CN102453245A - Polyester and preparation method thereof - Google Patents

Abstract

The invention provides a novel polyester and a preparation method thereof; the novel polyester is prepared by self-condensation of monomers with the structure shown in formula 1,

formula 1 wherein R₁Is C₁-C₂₀Alkyl or C₆-C₂₀The aromatic group of (1). The polyester has good heat resistance and crystallinity, and can reach the content of carbon from biological sources of more than 35 percent.

Description

A kind of polyester and preparation method thereof

Technical field

The present invention relates to a kind of new polyester and preparation method thereof.

Background technology

Along with current industrial development, be that raw material synthetic polyester material is ubiquitous in the mankind's life with the oil, also increasing to the demand of polyester material, cause that thus petroleum-based energy is gradually exhausted, demand and oil price continue to rise; Use oil as a large amount of CO in the production process of raw material and in final discarded simultaneously₂Discharging caused global warming, a series of environmental problems such as white pollution, environmental stress is heavy day by day, the direct threats human existence.Therefore in the whole world under the demand of Green Chemistry, low-carbon economy, bioenergy is shown one's talent, and how to utilize organism-based raw material research and development low toxicity, oligosaprobicly can reduce the destructive novel material to environment, is one of research problem of facing of people.

People have utilized renewable biological source to develop multiple polymers raw materials for production product and multiple new polymers at present.For example E.I.Du Pont Company through biology and chemical process, prepares 1 through corn is fermented, 3-PDO, and developed and contain that the 36wt% that has an appointment derives from biomaterial but not the PTT (PPT) of oil material.Natureworks company is raw material equally with farm crop, through biology and chemical process, has produced pure biogenetic derivation and has been easy to biodegradable POLYACTIC ACID (PLA) polymkeric substance.Utilize 1 among the Chinese patent CN101643946A, 2-Ucar 35 and terephthalic acid have synthesized high-molecular weight poly terephthalic acid 1, the 2-propylene glycol ester, and this molecular weight of polyesters distributes little, and color and luster is good, and catalyst levels is few, but used 1, and the 2-Ucar 35 is the oil source.And there is unstable in this polyester, makes goods have many problems, such as: thermotolerance is bad, and crystallinity is poor, so this kind polyester has all received restriction to a certain degree on range of application.

Summary of the invention

The object of the present invention is to provide a kind of have better thermotolerance and crystalline polyester, further provide a kind of polyester with better thermotolerance and crystalline biogenetic derivation; Have better heat-resisting property, crystallinity on the one hand, enlarged its range of application; Adopt the biogenetic derivation composition on the other hand in the polymer raw material, reduced cost, and solved environmental problem such as white pollution.

Technical solution of the present invention is:

A kind of polyester of the present invention is characterized in that: this polyester is formed from condensation by the monomer suc as formula structure shown in 1,

formula 1

R wherein₁Be C₁～C₂₀Alkyl or C₆～C₂₀Aromatic base.

Polyester according to the invention is characterized in that: the R in the formula 1₁Be C₆～C₂₀Aromatic base.

The intrinsicviscosity of polyester according to the invention is 0.50～1.0dl/g.

The preferred biogenetic derivation carbon content of polyester of the present invention is greater than 35%.Polymer biological source carbon content is confirmed through the mensuration of C14.This is because carbonic acid gas contains the C14 element in the atmosphere; In upper atmosphere; Bump takes place and generates the C14 element in itself and nitrogen, does not contain the C14 element in the oil, and this is because the transformation period of C14 element is 5370; This forms the needed time with oil and compares lessly, thereby can confirm its biological content through the mensuration to 14 elements of carbon in the sample.

The preparation method of said polyester comprises the steps:

(1) with 1, the 2-Ucar 35 with react under alkaline condition suc as formula the compound of structure shown in 2, carry out hydrogenation or hydrolysis again, acidifying obtains intermediate product, the intermediate product structure is shown in the formula 1:

formula 2

formula 1

R wherein₁Be C₁～C₂₀Alkyl or C₆～C₂₀Aromatic base, R₂Be C₁～C₅Alkyl, X is a halogen;

(2) intermediate product that step (1) is obtained carries out the vacuum polycondensation, obtains polyester; Polymeric reaction temperature is 210～290 ℃.

Described alkaline condition refers to the existence of one or more mixtures in sodium hydride, hydrolith, sodium sulphite, sodium hydroxide, Pottasium Hydroxide, hydrated barta, the calcium hydroxide.This is reflected in the solvent and carries out, and solvent is DMF (N, a dinethylformamide), DMSO (DMSO 99.8MIN.) etc.

Can use acetate, carbonate such as zinc, manganese, magnesium in the polycondensation process; Perhaps organometallic compound such as MOX such as zinc, manganese, magnesium and tin, zinc, titanium is as catalyzer, the mixture that one or more are arranged in tetrabutyl titanate, isopropyl titanate, n-butylstannoic acid, manganese acetate, Cobaltous diacetate, the magnesium acetate that specifically can enumerate.Also use the stablizer phosphorus compound in this step; Can be trivalent or phosphoric organic cpds and inorganic phosphorous compound; That can simply enumerate has trimethyl phosphite 99, a triphenylphosphate; Phosphoric acid etc. can be the trivalent of commercially available phosphorus system and the inhibitor of pentavalent, like commercially available PEP36, AP1500, AX-71.

Compound suc as formula structure shown in 2 can be 4-bromomethyl-benzoic acid methyl ester, 8-bromine ethyl octylate, 6-chlorine isopropyl hexylate, 11-bromo ethyl undecylate, 10-bromo-decane acetoacetic ester, 5-chloropentane acid methyl esters, 2-isobutyl ethyl bromide, 2 bromopropionic acid ethyl ester, 2-bromine butanic acid ethyl ester, bromo-acetic acid tert-butyl etc.Preferred 4-bromomethyl-benzoic acid methyl ester among the present invention, structural formula is:

Because many introduction aromatic ring structures can improve the thermotolerance of polyester material in macromolecular chain, but aromatic ring can make the molecular chain rigidity too big too much, has lost the plasticity of material, even can not machine-shaping.

Institute's raw material 1, the 2-Ucar 35 is R-type structure and/or S-type structure.

Used 1, the 2-Ucar 35 is obtained by biogenetic derivation.Biogenetic derivation can be glycerine (being USP Kosher), also can be the stalk of corn, sugarcane, wheat or other farm crop.

In the production of biodiesel process, every production 1t biofuel is with regard to by-product 0.1t glycerine.Biofuel (Biodiesel), promptly fatty acid methyl ester is a kind of cleaning of utilizing rapeseed oil, VT 18, recovery culinary art oil, animal wet goods renewable oils fat to prepare through esterification and transesterification reaction for raw material, the recyclability fuel of environmental protection.

Adopt novel non-noble metal nano-copper base catalytic material the glycerin by-products selective hydrogenation in the production of biodiesel to be prepared 1, the 2-Ucar 35.At present relevant glycerine preparation 1; The 2-Ucar 35 is (under 5～10MPa) conditions, to use Pt at high pressure hydrogen mostly; Non-precious metal catalysts such as noble metal catalyst such as Rh and Ru and Cu and Ni; Catalysis USP Kosher hydrocracking preparation 1 in the intermittent type autoclave, the 2-Ucar 35. this reaction comprises that the USP Kosher dehydration generates the hydroxyacetone midbody and the hydroxyacetone hydrogenation obtains 1, two processes of 2-Ucar 35.This not only forms cheap production 1, and the product technology of 2-Ucar 35 is polyester monocase 1, the synthetic non-petrochemical industry synthetic route that a low cost and environmental protection are provided of 2-Ucar 35.

Use among the present invention 1, the 2-Ucar 35 is the stalk that utilizes corn, wheat, sugarcane and other farm crop, makes through biological fermentation and/or the chemical industry course of processing.For example corn is through the bioprocess separating starch, and through processing the sugar that obtains 5 carbon and 6 carbon, these sugars can be prepared multicomponent binary alcohol through the technology of hydrogenation catalysts; Through after the purifies and separates general procedure, again to separation obtain 1, the 2-Ucar 35 carries out heat treated; Wherein the temperature of heating is 150～200 ℃, and the time of heating is 2～10 hours, contacts processing after cooling again with activated carbon; Just can obtain raw material 1 of the present invention, 2-Ucar 35 component.

The evaluation method of the rerum natura among the present invention is described below.

(1) through the mensuration of radiocarbon C14 element (C14) being confirmed the shared proportion of biogenetic derivation in the compound.

Mainly be sample to be carried out the C14 Determination on content through quickening machine mass spectrometer (AMS); This is because carbonic acid gas contains the C14 element in the atmosphere, and this is because in upper atmosphere, itself and nitrogen bump take place generates the C14 element; Do not contain the C14 element in the oil; This is because transformation period of C14 element is 5370, and this forms the needed time with oil and compares lessly, thereby can confirm its biological content through the mensuration to C14 element in the sample.

Promptly can calculate biological content source through following formula:

Total C content in content/sample of C14 in the biogenetic derivation C constituent content %=sample.

(2) DSC test:

DSC DSC (TA, Q100) be warmed up to 280 ℃ from 40 ℃ with 16 ℃/min after constant temperature 3 minutes, eliminate thermal history; Rapid cool to room temperature then, be warmed up to 320 ℃ from 40 ℃ with 16 ℃/min again after constant temperature 3 minutes, cool to 40 ℃ with 16 ℃/min again, finish.Melt temperature (Tm) and melting enthalpy according to obtaining in heating up for the second time carry out thermotolerance and crystalline evaluation.

(3) measurement of intrinsicviscosity:

Take by weighing 1.6 restrain PET Resin/Poyester Chips Bottle Grade in test tube, 100 ℃ dry 20 minutes down, add the 20ml ortho chloro phenol again and make it heating for dissolving.Sample solution joined in the capillary(tube)viscometer measure automatically, through calculating intrinsic viscosity.

Embodiment

Next with embodiment the present invention is further described.

Embodiment 1:

(1) be that corn is prepared 1 with biogenetic derivation, 2-Ucar 35 (R-type structure) and sodium hydride are dissolved among the DMF (N, dinethylformamide), and temperature of reaction is 0 ℃; Behind the reaction 5min, progressively be warmed up to 26 ℃ of room temperatures, the back adds 4-bromomethyl-benzoic acid methyl ester (structure is seen table 1) among the 20min, reacts extraction after 2 hours; Drying is separated through chromatographic column, again with its hydrogenation; Acidifying obtains intermediate product, and the structure of intermediate product is:

(2) be 290 ℃ with the above-mentioned intermediate product that obtains in temperature, vacuum polymerization gets polyester product; Polyester product is the following polyester product of coincidence unit structure (n=200).

Embodiment 2:

(1) be that glycerine is prepared 1 with biogenetic derivation, 2-Ucar 35 (R-type structure) and sodium hydride are dissolved among the DMF (N, dinethylformamide), and temperature of reaction is 0 ℃; Behind the reaction 5min, progressively be warmed up to 26 ℃ of room temperatures, the back adds 4-bromomethyl-benzoic acid methyl ester (structure is seen table 1) among the 20min, reacts extraction after 2 hours; Drying is separated through chromatographic column, again with its hydrogenation; Acidifying obtains intermediate product, and the structure of intermediate product is:

(2) be 290 ℃ with the above-mentioned product that obtains in temperature, vacuum polymerization gets polyester product; Polyester product is the following polyester product of coincidence unit structure (n=200).

Embodiment 3:

(1) be that corn is prepared 1 with biogenetic derivation, 2-Ucar 35 (R-type structure) be dissolved among the DMF (N, dinethylformamide) with sodium hydride, temperature of reaction is 0 ℃; Behind the reaction 5min, progressively be warmed up to 26 ℃ of room temperatures, the back adds 2-isobutyl ethyl bromide (structure is seen table 1) among the 20min, reacts extraction after 2 hours; Drying is separated through chromatographic column, again with its hydrogenation; Acidifying obtains intermediate product, and the structure of intermediate product is:

(2) be 290 ℃ with the above-mentioned product that obtains in temperature, vacuum polymerization gets polyester product; Polyester product is the following polyester product of coincidence unit structure (n=200).

Embodiment 4:

(1) be that corn is prepared 1 with biogenetic derivation, 2-Ucar 35 (S-type structure) be dissolved among the DMF (N, dinethylformamide) with sodium hydride, temperature of reaction is 0 ℃; Behind the reaction 5min, progressively be warmed up to 26 ℃ of room temperatures, the back adds 8-bromine ethyl octylate (structure is seen table 1) among the 20min, reacts extraction after 2 hours; Drying is separated through chromatographic column, again with its hydrogenation; Acidifying obtains intermediate product, and the structure of intermediate product is:

(2) be 290 ℃ with the above-mentioned product that obtains in temperature, vacuum polymerization gets polyester product; Polyester product is the following polyester product of coincidence unit structure (n=200).

Embodiment 5:

(1) be that corn is prepared 1 with biogenetic derivation, 2-Ucar 35 (racemic modification) be dissolved among the DMF (N, dinethylformamide) with sodium hydride, temperature of reaction is 0 ℃; Behind the reaction 5min, progressively be warmed up to 26 ℃ of room temperatures, the back adds 6-chlorine isopropyl hexylate (structure is seen table 1) among the 20min, reacts extraction after 2 hours; Drying is separated through chromatographic column, again with its hydrogenation; Acidifying obtains intermediate product, and the structure of intermediate product is: (racemic modification is the mixtinite of R-type structure and S-type structure)

(2) be 290 ℃ with the above-mentioned product that obtains in temperature, vacuum polymerization gets polyester product; Polyester product is the following polyester product of coincidence unit structure (n=200).

Comparative example 1:

With terephthalic acid, oil source 1,2-Ucar 35 (R-type structure) is put in the esterifying kettle; Under 225 ℃ of temperature and condition of normal pressure, carry out esterification; When water finishes esterification when no longer gold-plating goes out, move into poly-unit to esterification products, add conventional used catalyzer metatitanic acid four butyl esters, stablizer phosphoric acid, antioxidant 1010 (four [methyl-β-(3 again; The 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester); Stir, below vacuum 200Pa, carry out polycondensation under 265 ℃ of conditions and obtain PTT with conventional polycondensation method.

Terephthalic acid structural formula:

Comparative example 2:

With terephthalic acid, oil source 1,2-Ucar 35 (S-type structure) is put in the esterifying kettle; Under 225 ℃ of temperature and condition of normal pressure, carry out esterification; When water finishes esterification when no longer gold-plating goes out, move into poly-unit to esterification products, add conventional used catalyzer metatitanic acid four butyl esters, stablizer phosphoric acid, antioxidant 1010 (four [methyl-β-(3 again; The 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester); Stir, below vacuum 200Pa, carry out polycondensation under 265 ℃ of conditions and obtain PTT with conventional polycondensation method.

Comparative example 3:

With terephthalic acid, oil source 1,2-Ucar 35 (racemic modification) is put in the esterifying kettle; Under 225 ℃ of temperature and condition of normal pressure, carry out esterification; When water finishes esterification when no longer gold-plating goes out, move into poly-unit to esterification products, add conventional used catalyzer metatitanic acid four butyl esters, stablizer phosphoric acid, antioxidant 1010 (four [methyl-β-(3 again; The 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester); Stir, below vacuum 200Pa, carry out polycondensation under 265 ℃ of conditions and obtain PTT with conventional polycondensation method.

Each data of embodiment and comparative example are specifically seen table 1.

Table 1

Claims (7)

1. polyester; It is characterized in that: this polyester is formed from condensation by the monomer suc as formula structure shown in 1, formula 1

R wherein₁Be C₁～C₂₀Alkyl or C₆～C₂₀Aromatic base.

2. polyester according to claim 1 is characterized in that: the R in the formula 1₁Be C₆～C₂₀Aromatic base.

3. polyester according to claim 1 and 2 is characterized in that: the intrinsicviscosity of this polyester is 0.50～1.0dl/g.

4. polyester according to claim 1 and 2 is characterized in that: the biogenetic derivation carbon content of this polyester is greater than 35%.

5. the preparation method of the described polyester of claim 1 is characterized in that: comprise following steps:

(1) with 1, the 2-Ucar 35 with react under alkaline condition suc as formula the compound of structure shown in 2, carry out hydrogenation or hydrolysis again, acidifying obtains intermediate product, the intermediate product structure is shown in the formula 1:

formula 2

formula 1

R wherein₁Be C₁～C₂₀Alkyl or C₆～C₂₀Aromatic base, R₂Be C₁～C₅Alkyl, X is a halogen;

(2) intermediate product that step (1) is obtained carries out the vacuum polycondensation, obtains polyester; Polymeric reaction temperature is 210 ℃～290 ℃.

6. the preparation method of polyester according to claim 5 is characterized in that: said raw material 1,2-Ucar 35 are R-type structure and/or S-type structure.

7. according to the preparation method of claim 5 or 6 described polyester, it is characterized in that: said raw material 1, the 2-Ucar 35 is obtained by biogenetic derivation.