CN102977253A - Silicone modified acrylate hybrid emulsion and preparation method and application thereof - Google Patents
Silicone modified acrylate hybrid emulsion and preparation method and application thereof Download PDFInfo
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Abstract
The present invention discloses a silicone modified acrylate hybrid emulsion and a preparation method and application thereof. According to the present invention, the seed emulsion polymerization method is used, an acrylate monomer is taken as a raw material, the silsesquioxane group and the acrylate polymer are combined in the form of a covalent bond to prepare the silicone modified acrylate hybrid emulsion through the polyfunctional silsesquioxane reaction of the acrylate monomer with the carbon-carbon double bond, the high temperature resistance and low temperature resistance and water resistance performances of the acrylate polymer are improved, and the application range of the acrylate polymer is enlarged. The synthetic method of silicone modified acrylate provided by the present invention does not need a catalyst, has no byproducts, and is simple, high in product purity, and low in cost. The obtained silicone modified acrylate hybrid emulsion is stable in performance, and has excellent high and low temperature resistance, weather resistance, water resistance and other performances.
Description
Technical field
The invention belongs to the chemistry painting industry technical field, particularly a kind of organosilicon-modified acrylate hybridisation emulsion and preparation method thereof and application.
Background technology
Letex polymerization has low, fast, the environmental protection and separate the characteristics such as effect of conducting heat of system viscosity, and its product has been widely used in the fields such as coating, paint, tackiness agent, rubber and medicament slow release capsule carrier.The olefin(e) acid resin refer to acrylate monomer homopolymer, multipolymer and with the multipolymer of other vinyl monomers.Acrylic ester polymer is saturated compound, do not contain residual double bonds, have good anti-UV, resistance to acids and bases, oxidation-resistance, adhesivity, erosion resistance and weathering resistance have become the important kind in coating and the adhesive field and have been widely used in the industry-by-industries such as rubber, plastics, coating, tackiness agent, fabric finishing agent.
But acrylic ester polymer high-and low-temperature resistance and water resistance are relatively poor.Propylene vinegar polymkeric substance is because containing the polarity ester group in the molecular chain, therefore its water tolerance is relatively poor when having better adhesive power, easily turn white after the suction of filming, thus ester group even can decompose and affect the whole synthesis of product performance under certain condition.Simultaneously, the acrylic ester polymer particularly easy high temperature of linear polymer is clamminess, and contamination resistance descends, and low temperature becomes fragile, the toughness variation.The acrylate resin molecule mostly is linear structure, lacks cross-linking set, thereby heat impedance is relatively poor.
Si-O bond energy (450kJ/mol) is much larger than C-C bond energy (345kJ/mol) and C-O bond energy (351kJ/mol) in the organosilicon polymer, bibliographical information has been arranged synthesized the polyfunctionality silsesquioxane of carbon-carbon double bonds by silane coupling agent hydrolytic condensation method, to have good resistant of high or low temperature, weathering resistance, ventilation property, hydrophobicity and an anti-stain characteristic good and surface tension is low, protect the performances such as light, water-fast, anti-efflorescence and ultraviolet light because of its molecular structure characteristics, but its sticking power is relatively poor, can not normal temperature self-drying, film-forming properties is poor, and is bad to adhesion.Utilize the organosilicon component modification acrylic ester emulsion that bond energy is higher, surface energy is lower, can be in conjunction with the high-performance of the two, the complementation of making the most of the advantage improves high-and low-temperature resistance and the water resistance of acrylic ester polymer, thereby further enlarges its range of application.
Patent application 201010550379.5 discloses a kind of synthetic method of organic silicon modified propenoic ester copolymer, it adopts semicontinuous dripping method to synthesize the organosilicon seed emulsion, by semicontinuous dripping method, use acrylic ester monomer graft copolymerization, synthesized the organosilicon-modified acrylate graft copolymer of high silicone content.Patent 201010186222.9 discloses a kind of organosilicon (methyl) acrylate ABA block polymer and preparation method thereof and application; it adopts atom transfer radical polymerization synthetic; by bromine or chlorine polysiloxane or dimethyl siloxane and polysiloxane are carried out end-blocking; freezing by the cryosel bath, catalyzed reaction obtains the organic silicon acrylic ester ABA block polymer under nitrogen protection.The organosilicons such as siloxanes, polysiloxane and silane coupling agent contain siloxane structure, and siloxane structure is easy to be hydrolyzed and affects the package stability of emulsion.Above-mentioned document adopts these organosilicons that acrylate is carried out modification, owing to contain siloxane structure in these organosilicons, the acrylate hybrid stability of emulsion of preparing is poor, affects the practical application of acrylate hybrid emulsion.
Although both at home and abroad researcher is to organic silicon acrylic ester emulsion system contrast deep research and discussion, but the polymer-modified stability of emulsion that obtains is still not good enough, separate easily, coacervation, its reason is mainly manifested in: the emulsion that is difficult to obtain polymerization, stable storing when 1. the organosilicon addition is larger; 2. owing to hydrolysis, the polycondensation of siloxanes, crosslinked gel and the emulsion viscosity of causing too early increases; 3. an amount of acrylic acid or the like small molecules that adds for the mechanical stability that improves emulsion can impel the hydrolysis that contains the unsaturated double-bond silicon monomer, and the tendency of further autohemagglutination is arranged in emulsion polymerization process, causes the package stability variation of emulsion; 4. after polymerization is finished, the low molecule of emulsifying agent still exists with unbound state, they adsorb, contain, are scattered in the surperficial or inner of emulsion polymer micelle, unstable to light, heat, oxygen, the resistance to soiling that the meeting impact is filmed, water tolerance, weathering resistance etc., thereby the water-resistant coating for preparing, abrasion resistance and weathering resistance are not high.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of preparation method of organosilicon-modified acrylate hybridisation emulsion with not enough.
Another object of the present invention is to provide the organosilicon-modified acrylate that is obtained by above-mentioned preparation method hybridisation emulsion.
A further object of the present invention is to provide the application of described organosilicon-modified acrylate hybridisation emulsion.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of organosilicon-modified acrylate hybridisation emulsion comprises the steps:
The polyfunctionality silsesquioxane of 90～99 parts of acrylate monomers, 1～10 part of carbon-carbon double bonds, 2～3.5 parts of emulsifying agents and 80～100 parts of water are mixed, and pre-emulsification 10～30min obtains pre-emulsion while stirring; Get the pre-emulsion of 1/3～1/10 weight, be heated to 60～70 ℃, add 0.3～0.8 part of initiator A, in 70～80 ℃ of reaction 20～50min, obtain seed emulsion; Remaining pre-emulsion is added dropwise in 80～90 ℃ of seed emulsion, adds 0.3～0.8 part of initiator B, 80～90 ℃ were reacted 3～4 hours, and obtained the organosilicon-modified acrylate hybridisation emulsion;
Described umber is mass fraction;
The structural formula of the polyfunctionality silsesquioxane of described carbon-carbon double bonds is: R
mR ＇
n[SiO
1.5]
8
Described R is the substituting group of carbon-carbon double bonds, is preferably the alkyl of alkyl, thiazolinyl, aryl, arylidene, acrylate-based, methacrylate based or carbon-carbon double bonds;
Described R ＇ is preferably H;
Described m is preferably 2～8; Described n is preferably 0～6;
The polyfunctionality silsesquioxane of described carbon-carbon double bonds is preferably prestox methyl acrylate base silsesquioxane;
Described acrylate monomer is comprised of soft monomer and hard monomer;
Described soft monomer is preferably a kind of or at least two kinds of mixtures in n-butyl acrylate, isobutyl acrylate, vinylformic acid n-octyl, n octyl methacrylate, Isooctyl acrylate monomer and the Propylene glycol monoacrylate;
Described hard monomer is preferably a kind of or at least two kinds of mixtures in methyl methacrylate, vinylbenzene, vinylformic acid, the methacrylic acid;
The weight of described soft monomer is preferably 50%～70% of total monomer weight, and the weight of hard monomer is preferably 20%～40% of total monomer weight; The weight of the polyfunctionality silsesquioxane of described carbon-carbon double bonds is preferably 1%～10% of total monomer weight;
Described emulsifying agent is preferably a kind of or at least two kinds of mixtures in alkyl phenolic group Soxylat A 25-7, sodium lauryl sulphate, sodium laurylsulfonate and the Sodium dodecylbenzene sulfonate;
The weight of described emulsifying agent is preferably 2.0～3.5% of total monomer weight;
Described initiator A is preferably a kind of or at least two kinds of mixtures in Ammonium Persulfate 98.5, Potassium Persulphate and the S-WAT;
Described initiator B is preferably a kind of or at least two kinds of mixtures in Ammonium Persulfate 98.5, Potassium Persulphate and the S-WAT;
The weight of described initiator A is preferably 0.3%～0.8% of total monomer weight;
The weight of described initiator B is preferably 0.3%～0.8% of total monomer weight;
Described water is preferably deionized water; The weight of described water is preferably 80%～100% of total monomer weight;
Described total monomer weight refers to the gross weight of the polyfunctionality silsesquioxane of soft monomer, hard monomer and carbon-carbon double bonds;
The speed of described stirring is preferably 500～1000r/min;
Described pre-emulsification is preferably carried out at normal temperatures;
The time of described dropping is preferably 1～4 hour;
A kind of organosilicon-modified acrylate hybridisation emulsion is obtained by above-mentioned preparation method;
Described organosilicon-modified acrylate hybridisation emulsion can be applicable in the technical fields such as coating, paint, tackiness agent, rubber.
The present invention has following advantage and effect with respect to prior art:
The present invention adopts seed emulsion polymerization, take acrylate monomer as raw material, the reaction of the polyfunctionality silsesquioxane by acrylate monomer and carbon-carbon double bonds, the silsesquioxane group is combined with the form of covalent linkage with acrylic ester polymer, improve high-and low-temperature resistance and the water tolerance performance of acrylic ester polymer, further enlarged the range of application of acrylic ester polymer.
The synthetic method of organosilicon-modified acrylate provided by the invention need not catalyzer, and no coupling product produces, and synthetic method is simple, and product purity is high, and cost is low; The stable performance of resulting organosilicon-modified acrylate hybridisation emulsion has the performances such as good resistant of high or low temperature, weathering resistance and water tolerance.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1
50g methyl allyl acyloxypropyl trimethoxysilane, 12g water, 100ml ethanol and 1g Tetramethylammonium hydroxide five hydrates are added in the there-necked flask, 50 ℃ of magnetic agitation 48h, 50 ℃ of vacuum rotary steams are removed alcoholic solvent, obtain hydrolysate; Hydrolysate is dissolved in the 100ml toluene,, filters until neutrality adds five water magnesium sulfates and dewaters with saturated aqueous common salt solution washing toluene solution, 65 ℃ are reclaimed toluene, obtain prestox methyl acrylate base silsesquioxane.
Embodiment 2
Take the monomer total mass as 100 parts, (adopt the method for embodiment 1 to prepare 10 parts of 1 part of alkylphenol polyoxyethylene (OP-10), 1 part of sodium lauryl sulphate, 80 parts in water, 70 parts of n-butyl acrylates, 20 parts of methyl methacrylates and prestox methyl acrylate base silsesquioxanes.Together lower.) add among three mouthfuls of round-bottomed flask A, mixing, pre-emulsification 10min obtains pre-emulsion while stirring; Stirring velocity 500r/min;
The pre-emulsion of getting 1/10 part of pre-emulsion total mass adds among three mouthfuls of round-bottomed flask B, is heated to 60 ℃, adds ammonium persulfate solution and (gets 0.8 part of ammonium persulphate, be dissolved in 4 parts of water, and get final product.), in 70 ℃ of reaction 20min, obtain seed emulsion;
To remain pre-emulsion in 80 ℃ and be added dropwise to (the control rate of addition dropwised) in the seed emulsion in 3 hours, and add 0.8 part of ammonium persulphate, 80 ℃ of reactions were warming up to 90 ℃ after 1 hour, were incubated 2 hours, and cooling obtains organosilicon polyacrylic ester hybridisation emulsion.
Embodiment 3
Take the monomer total mass as 100 parts, 10 parts of 1.5 parts of alkylphenol polyoxyethylene (OP-10), 2 parts of sodium lauryl sulphate, 100 parts in water, 40 parts of Isooctyl acrylate monomers, 50 parts of methyl methacrylates and prestox methyl acrylate base silsesquioxanes are joined among three mouthfuls of round-bottomed flask A, mix, pre-emulsification 30min obtains pre-emulsion while stirring; Stirring velocity 1000r/min;
The pre-emulsion of getting 1/10 part of pre-emulsion total mass adds among three mouthfuls of round-bottomed flask B, is heated to 70 ℃, adds ammonium persulfate solution and (gets 0.3 part of ammonium persulphate, be dissolved in 4 parts of water, and get final product.), in 85 ℃ of reaction 30min, obtain seed emulsion;
To remain pre-emulsion in 85 ℃ and be added dropwise to (control rate of addition, monomer dropping is complete in 3 hours) in the seed emulsion, add 0.3 part of ammonium persulphate, 85 ℃ of reactions were warming up to 90 ℃ after 2 hours, be incubated 2 hours, cooling obtains organosilicon polyacrylic ester hybridisation emulsion.
Embodiment 4
Take the monomer total mass as 100 parts, in 1 part of alkylphenol polyoxyethylene (OP-10), 2 parts of sodium lauryl sulphate, 80 parts in water, 44 parts of n-butyl acrylates, 25 parts of Isooctyl acrylate monomers, 17 parts of methyl methacrylates, 13 parts of vinylbenzene and three mouthfuls of round-bottomed flask A of 1 part of adding of prestox methyl acrylate base silsesquioxane, mix, pre-emulsification 30min obtains pre-emulsion while stirring; Stirring velocity 800r/min;
The pre-emulsion of getting 1/6 part of pre-emulsion total mass adds among three mouthfuls of round-bottomed flask B, is heated to 65 ℃, adds ammonium persulfate solution (get 0.3 part of ammonium persulphate, be dissolved in 4 parts of water, and get final product), in 75 ℃ of reaction 30min, obtains seed emulsion;
To remain pre-emulsion in 80 ℃ and be added dropwise to (the control rate of addition dropwised) in the seed emulsion in 3 hours, and add 0.3 part of ammonium persulphate, 80 ℃ of reactions were warming up to 85 ℃ after 2 hours, were incubated 2 hours, and cooling obtains organosilicon polyacrylic ester hybridisation emulsion.
Embodiment 5
Take the monomer total mass as 100 parts, in 1 part of alkylphenol polyoxyethylene (OP-10), 2 parts of sodium lauryl sulphate, 90 parts in water, 60 parts of n-butyl acrylates, 35 parts of methyl methacrylates and three mouthfuls of round-bottomed flask A of 5 parts of addings of prestox methyl acrylate base silsesquioxane, mix, pre-emulsification 30min obtains pre-emulsion while stirring; Stirring velocity 800r/min;
The pre-emulsion of getting 1/5 part of pre-emulsion total mass adds among three mouthfuls of round-bottomed flask B, is heated to 70 ℃, adds ammonium persulfate solution (get 0.5 part of ammonium persulphate, be dissolved in 4 parts of water, and get final product), in 85 ℃ of reaction 30min, obtains seed emulsion;
To remain pre-emulsion in 85 ℃ and be added dropwise to (the control rate of addition dropwised) in the seed emulsion in 3 hours, and add 0.3 part of ammonium persulphate, 85 ℃ of reactions were warming up to 90 ℃ after 2 hours, were incubated 2 hours, and cooling obtains organosilicon polyacrylic ester hybridisation emulsion.
Embodiment 6
Take the monomer total mass as 100 parts, in 1 part of alkylphenol polyoxyethylene (OP-10), 2 parts of sodium lauryl sulphate, 80 parts in water, 60 parts of Isooctyl acrylate monomers, 35 parts of methyl methacrylates and three mouthfuls of round-bottomed flask A of 5 parts of addings of prestox methyl acrylate base silsesquioxane, mix, pre-emulsification 30min obtains pre-emulsion while stirring; Stirring velocity 800r/min;
The pre-emulsion of getting 1/6 part of pre-emulsion total mass adds among three mouthfuls of round-bottomed flask B, is heated to 70 ℃, adds ammonium persulfate solution (get 0.3 part of ammonium persulphate, be dissolved in 4 parts of water, and get final product), with 85 ℃ of reaction 30min, obtains seed emulsion;
To remain pre-emulsion in 85 ℃ and be added dropwise to (the control rate of addition dropwised) in the seed emulsion in 1 hour, and add 0.5 part of ammonium persulphate, 85 ℃ of reactions were warming up to 90 ℃ after 2 hours, were incubated 2 hours, and cooling obtains organosilicon polyacrylic ester hybridisation emulsion.
Embodiment 7
Take the monomer total mass as 100 parts, in 1 part of alkylphenol polyoxyethylene (OP-10), 2 parts of sodium lauryl sulphate, 80 parts in water, 60 parts of n-butyl acrylates, 35 parts of vinylbenzene and three mouthfuls of round-bottomed flask A of 5 parts of addings of prestox methyl acrylate base silsesquioxane, mix, pre-emulsification 30min obtains pre-emulsion while stirring; Stirring velocity 800r/min;
The pre-emulsion of getting 1/6 part of pre-emulsion total mass adds among three mouthfuls of round-bottomed flask B, is heated to 65 ℃, adds ammonium persulfate solution (get 0.3 part of ammonium persulphate, be dissolved in 4 parts of water, and get final product), in 75 ℃ of reaction 30min, obtains seed emulsion;
To remain pre-emulsion in 80 ℃ and be added dropwise to (the control rate of addition dropwised) in the seed emulsion in 3 hours, and add 0.3 part of ammonium persulphate, 80 ℃ of reactions were warming up to 85 ℃ after 2 hours, were incubated 2 hours, and cooling obtains organosilicon polyacrylic ester hybridisation emulsion.
Embodiment 8
Take the monomer total mass as 100 parts, in 1 part of alkylphenol polyoxyethylene (OP-10), 2 parts of sodium lauryl sulphate, 80 parts in water, 60 parts of Isooctyl acrylate monomers, 35 parts of vinylbenzene and three mouthfuls of round-bottomed flask A of 5 parts of addings of prestox methyl acrylate base silsesquioxane, mix, pre-emulsification 30min obtains pre-emulsion while stirring; Stirring velocity 800r/min;
The pre-emulsion of getting 1/6 part of pre-emulsion total mass adds among three mouthfuls of round-bottomed flask B, is heated to 65 ℃, adds ammonium persulfate solution (get 0.3 part of ammonium persulphate, be dissolved in 4 parts of water, and get final product), in 75 ℃ of reaction 50min, obtains seed emulsion;
To remain pre-emulsion in 80 ℃ and be added dropwise to (the control rate of addition dropwised) in the seed emulsion in 4 hours, and add 0.3 part of ammonium persulphate, 80 ℃ of reactions were warming up to 85 ℃ after 2 hours, were incubated 2 hours, and cooling obtains organosilicon polyacrylic ester hybridisation emulsion.
Embodiment 9
Take the monomer total mass as 100 parts, in 1 part of alkylphenol polyoxyethylene (OP-10), 2 parts of sodium lauryl sulphate, 80 parts in water, 40 parts of n-butyl acrylates, 30 parts of 25 parts of methyl methacrylates of Isooctyl acrylate monomer and three mouthfuls of round-bottomed flask A of 5 parts of addings of prestox methyl acrylate base silsesquioxane, mix, pre-emulsification 30min obtains pre-emulsion while stirring; Stirring velocity 500r/min;
The pre-emulsion of getting 1/10 part of pre-emulsion total mass adds among three mouthfuls of round-bottomed flask B, is heated to 70 ℃, adds ammonium persulfate solution (get 0.3 part of ammonium persulphate, be dissolved in 4 parts of water, and get final product), in 80 ℃ of reaction 30min, obtains seed emulsion;
To remain pre-emulsion in 80 ℃ and be added dropwise to (the control rate of addition dropwised) in the seed emulsion in 3 hours, and add 0.3 part of ammonium persulphate, 80 ℃ of reactions were warming up to 85 ℃ after 2 hours, were incubated 2 hours, and cooling obtains organosilicon polyacrylic ester hybridisation emulsion.
Embodiment 10
Take the monomer total mass as 100 parts, in 1 part of alkylphenol polyoxyethylene (OP-10), 2 parts of sodium lauryl sulphate, 80 parts in water, 40 parts of n-butyl acrylates, 25 parts of Isooctyl acrylate monomers, 30 parts of vinylbenzene and three mouthfuls of round-bottomed flask A of 5 parts of addings of prestox methyl acrylate base silsesquioxane, mix, pre-emulsification 30min obtains pre-emulsion while stirring; Stirring velocity 800r/min;
The pre-emulsion of getting 1/10 part of pre-emulsion total mass adds among three mouthfuls of round-bottomed flask B, is heated to 65 ℃, adds ammonium persulfate solution (get 0.4 part of ammonium persulphate, be dissolved in 4 parts of water, and get final product), in 75 ℃ of reaction 30min, obtains seed emulsion;
To remain pre-emulsion in 80 ℃ and be added dropwise to (the control rate of addition dropwised) in the seed emulsion in 3 hours, and add 0.3 part of ammonium persulphate, 80 ℃ of reactions were warming up to 85 ℃ after 2 hours, were incubated 2 hours, and cooling obtains organosilicon polyacrylic ester hybridisation emulsion.
Embodiment 11
Take the monomer total mass as 100 parts, in 1 part of alkylphenol polyoxyethylene (OP-10), 2 parts of sodium lauryl sulphate, 80 parts in water, 65 parts of n-butyl acrylates, 17 parts of methyl methacrylates, 13 parts of vinylbenzene and three mouthfuls of round-bottomed flask A of 5 parts of addings of prestox methyl acrylate base silsesquioxane, mix, pre-emulsification 30min obtains pre-emulsion while stirring; Stirring velocity 800r/min;
The pre-emulsion of getting 1/3 part of pre-emulsion total mass adds among three mouthfuls of round-bottomed flask B, is heated to 65 ℃, adds ammonium persulfate solution (get 0.3 part of ammonium persulphate, be dissolved in 4 parts of water, and get final product), in 75 ℃ of reaction 30min, obtains seed emulsion;
To remain pre-emulsion in 80 ℃ and be added dropwise to (the control rate of addition dropwised) in the seed emulsion in 3 hours, and add 0.3 part of ammonium persulphate, 80 ℃ of reactions were warming up to 85 ℃ after 2 hours, were incubated 2 hours, and cooling obtains organosilicon polyacrylic ester hybridisation emulsion.
Embodiment 12
Take the monomer total mass as 100 parts, in 1 part of alkylphenol polyoxyethylene (OP-10), 2 parts of sodium lauryl sulphate, 80 parts in water, 65 parts of Isooctyl acrylate monomers, 17 parts of methyl methacrylates, 13 parts of vinylbenzene and three mouthfuls of round-bottomed flask A of 5 parts of addings of prestox methyl acrylate base silsesquioxane, mix, pre-emulsification 30min obtains pre-emulsion while stirring; Stirring velocity 800r/min;
The pre-emulsion of getting 1/6 part of pre-emulsion total mass adds among three mouthfuls of round-bottomed flask B, is heated to 65 ℃, adds ammonium persulfate solution (get 0.3 part of ammonium persulphate, be dissolved in 4 parts of water, and get final product), in 75 ℃ of reaction 30min, obtains seed emulsion;
To remain pre-emulsion in 80 ℃ and be added dropwise to (the control rate of addition dropwised) in the seed emulsion in 3 hours, and add 0.3 part of ammonium persulphate, 80 ℃ of reactions were warming up to 85 ℃ after 2 hours, were incubated 2 hours, and cooling obtains organosilicon polyacrylic ester hybridisation emulsion.
Embodiment 13
Take the monomer total mass as 100 parts, in 1 part of alkylphenol polyoxyethylene (OP-10), 2 parts of sodium lauryl sulphate, 80 parts in water, 40 parts of n-butyl acrylates, 25 parts of Isooctyl acrylate monomers, 17 parts of methyl methacrylates, 13 parts of vinylbenzene and three mouthfuls of round-bottomed flask A of 5 parts of addings of prestox methyl acrylate base silsesquioxane, mix, pre-emulsification 20min obtains pre-emulsion while stirring; Stirring velocity 800r/min;
The pre-emulsion of getting 1/6 part of pre-emulsion total mass adds among three mouthfuls of round-bottomed flask B, is heated to 65 ℃, adds ammonium persulfate solution (get 0.3 part of ammonium persulphate, be dissolved in 4 parts of water, and get final product), in 75 ℃ of reaction 30min, obtains seed emulsion;
To remain pre-emulsion in 80 ℃ and be added dropwise to (the control rate of addition dropwised) in the seed emulsion in 3 hours, and add 0.3 part of ammonium persulphate, 80 ℃ of reactions were warming up to 85 ℃ after 2 hours, were incubated 2 hours, and cooling obtains organosilicon polyacrylic ester hybridisation emulsion.
Effect embodiment
Performance to the organosilicon-modified acrylate hybridisation emulsion of embodiment 10～13 preparation is tested (GB/T11175-2002), and test result is as shown in table 1:
The performance test results of the organosilicon-modified acrylate hybridisation emulsion of table 1 embodiment 10～13 preparations
As can be seen from Table 1, the stable performance of the organosilicon-modified acrylate hybridisation emulsion of the present invention's preparation has good resistant of high or low temperature, weathering resistance and water tolerance.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of an organosilicon-modified acrylate hybridisation emulsion is characterized in that comprising the steps:
The polyfunctionality silsesquioxane of 90～99 parts of acrylate monomers, 1～10 part of carbon-carbon double bonds, 2～3.5 parts of emulsifying agents and 80～100 parts of water are mixed, and pre-emulsification 10～30min obtains pre-emulsion while stirring; Get the pre-emulsion of 1/3～1/10 weight, be heated to 60～70 ℃, add 0.3～0.8 part of initiator A, in 70～80 ℃ of reaction 20～50min, obtain seed emulsion; Remaining pre-emulsion is added dropwise in 80～90 ℃ of seed emulsion, adds 0.3～0.8 part of initiator B, 80～90 ℃ were reacted 3～4 hours, and obtained the organosilicon-modified acrylate hybridisation emulsion;
Described umber is mass fraction.
2. the preparation method of organosilicon-modified acrylate hybridisation emulsion according to claim 1 is characterized in that:
Described acrylate monomer is comprised of soft monomer and hard monomer;
Described soft monomer is a kind of or at least two kinds of mixtures in n-butyl acrylate, isobutyl acrylate, vinylformic acid n-octyl, n octyl methacrylate, Isooctyl acrylate monomer and the Propylene glycol monoacrylate;
Described hard monomer is a kind of or at least two kinds of mixtures in methyl methacrylate, vinylbenzene, vinylformic acid, the methacrylic acid.
3. the preparation method of organosilicon-modified acrylate hybridisation emulsion according to claim 1 is characterized in that:
The structural formula of the polyfunctionality silsesquioxane of described carbon-carbon double bonds is: R
mR ＇
n[SiO
1.5]
8
Described R is the substituting group of carbon-carbon double bonds, and R ＇ is H; M is that 2～8, n is 0～6.
4. the preparation method of organosilicon-modified acrylate hybridisation emulsion according to claim 2, it is characterized in that: the weight of described soft monomer is 50%～70% of total monomer weight, the weight of hard monomer is 20%～40% of total monomer weight; Described total monomer weight refers to the gross weight of the polyfunctionality silsesquioxane of soft monomer, hard monomer and carbon-carbon double bonds.
5. the preparation method of organosilicon-modified acrylate hybridisation emulsion according to claim 1, it is characterized in that: described emulsifying agent is a kind of or at least two kinds of mixtures in alkyl phenolic group Soxylat A 25-7, sodium lauryl sulphate, sodium laurylsulfonate and the Sodium dodecylbenzene sulfonate.
6. the preparation method of organosilicon-modified acrylate hybridisation emulsion according to claim 1, it is characterized in that: described initiator A is a kind of or at least two kinds of mixtures in Ammonium Persulfate 98.5, Potassium Persulphate and the S-WAT.
7. the preparation method of organosilicon-modified acrylate hybridisation emulsion according to claim 1, it is characterized in that: described initiator B is a kind of or at least two kinds of mixtures in Ammonium Persulfate 98.5, Potassium Persulphate and the S-WAT; Described water is deionized water.
8. the preparation method of organosilicon-modified acrylate hybridisation emulsion according to claim 1, it is characterized in that: the speed of described stirring is 500～1000r/min; The time of described dropping is 1～4 hour.
9. organosilicon-modified acrylate hybridisation emulsion, each described preparation method obtains by claim 1～8.
10. the application of organosilicon-modified acrylate hybridisation emulsion claimed in claim 9 is characterized in that: use in the technical fields such as described organosilicon-modified acrylate hybridisation emulsion coating, paint, tackiness agent, rubber.
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