polymers

Review
Block Copolymers: Synthesis, Self-Assembly,
Review
Block
and Copolymers: Synthesis, Self-Assembly,
Applications
and Applications
Hongbo Feng 1, Xinyi Lu 1, Weiyu Wang 2, Nam-Goo Kang 1 and Jimmy W. Mays 1,3,*
1 Department 1of Chemistry,
Hongbo Feng , Xinyi Lu 1 ,University
Weiyu Wang 2 , Nam-Goo
of Tennessee, Knoxville,
KangTN 1 and
37996, USA;W.
Jimmy Mays 1,3, * (H.F.);
hfeng9@utk.edu
1 xlu8@utk.edu (X.L.); nkang1@utk.edu (N.-G.K.)
Department of Chemistry, University of Tennessee, Knoxville, TN 37996, USA; hfeng9@utk.edu (H.F.);
2 Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37830, USA;
xlu8@utk.edu (X.L.); nkang1@utk.edu (N.-G.K.)
2 wwang41@utk.edu
Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37830, USA;
3 Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37830, USA
wwang41@utk.edu
*3 Correspondence: jimmymays@utk.edu; Tel.: +1-865-974-0747
Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37830, USA
*Received: 19 September;
Correspondence: Accepted: 3 October
jimmymays@utk.edu; 2017;
Tel.: Published: 9 October 2017
+1-865-974-0747

Received: 19 September 2017; Accepted: 3 October 2017; Published: 9 October 2017

Abstract: Research on block copolymers (BCPs) has played a critical role in the development of
polymer chemistry,
Abstract: Research with numerous
on block pivotal(BCPs)
copolymers contributions that have
has played advanced
a critical role inour
theability to prepare,
development of
characterize, theoretically model, and technologically exploit this class of materials
polymer chemistry, with numerous pivotal contributions that have advanced our ability to in a myriad of
prepare,
ways in the fields
characterize, of chemistry,
theoretically physics,
model, material sciences,
and technologically and biological
exploit this classand medical sciences.
of materials The
in a myriad
breathtaking progress has been driven by the advancement in experimental techniques
of ways in the fields of chemistry, physics, material sciences, and biological and medical sciences. enabling the
synthesis and characterization of a wide range of block copolymers with tailored
The breathtaking progress has been driven by the advancement in experimental techniques enabling composition,
architectures,
the synthesis andandcharacterization
properties. In this
of a review, we of
wide range briefly
block discussed
copolymers thewith
recent progress
tailored in BCP
composition,
synthesis, followed by a discussion of the fundamentals of self-assembly of BCPs along with
architectures, and properties. In this review, we briefly discussed the recent progress in BCP synthesis, their
applications.
followed by a discussion of the fundamentals of self-assembly of BCPs along with their applications.

Keywords:
Keywords: block
block copolymers;
copolymers; synthesis;
synthesis; self-assembly; applications
self-assembly; applications

1.
1. Introduction
Introduction
Block
Block copolymers
copolymers (BCPs)
(BCPs) are
are aa specific
specific class
class ofof copolymers,
copolymers, in in which
which thethe chemically
chemically distinct
distinct
monomer units are grouped in discrete blocks along the polymer chain [1]. Figure
monomer units are grouped in discrete blocks along the polymer chain [1]. Figure 1 illustrates 1 illustrates a fewa
of
fewtheofmany architectures
the many of BCPs,
architectures of which
BCPs, can be configured
which into linear,
can be configured intobranched (graft and(graft
linear, branched star), and
and
cyclic molecular
star), and architectures.
cyclic molecular Thanks to
architectures. the advancement
Thanks of polymer
to the advancement synthetic
of polymer strategies
synthetic and
strategies
techniques, e.g., controlled polymerization techniques along with facile
and techniques, e.g., controlled polymerization techniques along with facile post-polymerizationpost-polymerization
functionalization,
functionalization, BCPsBCPs with
with precisely
precisely controlled
controlled molecular
molecular weights
weights and defined macromolecular
and defined macromolecular
architectures can be prepared [2–8]. The extraordinary structural and compositional
architectures can be prepared [2–8]. The extraordinary structural and compositional versatility versatility
of BCPsof
BCPs has facilitated an explosion in the discovery and implementation of innovative
has facilitated an explosion in the discovery and implementation of innovative synthetic strategiessynthetic strategies
capable
capable ofof generating
generating previously
previouslyunattainable
unattainablelevels
levelsofofman-made
man-madearchitectural
architecturalcomplexity.
complexity.

Linear block terpolymers "Comb" graft copolymers "Miktoarm" star terpolymers Cyclic block terpolymers

Figure 1. Representative architectures of linear block terpolymers, “comb” graft polymers, miktoarm
star terpolymers, and cyclic block terpolymers.

Polymers 2017, 9, 494; doi:10.3390/polym9100494 www.mdpi.com/journal/polymers

Polymers 2017, 9, 494; doi:10.3390/polym9100494 www.mdpi.com/journal/polymers

Polymers 2017, 9, 494 2 of 31
Polymers 2017, 9, 494 2 of 31

One of the ubiquitous features of BCPs is their ability to form a plethora of nanoscale ordered
structures.
One of By the manipulating
ubiquitous featuresthe molecular
of BCPs isparameters
their ability such as athe
to form Flory-Huggins
plethora of nanoscaleinteraction
ordered
parameter By
structures. (χ),manipulating
the degree ofthe polymerization (N), andsuch
molecular parameters the volume fraction (f), various
as the Flory-Huggins morphologies
interaction parameter
including
(χ), spherical,
the degree cylindrical, lamellar,
of polymerization (N), andand
the others
volumehave been(f revealed
fraction ), variousboth experimentally
morphologies and
including
theoretically
spherical, [9,10]. lamellar,
cylindrical, Furthermore, recent
and others havestudies have both
been revealed demonstrated that and
experimentally thetheoretically
macromolecular
[9,10].
architecture isrecent
Furthermore, another key factor
studies in controlling both
have demonstrated themacromolecular
that the resulting morphologies and their
architecture extentkey
is another of
long range
factor order [11].
in controlling bothDuethetoresulting
these fascinating features,
morphologies research
and their onof
extent BCPs
longhas
rangelong been
order a popular
[11]. Due to
topic worldwide.
these Figure 2research
fascinating features, shows the on number
BCPs hasoflong
publications with the
been a popular topic
topic “block copolymer”
worldwide. over
Figure 2 shows
the number
past fiveof decades.
publications with the topic “block copolymer” over the past five decades.

4500
4000
Number of Publications

3500
3000
2500
2000
1500
1000
500
0
1960 1970 1980 1990 2000 2010
Year

Figure
Figure 2. The number
2. The number of
of publications with block
publications with block copolymer
copolymer as
as topic
topic against
against year. The data
year. The data were
were
obtained
obtained from
from Web
Web of
of Science
Science (2017
(2017 Clarivate
Clarivate Analytics).
Analytics).

In addition to the academic interest in BCPs, the scope of applications for BCPs has been rapidly
expanding totothe
expanding the fields
fields of advanced
of advanced materials
materials (e.g., thermoplastic
(e.g., thermoplastic elastomers),
elastomers), drugpatterning,
drug delivery, delivery,
patterning, porous materials, and many others over the last two decades
porous materials, and many others over the last two decades [12]. Thermoplastic elastomers take [12]. Thermoplastic
elastomers take
advantage of theadvantage
combinationof the ofcombination of rubbery
rubbery segments and segments and rigid
rigid segments segments
within block within block
copolymers.
copolymers. Drug encapsulation and delivery are facilitated by the amphiphilicity
Drug encapsulation and delivery are facilitated by the amphiphilicity of block copolymers in solution. of block
copolymers
The applicationin solution. The application
of block copolymers of the
in both block
softcopolymers
lithography in and both the soft
synthesis lithography
of porous and
materials
synthesis
is based onofthe porous
variousmaterials
nanoscale is based on the various
morphologies inducednanoscale morphologies
by self-assembly. Each ofinduced by self-
the applications
assembly. Each
mentioned above ofwill
the applications
be elaboratedmentioned abovetext.
on in the main will be elaborated on in the main text.
This review
This reviewbriefly
briefly covers
covers the the recent
recent breathtaking
breathtaking progress progress in the synthesis,
in the synthesis, self-assembly
self-assembly behavior,
behavior, and applications of BCPs. Section 2 briefly describes the synthetic
and applications of BCPs. Section 2 briefly describes the synthetic strategies for the preparation strategies for the
of
preparation of BCPs. Section 3 discusses BCP self-assembly in bulk and in solution.
BCPs. Section 3 discusses BCP self-assembly in bulk and in solution. Section 4 presents several major Section 4 presents
several majorofapplications
applications of BCPs in elastomer,
BCPs in thermoplastic thermoplastic
drugelastomer,
delivery, softdrug delivery, soft
lithography, andlithography, and
porous material
porous material applications. The conclusions and future perspectives of BCP research
applications. The conclusions and future perspectives of BCP research are presented in the last section. are presented
in the
We lastthat
hope section. We hope
this review that
will this review
attract emergingwill attract emerging
researchers researchers
to this field to thisthe
and advance field and advance
understanding
the understanding
and utilization of the and utilizationBCP
fascinating of the fascinating BCP systems.
systems.

2. Synthesis of BCPs
Significant work has been focused on the synthesis of BCPs with with structural
structural and
and composition
composition
variety. The synthetic
variety. The synthetic strategies
strategies mainly
mainly include:
include: (1)
(1) the
the sequential
sequential addition
addition of monomers via
“living”/controlled polymerizationtechniques;
“living”/controlled polymerization techniques;
andand (2) coupling
(2) coupling reactions
reactions exploiting
exploiting the chain-
the active active
chain-ends of different
ends of different chain chain segments
segments [13]. [13].
Polymers 2017, 9, 494 3 of 31

Polymers 2017, 9, 494 3 of 31

2.1. Sequential Addtion Polymerization
2.1 Sequential Addtion Polymerization
2.1.1. Controlled Polymerization
2.1.1. Controlled Polymerization
Controlled radical polymerization (CRP) techniques represent the most versatile and facile
approach Controlled radical polymerization
for BCP synthesis, mainly due to (CRP) techniques represent
their compatibility with a wide thespectrum
most versatile and facile
of monomers, high
approach
tolerance for BCP synthesis,
of functional groups and mainly due to their
impurities, and compatibility with a wide
ease of experimental setupspectrum of monomers,
[14–16]. The preparation
of high
BCPstolerance of functional
using sequential CRPgroups
relies onandtheimpurities,
fact that and ease of experimental
the reactive polymer chain setup
end[14–16]. The
is preserved
preparation of BCPs using sequential CRP relies on the fact that the reactive polymer chain end is
by a reversible reaction between the active species and the dormant species [17–19]. Over the last
preserved by a reversible reaction between the active species and the dormant species [17–19]. Over
two decades, numerous literature has described the synthesis of BCPs via controlled polymerization
the last two decades, numerous literature has described the synthesis of BCPs via controlled
techniques including: atom transfer racial polymerization (ATRP), reversible addition-fragmentation
polymerization techniques including: atom transfer racial polymerization (ATRP), reversible
chain transfer (RAFT) radical polymerization, nitroxide-mediated polymerization (NMP), and many
addition-fragmentation chain transfer (RAFT) radical polymerization, nitroxide-mediated
others [20–22].
polymerization (NMP), and many others [20–22].
Polymer
Polymerchainchainends
ends equipped
equipped withwithan analkyl
alkyl halide
halide enables
enables ATRPATRP to prepare
to prepare BCPsBCPs
through through
the
theaddition
addition of a second monomer. For example, a series of biocompatible,
of a second monomer. For example, a series of biocompatible, thermo-responsive ABA thermo-responsive
ABA triblock
triblock copolymers
copolymers comprising
comprising poly(N-isopropyl
poly(N-isopropyl acrylamide)
acrylamide) (PNIPAM) (PNIPAM) as theand
as the A block A block
poly(2-and
poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) as the central
methacryloyloxyethyl phosphorylcholine) (PMPC) as the central B block was synthesized using B block was synthesized using
ATRP
ATRP initiated
initiatedbybyaa difunctional initiator,asas
difunctional initiator, illustrated
illustrated in Scheme
in Scheme 1 [23].1An[23]. An terminated
α,ω-Br α,ω-Br terminated
PMPC
PMPC wassynthesized
was first first synthesized in methanol,
in methanol, purified, purified,
and used and used subsequently
subsequently for the polymerization
for the polymerization of NIPAM. of
NIPAM. This doubly
This doubly amphiphilic
amphiphilic BCP exhibits
BCP exhibits interesting
interesting thermosensitive
thermosensitive properties,
properties, whereaswhereas
above above
the
thelower
lowercritical
criticalsolution
solution temperature
temperature (LCST) of PNIPAM,
(LCST) of PNIPAM, the BCP self-assembles
the BCP into a into
self-assembles physical gel.
a physical
gel.The
Thephosphoryl
phosphoryl choline
choline moiety
moietyis is
ananimportant
important component
component of of
cell membranes.
cell membranes. The
Thecellcell
viability
viability
experiments
experiments confirmedthat
confirmed thatthese
thesethermo-responsive
thermo-responsive gels gelsarearesufficiently
sufficientlybiocompatible
biocompatible to to
actact
as as
a a
culture medium for hamster
culture medium for hamster lung cells. lung cells.

Scheme
Scheme1. Synthesis
1. of theSynthesis
poly(N-isopropyl
of acrylamide-b-2-methacryloyloxyethylphosphorylcholine-
the poly(N-isopropyl acrylamide-b-2-
b-N-isopropyl acrylamide) (PNIPAM-b-PMPC-b-PNIPAM)
methacryloyloxyethylphosphorylcholine-b-N-isopropyl triblock copolymers
acrylamide) via atom transfer racial
(PNIPAM-b-PMPC-b-PNIPAM)
polymerization (ATRP) using
triblock copolymers a bifunctional
via atom transfer ATRP
racial initiator.
polymerization (ATRP) using a bifunctional
ATRP initiator.
Matyjaszewski et al. reported the preparation of poly(n-butyl acrylate-b-methyl methacrylate)
Matyjaszewski et al. reported the preparation of poly(n-butyl acrylate-b-methyl methacrylate)
(PBA-b-PMMA) by activators regenerated by electron transfer atom transfer radical polymerization
(PBA-b-PMMA) by activators regenerated by electron transfer atom transfer radical polymerization
(ARGET ATRP) with ppm levels of Cu catalyst [24]. Controlled polymerization was realized using
(ARGET ATRP) with ppm levels of Cu catalyst [24]. Controlled polymerization was realized using
tris(2-pyridylmethyl)amine (TPMA) as a ligand because of its strong binding interaction to copper.
tris(2-pyridylmethyl)amine (TPMA) as a ligand because of its strong binding interaction to copper.
This new ARGET system was also successfully applied to the efficient synthesis of styrene and
This new ARGET system was also successfully applied to the efficient synthesis of styrene and n-
n-butyl acrylate block copolymers [25]. Later on, miniemulsion ARGET ATRP was developed
butyl acrylate block copolymers [25]. Later on, miniemulsion ARGET ATRP was developed by the
bysame
the same
groupgroup andfor
and used used for the preparation
the preparation of homopolymers
of homopolymers and block copolymers
and block copolymers [26,27].
[26,27]. However,
However, ATRP still does not work for some monomers, though it has many advantages
ATRP still does not work for some monomers, though it has many advantages compared to other compared
to other polymerization
polymerization methodsmethods for block
for block copolymerization.
copolymerization. For For example,
example, some
some monomers
monomers contain
contain
functionality
functionality that can form complexes with transition metal catalyst and have a detrimental effecteffect
that can form complexes with transition metal catalyst and have a detrimental on
onpolymerization,
polymerization,such suchasasside
sidereactions
reactionsresulting
resultingin ina abroad
broadpolydispersity
polydispersity index
index (PDI)
(PDI) [15].
[15].
Polymers 2017, 9, 494 4 of 31

Tremendous efforts
Polymers 2017, have been devoted to developing novel ligands to minimize such side reactions
9, 494 4 of 31 [28].

ATRP-based dispersion polymerizations have also been developed. Armes and coworkers synthesized
Tremendous efforts have been devoted to developing novel ligands to minimize such side reactions
zwitterionic PMPC-based block copolymers by a dispersion ATRP process [29]. PEG–Br was used as
[28]. ATRP-based dispersion polymerizations have also been developed. Armes and coworkers
macroinitiator with CuBr/ 2,20 -bipyridine as the catalyst for the dispersion polymerization of PMPC
synthesized zwitterionic PMPC-based block copolymers by a dispersion ATRP process [29]. PEG–Br
in isopropanol/water (9:1, w/w). with
was used as macroinitiator UsingCuBr/
ethylene glycol dimethacrylate
2,2′-bipyridine (EGDMA)
as the catalyst for theasdispersion
a crosslinker,
hydrogel particles with
polymerization controllable
of PMPC sizes were obtained.
in isopropanol/water (9:1, w/w).The particle
Using sizeglycol
ethylene coulddimethacrylate
be controlled by
the block
(EGDMA) as a crosslinker, hydrogel particles with controllable sizes were obtained. Thethe
composition and initial MPC concentration. Using a similar strategy, samesize
particle group
synthesized
could bewell-defined
controlled by the PEG-b-PDMAEMA-b-PMPC.
block composition and initial MPC Huang and coworkers
concentration. Using asynthesized a series
similar strategy,
of ABAthe triblock
same group synthesized
copolymers, well-defined
consisting PEG-b-PDMAEMA-b-PMPC.
of double-bond-containing Huang and coworkers
poly(phenoxyallene) (PPOA),
PMMA, synthesized a series using
or PBA segments of ABA triblock
sequential freecopolymers, consisting of
radical polymerization anddouble-bond-containing
ATRP [30]. A bifunctional
initiator bearing azo and halogen-containing ATRP initiating groups wasradical
poly(phenoxyallene) (PPOA), PMMA, or PBA segments using sequential free polymerization
first used to initiate the
and ATRP [30]. A bifunctional initiator bearing azo and halogen-containing ATRP initiating groups
conventional free radical homopolymerization of phenoxyallene with a cumulated double bond to give
was first used to initiate the conventional free radical homopolymerization of phenoxyallene with a
a PPOA-based macroinitiator with ATRP-initiating groups at both ends. PMMA-b-PPOA-b-PMMA
cumulated double bond to give a PPOA-based macroinitiator with ATRP-initiating groups at both
and PBA-b-PPOA-b-PBA
ends. PMMA-b-PPOA-b-PMMA triblock copolymers were synthesized
and PBA-b-PPOA-b-PBA bycopolymers
triblock the ATRP were
of methyl methacrylate
synthesized by
and n-butyl acrylate, as depicted in Scheme 2.
the ATRP of methyl methacrylate and n-butyl acrylate, as depicted in Scheme 2.

Scheme 2. Synthesis of polyallene-based triblock copolymer using conventional free radical and
Scheme 2. Synthesis of polyallene-based triblock copolymer using conventional free radical and ATRP.
ATRP. Reprinted from Reference [30]. (Copyright (2017) Nature Publishing Group).
Reprinted from Reference [30]. (Copyright (2017) Nature Publishing Group).
RAFT, on the other hand, has seen rapid growth due to its superior compatibility with a broader
range of
RAFT, onfunctionalities
the other hand, and has
high seen
tolerance
rapidofgrowth
impurities.
due The creative
to its combination
superior of RAFT
compatibility with a
polymerization with other polymerization techniques, such as ATRP
broader range of functionalities and high tolerance of impurities. The creative combination of RAFT or ring-opening
polymerization,
polymerization withhas extended
other the array oftechniques,
polymerization available architectures
such as ATRP suchor as ring-opening
graft, star, hyperbranched,
polymerization,
etc. [31,32]. The general method for the preparation of BCPs using the RAFT process is through
has extended the array of available architectures such as graft, star, hyperbranched, etc. [31,32].
sequential polymerization. For the synthesis of an AB diblock copolymer, the first block was
The general method for the preparation of BCPs using the RAFT process is through sequential
synthesized via a RAFT process, followed by subsequent purification. The resulting end-reactive
polymerization.
polymer acts For the synthesis
as a macro-RAFT of an
agent forAB diblock
a second copolymer,step.
polymerization the To
first block
ensure was synthesized
complete end group via
a RAFT process, followed by subsequent purification. The resulting end-reactive
functionalization, the polymerization yield of the first block is usually kept rather low (<30%). polymer acts
In as a
macro-RAFT
contrast agent
to thisfortwo-step
a second polymerization
process, Chaduc etstep. To ensurea complete
al. reported end group
simple one-pot RAFTfunctionalization,
process for
the polymerization
amphiphilic blockyield of the firstinblock
copolymers wateris[33].
usually
Usingkept rather low (<30%). In contrast
4-cyano-4-thiothiopropylsulfanyl to this two-step
pentanoic acid
(CTPPA) as the RAFT agent, poly(acrylic acid), poly(methacrylic acid), or poly(methacrylic
process, Chaduc et al. reported a simple one-pot RAFT process for amphiphilic block copolymers acid-co-
poly(ethylene
in water [33]. Using oxide) methyl ether methacrylate) was first
4-cyano-4-thiothiopropylsulfanyl formedacid
pentanoic in water.
(CTPPA)The resulting macro-
as the RAFT agent,
poly(acrylic acid), poly(methacrylic acid), or poly(methacrylic acid-co-poly(ethylene oxide) methyl
Polymers 2017, 9, 494 5 of 31

ether methacrylate) was first formed in water. The resulting macro-RAFT agents were then directly
used without further purification for the RAFT polymerization of styrene in water in the same reactor.
This strategy leads to a very good control of the resulting amphiphilic block copolymers. Very recently,
short poly(ethylene glycol) (PEG) was employed as the solvent in the macromolecular RAFT
Polymers 2017, 9, 494 5 of 31
agent-mediated dispersion polymerization of BCPs such as PEG-b-PS, P4VP-b-PS, and PNIPAM-b-PS.
A new formulation
RAFT agents were of polymerization-induced
then directly used withoutself-assembly
further purificationof PEG named
for the RAFTPEG-PISA
polymerizationto synthesize
of
diblock styrene
copolymer nanoassemblies was reported. In PEG-PISA, the viscous
in water in the same reactor. This strategy leads to a very good control of the resulting PEG affords advantages
including fast polymerization
amphiphilic block copolymers. rate, good
Very control
recently, shortover the synthesis
poly(ethylene glycol) of diblock
(PEG) copolymers,
was employed as the and in
solvent in the macromolecular RAFT agent-mediated dispersion
situ synthesis of both amphiphilic and doubly hydrophobic diblock copolymer nanoassemblies polymerization of BCPs such as at a
PEG-b-PS, P4VP-b-PS, and PNIPAM-b-PS. A new formulation of polymerization-induced self-
polymer concentration of up to 50%. Furthermore, two new self-assembled morphologies of ellipsoidal
assembly of PEG named PEG-PISA to synthesize diblock copolymer nanoassemblies was reported.
vesiclesInand nanotubes were formed via PEG-PISA. Nevertheless, RAFT dispersion polymerization
PEG-PISA, the viscous PEG affords advantages including fast polymerization rate, good control
often suffers
over thefrom ratherofpoor
synthesis colloidal
diblock stability,
copolymers, andleading to low polymerization
in situ synthesis of both amphiphilic rate,and
broad
doublymolecular
weight hydrophobic
distribution,diblock and lack copolymer nanoassemblies at a polymer concentration of up to 50%. agent.
of control over molecular weight when using a small RAFT
Furthermore,
The reason for this istwo new self-assembled
believed morphologies
to be the superswelling of ellipsoidal
effect in the early vesicles and nanotubes
nucleation stage [34].were Zhu et al.
employed formed via PEG-PISA.oligomer,
an amphiphilic Nevertheless, RAFT dispersion
poly(acrylic polymerization
acid-b-styrene) often suffers fromas
trithiocarbonate, rather
bothpoorsurfactant
colloidal stability, leading to low polymerization rate, broad molecular weight distribution, and lack
and RAFT agent to polymerize styrene. This macro-RAFT agent was capable of enhancing the colloidal
of control over molecular weight when using a small RAFT agent. The reason for this is believed to
stabilitybe
and,
the as a result, theeffect
superswelling polymerization was successful
in the early nucleation [34,35].
stage [34]. Zhu Well-controlled
et al. employed anPS with a molecular
amphiphilic
weight oligomer,
up to 120poly(acrylic
kg/mol and PS-b-PBA were readily synthesized using this
acid-b-styrene) trithiocarbonate, as both surfactant and RAFT agent method. Furthermore,
to
the same group demonstrated
polymerize that this method
styrene. This macro-RAFT agent wascould be used
capable as a promising
of enhancing approach
the colloidal to synthesize
stability and, as
a result,elastomer
thermoplastic the polymerization
materialswas[36].
successful [34,35]. Well-controlled PS with a molecular weight up to
120 kg/mol and PS-b-PBA were
NMP is commonly used for the synthesis readily synthesizedof using this method.
block copolymers Furthermore, the same
consisting of group
PS, PMMA,
demonstrated that this method could be used as a promising approach to synthesize thermoplastic
poly(vinyl acetate) (PVAc) and poly(dimethyl acrylamide) (PDMA). In a typical process, styrene is
elastomer materials [36].
polymerizedNMP firstly
is using
commonly a bi-molecular
used for the initiator benzoyl
synthesis of blockperoxide and 2,2,6,6-tetramethylpiperidinoxy
copolymers consisting of PS, PMMA,
(TEMPO). The PSacetate)
poly(vinyl segment bearing
(PVAc) the TEMPO end
and poly(dimethyl group is
acrylamide) subsequently
(PDMA). In a typicalused as thestyrene
process, macroinitiator
is
for the polymerized
second block. firstlyWhile
usingthe amolecular
bi-molecularweight distributions
initiator benzoyl are usuallyand
peroxide broad, this may
2,2,6,6-
not limittetramethylpiperidinoxy
their practical applications.(TEMPO). The ThePS segment
monomer bearing the TEMPO
conversion is end
alsogroup
lowiswhen
subsequently
polymerized
used as the macroinitiator for the second block. While the molecular weight distributions are usually
at high temperature. The deviation from the target molecular weight became more significant,
broad, this may not limit their practical applications. The monomer conversion is also low when
especially when it became higher than 100,000 g/mol. Hawker et al. reported a modified NMP
polymerized at high temperature. The deviation from the target molecular weight became more
system significant,
for the controlled
especially when polymerization
it became higherofthan dienes
100,000 ing/mol.
the presence
Hawker et al. ofreported
alkoxyamine
a modified initiators
based on NMP a system
2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxy
for the controlled polymerization of dienes inskeleton the presence (Scheme 3). A initiators
of alkoxyamine detailed study
revealed based
thaton thisa 2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxy
modified system was able to controlskeleton (Scheme 3). A detailed
the homopolymerization of study
isoprene to
revealed that this modified system was able to control the homopolymerization
high conversion and molecular weights from 1000 to 100 000 g/mol with polydispersities of isoprene to high of
conversion and molecular weights from 1000 to 100 000 g/mol with polydispersities of 1.06–1.15.
1.06–1.15. Polyisoprene-containing BCPs, PI-b-PtBuA and PS-b-PI, were also prepared with similar
Polyisoprene-containing BCPs, PI-b-PtBuA and PS-b-PI, were also prepared with similar control. In
control.comparison
In comparison with with conventional
conventional TEMPO TEMPO
systems, systems,
these newthesesystems
new systemsexhibit exhibit a significant
a significant
improvement in theinability
improvement to control
the ability to controlthethepolymerization
polymerization and and further
further demonstrate
demonstrate the versatility
the versatility of of
nitroxide-mediated
nitroxide-mediated livingliving
freefree
radical procedures
radical procedures [37].
[37].

SchemeScheme 3. Syntheticscheme
3. Synthetic scheme ofofPI-b-PtBuA and PS-b-PI
PI-b-PtBuA block copolymers
and PS-b-PI using a modified
block copolymers nitroxide-
using a modified
mediated polymerization (NMP) initiator.
nitroxide-mediated polymerization (NMP) initiator.
Polymers 2017, 9, 494 6 of 31
Polymers 2017, 9, 494 6 of 31

2.1.2. Living
2.1.2. Anionic
Living AnionicPolymerization
Polymerization
The
The pioneering
pioneering work
work onon BCP
BCP synthesisusing
synthesis usingliving
livinganionic
anionicpolymerization
polymerization(LAP)
(LAP)was wasreported
reported by
by Szwarc
Szwarc et 1956
et al. in al. in[38,39].
1956 [38,39]. Thisoftype
This type of polymerization
polymerization proceeds
proceeds to quantitative
to quantitative conversion
conversion without
without chain transfer and/or chain termination. Although there might be
chain transfer and/or chain termination. Although there might be an argument that the demanding an argument that the
demanding experimental conditions is one of its limitations, LAP has proved itself
experimental conditions is one of its limitations, LAP has proved itself to be the best polymerization to be the best
polymerization
technique for thetechnique
preparation for the
of preparation
well-defined of BCPs
well-defined
based BCPs based
on vinyl on vinyl monomers
monomers such
such as styrene,
as styrene,
dienes, dienes, (meth)acrylates,
(meth)acrylates, vinylacrylonitriles,
vinyl pyridines, pyridines, acrylonitriles, as wellmonomers
as well as cyclic as cyclic monomers such
such as lactones,
as lactones, oxiranes, and siloxanes over the last 60 years [2,40,41]. Anionic polymerization is widely
oxiranes, and siloxanes over the last 60 years [2,40,41]. Anionic polymerization is widely exploited
exploited in industry to create BCPs on a massive scale. Because of its superior control over the
in industry to create BCPs on a massive scale. Because of its superior control over the molecular
molecular weight, architecture, composition, and functionality as compared to controlled radical
weight, architecture, composition, and functionality as compared to controlled radical polymerization,
polymerization, almost all well-defined BCPs with complex architectures such as star, comb, graft,
almost all well-defined BCPs with complex architectures such as star, comb, graft, dendritic, etc. are
dendritic, etc. are achievable via the combination of anionic polymerization and linking chemistry
achievable
[6,42–47].via the combination
There of anionicreviews
are several insightful polymerization
available andthat linking
describechemistry
the recent[6,42–47].
progressTherein theare
several insightful reviews available that
synthesis of well-defined BCPs via LAP [48,49]. describe the recent progress in the synthesis of well-defined
BCPs viaOneLAPkey[48,49].
condition that must be satisfied is that the nucleophilicity of the macroanion must be
One key high
sufficiently condition thatthe
to initiate must be satisfied
second monomer. is that
Thus, the
thenucleophilicity
monomers must ofbe
the macroanion
added must
in the order of be
sufficiently
increasing electron affinity: styrene < butadiene ~ isoprene < vinyl pyridine < methyl acrylate < of
high to initiate the second monomer. Thus, the monomers must be added in the order
increasing
ethyleneelectron
oxide. affinity:
One classicstyrene < butadiene
example of the~isoprene
synthesis <ofvinyl pyridinecopolymers
multiblock < methyl acrylate < ethylene
by sequential
oxide. One classicwas
polymerization example of the
reported by synthesis of multiblock
Hadjichristidis et al., as copolymers
shown in Schemeby sequential
4A [50]. polymerization
The resulting
was reported
BCPs by Hadjichristidis
exhibited a very low PDIetofal., asand
1.04 shown in Scheme 4Aobserved
the compositions [50]. Thefrom
resulting
1H-NMRBCPswereexhibited a very
consistent
with the feeding ratios. 1
low PDI of 1.04 and the compositions observed from H-NMR were consistent with the feeding ratios.

Scheme
Scheme 4. (A)
4. (A) Synthesis
Synthesis of PS-b-PI-b-P2VP-b-PtBA-b-PEO
of PS-b-PI-b-P2VP-b-PtBA-b-PEO pentablock
pentablock copolymers
copolymers via sequential
via sequential living
living anionic polymerization (LAP). (B) Synthesis of PDMS-b-PtBA diblock copolymers.
anionic polymerization (LAP). (B) Synthesis of PDMS-b-PtBA diblock copolymers.

Nevertheless, sequential LAP is restricted especially when the monomers exhibit different
Nevertheless, sequential LAP is restricted especially when the monomers exhibit different
reactivities. For example, the living polymer of polydimethylsiloxane is not sufficiently nucleophilic
reactivities. For example, the living polymer of polydimethylsiloxane is not sufficiently nucleophilic to
to initiate the polymerization of t-butyl methacrylate. In order to prepare PDMS-b-PtBA, a linking
initiate thebearing
reagent polymerization of t-butylmoiety
with chlorosilane methacrylate.
was usedIndueorder to prepare
to its PDMS-b-PtBA,
high reactivity (Scheme a linking
4B) reagent
[51]. Hirao
bearing with chlorosilane moiety was used due to its high reactivity (Scheme
et al. prepared a wide variety of block copolymers with extremely low PDI using new linking 4B) [51]. Hirao et al.
prepared a wide Another
methodology. variety ofadvantage
block copolymers with extremely
of this linking chemistry low PDIitusing
is that opensnew linking
endless methodology.
possibilities of
Another advantage of this linking chemistry is that it opens endless possibilities of
various molecular architectures [5,42,52,53], as demonstrated by the work of Mays, Hadjichristidis,various molecular
architectures
Hirao, Quirk, [5,42,52,53],
and many as demonstrated
others by the work
through chlorosilane andof1,1-diphenylethylene
Mays, Hadjichristidis, Hirao, Quirk,
(DPE)-based linkingand
many others (Figure
chemistry through3).chlorosilane
Well-defined and 1,1-diphenylethylene
BCPs with structural and (DPE)-based
compositional linking chemistryprepared
homogeneity (Figure 3).
Well-defined
using LAP BCPs with structural
have served as templatesand for
compositional homogeneity
structure-property prepared
relationship using
studies andLAP
havehave
alsoserved
found as
many important
templates industrial applications
for structure-property such studies
relationship as adhesives and sealants,
and have in automotive,
also found wire, industrial
many important paving,
and footwear
applications applications,
such as adhesives etc.and
[54].sealants, in automotive, wire, paving, and footwear applications,
etc. [54].
Polymers 2017, 9, 494 7 of 31

Polymers 2017, 9, 494 7 of 31

Polymers 2017, 9, 494 7 of 31

Star block copolymer Miktoarm Star Star-b-linear-b-star "Comb"

Star block copolymer Miktoarm Star Star-b-linear-b-star "Comb"

"Centipede" "Barbwire" Comb Star

Figure 3. Illustration of complex architectures using living anionic polymerization and coupling
"Centipede" "Barbwire" Comb Star
chemistry. Adapted from Reference [55]. (Copyright (2017) WILEY-VCH Verlag GmbH & Co. KGaA,
Weinheim).
Figure 3. Illustration
Figure of complex
3. Illustration architectures
of complex usingusing
architectures livingliving
anionic polymerization
anionic and coupling
polymerization chemistry.
and coupling
chemistry.
Adapted Adapted from
from Reference [55].Reference [55].(2017)
(Copyright (Copyright (2017) WILEY-VCH
WILEY-VCH Verlag
Verlag GmbH &GmbH & Co. Weinheim).
Co. KGaA, KGaA,
2.2. Combination of Different Polymerization Techniques
Weinheim).

2.2. Combination
In some cases, of Different
sequentialPolymerization Techniques
addition polymerization techniques are limited when the monomers
2.2. Combination of Different Polymerization Techniques
are not suitable to be polymerized using the same polymerization mechanism. A second approach to
In some cases,
In some sequential
cases, addition polymerization techniques are limited whenthethemonomers
monomers are
BCPs is the coupling ofsequential addition
two different polymerization
polymerization techniquesor
techniques are limited
block when
copolymer segments either
not suitable
are not suitable to be polymerized using the same polymerization mechanism. A second approachto
to be polymerized using the same polymerization mechanism. A second approach toBCPs
using a “click” reaction such as Diels–Alder cycloaddition reaction, a thiol-ene reaction, or a copper-
is theBCPs
coupling
is theof two different
coupling polymerization
of two different techniques
polymerization or block
techniques copolymer
or block segments
copolymer segmentseither using a
either
catalyzed azide–alkyne cycloaddition reaction (CuAAC). With appropriate care, this approach can
“click” reaction
using a “click”such as Diels–Alder
reaction cycloaddition
such as Diels–Alder reaction,reaction,
cycloaddition a thiol-ene reaction,
a thiol-ene or a copper-catalyzed
reaction, or a copper-
yieldcatalyzed
BCPs withoutazide–alkyne substantial homopolymers
cycloaddition reaction With and comparable
(CuAAC). With appropriate PDIs as this compared with the
azide–alkyne cycloaddition reaction (CuAAC). appropriate care, thiscare,
approach approach
can yieldcanBCPs
sequential
yield addition
BCPs without approach. Yagci
substantial and et al. reported
homopolymers a one-pot synthetic approach to BCPs using the
without substantial homopolymers comparableand PDIs comparable
as compared PDIswith as compared with addition
the sequential the
combination
sequential ofaddition
ATRP approach.
and ring Yagci
openinget polymerization
al. reported a one-pot(ROP) methods
synthetic simultaneously
approach to BCPs using [56].
the Two
approach. Yagci et al. reported a one-pot synthetic approach to BCPs using the combination of ATRP
structurally
combination different
of ATRPmonomers
and ringwere selected
opening and the polymerization
polymerization (ROP) methods was initiated simultaneously
simultaneously [56]. Two
and ring opening polymerization (ROP) methods simultaneously [56]. Two structurally different
usingstructurally
a difunctional different monomers
initiator, as were
shown selected and the polymerization
in Scheme 5. They foundwas initiated
that simultaneously
the two polymerization
monomers were selected and the polymerization was initiated simultaneously using a difunctional
using a difunctional initiator, as shown in Scheme 5.
mechanisms proceeded without affecting each other. The obtained products showed They found that the two polymerization
characteristic
initiator, as shown
mechanisms in Scheme
proceeded 5. They found eachthat theThetwoobtained
polymerization mechanisms proceeded
thermal transitions of bothwithout
PMMAaffecting other.
and polycaprolactone products
(PCL) blocks, showed
indicating characteristic
that BCPs were
without affecting
thermal each other.
transitions of bothThePMMAobtained products showed
and polycaprolactone characteristic
(PCL) thermalthat
blocks, indicating transitions
BCPs were of both
synthesized.
PMMA and polycaprolactone (PCL) blocks, indicating that BCPs were synthesized.
synthesized.

Scheme 5. One
One potpolymerization
pot polymerization of PMMA-b-PCL using combination of metal-free ATRP and ring and
Scheme
Scheme 5.
5. One pot polymerization ofof PMMA-b-PCL
PMMA-b-PCL using
using combination
combination of metal-free
of metal-free ATRPATRP
and ring
ring opening polymerization
opening polymerization (ROP)
(ROP)simultaneously under
simultaneously undersunlight. Reprinted
sunlight. fromfrom
Reprinted Reference [56]. [56].
Reference
opening polymerization (ROP) simultaneously under sunlight. Reprinted from Reference [56].
(Copyright (2017) Royal Society of Chemisty).
(Copyright
(Copyright (2017)
(2017) Royal
Royal Society
Societyof
ofChemisty).
Chemisty).
The synthesis of complex polymeric materials through post-polymerization coupling reactions
Thealso
The
has synthesis
synthesis
attractedof complex
of complex polymeric
significantpolymeric materials
materials
research interest. through
Vanthrough post-polymerization
post-polymerization
Hest et al. synthesized PMMA-b-PEG coupling
coupling reactions
reactions
diblock
has also
has also attracted
attracted
copolymers significant
viasignificant research
research
the combination interest.
interest.
of ATRP Van
and Van Hest et
Hest et al.
alkyne-azide al. synthesized
clicksynthesized PMMA-b-PEG
reaction, as PMMA-b-PEG
shown diblock
in Figurediblock
4.
copolymers
Terminal
copolymers via the
alkyne combination
and azide of ATRP
moieties were and alkyne-azide
conveniently click
introduced reaction,
via as
protected shown in Figure
functionalized 4.
initiators
Terminal alkyne
Terminal [57].
alkyne andand azide
azide moieties
moieties were
were conveniently
conveniently introduced
introduced via via protected
protected functionalized
functionalized
initiators Hawker
[57].
initiators [57]. et al. synthesized a series of cyclic PS-b-PEO BCPs using the ATRP and CuAAC of α,ω-
azide-functionalized
Hawker et al. PS and α,ω-alkyne PEOPS-b-PEO
homopolymers (Figurethe5)the
[11]. and
The CuAAC
α,ω-azide-
Hawker al. synthesized
synthesizeda aseries of of
series cyclic
cyclic PS-b-PEOBCPsBCPsusing
using ATRP ATRP and CuAACof α,ω-
of
functionalized PS was polymerized using a difunctional ATRP initiator, ethylene bis-(2-
azide-functionalized PS PS
α,ω-azide-functionalized andand α,ω-alkyne
α,ω-alkyne PEOPEOhomopolymers
homopolymers(Figure (Figure 5) 5) [11]. The
The α,ω-azide-
functionalizedPSPS
functionalized waswas polymerized
polymerized using a using a difunctional
difunctional ATRP initiator,ATRP initiator,
ethylene ethylene bis-(2-
bis-(2-bromoisobutyrate).
The α,ω-Br-terminated PS was then conveniently converted to the azide moiety. The α,ω-alkyne PEO
homopolymer was obtained by treating α,ω-hydroxyl PEO with propargyl bromide. The desired
Polymers
Polymers2017,
2017,9,9,494
494 88of
of31
31

Polymers 2017, 9, 494 8 of 31

bromoisobutyrate).
bromoisobutyrate).The Theα,ω-Br-terminated
α,ω-Br-terminatedPS PSwas
wasthen
thenconveniently
convenientlyconverted
convertedtotothe
theazide
azidemoiety.
moiety.
The
The α,ω-alkyne
α,ω-alkyne PEO PEO homopolymer
homopolymer was was obtained
obtained byby treating
treating α,ω-hydroxyl
α,ω-hydroxyl PEO PEO with
with propargyl
propargyl
bromide.
products The
bromide. The desired
were isolatedproducts
desired products were
were isolated
isolated
using preparative using
using preparative
preparative
gel permeation gel
gel permeation
permeation
chromatography. Tezukachromatography.
chromatography.
et al. reviewed
Tezuka
Tezuka et
etal.
interesting al.reviewed
aboutinteresting
reviewed
work topologicalwork
interesting work about
about
studies topological
[58]. studies
topological
of BCPs studiesof
ofBCPs
BCPs[58].
[58].

Figure4.4.4.(a)
Figure
Figure (a) Preparation
(a)Preparation
Preparation of of PMMA-b-PEG
ofPMMA-b-PEG
PMMA-b-PEG block block copolymer
blockcopolymer
copolymer via
viaATRPviaand
ATRP ATRP
and and azide-alkyne
azide-alkyne
azide-alkyne click click
clickreaction.
reaction.
reaction.
(b) Size (b)
exclusion Size exclusion chromatography
chromatography (SEC) curves(SEC)
of curves
PMMA, of PMMA,
polyethylene polyethylene
glycol (PEG),
(b) Size exclusion chromatography (SEC) curves of PMMA, polyethylene glycol (PEG), and PMMA- glycol
and (PEG),
PMMA-
and PMMA-b-PEG
b-PEG
b-PEG diblock diblock copolymer.
diblock copolymer.
copolymer. ReprintedReprinted
Reprinted from from Reference
from Reference
Reference [57]. [57]. (Copyright
[57]. (Copyright
(Copyright (2005)(2005)
(2005) Royal
RoyalRoyal Society
Society
Society of
of
of Chemistry).
Chemistry).
Chemistry).

Figure 5. Synthesis of cyclic PS-b-PEO copolymer. Reprinted from Reference [11]. (Copyright (2012)
American
Figure ChemicalofSociety).
Figure5.5.Synthesis
Synthesis ofcyclic
cyclicPS-b-PEO
PS-b-PEOcopolymer.
copolymer.Reprinted
Reprintedfrom
fromReference
Reference[11].
[11].(Copyright
(Copyright(2012)
(2012)
American Chemical Society).
American Chemical Society).
RAFT polymers can be conveniently converted to thiols by treating the chain end with aliphatic
RAFT
RAFT
amines. A polymers
polymers
block can
canbe
beconveniently
copolymer thereforeconverted
conveniently
can converted
be to
obtained thiols
thiolsby
tothrough treating
byrelated
treating the chain
chainend
thechemistry
thiol with
withaliphatic
end(Figure
aliphatic
6).
amines. A block copolymer can therefore be obtained through related thiol chemistry (Figure
amines. A block copolymer can therefore be obtained through related thiol chemistry (Figure 6). 6).
Polymers 2017, 9, 494 9 of 31
Polymers
Polymers 2017,9,9,494
2017, 494 9 of 3131
9 of

Figure 6. Synthetic strategies to block copolymers (BCPs) using thiol-based coupling reactions.
Figure 6. Synthetic strategies to block copolymers (BCPs) using thiol-based coupling reactions.
Figure 6. Synthetic
Reprinted strategies
from Reference [59]. to block copolymers
(Copyright (BCPs)
(2014) Royal Societyusing thiol-based coupling reactions.
of Chemistry).
Reprinted from Reference [59]. (Copyright (2014) Royal Society of Chemistry).
Reprinted from Reference [59]. (Copyright (2014) Royal Society of Chemistry).
Barner-Kowollik and Stenzel et al. first synthesized a series of star polymers by a combination
Barner-Kowollik
ofBarner-Kowollik
RAFT andStenzel
chemistryand
and Stenzel et al.
et al. first
first synthesized
hetero Diels-Alder synthesized aaseries
reaction [60], seriesofofstar
in which thepolymers
star reaction by
polymers a combination
by a combination
occurs between
of RAFT chemistry and hetero Diels-Alder reaction [60], in which the reaction occursbetween
of RAFT chemistry
thiocarbonyl group and ahetero
diene Diels-Alder
in a [4 + 2] reaction [60],
cycloaddition in
process which
(Scheme the reaction
6). occurs between
thiocarbonyl
thiocarbonyl groupand
group anda adiene
dieneininaa[4[4++ 2]
2] cycloaddition
cycloaddition process
process(Scheme
(Scheme6). 6).

Scheme 6. Formation of block copolymers via a reversible addition-fragmentation chain transfer

(RAFT) polymerization and a hetero Diels-Alder reaction. Adapted from Reference [60]. (Copyright
Scheme
Scheme 6.Formation
Formation
(2008)6.American ofofblock
Chemicalblock copolymers via a reversible
copolymers
Society). reversible addition-fragmentation
addition-fragmentation chain
chaintransfer
transfer
(RAFT)
(RAFT) polymerizationand
polymerization andaahetero
heteroDiels-Alder
Diels-Alder reaction.
reaction. Adapted
Adaptedfrom
fromReference
Reference[60]. (Copyright
[60]. (Copyright
(2008)
(2008) American
American ChemicalSociety).
Chemical Society).
Polymers 2017, 9, 494 10 of 31

The incorporation
Polymers 2017, 9, 494 of supramolecular chemistry also provides a very interesting pathway 10 ofto
31form
BCPs. Schubert et al. demonstrated that terpyridine-terminated PS and PEO can form BCPs with
RuCl3 [61]. TheThe
incorporation of supramolecular
coordination chemistry
junction point also provides
was formed in twoa very
steps: interesting pathway to form
the terpyridine-terminated
BCPs. Schubert et al. demonstrated that terpyridine-terminated PS and PEO can form BCPs with
PEO was selectively complexed with RuCl3 yielding monocomplex of Ru(III); terpyridine-terminated
RuCl3 [61]. The coordination junction point was formed in two steps: the terpyridine-terminated PEO
PS was then reacted with the monocomplex under the reduction of Ru(III) to Ru(II), resulting in
was selectively complexed with RuCl3 yielding monocomplex of Ru(III); terpyridine-terminated PS
PS-b-PEO.
was thenOnereacted
advantagewith of
thethis approach isunder
monocomplex that the non-covalent
the reduction junction
of Ru(III) point resulting
to Ru(II), can be broken
in PS-b- under
external stimuli.
PEO. One advantage of this approach is that the non-covalent junction point can be broken under
external stimuli.
3. Self-Assembly of BCPs
3. Self-Assembly of BCPs
3.1. Self-Assembly in Bulk
3.1. Self-Assembly in Bulk
Self-assembly of BCPs with immiscible blocks has been extensively studied via experiments and
simulations Self-assembly of BCPs
since the 1960s [62].with immiscible
Several reviewsblocks has been extensively
are available studied
on this topic via experiments
[22,63,64]. and
The self-assembly
processsimulations since
is driven by an the 1960s [62].mixing
unfavorable Several reviewscoupled
enthalpy are available
with aonsmall
this mixing
topic [22,63,64].
entropy. The self-
Composition
assembly
(f ), the number process is driven by
of repeating an unfavorable
units (N), and the mixing enthalpy coupled
Flory-Huggins with a small
interaction mixing entropy.
parameter (χ) are the
Composition (f), the number of repeating units (N), and the Flory-Huggins interaction parameter (χ)
important parameters that determine the morphologies, which include spheres (S), cylinders (C),
are the important parameters that determine the morphologies, which include spheres (S), cylinders
gyroids (G), and lamellae (L) [65,66]. The self-assembly behavior may also be influenced by other
(C), gyroids (G), and lamellae (L) [65,66]. The self-assembly behavior may also be influenced by other
external parameters
external such
parameters as as
such mechanical
mechanicalor orelectric fields[67,68].
electric fields [67,68].However,
However, it isitbeyond
is beyond the scope
the scope of of
this review to cover all these aspects. Therefore, we only address the basic concepts
this review to cover all these aspects. Therefore, we only address the basic concepts of microphase of microphase
separation and present
separation several
and present recent
several examples
recent of the
examples of morphological
the morphological behavior
behavior of of
BCPs. Figure
BCPs. 7 shows
Figure 7
that the different
shows morphologies
that the of a typicaloflinear
different morphologies diblock
a typical BCP
linear evolve
diblock BCPfrom spherical
evolve to lamellar
from spherical to and
lamellar disorder
can undergo and can undergo
to order disorder to order
transitions, as transitions,
a function as of af function
and χN.of f and χN.

Figure 7. 7.(a)
Figure Equilibrium
(a) Equilibrium morphologies
morphologies of AB of AB copolymers
diblock diblock copolymers
in bulk: S andinS’ bulk: S and S’ =
= body-centered-
cubic spheres, C and
body-centered-cubic C’ = hexagonally
spheres, C and C’ = packed cylinders,packed
hexagonally G and G’ = bicontinuous
cylinders, G andgyroids, and L =
G’ = bicontinuous
lamellae.
gyroids, and L(b) Theoretical
= lamellae. (b)phase diagram
Theoretical of ABdiagram
phase diblocksofpredicted by the
AB diblocks self-consistent
predicted by themean-field
self-consistent
theory,theory,
mean-field depending on volume
depending on fraction
volume(f)fraction
of the blocks
(f ) of and the segregation
the blocks and the parameter,
segregation χN; CPS and χN;
parameter,
CPS’ = closely packed spheres. (c) Experimental phase diagram of polystyrene-b-polyisoprene
CPS and CPS’ = closely packed spheres. (c) Experimental phase diagram of polystyrene-b-polyisoprene
copolymers, in which fA represents the volume fraction of polyisoprene, PL = perforated lamellae.
copolymers, in which f A represents the volume fraction of polyisoprene, PL = perforated lamellae.
Reproduced from Reference [69]. (Copyright (2012) Royal Society of Chemistry).
Reproduced from Reference [69]. (Copyright (2012) Royal Society of Chemistry).
Furthermore, the self-assembly of triblock copolymers of poly(styrene-b-isoprene-b-styrene) (PS-
b-PI-b-PS) has also
Furthermore, the been extensivelyofinvestigated
self-assembly using small-angle
triblock copolymers X-ray scattering (SAXS) and
of poly(styrene-b-isoprene-b-styrene)
(PS-b-PI-b-PS) has also been extensively investigated using small-angle X-ray scattering (SAXS)
 Polymers2017,
Polymers 2017,9,9,494
494 11ofof31
11 31

transmission electron microscopy (TEM) by Storey et al. and Elabd et al. [70,71]. Unlike the
and transmission
conventional studyelectron microscopy
on neutral BCPs, Mays (TEM)
et al.by Storey et
compared al.morphologies
the and Elabd etofal. [70,71]. Unlike
well-defined the
neutral
conventional study on neutral BCPs, Mays et al. compared the morphologies of well-defined
PS-b-PI and its charged counterpart, sulfonated PS-b-fluorinated PI (sPS-b-fPI). Interestingly, Inversedneutral
PS-b-PI and itswere
morphologies charged counterpart,
observed sulfonated
when the diblock PS-b-fluorinated
BCP, 25sPS-b-75fPI PI (sPS-b-f
(50% ofPI).
PS Interestingly, Inversed
block was sulfonated
morphologies were observed when the diblock BCP, 25sPS-b-75f PI (50% of PS block was sulfonated
to sulfonic form), was casted from tetrahydrofuran compared with its neutral counterpart, as shown to
sulfonic form),
in Figure 8 [72]. was casted from tetrahydrofuran compared with its neutral counterpart, as shown in
Figure 8 [72].

TEMand
Figure8.8.TEM
Figure andsmall-angle
small-angleX-ray
X-rayscattering
scattering(SAXS)
(SAXS)images
imagesof sPS-b-f PI.(A)
ofsPS-b-fPI. (A)ordered
orderedhexagonal
hexagonal
structureswithout
withoutannealing;
annealing;(B)
(B)less
lessordered
orderedstructures
structuresof
ofsample
sampleannealed
annealedatat120 ◦
120°C;C;(C)
(C)SAXS
SAXSofof
structures
the corresponding samples in (A,B). Reprinted from Reference [72]. (Copyright (2010) Royal
the corresponding samples in (A,B). Reprinted from Reference [72]. (Copyright (2010) Royal Society Society
ofofChemistry).
Chemistry).

Segalman
Segalman et al. al. prepared
prepareda seriesa series of ionic
of ionic conducting
conducting BCPsBCPs to investigate
to investigate the relationship
the relationship between
between ionic conductivity
ionic conductivity and domain andspacing
domain[73]. spacing [73]. A well-defined
A well-defined BCP PS-b-PI,
BCP precursor, precursor, wasPS-b-PI,
synthesizedwas
synthesized
followed byfollowed
a thiol-ene by areaction
thiol-ene toreaction
attach theto attach the ionic to
ionic moieties moieties to PI segments.
PI segments. The domain The domain
spacing
spacing was controlled
was controlled by keeping by keeping
the volume the fraction
volume of fraction of ionic constant
ionic moieties moieties and
constant
varying andthe varying
BCP chain the
BCP chain
length. length.
It was It wasthat
revealed revealed
the ionic that the ionic conductivity
conductivity was independent
was independent of domain
of domain spacing. Thespacing.
insights
The insights
gained by this gained by thisfacilitate
work could work could facilitate theofdevelopment
the development design rules forof the
design
nextrules for theof next
generation high
generation
performance ion-conducting membranes. Balsara et al. studied the effect of salt on the morphologyon
of high performance ion-conducting membranes. Balsara et al. studied the effect of salt of
the morphology
electron conducting of electron
poly(3-(2 0 -ethylhexyl)thiophene)-b-ethylene
conducting poly(3-(2′-ethylhexyl)thiophene)-b-ethylene
oxide) (P3EHT-b-PEO) oxide)
[74]. (P3EHT-
PEO was
b-PEO)
selected [74].
duePEO was
to its selected
good due to its capability.
salt solvation good salt solvation capability.
Their results showed Their results
that, in theshowed that, the
melt state, in
the melt state,
salt-free sample theexhibits
salt-freea sample exhibits a gyroid
gyroid morphology whilemorphology while the
the salt containing salt containing
sample (r = 0.125)sample
exhibits(ra
=lamellar
0.125) exhibits
morphology. a lamellar morphology.
Furthermore, quenchingFurthermore,
the salt-freequenching
sample totheroom salt-free sampleresults
temperature to room in a
temperature results in adue
lamellar morphology lamellar
to the morphology
breakout of the dueP3EHT
to the breakout of the
crystals. In P3EHT
contrast, crystals.
there In change
is little contrast, in
there is little change
the morphology of the insalt-containing
the morphology of the
sample salt-containing
upon quenching to sample upon quenching
room temperature. This to room
could be
temperature.
attributed to This could beinattributed
the increase χN. to the increase in χN.
Owing
Owingto toitsitsstructural
structuralversatility
versatilityand andprecise
precisetunability
tunabilityofofmorphology,
morphology,dimensionality,
dimensionality, and and
feature
featuresize,
size,BCP BCPisisanan ideal
ideal platform
platform forfor
studying
studying periodically ordered
periodically functional
ordered functionalmaterials
materialson the on
mesoscale.
the mesoscale.Wiesner et al. et
Wiesner demonstrated
al. demonstrated the utilization of triblock
the utilization copolymer
of triblock (PI-b-PS-b-PEO)
copolymer (PI-b-PS-b-PEO) self-
assembly to direct
self-assembly the synthesis
to direct the synthesis of aof
mesoporous
a mesoporous niobium
niobium nitride (NbN)
nitride (NbN) superconductor
superconductor(Figure (Figure9). 9).
The formation ofofa three-dimensionally
The formation a three-dimensionally continuous
continuous gyroidal
gyroidal mesoporous
mesoporous NbN superconductor
NbN superconductor exhibits
exhibits
a criticala temperature
critical temperature (Tc) of 7about
(Tc ) of about to 8 K,7 to 8 K, aexclusion
a flux flux exclusion of about
of about 5% compared
5% compared to a dense
to a dense NbN
NbN
solidsolid
[75]. [75].
MoreMore examples
examples will be will be given
given in Section
in Section 4. 4.
The
Themyriad
myriadmorphologies
morphologiesthat thatare
areformed
formedby byBCPs
BCPsare areusually
usuallyobtained
obtainedby byslow
slowcooling
coolingso sothat
that
the polymer chains have enough time to reach thermodynamically preferred
the polymer chains have enough time to reach thermodynamically preferred alignments. Rather than alignments. Rather than
using
using slow
slow cooling, Kim et et al.
al.rapidly
rapidlyquenched
quenchedpoly(isoprene-b-lactide)
poly(isoprene-b-lactide) diblock
diblock copolymers
copolymers from from
the
the disordered
disordered statestate and revealed
and revealed an extraordinary
an extraordinary thermal
thermal history history dependence
dependence [76]. Whereas [76]. Whereas
conventional
conventional
cooling results cooling
in theresults
formation in theof formation
documented of documented
morphologies, morphologies,
rapidly cooled rapidly
samples cooledthatsamples
are then
that are from
heated then lowheated from lowform
temperature temperature
the hexagonal form C14the hexagonal
and cubic C15 C14Laves
and cubic
phases C15 Laves phases
commonly found
commonly found in metal alloys. This unusual discovery reinforces fundamental analogies between
Polymers 2017, 9, 494 12 of 31

Polymers 2017, 9, 494 12 of 31

in metal alloys.
Polymers 2017, 9,This
494 unusual discovery reinforces fundamental analogies between the way metals
12 of 31
and self-assembled
the way metals soft and materials breaksoft
self-assembled symmetry
materialswhen
breaksubjected
symmetrytowhen
changes in thermodynamic
subjected to changes in state
the
variables way
thatmetals
thermodynamic and self-assembled
drive state variables
phase soft materials
that drive
transitions. break symmetry when subjected to changes in
phase transitions.
thermodynamic state variables that drive phase transitions.

Figure
Figure 9. Gyroid-formingPI-b-PS-b-PEO
9. Gyroid-forming PI-b-PS-b-PEO block
block copolymers
copolymersand andthethe
preparation
preparationprocess of NbN
process of NbN
Figure 9. Gyroid-forming
superconductors. ReprintedPI-b-PS-b-PEO block
with permission fromcopolymers and (Copyright
Reference [75]. the preparation
(2016) process of NbN
the authors).
superconductors. Reprinted with permission from Reference [75]. (Copyright (2016) the authors).
superconductors. Reprinted with permission from Reference [75]. (Copyright (2016) the authors).
3.2. Self-Assembly in Solution
3.2. Self-Assembly in Solution
3.2. Self-Assembly in Solution
The self-assembly of amphiphilic BCPs has been a popular topic in fields such as nano-cargo
The The
delivery, self-assembly
self-assembly of of amphiphilicand
amphiphilic
biomedical/pharmaceutics, BCPs
BCPs has been
has beenaapopular
nanotechnology popular topic
[77–79]. topicin in
fields
Although such
fields
the as nano-cargo
such as nano-cargo
self-assembly of
delivery,
delivery,
amphiphilic biomedical/pharmaceutics,
biomedical/pharmaceutics,
BCPs is also driven by the and
and nanotechnology
nanotechnology
minimization of free[77–79].
[77–79].
energy Although
in Although the the
the system, self-assembly of
self-assembly
self-assembly in of
amphiphilic
solution is BCPs
more is also driven
complicated by
than the
BCPminimization
self-assembly of free
in energy
bulk. The in
amphiphilic BCPs is also driven by the minimization of free energy in the system, self-assembly the system,
morphologies self-assembly
are in
primarily
solution
determined is more
by thecomplicated than BCP self-assembly
so-called packing (p = v/a0lc),inwherebulk.vThe morphologiesof theare primarily
in solution is more complicated thanparameter
BCP self-assembly in bulk. is the
Thevolume
morphologies hydrophobic
are primarily
determined
chain, a0by by
is the the so-called packing parameter (p = v/a l ), where v is the volume of the hydrophobic
the optimal area of the head group, (p
and= lv/a
c is the length of the hydrophobic tail (Figure 10)
0 c
determined so-called packing parameter 0 cl ), where v is the volume of the hydrophobic
chain,
[80]. a0 is the optimal area of the head group, and lc is the length of the hydrophobic tail (Figure 10)
chain,[80].
a0 is the optimal area of the head group, and lc is the length of the hydrophobic tail (Figure 10) [80].

Figure 10. The types of formed nanostructures of amphiphilic diblock copolymers due to the inherent
Figure 10. of
curvature Thethetypes of formed
polymer, nanostructures
as estimated ofpacking
by chainof amphiphilic diblock
parameter, p.copolymers
Reprinted due Reference
from to the inherent
Figure 10. The types of formed nanostructures amphiphilic diblock copolymers due to the[80].
inherent
curvature
(Copyrightof(2009)
the polymer,
WILEY-VCHas estimated
Verlag by chain&packing
GmbH parameter,
Co. KGaA, p. Reprinted from Reference [80].
Weinheim).
curvature of the polymer, as estimated by chain packing parameter, p. Reprinted from Reference [80].
(Copyright (2009) WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim).
(Copyright (2009) WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim).
Polymers 2017, 9, 494 13 of 31
Polymers 2017, 9, 494 13 of 31

ByBycontrolling the
controlling thefactors
factorsthat
thatare
areable
ableto
to change the
the packing
packingparameter
parametersuch
suchasas BCP
BCP composition
composition
andandconcentration,
concentration,water
watercontent,
content,common
common solvent, and additives,
solvent, and additives,aawide
widerange
rangeofofmorphologies
morphologies
have
have beenbeen reported
reported includingspherical
including sphericalmicelles,
micelles, cylindrical,
cylindrical, bi-continuous,
bi-continuous,lamella, vesicles,
lamella, tubules,
vesicles, tubules,
etc.etc.
[81][81] (Figure
(Figure 11).
11).

Figure
Figure 11.11.TEM
TEMimages
images and corresponding
correspondingschematic
schematic diagrams of various
diagrams of variousmorphologies formed
morphologies by
formed
amphiphilic PS -b-PAA copolymers( m and n denote the degrees of polymerization
by amphiphilic PSm -b-PAAn copolymers( m and n denote the degrees of polymerization of PS and
m n of PS and PAA,
respectively):
PAA, (a) spherical
respectively): micelles;
(a) spherical (b) (b)
micelles; rods; (c) (c)
rods; bicontinuous rods;
bicontinuous (d)(d)
rods; small lamellae;
small (e)(e)
lamellae; large
large
lamellae;
lamellae; (f)(f) vesicles;(g)
vesicles; (g)hexagonally
hexagonally packed
packed hollow
hollow hoops
hoops (HHHs);
(HHHs);(h) (h)large
largecompound
compound micelles
micelles
(LCMs).
(LCMs). Reprinted
Reprinted fromReference
from Reference[69].
[69].(Copyright
(Copyright (2012)
(2012) Royal
Royal Society
SocietyofofChemistry).
Chemistry).

Manners and Winnik reported a series of interesting rod-like micelles using

Manners and Winnik reported
poly(ferrocenyldimethylsilane) a series
(PFDMS). These micellesofare interesting rod-like by
able to grow epitaxially micelles using
the addition
poly(ferrocenyldimethylsilane)
of more polymer, leading to extended micelles with a very narrow size distribution (Figure 12) [82].the
(PFDMS). These micelles are able to grow epitaxially by
addition of more polymer,
Self-assembly leadingresearchers
of BCPs enables to extended micelles
to construct with a structures
nanoscale very narrow with size distribution
molecular level
(Figure 12) [82].
precision. Not only the chemical composition has significant effect on the properties of nanostructure;
Self-assembly
molecular of BCPs
architecture enables
also researchers
has profound to construct
effect, nanoscale
as revealed by thestructures with molecular
recent studies. Tezuka and level
precision.
Yamamoto Notetonly the chemical
al. explored composition
the effect hason
of topology significant
the thermaleffect on theofproperties
stability of nanostructure;
self-assembled structures
molecular architecture
of BCPs: linear poly(butylalsoacrylate-b-ethylene
has profound effect, as revealed
oxide-b-butyl by the
acrylate) recent studies. (1)
(PBA-b-PEO-b-PBA) Tezuka
and theand
cyclic counterpart (2) (Figure 13). Despite no distinctive change in the chemical
Yamamoto et al. explored the effect of topology on the thermal stability of self-assembled structures composition or
of structure
BCPs: linearof the micelles, they
poly(butyl found that the cloud
acrylate-b-ethylene point (Tcacrylate)
oxide-b-butyl ) was increased by more than 40
(PBA-b-PEO-b-PBA) (1)°Cand
thethrough the topological
cyclic counterpart (2) conversion.
(Figure 13).Moreover,
Despite no thedistinctive
Tc can be tuned
changeby the changing
in the the composition
chemical ratio of 1 and or
2 [83]. of the micelles, they found that the cloud point (Tc ) was increased by more than 40 ◦ C through
structure
the topological conversion. Moreover, the Tc can be tuned by the changing the ratio of 1 and 2 [83].
Polymers 2017, 9, 494 14 of 31
Polymers
Polymers 2017,
2017, 9,
9, 494
494 14
14 of
of 31
31

Figure 12.
Figure
Figure 12. The schematic
12. The
The schematic representation
schematic representation of
representation of the
of the micelles
the micelles from
micelles from polyferrocenylsilane
from polyferrocenylsilane (PFS)—containing
polyferrocenylsilane (PFS)—containing
(PFS)—containing
BCPs
BCPs via
via epitaxial
epitaxial growth.
growth. Reprinted
Reprinted from
from Reference
Reference[82]. (Copyright
[82]. (Copyright(2007) American
(2007)
BCPs via epitaxial growth. Reprinted from Reference [82]. (Copyright (2007) American Association
American for
Association
Association
the
for Advancement
for the
the Advancement of
Advancement of Science).
of Science).
Science).

Figure
Figure 13.
Figure 13.The
13. The schematic
schematic
The illustration
illustration
schematic of
of linear
linearofamphiphilic
illustration amphiphilic PBA-b-PEO-b-PBA
PBA-b-PEO-b-PBA
linear amphiphilic and
and cyclic
cyclic PBA-b-PEO-
PBA-b-PEO-b-PBA PBA-b-PEO-
and cyclic
b-PBA
b-PBA self-assembly
self-assembly
PBA-b-PEO-b-PBA in aqueous media.
in aqueousinmedia.
self-assembly aqueousThe
The cyclic BCP
cyclicThe
media. BCP shows
shows
cyclic an
BCPan increased
increased
shows T . Reprinted
Tc. Reprinted
c
an increased from
from
Tc . Reprinted
Reference
Reference [83].
[83]. (Copyright
from Reference (Copyright (2010) American
(2010)(2010)
[83]. (Copyright American Chemical
Chemical
American Society).
Society).
Chemical Society).

Using
Using poly(1,2-butadiene-b-ehtylene
poly(1,2-butadiene-b-ehtylene oxide)
oxide) (PB-b-PEO)
(PB-b-PEO) in
in water
water media,
media, Bates
Bates et
et al.
al. observed
observed the
the
Using poly(1,2-butadiene-b-ehtylene oxide) (PB-b-PEO) in water media, Bates et al. observed the
formation of “Y-junctions”, which further assembled to form a 3D network (Figure
formation of “Y-junctions”, which further assembled to form a 3D network (Figure 14). This 14). This
formation of “Y-junctions”, which further assembled to form a 3D network (Figure 14). This observation
observation
observation is is in
in contrast
contrast toto that
that of
of the
the low
low molecular
molecular weight
weight counterpart,
counterpart, where
where only
only spherical
spherical
is in contrast to that of the low molecular weight counterpart, where only spherical micelles, wormlike
micelles,
micelles, wormlike
wormlike micelles,
micelles, and
and vesicles
vesicles were
were obtained
obtained when
when mixed
mixed with
with water
water [84].
[84].
micelles, and vesicles were obtained when mixed with water [84].
Polymers 2017, 9, 494 15 of 31
Polymers 2017, 9, 494 15 of 31

Figure 14. Morphology diagram for PB-PEO in water (1 wt %) as a function of molecular size and
Figure 14. Morphology diagram for PB-PEO in water (1 wt %) as a function of molecular size and
composition, where NPB and WPEO are the degree of polymerization and weight fraction of the PB and
composition, where NPB and WPEO are the degree of polymerization and weight fraction of the PB and
PEO blocks, respectively. Reprinted from Reference [84]. (Copyright (2003) American Association for
PEO blocks, respectively. Reprinted from Reference [84]. (Copyright (2003) American Association for
the Advancement of Science).
the Advancement of Science).
4. Applications
4. Applications
4.1. Applications as Thermoplastic Elastomers
4.1. Applications as Thermoplastic Elastomers
One of the most important technical applications of BCPs is as thermoplastic elastomers (TPEs).
This One of BCP
type of the most important
typically containstechnical
physically applications
crosslinkedof BCPs
rigid is asdomains
glassy thermoplastic elastomerssoft
and a continuous (TPEs).
This‘type
rubbery domain. It offers the elasticity of conventional rubber and, since it is not chemically soft
of BCP typically contains physically crosslinked rigid glassy domains and a continuous
rubbery domain.
crosslinked, It offers
is suitable forthe elasticity
typical of conventional
plastic processes such rubber and, since
as injection it is notand
molding chemically crosslinked,
melt extrusion.
TPEs
is have for
suitable found applications
typical in adhesives,
plastic processes suchcoatings, foodmolding
as injection packaging,andand
meltmany other areas
extrusion. TPEs[85].
haveThefound
most commonly studied TPEs are poly(styrene-b-isoprene-b-styrene) (SIS)
applications in adhesives, coatings, food packaging, and many other areas [85]. The most commonlyand poly(styrene-b-
butadiene-b-styrene)
studied (SBS). These two types of BCPs were(SIS)
TPEs are poly(styrene-b-isoprene-b-styrene) firstly developed
and by Holden and Milkovich
poly(styrene-b-butadiene-b-styrene)
throughThese
(SBS). living two
anionic polymerization
types of BCPs were in the firstly
early 1960s [86]. Theby
developed remarkable
Holden mechanical properties
and Milkovich through
are attributed to the microphase separation of the two chemically incompatible
living anionic polymerization in the early 1960s [86]. The remarkable mechanical properties blocks, PS and PI (or are
PB). SIS with high 3,4-isoprene exhibits a broad glass transition close to room
attributed to the microphase separation of the two chemically incompatible blocks, PS and PI temperature, providing
a very
(or PB). good
SIS withvibration damping material
high 3,4-isoprene exhibitsata room
broad temperature
glass transition[54].close
Polyethylene (PE) or
to room temperature,
poly(ethylene-alt-propylene) can be obtained through the hydrogenation of the diene block; such
providing a very good vibration damping material at room temperature [54]. Polyethylene (PE)
products exhibit superior stability under light and oxygen. Hydrogenated SBS has been used in
or poly(ethylene-alt-propylene) can be obtained through the hydrogenation of the diene block; such
applications such as electrical wire and cable sheathing due to its cold temperature flexibility and
products exhibit superior stability under light and oxygen. Hydrogenated SBS has been used in
higher extendibility to incorporate flame retardants over conventional poly(vinyl chloride) (PVC)
applications such as electrical wire and cable sheathing due to its cold temperature flexibility and
[54]. Star-block copolymers of butadiene and styrene have found applications in adhesives and
higher extendibility to incorporate flame retardants over conventional poly(vinyl chloride) (PVC) [54].
sealants [87].
Star-block copolymers of butadiene and styrene have found applications in adhesives and sealants [87].
Polymers 2017, 9, 494 16 of 31
Polymers 2017, 9, 494 16 of 31

Because the precise control over composition and architecture is possible through LAP, the the
resulting BCPs can be tailored to a wide variety of applications
resulting BCPs can be tailored to a wide variety applications [88]. [88]. One research focus
focus is to improve
the
the upper
upperservice temperature
service temperature of styrenic thermoplastic
of styrenic elastomers
thermoplastic (S-TPEs),(S-TPEs),
elastomers which is mainly
which controlled
is mainly
by the Tg ofby
controlled thethe
hardTgdomain.
of the hardConsiderable research has focused
domain. Considerable research onhas
developing
focused high Tg glassy domains
on developing high Tg
such as poly(α-methyl styrene) (T ~173 ◦ C) [89], poly(α-methyl p-methyl styrene) (T ~183 ◦ C) [90],
glassy domains such as poly(α-methyl g styrene) (Tg ~ 173 °C) [89], poly(α-methyl p-methyl g styrene)
and ◦
(Tg ~poly(tert-butyl
183 °C) [90], and styrene) (PtBS, Tstyrene)
poly(tert-butyl g ~130 C) [91].TgIn
(PtBS, hydrocarbon
~ 130 °C) [91]. Insolvent at room
hydrocarbon temperature,
solvent at room
Mays et al. prepared a series of BCPs consisting of poly(benzofulvene (BF)-b-isoprene-b-benzofulvene)
temperature, Mays et al. prepared a series of BCPs consisting of poly(benzofulvene (BF)-b-isoprene-
(FIF), in which FIF
b-benzofulvene) within14which
(FIF), vol %FIF of PBF
withexhibited
14 vol %aof maximum 14.3 ± 1.3 stress
stress aofmaximum
PBF exhibited MPa and strain
of 14.3 at
± 1.3
break
MPa andof 1390 ± at
strain 66% fromoftensile
break 1390 ±tests
66%[92].
fromDynamic mechanical
tensile tests analysis
[92]. Dynamic showed that
mechanical the softening
analysis showed
temperature of PBF temperature
that the softening in FIF was 145 of ◦PBF
C, which
in FIFis much
was 145higher
°C, than
which thatisofmuch
thermoplastic
higher thanelastomers
that of
with PS hard blocks
thermoplastic (Figure
elastomers 15).PS hard blocks (Figure 15).
with

Figure 15.
Figure 15. The
The structure
structure of
of poly(benzofulvene
poly(benzofulvene (BF)-b-isoprene-b-benzofulvene) (FIF) block
(BF)-b-isoprene-b-benzofulvene) (FIF) block copolymer
copolymer
and mechanical analysis. Reprinted from Reference [92]. (Copyright (2016) American ChemicalChemical
and mechanical analysis. Reprinted from Reference [92]. (Copyright (2016) American Society).
Society).

In comparison with diene-based TPEs, all acrylic-based TPEs showed higher oxidation
In comparison with diene-based TPEs, all acrylic-based TPEs showed higher oxidation stability
stability and UV resistance. The same group synthesized a series of TP all acrylic-based high
and UV resistance. The same group synthesized a series of TP all acrylic-based high temperature
temperature thermoplastic elastomers containing poly(1-adamatyl acrylate) as a hard domain and
thermoplastic elastomers containing poly(1-adamatyl acrylate) as a hard domain and
poly(tetrahydrofurfuryl acrylate) as a soft domain by RAFT polymerization [93]. These TPEs exhibited
poly(tetrahydrofurfuryl acrylate) as a soft domain by RAFT polymerization [93]. These TPEs
superior stress-strain behavior compared to that of conventional all acrylic-based TPEs consisting
exhibited superior stress-strain behavior compared to that of conventional all acrylic-based TPEs
of PMMA and PBA made by controlled radical processes [94], while the tensile strength was lower
consisting of PMMA and PBA made by controlled radical processes [94], while the tensile strength
compared to that of similar products prepared via living anionic polymerization [95].
was lower compared to that of similar products prepared via living anionic polymerization [95].
TPEs with non-linear architectures have also been synthesized and investigated over the last three
TPEs with non-linear architectures have also been synthesized and investigated over the last
decades. Multigraft copolymers of PI-g-PS are found to have high tensile strength, high strain at break,
three decades. Multigraft copolymers of PI-g-PS are found to have high tensile strength, high strain
and low residue strain. Furthermore, Mays et al. synthesized a series of tetrafunctional multigraft
at break, and low residue strain. Furthermore, Mays et al. synthesized a series of tetrafunctional
copolymer (“centipede”) with varied branching points (Figure 16) [96]. The tetrafunctional copolymer
multigraft copolymer (“centipede”) with varied branching points (Figure 16) [96]. The tetrafunctional
with 10 branching points showed an exceptional elongation at break ~2100%, almost double that
copolymer with 10 branching points showed an exceptional elongation at break ~2100%, almost
of commercial Kraton® (1050% at ®similar composition), and only 40% residual strain on hysteresis
double that of commercial Kraton (1050% at similar composition), and only 40% residual strain on
experiments (elongated at 1400%) [97]. Detailed study revealed that the superelasticity was attributed
hysteresis experiments (elongated at 1400%) [97]. Detailed study revealed that the superelasticity was
to the distinct molecular architectures. Furthermore, the same group developed a low-cost emulsion
attributed to the distinct molecular architectures. Furthermore, the same group developed a low-cost
polymerization to prepare comb multigraft copolymers such as PI-g-PS and PBA-g-PS as well as
emulsion polymerization to prepare comb multigraft copolymers such as PI-g-PS and PBA-g-PS as
centipede PBA-g-PS for TPE applications [98,99].
well as centipede PBA-g-PS for TPE applications [98,99].
Polymers 2017, 9, 494 17 of 31

Figure 16. (A) Stress–strain behavior of tetrafunctional multigraft copolymers compared to commercial
thermoplastic elastomers. Reprinted from Reference [96]. (Copyright (2006) American Chemical
Society). (B) Hysteresis curve of a tetrafunctional multigraft copolymer with 14 vol % PS and
5.5 branching points. Reprinted from Reference [97]. (Copyright (2006) WILEY-VCH Verlag GmbH &
Co. KGaA, Weinheim).

4.2. Applications in Drug Delivery and Release

Advanced nanoscale systems created by self-assembly of BCPs have seen tremendous progress
for drug delivery applications over the last decade [100,101]. The advances in BCP self-assembly
offer effective control of morphology, surface chemistry, and the introduction of environmental
responsiveness. Among these nanostructures, micelles and vesicles are the most studied morphologies.
Block copolymer micelles are of interest for drug delivery applications for a number of reasons.
First of all, hydrophobic drugs can be entrapped in the core and transported at concentrations
that can exceed their intrinsic water solubility. Secondly, the hydrophilic blocks, which are often
composed of PEO, can form hydrogen bonds with the aqueous surroundings and form a tight
shell around the micellar core. Moreover, the PEO corona resists protein adsorption and cellular
adhesion, protecting the hydrophobic drug against hydrolysis and enzymatic degradation. In addition,
the PEO corona prevents recognition by the reticuloendothelial system and therefore increases the
blood circulation times [100]. Thermo-responsive micelles are the most widely investigated, such as
poly(N-isopropyl acrylamide-b-D,L-lactide), poly(N-isopropyl acrylamide-b-butyl methacrylate), and
poly(N-isopropyl acrylamide-co-N,N-dimethylacrylamide)-b-poly(D,L-lactide-co-glycolide) [102,103].
These micelles undergo reversible structural changes that facilitate drug release once the temperature
is elevated above the LCST of the polymers [104]. Other stimuli-responsive BCPs have also
been extensively studied. Park et al. developed an amphiphilic BCP composed of PEG and
poly(ε-(4-nitro)benzyloxycarbonyl-L-lysine) for hypoxia-sensitive drug delivery. The formed micelles
encapsulated doxorubicin (DOX) in an aqueous condition and exhibited rapid intracellular release of
DOX under the hypoxic condition [105].
BCPs used in drug delivery should have low toxicity or be non-toxic. BCP vesicles containing
biocompatible PEO, PLA, and PCL have been evaluated [106,107]. Both PEO-b-PLA and PEO-b-PCL
vesicles exhibit the controlled release of active dyes and anti-cancer drugs over periods of up to two
weeks [108,109]. Discher et al. employed vesicles made from a mixture of biocompatible PB-b-PEO
and PLA-b-PEO to simultaneously deliver two anti-cancer drugs, in which hydrophilic doxorubicin
was encapsulated in the cavity and hydrophobic paclitaxel was embedded in the vesicle wall [106,110].
In vivo studies revealed that the vesicle-loaded drugs are more effective and sustainable in tumor
shrinkage as compared with the direct injection of free drugs. Rates of encapsulant release from the
hydrolyzable vesicles are accelerated with an increased proportion of PEG and the molar ratio of
degradable copolymer. In particular, BCP vesicles modified with stimuli-responsive functionalities
have been studied for smart drug delivery. Attaching the vesicle with antibodies allows the delivery of
vesicles to targeted cells [111]. Other than their academic interest, thermosensitive liposomes (TSLs)
Polymers 2017, 9, 494 18 of 31

Polymers 2017, 9, 494 18 of 31

have already been investigated for the treatment of breast cancer and colorectal liver metastasis in
several clinical trials.
thermosensitive liposomes (TSLs) have already been investigated for the treatment of breast cancer
andIn colorectal
spite of the advances
liver in the
metastasis designclinical
in several of peptide
trials.drugs and the emergence of gene therapy, there
is still a In
need tooffurther
spite improve
the advances the design
in the performance of these
of peptide drugssystems that can precisely
and the emergence direct the
of gene therapy, drug to
there
the is still a need
desired to the
site in further improve
body and tothe performance
accurately of these
control systems
the rate that can
at which theprecisely direct the drug
drug is released.
to the desired site in the body and to accurately control the rate at which the drug is released.
4.3. Applications in Soft Lithography
4.3. Applications in Soft Lithography
One of the remarkable candidates for soft lithography is the directed self-assembly (DSA) of
One of the
BCPs, because theyremarkable
can form candidates for soft at
ordered features lithography is theasdirected
a length scale low as self-assembly (DSA) of
a few nanometers, which
BCPs, because they can form ordered features at a length scale as low as a few nanometers, which is
is required for many of the most demanding next generation patterning applications, including the
required for many of the most demanding next generation patterning applications, including the
fabrication of bit patterned media (BPM) for hard disk drives as well as fin field effect transistor
fabrication of bit patterned media (BPM) for hard disk drives as well as fin field effect transistor
(FinFETs) and contact holes for microelectronics [112–118]. Poly(styrene-b-methyl methacrylate)
(FinFETs) and contact holes for microelectronics [112–118]. Poly(styrene-b-methyl methacrylate) (PS-
(PS-b-PMMA)
b-PMMA) isisthethemost
moststudied
studiedBCPBCP system
system because
because it can
it can produce
produce lamellar
lamellar or cylinder
or cylinder morphologies,
morphologies,
which are perpendicularly oriented to the substrate simply via thermal treatment
which are perpendicularly oriented to the substrate simply via thermal treatment (Figure 17) [119]. (Figure 17) [119].
ThisThis
phenomenon
phenomenon is is
attributed
attributedtotothe
the similarity ofthe
similarity of theinterfacial
interfacial energies
energies between
between eacheach
blockblock and the
and the
air interface [120].
air interface Hawker
[120]. Hawkeretetal.al.reported
reported that the neutral
that the neutralsurface
surface(γPS-Air
(γPS-Air ≈ γPMMA-Air)
≈ γPMMA-Air) could
could be be
achieved with thermally annealed PS-b-PMMA at 225 C in air [121].
achieved with thermally annealed PS-b-PMMA at 225 ◦
°C in air [121].

Figure 17. Surface force microscopy (SFM) phase image of (A) cylinder-forming PS-b-PMMA and (B)
Figure 17. Surface force microscopy (SFM) phase image of (A) cylinder-forming PS-b-PMMA and
lamella-forming PS-b-PMMA on the substrate modified by R64 (PS mole fraction of 0.64) and R55 (PS
(B) lamella-forming PS-b-PMMA on the substrate modified by R64 (PS mole fraction of 0.64) and R55
mole fraction of 0.55), respectively, at various film thicknesses of block copolymer after thermally
(PS mole fraction of 0.55), respectively, at various film thicknesses of block copolymer after thermally
annealing thin films at 170 °C for 24 h. Reprinted from Reference [119]. (Copyright (2008) American
annealing thin films at 170 ◦ C for 24 h. Reprinted from Reference [119]. (Copyright (2008) American
Chemical Society).
Chemical Society).
Unfortunately, the minimum feature size is limited to ~13 nm due to its low χ (~0.039 at 150 °C)
[122]. To achieve very
Unfortunately, thehigh resolution
minimum (i.e., small
feature sizefeature size), to
is limited the~13
chemical structure
nm due to its of low
the BCP must at
χ (~0.039
be
◦ carefully designed to maximize the chemical incompatibility between blocks (i.e., high-χ,
150 C) [122]. To achieve very high resolution (i.e., small feature size), the chemical structure of low-N).
the Impressive
BCP must work has beendesigned
be carefully reported to
employing
maximize a variety of high-χ
the chemical BCPs. Russell etbetween
incompatibility al. were blocks
able to (i.e.,
achieve a 3-nm cylindrical domain size using PS-b-PEO on a surface of a sapphire single-crystal
high-χ, low-N). Impressive work has been reported employing a variety of high-χ BCPs. Russell et al.
(Figure 18) [123].
were able to achieve a 3-nm cylindrical domain size using PS-b-PEO on a surface of a sapphire
single-crystal (Figure 18) [123].
Polymers 2017, 9, 494 19 of 31
Polymers 2017, 9, 494 19 of 31

Figure
Figure 18.18. Atomicforce
Atomic forcemicroscopy
microscopy(AFM)
(AFM) height
height images
imagesofofsawtooth
sawtoothpatterns
patternsand
andphase
phase images
images of of
solvent-annealedPS-b-PEO
solvent-annealed PS-b-PEOthin
thin films.
films. (A,D)
(A,D) When
When the
the M-plane
M-planesapphire
sapphirewas wasannealed
annealed at at
1400
1400°C◦ C
andand 1500C,
1500 ◦ °C,a apitch
pitchofof~48
~48and
and~24
~24 nm
nm and
and aa peak-to-valley
peak-to-valley depth
depthofof~6~6and
and~3~3
nmnm were
were obtained,
obtained,
respectively.Highly
respectively. Highlyordered
ordered PEO
PEO cylindrical
cylindrical microdomains
microdomainshaving
havingareal
arealdensities of of
densities 0.74
0.74to to
10.5
10.5
terabit/inch2 from PS-b-PEO (M n = 26.5 kg/mol) (B), PS-b-PEO (Mn = 25.4 kg/mol) (C), PS-b-PEO (Mn =
terabit/inch2 from PS-b-PEO (Mn = 26.5 kg/mol) (B), PS-b-PEO (Mn = 25.4 kg/mol) (C), PS-b-PEO
(M21.0 kg/mol) (E), and PS-b-PEO (Mn = 7.0 kg/mol) (F) BCP thin films annealed in o-xylene vapor were
n = 21.0 kg/mol) (E), and PS-b-PEO (Mn = 7.0 kg/mol) (F) BCP thin films annealed in o-xylene
obtained. Scale bars, 100 nm. Reprinted from Reference [123]. (Copyright (2009) American Association
vapor were obtained. Scale bars, 100 nm. Reprinted from Reference [123]. (Copyright (2009) American
for the Advancement of Science).
Association for the Advancement of Science).

Hillmyer et al. synthesized poly(lactide-b-dimethylsiloxane-lactide) (PLA-PDMS-PLA) to

Hillmyer
achieve et al.
a 7-nm synthesized
pitch size [124].poly(lactide-b-dimethylsiloxane-lactide) (PLA-PDMS-PLA)
Some other BCPs that are capable of self-assembling to achieve
into sub-10 nm
a 7-nm
domain pitch size
sizes [124]. Some
include other [125],
PS-b-PDMS BCPs PS-b-P2VP
that are capable
[126], of
andself-assembling
PS-b-PLA [118]. into
Onsub-10 nm hand,
the other domain
sizes include
high-χ PS-b-PDMS
organic BCPs that[125], PS-b-P2VP
can form sub-10 [126], and PS-b-PLA
nm domains suffer from[118].
lowOn etchthe other hand,
contrast when sizeshigh-χ
organic
approachBCPs thattocan
down 10 form sub-10
nm. Since nm domains
organic polymerssuffer from low
that contain etch contrast
inorganic whensuch
constituents, sizes
as approach
silicon,
down to 10 nm.etch
are inherently Since organic
resistant, thepolymers
incorporationthat of
contain inorganic
one such block in constituents, such as
high-χ BCPs affords silicon, are
exceptional
etch contrast.
inherently etch Cushen
resistant,et the
al. synthesized
incorporation a series of high-χ
of one BCPs in
such block composed of oligosaccharides
high-χ BCPs coupled
affords exceptional etch
to a silicon-containing
contrast. polystyreneaderivative.
Cushen et al. synthesized The BCPs
series of high-χ BCPsexhibit hexagonally
composed packed cylinders
of oligosaccharides with to
coupled
a 5-nm feature size polystyrene
a silicon-containing in thin film [127]. A polarity-switchable
derivative. The BCPs exhibit top hexagonally
layer was alsopacked
appliedcylinders
to the surface
with a
of silicon-containing BCPs films to obtain perpendicular orientation of poly(styrene-b-trimethyl
5-nm feature size in thin film [127]. A polarity-switchable top layer was also applied to the surface silyl
of styrene-b-styrene)
silicon-containing (PS-b-PTMSS-b-PS)
BCPs films to obtain and poly(trimethyl
perpendicular silyl styrene-b-lactide)
orientation (PTMSS-b-PLA)
of poly(styrene-b-trimethyl silyl
after thermal annealing [128].
styrene-b-styrene) (PS-b-PTMSS-b-PS) and poly(trimethyl silyl styrene-b-lactide) (PTMSS-b-PLA) after
On the other hand, BCP architecture also plays a key role in controlling the feature size. Hawker
thermal annealing [128].
compared linear PS-b-PEO and cyclic PS-b-PEO and found that the thin film self-assembly of the latter
On the other hand, BCP architecture also plays a key role in controlling the feature size. Hawker
showed a ~30% decrease in domain spacing (Figure 19), which was attributed to the reduced
compared linear PS-b-PEO and cyclic PS-b-PEO and found that the thin film self-assembly of the
hydrodynamic radii of the cyclic systems [11].
latter showed a ~30% decrease in domain spacing (Figure 19), which was attributed to the reduced
Limited synthetic access has largely restricted the application of cyclic BCPs in soft lithography.
hydrodynamic radii of the cyclic systems [11].
Other complex architecture such as star copolymers, etc. remains a largely unexplored regime.
Limited synthetic
Nevertheless, access hasof
the advancement largely restricted
BCP design, the application
synthesis, processing of strategies,
cyclic BCPs andin morphological
soft lithography.
Other complex architecture such as star copolymers, etc. remains a largely
characterization tools (e.g., atomic force microscopy (AFM), tomographic TEM, grazing-incidence unexplored regime.
Nevertheless, the advancement of BCP design, synthesis, processing strategies,
small-angle scattering (GISAXS), etc.) offers hope that this technology may impact industry and and morphological
characterization tools (e.g.,
society in the coming years.atomic force microscopy (AFM), tomographic TEM, grazing-incidence
small-angle scattering (GISAXS), etc.) offers hope that this technology may impact industry and society
in the coming years.
Polymers 2017, 9, 494 20 of 31
Polymers 2017, 9, 494 20 of 31

Figure
Figure 19.
19.Atomic force force
Atomic microscopy height images
microscopy height for (a) cyclic
images for PS13K-b-PEO5K and (b) PS13K-b-
(a) cyclic PS13K-b-PEO5K and
PEO5K
(b) PS13K-b-PEO5K diblock copolymers (inlet: 2D fast Fourier transform (FFT) Scale
diblock copolymers (inlet: 2D fast Fourier transform (FFT) of AFM images). barsimages).
of AFM are 250
nm.
ScaleReprinted from
bars are 250 Reference
nm. Reprinted[11]. (Copyright
from Reference(2012) American Chemical
[11]. (Copyright Society).Chemical Society).
(2012) American

4.4.
4.4. Applications
Applications in in Mesoporous
Mesoporous Materials
Materials
Research
Research interest
interest in in ordered
ordered porous
porous materials
materials originated
originated fromfrom thethe successful
successful synthesis
synthesis of of porous
porous
silicates
silicates in the 1990s and soon spread to a variety of framework compositions including metal oxides,
in the 1990s and soon spread to a variety of framework compositions including metal oxides,
non-oxide inorganics, and carbon [129]. This group of materials exhibits
non-oxide inorganics, and carbon [129]. This group of materials exhibits periodically aligned structures periodically aligned
structures
and uniform andcavities
uniform withcavities with sizes
sizes ranging fromranging
micro-from micro-
(<2 nm), to (<2
meso-nm), to meso-
(2–50 nm), to (2–50 nm), to
macropores
macropores (>50 nm) [130], which lead to very high surface areas (up to 1500
(>50 nm) [130], which lead to very high surface areas (up to 1500 m2 /g) [131]. With these unique features, m 2/g) [131]. With these

unique features, porous

porous materials presentmaterials
great value present great valueinfor
for applications applications
energy conversionin energy conversion
and storage and
[132–135],
storage [132–135], catalysis [136], drug delivery [137], gas capture
catalysis [136], drug delivery [137], gas capture [138,139], and water purification [140,141]. [138,139], and water purification
[140,141].
As mentioned in the previous section, the self-assembly of BCPs may induce a series of interesting
2D or As3Dmentioned
morphologies, in thewhich previous
makesection,
them very the useful
self-assembly of BCPs may “templates”
as structure-directing induce a series of
for the
interesting 2D or 3D morphologies, which make them very useful
fabrication of porous materials. Generally, the formation of porous materials through polymeras structure-directing “templates”
for the fabrication
templating involves of porous materials.
the following Generally,
steps: the formation
(1) Cooperative of porousof
self-assembly materials
amphiphilicthroughBCPspolymer
in the
templating involves the following steps: (1) Cooperative self-assembly of
presence of a precursor for the framework (such as hydrolyzed silicate, metal oxides, or carbon source) amphiphilic BCPs in the
presence
where theof a precursor
precursor for thetoframework
is directed the hydrophilic (suchdomain
as hydrolyzed silicate, metal
through hydrogen bonding,oxides,
ion or carbon
pairing or
source) where the precursor is directed to the hydrophilic domain through
hydrophilic interactions; (2) solidification/condensation/crosslinking/curing of the precursor to form hydrogen bonding, ion
pairing or hydrophilic
the framework of the porous interactions;
material; and (2) (3)solidification/condensation/crosslinking/curing
removal of the BCP template by solvent washing of the
or
precursor to form the framework of the porous material; and (3) removal
thermal decomposition leaving spaces for pores. However, the specific procedures vary based on the of the BCP template by
solvent
final shapewashing or thermal
of the porous decomposition
material, namely membranes, leavingspheres,
spaces or formonoliths,
pores. However,
and detailed theexamples
specific
procedures vary
will be given below. based on the final shape of the porous material, namely membranes, spheres, or
monoliths,
The mostandcommonly
detailed examples will be given
used copolymer templatebelow.
are the commercial Pluronic surfactants, a group
of poly(ethylene glycol-b-propylene glycol-b-ethyleneare
The most commonly used copolymer template the commercial
glycol) Pluronic surfactants,
(PEG-b-PPG-b-PEG) with limitedaoptions
group
of poly(ethylene glycol-b-propylene glycol-b-ethylene glycol) (PEG-b-PPG-b-PEG)
for lengths of polymer blocks. Alternatively, amphiphilic BCPs with wider choices for composition with limited
options for lengths
and molecular weightofofpolymer
the polymer blocks. Alternatively,
segments are readilyamphiphilic
designed and BCPs with wider
synthesized in thechoices for
laboratory
composition and molecular weight of the polymer segments are readily
through controlled/“living” polymerization techniques [142]. These synthesized BCPs usually contain designed and synthesized in
the laboratory through controlled/“living” polymerization techniques
poly(2-vinylpyridine) (P2VP), poly(4-vinylpyridine) (P4VP), or poly(ethylene oxide) (PEO) as the [142]. These synthesized BCPs
usually contain
hydrophilic poly(2-vinylpyridine)
block, and PS, PMMA, PI, (P2VP), poly(4-vinylpyridine)
polyisobutylene (PIB), and (P4VP), or poly(ethylene
polyacrylonitrile (PAN) oxide)
as the
(PEO) as the hydrophilic block, and PS, PMMA, PI, polyisobutylene
hydrophobic block [143,144]. In addition to high versatility, BCPs synthesized in the laboratory show(PIB), and polyacrylonitrile
(PAN) as theashydrophobic
other merits compared toblock [143,144].
commercial In addition
Pluronic to high
copolymers. Theversatility,
contrast inBCPs synthesized
hydrophilicity in the
between
laboratory show other merits as compared to commercial Pluronic
the two selected blocks are usually higher than for the PEG and PPG pair in the Pluronics, which
copolymers. The contrast in
hydrophilicity between the two selected blocks are usually higher than for the PEG and PPG pair in
the Pluronics, which is beneficial for the self-assembly of polymer micelles in aqueous solution.
Moreover, hydrophobic blocks such as PS and PMMA exhibit much higher glass transition
Polymers 2017, 9, 494 21 of 31

is beneficial for the self-assembly of polymer micelles in aqueous solution. Moreover, hydrophobic
blocks such as PS and PMMA exhibit much higher glass transition temperatures than PPG,21resulting
Polymers 2017, 9, 494 of 31
in better stability of the self-assembled structures. In the case of copolymers containing PS and PAN,
the hydrophobic
temperaturessegments
than PPG,can be converted
resulting in better to carbonofresidue
stability in high yield
the self-assembled in the carbonization
structures. In the case of step,
whichcopolymers containing PS
provides additional and PAN, support
mechanical the hydrophobic segments canframework
to the mesoporous be converted to carbon residue
[145].
in high yield in the carbonization
Evaporation-induced self-assembly step,(EISA)
which is provides
widelyadditional
used in mechanical
the preparationsupport of to ordered
the
mesoporous framework [145].
mesoporous films and particles, which is especially important for oxides. In a typical EISA process, the
Evaporation-induced self-assembly (EISA) is widely used in the preparation of ordered
cooperative self-assembly of a precursor with an amphiphilic template is induced by a concentration
mesoporous films and particles, which is especially important for oxides. In a typical EISA process,
gradient of an organic solvent such as tetrahydrofuran (THF), chloroform, or dioxane. Different from
the cooperative self-assembly of a precursor with an amphiphilic template is induced by a
a general solvent-annealing
concentration gradient of an process, precursor
organic solvent suchmolecules are crosslinked
as tetrahydrofuran in EISA or
(THF), chloroform, asdioxane.
the solvent
evaporates,
Differentleaving no chance
from a general for structureprocess,
solvent-annealing refinement aftermolecules
precursor it is formed [146,147]. inWiesner
are crosslinked EISA as et al.
synthesized
the solvent evaporates, leaving no chance for structure refinement after it is formed [146,147]. as a
mesostructured silicate/copolymer composite film through EISA with PS-b-PEO
structure-directing agent in amesostructured
Wiesner et al. synthesized mixture of THF and water [148].
silicate/copolymer A largefilm
composite variety of mesoporous
through EISA with PS-metal
oxidesb-PEO
in theas form
a structure-directing
of powder were agent in a mixture
synthesized of THFEISA
through and water
using [148]. A large Pluronics
commercial variety of as a
mesoporous
template [149]. Inmetal oxidesmesoporous
addition, in the form ofcarbon
powderfilmswerewere
synthesized
prepared through EISA from
via EISA using acommercial
thermosetting
Pluronics
precursor as a template [149]. In system,
(phenol-formaldehyde addition,resol,
mesoporous carbonetc.)
resorcinol, filmsusing
were prepared
a varietyvia ofEISA
BCPfrom a
templates
thermosetting precursor (phenol-formaldehyde system, resol, resorcinol, etc.) using a variety of BCP
such as PS-b-P4VP, PEO-b-PS, PEO-b-PMMA, and PEO-b-PMMA-b-PS [143]. Recently, Wei and
templates such as PS-b-P4VP, PEO-b-PS, PEO-b-PMMA, and PEO-b-PMMA-b-PS [143]. Recently, Wei
coworkers reported the synthesis of nitrogen-doped mesoporous carbon in the form of powder
and coworkers reported the synthesis of nitrogen-doped mesoporous carbon in the form of powder
through EISA,
through using
EISA, usingPluoric
Pluoriccopolymer
copolymer as asthe
thetemplate,
template, with
with resol resol and dicyandiamide
and dicyandiamide as sourcesas sources
for
for CCand N, respectively [147]. For clarification, some research groups do
and N, respectively [147]. For clarification, some research groups do not consider systems involving not consider systems
involving formaldehyde
formaldehyde as an as an actual
actual EISA EISA
process,process,
since since the crosslinking
the crosslinking of precursors
of precursors occurs occurs
after after
the the
cooperative self-assembly,
cooperative self-assembly, instead ofof
instead simultaneously,
simultaneously, as as in many
manyEISAEISAprocesses
processes [146].
[146].
Following
Following the the traditional
traditional EISAmethod,
EISA method,an an evaporation-induced
evaporation-induced aggregationaggregation assembly
assembly(EIAA) (EIAA)
mechanism, was proposed [150]. This solution precipitation method
mechanism, was proposed [150]. This solution precipitation method can produce mesoporous materials can produce mesoporous
materialsshapes
with various with various shapes
including including
spheres, spheres,
fibers, and fibers, and polyhedrons
polyhedrons in the form in the
of form
powder of powder
[151]. [151].
Moreover,
Moreover, the EIAA method tolerates a greater portion of water compared to EISA, which makes it
the EIAA method tolerates a greater portion of water compared to EISA, which makes it more suitable
more suitable for scaling up. In detail, the water-insoluble template PEO-b-PMMA and silica
for scaling up. In detail, the water-insoluble template PEO-b-PMMA and silica precursor were first
precursor were first dissolved in a mixture of THF and water. As THF evaporated, the BCP and
dissolved
silicateinoligomers
a mixturewere of THF and
driven towater. As THF evaporated,
form composite micelles with the BCP located
silicates and silicate
at theoligomers
shell. Withwere
driven to form
further composite
removal of themicelles
solvent, with silicatesassembled
the micelles located atintothe shell. With further
mesostructured removal
particles of liquid-
at the the solvent,
the micelles assembled
liquid interface andinto mesostructured
precipitated from theparticles
solution.atSubsequent
the liquid-liquid interface
calcination of theand precipitated
precipitants
from completely
the solution. Subsequent
removed the PMMAcalcination
block toofform
the precipitants completely
pores. A schematic removed
illustration of EIAAthe PMMA
is shownblockin to
Figure 20.
form pores. A schematic illustration of EIAA is shown in Figure 20.

Figure 20. (A)

Figure 20. Formation
(A) Formation mechanism
mechanismof ofordered mesoporous
ordered mesoporous silica
silica through
through the solvent
the solvent evaporation
evaporation -
-induced
induced aggregating assembly (EIAA) process by using diblock copolymer PEO-b-PMMAa template,
aggregating assembly (EIAA) process by using diblock copolymer PEO-b-PMMA as as a
tetraethylorthosilicate (TEOS) as the(TEOS)
template, tetraethylorthosilicate silica source, and acidic
as the silica tetrahydrofuran
source, (THF)/H2 O(THF)/H
and acidic tetrahydrofuran mixture2Oas the
mixture
solvent; as the solvent;
(B) Typical (B) Typical
field-emission field-emission
scanning electronscanning electron
microscopy microscopy
(FESEM) image(FESEM) image ofsilica
of mesoporous
mesoporous silica ◦ calcinated in air at 550 °C. Reprinted from Reference [150].
calcinated in air at 550 C. Reprinted from Reference [150]. (Copyright (2011) American Chemical (Copyright (2011)
Society).
American Chemical Society).
Polymers 2017, 9, 494 22 of 31
Polymers 2017, 9, 494 22 of 31

More recently, Tang et al. proposed a facile micelle method to synthesize N-doped mesoporous
carbon spheres
More without
recently, Tangthe EISA
et al. processa (Figure
proposed 21). The
facile micelle key difference
method of this
to synthesize researchmesoporous
N-doped from EISA
lies in the
carbon formation
spheres without of the
stable
EISA micelles
processof(Figure
dopamine (both
21). The C difference
key and N sources)
of thisusing a high
research frommolecular
EISA lies
weight PS-b-PEO as a template. After the micelle was formed, dopamine was polymerized
in the formation of stable micelles of dopamine (both C and N sources) using a high molecular weight using
ammonia as an initiator. These “frozen” micelles joined together forming into
PS-b-PEO as a template. After the micelle was formed, dopamine was polymerized using ammonia larger spheres with
sizes around 200
as an initiator. nm.“frozen”
These These composite spheres
micelles joined wereforming
together easily separated
into largerfrom the with
spheres solution
sizesthrough
around
centrifugation and allowed for further carbonization to remove the template
200 nm. These composite spheres were easily separated from the solution through centrifugation and and fabricate
mesoporous spherescarbonization
allowed for further [152]. to remove the template and fabricate mesoporous spheres [152].

Figure 21. Synthesis of nitrogen-doped mesoporous carbon spheres (NMCS) with extra-large pores
through the assembly ofof diblock
diblock copolymer
copolymer micelles.
micelles. Reprinted from Reference
Reference [152].
[152]. (Copyright
(2015) WILEY-VCH
WILEY-VCH Verlag
VerlagGmbH
GmbH&&Co. Co.KGaA,
KGaA,Weinheim).
Weinheim).

Many
Many studies
studies demonstrated
demonstrated the the advantage
advantage of of mesopores
mesopores over over micropores
micropores in in the
the mass
mass transport
transport
process in
process in aa variety
variety of
of applications
applications [135,153].
[135,153]. Larger
Larger pore
pore size
size facilitates
facilitates aa more
more efficient diffusion of
efficient diffusion of
guest molecules within the pores [136], and also allows the loading of metal
guest molecules within the pores [136], and also allows the loading of metal catalyst particles [154,155]. catalyst particles
[154,155].
Thick poreThick
wallspore wallsfavorable
are also are also favorable
because ofbecause of the possibility
the possibility for further formodification
further modification
on the pore on
the pore[151,155].
surface surface [151,155].
Since
Since thethe pores
pores are
are produced
produced from from the
the calcination
calcination of of the
the hydrophobic
hydrophobic segment
segment of of the
the BCP,
BCP, high
high
molecular weight of the sacrificial block is highly desired. Unfortunately,
molecular weight of the sacrificial block is highly desired. Unfortunately, the mesoporous materialsthe mesoporous materials
templated
templated from fromcommercial
commercial Pluronic
Pluronic copolymers
copolymers show show
a porea pore size limited
size limited to 12 nm to and
12 nm and
a wall a wall
thickness
thickness no more than 6 nm [151]. BCPs with higher molecular weight
no more than 6 nm [151]. BCPs with higher molecular weight in the sacrificial segment (higher in the sacrificial segment
(higher hydrophobic
hydrophobic volume in volume in the copolymer)
the copolymer) have been have been extensively
extensively utilized
utilized for largerfor larger
pores pores
in the in the
resulting
resulting porous material. Using PEO-b-PS (M w = 29,700 g/mol) as the
porous material. Using PEO-b-PS (Mw = 29,700 g/mol) as the copolymer template, adding a special copolymer template, adding a
special hydrothermal treatment step, Deng et al. achieved mesoporous silica
hydrothermal treatment step, Deng et al. achieved mesoporous silica with pore diameters as large as with pore diameters as
large as 30.8
30.8 nm [156].nmBy[156].
varyingBy varying
the lengthsthe of
lengths of each segment
each segment of BCP templates,
of BCP templates, Tang et al.Tang et al. observed
observed a strong
acorrelation
strong correlation of the resulting pore size with the length of BCP, where PS
of the resulting pore size with the length of BCP, where PS37 -b-PEO114 , PS178 -b-PEO886 , 37-b-PEO114, PS178-b-

PEO 886, and PS173-b-PEO170 resulted in pore sizes of 5.4 nm, 16 nm and 16 nm, respectively [152]. In
and PS 173 -b-PEO 170 resulted in pore sizes of 5.4 nm, 16 nm and 16 nm, respectively [152]. In another
another
case, aluminum-organophosphonate films withfilms
case, aluminum-organophosphonate tunablewith tunable macropores
macropores (30–200 nm)(30–200 nm) were
were synthesized
synthesized via ultra-high molecular weight PEO-b-PS (250,000 g/mol)
via ultra-high molecular weight PEO-b-PS (250,000 g/mol) templates, though the resulting material templates, though the
resulting
exhibited material exhibited
a relatively disordereda relatively disordered
mesostructure mesostructure
[157]. In addition to [157]. In addition
utilizing to utilizing
high molecular high
weight
molecular weight BCPs as templates to target material with larger pores,
BCPs as templates to target material with larger pores, an additional hydrophobic component can be an additional hydrophobic
component
added to thecan be added
mixture as a poreto the mixture
swelling as aFor
agent. pore swelling
example, withagent. Forofexample,
the aid with the (TMB),
trimethylbenzene aid of
trimethylbenzene (TMB), the pore size of silica can be expanded to 30 nm [158]. Moreover, Deng et
Polymers 2017, 9, 494 23 of 31

Polymers 2017, 9, 494 23 of 31

the pore size of silica can be expanded to 30 nm [158]. Moreover, Deng et al. reported the use of PS
al. reported theas
homopolymer use
theofpore
PS homopolymer
expanding agentas the pore
in the expanding
synthesis agent in thecarbon,
of mesoporous synthesis of mesoporous
when PS-b-PEO is
carbon, when PS-b-PEO is selected as the template [159]. However, care must
selected as the template [159]. However, care must be taken when using the pore expanding agent be taken when using to
the
thepore expanding
composite agent
in order to to the composite
avoid the risk of in order tomesostructures
unstable avoid the risk of unstable mesostructures [160].
[160].
The
Thearrangement
arrangementofofaamesostructured
mesostructuredmaterial
material is is
closely
closelyrelated to to
related thethe
microphase
microphase separation
separationof
the BCP
of the BCPtemplate.
template.Interestingly,
Interestingly, simply
simplyvarying
varying thetheamount
amountofofthetheprecursor
precursorwith
withrespect
respecttoto the
the
copolymer
copolymer would
would also
also lead
lead toto morphological
morphological changes
changes in in the
the composite
composite system [148]. Garcia Garcia and
and
coworkers
coworkers fully explored
exploredthe thephase
phasediagram
diagramofof a polymer/alumina/silanecomposite
a polymer/alumina/silane composite system
system aimed
aimed for
for
thethe synthesis
synthesis of porous
of porous aluminosilicate
aluminosilicate usingusing PEO-b-PI
PEO-b-PI as a as a template.
template. As illustrated
As illustrated in Figure
in Figure 22,
22, eight
eight morphologies
morphologies of theof the composite
composite systemsystem were obtained
were obtained by adding by different
adding different
amounts amounts of the
of the inorganic
inorganic precursor into BCP templates [161]. Many interesting crystal symmetries
precursor into BCP templates [161]. Many interesting crystal symmetries could be achieved through could be achieved
through finethe
fine tuning tuning the template
template compositions,
compositions, and examples
and examples are substantially
are substantially reviewedreviewed
[151]. [151].

Figure
Figure22.
22.Ternary
Ternarydiagram
diagrammapping
mappingout the
out morphologies
the morphologies found
found forfor
various
variouscomposites
composites directed by
directed
PI-b-PEO using
by PI-b-PEO (3-glycidyloxypropyl)trimethoxysilane
using (3-glycidyloxypropyl)trimethoxysilane (GLYMO)
(GLYMO) andandaluminum
aluminumsec-butoxide
sec-butoxideas as
inorganic
inorganic precursors.
precursors. AtAt the
thebottom
bottomofofthethediagram,
diagram, schematics
schematics of the
of the morphologies
morphologies foundfound forpure
for the the
pure PI-b-PEO
PI-b-PEO are shown.
are shown. HatchedHatched areas the
areas along along the PI-b-PEO
PI-b-PEO axis indicate
axis indicate areas whereareasnowhere no data
data was was
available
from the diblock
available from thecopolymer diagram. Each
diblock copolymer whiteEach
diagram. region within
white the within
region diagram is diagram
the labeled with a schematic
is labeled with
arepresenting the morphology
schematic representing of the composites
the morphology formed.
of the The yellow
composites formed. (light)
The regions
yellow in theseregions
(light) schematicin
morphologies
these schematicon the right andonleft
morphologies theare a representation
right of the PEO/inorganic
and left are a representation domains. Closed
of the PEO/inorganic dark
domains.
points on
Closed a gray
dark background
points on a grayindicate areas where
background indicatebiphasic behavior
areas where is observed.
biphasic Reprinted
behavior from
is observed.
Reference [161]. (Copyright (2009) American Chemical Society).
Reprinted from Reference [161]. (Copyright (2009) American Chemical Society).

5.
5. Conclusions
Conclusionsand
andPerspectives
Perspectives
In
In this
this review,
review, wewe have
have discussed
discussed thethe robust
robust synthetic
synthetic approaches
approaches to to well-defined
well-defined block
block
copolymers
copolymers with controlled compositions and architectures, in which the sequential addition of
with controlled compositions and architectures, in which the sequential addition of
controlled/living
controlled/livingpolymerization
polymerizationtechniques
techniquesand and the
the combination
combination of of controlled
controlled polymerization
polymerization
techniques
techniques with
with facile
facile coupling
coupling chemistry
chemistry have
have expanded
expanded thethe spectrum
spectrum ofof available
available BCPs.
BCPs. OneOne of
ofthe
the
most fascinating features of BCPs is their ability to self-assemble into nanoscale ordered
most fascinating features of BCPs is their ability to self-assemble into nanoscale ordered structures structures
with
with various
various morphologies
morphologies such such as
asspheres,
spheres,cylinders,
cylinders,bicontinuous
bicontinuous structures,
structures, lamellae,
lamellae, etc.
etc. Detailed
Detailed
study
study both
bothfrom
from experiments
experimentsand andtheoretical
theoretical modeling
modeling hashas revealed
revealed that
that the
the nature
nature of
of morphologies
morphologies
is
is determined
determined by by factors
factors including
including interaction
interactionparameter
parameter(χ),
(χ), degree
degree ofof polymerization
polymerization(N), (N), and
and the
the
volume fraction (f), as well as molecular architecture. Due to these unique features, BCPs have
attracted massive attention as thermoplastic elastomers, as drug delivery systems, in soft lithography,
as mesoporous materials, and in many other areas.
Polymers 2017, 9, 494 24 of 31

volume fraction (f ), as well as molecular architecture. Due to these unique features, BCPs have
attracted massive attention as thermoplastic elastomers, as drug delivery systems, in soft lithography,
as mesoporous materials, and in many other areas.
These fascinating BCPs with chemical and topological diversity bring new challenges for the
establishment of structure-property relationships and novel applications. For instance, BCP materials
including rod–coil diblocks and bottlebrush materials should be investigated to create more elaborate
nanostructures. Recent advancements in BCP patterning have pushed the limits of feature sizes
to both smaller (<5 nm) and larger scales (>50 nm). We expect that these new challenges can
be coped with by precisely tunable interactions between blocks in terms of range and strength,
which further relies on their precise synthesis and guidance from theory and simulation. Strategical
placement of ionic moieties might offer a promising approach. Although significant work has been
reported, more interdisciplinary collaborations are still needed in order to advance the synthesis,
structural and dynamic characterization, theory and simulation, and to gain a clear picture of BCP
structure-property relationships.

Acknowledgments: This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy
Sciences, Materials Sciences, and Engineering Division. No funds were provided to cover the costs to publish in
open access.
Author Contributions: Jimmy W. Mays conceived the topic of this review. Hongbo Feng, Xinyi Lu, and
Weiyu Wang designed the structure of this manuscript and reviewed the literature. Hongbo Feng, Xinyi Lu,
Weiyu Wang, Nam-Goo Kang and Jimmy W. Mays edited the manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

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