/69顺式/反式)。As described below, the preparation of /trans) copolyester, which has the composition and properties shown in Table 4. The remainder of the diol component up to 100 mol% of the polyesters in Table 4 is 1,4-cyclohexanedimethanol (31/69 cis/trans).

将材料注塑成3.2mm和6.4mm厚的试条并随后切口进行伊佐德冲击测试。在23℃获得切口伊佐德冲击强度并报道在表4中。测量模塑试条的密度、Tg和结晶半衰期。在290℃测量粒料的熔体粘度。The material was injection molded into 3.2 mm and 6.4 mm thick bars and then notched for Izod impact testing. Notched Izod impact strengths were obtained at 23°C and are reported in Table 4. The density, Tg and crystallization half-life of the molded bars were measured. The melt viscosity of the pellets was measured at 290°C.

表4Table 4

对本发明有用的某些聚酯的各种性能汇编Compilation of various properties of certain polyesters useful in the present invention

NA＝不可得到的。NA = not available.

实施例4AExample 4A

在200ppm催化剂三(2-乙基己酸)丁基锡存在下，使21.24lb(49.71 gram-mol)对苯二甲酸二甲酯、11.82lb(37.28gram-mol)1，4-环己烷二甲醇和6.90lb(21.77gram-mol)2，2，4，4-四甲基-1，3-环丁二醇一起反应。反应在氮气吹扫下在配有冷凝柱、真空系统和HELICONE型搅拌器的18加仑不锈钢压力容器中进行。随着搅拌器以25RPM运转，反应混合物温度升高到250℃，压力升高到20psig。反应混合物在250℃和20psig压力下保持2小时。然后以3psig/min的速率将压力降至0psig。然后将反应混合物的温度升至270℃并将压力降至90mmHg。在270℃和90mmHg下的1小时的保持时间后，将搅拌器速度降至15RPM，反应混合物温度升高到290℃和将压力降至＜1mmHg。将反应混合物保持在290℃和＜1mmHg的压力下直到搅拌器的功率不再升高(50分钟)。然后使用氮气将压力容器的压力升高到1个大气压。随后从压力容器中挤出熔融聚合物。研磨冷却的、挤出的聚合物以便通过6-mm筛。聚合物的比浓对数粘度为0.714dL/g，Tg为113℃。NMR分析表明聚合物包含73.3mol％1，4-环己烷二甲醇残基和26.7mol％2，2，4，4-四甲基-1，3-环丁二醇残基。In the presence of 200 ppm catalyst tris(2-ethylhexanoate) butyltin, 21.24 lb (49.71 gram-mol) dimethyl terephthalate, 11.82 lb (37.28 gram-mol) 1,4-cyclohexanedimethanol Reaction with 6.90 lb (21.77 gram-mol) of 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Reactions were performed under a nitrogen purge in an 18 gallon stainless steel pressure vessel equipped with a condensation column, vacuum system and HELICONE type stirrer. With the agitator running at 25 RPM, the temperature of the reaction mixture was raised to 250°C and the pressure to 20 psig. The reaction mixture was maintained at 250°C and 20 psig pressure for 2 hours. The pressure was then reduced to 0 psig at a rate of 3 psig/min. The temperature of the reaction mixture was then raised to 270°C and the pressure was lowered to 90 mmHg. After a 1 hour hold time at 270°C and 90 mmHg, the stirrer speed was reduced to 15 RPM, the temperature of the reaction mixture was raised to 290°C and the pressure was reduced to <1 mmHg. The reaction mixture was maintained at 290°C and a pressure of <1 mmHg until the power of the stirrer was no longer increased (50 minutes). The pressure of the pressure vessel was then raised to 1 atmosphere using nitrogen. The molten polymer is then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass through a 6-mm sieve. The polymer had an inherent viscosity of 0.714 dL/g and a Tg of 113°C. NMR analysis indicated that the polymer contained 73.3 mol% 1,4-cyclohexanedimethanol residues and 26.7 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

实施例4BExample 4B

实施例4B的聚酯按照与实施例4A所述程序的相似程序制备。这种聚酯的组成和性能示于表4中。The polyester of Example 4B was prepared following a procedure similar to that described for Example 4A. The composition and properties of this polyester are shown in Table 4.

实施例5Example 5

本实施例举例说明2，2，4，4-四甲基-1，3-环丁二醇能够改善基于PCT的共聚酯(包含对苯二甲酸和1，4-环己烷二甲醇的聚酯)的韧性。This example illustrates the ability of 2,2,4,4-tetramethyl-1,3-cyclobutanediol to improve PCT-based copolyesters (containing terephthalic acid and 1,4-cyclohexanedimethanol) Polyester) toughness.

如下所述，制备基于对苯二甲酸二甲酯、2，2，4，4-四甲基-1，3-环丁二醇和1，4-环己烷二甲醇的共聚酯，其具有表5所示的组成和性能。表5中至多100mol％的聚酯的二醇组分的剩余部分为1，4-环己烷二甲醇(31/69顺式/反式)。Copolyesters based on dimethyl terephthalate, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol were prepared as follows, having Composition and properties shown in Table 5. The remainder of the diol component up to 100 mol% of the polyesters in Table 5 is 1,4-cyclohexanedimethanol (31/69 cis/trans).

将聚酯注塑成3.2mm和6.4mm厚的试条并随后切口进行伊佐德冲击测试。在23℃获得切口伊佐德冲击强度并报道在表5中。测量模塑试条的密度、Tg和结晶半衰期。在290℃测量粒料的熔体粘度。The polyester was injection molded into 3.2 mm and 6.4 mm thick bars and then notched for Izod impact testing. Notched Izod impact strengths were obtained at 23°C and are reported in Table 5. The density, Tg and crystallization half-life of the molded bars were measured. The melt viscosity of the pellets was measured at 290°C.

表5table 5

对本发明有用的某些聚酯的各种性能汇编Compilation of various properties of certain polyesters useful in the present invention

NA＝不可得到的。NA = not available.

实施例5AExample 5A

在200ppm催化剂三(2-乙基己酸)丁基锡存在下，使21.24lb(49.71gram-mol)对苯二甲酸二甲酯、8.84lb(27.88gram-mol)1，4-环己烷二甲醇和10.08lb(31.77gram-mol)2，2，4，4-四甲基-1，3-环丁二醇一起反应。反应在氮气吹扫下在配有冷凝柱、真空系统和HELICONE型搅拌器的18加仑不锈钢压力容器中进行。随着搅拌器以25RPM运转，反应混合物温度升高到250℃，压力升高到20psig。反应混合物在250℃和20psig压力下保持2小时。然后以3psig/min的速率将压力降至0psig。然后将搅拌器速度降至15RPM，然后将反应混合物的温度升至290℃，和将压力降至2mmHg。将反应混合物保持在290℃和2mmHg的压力下直到搅拌器的功率不再升高(80分钟)。然后使用氮气将压力容器的压力升高到1个大气压。随后从压力容器中挤出熔融聚合物。研磨冷却的、挤出的聚合物以便通过6-mm筛。聚合物的比浓对数粘度为0.657dL/g，Tg为119℃。NMR分析表明聚合物包含56.3mol％1，4-环己烷二甲醇残基和43.7mol％2，2，4，4-四甲基-1，3-环丁二醇残基。聚合物的色值为L^*＝75.04；a^*＝-1.82；和b^*＝6.72。In the presence of 200 ppm catalyst tris(2-ethylhexanoate) butyltin, 21.24 lb (49.71 gram-mol) dimethyl terephthalate, 8.84 lb (27.88 gram-mol) 1,4-cyclohexanedimethanol Reaction with 10.08 lb (31.77 gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Reactions were performed under a nitrogen purge in an 18 gallon stainless steel pressure vessel equipped with a condensation column, vacuum system and HELICONE type stirrer. With the agitator running at 25 RPM, the temperature of the reaction mixture was raised to 250°C and the pressure to 20 psig. The reaction mixture was maintained at 250°C and 20 psig pressure for 2 hours. The pressure was then reduced to 0 psig at a rate of 3 psig/min. The stirrer speed was then reduced to 15 RPM, then the temperature of the reaction mixture was raised to 290°C, and the pressure was lowered to 2mmHg. The reaction mixture was maintained at 290° C. and a pressure of 2 mmHg until the power of the stirrer was no longer increased (80 minutes). The pressure of the pressure vessel was then raised to 1 atmosphere using nitrogen. The molten polymer is then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass through a 6-mm sieve. The polymer had an inherent viscosity of 0.657 dL/g and a Tg of 119°C. NMR analysis indicated that the polymer contained 56.3 mol% 1,4-cyclohexanedimethanol residues and 43.7 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The color values of the polymer were L^* = 75.04; a^* = -1.82; and b^* = 6.72.

实施例6-对比例Embodiment 6-comparative example

本实施例显示了用于对比材料的数据，其示于表6中。PC为来自Bayer的Makrolon 2608，其标称组成为100mol％双酚A残基和100mol％碳酸二苯酯残基。Makrolon 2608具有使用1.2kg重量在300C测量的20g/10min的标称熔体流动速率。PET为来自Eastman ChemicalCompany的Eastar 9921，其标称组成为100mol％对苯二甲酸、3.5mol％环己烷二甲醇(CHDM)和96.5mol％乙二醇。PETG为来自EastmanChemical Company的Eastar 6763，其标称组成为100mol％对苯二甲酸、31mol％环己烷二甲醇(CHDM)和69mol％乙二醇。PCTG为来自EastmanChemical Company的Eastar DN001，其标称组成为100mol％对苯二甲酸、62mol％环己烷二甲醇(CHDM)和38mol％乙二醇。PCTA为来自Eastman Chemical Company的Eastar AN001，其标称组成为65mol％对苯二甲酸、35mol％间苯二甲酸和100mol％环己烷二甲醇(CHDM)。聚砜为来自Solvay的Udel 1700，其标称组成为100mol％双酚A残基和100mol％4，4-二氯磺酰基砜残基。Udel 1700具有使用2.16kg重量在343C测量的6.5g/10min的标称熔体流动速率。SAN为来自Lanxess的Lustran31，其标称组成为76wt％苯乙烯和24wt％丙烯腈。Lustran 31具有使用3.8kg重量在230C测量的7.5g/10min的标称熔体流动速率。与所有其它树脂相比，本发明的实施例在6.4mm厚试条中显示出改进的韧性。This example shows data for a comparative material, which is shown in Table 6. PC is Makrolon 2608 from Bayer with a nominal composition of 100 mol% bisphenol A residues and 100 mol% diphenyl carbonate residues. Makrolon 2608 has a nominal melt flow rate of 20 g/10 min measured at 300C using a 1.2 kg weight. The PET was Eastar 9921 from Eastman Chemical Company with a nominal composition of 100 mol% terephthalic acid, 3.5 mol% cyclohexanedimethanol (CHDM), and 96.5 mol% ethylene glycol. The PETG was Eastar 6763 from Eastman Chemical Company with a nominal composition of 100 mol% terephthalic acid, 31 mol% cyclohexanedimethanol (CHDM), and 69 mol% ethylene glycol. PCTG is Eastar DN001 from Eastman Chemical Company with a nominal composition of 100 mol% terephthalic acid, 62 mol% cyclohexanedimethanol (CHDM), and 38 mol% ethylene glycol. PCTA is Eastar AN001 from Eastman Chemical Company with a nominal composition of 65 mol% terephthalic acid, 35 mol% isophthalic acid and 100 mol% cyclohexanedimethanol (CHDM). The polysulfone was Udel 1700 from Solvay with a nominal composition of 100 mol% bisphenol A residues and 100 mol% 4,4-dichlorosulfonylsulfone residues. Udel 1700 has a nominal melt flow rate of 6.5 g/10 min measured at 343C using a 2.16 kg weight. The SAN was Lustran 31 from Lanxess with a nominal composition of 76 wt% styrene and 24 wt% acrylonitrile. Lustran 31 has a nominal melt flow rate of 7.5 g/10 min measured at 230C using a 3.8 kg weight. The inventive examples showed improved toughness in 6.4 mm thick bars compared to all other resins.

表6Table 6

某些商品聚合物的各种性能汇编Compilation of various properties of certain commercial polymers

NA＝不可得到的NA = not available

实施例7Example 7

本实施例举例说明用于制备本发明聚酯的2，2，4，4-四甲基-1，3-环丁二醇的量对聚酯的玻璃化转变温度的影响。在本实施例中制备的聚酯包含15-25mol％的2，2，4，4-四甲基-1，3-环丁二醇残基。This example illustrates the effect of the amount of 2,2,4,4-tetramethyl-1,3-cyclobutanediol used to prepare the polyesters of the invention on the glass transition temperature of the polyesters. The polyesters prepared in this example contained 15-25 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

实施例7A-实施例7GExample 7A-Example 7G

将对苯二甲酸二甲酯、1，4-环己烷二甲醇和2，2，4，4-四甲基-1，3-环丁二醇称重加入500-毫升单颈圆底烧瓶中。2，2，4，4-四甲基-1，3-环丁二醇起始材料的NMR分析显示顺式/反式比例为53/47。本实施例的聚酯采用1.2/1二醇/酸比例制备，全部过量均来自2，2，4，4-四甲基-1，3-环丁二醇。加入足够的氧化二丁锡催化剂以在最终聚合物中得到300ppm锡。烧瓶处于具有真空降低能力的0.2SCFC氮气吹扫下。将烧瓶浸入200℃的Belmont金属浴并在反应物熔融之后以200RPM搅拌。约2.5小时后，将温度升高至210℃并将这些条件保持另外的2小时。将温度升高至285℃(约25分钟)并在5分钟内将压力降低至0.3mmHg。随着粘度增加，降低搅拌，15RPM是所用的最小搅拌。改变总聚合时间以获得目标比浓对数粘度。聚合完成后，使Belmont金属浴下降并允许聚合物冷却到低于其玻璃化转变温度。约30分钟后，再次将烧瓶浸入Belmont金属浴(在这30分钟的等待中温度已升至295℃)并加热聚合物物质直到其脱离玻璃烧瓶。在烧瓶中以中等水平搅拌聚合物物质直到聚合物冷却。从烧瓶中取出聚合物并研磨以便通过3mm筛。对该程序进行改变以生产目标的组成为20mol％的如下所述的共聚酯。Dimethyl terephthalate, 1,4-cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol were weighed into a 500-mL single-necked round bottom flask middle. NMR analysis of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol starting material showed a cis/trans ratio of 53/47. The polyester of this example was prepared using a diol/acid ratio of 1.2/1, with all excess coming from 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Sufficient dibutyltin oxide catalyst was added to give 300 ppm tin in the final polymer. The flask was under a 0.2 SCFC nitrogen purge with vacuum reduction capability. The flask was immersed in a Belmont metal bath at 200°C and stirred at 200 RPM after the reactants were molten. After about 2.5 hours, the temperature was raised to 210°C and these conditions were maintained for an additional 2 hours. The temperature was raised to 285°C (about 25 minutes) and the pressure was reduced to 0.3 mmHg within 5 minutes. As the viscosity increased, the agitation was reduced, 15 RPM was the minimum agitation used. The total polymerization time was varied to achieve the target inherent viscosity. After the polymerization was complete, the Belmont metal bath was lowered and the polymer was allowed to cool below its glass transition temperature. After about 30 minutes, the flask was again immersed in the Belmont metal bath (the temperature had risen to 295°C during this 30 minute wait) and the polymer mass was heated until it came out of the glass flask. Stir the polymer mass in the flask on a medium level until the polymer cools. The polymer was removed from the flask and ground to pass through a 3 mm sieve. The procedure was modified to produce a copolyester as described below with a target composition of 20 mol%.

如以上“测量方法”部分所述测量比浓对数粘度。如在前面测量方法部分所述，由1H NMR测定聚酯的组成。在以20℃/min的速率骤冷后使用二次加热，由DSC测定玻璃化转变温度。Inherent viscosity was measured as described in the "Measurement Methods" section above. The composition of the polyesters was determined by 1H NMR as described above in the Measurement Methods section. Glass transition temperatures were determined by DSC using secondary heating after quenching at a rate of 20°C/min.

实施例7H-实施例7QExample 7H-Example 7Q

这些聚酯通过在分开的阶段进行酯交换和缩聚反应而制备。酯交换实验是在连续升温(CTR)反应器中进行的。CTR是装配有单轴叶轮片搅拌器、罩有电热套和配有加热的填充回流冷凝柱的3000ml玻璃反应器。反应器填装有777g(4mol)的对苯二甲酸二甲酯230g(1.6mol)的2，2，4，4-四甲基-1，3-环丁二醇、460.8g(3.2mol)的环己烷二甲醇和1.12g的三(2-乙基己酸)丁基锡(使得在最终聚合物中将存在200ppm锡金属)。手动设置加热套为100％输出。采用Camile过程控制系统使得设定点和数据采集变得方便。一旦反应物熔融，就开始搅拌并缓慢提高至250rpm。随着运转时间，反应器的温度逐渐升高。借助天平记录所收集的甲醇的重量。当甲醇逸出停止或处于预选的260℃的较低温度下时，停止反应。采用氮气吹扫排出低聚物并冷却到室温。采用液氮冷冻低聚物并破碎成足够小的小块，以经过称量后装入500ml圆底烧瓶中。These polyesters are prepared by performing transesterification and polycondensation in separate stages. The transesterification experiments were carried out in a continuous temperature rise (CTR) reactor. The CTR is a 3000ml glass reactor equipped with a single shaft impeller vane stirrer, covered with a heating mantle and equipped with a heated packed reflux condensation column. The reactor is filled with 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 460.8g (3.2mol) of dimethyl terephthalate 230g (1.6mol) of 777g (4mol) Cyclohexanedimethanol and 1.12 g of butyltin tris(2-ethylhexanoate) (so that 200 ppm tin metal will be present in the final polymer). Manually set the heating mantle to 100% output. The use of the Camile process control system facilitates set point and data collection. Once the reactants were molten, stirring was started and slowly increased to 250 rpm. With the running time, the temperature of the reactor gradually increased. The weight of methanol collected was recorded with the aid of a balance. The reaction was stopped when methanol evolution ceased or at a preselected lower temperature of 260°C. The oligomers were removed with a nitrogen purge and cooled to room temperature. The oligomer was frozen with liquid nitrogen and broken into pieces small enough to be weighed into a 500ml round bottom flask.

在缩聚反应中，500ml圆底烧瓶填装有约150g的以上所制备的低聚物。该烧瓶装备有不锈钢搅拌器和聚合物盖。将玻璃器皿设置在半摩尔聚合物成套设备(a half mole polymer rig)上并启动Camile序列。一旦低聚物熔融，将搅拌器定位为距离烧瓶底部一个完整的翻转(positioned one full turn from the flask bottom)。对于各个实施例的由Camile软件控制的温度/压力/搅动速率序列报告于下表中。In the polycondensation reaction, a 500 ml round bottom flask was filled with about 150 g of the oligomer prepared above. The flask was equipped with a stainless steel stirrer and a polymer cap. Set up the glassware on a half mole polymer rig and start the Camile sequence. Once the oligomer was molten, the stirrer was positioned one full turn from the flask bottom. The temperature/pressure/agitation rate sequences controlled by the Camile software for each example are reported in the table below.

实施例7H和实施例7I的Camile序列The Camile sequence of embodiment 7H and embodiment 7I

实施例7N-实施例7Q的Camile序列The Camile sequence of embodiment 7N-embodiment 7Q

实施例7K和实施例7L的Camile序列The Camile sequence of Example 7K and Example 7L

实施例7J和实施例7M的Camile序列The Camile sequence of embodiment 7J and embodiment 7M

从烧瓶中回收所得聚合物，使用液压切碎机切碎，并研磨至6mm筛孔尺寸。对各研磨的聚合物的样品进行如下测试：在25℃以0.5g/100ml的浓度在60/40(wt/wt)苯酚/四氯乙烷中测定比浓对数粘度、通过X射线荧光测量催化剂水平(Sn)和通过透射光谱获得颜色(L^*、a^*、b^*)。通过1H NMR获得聚合物组成。使用Rheometrics MechanicalSpectrometer(RMS-800)对样品进行热稳定性和熔体粘度的测试。The resulting polymer was recovered from the flask, chopped using a hydraulic chopper, and ground to a mesh size of 6 mm. Samples of each milled polymer were tested as follows: Inherent viscosity was measured in 60/40 (wt/wt) phenol/tetrachloroethane at 25° C. at a concentration of 0.5 g/100 ml, measured by X-ray fluorescence Catalyst level (Sn) and color (L^* , a^* , b^* ) obtained by transmission spectroscopy. Polymer compositions were obtained by 1H NMR. Rheometrics Mechanical Spectrometer (RMS-800) was used to test the thermal stability and melt viscosity of the samples.

下表显示了本实施例的聚酯的实验数据。数据表明，对于恒定的比浓对数粘度，2，2，4，4-四甲基-1，3-环丁二醇水平的增加以几乎线性的方式提高玻璃化转变温度。图3还显示了Tg对组成和比浓对数粘度的依赖性。The table below shows the experimental data for the polyesters of this example. The data show that for a constant inherent viscosity, increasing levels of 2,2,4,4-tetramethyl-1,3-cyclobutanediol increases the glass transition temperature in a nearly linear fashion. Figure 3 also shows the dependence of Tg on composition and inherent viscosity.

表7Table 7

作为比浓对数粘度和组成的函数的玻璃化转变温度Glass transition temperature as a function of inherent viscosity and composition

NA＝不可得到的NA = not available

实施例8Example 8

本实施例举例说明用于制备本发明聚酯的2，2，4，4-四甲基-1，3-环丁二醇的量对聚酯的玻璃化转变温度的影响。在本实施例中制备的聚酯包含大于25-小于40mol％的2，2，4，4-四甲基-1，3-环丁二醇残基。This example illustrates the effect of the amount of 2,2,4,4-tetramethyl-1,3-cyclobutanediol used to prepare the polyesters of the invention on the glass transition temperature of the polyesters. The polyesters prepared in this example contained greater than 25 to less than 40 mole percent 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

将对苯二甲酸二甲酯、1，4-环己烷二甲醇和2，2，4，4-四甲基-1，3-环丁二醇称重加入500-毫升单颈圆底烧瓶中。2，2，4，4-四甲基-1，3-环丁二醇起始材料的NMR分析显示顺式/反式比例为53/47。本实施例的聚酯采用1.2/1二醇/酸比例制备，全部过量均来自2，2，4，4-四甲基-1，3-环丁二醇。加入足够的氧化二丁锡催化剂以在最终聚合物中得到300ppm锡。烧瓶处于具有真空降低能力的0.2SCFC氮气吹扫下。将烧瓶浸入200℃的Belmont金属浴并在反应物熔融之后以200RPM搅拌。约2.5小时后，将温度升高至210℃并将这些条件保持另外的2小时。将温度升高至285℃(约25分钟)并在5分钟内将压力降低至0.3mmHg。随着粘度增加，降低搅拌，1RPM是所用的最小搅拌。改变总聚合时间以获得目标比浓对数粘度。聚合完成后，使Belmont金属浴下降并允许聚合物冷却到低于其玻璃化转变温度。约30分钟后，再次将烧瓶浸入Belmont金属浴(在这30分钟的等待中温度已升至295℃)并加热聚合物物质直到其脱离玻璃烧瓶。在烧瓶中以中等水平搅拌聚合物物质直到聚合物冷却。从烧瓶中取出聚合物并研磨以便通过3mm筛。对该程序进行改变以生产目标的组成为32mol％的如下所述的共聚酯。Dimethyl terephthalate, 1,4-cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol were weighed into a 500-mL single-necked round bottom flask middle. NMR analysis of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol starting material showed a cis/trans ratio of 53/47. The polyester of this example was prepared using a diol/acid ratio of 1.2/1, with all excess coming from 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Sufficient dibutyltin oxide catalyst was added to give 300 ppm tin in the final polymer. The flask was under a 0.2 SCFC nitrogen purge with vacuum reduction capability. The flask was immersed in a Belmont metal bath at 200°C and stirred at 200 RPM after the reactants were molten. After about 2.5 hours, the temperature was raised to 210°C and these conditions were maintained for an additional 2 hours. The temperature was raised to 285°C (about 25 minutes) and the pressure was reduced to 0.3 mmHg within 5 minutes. As viscosity increases, agitation is reduced, 1 RPM is the minimum agitation used. The total polymerization time was varied to achieve the target inherent viscosity. After the polymerization was complete, the Belmont metal bath was lowered and the polymer was allowed to cool below its glass transition temperature. After about 30 minutes, the flask was again immersed in the Belmont metal bath (the temperature had risen to 295°C during this 30 minute wait) and the polymer mass was heated until it came out of the glass flask. Stir the polymer mass in the flask on a medium level until the polymer cools. The polymer was removed from the flask and ground to pass through a 3 mm sieve. The procedure was modified to produce a copolyester as described below with a target composition of 32 mol%.

如以上“测量方法”部分所述测量比浓对数粘度。如在前面测量方法部分所述，由1H NMR测定聚酯的组成。在以20℃/min的速率骤冷后使用二次加热，由DSC测定玻璃化转变温度。Inherent viscosity was measured as described in the "Measurement Methods" section above. The composition of the polyesters was determined by 1H NMR as described above in the Measurement Methods section. Glass transition temperatures were determined by DSC using secondary heating after quenching at a rate of 20°C/min.

下表显示了本实施例的聚酯的实验数据。图3还显示了Tg对组成和比浓对数粘度的依赖性。数据表明，对于恒定的比浓对数粘度，2，2，4，4-四甲基-1，3-环丁二醇水平的增加以几乎线性的方式提高玻璃化转变温度。The table below shows the experimental data for the polyesters of this example. Figure 3 also shows the dependence of Tg on composition and inherent viscosity. The data show that for a constant inherent viscosity, increasing levels of 2,2,4,4-tetramethyl-1,3-cyclobutanediol increases the glass transition temperature in a nearly linear fashion.

表8Table 8

作为比浓对数粘度和组成的函数的玻璃化转变温度Glass transition temperature as a function of inherent viscosity and composition

NA＝不可得到的NA = not available

实施例9Example 9

本实施例举例说明用于制备本发明聚酯的2，2，4，4-四甲基-1，3-环丁二醇的量对聚酯的玻璃化转变温度的影响。在本实施例中制备的聚酯包含2，2，4，4-四甲基-1，3-环丁二醇残基，其数量为：40mol％或更多。This example illustrates the effect of the amount of 2,2,4,4-tetramethyl-1,3-cyclobutanediol used to prepare the polyesters of the invention on the glass transition temperature of the polyesters. The polyester prepared in this example contained 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues in an amount of 40 mol% or more.

实施例A-CExamples A-C

这些聚酯通过在分开的阶段进行酯交换和缩聚反应而制备。酯交换实验是在连续升温(CTR)反应器中进行的。CTR是装配有单轴叶轮片搅拌器、罩有电热套和配有加热的填充回流冷凝柱的3000ml玻璃反应器。反应器填装有777g的对苯二甲酸二甲酯、375g的2，2，4，4-四甲基-1，3-环丁二醇、317g的环己烷二甲醇和1.12g的三(2-乙基己酸)丁基锡(使得在最终聚合物中将存在200ppm锡金属)。手动设置加热套为100％输出。采用Camile过程控制系统使得设定点和数据采集变得方便。一旦反应物熔融，就开始搅拌并缓慢提高至250rpm。随着运转时间，反应器的温度逐渐升高。借助天平记录所收集的甲醇的重量。当甲醇逸出停止或处于预选的260℃的较低温度下时，停止反应。采用氮气吹扫排出低聚物并冷却到室温。采用液氮冷冻低聚物并破碎成足够小的小块，以经过称量后装入500ml圆底烧瓶中。These polyesters are prepared by performing transesterification and polycondensation in separate stages. The transesterification experiments were carried out in a continuous temperature rise (CTR) reactor. The CTR is a 3000ml glass reactor equipped with a single shaft impeller vane stirrer, covered with a heating mantle and equipped with a heated packed reflux condensation column. The reactor was charged with 777 g of dimethyl terephthalate, 375 g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 317 g of cyclohexanedimethanol and 1.12 g of tris Butyltin (2-ethylhexanoate) (so that 200 ppm tin metal will be present in the final polymer). Manually set the heating mantle to 100% output. The use of the Camile process control system facilitates set point and data acquisition. Once the reactants were molten, stirring was started and slowly increased to 250 rpm. With the running time, the temperature of the reactor gradually increased. The weight of methanol collected was recorded with the aid of a balance. The reaction was stopped when methanol evolution ceased or at a preselected lower temperature of 260°C. The oligomers were removed with a nitrogen purge and cooled to room temperature. The oligomer was frozen with liquid nitrogen and broken into pieces small enough to be weighed into a 500ml round bottom flask.

在缩聚反应中，500ml圆底烧瓶填装有150g的以上所制备的低聚物。该烧瓶装备有不锈钢搅拌器和聚合物盖。将玻璃器皿设置在半摩尔聚合物成套设备(a half mole polymer rig)上并启动Camile序列。一旦低聚物熔融，将搅拌器定位为距离烧瓶底部一个完整的翻转(positioned one full turn from the flask bottom)。对于这些实施例的由Camile软件控制的温度/压力/搅动速率序列报告于下表中，除非以下另作说明。In the polycondensation reaction, a 500 ml round bottom flask was filled with 150 g of the oligomer prepared above. The flask was equipped with a stainless steel stirrer and a polymer cap. Set up the glassware on a half mole polymer rig and start the Camile sequence. Once the oligomer was molten, the stirrer was positioned one full turn from the flask bottom. The temperature/pressure/agitation rate sequences controlled by the Camile software for these examples are reported in the table below unless otherwise noted below.

缩聚反应的Camile序列Camile sequence of polycondensation reaction

实施例A和B的Camile序列Camile sequences of Examples A and B

对于实施例C，使用上表中的相同序列，但是在阶段7中的时间为50分钟。For Example C, the same sequence as in the table above was used, but with a time of 50 minutes in stage 7.

从烧瓶中回收所得聚合物，使用液压切碎机切碎，并研磨至6mm筛孔尺寸。对各研磨的聚合物的样品进行如下测试：在25℃以0.5g/100ml的浓度在60/40(wt/wt)苯酚/四氯乙烷中测定比浓对数粘度、通过X射线荧光测量催化剂水平(Sn)和通过透射光谱获得颜色(L^*、a^*、b^*)。通过1H NMR获得聚合物组成。使用Rheometrics MechanicalSpectrometer(RMS-800)对样品进行热稳定性和熔体粘度的测试。The resulting polymer was recovered from the flask, chopped using a hydraulic chopper, and ground to a mesh size of 6 mm. Samples of each milled polymer were tested as follows: Inherent viscosity was measured in 60/40 (wt/wt) phenol/tetrachloroethane at 25° C. at a concentration of 0.5 g/100 ml, measured by X-ray fluorescence Catalyst level (Sn) and color (L^* , a^* , b^* ) obtained by transmission spectroscopy. Polymer compositions were obtained by 1H NMR. Rheometrics Mechanical Spectrometer (RMS-800) was used to test the thermal stability and melt viscosity of the samples.

实施例D-K和MExamples D-K and M

这些实施例的聚酯如以上对于实施例A-C所述制备，但是，对于实施例AD-K和M，在最终聚合物中目标锡的量为150ppm。下表描述了对于这些实施例的由Camile软件控制的温度/压力/搅拌速率序列。The polyesters of these examples were prepared as described above for Examples A-C, however, for Examples AD-K and M, the target amount of tin in the final polymer was 150 ppm. The table below describes the temperature/pressure/stirring rate sequence controlled by the Camile software for these examples.

实施例D、F和H的Camile序列Camile sequences of examples D, F and H

对于实施例D，在阶段7中搅拌器被调至25rpm，进行95分钟。For Example D, the stirrer was turned to 25 rpm in stage 7 for 95 minutes.

实施例E的Camile序列The Camile sequence of embodiment E

对于实施例K，使用上表中的相同序列，但是在阶段7中的时间为75分钟。For Example K, the same sequence as in the table above was used, but with a time of 75 minutes in stage 7.

实施例G的Camile序列The Camile sequence of embodiment G

实施例I的Camile序列The Camile sequence of embodiment 1

实施例J的Camile序列The Camile sequence of Example J

实施例L和KExamples L and K

将对苯二甲酸二甲酯、1，4-环己烷二甲醇和2，2，4，4-四甲基-1，3-环丁二醇称重加入500-毫升单颈圆底烧瓶中。本实施例的聚酯采用1.2/1二醇/酸比例制备，全部过量均来自2，2，4，4-四甲基-1，3-环丁二醇。加入足够的氧化二丁锡催化剂以在最终聚合物中得到300ppm锡。烧瓶处于具有真空降低能力的0.2SCFC氮气吹扫下。将烧瓶浸入200℃的Belmont金属浴并在反应物熔融之后以200RPM搅拌。约2.5小时后，将温度升高至210℃并将这些条件保持另外的2小时。将温度升高至285℃(约25分钟)并在5分钟内将压力降低至0.3mmHg。随着粘度增加，降低搅拌，15RPM是所用的最小搅拌。改变总聚合时间以获得目标比浓对数粘度。聚合完成后，使Belmont金属浴下降并允许聚合物冷却到低于其玻璃化转变温度。约30分钟后，再次将烧瓶浸入Belmont金属浴(在这30分钟的等待中温度已升至295℃)并加热聚合物物质直到其脱离玻璃烧瓶。在烧瓶中以中等水平搅拌聚合物物质直到聚合物冷却。从烧瓶中取出聚合物并研磨以便通过3mm筛。对该程序进行改变以生产目标的组成为45mol％的如下所述的共聚酯。Dimethyl terephthalate, 1,4-cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol were weighed into a 500-mL single-necked round bottom flask middle. The polyester of this example was prepared using a diol/acid ratio of 1.2/1, with all excess coming from 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Sufficient dibutyltin oxide catalyst was added to give 300 ppm tin in the final polymer. The flask was under a 0.2 SCFC nitrogen purge with vacuum reduction capability. The flask was immersed in a Belmont metal bath at 200°C and stirred at 200 RPM after the reactants were molten. After about 2.5 hours, the temperature was raised to 210°C and these conditions were maintained for an additional 2 hours. The temperature was raised to 285°C (about 25 minutes) and the pressure was reduced to 0.3 mmHg within 5 minutes. As the viscosity increased, the agitation was reduced, 15 RPM was the minimum agitation used. The total polymerization time was varied to achieve the target inherent viscosity. After the polymerization was complete, the Belmont metal bath was lowered and the polymer was allowed to cool below its glass transition temperature. After about 30 minutes, the flask was again immersed in the Belmont metal bath (the temperature had risen to 295°C during this 30 minute wait) and the polymer mass was heated until it came out of the glass flask. Stir the polymer mass in the flask on a medium level until the polymer cools. The polymer was removed from the flask and ground to pass through a 3 mm sieve. The procedure was modified to produce a copolyester as described below with a target composition of 45 mol%.

如以上“测量方法”部分所述测量比浓对数粘度。如在前面测量方法部分所述，由1H NMR测定聚酯的组成。在以20℃/min的速率骤冷后使用二次加热，由DSC测定玻璃化转变温度。Inherent viscosity was measured as described in the "Measurement Methods" section above. The composition of the polyesters was determined by 1H NMR as described above in the Measurement Methods section. Glass transition temperatures were determined by DSC using secondary heating after quenching at a rate of 20°C/min.

下表显示了本实施例的聚酯的实验数据。数据表明，对于恒定的比浓对数粘度，2，2，4，4-四甲基-1，3-环丁二醇水平的增加以几乎线性的方式提高玻璃化转变温度。图3还显示了Tg对组成和比浓对数粘度的依赖性。The table below shows the experimental data for the polyesters of this example. The data show that for a constant inherent viscosity, increasing levels of 2,2,4,4-tetramethyl-1,3-cyclobutanediol increases the glass transition temperature in a nearly linear fashion. Figure 3 also shows the dependence of Tg on composition and inherent viscosity.

表9Table 9

作为比浓对数粘度和组成的函数的玻璃化转变温度Glass transition temperature as a function of inherent viscosity and composition

NA＝不可得到的NA = not available

实施例10Example 10

本实施例举例说明2，2，4，4-四甲基-1，3-环丁二醇异构体(顺式或反式)的类型的主导地位对聚酯的玻璃化转变温度的影响。This example illustrates the effect of the dominance of the type of 2,2,4,4-tetramethyl-1,3-cyclobutanediol isomer (cis or trans) on the glass transition temperature of polyesters .

将对苯二甲酸二甲酯、1，4-环己烷二甲醇和2，2，4，4-四甲基-1，3-环丁二醇称重加入500-毫升单颈圆底烧瓶中。本实施例的聚酯采用1.2/1二醇/酸比例制备，全部过量均来自2，2，4，4-四甲基-1，3-环丁二醇。加入足够的氧化二丁锡催化剂以在最终聚合物中得到300ppm锡。烧瓶处于具有真空降低能力的0.2SCFC氮气吹扫下。将烧瓶浸入200℃的Belmont金属浴并在反应物熔融之后以200RPM搅拌。约2.5小时后，将温度升高至210℃并将这些条件保持另外的2小时。将温度升高至285℃(约25分钟)并在5分钟内将压力降低至0.3mmHg。随着粘度增加，降低搅拌，15RPM是所用的最小搅拌。改变总聚合时间以获得目标比浓对数粘度。聚合完成后，使Belmont金属浴下降并允许聚合物冷却到低于其玻璃化转变温度。约30分钟后，再次将烧瓶浸入Belmont金属浴(在这30分钟的等待中温度已升至295℃)并加热聚合物物质直到其脱离玻璃烧瓶。在烧瓶中以中等水平搅拌聚合物物质直到聚合物冷却。从烧瓶中取出聚合物并研磨以便通过3mm筛。对该程序进行改变以生产目标的组成为45mol％的如下所述的共聚酯。Dimethyl terephthalate, 1,4-cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol were weighed into a 500-mL single-necked round bottom flask middle. The polyester of this example was prepared using a diol/acid ratio of 1.2/1, with all excess coming from 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Sufficient dibutyltin oxide catalyst was added to give 300 ppm tin in the final polymer. The flask was under a 0.2 SCFC nitrogen purge with vacuum reduction capability. The flask was immersed in a Belmont metal bath at 200°C and stirred at 200 RPM after the reactants were molten. After about 2.5 hours, the temperature was raised to 210°C and these conditions were maintained for an additional 2 hours. The temperature was raised to 285°C (about 25 minutes) and the pressure was reduced to 0.3 mmHg within 5 minutes. As the viscosity increased, the agitation was reduced, 15 RPM was the minimum agitation used. The total polymerization time was varied to achieve the target inherent viscosity. After the polymerization was complete, the Belmont metal bath was lowered and the polymer was allowed to cool below its glass transition temperature. After about 30 minutes, the flask was again immersed in the Belmont metal bath (the temperature had risen to 295°C during this 30 minute wait) and the polymer mass was heated until it came out of the glass flask. Stir the polymer mass in the flask on a medium level until the polymer cools. The polymer was removed from the flask and ground to pass through a 3 mm sieve. The procedure was modified to produce a copolyester as described below with a target composition of 45 mol%.

如以上“测量方法”部分所述测量比浓对数粘度。如在前面测量方法部分所述，由1H NMR测定聚酯的组成。在以20℃/min的速率骤冷后使用二次加热，由DSC测定玻璃化转变温度。Inherent viscosity was measured as described in the "Measurement Methods" section above. The composition of the polyesters was determined by 1H NMR as described above in the Measurement Methods section. Glass transition temperatures were determined by DSC using secondary heating after quenching at a rate of 20°C/min.

下表显示了本实施例的聚酯的实验数据。数据表明，对于恒定的比浓对数粘度，在提高玻璃化转变温度方面，顺式2，2，4，4-四甲基-1，3-环丁二醇的效果约为反式2，2，4，4-四甲基-1，3-环丁二醇的两倍。The table below shows the experimental data for the polyesters of this example. The data show that for a constant inherent viscosity, cis 2,2,4,4-tetramethyl-1,3-cyclobutanediol is about as effective as trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol in increasing the glass transition temperature. 2,4,4-tetramethyl-1,3-cyclobutanediol twice.

表10Table 10

2，2，4，4-四甲基-1，3-环丁二醇顺式/反式组成对Tg的影响Effect of cis/trans composition on Tg of 2,2,4,4-tetramethyl-1,3-cyclobutanediol

NA＝不可得到的NA = not available

实施例11-对比例Embodiment 11-comparative example

本实施例举例说明基于100％2，2，4，4-四甲基-1，3-环丁二醇的聚酯具有慢的结晶半衰期。This example illustrates that a polyester based on 100% 2,2,4,4-tetramethyl-1,3-cyclobutanediol has a slow crystallization half-life.

以与实施例1A中所述方法类似的方法制备仅基于对苯二甲酸和2，2，4，4-四甲基-1，3-环丁二醇的聚酯，，性能示于表11中。采用300ppm氧化二丁锡制备该聚酯。2，2，4，4-四甲基-1，3-环丁二醇的顺式/反式比例为65/35。In a method similar to that described in Example 1A, only polyesters based on terephthalic acid and 2,2,4,4-tetramethyl-1,3-cyclobutanediol were prepared, and the properties are shown in Table 11 middle. The polyester was prepared using 300 ppm dibutyltin oxide. The cis/trans ratio of 2,2,4,4-tetramethyl-1,3-cyclobutanediol is 65/35.

在320℃由研磨的聚合物压制薄膜。在220-250℃以10℃为增量，进行自熔体的结晶半衰期的测量，并将测量结果记录在表11中。取样品的最快结晶半衰期作为随温度变化的结晶半衰期的最小值。这种聚酯的最快结晶半衰期为约1300分钟。该值与如下事实形成对比：仅基于对苯二甲酸和1，4-环己烷二甲醇(无共聚单体改性)的聚酯(PCT)具有极短的结晶半衰期(小于1分钟)，如图1所示。Films were pressed from the ground polymer at 320°C. Crystallization half-life measurements from the melt were performed at 220-250°C in 10°C increments and are reported in Table 11. The fastest crystallization half-life of the sample was taken as the minimum value of the crystallization half-life as a function of temperature. The fastest crystallization half-life for this polyester is about 1300 minutes. This value contrasts with the fact that only polyester (PCT) based on terephthalic acid and 1,4-cyclohexanedimethanol (without comonomer modification) has an extremely short crystallization half-life (less than 1 min), As shown in Figure 1.

表11Table 11

结晶半衰期(分钟)Crystallization half-life (minutes)

其中：F是2，2，4，4-四甲基-1，3-环丁二醇(65/35反式/顺式)Where: F is 2,2,4,4-tetramethyl-1,3-cyclobutanediol (65/35 trans/cis)

实施例12Example 12

使用3.5英寸单螺杆挤出机生产包含聚酯的薄板，所述聚酯已经以100mol％对苯二甲酸残基、80mol％1，4-环己烷二甲醇残基和20mol％2，2，4，4-四甲基-1，3-环丁二醇残基为目标组成进行制备。连续挤出薄板，测量厚度为177密耳，然后将各种薄板剪切到合适尺寸。对一个薄板测量比浓对数粘度和玻璃化转变温度。薄板的比浓对数粘度的测量结果为0.69dl/g。薄板的玻璃化转变温度的测量结果为106℃。然后将薄板在50％相对湿度和60℃下调理2周。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热，将热成形烘箱加热器设定为70/60/60％输出。将薄板留在烘箱中达不同的时间，以便测定薄板温度对部件质量的影响，如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的：部件体积除以在该组实验中获得的最大部件体积(实施例G)。目视检查热成形部件的任何起泡，并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明，这些玻璃化转变温度为106℃的热塑性薄板可以在以下所示的条件下热成形，如由在热成形前未预干燥薄板的情况下，这些薄板具有至少95％的拉伸和未起泡所证明的。A 3.5-inch single-screw extruder was used to produce sheets comprising polyester that had been prepared with 100 mol% terephthalic acid residues, 80 mol% 1,4-cyclohexanedimethanol residues, and 20 mol% 2,2, The 4,4-tetramethyl-1,3-cyclobutanediol residue was prepared as the target composition. Sheets were continuously extruded, measuring a thickness of 177 mils, and the various sheets were then cut to size. Inherent viscosity and glass transition temperature were measured on a thin plate. The inherent viscosity of the sheet was measured to be 0.69 dl/g. The measurement result of the glass transition temperature of the sheet was 106°C. The sheets were then conditioned at 50% relative humidity and 60°C for 2 weeks. The sheets were then thermoformed using a Brown thermoformer into a female mold with a draw ratio of 2.5:1. Using only tip heating, set the thermoforming oven heater to 70/60/60% output. The sheets were left in the oven for various times in order to determine the effect of sheet temperature on part quality, as shown in the table below. Part quality is determined by measuring the volume of the thermoformed part, calculating the stretch and visually inspecting the thermoformed part. Stretch was calculated by dividing the part volume by the largest part volume obtained in this set of experiments (Example G). The thermoformed parts were visually inspected for any blistering and the degree of blistering was graded as no (N), low (L) or high (H). The following results demonstrate that these thermoplastic sheets with a glass transition temperature of 106°C can be thermoformed under the conditions shown below, as determined by the fact that the sheets have at least 95% elongation and Proof of non-foaming.

实施例13Example 13

使用3.5英寸单螺杆挤出机生产包含聚酯的片材，所述聚酯已经以100mol％对苯二甲酸残基、80mol％1，4-环己烷二甲醇残基和20mol％2，2，4，4-四甲基-1，3-环丁二醇残基为目标组成进行制备。连续挤出薄板，测量厚度为177密耳，然后将各种薄板剪切到合适尺寸。对一个薄板测量比浓对数粘度和玻璃化转变温度。薄板的比浓对数粘度的测量结果为0.69dl/g。薄板的玻璃化转变温度的测量结果为106℃。然后将薄板在100％相对湿度和25℃下调理2周。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热，将热成形烘箱加热器设定为60/40/40％输出。将薄板留在烘箱中达不同的时间，以便测定薄板温度对部件质量的影响，如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的：部件体积除以在该组实验中获得的最大部件体积(实施例G)。目视检查热成形部件的任何起泡，并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明，这些玻璃化转变温度为106℃的热塑性薄板可以在以下所示的条件下热成形，如由在热成形前未预干燥薄板的情况下，生产的薄板具有至少95％的拉伸和未起泡所证明的。A 3.5-inch single-screw extruder was used to produce sheets comprising polyester that had been prepared with 100 mol% terephthalic acid residues, 80 mol% 1,4-cyclohexanedimethanol residues, and 20 mol% 2,2 , 4,4-tetramethyl-1,3-cyclobutanediol residue was prepared as the target composition. Sheets were continuously extruded, measuring a thickness of 177 mils, and the various sheets were then cut to size. Inherent viscosity and glass transition temperature were measured on a thin plate. The inherent viscosity of the sheet was measured to be 0.69 dl/g. The measurement result of the glass transition temperature of the sheet was 106°C. The sheets were then conditioned for 2 weeks at 100% relative humidity and 25°C. The sheets were then thermoformed using a Brown thermoformer into a female mold with a draw ratio of 2.5:1. Using only tip heating, set the thermoforming oven heater to 60/40/40% output. The sheets were left in the oven for various times in order to determine the effect of sheet temperature on part quality, as shown in the table below. Part quality is determined by measuring the volume of the thermoformed part, calculating the stretch and visually inspecting the thermoformed part. Stretch was calculated by dividing the part volume by the largest part volume obtained in this set of experiments (Example G). The thermoformed parts were visually inspected for any blistering and the degree of blistering was graded as no (N), low (L) or high (H). The following results demonstrate that these thermoplastic sheets with a glass transition temperature of 106°C can be thermoformed under the conditions shown below, as produced by the sheet without pre-drying the sheet prior to thermoforming, with an elongation of at least 95%. And unbubbled as proven.

实施例14-对比例Embodiment 14-comparative example

使用3.5英寸单螺杆挤出机生产由Kelvx 201组成的薄板。Kelvx是由69.85％PCTG(获自Eastman Chemical Co.的Eastar，其具有100mol％对苯二甲酸残基、62mol％1，4-环己烷二甲醇残基和38mol％乙二醇残基)；30％PC(双酚A聚碳酸酯)；和0.15％Weston 619(由CromptonCorporation出售的稳定剂)组成的共混物。连续挤出薄板，测量厚度为177密耳，然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度，其为100℃。然后将薄板在50％相对湿度和60℃下调理2周。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热，将热成形烘箱加热器设定为70/60/60％输出。将薄板留在烘箱中达不同的时间，以便测定薄板温度对部件质量的影响，如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的：部件体积除以在该组实验中获得的最大部件体积(实施例E)。目视检查热成形部件的任何起泡，并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明，这些玻璃化转变温度为100℃的热塑性薄板可以在以下所示的条件下热成形，如由在热成形前未预干燥薄板的情况下，生产的薄板具有至少95％的拉伸和未起泡所证明的。Sheets consisting of Kelvx 201 were produced using a 3.5 inch single screw extruder. Kelvx is composed of 69.85% PCTG (Eastar obtained from Eastman Chemical Co., which has 100 mol% terephthalic acid residues, 62 mol% 1,4-cyclohexanedimethanol residues, and 38 mol% ethylene glycol residues); A blend of 30% PC (bisphenol A polycarbonate); and 0.15% Weston 619 (stabilizer sold by Crompton Corporation). Sheets were continuously extruded, measuring a thickness of 177 mils, and the various sheets were then cut to size. The glass transition temperature was measured for one sheet and it was 100°C. The sheets were then conditioned at 50% relative humidity and 60°C for 2 weeks. The sheets were then thermoformed using a Brown thermoformer into a female mold with a draw ratio of 2.5:1. Using only tip heating, set the thermoforming oven heater to 70/60/60% output. The sheets were left in the oven for various times in order to determine the effect of sheet temperature on part quality, as shown in the table below. Part quality is determined by measuring the volume of the thermoformed part, calculating the stretch and visually inspecting the thermoformed part. Stretch was calculated by dividing the part volume by the largest part volume obtained in this set of experiments (Example E). The thermoformed parts were visually inspected for any blistering and the degree of blistering was graded as no (N), low (L) or high (H). The following results demonstrate that these thermoplastic sheets with a glass transition temperature of 100°C can be thermoformed under the conditions shown below, as produced by the sheet without pre-drying the sheet before thermoforming, with an elongation of at least 95%. And unbubbled as proven.

实施例15-对比例Embodiment 15-comparative example

使用3.5英寸单螺杆挤出机生产由Kelvx 201组成的薄板。连续挤出薄板，测量厚度为177密耳，然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度，其为100℃。然后将薄板在100％相对湿度和25℃下调理2周。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热，将热成形烘箱加热器设定为60/40/40％输出。将薄板留在烘箱中达不同的时间，以便测定薄板温度对部件质量的影响，如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的：部件体积除以在该组实验中获得的最大部件体积(实施例H)。目视检查热成形部件的任何起泡，并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明，这些玻璃化转变温度为100℃的热塑性薄板可以在以下所示的条件下热成形，如由在热成形前未预干燥薄板的情况下，生产的薄板具有大于95％的拉伸和未起泡所证明的。Sheets consisting of Kelvx 201 were produced using a 3.5 inch single screw extruder. Sheets were continuously extruded, measuring a thickness of 177 mils, and the various sheets were then cut to size. The glass transition temperature was measured for one sheet and it was 100°C. The sheets were then conditioned for 2 weeks at 100% relative humidity and 25°C. The sheets were then thermoformed using a Brown thermoformer into a female mold with a draw ratio of 2.5:1. Using only tip heating, set the thermoforming oven heater to 60/40/40% output. The sheets were left in the oven for various times in order to determine the effect of sheet temperature on part quality, as shown in the table below. Part quality is determined by measuring the volume of the thermoformed part, calculating the stretch and visually inspecting the thermoformed part. Stretch was calculated by dividing the part volume by the largest part volume obtained in this set of experiments (Example H). The thermoformed parts were visually inspected for any blistering and the degree of blistering was graded as no (N), low (L) or high (H). The following results demonstrate that these thermoplastic sheets with a glass transition temperature of 100°C can be thermoformed under the conditions shown below, as produced by the sheet without pre-drying the sheet before thermoforming, with a stretch of greater than 95%. And unbubbled as proven.

NR＝未记录的NR = not recorded

实施例16-对比例Embodiment 16-comparative example

使用3.5英寸单螺杆挤出机生产由PCTG 25976(100mol％对苯二甲酸残基、62mol％1，4-环己烷二甲醇残基和38mol％乙二醇残基)组成的薄板。连续挤出薄板，测量厚度为118密耳，然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度，其为87℃。然后将薄板在50％相对湿度和60℃下调理4周。水分含量的测量结果为0.17wt％。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热，将热成形烘箱加热器设定为70/60/60％输出。将薄板留在烘箱中达不同的时间，以便测定薄板温度对部件质量的影响，如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的：部件体积除以在该组实验中获得的最大部件体积(实施例A)。目视检查热成形部件的任何起泡，并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明，这些玻璃化转变温度为87℃的热塑性薄板可以在以下所示的条件下热成形，如由在热成形前未预干燥薄板的情况下，生产的薄板具有大于95％的拉伸和未起泡所证明的。Sheets consisting of PCTG 25976 (100 mol% terephthalic acid residues, 62 mol% 1,4-cyclohexanedimethanol residues, and 38 mol% ethylene glycol residues) were produced using a 3.5 inch single screw extruder. Sheets were continuously extruded, measuring a thickness of 118 mils, and the various sheets were then cut to size. The glass transition temperature was measured for one sheet and it was 87°C. The sheets were then conditioned for 4 weeks at 50% relative humidity and 60°C. The moisture content was measured to be 0.17 wt%. The sheets were then thermoformed using a Brown thermoformer into a female mold with a draw ratio of 2.5:1. Using only tip heating, set the thermoforming oven heater to 70/60/60% output. The sheets were left in the oven for various times in order to determine the effect of sheet temperature on part quality, as shown in the table below. Part quality is determined by measuring the volume of the thermoformed part, calculating the stretch and visually inspecting the thermoformed part. Stretch was calculated by dividing the part volume by the largest part volume obtained in this set of experiments (Example A). The thermoformed parts were visually inspected for any blistering and the degree of blistering was graded as no (N), low (L) or high (H). The following results demonstrate that these thermoplastic sheets with a glass transition temperature of 87°C can be thermoformed under the conditions shown below, as produced by sheets with greater than 95% elongation in the absence of pre-drying of the sheets prior to thermoforming And unbubbled as proven.

实施例17-对比例Embodiment 17-comparative example

使用1.25英寸单螺杆挤出机生产由20wt％Teijin L-1250聚碳酸酯(双酚A聚碳酸酯)、79.85wt％PCTG 25976和0.15wt％Weston 619组成的可混共混物。然后使用3.5英寸单螺杆挤出机生产由该共混物组成的薄板。连续挤出薄板，测量厚度为118密耳，然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度，其为94℃。然后将薄板在50％相对湿度和60℃下调理4周。水分含量的测量结果为0.25wt％。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热，将热成形烘箱加热器设定为70/60/60％输出。将薄板留在烘箱中达不同的时间，以便测定薄板温度对部件质量的影响，如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的：部件体积除以在该组实验中获得的最大部件体积(实施例A)。目视检查热成形部件的任何起泡，并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明，这些玻璃化转变温度为94℃的热塑性薄板可以在以下所示的条件下热成形，如由在热成形前未预干燥薄板的情况下，生产的薄板具有大于95％的拉伸和未起泡所证明的。A 1.25 inch single screw extruder was used to produce a miscible blend consisting of 20 wt% Teijin L-1250 polycarbonate (bisphenol A polycarbonate), 79.85 wt% PCTG 25976 and 0.15 wt% Weston 619. Sheets consisting of this blend were then produced using a 3.5 inch single screw extruder. Sheets were continuously extruded, measuring a thickness of 118 mils, and the various sheets were then cut to size. The glass transition temperature was measured for one sheet and it was 94°C. The sheets were then conditioned for 4 weeks at 50% relative humidity and 60°C. The moisture content was measured to be 0.25 wt%. The sheets were then thermoformed using a Brown thermoformer into a female mold with a draw ratio of 2.5:1. Using only tip heating, set the thermoforming oven heater to 70/60/60% output. The sheets were left in the oven for various times in order to determine the effect of sheet temperature on part quality, as shown in the table below. Part quality is determined by measuring the volume of the thermoformed part, calculating the stretch and visually inspecting the thermoformed part. Stretch was calculated by dividing the part volume by the largest part volume obtained in this set of experiments (Example A). The thermoformed parts were visually inspected for any blistering and the degree of blistering was graded as no (N), low (L) or high (H). The following results demonstrate that these thermoplastic sheets with a glass transition temperature of 94°C can be thermoformed under the conditions shown below, as produced by sheets with greater than 95% elongation without pre-drying the sheets prior to thermoforming And unbubbled as proven.

实施例18-对比例Embodiment 18-comparative example

使用1.25英寸单螺杆挤出机生产由30wt％Teijin L-1250聚碳酸酯、69.85wt％PCTG 25976和0.15wt％Weston 619组成的可混共混物。然后使用3.5英寸单螺杆挤出机生产由该共混物组成的薄板。连续挤出薄板，测量厚度为118密耳，然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度，其为99℃。然后将薄板在50％相对湿度和60℃下调理4周。水分含量的测量结果为0.25wt％。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热，将热成形烘箱加热器设定为70/60/60％输出。将薄板留在烘箱中达不同的时间，以便测定薄板温度对部件质量的影响，如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的：部件体积除以在该组实验中获得的最大部件体积(实施例A)。目视检查热成形部件的任何起泡，并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明，这些玻璃化转变温度为99℃的热塑性薄板可以在以下所示的条件下热成形，如由在热成形前未预干燥薄板的情况下，生产的薄板具有大于95％的拉伸和未起泡所证明的。A 1.25 inch single screw extruder was used to produce a miscible blend consisting of 30 wt% Teijin L-1250 polycarbonate, 69.85 wt% PCTG 25976 and 0.15 wt% Weston 619. Sheets consisting of this blend were then produced using a 3.5 inch single screw extruder. Sheets were continuously extruded, measuring a thickness of 118 mils, and the various sheets were then cut to size. The glass transition temperature was measured for one sheet and it was 99°C. The sheets were then conditioned for 4 weeks at 50% relative humidity and 60°C. The moisture content was measured to be 0.25 wt%. The sheets were then thermoformed using a Brown thermoformer into a female mold with a draw ratio of 2.5:1. Using only tip heating, set the thermoforming oven heater to 70/60/60% output. The sheets were left in the oven for various times in order to determine the effect of sheet temperature on part quality, as shown in the table below. Part quality is determined by measuring the volume of the thermoformed part, calculating the stretch and visually inspecting the thermoformed part. Stretch was calculated by dividing the part volume by the largest part volume obtained in this set of experiments (Example A). The thermoformed parts were visually inspected for any blistering and the degree of blistering was graded as no (N), low (L) or high (H). The following results demonstrate that these thermoplastic sheets with a glass transition temperature of 99°C can be thermoformed under the conditions shown below, as produced by sheets with greater than 95% tensile And unbubbled as proven.

NA＝不适用的。0值表明未形成薄板，因为其没有拉入模具(可能因为其温度太低)。NA = not applicable. A value of 0 indicates that no sheet was formed because it was not pulled into the die (probably because it was too cold).

实施例19-对比例Embodiment 19-comparative example

使用1.25英寸单螺杆挤出机生产由40wt％Teijin L-1250聚碳酸酯、59.85wt％PCTG 25976和0.15wt％Weston 619组成的可混共混物。然后使用3.5英寸单螺杆挤出机生产由该共混物组成的薄板。连续挤出薄板，测量厚度为118密耳，然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度，其为105℃。然后将薄板在50％相对湿度和60℃下调理4周。水分含量的测量结果为0.265wt％。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热，将热成形烘箱加热器设定为70/60/60％输出。将薄板留在烘箱中达不同的时间，以便测定薄板温度对部件质量的影响，如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的：部件体积除以在该组实验中获得的最大部件体积(实施例8A-8E)。目视检查热成形部件的任何起泡，并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明，这些玻璃化转变温度为105℃的热塑性薄板可以在以下所示的条件下热成形，如由在热成形前未预干燥薄板的情况下，生产的薄板具有大于95％的拉伸和未起泡所证明的。A 1.25 inch single screw extruder was used to produce a miscible blend consisting of 40 wt% Teijin L-1250 polycarbonate, 59.85 wt% PCTG 25976 and 0.15 wt% Weston 619. Sheets consisting of this blend were then produced using a 3.5 inch single screw extruder. Sheets were continuously extruded, measuring a thickness of 118 mils, and the various sheets were then cut to size. The glass transition temperature was measured for one sheet and it was 105°C. The sheets were then conditioned for 4 weeks at 50% relative humidity and 60°C. The moisture content was measured to be 0.265 wt%. The sheets were then thermoformed using a Brown thermoformer into a female mold with a draw ratio of 2.5:1. Using only tip heating, set the thermoforming oven heater to 70/60/60% output. The sheets were left in the oven for various times in order to determine the effect of sheet temperature on part quality, as shown in the table below. Part quality is determined by measuring the volume of the thermoformed part, calculating the stretch and visually inspecting the thermoformed part. Stretch was calculated by dividing the part volume by the largest part volume obtained in this set of experiments (Examples 8A-8E). The thermoformed parts were visually inspected for any blistering and the degree of blistering was graded as no (N), low (L) or high (H). The following results demonstrate that these thermoplastic sheets with a glass transition temperature of 105°C can be thermoformed under the conditions shown below, as produced by the sheet without pre-drying the sheet before thermoforming, with an elongation greater than 95%. And unbubbled as proven.

实施例20-对比例Embodiment 20-comparative example

使用1.25英寸单螺杆挤出机生产由50wt％Teijin L-1250聚碳酸酯、49.85wt％PCTG 25976和0.15wt％Weston 619组成的可混共混物。连续挤出薄板，测量厚度为118密耳，然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度，其为111℃。然后将薄板在50％相对湿度和60℃下调理4周。水分含量的测量结果为0.225wt％。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热，将热成形烘箱加热器设定为70/60/60％输出。将薄板留在烘箱中达不同的时间，以便测定薄板温度对部件质量的影响，如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的：部件体积除以在该组实验中获得的最大部件体积(实施例A-D)。目视检查热成形部件的任何起泡，并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明，这些玻璃化转变温度为111℃的热塑性薄板可以在以下所示的条件下热成形，如由在热成形前未预干燥薄板的情况下，生产的薄板具有大于95％的拉伸和未起泡所证明的。A 1.25 inch single screw extruder was used to produce a miscible blend consisting of 50 wt% Teijin L-1250 polycarbonate, 49.85 wt% PCTG 25976 and 0.15 wt% Weston 619. Sheets were continuously extruded, measuring a thickness of 118 mils, and the various sheets were then cut to size. The glass transition temperature was measured for one sheet and it was 111°C. The sheets were then conditioned for 4 weeks at 50% relative humidity and 60°C. The moisture content was measured to be 0.225 wt%. The sheets were then thermoformed using a Brown thermoformer into a female mold with a draw ratio of 2.5:1. Using only tip heating, set the thermoforming oven heater to 70/60/60% output. The sheets were left in the oven for various times in order to determine the effect of sheet temperature on part quality, as shown in the table below. Part quality is determined by measuring the volume of the thermoformed part, calculating the stretch and visually inspecting the thermoformed part. Stretch was calculated by dividing the part volume by the largest part volume obtained in the set of experiments (Examples A-D). The thermoformed parts were visually inspected for any blistering and the degree of blistering was graded as no (N), low (L) or high (H). The following results demonstrate that these thermoplastic sheets with a glass transition temperature of 111°C can be thermoformed under the conditions shown below, as produced by sheets with greater than 95% elongation in the absence of pre-drying of the sheets prior to thermoforming And unbubbled as proven.

NA＝不适用的。0值表明未形成薄板，因为其没有拉入模具(可能因为其温度太低)。NA = not applicable. A value of 0 indicates that no sheet was formed because it was not pulled into the die (probably because it was too cold).

实施例21-对比例Embodiment 21-comparative example

使用1.25英寸单螺杆挤出机生产由60wt％Teijin L-1250聚碳酸酯、39.85wt％PCTG 25976和0.15wt％Weston 619组成的可混共混物。然后使用3.5英寸单螺杆挤出机生产由该共混物组成的薄板。连续挤出薄板，测量厚度为118密耳，然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度，其为117℃。然后将薄板在50％相对湿度和60℃下调理4周。水分含量的测量结果为0.215wt％。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热，将热成形烘箱加热器设定为70/60/60％输出。将薄板留在烘箱中达不同的时间，以便测定薄板温度对部件质量的影响，如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的：部件体积除以在该组实验中获得的最大部件体积(实施例A)。目视检查热成形部件的任何起泡，并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明，这些玻璃化转变温度为117℃的热塑性薄板不能在以下所示的条件下热成形，如由在热成形前未预干燥薄板的情况下，不能生产出具有大于95％的拉伸和未起泡的薄板所证明的。A 1.25 inch single screw extruder was used to produce a miscible blend consisting of 60 wt% Teijin L-1250 polycarbonate, 39.85 wt% PCTG 25976 and 0.15 wt% Weston 619. Sheets consisting of this blend were then produced using a 3.5 inch single screw extruder. Sheets were continuously extruded, measuring a thickness of 118 mils, and the various sheets were then cut to size. The glass transition temperature was measured for one sheet and it was 117°C. The sheets were then conditioned for 4 weeks at 50% relative humidity and 60°C. The moisture content was measured to be 0.215 wt%. The sheets were then thermoformed using a Brown thermoformer into a female mold with a draw ratio of 2.5:1. Using only tip heating, set the thermoforming oven heater to 70/60/60% output. The sheets were left in the oven for various times in order to determine the effect of sheet temperature on part quality, as shown in the table below. Part quality is determined by measuring the volume of the thermoformed part, calculating the stretch and visually inspecting the thermoformed part. Stretch was calculated by dividing the part volume by the largest part volume obtained in this set of experiments (Example A). The thermoformed parts were visually inspected for any blistering and the degree of blistering was graded as no (N), low (L) or high (H). The following results demonstrate that these thermoplastic sheets with a glass transition temperature of 117°C cannot be thermoformed under the conditions shown below, e.g. by not pre-drying the sheets prior to thermoforming to produce and as evidenced by unfoamed sheets.

实施例22-对比例Embodiment 22-comparative example

使用1.25英寸单螺杆挤出机生产由65wt％Teijin L-1250聚碳酸酯、34.85wt％PCTG 25976和0.15wt％Weston 619组成的可混共混物。然后使用3.5英寸单螺杆挤出机生产由该共混物组成的薄板。连续挤出薄板，测量厚度为118密耳，然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度，其为120℃。然后将薄板在50％相对湿度和60℃下调理4周。水分含量的测量结果为0.23wt％。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热，将热成形烘箱加热器设定为70/60/60％输出。将薄板留在烘箱中达不同的时间，以便测定薄板温度对部件质量的影响，如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的：部件体积除以在该组实验中获得的最大部件体积(实施例A)。目视检查热成形部件的任何起泡，并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明，这些玻璃化转变温度为120℃的热塑性薄板不能在以下所示的条件下热成形，如由在热成形前未预干燥薄板的情况下，不能生产出具有大于95％的拉伸和未起泡的薄板所证明的。A 1.25 inch single screw extruder was used to produce a miscible blend consisting of 65 wt% Teijin L-1250 polycarbonate, 34.85 wt% PCTG 25976 and 0.15 wt% Weston 619. Sheets consisting of this blend were then produced using a 3.5 inch single screw extruder. Sheets were continuously extruded, measuring a thickness of 118 mils, and the various sheets were then cut to size. The glass transition temperature was measured for one sheet and it was 120°C. The sheets were then conditioned for 4 weeks at 50% relative humidity and 60°C. The moisture content was measured to be 0.23 wt%. The sheets were then thermoformed using a Brown thermoformer into a female mold with a draw ratio of 2.5:1. Using only tip heating, set the thermoforming oven heater to 70/60/60% output. The sheets were left in the oven for various times in order to determine the effect of sheet temperature on part quality, as shown in the table below. Part quality is determined by measuring the volume of the thermoformed part, calculating the stretch and visually inspecting the thermoformed part. Stretch was calculated by dividing the part volume by the largest part volume obtained in this set of experiments (Example A). The thermoformed parts were visually inspected for any blistering and the degree of blistering was graded as no (N), low (L) or high (H). The following results demonstrate that these thermoplastic sheets with a glass transition temperature of 120°C cannot be thermoformed under the conditions shown below, as shown by the fact that, without pre-drying the sheets before thermoforming, it is not possible to produce and as evidenced by unfoamed sheets.

实施例23-对比例Embodiment 23-comparative example

使用1.25英寸单螺杆挤出机生产由70wt％Teijin L-1250聚碳酸酯、29.85wt％PCTG 25976和0.15wt％Weston 619组成的可混共混物。然后使用3.5英寸单螺杆挤出机生产由该共混物组成的薄板。连续挤出薄板，测量厚度为118密耳，然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度，其为123℃。然后将薄板在50％相对湿度和60℃下调理4周。水分含量的测量结果为0.205wt％。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热，将热成形烘箱加热器设定为70/60/60％输出。将薄板留在烘箱中达不同的时间，以便测定薄板温度对部件质量的影响，如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的：部件体积除以在该组实验中获得的最大部件体积(实施例A和B)。目视检查热成形部件的任何起泡，并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明，这些玻璃化转变温度为123℃的热塑性薄板不能在以下所示的条件下热成形，如由在热成形前未预干燥薄板的情况下，不能生产出具有大于95％的拉伸和未起泡的薄板所证明的。A 1.25 inch single screw extruder was used to produce a miscible blend consisting of 70 wt% Teijin L-1250 polycarbonate, 29.85 wt% PCTG 25976 and 0.15 wt% Weston 619. Sheets consisting of this blend were then produced using a 3.5 inch single screw extruder. Sheets were continuously extruded, measuring a thickness of 118 mils, and the various sheets were then cut to size. The glass transition temperature was measured for one sheet and it was 123°C. The sheets were then conditioned for 4 weeks at 50% relative humidity and 60°C. The moisture content was measured to be 0.205 wt%. The sheets were then thermoformed using a Brown thermoformer into a female mold with a draw ratio of 2.5:1. Using only tip heating, set the thermoforming oven heater to 70/60/60% output. The sheets were left in the oven for various times in order to determine the effect of sheet temperature on part quality, as shown in the table below. Part quality is determined by measuring the volume of the thermoformed part, calculating the stretch and visually inspecting the thermoformed part. Stretch was calculated by dividing the part volume by the largest part volume obtained in this set of experiments (Examples A and B). The thermoformed parts were visually inspected for any blistering and the degree of blistering was graded as no (N), low (L) or high (H). The following results demonstrate that these thermoplastic sheets with a glass transition temperature of 123°C cannot be thermoformed under the conditions shown below, e.g. by not pre-drying the sheets prior to thermoforming to produce and as evidenced by unfoamed sheets.

NA＝不适用的。0值表明未形成薄板，因为其没有拉入模具(可能因为其温度太低)。NA = not applicable. A value of 0 indicates that no sheet was formed because it was not pulled into the die (probably because it was too cold).

实施例24-对比例Embodiment 24-comparative example

使用3.5英寸单螺杆挤出机生产由Teijin L-1250聚碳酸酯组成的薄板。连续挤出薄板，测量厚度为118密耳，然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度，其为149℃。然后将薄板在50％相对湿度和60℃下调理4周。水分含量的测量结果为0.16wt％。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热，将热成形烘箱加热器设定为70/60/60％输出。将薄板留在烘箱中达不同的时间，以便测定薄板温度对部件质量的影响，如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的：部件体积除以在该组实验中获得的最大部件体积(实施例A)。目视检查热成形部件的任何起泡，并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明，这些玻璃化转变温度为149℃的热塑性薄板不能在以下所示的条件下热成形，如由在热成形前未预干燥薄板的情况下，不能生产出具有大于95％的拉伸和未起泡的薄板所证明的。Sheets consisting of Teijin L-1250 polycarbonate were produced using a 3.5-inch single-screw extruder. Sheets were continuously extruded, measuring a thickness of 118 mils, and the various sheets were then cut to size. The glass transition temperature was measured for one sheet and it was 149°C. The sheets were then conditioned for 4 weeks at 50% relative humidity and 60°C. The moisture content was measured to be 0.16 wt%. The sheets were then thermoformed using a Brown thermoformer into a female mold with a draw ratio of 2.5:1. Using only tip heating, set the thermoforming oven heater to 70/60/60% output. The sheets were left in the oven for various times in order to determine the effect of sheet temperature on part quality, as shown in the table below. Part quality is determined by measuring the volume of the thermoformed part, calculating the stretch and visually inspecting the thermoformed part. Stretch was calculated by dividing the part volume by the largest part volume obtained in this set of experiments (Example A). The thermoformed parts were visually inspected for any blistering and the degree of blistering was graded as no (N), low (L) or high (H). The following results demonstrate that these thermoplastic sheets with a glass transition temperature of 149°C cannot be thermoformed under the conditions shown below, e.g. by not pre-drying the sheets prior to thermoforming to produce and as evidenced by unfoamed sheets.

NA＝不适用的。0值表明未形成薄板，因为其没有拉入模具(可能因为其温度太低)。NA = not applicable. A value of 0 indicates that no sheet was formed because it was not pulled into the die (probably because it was too cold).

从以上相关工作实施例中的数据的比较能够清楚地看出，在玻璃化转变温度、密度、慢的结晶速率、熔体粘度和韧性方面，与市售可得的聚酯相比，本发明的聚酯提供了明显的优点。From the comparison of the data in the above related working examples, it can be clearly seen that the present invention is superior to commercially available polyesters in terms of glass transition temperature, density, slow crystallization rate, melt viscosity and toughness. Polyester offers clear advantages.

本发明已经参考本文所公开的实施方案进行了详细描述，但是应该理解，在本发明的精神和范围内可以进行变化和改变。The invention has been described in detail with reference to the embodiments disclosed herein, but it is to be understood that changes and modifications may be made within the spirit and scope of the invention.

Claims (28)

Translated fromChinese

1.一种薄膜或者薄板，其包含聚酯组合物，该聚酯组合物包含至少一种聚酯，所述聚酯包含：1. A film or sheet comprising a polyester composition comprising at least one polyester comprising:(a)二羧酸组分，其包含：(a) a dicarboxylic acid component comprising:i)70-100mol％的对苯二甲酸残基；i) 70-100 mol% of terephthalic acid residues;ii)0-30mol％的芳族二羧酸残基，其具有至多20个碳原子；和ii) 0-30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; andiii)0-10mol％的脂族二羧酸残基，其具有至多16个碳原子；和iii) 0-10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and(b)二醇组分，其包含：(b) a diol component comprising:i)10-30mol％的2，2，4，4-四甲基-1，3-环丁二醇残基；和i) 10-30 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; andii)70-90mol％的1，4-环己烷二甲醇残基，ii) 70-90 mol % of 1,4-cyclohexanedimethanol residues,其中二羧酸组分的总摩尔百分数是100mol％，和wherein the total mole percent of the dicarboxylic acid component is 100 mole percent, and二醇组分的总摩尔百分数是100mol％；The total mole percentage of diol component is 100mol%;其中比浓对数粘度是0.60-0.75dL/g，在25℃在浓度为0.5g/100ml在60/40(wt/wt)苯酚/四氯乙烷中测定；和wherein the inherent viscosity is 0.60-0.75 dL/g, measured at 25° C. at a concentration of 0.5 g/100 ml in 60/40 (wt/wt) phenol/tetrachloroethane; and其中所述聚酯的Tg为85-120℃；Wherein the Tg of the polyester is 85-120°C;其中所述聚酯根据ASTM D256，在23℃下，采用带10-密耳切口的1/8-英寸厚试条测定的切口伊佐德冲击强度为至少7.5ft-lb/in；wherein the polyester has a notched Izod impact strength of at least 7.5 ft-lb/in at 23° C. using a 1/8-inch thick test bar with a 10-mil notch according to ASTM D256;其中所述聚酯的熔体粘度小于10,000泊，在旋转熔体流变仪上在290℃以1弧度/秒测量；wherein the polyester has a melt viscosity of less than 10,000 poise as measured on a rotational melt rheometer at 290°C at 1 rad/s;其中所述聚酯组合物不含聚碳酸酯。Wherein said polyester composition does not contain polycarbonate.2.权利要求1的薄膜或者薄板，其中比浓对数粘度为0.65-0.75dL/g，或0.60-0.72dL/g。2. The film or sheet of claim 1, wherein the inherent viscosity is 0.65-0.75 dL/g, or 0.60-0.72 dL/g.3.权利要求1的薄膜或者薄板，其中该二醇组分包含15-25mol％2，2，4，4-四甲基-1，3-环丁二醇残基和75-85mol％1，4-环己烷二甲醇残基，或其中该二醇组分包含17-23mol％2，2，4，4-四甲基-1，3-环丁二醇残基和77-83mol％1，4-环己烷二甲醇残基。3. The film or sheet of claim 1, wherein the diol component comprises 15-25 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75-85 mol% 1, 4-cyclohexanedimethanol residues, or wherein the diol component comprises 17-23mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 77-83mol% 1 , 4-cyclohexanedimethanol residue.4.权利要求1的薄膜或者薄板，其中所述聚酯的Tg为90-115℃，或85-115℃，或95-115℃。4. The film or sheet of claim 1, wherein the polyester has a Tg of 90-115°C, or 85-115°C, or 95-115°C.5.权利要求1的薄膜或者薄板，其中二羧酸组分包含80-100mol％的对苯二甲酸残基。5. The film or sheet of claim 1, wherein the dicarboxylic acid component comprises 80-100 mole % of terephthalic acid residues.6.权利要求1的薄膜或者薄板，其中二羧酸组分包含90-100mol％的对苯二甲酸残基。6. The film or sheet of claim 1, wherein the dicarboxylic acid component comprises 90-100 mole % of terephthalic acid residues.7.权利要求1的薄膜或者薄板，其中二羧酸组分包含95-100mol％的对苯二甲酸残基。7. The film or sheet of claim 1, wherein the dicarboxylic acid component comprises 95-100 mole % of terephthalic acid residues.8.权利要求6的薄膜或者薄板，其中二羧酸组分包含99-100mol％的对苯二甲酸残基。8. The film or sheet of claim 6, wherein the dicarboxylic acid component comprises 99-100 mole % of terephthalic acid residues.9.权利要求1的薄膜或者薄板，其中所述聚酯包含1，3-丙二醇残基、1，4-丁二醇残基或其混合物。9. The film or sheet of claim 1, wherein the polyester comprises residues of 1,3-propanediol, residues of 1,4-butanediol, or mixtures thereof.10.权利要求8的薄膜或者薄板，其中所述聚酯包含0.01-10mol％的1，3-丙二醇残基、1，4-丁二醇残基或其混合物。10. The film or sheet of claim 8, wherein the polyester comprises 0.01 to 10 mole % of residues of 1,3-propanediol, residues of 1,4-butanediol, or mixtures thereof.11.权利要求1的薄膜或者薄板，其中所述聚酯包含乙二醇残基，或其中所述聚酯包含0.01-15mol％的乙二醇残基，或0.01-10mol％的乙二醇残基。11. The film or sheet of claim 1, wherein said polyester comprises ethylene glycol residues, or wherein said polyester comprises 0.01-15 mol% ethylene glycol residues, or 0.01-10 mol% ethylene glycol residues base.12.权利要求1的薄膜或者薄板，其中所述2，2，4，4-四甲基-1，3-环丁二醇残基是包含大于50mol％的顺-2，2，4，4-四甲基-1，3-环丁二醇残基和小于50mol％的反-2，2，4，4-四甲基-1，3-环丁二醇残基的混合物。12. The film or sheet of claim 1, wherein said 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues are cis-2,2,4,4 - a mixture of tetramethyl-1,3-cyclobutanediol residues and less than 50 mol % of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.13.权利要求1的薄膜或者薄板，其中所述2，2，4，4-四甲基-1，3-环丁二醇残基是包含30-70mol％的顺-2，2，4，4-四甲基-1，3-环丁二醇残基和70-30mol％的反-2，2，4，4-四甲基-1，3-环丁二醇残基的混合物。13. The film or sheet of claim 1, wherein said 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues are cis-2,2,4, A mixture of 4-tetramethyl-1,3-cyclobutanediol residues and 70-30 mol % of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.14.权利要求13的薄膜或者薄板，其中所述2，2，4，4-四甲基-1，3-环丁二醇残基是包含40-60mol％的顺-2，2，4，4-四甲基-1，3-环丁二醇残基和60-40mol％的反-2，2，4，4-四甲基-1，3-环丁二醇残基的混合物。14. The film or sheet of claim 13, wherein said 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues are cis-2,2,4, A mixture of 4-tetramethyl-1,3-cyclobutanediol residues and 60-40 mol % of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.15.权利要求1的薄膜或者薄板，其中所述聚酯组合物包含至少一种选自以下中的至少一种的聚合物：聚(醚酰亚胺)、聚苯醚、聚苯醚/聚苯乙烯共混物、聚苯乙烯树脂、聚苯硫醚、聚苯硫醚/砜、聚砜；聚砜醚、和聚(醚-酮)。15. The film or sheet of claim 1, wherein said polyester composition comprises at least one polymer selected from at least one of the following: poly(etherimide), polyphenylene ether, polyphenylene ether/poly Styrenic blends, polystyrene resins, polyphenylene sulfide, polyphenylene sulfide/sulfone, polysulfone; polysulfone ethers, and poly(ether-ketones).16.权利要求1的薄膜或者薄板，其中所述聚酯包含至少一种支化剂的残基。16. The film or sheet of claim 1, wherein said polyester comprises the residue of at least one branching agent.17.权利要求16的薄膜或者薄板，其中所述聚酯包含至少一种支化剂的残基，其数量为：0.01-10wt％，基于二酸或二醇残基的总摩尔百分数。17. The film or sheet of claim 16, wherein said polyester comprises residues of at least one branching agent in an amount of: 0.01-10 wt%, based on the total mole percent of diacid or diol residues.18.权利要求1的薄膜或者薄板，其中所述聚酯的熔体粘度小于6,000泊，在290℃在旋转熔体流变仪上以1弧度/秒测量。18. The film or sheet of claim 1, wherein the polyester has a melt viscosity of less than 6,000 poise, measured at 290°C on a rotational melt rheometer at 1 rad/sec.19.权利要求1的薄膜或者薄板，其中所述聚酯具有在170℃大于5分钟的结晶半衰期，或其中所述聚酯具有在170℃大于50分钟的结晶半衰期。19. The film or sheet of claim 1, wherein said polyester has a crystallization half-life at 170°C of greater than 5 minutes, or wherein said polyester has a crystallization half-life of greater than 50 minutes at 170°C.20.权利要求1的薄膜或者薄板，其中在23℃所述聚酯组合物的密度为小于1.2g/ml。20. The film or sheet of claim 1, wherein said polyester composition has a density of less than 1.2 g/ml at 23°C.21.权利要求1的薄膜或者薄板，其中所述聚酯组合物包含至少一种热稳定剂或其反应产物。21. The film or sheet of claim 1, wherein said polyester composition comprises at least one thermal stabilizer or a reaction product thereof.22.权利要求1的薄膜或者薄板，其中根据ASTM D-1925测定，所述聚酯的黄度指数小于50。22. The film or sheet of claim 1 , wherein the polyester has a yellowness index of less than 50 as determined according to ASTM D-1925.23.权利要求1的薄膜或者薄板，根据ASTM D256，在23℃下，采用带10-密耳切口的1/8-in厚试条测试，所述聚酯的切口伊佐德冲击强度为至少10ft-lbs/in。23. The film or sheet of claim 1 , said polyester having a notched Izod impact strength of at least 10 ft according to ASTM D256 at 23° C. using a 1/8-in thick test bar with a 10-mil notch -lbs/in.24.权利要求1的薄膜或者薄板，其中聚酯包含至少一种催化剂的残余物，所述催化剂包含锡化合物或其反应产物。24. The film or sheet of claim 1, wherein the polyester comprises the residue of at least one catalyst comprising a tin compound or a reaction product thereof.25.一种制品，其包含权利要求1的薄膜或者薄板。25. An article comprising the film or sheet of claim 1.26.权利要求25的制品，其中根据ASTM D256，在23℃下，采用带10-密耳切口的1/4-in厚试条测试，聚酯的切口伊佐德冲击强度为至少10ft-lbs/in。26. The article of claim 25, wherein the polyester has a notched Izod impact strength of at least 10 ft-lbs/ in.27.一种液晶显示器薄膜，其包含权利要求1的薄膜或者薄板。27. A liquid crystal display film comprising the film or sheet of claim 1.28.权利要求27的液晶显示器薄膜，其中液晶显示器薄膜是漫射体薄板，或其中液晶显示器薄膜是补偿薄膜。28. The liquid crystal display film of claim 27, wherein the liquid crystal display film is a diffuser sheet, or wherein the liquid crystal display film is a compensation film.

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