CN104193916A - Heat-resistant waterborne polyurethane and preparation method thereof - Google Patents
Heat-resistant waterborne polyurethane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses heat-resistant waterborne polyurethane which comprises the following raw materials in percentage by mass: 27%-46.5% of polymer polyol, 15.5%-24.2% of isocyanate, 1.2%-6% of a hydrophilic chain extender, 0.05%-0.1% of a catalyst, 1.3%-2.6% of a crosslinker, 1.6%-7.5% of end-sealing monomers, 31.8%-33.6% of acrylate monomers, 0.8%-4% of volatile alkali and 1%-2% of an initiator based on the acrylate monomers. The invention further discloses a preparation method of heat-resistant waterborne polyurethane. Through the preparation method, the heat resistance of waterborne polyurethane can be improved; no VOC (volatile organic compound) is generated in the preparation process; the overall performance is optimized.
Description
Technical field
The invention belongs to fine chemicals and preparing technical field thereof, particularly a kind of heat resistant type aqueous polyurethane and preparation method thereof.
Background technology
In conventional solvent type polyurethane material building-up process, with an organic solvent cause in a large number volatile organic matter in product (VOC) content high, environment and people healthy had to harm, in recent years along with the enhancing of strict and people's environmental consciousness of environmental regulation, to strictly prevent the discharge of VOC, objectively impel the development of aqueous polyurethane.
Aqueous polyurethane is a kind of novel urethane of water consumption substitution organic solvent as dispersion medium, have pollution-free, safe and reliable, mechanical property is good, consistency is easy to well the advantages such as modification, be a kind of novel environment amenable material, since coming out the thirties in 20th century, be widely used in the fields such as coating, chemical building material, hide finishes, sheet surface treating agent and fiber surface treatment agent, there is good development prospect.
Along with the popularization of urethane application, aqueous polyurethane poor shortcoming in thermotolerance is also more and more outstanding, also there is a certain distance at the aspects such as construction, storage and solvent borne polyurethane, and the aspects such as traditional Water-resistance of Waterborne Polyurethane, solvent resistance, chemical-resistant, wear resistance, hardness still can not reach the performance of solvent borne polyurethane coating, these affect and restrict the development of aqueous polyurethane to a certain extent, thereby waterborne polyurethane modified research is become to an important directions, especially at the aspect such as thermotolerance and water tolerance.
Summary of the invention
The object of the invention is to overcome the thermotolerance of prior art existence and the shortcoming of poor water resistance, a kind of heat resistant type aqueous polyurethane and preparation method thereof is provided.
For achieving the above object, the technical scheme that the present invention takes is:
The embodiment of the present invention provides a kind of heat resistant type aqueous polyurethane, is made up of by mass percentage following material:
Polymer polyatomic alcohol 27% ~ 46.5%, isocyanic ester 15.5% ~ 24.2%, hydrophilic chain extender 1.2% ~ 6%, catalyzer 0.05% ~ 0.1%, linking agent 1.3% ~ 2.6%, end-blocking monomer 1.6% ~ 7.5%, acrylate monomer 31.8% ~ 33.6%, volatile alkali 0.8% ~ 4% and account for the initiator of acrylate monomer content 1% ~ 2%.
In such scheme, described polymer polyatomic alcohol is the mixture of one or both any proportionings in poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, poly-epsilon-caprolactone glycol, polycarbonate diol, polytetrahydrofuran diol.
In such scheme, described isocyanic ester is the mixture of one or both any proportionings in isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethanediisocyanate.
In such scheme, described hydrophilic chain extender is the mixture of one or both any proportionings in dimethylol propionic acid, dimethylolpropionic acid.
In such scheme, described catalyzer is the one in dibutyl tin laurate, dibutyltin diacetate, stannous octoate.
In such scheme, described linking agent is trimeric cyanamide.
In such scheme, described end-blocking monomer is the mixture of one or both any proportionings in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate, n-methylolacrylamide, acrylamide.
In such scheme, described Acrylic Acid Monomer is the mixture of a kind of, two or more any proportioning in methyl methacrylate, methyl acrylate, β-dimethyl-aminoethylmethacrylate, ethyl propenoate, butyl methacrylate, butyl acrylate, N-Hexyl methacrylate, Ethyl acrylate, n octyl methacrylate, vinylformic acid n-octyl, 2-Ethylhexyl Methacrylate, 2-EHA, vinylbenzene, alpha-methyl styrene.
In such scheme, described initiator is the one in Potassium Persulphate, ammonium persulphate, hydrogen peroxide, azo diisobutyl amidine hydrochloride.
The embodiment of the present invention also provides a kind of preparation method of heat resistant type aqueous polyurethane, and the method comprises the following steps:
Step 1: prepare base polyurethane prepolymer for use as: the polymer polyatomic alcohol that is 27% ~ 46.5% using mass percent respectively, 15.5% ~ 42.2% isocyanic ester are as raw material, the acrylate monomer that is 31.8% ~ 33.6% using mass percent is as solvent, the trimeric cyanamide that is 1.3% ~ 2.6% using mass percent adds and in reactor, carries out polyreaction as linking agent, and to add mass percent be that 0.05% ~ 0.1% catalyzer reacts, temperature of reaction is 75 DEG C, reaction times is 2 ~ 2.5 hours, forms base polyurethane prepolymer for use as;
Step 2: chain extending reaction: the hydrophilic chain extender that is 1.2% ~ 6% by mass percent joins in the base polyurethane prepolymer for use as that step 1 makes and carries out chain extending reaction, and temperature of reaction is 70 ~ 80 DEG C, and the reaction times is 2 ~ 2.5 hours;
Step 3: end capping: the end-blocking monomer that is 1.6% ~ 7.5% by mass percent joins in reactor and carries out end capping, and temperature of reaction is 70 ~ 80 DEG C, and the time is 1 ~ 2 hour;
Step 4: emulsification: temperature is cooled to 20 ~ 40 DEG C, after finally adding volatile alkali to regulate pH value to be 7.0～7.5, adds the deionized water of normal temperature under high-speed stirring, obtain white emulsion;
Step 5: trigger monomer polymerization: add the initiator that accounts for acrylate monomer content 1% ~ 2% in the white emulsion making to step 4, the reaction times is 2 ~ 6 hours, and temperature of reaction is 75 DEG C, obtains heat resistant type aqueous polyurethane emulsion.
Compared with prior art, beneficial effect of the present invention:
(1), improved resistance toheat: trimeric cyanamide is a kind of nitrogen heterocyclic ring organic compound, in molecule, there is large π key, there are three active aminos simultaneously, using trimeric cyanamide as linking agent, stable on heating triazine ring structure can be in polyurethane backbone, introduced, aqueous polyurethane resistance toheat can be improved.
(2), preparation process VOC free, optimized overall performance: gordian technique of the present invention be to adopt vinyl monomer as disperse phase to solve solvability and the viscosity problem of system, initiated polymerization under water soluble starter effect, obtain the aqueous polyurethane of modification, preparation process is simple, safety, taking water as solvent, thoroughly abandon the use of poisonous and harmful organic solvent, be VOC free (volatilizable organism) environment-friendly material truly, can significantly improve thermotolerance and the water tolerance of aqueous polyurethane simultaneously.
Brief description of the drawings
Fig. 1 adopts the present invention to make the thermogravimetric curve of the glued membrane of pattern of fever aqueous polyurethane.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The embodiment of the present invention provides a kind of heat resistant type aqueous polyurethane, is made up of by mass percentage following material:
Polymer polyatomic alcohol 27% ~ 46.5%, isocyanic ester 15.5% ~ 24.2%, hydrophilic chain extender 1.2% ~ 6%, catalyzer 0.05% ~ 0.1%, linking agent 1.3% ~ 2.6%, end-blocking monomer 1.6% ~ 7.5%, acrylate monomer 31.8% ~ 33.6%, volatile alkali 0.8% ~ 4% and account for the initiator of acrylate monomer content 1% ~ 2%.
Described polymer polyatomic alcohol is the mixture of one or both any proportionings in poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, poly-epsilon-caprolactone glycol, polycarbonate diol, polytetrahydrofuran diol.
Described isocyanic ester is the mixture of one or both any proportionings in isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethanediisocyanate.
Described hydrophilic chain extender is the mixture of one or both any proportionings in dimethylol propionic acid, dimethylolpropionic acid.
Described catalyzer is the one in dibutyl tin laurate, dibutyltin diacetate, stannous octoate.
Described linking agent is trimeric cyanamide.
Described end-blocking monomer is the mixture of one or both any proportionings in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate, n-methylolacrylamide, acrylamide.
Described Acrylic Acid Monomer is the mixture of a kind of, two or more any proportioning in methyl methacrylate, methyl acrylate, β-dimethyl-aminoethylmethacrylate, ethyl propenoate, butyl methacrylate, butyl acrylate, N-Hexyl methacrylate, Ethyl acrylate, n octyl methacrylate, vinylformic acid n-octyl, 2-Ethylhexyl Methacrylate, 2-EHA, vinylbenzene, alpha-methyl styrene.
Described initiator is the one in Potassium Persulphate, ammonium persulphate, hydrogen peroxide, azo diisobutyl amidine hydrochloride.
Described volatile alkali is triethylamine or ammoniacal liquor.
Embodiment 1, a kind of heat resistant type aqueous polyurethane of the embodiment of the present invention, is prepared by following method, and described method comprises the steps: successively
Step 101, prepare base polyurethane prepolymer for use as: the polytetrahydrofuran diol that is 46.5% by mass percent, 15.5% hexamethylene diisocyanate, 33.1% acrylate monomer (wherein vinylbenzene 20%, Ethyl acrylate 13.1%) and 0.74% trimeric cyanamide join in dry reactor, reactor is heated to 80 DEG C, stir, the catalyzer dibutyl tin laurate that is 0.1% by mass percent again carries out polyreaction 2.0 hours, forms base polyurethane prepolymer for use as;
Step 102, chain extending reaction: the hydrophilic chain extender dimethylolpropionic acid that is 1.2% by mass percent, temperature of reaction is 70 DEG C, the reaction times is 2.0 hours;
Step 103, end capping: the Hydroxyethyl acrylate that is 1.6% by mass percent joins in reactor and carries out end capping, and temperature of reaction is at 80 DEG C, and the time is 1.0 hours;
Step 104, emulsification: temperature is cooled to 40 DEG C, and adding mass percent is after 0.8% triethylamine regulates pH value to be 7.5, adds the deionized water of normal temperature under high-speed stirring, obtains white emulsion.
Step 105, trigger monomer polymerization: the persulfate aqueous solution that in the white emulsion making to step 104, slowly dropping mass percent is 0.5% is as initiator, and the reaction times is 4.0 hours, and temperature of reaction is 75 DEG C, obtains heat resistant type aqueous polyurethane emulsion.
Embodiment 2, the embodiment of the present invention provides a kind of heat resistant type aqueous polyurethane, is prepared by following method, and described method comprises the steps: successively
Step 201, prepare base polyurethane prepolymer for use as: the poly-epsilon-caprolactone glycol that is 40.7% by mass percent, 18.2% isoflurane chalcone diisocyanate, 33.3% acrylate monomer (wherein methyl methacrylate 22%, butyl acrylate 11.3%) and 1.3% trimeric cyanamide join in dry reactor, reactor is heated to 80 DEG C, stir, the catalyzer dibutyl tin laurate that is 0.09% by mass percent again carries out polyreaction 2.0 hours, forms base polyurethane prepolymer for use as;
Step 202, chain extending reaction: the hydrophilic chain extender dimethylolpropionic acid that is 2% by mass percent, temperature of reaction is 80 DEG C, the reaction times is 2.5 hours;
Step 203, end capping: the hydroxyethyl methylacrylate that is 2.8% by mass percent joins in reactor and carries out end capping, and temperature of reaction is at 70 DEG C, and the time is 1.0 hours;
Step 204, emulsification: temperature is cooled to 35 DEG C, and adding mass percent is after 1.4% triethylamine regulates pH value to be 7.5, adds the deionized water of normal temperature under high-speed stirring, obtains white emulsion.
Step 205, trigger monomer polymerization: the ammonium persulfate aqueous solution that in the white emulsion making to step 204, slowly dropping mass percent is 0.49% is as initiator, and the reaction times is 5.0 hours, and temperature of reaction is 75 DEG C, obtains heat resistant type aqueous polyurethane emulsion.
Embodiment 3, the embodiment of the present invention provides a kind of heat resistant type aqueous polyurethane, is prepared by following method, and described method comprises the steps: successively
Step 301, prepare base polyurethane prepolymer for use as: the polytetrahydrofuran diol that is 32.8% by mass percent, 21.8% isoflurane chalcone diisocyanate, 32.7% acrylate monomer (wherein methyl methacrylate 20.5%, vinylformic acid n-octyl 12.2%) and 2.1% trimeric cyanamide join in dry reactor, reactor is heated to 80 DEG C, stir, the catalyzer dibutyl tin laurate that is 0.07% by mass percent again carries out polyreaction 2.5 hours, forms base polyurethane prepolymer for use as;
Step 302, chain extending reaction: the hydrophilic chain extender dimethylolpropionic acid that is 3.2% by mass percent, temperature of reaction is 75 DEG C, the reaction times is 2.0 hours;
Step 303, end capping: the Propylene glycol monoacrylate that is 4.5% by mass percent joins in reactor and carries out end capping, and temperature of reaction is at 79 DEG C, and the time is 1.0 hours;
Step 304, emulsification: temperature is cooled to 30 DEG C, and adding mass percent is, after 2.2% ammoniacal liquor regulates pH value to be 7.5, under high-speed stirring, to add deionized water at normal temperature, obtains white emulsion.
Step 305, trigger monomer polymerization: in the white emulsion making to step 304, azo diisobutyl amidine hydrochloride (V-50) aqueous solution of slow dropping 0.48% is as initiator, reaction times is 4.5 hours, temperature of reaction is 75 DEG C, obtains heat resistant type aqueous polyurethane emulsion.
Embodiment 4, the embodiment of the present invention provides a kind of heat resistant type aqueous polyurethane, is prepared by following method, and described method comprises the steps: successively
Step 401, prepare base polyurethane prepolymer for use as: the polytetrahydrofuran diol that is 29.6% by mass percent, 15.67% tolylene diisocyanate, 32.9% acrylate monomer (wherein β-dimethyl-aminoethylmethacrylate 21.8%, butyl acrylate %11.1%) and 2.2% trimeric cyanamide join in dry reactor, reactor is heated to 80 DEG C, stir, the catalyzer dibutyl tin laurate that is 0.07% by mass percent again carries out polyreaction 2.0 hours, forms base polyurethane prepolymer for use as;
Step 402, chain extending reaction: the hydrophilic chain extender dimethylolpropionic acid that is 3.5% by mass percent, temperature of reaction is 70 DEG C, the reaction times is 2.0 hours;
Step 403, end capping: the Rocryl 410 that is 5.5% by mass percent joins in reactor and carries out end capping, and temperature of reaction is at 70 DEG C, and the time is 1.0 hours;
Step 404, emulsification: temperature is cooled to 25 DEG C, and adding mass percent is, after 2.4% triethylamine regulates pH value to be 7.5, under high-speed stirring, to add deionized water at normal temperature, obtains white emulsion.
Step 405, trigger monomer polymerization: the persulfate aqueous solution that in the white emulsion making to step 404, slowly dropping mass percent is 0.45% is as initiator, and the reaction times is 3.5 hours, and temperature of reaction is 75 DEG C, obtains heat resistant type aqueous polyurethane emulsion.
Embodiment 5, the embodiment of the present invention provides a kind of heat resistant type aqueous polyurethane, is prepared by following method, and described method comprises the steps: successively
Step 501, prepare base polyurethane prepolymer for use as: the poly-epsilon-caprolactone glycol that is 27% by mass percent, 22.5% diphenylmethanediisocyanate, 33% acrylate monomer (wherein methyl acrylate 19%, butyl methacrylate 14%) and 2.6% trimeric cyanamide join in dry reactor, reactor is heated to 80 DEG C, stir, the catalyzer dibutyl tin laurate that is 0.08% by mass percent again carries out polyreaction 2.0 hours, forms base polyurethane prepolymer for use as;
Step 502, chain extending reaction: the hydrophilic chain extender dimethylol propionic acid that is 4% by mass percent, temperature of reaction is 78 DEG C, the reaction times is 2.0 hours;
Step 503, end capping: the Hydroxyethyl acrylate that is 5.4% by mass percent joins in reactor and carries out end capping, and temperature of reaction is at 75 DEG C, and the time is 1.0 hours;
Step 504, emulsification: temperature is cooled to 20 DEG C, and adding mass percent is, after 2.8% ammoniacal liquor regulates pH value to be 7.5, under high-speed stirring, to add deionized water at normal temperature, obtains white emulsion.
Step 505, trigger monomer polymerization: the hydrogen peroxide solution that in the white emulsion making to step 504, slowly dropping mass percent is 0.46% is as initiator, and the reaction times is 3.0 hours, and temperature of reaction is 75 DEG C, obtains heat resistant type aqueous polyurethane emulsion.
Embodiment 6, the embodiment of the present invention provides a kind of heat resistant type aqueous polyurethane, is prepared by following method, and described method comprises the steps: successively
Step 601, prepare base polyurethane prepolymer for use as: the poly-hexanodioic acid hexylene glycol ester that is 33% by mass percent, 22.1% isoflurane chalcone diisocyanate, 33.4% acrylate monomer (wherein β-dimethyl-aminoethylmethacrylate 20.3%, Ethyl acrylate 13.1%) and 2.8% trimeric cyanamide join in dry reactor, reactor is heated to 80 DEG C, stir, the catalyzer dibutyl tin laurate that is 0.08% by mass percent again carries out polyreaction 2.5 hours, forms base polyurethane prepolymer for use as;
Step 602, chain extending reaction: the hydrophilic chain extender dimethylol propionic acid that is 1.3% by mass percent, temperature of reaction is 80 DEG C, the reaction times is 2.0 hours;
Step 603, end capping: the n-methylolacrylamide that is 2.8% by mass percent joins in reactor carries out end capping, and temperature of reaction is at 80 DEG C, and the time is 1.5 hours;
Step 604, emulsification: temperature is cooled to 25 DEG C, after adding 2.8% triethylamine to regulate pH value to be 7.5, under high-speed stirring, adds deionized water at normal temperature, obtain white emulsion.
Step 605, trigger monomer polymerization: the ammonium persulfate aqueous solution that in the white emulsion making to step 604, slowly dropping mass percent is 0.51% is as initiator, and the reaction times is 4.5 hours, and temperature of reaction is 75 DEG C, obtains heat resistant type aqueous polyurethane emulsion.
Experimental data:
the thermogravimetic analysis (TGA) of glued membrane:
The heat resistant type aqueous polyurethane emulsion that adopts German Netzsch thermal gravimetric analyzer TG-209 F1 to make any one embodiment of embodiment 1-6 is tested.
Test parameter: temperature rise rate is 10 DEG C/min, atmosphere is N
2, temperature test scope is 25～500 DEG C.
As seen from Figure 1, in Range of measuring temp, the heat decomposition temperature of heat resistant type aqueous polyurethane is than the height of aqueous polyurethane, and weight loss rate reduces, after introducing trimeric cyanamide is cross-linking modified, and half decomposition temperature (T of glued membrane
d, 1/2) be elevated to 383.6 DEG C from 335.2 DEG C, illustrate that the final thermostability of urethane of modification is improved.
Claims (10)
1. a heat resistant type aqueous polyurethane, is characterized in that: be made up of by mass percentage following material:
Polymer polyatomic alcohol 27% ~ 46.5%, isocyanic ester 15.5% ~ 24.2%, hydrophilic chain extender 1.2% ~ 6%, catalyzer 0.05% ~ 0.1%, linking agent 1.3% ~ 2.6%, end-blocking monomer 1.6% ~ 7.5%, acrylate monomer 31.8% ~ 33.6%, volatile alkali 0.8% ~ 4% and account for the initiator of acrylate monomer content 1% ~ 2%.
2. heat resistant type aqueous polyurethane according to claim 1, is characterized in that: described polymer polyatomic alcohol is the mixture of one or both any proportionings in poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, poly-epsilon-caprolactone glycol, polycarbonate diol, polytetrahydrofuran diol.
3. heat resistant type aqueous polyurethane according to claim 1 and 2, is characterized in that: described isocyanic ester is the mixture of one or both any proportionings in isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethanediisocyanate.
4. heat resistant type aqueous polyurethane according to claim 3, is characterized in that: described hydrophilic chain extender is the mixture of one or both any proportionings in dimethylol propionic acid, dimethylolpropionic acid.
5. heat resistant type aqueous polyurethane according to claim 4, is characterized in that: described catalyzer is the one in dibutyl tin laurate, dibutyltin diacetate, stannous octoate.
6. heat resistant type aqueous polyurethane according to claim 5, is characterized in that: described linking agent is trimeric cyanamide.
7. heat resistant type aqueous polyurethane according to claim 6, is characterized in that: described end-blocking monomer is the mixture of one or both any proportionings in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate, n-methylolacrylamide, acrylamide.
8. heat resistant type aqueous polyurethane according to claim 7, is characterized in that: described Acrylic Acid Monomer is the mixture of a kind of, two or more any proportioning in methyl methacrylate, methyl acrylate, β-dimethyl-aminoethylmethacrylate, ethyl propenoate, butyl methacrylate, butyl acrylate, N-Hexyl methacrylate, Ethyl acrylate, n octyl methacrylate, vinylformic acid n-octyl, 2-Ethylhexyl Methacrylate, 2-EHA, vinylbenzene, alpha-methyl styrene.
9. heat resistant type aqueous polyurethane according to claim 8, is characterized in that: described initiator is the one in Potassium Persulphate, ammonium persulphate, hydrogen peroxide, azo diisobutyl amidine hydrochloride.
10. a preparation method for heat resistant type aqueous polyurethane, is characterized in that, the method comprises the following steps:
Step 1: prepare base polyurethane prepolymer for use as: the polymer polyatomic alcohol that is 27% ~ 46.5% using mass percent respectively, 15.5% ~ 42.2% isocyanic ester are as raw material, the acrylate monomer that is 31.8% ~ 33.6% using mass percent is as solvent, the trimeric cyanamide that is 1.3% ~ 2.6% using mass percent adds and in reactor, carries out polyreaction as linking agent, and to add mass percent be that 0.05% ~ 0.1% catalyzer reacts, temperature of reaction is 75 DEG C, reaction times is 2 ~ 2.5 hours, forms base polyurethane prepolymer for use as;
Step 2: chain extending reaction: the hydrophilic chain extender that is 1.2% ~ 6% by mass percent joins in the base polyurethane prepolymer for use as that step 1 makes and carries out chain extending reaction, and temperature of reaction is 70 ~ 80 DEG C, and the reaction times is 2 ~ 2.5 hours;
Step 3: end capping: the end-blocking monomer that is 1.6% ~ 7.5% by mass percent joins in reactor and carries out end capping, and temperature of reaction is 70 ~ 80 DEG C, and the time is 1 ~ 2 hour;
Step 4: emulsification: temperature is cooled to 20 ~ 40 DEG C, after finally adding volatile alkali to regulate pH value to be 7.0～7.5, adds the deionized water of normal temperature under high-speed stirring, obtain white emulsion;
Step 5: trigger monomer polymerization: add the initiator that accounts for acrylate monomer content 1% ~ 2% in the white emulsion making to step 4, the reaction times is 2 ~ 6 hours, and temperature of reaction is 75 DEG C, obtains heat resistant type aqueous polyurethane emulsion.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104745069A (en) * | 2015-03-30 | 2015-07-01 | 广西吉顺能源科技有限公司 | Water-soluble polyurethane heat-insulating coating for external wall, and production method thereof |
| CN104745070A (en) * | 2015-03-30 | 2015-07-01 | 广西吉顺能源科技有限公司 | Polyurethane exterior-wall anti-corrosive flame-retarded coating and preparation method thereof |
| CN107602771A (en) * | 2017-09-20 | 2018-01-19 | 中国石油大学(北京) | Film forming agent suitable for CBM Drilling and preparation method thereof and drilling fluid and application |
| CN107699121A (en) * | 2017-09-19 | 2018-02-16 | 运研材料科技（上海）有限公司 | A kind of aqueous polyurethane coating and its film build method of resistance to butanone |
| WO2019157487A1 (en) * | 2018-02-12 | 2019-08-15 | Swimc Llc | Urethane acrylic hybrid polymer dispersion with robust dry/wet adhesion and basecoats prepared therefrom |
| CN110317558A (en) * | 2019-08-05 | 2019-10-11 | 陕西科技大学 | A kind of poly-dopamine acrylic adhesive for polyurethane and preparation method thereof |
| CN110540630A (en) * | 2019-10-08 | 2019-12-06 | 刘军 | Novel waterborne polyurethane composition and preparation method thereof |
| CN114031998A (en) * | 2021-11-10 | 2022-02-11 | 汉中聚智达远环能科技有限公司 | Heat-resistant waterborne polyurethane coating and preparation method thereof |
| CN114958271A (en) * | 2022-06-09 | 2022-08-30 | 南宁市匠心鸣居建筑材料有限公司 | Heat-resistant high-performance polyurethane adhesive and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508879A (en) * | 2009-03-17 | 2009-08-19 | 陕西科技大学 | Method of preparing watersoluble polyurethane adhesive |
| WO2011089154A2 (en) * | 2010-01-21 | 2011-07-28 | Bayer Materialscience Ag | A process for the production of water-emulsifiable polyurethane-polyacrylate hybrid systems |
| CN102757540A (en) * | 2012-07-10 | 2012-10-31 | 陕西科技大学 | Preparation method of waterborne polyurethane for synthetic leather |
-
2014
- 2014-09-16 CN CN201410468794.4A patent/CN104193916A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508879A (en) * | 2009-03-17 | 2009-08-19 | 陕西科技大学 | Method of preparing watersoluble polyurethane adhesive |
| WO2011089154A2 (en) * | 2010-01-21 | 2011-07-28 | Bayer Materialscience Ag | A process for the production of water-emulsifiable polyurethane-polyacrylate hybrid systems |
| CN102757540A (en) * | 2012-07-10 | 2012-10-31 | 陕西科技大学 | Preparation method of waterborne polyurethane for synthetic leather |
Non-Patent Citations (2)
| Title |
|---|
| 李艳辉 等: "聚丙烯酸酯改性聚氨酯乳液的研究进展", 《化工技术与开发》 * |
| 艾罡 等: "三聚氰胺改性聚氨酯的合成与研究", 《化工中间体》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104745070A (en) * | 2015-03-30 | 2015-07-01 | 广西吉顺能源科技有限公司 | Polyurethane exterior-wall anti-corrosive flame-retarded coating and preparation method thereof |
| CN104745070B (en) * | 2015-03-30 | 2017-12-08 | 广西吉顺能源科技有限公司 | A kind of polyurethane exterior wall antiseptic fire-retardation coating and preparation method thereof |
| CN104745069A (en) * | 2015-03-30 | 2015-07-01 | 广西吉顺能源科技有限公司 | Water-soluble polyurethane heat-insulating coating for external wall, and production method thereof |
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