Abstract
New synthetic routes for silicon-containing styrene derivatives were investigated using p-allylstyrene (AST) as starting material. Lithium diisopropylamide induced a lithiation reaction of AST to form p-(1-lithioallyl)styrene (LiAST) without any side reaction such as polymerization under appropriate reaction conditions. Utilizing this carbanion as intermediate, synthesis of organosilicon-containing AST monomers was carried out. By adding trimethylsilyl chloride to the reaction system, mono-trimethylsilylated AST, [p-(3-trimethylsilyl-1-propenyl)-styrene; SAS] and bis(trimethylsilylated) AST, [p-[1,3-bis(trimethylsilyl)-2-propenyl]styrene; BSAS] were obtained by one pot. The yields of SAS and BSAS attained up to 91.7% and 88.5%, respectively under the appropriate reaction conditions. Radical polymerization of these monomers proceeded smoothly to form high molecular weight polymers without any gel formation even in bulk polymerization. The resulting polymers showed good membrane formabilities. Permeabilities of oxygen were in the range of 17—26 Barrers, keeping their selectivities against nitrogen through these membranes to be 3.3—3.5.
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E. F. Vansant and R. Dewolfs, “Gas Separation Technology,” Elsevier, Amsterdam, 1990.
T. Masuda, E. Isobe, T. Higashimura, and K. Takada, J. Am. Chem. Soc., 105, 7473 (1983).
S.-B. Choi, A. Takahara, N. Amaya, Y. Murata, and T. Kajiyama, Polym. J., 21, 433 (1989).
For reviews, see: Yu. P. Yampol’skii and V. V. Volkov, J. Membr. Sci., 64, 191 (1991)
Y. Nagasaki and T. Tsuruta, Makromol. Chem., 187, 1583 (1986).
Y. Nagasaki and T. Tsuruta, Makromol. Chem., Rapid Commun., 7, 437 (1986).
Y. Nagasaki, K. Kurosawa, and T. Tsuruta, Bull. Chem. Soc. Jpn., 63, 3036 (1990).
Y. Nagasaki, M. Suda, T. Tsuruta, K. Ishihara, and Y. Nagase, Makromol. Chem., Rapid Commun., 10, 255 (1989).
Y. Nagasaki, K. Kurosawa, M. Suda, S. Takahashi, T. Tsuruta, K. Ishihara, and Y. Nagase, Makromol. Chem., 191, 2103 (1990).
D. D. Perrin, W. L. F. Armarego, and D. R. Perrin, Purification of Laboratory Chemicals, 1966.
H. Gilman and A. H. Haubeim, J. Am. Chem. Soc., 69, 2609 (1947).
G. Greber and G. Engle, Makromol. Chem., 54, 122 (1962).
SAS: 1H NMR (CDCl3): δ 0.12 (9H, s, H-1), δ 1.73 (2H, J2,6=6.9Hz, d, H-2), δ 5.24 (1lH, J3,7=10.8Hz, d, H-3), δ 5.76 (1H, J4,7=17.6Hz, d, H-4), δ 6.26 (1H, J5,6=15.6Hz, d, H-5), δ 6.32 (1H, J6,2=6.9Hz, J6,5=15.6Hz, q, H-6), δ 6.74 (1H, J7,3=10.8Hz, J7,4=17.6Hz, q, H-7), δ 7.32 (2H, J8,9=8.3Hz, d, H-8), δ 7.38 (2H, J9,8=8.3Hz, d, H-9) BSAS: 1H NMR (CDCl3): δ 0.02 (9H, s, H-1),13 δ 0.13 (9H, s, H-2),13 δ 3.09 (1H, J3,7=9.3Hz, d, H-3), δ 5.22 (1H, J4,8=10.7 Hz, d, H-4), δ 5.63 (1H, J5,7=18.5Hz, d, H-5), δ 5.74 (1H, J6,8=17.6Hz, d, H-6), δ 6.40 (1H, J7,3=9.3 Hz, J7,5=18.5 Hz, q, H-7), δ 6.74 (1H, J8,4=10.7Hz, J8,6=17.6Hz, q, H-8), δ 7.11 (2H, J9,10=6.8Hz, d, H-9), δ 7.38 (2H, J10,9=6.8 Hz, d, H-10).
Assignments of the silylmethyl protons, H-1 and H-2, were carried out using trimethylvinylsilane and 4-(trimethylsilylmethyl)styrene as reference compounds.
F. L. Boschke, W. Fresenius, J. F. K. Huber, E. Pungor, G. A. Rochnitz, W. Simon, and Th. S. West, Ed., “Tables of Spectral Data for Structure Determination of Organic Compounds,” Springer-Verlag, Berlin, 1983.
N. Kato, K. Takeda, Y. Nagasaki, and M. Kato, Ind. Eng. Chem. Res., in press.
T. H. Kim, W. J. Koros, G. R. Husk, and K. C. Obrien, J. Membr. Sci., 37, 45 (1988).
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Nagasaki, Y., Hashimoto, Y., Kato, M. et al. Synthesis and Gas Permeation Behavior of Organosilicon-Containing Poly(p-allylstyrene)s. Polym J 26, 745–753 (1994). https://doi.org/10.1295/polymj.26.745
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DOI: https://doi.org/10.1295/polymj.26.745