CN115246926A - Poly 2,6-pyridine dicarboxylic acid diol ester based thermoplastic polyester elastomer and preparation method and application thereof - Google Patents
Poly 2,6-pyridine dicarboxylic acid diol ester based thermoplastic polyester elastomer and preparation method and application thereof Download PDFInfo
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- CN115246926A CN115246926A CN202111605783.2A CN202111605783A CN115246926A CN 115246926 A CN115246926 A CN 115246926A CN 202111605783 A CN202111605783 A CN 202111605783A CN 115246926 A CN115246926 A CN 115246926A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention relates to a poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer, a preparation method and an application thereof, wherein the structural formula of the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer is shown as the formula (1):
in the formula (1), x and y are integers from 1 to 10, z is an integer from 10 to 100, m is an integer from 2 to 4, and n is an integer from 6 to 30. The poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer has excellent heat resistance and elastic recovery capability, so that medical equipment parts prepared by the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer have higher heat deformation temperature and elastic recovery performance, can bear higher use temperature and can be disinfectedThe temperature and the elastic recovery rate of the medical device part after thermal deformation are higher, and meanwhile, the medical device part also has excellent antibacterial performance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer and a preparation method and application thereof.
Background
The thermoplastic polyester elastomer (TPEE) is a copolymer formed by copolymerizing a short-chain polyester hard segment with high crystallinity and an amorphous long-chain polyether or polyester soft segment, and has the elastic recovery performance of the elastomer and the high modulus and strength of plastics. The hard segment and the soft segment have thermodynamic incompatibility, so that the two phases of the TPEE are subjected to microphase separation, the hardness, modulus, strength, heat resistance and oil resistance of the TPEE can be improved by increasing the proportion of the hard segment, the elasticity and low-temperature flexibility of the TPEE can be improved by increasing the proportion of the soft segment, but the heat resistance, the oil resistance and the mechanical strength are poor, and in addition, the type, the length and the content of the soft segment and the hard segment influence the performance of the TPEE.
At present, the common hard sections in the TPEE comprise polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polytrimethylene terephthalate (PPT) and the like, and the soft sections comprise Polytetrahydrofuran (PTMG), polyethylene glycol (PEG), ethylene oxide modified polypropylene glycol (PPG) and the like, so that the TPEE still has the problems of insufficient heat resistance and elastic recovery in application, and cannot be used at high temperature or be thermally deformed during use, and the deformation cannot be timely recovered, thereby limiting the application of the TPEE in medical equipment parts.
Disclosure of Invention
Therefore, in order to solve the above problems, a poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer, a preparation method and an application thereof are needed, wherein the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer has excellent heat resistance and elastic recovery capability, and medical device parts prepared by the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer have higher heat deformation temperature and elastic recovery performance, and meanwhile, the medical device parts also have excellent antibacterial performance.
A poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer, the structural formula of the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer is shown as formula (1):
in the formula (1), x and y are integers from 1 to 10, z is an integer from 10 to 100, m is an integer from 2 to 4, and n is an integer from 6 to 30.
The preparation method of the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer comprises the following steps:
reacting a first mixed reaction system containing 2,6-pyridinedicarboxylic acid or an esterified product thereof, dihydric alcohol, polytetrahydrofuran and an ester exchange catalyst in a protective atmosphere to obtain an intermediate product;
and (3) reacting the second mixed reaction system containing the intermediate product and the stabilizer under vacuum condition to obtain the poly 2,6-pyridine dicarboxylic acid diol ester based thermoplastic polyester elastomer.
In one embodiment, the first mixed reaction system is reacted under a protective atmosphere at the temperature of 160-200 ℃ for 2-6 h, and the second mixed reaction system is reacted under a vacuum condition at the temperature of 240-260 ℃ for 2-6 h.
In one embodiment, the 2,6-pyridinedicarboxylic acid or its esterified product is selected from at least one of 2,6-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid dimethyl ester.
In one embodiment, the diol is at least one selected from ethylene glycol, propylene glycol, butylene glycol.
In one embodiment, the molar ratio of the polytetrahydrofuran to the 2,6-pyridinedicarboxylic acid or its ester is from 0.05.
In one embodiment, the transesterification catalyst is selected from at least one of a zinc-based catalyst, a titanium-based catalyst, and an antimony-based catalyst, and the stabilizer is selected from a phosphorus-based stabilizer.
In one embodiment, when the transesterification catalyst is selected from zinc-based catalysts, a polycondensation catalyst is further added in the step of reacting the second mixed reaction system containing the intermediate product and the stabilizer under vacuum conditions, wherein the polycondensation catalyst is selected from at least one of titanium-based catalysts and antimony-based catalysts, and the molar ratio of the polycondensation catalyst to the 2,6-pyridinedicarboxylic acid or its ester is 0.5-1000.0.
The application of the poly 2,6-pyridinedicarboxylic acid glycol ester based thermoplastic polyester elastomer in preparing medical appliance parts.
In one embodiment, the medical device component is a medical gasket or a medical tubing.
In the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer, poly 2,6-pyridinedicarboxylic acid diol ester (PBD) with high melting point and high crystallization is used as a hard segment, polytetrahydrofuran (PTMG) is used as a soft segment, poly 2,6-pyridinedicarboxylic acid diol ester can improve the heat resistance and the elastic recovery capability of poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer, and the length of polytetrahydrofuran soft segment can optimize the heat resistance and the elastic recovery capability of poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer, so that the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer with excellent heat resistance and elastic recovery capability can be obtained through the synergistic effect of the poly 2,6-pyridinedicarboxylic acid diol ester and the polytetrahydrofuran.
Therefore, the medical device part prepared by the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer can bear higher use temperature and disinfection temperature, and the elastic recovery rate of the medical device part after thermal deformation is higher. In addition, a pyridine ring in the molecular structure of the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer has an N-polar atom and can be complexed with metal, so that a medical device part prepared from the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer can form a stable complex with metal antibacterial ions in a matched mode, and the antibacterial performance of the medical device part is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows nuclear magnetism of poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer prepared in example 1 of the present invention 1 An H-NMR spectrum;
FIG. 2 is a DSC plot of poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer prepared in example 1 of the present invention;
FIG. 3 is a TGA profile of poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer prepared according to example 1 of this invention.
Detailed Description
The following will further illustrate the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer provided by the present invention, its preparation method and application.
The structural formula of the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer provided by the invention is shown as the formula (1):
in the formula (1), x and y are integers from 1 to 10, z is an integer from 10 to 100, m is an integer from 2 to 4, and n is an integer from 6 to 30.
In the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer shown in formula (1), poly 2,6-pyridinedicarboxylic acid diol ester with high melting point and high crystallization is used as a hard segment, and polytetrahydrofuran is used as a soft segment, wherein poly 2,6-pyridinedicarboxylic acid diol ester can improve the heat resistance and the elastic recovery capability of poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer, and the length of the polytetrahydrofuran soft segment can optimize the heat resistance and the elastic recovery capability of poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer.
Therefore, through the synergistic effect of the poly 2,6-pyridinedicarboxylic acid diol ester and the polytetrahydrofuran, the elongation at break of the poly 2,6-pyridinedicarboxylic acid diol ester-based thermoplastic polyester elastomer is more than 700%, and can reach about 1400%, the melting point is more than 200 ℃, and can reach 235 ℃, and the poly 2,6-pyridinedicarboxylic acid diol ester-based thermoplastic polyester elastomer has excellent heat resistance and elastic recovery capability.
Therefore, the invention also provides a preparation method of the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer shown in the formula (1), which comprises the following steps:
s1, reacting a first mixed reaction system containing 2,6-pyridine dicarboxylic acid or an esterified product thereof, dihydric alcohol, polytetrahydrofuran and an ester exchange catalyst in a protective atmosphere to obtain an intermediate product;
s2, enabling the second mixed reaction system containing the intermediate product and the stabilizer to react under a vacuum condition to obtain the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer shown in the formula (1).
Specifically, in the first mixed reaction system in the step S1, the molar ratio of the polytetrahydrofuran to the 2,6-pyridinedicarboxylic acid or its esterified product is 0.1 to 100.5, the molar ratio of the sum of the amounts of the dihydric alcohol and the polytetrahydrofuran to the 2,6-pyridinedicarboxylic acid or its esterified product is 1.6 to 1.3.0, and the molar ratio of the transesterification catalyst to the 2,6-pyridinedicarboxylic acid or its esterified product is 0.5 to 1000 to 2.0. Further, the first mixed reaction system is reacted under a protective atmosphere at the temperature of 160-200 ℃ for 2-6 h, wherein the protective atmosphere can be a nitrogen atmosphere or an inert gas atmosphere.
Optionally, the 2,6-pyridinedicarboxylic acid or the esterified product thereof is at least one selected from 2,6-pyridinedicarboxylic acid and 2,6-pyridinedicarboxylic acid dimethyl ester, the dihydric alcohol is at least one selected from ethylene glycol, propylene glycol and butanediol, the relative number average molecular mass of the polytetrahydrofuran is 600g/mol to 2000g/mol, the transesterification catalyst is at least one selected from a zinc-based catalyst, a titanium-based catalyst and an antimony-based catalyst, wherein the zinc-based catalyst is selected from anhydrous zinc acetate, the titanium-based catalyst is at least one selected from tetrabutyl titanate and isopropyl titanate, and the antimony-based catalyst is at least one selected from antimony trioxide, ethylene glycol antimony, acetic acid and polyethylene glycol antimony.
In the second mixed reaction system of the step S2, the molar ratio of the stabilizer to the 2,6-pyridinedicarboxylic acid or the esterified product thereof is 0.5 to 1000, and further, the second mixed reaction system is used for reaction under vacuum conditions at a temperature of 240 ℃ to 260 ℃ for 2h to 6h.
Optionally, the stabilizer is selected from phosphorus stabilizers, specifically including at least one of phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, and ammonium dihydrogen phosphate.
When the transesterification catalyst in step S1 is selected from zinc-based catalysts, a polycondensation catalyst may be further added in the step of reacting the second mixed reaction system containing the intermediate product and the stabilizer under vacuum conditions in step S2, the molar ratio of the polycondensation catalyst to the 2,6-pyridinedicarboxylic acid or its esterified product is 0.5 to 1000.
The poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer is prepared by an esterification-polycondensation process, wherein the esterification product can be subjected to polycondensation reaction without purification, so that the preparation method is simple, the operation is simple and convenient, the controllability is strong, the implementation is easy, and the preparation method is suitable for large-scale industrial production.
The invention also provides application of the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer shown in the formula (1) in preparation of medical equipment parts.
Specifically, the medical device part is a medical gasket or a medical pipeline and the like.
The poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer shown in the formula (1) has excellent heat resistance and elastic recovery capability, so that the medical device part prepared by adopting the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer shown in the formula (1) has excellent heat resistance and elastic recovery capability, can further bear higher use temperature and disinfection temperature, and has higher elastic recovery rate after the medical device part is subjected to thermal deformation.
In addition, because the pyridine ring in the molecular structure of the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer has an N-polar atom and can be complexed with metal, the medical device part prepared by the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer can form a stable complex with metal antibacterial ions, and the antibacterial performance of the medical device part is improved.
Hereinafter, the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer, the preparation method and the application thereof will be further described by the following specific examples.
In the following examples, NMR spectra 1 H-NMR instrument model Bruker 400AVANCE III Spectrometer400MHz, CF measured on the instrument 3 COOD。
In the following examples, thermal analysis was carried out using a differential scanning calorimeter (Mettler Toledo DSC) at a temperature rise rate of 10 ℃/min under N 2 The atmosphere is carried out, and the temperature range is-50 ℃ to 300 ℃.
In the following examples, an Instron model 5567 Universal Material testing machine was used for the elongation at break, and the specimen dimensions were 20.0mm long, 2.0mm wide, 1.0mm thick and 20mm/min tensile speed.
Example 1
2,6-pyridine dicarboxylic acid dimethyl ester, polytetrahydrofuran (PTMG 1000) with the relative molecular mass of 1000 and 1,4-butanediol are added into a reactor according to the molar ratio of 1.23.
Then adding 2,6-pyridine dicarboxylic acid dimethyl ester triphenyl phosphate with 0.6 per mill of molar weight, gradually heating to 240 ℃, reducing the vacuum degree to 20Pa, reacting for 4.5h to obtain the poly-2,6-pyridine dicarboxylic acid diol ester based thermoplastic polyester elastomer with the intrinsic viscosity of 0.96dL/g and nuclear magnetism 1 H-NMR is shown in FIG. 1, DSC curve is shown in FIG. 2, elastic melting point of polyester is 212 ℃, elongation at break is 930%, and TGA curve is shown in FIG. 3.
Example 2
2,6-pyridine dicarboxylic acid dimethyl ester, polytetrahydrofuran (PTMG 1000) with the relative molecular mass of 1000 and 1,4-butanediol are added into a reactor according to the molar ratio of 1.077 to the mixture, then anhydrous zinc acetate with the molar mass of 2,6-pyridine dicarboxylic acid dimethyl ester being 0.6 per thousand is added, and the temperature is gradually increased to 180 ℃ under the protection of nitrogen for reaction for 4.0h.
Then adding 2,6-pyridine dicarboxylic acid dimethyl ester 0.8 per mill of antimony trioxide and 0.8 per mill of phosphorous acid, gradually heating to 260 ℃, reducing the vacuum degree to 30Pa, and reacting for 3.0h to obtain the poly 2,6-pyridine dicarboxylic acid diol ester-based thermoplastic polyester elastomer, wherein the intrinsic viscosity is 0.82dL/g, the melting point is 235 ℃, and the elongation at break is 710%.
Example 3
Adding 2,6-pyridine dicarboxylic acid dimethyl ester, polytetrahydrofuran (PTMG 1000) with the relative molecular mass of 1000 and 1,4-butanediol into a reactor according to a molar ratio of 1.16.
Then adding 2,6-trimethyl phosphate with the molar weight of dimethyl pyridine dicarboxylate of 0.7 per thousand, gradually heating to 255 ℃, reducing the vacuum degree to 15Pa, and reacting for 3.5 hours to obtain the poly 2,6-pyridine dicarboxylic acid diol ester-based thermoplastic polyester elastomer, wherein the intrinsic viscosity is 0.90dL/g, the melting point is 219 ℃, and the elongation at break is 860 percent.
Example 4
Adding 2,6-pyridine dicarboxylic acid dimethyl ester, polytetrahydrofuran (PTMG 1000) with the relative molecular mass of 1000 and 1,4-butanediol into a reactor according to a molar ratio of 1.42.
Then adding phosphorous acid of which the molar weight is 1.6 per thousand of 2,6-dimethyl dipicolinate, gradually heating to 250 ℃, reducing the vacuum degree to 55Pa, and reacting for 5.5 hours to obtain the poly-2,6-dipicolinate diol ester-based thermoplastic polyester elastomer, wherein the intrinsic viscosity is 0.87dL/g, the melting point is 202 ℃, and the elongation at break is 1400%.
Example 5
2,6-dimethyl pyridine dicarboxylate, polytetrahydrofuran (PTMG 1000) with the relative molecular mass of 1000 and 1,3-butanediol are added into a reactor according to the molar ratio of 1.22 to 1.60, and then anhydrous zinc acetate with the molar weight of 1.5 per thousand of 2,6-dimethyl pyridine dicarboxylate is added, and the temperature is gradually raised to 160 ℃ under the protection of nitrogen to react for 6.0h.
Then adding antimony trioxide with the molar weight of 2,6-dimethyl dipicolinate of 2.0 per thousand and triphenyl phosphate with the molar weight of 2,6 dimethyl dipicolinate of 2.5 per thousand, gradually heating to 245 ℃, reducing the vacuum degree to 60Pa, and reacting for 6.0 hours to obtain the poly 2,6-diol pyridinedicarboxylate based thermoplastic polyester elastomer with the intrinsic viscosity of 0.73dL/g, the melting point of 216 ℃ and the elongation at break of 890%.
Example 6
2,6-dimethyl pyridinedicarboxylate, polytetrahydrofuran (PTMG 1000) with the relative molecular mass of 1000 and ethylene glycol are added into a reactor according to the molar ratio of 1: 2.20, then anhydrous zinc acetate with the molar mass of 2,6-dimethyl pyridinedicarboxylate being 2.0 per thousand is added, and the temperature is gradually increased to 195 ℃ under the protection of nitrogen for reaction for 2.0h.
Then adding antimony trioxide with the molar weight of 2,6-dimethyl dipicolinate being 1.6 per thousand and pyrophosphoric acid with the molar weight of 2,6-dimethyl dipicolinate being 3.0 per thousand, gradually heating to 253 ℃, reducing the vacuum degree to 10Pa, and reacting for 2.0 hours to obtain the poly 2,6-dicarboxylic acid diol ester based thermoplastic polyester elastomer with the intrinsic viscosity of 1.12dL/g, the melting point of 225 ℃ and the elongation at break of 840%.
Comparative example 1
1,4-dimethyl terephthalate, polytetrahydrofuran (PTMG 1000) with the relative molecular mass of 1000 and 1,4-butanediol are added into a reactor according to the molar ratio of 1.23.
Then adding 1,4-triphenyl phosphate with 0.6 per mill of dimethyl terephthalate molar weight, gradually heating to 270 ℃, reducing the vacuum degree to 20Pa, and reacting for 4.5h to obtain the poly-1,4-terephthalic acid-polytetrahydrofuran butanediol ester, wherein the intrinsic viscosity is 0.81dL/g, the melting point is 173 ℃, and the elongation at break is 320%.
Comparative example 2
2,5-furandicarboxylic acid dimethyl ester, polytetrahydrofuran (PTMG 1000) with the relative molecular mass of 1000 and 1,4-butanediol are added into a reactor according to the molar ratio of 1.23.
Then adding triphenyl phosphate with the molar weight of 2,5-furandicarboxylic acid dimethyl ester of 0.6 per mill, gradually heating to 240 ℃, reducing the vacuum degree to 20Pa, and reacting for 4.5h to obtain the poly-2,5-furandicarboxylic acid-polytetrahydrofuranbutylene glycol ester, wherein the intrinsic viscosity is 0.77dL/g, the melting point is 130 ℃, and the elongation at break is 360 percent.
Comparative example 3
Adding 2,6-dimethyl pyridine dicarboxylate, polyethylene glycol (PEG 1000) with the relative molecular mass of 1000 and 1,3-propylene glycol into a reactor according to the molar ratio of 1.23.
Then adding triphenyl phosphate with the molar weight of 2,6-dimethyl pyridine dicarboxylate of 0.6 per thousand, gradually heating to 230 ℃, reducing the vacuum degree to 20Pa, and reacting for 4.0h to obtain the poly 2,6-dicarboxylic acid diol ester based thermoplastic polyester elastomer, wherein the intrinsic viscosity is 0.90dL/g, the elastic melting point of the polyester is 156 ℃, and the elongation at break is 428%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer is characterized in that the structural formula of the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer is shown as the formula (1):
in the formula (1), x and y are integers from 1 to 10, z is an integer from 10 to 100, m is an integer from 2 to 4, and n is an integer from 6 to 30.
2. The preparation method of the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer as claimed in claim 1, comprising the steps of:
reacting a first mixed reaction system containing 2,6-pyridinedicarboxylic acid or an esterified product thereof, dihydric alcohol, polytetrahydrofuran and an ester exchange catalyst in a protective atmosphere to obtain an intermediate product;
and (3) reacting the second mixed reaction system containing the intermediate product and the stabilizer under vacuum condition to obtain the poly 2,6-pyridine dicarboxylic acid diol ester based thermoplastic polyester elastomer.
3. The method for preparing the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer as claimed in claim 2, wherein the temperature of the first mixed reaction system is 160 ℃ -200 ℃ for 2h-6h under a protective atmosphere, and the temperature of the second mixed reaction system is 240 ℃ -260 ℃ for 2h-6h under a vacuum condition.
4. The method for preparing the poly 2,6-pyridinedicarboxylic acid diol ester-based thermoplastic polyester elastomer according to claim 2, wherein the 2,6-pyridinedicarboxylic acid or its esterified product is at least one selected from 2,6-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid dimethyl ester.
5. The method for preparing the poly 2,6-pyridinedicarboxylic acid diol ester-based thermoplastic polyester elastomer according to claim 2, wherein the diol is at least one selected from ethylene glycol, propylene glycol, and butylene glycol.
6. The method of claim 2, wherein the molar ratio of the polytetrahydrofuran to the 2,6-pyridinedicarboxylic acid or its ester is from 0.05 to 1 to 0.5, the molar ratio of the sum of the amounts of the glycol and the polytetrahydrofuran to the 2,6-pyridinedicarboxylic acid or its ester is from 1.6 to 1 to 3.0, the molar ratio of the transesterification catalyst to the 2,6-pyridinedicarboxylic acid or its ester is from 0.5 to 1000 to 2.0 1000, the molar ratio of the stabilizer to the 2,6-pyridinedicarboxylic acid or its ester is from 0.5 to 1000 to 3.
7. The method for preparing the poly 2,6-pyridinedicarboxylic acid diol ester based thermoplastic polyester elastomer as claimed in claim 2, wherein the transesterification catalyst is at least one selected from zinc catalyst, titanium catalyst, antimony catalyst, and the stabilizer is selected from phosphorus stabilizer.
8. The method for preparing the poly 2,6-pyridinedicarboxylic acid diol ester-based thermoplastic polyester elastomer according to claim 7, wherein when the transesterification catalyst is selected from zinc-based catalysts, a polycondensation catalyst is further added in the step of reacting the second mixed reaction system containing the intermediate product and the stabilizer under vacuum, the polycondensation catalyst is selected from at least one of titanium-based catalysts and antimony-based catalysts, and the molar ratio of the polycondensation catalyst to the 2,6-pyridinedicarboxylic acid or its esterified product is 0.5.
9. Use of the poly 2,6-pyridinedicarboxylic acid glycol ester based thermoplastic polyester elastomer of claim 1 in the preparation of a medical device part.
10. The use of the poly 2,6-pyridinedicarboxylic acid glycol ester-based thermoplastic polyester elastomer according to claim 9 in the preparation of a medical device component, wherein the medical device component is a medical gasket or a medical tubing.
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Application publication date: 20221028 |