CN1654533A - Nano silicon dioxide/acrylate composite emulsion and process for preparing same - Google Patents
Nano silicon dioxide/acrylate composite emulsion and process for preparing same Download PDFInfo
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- CN1654533A CN1654533A CN200510038154.0A CN200510038154A CN1654533A CN 1654533 A CN1654533 A CN 1654533A CN 200510038154 A CN200510038154 A CN 200510038154A CN 1654533 A CN1654533 A CN 1654533A
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- acrylate
- emulsion
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- nano
- composite emulsion
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- 239000000839 emulsion Substances 0.000 title claims abstract description 104
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 25
- 239000005543 nano-size silicon particle Substances 0.000 title claims description 40
- 235000012239 silicon dioxide Nutrition 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000004381 surface treatment Methods 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000003995 emulsifying agent Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002114 nanocomposite Substances 0.000 claims description 17
- 238000009413 insulation Methods 0.000 claims description 14
- -1 acrylic ester Chemical class 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 11
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 11
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 10
- 230000002776 aggregation Effects 0.000 claims description 9
- 238000004220 aggregation Methods 0.000 claims description 9
- 238000004945 emulsification Methods 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 238000000643 oven drying Methods 0.000 claims description 9
- 230000003252 repetitive effect Effects 0.000 claims description 9
- 238000005201 scrubbing Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 7
- 239000000872 buffer Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 4
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 claims description 4
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 4
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 4
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- KFGCNCWYUHCIBF-UHFFFAOYSA-N C(CCC(=O)O)(=O)O.C(C)C(CCCCC)[Na] Chemical compound C(CCC(=O)O)(=O)O.C(C)C(CCCCC)[Na] KFGCNCWYUHCIBF-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 9
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 12
- 229960001866 silicon dioxide Drugs 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 5
- 235000021050 feed intake Nutrition 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002265 electronic spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention discloses one kind of nanometer composite silica/acrylate emulsion and its preparation process. The present invention is superior to available technology, and the composite emulsion has dispersed nanometer inorganic silica phase in 0.1-5 % of the total weight of monomers for the acrylate copolymer emulsion. The preparation process includes the surface treatment of nanometer inorganic silica phase, and synthesizing nanometer inorganic phase/polymer emulsion in molecular level compounding through in-situ polymerization process or seed emulsion polymerization process. The composite emulsion of the present invention can form film with doubled tensile strength and breaking elongation. Adding nanometer silica in 0.2 % results in tensile strength of 5.25 MPa and breaking elongation of 1300 %.
Description
Technical field
The present invention relates to a kind ofly to be used for weaving, the composite emulsion of industry such as fiber, coating, tackiness agent and additives for plastics and preparation method thereof, more specifically to a kind of nano silicon dioxide/acrylate composite emulsion and preparation method thereof.
Background technology
Acrylate is the general name of the ester class of vinylformic acid and homologue thereof, can autohemagglutination or and other monomer copolymerizations.Because esters of acrylic acid is as the monomer of polymkeric substance, contain unsaturated double-bond and polar molecular structure, can be built into many polymer formulators with various performances, thereby can obtain the not equal characteristic of viscosity, hardness, weather resistance, second-order transition temperature, make its product have various purposes, be widely used in the industries such as weaving, fiber, coating, tackiness agent and additives for plastics.
Along with the whole society to raising healthy, the environmental protection attention degree, the development trend of world's coating, tackiness agent and textile auxiliary agent etc. is also gradually towards high-performance, oligosaprobic trend development, thereby also had higher requirement in fields such as coating.The acrylic ester emulsion coatings formulated has many outstanding characteristics at present, photostabilization, scrub resistance, resistance to acids and bases and erosion resistance etc. as excellence, but because acrylic ester emulsion poor water resistance, low temperature becomes fragile easily, high temperature becomes sticky easily, shortcoming such as ageing resistance difference particularly, the acrylic ester polymer moisture permeability is low during as fabric coating, water-repellancy is poor.In order to improve the performance of acrylic ester emulsion, people have developed new technologies such as core-shell emulsion polymerization, latex interpenetrating polymerization, emulsifier-free emulsion polymerization, group transfer polymerization, micro-emulsion polymerization in succession, but the ageing resistance of coating, erosion resistance and mechanical property etc. still need further to improve.
Nanometer SiO
2Because of having the distinctive small-size effect of nanoparticle, surface effects, quantum effect, macro quanta tunnel effect etc., more and more be subjected to investigator's favor.Utilize these characteristic synthesis of nano SiO of nano material
2/ polymer composites, this advanced composite material can with the elasticity of physical strength, modulus, thermostability and the high molecular polymer of inorganic nano-particle and easily characteristics such as processing ideally combine the tensile strength of raising material, hardness, snappiness, anti-scratch property, ultraviolet aging resistance, erosion resistance, wear resistance, heat-insulation and heat-preservation, static electricity resistance etc.
Because nanometer SiO
2Particle size is little, specific surface area is big, there is the hydroxyl of a large amount of unsaturated residual bonds and different bonding states in the surface, thereby very easy mutual generation hydrogen bond action and reuniting, this reunion causes decline, the stability decreases of the mechanical property of material, the unfavorable conditions such as transmittance step-down of material in polymkeric substance.Thereby nanometer SiO
2Dispersion to nanometer SiO
2It is particularly important that/polymer composites seems.
Many investigators adopt nanometer SiO both at home and abroad at present
2Come modified acrylic acid emulsion, its main method of modifying is blending method and sol-gel method.Blending method is with nanometer SiO
2A class matrix material that directly carries out dispersing and mixing with polymkeric substance and obtain.The characteristics of these class methods are that process is simpler, realize industrialization easily.Its shortcoming is to want nanometer SiO
2Particle is difficulty of the nano level homodisperse of ecosystem, thereby brings new problem also for the stability of product.
(Jose-Luiz is an initiator with cationic azo compd A IBA Luna-Xavier) to people such as 2002 250 volumes of " colloid and interface science " (Journal of Colloid and Interface Science) the 1st phase Louis, nanometer SiO
2Colloidal sol is nuclear, and polymethylmethacrylate is that shell has synthesized nanometer SiO
2/ polymethylmethacrylate emulsion polymer.
The tetraethoxy-silicane of employing butyl methacrylate polymer emulsion such as " applied polymer science " (Journal of Applied Polymer Science) 2002 83 volume the 2nd phase XIN TONG and prehydrolysis is mixed with out nanometer SiO
2-poly-n-butyl methacrylate nano composite material, and compared the nanometer SiO that sol-gel method and traditional blending method are prepared
2-poly-n-butyl methacrylate nano composite material, through TEM (scanning electronic microscope), AFM (atomic force microscope), the test of FT-IR (Fourier infrared spectrum) and XPS methods such as (electronic spectrums) obtains polymer emulsion particle and nanometer SiO that sol-gel method prepares
2Between than stronger interactional conclusion being arranged with traditional blending method.
Sol-gel method synthesis of nano SiO
2The characteristics of matrix material are: the condition of reaction is comparatively gentle, nanometer SiO
2Disperse comparatively evenly in polymkeric substance, main drawback is in gelation process because the volatilization of solvent and water molecules easily causes material generation embrittlement.
Summary of the invention
The object of the present invention is to provide a kind of nano silicon dioxide/acrylate composite emulsion that has good stability, to solve the deficiency that prior art exists, the coating that this emulsion makes has tensile strength, hardness, snappiness, anti-scratch property, ultraviolet aging resistance, erosion resistance, wear resistance, heat-insulation and heat-preservation, static electricity resistance etc. preferably, is widely used in fields such as coating, tackiness agent and textile auxiliary agent.
Another object of the present invention provides a kind of preparation method of nano silicon dioxide/acrylate composite emulsion.Thereby in order to improve the performance that the dispersiveness of silicon-dioxide in emulsion further improves emulsion, the present invention selects coupling agent treatment silicon-dioxide for use, use in-situ polymerization and two kinds of methods of seed emulsion polymerization, made have good stability have a molecular level compound nano silicon dioxide/acrylate composite emulsion, the result shows that emulsion, especially seed emulsion polymerization that two kinds of methods all can obtain to have good stability can make stability and the more superior emulsion of every performance.
Technical scheme of the present invention is:
Nano silicon dioxide/acrylate nano-composite emulsion of the present invention, it is the inorganic phase of nano silicon that in composite emulsion, is scattered here and there, wherein inorganic 0.1～5% of the acrylate eopolymerization emulsion monocase gross weight that accounts for mutually, described nano silicon is inorganic to be surface treated nano silicon mutually; The required monomer of described acrylate copolymer emulsion is the monomer as general formula (I):
CH
2＝CR
2(COOR
3)???????????????(I)
(I) R in the formula
2Expression hydrogen atom or methyl, R
3Expression hydrogen atom or carbonatoms are 1～9 monovalence alkyl.
Nano silicon dioxide/acrylate nano-composite emulsion of the present invention, the monomer of its acrylic ester emulsion copolymerization are to be selected from methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, acrylic or methacrylic acid a kind of or its combination wherein.
The surface treatment of the inorganic phase of nano silicon in the nano silicon dioxide/acrylate nano-composite emulsion of the present invention is: take by weighing 0.1～50 part of nanometer SiO
2Under 100 ℃, oven drying 2 hours, then with 5～500 parts of solvent after ultrasonic dispersing half an hour, add the coupling agent after 0.1～50 part of hydrolysis, stir 15min post-heating to 100 ℃ backflow 3 hours, filter then, get filter cake ethanol repetitive scrubbing, following evaporation is 1 hour to vacuum drying oven in 0.04Mpa, and is following dry 1 hour in 110 ℃ at last.
Used coupling agent was gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, second diamino propyl trimethoxy silicane, vinyl three (2-methoxyethoxy) silane, vinyl trichloro silane, vinyltriethoxysilane, vinyltrimethoxy silane or gamma-methyl allyl acyloxypropyl trimethoxysilane when nano-silica surface was handled among the present invention; Used solvent is toluene, dimethylbenzene or methyl ethyl ketone.
The preparation method of nano silicon dioxide/acrylate nano-composite emulsion of the present invention, be earlier to pass through surface treatment mutually with nano silicon is inorganic, again respectively through situ aggregation method or seed emulsion polymerization synthetic have the molecular level compound inorganic/the high molecular nanometer composite emulsion, step comprises:
A) nanometer SiO
2Pre-treatment: take by weighing 0.1～50 part of nanometer SiO
2Under 100 ℃, oven drying 2 hours, then with 5～500 parts of solvent after ultrasonic dispersing half an hour, add the coupling agent after 0.1～50 part of hydrolysis, stir 15min post-heating to 100 and ℃ refluxed 3 hours, filter then, get filter cake ethanol repetitive scrubbing, the down evaporation 1 hour to vacuum drying oven in 0.04Mpa, final sample in 110 ℃ dry 1 hour down, be placed in the moisture eliminator standby;
B) with the nano silicon nuclear preparation composite emulsion: get in the step a) through pretreated nanometer SiO
20.1～5 parts the water high speed mechanical dispersion that adds small amounts of emulsifiers 15 minutes, with scattered nanometer SiO
2Add flask and be heated to 75 ℃, will be added with buffer reagent, initiator, the pre-emulsion of emulsifying agent and 10～20 parts of mix monomers progressively is added dropwise to, and control reaction temperature is incubated 30 minutes at 75 ℃, allows monomer with nanometer SiO
2Coat and polymerization, and, progressively residual monomer and emulsifying agent and initiator are added dropwise to system in two batches then with this seed as composite emulsion, treat that monomer dropping is warming up to 80 ℃ of insulations 2 hours after intact, the slaking 30 minutes that heats up at last, pH value to 8～9 are regulated in the cooling back;
Perhaps
B) situ aggregation method prepares composite emulsion: with the pretreated nanometer SiO of process in the step a)
2With monomer, the pre-emulsification of emulsifying agent 15 minutes, the method that adopts fed batch to drip, getting 10～20 parts of pre-emulsions earlier feeds intake, question response drips the residue pre-emulsion after 30 minutes, initiator and buffer reagent also adopt the mode of dropping, and control reaction temperature is at 75 ℃, treat to be warming up to after pre-emulsion drips 80 ℃ of insulations 2 hours, the slaking that heats up at last, 30 minutes, pH value to 8～9 were regulated in the cooling back.
Used coupling agent is gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, second diamino propyl trimethoxy silicane, vinyl three (2-methoxyethoxy) silane, vinyl trichloro silane, vinyltriethoxysilane, vinyltrimethoxy silane or gamma-methyl allyl acyloxypropyl trimethoxysilane among the preparation method of nano silicon dioxide/acrylate nano-composite emulsion of the present invention; Used solvent is that the used buffer reagent of toluene, dimethylbenzene or methyl ethyl ketone is sodium bicarbonate or yellow soda ash; Used initiator is Sodium Persulfate or Potassium Persulphate; Used emulsifying agent is a kind of or its combination in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Succinic Acid ethylhexyl sodium sulfonate, sodium alkyl naphthalene sulfonate, alkylphenol polyoxyethylene, the fatty alcohol-polyoxyethylene ether; Monomer is to be selected from methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, acrylic or methacrylic acid a kind of or its combination wherein.
Beneficial effect of the present invention is:
The present invention combines the toughness of rigidity, hardness and the macromolecular material of inorganic nano-particle, obtain the material of mechanical property excellence, add a small amount of treated nano silicon, the tensile strength and the elongation at break of filming are multiplied, the nano silicon of adding 0.2%, it is 5.25Mpa that its tensile strength increases, and elongation at break is 1300%.The processing of coupling agent also has very big influence to the stability and the mechanical property of emulsion, adopts the nanometer SiO through coupling agent treatment
2The tensile strength of material than the raising of not adopting 35%, and elongation at break has improved 198%, and water tolerance, ageing resistance all are improved largely.This emulsion self-vulcanizing forms a kind of coating that the flexible excellent performance is arranged.The coating that this emulsion makes also has better hardness, snappiness, anti-scratch property, ultraviolet aging resistance, erosion resistance, wear resistance, heat-insulation and heat-preservation, static electricity resistance etc., can be widely used in fields such as coating, tackiness agent and textile auxiliary agent.
Embodiment
Further specify the present invention below by embodiment and Comparative Examples, in embodiment and Comparative Examples, with the water tolerance behind water-intake rate (%) the expression emulsion film forming, this numerical value is low more, illustrates that water tolerance is good more.
Embodiment 1:
The processing of nano silicon: take by weighing 10 gram gas phase nano SiO
2Under 100 ℃, oven drying 2 hours.Mixes afterwards ultrasonic dispersing half an hour then with 100 gram toluene, add 10 gram γ-An Jibingjisanyiyangjiguiwans, stir 15min post-heating to 100 ℃ backflow 3 hours, filter then, get filter cake ethanol repetitive scrubbing, evaporated 1 hour down to vacuum drying oven in 0.04Mpa.Final sample is following dry 1 hour in 110 ℃.Be placed in the moisture eliminator standby.
The preparation of composite emulsion: get above-mentioned treated nanometer SiO
20.3 gram is the water high speed mechanical dispersion that adds a small amount of sodium lauryl sulphate 15 minutes, with scattered nanometer SiO
2Add flask and be heated to 75 ℃, add water 90 grams, NaHCO
30.36 gram, (NH
4)
2S
2O
80.36 gram, sodium lauryl sulphate 0.9 gram, nonyl phenol polyethenoxy ether OP-10 emulsifying agent 0.9 gram, with monomers methyl methacrylate 24 grams, butyl acrylate 36 grams, methacrylic acid 1.2 gram is pre-mixed evenly, gets wherein 1/10th monomers earlier and adds flask and react after about 30 minutes and drip residual monomer, is warming up to 80 ℃ of insulations 2 hours after waiting to drip, the slaking 30 minutes that heats up at last, cooling back add ammoniacal liquor and regulate pH value to 8～9.Measure mechanical mechanics property and water tolerance behind the emulsion film forming then, the results are shown in Table 1.
Embodiment 2:
The processing of nano silicon: take by weighing 2 gram gas phase nano SiO
2Under 100 ℃, oven drying 2 hours.Mixes afterwards ultrasonic dispersing half an hour then with 20 gram toluene, add 2.5 gram gamma-methyl allyl acyloxypropyl trimethoxysilanes, stir 15min post-heating to 100 ℃ backflow 3 hours, filter then, get filter cake ethanol repetitive scrubbing, evaporated 1 hour down to vacuum drying oven in 0.04Mpa.Final sample is following dry 1 hour in 110 ℃.Be placed in the moisture eliminator standby.
The preparation of composite emulsion: the nanometer SiO that will handle through aforesaid method
20.5 gram adds water 90 grams, NaHCO
30.36 gram, (NH
4)
2S
2O
80.36 gram, sodium lauryl sulphate 0.9 gram, nonyl phenol polyethenoxy ether OP-10 emulsifying agent 0.9 gram, methyl methacrylate 24 grams, butyl acrylate 36 grams, methacrylic acid 1.2 grams, the pre-emulsification of emulsifying agent 15 minutes, adopt the synthetic composite emulsion of situ aggregation method, get 20 gram pre-emulsions earlier and feed intake, question response drips the residue pre-emulsion after 30 minutes.Control reaction temperature treats to be warming up to after pre-emulsion drips 80 ℃ of insulations 2 hours at 75 ℃, the slaking 30 minutes that heats up at last, and the cooling back adds ammoniacal liquor and regulates pH value to 8～9.Measure mechanical mechanics property and water tolerance behind the emulsion film forming then, the results are shown in Table 1.
Embodiment 3:
The processing of nano silicon: take by weighing 10 gram gas phase nano SiO
2Under 100 ℃, oven drying 2 hours.Mixes afterwards ultrasonic dispersing half an hour then with 100 gram toluene, add 10 gram gamma-amino propyl group diethoxy silanes, stir 15min post-heating to 100 ℃ backflow 3 hours, filter then, get filter cake ethanol repetitive scrubbing, evaporated 1 hour down to vacuum drying oven in 0.04Mpa.Final sample is following dry 1 hour in 110 ℃.Be placed in the moisture eliminator standby.
The preparation of composite emulsion: the nanometer SiO that will handle
21 gram adds water 90 grams, NaHCO
30.36 gram, (NH
4)
2S
2O
80.36 gram, sodium lauryl sulphate 0.9 gram, nonyl phenol polyethenoxy ether OP-10 emulsifying agent 0.9 gram, methyl methacrylate 24 grams, butyl acrylate 36 grams, methacrylic acid 1.2 grams, the pre-emulsification of emulsifying agent 15 minutes, adopt the synthetic composite emulsion of situ aggregation method, get 20 gram pre-emulsions earlier and feed intake, question response drips the residue pre-emulsion after 30 minutes.Control reaction temperature treats to be warming up to after pre-emulsion drips 80 ℃ of insulations 2 hours at 75 ℃, the slaking 30 minutes that heats up at last, and the cooling back adds ammoniacal liquor and regulates pH value to 8～9.Measure mechanical mechanics property and water tolerance behind the emulsion film forming then, the results are shown in Table 1.
Embodiment 4:
The processing of nano silicon: take by weighing 10 gram gas phase nano SiO
2Under 100 ℃, oven drying 2 hours.Mixes afterwards ultrasonic dispersing half an hour then with 100 gram dimethylbenzene, add 10 gram second diamino propyl trimethoxy silicanes, stir 15min post-heating to 100 ℃ backflow 3 hours, filter then, get filter cake ethanol repetitive scrubbing, evaporated 1 hour down to vacuum drying oven in 0.04Mpa.Final sample is following dry 1 hour in 110 ℃.Be placed in the moisture eliminator standby.
The preparation of composite emulsion: get above-mentioned treated nanometer SiO
28.09 gram is the water high speed mechanical dispersion that adds a small amount of sodium lauryl sulphate 15 minutes, with scattered nanometer SiO
2Add flask and be heated to 75 ℃, add water 90 grams, NaHCO
30.36 gram, (NH
4)
2S
2O
80.36 gram, sodium lauryl sulphate 0.9 gram, nonyl phenol polyethenoxy ether OP-10 emulsifying agent 0.9 gram, with monomer Jia Jibingxisuanyizhi 24 grams, ethyl propenoate 10 grams, butyl acrylate 26 grams, methacrylic acid 1.2 grams are pre-mixed evenly, getting wherein 1/10th monomers earlier adds flask and reacts after about 30 minutes and drip residual monomer, be warming up to 80 ℃ of insulations 2 hours after waiting to drip, the slaking 30 minutes that heats up at last, the cooling back adds ammoniacal liquor and regulates pH value to 8～9.Measure mechanical mechanics property and water tolerance behind the emulsion film forming then, the results are shown in Table 1.
Embodiment 5:
The processing of nano silicon: take by weighing 5 gram gas phase nano SiO
2Under 100 ℃, oven drying 2 hours.Mixes afterwards ultrasonic dispersing half an hour then with 100 gram toluene, add 3.5 gram gamma-methyl allyl acyloxypropyl trimethoxysilanes, stir 15min post-heating to 100 ℃ backflow 3 hours, filter then, get filter cake ethanol repetitive scrubbing, evaporated 1 hour down to vacuum drying oven in 0.04Mpa.Final sample is following dry 1 hour in 110 ℃.Be placed in the moisture eliminator standby.
The preparation of composite emulsion: the nanometer SiO that will handle through aforesaid method
22.5 gram adds water 90 grams, NaHCO
30.36 gram, (NH
4)
2S
2O
80.36 gram, sodium lauryl sulphate 0.9 gram, nonyl phenol polyethenoxy ether OP-10 emulsifying agent 0.9 gram, methyl methacrylate 14 grams, butyl methacrylate 10 grams, Ethyl acrylate 30 grams, the synthetic composite emulsion of situ aggregation method is adopted in methacrylic acid 1.2 grams, the pre-emulsification of emulsifying agent 15 minutes, get 20 gram pre-emulsions earlier and feed intake, question response drips the residue pre-emulsion after 30 minutes.Control reaction temperature treats to be warming up to after pre-emulsion drips 80 ℃ of insulations 2 hours at 75 ℃, the slaking 30 minutes that heats up at last, and the cooling back adds ammoniacal liquor and regulates pH value to 8～9.Measure mechanical mechanics property and water tolerance behind the emulsion film forming then, the results are shown in Table 1.
Comparative Examples 1 (contains nanometer SiO
2, be untreated in the surface)
Emulsion preparation step: with unmodified nanometer SiO
20.5 gram adds water 90 grams, NaHCO
30.36 gram, (NH
4)
2S
2O
80.36 gram, sodium lauryl sulphate 0.9 gram, OP10 0.9 gram, methyl methacrylate 24 grams, butyl acrylate 36 grams, methacrylic acid 1.2 grams, the pre-emulsification of emulsifying agent 15 minutes, adopt the synthetic composite emulsion of situ aggregation method, get 20 gram pre-emulsions earlier and feed intake, question response drips the residue pre-emulsion after 30 minutes.Control reaction temperature treats to be warming up to after pre-emulsion drips 80 ℃ of insulations 2 hours at 75 ℃, the slaking 30 minutes that heats up at last, and the cooling back adds ammoniacal liquor and regulates pH value to 8～9.Measure mechanical mechanics property and water tolerance behind the emulsion film forming then, the results are shown in Table 1.
Comparative Examples 2 (does not contain nanometer SiO
2)
Emulsion preparation step: deionized water 90 grams, NaHCO
30.36 gram, (NH
4)
2S
2O
80.36 gram, sodium lauryl sulphate 0.9 gram, OP10 0.9 gram, methyl methacrylate 24 grams, butyl acrylate 36 grams, methacrylic acid 1.2 grams, the pre-emulsification of emulsifying agent 15 minutes, adopt the synthetic composite emulsion of situ aggregation method, get 20 gram pre-emulsions earlier and feed intake, question response drips the residue pre-emulsion after 30 minutes.Control reaction temperature treats to be warming up to after pre-emulsion drips 80 ℃ of insulations 2 hours at 75 ℃, the slaking 30 minutes that heats up at last, and the cooling back adds ammoniacal liquor and regulates pH value to 8～9.Measure mechanical mechanics property and water tolerance behind the emulsion film forming then, the results are shown in Table 1.
Mechanical mechanics property in the following table 1 behind each embodiment and the Comparative Examples emulsion film forming and the explanation of water-proof test data, the performance of emulsion of the present invention obviously is better than the performance of the emulsion of Comparative Examples.
Table 1
| Performance behind the emulsion film forming | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 1 | Comparative Examples 2 |
| Tensile strength (MPa) | ??5.19 | ??5.77 | ??5.68 | ??5.38 | ??5.59 | ??2.77 | ??2.49 |
| Elongation at break (%) | ??1262 | ??1191 | ??1090 | ??1097 | ??1163 | ??400 | ??378 |
| Water-intake rate (%) | ??25.5 | ??27.7 | ??26.0 | ??26.9 | ??25.8 | ??31.0 | ??29.5 |
Claims (10)
1, a kind of nano silicon dioxide/acrylate nano-composite emulsion, the inorganic phase of nano silicon is characterized in that being scattered here and there in composite emulsion, wherein inorganic 0.1～5% of the acrylate eopolymerization emulsion monocase gross weight that accounts for mutually, described nano silicon is inorganic to be surface treated nano silicon mutually; The required monomer of described acrylate copolymer emulsion is the monomer as general formula (I):
CH
2＝CR
2(COOR
3)????????????????(I)
(I) R in the formula
2Expression hydrogen atom or methyl, R
3Expression hydrogen atom or carbonatoms are 1～9 monovalence alkyl.
2, nano silicon dioxide/acrylate nano-composite emulsion according to claim 1, the monomer that it is characterized in that described acrylic ester emulsion copolymerization is to be selected from methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, the vinylformic acid pentyl ester, Ethyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, the methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, acrylic or methacrylic acid a kind of or its combination wherein.
3, nano silicon dioxide/acrylate nano-composite emulsion according to claim 1 is characterized in that the surface treatment of the inorganic phase of described nano silicon is: take by weighing 0.1～50 part of nanometer SiO
2Under 100 ℃, oven drying 2 hours, then with 5～500 parts of solvent after ultrasonic dispersing half an hour, add the coupling agent after 0.1～50 part of hydrolysis, stir 15min post-heating to 100 ℃ backflow 3 hours, filter then, get filter cake ethanol repetitive scrubbing, following evaporation is 1 hour to vacuum drying oven in 0.04Mpa, and is following dry 1 hour in 110 ℃ at last.
4, nano silicon dioxide/acrylate nano-composite emulsion according to claim 3 is characterized in that described coupling agent is gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, second diamino propyl trimethoxy silicane, vinyl three (2-methoxyethoxy) silane, vinyl trichloro silane, vinyltriethoxysilane, vinyltrimethoxy silane or gamma-methyl allyl acyloxypropyl trimethoxysilane.
5, nano silicon dioxide/acrylate nano-composite emulsion according to claim 3 is characterized in that described solvent is toluene, dimethylbenzene or methyl ethyl ketone.
6, the preparation method of the described nano silicon dioxide/acrylate nano-composite emulsion of claim 1～5, it is characterized in that earlier passing through surface treatment mutually with nano silicon is inorganic, again respectively through situ aggregation method or seed emulsion polymerization synthetic have the molecular level compound inorganic/the high molecular nanometer composite emulsion, step comprises:
A) nanometer SiO
2Pre-treatment: take by weighing 0.1～50 part of nanometer SiO
2Under 100 ℃, oven drying 2 hours, then with 5～500 parts of solvent after ultrasonic dispersing half an hour, add the coupling agent after 0.1～50 part of hydrolysis, stir 15min post-heating to 100 and ℃ refluxed 3 hours, filter then, get filter cake ethanol repetitive scrubbing, the down evaporation 1 hour to vacuum drying oven in 0.04Mpa, final sample in 110 ℃ dry 1 hour down, be placed in the moisture eliminator standby;
B) with the nano silicon nuclear preparation composite emulsion: get in the step a) through pretreated nanometer SiO
20.1～5 parts the water high speed mechanical dispersion that adds small amounts of emulsifiers 15 minutes, with scattered nanometer SiO
2Add flask and be heated to 75 ℃, will be added with buffer reagent, initiator, the pre-emulsion of emulsifying agent and 10～20 parts of mix monomers progressively is added dropwise to, and control reaction temperature is incubated 30 minutes at 75 ℃, allows monomer with nanometer SiO
2Coat and polymerization, and, progressively residual monomer and emulsifying agent and initiator are added dropwise to system in two batches then with this seed as composite emulsion, treat that monomer dropping is warming up to 80 ℃ of insulations 2 hours after intact, the slaking 30 minutes that heats up at last, pH value to 8～9 are regulated in the cooling back;
Perhaps
B) situ aggregation method prepares composite emulsion: with the pretreated nanometer SiO of process in the step a)
2With monomer, the pre-emulsification of emulsifying agent 15 minutes, the method that adopts fed batch to drip, getting 10～20 parts of pre-emulsions earlier feeds intake, question response drips the residue pre-emulsion after 30 minutes, initiator and buffer reagent also adopt the mode of dropping, and control reaction temperature is at 75 ℃, treat to be warming up to after pre-emulsion drips 80 ℃ of insulations 2 hours, the slaking that heats up at last, 30 minutes, pH value to 8～9 were regulated in the cooling back.
7, the preparation method of nano silicon dioxide/acrylate nano-composite emulsion according to claim 6 is characterized in that described coupling agent is gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, second diamino propyl trimethoxy silicane, vinyl three (2-methoxyethoxy) silane, vinyl trichloro silane, vinyltriethoxysilane, vinyltrimethoxy silane or gamma-methyl allyl acyloxypropyl trimethoxysilane.
8, the preparation method of nano silicon dioxide/acrylate nano-composite emulsion according to claim 6 is characterized in that described solvent is toluene, dimethylbenzene or methyl ethyl ketone.
9, the preparation method of nano silicon dioxide/acrylate nano-composite emulsion according to claim 6 is characterized in that described buffer reagent is sodium bicarbonate or yellow soda ash; Described initiator is Sodium Persulfate or Potassium Persulphate; Described emulsifying agent is a kind of or its combination in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Succinic Acid ethylhexyl sodium sulfonate, sodium alkyl naphthalene sulfonate, alkylphenol polyoxyethylene, the fatty alcohol-polyoxyethylene ether.
10, the preparation method of nano silicon dioxide/acrylate nano-composite emulsion according to claim 6 is characterized in that described monomer is to be selected from methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, acrylic or methacrylic acid a kind of or its combination wherein.
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