Preparation of Butadiene-Isoprene Copolymer with High Vinyl Contents by Al(OPhCH3)(i-Bu)2/MoO2Cl2∙TNPP

Abstract

In this study, a butadiene-isoprene coordination polymerization was initiated by a binary molybdenum (Mo)-based catalytic system consisting of modified MoO2Cl2 as the primary catalyst, triethyl aluminum substituted by m-cresol as the co-catalyst and tris(nonyl phenyl) phosphate (TNPP) as the ligand. The effects of the amount of catalyst and type of co-catalyst were investigated in detail. Experimental results indicated that when the butadiene-isoprene coordination polymerization was initiated by the binary Mo-based catalytic system, the monomer conversion could reach 90%. The resulting butadiene units were primarily based on 1,2-structures, and the reactivity ratios of butadiene and isoprene were 1.13 and 0.31, respectively. The reaction in the catalytic system was attributed to the non-ideal and non-constant ratio copolymerization. When the addition of isoprene monomers was relatively low, the isoprene units on the butadiene-isoprene copolymers were primarily based on the 1,2- and 3,4-structures. Moreover, the orientation of active centers to 1,2- and 3,4-structures gradually decreased with an increase in the addition of isoprene monomers, which resulted in the generation of high vinyl butadiene-isoprene copolymers.

Randomly Coordinative Chain Transfer Copolymerization of 1,3-Butadiene and Isoprene: A Highly Atom-Economic Way for Accessing Butadiene/Isoprene Rubber

“…Therefore, synthesizing such copolymers with totally random structures, together with exactly tunable molecular weights, narrow molecular weight distributions, and precisely controllable compositions is a goal on which persistent endeavor has been implemented. To date, anionic living polymerization and coordination-insertion living polymerization are the two most widely reported strategies to achieve such a goal; however, despite extensive reports on the copolymerization of 1,3-butadiene and isoprene, − only a few of them proceed in a living fashion; − moreover, for these living systems, only one polymer chain is produced from each molecule of the catalyst, which represents a low atom-economic fashion. Tapping a high atom-economic alternative is the long-term goal that is being pursued.…”

Effect of Isomer Composition of Hydroxy Terminated Polybutadiene (HTPB) in Low Shear Flow Behavior (Efek dari Komposisi Isomer dari Hydroxy Terminated Polybutadiene (HTPB) terhadap Sifat Alir dalam Geseran Rendah)

“…1,2-vinyl isomer is also detected by peak at 990 cm -1 . The wavelengths are the same as previous reports (Li, et al, 2019), (Wibowo, et al, 2020). While, for out-ofplane wagging vibrations of CH groups near 1,4-trans isomer, the peak is shown broad and clear at 960 cm -1 and slightly different from the previous report.…”

Preparation and Characterization of Soft-Hard Block Copolymer of 3,4-IP-b-s-1,2-PBD Using a Robust Iron-Based Catalyst System

“…However, the catalytic activity of this catalyst system towards IP monomers still needs to be improved. Limited examples of 3,4-PI and 1,2-PBD copolymers have been reported so far, just random copolymers of both [ 26 , 27 , 28 , 29 ]. This is primarily subject to two critical constraints as follows.…”