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Thermophysical properties of the poly-1,1,1,3,3,3-hexafluoroisopropyl-2-fluoro acrylate


S. Zaitsev1, A. Markin1 and L. Kurushina1

1Nizhny Novrorod State University, Russia

Keywords: calorimetry, thermodynamics
property: thermodynamics, heat capacity, devitrification, thermal decomposition
material: polymer

The Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization of 1,1,1,3,3,3-hexafluoroisopropyl-2-fluoro acrylate (HFA) was carried studies in the presence of various concentrations of dibenzyl trithiocarbonate as a chain transfer agent, and various concentrations of AIBN as an initiator. Kinetic studies indicated that radical polymerization proceeded with apparent living character, deduced from experiments demonstrating an linear increase in number-average molecular weight with monomer conversion, narrow molecular weight distribution.

Firstly, the calorimetric study of the HFA by DCS204F1 Phoenix, equipped with the `mu` -sensor, from Netzsch-Geratebau GmbH over temperature range from 273 to 573 K was carry out. As results, the G-transition was revealed on DSC-curves for substances under study as well as the begining of thermal destruction temperature was determined. On obtained experimental results the standard thermodynamic characteristics of G-transition and glassy state were estimated. In addition, the some dependences in the parameters of G-transition vs. molecular weights and polydispersity index were determined and discussed.

The temperature dependence of heat capacity of HFA over the temperature range from 6 to 350 K was measured by adiabatic vacuum calorimetry for the first time. From obtained results the standard thermodynamic functions were calculated. Also, the zero entropy and configurational entropy were estimated and discussed. The low-temperature was analyzed based on Debye theory of solids and Tarasov theory for chain structures. As results, some conclusions about structure topology were proposed.

The research was supported by the Russian Foundation for Basic Research, project number 11-03-00782-a.


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