CN103073987B - Preparation method for organic silicon modified polyester type polyurethane emulsion leather finishing agent - Google Patents
Preparation method for organic silicon modified polyester type polyurethane emulsion leather finishing agent Download PDFInfo
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- CN103073987B CN103073987B CN201310017279.XA CN201310017279A CN103073987B CN 103073987 B CN103073987 B CN 103073987B CN 201310017279 A CN201310017279 A CN 201310017279A CN 103073987 B CN103073987 B CN 103073987B
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Abstract
The invention relates to a preparation method for an organic silicon modified polyester type polyurethane emulsion leather finishing agent. The conventional finishing agent is poor in comprehensive performance. The preparation method comprises the steps as follows: preparing an organic silicon modified cationic polyester type polyurethane emulsion and a finishing agent solution respectively at first and then uniformly mixing by a machine according to the weight ratio of 100:(5-10). The organic silicon modified cationic polyester type polyurethane emulsion is prepared by adding toluene diisocynate and a catalyst into dehydrated polyester polyol, reacting, adding N-methyldiethanolamine for continuing to react, and adding acetone and de-ionized water. The finishing agent solution is prepared by adding hydroxyethyl cellulose into a sodium hydroxide solution, adding epoxypropyl trimethyl ammonium chloride for reaction, washing and drying a solid product, and adding the solid product and polyvinylpyrrolidone into the de-ionized water for dissolution. The preparation method is simpler in process, and the prepared leather finishing agent is excellent in comprehensive performance and good in antibacterial properties.
Description
Technical field
The invention belongs to leather chemistry technical field, relate to a kind of preparation method of hide finishes, be specifically related to a kind of preparation method of organic-silicon-modified cationic polyester type polyurethane modifying casein emulsion leather.
Background technology
Hide finishes is the important leather chemicals of one that outward appearance, use properties and economic worth to leather promote.After leather being covered with paint, lacquer, colour wash, etc. with finishing agent, form the uniform thinfilm protective coating of one deck at leather surface, give the use properties of leather excellence as performances such as solvent resistant, flex endurant, Bearable dry and wet wipe, impact resistance and water-repellancies.Along with the development of science and technology, the demand of people to leather quality is more and more higher, and the quality of leather depends on the quality of hide finishes to a great extent.
Current hide finishes mainly contains nitrocellulose dope, polyhutadiene finishing agent, acrylic resin coating finiss, polyurethane finishing agent, organosilicon finishing agent and corresponding modified product etc., wherein waterborne polyurethane coating agent and its modified product are the research emphasis of numerous researcher, are also the Main way of hide finishes development in the future.As far back as 1972, polyurethane aqueous dispersion body formally used as leather finish by German Bayer company.China to begin one's study waterborne polyurethane coating agent application in the leather from 20 century 70s.Leather research institute of Shenyang City, Tianjin leather research institute and University of Anhui, morning twilight chemical research institute etc. successively successfully develop Aqueous Polyurethane Leather Finishing Agent.Aqueous Polyurethane Leather Finishing Agent in use nontoxic, pollution-free, film forming ability is strong, there is excellent winter hardiness, elasticity and hand feel and drape 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, formed the not resistance to wet rubbing of film, and the physical strength of film and glossiness not high.In recent years, domestic and international many scholars had carried out a large amount of linguistic term 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 linking agent effect, produce certain being cross-linked and forming nucleocapsid structure between polyurethane particulate and polyacrylic ester particulate, the hide finishes of acquisition has good elasticity and intensity.Li Wei, Qin Shufa, Zheng Xuejing, Tang Keyong, Wang Quanjie etc. propose a kind of collagen-modified polyurethane decorative paint for leather (polymer material science and engineering 2008, Vol.24, No.5), graft reaction is carried out with the active group of urethane by amino more on collagen protein, carboxyl and imino-etc., play the natural characteristic utilizing collagen protein, improve the effect of polyurethane finishing agent performance.(leather science and the engineering 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, improve the tensile strength of film, water-fast, resistance to, solvent resistant, acidproof, alkaline-resisting, salt resistant character.But these hide finishess are to the Shortcomings such as cohesive force, levelling property of bottom, and especially sanitation performance can not meet people's requirement.
Summary of the invention
Object of the present invention is not enough for prior art, provides one to have good combination property, and especially feel is smooth and have the preparation method of the organic-silicon-modified cationic polyester 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:
The inventive method prepares organic-silicon-modified cationic polyester type polyurethane emulsion and finish solution first respectively, then organic-silicon-modified cationic polyester type polyurethane emulsion and finish solution is even by weight 100:5 ~ 10 mechanically mixing, must have good combination property, especially feel is smooth and have the organic-silicon-modified cationic polyester type polyurethane modifying casein emulsion leather of sanitary disinfecting performance.
The preparation method of described organic-silicon-modified cationic polyester type polyurethane emulsion is:
Be the polyester polyol of 30 ~ 35 parts by parts by weight, the hydroxy silicon oil of 5 ~ 10 parts dewaters 1 ~ 2h under the vacuum condition of 110 ~ 120 DEG C, then cool the temperature to 50 ~ 70 DEG C; Be 10 ~ 15 parts of tolylene diisocyanates under nitrogen protection by parts by weight, 0.01 ~ 0.5 part of catalyzer adds in the polyester polyol after dehydration, react 2 ~ 3h at 65 ~ 75 DEG C, then cool the temperature to 30 ~ 40 DEG C; Adding parts by weight is 3 ~ 6 parts of N methyldiethanol amines, reacts 2 ~ 4h, then cool the temperature to 40 ~ 50 DEG C at 60 ~ 65 DEG C; Add Glacial acetic acid adjust ph to 5 ~ 7, then adding parts by weight is that 20 ~ 100 parts of acetone dilute, adding parts by weight is again that 80 ~ 100 parts of deionized waters carry out emulsify at a high speed, and vacuum obtains organic-silicon-modified cationic polyester type polyurethane emulsion after extracting acetone solvent;
Described polyester polyol is polyethylene glycol adipate glycol or poly-hexanodioic acid-BDO esterdiol;
The viscosity of described hydroxy silicon oil is less than or equal to 100mPa.S;
Described catalyzer is dibutyl tin dilaurate or stannous octoate.
The preparation method of described finish solution is:
Be that the Natvosol of 1 ~ 3 part joins that parts by weight are 20 ~ 40 parts, concentration is in the sodium hydroxide solution of 1.0 ~ 2.0M, stirring and dissolving under normal temperature by parts by weight; Add the epoxypropyltrimethylchloride chloride that parts by weight are 5 ~ 10 parts, after stirring, be warming up to 80 ~ 85 DEG C, reaction 5 ~ 10h; Regulate pH value to 6 ~ 7 of reaction system with hydrochloric acid, after filtration, obtain solid product; After solid product washing, vacuum-drying, obtain Powdered Natvosol quaternary ammonium salt; Getting parts by weight is that to join parts by weight be dissolve in 100 parts of deionized waters for the Natvosol quaternary ammonium salt of 1 ~ 5 part and 10 ~ 20 parts of polyvinylpyrrolidones, namely obtains finish solution after stirring.
The epoxypropyltrimethylchloride chloride used in the inventive method has good antimicrobial property, epoxypropyltrimethylchloride chloride is combined the Natvosol quaternary ammonium salt formed and not only has good antimicrobial property with Natvosol, and can promote the mortise of hide finishes and leather fiber.The inventive method technique is relatively simple, and the hide finishes excellent combination property of preparation, especially feel is smooth, and has sanitary disinfecting performance.
Embodiment
Prepare organic-silicon-modified cationic polyester type polyurethane emulsion and finish solution respectively.
Prepare 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 organic-silicon-modified cationic polyester type polyurethane emulsion:
Embodiment 1-1.
Dewater 3kg polyethylene glycol adipate glycol and 500g hydroxy silicon oil under the vacuum condition of 110 DEG C 1h, then cools the temperature to 50 DEG C; Add 1kg tolylene diisocyanate, 1g dibutyl tin dilaurate under nitrogen protection, at 65 DEG C, react 3h, then cool the temperature to 30 DEG C; Add 300g N methyldiethanol amine, at 60 DEG C, react 4h, then cool the temperature to 40 DEG C; Add Glacial acetic acid adjust ph to 6, then add 10kg acetone and dilute, then add 10kg deionized water and carry out emulsify at a high speed, vacuum obtains organic-silicon-modified cationic polyester type polyurethane emulsion after extracting acetone solvent.
Embodiment 2-1.
3.5kg is gathered hexanodioic acid-BDO esterdiol and 1kg hydroxy silicon oil to dewater under the vacuum condition of 120 DEG C 2h, then cool the temperature to 70 DEG C; Add 1.5kg tolylene diisocyanate, 50g stannous octoate under nitrogen protection, at 75 DEG C, react 2h, then cool the temperature to 40 DEG C; Add 600g N methyldiethanol amine, at 65 DEG C, react 2h, then cool the temperature to 50 DEG C; Add Glacial acetic acid adjust ph to 7, then add 2kg acetone and dilute, then add 8kg deionized water and carry out emulsify at a high speed, vacuum obtains organic-silicon-modified cationic polyester type polyurethane emulsion after extracting acetone solvent.
Embodiment 3-1.
Dewater 3.2kg polyethylene glycol adipate glycol and 600g hydroxy silicon oil under the vacuum condition of 115 DEG C 1.5h, then cools the temperature to 60 DEG C; 1.2kg tolylene diisocyanate, 5g stannous octoate will be added under nitrogen protection, at 70 DEG C, react 2.5h, then cool the temperature to 35 DEG C; Add 400g N methyldiethanol amine, at 62 DEG C, react 3h, then cool the temperature to 45 DEG C; Add Glacial acetic acid adjust ph to 5, then add 6kg acetone and dilute, then add 9kg deionized water and carry out emulsify at a high speed, vacuum obtains organic-silicon-modified cationic polyester type polyurethane emulsion after extracting acetone solvent.
Embodiment 4-1.
3.4kg is gathered hexanodioic acid-BDO esterdiol and 800g hydroxy silicon oil to dewater under the vacuum condition of 110 DEG C 2h, then cool the temperature to 65 DEG C; Add 1.4kg tolylene diisocyanate, 10g dibutyl tin dilaurate under nitrogen protection, at 73 DEG C, react 2.5h, then cool the temperature to 33 DEG C; Add 500g N methyldiethanol amine, at 63 DEG C, react 3.5h, then cool the temperature to 42 DEG C; Add Glacial acetic acid adjust ph to 6.5, then add 8kg acetone and dilute, then add 10kg deionized water and carry out emulsify at a high speed, vacuum obtains organic-silicon-modified cationic polyester type polyurethane 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 Natvosol being joined 2kg concentration is stirring and dissolving under normal temperature in the sodium hydroxide solution of 2.0M; Add 500g epoxypropyltrimethylchloride chloride, after stirring, be warming up to 80 DEG C, reaction 10h; Regulate the pH value to 6 of reaction system with hydrochloric acid, after filtration, obtain solid product; After solid product washing, vacuum-drying, obtain Powdered Natvosol quaternary ammonium salt; Get 100g Natvosol quaternary ammonium salt and 2kg polyvinylpyrrolidone to join in 10kg deionized water and dissolve, after stirring, namely obtain finish solution.
Embodiment 2-2.
300g Natvosol being joined 4kg concentration is stirring and dissolving under normal temperature in the sodium hydroxide solution of 1.0M; Add 1kg epoxypropyltrimethylchloride chloride, after stirring, be warming up to 85 DEG C, reaction 5h; Regulate the pH value to 7 of reaction system with hydrochloric acid, after filtration, obtain solid product; After solid product washing, vacuum-drying, obtain Powdered Natvosol quaternary ammonium salt; Get 500g Natvosol quaternary ammonium salt and 1kg polyvinylpyrrolidone to join in 10kg deionized water and dissolve, after stirring, namely obtain finish solution.
Embodiment 3-2.
200g Natvosol being joined 3kg concentration is stirring and dissolving under normal temperature in the sodium hydroxide solution of 1.5M; Add 700g epoxypropyltrimethylchloride chloride, after stirring, be warming up to 82 DEG C, reaction 7h; Regulate the pH value to 6.5 of reaction system with hydrochloric acid, after filtration, obtain solid product; After solid product washing, vacuum-drying, obtain Powdered Natvosol quaternary ammonium salt; Get 300g Natvosol quaternary ammonium salt and 1.5kg polyvinylpyrrolidone to join in 10kg deionized water and dissolve, after stirring, namely obtain finish solution.
Embodiment 4-2.
250g Natvosol being joined 3.5kg concentration is stirring and dissolving under normal temperature in the sodium hydroxide solution of 1.2M; Add 800g epoxypropyltrimethylchloride chloride, after stirring, be warming up to 84 DEG C, reaction 9h; Regulate the pH value to 6.5 of reaction system with hydrochloric acid, after filtration, obtain solid product; After solid product washing, vacuum-drying, obtain Powdered Natvosol quaternary ammonium salt; Get 400g Natvosol quaternary ammonium salt and 1.2kg polyvinylpyrrolidone to join in 10kg deionized water and dissolve, after stirring, namely obtain finish solution.
Embodiment I.
Any one obtained organic-silicon-modified cationic polyester type polyurethane emulsion in Example 1-1 ~ 4-1, even by weight 20:1 mechanically mixing with any one obtained finish solution in embodiment 1-2 ~ 4-2, must good combination property be had, and there is the organic-silicon-modified cationic polyester type polyurethane modifying casein emulsion leather of sanitary disinfecting.
Embodiment II.
Any one obtained organic-silicon-modified cationic polyester type polyurethane emulsion in Example 1-1 ~ 4-1, even by weight 15:1 mechanically mixing with any one obtained finish solution in embodiment 1-2 ~ 4-2, must good combination property be had, and there is the organic-silicon-modified cationic polyester type polyurethane modifying casein emulsion leather of sanitary disinfecting.
Embodiment III.
Any one obtained organic-silicon-modified cationic polyester type polyurethane emulsion in Example 1-1 ~ 4-1, even by weight 12:1 mechanically mixing with any one obtained finish solution in embodiment 1-2 ~ 4-2, must good combination property be had, and there is the organic-silicon-modified cationic polyester type polyurethane modifying casein emulsion leather of sanitary disinfecting.
Embodiment IV.
Any one obtained organic-silicon-modified cationic polyester type polyurethane emulsion in Example 1-1 ~ 4-1, even by weight 10:1 mechanically mixing with any one obtained finish solution in embodiment 1-2 ~ 4-2, must good combination property be had, and there is the organic-silicon-modified cationic polyester type polyurethane modifying casein emulsion leather of sanitary disinfecting.
Claims (3)
1. the preparation method of organosilicon modified polyester type polyurethane modifying casein emulsion leather, it is characterized in that the method prepares organosilicon modified polyester type polyurethane emulsion and finish solution first respectively, then organosilicon modified polyester type polyurethane emulsion and finish solution is even by weight 100:5 ~ 10 mechanically mixing, obtain organosilicon modified polyester type polyurethane modifying casein emulsion leather;
The preparation method of described organosilicon modified polyester type polyurethane emulsion is:
Be the polyester polyol of 30 ~ 35 parts by parts by weight, the hydroxy silicon oil of 5 ~ 10 parts dewaters 1 ~ 2h under the vacuum condition of 110 ~ 120 DEG C, then cool the temperature to 50 ~ 70 DEG C; Be 10 ~ 15 parts of tolylene diisocyanates under nitrogen protection by parts by weight, 0.01 ~ 0.5 part of catalyzer adds in the polyester polyol after dehydration, react 2 ~ 3h at 65 ~ 75 DEG C, then cool the temperature to 30 ~ 40 DEG C; Adding parts by weight is 3 ~ 6 parts of N methyldiethanol amines, reacts 2 ~ 4h, then cool the temperature to 40 ~ 50 DEG C at 60 ~ 65 DEG C; Add Glacial acetic acid adjust ph to 5 ~ 7, then adding parts by weight is that 20 ~ 100 parts of acetone dilute, adding parts by weight is again that 80 ~ 100 parts of deionized waters carry out emulsify at a high speed, and vacuum obtains organosilicon modified polyester type polyurethane emulsion after extracting acetone solvent;
The preparation method of described finish solution is:
Be that the Natvosol of 1 ~ 3 part joins that parts by weight are 20 ~ 40 parts, concentration is in the sodium hydroxide solution of 1.0 ~ 2.0M, stirring and dissolving under normal temperature by parts by weight; Add the epoxypropyltrimethylchloride chloride that parts by weight are 5 ~ 10 parts, after stirring, be warming up to 80 ~ 85 DEG C, reaction 5 ~ 10h; Regulate pH value to 6 ~ 7 of reaction system with hydrochloric acid, after filtration, obtain solid product; After solid product washing, vacuum-drying, obtain Powdered Natvosol quaternary ammonium salt; Getting parts by weight is that to join parts by weight be dissolve in 100 parts of deionized waters for the Natvosol quaternary ammonium salt of 1 ~ 5 part and 10 ~ 20 parts of polyvinylpyrrolidones, namely obtains finish solution after stirring;
Described polyester polyol is polyethylene glycol adipate glycol or poly-hexanodioic acid-BDO esterdiol.
2. the preparation method of organosilicon modified polyester 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 polyester type polyurethane modifying casein emulsion leather as claimed in claim 1, is characterized in that: described catalyzer 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 |
| CN103804613B (en) * | 2014-02-20 | 2015-11-18 | 江西省科学院应用化学研究所 | A kind of preparation method of organic-silicon-modified cation aqueous polyurethane antimicrobial emulsion |
| CN103965431B (en) * | 2014-05-16 | 2016-08-17 | 中国科学院兰州化学物理研究所 | Synthetic resin, preparation method and utilize back coating liquid prepared by this synthetic resin |
| CN104559730B (en) * | 2015-01-07 | 2017-05-17 | 佛山市顺德区国精合成材料有限公司 | Preparation method of organic silicon modified polyurethane resin coating |
| CN105482439A (en) * | 2016-01-07 | 2016-04-13 | 华南理工大学 | Silicone oil modified polyurethane feeling agent and preparation method and application thereof |
| CN107383375B (en) * | 2017-08-11 | 2021-03-30 | 烟台德邦科技股份有限公司 | Preparation method of organic silicon modified polyester for modifying TPU (thermoplastic polyurethane) |
| CN108130735A (en) * | 2017-12-07 | 2018-06-08 | 科凯精细化工（上海）有限公司 | A kind of dacron antibacterial hydrophilic finishing agent and preparation method thereof |
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| CN110540629A (en) * | 2019-09-30 | 2019-12-06 | 陕西科技大学 | Preparation method of organosilicon modified cationic waterborne polyurethane waterproofing agent |
| CN111321258A (en) * | 2020-02-19 | 2020-06-23 | 漳州信德皮革有限公司 | Production process of leather |
| CN114106942A (en) * | 2020-08-31 | 2022-03-01 | 万华化学集团股份有限公司 | Leather microemulsion cleaning agent composition containing aqueous polyurethane and preparation method thereof |
| CN113789114A (en) * | 2021-09-17 | 2021-12-14 | 卢超 | Self-repairing antibacterial polyurethane coating and preparation method thereof |
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