高玻璃化温度的环己基取代的聚乙交酯,Macromolecules

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高玻璃化温度的环己基取代的聚乙交酯
Macromolecules ( IF 5.1 ) Pub Date : November 29, 2007 , DOI: 10.1021/ma071430d
Feng Jing ₁ , Milton R. Smith ₁ , Gregory L. Baker ₁

Affiliation

取代的乙交酯rac-二环己基乙交酯（rac -3,6-二环己基-1,4-二恶烷-2,5-二酮），内消旋-二环己基乙交酯，R，R -R-二环己基乙交酯和rac-甲基环己基乙交酯（rac -3-环己基-6 -甲基-1，4-二恶烷-2，5-二酮已被合成，并且这些单体的溶液聚合和本体聚合均被报道。研究了这些新单体的聚合动力学和与用于数据外消旋-diisopropylglycolide（外消旋-3,6-二异丙基-1,4-二恶烷-2,5-二酮）和外消旋-丙交酯。溶液聚合速率遵循以下顺序： rac-二环己基乙交酯< rac-二异丙基乙交酯< rac-甲基环己基乙交酯< rac-丙交酯。聚（rac-二环己基乙交酯）的玻璃化转变温度为98°C，与坚硬的聚乙交酯骨架一致。合成并聚合了内消旋-二环己基乙交酯和R，R-二环己基乙交酯，研究了立体化学对聚合物性能的影响。内消旋-二环己基乙交酯的玻璃化转变温度为96℃，而聚（R，R-二环己基乙交酯）的玻璃化转变温度提高至104℃。核磁共振波谱表明，聚（R，R-二环己基乙交酯）在聚合过程中经历了最小的消旋作用，差示扫描量热法（DSC），X射线衍射（XRD）和偏振光学显微镜证实该聚合物是无定形的。

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Cyclohexyl-Substituted Polyglycolides with High Glass Transition Temperatures

The substituted glycolides rac-dicyclohexylglycolide (rac-3,6-dicyclohexyl-1,4-dioxane-2,5-dione), meso-dicyclohexylglycolide, R,R-dicyclohexylglycolide, and rac-methylcyclohexylglycolide (rac-3-cyclohexyl-6-methyl-1,4-dioxane-2,5-dione) have been synthesized, and both solution and bulk polymerizations of these monomers are reported. The polymerization kinetics of these new monomers were studied and compared to data for rac-diisopropylglycolide (rac-3,6-diisopropyl-1,4-dioxane-2,5-dione) and rac-lactide. The solution polymerization rates followed the order: rac-dicyclohexylglycolide < rac-diisopropylglycolide < rac-methylcyclohexylglycolide < rac-lactide. The glass transition temperature of poly(rac-dicyclohexylglycolide) is 98 °C, consistent with a stiff polyglycolide backbone. meso-Dicyclohexylglycolide and R,R-dicyclohexylglycolide were synthesized and polymerized to study the effect of stereochemistry on the polymer properties. The glass transition temperature of meso-dicyclohexylglycolide was 96 °C, while that of poly(R,R-dicyclohexylglycolide) increased to 104 °C. While NMR spectroscopy indicated that poly(R,R-dicyclohexylglycolide) undergoes minimal racemization during polymerization, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and polarized optical microscopy confirmed that the polymer was amorphous.

更新日期：2017-01-31

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