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Polymerization of octamethylcyclotetrasiloxane between montmorillonite nanoplatelets initiated by surface anions

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Abstract

Research deals with the assessment of grafting of cyclosiloxanes onto organically modified montmorillonite (MMT) layers through anionic ring-opening polymerization (AROP) without additional catalyst or initiator. Pristine Na+-MMT was organically modified by systematically varying the hexadecyltrimethylammonium bromide (HDTMABr) loading level. X-ray diffraction and thermogravimetric analysis of differently modified MMTs (OMMTs) showed that HDTMABr cations that exchanged sodium cations were strongly attracted to the silicate platelet surfaces. Part of HDTMABr formed a sandwiched HDTMABr layer between organically modified silicate platelets. The obtained OMMTs were tested as initiator material for AROP of octamethylcyclotetrasiloxane (D4) in the bulk, since the D4 polymerization may be initiated by oxygen anions located on the silicate surfaces. The highest monomer conversion (91 % after 24 h at 80 °C) was observed when OMMT with HDTMABr amount equal to cation exchange capacity was used. At lower amounts of HDTMABr, the MMT was less organically modified and thus less compatible with D4. On the other hand, when the HDTMABr sandwiched layer was thicker, lower rates of polymerization were observed due to the hindered transport of monomer to silicate platelet surfaces. The active function of surface anions in MMT platelets in the initiation process was confirmed experimentally by varying the OMMT/D4 ratio. It was observed that monomer conversion increased with increasing OMMT/D4 ratio. The obtained composites were exfoliated. In the last part of the research, OMMT was added to the formulation for D4 emulsion polymerization, where HDTMABr was also used as an emulsifier. The obtained composite material had a significantly improved thermal stability.

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Acknowledgments

The financial support of this work by the Slovenian Ministry of Higher Education, Science and Technology (Grant P2-0191) is gratefully acknowledged. The authors would like to express their gratitude to Dr. Ines Mohorič for the TGA analysis.

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  1. Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna Pot 113, 1000, Ljubljana, Slovenia

    A. Ručigaj, M. Krajnc & U. Šebenik

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  1. A. Ručigaj
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  2. M. Krajnc
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Correspondence to U. Šebenik.

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Ručigaj, A., Krajnc, M. & Šebenik, U. Polymerization of octamethylcyclotetrasiloxane between montmorillonite nanoplatelets initiated by surface anions. Polym. Bull. 72, 1863–1878 (2015). https://doi.org/10.1007/s00289-015-1377-5

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  • DOI: https://doi.org/10.1007/s00289-015-1377-5

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