CN1613882A - High performance silicon emulsion and its preparation - Google Patents
High performance silicon emulsion and its preparation Download PDFInfo
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- CN1613882A CN1613882A CN 200410066362 CN200410066362A CN1613882A CN 1613882 A CN1613882 A CN 1613882A CN 200410066362 CN200410066362 CN 200410066362 CN 200410066362 A CN200410066362 A CN 200410066362A CN 1613882 A CN1613882 A CN 1613882A
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Abstract
This invention relates to high performance of silicon emulsion and its production. It is prepared from octaalkyl cyclotetrasiloxane and octavinyl cyclotetrasiloxane mixed monomer, and acrylic acid monomer acted with catalyst, initiator, emusifier and pH regulator. Its process includes polymerizing seed emulsion, polymerizing nucleic emulsion, and polymerizing nucleic shell silicon emulsion. It has uniformly sized particles and is stable quality and production. Coatings with it are waterproof, weatherproof, washing resistant and stain-resistant.
Description
Technical field
The present invention relates to a kind of organosilicon-ACRYLIC EMULSION and production method thereof.
Background technology
At present coating in the world is made of three big series with the polymer emulsion kind, promptly vinyl acetate between to for plastic equal/copolymer emulsion series, (methyl) vinylformic acid (pure third) copolymer emulsion, and styrene/acrylic acid co-polymer emulsion.Acrylic polymers becomes the outstanding person with its superior film-forming properties, good oil-proofness and weathering resistance, good cementability in numerous polymer emulsion products.Because the membrane formation mechanism of emulsion has determined the ageing resistance of emulsion paint and contamination resistance all not ideal enough, therefore, compares with solvent based coating, widely used water-based (emulsion) coating property gap is bigger on the market.
The gordian technique of emulsion coatings replace solvents type coating is the challenge of performances such as hardness of film and weathering resistance, and this is the target that the ordinary emulsion product is difficult to realize.For this reason, the research of organosilicon-modified acrylate base polymer becomes a big focus.The synthesized polymer material that organosilicon mainly alternately is made up of Siliciumatom and Sauerstoffatom etc. has concurrently organic and performance inorganics, has good high-low temperature resistant, UV resistant and ir radiation, resistance to oxidation degraded and electrical insulating property and elasticity.The method of modification has two kinds of physical blending method and chemical reaction modifications, and the product of chemical modification is better than simple physical blending modification.Chemical modification mainly is to introduce active functional group on the end of the siloxane chain of organosilicon flexibility or side group, combines with other polymers and generates block, grafting or interpenetrating network copolymer.
The history of letex polymerization is year surplus in the of existing 80 so far.At present, except conventional emulsion polymerization, also have multiple technologies such as seeded emulsion polymerization, core-shell emulsion polymerization, emulsifier-free emulsion polymerization, micro-emulsion polymerization, ultra micro letex polymerization, inverse emulsion polymerization, conversed phase micro emulsion copolymerization, super-thick emulsion polymerization, dispersion polymerization.According to the report of document, the main mode of the preparation of organosilicon-acrylic resin emulsion is to adopt radical polymerization (the Japanese DAINIPPON INK ﹠amp of unsaturated double-bond; CHEMICALS company, calendar year 2001, U.S. Pat 2002065362; Germany BASF COATINGS AG company, 2000, German patent DE 10018601; Japan NIPPONPAINT company limited, 1997, Japanese Patent JP11090325), obtain organosilicon-acrylic resin emulsion by the unsaturated double-bond generation polymerization in unsaturated double-bond in the acrylic molecules and the organosilicon molecule.But the organosilane monomer kind is more, has complicated chemical reaction in water-based system.Such as, hydrolytic condensation takes place in organo-siloxane monomer easily that contain methoxyl group and oxyethyl group in water, and causes the pH value variation of system, and the organosilane monomer that contains vinyl has the tendency of autohemagglutination in letex polymerization.Therefore, organosilicon crylic acid latex polymeric technique controlling difficulty is bigger, is more difficult to get the regular product of paradigmatic structure.
The emulsion that adopts the conventional emulsion polymerization method to obtain need guarantee hardness of film relatively stable when envrionment conditions changes (so can reduce dust adhesion) by improving second-order transition temperature usually.Yet, use the emulsion preparation exterior coating of high Tg value to have some negative issues, as: the film process of this type of exterior coating has very big dependency to the furtherance film, and the use of the volume of furtherance film is disadvantageous to environment protection.
Core-shell emulsion polymerization can change the emulsion particle structure under the prerequisite that does not change emulsion monomer composition, thereby improves emulsion property.The maximum difference of the emulsion that core-shell emulsion polymerization and conventional emulsion polymerization obtain is: the anti-after tackiness of the emulsion that core-shell emulsion polymerization obtains is good, minimum film-forming temperature is low, better film-forming properties, stability and more superior mechanical property.
Core-shell emulsion polymerization can telomerized polymer the Tg value, i.e. the hardness of telomerized polymer film, and bring internal plasticization for system; Have different reactive groups by introducing, the monomer as carboxyl, hydroxyl, phenol amido etc. can bring polymeric film some specific physicomechanical properties.
Summary of the invention
For this reason, the present invention provides a kind of building coating organosilicon crylic acid latex and production method thereof.Adopt the organosilicon mix monomer of a certain proportion of eight vinyl cyclotetrasiloxanes and eight alkyl cyclotetrasiloxanes, under catalyzer and initiator effect, use emulsifying agent, pH regulator agent etc., adopt hud polymerization technology, make the double-bond polymerization of open loop of siloxanes ring body and Acrylic Acid Monomer, it is even to obtain particle diameter, good stability, glued membrane water tolerance height, the organosilicon crylic acid latex that ageing resistance is good.Silicon third exterior wall latex paint with this emulsion preparation has excellent ageing resistance, contamination resistance.
Organosilicon crylic acid latex of the present invention is the product that is formed by core-shell emulsion polymerization by organosilicon mix monomer and Acrylic Acid Monomer, wherein: the organosilicon mix monomer by eight vinyl cyclotetrasiloxanes and eight alkyl cyclotetrasiloxanes with 1-3: 1 weight ratio is formed, and the alkyl of eight alkyl cyclotetrasiloxanes is C
1-C
4Acrylic Acid Monomer is one or more the mixture that is selected from vinylformic acid, methacrylic acid, methyl methacrylate, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate or the Isooctyl acrylate monomer.The structural formula complexity of this polymkeric substance, the structure of this emulsion dispersion micelle can be represented by the formula:
R is C in the formula
1～C
4Alkyl, R
1Be the polymkeric substance of Acrylic Acid Monomer, n=5～10.
The production method of high performance silicon emulsion of the present invention
Emulsion employing seed emulsion is basic pre-emulsified core-shell emulsion polymerization production method in the silicon of the present invention, and this production method comprises three steps: the first step is earlier by the cross-linked polymer of Acrylic Acid Monomer letex polymerization generation as seed, i.e. seed emulsion; Second step was to carry out polymerization crosslinking with Acrylic Acid Monomer again on the surface of seed emulsion particle, was the polymerization of nuclear emulsion, thus the product nucleus structural sheet; The 3rd step was to continue to carry out polymerization crosslinking again at nuclear structure laminar surface and Acrylic Acid Monomer and organosilane monomer, generated a kind of new shell structure layer, was the polymerization of nucleocapsid organosilicon crylic acid latex.The processing condition of three steps are as follows:
The polymerization of the first step seed emulsion
Acrylic Acid Monomer carries out letex polymerization under initiator and emulsifying agent effect, promptly get seed emulsion.The viscosity of resulting seed emulsion is 1.0～1000mPas, and second-order transition temperature Tg is 5～15, and molecular weight is 100～500.In this reaction, the weight % content of reactant each component is as follows:
Component weight %
Acrylic Acid Monomer 5～25
Emulsifying agent 2～8
Initiator 0.1～1.0
Molecular weight regulator 0.02～0.2
PH regulator agent 0.01～0.1
Deionized water 70～90
65～85 ℃ of temperature of reaction, 30～60 minutes reaction times;
Wherein, the pH regulator agent is to be selected from SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic or sodium bicarbonate.
The polymerization of the second step nuclear emulsion
Above-mentioned seed emulsion and Acrylic Acid Monomer are carried out letex polymerization again, promptly obtain examining emulsion, the viscosity of resulting nuclear emulsion is 1.0～1000mPas, and second-order transition temperature Tg is 10～20, and molecular weight is 300～3000.In this emulsion polymerization, the weight % content of reactant each component is as follows:
Component weight %
Seed emulsion 35～55
Acrylic Acid Monomer 30～50
Emulsifying agent 0.4～2.0
Initiator 0.02～0.2
Molecular weight regulator 0.01～0.1
Deionized water 9～15
65～95 ℃ of temperature of reaction, 0.5～3.5 hour reaction times.
The polymerization of the 3rd step nucleocapsid organosilicon crylic acid latex
Above-mentioned nuclear emulsion and Acrylic Acid Monomer and organosilicon mix monomer are carried out letex polymerization, and 80～90 ℃ of temperature of reaction reaction times 4-8 hour, obtain the nucleocapsid organosilicon crylic acid latex.The weight % content of reactant each component is as follows:
Component weight %
Nuclear emulsion 53～56
Acrylic Acid Monomer 24～30
Organosilicon mix monomer 2.5～5.0
Catalyzer 0.001～0.01
Emulsifying agent 0.2～1.0
Initiator 0.02～0.2
Molecular weight regulator 0.04～0.2
Hydrolysis inhibitor 0.05～0.5
Mould inhibitor 0.05～0.5
PH regulator agent 0.2～2.0
Deionized water 8～11
Wherein: the organosilicon mix monomer by eight vinyl cyclotetrasiloxanes and eight alkyl cyclotetrasiloxanes with 1-3: 1 weight ratio is formed, and the alkyl of eight alkyl cyclotetrasiloxanes is C
1-C
4
Catalyzer is to be selected from potassium hydroxide, sodium hydroxide or triethylamine.
Hydrolysis inhibitor is to be selected from butyl glycol ether, propylene glycol or propylene glycol monobutyl ether.
The pH regulator agent is to be selected from sodium bicarbonate, ammoniacal liquor or 2-amino-2-methyl-1-propanol.
Mould inhibitor is to be selected from isothiazole miaow ketone, 2-methyl-4-isothiazole miaow-3-ketone or daconil M.
In above-mentioned three-step reaction:
Acrylic Acid Monomer is one or more the mixture that is selected from vinylformic acid, methacrylic acid, methyl methacrylate, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate or the Isooctyl acrylate monomer.
Emulsifying agent is one or more the mixture that is selected from sodium lauryl sulphate, nonylphenol polyethylene ether or the alkylphenol polyvinyl ether phosphoric acid ester.
Initiator is to be selected from ammonium persulphate, Potassium Persulphate or dicumyl peroxide.
Molecular weight regulator is to be selected from uncle's DDM dodecyl mercaptan, uncle's lauric acid alcohol or three-sulfonium base propyl alcohol.
The three-step reaction of production method of the present invention can carry out in same reactor continuously, and is therefore easy to operate, save energy.Gained organosilicon crylic acid latex outward appearance exquisiteness is crossed 200 eye mesh screens and is not had condensation product, and the latex particle size of size distribution test shows 99% is below 0.25 μ m.After tested, every index performance of this organosilicon crylic acid latex is as follows:
| Interventions Requested | Experiment condition and method standard | Assay |
| Outward appearance pH value molecular weight viscosity, Pas second-order transition temperature minimum film-forming temperature, ℃ Calcium ion stability mechanical stability dilution stability solids content, % | Range estimation pH test paper GB2794-81 GB/T9267-88 48h, 5% calcium chloride solution, 4000 commentaries on classics/min, 30min 72h, 110 ℃ ± 2 ℃ of 3% concentration, 2h GB/T1725-79 (89) | The milky white liquid 6 of little blueness～10 1 * 10 3～2×10 40.2～2.0 5～30 5～30 no layerings, there is not precipitation, there is not the no layering of flocculation, there is not precipitation, there is not the no layering of flocculation, do not have precipitation, do not have flocculation 49-52 |
After the film forming, glued membrane is transparent under standard conditions for this organosilicon crylic acid latex, and has excellent water tolerance: glued membrane soaks in water did not have the whiting sign in 30 days.
Adopt organosilicon crylic acid latex of the present invention, can be mixed with exterior wall latex paint, metal anti-corrosion paint etc. routinely.For example adopt organosilicon crylic acid latex of the present invention, methodology can make versicolor silicon third exterior wall latex paint through high speed dispersion routinely.According to GB9755-2001 testing standard test, this exterior wall latex paint: abrasion resistance, pass through for 10000 times; Anti-1000h temper(ing), efflorescence: 0 grade; Variable color: 1 grade.
Production method of the present invention is to adopt pre-emulsification technology to have the polymerization technique of nucleocapsid structure, and be characterized in: temperature of reaction is stablized easy to control, and latex particle is evenly distributed, and emulsification dosage can reduce, but soft, stone shell regulated at will can be improved emulsion property greatly.
In the core-shell emulsion polymerization process, add pH adjustment agent, hydrolysis inhibitor etc., synergistic effect by each component, the hydrolysis and the autohemagglutination that have suppressed organosilane monomer preferably, finally obtain particle diameter evenly (99% latex particle size is below 0.25 μ m), good stability, glued membrane water tolerance height, the organosilicon crylic acid latex that ageing resistance is good.
Organosilicon crylic acid latex of the present invention is by introducing organosilane monomer in housing, improved the second-order transition temperature of shell emulsion, because of the siloxane bond in the system has bigger bond energy and less surface energy, ageing resistance, water tolerance, contamination resistance and the abrasion resistance etc. of polymeric coating have been improved, simultaneously, in seeded emulsion polymerization and nuclear emulsion polymerization process, adopt conventional vinylformic acid system (not containing organic silicon monomer), reduced the cost of organosilicon crylic acid latex; And seed emulsion, nuclear emulsion and shell emulsion have different second-order transition temperatures respectively, and coating has higher hardness and better weather after the film forming.Use the emulsion paint of organosilicon crylic acid latex preparation of the present invention to have excellent contamination resistance, ageing resistance, water tolerance; abrasion resistance; performances such as contrast ratio height, over-all properties meets and exceeds the corresponding index of the solvent based coating of excellent property, and helps environment protection and HUMAN HEALTH.
Embodiment
Embodiment 1, the polymerization of seed emulsion
With deionized water 800Kg, Sodium phosphate dibasic 0.5Kg, sodium lauryl sulphate 52Kg, ammonium persulphate 3.6Kg adds in the reactor, under stirring condition, add methyl methacrylate 139Kg, methacrylic acid 4.5Kg, uncle's DDM dodecyl mercaptan 0.4Kg is after stirring 30 minutes, begin to warm to 65-77 ℃, stop heating, blue streak appears in emulsion, and thermopositive reaction appears in reaction system, temperature is raised to 80-85 ℃, keep 80-82 ℃ of temperature, isothermal reaction 30 minutes, the viscosity of resulting seed emulsion is about 600mPas, second-order transition temperature Tg is 12, and molecular weight is about 340.
Embodiment 2, the polymerization of seed emulsion
With deionized water 700Kg, SODIUM PHOSPHATE, MONOBASIC 1Kg, sodium lauryl sulphate 45Kg, nonylphenol polyethylene ether 35Kg, dicumyl peroxide 8.6Kg adds in the reactor, under stirring condition, add methyl acrylate 194Kg, methacrylic acid 14.4Kg, tert-dodecyl mercaptan 2Kg is after stirring 30 minutes, begin to warm to 65-77 ℃, stop heating, blue streak appears in emulsion, and thermopositive reaction appears in reaction system, temperature is raised to 80-85 ℃, keep 80-82 ℃ of temperature, isothermal reaction 30 minutes, the viscosity of resulting seed emulsion is about 800mPas, second-order transition temperature Tg is 8, and molecular weight is about 190.
Embodiment 3, the polymerization of seed emulsion
With deionized water 900Kg, sodium bicarbonate 0.1Kg, nonylphenol polyethylene ether 7Kg, alkylphenol polyvinyl ether phosphoric acid ester 20Kg, persulfuric acid clock 1.9Kg adds in the reactor, under stirring condition, add methyl methacrylate 65Kg, vinylformic acid 5Kg, uncle's DDM dodecyl mercaptan 1Kg is after stirring 30 minutes, begin to warm to 65-77 ℃, stop heating, blue streak appears in emulsion, and thermopositive reaction appears in reaction system, temperature is raised to 80-85 ℃, keep 80-82 ℃ of temperature, isothermal reaction 30 minutes, the viscosity of resulting seed emulsion is about 400mPas, second-order transition temperature Tg is 14, and molecular weight is about 260.
Embodiment 4, the polymerization of nuclear emulsion
The seed emulsion 535Kg of embodiment 1 is added reactor, keep 80-82 ℃ of temperature, drip the mixing Acrylic Acid Monomer (wherein: methyl methacrylate 75Kg, butyl acrylate 195Kg, Isooctyl acrylate monomer 45Kg, methacrylic acid 7Kg) of 322Kg and the mixed solution of forming by 0.7Kg uncle DDM dodecyl mercaptan, 1.3Kg ammonium persulphate, 9Kg sodium lauryl sulphate and 132Kg deionized water while stirring, dropping process 2 hours, insulation reaction is 30 minutes then.The viscosity of resulting nuclear emulsion is about 600mPas, and second-order transition temperature Tg is 13, and molecular weight is about 1200.
Embodiment 5, the polymerization of nuclear emulsion
The seed emulsion 375Kg of embodiment 2 is added reactor, keep 80-82 ℃ of temperature, drip the mixing Acrylic Acid Monomer (wherein: methyl acrylate 160Kg, butyl acrylate 225Kg, Isooctyl acrylate monomer 82Kg, vinylformic acid 31Kg) of 498Kg and the mixed solution of forming by 0.4Kg uncle DDM dodecyl mercaptan, 1.6Kg ammonium persulphate, 7Kg nonylphenol polyethylene ether, 8Kg alkylphenol polyvinyl ether phosphoric acid ester and 110Kg deionized water while stirring, dropping process 1.5 hours, insulation reaction is 30 minutes then.The viscosity of resulting nuclear emulsion is about 900mPas, and second-order transition temperature Tg is 18, and molecular weight is about 2600.
Embodiment 6, the polymerization of nucleocapsid organosilicon crylic acid latex
The nuclear emulsion 550Kg that adds embodiment 4 in the reactor, under agitation condition, control reaction temperature 80-82 ℃, drip and mix Acrylic Acid Monomer 280Kg (wherein: methyl methacrylate 75Kg, butyl acrylate 140Kg, Isooctyl acrylate monomer 60Kg, methacrylic acid 5Kg) and organosilane monomer 40Kg (wherein: eight alkyl cyclotetrasiloxane 10Kg, eight vinyl cyclotetrasiloxane 30Kg), drip DDM dodecyl mercaptan simultaneously by the 1.2Kg uncle, 0.05Kg potassium hydroxide, the ammonium persulphate of 100Kg deionized water and 1.1Kg, 2.7Kg propylene glycol monobutyl ether, the mixed solution that sodium lauryl sulphate 6.4Kg forms.Control reaction temperature 85-90 ℃, react after 5 hours, be cooled to below 45 ℃, add isothiazole miaow ketone 2.55Kg again, 2-amino-2 methyl isophthalic acids-propyl alcohol 16Kg.Discharging is filtered and is obtained organosilicon crylic acid latex, and the viscosity of resulting emulsion is 1.5Pa.s, solids content 50%., second-order transition temperature Tg is 21, and molecular weight is about 4800, and the pH value is 8.
Claims (12)
1, a kind of organosilicon crylic acid latex is characterized in that this organosilicon crylic acid latex is the product that is formed by core-shell emulsion polymerization by organosilicon mix monomer and Acrylic Acid Monomer,
Wherein: the organosilicon mix monomer by eight vinyl cyclotetrasiloxanes and eight alkyl cyclotetrasiloxanes with 1-3: 1 weight ratio is formed, and the alkyl of eight alkyl cyclotetrasiloxanes is C
1-C
4
Acrylic Acid Monomer is one or more the mixture that is selected from vinylformic acid, methacrylic acid, methyl methacrylate, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate or the Isooctyl acrylate monomer.
2, the production method of the described organosilicon crylic acid latex of claim 1 is characterized in that this production method comprises following three steps:
The polymerization of the first step seed emulsion
Acrylic Acid Monomer carries out letex polymerization under initiator and emulsifying agent effect, 65～85 ℃ of temperature of reaction, and 30～60 minutes reaction times, promptly get seed emulsion, the weight % content of reactant each component is as follows:
Component weight %
Acrylic Acid Monomer 5～25
Emulsifying agent 2～8
Initiator 0.1～1.0
Molecular weight regulator 0.02～0.2
PH regulator agent 0.01～0.1
Deionized water 70～90
The polymerization of the second step nuclear emulsion
Described seed emulsion and Acrylic Acid Monomer are carried out letex polymerization again, 65～95 ℃ of temperature of reaction, 0.5～3.5 hour reaction times, promptly get and examine emulsion, the weight % content of reactant each component is as follows:
Component weight %
Seed emulsion 35～55
Acrylic Acid Monomer 30～50
Emulsifying agent 0.4～2.0
Initiator 0.02～0.2
Molecular weight regulator 0.01～0.1
Deionized water 9～15
The polymerization of the 3rd step nucleocapsid organosilicon crylic acid latex
Described nuclear emulsion and Acrylic Acid Monomer and organosilicon mix monomer are carried out letex polymerization, 80～90 ℃ of temperature of reaction, reaction times 4-8 hour, the weight % content of reactant each component was as follows:
Component weight %
Nuclear emulsion 53～56
Acrylic Acid Monomer 24～30
Organosilicon mix monomer 2.5～5.0
Catalyzer 0.001～0.01
Emulsifying agent 0.2～1.0
Initiator 0.02～0.2
Molecular weight regulator 0.04～0.2
Hydrolysis inhibitor 0.05～0.5
Mould inhibitor 0.05～0.5
PH regulator agent 0.2～2.0
Deionized water 8～11.
3,, it is characterized in that at the Acrylic Acid Monomer described in the described three-step reaction be one or more the mixture that is selected from vinylformic acid, methacrylic acid, methyl methacrylate, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate or the Isooctyl acrylate monomer as the production method of organosilicon crylic acid latex as described in the claim 2.
4, as the production method of organosilicon crylic acid latex as described in the claim 2, it is characterized in that at the initiator described in the described three-step reaction be to be selected from ammonium persulphate, Potassium Persulphate or dicumyl peroxide.
5,, it is characterized in that at the molecular weight regulator described in the described three-step reaction it being to be selected from uncle's DDM dodecyl mercaptan, uncle's lauric acid alcohol or three-sulfonium base propyl alcohol as the production method of organosilicon crylic acid latex as described in the claim 2.
6,, it is characterized in that at the emulsifying agent described in the described three-step reaction be one or more the mixture that is selected from sodium lauryl sulphate, nonylphenol polyethylene ether or the alkylphenol polyvinyl ether phosphoric acid ester as the production method of organosilicon crylic acid latex as described in the claim 2.
7,, it is characterized in that in the pH regulator agent described in the described the first step reaction be to be selected from sodium bicarbonate, Sodium phosphate dibasic or SODIUM PHOSPHATE, MONOBASIC as the production method of organosilicon crylic acid latex as described in the claim 2.
8, as the production method of organosilicon crylic acid latex as described in the claim 2, it is characterized in that at the organosilicon mix monomer described in the described three-step reaction by eight vinyl cyclotetrasiloxanes and eight alkyl cyclotetrasiloxanes with 1-3: 1 weight ratio is formed, and the alkyl of eight alkyl cyclotetrasiloxanes is C
1-C
4
9, as the production method of organosilicon crylic acid latex as described in the claim 2, it is characterized in that described in the described three-step reaction catalyzer be to be selected from potassium hydroxide, sodium hydroxide or triethylamine.
10, as the production method of organosilicon crylic acid latex as described in the claim 2, it is characterized in that at the hydrolysis inhibitor described in the described three-step reaction be to be selected from butyl glycol ether, propylene glycol or propylene glycol monobutyl ether.
11, as the production method of organosilicon crylic acid latex as described in the claim 2, it is characterized in that at the mould inhibitor described in the described three-step reaction it being to be selected from isothiazole miaow ketone, 2-methyl-4-isothiazole miaow-3-ketone or daconil M.
12, as the production method of organosilicon crylic acid latex as described in the claim 2, it is characterized in that in the pH regulator agent described in the described three-step reaction be to be selected from sodium bicarbonate, ammoniacal liquor or 2-amino-2-methyl-1-propanol.
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| CN102516445A (en) * | 2011-11-29 | 2012-06-27 | 贵州大学 | Method for preparing silicone acrylic emulsion by adopting non-vinyl siloxane |
| CN101781390B (en) * | 2009-05-12 | 2013-08-07 | 天津城市建设学院 | Preparation method of nuclear shell structure high-silicon silicone acrylic emulsion used for building exterior wall |
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- 2004-09-14 CN CN 200410066362 patent/CN1244602C/en not_active Expired - Fee Related
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| CN101781390B (en) * | 2009-05-12 | 2013-08-07 | 天津城市建设学院 | Preparation method of nuclear shell structure high-silicon silicone acrylic emulsion used for building exterior wall |
| CN102516445A (en) * | 2011-11-29 | 2012-06-27 | 贵州大学 | Method for preparing silicone acrylic emulsion by adopting non-vinyl siloxane |
| CN103937362A (en) * | 2013-01-17 | 2014-07-23 | 上海绿色建材研究中心有限公司 | Thermal insulation sealing paint, preparation method and applications thereof |
| CN103937362B (en) * | 2013-01-17 | 2016-03-09 | 上海绿色建材研究中心有限公司 | A kind of insulation back cover coating and Synthesis and applications thereof |
| CN103525232A (en) * | 2013-10-24 | 2014-01-22 | 镇江威信广厦模块建筑有限公司 | Preparation method of mildewproof waterborne coating |
| CN103525232B (en) * | 2013-10-24 | 2016-01-20 | 威信广厦模块住宅工业有限公司 | A kind of preparation method of mildew-resistant water-borne coatings |
| CN104877141A (en) * | 2015-06-11 | 2015-09-02 | 深圳市安品有机硅材料有限公司 | Preparation method of polymerizable modifier |
| CN104877140A (en) * | 2015-06-11 | 2015-09-02 | 深圳市安品有机硅材料有限公司 | Polymerizable modifying agent and application thereof |
| CN107200821A (en) * | 2017-04-21 | 2017-09-26 | 苏州博纳化学科技有限公司 | Dispersant of acrylate vinyl siloxane copolymer and preparation method thereof |
| CN113321442A (en) * | 2021-07-12 | 2021-08-31 | 广州建涂堡建材有限公司 | Method for preparing redispersible latex powder by taking modified silicone-acrylic emulsion as raw material |
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| CN1244602C (en) | 2006-03-08 |
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