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Thermodynamics of 5,5‐dimethylperhydro‐1,3‐oxazin‐2‐one, its polymerization in bulk and poly(5,5‐dimethyl‐2‐oxo‐1‐oxa‐3‐azahexamethylene) between 0 K and 500 K
Author(s) -
Lebedev Boris,
Smirnova Natal'ya,
Telnoy Vadim
Publication year - 1996
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.1996.021971125
Subject(s) - polymerization , heat capacity , thermodynamics , monomer , chemistry , polymer , standard molar entropy , atmospheric temperature range , standard enthalpy of formation , calorimetry , polymer chemistry , organic chemistry , physics
The thermodynamic properties of the six‐membered cyclic urethane, viz. 5,5‐dimethylperhydro‐1,3‐oxazin‐2‐one (DIO, 1 ) and the corresponding polymer, poly(5,5‐dimethyl‐2‐oxo‐1‐oxa‐3‐azahexamethylene) (PDIO, 2 ) were studied by calorimetry. The temperature dependence of the heat capacity at constant pressure C p 0 of the monomer and the polymer was studied between 5 K and 500 K. Temperatures and enthalpies of physical transitions were determined. The energies of combustion of the above compounds were measured. From the results the thermodynamic functions C p 0 ( T )– H 0 (O), S 0 ( T ) G 0 ( T )– H 0 ( O ), were calculated for various physical states of the monomer and the polymer from 0 K to 500 K. The standard enthalpies of combustion Δ H comb 0 and the thermochemical parameters of formation of DIO and PDIO were estimated at temperature T = 298,15 K and pressure p = 101,325 kPa. The zero entropy S gt 0 (O) and configurational entropy S conf 0 of PDIO in the glassy state were evaluated. The thermodynamic parameters of the bulk polymerization of DIO were calculated in the range of 0 K to 400 K at standard pressure. It was established that an equilibrium of the polymerization reaction of DIO to PDIO is shifted towards the formation of the monomer in the whole temperature range studied from 0 K to 450 K.