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T- and Q-rich Linear Silicones from the Piers-Rubinsztajn Reaction

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Abstract

Most silicone polymers are linear compounds derived from dimethylsiloxane (D) monomers; the incorporation of tri- (T) and tetra-functional (Q) monomers usually leads to elastomers. MQ or MT resins, high value materials used as reinforcing agents, are exceptions in that they are very highly branched, and highly reticulated but remain mobile and fluid. We report the formation of analogous linear T- and Q-rich polymers. The Piers-Rubinsztajn (PR) reaction between Si(OEt)4 and HSiMe(OSiMe3)2 led to mixtures of highly branched monomers that were separated by distillation to provide mono- and dialkoxy-Q monomers. Chain extension, also using the PR reaction with telechelic HSi-modified silanes, led to small to medium size linear polymers that were rich in T and Q groups. The polymers were mobile fluids, typically with only slightly higher viscosities than their unbranched counterparts. Alternating silphenylene Q(TM2)2 copolymers were also fluids as a consequence of steric inhibition of aromatic group association. The PR reaction provides a simple and viable strategy to introduce spatially controlled branching in pure, linear silicone polymers.

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Data Availability

Data for this paper may be found in the main text and Supplementary Information.

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Acknowledgments

We acknowledge with gratitude the financial support of the Natural Sciences and Engineering Council of Canada and the Faculty of Science, McMaster University for an equipment grant.

Funding

This research was supported by the Natural Sciences and Engineering Council of Canada.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, McMaster University, 1280 Main St. W., Hamilton, ON, L8S 4M1, Canada

    Michael Yin Wong, Ian L. Vishnu, Robert Bui, Yang Chen, Alyssa F. Schneider & Michael A. Brook

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  1. Michael Yin Wong
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  2. Ian L. Vishnu
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  3. Robert Bui
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  4. Yang Chen
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  5. Alyssa F. Schneider
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  6. Michael A. Brook
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Contributions

The original concept of this research was proposed by Dr. Brook. All synthetic research on QT compounds was performed by Dr. Wong. These two coauthors shared the writing activities. Dr. Chen and Dr. Bui provided additional physical characterization, and Dr. Schneider and Mr. Vishnu prepared the D silphenylene polymers for comparison purposes. All authors consent to publication of the work in its current form.

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Correspondence to Michael A. Brook.

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Supplementary information associated with this article 1H NMR, 13C NMR, 29Si NMR of M2T2-2, Figure S1-S4.

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Wong, M.Y., Vishnu, I.L., Bui, R. et al. T- and Q-rich Linear Silicones from the Piers-Rubinsztajn Reaction. Silicon 15, 887–895 (2023). https://doi.org/10.1007/s12633-022-02064-0

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