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Influence of the tetraalkoxysilane crosslinker on the properties of polysiloxane-based elastomers prepared by the Lewis acid-catalysed Piers-Rubinsztajn reaction
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Hickman, Andrew, Chmel, Nikola Paul, Cameron, Neil R., Keddie, Daniel J. and Schiller, Tara L. (2021) Influence of the tetraalkoxysilane crosslinker on the properties of polysiloxane-based elastomers prepared by the Lewis acid-catalysed Piers-Rubinsztajn reaction. Polymer Chemistry, 12 (34). pp. 4934-4941. doi:10.1039/D1PY00872B ISSN 1759-9954.
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WRAP-influence-tetraalkoxysilane-crosslinker-properties-polysiloxane-based-elastomers-prepared-Lewis-acid-catalysed-Piers-Rubinsztajn-reaction-2021.pdf - Accepted Version - Requires a PDF viewer. Available under License Creative Commons Attribution Non-commercial. Download (635Kb) | Preview |
Official URL: http://dx.doi.org/10.1039/D1PY00872B
Abstract
We investigate the preparation of polysiloxane-based networks under solvent-free, ambient conditions using the Lewis acid catalysed Piers-Rubinsztajn (PR) reaction of hydride-terminated siloxanes with various tetrafunctional alkoxysilanes (tetraethoxysilane, tetrapropoxysilane, tetra-n-buxoxysilane, tetra-s-butoxysilane, tetra-s-butoxysilane, and tetrakis(2-ethylbutoxy)silane) as crosslinkers. We explore the effects of polysiloxane chain length and crosslinker alkyl group on the rheological performance of the elastomers. By analysing the reaction progress by grazing angle Fourier-transform infrared spectroscopy (FTIR) and determining the rheological properties of the resulting materials, we show that the use of linear or branched alkoxysilanes strongly influences the morphology and properties of these network polymers. We have shown the PR process is can be tailored to reliably produce homogeneous, polysiloxane network materials. This work provides information on the relative rates of network formation under ambient conditions with an emphasis on the impact of crosslinker alkyl chain length. Our results show that electronics and sterics both play critical roles in influencing the the rate of the curing reaction. Crucially, we newly demonstrate the benefit of a having tertiary carbon α to the SiO reaction centre, as is the case for the tetra-s-butoxysilane crosslinker, for delivering exceptionally rapid network cure and a concomitant enhancement in storage modulus of the resultant materials.
| Item Type: | Journal Article | ||||||||
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| Subjects: | Q Science > QD Chemistry | ||||||||
| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Engineering > Engineering Faculty of Science, Engineering and Medicine > Engineering > WMG (Formerly the Warwick Manufacturing Group) |
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| Library of Congress Subject Headings (LCSH): | Silicones, Elastomers -- Synthesis, Fourier transform infrared spectroscopy , Silicon polymers | ||||||||
| Journal or Publication Title: | Polymer Chemistry | ||||||||
| Publisher: | Royal Society of Chemistry | ||||||||
| ISSN: | 1759-9954 | ||||||||
| Official Date: | 14 September 2021 | ||||||||
| Dates: |
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| Volume: | 12 | ||||||||
| Number: | 34 | ||||||||
| Page Range: | pp. 4934-4941 | ||||||||
| DOI: | 10.1039/D1PY00872B | ||||||||
| Status: | Peer Reviewed | ||||||||
| Publication Status: | Published | ||||||||
| Access rights to Published version: | Open Access (Creative Commons) | ||||||||
| Date of first compliant deposit: | 23 July 2021 | ||||||||
| Date of first compliant Open Access: | 26 July 2021 |
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