CN110041498B - 耐水解腐蚀的聚氨酯合成革 - Google Patents

耐水解腐蚀的聚氨酯合成革 Download PDF

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CN110041498B
CN110041498B CN201910345629.2A CN201910345629A CN110041498B CN 110041498 B CN110041498 B CN 110041498B CN 201910345629 A CN201910345629 A CN 201910345629A CN 110041498 B CN110041498 B CN 110041498B
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Abstract

本发明公开了耐水解腐蚀的聚氨酯合成革，采用湿法制造工艺将改性聚氨酯乳液渗透到非织造布间得到，首先是利用1,4‑丁烯二醇与七甲基三硅氧烷进行硅氢加成反应得到了式A结构的硅醇化合物，接着异佛尔酮二异氰酸酯、聚丙二醇和硅醇化合物A进行嵌段共聚得到了式B结构的预聚物，在扩链剂DMPA的作用下进一步聚合得到了缩合物C，将低表面能的有机硅嵌入到聚氨酯的合成中，然后将以氢键的方式引入羧基化的碳纳米管，形成一层超疏水性保护层，大大提高了聚氨酯合成革的耐水解腐蚀性，具有良好的应用前景。

Description

耐水解腐蚀的聚氨酯合成革
技术领域
本发明属于革制品制造领域，具体涉及一种耐水解腐蚀的聚氨酯合成革。
背景技术
聚氨酯合成革属于聚氨酯弹性体的一类，具有光泽柔和、自然，手感柔软，真皮感强的外观，具有与基材粘接性能优异、抗磨损、耐挠曲、抗老化等优异的机械性能，同时还具备耐寒性好、透气、可洗涤、加工方便、价格优廉等优点，是天然皮革最为理想的替代品。
目前聚氨酯合成革的工艺化合成方法主要有干法和湿法两类。干法一般以离型纸为载体，将聚氨酯树脂浆料刮涂在离型纸上，加热烘干除去溶剂后形成连续均匀的聚氨酯薄膜，薄膜上刮涂粘结剂，与基布贴合，烘干固化后利用剥离装置将离型纸剥离并将成品人造革与离型纸分别成卷。干法制备的合成革致密、强度好、粘接牢固，但废气污染严重。湿法主要通过挤压使浆料充分渗透到非织造布间隙中，非织造布置于凝固浴中，利用“DMF-H2O”体系形成固体膜。湿法制备的合成革具有良好的透湿、透气性能，手感柔软轻盈。
目前的水性聚氨酯合成革虽然已经具备了良好的耐水解性，但是现有的聚氨酯是以使用含氟原料以增加其耐水性，但是含氟原料不仅会造成环境污染，还会影响人体健康，另外，其成品的后处理也比较麻烦，成品合成革的耐酸碱腐蚀性能差，沾上酸碱后会大大降低合成革的耐久性，促进聚氨酯树脂的分解反应，导致合成革表面开裂破损，大大降低了使用寿命。
发明内容
本发明的目的在于提供一种耐水解腐蚀的聚氨酯合成革，由于现有的水性聚氨酯由于以水为分散剂，含有亲水基团，其涂膜的耐水、耐化学性和耐溶剂性较差，本发明的耐水解腐蚀的聚氨酯合成革采用湿法制造工艺将改性聚氨酯乳液渗透到非织造布间得到，将低表面能的有机硅嵌入到聚氨酯的合成中，然后将以氢键的方式引入羧基化的碳纳米管，形成一层超疏水性保护层，大大提高了聚氨酯的耐水解腐蚀性，具有良好的应用前景。
本发明的目的可以通过以下技术方案实现：
耐水解腐蚀的聚氨酯合成革，采用湿法制造工艺将改性聚氨酯乳液渗透到非织造布间得到，所述的改性聚氨酯乳液的制备方法具体包括以下步骤：
第一步、将1.1-1.2mol1,4-丁烯二醇、1mol七甲基三硅氧烷和0.06mmol催化剂金属铂加入到反应瓶中，接着加入500ml甲苯，通入氮气保护，边搅拌边升温至110℃，搅拌反应7h，反应结束后，降低至室温，过滤，减压蒸馏除去甲苯，经柱层析分离，即得到式A结构的硅醇化合物；
第二步、将65g异佛尔酮二异氰酸酯、35g聚丙二醇、8g硅醇化合物A和1g催化剂，升温至80℃进行预聚2h,得到预聚物B，接着加入2.5gDMPA在80℃下继续缩聚3h，得到缩合物C；
第三步、称取1g碳纳米管和50ml酸溶液加入到反应瓶中，加热至95-100℃进行搅拌反应2-3h，反应结束后，冷却到室温，加入100ml去离子水，过滤，采用去离子水将固体化合物洗涤至pH为6.5-7.0,在85℃下进行干燥6-8h,即得到式D结构羧基化的碳纳米管；
第四步、将0.5g缩合物C、1g羧基化的碳纳米管D和0.8-1g尿素加入到100ml无水乙醇中，加热至回流反应15-20h，反应结束后，冷却至室温，过滤，洗涤，即得到式E结构的耐水解腐蚀聚氨酯，将离心后的耐水解腐蚀聚氨酯与0.01g消泡剂、0.02g增稠剂、0.01g流平剂搅拌混合均匀即得到改性聚氨酯乳液。
进一步，第一步中，所述的柱层析分离所用的洗脱剂为石油醚：甲醇：乙酸乙酯＝10:3:2。
进一步，第二步中，所述的催化剂为二月桂酸二正丁基锡。
进一步，第二步中，所述的所述的聚丙二醇在使用前在75-80℃、真空度为0.1MPa下进行脱水5-8h。
进一步，第三步中，所述的酸溶液为质量分数为65％的浓硝酸。
进一步，第四步中，所述的洗涤为采用40-45℃的无水乙醇离心洗涤8-10次。
本发明的有益效果：
本发明提供的一种耐水解腐蚀的聚氨酯合成革，是采用湿法制造工艺将改性聚氨酯乳液渗透到非织造布间得到，本发明的改性聚氨酯乳液的制备，首先是利用1,4-丁烯二醇与七甲基三硅氧烷进行硅氢加成反应得到了式A结构的硅醇化合物，接着异佛尔酮二异氰酸酯、聚丙二醇和硅醇化合物A进行嵌段共聚得到了式B结构的预聚物，在扩链剂DMPA的作用下进一步聚合得到了缩合物C，有机硅具有良好的耐氧化性和低表面能，将其嵌入到聚酯缩合物C，不仅赋予了聚氨酯合成革良好的柔软性和干爽舒适的触摸感，还弥补了聚氨酯的耐水性和耐溶剂性不足的缺点，将有机硅嵌入到聚氨酯中以化学键的方式连接，相比单独添加有机硅单体到聚氨酯乳液中，聚氨酯可改善有机硅的耐油性，不会出现混合不均的现象；
碳纳米管为超疏水材料，具有良好的耐腐蚀性能，用于合成革中，可提高材质的自清洁和抗菌性能，且耐冲击性好、防静电、耐磨损、稳定性高，但是碳纳米管强化学稳定性，不易进行反应，本发明将碳纳米管在浓硝酸的作用下，将碳纳米管进行羧基化，最后羧基化的碳纳米管、缩合物C与过量的尿素在无水乙醇中进行混合，首先尿素上的氨基进攻缩合物C上的-NCO基团进行缩合，然后一方面：羧基化的碳纳米管上的羧基与游离脲一侧的氨基形成稳定的分子间六元环氢键，游离脲另一侧的氨基分别与缩合物C上的羧基形成稳定的分子间六元环氢键；另一方面：羧基化的碳纳米管上的羧基还与缩合反应后的端氨基形成了稳定的六元环氢键；以氢键的方式将碳纳米管牢牢的连接在聚氨酯上，较大的高稳定性的侧链碳纳米管基团可确保酯键不会水解，结合有机硅的疏水性，大大提高了聚氨酯的耐水性和耐腐蚀性。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例描述所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明硅醇化合物A的反应式；
图2为本发明耐水解腐蚀聚氨酯E的反应流程图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，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。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
请参阅图1-2所示，本发明为一种耐水解腐蚀的聚氨酯合成革，是采用湿法制造工艺将改性聚氨酯乳液渗透到非织造布间得到，所述的改性聚氨酯乳液的制备方法具体包括以下步骤：
第一步、将1.1-1.2mol1,4-丁烯二醇、1mol七甲基三硅氧烷和0.06mmol催化剂金属铂加入到反应瓶中，接着加入500ml甲苯，通入氮气保护，边搅拌边升温至110℃，搅拌反应7h，反应结束后，降低至室温，过滤，减压蒸馏除去甲苯，经柱层析分离，柱层析分离所用的洗脱剂为石油醚：甲醇：乙酸乙酯＝10:3:2，即得到式A结构的硅醇化合物；
所得目标产物A的质谱结果为：HRMS m/z(ESI+)calcd for C11H30O4Si3([M+1]+),311.1425；
第二步、将65g异佛尔酮二异氰酸酯、35g聚丙二醇、8g硅醇化合物A和1g催化剂二月桂酸二正丁基锡，升温至80℃进行预聚2h,得到预聚物B，接着加入2.5gDMPA在80℃下继续缩聚3h，得到缩合物C；
缩合物C的红外表征如下所示：IR(KBr):
Figure BDA0002042189030000051
2271(-NCO),1712(-C＝O),796(-Si-CH3)cm-1；
第三步、称取1g碳纳米管和50ml质量分数为65％的浓硝酸加入到反应瓶中，加热至95-100℃进行搅拌反应2-3h，反应结束后，冷却到室温，加入100ml去离子水，过滤，采用去离子水将固体化合物洗涤至pH为6.5-7.0,在85℃下进行干燥6-8h,即得到式D结构羧基化的碳纳米管；
羧基化的碳纳米管D的红外表征如下所示：IR(KBr):
Figure BDA0002042189030000052
第四步、将0.5g缩合物C、1g羧基化的碳纳米管D和0.8-1g尿素加入到100ml无水乙醇中，加热至回流反应15-20h，反应结束后，冷却至室温，过滤，采用40-45℃的无水乙醇离心洗涤8-10次，即得到式E结构的耐水解腐蚀聚氨酯，将离心后的耐水解腐蚀聚氨酯与0.01g消泡剂、0.02g增稠剂、0.01g流平剂搅拌混合均匀即得到改性聚氨酯乳液；
耐水解腐蚀聚氨酯E的的红外表征如下所示：IR(KBr):
Figure BDA0002042189030000061
Figure BDA0002042189030000062
-COOH和-C＝O都发生了红移，是由于-COOH和-NH间形成氢键导致，在2240-2280cm-1处没有出现-NCO特征吸收峰，说明耐水解腐蚀聚氨酯E中没有-NCO基团，1633(-C＝C-)为碳纳米管的特征吸收；
所述的聚丙二醇在使用前在75-80℃、真空度为0.1MPa下进行脱水5-8h；
水性聚氨酯由于以水为分散剂，含有亲水基团，其涂膜的耐水、耐化学性和耐溶剂性较差；本发明提供的一种耐水解腐蚀的聚氨酯合成革，是采用湿法制造工艺将改性聚氨酯乳液渗透到非织造布间得到，所述的改性聚氨酯乳液的制备，首先是利用1,4-丁烯二醇与七甲基三硅氧烷进行硅氢加成反应得到了式A结构的硅醇化合物，接着异佛尔酮二异氰酸酯、聚丙二醇和硅醇化合物A进行嵌段共聚得到了式B结构的预聚物，在扩链剂DMPA的作用下进一步聚合得到了缩合物C，有机硅具有良好的耐氧化性和低表面能，将其嵌入到聚酯缩合物C，不仅赋予了聚氨酯合成革良好的柔软性和干爽舒适的触摸感，还弥补了聚氨酯的耐水性和耐溶剂性不足的缺点，将有机硅嵌入到聚氨酯中以化学键的方式连接，相比单独添加有机硅单体到聚氨酯乳液中，聚氨酯可改善有机硅的耐油性，不会出现混合不均的现象；
碳纳米管为超疏水材料，具有良好的耐腐蚀性能，用于合成革中，可提高材质的自清洁和抗菌性能，且耐冲击性好、防静电、耐磨损、稳定性高，但是碳纳米管强化学稳定性，不易进行反应，本发明将碳纳米管在浓硝酸的作用下，将碳纳米管进行羧基化，最后羧基化的碳纳米管、缩合物C与过量的尿素在无水乙醇中进行混合，首先尿素上的氨基进攻缩合物C上的-NCO基团进行缩合，然后一方面：羧基化的碳纳米管上的羧基与游离脲一侧的氨基形成稳定的分子间六元环氢键，游离脲另一侧的氨基分别与缩合物C上的羧基形成稳定的分子间六元环氢键；另一方面：羧基化的碳纳米管上的羧基还与缩合反应后的端氨基形成了稳定的六元环氢键；以氢键的方式将碳纳米管牢牢的连接在聚氨酯上，较大的高稳定性的侧链碳纳米管基团可确保酯键不会水解，结合有机硅的疏水性，大大提高了聚氨酯的耐水性和耐腐蚀性。
耐水解腐蚀的聚氨酯合成革的性能测试：
(1)接触角分析
对未改性的聚氨酯、缩合物C和耐水解腐蚀聚氨酯E的膜接触角进行测试
表一、聚氨酯膜的接触角
未改性的聚氨酯 缩合物C 耐水解腐蚀聚氨酯E
接触角/° 84.5 100.4 125.7
由表一可知，在成膜过程中，含Si链段更易迁移出膜的表面，由于Si的滑爽性和疏水性使得膜与水的接触角变大，碳纳米管的加入使得聚氨酯膜呈现超疏水状态，具有良好的耐水性。
(2)耐水性和耐溶剂性测试
对未改性的聚氨酯、缩合物C和耐水解腐蚀聚氨酯E的膜进行耐水性和耐溶剂性测试
表二、聚氨酯耐水性和耐溶剂性测试结果
未改性的聚氨酯 缩合物C 耐水解腐蚀聚氨酯E
吸水率/％ 73.4 34.2 21.6
甲苯吸收率/％ 283.1 82.1 53.4
由表二可知，，改性后的聚氨酯由于硅脂键的疏水性和碳纳米管的保护层，使得水分子和甲苯分子难以渗透，从而提高了聚氨酯合成革的耐水性和耐溶剂性。
(3)耐腐蚀性测试
参照行业标准CAB1001-2013《水性聚氨酯合成革》，耐腐蚀性分别采用质量分数为40wt％的氢氧化钠溶液和20wt％的盐酸溶液浸泡合成革，记录表面发生明显破裂的时间。分别采用未改性的聚氨酯乳液、缩合物C乳液和耐水解腐蚀聚氨酯E乳液(本发明的改性聚氨酯乳液)制得合成革，具体测试结果见下表三：
表三、聚氨酯合成革的耐腐蚀测试
Figure BDA0002042189030000081
由表三可知，本发明耐水解腐蚀的聚氨酯合成革具有良好的耐腐蚀性能。
以上内容仅仅是对本发明的构思所作的举例和说明，所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，只要不偏离发明的构思或者超越本权利要求书所定义的范围，均应属于本发明的保护范围。

Claims (6)

1.耐水解腐蚀的聚氨酯合成革，其特征在于：采用湿法制造工艺将改性聚氨酯乳液渗透到非织造布间得到，所述的改性聚氨酯乳液的制备方法具体包括以下步骤：
第一步、将1.1-1.2mol1,4-丁烯二醇、1mol七甲基三硅氧烷和0.06mmol催化剂金属铂加入到反应瓶中，接着加入500ml甲苯，通入氮气保护，边搅拌边升温至110℃，搅拌反应7h，反应结束后，降低至室温，过滤，减压蒸馏除去甲苯，经柱层析分离，即得到硅醇化合物A；
第二步、将65g异佛尔酮二异氰酸酯、35g聚丙二醇、8g硅醇化合物A和1g催化剂，升温至80℃进行预聚2h,得到预聚物B，接着加入2.5gDMPA在80℃下继续缩聚3h，得到缩合物C；
第三步、称取1g碳纳米管和50ml酸溶液加入到反应瓶中，加热至95-100℃进行搅拌反应2-3h，反应结束后，冷却到室温，加入100ml去离子水，过滤，采用去离子水将固体化合物洗涤至pH为6.5-7.0,在85℃下进行干燥6-8h,即得到羧基化的碳纳米管D；
第四步、将0.5g缩合物C、1g羧基化的碳纳米管D和0.8-1g尿素加入到100ml无水乙醇中，加热至回流反应15-20h，反应结束后，冷却至室温，过滤，洗涤，即得到耐水解腐蚀聚氨酯E，将耐水解腐蚀聚氨酯与0.01g消泡剂、0.02g增稠剂、0.01g流平剂搅拌混合均匀即得到改性聚氨酯乳液。
2.根据权利要求1所述的耐水解腐蚀的聚氨酯合成革，其特征在于：第一步中，所述的柱层析分离所用的洗脱剂为石油醚、甲醇、乙酸乙酯的混合物，其中石油醚：甲醇：乙酸乙酯=10:3:2。
3.根据权利要求1所述的耐水解腐蚀的聚氨酯合成革，其特征在于：第二步中，所述的催化剂为二月桂酸二正丁基锡。
4.根据权利要求1所述的耐水解腐蚀的聚氨酯合成革，其特征在于：第二步中，所述的聚丙二醇在使用前在75-80℃、真空度为0.1MPa下进行脱水5-8h。
5.根据权利要求1所述的耐水解腐蚀的聚氨酯合成革，其特征在于：第三步中，所述的酸溶液为质量分数为65%的浓硝酸。
6.根据权利要求1所述的耐水解腐蚀的聚氨酯合成革，其特征在于：第四步中，所述的洗涤为采用40-45℃的无水乙醇离心洗涤8-10次。
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