Controlled Radical

Polymerization
ATRP and RAFT Processes

Controlled Radical Polymerization

Controlled Radical Polymerization

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 Nitroxide (SFR) Controlled Radical Polymerizations
Scope and Limitations
Controllable Monomers
Styrene, Butadiene, Methyl Methacrylate, Styrene Sulfonate(Aq)

Problem Monomers
Alkyl Acrylates, Vinyl Acetate, Vinyl Chloride
Initiator Structure
Initiator formed in situ using commercial initiators
SFR adduct can be introduced to preformed structures including
dendrimers, functionalized polymers and telechelics
Useful Additives
Camphorsulfonic acid - deactivates styrene dimer

Chain Transfer Chemistry

• 1. Thiols:
• . .
P + H S(CH2)3CH3 P H + S(CH2)3CH3
•
CH2=CH
•CH2=CH
X . X CH3(CH2)3-S P .
CH3(CH2)3-S CH2CH
X

•To produce monofunctional polymers, use functionalized thiols:

HO-CH2CH2-SH HO-C-CH2-SH
O

2. Disulfides
. .S
P + S S P S +
X X X

S S
X X

Can lead to difunctional telechelics

Dithiauram disulfide extremely efficient

CH3 S
N C S CH3
CH3 S C N
CH3
S

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 Dithiauram Chain Transfer Process
P
. CH3 S S
P + N C S CH3 CH3
CH3 S C N N C. S CH3
CH3 CH3 S C N
S CH3
S

P P
CH3 S S
N C. S CH3 H3C . CH3
CH3 S C N N C + S C N
CH3 S CH3
S H3C S

H3C CH3
N C S S C N
H3C CH3
S S

Resultant polymer is difunctional iniferter, Useful in

controlled free radical polymerization

Iniferter Polymerization Technique

Initiator Transfer Terminator = Iniferter
CH3 S S
uv light CH3
N C S CH3 N C S. . S C N CH3
CH3 S C N CH3
CH3 CH3 S
S

CH3 S CH3 S . CH3

N C S. N C S CH2 CH + .S C N
CH3
CH3 CH3 S
Styrene
Primary radical termination
CH3 S CH3
N C S CH2 CH S C N
CH3 CH3
S

Otsu, et. al. Makromol. Chem., Rapid Commun., 1982. 3: 127-132; 133-
140.

Formation of Carbon Centered Radicals

CH3 S CH3 CH3 S . .
N C S CH2 CH S C N CH3
N C S CH2 CH S C N
CH3 CH3 CH3 CH3
S UV + S

CH3 S
CH3
N C S CH2 CH S C N
CH3 CH3
S

Alternate Initiators CH3 S CH3

CH3 N C S CH S C N
CH2 S C N CH3 2 CH2 CH3
CH3 S
S S
CH3 CH2 CH2
BDC N C S CH3
CH3 S C N
CH3
S
Durene tetrakis (N,N-diethyldithiocarbamate
(DDC)

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 Generic RAFT Agent

Chain transfer agent that acts by fragmentation

Monomer inserted into

R is free radical
weak single bond
leaving group (R.)
X=S X It must be able to
X R
reinitiate
Reactive polymerization
double bond Z

Z modifies addition and

fragmentation rates

Reversible Addition-Fragmentation Chain

Transfer Polymerization (RAFT)
Controlled with designed chain transfer agents (RAFT agents)
Chain transfer
k add kβ
. S S R
P + C P S . S R P S
C
S + R.
k -add C
Z Z Z
M Raft agent M .
Reinitiation R. RM
Chain Equilibration
k add
. S S Pn k
Pm + C Pm S . S Pn β Pm S S + Pn.
k -add C C
Z Z Z
M

Apparent Chain Transfer Constants

kβ
Ctr = ktr/kp where ktr = kadd
k-add + kβ
Useful Raft agents have Ctr > 2

Impact of Z substituents on reactivity

S S CH2 Raft agent Ctr at 80 C
Z = Ph 26
Z Z = CH3 10
with Z = OC6F6 2.3
Z = OPh 0.72
Styrene monomer Z = NEt2 0.01

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 Apparent Chain Transfer Constants
• Impact of R substituents on reactivity

S Raft agent Ctr at 80 C

S R R = C(CH3)2CN* 13
R = C(CH3)2Ph* 10
Ph R = C(CH3)2CO2Et 2
R=C(CH3)2CH2C(CH3)3 0.4
with
R = CH(CH3)Ph 0.16
Styrene monomer R = C(CH3)3 0.03
R = CH2Ph 0.03
* Dependent upon initial concentration of RAFT agent

Concentration effect of RAFT agent

CH3
S S C
CH3
Ph

Thermal initiated polymerization of

styrene at 110C for 16 hr

Mn, PDI, conv: control, 324K, 1.74, 72%;

0.0001RA, 189K, 1.59, 59%; 0.0004RA, 107K, 1.21, 60%
0.0010 RA, 48K, 1.07, 55%; 0.0029RA, 14.4K, 1.04, 55%

Factors responsible for retardation

• Slow fragmentation of initiator adduct

Slow fragmentation of polymer adducts during propagation

Slow reinitiation by expelled radicals

Selectivity for the expelled radical (R.) to add to the RAFT

agent rather than to monomer

Selectivity for the propagating radical (Pn.) to add to the RAFT

agent rather than to monomer, (i.e. transfer constant to high)

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 Star Polystyrene Synthesis
O S

C O S S Ph 4

styrene, 110 C
O S Ph

C O S S n Ph
4

Addition/fragmentation
S
Ph Ph
S S +
Ph
n Ph

Byproduct formation during star synthesis

Ph Ph
2
n Ph

Ph Ph

n Ph 2

+ Disproportionation
RI and LS detectors
Using UV detector, no shoulder detected

General Mechanism for Atom Transfer

Radical Polymerization (ATRP)

kact
n kt R
R X + Mt Y Ligand Termination
kdeact kp
Monomer
kact
Keq =
kdeact + X Mt n+1Y Ligand

Keq determines polymerization rate

Rp = kp[M][P*] =kpKeq[M][I]o x [CuI/[X-CuII]

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 Mechanism of ATRP Process

Initiation via Redox activation of alkyl halide

R X Mt n R X

Mt n+1X Y

ki R
R

Y Y

Mechanism of ATRP Process

Propagation via reversible activation steps
X
R X
Mt n
R
Y z Y
Mt n+1X Y
R
kp R kp R
Y z Y
z
Y Y Y

Mechanism of ATRP Process

T Termination reactions lead to enhanced concentration of

e persistent radicals--PRE H
R + R
z Y z Y
R
2 Mt n+1X Y Y
z Y Disproportionation
Y and coupling

+ 2 Mt n+1X

Persistent radicals shift equilibrium and

lower concentration of propagating radicals

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 Polymerization of Methyl Acrylate (MA)

Evolution of Mn and MWD, Mw/Mn with monomer

conversion for bulk polymerization of MA at 130
C[1-(PE)Cl]= [CuCl] = 0.038; [bpy] = 0.11

Polymerization of Methyl Acrylate (MA)

Mn and MWD, Mw/Mn on monomer conversion for

bulk polymerization of MA at 130 C
[1-(PE)Cl]= [CuCl] = 0.038; [bpy] = 0.11

Optimized MA Polymerization

Evolution of molecular weight and polydispersity in the ATRP of MA,

T = 90 C,[MA] = 11.2 M; [MA]/[MBP]= 1513;
[MBP/[CuBr]/[dtbpy] = 1/1/2
MBP = methyl 2-bromoporpionate, dTbpy = 4,4’-di-tert-butyl-
2,2’-bypyidine

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 Components of ATRP
• 1. Monomers—Stabilizing groups (phenyl or carbonyl)
adjacent to carbon radicals
2. Initiators-- Alkyl halides or psuedohalides
Structure should be similar to propagating halide
3. Catalysts-- Transition metal with two readily available
oxidation states
Ligands control solubility and dynamics of
ATRP equilibrium
4. Solvents—inert to chain transfer, non-poison to
catalysts but solvate catalyst initiator complex
5. Temperature—high temperature better but side
reactions and catalyst stability limit choice

ATRP Monomers
• Styrenes

Methacrylates

ATRP Monomers

• Acrylates

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 ATRP Monomers

• Acrylonitrile—need solvent like ethylene carbonate

(Meth)acrylamides—tend to deactivate catalysts

Acrylamide not successful

Methacrylic acids --poison catalysts

Can polymerize protected monomers

Initiators
• Halogenated Alkanes and Benzylic Halides

α-Haloesters, a-Haloketones, Alkyl and Aryl Sulfonyl Chlorides

Catalysts

• Transition metal complexes of:

• Rhenium,
• Ruthenium and Iron
• Rhodium,
• Nickel and Palladium
• Copper

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 Ligands for Copper Complexes

Reactivity
Bipyridines < < Me5DETA < Me6TREN

Block Copolymers
Best results with monomers in same class (i.e. acrylates)

Block Copolymers
• Sequence of addition critical for monomers
from different classes
Methyl acrylate then methyl methacrylate
poor transfer, broad PDI
Methyl methacrylate then methyl acrylate
good transfer, narrow PDI

Crosspropagation activity AN > MMA > Sty ~~MA

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 Functionalized Polymers via ATRP

Functionalized Polymers via ATRP

Nucleophilic modification of active halide end group

Molecular Architecture via ATRP

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Molecular Architecture via ATRP

Molecular Architecture via ATRP

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