Thermodynamics of triple alternating copolymer ethylene—carbon monoxide—propylene

Abstract

The temperature dependence of heat capacity of triple alternating copolymer ethyl ene-carbon monoxide-propylene with 23.4 mol.% of propane fragments was studied for the first time by adiabatic and dynamic calorimetry over the range of 6-480 K. The energy of copolymer combustion at 298.15 K was measured in isothermic calorimeter with stationary bomb. The thermodynamic parameters of phase and physical transitions were determined. The standard thermodynamic functions C p (T), H(T) -H(0), S(T) -S(0) and G(T) -H(0), for region from Т  0 to 320 K, the standard enthalpy of combustion and thermodynamic charac teristics of formation of the studied compound at 298.15 K were calculated from the experimen tal data. The thermodynamic parameters of alternating copolymerization of CO with ethylene and propylene at standard pressure over 0-300 К region were detemined.The production of biodegradable polymers, to which polyketones are related, is one of the ways to approach the problem of utilization of the polymer industry wastes.Polyketones represent a new generation of functional polymers with a complex of interesting properties. 1,2 There is an increasing research interest in the development and improvement of synthesis technologies and study of the features of the physicochemical properties of this class of (co)polymers. Earlier 3-8 we have published the results of calorimetric study of the thermodynamic properties of alternating double copolymers of carbon monoxide with ethylene, propylene, styrene, endo dicyclopentadiene, norbornadiene (keto ekzo cis structures), bicyclo[2,2,1] hepta 2,5 diene. Thermodynamic characteristics of rele vant polymerisation reactions were reported for tempera ture region of 0-500 K. This work is a continuation of studies on the thermodynamic properties of different rep resentatives of polyketones.The alternating double copolymer of ethylene-carb on monoxide (1:1) and triple copolymers of ethyl ene-carbon monoxide-propylene, synthesized from the mixtures with various ratio of ethylene and propylene and in the presence of 50 mol.% of carbon monoxide were studied 9 by the wide angle X ray scattering technique (WAXS), Raman spectroscopy and differential scanning calorimetry. It was shown that in double polyketone and triple copolymers, containing up to 2.9 mol.% of propyl ene, the two polymorphous phases ( and ) are observed, and in triple copolymers with high propylene content only  phase is presented. The results of study 9 of aliphatic ketone films of 150 μm thickness obtained by cooling the melt from a temperature above the melting tempera ture (Т fus ) to the room temperature with the rate of 15 K min -1 under the pressure were described. As the thermal behavior of polymers essentially depends on the prehistory of the sample, it is interesting to verify the pres ence of the  and  phases in the powder of the triple polyketone obtained during the synthesis at 363 K 10 with out preheating it over Т fus .The purpose of this work is the calorimetric study of the triple copolymer of ethyl...

Thermochemical Characteristics of Poly(olefins)ketones, Based on Carbon Monoxide, Ethylene and Butene-1

“…[20], H 2 (г), O 2 (г) [21] и энтропии СОЭБ-2 [12], были рассчитаны стандартные энтальпия Термодинамические характеристики сополимеризации монооксида углерода с этиле-ном и бутеном-1. Полученные выше данные были использованы для расчёта стандартных тер-модинамических характеристик сополимеризации монооксида углерода, этилена и бутена-1 при T = 298,15 К. Необходимые для расчётов данные об энтальпиях образования, абсолютных значе-ниях энтропии, температурах и теплотах фазовых превращений монооксида углерода, этилена и бутена-1 взяты из [19,20,[22][23][24]. Для расчёта термодинамических параметров сополимеризации при других температурах использовали форму Кирхгофа.…”