CN102382278A - 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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- CN102382278A CN102382278A CN2011102507178A CN201110250717A CN102382278A CN 102382278 A CN102382278 A CN 102382278A CN 2011102507178 A CN2011102507178 A CN 2011102507178A CN 201110250717 A CN201110250717 A CN 201110250717A CN 102382278 A CN102382278 A CN 102382278A
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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.
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 the 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, caused its water tolerance, elastic performance to descend because it introduces a large amount of hydrophilic radicals; With the thread-like molecule is that the master causes that thermotolerance is not enough, has limited its use in some higher occasion.
The waterborne polyurethane resin that is used for microfiber synthetic leather at present, and the corresponding rarely seen public reported of leather-making technology.
Summary of the invention
Goal of the invention: the deficiency to existing 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 scheme that the present invention adopts 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 and gathers adipate glycol pinakon esterdiol, gathers hexanodioic acid NSC 6366 pinakon esterdiol and gather hexanodioic acid NSC 6366 butanediol ester glycol etc.Polyether glycol comprises THF homopolymer divalent alcohol and polyoxytrimethylene triol etc.Polyester polyethers polyol is based on pinakon, butyleneglycol, NSC 6366, hexanodioic acid and THF homopolymer divalent alcohol synthetic polyester polyethers polyol; Molecular weight is 800～4000; Comprise and gather hexanodioic acid butyleneglycol pinakon ester erythritan, and gather hexanodioic acid NSC 6366 pinakon ester erythritan etc.
Described hydrophilic compounds is meant and has-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, NSC 115936,2-(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, terepthaloyl moietie, Ucar 35 and butyleneglycol etc.
Described auxiliary agent and additive can comprise neutralizing agent, skimmer and thickening material for auxiliary agent and additive commonly used in the industry.Neutralizing agent is sodium hydroxide, Pottasium Hydroxide, dimethylethanolamine, methyl-sulfate or hydrochloric acid; Skimmer 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 ROHM emulsion, and typical association type aqueous polyurethane has UH-420 (commercial name), and typical alkali swelling type ROHM emulsion has ASE-60 (commercial name).
Prepare aqueous polyurethane of the present invention, can use known method.Also can use following method:
In reaction kettle, add polyester polyol, polyether glycol, polyester polyethers polyol, isocyanic ester according to prescription; Temperature control 60-90 ℃; Normal pressure is reaction 3-5h down, adds 70-100 ℃ of hydrophilic compounds, low-molecular weight compound temperature control again, and normal pressure is reaction 1-3h down; After treating that system NCO content reaches theoretical value, be cooled to 40-70 ℃, add an amount of solvent and neutralizing agent, under the condition of high-speed stirring, add deionized water, 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)/Vilaterm (PE), solidify, wash, extract out, wash through toluene again, through oven dry, promptly get the superfine fiber chemical leather base cloth at last through the water-based solidification liquid.
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 skimmer, flow agent, wetting agent, hand feeling agent and last toner.
Skimmer is two acetylene compounds, and representative substances is Surfynol DF-75 (a commercial name); Flow agent is a modified polyorganosiloxane, and representative substances is Levaslip 455 (a commercial name); Wetting agent is polyether-modified YSR 3286, and representative substances is Wet-250 (a commercial name); Hand feeling agent is SP-735 (a commercial name); Last toner is SW (a commercial name).
Described organic complex is with Fe
2+, Cu
2+, Pt
2+With Ni be the complex compound of central atom, described ionic compound is with Na
+, K
+, Ca
2+, Mg
2+, Fe
3+The ionic compound that forms.
The time of in the water-based solidification liquid, solidifying 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.Near existing solvent-borne type microfiber synthetic leather technology, on existing production line, do very little change so largely, just can production water-based microfiber synthetic leather.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explanation.
Embodiment 1
In reaction kettle, add; 20kg hexamethylene diisocyanate, 10kg 4,4-diphenylmethanediisocyanate, 45kg gather adipate glycol pinakon esterdiol (molecular weight 1500), 10kg polyoxytrimethylene triol (molecular weight 3000), 5kg and gather hexanodioic acid butyleneglycol pinakon ester erythritan (molecular weight 2200); Temperature control 80-90 ℃; Normal pressure is reaction 5h down, adds 70-100 ℃ of 2.5kg dimethylolpropionic acid, 4.9kg terepthaloyl moietie temperature control again, and normal pressure is reaction 2h down; After treating that system NCO content reaches theoretical value; Being cooled to 40-70 ℃, adding 5kg acetone and 1.5kg dimethylethanolamine reaction 45min, is adding 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/ Vilaterm, solidify 10-60min, washing, extract out, wash through toluene again, through oven dry, promptly get the superfine fiber chemical leather base cloth at last through 15-50 ℃ of water-based solidification liquid.Wherein, the water-based solidification liquid is made up of the cupric tetramminosulfate of 92kg water, 6kg, the Surfynol DF-75 of 0.8kg, the Levaslip 455 of 0.4kg, the Wet-250 of 0.4kg, the SP-735 of 0.2kg and the SW of 0.2kg.
Embodiment 2
In reaction kettle, add; 30kg tolylene diisocyanate, 5kg HDI tripolymer (molecular weight 579), 40kg gather adipate glycol pinakon esterdiol (molecular weight 1500), 10kg THF homopolymer divalent alcohol (molecular weight 2000), 10kg and gather hexanodioic acid butyleneglycol pinakon ester erythritan (molecular weight 2200); Temperature control 80-90 ℃; Normal pressure is reaction 5h down, adds 70-100 ℃ of 3kg dimethylolpropionic acid, 8kg terepthaloyl moietie temperature control again, and normal pressure is reaction 3h down; 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/ Vilaterm, solidify 10-60min, washing, extract out, wash through toluene again, through oven dry, promptly get the superfine fiber chemical leather base cloth at last through 15-50 ℃ of water-based solidification liquid.Wherein, the water-based solidification liquid is made up of the Repone K of 91kg water, 8kg, the Surfynol DF-75 of 0.4kg, the Levaslip 455 of 0.25kg, the Wet-250 of 0.23kg, the SP-735 of 0.07kg and the SW of 0.05kg.
Embodiment 3
In reaction kettle, add; 30kg 4, and 4-diphenylmethanediisocyanate, 20kg gather hexanodioic acid NSC 6366 pinakon esterdiol (molecular weight 1500), and 20kg polyoxytrimethylene triol, 5kg gather hexanodioic acid butyleneglycol pinakon ester erythritan (molecular weight 2200); Temperature control 80-90 ℃; Normal pressure is reaction 5h down, adds 70-100 ℃ of N methyldiethanol amine, the 4.9kg butyleneglycol temperature control of 2.5kg again, and normal pressure is reaction 2h down; After treating that system NCO content reaches theoretical value, be cooled to 40-70 ℃, 4kg acetone and 0.8kg hydrochloric acid reaction 45min; Under the condition of 100r/min high-speed stirring, add deionized water, 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/ Vilaterm, solidify 10-60min, washing, extract out, wash through toluene again, through oven dry, promptly get the superfine fiber chemical leather base cloth at last through 15-50 ℃ of water-based solidification liquid.Wherein, the water-based solidification liquid is made up of the Repone K of 91kg water, 8kg, the Surfynol DF-75 of 0.4kg, the Levaslip 455 of 0.25kg, the Wet-250 of 0.23kg, the SP-735 of 0.07kg and the SW of 0.05kg.
Embodiment 4
In reaction kettle, add; 10kg xylylene diisocyanate, 20kg tolylene diisocyanate, 5kg poly methylene poly phenyl poly isocyanate, 40kg gather adipate glycol pinakon esterdiol (molecular weight 1500), 10kg THF homopolymer divalent alcohol (molecular weight 2000), 10kg and gather hexanodioic acid NSC 6366 pinakon ester erythritan (molecular weight 2200); Temperature control 80-90 ℃; Normal pressure is reaction 5h down; Add 70-100 ℃ of 3kg diamino sulfonic acid salt, 8kg Ucar 35 temperature control again, normal pressure is reaction 3h down; After treating that system NCO content reaches theoretical value, be cooled to 40-70 ℃, add 6kg acetone, under the 100r/min condition, add deionized water, 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/ Vilaterm, solidify 10-60min, washing, extract out, wash through toluene again, through oven dry, promptly get the superfine fiber chemical leather base cloth at last through 15-50 ℃ of water-based solidification liquid.Wherein, the water-based solidification liquid is made up of the Hexacyanoferrate potassium of 88kg water, 10kg, the Surfynol DF-75 of 0.8kg, the Levaslip 455 of 0.4kg, the Wet-250 of 0.4kg, the SP-735 of 0.2kg and the SW of 0.2kg.
The comparative example
In reaction kettle, add; 20kg1, hexamethylene-diisocyanate, 10kg4,4-diphenylmethanediisocyanate, 50kg THF homopolymer divalent alcohol (molecular weight 2000); Temperature control 80-90 ℃; Normal pressure is reaction 5h down, adds 70-100 ℃ of 2.5kg dimethylolpropionic acid, 4.9kg terepthaloyl moietie temperature control again, and normal pressure is reaction 2h down; After treating that system NCO content reaches theoretical value, be cooled to 40-70 ℃, add 5kg acetone and 1.5kg dimethylethanolamine reaction 45min; Under the condition of 100r/min, add deionized water, 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/ Vilaterm, solidify 10-60min, washing, extract out, wash through toluene again, through oven dry, promptly get the superfine fiber chemical leather base cloth at last through 15-50 ℃ of water-based solidification liquid.Wherein, the water-based solidification liquid is made up of the sodium-chlor of 91kg water, 8kg, the Surfynol DF-75 of 0.4kg, the Levaslip 455 of 0.25kg, the Wet-250 of 0.23kg, the SP-735 of 0.07kg 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
Through 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 of processing through the water-based solidifying process by this aqueous polyurethane simultaneously, mechanical property and feel preferably.
Claims (10)
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.
2. waterborne polyurethane resin according to claim 1; It is characterized in that 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.
3. waterborne polyurethane resin according to claim 1 is characterized in that, described polyol is that 20%-80% polyester polyol, 10%-60% polyether glycol and 5%-20% polyester polyethers polyol are formed by weight percent.
4. waterborne polyurethane resin according to claim 3; It is characterized in that; Described polyester polyethers polyol is based on pinakon, butyleneglycol, NSC 6366, hexanodioic acid and THF homopolymer divalent alcohol synthetic polyester polyethers polyol, and molecular weight is 800～4000.
5. waterborne polyurethane resin according to claim 1 is characterized in that, described hydrophilic compounds is meant and has-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.
6. waterborne polyurethane resin according to claim 1 is characterized in that described low-molecular weight compound comprises trivalent alcohol or tertiary amine.
7. the application of the described waterborne polyurethane resin of claim 1 in the leather-making technology of water-based microfiber synthetic leather impregnation; Waterborne polyurethane resin is contained in the compound sea-island fibre non-woven fabrics of immersion nylon 6/ Vilaterm; Solidify, wash through the water-based solidification liquid; Extract out, wash through toluene again, through oven dry, promptly get the superfine fiber chemical leather base cloth at last.
8. application according to claim 7 is characterized in that: 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% is formed; Described auxiliary addition agent comprises skimmer, flow agent, wetting agent, hand feeling agent and last toner.
9. application according to claim 8 is characterized in that: described complex compound is with Fe
2+, Cu
2+, Pt
2+With Ni be the complex compound of central atom, described inorganic ionic compound is with Na
+, K
+, Ca
2+, Mg
2+, Fe
3+The ionic compound that forms.
10. application according to claim 8 is characterized in that: the time of in the water-based solidification liquid, solidifying is 10-60min, and the temperature of water-based solidification liquid is 15-50 ℃.
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| CN107841881A (en) * | 2017-11-03 | 2018-03-27 | 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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| CN107841881A (en) * | 2017-11-03 | 2018-03-27 | 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 |
| 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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