Four polythiophenes based on poly(3,4-ethylenedioxythiophene) (PEDOT) framework have been successfully prepared by the facile thermal activated solid-state polymerization (SSP) process from their corresponding dibromothiophene derivatives, which were efficiently obtained using our improved methodology. Rates of polymerizations of these precursors were varied and most of the processes were incomplete under the reaction condition chosen for the synthesis. Raising the reaction temperature of the SSP further advanced the polymerization progress and improved the conductive properties of the polymer. The polymer of 3,4-ethylenedioxythiophene-methanol (EDTM) and its two related derivatives with functionalizable groups were prepared for the first time by the SSP method. The process and these new SSP-derived polymers could help solving the fabrication difficulty and expand the scope of their applications.
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