CN103539916A - Self-defoaming water-based polyurethane emulsion - Google Patents
Self-defoaming water-based polyurethane emulsion Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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Abstract
The invention relates to a self-defoaming water-based polyurethane emulsion which is prepared by the following steps: vacuum-heating macromolecular polyhydric alcohol to 110-140 DEG C, and dewatering for 0.5-2.0 hours; adding hydroxyl silicone oil and reducing the temperature to 60-75 DEG C, and stirring for 0.5-1.0 hour; adding isocyanate and stirring for reaction at 70-85 DEG C for 1.5-3.0 hours; adding a hydrophilic chain extender and a crosslinking agent, and stirring for reaction for 1.0-2.0 hours to obtain a prepolymer; reducing the temperature of the prepolymer to 40-50 DEG C; adding a solvent, dropwise adding a neutralizer and stirring for 15-45 minutes; and after the chain extender is dissolved in water, dropwise adding into the neutralized prepolymer, and stirring at a stirring rate of 1,000-3,000rpm for 20-40 minutes to obtain the emulsion. According to the self-defoaming water-based polyurethane emulsion provided by the invention, the chemical structure of the molecular chain segment of polyurethane is changed from a synthesis source of polyurethane, and the silicon with low surface energy is introduced so that the emulsion has excellent defoaming ability; and after film formation, the emulsion has good water resistance and solvent resistance.
Description
Technical field
The present invention relates to the technical field of polyaminoester emulsion, be specifically related to a kind of self-defoaming aqueous polyurethane emulsion.
Background technology
Along with human life quality's raising, environmental regulation is more and more stricter, and various environmental regulation rules have strict restriction to the content of the quantity discharged of volatile organic compounds (VOC), hazardous solvent.Aqueous polyurethane emulsion, because it take water as dispersion medium, has the advantages such as nontoxic, free from environmental pollution, nonflammable, energy-conservation, safe and reliable, and therefore waterborne polyurethane emulsion coating has obtained concern widely in recent years.Aspect industrialization, in early 1980s, formed certain industrial scale abroad.As the Wyandotte chemical company of Bayer A.G, Japan large ink company, the U.S. etc. has all released the aqueous polyurethane emulsion product of the different trades mark.Enter after the nineties in 20th century, domestic aqueous polyurethane emulsion device puts into production in succession, but scale is all little, and kind is also comparatively single.Enter after 21 century, the Application Areas of domestic aqueous polyurethane emulsion constantly expands, and the manufacturer of aqueous polyurethane emulsion constantly increases, and the development of aqueous polyurethane industry also enters a new developmental stage.
Use with polyaminoester emulsion is promoted, aqueous emulsion of polyurethane froth breaking problem becomes increasingly conspicuous, in painting, brush a large amount of foams of easy generation in machine process and cause production efficiency low, and additional defoamer froth breaking persistence is not good even because of defoamer and the bad stability decreases that causes emulsion of urethane consistency.
Summary of the invention
The object of the invention is to overcome the defect that above-mentioned prior art exists, a kind of self-defoaming aqueous polyurethane emulsion that can reach self-defoaming effect without additional defoamer is provided.Aqueous emulsion of polyurethane prepared by the present invention fast froth breaking does not even bubble, and has overcome aqueous product and has used a great problem in extension process; The present invention sets about from the synthetic source of urethane, change the chemical structure of polyurethane molecular segment, introduce the silicon of low surface energy, thereby make emulsion itself possess froth breaking ability, exist technique simple, easy control of structure, emulsification is convenient, the aqueous polyurethane making has good stability, good water tolerance and solvent resistance, is with a wide range of applications.
The object of the invention is to be achieved through the following technical solutions:
The present invention relates to a kind of self-defoaming aqueous polyurethane emulsion, described emulsion is that the method preparation by comprising following steps obtains:
Steps A, by macromolecular polyol heating under vacuum to the 110～140 ℃ 0.5～2.0h that dewaters, add hydroxy silicon oil and be cooled to 60～75 ℃ and stir after 0.5～1.0h, add isocyanic ester stirring reaction 1.5～3.0h at 70～85 ℃, add hydrophilic chain extender and linking agent, continue stirring reaction 1.0～2.0h, obtain prepolymer;
Step B, described prepolymer is cooled to 40～50 ℃, add solvent to reduce system viscosity, be added dropwise to neutralizing agent, stir 15～45min;
Step C, chainextender is dissolved in after water, is added drop-wise in the prepolymer after described neutralization, stir speed (S.S.) is controlled at 1000～3000rpm, stirs 20～40min, obtains described self-defoaming aqueous polyurethane emulsion.
Preferably, the weight ratio of described macromolecular polyol, hydroxy silicon oil, isocyanic ester, hydrophilic chain extender, linking agent, solvent, chainextender is: (20～30): (20～30): (10～20): (5～7): (1.5～7.5): (0.5～1.5): (3～4): (10～30).
Preferably, described macromole polyester polyol is one or more in polycarbonate polyol, polycaprolactone polyol, polyester adipate polyvalent alcohol, polyacrylate polyol, polyether glycol.
Preferably, described isocyanic ester is tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, 4, one or more in 6-Xylene Diisocyanate.
Preferably, described hydroxy silicon oil is the hydroxy silicon oil that molecular weight is 300～500, hydroxy radical content is 8.0～9.0%.
Preferably, described hydrophilic chain extender is 2,2-dimethylol propionic acid or 2,2-dimethylolpropionic acid.
Preferably, described chainextender is one or more in small molecules polyamine chainextender, small molecules polyvalent alcohol chainextender.
Preferably, described small molecules polyamine chainextender is one or more in isophorone diamine, quadrol, diethylenetriamine, triethylene tetramine.
Preferably, described small molecules polyvalent alcohol chainextender is ethylene glycol, BDO, tetraethylene-glycol, neopentyl glycol, 1, one or more in 6-hexylene glycol, cyclohexanedimethanol.
Preferably, described linking agent is TriMethylolPropane(TMP), trolamine or glycerol.
Preferably, described neutralizing agent is ammoniacal liquor, triethylamine, Trimethylamine 99, DIPEA or N, N-dimethylethanolamine.
Preferably, described solvent is ammonia ester grade acetone or ammonia ester level butanone.
Compared with prior art, the beneficial effect that the present invention has is: it is raw material that the present invention adopts vulcabond and macromolecular polyol, silicon by high hydroxyl content is hydroxyl silicon oil modified, then adopt the mode of emulsification limit, limit chain extension, introduce the internal cohesive energy that urea groups strengthens urethane, improve second-order transition temperature, effectively improved the molecular weight of polymkeric substance, second-order transition temperature and melt temperature are improved largely simultaneously, the film that utilizes it to make has good especially temperature tolerance and good feel, be difficult for decomposing, resistance to xanthochromia, can keep for a long time original gloss and color and luster, it also has acidproof preferably, alkali, salt, grease, the corrosion resistance nature of the chemical such as washing composition, mechanical property after film forming is also very excellent, in addition, because the low surface energy of silicon causes emulsion to be easy to there is good hydrophobic water-repellancy after froth breaking and film forming.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
embodiment 1
The self-defoaming aqueous polyurethane emulsion of the present embodiment is that the method preparation by comprising the following steps obtains:
(1) get the raw materials ready:
According to following component and quality, prepare raw material: 10.00g isophorone diisocyanate, 10.00g hexamethylene diisocyanate, the commercially available poly adipate succinic acid ester of 30.00g (Mn=3000), the commercially available hydroxy silicon oil (Mn=300 of 10.00g, hydroxy radical content 9.0%), 5.00g hydrophilic chain extender 2,2-dimethylolpropionic acid, 0.50g glycol chain extender, 1.00g chainextender diethylenetriamine, 0.50g linking agent glycerol, 3.00g neutralizing agent N, N-dimethylethanolamine, 30.00g ammonia ester grade acetone (about 38.00ml);
(2) preparation of prepolymer:
30.00g poly adipate succinic acid ester (Mn=3000) is added with thermometer, in the four-hole boiling flask of prolong and agitator, vacuumize and be heated to 110 ℃, 2.0h dewaters, then add 10.00g hydroxy silicon oil and be cooled to 75 ℃ and stir 0.5h, 10.00g isophorone diisocyanate and 10.00g hexamethylene diisocyanate are added in flask, slowly intensification temperature control are at 75～85 ℃, reaction 2.0h, add subsequently 5.00g dimethylolpropionic acid, 0.50g ethylene glycol and 0.50g glycerol, continue reaction 3.0h, then be cooled to 50 ℃, add 30.00g acetone to reduce system viscosity, adopt N, N-dimethylethanolamine is as neutralizing agent, with constant voltage titration funnel by 3.0g neutralizing agent N, N-dimethylethanolamine slowly adds in four-hole boiling flask, stir 30min, obtain prepolymer,
(3) preparation of emulsion:
Take 160g deionized water, 1.00g diethylenetriamine is dissolved in wherein, and the speed of controlling stirrer is 2000rpm, with constant voltage titration funnel, the above-mentioned aqueous solution is added drop-wise in prepolymer, stir and to take out after 30min standingly, can obtain self-defoaming aqueous polyurethane emulsion.
(4) emulsion property test:
Testing method: in clean 250ml graduated cylinder, add 50ml solution to be measured, with fish tank oxygen increasing machine, to passing into air in emulsion, carry out bubbling, record bubble overflow the time and stop ventilating after the foam time of foam.
Above-mentioned testing method contrast test for ADM-F217 polyaminoester emulsion by above-mentioned gained emulsion and the U.S. macromolecular material of commercially available Shandong Order company limited, the results are shown in following table 1:
Table 1
embodiment 2
The self-defoaming aqueous polyurethane emulsion of the present embodiment is that the method preparation by comprising the following steps obtains:
(1) get the raw materials ready:
According to following component and quality, prepare raw material: 25.00g hexamethylene diisocyanate, 25.00g commercial polycarbonate (Mn=2000), the commercially available hydroxy silicon oil (Mn=400 of 15.00g, hydroxy radical content 8.50%), 6.00g hydrophilic chain extender 2,2-dimethylolpropionic acid, 2.50g chainextender Triethylene glycol, 2.00g chainextender triethylene tetramine, 1.00g linking agent TriMethylolPropane(TMP), 3.50g neutralizing agent N, N-dimethylethanolamine, 20.00g acetone (about 25.00ml);
(2) preparation of prepolymer:
25.00g polycarbonate (Mn=2000) is added with thermometer, in the four-hole boiling flask of prolong and agitator, vacuumize and be heated to 120 ℃, 1.5h dewaters, then add 15.00g hydroxy silicon oil and be cooled to 75 ℃ and stir 40min, 25.00g hexamethylene diisocyanate is added in flask, slowly be warming up to 75～80 ℃, reaction 2.0h, add subsequently 6.00 dimethylolpropionic acids, 2.50g Triethylene glycol and 1.00g TriMethylolPropane(TMP), continue reaction 3.0h, then be cooled to 45 ℃, add 20.00g acetone to reduce system viscosity, adopt N, N-dimethylethanolamine is as neutralizing agent, with constant voltage titration funnel by 3.50 neutralizing agent N, N-dimethylethanolamine slowly adds in four-hole boiling flask, stir 20min, obtain prepolymer,
(3) preparation of emulsion:
Take 185g deionized water, 2.00g triethylene tetramine is dissolved in wherein, and the speed of controlling stirrer is 2000rpm, with constant voltage titration funnel, the above-mentioned aqueous solution is added drop-wise in prepolymer, stir and to take out after 40min standingly, can obtain self-defoaming aqueous polyurethane emulsion.
(4) emulsion property test:
Testing method: in clean 250ml graduated cylinder, add 50ml solution to be measured, with fish tank oxygen increasing machine, to passing into air in emulsion, carry out bubbling, record bubble overflow the time and stop ventilating after the foam time of foam.
By above-mentioned testing method contrast test for the PU-115 polyaminoester emulsion of above-mentioned gained emulsion and commercially available Hefei Anke Fine Chemicals Co., Ltd., the results are shown in following table 2:
Table 2
embodiment 3
The self-defoaming aqueous polyurethane emulsion of the present embodiment is that the method preparation by comprising the following steps obtains:
(1) get the raw materials ready:
According to following component and quality, prepare raw material: 30.00g hexamethylene diisocyanate, the commercially available polyneopentyl glycol adipate of 20.00g (Mn=3000), the commercially available hydroxy silicon oil (Mn=500 of 20.00g, hydroxy radical content 8.0%), 7.00g hydrophilic chain extender 2,2-dimethylolpropionic acid, 7.00g chainextender Triethylene glycol, 0.50g chainextender triethylene tetramine, 1.50g linking agent TriMethylolPropane(TMP), 4.00g neutralizing agent N, N-dimethylethanolamine, 10.00g butanone (about 13.00ml);
(2) preparation of prepolymer:
20.00g polyneopentyl glycol adipate (Mn=3000) is added with thermometer, in the four-hole boiling flask of prolong and agitator, vacuumize and be heated to 130 ℃, 1.0h dewaters, then add 20.00g hydroxy silicon oil and be cooled to 60～65 ℃ and stir 1.0h, 30.00g hexamethylene diisocyanate is added in flask, slowly be warming up to 70～80 ℃, reaction 2.0h, add subsequently 7.00g dimethylolpropionic acid 7.00g Triethylene glycol and 1.50g TriMethylolPropane(TMP), continue reaction 3.0h, then be cooled to 40 ℃, add 10.00g butanone to reduce system viscosity, adopt N, N-dimethylethanolamine is as neutralizing agent, with constant voltage titration funnel by 4.00 neutralizing agent N, N-dimethylethanolamine slowly adds in four-hole boiling flask, stir 15min, obtain prepolymer,
(3) preparation of emulsion:
Take 210g deionized water, 0.50g triethylene tetramine is dissolved in wherein, and the speed of controlling stirrer is 2000rpm, with constant voltage titration funnel, the above-mentioned aqueous solution is added drop-wise in prepolymer, stir and to take out after 30min standingly, can obtain self-defoaming aqueous polyurethane emulsion.
(4) emulsion property test:
Testing method: in clean 250ml graduated cylinder, add 50ml solution to be measured, with fish tank oxygen increasing machine, to passing into air in emulsion, carry out bubbling, record bubble overflow the time and stop ventilating after the foam time of foam.
Above-mentioned testing method contrast test for ADM-Z736 polyaminoester emulsion by above-mentioned gained emulsion and the U.S. macromolecular material of commercially available Shandong Order company limited, the results are shown in following table 3:
Table 3
embodiment 4
The self-defoaming aqueous polyurethane emulsion of the present embodiment is that the method preparation by comprising the following steps obtains:
(1) get the raw materials ready:
According to following component and quality, prepare raw material: 10.00g dicyclohexyl methane diisocyanate, 18.00g isophorone diisocyanate, the commercially available polyethers PPG-2000 of 23.00g, the commercially available hydroxy silicon oil (Mn=350 of 12.00g, hydroxy radical content 8.50%), 5.50g hydrophilic chain extender 2,2-dimethylol propionic acid, 1.80g chainextender 1,6-hexylene glycol, 0.80g chainextender isophorone diamine, 0.70g linking agent trolamine, 3.20g neutralizing agent DIPEA, 25.00g acetone (about 32.00ml);
(2) preparation of prepolymer:
23.00g polyethers PPG-2000 is added with thermometer, in the four-hole boiling flask of prolong and agitator, vacuumize and be heated to 130 ℃, 1.0h dewaters, then add 12.00g hydroxy silicon oil and be cooled to 65 ℃ and stir 1.0h, 10.00g dicyclohexyl methane diisocyanate and 18.00g isophorone diisocyanate are added in flask, slowly intensification temperature control are at 75～85 ℃, reaction 3.0h, add subsequently 5.50g dimethylol propionic acid 1.80gl, 6-hexylene glycol and 0.70g trolamine, continue reaction 3.0h, then be cooled to 50 ℃, add 25.00g acetone to reduce system viscosity, adopt N, N-diisopropylethylamine is as neutralizing agent, with constant voltage titration funnel by 3.20g neutralizing agent N, N-diisopropylethylamine slowly adds in four-hole boiling flask, stir 45min, obtain prepolymer,
(3) preparation of emulsion:
Take 180g deionized water, 0.80g isophorone diamine is dissolved in wherein, and the speed of controlling stirrer is 2000rpm, with constant voltage titration funnel, the above-mentioned aqueous solution is added drop-wise in prepolymer, stir and to take out after 30min standingly, can obtain self-defoaming aqueous polyurethane emulsion.
(4) emulsion property test:
Testing method: in clean 250ml graduated cylinder, add 50ml solution to be measured, with fish tank oxygen increasing machine, to passing into air in emulsion, carry out bubbling, record bubble overflow the time and stop ventilating after the foam time of foam.
By above-mentioned testing method contrast test for the PU-9130 polyaminoester emulsion of above-mentioned gained emulsion and commercially available Hefei Anke Fine Chemicals Co., Ltd., the results are shown in following table 4:
Table 4
embodiment 5
The self-defoaming aqueous polyurethane emulsion of the present embodiment is that the method preparation by comprising the following steps obtains:
(1) get the raw materials ready:
According to following component and quality, prepare raw material: 10.0g isophorone diisocyanate, 14.00g tolylene diisocyanate, commercially available polycaprolactone (PCL)-2000 of 27.0g, the commercially available hydroxy silicon oil (Mn=450 of 17.0g, hydroxy radical content 8.0%), 6.10g hydrophilic chain extender 2,2-dimethylol propionic acid, 1.60g chainextender isophorone diamine, 1.10g linking agent TriMethylolPropane(TMP), 3.70g neutralizing agent triethylamine, 19.00g acetone (about 24.00ml);
(2) preparation of prepolymer:
27.00g polycaprolactone (PCL)-2000 are added with thermometer, in the four-hole boiling flask of prolong and agitator, vacuumize and be heated to 140 ℃, 0.5h dewaters, then add 17.00g hydroxy silicon oil and be cooled to 60 ℃ and stir 0.5h, 10.00g isophorone diisocyanate and 14.00g tolylene diisocyanate are added in flask, slowly intensification temperature control are at 70～75 ℃, reaction 2.0h, add subsequently 6.10g dimethylol propionic acid and 1.10g TriMethylolPropane(TMP), continue reaction 1.5h, then be cooled to 40 ℃, add 19.00g acetone to reduce system viscosity, adopt triethylamine as neutralizing agent, with constant voltage titration funnel, 3.70g neutralizing agent triethylamine is slowly added in four-hole boiling flask, stir 45min, obtain prepolymer,
(3) preparation of emulsion:
Take 180g deionized water, 1.60g isophorone diamine is dissolved in wherein, and the speed of controlling stirrer is 2000rpm, with constant voltage titration funnel, the above-mentioned aqueous solution is added drop-wise in prepolymer, stir and to take out after 45min standingly, can obtain self-defoaming aqueous polyurethane emulsion.
(4) emulsion property test:
Testing method: in clean 250ml graduated cylinder, add 50ml solution to be measured, with fish tank oxygen increasing machine, to passing into air in emulsion, carry out bubbling, record bubble overflow the time and stop ventilating after the foam time of foam.
Above-mentioned testing method contrast test for ADM-Z709 polyaminoester emulsion by above-mentioned gained emulsion and the U.S. macromolecular material of commercially available Shandong Order company limited, the results are shown in following table 5:
Table 5
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned particular implementation, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (12)
1. a self-defoaming aqueous polyurethane emulsion, is characterized in that, described emulsion is that the method preparation by comprising following steps obtains:
Steps A, by macromolecular polyol heating under vacuum to the 110～140 ℃ 0.5～2.0h that dewaters, add hydroxy silicon oil and be cooled to 60～75 ℃ and stir after 0.5～1.0h, add isocyanic ester stirring reaction 1.5～3.0h at 70～85 ℃, add hydrophilic chain extender and linking agent, continue stirring reaction 1.0～2.0h, obtain prepolymer;
Step B, described prepolymer is cooled to 40～50 ℃, add solvent to reduce system viscosity, be added dropwise to neutralizing agent, stir 15～45min;
Step C, chainextender is dissolved in after water, is added drop-wise in the prepolymer after described neutralization, stir speed (S.S.) is controlled at 1000～3000rpm, stirs 20～40min, obtains described self-defoaming aqueous polyurethane emulsion.
2. self-defoaming aqueous polyurethane emulsion according to claim 1, it is characterized in that, the weight ratio of described macromolecular polyol, hydroxy silicon oil, isocyanic ester, hydrophilic chain extender, linking agent, solvent, chainextender, neutralizing agent is: (20～30): (10～20): (20～30): (5～7): (0.5～1.5): (10～30): (1.5～7.5): (3～4).
3. self-defoaming aqueous polyurethane emulsion according to claim 1 and 2, it is characterized in that, described macromole polyester polyol is one or more in polycarbonate polyol, polycaprolactone polyol, polyester adipate polyvalent alcohol, polyacrylate polyol, polyether glycol.
4. self-defoaming aqueous polyurethane emulsion according to claim 1 and 2, it is characterized in that, described isocyanic ester is tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, 4, one or more in 6-Xylene Diisocyanate.
5. self-defoaming aqueous polyurethane emulsion according to claim 1 and 2, is characterized in that, described hydroxy silicon oil is the hydroxy silicon oil that molecular weight is 300～500, hydroxy radical content is 8.0～9.0%.
6. self-defoaming aqueous polyurethane emulsion according to claim 1 and 2, is characterized in that, described hydrophilic chain extender is 2,2-dimethylol propionic acid or 2,2-dimethylolpropionic acid.
7. self-defoaming aqueous polyurethane emulsion according to claim 1 and 2, is characterized in that, described chainextender is one or more in small molecules polyamine chainextender, small molecules polyvalent alcohol chainextender.
8. self-defoaming aqueous polyurethane emulsion according to claim 7, is characterized in that, described small molecules polyamine chainextender is one or more in isophorone diamine, quadrol, diethylenetriamine, triethylene tetramine.
9. self-defoaming aqueous polyurethane emulsion according to claim 7, it is characterized in that, described small molecules polyvalent alcohol chainextender is ethylene glycol, BDO, tetraethylene-glycol, neopentyl glycol, 1, one or more in 6-hexylene glycol, cyclohexanedimethanol.
10. self-defoaming aqueous polyurethane emulsion according to claim 1 and 2, is characterized in that, described linking agent is TriMethylolPropane(TMP), trolamine or glycerol.
11. self-defoaming aqueous polyurethane emulsions according to claim 1 and 2, is characterized in that, described neutralizing agent is ammoniacal liquor, triethylamine, Trimethylamine 99, DIPEA or N, N-dimethylethanolamine.
12. self-defoaming aqueous polyurethane emulsions according to claim 1 and 2, is characterized in that, described solvent is ammonia ester grade acetone or butanone.
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| CN103755919A (en) * | 2014-02-13 | 2014-04-30 | 余姚市星银高分子材料有限公司 | Organosilicon modified polyurethane microsphere preparation method |
| CN106366255A (en) * | 2016-08-31 | 2017-02-01 | 陈雄 | Preparation method of self-defoaming acrylic emulsion |
| CN111675800A (en) * | 2020-06-11 | 2020-09-18 | 万华化学集团股份有限公司 | Self-foamable waterborne polyurethane resin emulsion and preparation method thereof |
| CN113321780A (en) * | 2021-06-11 | 2021-08-31 | 广州大学 | Preparation method of organic silicon modified polyurethane |
| CN113440436A (en) * | 2020-03-26 | 2021-09-28 | 万华化学集团股份有限公司 | BB cream containing nonionic silicon-containing modified aqueous polyurethane dispersion |
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| CN103073987A (en) * | 2013-01-17 | 2013-05-01 | 杭州电子科技大学 | Preparation method for organic silicon modified polyester type polyurethane emulsion leather finishing agent |
| CN103088644A (en) * | 2013-01-17 | 2013-05-08 | 杭州电子科技大学 | Method for preparing organosilicone modified polyether type polyurethane emulsion leather finishing agent |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103073987A (en) * | 2013-01-17 | 2013-05-01 | 杭州电子科技大学 | Preparation method for organic silicon modified polyester type polyurethane emulsion leather finishing agent |
| CN103088644A (en) * | 2013-01-17 | 2013-05-08 | 杭州电子科技大学 | Method for preparing organosilicone modified polyether type polyurethane emulsion leather finishing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103755919A (en) * | 2014-02-13 | 2014-04-30 | 余姚市星银高分子材料有限公司 | Organosilicon modified polyurethane microsphere preparation method |
| CN106366255A (en) * | 2016-08-31 | 2017-02-01 | 陈雄 | Preparation method of self-defoaming acrylic emulsion |
| CN113440436A (en) * | 2020-03-26 | 2021-09-28 | 万华化学集团股份有限公司 | BB cream containing nonionic silicon-containing modified aqueous polyurethane dispersion |
| CN113440436B (en) * | 2020-03-26 | 2022-08-05 | 万华化学集团股份有限公司 | BB cream containing nonionic silicon-containing modified aqueous polyurethane dispersion |
| CN111675800A (en) * | 2020-06-11 | 2020-09-18 | 万华化学集团股份有限公司 | Self-foamable waterborne polyurethane resin emulsion and preparation method thereof |
| CN113321780A (en) * | 2021-06-11 | 2021-08-31 | 广州大学 | Preparation method of organic silicon modified polyurethane |
| CN113999557A (en) * | 2021-11-23 | 2022-02-01 | 中山森柏雅新材料科技有限公司 | Wear-resistant hydrophobic oleophobic antibacterial nano-coating and preparation method thereof |
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