CN115612056A - High-toughness and high-mechanical-strength polyurethane elastomer with excellent water resistance and repairable and recyclable functions and preparation method thereof - Google Patents
High-toughness and high-mechanical-strength polyurethane elastomer with excellent water resistance and repairable and recyclable functions and preparation method thereof Download PDFInfo
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- CN115612056A CN115612056A CN202211288471.8A CN202211288471A CN115612056A CN 115612056 A CN115612056 A CN 115612056A CN 202211288471 A CN202211288471 A CN 202211288471A CN 115612056 A CN115612056 A CN 115612056A
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- polyurethane elastomer
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- elastomer
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 10
- 238000007731 hot pressing Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000005062 Polybutadiene Substances 0.000 claims description 13
- 229920002857 polybutadiene Polymers 0.000 claims description 13
- 229920001610 polycaprolactone Polymers 0.000 claims description 12
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000004632 polycaprolactone Substances 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 7
- YZVWKHVRBDQPMQ-UHFFFAOYSA-N 1-aminopyrene Chemical compound C1=C2C(N)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 YZVWKHVRBDQPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004970 Chain extender Substances 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 229920001195 polyisoprene Polymers 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 5
- VPRFQZSTJXHBHL-UHFFFAOYSA-N phenanthrene-9,10-diamine Chemical compound C1=CC=C2C(N)=C(N)C3=CC=CC=C3C2=C1 VPRFQZSTJXHBHL-UHFFFAOYSA-N 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 239000012745 toughening agent Substances 0.000 claims description 5
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 4
- NHEKBXPLFJSSBZ-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)CO NHEKBXPLFJSSBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 claims description 3
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 3
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 3
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- GSHJWFSWKUADLL-UHFFFAOYSA-N [8-(hydroxymethyl)anthracen-1-yl]methanol Chemical compound C1=CC(CO)=C2C=C3C(CO)=CC=CC3=CC2=C1 GSHJWFSWKUADLL-UHFFFAOYSA-N 0.000 claims description 3
- JBBHFHMVEOHFRE-UHFFFAOYSA-N anthracene-2,6-diol Chemical compound C1=C(O)C=CC2=CC3=CC(O)=CC=C3C=C21 JBBHFHMVEOHFRE-UHFFFAOYSA-N 0.000 claims description 3
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- MFUFBSLEAGDECJ-UHFFFAOYSA-N pyren-2-ylamine Natural products C1=CC=C2C=CC3=CC(N)=CC4=CC=C1C2=C43 MFUFBSLEAGDECJ-UHFFFAOYSA-N 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- LVGANCPXXODGKA-UHFFFAOYSA-N 1,8-diisothiocyanatooctane Chemical compound S=C=NCCCCCCCCN=C=S LVGANCPXXODGKA-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 54
- 230000008439 repair process Effects 0.000 abstract description 19
- 229920002635 polyurethane Polymers 0.000 abstract description 17
- 239000004814 polyurethane Substances 0.000 abstract description 17
- 229920001971 elastomer Polymers 0.000 abstract description 15
- 239000000806 elastomer Substances 0.000 abstract description 15
- 238000013461 design Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 229920006247 high-performance elastomer Polymers 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 24
- 150000003673 urethanes Chemical class 0.000 description 11
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 230000003993 interaction Effects 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 229920006311 Urethane elastomer Polymers 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000007634 remodeling Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- XLHRUAGFSBVDGL-UHFFFAOYSA-N ethyl carbamate;oxepan-2-one Chemical compound CCOC(N)=O.O=C1CCCCCO1 XLHRUAGFSBVDGL-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007656 fracture toughness test Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- 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
- C08G18/40—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
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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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- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C08G18/61—Polysiloxanes
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- Polyurethanes Or Polyureas (AREA)
Abstract
A high-toughness and high-mechanical-strength polyurethane elastomer with excellent water resistance, repairable and recyclable functions and a preparation method thereof belong to the technical field of polyurethane elastomer preparation. According to the invention, through molecular topological design, the segmented polyurethane with a crystallization and multiphase separation structure is constructed, and nonpolar dynamic supermolecule acting force is introduced into a system to serve as a sacrificial bond for dissipating energy, so that the strength and toughness of the elastomer are improved, and the water resistance and repair capability of the material are endowed. The elastomer material has excellent repairing and recycling capabilities, and the damaged elastomer can be completely repaired under the assistance of trace solvent at heating or room temperature; the scrapped materials can be completely recycled through processes such as solvent recasting or hot pressing. The invention can meet the requirements of people on high-performance elastomer materials to a great extent and has important significance for China.
Description
Technical Field
The invention belongs to the technical field of preparation of polyurethane elastomers, and particularly relates to a high-toughness and high-mechanical-strength polyurethane elastomer with excellent water resistance, repairable and recyclable functions and a preparation method thereof.
Technical Field
The elastomer material represented by polyurethane elastomer has a unique phase separation structure, can realize the coordination of the mechanical properties of the material based on the regulation and control of the phase structure, and can meet the requirements of various application scenes (mater.horiz., 2021,8,2238-2250). Therefore, elastomer materials are widely used in a large amount in industrial and agricultural industries and daily life such as tires, adhesives, biomedical materials, and fabrics. Conventional elastomeric articles are susceptible to breakage after soaking and frequent use. These damaged elastomeric articles generally have a stable covalent network structure, making them difficult to repair and recycle for eventual disposal by incineration, thereby causing significant waste of resources and environmental pollution. Therefore, the elastomer material is endowed with repairable and recyclable performance and excellent mechanical properties such as strength, toughness and the like, the service stability and the damage resistance of the material can be effectively improved, the service life is prolonged, and the elastomer material has important significance for China.
The achievement of repairable recyclability generally relies on a dynamic reversible polymer network (Langmuir 2022,38,9050-9063) crosslinked by reversible forces. However, the introduction of reversible force inevitably leads to the reduction of the stability of the polymer network, so that the prepared polymer elastomer has poor mechanical properties and is difficult to meet daily application. Meanwhile, the chemical group that forms a reversible force is generally a highly polar group having strong hydrophilicity, such as an amino group, a carboxyl group, a carbonyl group, and the like (mater. Horiz.,2021,8,2238-2250) that form a hydrogen bond, a pyridyl group, a carboxyl group, and the like (adv. Mater.2020,32,2005759) that form a metal coordinate bond, a boroester group (j. Mater. Chem.a,2021,9,22410-22417) that form a boroester bond, and the like. The introduction of a large amount of polar hydrophilic groups easily causes the reduction and even loss of the water resistance of the material, and the structural and performance stability of the material used in high-humidity or underwater environment for a long time is difficult to ensure. The traditional method for improving the water resistance of the material is that the obtained hydrophobic material has generally poor mechanical properties by introducing a hydrophobic main chain (ACS Appl.Mater. Interfaces 2018,10,30887-30894), introducing fluorine-containing hydrophobic groups (adv.Mater.2018, 30, 1706846) and the like. Therefore, elastomer materials with excellent water resistance, mechanical strength, toughness, repair and recycling capability are still difficult to be developed.
Disclosure of Invention
The invention aims to solve the problems that a polymer material is difficult to cooperate with water resistance, mechanical strength and repair performance by using a crystalline component formed by a polymer chain segment as a hydrophobic physical crosslinking site and using dynamic reversible nonpolar intermolecular acting force as a hydrophobic sacrificial bond capable of dissipating energy through molecular topological structure design, so that a high-performance polyurethane elastomer integrating the performances or functions of good water resistance, high strength, high toughness, high ductility, high elasticity, tear resistance, repair, recycling and the like is prepared.
The invention relates to a preparation method of a high-toughness and high-mechanical-strength polyurethane elastomer with excellent water resistance, repairable and recyclable functions, which comprises the following steps:
(1) Synthesis of a prepolymer: dissolving one or more crystalline or amorphous dihydroxyl or diamino terminated polymers A serving as main chain components in a dry solvent, then adding a diisocyanate terminated compound B, and reacting for 0.5-48 h at 30-120 ℃; wherein the molar weight of the compound B is 1.01 to 2.01 times that of the polymer A;
(2) Introduction of non-polar toughening sites: adding a hydroxyl or amino terminated hydrophobic toughening agent C with the molar weight 0.01-1.01 times that of the polymer A into the reaction system obtained in the step (1), and then reacting at 30-120 ℃ for 0.5-72 h;
(3) And (3) polymer chain extension: adding a dihydroxyl or diamino terminated chain extender D with the molar weight 0-1.00 times that of the polymer A into the reaction system obtained in the step (2), and then reacting at 30-120 ℃ for 0.5-72 h; and the molar amount of hydroxyl or amino groups of toughener C + the molar amount of hydroxyl or amino groups of chain extender D + the molar amount of hydroxyl or amino groups of polymer a = the molar amount of isocyanate groups of compound B;
(4) Molding: and (4) removing the solvent from the polymer solution obtained in the step (3) through a forming processing technology, and forming to obtain the polyurethane elastomer with high toughness and high mechanical strength, which has the functions of recycling and self-repairing.
The polymer A in the step (1) is one or more of dihydroxyl or diamino terminated polycaprolactone, polylactide, polyethylene, polybutadiene, polyethylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyisoprene and polypropylene oxide; the compound B is one or more of isophorone diisocyanate, 1,3-phenylene diisocyanate, 1,6-hexamethylene diisocyanate, diphenylmethane diisocyanate, 1,4-cyclohexane diisocyanate, dicyclohexylmethane 4,4' -diisocyanate, o-xylylene diisocyanate, 1,5-naphthalene diisocyanate and 1,8-octane diisothiocyanate; the solvent is one or more of chloroform, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dichloromethane, N-methylpyrrolidone or dimethyl sulfoxide.
The toughening agent C in the step (2) is one or more of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 1,5-naphthalenediol, 2,6-dihydroxyanthracene, 1,8-bis (hydroxymethyl) anthracene, 1-aminopyrene, 9,10-diaminophenanthrene;
the chain extender D in the step (3) is one or more of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol and diethylene glycol, 1,4-butanediamine and 1,6-hexanediamine;
the forming process in the step (4) of the invention comprises one or more of film casting, tape casting, hot pressing, mould pressing and solvent replacement.
After the polymer is prepared, processed and molded, a balance is used for measuring the mass change of the material before and after soaking in water, a universal material testing machine is used for representing the mechanical properties of the material such as ductility, toughness, strength, elasticity and the like in room temperature and underwater environment, and a rheometer is used for representing the viscoelasticity of the material in a shearing mode. Heating the damaged material or applying a trace amount of solvent at room temperature to verify the repair capability of the material, recycling the damaged material by hot pressing, extrusion and solvent recasting, and verifying the recycling efficiency by using a universal material testing machine.
According to the invention, through molecular topological design, the segmented polyurethane with a crystallization and multiphase separation structure is constructed, and nonpolar dynamic supermolecule acting force is introduced into a system to serve as a sacrificial bond for dissipating energy, so that the strength and toughness of the elastomer are improved, and the water resistance and repair capability of the material are endowed. The prepared material has the advantages of strong waterproofness, high breaking strength, good ductility, excellent toughness, good elasticity and the like, and can greatly meet the requirements of people on high-performance elastomers. In specific terms, the breaking strength of the material>40MPa, elongation at break>20mm/mm, the toughness reaches>500MJ m -3 (ii) a Most importantly, the elastomeric material has excellent water resistance and changes in quality after 20 days immersion in pure water<1%, the mechanical strength is basically kept unchanged. Meanwhile, the elastomer material has excellent repairing and recycling capabilities, and the damaged elastomer can be completely repaired under the assistance of trace solvent at the room temperature or under the heating condition; the scrapped materials can be completely recycled through processes such as solvent recasting or hot pressing. The invention can meet the requirements of people on high-performance elastomer materials to a great extent, and has important significance for China.
Drawings
FIG. 1: a) Stress-strain curve of high tenacity poly (caprolactone/ethylene glycol) urethane elastomer, b) continuous cyclic tensile curve of high tenacity poly (caprolactone/ethylene glycol) urethane elastomer, corresponding to example 1;
FIG. 2: a) Digital photographs of an initial sample of poly (tetrahydrofuran/ethylene glycol) urethane (i) and a sample after 20 days immersion in water (ii); b) Stress-strain curve of poly (tetrahydrofuran/ethylene glycol) urethane elastomer c) comparative graph of mass change and breaking strength before and after soaking poly (tetrahydrofuran/ethylene glycol) urethane in water for 20 days, corresponding to example 2;
FIG. 3: a) The digital photograph of the poly (caprolactone/butadiene) urethane solvent remodeling recycling process shows that, specifically, a sample cut into millimeter-sized fragments (as shown in figure i) is fully dissolved by a chloroform solvent and then is cast into a film (as shown in figure ii) in a glass ware, and a transparent and uniform film (as shown in figure iii) is obtained after the solvent is completely volatilized; b) Stress-strain curves before and after remodeling and recycling of the poly (caprolactone/butadiene) urethane solvent correspond to example 3;
FIG. 4: initial samples of poly (tetrahydrofuran/isoprene/butadiene) urethane elastomer and stress-strain curves of the samples after 6 hours of room temperature solvent-assisted repair correspond to example 4;
FIG. 5: a) Stress strain curves for poly (lactide/butadiene) urethanes; b) Figure (i) is a digital photograph showing puncture resistance tests of poly (lactide/butadiene) urethane; stress strain curve (ii) for the puncture test procedure corresponds to example 5.
FIG. 6: a) Stress strain curves for poly (ethylene/butadiene) urethanes; b) Fracture toughness test experiments for poly (ethylene/butadiene) urethanes. A 5mm wide strip of poly (ethylene/butadiene) urethane was cut on one side with a cut of about 1mm length and the material was gradually stretched to a stretch ratio of 200% (i), 600% (ii), 1200% (iii) without breaking and without extending the wound into the interior of the strip, demonstrating good tear toughness, corresponding to example 6.
FIG. 7: a) Stress strain curves for poly (tetrahydrofuran/dimethylsiloxane) urethanes; b) Continuous cyclic underwater tensile curves of poly (tetrahydrofuran/dimethylsiloxane) urethane correspond to example 7.
FIG. 8: the stress-strain curve of the poly (caprolactone) urethane corresponds to example 8.
Detailed Description
The following examples are presented to further illustrate the practice and results of the present invention and are not intended to limit the invention.
Example 1: high toughness poly (caprolactone/ethylene glycol) urethanes that function as a sacrificial bond and a driving force for repair with hydrogen bonding and pi-pi interactions.
1) End-capping of bishydroxy polycaprolactone (M) n 2000,4.0g,2.0 mmol) and bishydroxy terminated polyethylene glycol (M) n 400,0.4g, 1.0mmol) is dissolved in dehydrated tetrahydrofuran and reacts with 2 times of molar equivalent of dicyclohexylmethane 4,4' -diisocyanate (1.57g, 6.0mmol) at 50 ℃ for 48 hours to prepare a prepolymer;
2) Adding 9,10-diaminophenanthrene (0.44g, 2.1mmol) which is 0.7 time of the molar weight sum of the dihydroxy-terminated polycaprolactone and the dihydroxy-terminated polyethylene glycol into the reaction system obtained in the step 1), and continuously reacting for 48 hours at 50 ℃;
3) Adding 1,4-butanediol (0.081g, 0.9 mmol) which is 0.3 time of the molar weight sum of the bishydroxy terminated polycaprolactone and the bishydroxy terminated polyethylene glycol into the reaction system obtained in the step 2), and continuously reacting for 24 hours at 60 ℃;
4) And (4) casting the polymer solution obtained in the step 3) on a glass plate, and finishing the preparation of the polyurethane elastomer with excellent water resistance, repairability and recyclable function, high toughness and high mechanical strength after the solvent is completely volatilized naturally.
The stress-strain curve given in fig. 1 corresponds to this example. The polyurethane has good mechanical strength, the breaking strength of the polyurethane is as high as 60MPa, the breaking elongation of the polyurethane is 2805 percent, and the toughness of the polyurethane is as high as 602MJ m -3 (FIG. 1 a). Meanwhile, the elastomer has good elasticity, and the mechanical curve of stretching to 100% continuously and circularly for two times can obtain that the residual strain of the material is only 7% (figure 1 b).
Example 2: high toughness poly (tetrahydrofuran/ethylene glycol) urethanes that act as a sacrificial bond and a driving force for repair with hydrogen bonding and fluorine dipolar interactions.
1) Poly (tetrahydrofuran) (M) end-capped with dihydroxy group n 2000,2.0g,1.0 mmol) and crystalline bishydroxy-terminated polyethylene glycol (M) as a reinforcing component n 400,1.2g and 3.0mmol) are dissolved in the dehydrated dimethyl sulfoxide and reacted with 2 times of molar equivalent of 1,6-hexamethylene diisocyanate (1.34g and 8.0mmol) at the temperature of 80 ℃ for 0.5h to prepare the prepolymer；
2) Adding 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (0.52g, 2.0 mmol) which is 0.50 time of the molar weight sum of the bishydroxy-terminated polytetrahydrofuran and the bishydroxy-terminated polyethylene glycol into the reaction system obtained in the step 1), and continuing to react at 90 ℃ for 12 hours;
3) Adding 1,3-propylene glycol (0.15g, 2.0 mmol) which is 0.50 time of the molar weight sum of the bishydroxy-terminated polytetrahydrofuran and the bishydroxy-terminated polyethylene glycol into the reaction system obtained in the step 2), and continuously reacting for 24 hours at 90 ℃;
4) And (4) casting the polymer solution obtained in the step 3) on a glass plate to form a film, and completing the preparation of the polyurethane elastomer with excellent water resistance, repairability and recyclable functions, high toughness and high mechanical strength after the solvent is completely volatilized.
The polyurethane constructed by the embodiment has good transparency and underwater stability. FIG. 2a shows digital photographs of the polyurethane material (i) prepared and the material (ii) after 20 days of soaking in water; FIG. 2b shows the mechanical properties of the material, the breaking strength is 53MPa, the breaking elongation reaches 2200 percent, and the toughness reaches 516MJ m -3 (ii) a Fig. 2c shows the mass change and the mechanical strength comparison of the material before and after the material is soaked in water for 20 days, and it can be seen that the mechanical strength of the material can maintain the basic stability of the size and the mechanical property after being soaked in water, and the material has good underwater stability.
Example 3: poly (caprolactone/butadiene) urethanes that act as a driving force for toughening and repair with hydrogen bonding and pi-pi interactions.
1) End-capping of bishydroxy polycaprolactone (M) n 1,500,1.5g, 1.0 mmol) and bishydroxy-terminated polybutadiene (M) n 7,000,7.0g, 1.0mmol) is dissolved in chloroform with water removed, and reacts with 2 times of molar equivalent of 1,6-hexamethylene diisocyanate (0.67g, 4.0mmol) at the temperature of 50 ℃ for 6 hours to prepare a prepolymer;
2) Adding 0.1 time of the sum of the molar weight of the dihydroxyl terminated polycaprolactone and the molar weight of the dihydroxyl terminated polybutadiene 2,6-dihydroxyanthracene (0.042g, 0.2mmol) into the reaction system obtained in the step 1), and continuously reacting for 12h at 50 DEG C
3) Adding 1,6-hexanediamine (0.21g, 1.8mmol) which is 0.9 times of the molar weight sum of the bishydroxy terminated polycaprolactone and the bishydroxy terminated polybutadiene into the reaction system obtained in the step 1), and continuously reacting for 24h at 60 ℃.
4) And (3) settling the polymer solution obtained in the step 3) in water, collecting polymer precipitate, drying the precipitate, and carrying out hot pressing at 100 ℃ and 5MPa to finish the preparation of the high-toughness polyurethane.
In this example, the polyurethane elastomer prepared had good transparency, mechanical properties and remolding ability. FIG. 3a shows that the chopped material can be redissolved in tetrahydrofuran solution and cast into a film to give a uniform film that is also transparent (FIG. 3 a). As shown in FIG. 3b, the breaking strength of the polyurethane material reaches 40.5MPa, and the breaking elongation reaches 2735%; after solvent remodeling, the mechanical property of the polyurethane material can be recovered after remodeling.
Example 4: poly (tetrahydrofuran/isoprene/butadiene) urethanes that act as a sacrificial bond and a driving force for repair with hydrogen bonds and pi-pi interactions.
1) Poly (tetrahydrofuran) (M) end-capped with dihydroxy group n 1000,2.0g,2.0 mmol), bishydroxy-terminated polyisoprene (M) n 1500,1.5g,1.0 mmol) and bishydroxy-terminated polybutadiene (M) n 4000,4.0 g and 1.0 mmol) of the prepolymer are dissolved in dehydrated N, N-dimethylacetamide and reacted with 2.0 times of molar equivalent of 1,3-phenylene diisocyanate (1.28g and 8.0 mmol) at 50 ℃ for 12 hours to prepare a prepolymer;
2) Adding 0.50 times of 1-aminopyrene (0.44g, 2.0 mmol) of the molar sum of the dihydroxy-terminated polytetrahydrofuran, the dihydroxy-terminated polyisoprene and the dihydroxy-terminated polybutadiene to the reaction system obtained in the step 1), wherein the molar sum of the dihydroxy-terminated polytetrahydrofuran, the dihydroxy-terminated polyisoprene and the dihydroxy-terminated polybutadiene is 9,10-diaminophenanthrene (0.42g, 2.0 mmol) and the molar sum of the dihydroxy-terminated polytetrahydrofuran, the dihydroxy-terminated polyisoprene and the dihydroxy-terminated polybutadiene is 0.50 times, and continuously reacting at 70 ℃ for 8 hours;
3) Adding 0.25 time molar equivalent of 1,3-propylene glycol (0.075g, 1.0mmol) into the reaction system obtained in the step 2), and continuously reacting at 70 ℃ for 24 hours;
4) Concentrating the polymer solution obtained in the step 3) to 1/8 of the volume of the original solution, pouring the concentrated polymer solution into a large amount of n-hexane, and collecting precipitates; and then processing and forming in a double-screw extruder at 100 ℃, thus finishing the preparation of the material.
In this example, the elastomer constructed had good repair ability (FIG. 4). The polyurethane has excellent mechanical properties, and the initial material has a breaking stress of 55MPa and an elongation at break of 2360% (solid line in the figure). The cut sample strips are repaired for 6 hours under the assistance of trace dimethyl sulfoxide at room temperature, and the stress-strain curves of the repaired sample strips are tested, so that the breaking strength and the elongation of the repaired sample strips can be respectively repaired to 54MPa and 2330 percent (dotted lines in the figure). After the repair, the mechanical property of the elastomer is almost completely recovered, so that the polyurethane elastomer has good repair capability.
Example 5: poly (lactide/butadiene) urethanes that act as a sacrificial bond and a driving force for repair with hydrogen bonding and fluorine dipolar interactions.
1) End-capping of the dihydroxy Polylactide (M) n 10000,10.0g,1.0 mmol), dihydroxy-terminated polybutadiene (M) n 1000,2g and 2.0 mmol) are dissolved in dehydrated tetrahydrofuran and react with 2.0 times of molar equivalent of isophorone diisocyanate (1.33g and 6.0 mmol) at 50 ℃ for 12 hours to prepare a prepolymer;
2) Adding 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (0.78g, 3mmol) which is 1.0 time the molar weight sum of the dihydroxy-terminated polylactide and the dihydroxy-terminated polybutadiene into the reaction system obtained in step 1), and continuing to react at 70 ℃ for 24h.
3) Casting the polymer solution obtained in the step 2) on a glass plate to form a film, and completing the preparation of the high-toughness polyurethane after the solvent is completely volatilized.
The polyurethane elastomer constructed in the embodiment has better puncture resistance. As shown in FIG. 5, the material has excellent mechanical properties (breaking strength 48MPa, elongation at break 2440%, as shown in FIG. 5 a); when a film having a thickness of about 7mm is tried to be pierced by a flat head rod having a diameter of 4mm, the film is less likely to be broken, and has a piercing resistance of about 35mm (FIG. 5b (i)) and a piercing force of about 75N (FIG. 5b (ii)).
Example 6: poly (ethylene/butadiene) urethanes that act as a sacrificial bond and a driving force for repair with hydrogen bonds and pi-pi interaction forces.
1) Termination of the bishydroxy terminated polyethylene (M) n 15000,15.0g,1.0 mmol), bishydroxy-terminated polybutadiene (M) n 2000,2g,1.0 mmol) is dissolved in dimethyl sulfoxide which is removed with water, and reacts with 2.0 times of molar equivalent of isophorone diisocyanate (0.59g, 4.0 mmol) for 5 hours at 50 ℃ to prepare prepolymer;
2) 9,10-diaminophenanthrene (0.42g, 2mmol), which is 1.0 times the sum of the molar amounts of bishydroxy terminated polyethylene and bishydroxy terminated polybutadiene, was added to the reaction system from step 1) at room temperature and the reaction was continued at 70 ℃ for 12h.
3) Casting the polymer solution obtained in the step 2) on a glass plate to form a film, and completing the preparation of the high-toughness polyurethane after the solvent is completely volatilized.
The polyurethane elastomer prepared in this example had excellent tear resistance (fig. 6). The polyurethane has good mechanical properties, the breaking stress of the original material is 41.7MPa, and the breaking elongation is 2260 percent (figure 6 a). The 5mm wide strip of film of this material was cut on one side to a wound of approximately 1mm length (fig. 6 b) and the material was stretched to 200% (i), 600% (ii), 1200% (iii), with no break in the material and with the cuts not extending into the material during stretching. The fracture energy is determined to be 145kJ m -2 。
Example 7: poly (tetrahydrofuran/dimethylsiloxane) urethanes that act as a sacrificial bond and a driving force for repair with hydrogen bonds and pi-pi interactions.
1) Polytetrahydrofuran (M) blocked with dihydroxy groups n 2000,2.0g, 1.0mmol), bishydroxy-terminated polydimethylsiloxane (M) n 1500,1.5g and 1.0mmol) is dissolved in the dehydrated N, N-dimethylacetamide and reacts with 1,5-naphthalene diisocyanate (0.844g and 4.02mmol) with 2.01 times of molar equivalent for 3 hours at the temperature of 80 ℃ to prepare a prepolymer;
2) Adding 1,5-naphthalenediol (0.0032g, 0.02mmol) which is 0.01 time of the sum of the molar weight of the bishydroxy-terminated polytetrahydrofuran and the molar weight of the polydimethylsiloxane into the reaction system obtained in the step 1), and continuously reacting for 24 hours at 80 ℃;
3) Adding 1,6-hexanediol (0.236g, 2mmol) which is the sum of the molar weight of 1 time of the dihydroxy-terminated polytetrahydrofuran and the polydimethylsiloxane into the reaction system obtained in the step 2), and continuously reacting at 80 ℃ for 24h;
4) And 3) casting the polymer solution obtained in the step 3) on a glass plate to form a film, and completing the preparation of the high-toughness polyurethane after the solvent is completely volatilized.
The polyurethane elastomer prepared in this example has excellent mechanical properties, with a breaking stress of 45MPa and an elongation at break of 2475% (fig. 7 a). Meanwhile, the material has excellent underwater elasticity, and when the material is continuously and circularly stretched to the strain of 100 percent underwater, the residual strain is only 5 percent (figure 7 b).
Example 8: poly (caprolactone) urethanes that act as a sacrificial bond and a driving force for repair with hydrogen bonds and pi-pi interactions.
1) End-capping of bishydroxy polycaprolactone (M) n 2000,20.0g and 10.0mmol) is dissolved in the dehydrated N, N-dimethylformamide and reacts with 1.01 times of molar equivalent of 1,4-cyclohexane diisocyanate (1.7g and 10.1mmol) at the temperature of 75 ℃ for 3 hours to prepare a prepolymer;
2) Adding 1,8-bis (hydroxymethyl) anthracene (0.024g, 0.1 mmol) with the molar weight 0.01 times that of the dihydroxy-terminated polycaprolactone into the reaction system obtained in the step 1), and continuously reacting at 75 ℃ for 48h;
3) Casting the polymer solution obtained in the step 2) on a glass plate to form a film, and completing the preparation of the high-toughness polyurethane after the solvent is completely volatilized.
The polyurethane elastomer prepared in this example has excellent mechanical properties, with the initial material having a stress at break of 54MPa and an elongation at break of 2355% (fig. 8). Meanwhile, the material has excellent water resistance, and the mass change of the material is less than 0.8 percent after the material is soaked in water for 15 days.
Claims (8)
1. A preparation method of a polyurethane elastomer with excellent water resistance, repairability and recyclable functions, high toughness and high mechanical strength comprises the following steps:
(1) Synthesis of prepolymer: dissolving one or more crystalline or amorphous dihydroxyl or diamino terminated polymers A serving as main chain components in a dry solvent, then adding a diisocyanate terminated compound B, and reacting for 0.5-48 h at 30-120 ℃; wherein the molar weight of the compound B is 1.01 to 2.01 times of that of the polymer A;
(2) Introduction of non-polar toughening sites: adding a hydroxyl or amino terminated hydrophobic toughening agent C with the molar weight 0.01-1.01 times that of the polymer A into the reaction system obtained in the step (1), and then reacting at 30-120 ℃ for 0.5-72 h;
(3) And (3) polymer chain extension: adding a dihydroxyl or diamino terminated chain extender D with the molar weight 0-1.00 times that of the polymer A into the reaction system obtained in the step (2), and then reacting at 30-120 ℃ for 0.5-72 h; and the molar amount of hydroxyl or amino groups of toughener C + the molar amount of hydroxyl or amino groups of chain extender D + the molar amount of hydroxyl or amino groups of polymer a = the molar amount of isocyanate groups of compound B;
(4) Molding: and (4) removing the solvent from the polymer solution obtained in the step (3) through a forming processing technology, and obtaining the polyurethane elastomer with high toughness and high mechanical strength, which has the functions of recycling and self-repairing after forming.
2. The method for preparing the polyurethane elastomer with excellent water resistance, repairable and recyclable functions, and high toughness and high mechanical strength according to claim 1, wherein the polyurethane elastomer is prepared by the following steps: the polymer A is one or more of dihydroxyl or diamino terminated polycaprolactone, polylactide, polyethylene, polybutadiene, polyethylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyisoprene and polypropylene oxide.
3. The method for preparing the polyurethane elastomer with excellent water resistance, repairable and recyclable functions, and high toughness and high mechanical strength according to claim 1, wherein the polyurethane elastomer is prepared by the following steps: the compound B is one or more of isophorone diisocyanate, 1,3-phenylene diisocyanate, 1,6-hexamethylene diisocyanate, diphenylmethane diisocyanate, 1,4-cyclohexane diisocyanate, dicyclohexylmethane 4,4' -diisocyanate, o-xylylene diisocyanate, 1,5-naphthalene diisocyanate and 1,8-octane diisothiocyanate.
4. The method for preparing the polyurethane elastomer with excellent water resistance, repairable and recyclable functions, and high toughness and high mechanical strength according to claim 1, wherein the polyurethane elastomer is prepared by the following steps: the solvent is one or more of chloroform, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dichloromethane, N-methylpyrrolidone or dimethyl sulfoxide.
5. The method for preparing the polyurethane elastomer with excellent water resistance, repairable and recyclable functions, and high toughness and high mechanical strength according to claim 1, wherein the polyurethane elastomer is prepared by the following steps: the flexibilizer C is one or more of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 1,5-naphthalenediol, 2,6-dihydroxyanthracene, 1,8-bis (hydroxymethyl) anthracene, 1-aminopyrene, 9,10-diaminophenanthrene.
6. The method for preparing the polyurethane elastomer with excellent water resistance, repairable and recyclable functions, and high toughness and high mechanical strength according to claim 1, wherein the polyurethane elastomer is prepared by the following steps: the chain extender D is one or more of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol and diethylene glycol, 1,4-butanediamine and 1,6-hexanediamine.
7. The method for preparing the polyurethane elastomer with excellent water resistance, repairable and recyclable functions, and high toughness and high mechanical strength according to claim 1, wherein the polyurethane elastomer is prepared by the following steps: and (4) the forming processing technology comprises one or more of film casting, tape casting, hot pressing, mould pressing and solvent replacement.
8. A polyurethane elastomer with high toughness and high mechanical strength and excellent water resistance and repairable and recyclable functions is characterized in that: is prepared by the process of any one of claims 1 to 7.
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