Study on the formation of a supramolecular conjugated graft copolymer in solution

Abstract

The formation in solution of a supramolecular graft copolymer bearing conjugated blocks is demonstrated using diffusion ordered NMR spectroscopy (DOSY). A tailor-made poly(3-(2-ethylhexyl)thiophene) (P3EHT) with a phenol end group is synthesized. For this purpose, the chain-growth mechanism of the polymerization of 2-bromo-5-chloromagnesio-3-alkylthiophenes in the presence of a Ni(dppp) catalyst (dppp 5 1,3-bis(triphenylphosphino)propane) is exploited, as it enables the use of functionalized initiators to introduce specific end groups. The soobtained polythiophene was subsequently mixed in solution with poly(4-vinylpyridine) (P4VP) to enable phenol-pyridine hydrogen bonding. The formation of the supramolecular graft copolymer is studied using DOSY-measurements. Based on the results thereof, the amount of P3EHT attached to the P4VP is calculated and the association constant of the hydrogen bond is estimated. V C 2013

P4VP and oligo(phenylenevinylene)-perylenebisimide mixed donor-acceptor supramolecular comb polymer complexes with improved charge carrier mobility

“…Introduction of OPVCN‐OH into the P4VP‐UPBI complex resulted in reduction of average bulk electron mobility estimate to ∼ 10 − cm 2 V −1 s −1 in P4VP(OPV 0.25 + UPBI 0.75 ) and P4VP(OPV 0.50 + UPBI 0.50 ) . P4VP(OPV 0.75 + UPBI 0.25 ) exhibited average electron mobilities of 3.7 x 10 − cm 2 V −1 s −1 . It should be mentioned here that the complexes with higher OPV content exhibited poor film forming ability.…”

“…Noncovalent interactions like the hydrogen bonding and ionic interactions have been used to develop “bottle‐brush” polymeric structures between linear polymers and small surfactant molecules . Poly(4‐vinyl pyridine) (P4VP) is the most widely studied polymer that has been explored for the hydrogen bonding interactions of the pyridine nitrogen with aromatic hydroxyl or carboxyl units of small surfactant molecules . Most of these studies focused on the self‐organization in the bulk state .…”

Advances in the controlled polymerization of conjugated polymers

“…Initiators 3 to 13 were successfully used for the controlled synthesis of P3AT. 31,[43][44][45][46][47][48][49] In addition to the synthesis of P3AT, initiator 3 was also used for the synthesis of poly(3-alkoxythiophene) (P3AOT), although this was not controlled due to the intrinsic character of the alkoxythiophene monomer (see 2.2.1.…”

DOSY NMR as a tool for predicting optimal conditions for hydrogel formation: The case of a hyperbranched polyglycidol cross-linked with boronic acids

“…In polymer research, DOSY NMR has applications in the determination of the distribution and molecular weight of polymers . The technique focuses on supramolecular polymer formation and supramolecular complexes, such as graft copolymers or micelles from triblock copolymers . The gelation processes have been investigated by Nonappa et al for low molecular weight compounds in organic solvents …”