CN101550217A - Method for preparing soap-free silicone-acrylic emulsion with core-shell structure - Google Patents
Method for preparing soap-free silicone-acrylic emulsion with core-shell structure Download PDFInfo
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Abstract
本发明公开了一种无皂核壳型硅丙乳液的制备方法，本发明方法首先制备有机硅混合物，然后按质量比取：丙烯酸酯单体∶过硫酸盐∶无离子水∶有机硅混合物∶功能单体＝100∶0.4∶120∶5－15∶0.3～0.5；或丙烯酸酯∶过硫酸盐∶无离子水∶有机硅混合物∶反应性乳化剂＝100∶0.4∶120∶5－15∶1～5，后在反应釜中经反应制得无皂核壳型硅丙乳液；本发明的另一个实现方案是按质量比取：丙烯酸酯单体∶过硫酸盐∶亚硫酸盐∶无离子水∶有机硅混合物∶功能单体＝100∶0.4∶0.1∶120∶5－15∶0.3～0.5；或丙烯酸酯∶过硫酸盐∶亚硫酸盐∶无离子水∶有机硅混合物∶反应性乳化剂＝100∶0.4∶0.1∶120∶5－15∶1～5，后在反应釜中经反应制得无皂核壳型硅丙乳液。
The invention discloses a preparation method of a soap-free core-shell type silicon-acrylic emulsion. The method of the invention first prepares an organic silicon mixture, and then according to the mass ratio: acrylate monomer: persulfate: ion-free water: organic silicon mixture: Functional monomer = 100: 0.4: 120: 5-15: 0.3-0.5; or acrylate: persulfate: deionized water: silicone mixture: reactive emulsifier = 100: 0.4: 120: 5-15:1 ～5, after reacting in the reactor, make soap-free core-shell type silicon acrylic emulsion; Another realization scheme of the present invention is to get by mass ratio: acrylate monomer: persulfate: sulfite: deionized water : silicone mixture: functional monomer = 100: 0.4: 0.1: 120: 5-15: 0.3 ~ 0.5; or acrylate: persulfate: sulfite: deionized water: silicone mixture: reactive emulsifier = 100: 0.4: 0.1: 120: 5-15: 1-5, and then react in a reactor to prepare a soap-free core-shell silicone-acrylic emulsion.
Description
Technical field
The present invention relates to a kind of preparation method who does not have the soap organosilicon crylic acid latex.Be particularly related to a kind ofly be used for that having of exterior wall is pollution-free, weathering resistance, gloss retention, ventilation property, water-repellancy, the anti-contamination and the technology of preparing of the no soap organosilicon crylic acid latex of wear resistance characteristic.
Background technology
Acrylic ester emulsion is with its good film-forming property, the intensity height, and advantage such as cohesiveness is strong is widely used in inner wall of building, exterior wall, ceiling and ground application and produces with emulsion paint.Growing architectural latex coating no longer is satisfied with existing level, but acrylic ester emulsion has been proposed pollution-free, super durable and multi-functional requirement, to preserve the ecological environment, continues to improve the outward appearance and the inner quality of paint film.Silicone resin is to be major key with the siloxane bond, its bond energy: 452.5KJ/mol, the most significant two fundamental propertys are: high oxidation resistance voltinism and low surface energy make it show special weathering resistance, gloss retention, ventilation property, water-repellancy, the anti-contamination and wear resistance in application.But pure silicone resin cost height, paint film crosslinking temperature height, intensity is low, has limited its application.Organosilicon is introduced acrylic polymer, give full play to the good characteristic of the two, preparation environment-friendly type high performance latex coating is the research focus of building coating development field in recent years.
Adopting emulsion polymerisation process is the most promising method of preparation organosilicon-modified acrylate.The realization of this method needs emulsifying agent under the regular situation, though emulsifying agent plays crucial effect to the synthetic of emulsion and stablizing etc., also can make organosilicon crylic acid latex coating be not so good as similar solvent based coating at aspects such as gloss, water tolerance, weathering resistance, fullness ratio.
How synthesizing organosilicon crylic acid latex under emulsifier-free, solve these problems that organosilicon crylic acid latex exists, the application of organosilicon crylic acid latex is further enlarged, is a major issue during organosilicon crylic acid latex synthesizes.
Emulsifier-free emulsion polymerization just is meant not add emulsifying agent or only add micro-emulsifying agent when polyreaction and carries out letex polymerization.Compare with conventional emulsion, soap-free emulsion has surface cleaning, and homogeneous dispersive characteristics have improved water tolerance, optics, electricity and the thermal property of polymkeric substance and environmentally safe greatly.Solid polymer only needs the emulsion dehydration if desired, and operation is simple, and cost is low, and these advantages are that conventional emulsion is too far behind to catch up.Therefore, soap-free emulsion is used widely in fields such as optics, medical science, building, electric power.
Compare with traditional emulsion polymerization, the characteristics of emulsifier-free emulsion polymerization mainly are the formation mechanism of micelle and stable conditionally complete difference thereof.Do not have or only have the existence of few partial emulsifier in the emulsifier-free emulsion polymerization system, micelle mainly is able to stable by being combined in particle group on polymer chain or its end group, hydrophilic radical etc.Chinese patent 200410027970 is a reactive emulsifier with the alkyl vinyl sodium sulfonate, has introduced a kind of preparation method who does not have the soap organosilicon crylic acid latex, and this method adopts mixes reinforced method.Chinese patent 03115355 utilizes reactive emulsifier, a kind of preparation method who does not have the hud typed organosilicon crylic acid latex of soap nano level is disclosed, the emulsion paint of this emulsion preparation is better than the emulsion that general emulsifying agent obtains at aspects such as weathering resistance, ultraviolet resistance irradiation performances, but this method is with organosilane monomer and acrylate monomer copolymerization, and according to the document introduction, in silicon third copolymer emulsion, have only organosilicon to have its superiority of certain chain length and just can give full play to.
Summary of the invention
The invention discloses a kind of preparation method of soap-free silicone-acrylic emulsion with core-shell structure, that product of the present invention has is pollution-free, weathering resistance, gloss retention, ventilation property, water-repellancy, the anti-contamination and characteristics such as wear resistance.
The object of the present invention is to provide a kind of preparation method of soap-free silicone-acrylic emulsion with core-shell structure.
The present invention is achieved through the following technical solutions, and comprises step:
1) preparation organosilicon mixture: will wait the octamethylcyclotetrasiloxane of quality and the catalyzer of eight vinyl cyclotetrasiloxanes and the two total mass 0.6% to place in the reaction vessel of thorough drying, stir down and heat up, 100-110 ℃ of isothermal reaction, stopped reaction when liquid viscosity reaches 9.6 pools to reaction vessel, be cooled to room temperature, with HCl furnishing neutrality, get silicone intermediate.The silane coupling agent of adding and gained silicone intermediate equivalent mixes, and gets organosilicon mixture;
2) the no soap organosilicon crylic acid latex of preparation:
Get each material by following mass ratio: acrylate monomer: persulphate: deionized water: organosilicon mixture: function monomer=100: 0.4: 120: 5-15: 0.3～0.5; Or acrylate: persulphate: deionized water: organosilicon mixture: reactive emulsifier=100: 0.4: 120: 5-15: 1～5;
With deionized water persulphate being made into mass concentration is 4～8% the aqueous solution; In reactor, add the surplus deionized water of institute and reactive emulsifier or function monomer behind the preparation persulphate aqueous solution, stirring and dissolving, be warming up to 75-82 ℃, splash into the acrylate monomer of total mass 1/4 and the persulphate aqueous solution of cumulative volume 1/4 at the uniform velocity simultaneously, 30 minutes times spent; The wait blue light occurs; Treat that the persulphate aqueous solution that the back drips step 1) gained organosilicon mixture and cumulative volume 1/4 appears in blue light, drips off in 1.5 hours; Add the acrylate monomer of total mass 3/4 and the persulphate aqueous solution of cumulative volume 1/2 more simultaneously, dripped off in 1.5 hours; In 78 ℃ of insulations 1 hour; Naturally cool to room temperature, adjust pH to 8 is used the filtered through gauze discharging.
Except that technique scheme, the present invention can also realize by following technical scheme, comprise step:
1) preparation organosilicon mixture: will wait the octamethylcyclotetrasiloxane of quality and the catalyzer of eight vinyl cyclotetrasiloxanes and the two total mass 0.6% to place in the reaction vessel of thorough drying, stir down and heat up, 100-110 ℃ of isothermal reaction, stopped reaction when liquid viscosity reaches 9.6 pools to reaction vessel, be cooled to room temperature, with HCl furnishing neutrality, get silicone intermediate.The silane coupling agent of adding and gained silicone intermediate equivalent mixes, and gets organosilicon mixture;
2) the no soap organosilicon crylic acid latex of preparation:
Get each material by following mass ratio: acrylate monomer: persulphate: sulphite: deionized water: organosilicon mixture: function monomer=100: 0.4: 0.1: 120: 5-15: 0.3～0.5; Or acrylate: persulphate: sulphite: deionized water: organosilicon mixture: reactive emulsifier=100: 0.4: 0.1: 120: 5-15: 1～5;
With deionized water persulphate being made into mass concentration is 4～8% water solution A; Sulphite is made into the aqueous solution B of mass concentration 8～12%; Add the surplus deionized water of institute and reactive emulsifier or function monomer behind obtained aqueous solution A and the B in reactor, stirring and dissolving is warming up to 75-82 ℃, splashes into the water solution A of the acrylate monomer and the cumulative volume 1/4 of total mass 1/4 at the uniform velocity simultaneously, 30 minutes times spent; The wait blue light occurs; Treat that the solution A that the back at the uniform velocity splashes into the acrylate monomer and the cumulative volume 1/2 of total mass 3/4 simultaneously appears in blue light, drips off with 1.5 hours; Add solution B after being cooled to 60 ℃, mixing drips the solution A of step 1) gained organosilicon mixture and cumulative volume 1/4 simultaneously, drips off with 1.5 hours; In 60 ℃ of insulations 1 hour; Naturally cool to room temperature, adjust pH to 8 is used the filtered through gauze discharging.
In above-mentioned two kinds of technical schemes,
Described silane coupling agent contains the two keys that can participate in radical polymerization and the siloxane groups of facile hydrolysis, can be vinyltrimethoxy silane, vinyltriethoxysilane, a kind of or its mixture in the methyl allyl acyloxypropyl trimethoxysilane.
Described catalyzer is potassium hydroxide or sodium hydroxide.
Described function monomer is the mixture of ionic comonomer or it and non-ionic type comonomer; The mass ratio of mixture intermediate ion type and non-ionic type comonomer is 2: 1～4: 1.
Contain two key groups that can participate in radical polymerization and the functional group that plays emulsifying effect in the molecule of described reactive emulsifier; Comprise two kinds of anionic and non-ionic types:
The anionic reactive emulsifier can be: undecylenic acid sodium, allyloxy hydroxypropyl azochlorosulfonate acid sodium, 2-acrylamido-2-methyl=-propyl sulfonic acid sodium, allyloxy Nonyl pheno (10) ether ammonium sulfate or a-alkene sulfonate.Wherein the structure of a-alkene sulfonate is as follows:
RCH＝CH(CH
2)pSO
3Na
Annotate: R is a normal chain alkyl, and p=0 or 1～(n-3) positive integer n are the carbon number of alpha-olefin
Nonionic emulsifier can be polyoxyethylene glycol mono allyl ether, the ninth of the ten Heavenly Stems phenol polyethenoxy ether acrylate or octyl phenol Soxylat A 25-7 acrylate.Wherein the ninth of the ten Heavenly Stems phenol polyethenoxy ether acrylate or octyl phenol Soxylat A 25-7 acrylate structure as follows:
Wherein, R is nonyl or octyl group, n=1～30
Described acrylate monomer is a kind of in ethyl propenoate, butyl acrylate, isobutyl acrylate, the methyl methacrylate or their mixture.
Described persulphate is water miscible Potassium Persulphate, Sodium Persulfate or ammonium persulphate.
Described sulphite is S-WAT or sodium bisulfite.
Advantage of the present invention and characteristics are:
1, adopts two stage seeded emulsion polymerization technologies.When the nuclear emulsion is synthetic, because acrylate monomer is comparatively stable, adopt the persulphate thermal initiation, temperature of reaction is higher, when the shell emulsion is synthesized, because the easy hydrolysis of organic silicon high-temperature forms gel from polycondensation, adopts oxidation-reduction to cause, and has reduced temperature of reaction.
2, the emulsion particle of product soap-free silicone-acrylic emulsion with core-shell structure of the present invention is to be nuclear with no soap pure-acrylic emulsion, and silicone intermediate and silane coupling agent are that shell is formed.That product of the present invention has is pollution-free, weathering resistance, gloss retention, ventilation property, water-repellancy, the anti-contamination and characteristics such as wear resistance, is the film forming base-material that a kind of fine prepares exterior wall latex paint.
Description of drawings
Fig. 1 emulsion film water-intake rate relatively
The transmission electron microscope picture (2.9 ten thousand *) of Fig. 2 embodiment 3 pure-acrylic emulsions
The transmission electron microscope picture (2.9 ten thousand *) of Fig. 3 embodiment 4 gained product of the present invention
The transmission electron microscope picture (2.9 ten thousand *) of Fig. 4 embodiment 5 gained product of the present invention
Embodiment
In order to understand the present invention, the present invention will be further described below by embodiment, but do not limit the present invention.
The preparation of embodiment 1 organosilicon mixture
100 gram octamethylcyclotetrasiloxanes, 100 gram eight vinyl cyclotetrasiloxanes and 1.2 gram potassium hydroxide are placed the four-hole bottle of thorough drying, open and stir and intensification, the maintenance system temperature is between 100-110 ℃, the stopped reaction when viscosity for the treatment of bottle interior liquid reaches 9.6 pools, be cooled to room temperature, with HCl furnishing neutrality, get silicone intermediate.The vinyltriethoxysilane of adding and gained silicone intermediate equivalent mixes, and gets organosilicon mixture.
Embodiment 2 preparation ordinary emulsions
The Potassium Persulphate of 0.4 gram is dissolved in wiring solution-forming A in the 10 gram deionized waters; Butyl acrylate and methyl methacrylate are made acrylate monomer by 1.5: 1 mixed.
0.8 gram sodium lauryl sulphate, 2.2 gram sim alkylphenol Soxylat A 25-7s and 110ml deionized water are joined in the four-hole bottle successively, stir down and heat up, earlier to 40 ℃ of dissolvings down; Begin at the uniform velocity to drip the solution A of 25 gram acrylate monomers and 2.5ml during again to 78 ℃, 30 minutes times spent; The wait blue light occurs, and continues to drip 75 grams after blue light occurs again and mixes acrylate monomer and 7.5ml solution A, drips off with 1.5h; 78 ℃ of insulations 1 hour, naturally cool to room temperature afterwards, adjust pH to 8 is used the filtered through gauze discharging.
The no soap pure-acrylic emulsion of embodiment 3 preparations:
The Potassium Persulphate of 0.4 gram is dissolved in wiring solution-forming A in the 10 gram deionized waters; Butyl acrylate and methyl methacrylate are made acrylate monomer by 1.5: 1 mixed.
0.3 gram Sodium styrene sulfonate, 0.1 gram Jia Jibingxisuanβ-Qiang Yizhi and 110ml deionized water are added in the four-hole bottle stirring at room 2 hours successively; Be warming up to 78 ℃ again, drip 25 gram acrylate monomer and 2.5ml solution A at the uniform velocity simultaneously, 30 minutes times spent; The wait blue light occurs, and drips 75 grams after blue light occurs simultaneously and mixes acrylate monomer and 7.5ml solution A, drips off with 1.5h; 78 ℃ of insulations 1 hour, naturally cool to room temperature afterwards, adjust pH to 8 is used the filtered through gauze discharging.
Embodiment 4 preparation soap-free silicone-acrylic emulsion with core-shell structure (organosilicon adds earlier)
The Potassium Persulphate of 0.4 gram is dissolved in wiring solution-forming A in the 10 gram deionized waters; Butyl acrylate and methyl methacrylate are made acrylate monomer by 1.5: 1 mixed.
0.3 gram Sodium styrene sulfonate, 0.1 gram Jia Jibingxisuanβ-Qiang Yizhi and 110ml deionized water are added in the four-hole bottle stirring at room 2 hours successively; Be warming up to 78 ℃ again, beginning at the uniform velocity drips 25 gram acrylate monomer and 2.5ml solution A, 30 minutes times spent; The wait blue light occurs, and drips organosilicon mixture 10 gram and the solution A 2.5ml that prepare among the embodiment after blue light occurs simultaneously, and 1.5h drips off; Drip 75 gram acrylate monomer and 5.0ml solution A more simultaneously, 1.5h drips off; 78 ℃ are incubated 1 hour, naturally cool to room temperature afterwards, and adjust pH to 8 is used the filtered through gauze discharging.
The Potassium Persulphate of 0.4 gram is dissolved in wiring solution-forming A in the 10 gram deionized waters; 0.1 the gram sodium bisulfite is dissolved in wiring solution-forming B in the 10ml deionized water.
0.3 gram Sodium styrene sulfonate, 0.1 gram Jia Jibingxisuanβ-Qiang Yizhi and 110ml deionized water are added in the four-hole bottle stirring at room 2 hours successively; Be warming up to 78 ℃ again, beginning at the uniform velocity drips 25 gram acrylate monomer and 2.5ml solution A, 30 minutes times spent, wait for blue light, and blue light the back occurs and at the uniform velocity drips 75 gram acrylate monomer and 5.0ml solution A simultaneously, and 1.5h drips off; Add solution B after being cooled to 60 ℃, mixing drips organosilicon mixture 10 gram and the 2.5ml solution A that prepare among the embodiment simultaneously, and 1.5h drips off; 60 ℃ are incubated 1 hour, naturally cool to room temperature afterwards, and adjust pH to 8 is used the filtered through gauze discharging.
Embodiment 6 embodiment 7 and embodiment 8
With Sodium styrene sulfonate and Jia Jibingxisuanβ-Qiang Yizhi among the 0.4 gram allyloxy hydroxypropyl azochlorosulfonate acid sodium replacement embodiment 3,4 or 5, all the other remain unchanged.
Embodiment 9, embodiment 10 and embodiment 11
With Sodium styrene sulfonate and Jia Jibingxisuanβ-Qiang Yizhi among 0.4 gram allyloxy Nonyl pheno (10) the ether ammonium sulfate replacement embodiment 3,4 or 5, all the other remain unchanged.
Embodiment 12, embodiment 13 and embodiment 14
With Sodium styrene sulfonate and Jia Jibingxisuanβ-Qiang Yizhi among 0.4 gram allyloxy Nonyl pheno (10) the ether ammonium sulfate replacement embodiment 3,4 or 5, all the other remain unchanged.
Embodiment 15, embodiment 16 and embodiment 17
With Sodium styrene sulfonate and Jia Jibingxisuanβ-Qiang Yizhi among phenol polyethenoxy ether acrylate replacement in the ninth of the ten Heavenly Stems embodiment 3,4 or 5, all the other remain unchanged.
Embodiment 18, embodiment 19 and embodiment 20
With Sodium styrene sulfonate and Jia Jibingxisuanβ-Qiang Yizhi among the polyoxyethylene glycol mono allyl ether replacement embodiment 3,4 or 5, all the other remain unchanged.
The test of experimental example 1 water-resistance property of coating
The emulsion film of seasoning after three days immerses in the water on the sheet glass with being coated in, and soaked 7 days, whether seeing films turned white, and bubbled, and came off.
The emulsion film water tolerance
After organosilicon mixed, the water tolerance of polymer coating film obviously improved than pure-acrylic emulsion film water tolerance.Soak and take out after 7 days, the organosilicon crylic acid latex film does not almost have obvious variation.
Experimental example 2 water-intake rates are investigated
With filming of weighing after the drying soaked after, pull out every day, blots with thieving paper and survey its water-intake rate
Water-intake rate=(m
1-m
0)/m
0* 100%
m
0Be the quality before absorbing water, m
1For the quality results after the suction is seen accompanying drawing 1.
Experimental example 3 transmission electron microscope observing results
Is 0.5 ~ 1% with distilled water diluting to mass concentration with embodiment 3,4,5 gained emulsions, drips 1 and drips to and use TE after drying on the copper mesh that is covered with polyvinyl formal
M-100CX IIType transmission electron microscope (TEM) is observed.The results are shown in Figure 2,3,4.
From Fig. 2, Fig. 3 and Fig. 4 as can be seen, no matter pure third, silicon third, add mode regardless of organosilicon, the equal consistent face of land of the emulsion particle that obtains now is nucleocapsid structure, in conjunction with loose, particle diameter is big (～0.3 μ m) between the pure third emulsion particle nucleocapsid, and combination closely between the silicone acrylic emulsion particle nucleocapsid, particle diameter less (organosilicon adds the about 0.1 μ m of particle diameter earlier, adds the about 0.2 μ m of particle diameter behind the organosilicon).
Claims (10)
1, a kind of preparation method of soap-free silicone-acrylic emulsion with core-shell structure is characterized in that comprising step:
1) preparation organosilicon mixture: will wait the octamethylcyclotetrasiloxane of quality and the catalyzer of eight vinyl cyclotetrasiloxanes and the two total mass 0.6% to place in the reaction vessel of thorough drying, stir down and heat up, 100-110 ℃ of isothermal reaction, stopped reaction when liquid viscosity reaches 9.6 pools to reaction vessel, be cooled to room temperature, with HCl furnishing neutrality, get silicone intermediate.The silane coupling agent of adding and gained silicone intermediate equivalent mixes, and gets organosilicon mixture;
2) the no soap organosilicon crylic acid latex of preparation:
Get each material by following mass ratio: acrylate monomer: persulphate: deionized water: organosilicon mixture: function monomer=100: 0.4: 120: 5-15: 0.3～0.5; Or acrylate: persulphate: deionized water: organosilicon mixture: reactive emulsifier=100: 0.4: 120: 5-15: 1～5;
With deionized water persulphate being made into mass concentration is 4～8% the aqueous solution; In reactor, add the surplus deionized water of institute and reactive emulsifier or function monomer behind the preparation persulphate aqueous solution, stirring and dissolving, be warming up to 75-82 ℃, splash into the acrylate monomer of total mass 1/4 and the persulphate aqueous solution of cumulative volume 1/4 at the uniform velocity simultaneously, 30 minutes times spent; The wait blue light occurs; Treat that the persulphate aqueous solution that the back drips step 1) gained organosilicon mixture and cumulative volume 1/4 appears in blue light, drips off in 1.5 hours; Add the acrylate monomer of total mass 3/4 and the persulphate aqueous solution of cumulative volume 1/2 more simultaneously, dripped off in 1.5 hours; In 78 ℃ of insulations 1 hour; Naturally cool to room temperature, adjust pH to 8 is used the filtered through gauze discharging.
2, a kind of preparation method of soap-free silicone-acrylic emulsion with core-shell structure is characterized in that comprising step:
1) preparation organosilicon mixture: will wait the octamethylcyclotetrasiloxane of quality and the catalyzer of eight vinyl cyclotetrasiloxanes and the two total mass 0.6% to place in the reaction vessel of thorough drying, stir down and heat up, 100-110 ℃ of isothermal reaction, stopped reaction when liquid viscosity reaches 9.6 pools to reaction vessel, be cooled to room temperature, with HCl furnishing neutrality, get silicone intermediate.The silane coupling agent of adding and gained silicone intermediate equivalent mixes, and gets organosilicon mixture;
2) the no soap organosilicon crylic acid latex of preparation:
Get each material by following mass ratio: acrylate monomer: persulphate: sulphite: deionized water: organosilicon mixture: function monomer=100: 0.4: 0.1: 120: 5-15: 0.3～0.5; Or acrylate: persulphate: sulphite: deionized water: organosilicon mixture: reactive emulsifier=100: 0.4: 0.1: 120: 5-15: 1～5;
With deionized water persulphate being made into mass concentration is 4～8% water solution A; Sulphite is made into the aqueous solution B of mass concentration 8～12%; Add the surplus deionized water of institute and reactive emulsifier or function monomer behind obtained aqueous solution A and the B in reactor, stirring and dissolving is warming up to 75-82 ℃, splashes into the water solution A of the acrylate monomer and the cumulative volume 1/4 of total mass 1/4 at the uniform velocity simultaneously, 30 minutes times spent; The wait blue light occurs; Treat that the solution A that the back at the uniform velocity splashes into the acrylate monomer and the cumulative volume 1/2 of total mass 3/4 simultaneously appears in blue light, drips off with 1.5 hours; Add solution B after being cooled to 60 ℃, mixing drips the solution A of step 1) gained organosilicon mixture and cumulative volume 1/4 simultaneously, drips off with 1.5 hours; In 60 ℃ of insulations 1 hour; Naturally cool to room temperature, adjust pH to 8 is used the filtered through gauze discharging.
3, the preparation method of a kind of soap-free silicone-acrylic emulsion with core-shell structure according to claim 1 and 2, it is characterized in that described silane coupling agent is a vinyltrimethoxy silane, vinyltriethoxysilane, a kind of or its mixture in the methyl allyl acyloxypropyl trimethoxysilane.
4, the preparation method of a kind of soap-free silicone-acrylic emulsion with core-shell structure according to claim 1 and 2 is characterized in that described catalyzer is potassium hydroxide or hydroxide.
5, the preparation method of a kind of soap-free silicone-acrylic emulsion with core-shell structure according to claim 1 and 2 is characterized in that described function monomer is the mixture of ionic comonomer or it and non-ionic type comonomer.
6, the preparation method of a kind of soap-free silicone-acrylic emulsion with core-shell structure according to claim 1 and 2 is characterized in that described function monomer is the mixture of ionic comonomer and non-ionic type comonomer; The mixing quality ratio is: ionic: non-ionic type=2: 1～4: 1;
7, the preparation method of a kind of soap-free silicone-acrylic emulsion with core-shell structure according to claim 1 and 2, it is characterized in that described reactive emulsifier be undecylenic acid sodium, allyloxy hydroxypropyl azochlorosulfonate acid sodium, 2-acrylamido-2-methyl=-propyl sulfonic acid sodium, allyloxy Nonyl pheno (10) ether ammonium sulfate, a-alkene sulfonate, polyoxyethylene glycol mono allyl ether, the ninth of the ten Heavenly Stems phenol polyethenoxy ether acrylate or octyl phenol Soxylat A 25-7 acrylate.
8, the preparation method of a kind of soap-free silicone-acrylic emulsion with core-shell structure according to claim 1 and 2 is characterized in that described acrylate monomer is a kind of in ethyl propenoate, butyl acrylate, isobutyl acrylate, the methyl methacrylate or their mixture;
9, the preparation method of a kind of soap-free silicone-acrylic emulsion with core-shell structure according to claim 1 and 2 is characterized in that described persulphate is water miscible Potassium Persulphate, Sodium Persulfate or ammonium persulphate.
10, the preparation method of a kind of soap-free silicone-acrylic emulsion with core-shell structure according to claim 1 and 2 is characterized in that described sulphite is meant S-WAT or sodium bisulfite.
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