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乙酰丙酮锆引发的 D,L-丙交酯聚合动力学。

Kinetics of D,L-Lactide Polymerization Initiated with Zirconium Acetylacetonate.

机构信息

National Research Center Kurchatov Institute, 123098, Moscow, Russia.

出版信息

ChemistryOpen. 2020 Oct 13;9(10):1027-1032. doi: 10.1002/open.202000101. eCollection 2020 Oct.

Abstract

The kinetic of D,L-lactide polymerization in presence of biocompatible zirconium acetylacetonate initiator was studied by differential scanning calorimetry in isothermal mode at various temperatures and initiator concentrations. The enthalpy of D,L-lactide polymerization measured directly in DSC cell was found to be =-17.8±1.4 kJ mol. Kinetic curves of D,L-lactide polymerization and propagation rate constants were determined for polymerization with zirconium acetylacetonate at concentrations of 250-1000 ppm and temperature of 160-220 °C. Using model or reversible polymerization the following kinetic and thermodynamic parameters were calculated: activation energy =44.51±5.35 kJ mol, preexponential constant ln=15.47±1.38, entropy of polymerization =-25.14 J mol K. The effect of reaction conditions on the molecular weight of poly(D,L-lactide) was shown.

摘要

用差示扫描量热法在等温条件下,于不同温度和引发剂浓度下研究了生物相容性的乙酰丙酮氧锆引发剂存在下 D,L-丙交酯聚合的动力学。在 DSC 池内直接测量的 D,L-丙交酯聚合焓被发现为=-17.8±1.4 kJ/mol。在 160-220°C 的温度和 250-1000 ppm 的浓度下,对与乙酰丙酮氧锆的聚合进行了聚合动力学曲线和增长速率常数的测定。使用模型或可逆聚合计算了以下动力学和热力学参数:活化能 =44.51±5.35 kJ/mol,ln=15.47±1.38,聚合熵 =-25.14 J/mol/K。显示了反应条件对聚(D,L-丙交酯)分子量的影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6859/7552909/854d9f9217db/OPEN-9-1027-g007.jpg

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