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Terephthalate
G. W. TAYLOR
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 °
544
THE MELTING POINT OF POLYETHYLENE TEREPHTHALATE
M. pt, °C M. pt, °A
202 475
220 493
235 508
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.
~[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
546
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.
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
547