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CSIRO MATERIALS SCIENCE AND ENGINEERING
RAFT choosing the right agent
The fundamental polymer chemistry in this presentation is referred from
Moad G, Rizzardo E, Thang SH. 2005. Aust. J. Chem. 58: 379-410.
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Conventional free radical polymerisation

ADVANTAGES:
Simple to implement
Tolerant of a wide range of monomers and
reaction conditions
Inexpensive
LIMITATIONS:
Relatively broad molecular weight distribution
Copolymers heterogeneous in composition
Little scope for making blocks or more complex
architectures
20,000 monomers 500 monomers
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RAFT polymerisation technology
Living polymer chains:
Predetermined M
W
:
Narrow M
W
distribution:
M
w
/M
n
= 1.05 1.2
[ RAFT Agent ]
P
n
[ Monomer]
~
Active end-groups
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RAFT polymerisation technology
The RAFT agent (X-Y)
Z-group controls the
reactivity of the C-S double
bond; influences the rate of
radical addition and
fragmentation
Reactive C-S double bond
Free radical
leaving group R

must be able to reinitiate
polymerisation

Weak C-S bond
R S Z
S
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Types of RAFT agents
Uses are dependent upon the RAFT agent selected:
Dithiobenzoates
very high transfer constants
prone to hydrolysis
may cause retardation when used in high concentrations
Trithiocarbonates
are readily synthesized
high transfer constants
cause less retardation and are more hydrolytically stable (than dithiobenzoates)
Xanthates
lower transfer constants
more effective with less activated monomers
made more active by electron-withdrawing substituents
Dithiocarbamates
activity determined by substituents on N
effective with electron-rich monomers



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RAFT polymerisation technology
Retained RAFT group (Y)
allows for further
chemical manipulation
of the polymer
macro-RAFT agent
Polymer
R S Z
S
Monomer
Initiator
R
S Z
S
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Mechanism of RAFT polymerisation
X X
Z
R X X
Z
R P
n
X X
Z
P
n
R P
n
M
X X
Z
P
n
X X
Z
P
n
P
m
X X
Z
P
m
P
n
P
m
M M
P
m
R
monomer (M)
chain transfer
chain equilibration
reinitiation
k
add
k
-add
k

+
+
P
n
I
monomer (M)
initiation
P
n
P
m
termination
dead polymer +
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How to select RAFT agents
Ph MeS H
3
C N
F F
F
F F
O N
O
PhO EtO N
H
3
C
Ph
N
Et
Et
meth
y
l methacr
y
late
vin
y
l acetate
N-vin
y
lpy
rrolidinone
st
y
rene
,
meth
y
l acr
y
late
,
acr
y
lamide
,
acr
y
lonitrile
CH
3
NC
CH
3
CH
3
Ph
CH
3
H
NC
Ph
CH
3
EtO
2
C
CH
3
CH
3
CH
3
H
3
C
H
3
C
H
3
C
H
H
H
NC
CH
3
H
Ph
CH
3
H
3
C
H
3
C
H
3
C
H
Ph
H
H
NC
H
meth
y
l methacr
y
late
st
y
rene
,
meth
y
l acr
y
late
,
acr
y
lamide
,
acr
y
lonitrile
vin
y
l acetate
,
N-vin
y
lpy
rrolidinone
Z group: addition rates decrease and fragmentation rates increase from left to right
R group: fragmentation rates decrease from left to right
R S Z
S
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CTA structure Styrenes Acrylates Acrylamides Methacrylates Methacrylamides Vinyl Esters Vinyl Amides
o o
o o
o o
o o
o o o o
o o o o
RAFT agent monomer matching
o No control of molecular weight dispersity or severe retardation/inhibition
Limited control of molecular weight dispersity (<1.5) or significant retardation
Good control of molecular weight dispersity (<1.3) and no marked retardation
Excellent control (<1.2) of molecular weight dispersity
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CTA structure Styrenes Acrylates Acrylamides Methacrylates Methacrylamides Vinyl Esters Vinyl Amides
o o o o
o o
o o o
o o
o o
RAFT agent monomer matching (cont.)
o No control of molecular weight dispersity or severe retardation/inhibition
Limited control of molecular weight dispersity (<1.5) or significant retardation
Good control of molecular weight dispersity (<1.3) and no marked retardation
Excellent control (<1.2) of molecular weight dispersity
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RAFT agents core set
Vinyl acetate
N-vinylpyrrolidinone
N-vinyl carbazole
Styrene
Methyl acrylate
Acrylamide
Acrylonitrile
Methyl methacrylate
Methacrylamides
Styrene
Methyl acrylate
Acrylamide
Acrylonitrile
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End-functional PMMA synthesis
24 28 32 36 40
elution volume (min)
Moad G, Chong YK, Rizzardo E, Postma A, Thang SH. 2005. Polymer. 46: 8458-8468.
Over ~50-fold range of RAFT agent concentrations
Little retardation
Low dispersities/monomodal distributions
[RAFT] x10
2
M M
n
M
w
/M
n
% Conv.
19.92 2600 1.17 80
9.96 4600 1.15 80
4.95 9300 1.11 79
2.48 20600 1.09 91
1.24 39600 1.09 >99
0.61 8400 1.11 >99
0.32 12500 1.16 >99
MMA + Vazo-88 + HOOCCH
2
CH
2
SCS-R HOOC PMMASCS-R
90C
6 hrs

S S
CN
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A-B diblock copolymers
Poly(BA-b-AA)
M
n
= 52,400
M
w
/M
n
= 1.19
Poly(BA)
M
n
= 33,600
M
w
/M
n
= 1.13
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Time (hr) M
n
M
w
/M
n
% Conv.
8 55,400 1.05 31
16 86,200 1.04 50
40 135,900 1.05 83
Star polymers 6-arm star polystyrene
Mayadunne RTA, Moad G, Rizzardo E. 2002. Tetrahedron Letters. 43: 6811-6814.
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Luminescent block copolymers
Chen et al. 2008. Chem Comm. 1112.
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End-group removal/transformation
Chong YK, Moad G, Rizzardo E, Thang SH. 2007. Macromolecules. 40: 4446-4455.
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Polymer architectures through RAFT
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Summary
Powerful tool for controlled free radical polymerisation
living polymerisation can be stopped and restarted
ability to design-in features systematically
Synthesis of specifically tailored polymers
unprecedented control over size, composition and architecture
desired physical and chemical properties
narrow molecular weight distribution
end-group removal
Growth of well defined polymers from any surface
small molecules, proteins, etc
Exploration of structure-function relationships of polymer conjugates
rapid optimisation via high-throughput synthesis techniques
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For more information
RAFT Technology Team
CSIRO Materials Science and Engineering
t +61 3 9545 2435
e RAFT@csiro.au
w www.csiro.au/products/RAFT