Controlled synthesis of random, block-random and gradient styrene, methyl methacrylate and acrylonitrile Terpolymers via Nitroxide-mediated free radical polymerization

Controlled Synthesis of Poly(pentafluorostyrene-ran-methyl methacrylate) Copolymers by Nitroxide Mediated Polymerization and Their Use as Dielectric Layers in Organic Thin-film Transistors

“…Methacrylic monomers are notoriously challenging to polymerize in pseudo-living fashion, due to their large equilibrium constant for propagation and unwanted side reactions [ 26 , 27 ]. To increase the number of living propagating chains methacrylate monomers are often copolymerized with a slowly propagating comonomer, which is more compatible with NMP, such as styrenics [ 28 , 29 , 30 , 31 ], acrylonitrile [ 32 , 33 , 34 , 35 ] or cyclic ketene acetal 2-methylene-4-phenyl-1,3-dioxolane [ 36 , 37 ]. PFS has been demonstrated to behave as a controlling comonomer in the NMP of various methacrylic monomers, such as methacrylic acid [ 22 ], 5-methacryloyloxy-2,6-norboranecarbolactone (NLAM) [ 38 ], oligo(ethyleneglycol) methacrylate (OEGMA) [ 39 ] and, very recently, methyl methacrylate (MMA) [ 40 ].…”

Asymmetric Copolymers: Synthesis, Properties, and Applications of Gradient and Other Partially Segregated Copolymers

“…By increasing the number of blocks, a continuous composition profile can be approached as closely as desired. Stepwise gradient and related asymmetric copolymers have been prepared by different methods including NMP, ATRP, RAFT, as well as by living anionic polymerization and C1 copolymerization, a polyhomologation reaction that uses methylene and ethylidene ylide monomers as substrates …”

“…Many techniques have been used for the preparation of asymmetric copolymers, including anionic and cationic polymerizations, C1 polymerization, catalyst transfer polycondensation, catalyzed copolymerization of olefins and epoxides, ring‐opening metathesis polymerization (ROMP) and various RDRP techniques (e.g., atom transfer radical polymerization (ATRP), nitroxide‐mediated polymerization (NMP), organometallic‐mediated radical polymerization (OMRP), and reversible addition–fragmentation chain transfer (RAFT)).…”

“…Spontaneous gradient copolymers have been obtained via catalyst transfer polycondensation, catalyzed copolymerization of olefins and epoxides, diverse RDRP methods (ATRP, NMP, OMRP, RAFT,) as well as cationic ring opening polymerization . Also, the gradient‐composition backbone can be used as macroinitiators to synthesize high‐molecular‐weight brushes .…”

Synthesis and characterization of poly(styrene-b-methyl methacrylate) block copolymers via ATRP and RAFT

“…This technique offers a significant advantage in reducing the poly dispersion of the polymer chain. The balance between deactive and active species has been taken as the basis and therefore sometimes referred to as "living" polymerization (Zaremski, Eremeev et al 2017, Wilson, Magenau et al, 2018.…”