Block Copolymers by Mechanistic Transformation from PROAD to Iniferter Process

Abstract

A facile strategy for synthesizing block copolymers by the combination of two different living polymerization techniques, namely, photoinduced radical oxidation/addition/deactivation (PROAD) and iniferter processes is described. In the first step, PROAD polymerization of isobutyl vinyl ether using bromotriphenylmethane, dimanganese decacarbonyl (Mn (CO) ), and diphenyliodonium bromide (Ph I Br ) is carried out to yield polymers with triphenylmethyl (trityl) end groups. These prepolymers are used as macroiniferters in thermally induced free radical polymerization of vinyl monomers such as methyl methacrylate, tert-butyl acrylate, and styrene, resulting in the formation of corresponding block copolymers free from homopolymers. The precursor polymer and final block copolymers are characterized by H NMR, FT-IR, GPC, and DSC analyses.

Controlled Synthesis of Block Copolymers by Mechanistic Transformation from Atom Transfer Radical Polymerization to Iniferter Process

“…Moreover, correlated to the notable progress in controlled polymerizations, the method is further extended to these systems to give block copolymer with adjustable segment lengths and narrow molecular weight distributions. Previously, iniferter process was combined with PROAD facilitating formation of block copolymers from cationically polymerizable vinyl ether with vinyl monomers in a controlled manner . It should be pointed out that in the reported approach, iniferter end groups were attached to the poly(vinyl ether) segment in the initiation step.…”

“…Thus, with the purpose of employment of iniferter procedure for block copolymer synthesis, we first prepared PMMA‐Br via ATRP. Subsequently, trityl groups were attached to polymer chain end in a similar way as described previously . PMMA‐trityl was then used as a precursor for the polymerization of several vinyl monomers to give the corresponding block copolymers.…”

“…Previously, iniferter process was combined with PROAD facilitating formation of block copolymers from cationically polymerizable vinyl ether with vinyl monomers in a controlled manner. [43] It should be pointed out that in the reported approach, iniferter end groups were attached to the poly(vinyl ether) segment in the initiation step.…”

“…Subsequently, trityl groups were attached to polymer chain end in a similar way as described previously. [43] PMMA-trityl was then used as a precursor for the polymerization of several vinyl monomers to give the corresponding block copolymers. The overall process including trityl functionalization and the block copolymerization is illustrated in Scheme 1 on the example using styrene as the second monomer.…”

Synthesis of Polysulfone Based Amphiphilic Graft Copolymers by a ‘Grafting to’ Approach

“…21,22 Such processes provide numerous benefits including practicality at low temperatures, reduced energy consumptions, rapid reaction rates, and minimized side reactions. Utilization of the process in, synthesis of graft, 24-26 block 27 and hyperbranched polymers, 28 radical coupling, 29 controlled radical polymerization, and 30 promotion of cationic polymerization 31 have been reported and reviewed. in addition to some traditional applications (coatings, adhesives, etc.).…”