Abstract
Highly isotactic (it-) and highly syndiotactic (st-) 25mers and 50mers of MMA have been isolated from it- and st-PMMAs, respectively, by means of the preparative supercritical fluid chromatography (SFC) using carbon dioxide/ethanol as mobile phase and silica gel as stationary phase. The 25mers and 50mers with definite molecular weight (2561 and 5064) were useful as the standard materials in GPC for the calibration of molecular weight and the direct evaluation of instrumental spreading. The it-50mer eluted faster than the st-50mer in the GPC using THF as eluent. When a solution of a 1:1 mixture of the it- and st-50mers in THF was subjected to the GPC measurement at 3°C, the chromatogram showed two peaks at the elution volumes corresponding to the 50 and 100mers. The elution peak for the 100mer suggests that the it- and st-50mers form stereocomplex in a 1:1 ratio. The peak area for the stereocomplex varied from 0 to 9.0% of the whole chromatographic peaks, depending on the conditions (time and temperature) under which the mixed solution of the it- and st-50mers was allowed to stand. Stereocomplex formation was not observed for a mixture of the it- and st-25mers by similar GPC experiments.
Similar content being viewed by others
Article PDF
References
I. Bidd and M. C. Whiting, J. Chem. Soc., Chem. Commun., 543 (1985).
G. Ungar, J. Stejny, A. Keller, I. Bidd, and M. C. Whiting, Science, 229, 386 (1985).
K. S. Lee and G. Wegner, Makromol. Chem., Rapid Commun., 6, 203 (1985).
S. Kinugasa, A. Takatsu, H. Nakanishi, H. Nakahara, and S. Hattori, Macromolecules, 25, 4848 (1992).
R. E. Jentoft and T. H. Gouw, J. Polym. Sci., B7, 811 (1969).
E. Klesper and W. Hartmann, Eur. Polym. J., 14, 77 (1978).
F. P. Schmitz and E. Klesper, J. Supercritical Fluids, 3, 29 (1990).
K. Hatada, K. Ute, T. Nishimura, M. Kashiyama, T. Saito, and M. Takeuchi, Polym. Bull., 23, 157 (1990).
K. Ute, N. Miyatake, T. Asada, and K. Hatada, Polym. Bull., 28, 561 (1992).
A. M. Liquori, G. Anzuino, V. M. Corio, M. D’Alagni, P. de Santis, and A. Savino, Nature, 206, 358 (1965).
J. Spěváček and B. Schneider, Adv. Colloid Interface Sci., 27, 81 (1987).
I. A. Katime and J. R. Quintana, Makromol. Chem., 189, 1373 (1988).
C. J. Hawker and J. M. J. Fréchet, J. Am. Chem. Soc., 112, 7638 (1990).
T. M. Miller, T. X. Neeman, R. Zayas, and H. E. Bair, J. Am. Chem. Soc., 114, 1018 (1992).
K. Hatada, K. Ute, K. Tanaka, Y. Okamoto, and T. Kitayama, Polym. J., 18, 1037 (1986).
T. Kitayama, T. Shinozaki, T. Sakamoto, M. Yamamoto, and K. Hatada, Makromol. Chem., Suppl., 15, 167 (1989).
K. Ute, T. Asada, N. Miyatake, and K. Hatada, Makromol. Chem., Macromol. Symp., 67, 147 (1993).
K. Hatada and T. Kitayama, “Stereoregular Macromonomers with Respect to Main Chain and/or Side Chain” in “Macromonomers, Macroinitiators, Macroiniferters, Macroinifers—Design and Application,” M. K. Mishra, Ed., Polymer Frontiers Corp., 1993, p xxx.
J. M. G. Cowie, “Solutions of Stereoregular Polymers” in “Light Scattering from Polymer Solutions,” M. B. Huglin, Ed., Academic Press, London, 1972, p 605.
E. Heftmann “Chromatography,” Van Nostrand Reinhold Co., New York, 1975, p 334.
E. J. Vorenkamp, F. Bosschen, and G. Challa, Polymer, 20, 59 (1979).
T. Miyamoto and H. Inagaki, Polym. J., 1, 46 (1970).
J. Spěváček and B. Schneider, Makromol. Chem., 175, 2939 (1974).
R. Chiang, J. J. Burke, J. O. Threlkeld, and T. A. Orofino, J. Phys. Chem., 70, 3591 (1966).
J. Biros, Z. Masa, and J. Pouchly, Eur. Polym. J., 10, 629 (1974).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Ute, K., Miyatake, N., Osugi, Y. et al. Isotactic and Syndiotactic Pentacontamers (50mers) of Methyl Methacrylate Obtained by Fractionation with Preparative SFC: The GPC Analysis of the 50mers and Their Stereocomplex. Polym J 25, 1153–1160 (1993). https://doi.org/10.1295/polymj.25.1153
Issue Date:
DOI: https://doi.org/10.1295/polymj.25.1153
Keywords
This article is cited by
-
Uniform poly(methyl methacrylate) stereostars: synthesis, separation and stereocomplex formation
Polymer Journal (2010)
-
Preparation and solution properties of uniform three-arm star poly(methyl methacrylate)
Polymer Bulletin (1996)
-
Separation of poly(methyl methacrylate)s according to their tacticity
Polymer Bulletin (1994)