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Chemoselectivity in 4-methyl-1,3-pentadiene polymerization in the presence of homogeneous Ti-based catalysts

✍ Scribed by Pasquale Longo; Fabia Grisi; Antonio Proto; Adolfo Zambelli

Publisher
John Wiley and Sons
Year
1997
Tongue
English
Weight
267 KB
Volume
18
Category
Article
ISSN
1022-1336

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✦ Synopsis

Abstract

The homogeneous catalyst CpTiCl~3~‐MAO is able to produce a random copolymer of 4‐methyl‐1,3‐pentadiene with ethylene. ^13^C NMR analysis of the copolymers shows that after insertion of ethylene units, the next 4‐ymethyl‐1,3‐pentadiene unit can be inserted in either 1,2 or 1,4 arrangement. The high chemoselectivity observed in the 1,2‐syndiotactic homopolymerization of 4‐methyl‐1,3‐pentadiene with respect to the lower one observed in the copolymerization with ethylene is attributed to a back‐biting coordination to the Ti of the active species of the penultimate monomer unit of the growing chain.

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Polymerization of 4-Methyl-1,3-pentadiene with Catalysts Based on Cyclopentadienyl Titanium Chlorides: Effect of anti/syn Isomerism of the Allylic Group on the Chemoselectivity and the Role of Backbiting Coordination in 1,3-Diene Polymerization
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Copolymerization of styrene with (Z )-1,3-pentadiene affords copolymers mostly containing 1,2 pentadiene units. Both the styrene and the pentadiene units are in syndiotactic arrangement but the comonomer sequence distribution is far from bernoullian. Interestingly, the behavior of (Z )-1,3-pentadien