导电聚合物插层LDHs的组装及其性能研究
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摘要
本文依据插层组装理论，以层状双氢氧化物(Layered double hydroxides,LDHs)为主体，3-磺酸基苯胺(ANIS)和3-羧基噻吩(THC)两种可溶性导电聚合物单体为客体，采用原位聚合技术合成了聚磺酸基苯胺(PANIS)插层LDHs、聚羧基噻吩(PTHC)插层LDHs。对插层LDHs的超分子结构、聚合物单体在LDHs限域空间内的聚合机理、LDHs主体在层间聚合反应中的作用及其影响规律进行了系统而深入地研究，并探讨了此类插层材料在光、电、催化领域及制备导电聚合物齐聚物等方面的潜在应用前景。
采用XRD、FT-IR、UV-vis、TG-DTA-MS、in situ HT-XRD、MAS NMR及XPS等表征方法，建立了两种导电聚合物单体插层LDHs的超分子结构模型。ANIS插层LDHs的层间客体以双层交错式的定位方式排列于主体层板间，层间空隙由交换前体中的硝酸根和水分子填充，形成稳定的超分子结构。THC插层LDHs的层间客体以双层排列方式定位于主体层间，水分子位于层间空隙，形成稳定的超分子结构。
用外加氧化剂法成功实现了ANIS单体在LDHs层间的可控聚合。氧化剂中过硫酸根离子通过置换共插层的硝酸根离子进入LDHs层间，氧化层间单体聚合。层间单体的聚合方式为1和4位的首尾聚合。聚合产物氧化度与质子化率随氧化剂加入量的增加而升高。
Based on the conception of intercalation chemistry, polyaniline sulfonic (PANIS)-intercalated LDHs and polythiophene-3-carboxylie
(PTHC)-intercalated LDHs have been successfully synthesized by using in situ polymerization technique. The supramolecular structure, the mechanism for the interlayer polymerization as well as the relationship between the host (LDHs) and guest (polymeric monomers or polymers) in each interlayer polymerization have been systematically investigated. The results suggest potential applications of these intercalated materials in the fields of photochromic materials, electrochemistry and catalysis. The polymerization of polymeric monomers in the restricted environment between LDHs sheets opens new opportunities for further research in chemical reactions in inorganic hybrids at the nanoscale and for their use in preparation of conductive oligomers.
Characterizations by the use of XRD, FT-IR, UV-vis, TEM, TG-DTA-MS, in situ HT-XRD and XPS techniques confirm the supramolecular structure of
采用XRD、FT-IR、UV-vis、TG-DTA-MS、in situ HT-XRD、MAS NMR及XPS等表征方法，建立了两种导电聚合物单体插层LDHs的超分子结构模型。ANIS插层LDHs的层间客体以双层交错式的定位方式排列于主体层板间，层间空隙由交换前体中的硝酸根和水分子填充，形成稳定的超分子结构。THC插层LDHs的层间客体以双层排列方式定位于主体层间，水分子位于层间空隙，形成稳定的超分子结构。
用外加氧化剂法成功实现了ANIS单体在LDHs层间的可控聚合。氧化剂中过硫酸根离子通过置换共插层的硝酸根离子进入LDHs层间，氧化层间单体聚合。层间单体的聚合方式为1和4位的首尾聚合。聚合产物氧化度与质子化率随氧化剂加入量的增加而升高。
Based on the conception of intercalation chemistry, polyaniline sulfonic (PANIS)-intercalated LDHs and polythiophene-3-carboxylie
(PTHC)-intercalated LDHs have been successfully synthesized by using in situ polymerization technique. The supramolecular structure, the mechanism for the interlayer polymerization as well as the relationship between the host (LDHs) and guest (polymeric monomers or polymers) in each interlayer polymerization have been systematically investigated. The results suggest potential applications of these intercalated materials in the fields of photochromic materials, electrochemistry and catalysis. The polymerization of polymeric monomers in the restricted environment between LDHs sheets opens new opportunities for further research in chemical reactions in inorganic hybrids at the nanoscale and for their use in preparation of conductive oligomers.
Characterizations by the use of XRD, FT-IR, UV-vis, TEM, TG-DTA-MS, in situ HT-XRD and XPS techniques confirm the supramolecular structure of
引文
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