HIGHLIGHT

Ultrasound in Polymer Chemistry: Revival

of an Established Technique
JOS M. J. PAULUSSE, RINT P. SIJBESMA
Eindhoven University of Technology, Eindhoven, The Netherlands

Received 7 June 2006; accepted 20 June 2006

DOI: 10.1002/pola.21646
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: The history of

ultrasound in polymer chemistry
goes back a long way. Initially, its
uses were limited to being an alternative method of initiating radical
polymerizations through the decomposition of solvents to form
radicals or through the breakage of

polymers leading to macroradicals.

Recently, the raw power of ultrasound has been focused through
the use of weak linkages in polymer chains, which enables the production of well-dened macroradicals and coordinatively unsaturated metal complexes. VC 2006 Wiley

Periodicals, Inc. J Polym Sci Part A: Polym

Chem 44: 54455453, 2006

Keywords: block copolymers;

mechanochemistry; metal-polymer
complexes; radical polymerization; supramolecular structures;
ultrasound

Jos M. J. Paulusse obtained his masters degree from the Eindhoven University of Technology (Eindhoven, The Netherlands) in
2002. Thereafter, he joined the group of Professor E. W. Meijer
and Professor R. P. Sijbesma to start working toward his Ph.D.
degree. His research concerns the mechanical dissociation of
ligands from transition-metal complexes and the application of this
principle in coordination chemistry and catalysis.

JOS M. J. PAULUSSE
AND RINT P. SIJBESMA

Rint P. Sijbesma is a professor of supramolecular polymer chemistry at the Eindhoven University of Technology (Eindhoven, The
Netherlands). He received his Ph.D. in Organic Chemistry at the
University of Nijmegen in 1993, where he studied synthetic receptor molecules with Professor Roeland Nolte. From 1992 to 1993,
he worked as a postdoctoral research fellow with Professor Fred

Correspondence to: R. P. Sijbesma (E-mail: r.p.sijbesma@

tue.nl)
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Wudl (University of California, Santa Barbara, CA) on the synthesis of water-soluble C60 derivatives. In 1993, he moved to the
Eindhoven University of Technology as an assistant professor, and
he was appointed a full professor there in 2006. His research interests are focused on the principles and applications of polymer
self-assembly.

CHEMICAL AND MECHANICAL EFFECTS OF

ULTRASOUND
Ultrasound consists of high-frequency sound waves,
and depending on its frequency, it is denoted as either
destructive (20 kHz to 2 MHz) or nondestructive diagnostic ultrasound (5 MHz to 10 MHz). Although the
latter is mainly used in diagnostic applications, sonochemical applications require the high-energy waves of
destructive ultrasound. When a liquid is irradiated with
ultrasound, the sound waves locally compress and
expand the liquid (see Fig. 1). The liquid will follow
the movements, but the distance between the molecules
can become so large that the liquid is broken. Cavitation bubbles are then created, and they increase in size
during several compression and rarefaction cycles. When
a bubble grows beyond a certain size, it becomes unstable and collapses. During the collapse, the liquid surrounding the bubble is strongly accelerated, and collisions between the molecules create so-called hot spots
with very high temperatures and pressures. The effects
of ultrasound are usually divided into chemical and mechanical effects; the high temperatures are responsible
for chemical effects such as radical formation and sonoluminescence, whereas the strong shear gradients induce
mechanical effects. This highlight focuses on the uses of
ultrasound in polymer chemistry to initiate polymerizations and to produce block copolymers as well as its
newest applications in site-specic cleavage and reversible mechanochemistry.

merizations are among the most widely applied methods of producing polymers.2
After the discovery in the early 1950s that ultrasound can be used to split water into hydrogen and hydroxide radicals,35 several groups came up with the
idea of intercepting these radicals with reactive monomers, as shown in Scheme 1. Henglein and Schulz6
used the decomposition of water to polymerize acrylonitrile, which led to highly viscous products. Lindstrom
and Lamm3 used the polymerization of acrylamide to
gain more insight into the mechanism of radical formation. Unfortunately, the polymers were analyzed only
qualitatively.
Initially, ultrasound-induced polymerizations were
limited to water as a reaction medium. The breakdown
of organic solvents to form radicals was not observed
until Anbar et al.7 showed in 1965 that under ultrasonic irradiation, acetonitrile decomposes into nitrogen,
methane, and hydrogen. Since then, many ultrasoundinitiated polymerizations in organic solvents, in the absence of water, have been reported.
The rst reports concern rather ill-dened polymerizations of nitrobenzene8 and styrene, isoprene, and
methyl methacrylate,9 leading to pitchlike or dark, brittle
materials. Kruus et al.10 investigated why this coloration
took place and suggested that the collapse of cavitation
bubbles was powerful enough to induce reactions similar
to pyrolysis. It was shown that the addition of hexane

ULTRASOUND-INDUCED
POLYMERIZATIONS
Ultrasound has been used extensively for synthetic purposes. In many cases, the aim of ultrasonication in synthesis is merely the thorough homogenization of heterogeneous systems. Nevertheless, examples of true
sonochemical reactions are numerous. Cravotto and
Cintas1 reviewed the literature concerning ultrasound
in organic synthesis. Most reactions promoted by ultrasound involve the transfer of electrons, that is, the formation of radicals. The step from organic chemistry to
polymer chemistry is a small one because radical poly-

Figure 1. Schematic representation of the growth and collapse of cavitation bubbles. (From H. F. Mark, Encyclopedia
of Polymer Science and Technology; Wiley-Interscience:
New York, 2005, ' 2005 John Wiley & Sons, Inc., adapted
by permission.).
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HIGHLIGHT

Scheme 1. Ultrasonic degradation of water and subsequent

initiation of acrylonitrile (top) and acrylamide (bottom) radical polymerization.

increased the vapor pressure and thereby reduced the violence of cavitation, making the process more controlled.
This prevented coloration and resulted in the formation
of high-molecular-weight polystyrene.
Ultrasound has been used mainly as a replacement
of radical initiators such as 2,20 -azobisisobutyrylnitrile
(AIBN). However, ultrasound can also be used in combination with chemical radical initiators. Price et al.11
showed that ultrasound can cleave azo compounds at
25 8C and initiate the radical polymerization of methyl
methacrylate. The rate of ultrasonic decomposition of
AIBN at room temperature is comparable to the rate of
decomposition without ultrasound at 70 8C and enables
the use of radical initiators at much lower temperatures.
Keurentjes et al.12 showed that sonochemistry can be
performed even in liqueed carbon dioxide. Cavitation is
normally hampered by high pressures, although the high
vapor pressure of carbon dioxide compensates for this.
In a mixture of carbon dioxide and methyl methacrylate,
collapsing cavitation bubbles degrade the methyl methacrylate molecules to create radicals, which initiate the
polymerization of methyl methacrylate;13 polymerization up to molecular weights of nearly 500 kg/mol has
been achieved. This new polymerization process has

great potential because initiators or organic solvents are

no longer required. A continuous polymerization setup
has been worked out, but the low efciency of ultrasound
and the low polymerization rates are important hurdles
that have to be overcome.14 A complication in ultrasound-induced polymerizations is the increase in the viscosity during the polymerization of a monomer. This
slows down the production of cavitation bubbles and
therefore the production of radical initiators. Because of
the antisolvent effect of carbon dioxide, the hydrodynamic volume of the polymers is much smaller than that
in the bulk, so the viscosity buildup is also much slower
during polymerizations. However, as the molecular
weight increases, ultrasonic depolymerization also
becomes more pronounced, and this is a limitation for
the maximum molecular weight achievable.

ULTRASOUND-INDUCED
POLYMER SCISSION
In addition to the chemical effects of ultrasound, the
mechanical effects also play an important role in ultrasound-induced polymerizations because they may cause
scission of the polymers. Even before ultrasound was
used to initiate polymerizations, it was known that
ultrasound could also break polymer chains.15,16 The
collapse of cavitation bubbles induces strong shear gradients in addition to hot spots. Although the hot spots
have a very local character, the mechanical effects take
place over much larger distances (micrometers). Small
molecules are only translated by these forces, but the
effect of the gradient on polymers is much larger and
results in chain extension and even scission of covalent
bonds (see Fig. 2). Chain rupture caused by shear is
characterized by a limiting molecular weight. The
polymer chains must be long enough for the mechanical force to build up and reach the level necessary to

Figure 2. Collapse of a cavitation bubble, producing a shear gradient (left), and the shear gradient, able to stretch and break polymers (right).
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Figure 3. Ultrasonic scission of poly(methyl)methacrylate, end capping with a nitroxide radical, and subsequent nitroxide-mediated polymerization of styrene.

rupture the bond.17 This makes ultrasonic scission a

nonrandom technique that preferentially acts on the
highest molecular weight polymers. Chain scission can
result in either homolytic or heterolytic bond cleavage.
In either case, the chain ends that are formed are
highly reactive (charged species or radicals) and often
lead to intramolecular rearrangements or side reactions
with other molecules.18

ULTRASOUND-INDUCED BLOCK
COPOLYMER FORMATION
The macroradicals formed by the scission of polymer
chains can also be used to initiate new polymerizations. In effect, block copolymers can be produced
with material properties different from those of a blend
of homopolymers.19 Alexander and Fox20 were the rst
to exploit the ultrasonic scission of polymer chains in
this way, although initially they set out to investigate
the identity of the end groups formed by the breakage
of poly(methacrylic acid). When they sonicated the
polymer in the presence of styrene, a polymerization
was initiated, giving rise to block copolymers of poly
(methacrylic acid) and polystyrene and at the same
time conrming the formation of (macro)radicals.
Around the same time, Henglein21 investigated the ultrasonic degradation of polyacrylamide and combined
this with the ultrasound-induced polymerization of acrylonitrile in water. Polyacrylamide chains were broken
with ultrasound in the presence of acrylonitrile, and
block copolymers were prepared in this way.
Another way of producing block copolymers involves the reaction of two macroradicals. When polystyrene was sonicated together with several poly(alkyl

Scheme 2.

methacrylate)s, block copolymers were formed.22,23

ODriscoll and Sridharan24 developed a continuous polymerization setup for the production of homopolymers
and block copolymers, such as poly[styrene-block(methyl)methacrylate].
The formation of the second block by the reaction
of the macroinitiator with a different monomer cannot
always be performed under the conditions of sonication
(e.g., when ultrasound initiates side reactions or when
the vapor pressure of the monomer prevents cavitation
from taking place). To address this issue, Bartsch and
Schmidt-Naake25 divided ultrasound-induced block copolymer formation into two separate steps. The rst
step consisted of the scission of poly(methyl methacrylate) in the presence of a nitroxide [e.g., 4-hydroxy2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) or 2,2,5,
trimethyl-4-isopropyl-3-azahexane-3-oxyl (BIPNO)].26
The macroradicals were end-capped by the nitroxide.
In a second step, the nitroxide-terminated polymers
were mixed with styrene, and this resulted in a controlled radical polymerization (see Fig. 3). Yet some of
the initial homopolymer remained present after nitroxide end capping. Furthermore, because of the presence of residual nitroxide, homopolymers of the new
monomer were also formed. Through selective precipitations, the pure block copolymer was isolated. The
process is not complicated and can indeed easily give
new block copolymers. However, during the sonication
step, monofunctional and bifunctional macroinitiators
can form because the chain can be broken more than
once. In the following polymerization step, this will
then lead to AB and ABA block copolymers, assuming
no further combination of polymer chains takes place.
The production of block copolymers with ultrasound
has not yet led to well-dened products. High-molecular-weight polymers are required to form macroinitia-

Scission of a polystyrene chain, leading to primary and secondary macroradicals.

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HIGHLIGHT

Scheme 3.
ages.

Synthesis of PVP 1 containing peroxide link-

tors, but this condition is difcult to combine with a

single scission event on the polymer. To reduce this
problem, the molecular weight can be chosen just
below twice the limiting molecular weight, but this
will result in low scission efciency. For certain properties, well-dened products are not required. Therefore, ultrasound may be employed as a useful tool in
the (large-scale) production of block copolymers, even
though the process is not selective enough to prepare
new block copolymers for fundamental studies of their
material properties.

SITE-SPECIFIC CLEAVAGE
A disadvantage of using macroradical initiators is that
the chemical structure of the radicals is not uniform. In
simple vinyl polymers, such as acrylates and styrene,
the scission of carboncarbon bonds at chemically
equivalent positions leads to two different radicals, as
depicted in Scheme 2. The composition of the product
mixture is even more complex when polymers with
nonequivalent bonds in the main chain are subjected to
ultrasound. Although ultrasound will preferentially
break the weakest bonds, the process is not fully specic and will result in a mixture of different macroradicals.
This was shown by Encina et al.,27 who introduced
defects in poly(vinylpyrrolidone) (PVP). Vinylpyrrolidone was polymerized with AIBN in the presence of
oxygen-generating polymer 1 (see Scheme 3). This
caused some of the radicals to react with the oxygen
and form peroxide linkages; approximately 1 peroxide
bond was incorporated for every 500 carboncarbon
bonds. The average bond enthalpy of an O

O bond is
146 kJ/mol versus 347 kJ/mol for a C

C bond. Comparing the viscosity reduction of the peroxide-contain-

ing PVP and regular PVP samples showed that scission

was 10 times more rapid, and this showed that peroxide bonds broke 5000 times faster than the C

C
bonds in the polymer main chain.
More recently, Moore et al.28 synthesized polymers
containing a single weak linkage at a specic place.
Two chains of a-amino poly(ethylene glycol) (molecular weight 20 kg/mol) were connected through an
azo linkage (2a) and through an alkyl linkage (3), as
depicted in Figure 4. These polymers were sonicated,
and the molecular weight reduction of azo-functionalized polymer 2a was faster than that of the alkyllinked polymer. Site-specic cleavage was further
demonstrated with an off-center azo-functionalized poly(ethylene glycol) (2b). A short polymer chain
(number-average molecular weight 10 kg/mol) was
linked to a long polymer chain (number-average molecular weight 30 kg/mol) via an azo linkage. Polymer 2b was sonicated, and size exclusion chromatography measurements showed the appearance of two
peaks, one at 30 kg/mol and one at 10 kg/mol; this
was in agreement with the scission at the azo linkage.
In contrast to scission in regular polymers, this procedure yields macroradicals of low polydispersity. The
authors are currently studying the system as an alternative for thermally induced or photoinduced reactions.
The research on the site-specic cleavage of weak
bonds in coordination polymers indicates that even
higher selectivity can be obtained between covalent
and noncovalent bonds in supramolecular polymers.
This topic has only recently begun to be explored and
is discussed in the following section.

REVERSIBLE COORDINATION POLYMERS

When monomers in a polymer chain are connected by
noncovalent interactions, supramolecular polymers are
obtained.29 A wide range of interactions have been
used to connect the monomers, such as hydrogen
bonds, pp stacking, hydrophobic and hydrophilic
interactions, and ionic interactions. Coordination polymers are a special class of supramolecular polymers in
which the monomers are connected by ligand-to-metal

Figure 4. Poly(ethylene glycol) polymers with a centered azo linkage (2a) and an off-center
azo linkage (2b).
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Figure 5.

Schematic representation of the equilibrium between rings and chains.

coordinative bonds. Although the literature on coordination polymers in the solid state is extensive, the
number of reversible linear coordination polymers is
still rather limited.3037 Nonetheless, these polymers
have several advantages to offer over regular polymers.
The wealth of metals available together with many donor ligands allows for a virtually innite number of
combinations. Network structures can be made with
metal centers that coordinate more than two ligands.35
The incorporation of lanthanides has led to photoactive
coordination polymers.36 Ligand-exchange kinetics,
which to a large extent determine the mechanical properties of the polymer, can easily be altered to generate
softer or tougher materials.3739
The combination of stoichiometric amounts of a
bifunctional ligand and a metal that can accommodate
two donor atoms can lead to linear polymers and
cyclic structures. Reversible coordination polymers are
equilibrium systems, and so cyclic and linear species
interconvert. Theory on cyclization40,41 shows that
such systems are characterized by a critical concentration. Below this concentration, only cyclic oligomers
are present, whereas above this concentration, all the
additional material leads to the formation of linear
species with a concentration-dependent degree of polymerization. To form high-molecular-weight polymers,
either high concentrations or long monomer lengths are
required. One of the specic features of reversible
polymers is that in solution, the average degree of
polymerization is low and the materials are easy to
process, whereas in the melt, concentrations are very

high and the equilibrium shifts toward high degrees of

polymerization, giving rise to mechanical properties
typical for entangled polymers (see Fig. 5).

REVERSIBLE MECHANOCHEMISTRY OF
COORDINATION POLYMERS
We have developed high-molecular-weight linear coordination polymers by the complexation of diphenylphosphine telechelic polytetrahydrofuran with palladium(II) dichloride42 (see Fig. 6). At a concentration of
1.5 mM in toluene, an equilibrium mixture was
obtained that contained monomeric and dimeric cycles,
as well as high-molecular-weight material [peak molecular weight (Mtop) * 2.5  105 g/mol, degree of polymerization * 35].
This solution was sonicated for 1 h, and during the
experiment, samples were analyzed with size exclusion
chromatography (see Fig. 7, left). Upon sonication, the
molecular weight distribution shifted toward lower
masses. Interestingly, leaving the mixture standing for
a day caused the ring-chain equilibrium to revert to its
original composition. The equilibration kinetics of
coordination polymer 4a have a half-life of approximately 13 h.33 This process is highly reversible, as
proven by sequential periods of sonication (1 h) and
equilibration (23 h) of samples (see Fig. 7, right).
The reduction in the molecular weight can be
caused either by the introduction of new end groups or
by the formation of cyclic polymers. Furthermore,

Figure 6. Coordination polymers based on diphenylphosphine (4a) and dicyclohexylphosphine

(4b), telechelic polytetrahydrofuran, and palladium(II) dichloride. p degree of supramolecular
polymerization.
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5451

Figure 7. Size exclusion chromatography traces of samples taken during 60 min of sonication
of coordination polymer 4a (left) and weight-average molecular weight (Mw) during ve cycles
of 1-h sonication and 23-h equilibration (right).

because the reduction is reversible, no bonds are permanently broken, and this means that the polytetrahydrofuran chains remain intact. This also implies that
only the reversible palladiumphosphorus bonds are broken. Coordinatively unsaturated palladium complexes
are therefore produced by the application of mechanical
forces to the coordination polymer (see Fig. 8).

ULTRASOUND-INDUCED
LIGAND EXCHANGE
To perform chemistry with ultrasound-induced ligand
dissociation, it is necessary to assess the reactivity of
the species formed and to quantify the scission rate.
The size exclusion chromatography measurements give
us data on which polymers break rst and in what polymer lengths this results. However, it is difcult to
obtain quantitative data from this technique because of
the formation of cyclic polymers with different hydrodynamic volumes43 and repolymerization of the broken
polymers. Therefore, a new method of quenching the
broken polymers was developed.44 A kinetically inert
coordination polymer (4b; Fig. 6), based on dicyclohexylphosphine ligands, was prepared. In the presence
of a kinetically labile palladium(II) dichloride bis(dodecyldiphenylphosphine) complex (5), heterocomplex
formation can occur only when the dicyclohexylphosphine ligands are dissociated through ultrasonic scission. The process is schematically depicted in Figure
9. Upon the formation of a heterocomplex, the polymer
chain is terminated and cannot repolymerize. Because
of the two different phosphorus atoms in the heterocomplex, distinct signals can be identied in 31P
NMR, which allow the easy quantication of the scisJournal of Polymer Science: Part A: Polymer Chemistry
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sion process. Furthermore, because the liberated phosphine ligands rapidly react with stopper molecules, cyclization and redistribution reactions are suppressed,
and size exclusion chromatography can now be used
for quantication. After prolonged sonication, up to
50% of the bisdicyclohexylphosphine complexes in the
coordination polymer were converted into heterocomplexes.
Apart from merely reversibly changing the molecular weight of a polymer solution, coordination chemistry also can now be controlled by ultrasound in this
way. The use of mixed ligand complexes in catalytic
reactions such as hydrogenations has received much
attention lately.45,46 The current way of applying these
heterocomplexes is the preparation of statistical mixtures of homo- and heterocomplexes. Ultrasoundinduced ligand exchange can selectively produce a specic heterocomplex. Moreover, by sonicating during
the reaction, one can ensure that homocomplexes will

Figure 8. Ultrasonic scission of the coordinative palladiumphosphorus bond, leading to the formation of a free
phosphorus ligand and a coordinatively unsaturated palladium
center (PTHF polytetrahydrofuran).

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Figure 9. Ultrasonic scission of kinetically stable coordination polymer 4b and subsequent

end capping with kinetically labile palladium(II) dichloride bis(dodecyldiphenylphosphine) complex 5.

be broken because they exceed the limiting molecular

weight required for scission.

CONCLUSIONS
Although ultrasound has been used for many decades
in synthetic polymer chemistry, techniques such as
ultrasound-induced polymerizations or block copolymer formation have not yet reached industrial maturity.
So far, the advantages of ultrasound, that is, low-temperature radical production and the replacement of
chemical initiators, do not offset these limitations.
Scaling up ultrasound-induced reactions is possible but
certainly not trivial because issues such as the efcient
creation of cavitation bubbles are difcult to achieve
on an industrial scale. A further limitation to the application of ultrasound is the fact that several effects such
as radical formation and polymer scission may take
place simultaneously.
The ultrasound-induced synthesis of block copolymers, either by the ultrasonic scission of a polymer in
the presence of a second type of monomer or by the
sonication of a mixture of two homopolymers, is a
promising method with several advantages over chemical synthesis. Issues that need to be addressed are the
prevention of bifunctional initiation and the scission of
the nal product.
The ultrasonic scission of polymers containing
weaker bonds such as azo linkages or coordinative
bonds is of enormous interest because it enables sitespecic cleavage. Synthesis based on specic cleavage
may result in better dened products. Although the
preparation of polymers with weak links introduces
complications by itself, their use in ultrasonic scission
may give access to block copolymers that are difcult
to obtain by conventional means.
The sonication of reversible coordination polymers
can be used to control ligand exchange, thereby giving
rise to novel approaches in coordination chemistry.
Heterocomplexes that are difcult to prepare in other

ways can be synthesized, but one can also imagine

other functional groups being brought together via
ultrasound-induced ligand exchange. When ways are
found to increase the scission rate, the ultrasonic scission of transition-metal-containing coordination polymers may even lead to applications in catalysis.

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