CN115181468A - Super-hydrophilic self-cleaning coating sol and preparation method and application thereof - Google Patents
Super-hydrophilic self-cleaning coating sol and preparation method and application thereof Download PDFInfo
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- CN115181468A CN115181468A CN202210951100.7A CN202210951100A CN115181468A CN 115181468 A CN115181468 A CN 115181468A CN 202210951100 A CN202210951100 A CN 202210951100A CN 115181468 A CN115181468 A CN 115181468A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 97
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- 238000002360 preparation method Methods 0.000 title abstract description 13
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 19
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
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- 239000003999 initiator Substances 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 claims description 7
- ZEYUSQVGRCPBPG-UHFFFAOYSA-N 4,5-dihydroxy-1,3-bis(hydroxymethyl)imidazolidin-2-one Chemical compound OCN1C(O)C(O)N(CO)C1=O ZEYUSQVGRCPBPG-UHFFFAOYSA-N 0.000 claims description 6
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- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 claims description 4
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
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- 125000005647 linker group Chemical group 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
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- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 3
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 claims description 3
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 229960003330 pentetic acid Drugs 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 2
- QQLILYBIARWEIF-UHFFFAOYSA-N 2-(2-hydroxyethylsulfonyl)ethanol Chemical compound OCCS(=O)(=O)CCO QQLILYBIARWEIF-UHFFFAOYSA-N 0.000 claims description 2
- XYOSFLPUWVWHOA-UHFFFAOYSA-N 2-ethylidenepropane-1,3-diol;urea Chemical compound NC(N)=O.CC=C(CO)CO XYOSFLPUWVWHOA-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
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- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000001014 amino acid Nutrition 0.000 claims description 2
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- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- MIGNWTQKRPNYLP-UHFFFAOYSA-N but-2-ene-2,3-diol urea Chemical compound NC(=O)N.OC(=C(C)O)C MIGNWTQKRPNYLP-UHFFFAOYSA-N 0.000 claims description 2
- WVJOGYWFVNTSAU-UHFFFAOYSA-N dimethylol ethylene urea Chemical compound OCN1CCN(CO)C1=O WVJOGYWFVNTSAU-UHFFFAOYSA-N 0.000 claims description 2
- UPOVSWVIQVHMOK-UHFFFAOYSA-N ethyl n,n-bis(hydroxymethyl)carbamate Chemical compound CCOC(=O)N(CO)CO UPOVSWVIQVHMOK-UHFFFAOYSA-N 0.000 claims description 2
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
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- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 229960001484 edetic acid Drugs 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 28
- 239000000758 substrate Substances 0.000 abstract description 17
- 230000003373 anti-fouling effect Effects 0.000 abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 239000008279 sol Substances 0.000 description 49
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 20
- 239000011521 glass Substances 0.000 description 11
- 229910001629 magnesium chloride Inorganic materials 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- 238000000746 purification Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CLSIFQGHPQDTHQ-DTWKUNHWSA-N (2s,3r)-2-[(4-carboxyphenyl)methyl]-3-hydroxybutanedioic acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC1=CC=C(C(O)=O)C=C1 CLSIFQGHPQDTHQ-DTWKUNHWSA-N 0.000 description 2
- JRSCGPHVSNGOMK-UHFFFAOYSA-N 3-[methyl(propyl)amino]propyl 2-methylprop-2-enoate Chemical compound CCCN(C)CCCOC(=O)C(C)=C JRSCGPHVSNGOMK-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
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- DCCFDSVMGPRANE-UHFFFAOYSA-N dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;acetate Chemical compound CC(O)=O.CN(C)CCOC(=O)C(C)=C DCCFDSVMGPRANE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
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- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- TYFSYONDMQEGJK-UHFFFAOYSA-N 2-(2,2-dihydroxyethylamino)acetic acid Chemical compound OC(O)CNCC(O)=O TYFSYONDMQEGJK-UHFFFAOYSA-N 0.000 description 1
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- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
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- PZZHMLOHNYWKIK-UHFFFAOYSA-N eddha Chemical compound C=1C=CC=C(O)C=1C(C(=O)O)NCCNC(C(O)=O)C1=CC=CC=C1O PZZHMLOHNYWKIK-UHFFFAOYSA-N 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229950004354 phosphorylcholine Drugs 0.000 description 1
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
-
- 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
- C09D7/63—Additives non-macromolecular organic
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of high molecular materials, and discloses a super-hydrophilic self-cleaning coating sol containing a zwitterionic polymer, and a preparation method and application thereof. The sol comprises the following components in parts by mass: 100 parts of polymer containing zwitterion groups, 1-100 parts of cross-linking agent, 0.01-100 parts of carboxyl-containing compound, 0.01-20 parts of catalyst and water. After the super-hydrophilic self-cleaning coating sol is coated, the super-hydrophilic self-cleaning coating can be simply and conveniently constructed on the surfaces of different substrates in a large area, so that the surface of a material with the super-hydrophilic self-cleaning characteristic is obtained; the obtained coating can be firmly attached to the surface of a substrate, the water contact angle of the coating can be less than 10 degrees, the underwater oil drop contact angle is close to 180 degrees, and the coating can provide the product or the article with the following characteristics such as self-cleaning property, antifouling property, chemical resistance, antibacterial adhesion and the like besides super-hydrophilicity, and has very wide application.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a super-hydrophilic self-cleaning coating sol containing a zwitter-ion-group polymer, and a preparation method and application thereof.
Background
In recent years, super-wetting surfaces created by controlling the wettability of solid surfaces have received attention from the industry. The super-hydrophilic surface has unique self-cleaning performance, has good application prospect in the fields of bathroom materials, biomedical coatings, antifouling coatings and the like, and is rapidly developed in recent years. In order to obtain a super-hydrophilic surface, a coating with super-hydrophilic property is required to be coated on the surface of the material. Therefore, the research and development of the coating material with the super-hydrophilic performance have important application value and economic benefit.
The super-hydrophilic surfaces reported at present mainly comprise inorganic super-hydrophilic surfaces and macromolecular super-hydrophilic surfaces. Among the inorganic super-hydrophilic materials, tiO 2 And SiO 2 Of which TiO is most studied 2 The coating shows excellent photoinduced super-hydrophilicity, but the hydrophilic property of the coating is easily influenced by external factors, and the material cannot exert the effect in places without light or weak light; siO 2 2 The surface is very easy to generate hydroxyl groups to obtain super-hydrophilicity, but is based on SiO 2 The nano hydrophilic coating product has the problems of poor adhesive force and poor stability, and cannot meet the requirement of long-term use. The super-hydrophilic surface of the polymer is usually super-hydrophilic by absorbing water on the surface of the coating film by the water absorption of the resin by using a hydrophilic polymer having a polar group such as a hydroxyl group, a carboxyl group, or an amide group. The designability of the molecular structure of the high polymer material and the diversity of hydrophilic functional groups provide feasibility for the preparation and the application of the super-hydrophilic high polymer material.
From the bionics perspective, people carry out biomimetic molecular design according to the chemical composition and structure of the hydrophilic end group of cell membrane lecithin, and introduce zwitterionic groups (such as phosphorylcholine, sulfabetaine, carboxyamidobetaine and the like) into the surface of the material. The zwitterionic compound with the same quantity of positive and negative charges and water molecules have strong interaction through ion solvation, so that a firmer hydration layer is formed around the zwitterionic structure, and the characteristics of better hydrophilicity, excellent biocompatibility, blood compatibility, anti-biological adhesion and the like are endowed on the surface of the zwitterionic compound and the surface modified by the zwitterionic compound. At present, scientists have tried various methods to construct zwitterionic groups on the surface of materials, such as self-assembled monolayer films, surface atom transfer radical polymerization, surface grafting, etc., and these research methods are still under the research and study stage. How to modify the zwitterionic material to the surface of the substrate simply, conveniently, stably and in a large area is still one of the very challenging problems in the process of constructing the zwitterionic surface.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a super-hydrophilic self-cleaning coating sol containing a zwitterionic polymer.
The invention also aims to provide a preparation method of the super-hydrophilic self-cleaning coating sol containing the zwitterionic polymer.
The invention further aims to provide application of the super-hydrophilic self-cleaning coating sol containing the zwitterionic polymer.
The super-hydrophilic self-cleaning coating sol containing the zwitterionic polymer can be used for preparing a coating with super-hydrophilic characteristics on the surface simply, conveniently and in a large area after coating, the water contact angle of the coating can be smaller than 10 degrees, the underwater oil drop contact angle is close to 180 degrees, and the coating can be firmly attached to the surface of a substrate.
The purpose of the invention is realized by the following scheme:
a super-hydrophilic self-cleaning coating sol containing a zwitterionic group polymer comprises the following components in parts by mass: 100 parts of polymer containing zwitterion group, 1-100 parts of cross-linking agent, 0.01-100 parts of compound containing carboxyl, 0.01-20 parts of catalyst and water.
Further, the super-hydrophilic self-cleaning coating sol containing the zwitterionic group polymer comprises the following components in parts by mass: 100 parts of zwitterion group-containing polymer, 1-50 parts of cross-linking agent, 0.01-10 parts of carboxyl-containing compound, 0.01-10 parts of catalyst and water.
The super-hydrophilic self-cleaning coating sol containing the zwitterionic group polymer can obtain different solid contents by changing the water content, and the solid content can be 0.1-60%.
In the sol, the cross-linking agent can comprise at least one of urea-formaldehyde resin, trimethylol melamine, hexamethylol melamine, methylated trimethylol melamine, methylated hexamethylol melamine, dimethylol ethylene urea resin, dimethylol dihydroxy ethylene urea resin, dimethylol ethyl triazone, dimethylol propylene urea, dimethylol urethane, bisphenol A diglycidyl ether, beta-bis hydroxyethyl sulfone, dimethyl dihydroxy ethylene urea, waterborne polyurethane and the like.
The cross-linking agent adopted by the invention has a plurality of active groups, and can be combined with polar groups on other material molecular structures to form a covalent bond under a certain condition, such as reaction with hydroxyl groups on other material molecular structures, condensation to form ether bonds and the like; in addition, the crosslinking agent itself can be condensed into macromolecules, and can be stably deposited on the surface of the base material.
In the sol of the present invention, the carboxyl group-containing compound may include at least one of citric acid, malic acid, amino acids, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), ethyleneglycol bis (2-aminoethyl ether) tetraacetic acid (EGTA), ethylenediamine diacetic acid (EDDHA), cyclohexanediaminetetraacetic acid (CDTA), S-ethylenediamine disuccinic acid (S, S-EDDS), diethyltriacetic acid (NTA), glutamic acid N, N-tetrasodium diacetate (GLDA), methylglycinediacetic acid (MGDA), hydroxyethylethylenediamine triacetic acid (HEDTA), N-Dihydroxyethylglycine (DEG), salts thereof, and the like.
The carboxyl group in the carboxyl-containing compound has reactivity, and the carboxyl group is dehydrated into cyclic anhydride under certain conditions, so that the cyclic anhydride has high reactivity and is easy to react with polar groups on other material molecules, such as hydroxyl on other material molecules, to generate ester.
In the sol of the present invention, the catalyst may include at least one of inorganic acid, organic acid, ammonium salt, inorganic metal salt, basic aluminum chloride, sodium tetrafluoroborate, and the like.
Further, the ammonium salt may include at least one of ammonium chloride, ammonium sulfate, ammonium nitrate, triethanolamine hydrochloride, ammonium dihydrogen phosphate, ammonium thiocyanate, and the like.
Further, the inorganic metal salt may include at least one of magnesium chloride, magnesium nitrate, zinc chloride, zinc nitrate, and the like.
In the sol, the polymer containing the zwitterionic group can be obtained by reacting a zwitterionic monomer and a comonomer under the action of an initiator.
Further, the zwitterionic monomer comprises at least one of 2- (methacryloyloxy) ethyl-2- (trimethylamino) ethyl phosphate and betaine type zwitterionic vinyl monomer.
Further, the chemical formula of the betaine type zwitterionic vinyl monomer is CH 2 ＝C(Ra)-L1-N + (Rb)(Rc)-L2-A(＝O)O - Or CH 2 ＝C(Ra)-L1-N + (Rb)(Rc)-O - (ii) a Wherein, CH 2 = C (Ra) is a polymerizable group, ra being hydrogen or methyl; n is a radical of + Is a cationic center; a (= O) O - Is an anionic group, A is C, SO, P or PO; rb and Rc, which are the same or different, are each hydrogen, alkyl or aryl; l1 is a linking group from the cationic center to the polymerizable group and can be-C (= O) O- (CH) 2 ) n -or-C (= O) NH- (CH) 2 ) n -n is an integer from 1 to 10; l2 is a cationic to anionic center linker and can be- (CH) 2 ) n And n is an integer of 1 to 10.
For example, the betaine type zwitterionic vinyl monomer may include at least one of 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate (SBMA), methacryloyloxyethyl dimethyl ammonium acetate (CBMA), and the like.
Further, the comonomer may include at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and the like.
Further, the amount mass ratio of the zwitterionic monomer to the comonomer can be 100: (0-1000), more preferably 100: (0-100).
Further, the amount of the initiator is preferably 0.1 to 100% by mass based on the zwitterionic monomer. The initiator may include at least one of persulfate initiators, azo initiators, peroxide initiators, oxidation-reduction system initiators, and the like.
Further, the reaction temperature can be from normal temperature to 90 ℃; the reaction time may be 0.4 to 24 hours. The reaction is preferably carried out with stirring.
Further, the reaction is carried out in a solvent environment. The amount of the solvent used is preferably 1 to 100 times the mass of the zwitterionic monomer. The solvent may include at least one of water, ethanol, methanol, ethyl acetate, and the like.
Further, after the reaction, a purified polymer containing a zwitterionic group can be obtained by purification and drying. The purification can be carried out by precipitation with a poor solvent.
The super-hydrophilic self-cleaning coating sol containing the zwitterionic group polymer is prepared by mixing the components according to the using amount and uniformly stirring.
The polymer containing the zwitter-ion group with the hydroxyl/epoxy group is prepared by free radical polymerization, the hydroxyl/epoxy group on the structure can chemically react with an active group on a cross-linking agent to form a covalent bond under a certain condition, can chemically react with a carboxyl group on a carboxyl-containing compound and a cyclic anhydride group formed by dehydration of the carboxyl group to form a covalent bond, and the polymer containing the zwitter-ion group with the hydroxyl/epoxy group can also internally react with the molecular structure under a certain condition to form a cross-linking reaction and then is deposited on the surface of a base material.
The invention also provides the application of the super-hydrophilic self-cleaning coating sol containing the zwitterionic polymer in surface modification; the method comprises the application of preparing the super-hydrophilic self-cleaning coating, in particular to the super-hydrophilic self-cleaning coating sol containing the zwitterionic polymer, which is disclosed by the invention, is coated on a substrate and is cured for 0.5-200min at the temperature of 0-200 ℃, so that the super-hydrophilic self-cleaning coating is obtained.
After curing, post-treatment purification, such as cleaning, drying and the like, can be carried out.
The super-hydrophilic self-cleaning coating sol containing the zwitterionic polymer can be used for preparing a coating with super-hydrophilic characteristics on the surface simply, conveniently and in a large area after coating, and the coating can be firmly attached to the surface of a base material.
Based on the chemical properties of the cross-linking agent, the carboxyl-containing compound and the polymer containing the zwitter-ion groups in the super-hydrophilic self-cleaning coating sol component, the condensation of the cross-linking agent and the carboxyl-containing compound and the chemical reaction principle of the three, the zwitter-ion group polymer is simply, conveniently and stably constructed on the surface of the material through the synergistic promotion effect of the cross-linking agent and the carboxyl-containing compound, and the surface of the material with the super-hydrophilic self-cleaning characteristic is obtained.
The coating sol of the present invention is in a liquid form when used, and thus the coating method may include various coating processes suitable for liquid sol, such as dipping, spraying, curtain coating, wiping, and the like.
The super-hydrophilic self-cleaning coating sol can form coatings on the surfaces of different substrates, such as glass materials, metal materials, ceramic materials, high polymer materials, artificial high polymer fabrics, natural high polymer fabrics and the like, the water contact angle of the obtained coatings can be less than 10 degrees, the underwater oil drop contact angle is close to 180 degrees, and besides super-hydrophilicity, the super-hydrophilic self-cleaning coating sol can also provide the following characteristics for products or articles, such as self-cleaning property, antifouling property, chemical resistance, antibacterial adhesion and the like. Furthermore, the coating sol of the present invention can be made to have a very wide range of uses by adjusting the type of solvent in the formulation, the amount of compounding materials, and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention takes the polymer containing the zwitter-ion group as the functional material, constructs the surface of the functional coating with the super-hydrophilic self-cleaning characteristic under the combined action of the cross-linking agent and the carboxyl-containing compound, has simple and convenient preparation method, stable coating, low cost and easily controlled operation condition, and effectively solves the problems of poor durability, difficult and complex preparation process and the like of the existing super-hydrophilic coating.
2. The super-hydrophilic sol prepared by the invention has wide substrate adaptability, and can be used for treating different materials; the preparation of the surface of the coating with the large-area super-hydrophilic function can be realized, the cost is low, the application is convenient, and the application and the development of the super-hydrophilic self-cleaning function coating technology are facilitated.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a reaction schematic diagram of constructing a super-hydrophilic self-cleaning coating on the surface of a substrate by using the super-hydrophilic self-cleaning coating sol.
FIG. 2 is SEM images of the glass surface before and after the self-cleaning coating is formed.
FIG. 3 is SEM images of the surface of PET non-woven fabric before and after the self-cleaning coating is formed.
FIG. 4 is an infrared spectrum before and after the self-cleaning coating is constructed on the glass surface.
FIG. 5 is an infrared spectrum before and after the self-cleaning coating is constructed on the surface of the PET non-woven fabric.
FIG. 6 is a water contact angle diagram before and after the self-cleaning coating is constructed on the glass surface.
FIG. 7 is a diagram showing underwater oil drop contact angles before and after a self-cleaning coating constructed on a glass surface is modified.
FIG. 8 is a water contact angle diagram before and after the modification of the self-cleaning coating constructed on the surface of the PET non-woven fabric.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The materials referred to in the following examples are commercially available without specific reference. The method is a conventional method unless otherwise specified.
Example 1: preparation of zwitterionic group-containing polymers
Mixing 40 parts by mass of 3- (2-methacryloyloxyethyl dimethylamino) propane Sulfonate (SBMA), 10 parts by mass of hydroxyethyl methacrylate, 1 part by mass of ammonium persulfate and 500 parts by mass of water, heating and reacting at 80 ℃ for 8 hours, and purifying and drying to obtain the polymer containing the zwitterion group.
Example 2: preparation of zwitterionic group-containing polymers
Mixing 50 parts by mass of 3- (2-methacryloyloxyethyl dimethylamino) propane Sulfonate (SBMA), 1 part by mass of ammonium persulfate and 500 parts by mass of water, heating to react for 8 hours at the temperature of 80 ℃, and purifying and drying to obtain the polymer containing the zwitterion group.
Example 3: preparation of zwitterionic group-containing polymers
Mixing 40 parts by mass of methacryloyloxyethyl dimethylammonium acetate (CBMA), 10 parts by mass of glycidyl methacrylate, 1 part by mass of azobisisobutyronitrile and 500 parts by mass of methanol, heating and refluxing for reaction at 70 ℃ for 12 hours, and purifying and drying to obtain the polymer containing the zwitterion group.
Example 4: preparation of zwitterionic group-containing polymers
Mixing 40 parts by mass of 2- (methacryloyloxy) ethyl-2- (trimethylamino) ethyl phosphate, 15 parts by mass of glycidyl methacrylate, 1 part by mass of azobisisobutyronitrile and 500 parts by mass of methanol, heating and refluxing for reaction at 70 ℃ for 12 hours, and purifying and drying to obtain the polymer containing the zwitterion group.
Example 5
A super-hydrophilic self-cleaning coating sol containing a zwitterionic group polymer comprises the following components in parts by mass: 100 parts by mass of the zwitterionic group-containing polymer obtained in example 1, 30 parts by mass of dimethylol dihydroxy ethylene urea, 2 parts by mass of ethylenediaminetetraacetic acid, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; the components are mixed according to a proportion and stirred uniformly to obtain the super-hydrophilic self-cleaning coating sol.
Example 6
A super-hydrophilic self-cleaning coating sol containing a zwitterionic group polymer comprises the following components in parts by mass: 100 parts by mass of the polymer containing a zwitterionic group obtained in example 1, 30 parts by mass of hexamethylolmelamine, 1 part by mass of citric acid, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; the components are mixed according to a proportion and stirred uniformly to obtain the super-hydrophilic self-cleaning coating sol.
Example 7
A super-hydrophilic self-cleaning coating sol containing a zwitterionic group polymer comprises the following components in parts by mass: 100 parts by mass of the zwitterionic group-containing polymer obtained in example 2, 30 parts by mass of dimethylol dihydroxy ethylene urea, 2 parts by mass of ethylenediamine tetraacetic acid, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; the components are mixed according to a proportion and stirred uniformly to obtain the super-hydrophilic self-cleaning coating sol.
Example 8
A super-hydrophilic self-cleaning coating sol containing a zwitterionic group polymer comprises the following components in parts by mass: 100 parts by mass of the polymer containing a zwitterionic group obtained in example 3, 30 parts by mass of hexamethylolmelamine, 1 part by mass of citric acid, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; the components are mixed according to a proportion and stirred uniformly to obtain the super-hydrophilic self-cleaning coating sol.
Example 9
A super-hydrophilic self-cleaning coating sol containing a zwitterionic group polymer comprises the following components in parts by mass: 100 parts by mass of the polymer containing a zwitterionic group obtained in example 1, 20 parts by mass of dimethylol dihydroxy ethylene urea, 1.5 parts by mass of ethylenediamine tetraacetic acid, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; the components are mixed according to a certain proportion and stirred evenly to obtain the super-hydrophilic self-cleaning coating sol.
Example 10
A super-hydrophilic self-cleaning coating sol containing a zwitterionic group polymer comprises the following components in parts by mass: 100 parts by mass of the polymer containing a zwitterionic group obtained in example 1, 40 parts by mass of hexamethylolmelamine, 2 parts by mass of citric acid, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; the components are mixed according to a proportion and stirred uniformly to obtain the super-hydrophilic self-cleaning coating sol.
Comparative example 1
A coating sol comprises the following components in parts by mass: 100 parts by mass of the polymer containing a zwitterionic group obtained in example 1, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; the components are mixed according to the proportion and stirred evenly to obtain the coating sol.
Comparative example 2
A coating sol comprises the following components in parts by mass: 100 parts by mass of the polymer containing a zwitterionic group obtained in example 1, 30 parts by mass of dimethylol dihydroxy ethylene urea, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; the components are mixed according to the proportion and stirred evenly to obtain the coating sol.
Comparative example 3
The coating sol comprises the following components in parts by mass: 100 parts by mass of the polymer containing a zwitterionic group obtained in example 1, 2 parts by mass of ethylenediaminetetraacetic acid, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; the components are mixed according to the proportion and stirred evenly to obtain the coating sol.
The sols prepared in the above examples and comparative examples were coated on a substrate, respectively, cured at 200 ℃ for 10min, and post-treated and purified (e.g., cleaned, dried, etc.), to obtain a coating.
FIG. 1 is a reaction schematic diagram of constructing a super-hydrophilic self-cleaning coating on the surface of a substrate by using the super-hydrophilic self-cleaning coating sol. The hydrophilicity of the coating is tested, and the hydrophilicity stability of the coating is evaluated, namely the stability of the coating on the surface of the substrate is evaluated by recording the contact angle of water drops of the material before and after cleaning after 50 times of cleaning. The test results are shown in table 1 and fig. 2 to 8.
TABLE 1 contact angle of water drop on substrate surface
As can be seen from table 1, after the super-hydrophilic self-cleaning coating sol is modified, the super-hydrophilic self-cleaning coating is constructed on the surface of the substrate, and the water contact angles of the super-hydrophilic self-cleaning coating are less than 10 degrees, so that excellent hydrophilicity is shown. After multiple times of cleaning, in example 5, the contact angle of a water drop of different materials is still less than 10 degrees, and stable super-hydrophilicity is shown; in contrast, it can be seen from the results of comparative examples 1 to 3 that after a plurality of times of washing, the water contact angle of the material becomes large and the hydrophilic stability thereof becomes poor. Therefore, under the combined action of the cross-linking agent and the carboxyl-containing compound in the system, the coating can keep better hydrophilic stability.
FIGS. 2 to 8 are test charts before and after surface modification of various substrates with the sol prepared in example 5. As is apparent from FIGS. 2 and 3, the superhydrophilic self-cleaning coating sol of the present invention forms a uniform coating on the surface of the substrate. As can be seen from FIGS. 4 and 5, the infrared spectrum of the glass after modification is 1040cm -1 The telescopic vibration absorption peak of the sulfonic acid group appears at 1720cm -1 A stretching vibration absorption peak belonging to-C = O appears; the infrared spectrum of the modified PET is 1040cm -1 A telescopic vibration absorption peak of a sulfonic acid group appears; indicating that the coating is successfully built on the surface of the substrate. As can be seen from fig. 6 and 7, after the glass surface is modified, the glass surface has super-hydrophilic property, and the contact angle is less than 10 °; before modification, the contact angle of underwater oil drops on the surface of the glass is about 125 degrees, after modification, the surface of the glass shows the underwater super-oleophobic characteristic, the contact angle is close to 180 degrees, the excellent underwater super-oleophobic characteristic is shown, and the surface with the characteristic can show the oil stain prevention function underwater. As can be seen from FIG. 8, before modification, the water distribution contact angle of the PET non-woven fabric is close to 130 degrees, and the PET non-woven fabric presents hydrophobicity; after modification, the surface of the PET film shows super-hydrophilic characteristics, and water drops contact with the modified PET surface, namely are wetted and absorbed, so that the PET film shows super-hydrophilic characteristics. The test results of other embodiments are similar and are not repeated herein.
Therefore, the super-hydrophilic self-cleaning coating sol can form coatings on different substrate surfaces, such as glass materials, metal materials, ceramic materials, high polymer materials, artificial high polymer fabrics, natural high polymer fabrics and the like, the water contact angle of the obtained coatings is less than 10 degrees, the underwater oil drop contact angle is close to 180 degrees, and the super-hydrophilic self-cleaning coating sol can provide products or articles with the following characteristics such as self-cleaning property, antifouling property, chemical resistance, antibacterial adhesion and the like and has very wide application.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A super-hydrophilic self-cleaning coating sol containing a zwitterionic group polymer is characterized by comprising the following components in parts by mass: 100 parts of polymer containing zwitterion groups, 1-100 parts of cross-linking agent, 0.01-100 parts of carboxyl-containing compound, 0.01-20 parts of catalyst and water.
2. A super-hydrophilic self-cleaning coating sol containing a zwitterionic group polymer is characterized by comprising the following components in parts by mass: 100 parts of zwitterion group-containing polymer, 1-50 parts of cross-linking agent, 0.01-10 parts of carboxyl-containing compound, 0.01-10 parts of catalyst and water.
3. The superhydrophilic self-cleaning coating sol containing zwitterionic group-containing polymer of claim 1 or 2, characterized in that: the polymer containing the zwitter-ion group comprises a zwitter-ion monomer and a comonomer which are obtained by reaction under the action of an initiator.
4. The superhydrophilic self-cleaning coating sol containing zwitterionic group polymer of claim 3, characterized in that: the zwitterionic monomer comprises at least one of 2- (methacryloyloxy) ethyl-2- (trimethyl amino) ethyl phosphate and betaine type zwitterionic vinyl monomer.
5. The superhydrophilic self-cleaning coating sol containing zwitterionic group polymer of claim 4, characterized in that: the betaine type zwitterionic alkenesThe chemical formula of the monomer-like is CH 2 ＝C(Ra)-L1-N + (Rb)(Rc)-L2-A(＝O)O - Or CH 2 ＝C(Ra)-L1-N + (Rb)(Rc)-O - (ii) a Wherein, CH 2 = C (Ra) is a polymerizable group, ra is hydrogen or methyl; n is a radical of + Is a cationic center; a (= O) O - Is an anionic group, A is C, SO, P or PO; rb and Rc, which are the same or different, are each hydrogen, alkyl or aryl; l1 is a linking group from the cationic center to the polymerizable group and is-C (= O) O- (CH) 2 ) n -or-C (= O) NH- (CH) 2 ) n -n is an integer from 1 to 10; l2 is a linking group from a cationic center to an anionic center and is- (CH) 2 ) n And n is an integer of 1 to 10.
6. The superhydrophilic self-cleaning coating sol containing zwitterionic group polymer of claim 3, characterized in that: the comonomer comprises at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate and allyl glycidyl ether.
7. The superhydrophilic self-cleaning coating sol containing zwitterionic group-containing polymer of claim 1 or 2, characterized in that: the cross-linking agent comprises at least one of urea-formaldehyde resin, trimethylol melamine, hexamethylol melamine, methylated trimethylol melamine, methylated hexamethylol melamine, dimethylol ethylene urea resin, dimethylol dihydroxy ethylene urea resin, dimethylol ethyl triazone, dimethylol propylene urea, dimethylol urethane, bisphenol A diglycidyl ether, beta-bis hydroxyethyl sulfone, dimethyl dihydroxy ethylene urea and water-based polyurethane.
8. The superhydrophilic self-cleaning coating sol containing zwitterionic group-containing polymer of claim 1 or 2, characterized in that: the carboxyl-containing compound comprises at least one of citric acid, malic acid, amino acid, ethylene diamine tetraacetic acid, nitrilotriacetic acid, diethylene triamine pentaacetic acid, ethylene glycol bis (2-aminoethyl ether) tetraacetic acid, ethylene diamine diacetic acid, cyclohexane diamine tetraacetic acid, S-ethylene diamine disuccinic acid, diethyl triacetic acid, glutamic acid tetrasodium N, N-diacetate, methyl glycine diacetic acid, hydroxyethyl ethylene diamine triacetic acid, N-dihydroxyethyl glycine and salts thereof.
9. The superhydrophilic self-cleaning coating sol containing zwitterionic group-containing polymer of claim 1 or 2, characterized in that: the catalyst comprises at least one of inorganic acid, organic acid, ammonium salt, inorganic metal salt, basic aluminum chloride and sodium tetrafluoroborate.
10. Use of the superhydrophilic self-cleaning coating sol containing zwitterionic group-containing polymer as claimed in claim 1 or 2 in surface modification.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1782219A (en) * | 2004-12-01 | 2006-06-07 | 日清纺织株式会社 | Anti-pollution fiber structure and its processing method |
| CN105413236A (en) * | 2015-12-18 | 2016-03-23 | 华南理工大学 | Super-hydrophilic oil water separation net film with antifouling and antibacterial functions and preparation as well as application thereof |
| CN109890918A (en) * | 2016-12-28 | 2019-06-14 | 株式会社Lg化学 | Hydrophilic coating compositions |
| CN110804144A (en) * | 2017-07-21 | 2020-02-18 | 天津大学 | Cationic-zwitterionic block copolymers |
-
2022
- 2022-08-09 CN CN202210951100.7A patent/CN115181468B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1782219A (en) * | 2004-12-01 | 2006-06-07 | 日清纺织株式会社 | Anti-pollution fiber structure and its processing method |
| CN105413236A (en) * | 2015-12-18 | 2016-03-23 | 华南理工大学 | Super-hydrophilic oil water separation net film with antifouling and antibacterial functions and preparation as well as application thereof |
| CN109890918A (en) * | 2016-12-28 | 2019-06-14 | 株式会社Lg化学 | Hydrophilic coating compositions |
| CN110804144A (en) * | 2017-07-21 | 2020-02-18 | 天津大学 | Cationic-zwitterionic block copolymers |
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| CN115181468B (en) | 2024-03-05 |
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