Abstract
The polymerization of vinyl monomers with organometallic compounds was carried out in the presence of monodentate or bidentate phosphoryl compounds with —N(CH3)2 substituents. The polymerization of styrene or α-methylstyrene (α-MeSt) with organomagnesium compounds was more facilitated in the presence of the bidentate donors than in the presence of the monodentate type. In the polymerization of acrylonitrile (AN) with diethylzinc or organoaluminium compounds, the bidentate phosphoramides were less effective donors than the monodentate ones. The latter polymerization was considered to be caused by the coordination of both the phosphoramides and AN with the organometallic compounds, and to be reduced by the undesirable coordination of the bidentate phosphoramides to the sites required for the coordination of AN. The equilibrium monomer concentration ([M]e) in the polymerization of α-MeSt was dependent on the solvents used for the polymerization; the values of [M]e was smaller in toluene than in tetrahydrofuran.
Similar content being viewed by others
Article PDF
References
M. Tomoi and H. Kakiuchi, Kogyo Kagaku Zasshi (J. Chem. Soc. Japan, Ind. Chem. Sect.), 73, 2367 (1970).
M. Tomoi and H. Kakiuchi, Polym. J., 5, 195 (1973).
M. Tomoi, K. Sekiya, and H. Kakiuchi, Polym. J., 6, 438 (1974).
M. Ikeda, T. Hirano, and T. Tsuruta, Abstracts, SPSJ 23rd Annual Meeting, Tokyo, June 5, 1974, p 195 and references therein.
A. Akimoto and T. Okada, J. Macromol. Sci., Chem., A7, 1555 (1973).
M. Ikeda, T. Hirano, and T. Tsuruta, Makromol. Chem., 150, 127 (1971).
J. Furukawa, N. Kawabata, and A. Kato, J. Polym. Sci., Part A-1, 5, 3139 (1967).
T. Narita, T. Yasumura, and T. Tsuruta, Polym. J., 4, 421 (1973).
M. W. G. de Bolster and W. L. Groeneveld, Rec. Trav. Chim., 90, 687 (1971).
M. Pianka, J. Appl. Chem., 5, 109 (1955).
H. J. Vetter and H. Nöth, Chem. Ber., 96, 1308 (1963).
V. Mark, Org. Synth., 46, 42 (1966).
W. J. Pope and C. S. Gibson, J. Chem. Soc., 101, 735 (1912).
H. F. Ebel and B. O. Wagner, Chem. Ber., 104, 307 (1971).
R. Noller, “Org. Syntheses Coll. Vol. II,” John Wiley & Sons, Inc., New York, N.Y., 1948, p 184.
C. R. Bohn, J. R. Schaejgen, and W. O. Satton, J. Polym. Sci., 55, 531 (1961).
H. W. McCormick, J. Polym. Sci., 25, 488 (1957).
D. J. Worsfold and S. Bywater, J. Polym. Sci., 26, 299 (1957).
J. Leonard and S. L. Malhotra, J. Polym. Sci., Part A-1, 9, 1983 (1971).
M. W. G. de Bolster and W. L. Groeneveld, Rec. Trav. Chim., 91, 171 (1972).
M. W. G. de Bolster and W. L. Groeneveld, Rec. Trav. Chim., 91, 95 (1972).
M. D. Joesten, M. S. Hussain, and P. G. Lenhert, Inorg. Chem., 9, 151 (1970).
M. W. G. de Bolster and W. L. Groeveneveld, Rec. Trav. Chim., 90, 477 (1971) and references therein.
M. Levy and M. Szwarc, J. Am. Chem. Soc., 82, 521 (1960).
R. Waack, A. Rembaum, J. D. Coombes, and M. Szwarc, J. Am. Chem. Soc., 79, 2026 (1957).
H. L. Hsieh and O. F. McKinney, J. Polym. Sci., Part B, 4, 843 (1966).
J. F. Henderson and M. Szwarc, Macromol. Rev., 3, 317 (1968).
W. E. Goode, F. H. Owens, R. P. Fellmann, W. H. Synder, and J. E. Moore, J. Polym. Sci., 46, 317 (1960).
R. G. Pearson, J. Chem. Educ., 45, 581 (1968).
R. G. Pearson, J. Chem. Educ., 45, 643 (1968).
W. E. Slinkard and D. W. Meek, Inorg. Chem., 8, 1811 (1969).
H. F. Ebel, Tetrahedron, 24, 459 (1968).
M. Tomoi and H. Kakiuchi, Bull. Chem. Soc. Jpn., 46, 3233 (1973).
D. N. Bhattacharyya, C. L. Lee, J. Smid, and M. Szwarc, J. Am. Chem. Soc., 85, 533 (1963).
M. Kurata, H. Okamoto, M. Iwama, M. Abe, and T. Homma, Polym. J., 3, 739 (1972).
G. Schwarzenbach, “Die Komplexometrishe Titration,” F. Enke Verlag, Stuttgart, 1965.
N. L. Zutty and F. J. Welch, J. Polym. Sci., 43, 445 (1960).
L. Pauling, “The Nature of the Chemical Bond”, Cornell University Press, Ithaca, N.Y., 1960, p 93.
T. Mole and E. A. Jeffery, “Organoaluminium Compounds”, Elsevier Publishing Co., Amsterdam, 1972, Chapter 12.
T. Fujimoto, N. Kawabata, and J. Furukawa, J. Polym. Sci., Part A-1, 6, 1209 (1968).
B. Rickson, J. Am. Chem. Soc., 93, 1693 (1971).
J. L. Namy, E. Henry-Basch, and P. Freon, Bull. Soc. Chim. France, 2249 (1970).
Ref. 38, Chapter 4.
M. Tomoi and H. Kakiuchi, Unpublished results.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Tomoi, M., Onozawa, T., Seki, K. et al. Anionic Polymerization of Vinyl Monomers with Organometallic Compound—Phosphoramide Systems. Polym J 7, 372–381 (1975). https://doi.org/10.1295/polymj.7.372
Issue Date:
DOI: https://doi.org/10.1295/polymj.7.372