Syndiotactic polystyrene/atactic miscibility

Hong, B.K., Jo, W.H., and Kim. J. (1998) Miscibility of syndiotactic polystyrene/ atactic polystyrene blends by crystallization kinetics and enthalpy relaxation. Pdymer, 39, 3753. 

Poly(cyclohexyl acrylate) was shown to be miscible with PS with ucst behavior [720]. Random copolymers of cyclohexyl acrylate with n-butyl acrylate showed miscibility with PS above 50% cyclohexyl acrylate[721]. Poly(cyclohexyl methacrylate)/isotactic PS blends showed miscibility based on calorimetry and NMR studies [722]. The NMR results showed homogeneous behavior at a scale of 2.5-3.5 nm. Poly(4-trimethylsilyl styrene) miscibility with polyisoprene was observed with a lest behavior (critical temperature = 172 ° C at degree of polymerization of 370) [723]. The interaction parameter, showed the following relationship = 0.027—9.5/T. Isotactic and syndiotactic polystyrene both exhibit crystallinity, whereas atactic polystyrene is amorphous. Atactic PS/isotactic PS blends exhibited crystallization kinetics, which decreased linearly with atactic PS addition indicating miscibility [724]. The TgS of aPS and iPS are identical, thus Tg methods could not be employed to assess miscibility. Atactic PS/syndiotactic PS blends were also noted to be miscible with rejection of atactic PS in the interfibrillar region between the lamellar stacks of sPS [725]. 

Differential scanning calorimetry (DSC) experiments indicated that atactic polystyrene and polyvinyl methyl ether (PVME) form miscible blends [8,9]. Syndiotactic and isotactic polystyrene when blended with PVME, phase separate at aU temperatures above the glass transition temperature of PVME. Only weak van der Waals interactions between the phenyl rings in polystyrene with the methoxy group of PVME were detected using 2-dimensional nuclear magnetic resonance (NMR) spectroscopy. 

In conclusion, it was found from the SANS experiments that the change in tacticity of d-PS, that is, from atactic to syndiotactic, results in the decrease of miscibility of deutrated polystyrene (d-PS) with hydrogenous polystyrene (h-PS). 

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