CN102585073A - Fluorine silicon-modified acrylic ester emulsion and preparation method thereof - Google Patents
Fluorine silicon-modified acrylic ester emulsion and preparation method thereof Download PDFInfo
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- CN102585073A CN102585073A CN2012100135141A CN201210013514A CN102585073A CN 102585073 A CN102585073 A CN 102585073A CN 2012100135141 A CN2012100135141 A CN 2012100135141A CN 201210013514 A CN201210013514 A CN 201210013514A CN 102585073 A CN102585073 A CN 102585073A
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- emulsion
- monomer
- acrylic ester
- modified acrylic
- silicone modified
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- 239000000839 emulsion Substances 0.000 title claims abstract description 126
- -1 Fluorine silicon-modified acrylic ester Chemical class 0.000 title claims abstract description 50
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 14
- 239000011737 fluorine Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000004945 emulsification Methods 0.000 title description 5
- 239000003999 initiator Substances 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 239000006174 pH buffer Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 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 claims description 9
- 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 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 235000015424 sodium Nutrition 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000012874 anionic emulsifier Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 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 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000012875 nonionic emulsifier Substances 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 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
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- MORMPWNLQJTSOT-UHFFFAOYSA-L disodium;4-dodecyl-2-(4-sulfonatophenoxy)benzenesulfonate Chemical compound [Na+].[Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C(OC=2C=CC(=CC=2)S([O-])(=O)=O)=C1 MORMPWNLQJTSOT-UHFFFAOYSA-L 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 229960004249 sodium acetate Drugs 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 claims description 2
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 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
- 239000002245 particle Substances 0.000 abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 4
- 229920000620 organic polymer Polymers 0.000 abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 3
- 230000003111 delayed effect Effects 0.000 abstract 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 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000002966 varnish Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 41
- 238000000576 coating method Methods 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 24
- 230000003373 anti-fouling effect Effects 0.000 description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 241000238367 Mya arenaria Species 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 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
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 235000015193 tomato juice Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention discloses a fluorine silicon-modified acrylic ester emulsion and a preparation method thereof. The fluorine silicon-modified acrylic ester emulsion is a shell-core emulsion mainly prepared from a fluorine monomer, vinyl triisopropoxysilane, nano silica sol, a vinyl monomer, a long carbon chain monomer, an emulsifier, a pH buffer, an initiator, deionized water and the like. The fluorine monomer is delayed to be dripped during polymerization, so that the fluorine element is enriched on the surfaces of emulsion particles, the hydrophobic and oleophobic properties of fluorine elusion is given full play to, the use of the fluorine monomer is reduced, and the cost is reduced. The composition of inorganic silicon oxide particles and an organic polymer keeps the good film forming property of the polymer and has the weather resistance, high hardness and other characteristics of the inorganic matter, so as to improve the stain resistance of a varnish film.
Description
Technical field
The present invention can be used for the application of inner wall of building, relates to a kind of hud typed fluorinated silicone modified acrylic ester emulsion and preparation method thereof.
Background technology
The fluorine reforming polymer surface free energy that contains perfluoro alkyl group is low, can give the excellent hydrophobic oleophobic of material surface, anti-stain characteristic ability, at aspects such as building external paint, antifouling paint, anti-fog coatings important potential application is arranged.Zisman reported in 1962 in (methyl) perfluoroalkyl acrylate homopolymer side chain perfluoro MU just have when surpassing 7 extremely low surface energy (10～11mN/m) (and JPhys Chem, 1962,66:1207-1208).
The method of introducing fluoro-containing group mainly contains three kinds: the one, and adopt trifluorochloroethylene, tetrafluoroethylene and vinyl ethers/vinyl acetate between to for plastic class copolymerization to form (like the Chinese invention patent 200510135388.7 of application), the fluorocarbon resin of selling is in the market used this method more; The 2nd, add fluorochemical additive, like (like Chinese invention patent ZL200710090028.9) such as Perfluorocaprylic Acid, fluorocarbon surfactants; The 3rd, use the fluorinated acrylic ester monomer, this is present most widely used a kind of method, equally also is the most popular research direction.Cost an arm and a leg but perfluoroalkyl acrylate is monomeric, its homopolymer cost is too high, is difficult to widespread use.Utilize the reaction enthalpy of perfluorinated acrylate, Q-e value and propenoate are close, and itself and acrylic ester copolymer can be reduced cost, and are beneficial to the realization industriallization.
SiO in the Nano silica sol
2Penetrating power is very strong; Can be attached to the surface of base material and filler particles; Along with the evaporation of moisture, dehydration forms the firm solid netted skeleton of siliconoxygen bond between particle, but this filming lacks continuity and spreadability; And fluorinated acrylate polymer has good film-forming properties, both recombination energies can be overcome silicon sol film and be prone to embrittlement atomizing shortcoming.Because inorganics and organism are the materials of two kinds of different in kinds, both interfaces lack enough affinities, and the interface affinity that therefore improves both is the key of composite emulsion preparation.
Interior wall coating can be divided into high optical coating, mercerising coating, flat paint and low luster coating according to the glossiness of paint film.Since reflective more serious after the hard-gloss paint film forming, harmful to people's eyes; Human consumer's aesthetic standards more and more tend to have the coatings with low gloss finish of soft outward appearance in addition, so the demand of low luster coating sharply increases.Present low luster coating mainly is to make coating surface coarse through adding flatting silicas such as superfine silicon dioxide, talcum powder, to reach low gloss effect.Generally, the median size of flatting silica is big more, and porosity is high more, and then extinction effect is good more.But large particle size filler makes coating surface coarse, and high porosity reduces paint film compactness, causes stain to infiltrate paint film easily and be difficult to remove, and the coating resistance to soiling descends.
Summary of the invention
The emulsion that the purpose of this invention is to provide a kind of fluorinated silicone modified propenoate, this fluorinated silicone modified acrylic ester emulsion can be used for preparing the good low luster coating of resistance to soiling.
The technical scheme that realizes above-mentioned purpose is following:
A kind of fluorinated silicone modified acrylic ester emulsion, the raw material that it includes following weight part constitutes:
The stratum nucleare pre-emulsion that constitutes by following weight part raw material:
1) Nano silica sol 17-45 part
2) vinyl monomer 85-150 part
3) grow carbochain monomer 7-42 part
4) fluorochemical monomer is 0 part
5) vinyl silane triisopropoxide 2-15 part
6) emulsifying agent 2-7 part
7) deionized water 75-90 part;
The shell pre-emulsion that constitutes by following weight part raw material:
1) vinyl monomer 20-65 part
2) grow carbochain monomer 8-43 part
3) fluorochemical monomer 15-85 part
4) vinyl silane triisopropoxide 5-18 part
5) emulsifying agent 3-10 part
6) deionized water 70-80 part; And
150-165 part deionized water, 0.9-1.3 part emulsifying agent, 0.5-3.0 part pH buffer reagent, 1.0-3.0 part initiator; Said fluorochemical monomer is a perfluoroalkyl acrylate; Said long carbochain monomer is long carbon chain acrylate monomer.
Preferably, said vinyl monomer is one or more the mixture in TEB 3K, ethyl propenoate, Bing Xisuandingzhi, Isooctyl acrylate monomer, vinylbenzene, vinylformic acid, the methylacrylic acid.
Said perfluoroalkyl acrylate is preferably trifluoroethyl methacrylate, methylacrylic acid hexafluoro butyl ester, methylacrylic acid ten difluoro heptyl esters, methylacrylic acid ten trifluoro monooctyl esters, methylacrylic acid 17 fluorine monooctyl esters.Perfluorinated acrylate is on the side chain of original copolymer, to introduce full-fluorine group, because perfluor side chain orientation outwardly, main chain and interior molecules is shielded, and makes the polymer physics stable performance, weathering resistance and good endurance.The low surface energy of perfluorinated acrylate provides good hydrophobic oleophobic performance for emulsion again, makes water-based or oiliness stain be not easy to adhere to.
Long carbochain have excellent hydrophobicity can, can produce synergistic effect with fluorochemical monomer, improve hydrophobic nature and do not reduce oil repellency.Long carbochain monomer according to the invention is long carbon chain acrylate monomer, is preferably one or more mixtures in dodecylacrylate, vinylformic acid cetyl ester, vinylformic acid stearyl, lauryl methacrylate, methylacrylic acid cetyl ester, the methylacrylic acid stearyl.
The vinyl silane triisopropoxide that adopts in the present invention is easy to the main chain that vinyl and acrylic latex are gone in copolymerization, has extraordinary stability at aqueous based systems, and before coating condenses, can not react or crosslinked.General silane coupling agent; Like A-174, A-1100 etc., adding promptly has gel to produce on a small quantity, has limited the further raising of emulsion degree of crosslinking; And the addition of vinyl silane triisopropoxide can reach 10%; Thereby improve the degree of crosslinking of paint film significantly, can obtain hard and highly cross-linked coating after the curing, thereby improve the sticking power of solvent resistance, water tolerance, anti-scratch property and scrub resistance, hygrometric state and the dry state of paint film.The water-based paint prescription that contains this silane still keeps stability and validity after 1 year aging.
The Nano silica sol that the present invention adopts is an alkaline silica sol, and solid content is 30 ± 1%.Because the silanol base is contained on the silica sol particle surface; Can generate covalent linkage with the alcoxyl cardinal extremity reaction of vinyl silane triisopropoxide; And the vinyl terminal of vinyl silane triisopropoxide can generate covalent linkage with resin, thereby makes inorganic silicon oxide and organic polymer coupling.The structure of inorganic Si-O key belongs to ionic, has conductivity preferably, can not produce the electric charge accumulation, does not promptly produce static, and dust is difficult to adhere to.During the coating film forming; Latex particle is jam-packed and distortion fusion each other along with moisture evaporation, and dehydrating condensation between silica sol particle forms the Si-O reticulattion; Lean on organism to fill film forming; Form fine and close structure, make that fine dust particle is difficult for invading its gap, thereby coating has good stain resistance.The high firmness of inorganics also has very big contribution at the coating high temperature resistance aspect after-tacking.
Emulsifying agent according to the invention comprises has anionic emulsifier and nonionic emulsifier, and said anionic emulsifier is one or more the compsn in allyloxy hydroxypropyl azochlorosulfonate acid sodium (COPS-1), ethoxylated alkylphenol ammonium sulfate (CO436), alkyl polyoxyethylene acyl sodium sulfonate (073), disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate (2A1), the 1-propenyloxy group-2-hydroxypropanesulfonic acid sodium (AOPS-1); Said nonionic emulsifier is that the TX10 class is (like polyoxyethylene nonylphenol NP-10; Polyoxyethylene nonylphenol NP-40; TX10 OP-10; TX10 OP-40); The compsn of one or more in the non-ionic type fluorocarbon surfactant (like
FSO).In the shell pre-emulsion, be preferably the mixture of anionic emulsifier and fluorocarbon surfactant because fluorocarbon surfactant have with fluorochemical monomer and polymer phase like fluoroalkyl, the general emulsifying agent of emulsifying effectiveness will be got well.
Said pH buffer reagent is sodium hydrogencarbonate, yellow soda ash, sodium-acetate.
Said initiator is Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
Another object of the present invention provides above-mentioned fluorinated silicone modified preparing acrylate emulsion method.
The technical scheme that realizes above-mentioned purpose is following:
Fluorinated silicone modified preparing acrylate emulsion method may further comprise the steps:
(1) stratum nucleare pre-emulsion, shell pre-emulsion are pressed above-mentioned composition respectively, mixing stirs well even, subsequent use;
(2) in reaction kettle; The 10-20% that adds 90-105 part deionized water, 0.9-1.3 part emulsifying agent, 0.5-3.0 part pH buffer reagent and stratum nucleare pre-emulsion total amount is as seed emulsion; Be warming up to 74-76 ℃; Add after the 20-40% of initiator total amount is dissolved in deionized water, question response system blueing light drips remaining stratum nucleare pre-emulsion, shell pre-emulsion successively when being warming up to 79-81 ℃; And when dripping remaining stratum nucleare pre-emulsion, shell pre-emulsion, dripping remaining initiator, the time that drips remaining stratum nucleare pre-emulsion and shell pre-emulsion is 4-6 hour; Postpone half a hour and drip initiator;
(3) dropwise when initiator, be warmed up to 83-86 ℃ of slaking 0.8-1.2 hour, cool to then below 45 ℃, using ammoniacal liquor to regulate pH is 7, discharging.
In the emulsion polymerization process, adopt to postpone drip the method for fluorochemical monomer, make fluorine element be enriched in the emulsion particle surface, can not only give full play to the excellent properties such as hydrophobic oleophobic property, weathering resistance of fluorine emulsion, can reduce the consumption of fluorochemical monomer again, reduce the emulsion cost.
The present invention prepares a kind of mute light antifouling paint with above-mentioned fluorinated silicone modified acrylic ester emulsion, is formed by the feedstock production of following weight part:
(1) above-mentioned fluorinated silicone modified acrylic ester emulsion 25-50 part;
(2) titanium dioxide slurry 30-45 part;
(3) polyaminoester emulsion 14-30 part;
(4) wax dispersion 1-5 part of emulsifier-free;
(5) skimmer 0.2-0.3 part;
And the weight part ratio of said fluorinated silicone modified acrylic ester emulsion and polyaminoester emulsion is 1～3.5: 1.
The present invention has the distribution of the monomer of different glass temperature at the two-layer pre-emulsion of nucleocapsid through adjusting, emulsion particle is designed to stone soft shell type.For stone soft shell type emulsion, because softer shell is wrapped in the emulsion particle surface, so emulsion is easy to film forming; Because the molecular chain rotation is easier in the soft shell, help the carrying out of crosslinking reaction again, increase the paint film density, improve resistance to soiling; The stone that is wrapped has been given the emulsion particle certain rigidity, can prevent that paint film high temperature from after-tacking.
The present invention uses fluorine carbon emulsion and polyaminoester emulsion blend, utilizes both bigger surface energy difference, thereby increases the nano and micro relief of coatingsurface, reduces coatingsurface to the reflection of light ability, makes coating reach mute light effect.
Compared with prior art, the present invention has following beneficial effect:
The present invention adopts the core-shell emulsion polymerization method, and the organic fluorine of hydrophobic oleophobic is enriched in the latex surface, when not influencing the fluorochemical monomer excellent properties, reduces the emulsion cost, long carbochain monomer and fluorochemical monomer synergy, enhancing emulsion hydrophobicity.
The present invention adopts vinyl silane triisopropoxide in synthetic; Its good stability can not react before coating cohesion or crosslinked, ambient temperature curable; Can obtain hard and highly cross-linked coating after the curing; The molecular structure that is designed to the stone soft shell helps emulsion film forming and self-crosslinking reaction carries out, and improves the compactness of paint film, thereby improves anti-pollution characteristic.
The present invention is compound with inorganic silicon oxide particle and organic polymer, and the siliconoxygen bond reticulattion of utilizing good film-forming properties of polymkeric substance and silicon sol dehydrating condensation to form forms fine and close paint film, further improves contamination resistance.
The present invention adopts fluorine carbon emulsion and polyaminoester emulsion blend to reach low gloss effect, has overcome traditional flatting silica because particle diameter is big, the high paint film density that causes of porosity descends, thus the difficulty that causes stain to permeate easily and be difficult to remove.
Embodiment
Titanium dioxide slurry among the present invention is bought the wheat Brian Goodell chemistry ltd in the Longkou, and wherein the mass content of white titanium pigment is 68-69wt% in the titanium dioxide slurry.The wax dispersion of said emulsifier-free is a kind of low-molecular-weight polyolefin aqueous dispersion of not using any emulsifying agent, and its size distribution is narrow, and particle is spherical in shape.Used Nano silica sol is an alkaline silica sol in following examples, and its solid content is 30 ± 1%, buys Hang Seng's chemical industry N-30 of ltd in Shanghai.
Embodiment 1
One, the main composition of said fluorinated silicone modified acrylic ester emulsion is following:
The raw material consumption of the two-layer pre-emulsion of table 1 nucleocapsid
Stratum nucleare pre-emulsion, shell pre-emulsion respectively by above-mentioned composition, are mixed and stir 20-30min, rotating speed 500～600rpm, subsequent use.
Table 2 initiator solution
| The material title | Initial initiator/g | Drip initiator/g |
| Sodium Persulfate | 0.35 | 1.00 |
| Deionized water | 6 | 48 |
Emulsion viscosity is measured with NDJ-1 type Rotary Viscosimeter.Condition determination is following: probe temperature is 25 ℃; Use No. 1 rotor; Rotating speed is 60r/min, sees GB/T1723-1993.Down together.
Two, said fluorinated silicone modified preparing acrylate emulsion is following:
After stirring in 100 gram deionized waters, 0.4 gram allyloxy hydroxypropyl azochlorosulfonate acid sodium, 0.3 gram ethoxylated alkylphenol ammonium sulfate, 0.6 gram NP-10 and the 0.9g sodium hydrogencarbonate input reaction kettle, add 27g stratum nucleare pre-emulsion, be warming up to 75 ℃; Add initial initiator; Question response system blueing light drips the residue pre-emulsion simultaneously and drips initiator, wherein when being warmed up to 80 ℃; The dropping of residue pre-emulsion is in proper order: drip residue stratum nucleare pre-emulsion earlier, the back drips the shell pre-emulsion.With dripping off the residue pre-emulsion in 4 hours, with dripping off initiator in 4.5 hours.Be warmed up to 85 ℃ of slakings 1 hour, cool to then below 45 ℃, with discharging behind the ammoniacal liquor adjusting pH=7.
Gained emulsion white blueing light, solid content is that 45%, 25 ℃ of following viscosity is 1040mpas.
Three, this composition of implementing described mute light antifouling paint is following:
The mute light antifouling paint prescription of table 3
Four, the preparation of described mute light antifouling paint is following:
Take by weighing quantitative fluorinated silicone modified acrylic ester emulsion and drop in the titanium dioxide slurry, add polyaminoester emulsion, wax dispersion and skimmer again, stirring to make the mute light antifouling paint that is applicable to inner wall of building, and the concrete prescription of coating is seen table 3.
With 200 μ m blade applicators knifing on high-density plate, (25 ℃) maintenance is 7 days under the room temperature with the mute light antifouling paint of above-mentioned preparation.Measure 60 ° of gloss of paint film with the glossiness determinator.Selected pollutent is applied to coating surface, place 1h naturally after, clean back and forth 100 times with the cotton that is soaked with 5% washing powder water, rinse well and dry range estimation stain removing degree.Testing method following examples are identical therewith.
60 ° of gloss of paint film of the mute light antifouling paint of gained are 8, and anti-pollution characteristic is seen table 13.
Embodiment 2
One, the main composition of said fluorinated silicone modified acrylic ester emulsion is following:
The raw material consumption of the two-layer pre-emulsion of table 4 nucleocapsid
Stratum nucleare pre-emulsion, shell pre-emulsion respectively by above-mentioned composition, are mixed and stir 20-30min, rotating speed 500～600rpm, it is subsequent use to stir.
Table 5 initiator solution
| The material title | Initial initiator/g | Drip initiator/g |
| Potassium Persulphate | 0.8 | 2.2 |
| Deionized water | 10 | 50 |
[0081]Two, said fluorinated silicone modified preparing acrylate emulsion is following:
After stirring in 90 gram deionized waters, 0.5 gram alkyl polyoxyethylene acyl sodium sulfonate, 0.5 gram NP-40 and the 3.0g sodium hydrogencarbonate input reaction kettle; Add 44g stratum nucleare pre-emulsion, be warming up to 75 ℃, add initial initiator; Question response system blueing light; Being warmed up to 80 ℃ drips the residue pre-emulsion simultaneously and drips initiator (like embodiment 1, press the stratum nucleare pre-emulsion earlier, the order behind the shell pre-emulsion drips).With dripping off pre-emulsion in 6 hours, with dripping off initiator in 6.5 hours.Be warmed up to 86 ℃ of slakings 1.0 hours, cool to then below 45 ℃, with discharging behind the ammoniacal liquor adjusting pH=7.
Gained emulsion white blueing light, solid content is that 46%, 25 ℃ of following viscosity is 1350mpas.
Three, the composition of said antifouling paint is following:
Table 6 antifouling paint prescription
Take by weighing quantitative fluorinated silicone modified acrylic ester emulsion then and drop in the titanium dioxide slurry, add polyaminoester emulsion, wax dispersion and skimmer again, stirring to make the mute light antifouling paint that is applicable to inner wall of building, and the concrete prescription of antifouling paint is seen table 6.
60 ° of gloss of paint film of the mute light antifouling paint of gained are 5, and anti-pollution characteristic is seen table 13.
Embodiment 3
One, the main composition of said fluorinated silicone modified acrylic ester emulsion is following:
The raw material consumption of the two-layer pre-emulsion of table 7 nucleocapsid
Stratum nucleare pre-emulsion, shell pre-emulsion respectively by above-mentioned composition, are mixed and stir 20-30min, rotating speed 500～600rpm, subsequent use.
Table 8 initiator solution
| The material title | Initial initiator/g | Drip initiator/g |
| Ammonium persulphate | 0.6 | 1.4 |
| Deionized water | 10 | 50 |
Two, the main composition of said fluorinated silicone modified acrylic ester emulsion is following:
After stirring in 105 gram deionized waters, 0.5 gram 1-propenyloxy group-2-hydroxypropanesulfonic acid sodium, 0.6 gram OP-10 and the 1.5g yellow soda ash input reaction kettle; Add 37g stratum nucleare pre-emulsion; Be warming up to 75 ℃, add initial initiator, question response system blueing light; Being warmed up to 80 ℃ drips residue pre-emulsion (press the stratum nucleare pre-emulsion earlier, the order behind the shell pre-emulsion drips) simultaneously and drips initiator.With dripping off pre-emulsion in 5.5 hours, with dripping off initiator in 6.0 hours.Be warmed up to 83 ℃ of slakings 1.2 hours, cool to then below 45 ℃, with discharging behind the ammoniacal liquor adjusting pH=7.
Gained emulsion white blueing light, solid content is 46%, viscosity is 3370mpas under the room temperature.
Table 9 antifouling paint prescription
Take by weighing quantitative fluorinated silicone modified acrylic ester emulsion then and drop in the titanium dioxide slurry, add polyaminoester emulsion, wax dispersion and skimmer again, stirring to make the mute light antifouling paint that is applicable to inner wall of building, and the concrete prescription of antifouling paint is seen table 9.
60 ° of gloss of paint film of the mute light antifouling paint of gained are 7, and anti-pollution characteristic is seen table 13.
Embodiment 4
One, the main composition of said fluorinated silicone modified acrylic ester emulsion is following:
The raw material consumption of the two-layer pre-emulsion of table 10 nucleocapsid
Stratum nucleare pre-emulsion, shell pre-emulsion respectively by above-mentioned composition, are mixed and stir 20-30min, rotating speed 500～600rpm, it is subsequent use to stir.
Table 11 initiator solution
| The material title | Initial initiator/g | Drip initiator/g |
| Sodium Persulfate | 0.4 | 0.8 |
| Deionized water | 15 | 45 |
Two, said fluorinated silicone modified preparing acrylate emulsion is following:
After stirring in 95 gram deionized waters, 0.5 gram disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, 0.4 gram OP-40 and the 0.5g sodium-acetate input reaction kettle; Add 45g stratum nucleare pre-emulsion; Be warming up to 75 ℃, add initial initiator, question response system blueing light; Being warmed up to 80 ℃ drips residue pre-emulsion (press the stratum nucleare pre-emulsion earlier, the order behind the shell pre-emulsion drips) simultaneously and drips initiator.With dripping off pre-emulsion in 5 hours, with dripping off initiator in 5.5 hours.Be warmed up to 86 ℃ of slakings 0.8 hour, cool to then below 45 ℃, with discharging behind the ammoniacal liquor adjusting pH=7.
Gained emulsion white blueing light, solid content is 45%, viscosity is 510mpas under the room temperature.
Three, the composition of said antifouling paint is following:
Table 12 antifouling paint prescription
Take by weighing quantitative fluorinated silicone modified acrylic ester emulsion then and drop in the titanium dioxide slurry, add polyaminoester emulsion, wax dispersion and skimmer again, stirring to make the mute light antifouling paint that is applicable to inner wall of building, and the concrete prescription of antifouling paint is seen table 13.
60 ° of gloss of paint film of the mute light antifouling paint of gained are 6, and anti-pollution characteristic is seen table 15.
Table 13 resistant test result
| The stain title | Embodiment 1 coating | Embodiment 2 coating | Embodiment 3 coating | Embodiment 4 coating |
| China's pencil | ○ | □ | □ | ○ |
| Pencil is red | ○ | ○ | ○ | ○ |
[0123]
| Wax crayon is red | ||||
| Wax crayon is blue | Zero | Zero | Zero | Zero |
| Watercolor is red | ◇ | Zero | ||
| Watercolor is green | ◇ | ◇ | ||
| Watercolor is blue | Zero | Zero | ||
| The oil pen | △ | ◇ | △ | △ |
| Tomato juice | Zero | Zero | Zero | Zero |
| Coffee | Zero | Zero | Zero | Zero |
Annotate: zero cleans basically; is residual more shallow; ◇ is medium; △ is residual darker; * residual profound.
More than be merely specific embodiment of the present invention, do not limit protection scope of the present invention with this; Any replacement and the improvement on the basis of not violating the present invention's design, done all belong to protection scope of the present invention.
Claims (9)
1. a fluorinated silicone modified acrylic ester emulsion is characterized in that, it is mainly formed by the feedstock production of following weight part:
(A) the stratum nucleare pre-emulsion of forming by following weight part raw material:
1) Nano silica sol 17-45 part
2) vinyl monomer 85-150 part
3) grow carbochain monomer 7-42 part
4) fluorochemical monomer is 0 part
5) vinyl silane triisopropoxide 2-15 part
6) emulsifying agent 2-7 part
7) deionized water 75-90 part;
(B) the shell pre-emulsion of forming by following weight part raw material:
1) vinyl monomer 20-65 part
2) grow carbochain monomer 8-43 part
3) fluorochemical monomer 15-85 part
4) vinyl silane triisopropoxide 5-18 part
5) emulsifying agent 3-10 part
6) deionized water 70-80 part; And
(C) 0.9-1.3 part emulsifying agent, 0.5-3.0 part pH buffer reagent, 1.0-3.0 part initiator; 150-165 part deionized water, said fluorochemical monomer are perfluoroalkyl acrylate; Said long carbochain monomer is long carbon chain acrylate monomer.
2. fluorinated silicone modified acrylic ester emulsion according to claim 1; It is characterized in that said vinyl monomer is one or more the mixture in TEB 3K, ethyl propenoate, Bing Xisuandingzhi, Isooctyl acrylate monomer, vinylbenzene, vinylformic acid, the methylacrylic acid.
3. fluorinated silicone modified acrylic ester emulsion according to claim 1; It is characterized in that said perfluoroalkyl acrylate is trifluoroethyl methacrylate, methylacrylic acid hexafluoro butyl ester, methylacrylic acid ten difluoro heptyl esters, methylacrylic acid ten trifluoro monooctyl esters or methylacrylic acid 17 fluorine monooctyl esters.
4. fluorinated silicone modified acrylic ester emulsion according to claim 1; It is characterized in that said long carbon chain acrylate monomer is one or both mixtures in dodecylacrylate, vinylformic acid cetyl ester, vinylformic acid stearyl, lauryl methacrylate, methylacrylic acid cetyl ester, the methylacrylic acid stearyl.
5. fluorinated silicone modified acrylic ester emulsion according to claim 1 is characterized in that, said Nano silica sol is an alkaline silica sol, and its solid content is 30 ± 1%.
6. fluorinated silicone modified acrylic ester emulsion according to claim 1; It is characterized in that; Said emulsifying agent comprises has anionic emulsifier and nonionic emulsifier, and said anionic emulsifier is one or more the compsn in allyloxy hydroxypropyl azochlorosulfonate acid sodium, ethoxylated alkylphenol ammonium sulfate, alkyl polyoxyethylene acyl sodium sulfonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, the 1-propenyloxy group-2-hydroxypropanesulfonic acid sodium; Said nonionic emulsifier is one or more the compsn in polyoxyethylene nonylphenol NP-10, polyoxyethylene nonylphenol NP-40, TX10 OP-10, TX10 OP-40, the non-ionic type fluorocarbon surfactant.
7. fluorinated silicone modified acrylic ester emulsion according to claim 6 is characterized in that, in the said shell pre-emulsion, said emulsifying agent is the mixture of anionic emulsifier and fluorocarbon surfactant.
8. fluorinated silicone modified acrylic ester emulsion according to claim 1 is characterized in that, said pH buffer reagent is sodium hydrogencarbonate, yellow soda ash, sodium-acetate; Said initiator is Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
9. a method for preparing each said fluorinated silicone modified acrylic ester emulsion of claim 1-8 is characterized in that, may further comprise the steps:
(1) stratum nucleare pre-emulsion, shell pre-emulsion are formed by the said raw material of claim 1 respectively, mixing and stirring, subsequent use;
(2) in reaction kettle; The 10-20% that adds 90-105 part deionized water, 0.9-1.3 part emulsifying agent, 0.5-3.0 part pH buffer reagent and stratum nucleare pre-emulsion total amount is as seed emulsion; Be warming up to 74-76 ℃; Add after the 20-40% of initiator total amount is dissolved in deionized water; Question response system blueing light drips remaining stratum nucleare pre-emulsion, shell pre-emulsion successively when being warming up to 79-81 ℃, and when dripping remaining stratum nucleare pre-emulsion, shell pre-emulsion, drips with the remaining initiator of deionized water dissolved;
(3) dropwise when initiator, be warmed up to 83-86 ℃ of slaking 0.8-1.2 hour, be cooled to then below 45 ℃, using ammoniacal liquor to regulate pH is 7, and discharging promptly gets said fluorinated silicone modified acrylic ester emulsion.10, preparation method according to claim 9 is characterized in that, in the step (2), the time that drips remaining stratum nucleare pre-emulsion and shell pre-emulsion is 4-6 hour; Remaining initiator dropwises in back 0.5 hour at remaining stratum nucleare pre-emulsion, shell pre-emulsion and drips off.
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