Diastereoisomeric diversity dictates reactivity of epoxy groups in limonene dioxide polymerization

被引：17

作者：

Soto, M. ^{[1
]}

Koschek, K. ^{[1
]}

机构：

[1] Fraunhofer Inst Mfg Technol & Adv Mat Fraunhofer, Wiener Str 12, D-28359 Bremen, Germany

来源：

EXPRESS POLYMER LETTERS | 2018年 / 12卷 / 06期

关键词：

biopolymers; thermosetting resins; thermal properties; PHOTOINITIATED CATIONIC-POLYMERIZATION; DERIVATIVES; CHEMISTRY; SYSTEMS; OXIDE;

D O I：

10.3144/expresspolymlett.2018.48

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Limonene dioxide (LDO) has the potential to find a wide application as a bio-based epoxy resin. Its polymerizations by catalyzed ring-opening, and by polyaddition with diamines were compared with the polymerizations of the commercial epoxy resins bisphenol-A diglycidyl ether (BADGE), and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate (ECC). Differential scanning calorimetry (DSC) studies showed that LDO polymerizations suffer in all cases studied from incomplete conversions. Nuclear magnetic resonance (NMR) studies revealed that in cis-isomers of LDO the internal epoxide rings were not reacting. The low reactivity of this epoxide group was explained by mechanistic considerations making use of the Furst-Plattner rule, or trans-diaxial effect. Due to diastereomeric diversity approximately one-fourth of epoxide groups present in LDO could not react. Therefore, a diastereoselective epoxidation of limonene could provide a fully reactive bio-based epoxy resin.

引用

页码：583 / 589

页数：7

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