Polymerization of 2,2-dimethyltrimethylene carbonate with tri-sec-butoxyaluminium; a kinetic study

✍ Scribed by Birgid Wurm; Helmut Keul; Hartwig Höcker

• Book ID: 102483527
• Publisher: John Wiley and Sons
• Year: 1994
• Tongue: English
• Weight: 384 KB
• Volume: 195
• Category: Article
• ISSN: 1022-1352
• DOI: 10.1002/macp.1994.021951017

✦ Synopsis

Abstract

The polymerization of 2,2‐dimethyltrimethylene carbonate (DTC, 1) with tri‐sec‐butoxyaluminium (Al(O‐sec‐Bu)~3~) proceeds with suppression of macrocyclics formation. The propagation of the polymerization proceeds pseudoanionically via insertion. Within the scope of a kinetic treatment, the time‐conversion relationship was determined for the polymerization of DTC with Al(O‐sec‐Bu)~3~ as initiator and toluene as solvent. For a polymerization temperature between 15°C and 74°C, the apparent rate constant was found to be between 0,1 and 1,0 L · mol^−1^ · s^−1^. Using the Arrhenius plot the experimental temperature coefficient (20,6 kJ · mol^−1^) as well as the frequency factor of the polymerization (1,3 · 10^3^ L · mol^−1^ · s^−1^) were determined. Investigation of the dependence of the rate of polymerization on the initiator concentration revealed a degree of aggregation of 2 for the active species.