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Method for separating intramolecular and intermolecular interactions which influence polymer glass temperatures
Author(s) -
Wyman Donald P.
Publication year - 1967
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1967.070110807
Subject(s) - intermolecular force , mole fraction , polymer , intramolecular force , thermodynamics , alkyl , homologous series , intermolecular interaction , copolymer , glass transition , methacrylate , materials science , polymer chemistry , flory–huggins solution theory , chemistry , molecule , organic chemistry , physics
It is shown that the glass temperature ( T g ) for homopolymers of the type CH 2 CXYcan be expressed by a simple additive equation involving two terms: ( 1 ) a parameter E which is directly related to the molar cohesion energy and ( 2 ) a parameter E s * which is a measure of restricted rotation about valence bonds. E s * , at least for a large number of polymers, is related to the Mark‐Houwink K θ value (as measured in θ solvents at T θ ) via anti‐log E s * ∝ 1/ K θ 2/3 . It is also shown that for homologous series [e.g., poly( n ‐alkyl methacrylates)], there is a constant relationship between E and antilog E s * . The T g values for copolymers may be estimated by a simple weighted (via mole fraction) summation of the E and E s * values of the components. When used in this form, a linear variation between T g and composition is assumed, which may not be strictly correct but still yields useful approximations.