Atom Transfer Radical Polymerization ATRP: Concept, Application, Challenges and Future Development

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 Polymerization
M0
Mn
Conv.


Mm
Mn
I0
Conversion

• Mn
• Structure

3
Radical reactions

4
Suppressing radical termination
Rt/Rp kt P2/kpMP
ktP/kpM

5

6
ATRP Systems
Metal Ligand
Initiator CuBr CuCl
Bipyridine
Multidentate
amine RuBr2
PPh3 Al(OiPr)3 FeBr2
PPh3 NiBr2 PPh3 PdBr2
PPh3
7
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
14
(No Transcript)
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