LOGIN TO YOUR ACCOUNT

Username
Password
Remember Me
Or use your Academic/Social account:

CREATE AN ACCOUNT

Or use your Academic/Social account:

Congratulations!

You have just completed your registration at OpenAire.

Before you can login to the site, you will need to activate your account. An e-mail will be sent to you with the proper instructions.

Important!

Please note that this site is currently undergoing Beta testing.
Any new content you create is not guaranteed to be present to the final version of the site upon release.

Thank you for your patience,
OpenAire Dev Team.

Close This Message

CREATE AN ACCOUNT

Name:
Username:
Password:
Verify Password:
E-mail:
Verify E-mail:
*All Fields Are Required.
Please Verify You Are Human:
fbtwitterlinkedinvimeoflicker grey 14rssslideshare1
Jones, Richard G.; Budnik, Ulrich; Holder, Simon J.; Wong, William K.C. (1996)
Publisher: Amer chemical soc
Languages: English
Types: Article
Subjects: QD
Identifiers:doi:10.1021/ma960496y
Variations of yields and molecular weight parameters of poly(methylphenylsilylene) formed through sodium-mediated Wurtz reductive coupling of dichloromethylphenylsilane in toluene, xylene, diethyl ether, tetrahydrofuran, and diphenyl ether both in the presence and in the absence of 15-crown-5 and at different temperatures are described. The effects of various terminating reagents are also considered. The crown ether when it is present in the reaction mixture is shown to act as a phase transfer agent for the sodium and this is interpreted as having two effects. The first is to activate the alkali metal for reductive coupling, which at lower temperatures is a necessary condition for polymer formation. The other is to transport the alkali metal to points on the high molecular weight polymer chains where, as a prelude to backbiting, it induces a highly selective chain scission; this is explained by it occurring only at gauche defects in the otherwise rodlike all-trans sequences within the polymer in solution. The polymodal molecular weight distributions that are commonplace for polysilylenes are rationalized in terms of a competition between such activation and degradation processes.
  • The results below are discovered through our pilot algorithms. Let us know how we are doing!

    • (1) Miller, R. D.; Michel, J. Chem. Rev. 1989, 89, 1359 and references therein.
    • (2) Kipping, F. J. Chem. Soc. 1921, 119, 830.
    • (3) Kipping, F. J. Chem. Soc. 1924, 125, 2291.
    • (4) Trujillo, R. E. J. Organomet. Chem. 1980, 198, C27.
    • (5) Trefonas III, P. T.; Djurovich, P. I.; Zhang, X.-H.; West, R.; Miller, R. D.; Hofer, D. J. Polym. Sci. Polym. Lett. Ed. 1983, 21, 819.
    • (6) Wesson, J. P.; Williams, T. C. J. Polym. Sci. Polym. Lett. Ed. 1980, 18, 959.
    • (7) West, R.; David, L. D.; Djurovich, P. I.; Stearley, K. L.; Srinivasan, K. S. V.; Yu, H. 1981, 103, 7352.
    • (8) Mark, J. E.; Allcock, H. R.; West, R. Inorganic Polymers; Englewood Cliffs, Prentice-Hall Inc.: NJ, 1992; pp 186-236 and references therein.
    • (9) Gauthier, S.; Worsfold, D. Macromolecules 1989, 22, 2213.
    • (10) Miller, R. D.; Rabold, J.; Sooriyakumaran, R.; Flemming, W.; Fickes, G. N.; Farmer, B. L.; Kuzmany, H. In Inorganic and Organometallic Polymers; ACS Symposium Series 360; Zeldin, M., Wynne, K. H., Allcock, H. R., Eds.; American Chemical Society: Washington, DC, 1988; Chapter 4.
    • (11) West, R.; Wolff, A. R.; Peterson, D. J. J. Radiat. Curing 1986, 13, 35.
    • (12) Wolff, A. R.; West, R. Appl. Organomet. Chem. 1987, 1, 7.
    • (13) Yajima, S.; Hasegawa, Y.; Hayashi, J.; Iomora, M. J. Mater. Sci. 1980, 15, 720.
    • (14) Yajima, S.; Hayashi, J.; Omori, M. Chem. Lett. 1975, 931.
    • (15) Kepler, R. G.;Zeigler, J. M.; Harrah, L. A.; Kurtz, S. R. Bull. Am. Phys. Soc. 1983, 28, 362.
    • (16) Lovinger, A. J.; Davis, D. D.; Schilling, F. C.; Bovey, F. A.; Zeigler, J. M. Polym. Commun. 1989, 30, 356.
    • (17) Tilley, T. D. Acc. Chem. Res. 1993, 26, 22.
    • (18) Sakamoto, K.; Obata, K.; Hirata, H.; Nakajima, M.; Sakurai, H. J. Am. Chem. Soc. 1989, 111, 7641.
    • (19) Matyjaszewski, K.; Gupta, Y.; Cypryk, M. J. Am. Chem. Soc. 1991, 113, 1046.
    • (20) Miller, R. D.; Hofer, D.; McKean, D. R.; Willson, C. G.; West, R.; Trefonas III, P. T. In Materials for Microlithography; ACS Symposium Series 266; Thompson, L. F., Willson, C. G., Frechet, J. M. J., Eds.; American Chemical Society: Washington, DC, 1984; Chapter 14.
    • (21) Zeigler, J. M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1986, 27, 109.
    • (22) Cragg, R. H.; Jones, R. G.; Swain, A. C.; Webb, S. J. J. Chem. Soc., Chem. Commun. 1990, 1147.
    • (23) Chen, S. M.; David, L. D.; Haller, K. J.; Wadsworth, C. L.; West, R. Organometallics 1983, 2, 409.
    • (24) Zeigler, J. M.; McLoughlin, L. I.; Perry, R. J. J. Inorg. Organomet. Polym. 1991, 1, 531.
    • (25) Jones, R. G.; Benfield, R. E.; Cragg R. H.; Swain, A. C. J. Chem. Soc., Chem. Commun. 1992, 1022.
    • (26) Worsfold, D. J. In Inorganic and Organometallic Polymers; ACS Symposium Series 360; Zeldin, M., Wynne, K. H., Allcock, H. R., Eds.; American Chemical Society: Washington, DC, 1988; Chapters 8 and 9.
    • (27) Matyjaszewski, K.; Greszta, D.; Hrkach, J. S.; Kim, H. K. Macromolecules 1995, 28, 59.
    • (28) Miller, R. D.; Ginsburg, E. J.; Thompson, D. Polym. J. 1993, 25, 807.
    • (29) Jones, R. G.; Benfield, R. E.; Cragg, R. H.; Swain, A. C.; Webb, S. J. Macromolecules 1993, 26, 4878.
    • (30) Fujino, M.; Isaka, H. J. Chem. Soc., Chem. Commun. 1989, 466.
    • (31) Matyjaszewski, K. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1987, 28, 224.
    • (32) Zeigler, J. M.; Harrah, L. A.; Johnson, A. W. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1987, 28, 424.
    • (33) Jones, R. G.; Benfield, R. E.; Cragg, R. H.; Swain, A. C. J. Chem. Soc., Chem. Commun. 1992, 112.
    • (34) Benfield, R. E.; Cragg, R. H.; Jones, R. G.; Swain, A. C. Nature 1991, 353, 340.
    • (35) Kim, H. K.; Matyjaszewski, K. J. Am. Chem. Soc. 1988, 110, 3321.
    • (36) Miller, R. D.; Thompson, D.; Sooriyakumaran, R.; Fickes, G. N. J. Polym. Sci.: Part A: Polym. Chem. 1991, 29, 813.
    • (37) Jenkner, P. K.; Suzuki, H.; Miller, R. D. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1994, 35, 500.
    • (38) Jones, R. G.; Benfield, R. E.; Cragg, R. H.; Evans P. J.; Swain, A. C. Polym. Commun. 1994, 35, 4924.
    • (39) Lacave-Goffin, B.; Hevesi, L.; Devaux, J. J. Chem. Soc., Chem. Commun. 1996, 765.
    • (40) This reaction time was chosen as the standard reaction time for purposes of comparability between the different systems. In some cases, optimum yields or molecular weight parameters were established at shorter reaction times but we have no evidence of there being subsequent substantial polymer degradation unless reactions were sustained for far longer times.
    • (41) The boiling point of diphenyl ether, 259 °C, is so high as to be considered an unrealistic reaction temperature and even at the temperature chosen for this reaction it was thought prudent to reduce the reaction time.
    • (42) Wolff, A. R.; Nozue, I.; Maxka, J.; West, R. J. Polym. Sci., Polym. Chem. 1988, 26, 701.
    • (43) Jones, R. G.; Benfield, R. E.; Evans, P. J.; Swain, A. C. J. Chem. Soc., Chem. Commun. 1995, 1465.
    • (44) Lacave-Goffin, B.; Hevesi, L.; Devaux, J. J. Chem. Soc., Chem. Commun. 1995, 769.
    • (45) Jones, R. G.; Benfield, R. E.; Cragg, R. H.; Swain, A. C.; Webb S. J.; Went, M. J. Polymer 1995, 36, 393.
    • (46) Jones, R. G.; Swain, A. C.; Holder, S. J.; Benfield, R. E. In Silicon-containing Polymers; Special Publication No. 166; Jones, R. G., Ed.; The Royal Society of Chemistry: Cambridge, UK, 1995; p 132.
    • (47) Jones, R. G.; Swain, A. C.; Holder, S. J.; Benfield, R. E.; Went, M. J.; Wiseman, A. J. In Metal Containing Polymeric Materials; Plenum Publishing Corp.: New York, 1996; pp 161-175.
    • (48) Though this observation only applies to the polymer that is found within the solution phase there is no reason to believe that the situation is appreciably different for polymer that might have precipitated, except perhaps in extent.
    • (49) Dye, J. L.; Andrews, C. W.; Mathews, S. E. J. Phys. Chem. 1975, 79, 3065.
    • (50) Dye, J. L. Angew. Chem., Int. Ed. Engl. 1979, 18, 587.
    • (51) Cotts, P. M.; Miller, R. D.; Trefonas III, P. T.; West, R.; Fickes, G. N. Macromolecules 1987, 20, 1046.
    • (52) Klingensmith, K. A.; Downing, J. W.; Miller, R. D.; Michl, J. J. Am. Chem. Soc. 1986, 108, 7438.
    • (53) Takeda, K.; Teramae, H.; Matsumoto, N. J. Am. Chem. Soc. 1986, 108, 8186
    • (54) Strazielle, C.; de Mahieu, A.-F.; Daoust, D.; Devaux, J. Polymer 1992, 33, 4174.
  • No related research data.
  • Discovered through pilot similarity algorithms. Send us your feedback.

Share - Bookmark

Cite this article