CN102311522A - 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
Present most of water-based PU (aqueous polyurethane composite emulsion) mainly is to be prepared by self-emulsification; Indubitable; It is nontoxic, inexpensive, safe and advantage such as do not fire that water-based PU possesses, but contain hydrophilic radical in its molecular structure, has 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 propenoate; Emulsifying agent moves to the surface in goods and latex, and physicalies such as product water tolerance, bonding strength are descended, and because viscosity own is big; Mobile poor; Instability is brought a lot of inconvenience to operation, have slow, the multiple film of rate of drying usually after paper product be prone to defectives such as the moisture absorption, 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 environmental pollution with an organic solvent, and problem such as prepared composite emulsion poor stability, adhesiveproperties difference and coating outward appearance be bad.
The objective of the invention is to realize through following technical proposals:
Embodiment of the present invention provides a kind of preparation method of acrylate modified anionic polyurethane composite emulsion, and this method comprises:
A, polymer diatomic alcohol, carboxylic organic hydroxy compounds are joined in the reaction kettle, be heated to dissolving fully, be cooled to 60 ℃ and add isocyanic ester, keep 80～90 ℃ of constant temperature, reacted 2～4 hours;
B, in the reaction kettle of step a, add the acrylic ester monomer of hydroxyl,, reduce the viscosity of reaction system in the reaction process through continuous adding first part acrylic ester monomer 60～80 ℃ of reactions 1～3 hour down;
C, the reacted reaction kettle of step b is cooled to below 40 ℃; The second section and the initiator that in said reaction kettle, add the second section acrylic monomer stir; Adding an amount of neutralization reagent again neutralizes; Add deionized water after 10～30 minutes and carry out emulsion reaction, add quadrol then and carried out the back chain extending reaction 20～60 minutes;
D, make the reacted reaction kettle of step c after insulation for some time; In said reaction kettle, 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, promptly 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, adopting 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, through 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, will combine specific embodiment below, the technical scheme in the embodiment of the invention is carried out clear, intactly description, 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 are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
Embodiment of the present invention provides a kind of preparation method of acrylate modified anionic polyurethane composite emulsion, and this method may further comprise the steps:
A, polymer diatomic alcohol, carboxylic organic hydroxy compounds are joined in the reaction kettle, be heated to dissolving fully, be cooled to 60 ℃ and add isocyanic ester, keep 80～90 ℃ of constant temperature, reacted 2～4 hours;
B, in the reaction kettle of step a, add the acrylic ester monomer of hydroxyl,, reduce the viscosity of reaction system in the reaction process through continuous adding first part acrylic ester monomer 60～80 ℃ of reactions 1～3 hour down;
C, the reacted reaction kettle of step b is cooled to below 40 ℃; The second section and the initiator that in said reaction kettle, add the second section acrylic monomer stir; Adding an amount of neutralization reagent again neutralizes; Add deionized water after 10～30 minutes and carry out emulsion reaction, add quadrol then and carried out the back chain extending reaction 20～60 minutes;
D, make the reacted reaction kettle of step c after insulation for some time; In said reaction kettle, 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, promptly 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 being: said 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 second section acrylic ester monomer that adds among the first part's acrylic ester monomer that adds in the said 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 said 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 said initiator that adds among the said step c be in the system acrylic ester monomer gross weight 0.5～2.0%.
The consumption of deionized water can be confirmed 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 divalent 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 bearing active hydrogen that has, wherein the hydrophilic functional group is selected from any one or more in carboxylic acid, the sulfonic group; The compound bearing active hydrogen that has 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 Rocryl 400, the Hydroxyethyl acrylate.
Acrylic ester monomer in aforesaid method step b, step c and the steps d adopts: any one or more in Bing Xisuandingzhi, TEB 3K, vinylbenzene, the ethyl propenoate.
Initiator among the aforesaid method step c adopts: any one or more in Diisopropyl azodicarboxylate, Lucidol, Potassium Persulphate, the ammonium persulphate; The consumption of said 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, Pottasium Hydroxide, the trolamine.
The preparation method of the embodiment of the invention; Substitute conventional urethane with acrylic ester monomer and prepare employed organic cosolvent in the process; 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 monomeric polymerization of initiating methacrylates under action of evocating makes a kind of acrylate modified anionic polyurethane composite emulsion after neutralization, the water-dispersion.The advantage of this method is: 1) do not add any organic cosolvent in this kind acrylic ester modified water-soluble polyurethane emulsion, adopting 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, through formula adjustment, it both can be used for the compound adhesive field of using, and also can be used in the fabric coating.
Preparing method to urethane composite emulsion of the present invention is described further below in conjunction with specific embodiment.
Embodiment 1
Present embodiment provides a kind of preparation method of acrylate modified anionic polyurethane composite emulsion, can prepare a kind of urethane composite emulsion, and this method may further comprise the steps:
A. be that 2000 polyester diol 100 weight parts, dimethylol propionic acid 7 weight parts join in the reaction kettle earlier with molecular weight; Be heated to dissolving fully, 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 Rocryl 400 7 weight parts in the reaction kettle in step a; React 1h～3h down at 70 ℃; Constantly add Bing Xisuandingzhi (be first part's acrylic ester monomer, add 10 parts by weight of acrylic butyl esters altogether) in the reaction process to reduce the viscosity of reaction system;
C. make the reacted reaction kettle of step b be cooled to 40 ℃; The TEB 3K (being the second section acrylic ester monomer) and the initiator A IBN of 0.5 weight part that add 12 weight parts stir; Add the neutralization reagent triethylamine of 4.9 weight parts again, neutralize, add 350 parts by weight of deionized water behind the 15min and carry out emulsion reaction; Add chain extension 30min behind the chainextender quadrol of 0.8 weight part afterwards, obtain aqueous pu dispersions;
D. after being incubated for some time, in the aqueous pu dispersions that step c obtains, drip the Bing Xisuandingzhi of remaining 5 weight parts (being remaining acrylic ester monomer) and the initiator A IBN of 0.5 weight part, 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
Present embodiment provides a kind of preparation method of acrylate modified anionic polyurethane composite emulsion, can prepare a kind of urethane composite emulsion, and this method may further comprise the steps:
A. will join in the reaction kettle for polyether Glycols 100 weight parts, dimethylolpropionic acid 8 weight parts of 2000 molecular weight earlier, be heated to dissolving fully, be cooled to 60 ℃ and add 40 weight part isoflurane chalcone diisocyanates, keep 90 ℃ of constant temperature, reaction 2h～4h;
B. in the reaction kettle of a step, add Rocryl 400 7 weight parts again; React 1.5h down at 75 ℃; Constantly add Bing Xisuandingzhi (be first part's acrylic ester monomer, add 12 parts by weight of acrylic butyl esters altogether) in the reaction process to reduce the viscosity of reaction system;
C. be cooled to below 40 ℃; The adding 8 parts by weight of acrylic butyl esters (being the second section acrylic ester monomer) and the initiator A IBN of 0.15 weight part stir in the reaction kettle of b step again; Add 3.3 weight part neutralization reagent triethylamines again; Neutralize, add 170 parts by weight of deionized water behind the 30min and carry out emulsion reaction, add quadrol (EDA) 0.8 weight part then and carry out back chain extending reaction 20min;
D. after being incubated for some time, in the reaction kettle of c step, drip the initiator A IBN of remaining TEB 3K 5 weight parts (being remaining acrylic ester monomer) and 0.03 weight part, 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
Present embodiment provides a kind of preparation method of acrylate modified anionic polyurethane composite emulsion, can prepare a kind of urethane composite emulsion, and this 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 earlier; Dimethylol propionic acid 7 weight parts join in the reaction kettle; Be heated to dissolving fully; Be cooled to 60 ℃ and add 23 parts by weight of toluene vulcabond, keep 90 ℃ of constant temperature, reaction 2h～4h;
B. in the reaction kettle of a step, add Rocryl 400 7 weight parts again; React 1.5h down at 75 ℃; Constantly add first part's acrylic ester monomer (mix monomer of TEB 3K and Bing Xisuandingzhi adds 10 weight parts altogether) in the reaction process to reduce the viscosity of reaction system;
C. be cooled to below 40 ℃; In the reaction kettle of b step, add the second section Acrylic Acid Monomer (mix monomer of TEB 3K and Bing Xisuandingzhi again; Totally 12 weight parts) and the initiator A IBN of 0.20 weight part stir, add 5.0 weight part neutralization reagent triethylamines again, neutralize; Add 210 parts by weight of deionized water behind the 30min and carry out emulsion reaction, add quadrol (EDA) 0.9 weight part then and carry out back chain extending reaction 20min;
D. after being incubated for some time, in the reaction kettle of c step, drip the initiator A IBN of remaining acrylic ester monomer (mix monomer of TEB 3K and Bing Xisuandingzhi, totally 8 weight parts) and 0.03 weight part; Under 70 ℃ of temperature of reaction, 3h dropwises, insulation 2h; Be warming up to 85 ℃ of reaction 1h again; 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
Present embodiment provides a kind of preparation method of acrylate modified anionic polyurethane composite emulsion, can prepare a kind of urethane composite emulsion, and this method may further comprise the steps:
A. will join in the reaction kettle for polyether Glycols 100 weight parts, dimethylolpropionic acid 8 weight parts of 2000 molecular weight earlier, be heated to dissolving fully, be cooled to 60 ℃ and add 36 weight part isoflurane chalcone diisocyanates, keep 90 ℃ of constant temperature, reaction 2h～4h;
B. in the reaction kettle of a step, add Rocryl 400 5 weight parts again; React 1.5h down at 75 ℃; Constantly add TEB 3K (be first part's acrylic ester monomer, add 12 weight parts altogether) in the reaction process to reduce the viscosity of reaction system;
C. be cooled to below 40 ℃; The adding 8 parts by weight of acrylic butyl esters (being the second section acrylic ester monomer) and the initiator B PO of 0.15 weight part stir in the reaction kettle of b step again; Add 5.2 weight part neutralization reagent triethylamines again; Neutralize, add 205 parts by weight of deionized water behind the 30min and carry out emulsion reaction, add quadrol (EDA) 0.8 weight part then and carry out back chain extending reaction 20min;
D. after being incubated for some time, in the reaction kettle of c step, drip the initiator B PO of remaining TEB 3K 5 weight parts (being remaining acrylic ester monomer) and 0.03 weight part, 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
Present embodiment provides a kind of preparation method of acrylate modified anionic polyurethane composite emulsion, can prepare a kind of urethane composite emulsion, and this method may further comprise the steps:
A. will join in the reaction kettle for polyether Glycols 100 weight parts, dimethylol propionic acid 6 weight parts, dimethylolpropionic acid 2 weight parts of 2000 molecular weight earlier; Be heated to dissolving fully; Be cooled to 60 ℃ and add 36 weight part isoflurane chalcone diisocyanates, keep 90 ℃ of constant temperature, reaction 2h～4h;
B. in the reaction kettle of a step, add Rocryl 400 7 weight parts again; React 1.5h down at 75 ℃; Constantly add first part's acrylic ester monomer (mix monomer of ethyl propenoate and TEB 3K adds 12 weight parts altogether) in the reaction process to reduce the viscosity of reaction system;
C. be cooled to below 40 ℃; The initiator A PS that in the reaction kettle of b step, adds second section 8 parts by weight of acrylic esters monomers (mix monomer of ethyl propenoate and TEB 3K) and 0.15 weight part again stirs; Add 5.6 weight part neutralization reagent triethylamines again; Neutralize, add 205 parts by weight of deionized water behind the 30min and carry out emulsion reaction, add quadrol (EDA) 0.8 weight part then and carry out back chain extending reaction 20min;
D. after being incubated for some time, in the reaction kettle of c step, drip the initiator A PS of remaining acrylic ester monomer 5 weight parts (mix monomer of ethyl propenoate and TEB 3K) and 0.03 weight part, 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
Present embodiment provides a kind of preparation method of acrylate modified anionic polyurethane composite emulsion, can prepare a kind of urethane composite emulsion, and this 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 earlier; Dimethylol propionic acid 7 weight parts join in the reaction kettle; Be heated to dissolving fully; Be cooled to 60 ℃ and add 23 parts by weight of toluene vulcabond, keep 90 ℃ of constant temperature, reaction 2h～4h;
B. in the reaction kettle of a step, add Hydroxyethyl acrylate 5 weight parts again; React 1.5h down at 75 ℃; Constantly add first part's acrylic ester monomer (mix monomer of TEB 3K and Bing Xisuandingzhi, add-on are 10 weight parts) in the reaction process to reduce its viscosity;
C. be cooled to below 40 ℃; In the reaction kettle of b step, add the second section Acrylic Acid Monomer (mix monomer of TEB 3K and Bing Xisuandingzhi again; Add 12 weight parts altogether) and the initiator A PS of 0.20 weight part stir, add 5.0 weight part neutralization reagent triethylamines again, neutralize; The deionized water that adds 210 weight parts behind the 30min carries out emulsion reaction, adds quadrol (EDA) 0.9 weight part then and carries out back chain extending reaction 20min;
D. after being incubated for some time, in the reaction kettle of c step, drip the initiator A PS of residual acrylic acid esters monomer (mix monomer of TEB 3K and Bing Xisuandingzhi, add-on are 8 weight parts) and 0.03 weight part; Under 70 ℃ of temperature of reaction, 3h dropwises, insulation 2h; Be warming up to 85 ℃ of reaction 1h again; 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: in the acrylic ester modified water-soluble polyurethane emulsion, do not add any organic cosolvent, adopting 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, through 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; Be merely the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, any technician who is familiar with the present technique field is 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 (10)
1. the preparation method of an acrylate modified anionic polyurethane composite emulsion is characterized in that, this method comprises:
A, polymer diatomic alcohol, carboxylic organic hydroxy compounds are joined in the reaction kettle, be heated to dissolving fully, be cooled to 60 ℃ and add isocyanic ester, keep 80～90 ℃ of constant temperature, reacted 2～4 hours;
B, in the reaction kettle of step a, add the acrylic ester monomer of hydroxyl,, reduce the viscosity of reaction system in the reaction process through continuous adding first part acrylic ester monomer 60～80 ℃ of reactions 1～3 hour down;
C, the reacted reaction kettle of step b is cooled to below 40 ℃; The second section and the initiator that in said reaction kettle, add the second section acrylic monomer stir; Adding an amount of neutralization reagent again neutralizes; Add deionized water after 10～30 minutes and carry out emulsion reaction, add quadrol then and carried out the back chain extending reaction 20～60 minutes;
D, make the reacted reaction kettle of step c after insulation for some time; In said reaction kettle, 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, promptly obtain solid content after the cooling and be 30～50% urethane composite emulsion.
2. the preparation method of acrylate modified anionic polyurethane composite emulsion according to claim 1 is characterized in that:
In each step of aforesaid method, each raw material consumption of adding is by weight being: said 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 second section acrylic ester monomer that adds among the first part's acrylic ester monomer that adds in the said 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 said step c account for adding the acrylic ester monomer gross weight 20～40%;
The consumption of the said initiator that adds among the said step c be in the system acrylic ester monomer gross weight 0.5～2.0%.
3. the preparation method of acrylate modified anionic polyurethane composite emulsion according to claim 1 and 2; It is characterized in that: the polymer diatomic alcohol among the said step a adopts: any in polyether Glycols, polyester diol, polycaprolactone divalent alcohol, the PCDL, the molecular weight of polymer diatomic alcohol are 1000～3000.
4. the preparation method of acrylate modified anionic polyurethane composite emulsion according to claim 1 and 2; It is characterized in that: the carboxylic organic hydroxy compounds among the said step a is: can form hydrophilic functional group's the compound bearing active hydrogen that has, wherein the hydrophilic functional group is selected from any one or more in carboxylic acid, the sulfonic group.
5. the preparation method of acrylate modified anionic polyurethane composite emulsion according to claim 3 is characterized in that: said have compound bearing active hydrogen and adopt: any one or more in dimethylol propionic acid, dimethylolpropionic acid, quadrol base ethyl sulfonic acid sodium, the dihydroxyl half ester.
6. the preparation method of acrylate modified anionic polyurethane composite emulsion according to claim 1 and 2; It is characterized in that: the isocyanic ester among the said step a adopts: ditan-4; Any one or more of 4-vulcabond, hexamethylene vulcabond, isoflurane chalcone diisocyanate etc.
7. the preparation method of acrylate modified anionic polyurethane composite emulsion according to claim 1 and 2 is characterized in that: the acrylic ester monomer of the hydroxyl among the said step a adopts: any one or more in Rocryl 400, the Hydroxyethyl acrylate.
8. the preparation method of acrylate modified anionic polyurethane composite emulsion according to claim 1 and 2 is characterized in that: the acrylic ester monomer in said step b, step c and the steps d adopts: any one or more in Bing Xisuandingzhi, TEB 3K, vinylbenzene, the ethyl propenoate.
9. the preparation method of acrylate modified anionic polyurethane composite emulsion according to claim 1 and 2 is characterized in that: the initiator among the said step c adopts: any one or more in Diisopropyl azodicarboxylate, Lucidol, Potassium Persulphate, the ammonium persulphate.
10. the preparation method of acrylate modified anionic polyurethane composite emulsion according to claim 1 and 2 is characterized in that: the neutralizing agent among the said step c adopts: any one or more in triethylamine, sodium hydroxide, Pottasium Hydroxide, the trolamine.
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| CN114058316A (en) * | 2020-08-03 | 2022-02-18 | 浙江卫星石化股份有限公司 | Waterborne polyurethane dispersion with good wettability and preparation method thereof |
| CN114058316B (en) * | 2020-08-03 | 2023-08-25 | 卫星化学股份有限公司 | Aqueous polyurethane dispersion liquid with good wettability and preparation method thereof |
| CN115181218A (en) * | 2022-07-15 | 2022-10-14 | 青岛大学 | Preparation method and application of cationic polyurethane-acrylate water repellent |
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