CN102898578A - Self-crosslinking silicone-acrylate copolymer emulsion and preparation method - Google Patents
Self-crosslinking silicone-acrylate copolymer emulsion and preparation method Download PDFInfo
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Abstract
The invention relates to the organic compound technical field, which solves the problems of poor stability of the silicone-acrylate copolymer emulsion and poor water resistance and stain resistance performances of a film due to low silicon content. The invention relates to a self-crosslinking silicone-acrylate copolymer emulsion which comprises the following components by mass percentages: 10.0-30.0% of methacrylic acid alkylester, 15.0-30.0% of alkyl acrylate, 5-15% of organosiloxane, 0.5-2.5% of alkyl ester, 1.0-5.0% of organosilicone hydrolysis inhibitor, 0.5-2.0% of pH modifier, 0.5-2.0% of emulsifier, 0.5-1.0% of initiator and 40.0-60.0% of water. The emulsion good reaction and storage stability, the silicon content used for constituting colloidal particles and its functional group distribution is gradually increased from 60-80% of colloidal particle radius to the surface, the organosilicone segment function can fully performed, and the cost performance of product is enhanced.
Description
Technical field
The present invention relates to the organic compound technical field, be specially a kind of used for building exterior wall self-crosslinking silicone-acrylic polymer emulsion and preparation method thereof.
Background technology
Along with buildings to high stratification, maximization future development, the performances such as the weathering resistance of high-rise coating, contamination resistance, washability are had higher requirement, the application cycle of general requirement skin coating is at least more than 15 years.Acrylic resin has good weathering resistance, gloss retention and good film-forming properties usually, but lack cross-linking set on the linear molecule, be difficult to form three-dimensional netted crosslinked filming, cause that its high thermal resistance is poor, high temperature easily after-tacks, low temperature film easy embrittlement, lack flexibility.And the normal operation life-span of acrylic resin paint only has 5-10, can not reach the service requirements of external wall of building thing coating.In order to overcome the shortcoming of acrylic resin paint, adopt organosilicon that acrylic resin is carried out modification both at home and abroad and improve the performances such as it is water-fast, anti-contamination.Because silica bond energy (460kJ/mol) is higher than carbon-oxygen bond energy (351 kJ/mol) and carbon-carbon bond energy (347 kJ/mol), determined that organic-silicon-modified acrylic resin paint has good temperature tolerance, weathering resistance, simultaneously organosilicon is because having extremely low surface energy, organic-silicon-modified acrylic coating thereby have good contamination resistance, water tolerance.Therefore, high performance siloxane-acrylate copolymer emulsion has become the focus that coating industry is paid close attention to.
Organosilicon modified crylic acid resin generally has two kinds of methods of physical blending and chemical copolymerization.Physical blending is about to organo-siloxane and acrylic ester emulsion mixes with certain proportion, and this method technique is simple but limited to the raising of film performance, and has the shortcoming such as be separated.Chemical copolymerization is maximum method that adopts at present, the mode that organosilane monomer introducing acrylic ester polymer mainly adopts is with unsaturated silane monomer and acrylic ester monomer copolymerization with active group, make grafted-organosilicon oxygen alkane molecular chain on the acrylic ester polymer molecular chain, intermolecular condensation occurs and forms the Si-O-Si key in the Si-OH that active group in the curing of coating process (such as alkoxyl group) hydrolysis forms, or forms tridimensional network with hydroxy acrylate monomer (such as 2-Hydroxy ethyl acrylate)-OH generation condensation cross-linking.This copolymerization structure is conducive to the siloxane chain group arranges at the film surface orientation, improves the hydrophobicity that the copolymerization organosilicon-modified acrylic emulsion is filmed, and improves the contamination resistance of filming.But during the preparation organosilicon-modified acrylic emulsion, because the organo-siloxane monomer can be hydrolyzed autohemagglutination at aqueous phase, when particularly organosilane monomer content is larger, this hydrolysis autohemagglutination not only can reduce the reaction stability of polymer emulsion, when serious even produce gel reaction can't be carried out, cause emulsion organosilicon component content lower, and can produce the impact over-all properties of filming that is separated.And, when general introducing organo-siloxane monomer copolymerization prepares organosilicon-modified acrylic emulsion, the part organosilane monomer is in the latex particle interior polymeric, hydrolysis and crosslinked occurs in siloxanes when being unfavorable for film forming on the one hand, the Si-O-Si that is cross-linked to form on the other hand can not move to film coated surface, can not effectively bring into play the effect of Si-O-Si segment.At last, the general low molecular weight emulsifier that adopts easily moves to film coated surface in the organosilicon-modified acrylic emulsion polymerization process in film process, the impact performance such as water-fast of filming.Therefore, establishment organosilane monomer autohemagglutination how, improve stability of emulsion polymerization and silicone content, how aggregation technique makes the Si-O-Si that is cross-linked to form move to as far as possible film coated surface, giving full play to the Si-O-Si segment and do in order to improve the product cost performance, is the focus of high-grade exterior coating research.
Chinese patent CN200910068807 discloses a kind of preparation method of used for building exterior wall nuclear shell structure high-silicon silicone acrylic emulsion, and the method prepares first silicone oligomer, then carries out the organosilicon crylic acid latex that the core-shell emulsion polymerization preparation has nucleocapsid structure.For improving film performance, although designed the particle with nucleocapsid structure, can not eliminate the difference between the nucleocapsid structure composition, easily cause being separated of nucleocapsid part, when serious even the nucleocapsid obscission occurs, have a strong impact on the performances such as film hydrophobic, anti-contamination.In addition, this method has all been introduced organo-siloxane in the nucleocapsid part of particle, and the silicone content of emulsion has obtained large increase.But when emulsion film forming solidified, the silica segment of particle core part can not move to film coated surface, causes this part silica segment can not effectively bring into play the effects such as it is hydrophobic, anti-contamination.
Summary of the invention
Poor and the silicone content of siloxane-acrylate copolymer stability of emulsion is low to cause the problems such as water-resistance property of coating, contamination resistance be poor in order to solve, the invention provides a kind of self-crosslinking silicone-acrylic polymer emulsion, emulsion has good reaction and stability in storage, the silicone content and the functional group thereof that form micelle distribute from micelle radius 60 ~ 80% to surperficial progressive increase, give full play to the effect of organosilicon segment, improve the product cost performance.
Another object of the present invention provides a kind of preparation method of self-crosslinking silicone-acrylic polymer emulsion, and preparation method of the present invention is simple.
The present invention provides the application of self-crosslinking silicone-acrylic polymer emulsion on external wall simultaneously.
The present invention is achieved by the following technical solutions: a kind of self-crosslinking silicone-acrylic polymer emulsion, and described self-crosslinking silicone-acrylic polymer emulsion is to be made by following component, the mass percent of each component is:
Alkyl methacrylate 10.0 ~ 30.0%,
Alkyl acrylate 15.0 ~ 30.0%,
Organo-siloxane 5 ~ 15%,
Hydroxyalkyl acrylate 0.5 ~ 2.5%,
Organosilicon hydrolyzation inhibitor 1.0 ~ 5.0%,
PH adjusting agent 0.5 ~ 2.0%,
Emulsifying agent 0.5 ~ 2.0%,
Initiator 0.5 ~ 1.0%,
Water 40.0 ~ 60.0%,
Described alkyl methacrylate is selected from the mixture of one or more arbitrary proportions in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, the Isooctyl methacrylate;
Described alkyl acrylate is selected from the mixture of one or more arbitrary proportions in methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, the Isooctyl acrylate monomer;
Described organo-siloxane is selected from the mixture of one or more arbitrary proportions in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three butoxy silanes, the γ-methacryloxypropyl trimethoxy silane;
Described hydroxyalkyl acrylate is selected from the mixture of one or more arbitrary proportions in 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxyl butyl ester, vinylformic acid-5-hydroxyl pentyl ester, the vinylformic acid-own ester of 6-hydroxyl, methacrylic acid-2-hydroxy methacrylate, the methacrylic acid-3-hydroxy propyl ester;
Described organosilicon hydrolyzation inhibitor is selected from the mixture of one or more arbitrary proportions in the low molecular poly of propylene glycol, Isosorbide-5-Nitrae butyleneglycol, the polymerization degree 400 or 600;
Described initiator is selected from persulphate and sulfite oxidation-reduction system, and persulphate is 1.5 ~ 2.5 times of sulphite quality.Persulphate is selected from the mixture of one or more arbitrary proportions in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate, and sulphite is selected from the mixture of one or more arbitrary proportions in S-WAT, sodium bisulfite, potassium sulfite, Potassium hydrogen sulfite, ammonium sulphite, the ammonium bisulfite;
Described emulsifying agent is anionic emulsifier and reactive emulsifier compound, reactive emulsifier is 1 ~ 3 times of anionic emulsifier quality, and wherein anionic emulsifier is selected from the mixture of one or more arbitrary proportions in dodecyl diphenyl oxide disodium sulfonate (DSB), Sodium dodecylbenzene sulfonate (LAS), the sodium lauryl sulphate (SDS); Reactive emulsifier is selected from 2-acrylamido-2-methyl-propyl sulfonic acid sodium salt (AMPS-Na), 2-acrylamido-2-methyl-propyl sulfonic acid ammonium salt (AMPS-NH
4), the mixture of one or more arbitrary proportions in the 1-allyloxy-2-hydroxypropyl azochlorosulfonate acid sodium (HAPS), 2-acrylamido tetradecane sulfonate sodium (NaAMC14S), methacrylic acid hydroxide sodium dimercaptosulphanatein (HPMAS).
Described pH adjusting agent is selected from the mixture of one or more arbitrary proportions in sodium bicarbonate, the saleratus;
Described water is deionized water.
A kind of preparation method of self-crosslinking silicone-acrylic polymer emulsion is following steps:
(1) mass percent by self-crosslinking silicone-acrylic polymer emulsion component takes by weighing each component;
(2) 50% ~ 80% alkyl methacrylate, 30% ~ 70% alkyl acrylate in the step (1) are mixed and made into the monomer I, remaining alkyl methacrylate, alkyl acrylate are mixed and made into the monomer II, and hydroxyalkyl acrylate, organo-siloxane are mixed and made into the monomer III; As preferably, the mass ratio of monomer I and monomer II is 1.5 ~ 3:1.Calculate according to following FOX formula, described monomer I second-order transition temperature is 10 ~ 30 ℃, and monomer II second-order transition temperature is-40 ~-20 ℃.
Wherein, X
nBe the quality percentage composition of each component monomer in the mix monomer, T
GnAbsolute second-order transition temperature for each component monomer homopolymer.
(3) preparation seed emulsion: 60% ~ 80% water, 50% ~ 80% emulsifying agent, 50% ~ 70% initiator, hydrolysis inhibitor, pH adjusting agent in the step (1) are added in the reactor, stir and be warming up to 65 ~ 70 ℃ after 10 ~ 20 minutes, then the monomer I is added in the reactor, dripped off in 2 ~ 4 hours, dropwise rear insulation 15 ~ 30 minutes, make seed emulsion;
(4) with the monomer III in 1 ~ 2 hour, drop in the monomer II and continue and stir, then mixture and remaining water, emulsifying agent and the initiator with above-mentioned monomer II and monomer III is added drop-wise in the seed emulsion that obtains in the step (3) continuously, dropwised afterreaction 0.5 ~ 1 hour, be warming up to again 75 ~ 85 ℃ of insulations 1 ~ 2 hour, then be cooled to 40 ~ 50 ℃, filter discharging, namely obtain the self-crosslinking silicone-acrylic polymer emulsion.As preferably, per 20 ~ 40 minutes measured reaction system pH in the reaction process, if the pH value is outside 6.0 ~ 7.0 intervals, use between the material identical with the pH adjusting agent composition (the namely material the same with the component of foregoing pH adjusting agent) conditioned reaction system pH to 6.0 ~ 7.0, preferably be adjusted to 6.5.
The joining day that step (3), (4) limit material is for keeping thermal equilibrium and the certain speed of reaction of reaction mass in the reactor, and different weight of material can be by keeping the speed of response of material at the reactor of corresponding size.
This patent is introduced organo-siloxane on the seed emulsion basis, and silicone content and functional group thereof that the siloxane-acrylate copolymer emulsion forms micelle distribute from micelle radius 60 ~ 80% to surperficial progressive increase.Organosilicon segment and other monomer composition content increase gradually, have eliminated the difference of particle composition structure.On the other hand, when emulsion particle solidified, outer field silica segment easily moved to film coated surface, thereby can give full play to the effect of organosilicon segment, has improved the product cost performance.
Emulsifying agent of the present invention is the compound of anionic emulsifier and reactive emulsifier, and initiator is the compound of persulphate and sulphite, and initiator is oxidation-reduction system.At emulsifying agent, initiator, under the effect of organosilicon hydrolyzation inhibitor, adopt the reinforced method of gradient, the silicone content and the functional group thereof that make the siloxane-acrylate copolymer emulsion form micelle distribute from micelle radius 60 ~ 80% to surperficial progressive increase, made the self-crosslinking silicone-acrylic polymer emulsion that the latex particle particle diameter is about 100 nm, emulsion particle is whole in conjunction with very tight, phenomenon of phase separation can not occur, organo-siloxane monomer and segment mainly are distributed in micelle radius 60 ~ 80% places to the surface, given full play to the effect of Si-O-Si segment, improve the cost performance of organosilicon crylic acid latex, guaranteed the good film-forming properties of siloxane-acrylate copolymer emulsion, the performance such as water tolerance and anti-contamination.
The present invention is made by organo-siloxane and alkyl acrylate, alkyl methacrylate, hydroxyalkyl acrylate copolymerization.During preparation, first 50 ~ 80% alkyl methacrylate in the composition of raw materials, 30 ~ 70% alkyl acrylate are made the monomer I and polymerization makes seed emulsion, then alkyl methacrylate, the alkyl acrylate of remainder are made the monomer II, hydroxyalkyl acrylate and organo-siloxane are made the monomer III.When the monomer II evenly is added drop-wise to seed emulsion, simultaneously the monomer III evenly is added drop-wise in the monomer II, until the monomer III dropwises.Introduced reactive emulsifier and hydroxyl cross-linking monomer in the reaction, reduced and eliminated the micromolecular existence of emulsifying agent and cause the problems such as stability of emulsion, water-resistance property of coating be poor, the physical-chemical performance of emulsion film is improved.
The application of a kind of self-crosslinking silicone-acrylic polymer emulsion of the present invention on external wall.
Compared with prior art, the invention has the beneficial effects as follows:
(1) silicone content and the functional group thereof of prepared self-crosslinking silicone-acrylic polymer emulsion composition micelle distribute from micelle radius 60 ~ 80% to surperficial progressive increases, can give full play to the effect of organosilicon segment, improve the product cost performance.
(2) self-crosslinking silicone-acrylic polymer emulsion of the present invention has good reaction stability and stability in storage, films to have excellent contamination resistance, water tolerance, ageing resistance.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, raw materials used all commercially available among the embodiment, need to prove, embodiment does not consist of limiting the scope of the invention.
Embodiment 1:
(1) self-crosslinking silicone-acrylic polymer emulsion component is as shown in table 1 below:
(2) above-mentioned methyl methacrylate, butyl acrylate, 2-Hydroxy ethyl acrylate and vinyltriethoxysilane are mixed and made into respectively monomer I, monomer II and monomer III;
(3) preparation seed emulsion: with deionized water, SDS and the AMPS mixture quality of above-mentioned quality 80% 70%, Potassium Persulphate and sodium bisulfite mixture quality 60%, sodium bicarbonate, propylene glycol join in the reactor that thermometer, agitator, filling tube, condensing reflux pipe are housed, dispersed with stirring 15 minutes, treat that temperature rises to 68 ℃, the monomer I was dripped off in 3 hours, dropwise rear insulation 15 minutes, make seed emulsion;
(4) in 1.5 hours, slowly dropping to the monomer III in the monomer II and keeping to stir mixes it, then the mixture of above-mentioned monomer II and monomer III and remaining deionized water, emulsifying agent and initiator are added drop-wise to continuously in the seed emulsion that step (3) obtains, dropwised afterreaction 0.5 hour, be warming up to again 80 ℃ of insulations 1.5 hours, then be cooled to 40 ℃, filter discharging, namely get self-crosslinking siloxane-acrylate copolymer emulsion.
Per 20 minutes measured reaction system pH in step (4) reaction process are used sodium bicarbonate conditioned reaction system pH to 6.5 when the pH value is outside 6.0 ~ 7.0 intervals.
The self-crosslinking silicone-acrylic polymer seeds emulsion median size that experiment obtains is 65nm, and final median size is 95nm, narrowly distributing.Tem analysis shows self-crosslinking silicopropyl emulsion latex particle size evenly, is the sphere of rule.SEM and AFM the analysis showed that emulsion has good film-forming properties, and the film forming densification is without phenomenon of phase separation.NMR, FTIR and ultimate analysis etc. show, micelle is from particle diameter 65nm, and along with particle diameter increases gradually, the self-crosslinking silicone-acrylic polymer emulsion forms the silicone content of micelle and functional group thereof and distributes and also increase gradually.The self-crosslinking silicone-acrylic polymer emulsion water contact angle of filming is 115 °, and water-intake rate only was 2.3% in 24 hours.
Embodiment 2
(1) self-crosslinking silicone-acrylic polymer emulsion component is as shown in table 2 below:
(2) above-mentioned methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, vinylformic acid pentyl ester, 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, γ-methacryloxypropyl trimethoxy silane are mixed and made into respectively monomer I, monomer II and monomer III;
(3) preparation seed emulsion: with deionized water, DBS and the HAPS mixture quality of above-mentioned quality 70% 65%, ammonium persulphate and Potassium hydrogen sulfite mixture quality 50%, sodium bicarbonate, 1,4 butyleneglycols join in the reactor that thermometer, agitator, filling tube, condensing reflux pipe are housed, dispersed with stirring 10 minutes, treat that temperature rises to 65 ℃, the monomer I was dripped off at 3.5 hours, dropwise rear insulation 20 minutes, make seed emulsion;
(4) in 2 hours, slowly dropping to the monomer III in the monomer II and keeping to stir mixes it, and simultaneously the mixture of above-mentioned monomer II and monomer III and remaining deionized water, emulsifying agent and initiator are added drop-wise to continuously in the seed emulsion that step (3) obtains, dropwised afterreaction 0.5 hour, be warming up to again 78 ℃ of insulations 1 hour, then be cooled to 45 ℃, filter discharging, namely get self-crosslinking siloxane-acrylate copolymer emulsion.
Per 30 minutes measured reaction system pH in step (4) reaction process when the pH value is outside 6.0 ~ 7.0 intervals, are used sodium bicarbonate conditioned reaction system pH to 6.8.
The self-crosslinking silicone-acrylic polymer seeds emulsion median size that experiment obtains is 68nm, and final median size is 97nm, narrowly distributing.Tem analysis shows self-crosslinking silicone-acrylic polymer emulsion latex particle size evenly, is the sphere of rule.SEM and AFM the analysis showed that emulsion has good film-forming properties, and the film forming densification is without phenomenon of phase separation.NMR, FTIR and ultimate analysis etc. show, micelle is from particle diameter 68nm, and along with particle diameter increases gradually, the self-crosslinking silicone-acrylic polymer emulsion forms the silicone content of micelle and functional group thereof and distributes and also increase gradually.The self-crosslinking silicone-acrylic polymer emulsion water contact angle of filming is 112 °, and water-intake rate only was 2.8% in 24 hours.
Embodiment 3:
(1) self-crosslinking silicone-acrylic polymer emulsion component is as shown in table 3 below:
(2) above-mentioned β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl acrylate, 2-Hydroxy ethyl acrylate, vinylformic acid-5-hydroxyl pentyl ester and vinyl three butoxy silanes are mixed and made into respectively mix monomer I, mix monomer II and mix monomer III;
(3) preparation seed emulsion: with deionized water, LAS and the AMPS-NH of above-mentioned quality 75%
4Mixture quality 60%, Potassium Persulphate and sodium bisulfite mixture quality 70%, saleratus, the polymerization degree 400 low molecular polies join in the reactor that thermometer, agitator, filling tube, condensing reflux pipe are housed, dispersed with stirring 20 minutes, treat that temperature rises to 70 ℃, the mix monomer I was dripped off at 4 hours, dropwise rear insulation 30 minutes, make seed emulsion.
(4) in 2 hours, slowly dropping to the monomer III in the monomer II and keeping to stir mixes it, and simultaneously the mixture of above-mentioned monomer II and monomer III and remaining deionized water, emulsifying agent and initiator are added drop-wise to continuously in the seed emulsion that step (3) obtains, dropwised afterreaction 0.5 hour, be warming up to again 80 ℃ of insulations 1.5 hours, then be cooled to 50 ℃, filter discharging, namely get self-crosslinking siloxane-acrylate copolymer emulsion.
Per 30 minutes measured reaction system pH in step (4) reaction process when the pH value is outside 6.0 ~ 7.0 intervals, are used saleratus conditioned reaction system pH to 6.2.
The self-crosslinking silicone-acrylic polymer seeds emulsion median size that experiment obtains is 72nm, and final median size is 103nm, narrowly distributing.Tem analysis shows organosilicon crylic acid latex latex particle size evenly, is the sphere of rule.SEM and AFM the analysis showed that emulsion has good film-forming properties, and the film forming densification is without phenomenon of phase separation.NMR, FTIR and ultimate analysis etc. show, micelle is from particle diameter 72nm, and along with particle diameter increases gradually, the self-crosslinking silicone-acrylic polymer emulsion forms the silicone content of micelle and functional group thereof and distributes and also increase gradually.The self-crosslinking silicone-acrylic polymer emulsion water contact angle of filming is 110 °, and water-intake rate only was 3.2% in 24 hours.
Embodiment 4:
(1) self-crosslinking silicone-acrylic polymer emulsion component is as shown in table 4 below:
(2) above-mentioned methyl methacrylate, butyl methacrylate, Isooctyl methacrylate, ethyl propenoate, butyl acrylate, 2-Hydroxy ethyl acrylate, vinylformic acid-5-hydroxyl pentyl ester and vinyltrimethoxy silane are mixed and made into respectively monomer I, monomer II and monomer III;
(3) preparation seed emulsion: with deionized water, LAS, DSB, AMPS-Na, the AMPS-NH of above-mentioned quality 80%
4Mixture quality 60%, 65%, 80% saleratus, the polymerization degree 600 low molecular polies of Sodium Persulfate and sodium bisulfite mixture quality join in the reactor that thermometer, agitator, filling tube, condensing reflux pipe are housed, dispersed with stirring 15 minutes, treat that temperature rises to 68 ℃, the mix monomer I was dripped off at 2 hours, dropwise rear insulation 30 minutes, make seed emulsion.
(4) in 2 hours, slowly dropping to the mix monomer III in the monomer II and keeping to stir mixes it, and simultaneously the mixture of above-mentioned monomer II and monomer III and remaining deionized water, emulsifying agent and initiator are added drop-wise to continuously in the seed emulsion that step (3) obtains, dropwised afterreaction 1 hour, be warming up to again 85 ℃ of insulations 1 hour, then be cooled to 40 ℃, filter discharging, namely get self-crosslinking siloxane-acrylate copolymer emulsion.
Per 40 minutes measured reaction system pH in step (4) reaction process when the pH value is outside 6.0 ~ 7.0 intervals, are used saleratus conditioned reaction system pH to 6.5.
The self-crosslinking silicone-acrylic polymer seeds emulsion median size that experiment obtains is 62nm, and final median size is 98nm, narrowly distributing.Tem analysis shows organosilicon crylic acid latex latex particle size evenly, is the sphere of rule.SEM and AFM the analysis showed that emulsion has good film-forming properties, and the film forming densification is without phenomenon of phase separation.NMR, FTIR and ultimate analysis etc. show, micelle is from particle diameter 62nm, and along with particle diameter increases gradually, the self-crosslinking silicone-acrylic polymer emulsion forms the silicone content of micelle and functional group thereof and distributes and also increase gradually.The self-crosslinking silicone-acrylic polymer emulsion water contact angle of filming is 109 °, and water-intake rate only was 3.4% in 24 hours.
Claims (7)
1. a self-crosslinking silicone-acrylic polymer emulsion is characterized in that, described self-crosslinking silicone-acrylic polymer emulsion is to be made by following component, and the mass percent of each component is:
Alkyl methacrylate 10.0 ~ 30.0%,
Alkyl acrylate 15.0 ~ 30.0%,
Organo-siloxane 5 ~ 15%,
Hydroxyalkyl acrylate 0.5 ~ 2.5%,
Organosilicon hydrolyzation inhibitor 1.0 ~ 5.0%,
PH adjusting agent 0.5 ~ 2.0%,
Emulsifying agent 0.5 ~ 2.0%,
Initiator 0.5 ~ 1.0%,
Water 40.0 ~ 60.0%,
Described alkyl methacrylate is selected from the mixture of one or more arbitrary proportions in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, the Isooctyl methacrylate;
Described alkyl acrylate is selected from the mixture of one or more arbitrary proportions in methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, the Isooctyl acrylate monomer;
Described organo-siloxane is selected from the mixture of one or more arbitrary proportions in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three butoxy silanes, the γ-methacryloxypropyl trimethoxy silane;
Described hydroxyalkyl acrylate is selected from the mixture of one or more arbitrary proportions in 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxyl butyl ester, vinylformic acid-5-hydroxyl pentyl ester, the vinylformic acid-own ester of 6-hydroxyl, methacrylic acid-2-hydroxy methacrylate, the methacrylic acid-3-hydroxy propyl ester;
Described organosilicon hydrolyzation inhibitor is selected from the mixture of one or more arbitrary proportions in the low molecular poly of propylene glycol, Isosorbide-5-Nitrae butyleneglycol, the polymerization degree 400 or 600;
Described initiator is selected from persulphate and sulfite oxidation-reduction system, and persulphate is 1.5 ~ 2.5 times of sulphite quality,
Persulphate is selected from the mixture of one or more arbitrary proportions in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate, and sulphite is selected from the mixture of one or more arbitrary proportions in S-WAT, sodium bisulfite, potassium sulfite, Potassium hydrogen sulfite, ammonium sulphite, the ammonium bisulfite;
Described emulsifying agent is the compound of anionic emulsifier and reactive emulsifier, wherein reactive emulsifier is 1 ~ 3 times of anionic emulsifier quality, and anionic emulsifier is selected from the mixture of one or more arbitrary proportions in dodecyl diphenyl oxide disodium sulfonate (DSB), Sodium dodecylbenzene sulfonate (LAS), the sodium lauryl sulphate (SDS); Reactive emulsifier is selected from 2-acrylamido-2-methyl-propyl sulfonic acid sodium salt (AMPS-Na), 2-acrylamido-2-methyl-propyl sulfonic acid ammonium salt (AMPS-NH
4), the mixture of one or more arbitrary proportions in the 1-allyloxy-2-hydroxypropyl azochlorosulfonate acid sodium (HAPS), 2-acrylamido tetradecane sulfonate sodium (NaAMC14S), methacrylic acid hydroxide sodium dimercaptosulphanatein (HPMAS);
Described pH adjusting agent is selected from the mixture of one or both arbitrary proportions in sodium bicarbonate, the saleratus;
Described water is deionized water.
2. the preparation method of an a kind of self-crosslinking silicone-acrylic polymer emulsion as claimed in claim 1 is characterized in that, described preparation method is following steps:
(1) mass percent by component takes by weighing each component;
(2) 50% ~ 80% alkyl methacrylate, 30% ~ 70% alkyl acrylate in the step (1) are mixed and made into the monomer I, remaining alkyl methacrylate, alkyl acrylate are mixed and made into the monomer II, and hydroxyalkyl acrylate, organo-siloxane are mixed and made into the monomer III;
(3) preparation seed emulsion: 60% ~ 80% water, 50% ~ 80% emulsifying agent, 50% ~ 70% initiator, hydrolysis inhibitor, pH adjusting agent in the step (1) are added in the reactor, stir and be warming up to 65 ~ 70 ℃ after 10 ~ 20 minutes, then the monomer I is added in the reactor, dripped off in 2 ~ 4 hours, dropwise rear insulation 15 ~ 30 minutes, make seed emulsion;
(4) with the monomer III in 1 ~ 2 hour, drop in the monomer II and continue and stir, then mixture and remaining water, emulsifying agent and the initiator with above-mentioned monomer II and monomer III is added drop-wise in the seed emulsion that obtains in the step (3) continuously, dropwised afterreaction 0.5 ~ 1 hour, be warming up to again 75 ~ 85 ℃ of insulations 1 ~ 2 hour, then be cooled to 40 ~ 50 ℃, filter discharging, namely obtain the self-crosslinking silicone-acrylic polymer emulsion.
3. the preparation method of a kind of self-crosslinking silicone-acrylic polymer emulsion according to claim 2 is characterized in that, the mass ratio of monomer I and monomer II is 1.5 ~ 3:1 in the step (2).
4. according to claim 2 or the preparation method of 3 described a kind of self-crosslinking silicone-acrylic polymer emulsions, it is characterized in that, described monomer I second-order transition temperature is 10 ~ 30 ℃, and monomer II second-order transition temperature is-40 ~-20 ℃.
5. according to claim 2 or the preparation method of 3 described a kind of self-crosslinking silicone-acrylic polymer emulsions, it is characterized in that per 20 ~ 40 minutes measured reaction system pH in step (4) reaction process are regulated the pH value between 6.0 ~ 7.0.
6. the preparation method of a kind of self-crosslinking silicone-acrylic polymer emulsion according to claim 5 is characterized in that, uses the pH value of the material conditioned reaction system identical with the pH adjusting agent composition in the step (4).
7. the application of an a kind of self-crosslinking silicone-acrylic polymer emulsion as claimed in claim 1 on external wall.
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| CN103602193A (en) * | 2013-11-29 | 2014-02-26 | 深圳市安品有机硅材料有限公司 | Priming paint for water-borne heavy anti-corrosion coating and preparation method thereof |
| CN103626911A (en) * | 2013-10-14 | 2014-03-12 | 杭州师范大学 | Hydrophobic organic and inorganic acrylate polymer emulsion with high silicon content and preparation method and application thereof |
| CN105017903A (en) * | 2015-07-29 | 2015-11-04 | 广西梧州龙鱼漆业有限公司 | Scratch-resistant wall finish paint |
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| CN113698832A (en) * | 2021-07-13 | 2021-11-26 | 嘉宝莉化工集团股份有限公司 | Self-cleaning outdoor water-based nano tin antimony oxide-silicon dioxide/silicon acrylic composite transparent heat-insulating coating and preparation method thereof |
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| CN113336887A (en) * | 2021-07-01 | 2021-09-03 | 江苏华晟国联科技有限公司 | Preparation method of novel organic silicon modified amphiphilic acrylic emulsion |
| CN113698832A (en) * | 2021-07-13 | 2021-11-26 | 嘉宝莉化工集团股份有限公司 | Self-cleaning outdoor water-based nano tin antimony oxide-silicon dioxide/silicon acrylic composite transparent heat-insulating coating and preparation method thereof |
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| CN114989362A (en) * | 2022-07-11 | 2022-09-02 | 安徽科邦树脂科技有限公司 | Functional multifunctional siloxane prepolymer acrylate emulsion and preparation method thereof |
| CN114989362B (en) * | 2022-07-11 | 2024-03-01 | 安徽科邦树脂科技有限公司 | Functional polyfunctional siloxane prepolymer acrylate emulsion and preparation method thereof |
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