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Ring-Opening Metathesis Polymerization (ROMP)

Ring-Opening Metathesis Polymerization (ROMP). Supervisor : Prof. Ru-Jong Jeng Student : I-Chun Tang Date : 2013.12.20. P. Dubois, O. Coulembier and J.-M. Raquez , Handbook of Ring-Opening Polymerization. Outline. Chemistry of ROMP Ring-opening mechanism

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Ring-Opening Metathesis Polymerization (ROMP)

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  1. Ring-Opening Metathesis Polymerization (ROMP) Supervisor : Prof. Ru-JongJeng Student : I-Chun Tang Date : 2013.12.20. P. Dubois, O. Coulembierand J.-M. Raquez, Handbook of Ring-Opening Polymerization.

  2. Outline • Chemistry of ROMP • Ring-opening mechanism • Chain-transfer reaction • Living ROMP • Well-defined catalysts and application • Schrock-type initiators • Grubbs-type initiators • Recent application of ROMP • Novel catalysts • High and low ring-strain monomers • Stereoselective and regioselective ROMP • Conclusion

  3. ROMP Mechanism C.W. Bielawski , R.H. Grubbs , Prog. Polym. Sci. 32 (2007) 1–29

  4. Chain-Transfer Reaction C.W. Bielawski , R.H. Grubbs , Prog. Polym. Sci. 32 (2007) 1–29

  5. Outline • Chemistry of ROMP • Ring-opening mechanism • Chain-transfer reaction • Living ROMP • Well-defined catalysts and application • Schrock-type initiators • Grubbs-type initiators • Recent application of ROMP • Novel catalysts • High and low ring-strain monomers • Stereoselective and regioselective ROMP • Conclusion

  6. Living ROMP • Characteristics : • fast and complete initiation • exhibits a linear relationship between the degree of polymerization (typically measured as the number-average molecular weight of the polymer, Mn) and monomer consumption • (3) PDI<1.5 • Catalysts : • convert to growing polymer chains quantitatively and rapidly • react with accessible terminating agents to facilitate selective end-functionalization • display good solubilities in common organic solvents • show high stability toward moisture, air, and common organic functional groups C.W. Bielawski , R.H. Grubbs , Prog. Polym. Sci. 32 (2007) 1–29

  7. Living ROMP C.W. Bielawski , R.H. Grubbs , Prog. Polym. Sci. 32 (2007) 1–29

  8. Outline • Chemistry of ROMP • Ring-opening mechanism • Chain-transfer reaction • Living ROMP • Well-defined catalysts and application • Schrock-type initiators • Grubbs-type initiators • Recent application of ROMP • Novel catalysts • High and low ring-strain monomers • Stereoselective and regioselective ROMP • Conclusion

  9. Richard R. Schrock • (1945 - ) • Organic chemistry • Metathesis reaction • Nobel prize in chemistry • (2005) Schrock-Type Initiators Schrock , R.R. , Murdzek , J.S. , Bazan, G.C. , Robbins , J. , DiMare , M. and O ’ Regan , M. ( 1990 ) Journal of the American Chemical Society , 112 , 3875 – 86 .

  10. Robert Howard Grubbs • (1942 - ) • Methods in organic synthesis • The development of metathesis • Nobel prize in chemistry • (2005) Grubbs-Type Initiators Hoveyda-Grubbs Catalyst Grubbs , R.H. ( 2003 ) Handbook of Metathesis , Vols1 – 3 , 1st edn(ed. R.H. Grubbs ), Wiley – VCH Verlag GmbH , Weinheim.

  11. Catalysts Comparison Schrock (1990) Grubbs (1995) • Highly reactive. • Poor tolerance in functional group. • The catalytic activity increases with the electron withdrawing nature of the two alkoxyligands. • Metathesis of tri- and tetra-substituted olifens is possible. • Tolerance in functional group. (CO, OH, NH) • Selectivity towards sterically unhindered olefins and strained olefins. • Tri- and tetra-substituted olifens are not attacked.. C.W. Bielawski , R.H. Grubbs , Prog. Polym. Sci. 32 (2007) 1–29

  12. Nobel Prize in Chemistry (2005) “ for the development of the metathesis method in organic synthesis " • Robert Howard Grubbs • (1942 - ) ; USA • Field: organic chemistry • Methods in organic synthesis • The development of metathesis • Nobel prize in chemistry (2005) • Richard R. Schrock • (1945 - ) ; USA • Field: organic chemistry • Organic chemistry • Metathesis reaction • Nobel prize in chemistry • (2005) • Yves Chauvin • (1930 - ) ; Belgium • Field: organic chemistry • Metathesis • Nobel prize in chemistry • (2005)

  13. Outline • Chemistry of ROMP • Ring-opening mechanism • Chain-transfer reaction • Living ROMP • Well-defined catalysts and application • Schrock-type initiators • Grubbs-type initiators • Recent application of ROMP • Novel catalysts • High and low ring-strain monomers • Stereoselective and regioselective ROMP • Conclusion

  14. Novel Catalysts Opstal , T. , Couchez , K. and Verpoort , F. ( 2003 ) Advanced Synthesis Catalysis , 345 , 393 – 401 . Drozdzak , R. , Allaert , B. , Ledoux , N. ,Dragutan , I. , Dragutan , V. And Verpoort, F. ( 2005 ) Coordination Chemistry Reviews , 249 , 3055 – 74 . Love , J.A. , Morgan , J.P. , Trnka , T.M. and Grubbs , R.H. ( 2002 ) Angewandte Chemie, 114 , 4207 – 9 Frech , C.M. , Blacque , O. , Schmalle , H.W. , Berke , H. , Adlhart , C. and Chen , P. ( 2006 ) Chemistry – A European Journal , 12 , 3325 – 38 .

  15. High and Low Ring-Strain Monomers Singh , R. , Czekelius , C. and Schrock ,R.R. ( 2006 ) Macromolecules , 39 ,1316 – 7 . Lee , J.C. , Parker , K.A. and Sampson , N.S. ( 2007 ) Journal of the American Chemical Society , 128 , 4578 – 9 . Hejl , A. , Scherman , O.A. and Grubbs , R.H. ( 2005 ) Macromolecules , 38 , 7214 – 18 .

  16. Stereoselective and Regioselective ROMP Scherman , O.A. , Walker , R. and Grubbs , R.H. ( 2005 ) Macromolecules , 38 , 9009 – 14 . Yang , H. , Islam , M. , Budde , C. and Rowan , S.J. ( 2003 ) Journal of Polymer Science Part A – Polymer Chemistry , 41 ,2107 – 16 . Wang , D. , Yang , L. , Decker , U. ,Findeisen , M. and Buchmeiser , M.R. ( 2005 ) Macromolecular Rapid Communications , 26 , 1757 – 62 . Lehman , S.E. , Jr. , Wagener , K.B. , Baugh ,L.S. , Rucker , S.P. , Schulz , D.N et al.( 2007 ) Macromolecules , 40 , 2643 – 56 .

  17. Outline • Chemistry of ROMP • Ring-opening mechanism • Chain-transfer reaction • Living ROMP • Well-defined catalysts and application • Schrock-type initiators • Grubbs-type initiators • Recent application of ROMP • Novel catalysts • High and low ring-strain monomers • Stereoselective and regioselective ROMP • Conclusion

  18. Conclusion • Advantages • Well-defined catalysts • Living ROMP • → a narrow PDI • → tunable sizes, shapes, and functions. • Configuration control • Prospects • Recycling and reusing the precious metal (Mo . Ru …) • Further progress in both polymer and materials science. • (to break up the limitation of ROMP)

  19. Thanks for your listening !

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