Edward 1.

McCaRery'
Lowell Technological Institute
Kinetics of Condensation Polymerization
Lowell, Massachusetts 01850
Preparation o f a polyester

condensation polymerization (1) is char- measurement of the quantity of water produced, and it
acterized by the stepwise or progressive conversion of a will be confirmed by titration of the unreacted acid.
monomer with two reactive end groups to higher mo- Because the temperature of the reaction must be in-
lecular-weight homologs which, themselves, retain two creased periodically to produce high molecular-weight
reactive end groups. Condensation polymerization can product within the limits of the laboratory period, one is
be accompanied by the formation of a low-molecular- presented with an excellent opportunity to study the
weight by-product, as with polyesterification rate of polyesterification a t several temperatures,
thereby, to evaluate the energy of activation for the
process.
or, as with polyurethane formation, the polymer can be Experimental
the only product of the reaction
OCN(CH2).NC0 + HO(CHn)aOH (OCN). . . -
+oCNH(CH,).NHCoo(CH1)boff. . . H
A 1-1four-necked reaction kettle (see figure) provided
with a heating mantle is charged with 35 ml of decalin
and with 1 mole of the prescribed di-
Kinetically, polyesterifications of either type should basic acid2 (adipic, fumaric, maleic,
be identical to esterification provided that both the ~hthalic, or succinic acids); or if
increase in molecular weight accompanying the forma- ananhydride (maleic, phthalic, or
tion of the polyester does not alter the reactivity of succinic) is to be employed, the charge
the end groups, and the increase in viscosity associated should contain 0.5 mole of glycolS
with polymerization does not cause the process to be- (ethylene, diethylene, triethylene,
come diffusion controlled. The first objection was set tetraethylene, or other polyethylene
aside by Skrabal and Singer (8) who demonstrated that glycols) in addition to the anhydride
the influence which one carboxyl group exerts upon the and decalin. The rheostat should
other in dibasic acids rapidly disappears as the number be adjusted to permit maximum
of methylene groups separating the carboxyl groups safe heating of the mantle, and the
increases. Flory's (3) work on the kinetics of poly- charge should be preheated while
ester formation dispelled the second. the rest of the apparatus is being
The reaction-rate constant for polyesterification can assembled.
be calculated conveniently from the equation (4) : The reaction kettle is fitted with a
mechanical stirrer, a 25-1111 graduated
distillation-trap topped by a condenser,
when an external catalyst such as p-toluenesulfonic and a nitrogen inlet tube. A thermo-
Apparatus for poly- couple wire contained in a glass sleeve
acid is used. Because the quantities 5, (the number- e5ter formotion.
average degree of polymerization) or 111-p (where p is is connected to a pyrometer and is
the extent of reaction) are dimensionless, klco assumes positioned so that the wire will make
the dimensions of time-'. The pseudo-second-order contact with the reaction m i x t ~ r e . ~The distillation-
rate constant, k', and the actual rate constant, k (where trap should be filled with decalin to permit a reasonably
k = kf/[catalyst]), can be written.in more conventional constant weight to be maintained in the flask as the reac-
terms if both co and [catalyst] are expressed as tion proceeds.
mmoles/g. One mole of glycol (or the additional 0.5 mole of
The progress of the reaction will be determined by glycol if an anhydride is the coreactant) is introduced
into the reaction kettle along with 0.17 g (1 mmole) of
1 The material in this article is derived from the author's forth- p-toluene-snlfonic acid. If the acidic comer is un-
coming book: "Laboratory Preparation for Macromolecular saturated, 0.1 g of hydroquinone also should be added a t
Chemistry," to be published by the McGraw-Hill Book Company
and is used with the permission of the publisher. this point.
The total charge should he restricted to about 250 g. There- The temperature of the reaction should be permitted
fare, with the higher molecular-weight glycols, the charge must to rise rapidly until reflux commences; usually this will
he reduced proportionately. occur somewhere between 130'-180°C. Thereupon,
'The half mole of glycol is added at this point if anhydrides
rtre used in order to moderate the relatively vigorous anhydride-
the temperature should be maintained constant until
glycol reaction. one fourth of the total water of reaction has been col-
A long-stem thermometer also is satisfactory. lected in the distillation trap. The water level in the
Volume 46, Number 7, January 1969 / 59
trap should be recorded at 1-min intervals during this perature then is raised an additional lo0, and the
period. If the water-decalin interface is indistinct, a quantity of water evolved a t the usual 1-minintervals
few drops of bromthymol blue indicator solution may is observed until the rate of reaction perceptibly has
be added to the trap; the indicator will become con- diminished. The polyesterification reaction can be
centrated at the interface. completed a t the highest temperature attainab1e.O
After the first quarter of the water of reaction has Formulations which contain unsaturated-acid comers
been collected, the temperature of the reaction is per- cannot he permitted to react to their theoretical end
mitted to rise quickly about 10" where the temperature points since side reactions cause crosslinking and its
again is maintained. The quantity of water evolved consequence-gelation. If the reaction mixture thick-
again should be recorded a t 1-min intervals. After ens significantly in a short time and it ascends the
about one half of the water has been collected, a glass stirrer shaft, additional glycol should be introduced
tube is inserted into the kettle and about 2 g of the hot quickly to permit ester-interchange reactions which will
resin sample is withdrawn and is deposited into a small, serve to inhibit the crosslinking reaction of the decom-
weighed flask. The nitrogen-inlet tube is replaced and posing resin and will facilitate the removal of the resin
the temperature of the reactiou is permitted to rise an from the kettle. R4easurements made beyond the gel
additional 10". The reaction is conducted isothermally point are meaningless; the partially gelled resin should
a t this new temperature until about three quarters of he discarded.
the water has distilled. The decalin-polyester mixture will separate upon
Meanwhile the exact weight of the withdrawn resin is being cooled to room temperature. A characteristic
determined by difference, and the resin is diluted with resin sample will be obtained merely by decanting the
10 ml of acetone. After the sample has dissolved, i t supernatant decalin layer.
is titrated with 0.8 N methanolic IiOH solution to a Four different pseudo-second-order rate constants
phenolphthalein end-point! The extent. of reaction as (k') and four actual rate constants (k)can be determined
is determined by tit,ration should be compared with the from the data. Only those data secured isothermally
value calculated from the evolved water of reaction. should be included in the calculations. The energy
Before the temperature again is increased, a second of activation and the Arrhenius A factor for each
sample of resin is withdrawn and titrated. The tem- polymer prepared also can be evaluated.
Literature Cited
6Because of the presence of hydroquinone, the typical phenol- (1) MARK,H. and WHITBY,G . S., (Editors), "Collected Works of
phthalein end-point will not be observed. An easily discernible Wallace Hume Carothers on High Polymeric Substances,"
change from light yellow to violet-brown or to chocolate will Interscience (division of John Wiley & Sons, Inc.), New
take place.
"ometimes it will be necessary to raise the temperature as
York.
- ~- .
(2) SKRABAL,
1940.
-~ -~
A. AND SINGER, E., M n a l s h . , 41, 339 (1920).
high as 250°C, hut this temperature should be considered as an (3) FLORY,P. J., J. Am. Chem. Soe., 61, 3334 (1939).
upper limit. Any intermediate temperature at which rapid reflux (4) FWRY, P. J., "Principles of Polymer Chemistry," Cornell U.
is maintained and decomposition is absent will be satisfactory. Press, Ithaca, N. Y., 1953.

60 / Journal of Chemical Education