CN102649835B - Organic-inorganic hybrid high-silicon-content acrylic ester emulsion and preparation method thereof - Google Patents
Organic-inorganic hybrid high-silicon-content acrylic ester emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses organic-inorganic hybrid high-silicon-content acrylic ester emulsion and a preparation method thereof. The preparation method comprises the following steps: modifying silica sol by using a silane coupling agent; coupling the modified silicon sol with hydroxyl-containing hydrophilic functional monomers; and performing in-situ polymerization with acrylic ester monomers. The organic-inorganic hybrid high-silicon-content acrylic ester emulsion comprises the following raw materials in part by mass: 55 to 80 parts of deionized water, 20 to 70 parts of modified silicon sol, 15 to 40 parts of acrylic ester monomer, 0.01 to 1.5 parts of methacrylic acid, 0.1 to 2.5 parts of emulsifying agent, 0.02 to 1.5 parts of initiator and 0.01 to 1.0 part of sodium hydrogen carbonate, wherein the mass content (by SiO2) of silicon in the organic-inorganic hybrid high-silicon-content acrylic ester emulsion is 20 to 25 percent. The emulsion has an attractive appearance and high storage stability and freeze-thaw stability; the coating of the emulsion is smooth and has high transparency; the hardness is 5H and the adhesive force is 1 level; and excellent weather resistance and water resistance are achieved.
Description
Technical field
The present invention relates to a kind of acrylic ester emulsion, especially a kind of high-performance high silicon content acrylic ester emulsion and preparation method thereof, this emulsion can make the hybridized nanometer coating that has inorganic materials and organic polymer advantage concurrently as filmogen.
Technical background
Along with the day by day raising of people to environmental consciousness, the emulsion polymerization taking water as medium is subject to more multiple looking, and has also greatly promoted the development of emulsion polymerization technology simultaneously.The gordian technique of emulsion coatings replace solvents type coating is the challenge of the performance such as hardness of film and weathering resistance, and this is that ordinary emulsion product is difficult to the target realizing.And the compound macromolecule emulsion of organic-inorganic can prevent from inorganic particulate reunion from significantly improving the stability of emulsion and the wear resistance of material, weathering resistance and cohesive strength, and can significantly be lowered into film temperature, improve the moulding processability of material.When the special compound emulsion of organic-inorganic is used as coating, there is following feature: minimum film-forming temperature low (not containing film coalescence aid), and the anti-cementability of film forming is good; Various base materials are had to good sticking power; The water tolerance of film, solvent resistance, the more general emulsion of heat-resisting and resistance to flame retardant resistance all improves a lot; The mechanical property excellence of film.
Compared with solvent based coating, esters of acrylic acid latex coating film-forming properties is poor, still must add a certain amount of film coalescence aid, and what have also must add softening agent, and the water tolerance of system is reduced, and VOC is difficult to decline; Due to the existence of water-soluble, film-forming auxiliary agent, make the drying property of paint film, initial stage resistance to bond very poor, be not suitable for continuous suitability for industrialized production.The structural form of polyalcohol emulsion particle affects the performance of glued membrane, in order to obtain the high-compactness that can compare favourably with solvent-borne type film and the glued membrane of glossiness, need to improve conventional ACRYLIC EMULSION synthesis technique and method, comprise and add nanoparticle, the improvement of function monomer and the improvement of polymerization process.And by adding inorganic nano-particle can very effectively improve the film performance of emulsion, this has just promoted development and the application of the compound emulsion of organic-inorganic greatly.
Nano silicon/Polyacrylate Composites is the organic inorganic hybridization matrix material that a class has extensive use, nanometer silicon dioxide particle is evenly spread in acrylate resin by rights, the hardness that can overcome acrylate resin is low, the shortcoming such as wear no resistance, improve tensile strength and shock strength and resistance toheat, reach the object of improving unmodified resin material property.Using nanoparticle as filling modifier emulsion, prepare high performance composite, mainly contain at present 4 kinds of methods: sol-gel method, in-situ dispersion polymerization method, blending method and graft process.
The Chinese invention patent of publication number CN 101948561A discloses a kind of organic/inorganic silicon hybrid resin for coating and preparation method thereof.This hybrid resin is by inorganic SiO
2particle graftedly on organic fluoropolymer resin main chain, form organic-inorganic hybrid structure.Its preparation is the SiO that first takes sol-gel method prepared sizes moderate
2colloidal sol or by commercially available nanometer SiO
2powder body material is scattered in organic solvent and forms colloidal sol, with organo-siloxane to nanometer SiO
2carry out surface modification and make it have reactive and polymerization single polymerization monomer copolymerization and obtain the coating resin of hydridization.This resin combines the good characteristic of organic polymer and inorganic materials, has good mechanical property, resistance to elevated temperatures and good snappiness.But this method is made the SiO coming by sol-gel method
2siO in colloidal sol
2content is only 10%, again with its synthetic resin SiO
2content is also lower.And hardness of film is inadequate, be 2H to the maximum.
The Chinese invention patent of publication number CN 102020817A discloses a kind of preparation method of nano silicon oxide modified silicone acrylate emulsifier-free emulsion.The method apparatus respond polyacrylic acid-b-butyl polyacrylate (PAA-b-PBA) amphipathic nature block polymer replacement conventional emulsifier and the reactive emulsifier of active and surfactant properties, first make acrylic ester monomer, vinyl silicone oil and carry out emulsifier-free emulsion polymerization containing two key organoalkoxysilanes, then add tetraethoxy generation sol gel reaction, make organosilicon and nano-silicon dioxide modified acrylic resin soap-free emulsion.This invention can be eliminated the disadvantageous effect of small-molecular emulsifier to Emulsion acrylic resin completely, has reduced simultaneously and has adopted reactive emulsifier to prepare the cost of soap-free emulsion, by organosilicon and nanometer SiO
2good characteristic introduce acrylic resin, overcome the shortcomings such as acrylic resin hot sticky cold crisp, poor water resistance, good solubility-resistence be poor, improve its mechanical property, sticking power and wear resistance.But prepared organosilicon crylic acid latex particle diameter ratio is larger, and solid content is lower, its use is restricted.
The development of nano silicon/Polyacrylate Composites is just at the early-stage, and a large amount of work still needs to be carried out, but its outstanding advantages obviously shows.The development of nanotechnology, a large amount of uses of matrix material, for traditional industry injects vigour into, will have larger development in multiple science and technology field from now on.
Summary of the invention
The object of the invention is to solve the organosilicon crylic acid latex silicone content that prior art makes lower, to improving aspect of performance the inapparent deficiency such as hardness, weathering resistance, water tolerance of coating, provide a kind of organic inorganic hybridization high silicon content acrylic ester emulsion, its SiO
2content reaches more than 20%, has good outward appearance, well stability in storage and freeze-thaw stability, and its film transparency is high, and hardness has 5H, and adhesion 1 grade has good resistance to staining property, weathering resistance and water tolerance.
Another object of the present invention is to provide the method for the described high-performance organic inorganic hybridization high silicon content acrylic ester emulsion of preparation.
Object of the present invention is achieved through the following technical solutions:
A preparation method for organic inorganic hybridization high silicon content acrylic ester emulsion, comprises the steps and processing condition:
(1) silane coupler modified silicon sol preparation: in mass fraction, the cosolvent of 10～30 parts, the silane coupling agent of 0.8～3.5 part are added in 30～80 parts of silicon sol, stirring reaction 6～24h, obtains modified silicasol at 20～50 DEG C; Described silane coupling agent is one or more in vinyltriethoxysilane, vinyltrimethoxy silane, γ-(methacryloxy) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, 3-glycidyl ether oxygen propyl methyldiethoxysilane, γ aminopropyltriethoxy silane; Described cosolvent is the one in Virahol, the trimethyl carbinol, ethanol or ethylene glycol;
(2) organic inorganic hybridization acrylic ester emulsion is synthetic: in mass fraction, the formula of its raw material consists of:
Its preparation method is:
A, by organosilicon crylic acid latex prescription quality, the deionized water of formulation deionised water total mass 2～10% will be accounted for, the emulsifying agent that accounts for emulsifying agent total mass 5～30% mixes, after being uniformly dissolved, at the uniform velocity drip and account for acrylic ester monomer total mass 10～35% acrylic ester monomers, after dropwising, stir and carry out nuclear monomer pre-emulsification, make pre-emulsified nuclear monomer;
B, will account for formulation deionised water total mass 5～25% deionized waters, the emulsifying agent that accounts for emulsifying agent total mass 30～70% mixes, after being uniformly dissolved, inside at the uniform velocity drip and account for esters of acrylic acid total mass 50～90% acrylic ester monomers and methacrylic acid, after dropwising, shell monomers pre-emulsification is carried out in stirring, makes pre-emulsified shell monomers;
C, by formula in initiator be dissolved in the deionized water of the ionized water total mass 10～40% that accounts for;
D, in reactor, add modified silicasol in formula and the functional monomer of hydroxyl, remaining deionized water, remaining emulsifying agent and sodium bicarbonate as still liquid, after stirring, be warming up to 60～80 DEG C, after insulation 20～40min, be warming up to 85～95 DEG C, drip described pre-emulsified nuclear monomer and the initiator solution that accounts for step c total mass 20～50% simultaneously, insulation reaction 30～60min, makes core emulsion; Keep 85～95 DEG C of temperature, drip in described pre-emulsified shell monomers and step c simultaneously and remain initiator solution, insulation reaction 2～4h, finally cools to below 40 DEG C, regulate pH value to 7～8, obtain stable organic inorganic hybridization high silicon content acrylic ester emulsion; With SiO
2meter, in organic inorganic hybridization high silicon content acrylic ester emulsion, the mass content of silicon is 20～25%;
Described acrylic ester monomer is two or more in methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate and N hydroxymethyl acrylamide;
Described emulsifying agent is composite emulsifier, for anionic emulsifier and nonionic emulsifier are with (1～2): 1 mass ratio carries out composite, wherein anionic emulsifier is selected allyloxy nonyl phenolic ether and the sulfonated bodies series thereof of polymerizability, and nonionic emulsifier is selected the one in fatty alcohol-polyoxyethylene ether, OP series and tween series;
Described initiator is Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
For further realizing the object of the invention, described silicon sol is alkaline silica sol, with SiO
2meter, the mass content of silicon is 20～40%, particle diameter is 15～20nm.
It is to stir 10～30min in order to the speed of 1000～2000rpm that nuclear monomer pre-emulsification is carried out in described stirring, then stirs 3～10min with the speed of 500～1000rpm and carry out pre-emulsification.
It is at the uniform velocity to drip in 5～15min that described at the uniform velocity dropping accounts for acrylic ester monomer total mass 10～35% acrylic ester monomers.
It is to stir 10～30min with the speed of 1000～2000rpm that shell monomers pre-emulsification is carried out in described stirring, then stirs 3～10min with the speed of 500～1000rpm and carry out shell monomers pre-emulsification.
Described at the uniform velocity dropping accounts for esters of acrylic acid total mass 50～90% acrylic ester monomers and methacrylic acid is at the uniform velocity to drip in 10～30min.
The described initiator solution that simultaneously drips described pre-emulsified nuclear monomer and account for step c total mass 20～50% is to complete in 30～60min; Describedly drip that in described pre-emulsified shell monomers and step c, to remain initiator solution be to complete in 1.5～4.5h simultaneously; Described adjusting pH value to 7～8th, regulates with ammoniacal liquor.
A kind of organic inorganic hybridization high silicon content acrylic ester emulsion, is prepared by aforesaid method.
The emulsion appearance making is the milky emulsion of blueing light, and solid content is 30～40%, with SiO
2meter, in organic inorganic hybridization high silicon content acrylic ester emulsion, the mass content of silicon is 20～25%; Emulsion is coated on the glass or metal substrate after washes clean by pickling process or squeegee process, under 100～150 DEG C of conditions, toasts 5～30min, the hardness of film obtaining reaches 5H, and sticking power is 1 grade.
The present invention, in preparation process, first selects suitable silane coupling agent to carry out modification to silicon sol, makes SiO
2the hydroxyl on surface, with the group graft reaction in coupling agent, has increased the consistency between inorganics and organic monomer, carries out subsequently home position polymerization reaction.SiO
2there has been the macromolecular chain of aggregation growth on surface, then under effect under emulsifying agent coated, at initiator acrylic ester monomer directly at modification SiO
2upper beginning polymerization, bring out growth, the polymer that completes particle surface is coated, the compound acrylic ester emulsion that obtains stable high silicon content.Because silicone content is higher in emulsion, emulsion film can reach excellent hardness and weathering resistance, possesses all good advantages such as toughness and sticking power of acrylic ester emulsion simultaneously.
Compared with prior art, tool has the following advantages and beneficial effect in the present invention:
(1) the present invention is by selecting suitable silane coupling agent to carry out modification to silicon sol, and the nucleocapsid structure organosilicon crylic acid latex that heel acrylic ester monomer in-situ polymerization is prepared, its silicone content is (with SiO
2meter, accounts for emulsion solid content) reach more than 20%, there is good outward appearance, well stability in storage and freeze-thaw stability, its film transparency is high, and hardness has 5H, and adhesion 1 grade has good resistance to staining property, weathering resistance and water tolerance.
(2) the inventive method adopts pre-emulsification technology to have the polymerization technique of nucleocapsid structure, be characterized in: temperature of reaction is stablized easy to control, latex particle is evenly distributed, and emulsification dosage can reduce, nucleocapsid monomer can choose at random according to performance, can greatly improve emulsion property.
(3) the organic inorganic hybridization high silicon content acrylic ester emulsion inorganic silicon used that prepared by the inventive method is commercially available silicon sol, is easy to get and cheap, effectively reduces the production cost of organosilicon crylic acid latex.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further described, but the scope of protection of the invention is not limited to embodiment.
Embodiment 1:
The γ of 15g Virahol, 0.84g-(methacryloxy) propyl trimethoxy silicane is added in 35g silicon sol, and stirring reaction 8h at 50 DEG C, obtains modified silicasol.
By 3g deionized water, 0.1gDNS-86 and OP-10 (mass ratio of anionic emulsifier and nonionic emulsifier is 1: 1) join in wide-necked bottle, after being uniformly dissolved, in 10min, at the uniform velocity drip 2g mix monomer methyl methacrylate and butyl acrylate (mass ratio is 1: 1), after dropwising, speed stirring 15min with magnetic stirring apparatus with 2000rpm, then stir 5min with the speed of 500rpm, make pre-emulsified nuclear monomer.
By 5g deionized water, 0.3gDNS-86 and OP-10 (mass ratio of anionic emulsifier and nonionic emulsifier is 1: 1) join in wide-necked bottle, after being uniformly dissolved, in 20min, at the uniform velocity drip 10g mix monomer methyl methacrylate and butyl acrylate (mass ratio is 1: 1), and 0.15g methacrylic acid, after dropwising, speed stirring 20min with magnetic stirring apparatus with 2000rpm, stir 5min with the speed of 500rpm again, make pre-emulsified shell monomer.And 0.10g Potassium Persulphate is dissolved in 10g deionized water.
Agitator is being housed, reflux condensing tube, in the four-hole boiling flask of thermometer, add 25g modified silicasol and 0.5gN-n-methylolacrylamide, 0.2g DNS-86 and OP-10 (mass ratio of anionic emulsifier and nonionic emulsifier is 1: 1) and 5g deionized water and 0.05g sodium bicarbonate are as still liquid, after stirring, be warming up to 70 DEG C, after insulation 30min, be warming up to 85 DEG C, then in 30min, drip nuclear monomer and 5g initiator solution that pre-emulsification is good simultaneously, after dripping Bi Baowen 30min, keep homo(io)thermism, in 3h, drip shell pre-emulsion monomer and remaining initiator solution simultaneously, drip Bi Baowen 3h, cool to below 40 DEG C, the pH value of emulsion is adjusted to 8 with ammoniacal liquor, obtain stable organic inorganic hybridization high silicon content acrylic ester emulsion.The SiO of its emulsion
2content is 22%, resistance to 3 freeze thawing (GB/T11175-2002).Emulsion is coated on sheet glass and toasts 15min at 120 DEG C, and its film is transparent smooth, and hardness has 5H (GB/T6739-2006), adhesion 1 grade (GB/T 1720-1979).
Embodiment 2:
The vinyltriethoxysilane of 15g ethanol, 1.05g is added in 35g silicon sol, and stirring reaction 6h at 40 DEG C, obtains modified silicasol.
By 3g deionized water, 0.2gPEO-10 and T-80 (mass ratio of anionic emulsifier and nonionic emulsifier is 2: 1) join in wide-necked bottle, after being uniformly dissolved, in 5min, at the uniform velocity drip 4g mix monomer methyl methacrylate and butyl acrylate (mass ratio is 1: 1), after dropwising, speed stirring 30min with magnetic stirring apparatus with 1000rpm, then stir 5min with the speed of 800rpm, make pre-emulsified nuclear monomer.
By 13g deionized water, 0.9g PEO-10 and T-80 (mass ratio of anionic emulsifier and nonionic emulsifier is 2: 1) join in wide-necked bottle, after being uniformly dissolved, in 25min, at the uniform velocity drip 23g mix monomer methyl methacrylate and butyl acrylate (mass ratio is 1: 1), and all 0.7g methacrylic acids in formula, after dropwising, speed stirring 20min with magnetic stirring apparatus with 1500rpm, stir 5min with the speed of 800rpm again, make pre-emulsified shell monomer.And 0.6g Potassium Persulphate is dissolved in 25g deionized water.
Agitator is being housed, reflux condensing tube, in the four-hole boiling flask of thermometer, add 45g modified silicasol and 1.3gN-n-methylolacrylamide, 0.4g PEO-10 and T-80 (mass ratio of anionic emulsifier and nonionic emulsifier is 2: 1) and 3g deionized water and 0.4g sodium bicarbonate are as still liquid, after stirring, be warming up to 70 DEG C, after insulation 30min, be warming up to 85 DEG C, then in 40min, drip nuclear monomer and 10g initiator solution that pre-emulsification is good simultaneously, after dripping Bi Baowen 30min, keep homo(io)thermism, in 2.5h, drip shell pre-emulsion monomer and remaining initiator solution simultaneously, drip Bi Baowen 3h, cool to below 40 DEG C, the pH value of emulsion is adjusted to 8 left and right with ammoniacal liquor, obtain stable organic inorganic hybridization high silicon content acrylic ester emulsion.The SiO of its emulsion
2content is 23%, resistance to 5 freeze thawing (GB/T11175-2002).Emulsion is coated on sheet glass and toasts 15min at 120 DEG C, and its film is transparent smooth, and hardness has 5H (GB/T6739-2006), 0 grade of sticking power (GB/T 1720-1979).
Embodiment 3:
γ-glycidyl ether oxygen propyl trimethoxy silicane of 15g Virahol, 1.05g is added in 35g silicon sol, and stirring reaction 12h at 20 DEG C, obtains modified silicasol.
By 5g deionized water, 0.35g PEO-10 and T-80 (mass ratio of anionic emulsifier and nonionic emulsifier is 1: 1) join in wide-necked bottle, after being uniformly dissolved, in 10min, at the uniform velocity drip 7g mix monomer methyl methacrylate and butyl acrylate (mass ratio is 1: 1), after dropwising, speed stirring 15min with magnetic stirring apparatus with 1500rpm, then stir 5min with the speed of 500rpm, make pre-emulsified nuclear monomer.
By 10g deionized water, 0.7g PEO-10 and T-80 (mass ratio of anionic emulsifier and nonionic emulsifier is 1: 1) join in wide-necked bottle, after being uniformly dissolved, in 20min, at the uniform velocity drip 20g mix monomer methyl methacrylate and butyl acrylate (mass ratio is 1: 1), and all 0.3g methacrylic acids in formula, after dropwising, speed stirring 20min with magnetic stirring apparatus with 1500rpm, stir 5min with the speed of 500rpm again, make pre-emulsified shell monomer.And 0.35g ammonium persulphate is dissolved in 20g deionized water.
Agitator is being housed, reflux condensing tube, in the four-hole boiling flask of thermometer, add 40g modified silicasol and 1g hydroxyethyl methylacrylate, 0.6g PEO-10 and T-80 (mass ratio of anionic emulsifier and nonionic emulsifier is 1: 1) and 4g deionized water and 0.4g sodium bicarbonate are as still liquid, after stirring, be warming up to 70 DEG C, after insulation 30min, be warming up to 85 DEG C, then in 1h, drip nuclear monomer and 6g initiator solution that pre-emulsification is good simultaneously, after dripping Bi Baowen 30min, keep homo(io)thermism, in 3.5h, drip shell pre-emulsion monomer and remaining initiator solution simultaneously, drip Bi Baowen 2.5h, cool to below 40 DEG C, the pH value of emulsion is adjusted to 8 left and right with ammoniacal liquor, obtain stable organic inorganic hybridization high silicon content acrylic ester emulsion.The SiO of its emulsion
2content is 22%, resistance to 3 freeze thawing (GB/T11175-2002).Emulsion is coated on sheet glass and toasts 15min at 120 DEG C, and its film is transparent smooth, and hardness has 5H (GB/T6739-2006), adhesion 1 grade (GB/T 1720-1979).
Embodiment 4:
The γ of 20g Virahol, 3.15g-(methacryloxy) propyl trimethoxy silicane is added in 70g silicon sol, and stirring reaction 10h at 25 DEG C, obtains modified silicasol.
By 3g deionized water, 0.2gDNS-86 and T-80 (mass ratio of anionic emulsifier and nonionic emulsifier is 1: 1) join in wide-necked bottle, after being uniformly dissolved, in 15min, at the uniform velocity drip 3g mix monomer methyl methacrylate and butyl acrylate (mass ratio is 1: 1), after dropwising, speed stirring 15min with magnetic stirring apparatus with 2000rpm, then stir 5min with the speed of 500rpm, make pre-emulsified nuclear monomer.
By 15g deionized water, 0.8gDNS-86 and T-80 (mass ratio of anionic emulsifier and nonionic emulsifier is 1: 1) join in wide-necked bottle, after being uniformly dissolved, in 20min, at the uniform velocity drip 25g mix monomer methyl methacrylate and butyl acrylate (mass ratio is 1: 1), and all 0.8g methacrylic acids in formula, after dropwising, speed stirring 20min with magnetic stirring apparatus with 2000rpm, stir 5min with the speed of 500rpm again, make pre-emulsified shell monomer.And 0.30g ammonium persulphate is dissolved in 15g deionized water.
Agitator is being housed, reflux condensing tube, in the four-hole boiling flask of thermometer, add 50g modified silicasol and 1.5g hydroxyethyl methylacrylate, 0.7g DNS-86 and T-80 (mass ratio of anionic emulsifier and nonionic emulsifier is 1: 1) and 7g deionized water and 0.4g sodium bicarbonate are as still liquid, after stirring, be warming up to 70 DEG C, after insulation 30min, be warming up to 85 DEG C, then in 40min, drip nuclear monomer and 5g initiator solution that pre-emulsification is good simultaneously, after dripping Bi Baowen 40min, keep homo(io)thermism, in 4h, drip shell pre-emulsion monomer and remaining initiator solution simultaneously, drip Bi Baowen 2.5h, cool to below 40 DEG C, the pH value of emulsion is adjusted to 8 left and right with ammoniacal liquor, obtain stable organic inorganic hybridization high silicon content acrylic ester emulsion.The SiO of its emulsion
2content is 24%, resistance to 5 freeze thawing (GB/T11175-2002).Emulsion is coated on sheet glass and toasts 15min at 120 DEG C, and its film is transparent smooth, and hardness has 5H (GB/T6739-2006), adhesion 1 grade (GB/T 1720-1979).
Embodiment 5:
The vinyltriethoxysilane of 10g ethanol, 1.58g is added in 35g silicon sol, and stirring reaction 24h at 25 DEG C, obtains modified silicasol.
By 6g deionized water, 0.3gDNS-86 and OP-10 (mass ratio of anionic emulsifier and nonionic emulsifier is 2: 1) join in wide-necked bottle, after being uniformly dissolved, in 5min, at the uniform velocity drip 5g mix monomer methyl methacrylate and butyl acrylate (mass ratio is 1: 1), after dropwising, speed stirring 15min with magnetic stirring apparatus with 1500rpm, then stir 5min with the speed of 600rpm, make pre-emulsified nuclear monomer.
By 10g deionized water, 0.8gDNS-86 and OP-10 (mass ratio of anionic emulsifier and nonionic emulsifier is 2: 1) join in wide-necked bottle, after being uniformly dissolved, in 20min, at the uniform velocity drip 21g mix monomer methyl methacrylate and butyl acrylate (mass ratio is 1: 1), and all 0.7g methacrylic acids in formula, after dropwising, speed stirring 20min with magnetic stirring apparatus with 1500rpm, stir 5min with the speed of 600rpm again, make pre-emulsified shell monomer.And 0.38g ammonium persulphate is dissolved in 15g deionized water.
Agitator is being housed, reflux condensing tube, in the four-hole boiling flask of thermometer, add 40g modified silicasol and 1.2g hydroxyethyl methylacrylate, 0.5g DNS-86 and OP-10 (mass ratio of anionic emulsifier and nonionic emulsifier is 2: 1) and 4g deionized water and 0.4g sodium bicarbonate are as still liquid, after stirring, be warming up to 70 DEG C, after insulation 30min, be warming up to 85 DEG C, then in 1h, drip nuclear monomer and 5g initiator solution that pre-emulsification is good simultaneously, after dripping Bi Baowen 30min, keep homo(io)thermism, in 3h, drip shell pre-emulsion monomer and remaining initiator solution simultaneously, drip Bi Baowen 3h, cool to below 40 DEG C, the pH value of emulsion is adjusted to 8 left and right with ammoniacal liquor, obtain stable organic inorganic hybridization high silicon content acrylic ester emulsion.The SiO of its emulsion
2content is 22%, resistance to 5 freeze thawing (GB/T11175-2002).Emulsion is coated on sheet glass and toasts 15min at 120 DEG C, and its film is transparent smooth, and hardness has 5H (GB/T6739-2006), 0 grade of sticking power (GB/T 1720-1979).
Embodiment 6:
γ-glycidyl ether oxygen propyl trimethoxy silicane of 30g ethanol, 3.2g is added in 75g silicon sol, and stirring reaction 8h at 25 DEG C, obtains modified silicasol.
By 5g deionized water, 0.25g PEO-10 and T-80 (mass ratio of anionic emulsifier and nonionic emulsifier is 1: 1) join in wide-necked bottle, after being uniformly dissolved, in 15min, at the uniform velocity drip 4g mix monomer methyl methacrylate and butyl acrylate (mass ratio is 1: 1), after dropwising, speed stirring 15min with magnetic stirring apparatus with 1700rpm, then stir 5min with the speed of 500rpm, make pre-emulsified nuclear monomer.
By 12g deionized water, 0.9g PEO-10 and T-80 (mass ratio of anionic emulsifier and nonionic emulsifier is 1: 1) join in wide-necked bottle, after being uniformly dissolved, in 25min, at the uniform velocity drip 25g mix monomer methyl methacrylate and butyl acrylate (mass ratio is 1: 1), and all 0.5g methacrylic acids in formula, after dropwising, speed stirring 20min with magnetic stirring apparatus with 1700rpm, stir 5min with the speed of 500rpm again, make pre-emulsified shell monomer.And 0.38g Potassium Persulphate is dissolved in 20g deionized water.
Agitator is being housed, reflux condensing tube, in the four-hole boiling flask of thermometer, add 40g modified silicasol and 1gN-n-methylolacrylamide, 0.4g PEO-10 and T-80 (mass ratio of anionic emulsifier and nonionic emulsifier is 1: 1) and 5g deionized water and 0.4g sodium bicarbonate are as still liquid, after stirring, be warming up to 70 DEG C, after insulation 30min, be warming up to 85 DEG C, then in 40min, drip nuclear monomer and 8g initiator solution that pre-emulsification is good simultaneously, after dripping Bi Baowen 1h, keep homo(io)thermism, in 4h, drip shell pre-emulsion monomer and remaining initiator solution simultaneously, drip Bi Baowen 3h, cool to below 40 DEG C, the pH value of emulsion is adjusted to 8 left and right with ammoniacal liquor, obtain stable organic inorganic hybridization high silicon content acrylic ester emulsion.The SiO of its emulsion
2content is 21%, resistance to 4 freeze thawing (GB/T11175-2002).Emulsion is coated on sheet glass and toasts 15min at 120 DEG C, and its film is transparent smooth, and hardness has 5H (GB/T6739-2006), adhesion 1 grade (GB/T 1720-1979).
Claims (7)
1. a preparation method for organic inorganic hybridization high silicon content acrylic ester emulsion, is characterized in that:
The γ of 15g Virahol, 0.84g-(methacryloxy) propyl trimethoxy silicane is added in 35g silicon sol, and stirring reaction 8h at 50 DEG C, obtains modified silicasol; By 3g deionized water, 0.1gDNS ?86 and OP ?10 join in wide-necked bottle, DNS ?86 and OP ?10 mass ratio be 1:1, after being uniformly dissolved, in 10min, at the uniform velocity dripping 2g mass ratio is mix monomer methyl methacrylate and the butyl acrylate of 1:1, after dropwising, and the speed stirring 15min with magnetic stirring apparatus with 2000rpm, stir 5min with the speed of 500rpm again, make pre-emulsified nuclear monomer;
By 5g deionized water, 0.3gDNS ?86 and OP ?10 join in wide-necked bottle, DNS ?86 and OP ?10 mass ratio be 1:1, after being uniformly dissolved, in 20min, at the uniform velocity dripping 10g mass ratio is mix monomer methyl methacrylate and the butyl acrylate of 1:1, and 0.15g methacrylic acid, after dropwising, speed stirring 20min with magnetic stirring apparatus with 2000rpm, then stir 5min with the speed of 500rpm, make pre-emulsified shell monomer; And 0.10g Potassium Persulphate is dissolved in 10g deionized water;
Agitator is being housed, reflux condensing tube, in the four-hole boiling flask of thermometer, add 25g modified silicasol and 0.5gN ?n-methylolacrylamide, 0.2g DNS ?86 and OP ?10 and 5g deionized water and 0.05g sodium bicarbonate as still liquid, DNS ?86 and OP ?10 mass ratio be 1:1, after stirring, be warming up to 70 DEG C, after insulation 30min, be warming up to 85 DEG C, then in 30min, drip nuclear monomer and 5g initiator solution that pre-emulsification is good simultaneously, after dripping Bi Baowen 30min, keep homo(io)thermism, in 3h, drip shell pre-emulsion monomer and remaining initiator solution simultaneously, drip Bi Baowen 3h, cool to below 40 DEG C, the pH value of emulsion is adjusted to 8 with ammoniacal liquor, obtain stable organic inorganic hybridization high silicon content acrylic ester emulsion.
2. a preparation method for organic inorganic hybridization high silicon content acrylic ester emulsion, is characterized in that:
The vinyltriethoxysilane of 15g ethanol, 1.05g is added in 35g silicon sol, and stirring reaction 6h at 40 DEG C, obtains modified silicasol;
By 3g deionized water, 0.2gPEO ?10 and T ?80 join in wide-necked bottle, PEO ?10 and T ?80 mass ratio be 2:1, after being uniformly dissolved, at the uniform velocity drip 4g mix monomer methyl methacrylate and butyl acrylate in 5min, methyl methacrylate and butyl acrylate mass ratio are 1:1, after dropwising, speed stirring 30min with magnetic stirring apparatus with 1000rpm, then stir 5min with the speed of 800rpm, make pre-emulsified nuclear monomer;
By 13g deionized water, 0.9g PEO ?10 and T ?80 join in wide-necked bottle, PEO ?10 and T ?80 mass ratio be 2:1, after being uniformly dissolved, in 25min, at the uniform velocity drip 23g mix monomer methyl methacrylate and butyl acrylate, methyl methacrylate and butyl acrylate mass ratio are 1:1, and all 0.7g methacrylic acids in formula, after dropwising, speed stirring 20min with magnetic stirring apparatus with 1500rpm, stir 5min with the speed of 800rpm again, make pre-emulsified shell monomer; And 0.6g Potassium Persulphate is dissolved in 25g deionized water;
Agitator is being housed, reflux condensing tube, in the four-hole boiling flask of thermometer, add 45g modified silicasol and 1.3gN ?n-methylolacrylamide, 0.4g PEO ?10 and T ?80 and 3g deionized water and 0.4g sodium bicarbonate as still liquid, PEO ?10 and T ?80 mass ratio be 2:1, after stirring, be warming up to 70 DEG C, after insulation 30min, be warming up to 85 DEG C, then in 40min, drip nuclear monomer and 10g initiator solution that pre-emulsification is good simultaneously, after dripping Bi Baowen 30min, keep homo(io)thermism, in 2.5h, drip shell pre-emulsion monomer and remaining initiator solution simultaneously, drip Bi Baowen 3h, cool to below 40 DEG C, the pH value of emulsion is adjusted to 8 left and right with ammoniacal liquor, obtain stable organic inorganic hybridization high silicon content acrylic ester emulsion.
3. a preparation method for organic inorganic hybridization high silicon content acrylic ester emulsion, is characterized in that:
By 15g Virahol, 1.05g γ ?glycidyl ether oxygen propyl trimethoxy silicane be added in 35g silicon sol, stirring reaction 12h at 20 DEG C, obtains modified silicasol;
By 5g deionized water, 0.35g PEO ?10 and T ?80, PEO ?10 and T ?80 mass ratio be 1:1; Join in wide-necked bottle, after being uniformly dissolved, in 10min, at the uniform velocity drip 7g mix monomer methyl methacrylate and butyl acrylate, methyl methacrylate and butyl acrylate mass ratio are 1:1, after dropwising, speed stirring 15min with magnetic stirring apparatus with 1500rpm, then stir 5min with the speed of 500rpm, make pre-emulsified nuclear monomer;
By 10g deionized water, 0.7g PEO ?10 and T ?80 join in wide-necked bottle, PEO ?10 and T ?80 mass ratio be 1:1, after being uniformly dissolved, in 20min, at the uniform velocity drip 20g mix monomer methyl methacrylate and butyl acrylate, methyl methacrylate and butyl acrylate mass ratio are 1:1, and all 0.3g methacrylic acids in formula, after dropwising, speed stirring 20min with magnetic stirring apparatus with 1500rpm, stir 5min with the speed of 500rpm again, make pre-emulsified shell monomer, and 0.35g ammonium persulphate is dissolved in 20g deionized water,
Agitator is being housed, reflux condensing tube, in the four-hole boiling flask of thermometer, add 40g modified silicasol and 1g hydroxyethyl methylacrylate, 0.6g PEO ?10 and T ?80 and 4g deionized water and 0.4g sodium bicarbonate as still liquid, PEO ?10 and T ?80 mass ratio be 1:1, after stirring, be warming up to 70 DEG C, after insulation 30min, be warming up to 85 DEG C, then in 1h, drip nuclear monomer and 6g initiator solution that pre-emulsification is good simultaneously, after dripping Bi Baowen 30min, keep homo(io)thermism, in 3.5h, drip shell pre-emulsion monomer and remaining initiator solution simultaneously, drip Bi Baowen 2.5h, cool to below 40 DEG C, the pH value of emulsion is adjusted to 8 left and right with ammoniacal liquor, obtain stable organic inorganic hybridization high silicon content acrylic ester emulsion.
4. a preparation method for organic inorganic hybridization high silicon content acrylic ester emulsion, is characterized in that:
The γ of 20g Virahol, 3.15g-(methacryloxy) propyl trimethoxy silicane is added in 70g silicon sol, and stirring reaction 10h at 25 DEG C, obtains modified silicasol;
By 3g deionized water, 0.2gDNS ?86 and T ?80 join in wide-necked bottle, DNS ?86 and T ?80 mass ratio be 1:1, after being uniformly dissolved, at the uniform velocity drip 3g mix monomer methyl methacrylate and butyl acrylate in 15min, methyl methacrylate and butyl acrylate mass ratio are 1:1, after dropwising, speed stirring 15min with magnetic stirring apparatus with 2000rpm, then stir 5min with the speed of 500rpm, make pre-emulsified nuclear monomer;
By 15g deionized water, 0.8gDNS ?86 and T ?80 join in wide-necked bottle, DNS ?86 and T ?80 mass ratio be 1:1, after being uniformly dissolved, in 20min, at the uniform velocity drip 25g mix monomer methyl methacrylate and butyl acrylate, methyl methacrylate and butyl acrylate mass ratio are 1:1, and all 0.8g methacrylic acids in formula, methyl methacrylate and butyl acrylate mass ratio are 1:1, after dropwising, speed stirring 20min with magnetic stirring apparatus with 2000rpm, stir 5min with the speed of 500rpm again, make pre-emulsified shell monomer, and 0.30g ammonium persulphate is dissolved in 15g deionized water,
Agitator is being housed, reflux condensing tube, in the four-hole boiling flask of thermometer, add 50g modified silicasol and 1.5g hydroxyethyl methylacrylate, 0.7g DNS ?86 and T ?80 and 7g deionized water and 0.4g sodium bicarbonate as still liquid, DNS ?86 and T ?80 mass ratio be 1:1, after stirring, be warming up to 70 DEG C, after insulation 30min, be warming up to 85 DEG C, then in 40min, drip nuclear monomer and 5g initiator solution that pre-emulsification is good simultaneously, after dripping Bi Baowen 40min, keep homo(io)thermism, in 4h, drip shell pre-emulsion monomer and remaining initiator solution simultaneously, drip Bi Baowen 2.5h, cool to below 40 DEG C, the pH value of emulsion is adjusted to 8 left and right with ammoniacal liquor, obtain stable organic inorganic hybridization high silicon content acrylic ester emulsion.
5. a preparation method for organic inorganic hybridization high silicon content acrylic ester emulsion, is characterized in that:
The vinyltriethoxysilane of 10g ethanol, 1.58g is added in 35g silicon sol, and stirring reaction 24h at 25 DEG C, obtains modified silicasol;
By 6g deionized water, 0.3gDNS ?86 and OP ?10 join in wide-necked bottle, DNS ?86 and OP ?10 mass ratio be 2:1, after being uniformly dissolved, at the uniform velocity drip 5g mix monomer methyl methacrylate and butyl acrylate in 5min, methyl methacrylate and butyl acrylate mass ratio are 1:1, after dropwising, speed stirring 15min with magnetic stirring apparatus with 1500rpm, then stir 5min with the speed of 600rpm, make pre-emulsified nuclear monomer;
By 10g deionized water, 0.8gDNS ?86 and OP ?10 join in wide-necked bottle, DNS ?86 and OP ?10 mass ratio be 2:1, after being uniformly dissolved, in 20min, at the uniform velocity drip 21g mix monomer methyl methacrylate and butyl acrylate, and all 0.7g methacrylic acids in formula, methyl methacrylate and butyl acrylate mass ratio are 1:1, after dropwising, speed stirring 20min with magnetic stirring apparatus with 1500rpm, stir 5min with the speed of 600rpm again, make pre-emulsified shell monomer; And 0.38g ammonium persulphate is dissolved in 15g deionized water;
Agitator is being housed, reflux condensing tube, in the four-hole boiling flask of thermometer, add 40g modified silicasol and 1.2g hydroxyethyl methylacrylate, 0.5g DNS ?86 and OP ?10 and 4g deionized water and 0.4g sodium bicarbonate as still liquid, DNS ?86 and OP ?10 mass ratio be 2:1, after stirring, be warming up to 70 DEG C, after insulation 30min, be warming up to 85 DEG C, then in 1h, drip nuclear monomer and 5g initiator solution that pre-emulsification is good simultaneously, after dripping Bi Baowen 30min, keep homo(io)thermism, in 3h, drip shell pre-emulsion monomer and remaining initiator solution simultaneously, drip Bi Baowen 3h, cool to below 40 DEG C, the pH value of emulsion is adjusted to 8 left and right with ammoniacal liquor, obtain stable organic inorganic hybridization high silicon content acrylic ester emulsion.
6. a preparation method for organic inorganic hybridization high silicon content acrylic ester emulsion, is characterized in that:
By 30g ethanol, 3.2g γ ?glycidyl ether oxygen propyl trimethoxy silicane be added in 75g silicon sol, stirring reaction 8h at 25 DEG C, obtains modified silicasol;
By 5g deionized water, 0.25g PEO ?10 and T ?80 join in wide-necked bottle, PEO ?10 and T ?80 mass ratio be 1:1, after being uniformly dissolved, at the uniform velocity drip 4g mix monomer methyl methacrylate and butyl acrylate in 15min, methyl methacrylate and butyl acrylate mass ratio are 1:1, after dropwising, speed stirring 15min with magnetic stirring apparatus with 1700rpm, then stir 5min with the speed of 500rpm, make pre-emulsified nuclear monomer;
By 12g deionized water, 0.9g PEO ?10 and T ?80 join in wide-necked bottle, PEO ?10 and T ?80 mass ratio be 1:1, after being uniformly dissolved, in 25min, at the uniform velocity drip 25g mix monomer methyl methacrylate and butyl acrylate, and all 0.5g methacrylic acids in formula, methyl methacrylate and butyl acrylate mass ratio are 1:1, after dropwising, speed stirring 20min with magnetic stirring apparatus with 1700rpm, stir 5min with the speed of 500rpm again, make pre-emulsified shell monomer; And 0.38g Potassium Persulphate is dissolved in 20g deionized water;
Agitator is being housed, reflux condensing tube, in the four-hole boiling flask of thermometer, add 40g modified silicasol and 1gN ?n-methylolacrylamide, 0.4g PEO ?10 and T ?80 and 5g deionized water and 0.4g sodium bicarbonate as still liquid, PEO ?10 and T ?80 mass ratio be 1:1, after stirring, be warming up to 70 DEG C, after insulation 30min, be warming up to 85 DEG C, then in 40min, drip nuclear monomer and 8g initiator solution that pre-emulsification is good simultaneously, after dripping Bi Baowen 1h, keep homo(io)thermism, in 4h, drip shell pre-emulsion monomer and remaining initiator solution simultaneously, drip Bi Baowen 3h, cool to below 40 DEG C, the pH value of emulsion is adjusted to 8 left and right with ammoniacal liquor, obtain stable organic inorganic hybridization high silicon content acrylic ester emulsion.
7. an organic inorganic hybridization high silicon content acrylic ester emulsion, is characterized in that: it is prepared by method described in claim 1-6 any one.
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