CN112979911A - 氟化聚氨酯、壳层雾化喷液、人工仿生皮肤及制备方法 - Google Patents

氟化聚氨酯、壳层雾化喷液、人工仿生皮肤及制备方法 Download PDF

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CN112979911A
CN112979911A CN202110150310.1A CN202110150310A CN112979911A CN 112979911 A CN112979911 A CN 112979911A CN 202110150310 A CN202110150310 A CN 202110150310A CN 112979911 A CN112979911 A CN 112979911A
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parts
alcohol
shell
polyol
layer
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CN112979911B (zh
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闫成成
李维虎
董永红
刘辉
朱保凌
戴家兵
赵曦
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Hefei Flexible Ketian Robot Material Co ltd
Hefei Ketian Waterborne Technology Co ltd
Lanzhou Ketian Waterborne Polymer Material Co ltd
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Lanzhou Scisky Aqueous Polymer Material Co ltd
Hefei Scisky Technology Co ltd
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Abstract

本发明属于水性高分子功能材料领域，具体涉及醇溶性阳离子氟化聚氨酯、壳层雾化喷液、人工仿生皮肤及制备方法。本发明采用环保型的醇溶性方法合成分子量为3～8万、具有生物相容性的醇溶性阳离子氟化聚氨酯，并制得壳层雾化喷液，与水溶性聚苯胺复合液制得的核层雾化喷液通过核‑壳静电雾化技术制得人工仿生皮肤；制得的人工仿生皮肤具有透气透湿、疏水疏油、抗菌、高强度、高柔韧性(伸长率可达1800％)、高导电性低电阻(≤50Ω)的性能，静电雾化技术可对三维物体任意角度喷涂，实现了机器人三维机械结构及关节的包覆，可应用于医疗伤口皮肤修复，同时核层优异的导电性能使其可直接喷涂在人体心脏或者手腕部位，跟踪人体心跳监测。

Description

氟化聚氨酯、壳层雾化喷液、人工仿生皮肤及制备方法
技术领域
本发明属于水性高分子功能材料的合成及制备领域，更具体的涉及一种醇溶性阳离子氟化聚氨酯及其制备方法、由醇溶性阳离子氟化聚氨酯制备的壳层雾化喷液、由壳层雾化喷液制备的人工仿生皮肤及制备方法。
背景技术
众所周知，皮肤是人体器官的重要组成部分，可以辅助防御体外环境中的微生物及其他有害物质，同时具有排汗，调剂人体水分、排泄人体的新陈代谢产物以及维持人体体温等功能。而由于人的皮肤是最直接接触外部环境的器官，所以也是最易受到伤害的部分，比如遭到硬物撞击磕碰、高温或火烧伤、真菌感染、急性创伤等将产生皮肤破损甚至永久性的皮肤创面受损，而在医疗上比较快速的治疗手段则是进行植皮修复，因此在医疗领域对于人工仿生皮肤的需求日益增加。此外，随着以5G通信技术为载体的人工智能的快速发展，面向仿生机器人的可覆盖于机器人复杂的三维表面及活动关节的电子皮肤也得到市场的高度关注。
聚氨酯是一种分子主链上由软链段及硬链段交替镶嵌组成的含有大量氨基甲酸酯基团的极性高分子聚合物，是近年来快速发展的一种环保型高分子材料，其以优异的物理机械性能、良好的生物组织相容性及良好的血液相容性、低毒性、无致畸性、高柔韧延展性等特点在医学领域显示出了广阔应用价值。但是现有的聚氨酯乳液的合成方法，为了使乳化打开正常，所制备的聚氨酯分子量偏低(≤1万)，导致物性指标难以满足高韧性、高强度的需求，且传统的聚氨酯的耐水性较差，而且现有制备方法用聚氨酯作为原料制备人工皮肤的过程难以实现对于三维物体及关节的无缝衔接包覆，限制了其在当前阶段的人工智能领域中人工皮肤上的的应用。
发明内容
本发明要解决的技术问题为克服现有技术中的传统的人工皮肤的制备方法均是在将人工皮肤制备完成之后，再贴合用于人体或者仿生机械关节，存在界面结合性差、难以对仿生机械的信号进行传递，同时在人体医用领域，本发明可实现即喷即用的有点，可紧密贴合皮肤创面，克服了传统人工皮肤与体表皮肤结合不紧密、容易受感染等问题，提供一种醇溶性阳离子氟化聚氨酯及其制备方法、由醇溶性阳离子氟化聚氨酯制备的壳层雾化喷液、由壳层雾化喷液制备的人工仿生皮肤及制备方法。
为了解决本发明的技术问题，所采取的技术方案为，一种醇溶性阳离子氟化聚氨酯的制备方法，包括如下步骤：
首先将具有生物相容性的多元醇在90～105℃真空脱水处理，然后降温至45-55℃，加入异氰酸酯，升温至80～90℃下充分反应1-5h，测试剩余NCO基团达到理论剩余值后，降低温度至50～70℃，依次加入氟化小分子扩链剂、阳离子亲醇扩链剂、聚硅氧烷、氟化醇单体及催化剂，继续保温反应1～5h并在反应期间通入保护气体，待反应达到设定的NCO理论值后，继续降低温度至45-55℃，然后加入非亲醇小分子扩链剂、交联剂，然后继续保温反应1-5h，待反应至测试设定的剩余NCO值不再发生变化后，将温度降低至25～40℃加入酸中和剂及乙醇并在高速剪切力作用下乳化，得到阳离子氟化聚氨酯-乙醇溶剂混合体系，然后在该混合体系中滴加乳化剂及后扩链剂，在35～55℃下乳化1-2h，获得分子量为3-8万的醇溶性阳离子氟化聚氨酯。
作为上述醇溶性阳离子氟化聚氨酯的制备方法进一步改进：
优选的，各原料的质量份如下：具有生物相容性的多元醇95-200份、脂肪族多异氰酸酯30～150份，氟化小分子扩链剂5～30份，阳离子亲醇扩链剂5-25份、聚硅氧烷1-25份，氟化醇单体5～30份、催化剂0.1～10份，非亲醇小分子扩链剂8-20份，交联剂0.1-10份，酸中和剂5～30份，乙醇80～500份、乳化剂0.1～8份，后扩链剂5-8份。
优选的，所述具有生物相容性的多元醇为聚醚多元醇、聚酯多元醇、聚乳酸多元醇的组合，质量份比为(30～50):(50-100):(15-50)。
优选的，所述聚醚多元醇为聚氧化乙烯二醇、聚四氢呋喃醚二醇、大豆油聚醚多元醇、棕榈油聚醚多元醇、蓖麻油聚醚多元醇、Mannich聚醚二醇的一种或两种及以上的组合；所述聚酯多元醇为聚己内酯二元醇、聚丙交酯-co-己内酯多元醇、聚ε-己内酯聚醚多元醇、聚碳酸亚丙酯多元醇中的一种或两种及以上的组合；所述聚乳酸多元醇为可生物降解的多元醇软段。
优选的，所述氟化醇单体为氟化小分子一元醇、氟化小分子二元醇或长链含氟二元醇，所述长链含氟二元醇为PEVE型、含氟聚酯二醇、含氟聚醚二醇中的一种或者两种及以上的组合。
优选的，所述聚硅氧烷材料为环氧-聚硅氧烷、聚二甲基硅氧烷、聚醚硅氧烷、氟烷基聚硅氧烷中的一种或两种及以上的组合。
优选的，所述非亲醇小分子扩链剂为1,4丁二醇、乙二醇、一缩二乙二醇和新戊二醇、端氨基聚醚中的一种或两种及以上的组合。
优选的，所述交联剂为三羟甲基丙烷、1,2,6-己三醇，甲基葡萄糖苷和蔗糖、硅烷偶联剂KH550/KH560中的一种或两种及以上的组合。
优选的，在加入酸中和剂的同时，加入5-30份使用酸中和剂溶解的天蚕丝素和/或1-15份使用酸中和剂溶解的壳聚糖。
为了解决本发明的另一个技术问题，所采取的技术方案为，一种由上述制备方法制得的醇溶性阳离子氟化聚氨酯。
为了解决本发明的又一个技术问题，所采取的技术方案为，一种由上述醇溶性阳离子氟化聚氨酯制备的壳层雾化喷液，该壳层雾化喷液由以下方式制得：在制得的醇溶性阳离子氟化聚氨酯中加入1-10份消泡剂，在50℃下熟化24h，继续加入水溶性高分子量的聚丙烯酰胺和/或聚乙烯醇，高速搅拌混合均匀，超声分散配制成固含量为35～45％的雾化原液，即为壳层雾化喷液。
为了解决本发明的再一个技术问题，所采取的技术方案为，一种由上述壳层雾化喷液制得的人工仿生皮肤，其特征在于，由以下方式制得：以厚度0.5-1mm的PET板或PDMS基材作为支撑层，核层雾化喷液和壳层雾化喷液作为基础材料，利用带有核壳双层喷头的静电喷枪在支撑层上静电雾化喷涂，所述核壳双层喷头包括核层喷头和套设在核层喷头外的壳层喷头，所述核层喷头用于喷射核层雾化喷液、所述壳层喷头用于喷射壳层雾化喷液，所述核壳喷头的内直径为0.3-0.8mm，壳层喷头的内直径为0.5-2.5mm，静电喷枪的输入电压为15-50V、喷射速度为1-5ml/min，然后将喷涂后的支撑层置于室温25-35℃环境下自然干燥15-24h后即可获得人工仿生皮肤。
作为上述人工仿生皮肤进一步的改进：
优选的，所述核层雾化喷液由50-100质量份水溶性聚苯胺复合液中加入5-10质量份的高分子量聚丙烯酰胺和1-5质量份表面活性剂，搅拌均匀制得。
本发明相比现有技术的有益效果在于：
(1)高分子量的醇溶性阳离子氟化聚氨酯的合成；
本发明通过将具有生物相容性的多元醇、天蚕丝素、聚硅氧烷及脂肪族硬段合成具有良好生物相容性的、分子量在3～8万的高分子量醇溶性阳离子氟化聚氨酯，
所述氟化醇单体的作用旨在聚氨酯分子链结构中引入氟碳键，进一步降低材料界面的表面能。
所述阳离子亲醇扩链剂旨在合成聚氨酯链段上引入叔胺化基团，然后进行叔胺化，
所述聚硅氧烷材料主要为降低材料的表面能，并提升材料的抗水拒油性能，
所述非亲醇小分子扩链剂主要作用是进一步提高合成的氟化聚氨酯分子量，
所述交联剂为进一步提升材料层的强度及抗拉伸撕扯性能的小分子交联剂，
(2)壳层雾化喷液的制备特征在于在合成高分子量醇溶性阳离子氟化聚氨酯的基础上，将水溶性高分子聚丙烯酰胺或聚乙烯纯与聚氨酯-乙醇体系采用AK分散剂高速搅拌混合均匀，并经超声分散配制成35～45％的雾化原液，作为壳层雾化喷液待用；
(3)核层雾化喷液的制备：合成的水溶性聚苯胺与碳纳米管粒子、石墨烯粒子的混合体系难以实现分子级别的混合均匀，存在局部团聚的情况，本发明在该混合体系中加入高分子量的聚丙烯酰胺对进行粒子包裹固定以防止沉降，并加入表面活性剂降低表面能以防止粒子的团聚，复配好作为核层雾化喷液待用；
(4)酸中和剂的作用在于一部分提供中和作用，另外可溶解壳聚糖及天然丝素能生物组份，从而引入到体系中，可起到抗菌消炎、生物可降解作用；解决了现有技术中聚氨酯存在的抗菌性差、与人体皮肤创面的生物相容性差、不易体内生物降解等问题。本发明通过合成高分子量的聚氨酯乳液，同时通过引入氟元素提高其耐水性及肤感，在应用于皮肤创面后，待伤口愈合后可直接脱落或被人体吸收生物分解，且不对人体产生毒性危害等。
(5)静电雾化人工仿生皮肤喷层主要是采用上述两种制备合成的壳层雾化喷液和核层雾化喷液作为基础材料，同时以PET板或PDMS基材作为支撑层；然后利用实验室自制的简易手持静电喷枪及核壳双层喷头进行静电雾化喷涂，然后置于室温环境下自然干燥后获得；该人工仿生皮肤喷层表面触感柔和、高柔韧延展性且附着贴合力好，可有望在医疗创面的人工仿生皮移植及机器人电子皮肤等领域得到应用。通过本发明制备的人工仿生皮肤层，不仅具有抗菌、吸湿排汗、同时核层通过多壁碳纳米管及负载氧化铝纳米颗粒的石墨烯、聚苯胺引入进一步赋予其导电性能，从而可用于机器人皮肤传感及人体的心跳监测等方面。
(6)针对当前市场对于人工仿生皮肤需求，本发明首先通过聚乳酸多元醇、天蚕丝素、聚丙交酯-co-己内酯多元醇、聚硅氧烷及脂肪族硬段合成一种良好生物相容性的高分子量醇溶性阳离子氟化聚氨酯，并通过核-壳静电雾化技术实现人工仿生皮肤的制备。所制备的人工仿生皮肤不仅透气透湿性能良好，同时具有疏水疏油、抗菌、高强度、高柔韧性(伸长率最高可达到1800％)、高导电性和≤50Ω的低电阻，而现有人工皮肤没有没有引入聚苯胺及石墨烯导电介质的电阻为≥800Ω，不仅可应用于医疗伤口皮肤修复，同时采用制备的手持核壳静电雾化机可实现对于三维物体任意角度的喷涂，从而可实现对于机器人三维机械结构及关节的包覆，同时核层优异的导电性能使其可直接喷涂在人体心脏或者手腕部位，进而跟踪人体心跳监测。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
注意，如没有特别说明，本文中描述所示的“％”和“份”分别是指“质量％”和“质量份”。
在制备醇溶性阳离子氟化聚氨酯的制备中，其中几种原料优选的种类如下：
所述异氰酸酯为脂肪族多异氰酸酯，具体包括异氟尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、1,6己基二异氰酸酯、四甲基环己基甲烷二异氰酸酯、甲基环己基二异氰酸酯和降冰片烷二异氰酸酯中的一种或两种及以上的组合。
所述氟化小分子扩链剂为氟化二醇、氟化二胺的一种或两种及以上的组合。
所述阳离子亲醇扩链剂旨在合成聚氨酯链段上引入叔胺化基团，然后进行叔胺化，具体的叔胺化合物亲醇扩链剂为二乙醇胺、三乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、N-丙基二乙醇胺、叔丁基二乙醇胺、二甲基乙醇胺、双(2-羟丙基)苯胺中的一种或者两种及以上的组合。
所述催化剂二月桂酸二丁基锡、羧酸锌、羧酸铋和钛酸四丁酯中的一种或两种及以上的组合。
所述酸中和剂选自冰醋酸、乙醇酸、乙酸酐中的一种或两种及以上的组合。
所述乳化剂为OP-10，十二烷基苯磺酸钠中的至少一种或两种及以上的组合。
所述后扩链剂为乙二胺、异氟尔酮二胺中的一种或两种的组合。
所述乙醇为工业级浓度≥95％的乙醇溶液。
所述消泡剂为聚硅氧烷共聚物类消泡剂。
实施例1
本发明提供一种壳层雾化喷液的制备方法，具体包括：
S1、醇溶性高分子量阳离子氟化聚氨酯的合成：首先将35份聚氧化乙烯二醇、60份聚己内酯二元醇、聚乳酸多元醇25份、在90～105℃真空脱水1-1.5h；然后降温至45-55℃，并加入称量好的85份异氟尔酮二异氰酸酯，并升温至90℃下保温充分反应3h，测试剩余NCO基团达到理论剩余值后，降低温度至60℃，依次加入7份氟化小分子一元醇、氟化二醇6份、6份N-甲基二乙醇胺、10份聚二甲基硅氧烷、3份的有羧酸铋催化剂继续保温反应3h并在反应期间通入保护气体，待反应达到设定的NCO理论值后，继续降低温度至45℃，然后加入8份乙二醇扩链剂、1份三羟甲基丙烷，然后继续保温反应4h，待反应至测试设定的剩余NCO值不再发生变化后，将温度降低至25-40℃加入9.5份冰乙酸中和5-8min，同时加入采用10份冰乙酸溶解3份天蚕丝素、2份壳聚糖天然生物组分，然后再加入400份的95％稀释降粘乙醇并在高速剪切力作用下乳化，然后滴加2份OP-10乳化剂及5份乙二胺后扩链剂，然后继续乳化搅拌一段时间获得高分子量的醇溶性氟化聚氨酯；
S2、在上述醇溶性氟化聚氨酯溶液中加入1份聚硅氧烷共聚物消泡剂，然后将合成的醇溶性聚氨酯在50℃熟化24h，在制备上述高分子量醇溶性氟化聚氨酯的基础上，称量100份上述聚氨酯醇溶液加入5份分子量50W的聚丙烯酰胺并与AK分散剂上高速分散搅拌0.5h，并经超声分散0.5h后制备得到壳层雾化喷液。
实施例2
本发明提供一种核层雾化喷液的制备方法，具体包括：
S1、制备水溶性聚苯胺复合液，并引用导电纳米介质：将高分子酸、苯胺分别加入蒸馏水中，所述高分子酸、苯胺、蒸馏水的摩尔比为1.5:1:5，并在混合体系中通入氮气30min去除体系中溶解氧；随后将其置于5℃下保温反应4h，然后采用滴液漏斗滴加2mmol/L的过硫酸铵水溶液，过硫酸铵与苯胺的摩尔比为1:1，滴加时间控制在1.5h，滴加完成后再继续反应8h后得到酸掺杂的聚苯胺水溶液；随后称取50份聚苯胺溶液加入3份多壁碳纳米管及2份载有氧化铝纳米颗粒的石墨烯(石墨烯及碳纳米管均在球磨机上球磨30min)，随后进行AK高速分散并经超声分散0.5h，制得水溶性聚苯胺复合液；
S2、为防止纳米颗粒介质沉降及混合不均匀团聚，将上述聚苯胺混合溶液加入5份100w分子量的聚丙烯酰胺及1份十二烷基苯磺酸钠，搅拌混合均匀后制得核层雾化喷液。
实施例3
本发明提供一种由实施例7和8制得的壳层雾化喷液和核层雾化喷液制备人工仿生皮肤的方法，具体包括：
制备静电雾化人工仿生皮肤喷层：为了仿生层的收取及测试便利，本发明中采用以矿氧紫铜铜板作为负极基底(以利用形成稳定电场进行雾化粒子的收集)，然后在其上覆盖厚度0.5-1mm的PET板或PDMS基层作为支撑层；然后采用实验室自制的简易手持静电喷枪(35V电池组)及核壳双层(核层及壳层分别采用15ml的一次性注射器固定于喷枪内部，且喷射速度1.5ml/min，注射器核壳喷头的内直径为：核层为0.3-0.8mm，壳层为0.5-2.5mm)喷头进行垂直向下90°连续静电雾化喷涂10min，然后将其置于室温25-35℃环境下自然干燥15-24h后即可获得人工仿生皮肤；本发明的喷涂方法仅为了测试性能方便采用垂直向下喷涂，实际应用中才采用手持静电雾化喷枪任意角度喷涂，以便于跟三维物体或界面的紧密贴合；
所制备的人工仿生层的力学性能测试主要采用英斯特朗拉力机进行测试，将图层喷涂至PET板或PDMS板上并自然干燥后揭下，然后裁剪成宽10mm长5-8cm的长条进行力学拉伸试验。采用双电测四探针法进行仿生皮肤层的电阻值及电导率的性能测试。本实施例测试仿生层的伸长率为1300％、强度50MPa，电阻值为50Ω。
实施例4
本发明提供一种壳层雾化喷液的制备方法，具体包括：
本发明的一种基于醇溶性水性树脂的人工仿生皮肤的制备方法，具体包括：
S1、醇溶性高分子量阳离子氟化聚氨酯的合成：首先将35份聚四氢呋喃醚二醇、70份聚丙交酯-co-己内酯多元醇、45份聚乳酸多元醇在90～105℃真空脱水1.5h；然后降温至45℃，并加入称量好的105份异氟尔酮二异氰酸酯，并升温至90℃下保温充分反应4h，测试剩余NCO基团达到理论剩余值后，降低温度至60℃，然后加入10份氟化小分子一元醇、氟化二醇5份、6份N-甲基二乙醇胺、8份聚二甲基硅氧烷，同时加入5份的有机铋催化剂继续保温反应3h并在反应期间通入保护气体，待反应达到设定的NCO理论值后，继续降低温度至45℃，然后加入10份乙二醇扩链剂、2.5份三羟甲基丙烷，然后继续保温反应4h，待反应至测试设定的剩余NCO值不再发生变化后，将温度降低至25℃加入6份冰乳酸中和5-8min，同时加入采用10份冰乙酸溶解3份天蚕丝素、2份壳聚糖天然生物组分，然后再加入450份的95％稀释降粘乙醇并在高速剪切力作用下乳化，然后滴加2份OP-10乳化剂及5份异氟尔酮二胺后扩链剂，然后继续乳化搅拌一段时间获得高分子量的醇溶性氟化聚氨酯；
S2、最后加入1.5份聚硅氧烷共聚物消泡剂，然后将合成的醇溶性聚氨酯在50℃熟化24h，在制备上述高分子量醇溶性氟化聚氨酯的基础上，称量100份上述聚氨酯醇溶液加入5份分子量50W的聚丙烯酰胺并与AK分散剂上高速分散搅拌0.5h，并经超声分散0.5h后制备得到壳层雾化喷液待用。
实施例5
本发明提供一种核层雾化喷液的制备方法，具体包括：
S1、制备水溶性聚苯胺复合液，并引用导电纳米介质：将高分子酸、苯胺分别加入蒸馏水中，所述高分子酸、苯胺、蒸馏水的摩尔比为2:1:8，并在混合体系中通入氮气30min去除体系中溶解氧；随后将其置于5℃下保温反应4h，然后采用滴液漏斗滴加3mmol/L的过硫酸铵盐溶液，过硫酸铵与苯胺的摩尔比为1:0.5，滴加时间控制在2h，滴加完成后再继续反应8h后得到酸掺杂的聚苯胺水溶液；随后称取50份聚苯胺溶液加入5份多壁碳纳米管及5份载有氧化铝纳米颗粒的石墨烯(石墨烯及碳纳米管均在球磨机上球磨30min)，随后进行AK高速分散并经超声分散1h，制得水溶性聚苯胺复合液；
S2、为防止纳米颗粒介质沉降及混合不均匀团聚，将上述聚苯胺混合溶液加入5份100w分子量的聚丙烯酰胺及1份十二烷基苯磺酸钠、1份OP-10，搅拌混合均匀后制得核层雾化喷液。
实施例6
本发明提供一种由实施例7和8制得的壳层雾化喷液和核层雾化喷液制备人工仿生皮肤的方法，具体包括：
制备静电雾化人工仿生皮肤喷层：为了仿生层的收取及测试便利，本发明中采用以矿氧紫铜铜板作为负极基底(以利用形成稳定电场进行雾化粒子的收集)，然后在其上覆盖厚度0.5-1mm的PET板或PDMS基层作为支撑层；然后采用实验室自制的简易手持静电喷枪(35V电池组)及核壳双层(核层及壳层分别采用15ml的一次性注射器固定于喷枪内部，且喷射速度1.5ml/min，注射器核壳喷头的内直径为：核层为0.3-0.8mm，壳层为0.5-2.5mm)喷头进行垂直向下90°连续静电雾化喷涂10min，然后将其置于室温25-35℃环境下自然干燥15-24h后即可获得人工仿生皮肤；本发明的喷涂方法仅为了测试性能方便采用垂直向下喷涂，实际应用中才采用手持静电雾化喷枪任意角度喷涂，以便于跟三维物体或界面的紧密贴合；
所制备的人工仿生层的力学性能测试主要采用英斯特朗拉力机进行测试，将图层喷涂至PET板或PDMS板上并自然干燥后揭下，然后裁剪成宽10mm长5-8cm的长条进行力学拉伸试验。采用双电测四探针法进行仿生皮肤层的电阻值及电导率的性能测试。本实施例测试仿生层的伸长率为1500％、强度56MPa，电阻值为45Ω。
实施例7
本发明提供一种壳层雾化喷液的制备方法，具体包括：
S1、醇溶性高分子量阳离子氟化聚氨酯的合成：首先将10份聚四氢呋喃醚二醇、20份棕榈油聚醚多元醇、20份大豆油聚醚多元醇、80份聚ε-己内酯聚醚二元醇、50份聚乳酸多元醇在90～105℃真空脱水1.5h；然后降温至45℃，并加入称量好的125份异氟尔酮二异氰酸酯，并升温至90℃下保温充分反应5h，测试剩余NCO基团达到理论剩余值后，降低温度至60℃，然后加入12份氟化小分子一元醇、氟化二醇5份、15份N-甲基二乙醇胺、9.5份聚二甲基硅氧烷，同时加入投料总量的6份的羧酸铋催化剂继续保温反应4.5h并在反应期间通入保护气体，待反应达到设定的NCO理论值后，继续降低温度至55℃，然后加入10份1,4丁二醇扩链剂、3份三羟甲基丙烷，然后继续保温反应4h，待反应至测试设定的剩余NCO值不再发生变化后，将温度降低至35℃加入6份冰乳酸中和5-8min，同时加入采用15份冰乙酸溶解5份天蚕丝素、2份壳聚糖天然生物组分，然后再加入500份的95％稀释降粘乙醇并在高速剪切力作用下乳化，然后滴加2份OP-10乳化剂及5份异氟尔酮二胺、3份乙二胺后扩链剂，然后继续乳化搅拌一段时间获得高分子量的醇溶性氟化聚氨酯；
S2、最后加入2份聚硅氧烷共聚物消泡剂，然后将合成的醇溶性聚氨酯在50℃熟化24h，在制备上述高分子量醇溶性氟化聚氨酯的基础上，称量100份上述聚氨酯醇溶液加入5份分子量50W的聚丙烯酰胺并与AK分散剂上高速分散搅拌0.5h，并经超声分散0.5h后制备得到壳层雾化喷液。
实施例8
本发明提供一种核层雾化喷液的制备方法，具体包括：
S1、制备水溶性聚苯胺复合液，并引用导电纳米介质：将高分子酸、苯胺分别加入蒸馏水中，所述高分子酸、苯胺、蒸馏水的摩尔比为1.8:1:10，并在混合体系中通入氮气30min去除体系中溶解氧；随后将其置于5℃下保温反应4h，然后采用滴液漏斗滴加5mmol/L的过硫酸铵盐溶液，过硫酸铵与苯胺的摩尔比为1:0.5，滴加时间控制在2h，滴加完成后再继续反应8h后得到酸掺杂的聚苯胺水溶液；随后称取50份聚苯胺溶液加入5份多壁碳纳米管及5份载有氧化铝纳米颗粒的石墨烯(石墨烯及碳纳米管均在球磨机上球磨30min)，随后进行AK高速分散并经超声分散1h，制得水溶性聚苯胺复合液；
S2、为防止纳米颗粒介质沉降及混合不均匀团聚，将上述聚苯胺混合溶液加入6份100w分子量的聚丙烯酰胺及2.5份十二烷基苯磺酸钠、1份OP-10，搅拌混合均匀制得核层雾化喷液。
实施例9
本发明提供一种由实施例7和8制得的壳层雾化喷液和核层雾化喷液制备人工仿生皮肤的方法，具体包括：
制备静电雾化人工仿生皮肤喷层：为了仿生层的收取及测试便利，本发明中采用以矿氧紫铜铜板作为负极基底(以利用形成稳定电场进行雾化粒子的收集)，然后在其上覆盖厚度0.5-1mm的PET板或PDMS基层作为支撑层；然后采用实验室自制的简易手持静电喷枪(35V电池组)及核壳双层(核层及壳层分别采用15ml的一次性注射器固定于喷枪内部，且喷射速度1ml/min，注射器核壳喷头的内直径为：核层为0.3-0.8mm，壳层为0.5-2.5mm)喷头进行垂直向下90°连续静电雾化喷涂15min，然后将其置于室温25-35℃环境下自然干燥15-24h后即可获得人工仿生皮肤；本发明的喷涂方法仅为了测试性能方便采用垂直向下喷涂，实际应用中才采用手持静电雾化喷枪任意角度喷涂，以便于跟三维物体或界面的紧密贴合；
所制备的人工仿生层的力学性能测试主要采用英斯特朗拉力机进行测试，将图层喷涂至PET板或PDMS板上并自然干燥后揭下，然后裁剪成宽10mm长5-8cm的长条进行力学拉伸试验。采用双电测四探针法进行仿生皮肤层的电阻值及电导率的性能测试。本实施例测试仿生层的伸长率为1800％、强度60MPa，电阻值为43Ω。
本领域的技术人员应理解，以上所述仅为本发明的若干个具体实施方式，而不是全部实施例。应当指出，对于本领域的普通技术人员来说，还可以做出许多变形和改进，所有未超出权利要求所述的变形或改进均应视为本发明的保护范围。

Claims (13)

1.一种醇溶性阳离子氟化聚氨酯的制备方法，其特征在于，包括如下步骤：
首先将具有生物相容性的多元醇在90～105℃真空脱水处理，然后降温至45-55℃，加入异氰酸酯，升温至80～90℃下充分反应1-5h，测试剩余NCO基团达到理论剩余值后，降低温度至50～70℃，依次加入氟化小分子扩链剂、阳离子亲醇扩链剂、聚硅氧烷、氟化醇单体及催化剂，继续保温反应1～5h并在反应期间通入保护气体，待反应达到设定的NCO理论值后，继续降低温度至45-55℃，然后加入非亲醇小分子扩链剂、交联剂，然后继续保温反应1-5h，待反应至测试设定的剩余NCO值不再发生变化后，将温度降低至25～40℃加入酸中和剂及乙醇并在高速剪切力作用下乳化，得到阳离子氟化聚氨酯-乙醇溶剂混合体系，然后在该混合体系中滴加乳化剂及后扩链剂，在35～55℃下乳化1-2h，获得分子量为3-8万的醇溶性阳离子氟化聚氨酯。
2.根据权利要求1所述一种醇溶性阳离子氟化聚氨酯的制备方法，其特征在于，各原料的质量份如下：具有生物相容性的多元醇95-200份、脂肪族多异氰酸酯30～150份，氟化小分子扩链剂5～30份，阳离子亲醇扩链剂5-25份、聚硅氧烷1-25份，氟化醇单体5～30份、催化剂0.1～10份，非亲醇小分子扩链剂8-20份，交联剂0.1-10份，酸中和剂5～30份，乙醇80～500份、乳化剂0.1～8份，后扩链剂5-8份。
3.根据权利要求1或2所述一种醇溶性阳离子氟化聚氨酯的制备方法，其特征在于，所述具有生物相容性的多元醇为聚醚多元醇、聚酯多元醇、聚乳酸多元醇的组合，质量份比为(30～50):(50-100):(15-50)。
4.根据权利要求3所述一种醇溶性阳离子氟化聚氨酯的制备方法，其特征在于，所述聚醚多元醇为聚氧化乙烯二醇、聚四氢呋喃醚二醇、大豆油聚醚多元醇、棕榈油聚醚多元醇、蓖麻油聚醚多元醇、Mannich聚醚二醇的一种或两种及以上的组合；所述聚酯多元醇为聚己内酯二元醇、聚丙交酯-co-己内酯多元醇、聚ε-己内酯聚醚多元醇、聚碳酸亚丙酯多元醇中的一种或两种及以上的组合；所述聚乳酸多元醇为可生物降解的多元醇软段。
5.根据权利要求1或2所述一种醇溶性阳离子氟化聚氨酯的制备方法，其特征在于，所述氟化醇单体为氟化小分子一元醇、氟化小分子二元醇或长链含氟二元醇，所述长链含氟二元醇为PEVE型、含氟聚酯二醇、含氟聚醚二醇中的一种或者两种及以上的组合。
6.根据权利要求1或2所述一种醇溶性阳离子氟化聚氨酯的制备方法，其特征在于，所述聚硅氧烷材料为环氧-聚硅氧烷、聚二甲基硅氧烷、聚醚硅氧烷、氟烷基聚硅氧烷中的一种或两种及以上的组合。
7.根据权利要求1或2所述一种醇溶性阳离子氟化聚氨酯的制备方法，其特征在于，所述非亲醇小分子扩链剂为1,4丁二醇、乙二醇、一缩二乙二醇和新戊二醇、端氨基聚醚中的一种或两种及以上的组合。
8.根据权利要求1或2所述一种醇溶性阳离子氟化聚氨酯的制备方法，其特征在于，所述交联剂为三羟甲基丙烷、1,2,6-己三醇，甲基葡萄糖苷和蔗糖、硅烷偶联剂KH550/KH560中的一种或两种及以上的组合。
9.根据权利要求1或2所述一种醇溶性阳离子氟化聚氨酯的制备方法，其特征在于，在加入酸中和剂的同时，加入5-30份使用酸中和剂溶解的天蚕丝素和/或1-15份使用酸中和剂溶解的壳聚糖。
10.一种由权利要求1-9任意一项的制备方法制得的醇溶性阳离子氟化聚氨酯。
11.一种由权利要求10所述的醇溶性阳离子氟化聚氨酯制备的壳层雾化喷液，其特征在于，该壳层雾化喷液由以下方式制得：在制得的醇溶性阳离子氟化聚氨酯中加入1-10份消泡剂，在50℃下熟化24h，继续加入水溶性高分子量的聚丙烯酰胺和/或聚乙烯醇，高速搅拌混合均匀，超声分散配制成固含量为35～45％的雾化原液，即为壳层雾化喷液。
12.一种由权利要求11所述的壳层雾化喷液制得的人工仿生皮肤，其特征在于，由以下方式制得：以厚度0.5-1mm的PET板或PDMS基材作为支撑层，核层雾化喷液和壳层雾化喷液作为基础材料，利用带有核壳双层喷头的静电喷枪在支撑层上静电雾化喷涂，所述核壳双层喷头包括核层喷头和套设在核层喷头外的壳层喷头，所述核层喷头用于喷射核层雾化喷液、所述壳层喷头用于喷射壳层雾化喷液，所述核壳喷头的内直径为0.3-0.8mm，壳层喷头的内直径为0.5-2.5mm，静电喷枪的输入电压为15-50V、喷射速度为1-5ml/min，然后将喷涂后的支撑层置于室温25-35℃环境下自然干燥15-24h后即可获得人工仿生皮肤。
13.根据权利要求12所述的人工仿生皮肤，其特征在于，所述核层雾化喷液由50-100质量份水溶性聚苯胺复合液中加入5-10质量份的高分子量聚丙烯酰胺和1-5质量份表面活性剂，搅拌均匀制得。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115260434A (zh) * 2022-07-05 2022-11-01 合肥科天水性科技有限责任公司 一种高分子抗静电涂饰剂、抗静电涂饰制品及制备方法

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4841007A (en) * 1988-03-28 1989-06-20 Becton Dickinson And Company Fluorinated polyetherurethanes and medical devices therefrom
EP0533159A1 (en) * 1991-09-17 1993-03-24 SYREMONT S.p.A. Aqueous dispersions of fluorinated polyurethanes
EP0689908A1 (en) * 1994-06-13 1996-01-03 AUSIMONT S.p.A. Aqueous dispersions of fluorinated polyurethanes
US20020128337A1 (en) * 1999-09-10 2002-09-12 Logsdon Peter Brian Integral skin foams employing 1,1,1,3,3-pentafluoropropane as blowing agent
CN1445254A (zh) * 2003-04-10 2003-10-01 四川大学 侧链含氟聚氨酯材料及其制备方法
CN101230125A (zh) * 2008-02-29 2008-07-30 安徽大学 一种易溶于水的醇溶性聚氨酯及其制备方法
CN101824130A (zh) * 2009-12-31 2010-09-08 广东银洋树脂有限公司 一种软段侧链含氟水性聚氨酯的制备方法
US20110009510A1 (en) * 2008-02-25 2011-01-13 Dic Corporation Process for producing alcohol soluble urethane resin composition, polyurethane porous body, and moisture permeable film
CN103948960A (zh) * 2014-05-20 2014-07-30 四川大学 一种含纳米银多孔硅橡胶/聚氨酯双层人工皮肤及其制备方法
CN103992459A (zh) * 2014-05-26 2014-08-20 北京化工大学 一种可溶解于乙醇的聚氨酯树脂材料及其制备方法
WO2017151915A1 (en) * 2016-03-03 2017-09-08 National University Of Singapore Versatile, flexible and biocompatible elastomeric microtubes
CN110066379A (zh) * 2019-04-29 2019-07-30 四川大学 一种生物稳定性高的含氟含硅聚氨酯材料及其制备方法
CN111423554A (zh) * 2019-09-30 2020-07-17 四川大学 一种具有防水、防油、防污损性能的含氟水性聚氨酯材料
WO2020177068A1 (en) * 2019-03-05 2020-09-10 Dow Global Technologies Llc Waterborne polyurethane dispersion and method for preparing the same

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4841007A (en) * 1988-03-28 1989-06-20 Becton Dickinson And Company Fluorinated polyetherurethanes and medical devices therefrom
EP0533159A1 (en) * 1991-09-17 1993-03-24 SYREMONT S.p.A. Aqueous dispersions of fluorinated polyurethanes
EP0689908A1 (en) * 1994-06-13 1996-01-03 AUSIMONT S.p.A. Aqueous dispersions of fluorinated polyurethanes
US20020128337A1 (en) * 1999-09-10 2002-09-12 Logsdon Peter Brian Integral skin foams employing 1,1,1,3,3-pentafluoropropane as blowing agent
CN1445254A (zh) * 2003-04-10 2003-10-01 四川大学 侧链含氟聚氨酯材料及其制备方法
US20110009510A1 (en) * 2008-02-25 2011-01-13 Dic Corporation Process for producing alcohol soluble urethane resin composition, polyurethane porous body, and moisture permeable film
CN101230125A (zh) * 2008-02-29 2008-07-30 安徽大学 一种易溶于水的醇溶性聚氨酯及其制备方法
CN101824130A (zh) * 2009-12-31 2010-09-08 广东银洋树脂有限公司 一种软段侧链含氟水性聚氨酯的制备方法
CN103948960A (zh) * 2014-05-20 2014-07-30 四川大学 一种含纳米银多孔硅橡胶/聚氨酯双层人工皮肤及其制备方法
CN103992459A (zh) * 2014-05-26 2014-08-20 北京化工大学 一种可溶解于乙醇的聚氨酯树脂材料及其制备方法
WO2017151915A1 (en) * 2016-03-03 2017-09-08 National University Of Singapore Versatile, flexible and biocompatible elastomeric microtubes
WO2020177068A1 (en) * 2019-03-05 2020-09-10 Dow Global Technologies Llc Waterborne polyurethane dispersion and method for preparing the same
CN110066379A (zh) * 2019-04-29 2019-07-30 四川大学 一种生物稳定性高的含氟含硅聚氨酯材料及其制备方法
CN111423554A (zh) * 2019-09-30 2020-07-17 四川大学 一种具有防水、防油、防污损性能的含氟水性聚氨酯材料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115260434A (zh) * 2022-07-05 2022-11-01 合肥科天水性科技有限责任公司 一种高分子抗静电涂饰剂、抗静电涂饰制品及制备方法
CN115260434B (zh) * 2022-07-05 2024-02-02 合肥科天水性科技有限责任公司 一种高分子抗静电涂饰剂、抗静电涂饰制品及制备方法

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