Hypercrosslinked Polystyrene
Hypercrosslinked Polystyrene
Hypercrosslinked Polystyrene
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
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
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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
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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
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
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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)
(1)
HYPERCROSSLINKED POLYSTYRENE
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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.
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
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(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.
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HYPERCROSSLINKED POLYSTYRENE
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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-
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