CN115109226A - Polyurethane elastomer and preparation and application thereof - Google Patents
Polyurethane elastomer and preparation and application thereof Download PDFInfo
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- CN115109226A CN115109226A CN202210102130.0A CN202210102130A CN115109226A CN 115109226 A CN115109226 A CN 115109226A CN 202210102130 A CN202210102130 A CN 202210102130A CN 115109226 A CN115109226 A CN 115109226A
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- polyurethane elastomer
- solvent
- fppu
- polyester
- appu
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 150000002009 diols Chemical class 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- 239000004020 conductor Substances 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- -1 bisphenol compound Chemical class 0.000 claims description 10
- 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 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 229930185605 Bisphenol Natural products 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- 238000010494 dissociation reaction Methods 0.000 abstract description 9
- 230000005593 dissociations Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 238000012958 reprocessing Methods 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 description 26
- 239000000806 elastomer Substances 0.000 description 26
- 235000013824 polyphenols Nutrition 0.000 description 19
- 238000004140 cleaning Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 6
- 230000035876 healing Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 230000007017 scission Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 229920006311 Urethane elastomer Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007634 remodeling Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006023 eutectic alloy Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3804—Polyhydroxy compounds
- C08G18/3812—Polyhydroxy compounds having fluorine atoms
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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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/65—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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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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
- C08G18/65—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
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- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
- H02N1/04—Friction generators
Abstract
The invention relates to a polyurethane elastomer, and preparation and application thereof, and the polyurethane elastomer is shown as a structural formula I. The polyurethane elastomer material of the invention has the advantages of low dissociation temperature, high-efficiency self-healing property and excellent reprocessing performance, and has wide application in the electronic field.
Description
Technical Field
The invention belongs to the field of functional polymer materials, and particularly relates to a polyurethane elastomer, and preparation and application thereof.
Background
Polyurethane (PU) elastomers are a polymer material with strong structural adjustability, excellent mechanical properties, and a wide range of applications, and are often used to construct electronic skins, energy conversion devices, medical implant devices, and the like. Polyurethane elastomers can be subdivided into thermoplastic elastomers and thermoset elastomers based on their chemical structure, with the structural and performance properties of both types of materials being widely different. Thermoplastic PU elastomers are easy to process and recycle due to their linear structure, but their solvent resistance and modulus are generally low, creep deformation is large, mechanical strength is low, and thermal stability is poor. Compared with thermoplastic PU, the thermosetting PU elastomer has obviously improved mechanical and thermal properties due to the self three-dimensional crosslinking structure. However, the conventional thermosetting elastomer has a permanently crosslinked network, and is difficult to reprocess and recycle, thereby causing serious resource waste and environmental pollution.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polyurethane elastomer and preparation and application thereof.
The invention relates to a polyurethane elastomer shown in a structural formula I,
wherein R is 1 Is composed of
R 2 Is composed of
Wherein the wavy line indicates the attachment position of the group;
wherein the range values of m are cumbersome to define; m is an integer greater than or equal to 1;
the range value of n is troublesome to define; n is an integer of 1 or more;
the range value of x is troublesome to define. x is an integer of 1 or more.
The preparation method of the polyurethane elastomer comprises the following steps:
(1) under the protection gas, polyester or polyether diol and a solvent are mixed, and then isophorone diisocyanate (IPDI) and a catalyst are added for reaction to obtain a diisocyanate end-sealed prepolymer;
(2) and (2) mixing a bisphenol compound and a solvent, then dropwise adding the mixture into the isocyanate end-sealed prepolymer obtained in the step (1), reacting, and then adding glycerol to continue reacting to obtain the polyurethane elastomer.
The preferred mode of the above preparation method is as follows:
the protective gas in the step (1) is nitrogen; the average molecular weight of the polyester or polyether diol is 400-10000 g/mol; the polyester or polyether diol is polytetrahydrofuran diol; the solvent is tetrahydrofuran; the catalyst is dibutyltin dilaurate.
In the step (1), the molar ratio of the polyester or polyether diol to the isophorone diisocyanate (IPDI) is 1: 2.1-1: 12; the dosage ratio of the catalyst is 0.1-0.5% of the total mass fraction of all raw materials (polyester or polyether diol, isophorone diisocyanate (IPDI), bisphenol compounds and glycerin).
The step (1) is specifically as follows: vacuumizing and heating polyester or polyether diol at 80-120 ℃ to remove water for 0.5-4h, removing vacuum, cooling to 25-70 ℃ in a protective gas atmosphere, adding a solvent, isophorone diisocyanate (IPDI) and a catalyst, and reacting at 25-70 ℃ for 0.5-2h in the protective gas atmosphere.
In the step (2), the bisphenol compound is hexafluorobisphenol A or bisphenol A; the solvent is tetrahydrofuran.
In the step (2), the molar ratio of the bisphenol compound to the prepolymer of isocyanate end sealing to the glycerol is 0.5: 1.25: 0.5-5: 5.75: 0.5.
and (2) mixing a bisphenol compound and a solvent, then dropwise adding the mixture into the isocyanate end-sealed prepolymer obtained in the step (1), reacting for 0.5-5h at 25-70 ℃, then adding glycerol, and continuing to react for 4-24h at 25-70 ℃.
The invention relates to a film based on the polyurethane elastomer.
Further, pouring the polyurethane elastomer into a mold, standing for 12-36h at 30-80 ℃, and finally, standing for 24-60h at 40-80 ℃ under a vacuum condition to obtain the polyurethane elastomer film.
The composite conductor comprises the polyurethane elastomer.
Further, the composite conductor comprises a conductive medium and a protective layer covering the surface of the conductive medium; wherein the conductive medium is gallium indium tin eutectic alloy; the protective layer is the polyurethane elastomer.
The friction nano-generator comprises the polyurethane elastomer.
Further, the friction nanogenerator sequentially comprises: a polydimethylsiloxane PDMS layer, the polyurethane elastomer layer, a conductive metal plate (e.g., copper plate).
The polyurethane elastomer is applied to the electronic field, such as wearable electronic equipment and the like.
Advantageous effects
The invention discloses a novel FPPU elastomer, which shows lower dissociation temperature, high-efficiency self-healing property and excellent reprocessing performance. With FPPU as the elastomeric substrate, a triboelectric nanogenerator (TENG) with reworkable and self-cleaning properties was prepared. The device can be as the self-powered power supply of wearable equipment, can turn into the electric energy with external mechanical motion. Meanwhile, the FPPU elastomer is utilized to construct a stretchable self-healing composite conductor so as to explore the application of the conductor in the field of flexible electronics.
In addition, bisphenol A (BPA) is used for replacing bisphenol AF (BPAF) to synthesize the fluorine-free polyurethane elastomer (APPU), the feasibility of preparing PUs from bisphenol compounds with different substituents is explored, and the influence of fluorine atoms on the overall performance of the elastomer is systematically researched. In particular, the trifluoromethyl group having a strong electron-withdrawing ability is a key constituent of the elastomer, and it can significantly lower the dissociation temperature of the phenolic urethane bond, and impart a high self-healing efficiency and a significant reworkability to the FPPU. Compared with APPU, FPPU elastomer also shows higher self-cleaning efficiency and lower dielectric constant, which is also beneficial to the application of the FPPU elastomer in the electronic field.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a phenolic urethane elastomer (FPPU and APPU); wherein (a) is a polyphenol urethane elastomer structure; (b) is a molecular diagram and related properties;
FIG. 2 shows (a) the same heating time (5min) with-NCO/C 6 H 6 The ratio was measured as the degree of cleavage of the phenolic urethane bond at different temperatures. (b) Fitting relaxation time according to an Arrhenius equation, and determining the activation energy of the elastomer according to the slope;
FIG. 3 is a graph of the self-healing and post-processing performance of FPPU and APPU elastomers; (a) the stress-strain curves of FPPU and (b) APPU; (c) self-healing efficiency of FPPU and APPU elastomers after healing for 1 hour at 30, 50 and 70 ℃; (d) a molecular diagram of a self-healing process, wherein a scale bar is 1.0 cm; (e) photo of fragments of elastomer treated at 75 deg.C, 90 deg.C and 5MPa for 30 min; stress-strain curves of remolded samples FPPU (f) and APPU (g); (h) recovering the tensile strength under different processing periods;
FIG. 4 is FTIR spectra of raw and reshaped samples of FPPU and APPU;
FIG. 5 is a schematic diagram of a simple electronic circuit and composite conductor (a) and a cut-healing-tensile test of the conductor (b);
FIG. 6 is a TENG of (a) "sandwich" structure; (b) the working mechanism of TENG; (c) electric output performance of TENG before and after remodeling based on FPPU and APPU; (d) FPPU (upper) and APPU (lower) contact angle plots (e) surface energy from contact angle; (f) self-cleaning performance of TENG based on FPPU and APPU.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
Firstly, raw material sources are as follows:
bisphenol A (BPA) and hexafluorobisphenol A (BPAF) are both available from (Shanghai) Tantaceae technologies, Inc.; polytetrahydrofuran diol (PTMG-1000, Mn 1000g/mol) was purchased from alatin reagent (shanghai) ltd and dried under vacuum at 110 ℃ for 2h before use;
isophorone diisocyanate (IPDI) is commercially available from wawa chemical (shandong); tetrahydrofuran ultra-dry solvent (THF, 99.9%) was purchased from carbofuran (shanghai) technologies; glycerol (glycol, 98%) was purchased from alatin reagent (shanghai) ltd; dibutyl tin dilaurate (DBTDL, 95%) was purchased from shanghai mclin biochem technologies, ltd. All reagents were not further processed before use.
Second, test standards and methods
An electronic universal material testing machine is adopted to represent the mechanical property and the self-healing property of the material.
Tensile strength test method is as follows: selecting a uniaxial tension mode of an electronic universal material testing machine to carry out five tests on the same sample strip, averaging the results, and setting the tension rate to be 50mm min -1 。
Testing the healing efficiency: the material was cut into a rectangular shape (0.5mm (T) by 5mm (W) by 15mm (L)), and then completely cut and put together, and was healed under a specific condition without applying an external force. The healing efficiency of the material was characterized by the tensile strength of the specimen before and after healing.
Example 1
Synthesis of polyurethane elastomer FPPU
Polytetrahydrofuran diol (PTMG-1000, 4.000g, 4.000mmol) is firstly added into a 50ml reaction flask, the temperature of an oil bath is controlled at 110 ℃, and water is removed by heating under vacuum for 2 h. Then, the vacuum was removed, and a nitrogen ball was inserted to maintain an atmosphere of N2. When the temperature is reduced to 60 ℃, 8ml of ultra-dry solvent Tetrahydrofuran (THF) is added, isophorone diisocyanate (IPDI, 2.334g, 10.500mmol) is slowly dripped into a reaction bottle, a catalyst dibutyltin dilaurate (DBTDL) is added, and the reaction is carried out for 2h at 60 ℃ in a nitrogen atmosphere.
Hexafluorobisphenol A (BPAF, 1.345g, 4.000mmol) was dissolved in 5ml of ultra-dry reagent Tetrahydrofuran (THF), and added dropwise to a diisocyanate-terminated Prepolymer (Prepolymer) solution, and reacted at 60 ℃ for 1 h. Glycerol (0.147g, 1.600mmol) was added to the reaction solution, maintaining the temperature at 60 ℃. After 4 hours, the whole mixed solution is poured into a tetrafluoro mold and then transferred into an oven, and the mixed solution is respectively placed for 12 hours under the conditions of 40 ℃ and 60 ℃, and finally maintained for 24 hours under the vacuum condition of 80 ℃ to obtain the FPPU film.
Example 2
The preparation was carried out in detail as in example 1, except that BPAF in example 1 was replaced with bisphenol A (BPA, 0.913g, 4.000mmol) to synthesize an APPU film.
The FPPU of example 1 and the APPU of example 2 were characterized:
(1) study of dynamic Properties of phenolic urethane bond
Based on temperature-variable Fourier transform infrared spectroscopy and stress relaxation tests, the introduction of the fluorinated group is respectively verified from the thermodynamic and kinetic angles to effectively adjust the dynamic performance of the phenolic urethane bond. The phenolic urethane bonds belong to the cleavage type of dynamic covalent bonds, and the dynamic properties of the different phenolic urethane bonds can be determined from their initial cleavage temperature, which corresponds to the cleavage of the phenolic ester bonds to free-NCO groups (2270 cm) -1 ) The initial temperature of (a). As shown in FIG. 2a, after the two elastomers are heated at 50 ℃ for 5min, the phenolic urethane bond is not dissociated, and no absorption peak of free-NCO groups is detected in the infrared spectrum; it is heated at 60 deg.C for 5min, and in FPPU at 2270ccm -1 Where a weaker absorption peak appears. Whereas the initial dissociation temperature in the APPU corresponding to the free-NCO is 70 ℃. The initial dissociation temperature of FPPU is significantly lower compared to APPU, because the trifluoromethyl strong electron withdrawing action enhances the dynamic properties of the phenolic urethane bond. Thus, the lower the network rearrangement temperature in FPPU due to dissociation and association of the urethane bond in the medium phenol will be compared to that in APPU. In addition, in the range of 60-130 ℃, the dissociation rate and degree of the phenolic urethane bond are gradually increased along with the increase of the temperature. However, when the temperature is higher than 130 ℃, the amount of free-NCO is gradually decreased as the temperature increases, and it is preliminarily presumed that the dissociated-NCO at high temperature is consumed by moisture in hot air. In addition, the PU-CANs network rearrangement rate of the phenolic urethane bond based on different electronic effects is researched from the aspect of dynamics. At 30 ℃, FPPU has a slightly shorter characteristic relaxation time (τ ═ 18s) than APPU (τ ═ 25 s). With increasing temperature, τ @ of both elastomers decreases constantly and always less under the same conditions for FPPU than for APPU. As shown in FIG. 2b, Ea (of FPPU elastomer)48.8kJ mol -1 ) Slightly lower than Ea (53.9kJ mol) of the APPU elastomer -1 ) This indicates that the network of APPUs is more stable than FPPU. In other words, the dynamic characteristics of the phenolic urethane bond in FPPU are improved due to the electronic effect of the fluorinated group.
(2) Self-healing and removability properties of FPPU
The raw tensile strengths of FPPU and APPU at room temperature were 11.42 + -0.36 MPa and 11.10 + -0.92 MPa, respectively, as shown in FIGS. 3a and 3 b. To compare their self-healing properties, 0.5X 5X 20mm was cut with razor blades 3 Is cut into two parts. The two fractured parts were left to heal under different conditions after being touched for 10 s.
As shown in FIG. 3c and Table 1, the self-healing rate (65%) of the FPPU elastomer after being treated at 30 ℃ for 1h is higher than that (31%) of the APPU elastomer at the same temperature, which indicates that the fluorine-containing group has strong electron withdrawing effect and can improve the dynamic performance of the phenolic urethane bond. In addition, the self-healing efficiency of the two elastomers can be remarkably improved by increasing the temperature, because the mobility of molecular chains is higher under the high-temperature condition, and the dissociation rate and the dissociation degree of the phenolic urethane bonds are correspondingly improved. The self-healing rates of FPPU at 50 ℃ and 70 ℃ for 1 hour reach 85 percent and 98 percent respectively, and are higher than those of APPU under the same conditions (71 percent and 96 percent). For FPPU and APPU, these cleaved specimens are able to contact each other well and heal through dynamic bond exchange due to the large number of phenolic urethane bonds and hydrogen bonds contained in the elastomer network.
As shown in fig. 3d, the kinetics of the high temperature dissociative exchange of the phenolic urethane bond and its low temperature stability are vividly explained. To further evaluate the processability and recyclability of FPPU, the elastomers prepared were cut into small pieces, hot-pressed for 30min at a pressure of 5MPa and a temperature of 75 ℃ and the treated samples were heat-equilibrated at 50 ℃ for 24h to ensure complete reorganization and exchange of the phenolic urethane bonds (FIG. 3 e). In addition, the APPU was subjected to the same treatment at different hot-pressing temperatures (90 ℃ C.). By evaluating the samples before and after the remodeling, FTIR spectra as shown in FIG. 4 were obtained. The original and reshaped spectra were nearly identical, confirming that neither the FPPU nor the APPU had a change in chemical structure. Uniaxial tensile testing of the remolded samples showed (fig. 3f and 3g) that the reprocessed FPPU retained most of the mechanical properties of the original sample, with a recovery of tensile strength of over 95% comparable to the original tensile strength, while the recovery of tensile strength of APPU reached 90% under the same conditions (fig. 3 h).
TABLE 1 self-healing efficiency of FPPU and APPU under different conditions
Example 3
Stretchable and self-healing composite conductors:
FPPU can be prepared as a composite conductor having stretchability and self-healing properties due to its excellent self-healing efficiency and elongation at break. As shown in fig. 5 a. Gallium indium tin eutectic gold is used as a conductive medium, and the FPPU elastomer covers the outside of the conductive medium to serve as a protective layer. The device is connected with a 3V battery and a Light Emitting Diode (LED) to form a complete circuit. As shown in fig. 5b (i), the LED normally emits light, and when the composite conductor containing the liquid metal is divided into two parts, the LED is extinguished (II). The broken conductor was placed in an oven at 70 ℃ for 30min, after the circuit was switched in, the LED was lit up again (III), and the conductor could be stretched 4 times the original length after healing. The FPPU has good thermal self-healing property and mechanical property, and shows good application prospect in the field of flexible electronics.
Example 4
Remouldable and self-cleaning friction nano generator
TENG of "sandwich" structure (as shown in fig. 6a and 6 b), its structure and specific composition are as follows: the structure of the single electrode mode TENG included a self-cleaning, reprocessable and self-healing tribological positive electrode material (FPPU or APPU), a tribological negative electrode material (polydimethylsiloxane (PDMS) and a conductive electrode layer (copper sheet) and was tested for its electrical output performance as shown in FIG. 6c and the results in Table 2Open-circuit voltage, short-circuit current, and short-circuit charge amount of TENG based on FPPU are larger than open-circuit voltage (V) of TENG based on APPU OC ) The short-circuit current and the short-circuit charge amount are respectively higher than 45V, 1.1 muA and 16 nC. In addition, the FPPU elastomeric substrate was divided and cut into small pieces, then hot-pressed at 75 ℃ and 5MPa for 30min, and the remolded samples were heat-equilibrated at 50 ℃ for 24h, which were assembled into TENG. Test results show that the open-circuit voltage output efficiency of TENG of the remolded FPPU is as high as 93.2%. The output efficiencies of the short-circuit current and the short-circuit charge quantity corresponding to the reset TENG reach 93.6 percent and 93.0 percent respectively.
TABLE 2 remouldable TENG output Properties based on FPPU and APPU elastomeric substrates
| Sample | O V | R V | O-E(％) | O A | R A | O-E(％) | O Q | R Q | O-E(％) |
| TENG-FPPU | 103V | 96V | 93.2 | 4.7μA | 4.4μA | 93.6 | 43nC | 40nC | 93.0 |
| TENG-APPU | 58V | 53V | 91.4 | 3.6μA | 3.5μA | 97.2 | 27nC | 22nC | 81.5 |
O stands for original, R stands for remolded, V stands for open circuit voltage, a stands for short circuit current, Q stands for short circuit charge amount, and O-E (%) stands for electrical output efficiency.
Second, TENG antifouling capacity is characterized by calculating self-cleaning efficiency. FPPU, because of its higher hydrophobicity and lower surface energy, TENG made from it will be endowed with better self-cleaning performance, as shown in fig. 6d and 6e, FPPU has significantly higher water contact angle than APPU, and therefore the corresponding surface energy is lower. The FPPU substrate was placed in a dust-contaminated environment for 10h, and a defined amount of water (100mL min) -1 ) The two substrates are washed for 30min respectively and dried by a hot air gun for standby. The FPPU or APPU films treated as described above are reassembled into a complete TENG. As shown in FIG. 6f and Table 3, the self-cleaning efficiency of TENG prepared from FPPU was 92.2%, which is significantly higher than that of TENG prepared from APPUSelf-cleaning efficiency (-74.1%).
TABLE 3 self-cleaning TENG output efficiency based on FPPU and APPU elastomer substrates
| Sample | O V | S-C V | O-E(％) |
| TENG-FPPU | 103V | 95V | 92.2 |
| TENG-APPU | 58V | 43V | 74.1 |
O stands for original, S-C stands for after self-cleaning, V stands for open circuit voltage, and O-E (%) stands for electrical output efficiency.
Claims (10)
1. A polyurethane elastomer shown as a structural formula I,
wherein R is 1 Is composed of
R 2 Is composed of
Wherein the range values of m are cumbersome to define; m is an integer greater than or equal to 1;
the range value of n is troublesome to define; n is an integer of 1 or more;
the range value of x is troublesome to define. x is an integer of 1 or more.
2. A method of preparing a polyurethane elastomer, comprising:
(1) under the protection gas, polyester or polyether diol and a solvent are mixed, and then isophorone diisocyanate (IPDI) and a catalyst are added for reaction to obtain a diisocyanate end-sealed prepolymer;
(2) and (2) mixing a bisphenol compound and a solvent, then dropwise adding the mixture into the isocyanate end-sealed prepolymer obtained in the step (1), reacting, and then adding glycerol to continue reacting to obtain the polyurethane elastomer.
3. The method according to claim 2, wherein the protective gas in the step (1) is nitrogen; the average molecular weight of the polyester or polyether diol is 400-10000 g/mol; the polyester or polyether diol is polytetrahydrofuran diol; the solvent is tetrahydrofuran; the catalyst was dibutyltin dilaurate.
4. The preparation method according to claim 2, wherein the molar ratio of the polyester or polyether diol to the isophorone diisocyanate (IPDI) in the step (1) is 1: 2.1-1: 12; the dosage ratio of the catalyst is 0.1-0.5% of the total mass fraction of all the raw materials.
5. The preparation method according to claim 2, wherein the step (1) is specifically: vacuumizing and heating polyester or polyether diol at 80-120 ℃ to remove water for 0.5-4h, removing vacuum, cooling to 25-70 ℃ in a protective gas atmosphere, adding a solvent, isophorone diisocyanate (IPDI) and a catalyst, and reacting at 25-70 ℃ for 0.5-2h in the protective gas atmosphere.
6. The process according to claim 2, wherein the bisphenol compound in the step (2) is hexafluorobisphenol A or bisphenol A; the solvent is tetrahydrofuran; the molar ratio of the bisphenol compound, the isocyanate end-sealed prepolymer and the glycerol in the step (2) is 0.5: 1.25: 0.5-5: 5.75: 0.5.
7. the preparation method of claim 2, wherein in the step (2), the bisphenol compound and the solvent are mixed, and then the mixture is dropwise added into the isocyanate-terminated prepolymer in the step (1) to react for 0.5 to 5 hours at a temperature of between 25 and 70 ℃, and then glycerin is added to continue to react for 4 to 24 hours at a temperature of between 25 and 70 ℃.
8. A composite conductor comprising the polyurethane elastomer of claim 1.
9. A triboelectric nanogenerator, comprising the polyurethane elastomer of claim 1.
10. Use of the polyurethane elastomer of claim 1 in the electronic field.
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