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A first insight into the thermal degradation mechanism of silylated methacrylic homopolymers synthesized via the RAFT process

Abstract : The mechanism of thermal degradation of two series of methacrylic-based polymers was investigated. Unconventional methacrylic homopolymers bearing a tert-butyldimethylsilyl ester group were synthesized by Reversible Addition–Fragmentation chain Transfer (RAFT) and conventional free radical polymerizations using 2,2-azobis(isobutyronitrile) as initiator. 2-Cyanoprop-2-yl dithiobenzoate (CPDB) was used as chain transfer agent (CTA) in the RAFT process. The thermal stability of this polymer family was compared to the well-known thermal behavior of poly(methyl methacrylate) PMMA under nitrogen atmosphere. RAFT- and free radically-synthesized polymers were studied by non-isothermal thermogravimetric experiments (TGA). TGA data revealed two main degradation stages for all polymers. The chain transfer agent was shown to limit the production of unsaturated polymer end-groups during polymerization and consequently the thermal stability of the resulting RAFT-polymers was enhanced. Depolymerization was the main thermal degradation mechanism of silylated polymers associated with a side-group elimination for RAFT-synthesized polymers. Pyrolysis–Gas chromatography–Mass spectrometry (Py–GC/MS) experiments clearly demonstrated the formation of volatile tert-butyldimethylsilanol and bis(tert-butyldimethylsiloxane) side-products.
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https://hal-univ-tln.archives-ouvertes.fr/hal-01364142
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Submitted on : Monday, September 12, 2016 - 2:03:04 PM
Last modification on : Saturday, March 19, 2022 - 11:44:01 AM

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Christine Bressy, van Giang Ngo, André Margaillan. A first insight into the thermal degradation mechanism of silylated methacrylic homopolymers synthesized via the RAFT process. Polymer Degradation and Stability, Elsevier, 2013, 98 (1), pp.115--121. ⟨10.1016/j.polymdegradstab.2012.10.023⟩. ⟨hal-01364142⟩

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