Ab initio emulsion RAFT polymerization of vinylidene chloride mediated by amphiphilic macro‐RAFT agents

Abstract

An amphiphilic copolymer poly(acrylic acid)‐block‐poly(styrene) (PAA‐b‐PS) with a trithiocarbonate reactive group was used in the ab initio reversible addition‐fragmentation chain transfer (RAFT) emulsion polymerization of vinylidene chloride (VDC). The fast polymerization and high conversion were achieved. The parameters for a good control over the formation of well‐defined PAA‐b‐PS‐b‐PVDC amphiphilic block copolymers and self‐stabilized latexes were identified. To improve the emulsion stability and prevent the desorption of water‐soluble initiating radicals, the acid groups of PAA‐b‐PS were neutralized by NaOH at the later stage of polymerization. The PAA‐b‐PS‐b‐PVDC block copolymer with a high molar mass of 30 kg mol−1 and the stable latex with 30 wt % solid content was obtained. The kinetics of RAFT emulsion copolymerization of VDC in a living manner was first investigated. The as‐prepared PAA‐b‐PS‐b‐PVDC latex particles were further used as seeds in the emulsion polymerization of styrene, enabling the preparation of novel PAA‐b‐PS‐b‐PVDC‐b‐PS tetra‐block copolymers with a molar mass of 76 kg mol−1 and a relatively low molecular weight distribution of 1.6. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40391.

In situsynthesis of ABA triblock copolymer nanoparticles by seeded RAFT polymerization: Effect of the chain length of the third a block on the triblock copolymer morphology

“…This PISA strategy ensures good colloidal stability, and it produces nano‐objects with well‐defined morphologies including spheres, worms, and vesicles. Recently, the seeded RAFT polymerization based on the pre‐prepared block copolymer nano‐objects has been demonstrated to be a valid method to modify and/or prepare block copolymer nano‐objects . Following this seeded RAFT polymerization, a new block is introduced into the pre‐prepared diblock copolymer nano‐objects just as similarly as those in the graft‐through strategy to afford triblock copolymer nano‐objects.…”

Block copolymer synthesis by controlled/living radical polymerisation in heterogeneous systems

“…Arguably the most promising modification of ab initio CLRP is the use of a macroCTA or macroinitiator that also functions as a surfactant, which typically enables simultaneous control over the polymerisation and colloidal stability, and as such the strategy is now commonplace. [107][108][109]111,112,114,117,133 In RAFT, using an amphiphilic macro-RAFT agent immediately localises the CTA at the polymerisation loci, i.e. within micelles.…”