Synthesis of cyclic polybutadiene via ring-opening metathesis polymerization: The importance of removing trace linear contaminants

Journal of the American Chemical Society

Volumn 125, Issue 28, 2003, Pages 8424-8425

  Bielawski, Christopher W ^a   Benitez, Diego ^a   Grubbs, Robert H ^a  

^a California Institute of Technology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

1,3 BUTADIENE DERIVATIVE; ALKENE DERIVATIVE; POLYMER;

ARTICLE; CATALYST; CIS ISOMER; CIS TRANS ISOMERISM; CROSS LINKING; GAS CHROMATOGRAPHY; GEL PERMEATION CHROMATOGRAPHY; MOLECULAR WEIGHT; PROTON NUCLEAR MAGNETIC RESONANCE; RING OPENING METATHESIS POLYMERIZATION; SYNTHESIS; TRANS ISOMER;

EID: 0038713937     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja034524l     Document Type: Article

References (22)

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3. Bielawski, C. W.; Benitez, D.; Grubbs, R. H. Science 2002, 297, 2041.
4. For a review on olefin metathesis, see: Ivin, K. J.; Mol. J. C. Olefin Metathesis and Metathesis Polymerization; Academic Press: London, 1997.
5. Fürstner has reported the utility of "cyclic" Ru-based catalysts in the synthesis of small molecules, see: Fürstner, A.; Ackermann, L.; Gabor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem. - Eur. J. 2001, 7, 3236.
6. For a review on the development of Ru-based olefin metathesis catalysts, see: Trnka, T.; Grubbs, R. H. Acc. Chem. Res. 2001, 15, 2345.
7. Jafarpour, L.; Stevens, E. D.; Nolan, S. P. J. Organomet. Chem. 2000, 606, 49.
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12. 1/2 ≈ hours) at room temperature.
13. Extensive chain tranfer in olefin metathesis polymerizations approximates a step-growth polymerization where PDIs of 2.0 are expected at high conversion; see ref 3 for further details.
14. The critical monomer concentration of COD has previously been determined to be ∼0.25 M at 25 °C, see: Suter, U. W.; Höcker, H. Makromol. Chem. 1988, 189, 1603 and Höcker, H.; Reimann, W.; Reif, L.; Ribel, K. J. Mol. Catal. 1980, 8, 191.
15. The critical monomer concentration of COD has previously been determined to be ∼0.25 M at 25 °C, see: Suter, U. W.; Höcker, H. Makromol. Chem. 1988, 189, 1603 and Höcker, H.; Reimann, W.; Reif, L.; Ribel, K. J. Mol. Catal. 1980, 8, 191.
16. Linear polybutadienes were prepared by using linear Ru catalyst 2. For examples of preparing polybutadienes via the ROMP of COD with Ru complexes coordinated with N-heterocyclic carbenes, see: Bielawski, C. W.; Grubbs, R. H. Angew. Chem., Int. Ed. 2000, 39, 2903 and Frenzel, U.; Weskamp, T.; Kohl, F. J.; Schattenman, W. C.; Nuyken, O.; Herrmann, W. A. J. Organomet. Chem. 2000, 606, 8.
17. Linear polybutadienes were prepared by using linear Ru catalyst 2. For examples of preparing polybutadienes via the ROMP of COD with Ru complexes coordinated with N-heterocyclic carbenes, see: Bielawski, C. W.; Grubbs, R. H. Angew. Chem., Int. Ed. 2000, 39, 2903 and Frenzel, U.; Weskamp, T.; Kohl, F. J.; Schattenman, W. C.; Nuyken, O.; Herrmann, W. A. J. Organomet. Chem. 2000, 606, 8.
18. 3): δ 130.0, 129.9, 129.5, 129.3, 32.8, 32.8, 32.7, 27.5.
19. Burchard, W. In Cyclic Polymers; Semlyen, J. A., Ed.; Elsevier Applied Science: London, 1986; pp 43-84.
20. COD and CDT are industrially synthesized through a Ni-catalyzed oligomerization of 1,3-butadiene. The formation of 4VC is an unavoidable side reaction. For further details, see: Gerhartz, W. Ullmann's Encyclopedia of Industrial Chemistry; VCH: Weinheim, Federal Republic of Germany, 1985.
21. For an example of polymerizing CDT using ROMP, see: Thorn-Csanyi, E.; Hammer, J.; Pflug, K. P.; Zilles, J. U. Macromol. Chem. Phys. 1995, 196, 1043.
22. 2, 45 °C, 12 h.