Relationship of catalyst composition to catalytic activity for the polymerization of α-olefins†

H. W. Coover Jr., Richard L. McConnell, F. B. Joyner
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引用次数: 4

Abstract

Heterogeneous olefin polymerization catalysts generally consist of a transition metal compound from groups IVB or VB in combination with an organometallic compound from groups I, II, and III of the periodic table of the elements, but in some instances may contain a third component possessing at least one strongly complexing ligand atom. The composition of a coordination catalyst of this type determines both the rate of polymerization of the α-olefin and the stereoregularity of the polymer produced. In order to predict activity and stereospecificity of catalysts for the polymerization of α-olefins, data from the polymerization of propylene using catalysts of the following types were correlated: (1) titanium(III) chloride catalysts in which the organometallic component was varied, (2) coordination catalysts containinig a ligand third component in which the ligand was varied, and (3) coordination catalysts in which the transition metal component was varied.

The electronegativity of an orgariometallic compound is known to be important in determining its reactivity with ethers, hydrogen, and other reagents. Both the ionic size and the electronegativity of the central atom appear to be important in determining the utility of both the organometallic and the transition metal compounds as components for coordination catalysts. In general, organometallic and transition metal compounds having small central atoms with similar electronegativities favor the formation of stereospecific catalysts.

The present correlation has made it possible to predict the activity and stereospecificity of coordination catalysts for olefin polymerization.

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α-烯烃†聚合催化剂组成与催化活性的关系
非均相烯烃聚合催化剂通常由来自IVB或VB族的过渡金属化合物与元素周期表中I、II和III族的有机金属化合物结合而成,但在某些情况下可包含具有至少一个强络合配体原子的第三组分。这类配位催化剂的组成决定了α-烯烃的聚合速度和聚合物的立体规整性。为了预测α-烯烃聚合催化剂的活性和立体专一性,将以下类型催化剂聚合丙烯的数据进行了对比:(1)不同有机金属组分的氯化钛催化剂,(2)不同配体第三组分的配位催化剂,以及(3)不同过渡金属组分的配位催化剂。已知有机金属化合物的电负性在决定其与醚、氢和其他试剂的反应性方面是重要的。离子大小和中心原子的电负性似乎在决定有机金属和过渡金属化合物作为配位催化剂组分的效用方面都是重要的。一般来说,具有类似电负性的小中心原子的有机金属和过渡金属化合物有利于形成立体定向催化剂。该关系为预测烯烃聚合配位催化剂的活性和立体专一性提供了可能。
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