CN108084397A - 一种侧氨基聚硅氧烷改性聚氨酯涂层剂 - Google Patents

一种侧氨基聚硅氧烷改性聚氨酯涂层剂 Download PDF

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CN108084397A
CN108084397A CN201611038565.4A CN201611038565A CN108084397A CN 108084397 A CN108084397 A CN 108084397A CN 201611038565 A CN201611038565 A CN 201611038565A CN 108084397 A CN108084397 A CN 108084397A
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韩会义
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Abstract

一种侧氨基聚硅氧烷改性聚氨酯涂层剂，以侧氨基聚硅氧烷（SAPDMS）、聚四氢呋喃醚、聚乙二醇为混合软段，二羟甲基丙酸为亲水扩连剂，1,4‑丁二醇为硬段调节剂，与异佛尔酮二异氰酸酯反应合成了水性有机硅改性聚氨酯(WSSPU),并以WSSPU 为基础制备了防水透湿织物涂层剂。分别采用红外光谱、差热扫描量热仪、动态力学分析仪、正电子湮灭寿命谱等表征了WSSPU 膜的组成与微观结构，考察了WSSPU 膜的力学性能和涂层织物的防水透湿性能。结果表明，当侧氨基聚硅氧烷用量(质量比)<15%时，可以制得稳定的乳液。聚硅氧烷改性后膜内部微相分离结构更加明显，自由体积空洞变大，透湿性能提高。

Description

一种侧氨基聚硅氧烷改性聚氨酯涂层剂
技术领域
本发明涉及一种涂层剂，尤其涉及一种侧氨基聚硅氧烷改性聚氨酯涂层剂。
背景技术
防水透湿涂层织物，通常也叫防水透气织物或可呼吸织物，指一定压力的水不能透过织物，即织物能够防止雨水等液体透过，而人体运动散发出来的汗液蒸汽却能通过织物扩散或传导到外界，不会积聚在体表和织物之间，不会让人有发闷的感觉。聚氨酯类涂层具有一定的防水透湿性，但随着人们需求的不断提高，传统的聚氨酯涂层剂已不能满足市场需求。因此，对聚氨酯结构或加工工艺进行调整以改善其防水透湿性能的研究日益增多。
聚四氢呋喃醚（PTMG）微观上具有较大的自由体积，作为聚氨酯的软段，有利于水汽分子扩散透过，近年来被广泛用于防水透湿聚氨酯膜的合成；聚乙二醇（PEG）因为其具有不同于其他聚醚的72螺旋结构，成为了一种重要的导湿因子，近年来普遍用于无孔亲水透湿聚氨酯的合成。聚硅氧烷具有透气、耐高低温、整理织物具有滑软手感等特性，近年来已被广泛用于改性聚氨酯，相关文献多以改善聚氨酯的透气性、耐候性、生物相容性及表面手感为研究方向，而关于改善防水透湿性能的研究较为罕见。
发明内容
本发明的目的是为了开发一种性能良好的防水透湿织物涂层剂，设计了一种侧氨基聚硅氧烷改性聚氨酯涂层剂。
本发明解决其技术问题所采用的技术方案是：
侧氨基聚硅氧烷改性聚氨酯涂层剂的制备原料如下：聚四氢呋喃醚（PTMG，Mn=2000），工业级；聚乙二醇（PEG，Mn=1000），分析纯；β-氨乙基-γ-氨丙基聚二甲基硅氧烷（APDMS5），Mn=5000，氨值为0.8mmol·g−1，自制；异佛尔酮二异氰酸酯（IPDI），工业级；二羟甲基丙酸（DMPA），工业级，使用前100℃下真空除水5h；二月桂酸二丁基锡，分析纯；1,4-丁二醇（BDO），分析纯，使用前用4A分子筛浸泡7d；丁酮（MEK），分析纯，使用前用4A分子筛浸泡7d。TF-601增稠剂及涤丝纺布；氢氧化钾（KOH）、甲醇、丙酸、三乙胺（TEA）。
侧氨基聚硅氧烷改性聚氨酯涂层剂的制备步骤如下：将计量的PTMG、PEG置于装有搅拌、回流冷凝装置的四口瓶中，升温至100℃真空除水3h，降温至60～70℃，解除真空，通氮气，将IPDI/MEK（3/1）滴加入瓶中，升温至80℃反应1h；向体系滴加二月桂酸二丁基锡，其质量为混合聚醚质量0.5‰，继续反应1h后，依次滴入DMPA与BDO，继续反应3h；然后降温至50℃，加入定量的TEA中和，反应0.5h后，滴入SAPDMS5，滴毕，慢慢升温至80℃，保温反应3h，制得WSSPU预聚体。然后，将预聚体在水中高速剪切5～10min，即得固含量为25%的WSSPU乳液。
所述的模样品及涂层样品制备方法如下：将WSSPU乳液在聚四氟模具内流延成膜，自然干燥72h，置于真空烘箱内于60℃干燥1周，取出置于干燥器内备用；将WSSPU乳液加入适量TF-601增稠剂增稠，涂烘涤丝纺布面两次，涂烘温度为170℃，涂烘时间为45s，最终布面增重为15～20g·m−2，涂膜厚度为80～100μm，用于防水透湿测试。
本发明的有益效果是：
以聚四氢呋喃醚、聚乙二醇、侧氨丙基聚二甲基硅氧烷为混合软段，与异佛尔酮二异氰酸酯反应能够合成稳定的有机硅改性聚氨酯水乳液。一定量侧氨基聚硅氧烷的引入，使聚氨酯内部具有更明显的微相分离结构，使自由体积空洞变大，从而提高了透湿量。经过聚硅氧烷的改性，聚氨酯的防水性能变差了，但能够满足一般的服用要求（＞20 kPa）。WSSPU 膜具有较好的力学性能。因此，WSSPU 是一种性能良好的防水透湿织物涂层剂，具有较强的工业化推广价值。
具体实施方式
实施案例1：
侧氨基聚硅氧烷改性聚氨酯涂层剂的制备原料如下：聚四氢呋喃醚（PTMG，Mn=2000），工业级；聚乙二醇（PEG，Mn=1000），分析纯；β-氨乙基-γ-氨丙基聚二甲基硅氧烷（APDMS5），Mn=5000，氨值为0.8mmol·g−1，自制；异佛尔酮二异氰酸酯（IPDI），工业级；二羟甲基丙酸（DMPA），工业级，使用前100℃下真空除水5h；二月桂酸二丁基锡，分析纯；1,4-丁二醇（BDO），分析纯，使用前用4A分子筛浸泡7d；丁酮（MEK），分析纯，使用前用4A分子筛浸泡7d。TF-601增稠剂及涤丝纺布；氢氧化钾（KOH）、甲醇、丙酸、三乙胺（TEA）。侧氨基聚硅氧烷改性聚氨酯涂层剂的制备步骤如下：将计量的PTMG、PEG置于装有搅拌、回流冷凝装置的四口瓶中，升温至100℃真空除水3h，降温至60～70℃，解除真空，通氮气，将IPDI/MEK（3/1）滴加入瓶中，升温至80℃反应1h；向体系滴加二月桂酸二丁基锡，其质量为混合聚醚质量0.5‰，继续反应1h后，依次滴入DMPA与BDO，继续反应3h；然后降温至50℃，加入定量的TEA中和，反应0.5h后，滴入SAPDMS5，滴毕，慢慢升温至80℃，保温反应3h，制得WSSPU预聚体。然后，将预聚体在水中高速剪切5～10min，即得固含量为25%的WSSPU乳液。模样品及涂层样品制备方法如下：将WSSPU乳液在聚四氟模具内流延成膜，自然干燥72h，置于真空烘箱内于60℃干燥1周，取出置于干燥器内备用；将WSSPU乳液加入适量TF-601增稠剂增稠，涂烘涤丝纺布面两次，涂烘温度为170℃，涂烘时间为45s，最终布面增重为15～20g·m−2，涂膜厚度为80～100μm，用于防水透湿测试。
实施案例2：
红外光谱（FTIR）分析：使用Nicolet8700型傅里叶变换红外光谱仪，将已经提纯的聚氨酯预聚体涂于KBr晶体窗片上，待溶剂挥发干净后进行测试。结果：3326cm−1为氨酯键中NH键伸缩振动与弯曲振动的特征吸收峰；2945cm−1附近的吸收峰归属于甲基及亚甲基中CH的伸缩振动；1710cm−1为氨酯键中CO伸缩振动的特征吸收峰；1118cm−1归属于PTMG中COC的伸缩振动特征峰，同时在1042cm−1附近出现了归属于SAPDMS中SiOSi伸缩振动的特征峰，由于其与聚醚多元醇在此附近的吸收峰部分重叠，使得峰形略有变化，另外在803cm−1附近出现了归属于SiCH3中CH3对称变形振动的特征吸收峰；将谱线a与谱线b对比，发现两曲线在图上标记部分的峰形与峰位置均有较大差异，以上表明聚硅氧烷与聚氨酯预聚体发生了反应，而不是物理混合。
实施案例3：
乳液粒度及zeta电位测定：使用ZS90型纳米粒度及zeta电位分析仪，WSSPU乳液稀释至1%，在25℃下测试。结果：加入SAPDMS的WSSPU乳液粒径均大于WSSPU0的乳液粒径，随着SAPDMS含量的增加，粒径分布变宽（参数PDI增大）；zeta电位的绝对值均大于30mV，水分散体是稳定的。当SAPDMS含量为18%时，乳液出现漂浮物，乳液稳定性变差。
实施案例4：
示差扫描量热（DSC）测试：称取膜样约10mg，使用DSC1型示差扫描量热仪进行测试，升温速率为10℃·min−1。结果：与WSPU0相比较，SAPDMS5改性后的WSSPU系列膜均在−80℃附近和−45℃附近出现两个归属于软段的玻璃化转变过程，表明SAPDMS5改性的聚氨酯膜中，混合软段之间出现了微观相分离。同时，在DSC曲线上未发现归属于硬段的玻璃化转变过程或结晶过程。
实施案例5：
动态力学分析（DMA）：将聚氨酯膜制成约0.5cm×0.5cm×0.1cm的块样，使用DMA/SDTA861e型动态力学分析仪，测定频率1Hz，升温速率3℃·min−1，温度扫描范围为−150～150℃。结果：在WSSPU膜中，软硬段具有明显的微相分离结构；同时，随着SAPDMS5含量的增加，硬段与软段的tanδ峰值之差Δ(αh−αs)呈逐渐增大趋势，当SAPDMS5含量从5%增加到15%时，Δ(αh−αs)从57.4℃增加到92.5℃。这表明随着SAPDMS5含量的增加，改性聚氨酯膜的微相分离程度逐渐提高。
实施案例6：
正电子湮灭谱（PLS）：将聚氨酯膜制为1cm×1cm×0.1cm的样品，在中国科学院高能物理研究所核分析实验室的快-慢符合正电子湮没寿命谱仪上测定，谱仪分辨率202ps，扣源成分：385ps，13%，采用三寿命自由拟合。结果：WSSPU膜内部自由体积空洞半径与水分子直径（0.324nm）相当，随着SAPDMS5含量的增加，自由体积空洞的尺寸不断增大；相对自由体积分数也呈增大趋势。
实施案例7：
力学性能：使用AGS-J型力学试验机，按GB/T1040—2006测试，拉伸速度250mm·min−1，每组5个样条。透湿量测定：使用织物透湿量测定仪，按照GB/T12704—91A标准，测定涂层样品的透湿量。结果：由于SAPDMS5分子链中氨基含量大于2mol·mol−1，由其改性合成的聚氨酯具有轻度交联结构（常温固化膜样品不再溶于氯仿等有机溶剂），交联结构对膜的力学性质会有影响，随着SAPDMS5含量增加，拉伸强度不断增大，断裂伸长率逐渐降低。当SAPDMS5含量从0增加到15%时，断裂强度从10.5MPa增到15.3MPa，断裂伸长率从904%降到818%聚氨酯的力学性能主要由其微观结构决定，对于线性聚氨酯，其硬段起到物理交联点的作用，决定着膜的力学强度。对于WSSPU膜，其微观上具有轻度交联结构，辅助硬段的物理交联作用，提高了膜的力学强度；同时，由于WSSPU中的SAPDMS5含量增加，交联点增多，使聚合物分子柔性有所降低，断裂伸长率相应降低。
实施案例8：
防水性测定：使用YG(B)812D—20型数字渗水性测定仪，按照GB/T4744—1997标准，测定涂层样品所耐静水压。结果：透湿量随聚硅氧烷含量的增加呈先升高后降低的趋势，WSSPU涂层织物的最高透湿量达到1834g·m−2·d−1。由前面的微观结构表征结果可知，少量聚硅氧烷的引入，提高了聚氨酯微相分离的程度，自由体积大小与自由体积分数均有所增大，有利于水汽分子透过。另一方面，大量的PTMG被拒水性的SAPDMS取代，并且生成了大量疏水性的脲键，且膜表面富集大量的聚硅氧烷不利于水汽分子的“吸附”，致使透湿速度变慢，透湿量降低。随着聚硅氧烷含量的增加，涂层织物的静水压都在不断降低。从曲线中还可以看出，当有1%的聚硅氧烷引入到聚氨酯中时，涂层织物的静水压就急剧下降，随着聚硅氧烷含量的进一步增大，静水压降幅变小。尽管侧氨基聚硅氧烷改性聚氨酯形成了交联结构，但仍属于轻度交联（交联度太大时，预聚体出现凝胶，不能得到水分散体），不能根本改变聚硅氧烷使改性聚氨酯分子间距离增大的本质，且聚硅氧烷含量越大，使分子间距离增大的效应越强。因此，侧氨基聚硅氧烷改性聚氨酯涂层织物的静水压随着聚硅氧烷含量的增加逐渐降低。

Claims (3)

1.一种侧氨基聚硅氧烷改性聚氨酯涂层剂，其制备原料如下：聚四氢呋喃醚（PTMG，Mn=2000），工业级；聚乙二醇（PEG，Mn=1000），分析纯；β-氨乙基-γ-氨丙基聚二甲基硅氧烷（APDMS5），Mn=5000，氨值为0.8mmol·g−1，自制；异佛尔酮二异氰酸酯（IPDI），工业级；二羟甲基丙酸（DMPA），工业级，使用前100℃下真空除水5h；二月桂酸二丁基锡，分析纯；1,4-丁二醇（BDO），分析纯，使用前用4A分子筛浸泡7d；丁酮（MEK），分析纯，使用前用4A分子筛浸泡7d；TF-601增稠剂及涤丝纺布；氢氧化钾（KOH）、甲醇、丙酸、三乙胺（TEA）。
2.根据权利要求1所述的侧氨基聚硅氧烷改性聚氨酯涂层剂，其特征是制备步骤如下：将计量的PTMG、PEG置于装有搅拌、回流冷凝装置的四口瓶中，升温至100℃真空除水3h，降温至60～70℃，解除真空，通氮气，将IPDI/MEK（3/1）滴加入瓶中，升温至80℃反应1h；向体系滴加二月桂酸二丁基锡，其质量为混合聚醚质量0.5‰，继续反应1h后，依次滴入DMPA与BDO，继续反应3h；然后降温至50℃，加入定量的TEA中和，反应0.5h后，滴入SAPDMS5，滴毕，慢慢升温至80℃，保温反应3h，制得WSSPU预聚体；然后，将预聚体在水中高速剪切5～10min，即得固含量为25%的WSSPU乳液。
3.根据权利要求1所述的侧氨基聚硅氧烷改性聚氨酯涂层剂，其特征是所述的模样品及涂层样品制备方法如下：将WSSPU乳液在聚四氟模具内流延成膜，自然干燥72h，置于真空烘箱内于60℃干燥1周，取出置于干燥器内备用；将WSSPU乳液加入适量TF-601增稠剂增稠，涂烘涤丝纺布面两次，涂烘温度为170℃，涂烘时间为45s，最终布面增重为15～20g·m−2，涂膜厚度为80～100μm，用于防水透湿测试。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111663338A (zh) * 2020-07-07 2020-09-15 湖南工程学院 一种多功能水性温敏聚氨酯整理剂的制备方法
CN112851248A (zh) * 2021-01-29 2021-05-28 烟台华宝新材料科技有限公司 一种高强度混凝土及其制备方法
CN112962356A (zh) * 2021-01-26 2021-06-15 湖南工业大学 一种高抗压强度、防水纸浆模塑材料及其制备方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111663338A (zh) * 2020-07-07 2020-09-15 湖南工程学院 一种多功能水性温敏聚氨酯整理剂的制备方法
CN111663338B (zh) * 2020-07-07 2023-06-20 湖南工程学院 一种多功能水性温敏聚氨酯整理剂的制备方法
CN112962356A (zh) * 2021-01-26 2021-06-15 湖南工业大学 一种高抗压强度、防水纸浆模塑材料及其制备方法
CN112851248A (zh) * 2021-01-29 2021-05-28 烟台华宝新材料科技有限公司 一种高强度混凝土及其制备方法
CN112851248B (zh) * 2021-01-29 2022-07-08 烟台华宝新材料科技有限公司 一种高强度混凝土及其制备方法

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