Hypercrosslinked Polystyrene: A Polymer in a Non-Classical

Physical State
ALEXANDER V. PASTUKHOV, MARIA P. TSYURUPA, VADIM A. DAVANKOV
Nesmeyanov Institute of Organo-Element Compounds, Russian Academy of Sciences,
117813 Moscow, Russian Federation

Received 15 June 1998; revised 23 February 1999; accepted 15 April 1999

ABSTRACT: Deformation and relaxation properties of hypercrosslinked polystyrene

networks have been studied by thermomechanical method at a uniaxial compression
using individual spherical beads of the polymer. The networks examined were prepared
by postcrosslinking of highly swollen beads of a styrene-0.3% DVB copolymer with
0.3 0.75 mole of monochlorodimethyl ether, which results in the introduction of 0.6 1.5
methylene bridges between each two polystyrene phenyl rings. The polymers obtained
are shown to belong neither to typical glassy materials, nor to typical elastomers.
Though no characteristic plateau of rubberlike elasticity was observed on the deformation curves of the beads, the polymers exhibit two fundamentally important features of
the rubberlike state: The deformations are large (up to 30 40% of the initial diameter)
and reversible. Relaxation of residual deformations, however, requires prolonged heating of the sample, or a cycle of swelling and drying. The deformation can start in the
temperature range from 270 to 1150C depending on pressure applied. The crosslinking degree in the range from 40 100% and higher does not affect noticeably the
behavior of the hypercrosslinked polystyrene. Nature of the high mobility of the hypercrosslinked network is discussed. 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys
37: 2324 2333, 1999

Keywords: hypercrosslinked polystyrene; thermomechanical curves; deformation;

relaxation; physical state of polymers

INTRODUCTION
Three physical states, glassy, rubberlike (or rubbery) and viscous-flow states, are well known to be
characteristic of amorphous linear high molecular
weight polymers.1,2 The transition of polymers from
one state to another proceeds in response to changing temperature which affects the accumulated
heat energy of macromolecules and, therefore, their
mobility. Introduction of crosslinks between linear
chains of the polymer restricts the chain mobility,
which manifests itself in the elimination of the viscous-flow state and the shift of the glass transition
Correspondence to: A. V. Pastukhov (E-mail: davank
@ineos.ac.ru)
Journal of Polymer Science: Part B: Polymer Physics, Vol. 37, 2324 2333 (1999)
1999 John Wiley & Sons, Inc.
CCC 0887-6266/99/172324-10

2324

temperature, Tg, towards higher values. If the network was prepared in the absence of any solvent,
the entrapped entanglements or, which is the same,
interpenetration of network meshes are so significant that even a moderate amount of chemical
crosslinks can fully deprive the network of becoming elastic up to the temperature of chemical degradation. In styrene-DVB copolymers, such an elimination of the rubberlike state takes place at the
DVB content of above 25%. Concomitantly, such a
polymer does not swell with solvents, at all. However, a network does not necessarily need to lose its
mobility with increasing crosslinking degree, if the
conditions for the preparation of the network are
selected in such a manner as to substantially reduce
the interpenetration of the network meshes formed
in the process of crosslinking.

HYPERCROSSLINKED POLYSTYRENE

2325

Table I. Properties of Hypercrosslinked Polystyrene Networks

Run
1
2
3
4

Crosslinking
Degree
(%)
43
66
100
. 100

Amount of
Cross-agent
(mol/mol St)

S
(m2/g)

Swelling in
Toluene
(ml/g)

Swelling in
Methanol
(ml/g)

Residual Cl
(% wt)

0.3
0.4
0.5
0.75

90
750
1,000
1,300

2.3
2.8
3.0
3.0

1.6
2.5
2.7
3.0

,0.5
,0.5
0.6
1.0

Hypercrosslinked networks studied in this

work have been obtained by an extensive chemical postcrosslinking of polystyrene chains in
slightly crosslinked copolymer beads (0.3% DVB)
in the presence of an excess of solvent. Very large
amounts of -CH2- bridges, 0.6 to 1.5 per each two
phenyl groups, were introduced into the swollen
copolymer. The crosslinking degrees of networks
thus obtained are extremely high. If the crosslinking degree is defined as the portion of crossbridges in the total amount of structural units of
the network (i.e., the sum of the crossbridges and
unsubstituted styrene phenyl rings), then, involving 0.3 mole of a bifunctional reagent into the
process with 2 3 0.3 mole phenyl rings would
produce a material of a crosslinking degree of 100
3 0.3/[(0.3 1 (12 3 0.3)] 5 43%. A formal 100%crosslinking would result from consuming 0.5
mole of the reagent per 1 mole of repeat units,
whereas the use of 0.75 mole of the bifunctional
reagent would leave no initial polystyrene phenyl
rings unaffected and, moreover, would involve
half of them into participation in two crossbridges. As compared to the crosslinking densities
that high, the initial 0.3% DVB in the copolymer
was simply disregarded.
The bridges formed by each -CH2- group and
two phenyl rings have a structure of diphenylmethane and are therefore conformationally
rigid. Nevertheless, in spite of the high rigidity
and extremely high crosslinking density, the final
materials are capable of reversibly changing their
volume by a factor of 3 to 5 on swelling and
drying, which implies high mobility of the polymer network. Even more surprising is the fact
that the hypercrosslinked polystyrene readily
swells in any organic media, irrespective of its
thermodynamic affinity to polystyrene. Due to
this marked tendency of incorporating any organic matter, the hypercrosslinked polystyrene
provided a base for manufacturing a series of
novel adsorbents displaying unprecedented ad-

sorption capacities (see review3 and references

therein). They are used in large-scale industrial
adsorption technologies,4 as well as in analytical
chemistry for sample preconcentration and as
HPLC column packing materials.
However, the high mobility of hypercrosslinked
networks as well as the actual physical state of
hypercrosslinked polystyrene cannot be described
in terms of current theories of network elasticity.
This article deals with the physical properties of
the hypercrosslinked polystyrene networks as
studied by thermomechanical method on individual spherical beads. This technique usually gives
an idea of the physical state of the network over a
wide range of temperatures and reveals possible
phase transitions.

EXPERIMENTAL
The gel-type copolymers of styrene with 3 and
34% DVB and polydivinylbenzene were prepared
by conventional suspension polymerization using
0.6%-wt of 2,29-azo-bis-isobutyronitrile as initiator. Styrene was purified by vacuum distillation,
divinylbenzene (; 65% divinylbenzene total assay of isomers and ; 33% ethylvinylbenzene total
assay of isomers) and 2,29-azo-bis-isobutyronitrile
(both of Merk, Darmstadt, Germany) were used
without purification.
The hypercrosslinked networks have been prepared by crosslinking gel-type styrene-0.3% DVB
copolymer beads, fully swollen with ethylene dichloride, by means of monochlorodimethyl ether
in the presence of stannic tetrachloride as described elsewhere.5 The amount of the crossagent varied from 0.3 to 0.75 mole per one mole of
styrene repeating units (see Table I) and it was
completely used up in the crosslinking reaction .
The analysis of the liquid phase in the above
reaction mixture was performed by using gas
liquid chromatography technique. A Perkin

2326

PASTUKHOV, TSYURUPA, AND DAVANKOV

Elmer model Sigma 2000 gas chromatograph

(USA) was operated with a 25 m 3 0.1 mm ID
capillary column and flame ionization detector.
Bonded methyl silicone served as stationary liquid phase. The temperature of the column, the
injector, and the detector was 70, 90, and 100C,
respectively.
Infra-red spectra of polymers were recorded on
a Nicolet Magna IR Spectrometer (USA) using
pellets of KBr.
The swelling of polymers was determined by
weighting first the dry and then the swollen sample. The excess of solvent was removed from the
swollen polymer beads by centrifugation at 4,000
rpm for 15 min in a tube with a porous bottom.
The inner surface area, S, of dry polymers was
measured by the adsorption of argon at 2196C
(single-point BET-method).
The thermomechanical curves were recorded
using UIP-70 (Moscow, Russia) equipment. One
spherical bead of the crosslinked polymer with
the diameter of 0.7 6 0.03 mm was placed in a
cavity having a radius of 0.95 mm specially made
in a quartz plate. The uniaxial compression of the
bead was carried out with a quartz rod having a
complementary cavity of 0.89 mm in radius; heating rate, 5C/min. The relative change in the bead
size along the axis of compression, Dh, was calculated as:
Dh 5 ~D m 2 D!100/D o, ~%!

Figure 1. Thermomechanical curves for eight spherical beads of the sample 3. Loading, 400 g per bead.

loading of 0.5 g; heating rate, 5C/min. The relative change in the bead diameter DD, was calculated as:
DD 5 ~D 2 D o!100/D o, ~%!

(2)

where D, and Do are the current bead diameter,

and its initial diameter.

(1)

where D, Do, and Dm are the current bead size, its

initial diameter and its size in the moment of
applying the pressure, respectively. (Dm is
smaller than Do by about 4 7% due to the immediate elastic response of the bead). The diameter
of initial beads was measured under microscope
with the accuracy of 6 0.001 mm. Figure 1 demonstrates a superposition of thermomechanical
curves obtained for eight different beads of the
hypercrosslinked sample 3 in Table I. The reproducibility of measurements in this typical set of
curves amounts to 20C along the axis of temperature in the region of maximal slope of the curves
and 2 to 3% along the axis of deformation. In the
following, all measurements were performed using 3 to 5 hypercrosslinked beads. The reproducibility of measurements for the gel-type styrene-3% DVB copolymer is better, it amounts to
12C (in the transition zone from 90 110C) and
23% in the Dh-value.
The dilatometric measurements were performed using UIP-70 and spherical beads under a

RESULTS AND DISCUSSION

On the Structure of Hypercrosslinked
Polystyrene Networks
All samples of postcrosslinked polystyrene beads
obtained in this work (see Table I) represent typical hypercrosslinked networks. They exhibit two
fundamentally important properties which distinguish them from all gel type copolymers. First,
the samples have low density and are thus porous materials, the apparent inner surface area
being the higher, the higher the crosslinking degree of the network. Second, the polymers
strongly swell, i.e., increase in volume, not only
with the thermodynamically good solvent, toluene, but also with methanol, a typical precipitating media for linear polystyrene. The swelling
with the both above solvents increases with the
crosslinking degree. This phenomenon was earlier explained6 by that, when conducting the postcrosslinking reaction, the increase in the amount
of the cross-agent and the corresponding amount

HYPERCROSSLINKED POLYSTYRENE

of the catalyst in the starting reaction mixture

unavoidably results in the increase in the rate of
the chemical reaction between the cross-agent
and polystyrene chains. Taking into account that
the postcrosslinking of the initially highly swollen
beads is accompanied by certain shrinkage of the
beads and partial expulsion of the solvent (macrosyneresis), one can imagine that, with the rate
of reaction rising, less time is given for the solvent
to diffuse through and out of the shrinking beads.
With the rate of fixation of polymeric chains in
space being high, larger portions of the initial
solvent thus happen to be entrapped within the
bead. This decrease in the extent of the macrosyneresis during the crosslinking process of the gel
logically corresponds to the rising solvent uptake
ability of the final material when the latter is
taken in dry state.6
The crosslinking of polystyrene chains in swollen state by means of large amounts of rigid
bridges results in the formation of fully transparent homogeneous one-phase material, though
having a reduced density of about 0.7 g/cm3 (density of the initial styrene-DVB copolymer
amounts to about 1.05 g/cm3). Despite the high
porosity of the polymers, no signs of any supermolecular structure of the hypercrosslinked material could be revealed by electron microscopy.7
Inverse size exclusion chromatography testified
to the homogeneous distribution of cross-bridges.8
The pore size distribution of the swollen material
was found to display a sharp maximum in the
region of 1 nm, with only minor fraction of pores
larger that 2.5 nm in diameter.
Small angle X-ray scattering also confirmed the
one-phase nature of the hypercrosslinked network
prepared by crosslinking styrene-2% DVB copolymer beads with monochlorodimethyl ether to a
crosslinking degree of 100%.7 The initial gel-type
copolymer was found to scatter X-rays weakly. The
scattering intensity on both the dry and swollen
hypercrosslinked beads proved to be only slightly
higher. The total volume of scattering inhomogenieties in the final polymer was found to remain below
3 to 5%, whereas the real volume of voids in the dry
material, when estimated from the reduced density
of the latter, should amount to at least 30%. Conventional styrene-DVB copolymers with the total
porosity of a comparable size, scatter X rays much
more intensively.
To better characterize the hypercrosslinked
material, it would be important to determine experimentally its true crosslinking density, i.e., to
evaluate the ratio between the numbers of intro-

2327

duced bridges and remaining phenyl rings. First

13
C NMR analysis of the hypercrosslinked polystyrene arrived at a rather surprising result that
about 30 to 40% of phenyl rings (monosubstituted
benzene) escape additional substitution in the
polymer formally crosslinked to 100%.9 This could
be the case, if a significant portion of monochlorodimethyl ether taken as a crosslinking agent
would fail to react with polystyrene. However,
gasliquid chromatographic analysis of the liquid
phase in the reaction mixture shows that the concentration of the cross-agent decreases rapidly
and no traces of the ether can be detected in the
reaction medium after a couple of hours. Moreover, the final product contains very small
amounts of unreacted chloromethyl groups, only
(see Table I). Consequently, the cross-agent does
react with polystyrene with a really high degree
of conversion into -CH2- links. This implies that
the cross-agent attacks both the native and already substituted styrene units, and that bridges
more complex than of the diphenylmethane type
must also form in the network. In a material
crosslinked to formal 100% with the involvement
of 0.5 mole of the cross-agent per 1 mole of phenyl
groups, the amount of pendant monosubstituted
benzene rings should be equivalent to the amount
of tri-substituted benzene rings.
Unfortunately, infra-red spectroscopy does not
clear up the situation either. Figure 2 demonstrates
the FT-IR spectra for linear polystyrene and hypercrosslinked materials with varying crosslinking degrees. For all the hypercrosslinked samples, in the
range of out-of-plane vibrations, one can see one
large band at 815 cm-1 testifying to the formation of
p-disubstituted benzene rings. The intensity of this
band logically increases with the crosslinking degree. Two bands, one at 700 cm-1 and the other at
760 cm-1, are present in all spectra. In the spectrum
of linear polystyrene, these bands have equal intensity and characterize unambiguously the monosubstituted benzene rings. In the case of the hypercrosslinked networks, however, the absorption band
at 700 cm-1 is markedly stronger than that at 760
cm-1. These two bands could certainly belong to
monosubstituted (uncrosslinked) benzene rings, especially in the case of the polymer with the low
crosslinking degree of 43%. However, assignment of
these bands is ambiguous because they are known
to appear in spectra of 1,4-di and 1,2,4,-trisubstituted benzene, for example, in the spectra of pxylene or poly(p-methylstyrene).10 The absence of
any absorption band in the range 815760 cm-1
suggests that no 1,3,5-substitutions on benzene

2328

PASTUKHOV, TSYURUPA, AND DAVANKOV

Figure 2. FT-IR spectrum of (A) linear polystyrene; (BD), hypercrosslinked materials prepared by crosslinking styrene-0.5% DVB copolymer with 0.3, 0.5, and 1.0 mole of
monochlorodimethyl ether.

rings are present in hypercrosslinked polymers,

while the shoulder and the band at 893 cm-1 (for the
networks crosslinked with 0.5 and 1.0 mol of the
ether, respectively) give evidence that, possibly, the
hypercrosslinked networks incorporate a certain
amount of 1,2,4-trisubstituted benzene rings. A
small shift of polystyrene bands 1,500 and 1,600
cm-1 towards 1,511 and 1,607 cm-1, as well as the
band at 1,019 cm-1 confirm the above suggested
availability of 1,4- and 1,2,4-substitution on benzene rings in the hypercrosslinked networks.10,11
When considering the above results of the
chemical analysis of the reaction mixture and its
reaction product, combined with the information
provided by examining the latter by X-ray scat-

tering, gel permeation chromatography, IR and

13
C NMR spectroscopy, one arrives at the conclusion that the pore size distribution, i.e., the distribution of cross-bridges, is rather homogeneous
and that the portion of unreacted phenyl groups
in a network of a formal crosslinking degree of
100% is not large. In any case, the number of
pendant phenyls is really small in networks
crosslinked to higher densities by applying more
than 0.5 mole of the cross-agent.
Thermomechanical Analysis of Hypercrosslinked
Polystyrene
To understand peculiarities in the deformation
behavior of hypercrosslinked polystyrene, let us

HYPERCROSSLINKED POLYSTYRENE

Figure 3. Thermomechanical curves for styrene copolymers containing 3 % DVB (1,2), 34% DVB (5), polydivinylbenzene (6), and for the hypercrosslinked sample 3 (3,4). Loading, 10 g per bead (2,4,5) and 400 g per
bead (1,3,6).

first consider deformation properties of two typical representatives of standard networks, the geltype copolymers of styrene with 3 and 34% DVB
and polydivinylbenzene (Fig. 3). The 3% DVB incorporating copolymer exhibits two physical
states, glassy and rubbery, with a narrow transition zone in the range of 100C (glass transition
temperature), provided that the pressure applied
to the sample is small, i.e., 10 g per bead. The
increase in pressure to 400 g per bead causes a
shift of 10o in Tg towards lower temperatures,
because of developing of forced high-elasticity. It
also results in the increase in the deformation
extent from 17 to 40% when the copolymer
reaches the rubberlike elasticity. The highly
crosslinked conventional copolymer with 34%
DVB and polydivinylbenzene retain their glassy
state up to the temperature of chemical degradation, while only exhibiting small thermal expansion up to this point.
The hypercrosslinked bead with the crosslinking degree of 100% becomes noticeably deformed
under a loading of 10 g at 140C, already, that is
150 to 170C lower than the temperature of chemical degradation, 300 310C.12 Under a pressure
of 400 g (which, still, is 20 times smaller than the
breakdown loading at 25C), the deformation
starts at a temperature as low as 250C. Note,
the deformation of styrene-3% DVB copolymer
starts in the temperature zone almost 130C
higher.
The maximum Dh of the above 100% hypercrosslinked sample achieves a value as high as

2329

30% when the temperature approaches 300C.

Although this extent of deformation is characteristic of rubberlike elasticity (Fig. 3, lines 1 and 2),
no typical deformation plateau can be observed
(line 3). This statement is also valid for the whole
set of curves obtained at varying loading in the
interval from 10 to 450 g per bead examined (Fig.
4). All curves have a flat S-shaped form. The
position of inflection points (maximum on first
derivative curve) strongly depends on the pressure applied, steadily shifting some 200C towards lower temperatures with the force rising.
Interestingly, the rate of heating the sample,
ranging from 2.5 to 20C/min, does not tell practically upon the position of thermomechanical
curves (Fig. 5). Here, scattering in data remains
within the limits of reproducibility of measurements on different beads. On the contrary, the
glass transition temperature of linear polymers
and conventional slightly crosslinked networks is
well known to depend linearly on the logarithm of
heating rate. Indeed, in our experiments with
beads of the styrene-3% DVB copolymer, we also
observed a systematic shift in Tg amounting to
10C towards higher temperatures with the increase of heating rate, W, from 5 to 20C/min, as
in eq. (3):
1/T g 5 2.66 2 0.033 log W

(3)

Figure 6 illustrates another interesting peculiarity of thermomechanic curves of hypercrosslinked polystyrene, namely, that, with the

Figure 4. Effect of the loading on the form and position of the thermomechanical curves of the sample 3.

2330

PASTUKHOV, TSYURUPA, AND DAVANKOV

Figure 5. Effect of the heating rate on the position of

thermomechanical curves of the sample 3: (1) 2.5, (2) 5,
(3) 10, and (4) 20C/min. Loading, 400 g per bead.

crosslinking density increasing, there is no shift

of the inflection points toward higher temperatures. Rather an opposite tendency can be observed in that the noticeable deformation starts
at lowest temperatures for samples having highest crosslinking degrees. In the series of curves
presented in Figure 6, only the decrease of ultimate deformation at 300C with the rise in the
crosslinking degree can find a trivial explanation.
As shown in Figure 6, the deformation of all
hypercrosslinked beads becomes markedly higher

Figure 6. Effect of the degree of crosslinking on the

position of thermomechanical curves; the numbering of
curves corresponds to that of samples in Table I. Loading, 400 g per bead.

Figure 7. Thermomechanical curves of the sample 3

registered under constant loadings of (1) 400 and (3)
50 g, and under a varying (every 3 min.) loading between 400 g and 50 g.

above 100C. However, this phenomenon is not

related to trivial transition of polystyrene segments from glassy to rubberlike state. The very
nature of deformation of the hypercrosslinked
material differs fundamentally from that of conventional networks under rubberlike elasticity
conditions. This follows from Figure 7 where thermomechanical curves for beads of sample 3 were
registered under three different protocols,
namely, under constant loading of 400 and 50 g
and under a periodically (every 3 min.) varying,
between 400 g and 50 g, loading. The total deformation of a bead obviously consists of a constant
(at any temperature) portion of elastic deformation and an increasing (with the temperature rising up to 250C) portion of non-elastic deformation. The non-elastic residual deformations are
responsible for a gradual change of the form of the
initially spherical bead. When deformed with a
flat rod, instead of the rod with the cavity, we can
easily see under a microscope a flat circular print
on the top of the bead, without any signs of destruction or fragmentation of the sample (provided that the temperature of the experiment did not
exceed 250C). This picture could resemble plastic
deformation of a bead prepared from a linear
polymer. However, the residual deformation of
the hypercrosslinked network cannot be regarded
as plastic. Figure 8 gives sufficient evidence for
the reversibility of residual deformations of sample 3. Several hypercrosslinked beads, one by one,
were heated to 136C under a pressure of 400 g
and then were allowed to cool down to ambient

HYPERCROSSLINKED POLYSTYRENE

Figure 8. Effect of pretreatment of the sample 3 on

the position and form of thermomechanical curves: (1)
control sample 3; (2) the sample heated up to 136C
under a loading of 400 g and relaxed at 164C for 2 h
without pressure; (3) the sample heated up to 136C
and then cooled under a loading of 400 g (12% residual
deformations), then subjected to swelling and drying;
(4) the sample heated up to 136C and then cooled
under a loading of 400 g (10% residual deformations).
Loading, 400 g per bead.

temperature under that pressure. In the course of

a second cycle of heating under the same pressure, the deformation of thus pretreated beads
was observed to start at 136C only (Fig. 8, line 4).
The sample obviously stored the information of
the first cycle of deformation, possibly, by achieving higher mechanical strengths along the axis of
compression. Such a storage of information would
be unthinkable in a plastically deformed sample.
Lines 2 and 3 in Figure 8 demonstrate that both
the non-elastic residual deformations and the
memory effect in the above precompressed samples largely disappear if the deformations are allowed to relax. Line 2 represents the behavior in
the second cycle of deformation of beads relaxed
at 164C for 2 h without any pressure applied.
Line 3 relates to another set of beads with frozen deformations that was allowed to swell with
acetone, followed by washing with water and drying at 80C. As can be seen from Figure 8, the
deformation behavior of the precompressed and
then relaxed samples does not differ substantially
from the curves registered in the first cycle of
deformation (Fig.8, line 1). Taking into account
normal scattering of results registered for individual beads, one can state that the residual fro-

2331

zen deformations in hypercrosslinked materials

are completely reversible.
Beads of sample 3, including those differing in
their prehistory, were finally subjected to dilatometric analysis (Fig. 9). Normally, with minimum
pressure applied, the bead would slightly and linearly expand with the temperature rising to about
180C, after which a tendency for the bead to shrink
becomes evident (Fig. 9, line 1). A bead with frozen
(according to the above described protocol) residual
deformations, starts to intensively expand at a temperature slightly exceeding the ambient temperature (Fig. 9, line 4). It should be noted here that
relaxation of predeformed conventional networks
would require the temperature to reach the Tg
point. Substantial expansion is also characteristic of
the sample which frozen deformations were allowed
to partially relax for 2 h at 164C (Fig. 9, line 2). Full
relaxation would obviously require more time or
higher temperatures. On the contrary, swelling
with acetone fully returns all properties of the precompressed bead to normal levels (Fig. 9, line 3). In
total, Figure 9 speaks for full reversibility of nonelastic residual deformations inflected in hypercrosslinked polystyrene materials under temperatures below 250C. Above this point, probable chemical degradation of strained bonds followed by an
irreversible rearrangement of the network cannot
be excluded. Special experiments showed that heating the material to about 220C results in emergence of many unpaired paramagnetic electrons.
Nature of Mobility of Hypercrosslinked Networks
Chemical nature of conventional styrene-DVB copolymers is very similar to that of the hyper-

Figure 9. Thermodilatometric curves for the sample

3; numbering as in Figure 8.

2332

PASTUKHOV, TSYURUPA, AND DAVANKOV

crosslinked polymer obtained by introducing numerous methylene bridges between linear polystyrene chains. These two materials, however,
differ fundamentally in the network topology and,
as a consequence, in all properties which involve
rearrangement of the network, such as swelling
and mechanical deformation.
Conventional gel-type styrene-DVB copolymers are prepared in the absence of any solvent.
Their network meshes are fully stuffed with fragments of other polymeric chains which, in the dry
material, are densely packed and exert strong
attractions to each other. Under these conditions,
the material can only swell with thermodynamically good solvents which are able to replace the
strong polymerpolymer interactions with still
stronger polymersolvent interactions. In a hypercrosslinked gel, which is prepared in excess of
a good solvent, entrapped entanglements and interpenetration of network meshes are much less
abandoned. If the crosslinking degree is high and
the cross-bridges are conformationally rigid, the
polymeric chains are not in position to attain a
dense packing after removal of the solvent from
the gel. The final dry material, while remaining a
homogeneous polymeric phase, exhibits low density and substantially weakened polymerpolymer interactions. It is of fundamental importance
that the rigid open-work structure of the hypercrosslinked polymer exerts high inner stresses
which are caused by the unrealized desire of polymeric fragments to further approach each other
and minimize unsaturated van der Vaals potentials of dispersion forces. Relaxation of these inner strains can be achieved by expansion of the
network, only, and this is a strong additional driving force for the network to swell. The swelling
takes place on contacting any liquid, largely irrespective of its thermodynamic affinity to the polymer. It has been shown13 that the hypercrosslinked polystyrene does even swell with argon vapors at a temperature of liquid nitrogen. It
is not surprising therefore that a glassy state is
not characteristic of the hypercrosslinked polystyrene, at least, not in the temperature range from
270 to 1350C scanned in conventional thermomechanical technique. Substantial deformation of
the material can easily be accomplished in any
point of this temperature interval, depending on
mechanical force applied (Fig. 4). Accordingly, the
rise in the deformation extent with the temperature increasing has little in common with the
normal sharp transition from a glassy state to
rubberlike state which is exemplified in Figure 3

for the conventional gel-type styrene-3% DVB copolymer. Certainly, there are polymeric systems
known which are characterized by a broad temperature zone of transition from a glassy state to
rubberlike state. This is the case with heterogeneous two-phase systems, such as interpenetrating networks composed of partially compatible
components, semi-interpenetrating networks, or
polymeric blends. Here, phase transitions represent superposition of several transition zones corresponding to all segregated constituent components.14 16 This situation is not applicable to hypercrosslinked networks which are homogeneous
one-phase structures and should accordingly exhibit a much narrower zone of transition.
Besides, the inflection point on thermomechanical curves of the hypercrosslinked sample 3
changes its position along the axis of temperature
in the temperature range of about 200C, depending on the pressure applied. Though the forced
high-elasticity deformations for a butadiene resin
and polymethyl methacrylate are known17 to develop in a broad range of 70 and 90C, respectively (from the temperature of the brittle point to
the glassy transition temperature), still, the development of the forced high-elasticity in the
range as broad as 200C, as is the case with
hypercrosslinked polystyrene, seems to be unrealistic. Finally, the abovementioned inversed dependence of the deformation ability on the degree
of crosslinking is another feature of the hypercrosslinked material that cannot be explained in
terms of a glassrubber transition.
Hypercrosslinked polystyrene cannot be ascribed
to materials in rubberlike state, either. Though two
most important features of rubberlike elasticity,
namely, large values of deformations and reversibility of deformations, are characteristic of the hypercrosslinked polystyrene, still, the non-elastic part of
deformation is definitely too high. Reversal of this
non-elastic part of deformation requires a long heating of the material or treating the sample with a
solvent. Such kind of hindered relaxation is not
characteristic of typical rubbers.
A special and very important question is
whether removal of the solvent from the synthesized hypercrosslinked polymeric gel results in
the dry polymer that adopts an equilibrium state.
On the one hand, gradual contraction of the initially swollen gel slows down and finally stops in
the moment where the rising inner stresses in the
conformationally distorted network meshes prevent further contraction of the polymer phase. In
the final low-density material, these stresses are

HYPERCROSSLINKED POLYSTYRENE

definitely equilibrated with the unsaturated attraction forces of the chain fragments. On the
other hand, such an equilibration can be achieved
in many different sets of conformations. Uniaxial
compression of the sample distorts the initial conformations of such an equilibrated network and
results in replacing the initial strong interactions
in the initial contact points of polymeric chains by
a new set of contacts and interactions. The new
shape of the bead with non-relaxed residual deformations may also be characterized by a new
local minimum of the total network energy.
Therefore, even a prolonged heating of the mechanically deformed sample should not necessarily result in a complete shape relaxation to the
initially spherical bead. From this point of view,
the dry hypercrosslinked network may well exist
in several quasi-equilibrated states, depending
on the pre-history of the sample. Only a cycle of
swelling and drying of the precompressed sample
must fully restore its inner conformational structure and spherical outer shape, which, indeed,
corresponds to experimental findings.

CONCLUSION
Hypercrosslinked polystyrene represents a new
type of polymer networks which physical state
cannot be defined in generally accepted terms. We
can conclude with confidence that in a very wide
range of temperatures, from 270 to 1300C,
these highly crosslinked homogeneous networks
exhibit high deformation ability with no features
of a glassy state. The high mobility of the networks is realized through a cooperative conformational rearrangement of the whole ensemble of
network meshes. The mobility of hypercrosslinked open-work networks is facilitated by
strongly diminished between-chain interactions
and low degree of the interpenetration of network
meshes, rather than any residual sequences of
phenyl groups that escaped the postcrosslinking
process for one reason or another. The probability
of existence of such residual flexible linear segments is negligible, at least with networks
crosslinked more densely than just to 100%. Since
these networks undergo deformations as easily as
the products crosslinked to 43%, the very issue of
the real degree of crosslinking of networks considered becomes of minor importance. Much more
attention should be paid to the topological pecu-

2333

liarities and inner stresses inherent to the hypercrosslinked state of polymers.

This work was carried out with the support of the Civil
Research and Development Foundation, grant RC
1-179. The authors acknowledge Professors Boris V.
Lokshin for registering FT-IR-spectra and Alexander
N. Ozerin for examining the hypercrosslinked polymers
by small angle X-ray scattering technique.

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