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Effect of electronegativity and steric hindrance of the cocatalyst on the activity and selectivity of butadiene polymerization catalyzed by molybdenum
Author(s) -
Liu Jinhui,
Geng Jieting,
Liu Kai,
Zou Lingli,
Wang Zhaobo,
Hua Jing
Publication year - 2019
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.46906
Subject(s) - electronegativity , polybutadiene , steric effects , polymerization , polymer chemistry , polymer , molybdenum , monomer , materials science , crystallinity , cationic polymerization , catalysis , substituent , chemistry , copolymer , organic chemistry , composite material
ABSTRACT Molybdenum‐based random 1,2‐polybutadiene (1,2‐PB) rubber, with its excellent wet skid resistance, low rolling resistance, and low heat buildup, can be used for green tread rubber, and it has significant benefits for the enhancement of the mechanical strength of 1,2‐PB. In this study, we investigated in detail the effects of the electronegativity and steric hindrance of the cocatalyst on the stereoselectivity of the resulting polymers. In the case of cocatalysts with moderate electronegativities, the active centers were more stable; this resulted in a larger molecular weight and a higher conversion, whereas a cocatalyst with excessive electronegativity tended to initiate cationic polymerization. The high sterically hindered substituent restricted the coordination configuration of the monomer; this ultimately resulted in the increase in the 1,2 structure to 90%. Fourier transform infrared analysis showed that the content of trans ‐1,4 structure increased from 7 to 66%, and its crystallinity reached 59.2%, as calculated with differential scanning calorimetry when triethyl aluminum was used as the cocatalyst. Consequently, trans ‐1,4‐polybutadiene crystals were introduced into the 1,2‐PB elastomer in one step; this could be a promising facile route for strengthening 1,2‐PB. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136 , 46906.