CN115260446A - 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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- CN115260446A CN115260446A CN202210909166.XA CN202210909166A CN115260446A CN 115260446 A CN115260446 A CN 115260446A CN 202210909166 A CN202210909166 A CN 202210909166A CN 115260446 A CN115260446 A CN 115260446A
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- 229920006264 polyurethane film Polymers 0.000 title claims abstract description 46
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 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 17
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 150000002009 diols Chemical class 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 125000004427 diamine group Chemical group 0.000 claims abstract description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 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 16
- 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
- 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 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 238000001723 curing Methods 0.000 claims description 4
- JJSYPAGPNHFLML-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylpropanoic acid Chemical compound OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.CCC(CO)(CO)CO JJSYPAGPNHFLML-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000013007 heat curing Methods 0.000 claims description 2
- 238000009740 moulding (composite fabrication) 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
- 238000001879 gelation Methods 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- 238000007790 scraping Methods 0.000 abstract description 2
- 238000004383 yellowing Methods 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 2
- 238000003756 stirring Methods 0.000 description 30
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- 238000002834 transmittance Methods 0.000 description 17
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- 238000010438 heat treatment Methods 0.000 description 11
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
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- 229920001971 elastomer Polymers 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- DLLMHEDYJQACRM-UHFFFAOYSA-N 2-(carboxymethyldisulfanyl)acetic acid Chemical compound OC(=O)CSSCC(O)=O DLLMHEDYJQACRM-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 238000000879 optical micrograph Methods 0.000 description 1
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- 229920003229 poly(methyl methacrylate) Polymers 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
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing 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
- 229960003495 thiamine Drugs 0.000 description 1
- 235000019157 thiamine Nutrition 0.000 description 1
- 239000011721 thiamine Substances 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
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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
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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
- 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
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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
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- 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
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- 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 diol and asymmetric aliphatic ring diisocyanate under the action of a catalyst to obtain an isocyanate-terminated prepolymer; 2) Will be provided withCarrying out chain extension reaction on the prepolymer and a diamine chain extender; 3) And mixing the multi-mercapto crosslinking agent with the system after the chain extension reaction, 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) The self-healing light-transmitting material has excellent self-healing capability and recyclability, and is resistant to scraping, good in light transmission (the standard light transmission rate is 98.6 percent in a visible light range), high in refractive index (larger than 1.49), low in haze and resistant to yellowing.
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 same as optical plastics (PMMA, PC and PS), has unique high elasticity of an elastomer, namely, can generate large deformation under the action of external force, and can completely or mostly recover after the external force is removed. The self-repairing high polymer material can repair the damage of the self-repairing high polymer material spontaneously or completely, so that the hidden danger caused by the damage of the material is eliminated to a great extent. The self-repairing capability of the transparent flexible polymer is endowed, so that the service life and the use safety of the material can be improved, a more economical, convenient and effective recycling method is provided, and the material is a novel intelligent bionic material.
The cross-linked polyurethane has the properties of high mechanical strength, wear resistance, excellent aging resistance, chemical corrosion resistance and the like, and is widely applied to various industries such as buildings, houses, mechanical parts, sports equipment, national defense and military affairs and the like. However, the crosslinked structure also makes it difficult to reprocess and recycle, and the waste thermosetting polymer causes serious resource waste and environmental pollution. The polyurethane with the dynamic cross-linked structure can simultaneously endow the material with excellent mechanical property and recoverable reprocessing property, and can make certain contribution to the national energy-saving priority and environment-friendly sustainable development strategy.
Chinese patent CN 111518376B discloses a self-repairing polyurethane based on multiple hydrogen bonds, however, the elastomerThe tensile strength is not high and is only 14MPa. Chinese patent CN 111440315B discloses a transparent thermoplastic polyurea elastomer, which is endowed with self-repairing performance by introducing regular hydrogen bonds and irregular hydrogen bonds, the tensile strength of the elastomer is only 8MPa, and the toughness of the elastomer is less than 30MJ/m3. Chinese invention patent CN 108503782B discloses a full-transparent high-strength self-repairing polyurethane elastomer with tensile strength of 22MPa. The Chinese patent application CN 114085355A discloses a high-strength hydrolysis-resistant thermoplastic polyurethane elastomer, which has the strength as high as 52.1MPa but does not have the self-repairing performance. Chinese invention patent CN 107163214B discloses a reinforced cross-linked polyurethane elastomer, the highest strength of which can reach 22MPa, however, permanent covalent cross-linking makes it difficult to recycle, resulting in waste of resources. Therefore, it is still a great challenge to achieve the properties of high strength, stretchability, transparency, self-healing and recyclability of the polymer material at the same time.
Disclosure of Invention
In order to overcome the defects 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 disclosed by the invention has self-repairability and recyclability.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a recyclable high-strength scratch-resistant self-repairing transparent polyurethane film comprises the following steps:
1) Carrying out prepolymerization reaction on polyether diol and asymmetric aliphatic ring diisocyanate under the action of a catalyst to obtain an isocyanate-terminated prepolymer;
2) Carrying out chain extension reaction on the prepolymer and a diamine chain extender;
3) Mixing a multi-mercapto crosslinking agent with the system after the chain extension reaction, and curing and forming to obtain a high-strength scratch-resistant transparent self-repairing polyurethane film;
the diamine chain extender is one or two of Oxalyl dihydrazide (oxalysl dihydrazide) or Oxalyl diamine;
the multi-mercapto crosslinking agent is one or two of trimethylolpropane tri (3-mercaptopropionate) and pentaerythritol tetra (3-mercaptopropionate).
The polyether diol in the step 1) is one or two of polytetramethylene ether glycol (PTMO) and polyoxypropylene ether glycol (PPG);
the number average molecular weight of the polyether diol in the step 1) is 650-3000g/mol.
The asymmetric alicyclic diisocyanate in the 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 in the process of chain extension reaction (for example, 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 solvent is mixed with the prepolymer, and the like);
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 of the total weight of the composition.
The adding amount of the catalyst in the step 1) is 0.5 to 1 percent of the weight of the polyether glycol;
the molar ratio of diisocyanate to polyether diol is (1.9-2.6): 1, preferably (2 to 2.5): 1.
in the step 2), the molar ratio of the diamine-based chain extender to the polyether glycol is (0.6-0.8): 1.
the molar ratio of the multi-mercapto crosslinking 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 reaction.
The step 3) of curing refers to molding in a mold, removing the solvent and performing thermocuring.
The heat curing refers to the treatment for 6 to 12 hours at the temperature of between 60 and 80 ℃;
the solvent removal refers to the removal of the used organic solvent in a vacuum oven at 40-60 ℃.
Adding the mercapto-based crosslinking agent into the system after chain expansion in the step 3), uniformly stirring, and pouring into a polytetrafluoroethylene mold 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-repairing polyurethane film based on multiple hydrogen bonds and dynamic thiamine bonds comprises the following steps: the film with the scratch or the fracture is processed at the temperature of 60-110 ℃. The film with the scratches is processed for 2 to 6 hours at the temperature of between 60 and 80 ℃, and the scratches are repaired successfully by self; cutting the film, and treating at 60-110 deg.c for 12-36 hr.
The method for recovering the self-repairing polyurethane film based on multiple hydrogen bonds and dynamic sulfur-urethane bonds comprises the following steps: and (3) kneading the cut sample strips by using an open mill to remove air bubbles in gaps of the sample, putting the sample strips into a hot press die, carrying out hot pressing at 140 ℃ for 0.5 hour, demoulding to obtain a reprocessed sample, and testing the tensile strength.
The film is synthesized by polyether diol, asymmetric aliphatic ring diisocyanate, diamine chain extender and multi-mercapto crosslinking agent. Multiple hydrogen bonds can be formed between hard phases formed by the reaction of the amino chain extender with the unique structure and the isocyanic acid radical, 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 isocyanic acid radical to generate a dynamic exchangeable thiocarbamate bond (called a thiocarbamate bond for short) to form a covalent adaptive network. The dynamic cross-linked structure not only contributes to the self-repairability of the material, but also endows the material with the recyclable reprocessing capability. The material has high mechanical strength (61.6 MPa) and good toughness (105.6 MJ/m)3) The coating has excellent self-healing capability and recyclability, is resistant to scraping, has good light transmittance (the standard light transmittance is 98.6 percent in a visible light range), high refractive index (more than 1.49), low haze and yellowing resistance, and can be applied to the field of intelligent coatings for protecting optical devices, automobile surfaces and the likeThe domain has wide application prospect.
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 the self-repairability of the polymer at the same time, and the crosslinking effect of the dynamic sulfur-ammonia ester bonds in the film not only provides the stability of the molecular network structure 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 higher temperature (such as 140 ℃).
The self-repairing polyurethane film disclosed by the invention has high toughness and scratch resistance, and a copper brush is difficult to leave scratches on the surface of the film.
The self-repairing polyurethane film disclosed by the invention is of a condensed amorphous structure, excellent in transparency and low in haze, the average light transmittance within a visible light range (400-800 nm) is 91.3% (1.3 mm thick), the standard light transmittance is 98.6% (0.2 mm thick), and the average haze value is 2.9%. The light transmittance is not less than 90 percent after treatment for 800 hours at 80 ℃.
The self-repairing polyurethane film disclosed by the invention is high in refractive index, the refractive index is greater than 1.49 in a visible light range, and the standard of an optical lens is met.
Drawings
FIG. 1 is a schematic synthesis route for a self-healing polyurethane film of example 1 of the present invention;
FIG. 2 is an optical microscope image of a scratch self-repair test of the self-repair polyurethane film prepared in example 1; the left image is a diagram before the self-repairing of the film with the scratches, and the right image is a diagram after the self-repairing of the film with the scratches;
FIG. 3 is a graph comparing the 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 of light transmittance and haze for the self-healing polyurethane film prepared in example 3; (b) A refractive index map for the self-healing polyurethane films prepared in examples 1-4;
fig. 5 is a graph of 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 the embodiments of the present invention are not limited thereto.
The repairing method of the self-repairing polyurethane film comprises the following steps: processing the film with the scratches for 3 hours at the temperature of 80 ℃, and automatically repairing the scratches successfully; the film is cut into dumbbell-shaped or rectangular sample strips, the sample strips are cut by more than 80 percent by a scalpel, and the sample strips are placed at 80 ℃ for 24 hours to test the tensile strength.
The recovery method of the self-repairing polyurethane film comprises the following steps: and (3) kneading the cut sample strips by using an open mill to remove air bubbles in gaps of the sample, putting the sample strips into a hot press die, carrying out hot pressing at 140 ℃ for 0.5 hour, demoulding to obtain a reprocessed sample, and testing the tensile strength.
Example 1
A preparation method of a recyclable high-strength scratch-resistant self-repairing transparent film comprises the following steps:
mixing 4.45g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (molecular weight is 1000 g/mol) 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 (followed by addition of 30ml of N, N-dimethylacetamide for dilution), and reacted at 50 ℃ for 8 hours to dissolve oxalyl dihydrazide while reacting; then adding 0.80g of trimethylolpropane tris (3-mercaptopropionate) into the system, uniformly stirring, pouring the reaction product into a polytetrafluoroethylene mold to form a film, removing the used organic solvent in a vacuum oven at 40-60 ℃, and then treating for 12 hours in a forced air oven at 80 ℃ to obtain the polyurethane film. The film has the tensile strength of 49.5MPa, the elongation at break of 614.9 percent and the toughness of 93.4MJ/m3. After the sample strips are cut off by more than 80 percent, the sample strips are repaired for 24 hours at the temperature of 80 ℃, the tensile strength after the repair is 44MPa, and the repair efficiency is 88.9 percent.
The light transmittance of the film prepared in this example was 91% or more, as in example 3.
FIG. 1 is a schematic representation of the synthesis of a high strength scratch resistant self healing transparent film that can be recycled as in example 1. FIG. 2 is an optical microscope photograph of scratch self-repair of the film prepared in example 1. As can be seen from fig. 2, after the sample is scratched by the scalpel, an obvious incision is generated, the sample is repaired for 3 hours in an environment of 80 ℃, and the scratch can finish self-repairing.
The synthetic route of the following examples is the same as that of FIG. 1, and the repair picture of the optical microscope is similar to that of FIG. 2, but not provided.
Example 2
Mixing 4.80g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (molecular weight is 1000 g/mol) uniformly, adding 0.05g of dibutyltin dilaurate, heating in an oil bath at 80 ℃, stirring and reacting for 4 hours to obtain a prepolymer; adding 0.83g of oxalyl dihydrazide into the prepolymer, reacting for 8h at 50 ℃, adding 30ml of N, N-dimethylacetamide for dilution during the reaction, and dissolving the oxalyl dihydrazide while reacting; and then adding 1.20g of trimethylolpropane tris (3-mercaptopropionate) into the system, uniformly stirring, pouring a reaction product into a polytetrafluoroethylene mold, removing the used organic solvent in a vacuum oven at the temperature of 40-60 ℃, and treating for 12 hours in a forced air oven at the temperature of 80 ℃ to obtain the polyurethane film. The film has the tensile strength of 56.6MPa, the elongation at break of 575.4 percent and the toughness of 103.4MJ/m3. After the sample strips are cut off by more than 80 percent, the sample strips are repaired for 24 hours at the temperature of 80 ℃, the tensile strength after the repair is 49.4MPa, and the repair efficiency is 87.3 percent.
The film prepared in this example had a light transmittance of 91% or more, as in example 3.
Example 3
A recyclable high-strength scratch-resistant self-repairing transparent film and a preparation method thereof comprise the following steps:
mixing and stirring 5.11g of isophorone diisocyanate and 10g of polytetramethylene ether glycol with the molecular weight of 1000g/mol uniformly, adding 0.05g of dibutyltin dilaurate, heating and stirring in an oil bath at the temperature of 80 ℃, and reacting for 4 hours to obtain a prepolymer; adding 0.83g of oxalyl dihydrazide into the prepolymer, reacting for 8h at 50 ℃, adding 30ml of N, N-dimethylacetamide for dilution during the reaction, and dissolving oxalyl dihydrazide while reacting; then adding 1.59g of trimethylolpropane tri (3-mercaptopropionate) into the system, uniformly stirring, pouring a reaction product into a polytetrafluoroethylene mold, removing the used organic solvent in a vacuum oven at 40-60 ℃, then treating for 12 hours in a forced air oven at 80 ℃,a polyurethane film was obtained. The film has the tensile strength of 61.6MPa, the elongation at break of 539 percent and the toughness of 105.6MJ/m3. After the sample strips are cut off by more than 80 percent, the sample strips are repaired for 24 hours at the temperature of 80 ℃, the tensile strength after the repair is 50.4MPa, and the repair efficiency is 81.9 percent. The film obtained in example 3 was scratched with a copper brush for 500 cycles, and only a sparse scratch was observed under an optical microscope, and the scratch resistance was good.
FIG. 3 is a graph comparing the scratch resistance of the film prepared in example 3 with that of comparative example 1;
FIG. 4 (a) is a graph of light transmittance, haze versus wavelength for the film prepared in example 3; (b) Plots of refractive index as a function of wavelength for the films prepared in examples 1-4;
after the sample of example 3 was sheared, air bubbles in the voids of the sample were removed by open kneading, the sample was placed in a mold of a hot press, hot-pressed at 140 ℃ for 0.5 hour, demolded to obtain a reprocessed sample, the tensile strength was measured, and the processing was repeated three times, and the measured tensile curve was as shown in fig. 5. Fig. 5 is a graph of the recyclability of the self-healing polyurethane film prepared in example 3.
Example 4
A recyclable high-strength scratch-resistant self-repairing transparent film and a preparation method thereof comprise the following steps:
mixing and stirring 5.78g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (the molecular weight is 1000 g/mol) uniformly, adding 0.05g of dibutyltin dilaurate, heating and stirring in an oil bath at the temperature of 80 ℃, and reacting for 4 hours to obtain a prepolymer; adding 0.83g of oxalyl dihydrazide into the prepolymer, reacting for 8h at 50 ℃, adding 30ml of N, N-dimethylacetamide for dilution during the reaction, and reacting while dissolving oxalyl dihydrazide; then adding 2.39g of trimethylolpropane tris (3-mercaptopropionate) into the system, uniformly stirring, pouring the reaction product into a polytetrafluoroethylene mold, removing the used organic solvent in a vacuum oven at 40-60 ℃, and treating for 12 hours in a forced air oven at 80 ℃ to obtain the polyurethane film. The film has a tensile strength of 64.4MPa, an elongation at break of 489 percent and a toughness of 94.7MJ/m3. Cutting off the sample strips by more than 80%, repairing at 80 ℃ for 24h, wherein the tensile strength after repairing is 39.9MPa, and the repairing efficiency is highThe content was 61.2%. The film prepared in this example had a light transmittance of 91% or more, as in example 3.
Example 5
A recyclable 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 (the molecular weight is 1000 g/mol) uniformly, adding 0.05g of dibutyltin dilaurate, heating and stirring in an oil bath at the temperature of 80 ℃, and reacting for 4 hours to obtain a prepolymer; adding 0.71g of oxalyl dihydrazide into the prepolymer, reacting for 8h at 50 ℃, adding 30ml of N, N-dimethylacetamide for dilution during the reaction, and reacting while dissolving oxalyl dihydrazide; and then adding 0.80g of trimethylolpropane tris (3-mercaptopropionate) into the system, uniformly stirring, pouring a reaction product into a polytetrafluoroethylene mold, removing the used organic solvent in a vacuum oven at the temperature of 40-60 ℃, and treating for 12 hours in a forced air oven at the temperature of 80 ℃ to obtain the polyurethane film. The film has the tensile strength of 30.7MPa, the elongation at break of 613 percent and the toughness of 46.6MJ/m3. After the sample strips are cut off by more than 80 percent, the sample strips are repaired for 24 hours at the temperature of 80 ℃, the tensile strength after repair is 27.9MPa, and the repair efficiency is 90.9 percent. The film prepared in this example had a light transmittance of 91% or more, as in example 3.
Example 6
A recyclable high-strength scratch-resistant self-repairing transparent film and a preparation method thereof comprise the following steps:
mixing 4.56g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (molecular weight is 1000 g/mol) uniformly, adding 0.05g of dibutyltin dilaurate, heating in an oil bath at 80 ℃, stirring and reacting for 4 hours to obtain a prepolymer; adding 0.71g of oxalyl dihydrazide into the prepolymer, reacting for 8h at 50 ℃, adding 30ml of N, N-dimethylacetamide for dilution during the reaction, and reacting while dissolving oxalyl dihydrazide; and then adding 1.20g of trimethylolpropane tris (3-mercaptopropionate) into the system, uniformly stirring, pouring a reaction product into a polytetrafluoroethylene mold, removing the used organic solvent in a vacuum oven at the temperature of 40-60 ℃, and treating for 12 hours in a forced air oven at the temperature of 80 ℃ to obtain the polyurethane film. The film has high tensile strengthThe degree is 34.8MPa, the elongation at break is 605 percent, and the toughness is 48.9MJ/m3. After the sample strips are cut off by more than 80 percent, the sample strips are repaired for 24 hours at the temperature of 80 ℃, the tensile strength after the repair is 31.7MPa, and the repair efficiency is 91.1 percent.
The film prepared in this example had a light transmittance of 91% or more, as in example 3.
Example 7
A recyclable high-strength scratch-resistant self-repairing transparent film and a preparation method thereof comprise the following steps:
mixing and stirring 4.89g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (the molecular weight is 1000 g/mol) uniformly, adding 0.05g of dibutyltin dilaurate, heating and stirring in an oil bath at the temperature of 80 ℃, and reacting for 4 hours to obtain a prepolymer; adding 0.71g of oxalyl dihydrazide into the prepolymer, reacting for 8h at 50 ℃, adding 30ml of N, N-dimethylacetamide for dilution during the reaction, and reacting while dissolving oxalyl dihydrazide; and then adding 1.59g of trimethylolpropane tris (3-mercaptopropionate) into the system, uniformly stirring, pouring a reaction product into a polytetrafluoroethylene mold, removing the used organic solvent in a vacuum oven at 40-60 ℃, and treating for 12 hours in a forced air oven at 80 ℃ to obtain the polyurethane film. The film has tensile strength of 44.1MPa, elongation at break of 560% and toughness of 52.9MJ/m3. After the sample strip is cut off by more than 80 percent, the sample strip is repaired for 24 hours at the temperature of 80 ℃, the tensile strength after the repair is 37.5MPa, and the repair efficiency is 85 percent.
The film prepared in this example had a light transmittance of 91% or more, as in example 3.
Example 8
A recyclable high-strength scratch-resistant self-repairing transparent film and a preparation method thereof comprise the following steps:
mixing and stirring 5.22g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (molecular weight is 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 0.71g of oxalyl dihydrazide into the prepolymer, reacting for 8h at 50 ℃, adding 30ml of N, N-dimethylacetamide for dilution during the reaction, and reacting while dissolving oxalyl dihydrazide; then 1.99g trimethylolpropane tris (3-mercaptopropionate) was added) Adding the system, uniformly stirring, pouring the reaction product into a polytetrafluoroethylene mold, removing the used organic solvent in a vacuum oven at 40-60 ℃, and then treating for 12 hours in a forced air oven at 80 ℃ to obtain the polyurethane film. The film has a tensile strength of 49.3MPa, an elongation at break of 525% and a toughness of 54.3MJ/m3. After the sample strips are cut off by more than 80 percent, the sample strips are repaired for 24 hours at the temperature of 80 ℃, the tensile strength after the repair is 34.7MPa, and the repair efficiency is 70.4 percent.
The film prepared in this example had a light transmittance of 91% or more, as in example 3.
Comparative example 1
Mixing and stirring 5.11g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (molecular weight is 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; 0.81g of 1, 6-hexanediamine is added into the prepolymer drop by drop and reacted for 8 hours at room temperature, and 20ml of N, N-dimethylacetamide is added during the reaction; and then adding 1.59g of trimethylolpropane tris (3-mercaptopropionate) into the system, uniformly stirring, pouring a reaction product into a polytetrafluoroethylene mold, removing the used organic solvent in a vacuum oven at 40-60 ℃, and treating for 12 hours in a forced air oven at 80 ℃ to obtain the polyurethane film. The film has a tensile strength of 24.5MPa, an elongation at break of 669.5% and a toughness of 45.8MJ/m3. After the sample strips are cut off by more than 80 percent, the sample strips are repaired for 24 hours at the temperature of 80 ℃, the tensile strength after the repair is 22.5MPa, and the repair efficiency is 91.8 percent. The optical microscope pictures before and after the scratching of the film of comparative example 1 are shown in fig. 3, and a dense scratch is left on the surface of the film after 500 cycles of scratching with a copper brush, and the scratch resistance is poor. The film prepared in this comparative example had a light transmittance of 89.1%.
Comparative example 2
Mixing and stirring 5.11g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (molecular weight is 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 dihydrazide into the prepolymer, reacting for 8h at 50 ℃, adding 30ml of N, N-dimethylacetamide during the reaction; then 1.43g of 1, 4-butanediol bis (mercaptoacetic acid)Ester) is added into the system, after the mixture is uniformly stirred, the reaction product is poured into a polytetrafluoroethylene mold, the used organic solvent is removed in a vacuum oven at the temperature of 40-60 ℃, and then the mixture is treated in a forced air oven at the temperature of 80 ℃ for 12 hours to obtain the polyurethane film. The film has a tensile strength of 49.4MPa, an elongation at break of 560.4% and a toughness of 60.5MJ/m3. After the sample strips are cut off by more than 80 percent, the sample strips are repaired for 24 hours at the temperature of 80 ℃, the tensile strength after the repair is 43MPa, and the repair efficiency is 87 percent.
Comparative example 3
Mixing and stirring 5.11g of isophorone diisocyanate and 10g of polytetramethylene ether glycol (molecular weight is 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 dihydrazide into the prepolymer, reacting for 8h at 50 ℃, and adding 30ml of N, N-dimethylacetamide during the reaction; and then adding 0.54g of trimethylolpropane into the system, uniformly stirring, pouring a reaction product into a polytetrafluoroethylene mold, removing the used organic solvent in a vacuum oven at 40-60 ℃, and then treating for 12 hours in a forced air oven at 80 ℃ to obtain the polyurethane film. The film has a tensile strength of 64.5MPa, an elongation at break of 449.8 percent and a toughness of 94.7MJ/m3. After the sample strip is cut off by more than 80 percent, the sample strip is repaired for 24 hours at the temperature of 80 ℃, the tensile strength after the repair is 24.3MPa, and the repair efficiency is 37.7 percent. The film prepared in this comparative example had a light transmittance of 86.8%.
The above examples are examples of the present invention for preparing a 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 which do not depart from the spirit and principle of the present invention are all equivalent substitutions and are included in the scope of the present invention.
Claims (10)
1. A preparation method of a recyclable high-strength scratch-resistant self-repairing transparent polyurethane film is characterized by comprising the following steps: the method comprises the following steps:
1) Carrying out prepolymerization reaction on polyether diol and asymmetric aliphatic ring diisocyanate under the action of a catalyst to obtain an isocyanate-terminated prepolymer;
2) Carrying out chain extension reaction on the prepolymer and a diamine chain extender;
3) Mixing a multi-mercapto crosslinking agent with the system after the chain extension reaction, and curing and forming to obtain a high-strength scratch-resistant transparent self-repairing polyurethane film;
the diamine chain extender is one or two of oxalyl dihydrazide or oxalyl diamine;
the multi-mercapto crosslinking agent is one or two of trimethylolpropane tri (3-mercaptopropionate) and pentaerythritol tetra (3-mercaptopropionate).
2. The method for preparing the recyclable high-strength scratch-resistant self-repairing transparent polyurethane film as claimed in claim 1, which is characterized in that: the molar ratio of the diisocyanate to the polyether glycol is (1.9-2.6): 1; the molar ratio of the diamine chain extender to the polyether glycol is (0.6-0.8): 1; the molar ratio of the multi-mercapto crosslinking agent to the polyether glycol is (0.2-0.6): 1.
3. the method for preparing the recyclable high-strength scratch-resistant self-repairing transparent polyurethane film as claimed in claim 1, which is characterized in that: the polyether diol is one or two of polytetramethylene ether glycol and polypropylene oxide ether glycol, and the number average molecular weight is 650-3000g/mol;
the asymmetric alicyclic diisocyanate is isophorone diisocyanate.
4. The method for preparing the recyclable high-strength scratch-resistant self-repairing transparent polyurethane film as claimed in claim 1, characterized in that: 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.
5. The method for preparing the recyclable high-strength scratch-resistant self-repairing transparent polyurethane film as claimed in claim 1, characterized in that: the solidification is to form in a mould, remove the solvent and thermally solidify.
6. The method for preparing the recyclable high-strength scratch-resistant self-repairing transparent polyurethane film as claimed in claim 5, which is characterized in that: the heat curing refers to the treatment for 6 to 12 hours at the temperature of between 60 and 80 ℃;
the solvent removal refers to the removal of the used organic solvent in a vacuum oven at 40-60 ℃.
7. The method for preparing the recyclable high-strength scratch-resistant self-repairing transparent polyurethane film as claimed in claim 1, 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 to 1 percent of the weight of the polyether glycol;
the polyether glycol needs to be subjected to vacuum dehydration treatment before reaction.
8. The method for preparing the recyclable high-strength scratch-resistant self-repairing transparent polyurethane film as claimed in claim 1, characterized in that: in the chain extension reaction process, a solvent is required to be added to adjust the viscosity of the reaction system and prevent gelation; the solvent is one or more of N, N-dimethylacetamide, toluene and acetone.
9. A recyclable high-strength scratch-resistant self-repairing transparent polyurethane film obtained by the preparation method of any one of claims 1 to 8.
10. The method for repairing a recyclable high-strength scratch-resistant self-repairing transparent polyurethane film as claimed in claim 9, wherein the method comprises the following steps: the film with scratches or fractures is processed at the temperature of 60-110 ℃, and the film is repaired by itself.
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| YEN-HAO HSU: "Shape Memory Behavior of Biocompatible Polyurethane Stereoelastomers Synthesized via Thiol–Yne Michael Addition", 《BIOMACROMOLECULES》, vol. 23, no. 3, pages 1205 - 1213 * |
| 张士玉: "交联型聚氨酯的合成及其室温自修复性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 01, pages 016 - 127 * |
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