Synthesis of Blockcopolymers P3HT‐b‐PS Using a Combination of Grignard‐Metathesis and Nitroxide‐Mediated Radical Polymerization

Abstract

The synthesis of π‐conjugated NMRP‐macroinitiators using GRIGNARD‐metathesis polymerization in combination with azide/alkyne‐“click” chemistry has been investigated. Alkoxyamine‐functionalized poly(3‐hexylthiophene)s (P3HTs) have been used for block copolymer preparations in presence of styrene. Molecular weight and molecular weight distribution of the polymers have been determined in SEC‐measurements, while end‐group determination was performed with MALDI‐ToF‐MS. The molecular weight of the P3HT macroinitiators was influenced by the amount of Ni‐catalyst during the GRIM reaction. Those macroinitiators have been used to prepare block copolymers in subsequent nitroxide‐mediated radical polymerization (NMRP). Thin‐layer‐morphologies of the block copolymers were investigated using tapping‐mode AFM. Short and disordered rods were observed, as well as continuous and parallel fibrils. magnified image

Grignard metathesis (GRIM) polymerization for the synthesis of conjugated block copolymers containing regioregular poly(3-hexylthiophene)

“…Coil-like polystyrene, poly(methyl acrylate), poly(methyl methacrylate), poly(t-butyl acrylate), poly(t-butyl methacrylate), poly(isobornyl methacrylate), poly(2-(dimethylamino)ethyl methacrylate), poly(fluorooctyl methacrylate), poly(4-vinylpyridine), and polyisoprene were incorporated into diblock copolymer structures with P3HT. [24][25][26][27][28][29][30][31] The synthesized block copolymers display nanofibrillar morphology similar to that observed for the P3HT homopolymer. A P3HT diblock copolymer containing C 60 was reported by Jo.…”

Synthesis of Polyphthalaldehyde-Based Block Copolymers: Utilization of a Thermo-Sacrificial Segment for an Easy Access to Fine-Tuned Poly(3-hexylthiophene) Nanostructured Films

“…In organic electronics, the control over the materials morphology at the nanoscale has a huge interest to improve the electronic device performances, in particular for charge transport in field-effect transistors and for charge separation and transport in photovoltaic cells. − Rod–coil block copolymers containing one semiconducting segment, e.g., poly­(3-hexylthiophene) (P3HT), contribute to that issue by their tendency to nanophase separation upon self-assembly. Such copolymers have been used to produce nanofibrillar morphologies where the width of nanofibrils can be controlled by the length of the P3HT rod segment, the composition of the block copolymer, and the processing conditions. − To date a large number of active layers based on rod–coil and coil–rod–coil block copolymers containing P3HT as the “rod-like” segment have been reported. − As “coil-like” segments, poly­(urethane), poly­(styrene), − poly­(isoprene), poly­(methacrylate), , poly­(methyl acrylate), poly­(butyl acrylate), poly­(methyl methacrylate), poly­(acrylic acid), poly­(ε-caprolactone), poly­(2-(dimethylamino)­ethyl methacrylate), , poly­(4-vinylpyridine), poly­(2-vinylpyridine), poly­(ethylene glycol), , poly­(ethylene), poly­( p -styrenesulfonate), and stereocomplexed poly­(lactide) have been used. The presence of the nonconjugated block can have a strong influence on the crystallinity of the materials and allows for the formation of specific morphologies.…”

Alkyne–azide coupling of tailored poly(vinylidene fluoride) and polystyrene for the synthesis of block copolymers

“…Starting from different alkoxyamines like 2,2,5-trimethyl-3-(1 0 -(p-chloro-methyl)-phenylethoxy)-4-phenyl-3-azahexane (BnClTIPNO) 27,28 functionalization of alkoxyamines can be carried out to introduce azide-, hydroxy-, amine-, carboxylic acid-, ether-, thiol-, disulfide-or carbamate groups. [29][30][31][32] NMRP initiators with an alkyne group have also been prepared and investigated related to their polymerization behavior. Narrow molecular weight distributions as well as first order kinetics confirmed the controlled manner of the polymerization.…”