CN114561145A - Self-repairing waterborne polyurethane coating containing imine bond - Google Patents
Self-repairing waterborne polyurethane coating containing imine bond Download PDFInfo
- Publication number
- CN114561145A CN114561145A CN202210201176.8A CN202210201176A CN114561145A CN 114561145 A CN114561145 A CN 114561145A CN 202210201176 A CN202210201176 A CN 202210201176A CN 114561145 A CN114561145 A CN 114561145A
- Authority
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- China
- Prior art keywords
- self
- repairing
- polyurethane coating
- mixture
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 54
- 239000004970 Chain extender Substances 0.000 claims abstract description 23
- 239000004814 polyurethane Substances 0.000 claims abstract description 23
- 229920002635 polyurethane Polymers 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 48
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 150000002009 diols Chemical class 0.000 claims description 11
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 10
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 229940126062 Compound A Drugs 0.000 claims description 8
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 229920001610 polycaprolactone Polymers 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000003828 vacuum filtration Methods 0.000 claims description 7
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 5
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 5
- 235000012141 vanillin Nutrition 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 3
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000616 Poly(1,4-butylene adipate) Polymers 0.000 claims 1
- 150000003384 small molecules Chemical group 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 50
- 239000011248 coating agent Substances 0.000 abstract description 49
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003973 paint Substances 0.000 abstract description 4
- 239000006115 industrial coating Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 238000012423 maintenance Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 239000002262 Schiff base Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- -1 poly 1,4 butylene adipate Polymers 0.000 description 9
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 7
- 230000008439 repair process Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229920006273 intrinsic self-healing polymer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000002228 disulfide group Chemical group 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 239000013003 healing agent Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
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- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
-
- 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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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
Abstract
The invention discloses a self-repairing waterborne polyurethane coating containing imine bonds, which relates to the technical field of coatings, and is characterized in that a series of self-repairing waterborne polyurethane coatings containing imine bonds are prepared by synthesizing different polyurethane chain extenders containing imine bonds, and reacting the different polyurethane chain extenders with different polyurethane soft chain segments, isocyanate and hydrophilic chain extenders; the paint has good self-repairing effect at room temperature, and the repairing rate reaches 99.2% after the paint is repaired for 2 hours at 80 ℃. The self-repairing waterborne polyurethane coating prepared by the invention has the advantages of simple preparation process, cheap and easily-obtained raw materials, high self-repairing rate of the coating and convenience for maintenance of the industrial coating.
Description
Technical Field
The invention relates to the field of paint synthesis, and in particular relates to a green environment-friendly waterborne polyurethane paint with self-repairing performance.
Background
The water-based polyurethane coating replaces an organic solvent with water, and is more environment-friendly compared with the traditional solvent type polyurethane coating. The waterborne polyurethane coating is widely applied to various fields of clothing, buildings, transportation, aerospace, medical supplies and the like due to the advantages of excellent wear resistance, chemical corrosion resistance, high strength, easy modification design and the like, but the waterborne polyurethane coating can generate microcracks due to the influence of external environments such as collision, corrosion, photodegradation and the like in the use process, so that the mechanical property of the material is reduced, and the functionalization of the coating is influenced. Therefore, the development of the waterborne polyurethane coating with the self-repairing function has important application value.
According to a healing method, the method can be divided into exogenous self-healing and intrinsic self-healing by adding a healing agent, and exogenous self-healing. The intrinsic self-healing through the design and modification of the molecular structure of polyurethane is more concerned. Dynamic covalent bonds are commonly introduced into polyurethanes to achieve self-healing effects, such as imine bonds, acylhydrazone bonds, disulfide bonds, borate bonds, D-A reactions, and the like. Besides, non-covalent bonds such as hydrogen bonds, ionic bonds, host-guest interactions, metal ligands and the like are often introduced into polyurethane, and polyurethane chain segments flow under the stimulation of light, heat, microwaves and other conditions, so that cracks and damages are repaired. Chinese invention patent CN112210060A discloses a self-repairable, green high-toughness polyurethane elastomer and a preparation method thereof, specifically, polycaprolactone-polytetrahydrofuran-polycaprolactone (PCL-PTHF-PCL) serving as a soft segment part is dissolved in N, N-Dimethylformamide (DMF), and then a hydroxyl or amino terminated disulfide chain extender is added to obtain the self-repairable, green high-toughness polyurethane elastomer, wherein the tensile strength of the material is 9MPa, the material is placed at room temperature for 7 hours after being cut off, and the repair rate is only 93%. The Chinese invention patent CN111410731A discloses a preparation method of a self-repairing polyurethane elastomer based on carboxylate radical-ferric ion, the maximum tensile strength is only 5.2MPa, and the repairing rate is 92%.
Therefore, the problem of providing a product with high tensile strength and high repair rate is urgently needed.
Disclosure of Invention
The invention aims to provide a self-repairing waterborne polyurethane coating containing imine bonds, which aims to overcome the technical defect of low repairing rate of self-repairing materials in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a self-repairing waterborne polyurethane coating containing imine bonds, which is characterized in that a preparation method of the coating comprises the following steps:
step 1, preparation of polyurethane chain extender containing imine bond
Dissolving a compound A in a solvent A according to a mass ratio of 1: 4-1: 8 to obtain a mixture A, dissolving a compound B in the solvent A according to a mass ratio of 1: 15-1: 20 to obtain a mixture B, adding a catalyst A into the mixture A to obtain a mixture C, slowly dropping the mixture C into the mixture B, magnetically stirring, heating to 100 ℃ by adopting an oil bath, refluxing for 5 hours, cooling the obtained solution at room temperature, carrying out vacuum filtration, rinsing with absolute ethyl alcohol for 3-4 times, taking out a filter cake, and carrying out vacuum drying to obtain a target product A containing imine bonds; wherein, the compound A contains one-OH and one-CHO, and the compound B contains 2-NH2The molar ratio of the compound A to the compound B is 2: 1-2.2: 1;
step 2, preparation of aqueous polyurethane coating containing imine bond
Dehydrating polymer dihydric alcohol at 120 ℃ for 2h in advance in vacuum to obtain a raw material A for later use; mixing a raw material A, diisocyanate, a hydrophilic chain extender, a target product A, a micromolecular chain extender, a catalyst and a solvent B in a mass ratio of 20:8:1.25:1.25:1:0.5:31 under the protection of nitrogen, and reacting for 8 hours at 85 ℃;
and 3, cooling the reaction system obtained in the step 2 to 35 ℃, adding a neutralizer with the same molar amount as the hydrophilic chain extender into the reaction system to react for 5min, adding deionized water into the reaction system to emulsify the mixture, and rotatably removing the solvent B to obtain the self-repairing waterborne polyurethane coating containing imine bonds.
Further, the compound A is one of p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, salicylaldehyde and vanillin.
Further, the compound B is one of p-phenylenediamine, m-phenylenediamine and p-phenylenediamine.
Further, the polymer diol is one of poly 1,4 butylene adipate diol (PBA), polycaprolactone diol (PCL), polycarbonate diol (PCDL) and polytetrahydrofuran diol (PTMG).
Further, the diisocyanate is one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, or dicyclohexylmethane 4,4' diisocyanate.
Further, the catalyst is dibutyl tin dilaurate, the solvent A is absolute ethyl alcohol, and the solvent B is one of acetone or butanone.
Further, the hydrophilic chain extender is one of 2, 2-dimethylolpropionic acid or 2, 2-dimethylolbutyric acid, the micromolecule chain extender is 1, 4-butanediol, and the neutralizing agent is triethylamine.
The beneficial technical effects of the invention are as follows:
(1) the invention firstly uses the compounds containing-CHO, -OH and-NH2The compound of (2) reacts to generate a chain extender containing imine bonds, reacts with polymer polyol and diisocyanate, then carries out chain extension on the chain extender by using an anionic monomer, and finally neutralizes with acetic acid to form salt and emulsify to prepare the self-repairing waterborne polyurethane coating; the synthesized polyurethane coating does not need to be added with a repairing agent and does not containThe polyurethane matrix unit needs to be changed, the mechanical property is good, the self-repairing performance of the polyurethane coating can be maintained for a long time, and the further popularization of the self-repairing polyurethane coating is facilitated.
(2) The raw materials for synthesizing the imine bond are economical and cheap, the reaction is simple and rapid, and the process is green and environment-friendly.
(3) The self-repairing rate of the prepared self-repairing waterborne polyurethane coating is as high as 99.2%, the self-repairing effect is excellent, the mechanical property is strong and can reach 52MPa at most, and the self-repairing waterborne polyurethane coating has potential application prospects in the aspects of transportation, industrial coatings, flexible electronic devices and the like.
Drawings
FIG. 1 is an IR spectrum of the coating obtained in example 1;
FIG. 2 is a graph showing the results of the scratch self-repair test of the coating film obtained in example 1 at 0, 5, 10 and 30 min;
FIG. 3 is a graph showing the scratch self-repair test results of the coating film obtained in example 2 at 0, 5, 10 and 30 min;
fig. 4 is a graph showing the results of the self-healing polyurethane coating film obtained in example 1 after being subjected to a crushing treatment.
Fig. 5 is a graph showing the results of the self-repairing polyurethane coating film obtained in example 1 after fracture repairing.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the self-repairing waterborne polyurethane coating containing imine bonds comprises the following steps:
(1) preparation of polyurethane chain extender containing imine bond
Adding 10g of p-phenylenediamine and 150ml of absolute ethyl alcohol into a 500ml three-neck flask, heating until the p-phenylenediamine and the absolute ethyl alcohol are completely dissolved to obtain a mixture B, dissolving 12g of p-hydroxybenzaldehyde into 150ml of absolute ethyl alcohol to obtain a mixture A, adding 1.2ml of acetic acid serving as a catalyst into the mixture A to obtain a mixture C, slowly dripping the mixture C into the mixture B, magnetically stirring, and heating to 100 ℃ by adopting an oil bath to reflux for 5 hours. And cooling the obtained reaction system at room temperature to separate out a large amount of light yellow crystals, carrying out vacuum filtration, rinsing with absolute ethyl alcohol for 3-4 times, taking out a filter cake, and carrying out vacuum drying to obtain the compound C-p-phenylenediamine p-hydroxybenzaldehyde bis-Schiff base.
(2) Preparation of aqueous polyurethane coating containing imine bond
Polytetrahydrofurandiol (PTMG) was dehydrated beforehand at 120 ℃ under vacuum for 2h for subsequent use in the presence of N240g of PTMG, 16g of isophorone diisocyanate (IPDI), 2.5g of 2, 2-dimethylolbutyric acid (DMBA), 2.2g of p-phenylenediamine p-hydroxybenzaldehyde bis-Schiff base, 1.8g of 1, 4-Butanediol (BDO) and 2 drops of dibutyltin dilaurate (DBTDL) were added to a three-necked flask under protection, and 55g of butanone as a solvent were added to react at 85 ℃ for 8 hours.
Reducing the temperature to 35 ℃, adding a neutralizing agent Triethylamine (TEA) with the same molar amount as the DMBA, reacting for 5min, adding deionized water for emulsifying for 30min, and removing butanone by rotary evaporation to obtain the self-repairing aqueous polyurethane coating containing imine bonds.
And (3) taking 10g of the synthesized coating, spreading the coating into a polytetrafluoroethylene plate, naturally standing at room temperature for 48h to remove water, and standing in a 40 ℃ oven for 48h until the coating is completely dried to obtain a coating.
The prepared polyurethane coating film is subjected to total reflection test by a Fourier transform infrared spectrometer (FTIR), and the resolution ratio is 2cm–1The test range is 400-4000 cm–1The obtained result is shown in FIG. 1, and the main characteristic absorption peak is 3325cm-1、1701cm-1、1602cm-1、1515cm-1Etc., indicating that self-healing polyurethanes containing imine linkages have been successfully prepared.
Self-repairing test of the polyurethane coating:
and (3) testing mechanical properties: the completely dried coating film was cut into a dumbbell shape of 4mm × 25mm, a mechanical property test was performed at a tensile speed of 100mm/min using an electronic tensile tester, and data was recorded when the coating film was broken.
Scratch repair test: and scratching the surface of the coating film by a blade with the width of 20-50 mu m and the depth of 80% of the thickness of the coating film, and placing the coating film on a constant-temperature heating plate for heating to repair the scratch.
Self-repairing test: cutting the coating into a dumbbell shape with the diameter of 4mm multiplied by 25mm, dividing the coating into two parts by a blade, tightly attaching the two parts, and putting the two parts into an oven for repairing at fixed time and temperature.
The tensile strength of the coating film obtained in the example 1 is 31.94MPa, the elongation at break is 1154.2, the scratch completely disappears after the repair is carried out at 60 ℃ for 5min, as shown in the attached figure 2, and after the complete cut and the repair is carried out at 80 ℃ for 2h, the tensile strength of the coating film is 31.70MPa, the elongation at break is 1039.0, and the self-repairing rate is 99.2%.
The obtained coating film is crushed to obtain the result shown in figure 4, and is changed into a smooth and complete coating film again after being subjected to hot pressing treatment at 100 ℃, 10min and 5MPa in a hot press shown in figure 5.
Example 2
The preparation method of the self-repairing waterborne polyurethane coating containing imine bonds comprises the following steps:
(1) preparation of polyurethane chain extender containing imine bond
10g of o-phenylenediamine and 150ml of absolute ethanol are added into a 500ml three-neck flask and heated to be completely dissolved to obtain a mixture B, 12g of salicylaldehyde is dissolved into 150ml of absolute ethanol to obtain a mixture A, 1.2ml of acetic acid serving as a catalyst is added into the mixture A to obtain a mixture C, the mixture C is slowly dropped into the mixture B, the mixture C is magnetically stirred, and the mixture C is heated to 100 ℃ by adopting an oil bath and refluxed for 5 hours. And cooling the obtained reaction system at room temperature to separate out a large amount of light yellow crystals, carrying out vacuum filtration, rinsing with absolute ethyl alcohol for 3-4 times, taking out a filter cake, and carrying out vacuum drying to obtain the compound C-o-phenylenediamine salicylaldehyde bis-Schiff base.
(2) Preparation of aqueous polyurethane coating containing imine bond
Pre-dehydrating polycaprolactone diol (PCL) at 120 deg.C for 2h, and adding into N2Under protection, 40g of PCL, 16g of isophorone diisocyanate (IPDI), 2.3g of 2, 2-dimethylolpropionic acid (DMPA) and 2.2g of o-phenylenediamine salicyleneAldehyde bis-Schiff base, 1.8g of 1, 4-Butanediol (BDO) and 2 drops of DBTDL were added into a three-necked flask, and 55g of butanone as a solvent was added to react at 85 ℃ for 8 hours.
Reducing the temperature to 35 ℃, adding a neutralizing agent Triethylamine (TEA) with the same molar amount as the DMPA, reacting for 5min, and adding deionized water to emulsify for 30 min. And (3) removing butanone by rotary evaporation to obtain the self-repairing aqueous polyurethane coating containing imine bonds.
And (3) taking 10g of the synthesized coating, paving the coating in a polytetrafluoroethylene template, naturally standing at room temperature for 48h to remove water, and standing in a 40 ℃ oven for 48h until the coating is completely dried to obtain a coating film.
Performance testing as referred to in example 1 resulted in:
the self-repairing polyurethane coating with the tensile strength of 28.98MPa and the elongation at break of 1436% is prepared in the embodiment, and after the coating is completely cut off, scratches completely disappear after the coating is repaired at 60 ℃ for 30min, and the attached drawing 3 shows. After the film is repaired for 2 hours at 80 ℃, the tensile strength of the film is 28.40MPa, the elongation at break is 1364 percent, and the self-repairing rate is 98.0 percent.
Example 3
The preparation method of the self-repairing waterborne polyurethane coating containing imine bonds comprises the following steps:
(1) preparation of polyurethane chain extender containing imine bond
Adding 10g of p-phenylenediamine and 150ml of absolute ethyl alcohol into a 500ml three-neck flask, heating until the p-phenylenediamine and the absolute ethyl alcohol are completely dissolved to obtain a mixture B, dissolving 15g of vanillin into 150ml of absolute ethyl alcohol to obtain a mixture A, adding 1.5ml of acetic acid serving as a catalyst into the mixture A to obtain a mixture C, slowly dropping the mixture C into the mixture B, magnetically stirring, and heating to 100 ℃ by adopting an oil bath for refluxing for 6 hours. And cooling the obtained reaction system at room temperature, separating out a large amount of light yellow crystals, carrying out vacuum filtration, rinsing with absolute ethyl alcohol for 3-4 times, taking out a filter cake, and carrying out vacuum drying to obtain the compound C-p-phenylenediamine vanillin bis-Schiff base.
(2) Preparation of aqueous polyurethane coating containing imine bond
1, 4-butanediol adipate diol (PBA) is dehydrated in vacuum at 120 ℃ for 2h for backup, 40g of PBA, 20g of dicyclohexylmethane 4,4' -diisocyanate (HMDI), 2.5g of 2, 2-dimethylolbutyric acid (DMBA), 2.7g of p-phenylenediamine vanillin bis-Schiff base, 1.8g of 1, 4-Butanediol (BDO) and 2 drops of DBTDL are added into a three-neck flask under the protection of N2, and 60g of butanone is added as a solvent to react for 8h at 85 ℃.
Reducing the temperature to 35 ℃, adding a neutralizing agent Triethylamine (TEA) with the same molar amount as the DMBA, reacting for 5min, adding deionized water and emulsifying for 30 min. And (3) removing butanone by rotary evaporation to obtain the self-repairing aqueous polyurethane coating containing imine bonds.
And (3) taking 10g of the synthesized coating, paving the coating in a polytetrafluoroethylene template, naturally standing at room temperature for 48h to remove water, and standing in a 40 ℃ oven for 48h until the coating is completely dried to obtain a coating film.
Performing the performance tests referred to in example 1, one can obtain:
the self-repairing polyurethane coating with the tensile strength of 52.06MPa and the elongation at break of 1305% is prepared by the embodiment, and after the coating is completely cut off and repaired at 80 ℃ for 2 hours, the tensile strength of the coating is 39.41MPa, the elongation at break is 998%, and the self-repairing rate is 75.8%.
Example 4
The preparation method of the self-repairing waterborne polyurethane coating containing imine bonds comprises the following steps:
(1) preparation of polyurethane chain extender containing imine bond
10g of m-phenylenediamine and 150ml of absolute ethanol were charged into a 500ml three-necked flask and heated to be completely dissolved to obtain a mixture B, 12g of m-hydroxybenzaldehyde was dissolved in 150ml of absolute ethanol to obtain a mixture A, 1.2ml of acetic acid as a catalyst was added to the mixture A to obtain a mixture C, and the mixture C was slowly dropped into the mixture B, magnetically stirred, and heated to 100 ℃ with an oil bath for reflux for 5 hours. And cooling the obtained reaction system at room temperature, precipitating a large amount of light yellow crystals, carrying out vacuum filtration, rinsing with absolute ethyl alcohol for 3-4 times, taking out a filter cake, and carrying out vacuum drying to obtain the compound C-m-phenylenediamine m-hydroxybenzaldehyde bis-Schiff base.
(2) Preparation of aqueous polyurethane coating containing imine bond
Polytetrahydrofuran glycol (PTMG) was dehydrated in advance under vacuum at 120 ℃ for 2h for backup, 40g of PTMG, 12g of isophorone diisocyanate (IPDI), 2g of 2, 2-dimethylolbutyric acid (DMBA), 1.7g of m-phenylenediamine meta-hydroxybenzaldehyde bis-Schiff base, 1g of 1, 4-Butanediol (BDO) and 2 drops of DBTDL were added to a three-necked flask under the protection of N2, and 50g of acetone was added as a solvent and reacted at 60 ℃ for 12 h.
Reducing the temperature to 35 ℃, adding a neutralizing agent Triethylamine (TEA) with the same molar amount as the DMBA, reacting for 5min, adding deionized water and emulsifying for 30 min. And removing acetone by rotary evaporation to obtain the self-repairing aqueous polyurethane coating containing imine bonds.
And (3) taking 10g of the synthesized coating, paving the coating in a polytetrafluoroethylene template, naturally standing at room temperature for 48h to remove water, and standing in a 40 ℃ oven for 48h until the coating is completely dried to obtain a coating film.
Performing the performance tests referred to in example 1, one can obtain:
the self-repairing polyurethane coating with the tensile strength of 21.32MPa and the elongation at break of 1407% is prepared in the embodiment, after the polyurethane coating is completely cut off and repaired at 60 ℃ for 2 hours, the tensile strength of the coating is 19.88MPa, the elongation at break is 1236%, the self-repairing rate is 93.2%, and after the polyurethane coating is repaired at 80 ℃ for 2 hours, the tensile strength of the coating is 21.02MPa, the elongation at break is 1396%, and the self-repairing rate is 98.6%.
Example 5
The preparation method of the self-repairing waterborne polyurethane coating containing imine bonds comprises the following steps:
(1) preparation of polyurethane chain extender containing imine bond
10g of p-phenylenediamine and 150ml of absolute ethanol are added into a 500ml three-neck flask and heated to be completely dissolved to obtain a mixture B, 12g of p-hydroxybenzaldehyde is dissolved into 150ml of absolute ethanol to obtain a mixture A, 1.2ml of acetic acid is added into the mixture A as a catalyst to obtain a mixture C, the mixture C is slowly dropped into the mixture B, the mixture C is magnetically stirred, and the mixture C is heated to 100 ℃ by adopting an oil bath and refluxed for 5 hours. And cooling the obtained reaction system at room temperature to separate out a large amount of light yellow crystals, carrying out vacuum filtration, rinsing with absolute ethyl alcohol for 3-4 times, taking out a filter cake, and carrying out vacuum drying to obtain the compound C-p-phenylenediamine p-hydroxybenzaldehyde bis-Schiff base.
(2) Preparation of aqueous polyurethane coating containing imine bond
Will gather togetherTetrahydrofuranediol (PTMG) was dehydrated in advance at 120 ℃ for 2h for replacement in N240g of PTMG, 13.5g of dicyclohexylmethane 4, 4-diisocyanate (HMDI), 2g of 2, 2-dimethylolbutyric acid (DMBA), 1.7g of p-phenylenediamine p-hydroxybenzaldehyde bis-Schiff base, 1g of 1, 4-Butanediol (BDO) and 2 drops of DBTDL were added to a three-necked flask under protection, and 50g of acetone was added as a solvent and reacted at 60 ℃ for 12 hours.
Reducing the temperature to 35 ℃, adding a neutralizing agent Triethylamine (TEA) with the same molar amount as the DMBA, reacting for 5min, adding deionized water and emulsifying for 30 min. And removing acetone by rotary evaporation to obtain the self-repairing aqueous polyurethane coating containing imine bonds.
And (3) taking 10g of the synthesized coating, paving the coating in a polytetrafluoroethylene template, naturally standing at room temperature for 48h to remove water, and standing in a 40 ℃ oven for 48h until the coating is completely dried to obtain a coating film.
Performing the performance tests referred to in example 1, one can obtain:
the self-repairing polyurethane coating with the tensile strength of 25.06MPa and the elongation at break of 1364% is prepared in the embodiment, and after the coating is completely cut off and self-repaired for 24 hours at room temperature, the tensile strength of the coating is 18.72MPa, the elongation at break of the coating is 1023%, and the self-repairing rate of the coating is 74.7%. After the film is repaired for 2 hours at 80 ℃, the tensile strength of the film is 23.96MPa, the elongation at break is 1210 percent, and the self-repairing rate is 95.6 percent.
The highest tensile strength of the polyurethane prepared by the Chinese patent CN113651938A is only 8.46MPa, and the repair rate is 95%; the self-repairing polyurethane prepared by the Chinese invention patent CN113512173A has the highest repairing rate of 96.8 percent after being treated for 4 hours at the temperature of 80 ℃; the Chinese patent CN111875821A adopts tetrahydrofuran as a solvent to synthesize polyurethane with a self-repairing effect, and the highest repairing rate is 98%. Compared with the invention, the highest tensile strength of the waterborne polyurethane self-repairing coating film prepared by the invention is 52MPa, the highest repairing rate can reach 99.2% after the waterborne polyurethane self-repairing coating film is repaired in a short time at a low temperature (80 ℃ and 2 hours), the process is simple and easy to control, the synthesis process is green and economical, and the obtained self-repairing polyurethane can not cause harm to human bodies and natural environment due to solvent volatilization.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. The self-repairing waterborne polyurethane coating containing imine bonds is characterized by comprising the following steps:
step 1, preparation of polyurethane chain extender containing imine bond
Dissolving a compound A in a solvent A according to a mass ratio of 1: 4-1: 8 to obtain a mixture A, dissolving a compound B in the solvent A according to a mass ratio of 1: 15-1: 20 to obtain a mixture B, adding a catalyst A into the mixture A to obtain a mixture C, slowly dropping the mixture C into the mixture B, magnetically stirring, heating to 100 ℃ by adopting an oil bath, refluxing for 5 hours, cooling the obtained solution at room temperature, carrying out vacuum filtration, rinsing with absolute ethyl alcohol for 3-4 times, taking out a filter cake, and carrying out vacuum drying to obtain a target product A containing imine bonds; wherein, the compound A contains one-OH and one-CHO, and the compound B contains 2-NH2The molar ratio of the compound A to the compound B is 2: 1-2.2: 1;
step 2, preparation of aqueous polyurethane coating containing imine bond
Dehydrating polymer dihydric alcohol at 120 ℃ for 2h in advance in vacuum to obtain a raw material A for later use; mixing a raw material A, diisocyanate, a hydrophilic chain extender, a target product A, a micromolecular chain extender, a catalyst and a solvent B in a mass ratio of 20:8:1.25:1.25:1:0.5:31 under the protection of nitrogen, and reacting for 8 hours at 85 ℃;
and 3, cooling the reaction system obtained in the step 2 to 35 ℃, adding a neutralizer with the same molar amount as the hydrophilic chain extender into the reaction system to react for 5min, adding deionized water into the reaction system to emulsify the mixture, and rotatably removing the solvent B to obtain the self-repairing waterborne polyurethane coating containing imine bonds.
2. The self-repairing aqueous polyurethane coating material containing imine bonds according to claim 1, wherein the compound A is one of p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, salicylaldehyde and vanillin.
3. The self-repairing aqueous polyurethane coating containing an imine bond according to claim 2, wherein the compound B is one of p-phenylenediamine, m-phenylenediamine and p-phenylenediamine.
4. The self-repairing aqueous polyurethane coating containing imine bonds of claim 3, wherein the polymer diol is one of poly (1, 4-butylene adipate) diol, polycaprolactone diol, polycarbonate diol, and polytetrahydrofuran diol.
5. The self-repairing aqueous polyurethane coating containing an imine bond according to claim 4, wherein the diisocyanate is one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, or dicyclohexylmethane 4,4' diisocyanate.
6. The self-repairing aqueous polyurethane coating material containing an imine bond according to claim 5, wherein the catalyst is dibutyl tin dilaurate, the solvent A is absolute ethanol, and the solvent B is one of acetone or butanone.
7. The self-repairing aqueous polyurethane coating containing an imine bond according to claim 5, wherein the hydrophilic chain extender is one of 2, 2-dimethylolpropionic acid or 2, 2-dimethylolbutyric acid, the small-molecule chain extender is 1, 4-butanediol, and the neutralizing agent is triethylamine.
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| 刘超等: "基于可逆共价键自修复聚氨酯的研究进展", 《精细化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115197393A (en) * | 2022-07-06 | 2022-10-18 | 辽宁大学 | Preparation method of self-repairing material with synergistic effect of multiple mechanisms |
| CN115558074A (en) * | 2022-08-03 | 2023-01-03 | 重庆交通大学 | Polyurethane elastomer and preparation method thereof |
| CN115558074B (en) * | 2022-08-03 | 2024-02-02 | 重庆交通大学 | Polyurethane elastomer and preparation method thereof |
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