Journal
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
Volume 53, Issue 24, Pages 2898-2907Publisher
WILEY
DOI: 10.1002/pola.27769
Keywords
catalysts; copolymerization; ethylene; high performance polymers; isoprene
Categories
Funding
- National Natural Science Foundation of China [20974014, 21274012, 21322401]
- 111 project [B07012]
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Isoprene polymerization and copolymerization with ethylene can be carried out by using cationic half-sandwich fluorenyl scandium catalysts in situ generated from half-sandwich fluorenyl scandium dialkyl complexes Flu'Sc(CH2SiMe3)(2)(THF)(n), activator, and (AlBu3)-Bu-i under mild conditions. In the isoprene polymerization, all of these cationic half-sandwich fluorenyl scandium catalysts exhibit high activities (up to 1.89 x 10(7) g/mol(Sc) h) and mainly cis-1,4 selectivities (up to 93%) under similar conditions. In contrast, these catalysts showed different activities and regio-/stereoselectivities being significantly dependent on the substituents of the fluorenyl ligands in the copolymerization of isoprene with ethylene under an atmosphere of ethylene (1 atm) at room temperature, affording the random copolymers with a wide range of cis-1,4-isoprene contents (IP content: 64-97%, cis-1,4-IP units: 65-79%) or almost alternating copolymers containing mainly 3,4-IP-alt-E or/and cis-1,4-IP-alt-E sequences. Moreover, novel high performance polymers have been prepared via selective epoxidation of the vinyl groups of the 1,4-isoprene units in the IP-E copolymers. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2898-2907
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