Unusual cationic copolymerization behavior of a six-membered ring spiro-orthocarbonate bearing adamantane backbones with a monofunctional epoxide

Journal of Polymer Science, Part A: Polymer Chemistry

Volumn 43, Issue 8, 2005, Pages 1729-1740

  Hino, Tetsuo ^a   Ito, Yoshinori ^a   Endo, Takeshi ^a  

^a YAMAGATA UNIVERSITY   (Japan)

Author keywords

Adamantane; Cationic polymerization; Copolymerization; Networks; Ring opening polymerization; Spiro orthocarbonate

Indexed keywords

ADHESION; CARBONATES; DERIVATIVES; MONOMERS; POLYETHERS; REACTION KINETICS; RING OPENING POLYMERIZATION; THERMODYNAMIC STABILITY;

ADAMANTANE; CATIONIC COPOLYMERIZATION; NETWORKS; SPIRO-ORTHOCARBONATES;

COPOLYMERIZATION;

EID: 17644380272     PISSN: 0887624X     EISSN: None     Source Type: Journal    
DOI: 10.1002/pola.20633     Document Type: Article

References (55)

1. Kim, C. B.; Park, M. A.; Song, B.; Park, K. Bull Korean Chem Soc 2003, 24, 1371.
2. Alcoutlabi, M.; McKenna, G. B.; Simon, S. L. J Appl Polym Sci 2003, 88, 227.
3. Zhou, Z. Q.; Jin, B. K.; He, P. S. J Appl Polym Sci 2002, 84, 1457.
4. Takata, T.; Endo, T. Prog Polym Sci 1994, 18, 839.
5. Endo, T.; Sanda, F. In Polymeric Materials Encyclopedia; Salamone, J. C., Ed.; CRC: Boca Raton FL, 1996; p. 7554.
6. Baiely, W. J; Katsuki, H.; Endo, T. Am Chem Soc, Div Polym Chem Prepr 1974, 155, 445.
7. Endo, T.; Baiely, W. J. J Polym Sci Polym Chem Ed 1975, 13, 2525.
8. Endo, T.; Baiely, W. J. Makromol Chem 1975, 176, 2897.
9. Endo, T.; Arita, H. Makromol Chem Rapid Commun 1985, 6, 137.
10. Endo, T.; Maruoka, S.; Yokozawa, T. Macromolecules 1987, 20, 2690.
11. Takata, T.; Endo, T. Macromolecules 1988, 21, 900.
12. Takata, T.; Ariga, T.; Endo, T. Macromolecules 1992, 25, 3829.
13. Sakai, S.; Fujinami, T.; Sakurai, S. J Polym Sci, Polym Lett Ed 1973, 11, 631.
14. Fujinami, T.; Tsuji, H.; Sakai, S. Polym J 1977, 9, 552.
15. For example, cyclic monomers generally undergo polymerization with extensive volume shrinkage by ca. 10-20% (ref. 4), but the volume shrinkage can be depressed by copolymerization with an expanding monomer, such as SOC. See Hino, T.; Endo, T. Macromolecules 2003, 36, 5902; Hino, T.; Inoue, N.; Endo, T. J Polym Sci, Part A: Polym Chem 2004, 42, 5113; and references cited therein.
16. For example, cyclic monomers generally undergo polymerization with extensive volume shrinkage by ca. 10-20% (ref. 4), but the volume shrinkage can be depressed by copolymerization with an expanding monomer, such as SOC. See Hino, T.; Endo, T. Macromolecules 2003, 36, 5902; Hino, T.; Inoue, N.; Endo, T. J Polym Sci, Part A: Polym Chem 2004, 42, 5113; and references cited therein.
17. +) that were formed via cationic ring-opening reaction of each cyclic carbonate. In addition, in the case of N-SOC, the cation species might be more stabilized by (intramolecular) coordination of the cyclic olefin part than in the case of AD-SOC, and then decarboxylation of the cationic species might be depressed.
18. 2 units, although the monomer 1 has 6-SOC structure.
19. 3,7]decane), a highly symmetrical tricyclic hydrocarbon consisting of fused chair-form cyclohexane rings, has been inserted into the backbone of many polymers, including polysulfones, polyethers, polyamides, and polyimides, since these polymers exhibit high glass transition temperatures and chain stiffness with reduced crystallinity and enhanced solubility. See, for example: (a) Novikov, S. S.; Khardin, A. P.; Novako, I. A.; Radchenko, S. S. Vysokomol Soedin, Ser B 1974, 16, 155;
20. (b) Novikov, S. S.; Khardin, A. P.; Novako, I. A.; Radchenko, S. S. Vysokomol Soedin, Ser B 1976, 18, 462;
21. (c) Korshak, V. V.; Novikov, S. S.; Vinogradov, S. V.; Khardin, A. P.; Vygodskii, Y. S.; Novako, I. A.; Orlinson, B. S.; Radchenko, S. S. Vysokomol Soedin, Ser B 1979, 21, 248;
22. (d) Khardin, A. P.; Radchenko, S. S. Russ Chem Rev (Engl Transi) 1982, 51, 272;
23. (e) Novako, I. A.; Orlinson, B. S. Vysokomol Soedin, Ser B 1995, 37, 1209;
24. (f) Pixton, M. R.; Paul, D. R. Polymer 1995, 36, 3165;
25. (g) Chern, Y.-T.; Chung, W.-H. J Polym Sci, Part A: Polym Chem 1996, 34, 117;
26. (h) Chern, Y.-T.; Shiue, H.-C. Macromolecules 1997, 30, 4646;
27. (i) Watanabe, Y.; Shibasaki, Y.; Ando, S.; Ueda, M. J Polym Sci, Part A: Polym Chem 2004, 42, 144;
28. (j) Nemoto, N.; Ito, Y.; Endo, T. J Polym Sci, Part A: Polym Chem 2003, 41, 699;
29. (k) Liaw, D. J.; Hsu, C. Y.; Hsu, P. N.; Lin, S. L. J Polym Sci, Part A: Polym Chem 2002, 40, 2066;
30. (l) Liaw, D. J.; Hsu, J. J.; Liaw, B. Y. J Polym Sci, Part A: Polym Chem 2001, 39, 2951;
31. (m) Hsiao, S. H.; Li, C. T. J Polym Sci, Part A: Polym Chem 1999, 37, 1435;
32. (n) Hsiao, S. H.; Lee, C. T.; Chern, Y. T. J Polym Sci, Part A: Polym Chem 1999, 37, 1619;
33. (o) Chern, Y. T.; Shiue, H. C.; Kao, S. C. J Polym Sci, Part A: Polym Chem 1998, 36, 785;
34. (p) Jensen, J. J.; Grimsley, M.; Mathias, L. J. J Polym Sci, Part A: Polym Chem 1996, 34, 397;
35. (q) Malik, A. A.; Archibald, T. G.; Baum, K.; Unroe, M. R. J Polym Sci, Part A: Polym Chem 1992, 30, 1747;
36. (r) Kuntz, I.; Cheng, D. M.; Dekmezian, A. H.; Hsu, C. S. J Polym Sci, Part A: Polym Chem 1987, 25, 3127.
37. Hino, T.; Ito, Y.; Endo, T. J Polym Sci, Part A: Polym Chem 2004, 42, 3360.
38. Crivello, J. V.; Sasaki, H. J Macromol Sci Pure and Applied Chem 1993, A30 (2-3), 173.
39. Yashiro, T.; Saitou, T.; Kameyama, A.; Nishikubo, T. J Polym Sci Part A Polym Chem 2003, 41, 2304.
40. Kudo, H.; Ueda, K.; Sano, N.; Nishikubo, T. J Polym Sci Part A Polym Chem 2003, 41, 1952.
41. Kudo, H.; Morita, A.; Nishikubo, T. Polym J 2003, 35, 88.
42. Minegishi, S.; Tsutida, S.; Sasaki, M.; Kameyama, A.; Kudo, H.; Nishikubo, T. J Polym Sci Part A Polym Chem 2002, 40, 3835.
43. Kameyama, A.; Ueda, K.; Kudo, H.; Nishikubo, T. Macromolecules 2002, 35, 3792.
44. Inoue, S.; Aida, T. In Ring Opening Polymerization; Ivin, K. J.; Saegusa, T., Eds.; Elsevier: London, 1984; Vol. 1.
45. The reasons that we employed PGE as an epoxide in the present study are as follows: (a) In general, some bifunctional epoxides such as bisphenol A diglycidyl ether are highly viscous oils, and are extremely intractable, (b) PGE can be regarded as a half unit for bisphenol A diglycidyl ether, which is widely used as an epoxide model monomer, (c) The polymerization system with PGE can be carried out even at high temperature, due to its high boiling point.
46. Armarego, W. L. H.; Perrin, D. D. Purification of Laboratory Chemicals, 3rd ed.; Pergamon: Oxford, 1988.
47. Wenschuh, H.; Beyermann, M.; Krause, E.; Brudel, M.; Winter, R.; Schumann, M. J Org Chem 1994, 59, 3275.
48. 2 was confirmed from change of the color of the reagent.
49. The yields of the MeOH-insoluble copolymers were relatively low in the present case, presumably due to the incorporation of the adamantane unit into the polymer backbone, which generally gives the polymer enhancing solubility (ref. 6). However, our main purpose in the article is to clarify the copolymerization behavior of an epoxide and AD-SOC, which indicates unusual cationic ring-opening polymerization behavior. In addition, the yield should be increased by using appropriate solvent in the reprecipitation process, since the NMR spectra of the MeOH-soluble part did not exhibit peaks derived from the monomers (AD-SOC, 3, and 4). Moreover, the relatively low yield and Mn of the product in the present case might be improved by use of bifunctionalized epoxide and oxetane as a comonomer.
50. 3) δ 12.0, 28.8 (2 C), 31.6, 37.4, 38.7 (2 C), 39.9 (2 C), 40.6, 109.8, 147.9.
51. 3 [the monomer feed ratio: AD-SOC/PGE = 5/95], small signals around 3 ppm could be detected. However, the integration ratio of the z unit was nearly zero, as shown in Table 1. In addition, as described in the text, the peak pattern depending on the adamantane unit in the copolymerization with 10 mol % or 20 mol % of AD-SOC was found to be different from that with 5 mol % of AD-SOC.
52. Network polymer generally shows rather high mechanical strength and chemical and/or thermal stability. See, for example: (a) Seymour, R. B.; Carraher, C. E., Jr. Polymer Chemistry, 3rd ed.; Marcel Dekker: New York, 1992; and
53. (b) Griskey, R. G. Polymer Process Engineering; Chapman & Hall: New York, 1995.
54. 3, since the amount of such cation species including terminal active ones should inevitably increase with increase of the concentrate of the initiator, as described in the text.
55. Alder, R. W.; Phillips, J. G. E. In Encyclopedia of Reagents for Organic Synthesis; Paquette, L. A., Ed.; John Wiley & Sons: New York, 1995; Vol. 5, p. 3617.