Single-feed one-step block copolymerization of n-octyloxyallene with phenylallene using π-allylnickel as initiator

Abstract

The π-allylnickel initiated block copolymerization of n-octyloxyallene and phenylallene takes place in one step from a single-feed mixture of the two monomers.

References

1. See, for example: A. S. Hoffmann and R. Bacckai, in Highpolymers, Vol. XVIII, Copolymerization, ed. G. E. Ham, Wiley, New York, 1964, ch. 6, p. 135; I. Goodman, in Development in Block Copolymer I, ed. I. Goodman, Elsevier, Essex, 1982, ch. 5, p. 127; D. B. Johns, R. W. Lenz and A. Luick, in Ring-Opening Polymerization, Vol. I, ed. K. J. Ivin and T. Saegusa, Elsevier, London, 1984, ch. 5, p. 218; R. N. Young, Trends Polym. Sci., 1993, 1, 149.
2. T. Saegusa, Y. Chujo, K. Aoi and M. Miyamoto, Makromol. Chem., Macromol. Symp., 1990, 32, 1.
3. W. J. Feast, V. C. Gibson, K. J. Ivin, E. Khosravi, A. M. Kenwright, E. L. Marshall and J. P. Mitchell, Makromol. Chem., 1992, 193, 2103.
4. For the living polymerization of allene derivatives, see: I. Tomita, Y. Kondo, K. Takagi and T. Endo, Macromolecules, 1994, 27, 4413; K. Takagi, I. Tomita and T. Endo, Maclomolecules, 1997, 30, 7386.
5. We have recently reported the two-feed block polymerization of alkoxyallenes with phenylallene by a π-allylnickel catalyst, in which block copolymers with controlled segment lengths could be successfully obtained by using additives (PPh₃ or CuI) over the course of the polymerization. See: K. Takagi, I. Tomita and T. Endo, Polym. Bull., in the press.
6. The yield of 54% corresponds to 91 wt% of 2. Namely, 3 was untouched at least until the conversion of 2 reached to 91%.