Calcium–Lithium Systems as Innovative Bimetallic Initiators for the Anionic Polymerization of Butadiene: Toward Control and High 1,4-trans Microstructure

Polybutadiene architecture and microstructure are key parameters for the mechanical and viscoelastic properties of rubber materials. The versatility of anionic polymerization can supply a variety of polymers with different architectures and chain end functionalization, but few reports show the abili...

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Bibliographic Details
Published inMacromolecules Vol. 57; no. 5; pp. 2376 - 2384
Main Authors La Porta, Thomas, Perrin, Renaud, Ray, Mélanie, Gadenne, Benoit, Dire, Charlotte, Carlotti, Stéphane
Format Journal Article
LanguageEnglish
Published American Chemical Society 12.03.2024
Subjects
Chemical Sciences
Polymers
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Summary:Polybutadiene architecture and microstructure are key parameters for the mechanical and viscoelastic properties of rubber materials. The versatility of anionic polymerization can supply a variety of polymers with different architectures and chain end functionalization, but few reports show the ability to increase 1,4-trans units of polybutadiene. Herein, we report the first controlled anionic polymerization of butadiene using an innovative bimetallic Ca:Li initiator. [(THF)2Ca­(HMDS)2]:[n-BuLi] in situ prepared allowed the polymerization of butadiene in apolar medium, with the control of molar masses, a low dispersity (below 1.2), a living character, and the modulation of 1,4-trans units between 55 and 80% while maintaining a low vinyl content (below 10%). The influence of the [Ca]/[Li] ratio on the polybutadiene microstructure, kinetics, control, and living character of the polymerization are investigated and discussed.
ISSN:0024-9297
1520-5835
DOI:10.1021/acs.macromol.3c02160