Investigation of the Conditions for the Synthesis of Poly(3,4-ethylenedioxythiophene) ATRP Macroinitiator

One of the most widely used conductive polymers in the growing conductive polymer industry is poly(3,4-ethylenedioxythiophene) (PEDOT), whose main advantages are good thermal and chemical stability, a conjugated backbone, and ease of functionalization. The main drawback of PEDOT for use as wearable electronics is the lack of stretchable and self-healing properties. This can be overcome by grafting PEDOT with flexible side branches. As pure PEDOT is highly stable and grafting would not be possible, a new bromine-functionalized thiophene derivative, 2-(tiophen-3-yl) ethyl 2-bromo-2-methylpropanoate (ThBr), was synthesized and copolymerized with EDOT for the synthesis of a poly(EDOT-co-ThBr) ATRP macroinitiator. After the synthesis of the macroinitiator, flexible polymers could be introduced as side branches by atom-transfer radical polymerization (ATRP) to modify mechanical properties. Before this last synthesis step, the conditions for the synthesis of the ATRP macroinitiator should be investigated, as only functionalized units can function as grafting sites. In this study, nine new copolymers with different monomer ratios were synthesized to investigate the reactivity of each monomer. The ratios used in the different syntheses were ThBr:EDOT = 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1, 0.8:1, 0.6:1, 0.4:1, and 0.2:1. In order to determine the effect of reaction time on the final properties of the polymer, macroinitiator synthesis at a 1:1 ratio was carried out at different time periods: 8 h, 16 h, 24 h, and 48 h. The obtained products were characterized by different techniques, and it was found that polymerizations longer than 24 h yielded practically insoluble macroinitiators, thus limiting its further application. Reactivity ratios of both monomers were found to be similar and close to 1, making the copolymerization reaction symmetrical and the obtained macroinitiators almost random copolymers.