Macromolecular Stereochemistry: The Out-of-Proportion Influence of Optically Active Comonomers on the Conformational Characteristics of Polyisocyanates. The Sergeants and Soldiers Experiment

Journal of the American Chemical Society

Volumn 111, Issue 16, 1989, Pages 6452-6454

  Green, Mark M ^a   Reidy, Michael P ^a   Johnson, Robert J ^b   Darling, Graham ^b   O'Leary, Daniel J ^b   Willson, Grant ^b  

^a POLYTECHNIC UNIVERSITY   (United States)

^b IBM ALMADEN RESEARCH CENTER   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33845184268     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00198a084     Document Type: Article

References (16)

1. Carlini, C.; Ciardelli, F.; Pino, P. Makromol. Chem. 1968, 119, 244. Farina, M. Topics in Stereochemistry 1987, 17, 1, pp 84–86 in particular, is an excellent overview of this area.
2. Later work focused on copolymers with spectroscopically accessible chromophores. See: Ciardelli, F.; Salvadori, P. Pure Appl. Chem. 1985, 57, 931 and references therein.
3. A critical review is as follows: Bur, A. 1; Fetters, L. J. Chem. Rev. 1976, 76, 727. See, also: Berger, M. N.; Tidswell, B. M. J. Polym. Sci. Polym. Symp. 1973, No. 42, 1063. The most recent papers are the following: Itou, T.; Chirkiri, H.; Teramoto, A.; Aharoni, S. M. Polym. J. 1988, 20, 143. Itou, T.; Teramoto, A. Macromolecules 1988, 21, 2225.
4. The polymers were synthesized anionically following this reference: Shashoua, V. E.; Sweeny, W.; Tietz, R. F. J. Am. Chem. Soc. 1960, 82, 866.
5. For a good description of these methods see: Principles of Polymerization, 2nd ed.; Odian, G., Ed.; Wiley-Interscience: New York, 1981; Chapter 6.
6. Iwakura, Y.; Uno, K.; Kobayashi, N. J. Polym. Sci. Part A-1 1968, 6, 1087.
7. Although the sensitivity of the NMR was not reasonably adequate for the samples with less than 1% comonomer, mass spectrometric measurements (MS/MS) on cyclic trimers produced by pyrolysis of the copolymers confirm the random placement, including for sample H. Unpublished collaboration with R. G. Cooks and T. K. Majumdar (Purdue University). For related MS work, see: Durairaj, B.; Dimock, A. W.; Samulski, E. T.; Shaw, M. T. J. Polym. Sci. Polym. Chem. Ed., in press.
8. Also found for poly(n-butyl isocyanate), see: Milstein, J. B.; Charney, E. Macromolecules 1969, 2, 678. Troxell, T. C.; Scheraga, H. A. Macromolecules 1971. 4, 528.
9. Green, M. M.; Andreola, C.; Munoz, B.; Reidy, M. P.; Zero, K. J. Am. Chem. Soc. 1988, 110, 4063.
10. For a discussion of this characteristic and leading references, see: Green, M. M.; Gross, R. A.; Crosby, C., III; Schilling, F. C. Macromolecules 1987, 20, 992.
11. 13 Lifson, S.; Andreola, C.; Peterson, N. C.; Green, M. M. J. Am. Chem. Soc., in press.
12. Bovey, F. A. Chain Structure and Conformation of Macromolecules; Academic Press: New York, 1982. An especially clear discussion of random coil properties is found in the following: Mandelkern, L. An Introduction to Macromolecules, 2nd ed.; Springer-Verlag: New York, 1983. See, also: Morawetz, H. Macromolecules in Solution, 2nd ed.; Wiley-Interscience: New York, 1975; Chapter III.
13. These polymers are of theoretical interest: Mansfield, M. L. Macromolecules 1986, 19, 854. Cook, R. Macromolecules 1987, 20, 1961. For leading 4. references to liquid crystal formation, see: Itou, T.; Teramoto, A. in ref
14. Coles, H. J.; Gupta, A. K.; Marchal, E. Macromolecules 1977, 10, 182 and references therein.
15. The transition temperature (Figure 1) is unaffected by wide variation in concentration. Copolyisocyanates F, G, H, I (Table I) show parallel steep transitions. Hysteresis in moving to low temperature is observed, and at >5 mg/mL in sample F a thermally reversible gel appears to form. See: Reversible Polymer Gels and Related Systems; Russo, P. S., Ed.; ACS Symposium Series 350; American Chemical Society: Washington, DC, 1987. For related observations in other stiff polymers see: Rawiso, M.; Aime, J. P.; Fave, J. L.; Schott, M.; Muller, M. A.; Schmidt, M.; Baumgartl, H.; Wegner, G. J. Phys. France 1988, 49, 861.
16. High dipole moments in stiff polymers enhance aggregation in nonpolar solvents as best seen in poly(benzyl-L-glutamate). See: Poly(α-Benzyl-L-Glutamate) and Other Glutamic Acid Containing Polymers, Polymer Monographs, H. Block; Gordon and Breach Science: New York, 1983; Vol. 9, pp 81–84, and references therein.