CN102382278B - Waterborne polyurethane resin and preparation method and application thereof - Google Patents
Waterborne polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN102382278B CN102382278B CN 201110250717 CN201110250717A CN102382278B CN 102382278 B CN102382278 B CN 102382278B CN 201110250717 CN201110250717 CN 201110250717 CN 201110250717 A CN201110250717 A CN 201110250717A CN 102382278 B CN102382278 B CN 102382278B
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Abstract
The invention discloses a waterborne polyurethane resin and a preparation method and application of the watercraft polyurethane resin. The raw materials except water for preparation include, by weight, 10% to 50% of one or more kinds of aliphatic or aromatic isocyanate compound, 40% to 80% of at least one kind of polyol with the molecular weight ranging from 400 to 5000, 0.5% to 20% of at least one kind of ion or potential type hydrophilic compound, 0.5 % to 10% of at least one kind of low-molecular-weight compound containing hydroxide radical or amino with the molecular weight ranging from 40 to 500, and 0% to 10% of auxiliaries and additive agent. The waterborne polyurethane resin has excellent resistance to hot toluene, and microfibre synthetic leather made by the waterborne polyurethane resin by the waterborne solidifying technology is better in mechanical property and touch.
Description
Technical field
The invention belongs to the polyurethane synthetic material technical field, be specifically related to a kind of waterborne polyurethane resin and its preparation method and application.
Background technology
At present, solvent type polyurethane resin is as the basic raw material of traditional microfiber synthetic leather goods, and its production process adopts dimethyl methyl acid amide (DMF) etc. as solvent mostly.95% solvent is recovered utilization in solvent type wet production, but still has part to reclaim, and a large amount of wastes that this has not only caused organic solvent and the energy also will certainly have a strong impact on ecotope.But the up-to-date ecological criteria of the European Community has also had new defining with poisonous and hazardous solvent use range, simultaneously Environmental Protection in China department to the sewage discharge regulation DMF content of leather industry at 2 mg/below the L.
Waterborne polyurethane resin is dispersion medium with water, have do not fire, advantage such as nontoxic, safety, environmental protection, the Application and Development of waterborne polyurethane resin becomes the focus of domestic and international research, and great amount of manpower has all been dropped in the research centre of nearly all big chemical company, middle-size and small-size chemical company and university and material resources have been carried out the research and development of waterborne polyurethane resin.Because its environmental protection characteristic does not endanger the healthy of operator and human consumer in production and use, aspect a lot of, replaced the solvent borne polyurethane material simultaneously.Yet because it introduces a large amount of hydrophilic radicals, caused its water tolerance, elastic performance to descend; Cause that based on thread-like molecule thermotolerance is not enough, limited its use in some higher occasion.
The waterborne polyurethane resin that is used for microfiber synthetic leather at present, and the rarely seen open report of corresponding leather-making technology.
Summary of the invention
Goal of the invention: at the deficiencies in the prior art, the purpose of this invention is to provide a kind of waterborne polyurethane resin, make it have mechanical property preferably, higher characteristics such as elastic performance, can satisfy the preparation demand of microfiber synthetic leather.Another object of the present invention provides a kind of method for preparing above-mentioned waterborne polyurethane resin.The present invention also has a purpose to provide the application of waterborne polyurethane resin in the leather-making technology of water-based microfiber synthetic leather impregnation.
Technical scheme: in order to realize the foregoing invention purpose, the technical solution used in the present invention is:
A kind of waterborne polyurethane resin, preparation raw material dewater and comprise each component of following weight percent in addition: one or more aliphatics or the aromatic isocyanate compound of 10%-50%; At least a polyol of 40%-80%, its molecular weight are 400-5000; At least a ionic hydrophilic compound of 0.5%-20%; At least a hydroxyl or the amino low-molecular weight compound of containing of 0.5%-10%, its molecular weight is 40-500; The auxiliary agent of 0%-10% and additive, the weight content of water is 40%-75% in the waterborne polyurethane resin.
Described multiple aliphatics or aromatic isocyanate compound are that 0%-90% aliphatic diisocyanate compound, 10%-100% aromatic diisocyanate compounds and 0%-20% polyisocyanate compound are formed by weight percent.The aliphatic diisocyanate compound comprises hexamethylene diisocyanate, xylylene diisocyanate and isophorone diisocyanate etc.Aromatic diisocyanate compounds comprises 4,4-diphenylmethanediisocyanate and tolylene diisocyanate etc.Polyisocyanate compound is formed and is comprised poly methylene poly phenyl poly isocyanate and HDI tripolymer etc.
Described polyol is that 20%-80% polyester polyol, 10%-60% polyether glycol and 5%-20% polyester polyethers polyol are formed by weight percent.Polyester polyol comprises poly-adipate glycol hexylene glycol esterdiol, poly-hexanodioic acid neopentyl glycol hexylene glycol esterdiol and poly-hexanodioic acid neopentyl glycol butanediol ester glycol etc.Polyether glycol comprises polytetrahydrofuran dibasic alcohol and polyoxytrimethylene triol etc.Polyester polyethers polyol is based on the synthetic polyester polyethers polyol of hexylene glycol, butyleneglycol, neopentyl glycol, hexanodioic acid and polytetrahydrofuran dibasic alcohol, molecular weight is 800～4000, comprise poly-hexanodioic acid butyleneglycol hexylene glycol ester erythritan, and poly-hexanodioic acid neopentyl glycol hexylene glycol ester erythritan etc.
Described hydrophilic compounds refers to have-COOY, SO
3Y ,-PO (OY)
2,-NR
2Or-NR
3 +The compound of group; Wherein, Y is H, NH
4 +Or metallic cation, R is H, alkyl or aryl.Typical hydrophilic compounds comprises diamino sulfonic acid salt, dimethylol propionic acid, dimethylolpropionic acid, hydroxy new pentane acid, 2-(2-aminoethylamino) ethyl sulfonic acid and N methyldiethanol amine and cyclohexyl aminopropanesulfonic acid etc.
Described low-molecular weight compound comprises trivalent alcohol and tertiary amine etc.Typical low-molecular weight compound comprises triglycol, TriMethylolPropane(TMP), diethylenetriamine, ethylene glycol, propylene glycol and butyleneglycol etc.
Described auxiliary agent and additive can comprise neutralizing agent, defoamer and thickening material for auxiliary agent and additive commonly used in the industry.Neutralizing agent is sodium hydroxide, potassium hydroxide, dimethylethanolamine, methyl-sulfate or hydrochloric acid; Defoamer is the organic silicon modified by polyether compounds, and typical organic silicon modified by polyether compounds has BYK-020 (commercial name); Thickening material is association type aqueous polyurethane or alkali swelling type polyacrylic acid emulsion, and typical association type aqueous polyurethane has UH-420 (commercial name), and typical alkali swelling type polyacrylic acid emulsion has ASE-60 (commercial name).
Prepare aqueous polyurethane of the present invention, can use known method.Also can use following method:
In reactor, add polyester polyol, polyether glycol, polyester polyethers polyol, isocyanic ester according to prescription, temperature control 60-90 ℃, react 3-5h under the normal pressure, add 70-100 ℃ of hydrophilic compounds, low-molecular weight compound temperature control again, react 1-3h under the normal pressure; After treating that system NCO content reaches theoretical value, be cooled to 40-70 ℃, add an amount of solvent and neutralizing agent, add deionized water under the condition of high-speed stirring, emulsification extracts solvent, makes aqueous polyurethane.
The application of above-mentioned waterborne polyurethane resin in the leather-making technology of water-based microfiber synthetic leather impregnation.Concrete application method is: waterborne polyurethane resin is immersed nylon 6 (PA
6In the compound sea-island fibre non-woven fabrics of)/polyethylene (PE), solidify, wash through the water-based solidification liquid, extract out, wash through toluene again, finally by crossing oven dry, namely get the superfine fiber chemical leather base cloth.
Described water-based solidification liquid by weight percent be 50%-98% water, 0.5%-20% complex compound or ionic compound arranged, and the supplementary additive of 0.1%-8% is formed; Described auxiliary addition agent comprises defoamer, flow agent, wetting agent, hand feeling agent and last toner.
Defoamer is two acetylene compounds, and representative substances is Surfynol DF-75 (commercial name); Flow agent is modified polyorganosiloxane, and representative substances is Levaslip 455 (commercial name); Wetting agent is polyether-modified polydimethylsiloxane, and representative substances is Wet-250 (commercial name); Hand feeling agent is SP-735 (commercial name); Last toner is the commercial name of SW().
Described organic complex is with Fe
2+, Cu
2+, Pt
2+With the complex compound of atom centered by the Ni, described ionic compound is with Na
+, K
+, Ca
2+, Mg
2+, Fe
3+The ionic compound that forms.
The time of solidifying in the water-based solidification liquid is 10-60min, and the temperature of water-based solidification liquid is 15-50 ℃.
Beneficial effect: compared with prior art, the outstanding advantage that waterborne polyurethane resin of the present invention has is: heat-resisting toluene, suitable solidifying process, good springiness.Approach existing solvent-borne type microfiber synthetic leather technology largely, do very little change at existing production line like this, just can production water-based microfiber synthetic leather.
Embodiment
The present invention will be further explained below in conjunction with specific embodiment.
Embodiment 1
In reactor, add, 20kg 1, hexamethylene-diisocyanate, 10kg 4,4-diphenylmethanediisocyanate, the poly-adipate glycol hexylene glycol esterdiol (molecular weight 1500) of 45kg, 10kg polyoxytrimethylene triol (molecular weight 3000), the poly-hexanodioic acid butyleneglycol hexylene glycol ester erythritan (molecular weight 2200) of 5kg, temperature control 80-90 ℃, react 5h under the normal pressure, add 70-100 ℃ of 2.5kg dimethylolpropionic acid, 4.9kg ethylene glycol temperature control again, react 2h under the normal pressure; After treating that system NCO content reaches theoretical value, be cooled to 40-70 ℃, add 5kg acetone and 1.5kg dimethylethanolamine reaction 45min, be to add deionized water under the stirring of 100r/min at rotating speed, emulsification, add 0.1kg BYK-020 and 1kg ASE-60, extract solvent then, make aqueous polyurethane.
Waterborne polyurethane resin is immersed in the compound sea-island fibre non-woven fabrics of nylon 6/ polyethylene, solidify 10-60min, washing through 15-50 ℃ of water-based solidification liquid, extract out, wash through toluene again, finally by crossing oven dry, namely get the superfine fiber chemical leather base cloth.Wherein, the water-based solidification liquid is made up of the SP-735 of Wet-250, the 0.2kg of Levaslip 455, the 0.4kg of Surfynol DF-75, the 0.4kg of the cupric tetramminosulfate of 92kg water, 6kg, 0.8kg and the SW of 0.2kg.
Embodiment 2
In reactor, add, 30kg tolylene diisocyanate, 5kg HDI tripolymer (molecular weight 579), the poly-adipate glycol hexylene glycol esterdiol (molecular weight 1500) of 40kg, 10kg polytetrahydrofuran dibasic alcohol (molecular weight 2000), the poly-hexanodioic acid butyleneglycol hexylene glycol ester erythritan (molecular weight 2200) of 10kg, temperature control 80-90 ℃, react 5h under the normal pressure, add 70-100 ℃ of 3kg dimethylolpropionic acid, 8kg ethylene glycol temperature control again, react 3h under the normal pressure; After treating that system NCO content reaches theoretical value, be cooled to 40-70 ℃, add 5.5kg butanone and 2kg dimethylethanolamine reaction 45min, under the condition of 120r/min, add deionized water, emulsification, BYK-020 and the 0.5kg UH-420 of adding 0.1kg, extract solvent then, make aqueous polyurethane.
Waterborne polyurethane resin is immersed in the compound sea-island fibre non-woven fabrics of nylon 6/ polyethylene, solidify 10-60min, washing through 15-50 ℃ of water-based solidification liquid, extract out, wash through toluene again, finally by crossing oven dry, namely get the superfine fiber chemical leather base cloth.Wherein, the water-based solidification liquid is made up of the SP-735 of Wet-250, the 0.07kg of Levaslip 455, the 0.23kg of Surfynol DF-75, the 0.25kg of the Repone K of 91kg water, 8kg, 0.4kg and the SW of 0.05kg.
Embodiment 3
In reactor, add, 30kg 4,4-diphenylmethanediisocyanate, the poly-hexanodioic acid neopentyl glycol hexylene glycol esterdiol (molecular weight 1500) of 20kg, 20kg polyoxytrimethylene triol, the poly-hexanodioic acid butyleneglycol hexylene glycol ester erythritan (molecular weight 2200) of 5kg, temperature control 80-90 ℃, react 5h under the normal pressure, add 70-100 ℃ of N methyldiethanol amine, the 4.9kg butyleneglycol temperature control of 2.5kg again, react 2h under the normal pressure; After treating that system NCO content reaches theoretical value, be cooled to 40-70 ℃, 4kg acetone and 0.8kg hydrochloric acid reaction 45min, add deionized water under the condition of 100r/min high-speed stirring, emulsification adds 0.1kg BYK-020 and 1kg UH-420, extract solvent then, make aqueous polyurethane.
Waterborne polyurethane resin is immersed in the compound sea-island fibre non-woven fabrics of nylon 6/ polyethylene, solidify 10-60min, washing through 15-50 ℃ of water-based solidification liquid, extract out, wash through toluene again, finally by crossing oven dry, namely get the superfine fiber chemical leather base cloth.Wherein, the water-based solidification liquid is made up of the SP-735 of Wet-250, the 0.07kg of Levaslip 455, the 0.23kg of Surfynol DF-75, the 0.25kg of the Repone K of 91kg water, 8kg, 0.4kg and the SW of 0.05kg.
Embodiment 4
In reactor, add, 10kg xylylene diisocyanate, 20kg tolylene diisocyanate, 5kg poly methylene poly phenyl poly isocyanate, the poly-adipate glycol hexylene glycol esterdiol (molecular weight 1500) of 40kg, 10kg polytetrahydrofuran dibasic alcohol (molecular weight 2000), the poly-hexanodioic acid neopentyl glycol hexylene glycol ester erythritan (molecular weight 2200) of 10kg, temperature control 80-90 ℃, react 5h under the normal pressure, add 70-100 ℃ of 3kg diamino sulfonic acid salt, 8kg propylene glycol temperature control again, react 3h under the normal pressure; After treating that system NCO content reaches theoretical value, be cooled to 40-70 ℃, add 6kg acetone, add deionized water under the 100r/min condition, emulsification adds 0.1kg BYK-020 and 1kg UH-420, extracts solvent then, makes aqueous polyurethane.
Waterborne polyurethane resin is immersed in the compound sea-island fibre non-woven fabrics of nylon 6/ polyethylene, solidify 10-60min, washing through 15-50 ℃ of water-based solidification liquid, extract out, wash through toluene again, finally by crossing oven dry, namely get the superfine fiber chemical leather base cloth.Wherein, the water-based solidification liquid is made up of the SP-735 of Wet-250, the 0.2kg of Levaslip 455, the 0.4kg of Surfynol DF-75, the 0.4kg of the Hexacyanoferrate potassium of 88kg water, 10kg, 0.8kg and the SW of 0.2kg.
The comparative example
In reactor, add, 20kg1, hexamethylene-diisocyanate, 10kg4,4-diphenylmethanediisocyanate, 50kg polytetrahydrofuran dibasic alcohol (molecular weight 2000), temperature control 80-90 ℃, react 5h under the normal pressure, add 70-100 ℃ of 2.5kg dimethylolpropionic acid, 4.9kg ethylene glycol temperature control again, react 2h under the normal pressure; After treating that system NCO content reaches theoretical value, be cooled to 40-70 ℃, add 5kg acetone and 1.5kg dimethylethanolamine reaction 45min, add deionized water under the condition of 100r/min, emulsification adds 0.1kg BYK-020 and 1kg UH-420, extract solvent then, make aqueous polyurethane.
Waterborne polyurethane resin is immersed in the compound sea-island fibre non-woven fabrics of nylon 6/ polyethylene, solidify 10-60min, washing through 15-50 ℃ of water-based solidification liquid, extract out, wash through toluene again, finally by crossing oven dry, namely get the superfine fiber chemical leather base cloth.Wherein, the water-based solidification liquid is made up of the SP-735 of Wet-250, the 0.07kg of Levaslip 455, the 0.23kg of Surfynol DF-75, the 0.25kg of the sodium-chlor of 91kg water, 8kg, 0.4kg and the SW of 0.05kg.
Under the same conditions, with embodiment 1,2,3 and 4 and comparative example's product carry out Performance Detection, the result is as shown in table 1.
Table 1 performance test results table
By the aqueous polyurethane among contrast the present invention, the result is as shown in table 1, and obviously, embodiment 1 and 2 aqueous polyurethane have good heat-resisting toluene performance, the microfiber synthetic leather that while is made by the water-based solidifying process by this aqueous polyurethane, mechanical property and feel preferably.
Claims (2)
1. a waterborne polyurethane resin is characterized in that, comprises each component of following weight percent beyond the preparation raw material dewaters: one or more aliphatics or the aromatic isocyanate compound of 10%-50%; At least a polyol of 40%-80%, its molecular weight are 400-5000; At least a ionic hydrophilic compound of 0.5%-20%; At least a hydroxyl or the amino low-molecular weight compound of containing of 0.5%-10%, its molecular weight is 40-500; The auxiliary agent of 0%-10% and additive, the weight content of water is 40%-75% in the waterborne polyurethane resin; It is synthetic that described waterborne polyurethane resin is used for superfine fiber chemical leather;
Described polyol is that 20%-80% polyester polyol, 10%-60% polyether glycol and 5%-20% polyester polyethers polyol are formed by weight percent;
Described polyester polyethers polyol is based on the synthetic polyester polyethers polyol of hexylene glycol, butyleneglycol, neopentyl glycol, hexanodioic acid and polytetrahydrofuran dibasic alcohol, and molecular weight is 800～4000;
Described hydrophilic compounds refers to have-COOY, SO
3Y ,-PO (OY)
2,-NR
2Or-NR
3 +The compound of group; Wherein, Y is H, NH
4 +Or metallic cation, R is H, alkyl or aryl;
Described low-molecular weight compound comprises trivalent alcohol or tertiary amine.
2. the application of the described waterborne polyurethane resin of claim 1 in the leather-making technology of aqueous ultrafine fiber synthetic leather impregnation, waterborne polyurethane resin is contained in the compound sea-island fibre non-woven fabrics of immersion nylon 6/ polyethylene, solidify, wash through the water-based solidification liquid, extract out, wash through toluene again, finally by crossing oven dry, namely get the superfine fiber chemical leather base cloth; Described water-based solidification liquid is the water of 50%-98%, complex compound or the inorganic ionic compound of 0.5%-20% by weight percent, and the supplementary additive of 0.1%-8% composition, and each component summation is 100%; Described auxiliary addition agent comprises defoamer, flow agent, wetting agent, hand feeling agent and last toner;
Described complex compound is with Fe
2+, Cu
2+, Pt
2+With the complex compound of atom centered by the Ni, described inorganic ionic compound is with Na
+, K
+, Ca
2+, Mg
2+, Fe
3+The ionic compound that forms;
The time of solidifying in the water-based solidification liquid is 10-60min, and the temperature of water-based solidification liquid is 15-50 ℃.
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| CN102382278B true CN102382278B (en) | 2013-08-28 |
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| CN103469599A (en) * | 2012-06-06 | 2013-12-25 | 上海日多高分子材料有限公司 | Production method of unsmoothness increasing agent for polyurethane basketball leather |
| CN103044652A (en) * | 2013-01-05 | 2013-04-17 | 旭川化学（苏州）有限公司 | High-gloss water-base polyurethane resin for synthetic leather and preparation method of high-gloss water-base polyurethane resin |
| WO2015115290A1 (en) * | 2014-01-30 | 2015-08-06 | 東レ株式会社 | Sheet-like article, and method for producing same |
| WO2015129602A1 (en) * | 2014-02-27 | 2015-09-03 | 東レ株式会社 | Sheet-like material and method for producing same |
| CN107841881B (en) * | 2017-11-03 | 2019-05-21 | 江苏尚科聚合新材料有限公司 | A kind of cationic fiber can contaminate the preparation method of artificial leather |
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| CN101440253A (en) * | 2008-12-26 | 2009-05-27 | 郭琦 | Environment-friendly aqueous glove coating , and preparation thereof |
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| US6147155A (en) * | 1999-06-08 | 2000-11-14 | Bayer Corporation | Aqueous polyurethane dispersions containing non-cyclic diisocyanates and a process for their preparation |
| US20050020767A1 (en) * | 2001-12-04 | 2005-01-27 | Huey-Huey Lo | High performance aqueous polyurethanes dispersion and methods of fabricating the same |
| CN101481876B (en) * | 2008-01-31 | 2012-05-09 | 东莞市恩典皮具制品有限公司 | Aqueous polyurethane emulsion for synthetic leather and preparation thereof |
| CN101580577B (en) * | 2009-06-18 | 2011-05-18 | 建德市顺发化工助剂有限公司 | Modified waterborne polyurethane resin for artificial leather and preparation method thereof |
| CN101613448A (en) * | 2009-07-10 | 2009-12-30 | 烟台道成化学有限公司 | The preparation method of a kind of waterborne polyurethane resin and dipping sizing agent for synthetic leather base material |
| CN101666043A (en) * | 2009-09-15 | 2010-03-10 | 烟台万华超纤股份有限公司 | Waterborne polyurethane coating transfer synthetic leather and manufacturing method |
| CN101665675B (en) * | 2009-09-22 | 2012-03-28 | 烟台华大化学工业有限公司 | Method for preparing aqueous polyurethane adhesive and superfine fiber synthetic leather |
| CN101725052B (en) * | 2009-11-04 | 2012-06-13 | 烟台万华超纤股份有限公司 | Waterborne polyurethane resin superfiber leather and manufacturing method thereof |
| CN102115983B (en) * | 2011-01-26 | 2013-02-13 | 烟台华大化学工业有限公司 | Aqueous polyurethane superfine fiber synthetic leather and preparation method thereof |
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