Atom-Transfer Radical Polymerization of Dimethyl Itaconate

Nitroxide-Mediated Copolymerization of Itaconate Esters with Styrene

“…Initially, the homopolymerization of DBI via NMP at different temperatures was examined. Interestingly, although DBI was homopolymerized via conventional radical processes and RDRP processes such as RAFT [32,33] and the related dimethyl itaconate (DMI) by ATRP [34], DBI did not homopolymerize via NMP with no conversion after several hours at elevated temperatures of~110 • C. We also examined the homopolymerization of dimethyl itaconate (DMI) under the same conditions and again observed no conversion after several hours. We suspected this was due to a stable adduct formed by reaction of the alkoxyamine (NHS-BlocBuilder) and one unit of DBI (see Figure 1).…”

“…Further, chain transfer to monomer is prevalent in systems with sterically hindered monomers like DBI and were argued to be related to the very low k p of dialkyl itaconates [50]. In ATRP systems, for DMI with copper halides teamed with various ligands such as methyl 2-bromopropionate (MBrP), p-toluene 2-sulfonyl chloride, pentamethyl diethylenetriamine (PMDETA) and 2,2'bipyridine (bpy) at temperatures of 100 • C and 120 • C, were controlled up to about 50% conversion, with an abrupt decrease in polymerization rates at that juncture [34]. These variations did not enhance polymerization rate or control of the polymerization.…”

“…To impart a wider array of properties, itaconic acid derivatives such as poly(dialkyl itaconate)s have provided flexibility in blends or in statistical or block copolymers. For example, di-n-butyl itaconate (DBI) can impart lower glass transition temperatures in copolymers and consequently similar related dialkyl itaconates have been polymerized via conventional free radical polymerization (FRP) [2,11,[18][19][20][21][22][23][24][25][26][27][28][29][30][31] and more recently via reversible de-activation radical polymerization (RDRP), also known as controlled radical polymerization (CRP), specifically reversible addition fragmentation chain transfer polymerization (RAFT) [32,33] and atom transfer radical polymerization (ATRP) [34,35]. In one case, NMP has been reported using TEMPO-based initiators but no molecular weight distributions were provided, ascribed to the styrene/DBI copolymers adsorbing onto the gel permeation chromatography (GPC) columns [36].…”

Organocatalyzed Living Radical Polymerization of Itaconates and Self‐Assemblies of Rod−Coil Block Copolymers

“…Living radical polymerization, [ 22–25 ] also termed reversible−deactivation radical polymerization, was used for itaconates to synthesize well‐defined polymers with predicted molar masses and narrow molar mass distributions. For example, atom transfer radical polymerization (ATRP) and reversible addition−fragmentation chain transfer (RAFT) polymerization of DMI, DBI, and dicyclohexyl itaconate successfully yielded polymers with low dispersity ( Đ = M w / M n = 1.3−1.5), [ 26–28 ] where M n and M w are the number‐ and weight‐average molar masses, respectively. Because the chain transfer to monomer is generally significant for itaconates at high temperatures, the Đ value tended to increase as the polymerization proceeded.…”

Comb-like copolymers of n-alkyl monoitaconates and styrene

“…Fernández-García [16] investigated the kinetics of the atom-transfer radical polymerization of dimethyl itaconate, using a CuX/2,2 -bipyridine catalytic system (X = Cl, Br) and a variety of initiators. In an experimental and theoretical study, Szablan et al [17] carried out both ATRP and RAFT homopolymerizations of di-n-butyl itaconate (DBI), dicyclohexyl itaconate (DCHI) and dimethyl itaconate [17,18].…”