Crystalline−Crystalline Block Copolymers of Regioregular Poly(3-hexylthiophene) and Polyethylene by Ring-Opening Metathesis Polymerization

Abstract

Block copolymers of regioregular poly(3-hexylthiophene) (P3HT) and polyethylene (PE) were synthesized through the chain transfer of olefin-terminated P3HT in the presence of cyclooctene via ring-opening metathesis polymerization (ROMP). Subsequent hydrogenation of the poly(cyclooctene) block yielded high molecular weight, crystalline-crystalline P3HT-PE block copolymers, which are thermally stable and resistant to solvents under ambient conditions. These copolymers were characterized by 1H NMR, DSC, and WAXS and represent the first materials of a class of crystalline-crystalline semiconducting-insulating block copolymers.

Structure and morphology control in thin films of regioregular poly(3‐hexylthiophene)

“…[92][93][94][95] Correlations between the molecular structure of the monomeric units made of several chemical moities and the crystalline packing in the unit cells (especially the p-p-stacking) need still to be established. In this perspective, P3HT is certainly a case system to test the applicability of experimental methods and insights gained when investigating conventional polymer crystallization, for example, using epitaxial crystallization methods, self-seeding or nucleating agents.…”

Ring closing metathesis employing organometallic substrates and the templated synthesis of macrocycles

“…Removal of the solvent and further reaction generates an insoluble solid, which is presumably the ROMP polymer product 30, of which there may be a number of isomers [95]. Similar Lewis base containing poly(thiophene)-polyethylene block co-polymers, synthesized by metathesis, have recently been reported [104]. Attempts to perform the same reaction with the Schrock catalyst 3 under the same conditions (5 mol%) showed no reaction with either 18a or 24a over 16 h; raising the concentration of catalyst to 20 mol% results in 67% RCM with 18a with 20% starting material, 13% of an unidentified species ( 1 H NMR) and, in line with most previous studies, no olefin isomerization products.…”

Moderate doping leads to high performance of semiconductor/insulator polymer blend transistors

“…However, for a widespread application of these devices, air stability and material costs are important features that need to be improved. Blends of semiconducting and insulating polymers have recently been shown to exhibit reasonably high mobilities and on/off ratios [21][22][23][24][25][26][27][28] , often exceeding the corresponding values measured for pure layers of the semiconducting polymers. As high performance could be realized even for a low concentration of the active semiconductor component mixed into an inert polymer matrix, these blends allow a fine tuning of the active layer's rheological and optical properties without compromising charge transport.…”