Single-site β-diiminate zinc catalysts for the ring-opening polymerization of β-butyrolactone and β-valerolactone to poly(3-hydroxyalkanoates)

Journal of the American Chemical Society

Volumn 124, Issue 51, 2002, Pages 15239-15248

  Rieth, Lee R ^a   Moore, David R ^a   Lobkovsky, Emil B ^a   Coates, Geoffrey W ^a  

^a Department of Obstetrics Gynecology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ZINC ALKOXIDE INITIATOR;

BENZENE; CATALYSTS; COMPLEXATION; DEGRADATION; DIMERS; MOLECULAR WEIGHT; POLYMERS; REACTION KINETICS; ZINC;

POLYMERIZATION;

ALKANOIC ACID; AMIDE; BENZENE; BETA VALEROLACTONE; BUTYROLACTONE; DIMER; IMINE; LACTONE DERIVATIVE; MONOMER; OXIDE; POLY(3 HYDROXYBUTYRIC ACID); POLY(3 HYDROXYVALERATE); POLYMER; UNCLASSIFIED DRUG; ZINC;

ARTICLE; CATALYSIS; CATALYST; COMPLEX FORMATION; DEGRADATION; ELIMINATION REACTION; MOLECULAR WEIGHT; NUCLEAR MAGNETIC RESONANCE; POLYMERIZATION; REACTION ANALYSIS; RING OPENING; ROOM TEMPERATURE;

4-BUTYROLACTONE; CATALYSIS; CRYSTALLOGRAPHY, X-RAY; HYDROXYBUTYRATES; KINETICS; LACTONES; MAGNETIC RESONANCE SPECTROSCOPY; ORGANOMETALLIC COMPOUNDS; POLYESTERS; SOLUTIONS; STEREOISOMERISM; VALERATES; ZINC;

EID: 0037176278     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja020978r     Document Type: Article

References (59)

1. Müller, H.-M.; Seebach, D. Angew. Chem., Int. Ed. Engl. 1993, 32, 477-502.
2. Sudesh, K.; Abe, H.; Doi, Y. Prog. Polym. Sci. 2000, 25, 1503-1555.
3. Doi, Y.; Kumagai, Y.; Tanahashi, N.; Mukai, K. In Biodegradable Polymers and Plastics; Vert, M., Feijen, J., Albertsson, A., Scott, G., Chiellini, E., Eds.; The Royal Society of Chemistry: Cambridge, U.K., 1992; pp 139-148.
4. Cox, M. K. In Biodegradable Polymers and Plastics; Vert, M., Feijen, J., Albertsson, A., Scott, G., Chiellini, E., Eds.; The Royal Society of Chemistry: Cambridge, U.K., 1992; pp 95-99.
5. Okada, M. Prog. Polym. Sci. 2002, 27, 87-133.
6. Holmes, P. A. Phys. Technol. 1985, 16, 32-36.
7. Holmes, P. A. In Developments in Crystalline Polymers-2; Bassett. D. C., Ed.; Elsevier Applied Science: London, 1988; pp 1-66.
8. Billingham, N. C.; Proctor, M. G.; Smith, J. D. J. Organomet. Chem. 1988, 341, 83-93.
9. Leborgne, A.; Pluta, C.; Spassky, N. Macromol. Rapid Commun. 1994, 15, 955-960.
10. Möller, M.; Kånge, R.; Hedrick, J. L. J. Polym. Sci., Part A 2000, 38, 2067-2074.
11. Schechtman, L. A.; Kemper, J. J. PCT Int. Appl., WO 0077072, 2000; Chem. Abstr. 2001, 134, 57105.
12. Schechtman, L. A.; Kemper, J. J. PCT Int. Appl., WO 9520616, 1995; Chem. Abstr. 1995, 124, 9719.
13. Schechtman, L. A.; Kemper, J. J. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1999, 217, 508-509.
14. Jedlinski, Z.; Kowalczuk, M.; Kurcok, P.; Adamus, G.; Matuszowicz, A.; Sikorska, W.; Gross, R. A.; Xu, J.; Lenz, R. W. Macromolecules 1996, 29, 3773-3777.
15. Connor, E. F.; Nyce, G. W.; Myers, M.; Möck, A.; Hedrick, J. L. J. Am. Chem. Soc. 2002, 124, 914-915.
16. Kurcok, P.; Smiga, M.; Jedlinski, Z. J. Polym. Sci., Part A 2002, 40, 2184-2189.
17. Bloembergen, S.; Holden, D. A.; Bluhm, T. L.; Hamer, G. K.; Marchessault, R. H. Macromolecules 1989, 22, 1656-1663.
18. Leborgne, A.; Spassky, N. Polymer 1989, 30, 2312-2319.
19. Lenz, R. W.; Yang, J.; Wu, B.; Harlan, C. J.; Barron, A. R. Can. J. Microbiol. 1995, 41, 274-281.
20. Wu, B.; Lenz, R. W. Macromolecules 1998, 31, 3473-3477.
21. Hori, Y.; Hagiwara, T. Int. J. Biol. Macramol. 1999, 25, 237-245.
22. Kemnitzer, J. E.; McCarthy, S. P.; Gross, R. A. Macromolecules 1993, 26, 6143-6150.
23. Kemnitzer, J. E.: McCarthy, S. P.; Gross, R. A. Macromolecules 1993, 26 1221-1229.
24. Kricheldorf, H. R.; Lee, S.-R.; Scharnagl, N. Macromolecules 1994, 27, 3139-3146.
25. Kricheldorf, H. R.; Eggerstedt, S. Macromolecules 1997, 30, 5693-5697.
26. Hori, Y.; Suzuki, M.; Yamaguchi, A.; Nishishita, T. Macromolecules 1993, 26, 5533-5534.
27. Tanahashi, N.; Doi, Y. Macromolecules 1991, 24, 5732-5733.
28. Zhang, Y.: Gross, R. A.: Lenz, R. W. Macromolecules 1990, 23, 3206-3212.
29. Chamberlain, B. M.; Cheng, M.; Moore, D. R.; Ovitt, T. M.: Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 2001, 123, 3229-3238.
30. Cheng, M.; Attygalle, A. B.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 1999, 121, 11583-11584.
31. For other recent work on the polymerization of lactide with β-diiminate metal alkoxides, see: (a) Chisholm, M. H.; Gallucci, J.; Phomphrai, K. Inorg. Chem. 2002, 41, 2785-2794.
32. (b) Chisholm, M. H.; Huffman, J. C.; Phomphrai, K. J. Chem. Soc., Dalton Trans. 2001, 222-224.
33. (c) Dove, A. P.; Gibson, V. C.; Marshall, E. L.; White, A. J. P.; Williams, D. J. Chem. Commun. 2001, 283-284.
34. Cheng, M.; Moore, D. R.; Reczek, J. J.; Chamberlain, B. M.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 2001, 123, 8738-8749.
35. Cheng, M.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 1998, 120, 11018-11019.
36. Allen, S. D.; Moore, D. R.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc., in press.
37. Moore, D. R.; Cheng, M.; Lobkovsky, E. B.; Coates, G. W. Angew. Chem., Int. Ed. Engl. 2002, 41, 2599-2602.
38. Gross, R. A.; Zhang, Y.; Konrad, G.; Lenz, R. W. Macromolecules 1988, 21, 2657-2668.
39. In general, GPC number-average molecular weights do not correspond well with calculated theoretical molecular weights. In fact, for low [BBL]/[Zn] ratios (e.g., entry 1), GPC molecular weights are somewhat higher than calculated molecular weights, even though initiaton appears to be very fast and efficient for 1a (see Initiation). We tentatively attribute this mismatch to poor correlation between the polystyrene calibration of the GPC and the actual molecular weights of the PHB chains. However, as the [BBL]/ [Zn] ratio increases. GPC molecular weights do not grow proportionately. This could also be partly attributable to the GPC calibration, but there is evidence that side reactions play a role in this unexpected behavior.
40. Getzler, D. Y. L.; Mahadevan, V.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 2002, 124, 1174-1175.
41. For some recent examples of the copolymerization of β-butyrolactone and β-valerolactone, see: (a) Bloembergen, S.; Holden, D. A.; Bluhm, T. L.; Hamer, G. K.; Marchessault, R. H. Macromolecules 1987, 20, 3086-3089.
42. (b) Bloembergen, S.; Holden, D. A.; Bluhm, T. L.; Hamer, G. K.; Marchessault, R. H. Macromolecules 1989, 22, 1663-1669.
43. (c) Kobayashi, T.; Yamaguchi, A.; Hagiwara, T.; Hori, Y. Polymer 1995, 36, 4707-4710.
44. Noda, I. PCT Int. Appl., WO 0037544, 2000; Chem. Abstr. 2000, 133, 75001.
45. Noda, I. U.S. Patent 6,077,931, 2000; Chem. Abstr. 2000, 133, 59245.
46. n = 320 000 and PDI = 1.59. We are in the process of optimizing this reaction.
47. Lavallee, C.; Grenier, D.; Prud'homme, R. E.; Leborgne, A.; Spassky, N. In Advances in Polymer Synthesis; Culbertson, B. M., McGrath, J. E., Eds.; Plenum Press: New York, 1985; pp 441-460 and references therein.
48. 13C NMR indicates that the degree of isotacticity is very high (>95%).
49. Coates, G. W.; Cheng, M. PCT Int. Appl., WO 0008088, 2000; Chem Abstr. 2000, 132, 152332.
50. Cheng, M. Ph.D. Thesis, Cornell University, 2000.
51. The variable temperature NMR data described in the text were combined with an additional set of spectra recorded at 5 °C intervals from 25 °C to 5 °C with the same sample.
52. Interestingly, we had previously found an order in [Zn] of 1.56 for the polymerization of rac-lactide by 1a; see ref 29. We are currently seeking to understand the reason we obtained a higher order in catalyst for a seemingly similar polymerization.
53. Dubois, P.; Jacobs, C.; Jérôme, R.: Teyssié, P. Macromolecules 1991, 24. 2266-2270.
54. Kricheldorf, H. R.; Scharnagl, N.; Jedlinski, Z. Polymer 1996, 37, 1405-1411.
55. Kurcok, P.; Dubois, P.: Jérôme, R. Polym. Int. 1996, 41, 479-485.
56. Kricheldorf, H. R.: Berl. M.; Scharnagl, N. Macromolecules 1988, 21, 286-293.
57. Melchiors, M.; Keul, H.: Höcker, H. Macromol. Rapid Commun. 1994, 15, 497-506.
58. Melchiors, M.; Keul, H.; Höcker, H. Macromolerules 1996, 29, 6442-6451.
59. n = 43000.