Analysis of Excluded Volume Effect in Theta Solvent Systems of Polymethyl Methacrylate and Polystyrene by Means of a Modified Scaled Temperature Parameter

Analysis of Excluded Volume Effect in Theta Solvent Systems of Polymethyl Methacrylate and Polystyrene by Means of a Modified Scaled Temperature Parameter

The expansion of two different kinds of hydrodynamic size of polymethyl methacrylate (PMMA Mw: 1.56- 2.04 ${\times}$ 106 g/mol) has been measured by dynamic light scattering and viscometry above the Flory $\theta$ temperature of the variou s solvents such as n-butyl chloride, 3-heptanone, and 4-heptanone. The expansion of PMMA chains was analyzed in terms of universal temperature parameters and also compared with previous results of polystyrene (PS) system. First it was found that simple $\tau/{\tau}c$ parameter no longer had its universality for the expansion behavior of hydrodynamic size in the chemically different linear polymer chains. However after modifying ${\tau}/{\tau}c$ parameter into $(Mw/Ro2)3}2(\tau/\tauc)$, we observed a much better universality for both PMMA and PS systems. Here Mw, Ro, $\tau[=(T-{\theta}$)/${\theta}$]$, and ${\tau}c[=({\theta}-Tc)/Tc]$ are defined as the weight average molecular weight, the unperturbed end-to-end distance, the reduced temperature and the reduced critical temperature, respectively.