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Macromonomer
Molecular Weight
Telechelic (Chain Length and Polydispersity)
Y
X
Rate / Exotherm
Test for Living Polymerisation
ln [M]0/[M]
Mn
kp[Pol*]
0 20 40 60 80 100
% Conversion
time
Living Polymerisation
Anionic
Cationic
• Ring Opening
Living Polymerisation
• Rate of termination 0
No Termination
No Chain Transfer
INITIATION
I* + M IM* ki
PROPAGATION
[M*] = [I]
ln[M]0/[M] = kp[M*]t
[M*] is constant
i.e . D p
D p n = [M ]/[I] @ 1 0 0 % c o n v e rs io n
M n = D pn x M 0
(M 0 = m a s s o f th e re p e a t u n it)
T h u s a p lo t o f M n v s % C o n v e rs io n is lin e a r fo r
a liv in g p o ly m e ris a tio n
If Rate of initiation (Ri) or > Rate of
Propagation (Rp)
(Ideally Rt = 0)
Then
PDi = 1+1/[DPn]
[M]0
Mn
Mn= Mm Conv.
[I]0
Conversion
• Mn
• Structure
Radical reactions
P1 P2
P1 + P2
P1 + P2
?
P + M P + M
P + S P + S
P + Px P + Px
Free Radical Polymerisation
Widely used industrially
Advantages:
Disadvantages
X = Cl, Br
K. Matyjaszewski: Macromolecules 1997, 30, p7697; 7042; 7034; 7348; 8161; 7692; 6507,
6513, 6398 JACS 1997, 119, p674
V Percec: Macromolecules 1997, 30, p6705, 8526
M Sawamoto: Macromolecules 1997, 30, p2244, 2249
Teyssie: Macromolecules 1997, 30, p7631,
Haddleton: Macromolecules 1997, 30, p2190
Suppressing radical
termination
Rt/Rp =kt [P•]2/kp[M][P•]
=kt[P•]/kp[M]
ATRP Mechanism
CuBr/L + Br P CuBr2/L + P
Ligand M
Cu
ATRP Systems
Metal Ligand Initiator
CuBr, CuCl Bipyridine X
Multidentate amine
RuBr2 PPh3 + Al(OiPr)3
O
FeBr2 PPh3 O X
NiBr2 PPh3
O
PdBr2 PPh3 O
X
SO2Cl
Macromolecules, 30 (25), 7697 -7700, 1997 .
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.
Factors affecting the molecular
weight control
X O O
X O SO2Cl
O
X
O
O
Br
O O
O O
Rapid deactivation
Mw Kp[R-X]2
= 1 + 1
Mn Kd[CuX2] Conv
[CuX2][P ]
Kd =
[CuX][P-X]
Kp - Temperature
CuX/L M2
X
AB
X-R-X+ M1 CuX/L X X
CuX/L M 2
X X
ABA
C: Synthesis of star polymers
Br
Br
O O
O
Br
O
O O
O
O Br O O
O Br
O
O Br
O
Br
O O
O O
Cl
O O
O O
Br Br
Monomer-Initiator
*
*
*
* *
* * *
*
* *
A A A* *
A
*
* * * *
B* B* B A* * *
*
B* *
* *
*
* * *
*
* * * * *
* * **
* * *
*
*
* *
*
*
E. Synthesis of End-
functionalized Polymers
O
Br St, MMA, MA
HO O
O
St, MMA
Br
O O MA (at low conversion)
O
Cl
Cl MMA
O NH
Cl
O
St
Cl
O
Challenges for ATRP
Low catalyst
efficiency
15000 PS
or N N
2.5
Si Cu
Br
10000
Mw/Mn
Mn
5000
Theor. Mn 1.5
0 1
0 20 40 60 80
Conversion (%)
Haddleton,
Chem. Commun. 1999, 99.
Supported catalysts for ATP
Catalyst
N N
Cu
X
Spacer
Support
O
Cl
Potassium N NH2
Phthalimide N2H4
O
DMF
Crosslinked PSTY
bead with 2 %
chlorostyrene N
N
2-Pyridine carbaldehyde
WHY?
Mw Kp[R-X] 2
= 1 + 1
Mn Kd[CuX2] Conv
Future development
Develop high reactive catalysts
Catalyst Catalyst
Concentration. residual Color
Graft Copolymers
Brush Copolymer
Block copolymer side chains
Materials
2-(2-Bromoisobutyryloxy) ethyl methacrylate
(BIEM)
Ethyl -2-bromoisobutyrate
HAuCl4,4H2O
NaBH4