A preparation method and application of thermoplastic polyurethane elastomer
By introducing UPy-based hyperbranched polyamide into thermoplastic polyurethane to form quadrupole hydrogen bonds, the problem of poor tensile performance of polyurethane elastomers is solved, the hardness and shape memory characteristics are significantly improved, and its application prospects are broadened.
Patent Information
- Application Number
- CN202410558338.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-05-07
- Publication Date
- 2024-12-10
- Estimated Expiration
- 2044-05-07
AI Technical Summary
The tensile performance of existing thermoplastic polyurethane elastomers is poor and it is difficult to meet certain application needs.
By introducing UPy-based hyperbranched polyamide to form a quadrupole hydrogen bond with polyurethane, a three-dimensional physical crosslinking network is formed, which enhances the hardness and tensile properties of the polyurethane and imparts its self-healing and shape memory properties.
It significantly improves the hardness and tensile properties of polyurethane elastomers, and achieves high shape fixation and shape recovery rates, broadening its application prospects in self-healing shape memory materials.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of polyurethane, in particular to a preparation method and application of a thermoplastic polyurethane elastomer. Background Art
[0002] Shape memory materials can sense the stimulation of environmental changes, adjust their shape, strain and other properties, and restore them to their original state. As a new type of smart material, they are widely used in medical devices, bioengineering, artificial satellites and other fields. Compared with traditional alloy memory materials, polymer smart memory materials have the advantages of high elasticity, good toughness and excellent biocompatibility. They mainly include polyurethane, polylactic acid, polyacrylamide and other shape memory materials, which are widely used.
[0003] Thermoplastic polyurethane elastomers have excellent wear resistance, high and low temperature resistance, mildew resistance, hydrolysis resistance and other properties, and are widely used in sports goods, medical supplies, etc. The Chinese patent with patent number CN114736380B discloses a photocurable castor oil-based shape memory elastomer and its preparation method and application. Castor oil-based polyurethane prepolymer and bis (2-hydroxyethyl) disulfide are subjected to chain extension reaction, and then end-capped with hydroxyethyl methacrylate. The obtained shape memory elastomer has the advantages of rapid curing and reduced energy consumption. However, the tensile properties of the shape memory elastomer are poor.
[0004] Hyperbranched polymers can be used as toughening agents, reinforcing agents, plasticizers, etc., and are widely used in polymer materials. The present invention aims to use hyperbranched polymers to form quadruple hydrogen bonds with polyurethane to give thermoplastic polyurethane elastomers better mechanical properties and shape memory properties. Summary of the invention
[0005] Technical problem to be solved: The present invention provides a thermoplastic polyurethane elastomer with high mechanical properties and shape memory function.
[0006] Technical Solution
[0007] A method for preparing a thermoplastic polyurethane elastomer comprises the following steps:
[0008] Step S1, adding N-methylpyrrolidone, pyridine, triphenyl phosphite, and a structural formula of The UPy-based polymerization monomer is introduced with nitrogen to carry out a self-polymerization reaction. After cooling, methanol is added to the solution to precipitate a precipitate. The precipitate is filtered, washed with ethanol, and dried to obtain a UPy-based hyperbranched polyamide.
[0009] Step S2, add diol to the reaction container, vacuum dehydrate, then introduce nitrogen, heat to 65-75°C, add hexamethylene diisocyanate, react for 2-4h to obtain a polyurethane prepolymer; then, the polyurethane prepolymer, the structural formula is The UPy-based chain extender and the UPy-based hyperbranched polyamide are poured into a preheated mold, stirred, heat-cured, and then aged to obtain a thermoplastic polyurethane elastomer.
[0010] Wherein, the molar amount of pyridine and triphenyl phosphite in step S1 is 160-200% and 600-680% of the molar amount of UPy-based polymerization monomer.
[0011] Wherein, the polymerization reaction in step S1 is carried out at 90-110° C. for 2-5 hours.
[0012] Wherein, in step S2, the molar ratio of diol, hexamethylene diisocyanate and UPy-based chain extender is 1:(2-2.4):(1-1.4).
[0013] Wherein, the diol in step S2 includes polycarbonate diol, polycaprolactone diol, polytetramethylene glycol, and polyethylene glycol.
[0014] Wherein, in step S2, the heat curing is carried out in a flat vulcanizer at a pressure of 8-10 MPa and a temperature of 110-120° C. for 1-2 hours; and the curing is carried out in an oven at a temperature of 90-100° C. for 18-24 hours.
[0015] Wherein, the preparation method of UPy-based polymer monomer is:
[0016] (1) nitrogen was introduced into the reaction vessel, and chloroform solvent, 3-amino-5-boronic acid, and the structural formula The UPy-HD I semi-addition product is prepared by condensing and refluxing at 60-65° C. for 4-8 hours, and the solution is concentrated, washed with acetone, and dried to obtain UPy-5-borylbenzoic acid.
[0017] (2) nitrogen is introduced into a reaction container, and 1,4-dioxane, UPy-5-borylbenzoic acid, and 5-bromo-1,3-phenylenediamine are added, wherein the molar amount of UPy-5-borylbenzoic acid is 105-120% of the molar amount of 5-bromo-1,3-phenylenediamine; potassium carbonate and tetrakis(triphenylphosphine)palladium are added after stirring and dissolving, and the mixture is reacted at 90-100° C. for 18-24 hours, the solution is concentrated, washed with water and acetone, and dried to obtain a UPy-based polymerization monomer.
[0018] Technical effect: The present invention uses 3-amino-5-boronic acid, UPy-HDI semi-addition product, and 5-bromo-1,3-phenylenediamine as reactants to prepare a novel AB2-type UPy-based polymerization monomer, which contains a carboxyl group and two amino groups and can undergo hyperbranched self-polymerization reaction to obtain a novel hyperbranched polyamide containing UPy structural units.
[0019] The present invention introduces UPy structural units into the molecular chain of polyurethane, and simultaneously adds UPy-based hyperbranched polyamide, wherein the hyperbranched polyamide contains branched network molecular chains, and forms a three-dimensional physical cross-linked network with the polyurethane molecular chain, and the UPy structural units in the hyperbranched polyamide molecular chain form a unique quadruple hydrogen bond with the UPy structural units in the polyurethane molecular chain, thereby further enhancing the interface bonding strength between the polyurethane and the hyperbranched polyamide, forming a more stable cross-linked system, and significantly improving the hardness and tensile properties of the polyurethane elastomer.
[0020] The quadruple hydrogen bonds formed between the hyperbranched polyamide and the polyurethane of the present invention have strong cross-linking reversibility. When subjected to external force, the quadruple hydrogen bonds are broken. When the external force disappears, the quadruple hydrogen bonds have a cross-linking effect, thereby giving the polyurethane elastomer unique self-healing and shape memory properties, showing a high shape fixation rate and shape recovery rate, which makes the polyurethane elastomer have a broad application prospect in self-healing shape memory materials. DETAILED DESCRIPTION
[0021] Unless otherwise defined, all scientific and technical terms used in the present invention have the same meanings as those commonly understood by those skilled in the art to which the present invention relates. The present invention will be further illustrated below in conjunction with specific embodiments. It should be understood that the following specific embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention.
[0022] According to the method of the journal "Polyurethane Industry", Vol. 26, No. 2, 2011, the document "Synthesis of Quadruple Hydrogen Bond Chain Extender and Its Effect on Polyurethane Properties", UPy-HD I semi-addition product (structural formula: ) and UPy-based chain extender (structural formula: ).
[0023] Example 1
[0024] (1) Nitrogen was introduced into the reaction vessel, 200 mL of chloroform solvent, 0.02 mol 3-amino-5-borylbenzoic acid, and 0.026 mol UPy-HD I semi-addition product were added, and the mixture was condensed and refluxed at 60° C. for 6 h. The solution was concentrated, washed with acetone, and dried to obtain UPy-5-borylbenzoic acid. The reaction formula is as follows:
[0025]
[0026] (2) Nitrogen was introduced into the reaction vessel, 400 mL of 1,4-dioxane, 0.022 mol UPy-based-5-boronic acid, and 0.02 mmol 5-bromo-1,3-phenylenediamine were added, and after stirring and dissolving, 0.056 mol potassium carbonate and 1.1 mmol tetrakis(triphenylphosphine)palladium were added, and the mixture was reacted at 90° C. for 20 h. The solution was concentrated, washed with water and acetone, and dried to obtain a UPy-based polymer monomer. The reaction formula is as follows:
[0027]
[0028] (3) 150 mL of N-methylpyrrolidone, 0.3 mol of pyridine, 0.1 mol of triphenyl phosphite, and 0.05 mol of UPy-based polymerization monomer were added to a reaction container, nitrogen was introduced, and a self-polymerization reaction was carried out at 110° C. for 3 h. After cooling, methanol was added to the solution to precipitate the precipitate, which was filtered, washed with ethanol, and dried to obtain UPy-based hyperbranched polyamide.
[0029] (4) 0.1 mol polycarbonate diol (molecular weight 2000) was added to the reaction container, vacuum dehydration was carried out, nitrogen was then introduced, the temperature was raised to 65°C, 0.2 mol hexamethylene diisocyanate was added, and the reaction was carried out for 2 hours to obtain a polyurethane prepolymer; then the polyurethane prepolymer, 0.1 mol UPy-based chain extender, and UPy-based hyperbranched polyamide were rapidly stirred, and then quickly poured into a preheated mold, and heat-cured at 120°C for 1 hour in a flat vulcanizer under a pressure of 8 MPa, and then placed in an oven and aged at 100°C for 20 hours to obtain a thermoplastic polyurethane elastomer, and the mass fraction of UPy-based hyperbranched polyamide in the thermoplastic polyurethane elastomer was controlled to be 3%.
[0030] Example 2
[0031] (1) Nitrogen was introduced into a reaction vessel, and 200 mL of chloroform solvent, 0.02 mol 3-amino-5-borylbenzoic acid, and 0.026 mol UPy-HDI semi-addition product were added. The mixture was condensed and refluxed at 65° C. for 4 h. The solution was concentrated, washed with acetone, and dried to obtain UPy-5-borylbenzoic acid.
[0032] (2) Nitrogen was introduced into the reaction container, 500 mL of 1,4-dioxane, 0.024 mol UPy-5-boronic acid, and 0.02 mmol 5-bromo-1,3-phenylenediamine were added, and after stirring to dissolve, 0.056 mol potassium carbonate and 1.2 mmol tetrakis(triphenylphosphine)palladium were added, and the mixture was reacted at 100° C. for 18 h. The solution was concentrated, washed with water and acetone, and dried to obtain a UPy-based polymer monomer.
[0033] (3) 200 mL of N-methylpyrrolidone, 0.34 mol of pyridine, 0.1 mol of triphenyl phosphite, and 0.05 mol of UPy-based polymerization monomer were added to a reaction container, nitrogen was introduced, and a self-polymerization reaction was carried out at 90° C. for 5 h. After cooling, methanol was added to the solution to precipitate the precipitate, which was filtered, washed with ethanol, and dried to obtain UPy-based hyperbranched polyamide.
[0034] (4) 0.1 mol polycaprolactone diol (molecular weight 2000) was added to the reaction container, vacuum dehydration was carried out, nitrogen was then introduced, the temperature was raised to 65°C, 0.24 mol hexamethylene diisocyanate was added, and the reaction was carried out for 2 hours to obtain a polyurethane prepolymer; then the polyurethane prepolymer, 0.14 mol UPy-based chain extender, and UPy-based hyperbranched polyamide were rapidly stirred, and then quickly poured into a preheated mold, and heat-cured at 115°C for 2 hours under a pressure of 10 MPa in a flat vulcanizer, and then placed in an oven and aged at 90°C for 24 hours to obtain a thermoplastic polyurethane elastomer, and the mass fraction of UPy-based hyperbranched polyamide in the thermoplastic polyurethane elastomer was controlled to be 7%.
[0035] Example 3
[0036] (1) Nitrogen was introduced into a reaction vessel, and 150 mL of chloroform solvent, 0.02 mol 3-amino-5-borylbenzoic acid, and 0.018 mol UPy-HDI semi-addition product were added. The mixture was condensed and refluxed at 65° C. for 5 h. The solution was concentrated, washed with acetone, and dried to obtain UPy-5-borylbenzoic acid.
[0037] (2) Nitrogen was introduced into the reaction container, and 600 mL of 1,4-dioxane, 0.021 mol UPy-based-5-boronic acid, and 0.02 mmol 5-bromo-1,3-phenylenediamine were added. After stirring and dissolving, 0.052 mol potassium carbonate and 1.3 mmol tetrakis(triphenylphosphine)palladium were added. The mixture was reacted at 100° C. for 18 h. The solution was concentrated, washed with water and acetone, and dried to obtain a UPy-based polymer monomer.
[0038] (3) 200 mL of N-methylpyrrolidone, 0.34 mol of pyridine, 0.1 mol of triphenyl phosphite, and 0.05 mol of UPy-based polymerization monomer were added to a reaction container, nitrogen was introduced, and a self-polymerization reaction was carried out at 90° C. for 5 h. After cooling, methanol was added to the solution to precipitate the precipitate, which was filtered, washed with ethanol, and dried to obtain UPy-based hyperbranched polyamide.
[0039] (4) 0.1 mol polyethylene glycol (molecular weight 2000) was added to the reaction container, vacuum dehydration was carried out, nitrogen was then introduced, the temperature was raised to 75°C, 0.24 mol hexamethylene diisocyanate was added, and the reaction was carried out for 2 hours to obtain a polyurethane prepolymer; then the polyurethane prepolymer, 0.12 mol UPy-based chain extender, and UPy-based hyperbranched polyamide were rapidly stirred, and then quickly poured into a preheated mold, and heat-cured at 120°C for 1 hour in a flat vulcanizer under a pressure of 8 MPa, and then placed in an oven and aged at 100°C for 18 hours to obtain a thermoplastic polyurethane elastomer, and the mass fraction of UPy-based hyperbranched polyamide in the thermoplastic polyurethane elastomer was controlled to be 12%.
[0040] Example 4
[0041] (1) Nitrogen was introduced into a reaction vessel, and 150 mL of chloroform solvent, 0.02 mol 3-amino-5-borylbenzoic acid, and 0.02 mol UPy-HDI semi-addition product were added, and the mixture was condensed and refluxed at 60° C. for 8 h. The solution was concentrated, washed with acetone, and dried to obtain UPy-5-borylbenzoic acid.
[0042] (2) Nitrogen was introduced into the reaction container, 400 mL of 1,4-dioxane, 0.021 mol UPy-based-5-boronic acid, and 0.02 mmol 5-bromo-1,3-phenylenediamine were added, and after stirring to dissolve, 0.045 mol potassium carbonate and 1.1 mmol tetrakis(triphenylphosphine)palladium were added, and the mixture was reacted at 90° C. for 24 h. The solution was concentrated, washed with water and acetone, and dried to obtain a UPy-based polymer monomer.
[0043] (3) 200 mL of N-methylpyrrolidone, 0.3 mol of pyridine, 0.08 mol of triphenyl phosphite, and 0.05 mol of UPy-based polymerization monomer were added to a reaction container, nitrogen was introduced, and a self-polymerization reaction was carried out at 100° C. for 2 h. After cooling, methanol was added to the solution to precipitate the precipitate, which was filtered, washed with ethanol, and dried to obtain UPy-based hyperbranched polyamide.
[0044] (4) 0.1 mol polytetramethylene diol (molecular weight 2000) was added to the reaction container, vacuum dehydration was carried out, nitrogen was then introduced, the temperature was raised to 70°C, 0.22 mol hexamethylene diisocyanate was added, and the reaction was carried out for 3 hours to obtain a polyurethane prepolymer; then the polyurethane prepolymer, 0.1 mol UPy-based chain extender, and UPy-based hyperbranched polyamide were rapidly stirred, and then quickly poured into a preheated mold, and heat-cured at 110°C for 2 hours under a pressure of 8 MPa in a flat vulcanizer, and then placed in an oven and aged at 90°C for 24 hours to obtain a thermoplastic polyurethane elastomer, and the mass fraction of UPy-based hyperbranched polyamide in the thermoplastic polyurethane elastomer was controlled to be 15%.
[0045] Comparative Example 1
[0046] 0.1 mol polycarbonate diol (molecular weight 2000) was added to a reaction container, vacuum dehydration was carried out, nitrogen was then introduced, the temperature was raised to 65° C., 0.2 mol hexamethylene diisocyanate was added, and the reaction was carried out for 2 h to obtain a polyurethane prepolymer; then the polyurethane prepolymer, 0.1 mol 1,4-butanediol, and UPy-based hyperbranched polyamide (prepared according to the method of Example 1) were rapidly stirred, and then quickly poured into a preheated mold, and heat-cured at 120° C. for 1 h in a flat vulcanizer at a pressure of 8 MPa, and then placed in an oven and aged at 100° C. for 20 h to obtain a thermoplastic polyurethane elastomer, and the mass fraction of UPy-based hyperbranched polyamide in the thermoplastic polyurethane elastomer was controlled to be 3%.
[0047] Comparative Example 2
[0048] 0.1 mol polycarbonate diol (molecular weight 2000) was added to the reaction container, vacuum dehydration was carried out, nitrogen was then introduced, the temperature was raised to 65°C, 0.2 mol hexamethylene diisocyanate was added, and the reaction was carried out for 2 hours to obtain a polyurethane prepolymer; then the polyurethane prepolymer and 0.1 mol UPy-based chain extender were quickly stirred and quickly poured into a preheated mold, and heat cured at 120°C for 1 hour in a flat vulcanizer under a pressure of 8 MPa, and then placed in an oven and aged at 100°C for 20 hours to obtain a thermoplastic polyurethane elastomer.
[0049] The tensile properties of thermoplastic polyurethane elastomers were tested according to GB / T 528-2009. The Shore hardness of thermoplastic polyurethane elastomers was tested according to GB / T531.1-2009. The test results are shown in Table 1.
[0050] Table 1 Mechanical properties test of thermoplastic polyurethane elastomer
[0051]
[0052]
[0053] The thermoplastic polyurethane elastomer was made into a dumbbell-shaped specimen of 25mm×5mm×1mm (the middle length of the specimen was L0), placed in an oven at 80°C, left for 5mm, then slowly stretched to 200% (the middle length of the specimen was 2L0), then suddenly cooled to 0°C and left for 5min (the middle length of the specimen was L1), the load was removed, and the temperature was increased from 25°C to 90°C (the middle length of the specimen was L2) on a heat stage at a heating rate of 5°C / min, repeated 3 times, and the average value was taken to calculate the shape fixation rate and shape recovery rate. Shape fixation rate = (L1-L0) / L0×100%. Shape recovery rate = (2L0-L2) / L0×100%. The test results are shown in Table 2.
[0054] Table 2 Shape memory properties test of thermoplastic polyurethane elastomer
[0055] Shape fixation rate (%) Shape recovery rate (%) Example 1 98.01 99.15 Example 2 98.14 99.85 Example 3 94.78 98.13 Example 4 96.24 98.65 Comparative Example 1 39.24 58.12 Comparative Example 2 91.93 95.86
[0056] As shown in Table 1 and Table 2, the Shore hardness of the thermoplastic polyurethane elastomer of each embodiment reaches 79-88, the tensile strength reaches 26.4-44.6 MPa, and the elongation at break reaches 715.7-1125.0%. It shows excellent mechanical properties. At the same time, the shape fixation rate reaches 94.78-98.14%, and the shape recovery rate reaches 98.13-99.85%. This is because the UPy-based chain extender is added to the polyurethane, and the UPy structural unit ( ), and UPy-based hyperbranched polyamide is added at the same time. The hyperbranched polyamide contains a branched network molecular chain, which forms a three-dimensional physical cross-linked network with the polyurethane molecular chain. At the same time, the UPy structural unit in the hyperbranched polyamide molecular chain forms a unique quadruple hydrogen bond with the UPy structural unit in the polyurethane molecular chain, further enhancing the interface bonding strength between the polyurethane and the hyperbranched polyamide, forming a more stable cross-linked system, and significantly improving the hardness and tensile properties of the polyurethane elastomer. In addition, the quadruple hydrogen bond formed between the hyperbranched polyamide and the polyurethane has a strong cross-linking reversibility. When subjected to an external force, the quadruple hydrogen bond breaks. When the external force disappears, the quadruple hydrogen bond has a cross-linking effect, thereby giving the polyurethane elastomer unique self-healing and shape memory properties, showing a very high shape fixation rate and shape recovery rate.
[0057] In Comparative Example 1, 1,4-butanediol is used as a chain extender. The polyurethane elastomer molecular chain does not contain a UPy structural unit and cannot form a quadruple hydrogen bond with the UPy-based hyperbranched polyamide, resulting in low interfacial bonding strength between the polyurethane and the hyperbranched polyamide, and poor mechanical properties and shape memory properties.
[0058] Comparative Example 2 does not add UPy-based hyperbranched polyamide, and the hardness and tensile properties of the polyurethane elastomer are poor, which are lower than those of Comparative Example 1. It can be seen that UPy-based hyperbranched polyamide has a great influence on the mechanical properties of the polyurethane elastomer. However, the shape fixation rate and shape recovery rate of Comparative Example 2 are significantly higher than those of Comparative Example 1, and have certain shape memory properties. This is because the molecular chain of the polyurethane elastomer contains UPy structural units, so that quadruple hydrogen bonds can be formed between the polyurethane molecular chains, which can give the polyurethane elastomer good shape memory properties.
[0059] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.
Claims
1. A method for preparing a thermoplastic polyurethane elastomer, It is characterized in that The preparation method comprises the following steps: Step S1, adding N-methylpyrrolidone, pyridine, triphenyl phosphite, and a structural formula of UPy-based polymer monomers are introduced with nitrogen to perform a self-polymerization reaction, methanol is added to the solution after cooling, a precipitate is precipitated, and the precipitate is filtered, washed, and dried to obtain a UPy-based hyperbranched polyamide; Step S2, add diol to the reaction container, vacuum dehydrate, then introduce nitrogen, heat to 65-75°C, add hexamethylene diisocyanate, react for 2-4h to obtain a polyurethane prepolymer; then, the polyurethane prepolymer, the structural formula is The UPy-based chain extender and the UPy-based hyperbranched polyamide are poured into a preheated mold, stirred, heat-cured, and then aged to obtain a thermoplastic polyurethane elastomer.
2. The method for preparing a thermoplastic polyurethane elastomer according to claim 1, It is characterized in that In the step S1, the molar amounts of pyridine and triphenyl phosphite are 160-200% and 600-680% of the molar amount of the UPy-based polymerizable monomer.
3. The method for preparing a thermoplastic polyurethane elastomer according to claim 1, It is characterized in that The polymerization reaction in step S1 is carried out at 90-110° C. for 2-5 hours.
4. The method for preparing a thermoplastic polyurethane elastomer according to claim 1, It is characterized in that In step S2, the molar ratio of the diol, hexamethylene diisocyanate and UPy-based chain extender is 1:(2-2.4):(1-1.4); the diol includes any one of polycarbonate diol, polycaprolactone diol, polytetramethylene ether diol and polyethylene glycol.
5. The method for preparing a thermoplastic polyurethane elastomer according to claim 1, It is characterized in that In step S2, the heat curing is carried out in a flat vulcanizer at a pressure of 8-10 MPa and at 110-120° C. for 1-2 hours; and the curing is carried out in an oven at 90-100° C. for 18-24 hours.
6. The method for preparing a thermoplastic polyurethane elastomer according to claim 1, It is characterized in that In the step S2, the mass fraction of the UPy-based hyperbranched polyamide in the thermoplastic polyurethane elastomer is 3-15%.
7. The method for preparing a thermoplastic polyurethane elastomer according to claim 1, It is characterized in that The preparation method of the UPy-based polymer monomer is: (1) nitrogen is introduced into a reaction vessel, chloroform solvent, 3-amino-5-borylbenzoic acid, and UPy-HDI semi-addition product of the structural formula are added, and the reaction is condensed and refluxed at 60-65° C. for 4-8 hours, and the solution is concentrated, washed, and dried to obtain UPy-5-borylbenzoic acid; (2) nitrogen is introduced into a reaction container, 1,4-dioxane, UPy-based-5-boronic acid, and 5-bromo-1,3-phenylenediamine are added, and potassium carbonate and tetrakis(triphenylphosphine)palladium are added after stirring to dissolve, and the mixture is reacted at 90-100° C. for 18-24 hours. The solution is concentrated, washed, and dried to obtain a UPy-based polymerization monomer.
8. The method for preparing a thermoplastic polyurethane elastomer according to claim 7, It is characterized in that The molar amount of the UPy-HDI semi-addition product in (1) is 90-130% of the molar amount of 3-amino-5-boronic acid.
9. The method for preparing a thermoplastic polyurethane elastomer according to claim 7, It is characterized in that The molar amount of UPy-5-borylbenzoic acid in (2) is 105-120% of the molar amount of 5-bromo-1,3-phenylenediamine.
10. Use of the thermoplastic polyurethane elastomer obtained by the preparation method according to any one of claims 1 to 9 in shape memory materials.