Abstract

AbstractIron catalyst has been encountered with low activity and stereoselectivity sensitive to the operational conditions for diene polymerization. In this study, diphenylphosphite has been proved as an efficient donor in iron‐based tertiary catalyst for butadiene, isoprene and myrcene stereopolymerizations. Thermal robustness of active species has been demonstrated as the high activity and 1,2 stereoselectivity are survived in a wide temperature scope ranging from 5°C to 80°C. The resultant polybutadienes are found to have 1,2 incorporation up to 92.8% with syndiotactic conformation (rrrr: 95.1%), and more than 65% of irregular 3,4 enchainments are generated for polyisoprene and polymyrcene. The active species are formed preferably following addition sequence of iron compound, donor and activator in the presence of monomer. The development of this highly active and stable catalyst combining cost‐efficient components and mild operation parameters could provide accessible catalyst recipe to produce new types of polydienes.

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