CN108383991B - 可导电多臂交联剂的应用 - Google Patents

可导电多臂交联剂的应用 Download PDF

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CN108383991B
CN108383991B CN201810507523.3A CN201810507523A CN108383991B CN 108383991 B CN108383991 B CN 108383991B CN 201810507523 A CN201810507523 A CN 201810507523A CN 108383991 B CN108383991 B CN 108383991B
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王玮
谭宝玉
刘文广
贾慧珍
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Abstract

本发明公开可导电多臂交联剂的应用，以聚乙二醇二丙烯酸酯和苯胺四聚体为原料，在二甲基亚砜相中，在三乙胺的催化作用下，双键和胺基上的氢发生迈克尔加成反应，以得到多臂交联剂。同时本发明的优点在于其制备方法简单，反应条件温和，获得的交联剂具有多臂结构，而且具有导电特性，作为以碳碳双键进行交联反应的交联剂使用，与PEI交联反应成胶。

Description

可导电多臂交联剂的应用
本发明申请是母案申请“一种可导电的多臂交联剂及其制备方法”的分案申请，母案申请的申请号为2016108744470，申请日为2016年10月8日。
技术领域
本发明涉及一种可导电的多臂交联剂及其制备方法，更具体地说，涉及一种PEGDA700-苯胺四聚体的多臂结构交联剂及其制备方法，该交联剂具有多臂结构。
背景技术
苯胺四聚体是苯胺的一种低聚物，由于具有全还原态、半氧化态和全氧化态三种状态，在它们之间的变化过程中会产生电位的变化，使其具有导电性。其次，其环上的胺基具有一定的活性，使其可以作为枝化材料和超支化材料的反应原料之一。聚乙二醇二丙烯酸酯(PEGDA)被广泛地应用于水凝胶的制备中以及载体体系的构建中，由于PEGDA上的双键结构，使其能够很容易地被改性，得到所需的设计结构。同时，还可以通过对PEGDA的分子量大小的控制来调节双键的量，在不同体系中得到很好的应用。
发明内容
本发明旨在克服现有技术的不足，采用迈克尔加成反应，利用聚乙二醇二丙烯酸酯的双键与苯胺四聚体中胺基上的活泼氢，制备得到一种多臂交联剂。
本发明的目的通过下述技术方案得以实现：
一种可导电的多臂交联剂，苯胺四聚体的活泼氢与聚乙二醇二丙烯酸酯的碳碳双键通过迈克尔加成反应键接成一体，按照下述方法进行制备：
将聚乙二醇二丙烯酸酯和苯胺四聚体均匀分散在溶剂中形成反应体系，调节反应体系的pH值为8—10，并升温至80—100摄氏度进行反应。
而且，使用三乙胺作为催化剂，调节反应体系的pH值为8—10，优选8—9。
而且，反应温度为90—100摄氏度，反应时间至少8小时，优选8—14小时，更加优选10—14小时。
而且，在反应过程中采用机械或者超声或者磁力，以使反应体系保持均匀分散的状态。
而且，反应结束后先用去离子水搅拌稀释，然后将其透析处理三天后冻干，最后将冻干后的产物置于-40摄氏度中保存。
而且，相对于苯胺四聚体的活泼氢的物质的量，聚乙二醇二丙烯酸酯的碳碳双键处于过量状态，以使苯胺四聚体的活泼氢与聚乙二醇二丙烯酸酯碳碳双键的反应接近完全。
而且，聚乙二醇二丙烯酸酯和苯胺四聚体的质量比为(20—30)：(1—1.5)。
而且，聚乙二醇二丙烯酸酯的数均分子量为500—5000，优选500—700，或者1000—3000。
本发明以聚乙二醇二丙烯酸酯和苯胺四聚体为原料，在热水浴的条件下，在三乙胺的催化作用下，利用聚乙二醇二丙烯酸酯的碳碳双键和苯胺四聚体中胺基上的氢，发生迈克尔加成反应而制备得到多臂交联剂，即可作为进一步以碳碳双键进行交联反应的交联剂进行使用。本发明制备方法简单，材料来源广泛，生产效率高。
附图说明
图1是本发明制备方法的示意图。
图2是本发明技术方案中苯胺四聚体(曲线1)、PEGDA700-苯胺四聚体交联剂(曲线2)的紫外光谱图谱。
图3是本发明技术方案中苯胺四聚体(曲线1)、PEGDA700-苯胺四聚体交联剂(曲线2)的FT-IR图谱。
图4是本发明制备的可导电多臂交联剂的H1-NMR图谱。
具体实施方式
下面结合具体实施例进一步说明本发明的技术方案。聚乙二醇二丙烯酸酯选择PEGDA700(数均分子量700)，购自上海阿拉丁生化科技股份有限公司；N-苯基对苯二胺，购自上海阿拉丁生化科技股份有限公司；500MHz液体核磁共振谱仪购自Varian INOVA美国；傅里叶变换红外光谱仪购自梅特勒，瑞士；紫外可见分光光度计购自惠普公司。苯胺四聚体(TA)的合成依照参考文献(Wang Q,He W,Huang J,et al.Synthesis of Water Soluble,Biodegradable,and Electroactive Polysaccharide Crosslinker with Aldehyde andCarboxylic Groups for Biomedical Applications[J].Macromolecular Bioscience,2011,11(3):362-72)进行：将六水三氯化铁(2.7g,10mmol)溶解在HCL溶液中(10ml,0.1M)，随后缓慢滴加到N-苯基对苯二胺(2.56g,10mmol)的HCL溶液中(10ml,0.1M)，并在冰浴下搅拌2h.反应结束后，通过离心收集得到滤饼，并用大量0.1M的HCL溶液洗涤滤饼，直至上清液变为无色，再用300ml丙酮洗涤，过滤抽干后再用1M的氨水溶液对其进行掺杂，随后置于苯肼和HCL的混合溶液中处理一段时间，最后抽干，得到的固体置于真空干燥箱48h。
准备实验所需使用的器具，清洗反应所用的小玻璃瓶、旋蒸瓶并置于烘箱中烘干。用同样的方法清洗并烘干两个100mL的烧杯。分别用托盘天平称量1.5g PEGDA700和.0915g苯胺四聚体，再用托盘天平称量3.5g DMSO溶解PEGDA700，称量6g DMSO溶解苯胺四聚体，从而得到质量分数30％的PEGDA700(DMSO)溶液和质量分数1.5％的苯胺四聚体(DMSO)溶液。
设置好水浴锅的温度(100摄氏度)和转速(400rmp)，先往干净烘干的小玻璃瓶中加入配好的PEGDA700(DMSO)溶液，再加入配好的苯胺四聚体(DMSO)溶液，并加入小磁子，同时加入0.5mL三乙胺。然后将小玻璃瓶置于水浴锅中，使其充分搅拌混合均匀，反应10小时。
反应结束后，关闭水浴锅，戴上布手套取出小玻璃瓶，用洁净的卫生纸擦干小玻璃瓶，再打开瓶盖用磁铁吸出小磁子。待反应物冷却后加入20ml去离子水搅拌稀释，随后用塑料过滤器将其过滤，并旋蒸使其体积剩余约10ml。将反应产物倒入干净的截留分子量为4000的透析袋中，放入盛满去离子水的盆中进行透析处理，透析处理时间为三天。透析处理三天后，将产物装入冻干盒中，然后用保鲜膜包好，并将盖在冻干盒上面的保鲜膜上扎满小孔以方便冻干。冻干处理完成后，将冻干产物连同冻干盒一起，置于-40摄氏度中保存备用。
如附图2所示，查阅文献(Huang H,Li W,Wang H,et al.Conducting hydrogelsof tetraaniline-g-poly(vinyl alcohol)in situ reinforced by supramolecularnanofibers.[J].Acs Applied Materials&Interfaces,2014,6(3):1595-600)得知苯胺四聚体在紫外图谱上有两处电活性吸收峰，分别在320nm和600nm处，320nm代表的是苯环上π-π*分子轨道的转变，代表着由还原态向半氧化态的苯胺四聚体转变；600nm代表的是苯环型向醌环型发生的激化子的转变，代表着由半氧化态向全氧化态的苯胺四聚体的转变。同样的，在合成的PEGDA-苯胺四聚体聚合物的紫外图谱上在320nm和600nm处有相同的吸收峰，这表明在苯胺四聚体与PEGDA反应之后依然保持导电性。如附图3所示，查阅文献(Guo B,Finnewistrand A,Albertsson A C.Degradable and Electroactive Hydrogels withTunable Electrical Conductivity and Swelling Behavior[J].Chemistry ofMaterials,2011,23(5):1254-1262)得知苯胺四聚体的特征吸收峰分别在1510cm-1(苯环型中νC＝C伸缩振动，s,-N-B-N-)、1596cm-1(醌环型中νC＝C伸缩振动，s,-N＝Q＝N-)、1307cm-1(芳香胺中νC-N伸缩振动)，由此说明苯胺四聚体的成功合成。此外，在PEGDA-TA的红外图谱中，在3380cm-1活泼氢的消失以及在3425cm-1处PEGDA的特征峰，表明PEGDA-TA的成功合成。再以核磁共振进行产物的表征，如附图4所示，苯胺四聚体分子上的氢的化学位移约在5.5ppm、6.5ppm与07.0ppm附近，在本发明多臂交联剂的制备过程中，苯胺四聚体的氢参与了反应，因此制备得到的多臂交联剂的核磁共振氢谱图中应该没有密胺分子上原先存在的氢的化学位移，再加上双键上的氢5.9ppm和6.2ppm等处的化学位移与结构式中的氢成功对应，从而证明了PEGDA700分子成功接枝到苯胺四聚体分子上。
在上述实施例中PEGDA过量，以使交联剂中活拨氢参与反应，末端均为碳碳双键，除去红外和核磁表征外，以制备的交联剂中碳碳双键为官能集团进行交联，制备的交联剂整体外观为深色粘稠液体(颜色与聚苯胺颜色接近)，交联后整体为胶状：(1)以AIBN热引发：将产物溶于DMSO中配置质量百分含量20％的聚合物溶液，AIBN的量取产物固含量的5％，80摄氏度下30min后成胶(或者光引发剂)；(2)与PEI交联反应：将数均分子量为1800的PEI溶于DMSO，配置质量百分数为20％的溶液，所制备的产物PEG-TA也配置为质量百分数为20％的溶液。两者按照体积比1:1混合，1min中内成胶。
依照发明内容记载的工艺参数和组分含量进行调整，均可制备多臂交联剂并表现出与实施例基本一致的性质。以上对本发明做了示例性的描述，应该说明的是，在不脱离本发明的核心的情况下，任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。

Claims (8)

1.可导电多臂交联剂的应用，其特征在于，苯胺四聚体的活泼氢与聚乙二醇二丙烯酸酯的碳碳双键通过迈克尔加成反应键接成一体，形成可导电多臂交联剂，以碳碳双键进行交联反应。
2.根据权利要求1所述的可导电多臂交联剂的应用，其特征在于，可导电多臂交联剂按照下述方法进行制备：将聚乙二醇二丙烯酸酯和苯胺四聚体均匀分散在溶剂中形成反应体系，调节反应体系的pH值为8—10，并升温至80—100摄氏度进行反应，相对于苯胺四聚体的活泼氢的物质的量，聚乙二醇二丙烯酸酯的碳碳双键处于过量状态，以使苯胺四聚体的活泼氢与聚乙二醇二丙烯酸酯碳碳双键的反应接近完全。
3.根据权利要求2所述的可导电多臂交联剂的应用，其特征在于，聚乙二醇二丙烯酸酯和苯胺四聚体的质量比为(20—30)：(1—1.5)。
4.根据权利要求2所述的可导电多臂交联剂的应用，其特征在于，聚乙二醇二丙烯酸酯的数均分子量为500—5000。
5.根据权利要求2所述的可导电多臂交联剂的应用，其特征在于，聚乙二醇二丙烯酸酯的数均分子量为500—700，或者1000—3000。
6.根据权利要求2所述的可导电多臂交联剂的应用，其特征在于，使用三乙胺作为催化剂，反应时间至少8小时。
7.根据权利要求2所述的可导电多臂交联剂的应用，其特征在于，使用三乙胺作为催化剂，反应时间为8—14小时。
8.根据权利要求1或者2所述的可导电多臂交联剂的应用，其特征在于，以碳碳双键进行交联反应时，以引发剂引发双键进行交联，引发剂为热引发剂或者光引发剂。
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