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Communications and Notes

Thermal Transitions o f Synthetic and Biological Polymers in
Bulk and in Solution

Ir~ A recent communication to this Journal Moraglio et al. ~ reported some
very small thermal transitions in polystyrene occurring in the bulk phase
as well as in solution. Using a sensitive dilatometric technique Moraglio
and Danusso located a transition region some 8°C wide and centred at
about 50°C both for the bulk polymer and for toluene solutions of 0"5 to
1-0 per cent concentration; one of their published curves for the bulk
polymer is reproduced as curve P in Figure 1. Bianchi and Rossi confirmed
the location of the solid-state transition by measuring the internal pressure
at different temperatures, whilst Liquori and Quadrifoglio observed optical
density anomalies around 50°C in solutions of isotactic polystyrene in
Moraglio et al. recognized the essentially intramolecular nature of these
phenomena, but considered that the basic molecular process would not be
a major conformational change 'analogous to helix-coil shape transitions
.... in proteins'. They suggested instead some unspecified molecular
change whose effects would appear equally in solution or in the bulk
material. In view both of the smallness of the transitions in polystyrene
and of their location well below the glass-transition point (ca. 105°C) it
seems likely that only very local molecular motions are involved, e.g. the
/3- and -/-mechanisms studied in polymer viscoelasticity2. In polystyrene
the phenyl gro,ups are thought to be responsible for the small/3-transition
and the even smaller -/-transition has been attributed 3 to the presence of
adjacent ----CH2-- groups resulting from head-to-head polymerization. The
measurements of Illers and Jenckel" show the fl-transition (at 1 cycle/see)
lying between 40 ° and 50°C and it may be suggested that this mechanism
underlies the phenomena discussed above.
However, the main point we wish to make in this Note is that the
phenomena of solution- and bulk-transitions occurring at the same tempera-
tures is also found in the protein systems collagen-saline 3 and keratin-
water s where the solution mechanism at least is certainly a helix-coil
Optical rotation or viscosity measurements on dilute solutions prepared
from mammalian collagen r show a pronounced helix-coil transition over a
very narrow range of temperature; yon Hippel and Wong ~ have shown that
AT, the difference in temperature between the points at which the transition
is one quarter and three quarters complete, is only 2 +0-5°C. The location
of this transition is in the range 35 ° to 40°C for dilute saline solutions near
to neutrality. Measurements of the apparent specific volume of the bulk
material in dilute saline show a small and narrow volume transition in the

same region of temperature. The curve C in Figure 1 is an example of such
a 'minor' transition for kangaroo tail tendon in 0"9 per cent saline solution
(the 'major' transition in this system occurs at a higher temperature and
consists of melting of the crystalline phase). There is thus a formal identity
with the situation in polystyrene.
The comparable behaviour of keratin is less dear, partly because the
native material is insoluble, and measurements of the thermal stability of
solutions have therefore to be carried out on a-helix-forming proteins
extracted after reduction of the disulphide bonds responsible for the
original insolubility. In this way optical rotatory dispersion measurements 9
showed a very broad helix-coil transition at pH 9"1, centred on 55°C and
with a A T of approximately 23°C.
Specific volume measurements on solid keratin immersed in water s also
showed a transition region between about 45 ° and 65°C, having a qualitative
resemblance to the behaviour reported by Moraglio and Danusso for bulk
polystyrene. Curve K in Figure 1 illustrates a typical result for Corriedale
wool in water.


..d Figure /--Minor thermal expansion
nO transitions in bulk polymer. C - -
Collagen-saline solution; P--Poly-
styrene (after Moraglio et al.1); K - -

)(3 40 60 80
Temperature, °C

Notwithstanding the obvious structural differences between the three
polymer systems considered, it is seen that in polystyrene and collagen, and
perhaps also in keratin, the solution behaviour can be detected in the solid
state. It may be considered that on statistical grounds there will be regions
where the molecular packing is exceptionally open and the local free volume
so large that the molecular segments experience little interaction from
neighbouring molecules. The material in these regions will undergo any
transition which occurs in a dilute solution, and this will be detected if a
sufficiently sensitive technique is used. The extent of these regions may be
small and dependent on the thermal history of the specimen, varying for

instance between specimens which have been abruptly quenched from a
higher temperature or more slowly annealed. This would account for the
smallness and variability of the phenomena described. Nevertheless,
phenomena of this type may be expected to be found quite generally in
either glassy or partly crystalline polymers.
One difference between the situations in polystyrene and in collagen is
that the solution transition for collagen is a first-order effect involving
helix-coil transformations of every tropocollagen molecule in the solution.
The smallness of the bulk transition thus indicates that only a small fraction
of the molecules can be involved. Nevertheless, if this fraction is directly
involved in carrying the mechanical stresses, it may be crucial in certain
physiological situations. For example, in collagen the phenomena of stress
relaxation and length recovery show marked changes TM at approximately
38°C, the temperature of the transition in question. Permanent damage to
the tissue may then be produced by straining at temperatures much above
this value, which is significantly very close to normal deep-body
A polymer which could provide a clear test of the foregoing ideas is
poly(cyclohexyl methacrylate). This gives a well defined viscoelastic transi-
tion below the glass-transition point which has been shown 11 to arise from
alternation of the cyclohexane ring between two isomeric chair forms of
the molecule. Other polymers containing the cyclohexyl group exhibit
similar '/~-mechanisms' at the same frequency-temperature combinations,
indicating that the mechanism is operating independently of the environ-
ment. On this supposition, dilatometry of the polymer in bulk or in dilute
solution should reveal the same transition, as with the materials discussed
Division of Textile Physics,
C.S.I.R.O. Wool Research Laboratories,
Ryde, Sydney, Australia.
(Received October 1964)

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