CN101906192A - Method for preparing aqueous polyurethane-acrylate composite emulsion - Google Patents
Method for preparing aqueous polyurethane-acrylate composite emulsion Download PDFInfo
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- CN101906192A CN101906192A CN 201010244768 CN201010244768A CN101906192A CN 101906192 A CN101906192 A CN 101906192A CN 201010244768 CN201010244768 CN 201010244768 CN 201010244768 A CN201010244768 A CN 201010244768A CN 101906192 A CN101906192 A CN 101906192A
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- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- -1 vinyl compound Chemical class 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
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- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 4
- 229920003009 polyurethane dispersion Polymers 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000004814 polyurethane Substances 0.000 claims description 14
- 229920002635 polyurethane Polymers 0.000 claims description 14
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 238000009736 wetting Methods 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000004945 emulsification Methods 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000000903 blocking effect Effects 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 7
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 231100000614 poison Toxicity 0.000 description 1
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- 229920000058 polyacrylate Polymers 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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Landscapes
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a method for preparing aqueous polyurethane-acrylate composite emulsion. The method comprises the following steps of: synthesizing aqueous polyurethane prepolymer by using dihydric alcohol polymer, diisocyanate and hydrophilic chain extender in the absence of a metal catalyst and an organic solvent, blocking ends of the prepolymer by using a vinyl compound, then neutralizing the polymer, dripping water into the polymer to perform self-emulsification, extending the chain to obtain aqueous polyurethane dispersion, and dripping initiator dissolved acrylate monomer into the dispersion in the absence of additional emulsifier to perform polymerization so as to obtain the aqueous polyurethane-acrylate composite emulsion with high solid content. The solid content of the composite emulsion is over 45 percent; and the preparation process does not use any solvent or metal catalyst, has no pollutant discharge, and is a pollution-free production process. The obtained environmentally-friendly aqueous polyurethane-acrylate composite emulsion with high solid content can be used as adhesive, coating and the like.
Description
Technical field
The present invention relates to a kind of preparation method of polymer emulsion, be specifically related to a kind of preparation method of aqueous polyurethane-acrylate composite emulsion.
Background technology
Urethane is a kind of macromolecular material of excellent performance, has the flexible advantage such as good of low temperature resistant, resistance to chemical attack, antifriction scrape along, is used widely as coating, tackiness agent, fabric finishing agent etc. at present.Shortcomings such as traditional polyurethane material is based on solvent-borne type, and that used organic solvent generally has is inflammable, explosive, smell is big, poisonous, produce with use in easily human health and environment are worked the mischief.Last century, the seventies began the water-base polyurethane material that occurs and obtain developing rapidly, compared with traditional solvent borne polyurethane, had advantages such as little, nonflammable, the low pollution of toxicity.Along with improving constantly of aqueous polyurethane product performance, and much promulgations of country, department's correlation method order aspect the use of restriction volatile organic compounds (VOC), it is inevitable that the transformation from the solvent borne polyurethane to the aqueous polyurethane has become.
Yet aqueous polyurethane owing to introduced hydrophilic radical in the self structure, exist defectives such as water tolerance variation, surface gloss reduction, and production cost is higher when having excellent numerous advantages such as solvent resistance, wear resistance and snappiness.And be widely used in the polyacrylate material in fields such as coating, tackiness agent, printing and dyeing, then have and have weather-proof, anti-pollution, acidproof, alkaline-resisting, performance such as the transparency is good, and production cost is lower, but exists also that low temperature easily becomes fragile, shortcoming such as high temperature becomes glutinous, poor solvent resistance, the stretch-proof performance is not good.Therefore, by physics or chemical process both are combined, the preparation aqueous polyurethane-acrylate composite emulsion has not only reduced production cost, and has had both advantages concurrently, realizes having complementary advantages, and improves product performance.
The aqueous polyurethane-acrylate composite emulsion solid content of present domestic report is lower, be generally 30% ~ 40%, has nucleocapsid structure, and in preparation process, often need with an organic solvent to dissolve hydrophilic chain extender or reduce base polyurethane prepolymer for use as viscosity, final product need remove and reclaim organic solvent.Not not with an organic solvent, can save solvent removal and reclaim the back operation to enhance productivity, can avoid simultaneously producing with use in harm that human health and environment are caused, meet the notion of cleaner production; High solid content emulsion has fast drying, just advantage such as glues on the other hand, also reduces production, packing and transportation cost simultaneously.Therefore, do not use any solvent to prepare the aqueous polyurethane-acrylate composite emulsion of high solids content (more than 45%), will have important application value, relational approach rarely has report.
Summary of the invention
The objective of the invention is the shortcoming that exists among the present aqueous polyurethane-acrylate composite emulsion preparation method in order to overcome, a kind of new preparation method is provided, and this method need not solvent and can synthesize and have high-solid content water-based polyurethane-acrylate composite emulsion.
The present invention is achieved through the following technical solutions, and comprises the steps:
(1) under no any metal catalyst and solvent, adopts polymer diatomic alcohol, vulcabond, wetting ability chainextender synthetic water based polyurethane performed polymer;
(2) with vinyl compound performed polymer is carried out end-blocking, with post neutralization, add water self-emulsifying, chain extension, obtain aqueous polyurethane dispersion;
(3) in the presence of nothing adds emulsifying agent, drip the acrylic ester monomer that is dissolved with initiator in the dispersion and carry out polymerization, make the aqueous polyurethane-acrylate composite emulsion of high solids content.
Described polymer diatomic alcohol is one or both a mixture of poly adipate succinic acid ester (PBA), polypropylene glycol (PPG).
Described vulcabond is a hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) mixture formed of 2:1 in molar ratio.
Described wetting ability chainextender is dimethylolpropionic acid (DMBA), accounts for 3.2 ~ 4.0 % of aqueous polyurethane quality.Use hydrophilic chain extender more widely when dimethylol propionic acid (DMPA) is present synthetic water based polyurethane, but DMPA fusing point height (175～185 ℃) is difficult to heating for dissolving, this just need to add solvent as
N-methyl-2-pyrrolidone (NMP), acetone etc.NMP boiling point height be difficult to remove, and the solubleness of DMPA in acetone is less, needs to add a large amount of acetone in building-up process, takes off ketone process trouble and takes off untotally, brings potential safety hazard to production process.Dimethylolpropionic acid (DMBA) has the fusing point lower than DMPA, and DMBA is dissolved in polyvalent alcohol easily.Adopt DMBA to make hydrophilic chain extender, can reduce and even not use solvent, carry out the prepolymerization reaction of urethane.
In the step (1), in the described reaction system ,-NCO is 1.5 ~ 1.8 with the mol ratio of-OH, and described-NCO is the integral molar quantity of HDI and the contained isocyanate group of IPDI, and described-OH is the integral molar quantity of polymer diatomic alcohol and DMBA institute hydroxyl; Base polyurethane prepolymer for use as synthesizes under the nitrogen protection at 80 ℃, and the reaction times is 3.5h.
In the step (2), described vinyl compound is a hydroxyethyl methylacrylate, and the temperature of end capping is 70 ℃, and the end capping time is 1h; Neutralization reaction adopts triethylamine to carry out, and the temperature of neutralization reaction is 60 ℃, and the neutralization reaction time is 20min; By water droplet being added the aqueous polyurethane pre-emulsion that obtains self-emulsifying in the performed polymer, emulsifying temperature is 60 ℃, and emulsification times is 20min, and stirring velocity is 400r/min; Chain extension is carried out in gained urethane pre-emulsion employing two amine aqueous solutions, and temperature of reaction is 60 ℃.
In the step (3), described initiator is Diisopropyl azodicarboxylate (AIBN), acrylic ester monomer is one or more the mixture in methyl methacrylate, butyl methacrylate, the butyl acrylate, and the temperature of polyreaction is 79 ~ 90 ℃, and polymerization reaction time is 7h.
The aqueous polyurethane-acrylate composite emulsion solid content of the present invention's preparation is higher than 45%, and storage stability is greater than December.
Compared with prior art, the present invention has following beneficial effect:
The present invention replaces DMPA commonly used with novel hydrophilic chainextender DMBA, and make base polyurethane prepolymer for use as have suitable viscosity by the mol ratio (R value) of control-NCO and-OH, the realization building-up process is not used any solvent, not not with an organic solvent, can save needs solvent removal and reclaims the back operation to enhance productivity, can avoid simultaneously producing with use in the harm that causes of human health and environment; Do not use metal catalyst can avoid kish toxicity; Do not use and add emulsifying agent and can improve the product water tolerance; Solid content reaches 45%, has fast drying, just advantage such as glues, and can also reduce production, packing and transportation cost.
Embodiment
Further explain the present invention below in conjunction with embodiment, but embodiment does not do any type of qualification to the present invention.
Embodiment 1:The preparation of polyester type aqueous polyurethane-acrylate composite emulsion
Earlier 25.6g PBA is placed the 250mL three-necked flask, 120 ℃ of following vaccum dewatering 1h.Stop vacuum, logical nitrogen, add 1.304g DMBA, continue to be heated to its whole dissolvings.Be cooled to 80 ℃, add 2.26mL IPDI and 3.46mL HDI, 80 ℃, the following reaction of 300 r/min stirring 3.5h obtain the aqueous polyurethane performed polymer; Be cooled to 70 ℃, add HEMA0.82 g, continue reaction 1h.Be cooled to 60 ℃, add 0.85g TEA, reaction 20min.Drip 63mL water in reaction system, stirring and emulsifying under the 400r/min obtains pre-emulsion, drops in the above-mentioned pre-emulsion after 0.265g EDA is dissolved in 6.3mL water, and reaction 30min obtains aqueous polyurethane dispersion.Then 79 ℃, stir under (300r/min), in above-mentioned dispersion, drip the BA solution 22.68g that is dissolved with 0.204g AIBN, drip off in the 3h, continue reaction 2h.Be warming up to 82 ℃, reaction 1h is warming up to 85 ℃ again, and reaction 45min is warming up to 90 ℃ again, reaction 15min.Be cooled to normal temperature, discharging.Gained composite emulsion solid content is 45%, and viscosity is 52.8 cP, and the glued membrane tensile strength is 13.9MPa, and elongation at break is that 1022.0%, 25 ℃ of following 24h water-intake rate is that 1.07%, 60 ℃ of 36h water-intake rate is 5.87%.Average emulsion particle diameter is 87.5nm, and storage stability is greater than December.
Embodiment 2:The preparation of polyether type aqueous polyurethane-acrylate composite emulsion
Press the identical preparation method of embodiment 1, but 25.6g PBA changes 25.6g PPG into, 22.68g BA changes 22.68g MMA into.Gained composite emulsion solid content is 45%, and viscosity is 45.4cP, and median size is 138.9nm, and glued membrane is transparent, and tensile strength is 14.2MPa, and elongation at break is that 452.5%, 25 ℃ of following 24h water-intake rate is that 3.00%, 60 ℃ of 36h water-intake rate is 15.22%.
Embodiment 3:The preparation of polyester and polyether type aqueous polyurethane-acrylate composite emulsion
Press the identical preparation method of embodiment 1, but 25.6g PBA changes 20.48gPBA and 5.12g PPG into.Gained composite emulsion solid content is 45%, and viscosity is 93.2 cP, and median size is 93.1nm, and tensile strength is 7.1MPa, and elongation at break is that 882.8%, 25 ℃ of following 24h water-intake rate is that 1.91%, 60 ℃ of 36h water-intake rate is 7.53%.
Claims (10)
1. the preparation method of an aqueous polyurethane-acrylate composite emulsion is characterized in that comprising the steps:
(1) under no any metal catalyst and solvent, adopts polymer diatomic alcohol, vulcabond, wetting ability chainextender synthetic water based polyurethane performed polymer;
(2) with vinyl compound performed polymer is carried out end-blocking, carry out self-emulsifying with post neutralization, dropping water, chain extension obtains aqueous polyurethane dispersion then;
(3) in the presence of nothing adds emulsifying agent, drip the acrylic ester monomer that is dissolved with initiator in the dispersion and carry out polymerization, make the aqueous polyurethane-acrylate composite emulsion of high solids content.
2. preparation method as claimed in claim 1 is characterized in that described polymer diatomic alcohol is one or both the mixture in poly adipate succinic acid ester, the polypropylene glycol.
3. preparation method as claimed in claim 1 is characterized in that described vulcabond is hexamethylene diisocyanate and the isophorone diisocyanate mixture formed of 2:1 in molar ratio.
4. preparation method as claimed in claim 1 is characterized in that described wetting ability chainextender is a dimethylolpropionic acid, accounts for 3.2 ~ 4.0 % of aqueous polyurethane performed polymer quality.
5. preparation method as claimed in claim 1, it is characterized in that in the step (1), in the described reaction system,-NCO is 1.5 ~ 1.8 with the mol ratio of-OH, described-NCO is the integral molar quantity of hexamethylene diisocyanate and the contained isocyanate group of isophorone diisocyanate, and described-OH is the integral molar quantity of polymer diatomic alcohol and dimethylolpropionic acid institute hydroxyl.
6. preparation method as claimed in claim 1 is characterized in that in the step (1), described base polyurethane prepolymer for use as synthesizes under the nitrogen protection at 80 ℃, and the reaction times is 3.5 hours.
7. preparation method as claimed in claim 1 is characterized in that in the step (2), described vinyl compound is a hydroxyethyl methylacrylate, and the temperature of end capping is 70 ℃, and the end capping time is 1 hour.
8. preparation method as claimed in claim 1 is characterized in that in the step (2), and described neutralization is carried out neutralization reaction for adopting triethylamine, and the temperature of neutralization reaction is 60 ℃, and the neutralization reaction time is 20 minutes.
9. preparation method as claimed in claim 1 is characterized in that in the step (2), and described chain extension carries out chain extending reaction for adopting quadrol, and the temperature of chain extending reaction is 60 ℃, and the chain extending reaction time is 30 minutes.
10. preparation method as claimed in claim 1, it is characterized in that in the step (3), described initiator is a Diisopropyl azodicarboxylate, acrylic ester monomer is one or more the mixture in methyl methacrylate, butyl methacrylate, the butyl acrylate, the temperature of polyreaction is 79 ~ 90 ℃, and polymerization reaction time is 7 hours.
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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 |
| CN102417578A (en) * | 2011-11-01 | 2012-04-18 | 吴江市北厍盛源纺织品助剂厂 | Preparation method of high-solid-content waterborne polyurethane adhesive coating agent |
| CN102516465A (en) * | 2011-11-19 | 2012-06-27 | 烟台万华聚氨酯股份有限公司 | High-elasticity waterborne polyurethane-acrylate composite resin, and preparation method and application thereof |
| CN102757540A (en) * | 2012-07-10 | 2012-10-31 | 陕西科技大学 | Preparation method of waterborne polyurethane for synthetic leather |
| CN105085830A (en) * | 2015-08-13 | 2015-11-25 | 佛山市三水协佳化工有限公司 | Preparation method of high-water-resistant anti-freezing PUA resin |
| CN105199050A (en) * | 2015-09-11 | 2015-12-30 | 湘潭大学 | Polyurethane grafted copolymer and preparation method of polyurethane grafted copolymer |
| CN105294958A (en) * | 2015-11-30 | 2016-02-03 | 桂林市和鑫防水装饰材料有限公司 | Waterborne polyurethane modified acrylate emulsion preparation method |
| CN105884977A (en) * | 2014-12-30 | 2016-08-24 | 武汉源长科工贸有限责任公司 | Formula and preparation technology of waterborne resin |
| CN106065049A (en) * | 2016-06-01 | 2016-11-02 | 南雄市瑞晟化学工业有限公司 | High solids content environment-friendly water-based polyurethane acrylate composite emulsion and preparation method thereof |
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| CN107257812A (en) * | 2015-03-12 | 2017-10-17 | 汉高股份有限及两合公司 | The aqueous dispersion of urethane acrylate hybrid |
| CN107868167A (en) * | 2017-12-14 | 2018-04-03 | 武汉理工大学 | A kind of aqueous polyurethane Pickering acrylate composite emulsions of HEMA end-blockings and preparation method thereof |
| CN109251274A (en) * | 2017-07-13 | 2019-01-22 | 和友纺织股份有限公司 | The method for closing object with solvent-free processing procedure production ultra-soft matter water polyacrylic acid urethane copolymerization |
| CN109337632A (en) * | 2018-09-11 | 2019-02-15 | 万华化学（宁波）有限公司 | Aqueous one-component adhesive and its application in automobile interior decoration bonding |
| DE102017122633A1 (en) * | 2017-09-28 | 2019-03-28 | Ho Yu Textile Co., Ltd. | Process for the solvent-free preparation of a super-soft PAU core-shell copolymer dispersion |
| CN111454420A (en) * | 2020-04-13 | 2020-07-28 | 齐鲁工业大学 | Preparation method of high-solid carboxylic acid type waterborne polyurethane |
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