CN104109226A - Waterborne polyurethane emulsion and preparation method thereof - Google Patents
Waterborne polyurethane emulsion and preparation method thereof Download PDFInfo
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- CN104109226A CN104109226A CN201410359017.6A CN201410359017A CN104109226A CN 104109226 A CN104109226 A CN 104109226A CN 201410359017 A CN201410359017 A CN 201410359017A CN 104109226 A CN104109226 A CN 104109226A
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Abstract
The invention relates to a waterborne polyurethane polymerization monomer, and relates to a waterborne polyurethane emulsion which is obtained by polymerizing the waterborne polyurethane polymerization monomer. The waterborne polyurethane emulsion is prepared by the following raw materials in percentage by weight: 5-20% of oligomer polyols, 0-5% of micromolecule chain extender, 5-14% of diisocyanate, 1-5% of hydrophilic chain extender, 1-5% of saltifying reagent, 0.1-0.5% of catalyst and 50-70% of deionized water. The invention also relates to a preparation method of the waterborne polyurethane emulsion. The waterborne polyurethane emulsion provided by the invention has strong chemical stability, good water tolerance and solvent resistance, excellent adhesive force and favorable flame retardance, so that the research gap of waterborne polyurethane products simultaneously containing phosphoric acid hydrophilic group and carboxylic acid hydrophilic group in the prior art is filled.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of aqueous polyurethane emulsion and preparation method thereof.
Background technology
Aqueous polyurethane is to using water to replace organic solvent as the new polyurethane system of dispersion medium, also claims water dispersible polyurethane, aqueous polyurethane or waterbased urethane.Aqueous polyurethane be take water as solvent, have pollution-free, safe and reliable, mechanical property is good, consistency good, be easy to the advantages such as modification.The Water-borne modification of urethane resin progressively replaces solvent-borne type, becomes the important directions of polyurethane industrial development.Aqueous polyurethane can be widely used in coating, tackiness agent, fabric coating and finishing composition, hide finishes, sheet surface treating agent and fiber surface treatment agent.The whole building-up process of aqueous polyurethane can be divided into two stages.First stage is progressively polymerization in advance, by oligomer diol, chainextender, aqueous monomers, vulcabond by solution progressively polymerization to generate relative molecular mass be the Waterborne Polyurethane Prepolymer of l000 magnitude; Subordinate phase is the dispersion of the rear performed polymer of neutralization in water.
The synthetic basic self-emulsification that adopts of aqueous polyurethane is introduced hydrophilic radical in base polyurethane prepolymer for use as molecular chain, in and after salify, be directly scattered in water.Aqueous polyurethane is different according to the technique of self-emulsifying, can be divided into four kinds: cation-type water-thinned polyurethane, anion-type water-thinned polyurethane, amphoteric ion type aqueous polyurethane, non-ionic water polyurethane.The hydrophilic radical that wherein aqueous polyurethane of anionic is used is generally sulfonic acid group or hydroxy-acid group, use the chainextender with phosphoric acid hydrophilic radical to come the research of synthetic water based polyurethane less, and come synthetic water based polyurethane to have no report with the chainextender with phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical simultaneously.
Summary of the invention
Technical problem to be solved by this invention is: a kind of aqueous polyurethane emulsion that simultaneously contains phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical is provided, a kind of preparation method of this aqueous polyurethane emulsion is further provided.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
An aqueous polyurethane polymerization single polymerization monomer, is characterized in that, the structural formula of described aqueous polyurethane polymerization single polymerization monomer is:
Wherein, R
1for alkyl, m=1-20, n=1-20, m and n are integer, M is alkalimetal ion or ammonium ion.
The beneficial effect of aqueous polyurethane polymerization single polymerization monomer of the present invention is: comprise phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical simultaneously, for the superperformance of the aqueous polyurethane after polymerization lays the foundation, the research of having filled up the aqueous polyurethane polymerization single polymerization monomer product that simultaneously contains phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical in prior art is blank.
The present invention provides again a kind of aqueous polyurethane emulsion, raw material by following weight percent is prepared from: the oligomer polyol of 5-20%, the small molecule chain extender of 0-5%, the vulcabond of 5%-14%, the salt-forming reagent of the hydrophilic chain extender of 1-5%, 1-5%, the deionized water of the catalyzer of 0.1-0.5% and 50-70%, described oligomer polyol is polyester polyol or polyether glycol, the molecular weight of described oligomer polyol is 500-6000, and the structural formula of described hydrophilic chain extender is:
Wherein, R
1for alkyl, m=1-20, n=1-20, m and n are integer.
The beneficial effect of aqueous polyurethane emulsion of the present invention is:
(1) comprise phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical simultaneously, and with phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical, urethane is scattered in water, the existence of double-hydrophilic group has further improved the stability of aqueous polyurethane;
(2) because the bond energy of carbon phosphorus key is large and owing to having introduced amido linkage by wetting ability chainextender compared with the bond energy of carbon-carbon bond, the stability of amido linkage is than high several times of the stability of ester, make aqueous polyurethane emulsion be compared to traditional sulfonic acid type aqueous polyurethane and carboxylic acid type aqueous polyurethane, chemical stability is stronger and water-fast solvent resistance is better.Phosphate group has very strong polarity, and it can form hydrogen bond with the polar group of substrate surface, forms the larger joint of bonding action, thereby makes T-stripping strength become large, and peeling off is now the destruction of force of cohesion, shows excellent adhesion performance.
(3) due to the existence of phosphoric, make aqueous polyurethane emulsion there is excellent flame retardant properties, this is the performance that traditional sulfonic acid type or carboxylic acid type aqueous polyurethane all do not have;
(4) filled up the research blank of the aqueous polyurethane product that simultaneously contains phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical in prior art.
The present invention also provides a kind of preparation method of aqueous polyurethane emulsion, comprises the following steps:
(1) described oligomer polyol and described small molecule chain extender are carried out to processed, until the moisture content of described oligomer polyol and described small molecule chain extender is 0.05%;
(2) by described oligomer polyol and small molecule chain extender after dehydration in step (1), mix with described vulcabond, add solvent, at 60-85 ℃, carry out, in reaction process, measure the NCO content of reaction system;
(3) after NCO stable content is constant, add described hydrophilic chain extender and catalyzer, in the viscosity of reaction system, be no more than under the condition of 5000MPas and react, in reaction process, measure the NCO content of reaction system;
(4) after NCO stable content is constant, be cooled to 45-50 ℃, add described salt-forming reagent, carry out neutralization reaction, obtain aqueous polyurethane prepolymer;
(5) described aqueous polyurethane prepolymer is poured into water and carries out emulsion dispersion, the described aqueous polyurethane prepolymer desolvation by after emulsion dispersion, obtains described aqueous polyurethane emulsion.
The preparation method's of aqueous polyurethane emulsion of the present invention beneficial effect is:
(1) ignition-proof element is directly accessed to aqueous polyurethane segment by hydrophilic chain extender, when preparation has the aqueous polyurethane of fire-retardant requirement, do not need by extraordinary polyvalent alcohol, to reach fire-retardant object again, thereby when preparation has the aqueous polyurethane of fire-retardant requirement, synthetic materials and formula are had to larger selection space;
(2) aqueous polyurethane emulsion that the preparation method of aqueous polyurethane emulsion of the present invention prepares contains phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical simultaneously, has sticking power that strong, the water-fast solvent resistance of chemical stability is good, excellent and good flame retardant properties.
Embodiment
By describing technology contents of the present invention, structural attitude in detail, being realized object and effect, below in conjunction with embodiment, be explained in detail.
The design of most critical of the present invention is: design contains the aqueous polyurethane emulsion of phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical simultaneously, makes the aqueous polyurethane emulsion obtaining have advantages of that strong, the water-fast solvent resistance of chemical stability is good.
Aqueous polyurethane polymerization single polymerization monomer provided by the invention, the structural formula of described aqueous polyurethane polymerization single polymerization monomer is:
Wherein, R
1for alkyl, m=1-20, n=1-20, m and n are integer, M is alkalimetal ion or ammonium ion.
The beneficial effect of aqueous polyurethane polymerization single polymerization monomer of the present invention is: comprise phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical simultaneously, the research of having filled up the aqueous polyurethane polymerization single polymerization monomer product that simultaneously contains phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical in prior art is blank, for the superperformance of the aqueous polyurethane after polymerization lays the foundation.
A kind of aqueous polyurethane emulsion that the present invention provides again, raw material by following weight percent is prepared from: the oligomer polyol of 5-20%, the small molecule chain extender of 0-5%, the vulcabond of 5%-14%, the salt-forming reagent of the hydrophilic chain extender of 1-5%, 1-5%, the deionized water of the catalyzer of 0.1-0.5% and 50-70%, described oligomer polyol is polyester polyol or polyether glycol, the molecular weight of described oligomer polyol is 500-6000, and the structural formula of described hydrophilic chain extender is:
Wherein, R
1for alkyl, m=1-20, n=1-20, m and n are integer.
From foregoing description, the beneficial effect of aqueous polyurethane emulsion of the present invention is:
(1) comprise phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical simultaneously, and with phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical, urethane is scattered in water, the existence of double-hydrophilic group has further improved the stability of aqueous polyurethane;
(2) due to the existence of carbon phosphorus key, make aqueous polyurethane emulsion be compared to traditional sulfonic acid type aqueous polyurethane and carboxylic acid type aqueous polyurethane, it is good that it has strong, the water-fast solvent resistance of chemical stability, and show excellent adhesion performance;
(3) due to the existence of phosphoric, make aqueous polyurethane emulsion there is excellent flame retardant properties, this is the performance that traditional sulfonic acid type or carboxylic acid type aqueous polyurethane all do not have;
(4) filled up the research blank of the aqueous polyurethane product that simultaneously contains phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical in prior art.
Further, described oligomer polyol is one or more in polyoxyethylene glycol, PTMG, amino-polyether, polycaprolactone polyol, polycarbonate polyol and epoxy resin.
Further, described small molecule chain extender is one or more in glycol ether, ethylene glycol, glycol ether, butyleneglycol, TriMethylolPropane(TMP), quadrol, diethylenetriamine and isophorone diamine, small molecule chain extender can refer to various small molecules dibasic alcohol, small molecules diamines etc.
Further, described vulcabond is one or more in tolylene diisocyanate, diphenylmethanediisocyanate, polymethine polyphenyl polyisocyanate, six methylene diisocyanates, isophorone diisocyanate and hydrogenation methylenebis phenyl isocyanates.
Further, described salt-forming reagent is one or more in Trimethylamine 99, triethylamine, Tributylamine, ammoniacal liquor, potassium hydroxide and sodium hydroxide.
Further, described catalyzer is organotin catalysts and/or organic bismuth catalyst.
Further, described oligomer polyol is adipic acid type polyester polyol, wherein, and the polymkeric substance that described adipic acid type polyester polyol can generate for one or more and the hexanodioic acid polymerization in ethylene glycol, butyleneglycol, hexylene glycol.
The present invention also provides a kind of preparation method of aqueous polyurethane emulsion, comprises the following steps:
(1) described oligomer polyol and described small molecule chain extender are carried out to processed, until the moisture content of described oligomer polyol and described small molecule chain extender is 0.05%;
(2) by described oligomer polyol and small molecule chain extender after dehydration in step (1), mix with described vulcabond, add solvent, at 60-85 ℃, carry out, in reaction process, measure the NCO content of reaction system;
(3) after NCO stable content is constant, add described hydrophilic chain extender and catalyzer, in the viscosity of reaction system, be no more than under the condition of 5000MPas and react, in reaction process, measure the NCO content of reaction system;
(4) after NCO stable content is constant, be cooled to 45-50 ℃, add described salt-forming reagent, carry out neutralization reaction, obtain aqueous polyurethane prepolymer;
(5) described aqueous polyurethane prepolymer is poured into water and carries out emulsion dispersion, the described aqueous polyurethane prepolymer desolvation by after emulsion dispersion, obtains described aqueous polyurethane emulsion.
The preparation method's of aqueous polyurethane emulsion of the present invention beneficial effect is:
(1) ignition-proof element is directly accessed to aqueous polyurethane segment by hydrophilic chain extender, when preparation has the aqueous polyurethane of fire-retardant requirement, do not need by extraordinary polyvalent alcohol, to reach fire-retardant object again, thereby when preparation has the aqueous polyurethane of fire-retardant requirement, synthetic materials and formula are had to larger selection space;
(2) aqueous polyurethane emulsion that the preparation method of aqueous polyurethane emulsion of the present invention prepares contains phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical simultaneously, has sticking power that strong, the water-fast solvent resistance of chemical stability is good, excellent and good flame retardant properties.
Further, in described step (3), by the viscosity that adds described solvent to adjust reaction system, be no more than 5000MPas.
Further, described solvent is selected from one or more in acetone, butanone, pimelinketone, N-Methyl pyrrolidone and dimethyl formamide.
The preparation process of the hydrophilic chain extender that following embodiment adopts is as follows:
As above-mentioned reaction equation, it is in 20% sodium hydroxide that above-mentioned B material is dissolved in to massfraction, stirs and makes it abundant dissolving, pours four-hole boiling flask into.In constant pressure funnel, pack A material into, under nitrogen protection, be added drop-wise to four-hole boiling flask, 2h dropwises, and continues reaction 24h.Reaction solution regulates pH value to 0 or following with dense HCl, then with vacuum rotary evaporator distillation, precipitated sodium chloride.Filtrate regulates pH value to 4.0 left and right with NaOH solution again, is added drop-wise in dehydrated alcohol, separates out white flocculent substance.Product is dry 24h under vacuum drying oven, obtains white powder and is described hydrophilic chain extender.
Embodiment mono-
Step 1: polybutylene glyool adipate 50g, the neopentyl glycol 2g that the PTMG 50g that is 2000 by molecular weight, molecular weight are 2000, TriMethylolPropane(TMP) 2g, at 100 ℃, vacuumize dehydration 1h, vacuum tightness is-0.08～-0.1mPa, makes its water ratio be less than 0.05%; Because oligomer polyol or small molecule chain extender may absorb airborne moisture in depositing process, water can react with polyisocyanates, causes gel, so before use they are carried out to processed, is very important.
Step 2: the diol mixture will that step 1 is obtained drops in reactor, under 80 ℃ of conditions, add 40g isophorone diisocyanate, every half hour, use the NCO content in Di-n-Butyl Amine method measurement system, react after 2 hours, the content of NCO reaches stable no longer to be changed;
Step 3: temperature of reaction system is reduced to 75 ℃, add 18g hydrophilic chain extender and 0.1ml organic bismuth catalyst, every half hour, use the NCO content in Di-n-Butyl Amine method measurement system, react after 1 hour, system viscosity is excessive, add 40g butanone to continue reaction, react after 3 hours, the content of NCO reaches stable no longer to be changed;
Step 4: add after being cooled to 45-50 ℃ in 13g triethylamine and 10 minutes;
Step 5: the performed polymer making is poured into fast in the reactor that contains 270g deionized water, high-speed stirring, is scattered in water urethane;
Step 6: desolvation is 2 hours under the condition of underpressure distillation, obtains the aqueous polyurethane emulsion of the present embodiment.
The structural formula of the hydrophilic chain extender using in the building-up process of the present embodiment is:
The structure of the aqueous polyurethane polymerization single polymerization monomer making is:
Embodiment bis-
Step 1: the PTMG 120g that is 2000 by molecular weight vacuumizes dehydration 1h at 100 ℃, and vacuum tightness is :-0.08～-0.1mPa, makes its water ratio be less than 0.05%;
Step 2: by step: 1 dibasic alcohol obtaining drops in reactor, under 85 ℃ of conditions, add 40g isophorone diisocyanate, six methylene diisocyanates of 7.5g, every half hour, use the NCO content in Di-n-Butyl Amine method measurement system, react after 2 hours, the content of NCO reaches stable no longer to be changed;
Step 3: system temperature is reduced to 75 ℃, add 21.96g hydrophilic chain extender and 0.1ml organic bismuth catalyst, every half hour, use the NCO content in Di-n-Butyl Amine method measurement system, react after 1 hour, system viscosity is excessive, add 40g butanone to continue reaction, react after 3 hours, the content of NCO reaches stable no longer to be changed;
Step 4: add after being cooled to 45-50 ℃ in 13g triethylamine and 10 minutes;
Step 5: the performed polymer making is poured in the reactor with 270g deionized water fast, and high-speed stirring, is scattered in water urethane;
Step 6: desolvation is 2 hours under the condition of underpressure distillation, obtains the aqueous polyurethane emulsion of the present embodiment.
The hydrophilic chain extender using in above-mentioned building-up process is:
The structure of the aqueous polyurethane polymerization single polymerization monomer making is:
Embodiment tri-
Step 1: the polycarbonate diol 100g that is 2500 by molecular weight vacuumizes dehydration 1h at 100 ℃, and vacuum tightness is :-0.08～-0.1mPa, makes its water ratio be less than 0.05%;
Step 2: the dibasic alcohol that step 1 is obtained drops in reactor, under 80 ℃ of conditions, add 51.13g isophorone diisocyanate, every half hour, use the NCO content in Di-n-Butyl Amine method measurement system, react after 2 hours, the content of NCO reaches stable no longer to be changed;
Step 3: system temperature is reduced to 75 ℃, add 21.96g hydrophilic chain extender and 0.1ml organic bismuth catalyst,, react 3 hours with the NCO content in Di-n-Butyl Amine method measurement system every half hour, the content of NCO reaches stable no longer to be changed;
Step 4: add after being cooled to 45-50 ℃ in 15g triethylamine and 10 minutes;
Step 5: the performed polymer making is poured in the still with 270g deionized water fast, and high-speed stirring, is scattered in water urethane, obtains the aqueous polyurethane emulsion of the present embodiment.
Step 6: desolvation is 2 hours under the condition of underpressure distillation, obtains the aqueous polyurethane emulsion of the present embodiment.
The hydrophilic chain extender using in above-mentioned building-up process is:
The structure of the aqueous polyurethane polymerization single polymerization monomer making is:
Embodiment tetra-
Step 1: the poly-hexanodioic acid oxalic acid esterdiol 100g that is 2000 by molecular weight vacuumizes dehydration 1h at 100 ℃, and vacuum tightness is :-0.08～-0.1mPa, makes its water ratio be less than 0.05%;
Step 2: the dibasic alcohol that step 1 is obtained drops in reactor, under 65 ℃ of conditions, adds 40g tolylene diisocyanate,, reacted after 2 hours with the NCO content in Di-n-Butyl Amine method measurement system every half hour, and the content of NCO reaches stable no longer to be changed;
Step 3: system temperature is reduced to 60 ℃, add 21.96g hydrophilic chain extender and 0.1ml organic bismuth catalyst, 40g acetone solvent, uses the NCO content in Di-n-Butyl Amine method measurement system every half hour, react 3 hours, the content of NCO reaches stable no longer to be changed;
Step 4: add after being cooled to 45-50 ℃ in 6g sodium hydroxide and 10 minutes;
Step 5: the performed polymer making is poured in the still with 270g deionized water fast, and high-speed stirring, is scattered in water urethane, obtains the aqueous polyurethane emulsion of the present embodiment.
The hydrophilic chain extender using in above-mentioned building-up process is:
The structure of the aqueous polyurethane polymerization single polymerization monomer making is:
In sum, aqueous polyurethane emulsion provided by the invention has adhesion performance that strong, the water-fast solvent resistance of chemical stability is good, excellent and good flame retardant properties, and the research of having filled up the aqueous polyurethane product that simultaneously contains phosphoric acid hydrophilic radical and carboxylic acid hydrophilic radical in prior art is blank.The preparation method of aqueous polyurethane emulsion of the present invention directly accesses aqueous polyurethane segment by ignition-proof element by hydrophilic chain extender, when preparation has the aqueous polyurethane of fire-retardant requirement, do not need by extraordinary polyvalent alcohol, to reach fire-retardant object again, thereby when preparation has the aqueous polyurethane of fire-retardant requirement, synthetic materials and formula are had to larger selection space.
The foregoing is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or conversion of equivalent flow process that utilizes description of the present invention to do; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (12)
1. an aqueous polyurethane polymerization single polymerization monomer, is characterized in that, the structural formula of described aqueous polyurethane polymerization single polymerization monomer is:
Wherein, R
1for alkyl, m=1-20, n=1-20, m and n are integer, M is alkalimetal ion or ammonium ion.
2. an aqueous polyurethane emulsion, is characterized in that, by aqueous polyurethane polymerization single polymerization monomer described in claim 1, is polymerized.
3. an aqueous polyurethane emulsion, it is characterized in that, raw material by following weight percent is prepared from: the oligomer polyol of 5-20%, the small molecule chain extender of 0-5%, the vulcabond of 5%-14%, the salt-forming reagent of the hydrophilic chain extender of 1-5%, 1-5%, the deionized water of the catalyzer of 0.1-0.5% and 50-70%, described oligomer polyol is polyester polyol or polyether glycol, the molecular weight of described oligomer polyol is 500-6000, and the structural formula of described hydrophilic chain extender is:
Wherein, R
1for alkyl, m=1-20, n=1-20, m and n are integer, M is alkalimetal ion or ammonium ion.
4. aqueous polyurethane emulsion according to claim 3, it is characterized in that, described oligomer polyol is one or more in polyoxyethylene glycol, PTMG, amino-polyether, polycaprolactone polyol, polycarbonate polyol and epoxy resin.
5. aqueous polyurethane emulsion according to claim 3, it is characterized in that, described small molecule chain extender is one or more in glycol ether, ethylene glycol, glycol ether, butyleneglycol, TriMethylolPropane(TMP), quadrol, diethylenetriamine and isophorone diamine.
6. aqueous polyurethane emulsion according to claim 3, it is characterized in that, described vulcabond is one or more in tolylene diisocyanate, diphenylmethanediisocyanate, polymethine polyphenyl polyisocyanate, six methylene diisocyanates, isophorone diisocyanate and hydrogenation methylenebis phenyl isocyanates.
7. aqueous polyurethane emulsion according to claim 3, is characterized in that, described salt-forming reagent is one or more in Trimethylamine 99, triethylamine, Tributylamine, ammoniacal liquor, potassium hydroxide and sodium hydroxide.
8. aqueous polyurethane emulsion according to claim 3, is characterized in that, described catalyzer is organotin catalysts and/or organic bismuth catalyst.
9. aqueous polyurethane emulsion according to claim 4, is characterized in that, described oligomer polyol is adipic acid type polyester polyol.
10. the preparation method of the aqueous polyurethane emulsion described in claim 3-9 any one, is characterized in that, comprises the following steps:
(1) described oligomer polyol and described small molecule chain extender are carried out to processed, until the moisture content of described oligomer polyol and described small molecule chain extender is 0.05%;
(2) by described oligomer polyol and small molecule chain extender after dehydration in step (1), mix with described vulcabond, add solvent, at 60-85 ℃, carry out, in reaction process, measure the NCO content of reaction system;
(3) after NCO stable content is constant, add described hydrophilic chain extender and catalyzer, in the viscosity of reaction system, be no more than under the condition of 5000MPas and react, in reaction process, measure the NCO content of reaction system;
(4) after NCO stable content is constant, be cooled to 45-50 ℃, add described salt-forming reagent, carry out neutralization reaction, obtain aqueous polyurethane prepolymer;
(5) described aqueous polyurethane prepolymer is poured into water and carries out emulsion dispersion, the described aqueous polyurethane prepolymer desolvation by after emulsion dispersion, obtains described aqueous polyurethane emulsion.
The preparation method of 11. aqueous polyurethane emulsions according to claim 10, is characterized in that, described step is no more than 5000MPas by the viscosity that adds described solvent to adjust reaction system in (3).
The preparation method of 12. aqueous polyurethane emulsions according to claim 10, is characterized in that, described solvent is selected from one or more in acetone, butanone, pimelinketone, N-Methyl pyrrolidone and dimethyl formamide.
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| CN104804168A (en) * | 2015-04-30 | 2015-07-29 | 福建宝利特集团有限公司 | Waterborne polyurethane emulsion as well as preparation method thereof, application of waterborne polyurethane emulsion to wallpaper basement membrane, and wallpaper basement membrane |
| CN105175672A (en) * | 2015-10-22 | 2015-12-23 | 上海上萃精细化工有限公司 | Anionic polyurethane color fixative and synthesis method thereof |
| CN106243317A (en) * | 2016-07-28 | 2016-12-21 | 上海维凯光电新材料有限公司 | aqueous polyurethane synthetic method based on acetone method |
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| CN108359349A (en) * | 2018-02-05 | 2018-08-03 | 罗宇强 | A kind of water-based anticorrosive paint and preparation method thereof |
| CN108395513A (en) * | 2018-03-29 | 2018-08-14 | 苏州博莱特新材料有限公司 | A kind of flame-retardant aqueous polyurethane resin |
| CN111808260A (en) * | 2020-07-29 | 2020-10-23 | 四川尤博瑞新材料有限公司 | Thermosensitive condom based on waterborne polyurethane and preparation method thereof |
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| CN116042030B (en) * | 2022-12-08 | 2024-03-26 | 广州集泰化工股份有限公司 | Water-based acrylic acid-leaching paint and preparation method thereof |
| CN115820096A (en) * | 2022-12-15 | 2023-03-21 | 青岛科技大学 | Functional waterborne polyurethane emulsion and preparation method thereof |
| CN115820096B (en) * | 2022-12-15 | 2023-10-10 | 青岛科技大学 | Functional aqueous polyurethane emulsion and preparation method thereof |
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