CN1876731A - Aqueous coating containing three layer nuclear shell structure rubber particle latex and its preparation method - Google Patents
Aqueous coating containing three layer nuclear shell structure rubber particle latex and its preparation method Download PDFInfo
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- CN1876731A CN1876731A CN 200510075254 CN200510075254A CN1876731A CN 1876731 A CN1876731 A CN 1876731A CN 200510075254 CN200510075254 CN 200510075254 CN 200510075254 A CN200510075254 A CN 200510075254A CN 1876731 A CN1876731 A CN 1876731A
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- Prior art keywords
- monomer
- shell structure
- rubber particle
- layer
- nuclear shell
- Prior art date
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- Granted
Links
- 229920000126 latex Polymers 0.000 title claims abstract description 36
- 239000002245 particle Substances 0.000 title claims description 44
- 238000000576 coating method Methods 0.000 title claims description 35
- 239000004816 latex Substances 0.000 title claims description 35
- 229920001971 elastomer Polymers 0.000 title claims description 26
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000011248 coating agent Substances 0.000 title description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 70
- 150000001336 alkenes Chemical class 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 18
- 125000003368 amide group Chemical group 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000004132 cross linking Methods 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 150000002924 oxiranes Chemical group 0.000 claims description 8
- 150000008064 anhydrides Chemical group 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 239000004159 Potassium persulphate Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000004581 coalescence Methods 0.000 claims description 5
- 239000013530 defoamer Substances 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 230000008719 thickening Effects 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 3
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 3
- OWDBMKZHFCSOOL-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)propoxy]propoxy]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(C)COC(C)COC(=O)C(C)=C OWDBMKZHFCSOOL-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- -1 color stuffing Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 2
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000006224 matting agent Substances 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000006254 rheological additive Substances 0.000 claims description 2
- 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 1
- 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 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 101000962438 Homo sapiens Protein MAL2 Proteins 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 102100039191 Protein MAL2 Human genes 0.000 description 1
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000004658 ketimines Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates the water paint with three-layer shell sandwich rubber latex emulsion and preparing method. The method has the advantages of low cost, simple technology and improving fire-resisting property, water resistance and hardness of water paint film.
Description
Technical field:
The present invention relates to a kind of water-borne coatings that contains three layer nuclear shell structure rubber particle latex and preparation method thereof.
Background technology:
The esters of acrylic acid water-borne coatings is to be the coating that disperses thinner with water, the volatilization of organic solvent-free in application, and organic solvent-free is remaining in use, belongs to environmentally friendly coating, many is used for the building inside and outside wall application.When being used for the application of woodenware and metallic surface, require coating surface hardness height, good heat resistance, water-tolerant.But the esters of acrylic acid water-borne coatings is coated with when being contained in woodenware, metallic surface, water-borne coatings poor water resistance, poor heat resistance, and the problem that varnish hardness is low will highlight, and has limited the application of aqueous acrylic acid series water-borne coatings.
In order to improve the physical strength of filming, performances such as water tolerance, usually to macromolecular chain be cross-linked with each other, therefore people have carried out a large amount of research to emulsion that can room temperature film-forming, obtain normal temperature crosslinked emulsion as US4772680 by acetoacetyl and hydrazine reaction generation ketimine structure; EP567128, CN1144242 can at room temperature carry out stable reaction by having the polymkeric substance of holding carboxyl and the polymkeric substance of nitrogen heterocyclic ring propylene group, CN1537895 is two kinds of component coating, with the mixed in molar ratio of primary amine group/epoxide group by 1: 1, realizes crosslinking reaction.Above-mentioned normal temperature crosslinked system weak point is that material toxicity is big, costs an arm and a leg, and two-pack when construction, mix the back and in the construction time, solidify easily, the system viscosity is increased, the influence construction, human factor is bigger to the influence of filming.
Summary of the invention:
It is filmogen that the present invention attempts to contain three layer nuclear shell structure rubber particle latex, crosslinked mono-component aqueous coating of a kind of environmentally friendly self-vulcanizing and preparation method thereof is provided, make cost of material cheap, preparation and construction technology are simple, and improve performances such as water tolerance that water-borne coatings films, thermotolerance, hardness.
A kind of water-borne coatings that contains three layer nuclear shell structure rubber particle latex of the present invention, by polymer emulsion, multiple auxiliary agent, the water-borne coatings that color stuffing is formulated, it is characterized in that said polymer emulsion is a kind of emulsion with three-layer nuclear shell structure latex particle, solid content is 25～55%, the stratum nucleare of latex particle is an alkene class hard monomer, the multipolymer of alkene class soft monomer and polyenoid class cross-linking monomer, inferior skin is an alkene class hard monomer, alkene class soft monomer and contain epoxide group, the multipolymer of the vinyl monomer of anhydride group or reactive halogen group, outermost layer are alkene class hard monomer, alkene class soft monomer and contain carboxyl, hydroxyl, the multipolymer of the vinyl monomer of amido or amide group.
The stratum nucleare of three-layer nuclear shell structure latex particle accounts for 25～50% of total polymer mass, and inferior skin accounts for 25～50%, and outermost layer accounts for 25～50%.
The median size of latex particle is preferably less than 100 nanometers.
Said alkene class hard monomer is any in the following material or their combination: vinylbenzene, methyl methacrylate, isobornyl methacrylate, isobornyl acrylate, uncle's nine NSC 11801, uncle's ten NSC 11801, uncle's hendecoic acid vinyl acetate, acrylonitrile monemer.
Alkene class soft monomer is any in the following material or their combination: ethyl propenoate, butyl acrylate, vinylformic acid isopentyl ester, 2-EHA.
Polyenoid class cross-linking monomer is any in the following material or their combination: Vinylstyrene, bisacrylamide, ethylene glycol dimethacrylate, tirethylene glycol dimethacrylate, triethylene Glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethyl-acrylate.
The vinyl monomer that contains epoxide group, anhydride group or reactive halogen group is a kind of in the following material group or their combination: glycidyl methacrylate, glycidyl allyl ether, maleic anhydride, vinylchlorid vinyl ether, vinyl chloroacetate, p-chloromethyl styrene.
Have carboxyl, phosphate, hydroxyl, amido or amide group vinyl monomer and be a kind of in the following material group or their combination: vinylformic acid, methacrylic acid, acrylamide, Methacrylamide, n-methylolacrylamide, acrylic amine ethyl ester, methacrylic acid amino ethyl ester, methacrylic acid N, silomate base ethyl ester, Hydroxyethyl acrylate, Propylene glycol monoacrylate.
Three layer nuclear shell structure rubber particle latex adopts following method preparation:
In the reactor of protection of inert gas; under the agitation condition; add deionized water, emulsifying agent, nuclear layer monomer successively and carry out emulsification; be heated to 40～88 ℃; the aqueous solution initiated polymerization that adds initiator; finished stratum nucleare particle building-up reactions in 1～2 hour, the mass ratio of wherein used alkene class hard monomer, alkene class soft monomer and polyenoid class cross-linking monomer: 40～80: 20～60: 0.1～1.
Then inferior outer olefinic monomer is mixed, be added dropwise in the reactor simultaneously with initiator solution, after dropwising, reacted 0.5～2 hour, finish the synthetic of time outer particle, wherein used alkene class hard monomer, alkene class soft monomer and contain the mass ratio of the vinyl monomer of epoxide group, anhydride group or reactive halogen group: 25～60: 35～60: 5～40.
The outermost layer vinyl monomer being mixed is added drop-wise in the reactor gradually again, drip initiator solution simultaneously, after dropwising, reacted 0.5～2 hour, finish the synthetic of outermost layer particle, wherein used alkene class hard monomer, alkene class soft monomer and the mass ratio that contains the vinyl monomer of carboxyl, hydroxyl, amido or amide group are: 25～60: 35～90: 5～40.
In reactor, add the back and eliminate initiator solution, be incubated 1～2 hour,, filter discharging, obtain three layer nuclear shell structure rubber particle latex through cooling.Rubber particle latex prepares that nuclear layer monomer accounts for 25～50% of monomer total mass in the used monomer generally, and inferior outer monomer accounts for 25～50% of monomer total mass, and the outermost layer monomer accounts for 25～50% of monomer total mass.
Used initiator and consumption are with generally letex polymerization is similar in the three layer nuclear shell structure rubber particle latex preparation, be Potassium Persulphate, ammonium persulphate, Potassium Persulphate-sodium bisulfite or ammonium persulfate-sodium bisulfite, consumption is generally 0.005～1% of the used monomer mass of letex polymerization.
Used emulsifying agent is letex polymerization anionic, non-ionic type or negatively charged ion and non-ionic composite commonly used, perhaps reactive emulsifier.Consumption is similar with general letex polymerization, is generally 0.5～2% of monomer mass.
The present invention also provides a kind of preparation method who contains the water-borne coatings of three layer nuclear shell structure rubber particle latex, by three layer nuclear shell structure rubber particle latex, multiple auxiliary agent, color stuffing is formulated, concrete compound method is: be filmogen with the three layer nuclear shell structure rubber particle latex, composite with film coalescence aid, flow agent, defoamer, thickening material, rheology modifier, mould inhibitor, sanitas, wetting agent, anti-zoned colored agent, matting agent, and inorganic color stuffing makes water-borne coatings, and wherein the weight percentage of three layer nuclear shell structure rubber particle latex is 35～95%.
Key of the present invention is design and synthesized a kind of three layer nuclear shell structure rubber particle latex that contains, and as filmogen, realizes normal temperature crosslinked, the high heat resistance and the high rigidity of water-borne coatings with this particle emulsion.
The present invention is that the particle structure design by multi-layer core-shell will participate in two class functional groups of crosslinking reaction (class is an epoxide group, anhydride group, reactive halogen, another kind of be can with their the reaction carboxyl, hydroxyl, amido, amide group) is distributed in different shells respectively, hydrophilic functional group's (carboxyl, hydroxyl, amido, amide group) design is at outermost layer, owing to water is arranged as dispersion agent, when emulsion and water-borne coatings state, hydrophilic radical is all the time towards water, the appearance that has limited between inferior skin and outermost layer multipolymer is closed, therefore avoided when polymerization and water-dispersion emulsion system are deposited the reaction of the two, made emulsion and coating that good shelf stability energy be arranged; And when the paint spraying film forming, along with the volatilization of moisture, will lose the environment of water towards the hydrophilic radical of water, under the effect of suitable temperature and film coalescence aid, the polymer molecule chain movement, merge mutually between particle, the ectonexine infiltration, realize crosslinking reaction, nuclear polymer is designed to little crosslinked than hard polymer in addition, second-order transition temperature is higher, bring film higher hardness, shell polymeric is designed to be beneficial to room temperature film-forming than flexible polymer.The water-borne coatings excellent storage stability and the application operating procedure that obtain of method is simple thus, and the film performance that obtains is good.
Embodiment:
Embodiment 1:
(1) preparation of three-layer nuclear shell emulsion:
A. the preparation of stratum nucleare polymkeric substance:
Having water of condensation, stir, thermometer, add 34 kilograms of deionized waters in 100 liters of enamel reaction stills of Dropping feeder, 0.15 kilogram alkyl diphenyl disodium sulfonate, 0.30 the reactive emulsifier allyl group polyethoxye sulfonate (SEN-10) of kilogram, 9.1 kilogram vinylbenzene, 2.8 kilograms of butyl acrylates, 0.1 kilogram of Vinylstyrene, stirring and emulsifying, logical nitrogen 20min is warming up to 40 ℃ of initiated polymerizations, adds 0.012 kilogram of Potassium Persulphate and 0.012 kilogram of sodium bisulfite water liquid (water yield is 400 grams), after the initiation reaction 1 hour, the temperature of reaction of system remains on 60 ± 2 ℃ gradually.
B: the preparation of inferior outer layer copolymer:
With 2.5 kilograms of methyl methacrylates that mix, 5.0 kilogram butyl acrylate, 1.5 the kilogram glycidyl methacrylate drips (water yield is 900 grams) simultaneously with 0.009g Potassium Persulphate and 0.009 kilogram of aqueous solution of sodium bisulfite, is added dropwise to complete in 1 hour.
C: the preparation of outermost layer polymkeric substance:
With 3.3 kilograms of methyl methacrylates that mix, 5.0 kilogram butyl acrylate, 0.7 kilogram methacrylic acid and 0.009 kilogram of Potassium Persulphate and 0.009 kilogram of sodium bisulfite (be made into the aqueous solution, the water yield is 900 grams) dropping simultaneously dropwised afterreaction 1 hour.
Be warming up to 72 ± 2 ℃, add the rongalite of 0.015 kilogram of back elimination initiator and 0.015 kilogram tertbutyl peroxide and (be made into the aqueous solution, the water yield is 400 grams), reacted 1～2 hour, be cooled to below 40 ℃ and filter discharging, obtain solid content and be 45% three-layer nuclear shell structure emulsion, stable reaction in the polymerization process is not found gel.
(2) composite (following said umber all refers to mass fraction) of varnish type water-borne coatings
100 parts of three-layer nuclear shell structure emulsions of the present invention are added in the stirring tank, open and stir, drip 0.2 part pH value conditioning agent AMP95 gradually, 795,2 parts of furtherance films of film coalescence aid auxiliary agent (propylene glycol) of 5 parts, 0.5 part of wetting agent, 0.8 part flow agent 2020,0.2 part defoamer 681F, 5230,0.01 parts of mould inhibitors 1138 of 0.1 part of thickening material, 0.01 part sanitas MV, 5 parts of anti-zoned colored agent (anti-scraping 810) are fully stirred, and make varnish type water-borne coatings.
(3) performance measurement and measuring method thereof: (concrete data see Table 2)
The mensuration of degree of crosslinking: take by weighing a certain amount of film that in baking oven, dries to constant weight, pack in the load weighted in advance filter paper, in apparatus,Soxhlet's, use acetone extracting 48 hours, film after the extracting is dried to constant weight in baking oven, calculate the degree of crosslinking of film according to following formula: the quality (g) * 100% of weight (the g)/extracting cephacoria of film degree of crosslinking=extracting caudacoria.
Cup impression performance measurement that coating is water-fast:
In beaker, irritate 400ml water, boil.On tested base material, fall some boiling water, on will also having the beaker of boiling water to be positioned over then to film.Beaker is placed 15min on tested base material.After the 15min, take beaker away, grade to filming immediately; Wait to film and recover to grade after 6 hours.Nothing is turned white, and no impression is a top grade, and no impression has little turning white, but reverts to good level after doing, impression is arranged or turn white after can not revert to failure.
The water resistance test of film: GB/T1733-93 tests according to GB.
The test of film hardness: use paint film pencil scratch hardness instrument according to GB GB/T6739-1966.
Embodiment 2-12: used monomer of synthetic latex particle and consumption see Table 1, and other preparation condition is with embodiment 1.
Table 1: used monomer of embodiment 2-12 synthetic latex particle and consumption
Unit: kilogram
St is a vinylbenzene in the table, and MMA is a methyl methacrylate, and BA is a butyl acrylate, and DVB is a Vinylstyrene, and GMA is a glycidyl methacrylate, and AN is a vinyl cyanide, and AA is a vinylformic acid; TEGDA triethylene Glycol dimethacrylate, the MALl maleic anhydride, IBOMA isobornyl methacrylate, AM are acrylamide; IPA vinylformic acid isopentyl ester, IBOA is an isobornyl acrylate, HEA Hydroxyethyl acrylate, MAL2 are MALEIC ANHYDRIDE, and HAM is a n-methylolacrylamide, TPGDA tripropylene glycol dimethacrylate, the EA ethyl propenoate, VCA vinyl chloroacetate, uncle's VeoVa-10 ten NSC 11801, DMEA methacrylic acid N, silomate base ethyl ester.
Table 2: the every testing performance index result of varnish type water-borne coatings of embodiment 1-12
Embodiment 13-18: the configuration of colored paint type coating
200 liters at high speed dispersor are disperseed to add in the cylinder 100 parts of deionized waters, 5 parts of dispersion agent DP-270 consumptions, 1.5 parts of defoamer 681F, 1200 rev/mins were stirred 10 minutes, slowly add 50 parts of commercially available rutile titanium dioxides successively, 10 parts of kaolin, 5 parts of talcum powder continued dispersed with stirring 20 minutes, ground twice with sand mill, fineness reaches below 30 microns and forms pigment slurry, and is stand-by.
Three-layer nuclear shell structure emulsion with step (1) in the embodiment of the invention 2,4,6,8,10 or 12 in the paint still adds in the stirring tank for 100 parts, open and stir, 100-300 rev/min of stirring, drip 0.2 part pH value conditioning agent AMP95,5 parts film coalescence aid 795,2 parts of furtherance film auxiliary agents (propylene glycol), 0.5 part of wetting agent, 0.2 part of defoamer 681F.
Ground pigment slurry is slowly added in the emulsion in the paint still, slowly add 2.0 parts of flow agents then successively, 0.5 part of thickening material 5230,0.02 part 1138,0.02 parts of sanitas MV of mould inhibitor look color and require to add various color paste tonings, fully stir, make colored paint type water-borne coatings.
Table 3: the every testing performance index result of colored paint type water-borne coatings of embodiment 13-18
Claims (6)
1. water-borne coatings that contains three layer nuclear shell structure rubber particle latex, formulated by polymer emulsion and other auxiliary agents, it is characterized in that said polymer emulsion is a kind of emulsion with three-layer nuclear shell structure latex particle, solid content is 25～55%, the stratum nucleare of latex particle is an alkene class hard monomer, the multipolymer of alkene class soft monomer and polyenoid class cross-linking monomer, inferior skin is an alkene class hard monomer, alkene class soft monomer and contain epoxide group, the multipolymer of the vinyl monomer of anhydride group or reactive halogen group, outermost layer are alkene class hard monomer, alkene class soft monomer and contain carboxyl, hydroxyl, the multipolymer of the vinyl monomer of amido or amide group;
The stratum nucleare of said three-layer nuclear shell structure latex particle accounts for 25～50% of total polymer mass, and inferior skin accounts for 25～50%, and outermost layer accounts for 25～50%.
2. according to the water-borne coatings that contains three layer nuclear shell structure rubber particle latex of claim 1, it is characterized in that:
Said alkene class hard monomer is a kind of in the following material or their combination: vinylbenzene, methyl methacrylate, isobornyl methacrylate, isobornyl acrylate, uncle's nine NSC 11801, uncle's ten NSC 11801, uncle's hendecoic acid vinyl acetate, acrylonitrile monemer;
Alkene class soft monomer is a kind of in the following material or their combination: ethyl propenoate, butyl acrylate, vinylformic acid isopentyl ester, 2-EHA;
Polyenoid class cross-linking monomer is a kind of in the following material or their combination: Vinylstyrene, bisacrylamide, ethylene glycol dimethacrylate, tirethylene glycol dimethacrylate, triethylene Glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethyl-acrylate;
The vinyl monomer that contains epoxide group, anhydride group or reactive halogen group is a kind of in the following material group or their combination: glycidyl methacrylate, glycidyl allyl ether, maleic anhydride, vinylchlorid vinyl ether, vinyl chloroacetate, p-chloromethyl styrene;
Have carboxyl, hydroxyl, amido or amide group vinyl monomer and be a kind of in the following material group or their combination: vinylformic acid, methacrylic acid, acrylamide, Methacrylamide, n-methylolacrylamide, acrylic amine ethyl ester, methacrylic acid amino ethyl ester, methacrylic acid N, silomate base ethyl ester, Hydroxyethyl acrylate, Propylene glycol monoacrylate.
3. according to the water-borne coatings that contains three layer nuclear shell structure rubber particle latex of claim 1 or 2, it is characterized in that three layer nuclear shell structure rubber particle latex adopts following method preparation:
In the reactor of protection of inert gas, under the agitation condition, add deionized water, emulsifying agent, nuclear layer monomer successively and carry out emulsification, be heated to 40～88 ℃, the aqueous solution initiated polymerization that adds initiator, react and finished stratum nucleare particle building-up reactions in 1～2 hour, the mass ratio of wherein used alkene class hard monomer, alkene class soft monomer and polyenoid class cross-linking monomer: 40～80: 20～60: 0.1～1;
Then inferior outer olefinic monomer is mixed, be added dropwise in the reactor simultaneously with initiator solution, after dropwising, reacted 0.5～2 hour, finish the synthetic of time outer particle, wherein used alkene class hard monomer, alkene class soft monomer and contain the mass ratio of the vinyl monomer of epoxide group, anhydride group or reactive halogen group: 25～60: 35～60: 5～40;
The outermost layer vinyl monomer being mixed is added drop-wise in the reactor gradually again, drip initiator solution simultaneously, after dropwising, reacted 0.5～2 hour, finish the synthetic of outermost layer particle, wherein used alkene class hard monomer, alkene class soft monomer and contain the mass ratio of the vinyl monomer of carboxyl, hydroxyl, amido or amide group: 25～60: 35～90: 5～40;
In reactor, add the back and eliminate initiator solution, be incubated 1～2 hour, through cooling, filter discharging, obtain three layer nuclear shell structure rubber particle latex, wherein rubber particle latex prepares that nuclear layer monomer accounts for 25～50% of monomer total mass in the used monomer, and inferior outer monomer accounts for 25～50% of monomer total mass, and the outermost layer monomer accounts for 25～50% of monomer total mass.
4. according to the water-borne coatings of claim 3, it is characterized in that: the used initiator of preparation rubber particle latex is Potassium Persulphate, Sodium Persulfate, ammonium persulphate, Potassium Persulphate-sodium bisulfite, Sodium Persulfate-sodium bisulfite or ammonium persulfate-sodium bisulfite, and it is tertbutyl peroxide-formaldehyde sodium bisulfite that initiator is eliminated in the back.
5. according to the water-borne coatings of claim 3, it is characterized in that: the used emulsifying agent of preparation rubber particle latex is letex polymerization anionic, non-ionic type or negatively charged ion and non-ionic composite commonly used, perhaps reactive emulsifier.
6. preparation method who contains the water-borne coatings of three layer nuclear shell structure rubber particle latex, formulated by three layer nuclear shell structure rubber particle latex, multiple auxiliary agent, color stuffing, concrete compound method is: be filmogen with the three layer nuclear shell structure rubber particle latex, compositely make water-borne coatings with film coalescence aid, flow agent, defoamer, thickening material, rheology modifier, mould inhibitor, sanitas, wetting agent, anti-zoned colored agent, matting agent and color stuffing, wherein the weight percentage of three layer nuclear shell structure rubber particle latex is 35～95%.
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