CN115594815A - High-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, preparation method, recycling method, degradation method and surgical operation line thereof - Google Patents
High-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, preparation method, recycling method, degradation method and surgical operation line thereof Download PDFInfo
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- CN115594815A CN115594815A CN202211208746.2A CN202211208746A CN115594815A CN 115594815 A CN115594815 A CN 115594815A CN 202211208746 A CN202211208746 A CN 202211208746A CN 115594815 A CN115594815 A CN 115594815A
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- Prior art keywords
- polyurethane elastomer
- temperature
- sensitive polyurethane
- diol
- strength tear
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Links
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004064 recycling Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 230000015556 catabolic process Effects 0.000 title abstract description 10
- 238000006731 degradation reaction Methods 0.000 title abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 43
- 229920001971 elastomer Polymers 0.000 claims abstract description 36
- 239000000806 elastomer Substances 0.000 claims abstract description 35
- 150000002009 diols Chemical group 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 229920001610 polycaprolactone Polymers 0.000 claims description 16
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 14
- 229920000570 polyether Polymers 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004970 Chain extender Substances 0.000 claims description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 12
- 239000004632 polycaprolactone Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- PCYGLFXKCBFGPC-UHFFFAOYSA-N 3,4-Dihydroxy hydroxymethyl benzene Natural products OCC1=CC=C(O)C(O)=C1 PCYGLFXKCBFGPC-UHFFFAOYSA-N 0.000 claims description 6
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- -1 amine diol Chemical class 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 102000004882 Lipase Human genes 0.000 claims description 5
- 108090001060 Lipase Proteins 0.000 claims description 5
- 239000004367 Lipase Substances 0.000 claims description 5
- 235000019421 lipase Nutrition 0.000 claims description 5
- 239000008363 phosphate buffer Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000000593 degrading effect Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 11
- 230000032683 aging Effects 0.000 abstract description 8
- 238000000338 in vitro Methods 0.000 abstract description 4
- 238000001727 in vivo Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- BKUKXOMYGPYFJJ-UHFFFAOYSA-N 2-ethylsulfanyl-1h-benzimidazole;hydrobromide Chemical compound Br.C1=CC=C2NC(SCC)=NC2=C1 BKUKXOMYGPYFJJ-UHFFFAOYSA-N 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 229920002635 polyurethane Polymers 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 206010052428 Wound Diseases 0.000 description 15
- 208000027418 Wounds and injury Diseases 0.000 description 15
- 239000000523 sample Substances 0.000 description 7
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000002953 phosphate buffered saline Substances 0.000 description 6
- 150000004698 iron complex Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
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- 238000007605 air drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 210000003491 skin Anatomy 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000029663 wound healing Effects 0.000 description 3
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000699666 Mus <mouse, genus> Species 0.000 description 2
- 241000699670 Mus sp. Species 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
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- 210000002615 epidermis Anatomy 0.000 description 2
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- 230000002427 irreversible effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
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- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
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- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000007490 hematoxylin and eosin (H&E) staining Methods 0.000 description 1
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- 159000000014 iron salts Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 206010033675 panniculitis Diseases 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
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- 210000004304 subcutaneous tissue Anatomy 0.000 description 1
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Images
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
- A61L17/06—At least partially resorbable materials
- A61L17/10—At least partially resorbable materials containing macromolecular materials
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- 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
- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J11/04—Recovery or working-up of waste materials of polymers
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- 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
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- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
- C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
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- 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
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/105—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with enzymes
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- 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
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The application provides a degradable temperature sensitive polyurethane is torn to tearing of high strengthAn ester elastomer, a preparation method, a recovery method, a degradation method and a surgical operation line thereof, relating to the field of materials. A high strength tear resistant degradable temperature sensitive polyurethane elastomer comprising one or more of the following repeating units:the application provides a degradable temperature sensitive polyurethane elastomer is torn to high strength tearing has very strong ability and intensity of tearing, has good in vitro biocompatibility in vivo and has had recoverable and degradable performance and good ability of anti hot oxygen ageing concurrently.
Description
Technical Field
The application relates to the field of materials, in particular to a high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, and a preparation method, a recovery method, a degradation method and a surgical operation line thereof.
Background
Conventional elastomeric materials, such as rubber, are widely used in sealing devices, tires, brakes, and medical devices due to their good elasticity and mechanical properties. But its practical application is greatly limited due to some significant disadvantages such as non-degradability, weak resistance to breakage and poor biocompatibility.
At present, in order to meet the strategy of sustainable development, the preparation of degradable elastomer materials is mainly selected from raw materials, and degradable precursor materials such as polyethylene glycol, polycaprolactone and the like are selected. For enhancing mechanical properties and anti-damage capability, structures and interaction forces acting as sacrificial bonds are often introduced into a polymer system, such as fillers, hydrogen bonds, coordination bonds, crystalline structures, double networks, and the like. Inevitably, this makes recycling of these materials a difficult problem, since some irreversible sacrificial structural damage, such as phase separation of the filler, double network structure and irreversible crystallization, will lead to a sharp decrease in mechanical properties. The current common method is to introduce reversible structures such as ionic bonds, hydrogen bonds, coordination bonds and the like, and to realize complete recovery of mechanical properties of the recycled material through dynamic recovery after destruction.
At the same time, many elastomeric materials exhibit very low tear resistance. Once a defect has occurred in the material, the crack will rapidly grow and grow, so that the material is discarded too quickly, for example natural rubber, which resists tearing only 10kJ/m 2 This makes it difficult to meet its daily requirements even after vulcanizationThe tear resistance value at the end of the connection is only increased by dozens of kilojoules per square meter.
Though the introduction of dynamic networks and the design of structures, the mechanical properties of the materials are significantly improved and the recycling of the materials is made possible. However, due to weak interaction and insufficient structural recovery, the preparation process is relatively complicated, and the introduced structure has poor biocompatibility and nondegradability, so that the prepared elastomer material is not ideal.
Disclosure of Invention
The application aims to provide a high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, and a preparation method, a recovery method, a degradation method and a surgical operation line thereof, so as to solve the problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a high strength tear resistant degradable temperature sensitive polyurethane elastomer comprising one or more of the following repeating units:
wherein R is H or X-Y; x is a high molecular long-chain diol unit, and Y is a diisocyanate unit; z is-CHO or-COOH;
preferably, the high molecular long-chain diol unit comprises one or more of a polycaprolactone diol unit, a polyether diol unit and a polyether amine diol unit, and the diisocyanate unit is a hexamethylene diisocyanate unit.
The application also provides a preparation method of the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, which comprises the following steps:
carrying out polymerization reaction on raw materials including high-molecular long-chain diol, hexamethylene diisocyanate and a first organic solvent to obtain a precursor solution;
carrying out chain extension reaction on materials including the precursor solution and the chain extender, and then adding an iron source compound to carry out coordination reaction to obtain a reaction product solution;
and drying the reaction product solution to obtain the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer.
Preferably, the preparation method satisfies at least one of the following conditions:
a. the high-molecular long-chain diol comprises one or more of polycaprolactone diol, polyether diol and polyether amine diol;
b. the chain extender comprises 3, 4-dihydroxybenzaldehyde and/or 3, 4-dihydroxybenzoic acid;
c. the feedstock also includes a catalyst comprising dibutyltin dilaurate and/or tin acetate;
d. the iron source compound comprises ferric chloride and/or ferric sulfate;
e. the first organic solvent comprises a solvent capable of dissolving the high molecular long-chain diol without affecting polycondensation;
f. the first organic solvent comprises tetrahydrofuran and/or dimethylacetamide;
preferably, the mass ratio of the high-molecular long-chain diol to the hexamethylene diisocyanate, to the chain extender to the iron source compound is 1: (2-2.4): (0.8-1.0): (0.8-1.0).
Preferably, the preparation method satisfies at least one of the following conditions:
g. the temperature of the polymerization reaction is 60-80 ℃, and the time is 4-24h;
h. the temperature of the chain extension reaction is 60-80 ℃, and the time is 12-24h;
i. the temperature of the coordination reaction is 60-80 ℃, and the time is 0.5-2h.
Preferably, the drying temperature is 60-80 ℃ and the drying time is 6-24h.
Preferably, the drying further comprises:
soaking the dried material in alcohol until the color of the alcohol does not change, and repeating the drying process.
The application also provides a recycling method of the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, which comprises the following steps:
heating and dissolving the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer by using a second organic solvent, and then adding the obtained solution into a mold for drying to obtain a recovered elastomer material;
preferably, the second organic solvent comprises dimethylformamide and/or dimethylacetamide.
The application also provides a degradation method of the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, which comprises the following steps:
soaking the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer in a phosphate buffer containing lipase;
preferably, the phosphate buffer comprises PBS;
preferably, the soaking solution is replaced at intervals of 12-72 hours during the soaking process.
The application also provides a surgical operation line, and the raw materials of the surgical operation line comprise the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer.
Compared with the prior art, the beneficial effect of this application includes:
the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer provided by the application is a polyurethane elastomer material containing dynamic iron ion coordination, has very strong tear resistance and strength, and can reach the tensile strength of more than 35MPa, about 372MJ/m 3 And a toughness of about 646kJ/m 2 Is resistant to tearing. Meanwhile, the elastomer prepared by the invention selects high-molecular polyol which has good biocompatibility and can be degraded as a soft segment raw material, and the material obtained after the chain extender and the iron ions are added for reaction is not covalently crosslinked. The prepared elastomer has good in-vivo and in-vitro biocompatibility and simultaneously has the recoverable and degradable performances, the mechanical property of the elastomer prepared after the DMF solution is recovered is basically kept unchanged, and the introduced material of the 3, 4-dihydroxy benzaldehyde has good thermal oxidation aging resistance.
The preparation method of the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer is simple and convenient to operate, reaction conditions are mild, the obtained material has good mechanical properties, biocompatibility and anti-aging performance, and can be recycled, and the performance of the recycled material is basically unchanged.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a hydrogen spectrum of a complex of iron obtained in example 1;
FIG. 2 is a carbon spectrum of a substance obtained in example 1 without iron complex;
FIG. 3 is a graph of UV wavelength vs. absorbance of the product of each stage of the example;
FIG. 4 is a stained section of wound tissue on different days;
FIG. 5 is a graph showing the degradation effects of 3d to 60 d;
FIG. 6 is a schematic view of the temperature sensitive tightening of the pigskin incision by the pre-stretched elastomer at 40 ℃.
Detailed Description
The terms as used herein:
"consisting of 8230%" \8230, preparation "and" comprising "are synonymous. The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of 823070, 8230composition" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of 8230' \8230"; composition "appears in a clause of the subject matter of the claims and not immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4," "1 to 3," "1 to 2 and 4 to 5," "1 to 3 and 5," and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In the examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent an arbitrary unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A high strength tear resistant degradable temperature sensitive polyurethane elastomer comprising one or more of the following repeating units:
wherein R is H or X-Y; x is a high molecular long-chain diol unit, and Y is a diisocyanate unit; z is-CHO or-COOH;
preferably, the high molecular long-chain diol unit comprises one or more of a polycaprolactone diol unit, a polyether diol unit and a polyether amine diol unit, and the diisocyanate unit is a hexamethylene diisocyanate unit.
The application also provides a preparation method of the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, which comprises the following steps:
carrying out polymerization reaction on raw materials including high-molecular long-chain diol, hexamethylene diisocyanate and a first organic solvent to obtain a precursor solution;
carrying out chain extension reaction on materials including the precursor solution and the chain extender, and then adding an iron source compound to carry out coordination reaction to obtain a reaction product solution;
and drying the reaction product solution to obtain the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer.
In an alternative embodiment, the method of preparation, satisfies at least one of the following conditions:
a. the high-molecular long-chain diol comprises one or more of polycaprolactone diol, polyether diol and polyether amine diol; b. the chain extender comprises 3, 4-dihydroxybenzaldehyde and/or 3, 4-dihydroxybenzoic acid;
the chain extender may be any compound having a catechol structure.
c. The feedstock also includes a catalyst comprising dibutyltin dilaurate and/or tin acetate;
d. the iron source compound comprises ferric chloride and/or ferric sulfate;
trivalent soluble iron salts are all useful.
e. The first organic solvent comprises a solvent capable of dissolving the high molecular long-chain diol without affecting polycondensation;
f. the first organic solvent comprises tetrahydrofuran and/or dimethylacetamide;
in an alternative embodiment, the mass ratio of the high molecular long-chain diol, the hexamethylene diisocyanate, the chain extender, and the iron source compound is 1: (2-2.4): (0.8-1.0): (0.8-1.0).
Optionally, the mass ratio of the high-molecular long-chain diol, the hexamethylene diisocyanate, the chain extender and the iron source compound may be 1:2:0.8:0.8, 1:2.2:0.8:0.8, 1:2.4:0.8:0.8, 1:2:0.9:0.8, 1:2:1.0:0.8, 1:2:1.0:0.8, 1:2:1.0:0.9, 1:2:1.0:1.0, 1:2.4:1.0:1.0 or 1: (2-2.4): (0.8-1.0): (0.8-1.0).
In an alternative embodiment, the preparation method satisfies at least one of the following conditions:
g. the temperature of the polymerization reaction is 60-80 ℃, and the time is 4-24h;
h. the temperature of the chain extension reaction is 60-80 ℃, and the time is 12-24h;
i. the temperature of the coordination reaction is 60-80 ℃, and the time is 0.5-2h.
Optionally, the temperature of the polymerization reaction may be any value between 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 60-80 ℃, and the time may be any value between 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h or 4-24h; the temperature of the chain extension reaction can be any value between 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 60-80 ℃, and the time can be any value between 12h, 14h, 16h, 18h, 20h, 22h, 24h or 12-24h; the temperature of the coordination reaction can be any value between 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 60-80 ℃, and the time can be any value between 0.5h, 1h, 1.5h, 2h or 0.5-2h.
In an alternative embodiment, the drying is carried out at a temperature of 60 to 80 ℃ for a time of 6 to 24 hours.
Optionally, the drying temperature may be any value between 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 60-80 ℃, and the time may be any value between 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h or 6-24h.
In an alternative embodiment, the drying further comprises, after the drying:
soaking the dried material in alcohol until the color of the alcohol does not change, and repeating the drying process.
The application also provides a recycling method of the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, which comprises the following steps:
heating and dissolving the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer by using a second organic solvent, and then adding the obtained solution into a mold for drying to obtain a recovered elastomer material;
in an alternative embodiment, the second organic solvent comprises dimethylformamide and/or dimethylacetamide.
The application also provides a degradation method of the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, which comprises the following steps:
soaking the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer in a phosphate buffer solution containing lipase;
in an alternative embodiment, the phosphate buffer comprises PBS;
in an alternative embodiment, the soaking solution is replaced at intervals of 12-72 hours during the soaking process.
The application also provides a surgical operation line, and the raw materials of the surgical operation line comprise the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer.
The obtained elastomer material can be directly used for suturing surgical wounds after being sterilized by thread sterilization. In the application process of the surgical thread, if the wound is to be tightened by utilizing the temperature-sensitive property of the elastomer material, the elastomer needs to be pre-stretched and frozen and shaped under the low-temperature condition.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1
The application provides a high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, which is prepared by the following steps:
(1) 12g of dried polycaprolactone diol, 2g of hexamethylene diisocyanate and 0.1g of dibutyltin dilaurate were dissolved in 200ml of Tetrahydrofuran (THF), and oil bath reaction was carried out at 60 ℃ for 24 hours to obtain a precursor solution. After the reaction is finished, 0.82g of chain extension-3, 4-dihydroxybenzaldehyde (PA) is dissolved in 20ml of THF, then added into the precursor solution to continue the reaction for 24 hours at the temperature of 70 ℃, and then 0.8g of ferric chloride is added to be stirred for 0.5 hour to obtain a reaction solution;
(2) Pouring the obtained reaction solution into a glass mold, placing the glass mold in an oven to dry for 24 hours at 70 ℃, air-drying to obtain an elastomer material, immersing the elastomer material in alcohol to remove impurities until the alcohol does not change color any more, taking out the elastomer material, and repeating the drying process to obtain the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer.
The structural formula of the obtained elastomer is as follows:
wherein X is:
m and n are both 2000 (m and n are determined according to high-molecular long-chain diol);
y is:
z is-CHO.
The hydrogen spectrum of the substance without iron complex (PCL-PA) is shown in FIG. 1, the carbon spectrum of the substance without iron complex (PCL-PA) is shown in FIG. 2, and the ultraviolet wavelength-absorbance curves of PCL, PCL-PA and the elastomer (PCL-PA-Fe) are shown in FIG. 3.
FIG. 3 shows the formation of bidentate ligands after iron addition.
The recovery method of the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer comprises the following steps:
the prepared elastomer was dissolved by heating with Dimethylformamide (DMF) to obtain a polymer solution dissolved in DMF, and then the operation in the above step (2) was repeated.
The degradation method of the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer comprises the following steps:
the elastomer was degraded with lipase in Phosphate Buffered Saline (PBS) and the solution was changed every 24h.
Example 2
The application provides a high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, which is prepared by the following steps:
(1) Dissolving 12g of dried polycaprolactone diol, 2g of hexamethylene diisocyanate and 0.1g of dibutyltin dilaurate in 200ml of Tetrahydrofuran (THF), carrying out oil bath reaction at 60-80 ℃ for 4-24 hours to obtain a precursor solution, adding chain extension-3, 4-dihydroxybenzaldehyde (PA) for continuing reaction for 12-24 hours, adding ferric chloride, and stirring for 0.5-2 hours; the mass ratio of the raw materials in the reaction process is as follows: 1 part of polycaprolactone diol, 2-2.4 parts of hexamethylene diisocyanate, 0.8-1.0 part of 3, 4-dihydroxy benzaldehyde and 0.8-1.0 part of ferric chloride;
(2) Pouring the reaction solution obtained in the process into a glass mold, placing the glass mold in an oven for drying for 6-24h at the temperature of 60-80 ℃, air-drying to obtain an elastomer material, immersing the elastomer material in alcohol for impurity removal until the alcohol does not change color, taking out the elastomer material, and repeating the drying process to obtain the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer.
Example 3
The application provides a high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, which is prepared by the following steps:
(1) Dissolving 12g of dried polycaprolactone diol, 2g of hexamethylene diisocyanate and 0.1g of dibutyltin dilaurate in 200ml of Tetrahydrofuran (THF), carrying out oil bath reaction at the temperature of 60-80 ℃ for 4-24 hours to obtain a precursor solution, adding chain extension-3, 4-dihydroxybenzaldehyde (PA) for continuous reaction for 12-24 hours, adding ferric chloride, and stirring for 0.5-2 hours; the mass ratio of the raw materials in the reaction process is as follows: 1 part of polycaprolactone diol, 2-2.4 parts of hexamethylene diisocyanate, 0.8-1.0 part of 3, 4-dihydroxy benzaldehyde and 0.8-1.0 part of ferric chloride;
(2) Pouring the reaction solution obtained in the process into a glass mold, placing the glass mold in an oven for drying for 6-24h at the temperature of 60-80 ℃, air-drying to obtain an elastomer material, immersing the elastomer material in alcohol for impurity removal until the alcohol does not change color, taking out the elastomer material, and repeating the drying process to obtain the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer.
Comparative example 1
A conventional medical suture was used as a control (Tei filament 1604-51 type silk thread from Jiansheng medical supplies, suzhou).
Different high molecular diols were synthesized in the same ratio and tested for tensile properties, including polyethylene glycol (Mn = 2000) and polyether diol. Meanwhile, the influence of no iron ions is compared on the premise that PCL dihydric alcohol is used as a raw material.
TABLE 1 mechanical Properties of elastomers synthesized from different starting diols
PCL diol | PCL diol with no added iron | PEG diols | Polyether diol |
32.4MPa | 12.5MPa | 17.6MPa | 20.7MPa |
Deformation of about 2100% | 1750% deformation | Deformation of 1500% | Deformation of 1000% |
The elastomer obtained in example 1 was cut into thin threads of about 0.4mm, and the material was prestretched with a strain of 0%, 50% and 100%, and then the mice were sutured by surgery.
And in the pure shearing test, the distance between the clamps is controlled to be 5mm, the sample is controlled to be 25mm, a 10mm gap is parallelly cut in the middle by a blade, and the maximum value is taken.
The specific experimental method is as follows:
1. in vivo and in vitro biocompatibility and wound suture experiment: the 1.1CCK-8 method and Live/Dead fluorescent staining are adopted to detect the in vitro cell compatibility of the material, and the in vivo tissue compatibility is realized by implanting a sterile sample into the subcutaneous tissues on the two sides of the back of a mouse for a certain time, and then dissecting the skin on the back of the mouse for photographing and observation. And surrounding tissues of the sample are taken out, and whether inflammatory reaction is initiated or not is observed through HE staining after paraffin embedding.
2. Suture experiment:
the mice were anesthetized, a 1cm length wound was opened on the skin with a scalpel, and the prepared elastomer threads of different pre-stretched elongation were used to compare the wound recovery effect with commercial silk sutures.
A first group: the wound was closed with a normal medical suture (Control sample comparative example 1);
second group: the wound was sutured with undrawn suture (PCL-PA-Fe-0%);
third group: the wound was closed with 50% pre-stretched suture (PCL-PA-Fe-50%);
and a fourth group: the wound was closed with 100% pre-stretched suture (PCL-PA-Fe-100%).
The length of the thread is measured before the use, 4 groups of threads with the same length are selected, and the length of the residual thread is measured again after the sewing is finished.
7. Wound healing was observed by taking photographs on day 14 to see if suture contraction would promote tissue wound healing, and HE was sampled on day 14 and observed by Masson staining, with the results shown in figure 4.
3. Mechanical, anti-aging and aging tests: the tensile strength and the tear resistance of the material are tested by a pure shearing method under the condition of 30mm/min by using a universal testing machine, the aging test is carried out on the material at 100 ℃ by using a thermal oxidation aging machine in the aging process, and the change of the carbon and oxygen contents is tested by using an element analyzer.
4. Degradation test: the elastomer was degraded with lipase in Phosphate Buffered Saline (PBS) and inhibited bacterial growth with sodium azide, and the solution was changed every 24h.
The results obtained are shown in tables 2 and 3 below:
TABLE 2 mechanical Properties of the elastomers
Tensile strength | Tensile strength after recovery | Tensile strength after aging |
32.4MPa | 31.9MPa | 29.7MPa |
TABLE 3 comparison of carbon to oxygen content before and after elastomer aging
As shown in FIG. 4, it can be seen from the dynamic change of the suture thread that the suture thread 1,2,3 groups (second, third and fourth groups) is more durable than the medical suture thread because of the tensile property, and the thread length for closing a wound is less. The sutures 1,2,3, however, do not differ significantly from one suture to another, and do not undergo significant length changes as a result of the pre-tensioning treatment, and the length of thread required to suture the wound is approximately the same. The HE and Masson staining results of the samples taken on the 7 th and 14 th days showed that the wound sutured in the sample 1,2,3 on the 7 th day was scabbed and an intact epidermis was formed under the scab, while the wound sutured with the medical suture of the control group did not form an intact epidermis and was visible as a rupture at the wound and was not completely filled with collagen fibers. This indicates that the sample 1,2,3 suture is able to promote wound healing more quickly, which may be related to the tensile properties of the suture, enabling the suture to be more compact. All treatment groups healed on day 14, but the new skin of the sample 2,3 groups was more even and the collagen fibers were more densely and regularly arranged, indicating that the recovery effect of the suture of sample 2,3 may be better pre-stretched to promote wound recovery.
As shown in fig. 5, the obtained elastomer was significantly degraded in 3d to 60d, indicating that it had better degradability.
FIG. 6 is a schematic view of the temperature-sensitive tightening of the pigskin incision by the pre-stretched elastomer at 40 ℃. As can be seen from FIG. 6, the elastomer provided by the present application has a very significant temperature-sensitive effect.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A high strength tear resistant degradable temperature sensitive polyurethane elastomer comprising one or more of the following repeating units:
wherein R is H or X-Y; x is a high molecular long-chain diol unit, and Y is a diisocyanate unit; z is-CHO or-COOH;
preferably, the high molecular long-chain diol unit comprises one or more of a polycaprolactone diol unit, a polyether diol unit and a polyether amine diol unit, and the diisocyanate unit is a hexamethylene diisocyanate unit.
2. A method for preparing the high strength tear resistant degradable temperature sensitive polyurethane elastomer of claim 1, comprising:
carrying out polymerization reaction on raw materials including high-molecular long-chain diol, hexamethylene diisocyanate and a first organic solvent to obtain a precursor solution;
carrying out chain extension reaction on materials including the precursor solution and the chain extender, and then adding an iron source compound to carry out coordination reaction to obtain a reaction product solution;
and drying the reaction product solution to obtain the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer.
3. The production method according to claim 2, characterized in that at least one of the following conditions is satisfied:
a. the high-molecular long-chain diol comprises one or more of polycaprolactone diol, polyether diol and polyether amine diol;
b. the chain extender comprises 3, 4-dihydroxybenzaldehyde and/or 3, 4-dihydroxybenzoic acid;
c. the feedstock also includes a catalyst comprising dibutyltin dilaurate and/or tin acetate;
d. the iron source compound comprises ferric chloride and/or ferric sulfate;
e. the first organic solvent comprises a solvent which can dissolve the high-molecular long-chain diol and does not influence the polycondensation;
f. the first organic solvent includes tetrahydrofuran and/or dimethylacetamide.
4. The production method according to claim 3, wherein the mass ratio of the high-molecular long-chain diol to the hexamethylene diisocyanate to the chain extender to the ferric chloride is 1: (2-2.4): (0.8-1.0): (0.8-1.0).
5. The production method according to claim 2, characterized in that at least one of the following conditions is satisfied:
g. the temperature of the polymerization reaction is 60-80 ℃, and the time is 4-24h;
h. the temperature of the chain extension reaction is 60-80 ℃, and the time is 12-24h;
i. the temperature of the coordination reaction is 60-80 ℃, and the time is 0.5-2h.
6. The method according to claim 2, wherein the drying is carried out at a temperature of 60 to 80 ℃ for 6 to 24 hours.
7. The method according to any one of claims 2 to 6, further comprising, after the drying:
soaking the dried material in alcohol until the color of the alcohol does not change, and repeating the drying process.
8. The method for recycling the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer according to claim 1, wherein the method comprises the following steps:
heating and dissolving the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer by using a second organic solvent, and then adding the obtained solution into a mold for drying to obtain a recovered elastomer material;
preferably, the second organic solvent comprises dimethylformamide and/or dimethylacetamide.
9. The method for degrading the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer according to claim 1, wherein the method comprises the following steps:
soaking the high-strength tear-resistant degradable temperature-sensitive polyurethane elastomer in a phosphate buffer containing lipase;
preferably, the phosphate buffer comprises PBS;
preferably, the soaking solution is replaced at intervals of 12-72 hours during the soaking process.
10. A surgical cable characterized in that its raw material comprises the high strength tear resistant degradable temperature sensitive polyurethane elastomer of claim 1.
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