Surfactant-Free Controlled/Living Radical Emulsion (Co)polymerization ofn-Butyl Acrylate and Methyl Methacrylate via RAFT Using Amphiphilic Poly(ethylene oxide)-Based Trithiocarbonate Chain Transfer Agents

Abstract

The RAFT-mediated, surfactant-free, ab initio, batch emulsion polymerization of n-butyl acrylate (nBA) and its copolymerization with methyl methacrylate (MMA) were studied. The control agent was a surface-active trithiocarbonate macromolecular RAFT agent composed of a hydrophilic poly(ethylene oxide) (PEO) block and a hydrophobic dodecyl chain. The homopolymerizations of nBA were fast with high final conversions, and the polymer chains were well-controlled with narrow molar mass distribution. The length of the PEO chain was shown to affect the particle size and the polymerization kinetics directly. We found the conditions to tune the particle size independently from the poly(n-butyl acrylate) chain length by playing with a mixture of macro-RAFT agents with long and short PEO segment or by adding a PEO-based nonionic surfactant. The copolymerizations of nBA and MMA exhibited features very similar to those of the nBA homopolymerizations provided that the molar percentage of MMA did not exceed approximately 75%. In all cases, stable, submicrometric particles composed of amphiphilic diblock copolymer chains were formed.

Effect of stirring rate on particle formation in emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene

“…[18][19][20] As a solution of the problem, Hawkett and coworkers recently proposed an emulsifier-free reversible addition-fragmentation chain transfer emulsion polymerization method utilizing self-assembly. 21,22 Following this proposal, nitroxide-mediated radical polymerization [23][24][25][26][27][28] and reversible addition-fragmentation chain transfer [29][30][31][32][33][34][35] in emulsion polymerization systems have been successfully studied.…”

Emulsifier-free synthesis of crosslinkable ABA triblock copolymer nanoparticles via AGET ATRP

“…46 A PEO (800)-based ATRP initiator had been synthesized and utilized to emulsion polymerization of AMA, but coagulation occurred even at the early stage of the reaction. This indicates that the length of PEO chain must be long enough to stabilize the latex.…”

“…To the best our knowledge, it is the first time to synthesize such a crosslinkable block copolymer by AGET ATRP under emulsifier-free batch emulsion polymerization conditions. [45][46][47][48] Experimental Materials. Poly(ethylene oxide) (PEO), CuBr 2 , N,N-dimethyldodecylamine (DMDA), ascorbic acid (AA), neutral Al 2 O 3 , CaH 2 , NaOH were AR grade and were used directly as received from Sinopharm Chemical Reagent Co., Ltd (SCRC).…”

Preparation of Inert Polystyrene Latex Particles as MicroRNA Delivery Vectors by Surfactant-Free RAFT Emulsion Polymerization

“…[4][5][6][7] Surfactant-free reversible addition-fragmentation chain transfer (RAFT) emulsion polymerisation technique is an advantageous method to synthesise latex particles for potential bioapplications, [8][9][10] since this approach does not required the use of particle-stabilising surfactants, which may desorb from particles overtime and hampered therapeutic applications. 11 To act as particle stabiliser in the preparation of latex particles by surfactantfree RAFT emulsion polymerisation, two strategies have already been employed: the use of surface-active amphiphilic RAFT-capped block copolymers, [12][13][14][15][16] or a one-pot polymerisation of a hydrophobic monomer from a low molar mass surface-active RAFT agent. 17 While the particles formation kinetics and their morphology control have been studied extensively, there are only a few scarce examples describing the use of this technique to engineer latex particles for the attachment of biomolecules or therapeutic agents.…”