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Thermal ageing of polydicyclopentadiene

Abstract : Polydicyclopentadiene (PDCPD) is a thermoset polymer synthesized from ring opening metathesis polymerization with the advantage of short processing time due to the presence of double bonds and the use of organometallic catalysts. In this thesis, PDCPD is for example considered as a candidate for the field-joint in a marine environment. The question of the durability of PDCPD has to be assessed. The objective of this work is to establish a non-empirical kinetic model for the lifetime prediction of PDCPD during thermal oxidation. Firstly, the characterization by Infrared spectroscopy and peroxide titration of PDCPD during its thermal oxidation was conducted to set up a kinetic model for additive-free PDCPD. In particular, the initiation rate constants have been identified especially through hydroperoxide decomposition rates; the termination rate constants have been obtained by specific experiments under various oxygen pressures. The consumption of double bonds in the polymer causes a significant increase in crosslink concentration then increasing yield stress of PDCPD. The kinetic model predicts those trends as well as the thickness of the oxidized layer. The effect of stabilizer aimed at slowing down the oxidation rate was also experimentally studied and modeled. In particular, hindered amine stabilizers were shown to be promising candidates with good stabilizing properties and compatible with ROMP catalysts. Lastly, the effect of thermal oxidation of PDCPD on water sorption was investigated. Virgin PDCPD presents very low water absorption due to its apolar groups. Whereas, aged PDCPD shows increased hydrophilicity associated with polar groups build-up (which can probably impact its lifetime in marine conditions.
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Submitted on : Monday, February 3, 2020 - 3:17:11 PM
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  • HAL Id : tel-02464846, version 1


Jing Huang. Thermal ageing of polydicyclopentadiene. Other. Ecole nationale supérieure d'arts et métiers - ENSAM, 2019. English. ⟨NNT : 2019ENAM0050⟩. ⟨tel-02464846⟩



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