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Kinetics and Mechanism of the Cationic Polymerization of Trioxane. III. Copolymerization with Cyclic Formals

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Abstract

Kinetics and mechanism of three cationic copolymerization systems of trioxane (TO) and 1,3-dioxolane (DO) and/or 1,3,5-trioxepane (TOP) including TO/DO 2.0/0.1, TO/DO/TOP 2.0/0.1/0.055, and TO/TOP 2.0/0.1 in a unit of mol/L in 1,2-ethylene dichloride at 30 °C were investigated via evaluations of yields of copolymers and conversions of monomer and comonomer(s) using a gravimetric method and gas chromatography, respectively. The reactivity of DO or TOP was higher than that of TO toward the copolymerizations. Two byproducts, namely, TOP (or DO) and tetroxocane (TOC), were formed during the copolymerization of TO and DO (or TOP). The equilibrium concentrations of TO, DO, TOP, and TOC were ca 0.40, 0.02, 0.02, and 0.02 mol/L, respectively, for the TO/DO and TO/TOP systems whereas relatively high equilibrium concentrations of DO and TOP at ca 0.035 mol/L were for the TO/DO/TOP system. As compared with TO homopolymer, the thermal stability of the copolymers was increased with increasing conversion. The finding that the TO/DO/TOP system having a relatively high amount of cyclic formals consumed in the copolymerization exhibited a relatively low thermal stability suggested that the transacetalization reactions proceeded mainly via oxocarbenium species other than cyclic oxonium species, as compared with the TO/DO and TO/TOP systems.

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  1. Department of Chemical Engineering, National Yunlin University of Science and Technology, Yunlin, Taiwan, 640, R.O.C

    Yeong-Tarng Shieh & Show-An Chen

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  1. Yeong-Tarng Shieh
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  2. Meei-Ling Lay
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Shieh, YT., Lay, ML. & Chen, SA. Kinetics and Mechanism of the Cationic Polymerization of Trioxane. III. Copolymerization with Cyclic Formals. Journal of Polymer Research 10, 151–160 (2003). https://doi.org/10.1023/A:1026097215009

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