Ring-Opening Metathesis Polymerization(ROMP)

Supervisor : Prof. Ru-Jong Jeng

Student : I-Chun Tang

Date : 2013.12.20.

1P. Dubois, O. Coulembier and J.-M. Raquez, Handbook of Ring-Opening Polymerization.

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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

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ROMP Mechanism

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

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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

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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

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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

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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)

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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 .

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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

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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)

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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

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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 .

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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 .

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 .

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Stereoselective and Regioselective ROMP

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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

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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)

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Thanks for your listening !