CN103725141A - Water-based emulsion for protecting external wall of building and preparation method for water-based emulsion - Google Patents
Water-based emulsion for protecting external wall of building and preparation method for water-based emulsion Download PDFInfo
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Abstract
The invention provides a water-based emulsion material for protecting an external wall of a building under a subtropical monsoon climate condition and a preparation method for the water-based emulsion material. The water-based emulsion material is water-based emulsion with a core-shell structure and a cyclosiloxane structure, and comprises the following components in percentage by weight: 25.6 to 74.5 percent of core-shell latex particles, 0.1 to 0.6 percent of a bactericidal anti-alga agent, 0.01 to 0.1 percent of a pH modifier and the balance of de-ionized water. According to the water-based emulsion material and the preparation method, a core-shell emulsion polymerization technology and the hydrophobic effect of an organic silane coupling agent are utilized, and the prepared water-based emulsion material has high protective waterproof performance for the external wall of the building under the subtropical monsoon climate condition, and can also be used in the fields of engineering protection, building water-proofing, bridge maintenance and the like.
Description
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Technical field
The invention belongs to water-based emulsion field, be specifically related to a kind of water-based emulsion material simultaneously with nucleocapsid structure and cyclosiloxane structure and preparation method thereof, this water-based emulsion material is applicable to external wall protection under the monsoon climate condition of subtropics, also can be used for the fields such as engineering protection, buildings waterproof, bridge inspection and maintenance.
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Background technology
The work-ing life of material and performance are inseparable with the residing environment of material, and for protective material used for building exterior wall, the application performance of material is subject to building the weather restriction in area of living in greatly.On the south China the Changjiang river, the large portion in most area and the North China Plain all belongs to typical subtropics monsoon climate zone, and that its feature is is cold in winter and hot in summer, make a clear distinction between the four seasons, and precipitation is plentiful, and season, partition ratio was more even.The external wall material requirements being positioned under this climatope itself has excellent waterproof heat-resisting weather resistance, and this is also the key of current water-based emulsion research used for building exterior wall.
Compared with solvent borne emulsion, water-based emulsion is take water as solvent, eliminated the organic solvents such as acetone, benzene, toluene the volatilize HUMAN HEALTH and the problem of environmental pollution that bring.So, water-based emulsion was just received and has been paid close attention to widely and promote from research beginning, but with the alternative organic solvent of water, tend to affect the application performance of material, on polymerization technique, synthesis technique, all there is technical defect in the water-based material using acrylate as main polymerization single polymerization monomer, cause the deficiency of material on waterproof heat-resisting weather resistance, even if having at present many patents to occur, but still have the problems such as technology is single, performance is limited.
For example patent 102149769A discloses a kind of water-based emulsion, this water-based emulsion contains following (A), (B) and (C), (A) contain the structural unit from ethene and/or straight chain shape alpha-olefin, with from formula (I) CH2=CH-R(I) (in formula, R represents secondary alkyl, tertiary alkyl or alicyclic hydrocarbon radical) shown in the olefinic copolymer of structural unit of vinyl compound, or on this olefinic copolymer graft polymerization α, the polymkeric substance that beta-unsaturated carboxylic acid acid anhydride forms, (B) contain from α, the structural unit of beta-unsaturated carboxylic acid and from α, the acrylic resin of the structural unit of beta-unsaturated carboxylic acid ester, (C) water.This water-based emulsion is more excellent in adhesion property, but is only confined to polypropylene material class surface.
Patent 02132834.X discloses a kind of environment-protecting type water emulsion and preparation method thereof, by the method for oil phase, water processing and water oil mix and blend, obtain a kind of water-based emulsion of applicable bonding timber, solve the problem of polyvinyl alcohol water tolerance deficiency, but be only applicable to inner wall of building material.
Patent 200880118365.7 discloses a kind of water-based emulsion and preparation method thereof, described water-based emulsion comprises as the polyvinyl alcohol based resins of dispersion agent with as the polymkeric substance of dispersate, described polymkeric substance has the structural unit that comes from ethylenically unsaturated monomers, described water-based emulsion can form the film with excellent transparency, and has excellent mechanical stability, chemical stability, freeze-stable and stability in storage.In described water-based emulsion, described dispersate has the median size of 100～450 μ m, and the apparent percentage of grafting of described polyvinyl alcohol based resins based on dispersate is 65～75%.The adhesive property excellence of this kind of emulsion, but waterproof protective performance is limited.
Patent 00803430.3 discloses a kind of water-based emulsion of silicoorganic compound, relate to a kind of water-based being formed by following ingredients, abundant emulsion: (A) this composition be selected from (A1) C1-C20-alkyl-C2-C6 organoalkoxysilane and (A2) contain alkoxyl group organopolysiloxane, (C) emulsifying agent and (D) organic solvent.Described stable water-based emulsion is to be suitable for hydrophobic dipping or linging mineral building materials.This emulsion has good water resistance, but has comprised more organic solvent in emulsion preparation, and production cost is more expensive.
Patent 201010595777.9 discloses a kind of water-based emulsion and water-borne coatings, disclosing water-based emulsion is under (B) sulfonation modifying polyvinyl alcohol exists, emulsion polymerization (A) polymerizability unsaturated monomer obtains, (A) water-based emulsion that polymerizability unsaturated monomer comprises (methyl) acrylate, the water-based emulsion that this invention is relevant and water-borne coatings, can be used as coating timber use coating.But this water-based emulsion can decline work-ing life under the condition of high temperature and rainy.
Patent 200680007025.8 discloses a kind of water-based emulsion and coating, this water-based emulsion is selected from the polymkeric substance of at least one monomeric unit of (methyl) acrylic ester monomeric unit, styrenic monomers unit and diene monomer unit as dispersion to have, to there is 1.9%mol above 1,2-diol bond, saponification deg are that more than 70%mol vinyl alcohol system polymer (A) and tensio-active agent (B) are as dispersion agent, (A)/weight ratio (B) is 50/50-95/5, and the median size of discrete particles is below 0.5 μ m.This material preparation process is loaded down with trivial details, need repeatedly repeat the decompression operation that pressurizes, and the weather resistance of product is limited.
Summary of the invention
Existing patent and document are not studied for the protection waterproof heat-resisting weather resistance of water-based emulsion, have ignored the demand of the multifunctional alls such as water-based emulsion material environment friendly, protective, weathering resistance; For this problem, the invention provides a kind of water-based emulsion material simultaneously with nucleocapsid structure and cyclosiloxane structure and preparation method thereof, this water-based emulsion material is applicable to external wall protection under the monsoon climate condition of subtropics, also can be used for the fields such as engineering protection, buildings waterproof, bridge inspection and maintenance.
The invention provides a kind of environment-protecting type water emulsion for external wall protection, by weight percentage, its composition comprises:
Core-shell latex particles: 25.6% ~ 74.5%;
The anti-algae agent of sterilization: 0.1%～0.6%;
PH conditioning agent: 0.01%～0.1%;
Deionized water: surplus;
The kernel of described core-shell latex particles is polyacrylic ester or acrylate and the polymer that contains the organo silane coupling agent of ring texture, shell is polyacrylic ester or acrylate and the polymer that contains the organo silane coupling agent of ring texture, the proportional range in the function monomer of composition kernel with the polymer monomer of high glass-transition temperature and the polymer monomer of lower glass transition temperatures is 4:6 ~ 8:2, in the function monomer of composition shell, there is the polymer monomer of high glass-transition temperature and the polymer monomer proportional range of lower glass transition temperatures is 7:3 ~ 4:6, the repertoire monomer of composition kernel is 3:7 ~ 7:3 with the proportional range of the repertoire monomer of composition shell, the particle diameter of described core-shell latex particles is 50nm ~ 200nm,
The anti-algae agent of described sterilization is Kathon (OIT), 4, the chloro-Kathon of 5-bis-(DCOIT), MIT (MIT), 1,2-benzisothiazole-3-ketone (BIT), CMIT (CIT), 2-methyl-4, any one in 5-propylidene-4-isothiazoline-3-ketone (MTI) or quaternary ammonium salt;
Described pH adjusting agent is thanomin phosphoric acid ester, N-(3-aminopropyl) diethanolamine, ammoniacal liquor, thanomin or sodium bicarbonate.
Between nucleocapsid, reactive force is exactly that the common interior carbon-carbon bond of molecule connects, and Intermolecular Forces etc.
The water-based emulsion material simultaneously with nucleocapsid structure and cyclosiloxane structure of the present invention is a kind of white emulsion material of blueing light, material has the high temperature resistant weather-proof effect of excellent waterproof protective, be applicable to external wall protection under the monsoon climate condition of subtropics, also can be applicable to the fields such as engineering protection, buildings waterproof, bridge inspection and maintenance, and can prevent that mould, liver moss from producing, avoid polluting keeping clean.
This environment-friendly aqueous nanometer coating material described in this patent is applicable to external wall protection under the monsoon climate condition of subtropics.In described environment-friendly aqueous nanometer coating material, there is nucleocapsid structure and cyclosiloxane structure; Nucleocapsid structure gives emulsion material unique and good performance, the features such as the emulsion with nucleocapsid structure possesses that rebound resilience is good, film-forming temperature is low, film forming properties and mechanical property excellence.Emulsion particle core part and shell part can be optimized by Theoretical Calculation, to be met the nucleocapsid structure layer of different demands.Contain in addition ring texture organo-silicon coupling agent have a lifting that is beneficial to emulsion material barrier propterty, water resistance, weather resistance, and by the bonding of shell silane coupling agent and kernel polyacrylic ester, thereby obtain excellent integrated application performance.
The preparation method of the environment-friendly aqueous nanometer coating material for concrete protection of the present invention comprises the steps:
(1) prepare starting material: the starting material of preparing the environment-friendly aqueous nanometer coating material for concrete protection of the present invention comprise:
Acrylate monomer 15% ~ 45%;
Containing the organo silane coupling agent 5%～15% of unsaturated double-bond;
Ring structure organo silane coupling agent 5%～10%;
Emulsifying agent 0.3%～3%;
Persulphate 0.3% ~ 1.5%
The anti-algae agent 0.1%～0.6% of sterilization
PH adjusting agent 0.01%～0.1%
Deionized water surplus.
(2) prepare core emulsion: at 5 ℃～40 ℃, acrylate monomer is slowly added drop-wise in the deionized water that adds emulsifying agent and carries out emulsification with the rate of addition of 2～10 drops/sec, obtain the pre-emulsion A of finely dispersed core emulsion, the concentration range of pre-emulsion A is 40% ~ 75%, and wherein emulsifier component scope is 0.3% ~ 3%.Pre-emulsion A and the deionized water that adds persulphate are slowly added drop-wise in the deionized water of 60 ℃～90 ℃ with the rate of addition of 2～10 drops/sec simultaneously, keep 60 ℃～90 ℃ temperature dispersed with stirring, under 50rpm～250rpm stirring velocity, stir 15min～40min, each component is uniformly dispersed, obtains core emulsion B; The concentration range of core emulsion B is 30% ~ 55%.
(3) prepare nuclear-shell emulsion: at 5 ℃～40 ℃, by acrylate monomer, containing the organo silane coupling agent of unsaturated double-bond, organo silane coupling agent containing ring body structurc is slowly added drop-wise in the deionized water that adds emulsifying agent and carries out emulsification with the rate of addition of 2～10 drops/sec, obtain finely dispersed pre-emulsion C that can emulsion, pre-emulsion C and the deionized water that adds persulphate are slowly added drop-wise in the core emulsion B of 60 ℃～90 ℃ with the rate of addition of 2～10 drops/sec simultaneously, keep 60 ℃～90 ℃ temperature dispersed with stirring, under 50rpm～250rpm stirring velocity, stir 60min～120min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent, regulating the PH of nuclear-shell emulsion D is 7～8; To neutral emulsion D, drip the deionized water solution that is dispersed with the anti-algae agent of sterilization, regulate the sterilization and anticorrosion performance of neutral emulsion D to antibiotic rate >=99%; Thereby obtain having the water-based emulsion of protection water resistance.
The test of above-mentioned antibiotic rate is according to GB 21866-2008-T standard.
Described acrylate monomer comprises: any in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, ethyl acrylate, (methyl) glycidyl acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate or several arbitrarily;
The described organo silane coupling agent containing unsaturated double-bond comprise in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane any or several arbitrarily.Unsaturated double-bond provides effective reactive functional group group, and alkoxyl group is effective hydrolytic crosslinking group, is conducive to the lifting of later stage waterproof protective performance.
The described organo silane coupling agent containing ring body structurc comprise in hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, octaphenylcyclotetrasiloxane, decamethylcyclopentaandoxane any or several arbitrarily; Containing the organo silane coupling agent of ring body structurc, as rigid radical, can improve hardness intensity and the heatproof weather resistance of emulsion.
Described emulsifying agent is: alkylphenol polyoxyethylene OP series, Sulfonates anionic emulsifier, polyoxyethylene nonylphenol ether NP series, sorbitan fatty acid ester Soxylat A 25-7 Tween series, fatty alcohol-polyoxyethylene ether AEO series, sorbitan fatty acid ester Span series, sulfuric acid ester anionic emulsifier, methallyl hydroxide sodium dimercaptosulphanatein, allyloxy hydroxide sodium dimercaptosulphanatein, alkylamide vinyl sulfonic acid sodium, in sodium vinyl sulfonate reactive emulsifier any two or more with the composite mixture of any ratio,
Described persulphate is any in Potassium Persulphate, ammonium persulphate.
In step (2), under 50rpm～250rpm stirring velocity, stir 15min～40min, each component is uniformly dispersed.Too low stirring velocity is unfavorable for the dispersed of reaction system, causes reaction to occur a large amount of gels, and too high stirring velocity is unfavorable for the abundant reaction of polymerization system, causes system stability degradation.
In step (3): stir 60min～120min under 50rpm～250rpm stirring velocity, each component is uniformly dispersed.Too low stirring velocity is unfavorable for the dispersed of reaction system, causes reaction to occur a large amount of gels, and too high stirring velocity is unfavorable for the abundant reaction of polymerization system, causes system stability degradation.The present invention narrates water-based emulsion and is applying after concrete outside surface; along with the volatilization of moisture in materials, obtain curing protective layer; this protective layer provides excellent adhesion property by polyacrylic ester composition; and provide excellent weathering resistance, water resistance because of the existence of the organo-silicon coupling agent containing ring texture; thereby make protective layer keep long-lasting, can not occur peeling off because of climate reasons.
Product of the present invention has following advantage in sum:
(1) material is a kind of water-based material, the production of material and use in do not use the volatility poisonous and harmful solvents such as toluene, benzene, formaldehyde, to environmental and human health impacts without obvious harm.
(2) microtexture of material has obvious nucleocapsid structure, in material, used ring structure silane simultaneously, can effectively promote the water resistant, high temperature resistant performance of material, material also has good execution conditions and excellent use properties, the advantages such as concise production process.
(3) material has good protection, waterproof, high temperature resistant, weather resistance, has high stability and lower cost, can effectively improve the protection of external wall under high temperature and rainy condition.
accompanying drawing explanation:
Accompanying drawing 1: the emulsion particle diameter overhaul flow chart as an example of embodiment 5 example; Utilize dynamic light scattering ALV to test emulsion particle diameter, result proves that emulsion particle diameter, between 50nm ~ 200nm, has good monodispersity energy.
The nucleocapsid structure figure of the TEM transmission of accompanying drawing 2: embodiment 1, utilizes transmission electron microscope TEM to test emulsion structure, and result proves that emulsion has obvious nucleocapsid structure.
The nucleocapsid structure figure of the TEM transmission of accompanying drawing 3: embodiment 2, utilizes transmission electron microscope TEM to test emulsion structure, and result proves that emulsion has obvious nucleocapsid structure.
The nucleocapsid structure figure of the TEM transmission of accompanying drawing 4: embodiment 3, utilizes transmission electron microscope TEM to test emulsion structure, and result proves that emulsion has obvious nucleocapsid structure.
The nucleocapsid structure figure of the TEM transmission of accompanying drawing 5: embodiment 4, utilizes transmission electron microscope TEM to test emulsion structure, and result proves that emulsion has obvious nucleocapsid structure.
The nucleocapsid structure figure of the TEM transmission of accompanying drawing 6: embodiment 5, utilizes transmission electron microscope TEM to test emulsion structure, and result proves that emulsion has obvious nucleocapsid structure.
The nucleocapsid structure figure of the TEM transmission of accompanying drawing 7: embodiment 6, utilizes transmission electron microscope TEM to test emulsion structure, and result proves that emulsion has obvious nucleocapsid structure.
Embodiment
Below by embodiment, the present invention is specifically described, described embodiment is the specific descriptions to claim of the present invention just, and claim includes but not limited to described embodiment content.
Please contriver provide in existing water-based emulsion material, only there is nucleocapsid structure, only there is the water-based emulsion material of cyclosiloxane structure and the environmental protection of water-based emulsion material of the present invention, protective, the contrast of weathering resistance experimental data
Embodiment 1:
Take production material 500g of the present invention as example raw material used and preparation process thereof:
(1) prepare core emulsion: at 40 ℃, by methyl methacrylate 50g, butyl acrylate 40g, vinylformic acid-2 diethyl acetamidomalonate 15g, hydroxyethyl methylacrylate 15g monomer is slowly added drop-wise to and adds emulsifying agent 1.5gOP-10 emulsifying agent with the rate of addition of 2 drops/sec, 1.3gSpan-60 emulsifying agent, in the deionized water 50g of 1.7g sodium lauryl sulphate, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, pre-emulsion A and the deionized water 40g that adds Potassium Persulphate 4g are slowly added drop-wise in the deionized water 10g of 90 ℃ with the rate of addition of 2 drops/sec simultaneously, keep 90 ℃ of temperature dispersed with stirring, under 250rpm stirring velocity, stir 40min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 40 ℃, by methyl methacrylate 50g, butyl acrylate 60g, vinyltrimethoxy silane 10g, vinyltriethoxysilane 15g, octamethylcyclotetrasiloxane 25g, with the rate of addition of 2 drops/sec, be slowly added drop-wise to and add emulsifying agent 1.5gOP-10 emulsifying agent, 1.3gSpan-60 emulsifying agent, in the deionized water 50g of 1.7g sodium lauryl sulphate, carry out emulsification, obtain finely dispersed pre-emulsion C that can emulsion, pre-emulsion A and the deionized water 40g that adds Potassium Persulphate 3.5g are slowly added drop-wise in the core emulsion B of 90 ℃ with the rate of addition of 10 drops/sec simultaneously, keep 90 ℃ of temperature dispersed with stirring, under 250rpm stirring velocity, stir 120min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent ammoniacal liquor 0.05g, regulating the PH of nuclear-shell emulsion D is 7; To neutral emulsion D, drip the deionized water solution 10g that is dispersed with the anti-algae agent of sterilization Kathon (OIT) 0.5g, regulate the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain having the water-based emulsion of protection water resistance.
The water-based emulsion material appearance the making homogeneous latex emulsion shape that is white in color, store 6 months without precipitating without layering, 5000r/min centrifugal treating 30min is without precipitation without layering, and dilution process is without precipitating without layering, by 5.4.2 requirement in JC/T864-2008, make film sample, test sample tensile strength >=1.5MPa, elongation at break >=300%, low temperature flexibility,-20 ℃ of leakless, waterproof, within 6 months, without peeling off without skin effect phenomenon, the experiment of 75 ℃ of washing brushes of high temperature is without swelling in outdoor exposure experiment.
Embodiment 2:
Take production material 500g of the present invention as example raw material used and preparation process thereof:
(1) prepare core emulsion: at 40 ℃, by methyl methacrylate 45g, butyl acrylate 50g, butyl methacrylate 15g, hydroxyethyl methylacrylate 15g monomer is slowly added drop-wise to and adds emulsifying agent 1.8gOP-10 emulsifying agent with the rate of addition of 2～10 drops/sec, 1gSpan-80 emulsifying agent, 1.7g carry out emulsification in the deionized water 45g of sodium lauryl sulphate, obtain the pre-emulsion A of finely dispersed core emulsion, pre-emulsion A and the deionized water 50g that adds Potassium Persulphate 3g are slowly added drop-wise in the deionized water 10g of 75 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 75 ℃ of temperature dispersed with stirring, under 200rpm stirring velocity, stir 40min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 40 ℃, by methyl methacrylate 55g, butyl acrylate 55g, vinyl three ('beta '-methoxy oxyethyl group) silane 15g, vinyltriethoxysilane 10g, octamethylcyclotetrasiloxane 15g, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 10g, with the rate of addition of 5 drops/sec, be slowly added drop-wise to and add emulsifying agent 1.8gOP-10 emulsifying agent, 1gSpan-60 emulsifying agent, 1.7g carry out emulsification in the deionized water 45g of sodium lauryl sulphate, obtain finely dispersed pre-emulsion C that can emulsion, pre-emulsion A and the deionized water 43g that adds Potassium Persulphate 2.5g are slowly added drop-wise in the core emulsion B of 75 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 75 ℃ of temperature dispersed with stirring, under 150rpm stirring velocity, stir 120min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent ammoniacal liquor 0.05g, regulating the PH of nuclear-shell emulsion D is 8; To neutral emulsion D, drip the deionized water solution 10g that is dispersed with the anti-algae agent of sterilization Kathon (OIT) 0.5g, regulate the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain having the water-based emulsion of protection water resistance.
The water-based emulsion material appearance the making homogeneous latex emulsion shape that is white in color, store 6 months without precipitating without layering, 5000r/min centrifugal treating 30min is without precipitation without layering, and dilution process is without precipitating without layering, by 5.4.2 requirement in JC/T864-2008, make film sample, test sample tensile strength >=1.5MPa, elongation at break >=300%, low temperature flexibility,-20 ℃ of leakless, waterproof, within 6 months, without peeling off without skin effect phenomenon, the experiment of 75 ℃ of washing brushes of high temperature is without swelling in outdoor exposure experiment.
Embodiment 3:
Take production material 500g of the present invention as example raw material used and preparation process thereof:
(1) prepare core emulsion: at 5 ℃, by β-dimethyl-aminoethylmethacrylate 50g, ethyl propenoate 40g, vinylformic acid-2 diethyl acetamidomalonate 15g monomer is slowly added drop-wise to and adds emulsifying agent 1.5gNP-10 emulsifying agent with the rate of addition of 10 drops/sec, 1.5gSpan-60 emulsifying agent, in the deionized water 50g of 1.5g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, by pre-emulsion A and interpolation Potassium Persulphate 2g, the deionized water 40g of ammonium persulphate 2g is slowly added drop-wise in the deionized water 10g of 70 ℃ with the rate of addition of 3 drops/sec simultaneously, keep 70 ℃ of temperature dispersed with stirring, under 250rpm stirring velocity, stir 15min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 5 ℃, by methyl methacrylate 55g, ethyl propenoate 45g, butyl acrylate 20g, vinyltriethoxysilane 15g, vinyl three ('beta '-methoxy oxyethyl group) silane 10g, octamethylcyclotetrasiloxane 25g, with the rate of addition of 10 drops/sec, be slowly added drop-wise to and add emulsifying agent 1.5gNP-10 emulsifying agent, 1.5gSpan-60 emulsifying agent, in the deionized water 50g of 1.5g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain finely dispersed pre-emulsion C that can emulsion, by pre-emulsion A and interpolation Potassium Persulphate 2g, the deionized water 40g of ammonium persulphate 1.5g is slowly added drop-wise in the core emulsion B of 70 ℃ with the rate of addition of 3 drops/sec simultaneously, keep 70 ℃ of temperature dispersed with stirring, under 250rpm stirring velocity, stir 60min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent thanomin 0.05g, regulating the PH of nuclear-shell emulsion D is 7; To neutral emulsion D, drip the deionized water solution 10g that is dispersed with the anti-algae agent of sterilization Kathon (OIT) 0.5g, regulate the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain having the water-based emulsion of protection water resistance.
The water-based emulsion material appearance the making homogeneous latex emulsion shape that is white in color, store 6 months without precipitating without layering, 5000r/min centrifugal treating 30min is without precipitation without layering, and dilution process is without precipitating without layering, by 5.4.2 requirement in JC/T864-2008, make film sample, test sample tensile strength >=1.5MPa, elongation at break >=300%, low temperature flexibility,-20 ℃ of leakless, waterproof, within 6 months, without peeling off without skin effect phenomenon, the experiment of 75 ℃ of washing brushes of high temperature is without swelling in outdoor exposure experiment.
Embodiment 4:
Take production material 500g of the present invention as example raw material used and preparation process thereof:
(1) prepare core emulsion: at 5 ℃, by methyl methacrylate 45g, ethyl propenoate 45g, hydroxyethyl methylacrylate 15g monomer is slowly added drop-wise to and adds emulsifying agent 1.5gOP-15 emulsifying agent with the rate of addition of 8 drops/sec, 1.5gTwen-20 emulsifying agent, in the deionized water 50g of 1.5g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, pre-emulsion A and the deionized water 40g that adds ammonium persulphate 3g are slowly added drop-wise in the deionized water 10g of 60 ℃ with the rate of addition of 3 drops/sec simultaneously, keep 60 ℃ of temperature dispersed with stirring, under 250rpm stirring velocity, stir 15min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 5 ℃, by methyl methacrylate 45g, ethyl propenoate 45g, butyl acrylate 20g, glycidyl methacrylate 10g, vinyltrimethoxy silane 10g, vinyl three ('beta '-methoxy oxyethyl group) silane 15g, hexamethyl cyclotrisiloxane 10g, tetramethyl-tetrem alkenyl siloxane 15g is slowly added drop-wise to and adds emulsifying agent 1.5gOP-15 emulsifying agent with the rate of addition of 10 drops/sec, 1.5gTwen-20 emulsifying agent, in the deionized water 50g of 1.5g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain finely dispersed pre-emulsion C that can emulsion, by pre-emulsion A and interpolation Potassium Persulphate 2g, the deionized water 40g of ammonium persulphate 2.5g is slowly added drop-wise in the core emulsion B of 60 ℃ with the rate of addition of 3 drops/sec simultaneously, keep 60 ℃ of temperature dispersed with stirring, under 250rpm stirring velocity, stir 60min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent thanomin 0.25g, regulating the PH of nuclear-shell emulsion D is 7; To neutral emulsion D, drip and be dispersed with the anti-algae agent 4 of sterilization, the deionized water solution 10g of the chloro-Kathon of 5-bis-(DCOIT) 1.5g, regulates the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain having the water-based emulsion of protection water resistance.
The water-based emulsion material appearance the making homogeneous latex emulsion shape that is white in color, store 6 months without precipitating without layering, 5000r/min centrifugal treating 30min is without precipitation without layering, and dilution process is without precipitating without layering, by 5.4.2 requirement in JC/T864-2008, make film sample, test sample tensile strength >=1.5MPa, elongation at break >=300%, low temperature flexibility,-20 ℃ of leakless, waterproof, within 6 months, without peeling off without skin effect phenomenon, the experiment of 75 ℃ of washing brushes of high temperature is without swelling in outdoor exposure experiment.
Embodiment 5:
Take production material 500g of the present invention as example raw material used and preparation process thereof:
(1) prepare core emulsion: at 5 ℃, by β-dimethyl-aminoethylmethacrylate 30g, butyl acrylate 40g, ethyl acrylate 5g, vinyltriethoxysilane 15g, vinyl three ('beta '-methoxy oxyethyl group) silane 10g, monomer is slowly added drop-wise to and adds emulsifying agent 1gAEO-15 emulsifying agent with the rate of addition of 2 drops/sec, 1gOP-10 emulsifying agent, in the deionized water 50g of 1g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, by pre-emulsion A and interpolation Potassium Persulphate 2g, the deionized water 50g of ammonium persulphate 2g is slowly added drop-wise in the deionized water 10g of 75 ℃ with the rate of addition of 3 drops/sec simultaneously, keep 75 ℃ of temperature dispersed with stirring, under 50rpm stirring velocity, stir 40min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 5 ℃, by methyl methacrylate 25g, butyl methacrylate 45g, vinyltriethoxysilane 25g, vinyl three ('beta '-methoxy oxyethyl group) silane 25g, octamethylcyclotetrasiloxane 25g, with the rate of addition of 5 drops/sec, be slowly added drop-wise to and add emulsifying agent 1gAEO-15 emulsifying agent, 1gOP-10 emulsifying agent, in the deionized water 70g of 1g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain finely dispersed pre-emulsion C that can emulsion, by pre-emulsion A and interpolation Potassium Persulphate 2g, the deionized water 50g of ammonium persulphate 1.5g is slowly added drop-wise in the core emulsion B of 75 ℃ with the rate of addition of 2 drops/sec simultaneously, keep 75 ℃ of temperature dispersed with stirring, under 50rpm stirring velocity, stir 120min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent sodium bicarbonate 0.5g, regulating the PH of nuclear-shell emulsion D is 7; To neutral emulsion D, drip and be dispersed with the anti-algae agent 4 of sterilization, the deionized water solution 14g of the chloro-Kathon of 5-bis-(DCOIT) 3g, regulates the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain having the water-based emulsion of protection water resistance.
The water-based emulsion material appearance the making homogeneous latex emulsion shape that is white in color, store 6 months without precipitating without layering, 5000r/min centrifugal treating 30min is without precipitation without layering, and dilution process is without precipitating without layering, by 5.4.2 requirement in JC/T864-2008, make film sample, test sample tensile strength >=1.5MPa, elongation at break >=300%, low temperature flexibility,-20 ℃ of leakless, waterproof, within 6 months, without peeling off without skin effect phenomenon, the experiment of 75 ℃ of washing brushes of high temperature is without swelling in outdoor exposure experiment.
Embodiment 6:
Take production material 500g of the present invention as example raw material used and preparation process thereof:
(1) prepare core emulsion: at 25 ℃, by methyl methacrylate 30g, butyl acrylate 40g, Rocryl 410 5g, vinyltriethoxysilane 12.5g, vinyl three ('beta '-methoxy oxyethyl group) silane 12.5g, monomer is slowly added drop-wise to and adds emulsifying agent 1g methallyl hydroxide sodium dimercaptosulphanatein with the rate of addition of 5 drops/sec, 1gOP-10 emulsifying agent, in the deionized water 50g of 1g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, by pre-emulsion A and interpolation Potassium Persulphate 2g, the deionized water 50g of ammonium persulphate 2g is slowly added drop-wise in the deionized water 10g of 75 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 75 ℃ of temperature dispersed with stirring, under 100rpm stirring velocity, stir 40min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 25 ℃, by β-dimethyl-aminoethylmethacrylate 20g, butyl methacrylate 45g, vinyltriethoxysilane 25g, vinyl three ('beta '-methoxy oxyethyl group) silane 25g, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 30g, with the rate of addition of 5 drops/sec, be slowly added drop-wise to and add emulsifying agent 1g methallyl hydroxide sodium dimercaptosulphanatein, 1gOP-10 emulsifying agent, in the deionized water 70g of 1g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain finely dispersed pre-emulsion C that can emulsion, by pre-emulsion A and interpolation Potassium Persulphate 2g, the deionized water 50g of ammonium persulphate 1.5g is slowly added drop-wise in the core emulsion B of 75 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 75 ℃ of temperature dispersed with stirring, under 100rpm stirring velocity, stir 120min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent sodium bicarbonate 0.5g, regulating the PH of nuclear-shell emulsion D is 7; To neutral emulsion D, drip and be dispersed with the anti-algae agent 4 of sterilization, the deionized water solution 15g of the chloro-Kathon of 5-bis-(DCOIT) 2g, regulates the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain having the water-based emulsion of protection water resistance.
The water-based emulsion material appearance the making homogeneous latex emulsion shape that is white in color, store 6 months without precipitating without layering, 5000r/min centrifugal treating 30min is without precipitation without layering, and dilution process is without precipitating without layering, by 5.4.2 requirement in JC/T864-2008, make film sample, test sample tensile strength >=1.5MPa, elongation at break >=300%, low temperature flexibility,-20 ℃ of leakless, waterproof, within 6 months, without peeling off without skin effect phenomenon, the experiment of 75 ℃ of washing brushes of high temperature is without swelling in outdoor exposure experiment.
Embodiment 7:
Take production material 500g of the present invention as example raw material used and preparation process thereof:
(1) prepare core emulsion: at 20 ℃, by methyl methacrylate 15g, butyl acrylate 40g, Rocryl 410 5g, vinyltriethoxysilane 10g, vinyl three ('beta '-methoxy oxyethyl group) silane 5g, octamethylcyclotetrasiloxane 10g, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 10g monomer is slowly added drop-wise to and adds emulsifying agent 1g allyloxy hydroxide sodium dimercaptosulphanatein with the rate of addition of 5 drops/sec, class of 1g department 80 emulsifying agents, in the deionized water 70g of 1g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, by pre-emulsion A and interpolation Potassium Persulphate 2g, the deionized water 50g of ammonium persulphate 2g is slowly added drop-wise in the deionized water 10g of 72 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 72 ℃ of temperature dispersed with stirring, under 150rpm stirring velocity, stir 40min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 20 ℃, by β-dimethyl-aminoethylmethacrylate 20g, butyl methacrylate 45g, vinyl three ('beta '-methoxy oxyethyl group) silane 10g, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 30g, with the rate of addition of 5 drops/sec, be slowly added drop-wise to and add emulsifying agent 1g methallyl hydroxide sodium dimercaptosulphanatein, class of 1g department 80 emulsifying agents, in the deionized water 70g of 1g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain finely dispersed pre-emulsion C that can emulsion, by pre-emulsion A and interpolation Potassium Persulphate 2g, the deionized water 60g of ammonium persulphate 1.5g is slowly added drop-wise in the core emulsion B of 72 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 72 ℃ of temperature dispersed with stirring, under 150rpm stirring velocity, stir 90min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent thanomin 0.25g, regulating the PH of nuclear-shell emulsion D is 7; To neutral emulsion D, drip the deionized water solution 23.25g that is dispersed with the anti-algae agent of sterilization MIT (MIT) 1g, regulate the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain having the water-based emulsion of protection water resistance.
The water-based emulsion material appearance the making homogeneous latex emulsion shape that is white in color, store 6 months without precipitating without layering, 5000r/min centrifugal treating 30min is without precipitation without layering, and dilution process is without precipitating without layering, by 5.4.2 requirement in JC/T864-2008, make film sample, test sample tensile strength >=1.5MPa, elongation at break >=300%, low temperature flexibility,-20 ℃ of leakless, waterproof, within 6 months, without peeling off without skin effect phenomenon, the experiment of 75 ℃ of washing brushes of high temperature is without swelling in outdoor exposure experiment.
Embodiment 8:
Take production material 500g of the present invention as example raw material used and preparation process thereof:
(1) prepare core emulsion: at 20 ℃, by methyl methacrylate 15g, butyl acrylate 35g, vinyltriethoxysilane 10g, vinyl three ('beta '-methoxy oxyethyl group) silane 5g, octamethylcyclotetrasiloxane 10g, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 10g monomer is slowly added drop-wise to and adds emulsifying agent 1g alkylamide vinyl sulfonic acid sodium with the rate of addition of 5 drops/sec, 1g sodium vinyl sulfonate, in the deionized water 70g of 1g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, by pre-emulsion A and interpolation Potassium Persulphate 0.5g, the deionized water 65g of ammonium persulphate 0.25g is slowly added drop-wise in the deionized water 10g of 78 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 78 ℃ of temperature dispersed with stirring, under 150rpm stirring velocity, stir 40min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 20 ℃, by β-dimethyl-aminoethylmethacrylate 15g, butyl methacrylate 35g, vinyl three ('beta '-methoxy oxyethyl group) silane 10g, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 30g, with the rate of addition of 5 drops/sec, be slowly added drop-wise to and add emulsifying agent 1g methallyl hydroxide sodium dimercaptosulphanatein, 1g sodium vinyl sulfonate, in the deionized water 80g of 1g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain finely dispersed pre-emulsion C that can emulsion, by pre-emulsion A and interpolation Potassium Persulphate 0.5g, the deionized water 70g of ammonium persulphate 0.25g is slowly added drop-wise in the core emulsion B of 78 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 78 ℃ of temperature dispersed with stirring, under 150rpm stirring velocity, stir 90min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent ammoniacal liquor 0.5g, regulating the PH of nuclear-shell emulsion D is 7; To neutral emulsion D, drip the deionized water solution 20g that is dispersed with the anti-algae agent of sterilization MIT (MIT) 2g, regulate the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain having the water-based emulsion of protection water resistance.
The water-based emulsion material appearance the making homogeneous latex emulsion shape that is white in color, store 6 months without precipitating without layering, 5000r/min centrifugal treating 30min is without precipitation without layering, and dilution process is without precipitating without layering, by 5.4.2 requirement in JC/T864-2008, make film sample, test sample tensile strength >=1.5MPa, elongation at break >=300%, low temperature flexibility,-20 ℃ of leakless, waterproof, within 6 months, without peeling off without skin effect phenomenon, the experiment of 75 ℃ of washing brushes of high temperature is without swelling in outdoor exposure experiment.
Embodiment 9:
Take production material 500g of the present invention as example raw material used and preparation process thereof:
(1) prepare core emulsion: at 15 ℃, by methyl methacrylate 7.5g, butyl acrylate 30g, vinyltriethoxysilane 10g, vinyl three ('beta '-methoxy oxyethyl group) silane 5g, octamethylcyclotetrasiloxane 10g, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 10g monomer is slowly added drop-wise to and adds emulsifying agent 1g alkylamide vinyl sulfonic acid sodium with the rate of addition of 5 drops/sec, 1g allyloxy hydroxide sodium dimercaptosulphanatein, in the deionized water 60g of 1g sodium laurylsulfonate, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, by pre-emulsion A and interpolation Potassium Persulphate 0.5g, the deionized water 75g of ammonium persulphate 0.25g is slowly added drop-wise in the deionized water 10g of 78 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 78 ℃ of temperature dispersed with stirring, under 150rpm stirring velocity, stir 40min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 15 ℃, by β-dimethyl-aminoethylmethacrylate 7.5g, butyl acrylate 30g, vinyl three ('beta '-methoxy oxyethyl group) silane 10g, octamethylcyclotetrasiloxane 10g, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 20g, with the rate of addition of 5 drops/sec, be slowly added drop-wise to and add emulsifying agent 1g allyloxy hydroxide sodium dimercaptosulphanatein, 1g sodium vinyl sulfonate, in the deionized water 80g of 1g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain finely dispersed pre-emulsion C that can emulsion, by pre-emulsion A and interpolation Potassium Persulphate 0.5g, the deionized water 70g of ammonium persulphate 0.25g is slowly added drop-wise in the core emulsion B of 78 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 78 ℃ of temperature dispersed with stirring, under 150rpm stirring velocity, stir 90min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent ammoniacal liquor 0.05g, regulating the PH of nuclear-shell emulsion D is 8; To neutral emulsion D, drip the deionized water solution 21.95g that is dispersed with the anti-algae agent of sterilization MIT (MIT) 0.5g, regulate the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain having the water-based emulsion of protection water resistance.
The water-based emulsion material appearance the making homogeneous latex emulsion shape that is white in color, store 6 months without precipitating without layering, 5000r/min centrifugal treating 30min is without precipitation without layering, and dilution process is without precipitating without layering, by 5.4.2 requirement in JC/T864-2008, make film sample, test sample tensile strength >=1.5MPa, elongation at break >=300%, low temperature flexibility,-20 ℃ of leakless, waterproof, within 6 months, without peeling off without skin effect phenomenon, the experiment of 75 ℃ of washing brushes of high temperature is without swelling in outdoor exposure experiment.
Embodiment 10:
Take production material 500g of the present invention as example raw material used and preparation process thereof:
(1) prepare core emulsion: at 25 ℃, by methyl methacrylate 7.5g, vinylformic acid-2 diethyl acetamidomalonate 30g, vinyltriethoxysilane 10g, vinyl trimethoxy silane 5g monomer is slowly added drop-wise to and adds emulsifying agent 1g alkylamide vinyl sulfonic acid sodium with the rate of addition of 2 drops/sec, in the deionized water 60g of 1g allyloxy hydroxide sodium dimercaptosulphanatein, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, by pre-emulsion A and interpolation Potassium Persulphate 0.75g, the deionized water 55g of ammonium persulphate 0.5g is slowly added drop-wise in the deionized water 10g of 80 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 80 ℃ of temperature dispersed with stirring, under 250rpm stirring velocity, stir 15min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 25 ℃, by β-dimethyl-aminoethylmethacrylate 7.5g, vinylformic acid-2 diethyl acetamidomalonate 30g, vinyltriethoxysilane 5g, vinyltrimethoxy silane, 5g, octamethylcyclotetrasiloxane 15g, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 10g, with the rate of addition of 5 drops/sec, be slowly added drop-wise to and add emulsifying agent 1g allyloxy hydroxide sodium dimercaptosulphanatein, in the deionized water 80g of 1g sodium vinyl sulfonate, carry out emulsification, obtain finely dispersed pre-emulsion C that can emulsion, by pre-emulsion A and interpolation Potassium Persulphate 0.75g, the deionized water 66g of ammonium persulphate 0.5g is slowly added drop-wise in the core emulsion B of 80 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 80 ℃ of temperature dispersed with stirring, under 150rpm stirring velocity, stir 120min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent ammoniacal liquor 0.5g, regulating the PH of nuclear-shell emulsion D is 8; To neutral emulsion D, drip the deionized water solution 21.5g that is dispersed with the anti-algae agent of sterilization palmityl trimethyl ammonium chloride 0.5g, regulate the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain having the water-based emulsion of protection water resistance.
The water-based emulsion material appearance the making homogeneous latex emulsion shape that is white in color, store 6 months without precipitating without layering, 5000r/min centrifugal treating 30min is without precipitation without layering, and dilution process is without precipitating without layering, by 5.4.2 requirement in JC/T864-2008, make film sample, test sample tensile strength >=1.5MPa, elongation at break >=300%, low temperature flexibility,-20 ℃ of leakless, waterproof, within 6 months, without peeling off without skin effect phenomenon, the experiment of 75 ℃ of washing brushes of high temperature is without swelling in outdoor exposure experiment.
Embodiment 11:
Take production material 500g of the present invention as example raw material used and preparation process thereof:
(1) prepare core emulsion: at 25 ℃, by butyl methacrylate 9g, vinylformic acid-2 diethyl acetamidomalonate 30g, vinyltriethoxysilane 12.5g, vinyl trimethoxy silane 17.5g monomer is slowly added drop-wise to and adds emulsifying agent 0.5gOP-10 with the rate of addition of 2 drops/sec, 0.4gSpan60, 0.6gTwen60, in the deionized water 50g of 1g allyloxy hydroxide sodium dimercaptosulphanatein, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, by pre-emulsion A and interpolation Potassium Persulphate 0.75g, the deionized water 50g of ammonium persulphate 0.5g is slowly added drop-wise in the deionized water 10g of 80 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 80 ℃ of temperature dispersed with stirring, under 250rpm stirring velocity, stir 15min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 25 ℃, by β-dimethyl-aminoethylmethacrylate 6g, vinylformic acid-2 diethyl acetamidomalonate 30g, vinyltriethoxysilane 18g, vinyltrimethoxy silane 22g, octamethylcyclotetrasiloxane 15g, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 10g, with the rate of addition of 5 drops/sec, be slowly added drop-wise to and add emulsifying agent 0.5gOP-10, 0.4gSpan60, 0.6gTwen60, in the deionized water 60g of 1g sodium vinyl sulfonate, carry out emulsification, obtain finely dispersed pre-emulsion C that can emulsion, by pre-emulsion A and interpolation Potassium Persulphate 0.75g, the deionized water 55g of ammonium persulphate 0.5g is slowly added drop-wise in the core emulsion B of 75 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 75 ℃ of temperature dispersed with stirring, under 150rpm stirring velocity, stir 120min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent ammoniacal liquor 0.5g, regulating the PH of nuclear-shell emulsion D is 8; To neutral emulsion D, drip the deionized water solution 17.5g that is dispersed with the anti-algae agent of sterilization palmityl trimethyl ammonium chloride 0.5g, regulate the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain having the water-based emulsion of protection water resistance.
The water-based emulsion material appearance the making homogeneous latex emulsion shape that is white in color, store 6 months without precipitating without layering, 5000r/min centrifugal treating 30min is without precipitation without layering, and dilution process is without precipitating without layering, by 5.4.2 requirement in JC/T864-2008, make film sample, test sample tensile strength >=1.5MPa, elongation at break >=300%, low temperature flexibility,-20 ℃ of leakless, waterproof, within 6 months, without peeling off without skin effect phenomenon, the experiment of 75 ℃ of washing brushes of high temperature is without swelling in outdoor exposure experiment.
Embodiment 12:
Take production material 500g of the present invention as example raw material used and preparation process thereof:
(1) prepare core emulsion: at 25 ℃, by methyl methacrylate 6g, vinylformic acid-2 diethyl acetamidomalonate 30g, vinyltriethoxysilane 10g, vinyl trimethoxy silane 5g monomer is slowly added drop-wise to and adds emulsifying agent 0.4gNP10 with the rate of addition of 2 drops/sec, 0.4gSpan80, 0.7gTwen80, in the deionized water 60g of 1g sodium laurylsulfonate, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, by pre-emulsion A and interpolation Potassium Persulphate 0.75g, the deionized water 55g of ammonium persulphate 0.5g is slowly added drop-wise in the deionized water 10g of 80 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 80 ℃ of temperature dispersed with stirring, under 250rpm stirring velocity, stir 15min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 25 ℃, by β-dimethyl-aminoethylmethacrylate 9g, vinylformic acid-2 diethyl acetamidomalonate 30g, vinyltriethoxysilane 5g, vinyltrimethoxy silane, 5g, octamethylcyclotetrasiloxane 15g, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 10g, with the rate of addition of 5 drops/sec, be slowly added drop-wise to and add emulsifying agent 0.4gNP10, 0.4gSpan80, 0.7gTwen80, in the deionized water 80g of 1g sodium laurylsulfonate, carry out emulsification, obtain finely dispersed pre-emulsion C that can emulsion, by pre-emulsion A and interpolation Potassium Persulphate 0.75g, the deionized water 66g of ammonium persulphate 0.5g is slowly added drop-wise in the core emulsion B of 80 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 80 ℃ of temperature dispersed with stirring, under 150rpm stirring velocity, stir 120min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent ammoniacal liquor 0.5g, regulating the PH of nuclear-shell emulsion D is 8; To neutral emulsion D, drip the deionized water solution 21.5g that is dispersed with the anti-algae agent of sterilization palmityl trimethyl ammonium chloride 0.5g, regulate the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain having the water-based emulsion of protection water resistance.
The water-based emulsion material appearance the making homogeneous latex emulsion shape that is white in color, store 6 months without precipitating without layering, 5000r/min centrifugal treating 30min is without precipitation without layering, and dilution process is without precipitating without layering, by 5.4.2 requirement in JC/T864-2008, make film sample, test sample tensile strength >=1.5MPa, elongation at break >=300%, low temperature flexibility,-20 ℃ of leakless, waterproof, within 6 months, without peeling off without skin effect phenomenon, the experiment of 75 ℃ of washing brushes of high temperature is without swelling in outdoor exposure experiment.
Comparative example 1:
Take too low stirring velocity production material 500g of the present invention as example raw material used and preparation process thereof:
(1) prepare core emulsion: at 25 ℃, by butyl methacrylate 9g, vinylformic acid-2 diethyl acetamidomalonate 30g, vinyltriethoxysilane 12.5g, vinyl trimethoxy silane 17.5g monomer is slowly added drop-wise to and adds emulsifying agent 0.5gOP-10 with the rate of addition of 2 drops/sec, 0.4gSpan60, 0.6gTwen60, in the deionized water 50g of 1g allyloxy hydroxide sodium dimercaptosulphanatein, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, by pre-emulsion A and interpolation Potassium Persulphate 0.75g, the deionized water 50g of ammonium persulphate 0.5g is slowly added drop-wise in the deionized water 10g of 80 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 80 ℃ of temperature dispersed with stirring, under 40rpm stirring velocity, stir 15min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 25 ℃, by β-dimethyl-aminoethylmethacrylate 6g, vinylformic acid-2 diethyl acetamidomalonate 30g, vinyltriethoxysilane 18g, vinyltrimethoxy silane 22g, octamethylcyclotetrasiloxane 15g, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 10g, with the rate of addition of 5 drops/sec, be slowly added drop-wise to and add emulsifying agent 0.5gOP-10, 0.4gSpan60, 0.6gTwen60, in the deionized water 60g of 1g sodium vinyl sulfonate, carry out emulsification, obtain finely dispersed pre-emulsion C that can emulsion, by pre-emulsion A and interpolation Potassium Persulphate 0.75g, the deionized water 55g of ammonium persulphate 0.5g is slowly added drop-wise in the core emulsion B of 75 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 75 ℃ of temperature dispersed with stirring, under 40rpm stirring velocity, stir 120min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent ammoniacal liquor 0.5g, regulating the PH of nuclear-shell emulsion D is 8; To neutral emulsion D, drip the deionized water solution 17.5g that is dispersed with the anti-algae agent of sterilization palmityl trimethyl ammonium chloride 0.5g, regulate the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain water-based emulsion.
, all there are a large amount of gels in reactions steps (1) and (2) in the water-based emulsion material appearance the making emulsion form that is white in color, places and within one week, there will be precipitated and separated phenomenon, and film can not meet protection waterproof requirement.
Comparative example 2:
Take too high stirring velocity production material 500g of the present invention as example raw material used and preparation process thereof:
(1) prepare core emulsion: at 25 ℃, by butyl methacrylate 9g, vinylformic acid-2 diethyl acetamidomalonate 30g, vinyltriethoxysilane 12.5g, vinyl trimethoxy silane 17.5g monomer is slowly added drop-wise to and adds emulsifying agent 0.5gOP-10 with the rate of addition of 2 drops/sec, 0.4gSpan60, 0.6gTwen60, in the deionized water 50g of 1g allyloxy hydroxide sodium dimercaptosulphanatein, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, by pre-emulsion A and interpolation Potassium Persulphate 0.75g, the deionized water 50g of ammonium persulphate 0.5g is slowly added drop-wise in the deionized water 10g of 80 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 80 ℃ of temperature dispersed with stirring, under 300rpm stirring velocity, stir 15min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 25 ℃, by β-dimethyl-aminoethylmethacrylate 6g, vinylformic acid-2 diethyl acetamidomalonate 30g, vinyltriethoxysilane 18g, vinyltrimethoxy silane 22g, octamethylcyclotetrasiloxane 15g, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 10g, with the rate of addition of 5 drops/sec, be slowly added drop-wise to and add emulsifying agent 0.5gOP-10, 0.4gSpan60, 0.6gTwen60, in the deionized water 60g of 1g sodium vinyl sulfonate, carry out emulsification, obtain finely dispersed pre-emulsion C that can emulsion, by pre-emulsion A and interpolation Potassium Persulphate 0.75g, the deionized water 55g of ammonium persulphate 0.5g is slowly added drop-wise in the core emulsion B of 75 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 75 ℃ of temperature dispersed with stirring, under 300rpm stirring velocity, stir 120min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent ammoniacal liquor 0.5g, regulating the PH of nuclear-shell emulsion D is 8; To neutral emulsion D, drip the deionized water solution 17.5g that is dispersed with the anti-algae agent of sterilization palmityl trimethyl ammonium chloride 0.5g, regulate the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain water-based emulsion.
The water-based emulsion material appearance the making emulsion form that is white in color, places one week or 5000r/min centrifugal treating 30min there will be precipitated and separated phenomenon, and film can not meet protection waterproof requirement.
Comparative example 3
The water-based emulsion material 500g that only has nucleocapsid structure take preparation is as the needed raw material of example and preparation process:
(1) prepare core emulsion: at 25 ℃, by β-dimethyl-aminoethylmethacrylate 30g, butyl acrylate 60g, ethyl acrylate 5g, monomer is slowly added drop-wise to and adds emulsifying agent 1gAEO-15 emulsifying agent with the rate of addition of 2 drops/sec, 1gOP-10 emulsifying agent, in the deionized water 50g of 1g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, by pre-emulsion A and interpolation Potassium Persulphate 2g, the deionized water 75g of ammonium persulphate 2g is slowly added drop-wise in the deionized water 10g of 75 ℃ with the rate of addition of 3 drops/sec simultaneously, keep 75 ℃ of temperature dispersed with stirring, under 50rpm stirring velocity, stir 40min, each component is uniformly dispersed, obtain core emulsion B,
(2) prepare nuclear-shell emulsion: at 25 ℃, by methyl methacrylate 25g, butyl methacrylate 75g, with the rate of addition of 5 drops/sec, be slowly added drop-wise to and add emulsifying agent 1gAEO-15 emulsifying agent, 1gOP-10 emulsifying agent, in the deionized water 70g of 1g Sodium dodecylbenzene sulfonate, carry out emulsification, obtain finely dispersed pre-emulsion C that can emulsion, by pre-emulsion A and interpolation Potassium Persulphate 2g, the deionized water 75g of ammonium persulphate 1.5g is slowly added drop-wise in the core emulsion B of 75 ℃ with the rate of addition of 2 drops/sec simultaneously, keep 75 ℃ of temperature dispersed with stirring, under 50rpm stirring velocity, stir 120min, each component is uniformly dispersed.Obtain nuclear-shell emulsion D; In emulsion D, drip PH conditioning agent sodium bicarbonate 0.5g, regulating the PH of nuclear-shell emulsion D is 7; To neutral emulsion D, drip and be dispersed with the anti-algae agent 4 of sterilization, the deionized water solution 14g of the chloro-Kathon of 5-bis-(DCOIT) 3g, regulates the sterilization and anticorrosion performance of neutral emulsion D to excellent; Thereby obtain having the water-based emulsion of protection water resistance.
The water-based emulsion material appearance the making homogeneous latex emulsion shape that is white in color, film water resistance after outdoor exposure one month declines, and 48h water-intake rate exceedes 10%, can not meet high performance protection waterproof requirement.
Comparative example 4
The water-based emulsion material 500g that only has cyclosiloxane structure take preparation is as the needed raw material of example and preparation process:
At (1) 25 ℃, by methyl methacrylate 60g, vinylformic acid-2 diethyl acetamidomalonate 50g, butyl acrylate 80g, vinyltriethoxysilane 12.5g, tetrem thiazolinyl cyclotetrasiloxane 17.5g monomer is slowly added drop-wise to and adds emulsifying agent 1gOP-10 with the rate of addition of 2 drops/sec, 0.8gSpan60, 1.2gTwen60, in the deionized water 150g of 2g allyloxy hydroxide sodium dimercaptosulphanatein, carry out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, by pre-emulsion A and interpolation Potassium Persulphate 1.5g, the deionized water 100g of ammonium persulphate 1g is slowly added drop-wise in the deionized water 22.5g of 80 ℃ with the rate of addition of 5 drops/sec simultaneously, keep 80 ℃ of temperature dispersed with stirring, under 250rpm stirring velocity, stir 15min, each component is uniformly dispersed, obtain core emulsion B,
The water-based emulsion material appearance the making homogeneous latex emulsion shape that is white in color, the quite water-based emulsion material of nucleocapsid structure, its emulsion particle diameter wider distribution, grain size is larger, and package stability is poor, stores 3 months or high-temperature storage 30d there will be demixing phenomenon.
Claims (9)
1. for an environment-protecting type water emulsion for external wall protection, it is characterized in that: by weight percentage, its composition comprises:
Core-shell latex particles: 25.6% ~ 74.5%;
The anti-algae agent of sterilization: 0.1%～0.6%;
PH conditioning agent: 0.01%～0.1%;
Deionized water: surplus;
The kernel of described core-shell latex particles is polyacrylic ester or acrylate and the polymer that contains the organo silane coupling agent of ring texture, shell is polyacrylic ester or acrylate and the polymer that contains the organo silane coupling agent of ring texture, the proportional range in the function monomer of composition kernel with the polymer monomer of high glass-transition temperature and the polymer monomer of lower glass transition temperatures is 4:6 ~ 8:2, in the function monomer of composition shell, there is the polymer monomer of high glass-transition temperature and the polymer monomer proportional range of lower glass transition temperatures is 7:3 ~ 4:6, the repertoire monomer of composition kernel is 3:7 ~ 7:3 with the proportional range of the repertoire monomer of composition shell, the particle diameter of described core-shell latex particles is 50nm ~ 200nm,
The anti-algae agent of described sterilization is Kathon (OIT), 4, the chloro-Kathon of 5-bis-(DCOIT), MIT (MIT), 1,2-benzisothiazole-3-ketone (BIT), CMIT (CIT), 2-methyl-4, any one in 5-propylidene-4-isothiazoline-3-ketone (MTI) or quaternary ammonium salt;
Described pH adjusting agent is thanomin phosphoric acid ester, N-(3-aminopropyl) diethanolamine, ammoniacal liquor, thanomin or sodium bicarbonate.
2. the preparation method of the environment-protecting type water emulsion protecting for external wall described in claim 1, is characterized in that comprising the steps:
(1) prepare starting material, described starting material, in weight fraction, comprising:
Acrylate monomer 15% ~ 45%;
Containing the organo silane coupling agent 5%～15% of unsaturated double-bond;
Ring structure organo silane coupling agent 5%～10%;
Emulsifying agent 0.3%～3%;
Persulphate 0.3% ~ 1.5%
The anti-algae agent 0.1%～0.6% of sterilization
PH adjusting agent 0.01%～0.1%
Deionized water surplus;
(2) prepare core emulsion: at 5 ℃～40 ℃, acrylate monomer is added drop-wise in the deionized water that adds emulsifying agent and carries out emulsification, obtain the pre-emulsion A of finely dispersed core emulsion, by pre-emulsion A with add the deionized water of persulphate and be added drop-wise to simultaneously in the deionized water of 60 ℃～90 ℃, keep 60 ℃～90 ℃ temperature dispersed with stirring, obtain core emulsion B;
(3) prepare nuclear-shell emulsion: at 5 ℃～40 ℃, by acrylate monomer, containing the organo silane coupling agent of unsaturated double-bond, be added drop-wise in the deionized water that adds emulsifying agent and carry out emulsification containing the organo silane coupling agent of ring body structurc, obtain finely dispersed pre-emulsion C that can emulsion
By pre-emulsion A with add the deionized water of persulphate and be added drop-wise to simultaneously in the core emulsion B of 60 ℃～90 ℃, keep 60 ℃～90 ℃ temperature dispersed with stirring, obtain nuclear-shell emulsion D;
In emulsion D, drip PH conditioning agent, the PH that regulates nuclear-shell emulsion D is neutral;
To neutral emulsion D, drip the deionized water solution that is dispersed with the anti-algae agent of sterilization, regulate the sterilization and anticorrosion performance of neutral emulsion D to antibiotic rate >=99%; Thereby obtain having the water-based emulsion of protection water resistance.
3. method according to claim 2, is characterized in that: described acrylate monomer is selected from: any in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, Octyl acrylate, ethyl acrylate, (methyl) glycidyl acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate or several arbitrarily.
4. method according to claim 2, is characterized in that: the described organo silane coupling agent containing unsaturated double-bond be selected from vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane any or several arbitrarily.
5. method according to claim 2, is characterized in that: the described organo silane coupling agent containing ring body structurc comprise in hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, octaphenylcyclotetrasiloxane, decamethylcyclopentaandoxane any or several arbitrarily.
6. method according to claim 2, it is characterized in that: described emulsifying agent is: alkylphenol polyoxyethylene OP series, Sulfonates anionic emulsifier, polyoxyethylene nonylphenol ether NP series, sorbitan fatty acid ester Soxylat A 25-7 Tween series, fatty alcohol-polyoxyethylene ether AEO series, sorbitan fatty acid ester Span series, sulfuric acid ester anionic emulsifier, methallyl hydroxide sodium dimercaptosulphanatein, allyloxy hydroxide sodium dimercaptosulphanatein, alkylamide vinyl sulfonic acid sodium, in sodium vinyl sulfonate reactive emulsifier any two or more with the composite mixture of any ratio.
7. method according to claim 2, is characterized in that: described persulphate is any in Potassium Persulphate, ammonium persulphate.
8. method according to claim 2, is characterized in that, in step (2), under 50rpm～250rpm stirring velocity, stirring 15min～40min, and each component is uniformly dispersed.
9. method according to claim 2, is characterized in that in step (3): under 50rpm～250rpm stirring velocity, stir 60min～120min, each component is uniformly dispersed.
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