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Intrinsic viscosities of four homopolymers and one copolymer in nonpolar solvents. II. Effect of solvent steric hindrance

ISSN:0887-6266
1981年第19卷第5期
Article
Danielle Filiatrault,Genevi,#xe;ve Delmas


Intrinsic viscosities at 25°C of an ethylene-propylene copolymer containing 81% ethylene (81% E) of polypentenamer (PPmer), polyisobutylene (PIB), polypentene-1 (PP-1), and polydimethylsiloxane (PDMS) have been measured in n-C9 and three branched nonanes and n-C7 and five branched heptanes. The effect of the solvent steric hindrance on the free energy, i.e., on the χ parameter was investigated. The highly sterically hindered, cruciform molecules 3,3-dimethylpentane and 3,3-diethylpentane are the best solvents for four of the five polymers. The enhancement of solvent quality due to the steric hindrance diminishes when the polymer free volume increases. The difference in [η] between 2,4-dimethylpentane and 2,3-dimethylpentane is ?50%, ?35%, ?2% for PPmer, PIB, PDMS, and can be correlated to a measure of the polymer free volume, i.e., the lower critical solubility temperature. The χ, χH, and χS are calculated from [η] using the Stockmayer-Fixman relation and from hurn:x-wiley:00981273:media:POL180190506:tex2gif-stack-1, the heat of mixing at infinite dilution of the polymer, obtained previously. With each polymer, a good correlation is found between hurn:x-wiley:00981273:media:POL180190506:tex2gif-stack-2 and [η] obtained with the six heptanes and four nonanes. The correlation points to the same effect being at the origin of χH and χS but of different magnitude. In cases showing the steric hindrance effect, a negative contribution occurs in hurn:x-wiley:00981273:media:POL180190506:tex2gif-stack-3 (or χH) which is larger in magnitude than the corresponding negative entropic contribution leaving a net negative effect in χ itself. Probably due to their very compact shape and fewer degrees of freedom, the cruciform solvents lose less entropy than the chain solvents in mixing.

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ISSN:0887-6266
1981年第19卷第5期
Article

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