技术领域technical field
本发明涉及包括聚丙烯树脂的管道；优选地，包括间同立构聚丙烯树脂的管道。The present invention relates to pipes comprising polypropylene resin; preferably, pipes comprising syndiotactic polypropylene resin.
背景技术Background technique
聚合物材料常被用于制造适合于各种目的(例如，期间流体可被加压并且可具有变化的温度(最高达70℃)的流体输送，即，液体或者气体例如水或天然气的输送)的管道。这些管道通常由聚烯烃例如聚乙烯和聚丙烯制备。由于所涉及的高温，由聚烯烃制成的管道具有特殊要求。Polymer materials are often used to manufacture fluids suitable for various purposes (e.g. fluid transport during which fluids may be pressurized and may have varying temperatures (up to 70°C), i.e. transport of liquids or gases such as water or natural gas) pipeline. These pipes are usually prepared from polyolefins such as polyethylene and polypropylene. Pipes made from polyolefins have special requirements due to the high temperatures involved.
聚丙烯与其它聚烯烃相比的良好耐热性对于例如管道和压力管道的应用是特别有用的。压力管道树脂需要与高的抗慢速裂纹增长性以及抗快速裂纹扩展性(冲击韧性)组合的高的刚度(stiffness)(蠕变破裂强度)。所有三种主要类型的聚丙烯即均聚物、无规共聚物和嵌段共聚物均已经被用于制造管道。The good heat resistance of polypropylene compared to other polyolefins is particularly useful for applications such as pipes and pressure piping. Pressure piping resins require high stiffness (creep rupture strength) combined with high slow crack growth resistance and fast crack growth resistance (impact toughness). All three main types of polypropylene, homopolymers, random copolymers and block copolymers, have been used to make pipes.
根据标准DIN 8078，由聚丙烯制成的管道必须满足在95℃和3.5MPa压力下破坏之前至少1000小时的要求。满足这些要求的一种尝试一直都是提高用于这样的压力管道的聚烯烃组合物的刚性(rigidity)。然而，提高刚性有时导致抗慢速裂纹增长性(SCGR)的降低，从而导致较早的脆性破坏并且因此也对最小要求强度(MRS)等级有负面影响。这样，压力管道也柔性越来越低。期望改善或者保持为高水平的其它性质为管道材料的加工性、拉伸模量、短期和长期压力耐受性、和冲击性质。According to standard DIN 8078, pipes made of polypropylene must meet the requirements of at least 1000 hours before failure at 95°C and a pressure of 3.5MPa. One attempt to meet these requirements has been to increase the rigidity of polyolefin compositions used in such pressure pipes. However, increasing stiffness sometimes leads to a reduction in slow crack growth resistance (SCGR), leading to earlier brittle failure and thus also negatively affects the minimum required strength (MRS) rating. In this way, the pressure pipe is also less and less flexible. Other properties that are expected to be improved or maintained at high levels are processability, tensile modulus, short and long term pressure resistance, and impact properties of the piping material.
因此，仍然需要制造如下的“尽可能柔性的”聚丙烯管道：其能够长期经受高的压力，同时满足现有标准的加工性、抗慢速裂纹增长性和冲击韧性的标准。本发明潜藏的目的是提供如下的柔性管道：其能够长期经受高的压力，同时满足现有标准的加工性、抗慢速裂纹增长性和冲击韧性的标准。Therefore, there is still a need to produce "as flexible as possible" polypropylene pipes which are able to withstand high pressures for long periods of time while meeting the existing standard criteria of processability, slow crack growth resistance and impact toughness. The underlying object of the present invention is to provide a flexible pipe capable of withstanding high pressures for long periods of time while meeting existing standards of processability, slow crack growth resistance and impact toughness.
发明内容Contents of the invention
本发明人现已惊讶地发现，以上目的的一个或多个可通过使用间同立构聚丙烯来制造管道而实现。The inventors have now surprisingly found that one or more of the above objects can be achieved by using syndiotactic polypropylene for the manufacture of pipes.
根据第一方面,本发明提供管道，其包括组合物，其中所述组合物包括间同立构聚丙烯，其中所述间同立构聚丙烯具有如经由13C-NMR光谱法测量的至少70％的间同立构指数；和其中所述间同立构聚丙烯未呈现高于145℃的熔融温度峰，如通过差示扫描量热法测定的。13C-NMR分析如下文中在具体实施方式中所描述的那样进行。本发明人已经表明，所要求保护的管道在比现有技术管道柔性的同时，能够长期经受高的应力，并且同时，满足加工、抗慢速裂纹增长性和抗冲击性的现有标准。According to a first aspect, the present invention provides a pipe comprising a composition, wherein said composition comprises syndiotactic polypropylene, wherein said syndiotactic polypropylene has at least 70 as measured via13 C-NMR spectroscopy. % syndiotactic index; and wherein the syndiotactic polypropylene does not exhibit a melting temperature peak above 145°C, as determined by differential scanning calorimetry.13 C-NMR analysis was performed as described below in the detailed description. The inventors have shown that the claimed pipe, while being more flexible than prior art pipes, is capable of withstanding high stresses over long periods of time and, at the same time, meets existing standards for processing, resistance to slow crack growth and impact resistance.
优选地，本发明提供管道，其包括组合物，所述组合物包括至少一种间同立构聚丙烯，其中所述组合物包括基于所述组合物的总重量的至少80％重量的所述至少一种间同立构聚丙烯；其中所述至少一种间同立构聚丙烯具有如使用13C-NMR光谱法测量的至少70％的间同立构指数；和其中所述间同立构聚丙烯未呈现高于145℃的熔融温度峰，如通过差示扫描量热法测定的。Preferably, the present invention provides pipes comprising a composition comprising at least one syndiotactic polypropylene, wherein said composition comprises at least 80% by weight based on the total weight of said composition of said at least one syndiotactic polypropylene; wherein said at least one syndiotactic polypropylene has a syndiotactic index of at least 70% as measured using13 C-NMR spectroscopy; and wherein said syndiotactic Structural polypropylene does not exhibit a melting temperature peak above 145°C, as determined by differential scanning calorimetry.
根据第二方面，本发明还涵盖用于制造根据第一方面的管道的工艺，其包括如下步骤：According to a second aspect, the present invention also covers a process for manufacturing a pipe according to the first aspect, comprising the steps of:
(a)将所述间同立构聚丙烯树脂挤出为管道；(a) extruding the syndiotactic polypropylene resin into a pipe;
(b)将步骤(a)中形成的管道冷却；和(b) cooling the tube formed in step (a); and
(c)任选地将步骤(a)中形成的管道加热/退火。(c) optionally heating/annealing the tube formed in step (a).
优选地，本发明还涵盖用于制造根据第一方面的管道的工艺，其包括如下步骤：Preferably, the present invention also covers a process for manufacturing a pipe according to the first aspect, comprising the steps of:
(a)将组合物挤出为管道；所述组合物包括基于所述组合物的总重量的至少50％重量的至少一种间同立构聚丙烯；其中所述至少一种间同立构聚丙烯具有如使用13C-NMR光谱法测量的至少70％的间同立构指数；和其中所述间同立构聚丙烯未呈现高于145℃的熔融温度峰，如通过差示扫描量热法测定的；(a) extruding the composition into a pipe; said composition comprising at least 50% by weight of at least one syndiotactic polypropylene based on the total weight of said composition; wherein said at least one syndiotactic The polypropylene has a syndiotactic index of at least 70% as measured using13 C-NMR spectroscopy; and wherein the syndiotactic polypropylene does not exhibit a melting temperature peak above 145°C, as measured by differential scanning determined by thermal method;
(b)将步骤(a)中形成的管道冷却；和(b) cooling the tube formed in step (a); and
(c)任选地将步骤(a)中形成的管道加热/退火。(c) optionally heating/annealing the tube formed in step (a).
根据第三方面,本发明提供根据第一方面的和/或根据第二方面制造的管道用于输送处于压力下的流体的用途。According to a third aspect, the invention provides the use of a pipe according to the first aspect and/or manufactured according to the second aspect for conveying a fluid under pressure.
本发明还涵盖根据第一方面的和/或根据第二方面制造的管道用于制造医用制品的用途。The invention also covers the use of the tubing according to the first aspect and/or manufactured according to the second aspect for the manufacture of a medical article.
现在将进一步描述本发明。在以下段落中，更详细地定义本发明的不同方面。如此定义的各方面可与任何其它一个或多个方面组合，除非清楚地相反指示。特别地，被示为优选或者有利的任何特征可与被示为优选或有利的任何其它一个特征或多个特征组合。The present invention will now be further described. In the following passages, different aspects of the invention are defined in more detail. An aspect so defined may be combined with any other aspect or aspects, unless clearly indicated to the contrary. In particular, any feature shown as preferred or advantageous may be combined with any other feature or features shown as preferred or advantageous.
附图说明Description of drawings
图1为用于进行蠕变实验的水浴的照片。Figure 1 is a photograph of the water bath used to perform the creep experiments.
图2表示绘制由根据本发明一种实施方式的间同立构聚丙烯制成的拉伸样条的作为时间的函数的％伸长率的图。Figure 2 represents a graph plotting % elongation as a function of time for tensile splines made from syndiotactic polypropylene according to one embodiment of the present invention.
图3表示绘制由根据本发明一种实施方式的间同立构聚丙烯树脂制成的拉伸样条的作为所施加应力的函数的在拐点处的％伸长率的图。Figure 3 represents a graph plotting the % elongation at the point of inflection as a function of applied stress for a tensile spline made of a syndiotactic polypropylene resin according to one embodiment of the present invention.
图4表示绘制由与对比例相比的根据本发明一种实施方式的间同立构聚丙烯树脂制成的拉伸样条的作为拐点时间的函数的所施加应力的图。Figure 4 represents a graph plotting the applied stress as a function of the time at the inflection point for a tensile spline made of a syndiotactic polypropylene resin according to an embodiment of the present invention compared to a comparative example.
图5表示根据本发明一种实施方式的包括间同立构聚丙烯的管道的制造的照片。Figure 5 shows a photograph of the manufacture of a pipe comprising syndiotactic polypropylene according to one embodiment of the invention.
图6表示显示根据本发明一种实施方式的包括间同立构聚丙烯的管道的外表面(外)的DSC廓线和内表面(内)的DSC廓线的图。Figure 6 represents a graph showing the DSC profile of the outer surface (External) and the DSC profile of the inner surface (Inner) of a pipe comprising syndiotactic polypropylene according to one embodiment of the present invention.
图7表示显示在将根据本发明一种实施方式的包括间同立构聚丙烯树脂的管道在80℃下加热/退火之后的不同时间处所述管道的内表面的DSC廓线的图。Fig. 7 represents graphs showing DSC profiles of the inner surface of a pipe including a syndiotactic polypropylene resin according to an embodiment of the present invention at different times after heating/annealing the pipe at 80°C.
图8表示显示在将根据本发明一种实施方式的包括间同立构聚丙烯树脂的管道在80℃下加热/退火之后的不同时间处所述管道的外表面的DSC廓线的图。Fig. 8 represents graphs showing DSC profiles of the outer surface of a pipe comprising a syndiotactic polypropylene resin according to an embodiment of the present invention at different times after heating/annealing the pipe at 80°C.
图9表示显示根据本发明一种实施方式的在160℃下挤出并且在80℃下持续退火14天的包括间同立构聚丙烯树脂的管道的DSC廓线的图。Figure 9 represents a graph showing the DSC profile of a pipe comprising a syndiotactic polypropylene resin extruded at 160°C and continuously annealed at 80°C for 14 days according to one embodiment of the present invention.
图10表示显示根据本发明一种实施方式的在170℃下挤出并且在80℃下持续退火14天的包括间同立构聚丙烯树脂的管道的DSC廓线的图。Figure 10 represents a graph showing the DSC profile of a pipe comprising a syndiotactic polypropylene resin extruded at 170°C and continuously annealed at 80°C for 14 days according to one embodiment of the present invention.
图11表示显示根据本发明一种实施方式的在220℃下挤出并且在80℃下持续退火14天的包括间同立构聚丙烯树脂的管道的DSC廓线的图。Figure 11 represents a graph showing the DSC profile of a pipe comprising a syndiotactic polypropylene resin extruded at 220°C and annealed at 80°C for 14 days according to one embodiment of the present invention.
图12表示绘制与对比例相比的根据本发明一种实施方式的由间同立构聚丙烯制成的32mm直径管道在20℃的温度下的作为所施加的环向应力的函数的破坏时间的图。Figure 12 represents plotting the failure time as a function of the applied hoop stress at a temperature of 20° C. for a 32 mm diameter pipe made of syndiotactic polypropylene according to one embodiment of the present invention compared to a comparative example diagram.
具体实施方式Detailed ways
在描述本发明的本管道、组合物、工艺、制品、和用途之前，应理解，本发明不限于所描述的具体的管道、组合物、工艺、制品、和用途，因为这样的管道、组合物、工艺、制品、和用途当然可变化。还应理解，本文中使用的术语不意图为限制性的，因为本发明的范围将仅由所附权利要求限制。Before the present conduits, compositions, processes, articles, and uses of the present invention are described, it is to be understood that the invention is not limited to the particular conduits, compositions, processes, articles, and uses described, since such conduits, compositions , process, manufacture, and use may of course vary. It is also to be understood that the terms used herein are not intended to be limiting, since the scope of the invention will be limited only by the appended claims.
在描述本发明的管道和工艺时，所使用的术语应根据以下定义解释，除非上下文另有规定。In describing the piping and process of the present invention, the terms used are to be construed in accordance with the following definitions unless the context dictates otherwise.
如本文中使用的，单数形式“一个(种)(a、an)”、和“该(所述)”包含单数个和复数个指示物两者，除非上下文清楚地另有规定。As used herein, the singular forms "a, an", and "the" include both singular and plural referents unless the context clearly dictates otherwise.
如本文中使用的术语“包括”和“由...构组成(comprised of)”是与“包含”或者“含(有)”同义的，并且是包容性的或者开放式的并且不排除另外的、未列举的成员、要素或者方法步骤。术语“包括”和“由...构组成”也包含术语“由…构成(consisting of)”。As used herein, the terms "comprises" and "comprised of" are synonymous with "comprises" or "comprises" and are inclusive or open-ended and do not exclude Additional, unrecited members, elements or method steps. The terms "comprising" and "consisting of" also include the term "consisting of".
通过端点进行的数值范围的陈述包含所有的囊括在各自范围内的数和部分、以及所陈述的端点。The recitations of numerical ranges by endpoints include all subsumed numbers and moieties within the respective ranges, as well as the recited endpoints.
在本说明书中提及“一个实施方式”或“一种实施方式”意味着，关于该实施方式描述的具体特征、结构或特性被包含在本发明的至少一个实施方式中。因此，在本说明书中的不同位置中出现短语“在一个实施方式中”或者“在一种实施方式中”不一定均是指相同的实施方式，但是可以指相同的实施方式。此外，在一个或多个实施方式中，可将所述具体的特征、结构或特性以如本领域技术人员由本公开内容将明晰的任何合适的方式组合。此外，如本领域技术人员将理解的，虽然本文中描述的一些实施方式包含其它实施方式中包含的一些特征但是不包含所述其它实施方式中包含的其它特征，但是不同实施方式的特征的组合意图在本发明的范围内，并且形成不同的实施方式。例如，在所附权利要求中，任何所要求保护的实施方式可以任意组合使用。Reference in this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described with respect to the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases "in one embodiment" or "in one embodiment" in various places in this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner as would be apparent to one of skill in the art from this disclosure in one or more embodiments. Furthermore, although some embodiments described herein include some features included in other embodiments but not other features included in the other embodiments, combinations of features from different Different embodiments are intended to be within the scope of the invention and to form. For example, in the appended claims, any of the claimed embodiments may be used in any combination.
除非另有定义，否则在公开本发明时使用的所有术语，包含技术和科学术语，具有如本发明所属领域的普通技术人员通常理解的含义。作为进一步的指引，针对本说明书中使用的术语的定义是为了更好地领会本发明的教导而包含的。Unless otherwise defined, all terms used in disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. As a further guide, definitions for terms used in this specification are included for a better understanding of the teachings of the present invention.
下文中阐述本发明的管道、组合物、工艺、制品、和用途的优选陈述(特征)和实施方式。如此定义的本发明的各陈述和实施方式可与任何其它陈述和/或实施方式组合，除非清楚地相反指示。特别地，被示为优选或者有利的任何特征可与被示为优选或有利的任何其它特征或陈述组合。关于此，本发明特别地是通过以下编号的方面和实施方式1-34的任一个或者其一个或多个与任何其它陈述和/或实施方式的任意组合而赢得的。Preferred statements (features) and embodiments of the conduits, compositions, processes, articles, and uses of the invention are set forth below. Each statement and embodiment of the invention thus defined may be combined with any other statement and/or embodiment unless clearly indicated to the contrary. In particular, any feature which is stated as preferred or advantageous may be combined with any other feature or statement which is stated as preferred or advantageous. In this regard, the invention is notably achieved by any one or any combination of one or more of the following numbered aspects and embodiments 1-34 with any other statement and/or embodiment.
1.管道，其包括组合物，所述组合物包括至少一种间同立构聚丙烯，其中所述至少一种间同立构聚丙烯具有如使用13C-NMR光谱法测量的至少70％的间同立构指数；和其中所述间同立构聚丙烯未呈现高于145℃的熔融温度峰，如通过差示扫描量热法测定的。1. A pipe comprising a composition comprising at least one syndiotactic polypropylene, wherein said at least one syndiotactic polypropylene has at least 70% as measured using13 C-NMR spectroscopy and wherein the syndiotactic polypropylene does not exhibit a melting temperature peak above 145°C, as determined by differential scanning calorimetry.
2.管道，其包括组合物，所述组合物包括基于所述组合物的总重量的至少50％重量的至少一种间同立构聚丙烯；其中所述至少一种间同立构聚丙烯具有如使用13C-NMR光谱法测量的至少70％的间同立构指数；和其中所述间同立构聚丙烯未呈现高于145℃的熔融温度峰，如通过差示扫描量热法测定的。2. A pipe comprising a composition comprising at least 50% by weight of at least one syndiotactic polypropylene based on the total weight of the composition; wherein the at least one syndiotactic polypropylene having a syndiotactic index of at least 70% as measuredusing13C -NMR spectroscopy; and wherein the syndiotactic polypropylene does not exhibit a melting temperature peak above 145°C, as by differential scanning calorimetry Measured.
3.管道，其包括至少一种间同立构聚丙烯，其中所述至少一种间同立构聚丙烯具有如使用13C-NMR光谱法测量的至少70％的间同立构指数；和其中所述间同立构聚丙烯未呈现高于145℃的熔融温度峰，如通过差示扫描量热法测定的。3. Pipe comprising at least one syndiotactic polypropylene, wherein said at least one syndiotactic polypropylene has a syndiotactic index of at least 70% as measured using13 C-NMR spectroscopy; and wherein the syndiotactic polypropylene does not exhibit a melting temperature peak above 145°C, as determined by differential scanning calorimetry.
4.管道，其包括至少一种间同立构聚丙烯，其中所述至少一种间同立构聚丙烯具有如使用13C-NMR光谱法测量的至少70％的间同立构指数；其中所述管道包括基于所述管道的总重量的至少50％重量的所述至少一种间同立构聚丙烯和其中所述间同立构聚丙烯未呈现高于145℃的熔融温度峰，如通过差示扫描量热法测定的。4. Pipe comprising at least one syndiotactic polypropylene, wherein said at least one syndiotactic polypropylene has a syndiotactic index of at least 70% as measured using13 C-NMR spectroscopy; wherein Said pipe comprises at least 50% by weight of said at least one syndiotactic polypropylene, based on the total weight of said pipe, and wherein said syndiotactic polypropylene does not exhibit a melting temperature peak above 145°C, such as Determined by differential scanning calorimetry.
5.根据陈述1-4任一项的管道，其中所述间同立构聚丙烯未呈现高于140℃的熔融温度峰、优选地未呈现高于136℃的熔融温度峰。5. Pipe according to any one of statements 1-4, wherein the syndiotactic polypropylene does not exhibit a melting temperature peak above 140°C, preferably does not exhibit a melting temperature peak above 136°C.
6.根据陈述1-5任一项的管道，其中所述管道未呈现高于145℃的熔融温度峰，如通过差示扫描量热法测定的。6. The pipe according to any one of statements 1-5, wherein the pipe does not exhibit a melting temperature peak above 145°C, as determined by differential scanning calorimetry.
7.根据陈述1-6任一项的管道，其中通过差示扫描量热法测量的所述间同立构聚丙烯的最大熔融温度为至多145℃、优选地至多140℃。7. Pipe according to any one of statements 1-6, wherein the syndiotactic polypropylene has a maximum melting temperature measured by differential scanning calorimetry of at most 145°C, preferably at most 140°C.
8.根据陈述1-7任一项的管道，其具有如通过ISO 178测定的小于1000MPa、优选地小于700MPa、优选地小于500MPa的挠曲模量。8. Pipe according to any one of statements 1-7, having a flexural modulus as determined by ISO 178 of less than 1000 MPa, preferably less than 700 MPa, preferably less than 500 MPa.
9.根据陈述1-8任一项的管道，所述管道具有外推的50℃/50年至少7.0MPa的应力。9. The pipe according to any one of statements 1-8, which has an extrapolated 50°C/50 years stress of at least 7.0 MPa.
10.根据陈述1-9任一项的管道，其中所述组合物包括基于所述组合物的总重量的至少60％重量、优选地至少70％重量、优选地至少80％重量、优选地至少90％重量、优选地至少95％重量、还更优选地至少97％重量、还甚至更优选地至少98％重量的所述至少一种间同立构聚丙烯。10. The pipe according to any one of statements 1-9, wherein the composition comprises at least 60% by weight, preferably at least 70% by weight, preferably at least 80% by weight, preferably at least 90% by weight, preferably at least 95% by weight, still more preferably at least 97% by weight, still even more preferably at least 98% by weight of said at least one syndiotactic polypropylene.
11.根据陈述1-10任一项的管道，其中所述管道包括基于所述管道的总重量的至少60％重量、优选地至少70％重量、优选地至少80％重量、优选地至少90％重量、优选地至少95％重量的所述至少一种间同立构聚丙烯。11. Pipe according to any one of statements 1-10, wherein said pipe comprises at least 60% by weight, preferably at least 70% by weight, preferably at least 80% by weight, preferably at least 90% by weight, based on the total weight of said pipe % by weight, preferably at least 95% by weight, of said at least one syndiotactic polypropylene.
12.根据陈述1-11任一项的管道，其中所述管道由包括所述至少一种间同立构聚丙烯的组合物制成，优选地其中所述组合物包括基于所述组合物的总重量的至少80％重量、优选地至少90％重量、优选地至少95％重量的所述至少一种间同立构聚丙烯。12. Pipe according to any one of statements 1-11, wherein said pipe is made of a composition comprising said at least one syndiotactic polypropylene, preferably wherein said composition comprises At least 80% by weight of the total weight, preferably at least 90% by weight, preferably at least 95% by weight of said at least one syndiotactic polypropylene.
13.根据陈述1-12任一项的管道，其中所述至少一种间同立构聚丙烯具有如使用13C-NMR光谱法测定的至少73％、更优选地至少75％、优选地至多90％、优选地至多85％、最优选地至多80％的间同立构指数。13. Pipe according to any one of statements 1-12, wherein said at least one syndiotactic polypropylene has at least73 %, more preferably at least 75%, preferably at most A syndiotactic index of 90%, preferably at most 85%, most preferably at most 80%.
14.根据陈述1-13任一项的管道，其中所述至少一种间同立构聚丙烯具有如使用13C-NMR光谱法测定的至多90％的间同立构指数。14. The pipe according to any one of statements 1-13, wherein said at least one syndiotactic polypropylene has a syndiotactic index of at most 90% as determined using13C-NMR spectroscopy.
15.根据陈述1-14任一项的管道，其中所述至少一种间同立构聚丙烯具有如使用13C-NMR光谱法测定的约74％-90％的间同立构指数。15. The pipe according to any one of statements 1-14, wherein said at least one syndiotactic polypropylene has a syndiotactic index of about 74%-90% as determinedusing13C -NMR spectroscopy.
16.根据陈述1-15任一项的管道，其中所述至少一种间同立构聚丙烯具有如根据ASTM D-1505在23℃下测定的至多0.900g/cm3、例如至少0.800g/cm3且至多0.900g/cm3、优选地至少0.820g/cm3且至多0.900g/cm3、优选地至少0.840g/cm3且至多0.9000g/cm3、优选地至少0.8605g/cm3且至多0.900g/cm3、优选地至少0.870g/cm3且至多0.900g/cm3的密度。16. Pipe according to any one of statements 1-15, wherein said at least one syndiotactic polypropylene has at most 0.900 g/cm3 , such as at least 0.800 g/cm 3 , as determined according to ASTM D-1505 at 23° C. cm3 and at most 0.900 g/cm3 , preferably at least 0.820 g/cm3 and at most 0.900 g/cm3 , preferably at least 0.840 g/cm3 and at most 0.9000 g/cm3 , preferably at least 0.8605 g/cm3 And a density of at most 0.900 g/cm3 , preferably at least 0.870 g/cm3 and at most 0.900 g/cm3 .
17.根据陈述1-16任一项的管道，其中所述至少一种间同立构聚丙烯具有如根据ASTM D-1238条件L、在230℃下在2.16kg的负荷下测定的至少0.3g/10min、优选地至少0.5g/10min、优选地至少1.0g/10min、优选地至少1.5g/10min、优选地至少1.8g/10min的熔体流动速率。17. Pipe according to any one of statements 1-16, wherein said at least one syndiotactic polypropylene has at least 0.3 g as determined according to ASTM D-1238 condition L at 230°C under a load of 2.16 kg /10min, preferably at least 0.5g/10min, preferably at least 1.0g/10min, preferably at least 1.5g/10min, preferably at least 1.8g/10min melt flow rate.
18.根据陈述1-17任一项的管道，其中所述至少一种间同立构聚丙烯具有如根据ASTM D-1238条件L、在230℃下在2.16kg的负荷下测定的至多25.0g/10min、优选地至多20.0g/10min、优选地至多15.0g/10min、优选地至多10.0g/10min的熔体流动速率；优选地，所述至少一种间同立构聚丙烯树脂具有至少0.3g/10min且至多25.0g/10min的熔体流动速率；优选地至少0.5g/10min且至多20.0g/10min的熔体流动速率；优选地至少1.0g/10min且至多15.0g/10min的熔体流动速率；优选地至少1.0g/10min且至多10.0g/10min的熔体流动速率；最优选地至少1.8g/10min且至多10.0g/10min、优选地至少1.8g/10min且至多9.0g/10min的熔体流动速率；优选地至少1.9g/10min且至多8.0g/10min的熔体流动速率；优选地至少1.8g/10min且至多7.0g/10min的熔体流动速率；优选地至少1.8且至多6.0g/10min的MFR；优选地至少1.8g/10min且至多5.0g/10min的熔体流动速率；更优选地至少1.8g/10min且至多4.0g/10min的熔体流动速率；最优选地至少1.8g/10min且至多3.0g/10min的熔体流动速率。18. Pipe according to any one of statements 1-17, wherein said at least one syndiotactic polypropylene has at most 25.0 g as determined according to ASTM D-1238 condition L at 230°C under a load of 2.16 kg /10min, preferably at most 20.0g/10min, preferably at most 15.0g/10min, preferably at most 10.0g/10min melt flow rate; preferably, said at least one syndiotactic polypropylene resin has a melt flow rate of at least 0.3 Melt flow rate of g/10min and at most 25.0 g/10min; preferably at least 0.5 g/10min and at most 20.0 g/10min of melt flow rate; preferably at least 1.0 g/10min and at most 15.0 g/10min of melt Flow rate; preferably a melt flow rate of at least 1.0 g/10min and at most 10.0 g/10min; most preferably at least 1.8 g/10min and at most 10.0 g/10min, preferably at least 1.8 g/10min and at most 9.0 g/10min Preferably at least 1.9 g/10min and at most 8.0 g/10min of melt flow rate; preferably at least 1.8 g/10min and at most 7.0 g/10min of melt flow rate; preferably at least 1.8 and at most MFR of 6.0 g/10min; preferably a melt flow rate of at least 1.8 g/10min and at most 5.0 g/10min; more preferably a melt flow rate of at least 1.8 g/10min and at most 4.0 g/10min; most preferably at least Melt flow rate of 1.8 g/10 min and up to 3.0 g/10 min.
19.根据陈述1-18任一项的管道，其中所述至少一种间同立构聚丙烯为具有小于0.7％重量的乙烯或其它α-烯烃共聚单体(优选乙烯)、优选地小于0.5％重量的乙烯、优选地小于0.4％重量的乙烯、优选地小于0.1％重量的乙烯的间同立构聚丙烯均聚物。19. Pipe according to any one of statements 1-18, wherein said at least one syndiotactic polypropylene is having less than 0.7% by weight of ethylene or other alpha-olefin comonomers (preferably ethylene), preferably less than 0.5 % by weight ethylene, preferably less than 0.4% by weight ethylene, preferably less than 0.1% by weight ethylene, a syndiotactic polypropylene homopolymer.
20.根据陈述1-19任一项的管道，其中所述至少一种间同立构聚丙烯为纯的间同立构聚丙烯均聚物。20. The pipe according to any one of statements 1-19, wherein said at least one syndiotactic polypropylene is a pure syndiotactic polypropylene homopolymer.
21.根据陈述1-20任一项的管道，其中所述至少一种间同立构聚丙烯为由单中心催化剂催化的间同立构聚丙烯、优选地由茂金属催化的间同立构聚丙烯。21. Pipe according to any one of statements 1-20, wherein said at least one syndiotactic polypropylene is a syndiotactic polypropylene catalyzed by a single site catalyst, preferably a syndiotactic polypropylene catalyzed by a metallocene polypropylene.
22.根据陈述1-21任一项的管道，其具有如通过ISO 178测定的小于1000MPa的挠曲模量。22. The pipe according to any one of statements 1-21, having a flexural modulus as determined by ISO 178 of less than 1000 MPa.
23.根据陈述1-22任一项的管道，其具有如通过在23℃下的ISO 180-缺口悬臂梁试验测定的至少40kJ/m2的抗冲击性。23. The pipe according to any one of statements 1-22, which has an impact resistance of at least 40 kJ/m2 as determined by the ISO 180-notched Izod test at 23°C.
24.用于制造根据陈述1-23任一项的管道的工艺，其包括如下步骤：24. A process for manufacturing a pipe according to any one of statements 1-23, comprising the steps of:
(a)将组合物挤出为管道；所述组合物包括基于所述组合物的总重量的至少50％重量的至少一种间同立构聚丙烯；其中所述至少一种间同立构聚丙烯具有如使用13C-NMR光谱法测量的至少70％的间同立构指数；和其中所述间同立构聚丙烯未呈现高于145℃的熔融温度峰，如通过差示扫描量热法测定的；(a) extruding the composition into a pipe; said composition comprising at least 50% by weight of at least one syndiotactic polypropylene based on the total weight of said composition; wherein said at least one syndiotactic The polypropylene has a syndiotactic index of at least 70% as measured using13 C-NMR spectroscopy; and wherein the syndiotactic polypropylene does not exhibit a melting temperature peak above 145°C, as measured by differential scanning determined by thermal method;
(b)将步骤(a)中形成的管道冷却；和(b) cooling the tube formed in step (a); and
(c)任选地将步骤(a)中形成的管道加热/退火。(c) optionally heating/annealing the tube formed in step (a).
25.用于制造根据陈述1-23任一项的管道的工艺，其包括如下步骤：25. A process for manufacturing a pipe according to any one of statements 1-23, comprising the steps of:
(a)将所述至少一种间同立构聚丙烯挤出为管道；其中所述至少一种间同立构聚丙烯具有如使用13C-NMR光谱法测量的至少70％的间同立构指数；其中所述管道包括基于所述管道的总重量的至少50％重量的所述至少一种间同立构聚丙烯和其中所述间同立构聚丙烯未呈现高于145℃的熔融温度峰，如通过差示扫描量热法测定的；(a) extruding the at least one syndiotactic polypropylene into a pipe; wherein the at least one syndiotactic polypropylene has a syndiotacticity of at least 70% as measured using13 C-NMR spectroscopy wherein said pipe comprises at least 50% by weight of said at least one syndiotactic polypropylene based on the total weight of said pipe and wherein said syndiotactic polypropylene does not exhibit melting above 145°C Temperature peaks, as determined by differential scanning calorimetry;
(b)将步骤(a)中形成的管道冷却；和(b) cooling the tube formed in step (a); and
(c)任选地将步骤(a)中形成的管道加热/退火。(c) optionally heating/annealing the tube formed in step (a).
26.用于制造根据陈述1-23任一项的管道的工艺，其包括如下步骤：26. A process for manufacturing a pipe according to any one of statements 1-23, comprising the steps of:
(a)将所述至少一种间同立构聚丙烯挤出为管道；(a) extruding said at least one syndiotactic polypropylene into a pipe;
(b)将步骤(a)中形成的管道冷却；和(b) cooling the tube formed in step (a); and
(c)任选地将步骤(a)中形成的管道加热/退火。(c) optionally heating/annealing the tube formed in step (a).
27.陈述24-26任一项的工艺，其中步骤(c)在至少60℃的温度下进行。27. The process of any one of statements 24-26, wherein step (c) is performed at a temperature of at least 60°C.
28.陈述24-27任一项的工艺，其中步骤(c)在至多120℃的温度下进行。28. The process of any one of statements 24-27, wherein step (c) is carried out at a temperature of up to 120°C.
29.陈述24-28任一项的工艺，其中步骤(c)在至少70℃-至多120℃的温度下进行。29. The process of any of statements 24-28, wherein step (c) is carried out at a temperature of at least 70°C to at most 120°C.
30.陈述24-29任一项的工艺，其中步骤(c)进行至少3天。30. The process of any one of statements 24-29, wherein step (c) is carried out for at least 3 days.
31.陈述24-30任一项的工艺，其中步骤(c)进行至多20天。31. The process of any of statements 24-30, wherein step (c) is carried out for up to 20 days.
32.陈述24-31任一项的工艺，其中步骤(c)进行至少3天-至多14天。32. The process of any one of statements 24-31, wherein step (c) is carried out for at least 3 days to at most 14 days.
33.陈述24-32任一项的工艺，其中步骤(c)为退火步骤。33. The process of any one of statements 24-32, wherein step (c) is an annealing step.
34.根据陈述1-23任一项的和/或根据陈述24-33任一项的工艺制造的管道用于输送处于压力下的流体的用途。34. Use of a pipe manufactured according to any one of statements 1-23 and/or according to a process according to any one of statements 24-33 for conveying a fluid under pressure.
根据第一方面，本发明涵盖管道，其包括组合物，所述组合物包括至少一种间同立构聚丙烯，其中所述至少一种间同立构聚丙烯具有如经由13C-NMR光谱法测量的至少70％的间同立构指数；和其中所述间同立构聚丙烯未呈现高于145℃的熔融温度峰，如通过差示扫描量热法测定的。本发明还涵盖管道，其包括至少一种间同立构聚丙烯，其中所述至少一种间同立构聚丙烯具有如经由13C-NMR光谱法测量的至少70％的间同立构指数；和其中如通过差示扫描量热法测定的，所述间同立构聚丙烯未呈现高于145℃的熔融温度峰，如在实施例部分中描述的。According to a first aspect, the present invention covers pipes comprisinga composition comprising at least one syndiotactic polypropylene, wherein said at least one syndiotactic polypropylene has and wherein the syndiotactic polypropylene does not exhibit a melting temperature peak above 145°C, as determined by differential scanning calorimetry. The present invention also covers pipes comprising at least one syndiotactic polypropylene, wherein said at least one syndiotactic polypropylene has a syndiotactic index of at least 70% as measuredvia13C -NMR spectroscopy and wherein the syndiotactic polypropylene does not exhibit a melting temperature peak above 145°C as determined by differential scanning calorimetry, as described in the Examples section.
优选地，本发明提供管道，其包括组合物，所述组合物包括基于所述组合物的总重量的至少50％重量的至少一种间同立构聚丙烯；其中所述至少一种间同立构聚丙烯具有如使用13C-NMR光谱法测量的至少70％的间同立构指数；和其中所述间同立构聚丙烯未呈现高于145℃的熔融温度峰，如通过差示扫描量热法测定的。Preferably, the present invention provides a pipe comprising a composition comprising at least 50% by weight of at least one syndiotactic polypropylene, based on the total weight of said composition; wherein said at least one syndiotactic polypropylene The stereotactic polypropylene has a syndiotactic index of at least 70% as measured using13 C-NMR spectroscopy; and wherein the syndiotactic polypropylene does not exhibit a melting temperature peak above 145° C., as determined by differential determined by scanning calorimetry.
本发明还涵盖管道，其包括至少一种间同立构聚丙烯，其中所述至少一种间同立构聚丙烯具有如使用13C-NMR光谱法测量的至少70％的间同立构指数；其中所述管道包括基于所述管道的总重量的至少50％重量的所述至少一种间同立构聚丙烯和其中所述间同立构聚丙烯未呈现高于145℃的熔融温度峰，如通过差示扫描量热法测定的。The present invention also covers pipes comprising at least one syndiotactic polypropylene, wherein said at least one syndiotactic polypropylene has a syndiotactic index of at least 70% as measured using13 C-NMR spectroscopy ; wherein said pipe comprises at least 50% by weight based on the total weight of said pipe of said at least one syndiotactic polypropylene and wherein said syndiotactic polypropylene does not exhibit a melting temperature peak above 145°C , as determined by differential scanning calorimetry.
如本文中使用的“管道”意欲涵盖狭义上的管道、以及用于管道的补充(附属，supplementary)零件例如接头(fitting)、阀和通常对于(例如用于输送气体、冷水或热水的)管路系统而言必要的所有零件。根据本发明的管道还涵盖单层和多层管道，其中例如所述层的一个或多个是金属层并且其可包含胶粘剂层。管道的其它构造例如波纹管道(波纹管)也是可能的。"Pipeline" as used herein is intended to cover pipelines in a narrow sense, as well as supplementary (supplementary) parts for pipelines such as fittings, valves, and All parts necessary for the piping system. Pipes according to the invention also encompass single-layer and multi-layer pipes, where for example one or more of said layers is a metal layer and which may comprise an adhesive layer. Other configurations of pipes, such as corrugated pipes (bellows), are also possible.
如本文中使用的术语“间同立构聚丙烯”或“间同立构聚丙烯树脂”指的是经挤出、和/或熔融和/或造粒的间同立构聚丙烯绒毛或粉末并且可通过如本文中所教导的所述间同立构聚丙烯的配混和均化(例如用混合和/或挤出机设备)而制造。如本文中使用的，术语“间同立构聚丙烯”或“sPP”可用作“间同立构聚丙烯树脂”的简写。The term "syndiotactic polypropylene" or "syndiotactic polypropylene resin" as used herein refers to extruded, and/or melted and/or pelletized syndiotactic polypropylene fluff or powder And can be produced by compounding and homogenizing (for example with mixing and/or extruder equipment) the syndiotactic polypropylene as taught herein. As used herein, the term "syndiotactic polypropylene" or "sPP" may be used as an abbreviation for "syndiotactic polypropylene resin".
根据本发明的管道包括具有如经由13C-NMR光谱法测量的至少70％、优选地至少73％、更优选地至少75％、优选地至多90％的间同立构指数的间同立构聚丙烯。The conduit according to the invention comprises a syndiotactic structure having a syndiotactic index of at least 70%, preferably at least 73%, more preferably at least 75%, preferably at most 90%, as measuredvia13C -NMR spectroscopy polypropylene.
13C-NMR分析是使用500MHz Bruker NMR光谱仪在125MHz的操作频率下使用高温10mm冷冻探针在使得谱图中的信号强度与样品中的有贡献的碳原子的总数成正比的条件下进行的。这样的条件是技术人员公知的并且包含例如足够的弛豫时间等。实践中，信号的强度是由其积分即对应的面积获得的。数据是在130℃的温度下使用质子去耦、每张谱图240次扫描、11秒的脉冲重复延迟和26000Hz的谱宽采集的。样品是通过如下制备的：将足够量的聚合物在1,2,4-三氯苯(TCB，99％，光谱级)中在130℃下溶解并且偶尔搅动以使样品均匀化，之后添加六氘代苯(C6D6，光谱级)和较少量的六甲基二硅氧烷(HMDS，99.5+％)，其中HMDS充当内标物。举个例子来说，将约200mg聚合物溶解在2.0mL的TCB中，之后添加0.5mL的C6D6和2-3滴HMDS。13 C-NMR analysis was performed using a 500 MHz Bruker NMR spectrometer at an operating frequency of 125 MHz using a high temperature 10 mm cryoprobe under conditions such that the signal intensity in the spectrogram is proportional to the total number of contributing carbon atoms in the sample. Such conditions are well known to the skilled person and include, for example, sufficient relaxation times and the like. In practice, the strength of a signal is obtained from its integral, ie the corresponding area. Data were acquired at a temperature of 130°C using proton decoupling, 240 scans per spectrum, a pulse repetition delay of 11 seconds, and a spectral width of 26000 Hz. Samples were prepared by dissolving a sufficient amount of polymer in 1,2,4-trichlorobenzene (TCB, 99%, Spectroscopic Grade) at 130°C with occasional agitation to homogenize the sample, after which six Deuterated benzene (C6 D6 , spectroscopic grade) and to a lesser extent hexamethyldisiloxane (HMDS, 99.5+%), where HMDS served as internal standard. As an example, approximately 200 mg of polymer was dissolved in 2.0 mL of TCB, after which 0.5 mL of C6 D6 and 2-3 drops of HMDS were added.
在数据采集之后，化学位移参照内标物HMDS的信号(其被指认为δ2.03ppm的值)。间同立构规整度是通过对整个聚合物的13C-NMR分析而测定的。在甲基的光谱区域中，使用公布的数据指认与五元组rrrr、mrrr、mrrm、mrmr、mmrm、rrmr和mmrr对应的信号。间同立构指数是根据以下方程计算的：After data acquisition, chemical shifts were referenced to the signal of the internal standard HMDS (which was assigned a value of δ 2.03 ppm). Syndiotacticity was determined by13 C-NMR analysis of the entire polymer. In the spectral region of the methyl group, signals corresponding to the pentads rrrr, mrrr, mrrm, mrmr, mmrm, rrmr and mmrr were assigned using published data. The syndiotactic index was calculated according to the following equation:
间同立构指数＝rrrr+mrrr+mrrm+1/2*(mrmr+mmrm+rrmr+mmrr)Syndiotactic index = rrrr+mrrr+mrrm+1/2*(mrmr+mmrm+rrmr+mmrr)
在那些条件中13C-NMR检测极限为约0.6/10,000C。The detection limit of13 C-NMR under those conditions is about 0.6/10,000C.
间同立构聚丙烯均聚物是通过丙烯单体的催化聚合而形成的。在一些实施方式中，此处适合的间同立构聚丙烯均聚物具有70％-90％的间同立构规整度程度。优选地，所述间同立构聚丙烯均聚物具有约73％-90％、优选地75％-90％的间同立构规整度程度。Syndiotactic polypropylene homopolymers are formed by the catalytic polymerization of propylene monomers. In some embodiments, suitable syndiotactic polypropylene homopolymers herein have a degree of syndiotacticity of 70% to 90%. Preferably, the syndiotactic polypropylene homopolymer has a degree of syndiotacticity of about 73% to 90%, preferably 75% to 90%.
术语“立构规整度”指的是聚合物中的悬垂基团的排列。例如，聚合物在其悬垂基团以无规方式排列在聚合物链的两侧上时是“无规立构的”。相比之下，聚合物在其悬垂基团全部排列在链的相同侧上时是“全同立构的”和在其悬垂基团在链的相反侧上交替时是“间同立构的”。因此，间同立构聚丙烯是其中悬垂的甲基以从链的一侧至另一侧有规律的方式交替的聚丙烯。The term "tacticity" refers to the arrangement of pendant groups in a polymer. For example, a polymer is "atactic" when its pendant groups are arranged in a random fashion on either side of the polymer chain. In contrast, a polymer is "isotactic" when its pendant groups are all arranged on the same side of the chain and "syndiotactic" when its pendant groups alternate on opposite sides of the chain. ". Syndiotactic polypropylene is thus polypropylene in which the pendant methyl groups alternate in a regular fashion from one side of the chain to the other.
在一种优选实施方式中，合适的间同立构聚丙烯为均聚物。如本文中使用的，间同立构聚丙烯均聚物包含具有很少量的乙烯或其它α烯烃共聚单体(优选乙烯)、即整个聚合物组合物(成分)的小于约0.7％重量的、优选地小于0.5％重量、还更优选地小于0.1％重量的乙烯的间同立构聚丙烯的无规共聚物。具有小于约0.7％重量的乙烯的间同立构聚丙烯共聚物就大部分物理性质而言行为表现得非常像100％重量间同立构聚丙烯均聚物。除非相反地说明，否则术语间同立构聚丙烯均聚物将被理解为包含纯的间同立构聚丙烯均聚物和含有小于约0.7％重量的各种α烯烃、优选地小于0.7％重量的乙烯的间同立构聚丙烯共聚物。In a preferred embodiment, suitable syndiotactic polypropylenes are homopolymers. As used herein, a syndiotactic polypropylene homopolymer comprises ethylene or other alpha olefin comonomers (preferably ethylene) in small amounts, i.e., less than about 0.7% by weight of the entire polymer composition (ingredients). , preferably less than 0.5% by weight, still more preferably less than 0.1% by weight of ethylene, a random copolymer of syndiotactic polypropylene. Syndiotactic polypropylene copolymers having less than about 0.7 weight percent ethylene behave very much like 100 weight percent syndiotactic polypropylene homopolymers with respect to most physical properties. Unless stated to the contrary, the term syndiotactic polypropylene homopolymer is to be understood as comprising pure syndiotactic polypropylene homopolymer and containing less than about 0.7% by weight of each alpha olefin, preferably less than 0.7% Syndiotactic polypropylene copolymer of ethylene by weight.
在一些实施方式中，所述组合物包括基于所述组合物的总重量的至少50％重量、优选地至少60％重量、优选地至少70％重量、优选地至少80％重量、优选地至少90％重量、优选地至少95％重量、还更优选地至少97％重量、还甚至更优选地至少98％重量的所述至少一种间同立构聚丙烯。在一些实施方式中，所述管道包括基于所述管道的总重量的至少50％重量、优选地至少60％重量、优选地至少70％重量、优选地至少80％重量、优选地至少90％重量、优选地至少95％重量的所述至少一种间同立构聚丙烯。In some embodiments, the composition comprises at least 50% by weight, preferably at least 60% by weight, preferably at least 70% by weight, preferably at least 80% by weight, preferably at least 90% by weight, based on the total weight of the composition. % by weight, preferably at least 95% by weight, still more preferably at least 97% by weight, still even more preferably at least 98% by weight of said at least one syndiotactic polypropylene. In some embodiments, the conduit comprises at least 50% by weight, preferably at least 60% by weight, preferably at least 70% by weight, preferably at least 80% by weight, preferably at least 90% by weight, based on the total weight of the conduit , preferably at least 95% by weight of said at least one syndiotactic polypropylene.
在一些实施方式中，根据本发明的管道包括至少一种间同立构聚丙烯，其具有如根据ASTM D-1505在23℃下测定的至多0.900g/cm3的密度。在一些优选实施方式中，所述间同立构聚丙烯具有至少0.800g/cm3且至多0.900g/cm3、优选地至少0.820g/cm3且至多0.900g/cm3、优选地至少0.840g/cm3且至多0.900g/cm3、优选地至少0.8605g/cm3且至多0.9000g/cm3、优选地至少0.870g/cm3且至多0.900g/cm3的密度。所述间同立构聚丙烯的密度指的是不包含添加剂例如颜料如炭黑的原样的聚合物密度，除非另有说明。In some embodiments, pipes according to the invention comprise at least one syndiotactic polypropylene having a density of at most 0.900 g/cm3 as determined according to ASTM D-1505 at 23°C. In some preferred embodiments, the syndiotactic polypropylene has at least 0.800 g/cm3 and at most 0.900 g/cm3 , preferably at least 0.820 g/cm3 and at most 0.900 g/cm3 , preferably at least 0.840 A density of g/cm3 and at most 0.900 g/cm3 , preferably at least 0.8605 g/cm3 and at most 0.9000 g/cm3 , preferably at least 0.870 g/cm3 and at most 0.900 g/cm3 . The density of the syndiotactic polypropylene refers to the density of the polymer as such without additives such as pigments such as carbon black, unless otherwise stated.
适合用于本管道中的间同立构聚丙烯的实例包含如下而没有限制：1251、和1471间同立构聚丙烯，其是可从TotalPetrochemicals USA,Inc商购获得的。Examples of syndiotactic polypropylene suitable for use in the present piping include the following without limitation: 1251, and 1471 syndiotactic polypropylene, which is commercially available from Total Petrochemicals USA, Inc.
所述间同立构聚丙烯合意地是使用茂金属催化剂体系催化的。The syndiotactic polypropylene is desirably catalyzed using a metallocene catalyst system.
优选地，适合于本发明的间同立构聚丙烯可通过如下制造：使丙烯和一种或多种任选的共聚单体、任选的氢气在至少一种单中心催化剂体系、优选地茂金属催化剂体系存在下聚合。Preferably, syndiotactic polypropylenes suitable for the present invention can be produced by reacting propylene and one or more optional comonomers, optionally hydrogen, in at least one single-site catalyst system, preferably a Polymerization in the presence of a metal catalyst system.
如本文中使用的，术语“催化剂”指的是导致聚合反应速率的变化的物质。在本发明中，其尤其适用于适合于将丙烯聚合为间同立构聚丙烯的催化剂。本发明尤其涉及在单中心催化剂存在下制备的间同立构聚丙烯。在这些催化剂之中，茂金属催化剂是优选的。如本文中使用的，术语“经茂金属催化的间同立构聚丙烯树脂”和“经茂金属催化的间同立构聚丙烯”是同义的并且可互换地使用并且指的是在茂金属催化剂存在下制备的间同立构聚丙烯。As used herein, the term "catalyst" refers to a substance that causes a change in the rate of a polymerization reaction. In the present invention it is especially suitable for catalysts suitable for the polymerization of propylene to syndiotactic polypropylene. In particular, the present invention relates to syndiotactic polypropylenes prepared in the presence of single-site catalysts. Among these catalysts, metallocene catalysts are preferred. As used herein, the terms "metallocene-catalyzed syndiotactic polypropylene resin" and "metallocene-catalyzed syndiotactic polypropylene" are synonymous and used interchangeably and refer to Syndiotactic polypropylene prepared in the presence of metallocene catalysts.
术语“茂金属催化剂”或者简写“茂金属”在本文中用于描述任何包括与一种或多种配体键合的金属原子的过渡金属络合物。优选的茂金属催化剂为周期表第IV族过渡金属例如钛、锆、铪等的化合物，并且具有拥有如下的配位结构：金属化合物，和由环戊二烯基、茚基、芴基或它们的衍生物中的一种或两种基团组成的配体。取决于期望的聚合物，可改变所述茂金属的结构和几何形状以适应生产商的具体要求。茂金属典型地包括单个金属中心，这容许更多地控制聚合物的支化和分子量分布。单体被插入到所述金属与聚合物生长链之间。The term "metallocene catalyst" or the abbreviation "metallocene" is used herein to describe any transition metal complex comprising a metal atom bonded to one or more ligands. Preferred metallocene catalysts are compounds of Group IV transition metals of the periodic table such as titanium, zirconium, hafnium, etc., and have a coordination structure as follows: metal compound, and composed of cyclopentadienyl, indenyl, fluorenyl or their Ligands composed of one or two groups of derivatives. Depending on the desired polymer, the structure and geometry of the metallocene can be varied to suit the specific requirements of the manufacturer. Metallocenes typically include a single metal center, which allows greater control over the branching and molecular weight distribution of the polymer. Monomers are inserted between the metal and the growing chain of polymer.
在一些实施方式中，所述茂金属催化剂为式(I)的化合物：In some embodiments, the metallocene catalyst is a compound of formula (I):
R”(Ar)2MQj(I)，R”(Ar)2 MQj (I),
其中根据式(I)的茂金属是桥接的茂金属；wherein the metallocene according to formula (I) is a bridged metallocene;
其中所述根据式(I)的茂金属具有与M结合的两个Ar，其可彼此相同或不同；wherein said metallocene according to formula (I) has two Ar bound to M, which may be the same or different from each other;
其中j为选自1、2、3和4的整数，和当j为2或更大时，所述多个Q可彼此相同或不同；优选地j为2；wherein j is an integer selected from 1, 2, 3 and 4, and when j is 2 or greater, the plurality of Q may be the same or different from each other; preferably j is 2;
其中Ar为芳族环、基团或部分和其中各个Ar独立地选自环戊二烯基、芴基、茚基(IND)、和四氢茚基(THI)，其中所述基团各自可任选地被一个或多个各自独立地选自以下的取代基取代：具有1-20个碳原子的烃基、卤素、SiR”’3，其中R”’为具有1-20个碳原子的烃基，和其中所述烃基任选地含有一个或多个选自包括如下的组的原子：B、Si、S、O、F、Cl、和P；wherein Ar is an aromatic ring, group or moiety and wherein each Ar is independently selected from cyclopentadienyl, fluorenyl, indenyl (IND), and tetrahydroindenyl (THI), wherein each of said groups can be Optionally substituted with one or more substituents each independently selected from hydrocarbyl having 1-20 carbon atoms, halogen, SiR"'3 , wherein R"' is hydrocarbyl having 1-20 carbon atoms , and wherein the hydrocarbyl group optionally contains one or more atoms selected from the group comprising: B, Si, S, O, F, Cl, and P;
其中M为选自钛、锆、铪、和钒的过渡金属；并且优选为锆；wherein M is a transition metal selected from titanium, zirconium, hafnium, and vanadium; and is preferably zirconium;
其中各Q独立地选自卤素、具有1-20个碳原子的烃氧基、和具有1-20个碳原子的烃基和其中所述烃基任选地含有一个或多个选自包括如下的组的原子：B、Si、S、O、F、Cl、和P；和wherein each Q is independently selected from halogen, hydrocarbyloxy having 1-20 carbon atoms, and hydrocarbyl having 1-20 carbon atoms and wherein said hydrocarbyl optionally contains one or more selected from the group consisting of Atoms of: B, Si, S, O, F, Cl, and P; and
其中R”为桥接两个Ar基团的二价基团或部分并且选自C1-C20亚烷基、锗、硅、硅氧烷、烷基膦、和胺，和其中所述R”任选地被一个或多个各自独立地选自以下的取代基取代：具有1-20个碳原子的烃基、卤素、SiR3，其中R为具有1-20个碳原子的烃基；和其中所述烃基任选地含有一个或多个选自包括如下的组的原子：B、Si、S、O、F、Cl、Br、I和P。wherein R" is a divalent group or moiety bridging two Ar groups and is selected from C1 -C20 alkylene, germanium, silicon, siloxane, alkylphosphine, and amine, and wherein said R" Optionally substituted with one or more substituents each independently selected from: hydrocarbyl having 1-20 carbon atoms, halogen, SiR3 , wherein R is hydrocarbyl having 1-20 carbon atoms; and wherein The hydrocarbyl group optionally contains one or more atoms selected from the group comprising: B, Si, S, O, F, Cl, Br, I and P.
优选地，所述茂金属包括桥接的环戊二烯基-芴基组分。在一些实施方式中，所述茂金属催化剂为下式(II)的芴基型茂金属催化剂(FMC)：Preferably, the metallocene comprises a bridged cyclopentadienyl-fluorenyl component. In some embodiments, the metallocene catalyst is a fluorenyl-type metallocene catalyst (FMC) of the following formula (II):
其中M、Q和j如上文中所定义；和wherein M, Q and j are as defined above; and
其中R1、R2、R3和R4各自独立地选自氢、具有1-20个碳原子的烃基、卤素、SiR”’3，其中R”’为具有1-20个碳原子的烃基，和其中所述烃基任选地含有一个或多个选自包括如下的组的原子：B、Si、S、O、F、Cl、Br、I和P；和其中R1和R2未彼此键合而形成环；和其中R3和R4未彼此键合而形成环；wherein R1 , R2 , R3 and R4 are each independently selected from hydrogen, a hydrocarbon group having 1-20 carbon atoms, halogen, SiR"'3 , wherein R"' is a hydrocarbon group having 1-20 carbon atoms , and wherein the hydrocarbyl group optionally contains one or more atoms selected from the group comprising: B, Si, S, O, F, Cl, Br, I, and P; and wherein RandR are not each other bonded to form a ring; and wherein RandR are not bonded to each other to form a ring;
R5和R6各自独立地选自氢；具有1-20个碳原子的烃基、卤素、SiR3，其中R为具有1-20个碳原子的烃基；和其中所述烃基任选地含有一个或多个选自包括如下的组的原子：B、Si、S、O、F、Cl、Br、I和P。优选地，R1和R4相同。优选地，R2、R3相同。优选地R5和R6相同。R5 and R6 are each independently selected from hydrogen; a hydrocarbon group having 1-20 carbon atoms, halogen, SiR3 , wherein R is a hydrocarbon group having 1-20 carbon atoms; and wherein the hydrocarbon group optionally contains one or more atoms selected from the group comprising: B, Si, S, O, F, Cl, Br, I and P. Preferably,R1 andR4 are the same. Preferably, R2 and R3 are the same. PreferablyR5 andR6 are the same.
具有6-20个碳原子的合适烃基的实例包含：苯基、邻-氯苯基、间-氯苯基、对-氯苯基、溴代芳基例如邻-溴苯基、间-溴苯基、对-溴苯基、邻-碘苯基、间-碘苯基、对-碘苯基、萘基、氯代萘基、溴代萘基、碘代萘基、邻-甲苯基、间-甲苯基、对-甲苯基、溴甲基苯基、二溴甲基苯基、碘甲基苯基、二碘甲基苯基、乙基苯基、正丙基苯基、异丙基苯基、正丁基苯基、仲丁基苯基、叔丁基苯基、二甲苯基、苄基、间-氯苄基、对-氯苄基、间-溴苄基、对-溴苄基、间-碘苄基、对-碘苄基、[α]-苯乙基、[β]-苯乙基、二苯基甲基、萘基甲基和苯叔丁基。Examples of suitable hydrocarbyl groups having 6-20 carbon atoms include: phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, bromoaryl such as o-bromophenyl, m-bromobenzene Base, p-bromophenyl, o-iodophenyl, m-iodophenyl, p-iodophenyl, naphthyl, chloronaphthyl, bromonaphthyl, iodonaphthyl, o-tolyl, m -Tolyl, p-tolyl, bromomethylphenyl, dibromomethylphenyl, iodomethylphenyl, diiodomethylphenyl, ethylphenyl, n-propylphenyl, cumene Base, n-butylphenyl, sec-butylphenyl, tert-butylphenyl, xylyl, benzyl, m-chlorobenzyl, p-chlorobenzyl, m-bromobenzyl, p-bromobenzyl , m-iodobenzyl, p-iodobenzyl, [α]-phenethyl, [β]-phenethyl, diphenylmethyl, naphthylmethyl and phenyl-tert-butyl.
在一些实施方式中，所述茂金属催化剂为式(II)的FMC，其中R1、R2、R3和R4各自独立地选自氢、具有1-20个碳原子的烃基、和SiR”’3，其中R”’为具有1-20个碳原子的烃基；和其中R1和R2未彼此键合而形成环；和其中R3和R4未彼此键合而形成环。更优选地，R1和R4相同；并且R2和R3相同；并且特别优选的是，R2和R3为叔丁基。In some embodiments, the metallocene catalyst is an FMC of formula (II), wherein R1 , R2 , R3 and R4 are each independently selected from hydrogen, hydrocarbon groups having 1-20 carbon atoms, and SiR "'3 , wherein R"' is a hydrocarbon group having 1-20 carbon atoms; and wherein R1 and R2 are not bonded to each other to form a ring; and wherein R3 and R4 are not bonded to each other to form a ring. More preferably, R1 and R4 are the same; and R2 and R3 are the same; and especially preferably, R2 and R3 are tert-butyl.
在一些实施方式中，所述茂金属催化剂为式(II)的FMC，其中R5和R6各自独立地选自氢；具有1-20个碳原子的烃基和SiR3，其中R为具有1-20个碳原子的烃基；和其中所述烃基任选地含有一个或多个选自包括如下的组的原子：F、Cl、Br和I。更优选地R5和R6相同并且为具有6-20个碳原子的烃基。优选地，R1和R4相同并且R2和R3相同。In some embodiments, the metallocene catalyst is FMC of formula (II), wherein R5 and R6 are each independently selected from hydrogen; hydrocarbon groups having 1-20 carbon atoms and SiR3 , wherein R is - a hydrocarbyl group of 20 carbon atoms; and wherein said hydrocarbyl group optionally contains one or more atoms selected from the group comprising: F, Cl, Br and I. More preferablyR5 andR6 are the same and are hydrocarbon groups having 6-20 carbon atoms. Preferably,R1 andR4 are the same andR2 andR3 are the same.
在一些实施方式中，所述茂金属催化剂为式(II)的FMC，其中R1和R4各自优选为氢原子或者具有6-20个碳原子的烃基；更优选地氢原子或者具有6-10个碳原子的芳基；最优选地氢原子、苯基、邻-甲苯基、间-甲苯基、对-甲苯基、邻-氯苯基、间-氯苯基或对-氯苯基。优选地，R1和R4相同，R5和R6相同并且R2和R3相同。In some embodiments, the metallocene catalyst is FMC of formula (II), wherein each of R andR is preferably a hydrogen atom or a hydrocarbon group with6-20 carbon atoms; more preferably a hydrogen atom or a hydrocarbon group with 6- An aryl group of 10 carbon atoms; most preferably a hydrogen atom, phenyl, o-tolyl, m-tolyl, p-tolyl, o-chlorophenyl, m-chlorophenyl or p-chlorophenyl. Preferably,R1 andR4 are the same,R5 andR6 are the same andR2 andR3 are the same.
在一些实施方式中，所述茂金属催化剂为式(II)的FMC，其中R5和R6可彼此相同或不同，并且各自优选为具有6-10个碳原子的芳基或者具有6-10个碳原子的芳烷基；优选为苯基、苄基、间-氯苯基、对-氯苯基、间-氯苄基或者对-氯苄基。优选地，R1和R4相同，R5和R6相同并且R2和R3相同。In some embodiments, the metallocene catalyst is FMC of formula (II), wherein R andR canbe the same or different from each other, and each is preferably an aryl group with 6-10 carbon atoms or an aryl group with 6-10 Aralkyl of 2 carbon atoms; preferably phenyl, benzyl, m-chlorophenyl, p-chlorophenyl, m-chlorobenzyl or p-chlorobenzyl. Preferably,R1 andR4 are the same,R5 andR6 are the same andR2 andR3 are the same.
适合用于制备此处使用的间同立构聚丙烯的FMC的说明性实例包含二苄基亚甲基(环戊二烯基)(2,7-二甲基-3,6-二叔丁基芴基)二氯化锆[也称作1,3-二苯基异丙叉(环戊二烯基)(2,7-二甲基-3,6-二叔丁基芴基)二氯化锆；下文中，省略各化合物的别名]、二苄基亚甲基(环戊二烯基)(2,7-二(2,4,6-三甲基苯基)-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二(3,5-二甲基苯基)-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二(4-甲基苯基)-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二萘基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二(4-叔丁基苯基)-3,6-二叔丁基芴基)二氯化锆、二苯乙基亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆、二(二苯甲基)亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆、二(枯基)亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆、二苯基亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二-邻-甲苯基亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二-间-甲苯基亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二-对-甲苯基亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(邻-氯苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(间-氯苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对-氯苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(邻-溴苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(间-溴苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对-溴苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(邻-碘苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(间-碘苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对-碘苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(邻-三氟甲基苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(间-三氟甲基苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对-三氟甲基苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(2-萘基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(邻-氯苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(间-氯苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对-氯苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(邻-溴苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(间-溴苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对-溴苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(邻-碘苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(间-碘苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对-碘苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(邻-甲基苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(间-甲基苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对-甲基苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、(苄基)(苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、(苄基)(苯基)亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆、(苄基)(苯基)亚甲基(环戊二烯基)(2,7-二-邻-甲苯基-3,6-二叔丁基芴基)二氯化锆、(苄基)(苯基)亚甲基(环戊二烯基)(2,7-二-对-氯苯基-3,6-二叔丁基芴基)二氯化锆、(对-氯苄基)(苯基)亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆、(对-氯苄基)(苯基)亚甲基(环戊二烯基)(2,7-二-邻-甲苯基-3,6-二叔丁基芴基)二氯化锆、(对-氯苄基)(苯基)亚甲基(环戊二烯基)(2,7-二对-氯苯基-3,6-二叔丁基芴基)二氯化锆、(苄基)(对-氯苯基)亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆、(苄基)(对-氯苯基)亚甲基(环戊二烯基)(2,7-二-邻-甲苯基-3,6-二叔丁基芴基)二氯化锆、(苄基)(对-氯苯基)亚甲基(环戊二烯基)(2,7-二-对-氯苯基-3,6-二叔丁基芴基)二氯化锆、二苯基亚甲基(环戊二烯基)(2,7-二-邻-甲苯基-3,6-二叔丁基芴基)二氯化锆、二-对-甲苯基-亚甲基(环戊二烯基)(2,7-二-邻-甲苯基-3,6-二叔丁基芴基)二氯化锆、二(对-氯苯基)亚甲基(环戊二烯基)(2,7-二-邻-甲苯基-3,6-二叔丁基芴基)二氯化锆、二(对-三氟甲基苯基)亚甲基(环戊二烯基)(2,7-二-邻-甲苯基-3,6-二叔丁基芴基)二氯化锆、二(2-萘基)亚甲基(环戊二烯基)(2,7-二-邻-甲苯基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二-邻-甲苯基-3,6-二叔丁基芴基)二氯化锆、二(对-氯苄基)亚甲基(环戊二烯基)(2,7-二-邻-甲苯基-3,6-二叔丁基芴基)二氯化锆、二(对-甲基苄基)亚甲基(环戊二烯基)(2,7-二-邻-甲苯基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二-邻-甲苯基-芴基)二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二(邻-乙基苯基)-3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻-(正丙基)苯基]-3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻-(异丙基)苯基]-3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻-(正丁基)苯基]-3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻-(异丁基)苯基]-3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻-(仲丁基)苯基]-3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻-(叔丁基)苯基]-3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻-(正二十烷基)苯基]-3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二(邻-环己基苯基)-3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二(联苯-2-基)-3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻-(2-萘基)苯基]-3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻-(2-菲基)苯基]-3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二(邻-三甲基甲硅烷基苯基)-3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二(邻-三苯基甲硅烷基苯基)-3,6-二叔丁基芴基]二氯化锆、二苯基亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆、二苯基亚甲基(环戊二烯基)(2,7-二-对-氯苯基-3,6-二叔丁基芴基)二氯化锆、二-对-甲苯基-亚甲基(环戊二烯基)(2,7-二-对-氯苯基-3,6-二叔丁基芴基)二氯化锆、二(对-氯苯基)亚甲基(环戊二烯基)(2,7-二-对-氯苯基-3,6-二叔丁基芴基)二氯化锆、二(对-三氟甲基苯基)亚甲基(环戊二烯基)(2,7-二-对-氯苯基-3,6-二叔丁基芴基)二氯化锆、二(2-萘基)亚甲基(环戊二烯基)(2,7-二-对-氯苯基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二-对-氯苯基-3,6-二叔丁基芴基)二氯化锆、二(对-氯苄基)亚甲基(环戊二烯基)(2,7-二-对-氯苯基-3,6-二叔丁基芴基)二氯化锆、二(对-甲基苄基)亚甲基(环戊二烯基)(2,7-二-对-氯苯基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二-对-氯苯基-3,6-双三甲基甲硅烷基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二-对-氯苯基-3,6-二枯基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二-对-氯苯基-3,6-金刚烷基芴基)二氯化锆、二甲基亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二乙基亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二正丙基亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二异丙基亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二正丁基亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二异丁基亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二仲丁基亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二叔丁基亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二正辛基亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二正三十烷基亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、苯基亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二苯基亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二-对-甲苯基亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二(对-氯苯基)亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二(对-三氟甲基苯基)亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二(2-萘基)亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二(对-氯苄基)亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二(对-甲基苄基)亚甲基(环戊二烯基)(2,7-二-对-三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆；其中以上化合物的锆原子用铪原子或钛原子代替的化合物；其中以上化合物的氯原子用甲基或苄基代替的化合物；及其组合，而不限于此。在铪原子、锆原子和钛原子之中，优选锆原子。这些化合物可单独地使用，或者可将两种或更多中组合使用。Illustrative examples of FMCs suitable for use in preparing the syndiotactic polypropylene used herein include dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butyl fluorenyl) zirconium dichloride [also known as 1,3-diphenylisopropylidene (cyclopentadienyl) (2,7-dimethyl-3,6-di-tert-butylfluorenyl) dichloride Zirconium chloride; hereinafter, the aliases of each compound are omitted], dibenzylmethylene (cyclopentadienyl) (2,7-di(2,4,6-trimethylphenyl)-3,6 -Di-tert-butylfluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride , dibenzylmethylene (cyclopentadienyl) (2,7-bis(3,5-dimethylphenyl)-3,6-di-tert-butylfluorenyl) zirconium dichloride, dibenzyl Methylene(cyclopentadienyl)(2,7-bis(4-methylphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl) Pentadienyl)(2,7-dinaphthyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(2,7-di( 4-tert-butylphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride, diphenylethylmethylene(cyclopentadienyl)(2,7-diphenyl-3, 6-di-tert-butylfluorenyl)zirconium dichloride, bis(benzhydryl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluorenyl ) zirconium dichloride, bis(cumyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylene Methyl(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, di-o-tolylmethylene(cyclopentadienyl)(3,6-di-tert-butyl ylfluorenyl) zirconium dichloride, di-m-tolyl methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, di-p-tolyl methylene Base(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(o-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert- Butylfluorenyl)zirconium dichloride, bis(m-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(p-chloro Phenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(o-bromophenyl)methylene(cyclopentadienyl)(3 ,6-di-tert-butylfluorenyl)zirconium dichloride, bis(m-bromophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, Bis(p-bromophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(o-iodophenyl)methylene(cyclopentadiene Alkenyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(m-iodophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl) Zirconium dichloride, bis(p-iodophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(o-trifluoromethylphenyl) ) methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(inter-tri Fluoromethylphenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(p-trifluoromethylphenyl)methylene(cyclopentadienyl) Dienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(2-naphthyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl) Zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(o-chlorobenzyl)methylene(cyclopentadiene Alkenyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(m-chlorobenzyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl) Zirconium dichloride, bis(p-chlorobenzyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(o-bromobenzyl)methylene Base(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(m-bromobenzyl)methylene(cyclopentadienyl)(3,6-di-tert- Butylfluorenyl)zirconium dichloride, bis(p-bromobenzyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(o-iodo Benzyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(m-iodobenzyl)methylene(cyclopentadienyl)(3 ,6-di-tert-butylfluorenyl)zirconium dichloride, bis(p-iodobenzyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, Bis(o-methylbenzyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(m-methylbenzyl)methylene(cyclopentadienyl) Pentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(p-methylbenzyl)methylene(cyclopentadienyl)(3,6-di-tert-butyl Fluorenyl)zirconium dichloride, (benzyl)(phenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, (benzyl)(phenyl ) methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, (benzyl)(phenyl)methylene(cyclopentadienyl) Dienyl)(2,7-di-o-tolyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, (benzyl)(phenyl)methylene(cyclopentadienyl) (2,7-di-p-chlorophenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, (p-chlorobenzyl)(phenyl)methylene(cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, (p-chlorobenzyl)(phenyl)methylene(cyclopentadienyl)(2,7 -Di-o-tolyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, (p-chlorobenzyl)(phenyl)methylene(cyclopentadienyl)(2,7- Dip-chlorophenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, (benzyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-di Phenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, (benzyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-o-toluene -3,6-di-tert-butylfluorenyl)zirconium dichloride, (benzyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-p -Chlorophenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2,7-di-o-tolyl-3,6- Di-tert-butylfluorenyl)zirconium dichloride, bis-p-tolyl-methylene(cyclopentadienyl)(2,7-di-o-tolyl-3,6-di-tert-butylfluorene base) zirconium dichloride, bis(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-o-tolyl-3,6-di-tert-butylfluorenyl)dichloro Zirconium chloride, bis(p-trifluoromethylphenyl)methylene(cyclopentadienyl)(2,7-di-o-tolyl-3,6-di-tert-butylfluorenyl) dichloride Zirconium, bis(2-naphthyl)methylene(cyclopentadienyl)(2,7-di-o-tolyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, dibenzyl Methylene(cyclopentadienyl)(2,7-di-o-tolyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(p-chlorobenzyl)methylene( Cyclopentadienyl)(2,7-di-o-tolyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(p-methylbenzyl)methylene(cyclopentadiene Alkenyl)(2,7-di-o-tolyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(2,7-di -o-tolyl-fluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)[2,7-bis(o-ethylphenyl)-3,6-di-tert-butyl Fluorenyl]zirconium dichloride, dibenzylmethylene(cyclopentadienyl)[2,7-bis[o-(n-propyl)phenyl]-3,6-di-tert-butylfluorenyl] Zirconium dichloride, dibenzylmethylene(cyclopentadienyl)[2,7-bis[o-(isopropyl)phenyl]-3,6-di-tert-butylfluorenyl]dichloride Zirconium, dibenzylmethylene(cyclopentadienyl)[2,7-bis[o-(n-butyl)phenyl]-3,6-di-tert-butylfluorenyl]zirconium dichloride, di Benzylmethylene(cyclopentadienyl)[2,7-bis[o-(isobutyl)phenyl]-3,6-di-tert-butylfluorenyl]zirconium dichloride, dibenzylidene Methyl(cyclopentadienyl)[2,7-bis[o-(sec-butyl)phenyl]-3,6-di-tert-butylfluorenyl]zirconium dichloride, dibenzylmethylene ( Cyclopentadienyl)[2,7-bis[o-(tert-butyl)phenyl]-3,6-di-tert-butylfluorenyl]zirconium dichloride, dibenzylmethylene (cyclopentadiene Alkenyl)[2,7-bis[o-(n-eicosyl)phenyl]-3,6-di-tert-butylfluorenyl]zirconium dichloride, dibenzylmethylene (cyclopentadiene base)[2,7-bis(o-cyclohexylphenyl)-3,6-di-tert-butylfluorenyl]zirconium dichloride, dibenzylmethylene(cyclopentadienyl)[2,7 -Bis(biphenyl-2-yl)-3,6-di-tert-butylfluorenyl]zirconium dichloride, dibenzylmethylene(cyclopentadienyl)[2,7-bis[o-( 2-naphthyl)phenyl]-3,6-di-tert-butylfluorenyl]zirconium dichloride, dibenzylmethylene(cyclopentadienyl)[2,7-bis[o-(2- phenanthrenyl)phenyl]-3,6-di-tert-butylfluorenyl]zirconium dichloride, dibenzylmethylene (cyclopentadienyl)[2, 7-bis(o-trimethylsilylphenyl)-3,6-di-tert-butylfluorenyl]zirconium dichloride, dibenzylmethylene(cyclopentadienyl)[2,7- Bis(o-triphenylsilylphenyl)-3,6-di-tert-butylfluorenyl]zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2,7-diphenyl -3,6-di-tert-butylfluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluorenyl ) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-p-chlorophenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride, di- p-tolyl-methylene(cyclopentadienyl)(2,7-di-p-chlorophenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(p-chlorobenzene base) methylene(cyclopentadienyl)(2,7-di-p-chlorophenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(p-trifluoromethylbenzene base) methylene(cyclopentadienyl)(2,7-di-p-chlorophenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(2-naphthyl)methylene Base(cyclopentadienyl)(2,7-di-p-chlorophenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl) (2,7-di-p-chlorophenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(p-chlorobenzyl)methylene(cyclopentadienyl)(2, 7-di-p-chlorophenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, bis(p-methylbenzyl)methylene(cyclopentadienyl)(2,7- Di-p-chlorophenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(2,7-di-p-chlorophenyl- 3,6-bistrimethylsilylfluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(2,7-di-p-chlorophenyl-3,6-di Cumylfluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(2,7-di-p-chlorophenyl-3,6-adamantylfluorenyl)zirconium dichloride , Dimethylmethylene(cyclopentadienyl)(2,7-di-p-trifluoromethylphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, diethylidene Methyl(cyclopentadienyl)(2,7-di-p-trifluoromethylphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, di-n-propylmethylene(cyclo Pentadienyl)(2,7-di-p-trifluoromethylphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, diisopropylmethylene(cyclopentadienyl )(2,7-di-p-trifluoromethylphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, di-n-butylmethylene(cyclopentadienyl)(2, 7-di-p-trifluoromethylphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, diisobutylmethylene(cyclopentadienyl)(2,7-di- p-trifluoromethylphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, di-sec-butylmethylene(cyclopentadienyl)(2,7-di-p-trifluoro Methylphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, di-tert-butylmethylene(cyclopentadienyl)(2,7-di-p-tri Fluoromethylphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, di-n-octylmethylene(cyclopentadienyl)(2,7-di-p-trifluoromethylbenzene Base-3,6-di-tert-butylfluorenyl)zirconium dichloride, tri-n-tridecylmethylene(cyclopentadienyl)(2,7-di-p-trifluoromethylphenyl- 3,6-di-tert-butylfluorenyl)zirconium dichloride, phenylmethylene(cyclopentadienyl)(2,7-di-p-trifluoromethylphenyl-3,6-di-tert Butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-di-tert-butylfluorenyl) Zirconium dichloride, bis-p-tolyl methylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-di-tert-butylfluorenyl) dichloro Zirconium chloride, bis(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-p-trifluoromethylphenyl-3,6-di-tert-butylfluorenyl)dichloro Zirconium chloride, bis(p-trifluoromethylphenyl)methylene(cyclopentadienyl)(2,7-di-p-trifluoromethylphenyl-3,6-di-tert-butylfluorenyl ) zirconium dichloride, bis(2-naphthyl)methylene(cyclopentadienyl)(2,7-di-p-trifluoromethylphenyl-3,6-di-tert-butylfluorenyl) Zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride, Bis(p-chlorobenzyl)methylene(cyclopentadienyl)(2,7-di-p-trifluoromethylphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, Bis(p-methylbenzyl)methylene(cyclopentadienyl)(2,7-di-p-trifluoromethylphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride ; a compound wherein the zirconium atom of the above compound is replaced with a hafnium atom or a titanium atom; a compound wherein the chlorine atom of the above compound is replaced with a methyl group or a benzyl group; and combinations thereof, without being limited thereto. Among hafnium atoms, zirconium atoms and titanium atoms, zirconium atoms are preferred. These compounds may be used alone, or two or more may be used in combination.
如本文中使用的，术语“具有1-20个碳原子的烃基”指的是选自包括如下的组的部分：线型或支化的C1-C20烷基；C3-C20环烷基；C6-C20芳基；C7-C20烷基芳基和C7-C20芳基烷基、或其任意组合。示例性的烃基为甲基、乙基、丙基、丁基、戊基、异戊基、己基、异丁基、庚基、辛基、壬基、癸基、鲸蜡基、2-乙基己基、和苯基。As used herein, the term "hydrocarbyl having 1-20 carbon atoms" refers to a moiety selected from the group comprising: linear or branched C1 -C20 alkyl; C3 -C20 ring Alkyl; C6 -C20 aryl; C7 -C20 alkylaryl and C7 -C20 arylalkyl, or any combination thereof. Exemplary hydrocarbyl groups are methyl, ethyl, propyl, butyl, pentyl, isopentyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethyl Hexyl, and phenyl.
如本文中使用的，术语“具有1-20个碳原子的烃氧基”指的是具有式烃基-O-的部分，其中如本文中所描述的，所述烃基具有1-20个碳原子。优选的烃氧基选自包括如下的组：烷基氧基、烯基氧基、环烷基氧基或者芳烷氧基。As used herein, the term "hydrocarbyloxy having 1-20 carbon atoms" refers to a moiety having the formula hydrocarbyl-O-, wherein the hydrocarbyl group has 1-20 carbon atoms as described herein . Preferred hydrocarbyloxy groups are selected from the group comprising: alkyloxy, alkenyloxy, cycloalkyloxy or aralkoxy.
如本文中使用的，术语“烷基”(本身或者作为另一取代基的部分)指的是具有1个或更多个碳原子、例如1-20个碳原子、例如1-12个碳原子、例如1-6个碳原子、例如1-4个碳原子的通过碳-碳单键结合的直链或支化的饱和烃基团。当在本文中跟在碳原子之后使用下标时，该下标指的是所命名基团可含有的碳原子数。因此，例如，C1-12烷基意指1-12个碳原子的烷基。烷基的实例为甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、2-甲基丁基、戊基和其链异构体、己基和其链异构体、庚基和其链异构体、辛基和其链异构体、壬基和其链异构体、癸基和其链异构体、十一烷基和其链异构体、十二烷基和其链异构体。烷基具有通式CnH2n+1。As used herein, the term "alkyl" (by itself or as part of another substituent) refers to a group having 1 or more carbon atoms, such as 1-20 carbon atoms, such as 1-12 carbon atoms , for example 1-6 carbon atoms, for example 1-4 carbon atoms, a linear or branched saturated hydrocarbon group bonded by a carbon-carbon single bond. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. Thus, for example, C1-12 alkyl means an alkyl group of 1-12 carbon atoms. Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, pentyl and its chain isomers, hexyl and its chain isomers, heptyl and its chain isomers, octyl and its chain isomers, nonyl and its chain isomers, decyl and its chain isomers, undecyl and its chain isomers Isomers, dodecyl and its chain isomers. Alkyl groups have the general formula Cn H2n+1 .
如本文中使用的，术语“环烷基”(本身或者作为另一取代基的部分)指的是饱和或者部分地饱和的环状烷基自由基。环烷基具有通式CnH2n-1。当在本文中跟在碳原子之后使用下标时，该下标指的是所命名基团可含有的碳原子数。因此，C3-6环烷基的实例包含环丙基、环丁基、环戊基、或环己基。As used herein, the term "cycloalkyl" (by itself or as part of another substituent) refers to a saturated or partially saturated cyclic alkyl radical. Cycloalkyl groups have the general formula Cn H2n-1 . When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. Thus, examples of C3-6 cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.
如本文中使用的，术语“芳基”(本身或者作为另一取代基的部分)指的是由芳族环衍生的自由基例如苯基、萘基、茚满基、或者1,2,3,4-四氢-萘基。当在本文中跟在碳原子之后使用下标时，该下标指的是所命名基团可含有的碳原子数。As used herein, the term "aryl" (by itself or as part of another substituent) refers to a radical derived from an aromatic ring such as phenyl, naphthyl, indanyl, or 1,2,3 , 4-tetrahydro-naphthyl. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain.
如本文中使用的，术语“烷基芳基”(本身或者作为另一取代基的部分)指的是其中氢原子被如本文中定义的烷基代替的如本文中定义的芳基。当在本文中跟在碳原子之后使用下标时，该下标指的是所命名基团或者子基团可含有的碳原子数。As used herein, the term "alkylaryl" (by itself or as part of another substituent) refers to an aryl group as defined herein in which a hydrogen atom is replaced by an alkyl group as defined herein. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group or subgroup may contain.
如本文中使用的，术语“芳基烷基”(本身或者作为另一取代基的部分)指的是其中氢原子被如本文中定义的芳基代替的如本文中定义的烷基。当在本文中跟在碳原子之后使用下标时，该下标指的是所命名基团可含有的碳原子数。C6-10芳基C1-6烷基自由基的实例包含苄基、苯乙基、二苄基甲基、甲基苯基甲基、3-(2-萘基)-丁基等。As used herein, the term "arylalkyl" (by itself or as part of another substituent) refers to an alkyl group as defined herein in which a hydrogen atom is replaced by an aryl group as defined herein. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. Examples of the C6-10 aryl C1-6 alkyl radical include benzyl, phenethyl, dibenzylmethyl, methylphenylmethyl, 3-(2-naphthyl)-butyl and the like.
如本文中使用的，术语“亚烷基”(本身或者作为另一取代基的部分)指的是这样的烷基：其为二价的，即，具有两个单键用于与两个其它基团连接。亚烷基可为线型或支化的并且可如所指示那样被取代。亚烷基的非限制性实例包含亚甲基(-CH2-)、亚乙基(-CH2-CH2-)、甲基亚甲基(-CH(CH3)-)、1-甲基-亚乙基(-CH(CH3)-CH2-)、亚正丙基(-CH2-CH2-CH2-)、2-甲基亚丙基(-CH2-CH(CH3)-CH2-)、3-甲基亚丙基(-CH2-CH2-CH(CH3)-)、亚正丁基-CH2-CH2-CH2-CH2-)、2-甲基亚丁基(-CH2-CH(CH3)-CH2-CH2-)、4-甲基亚丁基(-CH2-CH2-CH2-CH(CH3)-)、亚戊基和其链异构体、亚己基和其链异构体、亚庚基和其链异构体、亚辛基和其链异构体、亚壬基和其链异构体、亚癸基和其链异构体、亚十一烷基和其链异构体、亚十二烷基和其链异构体。当在本文中跟在碳原子之后使用下标时，该下标指的是所命名基团可含有的碳原子数。例如，C1-C20亚烷基指的是具有1-20个碳原子的亚烷基。As used herein, the term "alkylene" (by itself or as part of another substituent) refers to an alkyl group that is divalent, that is, has two single bonds for bonding with two other group connection. Alkylene groups can be linear or branched and can be substituted as indicated. Non-limiting examples of alkylene groups include methylene (-CH2- ), ethylene (-CH2- CH2-), methylmethylene (-CH(CH3 )-), 1-methano -Ethylene (-CH(CH3 )-CH2 -), n-propylene (-CH2 -CH2 -CH2 -), 2-methylpropylene (-CH2 -CH(CH3 )-CH2 -), 3-methylpropylene (-CH2 -CH2 -CH(CH3 )-), n-butylene-CH2 -CH2 -CH2 -CH2 -), 2-methylbutylene (-CH2 -CH(CH3 )-CH2 -CH2 -), 4-methylbutylene (-CH2 -CH 2 -CH2-CH (CH3 )-), Pentylene and its chain isomers, hexylene and its chain isomers, heptylene and its chain isomers, octylene and its chain isomers, nonylene and its chain isomers, Decyl and its chain isomers, undecylene and its chain isomers, dodecylene and its chain isomers. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. For example, C1 -C20 alkylene refers to an alkylene group having 1-20 carbon atoms.
示例性的卤素原子包含氯、溴、氟和碘，其中氟和氯是优选的。Exemplary halogen atoms include chlorine, bromine, fluorine and iodine, with fluorine and chlorine being preferred.
本文中使用的合适的茂金属催化剂优选地提供于固体载体上。所述载体可为与常规茂金属催化剂的任意组分不具有化学反应性的惰性的有机或无机固体。用于该负载催化剂的合适的载体材料包含固体无机氧化物例如二氧化硅，氧化铝，氧化镁，氧化钛，三氧化硼，氧化钙，氧化锌，氧化钡，氧化钍，以及二氧化硅和一种或多种第2或13族金属氧化物的混合氧化物例如二氧化硅-氧化镁和二氧化硅-氧化铝混合氧化物。二氧化硅，氧化铝，以及二氧化硅和一种或多种第2或13族金属氧化物的混合氧化物是优选的载体材料。这样的混合氧化物的优选实例为二氧化硅-氧化铝。最优选的是二氧化硅化合物。在一种优选实施方式中，所述茂金属催化剂提供于固体载体、优选地二氧化硅载体上。所述二氧化硅可为粒状的、附聚的、热解的或其它形式。Suitable metallocene catalysts for use herein are preferably provided on a solid support. The support may be an inert organic or inorganic solid that is not chemically reactive with any component of a conventional metallocene catalyst. Suitable support materials for the supported catalyst include solid inorganic oxides such as silica, alumina, magnesia, titania, boron trioxide, calcium oxide, zinc oxide, barium oxide, thoria, and silica and Mixed oxides of one or more Group 2 or 13 metal oxides such as silica-magnesia and silica-alumina mixed oxides. Silica, alumina, and mixed oxides of silica and one or more Group 2 or 13 metal oxides are preferred support materials. A preferred example of such a mixed oxide is silica-alumina. Most preferred are silica compounds. In a preferred embodiment, the metallocene catalyst is provided on a solid support, preferably a silica support. The silica may be in granular, agglomerated, pyrogenic or other form.
所述FMC可与一种或多种助催化剂一起使用以形成催化剂体系。如本文中使用的“催化剂体系”指的是一致地起作用以提高反应速率的一种或多种化学试剂。包括本文中公开的类型的FMC的催化剂体系可用于催化丙烯聚合成间同立构聚丙烯。The FMC can be used with one or more co-catalysts to form a catalyst system. A "catalyst system" as used herein refers to one or more chemical reagents that act in concert to increase the rate of a reaction. Catalyst systems comprising FMCs of the type disclosed herein can be used to catalyze the polymerization of propylene to syndiotactic polypropylene.
在一些实施方式中，用于制造本文中使用的间同立构聚丙烯的催化剂体系包括助催化剂。在将本公开内容的催化剂组分(即FMC)用于聚合程序中时，它们可与活化用助催化剂一起使用。合适的活化用助催化剂可为已知用于该目的的任何助催化剂例如含铝助催化剂、含硼助催化剂或者氟化的催化剂。所述含铝助催化剂可包括铝氧烷、烷基铝、路易斯酸和/或氟化的催化性载体。In some embodiments, the catalyst system used to make the syndiotactic polypropylene used herein includes a cocatalyst. When using the catalyst components of the present disclosure (ie, FMCs) in polymerization procedures, they can be used with an activating cocatalyst. Suitable activating cocatalysts may be any cocatalysts known for this purpose, for example aluminum-containing cocatalysts, boron-containing cocatalysts or fluorinated catalysts. The aluminum-containing cocatalyst may include aluminoxanes, aluminum alkyls, Lewis acids, and/or fluorinated catalytic supports.
在一些实施方式中，使用铝氧烷作为用于所述茂金属催化剂的活化剂。如本文中使用的，术语“铝氧烷”和“铝烷”可互换地使用并且指的是能够活化所述茂金属催化剂的物质。在一种实施方式中，铝氧烷包括低聚的线型和/或环状的烷基铝氧烷。在进一步的实施方式中，所述铝氧烷具有式(V)或(VI)：In some embodiments, alumoxanes are used as activators for the metallocene catalysts. As used herein, the terms "aluminoxane" and "aluminum "Alkane" is used interchangeably and refers to a substance capable of activating the metallocene catalyst. In one embodiment, alumoxanes include oligomeric linear and/or cyclic alkylalumoxanes. In In a further embodiment, the aluminoxane has formula (V) or (VI):
Ra-(Al(Ra)-O)x-AlRa2(V)，对于低聚的线型铝氧烷；或者Ra -(Al(Ra )-O)x-AlRa 2(V), for oligomeric linear aluminoxanes; or
(-Al(Ra)-O-)y(VI)，对于低聚的环状铝氧烷(-Al(Ra )-O-)y (VI), for oligomeric cyclic aluminoxanes
其中x为1-40、且优选为10-20；Wherein x is 1-40, and preferably 10-20;
其中y为3-40、且优选为3-20；和wherein y is 3-40, and preferably 3-20; and
其中各Ra独立地选自C1-C8烷基，且优选为甲基。在一种优选实施方式中，所述铝氧烷为甲基铝氧烷(MAO)。Wherein each Ra is independently selected from C1 -C8 alkyl, and is preferably methyl. In a preferred embodiment, the aluminoxane is methylaluminoxane (MAO).
在一种优选实施方式中，所述茂金属催化剂为负载的茂金属-铝氧烷催化剂，其包括结合在多孔二氧化硅载体上的茂金属和铝氧烷。In a preferred embodiment, the metallocene catalyst is a supported metallocene-aluminoxane catalyst comprising a metallocene and an aluminoxane bound to a porous silica support.
可使用一种或多种由式AIRbx表示的烷基铝作为另外的助催化剂，其中各Rb相同或不同并且选自卤素或者具有1-12个碳原子的烷氧基或者烷基并且x为1-3。非限制性实例为三乙基铝(TEAL)、三异丁基铝(TIBAL)、三甲基铝(TMA)、和甲基-甲基-乙基铝(MMEAL)。尤其合适的是三烷基铝，最优选的是三异丁基铝(TIBAL)和三乙基铝(TEAL)。One or more aluminum alkyls represented by the formula AIRbx may be used as additional cocatalysts, wherein each Rb is the same or different and is selected from halogen or alkoxy or alkyl having 1 to 12 carbon atoms and x is 1-3. Non-limiting examples are triethylaluminum (TEAL), triisobutylaluminum (TIBAL), trimethylaluminum (TMA), and methyl-methyl-ethylaluminum (MMEAL). Especially suitable are trialkylaluminums, most preferred are triisobutylaluminum (TIBAL) and triethylaluminum (TEAL).
所述烷基铝氧烷助催化剂和FMC可以任何合适的量使用以提供烯烃聚合催化剂。合适的铝:FMC摩尔比在10:1-20,000:1的范围内，替代地，在50:1-10,000:1的范围内，替代地，在100:1-5,000:1的范围内。The alkylaluminoxane cocatalyst and FMC can be used in any suitable amount to provide an olefin polymerization catalyst. Suitable aluminum:FMC molar ratios are in the range of 10:1-20,000:1, alternatively in the range of 50:1-10,000:1, alternatively in the range of 100:1-5,000:1.
丙烯聚合以形成间同立构聚丙烯可使用例如溶液相、气相、淤浆相、本体相、高压工艺或其组合进行。气相聚合工艺的一个实例包含连续循环系统，其中将循环气体物流(也称作再循环物流或者流化介质)在反应器中通过聚合热而加热。通过在所述反应器外部的冷却系统将热量从所述循环气体物流移出到该循环的另一部分中。可将含有一种或多种单体的循环气体物流连续地循环通过在催化剂存在下在反应条件下的流化床。所述循环气体物流通常从所述流化床取出并且被再循环回到所述反应器中。同时，可将聚合物产物从所述反应器取出并且可添加新鲜单体以替代聚合的单体。气相工艺中的反应器温度可例如从-30℃到120℃、或者从60℃到115℃、或者从70℃到110℃、或者从70℃到95℃变化。Polymerization of propylene to form syndiotactic polypropylene can be performed using, for example, solution phase, gas phase, slurry phase, bulk phase, high pressure processes, or combinations thereof. One example of a gas phase polymerization process comprises a continuous cycle system in which a cycle gas stream (also referred to as recycle stream or fluidization medium) is heated in a reactor by the heat of polymerization. Heat is removed from the cycle gas stream to another part of the cycle by a cooling system external to the reactor. A recycle gas stream containing one or more monomers can be continuously circulated through the fluidized bed under reaction conditions in the presence of a catalyst. The recycle gas stream is typically withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product can be withdrawn from the reactor and fresh monomer can be added to replace polymerized monomer. The reactor temperature in the gas phase process may vary, for example, from -30°C to 120°C, or from 60°C to 115°C, or from 70°C to 110°C, or from 70°C to 95°C.
淤浆相工艺通常包含在添加有单体和任选的氢气、以及催化剂的液体聚合介质中形成固体的颗粒状聚合物的悬浮液。可将所述悬浮液(其可包含稀释剂)间歇地或者连续地从所述反应器除去，其中可将挥发性组分从聚合物分离并且再循环(任选地在蒸馏之后再循环)至所述反应器。聚合介质中采用的液化的稀释剂可包含例如C3-7烷烃(例如己烷或异丁烯)。所采用的介质通常在聚合条件下为液体并且是相对惰性的。本体相工艺与淤浆工艺类似。然而，工艺可为例如本体工艺、淤浆工艺或者本体淤浆工艺。Slurry phase processes generally involve forming a suspension of solid particulate polymer in a liquid polymerization medium to which monomers and optionally hydrogen, and a catalyst are added. The suspension (which may contain a diluent) can be intermittently or continuously removed from the reactor, wherein the volatile components can be separated from the polymer and recycled (optionally after distillation) to the reactor. The liquefied diluent employed in the polymerization medium may comprise, for example, aC3-7 alkane such as hexane or isobutene. The medium employed is generally liquid under the polymerization conditions and relatively inert. The bulk phase process is similar to the slurry process. However, the process may be, for example, a bulk process, a slurry process or a bulk slurry process.
优选地使用淤浆聚合来制备所述间同立构聚丙烯、优选地在淤浆环管反应器或者连续搅拌反应器中制备所述间同立构聚丙烯。如本文中使用的，术语“环管反应器”和“淤浆环管反应器”可在本文中互换地使用。可将所述环管反应器保持在例如27巴-45巴的压力和38℃-121℃的温度下。Preferably the syndiotactic polypropylene is produced using slurry polymerisation, preferably in a slurry loop reactor or in a continuous stirred reactor. As used herein, the terms "loop reactor" and "slurry loop reactor" are used interchangeably herein. The loop reactor may be maintained at, for example, a pressure of 27 bar to 45 bar and a temperature of 38°C to 121°C.
聚合可在一个反应器中或者在一序列反应器中进行。多种间同立构聚丙烯的共混物对于本发明也是合适的。Polymerization can be carried out in one reactor or in a series of reactors. Blends of various syndiotactic polypropylenes are also suitable for the present invention.
在一些实施方式中，所述管道由包括所述间同立构聚丙烯并且可进一步包括至少一种加工助剂的组合物制成。用于本发明中的合适的加工助剂的非限制性实例包含基于氟或者硅的加工助剂。In some embodiments, the pipe is made from a composition comprising the syndiotactic polypropylene and which may further comprise at least one processing aid. Non-limiting examples of suitable processing aids for use in the present invention include fluorine or silicon based processing aids.
优选的加工助剂可选自含氟聚合物，包含氟弹性体和结晶性或者半结晶性氟塑料或其共混物。将与所述间同立构聚丙烯共混的含氟聚合物可为任何含有氟的聚合物。作为一类的所述含氟聚合物可为结晶性的或者大体上无定形的。适合用于本发明中的可商购获得的加工助剂的示例包含可以如下名称获得的材料：DuPont的Viton Freeflow Z100、Viton Freeflow Z110、Viton Freeflow Z200、Viton Freeflow Z210、Viton FreeflowZ300、Viton Freeflow 10、Viton Freeflow RC；3M的Dynamar FX 5911、Dynamar FX 5912、Dynamar FX5920A、Dynamar FX 5926、Dynamar FX 5927、Dynamar FX 9613、Dynamar FX9614、Daikin的DAI-EL DA-410、DAI-EL DA-910和Solvay的Tecnoflon NM和SOLEF 11010。对于用于本发明中而言的一个合适类的含氟聚合物为由以下材料的一种或多种得到的聚合物：偏氟乙烯、六氟丙烯和四氟乙烯。Preferred processing aids may be selected from fluoropolymers, including fluoroelastomers and crystalline or semicrystalline fluoroplastics or blends thereof. The fluoropolymer to be blended with the syndiotactic polypropylene may be any fluorine-containing polymer. The fluoropolymers as a class may be crystalline or substantially amorphous. Examples of commercially available processing aids suitable for use in the present invention include materials available under the names Viton Freeflow Z100, Viton Freeflow Z110, Viton Freeflow Z200, Viton Freeflow Z210, Viton Freeflow Z300, Viton Freeflow 10, Viton Freeflow RC; 3M's Dynamar FX 5911, Dynamar FX 5912, Dynamar FX5920A, Dynamar FX 5926, Dynamar FX 5927, Dynamar FX 9613, Dynamar FX9614, Daikin's DAI-EL DA-410, DAI-EL DA-910 and Solvay's Tecnoflon NM and SOLEF 11010. One suitable class of fluoropolymers for use in the present invention are polymers derived from one or more of the following materials: vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene.
所述加工助剂可以母料或者纯净物在制造的任何阶段中(例如，在造粒、配混期间或者在管道生产线处)添加，如本领域中公知的。The processing aids can be added in masterbatch or neat at any stage of manufacture (eg, during pelletization, compounding, or at the pipeline line), as is known in the art.
例如，包括所述间同立构聚丙烯的所述组合物可包括至少50ppm的至少一种加工助剂、优选地至少100ppm、优选地至少200ppm的至少一种加工助剂、优选地基于硅或氟的加工助剂例如氟弹性体。For example, said composition comprising said syndiotactic polypropylene may comprise at least 50 ppm of at least one processing aid, preferably at least 100 ppm, preferably at least 200 ppm of at least one processing aid, preferably based on silicon or Fluorine processing aids such as fluoroelastomers.
包括所述间同立构聚丙烯的所述组合物可另外包含有效量的如本领域中已知的任何常规添加剂例如抗氧化剂、抗酸剂、润湿剂、成核剂等。The composition comprising the syndiotactic polypropylene may additionally comprise effective amounts of any conventional additives as known in the art such as antioxidants, antiacids, wetting agents, nucleating agents and the like.
优选的抗氧化剂可参见Zweifel,Hans,ISBN 354061690X,Springer-Verlag1998。优选的抗氧化剂为如以下所示的Irganox 1010和Irgafos 168。Preferred antioxidants can be found in Zweifel, Hans, ISBN 354061690X, Springer-Verlag 1998. Preferred antioxidants are Irganox 1010 and Irgafos 168 as shown below.
Irganox 1010：Irganox 1010:
Irgafos 168：Irgafos 168:
可添加硬脂酸钙作为加工助剂。所述添加剂可作为母料或者纯净物在制造的任何阶段中(例如，在造粒、配混期间或者在管道生产线处)添加，如本领域中公知的。Calcium stearate may be added as a processing aid. The additives may be added as a masterbatch or neat at any stage of manufacture (for example, during pelletization, compounding, or at the pipeline line), as is known in the art.
在一些实施方式中，用于管道的包括所述间同立构聚丙烯的所述组合物可含有其它辅助材料例如填料和/或稳定剂和/或抗静电剂和/或颜料和/或增强剂。In some embodiments, said composition comprising said syndiotactic polypropylene for pipes may contain other auxiliary materials such as fillers and/or stabilizers and/or antistatic agents and/or pigments and/or reinforcing agent.
间同立构聚丙烯与另外的聚合物的共混物也是可行的。在这样的情况下，所述另外的聚合物的比例必须低于30％重量、优选地低于10％重量、甚至更优选地低于2％重量。在可能的聚合物之中，添加小的聚乙烯含量(典型地1％重量)是优选的，因为聚乙烯起到间同立构聚丙烯的成核剂的作用。也可向所述间同立构聚丙烯添加其它成核剂。Blends of syndiotactic polypropylene with further polymers are also possible. In such cases, the proportion of the further polymer must be below 30% by weight, preferably below 10% by weight, even more preferably below 2% by weight. Among the possible polymers, the addition of small polyethylene contents (typically 1% by weight) is preferred, since polyethylene acts as a nucleating agent for syndiotactic polypropylene. Other nucleating agents may also be added to the syndiotactic polypropylene.
对于本申请的目的而言，成核剂定义为提高所述聚丙烯的结晶化温度的化合物。用于本发明中的合适的成核剂可选自技术人员已知的任何成核剂。在一些实施方式中，所述成核剂选自包括如下的组：滑石、羧酸盐、山梨醇缩醛、磷酸酯盐、取代的苯三甲酰胺和聚合物型成核剂、以及其共混物。For the purposes of this application, a nucleating agent is defined as a compound that increases the crystallization temperature of said polypropylene. Suitable nucleating agents for use in the present invention may be selected from any nucleating agent known to the skilled person. In some embodiments, the nucleating agent is selected from the group comprising talc, carboxylate salts, sorbitol acetals, phosphate ester salts, substituted benzenetricarboxamides and polymeric nucleating agents, and blends thereof thing.
合适的羧酸盐的实例包含有机羧酸盐。具体实例为苯甲酸钠和苯甲酸锂。所述有机羧酸盐还可为脂环族有机羧酸盐例如双环有机二羧酸盐和特别是双环[2.2.1]庚烷二羧酸盐。该类型的成核剂由Milliken Chemical作为HPN-68销售。合适的山梨醇缩醛的实例包含二亚苄基山梨醇(DBS)、双(对-甲基-二亚苄基山梨醇)(MDBS)、双(对-乙基-二亚苄基山梨醇)、双(3,4-二甲基-二亚苄基山梨醇)(DMDBS)、和双(4-丙基亚苄基)丙基山梨醇。双(3,4-二甲基-二亚苄基山梨醇)(DMDBS)和双(4-丙基亚苄基)丙基山梨醇是优选的。这些可例如从Milliken Chemical以Millad 3905、Millad 3940、Millad 3988和Millad NX8000的商品名获得。合适的磷酸酯盐的实例包含2,2'-亚甲基-双(4,6-二叔丁基苯基)磷酸酯的盐。这样的磷酸酯盐例如可从Asahi Denka作为NA-11或NA-21获得。合适的取代的三甲酰胺的实例包含通式(III)的化合物：Examples of suitable carboxylates include organic carboxylates. Specific examples are sodium benzoate and lithium benzoate. The organic carboxylates may also be cycloaliphatic organic carboxylates such as bicyclic organic dicarboxylates and especially bicyclo[2.2.1]heptanedicarboxylates. This type of nucleating agent is provided by Milliken Chemical as HPN-68 sales. Examples of suitable sorbitol acetals include dibenzylidene sorbitol (DBS), bis(p-methyl-dibenzylidene sorbitol) (MDBS), bis(p-ethyl-dibenzylidene sorbitol) ), bis(3,4-dimethyl-dibenzylidene sorbitol) (DMDBS), and bis(4-propylbenzylidene)propyl sorbitol. Bis(3,4-dimethyl-dibenzylidenesorbitol) (DMDBS) and bis(4-propylbenzylidene)propylsorbitol are preferred. These are available, for example, from Milliken Chemical under the tradenames Millad 3905, Millad 3940, Millad 3988 and Millad NX8000. Examples of suitable phosphate salts include salts of 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate. Such phosphate ester salts are available, for example, from Asahi Denka as NA-11 or NA-21. Examples of suitable substituted tricarboxamides include compounds of general formula (III):
其中，在式(III)的化合物中，R1、R2和R3彼此独立地选自C1-C20烷基、C5-C12环烷基、或者苯基，其各自本身又可被一个或多个C1-C20烷基、C5-C12环烷基、苯基、羟基、C1-C20烷基氨基或者C1-C20烷基氧基等取代。C1-C20烷基的实例包含甲基、乙基、正丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、1,1-二甲基丙基、1,2-二甲基丙基、3-甲基丁基、己基、庚基、辛基或1,1,3,3-四甲基丁基。C5-C12环烷基的实例包含环戊基、环己基、环辛基、环十二烷基、金刚烷基、2-甲基环己基、3-甲基环己基或2,3-二甲基环己基。在WO 03/102069中和Blomenhofer等人在Macromolecules 2005,38,3688-3695中公开了这样的成核剂。聚合物型成核剂的非限制性实例包含含有乙烯基化合物的聚合物型成核剂，例如公开于EP-A1-0152701和EP-A2-0368577中的那些。含有乙烯基化合物的聚合物型成核剂可与所述聚丙烯物理或化学共混。合适的乙烯基化合物包含具有至少6个碳原子的乙烯基环烷烃或乙烯基环烯烃例如乙烯基环戊烷、乙烯基-3-甲基环戊烷、乙烯基环己烷、乙烯基-2-甲基环己烷、乙烯基-3-甲基环己烷、乙烯基降莰烷、乙烯基环戊烯、乙烯基环己烯、乙烯基-2-甲基环己烯。聚合物型成核剂的进一步实例包含聚-3-甲基-1-丁烯、聚二甲基苯乙烯、聚硅烷和聚烷基二甲苯。这些聚合物型成核剂可通过化学或物理共混而引入到所述聚丙烯中。Wherein, in the compound of formula (III), R1, R2 and R3 are independently selected from C1 -C20 alkyl, C5 -C12 cycloalkyl, or phenyl, each of which itself can be replaced by one or Multiple C1 -C20 alkyl, C5 -C12 cycloalkyl, phenyl, hydroxyl, C1 -C20 alkylamino or C1 -C20 alkyloxy, etc. substitutions. Examples of C1 -C20 alkyl groups include methyl, ethyl, n-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 1,1-dimethylpropyl, 1,2-Dimethylpropyl, 3-methylbutyl, hexyl, heptyl, octyl or 1,1,3,3-tetramethylbutyl. Examples of C5 -C12 cycloalkyl include cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, adamantyl, 2-methylcyclohexyl, 3-methylcyclohexyl or 2,3- Dimethylcyclohexyl. Such nucleating agents are disclosed in WO 03/102069 and Blomenhofer et al. in Macromolecules 2005, 38, 3688-3695. Non-limiting examples of polymeric nucleating agents include polymeric nucleating agents containing vinyl compounds such as those disclosed in EP-A1-0152701 and EP-A2-0368577. Polymeric nucleating agents containing vinyl compounds can be physically or chemically blended with the polypropylene. Suitable vinyl compounds include vinylcycloalkanes or vinylcycloalkenes having at least 6 carbon atoms such as vinylcyclopentane, vinyl-3-methylcyclopentane, vinylcyclohexane, vinyl-2 - methylcyclohexane, vinyl-3-methylcyclohexane, vinylnorbornane, vinylcyclopentene, vinylcyclohexene, vinyl-2-methylcyclohexene. Further examples of polymeric nucleating agents include poly-3-methyl-1-butene, polydimethylstyrene, polysilanes, and polyalkylxylenes. These polymeric nucleating agents can be incorporated into the polypropylene by chemical or physical blending.
在本文中公开的实施方式中有用的其它成核剂可包含各种有机和无机成核剂例如：γ-晶形的喹吖啶酮着色剂永久红E3B“Q-Dye”；邻苯二甲酸的二钠盐；6-醌茜磺酸的铝盐；间苯二甲酸和对苯二甲酸；N',N'-二环己基-2,6-萘二甲酰胺，也称作NJStar NU-100，可得自New Japan Chemical Co.；基于松香/松脂酸(adiebetic acid)的盐的成核剂；单甘油锌(II)；如在美国专利No.6,235,823中公开的基于二酰胺化合物的成核剂，例如N-环己基-4-(N-环己基羰基氨基)苯甲酰胺和N,N'-1,4-环己烷-双-苯甲酰胺；基于苯均三酸衍生物的成核剂，例如在WO 02/46300、WO 03/102069、WO 2004/072168中公开的，其包含例如1,3,5-苯三羧酸三(环戊基酰胺)、1,3,5-苯三羧酸三(环己基酰胺)、和1,3,5-苯三羧酸三(叔丁基)酰胺。Other nucleating agents useful in the embodiments disclosed herein may include various organic and inorganic nucleating agents such as: quinacridone colorant Permanent Red E3B "Q-Dye" in gamma-crystalline form; Disodium salt; aluminum salt of 6-quininizarin sulfonic acid; isophthalic and terephthalic acids; N',N'-dicyclohexyl-2,6-naphthalene dicarboxamide, also known as NJStar NU-100 , available from New Japan Chemical Co.; rosin/adiebetic acid based nucleating agent; zinc(II) monoglycerol; diamide compound based nucleating agent as disclosed in U.S. Patent No. 6,235,823 agents such as N-cyclohexyl-4-(N-cyclohexylcarbonylamino)benzamide and N,N'-1,4-cyclohexane-bis-benzamide; synthetic compounds based on trimesic acid derivatives Nucleating agents, such as those disclosed in WO 02/46300, WO 03/102069, WO 2004/072168, comprising for example 1,3,5-benzenetricarboxylic acid tris(cyclopentylamide), 1,3,5- Benzenetricarboxylic acid tris(cyclohexylamide), and 1,3,5-benzenetricarboxylic acid tris(tert-butyl)amide.
所述成核剂可以粉末、粒料、液体、其它通常可用的形式、或者其组合使用以与聚丙烯掺混(熔融共混)。在另外的实施方式中，所述成核剂可与聚丙烯配混以形成成核用添加剂母料来与聚丙烯掺混(熔融共混)。包含根据本文中公开的实施方式的聚丙烯(一种或多种)和成核剂(一种或多种)的组合物可通过如下制备：将各个组分在所述共混物组分的一种或多种的熔点温度附近或以上的温度下混合或捏合。可采用能够达到期望的温度并且将所述混合物熔融塑化的典型的聚合物混合或捏合设备。这些包含磨机、捏合机、挤出机(单螺杆和双螺杆两者)、混合器、压延机等。混合顺序和方法可取决于最终组合物(组成)以及起始组分的形式(粉末、粒料、母料等)。The nucleating agent may be used in powder, pellet, liquid, other commonly available forms, or combinations thereof for blending (melt blending) with polypropylene. In other embodiments, the nucleating agent may be compounded with polypropylene to form a nucleating additive masterbatch for blending (melt blending) with polypropylene. Compositions comprising polypropylene(s) and nucleating agent(s) according to embodiments disclosed herein may be prepared by incorporating the individual components in the blend components Mixing or kneading at a temperature near or above the melting point temperature of one or more of them. Typical polymer mixing or kneading equipment capable of achieving the desired temperature and melt plasticizing the mixture can be used. These include mills, kneaders, extruders (both single and twin screw), Mixers, calenders, etc. The order and method of mixing may depend on the final composition (composition) as well as the form of the starting components (powder, pellets, masterbatch, etc.).
在一些优选实施方式中，包括所述间同立构聚丙烯的所述组合物可包括颜料。所述颜料的具体颜色可取决于将在所述管道中输送的流体(水或气体)以及国家(取决于强制施行的法规)。In some preferred embodiments, said composition comprising said syndiotactic polypropylene may comprise a pigment. The specific color of the pigment may depend on the fluid (water or gas) to be transported in the pipeline and on the country (depending on the regulations enforced).
用于根据本发明的管道的包括所述间同立构聚丙烯的所述组合物可含有例如最高达40％重量的填料和/或0.01％-2.5％重量的稳定剂和/或0.1％-1％重量的抗静电剂和/或0.2％-3％重量的颜料和/或0.2％-3％重量的增强剂，在各情况下基于所述间同立构聚丙烯的总重量。Said composition comprising said syndiotactic polypropylene for pipes according to the invention may contain, for example, up to 40% by weight of fillers and/or 0.01% to 2.5% by weight of stabilizers and/or 0.1% to 1% by weight of antistatic agent and/or 0.2% to 3% by weight of pigment and/or 0.2% to 3% by weight of reinforcing agent, based in each case on the total weight of the syndiotactic polypropylene.
根据本发明的管道可根据本领域中已知的方法制造。根据第二方面，本发明还涵盖用于制造根据第一方面的管道的工艺，其包括如下步骤：Pipes according to the invention can be manufactured according to methods known in the art. According to a second aspect, the present invention also covers a process for manufacturing a pipe according to the first aspect, comprising the steps of:
(a)将包括所述间同立构聚丙烯的组合物挤出为管道；(a) extruding a composition comprising said syndiotactic polypropylene into a pipe;
(b)将步骤(a)中形成的管道冷却；和(b) cooling the tube formed in step (a); and
(c)任选地将步骤(a)中形成的管道加热/退火。(c) optionally heating/annealing the tube formed in step (a).
挤出步骤(a)可在至少150℃的温度下进行。例如挤出步骤(a)可在范围为至少150℃-至多250℃、优选地至少160℃-至多230℃的温度下进行。在一些实施方式中，步骤(a)包括首先将所述间同立构聚丙烯组合物在挤出机中例如在至少150℃-至多250℃的温度下塑化，然后将其通过环模头挤出为期望的内径。The extrusion step (a) may be carried out at a temperature of at least 150°C. For example extrusion step (a) may be carried out at a temperature in the range of at least 150°C to at most 250°C, preferably at least 160°C to at most 230°C. In some embodiments, step (a) comprises first plasticizing the syndiotactic polypropylene composition in an extruder, for example at a temperature of at least 150°C to at most 250°C, and then passing it through a ring die Extrude to desired inner diameter.
用于制造根据本发明的管道的挤出机可为单螺杆挤出机、或双螺杆挤出机、或均化用挤出机(单螺杆或双螺杆)的挤出机级联。为了由绒毛制造粒料(在均化和引入所述添加剂时)，可使用单螺杆挤出机(优选地具有20-40的L/D)，或者使用双螺杆挤出机(优选地具有20-40的L/D)，优选地使用挤出机级联。在一些实施方式中，在挤出期间使用超临界CO2或水以帮助均化。可考虑多种变型，例如使用超临界CO2来帮助均化、在挤出期间使用水。任选地，可另外在挤出机和环模头之间使用熔体泵和/或静态混合器。具有范围为大约16-2000mm和甚至更大的直径的环状模头是可能的。The extruder used to manufacture the pipe according to the invention may be a single-screw extruder, or a twin-screw extruder, or an extruder cascade of homogenizing extruders (single-screw or twin-screw). For the manufacture of pellets from fluff (while homogenizing and introducing the additives), a single screw extruder (preferably with an L/D of 20-40) or a twin screw extruder (preferably with 20 -40 L/D), preferably using a cascade of extruders. In some embodiments, supercriticalCO2 or water is used during extrusion to aid in homogenization. Variations can be considered such as using supercriticalCO2 to aid homogenization, using water during extrusion. Optionally, a melt pump and/or a static mixer can additionally be used between the extruder and the ring die. Annular dies with diameters ranging from about 16-2000mm and even larger are possible.
来自挤出机的熔体可首先经由以锥形方式排列的孔分布在环状横截面上面，然后经由盘管(coil)分布器或者筛子进料至芯/模头组合。如果必要，可另外在模头出口之前安装用于保证均匀的熔体流动的限流环或者其它结构元件。The melt from the extruder can first be distributed over the annular cross-section via holes arranged in a conical manner, and then fed to the core/die combination via a coil distributor or a screen. If necessary, restrictor rings or other structural elements for ensuring uniform melt flow can additionally be installed before the die outlet.
在离开环模头之后，可将管道脱离到校准芯轴上面。一旦管道已经被形成为期望的直径和厚度，则步骤(b)管道的冷却发生。管道的冷却可通过空气冷却和/或通过水冷却进行、任选地还具有内部水冷却。After exiting the ring die, the pipe can be detached onto the calibration mandrel. Once the pipe has been formed to the desired diameter and thickness, step (b) cooling of the pipe occurs. The cooling of the pipes can be carried out by air cooling and/or by water cooling, optionally also with internal water cooling.
在冷却之后，可使管道任选地经历加热/退火步骤(c)。所述加热/退火步骤可在烘箱、或者任何其它合适的设备中进行确定长度的时间；所述工艺(过程)在本领域中称作热退火。在一些实施方式中，使管道经历在至少60℃的温度下的热退火。在一些实施方式中，使管道经历在至少60℃-至多120℃的温度下；优选地在至少70℃-至多110℃的温度下；更优选地在至少75℃-至多90℃的温度下的热退火。在一些实施方式中，使管道经历热退火至少3天。在一些实施方式中，使管道经历热退火至少3天-至多20天、例如至多14天；优选地至少4天-至多12天；更优选地至少5天-至多10天；最优选地至少6天-至多8天。After cooling, the pipe may optionally be subjected to a heating/annealing step (c). The heating/annealing step may be performed for a defined length of time in an oven, or any other suitable device; the process (process) is known in the art as thermal annealing. In some embodiments, the tubing is subjected to thermal annealing at a temperature of at least 60°C. In some embodiments, the pipeline is subjected to temperature at least 60°C to at most 120°C; preferably at least 70°C to at most 110°C; more preferably at least 75°C to at most 90°C thermal annealing. In some embodiments, the tubing is subjected to thermal annealing for at least 3 days. In some embodiments, the pipeline is subjected to thermal annealing for at least 3 days to at most 20 days, such as at most 14 days; preferably at least 4 days to at most 12 days; more preferably at least 5 days to at most 10 days; most preferably at least 6 days days - up to 8 days.
在一些实施方式中，使管道经历在至少70℃-至多120℃的温度下的热退火至少3天-至多14天。In some embodiments, the tubing is subjected to thermal annealing at a temperature of at least 70°C to at most 120°C for at least 3 days to at most 14 days.
根据本发明的管道令人惊讶地显示出改善的机械性质和/或强度。在一些实施方式中，根据本发明的管道具有如通过在23℃下的ISO 180-缺口悬臂梁试验测定的至少20kJ/m2；优选地至少30kJ/m2；优选地至少35kJ/m2；优选地至少38kJ/m2；优选地至少40kJ/m2；优选地至多45kJ/m2的抗冲击性。The pipes according to the invention surprisingly exhibit improved mechanical properties and/or strength. In some embodiments,the pipe according to the invention has at least 20 kJ/m 2 ; preferably at least 30 kJ/m 2; preferably at least 35 kJ/m2 , as determined by the ISO 180-notched Izod test at 23°C; Preferably an impact resistance of at least 38 kJ/m2 ; preferably at least 40 kJ/m2 ; preferably at most 45 kJ/m2 .
根据本发明的管道令人惊讶地显示出改善的柔性性质，如根据ISO 178通过其挠曲模量度量的。在一些实施方式中，根据本发明的管道具有小于1000MPa；优选地小于900MPa；优选地小于800MPa；优选地小于700MPa；优选地小于600MPa；更优选地小于500MPa的挠曲模量。The pipe according to the invention surprisingly exhibits improved flexibility properties, as measured by its flexural modulus according to ISO 178. In some embodiments, pipes according to the invention have a flexural modulus of less than 1000 MPa; preferably less than 900 MPa; preferably less than 800 MPa; preferably less than 700 MPa; preferably less than 600 MPa; more preferably less than 500 MPa.
在一些实施方式中，根据本发明的管道通常具有使得它们可被归于的根据ISO/TR9080标准的最小要求强度(MRS)等级(MRS 10等级)(对于PE100树脂)的抗蠕变性。该等级是根据统计方法测定的并且最小要求强度MRS定义为在97.5％置信区间下的所分类的预测下限(LPL)。In some embodiments, pipes according to the invention generally have a creep resistance such that they can be assigned a minimum required strength (MRS) grade (MRS 10 grade) (for PE100 resin) according to the ISO/TR9080 standard. The ratings are determined according to statistical methods and the minimum required strength MRS is defined as the lower prediction limit (LPL) of the class at the 97.5% confidence interval.
在一些实施方式中，根据本发明的管道通常具有外推的50℃/50年至少7.0MPa的应力。In some embodiments, pipes according to the invention typically have an extrapolated 50°C/50 year stress of at least 7.0 MPa.
根据本发明的管道具有优异的拉伸强度、模量和抗冲击性，并且具有杰出的透明性，并且可透明到足以在不向所述管道添加单独的澄清剂的情况下使用。The pipe according to the present invention has excellent tensile strength, modulus, and impact resistance, and has excellent transparency, and is transparent enough to be used without adding a separate clarifying agent to the pipe.
根据第三方面，本发明提供根据第一方面的和/或根据第二方面制造的管道用于输送处于压力下的流体的用途。根据本发明的管道非常适合于输送处于压力下的流体例如水和气体。它们可在非常宽的温度范围内使用。According to a third aspect, the invention provides the use of a pipe according to the first aspect and/or manufactured according to the second aspect for conveying a fluid under pressure. The pipe according to the invention is very suitable for conveying fluids under pressure such as water and gas. They can be used over a very wide temperature range.
根据本发明的管道还适合于在制药、化学和食品生产工业中输送流体。The pipe according to the invention is also suitable for conveying fluids in the pharmaceutical, chemical and food production industries.
本发明还涵盖根据第一方面的和/或根据第二方面制造的管道用于制造医用制品的用途。优选的制品为需要透视性能的那些。最优选的制品具有约2mm或更小的壁厚，例如采血管、离心管、培养瓶、注射器塞和筒等。The invention also covers the use of the tubing according to the first aspect and/or manufactured according to the second aspect for the manufacture of a medical article. Preferred articles are those requiring see-through properties. Most preferred articles have a wall thickness of about 2 mm or less, such as blood collection tubes, centrifuge tubes, culture bottles, syringe stoppers and barrels, and the like.
通过以下实施例说明本发明，但是本发明不受以下实施例限制。The invention is illustrated by the following examples, but the invention is not limited by the following examples.
实施例Example
试验方法：experiment method:
除非另有说明，否则密度是根据标准ASTM D-1505的方法在23℃下测量的。Unless otherwise stated, density is measured at 23°C according to the method of standard ASTM D-1505.
蠕变实验在两个不同的蠕变试验设备上进行(表2)。将间同立构聚丙烯(sPP)通过压缩而模塑成2mm厚片材，然后在所述片材中取样ISO527 5A型拉伸样条。将所述样品在恒定温度(用水浴或腔室实现)下插入蠕变机的夹具中，并且向所述样品施加负荷。对于各样品，记录破坏(变形或断裂)时间。Creep experiments were performed on two different creep test equipment (Table 2). Syndiotactic polypropylene (sPP) was molded by compression into 2 mm thick sheets, from which ISO527 type 5A tensile specimens were then sampled. The sample is inserted into the grips of a creep machine at a constant temperature (achieved with a water bath or chamber), and a load is applied to the sample. For each sample, the failure (deformation or fracture) time was recorded.
用于表征管道柔性的挠曲试验是由ISO 178三点弯曲试验修改而来的。唯一区别是，聚合物样品被40cm管道段(直径32mm-SDR 11)代替。将所述管道段引入到Zwick型1445机器中，在三点弯曲试验的中央(跨度＝200mm)。在试验期间，将力施加在所述跨度的中央处，其也对应于所述管道段的中央。试验的具体条件是(如果未提及试验的参数或者条件，则这意味着该值与对于基于ISO 178三点弯曲试验测量聚合物样品的挠曲模量而言所施加的值相同)：The flex test used to characterize the flexibility of pipes is a modification of the ISO 178 three-point bend test. The only difference is that the polymer sample is replaced by a 40cm pipe section (32mm diameter - SDR 11). The pipe section was introduced into a Zwick type 1445 machine at the center of a three-point bending test (span = 200 mm). During the test, a force is applied at the center of the span, which also corresponds to the center of the pipe segment. The specific conditions of the test are (if no parameters or conditions of the test are mentioned, this means that the values are the same as those applied for the measurement of the flexural modulus of polymer samples based on the ISO 178 three-point bending test):
-负荷(负载，loading)边缘的半径：10mm- Radius of the edge of the load: 10mm
-支撑体的半径：5mm- Radius of the support body: 5mm
-预先加载(pre-charge)：5N- Pre-charge: 5N
-测试速度：1mm/min-Test speed: 1mm/min
-温度：23℃-Temperature: 23°C
记录作为伸长率函数的力。力越低，则管道越柔性。Record the force as a function of elongation. The lower the force, the more flexible the pipe.
用使用铟作为标准物校准的Perkin-Elmer Pyris Diamond差示扫描量热仪(DSC)分析聚合物粒料或管道的热性质。将试样(取自所述聚合物粒料或者所述管道的2mg-10mg样品)以20℃/min的速率从-50℃加热至220℃，之后等温3min，随后为以-20℃/min的速率至-50℃的冷却扫描，之后等温3min，然后以20℃/min重新加热至220℃。在该第二次加热过程期间测量熔融温度(Tm)，其对应于在峰的最大值处的温度。The thermal properties of the polymer pellets or tubing were analyzed with a Perkin-Elmer Pyris Diamond Differential Scanning Calorimeter (DSC) calibrated using indium as a standard. The sample (2mg-10mg sample taken from the polymer pellet or the pipe) was heated from -50°C to 220°C at a rate of 20°C/min, followed by isothermal for 3min, followed by heating at -20°C/min Cooling sweep at -50°C at a rate of 0°C, followed by isothermal for 3 min and then reheated to 220°C at 20°C/min. The melting temperature (Tm), which corresponds to the temperature at the maximum of the peak, is measured during this second heating process.
环向应力试验是根据ISO 1167:1996(E)进行的。The hoop stress test is carried out according to ISO 1167:1996(E).
实施例1Example 1
通过使用1251(由茂金属催化的间同立构聚丙烯均聚物，其具有如使用13C-NMR测量的75％的间同立构指数，可从Total Petrochemicals USA,Inc.商购获得，性质示于表1中)在50℃下压缩模塑而制备ISO 527型5A拉伸样条。在进行蠕变实验之前，将这些拉伸样条在简单的炉子中在60℃下持续陈化3天。by using 1251 (a metallocene-catalyzed syndiotactic polypropylene homopolymer having a syndiotactic index of 75% as measured using13 C-NMR, commercially available from Total Petrochemicals USA, Inc., properties shown In Table 1) ISO 527 Type 5A tensile specimens were prepared by compression molding at 50°C. These tensile specimens were continuously aged at 60 °C for 3 days in a simple oven before creep experiments.
表1Table 1
蠕变实验在图1中所示的水浴中并且如表2中所列那样进行。Creep experiments were performed in the water bath shown in Figure 1 and as listed in Table 2.
表2Table 2
试验如下运行：向贯穿整个试验保持在50℃的恒定温度下的拉伸样条施加稳定的拉伸负荷，随时间测量样品的变形(伸长率)，直至发生样品的破坏；将所得的时间对％伸长率的数据作图。The test was run as follows: a steady tensile load was applied to a tensile specimen kept at a constant temperature of 50°C throughout the test, and the deformation (elongation) of the sample was measured over time until failure of the sample occurred; the resulting time Data are plotted against % elongation.
图2显示当施加8.5MPa的恒定应力时获得的蠕变曲线。在试验开始时，样品的变形急剧地发生；然而，变形速度逐渐变慢直至达到恒定的变形速率(曲线的中间部分)，随后发生拉伸样条的缩颈(曲线的拐点)，这意味着已经达到样品的屈服强度(该屈服对应于所述聚合物的可逆弹性区与不可逆塑性区之间的界限)。蠕变曲线的拐点是通过使用Matlab软件如本文中所描述的那样数学拟合而测定的。引入变形ε(在ε＝20％和50％之间)的时间演变作为统计中的“数据”。该依赖性已经被使用以下方程拟合：Figure 2 shows the creep curves obtained when a constant stress of 8.5 MPa was applied. At the beginning of the test, deformation of the specimen occurs sharply; however, the deformation rate gradually slows down until a constant deformation rate is reached (middle part of the curve), followed by necking of the tensile spline (inflection point of the curve), which means that The yield strength of the sample has been reached (the yield corresponds to the boundary between the reversible elastic and irreversible plastic regions of the polymer). The inflection point of the creep curve was determined by mathematical fitting using Matlab software as described herein. The temporal evolution of the deformation ε (between ε=20% and 50%) is introduced as "data" in the statistics. This dependence has been fitted using the following equation:
ε(t)＝x(1)*exp(x(2)*(t-x(3)))+x(4)*t+x(5)-x(6)*exp(-x(7)*(t-x(8)))。ε(t)=x(1)*exp(x(2)*(t-x(3)))+x(4)*t+x(5)-x(6)*exp(-x(7)* (t-x(8))).
其中x(i)是高度可自由调整参数。本质上，该方程含有Burger模型加上指数项(用于描述在高的变形/时间下的时间演变)。此外，其未强制(0,0)点(实际上，(0,0)坐标附近的小的波动容许将由于应力所施加的方式而引起的一些实验误差考虑进来)。where x(i) is a freely adjustable parameter of height. Essentially, the equation contains the Burger model plus an exponential term (for describing the time evolution at high deformation/time). Also, it does not enforce a (0,0) point (actually, small fluctuations around the (0,0) coordinate allow for some experimental error due to the way the stress is applied).
一旦确定x(i)参数，则经由作为时间函数的伸长率函数的二阶导数的环化(annulation)而分析地计算拐点。Once the x(i) parameter is determined, the point of inflection is calculated analytically via annulation of the second derivative of the elongation function as a function of time.
在图2的具体情况下，拐点在试验开始之后1047h出现，并且所记录的伸长率为35.5％。In the particular case of Figure 2, the point of inflection occurred 1047 h after the start of the test, and an elongation of 35.5% was recorded.
表3显示在将所获得的蠕变曲线进行数学拟合之后获得的平均拐点时间和相应的伸长率。Table 3 shows the average inflection point times and corresponding elongations obtained after mathematical fitting of the obtained creep curves.
表3table 3
图3显示在50℃下在多种恒定应力下进行的蠕变试验的拐点的伸长率。Figure 3 shows the elongation at the inflection point of creep tests performed at 50°C at various constant stresses.
对比例1Comparative example 1
对使用XT10N(聚乙烯PE100，可从Total Petrochemicals USA Inc商购获得，密度0.949g/cm3(ASTM D-792)，熔体指数7.5g/10min(21.6kg-190℃ASTM D-1238)和RA130E-8427(聚丙烯无规共聚物，由Borealis A/S提供，密度0.905g/cm3(ISO 1183)，MI2 0.25g/10min(230℃/2.16kg ISO 1133))通过在50℃下压缩模塑而制备的ISO 527型5A拉伸样条进行如实施例1中描述的蠕变试验。to use XT10N (polyethylene PE100, commercially available from Total Petrochemicals USA Inc, density 0.949 g/cm3 (ASTM D-792), melt index 7.5 g/10 min (21.6 kg-190 °C ASTM D-1238) and RA130E- 8427 (polypropylene random copolymer supplied by Borealis A/S, density 0.905g/cm3 (ISO 1183), MI2 0.25g/10min (230°C/2.16kg ISO 1133)) by compression molding at 50°C The ISO 527 Type 5A tensile bars prepared were then subjected to creep tests as described in Example 1.
图4显示对于实施例1和对比例1的样品两者，平均拐点时间对所施加应力的图。由该图可确定，用间同立构聚丙烯制成的拉伸样条可经受与用聚乙烯(XT10N)制成的拉伸样条一样大(或者更高的)应力。图4进一步显示实施例1中试验的间同立构聚丙烯(1251)的所得回归曲线(和方程)；基于该曲线外推至50年得到了约8MPa的耐压性。FIG. 4 shows a plot of the average time to inflection point versus applied stress for both the samples of Example 1 and Comparative Example 1. FIG. From this figure it can be determined that tensile splines made of syndiotactic polypropylene can withstand the same conditions as those made of polyethylene ( XT10N) made of tensile splines as large (or higher) stress. Figure 4 further shows the syndiotactic polypropylene tested in Example 1 ( 1251) from the resulting regression curve (and equation); extrapolation to 50 years based on this curve yields a pressure resistance of about 8 MPa.
测量实施例1中获得的拉伸样条和XT10N样条的挠曲模量和抗冲击性。抗冲击性是使用在23℃下的ISO 180-缺口悬臂梁试验测量的。结果示于表5中。Measuring the stretched splines obtained in Example 1 and Flexural modulus and impact resistance of XT10N splines. Impact resistance is measured using the ISO 180-notched Izod test at 23°C. The results are shown in Table 5.
表5table 5
实施例2Example 2
将1251(间同立构聚丙烯，由Total Petrochemicals USA,Inc.提供，性质示于实施例1中)在具有70mm直径并且L/D＝25的单螺杆挤出机(Reifenhauser)上挤出。生产量在范围15-20kg/h内。使用25mm模头以使熔融的聚合物符合32mm的最终直径。然后，使用32mm校准器来制造管道(图5显示在模头出口处和在校准器中的入口之前的熔融聚合物的照片)。于在水浴(10-15℃)内冷却之后，以容许管道的壁的最终厚度为～2mm的速率对管道进行缓慢牵引。表6显示用于制造管道的加工参数。管道1是由1251和1％重量的HD6081(高密度聚乙烯，由TOTAL Petrochemicals提供)的干混混合物挤出的，而管道2-6是由100％1251挤出的。管道1比由纯sPP制造的管道略白。在越高的熔体温度下制造的管道具有越光滑的外表面。Will 1251 (syndiotactic polypropylene supplied by Total Petrochemicals USA, Inc., properties shown in Example 1) was extruded on a single screw extruder (Reifenhauser) with a diameter of 70 mm and L/D=25. Throughput is in the range 15-20kg/h. A 25mm die was used to conform the molten polymer to a final diameter of 32mm. Then, a 32 mm calibrator was used to make the pipe (Figure 5 shows a photograph of the molten polymer at the exit of the die and before the entry in the calibrator). After cooling in a water bath (10-15°C), the tubing was pulled slowly at a rate that allowed the final thickness of the tubing's wall to be ~2mm. Table 6 shows the processing parameters used to make the pipes. Pipeline 1 is composed of 1251 and 1% by weight of HD6081 (high density polyethylene, provided by TOTAL Petrochemicals) dry blend extruded, while pipes 2-6 are made of 100% 1251 extruded. Pipe 1 is slightly whiter than the pipe made from pure sPP. Tubes produced at higher melt temperatures have smoother outer surfaces.
表6Table 6
根据ISO 178测量所得管道的挠曲模量并且其令人惊讶地对于所有所试验的管道都是低的(～450MPa)。The flexural modulus of the resulting pipes was measured according to ISO 178 and was surprisingly low (-450 MPa) for all pipes tested.
评价sPP的陈化条件。The aging conditions of the sPP were evaluated.
图6显示sPP管道2的内表面和外表面的DSC温谱图。外表面(由于管道的骤冷而)没有时间来结晶化，并且因此，DSC温谱图(标记为“外”)仅在125℃附近呈现出一个尖锐的熔融峰。内表面有时间来结晶化，并且其DSC温谱图(标记为“内”)呈现两个明显的熔融峰(～113℃和125℃)。因此，管道的内部具有更稳定的微晶结构。FIG. 6 shows the DSC thermograms of the inner and outer surfaces of the sPP pipe 2 . The outer surface (due to the quenching of the tube) did not have time to crystallize, and therefore, the DSC thermogram (labeled "outer") only exhibited a sharp melting peak around 125°C. The inner surface had time to crystallize and its DSC thermogram (labeled "inner") exhibited two distinct melting peaks (-113°C and 125°C). Therefore, the interior of the pipe has a more stable microcrystalline structure.
表7显示来自在不同挤出温度下制造的管道的DSC温谱图的数据。该数据显示，随着挤出温度升高，冷却速率也升高，并且在110℃与120℃之间中出现的sPP形式具有“低”熔融峰(～110℃)的逐渐消失。用1％HD6081制备的管道(管道1)提供具有最大的低熔融峰(～115℃)的温谱图，表明HD6081在辅助sPP的结晶化方面的效果。Table 7 shows data from DSC thermograms of pipes made at different extrusion temperatures. The data show that as the extrusion temperature increases, so does the cooling rate, and that the sPP form that occurs between 110°C and 120°C has a gradual disappearance of the "low" melting peak (~110°C). The pipe prepared with 1% HD6081 (pipe 1) provided a thermogram with the largest low melting peak (-115°C), indicating the effect of HD6081 in assisting the crystallization of sPP.
表7Table 7
在另一实验中，将一块sPP管道2置于设置在80℃的恒定温度下的烘箱内。以有规律的间隔切下所述管道的一小部分以通过DSC进行分析。图7显示所记录的管道内部的温谱图，而图8显示所记录的管道外部的温谱图。熔融峰的相对强度容许确定，在80℃下持续退火3天对于使管道中在内表面和外表面两者上的sPP微观结构进一步稳定化是有用的。In another experiment, a piece of sPP pipe 2 was placed in an oven set at a constant temperature of 80°C. Small sections of the tubing were cut at regular intervals for analysis by DSC. Figure 7 shows the recorded thermogram inside the pipeline, while Figure 8 shows the recorded thermogram outside the pipeline. The relative intensity of the melting peaks allowed it to be determined that continuous annealing at 80°C for 3 days was useful to further stabilize the sPP microstructure in the pipe on both the inner and outer surfaces.
将管道1、2和6在烘箱中在80℃下持续放置14天，该时间之后进行DSC分析。表8汇总了“低”温熔融峰的部分面积(部分区域，partial area)的百分比和总熔融焓。在不同挤出温度下制造，然后在80℃下持续退火14天的sPP管道的DSC温谱图示于图9-11中。图9显示对于管道1(sPP+1％HD6081，在160℃下)获得的DSC温谱图，图10显示对于管道2(纯sPP，在170℃下)获得的DSC温谱图，和图11显示对于管道6(纯sPP，在220℃下)获得的DSC温谱图。对于所有样品，总熔融焓从～29J/g升高至～39J/g。管道1的温谱图(图9)显示，两个熔融峰具有几乎相同的相对强度。所述部分面积的积分估计为约70％。在退火步骤之后，管道2的DSC温谱图(图10)和管道6的DSC温谱图(图11)几乎相同，表明在退火期间它们的微观结构已经演变而产生稳定且相当的(equivalent)结晶状态。Tubes 1, 2 and 6 were placed in an oven at 80°C for 14 days, after which time DSC analysis was performed. Table 8 summarizes the percentage of partial area and total melting enthalpy of the "low" temperature melting peak. The DSC thermograms of sPP pipes fabricated at different extrusion temperatures followed by continuous annealing at 80 °C for 14 days are shown in Figures 9-11. Figure 9 shows the DSC thermogram obtained for pipeline 1 (sPP + 1% HD6081 at 160°C), Figure 10 shows the DSC thermogram obtained for pipeline 2 (pure sPP at 170°C), and Figure 11 The DSC thermogram obtained for pipeline 6 (pure sPP at 220°C) is shown. The total melting enthalpy increased from -29 J/g to -39 J/g for all samples. The thermogram of Pipeline 1 (Figure 9) shows that the two melting peaks have almost the same relative intensity. The integral of the partial area is estimated to be about 70%. After the annealing step, the DSC thermograms of Pipeline 2 (Figure 10) and Pipeline 6 (Figure 11) are nearly identical, indicating that their microstructures have evolved during the annealing to produce stable and equivalent crystalline state.
表8Table 8
使管道1和2经历在80℃下的退火步骤7天，然后对所制造的管道进行在20℃的温度下的环向应力试验。结果示于表9中。Pipes 1 and 2 were subjected to an annealing step at 80°C for 7 days, after which the fabricated pipes were subjected to a hoop stress test at a temperature of 20°C. The results are shown in Table 9.
表9Table 9
对比例2Comparative example 2
使用XT10N(PE100，可从Total Petrochemicals USA Inc商购获得，密度0.949g/cm3(ASTM D-792)，熔体指数7.5g/10min(21.6kg，190℃，ASTM D-1238)制造具有32mm直径的管道。使用RA130E-8427(聚丙烯无规共聚物，可从Borealis A/S商购获得，密度0.905g/cm3(ISO 1183)，MI2 0.25g/10min(230℃/2.16kg ISO 1133))制造具有32mm直径的管道。使用MDPE 3802(PE80聚乙烯，可从TOTAL Refining&Chemicals商购获得，密度0.938g/cm3(ISO 1183)，MI2 20g/10min(230℃/21.6kg ISO 1133-G))制造具有32mm直径的管道。所述各管道是使用45mm模头制造的以使熔融的聚合物符合最终的32mm直径。使所述管道经历在80℃下的退火步骤7天。use XT10N (PE100, commercially available from Total Petrochemicals USA Inc, density 0.949 g/cm3 (ASTM D-792), melt index 7.5 g/10 min (21.6 kg, 190° C., ASTM D-1238) manufactured with a diameter of 32 mm RA130E-8427 (polypropylene random copolymer commercially available from Borealis A/S, density 0.905g/cm3 (ISO 1183), MI2 0.25g/10min (230°C/2.16kg ISO 1133) was used ) to make a pipe with a diameter of 32mm. Using MDPE 3802 (PE80 polyethylene, commercially available from TOTAL Refining & Chemicals, density 0.938g/cm3 (ISO 1183), MI2 20g/10min (230°C/21.6kg ISO 1133-G) ) to produce pipes with a diameter of 32 mm. The pipes were manufactured using a 45 mm die to conform the molten polymer to a final 32 mm diameter. The pipes were subjected to an annealing step at 80° C. for 7 days.
根据ISO 178测量所得管道的挠曲模量(1100-1300MPa)。包括sPP的管道比包括全同立构聚丙烯的管道柔性。The flexural modulus of the resulting pipes was measured according to ISO 178 (1100-1300 MPa). Pipes comprising sPP are more flexible than pipes comprising isotactic polypropylene.
对所制造的管道进行在20℃下的环向应力试验。图12显示对于在实施例2中制造的管道(管道5)和对于在对比例2中试验的管道，破坏时间对所施加的环向应力的图。由该图可确定，在20℃的温度下，用间同立构聚丙烯(1251)制成的管道可经受与用聚乙烯(XT10N，MDPE3802)制成的管道一样大(或者更高的)应力。A hoop stress test at 20° C. was performed on the fabricated pipes. Figure 12 shows a graph of time to failure versus applied hoop stress for the pipe manufactured in Example 2 (pipe 5) and for the pipe tested in Comparative Example 2. It can be determined from this figure that at a temperature of 20°C, syndiotactic polypropylene ( 1251) made of pipes can withstand the use of polyethylene ( XT10N, MDPE3802) made of pipes as large (or higher) stress.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP16151161 | 2016-01-13 | ||
| EP16151161.3 | 2016-01-13 | ||
| PCT/EP2017/050474WO2017121756A1 (en) | 2016-01-13 | 2017-01-11 | Pipes comprising syndiotactic polypropylene |
| Publication Number | Publication Date |
|---|---|
| CN108473622Atrue CN108473622A (en) | 2018-08-31 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780005805.7APendingCN108473622A (en) | 2016-01-13 | 2017-01-11 | Pipes comprising syndiotactic polypropylene |
| Country | Link |
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| JP (1) | JP2019503417A (en) |
| KR (1) | KR20180102577A (en) |
| CN (1) | CN108473622A (en) |
| WO (1) | WO2017121756A1 (en) |
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| WD01 | Invention patent application deemed withdrawn after publication | Application publication date:20180831 | |
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