A One‐Step Route to CO₂‐Based Block Copolymers by Simultaneous ROCOP of CO₂/Epoxides and RAFT Polymerization of Vinyl Monomers

Abstract

The one-step synthesis of well-defined CO -based diblock copolymers was achieved by simultaneous ring-opening copolymerization (ROCOP) of CO /epoxides and RAFT polymerization of vinyl monomers using a trithiocarbonate compound bearing a carboxylic group (TTC-COOH) as the bifunctional chain transfer agent (CTA). The double chain-transfer effect allows for independent and precise control over the molecular weight of the two blocks and ensures narrow polydispersities of the resultant block copolymers (1.09-1.14). Notably, an unusual axial group exchange reaction between the aluminum porphyrin catalyst and TTC-COOH impedes the formation of homopolycarbonates. By taking advantage of the RAFT technique, it is able to meet the stringent demand for functionality control to well expand the application scopes of CO -based polycarbonates.

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO2‐Based Block Copolymers from Monomer Mixtures

“…[11] In this context, we recently reported aonestep route to CO 2 -based block copolymers with tailorable functionalities and compositions by concurrent reversible addition-fragmentation chain-transfer (RAFT) polymerization of conjugated vinyl monomers and ROCOP of CO 2 / epoxides using ab ifunctional chain-transfer approach. [12] However,n ew methods need to be developed to further expand the structural diversity of CO 2 -based block copolymers.…”

One‐Step Ring Opening Metathesis Block‐Like Copolymers and their Compositional Analysis by a Novel Retardation Technique

“…Wurm's group reported the synthesis of block‐like copolymers from the mixture of epoxides and aziridines with different reactivities depending upon the electron‐withdrawing effect of a sulfonamide substituent on the aziridines . An alternative way to prepare block copolymers in one pot is the simultaneous polymerization from bifunctional initiators using different propagation mechanisms …”

“…[3,18] An alternative way to prepare block copolymers in one pot is the simultaneous polymerization from bifunctional initiators using different propagation mechanisms. [19][20][21][22][23][24][25] An interesting "fire and forget" approach based on anionic polymerization for one-shot block-like terpolymer synthesis from the mixture of butadiene, styrene, and diphenylethylene has recently been reported by Hutchings and co-workers. [26] A well-known one-step method for block-like copolymer synthesis from styrene and maleic anhydride is based on nitroxide-mediated polymerization.…”

Switchable Polymerization Triggered by Fast and Quantitative Insertion of Carbon Monoxide into Cobalt–Oxygen Bonds

“…In order to expand the application scopes of biodegradable polymers resulted from ROCOP, intensive research efforts have been directed to the rational design and synthesis of block copolymers by combining ROCOP and other living/controlled polymerization techniques . We have reported the one‐step synthesis of well‐defined CO 2 ‐based block copolymers via concurrent ROCOP and RAFT polymerization using a bifunctional chain transfer agent in 2018, however, only conjugated monomers such as methyl methacrylate (MMA) and styrene (St) were involved . In a recent contribution, we have illustrated a mechanistic switch involving ROCOP and OMRP with a (Salen)Co system as catalyst/mediator for both mechanisms.…”