Introduction to RAFT Polymerization
CHEM 654
Department of Chemistry
University of Wisconsin-Madison
March 4th, 2021
RAFT polymerization
Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization
• Controlled radical polymerization
• Wide range of monomers
• Synthesis of block copolymers or star polymers
• Polymers with functional, end groups
Moad, G.; Ezio Rizzardo, E.; Thang, S. Chem. Asian J. 2013, 8, 1634. 2
(Traditional) Free Radical Polymerization
3
(Traditional) Free Radical Polymerization
Why control MW?
Mechanical
strength
Molecular weight
Log η0
3.4
• Side (intramolecular chain transfer or termination) reactions 1
→ Lack of control in molecular weights, wide dispersity Me Log Mw
4
Odian, G. Principle of Polymerization, 4th Edition, 2004, John Wiley & Sons
Controlled (Living) Radical Polymerization
TEMPO: Nitroxide-Mediated
Polymerization (NMP)
: using alkoxyamines
1993, Georges
Halogen atom: Atom Transfer Radical
Polymerization (ATRP)
: using CuBr/ligand
1995, Matyjaszewski
Polymer chain: Reversible Addition
Fragmentation Chain Transfer
Polymerization (RAFT)
: using thiocarbonylthio RAFT agents
Odian, G. Principle of Polymerization, 4th Edition, 2004, John Wiley & Sons 5
RAFT polymerization - Introduction
• First reported by scientists at CSIRO in Australia
Living Free-Radical Polymerization by Reversible Addition-
Fragmentation Chain Transfer: The RAFT Process
Graeme Moad Ezio Rizzardo San Thang
Macromolecules 1998, 31, 5559-5562 (cited 5448 times)
• Living polymerization
Chiefari, J. et al. Macromolecules 1998, 31, 5559-5562.
Polymerization of MMA 6
Moad, G.; Rizzardo, E.; Thang, S. H. Acc. Chem. Res. 2008, 41, 1133-1142.
RAFT polymerization - Introduction
[𝒎𝒐𝒏𝒐𝒎𝒆𝒓]
• Predetermined MW ~ DPn =
[𝑹𝑨𝑭𝑻]
• Narrow molecular weight distribution
: Ð = 1.05 ~ 1.2
• Wide range of available monomers
→ aqueous polymerization
• Tolerance of functional groups in monomers
(OH, NR2, COOH, CONR2, SO3H)
• Disadvantages
o Need to prepare for
(or purchase) RAFT agents
o thiocarbonylthio end groups
Moad, G.; Rizzardo, E.; Thang, S. H. Acc. Chem. Res. 2008, 41, 1133-1142 7
RAFT polymerization
- how it works
macro-RAFT agent
addition fragmentation
macro-RAFT
agent addition
fragmentation
Moad, G.; Rizzardo, E.; Thang, S. H. Acc. Chem. Res. 2008, 41, 1133-1142 8
Choice of RAFT agents
Dithiobenzoates
• Very high transfer constants
• Prone to hydrolysis
• May cause retardation under high concentrations
Trithiocarbonates
• High transfer constants
• More hydrolytically stable (than dithiobenzoates)
• Cause less retardation
Dithiocarbamates
• Activity determined by substituents on N
• Effective with electron-rich monomers
https://www.sigmaaldrich.com/technical-documents/articles/materials-science/polymer-science/raft-polymerization.html 9
Choice of RAFT agents
More activated monomers Less activated monomers
10
Perrier, S. Macromolecules, 2017, 50, 7433
Choice of RAFT agents
Monomer RAFT agent
aromatic dithioesters or trithiocarbonates
More Acrylic acid
Methyl methacrylate Methacrylic acid
Activated
Monomers
(MAMs)
Acrylamide Acrylonitrile Styrene
dithiocarbamates or xanthates
Less Vinyl acetate N-Vinylpyrrolidone
Activated
Monomers
(LAMs)
N-vinylcarbazole (NVC)
N-vinylcaprolactame
http://www.sigmaaldrich.com/content/dam/sigma-aldrich/docs/Aldrich/Brochure/1/al_material_matters_v5n1.pdf 11
Choice of RAFT More activated monomers Less activated monomers
agents
Very reactive
Non-reactive
https://www.sigmaaldrich.com/technical-documents/articles/materials-science/polymer-science/raft-polymerization.html 12
Photo-controlled RAFT
Photopolymerization of MA
McKenzie, T.; Fu, Q.; Wong, E.; Dunstan, D.; Qiao, G. Macromolecules 2015, 48, 3864. 13
Photoinduced electron-transfer (PET) RAFT
Photopolymerization of MMA
Room temperature; 4.8 W blue LED light
[MMA] : [RAFT] : [catalyst] = 200 : 1 : 10 × 10-4
14
Boyer and co-workers, JACS, 2014, 136, 5508.
Photo-controlled RAFT
Perrier, S. Macromolecules, 2017, 50, 7433
McKenzie et al. Adv. Sci. 2016, 3,1500394
15
Applications: synthesis of diblock copolymers
pH and thermo-
responsive polymers
Schilli, C. M. et al. Macromolecules 2004, 37, 7861-7866 16
Applications: triblock terpolymers
ABA triblock terpolymers
Chong, Y. K. et al. Macromolecules 1999, 32, 2071-2074 17
Applications: triblock terpolymers for therapeutic delivery
Polymer–siRNA complex
Poly-Fluor570
Poly-Fluor570
RAFT polymer–siRNA complex
Huh7-GFP cells
(Huh7, a hepatocarcinoma cell line)
Moad, G.; Ezio Rizzardo, E.; Thang, S. Chem. Asian J. 2013, 8, 1634.
P. A. Gunatillake, P.; Guerrero-Sanchez, C.; Hinton, T.; Thang, S.; Tizard, M. (CSIRO), WO2013003887, 2013. 18
Applications: star polymers as a viscosity modifier
Chong, Y. K. et al. Macromolecules 1999, 32, 2071-2074
Star polymers
: improved viscosity index
(low viscosity change at temperature)
(Lubrizol)
Moad, G.; Ezio Rizzardo, E.; Thang, S. Chem. Asian J. 2013, 8, 1634 – 1644
19
A. J. Brzytwa, J. Johnson, Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem. 2011, 52, 533 –534.
Applications: polymers with functional end groups
ATRP
Block copolymers
Perrier, S. Macromolecules, 2017, 50, 7433
Moad G. et al. Polym Int 2011 60, 9–25 20
Applications: preparation of thiol-terminated polymers
Atom transfer radical polymerization (ATRP) and thiolation
(X)
(X)
p. 329
✓ Reverse addition fragmentation chain transfer (RAFT) polymerization
and hydrolysis with base 21
Preparation of thiol-terminated PSVPh
RAFT polymerization
b One step hydrazinolysis
22
Lee, C-U. et al. Polymer 2010, 51, 1244–1251
Preparation of PSVPh-coated gold nanoparticles
Average: 5.7 (±2.2) nm
23 23
Jang, S. G.; Khan, A.; Hawker, C. J.; Kramer, E. J. Macromolecules 2012, 3, 1553.
Applications: polymerization in aqueous media
Water-soluble,
RAFT-safe
monomers
Water-soluble,
RAFT-safe
RAFT agent
McCormick, C. L. et al. Chem. Res. 2004, 37, 312-325 24
Applications: polymerization in aqueous media
Diethylaminoethyl PDEAEMA:
methacrylate pH and thermo-responsive
(water-soluble at low pH)
block copolymers
High pH, PDEAEMA: hydrophobic High temp. PNIPAM: hydrophobic
Smith, A. E. et al. Macromolecules 2010, 43, 1210-1217 25
Summary
✓ RAFT polymerization: controlled radical
polymerization with thiocarbonylthio compounds
✓ Well-defined polymers by RAFT polymerization
• control of molecular weights
• diblock or multi-block copolymer
• complex architectures
• a variety of end group functionalities
• a variety of (aqueous) monomers
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