CN104530302A - Silica sol/polyacrylic ester emulsion with high silicon content and preparation method of silica sol/polyacrylic ester emulsion - Google Patents
Silica sol/polyacrylic ester emulsion with high silicon content and preparation method of silica sol/polyacrylic ester emulsion Download PDFInfo
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Abstract
The invention discloses silica sol/polyacrylic ester emulsion with high silicon content and a preparation method of the silica sol/polyacrylic ester emulsion. The method is characterized in that silica sol is physically modified by adopting water-soluble macromolecules, and the modified silica sol and acrylic ester monomer are subjected to in-situ polymerization to prepare the silica sol/polyacrylic ester emulsion. The formula of the silica sol/polyacrylic ester emulsion comprises the following raw materials in parts by weight: 50 to 70 parts of deionized water, 5 to 30 parts of silica sol, 0.01 to 0.5 part of water-soluble macromolecules, 20 to 53 parts of acrylic ester monomer, 1 to 5 parts of methacrylic acid or acrylic acid, 1 to 5 parts of emulsifier, 0.1 to 0.5 part of initiator and 0.1 to 0.5 part of pH buffering agent; accounting by SiO2, silicon content in the emulsion accounts for 5 to 30 percent of the entire solid content; the particle size of the emulsion particle is 60 to 100 nm; and the carboxyl and hydroxyl on a polymer molecular chain and the hydroxyl on the surface of the SiO2 particles can generate the cross-linking esterification, so that the hardness of the film can reach more than 5H, and the water resistance and weather resistance are prominent.
Description
Technical field
The present invention relates to a kind of polyacrylic ester composite polymer latex, silicon sol/polyacrylate dispersion particularly relating to a kind of high silicon content and preparation method thereof.
Technical background
In recent years, on the basis of letex polymerization theory and technology development, occurred composite polymer latex, particularly organo-mineral complexing emulsion causes the extensive concern of people.
After the eighties in 20th century, Okubo proposed the concept of " particle design ", adopt seed emulsion polymerization, prepared the new polymers emulsion with out-phase (core-shell structure copolymer) structure latex particle.Due to grafting, interpenetrating(polymer)networks or ionic bonding may be there is between the core of latex particle with core shell structure, shell, when same materials forms, the latex particle with this structure not only can significantly improve wear-resisting, water-fast, weather-proof, resistant, shielding property and the tensile strength of polymkeric substance, shock-resistance and cohesive strength, improve the transparency, but also significantly can be lowered into film temperature, improve processing characteristics.According to the nucleocapsid structure theoretical model of polymer emulsion, adopt seeded emulsion polymerization technique, introduce inorganic nano material in the course of the polymerization process, the composite emulsion that to define with inorganic nano material be core, macromolecular material is shell, this Core-Shell Type Hybrid Emulsions both overcome when nano material directly being introduced coating system easily reunite, with the shortcoming such as organism poor compatibility, maintain again the advantage that traditional polymer emulsion film forming is good, film is transparent and snappiness is excellent, have a wide range of applications in preparation high-performance and specific function coating.
Chinese invention patent application CN 102649835 A discloses a kind of with silane coupling agent surface-treated Nano-meter SiO_2
2for seed, suitable emulsion polymerization technique is adopted to prepare Nano-meter SiO_2
2the method of-poly acrylate composite emulsion.The method both overcome nano material easily reunite, with the shortcoming such as organism poor compatibility, maintain again the advantage that traditional polymer emulsion film forming is good, film is transparent and snappiness is excellent.
Chinese invention patent application CN 102140217 A discloses in a kind of process prepared at Core-Shell Polyacrylic-ester Copolymer shell the silicon sol that adds through modification to prepare the method for polyacrylate/silica solution composite material.The method silane coupling agent carries out modification to silicon sol, and the emulsion of preparation has nucleocapsid structure.
Chinese invention patent application CN 1036269ll A discloses a kind of method preparing hydrophobicity organic-inorganic high silicon content acrylate polymer emulsion with the coupling agent modified silicon sol of fluorine containing silane, emulsion nano silicon-dioxide prepared by the method is uniformly dispersed, and film has the hardness and hydrophobicity of becoming reconciled.
Above-mentioned prior art is all first utilize silane coupling agent to SiO
2carry out chemical modification, and then prepare the SiO of organic inorganic hybridization on this basis
2/ polyacrylate dispersion.At silane coupling agent to SiO
2carry out, in the process of chemical modification, easily causing SiO
2reunion, cause being difficult to the particle diameter controlling organic inorganic hybridization emulsion, thus affect the over-all properties such as film-forming properties, hardness, chemical-resistant of emulsion film.
Summary of the invention
The object of the invention is to the deficiency overcoming prior art existence, a kind of SiO is provided
2with polymer compatibility is good, emulsion particle diameter is little, hardness of film is high and silicon sol/polyacrylate dispersion of the high silicon content of the excellent propertys such as film-forming properties, water tolerance, weathering resistance and preparation method thereof.
The present invention adopts emulsion polymerization in situ, with silicon sol (Nano-meter SiO_2
2the colloidal sol of particle) be raw material, with water-soluble macromolecule to its physically modified, prepare silicon sol/polyacrylic ester nano-composite emulsion that emulsion particle is the high silicon content of 60 ~ 100nm on this basis.This emulsion both overcome nano material easily reunite, with the shortcoming such as organism poor compatibility, maintain again the advantage that traditional polymer emulsion film forming is good, film is transparent and snappiness is excellent, also there is the performances such as outstanding water tolerance, weathering resistance.
Invention also provides the method preparing above-mentioned emulsion, realize especially by following technical scheme:
A preparation method for the silicon sol/polyacrylate dispersion of high silicon content, comprises the steps:
1) deionized water of the ionized water total mass 10 ~ 30% that accounts for is got, water-soluble macromolecule is dissolved in ionized water and makes the water-soluble macromolecule aqueous solution, the water-soluble macromolecule aqueous solution is mixed with silicon sol, stirs, obtain water-soluble macromolecule modified silicasol;
2) using water-soluble macromolecule modified silicasol as still liquid, and add the emulsifying agent that accounts for emulsifying agent total mass 1 ~ 40% and the deionized water of the ionized water total mass 1 ~ 50% that accounts for, whole pH buffer reagents, stir, mix;
3) formula hydroxy acryl acid ester monomer, acrylic or methacrylic acid mono, acrylic ester monomer or methacrylate-based monomer is taken respectively, get the monomer accounting for total monomer quality 10 ~ 45% to mix as nuclear monomer, using remaining monomer mixing as shell monomer;
Get remaining emulsifying agent to mix with the deionized water of the ionized water total amount 25 ~ 70% that accounts for, fully dissolve, obtain emulsifier solution, the emulsifier solution taking out 10 ~ 30% quality is used for emulsification nuclear monomer, remaining for emulsification shell monomer;
Nuclear monomer is added, obtained nuclear monomer pre-emulsion in the emulsifier solution for emulsification nuclear monomer; Shell monomer is added, obtained shell monomer pre-emulsion in the emulsifier solution for emulsification shell monomer; With remaining deionized water dissolving initiator, make initiator solution;
4) by step 2) temperature of reaction is elevated to 60 ~ 90 DEG C, and drip the initiator solution and the nuclear monomer pre-emulsion that account for 30 ~ 50% quality simultaneously, carry out polyreaction, dropwise insulation 15 ~ 45min;
5) add remaining initiator solution and shell monomer pre-emulsion, at 70 ~ 90 DEG C, proceed polyreaction; Treat that shell monomer emulsion dropwises, insulation 1.5 ~ 4h, adjust ph is 7 ~ 8, filters discharging;
Described water-soluble macromolecule is carboxymethyl cellulose (CMC), Walocel MT 20.000PV (HMC), Natvosol (HEC), Vltra tears (HPMC), hydroxyethylmethyl-cellulose (HEMC), polyvinyl alcohol (PVA), polyoxyethylene glycol (PEG), polyacrylamide (PAM), hydro-polyacrylamide (HPAM)), one or more in polyvinylpyrrolidone (PVP), sodium polyacrylate and water soluble starch;
Described hydroxy acryl acid ester monomer is other hydroxy acryl acid ester monomers that Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, N hydroxymethyl acrylamide and the art are commonly used, and chooses one or more in above-mentioned monomer in emulsion preparation process;
Described acrylic ester monomer or methacrylate-based monomer are two or more in methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, N-Hexyl methacrylate, Octyl methacrylate and ethyl acrylate;
Described emulsifying agent is that anionic emulsifier and nonionic emulsifier are through the composite emulsifying agent obtained, the mass ratio of anionic emulsifier and nonionic emulsifier is 1 ~ 3:1, one or more wherein in anionic emulsifier allyloxy polyoxyethylene nonylphenol ether series and sulfonate or ammonium salt, vinyl sulphur sodium, methallylsulfonic acid sodium, allyloxy hydroxide sodium dimercaptosulphanatein, sodium oleate, stearic acid sodium, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate and the basic sodium sulfonate of two dodecane; Described nonionic emulsifier select in fatty alcohol polyethenoxy ether class, alkylphenol polyoxyethylene class and polyoxyethylene sorbitan fatty acid ester one or more;
Described water soluble starter is one or both in ammonium persulphate, Potassium Persulphate and Sodium Persulfate.
For realizing the object of the invention further, preferably, described pH buffer reagent is one or more in sodium bicarbonate, sodium hydrogen phosphate and SODIUM PHOSPHATE, MONOBASIC.
Described nuclear monomer pre-emulsion is prepared by the following method: under the stirring velocity of 800 ~ 2000rpm, the emulsifier solution being used for emulsification nuclear monomer is stirred 10 ~ 25min, drip nuclear monomer, after dropwising, continue to stir 20 ~ 30min with 1000-2000rpm rotating speed.
Described shell monomer pre-emulsion is prepared by the following method: under the stirring velocity of 800 ~ 2000rpm, the emulsifier solution being used for emulsification shell monomer is stirred 10 ~ 25min, drip shell monomer, after dropwising, continue to stir 20 ~ 30min with 1000-2000rpm rotating speed.
The time for adding of initiator solution and nuclear monomer pre-emulsion that described dropping accounts for 30 ~ 50% quality is 30 ~ 90min.
The described time adding remaining initiator solution and shell monomer pre-emulsion is 2.5 ~ 3.5h.
Described being stirred for stirs 6 ~ 24h at 30 ~ 75 DEG C.
Described pH value regulates by adding ammoniacal liquor.
Silicon sol/polyacrylate dispersion of high silicon content, is obtained by above-mentioned preparation method.Silicon sol/the polyacrylate dispersion of described high silicon content, is characterized in that, the solid content of described silicon sol/polyacrylate dispersion is 25 ~ 40%; In SiO2, inorganic silicon accounts for 5 ~ 30% of whole emulsion solid content; Emulsion appearance is light blue translucent liquid, and latex particle size is 60 ~ 100nm; Emulsion pickling process or squeegee process are coated on the glass after washes clean or metal substrate, under 120 DEG C of conditions, toast 5 ~ 30min, the hardness of film obtained reaches more than 5H, and sticking power reaches 0 grade, film room temperature water soaks and does not whiten for 20 days, and resistance to neutral salt spray 30 days is unchanged.
The present invention's water-soluble polymer is to SiO
2micelle processes, and makes its surface form an Adsorption of Organic layer, and shields SiO
2the negative charge on micelle surface, thus the affinity adding it and monomer, with such SiO
2micelle is core, carries out seeded emulsion polymerization, makes monomer radical energy target SiO
2micelle, obtains SiO
2-water-soluble polymer/PBA-MMA compound nucleus shell mould micelle.
Compared with prior art, the present invention has the following advantages:
1) preparation of the silicon sol/polyacrylate dispersion of a kind of high silicon content of the present invention, adopts water-soluble macromolecule to the modification of alkaline silica sol, belongs to physically modified, can retain SiO
2the hydroxyl on micelle surface.Carboxyl when high temperature (90 ~ 130 DEG C) film forming on polymer molecular chain and hydroxyl, SiO
2can be there is esterification and crosslinking generation esterification and crosslinking in the hydroxyl on micelle surface, improve the hardness of film, water tolerance and weathering resistance further.
2) emulsion preparation method disclosed by the invention, the use of inorganic nano silicon dioxide gel and water-soluble macromolecule, relative to traditional method, had both reduced the particle diameter of emulsion particle, had enhanced product performance, can reduce again the production cost of emulsion.
3) emulsion prepared by the present invention, its emulsion particle is that nano level can infiltrate in the micropore of base material, and simultaneously hydroxy acryl acid ester monomer is that necessary monomer to ensure that on polymer chain containing hydroxyl, makes the sticking power of film higher, reaches 0 grade.
4) silicon sol/polyacrylate dispersion of a kind of high silicon content of the present invention, obtained with acrylic ester monomer in-situ polymerization by physically modified silicon sol, method is simple.
Specific implementation method
For understanding the present invention better, below in conjunction with embodiment, the invention will be further described, but embodiment does not form limiting the scope of the present invention.The raw material related in embodiment, is commercially available except specified otherwise.
Below in embodiment, HEC selects viscosity to be that 50mPas, HEMC select viscosity to be 100mPas, is Shanghai Jing Chun biochemical technology limited-liability company and produces; The silicon sol that silicon sol selects in Foshan glasswork of flooding to produce, mass content is 30%, alkalescence.
Embodiment 1
Be dissolved in 5g deionized water by 0.18g HEC, then be added in 56g silicon sol by HEC solution, at 41 DEG C, stirring reaction 12h, obtains modified silicasol.
3.2g DNS-86 (allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate) and X-405 (polyoxyethylene octylphenol ether) compound emulsifying agent (mass ratio: 2:1) are dissolved in 38g deionized water and obtain emulsified soln, be divided into three parts: getting 8g is nuclear monomer emulsifier solution, 25g is as shell monomer emulsifier solution, and residual emulsifier solution mixes as still liquid with modified silicasol.
Monomer pre-emulsification: respectively nuclear monomer emulsifier solution and shell monomer emulsifier solution are added in two wide-necked bottles, 25min is stirred with the speed of 1500rpm, and in backward two bottles, instill 11g nuclear monomer (methyl methacrylate and butyl acrylate mass ratio are 1:1) and 32.2g shell monomer (methyl methacrylate, butyl acrylate and vinylformic acid three mass ratio are 2:1:0.1) respectively, after dropwising, continue with 1500rpm magnetic agitation 30min, obtained nuclear monomer pre-emulsion and shell monomer pre-emulsion.And 0.65g ammonium persulphate is dissolved in 10.8g deionized water.
In the four-hole boiling flask being provided with stirring rake, thermometer, reflux condensing tube, add still liquid, and add 0.6g NaHCO3, stir with the speed of 200rpm and be warming up to 75 DEG C, insulation 30min.With constant pressure funnel splendid attire nuclear monomer pre-emulsion, and at the uniform velocity drip 4g initiator ammonium sulfate solution, time for adding is 30min.Insulation 30min.Be warming up to 81 DEG C, with constant pressure funnel splendid attire shell monomer pre-emulsion, and at the uniform velocity drip 6.8g initiator ammonium sulfate solution, time for adding is 3h, insulation 3h.Be cooled to less than 50 DEG C, with ammoniacal liquor, the pH value be dissolved in be adjusted to about 8, obtain stable silicon sol/polyacrylate dispersion.After testing, the silicone content of this silicon sol/polyacrylate dispersion is 28%; The latex particle size particle diameter of micella (in the emulsion) is 98.5nm/PDI=0.303 (Malvern laser particle size analyzer); Emulsion is coated tinplate 120 DEG C baking 15min, its photocatalytic coating film slippery, transparency, hardness reaches 5H (GB/T6739-2006), sticking power is that 0 grade of (GB/T1720-1979) film is soaked in water do not whiten for 21 days (GB/T 1733-1993), resistance to neutral salt spray 31 days unchanged (GB/T1771-2007).
Performance comparison: the present embodiment gained hardness of film reaches 5H (GB/T6739-2006, suitable with patent CN102649835A and patent CN1O2731735A); Because the effect sticking power of nano-emulsion micelle and hydroxyl is 0 grade (GB/T1720-1979 is 1 grade in patent CN102649835A, is 0 ~ 1 grade in patent CN1O2731735A); Hydroxyl in baking on polymer molecular chain and carboxyl occur crosslinked, the present embodiment gained film is soaked in water (the GB/T 1733-1993 that do not whiten for 21 days, not explicitly pointing out water resistance in patent CN102649835A, is 7 ~ 10 days in patent CN1O2731735A); Film can resistance to neutral salt spray 31 days unchanged (GB/T1771-2007, does not explicitly point out salt spray resistance in patent CN102649835A, is 12 ~ 20 days in patent CN1O2731735A).
Present embodiments provide a kind of SiO as seen
2with polymer compatibility is good, latex particle size is little, hardness of film is high and silicon sol/the polyacrylate dispersion of the high silicon content of the excellent propertys such as film-forming properties, water tolerance, weathering resistance.
Embodiment 2
Be dissolved in 5g deionized water by 0.01g HEC, then be added in 30g silicon sol by HEC solution, at 41 DEG C, stirring reaction 12h, obtains modified silicasol.
1.6g DNS-86 and OP-10 (polyoxyethylene nonylphenol ether) compound emulsifying agent (mass ratio: 2:1) is dissolved in 20g deionized water, is divided into three parts: getting 3g is nuclear monomer emulsifier solution; 11g is nuclear monomer emulsifier solution; Residual emulsifier solution mixes as still liquid with modified silicasol.
Monomer pre-emulsification: respectively nuclear monomer emulsifier solution and shell monomer emulsifier solution are added in two wide-necked bottles, 15min is stirred with the speed of 1500rpm, then respectively to instilling 7g nuclear monomer (methyl methacrylate and butyl acrylate mass ratio are 1:1) and 23g shell monomer (methyl methacrylate in two bottles, butyl acrylate, methacrylic acid and Rocryl 410 three mass ratio are 2:1:0.1:0.1), after dropwising, continue with 1500rpm magnetic agitation 30min, obtained nuclear monomer pre-emulsion and shell monomer pre-emulsion respectively, for subsequent use.0.25g ammonium persulphate is dissolved in 30g deionized water, makes initiator solution.
In the four-hole boiling flask being provided with stirring rake, thermometer, reflux condensing tube, add still liquid (residual emulsifier and 39g modified silicasol), and add 0.4g NaHCO
3, stir with the speed of 200rpm and be warming up to 75 DEG C, insulation 30min.With constant pressure funnel splendid attire nuclear monomer pre-emulsion, and at the uniform velocity drip 10g initiator solution, time for adding is 30min, insulation 30min, is warming up to 81 DEG C, with constant pressure funnel splendid attire shell monomer pre-emulsion, and at the uniform velocity dripping 21g initiator solution, time for adding is 3h, insulation 2.5h.Be cooled to less than 50 DEG C, with ammoniacal liquor, the pH value of emulsion be adjusted to about 8, obtain stable silicon sol/polyacrylate dispersion.The silicone content of this silicon sol/polyacrylate dispersion is 22% (quality), and latex particle size is 63.4nm/PDI=0.350 (Malvern laser particle size analyzer); Emulsion is coated tinplate 120 DEG C baking 15min, its photocatalytic coating film slippery, transparency, hardness reaches 5H (GB/T6739-2006), sticking power is that 0 grade of (GB/T1720-1979) film is soaked in water do not whiten for 20 days (GB/T 1733-1993), resistance to neutral salt spray 30 days unchanged (GB/T1771-2007).
Embodiment 3
Be dissolved in 5g deionized water by 0.08g PEG (molecular weight 20000,1Guanghua Chemical Plant Co., Ltd., Guangdong), then be added in 25g silicon sol by PEG solution, at 60 DEG C, stirring reaction 10h, obtains modified silicasol.
3.5gSVS (sodium vinyl sulfonate) and AEO40 (fatty alcohol polyethenoxy ether class emulsifying agent) compound emulsifying agent (mass ratio: 1:4) is dissolved in 25g deionized water, be divided into three parts: get 5g as nuclear monomer emulsifier solution, 15g is as shell monomer emulsifier solution, and residual emulsifier solution mixes as still liquid with modified silicasol.
Monomer pre-emulsification: respectively nuclear monomer emulsifier solution and shell monomer emulsifier solution are added in two wide-necked bottles, 10min is stirred with the speed of 1500rpm, then instill 7g nuclear monomer (methyl methacrylate and butyl acrylate mass ratio are 1:1) and 23g shell monomer (methyl methacrylate, butyl acrylate and methacrylic acid three mass ratio are 2:1:0.1:0.2), after dropwising, continue with 1500rpm magnetic agitation 30min, obtained nucleocapsid pre-emulsion.And 0.25g ammonium persulphate is dissolved in 30g deionized water.
Still liquid (residual emulsifier and 39g modified silicasol) is added in the four-hole boiling flask being provided with stirring rake, thermometer, reflux condensing tube, and add 0.4g NaHCO3 and 0.5g methacrylic acid, stir with the speed of 200rpm and be warming up to 75 DEG C, insulation 30min.With constant pressure funnel splendid attire nuclear monomer pre-emulsion, and at the uniform velocity drip 10g initiator solution, time for adding is 30min.Insulation 30min.Be warming up to 81 DEG C, with constant pressure funnel splendid attire shell monomer pre-emulsion, and at the uniform velocity drip 21g initiator solution, time for adding is 3h, insulation 4h.Be cooled to less than 50 DEG C, with ammoniacal liquor, the pH value be dissolved in be adjusted to about 8, obtain stable silicon sol/polyacrylate dispersion.The silicone content of this emulsion is 20%, emulsion particle diameter is 62.5nm/PDI=0.377 (Malvern laser particle size analyzer), emulsion is coated tinplate 120 DEG C baking 15min, its photocatalytic coating film slippery, transparent excellence, hardness reaches 5H (GB/T6739-2006), sticking power is 0 grade (GB/T1720-1979), and film is soaked in water do not whiten for 20 days (GB/T 1733-1993), resistance to neutral salt spray 30 days unchanged (GB/T1771-2007).
Embodiment 4
Be dissolved in 5g deionized water by 0.06g HEMC, then be added in 42.5g silicon sol by HEMC solution, at 65 DEG C, stirring reaction 12h, obtains modified silicasol.
2.8g Sodium dodecylbenzene sulfonate and OP-10 compound emulsifying agent (mass ratio: 1:1) are dissolved in 25g deionized water, be divided into three parts: get 5g as nuclear monomer emulsifier solution, 15g is as shell monomer emulsifier solution, and residual emulsifier solution mixes as still liquid with modified silicasol.
Monomer pre-emulsification: respectively nuclear monomer emulsifier solution and shell monomer emulsifier solution are added in two wide-necked bottles, 10min is stirred with the speed of 1500rpm, then respectively to instilling 7g nuclear monomer (methyl methacrylate and butyl acrylate mass ratio are 1:1) and 23g shell monomer (methyl methacrylate, butyl acrylate and methacrylic acid three mass ratio are 2:1:0.1:0.2) in two bottles, after dropwising, continue with 1500rpm magnetic agitation 30min, obtained nucleocapsid pre-emulsion.And 0.25g ammonium persulphate is dissolved in 30g deionized water.
Still liquid (residual emulsifier and 39g modified silicasol) is added in the four-hole boiling flask being provided with stirring rake, thermometer, reflux condensing tube, and add 0.4g NaHCO3 and 0.5g methacrylic acid, stir with the speed of 200rpm and be warming up to 75 DEG C, insulation 30min.With constant pressure funnel splendid attire nuclear monomer pre-emulsion, and at the uniform velocity drip 10g initiator solution, time for adding is 30min.Insulation 30min.Be warming up to 81 DEG C, with constant pressure funnel splendid attire shell monomer pre-emulsion, and at the uniform velocity drip 21g initiator solution, time for adding is 3h, insulation 3h.Be cooled to less than 50 DEG C, with ammoniacal liquor, the pH value be dissolved in be adjusted to about 8, obtain stable silicon sol/polyacrylate dispersion.The silicone content of this emulsion is 30%, latex particle size is 99.2nm/PDI=0.377 (Malvern laser particle size analyzer), emulsion is coated tinplate 120 DEG C baking 15min, its photocatalytic coating film slippery, excellent clarity, hardness reaches 6H (GB/T6739-2006), sticking power is that 0 grade of (GB/T1720-1979) film is soaked in water do not whiten for 21 days (GB/T 1733-1993), resistance to neutral salt spray 30 days unchanged (GB/T1771-2007).
Embodiment 5
Be dissolved in 5g deionized water by 0.02g PVA (low viscosity adopts standard USP25), then be added in 18g silicon sol by HEMC solution, at 50 DEG C, stirring reaction 12h, obtains modified silicasol.
1.6g DNS-86 and polysorbate60 (polyoxyethylene sorbitan fatty acid ester emulsifying agent) compound emulsifying agent (mass ratio: 2:1) are dissolved in 25g deionized water, be divided into three parts: get 5g as nuclear monomer emulsifier solution, 15g is as shell monomer emulsifier solution, and residual emulsifier solution mixes as still liquid with modified silicasol.
Monomer pre-emulsification: respectively nuclear monomer emulsifier solution and shell monomer emulsifier solution are added in two wide-necked bottles, 15min is stirred with the speed of 1500rpm, then respectively to instilling 7g nuclear monomer (methyl methacrylate and butyl acrylate mass ratio are 1:1) and 23g shell monomer (methyl methacrylate, butyl acrylate, hydroxyethyl methylacrylate and methacrylic acid mass ratio are 2:1:0.1:0.2) in two bottles, after dropwising, continue with 1500rpm magnetic agitation 30min, obtained nucleocapsid pre-emulsion.And 0.25g ammonium persulphate is dissolved in 30g deionized water.
Still liquid (residual emulsifier and 39g modified silicasol) is added in the four-hole boiling flask being provided with stirring rake, thermometer, reflux condensing tube, and add 0.4g NaHCO3,1.5gN-n-methylolacrylamide and 0.5g methacrylic acid, stir with the speed of 200rpm and be warming up to 75 DEG C, insulation 30min.With constant pressure funnel splendid attire nuclear monomer pre-emulsion, and at the uniform velocity drip 10g initiator solution, time for adding is 30min.Insulation 30min.Be warming up to 81 DEG C, with constant pressure funnel splendid attire shell monomer pre-emulsion, and at the uniform velocity drip 21g initiator solution, time for adding is 3h, insulation 3h.Be cooled to less than 50 DEG C, with ammoniacal liquor, the pH value be dissolved in be adjusted to about 8, obtain stable hud typed silicon sol/polyacrylate dispersion.The silicone content of this emulsion is 20%, latex particle size is 75.3nm/PDI=0.321 (Malvern laser particle size analyzer), emulsion is coated tinplate 120 DEG C baking 15min, its photocatalytic coating film slippery, excellent clarity, hardness reaches 5H (GB/T6739-2006), sticking power is that 0 grade of (GB/T1720-1979) film is soaked in water do not whiten for 20 days (GB/T 1733-1993), resistance to neutral salt spray 30 days unchanged (GB/T1771-2007).
Embodiment 6
Emulsion in Example 5 coat tinplate and under room temperature drying and forming-film, its photocatalytic coating film slippery, excellent clarity, hardness has 4H (GB/T6739-2006), and sticking power is 0 grade (GB/T1720-1979); Film is soaked in water do not whiten for 7 days (GB/T 1733-1993); Film can resistance to neutral salt spray 8 days unchanged (GB/T1771-2007).
Claims (10)
1. a preparation method for the silicon sol/polyacrylate dispersion of high silicon content, is characterized in that comprising the steps:
1) deionized water of the ionized water total mass 10 ~ 30% that accounts for is got, water-soluble macromolecule is dissolved in ionized water and makes the water-soluble macromolecule aqueous solution, the water-soluble macromolecule aqueous solution is mixed with silicon sol, stirs, obtain water-soluble macromolecule modified silicasol;
2) using water-soluble macromolecule modified silicasol as still liquid, and add the emulsifying agent that accounts for emulsifying agent total mass 1 ~ 40% and the deionized water of the ionized water total mass 1 ~ 50% that accounts for, whole pH buffer reagents, stir, mix;
3) hydroxy acryl acid ester monomer, acrylic or methacrylic acid mono, acrylic ester monomer or methacrylate-based monomer in formula is taken respectively, get the monomer accounting for total monomer quality 10 ~ 45% to mix as nuclear monomer, using remaining monomer mixing as shell monomer;
Get remaining emulsifying agent to mix with the deionized water of the ionized water total mass 25 ~ 70% that accounts for, fully dissolve, obtain emulsifier solution, the emulsifier solution taking out 10 ~ 30% quality is used for emulsification nuclear monomer, remaining for emulsification shell monomer;
Nuclear monomer is added, obtained nuclear monomer pre-emulsion in the emulsifier solution for emulsification nuclear monomer; Shell monomer is added, obtained shell monomer pre-emulsion in the emulsifier solution for emulsification shell monomer; With remaining deionized water dissolving initiator, make initiator solution;
4) by step 2) temperature of reaction is elevated to 60 ~ 90 DEG C, and drip the initiator solution and the nuclear monomer pre-emulsion that account for 30 ~ 50% quality simultaneously, carry out polyreaction, dropwise insulation 15 ~ 45min;
5) add remaining initiator solution and shell monomer pre-emulsion, at 70 ~ 90 DEG C, proceed polyreaction; Treat that shell monomer emulsion dropwises, insulation 1.5 ~ 4h, adjust ph is 7 ~ 8, filters discharging;
Described water-soluble macromolecule is carboxymethyl cellulose (CMC), Walocel MT 20.000PV (HMC), Natvosol (HEC), Vltra tears (HPMC), hydroxyethylmethyl-cellulose (HEMC), polyvinyl alcohol (PVA), polyoxyethylene glycol (PEG), polyacrylamide (PAM), hydro-polyacrylamide (HPAM)), one or more in polyvinylpyrrolidone (PVP), sodium polyacrylate and water soluble starch;
Described hydroxy acryl acid ester monomer is other hydroxy acryl acid ester monomers that Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, N hydroxymethyl acrylamide and the art are commonly used, and chooses one or more in above-mentioned monomer in emulsion preparation process;
Described acrylic ester monomer or methacrylate-based monomer are two or more in methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, N-Hexyl methacrylate, Octyl methacrylate and ethyl acrylate;
Described emulsifying agent is that anionic emulsifier and nonionic emulsifier are through the composite emulsifying agent obtained, the mass ratio of anionic emulsifier and nonionic emulsifier is 1 ~ 3:1, one or more wherein in anionic emulsifier allyloxy polyoxyethylene nonylphenol ether series and sulfonate or ammonium salt, vinyl sulphur sodium, methallylsulfonic acid sodium, allyloxy hydroxide sodium dimercaptosulphanatein, sodium oleate, stearic acid sodium, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate and the basic sodium sulfonate of two dodecane; Described nonionic emulsifier select in fatty alcohol polyethenoxy ether class, alkylphenol polyoxyethylene class and polyoxyethylene sorbitan fatty acid ester one or more;
Described water soluble starter is one or both in ammonium persulphate, Potassium Persulphate and Sodium Persulfate.
2. the preparation method of the silicon sol/polyacrylate dispersion of high silicon content according to claim 1, is characterized in that, described pH buffer reagent is one or more in sodium bicarbonate, sodium hydrogen phosphate and SODIUM PHOSPHATE, MONOBASIC.
3. the preparation method of the silicon sol/polyacrylate dispersion of high silicon content according to claim 1, it is characterized in that, described nuclear monomer pre-emulsion is prepared by the following method: under the stirring velocity of 800 ~ 2000rpm, the emulsifier solution being used for emulsification nuclear monomer is stirred 10 ~ 25min, drip nuclear monomer, after dropwising, continue to stir 20 ~ 30min with 1000-2000rpm rotating speed.
4. the preparation method of the silicon sol/polyacrylate dispersion of high silicon content according to claim 1, it is characterized in that, described shell monomer pre-emulsion is prepared by the following method: under the stirring velocity of 800 ~ 2000rpm, the emulsifier solution being used for emulsification shell monomer is stirred 10 ~ 25min, drip shell monomer, after dropwising, continue to stir 20 ~ 30min with 1000-2000rpm rotating speed.
5. the preparation method of the silicon sol/polyacrylate dispersion of high silicon content according to claim 1, it is characterized in that, the time for adding of initiator solution and nuclear monomer pre-emulsion that described dropping accounts for 30 ~ 50% quality is 30 ~ 90min.
6. the preparation method of the silicon sol/polyacrylate dispersion of high silicon content according to claim 1, is characterized in that, described in add remaining initiator solution and shell monomer pre-emulsion time be 2.5 ~ 3.5h.
7. the preparation method of the silicon sol/polyacrylate dispersion of high silicon content according to claim 1, is characterized in that, described in be stirred for stir 6 ~ 24h at 30 ~ 75 DEG C.
8. the preparation method of the silicon sol/polyacrylate dispersion of high silicon content according to claim 1, is characterized in that, described pH value regulates by adding ammoniacal liquor.
9. silicon sol/polyacrylate dispersion of high silicon content, is characterized in that it is obtained by preparation method described in any one of claim 1-8.
10. silicon sol/the polyacrylate dispersion of high silicon content according to claim 9, is characterized in that, the solid content of described silicon sol/polyacrylate dispersion is 25 ~ 40%; With SiO
2meter, inorganic silicon accounts for 5 ~ 30% of whole emulsion solid content; Emulsion appearance is light blue translucent liquid, and latex particle size is 60 ~ 100nm; Emulsion pickling process or squeegee process are coated on the glass after washes clean or metal substrate, under 120 DEG C of conditions, toast 5 ~ 30min, the hardness of film obtained reaches more than 5H, and sticking power reaches 0 grade, film room temperature water soaks and does not whiten for 20 days, and resistance to neutral salt spray 30 days is unchanged.
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