CN110358115B - 一种3d打印制备生物质基导电水凝胶的方法 - Google Patents

一种3d打印制备生物质基导电水凝胶的方法 Download PDF

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CN110358115B
CN110358115B CN201910679806.0A CN201910679806A CN110358115B CN 110358115 B CN110358115 B CN 110358115B CN 201910679806 A CN201910679806 A CN 201910679806A CN 110358115 B CN110358115 B CN 110358115B
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hydrogel
biomass
printing
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CN110358115A (zh
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王基夫
卢传巍
储富祥
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Institute of Chemical Industry of Forest Products of CAF
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Abstract

一种3D打印制备生物质基导电水凝胶的方法，首先将纤维素基大分子单体、松香基单体、丙烯酸单体、引发剂按一定比例混合，在25～70℃下搅拌溶解，然后往混合液中加入单体质量总和的5～10wt％的二异氰酸酯混合均匀制得3D打印光敏树脂溶液。采用SLA光固化3D打印机打印具有复杂形状的水凝胶前驱体1，然后对水凝胶前驱体1进行热处理后得到具有双固化网络的水凝胶前驱体2。最后将得到水凝胶前驱体2在1～15wt％碱性溶液中在5～60℃下溶胀0.1～10h得到生物质基导电水凝胶。本发明可用于制备具有复杂形状、导电性能优良、机械强度高的生物质基水凝胶，可进一步拓宽生物质资源的应用领域。

Description

一种3D打印制备生物质基导电水凝胶的方法
技术领域
本发明属于高分子材料技术领域，涉及一种3D打印制备生物质基导电水凝胶的方法。
背景技术
随着石油化石资源的日益消耗以及对环境污染的日益关注，利用可再生资源制备高分子功能材料受到越来越多科研工作者的关注。水凝胶作为一种具有三维网状结构，同时能够吸水并保水而又不溶于水的高分子材料，已经被广泛的生物医药、石油化工、食品、化妆品和电子电器领域。纤维素作为世界上储量最丰富的可再生资源，具有来源广泛、价格低廉、生物相容性良好、力学性能优异的特点，目前已经被广泛地用于制备水凝胶材料。松香作为另一种可再生的自然资源，其所独有的三元菲骨架使其具有优异的疏水性性能，这极大地限制了松香在水凝胶领域的应用。虽然目前已经通过对松香进行改性制备了水溶性的可聚合松香单体，但存在制备过程复杂、成本较高的问题，利用常见的油溶性的丙烯酸基松香单体制备水凝胶的研究工作鲜有报道。
此外，按着对外界刺激的响应情况水凝胶可以分为传统型水凝胶和智能响应型水凝胶。导电水凝胶作为一种智能响应型水凝胶引起了人们极大的兴趣，并已被应用于传感器、电容器、组织材料等领域。然而，目前报道的这类水凝胶存在的一个明显问题就是其机械强度较低，远远不能满足实际应用的需要。并且所制备的水凝胶的形状较为单一，不能实现复杂形状的构筑，这也极大地限制了导电水凝胶的应用领域。3D打印作为一种先进的制备技术，可以利用3D模型或CAD文件通过逐层累积实现复杂的形状的构筑。因此通过3D打印技术，采用成型后再溶胀的策略，制备纤维素、松香衍生的生物质基导电水凝胶具有迫切的需求和重要的研究意义。
发明内容
解决的技术问题：本发明提供一种3D打印制备生物质基导电水凝胶的方法，制备的生物质基导电水凝胶具有可以定制的复杂形状和优异的导电性能，可作为一种新型的传感器、电容器、组织材料等，从而扩大了纤维素、松香等生物质资源的应用领域。
技术方案：一种3D打印制备生物质基导电水凝胶的方法，步骤为：
第一步：首先将乙基纤维素基大分子单体、松香基单体、丙烯酸单体、引发剂按一定比例混合，在25～70℃下搅拌溶解，然后往混合液中加入单体质量总和的5～10wt％的二异氰酸酯混合均匀制得3D打印光敏树脂溶液；
第二步：采用SLA光固化3D打印机打印具有复杂形状的水凝胶前驱体1，然后对水凝胶前驱体1进行热处理后得到具有双固化网络的水凝胶前驱体2；
第三步：最后将得到水凝胶前驱体2在1～15wt％的碱性溶液中在5～60℃下溶胀0.1～10h得到生物质基导电水凝胶。
优选的，上述第一步所述的乙基纤维素基大分子单体结构为：
Figure BSA0000186515590000021
其中所采用的乙基纤维素粘度为3～7、9～11、18～22、45～55、90～110、180～220、270～330mPa.s中的任一种。
优选的，上述第一步所述的松香基单体结构为：
Figure BSA0000186515590000031
其中R为松香结构，所采用的松香为左旋海松酸、枞酸、脱氢枞酸、海松酸、歧化松香中的任一种。
优选的，上述第一步所述的丙烯酸单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯中的一种。
优选的，上述第一步所述的引发剂为(2，4，6-三甲基苯甲酰基)二苯基氧化膦、安息香双甲醚、2-羟基-4′-(2-羟乙氧基)-2-甲基苯丙酮中的一种。
优选的，上述第一步所述的二异氰酸酯为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)、赖氨酸二异氰酸酯(LDI)中的一种。
优选的，上述第一步所述的一定量比例为质量比例[乙基纤维素大分子单体]：[松香单体]∶[丙烯酸单体]∶[引发剂]＝0.3∶2∶8∶0.2。
优选的，上述第二步所述的热处理条件为110℃，8小时。
优选的，上述第三步所述的碱性溶液为氢氧化钠、氢氧化钾中的一种。
有益效果：1.本发明涉及一种3D打印制备生物质基导电水凝胶的方法，通过该方法可以制备具有可定制形状的生物质基水凝胶，具有原料来源广泛，操作简单，制备过程绿色无害的优点，有利于进一步扩展生物质资源的应用领域。2、本发明所制备的生物质基导电水凝胶具有优异的导电性能和机械性能，可作为一种新型的传感器、电容器、组织材料等，从而实现了生物质资源的高值化利用。
附图说明
图1为实施例1中水凝胶前驱体2溶胀前后的图片。
图2为实施例1中水凝胶前驱体2溶胀后弯曲、导电测试图片。
图3为实施例1中水凝胶前驱体2溶胀后的应力-应变曲线。
具体实施方式
由于3D打印制备生物质基导电水凝胶的方法有很大影响，下面结合实施例进一步阐明本发明的内容，但是这些实施例并不限制本发明的保护范围。
实施例1：[乙基纤维素大分子单体]∶[松香单体]∶[丙烯酸单体]∶[引发剂]＝0.3∶2∶8∶0.2，制备生物质基导电水凝胶。
第一步：首先将粘度为3～7mPa.s的乙基纤维素基大分子单体0.9g、歧化松香单体6g、丙烯酸羟乙酯24g、(2，4，6-三甲基苯甲酰基)二苯基氧化膦0.6g混合，在70℃下搅拌充分溶解，然后往混合液中加入1.5g六亚甲基二异氰酸酯混合均匀制得3D打印光敏树脂溶液；
第二步：采用SLA光固化3D打印机打印具有复杂形状的水凝胶前驱体1，然后对水凝胶前驱体1在110℃下热处理8小时后得到具有双固化网络的水凝胶前驱体2；
第三步：最后将得到水凝胶前驱体2在10wt％的氢氧化钠溶液中在40℃下溶胀5h得到生物质基导电水凝胶。
实施例2：[乙基纤维素大分子单体]∶[松香单体]∶[丙烯酸单体]∶[引发剂]＝0.3∶2∶8∶0.2，制备生物质基导电水凝胶。
第一步：同实施例1；
第二步：采用SLA光固化3D打印机打印具有复杂形状的水凝胶前驱体1，然后对水凝胶前驱体1在80℃下热处理5小时后得到具有双固化网络的水凝胶前驱体2；
第三步：最后将得到水凝胶前驱体2在5wt％的氢氧化钾溶液中在20℃下溶胀4h得到生物质基导电水凝胶。
实施例3：[乙基纤维素大分子单体]∶[松香单体]∶[丙烯酸单体]∶[引发剂]＝0.5∶4∶6∶0.3，制备生物质基导电水凝胶。
第一步：首先将粘度为90～110mPa.s的乙基纤维素基大分子单体1g、脱氢枞酸单体8g、丙烯酸羟乙酯12g、安息香双甲醚0.6g混合，在60℃下搅拌充分溶解，然后往混合液中加入1.6g甲苯二异氰酸酯混合均匀制得3D打印光敏树脂溶液；
第二步：同实施例1；
第三步：同实施例1。
实施例4：[乙基纤维素大分子单体]∶[松香单体]∶[丙烯酸单体]∶[引发剂]＝0.5∶4∶6∶0.3，制备生物质基导电水凝胶。
第一步：同实施例3
第二步：采用SLA光固化3D打印机打印具有复杂形状的水凝胶前驱体1，然后对水凝胶前驱体1在80℃下热处理5小时后得到具有双固化网络的水凝胶前驱体2；
第三步：最后将得到水凝胶前驱体2在5wt％的氢氧化钾溶液中在20℃下溶胀4h得到生物质基导电水凝胶。
实施例5：[乙基纤维素大分子单体]∶[松香单体]∶[丙烯酸单体]∶[引发剂]＝0.5∶4∶6∶0.3，制备生物质基导电水凝胶。
第一步：首先将粘度为270～330mPa.s的乙基纤维素基大分子单体1g、脱氢枞酸单体8g、丙烯酸羟乙酯12g、(2，4，6-三甲基苯甲酰基)二苯基氧化膦0.6g混合，在60℃下搅拌充分溶解，然后往混合液中加入2g甲苯二异氰酸酯混合均匀制得3D打印光敏树脂溶液；
第二步：采用SLA光固化3D打印机打印具有复杂形状的水凝胶前驱体1，然后对水凝胶前驱体1在100℃下热处理8小时后得到具有双固化网络的水凝胶前驱体2；
第三步：最后将得到水凝胶前驱体2在10wt％的氢氧化钠溶液中在50℃下溶胀5h得到生物质基导电水凝胶。
实施例6：[乙基纤维素大分子单体]∶[松香单体]∶[丙烯酸单体]∶[引发剂]＝0.3∶2∶8∶0.2，制备生物质基导电水凝胶。
第一步：首先将粘度为3～7mPa.s的乙基纤维素基大分子单体0.9g、歧化松香单体6g、甲基丙烯酸羟乙酯24g、2-羟基-4′-(2-羟乙氧基)-2-甲基苯丙酮0.6g混合，在70℃下搅拌充分溶解，然后往混合液中加入1.5g六亚甲基二异氰酸酯混合均匀制得3D打印光敏树脂溶液；
第二步：采用SLA光固化3D打印机打印具有复杂形状的水凝胶前驱体1，然后对水凝胶前驱体1在110℃下热处理5小时后得到具有双固化网络的水凝胶前驱体2；
第三步：最后将得到水凝胶前驱体2在5wt％的氢氧化钠溶液中在40℃下溶胀8h得到生物质基导电水凝胶。
谱图分析
图1为实施例1中水凝胶前驱体2溶胀前后的图片。从图上可以发现溶胀后得到的水凝胶体积显著变大，但依旧保持3D立体形状，表明溶胀后得到的水凝胶具有优异的形状保真度，这也进一步说明采用本发明的制备方法可以制备具有复杂形状的水凝胶。
图2为实施例1中水凝胶前驱体2溶胀后弯曲、导电测试图片。从图上可以发现溶胀后得到的水凝胶具有非常好的柔性，可以任意弯曲，且表现出优异的导电性，接入电路中可以点亮灯泡。
图3为实施例1中水凝胶前驱体2溶胀后的应力-应变曲线。从图上可以发现溶胀后水凝胶表现出优异的机械性能。
以上所述的实施实例对本发明的技术方案进行了详细的说明，应理解的是，以上所述仅为本发明的较佳实施例，并不用于限制本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，当可利用上述揭示的技术内容做出些许改动或修饰为等同变化的等效实施例，但是，凡在本发明的原则范围内所做的任何修改或改进等，均应包含在本发明范围之内。

Claims (6)

1.一种3D打印制备生物质基导电水凝胶的方法，其特征在于步骤为：
第一步：首先将乙基纤维素基大分子单体、松香基单体、丙烯酸单体、引发剂按一定比例混合，在25～70℃下搅拌溶解，然后往混合液中加入单体质量总和的5～10wt％的二异氰酸酯混合均匀制得3D打印光敏树脂溶液； 所述的乙基纤维素基大分子单体结构为：
Figure FSB0000198391940000011
其中所采用的乙基纤维素粘度为3～7、9～11、18～22、45～55、90～110、180～220、270～330mPa.s中的任一种；
所述的松香基单体结构为：
Figure FSB0000198391940000012
其中R为松香结构，所采用的松香为左旋海松酸、枞酸、脱氢枞酸、海松酸、歧化松香中的任一种；
所述的丙烯酸单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯中的一种；
第二步：采用SLA光固化3D打印机打印具有复杂形状的水凝胶前驱体1，然后对水凝胶前驱体1进行热处理后得到具有双固化网络的水凝胶前驱体2；
第三步：最后将得到水凝胶前驱体2在1～15wt％的碱性溶液中在5～60℃下溶胀0.1～10h得到生物质基导电水凝胶。
2.根据权利要求1所述一种3D打印制备生物质基导电水凝胶的方法，其特征在于第一步所述的引发剂为(2，4，6-三甲基苯甲酰基)二苯基氧化膦、安息香双甲醚、2-羟基-4′-(2-羟乙氧基)-2-甲基苯丙酮中的一种。
3.根据权利要求1所述一种3D打印制备生物质基导电水凝胶的方法，其特征在于第一步所述的二异氰酸酯为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)、赖氨酸二异氰酸酯(LDI)中的一种。
4.根据权利要求1所述一种3D打印制备生物质基导电水凝胶的方法，其特征在于第一步所述的一定量比例为质量比例[乙基纤维素大分子单体]∶[松香单体]∶[丙烯酸单体]∶[引发剂]＝[0.2～1]∶[1～5]∶[5～9]∶[0.1～0.5]。
5.根据权利要求1所述一种3D打印制备生物质基导电水凝胶的方法，其特征在于第二步所述的热处理条件为70～150℃，0～10小时。
6.根据权利要求1所述一种3D打印制备生物质基导电水凝胶的方法，其特征在于第三步所述的碱性溶液为氢氧化钠、氢氧化钾中的一种。
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