CN102408513A - Preparation method of phosphate modified acrylate emulsion - Google Patents
Preparation method of phosphate modified acrylate emulsion Download PDFInfo
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- CN102408513A CN102408513A CN2011103098883A CN201110309888A CN102408513A CN 102408513 A CN102408513 A CN 102408513A CN 2011103098883 A CN2011103098883 A CN 2011103098883A CN 201110309888 A CN201110309888 A CN 201110309888A CN 102408513 A CN102408513 A CN 102408513A
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Abstract
The invention relates to a preparation method of phosphate modified acrylate emulsion. The preparation method not only has relatively low cost, but also can effectively improve the flame retardation property of polyacrylate emulsion. The preparation method of phosphate modified acrylate emulsion comprises the following steps of: (1) primary polymerization: pre-emulsifying 10-20 parts of methyl methacrylate, 2-3 parts of methacrylic acid, 1-2 parts of acrylonitrile and 10-15 parts of styrene, then performing primary emulsion polymerization, and adjusting the pH value to obtain the primary polymerized emulsion; and (2) secondary polymerization: pre-emulsifying 30-45 parts of hydroxyl methacrylate substance, then adding the pre-emulsified product and 5-10 parts of phosphate monomer into the primary polymerized solution, and performing secondary emulsion polymerization to obtain the phosphate modified acrylate emulsion with a core-shell structure, wherein the phosphate monomer is trichloroethyl phosphate, trichloropropyl phosphate or n-ethyl phosphate; the molecular weight of polymer in the obtained phosphate modified acrylate emulsion is 2000-3000; and the particle size is 0.2-0.6 mu m.
Description
Technical field
The present invention relates to a kind of phosphate modified preparing acrylate emulsion method.
Background technology
Acrylic ester emulsion is because its excellent in water resistance ability, agglutinating value(of coal), film-forming properties, weathering resistance and guarantor's light are protected advantages such as look and mechanical property; Be applied as rubber-emulsion paint widely, in textile fabric, leather, paper, glass fibre sleeve and external wall, be widely used, but because it belongs to organic substance; It is inflammable to meet fire after the film forming; Produce thick smoke and the generation of objectionable impuritiess in a large number, influenced its range of application, therefore it is carried out the flame retardant resistance modification and be very important.
The unsaturated monomer of in acrylic ester emulsion, introducing the phosphoric acid group carries out modification by copolymerization, can improve the flame retardant properties of emulsion.But the unsaturated monomer of this phosphoric acid group needs special preparation, and costs an arm and a leg.
Summary of the invention
The present invention provides a kind of phosphate modified preparing acrylate emulsion method, and not only cost is lower, and can effectively improve the flame retardant properties of polyacrylate emulsion.
Said phosphate modified preparing acrylate emulsion method is:
(1) polymerization
With carrying out a letex polymerization after 10-20 part TEB 3K, 2-3 part methylacrylic acid, 1-2 part vinyl cyanide and the preparatory emulsification of 10-15 part vinylbenzene; Obtain the polymerized emulsion of pH value after the adjustment pH value for 5-6; Wherein polymericular weight is 2000-4000, and particle diameter is the 0.2-1 micron;
(2) after polymerization
With after the preparatory emulsification of 30-45 part hydroxyethyl methacrylate Ester and 5-10 part phosphate ester monomer add together in polymerized emulsion, carry out the secondary letex polymerization, obtain the phosphate modified acrylic ester emulsion of nucleocapsid structure,
Above-mentioned umber is mass fraction, and said phosphate ester monomer is trichloroethyl phosphate, trichlorine propyl phosphate or the positive ethyl ester of phosphoric acid, and the molecular weight of polymkeric substance is 2000-3000 in the phosphate modified acrylic ester emulsion of gained, and particle diameter is the 0.2-0.6 micron.
The nucleocapsid structure of phosphate modified acrylic ester emulsion can be confirmed by transmission electron microscope (hereinafter to be referred as the TEM) testing method of routine.
Preferably, use emulsifying agent 2-5 part altogether in a said polymerization and the after polymerization process, initiator 0.3-0.6 part, chain-transfer agent 2-4 part.
As preferred version, said phosphate modified acrylic ester emulsion obtains through the core-shell emulsion polymerization method with the raw material that following quality group becomes: TEB 3K 10-20%, methylacrylic acid 2-3%, hydroxyethyl methacrylate Ester 30-45%; Vinyl cyanide 1-2%, vinylbenzene 10-15%, phosphoric acid ester material 5-10%, emulsifying agent 2-5%; Initiator 0.3-0.6%, chain-transfer agent 2-4%, buffered soln 3-5%; Surplus is a water, and wherein, said initiator is FeSO
47H
2The mass ratio of O, tertbutyl peroxide and rongalite is (0.5-1): (0.5-1): mixture (0.3-0.5), and the step of core-shell emulsion polymerization is following:
(1) polymerization
1.1 preparatory polymerized emulsion of emulsification: with the 20-35% of water inventory, the emulsifying agent of 20-30% and all TEB 3K, vinylbenzene, methylacrylic acid, vinyl cyanide, chain-transfer agent mixing prepare one time the polymerization pre-emulsion;
A 1.2 polymerization: the 35-50% that adds water inventory is added in the four-hole bottle, and one time the polymerization pre-emulsion also joins in the four-hole bottle, is heated to 60 ℃, adds the FeSO of 40-60%
47H
2O drips the 50-70% tertbutyl peroxide is dissolved in the solution that forms in the 2-5% water, and then drips rongalite and be dissolved in the solution that forms in the 2-5% water, and reaction adds buffered soln again and obtains polymerized emulsion one time after finishing;
(2) after polymerization
2.1 preparatory emulsification after polymerization emulsion: the 20-30% of water inventory, remaining emulsifying agent and hydroxyethyl methacrylate Ester are mixed, and preparation after polymerization pre-emulsion cools off for use;
2.2 after polymerization process: be heated to 80 ℃ to a polymerized emulsion, drip after polymerization pre-emulsion, phosphate ester monomer and remaining tertbutyl peroxide and be dissolved in the solution that forms in the 3-8% water, 3～4h dropwises, and adds remaining FeSO then
47H
2O, heat-retaining condition is reaction down.
The hydroxyethyl methacrylate Ester is preferably Rocryl 400 or hydroxyethyl methacrylate monooctyl ester.
Said emulsifying agent is preferably polyoxyethylene nonylphenol vitriol or allyl polyethenoxy ether verivate vitriol, and polyoxyethylene nonylphenol vitriol preferred molecular weight is 600-700.
Said chain-transfer agent is preferably Dodecyl Mercaptan.
It is 50% ammonia soln that said buffered soln is preferably massfraction.Buffered soln can disposable whole addings when a polymerization, also can when a polymerization and after polymerization, add in two batches, as long as guarantee that the pH value of polymerized emulsion makes it to stablize.
The present invention introduces the SULPHOSUCCINIC ACID ESTER with flame retardant properties in the acrylic ester emulsion building-up process; Through the transesterification reaction of comonomer vinylformic acid hydroxyl Ester and SULPHOSUCCINIC ACID ESTER, make phosphate group and multipolymer form covalent bonds, the acrylic ester emulsion after the modification has possessed the flame retarding efficiency height, corrodibility is little and eco-friendly characteristics; Reduced the heat decomposition temperature of acrylic ester emulsion effectively; Improved its thermal stability, simultaneously, the vertical combustion experimental result of the phosphate modified acrylic ester emulsion after the film forming shows; Belong to flameless combustion behind the emulsion film forming after the modification; And extinguish behind the 2s combustion time, smokeless, no dropping, and under the situation that thermostability improves greatly, guaranteed good mechanical performance and adhesive property.This invention has guaranteed the expansion of acrylic ester emulsion range of application, and has guaranteed at application safeties in particular cases such as high temperature, fire, and environmental protection is had important contribution.The SULPHOSUCCINIC ACID ESTER material that the present invention uses is common material, need not to prepare especially function monomer, and price is far below the unsaturated monomer of phosphoric acid group, so product cost is lower.
Description of drawings
Fig. 1 is a synthetic emulsion DSC curve: b (product of embodiment 2) after a, the modification before the modification.We can find out in the DSC curve, and we can find out from a curve, and 82.3 ℃ of endotherm(ic)peaks of locating are the endotherm(ic)peaks of sloughing planar water; 327.4 ℃ locate that organism decomposes pairing endotherm(ic)peak in water of constitution and the acrylic ester emulsion in order to slough; Through contrast a, the b curve finds that the pairing peak of b curve and a all to the high temperature direction migration has taken place, and explains that the adding of SULPHOSUCCINIC ACID ESTER can delay organic heat decomposition temperature effectively, improves the thermal stability of emulsion;
Fig. 2 is the infrared spectrogram of Comparative Examples 1 (emulsion before the modification) and embodiment 1 (phosphate modified back emulsion).Among the figure, 3300cm
-1Absorption peak be-stretching vibration of OH 2950cm
-1Bimodal then be the stretching vibration of alkyl-CH, 1730cm
-1Stretching vibration for-C=O.1530-1590cm
-1Between multiplet be the association peak of phenyl ring, 1100cm
-1Stretching vibration for-C-O.By finding out among the figure; Existence owing to vinylformic acid hydroxyl ester in the Comparative Examples 1 gained acrylic ester emulsion has the strongest-OH vibration peak, and embodiment 1 is phosphate modified owing to having added, and-OH weakens at the peak; The basic disappearance advantageously proved the formation of SULPHOSUCCINIC ACID ESTER-propenoate composite structure.
Embodiment
In following examples, the emulsion property testing method is following:
1) film-forming properties
Carry out polymer cement waterproof paint according to following proportioning and film, coating thickness 1.5mm ± 0.2mm, maintenance under the standard conditions after the demoulding (curing condition: 23 ± 2 ℃ of temperature, humidity 60 ± 5%) 168h observe and are coated with membrane stage:
| Starting material | Weight (g) |
| Emulsion | ?100 |
| Water | ?145 |
| FOAMASTER TMThe NXZ skimmer | ?0.5 |
| Silicate cement P.O.42.5 | ?100 |
| Talcum powder 800 orders | 80 |
2) thermostability behind the emulsion film forming
Take by weighing 10g emulsion film forming in the tetrafluoroethylene mould; 50 ℃ of dryings 4 hours; Carry out the DSC test; Reference standard: GB/T19466.3-2004 plastics dsc (DSC) third part: the mensuration of fusion and Tc and heat content, and reference standard GB/T2408-1996 " horizontal method of plastics combustibility test method and normal beam technique " carries out combustionproperty test, record heat decomposition temperature, combustion case and combustion time.
3) coating watertightness, cohesive strength, tensile property test
Reference standard: JC/T894-2001 " polymer cement waterproof paint " is according among the B 1) proportioning make an experiment.
Comparative Examples 1,
Component formula is formed as follows:
Testing sequence: the preparatory emulsification of (1) monomer: with 40% of water inventory; 50% polyoxyethylene nonylphenol vitriol, X 2073 emulsifying agent and whole ammonia soln join in the flask; Drip TEB 3K, Rocryl 400, vinylbenzene carries out the preparatory emulsification of monomer, drips time 50min; Temperature 40-50 ℃, stirring velocity 450-480r/min.
(2) letex polymerization: get 10% of above-mentioned preparatory emulsified monomer and join in the remainder water; Add 80 ℃ of stirrings of remaining emulsifying agent simultaneously, in this emulsion, add 10% ammonium persulphate stirring 30min, emulsion presents light blue fluorescence; Continue to drip remaining preparatory emulsified monomer and initiator; Time is controlled at 3-4h, and temperature is 75-80 ℃, obtains the emulsion of milky white colour band blue-fluorescence.
Comparative Examples 2,
Component formula is formed as follows:
Testing sequence: the preparatory emulsification of (1) monomer: with 40% of water inventory; 50% polyoxyethylene nonylphenol vitriol, X 2073 emulsifying agent and whole ammonia soln join in the flask; Drip TEB 3K, Rocryl 400, vinylbenzene carries out the preparatory emulsification of monomer, drips time 50min; Temperature 40-50 ℃, stirring velocity 450-480r/min.
(2) letex polymerization: get 10% of above-mentioned preparatory emulsified monomer and join in the remainder water, add 80 ℃ of stirrings of remaining emulsifying agent simultaneously, in this emulsion, add 10% ammonium persulphate stirring 30min; Emulsion presents light blue fluorescence; Continue to drip remaining preparatory emulsified monomer and initiator, in dripping the preparatory emulsified monomer process of residue, drip the positive ethyl ester monomer of phosphoric acid simultaneously, the preceding 30min of dropping; Emulsion is normal; Along with the emulsion viscosity that increases that drips the positive ethyl ester of phosphoric acid increases, there is gel seize phenomenon, the failure of an experiment to occur even occur.
Component formula is formed as follows:
Synthesis step is following:
(1) polymerization
With 20%, 30% emulsifying agent of water inventory and all TEB 3K, vinylbenzene, methylacrylic acid, vinyl cyanide, Dodecyl Mercaptan join in the four-hole boiling flask, 50 ℃ of following high-speed stirring prepare one time the polymerization pre-emulsion, cool off for use;
A polymerization process: add water inventory 50% in four-hole bottle, one time the polymerization pre-emulsion also joins in the four-hole bottle, is heated to 60 ℃, adds 40%FeSO
47H
2O drips 70% tertbutyl peroxide is dissolved in the solution that forms in 2% water, and then drips rongalite and be dissolved in the solution that forms in 5% water, reaction 30min.Add 50% massfraction again and be 50% ammonia soln.The molecular weight 2000 of a polymerized emulsion, 0.2 micron of particle diameter.
(2) after polymerization
With water inventory 20%, remaining emulsifying agent and Rocryl 400 be added in the four-hole boiling flask, 50 ℃ of following high-speed stirring, preparation after polymerization pre-emulsion cools off for use;
The after polymerization process: be heated to 80 ℃ to a polymerized emulsion, drip after polymerization pre-emulsion, the positive ethyl ester monomer of phosphoric acid and remaining tertbutyl peroxide and be dissolved in the solution that forms in 3% water, 3.5h dropwises, and adds remaining FeSO then
47H
2O, insulation 1h.
Show that through the scattering of light result emulsion molecular weight is 2800, particle diameter is 0.3 micron.
The emulsion property test result is following:
1) film-forming properties
Specimen surface after maintenance is uniform and smooth, no bubble, hollowing, pinprick and orange peel phenomenon.
2) thermostability behind the emulsion film forming
3) coating watertightness, cohesive strength, tensile property test
| Sample | Tensile strength/MPa | Elongation at break/% | Cohesive strength/MPa | Watertightness |
| Comparative Examples 1 | 1.85 | 307 | 1.13 | 0.3MPa 30min is |
| Embodiment | ||||
| 1 | 2.02 | 298 | 1.15 | 0.3MPa 30min is waterproof |
Embodiment 2,
Component formula is formed as follows:
Synthesis step is following:
(1) polymerization
With 20%, 30% emulsifying agent of water inventory and all TEB 3K, vinylbenzene, methylacrylic acid, vinyl cyanide, Dodecyl Mercaptan join in the four-hole boiling flask, 50 ℃ of following high-speed stirring prepare one time the polymerization pre-emulsion, cool off for use;
A polymerization process: add water inventory 50% in four-hole bottle, one time the polymerization pre-emulsion also joins in the four-hole bottle, is heated to 60 ℃, adds 40%FeSO
47H
2O drips 70% tertbutyl peroxide is dissolved in the solution that forms in 2% water, and then drips rongalite and be dissolved in the solution that forms in 5% water, reaction 30min.Add 50% massfraction again and be 50% ammonia soln.The molecular weight 2200 of a polymerized emulsion, 0.2 micron of particle diameter.
(2) after polymerization
With water inventory 20%, remaining emulsifying agent and Rocryl 400 class material be added in the four-hole boiling flask, 50 ℃ of following high-speed stirring, preparation after polymerization pre-emulsion cools off for use;
The after polymerization process: be heated to 80 ℃ to a polymerized emulsion, drip after polymerization pre-emulsion, trichloroethyl phosphate and remaining tertbutyl peroxide and be dissolved in the solution that forms in 3% water, 3.5h dropwises, and adds remaining FeSO then
47H
2O, insulation 1h.
Show that through the scattering of light result emulsion molecular weight is 3000, particle diameter is 0.3 micron.
The emulsion property test result:
1) film-forming properties
Specimen surface after maintenance is uniform and smooth, no bubble, hollowing, pinprick and orange peel phenomenon.
2) thermostability behind the emulsion film forming
3) coating watertightness, cohesive strength, tensile property test
| Sample | Tensile strength/MPa | Elongation at break/% | Cohesive strength/MPa | Watertightness |
| Comparative Examples 1 | 1.68 | 300 | 1.12 | 0.3MPa 30min is waterproof |
| Embodiment 2 | 1.81 | 287 | 1.15 | 0.3MPa 30min is waterproof |
Embodiment 3,
Component formula is formed as follows:
Synthesis step is following:
(1) polymerization
With 20%, 30% emulsifying agent of water inventory and all TEB 3K, vinylbenzene, methylacrylic acid, vinyl cyanide, Dodecyl Mercaptan join in the four-hole boiling flask, 50 ℃ of following high-speed stirring prepare one time the polymerization pre-emulsion, cool off for use;
A polymerization process: add water inventory 50% in four-hole bottle, one time the polymerization pre-emulsion also joins in the four-hole bottle, is heated to 60 ℃, adds 40%FeSO
47H
2O drips 70% tertbutyl peroxide is dissolved in the solution that forms in 2% water, and then drips rongalite and be dissolved in the solution that forms in 5% water, reaction 30min.Add 50% massfraction again and be 50% ammonia soln.The molecular weight 3000 of a polymerized emulsion, 0.4 micron of particle diameter.
(2) after polymerization
With water inventory 20%, remaining emulsifying agent and hydroxyethyl methacrylate monooctyl ester class material be added in the four-hole boiling flask, 50 ℃ of following high-speed stirring, preparation after polymerization pre-emulsion cools off for use;
The after polymerization process: be heated to 80 ℃ to a polymerized emulsion, drip after polymerization pre-emulsion, trichlorine propyl phosphate and remaining tertbutyl peroxide and be dissolved in the solution that forms in 3% water, 3.5h dropwises, and adds remaining FeSO then
47H
2O, insulation 1h.
Show that through the scattering of light result emulsion molecular weight is 4000, particle diameter is 0.4 micron.
The emulsion property test result is following:
1) film-forming properties
Specimen surface after maintenance is uniform and smooth, no bubble, hollowing, pinprick and orange peel phenomenon.
2) thermostability behind the emulsion film forming
3) coating watertightness, cohesive strength, tensile property test
| Sample | Tensile strength/MPa | Elongation at break/% | Cohesive strength/MPa | Watertightness |
| Comparative Examples 1 | 1.96 | 321 | 1.13 | 0.3MPa 30min is waterproof |
| Embodiment 3 | 2.12 | 308 | 1.15 | 0.3MPa 30min is waterproof |
Embodiment 4,
Component formula is formed as follows:
Synthesis step is following:
(1) polymerization
With 20%, 30% emulsifying agent of water inventory and all TEB 3K, vinylbenzene, methylacrylic acid, vinyl cyanide, Dodecyl Mercaptan join in the four-hole boiling flask, 50 ℃ of following high-speed stirring prepare one time the polymerization pre-emulsion, cool off for use;
A polymerization process: add water inventory 50% in four-hole bottle, one time the polymerization pre-emulsion also joins in the four-hole bottle, is heated to 60 ℃, adds 40%FeSO
47H
2O drips 70% tertbutyl peroxide is dissolved in the solution that forms in 2% water, and then drips rongalite and be dissolved in the solution that forms in 5% water, reaction 30min.Add 50% massfraction again and be 50% ammonia soln.The molecular weight 2600 of a polymerized emulsion, 0.3 micron of particle diameter.
(2) after polymerization
With water inventory 20%, remaining emulsifying agent and hydroxyethyl methacrylate monooctyl ester class material be added in the four-hole boiling flask, 50 ℃ of following high-speed stirring, preparation after polymerization pre-emulsion cools off for use;
The after polymerization process: be heated to 80 ℃ to a polymerized emulsion, drip after polymerization pre-emulsion, trichloroethyl phosphate and remaining tertbutyl peroxide and be dissolved in the solution that forms in 3% water, 3.5h dropwises, and adds remaining FeSO then
47H
2O, insulation 1h.
Show that through the scattering of light result emulsion molecular weight is 3000, particle diameter is 0.3 micron.
The emulsion property test result:
1) film-forming properties
Specimen surface after maintenance is uniform and smooth, no bubble, hollowing, pinprick and orange peel phenomenon.
2) thermostability behind the emulsion film forming
3) coating watertightness, cohesive strength, tensile property test
| Sample | Tensile strength/MPa | Elongation at break/% | Cohesive strength/MPa | Watertightness |
| Comparative Examples 1 | 1.76 | 300 | 1.10 | 0.3MPa 30min is waterproof |
| Embodiment 4 | 1.98 | 286 | 1.13 | 0.3MPa 30min is waterproof |
Through the TEM test, Comparative Examples 1 and the resulting emulsion of embodiment 1-4 are complete form of spherical particles, and the inside and outside bright-dark degree of particle is different, and internal color is outer layer depth, can be inferred as to have the spheric nucleocapsid structure.
Claims (7)
1. a phosphate modified preparing acrylate emulsion method is characterized in that,
(1) polymerization
With carrying out a letex polymerization after 10-20 part TEB 3K, 2-3 part methylacrylic acid, 1-2 part vinyl cyanide and the preparatory emulsification of 10-15 part vinylbenzene; Obtain the polymerized emulsion of pH value after the adjustment pH value for 5-6; Wherein polymericular weight is 2000-3000, and particle diameter is the 0.2-0.4 micron;
(2) after polymerization
With after the preparatory emulsification of 30-45 part hydroxyethyl methacrylate Ester and 5-10 part phosphate ester monomer add together in polymerized emulsion, carry out the secondary letex polymerization, obtain the phosphate modified acrylic ester emulsion of nucleocapsid structure,
Above-mentioned umber is mass fraction, and said phosphate ester monomer is trichloroethyl phosphate, trichlorine propyl phosphate or the positive ethyl ester of phosphoric acid, and the molecular weight of polymkeric substance is 2000-4000 in the phosphate modified acrylic ester emulsion of gained, and particle diameter is the 0.2-0.6 micron.
2. phosphate modified preparing acrylate emulsion method as claimed in claim 1 is characterized in that, uses emulsifying agent 2-5 part altogether in a said polymerization and the after polymerization process, initiator 0.3-0.6 part, chain-transfer agent 2-4 part.
3. phosphate modified preparing acrylate emulsion method as claimed in claim 2 is characterized in that, the raw material that becomes with following quality group obtains through the core-shell emulsion polymerization method: TEB 3K 10-20%; Methylacrylic acid 2-3%, hydroxyethyl methacrylate Ester 30-45%, vinyl cyanide 1-2%; Vinylbenzene 10-15%, phosphoric acid ester material 5-10%, emulsifying agent 2-5%; Initiator 0.3-0.6%, chain-transfer agent 2-4%, buffered soln 3-5%; Surplus is a water, and wherein, said initiator is FeSO
47H
2The mass ratio of O, tertbutyl peroxide and rongalite is (0.5-1): (0.5-1): mixture (0.3-0.5), and the step of core-shell emulsion polymerization is following:
(1) polymerization
1.1 preparatory polymerized emulsion of emulsification: with the 20-35% of water inventory, the emulsifying agent of 20-30% and all TEB 3K, vinylbenzene, methylacrylic acid, vinyl cyanide, chain-transfer agent mixing prepare one time the polymerization pre-emulsion;
A 1.2 polymerization: the 35-50% that adds water inventory is added in the four-hole bottle, and one time the polymerization pre-emulsion also joins in the four-hole bottle, is heated to 60 ℃, adds the FeSO of 40-60%
47H
2O drips the 50-70% tertbutyl peroxide is dissolved in the solution that forms in the 2-5% water, and then drips rongalite and be dissolved in the solution that forms in the 2-5% water, and reaction adds buffered soln again and obtains polymerized emulsion one time after finishing;
(2) after polymerization
2.1 preparatory emulsification after polymerization emulsion: the 20-30% of water inventory, remaining emulsifying agent and hydroxyethyl methacrylate Ester are mixed, and preparation after polymerization pre-emulsion cools off for use;
2.2 after polymerization process: be heated to 80 ℃ to a polymerized emulsion, drip after polymerization pre-emulsion, phosphate ester monomer and remaining tertbutyl peroxide and be dissolved in the solution that forms in the 3-8% water, 3～4h dropwises, and adds remaining FeSO then
47H
2O, heat-retaining condition is reaction down.
4. like each described phosphate modified preparing acrylate emulsion method among the claim 1-3, it is characterized in that the hydroxyethyl methacrylate Ester is Rocryl 400 or hydroxyethyl methacrylate monooctyl ester.
5. like each described phosphate modified preparing acrylate emulsion method among the claim 1-3, it is characterized in that said emulsifying agent is polyoxyethylene nonylphenol vitriol or allyl polyethenoxy ether verivate vitriol.
6. like each described phosphate modified preparing acrylate emulsion method among the claim 1-3, it is characterized in that said chain-transfer agent is a Dodecyl Mercaptan.
7. like each described phosphate modified preparing acrylate emulsion method among the claim 1-3, it is characterized in that said buffered soln is that massfraction is the ammonia soln of 30-50%.
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