CN106432667A - 自消光柔感水性聚氨酯皮革涂饰剂及制备方法 - Google Patents
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Abstract
本发明自消光柔感水性聚氨酯皮革涂饰剂及其制备方法,原料按重量配比:(1)将氢化二苯基甲烷二异氰酸酯30‑50、六亚甲基二异氰酸酯三聚体5‑20、线性双羟烷基硅氧烷5‑20、聚碳酸亚丙酯二醇30‑60、聚环氧乙烷二醇30‑50、2,2,4‑三甲基‑1,3戊二醇3‑5、二羟甲基丁酸2‑4加入反应釜中,升温至70‑90℃,反应4—6小时;(2)降温至50‑60℃,加入三乙胺1‑3,反应25‑35分钟;(3)加入去离子水430‑850,高速分散后加入水合肼4‑6,搅拌升温至50‑60℃,反应1‑2小时制得,产品不仅消光和柔感性好,具有优异的耐磨性、耐溶剂性。
Description
技术领域
本发明涉及的是一种水性聚氨酯皮革涂饰剂及制备方法,特别是一种自消光柔感水性聚氨酯皮革涂饰剂及制备方法。
背景技术
随着社会的发展,环保越来越受到人们的重视,传统聚氨酯皮革涂饰剂多为溶剂型聚氨酯,对环境污染严重,水性无溶剂产品对环境无污染、对人体无伤害,所以水性聚氨酯代替溶剂型聚氨酯已成为必然趋势。
消光型水性聚氨酯皮革涂饰剂分为添加消光剂和自消光两种水性聚氨酯皮革涂饰剂。目前添加消光剂和现有的自消光水性聚氨酯皮革涂饰剂都具有胶膜表面粗糙,影响了胶膜的耐刮性,耐候性,耐水性,且手感不够光滑细腻,乳液稳定性不理想。
CN103740250A专利公开了一种‘自消光皮革水性聚氨酯涂饰剂的制备方法’,该方法合成了一种具有交联结构较大粒径的聚氨酯A组分,使其与粒径较小的B组分进行混合。其中A组分分子结构支链较多,胶束粒子具有较大体积,其比重比B组分小,在成膜过程上浮在膜表面,使膜表面具有较高的粗糙度,从而达到消光效果。这种双组份不仅不便于工艺生产,而且成膜手感较硬,且粗糙,并不能完全像真皮具有细腻的手感。
CN104974324A专利公开了‘一种反应自消光型水性聚氨酯树脂及其制备方法与应用’,该专利公开了了一种大粒径的水性聚氨酯的制备方法,使涂膜干燥失水后收缩,致使表面涂膜粗糙度增加达到消光效果。这种大粒径的水性聚氨酯乳液一方面是稳定性较差,容易沉淀析出,另一方面大粒径致使胶膜成膜不连续影响胶膜的力学性能。
CN105506997A专利公开了‘一种消光型水性聚氨酯皮革涂饰剂及其制备方法’,其提供了一种利用引入有机硅单体合成自消光水性聚氨酯皮革涂饰剂的制备方法,该方法合成的水性聚氨酯由于没有加入多官能团结构的原料,所以属于线性结构的水性聚氨酯。而分子结构为线性的水性聚氨酯不仅在耐水,耐磨,耐溶剂等性能上不理想,且也没有接近真皮那种细腻的手感。
发明内容
本发明的目的是提供一种自消光柔感水性聚氨酯皮革涂饰剂及制备方法,且具有优异的耐磨性、耐溶剂性。
本发明自消光柔感水性聚氨酯皮革涂饰剂:
原料按重量配比:
氢化二苯基甲烷二异氰酸酯 (H12MDI) 30-50
六亚甲基二异氰酸酯三聚体(HDI三聚体) 5-20
线性双羟烷基硅氧烷 5-20
聚碳酸亚丙酯二醇 30-60
聚环氧乙烷二醇(分子量2000) 30-50
2,2,4-三甲基-1,3戊二醇 3-5
二羟甲基丁酸 2-4
三乙胺 1-3
水合肼 4-6
去离子水 430-850
经预聚反应、中和反应、扩链反应工艺制成;
产品化学指标如下:
外 观:半透明乳液
离子性:阴
pH 值:7±1
含固量:20±1%。
所述线性双羟烷基硅氧烷:为广州市斯洛柯高分子聚合物有限公司的Silok 3316产品。
所述聚碳酸亚丙酯二醇:为广东达志环保科技有限公司的PPC2000产品。
本发明自消光柔感水性聚氨酯皮革涂饰剂及制备方法:
原料按重量配比:
制备方法:
(1)预聚反应:将氢化二苯基甲烷二异氰酸酯30-50、六亚甲基二异氰酸酯三聚体5-20、线性双羟烷基硅氧烷5-20、聚碳酸亚丙酯二醇30-60、聚环氧乙烷二醇30-50、2,2,4-三甲基-1,3戊二醇3-5、二羟甲基丁酸2-4加入反应釜中,升温至70-90℃,反应4—6小时;
(2)中和反应:降温至50-60℃,加入三乙胺1-3,反应25-35分钟;
(3)扩链反应:加入去离子水430-850,高速分散后加入水合肼4-6,搅拌升温至50-60℃,反应1-2小时,得产品。
所述线性双羟烷基硅氧烷:为广州市斯洛柯高分子聚合物有限公司的Silok 3316产品。
所述聚碳酸亚丙酯二醇:为广东达志环保科技有限公司的PPC2000产品。
本发明自消光柔感水性聚氨酯皮革涂饰剂乳液生产简单方便,生产成本低,自消光,高耐磨,耐溶剂性好,触感绵柔滑爽,水性环保。
本发明原料组合中的六亚甲基二异氰酸酯三聚体具有环状三官能团结构,合成过程中环状三官能结构稳定,形成高聚物后仍能存在,此结构可以使聚氨酯形成交联网状结构,使成膜过程中与其他原料的相容性下降,结晶度提高致使成膜透明度下降,达到良好的消光效果并且大幅度提升了产品的弹性,耐水性、耐溶剂性、耐磨性能。
普通聚酯中酯键容易水解,使产品不稳定,而本发明选用碳酸亚丙酯二醇是二氧化碳与环氧丙烷共聚得到,它是一种新型热塑性脂肪族聚碳酸酯,它不仅有普通聚碳酸酯优异的耐水解性,耐溶剂性,耐拉伸性,耐磨性等特点,还具有良好的生物相容性和降解性,并且具有和聚环氧乙烷二醇相容性较差的特点,使成膜不透明,具有一定的消光性。
本发明使用的线性双羟烷基硅氧烷提供柔滑链段,线性双羟烷基硅氧烷结构具有特殊性,它是由硅原子和氧原子交替组成稳定骨架的高分子。由于Si-C键的键能也比较高,单纯的热运动很难使Si-O键和Si-C键发生断裂,因而聚硅氧烷具有良好的热稳定性。另外线性双羟烷基硅氧烷的主链由硅氧键组成,其键距长、键角和键能大,故硅氧烷非常柔顺,其粘流活化能很小,当温度降低到-136℃时,线性双羟烷基硅氧烷还存在链段运动,耐低温、耐寒性一直保持很好。其次,线性双羟烷基硅氧烷主链上无不饱和键,而Si-O-Si键对氧、臭氧及紫外线等十分稳定,因而具有良好的耐候性。从分子结构观察,线性双羟烷基硅氧烷中羟基以σ键与主链上的硅原子相连,增加了自由旋转的空间体积,羟基的氢原子和水氢原子相互排斥,是水分子难以与亲水的氧结合,因而提供了疏水效果。综上,线性双羟烷基硅氧烷具有良好柔软性、耐热性、耐寒性、耐候性、疏水性等。且本发明采用了分子量为800的小分子线性双羟烷基硅氧烷,它由于分子量小具有很高的反应活性,克服了普通线性双羟烷基硅氧烷很难与多异氰酸酯反应的缺点,并且与大分子量的聚二元醇比如本发明所用的碳酸亚丙酯二醇和聚环氧乙烷二醇相容性较差致使成膜不透明具有一定的消光性。
本发明采用的聚环氧乙烷二醇,由于聚环氧乙烷二醇的亲水链段的亲水性致使成膜过程中线性双羟烷基硅氧烷更容易在膜的表面舒展达到绵柔的滑爽手感,并且聚环氧乙烷二醇的结晶度较高常温为固态与常温为液态的聚碳酸亚丙酯二醇相容性较差,成膜结晶性提高,使胶膜具有很强的消光效果。
本发明采用2,2,4-三甲基-1,3戊二醇进行扩链,由于含有侧链甲基结构增加了产品分子间斥力,降低了乳液粘度,使水分散更容易,同时进一步增加了耐水、耐溶剂、耐磨性能;
本发明选用阴离子亲水基团和非离子亲水基团协同效用,乳液稳定性得到进一步加强,发明的产品制得的胶膜渗透性更好,与皮革的结合牢度好。
本发明合成中选用了不同种类的羟基原料使产品具有自消光,高耐磨,耐溶剂,触感绵柔等性能。
本发明具有良好的工艺实施性,环保无污染。
具体实施方式
实施例1
制备方法:
1、预聚反应:将氢化二苯基甲烷二异氰酸酯30、六亚甲基二异氰酸酯三聚体20、线性双羟烷基硅氧烷15、聚碳酸亚丙酯二醇30、聚环氧乙烷二醇50、2,2,4-三甲基-1,3戊二醇4、二羟甲基丁酸2加入反应釜中,升温至70℃,反应6小时;
2、中和反应:上述预聚体降温至50℃,加入三乙胺1.4,反应35分钟;
3、扩链反应:加入去离子水608,高速分散后加入水合肼4.6,继续搅拌,升温至50℃,反应2小时得产品,产品外观状态为半透明,固含量为20.2%。
该实施例产品由于六亚甲基二异氰酸酯三聚体较多,提高了产品的交联度,致使产品的消光性,耐水性,耐溶剂性,耐磨性大幅度提升。
实施例2
1、预聚反应:将氢化二苯基甲烷二异氰酸酯35、六亚甲基二异氰酸酯三聚体15、线性双羟烷基硅氧烷5、聚碳酸亚丙酯二醇50、聚环氧乙烷二醇45、2,2,4-三甲基-1,3戊二醇5、二羟甲基丁酸2加入反应釜中,升温至80℃,反应5小时;
2、中和反应:上述预聚体降温至50℃,加入三乙胺1.4,反应35分钟;
3、扩链反应:加入去离子水637,高速分散后加入水合肼4.8,继续搅拌升温至55℃,反应1.5小时,得产品,产品外观状态为半透明,固含量为20.1%。
该实施例产品由于原料配比中2,2,4-三甲基-1,3戊二醇和二羟甲基丁酸比例较大,少量的二羟甲基丁酸可以提高产品的耐水性。
实施例3
制备方法:
1、预聚反应:将氢化二苯基甲烷二异氰酸酯40、六亚甲基二异氰酸酯三聚体10、线性双羟烷基硅氧烷10、聚碳酸亚丙酯二醇60、聚环氧乙烷二醇40、2,2,4-三甲基-1,3戊二醇3、二羟甲基丁酸3加入反应釜中,升温至85℃,反应4.5小时;
2、中和反应:上述预聚体降温至55℃,加入三乙胺2,反应30分钟;
3、扩链反应:加入去离子水686,高速分散后加入水合肼5,继续搅拌升温至55℃,反应1.5小时得产品,产品外观状态为半透明,固含量为19.8%。
该实施例产品选用原料配比中聚碳酸亚丙酯二醇和聚环氧乙烷二醇较多,结晶性提高,使成膜消光性增强,且软锻比例增大手感柔软。
实施例4
制备方法:
1、预聚反应:将氢化二苯基甲烷二异氰酸酯50、六亚甲基二异氰酸酯三聚体5、线性双羟烷基硅氧烷20、聚碳酸亚丙酯二醇40、聚环氧乙烷二醇30、2,2,4-三甲基-1,3戊二醇4、二羟甲基丁酸4加入反应釜中,升温至90℃,反应4小时;
2、中和反应:上述预聚体降温至60℃,加入三乙胺2.7,反应25分钟;
3、扩链反应:加入去离子水621,高速分散后加入水合肼5.6继续搅拌,升温至60℃,反应1小时得产品,产品外观状态为半透明,固含量为20.1%。
该实施例产品由于提高了线性双羟烷基硅氧烷的比例,使体系相容性大幅降低,以及线性双羟烷基硅氧烷舒展性更强,致使增强了产品的消光性和绵柔的触感。
试验检测
将本发明实施例1- 4所得的产品做成2g/m2的膜,进行消光性,耐磨性,耐溶剂性能及手感测试,测试结果如下表。
编号 | 光泽(60℃) | 耐磨性能(次) | 耐溶剂性 | 手感 |
实施例1 | 4.5 | ≥5000 | 通过 | 滑爽柔软 |
实施例2 | 8.0 | ≥5000 | 通过 | 绵滑柔软 |
实施例3 | 6.2 | ≥5000 | 通过 | 滑爽柔软 |
实施例4 | 4.8 | ≥5000 | 通过 | 绵滑柔软 |
光泽度测试:按照GB 9754;光度仪 德国BYK AG-4446。
耐磨性检测:按照GB/T 21196-2007;织物平磨仪 FZ/T01011—91。
耐溶剂性:按照GB/T 23989-2009。
通过上述检测结果可以看出,本发明自消光柔感水性聚氨酯皮革涂饰剂的外观状态好,稳定性好,在不添加任何消光剂的情况下,可以达到自消光且手感绵柔滑爽;此外本发明自消光柔感水性聚氨酯皮革涂饰剂具有优异的耐磨性,耐溶剂性能。
Claims (3)
1.自消光柔感水性聚氨酯皮革涂饰剂,其特征是:
原料按重量配比:
氢化二苯基甲烷二异氰酸酯 30-50
六亚甲基二异氰酸酯三聚体 5-20
线性双羟烷基硅氧烷 5-20
聚碳酸亚丙酯二醇 30-60
聚环氧乙烷二醇(分子量2000) 30-50
2,2,4-三甲基-1,3戊二醇 3-5
二羟甲基丁酸 2-4
三乙胺 1-3
水合肼 4-6
去离子水 430-850
经预聚反应、中和反应、扩链反应制得;
产品化学指标如下:
外 观:半透明乳液
离子性:阴
pH 值:7±1
含固量:20±1%;
所述线性双羟烷基硅氧烷:为广州市斯洛柯高分子聚合物有限公司的Silok 3316产品;
所述聚碳酸亚丙酯二醇:为广东达志环保科技有限公司的PPC2000产品。
2.其特征是:
原料按重量配比:
制备方法:
(1)预聚反应:将氢化二苯基甲烷二异氰酸酯30-50、六亚甲基二异氰酸酯三聚体5-20、线性双羟烷基硅氧烷5-20、聚碳酸亚丙酯二醇30-60、聚环氧乙烷二醇30-50、2,2,4-三甲基-1,3戊二醇3-5、二羟甲基丁酸2-4加入反应釜中,升温至70-90℃,反应4—6小时;
(2)中和反应:降温至50-60℃,加入三乙胺1-3,反应25-35分钟;
(3)扩链反应:加入去离子水430-850,高速分散后加入水合肼4-6,搅拌升温至50-60℃,反应1-2小时,得产品:
所述线性双羟烷基硅氧烷:为广州市斯洛柯高分子聚合物有限公司的Silok 3316产品;
所述聚碳酸亚丙酯二醇:为广东达志环保科技有限公司的PPC2000产品。
3.如权利要求1制备方法得到的自消光柔感水性聚氨酯皮革涂饰剂。
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