The effect of the disperse composition of a titanium catalyst on the kinetic heterogeneity of isoprene polymerization centers

被引:4
|
作者
Mingaleev, V. Z. [1 ]
Zakharova, E. M. [1 ]
Zakharov, V. P. [1 ]
机构
[1] Russian Acad Sci, Inst Organ Chem, Ufa Res Ctr, Ufa 450054, Bashkortostan, Russia
基金
俄罗斯基础研究基金会;
关键词
STEREOSPECIFIC POLYMERIZATION; SYSTEMS;
D O I
10.1134/S1560090413080046
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
The kinetic heterogeneity of centers of isoprene polymerization on fractions of titanium catalyst particles is studied. It is found that the isoprene polymerization with a catalyst consisted of particles 0.03-0.14 mu m in diameter involves centers of one type with low reactivity. On catalyst particles 0.15-4.50 mu m in diameter, the active centers of polymerization of two types with high reactivity may be formed. The addition of modifiers, a reduced temperature of catalyst formation, and the hydrodynamic effect result in the appearance of a narrow fraction of particles 0.15-0.18 mu m in diameter with one type of surface active center that generates high-molecular-mass cis-1,4-polyisoprene. The obtained results are in accordance with the concept of particles 0.15-4.50 mu m in diameter as aggregates of the elementary crystallites of beta-TiCl3 connected via additional Al-Cl bonds to surface titanium atoms. At the same time, catalyst particles 0.03-0.14 mu m in diameter are formed by the minimum number of elementary crystallites, where titanium atoms are bound to a smaller number of chlorine atoms.
引用
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页码:497 / 507
页数:11
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