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Ring-Opening Metathesis Polymerization (ROMP) Supervisor : Prof. Ru-Jong Jeng Student : I-Chun Tang Date : 2013.12.20. 1 P. Dubois, O. Coulembier and J.-M.

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Presentation on theme: "Ring-Opening Metathesis Polymerization (ROMP) Supervisor : Prof. Ru-Jong Jeng Student : I-Chun Tang Date : 2013.12.20. 1 P. Dubois, O. Coulembier and J.-M."— Presentation transcript:

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

2 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 3 ROMP Mechanism C.W. Bielawski, R.H. Grubbs, Prog. Polym. Sci. 32 (2007) 1–29

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

5 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 6 Living ROMP  Characteristics : (1)fast and complete initiation (2)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 : (1)convert to growing polymer chains quantitatively and rapidly (2)react with accessible terminating agents to facilitate selective end-functionalization (3)display good solubilities in common organic solvents (4)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 7 Living ROMP C.W. Bielawski, R.H. Grubbs, Prog. Polym. Sci. 32 (2007) 1–29

8 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 9 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. Richard R. Schrock (1945 - ) Organic chemistry Metathesis reaction Nobel prize in chemistry (2005)

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

11 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 alkoxy ligands. 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 12 Nobel Prize in Chemistry (2005) Robert Howard Grubbs (1942 - ) ; USA Field: organic chemistry Methods in organic synthesis The development of metathesis Nobel prize in chemistry (2005) “ for the development of the metathesis method in organic synthesis " 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 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 14 Novel Catalysts Frech, C.M., Blacque, O., Schmalle, H.W., Berke, H., Adlhart, C. and Chen, P. ( 2006 ) Chemistry – A European Journal, 12, 3325 – 38. Love, J.A., Morgan, J.P., Trnka, T.M. and Grubbs, R.H. ( 2002 ) Angewandte Chemie, 114, 4207 – 9 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.

15 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 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. 16 Stereoselective and Regioselective ROMP

17 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 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 19 Thanks for your listening !


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