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Enhanced thermal stability of biobased crosslinked poly (isobornylacrylate-co-2-ethylhexylacrylate) copolymers

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Abstract

Polymerization kinetics as well as thermal properties of acrylic copolymers containing Isobornylacrylate- (IBOA) and 2-Ethylhexylacrylate- (2-EHA) units were investigated. Poly(IBOA-co-2-EHA) samples were synthesized via free radical photopolymerization/crosslinking reactions of IBOA and 2-EHA, in the presence of 1,6-hexanedioldiacrylate (HDDA) as crosslinking agent, to obtain chemically crosslinked polymer networks. High conversion rates of the acrylic double bonds of the monomers were obtained from investigation of the polymerization kinetics by infrared spectroscopy. Analysis of the thermal properties using differential scanning calorimetry revealed the appearance of a single glass transition of Poly(IBOA-co-2-EHA) over a large range of temperatures comprised between 208 and 321 K, depending on monomer composition. The evolution of the glass transition temperature was rationalized by applying the Fox, Gordon Taylor, and Brekner-Schneider-Cantow models, revealing presumably the existence of hydrogen bonding interaction involving the carbonyl groups of the acrylates. Several degradation processes were observed by thermogravimetrical analysis, especially that of the isobornylene group at low temperature followed by the degradation of the carbon backbone at higher temperatures. Increasing IBOA content leads to a higher thermal stability of Poly(IBOA-co-2-EHA). Each degradation step could be characterized separately exhibiting activation energies which strongly depend on the degradation time of each step.

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Acknowledgements

This work has been partially accomplished in the framework of an international research program (PHC Tassili). The authors gratefully acknowledge the support of the Algerian Ministry of Higher Education and Scientific Research (MESRS), the General Directorate of Scientific Research and Technological Development (DGRSDT) of Algeria, CampusFrance, the University of Tlemcen/Algeria, the CNRS, and the University and the CROUS of Lille/France.

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Authors and Affiliations

  1. UMR 8207 - UMET - Unité Matériaux Et Transformations, Univ. Lille, CNRS, INRAE, Centrale Lille, 59000, Lille, France

    Dounya Merah, Nouh Zeggai, Johan Sarazin, Donna Boutalbi, Ana Barrera, Hana Boughrara, Frédéric Cazaux, Philippe Supiot & Ulrich Maschke

  2. Laboratoire de Recherche sur les Macromolécules (LRM), Faculté des Sciences, Université Aboubakr Belkaïd de Tlemcen, 13000, Tlemcen, Algeria

    Dounya Merah, Lamia Bedjaoui & Nouh Zeggai

  3. Laboratoire Physico-Chimie des Matériaux-Catalyse et Environnement (LPCMCE), Université Des Sciences Et de La Technologie d’Oran Mohamed Boudiaf (USTOMB), 31000, Oran, Algeria

    Zohra Bouberka

  4. Unité de Dynamique et Structure des Matériaux Moléculaires (UDSMM), Université du Littoral - Côte d’Opale (ULCO), 62228, Calais Cedex, France

    Frédéric Dubois

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  1. Dounya Merah
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Correspondence to Ulrich Maschke.

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Appendix A

Appendix A

Table: Pyrolysis-GC/MS parameters used to perform pyrolysis experiments.

GC parameters

Oven temperature

40 °C

Colum flow

1.71 mL/min

Injector temperature

300 °C

Split ratio

1/100

Gas carrier

He

GC oven temperature program

(1) hold 95 min at 40 °C

(2) 40 °C to 320 °C at 10 °C/min

(3) hold 17 min at 320 °C

MS parameters

Source temperature

230 °C

Source type

Electron-Impact (EI) ionization source

m/z scan range

10—800

Software

GCMS real time analysis

F search (Frontier Lab)

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Merah, D., Bedjaoui, L., Zeggai, N. et al. Enhanced thermal stability of biobased crosslinked poly (isobornylacrylate-co-2-ethylhexylacrylate) copolymers. J Polym Res 29, 279 (2022). https://doi.org/10.1007/s10965-022-03139-7

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