Title

A precursor approach to the synthesis and fabrication of conducting polymers

Date of Completion

January 2010

Keywords

Chemistry, Polymer|Nanoscience

Degree

Ph.D.

Abstract

Poly(terthiophene) nanostructures consisting of periodic nanolines were prepared using the precursor polymer approach in conjunction with nanoimprint lithography. Precursor poly(norbornylene)s consisting of terthiophene side chains were prepared from their corresponding norbornylene monomers via ring opening metathesis polymerization. A copolymer consisting of terthiophene norbornylene and acetate norbornylene repeat units with a 50:50 composition exhibited a glass transition temperature of 52°C. Nanolines of percursor polynorbornylene were prepared by thermal nanoimprint lithography. The nanoimprinted precursor polymer was then converted to conjugated conductive polymer via chemical and electrochemical oxidation of the terthiophene side units. Nanoimprinted lines of conductive poly(terthiophene) exhibited high electrochromic contrast at 437 nm. Poly(arylenesilylene)s showed the promising aspects as a precursor polymer to form conducting polymers via oxidative electrochemical or chemical desilylation. Poly(arylenesilylene)s can be prepared in one pot reaction and their physical properties can be tuned by introducing different silane derivatives. Poly[(2,2'-bithienylene)dimethylsilylene] was prepared by coupling reaction between dilithiated 2,2'-bithiophene and dichlorodimethylsilane. Conversion of the precursor polymer to poly(bithiophene) was carried out via solid state electrochemical oxidation and confirmed by optical and electrochemical analyses. As a demonstration, poly[(2,2'-bithienylene)dimethylsilylene] was melt drawn into a fiber and converted to the poly(bithiophene) via solid state oxidative electrochemical conversion. Solution processable poly(arylenesilylene)s were prepared by introducing silanes having longer alkyl groups than methyl groups. Nanofibers of precursor polymers were obtained from precursor polymer solutions via electrospinning. The formation of poly(bithiophene) fibers via the solid-state oxidative conversion of electrospun precursor poly(bithienylenesilylene) nanofibers was confirmed electrochemically. The conductive polymer nanofiber mat obtained from the precursor polymer showed the similar electrochromic functionality to that of poly(bithiophene). ^