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LIVING POLYMERIZATION
Hà Thúc Huy
Khoa Hóa - ĐHKHTN
Cao học Hóa LýTổng hợp & Biến tính poloymer
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Polymers in everday use
• Mechanical properties
• New applications
• Personal care products• Pharmaceutical Applications
• BASF, Unilever, Geltex, Avecia, etc
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Control over Polymer
architecture• Graft Copolymers
• Star copolymers
• Dendrimers• Non covalent crosslinking
• Branching
• Narrow MWD• Blocks
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Control
•Molecular Weight
(Chain Length and Polydispersity)
•Chain Architecture
(Block, Comb, etc)
•
Functionality
•Rate / Exotherm
X
Y
Macromonomer
Telechelic
Block
Graft
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Radical reactions
P1 P2+
P1 P2
P1 P2+
P M P M
P S P S
P Px PxP
+
+
+
+
+
+
?
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Test for Living Polymerisation
0 20 40 60 80 100
M n
% Conversion
kp[Pol*]
l n [ M ] 0 / [ M ]
time
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Living Polymerisation
•Anionic
•Cationic
•Ring Opening
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Living Polymerisation
• Rate of termination ∼ 0
• Rate of Initiation > Rate of Propagation
• PDi (Mw/Mn) = 1 + 1/DP
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Living systems
*constant number of polymer chains
*no permanent chain stopping
reactions*dormant and active state
*control of chain-growth
*narrow MWD (Poisson)
*<Mn> vs. monomer conversion is
linear
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Living Polymerisation
◊ No Termination
◊ No Chain Transfer
INITIATION
I* + M→IM* k i
PROPAGATION
IM* + M→IMM* k p1
IM n* + M→IM nM* k pn
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Rate of Initiation = k i[I][M]
Rate of Propagation = k p[M*][M]
[M*] = [I]
Integration leads to,
ln[M]0/[M] = k p[M*]t
As the rate of termination = 0
[M*] is constant
Thus a plot of ln[M]0 /[M] vs t is linear
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Degree of Polymerisation = Dpn
i.e. Dp
Dpn = [M]/[I] @ 100% conversion
Mn = Dpn x M0
(M0 = mass of the repeat unit)
Thus a plot of Mn vs % Conversion is linear for
a living polymerisation
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If Rate of initiation (R i)≈or > Rate of
Propagation (R p)
and both R i and R p > Rate of termination (R t)
(Ideally R t = 0)
Then
PDi (MWD, Mn/Mw) is narrow and a Poisson
distribution.
PDi = 1+1/[DPn]
e.g. For a polymer with DPn = 100, PDi = 1.01
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ATRP ATOM TRANSFER RADICAL
POLYMERIZATION
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Living Polymer ization
Conversion
M n
Mn=
[M]0
[I]0
× Conv.×Mm
• Mn
• Structure
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Free Radical Polymerisation•Widely used industrially
•Advantages:
- Very Robust Technique
- Wide range of monomers and functionality’s
Almost anything with a double bond
- Wide range of operating conditions
- Aqueous Media: Emulsion polymerisation
•Disadvantages
•Highly non-selective reaction Non-trivial product control
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Living and ControlledPolymerisations
• Living systems – constant number of polymer chains
– no permanent chain stopping reactions
– dormant and active state – control of chain-growth
– narrow MWD (Poisson)
– <M n> vs. monomer conversion is linear
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R-X + M(n)↔R* + M(n+1)-X
X = Cl, Br
R* can propagate or terminate
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
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Suppressing radical
termination
Rt/Rp =k t [P•]2/k p[M][P•]
=k t
[P•]/k p
[M]
ATRP MechanismATRP Mechanism
CuBr/L + Br P CuBr 2/L+ P•
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Cu
MLigand
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ATRP Systems
Metal Ligand Initiator
CuBr, CuCl Bipyridine
Multidentate amine
RuBr2 PPh3 + Al(OiPr)3
FeBr 2 PPh3
NiBr 2 PPh3
PdBr 2 PPh3
X
X
O
O
X
O
O
SO2Cl
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Macromolecules, 30 (25), 7697 -7700, 1997.
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A: PS standard
B: PS by ATRP
C: PS by AIBN
Patten, T.E., Xia, J, Abernathy, T., Matyjaszewki, K. Science 1996 , 272, 866.
A: Synthesis of polymers with controlled molecular weightA: Synthesis of polymers with controlled molecular weight
2. ATRP Applications
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Factors affecting the molecularFactors affecting the molecular
weight controlweight control
• Fast initiation
• Rapid deactivation
Narrow
MWD
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SO2Cl
X
O
OX
O
O
X
OBr
O
O
O
O
O
C-XInitiator ≥ C-X polymer
Initiator matches Monomer
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Rapid deactivation
1 +Kp[R-X]
Kd[CuX2]
2
Conv1
Mw
Mn
=
[CuX2][P ]
[CuX][P-X]=Kd
Conv.-can not go too high
Kp - Temperature
B: Synthesis block
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B: Synthesis block
copolymers
Macroinitiator methodR-X +
CuX/LM X1
M2CuX/L
X
X-R-X+ M1 CuX/L XX
X
CuX/L 2M
X
AB
ABA
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C: Synthesis of star polymers
O
O
Br
O
Br
Br
O
O
O
O
O
Br
Br
O
O
O
O
Br
Br
O
O
Matyjaszewski, K., Miller, P. J. Pyun, J. Kickelbick, G.
Diaamanti, Macromolecules 1999, 32, 6526
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Macromolecules, 31 (20), 6762 -6768, 1998
Jiro Ueda, Masami Kamigaito, and Mitsuo Sawamoto
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Macromolecules, 31 (20), 6756 -6761, 1998
Hiroko Uegaki, Yuzo Kotani, Masami Kamigaito, and Mitsuo Sawamoto
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D: Hyperbranched Polymers
Cl
O
O
Br
O
O
O
O
Br
O
O
Monomer-Initiator
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A
B*
* * *
*
*
*
*
*
*
*
**
*
*
*
*
* *
*
*
*
*
*
*
* *
**
*
**
*
* *
*
*
*
*
*
**
*
*
*
*
*
A*
B*
A*BB*
AA
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E. Synthesis of End-functionalized Polymers
O OBr
O
O NH
Cl
Cl
ClO
O
ClO
HO OBr
O
St, MMA, MA
St, MMA
MA (at low conversion)
MMA
St
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Low catalystefficiency
High catalystresidual
Deep color in product
Purification Catalyst and
ligand waste
Challenges for ATRP
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Too much “catalyst” leads to problems of cost and
residual metal in products.
Rate can be accelerated;
Reduction of copper(II) to copper(I) e.g. disproportionation
with copper(0) - Matyjaszewski
Addition of rate enhancers e.g. acid, alcoholsUse of mildly co-ordinated solvents
However, for many applications we require
Much lower levels of metal
Recycling of metal
Acceptable rates of polymerisation
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•Catalyst supporting
Solution to the Problem ?
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Mn and PDI vs conversion in MMA
polymerization by supported catalysts
PS
or
SiN
N
Cu
Br
0
5000
10000
15000
0 20 40 60 80
Conversion (%)
M n
1
1.5
2
2.5
3
Mw / Mn
Theor. Mn
Haddleton,
Chem. Commun. 1999, 99.
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Cu
Support
Catalyst
Spacer
NN
X
ClN
O
O
NH2
N
N
Crosslinked PSTY bead with 2 %
chlorostyrene
PotassiumPhthalimide
DMF
N2H4
2-Pyridine carbaldehyde
Supported catalysts for ATP
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WHY?WHY?
1 +Kp[R-X]
Kd[CuX2]
2
Conv
Mw
Mn=
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Catalyst
Concentration.Catalyst
residual Color
Develop high reactive catalysts
Future development
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Materials
2-(2-Bromoisobutyryloxy) ethylmethacrylate (BIEM)
2-(Dimethylamino) ethyl methacrylate (DMAEMA)
Hydroxylethyl methacrylate (HEMA)
Ethyl -2-bromoisobutyrate
HAuCl4,4H2O
NaBH4
Potassium persulfate (KPS)
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Synthesis of PDMAEMA brushes on the surface of colloid particles by ATRP.
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