期刊
MACROMOLECULES
卷 46, 期 14, 页码 5473-5482出版社
AMER CHEMICAL SOC
DOI: 10.1021/ma401021d
关键词
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资金
- Cabinet Office, Government of Japan
- Grants-in-Aid for Scientific Research [25107714] Funding Source: KAKEN
Naturally occurring hydroxy-functionalized limonene analogues, i.e., monoterpene alcohols such as perillyl alcohol and carveol, were radically copolymerized with cyclohexylmaleimide (CyMI) in PhC(CF3)(2)OH via 1:2-sequence-regulated propagation to obtain periodically functionalized bio-based copolymers possessing one hydroxyl group in every three-monomer unit. Alternatively, a combination of hydroxy-functionalized maleimide (N-2-hydroxyethylmaleimide: HEMI) and limonene resulted in another periodically functionalized copolymer possessing two hydroxyl groups for every three-monomer unit. These copolymerizations were fitted well by the penultimate model, where the hydroxyl functions did not have a significant effect on the selective propagation, as has been reported for a combination of nonfunctionalized limonene and CyMI. The periodic hydroxyl groups can be quantitatively converted into carbamate moieties by a polymer reaction with isocyanate to result in another series of 1:2 and 2:1 periodically functionalized copolymers. Periodically grafted copolymers possessing one or two graft chains repeating in three-monomer units were prepared by radical copolymerization of chlorine-functionalized limonene or maleimide derivatives, which were synthesized from hydroxy-functionalized monomers, followed by ruthenium-catalyzed living radical polymerization of methyl methacrylate initiated from periodically introduced C-Cl bonds in the backbone copolymers.
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