期刊
POLYMER JOURNAL
卷 35, 期 8, 页码 652-661出版社
NATURE PUBLISHING GROUP
DOI: 10.1295/polymj.35.652
关键词
layered polymer crystals; intercalation; poly(muconic acid); solid-state photoreaction; polydiacetylene
We have investigated the intercalation of several unsaturated amines using poly(muconic acid) crystals as the layered organic polymer host. Allyl- and oleylamines are intercalated into the polymer crystals in order to introduce an olefin moiety in the side chain of poly(muconic acid). The oleylammonium polymer crystals are alternatively obtained by the topochemical polymerization of oleylammonium muconate as the corresponding ammonium monomer crystals under photoirradiation in the crystalline state, while the photoirradiation of the allylammonium muconate crystals results in the formation of isomers. The inner double bond of the intercalated oleyl group has a low reactivity under UV irradiation, and the allyl group has no reactions. In contrast, diene and diyne moieties introduced into the side chain by the intercalation using 2,4-hexadienyl-, 2,4-tetradecyldienyl-, and 10,12-pentacosadiynylamines as the guest amines readily react to give a new type of the polymer crystal consisting of alternately stacked polymer nano-sheets. We have revealed that the intercalation of long-chain unsaturated amines proceeds in a high conversion, and the photoreactivity of the unsaturated functional groups in the side chain is determined by the kind of unsaturated groups and the stacking distance of the amine molecules in the layers.
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