24 Solid-State Polymerization of Conjugated …
519
complexes of the monomers with aniline or TTF ring were able to be prepared.
However, their solid-state polymerization was not successful.
Monomers with phenylene or tetrafluorophenylene group sandwiched by two
butadiyne or hexatriyne moieties were prepared and polymerized. By cocrystallization of nonpolymerizable monomer 12 and polymerizable monomer 13, polydiacetylene copolymers, whose molar ratio of 13 was not less than approximately 60%, were
obtained. Both monomers 14 and 15 with hexatriyne moieties were polymerizable.
However, only one of the conjugated acetylenes reacted to form the single-chain
polydiacetylene and the polymers with two polydiacetylene backbones connected
by phenylene linkages seemed to be difficult to be synthesized.
Gel-formable butadiyne monomers 7–11 were able to be obtained by a simple
molecular design, in which 3,4,5-alkyloxyphenyl groups and hydrogen-bonding
groups were introduced. The nanofibrous structures as a microscopic view of the gels
were confirmed, and the macroscopic appearance of the gels depending on the solvent
used was explained by the fiber thicknesses. By extending the linear molecular design
of 10 into a ring shape, a macrocyclic monomer 16 with two butadiyne moieties was
synthesized, and the corresponding tubular polymer seemed to be obtained.
By applying appropriate combination of functional groups and hydrogen-bonding
groups to conjugated acetylene monomers, π-conjugated polymers with desired
optical and electronic functions can be synthesized via the solid-state polymerization. Further challenges to prepare polydiacetylenes with the single crystalline feature
advantageous to improve a variety of physical properties will be continued.
Acknowledgements Many of the results introduced in this chapter have been obtained in collaboration with professors in Yamagata University and the graduate and undergraduate students of our
laboratory, whose names are shown in the references. The authors thank them for their contribution
and effort.
References
1. Dunitz, J.D., Robertson, J.M.: The crystal and molecular structure of certain dicarboxylic acids.
Part III. Diacetylenedicarboxylic acid dehydrate. J. Chem. Soc., 1145–1156 (1947)
2. Wegner, G.: Topochemische Reaktionen von Monomeren mit konjugierten Dreifachbindungen
I. Mitt.: Polymerisation von Derivaten des 2.4-Hexadiin-1.6-diols im kristallinen Zustand. Z.
Naturforsch. 24b, 824–832 (1969)
3. Baughman, R.H., Yee, K.C.: Solid-state polymerization oflinear and cyclic acetylenes.
Macromol. Rev. 13, 219–239 (1978)
4. Enkelmann, V.: Structural aspects of the topochemical polymerization of diacetylenes.
in: Cantow H.J. (ed.) Polydiacetylenes, Advances in Polymer Science, vol. 63, pp. 91–136,
Springer, Berlin (1984)
5. Okawa, Y., Aono, M.: Linear chain polymerization initiated by a scanning tunneling microscope
tip at designated positions. J. Chem. Phys. 115, 2317–2322 (2001)
6. Okada, S., Nakanishi, H.: Recent progress in polydiacetylene material research for nonlinear
optics. Int. J. Nonlinear Opt. Phys. 3, 501–509 (1994)
519
complexes of the monomers with aniline or TTF ring were able to be prepared.
However, their solid-state polymerization was not successful.
Monomers with phenylene or tetrafluorophenylene group sandwiched by two
butadiyne or hexatriyne moieties were prepared and polymerized. By cocrystallization of nonpolymerizable monomer 12 and polymerizable monomer 13, polydiacetylene copolymers, whose molar ratio of 13 was not less than approximately 60%, were
obtained. Both monomers 14 and 15 with hexatriyne moieties were polymerizable.
However, only one of the conjugated acetylenes reacted to form the single-chain
polydiacetylene and the polymers with two polydiacetylene backbones connected
by phenylene linkages seemed to be difficult to be synthesized.
Gel-formable butadiyne monomers 7–11 were able to be obtained by a simple
molecular design, in which 3,4,5-alkyloxyphenyl groups and hydrogen-bonding
groups were introduced. The nanofibrous structures as a microscopic view of the gels
were confirmed, and the macroscopic appearance of the gels depending on the solvent
used was explained by the fiber thicknesses. By extending the linear molecular design
of 10 into a ring shape, a macrocyclic monomer 16 with two butadiyne moieties was
synthesized, and the corresponding tubular polymer seemed to be obtained.
By applying appropriate combination of functional groups and hydrogen-bonding
groups to conjugated acetylene monomers, π-conjugated polymers with desired
optical and electronic functions can be synthesized via the solid-state polymerization. Further challenges to prepare polydiacetylenes with the single crystalline feature
advantageous to improve a variety of physical properties will be continued.
Acknowledgements Many of the results introduced in this chapter have been obtained in collaboration with professors in Yamagata University and the graduate and undergraduate students of our
laboratory, whose names are shown in the references. The authors thank them for their contribution
and effort.
References
1. Dunitz, J.D., Robertson, J.M.: The crystal and molecular structure of certain dicarboxylic acids.
Part III. Diacetylenedicarboxylic acid dehydrate. J. Chem. Soc., 1145–1156 (1947)
2. Wegner, G.: Topochemische Reaktionen von Monomeren mit konjugierten Dreifachbindungen
I. Mitt.: Polymerisation von Derivaten des 2.4-Hexadiin-1.6-diols im kristallinen Zustand. Z.
Naturforsch. 24b, 824–832 (1969)
3. Baughman, R.H., Yee, K.C.: Solid-state polymerization oflinear and cyclic acetylenes.
Macromol. Rev. 13, 219–239 (1978)
4. Enkelmann, V.: Structural aspects of the topochemical polymerization of diacetylenes.
in: Cantow H.J. (ed.) Polydiacetylenes, Advances in Polymer Science, vol. 63, pp. 91–136,
Springer, Berlin (1984)
5. Okawa, Y., Aono, M.: Linear chain polymerization initiated by a scanning tunneling microscope
tip at designated positions. J. Chem. Phys. 115, 2317–2322 (2001)
6. Okada, S., Nakanishi, H.: Recent progress in polydiacetylene material research for nonlinear
optics. Int. J. Nonlinear Opt. Phys. 3, 501–509 (1994)