CN116396502A - 一种强力粘合水凝胶的制备方法及其应用 - Google Patents
一种强力粘合水凝胶的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种强力粘合水凝胶的制备方法及其应用,特点是先制备C18/SDS/NaCl胶束溶液并浓缩;然后将聚乙烯醇溶液、丙烯酸加入到浓缩后的胶束溶液中,固化后得到复合水凝胶;将复合水凝胶进行循环冷冻解冻后在氯化钙、氯化镁或氯化铝溶液中浸泡,用去离子水冲洗,最终得到强力粘合水凝胶;优点是通过本方法制备得到的强力粘合水凝胶在干、湿环境中均具有强大粘附力,适用范围广;且具备良好的力学性能、可重复粘附性和长期稳定性,在体内的生物相容性好且无毒。
Description
技术领域
本发明涉及水凝胶的制备,尤其涉及一种强力粘合水凝胶的制备方法及其应用。
背景技术
粘附水凝胶有着与人类具有皮肤组织类似的三维网络结构以及模量,可以像人体皮肤一样传递电信号,是用于柔性电子皮肤、组织胶粘剂、传感器等方面的理想材料。虽然粘附水凝胶在生物医学应用中已经取得实际应用,但大多数粘附水凝胶粘附强度弱、不具备可重复粘合性和抗菌能力、长期稳定性差、水中或恶劣条件下粘附能力丧失、力学性能差等缺点,导致其应用范围受限。因此制备一种水中或恶劣条件下具有强粘附力、较佳抗菌性能和力学性能、良好生物相容性的粘附水凝胶仍面临严峻的挑战。
发明内容
本发明所要解决的技术问题是提供一种强力粘合水凝胶的制备方法,其制备得到的粘附水凝胶在干、湿环境中均具有较强的粘附力和可重复的粘附性,且力学性能好,适用范围广。
本发明解决上述技术问题所采用的技术方案为:一种强力粘合水凝胶的制备方法,包括以下具体步骤:
(1)、配制3~9%w/v的氯化钠(NaCl)溶液;
(2)、在氯化钠溶液中加入十二烷基硫酸钠(SDS),控制十二烷基硫酸钠的浓度为4~10%w/v,在30~70℃水浴中进行机械搅拌,直至溶解完全,形成SDS/NaCl溶液;
(3)、在SDS/NaCl溶液中按浓度0.5~1%w/v加入疏水性单体碳18(C18),机械搅拌1~4h形成C18/SDS/NaCl胶束溶液;
(4)、将制备好的胶束溶液放置在室温下冷却直至胶束析出,然后在4℃的低温条件下以5000~8000转/分的转速离心10~30min,用移液枪吸出部分上清液,剩下的离心液放入水浴中使胶束溶解,使得胶束溶液被浓缩;
(5)、先在聚乙烯醇(PVA)中加入去离子水,调配出浓度为10~20%w/v的PVA溶液,然后将PVA溶液、丙烯酸(AAC)、α-酮戊二酸分别加入到浓缩后的胶束溶液中,控制聚乙烯醇在胶束溶液中的浓度为1~5%w/v、丙烯酸在胶束溶液中的浓度为10~50%w/v、α-酮戊二酸在胶束溶液中的浓度为1~3%w/v,并在30~70℃水浴中搅拌至完全溶解,然后将溶液移入模具中进行紫外光固化成复合水凝胶,光固化时间为2~30min;
(6)、将步骤(5)制备得到的水凝胶进行冷冻解冻并重复2~6次,最后在浓度为8~15%w/v的氯化钙、氯化镁或氯化铝溶液中浸泡1~4h,去离子水清洗,得到强力粘合水凝胶。
进一步地,配制含有1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC)和N-羟基磺基琥珀酰亚胺(NHS)的混合水溶液,控制EDC在混合水溶液中的浓度为0.5~1.2%w/v、NHS在混合水溶液中的浓度为0.3~1%w/v,然后将强力粘合水凝胶浸泡在上述混合水溶液中1~5h后,用去离子水清洗;再将强力粘合水凝胶在浓度为5~12%w/v的ε-聚赖氨酸(EPL)溶液中浸泡10~24h,去离子水清洗,得到抗菌粘合水凝胶。
根据所述的制备方法制备得到的强力粘合水凝胶作为电子皮肤应用。
与现有技术相比,本发明的优点是:
(1)、粘合水凝胶的制备过程中,采用两种方式共同赋予水凝胶强粘附力,一是通过阳离子调控胶束的疏水链段到水凝胶的外表面,使水凝胶表面疏水从而带有粘性;二是丙烯酸AAC含双键,通过紫外光固化形成复合水凝胶,AAC使水凝胶自身带有粘性;因此通过调控水凝胶表面疏水性和AAC自带粘性这两种方式的协同作用,最终制备得到强力粘合水凝胶,在干、湿环境中均具有强大粘附力,其最优粘附强度可达到70kPa,适用范围广。
(2)、聚乙烯醇通过冷冻解冻的方式,形成物理交联网络的水凝胶,其力学性能较好,提高了粘合水凝胶的力学性能和成型性。
(3)、在水凝胶中加入ε-聚赖氨酸,其具有抗菌性,结构式中含有氨基基团,通过EDC和NHS的作用,可与丙烯酸中的羧基基团反应生成酰胺键,稳定的固定在水凝胶中,防止抗菌药物突释不可控。
(4)、本发明制备得到的粘合水凝胶具备可重复粘附性和长期稳定性。
(5)、本发明制备得到的粘合水凝胶在体内的生物相容性好且无毒。
(6)、本发明制备得到的粘合水凝胶可牢固地粘附在皮肤上并能承受较大的力学变形,同时可以连续保持准确稳定的导电性,适合作为柔性电子皮肤使用,用于检测多种疾病。
附图说明
图1为本发明制备得到的粘合水凝胶与猪皮的粘附效果图;
图2为本发明制备得到的粘合水凝胶在水中的粘附效果图;
图3为本发明制备得到的粘合水凝胶经过剥离-粘合循环后粘附强度的实验结果图;
图4为本发明制备得到的粘合水凝胶经沸水和冷冻解冻后的粘性实验结果图;
图5为本发明制备得到的粘合水凝胶通过CCK-8成纤维细胞毒性测试结果图;
图6为本发明制备得到的粘合水凝胶作为电子皮肤使用时对手指指关节的测试结果图。
实施方式
以下结合附图实施例对本发明作进一步详细描述。
实施例一:一种强力粘合水凝胶的制备方法,包括以下具体步骤:
(1)、配制3%w/v的NaCl溶液;
(2)、在NaCl溶液中加入十二烷基硫酸钠(SDS),控制十二烷基硫酸钠的浓度为5%w/v,在45℃水浴中进行机械搅拌,直至溶解完全,形成SDS/NaCl溶液;
(3)、在SDS/NaCl溶液中加入疏水性单体碳18(C18),控制C18在SDS/NaCl溶液中的浓度为1%w/v,机械搅拌2h形成C18/SDS/NaCl胶束溶液;
(4)、将制备好的胶束溶液放置在室温下冷却直至胶束析出,然后在4℃的低温条件下以5000转/分的转速离心25min,用移液枪吸出部分上清液,剩下的离心液放入水浴中使胶束溶解,使得胶束溶液被浓缩;
(5)、先在聚乙烯醇(PVA)中加入去离子水,调配出浓度为20%w/v的PVA溶液,然后将PVA溶液、丙烯酸(AAC)、α-酮戊二酸分别加入到浓缩后的胶束溶液中,控制聚乙烯醇在胶束溶液中的浓度为5%w/v、丙烯酸在胶束溶液中的浓度为20%w/v、α-酮戊二酸在胶束溶液中的浓度为1%w/v,并在45℃水浴中搅拌至完全溶解,然后将溶液移入模具中进行紫外光固化成复合水凝胶,光固化时间为10min;
(6)、将步骤(5)制备得到的复合水凝胶进行冷冻解冻并重复3次,最后在浓度为10%w/v的氯化钙溶液中浸泡1h,去离子水清洗,得到强力粘合的Ca-水凝胶。
实施例二:一种强力粘合水凝胶的制备方法,包括以下具体步骤:
(1)、配制7%w/v的NaCl溶液;
(2)、在NaCl溶液中加入十二烷基硫酸钠(SDS),控制十二烷基硫酸钠的浓度为9%w/v,在60℃水浴中进行机械搅拌,直至溶解完全,形成SDS/NaCl溶液;
(3)、在SDS/NaCl溶液中加入疏水性C18,控制C18在SDS/NaCl溶液中的浓度为0.5%w/v,机械搅拌3h形成C18/SDS/NaCl胶束溶液;
(4)、将制备好的胶束溶液放置在室温下冷却直至胶束析出,然后在4℃的低温条件下以6500转/分的转速离心20min,用移液枪吸出部分上清液,剩下的离心液放入水浴中使胶束溶解,使得胶束溶液被浓缩;
(5)、先在聚乙烯醇(PVA)中加入去离子水,调配出浓度为15%w/v的PVA溶液,然后将PVA溶液、丙烯酸(AAC)、α-酮戊二酸分别加入到浓缩后的胶束溶液中,控制聚乙烯醇在胶束溶液中的浓度为2%w/v、丙烯酸在胶束溶液中的浓度为30%w/v、α-酮戊二酸在胶束溶液中的浓度为2%w/v,并在60℃水浴中搅拌至完全溶解,然后将溶液移入模具中进行紫外光固化成复合水凝胶,光固化时间为25min;
(6)、将步骤(5)制备得到的复合水凝胶进行冷冻解冻并重复4次,最后在浓度为13%w/v的氯化镁溶液中浸泡4h,去离子水清洗,得到强力粘合Mg-水凝胶;
(7)、配制含有1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC)和N-羟基磺基琥珀酰亚胺(NHS)的混合水溶液,控制EDC在混合水溶液中的浓度为1.0%w/v、NHS在混合水溶液中的浓度为0.5%w/v,然后将Mg-水凝胶浸泡在上述混合水溶液中3h后,用去离子水清洗;
(8)、再将Mg-水凝胶在浓度为6%w/v的ε-聚赖氨酸(EPL)溶液中浸泡12h,去离子水清洗,得到抗菌粘合Mg-水凝胶。
实施例三:一种强力粘合水凝胶的制备方法,包括以下具体步骤:
(1)、配制8%w/v的氯化钠溶液;
(2)、在氯化钠溶液中加入十二烷基硫酸钠(SDS),控制十二烷基硫酸钠的浓度为7%w/v,在50℃水浴中进行机械搅拌,直至溶解完全,形成SDS/NaCl溶液;
(3)、在SDS/NaCl溶液中加入疏水性C18,控制C18在SDS/NaCl溶液中的浓度为0.7%w/v,机械搅3h形成C18/SDS/NaCl胶束溶液;
(4)、将制备好的胶束溶液放置在室温下冷却直至胶束析出,然后在4℃的低温条件下以8000转/分的转速离心10min,用移液枪吸出部分上清液,剩下的离心液放入水浴中使胶束溶解,使得胶束溶液被浓缩;
(5)、先在聚乙烯醇(PVA)中加入去离子水,调配出浓度为10%w/v的PVA溶液,然后将PVA溶液、丙烯酸(AAC)、α-酮戊二酸分别加入到浓缩后的胶束溶液中,控制聚乙烯醇在胶束溶液中的浓度为3.5%w/v、丙烯酸在胶束溶液中的浓度为45%w/v、α-酮戊二酸在胶束溶液中的浓度为2.8%w/v,并在50℃水浴中搅拌至完全溶解,然后将溶液移入模具中进行紫外光固化成复合水凝胶,光固化时间为20min;
(6)、将步骤(5)制备得到的复合水凝胶进行冷冻解冻并重复5次,最后在浓度为8%w/v的氯化铝溶液中浸泡4h,去离子水清洗,得到强力粘合Al-水凝胶;
(7)、配制含有1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC)和N-羟基磺基琥珀酰亚胺(NHS)的混合水溶液,控制EDC在混合水溶液中的浓度为0.6%w/v、NHS在混合水溶液中的浓度为0.9%w/v,然后将Al-水凝胶浸泡在上述混合水溶液中4h后,用去离子水清洗;
(8)、再将Al-水凝胶在浓度为10%w/v的ε-聚赖氨酸(EPL)溶液中浸泡15h,去离子水清洗,得到抗菌粘合Al-水凝胶。
本发明所制备得到的粘合水凝胶的粘附机理为:
胶束中含有疏水性C18和两亲性表面活性剂十二烷基硫酸钠SDS,胶束和水凝胶制备为复合水凝胶后,当带正电荷的阳离子如:钙离子、镁离子或铝离子等作用于复合水凝胶时,可以吸引SDS带负电荷一端的硫酸根从而诱导SDS链段重排,亲水端(硫酸根)浮于水凝胶的最外侧,疏水端(烷基)位于水凝胶的次外侧,进一步经过去离子水冲洗后,结合后的正负电荷(钙离子与硫酸根)被水洗掉,水凝胶外表面留下SDS的疏水端(烷基)和疏水的C18链段,进而赋予复合水凝胶外表面高疏水性,高疏水性本身具备超强排水能力的特点,从而使得水凝胶具备强粘附性。另外,丙烯酸AAC含双键,α-酮戊二酸是光引发剂,紫外光固化形成水凝胶,使得水凝胶本身具有粘性但粘性弱,与上述水凝胶外表面的高疏水性性能两者结合后,使得制备得到的水凝胶形成表面有粘性且表面疏水性赋予粘性的强力粘合水凝胶。而聚乙烯醇通过冷冻解冻的方式,形成物理交联网络的水凝胶,无粘性、力学性能较好,提高了粘合水凝胶的力学性能和成型性。
将本申请制备得到的强力粘合水凝胶与猪皮粘合后,其剥离粘附强度为70kPa,如图1所示;如图2所示,该强力粘合水凝胶在水中可长期稳定的粘附石头和700g砝码,说明其在恶劣条件下仍能具备较强的粘附能力。
本发明制备得到的强力粘合水凝胶进行粘合—剥离重复粘附性测试实验,实验结果表明:经过18次剥离-粘合的过程以及室温存放30天后,粘合水凝胶仍能保持最初的粘附强度,如图3所示;且在100℃沸水中和负80℃冷冻后再恢复到室温,粘合水凝胶仍能保持强粘附性,如图4所示。
本发明制备得到的强力粘合水凝胶通过CCK-8成纤维细胞毒性测试,如图5所示,图中:胶、胶-Ca、胶-Mg和胶-Mg-EPL为4种水凝胶的浸提液,培养基作为阴性对照组,胶为步骤(5)制备得到的复合水凝胶,分别进行CCK-8成纤维细胞毒性测试,细胞培养时间分别是1天、3天和5天。实验结果表明:粘附水凝胶浸提液和培养基(阴性对照)液体中的成纤维细胞生长的一样好,说明本发明的粘合水凝胶具有较佳的细胞相容性,且无细胞毒性。
本发明制备得到的强力粘合水凝胶中,由于聚丙烯酸在水溶液中羧基官能团发生部分电离,因而具有导电性,称其为聚电解质。且钙离子、镁离子或铝离子也都能导电,其在电场作用下可以发生定向移动,同样能形成电流,因此,本发明的强力粘合水凝胶具有导电性。因此,本发明的粘合水凝胶可作为兼具强粘附性、抗菌、导电等多重功能的电子皮肤使用,其在手腕弯曲、额头晃动等情况下仍能牢固的粘附在原处,与现有电子皮肤采用胶带粘在身上相比,具有明显的优势。
本发明的粘合水凝胶作为电子皮肤在检测病人的指关节、手腕、手肘、膝关节等部位的运动情况时,通过运动的快慢和运动的幅度等信息反馈为电化学信号,从而建立水凝胶对疾病检测的评价标准。作为电子皮肤对手指指关节测试为例:
将粘合水凝胶粘贴在食指的指关节处,并在水凝胶的两端连接正负电极,电极与电化学工作站连接,随着食指的弯曲角度从90°减少到0°,相对电阻逐渐减小,在保持手指弯曲角度不变的情况下,信号是相对稳定的,如图6所示。这表明本发明的粘合水凝胶作为电子皮肤对手指运动的测量是即时、准确和稳定的。
本发明的保护范围包括但不限于以上实施方式,其保护范围以权利要求书为准,任何对本技术做出的本领域的技术人员容易想到的替换、变形、改进均落入本发明的保护范围。
Claims (3)
1.一种强力粘合水凝胶的制备方法,其特征在于包括以下具体步骤:
(1)、配制3~9%w/v的氯化钠(NaCl)溶液;
(2)、在氯化钠溶液中加入十二烷基硫酸钠(SDS),控制十二烷基硫酸钠的浓度为4~10%w/v,在30~70℃水浴中进行机械搅拌,直至溶解完全,形成SDS/NaCl溶液;
(3)、在SDS/NaCl溶液中按浓度0.5~1%w/v加入疏水性单体碳18(C18),机械搅拌1~4h形成C18/SDS/NaCl胶束溶液;
(4)、将制备好的胶束溶液放置在室温下冷却直至胶束析出,然后在4℃的低温条件下以5000~8000转/分的转速离心10~30min,用移液枪吸出部分上清液,剩下的离心液放入水浴中使胶束溶解,使得胶束溶液被浓缩;
(5)、先在聚乙烯醇(PVA)中加入去离子水,调配出浓度为10~20%w/v的PVA溶液,然后将PVA溶液、丙烯酸(AAC)、α-酮戊二酸分别加入到浓缩后的胶束溶液中,控制聚乙烯醇在胶束溶液中的浓度为1~5%w/v、丙烯酸在胶束溶液中的浓度为10~50%w/v、α-酮戊二酸在胶束溶液中的浓度为1~3%w/v,并在30~70℃水浴中搅拌至完全溶解,然后将溶液移入模具中进行紫外光固化成复合水凝胶,光固化时间为2~30min;
(6)、将步骤(5)制备得到的水凝胶进行冷冻解冻并重复2~6次,最后在浓度为8~15%w/v的氯化钙、氯化镁或氯化铝溶液中浸泡1~4h,去离子水清洗,得到强力粘合水凝胶。
2.如权利要求1所述的一种强力粘合水凝胶的制备方法,其特征在于:配制含有1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC)和N-羟基磺基琥珀酰亚胺(NHS)的混合水溶液,控制EDC在混合水溶液中的浓度为0.5~1.2%w/v、NHS在混合水溶液中的浓度为0.3~1%w/v,然后将强力粘合水凝胶浸泡在上述混合水溶液中1~5h后,用去离子水清洗;再将强力粘合水凝胶在浓度为5~12%w/v的ε-聚赖氨酸溶液中浸泡10~24h,去离子水清洗,得到抗菌粘合水凝胶。
3.根据权利要求1或2所述的制备方法制备得到的强力粘合水凝胶作为电子皮肤应用。
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