CN104558699B - 一种弹性导电胶体、制备方法及其应用 - Google Patents

一种弹性导电胶体、制备方法及其应用 Download PDF

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CN104558699B
CN104558699B CN201510004341.0A CN201510004341A CN104558699B CN 104558699 B CN104558699 B CN 104558699B CN 201510004341 A CN201510004341 A CN 201510004341A CN 104558699 B CN104558699 B CN 104558699B
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nitrate
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CN104558699A (zh
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林潇
关莹
白艳洁
杨磊
杨惠林
孙宁
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Beijing Wanjia High Tech Pharmaceutical Technology Co ltd
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Suzhou University
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Abstract

本发明公开了一种弹性导电胶体、制备方法及其应用。该弹性导电胶体由淀粉凝胶弹性基质和高浓度电解质构成，该胶体弹性伸长率为1000%～2500%，断裂伸长率为1500%～9000%，体积电阻率1～1×104Ω·cm，而且该胶体同时具有自发荧光性、生物降解性、粘性、透明度高、绿色无毒等特点。本发明同时涉及该弹性导电胶体的制备方法，其特征是在高浓度金属盐溶液中加入淀粉后加温、糊化、保温、冷却后即得到弹性导电胶体。本发明的制备方法具有成本低廉、工艺简单、设备要求低、绿色环保等特点。本发明所述胶体可用于柔性电路制备、导电粘合剂、导电织物制备、医用敷料、药物缓释、组织粘接等。

Description

一种弹性导电胶体、制备方法及其应用
技术领域
本发明涉及一种胶体、制备方法及其应用，特别涉及一种导电弹性胶体制备方法及其应用。本发明涉及柔性电路、导电粘结剂、导电织物，医药卫生等技术领域。
背景技术
淀粉作为一种多糖类天然高分子，具有可再生不枯竭、可生物降解、稳定性高、安全无毒等特点，很早就被应用于医药卫生等领域。传统的淀粉糊化后具有一定的粘性，在空气中室温下很快会失水变干。如中国发明专利CN 101054501A、CN 102493274 A、CN102757744 A和CN 103897629 A所提供的大多淀粉基的胶黏剂就是基于淀粉的这个特性。
已有报道显示，通过调控淀粉的主要结构特性，或将淀粉与其它高分子交联，可制备稳定的凝胶材料，其具有较为优异的溶胀性和保湿（水）性。例如，中国发明专利CN1480224A公开了一类由淀粉、聚乙烯吡咯烷酮、聚乙烯醇、水溶性纤维素和水制备的水凝胶。其中淀粉的质量分数优选范围为5～15%。混合物开始制备成半凝胶状态，通过暴露在电子束或γ辐射下，总吸收剂量在5～50kGy的范围内来完成凝胶化。高于20kGy的辐射量可以导致片层形式的凝胶粘连；低辐射量会导致形成膏状或半液体凝胶。制备的水凝胶具有非常优异的溶胀性和粘性，凝胶强度在10-2MPa数量级，断裂伸长率在300%左右，吸水性为1000%～8000%，可以作为一种敷料和药物缓释材料。中国发明专利CN 101982202A公开了一类淀粉基的水凝胶。该水凝胶包含质量分数为10～30％的淀粉，2～15％的水溶性高分子。此外，制备中加入了胍盐缩聚物和交联剂，溶剂为去离子水。其具有较高的溶胀度（平衡溶胀率为300%左右），并能保持湿润，此外其透明度高、力学强度适中。中国发明专利CN103833916 A公开了一种医用淀粉丙烯酸基复合水凝胶的制备工艺。该水凝胶由糊化的淀粉、15～20％用碱中和后的丙烯酸、12-16％的N，N’- 亚甲基双丙烯酸胺、20～40％的蒸馏水制成。制备的水凝胶不易变色，保湿效果良好，使用时效超过720 小时且防菌杀毒，适合作为医用复合敷料。上述专利均制备出淀粉基的水凝胶。所述制备过程中，均采用了除淀粉外的高分子作为原料，并加入交联剂。制备工艺较为复杂，而且对环境影响较大。制备的水凝胶延展性有限，而且几乎没有导电性，限制了其在某些方向的应用。
目前的导电弹性材料绝大部分是通过在普通弹性体材料中加入导电颗粒或纤维，制备出的电子导电型弹性材料。中国发明专利CN 101918495 A公开了一种电子导电型导电弹性体材料。该材料是将碳纳米管分散于热塑性弹性体组成的基体中制备而成。碳纳米管的直径为30～300nm，纵横比为10～1000；热塑性弹性体仅由聚酯系热塑性弹性体构成。相对于100质量份上述基本成分，碳纳米管以0.01～10 质量份的比例进行混合。该材料体积电阻率在1011Ω·cm以下。中国发明专利CN 102702662 A公开了一种导热导电弹性体材料及其制备方法。具体为在苯乙烯弹性体中加入金属纤维（包括铜纤维和铝纤维）、纳米铜粉和膨胀石墨作为导电物质，并加入矿物油、聚烯烃、抗氧剂作为辅料。制备的材料导热、导电（体积电阻率在103Ω·cm左右）、柔软、硬度低。
除了在弹性体基体中添加导电性单质，也可以添加金属盐，通过碱金属离子与聚醚嵌段的络合配位制备有机高分子聚电解质，其为一种离子导电型弹性材料。如中国发明专利CN 103131165 A公开了一种导电PA12 弹性体材料及制备方法。该材料是通过将碱金属盐加入到PA12 弹性体中，并添加抗氧剂，热稳定剂，助导电剂制备而成。其中碱金属盐中阳离子可为Li+、Na+或K+，阴离子为C1-、Br-、I-或ClO4 -。该弹性体具有导电效果持久、导电效果好（表面电阻率102～103Ω·m）、成本低、耐热性好等优点。上述导电弹性体采用热塑性弹性体作为基体，延展性有限，限制了其应用领域和应用效果。
发明内容
本发明的目的是，针对现有的导电弹性材料存在的不足，提供一种具有生物降解性、粘性、透明度高、绿色无毒特点的弹性导电胶体、制备方法及其应用。
实现本发明目的的技术方案是：一种弹性导电胶体的制备方法，包括如下步骤：
1、按质量百分比20～75 %，将金属盐溶解于去离子水中，得到电解质溶液；所述金属盐为硝酸镁、硝酸钠、硝酸锌、硝酸铯、硝酸钙、硝酸钕、硝酸铝、硝酸钾、氯化钾、氯化镁、氯化钙、氯化钠、氯化锌、氯化铯、氯化铝中的一种，或它们的任意组合；
2、按质量百分比10～40 %，将淀粉加入到步骤1制备的溶液中，在温度为33℃～120℃的条件下充分搅拌，至淀粉完全糊化，得到粘稠液体；
3、将步骤2得到的粘稠液体在温度为25℃～90℃的条件下静置10分钟至48小时,得到弹性导电胶体。
本发明所述的淀粉为玉米、马铃薯、麦类、红薯、山芋、木薯、糯米原淀粉及其改性淀粉中的一种，或它们的任意组合。
本发明技术方案还包括一种按上述制备方法得到的弹性导电胶体，弹性导电胶体的电阻率为1～1×104Ω·cm，弹性伸长率为1000%～2500%, 断裂延伸率为1500%～9000%；它具有可生物降解性；具有自发荧光性，发射光波长为400nm～500nm。
在本发明技术方案中，当所述的金属盐为硝酸锌、硝酸铯、硝酸钙、硝酸钕、硝酸铝、硝酸钾、氯化钾、氯化钙、氯化锌、氯化铯、氯化铝中的一种，或它们的任意组合时，制备的弹性导电胶体具有水溶性。
本发明提供的一种弹性导电胶体的应用，它可用于柔性电路制备、导电粘结剂、导电织物制备、医用敷料、组织粘接、药物缓释领域。
将特定糊化淀粉的凝胶作为弹性基质，高浓度金属盐的溶液电解质作为导电剂，提供了一种弹性导电胶体，它是通过将特定无机盐电解质参与到特定淀粉的糊化过程中而制备得到。本发明所制备的胶体弹性伸长率为1000%～2500%, 断裂延伸率1500%～9000%，体积电阻率1～1×104Ω·cm，而且同时具有自发荧光性。
与现有技术相比，本发明克服了单纯淀粉糊化后易挥发失水，变干变脆的缺陷，通过将特定无机盐电解质参与到特定淀粉的糊化过程中制备了一种稳定的弹性导电胶体，该胶体可用于柔性电路制备、导电粘合剂、导电织物制备、医用敷料、组织粘接、药物缓释等领域。
更为重要的是，本发明所制备胶体与现有导电胶体相比，第一，其具有生物降解性，因此可用于可生物降解柔性电路设计，可生物降解导电粘合剂、导电织物的制备；第二，其具有优异的延展性和一定的粘性，可用于大延展电子器件的制备，人体柔性组织和器官的粘接；第三，其具有荧光性，可用于柔性器件中和体内胶体的检测和追踪。
综上所述，与现有材料及制备方法相比，本发明具有如下有益效果：
1、本发明制备弹性导电胶体的原料来源丰富、成本低廉，且绿色环保、对人体无害；
2、本发明所制备的弹性导电胶体制备工艺简单，对设备要求较低，易实现大规模生产，而且制备过程环境友好。
3、本发明所制备的弹性导电胶体，兼具高弹性、导电性、生物降解性、自发荧光、粘性、透明度高、绿色无毒等多种性能，可用于柔性电路制备、导电粘结剂、导电织物制备、医用敷料、组织粘接、药物缓释等多个领域。
具体实施方式
下面结合实施例对本发明作进一步说明。
实施例1：
将3.5g 氯化镁加入到9ml去离子水中，在室温下或加热搅拌至完全溶解，得到电解质溶液；然后将4g玉米淀粉加入电解质溶液并加热，在60℃搅拌直至淀粉完全糊化，得到粘稠液体。将粘稠液体置于容器中在25℃静置40小时，得到半透明弹性导电胶体。用万能力学试验机对胶体做单轴拉伸试验，结果显示其弹性伸长率为1100%，断裂延伸率为1700%。用恒电压法测量其体积电阻率为5.7×103Ω·cm。光谱法测量显示其具有自发荧光性能，发射光波长为450nm。用拉伸法测得该胶体对抛光后纯铜的粘结强度为50 kPa。
将本实施例提供的胶体用于柔性电路的制备：将淀粉糊化后的粘稠液体装于打印机中，印刷于柔性基板上，室温静置24小时，即得柔性电路。
将本实施例提供的胶体用于导电织物的制备：将实施例1中淀粉糊化后的粘稠液体于10KPa以下的真空抽气15min后，均匀涂于织物表面，40℃下静置12小时即得导电织物。测得该织物的表面电阻率为2.4×104Ω/□。
将该弹性导电胶体放入15倍于其体积的去离子水中搅拌，可以观察到胶体最终完全溶解。
实施例2：
将表1中各种无机盐按相应质量百分比分别加入到10ml去离子水中，完全溶解，然后将3g红薯淀粉加入到上述溶液中，在50℃搅拌直至淀粉完全糊化，得到粘稠液体，将粘稠液体置于容器中在37℃静置24小时，得到不同的半透明弹性导电胶体，测量各自的体积电阻率、弹性伸长率和断裂延伸率，结果列于表1。
表1 含不同金属盐的胶体的体积电阻率、弹性伸长率和断裂延伸率
。
实施例3：
将4g氯化锌加入到8ml去离子水中，完全溶解，然后将表2中的各种淀粉按相应质量百分比分别加入到上述溶液中, 在表2中给定温度下搅拌直至淀粉完全糊化，得到粘稠液体，将粘稠液体置于容器中在60℃静置4小时，得到不同的弹性导电半透明胶体，测量各自的体积电阻率、弹性伸长率和断裂延伸率，结果列于表2。
表2不同淀粉制备的胶体的体积电阻率、弹性伸长率和断裂延伸率
。
实施例4：
将实施例1中淀粉糊化后的粘稠液体剧烈搅拌以混入大量气体，再将粘稠液体置于容器中在50℃保温2小时，则得到弹性导电不透明胶体。若将实施例1中淀粉糊化后的粘稠液体10KPa以下的真空抽气15 min，再将粘稠液体置于容器中于50℃保温20小时，则得到弹性导电透明胶体。
将本实施例提供的弹性导电透明胶体用于心肌缺损部位的组织粘接：制造大鼠心肌缺损动物模型，然后将胶体（经过紫外照射灭菌）涂敷于缺损处，观察到胶体可以紧密贴附于心肌表面并将缺损部位粘合在一起。3周后，观察到缺损心肌有部分得到修复。

Claims (6)

1.一种弹性导电胶体的制备方法，其特征在于包括如下步骤：
（1）按质量百分比20～75 %，将金属盐溶解于去离子水中，得到电解质溶液；所述金属盐为硝酸镁、硝酸钠、硝酸锌、硝酸铯、硝酸钙、硝酸钕、硝酸铝、硝酸钾、氯化钾、氯化镁、氯化钙、氯化钠、氯化锌、氯化铯、氯化铝中的一种，或它们的任意组合；
（2）按质量百分比10～40 %，将淀粉加入到步骤（1）制备的溶液中，在温度为33℃～120℃的条件下充分搅拌，至淀粉完全糊化，得到粘稠液体；
（3）将步骤（2）得到的粘稠液体在温度为25℃～90℃的条件下静置10分钟至48小时,得到弹性导电胶体，所述的弹性导电胶体的电阻率为1～1×104Ω·cm，弹性伸长率为1000%～2500%, 断裂延伸率为1500%～9000%。
2.根据权利要求1所述的一种弹性导电胶体的制备方法，其特征在于：所述的金属盐为硝酸锌、硝酸铯、硝酸钙、硝酸钕、硝酸铝、硝酸钾、氯化钾、氯化钙、氯化锌、氯化铯、氯化铝中的一种或它们的任意组合。
3.根据权利要求1所述的一种弹性导电胶体的制备方法，其特征在于：所述的淀粉为玉米、马铃薯、麦类、红薯、山芋、木薯、糯米原淀粉及其改性淀粉中的一种或它们的任意组合。
4.一种按权利要求1制备方法得到的弹性导电胶体，其特征在于：所述的弹性导电胶体的电阻率为1～1×104Ω·cm，弹性伸长率为1000%～2500%, 断裂延伸率为1500%～9000%；所述的弹性导电胶体具有可生物降解性。
5.一种按权利要求2制备方法得到的弹性导电胶体，其特征在于：所述的弹性导电胶体具有水溶性。
6.一种按权利要求1或2制备方法得到的弹性导电胶体的应用，其特征在于：用于柔性电路制备、导电粘结剂、导电织物制备、医用敷料、组织粘接或药物缓释。
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