Molecular modeling of polymers 16. Gaseous diffusion in polymers : A quantitative structure-property relationship (QSPR) analysis

• Published in: Pharmaceutical research 1997-10, Vol.14 (10), p.1349-1354
• Main Authors: PATEL, H. C, TOKARSKI, J. S, HOPFINGER, A. J
• Format: Article
• Language: English
• Subjects: Biological and medical sciences; Carbon Dioxide - chemistry; Diffusion; General pharmacology; Medical sciences; Models, Molecular; Multivariate Analysis; Nitrogen - chemistry; Oxygen - chemistry; Pharmacology. Drug treatments; Physicochemical properties. Structure-activity relationships; Polymers - chemistry; Regression Analysis; Structure-Activity Relationship
• ISSN: 0724-8741; 1573-904X
• DOI: 10.1023/A:1012156318612

The purpose of this study was to identify the key physicochemical molecular properties of polymeric materials responsible for gaseous diffusion in the polymers. Quantitative structure-property relationships, QSPRs were constructed using a genetic algorithm on a training set of 16 polymers for which CO2, N2, O2 diffusion constants were measured. Nine physicochemical properties of each of the polymers were used in the trial basis set for QSPR model construction. The linear cross-correlation matrices were constructed and investigated for colinearity among the members of the training sets. Common water diffusion measures for a limited training set of six polymers was used to construct a "semi-QSPR" model. The bulk modulus of the polymer was overwhelmingly found to be the dominant physicochemical polymer property that governs CO2, N2 and O2 diffusion. Some secondary physicochemical properties controlling diffusion, including conformational entropy, were also identified as correlation descriptors. Very significant QSPR diffusion models were constructed for all three gases. Cohesive energy was identified as the main correlation physicochemical property with aqueous diffusion measures. The dominant role of polymer bulk modulus on gaseous diffusion makes it difficult to develop criteria for selective transport of gases through polymers. Moreover, high bulk moduli are predicted to be necessary for effective gas barrier materials. This property requirement may limit the processing and packaging features of the material. Aqueous diffusion in polymers may occur by a different mechanism than gaseous diffusion since bulk modulus does not correlate with aqueous diffusion, but rather cohesive energy of the polymer.