Abstract
Living polymerization of several substituted acetylenes such as [o-(trimethylsilyl)phenyl]acetylene (o-Me3Si- phenylacetylene), 1-chloro-1-octyne, (o-methylphenyl)acetylene (o-Me-phenylacetylene) was investigated by using a MoOCl4-based catalyst, MoOCl4–Et3Al–EtOH (1:1:3—4). It was proved that o-Me3Si-phenylacetylene polymerizes in a living fashion with the MoOCl4–Et3Al–EtOH catalyst in the temperature range 0—30°C. The Mw/Mn was as small as 1.05. The absolute Mn values of poly(o-Me3Si-phenylacetylene) were determined by vapor pressure osmometry (VPO), and the following relationship was obtained; Mn(VPO)=1.28×Mn (GPC; polystyrene calibration). The activation parameters for the polymerization of o-Me3Si-phenylacetylene were determined as ΔH≠=73 kJ mol−1 and ΔS≠=−13 J mol−1 K−1. MoOCl4–Et3Al–EtOH induced the living polymerization of 1-chloro-1-octyne as well to give a polymer with small polydispersity. Polymerization of o-Me-phenylacetylene formed a stereoregular living polymer having an Mw/Mn of 1.2 and 90% cis structure. Polymerizations of a few other phenylacetylenes having bulky ortho substituents also yielded living polymers, which is a tendency similar to those with previous MoOCl4-based catalysts.
Similar content being viewed by others
Article PDF
References
S. Kobayashi, Ed., “Catalysis in Precision Polymerization,” Wiley, Chichester, 1997.
J. D. Scollard and D. H. McConville, J. Am. Chem. Soc., 118, 10008 (1996).
C. M. Killian, D. J. Tempel, L. K. Johnson, and M. Brookhart, J. Am. Chem. Soc., 118, 11664 (1996).
K. Mashima, S. Fujiwara, Y. Tanaka, H. Urata, T. Oshiki, E. Tanaka, and A. Nakamura, Organometallics, 14, 2633 (1995).
B. L. Small, M. Brookhart, and A. M. A. Bennett, J. Am. Chem. Soc., 120, 4049 (1998).
S. T. Nguyan, L. K. Johnson, and R. H. Grubbs, J. Am. Chem. Soc., 114, 3974 (1992).
S. T. Nguyan, R. H. Grubbs, and J. W. Ziller, J. Am. Chem. Soc., 115, 9858 (1993).
E. L. Dias, S. T. Nguyan, and R. H. Grubbs, J. Am. Chem. Soc., 119, 3887 (1997).
H. H. Fox and R. R. Schrock, Organometallics, 11, 2763 (1992).
H. H. Fox, M. O. Wolf, R. O’Dell, B. L. Lin, R. R. Schrock, and M. S. Wrighton, J. Am. Chem. Soc., 116, 2827 (1994).
M. Bachmeiser and R. R. Schrock, Macromolecules, 28, 6642 (1995).
R. R. Schrock, S. Luo, N. Zanetti, and H. H. Fox, Organometallics, 13, 3396 (1994).
R. R. Schrock, S. Luo, J. C. Lee, N. Zanetti, and W. M. Davis, J. Am. Chem. Soc., 118, 3883 (1996).
T. Masuda, T. Yoshimura, J. Fujimori, and T. Higashimura, J. Chem. Soc., Chem. Commun., 1805 (1987).
T. Masuda, S. Hayano, E. Iwawaki, and R. Nomura, J. Mol. Catal. A, 133, 213 (1998).
S. Hayano, H. Kaneshiro, and T. Masuda, Kobunshi Ronbunshu, 54, 587 (1997).
Y. Kishimoto, P. Eckerle, T. Miyatake, T. Ikariya, and R. Noyori, J. Am. Chem. Soc., 116, 12131 (1994).
Y. Kishimoto, T. Miyatake, T. Ikariya, and R. Noyori, Macromolecules, 29, 5054 (1996).
S. Hayano and T. Masuda, Macromol. Chem. Phys., 198, 3041 (1997).
S. Hayano and T. Masuda, Macromolecules, 31, 3170 (1998).
H. Kaneshiro, S. Hayano, and T. Masuda, Macromol. Chem. Phys., 200, 113 (1999).
T. Masuda, H. Kaneshiro, S. Hayano, Y. Misumi, and L. Bencze, J. Macromol. Sci., Pure Appl. Chem., A34, 1977 (1997).
H. C. Brown, “Organic Synthesis via Boranes,” Wiley-Interscience: New York, N.Y., 1975, p 184.
K. Sonogashira, Y. Tohda, and N. Hagihara, Tetrahedron Lett., 50, 4467 (1975).
L. Brandsma, H. Hommes, R. L. P. de Jong, and H. D. Verkruijsse, Recl. Trav. Chim. Pays-Bas, 104, 226 (1985).
The polymerization of o-Me-phenylacetylene was too fast to monitor the monomer consumption.
H. Kaneshiro, T. Masuda, and T. Higashimura, Polym. Bull., 35, 17 (1995).
T. Masuda, T. Izumikawa, Y. Misumi, and T. Higashimura, Macromolecules, 29, 1167 (1996).
T. Mizumoto, T. Masuda, and T. Higashimura, Macromol. Chem. Phys., 196, 1769 (1995).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Kaneshiro, H., Hayano, S. & Masuda, T. Living Metathesis Polymerization of Several Substituted Acetylenes by MoOCl4–Et3Al–EtOH. Polym J 31, 348–352 (1999). https://doi.org/10.1295/polymj.31.348
Issue Date:
DOI: https://doi.org/10.1295/polymj.31.348