Issue 23, 2022

Scandium-catalyzed stereoselective block and alternating copolymerization of diphenylphosphinostyrenes and isoprene

Abstract

The coordination copolymerization of polar diphenylphosphinostyrenes (StPPh2) and isoprene (IP) by a half-sandwich scandium catalyst (C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2 afforded a new series of phosphine-functionalized alternating and block isoprene–styrene copolymers. In the copolymerization of p-StPPh2 with IP, the incorporation of p-StPPh2 into the polymer chains started after IP was almost completely consumed, yielding the p-StPPh2–IP diblock copolymers containing a syndiotactic-rich poly(p-StPPh2) block and a poly(IP) block containing 1,4- and 3,4-structures, probably because the coordination of IP to the catalyst is favored over that of p-StPPh2. In the copolymerization of o-StPPh2 with IP, the o-StPPh2–IP alternating copolymer was exclusively formed with the coexistence of the two monomers, because the successive insertion of o-StPPh2 was difficult due to steric hindrance caused by the phosphine/styrene chelation to the catalyst metal center. When an excess amount of IP was used in the copolymerization of o-StPPh2 and IP, the formation of a poly(IP) block was achieved after o-StPPh2 was consumed in the alternating copolymerization, thus affording block copolymers containing an o-StPPh2–IP alternating block and a poly(IP) block. Moreover, the incorporation of IP in the alternating copolymerization with o-StPPh2 took place in a regio- and stereospecific cis-1,4-fashion (95%), suggesting that the coordination (chelation) of o-StPPh2 to the catalyst could influence the regio- and stereoselectivity of IP polymerization.

Graphical abstract: Scandium-catalyzed stereoselective block and alternating copolymerization of diphenylphosphinostyrenes and isoprene

Supplementary files

Article information

Article type
Paper
Submitted
07 Mar 2022
Accepted
18 May 2022
First published
19 May 2022

Polym. Chem., 2022,13, 3498-3505

Scandium-catalyzed stereoselective block and alternating copolymerization of diphenylphosphinostyrenes and isoprene

T. Fu, L. Jiang, H. Sun, Z. Hou and F. Guo, Polym. Chem., 2022, 13, 3498 DOI: 10.1039/D2PY00290F

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