Ring-opening metathesis copolymerization behaviors of cyclooctene and norbornene bearing a five- or six-membered ring cyclic carbonate

Journal of Polymer Science, Part A: Polymer Chemistry

Volumn 43, Issue 24, 2005, Pages 6599-6604

  Hino, Tetsuo ^a   Inoue, Naoto ^a   Endo, Takeshi ^a  

^a YAMAGATA UNIVERSITY   (Japan)

Author keywords

Copolymerization; Metathesis; ROMP

Indexed keywords

COPOLYMERIZATION; INFRARED SPECTROSCOPY; RUTHENIUM COMPOUNDS; THERMAL EFFECTS;

CYCLIC CARBONATE; METATHESIS; ROMP; VOLUME SHRINKAGE;

AROMATIC POLYMERS;

EID: 29144452831     PISSN: 0887624X     EISSN: None     Source Type: Journal    
DOI: 10.1002/pola.21124     Document Type: Review

References (26)

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9. For the past several decades, several volume-expanding monomers, including spiro orthocarbonates, cyclic carbonates, and bicyclic bis(γ-lactone)s, have been developed, and these monomers show volume expansion of several percent or no volume shrinkage during the ring-opening polymerization; see (a) Luck, R. M.; Sadhir, R. S. In Expanding Monomers: Synthesis, Characterization, and Applications; Sadhir, R. K.; Luck, R. M., Eds.; CRC: Boca Raton, FL, 1992;
10. (b) Endo, T.; Sanda, F. In Polymeric Materials Encyclopedia; Salamone, J. C., Ed.; CRC: Boca Raton, FL, 1996; p 7554;
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17. Hino, T.; Endo, T. Macromolecules 2003, 36, 5902;
18. (j) Hino, T.; Inoue, N.; Endo, T. J Polym Sci Part A: Polym Chem 2004, 42, 5113;
19. (k) Hino, T. J Polym Sci Part A Polym Chem 2005, 43, 5323.
20. Most polymerizations, including ROMP, generally are carried out with volume shrinkage, which usually causes serious problems in materials science, such as lowering of adhesion, voids, microcracks, and remaining stresses. This shrinkage is mainly considered to be derived from the proximity of monomer molecules caused by the polymerization. For example, vinyl and cyclic monomers generally undergo polymerization with extensive volume shrinkage (ca. 10-20%); see ref. 4(a) and references cited therein.
21. (a) Hino, T.; Inoue, N.; Endo, T. Macromolecules 2004, 37, 9660;
22. (b) Hino, T.; Inoue, N.; Endo, T. J Polym Sci Part A: Polym Chem, in press. Such volume-expanding behavior has not been reported before a polymerization versus after a polymeriza tion, except for the ring-opening polymerizations of cyclic carbonate moieties [see ref. 4(g)]. In addition, the specific volume expansion can be roughly explained as follows: Before the ROMP, monomers 2 and 3 should exist rather close to each other because of the relatively large dipole - dipole interaction based on the cyclic carbonate structure. However, this state should be disturbed along with the propagation of ROMP on the norbornene unit, mainly because of steric factors, including steric hindrance in the molecular/polymer structures. Thus, the ROMP of norbornene-containing five- or six-membered-ring cyclic carbonates (2 and 3, respectively) should specifically overcome the volume shrinkage derived from the formation of new bonds between monomers. Incidentally, cyclic carbonates have relatively large dipole moments. For example, the dipole moment of 2-oxo-1,3-dioxane (six-membered-ring cyclic carbonate) has been calculated to be 5.38 D.
23. The ROMP of norbornene itself proceeds along with approximately 2% volume shrinkage before the treatment versus after the treatment.
24. Perrin, D. D. Purification of Laboratory Chemicals, 3rd ed.; Pergamon: Oxford, 1988.
25. The norbornenes bearing cyclic carbonate units (2 and 3) were prepared according to the reported procedures. For 2, see (a) Chen, X.; McCarthy, S. P.; Gross, R. A. Macromolecules 1997, 30, 3470. For 3,
26. see (b) Newman, M. S.; Addor, R. W. J Am Chem Soc 1955, 77, 3789. See also our previous article (ref. 6).