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Anionic Polymerization of Cyclohexa-1,3-diene in Cyclohexane with High Stereoregularity and the Formation of Crystalline Poly(cyclohexa-1,3-diene)

✍ Scribed by Roderic P. Quirk; Fengxiang You; Lei Zhu; Stephen Z. D. Cheng

Publisher
John Wiley and Sons
Year
2003
Tongue
English
Weight
120 KB
Volume
204
Category
Article
ISSN
1022-1352

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✦ Synopsis

Abstract

Polymerization of cyclohexa‐1,3‐diene using sec‐BuLi as initiator in cyclohexane produces both soluble (70–90 wt.‐%) and insoluble (10–30 wt.‐%) fractions depending on the temperature. The insoluble poly(cyclohexa‐1,3‐diene) was crystalline as determined by X‐ray diffraction and differential scanning calorimetry analysis (T~m~ = 178 °C). Both fractions were characterized by size exclusion chromatography and by ^1^H NMR and ^13^C NMR spectroscopy. The microstructures of both fractions were determined by high‐resolution ^1^H NMR and quantitative ^13^C NMR spectroscopy and compared to those poly(cyclohexa‐1,3‐diene)s prepared in benzene and in cyclohexane with 1,4‐diazobicyclo[2.2.2]octane (DABCO) as additive. The amount of 1,4‐addition of the insoluble fraction in cyclohexane was ≥ 97% and the cis planomer content was higher in cyclohexane than in benzene or in cyclohexane with DABCO as additive.

DSC traces for the insoluble PCHD recrystallized from dichloroethane.

magnified imageDSC traces for the insoluble PCHD recrystallized from dichloroethane.

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