CN103088644B - Method for preparing organosilicone modified polyether type polyurethane emulsion leather finishing agent - Google Patents
Method for preparing organosilicone modified polyether type polyurethane emulsion leather finishing agent Download PDFInfo
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- CN103088644B CN103088644B CN201310017308.2A CN201310017308A CN103088644B CN 103088644 B CN103088644 B CN 103088644B CN 201310017308 A CN201310017308 A CN 201310017308A CN 103088644 B CN103088644 B CN 103088644B
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Abstract
The invention relates to a method for preparing an organosilicone modified polyether type polyurethane emulsion leather finishing agent. The existing finishing agent has poor combination property. The method comprises the following steps of firstly preparing the organosilicone modified cation polyether type polyurethane emulsion and a finishing agent solution respectively, and mechanically mixing uniformly according to weight ratio of 100:5-10, wherein the preparation method for the organosilicone modified cation polyether type polyurethane emulsion comprises the following steps of adding toluene diisocynate and a catalyst into dehydrated polyoxyethylene dihydric alcohol, reacting, adding N-methyldiethanolamine for further reaction, and then adding acetone and deionized water; and the preparation method for the finishing agent solution comprises the following steps of adding hydroxyethyl cellulose into sodium hydroxide solution, adding glycidyl trimethyl ammonium chloride for reaction, then washing and drying the solid product, and adding the solid product and polyvinylpyrrolidone into the deionized water solution. The method has relatively simple processes; and the prepared leather finishing agent not only has excellent combination property, but also has good antibacterial property.
Description
Technical field
The invention belongs to leather chemistry technical field, relate to a kind of preparation method of leather finishing agent, be specifically related to a kind of preparation method of organic-silicon-modified cation polyether type polyurethane modifying casein emulsion leather.
Background technology
Leather finishing agent is a kind of important leather chemicals that outward appearance, serviceability and the economic worth to leather promotes.After leather being covered with paint, lacquer, colour wash, etc. with finishing agent, at leather surface, form the uniform thinfilm protective coating of one deck, give the serviceability of leather excellence as performances such as resistance to solvent, resistance to deflection, Bearable dry and wet wipe, impact resistance and water proofing properties.Along with scientific and technical development, people are more and more higher to the demand of leather quality, and the quality of leather depends on the quality of leather finishing agent to a great extent.
Leather finishing agent mainly contains dope, polybutadiene finishing agent, acrylic resin coating finiss, polyurethane finishing agent, organosilicon finishing agent and corresponding modified product etc. at present, wherein waterborne polyurethane coating agent with and modified product be the research emphasis of numerous researchers, be also the main direction of in the future leather finishing agent development.As far back as 1972, German Bayer company was formally used polyurethane aqueous dispersion body as leather finish.China is from the application of waterborne polyurethane coating agent leather that begin one's study of 20 century 70s.The priorities such as leather research institute, Shenyang City, leather research institute, Tianjin and University of Anhui, morning twilight chemical research institute are successfully developed Aqueous Polyurethane Leather Finishing Agent.Aqueous Polyurethane Leather Finishing Agent in use nontoxic, pollution-free, film forming ability is strong, there is excellent cold resistance, elasticity and comfortable feel nature, but because containing an a certain amount of COOH, an OH, the first-class hydrophilic radical of an O in aqueous polyurethane molecular structure, the not moisture-proof of filming forming is wiped, and the mechanical strength of filming and glossiness not high.In recent years, domestic and international many scholars had carried out a large amount of improvement research to Aqueous Polyurethane Leather Finishing Agent.Wang Nan invents a kind of composite dubbing of polyurethane-polyacrylate for leather (Chinese invention patent CN1046952C), polyaminoester emulsion and polyacrylate dispersion are carried out compound, under crosslinking agent effect, between polyurethane particulate and polyacrylate particulate, produce certain nucleocapsid structure that is cross-linked and forms, the leather finishing agent of acquisition has good elasticity and intensity.Li Wei, Qin Shufa, Zheng Xuejing, Tang Keyong, Wang Quanjie etc. have proposed a kind of collagen-modified polyurethane decorative paint for leather (polymer material science and engineering 2008, Vol.24, No.5), by amino more on collagen, carboxyl and imino group etc., carry out graft reaction with the active group of polyurethane, play the natural characteristic that utilizes collagen, improve the effect of polyurethane finishing agent performance.(leather science and the engineerings 2011 such as Dong Wei, Chen Zheng, Xin Zhongyin, Wu Yangyuan, Vol.21, No.4) adopt mechanical blending legal system for epoxy resin modified aqueous polyurethane finishing agent, improved the tensile strength of filming, water-fast, resistance to, resistance to solvent, acidproof, alkaline-resisting, salt resistant character.Yet these leather finishing agents can not meet people's requirement to Shortcomings, especially sanitation performances such as the cohesive force of bottom, levelabilities.
Summary of the invention
Object of the present invention is not enough for prior art, provides a kind of good combination property that has, especially feel smooth and have a preparation method of the organic-silicon-modified cation polyether type polyurethane modifying casein emulsion leather of sanitary disinfecting performance.
For solving the problems of the technologies described above, the method applied in the present invention step is as follows:
Prepare organosilicon modified cation EU emulsion and finish solution first respectively, then organic-silicon-modified cation polyether type polyurethane emulsion and finish solution is even by weight 100:5～10 mechanical mixture, must have good combination property, especially feel is smooth and have an organic-silicon-modified cation polyether type polyurethane modifying casein emulsion leather of sanitary disinfecting performance.
The preparation method of described organic-silicon-modified cation polyether type polyurethane emulsion is:
By parts by weight, be the polyoxyethylene glycol of 25～30 parts, the hydroxy silicon oil of 5～10 parts 1～2h that dewaters under the vacuum condition of 110～120 ℃, then cool the temperature to 50～70 ℃; Under nitrogen protection, by parts by weight, be that 10～15 parts of toluene di-isocyanate(TDI)s, 0.01～0.5 part of catalyst add in the polyoxyethylene glycol after dehydration, react 2～3h at 75～85 ℃, then cool the temperature to 30～40 ℃; Adding parts by weight is 3～6 parts of N methyldiethanol amines, reacts 2～4h at 60～65 ℃, then cools the temperature to 40～50 ℃; Add glacial acetic acid to regulate pH value to 5～7, then adding parts by weight is that 20～100 parts of acetone dilute, then to add parts by weight be that 80～100 parts of deionized waters carry out emulsify at a high speed, and vacuum obtains EU emulsion after extracting acetone solvent;
The viscosity of described hydroxy silicon oil is less than or equal to 100mPa.S;
Described catalyst is dibutyl tin dilaurate or stannous octoate.
The preparation method of described finish solution is:
It is in 20～40 parts, the concentration sodium hydroxide solution that is 1.0～2.0M that the hydroxyethylcellulose that is 1～3 part by parts by weight joins parts by weight, stirring and dissolving under normal temperature; Adding parts by weight is the epoxypropyltrimethylchloride chloride of 5～10 parts, is warming up to 80～85 ℃ after stirring, reaction 5～10h; With hydrochloric acid, regulate pH value to 6～7 of reaction system, after filtering, obtain solid product; By after solid product washing, vacuumize, obtain Powdered hydroxyethylcellulose quaternary ammonium salt; Getting parts by weight and be the hydroxyethylcellulose quaternary ammonium salt of 1～5 part and 10～20 parts of polyvinylpyrrolidones, to join parts by weight be to dissolve in 100 parts of deionized waters, obtains finish solution after stirring.
The epoxypropyltrimethylchloride chloride using in the inventive method has good anti-microbial property, epoxypropyltrimethylchloride chloride is combined the hydroxyethylcellulose quaternary ammonium salt forming and is not only had good anti-microbial property with hydroxyethylcellulose, and can promote the strong bonded of leather finishing agent and leather fiber.The inventive method technique is relatively simple, the leather finishing agent excellent combination property of preparation, and especially feel is smooth, and has sanitary disinfecting performance.
The specific embodiment
Prepare respectively organosilicon modified cation EU emulsion and finish solution.
The specific embodiment following (hydroxy silicon oil in following examples is the low-molecular-weight hydroxyl silicone oil that viscosity is less than or equal to 100mPa.S) of preparing organosilicon modified cation EU emulsion:
Embodiment 1-1.
By 2.5kg polyoxyethylene glycol and the 500g hydroxy silicon oil 1h that dewaters, then cool the temperature to 50 ℃ under the vacuum condition of 110 ℃; Under nitrogen protection, add 1kg toluene di-isocyanate(TDI) and 1g dibutyl tin dilaurate, react 3h at 75 ℃, then cool the temperature to 30 ℃; Add 300g N methyldiethanol amine, react 4h at 60 ℃, then cool the temperature to 40 ℃; Add glacial acetic acid to regulate pH value to 6, then add 10kg acetone to dilute, then add 10kg deionized water to carry out emulsify at a high speed, vacuum obtains EU emulsion after extracting acetone solvent.
Embodiment 2-1.
By 3kg polyoxyethylene glycol and the 1kg hydroxy silicon oil 2h that dewaters, then cool the temperature to 70 ℃ under the vacuum condition of 120 ℃; Under nitrogen protection, add 1.5kg toluene di-isocyanate(TDI) and 50g stannous octoate, react 2h at 85 ℃, then cool the temperature to 40 ℃; Add 600g N methyldiethanol amine, react 2h at 65 ℃, then cool the temperature to 50 ℃; Add glacial acetic acid to regulate pH value to 7, then add 2kg acetone to dilute, then add 8kg deionized water to carry out emulsify at a high speed, vacuum obtains EU emulsion after extracting acetone solvent.
Embodiment 3-1.
By 2.6kg polyoxyethylene glycol and the 600g hydroxy silicon oil 1.5h that dewaters, then cool the temperature to 60 ℃ under the vacuum condition of 115 ℃; Under nitrogen protection, add 1.2kg toluene di-isocyanate(TDI) and 5g stannous octoate, react 2.5h at 80 ℃, then cool the temperature to 35 ℃; Add 500g N methyldiethanol amine, react 3h at 62 ℃, then cool the temperature to 45 ℃; Add glacial acetic acid to regulate pH value to 5, then add 5kg acetone to dilute, then add 9kg deionized water to carry out emulsify at a high speed, vacuum obtains EU emulsion after extracting acetone solvent.
Embodiment 4-1.
By 2.8kg polyoxyethylene glycol and the 800g hydroxy silicon oil 2h that dewaters, then cool the temperature to 65 ℃ under the vacuum condition of 110 ℃; Under nitrogen protection, add 1.1kg toluene di-isocyanate(TDI) and 10g dibutyl tin dilaurate, react 2.5h at 82 ℃, then cool the temperature to 38 ℃; Add 400g N methyldiethanol amine, react 2.5h at 63 ℃, then cool the temperature to 42 ℃; Add glacial acetic acid to regulate pH value to 6.5, then add 8kg acetone to dilute, then add 10kg deionized water to carry out emulsify at a high speed, vacuum obtains EU emulsion after extracting acetone solvent.
(model specification of the polyvinylpyrrolidone in following examples is PVP-K to the specific embodiment of preparation finish solution method as follows
15or PVP-K
30):
Embodiment 1-2.
100g hydroxyethylcellulose is joined in the sodium hydroxide solution that 2kg concentration is 2.0M to stirring and dissolving under normal temperature; Add 500g epoxypropyltrimethylchloride chloride, after stirring, be warming up to 80 ℃, reaction 10h; With hydrochloric acid, regulate the pH value to 6 of reaction system, after filtering, obtain solid product; By after solid product washing, vacuumize, obtain Powdered hydroxyethylcellulose quaternary ammonium salt; Get 100g hydroxyethylcellulose quaternary ammonium salt and 2kg polyvinylpyrrolidone and join in 10kg deionized water and dissolve, after stirring, obtain finish solution.
Embodiment 2-2.
300g hydroxyethylcellulose is joined in the sodium hydroxide solution that 4kg concentration is 1.0M to stirring and dissolving under normal temperature; Add 1kg epoxypropyltrimethylchloride chloride, after stirring, be warming up to 85 ℃, reaction 5h; With hydrochloric acid, regulate the pH value to 7 of reaction system, after filtering, obtain solid product; By after solid product washing, vacuumize, obtain Powdered hydroxyethylcellulose quaternary ammonium salt; Get 500g hydroxyethylcellulose quaternary ammonium salt and 1kg polyvinylpyrrolidone and join in 10kg deionized water and dissolve, after stirring, obtain finish solution.
Embodiment 3-2.
200g hydroxyethylcellulose is joined in the sodium hydroxide solution that 3kg concentration is 1.5M to stirring and dissolving under normal temperature; Add 700g epoxypropyltrimethylchloride chloride, after stirring, be warming up to 82 ℃, reaction 7h; With hydrochloric acid, regulate the pH value to 6.5 of reaction system, after filtering, obtain solid product; By after solid product washing, vacuumize, obtain Powdered hydroxyethylcellulose quaternary ammonium salt; Get 300g hydroxyethylcellulose quaternary ammonium salt and 1.5kg polyvinylpyrrolidone and join in 10kg deionized water and dissolve, after stirring, obtain finish solution.
Embodiment 4-2.
250g hydroxyethylcellulose is joined in the sodium hydroxide solution that 3.5kg concentration is 1.2M to stirring and dissolving under normal temperature; Add 800g epoxypropyltrimethylchloride chloride, after stirring, be warming up to 84 ℃, reaction 9h; With hydrochloric acid, regulate the pH value to 6.5 of reaction system, after filtering, obtain solid product; By after solid product washing, vacuumize, obtain Powdered hydroxyethylcellulose quaternary ammonium salt; Get 400g hydroxyethylcellulose quaternary ammonium salt and 1.2kg polyvinylpyrrolidone and join in 10kg deionized water and dissolve, after stirring, obtain finish solution.
Embodiment I.
Get the organic-silicon-modified cation polyether type polyurethane emulsion that in embodiment 1-1～4-1, any one makes, even by weight 20:1 mechanical mixture with any one finish solution making in embodiment 1-2～4-2, must there is good combination property, and there is the organic-silicon-modified cation polyether type polyurethane modifying casein emulsion leather of sanitary disinfecting.
Embodiment II.
Get the organic-silicon-modified cation polyether type polyurethane emulsion that in embodiment 1-1～4-1, any one makes, even by weight 15:1 mechanical mixture with any one finish solution making in embodiment 1-2～4-2, must there is good combination property, and there is the organic-silicon-modified cation polyether type polyurethane modifying casein emulsion leather of sanitary disinfecting.
Embodiment III.
Get the organic-silicon-modified cation polyether type polyurethane emulsion that in embodiment 1-1～4-1, any one makes, even by weight 12:1 mechanical mixture with any one finish solution making in embodiment 1-2～4-2, must there is good combination property, and there is the organic-silicon-modified cation polyether type polyurethane modifying casein emulsion leather of sanitary disinfecting.
Embodiment IV.
Get the organic-silicon-modified cation polyether type polyurethane emulsion that in embodiment 1-1～4-1, any one makes, even by weight 10:1 mechanical mixture with any one finish solution making in embodiment 1-2～4-2, must there is good combination property, and there is the organic-silicon-modified cation polyether type polyurethane modifying casein emulsion leather of sanitary disinfecting.
Claims (3)
1. the preparation method of organosilicon modified polyether type polyurethane modifying casein emulsion leather, it is characterized in that the method prepares first respectively organosilicon modified polyether type polyurethane emulsion and finish solution, then organosilicon modified polyether type polyurethane emulsion and finish solution is even by weight 100:5～10 mechanical mixture, obtain organosilicon modified polyether type polyurethane modifying casein emulsion leather;
The preparation method of described organosilicon modified polyether type polyurethane emulsion is:
By parts by weight, be the polyoxyethylene glycol of 25～30 parts, the hydroxy silicon oil of 5～10 parts 1～2h that dewaters under the vacuum condition of 110～120 ℃, then cool the temperature to 50～70 ℃; Under nitrogen protection, by parts by weight, be that 10～15 parts of toluene di-isocyanate(TDI)s, 0.01～0.5 part of catalyst add in the polyoxyethylene glycol after dehydration, react 2～3h at 75～85 ℃, then cool the temperature to 30～40 ℃; Adding parts by weight is 3～6 parts of N methyldiethanol amines, reacts 2～4h at 60～65 ℃, then cools the temperature to 40～50 ℃; Add glacial acetic acid to regulate pH value to 5～7, then adding parts by weight is that 20～100 parts of acetone dilute, then to add parts by weight be that 80～100 parts of deionized waters carry out emulsify at a high speed, and vacuum obtains EU emulsion after extracting acetone solvent;
The preparation method of described finish solution is:
First by parts by weight, be the hydroxyethylcellulose of 1～3 part to join parts by weight be in 20～40 parts, the concentration sodium hydroxide solution that is 1.0～2.0M, stirring and dissolving under normal temperature; Adding parts by weight is the epoxypropyltrimethylchloride chloride of 5～10 parts, is warming up to 80～85 ℃ after stirring, reaction 5～10h; With hydrochloric acid, regulate pH value to 6～7 of reaction system, after filtering, obtain solid product; By after solid product washing, vacuumize, obtain Powdered hydroxyethylcellulose quaternary ammonium salt; Getting parts by weight and be the hydroxyethylcellulose quaternary ammonium salt of 1～5 part and 10～20 parts of polyvinylpyrrolidones, to join parts by weight be to dissolve in 100 parts of deionized waters, obtains finish solution after stirring.
2. the preparation method of organosilicon modified polyether type polyurethane modifying casein emulsion leather as claimed in claim 1, is characterized in that: the viscosity of described hydroxy silicon oil is less than or equal to 100mPa.S.
3. the preparation method of organosilicon modified polyether type polyurethane modifying casein emulsion leather as claimed in claim 1, is characterized in that: described catalyst is dibutyl tin dilaurate or stannous octoate.
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| CN103539916B (en) * | 2013-09-30 | 2015-07-15 | 上海乘鹰新材料有限公司 | Self-defoaming water-based polyurethane emulsion |
| CN112279994B (en) * | 2020-11-06 | 2022-08-16 | 江苏海洋大学 | Application of polyurethane-based interpenetrating network polymer in surface modification of medical catheter |
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| CN1693578A (en) * | 2005-05-25 | 2005-11-09 | 浙江科技学院 | Poly siloxane leather coating material and its preparation method |
| CN101225150A (en) * | 2008-01-28 | 2008-07-23 | 浙江大学 | Method for synthesizing water-dispersion organosilicon-polyurethane block copolymer |
| CN102417582A (en) * | 2011-11-01 | 2012-04-18 | 吴江市北厍盛源纺织品助剂厂 | Preparation method of cationic polyurethane organosilicon weaving finishing agent |
| CN102517900A (en) * | 2011-09-29 | 2012-06-27 | 江苏君锐高新材料有限公司 | Finishing agent capable of endowing thick and smooth feel style and preparation method of special polysiloxane |
| CN102786649A (en) * | 2012-07-06 | 2012-11-21 | 淮安凯悦科技开发有限公司 | Aqueous fluorine-silicon polyurethane resin prepolymer dispersion solution and aqueous artificial leather fog washing bright finishing agent |
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2013
- 2013-01-17 CN CN201310017308.2A patent/CN103088644B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3983291A (en) * | 1975-01-02 | 1976-09-28 | Minnesota Mining And Manufacturing Company | Silanol-containing urethane dispersions |
| CN1693578A (en) * | 2005-05-25 | 2005-11-09 | 浙江科技学院 | Poly siloxane leather coating material and its preparation method |
| CN101225150A (en) * | 2008-01-28 | 2008-07-23 | 浙江大学 | Method for synthesizing water-dispersion organosilicon-polyurethane block copolymer |
| CN102517900A (en) * | 2011-09-29 | 2012-06-27 | 江苏君锐高新材料有限公司 | Finishing agent capable of endowing thick and smooth feel style and preparation method of special polysiloxane |
| CN102417582A (en) * | 2011-11-01 | 2012-04-18 | 吴江市北厍盛源纺织品助剂厂 | Preparation method of cationic polyurethane organosilicon weaving finishing agent |
| CN102786649A (en) * | 2012-07-06 | 2012-11-21 | 淮安凯悦科技开发有限公司 | Aqueous fluorine-silicon polyurethane resin prepolymer dispersion solution and aqueous artificial leather fog washing bright finishing agent |
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