CN104193941B - 超支化非离子型水性聚氨酯皮革涂饰剂及其制备方法 - Google Patents

超支化非离子型水性聚氨酯皮革涂饰剂及其制备方法 Download PDF

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CN104193941B
CN104193941B CN201410467668.7A CN201410467668A CN104193941B CN 104193941 B CN104193941 B CN 104193941B CN 201410467668 A CN201410467668 A CN 201410467668A CN 104193941 B CN104193941 B CN 104193941B
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黄凯
孙海园
刘娅林
马金明
闫克辉
陈建栋
王铁森
陈玉国
于福哲
苗吉宾
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Abstract

本发明提供一种超支化非离子型水性聚氨酯皮革涂饰剂及其制备方法，该皮革涂饰剂，主要由低聚物多元醇、异氰酸酯、聚硅氧烷、三羟甲基丙烷聚乙二醇单甲醚、端羟基超支化聚合物等原料制备而成。本发明所述涂饰剂、固含量高、耐水性强、对电解质的化学稳定性高。

Description

超支化非离子型水性聚氨酯皮革涂饰剂及其制备方法
技术领域
本发明属于化工技术领域，特别涉及一种非离子型水性聚氨酯皮革涂饰剂及其制备方法。
背景技术
现有的离子型聚氨酯大部分使用内乳化法将聚氨酯乳化与水中，当亲水性扩链剂使用较少时，乳化困难，并且聚氨酯颗粒较大，稳定性较差，并且产品成膜外观较差；当亲水性扩链剂使用较多时，成膜时耐水性较差。由于制备的聚氨酯为离子型聚氨酯，对电解质敏感，使得聚氨酯产品与其他离子型聚氨酯和各种助剂的配伍性较差，稳定性低，不利于长期储存。
超支化聚合物（hyperbranched polymer）是最近几年发展起来的特殊大分子结构的聚合物，关于超支化聚合物在皮革、合成革、发光材料和纳米材料等功能材料的涂饰方面的应用屡见不鲜。近年来，超支化聚合物由于其具有高度支化的三维结构和大量的端基基团以及其显示出与线性高分子许多不同的优良性能引起皮革界的广泛关注。
发明内容
本发明提供一种超支化非离子型水性聚氨酯皮革涂饰剂及其制备方法，以克服现有离子型聚氨酯存在的固含量低、耐水性差和对电解质敏感的缺点。
本发明所述超支化非离子型水性聚氨酯皮革涂饰剂，主要由以下重量份数的原料制备而成：低聚物多元醇22.3-62.5份、异氰酸酯18-36份、聚硅氧烷1.2-3.6份、三羟甲基丙烷聚乙二醇单甲醚2.4-19.1份、羟基二醇1.2-2份、催化剂0.03-0.07份、去离子水102-205份、烷醇胺0.8-4.3份、端羟基超支化聚合物8.3-32.6份、己二酰肼交联剂0.2-2份。
根据本发明，所述低聚物多元醇选自分子量为2000，羟值为55-60 KOH mg/g的聚四亚甲基醚二醇；分子量为2000，羟值为55-60 KOH mg/g的聚四氢呋喃醚二醇；分子量为2000，羟值为55-60 KOH mg/g的聚碳酸酯二醇中的一种。
所述异氰酸酯选自甲苯二异氰酸酯（TDI），二苯甲基二异氰酸酯（MDI），异氟尔酮二异氰酸酯（IPDI），己二异氰酸酯，辛二异氰酸酯（ODI），癸二异氰酸酯，萘二异氰酸酯（NDI）、六氢甲苯二异氰酸酯。
所述催化剂为辛酸亚锡。
所述羟基二醇选自1,4-丁二醇、1,6-己二醇、新戊二醇。
所述端羟基超支化聚合物为超支化聚酯Boltorn H40。
Boltorn H40为市售商品。
所述烷醇胺为三乙胺、二甲基氨基乙醇。
本发明所述超支化非离子型水性聚氨酯皮革涂饰剂的制备方法，主要包括如下步骤：
首先将低聚物多元醇与异氰酸酯进行混合，在60-100 ℃搅拌反应60-180 min，再加入聚硅氧烷通过逐步聚合反应获得预聚体，加入三羟甲基丙烷聚乙二醇单甲醚、羟基二醇和催化剂，50-80 ℃反应30-90 min后加入非质子性有机溶剂调节黏度至70-80 mPa.s，降温至50-70 ℃缓慢加入端羟基超支化聚合物继续搅拌30-90 min，期间用非质子性有机溶剂维持黏度至70-80 mPa.s，制得聚氨酯中间产物；在搅拌下将聚氨酯中间产物与烷醇胺加入到-10-0℃的冰水中混合，-10-0 ℃搅拌反应，搅拌30-120 min制得聚氨酯水分散体；向聚氨酯水分散体中加入己二酰肼交联剂搅拌反应10-30min，得到乳白色的超支化非离子型水性聚氨酯乳液。
根据本发明，所述非质子性有机溶剂选自丙酮、甲乙酮或N,N-二甲基吡咯烷酮。
与现有技术相比，本发明所述皮革涂饰剂有以下优点：
1、固含量高：超支化聚氨酯合成过程中，由于引入了超支化结构聚合物，使产品的固含量提高；
2、耐水性强：通过有机硅功能单体的引入，使有机硅与聚氨酯化学结合，在制备聚氨酯水分散体中加入己二酰肼交联剂，使产品在成膜过程中自交联，提高了膜的耐水性，吸水率明显优于普通聚氨酯；
3、对电解质的化学稳定性高：由于使用了非离子型亲水扩链剂，使聚氨酯水分散液对电解质溶液有较好的化学稳定性。
附图说明
图1为聚氨酯预聚体的合成示意图；
图2为超支化非离子型水性聚氨酯的合成示意图。
具体实施方式
实施例1
参见附图1-2，首先将62.5 kg聚四氢呋喃醚二醇(PTMG，Mn=2000，羟值=57.4 KOH mg/g)与22 kg异氟尔酮二异氰酸酯进行混合，在80 ℃搅拌反应180 min，再加入1.7 g聚硅氧烷（涌奇FS6098）通过逐步聚合反应获得聚氨酯预聚体，加入4 kg三羟甲基丙烷聚乙烯二醇单甲醚和1.2 kg二羟甲基丙酸作为扩链剂，0.03 g辛酸亚锡催化剂，70 ℃反应90 min后加入丙酮调节黏度至70-80 mPa.s，降温至50℃缓慢加入12.5 kg超支化聚酯Boltorn H40（瑞典柏斯托公司 Boltorn™ H40）继续搅拌60 min，期间用非质子性有机溶剂维持黏度至70-80 mPa.s，制得聚氨酯中间产物；在高剪切力（转速控制在1000-2000r/min）下将中间产物与0.8 kg二甲氨基乙醇加入到205 kg冰水（温度-10℃）中，低温混合，-5 ℃搅拌反应60min后制的聚氨酯水分散体，在制备聚氨酯水分散体中加入0.4 kg己二酰肼交联剂搅拌反应10min，得到乳白色的超支化非离子型水性聚氨酯乳液。
实施例2
参见附图1-2，首先将53.6 kg聚四氢呋喃醚二醇(PTMG，Mn=2000，羟值=57.4 KOH mg/g)与36 kg异氟尔酮二异氰酸酯进行混合，在70 ℃搅拌反应180 min，再加入2.6 g聚硅氧烷（涌奇FS6098）通过逐步聚合反应获得聚氨酯预聚体，加入6 kg三羟甲基丙烷聚乙烯二醇单甲醚和1.6 kg二羟甲基丙酸作为扩链剂，0.06 g辛酸亚锡催化剂， 70 ℃反应90 min后加入丙酮调节黏度至70-80 mPa.s，降温至50℃缓慢加入10.8 kg超支化聚酯Boltorn H40（瑞典柏斯托公司 Boltorn™ H40）继续搅拌60 min，期间用非质子性有机溶剂维持黏度至70-80 mPa.s，制得聚氨酯中间产物；在高剪切力（转速控制在1000-2000r/min）下将中间产物与1.06 kg二甲氨基乙醇加入到200 kg冰水（温度-5℃）中，低温混合，-5 ℃搅拌反应60min后制的聚氨酯水分散体，在制备聚氨酯水分散体中加入0.6 kg己二酰肼交联剂搅拌反应10min，得到乳白色的超支化非离子型水性聚氨酯乳液。
实施例3
参见附图1-2，首先将58.2 kg聚四亚甲基醚二醇(Mn=2000，羟值=57.4 KOH mg/g)与27 kg异氟尔酮二异氰酸酯进行混合，在80 ℃搅拌反应180 min，再加入2.1 g聚硅氧烷（涌奇FS6098）通过逐步聚合反应获得聚氨酯预聚体，加入8 kg三羟甲基丙烷聚乙烯二醇单甲醚和2 kg二羟甲基丙酸作为扩链剂，0.03 g辛酸亚锡催化剂， 70 ℃反应90 min后加入丙酮调节黏度至70-80 mPa.s，降温至50℃缓慢加入7.9 kg超支化聚酯Boltorn H40（瑞典柏斯托公司 Boltorn™ H40）继续搅拌60 min，期间用非质子性有机溶剂维持黏度至70-80 mPa.s，制得聚氨酯中间产物；在高剪切力（转速控制在1000-2000r/min）下将中间产物与1.3 kg二甲氨基乙醇加入到195 kg冰水（温度-10℃）中，低温混合，-5 ℃搅拌反应60min后制的聚氨酯水分散体，在制备聚氨酯水分散体中加入0.6 kg己二酰肼交联剂搅拌反应10min，得到乳白色的超支化非离子型水性聚氨酯乳液。

Claims (8)

1.一种超支化非离子型水性聚氨酯皮革涂饰剂，其特征在于，主要由以下重量份数的原料制备而成：低聚物多元醇22.3-62.5份、异氰酸酯18-36份、聚硅氧烷1.2-3.6份、三羟甲基丙烷聚乙二醇单甲醚2.4-19.1份、羟基二醇1.2-2份、催化剂0.03-0.07份、去离子水102-205份、烷醇胺0.8-4.3份、端羟基超支化聚合物8.3-32.6份、己二酰肼交联剂0.2-2份；
其中，所述低聚物多元醇选自分子量为2000，羟值为55-60KOHmg/g的聚四亚甲基醚二醇；分子量为2000，羟值为55-60KOH mg/g的聚四氢呋喃醚二醇；分子量为2000，羟值为55-60KOH mg/g的聚碳酸酯二醇中的一种；
所述聚硅氧烷为
所述超支化非离子型水性聚氨酯皮革涂饰剂的制备方法，主要包括如下步骤：
首先将低聚物多元醇与异氰酸酯进行混合，在60-100℃搅拌反应60-180min，再加入聚硅氧烷通过逐步聚合反应获得预聚体，加入三羟甲基丙烷聚乙二醇单甲醚、羟基二醇和催化剂，50-80℃反应30-90min后加入非质子性有机溶剂调节黏度至70-80mPa.s，降温至50-70℃缓慢加入端羟基超支化聚合物继续搅拌30-90min，期间用非质子性有机溶剂维持黏度至70-80mPa.s，制得聚氨酯中间产物；在搅拌下将聚氨酯中间产物与烷醇胺加入到-10-0℃的冰水中混合，-10-0℃搅拌反应，搅拌30-120min制得聚氨酯水分散体；向聚氨酯水分散体中加入己二酰肼交联剂搅拌反应10-30min，得到乳白色的超支化非离子型水性聚氨酯乳液。
2.如权利要求1所述皮革涂饰剂，其特征在于，所述异氰酸酯选自甲苯二异氰酸酯(TDI)，二苯甲基二异氰酸酯(MDI)，异氟尔酮二异氰酸酯(IPDI)，己二异氰酸酯，辛二异氰酸酯(ODI)，癸二异氰酸酯，萘二异氰酸酯(NDI)、六氢甲苯二异氰酸酯。
3.如权利要求1所述皮革涂饰剂，其特征在于，所述催化剂为辛酸亚锡。
4.如权利要求1所述皮革涂饰剂，其特征在于，所述羟基二醇选自1,4-丁二醇、1,6-己二醇、新戊二醇。
5.如权利要求1所述皮革涂饰剂，其特征在于，所述端羟基超支化聚合物为超支化聚酯Boltorn H40。
6.如权利要求1所述皮革涂饰剂，其特征在于，所述烷醇胺为三乙胺、二甲基氨基乙醇。
7.如权利要求1-6任一项所述超支化非离子型水性聚氨酯皮革涂饰剂的制备方法，其特征在于，主要包括如下步骤：
首先将低聚物多元醇与异氰酸酯进行混合，在60-100℃搅拌反应60-180min，再加入聚硅氧烷通过逐步聚合反应获得预聚体，加入三羟甲基丙烷聚乙二醇单甲醚、羟基二醇和催化剂，50-80℃反应30-90min后加入非质子性有机溶剂调节黏度至70-80mPa.s，降温至50-70℃缓慢加入端羟基超支化聚合物继续搅拌30-90min，期间用非质子性有机溶剂维持黏度至70-80mPa.s，制得聚氨酯中间产物；在搅拌下将聚氨酯中间产物与烷醇胺加入到-10-0℃的冰水中混合，-10-0℃搅拌反应，搅拌30-120min制得聚氨酯水分散体；向聚氨酯水分散体中加入己二酰肼交联剂搅拌反应10-30min，得到乳白色的超支化非离子型水性聚氨酯乳液。
8.如权利要求7所述制备方法，其特征在于，所述非质子性有机溶剂选自丙酮、甲乙酮或N,N-二甲基吡咯烷酮。
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