LIVING POLYMERIZATION

Polymers in everday use

• Mechanical properties
• New applications
• Personal care products
• Pharmaceutical Applications
• BASF, Unilever, Geltex, Avecia, etc
 Control over Polymer
architecture
• Graft Copolymers
• Star copolymers
• Dendrimers
• Non covalent crosslinking
• Branching
• Narrow MWD
• Blocks
 Control

Macromonomer

 Molecular Weight
Telechelic (Chain Length and Polydispersity)
Y
X

Block  Chain Architecture

(Block, Comb, etc)
Graft
 Functionality

 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

• Rate of Initiation > Rate of Propagation

• PDi (Mw/Mn) = 1 + 1/DP

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
 Living Polymerisation

 No Termination
 No Chain Transfer

INITIATION

I* + M  IM* ki

PROPAGATION

IM* + M  IMM* kp1

IMn* + M  IMnM* kpn

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

D e g re e o f P o ly m e ris a tio n = D p n

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)

and both Ri and Rp > Rate of termination (Rt)

(Ideally Rt = 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

 Living Polymerization

[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:

- 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
 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
 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
 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

• Fast initiation Narrow

• Rapid deactivation MWD
 C-XInitiator  C-Xpolymer

Initiator matches Monomer

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

Conv.-can not go too high

 B: Synthesis block
copolymers
Macroinitiator method
CuX/L
R-X + M1 X

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

Matyjaszewski, K., Miller, P. J. Pyun, J. Kickelbick, G. Diaamanti,

Macromolecules 1999, 32, 6526
Macromolecules, 31 (20), 6762 -6768, 1998
Jiro Ueda, Masami Kamigaito, and Mitsuo Sawamoto
Macromolecules, 31 (20), 6756 -6761, 1998
Hiroko Uegaki, Yuzo Kotani, Masami Kamigaito, and Mitsuo Sawamoto
D: Hyperbranched Polymers

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

High catalyst Deep color in

residual product

Purification Catalyst and

ligand waste
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, alcohols
Use of mildly co-ordinated solvents

However, for many applications we require

Much lower levels of metal
Recycling of metal

Acceptable rates of polymerisation

Solution to the Problem ?
• Catalyst supporting
 Mn and PDI vs conversion in MMA
polymerization by supported catalysts
3

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)

2-(Dimethylamino) ethyl methacrylate (DMAEMA)

Hydroxylethyl methacrylate (HEMA)

Ethyl -2-bromoisobutyrate

HAuCl4,4H2O

NaBH4

Potassium persulfate (KPS)

Synthesis of PDMAEMA brushes on the surface of colloid particles by ATRP.