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Issue 20, 2020
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Syndio-and cis-1,4 dually selective copolymerization of polar fluorostyrene and butadiene using rare-earth metal catalysts

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Abstract

Synthesizing functional butadiene–styrene rubber through coordination polymerization is a theoretical challenge for polymer science, since functional monomers usually deactivate to the applied catalyst. Herein, we report the coordination copolymerization of polar para-fluorostyrene (pFS) and butadiene (BD) using pyridyl–methylene–fluorenyl supported complexes [(Py-CH2-Flu)Ln(CH2SiMe3)2(THF)n (Ln = Sc (1a), n = 0; Ln = Lu (1b), n = 1)] and pyridyl–cyclopentadienyl supported complexes [(Py-Cp)Ln(η3-C3H5)2 (Ln = Sc (2a), Lu (2b))]. Strikingly, complexes 2a and 2b exhibited dually >99% syndio- and >95% cis-1,4 regio- selectivities and showed obvious characteristics of living polymerization. The insertion of pFS can be facilely tuned in the full range of 0–100% by changing the pFS-to-BD feed ratio. Diblock P(pFS-BD) copolymers were isolated by concurrent addition of monomers and the kinetics study of the copolymerization reaction revealed that BD had the privilege to coordinate to the active metal center. Interestingly, the polymerizations of BD and pFS via pulse loading of BD afforded multi-block copolymers of a novel type of fluoro styrene–butadiene rubber with high thermal stability (Td = 368 °C). The microstructures of resultant copolymers were confirmed by 1H and 13C NMR measurements and different phase morphologies of the di- and multi-block polymers were displayed through atomic force microscopy (AFM).

Graphical abstract: Syndio-and cis-1,4 dually selective copolymerization of polar fluorostyrene and butadiene using rare-earth metal catalysts

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Supplementary files

Article information


Submitted
18 Jun 2020
Accepted
21 Aug 2020
First published
25 Aug 2020

Inorg. Chem. Front., 2020,7, 3961-3968
Article type
Research Article

Syndio-and cis-1,4 dually selective copolymerization of polar fluorostyrene and butadiene using rare-earth metal catalysts

Y. Zhong, C. Wu and D. Cui, Inorg. Chem. Front., 2020, 7, 3961
DOI: 10.1039/D0QI00719F

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