CN1103341C - Organosilicon modified acrylate latex with core-shell structure and its preparing process - Google Patents
Organosilicon modified acrylate latex with core-shell structure and its preparing process Download PDFInfo
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- CN1103341C CN1103341C CN99119980A CN99119980A CN1103341C CN 1103341 C CN1103341 C CN 1103341C CN 99119980 A CN99119980 A CN 99119980A CN 99119980 A CN99119980 A CN 99119980A CN 1103341 C CN1103341 C CN 1103341C
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- Prior art keywords
- acrylate
- monomers
- latex
- methacrylate
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- 239000004816 latex Substances 0.000 title claims abstract description 68
- 229920000126 latex Polymers 0.000 title claims abstract description 68
- 239000011258 core-shell material Substances 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 15
- 150000001252 acrylic acid derivatives Chemical class 0.000 title abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 54
- -1 alkyl methacrylate Chemical compound 0.000 claims abstract description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 7
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- 238000004132 cross linking Methods 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 15
- 239000003995 emulsifying agent Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- RDEKJZXDABIQKL-UHFFFAOYSA-N ethylamino prop-2-enoate Chemical compound CCNOC(=O)C=C RDEKJZXDABIQKL-UHFFFAOYSA-N 0.000 claims description 5
- 239000012986 chain transfer agent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012966 redox initiator Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 claims description 2
- CDUQMGQIHYISOP-UHFFFAOYSA-N 2-cyano-3-phenylprop-2-enoic acid Chemical compound OC(=O)C(C#N)=CC1=CC=CC=C1 CDUQMGQIHYISOP-UHFFFAOYSA-N 0.000 claims description 2
- PMZXJPLGCUVUDN-UHFFFAOYSA-N 4-ethenyl-1,2-dimethylbenzene Chemical compound CC1=CC=C(C=C)C=C1C PMZXJPLGCUVUDN-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 claims description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 2
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 claims description 2
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 2
- 238000003756 stirring Methods 0.000 claims 2
- IUSXXDHQFMPZQX-UHFFFAOYSA-N (2-hydroxyphenyl) prop-2-enoate Chemical compound OC1=CC=CC=C1OC(=O)C=C IUSXXDHQFMPZQX-UHFFFAOYSA-N 0.000 claims 1
- OBRYRJYZWVLVLF-UHFFFAOYSA-N 1-ethenyl-4-ethoxybenzene Chemical compound CCOC1=CC=C(C=C)C=C1 OBRYRJYZWVLVLF-UHFFFAOYSA-N 0.000 claims 1
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 claims 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 claims 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 claims 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims 1
- INRQKLGGIVSJRR-UHFFFAOYSA-N 5-hydroxypentyl prop-2-enoate Chemical compound OCCCCCOC(=O)C=C INRQKLGGIVSJRR-UHFFFAOYSA-N 0.000 claims 1
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 claims 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical group CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims 1
- 238000001802 infusion Methods 0.000 claims 1
- 239000002736 nonionic surfactant Substances 0.000 claims 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 17
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000007334 copolymerization reaction Methods 0.000 abstract description 8
- 239000003607 modifier Substances 0.000 abstract description 3
- 238000005034 decoration Methods 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 125000005395 methacrylic acid group Chemical group 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 3
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 241000238367 Mya arenaria Species 0.000 description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000009991 scouring Methods 0.000 description 3
- 238000006884 silylation reaction Methods 0.000 description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- MCEBKLYUUDGVMD-UHFFFAOYSA-N [SiH3]S(=O)=O Chemical compound [SiH3]S(=O)=O MCEBKLYUUDGVMD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 2
- SOGFHWHHBILCSX-UHFFFAOYSA-J prop-2-enoate silicon(4+) Chemical compound [Si+4].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C SOGFHWHHBILCSX-UHFFFAOYSA-J 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- SMSKIVCCLIQXFD-UHFFFAOYSA-N 1-tert-butyl-3-ethenylbenzene Chemical compound CC(C)(C)C1=CC=CC(C=C)=C1 SMSKIVCCLIQXFD-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- IYRHBDVSMINOTQ-UHFFFAOYSA-N aniline;ethene Chemical compound C=C.NC1=CC=CC=C1 IYRHBDVSMINOTQ-UHFFFAOYSA-N 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- UANQBSLQFDXBAX-UHFFFAOYSA-N diethyl butanedioate;sodium Chemical compound [Na].CCOC(=O)CCC(=O)OCC UANQBSLQFDXBAX-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- WDSSTLCJMOISES-UHFFFAOYSA-N hydrogen peroxide;iron Chemical compound [Fe].OO WDSSTLCJMOISES-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229940093916 potassium phosphate Drugs 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
本发明属化工技术领域，涉及一种具有核壳结构的有机硅改性丙烯酸酯胶乳及其制备方法。丙烯酸酯胶乳由乙烯基烷氧基硅烷单体作为改性剂，与甲基丙烯酸烷基酯、丙烯酸烷基酯、丙烯酸羟烷基酯和烯基芳族化合物等单体通过种子乳液聚合方式进行共聚获得。产品稳定性好，可放置一年以上，并可明显提高涂膜的硬度、拉伸强度、耐水性、附着力及耐擦洗性，广泛用于外墙涂料、防水涂料和玻璃装璜涂料等。The invention belongs to the technical field of chemical industry, and relates to an organosilicon-modified acrylate latex with a core-shell structure and a preparation method thereof. Acrylate latex is made of vinyl alkoxysilane monomer as modifier, and monomers such as alkyl methacrylate, alkyl acrylate, hydroxyalkyl acrylate and alkenyl aromatic compound are carried out by seed emulsion polymerization obtained by copolymerization. The product has good stability and can be placed for more than one year, and can significantly improve the hardness, tensile strength, water resistance, adhesion and scrub resistance of the coating film. It is widely used in exterior wall coatings, waterproof coatings and glass decoration coatings.
Description
The invention belongs to chemical technology field, relate to a kind of modification acrylate latex and preparation method thereof.
Acrylate latex has many outstanding advantages, and photostabilization, weathering resistance, resistance to acids and bases and erosion resistance as excellence are widely used at aspects such as coating, tackiness agents.But, wish it is carried out modification because acrylate latex has shortcomings such as poor water resistance and low temperature become fragile easily, high temperature becomes sticky easily.If adopt high temperature resistant, surface energy low and the organosilicon function monomer of water-tolerant carries out modification to acrylate latex, then organic silicone modified acrylate coating material can improve the hardness of filming, tensile strength, ventilation property, wear resistance, sticking power, anti-stickly put forth effort, water tolerance, solvent resistance and scrub resistance.According to foreign literature, organic silicon-acrylate paint coatings ultraviolet resistance irradiation can reach more than 2000 hours, require much larger than common coating 250 hours.
At present, acrylate is being carried out in the research of modification with the organosilicon function monomer, usually adopt mechanical blending or means such as grafting copolymerization process, segment copolymerization method and interact network method, as US4491650, day disclosure special permission communique [putting down] 02127458, EP297505 etc., but these methods all are solvent polymerization method basically.Along with requirement on environmental protection improves day by day, various countries are strict day by day to the regulation of VOC quantity discharged, and therefore, the research and development water-borne coatings has become coating researchist's goal in research.The emulsion polymerization modification acrylate mainly is to utilize the organosilane monomer contain vinyl-functional or performed polymer and acrylic ester monomer to carry out emulsion copolymerization.Because the existence of water in the letex polymerization, the hydrolysis-condensation reaction of alkoxyl group can take place, it forms with the addition reaction of vinyl-functional and competes.And addition reaction than hydrolysis-condensation reaction slowly many, therefore to the selection of comonomer difficulty relatively.The general emulsion polymerization synthetic organic silicon-acrylate latex stability that adopts is bad, and the organosilicon addition is little, is not easy and other monomer copolymerization.
The objective of the invention is to propose organosilicon-modified acrylate latex of a kind of synthetic easily, good stability and preparation method thereof.
The acrylate latex that the present invention proposes is a kind of organosilicon-modified acrylate latex with nucleocapsid structure.It adopts emulsion polymerization to prepare.
Among the present invention, the consisting of of acrylate: (1) contains C
1～C
10Alkyl acrylate; (2) contain C
1～C
10Alkyl methacrylate; (3) contain C
2～C
10Acrylic acid hydroxy alkyl ester; (4) contain C
3～C
6The thiazolinyl carboxylic acid; (5) contain C
4～C
15The vinylformic acid cross-linking monomer; (6) contain the aromatics of vinyl.
The present invention uses and contains C
7～C
18Vinyl alkoxy silane as organosilicon modifier.
The present invention uses and contains C
2～C
12Alkyl sulfhydryl or hydrosulphonyl silane as chain-transfer agent.
The present invention uses negatively charged ion and nonionic compound emulsifier.
The present invention uses redox initiator.
The present invention uses carbonate, supercarbonate, phosphoric acid salt or the hydrosulfate of basic metal, alkaline-earth metal or ammonium as the pH regulator agent.
The present invention specifically describes as follows:
In the present invention, consisting of of acrylate: (1) contains C
1～C
10Alkyl acrylate, consumption is the 30-50% (weight percent of monomer total amount, following monomer is together), as ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, ethyl acrylate, vinylformic acid-2-ethylamino ester, vinyl acrylate etc.(2) contain C
1～C
10Alkyl methacrylate, consumption is the 20-40% of monomer total amount, as Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, methacrylic acid-2-methyl ester, dimethylaminoethyl methacrylate, n octyl methacrylate etc.(3) contain C
2～C
10Acrylic acid hydroxy alkyl ester, consumption is the 10-20% of monomer total amount, as 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxyl butyl ester, vinylformic acid-4-hydroxyl butyl ester, vinylformic acid-5-hydroxyl pentyl ester, the vinylformic acid-own ester of 6-hydroxyl, vinylformic acid hydroxyl phenolic ester, methacrylic acid-2,3-dihydroxyl propyl ester etc.(4) contain C
3～C
6The thiazolinyl carboxylic acid, consumption is the 2-10% of monomer total amount, as vinylformic acid, methacrylic acid, alpha-cyano-β phenylacrylic acid etc.(5) contain C
4～C
15The vinylformic acid cross-linking monomer, consumption is the 0.5-3% of monomer total amount.(6) contain the aromatics of vinyl, consumption is the 10-60% of monomer total amount, as vinylbenzene, alpha-methyl styrene, amino-benzene ethene, 2-chlorostyrene, 3-t-butyl styrene, 3, and 4-dimethyl styrene, 4-phenetole ethene etc.
The present invention's redox initiator, preparation earlier has the latex seed of stone, again with after the pre-emulsification of soft shell monomer, adopts continuous dripping method in 2-4 hour pre-emulsion to be added drop-wise in the latex seed, reaction finishes, and can obtain having the organosilicon-modified acrylate latex of stone soft shell structure.Concrete steps are as follows:
1. prepare the latex seed
Composition and usage ratio by the aforesaid propylene acid esters take by weighing each component.The reactor of thermometer, well heater, agitator, filling tube and constant current tubing is equipped with in employing.Elder generation is with vinyl aromatic compounds, water and the corresponding emulsifying agent of 10%～20% alkyl acrylate, thiazolinyl carboxylic acid, 30%-100%, high-speed stirring 5-20 minute, when slowly being warming up to temperature and being 45 ℃-65 ℃, add initiator, behind the several minutes, faint blue light appears in emulsion, restir 5-10 minute, promptly forms stone latex seed.
2. prepare organic-silicon-modified nucleocapsid cinnamic acrylic ester emulsion
Remaining alkyl acrylate, alkyl methacrylate, acrylic acid hydroxy alkyl ester, vinyl aromatic compounds, vinylformic acid cross-linking monomer, organosilicon function monomer, chain-transfer agent, water and emulsifying agent etc. were stirred at a high speed 20-30 minute, make it fully emulsified, obtain monomer pre-emulsion.In 2-4 hour that emulsification is good monomer pre-emulsion, initiator are added drop-wise in the reactor continuously, react with the latex seed, temperature of reaction remains on 50 ℃-65 ℃, after reaction finishes, be incubated 1-2 hour, can obtain the organosilicon-modified acrylate latex of nucleocapsid structure, the latex solid content is 45%-50%.
In the present invention, the organosilicon modifier of use is for containing C
7～C
18Vinyl alkoxy silane, consumption is the 3-20% of monomer total amount.Chain-transfer agent is C
2～C
12Alkyl sulfhydryl or hydrosulphonyl silane, consumption is the 2-5% of monomer total amount, as mercaptoethanol, 2-mercaprol, butanethiol, lauryl mercaptan etc.Compound emulsifying agent employing anion surfactant and nonionogenic tenside are composite, consumption is the 7-20% of monomer total amount, as sodium lauryl sulphate-sorbitan trioleate, Sodium dodecylbenzene sulfonate-polyoxyethylene sorbitan monooleate, Succinic Acid diethyl ester sodium sulfonate-polyoxyethylene sorbitol acid anhydride laurate etc.Initiator is a redox initiator, and consumption is the 1-6% of monomer total amount, as hydrogen peroxide-iron protochloride, Potassium Persulphate-iron protochloride, Potassium Persulphate-sodium bisulfite, hyperis-iron protochloride etc.The pH regulator agent is carbonate, supercarbonate, phosphoric acid salt or the hydrosulfate of basic metal, alkaline-earth metal or ammonium, and consumption is the 0.2-1% of monomer total amount, as sodium bicarbonate, yellow soda ash, potassiumphosphate, sal enixum etc.
The present invention adopts emulsion polymerization to prepare nucleocapsid structure organosilicon-modified acrylate latex, compares with the preparation method of existing organosilicon-modified acrylate, can obtain narrow diameter distribution, nontoxic, do not fire, stable latex.The exterior coating that makes with it can replace mechanical commixed type and solvent borne organosilicon-modified acrylate exterior coating.
Adopt the organosilicon-modified acrylate latex of the present invention's preparation, have the following advantages:
1. the latex of the present invention's preparation is stone soft shell structure, both can reduce the second-order transition temperature of latex, reduces raw materials cost, can improve the mechanical property of filming again, increases the weathering resistance of filming.
2. the organosilicon function monomer that uses among the present invention is water miscible, is very easy to carry out copolymerization with other monomer, can hydrolysis before the copolymerization, and therefore the latex of preparation can be stablized storage more than 1 year.
3. the present invention adds the vinylformic acid cross-linking monomer in emulsion polymerization process, can improve the degree of crosslinking and the sticking power of latex, and need not add and after catalyzer can make organosilicon and other monomer copolymerization hydrolytic crosslinking take place, reduce emulsifying agent and catalyst consumption, increase the water tolerance of latex.
4. this method technology is simple, is easy to control, all can produce stable organosilicon-modified acrylate latex in certain temperature range.
5. this process using emulsion polymerisation process; solvent for use is a water, and the latex of preparation is nontoxic, do not fire, and has both helped environment protection; can reduce production costs again, the exterior coating that makes with it can replace mechanical commixed type and solvent borne organosilicon-modified acrylate exterior coating.
The organosilicon-modified acrylate latex of the present invention preparation than the non-silylation acrylate latex of the following preparation of similarity condition have much better water tolerance, scrub resistance, anti-stickly put forth effort, degree of crosslinking, sticking power, hardness and tensile strength.Can be used as high-grade exterior coating, waterproof paint, glass decoration coating etc.
Latex performance to the present invention's preparation can characterize with the following method: the particle diameter of organosilicon-modified acrylate latex adopts Coulter LS230 particle size analyzer to measure, being coated with film dynamic performance tests with the Instron electronic tension tester, the method that the latex degree of crosslinking was weighed by reflux in 24 hours is measured, adopt GB/T9286-88 cross cross-hatching measure sticking power (wherein 0 grade best, 5 grades the poorest), the test of anti-MEK (methyl ethyl ketone) solvent scouring number of times is to use by the saturated non-woven paper of MEK to come and go the scouring film coated surface, the scouring number of times that record is filmed and just frayed, the pencil hardness of filming is measured by ASTM D-3364.
Embodiment:
Example 1: set of monomers becomes butyl acrylate, 3,4-dimethyl styrene, the vinylformic acid-own ester of 6-hydroxyl, methacrylic acid, contains C
7～C
12Vinyl alkoxy silane, latex component prescription is as follows:
| Form | Weight percent (%) | |
| 1 | Emulsifying agent | 2 |
| 2 | Water | 45 |
| 3 | Methacrylic acid | 1 |
| 4 | Butyl acrylate | 20 |
| 5 | 3, the 4-dimethyl styrene | 20 |
| 6 | Vinylformic acid-own the ester of 6-hydroxyl | 5 |
| 7 | Vinylic organosiloxane | 1 |
| 8 | Potassium Persulphate-ferrous salt | 0.5 |
| 9 | Lauryl mercaptan | 2 |
| 10 | Sodium bicarbonate | 0.2 |
| Latex solid content (%) | 50 | |
With 1 part of emulsifying agent, 13 parts of water, 1 part of methacrylic acid, 3 parts of butyl acrylates, 8 part 3, the 4-dimethyl styrene, 2 parts of own esters of vinylformic acid-6-hydroxyl add in the reactor, stirred 20 minutes, temperature of reaction kettle is heated to 50 ℃, drip initiator, continue to be stirred to latex and faint blue light occurs, after 5 minutes, begin to drip good pre-emulsion of pre-emulsification (residual monomers and 30 parts water high-speed stirring 20 minutes) and initiator, in 3 hours pre-emulsion and initiator are all dripped, continue insulation 1.5 hours, add the pH to 9 that latex is regulated in the pH regulator agent, cold filtration promptly gets organosilicon-modified acrylate latex.
Example 2: set of monomers becomes butyl methacrylate, vinylformic acid-2-ethylamino ester, vinylformic acid hydroxy butyl ester, vinylformic acid, contains C
7～C
12Vinyl alkoxy silane, contain C
4～C
12The vinylformic acid cross-linking monomer, latex formulations is as follows:
| Form | Weight percent (%) | |
| 1 | Emulsifying agent | 4 |
| 2 | Water | 50 |
| 3 | Vinylformic acid | 1 |
| 4 | Vinylformic acid-2-ethylamino ester | 14 |
| 5 | Butyl methacrylate | 16 |
| 6 | The vinylformic acid hydroxy butyl ester | 4 |
| 7 | The vinylformic acid cross-linking monomer | 1 |
| 8 | Vinylic organosiloxane | 3 |
| 9 | Potassium Persulphate-ferrous salt | 0.6 |
| 10 | Mercaptoethanol | 1 |
| 11 | Sal enixum | 0.1 |
| Latex solid content (%) | 47 | |
1 part of emulsifying agent, 13 parts of water, 1 part of vinylformic acid-2-ethylamino ester, 8 parts of butyl methacrylate are added in the reactor, stirred 10 minutes, temperature of reaction kettle is heated to 55 ℃, drip initiator, continue to be stirred to latex and faint blue light occurs, after 5 minutes, begin to drip good pre-emulsion of pre-emulsification (residual monomers and 37 parts water high-speed stirring 30 minutes) and initiator, 2.5 in hour pre-emulsion and initiator are all dripped, continue insulation 2 hours, add the pH regulator agent and regulate the pH to 8 of latex, cold filtration promptly gets organosilicon-modified acrylate latex.
Example 3: set of monomers becomes methacrylic acid-2-methyl ester, ethyl propenoate, Propylene glycol monoacrylate, methacrylic acid, vinylbenzene, contains C
7～C
12Vinyl alkoxy silane, contain C
4～C
12The vinylformic acid cross-linking monomer, latex formulations is as follows:
| Form | Weight percent (%) | |
| 1 | Emulsifying agent | 3 |
| 2 | Water | 50 |
| 3 | Methacrylic acid | 2 |
| 4 | Ethyl propenoate | 10 |
| 5 | Methacrylic acid-2-methyl ester | 16 |
| 6 | Propylene glycol monoacrylate | 5 |
| 7 | Vinylbenzene | 5 |
| 8 | The vinylformic acid cross-linking monomer | 1.5 |
| 9 | Vinylic organosiloxane | 6 |
| 10 | Ammonium persulphate-ferrous salt | 0.6 |
| 11 | Mercaptoethanol | 1 |
| 12 | Yellow soda ash | 0.1 |
| Latex solid content (%) | 45 | |
With 1 part of emulsifying agent, 15 parts of water, 1 part of methacrylic acid, 2 parts of ethyl propenoates, 6 parts of methacrylic acid-2-methyl ester, 1 part of vinylbenzene and 1 part of Propylene glycol monoacrylate add in the reactor, stirred 30 minutes, temperature of reaction kettle is heated to 65 ℃, drip initiator, continue to be stirred to latex and faint blue light occurs, after 15 minutes, begin to drip good pre-emulsion of pre-emulsification (residual monomers and 35 parts water high-speed stirring 20 minutes) and initiator, in 3 hours pre-emulsion and initiator are all dripped, continue insulation 1 hour, add the pH regulator agent and regulate the pH to 7.5 of latex, cold filtration promptly gets organosilicon-modified acrylate latex.
The performance characterization of example 1-3 is as follows:
| Non-silylation latex | Example 1 | Example 2 | Example 3 | |
| Latex particle size (μ m) | 0.114 | 0.116 | 0.118 | 0.113 |
| The latex particle size distribution (plastisied dispersion, %) | 42.2 | 12.5 | 11.7 | 11.2 |
| The latex package stability | Still stable more than 1 year | Still stable more than 1 year | Still stable more than 1 year | |
| Film adhesive/level | 5 | 0 | 0 | 0 |
| Water-resistance property of coating | There is water to film and whitens immediately, film and to peel off | Film after 5 hours and slightly whiten, film not | Film after 15 hours and slightly whiten, film not | Film after 20 hours and slightly whiten, be coated with |
| Can peel off | Can peel off | Film can not peel off | ||
| Anti-stick the putting forth effort of filming | Sticking hand | Tack-free | Tack-free | Tack-free |
| The tensile strength of filming (Mpa) | 1.01 | 1.75 | 2.03 | 2.59 |
| Degree of crosslinking (%) | 20.5 | 70.2 | 83.6 | 92.8 |
| Pencil hardness | 2B | HB | H | 2H |
| Anti-MEK cleans number of times | 30 | ＞200 | ＞300 | ＞300 |
Under same test conditions, the organosilicon modified acrylate latex with core-shell structure of the present invention preparation than the non-silylation acrylate latex of the following preparation of similarity condition have much better water tolerance, scrub resistance, anti-stickly put forth effort, degree of crosslinking, sticking power, hardness and tensile strength.
Claims (10)
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| CN105601799B (en) * | 2016-01-05 | 2018-03-16 | 广州中国科学院工业技术研究院 | Core/shell type organosilicon-modified acrylate emulsion and its preparation method and application |
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| CN113402681A (en) * | 2021-06-24 | 2021-09-17 | 中科院广州化学有限公司 | Mercapto-containing organic silicon modified styrene-acrylic emulsion and preparation method and application thereof |
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| CN1217360A (en) * | 1997-11-13 | 1999-05-26 | 中国石油化工总公司 | Process for preparing organosilicon modified propenoic acid emulsion paint |
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| CN1217360A (en) * | 1997-11-13 | 1999-05-26 | 中国石油化工总公司 | Process for preparing organosilicon modified propenoic acid emulsion paint |
| CN1217361A (en) * | 1997-11-13 | 1999-05-26 | 中国石油化工总公司 | Organosilicon modified propenoic acid emulsion paint |
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