Herein, a simple synthetic method to functionalize norbornene at the 5-position with a base-stable tetraaminophosphonium cation was developed. Upon confirmation that the cationic monomer could be polymerized in a living fashion, statistical and diblock copolymers were synthesized with norbornene as a comonomer. After hydrogenation, the statistical copolymers were effective anion-exchange materials, while the diblock did not produce a free-standing film. Differential scanning calorimetry and atomic force microscopy indicated that crystallinity was mostly suppressed by the bulky phosphonium cations in the statistical copolymers, with the impact somewhat dependent on the amino groups bound to the phosphorus atom. Small-angle X-ray scattering profiles revealed a two-phase morphology with 3 nm domains arising from ion clustering in the film. Altogether, the study revealed the large impact these novel phosphonium cations have on polymer organization and packing, which is a critical consideration when targeting larger delocalized cations in anion-transport materials.

Semiconducting polythiophenes display electroactive properties which make them excellent candidates for applications as electroactive materials. Ability to undergo doping and to switch between different oxidation states allow tuning the chemical and physical properties of polythiophenes. Furthermore, the ability to integrate polythiophenes into copolymers, hybrid composites with metals and inorganic materials make them useful in electronic and biomedical applications. The capability to vary the properties of the final material with low production cost and high processability into thin films makes polythiophenes desirable materials for many applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3327–3346

A liquid crystalline diblock copolymer P3HT-b-PHIC was synthesized and investigated.

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A 250 mL three neck flask with stir bar was flushed with nitrogen for 5 minutes.Tetrahydrofuran (THF) (10 mL) and 2, 5-dibromo-3-hexylthiophene (1.63 g, 5.0 mmol) were injected into the flask via syringe. t-Butylmagnesium chloride (2.5 mL, 5.0 mmol) was added into the reaction mixture and stirred for 90 minutes. Samples from the reaction mixture were taken and analyzed with GC-MS to monitor the monomer conversion. Catalyst, Ni(dppp)Cl 2 (0.04 g) (0.07 mmol) was added into the reaction mixture and stirred for 8 minutes followed by injection of allyl magnesium bromide (3 mL), (3.0 mmol) into the reaction mixture. The polymer was quenched in methanol and purified by the Soxhlet extraction with methanol,