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EXPERIMENTAL
The polyethylene terephthalate used was essentially amorphous film, 0.008
in. in thickness. Preliminary measurements showed it to have a density of
l'340g/cm ~ at 25°C, corresponding to a degree of crystallinity of 4-2 per
cent. The following liquids were used: hexane, carbon tetrachloride, ethanol,
n-butanol, benzyl alcohol, acrylonitrile, dioxan, ethyl formate, m-cresol,
aniline, nitromethane, nitroethane, acetic acid, dimethyl phthalate, benzene,
toluene, nonyl methyl ketone, n-amyl methyl ketone, ethyl methyl ketone
and acetone. The best available grades were further purified, dried by
appropriate agents and fractionally distilled before use.
315
W. R. MOORE, A N D R. P. SHELDON
RESULTS
Plots of density against time of immersion are shown in Figure 1. An
equilibrium density is reached with each liquid and these densities are
collected in Table 1 together with corresponding percentage crystaUinities
x~ obtained from
x,-- 100 (d~ -dA) / (de -dA)
where dA is the density of the completely amorphous polymer, taken5 to be
1-335 and de that of the completely crystalline, taken 6 as 1"455. Values for
316
THE CRYSTALLIZATION OF POLYETHYLENE TEREPHTHALATE
-- s ~ Dioxan
,
12
I
Time
+
×o--e~
l
24
,
h
"t"
1"38[~ ~ I ~ ~ ~o-
12 Time 24 h
1.40[- x ~ Benzene ~ Toluene
I.--I-"
D
1'34g I I I
1 Time 2 3 day
.x-
1"401- Benzyl alcohol ~x~ ~-'x" Dimethyl phthalate o-.
1'36i-~
1 " 3 M I I I I
0 I 2 3 4
Ti me day
Table 1
Equilibrium values of density, swelling and degree of crystallinity
317
W. R. M O O R E A N D R. P. SHELDON
the ketones are somewhat lower than those previously reported" and the
reason for this is not clear. As mentioned previously, some polymer, pre-
sumably of low molecular weight, was soluble in m-cresol. By taking into
account the weights of precipitated and undissolved polymer and also a
presumably proportional loss of m-cresol from the sample by extraction
with ethanol, corrections were applied to the density and swelling of the
undissolved polymer. Since the soluble fraction may behave differently
from the insoluble and very low molecular weight polymer may not be
precipitated by ethanol the corrected value given in Table 1 should be
regarded as approximate. The development of crystallinity was always
accompanied by increasing opacity of the film and, when absorbed solvent
was removed, by increased brittleness. The latter effect has been previously
noted 7 after prolonged heating in an aqueous dye bath at 100°C. Values of
equilibrium swelling are also given in Table 1.
DISCUSSION
Figure 1 shows that the rate of increase of density and hence of crystallinity
varies markedly with the liquid. In some cases crystallization is rapid while
in others it occurs at a rate convenient for measurement. Figure 1 also
shows that although molecular size may be a factor affecting the rate of
crystallization it is not the only one. Dioxan, ethyl formate, acrylonitrile,
m-cresol, aniline, nitromethane and nitroethane induce much more rapid
crystallization than benzene, toluene, acetic acid, benzyl alcohol and
dimethyl phthalate. Kinetic studies of this induced crystallization will be
discussed in a later communication and are not further considered here,
but it may be noted that the rate of disappearance of available amorphous
content at any given time seems to follow a first order equation.
The equilibrium values of density and crystallinity also vary with the
liquid. The non-polar hexane and carbon tetrachloride do not induce
crystallinity and neither do ethanol and n-butanol. The polarizable aromatic
hydrocarbons benzene and toluene do so, however, and so does benzyl
alcohol. Other liquids inducing crystallinity are polar but there seems to
be no obvious relationship between the equilibrium density of the polymer
and the polarity of the liquid. Results for acetone and n-amyl methyl ketone
and for nitromethane and nitroethane suggest that molecular size may be a
factor with liquids of the same type but this is not general.
Table 1 shows that, in general, the greater the equilibrium density the
greater the swelling of the polymer although density and swelling are not
linearly related. Swelling may be regarded as a measure of the interaction
between polymer and liquid and the development of crystaUinity may
depend on such interaction. Figures 2 and 3 show equilibrium density and
swelling respectively as functions of the solubility parameter 3 of the liquid.
3 =[(L, - R T ) / V ] }
where Le is the molar latent heat of vaporization of the liquid and V is
molar volume, both at the absolute temperature T. Values of 3, which are
given in Table 1, were taken from published values 8' 9 or calculated using
values of Le obtained by use of the Hildebrand rule 1°. The difference
318
THE CRYSTALLIZATION OF POLYETHYLENE TEREPHTHALATE
between the solubility parameters of a liquid and a not too polar amorphous
polymer can be related to the heat change in their mixing and the interaction
of polymer and liquid will therefore depend, in part, on the solubility para-
meter of the latter.
"E 1"42
..90
1-40
Figure 2 - - Equilibrium
-~ i.3B density as a function of
C
Q solubility parameter of
liquid
1-36
oJ I I I I
7 8 9 10 11 12 13
Solubility parameter (cal/cm3) ~h
120
I00
80
~C
60- Figure 3--Equilibrium swel-
03 ling as a function of solu-
>o 4 0 - bility parameter of liquid
20
0
7 8 9 10 11 12 13
Solubility parameter (cal/cm3)Y2
P o l y m e r R e s e a r c h Laboratories,
D e p a r t m e n t o f C h e m i c a l Technology,
Institute o f Technology, Brad[ord, Y o r k s .
( R e c e i v e d M a r c h 1961)
REFERENCES
1 SPENCE, J. J. phys Chem. 1941, 45, 401
2 BAKER, W. O., FULLER, C. S. and PAPE, N. R. J. Amer. chem. Soc. 1942, 64, 776
KOLB, J. and IZARD, E. F. J. appl. Phys. 1949, 20, 571
a MOORE, W, R., RICHARDS, D. O. and. SHELDON, R. P, J. Text. lnst. 1960, 51, T438
5 THOMPSON, A. B. and WOODS, D. W. Nature, Lond. 1955, 176, 78
BUNN, C. W. in Fibres jrom Synthetic Polymers edited by R. HILL. Elsevier:
Amsterdam, 1953
r SHELDON, R. P. Unpublished Results
8 MOORE, W. R., EPSTEIN. J. A., BROWN, A. M. and TIDSWELL B. M. J. Polym.
Sci. 1957, 23, 23
9 BURRELL, H. lnterchemical Review, 1955, Spring, 3
~°H1LDF.aR.'e~D, J. L." and SCOTT, R. L. Solubility of Non-Electrolytes, 3rd ed.
Reinhold : New York, 1950
11 BARKER, J. A. and SMITFI, F. J. chem. Phys. 1954, 22, 375
15 ALLINGHAM, M. M., GILES, C. H. and NEUSTADTER, E. L. Disc. Faraday Soc. 1954,
16, 92; ARSHID, F. M., GILES, C. H. and JAIn, S. K. J. chem. Soc. 1956, 260, 1272
~3 MOORE, W. R. J. Soc. Dy. Col. 1958, 74, 500
14 MOORE, W. R. and RUSSELL, J. J. Colloid Sci. 1953, 8, 243
~5 Aus. Patent No. 36684
~ MOORE, W. R. and RUSSELL, J. J. appl. Chem. 1954, 4, 369
321