CN102617822A - Preparation method of pyridine sulfonic acid type water-based polyurethane emulsion - Google Patents
Preparation method of pyridine sulfonic acid type water-based polyurethane emulsion Download PDFInfo
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Abstract
The invention relates to a preparation method of a pyridine sulfonic acid type water-based polyurethane emulsion, which comprises the following steps: (1) carrying out prepolymerization reaction on polyester polyol, organic diisocyanate and dihydroxymethylpropionic acid in the presence of a catalyst; (2) dissolving in acetone, and neutralizing by adding a salifying reagent; (3) adding a pyridine sulfonic acid diamine hydrophilic chain extender to carry out chain extension reaction, thereby obtaining a polymer of which the terminal group contains an NCO group; (4) adding deionized water, stirring at high speed to be dispersed into an emulsion, and adding low-molecular weight polyamine to carry out secondary chain extension reaction; and (5) distilling under reduced pressure to remove the acetone, thereby obtaining the pyridine sulfonic acid type water-based polyurethane emulsion. Since the diamine containing pyridine sulfonic acid structure is used as the hydrophilic chain extender, the prepared polyurethane emulsion has the advantages of high adhesive strength and yellowing resistance.
Description
Technical field
The invention belongs to the fine polymer field, relate to a kind of preparation method of pyridine-sulfonic acid type aqueous polyurethane emulsion.
Background technology
Aqueous polyurethane is as a kind of environmentally friendly macromolecular material; Have solvent-free, no stink, pollution-free, do not fire, be prone to blending, help characteristics such as modification with other emulsions; Be widely used in the products such as tackiness agent, coating, paper coating, hide finishes, fiber or fabric-treating agent, wherein used the most extensive at tackiness agent and paint field.
U.S. Pat 3036998, US3756992 had once reported the preparation method of aqueous polyurethane emulsion, but the aqueous polyurethane emulsion solid content of this method preparation is lower.Because the low-solid content tackiness agent exists moisture evaporation speed slow, gluing often, problems such as storage and transportation, therefore limited its application.U.S. Pat 4870129 has been reported a kind of method that adopts the sulfonate type hydrophilic chain extender to prepare water-based polyurethane adhesive.The POLYMETHYLENE POLYPHENYLISOCYANATE and the hydrophilic chain extender that adopt in this patent are aliphatics, and therefore, the aqueous polyurethane crystal property for preparing, tack and anti-physics shrinkage still can't satisfy the requirement of aqueous adhesive.2007 Zhongshan University's master thesis " preparation of footwear use polyurethane adhesive " (Qin Chang rolling) reported that employing sulfonic acid type aromatic ring diamines prepares aqueous polyurethane as hydrophilic chain extender; Crystal property and tack improve; But owing to contain benzene ring structure in the hydrophilic chain extender that uses, so not anti-xanthochromia.
Summary of the invention
The purpose of this invention is to provide a kind of good film-forming property, crystal property is good, and cohesive strength is high, the preparation method of the pyridine-sulfonic acid type aqueous polyurethane emulsion of anti-xanthochromia, high solids content.
The preparation method of this pyridine-sulfonic acid type aqueous polyurethane emulsion may further comprise the steps:
(1) polyester polyol is carried out vacuum hydro-extraction and handle, in the presence of catalyzer, carry out prepolymerization reaction with organic diisocyanate, dimethylol propionic acid then, the reaction times is 2～5 hours, and temperature of reaction is 75～85 ℃;
(2) will go up step gained prepolymer and cool to below 50 ℃, and use acetone solution then, and then add the salt-forming reagent neutralization, the neutral time is 10～30 minutes;
(3) in last step gained material, add pyridine-sulfonic acid diamines hydrophilic chain extender and carry out chain extending reaction; Obtain the polymkeric substance that end group contains the NCO group; The temperature of reaction is 10～60 ℃, and the reaction times is 0.5～1h, and described pyridine-sulfonic acid diamines hydrophilic chain extender is represented by following general formula:
N=2,3 or 4 in the formula;
(4) in the polymkeric substance of last step gained, add the deionized water high-speed stirring and be dispersed into emulsion, add low-molecular-weight polyamine then and carry out the secondary chain extension reaction, the reaction times is 0.5～1h;
(5) decompression steams acetone, promptly makes pyridine-sulfonic acid type aqueous polyurethane emulsion.
The preparation method of pyridine-sulfonic acid type aqueous polyurethane emulsion of the present invention is owing to used the diamines that contains the pyridine-sulfonic acid structure as hydrophilic chain extender; It had both contained regular pyridine ring structure, can improve crystal property and initial adhesion intensity, and possessed anti-preferably physics shrinkage; Pyridine ring is the electron deficiency system on organic chemistry simultaneously; It is difficult for oxidized and makes color burn, has anti-xanthochromic performance, thereby makes the high and anti-xanthochromia of the polyurethane dispersions cohesive strength that makes.
Embodiment
The preparation method of this pyridine-sulfonic acid type aqueous polyurethane emulsion may further comprise the steps:
(1) polyester polyol is carried out vacuum hydro-extraction and handle, in the presence of catalyzer, carry out prepolymerization reaction with organic diisocyanate, dimethylol propionic acid (DMPA) then, the reaction times is 2～5 hours, is preferably 4h; 70～100 ℃ of temperature of reaction are preferably 75～85 ℃;
(2) will go up step gained prepolymer and cool to below 50 ℃, and use acetone solution then, and then add the salt-forming reagent neutralization, the neutral time is 10～30 minutes;
(3) in last step gained material, add pyridine-sulfonic acid diamines hydrophilic chain extender and carry out chain extending reaction, obtain the polymkeric substance that end group contains the NCO group, the temperature of reaction is 10～60 ℃, and the reaction times is 0.5～1h.Described pyridine-sulfonic acid diamines hydrophilic chain extender is represented by following general formula:
N=2,3 or 4 in the formula;
(4) in the polymkeric substance of last step gained, add the deionized water high-speed stirring and be dispersed into emulsion, add low-molecular-weight polyamine then and carry out the secondary chain extension reaction, the reaction times is 0.5～1h;
(5) decompression steams acetone, promptly makes the pyridine-sulfonic acid type aqueous polyurethane emulsion of high solids content.
Among the preparation method of this pyridine-sulfonic acid type aqueous polyurethane emulsion, the molar ratio of organic diisocyanate and polyester polyol can be 1.2～2.0 in the prepolymerization reaction in (1) step, and the quality of the dimethylol propionic acid of adding is 0.3～2% of a prepolymer total mass; Described catalyzer is dibutyl tin laurate (DBTDL) or stannous octoate, and add-on is 0.01～0.1% of a prepolymer total mass, is preferably 0.01～0.03%; The acetone quality that adds in (2) step be in the emulsion contained solid quality 40～120%, be preferably 50～100%; The salt-forming reagent that adds be for can generating the reagent of salt or ionic group with carboxyl, and common have triethylamine, ammoniacal liquor, Pottasium Hydroxide, sodium hydroxide, is preferably triethylamine; Degree of neutralization is 70～100%; The quality of the pyridine-sulfonic acid diamines hydrophilic chain extender that adds in (3) step is that the quality that 1～5%, the (4) step of contained solid quality adds entry in the emulsion is 40～60% of total aqueous polyurethane emulsion quality; The low-molecular-weight polyamine that adds is a quadrol, and the quadrol amount of adding is: the amido in the quadrol: the isocyano in the aqueous polyurethane emulsion=1: 0.6～1.8 (mol ratio).
Among the preparation method of this pyridine-sulfonic acid type aqueous polyurethane emulsion; Organic diisocyanate in the prepolymerization reaction in (1) step can be isophorone diisocyanate (IPDI) or 1; The mixture of one or more of hexamethylene-diisocyanate (HDI), Methylcyclohexyl diisocyanate (HTDI); Be preferably a kind of in isophorone diisocyanate (IPDI) and the hexamethylene diisocyanate (HDI) or two kinds; Described polyester polyol is polyester glycol, polylactone two pure and mild polycarbonate diols, and preferred polyester glycol or polylactone glycol, molecular weight are 500～5000, and preferred molecular weight is 1000～3000.
Among the preparation method of this pyridine-sulfonic acid type aqueous polyurethane emulsion; Polyester glycol described in the prepolymerization reaction in (1) step can be one or both di-carboxylic acid (succsinic acid, tartrate, pentanedioic acid, hexanodioic acid, toxilic acid, certain herbaceous plants with big flowers diacid, 1; Di-carboxylic acid such as 4-cyclohexyl dicarboxylic acid) with a kind of or two kinds of low molecular weight polyols (terepthaloyl moietie, Ucar 35,1,2-butyleneglycol, 1,3 butylene glycols, 1; 4-butyleneglycol, NSC 6366,1; 6-pinakon, 1,8-ethohexadiol, 1, low molecular weight polyols such as 9-nonanediol, Diethylene Glycol) make through method of condensing.The polylactone glycol can replace cyclic ester monomer ring-opening polymerizations such as 6-caprolactone, δ-Wu Neizhi through 6-caprolactone, alkyl and make, and preferably gathers hexanodioic acid-1,4-butanediol ester (PBA) and poly-epsilon-caprolactone (PCL).
Among the preparation method of this pyridine-sulfonic acid type aqueous polyurethane emulsion, (3) step described in the pyridine-sulfonic acid diamines can by
With H
2N (CH
2)
nNH
2After the reaction again with NaHSO
3Reaction makes, n=2,3 or 4 in the formula.
Concrete preparation method is following:
(1) preparation method of 2-[6-(2-aminoethylamino) picolyl] ethylsulfonic acid sodium:
(2) preparation method of 2-[6-(2-amino propyl amino) picolyl] ethylsulfonic acid sodium:
(3) preparation method of 2-[6-(the amino butyl of 2-is amino) picolyl] ethylsulfonic acid sodium:
The preparation method of this pyridine-sulfonic acid type aqueous polyurethane emulsion adopts the pyridine-sulfonic acid diamines as the synthetic aqueous polyurethane emulsion of hydrophilic chain extender; The crystal property and the anti-yellowing property of aqueous polyurethane emulsion have been improved greatly; Synthesis technique is simple; Synthetic aqueous polyurethane emulsion solid content is between 40～60%, and particle diameter is 70～200nm.
With specific embodiment technical scheme of the present invention is further described below, but protection scope of the present invention is not limited thereto:
Embodiment 1:
In the reactor drum that has whisking appliance, TM, water cooler, add the PBA (number-average molecular weight is 2000) of 200g, in 100～120 ℃ of fusings, vacuum hydro-extraction 1h, sampling is surveyed moisture content and was begun to lower the temperature less than 0.1% o'clock; When temperature drops to 80 ℃, add 13.3g IPDI, 19.5g HDI, 11g DMPA and 0.05g DBTDL catalyzer and carry out prepolymerization reaction, obtain prepolymer behind the about 4h of stirring reaction.Above-mentioned prepolymer is cooled to 50 ℃, adds 170g acetone solution prepolymer, then add the neutralization of 0.7g triethylamine, in the time be 15min; Add 4.2g 2-[6-(2-aminoethylamino) picolyl] ethylsulfonic acid sodium and carry out chain extending reaction, reaction times 0.5h obtains the polymkeric substance that end group contains the NCO group; In above-mentioned polymkeric substance, add the 210g deionized water, high-speed stirring is dispersed into emulsion, adds the 1.5g quadrol then and carries out secondary chain extension, reaction times 0.5h; At last, acetone is extracted in decompression out, promptly makes the high solid content aqueous polyurethane emulsion (WPU-1) that contains pyridine-sulfonic acid diamines hydrophilic chain extender.
The solid content of WPU-1 is 51.5%, appearance milky white band blue light, and median size is 176nm.
Embodiment 2:
In the reactor drum that has whisking appliance, TM, water cooler, add 200g PBA (number-average molecular weight is 2000), in 100～120 ℃ of fusings, vacuum hydro-extraction 1h, sampling is surveyed moisture content and was begun to lower the temperature less than 0.1% o'clock; When temperature drops to 80 ℃, add 38.1g IPDI, 3.1g DMPA and 0.05g DBTDL catalyzer and carry out prepolymerization reaction, obtain prepolymer behind the about 4h of stirring reaction.Above-mentioned prepolymer is cooled to 50 ℃, adds 210g acetone solution prepolymer, then add the neutralization of 2.1g triethylamine, in the time be 15min; Add 3.5g 2-[6-(2-amino propyl amino) picolyl] ethylsulfonic acid sodium and carry out chain extending reaction, reaction times 0.5h obtains the polymkeric substance that end group contains the NCO group; In above-mentioned polymkeric substance, add the 225g deionized water, high-speed stirring is dispersed into emulsion, adds the 1.5g quadrol then and carries out secondary chain extension, reaction times 0.5h; At last, acetone is extracted in decompression out, promptly makes the high solid content aqueous polyurethane emulsion (WPU-2) that contains pyridine-sulfonic acid diamines hydrophilic chain extender.
The solid content of WPU-2 is 51.9%, appearance milky white band blue light, and median size is 154nm.
Embodiment 3:
In the reactor drum that has whisking appliance, TM, water cooler, add 250g PCL (number-average molecular weight is 2000), in 100～120 ℃ of fusings, vacuum hydro-extraction 1h, sampling is surveyed moisture content and was begun to lower the temperature less than 0.1% o'clock; When temperature drops to 80 ℃, add 46.9g HDI, 3.9g DMPA and 0.06g DBTDL catalyzer and carry out prepolymerization reaction, obtain prepolymer behind the about 4h of stirring reaction.Above-mentioned prepolymer is cooled to 50 ℃, adds 265g acetone solution prepolymer, then add the neutralization of 2.4g triethylamine, in the time be 15min; Add 3g 2-[6-(the amino butyl of 2-is amino) picolyl] ethylsulfonic acid sodium and carry out chain extending reaction, reaction times 0.5h obtains the polymkeric substance that end group contains the NCO group; In above-mentioned polymkeric substance, add the 290g deionized water, high-speed stirring is dispersed into emulsion, adds the 2.3g quadrol then and carries out secondary chain extension, reaction times 0.5h; At last, acetone is extracted in decompression out, promptly makes the high solid content aqueous polyurethane emulsion (WPU-3) that contains pyridine-sulfonic acid diamines hydrophilic chain extender.
The solid content of WPU-3 is 48.9%, appearance milky white band blue light, and median size is 110nm.
Embodiment 4:
In the reactor drum that has whisking appliance, TM, water cooler, add the PBA (number-average molecular weight is 3000) of 268g, the PBA (number-average molecular weight is 1000) of 124g, in 100～120 ℃ of fusings, vacuum hydro-extraction 1h, sampling is surveyed moisture content and was begun to lower the temperature less than 0.1% o'clock; When temperature drops to 80 ℃, add 50.1g IPDI, 16.2g HDI, 2.2g DMPA and 0.11g DBTDL catalyzer and carry out prepolymerization reaction, obtain prepolymer behind the about 4h of stirring reaction.Above-mentioned prepolymer is cooled to 50 ℃, adds 260g acetone solution prepolymer, then add the neutralization of 1.6g triethylamine, in the time be 15min; Add 9.8g2-[6-(2-aminoethylamino) picolyl] ethylsulfonic acid sodium and carry out chain extending reaction, reaction times 0.5h obtains the polymkeric substance that end group contains the NCO group; In above-mentioned polymkeric substance, add the 440g deionized water, high-speed stirring is dispersed into emulsion, adds the 2.1g quadrol then and carries out secondary chain extension, reaction times 0.5h; At last, acetone is extracted in decompression out, promptly makes the high solid content aqueous polyurethane emulsion (WPU-4) that contains pyridine-sulfonic acid diamines hydrophilic chain extender.
The solid content of WPU-4 is 50.1%, appearance milky white band blue light, and median size is 178nm.
Embodiment 5:
In the reactor drum that has whisking appliance, TM, water cooler, add the PBA (number-average molecular weight is 2000) of 176g, the PCL (number-average molecular weight is 2000) of 64g, in 100～120 ℃ of fusings, vacuum hydro-extraction 1h, sampling is surveyed moisture content and was begun to lower the temperature less than 0.1% o'clock; When temperature drops to 80 ℃, add 10.8g IPDI, 32.7g HDI, 4.3g DMPA and 0.08gDBTDL catalyzer and carry out prepolymerization reaction, obtain prepolymer behind the about 4h of stirring reaction.Above-mentioned prepolymer is cooled to 50 ℃, adds 260g acetone solution prepolymer, then add the neutralization of 2.8g triethylamine, in the time be 15min; Add 3.1g2-[6-(2-aminoethylamino) picolyl] ethylsulfonic acid sodium and carry out chain extending reaction, reaction times 0.5h obtains the polymkeric substance that end group contains the NCO group; In above-mentioned polymkeric substance, add the 280g deionized water, high-speed stirring is dispersed into emulsion, adds the 1.9g quadrol then and carries out secondary chain extension, reaction times 0.5h; At last, acetone is extracted in decompression out, promptly makes the high solid content aqueous polyurethane emulsion (WPU-5) that contains pyridine-sulfonic acid diamines hydrophilic chain extender.
The solid content of WPU-5 is 49.8%, appearance milky white band blue light, and median size is 122nm.
Embodiment 6:
In the reactor drum that has whisking appliance, TM, water cooler, add the PBA (number-average molecular weight is 3000) of 120g, the PCL (number-average molecular weight is 2000) of 202g, in 100～120 ℃ of fusings, vacuum hydro-extraction 1h, sampling is surveyed moisture content and was begun to lower the temperature less than 0.1% o'clock; When temperature drops to 80 ℃, add 27.8gIPDI, 211gHDI, 1.9gDMPA and 0.1gDBTDL catalyzer and carry out prepolymerization reaction, obtain prepolymer behind the about 4h of stirring reaction.Above-mentioned prepolymer is cooled to 50 ℃, adds 360g acetone solution prepolymer, then add the neutralization of 1.4g triethylamine, in the time be 15min; Add 7.5g2-[6-(2-amino propyl amino) picolyl] ethylsulfonic acid sodium and carry out chain extending reaction, reaction times 0.5h obtains the polymkeric substance that end group contains the NCO group; In above-mentioned polymkeric substance, add the 360g deionized water, high-speed stirring is dispersed into emulsion, adds the 2.1g quadrol then and carries out secondary chain extension, reaction times 0.5h; At last, acetone is extracted in decompression out, promptly makes the high solid content aqueous polyurethane emulsion (WPU-6) that contains pyridine-sulfonic acid diamines hydrophilic chain extender.
The solid content of WPU-6 is 50.2%, appearance milky white band blue light, and median size is 110nm.
Above-mentioned 6 embodiment gained polyaminoester emulsions are carried out the T-peel strength test, and the mensuration of T-stripping strength is carried out with reference to GB/T27912-1995, and its draw speed is 100mm/min, and base material is PVC.Test-results is as shown in the table:
Claims (5)
1. the preparation method of a pyridine-sulfonic acid type aqueous polyurethane emulsion is characterized in that it may further comprise the steps:
(1) polyester polyol is carried out vacuum hydro-extraction and handle, in the presence of catalyzer, carry out prepolymerization reaction with organic diisocyanate, dimethylol propionic acid then, the reaction times is 2～5 hours, and temperature of reaction is 75～85 ℃;
(2) will go up step gained prepolymer and cool to below 50 ℃, and use acetone solution then, and then add the salt-forming reagent neutralization, the neutral time is 10～30 minutes;
(3) in last step gained material, add pyridine-sulfonic acid diamines hydrophilic chain extender and carry out chain extending reaction; Obtain the polymkeric substance that end group contains the NCO group; The temperature of reaction is 10～60 ℃, and the reaction times is 0.5～1h, and described pyridine-sulfonic acid diamines hydrophilic chain extender is represented by following general formula:
N=2,3 or 4 in the formula;
(4) in the polymkeric substance of last step gained, add the deionized water high-speed stirring and be dispersed into emulsion, add low-molecular-weight polyamine then and carry out the secondary chain extension reaction, the reaction times is 0.5～1h;
(5) decompression steams acetone, promptly makes pyridine-sulfonic acid type aqueous polyurethane emulsion.
2. the preparation method of pyridine-sulfonic acid type aqueous polyurethane emulsion as claimed in claim 1; The molar ratio that it is characterized in that organic diisocyanate and polyester polyol in the prepolymerization reaction in described (1) step is 1.2～2.0, and the quality of the dimethylol propionic acid of adding is 0.3～2% of a prepolymer total mass; Described catalyzer is dibutyl tin laurate or stannous octoate, and add-on is 0.01～0.03% of a prepolymer total mass; The acetone quality that adds in (2) step be in the emulsion contained solid quality 50～100%; The salt-forming reagent that adds is a triethylamine, and degree of neutralization is 70～100%; The quality of the pyridine-sulfonic acid diamines hydrophilic chain extender that adds in (3) step is that the quality that adds entry 1～5%, the (4) step of the contained solid quality of emulsion is 40～60% of total aqueous polyurethane emulsion quality; The low-molecular-weight polyamine that adds is a quadrol, the amount of the quadrol of adding through molar ratio computing be: the amido in the quadrol: the isocyano in the aqueous polyurethane emulsion=1: 0.6～1.8.
3. the preparation method of pyridine-sulfonic acid type aqueous polyurethane emulsion as claimed in claim 2; It is characterized in that organic diisocyanate in the prepolymerization reaction in described (1) step is the mixture of a kind of in isophorone diisocyanate or the hexamethylene diisocyanate or two kinds; Described polyester polyol is polyester glycol or polylactone glycol, and molecular weight is 1000～3000.
4. the preparation method of pyridine-sulfonic acid type aqueous polyurethane emulsion as claimed in claim 3; It is characterized in that the polyester glycol described in the prepolymerization reaction in described (1) step makes through method of condensing for one or both di-carboxylic acid and a kind of or two kinds of low molecular weight polyols; Described polylactone glycol is for gathering hexanodioic acid-1,4-butanediol ester or poly-epsilon-caprolactone.
5. the preparation method of pyridine-sulfonic acid type aqueous polyurethane emulsion as claimed in claim 4 is characterized in that described
(3) step described in the pyridine-sulfonic acid diamines by
With H
2N (CH
2)
nNH
2After the reaction again with NaHSO
3Reaction makes, n=2,3 or 4 in the formula.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634779A (en) * | 2016-12-28 | 2017-05-10 | 上海飞顿新材料科技有限公司 | Preparation method of adhesive for aramid fiber no-woven cloth |
| CN109251291A (en) * | 2017-07-12 | 2019-01-22 | 广州冠志新材料科技有限公司 | A kind of alicyclic sulfonic acid type hydrophilic chain extending agent and preparation method thereof |
| CN110330618A (en) * | 2019-07-30 | 2019-10-15 | 嘉兴学院 | Aqueous polyurethane emulsion, preparation method and application |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862506A (en) * | 2019-10-29 | 2020-03-06 | 中国科学院山西煤炭化学研究所 | Synthetic method of waterborne polyurethane primer |
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| US5177171A (en) * | 1989-09-14 | 1993-01-05 | Asahi Kasei Kogyo Kabushiki Kaisha | Sulfonic acid group-containing polyurethane and a photosensitive resin composition containing the same |
| CN101597369A (en) * | 2008-06-06 | 2009-12-09 | 佛山市南海霸力化工制品有限公司 | Contain high solid content polyurethane emulsion of alicyclic sulfonic acid type hydrophilic chain extending agent and preparation method thereof |
| US20090312488A1 (en) * | 2006-07-07 | 2009-12-17 | Takao Kamohara | Aqueous polyurethane fluid dispersion and method for producing the same |
| CN101638468A (en) * | 2009-09-04 | 2010-02-03 | 安徽大学 | Preparation method of sulfonate amphoteric polyurethane emulsion |
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2012
- 2012-03-21 CN CN2012100774751A patent/CN102617822B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5177171A (en) * | 1989-09-14 | 1993-01-05 | Asahi Kasei Kogyo Kabushiki Kaisha | Sulfonic acid group-containing polyurethane and a photosensitive resin composition containing the same |
| US20090312488A1 (en) * | 2006-07-07 | 2009-12-17 | Takao Kamohara | Aqueous polyurethane fluid dispersion and method for producing the same |
| CN101597369A (en) * | 2008-06-06 | 2009-12-09 | 佛山市南海霸力化工制品有限公司 | Contain high solid content polyurethane emulsion of alicyclic sulfonic acid type hydrophilic chain extending agent and preparation method thereof |
| CN101638468A (en) * | 2009-09-04 | 2010-02-03 | 安徽大学 | Preparation method of sulfonate amphoteric polyurethane emulsion |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634779A (en) * | 2016-12-28 | 2017-05-10 | 上海飞顿新材料科技有限公司 | Preparation method of adhesive for aramid fiber no-woven cloth |
| CN109251291A (en) * | 2017-07-12 | 2019-01-22 | 广州冠志新材料科技有限公司 | A kind of alicyclic sulfonic acid type hydrophilic chain extending agent and preparation method thereof |
| CN110330618A (en) * | 2019-07-30 | 2019-10-15 | 嘉兴学院 | Aqueous polyurethane emulsion, preparation method and application |
| CN110330618B (en) * | 2019-07-30 | 2021-05-18 | 嘉兴学院 | Waterborne polyurethane emulsion, preparation method and application thereof |
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