CN117487447A - Self-repairing visible light curing elastic coating and preparation method thereof - Google Patents
Self-repairing visible light curing elastic coating and preparation method thereof Download PDFInfo
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- CN117487447A CN117487447A CN202211450155.6A CN202211450155A CN117487447A CN 117487447 A CN117487447 A CN 117487447A CN 202211450155 A CN202211450155 A CN 202211450155A CN 117487447 A CN117487447 A CN 117487447A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000004814 polyurethane Substances 0.000 claims abstract description 42
- 229920002635 polyurethane Polymers 0.000 claims abstract description 42
- 239000012948 isocyanate Substances 0.000 claims abstract description 40
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 22
- 239000000945 filler Substances 0.000 claims abstract description 18
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004220 glutamic acid Substances 0.000 claims abstract description 16
- 235000013922 glutamic acid Nutrition 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 13
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
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- 238000001723 curing Methods 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000010453 quartz Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229920000768 polyamine Polymers 0.000 claims description 14
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- 238000000034 method Methods 0.000 claims description 12
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 10
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- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
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- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
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- 125000003277 amino group Chemical group 0.000 claims description 5
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical group O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002685 polymerization catalyst Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
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- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 11
- 239000003973 paint Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000007098 aminolysis reaction Methods 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical group NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000000291 glutamic acid group Chemical group N[C@@H](CCC(O)=O)C(=O)* 0.000 description 2
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical group NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000010835 comparative analysis Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000005187 foaming Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
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- 239000003999 initiator Substances 0.000 description 1
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- 239000002973 irritant agent Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 230000000630 rising effect Effects 0.000 description 1
- 102200017049 rs779432560 Human genes 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- KCIKCCHXZMLVDE-UHFFFAOYSA-N silanediol Chemical compound O[SiH2]O KCIKCCHXZMLVDE-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a self-repairing visible light curing elastic coating and a preparation method thereof. The self-repairing visible light curing elastic coating comprises the following components in parts by weight: 30-65 parts of non-isocyanate polyurethane polymer, 2-3 parts of photoinitiator, 8-13 parts of filler, 1-2 parts of aqueous auxiliary agent, 9-12 parts of pH balancing agent and 120-130 parts of deionized water; the non-isocyanate polyurethane polymer comprises two parts, namely an A premix and a B premix, wherein the A premix is prepared by carrying out polyester polycondensation on a non-isocyanate polyurethane monomer and glutamic acid, and the B premix is prepared by carrying out polyester polycondensation on the non-isocyanate polyurethane monomer and tricarballylic acid. The self-repairing visible light curing elastic coating provided by the invention can realize self-repairing at room temperature without additional energy input, and has good wear resistance, low-temperature water resistance, solvent resistance, thermal stability and mechanical property.
Description
Technical Field
The invention relates to the field of coatings, in particular to a self-repairing visible light curing elastic coating and a preparation method thereof.
Background
As one of the common crosslinking matrixes of the coating, the polyurethane acrylate contains an acrylic acid functional group and a urethane bond in the molecule, and the structure ensures that the coating has high wear resistance, adhesive force, flexibility and low temperature resistance. In industry, polyurethanes are generally prepared by reacting an isocyanate with a polyol in the presence of a catalyst. Isocyanate is a highly toxic substance harmful to the environment and human health, and inhalation is prone to cause asthma, and even death after accumulation of a certain dose. And, in the process of preparing isocyanate, highly toxic phosgene is used. Phosgene is a highly irritating gas, and once leakage results are not envisaged, it is necessary to popularize non-isocyanate polyurethane (NIPU) coatings based on this.
The non-isocyanate polyurethane generally refers to a novel environment-friendly polyurethane formed by reacting a cyclic carbonate compound with a polyamine. The polyurethane has the characteristics that each carbamate group on the molecule is provided with a hydroxyl group connected with a beta-position carbon atom of the carbamate group, and the hydrogen atom of the hydroxyl group can form an intramolecular hydrogen bond with a carbonyl oxygen atom in the carbamate group to form a stable six-membered ring structure, so that the six-membered ring structure is very stable, and the hydrolytic stability, chemical resistance and permeation resistance of the NIPU can be improved. Meanwhile, with the development of reversible crosslinked polymers, dynamic characteristics between urethane bonds and hydroxyl groups in non-isocyanate polyurethane structures have been increasingly emphasized. Based on the bond exchange reaction between the carbamate and the hydroxyl groups, the polyurethane can be endowed with self-repairing and reprocessing properties. However, the conditions for self-repairing and reprocessing are severe due to the high temperature required for the bond exchange reaction, which is unfavorable for large-scale application.
The prior art CN114380994A discloses a bio-based non-isocyanate polyurethane and a preparation method thereof, wherein the bio-based non-isocyanate polyurethane is obtained by condensation reaction of bio-based bicyclic carbonate and amine compounds, and carbamate and hydroxyl functional groups in the structure can undergo transesterification under a heating state, so that the self-repairing performance of the material is endowed. However, achieving self-healing requires additional energy input, which in some areas may limit the application of non-isocyanate polyurethane coatings. Therefore, the research of the low-energy-driven self-repairing material has important application value.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a visible light curing elastic coating which is environment-friendly in formula and can be self-repaired at room temperature.
In order to achieve the above purpose, the present invention provides the following technical solutions: the self-repairing visible light curing elastic coating comprises the following raw materials in parts by weight:
30-65 parts of non-isocyanate polyurethane polymer, 2-3 parts of photoinitiator, 7-12 parts of filler, 3-5 parts of aqueous auxiliary agent, 6-10 parts of pH balancing agent and 120-130 parts of deionized water;
the non-isocyanate polyurethane polymer comprises a pre-mixture A and a pre-mixture B, wherein the pre-mixture A is prepared by the polycondensation reaction of a non-isocyanate polyurethane monomer and glutamic acid through polyester, and the pre-mixture B is prepared by the polycondensation reaction of the non-isocyanate polyurethane monomer and tricarballylic acid through polyester;
further, the preparation method of the non-isocyanate polyurethane polymer comprises the following steps:
(1) Preparation of non-isocyanate polyurethane monomer: adding ethylene carbonate, aliphatic polyamine shown in a formula I and an organic solvent into a reactor, fully stirring, increasing the temperature of the system to 70-100 ℃ for accelerating reaction, filtering after the reaction is finished, and drying filter residues to obtain a non-isocyanate polyurethane monomer shown in a formula II (NIPU monomer for short);
wherein R is an alkylene group of carbon chain length C2-C7 or an alkylene group of carbon chain length C2-C7 substituted with an amino group;
(2) A premix preparation: the NIPU monomer prepared above and glutamic acid are mixed according to the proportion of 1.0-1.5:1.0, adding the mixture into a reaction container together with a pre-polymerization catalyst and a polymerization inhibitor, introducing nitrogen into the reaction container, keeping the reaction temperature at 95-120 ℃ for pre-polymerization, adding a polycondensation catalyst for reaction after no moisture is generated, controlling the temperature at 150-170 ℃ and the vacuum degree at 0.092-0.096MPa, pouring out the product after the reaction is finished and cooling to room temperature, and storing in a low-temperature drying place for later use;
b premix preparation: the NIPU monomer prepared above and the tricarballylic acid are mixed according to the ratio of 1.0-1.5:1.0, adding the mixture into a reaction container together with a pre-polymerization catalyst and a polymerization inhibitor, introducing nitrogen into the reaction container, keeping the reaction temperature at 95-120 ℃ for pre-polymerization, adding a polycondensation catalyst for reaction after no moisture is generated, controlling the temperature at 150-170 ℃ and the vacuum degree at 0.092-0.096MPa, pouring out the product after the reaction is finished and cooling to room temperature, and storing in a low-temperature drying place for later use;
(3) Preparation of non-isocyanate polyurethane polymer: respectively dissolving an A premix and a B premix with the mass ratio of 1.0:1.0-1.5 in an organic solvent, dropwise adding the A premix solution into the B premix solution, stirring overnight, pouring the obtained viscous polymer solution into a polytetrafluoroethylene mold, standing overnight at room temperature, naturally volatilizing the solvents, and then placing the mold into a vacuum drying oven to further remove the solvents, thereby obtaining the non-isocyanate polyurethane polymer (NIPU polymer for short).
The organic solvent used in the preparation process of the NIPU monomer is one of dimethyl sulfoxide (Dimethyl sulfoxide, DMSO) and Dimethylformamide (DMF), the pre-polycondensation catalyst can be p-toluenesulfonic acid monohydrate, the polymerization inhibitor is one of p-benzoquinone and methyl hydroquinone, the polycondensation catalyst is one of antimony trioxide, antimony acetate and ethylene glycol antimony, and the organic solvent used in the preparation step of the NIPU polymer can be one of sulfolane, acetone, acetonitrile and tetrahydrofuran.
The NIPU polymer prepared by the invention has carbamate group, ester group, side chain amino group and carboxyl group on the structure, so that the NIPU polymer has more excellent mechanical property, solvent resistance, hydrolysis resistance and the like than the conventional polyurethane. When the NIPU polymer is used as a main resin of the photo-curing coating, the thermal stability of the coating is enhanced by the existence of the carbamate group, and the intermolecular force in the coating is very large by the existence of the carbamate group and the ester group, so that the coating has good low-temperature water resistance. More importantly, carboxyl and amino exist in the molecule of the NIPU polymer prepared by the invention at the same time, and a weak-interaction ionic hydrogen bond is formed between the carboxyl and amino, so that relatively easier dynamic bonding and bond breaking provide a greater possibility for self-repairing of the coating. Meanwhile, the ionic hydrogen bond can lead the interior of the coating to have rich cross-linked network, thereby endowing the coating with considerable mechanical property and excellent ductility.
The research shows that the longer the aliphatic chain of the aliphatic polyurethane resin molecule is, the stronger the molecular mobility is, and the higher the intermolecular crosslinking density is, but too long the aliphatic chain also increases the rigidity, inhibits the intermolecular crosslinking, and leads to the reduction of the mechanical property and the stability of the coating. Also because the activity of the polyamines is related to their structure and relative molecular mass, it is preferred that the aliphatic polyamines of the present invention are primary amines having carbon chain lengths between C2 and C7 or primary amines having carbon chain lengths between C2 and C7 substituted with amino groups.
The self-repairing visible light-curable elastic coating material according to the invention preferably comprises at least two photoinitiators, particularly preferably a mixture of photoinitiators 784 and 4265 mixed in a mass ratio of 1.2 to 1.5:1.0.
The inventors of the present invention found that photoinitiator 784 is a good visible light initiator, and its initiation process is neither cleavage type nor hydrogen abstraction type, but after light energy absorption, photoisomerization becomes a cyclic photoreaction intermediate, and ligand substitution occurs with ester carbonyl in the oligomer to generate free radicals, which initiate polymerization and crosslinking; the coating has good absorption at visible light, has bleaching effect after photolysis, is suitable for visible light curing of thick coatings, and can cure coatings with thickness of more than 70 mu m; the photoinitiator 4265 is a highly efficient liquid photoinitiator consisting of 50% tpo and 50% Irgacure1173 suitable for use in curing coatings for water-based systems. The invention mixes the photoinitiator 784 and the photoinitiator 4265 for use, which can further accelerate the curing rate of the coating, and can also reduce the use amount of the photoinitiator to a great extent, thereby reducing the probability of migration of the photoinitiator to the surface.
The filler is at least one selected from active kaolin, porous powder quartz and mica powder, wherein the active kaolin is preferably amino silane coupling agent modified active kaolin. Further, the filler is preferably a mixture of active kaolin modified by an amino silane coupling agent and porous powder quartz according to a mass ratio of 6-10:1-2. The hydroxyl formed by the silane coupling agent for modifying the active kaolin after hydrolysis reacts with the active group on the surface of the kaolin to form a hydrogen bond, the hydrogen bond is coated on the surface of the kaolin, the exposed hydrophobic group at the other end of the silane coupling agent reacts with the active group of the NIPU polymer to form a strong chemical bond, so that the mechanical property of the product is improved, the amino on the silane coupling agent is provided with active hydrogen and can react with various polymers, and two materials with completely different properties are tightly combined through the chemical bond; the active kaolin can also play a role of filling a framework, and has high dispersion capacity, chemical stability and corrosion resistance; on the other hand, the surface of the porous powder quartz contains a certain amount of hydroxyl-silanol, which is helpful for improving the adhesive force and cohesiveness of the coating, and hydroxyl can form ion hydrogen bonds with a crosslinked network in a system, so that the tensile strength of the coating is improved; the aqueous auxiliary agent is at least one of an aqueous wetting agent, an aqueous defoaming agent and an aqueous leveling agent; preferably, the aqueous wetting agent may be TRITON X-405, TRITON BD-405, both of which are nonionic wetting agents having a high HLB (Hydrophile-Lipophile Balance) value and a strong emulsifying and wetting ability; the aqueous defoaming agent and/or the leveling agent are TEGO Glide410 and TEGO Glide450, and are used in the coating and have the effects of inhibiting foam and defoaming, reducing shrinkage cavity and promoting leveling, so that the use of auxiliary agents can be reduced, and the use cost is reduced;
a preparation method of self-repairing visible light curing elastic coating comprises the following steps:
(1) Weighing the photoinitiator and deionized water according to parts by weight, adding the photoinitiator and the deionized water into a clean reaction container, stirring and pre-dispersing the mixture to a particle-free state, and controlling the stirring speed to be 150-250 r/min;
(2) Adding the prepared non-isocyanate polyurethane into a stirred reactor, heating the system to 45-60 ℃, adding a pH regulator, adjusting the stirring rate to 500-750 rpm, and adding a certain amount of deionized water to adjust the solid content;
(3) Sequentially adding the filler and the auxiliary agent, uniformly mixing and stirring, dispersing for 20-30 minutes, and filtering to obtain the self-repairing visible light curing elastic coating.
The use of the non-isocyanate polyurethane coatings described above is also within the scope of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
1. the non-isocyanate polyurethane monomer obtained by the reaction of ethylene carbonate and aliphatic polyamine is reacted with glutamic acid and tricarballylic acid to prepare a premix, and the premix is mixed under certain conditions to obtain the non-isocyanate polyurethane polymer, so that the use of polyisocyanate is avoided, and simultaneously, the carbamate group improves the low-temperature water resistance and solvent resistance of the coating. In addition, the introduced carboxyl and amino enable reversible ion hydrogen bonds to exist between molecular crosslinking networks in the paint, so that the paint has good flexibility, and the paint surface can be self-healed at room temperature after being damaged;
2. the full utilization of the paint to the light source is ensured by adding the multiband absorption aqueous photoinitiator, and the curing of the paint under visible light is realized;
3. and proper fillers and auxiliary agents are utilized to improve the adhesive force and mechanical property of the coating.
Detailed Description
The present invention will be described in further detail with reference to examples. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
Some of the component sources in the examples and comparative examples are:
glutamic acid is commercially available; photoinitiators 784 and 4265 used were from basf Irgacure784 and Irgacure4265, germany; the modified active kaolin is 2000 mesh modified kaolin purchased from rich mineral products, the porous powder quartz is 12000 mesh porous powder quartz purchased from rich mineral products, and the mica powder is sericite powder purchased from rich mineral products.
The following are illustrative of the preparation methods of NIPU-1-11 used in the examples and comparative examples, respectively, as follows:
preparation of NIPU-1
(1) NIPU monomer preparation: adding ethylene carbonate (Ethylene Carbonate, EC) and ethylenediamine into a reactor filled with DMSO according to the ratio of 2.0:1.0, fully stirring, heating the system to 70 ℃ to start aminolysis reaction, and filtering and drying the precipitate for later use after the reaction is finished;
(2) A premix preparation: the NIPU monomer prepared above and glutamic acid were mixed according to the ratio of 1.2:1.0, then adding the mixture into a reaction vessel together with a pre-polycondensation catalyst, namely paratoluenesulfonic acid monohydrate and a polymerization inhibitor, namely paratoluenesulfonic acid, introducing nitrogen into the reaction vessel, firstly keeping the reaction temperature at 100 ℃, carrying out pre-polycondensation, adding a polycondensation catalyst, namely antimonous oxide to react after no water is generated basically, controlling the temperature at 150 ℃ and the vacuum degree at 0.094MPa, stopping heating after the reaction is finished, pouring out the product after cooling, and storing the product at a low-temperature drying place for later use;
b premix preparation: the same as the preparation of premix a except that glutamic acid was replaced with tricarballylic acid;
(3) NIPU-1 preparation: respectively dissolving an A premix and a B premix with the mass ratio of 1.0:1.0 in THF, dropwise adding the A premix solution into the B premix solution, stirring overnight, pouring the obtained viscous polymer solution into a polytetrafluoroethylene mold, standing overnight at room temperature, naturally volatilizing the solvent, and then placing into a vacuum drying oven to further remove the solvent to obtain the NIPU-1 polymer.
NIPU-2 preparation
The preparation method is similar to the preparation method of NIPU-1, except that in the monomer preparation process, the aliphatic polyamine is selected from the group consisting of the trimellitamide, EC is that the trimellitamide=2.1:1.0, the organic solvent is selected from the group consisting of DMF, and the aminolysis reaction temperature is 80; NIPU monomer in premix A: NIPU monomer in glutamic acid and B premix: the molar ratio of the tricarballylic acid is 1.3:1.0, antimony acetate is used as a polycondensation catalyst, and the reaction conditions are as follows: the mass ratio of premix A to premix B was 1.0:1.2 at 105 ℃, 155 ℃, 0.095 MPa.
NIPU-3 preparation
The preparation method is similar to the preparation method of NIPU-1, except that 1, 5-butanediamine is selected as aliphatic polyamine in monomer preparation, EC is 1, 5-butanediamine=2.2:1.0, and the aminolysis reaction temperature is 90 solutions; NIPU monomer in premix A: NIPU monomer in glutamic acid and B premix: the mole ratio of the tricarballylic acid is 1.25:1.0, the polycondensation catalyst is ethylene glycol antimony, and the reaction conditions are respectively as follows: the mass ratio of premix A to premix B was 1.0:1.3 at 110deg.C, 160deg.C, 0.096 MPa.
NIPU-4 preparation
The method is similar to the preparation method of NIPU-1, except that in the monomer preparation, aliphatic polyamine is 1, 5-pentanediamine, EC is 1, 5-pentanediamine=2.3:1.0, organic solvent is DMF, and the aminolysis reaction temperature is 100; NIPU monomer in premix A: NIPU monomer in glutamic acid and B premix: the mole ratio of the tricarballylic acid is 1.3:1.0, the polymerization inhibitor is methyl hydroquinone, the polycondensation catalyst is ethylene glycol antimony, and the reaction conditions are respectively as follows: the mass ratio of premix A to premix B was 1.0:1.4 at 115℃and 165℃at 0.096 MPa.
NIPU-5 preparation
The method is similar to the preparation method of NIPU-1, except that 1, 6-hexamethylenediamine is selected as aliphatic polyamine in monomer preparation, EC is 1, 6-hexamethylenediamine=2.4:1.0, and the aminolysis reaction temperature is 95 solution; NIPU monomer in premix A: NIPU monomer in glutamic acid and B premix: the mole ratio of the tricarballylic acid is 1.35:1.0, the polymerization inhibitor is methyl hydroquinone, the polycondensation catalyst is antimony acetate, and the reaction conditions are as follows: the mass ratio of premix A to premix B was 1.0:1.5 at 120deg.C, 170deg.C, and 0.096 MPa.
NIPU-6 preparation
The method is similar to the preparation method of NIPU-1, except that in the monomer preparation, aliphatic polyamine is 1, 7-heptanediamine, EC is 1, 7-heptanediamine=2.5:1.0, organic solvent is DMF, and the aminolysis reaction temperature is 85 degrees; NIPU monomer in premix A: NIPU monomer in glutamic acid and B premix: the mole ratio of the tricarballylic acid is 1.4:1.0, the polymerization inhibitor is methyl hydroquinone, the polycondensation catalyst is antimonous oxide, and the reaction conditions are respectively as follows: 110 ℃, 160 ℃ and 0.093MPa.
NIPU-7 preparation
The same method as NIPU-6 is different in that 1, 8-octanediamine is selected as aliphatic polyamine in monomer preparation.
NIPU-8 preparation
The same method as NIPU-6 is different in that 1, 9-nonanediamine is selected as aliphatic polyamine in monomer preparation.
NIPU-9 preparation
The same procedure as for NIPU-3 was followed except that glutamic acid was replaced with maleic acid having no amino group.
NIPU-10 preparation
The same process as that of NIPU-3 except that no tricarballylic acid is added.
NIPU-11 preparation
The same procedure as for NIPU-3 was followed except that glutamic acid was not added.
The following illustrates the preparation method of the self-repairing visible light curing elastic coating in examples and comparative examples, comprising the following steps:
(1) Adding the photoinitiator and a part of deionized water into a clean reaction container, stirring and pre-dispersing to a particle-free state, wherein the stirring speed is controlled to be 150-250 revolutions per minute;
(2) Adding the prepared NIPU into a stirred reactor, heating the system to 45-60 ℃, adding a pH regulator, adjusting the stirring speed to 500-750 r/min, and then adding the rest deionized water to adjust the solid content;
(3) Sequentially adding the filler and the auxiliary agent, uniformly mixing and stirring, dispersing for 20-30 minutes, and filtering to obtain the self-repairing visible light curing elastic coating.
Example 1
A self-healing visible light-cured elastomeric coating comprising the components of: 30 parts of NIPU-1,2 parts of photoinitiator (Irgacure 784: irgacure 4265=1.2:1.0), 7 parts of mixed filler with the mass ratio of modified kaolin to porous powder quartz being 6:1, 3 parts of TEGO Glide410 flatting agent, 6 parts of pH regulator (NaHCO 3 /H 2 CO 3 ) 120 parts of deionized water.
Example 2
A self-healing visible light-cured elastomeric coating comprising the components of: 45 parts of NIPU-2,2.5 parts of photoinitiator (Irgacure 784: irgacure 4265=1.2:1.0), 10 parts of mixed filler with a mass ratio of modified kaolin to porous powder quartz of 8:2, 1 part of TRITON X-405,2 parts of TEGO Glide410,7 parts of pH regulator (NaHCO) 3 /H 2 CO 3 ) 125 parts of deionized water.
Example 3
A self-healing visible light-cured elastomeric coating comprising the components of: 55 parts of NIPU-3,3 parts of photoinitiator (Irgacure 784: irgacure 4265=1.5:1.0), 12 parts of mixed filler with a mass ratio of modified kaolin to porous powder quartz of 10:2, 2 parts of TRITON BD-405,2 parts of TEGO Glide450,8 parts of pH regulator (KHCO 3 /H 2 CO 3 ) 130 parts of deionized water.
Example 4
A self-healing visible light-cured elastomeric coating comprising the components of: 65 parts of NIPU-4,2.5 parts of photoinitiator (Irgacure 784: irgacure 4265=1.3:1.0), 10 parts of modified kaolin, 2 parts of TRITON X-405,1 parts of TEGO Glide410,9 parts of pH regulator (NaAc/HAc) and 125 parts of deionized water.
Example 5
A self-healing visible light-cured elastomeric coating comprising the components of: 50 parts of NIPU-5,3 parts of photoinitiator (Irgacure 784: irgacure 4265=1.4:1.0), 9 parts of modified kaolin, 1 part of TRITON X-405,1 parts of TEGO Glide450, 10 parts of pH regulator (NaAc/HAc) and 120 parts of deionized water.
Example 6
A self-healing visible light-cured elastomeric coating comprising the components of: 50 parts of NIPU-6,2 parts of photoinitiator (Irgacure 784: irgacure 4265=1.4:1.0), 11 parts of porous powder quartz, 1 part of TRITON BD-405,1 parts of TEGO Glide410, 10 parts of pH regulator (NaAc/HAc) and 130 parts of deionized water.
Example 7
A self-healing visible light-cured elastomeric coating comprising the components of: 30 parts of NIPU-7,2 parts of photoinitiator (Irgacure 784: irgacure 4265=1.2:1.0), 7 parts of mixed filler with the mass ratio of modified kaolin to porous powder quartz being 9:1, 3 parts of TEGO Glide410 flatting agent, 6 parts of pH regulator (NaHCO 3 /H 2 CO 3 ) 120 parts of deionized water.
Example 8
A self-healing visible light-cured elastomeric coating comprising the components of: 30 parts of NIPU-8,2 parts of photoinitiator (Irgacure 784: irgacure 4265=1.2:1.0), 7 parts of mica powder, 3 parts of TEGO Glide410 leveling agent, 6 parts of pH regulator (NaHCO 3 /H 2 CO 3 ) 120 parts of deionized water.
Comparative example 1
A self-healing visible light-cured elastomeric coating comprising the components of: 55 parts of NIPU-9,3 parts of photoinitiator (Irgacure 784: irgacure 4265=1.5:1.0), 12 parts of mixed filler with a mass ratio of modified kaolin to porous powder quartz of 10:2, 2 parts of TRITON BD-405,2 parts of TEGO Glide450,8 parts of pH regulator (KHCO 3 /H 2 CO 3 ) 130 parts of deionized water.
Comparative example 2
A self-healing visible light-cured elastomeric coating comprising the components of: 55 parts of NIPU-10,3 parts of photoinitiator (Irgacure 784: irgacure 4265=1.5:1.0), 12 parts of mixed filler with a mass ratio of modified kaolin to porous powder quartz of 10:2, 2 parts of TRITON BD-405,2 parts of TEGO Glide450,8 parts of pH regulator (KHCO 3 /H 2 CO 3 ) 130 parts of deionized water.
Comparative example 3
A self-healing visible light-cured elastomeric coating comprising the components of: 55 parts of NIPU-11,3 parts of photoinitiator (Irgacure 784: irgacure 4265=1.5:1.0), 12 parts of mixed filler with the mass ratio of modified kaolin to porous powder quartz being 10:2, 2 parts of TRITON BD-405,2 parts of TEGO Glide450,8 parts of pH regulator (KHCO 3 /H 2 CO 3 ) 130 parts of deionized water.
Comparative example 4
A visible light-curable elastic coating, comprising the components of: 55 parts of Pasteur C95A (polyester polyurethane), 3 parts of photoinitiator (Irgacure 784: irgacure 4265=1.5:1.0), 12 parts of a mixed filler with a mass ratio of modified kaolin to porous powder quartz of 10:2, 2 parts of TRITON BD-405,2 parts of TEGO Glide450,8 parts of pH regulator (KHCO 3 /H 2 CO 3 ) 130 parts of deionized water.
Performance testing
Mixing 10 parts of the paint prepared in the examples 1-8 and the comparative examples 1-4 with a diluent to adjust the viscosity required by spraying, wherein the spraying mode adopts compressed air to spray the paint onto the surface of a PC substrate, the caliber of a spray gun is 0.8-1.4mm, and the air pressure is 0.3-0.5MPa; baking at 55+ -5deg.C for 8-10min to form a coating with a film thickness of 20+ -3 μm, and curing under visible light with light source energy of 200-250mJ/cm 2 。
Hardness testing: according to GB/T13448-2006, selecting a Chinese brand pencil with the hardness range of 6B-6H to measure the pencil hardness of the cured coating;
tensile strength measurement: cutting a dumbbell-shaped test piece meeting the GB/T528 requirement, marking parallel marks of 25mm, and testing the tensile property of the coating according to the test method of building waterproof paint of GB/T16777-2008, 9.2.1 untreated tensile test, wherein the tensile rate is 500mm/min, and the test temperature is 25;
thermal stability determination: adopting an STA 449F 3 synchronous thermal analyzer produced by German relaxation-resistant company to perform thermal stability test on the coating, wherein the temperature rising rate is 20 steps of thermal analyzers in nitrogen atmosphere, and the temperature is 50-600;
low temperature water resistance test: the low temperature water resistance of the coating was evaluated according to ASTM D870-15, primarily by observing the surface change of the coating after soaking in 38 water for a period of time, to see through the phenomena of no blistering, no peeling;
solvent resistance test: the solvent resistance of the coating was determined by cyclic wiping with cotton wool saturated with the specified solvent according to ASTM D5402-15, with no foaming, no flaking phenomena being considered as passing;
healing ability test: the coating was scratched with sharp corners of a 250 μm thick PET substrate and the time required for the scratch to disappear was visually observed.
The test results of examples 1-8 and comparative examples 1-4 are shown in Table 2.
TABLE 2 Performance test results of the coatings prepared in examples 1-8 and comparative examples 1-4
As can be seen from the test results of comparative analysis examples 1-8 and comparative examples 1-4, the non-isocyanate polyurethane provided by the invention is applied to the coating, so that the tensile strength and the thermal stability of the coating are greatly improved, and the film layer has good hardness, low-temperature water resistance and solvent resistance. More importantly, the paint prepared from the non-isocyanate polyurethane provided by the invention has obvious self-repairing performance at room temperature, and can recover after being scratched for about 15 minutes without additional energy input, thereby greatly saving the use cost.
The present invention is capable of other and further embodiments and its several details are capable of modification and variation in light of the present invention, as will be apparent to those skilled in the art, without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The self-repairing visible light curing elastic coating is characterized by comprising the following components in parts by weight: 30-65 parts of non-isocyanate polyurethane polymer, 2-3 parts of photoinitiator, 8-13 parts of filler, 1-2 parts of aqueous auxiliary agent, 9-12 parts of pH balancing agent and 120-130 parts of deionized water; wherein the non-isocyanate polyurethane polymer comprises two parts, namely an A premix and a B premix, wherein the A premix is prepared by the polycondensation reaction of non-isocyanate polyurethane monomers and glutamic acid through polyester, and the B premix is prepared by the polycondensation reaction of non-isocyanate polyurethane monomers and tricarballylic acid through polyester.
2. The self-healing visible light-cured elastomeric coating of claim 1, wherein said non-isocyanate polyurethane polymer is prepared by the process comprising:
(1) Preparation of non-isocyanate polyurethane monomer: adding ethylene carbonate, aliphatic polyamine shown in a formula I and an organic solvent into a reactor, fully stirring, increasing the temperature of the system to 70-100 ℃ to accelerate the reaction, filtering after the reaction is finished, and drying filter residues to obtain a non-isocyanate polyurethane monomer shown in a formula II;
wherein R is an alkylene group of carbon chain length C2-C7 or an alkylene group of carbon chain length C2-C7 substituted with an amino group;
(2) A premix preparation: mixing the non-isocyanate polyurethane monomer prepared in the step (1) with glutamic acid according to the ratio of 1.0-1.5:1.0, adding the mixture into a reaction container together with a pre-polymerization catalyst and a polymerization inhibitor, introducing nitrogen into the reaction container, keeping the reaction temperature at 95-120 ℃ for pre-polymerization, adding a polycondensation catalyst for reaction after no moisture is generated, controlling the temperature at 150-170 ℃ and the vacuum degree at 0.092-0.096MPa, cooling to room temperature after the reaction is finished, pouring out the product, and storing in a low-temperature drying place for later use;
b premix preparation: mixing the non-isocyanate polyurethane monomer prepared in the step (1) with tricarballylic acid according to the ratio of 1.0-1.5:1.0, adding the mixture into a reaction container together with a pre-polymerization catalyst and a polymerization inhibitor, introducing nitrogen into the reaction container, keeping the reaction temperature at 95-120 ℃ for pre-polymerization, adding a polycondensation catalyst for reaction after no moisture is generated, controlling the temperature at 150-170 ℃ and the vacuum degree at 0.092-0.096MPa, cooling to room temperature after the reaction is finished, pouring out the product, and storing in a low-temperature drying place for later use;
(3) Preparation of non-isocyanate polyurethane polymer: the mass ratio is 1.0:1.0-1.5 of A premix and B premix are respectively dissolved in an organic solvent, the A premix solution is dropwise added into the B premix solution, stirring is carried out overnight, the obtained viscous polymer solution is poured into a polytetrafluoroethylene mould, the room temperature is carried out overnight, after the solvent is naturally volatilized, the solution is put into a vacuum drying oven to remove the solvent, and the non-isocyanate polyurethane polymer is obtained.
3. The self-healing visible light-cured elastomeric coating of claim 2, wherein the ratio of ethylene carbonate to aliphatic polyamine is 2.0-2.5:1.0; the organic solvent is one of dimethyl sulfoxide and dimethylformamide.
4. The self-repairing visible light-cured elastic coating according to claim 2, wherein the pre-polycondensation catalyst is p-toluenesulfonic acid monohydrate, the polymerization inhibitor is one of p-benzoquinone and methyl hydroquinone, and the polycondensation catalyst is one of antimony trioxide, antimony acetate and ethylene glycol antimony.
5. Self-healing visible light-curable elastomeric coating according to claim 1, characterized in that it contains at least two photoinitiators, preferably photoinitiators 784 and 4265, in a mass ratio of 1.2-1.5:1.0.
6. The self-repairing visible light-cured elastic coating according to claim 1, wherein the filler is one or any combination of active kaolin, porous powder quartz and mica powder.
7. The self-healing visible light-cured elastic coating according to claim 1, wherein the aqueous auxiliary agent is at least one of an aqueous wetting agent, an aqueous defoaming agent and an aqueous leveling agent.
8. The self-healing visible light-cured elastomeric coating according to claim 7, wherein the pH balancing agent is NaHCO 3 /H 2 CO 3 、KHCO 3 /H 2 CO 3 Any one of NaAc/HAc buffer pair.
9. A method of preparing a self-healing visible light cured elastomeric coating according to any one of claims 1 to 8, comprising the steps of:
(1) Weighing the photoinitiator according to parts by weight and adding part of deionized water into a clean reaction container for stirring and pre-dispersing until no particles exist, wherein the stirring speed is controlled to be 150-250 revolutions per minute;
(2) Adding non-isocyanate polyurethane polymer into a stirring reactor, heating the system to 45-60 ℃, adding a pH regulator, adjusting the stirring rate to 500-750 r/min, and then adding the rest deionized water to adjust the solid content;
(3) Sequentially adding the filler and the auxiliary agent, uniformly mixing and stirring, dispersing for 20-30 minutes, and filtering to obtain the self-repairing visible light curing elastic coating.
10. Use of the self-healing visible light curing elastic coating according to claim 1.
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