CN102295735B - Polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion and preparation method thereof - Google Patents
Polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN102295735B CN102295735B CN 201110134889 CN201110134889A CN102295735B CN 102295735 B CN102295735 B CN 102295735B CN 201110134889 CN201110134889 CN 201110134889 CN 201110134889 A CN201110134889 A CN 201110134889A CN 102295735 B CN102295735 B CN 102295735B
- Authority
- CN
- China
- Prior art keywords
- epoxy
- emulsion
- polyurethane
- preparation
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 53
- 239000000839 emulsion Substances 0.000 title claims abstract description 27
- 238000004945 emulsification Methods 0.000 title claims abstract description 20
- 229920003226 polyurethane urea Polymers 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims abstract description 22
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 239000004816 latex Substances 0.000 claims description 7
- 229920000126 latex Polymers 0.000 claims description 7
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229950009789 cetomacrogol 1000 Drugs 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- TZBAVQKIEKDGFH-UHFFFAOYSA-N n-[2-(diethylamino)ethyl]-1-benzothiophene-2-carboxamide;hydrochloride Chemical compound [Cl-].C1=CC=C2SC(C(=O)NCC[NH+](CC)CC)=CC2=C1 TZBAVQKIEKDGFH-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229920002396 Polyurea Polymers 0.000 description 11
- 239000002904 solvent Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 230000005226 mechanical processes and functions Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 2
- 230000037452 priming Effects 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion and a preparation method thereof. The emulsion has solid content of 40-50%, an average particle size of less than 500nm and a viscosity of 500-650(mPa*S). A chain segment in the self-emulsifying nanometer waterborne emulsion of the invention is introduced with a compound containing a nonionic hydrophilic chain segment, so that epoxy resin can have a self-emulsifying property, and the corrosion resistance and curing time of a coating can be improved by the polyurethane-urea based chain segment.A water dispersion system formed by the modified epoxy resin is then subjected to high pressure emulsification by a homogenizer and the particle size is dispersed to a nanoscale, and after a long time storage, physicochemical properties change little. Thus, the emulsion of the invention has good stability. The synthesis process of the method provided in the invention adds no organic solvent and has simple operation, thus being easy to realize.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion and preparation method.
Background technology
Particularly Water-borne modification epoxypaint and nanometer modified epoxy cold coating develop rapidly epoxypaint in recent years.Because Resins, epoxy has excellent physics and chemical property, as good sticking power, chemical proofing and solvent resistance excellence, hardness height, corrosion-resistant, good heat stability, so cause people's attention always.Common solvent type epoxypaint contains the organic volatile solvent, and these organic solvents entered in the atmosphere owing to solvent evaporates in production and the construction stage of coating, environment were polluted harm humans health.Compare with solvent based coating, aqueous epoxy coating has many advantages, low such as organic volatile content, smell is little, use is safe, even do not contain organic solvent, can wash by water etc., so be widely used as high-performance building coating, equipment priming paint, transportation means priming paint, vehicle paint base and industrial maintenance finish paint etc.
The Resins, epoxy Water-borne modification mainly contains mechanical process, phase reversion method and three kinds of methods of chemic modified method in the worldwide at present: the less stable of the epoxy emulsion of mechanical process and the preparation of phase reversion method is used poor effect with aqueous epoxy curing agent, filler and various auxiliary agent; Chemic modified method is that the size of dispersed phase particles can reach nano level in the aqueous epoxy resin emulsion of self-emulsification preparation, can form the stabilized aqueous epoxy resin latex.
Chemical modification Resins, epoxy can be introduced hydrophilic polar group on the one hand, and these hydrophilic radicals can help Resins, epoxy to disperse in water; Also can introduce group or the macromolecular chain of other senses on the other hand, in order to the physicals of improving Resins, epoxy or give its more good characteristic.For example utilize the research of polyurethane modified epoxy resin to emerge in an endless stream in the oiliness system, and also begin in water-based system, to use, can improve the fragility of epoxy, increase toughness, but simple polyurethane-modified set time is longer, is unfavorable for spraying application, therefore need improve.Can utilize the high reactivity of urea groups to solve the problem of set time, can also improve corrosive nature simultaneously.
Summary of the invention
The preparation method of the polyurethane-urea modified self-emulsifying nanometer epoxy emulsion that the present invention proposes uses chemic modified method, hydrophilic segment, polyurethane-urea segment are introduced Resins, epoxy, it is the polyurethane-urea modified aqueous epoxy resin, again in conjunction with processing means such as high speed dispersor, colloidal mill, clarifixators, it is even to obtain particle diameter, nano level, and the polyurea modified self-emulsifying nanometer waterborne epoxy emulsion of excellent property.
Technical scheme of the present invention is as follows:
Polyurethane-polyurea modified self-emulsifying nanometer waterborne epoxy emulsion of the present invention, emulsion solid content 40-50%, median size<500nm, viscosity 500-650 (mPaS).
The preparation method of polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion of the present invention, step is as follows:
1) adding is preheating to 50~60 ℃ non-ionic hydrophilic chain segment compounds in Resins, epoxy, adds boron trifluoride diethyl etherate or triphenylphosphine catalyzer again, and reaction 4~6h obtains modified epoxy under 80~100 ℃; Catalyst levels is 1~3% of weight epoxy;
2) drip the polyisocyanates reaction in the modified epoxy of step 1) and obtain performed polymer, 50~70 ℃ of temperature of reaction, reaction times 1~2h; Isocyanate group and 1) step institute to add the amido ratio be 1: 1~3;
3) with step 2) performed polymer that obtains mixes 60~90 ℃ of temperature of reaction, time 1~3h with raw material epoxy resin (identical with step (1)); The addition of performed polymer is 10~20% of weight epoxy;
4) the polyurea modified Resins, epoxy with the step 3) preparation drips deionized water under high speed dispersion, descends suddenly until system viscosity, obtains epoxy resin latex;
5) with 4) preparation emulsion grind through colloidal mill, carry out high-pressure emulsification with clarifixator again, obtain stable polyurea modified self-emulsifying nanometer waterborne epoxy emulsion.
The non-ionic hydrophilic chain segment compounds that adopts in the described step 1) is cetomacrogol 1000 or 4000 and the mixture of Amino Terminated polyether(ATPE) D2000, mass ratio 10: 1;
Described step 2) polyisocyanates that adopts in is tolylene diisocyanate, MDI or hexamethylene diisocyanate.
The rate of dispersion of described step 3 high speed dispersion machine is 1000~4000r/min.
The colloidal mill milling time is 0.5~1.5h in the described step 4, and rotating speed is 2500~3500r/min; High pressure homogenizer emulsification pressure is 30~100MPa, and emulsification times is 0.5~1.5h.
The self-emulsifying nanometer waterborne emulsion that the present invention proposes makes Resins, epoxy have automatic emulsifying performance owing to introduced a kind of compound that contains the non-ionic hydrophilic segment in the segment, and polyurethane-urea base segment has improved corrosion resistance nature and the set time of filming.The aqueous dispersion that modified epoxy forms passes through the clarifixator high-pressure emulsification again, disperses particle diameter to reach nano level, the long-time storage, and physical and chemical performance does not have considerable change, has good stability.This kind method building-up process is not added any organic solvent, and simple to operate, is easy to realize.
Adopt the performance of gained aqueous epoxy emulsion of the present invention as follows:
Embodiment
Below by example the present invention is described in further detail:
Embodiment 1
1, modified epoxy is synthetic: add the 13.6g epoxy resin E-44 in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed earlier, be warmed up to 50 ℃, slowly drip the mixture of 23.1gD2000 and PEG1000, be warmed up to 80 ℃, reaction 4h gets modified epoxy.
2, performed polymer is synthetic: above-mentioned reaction system is cooled to 50 ℃, slowly drips 1.7gTDI, and reaction 1h obtains epoxy prepolymer.
3, get the above-mentioned epoxy resin prepolymer 4g that obtains and mix with 40g E-44, react 1h down at 60 ℃, from reaction vessel, take out.
4, with above-mentioned product under the 1000r/min high speed dispersion, drip 110g distilled water, obtain the polyurea modified epoxy resin latex.
5, with under the above-mentioned emulsion process vertical colloid mill 2500r/min condition, disperse 30min, use the nanometer clarifixator to carry out 30MPa high-pressure emulsification 30min then, obtain stable polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion.
Embodiment 2
1, modified epoxy is synthetic: add the 4.5g epoxy resin E-44 in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed earlier, be warmed up to 60 ℃, slowly drip the mixture of 23.1gD2000 and PEG4000, be warmed up to 100 ℃, reaction 6h gets modified epoxy.
2, performed polymer is synthetic: above-mentioned reaction system is cooled to 70 ℃, slowly drips 2.6g MDI, and reaction 2h obtains epoxy prepolymer.
3, get the above-mentioned epoxy resin prepolymer 4g that obtains and mix with 20g E-44, react 3h down at 90 ℃, from reaction vessel, take out.
4, with above-mentioned product under the 1000r/min high speed dispersion, drip 48g distilled water, obtain the polyurea modified epoxy resin latex.
5, with under the above-mentioned emulsion process vertical colloid mill 3500r/min condition, disperse 1.5h, use the nanometer clarifixator to carry out 100MPa high-pressure emulsification 1.5h then, obtain stable polyurea modified self-emulsifying nanometer waterborne epoxy emulsion.
Embodiment 3
1, modified epoxy is synthetic: add the 13.6g epoxy resin E-44 in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed earlier, be warmed up to 55 ℃, slowly drip the mixture of 23.1g D2000 and PEG4000, be warmed up to 90 ℃, reaction 5h gets modified epoxy.
2, performed polymer is synthetic: above-mentioned reaction system is cooled to 60 ℃, slowly drips 1.7g HDI, and reaction 1.5h obtains epoxy prepolymer.
3, get the above-mentioned epoxy resin prepolymer 4g that obtains and mix with 40g E-44, react 2h down at 70 ℃, from reaction vessel, take out.
4, with above-mentioned product under the 1000r/min high speed dispersion, drip 88g distilled water, obtain the polyurea modified epoxy resin latex.
5, with under the above-mentioned emulsion process vertical colloid mill 2500r/min condition, disperse 1h, use the nanometer clarifixator to carry out 50MPa high-pressure emulsification 1h then, obtain stable polyurea modified self-emulsifying nanometer waterborne epoxy emulsion.
Embodiment 4
1, modified epoxy is synthetic: add the 4.5g epoxy resin E-44 in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed earlier, be warmed up to 60 ℃, slowly drip the mixture of 23.1gD2000 and PEG1000, be warmed up to 95 ℃, reaction 4h gets modified epoxy.
2, performed polymer is synthetic: above-mentioned reaction system is cooled to 65 ℃, slowly drips 1.3g MDI, and reaction 1.5h obtains epoxy prepolymer.
3, get the above-mentioned epoxy resin prepolymer 4g that obtains and mix with 20g E-44, react 2h down at 80 ℃, from reaction vessel, take out.
4, with above-mentioned product under the 1000r/min high speed dispersion, drip 60g distilled water, obtain the polyurea modified epoxy resin latex.
5, with under the above-mentioned emulsion process vertical colloid mill 3000r/min condition, disperse 1h, use the nanometer clarifixator to carry out 70MPa high-pressure emulsification 1h then, obtain stable polyurea modified self-emulsifying nanometer waterborne epoxy emulsion.
The present invention is not limited to the technology described in the embodiment; its description is illustrative; and it is nonrestrictive; authority of the present invention is limited by claim; based on the art personnel according to the present invention can change, technology related to the present invention that method such as reorganization obtains, all within protection scope of the present invention.
Claims (4)
1. the preparation method of polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion is characterized in that the polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion, emulsion solid content 40-50%, median size<500nm, viscosity 500-650mPaS; The preparation method, step is as follows:
1) adding is preheating to 50~60 ℃ non-ionic hydrophilic chain segment compounds in Resins, epoxy, adds boron trifluoride diethyl etherate or triphenylphosphine catalyzer again, and reaction 4~6h obtains modified epoxy under 80~100 ℃; Catalyst levels is 1~3% of weight epoxy;
2) drip the polyisocyanates reaction in the modified epoxy of step 1) and obtain performed polymer, 50~70 ℃ of temperature of reaction, reaction times 1~2h; Isocyanate group and 1) step institute to add the amido ratio be 1:1~3;
3) with step 2) performed polymer and the raw material epoxy resin that obtain mix 60~90 ℃ of temperature of reaction, time 1~3h; The addition of performed polymer is 10~20% of weight epoxy;
4) the polyurethane-urea modified epoxy with the step 3) preparation drips deionized water under high speed dispersion, descends suddenly until system viscosity, obtains epoxy resin latex;
5) emulsion of step 4) preparation is ground through colloidal mill, carry out high-pressure emulsification with clarifixator again, obtain stable polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion;
The non-ionic hydrophilic chain segment compounds is the mixture of a kind of of cetomacrogol 1000 and Macrogol 4000 and Amino Terminated polyether(ATPE) D2000, mass ratio 10:1.
2. the method for claim 1 is characterized in that described step 2) in the polyisocyanates that adopts be tolylene diisocyanate, '-diphenylmethane diisocyanate or hexamethylene diisocyanate.
3. the method for claim 1, the rate of dispersion that it is characterized in that described step 3) high speed dispersion machine is 1000~4000r/min.
4. the method for claim 1 is characterized in that the colloidal mill milling time is 0.5~1.5h in the described step 4), and rotating speed is 2500~3500r/min; High pressure homogenizer emulsification pressure is 30~100MPa, and emulsification times is 0.5~1.5h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 201110134889 CN102295735B (en) | 2011-05-23 | 2011-05-23 | Polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 201110134889 CN102295735B (en) | 2011-05-23 | 2011-05-23 | Polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102295735A CN102295735A (en) | 2011-12-28 |
CN102295735B true CN102295735B (en) | 2013-07-17 |
Family
ID=45356428
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN 201110134889 Expired - Fee Related CN102295735B (en) | 2011-05-23 | 2011-05-23 | Polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102295735B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110452768A (en) * | 2018-05-07 | 2019-11-15 | 天津科技大学 | A kind of preparation of greases method of viscoelasticity characteristic and obtained product |
CN111019082B (en) * | 2019-12-16 | 2021-07-27 | 东南大学 | Nonionic photo-curing polyurethane aqueous dispersion resin composition with excellent compatibility and preparation method and application thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101003715A (en) * | 2007-01-05 | 2007-07-25 | 华南理工大学 | Method for preparing modified aqueous adhesion agent of polyurethane |
CN101402739A (en) * | 2008-11-14 | 2009-04-08 | 天津大学 | Production process for water-soluble epoxy resin emulsions |
CN101717484A (en) * | 2009-11-20 | 2010-06-02 | 天津大学 | Method for preparing polyurethane-modified self-emulsifying nanometer waterborne epoxy emulsion |
CN101798484A (en) * | 2010-03-05 | 2010-08-11 | 四川大学 | Dendritic organic-inorganic hybrid water-borne nano polyurethane-epoxy anticorrosive coating and preparation method thereof |
CN101824133A (en) * | 2010-04-28 | 2010-09-08 | 天津大学 | Preparation method for waterborne polyurethane modified epoxy resin curing agent |
CN101880508A (en) * | 2010-06-24 | 2010-11-10 | 同济大学 | Preparation method of high abrasion water-borne wood coating |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6797789B2 (en) * | 2001-10-19 | 2004-09-28 | Visuron Technologies, Inc. | Phenolic/polyurea coating co-polymer compositions and process |
-
2011
- 2011-05-23 CN CN 201110134889 patent/CN102295735B/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101003715A (en) * | 2007-01-05 | 2007-07-25 | 华南理工大学 | Method for preparing modified aqueous adhesion agent of polyurethane |
CN101402739A (en) * | 2008-11-14 | 2009-04-08 | 天津大学 | Production process for water-soluble epoxy resin emulsions |
CN101717484A (en) * | 2009-11-20 | 2010-06-02 | 天津大学 | Method for preparing polyurethane-modified self-emulsifying nanometer waterborne epoxy emulsion |
CN101798484A (en) * | 2010-03-05 | 2010-08-11 | 四川大学 | Dendritic organic-inorganic hybrid water-borne nano polyurethane-epoxy anticorrosive coating and preparation method thereof |
CN101824133A (en) * | 2010-04-28 | 2010-09-08 | 天津大学 | Preparation method for waterborne polyurethane modified epoxy resin curing agent |
CN101880508A (en) * | 2010-06-24 | 2010-11-10 | 同济大学 | Preparation method of high abrasion water-borne wood coating |
Non-Patent Citations (1)
Title |
---|
张郃,吴跃焕.环氧-聚氨酯乳液合成涂料的研究.《山西化工》.2006,第26卷(第3期), * |
Also Published As
Publication number | Publication date |
---|---|
CN102295735A (en) | 2011-12-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101717484A (en) | Method for preparing polyurethane-modified self-emulsifying nanometer waterborne epoxy emulsion | |
CN102690404A (en) | Nonionic waterborne polyurethane dispersoid and preparation method thereof | |
CN103555192B (en) | A kind of organic-silicon-modified waterborne UV coating and preparation method thereof | |
CN101475742B (en) | Aromatic yellow-stain resistant polyurethane resin for synthetic leather and preparation thereof | |
CN102504166B (en) | Preparation method of hyperbranched water-based polyurethane hydroxy component | |
CN107022297A (en) | A kind of water-fast aqueous polyurethane coating with bi component and preparation method thereof | |
CN107586510B (en) | Preparation method of corrosion-resistant polyurethane modified epoxy resin emulsion | |
CN102181037B (en) | Method for preparing 3,3'-dimethyl-4,4'-biphenyl diisocyanate (TODI)-based thermoplastic polyurethane elastomer | |
CN101121869A (en) | Method for preparing water polyurethane binder for shoe | |
CN103146181B (en) | Preparation method of high-solid content wide-temperature range damping polyurethane aqueous dispersion containing nanofiller | |
CN102241956A (en) | Poly(propylene carbonate)-based water-borne polyurethane adhesive and preparation method thereof | |
CN105131227B (en) | A kind of use for synthetic leather UV cured flame-retardant polyurethane and preparation method thereof | |
CN105367733B (en) | A kind of preparation method and purposes based on benzoic anhydride polyester polyol aqueous polyurethane film | |
CN104974703A (en) | Double-component hyper-branched polyurethane adhesive and preparation method therefor | |
CN103980810A (en) | Waterproof solvent-free single-component polyurethane lacquer used on wet surface and preparation method thereof | |
CN101775117A (en) | Waterborne polyurethane with lateral chain containing fluoroalkyl and preparation method thereof | |
CN101857721A (en) | Cold-resistant, solvent-resistant and yellowing-resistant polyurethane resin and preparation method thereof | |
CN102295735B (en) | Polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion and preparation method thereof | |
CN107151520B (en) | A kind of tung oil base water polyurethane coating and preparation method thereof | |
CN103012725A (en) | Polyurethane raw liquid for rubber rolls available for mould-free casting | |
CN107428914B (en) | Composition epoxy resin | |
Vaidya et al. | Recent developments in waterborne polyurethane dispersions (WPUDs): a mini-review on thermal and mechanical properties improvement | |
Zhang et al. | High-gravity-assisted emulsification for continuous preparation of waterborne polyurethane nanodispersion with high solids content | |
CN104910342A (en) | Preparation method of waterborne polyurethane | |
CN106750149A (en) | A kind of preparation method and application method of expansion type aqueous polyurethane |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130717 |
|
CF01 | Termination of patent right due to non-payment of annual fee |