Original approach to multiblock copolymers via reversible addition–fragmentation chain transfer polymerization

Abstract

α,ω‐Thiol‐terminated (co)polymers synthesized via reversible addition–fragmentation chain transfer polymerization can be oxidized to yield multiblock copolymers via the formation of disulfide bridges.

Living Radical Polymerization by the RAFT Process - A Second Update

“…St [184] MMA [88] 323 [185] 40 [186] S S O O St [186] St-b-MAH [186] St-b-MAH-b-NIPAM [186] 41* [187,188] S S (MMA) [64,187,189] BA [187] EHA [188] St [190] TBAM [191] DEAM [187] DMAM [187] NAM [191] NIPAM [187,189] BA/St [192] EHA-b-MA [188] TBAM-b-NAM [191] DMAM/NAS [193] NAM-b-TBAM [191] 42* S S Ph CN MMA [194] 376 [195] 376-b-MMA [195] BA [196] MMA [189] NIPAM [189] MMA-b-NIPAM [189] MMA/283 [197] MMA/284 [197] St/2VP [198] St/348 [199] THPA-b-St [200] THPA-b-St/373 [201] 44 [202] [200] 47 [203] …”

“…[117,130,479] This methodology has been applied to the synthesis of three-armed stars by an in-situ thiol-ene reaction with a triacrylate [130] and has been applied to directly make biopolymer conjugates. [479] A recent study shows that dithioester and trithiocarbonate RAFT agents [R-SC(S)Z] undergo a radical-catalyzed reaction with thiols that results in oxidation of the thiol to a disulfide and concomitant reduction of the RAFT agent to R-H. [481] The relative rates of reaction suggested that dithioester RAFT agents [204] PEGA Ph (58) Butylamine Used in thiol-ene [204] NIPAM SCH 2 CH(CH 3 ) 2 (188) Butylamine/TCEP/HEA butylamine/TCEP/BA One-pot thiol-ene [373] NIPAM SCH 2 CH(CH 3 ) 2 (188) Butylamine/TCEP Used in thiol-ene [371,372] NIPAM Ph (25) LiB(C 2 H 5 ) 3 H Used in thiol-ene [151] NIPAM S(CH 2 ) 2 CO 2 H (170) NaBH 4 Used in thiol-ene [355] NIPAM SC 4 H 9 (166) NaOH/MeOH/EDTA Used in thiol-ene [412] NIPAM Ph (24) Octylamine/DMPP/AMA One-pot thiol-ene [132] NIPAM Ph (24) Octylamine/DMPP/PMA One-pot thiol-ene [132] DEAM Ph (24) Hexylamine/DMPP/MA One-pot thiol-ene [130] St Ph (24) Propylamine/PBu 3 /MA NaBH 4 /PBu 3 /MA One-pot thiol-ene [117] St Ph (24) Propylamine NaBH 4 [205] MMA Ph (82) Hexylamine Conditions to favour disulfide formation [196] MMA Ph (22) Propylamine One-pot methanethiosulfonate [480] NVP OC 2 H 5 (228) NaBH 4 Used in peptide/nucleotide conjugation [396] A Monomer unit adjacent to thiocarbonylthio group. B TCEP -tris(2-carboxyethyl) phosphine hydrochloride, EDTA -ethylenediaminetetraacetic acid, TCEP -tris(2-carboxyethyl phosphine), DMPPdimethylphenylphosphine.…”

“…[503] Another RAFT-based approach to multiblock copolymers is based on oxidative coupling of telechelic polymers with thiol end-groups. [196,[240][241][242]260] The telechelics are synthesized by RAFT polymerization making use of a bis-RAFT agent with subsequent end-group transformation to form the bis-thiol. The procedure was also applied to synthesize cyclic polymers by using high dilution conditions.…”

Lateral Phase Separation in Grafted Diblock Copolymer Films

“…The thiol-terminated PMMA-b-PS-SH polymers were synthesized by RAFT polymerization as previously described, [13][14][15][16] while the hydroxyl-terminated, polystyrene-deuterated polymers, dPS-b-PMMA-OH were purchased from Polymer Standards Service (Mainz, Germany). All remaining chemicals were purchased from Aldrich or Fisher, were of AR grade or better, and were used without further purification.…”

Versatile synthetic approach to reversible crosslinked polystyrene networks via RAFT polymerization

“…16 We have also described the synthesis of multiblocks comprising poly(methyl methacrylate), poly(butyl acrylate), and poly(acrylic acid). 17 Importantly, all these polymers can be reduced to the starting polymer-a reversible process.…”