Anionic polymerization of cyclohexa-1,3-diene in cyclohexane with high stereoregularity and the formation of crystalline poly(cyclohexa-1,3-diene)

作者：Quirk RP^*; You FX; Zhu L; Cheng SZD

来源：Macromolecular Chemistry and Physics, 2003, 204(5-6): 755-761.

DOI：10.1002/macp.200390048

• anionic polymerization
• crystalline poly(cyclohexa-1,3-diene)
• poly(cyclohexa-1,3-diene)
• microstructure

Polymerization of cyclohexa-1,3-diene using sec-BuLi as initiator in cyclohexane produces both soluble (70-90 wt.-%) and insoluble (10-3 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 degreesC). Both fractions were characterized by size exclusion chromatography and by H-1 NMR and C-13 NMR spectroscopy. The microstructures of both fractions were determined by high-resolution H-1 NMR quantitative C-13 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 greater than or equal to97% and the cis planomer content was higher in cyclohexane than in benzene or in cyclohexane with DABCO as additive.

• 出版日期2003-4-17