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Volumn 107, Issue 6, 2007, Pages 2388-2410

Making plastics from carbon dioxide: Salen metal complexes as catalysts for the production of polycarbonates from epoxides and CO2

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOHEXENE OXIDE; EPOXIDE MONOMERS; PROPYLENE OXIDE;

EID: 34447095233     PISSN: 00092665     EISSN: None     Source Type: Journal    
DOI: 10.1021/cr068363q     Document Type: Review
Times cited : (1445)

References (133)
  • 1
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    • Advances in Polycarbonates. Proceedings of Symposium of the American Chemical Society, March 2003, Washington, DC; Brunelle, D. J., Korn, M. R., Eds.; ACS Symposium Series 898; American Chemical Society: Washington, DC, 2005; 281 pp.
    • Advances in Polycarbonates. Proceedings of Symposium of the American Chemical Society, March 2003, Washington, DC; Brunelle, D. J., Korn, M. R., Eds.; ACS Symposium Series 898; American Chemical Society: Washington, DC, 2005; 281 pp.
  • 7
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    • Early efforts from this laboratory are summarized in a review by
    • Early efforts from this laboratory are summarized in a review by Rokicki, A.; Kuran, W. J. Macromol. Sci., Rev. Macromol. Chem. 1981, C21, 135.
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    • Rokicki, A.1    Kuran, W.2
  • 9
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    • (a) Rokicki, A.; Air Products and Chemicals, Inc.; Arco Chemicals Co. U.S. Patent 4,943,677, 1990.
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  • 10
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    • Air Products and Chemicals, Inc.; Arco Chemicals Co.; Mitsui Petrochemical Industries Ltd
    • U.S. Patent 5,026,676
    • (b) Motika, S.; Air Products and Chemicals, Inc.; Arco Chemicals Co.; Mitsui Petrochemical Industries Ltd. U.S. Patent 5,026,676, 1991.
    • (1991)
    • Motika, S.1
  • 11
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    • accessed May 29, 2006
    • http://www.empowermaterials.com (accessed May 29, 2006).
  • 27
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    • My widely employed reaction protocol is to dissolve the metal catalyst in the epoxide monomer prior to addition to an evacuated stainless steel reactor and pressurization with CO2. As inferred by the heat generated upon mixing the catalyst and epoxide, it is apparent that homopolymerization takes place before the copolymerization process is initiated. That is, the polymer afforded is a mixture of polycarbonate and polyether. This was verified in later studies.25 High CO2-containing copolymers were obtained by adding the catalyst to a reactor that contains the epoxide monomer under an elevated pressure of CO2
    • 2.
  • 38
    • 34447093033 scopus 로고    scopus 로고
    • It should be noted that there are several rather recent reviews covering the published literature through 2003, which encompass some of the subjects discussed here.3,36-39
    • 3,36-39
  • 45
    • 34447109403 scopus 로고    scopus 로고
    • -1 upon addition of a coordinating ligand, such as THF or cyclohexene oxide.
    • -1 upon addition of a coordinating ligand, such as THF or cyclohexene oxide.
  • 54
    • 34447101316 scopus 로고    scopus 로고
    • Upon heating the polycarbonate product, the cyclic carbonate thus formed was shown to be optically active
    • Upon heating the polycarbonate product, the cyclic carbonate thus formed was shown to be optically active.
  • 55
    • 34447109042 scopus 로고    scopus 로고
    • Sixth International Conference on Carbon Dioxide Utilization (ICCDU), Breckenridge, CO, September 9-14, 2001; released in abstract form on the conference website in July 2001.
    • Sixth International Conference on Carbon Dioxide Utilization (ICCDU), Breckenridge, CO, September 9-14, 2001; released in abstract form on the conference website in July 2001.
  • 58
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    • It should be noted parenthetically that I have generally found it difficult to isolate X-ray suitable crystals of five-coordinate (salen)-CrX complexes. That is, these molecules have a propensity to crystallize with a second axial ligand, salen)Cr(X)L, where L can be adventitious water
    • It should be noted parenthetically that I have generally found it difficult to isolate X-ray suitable crystals of five-coordinate (salen)-CrX complexes. That is, these molecules have a propensity to crystallize with a second axial ligand, (salen)Cr(X)L, where L can be adventitious water.
  • 64
    • 34447109617 scopus 로고    scopus 로고
    • Importantly, in this time regime, the monomer enchainment process has been shown to be first-order in catalyst and monomer concentrations
    • Importantly, in this time regime, the monomer enchainment process has been shown to be first-order in catalyst and monomer concentrations.
  • 74
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    • A similar zwitterion has been proposed as an intermediate in the oxidation of trialkyl phosphites by epoxides. Scott, C. B. J. Org. Chem. 1957, 22, 1118
    • A similar zwitterion has been proposed as an intermediate in the oxidation of trialkyl phosphites by epoxides. Scott, C. B. J. Org. Chem. 1957, 22, 1118.
  • 77
    • 0001254509 scopus 로고    scopus 로고
    • Precipitation and Crystallization Techniques
    • Jessop, P. G, Leitner, W, Eds, Wiley-VCH: Weinheim
    • Bertocco, A. Precipitation and Crystallization Techniques. In Chemical Synthesis Using Supercritical Fluids; Jessop, P. G., Leitner, W., Eds.; Wiley-VCH: Weinheim, 1999; p 108.
    • (1999) Chemical Synthesis Using Supercritical Fluids , pp. 108
    • Bertocco, A.1
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    • 34447095253 scopus 로고    scopus 로고
    • This study was performed in a similar manner to that employed for the related investigation involving cyclohexene oxide and CO2, except that it was necessary to add a cosolvent (toluene) due to the insolubility of poly(propylene carbonate) in neat propylene oxide
    • 2, except that it was necessary to add a cosolvent (toluene) due to the insolubility of poly(propylene carbonate) in neat propylene oxide.
  • 85
    • 34447102403 scopus 로고    scopus 로고
    • Some success in this area employing unsymmetrically substituted (β-diiminate)ZnOAc catalysts was mentioned in the Introduction of this review
    • Some success in this area employing unsymmetrically substituted (β-diiminate)ZnOAc catalysts was mentioned in the Introduction of this review.
  • 95
    • 34447103620 scopus 로고    scopus 로고
    • It should be noted that the analogous Co(II) porphyrin derivative in the presence of two equivalents of DMAP was relatively ineffective at producing propylene carbonate from propylene oxide and CO2, with a TOF of only 16 h-1 at 120 °C.88 On the other hand, Co(III)-TPP(Cl) and DMAP under identical conditions afforded a TOF value of 826 h-1
    • -1.
  • 99
    • 34447107159 scopus 로고    scopus 로고
    • The selectivity factor, S, is computed using the equation: S = In[1 - C(1 + ee)]/In[1 - C(1 -ee)], where the conversion C and ee are for the propylene carbonate product.
    • The selectivity factor, S, is computed using the equation: S = In[1 - C(1 + ee)]/In[1 - C(1 -ee)], where the conversion C and ee are for the propylene carbonate product.
  • 131
    • 34447098415 scopus 로고    scopus 로고
    • In reference 125, Sugimoto and co-worker explored the use of (salen)-MnOAc for the copolymerization of cyclohexene oxide and CO2
    • 2
  • 132
    • 34447093951 scopus 로고    scopus 로고
    • 3 complexes do not readily coordinate a sixth ligand, and only reluctantly afforded six-coordinate complexes in the presence of very strong nitrogen donors such as DMAP. Frantz, E. B. Unpublished observations.
    • 3 complexes do not readily coordinate a sixth ligand, and only reluctantly afforded six-coordinate complexes in the presence of very strong nitrogen donors such as DMAP. Frantz, E. B. Unpublished observations.


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