A Novel Poly(vinylidene fluoride)-Based 4-Miktoarm Star Terpolymer: Synthesis and Self-Assembly

Abstract

A well-defined amphiphilic miktoarm polymer incorporating poly(vinylidene fluoride) (PVDF), polystyrene (PS), and poly(ethylene glycol) (PEG) blocks was synthesized via a combination of atom-transfer radical polymerization (ATRP), iodine transfer radical polymerization (ITP), and copper-catalyzed azide-alkyne cycloaddition (CuAAC). Morphology and self-assembly of this star polymer were examined in organic solvents and in water. The aggregates formed in water were found to possess unusual frustrated topology due to immiscibility of PS and PVDF. The polymer was evaluated for transport of small hydrophobic molecules in water.

“One-pot” aminolysis/thia-Michael addition preparation of well-defined amphiphilic PVDF-b-PEG-b-PVDF triblock copolymers: self-assembly behaviour in mixed solvents

“…39 Rodionov et al prepared interesting 4miktoarm star copolymers containing 2 PVDF-b-PS arms and 2 PEG arms via the combination of ATRP, Iodine Transfer Polymerization (ITP) and copper-catalyzed azide-alkyne cycloaddition (CuAAC); and studied their self-assembly in organic solvents and water. 40 Over the last two years we developed the RAFT polymerization of VDF, 41 and prepared some PVDF-containing block copolymers, 42 which selfassembled in water and organic solvents. PVDF-b-PVA (PVA = poly(vinyl alcohol)) formed spherical particles in water, 43 PVDF-b-PDMAEMA (PDMAEMA = poly (2-dimethylaminoethyl methacrylate) in water displayed spherical aggregates and rigid rods which are thought to be generated via crystallisation-driven self-assembly; 44 and PVAc-b-PVDF (PVAc = poly(vinyl acetate)) readily self-assembled in dimethyl carbonate under polymerization-induced self-assembly conditions into highly crystalline micrometric structures.…”

Miktoarm Star Polymers: Branched Architectures in Drug Delivery

“…Rather than assembling a structure defined by fractional hydrophilicity, (AB) 2 C 2 (A = PS, B = poly(vinylidene fluoride) (PVDF), C = PEG) miktoarm stars were observed to self-assemble into 99 nm micelles in aqueous solution with distinct wrinkled cores [ 69 ]. PVDF in the micellar inner core blocks had both lipo-philicity and -phobicity.…”

Iodine‐transfer polymerization and CuAAC “click” chemistry: A versatile approach toward poly(vinylidene fluoride)‐based amphiphilic triblock terpolymers

“…PEO-alkyne was synthesized following the procedure reported in the literature. 21 PEO monomethyl ether (Mn = 5000, 30.0 g, 6.0 mmol) was dissolved in dioxane (600 mL) and gentle heating was applied to completely dissolve the polymer. Boron trifluoride diethyl etherate (0.17 g, 1.19 mmol, 0.15 mL) was added to the solution.…”

“…14,[18][19][20] Until now, the number of reports on PVDF-based BCPs is limited. Three main strategies involving degenerative chain transfer such as macromolecular design via the interchange of xanthates, reversible addition-fragmentation chain-transfer polymerization, 4,[21][22][23][24][25] and iodine-transfer radical polymerization (ITP) [26][27][28][29][30][31] have been applied for the synthesis of PVDF BCPs. ITP is the most robust technique to synthesize PVDF-based BCPs with tunable iodine chain-end functionality that can provide easy access to incorporate an additional block.…”

“…The vital steps of this methodology are the synthesis of azideterminated PVDF BCPs and alkyne-terminated hydrophilic polymer, which are subsequently used for "click" reaction. We first prepared PVDF-b-PS-I diblock copolymers via ITP (Scheme 1) and converted into PVDF-b-PS-N 3 by reaction with sodium azide 18,21 and then "clicked" with alkyne-terminated PEO to produce amphiphilic PVDF-b-PS-b-PEO triblock terpolymers (Scheme 1). Furthermore, the self-assemblies in films and organic solvents or water, the thermal properties, the crystalline phases of PVDF, and the carrier ability of the terpolymers were reported.…”