CN104193916A - Heat-resistant waterborne polyurethane and preparation method thereof - Google Patents

Heat-resistant waterborne polyurethane and preparation method thereof Download PDF

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CN104193916A
CN104193916A CN201410468794.4A CN201410468794A CN104193916A CN 104193916 A CN104193916 A CN 104193916A CN 201410468794 A CN201410468794 A CN 201410468794A CN 104193916 A CN104193916 A CN 104193916A
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heat
reaction
acrylate
based polyurethane
monomer
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赖小娟
宫米娜
王磊
闫蓓
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

本发明公开了一种耐热型水性聚氨酯，由以下材料按质量百分比组成：聚合物多元醇27%~46.5%、异氰酸酯15.5%~24.2%、亲水扩链剂1.2%~6%、催化剂0.05%~0.1%、交联剂1.3%~2.6%、封端单体1.6%~7.5%、丙烯酸酯单体31.8%~33.6%、可挥发性碱0.8%~4%、和占丙烯酸酯单体含量1%~2%的引发剂；本发明还公开了一种耐热型水性聚氨酯的制备方法，通过本发明可以提高水性聚氨酯耐热性能，制备过程无VOC，优化了总体性能。

The invention discloses a heat-resistant water-based polyurethane, which is composed of the following materials by mass percentage: 27%-46.5% of polymer polyol, 15.5%-24.2% of isocyanate, 1.2%-6% of hydrophilic chain extender, and 0.05% of catalyst %~0.1%, crosslinking agent 1.3%~2.6%, capping monomer 1.6%~7.5%, acrylate monomer 31.8%~33.6%, volatile base 0.8%~4%, and accounting for acrylate monomer An initiator with a content of 1% to 2%; the invention also discloses a preparation method of a heat-resistant water-based polyurethane, through which the heat-resistant performance of the water-based polyurethane can be improved, the preparation process has no VOC, and the overall performance is optimized.

Description

A kind of heat resistant type aqueous polyurethane and preparation method thereof
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)

1.一种耐热型水性聚氨酯，其特征在于：由以下材料按质量百分比组成： 1. A heat-resistant water-based polyurethane, characterized in that: it is composed of the following materials by mass percentage: 聚合物多元醇27%~46.5%、异氰酸酯15.5%~24.2%、亲水扩链剂1.2%~6%、催化剂0.05%~0.1%、交联剂1.3%~2.6%、封端单体1.6%~7.5%、丙烯酸酯单体31.8%~33.6%、可挥发性碱0.8%~4%、和占丙烯酸酯单体含量1%~2%的引发剂。 Polymer polyol 27%~46.5%, isocyanate 15.5%~24.2%, hydrophilic chain extender 1.2%~6%, catalyst 0.05%~0.1%, crosslinking agent 1.3%~2.6%, end-capping monomer 1.6% ~7.5%, 31.8%~33.6% of acrylate monomer, 0.8%~4% of volatile base, and 1%~2% of acrylate monomer content initiator. 2.根据权利要求1所述的耐热型水性聚氨酯，其特征在于：所述聚合物多元醇为聚己二酸己二醇酯、聚己二酸丁二醇酯、聚ε-己内酯二醇、聚碳酸酯二醇、聚四氢呋喃二醇中的一种或两种任意配比的混合物。 2. The heat-resistant water-based polyurethane according to claim 1, characterized in that: said polymer polyol is polyhexamethylene adipate, polybutylene adipate, polyε-caprolactone One of diol, polycarbonate diol and polytetrahydrofuran diol or a mixture of two in any proportion. 3.根据权利要求1或2所述的耐热型水性聚氨酯，其特征在于：所述异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或两种任意配比的混合物。 3. The heat-resistant water-based polyurethane according to claim 1 or 2, characterized in that: said isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate One or two mixtures in any ratio. 4.根据权利要求3所述的耐热型水性聚氨酯，其特征在于：所述亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸中的一种或两种任意配比的混合物。 4. The heat-resistant water-based polyurethane according to claim 3, characterized in that: the hydrophilic chain extender is one or both of dimethylol propionic acid and dimethylol butyric acid in any proportion mixture. 5.根据权利要求4所述的耐热型水性聚氨酯，其特征在于：所述催化剂为二月桂酸二丁基锡、二醋酸二丁基锡、辛酸亚锡中的一种。 5. The heat-resistant water-based polyurethane according to claim 4, characterized in that: the catalyst is one of dibutyltin dilaurate, dibutyltin diacetate and stannous octoate. 6.根据权利要求5所述的耐热型水性聚氨酯，其特征在于：所述交联剂为三聚氰胺。 6. The heat-resistant water-based polyurethane according to claim 5, characterized in that: the crosslinking agent is melamine. 7.根据权利要求6所述的耐热型水性聚氨酯，其特征在于：所述封端单体为甲基丙烯酸羟乙酯、丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯酸羟丙酯、羟甲基丙烯酰胺、丙烯酰胺中的一种或两种任意配比的混合物。 7. The heat-resistant water-based polyurethane according to claim 6, characterized in that: the end-capping monomer is hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, One of methylol acrylamide and acrylamide or a mixture of two in any proportion. 8.根据权利要求7所述的耐热型水性聚氨酯，其特征在于：所述丙烯酸单体为甲基丙烯酸甲酯、丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸乙酯、甲基丙烯酸丁酯、丙烯酸丁酯、甲基丙烯酸己酯、丙烯酸己酯、甲基丙烯酸正辛酯、丙烯酸正辛酯、甲基丙烯酸2-乙基己酯、丙烯酸2-乙基己酯、苯乙烯、α-甲基苯乙烯中的一种、两种或两种以上任意配比的混合物。 8. The heat-resistant water-based polyurethane according to claim 7, characterized in that: the acrylic acid monomer is methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate , butyl acrylate, hexyl methacrylate, hexyl acrylate, n-octyl methacrylate, n-octyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, styrene, α- A mixture of one, two or more than two kinds of methyl styrene in any ratio. 9.根据权利要求8所述的耐热型水性聚氨酯，其特征在于：所述引发剂为过硫酸钾、过硫酸铵、双氧水、偶氮二异丁基脒盐酸盐中的一种。 9. The heat-resistant water-based polyurethane according to claim 8, characterized in that: the initiator is one of potassium persulfate, ammonium persulfate, hydrogen peroxide, and azobisisobutylamidine hydrochloride. 10.一种耐热型水性聚氨酯的制备方法，其特征在于，该方法包括以下步骤： 10. A preparation method for heat-resistant waterborne polyurethane, characterized in that the method may further comprise the steps: 步骤1：制备聚氨酯预聚体：分别将质量百分比为27%~46.5%的聚合物多元醇、15.5%~42.2%的异氰酸酯作为原料，将质量百分比为31.8%~33.6%的丙烯酸酯单体作为溶剂，将质量百分比为1.3%~2.6%的三聚氰胺作为交联剂加入反应器中进行聚合反应，并加入质量百分比为0.05%~0.1%催化剂进行反应，反应温度为75℃，反应时间为2~2.5小时，形成聚氨酯预聚体； Step 1: Prepare polyurethane prepolymer: use 27%~46.5% polymer polyol and 15.5%~42.2% isocyanate as raw materials respectively, and use 31.8%~33.6% acrylate monomer as Solvent, melamine with a mass percentage of 1.3%~2.6% is added to the reactor as a cross-linking agent for polymerization reaction, and a catalyst with a mass percentage of 0.05%~0.1% is added for reaction, the reaction temperature is 75°C, and the reaction time is 2~ 2.5 hours, form polyurethane prepolymer; 步骤2：扩链反应：将质量百分比为1.2%~6%的亲水扩链剂加入到步骤1制得的聚氨酯预聚体中进行扩链反应，反应温度为70~80℃，反应时间为2~2.5小时； Step 2: Chain extension reaction: Add a hydrophilic chain extender with a mass percentage of 1.2%~6% to the polyurethane prepolymer prepared in step 1 for chain extension reaction, the reaction temperature is 70~80°C, and the reaction time is 2~2.5 hours; 步骤3：封端反应：将质量百分比为1.6%~7.5%的封端单体加入到反应器中进行封端反应，反应温度为70~80℃，时间为1~2小时； Step 3: capping reaction: add capping monomer with a mass percentage of 1.6%~7.5% into the reactor for capping reaction, the reaction temperature is 70~80°C, and the time is 1~2 hours; 步骤4：乳化：将温度冷却至20~40℃，最后加入可挥发性碱调节pH值为7.0～7.5后，高速搅拌下加入常温的去离子水，得白色乳液； Step 4: Emulsification: Cool the temperature to 20~40°C, finally add volatile alkali to adjust the pH value to 7.0~7.5, then add deionized water at room temperature under high-speed stirring to obtain a white emulsion; 步骤5：引发单体聚合：向步骤4制得的白色乳液中加入占丙烯酸酯单体含量1%~2%的引发剂，反应时间为2~6小时，反应温度为75℃，得耐热型水性聚氨酯乳液。 Step 5: Initiate monomer polymerization: Add an initiator accounting for 1% to 2% of the acrylate monomer content to the white emulsion prepared in step 4. The reaction time is 2 to 6 hours, and the reaction temperature is 75°C to obtain heat-resistant Type water-based polyurethane emulsion.
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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
CN107602771B (en) * 2017-09-20 2018-06-26 中国石油大学(北京) Film forming agent suitable for CBM Drilling and preparation method thereof and drilling fluid and application
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CN110540630A (en) * 2019-10-08 2019-12-06 刘军 Novel waterborne polyurethane composition and preparation method thereof
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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
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