Bulk functionalization of ethylene-propylene copolymers I. Influence of temperature and processing on the reaction kinetics
Bulk functionalization of ethylene-propylene copolymers I. Influence of temperature and processing on the reaction kinetics
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DOI：
10.1002/app.1987.070330720
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发表时间：
1987-05
影响因子：
3
通讯作者：
R. Greco;G. Maglio;P. Musto
中科院分区：
文献类型：
--
作者：
R. Greco;G. Maglio;P. Musto
在140~200℃温度范围内，研究了过氧化二异丙苯(DCPO)对马来酸二丁酯(DBM)促进的乙烯-丙烯共聚物(EPR)官能化反应。这是在聚烯烃官能化的一般性讨论框架内完成的，以确保反应发生前反应物混合物的均质性。反应动力学和红外(IR)技术按两个不同的过程进行：在恒温浴中的静态反应和在用于预混步骤的同一混合器中的动态反应。两种情况下的反应动力学非常相似，并测得共同活化能为40千卡/摩尔。然而，存在一些微小的差异，从科学的角度来看，这是非常有趣的。用溶液粘度法间接监测了EPR在反应过程中的降解动力学。将计算结果与反应动力学进行了比较。文中还对所提出的接枝和降解反应机理进行了深入的讨论。进一步的工作正在进行，以分析EPR共聚物和反应物组成对官能化和降解反应的影响。
The dicumylperoxide (DCPO) promoted functionalization of an ethylene-propylene copolymer (EPR) by means of dibutyl meleate (DBM) has been studied in bulk at constant reactant composition (100 : 10 : 1 by wt EPR-DBM-DCPO) in the range of temperature from 140 to 200°C. The reactants have been premixed in a Brabender-like apparatus at 90°C in which no decomposition of the radical initiator could occur. This was done in the frame of a general discussion of polyolefin functionalization, to assure the homogeneity of the reactant mixture before the reaction occurred. The kinetics of the reaction followed by an infrared (IR) technique was carried out according to two different procedures: a static one in a thermostatic bath and a dynamic one in the same mixer used for the premixing step. The kinetics in the two cases are very comparable, and a common activation energy of 40 kcal/mol has been measured. Some minor differences exist, however, which are very interesting from a scientific point of view. The kinetics of EPR degradation during the reaction has been indirectly monitored by means of solution viscosimetry. The results have been compared with the reaction kinetics. A thorough discussion of the proposed mechanism for grafting and degradation reactions has been also provided. Further work is in progress to analyze the effect of the EPR copolymer and of reactant composition on the functionalization and degradation reactions.