Thermal Decomposition of Poly(butylene

Terephthalate)
RICHARD M. LUM, Bell Laboratories, Murray Hill,New Jersey 07974

Synopsis
Detailed results of the overall thermal degradation of poly(buty1ene terephthalate) are reported.
Laser microprobe analysis and dynamic mass spectrometric techniques were used to identify the
primary volatile degradation products and initial pyrolysis reactions that control polymer degra-
dation. A complex multistage decomposition mechanism was observed which involves two major
reaction pathways. Initial degradation occurs by an ionic decomposition process that results in the
evolution of tetrahydrofuran. This is followed by concerted ester pyrolysis reactions that involve
an intermediate cyclic transition state and yield 1,3-butadiene. Simultaneous decarboxylation re-
actions occur in both decomposition regimes. Finally, the latter stages of polymer decomposition
were characterized by evolution of CO and complex aromatic species such as toluene, benzoic acid,
and terephthalic acid. Activation energies of formation for the main pyrolysis products were de-
termined from the dynamic measurements of the major ion species and indicate values of E = 27.9
kcal/mole for the production of tetrahydrofuran and E = 49.7 kcal/mole for the production of bu-
tadiene.

INTRODUCTION
Poly(buty1ene terephthalate) (PBT) is a polyester thermoplastic material
used in the fabrication of a wide variety of molded components. The polymer
chain consists of a mixed aliphatic-aromatic structure:

PBT is prepared by condensation polymerization of dimethyl terephthalate with

1,4-butanediol. The resulting polymer possesses a high degree of crystallinity132
(-30%), average molecular weight M,, = 25,000, glass transition temperature3
Tg = 50C, and melting temperaturel~~ T,,, = 226-228OC.
During processing high melt temperatures and moisture can result in polymer
degradati~n.~ Although investigation of the initial weight-loss behavior of PBT
has been reported: no work has appeared on the characterization of the volatile
products of thermal degradation. Measurements of the composition and rates
of evolution of the volatile products provide important information from which
details of the decomposition process may be determined.
This article presents the first detailed studies of the overall thermal degra-
dation (inuacuo) of PBT. Laser microprobe analysis7is used to determine the
primary volatile degradation products and initial pyrolysis reactions that control
polymer degradation. Dynamic mass spectrometric sampling techniques are
used to complement the laser microprobe measurements by providing detailed
temperature profiles of the partial pressures of the various evolved species. From

Journal of Polymer Science: Polymer Chemistry Edition, Vol. 17,203-213 (1979)

0 1979 John Wiley & Sons, Inc. 0360-6376/79/0017-0203$01.00
204 LUM

these data kinetic parameters of the decomposition reactions may be determined.

In addition, the overall course of thermal decomposition is directly followed with
measurements of the dynamic variations in total pressure in the pyrolysis
chamber as a function of temperature.
PBT undergoes degradation by a complex multistage decomposition mecha-
nism. Although butadiene is the major volatile product, initial polymer de-
composition is characterized by the elimination of tetrahydrofuran-contrary
to the results reported by Passalacqua et aL6 Formation of significant amounts
of carbon dioxide by decarboxylation reactions and carbon monoxide are also
observed, as well as volatile aromatic compounds that evolve during the latter
stages of polymer degradation. Activation energies for the production of volatile
species from the main pyrolysis reactions characteristic of PBT degradation are
determined from the dynamic measurements of the major ion signals. These
are compared with reported values for PBT and lower member homologs.

EXPERIMENTAL
PBT samples for the laser microprobe and dynamic mass spectrometric (MS)
analyses were obtained from virgin resin pellet stock without further preparation.
These samples contained no flame-retardant or filler (glass fiber) additives.
Sample weights ranged from 20 to 30 mg.
Details of the laser microprobe apparatus appear elsewhere718and only a brief
description is given here. Focused radiation (beam diameter = 1 mm) from a
COz laser (A = 10.6 pm) was used to probe the polymer samples. Laser beam
intensities a t the sample surface were varied from 200 to 500 W/cmz. The sample
cell is directly coupled to the inlet of an MS system via a 0.5-mm diameter orifice
and is evacuated through this orifice by the MS vacuum pumps. On laser irra-
diation a plume of volatile products is generated from the polymer surface, im-
mediately formed into a molecular beam, ionized by electron impact (70-eV
electron energy), and analyzed with a quadrupole mass filter. Detection sensi-
tivity is increased by mechanical modulation of the molecular beam which con-
sists solely of the volatile pyrolysis fragments.
Evolved gas analysis measurements as a function of temperature were made
by using the modified apparatus described by Lum.9 A schematic of the ex-
perimental arrangement is shown in Figure 1. Polymer samples are heated in

BUFFER ANALYSIS
CHAMBER CHAMBER
GAS

THERMOCOU

BACKGROUND

Fig. 1. Experimental schematic of dynamic sampling MS apparatus.

 THERMAL DECOMPOSITION OF PBT 205

a Pyrex glass tube attached directly to the inlet flange of the MS system. As the
sample tube is heated, gases evolved from the degrading polymer are dynamically
sampled via a 0.5-mm diameter orifice, formed into a modulated molecular beam,
and mass analyzed. The sample-tube volume (-60 cm3) is evacuated through
the sampling orifice by the MS pumps to a background pressure of Torr.
Heating rates of 3-lO"C/min were used. Repetitive mass spectral scans from
m/e = 12-150 were automatically obtained at 3-min intervals. Time- and
temperature-resolved partial pressure profiles of the pyrolysis fragment ion
signals were thus obtained.
In addition to the partial pressure measurements, the dynamic variation in
total pressure in the sample tube is monitored with an MKS Baratron pressure
gauge. The total pressure data provide information on the overall course of
polymer thermal degradation similar to that obtained from derivative thermo-
gravimetric measurements (rate of weight loss versus temperature or time).
Measurements of both total and partial pressure variations permit detection and
identification of simultaneously occurring decomposition reactions. Details
of complex reactions may be unraveled by exact identification of product species,
order of product evolution, rate of evolution, and determination of kinetic pa-
rameters (e.g., apparent activation energies of product formation).
RESULTS
Laser Microprobe Analysis
Results from laser irradiation of PBT are shown in the modulated mass spectra
in Figure 2. The upper scan represents the first spectrum obtained after expo-
sure of the sample to the laser beam. The two peaks at mle = 71 and 72 form
a distinctive doublet not usually observed in the mass spectra of organic com-
pounds, as, for instance, are the series of fragment peaks appearing at m/e =
25-31 and 39-43. From the structure of PBT, as given in eq. (l ), it is clear that
the m/e = 71,72 doublet can be attributed to volatile tetramethylene oxide; that
is, tetrahydrofuran (THF), which is a heterocyclic compound:

H&-CH,
/ \
HF, ,CH,
0

SCAN # 1

17 .I XI0
71.72
K .

54

SCAN C 5

I I I I I I I
20 30 40 50 60 70 00
m/e (amu)
Fig. 2. Laser microprobe spectra: scan No. 1is the first spectrum obtained after exposure of PBT
sample to the laser beam. Scan time = 2 min.
206 LUM

Initial decomposition of PBT is thus characterized by the elimination of THF

from the polymer chain.
On continued irradiation, however, it is seen that 1,3-butadiene (mle = 54),
COz, and CO become the dominant volatile products, as shown in scan No. 5;
THF is now only a minor species. The presence of water is indicated by the rnle
= 17 signal (overloading the lock-in amplifier causes the irregular peak shape
exhibited by the HzO+ parent ion signal). Trace amounts of aromatic fragments
in the volatile degradation products are indicated by the peaks at rnle = 77-
79.
Spectra obtained at increased sensitivity in a higher mass range, shown in
Figure 3, reveal the presence of several high-molecular-weightcompounds. The
peaks at mle = 105,122 (and mle = 77) form the characteristic ion fragmentation
pattern of benzoic acid, whereas the peaks at mle = 121,149 and 166 are indic-
ative of terephthalic acid. The highest mass peak observed in the laser micro-
probe spectra occurs at mle = 220, which is the molecular weight of PBT
monomer species. NMR data6 indicate that this volatile species may be an
unsaturated ester of terephthalic acid; namely terephthalic acid mono-3-butenyl
(I):
0 0

Ho- !!+!!-o-c~2--cH2--cH=cHI (3)

On electron impact this species would be expected to yield the parent minus OH
(mle = 203) as the most intense ion peak. Also detected, but not shown in these
spectra, are toluene ( m / e = 92) and phenol (mle = 94), plus minor amounts of
benzene (mle = 78).
From laser vaporization of PBT it is clear that polymer thermal degradation
is rather complex, for it involves several separate decomposition reactions. Initial
degradation involves splitting off the glycol portion of the polyester followed by
cyclization to form THF. Subsequent pyrolysis reactions include formation of
COn by decarboxylation, and polymer chain scission which result in the evolution
of 1,3-butadiene and various aromatic compounds. Details of these reactions
are discussed separately in another section.

203
149 n

100 120 140 160 180 200 220

m/e (omu)
Fig. 3. Laser microprobe spectra: mass range 100-230 amu scanned at increased sensitivity.
 THERMAL DECOMPOSITION OF PBT 207

Total Pressure Data

Measurements of the rate of pressure increase in the sample tube during py-
rolysis of PBT yield information on the overall evolution rate of volatile species
from the polymer. Before sample pyrolysis the pressure in the sample tube was
approximately 1 X 10-7 Torr. As the temperature is increased, the polymer
degrades and its weight loss by volatilization results in a corresponding increase
in system pressure. Maximum pressures recorded with a Baratron gauge (sen-
sitivity 0.1 mTorr) during pyrolysis were on the order of 200 mTorr.
The resulting pressure profiles are presented in Figure 4 for two different
heating rates: 3 and 7"C/min. The multiple pressure peaks observed a t the
lower heating rate substantiate the laser microprobe findings of a multistage
decomposition process for PBT. At the higher heating rate these peaks are not
resolved, although some slight evidence of structure in the curve shape remains.
An analysis of the degradation mechanisms involved in the separate stages of
decomposition requires detailed knowledge of the partial pressure behavior of
the major volatile species and is presented in the next section.
The total pressure measurements, which proved to be a sensitive indicator
of the onset of thermal degradation, detected initial volatilization that corre-
sponded to less than 0.1-pg weight loss of the sample. Figure 4 shows that initial
volatilization occurs slightly below 15OOC at the lower heating rate. The per-
centage of decomposition up to 3OOOC is 3.6 for the 3"C/min heating rate and
1.8 for the 7"CImin heating rate.

Fig. 4. Total pressure profiles observed for heating rates of (-) 3 and ( - 0 ) 7"C/min. Multiple
pressure peaks indicate a complex decomposition process for PBT.
208 LUM

Dynamic MS Sampling of Pyrolysis Species

During pyrolysis of PBT evolution of volatile products from the polymer was
monitored simultaneouslywith a Baratron pressure gauge and a quadrupole mass
analyzer. Continuous mass spectral scans (mle = 12-150) were performed au-
tomatically throughout the pyrolysis experiment. For runs at the 3"Clmin
heating rate complete spectra were thus obtained approximately every 10C.
Although the spectra were acquired in analog form, subsequent storage on
magnetic tape was performed to permit digital processing of the raw data. A
Tektronix model 4051 interactive-graphics microcomputer system was used in
the data analysis. Plot routines were developed which enabled "mass chro-
matograms" of a specific ion, selected ion sum or total ion sum to be generated
by searching through each stored spectrum to retrieve the peak amplitudes at
the specified mass values. The resulting ion current plots represent rate curves
of evolution for the selected ion species.
The general features of the mass spectra obtained were similar to those gen-
erated by laser microprobe analysis, with the exception of somewhat lower rel-
ative intensities for the higher-molecular-weight aromatic compounds. Selected
ion profiles for ion species characteristic of the major pyrolysis products observed
are presented in the computer plots of Figure 5: THF (mle = 72,71,42); CO
(mle = 28); 1,3-butadiene (mle = 54,53,51,50,49); COa (mle = 44). THF is
observed as the first species evolved (220OC) in agreement with the laser mi-
croprobe results. Two peaks are detected in the evolution of Cop, the first
coincident with the maximum in THF evolution (290C) and the second oc-
curring at approximately 340C. Evolution of the major product, 1,3-butadiene,
begins at approximately 27OOC and reaches a maximum at about 340C.
Maximum evolution for CO is observed at 350C.
These ion profiles are in excellent qualitative agreement with the variations
observed in the total pressure (Fig. 4). A more quantitative comparison requires
faster scanning rates or selected ion monitoring,1 both of which necessitate
automated data acquisition. This capability is presently .being implemented
by additions to the apparatus already described.

DISCUSSION
Decomposition Reactions
The observations suggest that initial polymer scission occurs via the following
cyclic transition state (I), which is commonly invoked for ester pyrolysis.ll

-+ ---@XOH + CH,=CH-CH,-CH,-0-C I+- (4)

Both the laser microprobe and dynamic MS data suggest that subsequent PBT
thermal decomposition proceeds along two different reaction pathways.
 THERMAL DECOMPOSITION OF PBT 209

Decomposition of I1 via an ionic mechanism yields the initially observed py-

rolysis product THF.

-+E'+v 0

In addition, because the mle = 17 signal indicates the presence of water in the
decomposition products, acid-catalyzed hydrolysis of I11 may also be important
in THF production.

bH

At higher temperatures the second reaction pathway, which involves 11, results
in the elimination of 1,3-butadiene by concerted ester pyrolysis.6

---t i- CH2=CH-CH=CH, (7)

bH

The possibility of butadiene production by secondary reactions is countered

by the double peaks observed in the evolution of C02, the first being coincident
with the maximum in the rate of THF formation and the second correlating well
with the butadiene maximum. Formation of C02 in both cases arises from
separate decarboxylation processes that involve the products accompanying
reactions (5)-(6c) and (7).
210 LUM

88

60
>.
I-
H

2
I-
40

s
20

20200
0 w 258 300

TEMP CC)
358 400

TEMP CC)
Fig. 5. Computer plots of species evolution rates. Ion profiles for fragments characteristic of the
major pyrolysis products upper left-THF (selected ion sum: mle = 72,71,42);upper right-CO
(mle = 28); lower left-COz (m/e = 44); lower right-1,3-butadiene (selected ion sum: mle = 54,
53,51,50,49).

Determination of Activation Energies

Polymer thermal decomposition can often be represented by the following
simplified reaction:
-
A(so1id) B(so1id) C(gas) +
Details of the gas evolution profiles depend largely on the kinetic parameters
(8)

characteristic of the decomposition process (i.e., activation energy, frequency

factor, and reaction order). These kinetic parameters can be determined from
the ion signal profiles in Figure 5 by application of analysis techniques similar
to those used in thermogravimetric measurements. With the assumption that
the rate of evolution and total weight of evolved gas are proportional to the
weight-loss rate and the total weight.loss, the following equation is derived.12
KI E
= l0gC - ___
log (KSo - KS,)" 2.3 RT
Here I is the MS ion current for a given species, So is the area under the MS ion
current curve as a function of temperature, St is the corresponding area between
the initial reaction temperature and a given temperature T,R is the gas constant,
n, the reaction order, E , the activation energy, and K and C, constants.
With the help of the dedicated data-handling system described earlier values
for the parameters I , So,and St are readily obtained and eq. (9) can be solved
for various trial values of n in an Arrhenius-type plot. This technique is espe-
cially valuable for complex decomposition processes involving simultaneously
competing reactions; for example,
 THERMAL DECOMPOSITION OF PBT 21 1

Conventional weight-loss measurements actually represent the composite effect

of these two reactions. The dynamic MS measurements, however, enable the
evolution rates of C and E to be determined separately by following the behavior
of the corresponding ion species characteristic of these products. Hence acti-
vation energies can be directly calculated for the separate reactions (10a) and
(lob).
Arrhenius plots for the ion species characteristic of the major decomposition
products from PBT are presented in Figures 6 and 7. In Figure 6 an activation
energy of 27.9 kcal/mole is calculated for production of THF. For the concerted
ester pyrolysis reaction yielding butadiene, which is usually taken as the sole
degradation reaction,6the data in Figure 6 indicate a value E = 49.7 kcal/mole
for the activation energy. This compares with E = 41 kcal/mole determined by
Passalacqua et a1.6 (based on butadiene being the only volatile decomposition
product) and is in good agreement with recent values reported for similar poly-
esters such as poly(ethy1ene terephthalate).13J4 From Figure 7 a value E = 60.1
kcal/mole is calculated for CO evolution. Finally, the two-stage evolution of
C02 results in a calculated activation energy of 52.6 kcal/mole for the high-
temperature reaction. The scatter in the data of Figure 7 for the low-tempera-
ture C02 reaction makes determination of the activation energy difficult. As
shown by the dashed line, however, the data agree reasonably well with the
high-temperature determination of the activation energy, which indicates that
production of COa occurs via the same mechanism in both stages. Decarbox-
ylation most likely involves the COOH end groups produced by the separate

-2 2
a -3
(3
J
-s
W
-4 -
l-
a
(L

z
f -5-
a
D
a
(L
W
-6-
a
W
E
-1

z
a -7-
0
z
I I I I I 1
-714 1.5 1.6 1.7 1.8 1.9 2 .o
1000/T("K)

THF (selected ion sum: mle = 72,71,42) and (0)

Fig. 6. Arrhenius plots for (0) 1,3-butadiene
(selected ion sum: mle = 54,53,51,50,49).
212 LUM

t -

E l aB
O
y
W -4
A0
\

1000/T("K)
Fig. 7. Arrhenius plots for ( 0 )CO (mle = 28) and (0)
COz (mle = 44).

TABLE I
Calculated Activation Energies
Temperature E
Species range ("C) (kcallmole)
THF 235-360 27.9
1,3-butadiene 275-360 49.7
coz 250-295 52.6
coz 320-360 52.6
co 325-360 60.1

decomposition processes [eqs. (6c) and (7)] that yield THF and butadiene. A
summary of these values is presented in Table I. In all cases the data were best
represented by a second-order rate law: that is, n = 2.

CONCLUSION
Thermal decomposition of PBT proceeds along two distinct major reaction
pathways. Initial polymer degradation involves an ionic decomposition process
that results in the evolution of T H F with an apparent activation energy of 27.9
kcal/mole. This is followed by a concerted ester pyrolysis reaction involving
an intermediate cyclic transition state that yields volatile butadiene species. An
activation energy of 49.7 kcal/mole is calculated for butadiene production. The
dynamic behavior exhibited in the COz evolution profile provides confirming
evidence that THF and butadiene arise from separate primary pyrolysis reac-
tions. Volatilization of CO as well as more complex aromatic species such as
toluene, benzoic acid, and terephthalic acid is observed during the latter stages
of polymer decomposition. Aromatic species are detected only a t trace levels,
however.
 THERMAL DECOMPOSITION OF PBT 213

The author would like to thank P. G. Kelleher for informative discussions of the properties and
applications of PBT that led to the initiation of this work and W. H. Starnes, Jr., who kindly shared
his expertise in discussions of the various thermal decomposition processes.

References
1. M. Pietrzak and J. Kroh, Eur. Polym. J., 8,237 (1972).
2. M. Gilbert and F. J. Hybart, Polymer, 13,327 (1972).
3. P. G. Kelleher, private communication (1977).
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5. G. H. Bebbington, private communication, TM76-1516-44 (1976).
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(1976).
7. R. M. Lum, Thermochim. Acta, 18,73 (1977).
8. R. M. Lum,J. Appl. Polym. Sci., 20,1635 (1976).
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10. J. Houseman and F. W. Hafner, J. Sci. Znstrum., 4,46 (1971).
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pp. 285-294.
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D. Garn, Eds., Academic, New York, 1969, p. 517.
13. W. L. Hergenrother, J. Polym. Sci. Chem. Ed., 12,875 (1974).
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Received October 5,1977

Revised November 16,1977