Copper mediated RDRP of thioacrylates and their combination with acrylates and acrylamides

Abstract

Ethyl thioacrylate was polymerised via Cu-RDRP and subjected to amidation to obtain the first “all-acrylic” copolymer.

Synthesis of Biobased Block Copolymers Using A Novel Methacrylated Methyl Salicylate and Poly(3‐Hydroxybutyrate)

“…RAFT polymerization is a versatile process that, with appropriate selection of reagents and reaction conditions, satisfies most of the established criteria for living polymerization. [34][35][36][37][38][39][40][41][42] The obtained macro RAFT agents were used in the RAFT polymerizations of methacrylated methyl salicylate (KzSA-MA) in the presence of AIBN to yield PHB-b-KzSA-MA block copolymers. The polymerization conditions and the results were shown in Table 1.…”

“…These results were consistent with the RAFT polymerization kinetics. [41,42] Under the same reaction conditions, the RAFT polymerization of KzSA-MA was carried out using PHBdea-R1 and PHBmae-R1 in order to understand the difference in molar masses of the obtained PHB-KzSA block copolymers. Figure 12 shows the variation of molar mass (M n ) against time in the RAFT polymerization of KzSA-MA using (a) PHBdea-R1, and (b) PHBmae-R1 at 90 °C.…”

Bromoform-assisted aqueous free radical polymerisation: a simple, inexpensive route for the preparation of block copolymers

“…Kinetic studies shown in Figure 1(b) suggest that the evolution of molar mass with monomer conversion is in line with conventional free radical polymerisation [78][79][80] , rather than RDRP [81][82][83][84][85] , where the relationship would be linear. The final molar mass appears to increase on addition of 0.5 mol % bromoform, however, closer inspection of the broad GPC curves indicates that the molar mass profiles for the PDMA synthesised are near-identical in all cases (see Figure S6).…”

Degradable thioester core-crosslinked star-shaped polymers

“…27,28 20,23,27,28 For instance, polymers and block copolymers from thioacrylates became accessible via RAFT, NMP and Cu (0)-RDRP. 20,23,30,31 Subsequently, post-polymerisation modifications of the thioester side chains, such as amidation to form polyacrylamides, have been successfully achieved. 20,23,30,31 While amidation, hydrolysis, transthioesterification and oxidative hydrolysis have previously been reported for the complete and selective degradation of polymers containing thioesters in the backbone, they remain unexplored for the design of degradable core-crosslinked star-shaped polymers.…”

“…20,23,30,31 Subsequently, post-polymerisation modifications of the thioester side chains, such as amidation to form polyacrylamides, have been successfully achieved. 20,23,30,31 While amidation, hydrolysis, transthioesterification and oxidative hydrolysis have previously been reported for the complete and selective degradation of polymers containing thioesters in the backbone, they remain unexplored for the design of degradable core-crosslinked star-shaped polymers. 18,[21][22][23][30][31][32] Herein, we introduce thioester linkages into the crosslinked core of star-shaped polymers in order to exploit their more pronounced reactivity and degradability compared to ester derivatives.…”