CN114703600A - 一种防水透气聚氨酯马靴内衬膜的制备方法 - Google Patents

一种防水透气聚氨酯马靴内衬膜的制备方法 Download PDF

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CN114703600A
CN114703600A CN202210375137.XA CN202210375137A CN114703600A CN 114703600 A CN114703600 A CN 114703600A CN 202210375137 A CN202210375137 A CN 202210375137A CN 114703600 A CN114703600 A CN 114703600A
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Abstract

本发明涉及一种防水透气马靴内衬膜的制备方法，属于功能性纺织薄膜技术领域。本发明首先通过巯基‑烯点击化学反应采用3‑巯基‑1,2‑丙二醇对亚油酸甲酯进行改性，引入端羟基基团；然后以带端羟基的亚油酸甲酯、聚丁二醇和异佛尔酮二异氰酸酯、2,2‑二羟甲基丙酸、1,4‑丁二醇等为主要原料合成亚油酸甲酯改性的聚氨酯，并采用本发明合成聚氨酯通过静电纺丝技术制备防水透气聚氨酯马靴内衬膜。本发明制备的防水透气聚氨酯马靴内衬膜的防水效果和透气性能优异，采用C‑C长链起到疏水效果，属于环保型防水透气膜。本发明疏水C‑C长链在聚氨酯大分子链段侧端，不影响主体结构，不影响聚氨酯原有的力学性能，且疏水长链使得聚氨酯马靴内衬膜具有耐久的疏水效果，并保持较好的透气性，具有重要的实际应用价值。

Description

一种防水透气聚氨酯马靴内衬膜的制备方法
技术领域
本发明涉及功能性纺织薄膜技术领域，尤其是指一种防水透气聚氨酯马靴内衬膜的制备方法。
背景技术
马靴是重要的马术装备之一，是防止马裤被马的汗水弄脏并且在骑马时起防护作用。由于其美观、舒适也在生活和时尚中受到人们的追捧，但是马靴由皮革制成，吸湿性、透气性较差，故穿着过程中会有汗液的渗出与聚集，并且过多的汗液无法顺利排出，导致马靴内温度与湿度的升高，容易滋生真菌引起“脚气”等问题。现有的内衬常为海绵、无纺布、帆布等，尽管会带来舒适的作用，但是透气透湿性较差，依然会让马靴处于一种相对湿热的环境，并且市面上的吸汗鞋垫的比表面积小，吸湿能力有限。
水性聚氨酯薄膜具有优异的成膜性和物理机械性能，安全环保，价格低廉，被广泛地应用于涂料、胶黏剂、纺织印染、薄膜等领域。采用水性聚氨酯开发防水透气薄膜引起了广泛关注。文献(朱敏,周向东.短链含氟PU防水透湿整理剂的合成及应用性能[J].印染,2012,38(16):13-17.)以聚丙二醇、异佛尔酮二异氰酸酯和甲基丙烯酸六氟丁酯等为主要原料，合成聚氨酯-含氟丙烯酸酯复合乳液，该PU涂层的防水效果较好。
文献(李智勇,周惠敏,夏鑫.含氟聚氨酯/聚氨酯纳米纤维膜复合织物的制备及其防水透湿性能[J].纺织学报,2016,37(10):83-88.)首先将一种含氟聚氨酯疏水剂引入聚氨酯纺丝液，通过静电纺丝技术制备了具有珠丝结构粗糙表面的含氟聚氨酯纳米纤维膜复合织物，最终获得了良好的防水透湿性能的织物。但该类该方法的疏水性能主要靠对环境有危害的含氟单体产生，而部分含氟防水剂因环保问题已经逐渐被市场淘汰。
发明内容
为解决上述技术问题，本发明提供了一种防水透气马靴内衬膜的制备方法，本发明通过巯基-烯点击化学反应采用3-巯基-1,2-丙二醇对亚油酸甲酯进行改性，引入端羟基基团；然后以带端羟基的亚油酸甲酯、聚丁二醇和异佛尔酮二异氰酸酯、2,2-二羟甲基丙酸、1,4-丁二醇等为主要原料合成亚油酸甲酯改性的聚氨酯，并采用本发明合成聚氨酯通过静电纺丝技术制备防水透气马靴内衬膜；本发明疏水C-C长链通过聚合反应接枝在聚氨酯分子链段的侧端，不影响聚氨酯原有的优良性能，且疏水长链使得聚氨酯薄膜具有耐久的疏水效果，并保持较好的透气性，具有重要的实际应用价值。
本发明的第一个目的是提供一种防水透气马靴内衬膜的制备方法，包括如下步骤：
(1)将3-巯基-1,2-丙二醇和亚油酸甲酯加入圆底烧瓶中，采用三乙胺作为催化剂、四氢呋喃作为溶剂，升高至一定温度反应一定时间，制得带端羟基的亚油酸甲酯；
(2)将聚丁二醇和异佛尔酮二异氰酸酯溶于四氢呋喃中，采用二丁基二月桂酸锡作为催化剂，升高至一定温度反应一定时间，制得聚氨酯预聚体；
(3)然后将2,2-二羟甲基丙酸和带端羟基的亚油酸甲酯加入聚氨酯预聚体，升高一定温度反应一定时间，将亚油酸甲酯的疏水长链引入聚氨酯预聚体；
(4)将1,4-丁二醇键入继续反应一定时间对聚氨酯预聚体扩链，并采用三乙胺进行中和，最后加入去离子水高速搅拌，乳化0.5～1h,并通过减压蒸馏去除溶剂得到疏水聚氨酯；
(5)最后采用静电纺丝技术采用疏水聚氨酯制备马靴内衬膜。
在本发明的一个实施例中，在步骤(1)中，所述的3-巯基-1,2-丙二醇与亚油酸甲酯的摩尔比为1～1.2:1，3-巯基-1,2-丙二醇稍微过量，保证亚油酸甲酯完全反应；
在本发明的一个实施例中，在步骤(1)中，所述的反应温度为70～85℃，反应时间为1～2h；
在本发明的一个实施例中，在步骤(2)中，所述的聚丁二醇和异佛尔酮二异氰酸酯摩尔比为1:2～2.2，异佛尔酮二异氰酸酯稍微过量，有助于促进聚氨酯预聚体的生成；
在本发明的一个实施例中，在步骤(2)中，所述的反应温度为40～60℃，反应时间为5～6h；
在本发明的一个实施例中，在步骤(3)中，所述的2,2-二羟甲基丙酸、带端羟基的亚油酸甲酯与聚丁二醇的摩尔比为1:1:1，所述的反应温度为75～80℃，反应时间为3～4h；
在本发明的一个实施例中，在步骤(4)中，所述的1,4-丁二醇扩链反应温度为75～80℃，反应时间为2～3h；
在本发明的一个实施例中，在步骤(4)中，所述的三乙胺中和温度为40～50℃，中和0.5～1h；
在本发明的一个实施例中，在步骤(5)中，所述的静电纺丝电压为15kV，注射速度为0.5mL/h，采用四氢呋喃作为溶剂。
本发明的原理是：3-巯基-1,2-丙二醇的硫醇与亚油酸甲酯的不饱和双键通过巯基-烯点击化学反应合成带端羟基的亚油酸甲酯，在聚氨酯聚合反应过程中，采用带端羟基的亚油酸甲酯作为扩链剂与异氰酸酯基团反应，将疏水C-C链段通过共价键引入到聚氨酯大分子链段的侧端合成疏水改性的聚氨酯；采用改性聚氨酯通过静电纺丝技术制备防水透气马靴内衬膜，疏水链段裸露在静电纺丝纤维的外侧表面，起到疏水作用。
本发明的上述技术方案相比现有技术具有以下优点：
本发明制备的防水透气马靴内衬膜的防水效果和透气性能优异，采用疏水C-C长链起到疏水效果，未采用对人体有害的含氟疏水长链，属于环保型防水透气膜。本发明疏水C-C长链在聚氨酯大分子链段侧端，不影响主体结构，不影响聚氨酯原有的优良性能，且疏水C-C长链通过共价键固定在聚氨酯大分子链上，因此防水透气聚氨酯马靴内衬膜的功能性耐久，具有广阔的应用前景和重要的实际应用价值。
附图说明
图1为本发明端羟基改性的亚油酸甲酯的合成路线。
图2为本发明疏水改性聚氨酯的结构示意图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
实施例1
(1)将10.8g(0.1mol)3-巯基-1,2-丙二醇、29.4g(0.1mol)亚油酸甲酯和10.1g(0.1mol)三乙胺和50mL四氢呋喃加入圆底烧瓶中，升温至80℃反应1.5h，制得带端羟基的亚油酸甲酯；
(2)将9g(相当于0.1mol丁二醇单体)聚丁二醇和44.4g(0.2mol)异佛尔酮二异氰酸酯和5滴二丁基二月桂酸锡溶于50mL四氢呋喃中，升高温度至50℃反应5h，制得聚氨酯预聚体；然后将13.4g(0.1mol)2,2-二羟甲基丙酸和步骤(1)制得的带端羟基的亚油酸甲酯加入聚氨酯预聚体，升高温度至80℃反应3h，将亚油酸甲酯的疏水长链引入聚氨酯预聚体；然后加入18.0g(0.2mol)1,4-丁二醇继续在80℃反应2h对聚氨酯预聚体扩链，缓慢滴加三乙胺进行中和，于40℃反应1h。最后加入去离子水高速搅拌，乳化1h,并通过减压蒸馏去除溶剂得到疏水聚氨酯。
实施例2
(1)将12.9g(0.12mol)3-巯基-1,2-丙二醇、29.4g(0.1mol)亚油酸甲酯和10.1g(0.1mol)三乙胺和50mL四氢呋喃加入圆底烧瓶中，升温至85℃反应1h，制得带端羟基的亚油酸甲酯；
(2)将9g(相当于0.1mol丁二醇单体)聚丁二醇和48.8g(0.22mol)异佛尔酮二异氰酸酯和5滴二丁基二月桂酸锡溶于50mL四氢呋喃中，升高温度至60℃反应6h，制得聚氨酯预聚体；然后将13.4g(0.1mol)2,2-二羟甲基丙酸和步骤(1)制得的带端羟基的亚油酸甲酯加入聚氨酯预聚体，升高温度至75℃反应2h，将亚油酸甲酯的疏水长链引入聚氨酯预聚体；然后加入18.0g(0.2mol)1,4-丁二醇继续在75℃反应3h对聚氨酯预聚体扩链，缓慢滴加三乙胺进行中和，于50℃反应0.5h。最后加入去离子水高速搅拌，乳化1h,并通过减压蒸馏去除溶剂得到疏水聚氨酯。
对比例1
将9g(相当于0.1mol丁二醇单体)聚丁二醇和48.8g(0.22mol)异佛尔酮二异氰酸酯和5滴二丁基二月桂酸锡溶于50mL四氢呋喃中，升高温度至60℃反应6h，制得聚氨酯预聚体；然后将13.4g(0.1mol)2,2-二羟甲基丙酸加入聚氨酯预聚体，升高温度至75℃反应2h，将亚油酸甲酯的疏水长链引入聚氨酯预聚体；然后加入18.0g(0.2mol)1,4-丁二醇继续在75℃反应3h对聚氨酯预聚体扩链，缓慢滴加三乙胺进行中和，于50℃反应0.5h。最后加入去离子水高速搅拌，乳化1h,并通过减压蒸馏去除溶剂得到聚氨酯。
实施例3
将实施案例1所制备的疏水聚氨酯加入四氢呋喃中，常温下搅拌至完全溶解制备含量为20％的聚氨酯纺丝液。采用静电纺丝设备将聚氨酯纺丝液制备防水透气膜，其中纤维直径为500nm，厚度为100um，纺丝电压为15kV，注射速度为0.5mL/h。最后，将制得的聚氨酯纤维膜放入60℃的真空烘箱中烘燥以确保溶剂全部挥发。
实施例4
将实施案例2所制备的疏水聚氨酯加入四氢呋喃中，常温下搅拌至完全溶解制备含量为20％的聚氨酯纺丝液。采用静电纺丝设备将聚氨酯纺丝液制备防水透气膜，其中纤维直径为1000nm，厚度为200um，纺丝电压为15kV，注射速度为0.5mL/h。最后，将制得的聚氨酯纤维膜放入60℃的真空烘箱中烘燥以确保溶剂全部挥发。
对比例2
将对比例1所制备的聚氨酯加入四氢呋喃中，常温下搅拌至完全溶解制备含量为20％的聚氨酯纺丝液。采用静电纺丝设备将聚氨酯纺丝液制备防水透气膜，其中纤维直径为1000nm，厚度为200um，纺丝电压为15kV，注射速度为0.5mL/h。最后，将制得的聚氨酯纤维膜放入60℃的真空烘箱中烘燥以确保溶剂全部挥发。
对上述马靴内衬膜的防水性能、透气性能和力学性能进行测试。
马靴内衬膜的防水性能按照GB/T 30447-2013《纳米薄膜接触角测量方法》标准测定。
马靴内衬膜的水洗方法参照AATCC 61-2006《家用和商用耐洗涤色牢度的加速试验》。
马靴内衬膜的透气性能按照GB/T 5453-1997《纺织品织物透气性的测定》标准测定。
马靴内衬膜的力学性能按照GB/T 3923.1-2013《纺织品织物拉伸性能第1部分：断裂强力和断裂伸长率的测定(条样法)》标准测定。
表1 所示为最终测得马靴内衬膜的防水性能、透气性能和力学性能：
Figure BDA0003590052720000051
从表1中可以看出，如对比例2所示，常规聚氨酯制备的马靴内衬膜的接触角为0o，表明其防水性能差；经本发明疏水聚氨酯制备的马靴内衬膜的接触角升高至130o左右，表明其具有较好的防水性能。且经20次水洗后，马靴内衬膜的接触角仍保持较高值，表明其疏水性能具有较好的耐水洗性能。经疏水改性后，聚氨酯马靴内衬膜的透气性未受到影响，均具有较好的透气性，且拉伸断裂应力未受到影响，表明疏水改性并未影响聚氨酯马靴内衬膜的透气性和强力性能。
上述结果表明，经本发明方法制备的聚氨酯马靴内衬膜具有较好的防水性能和透气性能。
显然，上述实施例仅仅是为清楚地说明所作的举例，并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (9)

1.一种防水透气聚氨酯马靴内衬膜的制备方法，其特征在于，包括如下步骤：
(1)将3-巯基-1,2-丙二醇和亚油酸甲酯加入圆底烧瓶中，采用三乙胺作为催化剂、四氢呋喃作为溶剂，升高至一定温度反应一定时间，制得带端羟基的亚油酸甲酯；
(2)将聚丁二醇和异佛尔酮二异氰酸酯溶于四氢呋喃中，采用二丁基二月桂酸锡作为催化剂，升高至一定温度反应一定时间，制得聚氨酯预聚体；
(3)然后将2,2-二羟甲基丙酸和带端羟基的亚油酸甲酯加入聚氨酯预聚体，升高一定温度反应一定时间，将亚油酸甲酯的疏水长链引入聚氨酯预聚体；
(4)将1,4-丁二醇加入继续反应一定时间对聚氨酯预聚体扩链，并采用三乙胺进行中和，最后加入去离子水高速搅拌，乳化0.5～1h,并通过减压蒸馏去除溶剂得到疏水聚氨酯；
(5)最后采用静电纺丝技术采用疏水聚氨酯制备马靴内衬膜。
2.根据权利要求1所述的一种防水透气聚氨酯马靴内衬膜的制备方法，其特征在于：在步骤(1)中，所述的3-巯基-1,2-丙二醇与亚油酸甲酯的摩尔比为1～1.2:1，3-巯基-1,2-丙二醇稍微过量，保证亚油酸甲酯完全反应。
3.根据权利要求1所述的一种防水透气聚氨酯马靴内衬膜的制备方法，其特征在于：在步骤(1)中，所述的反应温度为70～85℃，反应时间为1～2h。
4.根据权利要求1所述的一种防水透气聚氨酯马靴内衬膜的制备方法，其特征在于：在步骤(2)中，所述的聚丁二醇和异佛尔酮二异氰酸酯摩尔比为1:2～2.2，异佛尔酮二异氰酸酯稍微过量，有助于促进聚氨酯预聚体的生成。
5.根据权利要求1所述的一种防水透气聚氨酯马靴内衬膜的制备方法，其特征在于：在步骤(2)中，所述的反应温度为40～60℃，反应时间为5～6h。
6.根据权利要求1所述的一种防水透气聚氨酯马靴内衬膜的制备方法，其特征在于：在步骤(3)中，所述的2,2-二羟甲基丙酸、带端羟基的亚油酸甲酯与聚丁二醇的摩尔比为1:1:1，所述的反应温度为75～80℃，反应时间为3～4h。
7.根据权利要求1所述的一种防水透气聚氨酯马靴内衬膜的制备方法，其特征在于：在步骤(4)中，所述的1,4-丁二醇扩链反应温度为75～80℃，反应时间为2～3h。
8.根据权利要求1所述的一种防水透气聚氨酯马靴内衬膜的制备方法，其特征在于：在步骤(4)中，所述的三乙胺中和温度为40～50℃，中和0.5～1h。
9.根据权利要求1所述的一种防水透气聚氨酯马靴内衬膜的制备方法，其特征在于：在步骤(5)中，所述的静电纺丝电压为15kV，注射速度为0.5mL/h，采用四氢呋喃作为溶剂。
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