Hostname: page-component-586b7cd67f-dlnhk Total loading time: 0 Render date: 2024-11-25T15:39:38.188Z Has data issue: false hasContentIssue false

Conformational Rearrangement in the Nematic Phase of a Polymer Comprising Rigid and Flexible Sequences in Alternating Succession. II. Theoretical Results and Comparison with Experiments

Published online by Cambridge University Press:  26 February 2011

D. Y. Yoon
Affiliation:
IBM Almaden Research Center, 650 Harry Road, San Jose, California 95120
P. J. Flory
Affiliation:
Department of Chemistry, Stanford University, Stanford, California 94305
Get access

Abstrract

Theory predicts that the nematic state of a homopolymer comprising rigid and flexible sequences in alternating succession depends critically on the tendency of the flexible units to reconform to ordered extended conformations. When the relative statistical weight s* of such extended conformations is very small (very flexible), the chains undergo only a minor conformational rearrangement in the nematic state. Moreover, the clearing temperature and the orientational order of these nematic polymers are not much different from those of the monomeric liquid crystals. Hlowever, as the value of s* becomes larger than a certain critical value, an ordered (nematic) state exhibiting perfect orientational order and completely rodlike conformations becomes more stable than the state of only partial order. Hlence, an extensive conformational rearrangement is predicted to occur in nematic melts of the polymers when the flexible sequences are niot very flexible. These predictions are in good qualitative agreement with the conclusions from the thermodynamic and NMR measurements on two thermotropic polymers comprising identical rigid groups joined by flexible sequences of substantially different flexibility.

Type
Research Article
Copyright
Copyright © Materials Research Society 1989

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1. Flory, P.J., Advances in Polymer Science, 59, 1 (1984).CrossRefGoogle Scholar
2. Flory, P.J., Proc. R. Soc. London, Ser. A, 234, 73 (1956).Google Scholar
3. Flory, P.J. and Ronca, G., Mol. Cryst. Liq. Cryst., 54, 289 (1979).Google Scholar
4. Flory, P.J. and Abe, A., Macromolecules, 11, 1119 (1978).Google Scholar
5. Flory, P.J., Macromolecules, 11, 1138 (1978).Google Scholar
6. Flory, P.J. and Ronca, G., Mol. Cryst. Liq. Cryst., 54, 311 (1978).CrossRefGoogle Scholar
7. Warner, M. and Flory, P.J., J. Chem. Phys., 73, 6327 (1980).Google Scholar
8. Flory, P.J. and Irvine, P.A., J. Chem. Soc., Faraday Trans. I. 80, 1807 (1984).CrossRefGoogle Scholar
9. Bianchi, E., A. Cifferi and Tealdi, A., Macromolecules, 15, 1268 (1982).Google Scholar
10. Flory, P.J., Macromolecules, 11, 1141 (1978).Google Scholar
11. Matheson, R.R. Jr., and Flory, P.J.. Macromolecules. 14, 954 (1981).CrossRefGoogle Scholar
12. Flory, P.J. and Matheson, R.R. Jr., J. Phys. Chem., 88, 6606 (1984).CrossRefGoogle Scholar
13. Flory, P.J., the preceding paper of this volume.Google Scholar
14. Flory, P.J., Statistical Mechanics of Chain Molecules, (John Wiley & Sons, New York, 1969).Google Scholar
15. Tasaki, K. and Abe, A., Polym. J., 17, 641 (1985).Google Scholar
16. Sigaud, S., Yoon, D.Y. and Griffin, A.C., Macromolecules, 16, 875 (1983).Google Scholar
17. Volksen, W., Yoon, D.Y. and Cotts, P., Macronmolecules, 22, 3846 (1989).Google Scholar
18. Ballauffand, M. Floty, P.J., Ber. Bunsenges. Phys. Chem., 88, 530 (1984).CrossRefGoogle Scholar
19. Bruckner, S., Scott, J.C., Yoon, D.Y. and Griflin, A.C., Macromolecules. 18, 2709 (1985).Google Scholar
20. Yoon, D.Y., Bruckner, S., Volksen, W., Scott, I.C. and Griffin, A.C., Faraday Discuss. Cheim. Soc., 79, 41 (1985).Google Scholar
21. Boeffel, C., Ph.D. Thesis, Univ. Mainz, 1987.Google Scholar
22. Stoecklein, V., Scott, I.C., Volksen, W. and Yoon, D. Y., in preparation.Google Scholar
23. Ronca, G. and Yoon, D.Y., J. Chen. Phys., 76, 3295 (1984).CrossRefGoogle Scholar
24. Khokhlov, A.R. and Semenov, A.N., J. Stat. Phys., 38, 161 (1985)CrossRefGoogle Scholar