CN115260446B - Recyclable high-strength scratch-resistant self-repairing transparent polyurethane film and preparation method thereof - Google Patents
Recyclable high-strength scratch-resistant self-repairing transparent polyurethane film and preparation method thereof Download PDFInfo
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- CN115260446B CN115260446B CN202210909166.XA CN202210909166A CN115260446B CN 115260446 B CN115260446 B CN 115260446B CN 202210909166 A CN202210909166 A CN 202210909166A CN 115260446 B CN115260446 B CN 115260446B
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- 229920006264 polyurethane film Polymers 0.000 title claims abstract description 44
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 18
- 229920000570 polyether Polymers 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000004970 Chain extender Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 150000004985 diamines Chemical class 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims abstract description 5
- 150000002513 isocyanates Chemical group 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 claims description 20
- -1 oxalyl diamine Chemical class 0.000 claims description 17
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 13
- 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 13
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- JJSYPAGPNHFLML-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylpropanoic acid Chemical group OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.CCC(CO)(CO)CO JJSYPAGPNHFLML-UHFFFAOYSA-N 0.000 claims description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 10
- 238000001723 curing Methods 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- 238000013007 heat curing Methods 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 125000004427 diamine group Chemical group 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- 238000004383 yellowing Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 34
- 239000000463 material Substances 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 6
- 238000007865 diluting Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920005570 flexible polymer Polymers 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 125000003431 oxalo group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
-
- 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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of self-repairing transparent films, and discloses a recyclable high-strength scratch-resistant self-repairing transparent polyurethane film and a preparation method thereof. The method comprises the following steps: 1) Carrying out prepolymerization reaction on polyether glycol and asymmetric alicyclic diisocyanate under the action of a catalyst to obtain an isocyanate group-terminated prepolymer; 2) Carrying out chain extension reaction on the prepolymer and a diamine-based chain extender; 3) And mixing the multi-mercapto cross-linking agent with the system with the chain extension reaction completed, and curing and forming to obtain the high-strength scratch-resistant transparent self-repairing polyurethane film. The film of the invention has multiple hydrogen bonds and dynamic thiourethane bonds; the structure ensures that the film of the invention has high mechanical strength (61.6 MPa) and good toughness (105.6 MJ/m) 3 ) Has excellent self-healing capability and recoverability, good scratch resistance, good light transmittance (98.6% of standard light transmittance in the visible light range), high refractive index (more than 1.49), low haze and yellowing resistance.
Description
Technical Field
The invention belongs to the technical field of self-repairing materials, and particularly relates to a recyclable high-strength scratch-resistant self-repairing transparent polyurethane film and a preparation method thereof.
Background
The transparent flexible polymer is a functional material which develops rapidly, has high light transmittance as well as high elasticity as optical plastic (PMMA, PC, PS), and also has the unique high elasticity of an elastomer, namely, can generate large deformation under the action of external force, and can completely or mostly recover the deformation after the external force is removed. The self-repairing high polymer material can spontaneously repair or completely repair the damaged part, thereby eliminating hidden trouble caused by the damaged part to a great extent. The transparent flexible polymer self-repairing capability is endowed, the service life and the use safety of the material can be improved, and a more economical, convenient and effective recycling method is provided, so that the material is an emerging intelligent bionic material.
The cross-linked polyurethane has the properties of high mechanical strength, wear resistance, excellent ageing resistance, chemical corrosion resistance and the like, and is widely applied to various industries such as buildings, households, mechanical accessories, sports equipment, national defense and military. However, the crosslinked structure also makes it difficult to reprocess and recycle, and the waste thermosetting polymer causes serious waste of resources and environmental pollution. The polyurethane with the dynamic cross-linking structure can simultaneously endow the material with excellent mechanical property and recycling reworkability, and can make a certain contribution to the national energy conservation priority and environmental friendly sustainable development strategy.
Chinese patent No. CN 111518376B discloses a self-healing polyurethane based on multiple hydrogen bonds, however, the tensile strength of the elastomer is not high, only 14MPa. Chinese patent No. 111440315B discloses a transparent thermoplastic polyurea elastomer, which is endowed with self-repairing property by introducing regular hydrogen bonds and irregular hydrogen bonds, and has tensile strength of only 8MPa and toughness of less than 30MJ/m 3 . Chinese patent No. CN 108503782B discloses a fully transparent high strength self-repairing polyurethane elastomer with tensile strength of 22MPa. Chinese patent application No. CN 114085355A discloses a high-strength water-resistant thermoplastic polyurethane elastomer with strength up to 52.1MPa but no self-repairing propertyCan be used. Chinese patent No. 107163214B discloses an enhanced crosslinked polyurethane elastomer with a maximum strength of 22MPa, which is difficult to recycle due to permanent covalent crosslinking, thus wasting resources. Thus, achieving the properties of high strength, stretchability, transparency, self-healing, and recyclability of polymeric materials at the same time has remained a great challenge to date.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a high-strength scratch-resistant self-repairing transparent polyurethane film and a preparation method thereof. The high-strength scratch-resistant transparent film has self-repairing property and recycling property.
The aim of the invention is achieved by the following technical scheme:
the preparation method of the recyclable high-strength scratch-resistant self-repairing transparent polyurethane film comprises the following steps:
1) Carrying out prepolymerization reaction on polyether glycol and asymmetric alicyclic diisocyanate under the action of a catalyst to obtain an isocyanate group-terminated prepolymer;
2) Carrying out chain extension reaction on the prepolymer and a diamine-based chain extender;
3) Mixing the multi-mercapto cross-linking agent with the system with the chain extension reaction completed, and curing and forming to obtain the high-strength scratch-resistant transparent self-repairing polyurethane film;
the diamine-based chain extender is one or two of oxalyl dihydrazide (Oxalyl dihydrazide) or oxalyl diamine;
the multi-mercapto cross-linking agent is one or two of trimethylolpropane tri (3-mercaptopropionate) and tetra (3-mercaptopropionic acid) pentaerythritol ester.
The polyether glycol in the step 1) is one or two of polytetramethylene ether glycol (PTMO) and polypropylene oxide ether glycol (PPG);
the number average molecular weight of the polyether glycol in the step 1) is 650-3000g/mol.
The asymmetric alicyclic diisocyanate in step 1) is isophorone diisocyanate (IPDI).
The temperature of the prepolymerization reaction in the step 1) is 75-85 ℃ and the time is 3-5 hours;
the temperature of the chain extension reaction in the step 2) is 40-50 ℃ and the time is 6-10 hours.
The catalyst in the step 1) is one or more of triethylamine, stannous octoate or dibutyltin dilaurate.
Adding a solvent during the chain extension reaction in the step 2); the solvent is added or mixed with the chain extender and the prepolymer during the chain extension reaction (e.g., the chain extender is mixed with the prepolymer and then the solvent is added; or the chain extender is mixed with the solvent and then the prepolymer, etc.);
the solvent in the step 2) is one or more of N, N-dimethylacetamide, toluene and acetone; the volume mass ratio of the solvent to the polyether glycol is (2-5) mL:1g.
The addition amount of the catalyst in the step 1) is 0.5-1% of the weight of the polyether glycol;
the molar ratio of diisocyanate to polyether glycol is (1.9-2.6): 1, preferably (2 to 2.5): 1.
the molar ratio of the diamine-based chain extender to the polyether glycol in the step 2) is (0.6-0.8): 1.
the molar ratio of the multi-mercapto cross-linking agent to the polyether glycol in the step 3) is (0.2-0.6): 1.
the polyether glycol in the step 1) needs to be subjected to vacuum dehydration treatment before the reaction.
The curing in the step 3) refers to molding in a mold, removing the solvent and thermally curing.
The heat curing is to treat for 6 to 12 hours at the temperature of 60 to 80 ℃;
the solvent removal refers to removal of the organic solvent used under the condition of a vacuum oven at 40-60 ℃.
And 3) adding the sulfhydryl crosslinking agent into the system after chain extension, uniformly stirring, and pouring into a polytetrafluoroethylene mould for curing and molding.
The high-strength scratch-resistant transparent self-repairing polyurethane film is a polyurethane film based on multiple hydrogen bonds and dynamic thiourethane bonds.
The repair method of the self-repair polyurethane film based on multiple hydrogen bonds and dynamic thiourethane bonds comprises the following steps: the scratched or broken film is treated at 60-110 deg.c. The film with scratches is treated for 2 to 6 hours at the temperature of 60 to 80 ℃ and the scratches are repaired successfully by themselves; cutting the film, and treating at 60-110 deg.c for 12-36 hr.
The recovery method of the self-repairing polyurethane film based on multiple hydrogen bonds and dynamic thiourethane bonds comprises the following steps: and (3) carrying out open mill kneading on the sheared sample strips to remove bubbles in the gaps of the sample, putting the sample strips into a hot press die, hot-pressing for 0.5 hour at 140 ℃, demoulding to obtain a reprocessed sample, and testing the tensile strength.
The film is synthesized by polyether glycol, asymmetric alicyclic diisocyanate, diamine-based chain extender and multi-mercapto cross-linking agent. The amino chain extender with a unique structure and the hard phase formed by the reaction of isocyanate can form multiple hydrogen bonds, and the formation of the multiple hydrogen bonds can greatly improve the mechanical strength of the polymer and endow the material with self-repairing characteristics; the mercapto compound reacts with isocyanate to form thiocarbamate bond with dynamic exchange property, so forming covalent adaptive network. The dynamic cross-linked structure not only contributes to the self-repairing property of the material, but also endows the material with the capability of recycling and reprocessing. The material has high mechanical strength (61.6 MPa) and good toughness (105.6 MJ/m) 3 ) The self-healing coating has excellent self-healing capacity and recoverability, is scratch-resistant, has good light transmittance (standard light transmittance is 98.6% in a visible light range), has high refractive index (more than 1.49), low haze and yellowing resistance, and has wide application prospect in the intelligent coating fields such as optical devices, automobile surface protection and the like.
Compared with the prior art, the invention has the following characteristics:
the film of the invention has multiple hydrogen bonds, the introduction of the multiple hydrogen bonds improves the mechanical property and self-repairing property of the polymer, and the crosslinking effect of the dynamic thiourethane bond in the film not only provides the molecular network structure stability at the use temperature (the film of the invention has better stability at 60 ℃ and better stability at room temperature) but also endows the material with the recoverability at the higher temperature (such as 140 ℃).
The self-repairing polyurethane film has high toughness and scratch resistance, and the copper brush is difficult to leave scratches on the surface of the film.
The self-repairing polyurethane film is of a condensed amorphous structure, is excellent in transparency and low in haze, has an average light transmittance of 91.3% (1.3 mm thick) in a visible light range (400-800 nm), has a standard light transmittance of 98.6% (0.2 mm thick), and has an average haze value of 2.9%. The light transmittance is not lower than 90 percent after the treatment for 800 hours at 80 ℃.
The self-repairing polyurethane film has high refractive index, the refractive index is more than 1.49 in the visible light range, and the self-repairing polyurethane film meets the standard of an optical lens.
Drawings
FIG. 1 is a synthetic route diagram of the self-repairing polyurethane film of example 1 of the present invention;
FIG. 2 is an optical microscope image of a scratch self-repairing test of the self-repairing polyurethane film prepared in example 1; the left graph is a graph before self-repairing the scratched film, and the right graph is a graph after self-repairing the scratched film;
FIG. 3 is a graph comparing scratch resistance of the self-healing polyurethane film prepared in example 3 and the film prepared in comparative example 1;
FIG. 4 (a) is a graph showing the transmittance and haze of the self-repairing polyurethane film prepared in example 3; (b) Refractive index maps for the self-healing polyurethane films prepared in examples 1-4;
FIG. 5 is a graph showing the recyclability of the self-healing polyurethane film prepared in example 3.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto.
The repairing method of the self-repairing polyurethane film comprises the following steps: treating the film with scratches at 80 ℃ for 3 hours, and automatically repairing the scratches successfully; cutting the film into dumbbell-shaped or rectangular sample strips, cutting the sample strips by a surgical knife to more than 80%, standing at 80 ℃ for 24 hours, and testing the tensile strength.
The recovery method of the self-repairing polyurethane film comprises the following steps: and (3) carrying out open mill kneading on the sheared sample strips to remove bubbles in the gaps of the sample, putting the sample strips into a hot press die, hot-pressing for 0.5 hour at 140 ℃, demoulding to obtain a reprocessed sample, and testing the tensile strength.
Example 1
The preparation method of the recyclable high-strength scratch-resistant self-repairing transparent film comprises the following steps:
mixing and stirring 4.45g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (with the molecular weight of 1000 g/mol) uniformly, adding 0.05g of dibutyltin dilaurate, heating and stirring in an oil bath at 80 ℃ for reacting for 4 hours to obtain a prepolymer; 0.83g of oxalyl dihydrazide is added into the prepolymer (30 ml of N, N-dimethylacetamide is added for dilution), and the reaction is carried out for 8 hours at 50 ℃ to dissolve the oxalyl dihydrazide while reacting; then adding 0.80g of trimethylolpropane tri (3-mercaptopropionate) into the system, uniformly stirring, pouring the reaction product into a polytetrafluoroethylene mould to form a film, removing the used organic solvent under the condition of a vacuum oven at 40-60 ℃, and then treating for 12 hours under the condition of a blast oven at 80 ℃ to obtain the polyurethane film. The tensile strength of the film is 49.5MPa, the elongation at break is 614.9 percent, and the toughness is 93.4MJ/m 3 . After the spline is cut off to be more than 80%, repairing is carried out for 24 hours at 80 ℃, the tensile strength after repairing is 44MPa, and the repairing efficiency is 88.9%.
The film prepared in this example had a light transmittance of 91% or more as in example 3.
FIG. 1 is a synthetic route for the recyclable high strength scratch resistant self healing transparent film of example 1. FIG. 2 is a scratch self-repairing optical microscope image of the film prepared in example 1. As can be seen from fig. 2, the sample was scratched by the scalpel to generate an obvious incision, and the incision was repaired for 3 hours in an environment of 80 ℃, and the scratch was self-repaired.
The synthetic route of the following examples is the same as that of fig. 1, and the optical microscope restoration picture is similar to that of fig. 2, but is not provided one by one.
Example 2
Mixing and stirring 4.80g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (with the molecular weight of 1000 g/mol) uniformly, adding 0.05g of dibutyltin dilaurate, heating and stirring in an oil bath at 80 ℃ for reaction for 4 hours to obtain a prepolymer; adding 0.83g of oxalyl dihydrazideAdding the mixture into a prepolymer, reacting for 8 hours at 50 ℃, and adding 30ml of N, N-dimethylacetamide for dilution during the reaction, so as to dissolve oxalyl dihydrazide while reacting; then adding 1.20g of trimethylolpropane tri (3-mercaptopropionate) into the system, uniformly stirring, pouring the reaction product into a polytetrafluoroethylene mould, removing the used organic solvent under the condition of a vacuum oven at 40-60 ℃, and then treating for 12 hours under the condition of a blast oven at 80 ℃ to obtain the polyurethane film. The tensile strength of the film is 56.6MPa, the elongation at break is 575.4 percent, and the toughness is 103.4MJ/m 3 . After the spline is cut off to be more than 80%, repairing is carried out for 24 hours at 80 ℃, the tensile strength after repairing is 49.4MPa, and the repairing efficiency is 87.3%.
The film prepared in this example had a light transmittance of 91% or more as in example 3.
Example 3
A recoverable high-strength scratch-resistant self-repairing transparent film and a preparation method thereof comprise the following steps:
uniformly mixing and stirring 5.11g of isophorone diisocyanate and 10g of polytetramethylene ether glycol with the molecular weight of 1000g/mol, adding 0.05g of dibutyltin dilaurate into the mixture, heating and stirring the mixture in an oil bath at 80 ℃ for reacting for 4 hours to obtain a prepolymer; adding 0.83g of oxalyl dihydrazide into the prepolymer, reacting for 8 hours at 50 ℃, and adding 30ml of N, N-dimethylacetamide to dilute during the reaction, so that the oxalyl dihydrazide is dissolved while reacting; then adding 1.59g of trimethylolpropane tri (3-mercaptopropionate) into the system, uniformly stirring, pouring the reaction product into a polytetrafluoroethylene mould, removing the used organic solvent under the condition of a vacuum oven at 40-60 ℃, and then treating for 12 hours under the condition of a blast oven at 80 ℃ to obtain the polyurethane film. The film had a tensile strength of 61.6MPa, an elongation at break of 539% and a toughness of 105.6MJ/m 3 . After the spline is cut off to be more than 80%, repairing is carried out for 24 hours at 80 ℃, the tensile strength after repairing is 50.4MPa, and the repairing efficiency is 81.9%. The film obtained in example 3 was scratched with a copper brush for 500 cycles, and only sparse scratches were observed under an optical microscope, and the scratch resistance was excellent.
FIG. 3 is a graph comparing scratch resistance of the film prepared in example 3 with that of the film prepared in comparative example 1;
FIG. 4 (a) is a graph showing the change in transmittance and haze with wavelength of the film prepared in example 3; (b) Graphs of refractive index versus wavelength for the films prepared for examples 1-4;
after the sample of example 3 was sheared, air bubbles in the voids of the sample were removed by open mill kneading, the sample was put into a hot press mold, hot pressed at 140℃for 0.5 hours, and the reprocessed sample was obtained by demolding, and the tensile strength was measured, and the processing was repeated three times, and the measured tensile curve was shown in FIG. 5. FIG. 5 is a graph showing the recyclability of the self-healing polyurethane film prepared in example 3.
Example 4
A recoverable high-strength scratch-resistant self-repairing transparent film and a preparation method thereof comprise the following steps:
mixing 5.78g isophorone diisocyanate and 10g polytetramethylene ether glycol (molecular weight 1000 g/mol), stirring uniformly, adding 0.05g dibutyltin dilaurate, heating in an oil bath at 80 ℃ and stirring for 4 hours to obtain a prepolymer; adding 0.83g of oxalyl dihydrazide into the prepolymer, reacting for 8 hours at 50 ℃, and diluting with 30ml of N, N-dimethylacetamide during the reaction, so that the oxalyl dihydrazide is dissolved and reacted at the same time; then adding 2.39g of trimethylolpropane tri (3-mercaptopropionate) into the system, uniformly stirring, pouring the reaction product into a polytetrafluoroethylene mould, removing the used organic solvent under the condition of a vacuum oven at 40-60 ℃, and then treating for 12 hours under the condition of a blast oven at 80 ℃ to obtain the polyurethane film. The tensile strength of the film is 64.4MPa, the elongation at break is 489 percent, and the toughness is 94.7MJ/m 3 . After the spline is cut off to be more than 80%, repairing is carried out for 24 hours at 80 ℃, the tensile strength after repairing is 39.9MPa, and the repairing efficiency is 61.2%. The film prepared in this example had a light transmittance of 91% or more as in example 3.
Example 5
A recoverable high-strength scratch-resistant self-repairing transparent film and a preparation method thereof comprise the following steps:
mixing and stirring 4.22g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (with the molecular weight of 1000 g/mol) uniformly, adding 0.05g of dibutyltin dilaurate, heating and stirring in an oil bath at 80 ℃ for reacting for 4 hours to obtain a prepolymer; 0.71g of oxalyl dihydrazide was added to the prepolymerIn the body, reacting for 8 hours at 50 ℃, and adding 30ml of N, N-dimethylacetamide to dilute the solution, so that the oxalyl dihydrazide reacts while dissolving; then adding 0.80g of trimethylolpropane tri (3-mercaptopropionate) into the system, uniformly stirring, pouring the reaction product into a polytetrafluoroethylene mould, removing the used organic solvent under the condition of a vacuum oven at 40-60 ℃, and then treating for 12 hours under the condition of a blast oven at 80 ℃ to obtain the polyurethane film. The tensile strength of the film is 30.7MPa, the elongation at break is 613 percent, and the toughness is 46.6MJ/m 3 . After the spline is cut off to be more than 80%, repairing is carried out for 24 hours at 80 ℃, the tensile strength after repairing is 27.9MPa, and the repairing efficiency is 90.9%. The film prepared in this example had a light transmittance of 91% or more as in example 3.
Example 6
A recoverable high-strength scratch-resistant self-repairing transparent film and a preparation method thereof comprise the following steps:
mixing and stirring 4.56g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (with the molecular weight of 1000 g/mol) uniformly, adding 0.05g of dibutyltin dilaurate, heating and stirring in an oil bath at 80 ℃ for reacting for 4 hours to obtain a prepolymer; adding 0.71g of oxalyl dihydrazide into the prepolymer, reacting for 8 hours at 50 ℃, and diluting with 30ml of N, N-dimethylacetamide during the reaction, so that the oxalyl dihydrazide is dissolved and reacted at the same time; then adding 1.20g of trimethylolpropane tri (3-mercaptopropionate) into the system, uniformly stirring, pouring the reaction product into a polytetrafluoroethylene mould, removing the used organic solvent under the condition of a vacuum oven at 40-60 ℃, and then treating for 12 hours under the condition of a blast oven at 80 ℃ to obtain the polyurethane film. The tensile strength of the film is 34.8MPa, the elongation at break is 605%, and the toughness is 48.9MJ/m 3 . After the spline is cut off to be more than 80%, repairing is carried out for 24 hours at 80 ℃, the tensile strength after repairing is 31.7MPa, and the repairing efficiency is 91.1%.
The film prepared in this example had a light transmittance of 91% or more as in example 3.
Example 7
A recoverable high-strength scratch-resistant self-repairing transparent film and a preparation method thereof comprise the following steps:
4.89g of isophorone diisocyanateMixing and stirring acid ester and 10g of polytetramethylene ether glycol (with the molecular weight of 1000 g/mol) uniformly, adding 0.05g of dibutyltin dilaurate into the mixture, heating and stirring the mixture in an oil bath at the temperature of 80 ℃ for reacting for 4 hours to obtain a prepolymer; adding 0.71g of oxalyl dihydrazide into the prepolymer, reacting for 8 hours at 50 ℃, and diluting with 30ml of N, N-dimethylacetamide during the reaction, so that the oxalyl dihydrazide is dissolved and reacted at the same time; then adding 1.59g of trimethylolpropane tri (3-mercaptopropionate) into the system, uniformly stirring, pouring the reaction product into a polytetrafluoroethylene mould, removing the used organic solvent under the condition of a vacuum oven at 40-60 ℃, and then treating for 12 hours under the condition of a blast oven at 80 ℃ to obtain the polyurethane film. The tensile strength of the film is 44.1MPa, the elongation at break is 560 percent, and the toughness is 52.9MJ/m 3 . After the spline is cut off to be more than 80%, repairing is carried out for 24 hours at 80 ℃, the tensile strength after repairing is 37.5MPa, and the repairing efficiency is 85%.
The film prepared in this example had a light transmittance of 91% or more as in example 3.
Example 8
A recoverable high-strength scratch-resistant self-repairing transparent film and a preparation method thereof comprise the following steps:
mixing 5.22g isophorone diisocyanate and 10g polytetramethylene ether glycol (molecular weight 1000 g/mol), stirring uniformly, adding 0.05g dibutyltin dilaurate, heating in an oil bath at 80 ℃ and stirring for 4 hours to obtain a prepolymer; adding 0.71g of oxalyl dihydrazide into the prepolymer, reacting for 8 hours at 50 ℃, and diluting with 30ml of N, N-dimethylacetamide during the reaction, so that the oxalyl dihydrazide is dissolved and reacted at the same time; then adding 1.99g of trimethylolpropane tri (3-mercaptopropionate) into the system, uniformly stirring, pouring the reaction product into a polytetrafluoroethylene mould, removing the used organic solvent under the condition of a vacuum oven at 40-60 ℃, and then treating for 12 hours under the condition of a blast oven at 80 ℃ to obtain the polyurethane film. The tensile strength of the film is 49.3MPa, the elongation at break is 525 percent, and the toughness is 54.3MJ/m 3 . After the spline is cut off to be more than 80%, repairing is carried out for 24 hours at 80 ℃, the tensile strength after repairing is 34.7MPa, and the repairing efficiency is 70.4%.
The film prepared in this example had a light transmittance of 91% or more as in example 3.
Comparative example 1
Mixing 5.11g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (molecular weight is 1000 g/mol), stirring uniformly, adding 0.05g of dibutyltin dilaurate, heating in an oil bath at 80 ℃, stirring and reacting for 4 hours to obtain a prepolymer; 0.81g of 1, 6-hexamethylenediamine was added dropwise to the prepolymer and reacted at room temperature for 8 hours, during which 20ml of N, N-dimethylacetamide was added; then adding 1.59g of trimethylolpropane tri (3-mercaptopropionate) into the system, uniformly stirring, pouring the reaction product into a polytetrafluoroethylene mould, removing the used organic solvent under the condition of a vacuum oven at 40-60 ℃, and then treating for 12 hours under the condition of a blast oven at 80 ℃ to obtain the polyurethane film. The tensile strength of the film is 24.5MPa, the elongation at break is 669.5 percent, and the toughness is 45.8MJ/m 3 . After the spline is cut off to be more than 80%, repairing is carried out for 24 hours at 80 ℃, the tensile strength after repairing is 22.5MPa, and the repairing efficiency is 91.8%. As shown in fig. 3, the optical microscope pictures before and after scratching the film of comparative example 1 showed that a dense scratch was left on the film surface after scratching with a copper brush for 500 cycles, and the scratch resistance was poor. The transmittance of the film prepared in this comparative example was 89.1%.
Comparative example 2
Mixing 5.11g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (molecular weight is 1000 g/mol), stirring uniformly, adding 0.05g of dibutyltin dilaurate, heating in an oil bath at 80 ℃, stirring and reacting for 4 hours to obtain a prepolymer; 0.83g of oxalyl dihydrazide was added to the prepolymer and reacted at 50℃for 8 hours, during which 30ml of N, N-dimethylacetamide was added; then adding 1.43g of 1, 4-butanediol bis (thioglycollate) into the system, uniformly stirring, pouring the reaction product into a polytetrafluoroethylene mould, removing the used organic solvent under the condition of a vacuum oven at 40-60 ℃, and then treating for 12 hours under the condition of a blast oven at 80 ℃ to obtain the polyurethane film. The tensile strength of the film is 49.4MPa, the elongation at break is 560.4 percent, and the toughness is 60.5MJ/m 3 . After the spline is cut off to be more than 80%, repairing is carried out for 24 hours at 80 ℃, the tensile strength after repairing is 43MPa, and the repairing efficiency is 87%.
Comparative example 3
5.11g of isophorone diisocyanateMixing and stirring acid ester and 10g of polytetramethylene ether glycol (with the molecular weight of 1000 g/mol) uniformly, adding 0.05g of dibutyltin dilaurate into the mixture, heating and stirring the mixture in an oil bath at the temperature of 80 ℃ for reacting for 4 hours to obtain a prepolymer; 0.83g of oxalyl dihydrazide was added to the prepolymer and reacted at 50℃for 8 hours, during which 30ml of N, N-dimethylacetamide was added; then adding 0.54g of trimethylolpropane into the system, uniformly stirring, pouring the reaction product into a polytetrafluoroethylene mould, removing the used organic solvent under the condition of a vacuum oven at 40-60 ℃, and then treating for 12 hours under the condition of a blast oven at 80 ℃ to obtain the polyurethane film. The tensile strength of the film is 64.5MPa, the elongation at break is 449.8 percent, and the toughness is 94.7MJ/m 3 . After the spline is cut off to be more than 80%, repairing is carried out for 24 hours at 80 ℃, the tensile strength after repairing is 24.3MPa, and the repairing efficiency is 37.7%. The transmittance of the film prepared in this comparative example was 86.8%.
The above examples are examples of the present invention for preparing the high strength scratch-resistant recyclable self-healing transparent film based on multiple hydrogen bonds and dynamic thiourethane bonds, but the present invention is not limited to the above examples, and the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be equivalent are included in the scope of the present invention.
Claims (7)
1. A preparation method of a recyclable high-strength scratch-resistant self-repairing transparent polyurethane film is characterized by comprising the following steps of: the method comprises the following steps:
1) Carrying out prepolymerization reaction on polyether glycol and asymmetric alicyclic diisocyanate under the action of a catalyst to obtain an isocyanate group-terminated prepolymer;
2) Carrying out chain extension reaction on the prepolymer and a diamine-based chain extender;
3) Mixing the multi-mercapto cross-linking agent with the system with the chain extension reaction completed, and curing and forming to obtain the high-strength scratch-resistant transparent self-repairing polyurethane film;
the diamine-based chain extender is one or two of oxalyl dihydrazide and oxalyl diamine;
the multi-mercapto cross-linking agent is trimethylolpropane tri (3-mercaptopropionate);
the molar ratio of the diisocyanate to the polyether glycol is (2-2.5): 1, a step of; the molar ratio of the diamine chain extender to the polyether glycol is (0.6-0.8): 1, a step of; the molar ratio of the multi-mercapto cross-linking agent to the polyether glycol is (0.2-0.6): 1, a step of;
the polyether glycol is one or two of polytetramethylene ether glycol and polyoxypropylene ether glycol, and the number average molecular weight is 650-3000g/mol;
the asymmetric alicyclic diisocyanate is isophorone diisocyanate;
the temperature of the prepolymerization reaction is 75-85 ℃ and the time is 3-5 hours;
the temperature of the chain extension reaction is 40-50 ℃ and the time is 6-10 hours.
2. The method for preparing the recyclable high-strength scratch-resistant self-repairing transparent polyurethane film according to claim 1, which is characterized in that: the curing refers to molding in a mold, removing the solvent and thermally curing.
3. The method for preparing the recyclable high-strength scratch-resistant self-repairing transparent polyurethane film according to claim 2, which is characterized in that: the heat curing is carried out for 6-12 hours at the temperature of 60-80 ℃;
the solvent removal step is to remove the used organic solvent in a vacuum oven at 40-60 ℃.
4. The method for preparing the recyclable high-strength scratch-resistant self-repairing transparent polyurethane film according to claim 1, which is characterized in that: the catalyst is one or more of triethylamine, stannous octoate or dibutyltin dilaurate;
the addition amount of the catalyst is 0.5% -1% of the weight of the polyether glycol;
the polyether glycol is subjected to vacuum dehydration treatment before reaction.
5. The method for preparing the recyclable high-strength scratch-resistant self-repairing transparent polyurethane film according to claim 1, which is characterized in that: in the chain extension reaction process, a solvent is required to be added to adjust the viscosity of a reaction system so as to prevent gel; the solvent is one or more of N, N-dimethylacetamide, toluene and acetone.
6. A recyclable high strength scratch resistant self-healing transparent polyurethane film obtained by the method of any one of claims 1 to 5.
7. The method for repairing the recyclable high-strength scratch-resistant self-repairing transparent polyurethane film according to claim 6, which is characterized in that: and (3) treating the film with scratches or cracks at the temperature of 60-110 ℃ to ensure that the film is repaired successfully.
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