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Synthesis and coupling of ABx polysiloxane macromonomers to form highly branched polysiloxanes.

Yolsal, Utku and Hutchings, Lian R. (2019) 'Synthesis and coupling of ABx polysiloxane macromonomers to form highly branched polysiloxanes.', European polymer journal., 113 . pp. 254-259.


This work focuses on the synthesis of polysiloxane ABx macromonomers with functional groups (A [Si-H] and B [vinyl]) incorporated on to the polymer backbone, and the coupling of these functionalities to form randomly, but highly, branched polymers. The synthesis of the ABx macromonomers was performed by the anionic copolymerization of hexamethylcyclotrisiloxane (D3) and 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane (V3) monomers, followed by an end-capping/termination reaction with chloro(methyl)phenylsilane. The resulting macromonomers were coupled by a Pt(0) catalyzed hydrosilylation reaction, to yield highly branched polysiloxanes. The coupling reaction was investigated at different solution concentrations and using macromonomers with different extents of vinyl content. It was shown that a higher solution concentration resulted in higher degrees of chain coupling and branching, arising from efficient intermolecular coupling in preference to (the competing) intramolecular coupling (cyclization) reaction. Moreover, an increase in the mole fraction of vinyl monomer also resulted in higher levels of branching. With the ability to control the degree of branching, the strategy reported here provides a facile route to synthesize branched polysiloxanes (silicones) with varying flexibility and elasticity

Item Type:Article
Full text:(AM) Accepted Manuscript
Available under License - Creative Commons Attribution Non-commercial No Derivatives.
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Publisher statement:© 2019 This manuscript version is made available under the CC-BY-NC-ND 4.0 license
Date accepted:30 January 2019
Date deposited:01 February 2019
Date of first online publication:31 January 2019
Date first made open access:31 January 2020

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