CN113004499B - Biodegradable polyester elastomer and preparation method and application thereof - Google Patents
Biodegradable polyester elastomer and preparation method and application thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 33
- 239000000806 elastomer Substances 0.000 title claims abstract description 33
- 229920000229 biodegradable polyester Polymers 0.000 title claims abstract description 16
- 239000004622 biodegradable polyester Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 34
- 229920000728 polyester Polymers 0.000 claims abstract description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 11
- XLKZJJVNBQCVIX-UHFFFAOYSA-N tetradecane-1,14-diol Chemical compound OCCCCCCCCCCCCCCO XLKZJJVNBQCVIX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002520 smart material Substances 0.000 claims abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 31
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 19
- 238000006068 polycondensation reaction Methods 0.000 claims description 19
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 14
- 235000011090 malic acid Nutrition 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000001630 malic acid Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 5
- 229940068886 polyethylene glycol 300 Drugs 0.000 claims description 4
- -1 carboxyl-hydroxyl Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000003431 cross linking reagent Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000463 material Substances 0.000 description 19
- 239000012716 precipitator Substances 0.000 description 17
- 229940099690 malic acid Drugs 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 229940116298 l- malic acid Drugs 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007334 memory performance Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000001851 biosynthetic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000021022 fresh fruits Nutrition 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明公开了一种生物可降解的聚酯弹性体的制备方法。所述方法以聚乙二醇或1,14‑十四碳二醇为交联剂，形成与聚苹果酸的交联体系，构建聚苹果酸中的化学网络制得聚酯弹性体。本发明的聚酯弹性体的强度高，断裂伸长率大，由于聚苹果酸的存在，使其可以生物降解，由于聚乙二醇的存在，使其具有良好的韧性，其强度优于一般的聚酯弹性体强度，并且拥有形状记忆性能，适用于柔性可穿戴智能材料领域。
The invention discloses a preparation method of a biodegradable polyester elastomer. The method uses polyethylene glycol or 1,14-tetradecanediol as a cross-linking agent, forms a cross-linking system with polymalic acid, and constructs a chemical network in the polymalic acid to obtain a polyester elastomer. The polyester elastomer of the present invention has high strength and high elongation at break, can be biodegraded due to the existence of polymalic acid, has good toughness due to the existence of polyethylene glycol, and its strength is better than that of ordinary The strength of polyester elastomer is high, and it has shape memory properties, which is suitable for the field of flexible wearable smart materials.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and relates to a biodegradable polyester elastomer, and a preparation method and application thereof.
Background
L-malic acid is a biomass that can be derived from eggshells or fresh fruits and has been industrialized by chemical or biosynthetic means, widely used in the food, beverage, pharmaceutical, chemical and medical industries. Poly L-malic acid (PLMA) or copolymers based on L-malic acid are derivatives of L-malic acid whereas the synthesis of poly malic acid is not so easy. If ring-opening polymerization is used, many reaction steps are involved, whereas only low molecular weight polymers can be obtained using direct polycondensation. Therefore, the research on polymalic acid is mainly focused on the copolymerization or grafting of polymalic acid with other biodegradable aliphatic polyesters, aiming at improving the molecular weight and mechanical strength of the polymalic acid in order to find possible applications in the biomedical field.
The polymalic acid has a large number of active sites in the backbone. Thus, modification of polymalic acid can be achieved in a variety of ways, not just chain extension. Crosslinking is also a good option for improving the overall properties of the polymalic acid. However, the crosslinking of polymalic acid is currently mainly around plastic articles ([1] Qiu YX, Wanyan QR, Xie WY, et al, Green and biobased-derived Materials with controllable Shape Memory transition temperature treated based on cross-linked poly (L-male acid) Polymer 2019; 180: 121733; [2] Yanxin Qiu, Qianru Wanyan, Wenting Zhang, et al, Programmabable and Sophimed Shape-Memory device video tissue modification Distribution of Polymer Cross crack. journal of Materials Chemistry A, ion, 8,17193 17201. the above method uses fatty diol as crosslinking agent, the above method uses large transition strength, but the glass transition strength is not much higher, and the recovery of Shape is not much more limited at room temperature, the above method also uses a material with a high glass transition temperature, and the above-mentioned material has a very low elongation at room temperature.
The polyethylene glycol has good water solubility and good compatibility with a plurality of organic components. They have excellent lubricity, moisture retention and dispersibility, can be used as adhesives, antistatic agents, softeners and the like, and are widely applied to industries such as cosmetics, pharmacy, chemical fibers and the like.
Disclosure of Invention
The invention aims to provide a biodegradable polyester elastomer, and a preparation method and application thereof. The polyester elastomer has high strength, large elongation at break, degradability and shape memory property.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the biodegradable polyester elastomer takes polyethylene glycol or 1, 14-tetradecanediol as a cross-linking agent to construct a chemical network in poly-L-malic acid, and comprises the following steps:
1) melting a malic acid monomer in an oil bath at 130 +/-5 ℃, then polycondensing at 110 +/-2 ℃ and 133 +/-5 Pa in vacuum state, and stirring for reacting for 45 +/-5 hours;
2) dissolving the reactant obtained by the polycondensation in the step 1) in tetrahydrofuran, adding the tetrahydrofuran into a reverse precipitator for precipitation for 10 +/-2 hours, and drying the obtained precipitate at 50 +/-5 ℃;
3) adding the polymalic acid obtained by the polycondensation into a reaction kettle, adding polyethylene glycol 300 or 1, 14-tetradecanediol, carrying out vacuum pumping reaction at 130 +/-2 ℃ for 15-45 min, and curing at 130 +/-2 ℃ for 4-24 h in a nitrogen atmosphere to obtain the biodegradable polyester elastomer.
In the step 1), melting is carried out under 130 +/-5 ℃ oil bath, vacuum pumping reaction is carried out at 110 +/-2 ℃, and the reaction is slowly carried out at too low temperature, so that an expected product cannot be obtained; when the temperature is too high, byproducts are easily generated, so that the purity of the product is reduced.
In the step 1), the stirring speed is 200 +/-20 r/min.
In the step 2), the reverse precipitator is a mixture of petroleum ether and anhydrous ether, and the mass ratio of the petroleum ether to the anhydrous ether is 1: 0.90-1.10, wherein the volume of the reverse precipitator is 9-10 times of that of tetrahydrofuran. The step can remove the unreacted malic acid monomer, and the obtained product has uniform molecular weight and high yield.
In the step 3), the reaction conditions need to be strictly controlled, so that the ideal cross-linked polymalic acid can be obtained; the material needs to be fully cured to achieve stable performance, and the curing time is 22 +/-2 h.
In the step 3), the dosage of the polyethylene glycol is measured according to the polymalic acid in the reactant obtained by in-situ polymerization, and the ratio of the polymalic acid to the carboxyl hydroxyl of the polyethylene glycol or the 1, 14-tetradecanediol is 1: 0.5.
compared with the prior art, the invention has the following advantages:
according to the invention, the network geometry of the crosslinked PLMA is adjusted by adjusting and controlling the chain lengths of the crosslinking agents polyethylene glycol and 1, 14-tetradecanediol, so that the mechanical property of the polyester elastomer is adjusted and controlled. The polyester elastomer prepared by the method has high strength and large elongation at break, can be degraded due to the existence of polymalic acid, has good toughness due to the existence of polyethylene glycol and 1, 14-tetradecanediol, has strength superior to that of a common polyester elastomer, has shape memory performance, and is suitable for the field of flexible wearable intelligent materials.
Drawings
FIG. 1 is a weight diagram of materials prepared in examples 1 and 2 and comparative examples 1, 2 and 5.
Fig. 2 is a stress/strain diagram of the materials prepared in comparative examples 1, 2, 5.
Fig. 3 is a stress/strain diagram of the materials prepared in examples 1 and 2 and comparative examples 3 and 4.
FIG. 4 is a diagram showing a shape memory process of the material prepared in example 1.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1
(1) Melting 28g of malic acid monomer in an oil bath at 130 ℃, polycondensing at 110 ℃ under 133Pa vacuum, stirring at the rotation speed of 200r/min, and reacting for 45 h.
(2) Dissolving the polymalic acid obtained by the polycondensation in 150ml of tetrahydrofuran, and pouring into 1500ml of reverse precipitator for precipitation for 12 hours, wherein the reverse precipitator is petroleum ether: the mass ratio of the anhydrous ether is 1: 1 and drying the obtained precipitate in a vacuum drying oven at 40 ℃.
(3) Weighing 4.5g of polymalic acid obtained by the polycondensation, adding into a reaction kettle, 2.893g of polyethylene glycol 300, carrying out vacuum pumping reaction at 130 ℃ for 15min, and curing at 130 ℃ for 24h in a nitrogen atmosphere to obtain the biodegradable polyester elastomer.
Example 2
(1) Melting 28g of malic acid monomer in an oil bath at 130 ℃, polycondensing at 110 ℃ under 133Pa vacuum, stirring at the rotation speed of 200r/min, and reacting for 45 h.
(2) Dissolving the polymalic acid obtained by the polycondensation in 150ml of tetrahydrofuran, and pouring into 1500ml of reverse precipitator for precipitation for 12 hours, wherein the reverse precipitator is petroleum ether: the mass ratio of the anhydrous ether is 1: 1 and drying the obtained precipitate in a vacuum drying oven at 40 ℃.
(3) Weighing 4.5g of polymalic acid obtained by the polycondensation, adding into a reaction kettle, 2.231g of 1, 14-tetradecanediol, carrying out vacuum pumping reaction at 130 ℃ for 15min, and curing at 130 ℃ for 24h in a nitrogen atmosphere to obtain the biodegradable polyester elastomer.
Comparative example 1
(1) Melting 28g of malic acid monomer in 130 ℃ oil bath, polycondensing at 110 ℃ under 133Pa vacuum state, stirring at the rotation speed of 200r/min, and reacting for 45 h.
(2) And dissolving the reactant obtained by the polycondensation in 150ml of tetrahydrofuran, and pouring the reactant into 1300ml of reverse precipitator for precipitation for 12 hours, wherein the reverse precipitator is petroleum ether: the mass ratio of the anhydrous ether is 1: 1 and drying the obtained precipitate in a vacuum drying oven at 40 ℃.
(3) Weighing 6.0g of polymalic acid obtained by the polycondensation, adding the polymalic acid into a reaction kettle, adding 1.363g of polyethylene glycol 100, carrying out vacuum pumping reaction at 130 ℃ for 15min, and curing at 130 ℃ for 24h in a nitrogen atmosphere to obtain the biodegradable polyester elastomer.
Comparative example 2
(1) Melting 28g of malic acid monomer in 130 ℃ oil bath, polycondensing at 110 ℃ under 133Pa vacuum state, stirring at the rotation speed of 200r/min, and reacting for 45 h.
(2) Dissolving the polymalic acid obtained by the polycondensation in 150ml of tetrahydrofuran, and pouring into 1500ml of reverse precipitator for precipitation for 12 hours, wherein the reverse precipitator is petroleum ether: the mass ratio of the anhydrous ether is 1: 1 and drying the obtained precipitate in a vacuum drying oven at 40 ℃.
(3) Weighing 5g of polymalic acid obtained by polycondensation, adding the polymalic acid into a reaction kettle, 2.143g of polyethylene glycol 200, carrying out vacuum pumping reaction at 130 ℃ for 15min, and curing at 130 ℃ for 24h in a nitrogen atmosphere to obtain the biodegradable polyester elastomer.
Comparative example 3
(1) Melting 28g of malic acid monomer in 130 ℃ oil bath, polycondensing at 110 ℃ under 133Pa vacuum state, stirring at the rotation speed of 200r/min, and reacting for 45 h.
(2) Dissolving the polymalic acid obtained by the polycondensation in 150ml of tetrahydrofuran, and pouring into 1500ml of reverse precipitator for precipitation for 12 hours, wherein the reverse precipitator is petroleum ether: the mass ratio of the anhydrous ether is 1: 1 and drying the obtained precipitate in a vacuum drying oven at 40 ℃.
(3) Weighing 4g of polymalic acid obtained by polycondensation, adding into a reaction kettle, 3.448g of polyethylene glycol 400, carrying out vacuum pumping reaction at 130 ℃ for 15min, and curing at 130 ℃ for 24h in nitrogen atmosphere to obtain the biodegradable polyester elastomer.
Comparative example 4
(1) Melting 28g of malic acid monomer in 130 ℃ oil bath, polycondensing at 110 ℃ under 133Pa vacuum state, stirring at the rotation speed of 200r/min, and reacting for 45 h.
(2) Dissolving the polymalic acid obtained by the polycondensation in 150ml of tetrahydrofuran, and pouring into 1500ml of reverse precipitator for precipitation for 12 hours, wherein the reverse precipitator is petroleum ether: the mass ratio of the anhydrous ether is 1: 1 and drying the obtained precipitate in a vacuum drying oven at 40 ℃.
(3) Weighing 4.5g of polymalic acid obtained by polycondensation, adding into a reaction kettle, 2.893g of polyethylene glycol 300, carrying out vacuum pumping reaction at 130 ℃ for 15min, and curing at 130 ℃ for 4h in nitrogen atmosphere to obtain the biodegradable polyester elastomer.
Comparative example 5
(1) Melting 28g of malic acid monomer in an oil bath at 130 ℃, polycondensing at 110 ℃ under 133Pa vacuum, stirring at the rotation speed of 200r/min, and reacting for 45 h.
(2) Dissolving the polymalic acid obtained by the polycondensation in 150ml of tetrahydrofuran, and pouring into 1500ml of reverse precipitator for precipitation for 12 hours, wherein the reverse precipitator is petroleum ether: the mass ratio of the anhydrous ether is 1: 1 and drying the obtained precipitate in a vacuum drying oven at 40 ℃.
(3) Weighing 6g of polymalic acid obtained by the polycondensation, adding the polymalic acid into a reaction kettle, adding 1.344g of 1, 5-pentanediol, carrying out vacuum pumping reaction at 130 ℃ for 15min, and curing at 130 ℃ for 24h in a nitrogen atmosphere to obtain the biodegradable polyester elastomer.
The products obtained in examples 1 and 2 and comparative examples 1, 2, 3, 4 and 5 were of the same morphology. FIG. 1 shows visually the fact that the materials prepared in examples 1 and 2 and comparative examples 1, 2 and 5 were stretched under a weight of 50g, and it can be seen that the material prepared in example 1 has the best tensile properties, followed by example 2; the material prepared in comparative example 1 had almost no stretching phenomenon; comparative example 2 the material prepared was more stretchable than comparative example 1, but was still less stretchable than examples 1 and 2. In addition, the tensile strength of the materials obtained in comparative examples 3 and 4 was weak and could not withstand the tensile force of a 50g weight.
FIG. 2 is a stress-strain curve of the composites prepared in comparative examples 1, 2, 5, and it can be seen that all the samples have higher strength but lower elongation at break, not more than 40%.
It can be seen from the comparison of example 1 and comparative examples 1 to 3 that the chain length of the polyethylene glycol as the crosslinking agent affects the mechanical properties of the finally prepared polyester elastomer, that when the chain length is too short (100 to 200), the tensile property of the prepared polyester elastomer is poor, and when the chain length is too long (400), the strength of the prepared polyester elastomer is weak. It can be seen from the comparison of example 1 and comparative example 4 that the curing time also affects the mechanical properties of the finally obtained polyester elastomer, and when the curing time is too short (4h), the overall tensile properties of the obtained polyester elastomer are weaker. As can be seen from the comparison of example 1 and comparative example 5, the choice of the crosslinking agent also affects the mechanical properties of the finally obtained polyester elastomer. The polyester elastomer prepared by using 1, 5-pentanediol as a crosslinking agent has high strength, but has low elongation at break.
Fig. 3 is a stress-strain curve of the composite materials prepared in examples 1 and 2 and comparative examples 3 and 4, and it can be seen that both examples 1 and 2 exhibit good elongation at break, with example 1 having an elongation at break of up to 110% and example 2 having an elongation at break of about 90%, but having a higher strength than example 1. The elongation at break of comparative example 3 is only 85%, and the strength and elongation at break of comparative example 4 are very low. The materials obtained in examples 1 and 2 therefore have the best overall properties.
FIG. 4 is a graph showing the shape memory properties of the material of example 1, the original shape of which is shown in FIG. 4(a), the material being heated above its glass transition temperature to change its shape and cooled below its glass transition temperature to fix its temporary shape, FIG. 4 (b); and increasing the temperature to be higher than the glass transition temperature, and recovering the temporary shape to the original shape, as shown in fig. 4(c), which shows that the polyester elastomer prepared by the method of the invention has good shape memory performance and is suitable for the field of flexible wearable intelligent material preparation.
The present invention is not limited to the above-mentioned embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts according to the disclosed technical contents, and these substitutions and modifications are all within the protection scope of the present invention.
Claims (8)
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