Complex Macromolecular Architectures by Living Cationic Polymerization
Living Polymerization
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Transcript of Living Polymerization
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LIVING POLYMERIZATION
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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
XY
Macromonomer
Telechelic
Block
Graft
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Test for Living Polymerisation
0 20 40 60 80 100
Mn
% Conversion
kp[Pol*]
ln [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* ki
PROPAGATION
IM* + M IMM* kp1
IMn* + M IMnM* kpn
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Rate of Initiation = ki[I][M]
Rate of Propagation = kp[M*][M]
[M*] = [I]
Integration leads to,
ln[M]0/[M] = kp[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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D e g r e e o f P o l y m e r i s a t i o n = D p n
i . e .
D p
D p n = [ M ] / [ I ] @ 1 0 0 % c o n v e r s i o n
M n = D p n x M 0
( M 0 = m a s s o f t h e r e p e a t u n i t )
T h u s a p l o t o f M n v s % C o n v e r s i o n i s l i n e a r f o ra l i v i n g p o l y m e r i s a t i o n
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If Rate of initiation (Ri) or > Rate ofPropagation (Rp)
and both Ri and Rp > Rate of termination (Rt)
(Ideally Rt = 0)
Then
PDi (MWD, Mn/Mw) is narrow and a Poissondistribution.
PDi = 1+1/[DPn]
e.g. For a polymer with DPn = 100, PDi = 1.01
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Living Polymerization
Conversion
Mn
Mn=[M]0
[I]0
Conv.Mm
• Mn
• Structure
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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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Free Radical Polymerisation
Widely used industrially
Advantages:
- Very Robust Technique
- Wide range of monomers and functionality’sAlmost anything with a double bond
- Wide range of operating conditions
- Aqueous Media: Emulsion polymerisation
Disadvantages
Highly non-selective reactionNon-trivial product control
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Living and Controlled Polymerisations
• 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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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, p674V Percec: Macromolecules 1997, 30, p6705, 8526M Sawamoto: Macromolecules 1997, 30, p2244, 2249Teyssie: Macromolecules 1997, 30, p7631, Haddleton: Macromolecules 1997, 30, p2190
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Suppressing radical termination
Rt/Rp =kt [P•]2/kp[M][P•]
=kt[P•]/kp[M]
ATRP MechanismATRP Mechanism
CuBr/L + Br P CuBr2/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
FeBr2 PPh3
NiBr2 PPh3
PdBr2 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 molecular Factors affecting the molecular weight controlweight control
• Fast initiation
• Rapid deactivation
Narrow
MWD
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SO2ClX
O
OX
O
O
X
OBr
O
O
OO
O
C-XInitiator C-Xpolymer
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
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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 NHCl
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 inproduct
Purification Catalyst andligand waste
Challenges for ATRP
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Too much “catalyst” leads to problems of cost andresidual metal in products.
Rate can be accelerated;Reduction of copper(II) to copper(I) e.g. disproportionation with copper(0) - MatyjaszewskiAddition of rate enhancers e.g. acid, alcoholsUse of mildly co-ordinated solvents
However, for many applications we requireMuch lower levels of metalRecycling 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
PSorSi
N N
Cu
Br
0
5000
10000
15000
0 20 40 60 80
Conversion (%)
Mn
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 PSTYbead 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
Conv1
Mw
Mn=
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Catalyst
Concentration.Catalystresidual Color
Develop high reactive catalysts
Future development
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Graft Copolymers
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Brush Copolymer
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Block copolymer side chains
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Materials2-(2-Bromoisobutyryloxy) ethyl methacrylate (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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