• Bulletin of the Korean Chemical Society
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• v.22 no.11
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• pp.1255-1260
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• 2001

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.

• Polymer(Korea)
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• v.27 no.3
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• pp.255-264
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• 2003

Various chain sizes 3-arm star polystyrenes (PS, $M_{w}$=2.80$\times$10$^{5}$ , 2.49$\times$10$^{6}$ g/mol) in t-decalin solution were measured at the temperature range of 20~7$0^{\circ}C$ by means of viscometry and laser light scattering. In order to show universality in the expansion factor of 3-arm star polymer, it was expected that (N/ $R_{G,Br,o}$$^{2}$)$^{3}$2/$\tau$/$\tau$$_{C}$ would be used as an universal parameter, where $R_{G,Br,o}$ was the unperturbed radius of gyration of star PS. However, much better universality had been observed when (N/ $R_{G,Br,o}$$^{2}$)$^{3}$2/$\tau$/$\tau$$_{C}$ parameter of the linear PS was used even for the 3-arm star PS. It could be explained if branching effect had been already taken into account in the part of $\tau$/$\tau$$_{C}$(=[(Τ-Θ$_{Tc}$ )/Θ$_{Tc}$ ]/[(Θ$_{Tc}$ -Τ$_{c}$)/ $T_{c}$]). Here N and Θ$_{Tc}$ stand for the number of monomer unit in a single polymer chain and a kind of theta temperature as the critical solution temperature $T_{c}$ of the infinite molecular weight, respectively.ely.y.ely.