Study of the dilute solution properties of various homo- and block co-polymers by variable temperature size exclusion chromatography
Das, Pradip Kumar
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The Variable Temperature Size Exclusion Chromatography (VTSEC) was used to study the dilute solution properties of various homo- and block copolymers as well as polymer blends, focus being primarily on the configuration-dependent properties such as average chain dimensions and hydrodynamic behavior of polymers. The study constituted of three parts. In the first part, the dilute solution properties of a series of poly(alkyl methacrylates) with varying side alkyl(ester) group were investigated as to the effect of the size of the side group on the average chain dimensions at various temperatures. The VTSEC results were found to reveal that the effect of the side group depends on the extent of chain flexibility imparted by the side group. In the second part, VTSEC was employed to investigate the applicability and validity of the various models for block copolymers in solution. For this purpose, several series of samples (all anionically synthesized) with various composition and molecular weight were used: i) poly(alkyl methacrylates), their diblock copolymers and blends and ii) diblock and triblock copolymers of poly(styrene/substituted styrene) and poly(butadiene/isoprene). VTSEC results showed that the applicability of each model to a block copolymer in solution depends on the compatibility among the components, the composition of the samples, the solvating power of the solvent used and the operating temperature. Micellization in the hydrocarbon diblock copolymer solutions was found to occur in selective solvent, its extent depending on the solubility parameter difference between the components, molecular weight, composition and solvent power. In the third part, poly(methyl methacrylate) samples with varying tacticities were studied as to the effect of stereochemical configuration on their dilute solution behavior and found to indicate that both syndiotactic and isotactic stereosequences are required for stereoassociation. Two new VTSEC data reduction procedures were devised in order to correct for the temperature drifts due to instrumentation in the first and to neutralize the effect of molecular weight in the second. In the second, termed as the Molecular Weight-Elution Volume Superposition Procedure, the effect of molecular weight alone was enutralized leaving only the effect of the intrinsic character (such as the size of the side group) of the sample in the elution behavior. Numerical computations, using the Matxrix Generation method based on the Rotational Isomeric State approximation, were carried out for stereoregular chains in order to evaluate their chain dimensions at various temperatures.
- Doctoral Dissertations