Conducting graft copolymers of pyrrole and thiophene with random copolymers of methyl methacrylate and 3-methylthienyl methacrylate

doi:10.1016/j.eurpolymj.2004.03.029

European Polymer Journal

Volume 40, Issue 8, August 2004, Pages 1799-1806

https://doi.org/10.1016/j.eurpolymj.2004.03.029 Get rights and content

Abstract

Random copolymers of 3-methyl thienylmethacrylate and methyl methacrylate were synthesized via free radical polymerization. Electro-copolymerizations of random copolymers with thiophene and/or pyrrole were carried out in acetonitrile–tetrabutylammonium tetrafluoroborate (TBAFB), water–p-toluene sulfonic acid (PTSA) solvent–electrolyte couples. Oxidative polymerization of thiophene functionalized random copolymer was also achieved by constant current electrolysis and chemical polymerization. The characterizations were done by conductivity measurements, cyclic voltammetry (CV), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetry analysis (TGA), scanning electron microscopy (SEM).

Introduction

Conducting polymers (CPs) are an exciting new class of electronic materials, which have attracted rapidly increasing interest since Shirakawa's report in 1977 [1]. CPs are beginning to find applications in the fields of battery materials [2], electrochromic devices [3], [4], electromagnetic shielding [5], sensor technology [6], non-linear optics [7], molecular electronics [8] and enzyme immobilization matrices [9], [10] since they have combined properties of metals and polymers. Many unsubstituted conducting polymer systems have limited solubility and are intractable and infusible. This is due to the rigid rod nature of CPs, arising from their extended-delocalization. In order to make the polymer soluble, fusible and processable, polythiophene substitution at three and/or four position was achieved by various groups [11], [12]. Synthesis of conducting polymer composites, graft and block copolymers were shown to be effective ways to compensate for the certain deficiencies of conducting polymers like poor mechanical and physical properties. Electropolymerization of the conducting component on an electrode previously coated with the insulating polymer is one of the most widely used method for that purpose [13], [14], [15].

Recently, conducting copolymers of thiophene functionalized methyl methacrylate with thiophene and/or pyrrole have been utilized [16], [17]. In this work, syntheses of random copolymers (RC) of 3-methylthienyl methacrylate (MTM) and methyl methacrylate (MMA) were achieved by free-radical polymerization with the use of azobisisobutyronitrile (AIBN) as the initiator. Conducting graft copolymerization of random copolymers with thiophene and/or pyrrole was achieved by constant potential electrolysis. The grafting process was elucidated with conductivity measurements, cyclic voltammetry, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermal gravimetry analysis, scanning electron microscopy studies.

Section snippets

Materials

The monomers, pyrrole (Py) (Aldrich), thiophene (Th) (Sigma), methyl methacrylate (MMA) (Aldrich), dimethyl formamide (Aldrich) and methacryloyl chloride (Aldrich) were purified by conventional distillation procedures prior to use. 2,2-Azobisisobutyronitrile (AIBN) (Aldrich) was recrystallized from ethanol. The electrolysis solvents, acetonitrile (AN) (Merck), and dichloromethane (Merck) were used without further purification. The supporting electrolytes, p-toluene sulfonic acid (PTSA) (Sigma)

Synthesis of random copolymers 3-methylthienyl methacrylate and methyl methacrylate

MTM and MMA of random copolymers of three different compositions were polymerized by free radical bulk polymerization in the presence of AIBN as the initiator (Scheme 1).The results of the polymerization are presented in Table 1 (RC1, RC2, and RC3).

Cyclic voltammetry

CV experiments were carried out in an ACN–TBAFB system under N₂ atmosphere by a Bank Pos2 potentiostat/galvanostat. Fig. 1 depicts the redox behavior of pyrrole, thiophene, and RC1 in the presence of thiophene and pyrrole. In the cyclic voltammogram

Conclusions

Random copolymers of methyl methacrylate and 3-methylthienyl methacrylate were successfully synthesized by free radical polymerization with AIBN as the initiator. Graft copolymers of RC with polypyrrole were further synthesized by two different electrochemical methods. Constant potential electrolyses (CPE) were carried out in ACN–TBAFB and water–PTSA solvent–electrolyte couples, with 1.1 V at room temperature. Graft copolymers of RC were also synthesized with polythiophene in the presence of

Acknowledgements

This work was supported by DPT2003K120920-02, METU BAP-2003-01-03-02, Istanbul Technical University Research Fund and Turkish Academy of Sciences (TUBA).

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Conducting graft copolymers of pyrrole and thiophene with random copolymers of methyl methacrylate and 3-methylthienyl methacrylate

Abstract

Introduction

Section snippets

Materials

Synthesis of random copolymers 3-methylthienyl methacrylate and methyl methacrylate

Cyclic voltammetry

Conclusions

Acknowledgements

Electrochim. Acta

Bioelectrochemistry

Synth. Met.

Synthesis of electrically conducting organic polymers––halogen derivatives of polyacetylene, (CH)X

J. Chem. Soc. Chem. Commun.

J. Chem. Soc. Chem. Commun.

Chem. Mater.

Polyheterocyclic conducting polymers and composites derivatives

Synth. Met.

J. Chem. Soc. Chem. Commun.