AAB-sequence living radical chain copolymerization of naturally occurring limonene with maleimide: an end-to-end sequence-regulated copolymer.
Sequence control in chain-growth polymerization is still one of the most challenging topics in synthetic polymer chemistry in contrast to natural macromolecules with completely sequence-regulated structures like proteins and DNA. Here, we report the quantitative and highly selective 1:2 sequence-regulated radical copolymerization of naturally occurring (+)-d-limonene (L) and a maleimide (M) in fluoroalcohol giving chiral copolymers with high glass transition temperatures (220-250 degrees C) originating from the specific rigid cyclic structures of the monomers. Furthermore, the combination with a reversible addition-fragmentation chain transfer (RAFT) agent (C-S) via the controlled/living radical polymerization resulted in end-to-end sequence-regulated copolymers [C-(M-M-L)(n)-M-S] with both highly sequenced chain ends and main-chain repeating units as well as controlled molecular weights.
Satoh
Kotaro
K
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan.
Matsuda
Masaru
M
Nagai
Kanji
K
Kamigaito
Masami
M
D000438:Alcohols / Q000737:chemistry; D001688:Biological Products / Q000737:chemistry*; D053138:Cyclohexenes / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D007700:Kinetics; D000077222:Limonene; D008301:Maleimides / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D013237:Stereoisomerism; D013696:Temperature; D013729:Terpenes / Q000737:chemistry*
D000438:Alcohols; D001688:Biological Products; D053138:Cyclohexenes; D005609:Free Radicals; D008301:Maleimides; D011108:Polymers; D013729:Terpenes; C043592:maleimide; D000077222:Limonene