Abstract

AbstractIn order to find out correlations between the structure of an external donor and the obtained polymer, the effects of different external donors on the activity and stereospecificity of the MgCl2/TiCl4 catalytic system in the bulk polymerization of 4‐methyl‐1‐pentene (4MP) were carefully studied. Different silane compounds of the structure RnSi(OR')4‐n (where: n = 1–3, R = alkyl/phenyl, R = alkyl) and Al(i‐Bu)3 (TIBA) were used as external donors and cocatalyst, respectively. The effect of the donor/TIBA mole ratio on the activity and stereospecificity of the catalytic system was studied. Some major effects were observed for the three different external donors, namely, Me3Si(OMe), Me2Si(OMe)2, and Me3Si(OBu)3, in the 4MP polymerization process. It was observed that the effect of the external silane donor on the polymerization strongly depends upon the size of the alkoxy and hydrocarbon (alkyl/phenyl) groups which are attached to the silicon atom. A selective deactivation of the non‐stereospecific centers, as well as a transformation of the non‐stereospecific into isospecific centers, is assumed to occur. On the basis of the obtained results and literature data available for the propene polymerization, the concept of structural conformity between the ligand‐surrounded active center and the monomer molecule was carried forward.

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