CN115044003B - 一种含氟自愈合水性聚氨酯人工皮肤材料的制备方法 - Google Patents

一种含氟自愈合水性聚氨酯人工皮肤材料的制备方法 Download PDF

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CN115044003B
CN115044003B CN202210163139.2A CN202210163139A CN115044003B CN 115044003 B CN115044003 B CN 115044003B CN 202210163139 A CN202210163139 A CN 202210163139A CN 115044003 B CN115044003 B CN 115044003B
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chain extender
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戴家兵
王启东
李维虎
钦洋
吴旻晨
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Hefei Flexible Ketian Robot Material Co ltd
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Abstract

本发明公开了一种含氟自愈合水性聚氨酯人工皮肤材料的制备方法，涉及水性聚氨酯材料技术领域，先由异氰酸酯、大分子多元醇、有机硅聚醚多元醇、亲水扩链剂、2,2,3,3,4,4‑六氟‑1,5‑戊二醇、小分子扩链剂在催化剂的作用下反应制备预聚体，然后加入中和剂、后扩链剂反应制得含氟自愈合水性聚氨酯；本发明制备的含氟水性聚氨酯具有十分优异的自愈合能力、环保性能、耐热性能及近似人体皮肤的触感，该发明填补了国内外未开发出具有自愈合及亲水性能材料的空白。

Description

一种含氟自愈合水性聚氨酯人工皮肤材料的制备方法
技术领域：
本发明涉及水性聚氨酯材料技术领域，具体涉及一种含氟自愈合水性聚氨酯人工皮肤材料的制备方法。
背景技术：
随着智能可穿戴设备的需求越来越高，制备一种与人体皮肤十分类似材料的市场越来越急切。目前很多科研机构及高校目前主要集中于利用硅橡胶等材料模拟人体皮肤，但是该类材料亲水性能不足，而人体表皮是具有亲水性能的，因此在潮湿环境下，该类材料与人体皮肤的性能出入较大；国内外也有科研人员研究出亲水性能的人工皮肤材料，但是其自愈合性能不佳，而人体皮肤本身具有自愈合性能。综上考虑，具有自愈合且亲水性能优异的材料将十分接近人体皮肤。
发明内容：
本发明所要解决的技术问题在于提供一种含氟自愈合水性聚氨酯的制备方法，该材料具有优异的自愈合能力，亲水性能优异，环保性能好，耐热性能好及具有接近人体皮肤的触感，其在人工皮肤、可穿戴设备及假肢表皮等方面具有广阔的应用前景。
本发明所要解决的技术问题采用以下的技术方案来实现：
本发明提供了一种含氟自愈合水性聚氨酯人工皮肤材料的制备方法，先由异氰酸酯、大分子多元醇、有机硅聚醚多元醇、亲水扩链剂、2,2,3,3,4,4-六氟-1,5-戊二醇、小分子扩链剂在催化剂的作用下反应制备预聚体，然后加入中和剂、后扩链剂反应制得含氟自愈合水性聚氨酯。
由于该水性聚氨酯中引入了2,2,3,3,4,4-六氟-1,5-戊二醇，该物质赋予水性聚氨酯主链中含有适量的氟官能团，使其具有较强的氢键作用，其分子间作用力很强，因此该材料具有优异的自愈合能力；由于亲水扩链剂的存在，该材料亲水性能极佳，具有类似表皮的亲水特性；由于该材料以水作为溶剂，因此其环保性能优良；由于分子链中存在氟元素，因此该材料的耐热性能较为优异；由于水性聚氨酯主链中引入了有机硅聚醚多元醇，因此该材料具有十分接近皮肤的触感。
所述异氰酸酯包括异佛尔酮二异氰酸酯(IPDI)、4,4-二环己基甲烷二异氰酸酯(HMDI)、六甲撑二异氰酸酯(HDI)、甲苯-2,4-二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)中的一种或多种。
所述大分子多元醇包括聚醚多元醇(PPG系列)、聚四氢呋喃多元醇(PTMG系列)、聚酯多元醇、聚碳多元醇中的一种或多种。
所述亲水扩链剂包括二羟甲基丙酸、二羟甲基丁酸、磺酸盐型亲水扩链剂中的一种或多种。
所述小分子扩链剂包括2-甲基-1,3-丙二醇(MPO)、1,4-丁二醇(BDO)、环己烷二甲醇(CHDM)、三羟甲基丙烷(TMP)中的一种或多种。
所述后扩链剂包括乙二胺、己二胺、异氟尔酮二胺、1,4-环己二甲胺中的一种或多种。
所述催化剂包括有机铋类催化剂、锆类催化剂、锰类催化剂中的一种或多种。
所述中和剂包括三乙胺、氨水、三乙醇胺和氢氧化钠中的一种或多种。
所述2,2,3,3,4,4-六氟-1,5-戊二醇占比为水性聚氨酯预聚体质量的1-10％。
所述有机硅聚醚多元醇占比为水性聚氨酯预聚体质量的5％-35％。
所述催化剂占比为水性聚氨酯预聚体质量的0.1％～0.3％。
本发明还将上述含氟自愈合水性聚氨酯人工皮肤材料用于制备可穿戴设备及假肢表皮。
本发明的有益效果是：本发明含氟自愈合水性聚氨酯由异氰酸酯、大分子多元醇、有机硅聚醚多元醇、亲水扩链剂及2,2,3,3,4,4-六氟-1,5-戊二醇按一定比例在一定温度下反应形成预聚体，然后乳化打开加入后扩链制备而来；由于该水性聚氨酯中引入2,2,3,3,4,4-六氟-1,5-戊二醇、有机硅聚醚多元醇及亲水扩链剂，因此该材料具有十分优异的自愈合能力、环保性能、耐热性能及近似人体皮肤的触感，该发明填补了国内外未开发出具有自愈合及亲水性能材料的空白。
附图说明：
图1为样条在不同时间段自愈合变化情况的光学显微镜图。
具体实施方式：
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施例和图示，进一步阐述本发明。
下面实施例和对比例除了催化剂购自于德音化学，其余原材料均购买自阿拉丁试剂有限公司。
实施例1
一种含氟自愈合水性聚氨酯的制备方法，包括以下步骤：
称取90g聚四氢呋喃多元醇(分子量3000)，18g有机硅聚醚多元醇(分子量1800)和37.73g 4,4-二环己基甲烷二异氰酸酯加入三口烧瓶中，在90℃下搅拌反应2h；然后向三口烧瓶中分别添加4.9g二羟甲基丙酸，8g 2,2,3,3,4,4-六氟-1,5-戊二醇，0.1g三羟甲基丙烷和15g丙酮，在80℃下继续搅拌反应2h；然后加入0.3g有机铋催化剂DY-20和10g丙酮，反应温度降温至70℃，继续反应3h；然后加入120g丙酮，将得到的预聚体降温至50℃，加入3.69g三乙胺反应3min，将预聚体降温至10℃，然后将预聚体出料至梅花桶，加入307g蒸馏水于分散机中乳化打开，分散机转速为2800r/min，最后加入2.81g 1,4-环己二甲胺进行后扩链反应，放置8h后脱去丙酮，即得到含氟自愈合水性聚氨酯。
实施例2
一种含氟自愈合水性聚氨酯的制备方法，包括以下步骤：
称取90g聚醚多元醇PPG-3000(分子量3000)，18g有机硅聚醚多元醇(分子量1800)和31.97g异佛尔酮二异氰酸酯加入三口烧瓶中，在90℃下搅拌反应2h；然后向三口烧瓶中分别添加4.9g二羟甲基丙酸，8g 2,2,3,3,4,4-六氟-1,5-戊二醇，0.1g三羟甲基丙烷和15g丙酮，在80℃下继续搅拌反应2h；然后加入0.3g有机铋催化剂DY-20和10g丙酮，反应温度降温至70℃，继续反应3h；然后加入120g丙酮，将得到的预聚体降温至50℃，加入3.69g三乙胺反应3min，将预聚体降温至10℃，然后将预聚体出料至梅花桶，加入296g蒸馏水于分散机中乳化打开，分散机转速为2800r/min，最后加入2.81g 1,4-环己二甲胺进行后扩链反应，放置8h后脱去丙酮，即得到含氟自愈合水性聚氨酯。
实施例3
一种含氟自愈合水性聚氨酯的制备方法包括以下步骤：
称取90g聚碳多元醇PCD-3000(分子量3000)，18g有机硅聚醚多元醇(分子量1800)和37.73g 4,4-二环己基甲烷二异氰酸酯加入三口烧瓶中，在90℃下搅拌反应2h；然后向三口烧瓶中分别添加4.9g二羟甲基丙酸，8g 2,2,3,3,4,4-六氟-1,5-戊二醇，0.1g三羟甲基丙烷和15g丙酮，在80℃下继续搅拌反应2h；然后加入0.3g有机铋催化剂DY-20和10g丙酮，反应温度降温至70℃，继续反应3h；然后加入120g丙酮，将得到的预聚体降温至50℃，加入3.69g三乙胺反应3min，将预聚体降温至10℃，然后将预聚体出料至梅花桶，加入307g蒸馏水于分散机中乳化打开，分散机转速为2800r/min，最后加入2.81g 1,4-环己二甲胺进行后扩链反应，放置8h后脱去丙酮，即得到含氟自愈合水性聚氨酯。
对比例1
一种含氟自愈合水性聚氨酯的制备方法，包括以下步骤：
称取90g聚四氢呋喃多元醇(分子量3000)，18g有机硅聚醚多元醇(分子量1800)和37.73g 4,4-二环己基甲烷二异氰酸酯加入三口烧瓶中，在90℃下搅拌反应2h；然后向三口烧瓶中分别添加4.9g二羟甲基丙酸，3.97g 2,2,3,3,4,4-六氟-1,5-戊二醇，0.84g三羟甲基丙烷和15g丙酮，在80℃下继续搅拌反应2h；然后加入0.29g有机铋催化剂DY-20和10g丙酮，反应温度降温至70℃，继续反应3h；然后加入120g丙酮，将得到的预聚体降温至50℃，加入3.69g三乙胺反应3min，将预聚体降温至10℃，然后将预聚体出料至梅花桶，加入303g蒸馏水于分散机中乳化打开，分散机转速为2800r/min，最后加入4.12g 1,4-环己二甲胺进行后扩链反应，放置8h后脱去丙酮，即得到含氟自愈合水性聚氨酯。
对比例2
一种常规水性聚氨酯的制备方法，包括以下步骤：
称取90g聚四氢呋喃多元醇(分子量3000)，18g有机硅聚醚多元醇(分子量1800)和37.73g 4,4-二环己基甲烷二异氰酸酯加入三口烧瓶中，在90℃下搅拌反应2h；然后向三口烧瓶中分别添加4.9g二羟甲基丙酸，1.66g 1,4-丁二醇，0.84g三羟甲基丙烷和15g丙酮，在80℃下继续搅拌反应2h；然后加入0.29g有机铋催化剂DY-20和10g丙酮，反应温度降温至70℃，继续反应3h；然后加入120g丙酮，将得到的预聚体降温至50℃，加入3.69g三乙胺反应3min，将预聚体降温至10℃，然后将预聚体出料至梅花桶，加入299g蒸馏水于分散机中乳化打开，分散机转速为2800r/min，最后加入4.12g 1,4-环己二甲胺进行后扩链反应，放置8h后脱去丙酮，即得到水性聚氨酯。
上述实施例1、实施例2、实施例3、对比例1、对比例2中2,2,3,3,4,4-六氟-1,5-戊二醇含量占比预聚体分别为5％、5％、5％、2.5％、0％，分别将实施例1、实施例2、实施例3、对比例1、对比例2制备的树脂成膜，然后每组分别取2块10cm*1cm*0.1cm的样条，其中一组直接进行力学性能测试，得到原样的力学性能测试结果；另外一组切割宽2mm的裂口，然后放入150℃烘箱加热1h并观察自愈合情况，最后进行力学性能测试，得到缺口自愈合样的力学性能测试结果。力学性能测试标准参照GB/T 1040-1992。力学性能测试结果表1所示，图1为样条在不同时间段自愈合变化情况的光学显微镜图。
表1
通过上述测试可知，实施例1、实施例2、实施例3、对比例1有缺口的样条在烘箱中加热后基本上都能自愈合，且随着含氟基团含量增加，其愈合效果越好，对比例2并未愈合。实施例1、实施例2、实施例3、对比例1没缺口的样条和有缺口但自愈合后的样条在力学性能上基本一致，而对比例2有缺口的样条不能自愈合，且该缺口样条力学数据无法得到，测试过程中拉力机刚施力后直接断裂。
本发明利用小分子含氟二元醇(2,2,3,3,4,4-六氟-1,5-戊二醇)作为水性聚氨酯扩链剂合成制备了具有自愈合功能的材料，该材料主链含有氟官能团，其具有较强的氢键作用，因此其分子间作用力很强，从而赋予该材料具有十分优异的自愈合性能；由于亲水扩链剂的存在，该材料亲水性能极佳，有类似表皮的亲水特性；由于该材料以水作为溶剂，因此其环保性能优良；由于分子链中存在氟元素，因此该材料的耐热性能较为优异；由于水性聚氨酯主链中引入了有机硅聚醚多元醇，因此该材料具有十分接近皮肤的触感。基于该材料优异的性能，因此其在人工皮肤、可穿戴设备及假肢表皮等方面具有广阔的应用前景。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (10)

1.一种含氟自愈合水性聚氨酯人工皮肤材料的制备方法，其特征在于：先由异氰酸酯、大分子多元醇、有机硅聚醚多元醇、亲水扩链剂、2,2,3,3,4,4-六氟-1,5-戊二醇、小分子扩链剂在催化剂的作用下反应制备预聚体，然后加入中和剂、后扩链剂反应制得含氟自愈合水性聚氨酯。
2.根据权利要求1所述的制备方法，其特征在于：所述异氰酸酯包括异佛尔酮二异氰酸酯、4,4-二环己基甲烷二异氰酸酯、六甲撑二异氰酸酯、甲苯-2,4-二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或多种。
3.根据权利要求1所述的制备方法，其特征在于：所述大分子多元醇包括聚醚多元醇、聚四氢呋喃多元醇、聚酯多元醇、聚碳多元醇中的一种或多种。
4.根据权利要求1所述的制备方法，其特征在于：所述亲水扩链剂包括二羟甲基丙酸、二羟甲基丁酸、磺酸盐型亲水扩链剂中的一种或多种。
5.根据权利要求1所述的制备方法，其特征在于：所述小分子扩链剂包括2-甲基-1,3-丙二醇、1,4-丁二醇、环己烷二甲醇、三羟甲基丙烷中的一种或多种。
6.根据权利要求1所述的制备方法，其特征在于：所述后扩链剂包括乙二胺、己二胺、异氟尔酮二胺、1,4-环己二甲胺中的一种或多种。
7.根据权利要求1所述的制备方法，其特征在于：所述催化剂包括有机铋类催化剂、锆类催化剂、锰类催化剂中的一种或多种。
8.根据权利要求1所述的制备方法，其特征在于：所述中和剂包括三乙胺、氨水、三乙醇胺和氢氧化钠中的一种或多种。
9.根据权利要求1所述的制备方法，其特征在于：所述2,2,3,3,4,4-六氟-1,5-戊二醇占比为水性聚氨酯预聚体质量的1-10％；所述有机硅聚醚多元醇占比为水性聚氨酯预聚体质量的5％-35％；所述催化剂占比为水性聚氨酯预聚体质量的0.1％～0.3％。
10.将权利要求1-9任意一项所述的含氟自愈合水性聚氨酯人工皮肤材料用于制备可穿戴设备及假肢表皮。
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