Abstract
The stereocomplex formation between isotactic and syndiotactic poly(methyl methacrylate) (PMMA) molecules is studied in detail, using the techniques of thin layer chromatography (TLC), ultracentrifugation, X-ray diffraction, viscometry, and high-resolution NMR. It is shown that the 1:1 (iso/synd) complex is formed as the primary structure; further associations between the 1:1 complex and free syndiotactic molecules, when they exist in solution, occur to form the 1:2 (iso/synd) complex.The so-called “stereoblock” PMMA samples prepared with n-butylmagnesium chloride and diphenylmagnesium are analyzed by using tic technique. Evidence is thus shown for the stereochemical identity between the stereoblock PMMA and the stereocomplex which is formed by isotactic and syndiotactic PMMA in the ratio 1:2 (iso/synd). On the basis of this result, we conclude that the 1:2 stereocomplex may be formed during stereospecific polymerization of methyl methacrylate (MMA) with different Grignard’s types of catalysts.In relation to the above conclusion stereospecific polymerizations of MMA at −50°C with n-butylmagnesium chloride in toluene were carried out in the presence of either isotactic or syndiotactic PMMA. The results suggest that the stereospecific polymerization of MMA is closely linked to the stereocomplex formation. The presence of the isotactic polymer chains promotes preferentially the polymerization of MMA to the syndiotactic polymer chains, while the presence of the syndiotactic polymer chains appears to be a prerequisite for initiating the polymerization to the isotactic polymer chains so far as this catalytic system is employed at −50°C.
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Miyamoto, T., Inagaki, H. The Stereocomplex Formation in Poly(methyl methacrylate) and the Stereospecific Polymerization of Its Monomer. Polym J 1, 46–54 (1970). https://doi.org/10.1295/polymj.1.46
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DOI: https://doi.org/10.1295/polymj.1.46
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