CN101712767A - Preparation method of organic silicon acrylic ester self-organizing gradient emulsion film - Google Patents
Preparation method of organic silicon acrylic ester self-organizing gradient emulsion film Download PDFInfo
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Abstract
The invention relates to a preparation method of an organic silicon acrylic ester self-organizing gradient emulsion film, which in particular comprises the following steps: firstly adopting a soap-free emulsion method to prepare organic silicon acrylic ester copolymer soap-free emulsion and methyl methacrylate copolymer soap-free emulsion; blending the two emulsion according to the weight ratio of 1:1; and self-organizing to form the emulsion film of which the content of silicon element is in gradient change from the surface of the base material to the surface of the air by utilizing the difference of surface energy between different emulsion particles and the difference of selected wettability to the base material. The invention solves the hydrolysis problem of multiple organic silicon monomers in the emulsion polymerization process, improves the silicon content and hydrophobic nature of the polymer; the surface on one side of the formed gradient emulsion film possesses excellent film forming property and caking property of acrylic ester polymer, and the surface on the other side possesses the advantages of excellent high temperature resistance, ultraviolet resistance, infrared radiation resistance, oxidation degradability resistance, low surface energy and the like of organic silicon; and the preparation method is simple and easy to control, has no pollution to the environment and is applied widely.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of preparation method of organic silicon acrylic ester self-organizing gradient emulsion film.
Background technology
Organosilicon polymer is the element polymer of using as far back as industrial acquisition, and it has good performance.At present, Chang Yong organosilane monomer has: vinyltrimethoxy silane, vinyl triethoxyl silicon, vinyl silane triisopropoxide, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-Ji acryloyl-oxy propyl-triethoxysilicane, gamma-methyl allyl acyloxypropyl three isopropoxy silane.These monomers mostly are double bond containing silane coupling agent greatly, owing to contain hydrolysable group Si-O-C, in the letex polymerization journey, hydrolytic condensation to a certain degree can take place in these groups, thereby make the excessive crosslinked unstability that causes reacting between polymer molecule, be difficult to obtain the polyacrylate dispersion of high silicon content.
In research in the past, although adopted monomer to postpone the dropping technology, add hydrolysis inhibitor (SCI, 1995,10:1810) etc., the amount of organosilane monomer also only accounts for 2%～5% of monomer total mass.Even utilize alcoholysis reaction with in γ-methacryloxy third Trimethoxy silane-OCH
3Group displacement become sterically hindered bigger-OCH
2CH
3Or-OCH (CH
3)
2, regulate monomer hydrolytic condensation speed in the polymerization process, silane contents also only accounts for amount of monomer 15% in the organic silicon acrylic ester copolymer emulsion of preparation.
Because gamma-methyl allyl acyloxypropyl three (trimethylsiloxy group) silane molecule volume is big, solubleness is little in the water, be difficult to emulsification, rarely have report up to now about the letex polymerization aspect of high silicon content organosilane monomer gamma-methyl allyl acyloxypropyl trimethoxysilane.
Organosilicon is introduced gradient material to be significant.Gradient material is meant that the component of constituent material is the successive graded along thickness direction from a side to opposite side, thereby makes the performance of material also become a kind of material with special performance of graded.CN 1339520A discloses a kind of utilization electric field and prepared the continually varying polymer blending material in aqueous solutions of polymers.CN 1510069A discloses a kind of by regulating the raw material composition, and means such as control extruder temperature are prepared the polymers function gradient material.CN1640914A discloses a kind of Prepared by Solution Mixing Method gradient film, and their shortcoming is to adopt solution system or molten system preparation, process complexity, energy consumption height, contaminate environment.Opposite self-organization polymer gradient latex film, adopt emulsion system, utilize the different of surface energy between the emulsion particle particle and to the difference of base material selective wetting, blend components can self-organization form gradient-structure, and environmentally safe causes more and more people's concern.
Summary of the invention
The technical problem to be solved in the present invention is: the preparation method that a kind of organic silicon acrylic ester self-organizing gradient emulsion film is provided, this method is not only simple to operate than molten system, energy consumption is low, and adopt eco-friendly emulsion system, avoided the problem of environmental pollution that solution system brought.
The technical scheme that the present invention solves its technical problem employing is: at first adopt the soap-free emulsion method to prepare organic silicon acrylic ester copolymerization soap-free emulsion and methyl methacrylate copolymer soap-free emulsion, again with two kinds of emulsions with weight ratio blend in 1: 1, utilize the different of surface energy between the different emulsion particle particles and to the difference of base material selective wetting, self-organization forms the latex film that silicon content changes in gradient from the substrate surface to the air surface.
The reaction formula of organic silicon acrylic ester copolymerization soap-free emulsion is:
The present invention compared with prior art has following main advantage:
One all adopts environmental friendliness, emulsion system that energy consumption is low, thus the shortcoming of having avoided solution system and molten system blend to be brought.
Its two, select for use gamma-methyl allyl acyloxypropyl three (trimethylsiloxy group) silane as organosilane monomer, not only solved the hydrolysis problem of most organosilane monomers in emulsion polymerization process, and because introducing-OSi (CH
3)
3The silicone content and the hydrophobic nature of polymkeric substance have been improved greatly, preparing a kind of gamma-methyl allyl acyloxypropyl three (trimethylsiloxy group) silane that contains is the acrylic ester copolymer soap-free emulsion of the high silicon content of organosilane monomer, and methacrylic ester copolymerization soap-free emulsion.
They are three years old, adopt emulsion blending, utilize blending emulsion self-organization film forming mechanism, self-organization forms the latex film that a kind of silicon content changes in gradient from the substrate surface to the air surface, make gradient latex film one side surface possess the film-forming properties and the weathering resistance of acrylic polymer excellence, the opposite side surface possesses advantages such as the good high thermal resistance of organosilicon, ultraviolet resistance, ir radiation and durability in oxidative degradation, low surface energy.
Its four, the preparation method is simple, be easy to control, environmentally safe can be widely used in fields such as building coating, tackiness agent and pressure sensitive adhesive.
Description of drawings
Fig. 1 is the infared spectrum of organic silicon acrylic ester copolymer emulsion.
As shown in Figure 1, organic silicon acrylic ester multipolymer infared spectrum is at 1056cm
-1There is the flexible absorption peak of the unsymmetrically of Si-O-Si key equally in the place, at 842cm
-1, 756cm
-1There is Si-CH
3Charateristic avsorption band, 1726cm simultaneously
-1The place is the charateristic avsorption band of ester group, and intensity is bigger, and does not have 1640cm in the infared spectrum
-1The stretching vibration absorption peak of the C=C at place disappears, and illustrates that gamma-methyl allyl acyloxypropyl three (trimethylsiloxy group) silane and methyl methacrylate participate in polymerization fully.
Fig. 2 is the two surface contact angle analyses of organosilicon gradient blending material.
As shown in Figure 2, be two surface contact angle data of silyl acrylate ester copolymer/pure acrylic acid ester copolymer blend film.A, b, c, d represent film and the air interface contact angle to water respectively, and film and air interface are to the contact angle of methylene iodide, and film and substrate interface are to the contact angle of water, and film and substrate interface are to the contact angle of methylene iodide.The siliceous segment of the significantly different explanations of the hydrophilic and hydrophobic on two surfaces is enriched in film and air interface.
Fig. 3 be organosilicon gradient blending material along thickness direction scanning electron microscope power spectrum SEM-EDS silicon content figure, wherein X-coordinate is represented the length of film section along thickness direction, ordinate zou is represented the relative content of element silicon.Analyze the section distribution collection of illustrative plates obtain as can be seen by scanning electron microscope power spectrum SEM-EDS, organosilicon is tangible Gradient distribution in this gradient blending thickness direction.
Embodiment
The invention provides the preparation method of organic silicon acrylic ester self-organizing gradient emulsion film, specifically: at first adopt the soap-free emulsion method to prepare organic silicon acrylic ester copolymerization soap-free emulsion and methyl methacrylate copolymer soap-free emulsion, again with two kinds of emulsions with weight ratio blend in 1: 1, utilize the different of surface energy between the different emulsion particle particles and to the difference of base material selective wetting, self-organization forms the latex film that silicon content changes in gradient from the substrate surface to the air surface.
Described organic silicon acrylic ester copolymerization soap-free emulsion can adopt the preparation of semi-continuous seed soap-free emulsion method, and its second-order transition temperature is 20～50 ℃.
Described organic silicon acrylic ester copolymerization soap-free emulsion can be made by the method for following steps, and its step comprises:
(1) preparation of pre-emulsion 1:
Deionized water and 1-propenyl-2-hydroxy alkyl sulfonic acid sodium added condensation reflux unit is housed, in the constant speed feeding device there-necked flask, stirred fast after 5～60 minutes ultrasonic 0～20 minute, add mix monomer again, obtain pre-emulsion 1; Mix monomer is made up of organosilane monomer and two kinds of monomers of methyl methacrylate, and two kinds of monomeric weight ratios are 1: 4～4: 1; Organosilane monomer is meant gamma-methyl allyl acyloxypropyl three (trimethylsiloxy group) silane, and the amount of 1-propenyl-2-hydroxy alkyl sulfonic acid sodium is 4%～10% of two kinds of monomeric total masses; The structural formula of 1-propenyl-2-hydroxy alkyl sulfonic acid sodium is: CH
2=CH-CH
2-O-CH
2-CH (OH)-CH
2-SO
3Na.
(2) preparation of pre-emulsion 2:
Deionized water and 1-propenyl-2-hydroxy alkyl sulfonic acid sodium is added in the there-necked flask, stirred fast after 5～60 minutes ultrasonic 0～20 minute, add mix monomer again, obtain pre-emulsion 2; Mix monomer is made up of organosilane monomer and two kinds of monomers of methyl methacrylate, and two kinds of monomeric weight ratios are 1: 4～4: 1.
The amount of 1-propenyl-2-hydroxy alkyl sulfonic acid sodium is 4%～10% of two kinds of monomeric total masses.
(3) preparation of organic silicon acrylic ester copolymerization soap-free emulsion:
Earlier with the logical nitrogen of pre-emulsion 1 half an hour, add disodium phosphate soln and Potassium Persulphate, disodium phosphate soln solute quality accounts for total monomer weight 1.2%; Heat up 70～75 ℃ again, reaction is warming up to 80 ℃ after half an hour, pre-emulsion 2 is slowly dripped by the constant speed feeding device, dripped 2～4 hours, add one time initiator during this time every half an hour, be incubated 2～5 hours, be cooled to room temperature after, drip several ammoniacal liquor and regulate emulsions, obtain theoretical solid content and be 20% organic silicon acrylic ester copolymerization soap-free emulsion to neutral.
The structural formula of described gamma-methyl allyl acyloxypropyl three (trimethylsiloxy group) silane is:
CH
2＝C(CH
3)-CO-(CH
2)
3-Si-(OSi(CH
3)
3)
3。
Described methyl methacrylate copolymer soap-free emulsion can adopt the emulsifier-free emulsion polymerization method preparation that once feeds intake, and its second-order transition temperature is less than 40 ℃.
Described methyl methacrylate copolymer soap-free emulsion can be made by the method for following steps, and its step comprises:
(1) preparation of pre-emulsion:
Deionized water and reactive emulsifier added be equipped with in the condensation reflux unit there-necked flask, stir the back fast and add mix monomer, pre-emulsification was stirred after 5～60 minutes ultrasonic 0～20 minute, obtained pre-emulsion.Mix monomer is made up of methyl methacrylate and two kinds of monomers of butyl acrylate, two kinds of monomeric weight ratios are 7: 3～5: 5, reactive emulsifier is that its structural formula is: R-NH-CO-CH=CH-SO based on the alkylamide vinyl sulfonic acid sodium of mix monomer (methyl methacrylate and butyl acrylate) total mass 3%～5%
3Na.
(2) preparation of methyl methacrylate copolymer soap-free emulsion:
Phosphoric acid hydrogen two is received solution and initiator to join in the above-mentioned pre-emulsion; under nitrogen protection; they are by heating in water bath to 75 ℃; there is blue light to occur continuing reaction 3 hours down in 80 ℃ after 15 minutes in the question response system; question response is cooled to fully and drips several ammoniacal liquor after the room temperature and regulate emulsions to neutral, obtains theoretical solid content and be 20% methyl methacrylate copolymer emulsion.Phosphoric acid hydrogen two is received the amount of solution's solute and the amount of initiator and is respectively 1.2%, 0.3%～1.2% of mix monomer total mass; Mix monomer is made up of methyl methacrylate and butyl acrylate.
The present invention after organic silicon acrylic ester copolymerization soap-free emulsion and methyl methacrylate copolymer soap-free emulsion are diluted respectively, with weight ratio blend in 1: 1, and fully mixes under 50 ℃.With blending emulsion film forming on base material of preparation, film-forming temperature is 30～75 ℃.Base material can adopt clean sheet glass.
Further illustrate content of the present invention below in conjunction with embodiment, but not only be confined to the following examples.
Embodiment 1, the preparation of organic silicon acrylic ester copolymerization soap-free emulsion:
A certain amount of water and 0.02g 1-propenyl-2-hydroxy alkyl sulfonic acid sodium adding are equipped with condensation reflux unit, in the constant speed feeding device there-necked flask, stir the back fast and add mix monomer (0.1g gamma-methyl allyl acyloxypropyl three (trimethylsiloxy group) silane, 0.4g methyl methacrylate).Pre-emulsification was stirred 5 minutes, obtained pre-emulsion 1.Remainder water and 0.04g 1-propenyl-2-hydroxy alkyl sulfonic acid sodium are added in the there-necked flask, stir the back fast and add mix monomer (0.2g gamma-methyl allyl acyloxypropyl three (trimethylsiloxy group) silane, 0.8g methyl methacrylate).Pre-emulsification was stirred 5 minutes, obtained pre-emulsion 2.With the logical nitrogen of pre-emulsion 1 half an hour, the disodium phosphate soln and the part Potassium Persulphate that add 0.0178g, heat up 75 ℃, be warming up to 80 ℃ after about reaction half an hour, pre-emulsion 2 is slowly dripped by the constant speed feeding device, dripped 2 hours, add one time initiator during this time every half an hour, be incubated 5 hours, be cooled to room temperature after, drip several ammoniacal liquor and regulate emulsion, obtain organic silicon acrylic ester copolymerization soap-free emulsion to neutral.Theoretical solid content is 20%.
Embodiment 2, the preparation of organic silicon acrylic ester copolymerization soap-free emulsion:
A certain amount of water and 0.05g 1-propenyl-2-hydroxy alkyl sulfonic acid sodium adding are equipped with condensation reflux unit, in the constant speed feeding device there-necked flask, stir the back fast and add mix monomer (0.4g gamma-methyl allyl acyloxypropyl three (trimethylsiloxy group) silane, 0.1g methyl methacrylate).Pre-emulsification was stirred 60 minutes, ultrasonic 20 minutes, obtained pre-emulsion 1.Remainder water and 0.1g 1-propenyl-2-hydroxy alkyl sulfonic acid sodium are added in the there-necked flask, stir the back fast and add mix monomer (0.8g gamma-methyl allyl acyloxypropyl three (trimethylsiloxy group) silane, 0.2g methyl methacrylate).Pre-emulsification was stirred 60 minutes, ultrasonic 20 minutes, obtained pre-emulsion 2.With the logical nitrogen of pre-emulsion 1 half an hour, the disodium phosphate soln and the part Potassium Persulphate that add 0.0178g, heat up 75 ℃, be warming up to 80 ℃ after about reaction half an hour, pre-emulsion 2 is slowly dripped by the constant speed feeding device, dripped 4 hours, add one time initiator during this time every half an hour, be incubated 2 hours, be cooled to room temperature after, drip several ammoniacal liquor and regulate emulsion, obtain organic silicon acrylic ester copolymerization soap-free emulsion to neutral.Theoretical solid content is 20%.
Embodiment 3, the preparation of methyl methacrylate copolymer soap-free emulsion:
With the 10.3g deionized water, the adding of 0.12g reactive emulsifier is equipped with in the condensation reflux unit there-necked flask, stirs the back fast and adds mix monomer (1.2g methyl methacrylate and 2.8g butyl acrylate).Pre-emulsification was stirred 45 minutes, and ultra-sonic dispersion is after 10 minutes, add 0.048g phosphoric acid hydrogen two and receive solution and 0.04g Potassium Persulphate, then reaction system under nitrogen protection by heating in water bath to 75 ℃.Treat to have in the system blue light to occur after 15 minutes, continue reaction 3 hours down in 80 ℃.Question response is complete, is cooled to room temperature, drips several ammoniacal liquor and regulates emulsion to neutral, obtains stable methyl methacrylate copolymer emulsion.Theoretical solid content 20%.
Embodiment 4, the preparation of organic silicon acrylic ester self-organizing gradient emulsion film:
A certain amount of water and 0.03g 1-propenyl-2-hydroxy alkyl sulfonic acid sodium adding are equipped with condensation reflux unit, in the constant speed feeding device there-necked flask, stir the back fast and add mix monomer (0.3g gamma-methyl allyl acyloxypropyl three (trimethylsiloxy group) silane, 0.2g methyl methacrylate).Pre-emulsification was stirred 60 minutes, and ultra-sonic dispersion 20 minutes obtains pre-emulsion 1.Remainder water and 0.06g 1-propenyl-2-hydroxy alkyl sulfonic acid sodium are added in the there-necked flask, stir the back fast and add mix monomer (0.6g gamma-methyl allyl acyloxypropyl three (trimethylsiloxy group) silane, 0.4g methyl methacrylate).Pre-emulsification was stirred 60 minutes, and ultra-sonic dispersion 20 minutes obtains pre-emulsion 2.With the logical nitrogen of pre-emulsion 1 half an hour, the disodium phosphate soln and the part Potassium Persulphate that add 0.0178g, heat up 75 ℃, be warming up to 80 ℃ after about reaction half an hour, pre-emulsion 2 is slowly dripped by the constant speed feeding device, dripped 3 hours, add one time initiator during this time every half an hour, be incubated 2 hours, be cooled to room temperature after, drip several ammoniacal liquor and regulate emulsion, obtain organic silicon acrylic ester copolymerization soap-free emulsion to neutral.Theoretical solid content is 20%.
With the 10.3g deionized water, the adding of 0.2g reactive emulsifier is equipped with in the condensation reflux unit there-necked flask, stirs the back fast and adds mix monomer (1.2g methyl methacrylate and 2.8g butyl acrylate).Pre-emulsification was stirred 1 hour, and ultra-sonic dispersion is after 20 minutes, add 0.048g phosphoric acid hydrogen two and receive solution and 0.04g Potassium Persulphate, then reaction system under nitrogen protection by heating in water bath to 75 ℃.Treat to have in the system blue light to occur after 15 minutes, continue reaction 3 hours down in 80 ℃.Question response is complete, is cooled to room temperature, drips several ammoniacal liquor and regulates emulsion to neutral, obtains methyl methacrylate copolymer emulsion.Theoretical solid content is 20%.
After organic silicon acrylic ester copolymer emulsion and methyl methacrylate copolymer emulsion be diluted to 5% respectively, with ratio blend in 1: 1.Blending emulsion descends stirring after 1 hour at 50 ℃, stirring at room 12 hours.Blending emulsion is dripped film forming on clean sheet glass.Film-forming temperature is 75 ℃.Obtain organic silicon acrylic ester self-organizing gradient emulsion film.
Embodiment 5, the preparation of organic silicon acrylic ester self-organizing gradient emulsion film:
The preparation method of blending emulsion is with embodiment 4.Film-forming temperature is 30 ℃.Obtain organic silicon acrylic ester self-organizing gradient emulsion film.
Embodiment 6, the preparation of organic silicon acrylic ester self-organizing gradient emulsion film:
The preparation method of blending emulsion is with embodiment 4.Film-forming temperature is 50 ℃.Obtain organic silicon acrylic ester self-organizing gradient emulsion film.
Embodiment 7, the preparation of organic silicon acrylic ester self-organizing gradient emulsion film:
Organic silicon acrylic ester copolymerization soap-free emulsion synthetic method is with example 4.
With the 10.3g deionized water, the adding of 0.2g reactive emulsifier is equipped with in the condensation reflux unit there-necked flask, stirs the back fast and adds mix monomer (1.6g methyl methacrylate and 2.4g butyl acrylate).Pre-emulsification was stirred 1 hour, and ultra-sonic dispersion is after 20 minutes, add 0.048g phosphoric acid hydrogen two and receive solution and 0.04g Potassium Persulphate, then reaction system under nitrogen protection by heating in water bath to 75 ℃.Treat to have in the system blue light to occur after 15 minutes, continue reaction 3 hours down in 80 ℃.Question response is complete, is cooled to room temperature, drips several ammoniacal liquor and regulates emulsion to neutral, obtains methyl methacrylate copolymer emulsion.
After organic silicon acrylic ester copolymer emulsion and methyl methacrylate copolymer emulsion be diluted to 5% respectively, with ratio blend in 1: 1.Blending emulsion descends stirring after 1 hour at 50 ℃, stirring at room 12 hours.Blending emulsion is dripped film forming on clean sheet glass.Film-forming temperature is 75 ℃.Obtain organic silicon acrylic ester self-organizing gradient emulsion film.
Embodiment 8, the preparation of organic silicon acrylic ester self-organizing gradient emulsion film:
Organic silicon acrylic ester copolymerization soap-free emulsion synthetic method is with example 4.
With the 10.3g deionized water, the adding of 0.2g reactive emulsifier is equipped with in the condensation reflux unit there-necked flask, stirs the back fast and adds mix monomer (2.0g methyl methacrylate and 2.0g butyl acrylate).Pre-emulsification was stirred 1 hour, and ultra-sonic dispersion is after 20 minutes, add 0.048g phosphoric acid hydrogen two and receive solution and 0.04g Potassium Persulphate, then reaction system under nitrogen protection by heating in water bath to 75 ℃.Treat to have in the system blue light to occur after 15 minutes, continue reaction 3 hours down in 80 ℃.Question response is complete, is cooled to room temperature, drips several ammoniacal liquor and regulates emulsion to neutral, obtains methyl methacrylate copolymer emulsion.
After organic silicon acrylic ester copolymer emulsion and methyl methacrylate copolymer emulsion be diluted to 5% respectively, with ratio blend in 1: 1.Stirring is after 1 hour down at 50 ℃ for blending emulsion, and stirring at room is more than 12 hours.Blending emulsion is dripped film forming on clean sheet glass.Film-forming temperature is 75 ℃.Obtain organic silicon acrylic ester self-organizing gradient emulsion film.
Claims (9)
1. the preparation method of an organic silicon acrylic ester self-organizing gradient emulsion film, it is characterized in that: at first adopt the soap-free emulsion method to prepare organic silicon acrylic ester copolymerization soap-free emulsion and methyl methacrylate copolymer soap-free emulsion, again with two kinds of emulsions with weight ratio blend in 1: 1, utilize the different of surface energy between the different emulsion particle particles and to the difference of base material selective wetting, self-organization forms the latex film that silicon content changes in gradient from the substrate surface to the air surface.
2. the preparation method of organic silicon acrylic ester self-organizing gradient emulsion film according to claim 1, it is characterized in that: described organic silicon acrylic ester copolymerization soap-free emulsion adopts the preparation of semi-continuous seed soap-free emulsion method, and its second-order transition temperature is 20～50 ℃.
3. the preparation method of organic silicon acrylic ester self-organizing gradient emulsion film according to claim 2 is characterized in that organic silicon acrylic ester copolymerization soap-free emulsion made by the method for following steps, and its step comprises:
(1) preparation of pre-emulsion 1:
Deionized water and 1-propenyl-2-hydroxy alkyl sulfonic acid sodium added condensation reflux unit is housed, in the constant speed feeding device there-necked flask, stirred fast after 5～60 minutes ultrasonic 0～20 minute, add mix monomer again, obtain pre-emulsion 1; Mix monomer is made up of organosilane monomer and two kinds of monomers of methyl methacrylate, and two kinds of monomeric weight ratios are 1: 4～4: 1; Organosilane monomer is meant gamma-methyl allyl acyloxypropyl three (trimethylsiloxy group) silane, and the amount of 1-propenyl-2-hydroxy alkyl sulfonic acid sodium is 4%～10% of two kinds of monomeric total masses; The structural formula of 1-propenyl-2-hydroxy alkyl sulfonic acid sodium is: CH
2=CH-CH
2-O-CH
2-CH (OH)-CH
2-SO
3Na;
(2) preparation of pre-emulsion 2:
Deionized water and 1-propenyl-2-hydroxy alkyl sulfonic acid sodium is added in the there-necked flask, stirred fast after 5～60 minutes ultrasonic 0～20 minute, add mix monomer again, obtain pre-emulsion 2; Mix monomer is made up of organosilane monomer and two kinds of monomers of methyl methacrylate, and two kinds of monomeric weight ratios are 1: 4～4: 1,
The amount of 1-propenyl-2-hydroxy alkyl sulfonic acid sodium is 4%～10% of two kinds of monomeric total masses;
(3) preparation of organic silicon acrylic ester copolymerization soap-free emulsion:
Earlier with the logical nitrogen of pre-emulsion 1 half an hour, add disodium phosphate soln and Potassium Persulphate, disodium phosphate soln solute quality accounts for total monomer weight 1.2%; Heat up 70～75 ℃ again, reaction is warming up to 80 ℃ after half an hour, pre-emulsion 2 is slowly dripped by the constant speed feeding device, dripped 2～4 hours, add one time initiator during this time every half an hour, be incubated 2～5 hours, be cooled to room temperature after, drip several ammoniacal liquor and regulate emulsions, obtain theoretical solid content and be 20% organic silicon acrylic ester copolymerization soap-free emulsion to neutral.
4. the preparation method of organic silicon acrylic ester self-organizing gradient emulsion film according to claim 3 is characterized in that the structural formula of gamma-methyl allyl acyloxypropyl three (trimethylsiloxy group) silane is:
CH
2＝C(CH
3)-CO-(CH
2)
3-Si-(OSi(CH
3)
3)
3。
5. the preparation method of organic silicon acrylic ester self-organizing gradient emulsion film according to claim 1, it is characterized in that: described methyl methacrylate copolymer soap-free emulsion adopts the emulsifier-free emulsion polymerization method preparation that once feeds intake, and its second-order transition temperature is less than 40 ℃.
6. the preparation method of organic silicon acrylic ester self-organizing gradient emulsion film according to claim 5 is characterized in that the methyl methacrylate copolymer soap-free emulsion made by the method for following steps, and its step comprises:
(1) preparation of pre-emulsion:
Deionized water and reactive emulsifier added be equipped with in the condensation reflux unit there-necked flask, stir the back fast and add mix monomer, pre-emulsification was stirred after 5～60 minutes ultrasonic 0～20 minute, obtained pre-emulsion.Mix monomer is made up of methyl methacrylate and two kinds of monomers of butyl acrylate, two kinds of monomeric weight ratios are 7: 3～5: 5, reactive emulsifier is that its structural formula is: R-NH-CO-CH=CH-SO based on the alkylamide vinyl sulfonic acid sodium of mix monomer (methyl methacrylate and butyl acrylate) total mass 3%～5%
3Na;
(2) preparation of methyl methacrylate copolymer soap-free emulsion:
Phosphoric acid hydrogen two is received solution and initiator to join in the above-mentioned pre-emulsion; under nitrogen protection by heating in water bath to 75 ℃; there is blue light to occur continuing reaction 3 hours down in 80 ℃ after 15 minutes in the question response system; question response is cooled to fully and drips several ammoniacal liquor after the room temperature and regulate emulsions to neutral, obtains theoretical solid content and be 20% methyl methacrylate copolymer emulsion.Phosphoric acid hydrogen two is received the amount of solution's solute and the amount of initiator and is respectively 1.2%, 0.3%～1.2% of mix monomer total mass; Mix monomer is made up of methyl methacrylate and butyl acrylate.
7. the preparation method of organic silicon acrylic ester self-organizing gradient emulsion film according to claim 1, it is characterized in that: after organic silicon acrylic ester copolymerization soap-free emulsion and methyl methacrylate copolymer soap-free emulsion dilute respectively, with weight ratio blend in 1: 1, and under 50 ℃, fully mix.
8. according to the preparation method of the described organic silicon acrylic ester self-organizing gradient emulsion film of arbitrary claim in the claim 1 to 7, it is characterized in that: with the organic silicon acrylic ester multipolymer/methylmethacrylate copolymer blending emulsion of preparation, in the base material film forming, film-forming temperature is 30～75 ℃.
9. the preparation method of organic silicon acrylic ester self-organizing gradient emulsion film according to claim 8 is characterized in that: the sheet glass that the base material employing is clean.
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