CN115181468B - 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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- CN115181468B CN115181468B CN202210951100.7A CN202210951100A CN115181468B CN 115181468 B CN115181468 B CN 115181468B CN 202210951100 A CN202210951100 A CN 202210951100A CN 115181468 B CN115181468 B CN 115181468B
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- 238000000576 coating method Methods 0.000 title claims abstract description 96
- 239000011248 coating agent Substances 0.000 title claims abstract description 88
- 238000004140 cleaning Methods 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- -1 carboxyl compound Chemical class 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 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
- 150000001875 compounds Chemical class 0.000 claims description 15
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 8
- 238000000034 method Methods 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
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 6
- 229960003237 betaine Drugs 0.000 claims description 6
- 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
- 230000009471 action Effects 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
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- 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
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 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
- 229960003330 pentetic acid Drugs 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 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
- DFGLHEOSIBIARJ-UHFFFAOYSA-N 5-[3-hydroxy-2-(hydroxymethyl)propyl]-1H-triazin-6-one Chemical compound C(O)C(CC=1C(NN=NC=1)=O)CO DFGLHEOSIBIARJ-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 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
- 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
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 28
- 239000000758 substrate Substances 0.000 abstract description 20
- 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
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 229910001629 magnesium chloride Inorganic materials 0.000 description 10
- 238000002156 mixing Methods 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 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 235000015165 citric acid Nutrition 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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
- 238000000746 purification Methods 0.000 description 3
- 239000007787 solid Substances 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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 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
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 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
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GJMPSRSMBJLKKB-UHFFFAOYSA-N 3-methylphenylacetic acid Chemical compound CC1=CC=CC(CC(O)=O)=C1 GJMPSRSMBJLKKB-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000035587 bioadhesion Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 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
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229950004354 phosphorylcholine Drugs 0.000 description 1
- PYJNAPOPMIJKJZ-UHFFFAOYSA-N phosphorylcholine chloride Chemical compound [Cl-].C[N+](C)(C)CCOP(O)(O)=O PYJNAPOPMIJKJZ-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229940117957 triethanolamine hydrochloride Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- 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
Abstract
The invention belongs to the technical field of high molecular materials, and discloses a super-hydrophilic self-cleaning coating sol containing a zwitterionic group polymer, and a preparation method and application thereof. The sol comprises the following components in parts by mass: 100 parts of polymer containing zwitterionic groups, 1-100 parts of cross-linking agent, 0.01-100 parts of carboxyl compound, 0.01-20 parts of catalyst and water. The super-hydrophilic self-cleaning coating sol disclosed by the invention can simply, conveniently and widely construct super-hydrophilic coatings on different substrate surfaces to obtain the material surface with super-hydrophilic self-cleaning characteristics; the obtained coating can be firmly adhered to the surface of a substrate, the water contact angle of the coating can be less than 10 degrees, the contact angle of underwater oil drops is close to 180 degrees, and the coating can provide products or articles 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 molecular materials, and particularly relates to a super-hydrophilic self-cleaning coating sol containing a polymer with zwitterionic groups, and a preparation method and application thereof.
Background
In recent years, super-wetted surfaces produced 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 has been rapidly developed in recent years. In order to obtain a super-hydrophilic surface, a coating layer with super-hydrophilic performance needs to be coated on the surface of the material. Therefore, the development of the coating material with super-hydrophilic property has important application value and economic benefit.
The super-hydrophilic surfaces reported at present mainly comprise inorganic super-hydrophilic surfaces and high-molecular super-hydrophilic surfaces. In the inorganic super-hydrophilic material, tiO 2 And SiO 2 Most studied, among them, tiO 2 The coating shows excellent photoinduced super-hydrophilicity, but the hydrophilic performance is easily influenced by external factor light, and the material cannot exert effect in places without light or weak light; siO (SiO) 2 The surface is extremely 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 stability, and can not meet the long-term use requirement. The super-hydrophilic surface of polymer is usually prepared by hydrophilic polymer containing polar groups such as hydroxyl, carboxyl, amide, etcThe water absorption of the resin is used to absorb the water on the surface of the coating film to realize the super-hydrophilicity of the coating. The designability of the molecular structure of the high molecular material and the diversity of the hydrophilic functional groups provide feasibility for the preparation and application of the super-hydrophilic high molecular material.
From the bionics perspective, people carry out biomimetic molecular design according to the chemical composition and structure of the cell membrane lecithin hydrophilic end group, and zwitterionic groups (such as phosphorylcholine, sulfabetaine, carboxyamine betaine and the like) are introduced into the surface of the material. The zwitterionic compound with equivalent positive and negative charges has strong interaction with water molecules through ion solvation, so that a firmer hydration layer is formed around the zwitterionic structure, and the characteristic of the zwitterionic compound endows the surface of the zwitterionic compound and the surface modified by the zwitterionic compound with better hydrophilicity, excellent biocompatibility, blood compatibility, bioadhesion resistance and other characteristics. Currently, scientists have tried various methods for constructing zwitterionic groups on the surface of materials, such as self-assembled monolayer films, surface atom transfer radical polymerization methods, surface grafting methods, and the like, and all of these research methods are still in the research stage. How to simply, conveniently and firmly modify zwitterionic materials to substrate surfaces over large areas remains one of the very challenging challenges faced in the current process of constructing zwitterionic surfaces.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the primary purpose of the invention is to provide a super-hydrophilic self-cleaning coating sol containing a polymer with zwitterionic groups.
The invention also aims at providing a preparation method of the super-hydrophilic self-cleaning coating sol containing the polymer with the zwitterionic groups.
It is a further object of the present invention to provide the use of the above-mentioned super hydrophilic self-cleaning coating sol containing a zwitterionic group polymer.
The super-hydrophilic self-cleaning coating sol containing the zwitterionic group polymer can be coated to prepare the coating with super-hydrophilic characteristic on the surface simply, conveniently and in a large area, the water contact angle of the coating can be smaller than 10 degrees, the contact angle of underwater oil drops is close to 180 degrees, and the coating can be firmly attached to the surface of a substrate.
The aim of the invention is achieved by the following scheme:
the super-hydrophilic self-cleaning coating sol containing the zwitterionic group polymer comprises the following components in parts by mass: 100 parts of polymer containing zwitterionic groups, 1-100 parts of cross-linking agent, 0.01-100 parts of carboxyl compound, 0.01-20 parts of catalyst and water.
Further, the super-hydrophilic self-cleaning coating sol containing the polymer with the zwitterionic groups comprises the following components in parts by mass: 100 parts of polymer containing zwitterionic groups, 1-50 parts of cross-linking agent, 0.01-10 parts of carboxyl 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 of the present invention, the crosslinking agent may include 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 triazinone, dimethylol propylene urea, dimethylol urethane, bisphenol a diglycidyl ether, beta-bis hydroxyethyl sulfone, dimethyl dihydroxy ethylene urea, aqueous 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 molecular structures of other materials to form covalent bonds under certain conditions, such as reaction with hydroxyl groups on molecular structures of other materials, condensation to form ether bonds and the like; in addition, the cross-linking agent can be condensed into macromolecules, so that the cross-linking agent can be stably deposited on the surface of the substrate.
In the sol of the present invention, the carboxyl group-containing compound may include at least one of citric acid, malic acid, amino acid, ethylenediamine tetraacetic acid (EDTA), aminotriacetic acid (NTA), diethylenetriamine pentaacetic acid (DTPA), ethyleneglycol bis (2-aminoethylether) tetraacetic acid (EGTA), ethylenediamine diacetic acid (EDDHA), cyclohexanediamine tetraacetic acid (CDTA), S-ethylenediamine disuccinic acid (S, S-EDDS), diethylenetriacetic acid (NTA), glutamic acid N, N-tetraacetic acid (GLDA), methylglycine diacetic acid (MGDA), hydroxyethylethylenediamine triacetic acid (HEDTA), N-Dihydroxyethylglycine (DEG), and salts thereof.
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 higher reactivity, and is easy to react with polar groups on other material molecules, such as hydroxyl groups on other material molecules to generate esters.
In the sol of the present invention, the catalyst may include at least one of an inorganic acid, an organic acid, an ammonium salt, an 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, monoammonium 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 groups 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 amphoteric ion alkene monomer is CH 2 ＝C(Ra)-L1-N + (Rb)(Rc)-L2-A(＝O)O - Or CH (CH) 2 ＝C(Ra)-L1-N + (Rb)(Rc)-O - The method comprises the steps of carrying out a first treatment on the surface of the Wherein CH is 2 =c (Ra) is a polymerizable group, ra is hydrogen or methyl; n (N) + Is a cationic center; a (=o) O - Is an anionic group, A is C, SO, P or PO; rb and Rc are the same or different and are each hydrogen, alkyl or aryl; l1 is a cationic center to polymerizable group linker, which 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 linker and may be- (CH) 2 ) n -n is an integer from 1 to 10.
For example, the betaine type zwitterionic vinyl monomer may include at least one of 3- (2-methacryloxyethyl dimethylamino) propane Sulfonate (SBMA), methacryloxyethyl 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 mass ratio of the amount of the zwitterionic monomer to the comonomer may be 100: (0-1000), more preferably 100: (0-100).
Further, the initiator is preferably used in an amount of 0.1 to 100% by mass of the zwitterionic monomer. The initiator may include at least one of persulfate initiator, azo-type initiator, peroxide-type initiator, oxidation-reduction system initiator, and the like.
Further, the temperature of the reaction may be from ambient 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 solvent is preferably used in an amount of 1 to 100 times the mass of the zwitterionic monomer. The solvent may include at least one of water, ethanol, methanol, ethyl acetate, etc.
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 adopting a non-good solvent for precipitation purification.
The super-hydrophilic self-cleaning coating sol containing the zwitterionic group polymer is prepared by mixing the components according to the amount and stirring uniformly.
The invention prepares the polymer containing the amphoteric ion group with the hydroxyl/epoxy group through free radical polymerization, the hydroxyl/epoxy group on the structure can be chemically reacted with the active group on the cross-linking agent to form a covalent bond under certain conditions, the polymer containing the amphoteric ion group with the hydroxyl/epoxy group can be chemically reacted with the carboxyl group on the carboxyl-containing compound and the cyclic anhydride group formed by dehydration of the carboxyl-containing compound to form a covalent bond, and the polymer containing the amphoteric ion group with the hydroxyl/epoxy group can be crosslinked in the molecular structure under certain conditions so as to be deposited on the surface of a substrate.
The invention also provides application of the super-hydrophilic self-cleaning coating sol containing the zwitterionic group polymer in surface modification; the application of the super-hydrophilic self-cleaning coating sol containing the zwitterionic group polymer is coated on a substrate, and the super-hydrophilic self-cleaning coating is obtained after curing for 0.5-200min at the temperature of 0-200 ℃.
The cured product can be purified by post-treatment, such as cleaning, drying, etc.
The super-hydrophilic self-cleaning coating sol containing the zwitterionic group polymer can be coated to prepare the coating with super-hydrophilic property on the surface simply, conveniently and in a large area, and the coating can be firmly attached to the surface of a substrate.
Based on the chemical properties of the cross-linking agent, the carboxyl-containing compound and the zwitterionic group-containing polymer in the super-hydrophilic self-cleaning coating sol component, the condensation of the cross-linking agent, the carboxyl-containing compound and the zwitterionic group-containing polymer and the chemical reaction principle of the cross-linking agent, the carboxyl-containing compound and the zwitterionic group-containing polymer, the amphoteric ionic group-containing polymer is simply, conveniently and firmly 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 super-hydrophilic self-cleaning property is obtained.
The coating sol of the present invention is in liquid form when in use, and thus the coating process may include dipping, spraying, curtain coating, wiping, and the like, in a variety of coating processes suitable for liquid sols.
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 can be smaller than 10 degrees, the contact angle of underwater oil drops is close to 180 degrees, and besides super-hydrophilicity, the 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. In addition, the coating sol of the invention can be widely used by adjusting the type of solvent, the amount of compounding materials and the like in the formula.
Compared with the prior art, the invention has the following advantages:
1. the invention uses the polymer containing the zwitterionic group as the functional material, builds the surface of the functional coating with super-hydrophilic self-cleaning property 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 easy control of operation conditions, 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 treat different materials; and the preparation of the surface of the large-area super-hydrophilic functional coating can be realized, the cost is low, the application is convenient, and the application and development of the super-hydrophilic self-cleaning functional coating technology are promoted.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic reaction diagram of the sol of the super-hydrophilic self-cleaning coating of the present invention for constructing a super-hydrophilic self-cleaning coating on a substrate surface.
Fig. 2 is an SEM image of the glass surface before and after modification of the self-cleaning coating.
Fig. 3 is an SEM image of the PET nonwoven fabric surface structure before and after modification of the self-cleaning coating.
FIG. 4 is an infrared spectrum of a glass surface before and after modification of a self-cleaning coating.
FIG. 5 is an infrared spectrum of PET nonwoven fabric before and after surface modification of the self-cleaning coating.
FIG. 6 is a graph of water contact angle before and after modification of a glass surface build self-cleaning coating.
Fig. 7 is a graph of contact angle of underwater oil drops before and after modification of a self-cleaning coating constructed on a glass surface.
FIG. 8 is a graph showing the water contact angle before and after modification of the PET nonwoven fabric surface structure.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. The materials referred to in the examples below are available commercially unless otherwise specified. The method is conventional unless otherwise specified.
Example 1: preparation of polymers containing zwitterionic groups
40 parts by mass of 3- (2-methacryloxyethyldimethylamino) propanesulfonate (SBMA), 10 parts by mass of hydroxyethyl methacrylate, 1 part by mass of ammonium persulfate and 500 parts by mass of water are mixed, heated at 80 ℃ for reaction for 8 hours, purified and dried to obtain a polymer containing zwitterionic groups.
Example 2: preparation of polymers containing zwitterionic groups
50 parts by mass of 3- (2-methacryloxyethyldimethylamino) propanesulfonate (SBMA), 1 part by mass of ammonium persulfate and 500 parts by mass of water are mixed, heated at 80 ℃ for reaction for 8 hours, purified and dried to obtain a polymer containing zwitterionic groups.
Example 3: preparation of polymers containing zwitterionic groups
40 parts by mass of methacryloxyethyl dimethyl ammonium acetate (CBMA), 10 parts by mass of glycidyl methacrylate, 1 part by mass of azobisisobutyronitrile and 500 parts by mass of methanol are mixed, heated and refluxed at 70 ℃ for reaction for 12 hours, and purified and dried to obtain a polymer containing zwitterionic groups.
Example 4: preparation of polymers containing zwitterionic groups
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 were mixed, heated and refluxed at 70 ℃ for reaction for 12 hours, and purified and dried to obtain a polymer containing zwitterionic groups.
Example 5
The super-hydrophilic self-cleaning coating sol containing the 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 ethylenediamine tetraacetic acid, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; mixing the components according to the proportion, and uniformly stirring to obtain the super-hydrophilic self-cleaning coating sol.
Example 6
The super-hydrophilic self-cleaning coating sol containing the 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 hexamethylol melamine, 1 part by mass of citric acid, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; mixing the components according to the proportion, and uniformly stirring to obtain the super-hydrophilic self-cleaning coating sol.
Example 7
The super-hydrophilic self-cleaning coating sol containing the 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; mixing the components according to the proportion, and uniformly stirring to obtain the super-hydrophilic self-cleaning coating sol.
Example 8
The super-hydrophilic self-cleaning coating sol containing the zwitterionic group polymer comprises the following components in parts by mass: 100 parts by mass of the zwitterionic group-containing polymer obtained in example 3, 30 parts by mass of hexamethylol melamine, 1 part by mass of citric acid, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; mixing the components according to the proportion, and uniformly stirring to obtain the super-hydrophilic self-cleaning coating sol.
Example 9
The super-hydrophilic self-cleaning coating sol containing the 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, 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; mixing the components according to the proportion, and uniformly stirring to obtain the super-hydrophilic self-cleaning coating sol.
Example 10
The super-hydrophilic self-cleaning coating sol containing the 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, 40 parts by mass of hexamethylol melamine, 2 parts by mass of citric acid, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; mixing the components according to the proportion, and uniformly stirring to obtain the super-hydrophilic self-cleaning coating sol.
Comparative example 1
The coating sol comprises the following components in parts by mass: 100 parts by mass of the zwitterionic group-containing polymer obtained in example 1, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; mixing the components according to the proportion, and uniformly stirring to obtain the coating sol.
Comparative example 2
The coating sol 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, 5 parts by mass of magnesium chloride, 1000 parts by mass of water; mixing the components according to the proportion, and uniformly stirring 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 zwitterionic group-containing polymer obtained in example 1, 2 parts by mass of ethylenediamine tetraacetic acid, 5 parts by mass of magnesium chloride, and 1000 parts by mass of water; mixing the components according to the proportion, and uniformly stirring to obtain the coating sol.
The sol prepared in the above examples and comparative examples is coated on a substrate, cured at 200deg.C for 10min, and purified (e.g. cleaned, dried, etc.) to obtain a coating.
FIG. 1 is a schematic reaction diagram of the sol of the super-hydrophilic self-cleaning coating of the present invention for constructing a super-hydrophilic self-cleaning coating on a substrate surface. The invention carries out hydrophilicity test on the coating and evaluates the hydrophilicity stability of the coating, 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 FIGS. 2-8.
TABLE 1 contact angle of water drops 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 all smaller than 10 degrees, so that the super-hydrophilic self-cleaning coating has excellent hydrophilicity. After multiple cleaning, in example 5, the contact angle of water drops of different materials is still smaller than 10 degrees, and the stable super-hydrophilicity is shown; as can be seen from the results of comparative examples 1 to 3, the water contact angle of the material became large after a plurality of times of washing, and the hydrophilic stability thereof became 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. 2-8 are graphs showing the test of the sol prepared in example 5 before and after surface modification of various substrates. As is evident from fig. 2 and 3, the super-hydrophilic 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 after glass modification is 1040cm in the infrared spectrum -1 The sulfonate group has a telescopic vibration absorption peak at 1720cm -1 A telescopic vibration absorption peak belonging to-c=o appears at the position; 1040cm in PET modified infrared spectrum -1 Where sulfonate groups appearIs a telescopic vibration absorption peak; indicating successful build-up of the coating on the substrate surface. As can be seen from fig. 6 and 7, after the glass surface is modified, the glass surface exhibits super-hydrophilic properties, and the contact angle is less than 10 °; before modification, the contact angle of the underwater oil drop on the glass surface is about 125 degrees, after modification, the glass surface presents an underwater super-oleophobic characteristic, the contact angle is close to 180 degrees, the excellent underwater super-oleophobic characteristic is presented, and the surface with the characteristic can present an oil stain preventing function under water. As can be seen from fig. 8, the PET nonwoven fabric before modification has a water contact angle close to 130 °, and exhibits hydrophobicity; after modification, the surface presents super-hydrophilic property, and water drops contact the modified PET surface, namely are wetted and sucked, and the super-hydrophilic property is presented. Other embodiments have similar test results and are not described in detail.
Therefore, the super-hydrophilic self-cleaning coating sol can form coatings on different substrate surfaces, such as glass materials, metal materials, ceramic materials, polymer materials, artificial polymer fabrics, natural polymer fabrics and the like, the water contact angle of the obtained coating is smaller than 10 degrees, the contact angle of underwater oil drops is close to 180 degrees, and besides super-hydrophilicity, the coating sol can also 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 examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (5)
1. The super-hydrophilic self-cleaning coating sol containing the zwitterionic group polymer is characterized by comprising the following components in parts by mass: 100 parts of polymer containing zwitterionic groups, 1-100 parts of cross-linking agent, 0.01-100 parts of carboxyl compound, 0.01-20 parts of catalyst and water;
the polymer containing the zwitterionic groups is obtained by reacting a zwitterionic monomer and a comonomer under the action of an initiator;
the zwitterionic monomer comprises at least one of 2- (methacryloyloxy) ethyl-2- (trimethylamino) ethyl phosphate and betaine type zwitterionic vinyl monomer;
the comonomer comprises at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate and allyl glycidyl ether;
the carboxyl-containing compound comprises at least one of citric acid, malic acid, amino acid, ethylenediamine tetraacetic acid, aminotriacetic acid, diethylenetriamine pentaacetic acid, ethylene glycol bis (2-aminoethyl ether) tetraacetic acid, ethylenediamine diacetic acid, cyclohexanediamine tetraacetic acid, S-ethylenediamine disuccinic acid, diethyl triacetic acid, methylglycine diacetic acid, hydroxyethyl ethylenediamine triacetic acid and N, N-dihydroxyethyl glycine;
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 triazinone, dimethylol propylene urea, dimethylol urethane, bisphenol A diglycidyl ether, beta-bis hydroxyethyl sulfone, dimethyl dihydroxy ethylene urea and water-based polyurethane.
2. The super-hydrophilic self-cleaning coating sol containing the zwitterionic group polymer according to claim 1, which is characterized by comprising the following components in parts by mass: 100 parts of polymer containing zwitterionic groups, 1-50 parts of cross-linking agent, 0.01-10 parts of carboxyl compound, 0.01-10 parts of catalyst and water.
3. The super hydrophilic self-cleaning coating sol containing a zwitterionic group polymer according to claim 1, characterized in that: the chemical formula of the betaine type amphoteric ion alkene monomer is CH 2 =C(Ra)-L1-N + (Rb)(Rc)-L2-A(=O)O - Or CH (CH) 2 =C(Ra)-L1-N + (Rb)(Rc)-O - The method comprises the steps of carrying out a first treatment on the surface of the Wherein CH is 2 =c (Ra) is a polymerizable group, ra is hydrogen or methyl; n (N) + Is a cationic center; a (=o) O - Is an anionic group, A is C or SO; rb and Rc are the same or different and are each hydrogen, alkyl or aryl; l1 is a linker from the cationic center to the polymerizable group, 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 cation-to-anion-centered linker of- (CH) 2 ) n -n is an integer from 1 to 10.
4. Super hydrophilic self cleaning coating sol of polymers containing zwitterionic groups according to claim 1 or 2, characterized in that: the catalyst comprises at least one of inorganic acid, organic acid, ammonium salt and inorganic metal salt.
5. Use of a super hydrophilic self cleaning coating sol of a polymer containing zwitterionic groups according to claim 1 or 2 for surface modification.
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| 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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|---|---|---|---|---|
| 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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