DOI: 10.1002/ijch.

201100101
Atom Transfer Radical Polymerization: From Mechanisms
to Applications
Krzysztof Matyjaszewski*
[a]
Introduction
Polymers are used every day by all of us and annual poly-
mer production exceeds 200 million tons (i.e. 2 kilograms
per capita every month!). Essentially all modern technol-
ogies rely on polymers, from transportation (automotive
and aircraft), microelectronics (all computers and cell
phones are enabled by polymeric photoresists and LCD
or OLED displays also require polymers), textile fibers,
food packaging, paints, health and beauty products, to
drugs for targeted delivery and other biomedical materi-
als. Recent technological progress in functional materials
was enabled by advances in polymer science, processing,
characterization and especially in synthesis.
Synthesis of uniform macromolecules with precisely
controlled size, novel topology, composition and function-
ality is a prerequisite for the development of new ad-
vanced materials targeting specific applications.
[1]
Precise
synthesis requires living polymerization techniques, where
all chains are instantaneously initiated and grow concur-
rently without significant occurrence of chain breaking re-
actions, such as termination and transfer.
[2]
Typically, such
living polymerizations are accomplished by anionic proce-
dures in very stringently purified systems (with <1 ppm
moisture or air).
[3]
However, the majority of commodity
polymers are prepared under more relaxed conditions,
using polycondensation and radical polymerization (RP)
processes, resulting in poorly controlled structures. There-
fore, it was very desirable to extend the equivalent of
living polymerizations techniques to RP systems.
[4]
At
first glance living RP seemed impossible, because radicals
terminate at diffusion controlled rates. In order to form
well-defined polymers by RP, with sufficiently high mo-
lecular weight (MW), one must minimize the probability
of radical termination relative to propagation. This can
be accomplished by creating and maintaining very low
concentrations of propagating radicals ([P*] =ppb to
ppm) because the rate of termination depends on [P*]
2
and the rate of propagation on [P*]. Such a low and
steady [P*] is established in RP by balancing the rates of
termination and initiation. In conventional RP it is impos-
sible to prepare (co)polymers with controlled architecture
because chains are continuously generated and terminat-
ed in a very short time frame. In a typical RP, chains are
initiated and terminate after about 1 s, a propagating radi-
cal reacts with a monomer ca. every 1 ms and, during its
lifetime of 1 s, it forms a high MW polymer chain with
degree of polymerization, DP10
3
. At any given
moment during the polymerization, the number of grow-
ing chains which can be functionalized or chain-extended
is very small (<0.1%), therefore it is not possible to pre-
pare (co)polymers with well-defined architecture via con-
ventional RP.
Many of the new precise polymerization techniques de-
veloped during the last 30 years employ the formation of
dynamic equilibria between active and dormant species in
[a] K. Matyjaszewski
Department of Chemistry
Carnegie Mellon University
4400 Fifth Ave.
Pittsburgh, PA 15213 (USA)
phone: 412 268 3209
fax: 412 268-6897
e-mail : km3b@andrew.cmu.edu
Abstract: Atom transfer radical polymerization (ATRP) is
currently one of the most often used synthetic polymeri-
zation methods to prepare well-defined polymers with com-
plex architecture. This review covers some fundamentals of
copper-based ATRP, presents basic structurereactivity cor-
relation for initiators and catalyst complexes and discusses
the radical nature of reactive intermediates. New ATRP ini-
tiating processes with ppm amounts of copper catalysts and
various reducing agents are described together with recent
electrochemically controlled ATRP and polymerization in
aqueous homogeneous and dispersed media. Examples of
polymers with precisely controlled architecture are present-
ed together with the effect of variable amounts of catalysts
on molecular weight distribution and morphology of nano-
structured block copolymers. Some current and forthcoming
applications of polymers made by ATRP are presented.
Keywords: atom transfer radical polymerization controlled radical polymerization copper homogeneous catalysis well-defined polymers
206 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim Isr. J. Chem. 2012, 52, 206 220
Review
K. Matyjaszewski
order to minimize the proportion of terminated chains.
This was extended to RP using conditions that create
equilibria between growing radicals and dormant spe-
cies.
[4, 5]
The dormant species cannot terminate but can be
intermittently activated to form radicals that, after addi-
tion of a few monomer units, are converted back to the
dormant state. The controlled radical polymerization
(CRP) methods, developed during the past 1015 years,
allow the preparation of a multitude of previously unat-
tainable well-defined polymeric materials.
[6]
Atom trans-
fer radical polymerization (ATRP) is the most widely
used CRP method.
[7]
This minireview focuses on the
mechanistic understanding of ATRP, aided by computa-
tional studies, as well as synthesis of well-defined poly-
mers and their targeted applications.
Fundamentals of ATRP
In an ATRP, alkyl (pseudo)halide initiators/dormant mac-
romolecular species (RX/P
n
X) react with activators, tran-
sition-metal complexes in their low-oxidation state Mt
m
/
L, (Mt
m
represents the transition-metal species in oxida-
tion state m and L is a ligand; the charges of ionic species
are omitted for clarity), to reversibly form propagating
radicals (P
n
C), and deactivators, the transition-metal com-
plexes in the higher-oxidation state coordinated with
(pseudo)halide ligands X-Mt
m+1
/L. (Scheme 1).
ATRP is a catalytic process and can be mediated by
many redox-active transition-metal complexes (Cu
I
/L and
X-Cu
II
/L are the most frequently used transition metals,
but other metals studied include Ru, Fe, Mo, Os, etc.).
[8]
The rate of ATRP depends on the rate constant of
propagation and on the concentrations of monomer and
growing radicals. The latter is defined by the ATRP equi-
librium constant, the concentration of dormant species
and the ratio of the concentrations of activator and deac-
tivator, as illustrated in Equation (1).
R
p
k
p
K
ATRP
P
n
XCu
I
=LM
X Cu
II
=L

1
The nature of the ligand, L, and monomer/dormant
species as well as reaction conditions, solvent, tempera-
ture and pressure dramatically affects the values of both
rate constants, k
act
[9]
and k
deact
,
[10]
and therefore their ratio,
K
ATRP
. Quantifying K
ATRP
, therefore, provides an appropri-
ate measure of the catalysts activity in a polymerization
reaction.
[10b, 11]
It should be noted that catalyst complexes
are formed dynamically and are characterized by certain
stability constants. Thus, the concentration of catalytic
species and their speciation depends on the stability con-
stants, hence reaction medium, and concentration.
[12]
The
rates of an ATRP increase with catalysts activity (K
ATRP
),
but under some conditions may become slower due to
radical termination and a significant reduction of [Cu
I
/L]/
[ X-Cu
II
/L] ratio, due to the persistent radical effect.
[13]
Equation (2) illustrates how chain uniformity, i.e. , dis-
persity of molecular weights (M
w
/M
n
) of polymers pre-
pared by ATRP, in the ideal case with the absence of
chain termination and transfer reactions, relates to the
concentration of dormant species (P
n
X) and deactivator
(X-Cu
II
) the rate constants of propagation (k
p
) and deac-
tivation (k
deact
), and monomer conversion (p).
[14]
M
w
M
n
1
k
p
P
n
X
k
deact
X Cu
II
=L

2
p
1

2
Thus, for the same monomer, a catalyst that deactivates
the growing chains faster will result in smaller k
p
/k
deact
and will produce polymers with a narrower MWD,
a smaller value for M
w
/M
n
.
[15]
This value can also be de-
creased by increasing the concentration of deactivator, re-
ducing the concentration of the dormant species (target-
ing higher MW) and attaining higher conversion.
StructureReactivity Correlation in ATRP
Equilibrium constants in ATRP depend on the structure
of the catalysts and alkyl halide (i.e. , monomer) and also
on the polymerization medium. Generally, ATRP equilib-
rium constants increase strongly with solvent polarity, by
stabilization of more polar Cu
II
species, and also with
temperature. Deactivation rate constants are usually very
Krzysztof Matyjaszewski (PhD 1976 at
the Polish Academy of Sciences under
Prof. S. Penczek) is J. C. Warner Profes-
sor of Natural Sciences and director of
the Center for Macromolecular Engi-
neering at Carnegie Mellon University.
His main research interests include
controlled/living radical polymeri-
zation, catalysis, environmental
chemistry, and the synthesis of ad-
vanced materials for optoelectronic
and biomedical applications. He has
co-authored over 700 publications
cited over 50,000 times. In 2011, Maty-
jaszewski received the Wolf Prize in Chemistry, Japanese Polymer
Society Award, ACS Hermann Mark Award, and ACS Applied Poly-
mer Science Award. He is a member of the USA National Academy
of Engineering, Russian Academy of Sciences, and Polish Academy
of Sciences.
Scheme 1. ATRP equilibrium.
Isr. J. Chem. 2012, 52, 206 220 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim www.ijc.wiley-vch.de 207
Atom Transfer Radical Polymerization: From Mechanisms to Applications
high and may approach diffusion control limits (k
deact
>
10
7
m
1
s
1
) but they are less influenced by the structure of
the involved reagents than the activation rate constant-
s.
[10a]
Figures 1 and 2 show how k
act
varies with the ligand
structure and selected alkyl (pseudo)halides. The range of
k
act
spans over six orders of magnitude. An examination
of the structure of the ligands shows that the general
order of Cu complex activity for ligands is: tetradentate
(cyclic-bridged) >tetradentate (branched) >tetradentate
(cyclic) >tridentate>bidentate ligands. Bridged cyclam,
tris(2-dimethylaminoethyl)amine (Me
6
TREN) and tris(2-
pyridylmethyl)amine (TPMA) are among most active and
2,2-bipyridine and pyridineimine the least active.
[16]
The
nature of nitrogen atoms in ligands also plays a significant
role in the activity of the Cu complexes and follows the
order pyridine aliphatic amine>imine.
[9]
The presence
of a C2 bridge between N atoms generates complexes
with higher activities than ligands with C3 or C4 bridges.
Steric effects around the Cu center are very important,
with Me
6
TREN complex over 10,000 times more active
than for Et
6
TREN complex.
[17]
Figure 1. ATRP activation rate constants for various ligands with EtBriB in the presence of Cu
I
Br in MeCN at 358C. N2: red, N3: black, N4:
blue; Amine/imine: solid, Pyridine: open, Mixed: left-half solid; Linear: &, Branched: ~, Cyclic: *. Reprinted with permission from Ref. [9] .
Figure 2. ATRP activation rate constants for various initiators with Cu
I
X/PMDETA (X=Br or Cl) in MeCN at 358C: 38 : red, 28 : blue, 18 :
black; isothiocyanate/thiocyanate: left half-filled, chloride: open, bromide: filled, iodide: bottom half-filled; Amide: !, Benzyl : ~, Ester: &,
Nitrile: *, Phenyl-ester: ^. Reprinted with permission from Ref. [18a].
208 www.ijc.wiley-vch.de 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim Isr. J. Chem. 2012, 52, 206 220
Review
K. Matyjaszewski
The reactivity of alkyl halides is also quite different
and it is important to select a sufficiently reactive species
for efficient initiation of an ATRP. Figure 2 shows that
the reactivity of alkyl halides follows the order of 38 >
28 >18, in agreement with bond dissociation energy
needed for homolytic bond cleavage. Radical stabilization
is enhanced by the presence of an a-cyano group, which
is more active than either an a-phenyl or ester group.
The most active initiator is ethyl bromophenylacetate
with combined effects of benzyl and ester species, and is
over 10,000 times more active than PEBr and over
100,000 times more active than MBrP. Alkyl halide reac-
tivities follow the order I >Br >Cl and they are much
higher than alkyl pseudohalides.
[18]
Radical Nature of the Propagating Species
The polymers in ATRP are formed by reaction of mono-
mers with propagating radicals, as in conventional RP.
The living nature of ATRP originates in combining fast
initiation and concurrent growth of all chains via inter-
mittent activation of dormant species catalyzed by Cu
complexes. Radical termination cannot be fully avoided
and the fraction of terminated chains depends on radical
concentration, that is, the polymerization rate. Slower re-
actions with lower [P*] result in smaller amounts of ter-
minated chains.
There is abundant evidence that ATRP operates via
a radical mechanism: cross-propagation kinetics, reactivi-
ty ratios;
[19]
regioselectivity and stereoselectivity;
[19c, 20]
tac-
ticity,
[21]
racemization, chemoselectivity with various traps
and transfer agents,
[22]
radical termination products, and
kinetic isotope effects,
[23]
which all have values similar to
those in conventional RP. In addition, propagating radi-
cals have been observed directly by EPR in the polymeri-
zation of dimethacrylates
[24]
and EPR revealed the pres-
ence of X-Cu
II
species resulting from the persistent radi-
cal effect in ATRP.
[25]
Nevertheless, the multiple interre-
lated equilibria involved in CRP, combined with intermit-
tent activation of a relaxed dormant species, can result in
some deviation in cross-propagation kinetics or branching
from those in a standard RP.
[25g, 26]
Therefore, ATRP is a radical-based process. However,
the radicals can be formed from the dormant species by
several pathways.
ISET vs. OSET
Mechanistically, halogen transfer from an alkyl halide to
the Cu
I
complex can occur via either an outer-sphere
electron transfer (OSET), or an inner-sphere electron
transfer (ISET) i.e. , atom transfer occurs by passing
through a Cu-X-C transition state, which is formally also
a single electron transfer process. OSET can proceed via
a stepwise manner with radical anion intermediates or
through a concerted process with simultaneous dissocia-
tion of the alkyl halide to a radical and an anion. Accord-
ing to Marcus analysis of the electron transfer processes
(Figure 3) OSET should have an energy barrier ~15 kcal
mol
1
higher than the values that were measured experi-
mentally, that is, activation by OSET should be ~10
10
times slower than ISET.
[27]
The differences are much greater than any computa-
tional or experimental errors and, consequently, a copper-
catalyzed ATRP occurs via concerted homolytic dissocia-
tion of the alkyl halide. Moreover, the one-step dissocia-
tive electron transfer to form a radical and an anion is en-
ergetically more favorable than the two-step process via
the radical anion intermediates.
[28]
Figure 3. Comparison of the free energies required for an ISET and a concerted OSET process for the reaction of bromoacetonitrile with
Cu
I
/TPMA catalyst in acetonitrile at 258C. Reprinted with permission from Ref. [27] .
Isr. J. Chem. 2012, 52, 206 220 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim www.ijc.wiley-vch.de 209
Atom Transfer Radical Polymerization: From Mechanisms to Applications
Initiating Systems for ATRP with ppm Copper
One limitation of a classic ATRP is the relatively large
amount of catalyst used to overcome the effect of termi-
nation reactions that increase the concentration of the
equivalent of the persistent radical, the X-Cu
II
L complex,
typically of the order of 0.11 mol %, relative to the mo-
nomer. Therefore, the final products may contain a signifi-
cant amount of residual metal. Several strategies were in-
troduced to remove the catalyst from the final pro-
duct,
[7d, 29]
or to carry out the reactions with lower concen-
trations of catalyst. However, as noted in an ATRP, as in
any CRP, bimolecular radical termination typically in-
volves 1 to 10% of chains. Each termination step leads to
irreversible transformation of two equivalents of the acti-
vator (Cu
I
L in copper-mediated ATRP) into the higher
oxidation state deactivating complex (X-Cu
II
L). There-
fore, due to inevitable termination, the amount of catalyst
could not be decreased to the desired lower concentra-
tions; for example, if the initial concentration of Cu
I
is
1 mol % relative to polymer chains, the polymerization
could stop before 10% conversion, as the chains that
have participated in termination reactions have converted
nearly all the Cu
I
to the Cu
II
deactivator, even at relative-
ly low monomer conversion.
According to Equation (1), the rate of an ATRP does
not depend on the absolute catalyst concentration, but on
the ratio of concentrations of activator and deactivator.
Therefore, new ATRP initiation techniques were devel-
oped focused on keeping this ratio constant with very
strongly diminished catalyst concentrations, down to ppm
level. In these systems a very small amount of active cata-
lyst was used, and the activator lost due to radical termi-
nation was constantly regenerated via a redox process.
Simple reducing agents such as ascorbic acid, sugars,
tin(II) octanoate, or amines were employed in ARGET
(activators regenerated by electron transfer) ATRP,
[30]
or
radical initiators in ICAR (initiators for continuous acti-
vator regeneration) ATRP (Scheme 2).
[31]
ATRP can now
be successfully conducted with very low amounts of cata-
lyst. This approach has been now successfully extended to
organic synthesis radical addition and cyclization reac-
tions based on ARGET and ICAR procedures.
[32]
These new ATRP initiation techniques allow synthesis
of well-defined high MW polymers, markedly higher than
in traditional ATRP, because catalyst-related side reac-
tions that previously limited the polymer MW are mini-
mized at lower catalyst concentrations. For many applica-
tions, the removal of the small amount of catalyst is un-
necessary, and when polymers containing no metal impur-
ities are needed, purification is significantly simpler than
for classical ATRP.
Zero-Valent Metals as Reducing Agents (and
Supplemental Activators)
Metals such as Cu, Fe, Mg or Zn can also be used as the
reducing agent.
[33]
In addition, they can act as direct sup-
plemental activators. However, transition-metal com-
plexes other than Cu, Ru, or Fe are generally relatively
poor deactivators. ATRP with Cu
0
can be considered as
a special case, because it produces in situ the deactivating
species. However, despite the significant amount of work
on the role of Cu
0
and the effect of polar solvents on the
kinetics of an ATRP,
[34]
it was proposed that the high ac-
tivity observed form an ATRP in the presence of one of
the most powerful ligands, Me
6
TREN, and Cu
0
(one of
several possible reducing agents) in polar solvents indicat-
ed a change in mechanism
[35]
rather than merely reflecting
a change in reaction conditions.
[27, 34b]
The alternative
mechanistic proposal for the ATRP of methyl acrylate in
DMSO in the presence of Cu
0
and Me
6
TREN
[35a]
was
named SET LRP (single electron transfer living radical
polymerization).
[35c]
The proposed mechanistic scheme
relies on an outer-sphere electron transfer from Cu
0
to
the alkyl halide to form the Cu
I
species and radical
anions. The resulting Cu
I
species was assumed to instan-
taneously disproportionate back to Cu
0
and Cu
II
species.
The intermediate radical anions were proposed to cleave
to form propagating radicals and anions that associate
with the Cu
II
species. Growing radicals were postulated to
be trapped exclusively by Cu
II
species to form the dor-
mant species and a Cu
I
complex that would not activate
the dormant species but again instantaneously dispro-
portionate.
Detailed kinetic and mechanistic studies show that
alkyl halides react preferentially with the soluble Cu
I
/
Me
6
TREN complex, due to its very high ATRP activity,
rather than with solid Cu
0
that has a relatively small sur-
face area. The Cu
0
serves as a reducing agent and actually
comproportionates with Cu
II
, formed as a persistent rad-
ical in the radical termination process. Cu
0
also slowly
reacts directly with alkyl halides, acting as a supplemental
activator.
[33, 34b]
Only ~10% of CuBr/Me
6
TREN dispro-
portionates in DMSO, and this degree of disproportiona-
tion is even lower in mixtures containing the less polar
methyl acrylate monomer. Disproportionation/compro-
portionation is a relatively slow process rather than in-
stantaneous and since disproportionation is only partial
in most systems, comproportionation dominates. Cu
I
is
always present in the system and is the predominant acti- Scheme 2. ARGET and ICAR ATRP.
210 www.ijc.wiley-vch.de 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim Isr. J. Chem. 2012, 52, 206 220
Review
K. Matyjaszewski
vator. The faster rate of polymerization in DMSO is due
to a larger ATRP equilibrium constant in DMSO than in
other solvents.
[34c]
Moreover, the OSET process is much
slower than the ISET process, due to very slow electron
transfer to alkyl halides
[28, 33, 34b]
and the proposed SET-
LRP mechanism is not viable, since it violates the princi-
ple of microscopic reversibility.
[34b]
Electrochemically Controlled ATRP
In ARGET processes the reducing agent is oxidized and
the byproducts could present purification problems
whereas in ICAR new chains are generated from the
small amount of radical initiator, as in the RAFT process,
and they could be considered as impurities.
[36]
It was,
therefore, both interesting and challenging to avoid for-
mation of these side products and regenerate activators in
a cleaner way. This was accomplished by an electro-
chemical process. Polymerization rates in the electro-
chemical process can be controlled by applied current,
potential, and total charge passed. The concept behind
electrochemically controlled ATRP, or eATRP, is shown
below in Scheme 3.
[37]
Electrochemical methods allow the lower oxidation
state catalyst (e.g., Cu
I
Br/Me
6
TREN) to be reverted back
to its original higher oxidation state, by simply shifting
E
app
to more positive values, thereby providing a means
to rapidly deactivate an ongoing polymerization.
[38]
This
means that polymerizations can be also stopped and re-
started any time simply by switching reversibly from
a cathodic to an anodic current. In Figure 4A the poly-
merization of methyl acrylate conducted in 50% (v/v)
MeCN at 258C is switched on and off simply by
changing the applied E
app
values from 0.69 V to
0.40 V vs. Ag
+
/Ag, respectively. The figure clearly
shows that the polymerization stopped soon after chang-
ing E
app
and started again when E
app
was reduced. Fig-
ure 4B shows that the molecular weight of the formed
polymer increased regularly with conversion and that
there was no change in the degree of livingness of the
formed polymer during the enforced dormancy periods. It
should be noted that electrodeposition can be used to
remove copper from an ATRP.
[39]
ATRP in Aqueous Systems
Water is an inexpensive environmentally friendly solvent
with high thermal capacity. It is an attractive medium for
exothermic radical copolymerization reactions, particular-
ly since both solution polymerization of water-soluble
monomers and biphasic polymerization of hydrophobic
monomers in latexes have found direct industrial scale
applications in various practical fields. It is possible to
prepare polymer latexes and solid particles over a wide
range of size, nm to mm, by employing the full spectrum
of aqueous dispersed media: suspension, dispersion,
emulsion, miniemulsion, microemulsion and inverse mini-
emulsion systems.
[40]
One advantage of biphasic media for
the preparation of polymers from initiators containing
multiple initiation sites is that there is a further segrega-
tion of the low concentration of active radicals through
compartmentalization
[41]
which reduces the formation of
macroscopic crosslinked gels.
Selection of a suitable ligand is a critical first step in
order to conduct a controlled ATRP in any aqueous sys-
tem.
[22d]
Conditions should be adjusted in homogeneous
systems to account for lower complex stability, very high
Scheme 3. Electrochemically controlled ATRP.
Figure 4. A) Conversion (solid circles) and applied potential (dashed line) with respect to time, and B) number average molecular weight
(M
n
) and M
w
/M
n
with respect to conversion. Reprinted with permission from Ref. [37] .
Isr. J. Chem. 2012, 52, 206 220 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim www.ijc.wiley-vch.de 211
Atom Transfer Radical Polymerization: From Mechanisms to Applications
equilibrium constant and also Cu
II
X bond hydrolysis. In
heterogeneous systems, the catalyst complexes should be
sufficiently hydrophobic to be preferentially located in or-
ganic phase and the choice of surfactant is important. An-
other option that has recently been exemplified is using
reactive surfactants or dual reactive surfactants that are
anchored to particle surface and provide not only better
stability but also latent functionality.
[42]
In addition to emulsion, miniemulsion, microemulsion,
dispersion and precipitation polymerization, inverse mini-
emulsion polymerization was also successful. It provided
a new method for the synthesis and functionalization of
well-defined water-soluble or cross-linked polymeric
nanoparticles.
[43]
Stable colloidal nanoparticles of well-
controlled water-soluble poly(oligo(ethylene glycol) mon-
omethyl ether methacrylate) (P(OEOMA)) homopoly-
mers and copolymers were successfully synthesized by in-
verse miniemulsion AGET ATRP at ambient tempera-
tures.
[44]
This procedure allows preparation of well-de-
fined microgels/nanogels with narrow size distribution,
a high degree of chain end functionality, a uniform cross-
linked network, and properties (i.e. swelling ratio, degra-
dation behavior and colloidal stability) superior to micro-
gels prepared by conventional free radical polymeri-
zation.
[45]
ATRP can be also carried out under homogene-
ous conditions in water or in ionic liquids.
[46]
Controlling Polymer Structure
ATRP, as other controlled/living polymerization meth-
ods,
[47]
provides a versatile toolbox for preparation of var-
ious polymers with precisely controlled macromolecular
architectures.
[48]
Since ATRP is a radical process, it is tol-
erant to many impurities and functionalities and can be
carried out under undemanding conditions. Scheme 4 il-
lustrates some examples of polymers with controlled
chain composition, topology and functionality prepared
by ATRP.
Concerning polymer composition, one can use ATRP
to prepare not only homopolymers but also statistical
(random) copolymers from monomers with similar reac-
tivities. However, if the comonomer reactivities are differ-
ent, then gradient copolymers, with continuously varied
composition along the polymer chain, can be formed.
Gradient copolymers can also be formed from comono-
mers with the same reactivity by using a feeding tech-
nique.
[49]
Alternating or periodic copolymers can be pre-
pared by copolymerization of comonomers with very low
reactivity ratios. They can also be formed if one less reac-
tive comonomer, such as a simple alkene, is used in large
excess. Complexation with a Lewis acid can additionally
enhance the tendency for alternation.
[50]
Block and graft copolymers are the most common form
of segmented copolymers. The former can be formed by
sequential addition of comonomers to an ongoing reac-
tion or by segmental coupling (using, for example, click
chemistry), use of mechanistic transformation (from/to
ATRP and ionic, coordination or polycondensation) or
even 2-directional concurrent growth using different poly-
merization mechanisms for the preparation of each seg-
ment.
[51]
An appropriate sequence of comonomer addition
is very important when targeting block copolymeriza-
tion,
[52]
moving from more active to less active monomers,
but sometimes the efficiency of cross-propagation can be
additionally enhanced by the halogen exchange pro-
cess.
[53]
Radical polymerization is generally not efficient
for the control of stereochemistry and polymer tacticity.
Scheme 4. Examples of polymers with controlled architecture prepared by ATRP.
212 www.ijc.wiley-vch.de 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim Isr. J. Chem. 2012, 52, 206 220
Review
K. Matyjaszewski
However, in the presence of Lewis acids such as Y(OTf)
3
and Yb(OTf)
3
not only poly(dimethylacrylamide) with
strongly enhanced isotacticity was prepared but also first
block copolymers with atactic and isotactic segments.
[53a]
There are many examples of controlling polymer chain
topology to form branched architectures including star
polymers prepared using either core-first or arm-first ap-
proaches.
[54]
The latter relies on using macroinitiators or
macromonomers in an ATRP with divinyl crosslinking
agents, under appropriate conditions; instead of forming
macroscopic gels/networks, stars are formed in high yield
and with high uniformity. Gels prepared by ATRP are
different from those made by conventional RP; due to
higher chain uniformity and formation of more regular
network structures they swell more and can be degraded
more easily.
[46a, 55]
One can also prepare comb-like polymers by grafting
from, onto or through, using macromonomers. Very
dense grafting along the copolymer backbone results in
macromolecular bottle-brush structures. These very large
macromolecules, with M
n
values that can exceed several
millions, can be not only visualized by AFM as single
molecules but can also be used as sensors and model ten-
sile machines.
[56]
ATRP has been also used for synthesis of randomly
branched and hyperbranched polymers and even for den-
dritic systems. Cyclic polymers have been prepared by
ATRP or ATRP and nitroxide coupling.
[57]
ATRP is tolerant to many functional groups such as hy-
droxy, cyano, amino, amido, esters and others.
[48f]
Acids
should be protected to prevent protonation of N-based li-
gands. This can be accomplished at higher pH or in the
presence of amines that scavenge protons. Functionalities
can be incorporated via monomers, initiators or through
post-polymerization reactions. One of many advantages
of ATRP is the availability of various functional initiators
and known procedures for the facile preparation of multi-
functional systems, for example, by simple esterification
reactions to form 2-bromopropionates or 2-bromoisobuty-
rates. The list of suitable starting materials includes not
only simple organic polyols, but also natural products and
flat, concave or convex inorganic surfaces.
[7 g, 58]
Moreover,
displacement of halides from the chain ends provides not
only a variety of homo and hetero telechelics but also
many multifunctional stars or (hyper)branched systems
with peripheral functionalities.
[59]
The final properties of many materials are defined not
only by architecture of a single macromolecule but, as
shown in Scheme 4, by their self-assembly to various
nanostructured materials. In addition, controlled pre-as-
sembly is also possible by surface patterning, grafting
from various functional surfaces and even from linear
polymer chains. There are many morphologies available
from self-assembly of block copolymers, depending on
the block order, interaction parameters and volume frac-
tions that constitute spheres, cylinders and lamellae in
various combinations.
[60]
In the next section, it will be
shown that in addition to segment size, segment dispersity
can also become a very important factor in defining mor-
phological features.
Effect of Molecular Weight Distribution on
Morphology of Diblock Copolymers Prepared by
ATRP
It has been theoretically predicted and experimentally
confirmed that molecular weight distribution (MWD) or
dispersity can affect polymer morphology.
[61]
As indicated
earlier in Equation (2), ARGET ATRP should be an effi-
cient method to control MWD by changing the amount
of Cu
II
catalyst in the system. With less Cu deactivator
present in the reaction medium chains grow longer seg-
ments at each intermittent activation step and will pro-
duce polymers with higher dispersity. In order to analyze
the effect of dispersity on morphology of block copoly-
mers, a polystyrene (PS) macroinitiator block was pre-
pared by ARGET ATRP of S with 50 ppm of CuBr
2
/
Me
6
TREN catalyst in the presence of Sn(EH)
2
as reduc-
ing agent, resulting in PS with M
n
=31,100, M
w
/M
n
=
1.11.
[62]
The PS was then chain extended by polymeri-
zation of methyl acrylate with 50 and 5 ppm of CuBr
2
/
Me
6
TREN catalyst resulting in formation of a block co-
polymer with narrow distribution of both blocks, (PS-
PMA)
NN
M
n
=47, 200, M
w
/M
n
=1.11, and a copolymer
with narrow distribution of the first block and broader
distribution of the second one, (PS-PMA)
NB
M
n
=51,700
PDI =1.13. PMA homopolymers prepared under identical
conditions had the following properties: PMA
N
(ARGET
ATRP with 50 ppm Cu catalyst, M
n
=18,300, M
w
/M
n
=
1.11) and PMA
B
(ARGET ATRP with 5 ppm of Cu cata-
lyst, M
n
=18,500, M
w
/M
n
=1.77). Blocking efficiency for
both systems were similar, as determined by liquid chro-
matography. The amount of residual PS homopolymer
was 4% for (PS-PMA)
NN
, and 7% for (PS-PMA)
NB
.
[62]
However, in spite of the overall similar compositions, the
morphologies of the two block copolymers were very dif-
ferent. Figure 5 shows bright field electron micrographs
of PS-PMA samples. The block copolymer (PS-PMA)
NN
showed a typical cylindrical microstructure whereas (PS-
PMA)
NB
showed a hexagonally perforated lamellar mi-
crostructure. The latter, typically a metastable morpholo-
gy, was stable after annealing at 1208C for 72 h. It is pos-
sible that broader MWD of the PMA segment stabilizes
the bicontinuous morphology, as the lower MW fraction
may tend to form a spherical microstructure and higher
MW fraction a lamellar microstructure, thereby finding
a compromise in a hexagonally perforated lamellar mor-
phology.
This study was extended to other PS-PMA systems as
summarized in Scheme 5. Large differences were ob-
served for several block copolymers. Increased dispersity
Isr. J. Chem. 2012, 52, 206 220 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim www.ijc.wiley-vch.de 213
Atom Transfer Radical Polymerization: From Mechanisms to Applications
converted cylindrical morphology to uneven lamellae
with the ratio of PS to PMA segments 70
B
/30
N
or 16
N
/84
B
.
In some other cases disordered cylinders were observed.
These results indicate that MWD becomes an important
tool to control polymer morphology and gives access to
stable bicontinuous microstructures, which would be espe-
cially interesting for membranes, biomedical applications
and conducting polymers including photovoltaics and
bulk heterojunction systems.
[63]
However, it should be
noted that in some cases increased dispersity may also en-
hance formation of a fraction of a homopolymer. This
can lead to enrichment of one of the phases with a homo-
polymer and increased dimensions of the microphase sep-
arated domains.
[64]
The nanostructured morphologies observed in block
copolymers may be thermodynamically stable but may
also be kinetically trapped. Therefore, processing of poly-
mers with complex architecture is very important as this
will also affect the properties of the final materials. An
important challenge for materials science is how to corre-
late molecular structure with macroscopic properties.
[48a, 65]
Processing is a very important link between synthesis and
properties, and hence applications. Another important
factor is an appropriate balance between cost and perfor-
mance. New initiating systems for ATRP such as
ARGET and ICAR not only reduce the amount of
copper, which lowers cost and environmental impact, but
allows control over dispersity and can lead to materials
with new nanostructured morphologies. There are several
other important issues in material development, such as
the fraction of unfunctionalized (dead) chains, the
amount of missing arms in star polymers, or the presence
of non-extended segments in block copolymers. It will be
beneficial if the final product can tolerate such imperfec-
tions but it is also important to quantify to what extent
they will affect material properties. Scheme 6 illustrates
Figure 5. Bright field electron micrographs of PS-PMA samples
after 72 h thermal annealing at T=1208C and staining with RuO
4
(PS is the dark domain); a: (PS-PMA)
NN
, revealing cylindrical micro-
structure imaged along [001]; b: (PS-PMA)
NB
, revealing hexagonally
perforated lamellar microstructure imaged approximately normal
to the layer direction. Inset shows plan view revealing the hexago-
nal arrangement of PS perforations. Reprinted with permission
from Ref. [62] .
Scheme 5. Examples of morphologies for the PS-PMA block copolymers with one of the block with narrow and the other with broad
MWD.
214 www.ijc.wiley-vch.de 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim Isr. J. Chem. 2012, 52, 206 220
Review
K. Matyjaszewski
a concept of retro-designing polymers with controlled ar-
chitecture, taking into account contributions from con-
trolled processing.
Current and Future Applications of Polymers
Made by ATRP
Polymers prepared by ATRP have been commercially
produced in US, Japan and Europe since 2002.
[66]
Poly-
mers made by ATRP find use in many applications, in-
cluding sealants,
[67]
lubricants,
[68]
oil additives with im-
proved thickening behavior, shear stability, and tempera-
ture independent viscosity.
[69]
Telechelic copolymers,
[70]
gradient copolymers,
[71]
block copolymers
[72]
and comb
polymers can be used as wetting agents, pigment disper-
sants
[73]
and various surfactants.
[74]
The pigment stabilizers
can be used for coating compounds, prints, images, inks
or lacquers and other disperse systems.
[73b, 75]
A potential
loss of transparency due to scattering from the embedded
particles, a consequence of the significantly different re-
fractive index of inorganic materials and organic matrix
materials, can be suppressed by means of appropriate sur-
face modification of the particle using ATRP to match
the effective refractive index of the resulting coreshell
particle to the refractive index of the embedding
medium.
[76]
End-functionalized polymers can be used for blend
compatibilization
[77]
during reactive processing and in
many thermosetting compositions; for example, epoxy-
functional polymers and functional materials form the
basis of the majority of products prepared for dispersant,
coating, adhesive, and sealant, etc. applications. Several
polyolefin segmented copolymers containing polar
blocks/grafts were developed to provide surface hydrophi-
licity, conductivity and antibacterial properties to materi-
als.
[78]
A higher value application, based on ATRP functional-
ization of a solid particle, is the development of the sta-
tionary phase of nano-engineered analytical immobilized
metal affinity chromatography columns for separation of
proteins and synthetic prion peptides.
[79]
Core-shell-type hyperbranched polymers form resists
with improved adhesion properties and surface smooth-
ness that are suitable in photolithography and nano-fabri-
cation when spin-coated on a Si wafer and baked to form
a 100 nm thick film showing 254 nm UV sensitivity of
2 mJcm
2
allowing manufacture of the semiconductor de-
vices.
[80]
Polar thermoplastic elastomers can be prepared by
a continuous bulk ATRP process
[81]
or by sequential addi-
tion of monomers to an ongoing emulsion ATRP.
[82]
The
major benefit of polar TPEs is that they are oil resistant
and recyclable, that is, it is possible to injection mold the
materials and minimize waste. Thermoplastic elastomers
(TPEs) can be synthesized in a one-pot process using
ARGET ATRP. PS-PEA-PS and PMMA-PBA-PMMA
TPEs were made in such a process.
[81]
Since multi-func-
tional initiators are easily prepared and polymer topology
affects properties, other non-linear architectures can be
considered; e.g., star-blocks, grafts, or brushes with block
side chains.
[83]
The properties of PBA-b-PAN 3-arm star
block copolymers
[84]
show that these polar materials with
properties that are easily adjustable, based on composi-
tion, retain their useful properties over a broad tempera-
ture range, from 50 to +2708C.
Bottle-brush macromolecules with a very long back-
bone and densely grafted PnBA side chains behave as su-
persoft elastomers with an environmentally stable ultra
low modulus plateau in the soft gel range of 1 kPa.
[85]
The
plateau modulus is much lower than seen for typical poly-
meric rubbers, which can be attributed to the large frac-
tion of the short dangling chains in the system. Such
chains provide significant mobility, making the material
extremely soft and also excellent ionic conductors.
[86]
ATRP provides many advantages in grafting from
a flat surface reaction as the thickness of the tethered
polymer brush can be precisely controlled by systematic
variation of grafting density and DP
n
of the tethered
polymers.
[87]
Modification of surfaces with thin polymer
films can be used to tailor the surface properties such as
hydrophilicity/-phobicity, biocompatibility, adhesion, ad-
sorption, corrosion resistance and friction. The surface
properties can be tuned by the tethering of block copoly-
mers, where the composition and size of each polymer
segment affects the morphology and behavior of the poly-
mer brushes.
[88]
Grafted chains in such a high-density
polymer brush are highly extended, even to their fully ex-
tended lengths in good solvent. A high-density polymer
brush has a different set of characteristic properties, in
both swollen and dry states, that are quite different from
those of the semi-dilute or moderately dense polymer
brushes previously studied.
[89]
Polymers with quaternary
ammonium ions (PQA) effectively kill cells and spores by
disrupting cell membranes. Monomers such as 2-dimethy-
laminoethyl methacrylate (DMAEMA) or 4-vinylpyridine
that can be quaternized, thereby providing biocidal activi-
ty, were polymerized by ATRP.
[90]
Antimicrobial surfaces
Scheme 6. Retro-design of targeted materials properties.
Isr. J. Chem. 2012, 52, 206 220 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim www.ijc.wiley-vch.de 215
Atom Transfer Radical Polymerization: From Mechanisms to Applications
were prepared by grafting from
[78a, 91]
or grafting onto sur-
faces,
[91a, 92]
blended with
[93]
or deposited on other poly-
mers.
[94]
Functional copolymers prepared by ATRP were used
for drug delivery.
[22g, 95]
The diblock copolymer poly(2-
methacryloyloxyethylphosphorylcholine-b-2-(diethylami-
no)ethyl methacrylate) dissolved in acidic solutions, due
to protonation of the amino residues, but formed micelles
at pH 8. The diblock copolymer micelles are biocompat-
ible and show considerable promise for drug delivery ap-
plications.
[95a]
Triblock acrylate-based block copolymers
were prepared by ATRP as matrices for paclitaxel deliv-
ery from coronary stents.
[96]
Stable biodegradable poly-
(oligo (ethylene oxide) monomethyl ether methacrylate)
nanogels, cross-linked with cleavable disulfide linkages,
were prepared by ATRP in inverse miniemulsion.
[97]
These nanogels could be used for targeted drug delivery
scaffolds for biomedical applications since they can be de-
graded into lower molecular weight polymers to release
the encapsulated (bio)molecules.
[45, 95d]
Nanostructured
hybrid hydrogels with sizes ca. 100 nm were incorporated
into larger three-dimensional matrix generating drug de-
livery scaffolds suitable for tissue engineering applica-
tions.
[22g]
Poly(ethylene glycol) (PEG) star polymers con-
taining GRGDS peptide sequences on the star periphery
were synthesized by ATRP of poly(ethylene glycol)
methyl ether methacrylate via an arm-first method.
These star polymers were biocompatible, with greater
than 90% cell viability after 24 h of incubation with
MC3T3-E1.4 cells. Rapid cellular uptake of PEG star
polymers with GRGDS peptides, essentially 100% within
15 min, was observed by flow cytometry, suggesting en-
hanced delivery potential of these functional star poly-
mers.
[98]
Natural products were successfully covalently
conjugated with polymers prepared by ATRP via grafting
from and grafting onto procedures.
[46b, c, 57, 99]
Summary and Outlook
ATRP is among the most versatile synthetic techniques
for preparation of polymers with precisely controlled ar-
chitecture and site specific functionality. The prerequisite
for the precise synthesis is an accurate mechanistic under-
standing of the ATRP process through detailed structure
reactivity correlation including the effect of solvent, tem-
perature and pressure on the reaction. This fundamental
understanding helps in the design of better catalysts, de-
velopment of procedures to reduce the amount of transi-
tion metal, and the ability to carry out environmentally
benign reactions. The second important area is correla-
tion between controlled structure and properties of the
obtained polymers. This relationship includes not only
chain topology, composition and functionality but also
chain length uniformity. An interesting opportunity is of-
fered by incorporating controlled heterogeneities, such as
designed molecular weight distribution, branching and
composition in the form of gradients, into the final prod-
uct. A combination of controlled synthesis with con-
trolled processing paves many efficient avenues for devel-
opment of advanced materials with new targeted proper-
ties that can benefit our society.
Acknowledgements
Creative contributions and discussions with many collabo-
rators and over 100 postdocs and graduate students at
Carnegie Mellon University are gratefully acknowledged.
Financial support from NSF (DMR 09-69301, CHE 10-
26060, DOE ER 45998) and CRP Consortium is acknowl-
edged.
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Received: September 3, 2011
Accepted: October 21, 2011
Published online: April 16, 2012
220 www.ijc.wiley-vch.de 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim Isr. J. Chem. 2012, 52, 206 220
Review
K. Matyjaszewski