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The Melt&g Point of Polyethylene

Terephthalate
G. W. TAYLOR

The thermodynamic relation between heat, entropy of fusion and melting
point is used to calculate the melting point o] polyethylene terephthalate from
the melting points of several series of oligomers. The success of the method
depends on the assumption that the heat and entropy o] fusion per repeat unit
are constant, in a series of oligomers, and it is shown that, in the series of
linear diol oligomers higher than dimer, this assumption is approximately
justified. This finding is in accord with crystallographic data.

THE problem of the melting points of members of homologous series, and
the limiting melting point of the member of infinite chain length, has
occupied considerable attention for many years. King and Garner 1,
summarizing their work on the melting points of members of homologous
series containing methylene as repeat unit, showed experimentally in the
even-membered linear aliphatic saturated hydrocarbons, that if the number
of methylene units was ten or more, there was a constant increment in each
of the heat and entropy of fusion as methylene units were added to the
chain. That is to say, the melting point of a high member of the series
could be calculated from a relationship of the form
Tm=(Ho + nH~) / (So + ha1) (1)
where Tm denotes the melting point of the member with n methylene units,
H0 is the heat of fusion of (hypothetical) zeromer, So is the entropy of
fusion" of zeromer, H1 is the heat of fusion per methylene unit, Sx is the
entropy of fusion per methylene unit and n is the number of methylene
units in the molecule.
Hx and $1 were determined from the known melting points and heats of
fusion for a number of oligomers.
The melting point, T~, of the member of infinite chain length is readily
obtained from expression (1). Thus
T~=H1/S1
For the hydrocarbon containing an infinite number of methylene units
(polymethylene), King and Garner ~ calculated a melting point of about
135°C, very close to the actual melting point of polymethylene, 136"5°CL
Garner and his co-workers showed experimentally that expression (1)
could be used to calculate the melting point of a high polymer. In the
present work, it is assumed that expression (1) holds for oligomeric series
related to polyethylene terephthalate, and it is used to calculate the melting
point of the polymer from the melting points of the members of several
series of low oligomers.
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G. W. TAYLOR

The actual melting point of polyethylene terephthalate is still open to
dispute. Let us define the melting point as that temperature at which a
perfect crystal is in equilibrium with a liquid phase, It is well known that
high polymers are not completely crystalline, and hence the individual
crystallites are probably imperfect; but by a process of slow annealing, most
of these can be obtained as nearly perfect crystals. The melting point of
the nearest perfect crystals so obtained is thus closest to the 'true' melting
point as defined above. By several cycles of slow annealing, Hartley~ raised
the melting point of polyethylene terephthalate from the 'usual' value of
264°C 4 to 278°C.
The melting point of polyethylene terephthalate is here calculated from
the following series of oligomers: (0 the linear diols, (il) benzyl ester-ended
oligomers, and (iii) phenyl ester-ended oligomers. The values so obtained
are compared with the value obtained by Hartley, and possible reasons for
the discrepancies among the values are briefly discussed.

I. LINEAR DIOL OLIGOMERS
The melting points of a series of linear diol oligomers have been determined
by Zahn and Krzikalla 5.

Table 1. Melting points of linear diol oligomers

HOCH2CHzOIOC-~~COOCH2CHzO]nH
M. pt, °C M. pt, °A
109"5 383
169 442
201 474
2185 492

The melting points in Table 1 allow the following equations to be set up:
Ho + H1 =383 (So + $1) (2)
Ho + 2Hx = 442 (So + 2Sx) (3)
Ho + 3H1 =474 (So + 3S1) (4)
Ho + 4H~ = 492 (So + 4S~) (5)
We require H1/SI = T,~.
Equations (2) to (5) solved simultaneously give T~=571 ° (298°C).
Solved in two groups of three, corresponding to extrapolating the melting
points of monomer, dimer and trimer, and those of dimer, trimer and
tetramer, the equations give the following values of T.~"
(2) to (4), T~=581 °
(3) to (5), T,~=557 °
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THE MELTING POINT OF POLYETHYLENE TEREPHTHALATE

These findings are summarized in Table 2.
Table 2. Melting point of polyethylene terephthalate predicted from
diol oligomers
Oligomers used Predicted m. pt, (°C)
All four 298
Monomer, dimer, trimer 308
Dimer, trimer, tetrarner 284

It is seen that the series dimer, trimer, tetramer predicts a polymer
melting point of 284°C, a value close to Hartley's experimental value of
278°C. The discrepancy between any of the calculated values and the
experimental value may be due to any of the following causes: (a) the
experimental value is incorrect, (b) the oligomeric melting points are
incorrect and (c) the assumptions made in setting up equations (2) to (5) do
not hold. The latter two causes are now considered.

II. BENZYL ESTER-ENDED OLIGOMERS
The melting points of the benzyl ester-ended oligomers have been determined
by Zahn and SeideP, and are given in Table 3.
Table 3. Melting points of benzyl ester-ended oligomers

~CH zOO[C- ~ OOH
C2CH2O]O
n~OOCH2
C ~

M. pt, °C M. pt, °A
202 475
220 493
235 508

The melting points in Table 3 predict a polyethylene terephthalate
melting point of 400°C. This deviates widely from Hartley's value of 278°C.
The following exercise shows that small errors in the oligomeric melting
points can give rise to a large discrepancy between the calculated polymeric
melting point and the experimental value.
The twenty seven possible melting points, obtainable by varying each
of the oligomeric melting points by + 1°, range between - 5 2 ° A and
infinity. This wide range arises because, as the oligomeric melting points
are relatively close together, the variation of + 1 ° gives rise to dispro-
portionately large changes in the differences between successive melting
points within the oligomeric series; and this is reflected mathematically in
the set of three equations from which T~o is derived. Indeed, certain com-
binations of oligomeric melting points result in a constant increment in
melting point per chain segment as the series is ascended, and in this case,
the value of T~ is infinity.
The above result shows that in using the melting points of the diol
oligomers to calculate T~, part of the discrepancy between the two calcu-
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G. W. T A Y L O R

lated values of T,~o (308 ° and 2840C) and the experimental value (278°C)
may well be due to small errors in the oligomeric melting points. However,
part is probably due to physical differences between monomer and dimer,
and higher oligomers. These differences are now considered.

~III. CRYSTAL STRUCTURES OF THE LINEAR DIOL
OLIGOMERS
The crystal structures of the linear diol oligomers have been investigated
by Zahn and Krzikalla 5 using X-ray photography. The authors concluded
that, while the structures of all the oligomers and of polyethylene
terephthalate itself showed similarities, the structures of the monomer and
dimer could not be classed as the same as that of polyethylene terephthalate.
On the other hand, the principal reflections for trimer and tetramer were
much the same as those for polyethylene terephthalate. It is concluded that
the crystal structures of oligomers higher than dimer are much like that of
the high polymer, whereas those of monomer and dimer show some dis-
similarity. It is not surprising, therefore, that the melting points of dimer,
trimer and tetramer predict a more 'realistic' value for the melting point
of polyethylene terephthalate than do those of monomer, dimer and trimer.

IV. NATURE OF THE LINEAR DIOL ZEROMER
If n = 0 in the formula for the linear diol oligomers, the formula of zeromer
is obtained.
HOCH2CH20--H
Linear diol zeromer thus appears to be ethylene glycol itself. Though it
is tempting, it is probably not profitable, to press the comparison between
zeromer and glycol too far. Let it be observed that the predicted melting
point is -36°C; this is close (on the absolute scale) to the actual value
( - 13 °C).

V. THE PHENYL-ENDED OLIGOMERS
Yet a third o!igomeric series from which the melting point of polyethylene
terephthalate can be calculated is that of the phenyl-ended oligomers. The
melting point data are given in Table 4.

Table 4. Melting-points of the phenyl-ended oligomers

~[COOCH2CHzOOC~] nH
111
n M. pt, ° C M . pt, °A
0 5"5 278"7
1 73'5 346-7
2 114"5 387'7

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T H E M E L T I N G P O I N T OF P O L Y E T H Y L E N E T E R E P H T H A L A T E

The dimer has been prepared and characterized by Allan, Iengar and
Ritchie 7.
The data in Table 4 predict the melting point of (phenyl-ended) poly-
ethylene terephthalate to be 279°C. This is remarkably close to the experi-
mental value of 278°C obtained by Hartley3. The coincidence may be due to
mathematics--the differences between successive melting points in the
oligomeric series are relatively high--but physical reasons may be partly
responsible also. However, there is only a superficial resemblance between
the crystal structure of benzene and that of polyethylene terephthalate!

CONCLUSIONS
If it is assumed that the heat and entropy of fusion per repeat unit are
constant for polyethylene terephthalate diol oligomers corresponding to
dimer and higher, then the melting point of polyethylene terephthalate itself
can be calculated with a fair degree of accuracy from the melting points of
dimer, trimer and tetramer. The series monomer, dimer, trimer gives a
less satisfactory value probably because the crystal structure of monomer
(and to some extent, dimer) differs from that of the higher oligomers, and
polyethylene terephthalate itself.

The author thanks Dr C. W. )3unn and various o[ his colleagues [or
valuable discussions. He is particularly indebted to Mr P. L. Goldsmith
for mathematical assistance.
I.C.I. Ltd, Fibres Division,
Hookstone Road,
Harrogate, Yorkshire

(Received February 1962)

REFERENCES
1 KING, A. M. and GARNER, W. E. J. chem. Soc. 1936, 1368
2 MANDELKERN, L., HELLMANN, M., BROWN, D. W., ROBERTS, D. E. and QUINN, F. A.
J. Amer. chem. Scc. 1953, 75, 4093
HARTLEY, F. D. Private communication
4 HILL, R. and WALKER, E. E. J. Polym. Sci. 1948, 3, 609
ZAHN, H. and KRZIKALLA, R. Makromol. Chem. 1957, 23, 31
ZAHN, H. and SEIDEL, B. Makromol. Chem. 1959, 29, 70
: ALLAN, R. J. P., IENGAR, H. V. R. and RITCmE, P. D. J. chem. Soc. 1957, 2107

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