Abstract
It is shown that heat capacities of linear macromolecules consisting of all-carbon single-bonded backbones can be calculated from the appropriate contributions of substituted carbon atoms to a precision of about − 0.2±2.5% (155 data points), which is similar to the experimental precision. Heat capacity contributions of 42 groups are given over the full range of measurement and reasonable extrapolation. The quality of the addition scheme is tested on 16 series of measurements on homopolymers, copolymers and blends. The addition scheme works for all these different states of aggregation of the constituent groups. The basis of the addition scheme is discussed.
Zusammenfassung
Es wird gezeigt, daß Wärmekapazitäten von aus Hauptketten mit ausschließlich C-C-Einfachbindungen bestehenden Makromolekülen aus geeigneten Beiträgen der substituierten Kohlenstoffatome mit einer Genauigkeit bis etwa −0.2±2.5% (155 Datenpunkte) berechnet werden können, was der experimentellen Genauigkeit nahe kommt. Wärmekapazitätsbeiträge von 42 Gruppen wurden über den vollen Meßbereich hinweg und durch sinnvolle Extrapolation bestimmt und angegeben. Die Zuverlässigkeit des Additionsschemas wurde in 16 Meßreihen an Homopolymeren, Kopolymeren und Mischungen getestet. Das Additionsschema ist für alle diese verschiedenen Anordnungen der konstitutionellen Gruppen zutreffend. Die Grundlagen des Additionsschemas werden diskutiert.
Резюме
Показано, что теплоем косщи линейных макромолекул, состоя щих только из углерод углерод одинарных связей, мог ут быть вычислены, исх одя из отдельных вкладов замешенных атомов углерода, с точ ностью около −0,2 ±2,5% (155 точ ечных данных), что соответст вует экспериментальной т очногти. Теплоемкост и 42 групп-вкладов привед ены в широкой области измерений и дана их пр иемлемая экстраполя ция. Качество этой аддити вной схемы проверено на 16 серии измерений гомо полимеров, сополимер ов и смесей. Аддитивная схема спр аведлива для всех различных типов сочетания этих соста вных групп. Обсуждены основы пре дложенной аддитивной схемы.
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On leave from the University of Science and Technology of China, Hefei, Peoples Republic of China.
This work was supported through the many years it took to assemble the needed experimental data by the National Science Foundation,-Polymers Program, Grant # DMR 8317097.
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Gaur, U., Cao, M.Y., Pan, R. et al. An addition scheme of heat capacities of linear macromolecules. Carbon backbone polymers. Journal of Thermal Analysis 31, 421–445 (1986). https://doi.org/10.1007/BF01911074
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DOI: https://doi.org/10.1007/BF01911074