CN111393617A - 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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- CN111393617A CN111393617A CN201911198333.9A CN201911198333A CN111393617A CN 111393617 A CN111393617 A CN 111393617A CN 201911198333 A CN201911198333 A CN 201911198333A CN 111393617 A CN111393617 A CN 111393617A
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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
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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. The polyester-based thermoplastic elastomer in chemical structure is usually copolymerized into a block polymer material by using crystalline, high-melting-point polyester such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) as a hard segment and amorphous aliphatic polyether with lower glass transition temperature such as polyethylene glycol (PEO) and Polytetrahydrofuran (PTMO) as a soft segment. 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 of the competitive reaction in the reaction process, the product structure is complex, 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. Patent CN101768246B discloses a multi-block copolyester and a preparation method thereof, the controllability and the repeatability are better than those of the traditional ester exchange method, the tensile strength is 10-67MPa, the elongation at break is 20-1080%, the mechanical property is better, and diisocyanate is used as a chain extender and has no biodegradability. Patent CN105524259A discloses a polyester elastomer and a preparation method thereof, wherein succinic acid (ester) and isophthalic acid (ester) are used as raw materials, so that the obtained polyester elastomer has biodegradability and elastomer performance, but random polycondensation makes the reaction process difficult to control, a heat stabilizer, an antioxidant and the like are required to be added, and the prepared elastomer is an isophthalic acid (ester) or a part of isophthalic acid (ester) is substituted for 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 oligoester, which has no small molecule by-product and mild reaction conditions, and further, we imagine that the target polyester elastomer is obtained 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: 0.8-1.5 (preferably, the molar ratio of the ethylene glycol to the aliphatic dicarboxylic acid is more than 1:1), and carrying out esterification reaction at 180-200 ℃ for 80-100 min; then cooling to room temperature, adding a catalyst tetrabutyl titanate with the mass of 0.1-0.2% of the total reaction mass, 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:
adding the aliphatic diacid diol ester diol 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 polydiol ester diol macroinitiator to the cyclic oligomeric ester is 1: 0.5-3, wherein the polymerization process is a ring-opening-condensation cascade polymerization process, the polymerization temperature is 220-240 ℃, the polymerization time is 60-90 min, the selected catalyst is tetrabutyl titanate, and the addition amount of the tetrabutyl titanate is 0.1-0.2% of the total reaction mass; the vacuumizing 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), and the initiator is prepared by carrying out polycondensation reaction on 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 with 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
Adding 50g of adipic acid and 50g of ethylene glycol into a 500m L three-neck flask, introducing nitrogen under mechanical stirring, esterifying for 90min at 180-200 ℃, cooling to room temperature, adding 0.20g of tetrabutyl titanate, vacuumizing and polymerizing at 220-240 ℃ under the pressure of 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. the gel permeation chromatography shows that the number average molecular weight is 3230g/mol, and is shown in figure 1.
50g of polyethylene glycol adipate synthesized in the step and 50g of Cyclic Oligomeric Butylene Terephthalate (COBTs) are added into a 500m L 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, and a light yellow polymer product A1 with obvious elasticity is obtained, and film pressing and sample preparation can be carried out.
Example 2
Adding 50g of adipic acid and 50g of ethylene glycol into a 500m L three-neck flask, introducing nitrogen under mechanical stirring, esterifying for 90min at 180-200 ℃, adding 0.20g of tetrabutyl titanate, vacuumizing and polymerizing at 220-240 ℃, wherein the pressure is 400Pa, stopping the reaction when 41.5g of liquid is pumped out, and the reaction time is 40min at the moment, so that white solid polyethylene glycol adipate glycol is obtained, wherein the gel permeation chromatography shows that the number-average molecular weight is 6400g/mol, and is shown in figure 2.
50g of polyethylene glycol adipate glycol synthesized in the step and 50g of Cyclic Oligomeric Butylene Terephthalate (COBTs) are added into a 500m L 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, film pressing and sample preparation can be carried out, and the performance data of the sample are shown in Table 1.
Example 3
The procedure for the synthesis of polyethylene adipate glycol corresponds to example 1.
50g of polyethylene glycol adipate synthesized in the step and 50g of polyethylene terephthalate (COETs) are added into a 500m L 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 yellow polymer product A3 with obvious elasticity is obtained, film pressing and sample preparation can be carried out, and the performance data of the sample 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 500m L three-neck flask, 0.15g 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 A4 with obvious elasticity is obtained, film pressing and sample preparation can be carried out, and the performance data of the sample are shown in Table 1.
Example 5
Adding 50g of glutaric acid and 50g of ethylene glycol into a 500m L three-neck flask, introducing nitrogen under mechanical stirring, esterifying for 60min at 180-200 ℃, cooling to room temperature, adding 0.20g of tetrabutyl titanate, vacuumizing and polymerizing at 220-240 ℃ under the pressure of 340Pa, stopping the reaction when 20g of liquid is pumped out, wherein the reaction time is 20min at the moment, and obtaining white solid polyethylene glycol glutarate glycol, and the gel permeation chromatography shows that the number average molecular weight is 3400g/mol, which is shown in figure 3.
50g of polyethylene glycol glutarate synthesized in the step and 50g of Cyclic Oligomeric Butylene Terephthalate (COBTs) are added into a 500m L 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, a white polymer product A5 with obvious elasticity is obtained, film pressing and sample preparation can be carried out, and the performance data of the sample 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 500m L three-neck flask, 0.40g 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 A6 with obvious elasticity is obtained, film pressing and sample preparation can be carried out, and the performance data of the sample 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 at 80 ℃ for 12h in vacuum, hot-pressing the cut sample at 90-180 ℃ to form a film, cutting out 50/3/0.5mm dumbbell-shaped standard sample strips, and testing the sample strips after the sample strips are placed in a vacuum drying oven and dried for 12h at normal temperature.
Gel Permeation Chromatography (GPC) test (molecular weight): GPC testing system includes Waters1515 pump, 717 fromMoving sample injector, 2414 ultraviolet detector, and P L Mixed-C chromatographic column dissolving sample to be tested in Tetrahydrofuran (THF) or chloroform (CDCl)3) In solvent, a 1.0mg/m L solution was prepared, filtered through a 0.45 μm PTFE filter and tested GPC mobile phase THF or CDCl3The flow rate was 1m L/min, the measurement temperature was 35 ℃ and calibration was carried out with narrow-distribution polystyrene standards.
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: using an enzyme solution (1 mg/ml) prepared from Pseudomonas cepacia lipase and a phosphate buffer solution as a degradation solution, keeping the temperature at 25 ℃, periodically sampling, washing with deionized water, drying at normal temperature in vacuum for 12 hours, and weighing to calculate the degradation rate.
Table 1 example performance data for each sample
The melting point of "-" corresponding to A4 means that no specific melting point could be detected by DSC under the conditions of the present invention.
Claims (9)
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 and takes a cyclic oligomer as a hard segment of a 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 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: 0.8-1.5, carrying out esterification reaction at 180-200 ℃, wherein the esterification time is 80-100 min; then cooling to room temperature, adding a catalyst tetrabutyl titanate with the mass of 0.1-0.2% of the total reaction mass, 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;
(2) preparation of a multiblock copolyester elastomer:
adding the aliphatic diacid diol ester diol 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 polydiol ester diol macroinitiator to the cyclic oligomeric ester is 1: 0.5-3, wherein the polymerization process is a ring-opening-condensation cascade polymerization process, the polymerization temperature is 220-240 ℃, the polymerization time is 60-90 min, the selected catalyst is tetrabutyl titanate, and the addition amount of the tetrabutyl titanate is 0.1-0.2% of the total reaction mass; the vacuumizing pressure is 50-300 Pa.
2. The preparation method of the thermoplastic polyester elastomer with controllable properties according to claim 1, wherein the step (1) is to obtain the aliphatic diacid glycol diol macroinitiator with controllable molecular weight, the aliphatic diacid glycol diol macroinitiator is prepared by the polycondensation reaction of aliphatic dicarboxylic acid and glycol, and the number average molecular weight is 2000-8000 g/mol.
3. The process for producing a thermoplastic polyester elastomer with controlled properties according to claim 1, wherein the molecular weight of the aliphatic poly (diol ester) diol is controlled or adjusted in the step (1) depending on the amount of the liquid ethylene glycol to be distilled out.
4. The method for preparing a thermoplastic polyester elastomer with controllable properties according to claim 1, wherein the aliphatic dicarboxylic acid is a coal-based aliphatic dicarboxylic acid.
5. 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.
6. The method for preparing a thermoplastic polyester elastomer with controllable properties according to claim 1, wherein the cyclic oligomer is an aromatic cyclic oligomer.
7. The method for preparing a thermoplastic polyester elastomer with controllable properties according to claim 1, wherein the cyclic oligomer is selected from cyclic oligomer ethylene terephthalate, cyclic oligomer butylene terephthalate, etc., and the polyester obtained after polymerization is one of polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
8. The preparation method of the thermoplastic polyester elastomer with controllable properties according to claim 1, wherein the properties of the elastomer are adjusted by adjusting the ratio of soft segments to soft segments in the step (2), the glass transition temperature can be-28 to 1 ℃, the melting point can be 90 to 128 ℃, the elongation at break can be 200 to 1300%, the Young modulus can be 3.6 to 148MPa, and the number average molecular weight can be 20000 to 35000 g/mol.
9. Thermoplastic polyester elastomers obtainable by the process according to any one of claims 1 to 8.
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