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Atom transfer radical polymerization of hydrophilic
monomers and its applications
Cite this: Polym. Chem., 2013, 4, 2919
Weiwei He, Hongjuan Jiang, Lifen Zhang, Zhenping Cheng* and Xiulin Zhu*
Published on 30 January 2013 on http://pubs.rsc.org | doi:10.1039/C3PY00122A
Atom transfer radical polymerization (ATRP) has become one of the most widely used living radical
polymerization techniques for preparation of polymers with pre-designed compositions, topologies and
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functionalities. Hydrophilic (co)polymers are broadly used in various fields, such as hybrid materials,
surface modification and delivery carriers in biomedical areas because of their diverse functionalities
and ideal characters, including their non-toxicity, biocompatibility and environmentally friendly nature.
Polymerization of hydrophilic monomers by ATRP provides polymers with more colorful structures, as
well as novel properties and extends the application scope of hydrophilic polymers due to its facile
operation and commercially available catalysts, ligands and initiators of the methodology. This review
focuses on ATRP of hydrophilic monomers, as well as its application as detailed in five aspects: (1) basic
Received 24th January 2013
Accepted 29th January 2013
understanding of the ATRP mechanism and polymerization kinetics of hydrophilic monomers; (2)
polymerization media for hydrophilic monomers; (3) topologies of polymers based on hydrophilic
DOI: 10.1039/c3py00122a
monomers; (4) polymerization by combination of ATRP with other techniques, and (5) applications of
www.rsc.org/polymers polymerization of hydrophilic monomers.
1 Introduction living polymerization,1 such as anionic polymerization, where
no irreversible chain transfer and chain termination occur.
Well-dened polymers with pre-designed structures have long Harsh conditions and strict procedures are usually required in
been desirable in the area of polymer chemistry. In its early living polymerization, and it oen take researchers a relatively
stage, the synthesis of such polymers could only be achieved by long time to become familiar with its operation, and besides,
the monomers that can be used are quite limited. Such a state
in polymer chemistry lasts a long time and hinders the
Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, development of living polymerization for industrial
Department of Polymer Science and Engineering, College of Chemistry, Chemical applications.
Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
In industry, radical polymerization is still the mainstream
E-mail: [email protected]; [email protected]; Fax: +86-512-65882787;
+86-512-65112796 method to produce polymers because the process is more
Weiwei He was born in Jiangsu, Hongjuan Jiang was born in
China, in 1987. He received his Jiangsu, China, in 1988. She
BS degree in Chemical Engi- received her BS degree in
neering and Technology in June Chemical Engineering and
2009 from Soochow University. Technology in June 2010 from
Since September 2009, he has Soochow University. Since
been performing his PhD September 2010, she has been
research working on atom performing her PhD research
transfer radical polymerization working on atom transfer
(ATRP) with Professor Zhenping radical polymerization (ATRP)
Cheng at Soochow University in and reversible addition–frag-
Suzhou, China. His main mentation chain transfer (RAFT)
research interest is polymeriza- polymerization with Professor
tion of hydrophilic monomers using ATRP and design of biocom- Zhenping Cheng at Soochow University in Suzhou, China. Her
patible functional organic/inorganic hybrid nanoparticles. He has main research interest is polymer chemistry, including ATRP and
published 2 papers and obtained 1 patent (China). RAFT. She has published 2 papers.
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tolerant to functional groups and impurities and because of its functionalities and has received great attention since it
simple procedure. Accordingly, “living” radical polymerization emerged in 1995.4 Aerwards lots of catalyst systems6 and
(LRP, or “living”/controlled radical polymerization) had been a several kinds of ATRP, namely normal ATRP, reverse ATRP,7
longstanding goal in polymer science. Even still, such a wish simultaneous reverse and normal initiation (SR and NI)
was not realized until the 1980s, and the following few years ATRP,8 activators (re)generated by electron transfer (A(R)
witnessed rapid development. During that time, several tech- GET) ATRP,9 and initiators for continuous activator regen-
niques were developed, including initiator-transfer agent- eration (ICAR) ATRP,10 were developed either to reduce the
terminator (iniferter),2 nitroxide-mediated polymerization level of catalyst, lower the toxicity of the transition metal or
(NMP) or stable free radical polymerization (SFRP),3 atom extend the monomer ranges available, to meet various
transfer radical polymerization (ATRP) or transition metal- demands in practical applications. With collective effort
catalyzed living radical polymerization,4 and reversible addi- from a number of research groups worldwide, ATRP has
tion–fragmentation chain transfer (RAFT) polymerization.5 All been so well developed that it is capable of polymerizing a
of these methods are based on a rapid dynamic equilibration wide range of monomers in well controlled manners over
Published on 30 January 2013 on http://pubs.rsc.org | doi:10.1039/C3PY00122A
established between a few free radicals and an excess amount of the past two decades.
the dormant species. The composition, mainly depending on the employed
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ATRP has been acting as a robust tool to prepare poly- monomers, oen plays a critically important role in the
mers with different compositions, topologies and physical properties of obtained polymers that decide their
potential applications. Generally, monomers could be
roughly divided into two groups, hydrophobic and hydro-
philic ones. The latter group, in general, bear a functional
Lifen Zhang was born in Jiangsu, group that can form hydrogen bonds with water, rendering
China, in 1969. She received her them with good water solubility and excellent biocompati-
BS degree in Chemical Engi- bility that make them more attractive to scientists and
neering in June 1991 from Nanj- researchers than the former ones. Due to their unique
ing University of Technology, and characteristics, polymers based on hydrophilic monomers
her MS Degree in Chemical show alluring promise and application potential in many
Engineering in June 1994 from areas, especially in bio-related elds.11 In the present work,
Dalian University of Technology. we review the ATRP of hydrophilic monomers and its
She then worked at Soochow application in terms of 5 aspects: (1) basic understanding of
University as an assistant the ATRP mechanism and polymerization kinetics of
lecturer, lecturer, and associate hydrophilic monomers; (2) polymerization media for
professor, where she was awar- hydrophilic monomers; (3) topologies of polymers based on
ded a PhD degree in Polymer hydrophilic monomers; (4) polymerization by combination
Chemistry & Physics in June 2010 from Soochow University, and of ATRP with other techniques, and (5) applications of
has been a professor since May 2011. She is interested in research polymerization of hydrophilic monomers.
on living radical polymerization, and has published about 20
papers and 9 patents (China).
Zhenping Cheng was born in Xiulin Zhu was born in Jiangsu,
Jiangxi, China, in 1966. He China, in 1955. He received his
received his MS degree in BS degree in 1982, MS Degree in
Chemical Engineering in June 1985 and PhD degree in 1987 in
1994 from Dalian University of Macromolecule Chemical Engi-
Technology, and then worked at neering from Zhejiang Univer-
Soochow University as an assis- sity. He then joined Soochow
tant lecturer, lecturer, and University in January 1988 as a
associate professor, respectively. lecturer, became an associate
He was awarded a PhD degree in professor in 1990, and has been
Polymer Chemistry & Physics in a professor since 1994. His main
June 2003 from Soochow research interests are polymer
University, and has been a synthesis chemistry, including
professor at Soochow University since November 2007. He is mechanism and techniques for living radical polymerization, and
interested in research on living radical polymerization, surface the precise design and synthesis of functional macromolecules and
modication of different substrates and functional inorganic/ their performance. He has published about 190 papers and 15
organic hybrid nanomaterials, and has published about 160 patents (China).
papers and obtained 14 patents (China).
2920 | Polym. Chem., 2013, 4, 2919–2938 This journal is ª The Royal Society of Chemistry 2013
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2 Basic understanding of the ATRP
mechanism and polymerization kinetics of
hydrophilic monomers
2.1 Overview of mechanism
The ATRP technique was proposed as a living/controlled radical
polymerization methodology depending on a reversible equi-
librium between free radicals and dormant species realized by a
redox reaction of a particular transition metal complex. The
general mechanism of such a polymerization process is illus-
trated in Scheme 1. The key to such a procedure to control the
polymerization behavior is the transition metal catalyst, which
plays a critically important role in the whole process.
Published on 30 January 2013 on http://pubs.rsc.org | doi:10.1039/C3PY00122A
In the process of ATRP of hydrophobic monomers, the
monomers are usually inert toward the catalyst system; the
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transition metal forms a complex with certain ligands, which
modulates the polymerization behavior by controlling the
amount of free radicals. A low level of termination reaction
occurs because of the nature of the radicals, and sometimes a
few undesired chain transfer reactions occur. The side reactions
could be suppressed by optimizing the polymerization condi-
tions, for example, by employing a suitable ligand and/or
solvent. However, things are a little different in the ATRP of
hydrophilic monomers. Obviously, hydrophilic monomers,
bearing certain active groups, are generally much more reactive
than hydrophobic ones, which means they will not allow the
controlled polymerization to undergo smoothly. Some addi-
tional sides reactions involving monomers, which are unex-
pected in ATRP of hydrophobic ones, might happen. In most
cases, these effects generated from monomers are deleterious to
the whole polymerization, for example the complexation Scheme 2 Chemical structures of commonly used hydrophilic monomers.
between monomers and transition metals may cause it to lose
activity. As a result, ATRP of hydrophilic monomers is far more
difficult than ATRP of hydrophobic ones, and constructing an ATRP to control the polymerization; as a result, only a few
effective and versatile catalyst system is more challenging but hydrophilic monomers could be performed by ATRP under
meaningful for practical application. certain conditions. The most investigated three monomers are
N,N-(dimethylamino)ethyl methylate (DMAEMA), 2-hydroxy-
ethyl methacrylate (HEMA) and polyethylene glycol methacry-
2.2 Overview of the polymerization kinetics
late (PEGMA or OEGMA), which might be because the proper-
The chemical structures of common hydrophilic monomers ties of the polymers from these three monomers are more
polymerized by ATRP reviewed in the present work are listed in attractive to researchers; however, the absence of an effective
Scheme 2. As we can see, (meth)acrylate and analogues such as catalyst system to well control the polymerization behavior also
acrylamide (AM) and N-isopropylacrylamide (NIPAM) compose contributes to the lack of reports of ATRP of other hydrophilic
the main part, besides there are also some articles about styrene monomers. In summary, ATRP of hydrophilic monomers is
sulfonate and vinyl pyridines. Here, we give a brief summary of more difficult and less published than that of hydrophobic
the situation of the polymerization kinetics from different monomers.
points and detailed information is shown in the other parts. 2.2.2 Catalyst system. Since the emergence of ATRP in
2.2.1 Monomer ranges. Hydrophilic monomers might be 1995, a variety of transition metal catalysts have been devel-
involved in side reactions, which greatly limit the ability of oped, and most of them have been adopted to investigate the
polymerization behavior of hydrophobic monomers; however,
few of them have been applied in polymerization of hydrophilic
ones, which is probably due to side reactions between the
catalyst and monomers, and the low activity of the catalyst
towards hydrophilic monomers. As far as we know, only Cu, Ru
and Fe have been successfully employed in the investigation of
polymerization kinetics of hydrophilic monomers. Among
Scheme 1 The proposed mechanism of ATRP. them, Cu complexes are the most widely used, because of their
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higher efficiency and better suitability than the others. Never- convenient choice from a number of transition metal catalyst
theless, Fe catalysts are more appealing and attractive when systems, render it a powerful candidate to prepare polymers in
preparing biomaterials because of their biocompatibility. The varying conditions that could fulll various requirements.
structures of the common ligands (or complex) for these tran-
sition metals are listed in Scheme 3. 3.1 Polymerization in bulk or organic solvents
2.2.3 Polymerization dispersion phase and adopted
temperature. The dispersion and the adopted temperature are ATRP can be simply carried out in bulk.12 However, more oen,
more related in the polymerization of hydrophilic monomers a suitable solvent is needed, not only to dissolve monomers and
than for hydrophobic ones. Generally, a high temperature (70– polymers, as well as the catalyst, but also to decrease/accelerate
90 C) is oen adopted when polymerizations are performed in the polymerization rate for better control. The solvent may have
nonpolar solvents and low temperature (30–70 C) is used for an important role in polymerization, and a totally different
those in polar and protic solvents. Polymerizations in aqueous polymerization behavior, more specically, the polymerization
media by a Cu catalyst are oen carried out at room tempera- rate and controllability, oen occurs when altering the
Published on 30 January 2013 on http://pubs.rsc.org | doi:10.1039/C3PY00122A
ture (20–30 C) or even lower (0–5 C). The only emulsion solvent.13 The solvent affects the ATRP equilibrium constant
polymerizations of hydrophilic monomers were developed (KATRP) and therefore has an impact on the limits of control (i.e.,
employing Cu as catalyst at 30 C by Matyjaszewski, and PEGMA the apparent rate constant above which control is lost). Helena
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and HEMA were successfully polymerized (see part 3.4). Bergenudd took advantage of ve copper complexes combined
with six monomer–solvent mixtures to investigate the solvent
effects on ATRP of PEGMA. The redox properties of the poly-
3 Polymerization media merization mixtures and the apparent rate constants (kapp p ) for
ATRP of PEGMA were correlated in order to control the poly-
An appropriate polymerization medium, including solvent, merizations.13a ATRP of hydrophilic monomers was successfully
catalyst system, and polymerization site is of crucial importance performed by employing several kinds of solvents, including
for controlling the properties of polymers, such as molecular nonpolar ones such as anisole14 and toluene,15 or polar ones like
weight, molecular weight distribution tacticity, etc., accordingly N,N-dimethylformamide (DMF)16 and dimethyl sulfoxide
deciding its performance in applications. The capability of (DMSO).17 It is quite interesting that polymerization of
ATRP to be carried out either in solution or in bulk and the DMAEMA in anisole could undergo smoothly without the
addition of any external reducing agents because of the tertiary
amine group in the monomer, which served as an internal
reducing agent in ARGET ATRP (Scheme 4). Various external
reducing agents were also investigated for the polymer-
ization.14b Even in protic solvents, such as methanol,18
ethanol,19 and ethylene glycol,20 polymerization can also
undergo with excellent controlled behavior. Sometimes, a
mixed solvent is needed in order to get well-dened polymers.21
A 3/2 (v/v) mixture of methyl ethyl ketone and methanol was
employed to investigate the polymerization of hydroxyethyl
methacrylate by using activators generated by electron transfer
(AGET) ATRP.21a A satisfying result with a narrow dispersion of
polymers was obtained.
3.2 Polymerization in aqueous media
3.2.1 In a mixture of water and organic solvent. Water is
not only tolerant of the process of polymerization in ATRP, but is
also necessary to solubilize the monomer bearing hydrophilic or
ionic groups to make the medium homogeneous to achieve
Scheme 4 The proposed mechanism of ARGET ATRP of DMAEMA with internal
Scheme 3 The structures of ligands (or complexes) for transition metals. reducing agent in the presence of air. From ref. 14b.
2922 | Polym. Chem., 2013, 4, 2919–2938 This journal is ª The Royal Society of Chemistry 2013
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better control. A certain amount of water was added to several several advantages to polymerization in scCO2: (1) low viscosity
water-miscible organic solvents in the polymerization of NIPAM, which gives it liquid-like density and gas-like diffusivity; (2)
and a relatively fast polymerization and well controlled behavior being inert to radical species which guarantees no chain
appeared, while remaining at a low temperature.22 The low transfer occurs, a precondition for a well controlled process,
polymerization rate in pure alcoholic media (methanol, ethanol and (3) facile adjustment of solvent strength by altering the
and n-propanol) is attributed to the poor solubility of the olig- temperature and pressure. Besides, the solvent can be conve-
omer in such solvents; thus PNIPAM chains aggregate, resulting niently removed aer polymerization. A specic catalyst with
in the inaccessibility of halide atoms to the copper catalyst due to good enough solubility in scCO2 has to be used. To achieve this,
embedding in the polymer chains. Many successful cases of a uorinated derivative of 4,40 -dinoyl-2,20 -bipyridyl (dNbpy) was
polymerization of hydrophilic monomers have been reported in employed as the ligand.33 Well-dened acrylates and methac-
water containing solvents, including DMF,23 2-propanol,24 rylates with uorinated alkyl groups were thus prepared in
ethanol25 and methanol.26 ATRP using ethyl 2-chloropropionate scCO2 which was used as a macro-initiator for further chain
(ECP) as the initiator and CuCl/tris(2-dimethylaminoethyl) extension of DMAEMA. Sometimes, a cosolvent should be
Published on 30 January 2013 on http://pubs.rsc.org | doi:10.1039/C3PY00122A
amine (Me6TREN) as the catalytic system was carried out in added if needed, caprolactone (CL) was included when utilizing
DMF–water (50 : 50, v/v) mixed solvent at 20 C.23a The poly- CuBr/bpy as the catalyst in the ATRP of methyl methacrylate
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merization rate increased signicantly with decreasing DMF– (MMA) and HEMA in scCO2.34 The copolymer can be further
water ratio. This acceleration phenomenon by adding water in graed by PCL via an ROP process. Reverse ATRP of an acidic
the polymerization was attributed to the positive interaction monomer, namely AA, was also successfully conducted in scCO2
between copper species and water, which was also observed and by using V-70 as the free radical source, and CuCl2/bpy as the
conrmed in many other copper-mediated ATRP. catalyst, very recently.35
3.2.2 In pure water. Obviously, water is the most environ-
mentally friendly and inexpensive solvent of all, and the driving
force for using such an ideal solvent has led researchers to 3.4 Inverse miniemulsion polymerization
develop polymerization systems in water. A decade ago, Char- Emulsion systems are widely employed in industry to produce
leux et al. reviewed LRP in aqueous media.27 Unfortunately, few commercial products such as paints, coatings and adhesives. A
successful examples were demonstrated by then, especially miniemulsion system shares many similarities with emulsions,
polymerizations in pure water. Compared to NMP and RAFT, although presenting a different nucleation mechanism; the
ATRP in water has made more progress to date. Aer the rst details have been thoroughly discussed in former reviews.27,36
ATRP case of 2-hydroxyethyl acrylate (HEMA) in aqueous solu- The monomers used in such systems are typically hydrophobic
tion employed CuIBr/bpy as the catalyst and diethyl 2-methyl-2- (e.g., styrene, acrylates and methacrylates). Inverse mini-
bromomalonate (MBP) as the initiator,28 some other water- emulsion (O/W), however, with a hydrophobic continuous
soluble or hydrophilic monomers have been employed for ATRP phase and an aqueous dispersed phase, facilitates polymeriza-
in water, such as AM,29 sodium methacrylate (NaMA)30 and tion of hydrophilic monomers. Matyjaszewski and co-workers
PEGMA.31 Among them, polymerization of PEGMA is the most developed the rst application of ATRP in an inverse mini-
investigated, and several catalyst systems have been developed. emulsion to prepare poly[oligo(ethylene glycol) monomethyl
Various bromide-based initiators in conjunction with a copper- ether methacrylate] particles with colloidal stability, while
based catalyst afforded the rapid homopolymerization of maintaining a well controlled manner in 2006 (Scheme 5).37 A
PEGMA in water at 20 C.31c It is more exciting that recently, nonionic emulsier, Span 80 (HLB value ¼ 4.3), was used to
Cheng et al. developed an iron-mediated catalyst for polymeri- stabilize the emulsion and tris(2-pyridylmethyl)amine (TPMA)
zation of PEGMA in water by using FeCl3$6H2O as the catalyst, and 2,20 -bipyridyl (bpy) were selected as the ligands, consid-
tris-(3,6-dioxaheptyl) amine (TDA-1) as the ligand, and ascorbic ering the water solubility and activity of the complex with Cu
acid as the reducing agent.31a In contrast to the cases in copper-
mediated aqueous ATRP, no acceleration was detected in this
work. Although a few successful cases of aqueous ATRP have
been reported, it is still challenging to perform polymerization
in water because of several side reactions involved in such a
process, such as undesired irreversible chain transfer and
termination, which might cause the catalyst or initiator to lose
activity.27,32 Hence, much basic work on ATRP in water still
needs to be investigated in detail to satisfy various demands,
since it has quite promising potential in lots of areas, especially
in bio-related areas.
3.3 Polymerization in supercritical carbon dioxide (scCO2)
Aside from water, scCO2 is another environment benign solvent
which is nonammable, nontoxic and inexpensive. There are Scheme 5 Illustration of inverse miniemulsion, AGET ATRP. From ref. 37b.
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halide. As for the initiator, the macro-initiator PEO-Br was also different solvents due to a solvent induced rearrangement of the
synthesized to replace the commonly used ethyl bromoisobu- polymer brushes for the same feed ratio. It is more exciting that
tylate (EBiB), which is widely adopted in polymerization in bulk this change was reversible. Hydrophilic monomers are always
or organic solvents, as it is much more hydrophilic. The results preferred options to modify materials for optimum properties
also proved that this choice led to a better outcome. Another and varying functionalities. Hydrophilic/amphiphilic polymer
successful case of ATRP in inverse miniemulsion is the brushes were successfully graed onto various materials,
synthesis of di- and triblock copolymers (PEO-b-PHEMA and including silica,43 silicon,44 lms,45 bers,46 carbon nanotubes,47
PHEMA-b-PEO-b-PHEMA) by using monofunctional and metals and their oxides,48 etc. Formation, as well as the
difunctional macro-initiators, respectively.38 Since then, several assembly of polyampholytic block copolymer brushes by the
biodegradable nanogels using a disulde-functionalized dime- sequential polymerization of DMAEMA and sodium methacry-
thacrylate cross-linker, as well as nanostructured hybrid late (NaMA), followed by protonation of the PNaMA block on at
hydrogels based on PEGMA for drug delivery, were prepared by impenetrable silica in solution was discussed. The conforma-
taking advantage of this inverse miniemulsion.39 ATRP in tion of such an individual polyelectrolyte block can be regulated
Published on 30 January 2013 on http://pubs.rsc.org | doi:10.1039/C3PY00122A
inverse miniemulsion can be considered as a versatile route to in solution, as a function of solution pH.44d Because of the
prepare gels for drug release which were reviewed by graing of hydrophilic polymers, materials aer modication
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Matyjaszewski.40 possess better dispersibility in polar solvents, as well as in
water, and are more biocompatible.49 To execute ATRP of
PEGMA on magnetic nanoparticles (MNPs), macro-initiators
3.5 Substrate supported polymerization were immobilized on the surface via effective ligand exchange
3.5.1 Supported catalyst. ATRP is a versatile method to of oleic acid with 3-chloropropionic acid (CPA). The obtained
prepare functional materials; however, before AGET ATRP was PPEGMA graed MNPs with a uniform hydrodynamic particle
developed, a high concentration of transition metal was oen size are hydrophilic and biocompatible, exhibiting low cyto-
needed to maintain a controlled polymerization manner toxicity, and accordingly showing great potential for application
because of its low efficiency; consequently, there are always in magnetic resonance imaging (MRI) of specic biotargets.49c
metals present in the nal products, resulting in a deep color Several interesting characteristics including environmental
and lowering their quality, and therefore limiting the applica- response50 were also introduced to materials by SI ATRP of
tions of ATRP. In order to widen its applications, various means hydrophilic monomers. 2-Bromoisobutyryl bromide (BiBB) was
have been employed. Heterogeneous polymerization with a used to react hydroxyl groups on the surface of regenerated
solid xed catalyst was exploited to enhance the efficiency of the cellulose (RC) membranes to immobilize the ATRP initiator,
catalyst and improve the product quality.41 A highly effective from which a polymer chain of acrylic acid (AA) grew. The
copper ligand, hexamethyltriethylenetetramine (HMTETA) xed permeability of the membranes aer modication can be
on silica gel, along with CuBr, was chosen to synthesize poly- modulated by regulating the pH value. In summary, materials
(methyl methacrylate) (PMMA) and PDMAEMA macro- aer modication with hydrophilic monomers exhibit more
monomers with terminal vinyl or allyl groups by ATRP with attractive properties and could meet more and more strict
vinyloxyethyl 2-bromoisobutyrate (VBIB) or allyl 2-bromoisobu- requirements in different elds in the future.
tyrate (ABIB) as initiator. The catalysts were recycled and could Anchoring of initiators on the surface is considered to be the
still mediate a living radical polymerization of MMA or most important step in SI ATRP to achieve a good modication
DMAEMA with decreasing of their catalytic activities due to process. Generally, an ATRP initiator consists of a simpler
radical side reactions, as well as catalyst loss during recycling.41a structure, compared to other living radical polymerization
JandaJels resins were selected as the substrates to immobilize mediators, which could be easily prepared. For example, lots of
ligands, in an attempt to obtain a high polymerization rate and materials bear or could introduce numbers of hydroxyl groups
narrow molar mass distribution, since they have good organic on the surface that could readily react with BiBB to immobilize
solvent compatibility and site accessibility due to the exible the ATRP initiator. Scheme 6 lists the main synthetic routes
cross-linker. The catalyst–ligand complex could be easily used to immobilize ATRP initiators on substrate surfaces. Of
removed by ltration aer polymerization with a trace amount course, some special methods should be introduced to attempt
of residual copper (0.05–0.07% by elemental analysis) in the to acquire satisfactory effects. Polymer macroinitiators carrying
products without purication.41b lots of active sites were deposited on substrates, aiming to
3.5.2 Supported initiator. An ATRP initiator, generally obtain dense polymer brushes.51 Layer-by-layer (L-b-L) deposi-
containing a second or tertiary halogen, can be readily intro- tion of oppositely charged polyelectrolytic macroinitiators has
duced on a substrate because of the existence of a great number been demonstrated to control the surface density of bromoester
of hydroxyl groups on the surfaces of lots of materials. Subse- initiator groups, simply by changing the number of macro-
quently, polymer brushes can be conveniently formed by a so- initiator layers. A dense and thick brush formed due to the good
called “graing from” method.42 Tapered copolymer brushes surface graing density from SI ATRP of HEMA in a 1 : 1
responding to selective solvent treatments were synthesized via methanol–water mixture at ambient temperature.51a Poly(tetra-
surface-initiated (SI) ATRP by gradually adding HEMA to a uoroethylene) (PTFE) membranes have a great number of C–F
reaction mixture that originally only had MMA as monomer.42c groups, an analogue of the widely used ATRP initiators C–Cl and
The hydrophilicity of the surface could be tuned by treating with C–Br. The C–F groups became effective initiators through
2924 | Polym. Chem., 2013, 4, 2919–2938 This journal is ª The Royal Society of Chemistry 2013
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are diverse, copper, as we can see, is the most studied and
applied one since it is more effective and powerful than the
others. Actual cases of polymerization of hydrophilic mono-
mers employing other transition metal catalysts are even rarer.
Pd and Ni based catalysts showed a capability to polymerize
DMAEMA in a combined manner of ATRP and free radical
polymerization.54 Copolymerization of HEMA with an excess of
MMA was also carried out in toluene by Ni-mediated radical
polymerization.55 Cationic coordinatively saturated complexes
of ruthenium(II), [Ru(o-C6H4-2-py)(phen)(MeCN)2]+, conducted
polymerization of HEMA in protic media and acetone under
homogeneous conditions.56 Sawamoto et al. developed a kind
of versatile ruthenium catalyst, [Cp*Ru(Cl)L1L2, by judiciously
Published on 30 January 2013 on http://pubs.rsc.org | doi:10.1039/C3PY00122A
selecting ligands (phosphines) and cocatalysts (amines), which
proved to have a powerful capability for living radical homo-
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and copolymerization of a variety of functional methacrylates,
including PEGMA, DMAEMA and HEMA in polar media.57
Among these metals, iron has attracted the interest of more
and more researchers because of its unique characteristics
over the others, namely its abundance, low cost, environmen-
tally benign nature and biocompatibility. Iron based catalysts
have been widely employed for homopolymerization31a,58 of
hydrophilic monomers and surface modication of several
kinds of material, including chitosan,59 stainless steel,60 iron
oxide61 and poly(vinylidene uoride) (PVDF)62 via AGET ATRP.
The polymerization behavior of SI AGET ATRP by iron catalyst
was investigated in detail using SiO2 nanoparticles as the
substrate, which can be easily removed by hydrouoric acid,
and the living features were conrmed by the polymerization
kinetics of MMA and the evolution of the number-average
molecular weights and molecular weight distributions for
graed PMMAs obtained by removing the SiO2 core with total
monomer conversion and chain extension with PEGMA as
monomer for the rst time.63
4 Topology
4.1 Linear polymers
To date, the great majority of monomers are polymerizable by
ATRP with narrow molecular weight distributions and pre-
determined molecular weights. Polymers by homopolymeriza-
tion usually exhibit monotonous physical/chemical properties
which could not satisfy ever-increasing demands for novel
Scheme 6 Generally synthetic routes to immobilize ATRP initiator on materials
materials nowadays. Copolymerization of different monomers
surfaces.
with the optimum option oen results not only in the combined
properties, but also sometimes introduces a novel synergetic
character to the products. A simple procedure is mixing two or
hydrogen plasma treatment and could mediate SI ATRP of
more monomers before they are subjected to polymerization.64
PEGMA directly.52
Polymers prepared by this strategy generally have a random
sequence of monomer units, which might decrease the product
3.6 Non-copper mediated polymerization quality. Copolymers with high order, such as block copolymers,
The key part of ATRP is the transition metal catalyst, which, normally show better and more exible properties by tuning the
together with the radical species, establishes the fundamental sequence, as well as the block chain length. There are basically
reversible equilibrium to keep free radicals at low concentra- two means to prepare block copolymers: the rst is sequence
tion. Many transition metals were demonstrated to qualify for polymerization,65 polymers synthesized by ATRP usually have a
this role soon aer the appearance of ATRP and details have high end functionality, which could be used as a macroinitiator
been reviewed before.53 Although the transition metal catalysts to polymerize another monomer further. The other is to employ
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a macroinitiator to directly synthesize the block copolymer, route is by modifying these biomaterials as initiators to initiate
which is called a macroinitiator approch.66 Rod–coil diblock polymerization of functional monomers.
copolymers were synthesized by polymerization of HEMA with a
well-dened oligouorene initiator.67 Multiblock copolymers
can be readily prepared by choosing difunctional macro- 4.3 Star polymers
initiators. Novel amphiphilic ABA triblock copolymers suitable Star polymers can be easily prepared by using a multifunctional
for surface modication of polysulfone membranes were initiator that was recognized soon aer advent of ATRP. With
successfully synthesized using a bromo-terminated difunc- such readily prepared initiators with multiple active sites of
tional polysulfone as macroinitiator.68 Modied poly(ethylene equal reactivity, it is relatively convenient to synthesize poly-
oxide)100-poly(propylene oxide)65-poly(ethylene oxide)100 was mers with one core and multiple identical arms. Because of the
used to initiate polymerization of NIPAM, giving rise to double facile synthesis of the ATRP initiator, star polymers with diverse
thermosensitive and narrow dispersed PNIPAm110-PEO100- cores were prepared ranging from small molecules80 and bio-
PPO65-PEO100-PNIPAm110 pentablock terpolymer.69 Composi- compounds73 to complex topological polymers81 and even
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tion or functionality can be facilely planted into a block copol- inorganic materials (e.g., silsesquioxane82 and phthalocyanine
ymer with these two methods. Fluoride could be introduced by as well as its analogues83). Block copolymers arms with richer
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either a macroinitiator approach70 or sequence polymerization functionalities were prepared for the purpose of synthesizing
of monomers consisting of uorinated ones.71 smart materials.84
Miktoarm star polymers sometimes might have novel prop-
erties, however their preparation is oen more complicated and
4.2 Bio-hybrid copolymers time-consuming. Y-shaped polymers (three arm star polymer
Natural polymer based materials are of great interest to with two identical arms) were synthesized by ATRP using a
researchers and engineers due to their unique excellent difunctional macroinitiator. 2,2-Dichloroacetyl chloride was
structures and properties. However, their properties are employed to esterify PEG to form an adjacent difunctional site
limited, and synthetic polymers, a diverse category, are oen from which polymerization could be simultaneously carried
made use of to make up for the deciency. Cyclodextrins (CD) out.85 Well-dened Y-shaped zwitterionic block copolymers
are a series of cyclic oligosaccharides consisting of 6–8 glucose were synthesized by a two step ATRP.86 First, an ATRP initiator
units that are water soluble but have hydrophobic internal bearing two identical hydroxyl groups was synthesized, followed
cavities, with diameters range from 0.42 to 0.83 nm that are by polymerization of DEAEMA. The bromine end groups of
available for capturing various small compounds and poly- PDEAEMA were then completely removed by radical chain
mers. CDs have been widely used in pharmaceutical applica- transfer by dealing with excess N,N,N0 ,N00 ,N00 -pentamethyldi-
tions. Supramolecular hydrogels were prepared by the ethylenetriamine (PMDETA). Secondly, hydroxyl groups at the
inclusion complexation of PEG102-b-PDMEMA96 and a-CD in other end were esteried using excess BiBB to afford a
water under stirring with ultrasonic agitation. The resulting PDEAEMA-based difunctional macroinitiator [PDEAEMA-(Br)2],
composite showed a response to solution pH and ionic which was employed to mediate ATRP of HEMA. Aer poly-
strength.72 A star shaped PNIPAM with CD end groups (star- merization, the hydroxyl groups in the PHEMA side chains were
PNIPAM-CD) was synthesized by an ATRP process: rst, a b-CD- treated with excess succinic anhydride to form Y-shaped zwit-
core with 21 initiation sites was synthesized by the reaction of terionic block copolymers.
b-CD with 2-chloropropionyl chloride (CPC); then a 21-arm A supramolecular star shaped ABC terpolymer was synthe-
star-PNIPAm with partial b-CD termination was synthesized by sized by a facile strategy with the aid of molecular recognition
sequence ATRP of NIPAM and monovinyl b-CD (GMA-EDA-b- between the b-cyclodextrin-(b-CD–)based host and the
CD).73 A series of interesting polyrotaxanes was prepared by adamantine-(AD–) modied guest, as well as “click” reaction.87
Feng et al. via ATRP, as well as inclusion complexation of CD Firstly, b-CD with two different functional groups was prepared
with linear poly(ethylene glycol) (PEG). Difunctional initiators to construct a diblock copolymer host via “click” reaction with
based on linear PEG or PEG-b-PPO-b-PEG were synthesized and alkynyl-poly(ethylene glycol) (alkynyl-PEG) and ATRP of
assembled with CDs to form hybrid initiators, followed by DMAEMA, respectively. In the meantime, the AD-modied
polymerization of different monomers through ATRP or polymeric guest was obtained by ATRP of MMA. Molecular
combined techniques.74 recognition between b-CDs and adamantyl moieties led to an
Cellulose is the most abundant polymer in nature, mainly ABC miktoarm terpolymer by a simple mixing procedure. The
found in plant cell walls, which is widely used in many elds reversible transition between assembly and disassembly of this
such as membranes, pharmaceuticals, and food.75 Bearing three supramolecular ABC miktoarm star terpolymer was realized by
reactive hydroxyl groups per anhydroglucopyranose unit makes adding a competitive host or guest.
cellulose facile to modify for the design of advanced polymeric Most star polymers were prepared by a “core rst” method,
materials with elaborate considerations. Regioselective poly- namely by a simultaneous multi-initiated polymerization, while
merization of NIPAM or PEGMA onto cellulose was realized by there are a few exceptions. Star polymers containing GRGDS
ATRP with a selectively modied cellulose macroinitiator. Other (Gly-Arg-Gly-Asp-Ser) peptide sequences on the star periphery
bio-hybrid copolymers based on amino acid,76 lignin,77 were synthesized via an “arm-rst” method.88 GRGDS was
peptide78 and protein79 were also synthesized by ATRP. A general modied to be a monomer poly(ethylene glycol)acrylate
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(GRGDS-PEG-Acryl) which was used for ATRP along with
PPEGMA macromonomer, uorescein o-methacrylate (FMA)
and ethyleneglycol dimethacrylate (EGDMA). The resulting
polymer displayed rapid uptake of GRGDS peptides, indicating
enhanced delivery potential.
4.4 Branched (co)polymers
Branched polymers have become of special interest because of
their interesting properties and industrial importance.89
Generally, branched polymers could be easily synthesized by
using an AB* inimer (monomer consisting of an initiating
group). The preparation route, as well as its working mecha-
Published on 30 January 2013 on http://pubs.rsc.org | doi:10.1039/C3PY00122A
nism is illustrated in Scheme 7. Various functional hydrophilic
monomers, including DEAEMA,90 DMAEMA,91 HEMA92 and
NIPAM were employed accompanying these inimers to form
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random branched polymers with enhanced properties. A series Scheme 8 Schematic of formation of branched copolymers by ATRP by
of macromonomer initiators based on PEG (Mn ¼ 490, 2200, employing a divinyl monomer. From ref. 89.
and 4200 g mol1) were synthesized, which aerwards were
used to initiate ATRP of NIPAM to obtain PEG-b-PNIPAM
branched copolymers.93 The resulting branched copolymer 4.5 Gra polymers
exhibited a volume phase transition at ca. 36 C and the plas-
4.5.1 Graing from polymer chains. It is quite convenient
ticizer effect of PEG in gra copolymers was also observed,
to obtain polymers with ATRP initiators on the pendent side
indicating a lower glass transition temperature than that of
chains by either polymerization of initiator bearing monomers
pure PNIPAM.
or post-modication of the functional side chains. By using
Branched polymers can also be obtained by copolymeriza-
such polymers as macroinitiators, new monomers could
tion of monomers consisting of a divinyl under specic condi-
directly grow from the backbone, resulting in comb–like poly-
tions. Copolymerization of 2-hydroxypropyl methacrylate
mers, which is widely considered as a “gra from” method.
(HPMA) with a low level of either EGDMA or bisphenol A
Amphiphilic cylindrical polymer brushes were prepared by the
dimethacrylate (BPDMA) as the branching agent was carried out
following procedures: (1) ATRP of HEMA gave well-dened
using ATRP (see Scheme 8).94 Analysis of the molecular weight
PHEMA; (2) esterication of the pendent hydroxyl groups with
and polydispersity of the polymers indicated that highly
BiBB to yield a macroinitiator denoted as PBIEM, and (3)
branched chains only formed at high conversions (>90%).
sequence ATRP of various monomers using PBIEM as the
Dendritic copolymers A(BC)n containing m-PEG (block A), MMA
initiator and post-modication to form amphiphilic core–shell
and nonquaternized DMAEMA (blocks BC) were reported using
polymer brushes.96 Gra polymers based on several polymer
a star like multi-initiator.95
backbones from (co)polymerization of functional monomers
were prepared. The polymer backbone with a number of initi-
ating sites is the most crucial intermediate. Some of them arise
from post-modication of the pendent chains bound to the
backbones, such as poly(ether sulfone ether ketone ketone)
based gra polymers,97 polymers originating from polymeriza-
tion of a HEMA derivative (HEMA-TMS),98 cyclic PEG,99
PHEMA100 and polypropylene,101 while the others formed
directly from copolymerization of monomers with an inimer.
Helical polyacetylenes bearing –Br moieties in their side chains
were prepared by catalytic copolymerization, which were
employed as macroinitiators for the subsequent ATRP of
DMAEMA.102 Poly((N-vinylcarbazole)-co-(4-vinylbenzyl chloride))
(P(NVK-co-VBC)) copolymer backbone was synthesized by free
radical polymerization and was used as an ATRP mediator for
polymerization of DMAEMA and tert-butyl acrylate (t-BA).103
Hydrophilic PVDF was realized by gra polymerization of
DMAEMA using C–F bonds as the initiator.104
Apart from the “gra from” method, there are another two
means to produce gra polymers, namely “gra through” and
Scheme 7 Schematic showing formation of branched polymers using an inimer. “gra to” techniques. The former one is based on the poly-
From ref. 94. merization of macromonomers,105 the latter one, however,
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undergoes such a procedure: two types of polymers carrying could be used as a container to capture molecules, drugs and so
active groups on the side chains and the ends, respectively, are on. Au nanocrystals were used as the template and modied
prepared independently, followed by a chemical coupling with an ATRP initiator on the surface by a ligand exchange
reaction at the active sites between these two polymers, result- process. Subsequently, SI ATRP of DMAEMA or PEGMA was
ing in a gra topology. Polystyrene (PS-Br) obtained by ATRP carried out in the presence of a selective chemical cross-
was treated with hydroxyl benzodioxinone (HDPD).106 The linker.114 Capsules were then constructed by etching the Au
resulting functional polystyrene (PS-B) was graed on the cores with KCN aqueous solutions (15 and 0.15 mg mL1).
statistical PMMA-co-PHEMA backbone with the aid of photol- Capsules may also be prepared by a substrate-free process. The
ysis at linc > 300 nm. In order to improve the quality of chitosan addition of EGDMA aer ATRP of MMA and PEGMA for further
with 88.5% degree of deacetylation, PDMAEMA was prepared by suspension polymerization in an oil/water bath gave capsules at
ATRP with an initiator bearing N-succimidyl (NSI) groups.107 17 mol% PEGMA by ATRP, whereas conventional free-radical
The NSI capped PDMAEMA was easily graed to the chitosan by polymerization required 24 mol% PEGMA due to a low poly-
active ester conjugation. merization rate in ATRP.115
Published on 30 January 2013 on http://pubs.rsc.org | doi:10.1039/C3PY00122A
4.5.2 Graing from polymer particles. Polymer particles 4.6.3 Hydrogels. Gels could be easily prepared by adding a
are an important member of the polymer family, which have cross-linker or by complexation of reactive groups among
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promising potential in coatings, drug delivery, etc. Polymer polymer chains. Hydrogels, made from hydrophilic mono-
particles usually need to be modied with linear polymers on mers, usually show an environmental response because of the
the surface to alter the surface properties to satisfy the functional groups in the side chains. Thermo-responsive
requirements in special occasions. Stöver et al. demonstrated a hydrogels based on NIPAM116 and PEGMA,117 respectively,
series of polymer graed microspheres based on swellable were prepared. A hydrogel based on triblock copolymers
poly(DVB80-co-HEMA). First, the poly(DVB80-co-HEMA) of P(DMAEMA-co-HEMA)-b-P(NIPAM)-b-P(DMAEMA-co-HEMA)
substrate was synthesized by a free radical polymerization was synthesized by consecutive ATRP using ethylene glycol di-
process; the pendent hydroxyl groups, as well as the residual 2-bromoisobutyrate (Br–EG–Br) as the starting ATRP initiator,
vinyl groups in the outer zone were taken advantage of to react followed by a cross-linking process, taking advantage of the
with BiBB to form an ATRP initiator for post-modication by hydroxyl groups of the incorporated HEMA units.118 The as-
polymerization of selective monomers.108 Polystyrene based prepared hydrogels exhibited responses to both temperature
particles obtained by either employing divinylbenzene (DVB) as and solution pH, arising from the PNIPAM blocks and
the cross-linker,109 from self-assembly110 or by copolymerization PDMAEMA segments in the cross-linked matrices,
with functional monomer (HEA-Cl),111 were also successfully respectively.
decorated by graing polymerization by ATRP. Cross-linked Macroporous hydrogels (MHs) with pore sizes up to 100 mm
microspheres were prepared by polymerization using 4-vinyl- and a total porosity of 94–97% were prepared by cross-linking
benzyl chloride (VBC) as the monomer and EGDMA as the cross- polymerization of HEMA or cross-linking co-polymerization of
linking agent. Subsequent modication of the microsphere HEMA with dimethylacrylamide (DMAA) in semi-frozen state.119
surfaces was achieved via SI ATRP of DMAEMA using the benzyl Hydrogels with interpenetrating networks were also demon-
chloride moiety as initiator.112 strated by the simultaneous effects of “Click Chemistry” and
ATRP.120 Recently, biodegradable hydrogels have attracted more
attention than before because of their promising applications
4.6 Cross-linked networks in biomedical areas.121
Cross-linked networks exhibit relatively higher stability The network in a hydrogel is normally realized by covalent
compared to the assembly of polymers because of their 3- bonds, while some were achieved by other forces. Star-like
dimensional structures. As a consequence, cross-linked polycations based on b-CD-g-PDMA and linear polyanions based
networks are quite prevalent in many application elds. For on triblock copolymers PMAA30-b-PEG-b-PMAA30 were synthe-
example, delivering drugs using cross-linked network carriers sized by ATRP using b-CD as the macro-initiator and ring
could effectively protect from premature release of the drug at opening polymerization (ROP) independently. Then, hydrogels
undesired sites, which might cause serious side effects or even were formed by supramolecular assembly through electrostatic
poisoning of living beings. interactions.122
4.6.1 Polymer particles. Well-dened pH-responsive poly-
mer nanoparticles were prepared in water directly by dialysis 5 Combination with other methodologies
from a branched AB diblock copolymer precursor without self-
assembled interactions. The branched AB diblock copolymers The charm of polymers lie in their diversity, which is brought
were achieved by one-pot sequence ATRP of PEGMA and about by not only the various monomers, but also by novel and
DMAEMA/DEAEMA, employing a difunctional monomer well dened topology realized by some powerful polymerization
EGDMA in the second phase.113 Clear polymer nanoparticle techniques. Normally, it is impossible or difficult and time-
(170–244 nm) suspensions were obtained aer dialysis against consuming to achieve polymers with complicated structures by
water. using only one technique. Thus, a combination of two or more
4.6.2 Polymer capsules. A substrate is usually needed for methodologies emerges and is becoming a trend for design of
preparing polymer capsules with a hollow structure, which desired topological polymers.
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5.1 Ring opening polymerization (ROP) readily prepared by just introducing alkynyl or azido groups into
the side chains of one polymer, followed by ‘click’ reaction with
ROP is an effective tool to prepare polyesters such as PCL and
end capped polymers.139 A well-dened amphiphilic and ther-
polylactide (PLA), which are degradable under specic condi-
moresponsive ABC miktoarm star terpolymer, PEG(-b-P(t-
tions and therefore, environmentally friendly. A combination of
BMA))-b-PNIPAM, was synthesized via a combination of
ATRP with ROP might make it much more convenient to
consecutive click reaction and ATRP.140 Macrocyclic molecular
synthesize materials with more preferable functionalities.
brushes of c-PHEMA-g-(PS-b-PEO) based on PHEMA (the back-
The initiator, as well as the product of ROP, in general,
carries hydroxyl groups which could be readily converted to bone) were synthesized by the combination of ATRP and click
ATRP initiator by treating with a halide, BiBB for example. chemistry, together with single-electron transfer nitroxide
radical coupling (SET-NRC): ATRP of HEMA using 3-(trime-
Therefore, ROP and ATRP could be carried out in a sequence
thylsilyl)propargyl 2-bromoisobutyrate as initiator to give linear
and functional polymers can be prepared by choosing different
a-alkyne PHEMA, then chlorine end groups were transformed to
monomers. ROP of epsilon-caprolactone123 and lactide,124 fol-
–N3 groups by nucleophilic substitution reaction in DMF, fol-
Published on 30 January 2013 on http://pubs.rsc.org | doi:10.1039/C3PY00122A
lowed by esterication of end hydroxyl groups with halide for
lowed by ‘click’ in high dilution conditions, resulting in a cyclic
further ATRP of DMAEMA gave amphiphilic diblock polymers.
PHEMA. The hydroxyl groups on c-PHEMA were transformed
Starting from difunctional125 or multifunctional126 initiators
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gave rise to triblock and star shaped amphiphilic copolymers. A into bromine groups by esterication with BiBB for ATRP of
hydrolysis-resistant amide-linked heterofunctional initiator was styrene and further coupling with TEMPO–PEO afforded the
target macrocyclic molecular brushes c-PHEMA-g-(PS-b-PEO) by
synthesized for ATRP of NIPAM, and the end group was then
SET-NRC with high efficiency (ca. 80–85%).141
replaced by amine hydrochloride which was used for further
The properties of polymers can be facilely improved by
ROP of N3-(carbobenzoxy)-L-lysine N-carboxyanhydride in DMF
substitution with different groups which could be easily real-
at 20 C, resulting in a polypeptide diblock copolymer.127 Direct
ized by ‘click’ reaction. An azido group is used as the initiator
ROP of L,L-dilactide or 3-caprolactone from PHEMA prepared by
for the ATRP of NIPAM to produce end-functionalized PNIPAM.
ATRP at the sites of the pendent hydroxyl groups gave well-
dened graed polymers.128 Subsequently, the ‘click’ reaction between the azido end-group
A bifunctional initiator, 2-hydroxyethyl 2-bromoisobutyrate and various acetylene derivatives is demonstrated to provide
PNIPAMs with an LCST that ranges from 34.8 to 44.6 C.142
(HEBI), was synthesized to produce diblock copolymers by ROP
and ATRP, respectively and independently. To avoid the effect of
hydroxyl groups on the process of ATRP, ROP is oen executed 5.3 Other methodologies
rst, followed by an ATRP route. Different composition diblock
Along with ATRP, RAFT is another versatile technique to
copolymers were produced, including PLLA-b-PHEMA,129 PLLA-
prepare polymers. A combination of these two methodologies
b-PDMAEMA130 and PEEP-b-PDMAEMA.131 An ATRP initiator
bearing two hydroxyl groups was also employed to prepare Y- may enrich the polymer products. PNIPAM graed poly-
shaped polymers.132 Amphiphilic ABA133 and AB(2)134 shaped acrylonitrile (PAN) was synthesized by RAFT copolymerization
copolymers were synthesized by a combination of ring-opening of HEMA and AN followed by esterication of the pendent
metathesis polymerization (ROMP) and ATRP. hydroxyl groups on the PHEMA moieties with BiBB and further
ATRP of NIPAM.143 The combination of ATRP and RAFT aided by
‘click’ reaction and electrospinning makes it practical to make
5.2 ‘Click’ reaction solvent-resistant nanobers based on copolymers of 4-vinyl-
The azide/alkyne ‘click’ reaction135 is a recent re-discovery of a benzyl chloride (VBC) and glycidylmethacrylate (GMA) (PVBC-b-
reaction combining several advantages: (1) quantitative yields PGMA) with a thermally-sensitive surface, which was realized by
(usually above 95%), (2) high tolerance toward functional PNIPAM.144 Solvent-resistant antibacterial microbers were also
groups, and (3) insensitivity to solvents. In addition, the reac- prepared by ATRP and electrospinning.145
tion could be realized at various interfaces, as a result, ‘click’ In order to introduce polymer moieties consisting of other
reactions have made a signicant contribution in producing monomers, such as alkenes, into the nal products, some other
and modifying polymer materials.136 techniques can be adopted. Di- or triblock cationomers con-
Along with ‘click’, ATRP shows a more powerful capability sisting of polyisobutylene (PIB) and PDMAEMA segments were
and convenient method for designing polymers with different synthesized by a synthetic strategy including four steps: (1)
structures. ATRP of various monomers mediated by an azido a- synthesizing mono- and diallyltelechelic polyisobutylenes by
functionalized initiator gave homopolymer precursors that were living cationic polymerization, (2) transferring the end-group to
then efficiently clicked with either propargyl methacrylate or PIBs capable of mediating ATRP of DMAEMA, (3) ATRP of
propargyl acrylate to yield narrow-disperse (meth)acrylate-cap- DMAEMA, and (4) quaternization of PDMAEMA to
ped macromonomers with either cationic, anionic, nonionic, or PDMAEMA+I by CH3I.146 Amphiphilic poly[bis(triuoroethoxy)
zwitterionic character.137 Block copolymers might be facilely phosphazene]-b-poly[(dimethylamino)ethyl methacrylate]
obtained by coupling two individual polymers with alkynyl and copolymers were prepared by a similar procedure,147 except that
azido groups, respectively, which could be prepared by two the homopolymer achieved by living cationic polymerization
techniques independently,138 therefore largely widening the bears an alkynyl group and its transformation to a macro-
polymer resource. By the same route, gra polymers were initiator for ATRP was accomplished by ‘click’ reaction.
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6 Applications 6.2 Adsorption/separation
Functionalities in hydrophilic polymer brushes endow them
ATRP of hydrophilic monomers gives polymers with a wide
with an ability to form complexes with specic chemicals.
range of functionalities and topologies. The natural character-
Highly selective adsorption of specic compounds makes
istics, as well as novel properties brought about by polymeri-
separation from a mixture or concentration possible, which
zation by ATRP or a combination of techniques of the
means a lot in both academic and industrial areas.
hydrophilic monomers render them with broad application
Polyacrylic acid sodium (P(NaA))-graed cotton was
potential in various elds.
prepared by SI ATRP for the efficient removal of Cu(II) and Pb(II)
from aqueous media with good maximum sorption capacities of
6.1 Antibacterial/antifouling surface construction 2.45 and 2.44 mmol g1, respectively.162 The PHEMA brushes
graed from patterned Si(100) surfaces behaved as “tentacles”
Reducing or eliminating non-specic adsorption is always one that could captured ferritin complexes from aqueous solution
of the important tasks in manufacturing biomaterials, espe-
Published on 30 January 2013 on http://pubs.rsc.org | doi:10.1039/C3PY00122A
through entanglement between the brushes and the ferritin
cially implanted materials for human beings. As reported by
proteins.163 Magnetic iron oxide (Fe3O4) nanoparticles were
previous papers, many hydrophilic polymers show antifouling
attracted onto quaternized PDEAEMA-graed MWNTs prepared
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properties or play an important role in the process of producing by SI ATRP by electrostatic effects. The resulting magnetic
antibacterial substrates. MWNTs show fascinating potential applications in bionano-
Quaternized PDMAEMA was proved to have excellent anti- science and technology.164
fouling properties and it has been widely used to modify diverse SI ATRP of acrylic acid (AA) was conducted from the
substrates, such as hollow ber membranes,148 stainless steel,149 macromolecule initiators of poly(4-vinylbenzyl chloride-co-
poly(vinylidene uoride) membranes,150 silicon nanowire divinylbenzene) (PCMS/DVB) beads to prepare a stationary
arrays,151 magnetic nanoparticles152 and tissue culture
phase for weak cation exchange (WCX) chromatography for
substrates.153 Generally, the process contains three main steps:
separation of proteins by ion-exchange chromatography.165
(1) immobilization of ATRP initiators on the surface of the High-capacity anion-exchange membranes for chromato-
substrates; (2) (co)polymerization of DMAEMA and (3) quater- graphic bioseparation were prepared by graing PDMAEMA
nization of PDMAEMA segments. The formation of tertiary nanolayers from the pore surfaces of commercially available
amino groups of PDMAEMA brushes is oen achieved by add- regenerated cellulose membranes.166 The modied membranes
ing a simple alkyl halide such as methyl iodide, ethyl iodide or exhibited good adsorption of bovine serum albumin (BSA), and
benzyl chloride. Non-quaternized PDMAEMA-b-PS or PPEGMA- therefore a good separation efficiency by applying a mixture of
b-PS diblock polymer brushes graed PVDF membranes also
bovine serum albumin and hemoglobin.
exhibit resistance to protein.154
Positively charged PDMAEMA brushes end-graed gold
Other hydrophilic polymer brushes including PHEMA,155 could adsorb negatively charged BSA and completely reject net
PHPMA,156 PPEMGA157 and PHEMA-g-PPEGMA158 may also positively charged lysozyme.167 PNIPAM-co-2-PDMAEMA brush-
result in antifouling character in materials. The thickness of graed silica beads were employed as stationary phases in
polymer lms has a considerable impact on their antifouling chromatographic analysis. Chromatographic retention times
performance as illustrated by Zheng et al.159 They found that for adenosine nucleotides in aqueous mobile phases are
polymer brushes based on PHEMA and PHPMA with a medium signicantly increased, and decreased with increasing column
thickness xed on a gold surface were suitable considering their
temperature, indicating the temperature response of the
good antifouling performances. As reported, surfaces with an
modied surface.168 Collagen was immobilized on PHEMA
appropriate lm thickness of 25 to 45 nm for PHPMA and 20 modied titanium surfaces, promoting broblast and osteo-
to 45 nm for PHEMA can achieve almost zero protein adsorption blast cell adhesion and proliferation, a requirement for
(<0.3 ng cm2) from single-protein solution and diluted human biomedical implants.169
blood plasma and serum.
Hydrophilic polymers bearing functionalities provide active
group sites for themselves to be bound onto some substances by 6.3 Functional and organic/inorganic hybrid materials
coupling for improving material performance. The hydroxyl With the help of ATRP, fabrication of many functional materials
groups from PHEMA brushes on stainless steel (SS) were con- has become reality. Various membranes based on diverse
verted to carboxyl groups for coupling of chitosan (CS). Surface- substrates such as nylon,170 PVDF171 and polysulfone (PSf),172 as
functionalized SS showed resistance to bovine serum albumin well as supports for ion-exchange chromatography173 have been
adsorption as well as bacterial adhesion, and it also exhibited demonstrated.
antibacterial efficacy against Escherichia coli (E. coli).160 Tita- Organic/inorganic hybrid materials prepared by ATRP and
nium surfaces were modied with poly(methacrylic acid) other LRP methods are one of the most dynamically developing
(PMAA) for immobilization of silk sericin via carbodiimide areas of polymer and materials science.174 Hybrids with well-
chemistry. PMMA silk functionalized surfaces promote osteo- dened gras are quite interesting because they allow efficient
blast cells' adhesion, proliferation, and alkaline phosphatase dispersion in certain media and prevent aggregation of the
activity, and have potential applications combating biomaterial- inorganic particles. Many inorganic materials, including
centered infection and promoting osseointegration.161 carbon black,175 nanodiamond,176 gold nanoparticles,177
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phthalocyanine,178 polyhedral oligomeric silsesquioxane was utilized to encapsulate and release doxorubicin (DOX).192 A
(POSS),179 and magnetic iron oxide180 were modied with poly- hyperbranched DMAEMA based polymer was also demon-
mer gras by a supported initiator method, which is discussed strated to possess as high a transfection ability as well known
in the former part of this context. The organic layer graed on branched PEI.193 PCL based amphiphilic polymers were also
the surface brings more functionality to the substrates. Folic proposed as effective gene transfection systems.194
acid was decorated on the surface of magnetite nanoparticles by Natural polymers are considered as good candidates for
covalent bonds, which makes cell targeted imaging possible.181 drug/gene delivery since they are generally nontoxic, biocom-
Organic/inorganic composites with novel structures were patible and degradable. Xu et al. exploited several gene trans-
also constructed via ATRP. Silica decorated core–shell organic portation carriers based on different backbones including
particles was prepared by the following method:182 (1) emulsi- dextran,195 cellulose,196 chitosan,197 dextran198 and cyclodex-
er-free emulsion polymerization of styrene with 2-chlor- trin,199 along with cationic PDMAEMA side chains. All of them
opropionyloxyethyl methacrylate (CPEM) using potassium exhibited good delivery performance and promising potential
persulfate as an initiator; (2) SI ATRP of DMAEMA, and (3) for future gene delivery.
Published on 30 January 2013 on http://pubs.rsc.org | doi:10.1039/C3PY00122A
catalytic hydrolysis and subsequent condensation of tetrae- Researchers are paying more and more attention to star
thoxysilane (TEOS) in the shell layer. Hollow silica shell parti- shaped polymers due to their branched structures and unique
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cles were also obtained by removal of polymer components physicochemical properties which are signicantly different
from the composites with tetrahydrofuran. Gold nanoparticle from their linear counterparts. More specically, amphiphilic
dotted PS-PDMAEMA core–shell particles were prepared using star block copolymers have an extremely low critical micelle
the same route also.183 Thermoresponsive cross-linked hollow concentration so that they can even exist as unimolecular core–
PNIPAM nanocapsules and silver184 or gold185 nanoparticle- shell micelles. Therefore, star shaped amphiphilic block poly-
embedded hybrid PNIPAM nanocapsules with controlled shell mers consisting of a hydrophobic core and hydrophilic shell
thickness were prepared via the combination of SI ATRP and were considered as competitive candidates as drug/gene
“click” methods. Silica nanoparticles were used as the substrate delivery supports.200 Star polymers consisting of PS or PBuA as
for fabrication of the thermally cross-linked shell, and it was the core and PDMAEMA as the shell were synthesized and their
removed by HF etching aer package and reduction of Au+ or self-assembly and complexation with DNA were studied.201 Star
Au+. Polymeric nanocapsules with movable magnetic cores were polymers with PEG arms and a degradable cationic core for
prepared by SI ATRP of NIPAM and N,N0 -methyl- siRNA Delivery were synthesized by using disulde dimetha-
enebisacrylamide (MBA) from the surfaces of the Fe3O4@SiO2 crylate (cross-linker, SS) via an “arm-rst” approach.202 Unim-
nanoparticles, followed by the selective removal of the silica olecular containers based on multiarm amphiphilic block
layer.186 polymers were also developed as potential drug carriers in
biomedical areas.203
Micelles are the assembly product of amphiphilic copoly-
6.4 Drug/gene delivery mers and the assembled entity in water contains a hydrophobic
The poor water solubility of hydrophobic drugs and natural core as a container and a hydrophilic shell for maintaining good
toxicity are among the main limits to therapeutic efficacy of dispersity. Various non-water soluble drugs such as dipyr-
conventional small molecule drug therapeutics. Conventional idamole,204 DOX,205 ibuprofen (IBU),206 and amphotericin B,207
chemotherapeutics with no specicity oen cause serious side could be packed into the hydrophobic core and released under
effects and toxicity towards normal tissues and as a conse- certain conditions. Hybrid gene vectors based on magnetic iron
quence, targeted drug delivery systems have been extensively oxide208 and hydroxyapatite209 have also been developed.
explored. A variety of polymers for gene delivery have been
synthesized by CRP methods187 and well-dened amphiphilic
block copolymer-based vectors via ATRP have already been 6.5 Coupling biomolecules (bioconjugation)
summarized in other reviews.188 This section describes Hydrophilic polymers are widely adopted to form bioconjugates
construction of a drug/gene delivery system with different for various applications in bio-related areas because they are
compositions and structures via ATRP of hydrophilic biocompatible and/or bear functionalities.
monomers. Functional groups in hydrophilic polymers make it quite
Various homo/block (co)polymers were proposed as delivery easy to combine them with reactive biomolecules. The epoxy
vectors. Optimized p(DMAEMA-co-PEGMA) gene vectors are groups of the copolymer PPEGMA-co-PGMA could be used
stable under similar in vivo conditions showing 7-fold greater directly for covalent coupling of human immunoglobulin (IgG)
gene expression in the lungs compared with polyethylenimine via a ring-opening reaction to produce IgG-coupled micro-
(PEI).189 PHEMA-b-PDMAEMA-b-PEG-b-PDMAEMA-b-PHEMA domains.210 Hydroxyl group capped PEGMA can also be
pentablock copolymers showed a comparable transfection effi- employed to form a complex with biomolecules, and lysome211
ciency to those of PEI (25 kDa).190 The inuence of block and IgG212 were successfully coupled by esterication employing
sequences of polymer vectors on gene transfection efficiency either hydroxyl groups or a reactive one by modication of the
was discussed by using a triblock copolymer PDMAEMA-b- hydroxyl groups for improving effectiveness.
PPEGMA-b-PDMAEMA (DED) and a diblock copolymer It is well known that the chain ends of polymers prepared by
PDMAEMA-b-PPEGMA (DE).191 High molecular weight PNIPAM ATRP usually have a high end function degree, and polymers are
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Polymer Chemistry Review
generally capped with halides, according to the proposed ATRP of hydrophobic and hydrophilic monomers could dissolve
mechanism. It is considered that such halides at the chain ends in both water and organic solvents that can be used as
of polymers can be reacted with amine groups, therefore surfactants.226
biomolecules bearing amine groups can be facilely linked to
polymers to form bioconjugates. Thermoresponsive PNIPAM 7 Conclusion and perspectives
was prepared on the surface of PCL lms; the alkyl bromide end
groups were used to directly couple collagen to produce a ATRP of hydrophilic monomers has been intensively studied
collagen-immobilized thermo-sensitive PCL surface to improve and several monomers can be polymerized in a well controlled
cell adhesion and proliferation above the lower critical solution manner. However, it is still changing to develop a versatile
temperature (LCST, 32 C).213 It is interesting that the cell catalyst system which ts polymerization of all monomers. A
attachment was enhanced substantially at 37 C; besides, the few successful cases were demonstrated for some specic
attached cells could be recovered simply by lowering the culture monomers. Most of the reported polymerizations are mediated
temperature which gives it potential as an adhesion modier for by a copper catalyst, which is toxic and has become an obstacle
Published on 30 January 2013 on http://pubs.rsc.org | doi:10.1039/C3PY00122A
advanced cell culture and tissue engineering applications. toward practical application. Fortunately, we also have seen
Heparin was also attached to PPEGMA graed silicon through some successful examples of iron-catalyzed polymerization that
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the reaction manner.214 exhibits promising potential since the iron catalyst is biocom-
Beside halides, the other end of the polymer in ATRP is the patible, low cost and abundant. A large amount of fundamental
initiator. Selective choice of reactive groups bearing an initiator work is still needed to widen the polymer categories, and
can directly produce an active polymer which could be reacted polymerization by green procedures should be paid more
with some specic biomolecules. By such a process, aminooxy attention for application in bio-related areas.
end-functionalized PPEGMA and PHEMA were prepared to As we have highlighted above, ATRP of hydrophilic mono-
produce well-dened bioconjugates by chemoselective oxime mers has great application potential in various areas. Detailed
formation with levulinyl-modied protein;215 aldehyde termi- work and progresses have been undergoing smoothly. We
nally functionalized double hydrophilic diblock or triblock believe it has a bright future accompanied by the dramatic
copolymers of DMAEMA, DEAEMA, and PEGMA were prepared development of versatile and environmentally benign catalysts
to form bioconjugates with lysome.216 such as iron catalysts.
The convenient process for preparation of ATRP initiators
makes it possible to modify biomolecules themselves to be Acknowledgements
initiators to directly initiate polymerization of monomers and
form polymer–biomolecule conjugates. Streptavidin (SAv) was The nancial support from the National Natural Science
modied to be an ATRP initiator to polymerize NIPAM to form Foundation of China (nos 20974071, 21174096, 21274100 and
an SAv–PNIPAM conjugate;217 a recombinant human growth 21234005), the Specialized Research Fund for the Doctoral
hormone (rh-GH) PEGMA hybrid was prepared by modifying rh- Program of Higher Education (no. 20103201110005), the Project
GH protein via a bromo-ester functionalized linker to be a of International Cooperation of the Ministry of Science and
macroinitiator to polymerize the hydrophilic monomer Technology of China (no. 2011DFA50530), the Qing Lan Project,
PEGMA.218 Electrostatic effects could be also used to form the Program of Innovative Research Team of Soochow Univer-
complexes between polymers and biomolecules; PCL lm sity, and the Project Funded by the Priority Academic Program
surface was decorated with positively charged PDMAEMA which Development of Jiangsu Higher Education Institutions (PAPD)
can form complexes with negative gelatin by SI ATRP to improve is gratefully acknowledged.
cell immobilization and subsequent gene transfection.219
Notes and references
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