CN109535377A - 一种具有自稳泡功能的水性聚氨酯及其制备方法与应用 - Google Patents

一种具有自稳泡功能的水性聚氨酯及其制备方法与应用 Download PDF

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CN109535377A
CN109535377A CN201811474275.3A CN201811474275A CN109535377A CN 109535377 A CN109535377 A CN 109535377A CN 201811474275 A CN201811474275 A CN 201811474275A CN 109535377 A CN109535377 A CN 109535377A
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宁继鑫
刘娅林
徐旭东
胡文翠
闫克辉
陈建栋
王铁森
陈玉国
郑萍
苗吉宾
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SHANDONG TIANQING TECHNOLOGY DEVELOPMENT Co Ltd
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Abstract

本发明公开了一种具有自稳泡功能的水性聚氨酯及其制备方法与应用，主要用于皮革和合成革发泡层，其中，所述的具有自稳泡功能的水性聚氨酯由以下重量份数的原料组成：二异氰酸酯50‑150份，二元醇150‑350份，小分子扩链剂5‑25份，聚乙二醇单丁醚10‑50份，催化剂0.01‑0.1份，中和剂3‑15份。本发明水性发泡浆料，从源头彻底消除了有机污染，节约了有机溶剂资源，消除了安全隐患，改善了劳动者就业环境，同时减少了稳泡助剂的使用，符合国家绿色环保和新旧能转换政策；制得的革制品剥离强度和常温耐折性能高、手感柔软、透气性优良。

Description

一种具有自稳泡功能的水性聚氨酯及其制备方法与应用
技术领域
本发明属于高分子材料领域，具体涉及一种具有自稳泡功能的水性聚氨酯及其制备方法与应用。
背景技术
我国是皮革和合成革生产消费大国，但传统的革制品产业一般采用溶剂型聚氨酯作为发泡层材料，生产过程中产生大量的废气、废水污染物，随着国家倡导绿色环保生产，该行业也面临着如何消除或减少废气污染物排放所带来的环境污染的严峻挑战。
现有技术中，革制品后整理阶段用到的发泡树脂通常为溶剂型树脂，少量采用水性发泡树脂，现有发泡树脂存在以下问题：1、溶剂型发泡树脂使用过程中产生大量废气、废水，对劳动者和环境产生不利影响。2、传统的水性机械发泡树脂中必须加入稳泡助剂，从而延长发泡浆料的使用时间，增加了生产成本,通过添加稳泡助剂的方法在烘干过程中，泡沫中的气体会受热膨胀，导致泡沫破裂或融合，影响手感和美观。
专利CN104231300A提供了一种聚氨酯发泡树脂，主要用于刨层皮和合成革后处理工序该树脂主要由以下重量分数的原料：水性阴离子聚氨酯树脂100份，发泡助剂1-5份，稳泡助剂1-5份，阳离子凝结剂0-5份，交联剂0-10份，增稠剂0.2-5份，水性着色剂0-6份，搅拌均匀制成泡沫材料。该方法必须加入稳泡助剂才可延长使用时间，同时在使用过程中气体受热膨胀，稳泡助剂迁移，导致泡沫破裂或融合，影响手感和美观。
专利CN107059420A提供了一种水性干法发泡服装革的制备方法，包括基布，基布上依次涂覆发泡层和面层；发泡层的浆料依次包括以下重量份原料组份：水性聚氨酯树脂250份，水性增稠剂0.2-1.2份，发泡剂1-5份，稳泡剂1-5份，水性交联剂1-1.5份。该方法必须加入稳泡助剂才可延长使用时间，同时在使用过程中气体受热膨胀，稳泡助剂迁移，导致泡沫破裂或融合，影响手感和美观。
发明内容
发明目的：为了解决现有技术的不足，本发明提供了一种具有自稳泡功能的水性聚氨酯树脂，主要用于合成革和皮革发泡层，解决了目前溶剂型聚氨酯湿法工艺中污染及安全问题，发泡浆料中采用的主体树脂为具有自稳泡功能的水性聚氨酯，可以不用或少用稳泡助剂，降低了生产成本。
技术方案：为解决上述技术问题，本发明提供一种具有自稳泡功能的水性聚氨酯，所述的具有自稳泡功能的水性聚氨酯由以下重量份数的原料组成：二异氰酸酯50-150份，二元醇150-350份，小分子扩链剂5-25份，聚乙二醇单丁醚10-50份，催化剂0.01-0.1份，中和剂3-15份；其中：
所述的二异氰酸酯包括：六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯中的一种或几种组合；
所述的二元醇包括：聚四氢呋喃二元醇、聚酯二元醇、聚丙二醇中的一种或几种组合，所述二元醇数均分子量为650-4000；
所述的小分子扩链剂包括：1,4-丁二醇、1,6-己二醇、新戊二醇、二羟甲基丙酸中的一种或几种组合；
所述聚乙二醇单丁醚数均分子量为350-1000。
作为进一步的优化，所述的催化剂包括：有机银催化剂、有机铋催化剂或辛酸亚锡催化剂中的一种或几种组合。
作为进一步的优化，所述的中和剂包括：三乙胺、二甲基乙醇胺、三乙醇胺、二乙醇胺中的一种。
为解决上述技术问题，本发明提供一种所述的具有自稳泡功能的水性聚氨酯的制备方法，包括以下步骤：
(1)聚氨酯预聚物的制备：将二元醇于120℃真空脱水1小时，降温至50-70℃，加入二异氰酸酯、催化剂，在机械搅拌下，60-90℃反应2-4小时，投入小分子扩链剂，在70-85℃下反应3-4小时；
(2)具有稳泡单体预聚物的制备：将稳泡单体聚乙二醇单丁醚投入聚氨酯预聚物中,在60-85℃下反应2-4小时；
(3)中和反应：将上述的具有稳泡单体预聚物降温至30-55℃，加入三乙胺，搅拌5-30分钟；
(4)具有自稳泡功能的水性聚氨酯的制备：在高速搅拌下，将去离子水加入上述反应液中，然后减压蒸馏脱出丙酮，得到具有自稳泡功能的水性聚氨酯。
为解决上述技术问题，本发明提供一种具有自稳泡功能的应用，所述的具有自稳泡功能的水性聚氨酯用于制成发泡浆料，所述的发泡浆料由以下重量份数的原料组成：发泡助剂1-5份，交联剂0-6份，增稠剂0.1-5份，着色剂0-6份，具有自稳泡功能的水性聚氨酯树脂100份；将上述原料混合搅拌均匀，制成发泡浆料；其中：
所述的发泡助剂为氨基有机硅改性的表面活性剂，十二烷基硫酸钠，十二烷基苯磺酸钠中的任意一种或多种。
作为进一步的优化，所述的交联剂为氮丙啶类交联剂，碳化二亚胺类交联剂，水性异氰酸酯类交联剂中任意一种或两种；其中，水性交联剂为Covestro N 3800。
作为进一步的优化，所述的增稠剂为聚氨酯类增稠剂、丙烯酸类增稠剂或纤维素类增稠剂中任意一种或两种。
作为进一步的优化，所述的着色剂为水性颜料膏或染料。
作为进一步的优化，所述的具有自稳泡功能的水性聚氨酯的固含量为35％-65％。
为解决上述技术问题，本发明提供一种所述的发泡浆料在丰满度要求较高的真皮革和合成革中的应用，所述的发泡浆料涂覆于真皮革和合成革中，手指压发泡层撤力后发泡层可以迅速回弹至原厚度。
有益效果：本发明主要用于合成革和皮革发泡层，解决了目前溶剂型聚氨酯湿法工艺中污染及安全问题，发泡浆料中采用的主体树脂为具有自稳泡功能的水性聚氨酯，可以不用或少用稳泡助剂，降低了生产成本。其中，二异氰酸酯和小分子扩链剂可以提供支撑泡孔和丰满度的作用，二元醇提供柔软的手感，聚乙二醇单丁醚在应用时提供稳定泡沫的作用。
本发明水性发泡浆料，从源头彻底消除了有机污染，节约了有机溶剂资源，消除了安全隐患，改善了劳动者就业环境，同时稳泡效果好，以水作溶剂，减少了稳泡助剂的使用，符合国家绿色环保和新旧能转换政策；制得的革制品剥离强度和常温耐折性能高、手感柔软、透气性优良。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，以使本领域的技术人员能够更好的理解本发明的优点和特征，从而对本发明的保护范围做出更为清楚的界定。本发明所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例，还应包括在本发明所要求的权利范围内其他任何公知的改变,基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1：具有自稳泡功能的水性聚氨酯
将300克聚四氢呋喃二元醇(数均分子量为3000)于120℃真空脱水1小时，降温至50℃，加入64克甲苯二异氰酸酯、0.08克辛酸亚锡催化剂，在机械搅拌下，65℃反应3小时，将5.3克1,4-丁二醇、13.8克二羟甲基丙酸、30克丙酮投入混合物中70℃反应3.5小时，加入20克聚乙二醇丁醚(数均分子量为350),70℃反应2小时，加入50克丙酮降温至40℃，加入9.9克三乙胺搅拌15分钟，高速搅拌下，将417克去离子水加入上述反应液中，然后减压蒸馏脱出丙酮，得到固含量为49.6％的水性聚氨酯。
实施例2：具有自稳泡功能的水性聚氨酯
将200克聚四氢呋喃二元醇(数均分子量为1000)、100克聚丙二醇(数均分子量为2000)于120℃真空脱水1小时，降温至70℃，加入148克异佛尔酮二异氰酸酯、0.1克辛酸亚锡催化剂，在机械搅拌下，85℃反应3小时，将4克1,6-己二醇、14克二羟甲基丙酸、50克丙酮投入混合物中80℃反应2.5小时，加入50克聚乙二醇丁醚(数均分子量为750),80℃反应2.5小时，加入50克丙酮降温至40℃，加入10.03克三乙胺搅拌30分钟，高速搅拌下，将376克去离子水加入上述反应液中，然后减压蒸馏脱出丙酮，得到固含量为54.8％的水性聚氨酯。
实施例3：具有自稳泡功能的水性聚氨酯
将200克聚己二酸丁二醇酯二元醇(数均分子量为2000)、100克聚四氢呋喃二元醇(数均分子量为2000)于120℃真空脱水1小时，降温至75℃，加入110克二环己基甲烷二异氰酸酯、0.1克有机铋催化剂，在机械搅拌下，90℃反应2.5小时，将5克新戊二醇、13.6克二羟甲基丙酸、60克丙酮投入混合物中85℃反应2.5小时，加入80克聚乙二醇丁醚(数均分子量为1000),85℃反应2.5小时，加入30克丙酮降温至40℃，加入9.74克三乙胺搅拌20分钟，高速搅拌下，将595克去离子水加入上述反应液中，然后减压蒸馏脱出丙酮，得到固含量为42.5％的水性聚氨酯。
实施例4：具有自稳泡功能的水性聚氨酯浆料
在机械搅拌的同时，将3份发泡助剂、3份水性黑色浆加入100份上述1-3实施例中的具有自稳泡功能的水性聚氨酯中，混合均匀后，加入2份水性异氰酸酯固化剂，继续搅拌均匀，加入非离子聚氨酯增稠剂调节黏度至8000-12000mp.s范围，获得具有自稳泡功能的水性聚氨酯发泡浆料。
实施例5：具有自稳泡功能的水性聚氨酯浆料
在机械搅拌的同时，将5份发泡助剂、2份水性红色浆、2份氮丙啶固化剂加入100份上述1-3实施例中的具有自稳泡功能的水性聚氨酯中，混合均匀后，加入二甲基乙醇胺调节pH至8-9，加入丙烯酸类增稠剂调节黏度至8000-12000mp.s范围，获得具有自稳泡功能的水性聚氨酯发泡浆料。
该发泡浆料的性能采用国家标准测试方法，具体如表1浆料的性能测试所示：
表1浆料的性能测试
序号 项目 指标
1 剥离强度(N/3cm) ＞80
2 25℃常温耐折性能(次) ＞10万
3 拉伸强度(MPa) ＞2
4 透气性(ml/cm<sup>2</sup>.h) ＞3500
本发明制备的具有自稳泡功能水性聚氨酯浆料，稳泡效果好，以水作溶剂，减少了稳泡助剂的使用，符合国家绿色环保和新旧能转换政策；制得的革制品剥离强度和常温耐折性能高、手感柔软、透气性优良。

Claims (10)

1.一种具有自稳泡功能的水性聚氨酯，其特征在于：所述的具有自稳泡功能的水性聚氨酯由以下重量份数的原料组成：二异氰酸酯50-150份，二元醇150-350份，小分子扩链剂5-25份，聚乙二醇单丁醚10-50份，催化剂0.01-0.1份，中和剂3-15份；其中：
所述的二异氰酸酯包括：六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯中的一种或几种组合；
所述的二元醇包括：聚四氢呋喃二元醇、聚酯二元醇、聚丙二醇中的一种或几种组合，所述二元醇数均分子量为650-4000；
所述的小分子扩链剂包括：1,4-丁二醇、1,6-己二醇、新戊二醇、二羟甲基丙酸中的一种或几种组合；
所述聚乙二醇单丁醚数均分子量为350-1000。
2.根据权利要求1所述的具有自稳泡功能的水性聚氨酯，其特征在于：所述的催化剂包括：有机银催化剂、有机铋催化剂或辛酸亚锡催化剂中的一种或几种组合。
3.根据权利要求1所述的具有自稳泡功能的水性聚氨酯，其特征在于：所述的中和剂包括：三乙胺、二甲基乙醇胺、三乙醇胺、二乙醇胺中的一种。
4.根据权利要求1-3任一项所述的具有自稳泡功能的水性聚氨酯的制备方法，其特征在于：包括以下步骤：
(1)聚氨酯预聚物的制备：将二元醇于120℃真空脱水1小时，降温至50-70℃，加入二异氰酸酯、催化剂，在机械搅拌下，60-90℃反应2-4小时，投入小分子扩链剂，在70-85℃下反应3-4小时；
(2)具有稳泡单体预聚物的制备：将稳泡单体聚乙二醇单丁醚投入聚氨酯预聚物中,在60-85℃下反应2-4小时；
(3)中和反应：将上述的具有稳泡单体预聚物降温至30-55℃，加入三乙胺，搅拌5-30分钟；
(4)具有自稳泡功能的水性聚氨酯的制备：在高速搅拌下，将去离子水加入上述反应液中，然后减压蒸馏脱出丙酮，得到具有自稳泡功能的水性聚氨酯。
5.一种根据权利要求1所述的具有自稳泡功能的水性聚氨酯的应用，其特征在于：所述的具有自稳泡功能的水性聚氨酯用于制成发泡浆料，所述的发泡浆料由以下重量份数的原料组成：发泡助剂1-5份，交联剂0-6份，增稠剂0.1-5份，着色剂0-6份，具有自稳泡功能的水性聚氨酯树脂100份；将上述原料混合搅拌均匀，制成发泡浆料；其中：
所述的发泡助剂为氨基有机硅改性的表面活性剂，十二烷基硫酸钠，十二烷基苯磺酸钠中的任意一种或多种。
6.根据权利要求5所述的具有自稳泡功能的水性聚氨酯的发泡浆料，其特征在于：所述的交联剂为氮丙啶类交联剂，碳化二亚胺类交联剂，水性异氰酸酯类交联剂中任意一种或两种；其中，水性交联剂为Covestro N 3800。
7.根据权利要求5所述的具有自稳泡功能的水性聚氨酯的发泡浆料，其特征在于：所述的增稠剂为聚氨酯类增稠剂、丙烯酸类增稠剂或纤维素类增稠剂中任意一种或两种。
8.根据权利要求5所述的具有自稳泡功能的水性聚氨酯的发泡浆料，其特征在于：所述的着色剂为水性颜料膏或染料。
9.根据权利要求5所述的具有自稳泡功能的水性聚氨酯的发泡浆料，其特征在于：所述的具有自稳泡功能的水性聚氨酯的固含量为35％-65％。
10.一种根据权利要求5所述的发泡浆料在真皮革和合成革中的应用。
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