Advances in Living Anionic Polymerization

Perspective
pubs.acs.org/Macromolecules
Advances in Living Anionic Polymerization: From Functional

Monomers, Polymerization Systems, to Macromolecular
Architectures
Akira Hirao,*,,, Raita Goseki, and Takashi Ishizone
Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology,
2-12-1-S1-13, Ohokayama, Meguro-ku, Tokyo 152-8552, Japan
Institute of Polymer Science and Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren Ai Road, Suzhou Industrial Park,
Suzhou 215123, China
ABSTRACT: This Perspective presents the development in living anionic polymerization since 1990. The main subjects involve
the following concerns of living anionic polymerization: functional styrene derivatives, new monomers and promising additives,
the regio- and stereoselective polymerization, special polymers having rigid-rod-like or helical conformations, the synthesis of
complex branched polymers composed of comblike segments via living anionic poly(macromonomer)s, and the precise synthesis
of macromolecular architectures including multiblock polymers, exact graft polymers, multicomponent -star polymers,
dendrimer-like star-branched polymers, and hyperbranched polymers by the recently developed methodologies and a new allaround iterative methodology. Throughout the Perspective, attention has focused on recent advances both in the precisely
controlled functional polymer syntheses and in various structurally elaborate complex macromolecular architectures. Such
advances have signicantly expanded the range of available well-dened specialty functional polymers, which have been dicult
to synthesize until recently. The future perspectives based on the present situation will also be described.
1. INTRODUCTION
Mn values being 1.05 or even lower. Finally, the resulting living

anionic polymers have chain-end anions, which are highly
reactive but stable under appropriate conditions. Such
characteristics are ideally suited for the tailor-made synthesis
of various linear and branched macromolecular architectures.
Since the discovery of living anionic polymerization, this
polymerization system has signicantly contributed to the
precise polymer synthesis from both academic and industrial
viewpoints.1 For instance, the kinetic and thermodynamic
studies of polymerization systems involving various ion pairs
and free ions, the achievements in living anionic polymerization
of functional monomers, the nding of eective additives to
realize the regio- and stereoselective living anionic polymer-
In the past 25 years, remarkable advances in various living/

controlled polymerization systems via dierent mechanisms,
such as not only anionic, but also cationic, radical, transition
metal-mediated, and other mechanisms, have been achieved. In
particular, the living/controlled radical polymerization has
recently received much attention because it embodies attractive
features such as the simple experimental operation, tolerance of
many functional groups, and applicability of many kinds of
monomers in the structure. Among these living polymerization
systems, however, living anionic polymerization of certain
monomers, such as styrene, 1,3-butadiene, isoprene, 2-vinylpyridine (2VP), and alkyl methacrylate monomers, is still the
best system from the viewpoint of the following features: rst,
the molecular weights can be precisely controlled over a wide
range from 103 to even 106 g/mol. Second, extremely narrow
molecular weight distributions (MWDs) are attained, with Mw/
XXXX American Chemical Society
Received: June 7, 2013

Revised: February 4, 2014
dx.doi.org/10.1021/ma401175m | Macromolecules XXXX, XXX, XXXXXX
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Perspective
Figure 1. Functional styrene derivatives capable of living anionic polymerization.
2. LIVING ANIONIC POLYMERZATION OF

FUNCTIONAL STYRENE DERIVATIVES
Living anionic polymerization of styrene is the most ideal living
system and allows ready access to a variety of well-dened
macromolecular architectures. However, it has long been
believed that the major drawback is the intolerance to most
of the useful functional groups. Accordingly, styrene derivatives
substituted with such functionalities were considered not to be
subjected to living anionic polymerization because they readily
react with highly reactive initiators and propagating chain-end
anions. Nevertheless, some functional styrene derivatives were
previously known to undergo living anionic polymerization.46
They involve styrenes para-substituted with alkenes,7,8a,b
alkynes,9 aromatics,10 ethers,11ac thioethers,12 tert-amines,13
and uorine.14 Recently, living anionic polymerization of
interesting styrenes substituted with cyclobutane (cross-linking
ability at high temperatures),15 adamantanes (high thermal
stability, Tg > 230 C),16a,b -conjugated oligo(uorene)s
(electronic/optoelectronic properties),17 and diphenylamine
(chromophore, hole-transporting character)18 have been
reported. Their successful living anionic polymerization are
not very surprising, since these functionalities are proved to be
stable toward the highly reactive anionic initiators like RLi
reagents under selected conditions. Furthermore, CSi,19 C
Ge,20 CSn,21 CBi,22 and CP23 are reported to be stable
under similar conditions. Moreover, we observed that CSi
Si,24 CSiSiSi,24 SiOR,25a,b SiNR2,26 and SiH bonds27
were also stable under similar conditions. In fact, living anionic
polymerization of all styrenes containing such bonds was
successfully achieved (see Figure 1).
ization, and the synthesis of living anionic polymers having

rigid-rod-like and helical conformations are typical examples.
Such advances also provide the most versatile state-of-the-art
tools to synthesize a wide variety of macromolecular
architectures with a high compositional and molecular
homogeneity. Among them, block polymers and multiphase
macromolecular architectures synthesized by living anionic
polymerization are undoubtedly the most promising high
quality nanostructured materials via a morphological approach
to fabricate molecular devices in the eld of nanoscience. From
an industrial viewpoint, living anionic polymerization plays an
important role in producing several industrial materials, such as
a solution styrenebutadiene rubber (S-SBR), and thermoplastic elastomers having both the elasticity and the
processability, such as polystyrene (PS)-b-poly(1,3-butadiene)
(PB)-b-PS (SBS), PS-b-polyisoprene (PI)-b-PS (SIS), and the
corresponding hydrogenated triblock polymers. Very recently,
new block polymers composed of all poly(meth)acrylate
segments have been developed as the next generation of
thermoplastic elastomers.
This Perspective presents the comprehensive development
since 1990 of various living anionic polymerization systems and
the synthesis of elaborate and complex macromolecular
architectures, which has been synthetically dicult until
recently, and view the future perspectives based on the present
situation. Morphological and nanostructural studies are,
although they are interesting, beyond the scope of this
Perspective and may be found elsewhere.2,3
B
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Perspective
Scheme 1. Protection and Living Anionic Polymerization of Functional Styrenes
Figure 2. Styrene derivatives substituted with protected functionalities.
Figure 3. Styrene derivatives para-substituted with electron-withdrawing groups.
Functional groups having active hydrogen(s) and carbonyl

groups, such as OH, SH, SiOH, NH2, CCH, CHO, COR,
and COOH, are not compatible with anionic initiators and
chain-end anions, thus rendering living anionic polymerization
of substituted styrenes with such functionalities dicult or
probably impossible. To overcome this long-standing problem,
Nakahama and Hirao introduced a protective strategy into
living anionic polymerization of functional styrenes.46,2830 It
involved the following three reaction steps (Scheme 1): (1) the
functional group, such as OH,31ae SH,32 SiOH,25a,b NH2,33a,b
CCH,34 CHO,35a,b COR,36 or COOH,37 is suitably masked
by an appropriate protective group to convert it to a stable form
under the conditions of anionic polymerization, (2) the
resulting styrene with the protected functionality is subjected
to living anionic polymerization, and (3) the protective group is
removed to regenerate the original functional group after the
polymerization. With this protective strategy, a wide variety of
styrene derivatives substituted with the readily reactive
functionalities successfully underwent living anionic polymerization for the rst time. These functional styrenes and the
corresponding protected functionalities are shown in Figure 2.
All the styrenes substituted with protected functionalities are
almost the same as styrene regarding their living anionic
polymerization behavior.
Living anionic polymerization of styrene is generally carried
out under the following two dierent conditions: In a polar
solvent, like THF, at low temperature (typically 78 C) and in
nonpolar solvents, such as benzene and cyclohexane, at room or
higher temperature. It should be noted that most of the
monomers, listed in Figures 1 and 2, underwent living anionic
polymerization under the former conditions. Since the latter
conditions are used for the industrial production of polystyrene,
it is important to further examine the anionic polymerization of
these functional styrenes under the latter conditions.
As another eective strategy, Ishizone et al. introduced a

series of electron-withdrawing groups (EWGs) into styrene
monomers to signicantly change the reactivities of the
monomers and chain-end anions.46,38,39 Such EWGs involve
N-alkyl- and N-arylimines,40ac N,N-dialkylamides,41 2-oxazoline,42ac alkyl43 and aryl esters,44 N,N-dialkylsulfonamides,45
and nitrile.46ad Although they were susceptible to react with
anionic initiators and living polystyrene, very surprisingly, all of
the styrenes para-substituted with these EWGs successfully
underwent the anionic polymerization in a living manner. It was
observed that the anionic polymerizabilities of the EWGfunctionalized styrenes were remarkably enhanced by the
strong electron-withdrawing eects of the EWGs to reduce the
electron densities on vinyl groups, as evidenced by the lower
13
C NMR chemical shifts of the vinyl -carbons of these
monomers, while the nucleophilicities of the chain-end anions
were signicantly lowered by reducing the electron densities on
the anions through the EWGs, as conrmed by the crossover
polymerization of other monomers. Thus, a well-balanced
combination between the enhanced monomer reactivity and
the reduced chain-end reactivity makes living anionic polymerization of the EWG-functionalized styrenes possible (Figure 3).
Such reduced reactivities of the chain-end anions may be
attributed to the tolerance of these electron-withdrawing
functional groups. Moreover, the hydrolysis of polystyrenes
para-substituted with tert-butyl ester, 2-oxazoline, and Ncyclohexylimine yielded well-dened poly(4-carboxystyrene)s
and poly(4-formylstyrene). The successful development of this
strategy further broadened the range of functional groups
applicable for living anionic polymerization.
Thus, overall, styrene derivatives carrying almost all of the
useful functionalities now acquire the ability to undergo living
anionic polymerization. It should be noted that most of such
functionalities were believed to be incompatible with living
C
Macromolecules
Perspective
anionic polymerization until the 1980s. Most importantly, the

anion-stable functionalities and two strategies successful in
living anionic polymerization may be applied to living anionic
polymerization of other monomers, such as 1,3-butadiene, 2vinylpyridine (2VP), alkyl methacrylates, N,N-dialkylacrylamides, and cyclic monomers, since their living chain-end anions
have similar or lower reactivities for the living polystyrene. This
will enable the synthetic range of available living anionic
polymers with functional groups to be signicantly broadened.
The suppression of the unwanted addition reaction to the

pendant vinyl group, which essentially occurred during the
polymerization of p-DVB, may possibly be explained as follows:
the countercation of the chain-end anion is considered to be
completely replaced by K+ with an excess K+ and signicantly
shifted to ion pairs via the equilibrium in a high concentration
of KOBut. The coordination of some KOBut molecules to the
chain-end anion by the ionic interaction may provide the steric
hindrance around the chain-end anion. Although the vinyl
group of p-DVB is activated by the long -conjugation system
from the vinyl group to the other one, the pendant vinyl group
attached to the main chain becomes less reactive due to the
disappearance of the long conjugation system by the polymerization and the electron-donating eect of the main chain alkyl
(CH2CH). Thus, the resulting less reactive and sterically
bulkier chain-end anion may add much more slowly to the less
reactive pendant vinyl group on the polymer chain than p-DVB,
while one of the activated vinyl groups of p-DVB preferentially
undergoes the anionic polymerization.
3.2. N,N-Dialkylmethacrylamides. N,N-Dialkylacrylamides show a high anionic polymerizability due to the
electron-withdrawing eect of the amide carbonyl groups,
aording stable living polymers.49 In contrast, the corresponding N,N-dialkylmethacrylamides could not be polymerized at all
under similar conditions50ac and even with radical initiators.
From several studies using 1H and 13C NMR analyses and
modied neglect of diatomic overlap (MNDO) calculations, a
twisted conformation is estimated between the CC and C
O groups due to the intramolecular steric repulsion between
the -CH3 or CH2= group and N-alkyl substituents and the
planarity of the OCNR2 moiety.49,50ac Accordingly, the
observed nonpolymerizability can be explained by the twisted
conformation where the CO function is not well conjugated
with the CC group. In addition, the N,N-dialkylmethacrylamides might have a very low ceiling temperature, which
hinders their polymerization.
In order to clarify the above hypothesis, Ishizone et al.51,52
introduced small membered ring structures in the N-alkyl
substituents to achieve an eective resonance between the C
C and CO groups by breaking the planarity of the OC
NR2 moiety. A series of newly synthesized N,N-dialkylmethacrylamides carrying cyclic substituents, such as aziridine (MAz),
azetidine (MAzt), pyrrolidine (MPy), and piperidine (MPi)
rings, were subjected to the anionic polymerization. As
expected, the anionic polymerization of MAz and MAzt with
three- and four-membered rings quantitatively proceeded in a
living manner (Mn 50 000 g/mol and Mw/Mn < 1.1). In
contrast, the anionic polymerization of MPy having a vemembered ring aorded polymers in 3077% yields under the
same conditions. MPi, having a six-membered ring, could not
be polymerized at all even under drastic conditions. Thus, the
3. NEW MONOMERS AND ADDITIVES FEASIBLE FOR

LIVING ANIONIC POLYMERIZATION
3.1. 1,4-Divinylbenzene. As is well-known, the radical or
anionic polymerization of 1,4-divinylbenzene (p-DVB) usually
produces highly cross-linked polymers insoluble in organic
solvents. Very recently, Hirao et al. successfully demonstrated
for the rst time that one of the two vinyl groups of p-DVB
exclusively undergoes selective polymerization in a living
manner in THF at 78 C with a specially designed initiator
system prepared from oligo(-methylstyryl)lithium and a 10fold excess of KOBut.47 Indeed, soluble linear poly(p-DVB)s
with well-controlled Mn values and nearly monodisperse
distributions were quantitatively obtained, as shown in the
SEC proles of the poly(p-DVB)s (Figure 4). The resulting
Figure 4. SEC proles of poly(p-DVB): (a) without KOBut, Mn = 22

200 g/mol, Mw/Mn = 3.53; (b) in the presence of 15 equiv of KOBut,
Mn = 24 900 g/mol, Mw/Mn = 1.04.
living polymers were stable only for a few minutes at 78 C,

but stable even after 30 min at 95 C.48 Under such
conditions, the undesired addition reaction of the chain-end
anion to the pendant vinyl group was almost suppressed, and
soluble polymers with controlled Mns of up to 60 500 g/mol
and narrow MWDs (Mw/Mn < 1.05) were obtained. The living
nature of the polymerization was also supported by the
successful synthesis of the well-dened diblock polymers,
poly(p-DVB)-b-P2VP and poly(p-DVB)-b-PtBMA. They also
found that eective additives include several potassium
alkoxides and phenoxides derived from 1-methylpropanol,
2,4-dimethyl-3-pentanol, 1-methylcyclohexanol, 1,2:5,6-di-Oisopropylidene--D-glucofuranose, phenol, 1-naphthol, 2,6-di(tert-butyl)-4-methylphenol, and even the potassium salt of
pivalic acid.48
Figure 5. Exo-methylene type and the corresponding acyclic monomers.

D
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Perspective
anionic polymerizability of the N,N-dialkylmethacrylamides

with cyclic substituents dramatically decreases by increasing the
ring number from three to six. The polymerizability of MAz
and MAzt can be explained by the eective -conjugation
between the CC and CO double bonds. In these
monomers, the planar amide conjugation between the CO
and NR2 groups might be strongly prohibited and the
pyramidal structures of the highly strained small rings in
MAz and MAzt were maintained. On the other hand, the CC
and CO double bonds of MPi may not be on the same plane,
since the amide conjugation between the CO and NR2 group
is predominant.52
3.3. Exo-methylene-Type Monomers. -Methylene-Nmethylpyrrolidone (MMP), a cyclic analogue of N,Ndimethylmethacrylamide (DMMA) (Figure 5), was reported
to undergo radical polymerization to give a unique polymer
possessing a ring structure perpendicular to the main chain via
the vinyl polymerization.53 Recently, Ishizone et al. succeeded
in living anionic polymerization of MMP in THF at 780 C
with Ph2CHK or Ph2CHLi by the addition of the weak Lewis
acidic Et2Zn.54 The resulting polymers possessed predicted
molecular weights (Mn 26 000 g/mol) and narrow MWDs
(Mw/Mn < 1.1). The CC bond and the adjacent CO bond
in MMP should be almost at and may eectively conjugate
with each other because of the restricted conformation derived
from the cyclic structure. Thus, the introduction of an exomethylene group can allow the nonpolymerizable N,Ndialkylmethacrylamide to be polymerized.
A similar relationship between structure and polymerizability
is observed between DPE and dibenzofulvene (DBF). DPE is
known not to undergo homopolymerization due to its very low
ceiling temperature. On the other hand, DBF exclusively
undergoes radical, cationic, and anionic polymerization to form
a vinyl polymer possessing a ring structure vertical to the main
chain.55 Thus, the exo-methylene monomer again shows a
higher polymerizability compared to the acyclic counterpart.
The connection of two phenyl groups converts DPE into a
planar molecule to induce the homopolymerizability.
Very recently, Ishizone et al. have succeeded in polymerizing
a new exo-methylene monomer, benzofulvene (BF, methyleneindene).56 BF, a cyclic analogue of 2-phenyl-1,3butadiene (2PhBd), possesses a planar xed transoid 1,3-diene
framework including an exo-methylene group. The anionic
polymerization of BF quantitatively proceeded with sBuLi or
Ph2CHK in THF at 78 C for 1 h to give polymers with
predicted molecular weights (Mn 28 000 g/mol) and narrow
MWDs (Mw/Mn < 1.1). NMR analyses indicated that the
repeating units of the resulting PBF consisted of a 1,2-addition
unit (41%) and a 1,4-addition unit (59%). This suggested that
BF acts as a polymerizable transoid 1,3-diene and the exomethylene group always participates in the propagation
(Scheme 2). Interestingly, BF exhibited an unexpectedly high
anionic polymerizability. A low nucleophilic living PMMA
quantitatively initiated the polymerization of BF to aord a
well-dened diblock polymer, PMMA-b-PBF, while 2PhBd

cannot be polymerized with the living PMMA. Thus, the higher
polymerizability of BF is substantiated by changing to the
corresponding exo-methylene type structure.
3.4. Ferrocenyldialkylsilanes. Inorganic polymers with
backbones containing transition metal atoms are of signicant
interest because of their unique properties, behavior, and ability
to prepare inorganicorganic hybrid materials. Although they
are usually synthesized by polycondensation routes, a series of
poly(ferrocenylsilane)s can be produced via the thermal ringopening polymerization of strained, ring-tilted, and siliconbridged [1]ferrocenophanes like ferrocenyldimethylsilane
(FDS). Very interestingly, they underwent the living anionic
ring-opening polymerization with BuLi, PhLi, or ferrocenyllithium in THF at 25 C to aord well-dened polymers
containing Fe and Si atoms in their main chains (Mn 83 000
g/mol, Mw/Mn < 1.10),57ac as shown in Scheme 3. The
resulting polymers exhibited high refractive indices, a redox
activity, and potentials as precursors for semiconductors under
oxidative doping. They also showed an excellent thermal
stability to weight loss (up to 350400 C) and yielded
ferromagnetic Fe/Si/C ceramic composites at elevated temperatures (5001000 C).
Various well-dened block polymers containing PFDS
segments, such as PFDS-b-poly(dimethylsiloxane), PS-bPFDS, PI-b-PFDS, P2VP-b-PFDS, and PFDS-b-PMMA,58,59
were synthesized by the sequential anionic polymerization.
These block polymers containing PFDS segments often formed
ber-like micelles with a semicrystalline PFDS core in selective
solvents.60a,b Very interestingly, micelles with a narrow length
distribution were formed, and the length increased in
proportion to the amount of added polymer.
The living anionic ring-opening polymerization of a novel
phosphorus-bridged [1] ferrocenophane, a phosphorus analogue of FDS, was also achieved.61 It is possible to incorporate
ferrocene and a phosphorus atom into the main chain, showing
the unique property, behavior, and coordination ability to
transition-metal catalysts.
3.5. Living Anionic Polymerization of Cyclic Monomers Using Phosphazene Bases as Metal-Free Organocatalyst Systems. Seebach et al. rst reported that 1-tertbutyl-4,4,4-tris(dimethylamino)-2,2-bis(tris(dimethylamino)phosphoranylidenamino)-25,44-catenadi(phosphazene), the
so-called P4-t-Bu phosphazene base, eectively functioned as a
metal-free organocatalyst for the polymerization of MMA.62 A
polymer with an Mn value of 15 200 g/mol and an Mw/Mn
value of 1.11 was obtained in THF at the surprisingly high
temperature of 60 C. Soon after, Moller et al. reported that
ethylene oxide (EO) and D3 were anionically polymerized in a
controlled manner with 1-ethyl-2,2,4,4,4-pentakis(dimethylamino)-25,44-catenadi(phosphazene) (P2-Et) and
P4-t-Bu.63ac They also demonstrated the one-step synthesis of
the diblock polymer, PS-b-PEO, by the sequential polymerization of styrene with sBuLi, followed by EO, in the presence
of P4-t-Bu. In general, the PS-CH2CH2OLi cannot further
polymerize EO due to the strong association. However, the
extremely strong base, P4-t-Bu, can complex Li+ to suppress the
association and facilitate the polymerization of EO. Similarly,
PB-b-PEO, PI-b-PEO, PB-b-PI-b-PEO, and PS-b-PEO-b-poly(glycidol) were synthesized by the addition of P4-t-Bu to the
polymerization systems.64ae A diblock polymer of PEO-bpoly(2-(dimethylamino)ethyl methacrylate) was obtained in
Scheme 2. Microstructure of Poly(benzofulbene) (PBF)

Obtained by the Anionic Polymerization
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Perspective
Scheme 3. Anionic Ring-Opening Polymerization of Ferrocenyldimethylsilane (FDS)
the presence of P4-t-Bu, enabling the facile changeover from an

oxyanion to a carbanion.65
Recently, Hedrick and Wade et al. reported that P2-t-Bu
satisfactorily functions during the polymerization of lactide
(LA) using 1-pyrenebutanol as the initiator.66 The polymerization proceeded in a controlled manner to aord the
corresponding polyesters (Mn 27 200 g/mol and Mw/Mn
1.1). The same group also demonstrated that both 2-tertbutylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphrine and N-tert-butyl-N,N,N,N,N,N-hexamethylphosphorimidic triamide (P1-t-Bu) are eective for the living
polymerization of LA, -caprolactone, and -valerolactone.
Well-dened PEO-b-PLA, PS-b-PLA, and PMMA-b-PLA were
successfully synthesized using the corresponding -OHfunctionalized polymers as the macroinitiators for the polymerization of LA.67 It was recently found that the anionic
polymerization of dipropylcyclopropane-1,1-dicarboxylate68a,b
and [R,S]-4-benzyloxycarbonyl-3,3-dimethyl-2-oxetanone69 are
eectively controlled by the addition of P4-t-Bu and other
phosphazene bases. Very recently, Hadjichristidis et al. reported
the synthesis of high-molecular-weight comb polymers with a
single- or double-graft homopolymer, block polymer, and
statistical copolymer by the P4-t-Bu-promoted metal-free graft
polymerization utilizing the CONH2 moieties as the initiating
site in the poly(N,N-dimethylacrylamide-co-acrylamide).70
Thus, the addition of phosphazene bases to the anionic
polymerization of cyclic monomers can eectively control the
polymerization, rendering the synthesis of a variety of precisely
controlled polymers, block polymers, and other macromolecular architectures possible.
In the past 15 years, living anionic polymerization systems of
LA, alkylene oxides, lactones, and other cyclic monomers have
been signicantly advanced by using not only phosphazene
bases and several other amines but also the combination of
other reagents with these bases. Although such polymerization
systems are interesting in terms of a precision polymer
synthesis, these systems are not herein described due to the
limited space and have already been covered in an
comprehensive review71 and recent papers.72ae
3.6. Living Anionic Polymerization of Polar Vinyl
Monomers. One of the most important challenges in this eld
is controlling the anionic polymerization of polar vinyl
monomers like alkyl (meth)acrylates and N,N-dialkylacrylamides.73,74 They generally show high polymerization abilities
due to the electron-withdrawing eects of the substituents.
However, their anionic polymerization are accompanied by
serious side reactions such as a carbonyl attack and/or -proton
abstraction with the anionic initiators and chain-end anions.
Moreover, the intramolecular Claisen-type condensation of the
propagating chain-end enolate anions with the ester group at
the antepenultimate unit, the so-called backbiting reaction,
often occurs during the polymerization. Therefore, the careful
choice of initiator, counterion, solvent, and temperature is
crucial to achieve living anionic polymerization of such polar

monomers.73,74,75ac
Several new systems successfully achieving the living
polymerization of (meth)acrylate monomers have been so far
developed in order to overcome the above-mentioned drawbacks. Typically, the following two systems were developed:
rst, common salts, such as LiCl, LiClO4, LiOBut, KOBut,
lithium 2-(2-methoxyethoxy)ethoxide, and MgBr2,76ae are
added to the polymerization system, by which the propagating
chain-end anions are converted to a less reactive ion-pair to
suppress the undesired side reactions. As a representative
example, Teyssie et al.77 previously reported that the addition
of LiCl to a bulky 1,1-diphenylhexyllithium could remarkably
control the anionic polymerization of tert-butyl acrylate (tBA)
in THF resulting in a well-dened PtBA (Mn = 60 000 g/mol,
Mw/Mn = 1.20). Thus, the serious side reactions of the carbonyl
attack and -proton abstraction were almost suppressed in the
presence of LiCl. The addition of LiCl to the polymerization of
methacrylate monomers is also eective to narrow the MWD of
the resulting polymers and their Mw/Mn values being less than
1.05. A kinetic study indicated that LiCl eectively dissociates
their aggregated propagating enolate anions, followed by
producing simple active species, resulting in the formation of
polymers with low polydispersities.
The second system involves the addition of weak Lewis acids,
such as R3Al, R3n(RO)nAl, Et2Zn, and Et3B, to stabilize the
propagating chain-end anions.78ah Nakahama et al.78f,g rst
reported that the addition of Et2Zn to Ph2CHK in THF
induces living anionic polymerization of tBA, alkyl methacrylates, and N,N-dialkylacrylamides. Slower propagations were
apparently observed in those systems, where Et2Zn might
predominantly coordinate with the propagating chain-end
enolate anions to stabilize the anions. Some binary initiator
systems, including RLi/LiCl, RLi/Et2Zn, and RK/Et2Zn in
THF, were often utilized for the synthesis of block polymers of
(meth)acrylates and other comonomers such as styrene, 1,3dienes, and 2VP.
A more drastic eect was observed in the polymerization of
methacrylonitrile (MAN), tBA, and N,N-dialkylacrylamides by
the addition of R3B, such as Et3B and Ph3B.79a,b In these
systems, R3B may strongly coordinate to the initiator and/or
the propagating chain-end anion at 78 C and no appreciable
polymerization occurs. At a higher temperature, the coordinated species barely dissociates to aord the active chain-ends
to initiate the polymerization. Ishizone et al. successfully
demonstrated that MAN underwent living anionic polymerization by the addition of Et3B to the conventional system.80 As
mentioned above, no apparent polymerization of MAN
occurred with the binary initiator system of Ph2CHK/Et3B at
78 C even after 28 h. However, the polymerization
immediately took place and was completed within 1 min by
raising the temperature to 0 C, resulting in the formation of
PMANs possessing predicted molecular weights (Mn 32 000
g/mol) and narrow MWDs (Mw/Mn < 1.1). The side reactions
F
Macromolecules
Perspective
Scheme 4. Estimated Mechanism of Living Anionic Polymerization of Methacrylonitrile (MAN) in the Presence of Et3B
Scheme 5. Stereospecic Living Anionic Polymerization of MMA
narrow MWDs (Mw/Mn 1.1) were produced even at room

temperature.
may be eectively suppressed by the coordination of Et3B to

the initiator and/or the propagating enolate anion to stabilize
the anionic species (Scheme 4). Based on the polymerization
behavior at dierent temperatures, the dormant species
between the propagating polymer anion and Et3B might form
in the polymerization system. Unfortunately, the same binary
initiator system could not achieve any degree of molecular
weight control during the polymerization of acrylonitrile.
Several eective polymerization systems of acrylate and
methacrylate monomers by the addition of the bulky R3Al and
R3n(RO)nAl were reported by Kitayama et al.,78e Muller et
al.,81 and Kuraray Co., Ltd.82 More details are discussed in the
next section. Interestingly, the acceleration of polymerization
was often observed in these systems in a nonpolar solvent like
toluene, probably due to the coordination of the Lewis acids to
the (meth)acrylate monomers.
Another interesting example was living anionic polymerization of MMA at ambient temperatures in the presence of the
tetraphenylphosphonium cation reported by Hogen-Esch et
al.83 The in situ formed Ph3CPh4P+ from Ph3CK and
Ph4P+Cl initiated the polymerization of MMA at temperatures
between 0 and 20 C to quantitatively aord (PMMA)s with
predictable molecular weights (Mn 29 100 g/mol) and
narrow MWDs (Mw/Mn 1.1). The bulky Ph4P+ cation
probably facilitates the formation of the narrowly distributed
PMMA by reducing the rate of the side reactions.
Very recently, Kakuchi et al. reported a signicant improvement in the group transfer polymerization (GTP) system using
1-triisopropylsiloxy-1-methoxy-2-methyl-1-propene in the presence of pentauorophenylbis(triyl)methane as the organocatalyst. With this system, the polymerization of methyl acrylate
(MA) rapidly and quantitatively proceeded to aord a welldened PMA (Mn = 108 000 g/mol, Mw/Mn = 1.07) at room
temperature in toluene.84 The use of the bulky triisopropylsilyl
group in the silyl enolate initiator may play a key role in
controlling the polymerization of the acrylate monomer. The
same group also succeeded in the GTP of MMA using either
triuoromethanesulfonimide as a strong Brnsted acid85 or P4t-Bu as an organic superbase catalyst.86 In both systems, the
PMMAs with predicted Mn values (50 000 g/mol) and very
4. REGIO- AND STEREOSELECTIVE POLYMERIZATION

The stereoregularity of vinyl polymers and/or microstructure of
the poly(1,3-diene)s that determine the thermal and/or
mechanical properties are known to be signicantly aected
by the polymerization variables, since they can change the
coordination states of the propagating species. As the most
important example, a series of stereoregulated PMMAs with
highly isotactic, syndiotactic, and heterotactic congurations
were successfully synthesized by carefully choosing the initiator
systems and solvents (Scheme 5).76e,78ac,e In particular, the
combination of RLi or RMgX with appropriate Lewis acids in
hydrocarbon media were eective in optimizing the stereoregularity.
Kitayama et al. recently succeeded in synthesizing almost
perfect isotactic PMMAs with the mm content of up to 99.5%
using the binary initiator system (-lithioisobutyrate/
Me3SiOLi) in toluene.87 Since such highly stereoregular
PMMAs are ideal model polymers for various basic properties,
the dierences in the Tgs and hydrodynamic volume are
discussed.78c,88,89 Very interestingly, a mixture of isotactic and
syndiotactic PMMAs forms an intermolecular stereocomplex, in
which a double-stranded isotactic PMMA helix is included in a
single syndiotactic PMMA helix.90ac Kitayama et al. also
reported that various highly stereoregular poly(alkyl
methacrylate)s were successfully prepared using specic
initiator systems and/or solvents.78e
Kuraray Co., Ltd., in Japan, successfully developed living
anionic polymerization of (meth)acrylate monomers at ambient
temperature by designing the initiator system containing the
bulky Lewis acidic diphenoxyalkylaluminum compound.82a,b
This is the rst example of poly((meth)acrylate)s industrially
produced by living anionic polymerization. All (meth)acrylic
ABA type triblock polymers, for instance, PMMA-b-poly(nbutyl acrylate)-b-PMMA, were synthesized as a next-generation
thermoplastic elastomer.
The stereospecic living anionic polymerization of N,Ndiethylacrylamide (DEA) was also developed in THF.79b,91ac
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selectivities were perfectly controlled in the polymerization of

2-triisopropoxysilyl-1,3-butadiene (iPOSBd) among such
monomers.97a,b In practice, the polymerization of iPOSBd
exclusively proceeded in the 1,4-addition mode even in THF
with the various initiators carrying a Li+, Na+, or K+. The
stereoselectivity was completely regulated as the E conguration (cis conguration in terms of the main chain, Scheme
6). Thus, the anionic polymerization of iPOSBd occurred in
For example, the syndiotactic-rich (rr = 78%) PDEA was

prepared using Ph2CHLi/Et2Zn, while isotactic-rich (mm =
8090%) (PDEA)s were produced using the initiator systems
like RLi/LiCl and tBuMgBr/Et2Zn. The addition of Et2Zn to
Ph2CHK in THF at 0 C induced the heterotactic-specic
polymerization of DEA (mr = 92%). It should be noted that the
stereoregularity of PDEA strongly aects the water solubility
and the cloud point (Tc) of the aqueous solution. Although it is
believed that PDEA is a water-soluble polymer, highly
syndiotactic polymers were observed to be insoluble in water
at any temperature. Both isotactic and heterotactic (PDEA)s
showed water solubilities, but their aqueous solutions had Tc
values of 38 and 28 C, respectively. Thus, the stereospecic
anionic polymerization of DEA evidently contributes to the
polymer solution property and behavior.
A similar relationship between the stereoregularity and
solution property was recently found in poly(Nisopropylacrylamide)s (PNIPAM)s. Since the direct anionic
polymerization of NIPAM is dicult due to the presence of the
acidic amide proton, the amide proton must be protected prior
to the anionic polymerization. Kitayama et al. succeeded in
synthesizing a highly isotactic PNIPAM (m = 97%) by the
anionic polymerization of a trimethylsilyl-protected NIPAM
with t-BuLi/AlR3 in toluene.92 Surprisingly, the polymer was
insoluble in water. Ishizone et al. synthesized an acetalprotected NIPAM, N-methoxymethyl-N-isopropylacrylamide,
and carried out the anionic polymerization.93ac This protected
monomer readily underwent living anionic polymerization in
THF at 78 C with Ph2CHM (M = Li, K, and Cs) in the
presence of either LiCl or Et2Zn (Mn 48 000 g/mol and Mw/
Mn < 1.1). The initiator system of Ph2CHK/Et2Zn aorded an
atactic PNIPAM (r = 50%) showing a Tc value of 32 C. On
the other hand, the Tc value of 37 C was observed for a
syndiotactic-rich polymer (r = 83%) produced by the
Ph2CHLi/Et2Zn initiator system. A water-insoluble isotacticrich PNIPAM (m = 69%) was obtained with the Ph2CHLi/LiCl
system.
Hogen-Esch et al. demonstrated the synthesis of isotacticrich PS (mm = 5572%) by the anionic polymerization with
3,3-dimethyl-1,1-diphenyl-1-lithiobutane in hexane at 30 C
in the presence of lithium hydroxide.94 On the other hand, the
triad (mm) and pentad (mmmm) contents of the PS segment
reached 95 and 90%, respectively, when the polymerization of
styrene was carried out with polyisopropenyllithium at 60 C.
The control of the regio- and stereoselectivities of PB and PI
is an industrially important subject, since their elastic properties
strongly depend on the microstructures of the repeating units.95
During the polymerization in hydrocarbon media with RLi, the
microstructures of the resulting poly(diene)s are regulated to
be 1,4-, especially the cis-1,4-mode, showing the desired elastic
properties.1 The signicance of high 1,4-mode for poly(diene)s
is that such polymers exhibit low Tg (e.g., 64 to 70 C for PI
and 94 C for PB). The Tg rises linearly as the concentration
of 1,2-mode increases. Although numerous studies have been so
far dedicated to control the microstructures, perfect control of
both the regioselectivity and stereoselectivity has not yet been
realized and is still challenging subjects. The highest cis-1,4
microstructures were obtained so far in the absence of solvent
at low concentrations of RLi (106 M): 98% cis-1,4-PI and
86% cis-1,4-PB.95,96
Takenaka et al. reported that a seires of 2-trialkoxysilyl-1,3butadienes underwent living anionic polymerization in THF at
78 C. It was observed that both the regio- and stereo-
Scheme 6. Stereoselective and Regioselective Living Anionic

Polymerization of 2-Triisopropoxysilyl-1,3-butadiene
(iPOSBd)
regioselective and stereoselective fashions in addition to the

living mechanism. The resulting polymers not only show
elastomers in character but also have the advantage to have
alkoxysilyl functions capable of linking with metal and inorganic
materials.
Another interesting example is living anionic polymerization
of 1,3-butadiene carrying a bulky and rigid adamantyl
substituent, i.e., 2-(1-adamantyl)-1,3-butadiene (AdBd).98a,b
The PAdBd with a high cis 1,4-repeating unit (96%, cis/trans
= 93/7) was obtained using sBuLi in cyclohexane. Interestingly,
even in THF, the microstructure was predominantly regulated
in the cis 1,4-addition mode (88%, cis/trans = 82/18). These
results suggest that the introduction of a bulky function at the
2-position can potentially control the regio- and stereoselectivity to the cis 1,4-addition mode.
Several research groups have focused on living anionic
polymerization of 1,3-cyclohexadiene (CHD), a cyclic monomer with a xed cisoid 1,3-diene structure.99ad The polymerization of CHD with BuLi in the presence of N,N,N,Ntetramethylethylenediamine in cyclohexane at 40 C aorded a
polymer containing 52% 1,2- and 48% 1,4-repeating units.
Since the cyclohexene moiety in the resulting PCHD can be
converted into either a saturated cyclohexane ring or a
phenylene ring via hydrogenation or oxidation, the resulting
PCHD is considered to be an attractive precursor for rigid
poly(cyclohexane)s with a high Tg value and conductive conjugated poly(phenylene)s.
5. LIVING ANIONIC POLYMERS WITH UNIQUE

CONFORMATIONS
Polyacetylene (PA) has been extensively studied as a
conductive and nonlinear optically active specialty polymer.
PA adopts a rodlike conformation due to the conjugated
resonance structure, exhibiting a rigid and mechanically tough
chain structure. Accordingly, the PAvinyl polymer molecular
conjugates are expected to be new functional materials, which
combine advantageous features of PA with the characteristics of
vinyl polymers such as solubility, exibility, elasticity, and
processability. Unfortunately, acetylene cannot be directly
polymerized under the conditions of anionic polymerization.
Hogen-Esch et al. developed an ecient two-step methodology for the synthesis of a well-dened PA via living anionic
polymerization of phenyl vinyl sulfoxide (PVS), followed by
conversion to the PA segment simply by thermal treatment, as
shown in Scheme 7.100 By using this methodology, PAs with
H
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Scheme 7. Synthesis of Polyacetylene (PA) by Living Anionic Polymerization of Phenyl Vinyl Sulfoxide (PVS), Followed by
Thermal Degradation of the Resulting PPVS
Scheme 8. Complex Branched Polymers by Using Living Poly(macromonomer)s
CBABC pentablock terpolymer, PHI-b-PI-b-PS-b-PI-b-PHI,

could be synthesized.104 Interesting and unique morphologies
and the formation of supramolecular assemblies have recently
been observed from these block polymers.105ae
-Amino acid N-carboxy anhydrides (NCAs) are anionically
polymerized to aord poly(-amino acid)s, some of which
adopt ordered conformations of the -helices or -strands.
Although the anionic polymerization of NCA was not
satisfactorily controlled for a long time, it has recently been
much improved to proceed in a living manner.106ad The
molecular weights could be controlled up to a 100 000 g/mol
order, and narrow MWDs (Mw/Mn < 1.2) were attained.
Various block polymers and even -star polymers containing
poly(-amino acid)s were successfully synthesized using chainNH2-functionalized polymers as macroinitiators.107af,108 The
incorporation of poly(-amino acid) sequences into block
polymers are particularly interesting for the generation of
unusual nanostructures and enhanced control over nanoscale
structures through intermolecular hydrogen bonding.108 It is
also interesting that the resulting biomimetic hybrid polymers
behave as potentially biocompatible materials and new smart
materials, whose conformation and association properties can
reversibly respond by changing pH and temperature.108,109
Thus, living anionic polymers possessing rigid-rod-like or
ordered -helical and -strand conformations are now available.
Accordingly, the molecular design and synthesis of macromolecular architectures containing such characteristic segments
become possible. Furthermore, since they possess intriguing
properties including conductivity, nonlinear optical activity,
liquid crystallinity, biocompatibility, etc., combining such
polymer segments with synthetic polymers oers many
controllable molecular weights and narrow MWDs (Mw/Mn <

1.2) could be successfully synthesized for the rst time in the
eld of living anionic polymerization. The success of this
methodology provides a new route to the incorporation of the
PA segment into elaborate polymer structures accessible
through anionic polymerization. The same group synthesized
new PA-containing block polymers, PS-b-PA and PA-b-PS-bPA, by the sequential polymerization of styrene and PVS,
followed by thermal treatment.100 Soon after, several PAcontaining block polymers101ae as well as asymmetric starbranched polymers containing one or two PA arms102a,b were
synthesized using the two-step synthesis. The resulting
polymers are of special interest in that the PA segments are
phase-separated at the molecular level, followed by selforganizing, to arrange the conductive PA assemblies inside
the microdomains. Moreover, their rigid rodcoil structures are
interesting in terms of their physical, mechanical, and solution
properties.
Poly(alkyl isocyanate)s (PRI)s are interesting polymers that
adopt an extended rodlike helical conformation and possess a
unique optical activity and liquid crystallinity. Lee et al. rst
succeeded in achieving living anionic polymerization of RIs
under the conditions at 98 C with the initiators having Na+
in the presence of 15-crown-5 or NaBPh4.103ac The addition
of such additives to the polymerization system is essential to
prevent any undesired trimer formation by backbiting from the
living polymer chain-end anion. With this living polymerization
system, not only well-dened PRIs (Mn 50 000 g/mol and
Mw/Mn < 1.1) but also various well-dened AB diblock
polymers, ABA and BAB triblock polymers (A: PS and P2VP;
B: poly(hexyl isocyanate) (PHI)), and even a particular
I
Macromolecules
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Scheme 9. Complex Branched Polymers by Using Living Double, Triple, and Star-Tailed Comb Polymers
monomers and the resulting living anionic poly(macromonomer)s can be utilized for all molecular designs
and architectural polymer syntheses developed by living anionic
polymerization. The complex branched polymers thus synthesized are very dicult in synthesis by any other methods.
Various macromonomers herein synthesized should be added
to the list of new monomers capable of living anionic
polymerization.
opportunities for the development of new functional specialty

polymers for both academic and industrial interests and the
next-generation nanomaterials.110a,b,111
6. LIVING ANIONIC POLY(MACROMONOMER)S

Poly(macromonomer)s are extremely high-density graft polymers with a polymer chain in each repeating unit.
Hadjichristidis et al.112ai were the rst to successfully prepare
a series of living anionic poly(macromonomer)s by the direct
anionic polymerization of in situ prepared macromonomers
without isolation and further rendered them capable of
synthesis of complex branched polymers.
A living poly(-styryl macromonomer) was prepared as
follows:112a PSLi was rst reacted with 4-(chlorodimethylsilyl)styrene (CDMSS), followed by anionic polymerization of the
resulting -styryl macromonomer with sBuLi. Thus, the
macromonomer is not isolated and directly in situ polymerized
to prepare the living anionic poly(macromonomer). The key
for the preparation of the macromonomer is the faster reaction
of the PSLi with the silyl chloride function than with the vinyl
group of CDMSS. The anionic polymerization of the prepared
macromonomers (Mn = (1.315.0) 103 g/mol, Mw/Mn =
1.031.10) was achieved by the addition of sBuLi to the vinyl
double bond of styrene monomer produce a series of welldened living anionic poly(macromonomer)s (Mw = (30.8
125.5) 103 g/mol and Mw/Mn = 1.021.11).
As shown in Scheme 8, the in situ prepared dierent
macromonomers were sequentially polymerized to aord ABC
triblock terpolymers composed of all comblike segments. The
in situ linking reaction of the living poly(macromonomer)s
with either MeSiCl3 or SiCl4 gave completely new 3- and 4-arm
star-comb polymers. A series of comb-b-linear and linear-bcomb-b-linear block polymers were also synthesized by the
sequential addition of another monomer or the in situ prepared
macromonomer(s) to the living poly(macromonomer).112bf
The same group successfully synthesized new double- and
triple-tailed -styryl macromonomers by the reaction of PSLi
with 4-(dichloromethylsilyl)styrene and 4-(2(dichloromethylsilyl)ethylchloromethylsilyl)styrene.112g,h Furthermore, single and double star-tailed -styryl macromonomers were prepared by modifying the procedure using
an o-center living polymer composed of three polymer chains.
By converting these new macromonomers to the corresponding
living poly(macromonomer)s, more complex macromolecular
architectures can be synthesized (Scheme 9).112i
The key factor in this study is that all of the macromonomers, without isolation, can be handled as conventional
7. PRECISE SYNTHESIS OF MACROMOLECULAR

ARCHITECTURES
One of the most advantageous features of living anionic
polymerization is the synthetic ability of various well-dened
macromolecular architectures according to their molecular
designs. Since many macromolecular architectures have been
reviewed in several articles and books, only recent synthetic
advances have been briey described, and a new conceptual allaround iterative methodology developed by us will be
introduced as a future perspective approach for architectural
polymer synthesis. We involve block polymers, although they
are not macromolecular architectures in the strict sense, graft
polymers, star-branched polymers, dendrimer-like starbranched polymers, and hyperbranched polymers in the
category of macromolecular architectures because they are all
composed of several polymer chains connected with linking
point(s) at appropriate position(s).
7.1. Recent Synthetic Advances of Macromolecular
Architectures. A huge number of di- and triblock polymers
have been synthesized by living anionic polymerization in
which two dierent monomers are sequentially added, the socalled sequential polymerization, and widely studied regarding their morphologies, properties, and behavior. The synthesis
of alternate multiblock polymers of the (AB)n type is also
possible by the sequential addition of both monomers several
times. With three monomers having similar reactivities, the
ABC, ACB, and BAC triblock terpolymers with dierent
sequential order can be synthesized by the sequential
polymerization. The successful synthesis of a particular
tetrablock quarterpolymer, PS-b-PB-b-PI-b-poly(1,3-cyclohexadiene), was reported.113
On the other hand, the block polymer synthesis by sequential
polymerization using monomers with dierent reactivities is
problematic. Since more reactive monomers usually produce
less reactive chain-end anions and vice versa, less reactive chainend anions often cannot polymerize other less reactive
monomers. Accordingly, block polymers can be synthesized
only by the sequential addition of monomers in the order of
J
Macromolecules
Perspective
methodology using multifunctional chlorosilanes seems attractive because certain -star polymers are synthesized in one-pot,
while a multiple-pot synthesis is required by other methodologies. The synthetic limitation is undoubtedly attributed to
the fact that a multiple number of reaction sites disappear after
the introduction of the arm, and thereby the arm can no longer
be introduced. In the next section, we will introduce a new
methodology by which the above synthetic limitation is
overcome to synthesize a series of multicomponent -star
polymers.
A dendrimer-like star-branched polymer (DSP) has emerged
as a novel class of well-dened hyperbranched polymers since
1995.126 To understand the structures of the DSPs, the fthgeneration (5G) DSP and its generation-based block
terpolymer composed of three dierent segments are shown
in Figure 7. As it can see, they are similar in branched
decreasing chain-end anion reactivity. Thus, special care is

needed for the monomer addition order. Nevertheless, several
interesting block polymers has been reported. Stadler et al. and
then Muller et al. were successful in synthesizing the triblock
terpolymers, PS-b-P2VP-b-P t BMA and PB-b-P2VP-bPtBMA.114ac Hydrolysis of the PtBMA block with HCl
produced a new ABC triblock terpolymer of PS-b-P2VP-bpoly(methacrylic acid), which exhibited pH-dependent solution
properties. The following triblock terpolymers were also
synthesized by using monomers with similar and/or dierent
reactivities: PS-b-PB-b-PMMA,115 poly(tert-butoxystyrene)-bPB-b-PtBMA,116 poly((5-N,N-dimethylamino)isoprene)-b-PSb-PtBMA,117 PB-b-PtBMA-b-poly(2-dimethylaminoethyl methacrylate),118 and PS-b-poly(2-trimethylsilyloxyethyl methacrylate)-b-PMMA.119 Hadjichristidis et al. reported the successful
synthesis of multiblock polymers, i.e., PI-b-P2VP-b-PEO, PS-bPI-b-P2VP-b-PEO, PS-b-PI-b-P2VP-b-PtBMA-b-PEO, PS-b-PIb-PHI, and PHI-b-PI-b-PS-b-PI-b-PHI.120ac Multiblock polymers with unusual sequences will be described in the next
section.
Like block polymers, graft polymers have long been studied
and reviewed as representative branched polymers and
reviewed.121123 The structure of a graft polymer is dened
by the following three factors: (1) the molecular weight of the
main chain, (2) the molecular weight of the graft chain, and (3)
the distance between the graft chains, as shown in Figure 6. A
Figure 7. 5G dendrimer-like star branched polymer and its block

terpolymer.
architecture to the dendrimers but composed of many polymer

chains linked to each other between the junctions. Therefore,
DSPs are much higher in molecular weight and much larger in
molecular size than the dendrimers. DSPs, believed to be
globular macromolecules in shape, have many characteristic and
potentially applicable features such as specic topological
hyperbranched architectures, hierarchic generation-based structures, dierent branched densities between the core and
outermost layer, and many junctions and terminal
groups.127131
Similar to the dendrimers, stepwise iterative methodologies
based on two complementary approaches,132 the divergent and
the convergent, were employed for the synthesis of the DSPs.
Since DSPs are composed of polymer segments, one more
reaction step to introduce the polymer chain is required, and
the living polymers are usually used to make the synthesized
DSPs well-dened in structure. Various DSPs and their block
polymers have been synthesized by stepwise iterative methodologies based on either a core-rst divergent or an arm-rst
convergent approach, which combines the appropriate linking
reactions with living polymerization systems. Since they have
been introduced in some recent reviews,127131 the detailed
synthetic procedures are omitted due to lack of space, To date,
most DSPs synthesized by such methodologies were limited to
2G4G polymers with molecular weights on the order of 100
000 g/mol because of the required use of high-molecularweight polymers in all the steps. The following examples appear
to be noteworthy, involving those by Hedrick et al.,133 Gnanou
et al.,134a,b Percec et al.,135 Hadjichristidis et al.,136a,b Hutchings
et al.,137 and Monteiro et al.138
For the synthesis of high-generation (5G) and highmolecular-weight (>106 g/mol) DSPs, only one example has
recently been reported, except for our examples described later.
Gnanou et al.139 reported the synthesis of a 7G DSP consisting
of 508 PS segments by the stepwise iterative methodology
Figure 6. Three structural factors of graft polymer.
graft polymer, in which all three factors are perfectly controlled,

is called an exact graft polymer by Hadjichristidis, but almost
all the graft polymers so far synthesized are not categorized as
an exact graft polymer due to their imperfect structural control.
In 2000, Hadjichristidis et al. were the rst to successfully
synthesize an exact graft copolymer of styrene and isoprene
having two graft units by multireaction steps including living
anionic polymerization.124 The synthesis of exact graft
polymers with more graft units will be shown in the next
section.
Among the star-branched polymers, the asymmetric starbranched polymers having chemically dierent arms, the socalled miktoarm star polymers, or -star polymers, have
recently received much attention because of their unique and
unusual morphologies. However, it is far more dicult to
synthesize -star polymers than regular stars because the
synthesis always requires selective multistep reactions that
correspond to the number of dierent arms, and isolation of the
intermediate polymers is often needed to obtain pure products.
For these reasons, the methodologies developed so far by living
anionic polymerization can allow the synthesis of a twocomponent AxBy type, several 3-arm three-component ABC
and 4-arm four-component ABCD -star polymers.125au In
addition, structural variation of such -stars is quite limited.
Among the methodologies, it is worth noting that the
K
Macromolecules
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Scheme 10. Synthesis of Dendrimer-like Star-Branched PSs up to 7G by Stepwise Iterative Methodology Based on Core-First
Divergent Approach
Scheme 11. Synthesis of Dendritic Polystyrenes by Convergent Living Anionic Polymerization
based on the core-rst divergent approach (Scheme 10). By

repeating the reaction sequence, the 7G polymer (Mn = 1.92
106 g/mol, Mw/Mn = 1.04) was successfully synthesized. In the
next section, the iterative methodology developed by our group
will be introduced, which is also eective for the synthesis of
high-generation and high-molecular-weight DSPs.
In addition to DSPs, other types of hyperbranched polymers
consisting entirely of branched polymers have recently been
reported. The rst example was dendrigraft (or arborescent)
polymers reported by Gauthier et al.140 These polymers were
synthesized by repeating the reaction sequence involving living
anionic polymerization of styrene and the subsequent
functionalization (chloromethylation or acetylation), followed
by a grafting reaction of the resulting functionalized PS with the
living PS. Since a large number of reaction sites were
introduced in each reaction sequence, a very rapid molecular
weight growth was observed by repeating the reaction
sequence. Even after repeating the same reaction sequence
four times, highly branched PSs with Mn values up to 107 g/mol
were obtained, and their molecular weight distributions still
remained narrow (Mw/Mn < 1.1).141a,b The resulting polymers
were found to possess generation-based architectures analogous
to the DSPs. Hirao et al. reported the synthesis of highly
branched PSs with more controlled architectures by a similar
methodology.142 A living anionic block polymer of PS-bpoly(3-(tert-butyldimethylsilyloxy)methylstyrene) was rst prepared and in situ coupled with the tetrafunctional core agent,
resulting in a 4-arm star-branched polymer. The silyl ether
function was then transformed to the bromide, followed by a
coupling reaction of the resulting brominated block polymer

with the same living block polymer. The reaction sequence was
repeated one more time to aord a generation-based
hyperbranched PS, 4-branched at the core and average 12branched in the second or third layer. The nal PS had a Mn of
1.4 107 g/mol (Mw/Mn = 1.08) and very close to DSP in
architecture. Very recently, He et al. reported the synthesis of
the same hyperbranched polymers by repeating the reaction
sequence involving the preparation of a living anionic PS-b-PI,
followed by epoxidation of the PI side chain, and a coupling
reaction of the epoxide-functionalized block polymer with the
living PS-b-PI (Mn 4 107 g/mol, Mw/Mn 1.3).143
Dendrimer-like PEOs were synthesized by repeating the
anionic ring-opening polymerization of EO, followed by the
same polymerization of a mixture of glycidol and propylene
oxide using a 3-arm PEO star as the starting precursor (Mn
105 g/mol and Mw/Mn 1.3).144
Kunaus et al. synthesized a series of dendritc PSs in a one-pot
reaction by a method that combines living anionic polymerization with a convergent process.145 As illustrated in Scheme
11, the synthesis is achieved by reacting PSLi with CDMSS,
which contains a polymerizable vinyl group and a moiety
capable of undergoing the linking reaction. Adding styrene
along with CDMSS allowed for the synthesis of high-molecularweight dendritic PSs (Mn > 600 000 g/mol) with rather narrow
polydispersities (Mw/Mn 1.3) and generational growth
approaching an average of 6G.
The other type of hyperbranched polymers is prepared by
the self-condensing vinyl polymerization (SCVP) of inimers,
L
Macromolecules
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Scheme 12. Synthesis of Hyperbranched Polystyrenes Using an Anionic Inimer
methodologies via dierent mechanisms will not be discussed,

since an previous review by Frey et al. has recently been
published.150
7.2. Syntheses of Macromolecular Architectures by
New Conceptual All-Around Iterative Methodologies.
Macromolecular architectures are composed of several polymer
chains connected at the linking point(s) via suitable reaction
sites. However, a serious synthetic limitation is present for such
polymer syntheses because the reaction site always disappears
after the introduction of a polymer segment, and the polymer
segment can no longer be introduced. Because of this
limitation, it is long believed that the synthesis of complex
macromolecular architectures, such as multiblock polymers,
exactly dened graft polymers, multicomponent -star
polymers, and high-generation and high-molecular-weight
DSPs, is very dicult or even impossible. In order to overcome
this diculty, an all-around methodology has been developed
based on a new conceptual stepwise iterative approach in
conjunction with a living anionic polymerization system. In this
methodology, the system is designed in such a way that the
reaction site is always regenerated after the introduction of the
polymer segment in each reaction sequence, and this polymer
segment introduction and regeneration of the reaction site
sequence is repeatable. If this methodology satisfactorily works,
the polymer segment can be successively and, in principle,
limitlessly introduced to construct all of the above-mentioned
macromolecular architectures. This methodology was rst
proposed for the synthesis of multicomponent -star polymers.
After its successful development, the methodology has been
extended to the synthesis of high-generation and highmolecular-weight DSPs, multiblock polymers, and exactly
dened graft polymers in the same synthetic sense.
The iterative methodology was rst proposed for the
synthesis of -star polymers, as it is shown in Scheme 14.151
At rst, the chain-end-B-functionalized living polymer is
prepared, and the B function is transformed to the A
function capable of reacting with a living polymer. The second
B-functionalized living polymer then reacts with the Afunctionalized polymer to link the two polymer chains. After
which are monomers with latent initiating moieties. Although

this methodology has been successfully used for the synthesis of
various hyperbranched polymers via dierent mechanisms,
there are only a few reports by Baskaran et al. and He et al.
about the synthesis of hyperbranched polymers from anionic
inimers (Scheme 12).146,147a,b
Frey et al. reported the synthesis of a variety of hyperbranched poly(ether)s with many hydroxyl groups via the
anionic ring-opening polymerization of glycidol, representing a
latent AB2 monomer (Scheme 13).148a,b Glycidol was slowly
Scheme 13. Synthesis of Hyperbranched Polyethers by the
Anionic Ring-Opening Polymerization of Glycidol
added to a trifunctional initiator core for the polymerization.

Because of the fast proton exchange during the polymerization,
dierent chain ends are able to simultaneously grow into a
branched structure. This approach was extended to the
synthesis of linear-b-hyperbranched diblock and hyperbranched-b-linear-b-hyperbranched triblock polymers.149a,b
The above-mentioned procedures were facile and more
conveniently accessible to synthesize hyperbranched polymers
on a large scale, but all the resulting polymers exhibited an
imperfect structure. Although only a few examples via the
(living) anionic polymerization have now been introduced, the
synthesis of many other hyperbranched polymers by similar
Scheme 14. Synthesis of -Star Polymers by Iterative Methodology Using A and B Functions: (a) Arm Introduction and (b)
Regeneration of Reaction Site
Macromolecules
Perspective
Scheme 15. Synthesis of DSPs by Iterative Methodology: (a) Arm Introduction and (b) Regeneration of Reaction Site
Figure 8. Synthesis of DSPs up to 7G by iterative methodology.
respectively. The reaction sequence involving two steps is

repeated. Finally, the 7G DSP is successfully synthesized
(Figure 8). Herein, both the A and B functions are exactly the
same as those used in Scheme 14 . In general, the A and B
functions are the BnBr or -phenylacrylate (PA) moiety and
the 3-tert-butyldimethylsilyloxymethylphenyl (SiOMP) moiety,
respectively.
For this iterative methodology, an -terminal-B2-functionalized living PMMA was used as the starting polymer, obtained
by living anionic polymerization of MMA with the initiator
prepared from sBuLi and 1,1-bis(3-tertbutyldimethylsilyloxymethylphenyl)ethylene and after transformation of the silyl group to the BnBr or PA functions as
A reaction sites by treatment with Me3SiCl/LiBr or with
Bu4NF, followed by esterication with -phenylacrylic acid.
The nal DSP is a huge macromolecule with a precisely
controlled Mn value of 1.94 106 g/mol and a narrowly
distributed Mw/Mn value of 1.02. It consists of 508 PMMA
segments and possessed 512 BnBr reactive termini capable of
continuing the DSP synthesis. The success of this methodology
made it possible to synthesize various DSPs composed of not
only PMMA but also PtBMA, PS, and a mixture of these
segments by slightly modifying the methodology.156,157
As already mentioned, DSPs are well-dened huge macromolecules with regulated hyperbranched architectures. Furthermore, a variety of functional groups can be appropriately
introduced into any generation, at any internal and/or external
position, and/or at the periphery, resulting in functionalized
hyperbranched and nanosize globular macromolecules. However, interesting properties and behavior have not yet been
suciently characterized; morphological and rheological studies
have just started. Very recently, Hutchings has reviewed that
temperature gradient interaction chromatography (TGIC), rst
developed by Chang et al.,158 is an indispensable analytical
technique to reveal the structural dispersity in complex
branched polymers, like DSPs, and other branched polymers.159
TGIC is an interaction chromatography technique. The
resolution power of TGIC is far superior to SEC, and especially
for branched polymers, the reliability of SEC is low. Actually, it
has been demonstrated that several side products and structural
the transformation to A, the third B-functionalized living

polymer reacts with the in-chain-A-functionalized block
polymer, resulting in a 3-arm ABC -star core-functionalized
with B. As can be seen, the B function is stable toward the
anion and transformable into the A function. Both the (a) and
(b) steps correspond to the polymer segment (or arm)
introduction and regeneration of the reaction site,
respectively. Since both steps quantitatively proceed, the
reaction sequence involving both steps can be repeated. By
repeating the same reaction sequence one more time, a 4-arm
ABCD -star is synthesized. Since the B function is introduced
at the core, it may be possible to continue the synthesis to
aord a 5-arm or more armed -star polymers. The Bfunctionalized living polymer is obtained by the 1:1 addition
reaction of the living polymer with 1-phenyl-1-(3-tertbutyldimethylsilyloxymethylphenyl)ethylene. After the reaction,
the silyl group is quantitatively transformed into benzyl
bromide (BnBr) reaction site (A) by treatment with
Me3SiCl/LiBr. Very recently, basically a similar iterative
methodology using an -phenylacrylate (PA) function as a
new reaction site for the synthesis of the -star polymers has
been developed.152,153 Since the PA reaction site is capable of
reacting with less reactive living poly(alkyl methacrylate)s
(PRMAs) and P2VP, the connection of PRMAs as well as
P2VP is possible. Thus, several 3-arm ABC, 4-arm ABCD, 5arm ABCDE, 6-arm ABCDEF, and even 7-arm ABCDEFG stars composed of PRMA and/or P2VP arm segments were
successfully synthesized.154ac A more ecient iterative
methodology will be introduced later.
The methodology was further developed for synthetically
dicult high-generation and high-molecular-weight DSPs.155ac
As shown in Scheme 15, a chain-end-B2-functionalized living
polymer is prepared and reacts with a core compound having
four A functions to aord a 4-arm star polymer. The B function
is then transformed into the A function, followed by reacting
with the starting B2-functionalized living polymer, resulting in a
2G DSP. The B functions are again transformed to the A
functions, and the same reaction sequence is continued. As can
be seen, both the (a) and (b) steps correspond to the arm
introduction and regeneration of the reaction site,
N
Macromolecules
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Scheme 16. Synthesis of Multiblock polymers by Iterative Methodology Using A and B Functionalities: (a) Arm Introduction
and (b) Regeneration of Reaction Site
Table 1. Synthesis of a Series of Alternate (AB)n Multiblock Polymers

Mn 103 (g/mol)
polymer
composition (%wb/wc)
type
calcd
RALLSa
Mw/Mna
calcd
PS
PMMA
AB
(AB)2
(AB)3
(AB)4
(AB)5
10.5
26.4
37.0
51.0
64.5
11.4
28.2
40.5
53.6
66.4
1.03
1.03
1.03
1.04
1.06
50/50
48/52
45/55
45/55
45/55
H NMR
48/52
47/53
43/57
43/57
45/55
Determined by SEC equipped with triple detectors. bPS. cPMMA.
Scheme 17. Synthesis of PDMS-b-PtBMA by Reacting -Chain-End-BnCl-Functionalized PDMS with Living PtBMA
of these multiblock polymers and triblock terpolymers were not

synthesized by the sequential polymerization because of the
mismatch in reactivity between the chain-end anion and the
monomer. The resulting multiblock polymers possessed
predicted Mn values and compositions, as well as narrow
MWDs, as summarized in Table 1.
Since a variety of functional MMA derivatives applicable to
the living polymerization are now available, the following
functional triblock terpolymers could also be synthesized:
P2VP-b-PS-b-poly(2-tert-butyldimethylsilyloxethyl methacrylate), P2VP-b-PS-b-poly(2,3-dimethyl-1,3-dioxolan-4-yl)methyl
methacrylate), P2VP-b-PS-b-PtBMA, and P2VP-b-PS-b-poly(ferrocenylmethyl methacrylate).162 The rst three block
terpolymers could be converted by hydrolysis to aord the
following three new functional block terpolymers: P2VP-b-PSb-poly(2-hydroxyethyl methacrylate), P2VP-b-PS-b-poly(2,3dihydroxypropyl methacrylate), and P2VP-b-PS-b-poly(methacrylic acid).
Hadjichristidis et al. previously reported the successful
synthesis of PDMS containing block polymers by developing
an ecient linking methodology using 2-(4chloromethylphenyl)ethyldimethylchlorosilane (CMPDMS) as
a heterofunctional linking agent on the basis of the greater
reactivity of the silyl chloride than the benzyl chloride (BnCl)
function toward the silanolate anion.163 As illustrated in
Scheme 17, the living PDMS was rst prepared by the anionic
polymerization of D3 and then reacted with CMPDMS. The
reaction of the silanolate anion with the silyl chloride function
was quite selective, resulting in an -terminal-BnCl-function-
defects can be detected by TGIC in such branched polymers,

whose SEC proles suggest an essentially pure product.
Next, the further extension of the iterative methodology for
the synthesis of multiblock polymers as well as exact graft
polymers is demonstrated. The synthetic outline of multiblock
polymers ((AB)n) by the iterative methodology is illustrated in
Scheme 16. At rst, an -terminal-B-functionalized living AB
diblock polymer is prepared by the sequential polymerization of
two monomers with the B-functionalized initiator. The B is
transformed to the A, followed by the subsequent reaction of
the resulting A-functionalized block polymer with the above terminal-B-functionalized living block polymer to link the two
block polymer chains, resulting in an -terminal-B-functionalized (AB)4 tetrablock polymer. By repeating the same
reaction sequence three more times, the (AB)6, (AB)8, and
(AB)10 multiblock polymers were successively synthesized.160
The -terminal-B-functionalized AB block polymer was readily
prepared by the sequential polymerization of styrene and MMA
(or 2-VP, tBMA) with 3-(tert-butyldimethylsilyloxy)-1-propyllithium. The resulting block polymer was treated with Bu4NF
and the subsequent esterication with -phenylacrylic acid was
performed to convert the PA function (A reaction site).
This procedure could be applied to the synthesis of triblock
terpolymers with an unusual block sequence. For example,
synthetically dicult PS-b-PMMA-b-P2VP and P2VP-b-PS-bPMMA triblock terpolymers could be synthesized by the
linking reactions of the living PS-b-PMMA with the -terminalPA-functionalized P2VP and of the living P2VP with the terminal-PA-functionalized PS-b-PMMA, respectively.161,162 All
O
Macromolecules
Perspective
Scheme 18. Synthesis of Exact Graft Copolymers by Iterative Methodology
alized PDMS. The living PtBMA was then reacted with the
BnCl-functionalized PDMS to aord a well-dened PDMS-bPtBMA, dicult to be linked by sequential polymerization. By
extending this methodology, a new tetrablock quarter polymer,
PS-b-PI-b-PDMS-b-P2VP, was synthesized by the linking
reaction of the living P2VP with an -terminal-BnCl-functionalized PS-b-PI-b-PDMS, prepared by the reaction of the living
PS-b-PI-b-PDMS with CMPDMS.164 Moreover, a particular
pentablock quintopolymer of PS-b-PI-b-PDMS-b-PtBMA-bP2VP was successfully synthesized by reacting the living
P2VP-b-PtBMA with the same BnCl-functionalized PS-b-PI-bPDMS.164
Finally, the synthesis of exact graft polymers by the iterative
methodology is introduced. As mentioned above, a successful
example of exact graft polymers has not yet been reported,
except for one example having a minimum of two graft units.125
Scheme 18 shows the synthetic outline of exact graft polymers
by the iterative methodology, which is basically same as those
developed above.166a,b At rst, an in-chain-B-functionalized AB
living diblock polymer is prepared. After transformation to the
A, the resulting in-chain-A-functionalized AB diblock polymer
is reacted with the above in-chain-B-functionalized AB living
diblock polymer to connect the two block polymers. Thus, one
graft unit is prepared. The B function is transformed to the A,
followed by reacting with the B-functionalized AB living
diblock polymer to prepare two graft units. The linking and
transformation reactions correspond to the arm introduction
(a) and regeneration of reaction site (b) steps. By repeating
the reaction sequence involving the two steps three more times,
a graft copolymer having ve graft units was successively
synthesized. As the in-chain-B-functionalized living diblock
polymer, a living in-chain-(3-tert-butyldimethylsilyloxymethylphenyl)-functionalized PS-b-PMMA was prepared by the
sequential addition of styrene, 1-(3-tert-butyldimethylsilyloxymethylphenyl)-1-phenylethylene, and MMA to sBuLi.166a,b
The silyl group was deprotected with Bu4NF to generate the
hydroxyl function, which was subsequently esteried with phenylacrylic acid into the PA function (A reaction site). In all
the resulting graft copolymers, the molecular weights and
compositions agreed with the calculated values (Table 2). For
the resulting graft copolymers, the molecular weight of the
main chain was exactly equal to the total molecular weight of
PMMA blocks, the molecular weight of PS corresponds to that
of the graft chain, and the distance between the PS graft chains
was the same as the molecular weight of each PMMA block.
Thus, obviously, the resulting polymers were all exact graft
copolymers where the above-mentioned three variables are
perfectly controlled. The living in-chain-functionalized PS-bPtBMA and PS-b-P2VP diblock polymers were also used in the
Table 2. Synthesis of a Series of Exact Graft Copolymers up

to Five PS Grafts
Mn 103 (g/mol)
type
calcd
RALLS
block
2 grafts
3 grafts
4 grafts
5 grafts
12.5
22.2
33.8
43.5
56.2
12.6
23.6
34.6
45.6
55.0
composition (%wb/wc)
Mw/Mn
calcd
1.03
1.03
1.02
1.04
1.04
50/50
51/49
50/50
49/51
50/50
H NMR
48/52
50/50
49/51
50/50
50/50
Determined by SEC equipped with triple detectors. bPS. cPMMA.
same methodology to successfully synthesize the corresponding

exact graft copolymers.166b A basically similar iterative methodology was also developed to successfully synthesize two exact
graft copolymers and a super H-shaped exact graft PS (Figure
9).167a,b Thus, the success of the iterative methodology allows
the synthesis of various complex macromolecular architectures
including -star polymers, DSPs, multiblock, and exact graft
polymers.
Concerning the -star synthesis, a more eective design of
the iterative methodology is possible (Scheme 19).168ad In this
methodology, the A is reacted with the living polymer to
change the B, capable of transforming into the A. Another
living polymer then reacts with the chain-end-A-functionalized
polymer to connect the polymer chain, resulting in the inchain-B-functionalized block polymer. By transformation to the
A, followed by reacting with another living polymer, a 3-arm star polymer core-B-functionalized polymer is obtained. The
repletion of the same reaction sequence one more time
produces a 4-arm -star. Since the 4-arm -star possesses the B
function at the core, it may be possible to continue the reaction
sequence to aord a 5-arm or more armed -stars. Herein, DPE
and its anion were utilized as the A and B functions. The
transformation was carried out by the reaction of the B with 1(4-(3-bromopropyl)phenyl)-1-phenylethylene (1) to regenerate the DPE of A. The DPE function not only is used to react
with a living anionic polymer to link the polymer chain (arm
introduction step) but also oers a reaction point for the
introduction of the same DPE function (regeneration of the
reaction site). With the use of 1,3-bis(1-phenylethyenyl)benzene represented as the AA and 1, the 4-arm A2B2 and 6arm A2B2C2 -stars were successively synthesized (Scheme
20).168c,d
In order to further increase the number of arms in each
sequence, we designed a new agent, 3,5-bis(3-(4-(1phenylethenyl)phenyl)propoxy)benzyl bromide (2), with
which two DPE reaction sites can be introduced via one DPE
anion produced by the addition reaction.169a,b As illustrated in
P
Macromolecules
Perspective
Figure 9. Synthesis of exact graft (co)polymers and super H-shaped exact graft PS.
Scheme 19. Synthesis of -Star Polymers up to 4-Arm ABCD by Iterative Methodology: (a) Arm Introduction and (b)
Regeneration of Reaction Site
Scheme 20. Synthesis of -Stars by Iterative Methodology Using AA
Scheme 21. Synthesis of -Star Polymers up to 31-Arm AB2C4D8E16 Type by Iterative Methodology Using 2
enables the synthetic range of multicomponent -star polymers

to be signicantly broadened. Although the synthesized -star
polymers are expected to create quite novel morphologies, the
morphological studies of -star polymers even with three
dierent arms are complicated because of the diculty in
obtaining clear phase-separated structures in their equilibrium
states.170
It has been demonstrated that the developed iterative
methodology is actually very eective not only for the synthesis
of multicomponent -star polymers but also for the abovementioned complex macromolecular architectures such as highgeneration high-molecular-weight DSPs, multiblock polymers,
and even exact graft polymers. The success of the methodology
Scheme 21, the methodology using 2 is basically similar to

those mentioned above. Compound 2 rst functions as the core
agent and then the agent to introduce two DPE reaction sites.
The number of regenerated DPE reaction sites and hence the
number of arm segments to be connected exponentially
increase in each reaction sequence. By repeating the same
reaction sequence with the use of living polymers (B), (C),
(D), and (E), the 3-arm AB2, 7-arm AB2C4, 15-arm AB2C4D8,
and 31-arm AB2C4D8E16 -star polymer having 32 DPE
reaction sites at the core were successively synthesized. The
iterative methodology using 2 also operates very eectively for
the synthesis of multiarmed multicomponent -star polymers.
Thus, the appearance of the aforementioned methodology
Q
Macromolecules
Perspective
anionic poly(macromonomer)s was described. In section 7, we

introduced the recent synthetic advances of complex macromolecular architectures as well as the new conceptual iterative
methodology adaptable to the synthesis of almost all macromolecular architectures. With these methodologies, the synthesis of various as-designed macromolecular architectures has
now become possible.
The future perspectives are as follows: Two main subjects
related to the future perspectives remain as unsolved problems.
The rst one is to achieve the perfect control of the regio- and
stereoselectivities. Ideas and proposals based on coordination
chemistry successful for the transition-metal-mediated polymerization are needed for this objective. The likeliest candidates are
specially designed Lewis acids and phosphazene bases, which
might be strongly coordinated to anions or cations to make
suitable circumstances for highly selective monomer insertion.
Multidentate ligands, such as polyamines, polyethers, crown
ethers, and their designed derivatives, may also be utilized.
Since the polymer properties and behavior are signicantly
inuenced even by a small dierence in the selectivity, these
investigations should be continued for the development of new
materials.
The second one is the achievement of the living polymerization of highly reactive polar monomers, such as acrylonitrile,
nitroethylene, vinylidene cyanide, and -cyanoacrylate. Since
the anionic polymerization of acrylate, methacrylates, N,Ndialkylacrylamides, and methacrylonitrile have been signicantly improved in livingness by the addition of weak Lewis
acids and/or several ligands, these additives are also expected to
control the anionic polymerization of such reactive polar
monomers. Their growing chain-end anions seem stable even in
the presence of oxygen and water, thus rendering the (living)
anionic polymerization of aqueous media in air possible. The
resulting polymers are highly functionalized living anionic
polymers and can be directly used in water in the presence of
oxygen.
The nal perspective is the precise synthesis of complex
architectural f unctional polymers. Throughout this Perspective,
the synthesis of various new-type living anionic polymers
having functionalities, specic structures, regio- and stereoselectivites, although not perfectly controlled, and comblike
segments, as well as adopting rigid-rod-like and -helix and strand conformations, were introduced along with the
eectiveness. We demonstrated the eectiveness of a newly
developed all-around iterative methodology, which is adaptable
to almost all complex architectural polymer synthesis. Thus,
versatile state-of-the-art synthetic tools with many functions
and the know-how for the synthesis of macromolecular
architectures are available. The combination of such tools and
the know-how oers exciting possibilities for the development
of high performance specialty polymers and high-quality
nanostructural materials.
Unfortunately, morphological and other related studies of
supramolecular nanostructures and molecular assemblies, one
of the key factors in nanoscience, have not suciently
progressed. The development of new analytical methodologies
and even more improved analytical techniques are now matters
of urgency. It is time to truly fulll the collaborations among
the polymer chemists and physicists to make real advances in
polymer chemistry. As an insightful proposal, a few practical
examples (-star polymers and their novel morphologies) about
the constructive partnership and mutual understanding among
strongly indicates that various macromolecular architectures

can be readily synthesized by developing only one methodology
based on the same concept. This means that a methodology
developed for -star polymer synthesis may also be applied to
other architectural polymer synthesis by modifying the
methodology to change the numbers and/or positions of the
polymer chains and linking points. Since many ecient
methodologies individually designed for each of the macromolecular architectures have already been reported, they should
be reconsidered from this applicable point. For this reason, we
consider the all-around iterative methodology and possible
synthesis of various macromolecular architectures introduced in
7.2 to be an eective promising strategy from the viewpoint of
future perspectives.
8. CONCLUSIONS AND FUTURE OUTLOOK

The recent advances in living anionic polymerization systems
and the synthesis of structurally complex macromolecular
architectures, which were synthetically dicult until recently, in
addition to the principal strengths of this eld, have been
reviewed. In all the reports, reviews, and books until the mid1980s, it had been recognized that the major drawback in living
anionic polymerization was its intolerance to most of the
functionalities, thus rendering it dicult or even impossible for
functional monomers. In section 2, it was demonstrated that
almost all essentially useful functionalities are compatible with
living anionic polystyrene, although some of them need to be
protected. All these functionalities may possibly be used in
other living anionic polymerization systems because their living
chain-end anions are comparable to or less reactive than living
polystyrene. Accordingly, no special care is now needed when
using the many useful functional groups in living anionic
polymerization. In section 3, new types of living anionic
polymers that appeared by employing specially designed
initiator systems and by changing the monomer structures to
be feasible for the polymerization were introduced. Living
anionic polymerization of cyclic monomers, (meth)acrylates,
N,N-dialkylacrylamides, and even methacrylonitrile was practically achieved by adding several promising additives such as
phosphazene bases and weak Lewis acids. Among these
systems, the high-temperature living anionic polymerization
of alkyl (meth)acrylates by the addition of the modied Lewis
acid(s) made it possible to use the system in industry. As
described in section 4, the stereoselective control was much
improved for the living polymerization of (meth)acrylates and
N,N-dialkylacrylamides in the presence of several modied
Lewis acids. Although living anionic polymerization of 2triisopropoxysilyl-1,3-butadiene was found to completely occur
in both regio- and stereoselective manners, as the only
exceptional case, the regio- and stereoselectivities have not
yet been perfectly controlled for the polymerization of 1,3butadiene and isoprene. In section 5, we introduced the
synthesis of special living anionic polymers adopting rigid-rodlike conformations and ordered conformations of -helices or
-strands. They could be synthesized by living anionic
polymerization of phenyl vinyl sulfoxide (followed by thermal
treatment), alkyl isocyanates, and NCAs. Moreover, several
block polymers and even star-branched polymers consisting of
such unique and characteristic segments were synthesized and
examined as potentially useful specialty polymers in the elds of
nano- and biocompatible materials. In section 6, the successful
synthesis of various complex branched polymers composed of
comblike polymers by directly using in situ prepared living
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Macromolecules
Perspective
them have been demonstrated in the review article recently

reported by Hadjichristidis.171
is an assistant professor of Department of Organic and Polymeric

Materials at Tokyo Institute of Technology. His research interests are
the precise synthesis and phase-selective chemistry in block copolymer
system and the synthesis of star-branched polymers and block
copolymers for applications in nanomaterials.
AUTHOR INFORMATION
Corresponding Author
*E-mail ahirao@email.plala.or.jp (A.H.).

Notes
The authors declare no competing nancial interest.

Biographies
Takashi Ishizone was born in Saitama, Japan, in 1963. He received a

masters degree in polymer chemistry from Tokyo Institute of
Technology in 1988 under the supervision of Professors Seiichi
Nakahama and Akira Hirao and started his academic career as an
assistant professor in the same institution from 1989. After receiving a
doctorate degree in 1994, he studied organic chemistry as a visiting
scientist at The University of Chicago in the group of Professor P. E.
Eaton from 1995 to 1996. Since 2000, he is an Associate Professor of
Department of Organic and Polymeric Materials at Tokyo Institute of
Technology. His main research areas center on the synthesis of novel
thermally stable polymers possessing adamantane skeletons and the
synthesis of novel functional polymers showing water solubility and
thermoresponsive property by means of living anionic polymerization.
Professor Akira Hirao graduated with his doctorate degree in 1975

from Tokyo Institute of Technology (Titech), Japan, in chemical
engineering. After one and half years as a postdoctoral fellow at the
University of Alabama in the USA, he was appointed as an Assistant
Professor at Titech and promoted to Full Professor in 1996, via an
Associate Professor, and retired from Titech in 2013 to be an Emeritus
Professor. He is currently a Distinguished Chair Professor of National
Taiwan University (Taiwan), a Chair Professor of Soochow University
(China), and Visiting Professors in Pohang University of Science and
Technology (Korea) and Fudan University (China) to deliver lectures
for a few years. He has published over 300 papers in peer reviewed
journals, 20 book chapters including coeditors, and given 80 keynote,
plenary, and invited lectures at International Conferences and over 300
invited lectures including Polymer Societies, Chemical Societies,
Universities, and companies in Japan (>200) as well as overseas
(>100). He was awarded the Japan Polymer Society Award (2010) and
the Publication Award for the year 2011, Society of Rheology (USA).
His research interests lie at the molecular design and precise synthesis
of macromolecular architectures by living anionic polymerization and
nano surface structural control using well-dened peroroalkylated
polymers.
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Advances in Living Anionic Polymerization: From Functional

Mn values being 1.05 or even lower. Finally, the resulting living

In the past 25 years, remarkable advances in various living/

Received: June 7, 2013

dx.doi.org/10.1021/ma401175m | Macromolecules XXXX, XXX, XXXXXX

Figure 1. Functional styrene derivatives capable of living anionic polymerization.

2. LIVING ANIONIC POLYMERZATION OF

ization, and the synthesis of living anionic polymers having

dx.doi.org/10.1021/ma401175m | Macromolecules XXXX, XXX, XXXXXX

Scheme 1. Protection and Living Anionic Polymerization of Functional Styrenes

Figure 2. Styrene derivatives substituted with protected functionalities.

Figure 3. Styrene derivatives para-substituted with electron-withdrawing groups.

Functional groups having active hydrogen(s) and carbonyl

As another eective strategy, Ishizone et al. introduced a

dx.doi.org/10.1021/ma401175m | Macromolecules XXXX, XXX, XXXXXX

anionic polymerization until the 1980s. Most importantly, the

The suppression of the unwanted addition reaction to the

3. NEW MONOMERS AND ADDITIVES FEASIBLE FOR

Figure 4. SEC proles of poly(p-DVB): (a) without KOBut, Mn = 22

living polymers were stable only for a few minutes at 78 C,

Figure 5. Exo-methylene type and the corresponding acyclic monomers.

dx.doi.org/10.1021/ma401175m | Macromolecules XXXX, XXX, XXXXXX

anionic polymerizability of the N,N-dialkylmethacrylamides

well-dened diblock polymer, PMMA-b-PBF, while 2PhBd

Scheme 2. Microstructure of Poly(benzofulbene) (PBF)

dx.doi.org/10.1021/ma401175m | Macromolecules XXXX, XXX, XXXXXX

Scheme 3. Anionic Ring-Opening Polymerization of Ferrocenyldimethylsilane (FDS)

the presence of P4-t-Bu, enabling the facile changeover from an

crucial to achieve living anionic polymerization of such polar

dx.doi.org/10.1021/ma401175m | Macromolecules XXXX, XXX, XXXXXX

Scheme 5. Stereospecic Living Anionic Polymerization of MMA

narrow MWDs (Mw/Mn 1.1) were produced even at room

may be eectively suppressed by the coordination of Et3B to

4. REGIO- AND STEREOSELECTIVE POLYMERIZATION

dx.doi.org/10.1021/ma401175m | Macromolecules XXXX, XXX, XXXXXX

selectivities were perfectly controlled in the polymerization of

For example, the syndiotactic-rich (rr = 78%) PDEA was

Scheme 6. Stereoselective and Regioselective Living Anionic

regioselective and stereoselective fashions in addition to the

5. LIVING ANIONIC POLYMERS WITH UNIQUE

dx.doi.org/10.1021/ma401175m | Macromolecules XXXX, XXX, XXXXXX

Scheme 8. Complex Branched Polymers by Using Living Poly(macromonomer)s

CBABC pentablock terpolymer, PHI-b-PI-b-PS-b-PI-b-PHI,

controllable molecular weights and narrow MWDs (Mw/Mn <

dx.doi.org/10.1021/ma401175m | Macromolecules XXXX, XXX, XXXXXX

opportunities for the development of new functional specialty

6. LIVING ANIONIC POLY(MACROMONOMER)S

7. PRECISE SYNTHESIS OF MACROMOLECULAR

dx.doi.org/10.1021/ma401175m | Macromolecules XXXX, XXX, XXXXXX

decreasing chain-end anion reactivity. Thus, special care is

Figure 7. 5G dendrimer-like star branched polymer and its block

architecture to the dendrimers but composed of many polymer

Figure 6. Three structural factors of graft polymer.

graft polymer, in which all three factors are perfectly controlled,

dx.doi.org/10.1021/ma401175m | Macromolecules XXXX, XXX, XXXXXX

Scheme 11. Synthesis of Dendritic Polystyrenes by Convergent Living Anionic Polymerization

based on the core-rst divergent approach (Scheme 10). By

coupling reaction of the resulting brominated block polymer

dx.doi.org/10.1021/ma401175m | Macromolecules XXXX, XXX, XXXXXX

Scheme 12. Synthesis of Hyperbranched Polystyrenes Using an Anionic Inimer

methodologies via dierent mechanisms will not be discussed,

which are monomers with latent initiating moieties. Although

added to a trifunctional initiator core for the polymerization.