CN112759737B - Triple shape memory polymer and preparation method thereof - Google Patents
Triple shape memory polymer and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
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- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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Abstract
The invention belongs to the technical field of high molecular materials synthesized in a chemical industry, and discloses a triple shape memory polymer and a preparation method thereof. The triple shape memory polymer is prepared by the following method: dissolving polybutylene terephthalate-co-polybutylene succinate copolyester and polycaprolactone in a solvent, adding diisocyanate and a catalyst, and reacting to obtain the triple shape memory polymer; the number average molecular weight of the polybutylene terephthalate-co-polybutylene succinate copolyester is 6000-30000; the number average molecular weight of the polycaprolactone is 5000-30000. The triple shape memory polymer has good triple shape memory performance and biodegradability.
Description
Technical Field
The invention belongs to the technical field of high molecular materials synthesized in a chemical industry, and particularly relates to a triple shape memory polymer and a preparation method thereof.
Background
Shape Memory Polymer (SMP for short) is a stimulus-responsive intelligent material, can be endowed with a temporary Shape under the action of certain temperature and external force, and then is recovered to an initial Shape from the temporary Shape under the condition of external stimulus (including heat, light, electricity, magnetism, solvent and the like) to complete a Shape Memory cycle. Compared with shape memory alloy, SMP has the advantages of light weight, quick recovery, mild recovery conditions, easy molding and processing, etc., and has great development prospect.
From the perspective of molecular structure, SMP has shape memory property, and needs to have both stationary phase and reversible phase. The fixed phase ensures the memory and recovery of the initial shape of the material, and the reversible phase changes reversibly according to the response of external stimulus, thereby ensuring the material to have a temporary shape. Among them, the polymer segment capable of undergoing reversible transformation is the molecular switch with shape change of SMP. With the more intensive research on the mechanism of SMP, novel molecular switches (reversible phase transition) are emerging in addition to the traditional crystal melting transition and glass transition, such as liquid crystal phase, coordination bond, multiple hydrogen bond, photoreversible transition, cellulose whisker network, even-even action, host-guest recognition and the like.
The shape memory polymer belongs to a stimulus response shape changing material, and the shape change and the shape transition temperature of the stimulus response shape changing material can be designed according to requirements. A typical SMP material can be designed to have a wide range of flexibility in terms of its shape transition temperature, temporary shape, and recovery to its set shape under any stimulus. Among shape memory polymers, those having a temporary shape and capable of returning to an original shape are called Dual Shape Memory Polymers (DSMP). A polymer having two temporary shapes and capable of returning to the original shape is called a triple shape memory polymer (TSPM). Generally, TSMP is more complex than dual shape memory polymers.
Patent document CN108264623A describes a polyester type polyurethane shape memory material, which is prepared by prepolymerizing poly (L-lactide), polycaprolactone and diisocyanate into linear polymer chains with the end group of diisocyanate, and then chain-extending with small-molecule diol, wherein both poly (L-lactide) and polycaprolactone adopt a solution polymerization method, the yield is low, the reaction time is long, the solvent needs to be recovered, and the recovery performance of the polymer is reduced because the polymer is a linear chain. Patent document CN108586693A is to blend low molecular weight polycaprolactone (molecular weight is 1000-.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a ternary shape memory polymer and a preparation method thereof.
In a first aspect of the present invention, there is provided a triple shape memory polymer prepared by the following process: dissolving polybutylene terephthalate-co-polybutylene succinate copolyester and polycaprolactone in a solvent, adding diisocyanate and a catalyst, and reacting to obtain the triple shape memory polymer;
the number average molecular weight of the polybutylene terephthalate-co-polybutylene succinate copolyester is 6000-30000; the number average molecular weight of the polycaprolactone is 5000-.
In a second aspect of the present invention, there is provided a method for preparing a triple shape memory polymer, the method comprising the steps of:
1) preparing polybutylene terephthalate-co-polybutylene succinate copolyester: under the inert atmosphere, reacting terephthalic acid, succinic acid, 1, 4-butanediol and polyalcohol under the action of a compound catalyst until no small molecular fraction is evaporated out, and then reacting under the condition of reduced pressure distillation to obtain multi-arm poly (butylene terephthalate) -co-poly (butylene succinate) copolyester with the number average molecular weight of 6000-30000;
2) preparing polycaprolactone: under the inert atmosphere, caprolactone monomers react under the action of an initiator and a catalyst to obtain the multi-arm polycaprolactone with the number average molecular weight of 5000-30000;
3) dissolving the multi-arm polybutylene terephthalate-co-polybutylene succinate copolyester and the multi-arm polycaprolactone in a solvent, adding diisocyanate and a catalyst, and reacting to obtain the triple shape memory polymer.
The PBTS-b-PCL triple shape memory polymer provided by the invention is a triple thermally-driven shape memory polymer material, and the multi-arm PBTS and the multi-arm PCL have long branched chain segments, can generate crystal melting transition, are shape memory switches of the shape memory polymer and have shape transition temperature (T)trans) Melting Point T for PBTS and PCLmPlus or minus 3 ℃; the addition of the diisocyanate enables the multi-arm long branched chain PBTS and PCL to form a PBTS-b-PCL triple shape memory polymer with a multi-arm star-shaped network structure, has a certain cross-linking point, and ensures the recovery characteristic of the shape memory polymer.
The triple shape memory polymer can adjust the structure, performance and shape transition temperature of the memory material by adjusting the proportion of aliphatic and aromatic substances of PBTS and the charge ratio of PBTS and PCL, has a shape fixing rate of more than or equal to 80 percent and a shape recovery rate of more than or equal to 80 percent, has a good triple shape memory effect, and expands the application range of the material.
In addition, the ternary shape memory polymer of the invention selects biodegradable polybutylene terephthalate-co-polybutylene succinate copolyester and polycaprolactone as base materials, and the obtained ternary shape memory polymer also has good biodegradability, does not cause environmental pollution, meets social requirements and can be better applied.
The multi-arm star-shaped network structure PBTS-b-PCL shape memory polymer provided by the invention has the advantages that due to the long-chain branch structures of PBTS and PCL, the PBTS and PCL have respective melt crystallization transformation, the difference between the melting points is more than 20 ℃, and the triple shape memory capability is endowed. Secondly, the existence of the multi-arm long-chain branches enables more physical entanglement among the long-chain branches, and the physical entanglement points can also be used as reversible transformation phases of the shape memory polymer. In addition, the existence of the cross-linking points ensures the recovery property of the shape memory material.
The shape transition recovery process of the PBTS-b-PCL triple shape memory polymer is as follows: when the polymer is heated from the initial shape A to a first transition temperature (T)trans，1T of PBTSmNear) is deformed at a second transition temperature (T)trans，2T of PCLmNearby), the shape is a first temporary shape B, at this time, PBTS is melted and crystallized into a reversible phase, and a cross-linking point is a fixed phase; at the second transition temperature, since the PCL can undergo a crystalline melt transition near the PCL melting point, the shape memory material can continue to deform and set at room temperature, which is the second temporary shape C, at which time the PCL crystalline melt transitions to a reversible transition phase and the PBTS crystalline phase and the crosslink point are stationary phases. Heating to Ttrans，2The material returns from the temporary shape C to the temporary shape B and then is heated to Ttrans，1The material reverts from the temporary shape B to the original shape a.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, there is provided a triple shape memory polymer prepared by the process of: dissolving polybutylene terephthalate-co-polybutylene succinate copolyester and polycaprolactone in a solvent, adding diisocyanate and a catalyst, and reacting to obtain the triple shape memory polymer;
the number average molecular weight of the polybutylene terephthalate-co-polybutylene succinate copolyester is 6000-30000; the number average molecular weight of the polycaprolactone is 5000-30000.
According to the present invention, the polybutylene terephthalate-co-polybutylene succinate copolyester and polycaprolactone can be prepared by conventional methods in the art, and both are multi-arm polymers having long chain segments with branched chains. Preferably, the number average molecular weight of the polybutylene terephthalate-co-polybutylene succinate copolyester is 8000-25000; the number average molecular weight of the polycaprolactone is 8000-20000.
Preferably, the solvent is selected from at least one of N, N-dimethylformamide, toluene, N-dimethylacetamide, tetrahydrofuran, chloroform, and dichloromethane.
According to the invention, the catalyst is an organotin catalyst, preferably stannous octoate, dibutyltin dilaurate or dibutyltin maleate; the dosage of the catalyst is 0.1-0.5 percent of the total weight of the polybutylene terephthalate-co-poly (butylene succinate) copolyester and the polycaprolactone, and is preferably 0.1-0.3 percent.
Preferably, the diisocyanate is selected from at least one of 2, 4-toluene diisocyanate, 4, 4' -diphenylmethane diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, trans-1, 4-cyclohexane diisocyanate, 1, 6-diisocyanate-2, 2, 4-trimethylcyclohexane and 1, 6-diisocyanate-2, 4, 4-trimethylcyclohexane.
The addition amount of the diisocyanate is 1-3 times, preferably 1-1.5 times of the mole number of the terminal hydroxyl in the polybutylene terephthalate-co-polybutylene succinate copolyester and the polycaprolactone.
In the present invention, the feeding ratio of polybutylene terephthalate-co-polybutylene succinate copolyester and polycaprolactone can be adjusted according to actual needs, for example, the feeding ratio (weight ratio) of the polybutylene terephthalate-co-polybutylene succinate copolyester and polycaprolactone can be 1: 5-5: 1, preferably 1: 2-2: 1.
On the basis of the disclosures of the above reaction materials, the conventional reaction conditions in the field are combined to obtain the triple shape memory polymer.
According to a second aspect of the present invention, there is provided a method for preparing a triple shape memory polymer, the method comprising the steps of:
1) preparing polybutylene terephthalate-co-polybutylene succinate copolyester: in an inert atmosphere, reacting terephthalic acid, succinic acid, 1, 4-butanediol and polyhydric alcohol under the action of a compound catalyst until no small molecular fraction is evaporated out, and then reacting under the condition of reduced pressure distillation to obtain polybutylene terephthalate-co-poly (butylene succinate) copolyester with the number average molecular weight of 6000-30000;
2) preparing polycaprolactone: in an inert atmosphere, reacting a caprolactone monomer under the action of an initiator and a catalyst to obtain polycaprolactone with the number average molecular weight of 5000-30000;
3) dissolving the polybutylene terephthalate-co-polybutylene succinate copolyester and polycaprolactone in a solvent, adding diisocyanate and a catalyst, and reacting to obtain the triple shape memory polymer.
In the invention, the molar ratio of the terephthalic acid to the succinic acid is 10-35: 65-90, preferably 10-25: 75-90. In this case, the multi-arm PBTS has a distinct crystalline peak and can be used as a molecular switch for controlling temporal shape.
Preferably, the molar ratio of the total moles of terephthalic acid and succinic acid (diacid) to 1, 4-butanediol (diol) is 1: 1.05-1.4, more preferably 1: 1.1-1.3.
The polyhydric alcohol can be glycerol, pentaerythritol or trimethylolpropane, and the amount of the polyhydric alcohol is 0.05-1%, preferably 0.1-0.8% of the total molar number of the terephthalic acid and the succinic acid.
According to the invention, the preparation process of the multi-arm PBTS comprises an esterification reaction and a polycondensation reaction, and the compound catalyst comprises an esterification catalyst and a polycondensation catalyst.
The esterification catalyst is p-toluenesulfonic acid, antimony trioxide, germanium dioxide, germanium chloride, alkoxy germanium, tetrabutyl titanate, alkyl titanium, stannic chloride or magnesium acetate, and the amount of the esterification catalyst can be 0.01-0.5 part by weight, preferably 0.05-0.3 part by weight, and more preferably 0.06-0.2 part by weight based on 100 parts by weight of terephthalic acid and succinic acid.
The polycondensation catalyst can be a rare earth catalyst, preferably anhydrous lanthanum chloride, lanthanum acetylacetonate or neodymium isopropoxide, and the weight ratio of the polycondensation catalyst to the esterification catalyst is 0.5-1.3: 1, preferably 0.6-1.1: 1.
According to the invention, the reaction of terephthalic acid, succinic acid, 1, 4-butanediol and a polyol is first carried out in a reaction vessel under reaction conditions under an inert atmosphere; the reaction temperature is 130-240 ℃, preferably 140-230 ℃, and the reaction time is 0.1-8h, preferably 3-6h, until no small molecular fraction is distilled; then, the reaction kettle is switched to a reduced pressure distillation device, and the reaction conditions of the reduced pressure distillation comprise: the reaction temperature is 200-260 ℃, preferably 220-250 ℃, the vacuum degree is less than 200PaA, preferably less than 90PaA, and the reaction time is 0.1-8h, preferably 2-5 h.
The inert gas atmosphere in the present invention may be provided by a gas which does not react with the monomer (e.g., a conventional inert gas such as nitrogen).
According to the invention, in the preparation of the multi-arm PCL polymer in the step 2), caprolactone monomers, catalysts and initiators are added into a reaction system according to a preset molecular weight in proportion, and the reaction system is heated for reaction after 30 minutes in an inert atmosphere.
The initiator is a polyol, preferably glycerol, pentaerythritol, trimethylolpropane or di-trimethylolpropane. The polyols are used in conventional amounts, calculated in particular on the basis of a predetermined molecular weight.
The catalyst is stannous octoate, dibutyltin dilaurate or dibutyltin maleate, and the dosage of the catalyst is 0.3-2wt% of caprolactone monomer.
The reaction conditions include: the reaction temperature is 130-190 ℃, preferably 140-170 ℃, and the reaction time is 0.1-8h, preferably 3-6 h.
According to the invention, in the step 3) of preparing the PBTS-b-PCL triple shape memory polymer, firstly, the multi-arm PBTS and the multi-arm PCL are dried at 50 ℃ for 8hr, then are dissolved in a solvent, diisocyanate and a catalyst are added for reaction, after the reaction is finished, the solvent is removed from the reaction product, and then the reaction product is dried in vacuum at 50 ℃ for 2 to 8 hours, so that the triple shape memory polymer is obtained.
Preferably, the solvent is selected from at least one of N, N-dimethylformamide, toluene, N-dimethylacetamide, tetrahydrofuran, chloroform, and dichloromethane.
The catalyst is an organic tin catalyst, preferably stannous octoate, dibutyltin dilaurate or dibutyltin maleate. The dosage of the catalyst is 0.1-0.5 percent of the total weight of the polybutylene terephthalate-co-polybutylene succinate copolyester and the polycaprolactone, and the preferred dosage is 0.1-0.3 percent.
Preferably, the diisocyanate is selected from at least one of 2, 4-toluene diisocyanate, 4, 4' -diphenylmethane diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, trans-1, 4-cyclohexane diisocyanate, 1, 6-diisocyanate-2, 2, 4-trimethylcyclohexane and 1, 6-diisocyanate-2, 4, 4-trimethylcyclohexane.
The addition amount of the diisocyanate can be 1-3 times, preferably 1-1.5 times of the mole number of the terminal hydroxyl in the polybutylene terephthalate-co-polybutylene succinate copolyester and the polycaprolactone.
The reaction conditions include: the reaction temperature is 30-80 ℃, preferably 40-70 ℃, and the reaction time is 2-20h, preferably 4-12 h.
The triple shape memory polymer can be obtained by adopting the preparation method. In addition, the process parameters which are not limited in the invention can be selected conventionally according to the prior art.
The present invention is further illustrated by the following examples. It is to be understood, however, that these examples are for the purpose of illustration and explanation only and are not intended to limit the present invention.
In the following examples, properties such as transition temperature, shape fixation rate and shape recovery rate of PBTS-b-PCL triple shape memory polymer were measured by conventional methods in the art. For example, the shape memory performance of the PBTS-b-PCL triple shape memory polymer is measured by an Instron5965 tensile tester with an environment box, the polymer is prepared into a dumbbell-shaped sample bar, the effective size is 40mm multiplied by 2mm, after the polymer is stretched to the elongation of 150% at the transition temperature at the speed of 20mm/min, the polymer is rapidly cooled for 10min at the temperature of 30 ℃ lower than the transition temperature or at the room temperature under the condition of keeping the existence of stress, the stress is removed, and the change of the effective length is measured, so that the shape fixing rate of the shape memory material is obtained; and heating the sample strip to the transition temperature at the speed of 3 ℃/min again, and measuring the change of the effective length to obtain the shape recovery rate of the shape memory material.
Examples 1-5 are provided to illustrate the triple shape memory polymer of the present invention and the method of preparing the same.
Example 1
Adding terephthalic acid, succinic acid, 1, 4-butanediol and pentaerythritol into a reaction kettle, wherein the molar ratio of the terephthalic acid to the succinic acid is 20: 80, the molar ratio of dibasic acid (the terephthalic acid and the succinic acid) to the dihydric alcohol (1, 4-butanediol) is 1: 1.2, the addition amount of the pentaerythritol is 0.2 percent of the mole number of the dibasic acid monomer, adding a compound catalyst, 0.1 weight part (relative to 100 weight parts of the succinic acid) of tetrabutyl titanate and 0.1 weight part of lanthanum acetylacetonate (the weight ratio of the tetrabutyl titanate is 1: 1), and reacting for 5 hours at 140-; then, the reaction kettle is switched to a reduced pressure distillation device, the temperature is raised to 250 ℃, the vacuum degree of the system is gradually adjusted to be less than 90PaA, and the reaction is carried out for 4 hours to obtain the multi-arm polybutylene terephthalate-co-butylene succinate copolyester (PBTS) with the molecular weight of 14000 g/mol.
Pentaerythritol is taken as an initiator, if the preset molecular weight is 9000g/mol, 0.8mol of caprolactone monomer, 0.01mol of pentaerythritol, 1.37g of stannous octoate and inert gas atmosphere are added into a reaction system, the temperature is raised to 130-170 ℃ after 30 minutes, and the multi-arm Polycaprolactone (PCL) is obtained after reaction for 4 hours.
After drying the multi-arm PBTS and multi-arm PCL at 50 ℃ for 8hr, 5g of each was dissolved in chloroform, and 0.54g of Hexamethylene Diisocyanate (HDI) and 0.03g of dibutyltin dilaurate were added thereto at 50 ℃ for 6 hours. Removing the solvent, and drying the mixture at 50 ℃ for 2-8 hours in vacuum to obtain the PBTS-b-PCL triple shape memory polymer.
The first transition temperature (T) of the product was testedtrans，1) 90 deg.C, 95% shape fixation rate, 93% shape recovery rate, and second transition temperature (T)trans，2) At 60 deg.C, shape fixing rate of 90%The recovery rate of shape was 91%.
Example 2
The PBTS-b-PCL triple shape memory polymer was prepared according to the method of example 1, except that the molar ratio of terephthalic acid and succinic acid in the PBTS polyester was 10: 90, the amount of pentaerythritol added was 0.1% of the molar amount of the dibasic acid monomer, and the polycondensation time was 6 hours, to obtain multi-arm PBTS.
The first transition temperature (T) of the product was testedtrans，1) 100 ℃ C., shape fixation rate of 95%, shape recovery rate of 93%, second transition temperature (T)trans，2) The shape fixation rate was 97% at 60 ℃ and the shape recovery rate was 95%.
Example 3
PBTS-b-PCL triple shape memory polymer was prepared according to the method of example 1 except that the weight ratio of PBTS to PCL was 2: 1.
The first transition temperature (T) of the product was testedtrans，1) 90 deg.C, shape fixation rate of 90%, shape recovery rate of 93%, and second transition temperature (T)trans，2) The shape fixation rate was 97% at 60 ℃ and the shape recovery rate was 95%.
Example 4
A PBTS-b-PCL triple shape memory polymer was prepared according to the method of example 1, except that diisocyanate 4, 4' -diphenylmethane diisocyanate (MDI) and dibutyltin dilaurate were added at 50 ℃ for 8 hours, the solvent was removed, and it was vacuum-dried at 50 ℃ for 8 hours to obtain a PBTS-b-PCL triple shape memory polymer.
The first transition temperature (T) of the product was testedtrans，1) 90 deg.C, 97% shape fixation, 94% shape recovery, and a second transition temperature (T)trans，2) The shape fixation rate was 87% at 60 ℃ and the shape recovery rate was 92%.
Example 5
The PBTS-b-PCL triple shape memory polymer is prepared according to the method of the embodiment 1, except that when the multi-arm PCL is prepared, the initiator is trimethylolpropane, if the preset molecular weight is 10000g/mol, 0.9mol of caprolactone monomer, 0.01mol of trimethylolpropane and 1.02g of stannous octoate are added into the reaction system, the temperature is raised to 130-170 ℃ after 30 minutes, and the multi-arm Polycaprolactone (PCL) is obtained after 4 hours of reaction.
The first transition temperature (T) of the product was testedtrans，1) 90 deg.C, shape fixation rate of 90%, shape recovery rate of 91%, and second transition temperature (T)trans，2) The shape fixation rate was 95% and the shape recovery rate was 90% at 60 ℃.
The data of the embodiment shows that the triple shape memory polymer has adjustable properties such as shape transition temperature, the shape fixing rate can reach more than 87 percent, the shape recovery rate can reach more than 90 percent, and the triple shape memory polymer has good triple shape memory effect and larger applicable range. In addition, the triple shape memory polymer has better biodegradation performance.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (26)
1. A triple shape memory polymer, characterized in that it is prepared by the following method: dissolving polybutylene terephthalate-co-polybutylene succinate copolyester and polycaprolactone in a solvent, adding diisocyanate and a catalyst, and reacting to obtain the triple shape memory polymer;
the number average molecular weight of the polybutylene terephthalate-co-polybutylene succinate copolyester is 8000-25000; the number average molecular weight of the polycaprolactone is 8000-;
the polybutylene terephthalate-co-polybutylene succinate copolyester and the polycaprolactone are multi-arm polymers with long-chain-branch chain segments.
2. The triple shape memory polymer according to claim 1, wherein the solvent is selected from at least one of N, N-dimethylformamide, toluene, N-dimethylacetamide, tetrahydrofuran, chloroform, and dichloromethane;
the catalyst is an organic tin catalyst; the dosage of the catalyst is 0.1-0.5% of the total weight of the polybutylene terephthalate-co-poly (butylene succinate) copolyester and the polycaprolactone.
3. A ternary shape memory polymer according to claim 2 wherein the catalyst is stannous octoate, dibutyltin dilaurate or dibutyltin maleate.
4. A triple shape memory polymer according to claim 2 wherein the catalyst is used in an amount of 0.1-0.3% by weight of the polybutylene terephthalate-co-polybutylene succinate copolyester and polycaprolactone.
5. The triple shape memory polymer according to claim 1, wherein the diisocyanate is selected from at least one of 2, 4-toluene diisocyanate, 4, 4' -diphenylmethane diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, trans 1, 4-cyclohexane diisocyanate, 1, 6-diisocyanate-2, 2, 4-trimethylcyclohexane, and 1, 6-diisocyanate-2, 4, 4-trimethylcyclohexane;
the addition amount of the diisocyanate is 1-3 times of the mole number of the terminal hydroxyl in the polybutylene terephthalate-co-polybutylene succinate copolyester and the polycaprolactone.
6. A ternary shape memory polymer according to claim 5 wherein the diisocyanate is added in an amount of 1 to 1.5 times the molar number of the terminal hydroxyl groups in the polybutylene terephthalate-co-polybutylene succinate copolyester and the polycaprolactone.
7. A method for preparing a triple shape memory polymer, comprising the steps of:
1) preparing polybutylene terephthalate-co-polybutylene succinate copolyester: in an inert atmosphere, reacting terephthalic acid, succinic acid, 1, 4-butanediol and polyhydric alcohol under the action of a compound catalyst until no small molecular fraction is evaporated out, and then reacting under the condition of reduced pressure distillation to obtain polybutylene terephthalate-co-poly (butylene succinate) copolyester with the number average molecular weight of 8000-25000;
2) preparing polycaprolactone: under the inert atmosphere, caprolactone monomers react under the action of an initiator and a catalyst to obtain polycaprolactone with the number average molecular weight of 8000-20000;
3) dissolving the polybutylene terephthalate-co-polybutylene succinate copolyester and polycaprolactone in a solvent, adding diisocyanate and a catalyst, and reacting to obtain the triple shape memory polymer;
the polyalcohol is glycerol, pentaerythritol or trimethylolpropane;
the initiator is glycerol, pentaerythritol, trimethylolpropane or di-trimethylolpropane.
8. The method of claim 7, wherein the molar ratio of terephthalic acid to succinic acid is 10-35: 65-90;
the molar ratio of the total molar number of the terephthalic acid and the succinic acid to the 1, 4-butanediol is 1: 1.05-1.4;
the using amount of the polyalcohol is 0.05-1% of the total mole number of the terephthalic acid and the succinic acid.
9. A method of preparing a triple shape memory polymer according to claim 8 wherein the molar ratio of terephthalic acid to succinic acid is 10-25: 75-90.
10. The method of claim 8, wherein the molar ratio of the total moles of terephthalic acid and succinic acid to the moles of 1, 4-butanediol is 1: 1.1-1.3.
11. A method of making a triple shape memory polymer according to claim 8 wherein the polyol is used in an amount of 0.1 to 0.8% of the total moles of terephthalic acid and succinic acid.
12. A method of preparing a triple shape memory polymer according to claim 7 wherein the built catalyst comprises an esterification catalyst and a polycondensation catalyst;
the esterification catalyst is p-toluenesulfonic acid, antimony trioxide, germanium dioxide, germanium chloride, alkoxy germanium, tetrabutyl titanate, alkyl titanium, stannic chloride or magnesium acetate, and the amount of the esterification catalyst is 0.01-0.5 part by weight based on 100 parts by weight of terephthalic acid and succinic acid;
the polycondensation catalyst is anhydrous lanthanum chloride, lanthanum acetylacetonate or neodymium isopropoxide, and the weight ratio of the polycondensation catalyst to the esterification catalyst is 0.5-1.3: 1.
13. A method of preparing a triple shape memory polymer according to claim 12, wherein the esterification catalyst is used in an amount of 0.05 to 0.3 parts by weight, based on 100 parts by weight of terephthalic acid and succinic acid.
14. A method of preparing a triple shape memory polymer according to claim 13, wherein the esterification catalyst is used in an amount of 0.06 to 0.2 parts by weight, based on 100 parts by weight of terephthalic acid and succinic acid.
15. A method of preparing a triple shape memory polymer according to claim 12 wherein the weight ratio of polycondensation catalyst to esterification catalyst is 0.6-1.1: 1.
16. The method for preparing a triple shape memory polymer according to claim 7, wherein the reaction conditions under an inert atmosphere in step 1) comprise: the reaction temperature is 130-240 ℃, and the reaction time is 0.1-8 h;
the reaction conditions of the reduced pressure distillation include: the reaction temperature is 200 ℃ and 260 ℃, the vacuum degree is below 200PaA, and the reaction time is 0.1-8 h.
17. The method for preparing a triple shape memory polymer according to claim 16, wherein the reaction conditions under the inert atmosphere comprise a reaction temperature of 140 ℃ and a reaction temperature of 230 ℃ and a reaction time of 3-6 h.
18. A method of preparing a ternary shape memory polymer according to claim 16 wherein the reaction conditions of reduced pressure distillation comprise: the reaction temperature is 220 ℃ and 250 ℃, the vacuum degree is below 90PaA, and the reaction time is 2-5 h.
19. A method of preparing a ternary shape memory polymer according to claim 7 wherein, in step 2),
the catalyst is stannous octoate, dibutyltin dilaurate or dibutyltin maleate, and the using amount of the catalyst is 0.3-2wt% of caprolactone monomer;
the reaction conditions include: the reaction temperature is 130 ℃ and 190 ℃, and the reaction time is 0.1-8 h.
20. A method of making a triple shape memory polymer according to claim 19 wherein the conditions of the reaction comprise: the reaction temperature is 140 ℃ and 170 ℃, and the reaction time is 3-6 h.
21. The method for preparing a triple shape memory polymer according to claim 7, wherein the solvent is at least one selected from the group consisting of N, N-dimethylformamide, toluene, N-dimethylacetamide, tetrahydrofuran, chloroform and dichloromethane in step 3);
the catalyst is an organic tin catalyst; the dosage of the catalyst is 0.1-0.5% of the total weight of the polybutylene terephthalate-co-poly (butylene succinate) copolyester and the polycaprolactone.
22. A method of preparing a ternary shape memory polymer according to claim 21 wherein the catalyst is stannous octoate, dibutyltin dilaurate or dibutyltin maleate.
23. A method of preparing a triple shape memory polymer according to claim 21 wherein the amount of the catalyst is 0.1-0.3% by weight of the polybutylene terephthalate-co-polybutylene succinate copolyester and polycaprolactone.
24. A method of preparing a triple shape memory polymer according to claim 7, wherein, in step 3), the diisocyanate is selected from at least one of 2, 4-toluene diisocyanate, 4, 4' -diphenylmethane diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, trans 1, 4-cyclohexane diisocyanate, 1, 6-diisocyanate-2, 2, 4-trimethylcyclohexane, and 1, 6-diisocyanate-2, 4, 4-trimethylcyclohexane; the adding amount of the diisocyanate is 1-3 times of the mole number of the terminal hydroxyl in the polybutylene terephthalate-co-polybutylene succinate copolyester and the polycaprolactone;
the reaction conditions include: the reaction temperature is 30-80 ℃, and the reaction time is 2-20 h.
25. A method of preparing a triple shape memory polymer according to claim 24 wherein the diisocyanate is added in an amount of 1 to 1.5 times the moles of the terminal hydroxyl groups in the polybutylene terephthalate-co-polybutylene succinate copolyester and polycaprolactone.
26. A method of making a triple shape memory polymer according to claim 24 wherein the conditions of the reaction include: the reaction temperature is 40-70 ℃, and the reaction time is 4-12 h.
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