Synthesis of Poly(3-vinylpyridine)-Block-Polystyrene Diblock Copolymers via Surfactant-Free RAFT Emulsion Polymerization

Abstract

In this work, we present a novel synthetic route to diblock copolymers based on styrene and 3-vinylpyridine monomers. Surfactant-free water-based reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization of styrene in the presence of the macroRAFT agent poly(3-vinylpyridine) (P3VP) is used to synthesize diblock copolymers with molecular weights of around 60 kDa. The proposed mechanism for the poly(3-vinylpyridine)-block-poly(styrene) (P3VP-b-PS) synthesis is the polymerization-induced self-assembly (PISA) which involves the in situ formation of well-defined micellar nanoscale objects consisting of a PS core and a stabilizing P3VP macroRAFT agent corona. The presented approach shows a well-controlled RAFT polymerization, allowing for the synthesis of diblock copolymers with high monomer conversion. The obtained diblock copolymers display microphase-separated structures according to their composition.

Well-defined polyvinylpyridine-block-polystyrene diblock copolymers via RAFT aqueous-alcoholic dispersion polymerization: synthesis and isoporous thin film morphology

“…16,17 These methods provide efficient heat transfer, low viscosity during the entire reaction time and enable the production of well-defined polymers. 14,[16][17][18] Dispersion polymerization initially involves a completely homogeneous solution. [19][20][21][22] However, the resultant polymer is not soluble in the polymerization medium.…”

“…47,51,56,57 A convenient approach to synthesize medium molecular weight poly(3-vinylpyridine)-b-polystyrene via RAFT emulsion polymerization and their thin film morphology were presented before. 18 In the present study, poly(4-vinylpyridine) (P4VP) and poly(2-vinylpyridine) (P2VP) were employed as macroRAFT agents. Here, a two-step synthetic route to poly(4-vinylpyridine)-b-polystyrene and poly(2-vinylpyridine)-b-polystyrene is described via a RAFT aqueous-alcoholic dispersion polymerization, which takes advantage of the PISA approach.…”

Acidity effects of medium fluids on anhydrous proton conductivity of acid-swollen block polymer electrolyte membranes

“…S-P-S was synthesized by mixing the macro-RAFT agent, AIBN, and a 4vinylpyridine monomer (Sigma-Aldrich) and the mixture was heated at 80 C for 1.5 hours, where the 4-vinylpyridine monomers were inserted next to the sulfur atoms of trithiocarbonate unit in the precursor S. 68,69 See also details of synthesis of a similar block copolymer by RAFT polymerizations in the previous literature. 67,71- 73 1 H NMR spectroscopy by an Ascend 500 MHz (Bruker Corp.)…”

Polymerizations by RAFT: Developments of the Technique and Its Application in the Synthesis of Tailored (Co)polymers

“…After annealing at different temperatures, the thin films displayed interesting microphase‐separated structures according to their composition and annealing temperature. [ 113 ]…”