Synthesis of SAN‐containing block copolymers using RAFT polymerization

Abstract

Copolymerization of styrene and acrylonitrile was carried out via reversible addition‐fragmentation chain transfer process (RAFT) in the presence of cumyl dithiobenzoate with AIBN as initiator. Copolymerization proceeded in a controlled/“living” fashion, and the copolymer composition depended on the feed ratio of monomer pairs. Block copolymers comprising styrene and acrylonitrile (SAN) segments and various functional blocks were synthesized through chain extension using the first blocks as macromolecular chain transfer agents (macroCTAs). Since the polymerization of both blocks proceeded through the RAFT process, the resulting block copolymers exhibited relatively narrow molecular weight distribution, with polydispersity indices in the range of 1.29–1.46. Gel permeation chromatography (GPC), and 1H NMR and FTIR measurements confirmed the successful synthesis of the functionalized block copolymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2260–2269, 2006

Reactivity ratios of controlled/living copolymerization of styrene and acrylonitrile in ionic liquid microemulsion

“…The obtained reactivity ratios in this work are different from that of reported conventional microemulsion copolymerization of St and AN (r St =0.61-2.98, r AN =0-0.039) [35]. The reported reactivity ratios for the controlled/living copolymerization of St and AN calculated by the Jaacks's method were r St =0.46, r AN =0.19 [36]. The deviation of reactivity ratios may be due to different reaction media and different mechanism.…”

Living Radical Polymerization by the RAFT Process—A First Update

“…[135] [61] S/VBSC [62] 8* AN [63] (DBI) [64] DMAEMA [65] 9* (DBI) [64] DMAEMA [68] GMA [68] HPMAM/NMS [66] MMA [67] HEMA [68] (MA) [69] MMA [46,70,71] NIPAM [72] PFMA [73] (S) [44,74] S [75] S [76] S/AN [68] S/MAH [68] S S CN S S CN…”

“…Other examples of block copolymers are acrylamidebased block copolymers, [105] PAN-block-PMA, [207] poly-(styrene-co-AN) (SAN) block copolymers from methacrylate (DMAEMA, GMA, MMA) or poly(styrene-co-MAH) macro-RAFT agents (note that SAN and SAN block copolymers by RAFT have been reported previously [4] ), [68] and PBMAblock-PDMAEMA-block-PBMA and PDMAEMA-block-PBMA-block-PDMAEMA, [208] hydrophilic-hydrophobic block copolymers (including PBA-block-PDMA, PBAblock-PNAP, PBA-block-poly(2-(methylsulfinyl)ethyl acrylate)). [72,209,210] Further examples with specific applications are mentioned in the other sections of this review.…”

Compatibilization of Poly(styrene‐acrylonitrile) (SAN)/Poly(ethylene) Blends via Amine Functionalization of SAN Chain Ends

“…SAN copolymers can easily be made using NMP, [40][41][42] ATRP [43][44][45] and RAFT. [46,47] CRP techniques are also very useful in synthesizing functional polymers. This will be further explained in Section 2.1.…”

“…SAN copolymers can easily be made using nitroxide mediated polymerization (NMP), [40][41][42] atom transfer radical polymerization (ATRP), [43,45,53] and reverse atom transfer radical polymerization (RAFT). [46,47,54] The ability to form SAN-containing block copolymers allows for additional tailoring of properties for the blend.…”