Mark-Houwink-Sakurada characterization

An appropriate formalism for Mark-Houwink-Sakurada (M-H-S) equations for copolymers and higher multispecies polymers has been developed, with specific equations for copolymers and terpolymers created by addition across single double bonds in the respective monomers. These relate intrinsic viscosity to both polymer MW and composition. Experimentally determined intrinsic viscosities were obtained for poly(styrene-acrylonitrile) in three solvents, DMF, THF, and MEK, and for poly(styrene-maleic anhydride-methyl methacrylate) in MEK as a function of MW and composition, where SEC/LALLS was used for MW characterization. Results demonstrate both the validity of the generalized equations for these systems and the limitations of the specific (numerical) expressions in particular solvents. 

Table 5. Polymer-solvent systems characterized by a rdatively large exponent v in the Mark-Houwink-Sakurada equation...

Osmotic pressure measurements for the determination of MW were used in 1900 to characterize starch. Twenty years later, the solution viscosity measurements were introduced by Staudinger for this purpose. However, it was Mark and his collaborators who developed the concept of the intrinsic viscosity ([r ]) and demonstrated that it provides information on the volume of individual colloidal particles, thus on MW. For the freely rotating chains the dependence (today known as Mark-Houwink-Sakurada equation) was obtained [Guth and Mark, 1934] ... 

Dilute Solution Properties. The rheology of dilute polymer solutions has been used extensively to gain insight into the structure and conformation of polymers in solution (11). The intrinsic viscosity provides a measure of the molecular weight of a polymer through a relationship such as the Mark-Houwink-Sakurada equation. Earlier studies of polyacrylamide (PAM) systems and details of the complexity of the characterization of high-molecular-weight water-soluble systems can be found in references 9, 13, and 14. 

The three-dimensional property was characterized based on a viscosity study. The [rj] value increased with the increasing M sls value and the a value of the Mark-Houwink-Sakurada equation was found to be 0.29, which was obtained from the slope of the logarithmic plots of [rj] versus Mw,sls- H is well known that the a value is less than 0.5 for the various hyperbranched polymers, so that Poly 13 had a spherical shape in solution (Jikei and Kakimoto, 2001). 

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