CN102311522B - Method for preparing acrylate-modified anionic polyurethane composite emulsion - Google Patents
Method for preparing acrylate-modified anionic polyurethane composite emulsion Download PDFInfo
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Abstract
The invention discloses a method for preparing an acrylate-modified anionic polyurethane composite emulsion, belonging to the technical field of adhesive preparation. The method disclosed by the invention comprises the following steps: carrying out polymerization on isocyanate and polymer dihydric alcohol through replacing an organic cosolvent used in the traditional polyurethane preparation process with an acrylate monomer so as to obtain a hydroxyl-obtaining polyurethane prepolymer; after cooling, introducing a proper amount of acrylate monomer and an initiator; and further initiating the polymerization of the acrylate monomer under the action of the initiator after neutralization and water dispersion so as to prepare the acrylate-modified anionic polyurethane composite emulsion. The method disclosed by the invention has the advantages that through taking the acrylate monomer as a solvent in the process of reaction without any organic cosolvent, the real environmental friendliness is achieved; the cost is lowered, and the adhesive performance of a water-gel and the appearance performance of a coating are improved; and no emulsifying agent is required to be added in the process of emulsion preparation, and the prepared product is excellent in performance, can be used in the field of composite adhesives and can also be used in fabric coatings.
Description
Technical field
The present invention relates to adhesive field, especially relate to a kind of preparation method of acrylate-modified anionic polyurethane composite emulsion.
Background technology
Most water-based PU (aqueous polyurethane composite emulsion) mainly is to be prepared by self-emulsification, indubitable, it is nontoxic, inexpensive, safe and the advantage such as do not fire that water-based PU possesses, but contain hydrophilic radical in its molecular structure, have the shortcomings such as the water tolerance of filming, solvent resistance deficiency, and its price is higher, and application is restricted.And contain small-molecular emulsifier in the multiple film glue of some simple acrylate, emulsifying agent moves to the surface in goods and latex, the physicalies such as product water tolerance, bonding strength are descended, and because viscosity own is large, poor fluidity, unstable, bring a lot of inconvenience to operation, usually there are the defectives such as the easy moisture absorption of paper product behind slow, the multiple film of rate of drying, deflection deformation or the foaming of in heat pressure forming process, being heated.
Summary of the invention
Embodiment of the present invention provides a kind of preparation method of acrylate-modified anionic polyurethane composite emulsion, can solve existing method and prepare in the urethane composite emulsion with an organic solvent environmental pollution, and prepared composite emulsion poor stability, the problem such as adhesiveproperties is poor and the coating outward appearance is bad.
The objective of the invention is to be achieved through the following technical solutions:
Embodiment of the present invention provides a kind of preparation method of acrylate-modified anionic polyurethane composite emulsion, and the method comprises:
A, polymer diatomic alcohol, carboxylic organic hydroxy compounds are joined in the reactor, be heated to fully dissolving, be cooled to 60 ℃ and add isocyanic ester, keep 80～90 ℃ of constant temperature, reacted 2～4 hours;
B, add the acrylic ester monomer of hydroxyl in the reactor of step a, 60～80 ℃ of lower reactions 1～3 hour, reduce the viscosity of reaction system in the reaction process by continuous adding first part acrylic ester monomer;
C, the reacted reactor of step b is cooled to below 40 ℃, the second section and the initiator that add the second section acrylic monomer in the described reactor stir evenly, adding an amount of neutralization reagent neutralizes again, add deionized water after 10～30 minutes and carry out emulsion reaction, then add quadrol and carried out rear chain extending reaction 20～60 minutes;
D, make the reacted reactor of step c after insulation for some time, in described reactor, drip remaining acrylic ester monomer and initiator, under 65～80 ℃ of temperature of reaction, dropwised in 3～5 hours, be incubated 0.5～2 hour, be warming up to 85 ℃ of reactions 1～2 hour, make to react completely, namely obtain solid content after the cooling and be 30～50% urethane composite emulsion
Beneficial effect of the present invention is: 1) do not add any organic cosolvent in this kind acrylic ester modified water-soluble polyurethane emulsion, the employing acrylic ester monomer is the solvent in the reaction process, reaches the environment friendly of its real meaning; 2) when reducing cost, improve the adhesiveproperties of glue and the appearance property of coating; 3) and in the emulsion preparation process, need not to add emulsifying agent, the products made thereby excellent property, by formula adjustment, it both can be used for the compound adhesive field of using, and also can be used in the fabric coating.
Embodiment
For ease of understanding, below in conjunction with specific embodiment, the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
Embodiment of the present invention provides a kind of preparation method of acrylate-modified anionic polyurethane composite emulsion, and the method may further comprise the steps:
A, polymer diatomic alcohol, carboxylic organic hydroxy compounds are joined in the reactor, be heated to fully dissolving, be cooled to 60 ℃ and add isocyanic ester, keep 80～90 ℃ of constant temperature, reacted 2～4 hours;
B, add the acrylic ester monomer of hydroxyl in the reactor of step a, 60～80 ℃ of lower reactions 1～3 hour, reduce the viscosity of reaction system in the reaction process by continuous adding first part acrylic ester monomer;
C, the reacted reactor of step b is cooled to below 40 ℃, the second section and the initiator that add the second section acrylic monomer in the described reactor stir evenly, adding an amount of neutralization reagent neutralizes again, add deionized water after 10～30 minutes and carry out emulsion reaction, then add quadrol and carried out rear chain extending reaction 20～60 minutes;
D, make the reacted reactor of step c after insulation for some time, in described reactor, drip remaining acrylic ester monomer and initiator, under 65～80 ℃ of temperature of reaction, dropwised in 3～5 hours, be incubated 0.5～2 hour, be warming up to 85 ℃ of reactions 1～2 hour, make to react completely, namely obtain solid content after the cooling and be 30～50% urethane composite emulsion.
In each step of aforesaid method, each raw material consumption of adding is by weight: described polymer diatomic alcohol 100: carboxylic organic hydroxy compounds 4～8: isocyanic ester 16～40: the acrylic ester monomer 2.0～8.0 of hydroxyl: neutralizing agent 3.0～6.0: quadrol 0.8～0.9;
The total amount of the remaining acrylic ester monomer that adds in the second section acrylic ester monomer that adds among the first part's acrylic ester monomer that adds in the described step b reaction process, the step c and the steps d accounts for 10～30% of system total solid content, the consumption of the first part's acrylic ester monomer that adds among the wherein said step b account for adding the acrylic ester monomer gross weight 10～40%; The consumption of the second section acrylic ester monomer that adds among the described step c account for adding the acrylic ester monomer gross weight 20～40%; Remaining acrylic ester monomer account for adding the acrylic ester monomer gross weight 20～40%;
The consumption of the described initiator that adds among the described step c be in the system acrylic ester monomer gross weight 0.5～2.0%.
The consumption of deionized water can be determined according to the solid content of the urethane composite emulsion of preparing to make in the aforesaid method.
Polymer diatomic alcohol among the aforesaid method step a adopts: any in polyether Glycols, polyester diol, polycaprolactone dibasic alcohol, the PCDL, the molecular weight of polymer diatomic alcohol are 1000～3000;
Carboxylic organic hydroxy compounds among the above-mentioned steps a is: can form hydrophilic functional group's the compound with active hydrogen, wherein the hydrophilic functional group is selected from any one or more in carboxylic acid, the sulfonic group; The compound with active hydrogen wherein adopts: any one or more in dimethylol propionic acid, dimethylolpropionic acid, quadrol base ethyl sulfonic acid sodium, the dihydroxyl half ester.
Isocyanic ester among the above-mentioned steps a adopts: ditan-4, any one or more of 4-vulcabond, hexamethylene vulcabond, isoflurane chalcone diisocyanate etc.
The acrylic ester monomer of the hydroxyl among the above-mentioned steps a adopts: any one or more in hydroxyethyl methylacrylate, the Hydroxyethyl acrylate.
Acrylic ester monomer in aforesaid method step b, step c and the steps d adopts: any one or more in butyl acrylate, methyl methacrylate, vinylbenzene, the ethyl propenoate.
Initiator among the aforesaid method step c adopts: any one or more in Diisopropyl azodicarboxylate, benzoyl peroxide, Potassium Persulphate, the ammonium persulphate; The consumption of described initiator accounts for 0.5～2.0% of system acrylic ester monomer gross weight.
Neutralizing agent among the aforesaid method step c adopts: any one or more in triethylamine, sodium hydroxide, potassium hydroxide, the trolamine.
The preparation method of the embodiment of the invention, substitute employed organic cosolvent in the conventional urethane preparation process with acrylic ester monomer, carry out the polymerization of isocyanic ester and polymer diatomic alcohol, make the base polyurethane prepolymer for use as of hydroxyl, after cooling, introduce an amount of acrylate monomer and initiator, the further polymerization of initiating methacrylates monomer under the effect of initiator makes a kind of acrylate-modified anionic polyurethane composite emulsion after neutralization, the water-dispersion.The advantage of the method is: 1) do not add any organic cosolvent in this kind acrylic ester modified water-soluble polyurethane emulsion, the employing acrylic ester monomer is the solvent in the reaction process, reaches the environment friendly of its real meaning; 2) when reducing cost, improve the adhesiveproperties of glue and the appearance property of coating; 3) and in the emulsion preparation process, need not to add emulsifying agent, the products made thereby excellent property, by formula adjustment, it both can be used for the compound adhesive field of using, and also can be used in the fabric coating.
Preparation method to urethane composite emulsion of the present invention is described further below in conjunction with specific embodiment.
Embodiment 1
The present embodiment provides a kind of preparation method of acrylate-modified anionic polyurethane composite emulsion, can prepare a kind of urethane composite emulsion, and the method may further comprise the steps:
A. be first that 2000 polyester diol 100 weight parts, dimethylol propionic acid 7 weight parts join in the reactor with molecular weight, be heated to fully dissolving, be cooled to 60 ℃ of ditans-4 that add 23 weight parts, the 4-vulcabond, keep 80～90 ℃ of constant temperature, reaction 2h～4h;
B. add hydroxyethyl methylacrylate 7 weight parts in the reactor in the step a, at 70 ℃ of lower reaction 1h～3h, constantly add butyl acrylate (be first part's acrylic ester monomer, add altogether the butyl acrylate of 10 weight parts) in the reaction process to reduce the viscosity of reaction system;
C. make the reacted reactor of step b be cooled to 40 ℃, the methyl methacrylate (being the second section acrylic ester monomer) and the initiator A IBN of 0.5 weight part that add 12 weight parts stir evenly, the neutralization reagent triethylamine that adds again 4.9 weight parts, neutralize, add 350 parts by weight of deionized water behind the 15min and carry out emulsion reaction, add afterwards chain extension 30min behind the chainextender quadrol of 0.8 weight part, obtain aqueous polyurethane dispersion;
D. after being incubated for some time, drip the butyl acrylate of remaining 5 weight parts (being remaining acrylic ester monomer) and the initiator A IBN of 0.5 weight part in the aqueous polyurethane dispersion that obtains to step c, under 75 ℃ of temperature of reaction, 4h dropwises, insulation 1h is warming up to 85 ℃ of reaction 1h again, makes to react completely, cooling obtains the PUA white emulsion of solid content about 30%, is acrylate-modified anionic polyurethane composite emulsion.
Embodiment 2
The present embodiment provides a kind of preparation method of acrylate-modified anionic polyurethane composite emulsion, can prepare a kind of urethane composite emulsion, and the method may further comprise the steps:
A. will join in the reactor for polyether Glycols 100 weight parts, dimethylolpropionic acid 8 weight parts of 2000 molecular weight first, be heated to fully dissolving, be cooled to 60 ℃ and add 40 weight part isoflurane chalcone diisocyanates, keep 90 ℃ of constant temperature, reaction 2h～4h;
B. in the reactor of a step, add hydroxyethyl methylacrylate 7 weight parts again, at 75 ℃ of lower reaction 1.5h, constantly add butyl acrylate (be first part's acrylic ester monomer, add altogether the butyl acrylate of 12 weight parts) in the reaction process to reduce the viscosity of reaction system;
C. be cooled to below 40 ℃, the butyl acrylate (being the second section acrylic ester monomer) and the initiator A IBN of 0.15 weight part that add 8 weight parts in the reactor of b step stir evenly again, add again 3.3 weight part neutralization reagent triethylamines, neutralize, add 170 parts by weight of deionized water behind the 30min and carry out emulsion reaction, then add quadrol (EDA) 0.8 weight part and carry out rear chain extending reaction 20min;
D. after being incubated for some time, drip the initiator A IBN of remaining methyl methacrylate 5 weight parts (being remaining acrylic ester monomer) and 0.03 weight part in the reactor of c step, under 70 ℃ of temperature of reaction, 3h dropwises, insulation 2h is warming up to 85 ℃ of reaction 1h again, makes to react completely, cooling obtains the PUA white emulsion of solid content about 50%, is acrylate-modified anionic polyurethane composite emulsion.
Embodiment 3
The present embodiment provides a kind of preparation method of acrylate-modified anionic polyurethane composite emulsion, can prepare a kind of urethane composite emulsion, and the method may further comprise the steps:
A. will be polyether Glycols 70 weight parts of 2000 molecular weight, polyester diol 30 weight parts of 2000 molecular weight first, dimethylol propionic acid 7 weight parts join in the reactor, be heated to fully dissolving, be cooled to 60 ℃ and add 23 parts by weight of toluene vulcabond, keep 90 ℃ of constant temperature, reaction 2h～4h;
B. in the reactor of a step, add hydroxyethyl methylacrylate 7 weight parts again, at 75 ℃ of lower reaction 1.5h, constantly add first part's acrylic ester monomer (mix monomer of methyl methacrylate and butyl acrylate adds 10 weight parts altogether) in the reaction process to reduce the viscosity of reaction system;
C. be cooled to below 40 ℃, in the reactor of b step, add the second section Acrylic Acid Monomer (mix monomer of methyl methacrylate and butyl acrylate again, totally 12 weight parts) and the initiator A IBN of 0.20 weight part stir evenly, add again 5.0 weight part neutralization reagent triethylamines, neutralize, add 210 parts by weight of deionized water behind the 30min and carry out emulsion reaction, then add quadrol (EDA) 0.9 weight part and carry out rear chain extending reaction 20min;
D. after being incubated for some time, in the reactor of c step, drip the remaining acrylic ester monomer (mix monomer of methyl methacrylate and butyl acrylate, totally 8 weight parts) and the initiator A IBN of 0.03 weight part, under 70 ℃ of temperature of reaction, 3h dropwises, insulation 2h, be warming up to again 85 ℃ of reaction 1h, make to react completely, it is about 40% PUA white emulsion that cooling obtains solid content, is acrylate-modified anionic polyurethane composite emulsion.
Embodiment 4
The present embodiment provides a kind of preparation method of acrylate-modified anionic polyurethane composite emulsion, can prepare a kind of urethane composite emulsion, and the method may further comprise the steps:
A. will join in the reactor for polyether Glycols 100 weight parts, dimethylolpropionic acid 8 weight parts of 2000 molecular weight first, be heated to fully dissolving, be cooled to 60 ℃ and add 36 weight part isoflurane chalcone diisocyanates, keep 90 ℃ of constant temperature, reaction 2h～4h;
B. in the reactor of a step, add hydroxyethyl methylacrylate 5 weight parts again, at 75 ℃ of lower reaction 1.5h, constantly add methyl methacrylate (be first part's acrylic ester monomer, add altogether 12 weight parts) in the reaction process to reduce the viscosity of reaction system;
C. be cooled to below 40 ℃, the butyl acrylate (being the second section acrylic ester monomer) and the initiator B PO of 0.15 weight part that add 8 weight parts in the reactor of b step stir evenly again, add again 5.2 weight part neutralization reagent triethylamines, neutralize, add 205 parts by weight of deionized water behind the 30min and carry out emulsion reaction, then add quadrol (EDA) 0.8 weight part and carry out rear chain extending reaction 20min;
D. after being incubated for some time, drip the initiator B PO of remaining methyl methacrylate 5 weight parts (being remaining acrylic ester monomer) and 0.03 weight part in the reactor of c step, under 70 ℃ of temperature of reaction, 3h dropwises, insulation 2h is warming up to 85 ℃ of reaction 1h again, makes to react completely, it is about 45% PUA white emulsion that cooling obtains solid content, is acrylate-modified anionic polyurethane composite emulsion.
Embodiment 5
The present embodiment provides a kind of preparation method of acrylate-modified anionic polyurethane composite emulsion, can prepare a kind of urethane composite emulsion, and the method may further comprise the steps:
A. will join in the reactor for polyether Glycols 100 weight parts, dimethylol propionic acid 6 weight parts, dimethylolpropionic acid 2 weight parts of 2000 molecular weight first, be heated to fully dissolving, be cooled to 60 ℃ and add 36 weight part isoflurane chalcone diisocyanates, keep 90 ℃ of constant temperature, reaction 2h～4h;
B. in the reactor of a step, add hydroxyethyl methylacrylate 7 weight parts again, at 75 ℃ of lower reaction 1.5h, constantly add first part's acrylic ester monomer (mix monomer of ethyl propenoate and methyl methacrylate adds 12 weight parts altogether) in the reaction process to reduce the viscosity of reaction system;
C. be cooled to below 40 ℃, adding the acrylic ester monomer (mix monomer of ethyl propenoate and methyl methacrylate) of second section 8 weight parts and the initiator A PS of 0.15 weight part in the reactor of b step stirs evenly again, add again 5.6 weight part neutralization reagent triethylamines, neutralize, add 205 parts by weight of deionized water behind the 30min and carry out emulsion reaction, then add quadrol (EDA) 0.8 weight part and carry out rear chain extending reaction 20min;
D. after being incubated for some time, drip the initiator A PS of remaining acrylic ester monomer 5 weight parts (mix monomer of ethyl propenoate and methyl methacrylate) and 0.03 weight part in the reactor of c step, under 70 ℃ of temperature of reaction, 3h dropwises, insulation 2h is warming up to 85 ℃ of reaction 1h again, makes to react completely, it is about 45% PUA white emulsion that cooling obtains solid content, is acrylate-modified anionic polyurethane composite emulsion.
Embodiment 6
The present embodiment provides a kind of preparation method of acrylate-modified anionic polyurethane composite emulsion, can prepare a kind of urethane composite emulsion, and the method may further comprise the steps:
A. will be polyether Glycols 50 weight parts of 2000 molecular weight, polyester diol 50 weight parts of 2000 molecular weight first, dimethylol propionic acid 7 weight parts join in the reactor, be heated to fully dissolving, be cooled to 60 ℃ and add 23 parts by weight of toluene vulcabond, keep 90 ℃ of constant temperature, reaction 2h～4h;
B. in the reactor of a step, add Hydroxyethyl acrylate 5 weight parts again, at 75 ℃ of lower reaction 1.5h, constantly add first part's acrylic ester monomer (mix monomer of methyl methacrylate and butyl acrylate, add-on are 10 weight parts) in the reaction process to reduce its viscosity;
C. be cooled to below 40 ℃, in the reactor of b step, add the second section Acrylic Acid Monomer (mix monomer of methyl methacrylate and butyl acrylate again, add altogether 12 weight parts) and the initiator A PS of 0.20 weight part stir evenly, add again 5.0 weight part neutralization reagent triethylamines, neutralize, the deionized water that adds 210 weight parts behind the 30min carries out emulsion reaction, then adds quadrol (EDA) 0.9 weight part and carries out rear chain extending reaction 20min;
D. after being incubated for some time, in the reactor of c step, drip the residual acrylic acid esters monomer (mix monomer of methyl methacrylate and butyl acrylate, add-on is 8 weight parts) and the initiator A PS of 0.03 weight part, under 70 ℃ of temperature of reaction, 3h dropwises, insulation 2h, be warming up to again 85 ℃ of reaction 1h, make to react completely, it is about 40% PUA white emulsion that cooling obtains solid content, is acrylate-modified anionic polyurethane composite emulsion.
In sum, the preparation method of the embodiment of the invention: do not add any organic cosolvent in the acrylic ester modified water-soluble polyurethane emulsion, the employing acrylic ester monomer is the solvent in the reaction process, reaches the environment friendly of its real meaning; When reducing cost, improve the adhesiveproperties of glue and the appearance property of coating; And in the emulsion preparation process, need not to add emulsifying agent, and the products made thereby excellent property, by formula adjustment, it both can be used for the compound adhesive field of using, and also can be used in the fabric coating.
The above; only for the better embodiment of the present invention, but protection scope of the present invention is not limited to this, anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (6)
1. the preparation method of an acrylate-modified anionic polyurethane composite emulsion is characterized in that, the method comprises:
A, polymer diatomic alcohol, carboxylic organic hydroxy compounds are joined in the reactor, be heated to fully dissolving, be cooled to 60 ℃ and add isocyanic ester, keep 80～90 ℃ of constant temperature, reacted 2～4 hours;
Carboxylic organic hydroxy compounds among the described step a is: can form hydrophilic functional group's the compound with active hydrogen, wherein the hydrophilic functional group is selected from any one or more in carboxylic acid, the sulfonic group;
Described compound with active hydrogen adopts: any one or more in dimethylol propionic acid, dimethylolpropionic acid, quadrol base ethyl sulfonic acid sodium, the dihydroxyl half ester;
B, add the acrylic ester monomer of hydroxyl in the reactor of step a, 60～80 ℃ of lower reactions 1～3 hour, reduce the viscosity of reaction system in the reaction process by continuous adding first part acrylic ester monomer;
The acrylic ester monomer of the hydroxyl among the described step b adopts: any one or more in hydroxyethyl methylacrylate, the Hydroxyethyl acrylate;
C, the reacted reactor of step b is cooled to below 40 ℃, add the second section acrylic ester monomer in the described reactor and initiator stirs evenly, adding an amount of neutralization reagent neutralizes again, add deionized water after 10～30 minutes and carry out emulsion reaction, then add quadrol and carried out rear chain extending reaction 20～60 minutes;
D, make the reacted reactor of step c after insulation for some time, in described reactor, drip remaining acrylic ester monomer and initiator, under 65～80 ℃ of temperature of reaction, dropwised in 3～5 hours, be incubated 0.5～2 hour, be warming up to 85 ℃ of reactions 1～2 hour, make to react completely, namely obtain solid content after the cooling and be 30～50% urethane composite emulsion;
Acrylic ester monomer in described step b, step c and the steps d adopts: any one or more in butyl acrylate, methyl methacrylate, vinylbenzene, the ethyl propenoate;
In each step of aforesaid method, each raw material consumption of adding is by weight: described polymer diatomic alcohol 100: carboxylic organic hydroxy compounds 4～8: isocyanic ester 16～40: the acrylic ester monomer 2.0～8.0 of hydroxyl: neutralizing agent 3.0～6.0: quadrol 0.8～0.9;
The total amount of the remaining acrylic ester monomer that adds in the second section acrylic ester monomer that adds among the first part's acrylic ester monomer that adds in the described step b reaction process, the step c and the steps d accounts for 10～30% of system total solid content, the consumption of the first part's acrylic ester monomer that adds among the wherein said step b account for adding the acrylic ester monomer gross weight 10～40%; The consumption of the second section acrylic ester monomer that adds among the described step c account for adding the acrylic ester monomer gross weight 20～40%;
The consumption of the described initiator that adds among the described step c be in the system acrylic ester monomer gross weight 0.5～2.0%.
2. the preparation method of acrylate-modified anionic polyurethane composite emulsion according to claim 1, it is characterized in that: the polymer diatomic alcohol among the described step a adopts: any in polyether Glycols, polyester diol, polycaprolactone dibasic alcohol, the PCDL, the molecular weight of polymer diatomic alcohol are 1000～3000.
3. the preparation method of acrylate-modified anionic polyurethane composite emulsion according to claim 1, it is characterized in that: the isocyanic ester among the described step a adopts: ditan-4, in 4-vulcabond, hexamethylene vulcabond, the isoflurane chalcone diisocyanate any one or more.
4. the preparation method of acrylate-modified anionic polyurethane composite emulsion according to claim 1 is characterized in that: the acrylic ester monomer employing in described step b, step c and the steps d: any one or more in butyl acrylate, methyl methacrylate, the ethyl propenoate.
5. the preparation method of acrylate-modified anionic polyurethane composite emulsion according to claim 1 is characterized in that: the initiator employing among the described step c: any one or more in Diisopropyl azodicarboxylate, benzoyl peroxide, Potassium Persulphate, the ammonium persulphate.
6. the preparation method of acrylate-modified anionic polyurethane composite emulsion according to claim 1 is characterized in that: the neutralizing agent employing among the described step c: any one or more in triethylamine, sodium hydroxide, potassium hydroxide, the trolamine.
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| CN102093516A (en) * | 2010-12-28 | 2011-06-15 | 东莞市英科水墨有限公司 | Waterborne polyurethane-acrylate emulsion prepared by seed emulsion polymerization method |
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| CN101717468A (en) * | 2009-11-18 | 2010-06-02 | 北京高盟化工有限公司 | Aqueous acrylic emulsion, aqueous adhesive for plastic-plastic composite materials and preparation method thereof |
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