Reduction of dichlorosilanes with Mg metal in the presence of LiCl and Lewis acid such as FeCl2 or ZnCl2 was found to be the highly practical method for the synthesis of polysilanes (PS). This method is so useful and practical that PS can be prepared by stirring dichlorosilanes at room temperature. This method was successfully applied for the synthesis of various types of PS having a linear structure, a cyclic structure and silane-styrene copolymers as another type of PS. The structure of the reaction intermediates was also analyzed. At the initiation stage the results of FD-MS (Field desorption mass spectrometry) and GPC (Gel permeation chromatography) showed that linear oligomers were mainly formed by stepwise reactions, and then the high polymers and cyclic oligomers were formed in parallel.
KeywordsPolysilaneMagnesiumLewis Acid Catalysts
Yajima, S., Hayashi, J. and Omori, M. (1975) Continuous Silicon Carbide Fiber of High Tensile Strength. Chemical Letters, 9, 931-934. http://dx.doi.org/10.1246/cl.1975.931
Hasegawa, Y. and Okamura, K. (1986) Synthesis of Continuous Silicon Carbide Fibre. Journal of Materials Science, 21, 321-328. http://dx.doi.org/10.1007/BF01144739
Srinivasan, R. (1986) Ablation of Polymers and Biological Tissue by Ultraviolet Lasers. Science, 234, 559-565. http://dx.doi.org/10.1126/science.3764428
Miller, R.D., Willson, C.G., Wallraff, G.M., Clecak, N., Sooriyakumaran, R., Michl, J., Karatsu, T., McKinley, A.J., Klingensmith, K.A. and Downing, J. (1989) Polysilanes: Photochemistry and Deep UV Lithography. Polymer Engineering & Science, 29, 882-886. http://dx.doi.org/10.1002/pen.760291311
Miller, R.D., Wallraff, G.M., Clecak, N., Sooriyakumaran, R., Michl, J., Karatsu, T., McKinley, A.J., Klingensmith, K.A. and Downing, J. (1989) Polysilanes: Photochemistry and Deep UV lithography. Polymer Engineering & Science, 29, 882-886. http://dx.doi.org/10.1002/pen.760291311
Oku, T., Zushi, M., Yamada, M., et al. (2014) Next Generation Solar Battery Materials. Chemical Engineering, 59, 917-927.
Murase, H., Nishimura, H., et al. (2001) A New Technology for Maintaining the Strength of Electrofusion Joints by Using Polysilane. International Gas Research Conference (IGRC2001), Amsterdam, 5-8 November 2001, 134.
Murase, H. (2012) Fusion Bonding Agent Containing Polysilane Derivative and Its Bonding Method. JP 5021875.
Miller, R.D. (1989) Polysilane High Polymers. Chemical Reviews, 89, 1359-1410. http://dx.doi.org/10.1021/cr00096a006
Kashimura, S., Ishifune, M., Yamashita, N., Bu, H.B., Takebayashi, M., Kitajima, S., Yoshiwara, D., Kataoka, Y., Nishida, R., Kawasaki, S., Murase, H. and Shono, T. (1999) Electroreductive Synthesis of Polysilanes, Polygermanes, and Related Polymers with Magnesium Electrodes. The Journal of Organic Chemistry, 64, 6615-6621. http://dx.doi.org/10.1021/jo990180z
Shono, T., Kashimura, S. and Murase, H. (1992) Electroreductive Synthesis of Polygermane and Germane-Silane Copolymer. Journal of the Chemical Society, Chemical Communications, No. 12, 896-897. http://dx.doi.org/10.1039/c39920000896
Kashimura, S., Ishifune, M., Bu, H.B., Takebayashi, M., Kitajima, S., Yoshiwara, D., Nishida, R., Kawasaki, S., Murase, H. and Shono, T. (1997) Electroreductive Synthesis of Some Functionalized Polysilanes and Related Polymers. Tetrahedron Letters, 38, 4607-4610. http://dx.doi.org/10.1016/S0040-4039(97)00987-8
Ishifune, M., Kashimura, S., Kogai, Y., Fukuhara, Y., Kato, T., Bu, H.B., Yamashita, N., Murai, Y., Murase, H. and Nishida, R. (2000) Electroreductive Synthesis of Oligosilanes and Polysilanes with Ordered Sequences. Journal of Organometallic Chemistry, 611, 26-31. http://dx.doi.org/10.1016/S0022-328X(00)00327-2
Kashimura, S., Tane, Y., Ishifune, M., Murai, Y., Kataoka, Y., Murase, H. and Nishida, R. (2005) Electroreductive Synthesis of Polysilanes Promoted by the Anodically Dissolved Magnesium Ion. Electrochemistry, 73, 419-423.
Aitken, C., Harrod, J.F. and Samuel, E. (1986) Synthesis and Structural Characterization of an Unusual Silylzirconium Hydride Complex. Canadian Journal of Chemistry, 64, 1677-1679. http://dx.doi.org/10.1139/v86-276
Tilley, T.D. (1993) The Coordination Polymerization of Silanes to Polysilanes by a “.Sigma.-Bond Metathesis” Mechanism. Implications for Linear Chain Growth. Accounts of Chemical Research, 26, 22-29. http://dx.doi.org/10.1021/ar00025a004
Sakamoto, K., Obata, K., Hirata, H., Nakajima, M. and Sakurai, H. (1989) Chemistry of Organosilicon Compounds. 257. Novel Anionic Polymerization of Masked Disilenes to Polysilylene High Polymers and Block Copolymers. Journal of the American Chemical Society, 111, 7641-7643. http://dx.doi.org/10.1021/ja00201a070
Sakurai, H. (1989) Chemistry of Polysilanes and Development of New Preparations. Journal of Synthetic Organic Chemistry, Japan, 47, 1051-1059.
Yoshida, M., Seki, T., Nakanishi, F., Sakamoto, K. and Sakurai, H. (1996) Surface-Mediated Chromism in a Polysilane Langmuir-Blodgett Film. Journal of the Chemical Society, Chemical Communications, 11, 1381-1382. http://dx.doi.org/10.1039/cc9960001381
Matyjaszewski, K., Gupta, Y. and Cypryk, M. (1991) Anionic Ring-Opening Polymerization of 1,2,3,4-Tetramethyl- 1,2,3,4-Tetraphenylcyclotetrasilane. Journal of the American Chemical Society, 113, 1046-1047. http://dx.doi.org/10.1021/ja00003a050
Suzuki, M., Kotani, J., Gyobu, S., Kaneko, T. and Saegusa, T. (1994) Synthesis of Sequence-Ordered Polysilane by Anionic Ring-Opening Polymerization of Phenylnonamethylcyclopentasilane. Macromolecules, 27, 2360-2363. http://dx.doi.org/10.1021/ma00086a066
Murase, H., Fujiki, T. and Sakamoto, H. (2000) Synthesis of Polysilanes and Related Polymers Using Magnesium and Metal Chloride Catalysts. RadTech Japan 2000 Symposium, Yokohama, 13-15 November 2000, 110-111.
Murase, H., Sakamoto, H. and Fujiki, T. (2010) Active Metal Magnesium and Method for Producing Polysilane by Using the Same. JP 4559642.
Kashimura, S. and Murase, H. (2008) Practical Method for the Synthesis of Polysilanes Using Mg and Lewis Acid System. Tetrahedron Letters, 49, 269-271. http://dx.doi.org/10.1016/j.tetlet.2007.11.088
Ishikawa, M. and Kumada, M. (1970) Aluminium Chloride-Catalysed Skeletal Rearrangement of Permethylated Linear Polysilanes. Journal of the Chemical Society D: Chemical Communications, No. 3, 157a. http://dx.doi.org/10.1039/c2970000157a
Ishikawa, M. and Kumada, M. (1969) Ring contraction of Cyclohexasilanes to Silylcyclopentasilanes and the Preparation of Monofunctional Nonamethylcyclopentasilanes. Journal of the Chemical Society D: Chemical Communications, 567b-568. http://dx.doi.org/10.1039/c2969000567b
Kumada, M. (1975) Some Recent Studies of the Skeletal Transformations of Organopolysilanes. Journal of Organometallic Chemistry, 100, 127-138. http://dx.doi.org/10.1016/S0022-328X(00)88938-X
Tokumitsu, K., Yamada, M., Nakamura, M. and Kobori, K. (2012) The Effect of Adding Polysilane on Heat Fusion Properties of Various Kinds of Polyethylene. Journal of Applied Polymer Science, 126, E188-E194.
Tokumitsu, K., Kitagawa, Y., Murase, H. and Kobori, K. (2009) The Effect of Adding Polysilane Materials into Cyclo- Olefins on their Characteristics. Journal of the Society of Materials Science, Japan, 58, 741-746.
Murase, H., Kawasaki, S., Kitaoka, T., Furukawa, J., Ueda, H., Nishimura, H. and Yamada, K. (2015) Effects of Polysilane-Coating on Interface of Electrofusion Joints for Maintaining Strength. Materials Sciences and Applications, 6, 322-331. http://dx.doi.org/10.4236/msa.2015.64037