Abstract

The kinetics of formation of a three-dimensional structure in compositions based on butyl rubber and silicon-containing hyperbranched polymethylsilsesquioxanes and MQ copolymers is studied in comparison with compositions containing common dispersed phases: carbon black and silica. Features of the chemical structure of the synthesized organosilicon polymers make it possible to treat the morphology of their elementary particles as core–shell. The role of an inorganic “core” is played by silica structures, whereas methyl shells should ensure compatibility with the carbochain matrix of the rubber. Quinol ether is used as an agent of crosslinking via double bonds of the isoprene part of the rubber. The crosslinking process is carried out in the mode of continuous heating of compositions with registration of thermal effects by differential scanning calorimetry and dynamic moduli by oscillatory rheometry. The apparent activation energies of the process of chemical crosslinking under nonisothermal conditions are calculated in terms of various models. It is shown that the apparent activation energy of crosslinking is lower for filled systems. This indicates that rubber macromolecules are partially uninvolved in chemical crosslinking as a result of adsorption and loss of relaxation mobility. The adsorption activity of fillers is estimated from a difference in the activation energies of the initial rubber and filled compositions; this parameter is the lowest for polymethylsilsesquioxanes.

中文翻译：

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基于丁基橡胶和分散填料的组合物交联过程的动力学特征

摘要

与含有常见分散相：炭黑和二氧化硅的组合物相比，研究了基于丁基橡胶和含硅超支化聚甲基倍半硅氧烷和 MQ 共聚物的组合物中三维结构的形成动力学。合成的有机硅聚合物的化学结构特征使其可以将其基本粒子的形态视为核壳。无机“核”的作用由二氧化硅结构发挥，而甲基壳应确保与橡胶的碳链基质相容。喹诺醚用作通过橡胶异戊二烯部分的双键进行交联的试剂。交联过程以连续加热组合物的方式进行，通过差示扫描量热法记录热效应，并通过振荡流变测定法记录动态模量。根据各种模型计算非等温条件下化学交联过程的表观活化能。结果表明，填充体系的交联表观活化能较低。这表明橡胶大分子由于吸附和松弛迁移率的丧失而部分不参与化学交联。填料的吸附活性通过初始橡胶和填充组合物的活化能差异来估计；该参数对于聚甲基倍半硅氧烷而言是最低的。根据各种模型计算非等温条件下化学交联过程的表观活化能。结果表明，填充体系的交联表观活化能较低。这表明橡胶大分子由于吸附和松弛迁移率的丧失而部分不参与化学交联。填料的吸附活性通过初始橡胶和填充组合物的活化能差异来估计；该参数对于聚甲基倍半硅氧烷而言是最低的。根据各种模型计算非等温条件下化学交联过程的表观活化能。结果表明，填充体系的交联表观活化能较低。这表明橡胶大分子由于吸附和松弛迁移率的丧失而部分不参与化学交联。填料的吸附活性是根据初始橡胶和填充组合物的活化能差异估算的；该参数对于聚甲基倍半硅氧烷而言是最低的。这表明橡胶大分子由于吸附和松弛迁移率的丧失而部分不参与化学交联。填料的吸附活性通过初始橡胶和填充组合物的活化能差异来估计；该参数对于聚甲基倍半硅氧烷而言是最低的。这表明橡胶大分子由于吸附和松弛迁移率的丧失而部分不参与化学交联。填料的吸附活性通过初始橡胶和填充组合物的活化能差异来估计；该参数对于聚甲基倍半硅氧烷而言是最低的。