CN101724326A - Waterborne organic silicon-acrylic acid self-stratifying coating - Google Patents
Waterborne organic silicon-acrylic acid self-stratifying coating Download PDFInfo
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- CN101724326A CN101724326A CN200910311314A CN200910311314A CN101724326A CN 101724326 A CN101724326 A CN 101724326A CN 200910311314 A CN200910311314 A CN 200910311314A CN 200910311314 A CN200910311314 A CN 200910311314A CN 101724326 A CN101724326 A CN 101724326A
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- Prior art keywords
- emulsion
- coating
- acrylic
- organic silicon
- silicone
- Prior art date
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- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 63
- 239000011248 coating agent Substances 0.000 title claims abstract description 61
- BKLGNGGEJNHIQT-UHFFFAOYSA-N prop-2-enoic acid;silicon Chemical compound [Si].OC(=O)C=C BKLGNGGEJNHIQT-UHFFFAOYSA-N 0.000 title description 16
- 239000000839 emulsion Substances 0.000 claims abstract description 70
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000003973 paint Substances 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 8
- 239000000049 pigment Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000002562 thickening agent Substances 0.000 claims abstract 5
- 238000002156 mixing Methods 0.000 claims abstract 4
- 239000000654 additive Substances 0.000 claims abstract 2
- 238000000227 grinding Methods 0.000 claims abstract 2
- -1 aminopropyl Chemical group 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 28
- 229920001296 polysiloxane Polymers 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000000080 wetting agent Substances 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 claims description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims 2
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 claims 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 claims 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims 1
- 229940121375 antifungal agent Drugs 0.000 claims 1
- 239000003429 antifungal agent Substances 0.000 claims 1
- 239000002270 dispersing agent Substances 0.000 claims 1
- HBWGDHDXAMFADB-UHFFFAOYSA-N ethenyl(triethyl)silane Chemical compound CC[Si](CC)(CC)C=C HBWGDHDXAMFADB-UHFFFAOYSA-N 0.000 claims 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 claims 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims 1
- 239000003755 preservative agent Substances 0.000 claims 1
- 230000002335 preservative effect Effects 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 31
- 239000010703 silicon Substances 0.000 abstract description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 26
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 239000004925 Acrylic resin Substances 0.000 description 11
- 229920000178 Acrylic resin Polymers 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000004816 latex Substances 0.000 description 9
- 229920000126 latex Polymers 0.000 description 9
- 150000001282 organosilanes Chemical class 0.000 description 8
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000005304 joining Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- 239000004160 Ammonium persulphate Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 235000019395 ammonium persulphate Nutrition 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- NJOPBCZQSPNWLW-UHFFFAOYSA-N C(C)O[SiH2]OCC.CC=C Chemical compound C(C)O[SiH2]OCC.CC=C NJOPBCZQSPNWLW-UHFFFAOYSA-N 0.000 description 2
- 239000004159 Potassium persulphate Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PXJZCBUXFVZSLL-UHFFFAOYSA-N CO[SiH2]OC.C=CC Chemical compound CO[SiH2]OC.C=CC PXJZCBUXFVZSLL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
本发明涉及一种水性有机硅-丙烯酸自分层涂料。它需要解决自分层性能差的技术问题，供一种水性有机硅-丙烯酸自分层涂料及其制造方法，实现在较低有机硅含量的情况下，达到较高有机硅含量的传统硅丙乳液的性能，且成本优势明显。本发明的涂料，其特征在于：它以下列重量百分比的物料为原料，经过制备得到产品：有机硅乳液10～15％，丙烯酸乳液50～60％，有机硅改性丙烯酸乳液5～10％，填料5～7％，颜料5～7％，增稠剂0.2～0.5％，助剂2～3％，水10～20％。其制备方法为：1)在配浆容器中加入水和助剂；2)加入填料和颜料；3)研磨得到色浆；4)在调漆容器内加入其余原料；5)加入增稠剂；6)混合料过滤，得产品。The invention relates to a waterborne silicone-acrylic self-layering coating. It needs to solve the technical problem of poor self-delamination performance, provide a water-based silicone-acrylic self-delamination coating and its manufacturing method, and achieve the traditional silicon-acrylic emulsion with higher organic silicon content under the condition of lower organic silicon content. performance, and the cost advantage is obvious. The coating of the present invention is characterized in that: it uses the following materials by weight percentage as raw materials to obtain products through preparation: 10-15% of organic silicon emulsion, 50-60% of acrylic emulsion, 5-10% of organic silicon-modified acrylic emulsion, Filler 5-7%, pigment 5-7%, thickener 0.2-0.5%, auxiliary agent 2-3%, water 10-20%. The preparation method is as follows: 1) adding water and additives into a slurry mixing container; 2) adding fillers and pigments; 3) grinding to obtain a color paste; 4) adding other raw materials into a paint mixing container; 5) adding a thickener; 6) The mixture is filtered to obtain the product.
Description
Technical field
The present invention relates to a kind of chemistry painting industry, specifically is a kind of waterborne organic silicon-acrylic acid self-stratifying coating.
Background technology
Organosilicon-acrylic coating is the new coating that development in recent years is rapid and have wide market application foreground.It had both had organosilicon fire-resistant, ultra-violet resistance, durability in oxidative degradation, low, the good permeability of surface energy, had snappiness, guarantor's light, tint retention, the high tack of acrylic resin again, was the coating variety of a class excellent combination property.Waterborne organic silicon-acrylic coating environmental friendliness, be widely used as building coating, hide finishes and tackiness agent etc., the exterior coating that particularly can be used for important building or high-rise high-rise building from the nineties in 20th century, becomes the focus product that people competitively develop, produce always.
Waterborne organic silicon-acrylic acid self-stratifying coating has gradient from layer functions.In the coating film process, acrylic resin moves to basic unit, the sticking power of increase and building surface, and the organosilicon component is moved to the top layer, improves the pollution resistance and the weathering resistance of surface coatings.It is ultimate attainment from layering organosilicon-acrylic coating organosilicon performance limited in the coating to be performed to, and can be implemented under the situation of low organosilicon content, reach the performance of the traditional silicon acrylic emulsion of higher organosilicon content, and cost advantage is obvious.
The preparation method of existing waterborne organic silicon-acrylic coating has two kinds: physical blending and chemical modification.For physical blending organosilicon-acrylic coating, be directly to add organic silicon emulsion or dispersion liquid in the acrylic ester emulsion, chemical reaction does not take place between two kinds of emulsions, because organosilicon and vinylformic acid surface energy difference are big, the requirement of each component polymer stable existence in the self stratifying coating is not satisfied in easily layering; Equally for chemical modification organosilicon-acrylic resin, adopt organosilane monomer and Acrylic Acid Monomer emulsion copolymerization, molecule is with chemical bond combination, good stability, in the film-forming process, be difficult to automatic separation, so can not directly be used for preparation from layering organosilicon-acrylic coating.
Employing silicone resins such as Li Yonghua and organosilicon inarch acrylic copolymer and acrylic resin have been feedstock production solvent type organic silicone modified acrylic resin self stratifying coating.These solvents evaporate in construction process in the atmosphere, and not only the health of human body to the constructor works the mischief, and pollutes the environment, and cause the hidden danger of fire in addition.Synthesis technique and organo-siloxane open loop polycondensation and the reaction principle free-radical polymerized with acrylate thereof that Yang Zesheng etc. utilize pre-emulsification to drip have continuously prepared from stratified organosilicon-modified acrylate emulsion.In this method owing to take the method for copolymerization to prepare polymeric constituent in the coating, be difficult to the molecular structure of controlling polymers, cause product from shortcomings such as layering performance poor repeatability.
Summary of the invention
The technical issues that need to address of the present invention are: existing waterborne organic silicon-acrylic coating for reaching coating performance preferably, needs to improve the organosilicon components contents from the layering poor performance.The invention provides a kind of waterborne organic silicon-acrylic acid self-stratifying coating and manufacture method thereof, be implemented under the situation of low organosilicon content, reach the performance of the traditional silicon acrylic emulsion of higher organosilicon content.
For the waterborne organic silicon acrylic coating is had from the layering performance, the technical scheme that adopts physical mixed and chemical modification to combine among the present invention,
Waterborne organic silicon-acrylic acid self-stratifying coating of the present invention is characterized in that: it comprises that the material of following weight percent is a raw material, through preparing product:
Organic silicon emulsion 10～15%,
ACRYLIC EMULSION 50～60%,
Organosilicon-modified acrylic emulsion 5～10%,
Filler 5～7%,
Pigment 5～7%,
Thickening material 0.2～0.5%,
Auxiliary agent 2～3%,
Water 10～20%;
Described organic silicon emulsion is to pass through RSiX
3Monomer and R
1R
2SiX
2Monomer is 1: 10～20 in molar ratio, carries out the emulsion copolymerization reaction and obtains; Wherein: R, R
1, R
2Respectively be selected from a kind of (wherein methyl best results) in methyl, ethyl, propyl group, phenyl, vinyl, trifluoro propyl, aminopropyl, chloropropyl, epoxypropyl, hydroxypropyl, the mercapto propyl group, X is selected from oxyethyl group, methoxyl group;
Described organosilicon-modified acrylic emulsion is by functional group polysiloxane, organosilane monomer, press mass ratio 10～20 with Acrylic Acid Monomer or acrylate monomer: 1: 20～40, get through letex polymerization; Wherein: vinylformic acid or acrylate monomer are the methacrylic acid methyl, Jia Jibingxisuanyizhi, butyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid, the mixture of one or more in the methacrylic acid, the functional group polysiloxane is ethenyl blocking polydimethylsiloxane or hydroxyl endblocked polydimethylsiloxane, and organosilane monomer is a vinyltrimethoxy silane, vinyltriethoxysilane, methyl ethylene dimethoxy silane, the methyl ethylene diethoxy silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, the gamma-methyl allyl acyloxypropyl triethoxyl silane, the gamma-methyl allyl acyloxypropyl methyl dimethoxysilane, the mixture of one or more in the gamma-methyl allyl acyloxypropyl methyldiethoxysilane;
Its preparation method is following steps:
1) in joining the slurry container, adds entry and auxiliary agent, stir;
2) add filler and pigment in the compound that in step 1), obtains, stir;
3) with step 2) in the mixture that obtains be ground to below the fineness 30 μ m, obtain mill base;
4) in the paint container, add mill base, organic silicon emulsion, organosilicon-modified acrylic emulsion, ACRYLIC EMULSION, stir;
5) add thickening material in the compound that in step 4), obtains, stir;
6) compound that step 5) is obtained filters (filtering larger particles), obtains waterborne organic silicon-acrylic acid self-stratifying coating.
Organic silicon emulsion of the present invention passes through RSiX
3Monomer and R
1R
2SiX
2Monomer adds emulsifying agent and makes through the emulsion copolymerization reaction, contains trifunctional silica chain link (RSiO
1.5), when organic silicon components migrates to coatingsurface, finish the curing of coatingsurface by the polycondensation of functional group, make coatingsurface bright and clean, have best waterproof and dustproof effect.
ACRYLIC EMULSION of the present invention can adopt commercially available ACRYLIC EMULSION, for example B-96 emulsion, AC-261 emulsion.
Organosilicon modified crylic acid resin emulsion of the present invention by functional group polysiloxane, organosilane monomer and Acrylic Acid Monomer or acrylate monomer (letter is vinylformic acid (ester) monomer) add emulsifying agent, initiator gets through letex polymerization.
Because the consistency of silicone resin and acrylic resin is poor, be easy to layering, directly adopt silicone resin and acrylic resin blend, be difficult to stable existence in same system.In system, when adding organosilicon modified crylic acid resin, played the effect of compatilizer, thereby realized the stability of system at both.The applicant discovers, adopt functional group polysiloxane and organosilane monomer jointly and vinylformic acid (ester) class monomer carry out the emulsion copolymerization grafting, the consistency effect that obtains multipolymer is best.Contain two keys in the organosilane monomer, can carry out free-radical polymerizedly, contain alkoxyl group in the organosilane monomer simultaneously,, improve the grafting efficiency of multipolymer with the hydroxyl generation polycondensation in the polysiloxane with vinylformic acid (ester) monomer.When the employing of functional group polysiloxane contained the vinyl polysiloxane, vinyl can carry out free-radical polymerized with organosilane monomer and vinylformic acid (ester) monomer equally.The consumption of organosilicon modified crylic acid resin also has certain scope, and consumption is too big, and the stability of coating strengthens, but in the film forming process of coating, organosilicon and acrylic resin are difficult to layering, have lost from the layering performance.Consumption very little, silicone resin and acrylic resin are difficult to stable existence, have influenced the use properties of coating, cause simultaneously that to be coated with the interlayer bonding force poor, easily come off.The consumption of organosilicon modified crylic acid resin emulsion is 5～10%.
Organic silicon emulsion polymerization of the present invention and organosilicon-modified acrylic emulsion polymeric emulsifying agent are: a kind of in sodium lauryl sulphate, the Sodium dodecylbenzene sulfonate; Used initiator is Potassium Persulphate or ammonium persulphate.
Filler commonly used is a kind of in light calcium carbonate, process white, talcum powder or the mica powder in the production; Pigment is a kind of in iron oxide black, red iron oxide, iron oxide yellow, the titanium dioxide; Thickening material is a kind of in Natvosol, the sodium polyacrylate.
The auxiliary agent that also should add coating weight 2～3% in the preparation process of coating.Auxiliary agent comprises dispersion agent, wetting agent, defoamer, mould inhibitor, sanitas and membrane-forming agent.Used dispersion agent is sodium, ammonium, the amine salt of alkenyl monomer and unsaturated carboxylic acid and lipid multipolymer thereof, and for example: 5040 dispersion agents, 5027 dispersion agents, T-731 dispersion agent, consumption are 0.1～0.3% of coating content; Wetting agent is selected polyether-modified alkynol for use, and as SURFYNOLGA, SURFYNOL TG, consumption is 0.1～0.3% of a coating content; Defoamer is selected organic silicon modified by polyether for use, and as SN313, NXZ, NDW, BYK 024, consumption is 0.01～0.1% of a coating content; Sanitas can be KATHONLXE, HX-89, and consumption is 0.1～0.3% of a coating; Mould inhibitor can be SKANE M-8, BCM sanitas, and consumption is 0.1～0.5% of a coating; Membrane-forming agent is one or more the mixture in ethylene glycol ethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene glycol, the propylene glycol, and consumption is 1.5～2% of a coating content.
The present invention makes the water-soluble organic silicon acrylic coating of development have gradient from layer functions by Molecular Structure Design and component collocation cleverly.In the coating film process, acrylic resin moves to basic unit, the sticking power of increase and building surface, and the organosilicon component is moved to the top layer, improves the pollution resistance and the weathering resistance of surface coatings.Compared with prior art, it is ultimate attainment that organosilicon performance limited in the coating is performed to, and can be implemented under the situation of low organosilicon content, reach the performance of the traditional silicon acrylic emulsion of higher organosilicon content, and cost advantage is obvious.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1
The preparation of organic silicon emulsion: in three mouthfuls of reaction flasks of the 500ml that stirring, reflux exchanger and constant pressure funnel are housed, add 100g water, 15g sodium lauryl sulphate, 0.3g sodium hydroxide, start stirring and make emulsifiers dissolve.Be warming up to 80 ℃, drip the mixture of 65g dimethyldiethoxysilane and 5g Union carbide A-162,10min dropwises.Continue reaction 6h.After reaction finishes,, obtain organic silicon emulsion with the Glacial acetic acid neutralization.
The preparation of organosilicon-modified acrylic emulsion: 20g ethenyl blocking polydimethylsiloxane (molecular weight is 2000), 1g vinyltriethoxysilane, 18g butyl acrylate, 18g methyl methacrylate, 0.8g Sodium dodecylbenzene sulfonate and 100g deionized water are joined in the four-necked bottle, fully stir, logical nitrogen 30min deoxygenation, with after the warming-in-water to 70 ℃, add the 0.4g ammonium persulphate, insulation 6h obtains organosilicon-modified acrylic emulsion.
The composition of waterborne organic silicon-acrylic acid self-stratifying coating: organic silicon emulsion 10g, ACRYLIC EMULSION 57g, organosilicon-modified acrylic emulsion 8g, light calcium carbonate 6g, titanium dioxide 6g, Natvosol 0.3g, 5040 dispersion agent 0.1g, SURFYNOL GA 0.2g, SN 313 0.05g, KATHON LXE 0.2g, SKANE M-8 0.5g, ethylene glycol 1.5g, water 10.15g.
Waterborne organic silicon-acrylic acid self-stratifying coating prepares by following steps:
1) in joining the slurry container, adds 10.15g water and 0.1g 5040 dispersion agents, 0.2g SURFYNOL GA, 0.05g SN313,0.2g KATHON LXE, 0.5g SKANE M-8,1.5g ethylene glycol, stir;
2) add 6g light calcium carbonate and 6g titanium dioxide in the compound that in step 1), obtains, stir;
3) with step 2) in the mixture that obtains be ground to fineness 25 μ m, obtain mill base;
4) in the paint container, add mill base, 10g organic silicon emulsion, 8g organosilicon-modified acrylic emulsion, 57g AC-261 Emulsion acrylic resin, stir;
5) add the 0.3g Natvosol in the compound that in step 4), obtains, stir;
6) compound that step 5) is obtained filters, and the filtering larger particles obtains waterborne organic silicon-acrylic acid self-stratifying coating.
Prepared organosilicon-acrylic coating is cured, and with each layer silicone content in the X-gamma spectrometer test latex film cross section, the result is:
| The latex film cross section number of plies | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Silicon content (%) | 3.5 | 3.6 | 3.2 | 3.0 | 2.6 | 2.1 | 1.7 | 1.5 | 1.3 | 1.2 |
Annotate: the latex film cross section is divided into 10 layers, and the 1st layer is upper surface, and 10 layers is lower surface.
As can be seen, the content difference of different sectional position element silicons illustrates that the coating of preparation has significantly from layer functions.
Embodiment 2
The preparation of organic silicon emulsion: in three mouthfuls of reaction flasks of the 500ml that stirring, reflux exchanger and constant pressure funnel are housed, add 100g water, 10g Sodium dodecylbenzene sulfonate, 0.5g sodium hydroxide, start stirring and make emulsifiers dissolve.Be warming up to 70 ℃, drip the mixture of 60g dimethyldimethoxysil,ne and 9.0g aminopropyl trimethoxysilane, 15min dropwises.Continue reaction 6h.After reaction finishes,, obtain organic silicon emulsion with the Glacial acetic acid neutralization.
The preparation of organosilicon-modified acrylic emulsion: 20g hydroxyl endblocked polydimethylsiloxane (molecular weight is 3500), 1g gamma-methyl allyl acyloxypropyl trimethoxysilane, 1g methyl ethylene diethoxy silane, 20g butyl acrylate, 25g vinylformic acid, 1.2g sodium lauryl sulphate and 150g deionized water are joined in the four-necked bottle, fully stir, logical nitrogen 30min deoxygenation, with after the warming-in-water to 70 ℃, add the 0.6g Potassium Persulphate, insulation 6h obtains organosilicon-modified acrylic emulsion.
The composition of waterborne organic silicon vinylformic acid self stratifying coating: organic silicon emulsion 15g, ACRYLIC EMULSION 50g, organosilicon-modified acrylic emulsion 5g, talcum powder 5g, red iron oxide 5g, sodium polyacrylate 0.3g, 5027 dispersion agent 0.3g, SURFYNOL TG 0.1g, NDW 0.1g, HX-89 0.1g, BCM sanitas 0.1g, propylene glycol monomethyl ether 2.0g, water 17g.
Waterborne organic silicon-acrylic acid self-stratifying coating prepares by following steps:
1) in joining the slurry container, adds 17g water and 0.3g 5027 dispersion agents, 0.1g SURFYNOL TG, 0.1g NDW, 0.1gKHX-89,0.1g BCM sanitas, 2.0g propylene glycol monomethyl ether, stir;
2) add 5g talcum powder and 5g red iron oxide in the compound that in step 1), obtains, stir;
3) with step 2) in the mixture that obtains be ground to fineness 28 Jing, obtain mill base;
4) in the paint container, add mill base, 15g organic silicon emulsion, 5g organosilicon-modified acrylic emulsion, 50g B-96 ACRYLIC EMULSION, stir;
5) add the 0.3g sodium polyacrylate in the compound that in step 4), obtains, stir;
6) compound that step 5) is obtained filters, and the filtering larger particles obtains waterborne organic silicon-acrylic acid self-stratifying coating.
Prepared organosilicon-acrylic coating is cured, and with each layer silicone content in the X-gamma spectrometer test latex film cross section, the result is:
| The latex film cross section number of plies | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Silicon content (%) | 4.7 | 4.5 | 4.4 | 4.2 | 3.5 | 3.1 | 2.5 | 1.9 | 1.4 | 1.2 |
Annotate: the latex film cross section is divided into 10 layers, and the 1st layer is upper surface, and 10 layers is lower surface.
As can be seen, the content difference of different sectional position element silicons illustrates that the coating of preparation has significantly from layer functions.
Embodiment 3
The preparation of organic silicon emulsion: in three mouthfuls of reaction flasks of the 500ml that stirring, reflux exchanger and constant pressure funnel are housed, add 100g water, 10g Sodium dodecylbenzene sulfonate, 0.5g sodium hydroxide, start stirring and make emulsifiers dissolve.Be warming up to 80 ℃, drip the mixture of 75g aminomethyl phenyl dimethoxy silane and 4.1g mercaptopropyl trimethoxysilane, 20min dropwises.Continue reaction 6h.After reaction finishes,, obtain organic silicon emulsion with the Glacial acetic acid neutralization.
The preparation of organosilicon-modified acrylic emulsion: 15g hydroxyl endblocked polydimethylsiloxane (molecular weight is 2800), 1g gamma-methyl allyl acyloxypropyl triethoxyl silane, 10g methacrylic acid, 20g methyl acrylate, 0.8g Sodium dodecylbenzene sulfonate and 120g deionized water are joined in the four-necked bottle, fully stir, logical nitrogen 30min deoxygenation, with after the warming-in-water to 80 ℃, add the 0.5g ammonium persulphate, insulation 6h obtains organosilicon-modified acrylic emulsion.
The composition of waterborne organic silicon vinylformic acid self stratifying coating: organic silicon emulsion 12g, ACRYLIC EMULSION 50g, organosilicon-modified acrylic emulsion 7g, mica powder 6g, iron oxide yellow 5g, sodium polyacrylate 0.5g, T-731 dispersion agent 0.1g, SURFYNOL TG 0.1g, NXZ 0.05g, HX-89 0.1g, BCM sanitas 0.1g, ethylene glycol 0.8g, ethylene glycol ethyl ether 1.5g, water 11.75g.
The manufacture method of waterborne organic silicon vinylformic acid self stratifying coating may further comprise the steps:
1) in joining the slurry container, adds 11.75g water and 0.1g T-731 dispersion agent, 0.1g SURFYNOL TG, 0.05g NXZ, 0.1g KHX-89,0.1g BCM sanitas, 0.8g ethylene glycol, 1.5g ethylene glycol ethyl ether, stir;
2) add 6g mica powder and 5g iron oxide yellow in the compound that in step (1), obtains, stir;
3) mixture that obtains in the step (2) is ground to fineness 29 μ m, obtains mill base;
4) in the paint container, add mill base, 12g organic silicon emulsion, 7g organosilicon-modified acrylic emulsion, 50gB-96 ACRYLIC EMULSION, stir;
5) add the 0.5g sodium polyacrylate in the compound that in step (4), obtains, stir;
6) compound that step (5) is obtained filters, and the filtering larger particles obtains waterborne organic silicon-acrylic acid self-stratifying coating.
Prepared organosilicon-acrylic coating is cured, and with each layer silicone content in the X-gamma spectrometer test latex film cross section, the result is:
| The latex film cross section number of plies | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Silicon content (%) | 4.2 | 4.1 | 3.9 | 3.5 | 3.1 | 2.9 | 1.9 | 1.6 | 1.4 | 1.2 |
Annotate: latex film is divided into 10 layers, and the 1st layer is upper surface, and 10 layers is lower surface.
As can be seen, the content difference of different sectional position element silicons illustrates that the coating of preparation has significantly from layer functions.
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