1. Atom Transfer Radical Polymerization (ATRP): Concept, Application, Challenges and Future Development
Youqing Shen
Departments of Chemical Engineering and
Materials Science and Engineering
McMaster University
Hamilton, Ontario, CANADA L8S 4L7

2. Living PolymerizationMn
[M]0
Conv.  Mm 
Mn=
[I]0
Conversion Mn
Structure

3. Radical reactions ?

4. Suppressing radical termination
Rt/Rp =kt [P•]2/kp[M][P•]
=kt[P•]/kp[M]

6. ATRP Systems Metal Ligand Initiator CuBr, CuCl Bipyridine
Multidentate amine
RuBr PPh3 + Al(OiPr)3
FeBr PPh3
NiBr PPh3
PdBr PPh3

7. A: Synthesis of polymers with controlled molecular weight
2. ATRP Applications
A: Synthesis of polymers with controlled molecular weight
A: PS standard
B: PS by ATRP
C: PS by AIBN
Patten, T.E., Xia, J, Abernathy, T., Matyjaszewki, K. Science 1996, 272, 866.

8. Factors affecting the molecular weight control
Fast initiation
Rapid deactivation
Narrow
MWD

9. C-XInitiator  C-Xpolymer
Initiator matches Monomer

10. Rapid deactivation
Kp - Temperature
Conv.-can not go too high

11. B: Synthesis block copolymers
Macroinitiator method

12. C: Synthesis of star polymers
Matyjaszewski, K., Miller, P. J. Pyun, J. Kickelbick, G. Diaamanti, Macromolecules 1999, 32, 6526

13. D: Hyperbranched Polymers
Monomer-Initiator

15. E. Synthesis of End-functionalized Polymers

16. Challenges for ATRP

17. Solution to the Problem ?
Catalyst supporting

18. Mn and PDI vs conversion in MMA polymerization by supported catalysts
Haddleton,
Chem. Commun. 1999, 99.

19. WHY?

20. Future development
Develop high reactive catalysts