CN111393617B - Performance-adjustable thermoplastic polyester elastomer and preparation method thereof - Google Patents
Performance-adjustable thermoplastic polyester elastomer and preparation method thereof Download PDFInfo
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Abstract
A thermoplastic polyester elastomer with adjustable performance and a preparation method thereof belong to the technical field of polymer preparation. The aliphatic poly (ethylene glycol) diacid is used as a macroinitiator (soft segment), and the cyclic oligomer is used as a monomer (hard segment), and the aliphatic poly (ethylene glycol) diacid is prepared by a ring-opening condensation cascade polymerization method under the action of a catalyst. The polyester elastomer prepared by the invention has good thermodynamic property, degradability and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of polymer preparation, and particularly relates to a preparation method of a thermoplastic polyester elastomer.
Background
Thermoplastic elastomer (TPE) is a material having elasticity of rubber at normal temperature and moldability and processability of plastic at high temperature. Generally consisting of a plastic phase and a rubber phase having a phase separation structure, wherein the rubber phase makes the material exhibit elasticity, and the plastic phase functions as a thermally reversible physical crosslinking point and imparts strength to the material. The polyester thermoplastic elastomer (TPEE) is a thermoplastic elastomer with excellent performance, and has excellent fatigue resistance, chemical resistance, heat resistance, low-temperature toughness and flexural resistance, and higher mechanical strength and flexural modulus. In terms of chemical structure, polyester-based thermoplastic elastomers usually use crystalline, high-melting point polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) as hard segments, and amorphous aliphatic polyethers with low glass transition temperature such as polyethylene glycol (PEO) and Polytetrahydrofuran (PTMO) as soft segments to copolymerize into block polymer materials. The reaction process is generally synthesized by a traditional ester exchange method, the reaction process is a random polycondensation process, the molecular weight is slowly increased in the early stage of the reaction, and because a competitive reaction exists in the reaction process, the product has a complex structure, the reaction repeatability is poor, the characterization is difficult, and a high molecular weight polymer is difficult to obtain. In addition, with the increasing environmental pollution and environmental awareness and the demand for applications, there is a need for a thermoplastic elastomer having a certain biocompatibility, biodegradability, stretchability, and high mechanical strength and flexural modulus. The patent CN101768246B discloses a multi-block copolyester and a preparation method thereof, controllability and repeatability are better than those of a traditional ester exchange method, tensile strength is 10-67MPa, elongation at break is 20-1080%, mechanical properties are better, and diisocyanate is used as a chain extender, so that biodegradability is avoided. Patent CN105524259a discloses a polyester elastomer and a preparation method thereof, which uses succinic acid (ester) and isophthalic acid (ester) as raw materials to make the obtained polyester elastomer have biodegradability and elastomer performance, but random polycondensation makes the reaction process difficult to control, and a heat stabilizer, an antioxidant and the like are required to be added, and the prepared elastomer is made of isophthalic acid (ester) instead of or partially replaces terephthalic acid (ester), so that the elastomer performance is improved, but the mechanical strength is poor. In patent CN106008945a, we propose a method for preparing high molecular weight linear polyester by ring-opening polymerization of cyclic oligo-polyester, which has no small molecular by-product and mild reaction conditions, and further, we envision to obtain the target polyester elastomer by ring-opening polymerization by controlling the synthesis of soft segment molecular weight.
Disclosure of Invention
The invention aims to provide a preparation method of a thermoplastic polyester elastomer with good tensile property, low-temperature toughness and higher mechanical strength from the requirement on the performance of the existing thermoplastic polyester, and the elastomer has certain biocompatibility and biodegradability.
The second purpose of the invention is to regulate and control the number of blocks by controlling the molecular weight of the soft segment of the polyester elastomer and obtain the expected performance index of the elastomer after melt polymerization with the hard segment polyester.
The technical scheme of the invention is as follows: a preparation method of a thermoplastic polyester elastomer with adjustable and controllable performance, which takes aliphatic polyethylene glycol diacid glycol as a macroinitiator as a soft segment and takes a cyclic oligomer as a monomer hard segment, and is prepared by a ring-opening-condensation cascade polymerization method under the action of a catalyst, and comprises the following steps:
(1) Preparation of aliphatic poly (diacid diol ester) diol macroinitiator, namely soft segment:
under the protection of nitrogen, adding aliphatic dicarboxylic acid and ethylene glycol into a reaction device, and carrying out esterification under the stirring condition; the mass ratio of dicarboxylic acid to glycol is 1:0.8 to 1.5 (preferably, the molar ratio of the glycol to the aliphatic dicarboxylic acid is more than 1:1), and esterification reaction is carried out at 180 to 200 ℃ for 80 to 100min; then cooling to room temperature, adding tetrabutyl titanate catalyst which accounts for 0.1-0.2% of the total mass of the reactants, raising the temperature to 220-240 ℃, carrying out condensation polymerization under the vacuum pressure of 300-400 Pa, evaporating liquid in the polymerization process, and polymerizing for 20-40 min; further controlling or regulating the molecular weight of the aliphatic diacid glycol ester according to the distilled liquid glycol amount;
(2) Preparation of a multiblock copolyester elastomer:
under the condition of nitrogen protection, adding the aliphatic poly diacid diol ester diol macroinitiator prepared in the step (1), cyclic oligoester and a catalyst into a vacuum reaction device, and carrying out melt polymerization under the stirring condition; the mass ratio of the aliphatic polydiol ester diol macroinitiator to the cyclic oligomeric ester is 1:0.5 to 3, the polymerization process is a ring-opening-condensation cascade polymerization process, the polymerization temperature is 220 to 240 ℃, the polymerization time is 60 to 90min, the selected catalyst is tetrabutyl titanate, and the adding amount is 0.1 to 0.2 percent of the total reaction mass; the vacuum pressure is 50-300 Pa.
The invention obtains the aliphatic poly diacid glycol ester diol macroinitiator with controllable molecular weight through the preparation method step (1), the initiator is prepared by the condensation polymerization of aliphatic dicarboxylic acid and glycol, and the number average molecular weight is 2000-8000 g/mol.
The aliphatic dicarboxylic acid is coal-based aliphatic dicarboxylic acid, preferably one of adipic acid, glutaric acid and succinic acid.
The thermoplastic polyester elastomer with adjustable performance is obtained by the preparation method step (2), is obtained by initiating ring-opening polymerization of cyclic oligoester by polyester glycol, has good reaction repeatability, can adjust the proportion of soft segments and hard segments to adjust the performance of the elastomer, has the glass transition temperature of-28-1 ℃, the melting point of 90-128 ℃, the elongation at break of 200-1300%, the Young modulus of 3.6-148 MPa and the number average molecular weight of 20000-35000 g/mol.
The cyclic oligomer is an aromatic cyclic oligomer, preferably cyclic oligomer such as ethylene terephthalate and cyclic oligomer butylene terephthalate, and the polyester obtained after polymerization is one of polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
The invention has the beneficial effects that: the polyester elastomer prepared by the two-step method can obtain a soft segment with a target molecular weight by controlling the molecular weight of the synthesized polyester glycol macroinitiator, and further has adjustable elastomer performance by regulating and controlling the feeding proportion of the soft segment and the soft segment.
Drawings
FIG. 1 is a gel permeation chromatogram of the macroinitiator polyethylene glycol adipate diol of example 1;
FIG. 2 is a gel permeation chromatogram of the macroinitiator polyethylene glycol adipate diol of example 2;
FIG. 3 is a gel permeation chromatogram of the macroinitiator polyethylene glutarate diol of example 5.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
50g of adipic acid and 50g of ethylene glycol are added into a 500mL three-neck flask, nitrogen is introduced under mechanical stirring, and esterification is carried out for 90min at 180-200 ℃. Cooling to room temperature, adding 0.20g of tetrabutyl titanate, carrying out vacuum polymerization at 220-240 ℃, keeping the pressure at 400Pa, stopping the reaction when 20g of liquid is pumped out, wherein the reaction time is 30min, and obtaining a white solid, namely the polyethylene glycol adipate glycol, and the reaction synthetic route is shown in figure 1. Gel permeation chromatography showed a number average molecular weight of 3230g/mol, see FIG. 1.
50g of polyethylene glycol adipate glycol synthesized in the step and 50g of Cyclic Oligomeric Butylene Terephthalate (COBTs) are added into a 500mL three-neck flask, 0.20g of tetrabutyl titanate is added, nitrogen is introduced under mechanical stirring, vacuum polymerization is carried out at 220-240 ℃ under the pressure of 130Pa, reaction is carried out for 90min, and a light yellow polymer product A1 with obvious elasticity is obtained and can be pressed into a film to prepare a sample strip. Molecular weight is determined by Gel Permeation Chromatography (GPC), glass transition temperature, melting point are measured by Differential Scanning Calorimetry (DSC), modulus is measured by dynamic thermo-mechanical analysis (DMA), and elongation at break is measured by tensile (stress-strain). Biodegradability was tested by the enzymatic method. The specific data are shown in Table 1.
Example 2
50g of adipic acid and 50g of ethylene glycol are added into a 500mL three-neck flask, nitrogen is introduced under mechanical stirring, and esterification is carried out for 90min at 180-200 ℃. Adding 0.20g of tetrabutyl titanate, vacuumizing and polymerizing at 220-240 ℃ under the pressure of 400Pa, and stopping the reaction when 41.5g of liquid is pumped out, wherein the reaction time is 40min, thus obtaining white solid poly (ethylene glycol adipate) glycol. Gel permeation chromatography showed a number average molecular weight of 6400g/mol, see FIG. 2.
50g of polyethylene glycol adipate glycol synthesized in the step and 50g of Cyclic Oligomeric Butylene Terephthalate (COBTs) are added into a 500mL three-neck flask, 0.20g of tetrabutyl titanate is added, nitrogen is introduced under mechanical stirring, vacuum polymerization is carried out at 220-240 ℃, the pressure is 130Pa, reaction is carried out for 90min, a light yellow polymer product A2 with obvious elasticity is obtained, and film pressing and sample strip preparation can be carried out. Sample performance data are shown in table 1.
Example 3
The procedure for the synthesis of polyethylene glycol adipate was identical to that of example 1.
50g of polyethylene glycol adipate synthesized in the step and 50g of polyethylene terephthalate (PEETs) are added into a 500mL three-neck flask, 0.20g of tetrabutyl titanate is added, nitrogen is introduced under mechanical stirring, vacuum polymerization is carried out at 220-240 ℃ under the pressure of 130Pa, reaction is carried out for 90min, and a yellow polymer product A3 with obvious elasticity is obtained and can be pressed into a film to prepare a sample strip. Sample performance data are shown in table 1.
Example 4
The procedure for the synthesis of polyethylene adipate glycol corresponds to example 1.
50g of polyethylene glycol adipate glycol synthesized in the step and 25g of Cyclic Oligomeric Butylene Terephthalate (COBTs) are added into a 500mL three-neck flask, 0.15g of tetrabutyl titanate is added, nitrogen is introduced under mechanical stirring, vacuum polymerization is carried out at 220-240 ℃ under the pressure of 130Pa, reaction is carried out for 90min, and a light yellow polymer product A4 with obvious elasticity is obtained and can be pressed into a film to prepare a sample strip. Sample performance data are shown in table 1.
Example 5
50g of glutaric acid and 50g of ethylene glycol are added into a 500mL three-neck flask, nitrogen is introduced under mechanical stirring, and esterification is carried out for 60min at 180-200 ℃. Cooling to room temperature, adding 0.20g of tetrabutyl titanate, vacuumizing at 220-240 ℃ for polymerization under the pressure of 340Pa, and stopping the reaction when 20g of liquid is pumped out, wherein the reaction time is 20min, thus obtaining white solid polyethylene glycol glutarate. Gel permeation chromatography showed a number average molecular weight of 3400g/mol, see FIG. 3.
50g of polyethylene glycol glutarate and 50g of Cyclic Oligomeric Butylene Terephthalate (COBTs) synthesized in the previous steps are added into a 500mL three-neck flask, 0.20g of tetrabutyl titanate is added, nitrogen is introduced under mechanical stirring, vacuum polymerization is carried out at 220-240 ℃, the pressure is 240Pa, reaction is carried out for 60min, and a white polymer product A5 with obvious elasticity is obtained and can be subjected to film pressing to prepare a sample strip. Sample performance data are shown in table 1.
Example 6
The procedure for the synthesis of polyethylene adipate glycol corresponds to example 1.
50g of polyethylene glycol adipate glycol synthesized in the step and 150g of Cyclic Oligomeric Butylene Terephthalate (COBTs) are added into a 500mL three-neck flask, 0.40g of tetrabutyl titanate is added, nitrogen is introduced under mechanical stirring, vacuum polymerization is carried out at 220-240 ℃ under the pressure of 130Pa, reaction is carried out for 90min, and a light yellow polymer product A6 with obvious elasticity is obtained and can be pressed into a film to prepare a sample strip. Sample performance data are shown in table 1.
The sample property test conditions were as follows.
Preparation of sample strips: weighing 5.8g of a sample to be tested, shearing the sample into pieces, drying the sample in vacuum at 80 ℃ for 12h, hot-pressing the cut sample into a film at 90-180 ℃, cutting a dumbbell type standard sample strip with the thickness of 50/3/0.5mm, drying the sample strip in a vacuum drying oven at normal temperature for 12h, and testing.
Gel Permeation Chromatography (GPC) test (molecular weight): the GPC testing system included a Waters1515 pump, 717 autosampler, 2414 UV detector, PL Mixed-C chromatography column. Dissolving the sample to be tested in Tetrahydrofuran (THF) or chloroform (CDCl) 3 ) In the solvent, a 1.0mg/mL solution was prepared, filtered through a 0.45 μm PTFE filter and tested. GPC as mobile phase THF or CDCl 3 The flow rate is 1mL/min, the measurement temperature is 35 ℃, and narrow-distribution polystyrene is used for calibration of a standard sample.
Differential Scanning Calorimetry (DSC) test (glass transition temperature, melting point): measured using Q200 from TA, USA. Under the nitrogen atmosphere, the temperature is raised from 25 ℃ to 250 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 2min, then the temperature is lowered to-90 ℃, the temperature is kept for 2min, and then the temperature is raised to 300 ℃.
Dynamic thermomechanical analysis (DMA) test (modulus): the measurement was carried out using Q800 of TA, USA. The test frequency was 1Hz, the temperature was increased from-110 ℃ at a rate of 3 ℃/min until the modulus decreased to the lower limit of the machine test. The test samples were bars.
Tensile (stress-strain) test (elongation at break): an Instron 5966 universal materials tester was used, with a beam tensile rate of 10mm/min and a test temperature of about 30 ℃. The test samples were bars.
Biodegradability test: an enzyme solution (1 mg/ml) prepared from Pseudomonas cepacia lipase and a phosphate buffer solution is used as a degradation solution, the temperature is kept at 25 ℃, samples are taken regularly, washed by deionized water, dried for 12 hours in vacuum at normal temperature, and the degradation rate is weighed and calculated.
Table 1 example performance data for each sample
The melting point of "-" corresponding to A4 means that a specific melting point cannot be detected by DSC under the conditions of the present invention.
Claims (6)
1. A preparation method of a thermoplastic polyester elastomer with adjustable and controllable performance is characterized in that the method takes aliphatic polyethylene glycol diacid glycol as a macroinitiator as a soft segment monomer and takes a cyclic oligomer as a hard segment monomer, and the thermoplastic polyester elastomer is prepared by a ring-opening condensation cascade polymerization method under the action of a catalyst; the method comprises the following specific steps:
(1) Preparation of aliphatic polyethylene glycol diacid diol macroinitiator, namely soft segment:
under the protection of nitrogen, adding aliphatic dicarboxylic acid and ethylene glycol into a reaction device, and carrying out esterification under the stirring condition; the mass ratio of aliphatic dicarboxylic acid to ethylene glycol is 1:0.8 to 1.5, and carrying out esterification reaction at 180 to 200 ℃ for 80 to 100min; then cooling to room temperature, adding tetrabutyl titanate serving as a catalyst and accounting for 0.1-0.2% of the total mass of the reaction, raising the temperature to 220-240 ℃, carrying out condensation polymerization under the vacuum pressure of 300-400 Pa, and distilling out liquid in the polymerization process for 20-40 min;
(2) Preparation of a multiblock copolyester elastomer:
adding the aliphatic polyethylene glycol diacid glycol macroinitiator prepared in the step (1), the cyclic oligoester and the catalyst into a vacuum reaction device under the protection of nitrogen, and carrying out melt polymerization under the stirring condition; the mass ratio of the aliphatic polyethylene glycol diacid glycol macroinitiator to the cyclic oligomeric ester is 1:0.5 to 3, wherein the polymerization process is an open-loop condensation cascade polymerization process, the polymerization temperature is 220 to 240 ℃, the polymerization time is 60 to 90min, the selected catalyst is tetrabutyl titanate, and the addition amount of the tetrabutyl titanate is 0.1 to 0.2 percent of the total mass of the reaction; vacuumizing at the pressure of 50-300 Pa;
the aliphatic polyethylene glycol diacid glycol macroinitiator with controllable molecular weight is obtained in the step (1), and is prepared by carrying out polycondensation reaction on aliphatic dicarboxylic acid and glycol, wherein the number average molecular weight is 2000 to 8000 g/mol; the cyclic oligomer is aromatic cyclic oligomer; the aliphatic dicarboxylic acid is coal-based aliphatic dicarboxylic acid.
2. The process for producing a thermoplastic polyester elastomer with controlled properties according to claim 1, wherein the molecular weight of the aliphatic polyethylene glycol diacid is controlled or adjusted in the step (1) according to the amount of the liquid ethylene glycol distilled off.
3. The method for preparing a thermoplastic polyester elastomer with controllable properties according to claim 1, wherein the aliphatic dicarboxylic acid is one of adipic acid, glutaric acid and succinic acid.
4. The method for preparing a thermoplastic polyester elastomer with controllable properties according to claim 1, wherein the cyclic oligomer is selected from the group consisting of cyclic oligomer ethylene terephthalate and cyclic oligomer butylene terephthalate, and the polyester obtained after polymerization is one of polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
5. The preparation method of the thermoplastic polyester elastomer with controllable performance according to claim 1, characterized in that the performance of the elastomer is adjusted by adjusting the proportion of soft segments and hard segments in the step (2), the glass transition temperature of the elastomer is-28 to 1 ℃, the melting point of the elastomer is 90 to 128 ℃, the elongation at break of the elastomer is 200 to 1300%, the Young modulus of the elastomer is 3.6 to 148MPa, and the number average molecular weight of the elastomer is 20000 to 35000g/mol.
6. Thermoplastic polyester elastomers obtainable by the process according to any one of claims 1 to 5.
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| US4031165A (en) * | 1974-09-30 | 1977-06-21 | Teijin Limited | Process for preparing polyester elastomers |
| EP1314749A3 (en) * | 1996-12-30 | 2006-03-15 | Daicel Chemical Industries, Ltd. | Polyester elastomers, processes for preparing the same, and compositions of the same |
| US6436549B1 (en) * | 2001-07-16 | 2002-08-20 | Cyclics Corporation | Block copolymers from macrocyclic oligoesters and dihydroxyl-functionalized polymers |
| JP5339519B2 (en) * | 2009-02-18 | 2013-11-13 | ユニチカ株式会社 | Polyester block copolymer and method for producing the same |
| JP2011000816A (en) * | 2009-06-19 | 2011-01-06 | Toyobo Co Ltd | Manufacturing method of electric and electronic component sealed with polyester resin of polymerized cyclic polyester oligomer |
| CN102516517A (en) * | 2011-12-13 | 2012-06-27 | 金发科技股份有限公司 | Method for preparing polyester-polyester blocked copolyester |
| CN103254412B (en) * | 2012-10-31 | 2015-08-05 | 苏州大学 | A kind of preparation method of polyether ester block polymer |
| CN105524259A (en) * | 2014-10-23 | 2016-04-27 | 中国石油化工股份有限公司 | Polyester elastomer and preparation method thereof |
| CN106589328B (en) * | 2015-10-20 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of polyester elastomer and preparation method thereof |
| CN106835438B (en) * | 2016-12-15 | 2019-08-20 | 中国纺织科学研究院有限公司 | It is a kind of containing aromatic polyester-aliphatic polyester block copolymerization ester fiber stockinette |
| CN106835406B (en) * | 2016-12-15 | 2020-01-24 | 中国纺织科学研究院有限公司 | Fabric containing aromatic polyester-aliphatic polyester block copolyester fiber and regenerated cellulose fiber and preparation method thereof |
| EP3591006B1 (en) * | 2017-02-28 | 2021-05-26 | Toyobo Co., Ltd. | Polyester elastomer resin composition having improved mold fouling |
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