CN104448193A - 一种水性聚氨酯皮革涂饰剂及其制备方法 - Google Patents

一种水性聚氨酯皮革涂饰剂及其制备方法 Download PDF

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CN104448193A
CN104448193A CN201410708489.8A CN201410708489A CN104448193A CN 104448193 A CN104448193 A CN 104448193A CN 201410708489 A CN201410708489 A CN 201410708489A CN 104448193 A CN104448193 A CN 104448193A
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赵志辉
刘涛
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TAIXING HUASHENG YINYANG RESIN Co Ltd
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Abstract

本发明公开一种水性聚氨酯皮革涂饰剂及其制备方法，所述方法为：用二异氰酸酯、醋酸丁酸纤维素和聚醚多元醇生成以异氰酸酯基封端的聚预体，然后用亲水扩链剂扩链后再用三乙胺中和，最后再用乙二胺扩链形成醋酸丁酸纤维素改性的水性聚氨酯分散体，从而制得水性聚氨酯皮革涂饰剂。本发明的水性聚氨酯皮革涂饰剂及其制备方法，通过采用醋酸丁酸纤维素对水性聚氨酯进行改性，得到CAB改性水性聚氨酯分散体。该树脂成膜光亮，坚韧，耐曲挠性好，赋予皮革极佳的高光泽，平滑、柔软的手感和良好的熨平性能，以及优良的耐光、耐热，不变黄等特性，顶涂后大大提高了皮革的精选率，提高了皮革档次。

Description

一种水性聚氨酯皮革涂饰剂及其制备方法
技术领域
本发明涉及皮革表明涂层技术领域，尤其涉及一种水性聚氨酯皮革涂饰剂及其制备方法。
背景技术
涂饰在皮革生产中是一个非常重要的手段，能显著提高成革的质量和档次，增加革的品种和商业价值，是制革生产中的最后一道“生命线”。而聚氨酯（PU）皮革涂饰剂因具有光亮、丰满、耐磨耗，成膜性能好、富有弹性、耐低温、耐曲挠、手感好等优点，已成为一个重要的皮革涂饰剂体系。尤其是水性PU涂饰剂因其以水为介质，具有不燃、气味小、不污染环境、节能、操作加工方便等优点，在很大的程度上取代了溶剂型PU涂饰剂,成为一种极具潜力的"绿色材料"，尤其与清洁工艺配套进行皮革产品生产。
目前水性聚氨酯皮革光亮剂多以聚碳酸酯、聚醚等为多元醇原料，制备出的水性聚氨酯其机械性能、耐热性、柔韧性都很好,成膜后亮度也较为理想，但其光泽度和油性聚氨酯还存在一定的差距。
因此，现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足，本发明的目的在于提供一种水性聚氨酯皮革涂饰剂及其制备方法，旨在解决目前水性皮革涂饰剂光泽度不理想的问题。
本发明的技术方案如下：
一种水性聚氨酯皮革涂饰剂的制备方法，其中，所述方法为：
用二异氰酸酯、醋酸丁酸纤维素（CAB）和聚醚多元醇生成以异氰酸酯基封端的聚预体，然后用亲水扩链剂扩链后再用三乙胺中和，最后再用乙二胺扩链形成醋酸丁酸纤维素改性的水性聚氨酯分散体，从而制得水性聚氨酯皮革涂饰剂。
所述的水性聚氨酯皮革涂饰剂的制备方法，其中，所述用二异氰酸酯、醋酸丁酸纤维素和聚醚多元醇生成以异氰酸酯基封端的聚预体具体为：
在氮气保护下，将醋酸丁酸纤维素10-20重量份、聚醚多元醇40-60重量份、二异氰酸酯30-50重量份在80-85℃反应2-3 h得到以异氰酸酯基封端的聚预体。
所述的水性聚氨酯皮革涂饰剂的制备方法，其中，所述用亲水扩链剂扩链后再用三乙胺中和，最后再用乙二胺扩链形成醋酸丁酸纤维素改性的水性聚氨酯分散体具体为：
向预聚体中加亲水扩链剂3-6重量份在80-85℃继续反应3-5 h，降温至40℃后加三乙胺3-6重量份反应30 min，用水高速分散后，加入乙二胺6-10重量份分散0.5-1h，即得到醋酸丁酸纤维素改性水性聚氨酯分散体。
    所述的水性聚氨酯皮革涂饰剂的制备方法，其中，所述的聚醚多元醇聚丙二醇或聚氧化四亚甲基二醇，其中，所述聚丙二醇规格为PPG-1000或PPG-2000, 所述聚氧化四亚甲基二醇规格为PTMG-1000或PTMG-2000。
所述的水性聚氨酯皮革涂饰剂的制备方法，其中，所述的二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯或甲苯二异氰酸酯。
所述的水性聚氨酯皮革涂饰剂的制备方法，其中，所述的亲水扩链剂为2,2-二羟甲基丁酸或2,2-二羟甲基丙酸。
有益效果：本发明提供一种水性聚氨酯皮革涂饰剂及其制备方法，通过采用醋酸丁酸纤维素对水性聚氨酯进行改性，得到CAB改性水性聚氨酯分散体。该树脂成膜光亮，坚韧，耐曲挠性好，赋予皮革极佳的高光泽，平滑、柔软的手感和良好的熨平性能，以及优良的耐光、耐热，不变黄等特性，顶涂后大大提高了皮革的精选率，提高皮革档次。
具体实施方式
本发明提供一种水性聚氨酯皮革涂饰剂及其制备方法，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明本发明提供一种水性聚氨酯皮革涂饰剂的制备方法，该方法是用二异氰酸酯、醋酸丁酸纤维素和聚醚多元醇生成以异氰酸酯基（-NCO）封端的聚预体，然后用亲水扩链剂扩链后再用三乙胺中和，最后再用乙二胺扩链形成醋酸丁酸纤维素改性的水性聚氨酯分散体，从而制得水性聚氨酯皮革涂饰剂。  
作为皮革光亮剂醋酸丁酸纤维素（CAB）具有优良的耐光性能，成膜光亮，坚韧，耐曲挠性好，赋予皮革极佳的高光泽，平滑、柔软的手感和良好的熨平性能，以及优良的耐光、耐热，不变黄等特性，顶涂后大大提高了皮革的精选率，提高皮革档次，其分子结构如下：
,其中，R=H或或。
本发明如上所述的利用CAB改性水性聚氨酯分散体的制备反应过程可表示如下：
通过上述反应可制备出高光泽、高丰满度、平滑、柔软的水性聚氨酯。
进一步地，上述制备方法具体为：
在氮气保护下，将醋酸丁酸纤维素10-20重量份、聚醚多元醇40-60重量份、二异氰酸酯30-50重量份在80-85℃反应2-3 h得到以异氰酸酯基团封端的聚预体。向预聚体中加亲水扩链剂3-6重量份在80-85℃继续反应3-5 h，降温至40℃后加三乙胺3-6重量份反应30 min，用水高速分散后，加入乙二胺6-10重量份分散0.5-1h，即得到醋酸丁酸纤维素改性水性聚氨酯分散体。
其中，所述的聚醚多元醇聚丙二醇或聚氧化四亚甲基二醇，所述聚丙二醇规格为PPG-1000或PPG-2000, 所述聚氧化四亚甲基二醇规格为PTMG-1000或PTMG-2000。
所述的二异氰酸酯为异佛尔酮二异氰酸酯（IPDI）、六亚甲基二异氰酸酯（HDI）、二环己基甲烷二异氰酸酯（HMDI）或甲苯二异氰酸酯（TDI）。  
所述的亲水扩链剂为2,2-二羟甲基丁酸（DMPA）或2,2-二羟甲基丙酸（DMBA）。
下面通过具体实施例对本发明的方案作进一步地说明：
实施例1
按重量份数计，在氮气保护下，将CAB,10份、PTMG-2000,40份、IPDI，35份在80-85℃反应2-3h，加DMPA，5份，在80-85℃继续反应3-5h，降温至40℃，加三乙胺4份，反应30min，用水高速分散后，加入6份乙二胺分散1h，即得到CAB改性水性聚氨酯分散体。其产品典型特性如下：
实施例2
按重量份数计，在氮气保护下，将CAB,15份、PTMG-2000,35份、IPDI，40份在80-85℃反应2-3h，加DMPA，5份，在80-85℃继续反应3-5h，降温至40℃，加三乙胺4份，反应30min，用水高速分散后，加入6.3份乙二胺分散0.5 h，即得到CAB改性水性聚氨酯分散体。其产品典型特性如下：
实施例3
按重量份数计，在氮气保护下，将CAB,20份、PTMG-2000,30份、IPDI，40份在80-85℃反应2-3h，加DMPA，5份在80-85℃继续反应3-5h，降温至40℃，加三乙胺4份，反应30min，用水高速分散后，加入5份乙二胺分散1h，即得到CAB改性水性聚氨酯分散体。其产品典型特性如下：
本发明提供一种水性聚氨酯皮革涂饰剂及其制备方法，通过采用醋酸丁酸纤维素对水性聚氨酯进行改性，得到CAB改性水性聚氨酯分散体。该树脂成膜光亮，坚韧，耐曲挠性好，赋予皮革极佳的高光泽，平滑、柔软的手感和良好的熨平性能，以及优良的耐光、耐热，不变黄等特性，顶涂后大大提高了皮革的精选率，提高皮革档次。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (6)

1.一种水性聚氨酯皮革涂饰剂的制备方法，其特征在于，所述方法为：
用二异氰酸酯、醋酸丁酸纤维素和聚醚多元醇生成以异氰酸酯基封端的聚预体，然后用亲水扩链剂扩链后再用三乙胺中和，最后再用乙二胺扩链形成醋酸丁酸纤维素改性的水性聚氨酯分散体，从而制得水性聚氨酯皮革涂饰剂。
2.根据权利要求1所述的水性聚氨酯皮革涂饰剂的制备方法，其特征在于，所述用二异氰酸酯、醋酸丁酸纤维素和聚醚多元醇生成以异氰酸酯基封端的聚预体具体为：
在氮气保护下，将醋酸丁酸纤维素10-20重量份、聚醚多元醇40-60重量份、二异氰酸酯30-50重量份在80-85℃反应2-3 h得到以异氰酸酯基封端的聚预体。
3.根据权利要求1所述的水性聚氨酯皮革涂饰剂的制备方法，其特征在于，所述用亲水扩链剂扩链后再用三乙胺中和，最后再用乙二胺扩链形成醋酸丁酸纤维素改性的水性聚氨酯分散体具体为：
向预聚体中加亲水扩链剂3-6重量份在80-85℃继续反应3-5 h，降温至40℃后加三乙胺3-6重量份反应30 min，用水高速分散后，加入乙二胺6-10重量份分散0.5-1h，即得到醋酸丁酸纤维素改性水性聚氨酯分散体。
4. 根据权利要求2所述的水性聚氨酯皮革涂饰剂的制备方法，其特征在于，所述的聚醚多元醇聚丙二醇或聚氧化四亚甲基二醇，其中，所述聚丙二醇规格为PPG-1000或PPG-2000, 所述聚氧化四亚甲基二醇规格为PTMG-1000或PTMG-2000。
5.根据权利要求2所述的水性聚氨酯皮革涂饰剂的制备方法，其特征在于，所述的二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯或甲苯二异氰酸酯。
6.根据权利要求3所述的水性聚氨酯皮革涂饰剂的制备方法，其特征在于，所述的亲水扩链剂为2,2-二羟甲基丁酸或2,2-二羟甲基丙酸。
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