CN102898578B - Self-crosslinking silicone-acrylate copolymer emulsion and preparation method - Google Patents
Self-crosslinking silicone-acrylate copolymer emulsion and preparation method Download PDFInfo
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- CN102898578B CN102898578B CN201210243411.4A CN201210243411A CN102898578B CN 102898578 B CN102898578 B CN 102898578B CN 201210243411 A CN201210243411 A CN 201210243411A CN 102898578 B CN102898578 B CN 102898578B
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- 239000000839 emulsion Substances 0.000 title claims abstract description 96
- 238000004132 cross linking Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims description 15
- 229920001577 copolymer Polymers 0.000 title abstract description 13
- 238000004945 emulsification Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 16
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 14
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 86
- 239000000203 mixture Substances 0.000 claims description 60
- 229920000058 polyacrylate Polymers 0.000 claims description 40
- -1 Alkyl methacrylate Chemical compound 0.000 claims description 30
- 239000000693 micelle Substances 0.000 claims description 19
- 229920001296 polysiloxane Polymers 0.000 claims description 19
- 238000009413 insulation Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 9
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000012874 anionic emulsifier Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000000750 progressive effect Effects 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- 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 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 230000033116 oxidation-reduction process Effects 0.000 claims description 3
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 3
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 3
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 claims description 2
- PBCKVROHSSNSDY-UHFFFAOYSA-N 2-methylprop-2-enoic acid;sodium Chemical compound [Na].CC(=C)C(O)=O PBCKVROHSSNSDY-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 2
- GZGWBUJWNXQXKV-UHFFFAOYSA-N n-tetradecan-2-ylprop-2-enamide Chemical compound CCCCCCCCCCCCC(C)NC(=O)C=C GZGWBUJWNXQXKV-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
- VYDYYGLAYDLGRT-UHFFFAOYSA-N phenoxybenzene;sodium Chemical compound [Na].[Na].C=1C=CC=CC=1OC1=CC=CC=C1 VYDYYGLAYDLGRT-UHFFFAOYSA-N 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 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
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 23
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 2
- 125000005907 alkyl ester group Chemical group 0.000 abstract 1
- 239000004816 latex Substances 0.000 description 10
- 229920000126 latex Polymers 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229910002808 Si–O–Si Inorganic materials 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920006222 acrylic ester polymer Polymers 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000011430 maximum method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to the organic compound technical field, which solves the problems of poor stability of the silicone-acrylate copolymer emulsion and poor water resistance and stain resistance performances of a film due to low silicon content. The invention relates to a self-crosslinking silicone-acrylate copolymer emulsion which comprises the following components by mass percentages: 10.0-30.0% of methacrylic acid alkylester, 15.0-30.0% of alkyl acrylate, 5-15% of organosiloxane, 0.5-2.5% of alkyl ester, 1.0-5.0% of organosilicone hydrolysis inhibitor, 0.5-2.0% of pH modifier, 0.5-2.0% of emulsifier, 0.5-1.0% of initiator and 40.0-60.0% of water. The emulsion good reaction and storage stability, the silicon content used for constituting colloidal particles and its functional group distribution is gradually increased from 60-80% of colloidal particle radius to the surface, the organosilicone segment function can fully performed, and the cost performance of product is enhanced.
Description
Technical field
The present invention relates to organic compound technical field, be specially a kind of self-crosslinking silicone-acrylic polymer emulsion used for building exterior wall and preparation method thereof.
Background technology
Along with buildings is to high stratification, maximization future development, have higher requirement to the performance such as weathering resistance, contamination resistance, washability of high-rise coating, the application cycle of general requirement skin coating is at least more than 15 years.Acrylic resin has good weathering resistance, gloss retention and good film-forming properties usually, but linear molecule lacks cross-linking set, be difficult to form three-dimensional netted crosslinked film, cause that its high thermal resistance is poor, high temperature easily after-tacks, the easy embrittlement of low temperature film, to lack flexibility.And the general work-ing life of acrylic resin paint only has 5-10, can not reach the service requirements of external wall of building thing coating.In order to overcome the shortcoming of acrylic resin paint, adopt both at home and abroad organosilicon to acrylic resin carry out modification to improve the performance such as it is water-fast, stain resistant.Because silica bond energy (460kJ/mol) is higher than carbon-oxygen bond energy (351 kJ/mol) and carbon-carbon bond energy (347 kJ/mol), determine organic-silicon-modified acrylic resin paint and there is excellent temperature tolerance, weathering resistance, organosilicon is because having extremely low surface energy simultaneously, and thus organic-silicon-modified acrylic coating has excellent contamination resistance, water tolerance.Therefore, high performance siloxane-acrylate copolymer emulsion has become the focus that coating industry is paid close attention to.
Organosilicon modified crylic acid resin, generally has physical blending and chemical copolymerization two kinds of methods.Physical blending mixes with certain proportion with acrylic ester emulsion by organo-siloxane, and this method technique is simple but limited to the raising of film performance, and there is shortcomings such as being separated.Chemical copolymerization adopts maximum methods at present, the mode that organosilane monomer introducing acrylic ester polymer mainly adopts is unsaturated silane monomer and the acrylic ester monomer copolymerization that will be with active group, make grafted-organosilicon oxygen alkane molecular chain on acrylic ester polymer molecular chain, there is intermolecular condensation and form Si-O-Si key in the Si-OH that in curing of coating process, active group (as alkoxyl group) hydrolysis is formed, or with hydroxy-acrylate monomer (as 2-Hydroxy ethyl acrylate)-OH, condensation cross-linking occurs and form tridimensional network.This copolymeric structure is conducive to siloxane chain group in the arrangement of film surface orientation, improves the hydrophobicity of copolymerization organosilicon-modified acrylic emulsion film, improves film contamination resistance.But when preparing organosilicon-modified acrylic emulsion, because organo-siloxane monomer can occur to be hydrolyzed autohemagglutination in aqueous phase, when particularly organosilane monomer content is larger, this hydrolysis autohemagglutination not only can reduce the reaction stability of polymer emulsion, even producing gel time serious makes reaction carry out, cause emulsion organosilicon component content lower, and can produce to be separated and affect film over-all properties.And, when general introducing organo-siloxane monomer copolymerization prepares organosilicon-modified acrylic emulsion, part silicone monomer is in latex particle interior polymeric, when being unfavorable on the one hand film forming there is hydrolysis and crosslinked in siloxanes, the Si-O-Si be cross-linked to form on the other hand can not move to film coated surface, effectively can not play the effect of Si-O-Si segment.Finally, generally adopt low molecular weight emulsifier in organosilicon-modified acrylic emulsion polymerization process, in film process, easily move to film coated surface, affect the performances such as film is water-fast.Therefore, how effectively to suppress organosilane monomer autohemagglutination, improve stability of emulsion polymerization and silicone content, how aggregation technique makes the Si-O-Si be cross-linked to form move to film coated surface as far as possible, giving full play to Si-O-Si segment to do in order to improve product cost, is the focus of high-grade exterior coating research.
Chinese patent CN200910068807 discloses a kind of preparation method of nuclear shell structure high-silicon silicone acrylic emulsion used for building exterior wall, and the method first prepares silicone oligomer, then carries out the organosilicon crylic acid latex that core-shell emulsion polymerization preparation has nucleocapsid structure.For improving film performance, although devise the particle with nucleocapsid structure, the difference between nucleocapsid structure composition can not be eliminated, easily cause being separated of nucleocapsid part, even there is nucleocapsid obscission time serious, have a strong impact on the performances such as hydrophobic, the stain resistant of film.In addition, this method all introduces organo-siloxane in the nucleocapsid part of particle, and the silicone content of emulsion obtains large increase.But during emulsion film forming solidification, the silica segment of particle core part can not move to film coated surface, causes this part silica segment effectively can not play the effects such as it is hydrophobic, stain resistant.
Summary of the invention
The problems such as water-resistance property of coating, contamination resistance difference are caused for solution siloxane-acrylate copolymer stability of emulsion is poor and silicone content is low, the invention provides a kind of self-crosslinking silicone-acrylic polymer emulsion, emulsion has good reaction and stability in storage, the silicone content of composition micelle and functional group's distribution thereof are from micelle radius 60 ~ 80% to surperficial progressive increase, give full play to silicone segments effect, improve product cost.
Another object of the present invention is to provide a kind of preparation method of self-crosslinking silicone-acrylic polymer emulsion, and preparation method of the present invention is simple.
The present invention provides the application of self-crosslinking silicone-acrylic polymer emulsion on external wall simultaneously.
The present invention is achieved by the following technical solutions: a kind of self-crosslinking silicone-acrylic polymer emulsion, and described self-crosslinking silicone-acrylic polymer emulsion is made up of following component, and the mass percent of each component is:
Alkyl methacrylate 10.0 ~ 30.0%,
Alkyl acrylate 15.0 ~ 30.0%,
Organo-siloxane 5 ~ 15%,
Hydroxyalkyl acrylate 0.5 ~ 2.5%,
Organosilicon hydrolyzation inhibitor 1.0 ~ 5.0%,
PH adjusting agent 0.5 ~ 2.0%,
Emulsifying agent 0.5 ~ 2.0%,
Initiator 0.5 ~ 1.0%,
Water 40.0 ~ 60.0%,
Described alkyl methacrylate is selected from the mixture of one or more arbitrary proportions in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, pentylmethacrylate, N-Hexyl methacrylate, Isooctyl methacrylate;
Described alkyl acrylate is selected from the mixture of one or more arbitrary proportions in methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, amyl acrylate, Ethyl acrylate, Isooctyl acrylate monomer;
Described organo-siloxane is selected from the mixture of one or more arbitrary proportions in vinyltrimethoxy silane, vinyltriethoxysilane, vinyltributoxysilane, γ-methacryloxypropyl trimethoxy silane;
Described hydroxyalkyl acrylate is selected from the mixture of one or more arbitrary proportions in 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxybutyl, vinylformic acid-5-hydroxyl pentyl ester, the own ester of vinylformic acid-6-hydroxyl, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-3-hydroxy propyl ester;
Described organosilicon hydrolyzation inhibitor is selected from the mixture of one or more arbitrary proportions in the low molecular poly of propylene glycol, Isosorbide-5-Nitrae butyleneglycol, the polymerization degree 400 or 600;
Described initiator is selected from persulphate and sulfite oxidation-reduction system, and persulphate is 1.5 ~ 2.5 times of sulphite quality.Persulphate is selected from the mixture of one or more arbitrary proportions in Potassium Persulphate, Sodium Persulfate, ammonium persulphate, and sulphite is selected from the mixture of one or more arbitrary proportions in S-WAT, sodium bisulfite, potassium sulfite, Potassium hydrogen sulfite, ammonium sulphite, ammonium bisulfite;
Described emulsifying agent is anionic emulsifier and reactive emulsifier compound, reactive emulsifier is 1 ~ 3 times of anionic emulsifier quality, and wherein anionic emulsifier is selected from the mixture of one or more arbitrary proportions in dodecyl diphenyl oxide disodium sulfonate (DSB), Sodium dodecylbenzene sulfonate (LAS), sodium lauryl sulphate (SDS); Reactive emulsifier is selected from 2-acrylamido-2-methyI-oropvD sulfonate sodium (AMPS-Na), 2-acrylamido-2-methyI-oropvD sulfonic acid ammonium salt (AMPS-NH
4), the mixture of one or more arbitrary proportions in 1-allyloxy-2-hydroxypropyl azochlorosulfonate acid sodium (HAPS), 2-acrylamido tetradecane sulfonate sodium (NaAMC14S), methacrylic acid hydroxide sodium dimercaptosulphanatein (HPMAS).
Described pH adjusting agent is selected from the mixture of one or more arbitrary proportions in sodium bicarbonate, saleratus;
Described water is deionized water.
A preparation method for self-crosslinking silicone-acrylic polymer emulsion is following steps:
(1) each component is taken by the mass percent of self-crosslinking silicone-acrylic polymer emulsion component;
(2) alkyl methacrylate of 50% ~ 80%, the alkyl acrylate of 30% ~ 70% in step (1) are mixed and made into monomer I, remaining alkyl methacrylate, alkyl acrylate are mixed and made into monomer II, and hydroxyalkyl acrylate, organo-siloxane are mixed and made into monomer III; As preferably, monomer I is 1.5 ~ 3:1 with the mass ratio of monomer II.According to following FOX formulae discovery, described monomer I second-order transition temperature is 10 ~ 30 DEG C, and monomer II second-order transition temperature is-40 ~-20 DEG C.
Wherein, X
nfor the mass percentage of each component monomer in mix monomer, T
gnfor the absolute second-order transition temperature of each component monomer homopolymer.
(3) prepare seed emulsion: by step (1) 60% ~ 80% water, the emulsifying agent of 50% ~ 80%, initiator, hydrolysis inhibitor, the pH adjusting agent of 50% ~ 70% add in reactor, stir and be warming up to 65 ~ 70 DEG C after 10 ~ 20 minutes, then monomer I is added in reactor, within 2 ~ 4 hours, drip off, dropwise rear insulation 15 ~ 30 minutes, make seed emulsion;
(4) by monomer III in 1 ~ 2 hour, to drop in monomer II and Keep agitation, then the mixture of above-mentioned monomer II and monomer III and remaining water, emulsifying agent and initiator are added drop-wise in the seed emulsion obtained in step (3) continuously, dropwise rear reaction 0.5 ~ 1 hour, be warming up to 75 ~ 85 DEG C of insulations 1 ~ 2 hour again, then be cooled to 40 ~ 50 DEG C, filter discharging, namely obtain self-crosslinking silicone-acrylic polymer emulsion.As preferably, every 20 ~ 40 minutes measured reaction system pH in reaction process, if pH value is outside 6.0 ~ 7.0 intervals, use the material (namely with the component of foregoing pH adjusting agent the same material) identical with pH adjusting agent composition to regulate between pH value of reaction system to 6.0 ~ 7.0, be preferably adjusted to 6.5.
It is that different weight of material is by keeping the speed of response of material at the reactor of corresponding size in order to maintain thermal equilibrium in reactor and the certain speed of reaction of reaction mass that step (3), (4) limit joining day of material.
This patent introduces organo-siloxane on seed emulsion basis, and the silicone content of siloxane-acrylate copolymer emulsion composition micelle and functional group's distribution thereof are from micelle radius 60 ~ 80% to surperficial progressive increase.Silicone segments and other set of monomers become content to increase gradually, eliminate the difference of particle composition structure.On the other hand, during emulsion particle solidification, outer field silica segment easily moves to film coated surface, thus can give full play to the effect of silicone segments, improve product cost.
Emulsifying agent of the present invention is the compound of anionic emulsifier and reactive emulsifier, and initiator is the compound of persulphate and sulphite, and initiator is oxidation-reduction system.At emulsifying agent, initiator, under the effect of organosilicon hydrolyzation inhibitor, gradient is adopted to feed in raw material method, the silicone content of siloxane-acrylate copolymer emulsion composition micelle and functional group thereof is made to distribute from micelle radius 60 ~ 80% to surperficial progressive increase, obtain the self-crosslinking silicone-acrylic polymer emulsion that latex particle particle diameter is about 100 nm, emulsion particle entirety combines closely, phenomenon of phase separation can not be there is, organo-siloxane monomer and segment are mainly distributed in micelle radius 60 ~ 80% place to surface, give full play to the effect of Si-O-Si segment, improve the cost performance of organosilicon crylic acid latex, ensure that the film-forming properties that siloxane-acrylate copolymer emulsion is good, the performance such as water tolerance and stain resistant.
The present invention is obtained by organo-siloxane and alkyl acrylate, alkyl methacrylate, hydroxyalkyl acrylate copolymerization.During preparation, first the alkyl methacrylate of 50 ~ 80%, the alkyl acrylate of 30 ~ 70% in composition of raw materials are made monomer I and the obtained seed emulsion of polymerization, then the alkyl methacrylate of remainder, alkyl acrylate are made monomer II, hydroxyalkyl acrylate and organo-siloxane are made monomer III.When monomer II is evenly added drop-wise to seed emulsion, monomer III is evenly added drop-wise in monomer II, until monomer III dropwises simultaneously.Introduce reactive emulsifier and hydroxyl cross-linking monomer in reaction, reduce and eliminate the problems such as the micromolecular existence of emulsifying agent causes stability of emulsion, water-resistance property of coating poor, the physical-chemical performance of emulsion film is improved.
The application of a kind of self-crosslinking silicone-acrylic polymer emulsion of the present invention on external wall.
Compared with prior art, the invention has the beneficial effects as follows:
(1) silicone content of the self-crosslinking silicone-acrylic polymer emulsion composition micelle obtained by and functional group's distribution thereof, from micelle radius 60 ~ 80% to surperficial progressive increase, can give full play to the effect of silicone segments, improve product cost.
(2) self-crosslinking silicone-acrylic polymer emulsion of the present invention has good reaction stability and stability in storage, and film has excellent contamination resistance, water tolerance, ageing resistance.
Embodiment
Be described in further detail the present invention below in conjunction with embodiment, raw materials used all commercially available in embodiment, it should be noted that, embodiment does not form limiting the scope of the invention.
Embodiment 1:
(1) self-crosslinking silicone-acrylic polymer emulsion component is as shown in table 1 below:
(2) above-mentioned methyl methacrylate, butyl acrylate, 2-Hydroxy ethyl acrylate and vinyltriethoxysilane are mixed and made into monomer I, monomer II and monomer III respectively;
(3) prepare seed emulsion: by the deionized water of above-mentioned quality 80%, SDS and AMPS mixture quality 70%, Potassium Persulphate and sodium bisulfite mixture quality 60%, sodium bicarbonate, propylene glycol join in the reactor that thermometer, agitator, filling tube, condensing reflux pipe are housed, dispersed with stirring 15 minutes, treat that temperature rises to 68 DEG C, monomer I was dripped off in 3 hours, dropwise rear insulation 15 minutes, make seed emulsion;
(4) in 1.5 hours, slowly being dropped to by monomer III in monomer II and maintaining stirring makes it mix, then the mixture of above-mentioned monomer II and monomer III and remaining deionized water, emulsifying agent and initiator are added drop-wise to continuously in the seed emulsion that step (3) obtains, dropwise rear reaction 0.5 hour, be warming up to 80 DEG C of insulations 1.5 hours again, then be cooled to 40 DEG C, filter discharging, obtain self-crosslinking siloxane-acrylate copolymer emulsion.
Every 20 minutes measured reaction system pH in step (4) reaction process, when pH value uses sodium bicarbonate to regulate pH value of reaction system to 6.5 when 6.0 ~ 7.0 intervals are outer.
Testing the self-crosslinking silicone-acrylic polymer seeds emulsion median size obtained is 65nm, and final median size is 95nm, narrowly distributing.Tem analysis display self-crosslinking silicopropyl emulsion latex particle size is even, is the spherical of rule.SEM and AFM analyzes and shows that emulsion has good film-forming properties, and film forming is fine and close in phenomenon of phase separation.NMR, FTIR and ultimate analysis etc. show, micelle is from particle diameter 65nm place, and along with particle diameter increases gradually, silicone content and functional group's distribution thereof of self-crosslinking silicone-acrylic polymer emulsion composition micelle also increase gradually.Self-crosslinking silicone-acrylic polymer emulsion film water contact angle is 115 °, and within 24 hours, water-intake rate is only 2.3%.
Embodiment 2
(1) self-crosslinking silicone-acrylic polymer emulsion component is as shown in table 2 below:
(2) above-mentioned methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, amyl acrylate, 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, γ-methacryloxypropyl trimethoxy silane are mixed and made into monomer I, monomer II and monomer III respectively;
(3) prepare seed emulsion: by the deionized water of above-mentioned quality 70%, DBS and HAPS mixture quality 65%, ammonium persulphate and Potassium hydrogen sulfite mixture quality 50%, sodium bicarbonate, 1,4 butyleneglycols join in the reactor that thermometer, agitator, filling tube, condensing reflux pipe are housed, dispersed with stirring 10 minutes, treat that temperature rises to 65 DEG C, monomer I was dripped off at 3.5 hours, dropwise rear insulation 20 minutes, make seed emulsion;
(4) in 2 hours, slowly being dropped to by monomer III in monomer II and maintaining stirring makes it mix, and the mixture of above-mentioned monomer II and monomer III and remaining deionized water, emulsifying agent and initiator are added drop-wise to continuously in the seed emulsion that step (3) obtains simultaneously, dropwise rear reaction 0.5 hour, be warming up to 78 DEG C of insulations 1 hour again, then be cooled to 45 DEG C, filter discharging, obtain self-crosslinking siloxane-acrylate copolymer emulsion.
Every 30 minutes measured reaction system pH in step (4) reaction process, when pH value is when 6.0 ~ 7.0 intervals are outer, use sodium bicarbonate to regulate pH value of reaction system to 6.8.
Testing the self-crosslinking silicone-acrylic polymer seeds emulsion median size obtained is 68nm, and final median size is 97nm, narrowly distributing.Tem analysis display self-crosslinking silicone-acrylic polymer emulsion latex particle size is even, is the spherical of rule.SEM and AFM analyzes and shows that emulsion has good film-forming properties, and film forming is fine and close in phenomenon of phase separation.NMR, FTIR and ultimate analysis etc. show, micelle is from particle diameter 68nm place, and along with particle diameter increases gradually, silicone content and functional group's distribution thereof of self-crosslinking silicone-acrylic polymer emulsion composition micelle also increase gradually.Self-crosslinking silicone-acrylic polymer emulsion film water contact angle is 112 °, and within 24 hours, water-intake rate is only 2.8%.
Embodiment 3:
(1) self-crosslinking silicone-acrylic polymer emulsion component is as shown in table 3 below:
(2) above-mentioned β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl acrylate, 2-Hydroxy ethyl acrylate, vinylformic acid-5-hydroxyl pentyl ester and vinyltributoxysilane are mixed and made into mix monomer I, mix monomer II and mix monomer III respectively;
(3) seed emulsion is prepared: by deionized water, LAS and the AMPS-NH of above-mentioned quality 75%
460% of mixture quality, 70% of Potassium Persulphate and sodium bisulfite mixture quality, saleratus, the polymerization degree 400 low molecular poly join in the reactor that thermometer, agitator, filling tube, condensing reflux pipe are housed, dispersed with stirring 20 minutes, treat that temperature rises to 70 DEG C, mix monomer I was dripped off at 4 hours, dropwise rear insulation 30 minutes, make seed emulsion.
(4) in 2 hours, slowly being dropped to by monomer III in monomer II and maintaining stirring makes it mix, and the mixture of above-mentioned monomer II and monomer III and remaining deionized water, emulsifying agent and initiator are added drop-wise to continuously in the seed emulsion that step (3) obtains simultaneously, dropwise rear reaction 0.5 hour, be warming up to 80 DEG C of insulations 1.5 hours again, then be cooled to 50 DEG C, filter discharging, obtain self-crosslinking siloxane-acrylate copolymer emulsion.
Every 30 minutes measured reaction system pH in step (4) reaction process, when pH value is when 6.0 ~ 7.0 intervals are outer, use saleratus to regulate pH value of reaction system to 6.2.
Testing the self-crosslinking silicone-acrylic polymer seeds emulsion median size obtained is 72nm, and final median size is 103nm, narrowly distributing.Tem analysis display organosilicon crylic acid latex latex particle size is even, is the spherical of rule.SEM and AFM analyzes and shows that emulsion has good film-forming properties, and film forming is fine and close in phenomenon of phase separation.NMR, FTIR and ultimate analysis etc. show, micelle is from particle diameter 72nm place, and along with particle diameter increases gradually, silicone content and functional group's distribution thereof of self-crosslinking silicone-acrylic polymer emulsion composition micelle also increase gradually.Self-crosslinking silicone-acrylic polymer emulsion film water contact angle is 110 °, and within 24 hours, water-intake rate is only 3.2%.
Embodiment 4:
(1) self-crosslinking silicone-acrylic polymer emulsion component is as shown in table 4 below:
(2) above-mentioned methyl methacrylate, butyl methacrylate, Isooctyl methacrylate, ethyl propenoate, butyl acrylate, 2-Hydroxy ethyl acrylate, vinylformic acid-5-hydroxyl pentyl ester and vinyltrimethoxy silane are mixed and made into monomer I, monomer II and monomer III respectively;
(3) seed emulsion is prepared: by the deionized water of above-mentioned quality 80%, LAS, DSB, AMPS-Na, AMPS-NH
4saleratus, the polymerization degree 600 low molecular poly of 60% of mixture quality, 65%, 80% of Sodium Persulfate and sodium bisulfite mixture quality join in the reactor that thermometer, agitator, filling tube, condensing reflux pipe are housed, dispersed with stirring 15 minutes, treat that temperature rises to 68 DEG C, mix monomer I was dripped off at 2 hours, dropwise rear insulation 30 minutes, make seed emulsion.
(4) in 2 hours, slowly being dropped to by mix monomer III in monomer II and maintaining stirring makes it mix, and the mixture of above-mentioned monomer II and monomer III and remaining deionized water, emulsifying agent and initiator are added drop-wise to continuously in the seed emulsion that step (3) obtains simultaneously, dropwise rear reaction 1 hour, be warming up to 85 DEG C of insulations 1 hour again, then be cooled to 40 DEG C, filter discharging, obtain self-crosslinking siloxane-acrylate copolymer emulsion.
Every 40 minutes measured reaction system pH in step (4) reaction process, when pH value is when 6.0 ~ 7.0 intervals are outer, use saleratus to regulate pH value of reaction system to 6.5.
Testing the self-crosslinking silicone-acrylic polymer seeds emulsion median size obtained is 62nm, and final median size is 98nm, narrowly distributing.Tem analysis display organosilicon crylic acid latex latex particle size is even, is the spherical of rule.SEM and AFM analyzes and shows that emulsion has good film-forming properties, and film forming is fine and close in phenomenon of phase separation.NMR, FTIR and ultimate analysis etc. show, micelle is from particle diameter 62nm place, and along with particle diameter increases gradually, silicone content and functional group's distribution thereof of self-crosslinking silicone-acrylic polymer emulsion composition micelle also increase gradually.Self-crosslinking silicone-acrylic polymer emulsion film water contact angle is 109 °, and within 24 hours, water-intake rate is only 3.4%.
Claims (6)
1. a self-crosslinking silicone-acrylic polymer emulsion, it is characterized in that, described self-crosslinking silicone-acrylic polymer emulsion is made up of following component, and the silicone content of composition micelle and functional group's distribution thereof are from micelle radius 60 ~ 80% to surperficial progressive increase, and the mass percent of each component is:
Alkyl methacrylate 10.0 ~ 30.0%,
Alkyl acrylate 15.0 ~ 30.0%,
Organo-siloxane 5 ~ 15%,
Hydroxyalkyl acrylate 0.5 ~ 2.5%,
Organosilicon hydrolyzation inhibitor 1.0 ~ 5.0%,
PH adjusting agent 0.5 ~ 2.0%,
Emulsifying agent 0.5 ~ 2.0%,
Initiator 0.5 ~ 1.0%,
Water 40.0 ~ 60.0%,
Described alkyl methacrylate is selected from the mixture of one or more arbitrary proportions in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, pentylmethacrylate, N-Hexyl methacrylate, Isooctyl methacrylate;
Described alkyl acrylate is selected from the mixture of one or more arbitrary proportions in methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, amyl acrylate, Ethyl acrylate, Isooctyl acrylate monomer;
Described organo-siloxane is selected from the mixture of one or more arbitrary proportions in vinyltrimethoxy silane, vinyltriethoxysilane, vinyltributoxysilane, γ-methacryloxypropyl trimethoxy silane;
Described hydroxyalkyl acrylate is selected from the mixture of one or more arbitrary proportions in 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxybutyl, vinylformic acid-5-hydroxyl pentyl ester, the own ester of vinylformic acid-6-hydroxyl, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-3-hydroxy propyl ester;
Described organosilicon hydrolyzation inhibitor is selected from the mixture of one or more arbitrary proportions in the low molecular poly of propylene glycol, Isosorbide-5-Nitrae butyleneglycol, the polymerization degree 400 or 600;
Described initiator is selected from persulphate and sulfite oxidation-reduction system, and persulphate is 1.5 ~ 2.5 times of sulphite quality;
Persulphate is selected from the mixture of one or more arbitrary proportions in Potassium Persulphate, Sodium Persulfate, ammonium persulphate, and sulphite is selected from the mixture of one or more arbitrary proportions in S-WAT, sodium bisulfite, potassium sulfite, Potassium hydrogen sulfite, ammonium sulphite, ammonium bisulfite;
Described emulsifying agent is the compound of anionic emulsifier and reactive emulsifier, wherein reactive emulsifier is 1 ~ 3 times of anionic emulsifier quality, and anionic emulsifier is selected from the mixture of one or more arbitrary proportions in dodecyl diphenyl oxide disodium sulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate; Reactive emulsifier is selected from the mixture of one or more arbitrary proportions in 2-acrylamido-2-methyI-oropvD sulfonate sodium, 2-acrylamido-2-methyI-oropvD sulfonic acid ammonium salt, 1-allyloxy-2-hydroxypropyl azochlorosulfonate acid sodium, 2-acrylamido tetradecane sulfonate sodium, methacrylic acid hydroxide sodium dimercaptosulphanatein;
Described pH adjusting agent is selected from the mixture of one or both arbitrary proportions in sodium bicarbonate, saleratus;
Described water is deionized water;
Preparation method is following steps:
(1) each component is taken by the mass percent of component;
(2) alkyl methacrylate of 50% ~ 80%, the alkyl acrylate of 30% ~ 70% in step (1) are mixed and made into monomer I, remaining alkyl methacrylate, alkyl acrylate are mixed and made into monomer II, hydroxyalkyl acrylate, organo-siloxane are mixed and made into monomer III, the polymers obtained second-order transition temperature of described monomer I is 10 ~ 30 DEG C, and the polymers obtained second-order transition temperature of monomer II is-40 ~-20 DEG C;
(3) prepare seed emulsion: by step (1) 60% ~ 80% water, the emulsifying agent of 50% ~ 80%, initiator, hydrolysis inhibitor, the pH adjusting agent of 50% ~ 70% add in reactor, stir and be warming up to 65 ~ 70 DEG C after 10 ~ 20 minutes, then monomer I is added in reactor, within 2 ~ 4 hours, drip off, dropwise rear insulation 15 ~ 30 minutes, make seed emulsion;
(4) by monomer III in 1 ~ 2 hour, to drop in monomer II and Keep agitation, then the mixture of above-mentioned monomer II and monomer III and remaining water, emulsifying agent and initiator are added drop-wise in the seed emulsion obtained in step (3) continuously, dropwise rear reaction 0.5 ~ 1 hour, be warming up to 75 ~ 85 DEG C of insulations 1 ~ 2 hour again, then be cooled to 40 ~ 50 DEG C, filter discharging, namely obtain self-crosslinking silicone-acrylic polymer emulsion.
2. a preparation method for a kind of self-crosslinking silicone-acrylic polymer emulsion as claimed in claim 1, is characterized in that, described preparation method is following steps:
(1) each component is taken by the mass percent of component;
(2) alkyl methacrylate of 50% ~ 80%, the alkyl acrylate of 30% ~ 70% in step (1) are mixed and made into monomer I, remaining alkyl methacrylate, alkyl acrylate are mixed and made into monomer II, and hydroxyalkyl acrylate, organo-siloxane are mixed and made into monomer III;
(3) prepare seed emulsion: by step (1) 60% ~ 80% water, the emulsifying agent of 50% ~ 80%, initiator, hydrolysis inhibitor, the pH adjusting agent of 50% ~ 70% add in reactor, stir and be warming up to 65 ~ 70 DEG C after 10 ~ 20 minutes, then monomer I is added in reactor, within 2 ~ 4 hours, drip off, dropwise rear insulation 15 ~ 30 minutes, make seed emulsion;
(4) by monomer III in 1 ~ 2 hour, to drop in monomer II and Keep agitation, then the mixture of above-mentioned monomer II and monomer III and remaining water, emulsifying agent and initiator are added drop-wise in the seed emulsion obtained in step (3) continuously, dropwise rear reaction 0.5 ~ 1 hour, be warming up to 75 ~ 85 DEG C of insulations 1 ~ 2 hour again, then be cooled to 40 ~ 50 DEG C, filter discharging, namely obtain self-crosslinking silicone-acrylic polymer emulsion.
3. the preparation method of a kind of self-crosslinking silicone-acrylic polymer emulsion according to claim 2, is characterized in that, in step (2), monomer I is 1.5 ~ 3:1 with the mass ratio of monomer II.
4. the preparation method of a kind of self-crosslinking silicone-acrylic polymer emulsion according to Claims 2 or 3, is characterized in that, every 20 ~ 40 minutes measured reaction system pH in step (4) reaction process, adjust ph is between 6.0 ~ 7.0.
5. the preparation method of a kind of self-crosslinking silicone-acrylic polymer emulsion according to claim 4, is characterized in that, uses the material identical with pH adjusting agent composition to regulate the pH value of reaction system in step (4).
6. the application of an a kind of self-crosslinking silicone-acrylic polymer emulsion as claimed in claim 1 on external wall.
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Effective date of registration: 20210802 Address after: 311604 No. 58 hejiagang Road, Meicheng Town, Jiande City, Hangzhou City, Zhejiang Province Patentee after: Jiande Xin'an silicone new material Research Institute Address before: 310036 No. 16 Xuelin Road, Xiasha Economic Development Zone, Hangzhou City, Zhejiang Province Patentee before: Hangzhou Normal University |