Atom Transfer Radical Polymerization

Encyclopedia of Polymer Sceince and Technology
Copyright c 2007 John Wiley & Sons, Inc. All rights reserved.
FUNDAMENTALS OF ATOM TRANSFER RADICAL
POLYMERIZATION
Introduction
The development of living polymerization (1,2) enabled the production of polymers
with precisely controlled molecular weight, narrowmolecular weight distribution,
and well-dened architecture and composition. For the most recent compilation of
controlled/living polymerization techniques, see references (3,4). There are a num-
ber of advantages of controlled/living radical polymerization (CRP) (510) as com-
pared to ionic polymerization, such as applicability to a wide range of monomers
and solvents, tolerance to impurities and functional groups, and ease of experi-
mental set-up. The most widely used CRP techniques include atom transfer rad-
ical polymerization (ATRP) (1114), nitroxide-mediated polymerization (NMP)
(1517), organometallic-mediated radical polymerization (OMRP), (1820), and
degenerative transfer polymerization (2125). In each case, control is maintained
via fast dynamic equilibrium between dormant species and propagating chains
(26,27).
Fundamentals of ATRP
The dynamic equilibrium that mediates control during ATRP is established be-
tween a low oxidation-state transition metal complex (Mt
n
L
m
) and its higher
oxidation-state complex (X-Mt
n+1
L
m
). The mechanisminvolves reversible reaction
of Mt
n
L
m
with an alkyl halide initiator RX by a one-electron redox process with
concurrent halogen abstraction from the dormant species. This occurs via inner
sphere electron transfer (28) and generates X-Mt
n+1
L
m
and an organic radical R
,
with a rate constant of activation k
act
. The radical can add to vinyl monomer with
a rate constant of propagation k
p
, terminate by coupling or disproportionation (k
t
),
or be reversibly deactivated by X-Mt
n+1
L
m
(k
deact
) (Fig. 1). The termination of a
small amount (5%) of growing polymer chains at the initial stage of polymeriza-
tion prevents halogen abstraction from oxidized metal complexes that suppress
further termination reactions via the persistent radical effect (29,30). The ATRP
equilibrium (K
ATRP
=k
act
/k
deact
) is, thus, heavily shifted towards dormant species,
and the polymerization is characterized by uniform growth of polymer chains.
A broad body of evidence has conrmed the presence of intermediate radical
species in this process. This support includes an abundance of similarities between
1
2 FUNDAMENTALS OF ATOM TRANSFER RADICAL POLYMERIZATION
k
act
k
deact
k
p
Bimolecular
termination
+M
Mt
n
L
m
+ P
n
-X X-Mt
n+1
L
m
+ P
n
k
t
Fig. 1. Mechanism of transition metal complex-mediated ATRP.
conventional free-radical polymerization and ATRP, such as the lack of effect of
protic solvents, radical scavengers, and transfer agents (31), the atacticity of poly-
mers prepared by ATRP (3234), similar reactivity ratios in copolymerization
(3539), similar rates of racemization, exchange, and trapping reactions (40,41),
and indistinguishable
13
C kinetic isotope effects (42); concomitant formation of
higher oxidation state metal species during the polymerization (43); and direct
electron spin resonance observation of radicals (44).
The rate of polymerization in ATRP is proportional to initiator concentration
and the ratio of activator to deactivator concentrations, according to eq. 1.
R
p
=d[M]/dt=k
p
[M][P
]=k
p
[M]K
ATRP
[RX]([Mt
n
/L]/[Mt
n+1
X/L]) (1)
It is noteworthy that polymerization rate does not depend on the absolute amount
of catalyst in the system, which suggests that catalyst concentration can be de-
creased without affecting R
p
, as long as the ratio of activator to deactivator concen-
trations remains constant. However, the synthesis of polymers with low polydis-
persity requires sufcient concentration of deactivator (eq. 2) in order to reduce
the number of monomer units added during each activation step and equalize
probability of growth of all chains.
PDI=
M
w
M
n
=1+
1
DP
n
+
[RX]
0
k
p
k
deact
[Mt
n+1
X/L]
2
Conv.
1
(2)
Components
A wide range of monomers have been successfully polymerized by ATRP, includ-
ing various styrenes, (meth)acrylates, (meth)acrylamides, and acrylonitrile, each
of which contains substituents that can stabilize propagating radicals. The poly-
merization rate of each monomer is determined by its unique values of k
p
and
K
ATRP
, the latter of which can be adjusted by modication of the catalytic complex.
Optimal ATRP conditions, including catalyst type and concentration, solvent, and
temperature, must be selected for each monomer in order to obtain a sufciently
high polymerization rate while maintaining a low concentration of radicals and,
thus, a controlled polymerization. The successful ATRP of acidic monomers, vinyl
acetate, and dienes remains a challenge, for a variety of reasons. Acidic monomers
poison the ATRP catalyst by coordination to the metal and protonation of the N-
based ligand; poly(meth)acrylic acids are typically prepared by polymerization of
FUNDAMENTALS OF ATOM TRANSFER RADICAL POLYMERIZATION 3
a protected monomer, such as trimethylsilyl methacrylate or tert-butyl methacry-
late, followed by deprotection (45). The controlled polymerization of vinyl acetate
is limited by a low value of K
ATRP
, which is due to the high carbon-halogen bond
strength exhibited by this monomer (46,47). Solving these challenges requires a
thorough understanding of the rules for rational catalyst selection (see section
4.3).
A variety of commercially available alkyl halides can be employed as initia-
tors for ATRP. A typical initiator is comprised of a transferable halogen that is
activated by -carbonyl, phenyl, vinyl, or cyano substitutents. If initiation is fast
and quantitative, the relative concentrations of monomer and initiator determine
the number of growing chains and therefore the degree of polymerization (DP) or
molecular weight of the polymer (eq. 3).
DP=[M]
0
/[initiator]
0
conversion (3)
The transition metal complex that mediates ATRP is typically Cu-based, but
a multitude of other metals have been demonstrated to successfully control the
process, such as Ti (48), Mo (4951), Re (52), Fe (5356), Ru (12,57), Os (58), Rh
(59), Co (60), Ni (61,62), and Pd (63). The characteristics that a transition metal
center must possess in order to be an efcient catalyst include at least two acces-
sible oxidation states separated by one electron, afnity towards a halogen, and
an expandable coordination sphere. The complexing ligand serves to solubilize
the transition metal and adjust the catalyst redox potential in order to ensure an
appropriate equilibriumbetween dormant and propagating species. Typically em-
ployed nitrogen-based ligands include derivatives of 2,2-bipyridine (bpy) (11,64),
pyridine imine (65,66), diethylenetriamine (DETA) (67), tris[2-aminoethyl]amine
(TREN) (68), and tetraazacyclotetradecane (CYCLAM) (69), among others (70,71).
Phosphorous-based ligands are used in ATRP catalyzed by complexes of Re (52),
Ru (12,57), Fe (53,54), Rh (59,72), Ni (62,73), and Pd (63), but not Cu.
Mechanistic Considerations
Measuring K
ATRP
. Successful polymerization of new or challenging
monomers will require a thorough understanding of the factors that affect the
ATRP equilibrium. The value of K
ATRP
for any particular catalyst and initiator
system must be determined experimentally, which can be easily accomplished by
reacting alkyl halide with transition metal activator and monitoring the increase
in deactivator concentration over time. A plot of F([Cu
II
L
n
X]) versus time is then
constructed, and K
ATRP
is calculated fromthe slope of the linear dependence (eq. 4)
(30). Typical values for various initiators and Cu(I) complexes are between 10
10
10
4
(30,7476). A large value of K
ATRP
is characteristic of an active catalyst
(eq. 4).
F([Cu(II)L
n
X])
[Cu(I)L
n
]
2
0
3([Cu(I)L
n
]
0
[Cu(II)L
n
X])
3
[Cu(I)L
n
]
0
([Cu(I)L
n
]
0
[Cu(II)L
n
X])
2
+
1
[Cu(I)L
n
]
0
[Cu(II)L
n
X]
=2k
t
K
2
ATRP
t+
1
3[Cu(I)L
n
]
0
(4)
H
3
C
H
3
C CH
3
H
3
C CH
3
CH
3
CN
H
3
C
Cl
H
3
C Br
H
3
C
H
3
C
O
CH
3
C
H
H
3
C
CH
2
Cl
Cl
Cl
OCH
3
H
3
C
O
S
H
3
C
O
H
3
C
O
N(CH
3
)
2
F
H
3
C
H
3
C
O
OCH
3
CH
3
O
H
3
C
O
CH
3
CH
3
H
3
C
O
OCH
3
63. 3 (4 10
-9
) 62.1 ( 3 10
-8
) 63.2 (5 10
-9
) 61.7 (6 10
-8
) 60.1 (9 10
-7
) 59.5 (2 10
-6
)
57.5 (7 10
-5
) 55.9 (1 10
-3
) 54.2 (2 10
-2
) 53.3 (8 10
-2
) 52.5 (3 10
-1
)
G
o
298
=51.8 kcal/mol (K
ATRP
=1)
50.3 ( 14) 49.4 (60) 47.2 (2.5 10
3
) 46.9 (4 10
3
) 43.3 (2 10
6
) 39.6 (9 10
8
)
Fig. 2. Free energy change and relative K
ATRP
values for homolytic bond cleavage of alkyl
bromides at 25

C relative to methyl 2-bromopropionate, as determined by DFT (47).
ATRP Subequilibria. In order to critically evaluate the factors that af-
fect the ATRP equilibrium, it is convenient to express this equilibrium as the
product of four reversible reactions: oxidation of the transition metal activator, or
electron transfer (K
ET
); formation of halide anion, or electron afnity (K
EA
); bond
homolysis of the alkyl halide initiator (K
BH
); and association of halide anion with
deactivator, or halidophilicity (K
X
) (eq.59) (77). Bond homolysis is the only of
the four reactions that does not depend on the nature of the catalyst. Alkyl halide
bond dissociation energies have been reported to correlate well with measured
values of K
ATRP
(Fig. 2) (47). For systems employing the same catalyst and con-
ditions, the rate of polymerization can therefore be predicted from the calculated
bond dissociation energies.
Mt
n
/L Mt
n+1
X/L + e
K
ET
(5)
X + e X
K
EA
(6)
R-X
R + X
K
BH
(7)
X + Mt
n+1
/L
K
X
Mt
n+1
X/L
(8)
K
ATRP
=
k
act
k
deact
= K
BH
K
EA
K
X
K
ET
(9)
The concentration of deactivator present in the system and, thus, the extent
of control over the polymerization, depends on the value of halidophilicity, K
X
.
This value is strongly solvent dependent, and is signicantly higher in nonprotic
solvents than in protic solvents where the halide anion is efciently solvated (78).
Conducting ATRP in aqueous solvents typically leads to fast polymerization and
loss of control as the majority of the halogen is dissociated from the deactivating
species. This can be partially suppressed by the addition a large initial amount of
X-Mt
z+1
L
m
or halide salts (79).
ATRP is a redox process, and therefore catalyst activity depends on the re-
dox potential of the transition metal/ligand complex. Alinear correlation has been
established between K
ATRP
and E
1/2
values for Cu complexes with a variety of N-
based ligands (80,81). Similar correlations between redox potential and ATRP
catalytic activity have been demonstrated for Fe (55) and Ru (82,83) complexes.
The relative activities of catalysts derived from different transition metals can-
not be predicted solely by examining redox potentials due to the differences in
halidophilicity of each metal center.
Rational Catalyst Selection.
Predicting Catalytic Activity. In order to obtain a sufciently fast polymer-
ization while maintaining control, a catalyst must be selected that exhibits high
activity and stability. The rules for rational selection of ATRP catalysts have been
thoroughly described (84,85) and is briey in this article. Although these rules
have been developed using Cu-based ATRP, they are applicable to all transition
metals that catalyze this process.
The activity of an ATRP catalyst is related to its reducing power, which in
turn depends on the relative stabilities of the Cu(I) and Cu(II) oxidation states
(quantied by the stability constants (I) and (II), see eq. 10). A ligand that
strongly stabilizes the Cu(II) state will generate a corresponding Cu(I) complex
with high activity. In addition, stabilization of both oxidation states (ie, large val-
ues of (II) and (I)) will yield a catalyst that is signicantly less susceptible
to ligand substitution reactions with monomer, polymer, or solvent, even at low
catalyst concentration. Therefore, knowledge of the readily measurable stability
constants of each oxidation state allows for prediction of the activity and sta-
bility of a catalytic complex. The most active Cu-based ATRP catalyst known to
date is the complex with 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane
(dimethyl cross-bridged cyclam, DMCBCy) (76), which is also exceptionally stable.
EE
0
+
RT
F
ln
[Cu(II)]
tot
[Cu(I)]
tot

RT
F
ln
(II)
(I)
(10)
N N
N
N
N
N
N
N
N
N
N
N N
TPMA (62)
N N
N N
N N
bpy (0.066) PMDETA (2.7) dNbpy (0.6) Me
6
TREN (450) DMCBCy (710)
Fig. 3. Rate constants of activation (M
1
s
1
) for nitrogen-based ligands with ethyl 2-
bromoisobutyrate and CuBr in acetonitrile at 35

C.(89).
Although values of K
ATRP
for Cu complexes can be predicted using stabil-
ity constants and redox potentials, knowledge of K
ATRP
is not sufcient to deter-
mine whether a polymerization will be controlled. Fast activation and deactivation
(with k
act
k
deact
) are required to obtain polymers with predetermined molecular
weight and narrow molecular weight distribution. The rate constant k
act
can be
determined by spectroscopically or chromatographically monitoring the consump-
tion of alkyl halide upon activation by a Cu(I) complex, which generates radicals
that are trapped by an excess of scavenging agents such as nitroxides (86). The
value of k
deact
can be measured by a type of clock reaction in which radicals are si-
multaneously trapped by a nitroxide and transition metal deactivator (87). It can
also be estimated from initial molecular weight and polydispersity index values
(88), as well as measured values of K
ATRP
and k
act
(41).
The rate of activation in Cu-based ATRP has been shown to strongly depend
on the structure of the complexing nitrogen-based ligand. The values of k
act
span
more than six orders of magnitude and generally obey several trends, with activ-
ity depending on: linking unit between nitrogen atoms (C4 C3 < C2) and/or
coordination angle; ligand topology (cyclic linear < branched); nature of the lig-
and (aryl amine < aryl imine < alkyl imine < alkyl amine pyridine); and steric
bulk around the metal (Fig. 3) (89) A seemingly minor change in ligand structure
can have a pronounced effect on catalytic activity; for example, the Cu(I) complex
of DMCBCy is 1000 more active than that of Me
4
Cyclam. A similar correla-
tion between ligand structure and k
deact
has not been observed, although it has
been proposed that the ease of structural reorganization of the Cu(II) complex
upon halogen abstraction should be a determining factor in the observed rate of
deactivation (90).
Inadditionto rational selectionof the catalyst, considerationmust be givento
employing the most appropriate initiator for a particular polymerization. As men-
tioned earlier, fast and quantitative initiation is necessary to obtain polymers of
predetermined molecular weight. An initiator that is characterized by sufciently
fast activation must be selected according to the following rules: activity depends
on the degree of substitution (primary <secondary <tertiary), transferable group
(Cl < Br < I), and radical stabilizing group (Ph C(O)OR CN) (Fig. 4).
Avoiding and Exploiting Side Reactions. Choosing the appropriate cat-
alyst for a particular ATRP system requires consideration of the side reac-
tions that may take place during polymerization (Fig. 5). These reactions have
been thoroughly discussed (10,85), and are briey outlined in this article. Outer
sphere electron transfer involves the catalytic reduction of propagating radicals to
O
Br
O
O
Br
O
O
Br
O
O
Cl
O
O
I
O
Br
Br
CN
0.030
0.33
2.6
0.015 0.17
0.53 23
Fig. 4. Values of k
act
(in M
1
s
1
) for various initiators with CuX/PMDETAin acetonitrile
at 35

C (91).
carbanions or oxidation to carbocations (28). For example, the former can occur
when a highly active (ie. reducing) catalyst is employed in the polymerization
of an electrophilic monomer, such as acrylonitrile (9295). Coordination of vinyl
monomer to the catalyst (96,97) does not signicantly affect polymerization un-
der normal conditions, but may become an issue at low catalyst concentration.
Conducting ATRP in protic media can be accompanied by several side reactions
(79,98,99), including loss of deactivator via solvation of halide anion (as discussed
earlier) and disproportionation of the metal center. The latter reaction can be
avoided by choice of a ligand that sufciently stabilizes the Cu(I) oxidation state
relative to the Cu(II) state in protic media.
Finally, it should be noted that certain side reactions can be exploited as
efcient techniques for materials synthesis and the investigation of newcatalysts.
These include atom transfer radical coupling (a manipulation of bimolecular ter-
mination) as a route to telechelic polystyrene, (100,101) -H abstraction from
growing polymer chains for the generation of oligomers (49,102), and the forma-
tion of organometallic species that may be able to simultaneously mediate ATRP
and OMRP (18,49,103).
Initiation Systems.
Normal/Reverse/Simultaneous Reverse and Normal ATRP. Normal
ATRP consists of an alkyl halide initiator and transition metal catalyst initially
in its lower oxidation state. Although this technique is easily applicable in an aca-
demic setting, the oxidative instability of the catalyst and relatively large amounts
typically employed may pose difculties on an industrial scale. Reverse ATRP was
developed in order to circumvent oxidation problems. This method utilizes a con-
ventional radical initiator (such as AIBN) to generate propagating radicals that
are reversibly deactivated by a higher oxidation state metal, in order to generate
the ATRP activator in situ (104106).
Although reverse ATRP provides a convenient alternative to handling air-
sensitive catalysts, it cannot be used in chain extension reactions for the prepara-
tion of block copolymers because the radical source does not contain a transferable
atom. Simultaneous reverse and normal initiation (SR&NI) is conducted in the
presence of an alkyl halide initiator, and AIBN is used to generate the ATRP acti-
vator fromits higher oxidation state complex (107) In this way, handling problems
can be avoided while the ability to prepare block copolymers is maintained. This
technique has been utilized in bulk and miniemulsion (108,109).
Activators Generated by Electron Transfer (AGET). Due to the presence
of a radical source that can initiate new chains, SR&NI is limited in its ability
to prepare clean block copolymers. AGET ATRP circumvents this difculty by
Outer Sphere Electron Transfer
Monomer Coordination
Formation of Organometallic Species
-H Abstraction
Halide Dissociation
R + Mt
n+1
/L
m
R
+
+ Mt
n
/L
m
R + Mt
n
/L
m
R
-
+ Mt
n+1
/L
m
+ Mt
n
/L
m
R
Mt
n
/L
m
R
R + Mt
n
/L
m
R-Mt
n+1
/L
m
H
+ Mt
n
/L
m
H-Mt
n+1
/L
m
+
n n
X-Mt
n+1
/L
m
Mt
n+1
/L
m
+ X
-
2Mt
n
/L
m
Mt
n+1
/L
m
+ Mt
n-1
/L
m
(Mt = Cu, Os)
Disproportionation
R R R R
Fig. 5. Possible side reactions during ATRP.
generation of the lower oxidation state activator via reducing agents that cannot
produce new radicals. A variety of reducing agents can be used for this process,
including zero valent Cu, (110,111) tin
(II)
2-ethylhexanoate, (112) ascorbic acid,
(113,114) and triethylamine (115). This technique is particularly applicable to
aqueous and miniemulsion systems (116118).
Decreasing Catalyst Concentration by New Initiation Processes (ICAR
and ARGET). As described earlier, the total catalyst concentration in ATRP
can be reduced without affecting polymerization rate because R
p
depends on the
ratio of activator to deactivator concentrations. However, the amount of catalyst
cannot be decreased indenitely in normal ATRP due to unavoidable radical ter-
mination reactions that occur at the initial stages of polymerization. If catalyst
concentration is less than the concentration of terminated chains, all of the ac-
tivator will eventually be present as a persistent radical and the reaction will
stop at low conversion. A new initiation process known as initiators for continu-
ous activator regeneration (ICAR) allows ATRP to be conducted in the presence
of ppm amounts of catalyst. The technique works by the continuous generation
of radicals by decomposition of a conventional radical initiator (such as AIBN),
R
+M
R-R
R-X + +
k
act
k
deact
k
p
Mt
n
/ L Mt
n+1
X / L
k
t
ICAR I-X I 1/2 AIBN (or thermal)
ARGET Oxidized form of RA + HX Excess Reducing Agent (RA)
Fig. 6. Mechanism of ICAR and ARGET ATRP.
which reduces Cu that is present as a persistent radical to the corresponding lower
oxidation state activator (Fig. 6) (119) In the polymerization of styrene, thermal
initiation generates a sufcient amount of radicals without the need for an ad-
ditional radical source. Polymerization rate during ICAR ATRP depends on the
concentration of the radical source, and not on the nature of the catalyst.
A dramatic reduction in catalyst concentration can also be achieved using an
excess of reducing agent instead of a radical source (Fig. 6). This technique, which
is known as activators regenerated by electron transfer (ARGET) (120), has been
utilized to prepare homopolymers and clean block copolymers in the presence of <
50 ppm of Cu catalyst (121) The reducing agents employed in this process include
hydrazine, phenol, glucose, ascorbic acid, Sn(II) species, and Cu(0). Careful consid-
eration must be given to choice of catalyst for this process (119), since a number
of side reactions that can occur during ATRP (such as halide dissociation and
monomer coordination) are exacerbated during polymerization in the presence
of low catalyst concentration (85). However, it is noteworthy that a diminished
concentration of catalyst can reduce the occurrence of certain side reactions, such
as outer sphere electron transfer and -H elimination. This has recently allowed
the preparation of high molecular weight poly(styrene-co-acrylonitrile) (122) and
polyacrylonitrile (95) by ATRP.
Conducting ATRP
ATRP can be conducted in bulk, solution, or a variety of heterogeneous media,
(123) including miniemulsion(113,124126), microemulsion(127), emulsion(128),
suspension (129132), dispersion (133), and inverse miniemulsion (118,134,135)
The choice of polymerization media depends primarily on solubility considera-
tions. A solvent is necessary in certain instances, such as during polymerization
of acrylonitrile (the formed polymer is not soluble in its monomer) or room tem-
perature polymerization of methyl methacrylate (the system will vitrify at high
conversion). It should be noted that the chosen solvent should be suitable not only
for monomer and obtained polymer, but also for the catalytic complex.
Judiciously selected additives can enhance the capabilities of ATRP. Lewis
acid complexing agents have been shown to increase polymerization rate and
in some cases decrease molecular weight distribution (136,137). They can also
increase the extent of syndiotacticity and isotacticity in a polymer (138,139).
Fig. 7. Illustration of polymers with controlled functionality, composition, and topology.
Reducing agents, such as tin(II) octanoate (119), ascorbic acid (114), and Cu(0)
(114), can reduce handling difculties and allow ATRP to be conducted in the
presence of signicantly lower amounts of catalyst.
Materials
ATRP has been used to prepare polymers with various functionalities, composi-
tions, and topologies (Fig. 7) (140). Highlights from each of these categories are
discussed in the following sections.
Functionality. The presence of functional groups within a polymer are
important in ne-tuning many properties, such as solubility, polarity, biocom-
patibility, melting/glass transition temperatures, elasticity, tensile strength, crys-
tallinity, electrical conductivity, etc. Functionality can be incorporated within a
polymer via modied monomers, initiators, or chainends (Fig. 7). The use of a func-
tional monomer will have the greatest effect over bulk properties, while chain end
functionality can lead to materials good for blend compatibilzation. ATRP is tol-
erant to several types of functional groups, although certain groups may interfere
with the ATRP mechanism (eg, acidic groups). These can be easily incorporated
through post polymerization modication, as discussed earlier.
Functional monomers. The various monomers polymerizable by ATRP in-
clude styrene derivatives, (meth)acrylates, (meth)acrylamides, and acrylonitrile.
These monomers can be modied accordingly in order to incorporate more sophis-
ticated functional groups (Fig. 8). Other classes of functional monomers include
macromonomers (which consist of a polymer chain with a polymerizable group at
its terminus), monomers containing an ATRP initiator (leading to hyperbranched
polymers), and monomers displaying two or more polymerizable groups (leading
to a cross-linked network).
SO
3
-
Na
+
COO
-
Na
+
N N
+
F
Cl
-
F
F
F
F
O
O
O
O
O
O
O
O
O
O
+
Na
-
O
3
S
N N
O
N
3
O
H
OH
H
OH
H
O
OH
H
H
HO
O
N HN
O O
HN
SO
3
H
Fig. 8. Various classes of functional monomers.
A multitude of styrene derivatives have been polymerized via ATRP, ex-
hibiting both electron-withdrawing and weakly electron-donating substituents
on the aromatic ring (141). The presence of electron withdrawing groups (such
as sulfonates, carbonyls, and halogens) leads to a faster polymerization, due to
decreased stability of the dormant species and thus increased propagation rates.
The polymerization of 4-acetoxystyrene has been demonstrated (142), and styrene
derivatives containing alkyl substituents were also successfully polymerized. As
mentioned earlier, acidic derivatives (such as 4-vinylbenzenesulfonic acid and 4-
vinylbenzoic acid) are typically protected as a salt in order to prevent catalyst dis-
ruption (143). The ATRP of 4-vinylpyridine has also been accomplished, although
the catalytic complex was carefully selected in order to prevent side reactions with
this nucleophilic and basic monomer (74).
(Meth)acrylates represent the broadest range of monomers polymer-
izable by ATRP. Some of the many examples of functional (meth)acrylates
include 2-hydroxyethyl (meth)acrylate, (79) glycidyl (meth)acrylate (144),
2-trimethylsilyloxyethyl (meth)acrylate (145147), 2-(dimethylamino)ethyl
methacrylate (148), and allyl (meth)acrylate, among others. Various bioconju-
gates have been prepared by attachment of sugars (149) and short sequences of
nucleotides (150,151) to vinyl monomers. ATRP of several (meth)acrylamides has
also been demonstrated (152155).
Each of the functional monomers illustrated above yields polymers with
unique properties. Particularly interesting properties are found in smart
materials, which are polymers that respond to environmental changes.
These materials contain functionality that contributes to thermo- (154,156),
light- (157), and/or chemo-responsive behaviors (158). For example, poly(2-
(dimethylamino)ethyl methacrylate) (PDMAEMA) exhibits thermo-responsive be-
havior, and is characterized by a lower critical solution temperature (LCST) of 32
C. Below this temperature, PDMAEMA is water-soluble while above its LCST,

the polymer becomes hydrophobic and precipitates from aqueous solution. Light-
responsive polymers include (meth)acrylates containing azobenzene or spyropy-
ran units, and will undergo a change in molecular structure upon ultraviolet
irradiation (159,160). This leads to changes in dimension and polarity. There are
other classes of polymers which respond to changes in pH or polarity of solvent.
Functional Initiators. Initiators can be modied in a variety of ways, pro-
vided that the functional group does not interfere with the ATRP mechanism. The
use of a functional initiator allows for direct incorporation of a functional group
onto a chain end, yielding a telechelic polymer. Telechelic polymers have also been
synthesized using functional initiators and atom transfer radical coupling (101).
Several examples of functional initiators that have been successful for the ATRP
of styrene are illustrated in Table 1. Polymers prepared by ATRP are halogen-
terminated and can subsequently be used as macroinitiators to form block copoly-
mers. An initiator can also contain multiple initiating sites. Difunctional ATRP
initiators have been used in the synthesis of multiblock copolymers, building from
the core out (161). Other difunctional initiators can contain one ATRP site and an
initiating group for another polymerization mechanism to make block copolymers
through mechanistic transformation (162). Multifunctional ATRP initiators can
be used to synthesize star (co)polymers and other hyperbranched materials as
well.
Chain End Functionality. The halogen located at the end of a polymer pre-
pared by ATRP can be easily displaced by numerous other functionalities (Fig. 9).
Some examples include initiating sites for other polymerization mechanisms, a
polymerizable double bondfor the generationof a macromonomer, or precursors for
click chemistry. Currently, the most popular click reaction is the Cu(I)-catalyzed
azide-alkyne cycloaddition (164,165), which has been prolically combined with
ATRP to prepare pendant-functionalized polymers (166), end-functional polymers
(167,168), multisegmented block copolymers (169), stars (170), brushes (144,171),
and other architectures (172).
Polymer Composition and Microstructure. There are several combi-
nations in which monomers can be arranged along a linear polymer chain, which
is described by the instantaneous composition (Fig. 7). A linear polymer chain
consisting of one type of monomer is known as a homopolymer. When more than
one monomer is polymerized, random, periodic, block, or gradient copolymers are
possible, depending both on the reactivities of each monomer and the method
through which they were polymerized. Different properties can be obtained from
polymers that have the same ratio of monomers and molecular weights, but dif-
fering instantaneous chain composition. Precise control over the composition of
a single polymer chain is possible by ATRP, because essentially all the polymer
chains grow at the same rate throughout the polymerization. Control over poly-
meric microstructure in terms of tacticity is not as simple, and can be developed
further.
Table 1. Functional initiators used for the polymerization of styrene in bulk.
a
Initiator Conv. M
n,SEC
(g/mol) M
w
/M
n
NC-Ph-CH
2
-Br 4-cyanobenzyl bromide 0.48 5,500 1.10
Br-Ph-CH
2
-Br 4-bromobenzyl bromide 0.48 4,500 1.16
CH
3
-CH(CN)-Br 2-bromopropionitrile 0.48 5,100 1.09
CN-CH
2
-Br bromoacetonitrile 0.48 4,500 1.10
O
O
Br
O
glycidol 2-bromopropionate 0.62 6,800 1.12
O
O
Br
t-butyl 2-bromopropionate 0.41 4,000 1.17
O
O
Br HO
hydroxyethyl 2-bromopropionate 0.48 7,500 1.10
O
O
Cl
vinyl chloroacetate 0.94 5,800 1.12
O
O
Br
-bromo butyrolactone 0.41 4,000 1.17
O
Cl
H
2
N
2-chloroacetamide 0.12 4,000 1.51
a
At 110

C, with [M]
0
/[I]
0
/[CuBr]
0
/[dNbpy]
0
= 100/1/1/2 (163).
Random/Gradient Copolymers. Reactivity ratio is dened as the ratio of
the rate constants of homopropagationto cross-propagation. If the reactivity ratios
of comonomers are similar, a polymer with a random/stastical distribution of each
monomer along the chain will be obtained. If one monomer has a signicantly
higher reactivity ratio than the other, a gradient copolymer is formed (173).
Gradient copolymers cannot be prepared by conventional radical polymeriza-
tion due to rapid monomer propagation and a very short chain lifetime. Copolymer
chains rich in one comonomer are initially formed, while chains rich in the other
comonomer form later in the polymerization. These materials typically exhibit
poor properties and macroscopic phase separation. In ATRP, however, the gradi-
ent exists along each chain instead of between chains (174).
Gradient copolymers can be synthesized by two methods, batch or semi-
batch. A batch process is used to prepare a spontaneous gradient copolymer if
the reactivity ratios of the two monomers signicantly differ. For comonomers
with similar reactivity ratios, the semi-batch process can be used to generate a
forced gradient by controlled addition of one comonomer to the reaction mixture
throughout the reaction. Aspects of bothrandomand block copolymers are brought
together in gradient copolymers. These materials possess a broader glass transi-
tion temperature range, reduced order-disorder temperature, and can form new
types of morphologies through self assembly (175). These properties can lead to
X
R R R R
P(n-Bu)
3
,
10 eq.
Cu(0), 0.5 eq./
CuBr
Bu
3
SnH
in situ
benzene
TiCl,
CH
2
Cl
2
NaN
3
, DMF >95%
H
2
O,
THF,
RT
>95%
Et
3
N
>95% (PSt)
PBu
3
O
25 eq.
CH
2
CH X
CH
2
CH
2
O
OH
>95%
CH
2
CH X
CH
2
OH
H
Bu
3
Sn
3 eq.
CH
2
SiMe
3
CH
2
N
3
PPh
3
THF, RT
>95%
N PPh
3
NH
2
H
2
N
OH
NH CH
2
CH
2
OH
X = Br,Cl
Fig. 9. Examples of post-polymerization modication of a polymer chain prepared via
ATRP.
several desirable applications, such as vibration- and noise-dampening materials,
compatibilizers for immiscible blends, and surfactants in emulsion polymeriza-
tions (176,177).
Alternating/Periodic Copolymers. Comonomers that exhibit a tendency to
polymerize inanalternating fashionformperiodic, or alternating copolymers. This
occurs when both monomer reactivity ratios are much less than one, indicating
cross-propagation is preferred to homopropagation. The most common example
is the copolymerization of styrene (an electron-donating monomer) with maleic
anhydride (a strong electron acceptor) (178). Tendency to alternate can also be
strongly increased in the presence of additives, such as Lewis acids (Fig. 10) (179).
Block Copolymers. Block copolymers are prepared by extension of a pure
macroinitiator with another monomer (180,181). The order of monomer reactivity
must be obeyed during block copolymer synthesis. If the rst monomer is simi-
larly or more ATRP active than the second monomer, a clean extension occurs to
form well-dened block copolymers. However, if the rst monomer is less reactive,
inefcient extension of the macroinitiator will result in a product exhibiting bi-
modal molecular weight distribution (91). A method known as halogen exchange
was developed to overcome this problem in ATRP (182,183). Halogen exchange
requires sufcient amount of the catalyst to be present in order for less reac-
tive chloride-terminated chain ends to form, and therefore it cannot be employed
in polymerization techniques that utilize low catalyst concentration, such as
ARGETATRP. Arecent report demonstrates that efcient chain extension of a less
MMA-LA
MMA
LA
St + MMA
LA
St MMA
LA
St MMA
LA
MMA
LA
St MMA
LA
MMA-LA
MMA
LA
St + MMA
LA
St MMA
LA
St MMA
LA
St MMA
LA
MMA
LA
St MMA
LA
MMA
LA
St MMA
LA
MMA
LA
St MMA
LA
Fig. 10. Formation of poly(methyl methacrylate-alt-styrene) in the presence of a Lewis
acid.
+
meso
racemo
LA LA LA
meso
+
+
meso
racemo
(a)
LA LA LA LA LA LA
(b)
meso
+
Fig. 11. Free radical propagation in the absence (a) or presence (b) of Lewis acid (LA).
reactive monomer with a more reactive one can be achieved during ARGET and
ICAR by conducting the reaction in the presence of a small amount of styrene
(184).
An enormous variety of block copolymers have been prepared by ATRP, in-
cluding diblock, triblock, and multisegmented; block copolymers by mechanistic
transformation; and organic/inorganic hybrid block copolymers. Many of these
materials are used commercially, for example, as thermoplastic elastomers, adhe-
sives, and surfactants.
Control of Tacticity/Stereoblocks. Control over tacticity is difcult in a
radical polymerization because the propagating center is a nearly planar sp
2
hy-
bridized carbon, which results in poor stereoselectivity (Fig. 11a). However, the
use of Lewis acids to prepare highly isotactic acrylic polymers via ATRP has been
demonstrated (185187). Lewis acids coordinate to the carbonyl group of acrylic-
based monomers. If the complex is located between the last two segments of a
growing polymer chain, they will be forced into a meso conguration (Fig. 11b).
This produces an isotactic polymer that contains a high percentage of meso dyads.
+
+
+
R
+
+
Macromonomer
+
Initiator
Macroinitiator
R
Monomer
Telechelic
polymer
Functional polymer
Fig. 12. Methods to obtain a polymeric brush.
ATRP
Initiator F-Br
(F: functionality)
[F-Br]/[MM] < 1
Macromonomer
Crosslinker
Core-functionality (F)
Low M
w
/M
n
Br
Br
F
F
Br
F
RR
Fig. 13. Preparation of star copolymers with narrow molecular weight distribution.
This method has also been utilized for the formation of stereoblock copolymers.
A Lewis acid was added to the polymerization of N,N-dimethylacrylamide after a
certain conversion, which yielded an atactic-b-isotactic polymer.
Topology. The various topologies available by ATRP include graft copoly-
mers, star copolymers, cyclic polymers, (hyper)branched materials, and cross-
linked networks (Fig. 7).
Graft/Brush Copolymers. Agraft or brushcopolymer consists of many poly-
mer chains originating from a linear polymer backbone. Due to the unique struc-
ture of polymeric brushes, they can form super soft-elastomers (188,189) or can be
used as templates for semiconducting or magnetic nanorods (190). The three meth-
ods to synthesize brushes are grafting from(191196), grafting onto (166,197), and
grafting through (Fig. 12) (198204).
Grafting onto involves reaction of a pre-formed polymeric side chain with a
backbone polymer. This method typically cannot be used to synthesize brushes
with a high grafting density due to steric crowding of the reactive sites. In the
grafting through method, macromonomers are directly polymerized to form the
brush copolymer. This method is often limited in the degree of polymerization that
can be obtained. The most often used method is grafting from, in which monomer
is grown from a linear polymer backbone that is functionalized with many ATRP
initiating sites along the chain. This method allows signicant control over the
O
O
Br
O
S
O
O
S
O
CuBr / bpy, Me
2
CO, 50
o
C
2
2
S
2
S
2
S
2
S
2
S
2
S
2
S
2
S
2
S
2
S
2
S
2
S
2
S
2
S
2
Bu
3
P, H
2
O - Bu
3
PO
SH
SH SH
O
O
Br
O
S
O
O
S
O
CuBr / bpy, Me
2
CO, 50
o
C
2
2
Fig. 14. Formation of a biodegradable nanogel.
grafting density, which depends on how the polymer backbone is synthesized.
In order to prevent brush-brush coupling, dilute solutions are required during
polymerization. Coupling can also be prevented using a miniemulsion method.
A variety of molecular brushes have been prepared by ATRP, including brushes
with a gradient in grafting density (205), block copolymer side chains, (206), and
a block copolymer backbone with different types of polymers grafted onto each
block. Polymer chains can also be grafted from surfaces or particles to create a
multitude of hybrid materials (207,208).
Star Copolymers. A star copolymer is a nonlinear structure with a central
branch point (209). The polymer chains radiating out from this point are known
as arms. It is possible for a star copolymer to have multiple arms with multi-
ple functionalities. Star copolymers typically exhibit high molecular weights and
low viscosities, and can be used as lubricants, coatings, and carriers for small
molecules. There are two general methods to synthesize a star copolymer: poly-
merizing the arms fromthe core, or attaching pre-polymerized arms to the core. In
the rst method, organic or inorganic multifunctional cores can be used to prepare
3, 4, 6, or 8 armed stars (210216). A hyperbranched core with many functional
sites (created by the polymerization of a monomer functionalized with an ATRP
initiator) was also reported to yield a star with 80 arms (140). To generate stars
starting from pre-formed arms, the arms can be attached to a functionalized core
(for example, using click chemistry) (170,217) or cross-linked in the presence of
divinyl compounds (218220). Arms that are cross-linked and still contain ATRP
initiating groups at the core may be used for the generation of miktoarm stars,
which contain arms of different functionality and different lengths (220). A recent
technique using macromonomers has been developed to create stars with excep-
tionally low polydispersity (Scheme 13) (221,222). Polymeric brushes with a star
structure have also been synthesized by grafting polymer branches from the arms
of a star-shaped backbone (223).
Hyperbranched/Cross-linked Networks. The synthesis of hyperbranched
and cross-linked networks with well-dened structures has been realized through
ATRP and other CRP processes. Branching is often unavoidable in radical poly-
merizations due to radical transfer to polymer. The amount of branching can be
controlled in ATRP by polymerizing monomers containing initiator functional-
ity (224226), or by polymerizing a dilute solution of divinyl monomer (227).
Branching is regulated in each case by controlling the degree of polymeriza-
tion. Cross-linked topologies can be obtained directly by polymerization of divinyl
monomers, or monomers containing cross-linkable pendant functionalities which
are then connected in a post-polymerization step (228). If the amount of cross-
linker is high enough, a network is obtained. Reversibly degradable gels have
been prepared using ATRP by utilizing disulde bonds as the crosslinking points
(228). The disulde bond is broken under reductive conditions, and can be re-
formed under oxidizing conditions. Biodegradable nanogels were also prepared
using disulde linkages, which have potential as drug delivery systems (Fig. 14)
(229).
Cyclic Polymers. The formation of cyclic polymers via condensation and
ionic polymerization methods has been well documented. Generating cyclic poly-
mers through a radical polymerization mechanism, however, is difcult due to the
unselective reactivity of the propagating radical. Cyclization of a telechelic poly-
mer chain synthesized via ATRP has been reported (230,231). Heterotelechelic
azide- and acetylene-terminated polystyrene was cyclized using Cu(I)-catalyzed
click chemistry under high dilution. This method can be extended to other func-
tional polymers as well.
Green ATRP
Recent advances in catalyst design, initiation systems, and materials synthe-
sis have expanded the potential of ATRP as an environmentally benign process
(98,99). The rational selection of highly active and stable catalytic complexes and
the development of ICAR and ARGET have allowed ATRP to be controlled ef-
ciently by essentially insignicant amounts of catalyst. It has been abundantly
demonstrated that ATRP is compatible with environmentally friendly reaction
media, such as water (79,123,232,233) and carbon dioxide (234236). Finally, a va-
riety of green materials have been prepared by ATRP, including self-plasticized
polymers (237), degradable polymers(126,238243), materials for water purica-
tion (244), and nonionic polymeric surfactants (245).
Summary and Outlook
Since the emergence of ATRP over a decade ago, this powerful process has been
enthusiastically explored in order to enhance mechanistic understanding and pre-
pare a wide variety of new materials. Exquisite process control can be attained
by appropriate choice of initiator and transition metal catalyst, both of which can
be selected from a multitude of commercially available compounds. Recent funda-
mental investigations into the factors that affect activation, deactivation, and the
position of the ATRP equilibriumhave provided the polymer synthesis community
with rules for the rational selection of the most suitable catalyst for almost any
ATRP system. This can potentially provide newapproaches for the polymerization
of currently challenging monomers, such as -olens and (meth)acrylic acids. The
development of new initiation systems, such as ICAR and ARGET, has allowed
ATRP to be successfully controlled in the presence of only 10 ppm of catalyst
and can provide an avenue for facile industrial scale-up and the preparation of
sensitive biomaterials. Indeed, a number of companies specializing in the produc-
tion of polymers using ATRP are currently in operation. The materials that have
been prepared by ATRP include functional polymers; random, gradient, and block
copolymers; graft and brush copolymers; star polymers; surface-grafted materi-
als; hyperbranched polymers; and cross-linked networks. In addition, due to their
well-dened structure and composition, polymers prepared by controlled/living
methods are ideal candidates for structureproperty studies. Finally, ATRP has
exhibited increasing potential to not only be conducted in an environmentally
friendly manner, but also to provide materials that can help combat current envi-
ronmental problems.
Acknowledgements
The authors are grateful to the members of the CRP Consortium at Carnegie
Mellon University and the National Science Foundation (Grant DMR 0549353)
for funding. Sincere thanks to Wade Braunecker for detailed discussions and help
in preparation of the manuscript.
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PATRICIA L. GOLAS
LAURA A. MUELLER
KRZYSZTOF MATYJASZEWSKI

Atom Transfer Radical Polymerization

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Encyclopedia of Polymer Sceince and Technology

C. Below this temperature, PDMAEMA is water-soluble while above its LCST,

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