CN1456577A - Organic siloxane modified phenylethylene-acrylic ester nano-emulsion and preparing method thereof - Google Patents
Organic siloxane modified phenylethylene-acrylic ester nano-emulsion and preparing method thereof Download PDFInfo
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- CN1456577A CN1456577A CN 03126653 CN03126653A CN1456577A CN 1456577 A CN1456577 A CN 1456577A CN 03126653 CN03126653 CN 03126653 CN 03126653 A CN03126653 A CN 03126653A CN 1456577 A CN1456577 A CN 1456577A
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- acrylate
- methacrylate
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- 239000007908 nanoemulsion Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 14
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims abstract description 63
- -1 organosiloxane modified styrene-acrylate Chemical class 0.000 claims abstract description 47
- 239000000839 emulsion Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 20
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 239000003112 inhibitor Substances 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims description 24
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 13
- 239000004530 micro-emulsion Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical class OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 claims description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000012986 chain transfer agent Substances 0.000 claims description 4
- 230000033116 oxidation-reduction process Effects 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- SMSKIVCCLIQXFD-UHFFFAOYSA-N 1-tert-butyl-3-ethenylbenzene Chemical compound CC(C)(C)C1=CC=CC(C=C)=C1 SMSKIVCCLIQXFD-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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-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
- 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 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 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
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 claims description 2
- 238000010556 emulsion polymerization method Methods 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 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
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 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
- 238000003756 stirring Methods 0.000 claims 2
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-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
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims 1
- KNLPTHYTZVVNEP-UHFFFAOYSA-N C(=C)CCO[SiH](OC(C)C)OC(C)C Chemical compound C(=C)CCO[SiH](OC(C)C)OC(C)C KNLPTHYTZVVNEP-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical group 0.000 claims 1
- 235000012501 ammonium carbonate Nutrition 0.000 claims 1
- 239000001099 ammonium carbonate Substances 0.000 claims 1
- 150000001491 aromatic compounds Chemical class 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 claims 1
- 125000005821 ethenylmethoxy group Chemical group [H]\[#6]([H])=[#6](\[H])C([H])([H])[#8]-* 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
- 150000002334 glycols Chemical class 0.000 claims 1
- 235000003642 hunger Nutrition 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims 1
- 239000002736 nonionic surfactant Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 230000037351 starvation Effects 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
- 238000007334 copolymerization reaction Methods 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000077 silane Inorganic materials 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 229910001092 metal group alloy Inorganic materials 0.000 abstract description 3
- 239000002023 wood Substances 0.000 abstract description 3
- 238000005034 decoration Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 239000004816 latex Substances 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000005395 methacrylic acid group Chemical group 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000003750 conditioning effect Effects 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004159 Potassium persulphate Substances 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 235000019394 potassium persulphate Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- WGXGKXTZIQFQFO-UHFFFAOYSA-N ethenyl 3-phenylprop-2-enoate Chemical class C=COC(=O)C=CC1=CC=CC=C1 WGXGKXTZIQFQFO-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- AGUIILSGLFUTKG-UHFFFAOYSA-N CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] Chemical compound CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] AGUIILSGLFUTKG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- MCEBKLYUUDGVMD-UHFFFAOYSA-N [SiH3]S(=O)=O Chemical compound [SiH3]S(=O)=O MCEBKLYUUDGVMD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- YEMJITXWLIHJHJ-UHFFFAOYSA-N di(propan-2-yloxy)silane Chemical compound CC(C)O[SiH2]OC(C)C YEMJITXWLIHJHJ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012545 processing Methods 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
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 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
本发明涉及涂料技术领域，具体地是核/壳结构有机硅氧烷改性苯乙烯－丙烯酸酯纳米乳液及其制备方法，所述纳米乳液由乙烯基烷氧基多官能团硅烷功能性单体与苯乙烯、甲基丙烯酸烷基酯、甲基丙烯酸羟烷基酯、丙烯酸烷基酯和(甲基)丙烯酸等单体在有机硅氧烷水解抑制剂的作用下通过阻碍乳液聚合方式进行共聚获得；所得纳米乳液具有低乳化剂含量、高固体份含量的特性，其贮存稳定性好，可稳定放置一年以上，并且乳胶膜的耐候性、耐沾污性、耐水、耐化学溶剂性、耐碱性及耐擦洗性、附着力、拉伸强度及柔韧性等综合物理性能较现有乳液有显著的提高，广泛用于建筑外墙涂料、水性木器涂料、防水涂料和金属合金板材装潢涂料以及水性胶粘剂等。The invention relates to the technical field of coatings, in particular to a core/shell structure organosiloxane modified styrene-acrylate nanoemulsion and a preparation method thereof. The nanoemulsion is composed of vinyl alkoxy polyfunctional silane functional monomer and Monomers such as styrene, alkyl methacrylate, hydroxyalkyl methacrylate, alkyl acrylate and (meth)acrylic acid are obtained by copolymerization by hindering emulsion polymerization under the action of organosiloxane hydrolysis inhibitors Gained nanoemulsion has the characteristics of low emulsifier content, high solids content, good storage stability, can be placed stably for more than one year, and the weather resistance, stain resistance, water resistance, chemical solvent resistance, and Alkaline and scrub resistance, adhesion, tensile strength and flexibility and other comprehensive physical properties are significantly improved compared with existing emulsions, and are widely used in building exterior wall coatings, water-based wood coatings, waterproof coatings and metal alloy sheet decoration coatings and Water-based adhesives, etc.
Description
Technical field
The present invention relates to be used for the technical field of coatings of building external paint, water-borne wood coating, waterproof paint and metal alloy sheet material decoration coating and aqueous adhesive etc., siloxane modified vinylbenzene-acrylate nano emulsion of a kind of specifically high performance organo-silicon and preparation method thereof.
Background technology
Vinylbenzene-acrylic ester emulsion has many outstanding advantages, photostabilization, weathering resistance, resistance to acids and bases and erosion resistance as excellence, be widely used at aspects such as coating, tackiness agents, but because vinylbenzene-acrylic ester emulsion has shortcomings such as tint retention, water tolerance and tack difference.The organo-siloxane main chain is the Si-O-Si key, has the kindliness of height, and its high and low temperature resistance is good, and surface energy is low and have excellent water-resistance.
Adopt high-low temperature resistant, the low polyfunctional group organosilicon functional monomer that reaches water-tolerant of surface energy that vinylbenzene-ACRYLIC EMULSION is carried out modification, and it is made nanoemulsions, then organosilicon modified styrene-acrylate nano emulsion coating can significantly improve the hardness of filming, tensile strength, ventilation property, wear resistance, sticking power, anti-stickly put forth effort, water tolerance, chemical solvent resistance, scrub resistance, weathering resistance and contamination resistance.
At present, vinylbenzene-acrylic ester emulsion is carried out in the research of modification at polyfunctional group 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.The emulsion copolymerization method of adopting is also arranged, as the CN1319616A[publication number], the CN1251843[publication number] etc., but that obtain all is conventional emulsions (latex particle size is greater than 100nm).
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 the exploitation water-borne coatings has become coating researchist's goal in research.Emulsion polymerization modified phenylethylene-acrylic ester emulsion mainly is to utilize the organosilicon function monomer contain vinyl-functional or performed polymer and vinylbenzene, acrylic ester monomer to carry out emulsion copolymerization, but both at home and abroad about organic siloxane modified vinylbenzene-acrylic ester emulsion polymeric present Research, remain in some problems from present.As owing in the letex polymerization existence of water is arranged, hydrolysis-condensation reaction can take place in the alkoxyl group in the organo-siloxane, has a strong impact on the stability in storage of polymer emulsion; Because there are huge spread in organo-siloxane and vinylbenzene, acrylate on molecular structure and polarity, can being separated etc. in various degree appear because of compatibility problem, therefore to the selection of comonomer difficulty relatively.Adopt that conventional the organic siloxane modified vinylbenzene of emulsion polymerization synthetic-acrylic ester emulsion stability is bad, the organo-siloxane addition is little, is difficult for and other monomer copolymerization.
Summary of the invention
The objective of the invention is to propose the organic siloxane modified vinylbenzene-acrylate nano emulsion of core/shell structure of a kind of synthetic easily, good stability, excellent performance.
The present invention also aims to provide the preparation method of described nanoemulsions.
Nanoemulsions is by oil, water, the thermodynamically stable transparent or semitransparent colloidal dispersion system that emulsifying agent and assistant for emulsifying agent are formed, because its emulsion particle diameter is very little, and surface tension is very low, so they have fabulous perviousness, wettability, levelling property and rheological, can infiltrate atomic thin bump maps line, in the fine capillary channel and the unusual complicated matrix surface of geometrical shape, thereby it can be used as coating, tackiness agent, goods such as soaker and printing ink are to woodenware, building stones, concrete, paper, fabric and metallic article etc. carry out high quality processing and high gloss application.Formed the filming of nanometer polymer emulsion has the fabulous transparency, can make the transparency protected varnish of material surface such as metal; Can be made into have high transparent, the polishing material of glossiness and smooth property; Can make the filler of transparent material, to improve its smoothness and glossiness; Can carry out composite use with conventional emulsions, because nanoemulsions can infiltrate space and capillary channel inside that large size emulsion particle institute can not reach, and can be filled in the space between the big emulsion particle, can significantly improve latex film strength, sticking power, smoothness and glossiness.
The nanoemulsions that the present invention proposes is the organic siloxane modified vinylbenzene-acrylate nano emulsion of a kind of core/shell structure, and it adopts the obstruction emulsion polymerization to prepare, and vinylbenzene wherein, the monomer component of acrylate are:
1) contain the alkyl acrylate of C1-C10, consumption is the 20-40% of monomer total mass;
2) contain the alkyl methacrylate of C1-C10, consumption is the 20-40% of monomer total mass;
3) contain the hydroxyalkyl methacrylate of C2-C10, consumption is the 2-10% of monomer total mass;
4) contain the thiazolinyl carboxylic acid cross-linking monomer of C3-C6, consumption is the 2-10% of monomer total mass;
5) contain the aromatics of vinyl, consumption is the 10-50% of monomer total mass.
6) contain the polyfunctional group organo-siloxane function monomer of vinyl, consumption is the 1-10% of monomer total mass.
The alkyl acrylate of described C1-C10 is one or more mixtures of methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, hexyl acrylate, Isooctyl acrylate monomer.
The alkyl methacrylate of described C1-C10 is one or more mixtures of methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, n octyl methacrylate, Isooctyl methacrylate.
The acrylic acid hydroxy alkyl ester of described C2-C10 is 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxyl butyl ester, vinylformic acid-5-hydroxyl pentyl ester, vinylformic acid-6-hydroxyl one or more mixtures of ester, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester.
Described C3-C6 thiazolinyl carboxylic acid cross-linking monomer is vinylformic acid or methacrylic acid and composition thereof.
Described vinyl aromatic compounds is one or more mixtures of vinylbenzene, alpha-methyl styrene, 2-chlorostyrene, 3-t-butyl styrene, 3,4-dimethyl styrene.
Described vinyl polyfunctional group organo-siloxane function monomer is one or more mixtures of vinyltrimethoxy silane, vinyl methoxyl group diethoxy silane, vinyltriethoxysilane, vinyl oxyethyl group diisopropoxy silane, vinyl silane triisopropoxide.
The present invention can adopt the semi-continuous seed emulsion polymerization method, use extraordinary emulsifying agent, adopt direct initiator or oxidation-reduction initiator, prepare the seed microemulsion earlier, again will be through pre-emulsified monomer, adopt hungry charging method in 3-5 hour, to be added drop-wise in the seed microemulsion and react, can obtain translucent organic siloxane modified vinylbenzene-acrylate nano emulsion of the present invention.
Its more specifically step comprise:
1. prepare the seed microemulsion
Water, 10-50% emulsifying agent with 20-50% joins in the reactor earlier, high-speed stirring was disperseed 10-20 minute, add aforesaid propylene acid alkyl ester, the thiazolinyl carboxylic acid of 5-20%, the vinyl aromatic compounds of 50-100% again, be warming up to 75-85 ℃, add the part initiator again, behind the stoichiometric number minute, faint blue light appears in emulsion, restir 5-20 minute, promptly form transparent seed microemulsion.
2. prepare organic siloxane modified vinylbenzene-acrylate/nano emulsion
Remaining alkyl acrylate, alkyl methacrylate, acrylic acid hydroxy alkyl ester, vinyl aromatic compounds, vinylformic acid cross-linking monomer, vinyl polyfunctional group organosilicon functional monomer, vinyl polyfunctional group organosilicon functional monomer hydrolysis inhibitor, chain-transfer agent, water and emulsifying agent etc. were stirred at a high speed 10-30 minute, make it fully emulsified, obtain monomer pre-emulsion; In 3-5 hour, be added drop-wise in the reactor continuously, react with the seed microemulsion, temperature of reaction maintains 75-85 ℃, reaction finishes, insulation 1-2 hour, cooling, the pH value of regulating microemulsion with pH value conditioning agent, filter discharging, promptly get translucent organosilicon modified styrene-acrylate/nano emulsion.
Emulsion solid content is about 45%, and particle diameter is 30-60nm.
Described chain-transfer agent can be alkyl sulfhydryl or the hydrosulphonyl silane of C5-C15, and consumption is the 1-5% of monomer total mass.
Described emulsifying agent is response type anion surfactant and nonionogenic tenside, and consumption is at below 3% of monomer total mass, and the first step consumption accounts for the 10-60% of emulsifying agent total mass.
Described initiator can be the direct initiator of persulphate, or the oxidation-reduction initiator, and consumption is below 1% of monomer total mass, and the first step consumption accounts for the 20-80% of initiator total mass.
Described pH value conditioning agent can be carbonate, supercarbonate, phosphoric acid salt, hydrophosphate or the hydrosulfate of basic metal, alkaline-earth metal or ammonium, and consumption is the 0.1-2% of monomer total amount.
The monomeric hydrolysis inhibitor of described organosilicon alcoxyl alkoxyl functional can be the di-alcohols of C2-C8, and consumption is the 0.1-2% of monomer total mass.
Organic siloxane modified vinylbenzene one acrylate nano emulsion of the core/shell structure that the present invention makes is compared with existing conventional emulsions, has the following advantages:
1. the core/shell structure nanoemulsions of the present invention's preparation had both had higher second-order transition temperature, had lower minimum film-forming temperature again, had both reduced raw materials cost, had improved the mechanical property of filming again, had increased the weathering resistance of filming.
2. the core/shell structure emulsion of the present invention's preparation is translucent nanoemulsions, and Thermodynamically stable can be stablized and store more than 1 year.
3. the core/shell structure emulsion of the present invention's preparation is translucent nanoemulsions, the emulsion particle diameter is very little, and surface tension is very low, so they have fabulous perviousness, wettability, levelling property and rheological, can infiltrate in atomic thin bump maps line, the fine capillary channel and the unusual complicated matrix surface of geometrical shape.
4. the nanoemulsions of the present invention preparation, formed filming has the fabulous transparency; Carry out composite use with conventional emulsions, can significantly improve latex film strength, sticking power, smoothness and glossiness.
5. the present invention adds acrylic or methacrylic acid cross-linking monomer in emulsion polymerization process, significantly improve the degree of crosslinking and the sticking power of latex film, need not add and after catalyzer just can make organo-siloxane and other monomer copolymerization hydrolytic crosslinking take place, reduce the consumption of emulsifying agent and initiator, increased the water tolerance of filming.
6. the present invention adds a kind of hydrolysis inhibitor of organo-siloxane in emulsion polymerization process, makes the organosilicon function monomer hydrolysis reaction can not take place before copolymerization, has increased the stability of polyreaction.
7. the present invention prepares nanoemulsions employing obstruction emulsion polymerisation process; solvent for use is a water; the emulsion of preparation is nontoxic; nonflammable; both helped environment protection; can reduce production costs again, the exterior coating ultraviolet resistance accelerated weathering test that makes with it can reach more than 3000 hours, water-proof surpasses 10000 times, can replace solvent type organic silicone modified vinylbenzene-acrylate paint for external wall fully.
Core/shell structure organosilicon-the acrylate nano emulsion of the present invention preparation than the non-silylation vinylbenzene-acrylic ester emulsion similarity condition under and silylation vinylbenzene-acrylate conventional emulsions have more superior water tolerance, scrub resistance, chemical solvent resistance, weathering resistance, contamination resistance, anti-stickly put forth effort, degree of crosslinking, sticking power, hardness and tensile strength, be widely used in top-grade building exterior coating, water-borne wood coating, waterproof paint and metal alloy sheet material decorate coating and aqueous adhesive etc.
9. nanoemulsions of the present invention, it adopts the obstruction emulsion polymerisation process to prepare.Compare with the preparation method of existing organosilicon modified styrene-acrylate, this novel polymerization process had both guaranteed the reactive behavior of unsaturated double-bond by means of chemical bond and intermolecular mechanical interlocking, the problem of phase separation that has overcome the hydrolytie polycondensation of organo-siloxane again and caused greatly owing to the polarity gap, realize the stable emulsion copolymerization of the polymkeric substance that two kinds of polarity differ greatly, and improved the package stability of polymer emulsion.The organic-silicon-modified nanoemulsions particle diameter for preparing is controlled at 30-60nm, has high performance, multifunction, and has realized the ultra micro refinement of latex particle.
Performance to the nanoemulsions of the present invention preparation can characterize with the following method: particle size of emulsion adopts Coulter LS230 particle size analyzer to measure; Being coated with film dynamic performance tests with the Instron electronic tension tester; The emulsion polymer structure is measured with Fourier infrared spectrograph (FTIR); The emulsion second-order transition temperature is measured with the trapezoidal thermometer of minimum film forming with differential scanning calorimeter (DSC), minimum film-forming temperature; The latex particle form of emulsion is measured with the micro-Electronic Speculum of scanning (TEM); The emulsion latex film is crosslinked to be measured by MEK (methyl ethyl ketone) reflux method of extraction; The pencil hardness of filming is measured by ASTM-3364; Sticking power is pressed GB/T9286-88 cross cross-hatching and is measured; The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
Embodiment
Embodiment 1
Set of monomers becomes vinylbenzene, butyl acrylate, methyl methacrylate, methacrylic acid, hydroxyethyl methylacrylate, contains the vinyl alkoxy silane of C5-C20, and its component prescription is as table 1.
Table 1
Form mass percent, %1 vinylbenzene 252 methacrylic acids (MAA) 23 butyl acrylates (BA) 164 hydroxyethyl methylacrylates 25 vinylic organosiloxanes 16 emulsifying agents 2.57 Potassium Persulphate (K
2S
2O
8) 0.28 sodium bicarbonate, 0.19 lauryl mercaptan, 0.510 propylene glycol, 0.211 secondary deionized water, 5012 ammoniacal liquor (28%) 0.5
With 1 part of emulsifying agent, 18 parts of water, 1 part of methacrylic acid, 3 parts of butyl acrylates, 8 parts of vinylbenzene add in the reactor, stirred 20 minutes, temperature of reaction kettle is heated to 80C, drip initiator, continue to be stirred to emulsion and faint blue light occurs, after 15 minutes, begin to drip good monomer of pre-emulsification (the water high-speed stirring emulsification of remaining monomer and 30 parts 25 minutes) and initiator, in 4 hours pre-emulsion and initiator are all dripped, continue insulation 1.5 hours, cooling adds ammoniacal liquor and regulates the pH value to 7.5-8.5, the cold filtration discharging promptly gets translucent nanoemulsions of the present invention.
Embodiment 2
Set of monomers becomes butyl acrylate, vinylbenzene, vinylformic acid, Rocryl 410, contains the vinyl alkoxy silane of C5-C20, and its component prescription is as table 2.
Table 2
Form mass percent, %1 vinylbenzene (St) 252 vinylformic acid (AA) 13 butyl acrylates (BA) 154 Rocryl 410s 25 vinylic organosiloxanes 36 emulsifying agents 2.57 Potassium Persulphate (K
2S
2O
8) 0.28 sodium bicarbonate, 0.19 lauryl mercaptan, 110 ethylene glycol, 0.211 secondary deionized water 50
With 1 part of emulsifying agent, 20 parts of water, 1 part of vinylformic acid, 2 parts of butyl acrylates, 8 parts of vinylbenzene add in the reactor, stirred 20 minutes, temperature of reaction kettle is heated to 80 ℃, drip initiator, continue to be stirred to emulsion and faint blue light occurs, after 15 minutes, begin to drip good monomer of pre-emulsification (the water high-speed stirring emulsification of remaining monomer and 30 parts 25 minutes) and initiator, in 3 hours pre-emulsion and initiator are all dripped, continue insulation 2 hours, add pH value conditioning agent and regulate the pH value to 7-8, cold filtration promptly gets translucent core/shell structure organosilicon modified styrene-acrylate nano emulsion.
Embodiment 3
Set of monomers becomes vinylbenzene, Isooctyl acrylate monomer, methacrylic acid, hydroxyethyl methylacrylate, contains the vinyl alkoxy silane of C5-C20, and its component prescription is as table 3
Table 3
Form mass percent, %1 vinylbenzene 242 methacrylic acids (MAA) 13 Isooctyl acrylate monomers 164 hydroxyethyl methylacrylates 15 vinylic organosiloxanes 3.56 emulsifying agents 1.37 Potassium Persulphate (K
2S
2O
8) 0.28 sodium bicarbonate, 0.59 mercaptoethanol, 0.310 propylene glycol, 0.211 secondary deionized water 52
With 1 part of emulsifying agent, 15 parts of water, 1 part of methacrylic acid, 1 part of Isooctyl acrylate monomer, 6 parts of vinylbenzene, 1 part of hydroxyethyl methylacrylate adds in the reactor, stirred 20 minutes, temperature of reaction kettle is heated to 80 ℃, drip initiator, continue to be stirred to emulsion and faint blue light occurs, after 15 minutes, begin to drip good monomer of pre-emulsification (the water high-speed stirring emulsification of remaining monomer and 35 parts 25 minutes) and initiator, in 4 hours pre-emulsion and initiator are all dripped, continue insulation 1 hour, add pH value conditioning agent and regulate pH value to 8.5, cold filtration promptly gets the organic siloxane modified vinylbenzene-acrylate nano emulsion of translucent core/shell structure.
Claims (9)
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