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CN103819646A - Ultraviolet-curable waterborne polyurethane and preparation method thereof - Google Patents

Ultraviolet-curable waterborne polyurethane and preparation method thereof Download PDF

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Publication number
CN103819646A
CN103819646A CN201310231599.5A CN201310231599A CN103819646A CN 103819646 A CN103819646 A CN 103819646A CN 201310231599 A CN201310231599 A CN 201310231599A CN 103819646 A CN103819646 A CN 103819646A
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吴晓波
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JIANGYIN MORE CHEMICAL NEW MATERIALS CO Ltd
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JIANGYIN MORE CHEMICAL NEW MATERIALS CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention discloses a composite used for synthesizing ultraviolet-curable waterborne polyurethane. The ultraviolet-curable composite mainly comprises deionized water, a solvent and metered (A) methacrylic acid alpha-hydroxy triamino alcohol ester, (B) low polyethylene glycol and (C) diisocyanate. The polyurethane synthesized by the composite has the characteristics of high content of double bonds, high content density of double bonds and high hard segment content, and a polyurethane coating film also has the characteristics of high hardness, fast curing and butanone wiping resistance in physics.

Description

Aqueous polyurethane of uV curable and preparation method thereof
Technical field
The present invention relates to a kind of urethane, particularly be that a kind of self-control chainextender that adopts is prepared the method for photocuring aqueous polyurethane.
Background technology
Ultraviolet light polymerization general reference rapid polymerization after UV-irradiation reacts and curing process.Because this technology has fast setting, production efficiency is high, energy-conservation, environmental protection, and high-quality, economy, is applicable to the advantages such as multiple base material, and now widespread use has printing, packing, electronics, household electrical appliances, auto lamp all trades and professions.The present invention is about a kind of aqueous polyurethane acrylate.
Traditionally, the synthetic method of photo curable aqueous polyurethane is all, with the monohydroxy such as Hydroxyethyl acrylate or hydroxypropyl acrylate acrylate, urethane is carried out to end-blocking, introduce two keys with this, but two key amounts that these class methods are introduced are limited, the degree of crosslinking of the polyurethane coating film after solidifying is not high, maybe the unsaturated polyester that contains two keys is incorporated in polyurethane molecular chain as soft section, although improved to a certain extent the content of two keys, but the hard segment content of its building block will decline, thus cause solidify after polyurethane coating film hardness do not have too large raising yet.
CN200810039199.3 discloses a kind of mercaptan-alkene system of introducing to polyurethane polyol or isocyanate-terminated base polyurethane prepolymer for use as, prepare the synthetic method containing the aqueous polyurethane ultraviolet light solidfication water polyurethane of multi-thiol and polynary alkene by self-emulsifying again, to improving functional group transformation efficiency, overcome oxidation and hinder and improve the mechanical property that high double bond content brings.
CN200910017333.4 discloses one polyether glycol has been introduced in polyurethane backbone, and prepare the synthetic method having compared with high molecular weight thereby raising double key number object ultraviolet light solidfication water polyurethane with the monomer end-blocking of monohydroxy esters of acrylic acid, to improving the chemical resistance of urethane and taking into account hardness and suppleness.
CN201210206961.9 discloses a kind of synthetic method of two hydroxy fatty acids as the ultraviolet light solidfication water polyurethane of chainextender of utilizing, to improving relative molecular mass and stability in storage.
As can be seen here, the mode that prior art improves double bond content is increase transformation efficiency or improve relative molecular mass, thereby cannot improve the density of two keys in polyurethane molecular, also cannot improve theoretically the hard segment content of urethane.
Summary of the invention
In view of the above-mentioned defect of prior art, the hard segment content that the present invention seeks to improve two key density and improve in theory aqueous polyurethane.
Therefore, the invention provides a kind of small molecule chain extender by the end amino that contains two keys and be present in aqueous polyurethane of the uV curable in urethane chain link and preparation method thereof with hard section of form.
The present invention also provides the preparation method of the amino small molecule chain extender of described double bond containing end.
Described aqueous polyurethane preparation method comprises the following steps:
(1) hold the synthetic of amino small molecule chain extender methacrylic acid Alpha-hydroxy triamino alcohol ester
In dry reactor, add diethylenetriamine, by appropriate acetone diluted, be heated to 60 ℃ of left and right, now acetone has backflow, drips the glycidyl methacrylate of crossing by acetone diluted, within 2-2.5 hour, drips off, be incubated about 10 minutes, cooling extraction acetone; Open loop condensation reaction obtains holding amino methacrylic acid Alpha-hydroxy triamino alcohol ester.Be shown below:
Figure BDA00003332341000021
(2) by about 100 parts of low poly-dihydric alcohols of weight in reactor under 120 ℃, the condition of about-0.09MPa processed after approximately 1 hour, be down to room temperature, add the vulcabond of about 100 parts of weight to react 2 hours at about 95 ℃; Add about 2 hours of about 85 ℃ reactions of the hydrophilic chain extender dimethylol propionic acid of about 15 parts of weight and N-Methyl pyrrolidone (a small amount of dibutyl tin laurate), to theoretical NCO content, be cooled to 50 ℃ of left and right, add the methacrylic acid Alpha-hydroxy triamino alcohol ester that about 10 parts of weight contain stopper to react about 30 minutes, finally add Hydroxyethyl acrylate or the hydroxypropyl acrylate of metering, 60 ℃ of left and right are incubated about 2 hours, to system, do not contain NCO, be cooled to 40 ℃ of left and right, add triethylamine neutralization, add deionized water emulsification.
Figure BDA00003332341000031
The preparation method of UV curable aqueous polyurethane resin of the present invention compared with prior art has the following advantages:
Owing in the present invention, the small molecule chain extender of the end amino that contains two keys being carried out to chain extension to urethane, use again monohydroxy acrylate to its end-blocking, this preparation method not only than existing employing monohydroxy acrylate to its end-blocking, be incorporated into method in urethane chain link with unsaturated polyester as the mode of soft section and introduce more double key number amount and more sp2 hydridization nitrogen-atoms, thereby not only improve double bond content and density, increase resonance simultaneously, thereby make the also corresponding raising of hard segment content in urethane chain link, film cross-linking density after gained solidifies is larger, simultaneously, this chainextender is that end is amino, be incorporated in polyurethane chain, its urea linkage content also can correspondingly improve, further make the hardness of film after solidifying increase substantially.
In the present invention, by glycidyl methacrylate and diethylenetriamine, 60 ℃ of left and right open loop condensation reactions in acetone solvent obtain methacrylic acid Alpha-hydroxy triamino alcohol ester.
Embodiment
Embodiment 1
(1) in dry reactor, add diethylenetriamine, by appropriate acetone diluted, be heated to 60 ℃ of left and right, now acetone has backflow, drips the glycidyl methacrylate of crossing by acetone diluted, within 2-2.5 hour, drips off, be incubated 10 minutes, cooling extraction acetone; Open loop condensation reaction obtains methacrylic acid Alpha-hydroxy triamino alcohol ester.
(2) by 100 parts of weight polytetrahydrofuran diols in reactor under 120 ℃ ,-0.09MPa condition processed after approximately 1 hour, be down to room temperature, add 96.2 parts of weight isophorone diisocyanates about 95 ℃ reactions 2 hours; Add 85 ℃ of reactions of 8 parts of weight hydrophilic chain extender dimethylol propionic acids and 5 parts of weight N-Methyl pyrrolidone (a small amount of dibutyl tin laurate) 2 hours, to theoretical NCO content, be cooled to 50 ℃ of left and right, add the methacrylic acid Alpha-hydroxy triamino alcohol ester that 10 parts of weight contain hydroquinone of polymerization retarder to react 30 minutes, finally add 55 parts of weight percent acrylic acid hydroxyl ethyl esters, 60 ℃ are incubated 2 hours, to system, do not contain NCO, be cooled to 40 ℃ of left and right, add 5.25 parts of weight triethylamine neutralizations, add deionized water emulsification.
Embodiment 2
(1) with embodiment 1 (1) step.
(2) by 40 parts of weight polytetrahydrofuran diols and 60 parts of weight N220 polyether Glycols in reactor under 120 ℃ ,-0.09MPa condition processed after approximately 1 hour, be down to room temperature, add 96.2 parts of weight isophorone diisocyanates about 95 ℃ reactions 2 hours; Add 85 ℃ of reactions of 8 parts of weight hydrophilic chain extender dimethylol propionic acids and 5 parts of weight N-Methyl pyrrolidone (a small amount of dibutyl tin laurate) 2 hours, to theoretical NCO content, be cooled to 50 ℃ of left and right, add the methacrylic acid Alpha-hydroxy triamino alcohol ester that 10 parts of weight contain stopper p methoxy phenol to react 30 minutes, finally add 55 parts of weight percent acrylic acid hydroxyl ethyl esters, 60 ℃ are incubated 2 hours, to system, do not contain NCO, be cooled to 40 ℃ of left and right, add 5.25 parts of weight triethylamine neutralizations, add deionized water emulsification.
Embodiment 3
(1) with embodiment 1 (1) step.
(2) by 40 parts of weight polytetrahydrofuran diols and 60 parts of weight polycaprolactone glycols in reactor under 120 ℃ ,-0.09MPa condition processed after approximately 1 hour, be down to room temperature, add 64.13 parts of weight isophorone diisocyanates and 37.8 parts of weight dicyclohexyl methane diisocyanates about 95 ℃ reactions 2 hours; Add 85 ℃ of reactions of 10 parts of weight hydrophilic chain extender dimethylol propionic acids and 5 parts of weight N-Methyl pyrrolidone (a small amount of dibutyl tin laurate) 2 hours, to theoretical NCO content, be cooled to 50 ℃ of left and right, add the base vinylformic acid Alpha-hydroxy triamino alcohol ester that 15.6 parts of weight first contain hydroquinone of polymerization retarder to react 30 minutes, finally add 47.8 parts of weight percent acrylic acid hydroxyl ethyl esters, 60 ℃ are incubated 2 hours, to system, do not contain NCO, be cooled to 40 ℃ of left and right, add 6.65 parts of weight triethylamine neutralizations, add deionized water emulsification.
Embodiment 4
(1) with embodiment 1 (1) step.
(2) by poly-100 parts of weight DOPCP in reactor under 120 ℃ ,-0.09MPa condition processed after approximately 1 hour, be down to room temperature, add 48.1 parts of weight dicyclohexyl methane diisocyanates and 36.35 parts of weight hexamethylene diisocyanates to react 2 hours at about 95 ℃; Add 85 ℃ of reactions of 9.3 parts of weight hydrophilic chain extender dimethylol propionic acids and 7 parts of weight N-Methyl pyrrolidone (a small amount of dibutyl tin laurate) 2 hours, to theoretical NCO content, be cooled to 50 ℃ of left and right, add the methacrylic acid Alpha-hydroxy triamino alcohol ester that 12.1 parts of weight contain stopper 2-Tert. Butyl Hydroquinone to react 30 minutes, finally add 51.5 parts of weight percent acrylic acid hydroxyl ethyl esters, 60 ℃ are incubated 2 hours, to system, do not contain NCO, be cooled to 40 ℃ of left and right, add 6.3 parts of weight triethylamine neutralizations, add deionized water emulsification.
Embodiment 5
(1) in dry reactor, add diethylenetriamine, with appropriate butanone dilution, be heated to 80 ℃ of left and right, now butanone has backflow, drips the glycidyl methacrylate of diluting with butanone, within 2-3 hour, drips off, be incubated 10 minutes, cooling extraction butanone; Open loop condensation reaction obtains methacrylic acid Alpha-hydroxy triamino alcohol ester.
(2) by 100 parts of weight polytetrahydrofuran diols in reactor under 120 ℃ ,-0.09MPa condition processed after approximately 1 hour, be down to room temperature, add 76.3 parts of weight of toluene vulcabond about 95 ℃ reactions 2 hours; Add 85 ℃ of reactions of 8 parts of weight hydrophilic chain extender dimethylol propionic acids and 5 parts of weight N-Methyl pyrrolidone (a small amount of dibutyl tin laurate) 2 hours, to theoretical NCO content, be cooled to 50 ℃ of left and right, add the methacrylic acid Alpha-hydroxy triamino alcohol ester that 10 parts of weight contain stopper 2-Tert. Butyl Hydroquinone to react 30 minutes, finally add 64 parts of weight percent acrylic acid hydroxypropyl acrylates, 60 ℃ are incubated 2 hours, to system, do not contain NCO, be cooled to 40 ℃ of left and right, add 5.25 parts of weight triethylamine neutralizations, add deionized water emulsification.
Embodiment 6
(1) in dry reactor, add diethylenetriamine, with appropriate N-BUTYL ACETATE dilution, be heated to 130 ℃ of left and right, now N-BUTYL ACETATE has backflow, drip the glycidyl methacrylate of diluting with N-BUTYL ACETATE, within 2-3 hour, drip off, be incubated 10 minutes, cooling extraction N-BUTYL ACETATE; Open loop condensation reaction obtains methacrylic acid Alpha-hydroxy triamino alcohol ester.
(2) by 100 parts of weight polytetrahydrofuran diols in reactor under 120 ℃ ,-0.09MPa condition processed after approximately 1 hour, be down to room temperature, add 48.1 parts of weight isophorone diisocyanates and 38.1 parts of weight of toluene vulcabond about 95 ℃ reactions 2 hours; Add 85 ℃ of reactions of 12 parts of weight N-Methyl pyrrolidone (a small amount of dibutyl tin laurate) 2 hours, to theoretical NCO content, be cooled to 50 ℃ of left and right, add the methacrylic acid Alpha-hydroxy triamino alcohol ester that 10 parts of weight contain stopper p methoxy phenol to react 30 minutes, finally add 64 parts of weight percent acrylic acid hydroxypropyl acrylates, 60 ℃ are incubated 2 hours, to system, do not contain NCO, be cooled to 40 ℃ of left and right, add 5.25 parts of weight triethylamines neutralizations, add deionized water emulsification.
Embodiment 7
(1) in dry reactor, add diethylenetriamine, with appropriate N-Methyl pyrrolidone dilution, be heated to 205 ℃ of left and right, now N-Methyl pyrrolidone has backflow, drip the glycidyl methacrylate of diluting with N-Methyl pyrrolidone, within 2-2.5 hour, drip off, be incubated 10 minutes, cooling extraction N-Methyl pyrrolidone; Open loop condensation reaction obtains methacrylic acid Alpha-hydroxy triamino alcohol ester.
(2) by 100 parts of weight polytetrahydrofuran diols in reactor under 120 ℃ ,-0.09MPa condition processed after approximately 1 hour, be down to room temperature, add 96.2 parts of weight isophorone diisocyanates about 95 ℃ reactions 2 hours; Add 85 ℃ of reactions of 8 parts of weight hydrophilic chain extender dimethylol propionic acids and 5 parts of weight N-Methyl pyrrolidone (a small amount of dibutyl tin laurate) 2 hours, to theoretical NCO content, be cooled to 50 ℃ of left and right, add the methacrylic acid Alpha-hydroxy triamino alcohol ester that 10 parts of weight contain hydroquinone of polymerization retarder to react 30 minutes, finally add 55 parts of weight percent acrylic acid hydroxyl ethyl esters, 60 ℃ are incubated 2 hours, to system, do not contain NCO, be cooled to 40 ℃ of left and right, add 5.25 parts of weight triethylamine neutralizations, add deionized water emulsification.

Claims (11)

1. the aqueous polyurethane of uV curable, is characterized in that: this urethane has following chemical formula:
Figure FDA00003332340900011
Wherein n >=2, m >=2, the arbitrary unit of m and n position relationship can exchange.Wavy line represents the urea key link between monomer.
2. the method for the aqueous polyurethane of preparation uV curable claimed in claim 1, is characterized in that:
(1) low poly-dihydric alcohol, vulcabond and the hydrophilic chain extender of metering are prepared base polyurethane prepolymer for use as;
(2) described performed polymer reacts 20-40 minute with the methacrylic acid Alpha-hydroxy triamino alcohol ester of the metering containing stopper at 40 ℃-60 ℃;
(3) described product carries out end-blocking by end-capping reagent at 55 ℃-65 ℃ again; With
(4) be finally cooled to 35 ℃-45 ℃ aqueous polyurethanes that add triethylamine reaction to obtain uV curable claimed in claim 1.
3. preparation method according to claim 2, is characterized in that, described methacrylic acid Alpha-hydroxy triamino alcohol ester is under the suitable reflux temperature of solvent, to be reacted and obtain in solvent by diethylenetriamine and glycidyl methacrylate.
4. preparation method according to claim 2, is characterized in that, the base polyurethane prepolymer for use as of described metering reacts described base polyurethane prepolymer for use as reactant and comprises:
(1) the low poly-dihydric alcohol that molar percentage is 35%-65%;
(2) vulcabond that molar percentage is 35%-65%; With
(3) molar percentage is less than or equal to 30% hydrophilic chain extender.
5. method claimed in claim 2, is characterized in that, described low poly-dihydric alcohol is selected from: one or more in polycaprolactone dibasic alcohol, PTMG, copolyether, poly-DOPCP.
6. method claimed in claim 2, is characterized in that, described vulcabond is selected from: one or more in isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, tolylene diisocyanate.
7. method claimed in claim 2, is characterized in that, described hydrophilic chain extender is selected from: one or both in diformazan hydroxy-propionic acid or N-Methyl pyrrolidone.
8. preparation method according to claim 3, is characterized in that, described solvent is selected from one or both in acetone, butanone, N-BUTYL ACETATE, N-Methyl pyrrolidone.
9. preparation method according to claim 2, is characterized in that, the reactant of the metering of the described aqueous polyurethane of preparing uV curable comprises:
(1) polyurethane prepolymer that weight percent is 65%-80%;
(2) the methacrylic acid Alpha-hydroxy triamino alcohol ester that weight percent is 3%-5%;
(3) end-capping reagent that weight percent is 15%-20%; With
(4) triethylamine that weight percent is 1%-3%.
10. preparation method according to claim 2, is characterized in that: described end-capping reagent is selected from Hydroxyethyl acrylate or Propylene glycol monoacrylate.
11. preparation methods according to claim 2, is characterized in that: described stopper is selected from Resorcinol, 2-Tert. Butyl Hydroquinone or p methoxy phenol.
CN201310231599.5A 2013-06-09 2013-06-09 Ultraviolet-curable waterborne polyurethane and preparation method thereof Pending CN103819646A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107177031A (en) * 2017-04-17 2017-09-19 烟台大学 A kind of GMA modified amine curing agent and resist sagging coating
CN110669201A (en) * 2019-11-15 2020-01-10 宜兴市华夏化工材料有限公司 A kind of preparation method of water-based polyurethane emulsion and use thereof
CN115160920A (en) * 2022-08-11 2022-10-11 苏州合邦鑫材科技有限公司 Three-proofing paint and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1844182A (en) * 2006-03-22 2006-10-11 中国科学技术大学 Process for preparing ultraviolet curable aqueous polyurethane resin
CN101544739A (en) * 2009-05-07 2009-09-30 合肥工业大学 Acrylic ester modified water-soluble polyurethane with comb shaped structure and preparation method
US20120041145A1 (en) * 2009-02-13 2012-02-16 Bayer Materialscience Ag Aqueous coating systems based on physically drying urethane acrylates

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1844182A (en) * 2006-03-22 2006-10-11 中国科学技术大学 Process for preparing ultraviolet curable aqueous polyurethane resin
US20120041145A1 (en) * 2009-02-13 2012-02-16 Bayer Materialscience Ag Aqueous coating systems based on physically drying urethane acrylates
CN101544739A (en) * 2009-05-07 2009-09-30 合肥工业大学 Acrylic ester modified water-soluble polyurethane with comb shaped structure and preparation method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107177031A (en) * 2017-04-17 2017-09-19 烟台大学 A kind of GMA modified amine curing agent and resist sagging coating
CN110669201A (en) * 2019-11-15 2020-01-10 宜兴市华夏化工材料有限公司 A kind of preparation method of water-based polyurethane emulsion and use thereof
CN115160920A (en) * 2022-08-11 2022-10-11 苏州合邦鑫材科技有限公司 Three-proofing paint and preparation method thereof

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Application publication date: 20140528