Synthesis of transparent block copolymers consisting of poly(diisopropyl fumarate) and poly(2‐ethylhexyl acrylate) segments by reversible addition‐fragmentation chain transfer polymerization using trithiocarbonates as the chain transfer agents

Abstract

The reversible addition‐fragmentation chain transfer polymerization of diisopropyl fumarate (DiPF) was carried out using ethyl 2‐[[(dodecylthio)thioxymethyl]thio]‐2‐methylpropionate (T1) and 1,1′‐(1,2‐ethanediyl) bis[2‐[[(dodecylthio)thioxymethyl]thio]‐2‐methylpropionate] (T2) as the monofunctional and difunctional chain transfer agents (CTAs) to synthesize poly(diisopropyl fumarate) (PDiPF) with a rigid chain conformation. The obtained PDiPF had a well‐controlled molecular weight, molecular weight distribution, and structure of the chain ends. Size exclusion chromatography and NMR measurements revealed an excellent introduction efficiency (84–98%) of the terminal trithiocarbonate group into the polymer chain end. They were available as the monofunctional and difunctional macro‐CTAs to synthesize the AB and ABA block copolymers, respectively. While the well‐controlled block copolymers were solely obtained by the polymerization of 2‐ethylhexyl acrylate as the second monomer in the presence of PDiPF as the macro‐CTA, the block copolymerization of DiPF using poly(2‐ethylhexyl acrylate) as the macro‐CTA failed. The trithiocarbonate group at the chain end was completely removed by the reaction with n‐butylamine and it was valid for the improvement of the coloration and other optical properties of the transparent polymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2584–2594

Homo- and copolymers based on dialkyl fumarates: A review on radical polymerization, properties, current and future applications

“…In addition, reverse copolymerization (from macro-DIPF as CTA) were tested but the process was less efficient. Takada et al also synthesized AB and ABA block copolymers employing DIPF and HEA monomers by RAFT mechanisms, using an adequate CTA for each case [35,36]. The yellow polymers were discolored by reaction with n-butylamine in order to improve the coloration and other optical properties of the transparent polymers.…”

Production and Polymerization of Biobased Acrylates and Analogs

“…The same group investigated the use of various chain transfer agents such as dithiobenzoates and trithiocarbonates. [ 513–515 ] Careful selection of the RAFT agent was essential as a balance must be found between fragmentation and reinitiation. Recently, Sato et al.…”

RAFT Polymerization of 2‐(tert‐Butoxycarbonyloxy)Ethyl Methacrylate and Transformation to Functional Polymers via Deprotection and the Subsequent Polymer Reactions

“…Reversible addition–fragmentation chain transfer (RAFT) polymerization is the most important and useful living radical polymerization process for a wide range of vinyl monomers including methacrylates. [ 33–37 ] The polymer structure control for methyl methacrylate (MMA) and other many kinds of conjugated monomers were performed using trithiocarbonate compounds as the RAFT agent. [ 38–43 ] In many cases, however, it has been reported that the precise control of the living radical polymerization is interfered by polar and functional groups included in the methacrylate monomers, such as HEMA.…”