CN106739309B - 一种赋型聚氨酯复合薄膜及其制备方法 - Google Patents

一种赋型聚氨酯复合薄膜及其制备方法 Download PDF

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CN106739309B
CN106739309B CN201611058993.3A CN201611058993A CN106739309B CN 106739309 B CN106739309 B CN 106739309B CN 201611058993 A CN201611058993 A CN 201611058993A CN 106739309 B CN106739309 B CN 106739309B
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谢伟娟
钦湘
吴勇
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NANJING SHUANGWEI BIOTECHNOLOGY CO Ltd
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Abstract

本发明公开了一种赋型聚氨酯复合薄膜，由聚氨酯A制成的弹性层、以及聚氨酯B制成的织网层热压合制成，织网层是基于聚氨酯B的纤维细丝交织制成；聚氨酯A或聚氨酯B通过使至少一种聚合多元醇与至少一种二异氰酸酯和至少一种扩链剂反应制备获得。本发明的复合膜解决了现有TPU材料同时提高薄膜拉升性能、弹性以及硬度、撕裂强度相悖的情形，通过将两种不同力学性能的热塑性聚氨酯材料热压，获得生物相容性高，安全性能稳定的产品，产品透光率高，可适用于诸多应用领域。

Description

一种赋型聚氨酯复合薄膜及其制备方法
技术领域
本发明涉及材料化学领域，具体地说涉及一种赋型聚氨酯复合薄膜及其制备方法。
背景技术
聚氨酯材料目前广泛地被应用在医疗卫生领域，其具备优良的物理机械性能和生物相容性，TPU又称为聚氨基甲酸酯弹性体，其主链上含有较多氨基甲酸酯基团，与异氰酸酯及二醇或二胺类扩链剂逐步加成聚合而成。从分子结构上看，其主要包含以大分子二醇为主的软段、以及异氰酸酯为主的硬段。软段占比高会提升TPU的拉伸性能；硬段占比高会增加其弹性和强度。通过硬段和软段的相邻组合，使TPU材料不仅具备橡胶的高弹性性能，同时也具备较好的强度。
现有的TPU材料在分子设计阶段根据产品拉伸性能、硬度上的需求进行设定，但从材料本身来讲，很难同时满足前述两个特点。
随着现代医疗行业和医疗材料的发展，提出了需要介入人体实现充盈的薄膜材料，该材料制成的充盈薄膜囊，需能承受至少3个大气压不破裂，且尽量减小对人体的异物感和不适感，尤其是要具备一定的透光率。目前还没有任何一种TPU材料能达到该要求。其中不少TPU材料虽然拥有不错的性能，但颜色会变黄，透光率不足80％。
发明内容
发明目的：本发明的目的是提供一种兼具拉伸性能、硬度和弹性的聚氨酯复合薄膜；本发明还有一个目的是提供前述复合膜的制备方法。
技术方案：为了实现上述发明目的，本发明的一种赋型聚氨酯复合薄膜，由聚氨酯A制成的弹性层、以及聚氨酯B制成的织网层热压合制成，所述织网层是基于聚氨酯B的纤维细丝交织制成；所述聚氨酯A或聚氨酯B通过使至少一种聚合多元醇与至少一种二异氰酸酯和至少一种扩链剂反应制备获得。
本发明是采用两种TPU聚氨酯材料制成的复合膜，弹性层材料的软段浓度相对较高，生物相容性好，该材料要求其弹性性能好，虽然这样模量和强度会有所下降，其硬度满足40邵尔D即可。为了提高材料的强度，本发明还提供了通过织网层复合的方法，提高整体材料的强度。织网层材料的强度和硬度远高于聚氨酯A的性能，但该类材料一般需要采用芳香族异氰酸酯才能达到70邵尔D以上的硬度，该类材料制备获得的TPU薄膜透光率不佳，且柔韧性不足，因此通过设计成大孔径织网，以克服其透光率不足的缺陷。
进一步地，所述聚合多元醇为聚己二酸丁二醇、聚丁二醇、聚ε-己内酯二醇的任意一种。优选为聚己二酸丁二醇或聚丁二醇。
进一步地，所述聚氨酯A制备时用的二异氰酸酯为脂肪族异氰酸酯，包括异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯的任意一种。
进一步地，所述聚氨酯B制备时用的二异氰酸酯为芳香族异氰酸酯，包括对苯二异氰酸酯、甲苯二异氰酸酯、4，4’-二苯甲烷二异氰酸酯的任意一种。
作为本发明的进一步优化，所述聚氨酯A的软段来自聚丁二醇酯，聚氨酯B的软段来自聚己二酸丁二醇酯。优选的，聚氨酯A的软段相对分子质量在1500-3000之间。选用聚丁二醇作为聚氨酯A的聚合多元醇，其获得的产品弹性性能更好。聚氨酯B的软段相对分子质量在1000-2000之间，基于聚己二酸丁二醇作为聚合多元醇制得的聚氨酯材料其抗撕裂强度高，硬度大，力学性能要高于聚氨酯A。
进一步地，所述扩链剂包括但不限于乙二醇、1，3-丙二醇、1，4-丁二醇、1，6-己二醇的任意一种或多种的组合。
须说明的时候，以上聚氨酯A和聚氨酯B制备对应的当量比，本领域技术人员可根据异氰酸酯基团与羟基反应的当量比进行适应性调整。另外，为了提高产品综合性能，可根据需要加入助剂，例如有机锡类催化剂、紫外线吸收剂、抗氧化剂等。
所述聚氨酯B制成的纤维细丝直径不超过0.2mm，相邻两根平行距离在5～15mm。纤维细丝的纤维间距较大，同时保证一定的塑形强度。所述纤维细丝的排布方式优选相互交织的方式，其中一种较常见的，将经线、纬线逐个交替组合，形成两组平行交织的织网型聚氨酯层。
如前述复合薄膜的制备方法，是将聚氨酯A各组分混合，经螺杆挤出机挤压反应，然后送经压延成型设备获得弹性层；利用静电纺丝技术对聚氨酯B进行加工，获得直径不超过0.2mm的聚氨酯纤维细丝；纤维细丝加工排列后于弹性层的一侧热压，获得赋型聚氨酯复合薄膜。
纤维细丝相邻两根平行距离在2～5mm，直径不超过0.2mm，在至少85℃下热压于弹性层表面。热压后弹性层和织网层的复合薄膜厚度是热压前弹性层的70～90％，由于聚氨酯A的玻璃化温度低于聚氨酯B，在加热状态下使织网层嵌于弹性层中。
该产品未经织网层热压的一面为有效表面，薄膜弹性高，生物相容性好。当其受应力变形到一定程度后，具有较高硬度和撕裂强度的织网层起到赋型的作用，防止整个复合膜进一步变形，甚至超过弹性层的撕裂强度。该复合膜未热压织网层的弹性层部分透光率在95％以上，整体平均透光率在90.3％以上。
有益效果：本发明的复合膜解决了现有TPU材料同时提高薄膜拉升性能、弹性以及硬度、撕裂强度相悖的情形，通过将两种不同力学性能的热塑性聚氨酯材料热压，获得生物相容性高，安全性能稳定的产品，产品透光率高，可适用于诸多应用领域。
具体实施方式
下面结合具体实施例对本发明进行进一步说明，在未经特殊说明的情况下，所述分子量的单位为g/mol，产品浓度为质量百分比计算。
实施例1
一种赋型聚氨酯复合薄膜，由如下两种热塑性聚氨酯材料热合制成：
聚氨酯A
聚丁二醇(分子量2000)
异佛尔酮二异氰酸酯
1，4-丁二醇
聚氨酯B
聚己二酸丁二醇(分子量1200)
4，4’-二苯甲烷二异氰酸酯
1，6-己二醇
利用雾度标准测量聚氨酯A材料透光率为96.8％
实施例2
一种赋型聚氨酯复合薄膜，由如下两种热塑性聚氨酯材料热合制成：
聚氨酯A
聚丁二醇(分子量1500)
六亚甲基二异氰酸酯
1，3-丙二醇
聚氨酯B
聚ε-己内酯二醇(分子量1000)
甲苯二异氰酸酯
1，4-丁二醇
利用雾度标准测量聚氨酯A材料透光率为95.2％
实施例3
一种赋型聚氨酯复合薄膜，由如下两种热塑性聚氨酯材料热合制成：
聚氨酯A
聚丁二醇(分子量2250)
异佛尔酮二异氰酸酯
1，3-丙二醇
聚氨酯B
聚己二酸丁二醇(分子量1500)
甲苯二异氰酸酯
1，4-丁二醇
利用雾度标准测量聚氨酯A材料透光率为94.9％
实施例4
一种赋型聚氨酯复合薄膜，由如下两种热塑性聚氨酯材料热合制成：
聚氨酯A
聚丁二醇(分子量2500)
六亚甲基二异氰酸酯
1，6-己二醇
聚氨酯B
聚己二酸丁二醇(分子量1750)
4，4’-二苯甲烷二异氰酸酯
1，4-丁二醇
利用雾度标准测量聚氨酯A材料透光率为95.8％
实施例5
一种赋型聚氨酯复合薄膜，由如下两种热塑性聚氨酯材料热合制成：
聚氨酯A
聚丁二醇(分子量1750)
异佛尔酮二异氰酸酯
1，3-丙二醇、1，4-丁二醇
聚氨酯B
聚ε-己内酯二醇(分子量1750)
对苯二异氰酸酯
1，6-己二醇
利用雾度标准测量聚氨酯A材料透光率为96.2％
实施例6
一种赋型聚氨酯复合薄膜，由如下两种热塑性聚氨酯材料热合制成：
聚氨酯A
聚丁二醇(分子量2750)
六亚甲基二异氰酸酯
1，4-丁二醇
聚氨酯B
聚己二酸丁二醇(分子量1500)
甲苯二异氰酸酯
1，4-丁二醇、1，6-己二醇
利用雾度标准测量聚氨酯A材料透光率为94.4％
实施例7
一种赋型聚氨酯复合薄膜，由前述实施例1-6所述聚氨酯A制成的弹性层、以及聚氨酯B制成的织网层热压合制成。
根据聚氨酯A异氰酸酯基团和羟基的当量比投入对应配料，利用双螺杆挤出机在110～140摄氏度下挤出反应，然后送经压延成型设备获得弹性层。
利用静电纺丝技术对聚氨酯B进行加工，获得直径不超过0.2mm的聚氨酯纤维细丝；纤维细丝加工排列后于弹性层的一侧热压，排列方式可将经线、纬线逐个交替组合，形成两组平行交织的织网结构。纤维细丝直径不超过0.2mm，相邻两根平行距离在5～15mm，获得赋型聚氨酯复合薄膜。热压后弹性层和织网层的复合薄膜厚度是热压前弹性层的70～90％，由于聚氨酯A的玻璃化温度低于聚氨酯B，在加热状态下使织网层嵌于弹性层中。
以上所述仅是本发明的优选实施方式，应当指出：对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (5)

1.一种赋型聚氨酯复合薄膜，其特征在于：该复合膜由聚氨酯A制成的弹性层、以及聚氨酯B制成的织网层热压合制成，所述织网层是基于聚氨酯B的纤维细丝交织制成；所述聚氨酯A通过聚丁二醇、一种脂肪族二异氰酸酯和至少一种扩链剂反应制备获得，所述聚氨酯B通过聚己二酸丁二醇、一种芳香族二异氰酸酯和至少一种扩链剂反应制备获得；
所述聚氨酯A制备时用的脂肪族二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯的任意一种，聚氨酯A的软段相对分子质量在1500-3000之间；
所述聚氨酯B制备时用的芳香族二异氰酸酯为对苯二异氰酸酯、甲苯二异氰酸酯、4,4’-二苯甲烷二异氰酸酯的任意一种，聚氨酯B的软段相对分子质量在1000-2000之间；
所述聚氨酯B制成的纤维细丝相邻两根平行距离在5~15mm。
2.根据权利要求1所述的一种赋型聚氨酯复合薄膜，其特征在于：所述扩链剂为乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇的任意一种或多种的组合。
3.根据权利要求1所述的一种赋型聚氨酯复合薄膜，其特征在于：所述聚氨酯B制成的纤维细丝直径不超过0.2mm。
4.如权利要求1所述复合薄膜的制备方法，其特征在于：将聚氨酯A各组分混合，经螺杆挤出机挤压反应，然后送经压延成型设备获得弹性层；利用静电纺丝技术对聚氨酯B进行加工，获得直径不超过0.2mm的聚氨酯纤维细丝；纤维细丝加工排列后于弹性层的一侧热压，获得赋型聚氨酯复合薄膜。
5.根据权利要求4所述的方法，其特征在于：纤维细丝相邻两根平行距离在2~5mm，在至少85℃下热压于弹性层表面。
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