POLYMERS FOR ADVANCED TECHNOLOGIES

Polym. Adv. Technol. 2004; 15: 691–700

Published online in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/pat.526

A review on thermal decomposition and combustion of

thermoplastic polyesters
Sergei V. Levchik1* and Edward D. Weil2
1
Akzo Nobel Chemicals, 1 Livingstone Ave., Dobbs Ferry, NY 10522, USA
2
Polytechnic University, Six Metrotech Center, Brooklyn, NY 11201, USA
Received 25 February 2004; Accepted 2 September 2004

An overview is presented of the literature on the thermal decomposition and combustion of ther-
moplastic polyesters, especially commercially important poly(ethylene terephthalate) (PET) and
poly(1,4-butylene terephthalate) (PBT). Although the literature is not clear as to whether heterolytic
or homolytic scission of aliphatic fragments is the first step in the thermal decomposition of polye-
sters, in any case volatilization of light aliphatic fragments make polyesters easily ignitable poly-
mers. Despite the presence of benzene groups in the main polymer chain, thermoplastic polyesters
show very limited tendency to char, but instead, aromatic-containing polymer fragments volatilize
and feed the flame. Fire retardant additives, although they usually facilitate decomposition of the
polyesters at lower temperature, also usually promote charring and therefore suppress combustion.
Copyright # 2004 John Wiley & Sons, Ltd.

KEYWORDS: thermoplastics; polyesters; thermal properties; combustion; toxicity

INTRODUCTION THERMAL DECOMPOSITION

Partly aromatic polyesters obtained from aliphatic glycols Poly(ethylene terephthalate) (PET)
and aromatic dicarboxylic acids or esters are important com- The quantitative analysis of gases evolved from PET and PBT
mercially.1 The largest volume is represented by poly(alky- was carried out using a thermogravimetric analysis-differen-
lene terephthalate)s and, more specifically, poly(ethylene tial thermal analysis (TGA-DTA)/FT-IR system.2 The
terephthalate) (PET) and poly(1,4-butylene terephthalate) evolved gases from PET at 4508C, where the derivative
(PBT). PET was introduced commercially in 1953 as a textile TGA curve showed the maximum rate, included benzoic
fiber and shortly thereafter as a film. Later, PET resins for acid, carbon dioxide, carbon monoxide and benzoic acid deri-
injection molding were marketed. PBT was introduced in vatives. It was believed that carbon dioxide, benzoic acid and
1970 and grew rapidly as it found utility in various high aromatic esters were evolved in the initial stage of decompo-
volume automotive, electrical, and other engineering applica- sition. The spectrum obtained by subtracting the spectrum at
tions. An amorphous, transparent, injection-moldable 4008C from the spectrum at 5008C suggested that more ben-
poly(1,4-cyclohexylenemethylene terephthalate) (PCT) and zoic acid is evolved at 5008C. The subtraction spectrum also
poly(1,4-cyclohexylenemethylene terephthalate-co-isophtha- showed terephthalic acid esters.
late) (PCTI) have also found commercial use. Recently, An early comprehensive overview of the thermal decom-
poly(1,3-propylene terephthalate) was introduced, which position of PET was reported by Buxbaum.3 It was
shows intermediate properties between PET and PBT. postulated that the primary scission of the ester linkage in
Although thermal decomposition of PET and PBT is the polymer is probably not a homolytic reaction, since
intensively reported in the literature there still are ongoing thermal degradation was not inhibited by free radical
disagreements over the mechanism of thermal decomposi- trapping agents. Based on the mechanism of thermal
tion. This review discusses thermal and thermal oxidative decomposition of model esters it was established that esters
decomposition of thermoplastic polyesters especially in containing at least one b-hydrogen atom decompose to an
relation to combustion of these plastics. Thermal decomposi- olefin and acid through a cyclic transition state (Scheme 1). It
tion in the presence of flame retardant additives is discussed has been shown that the C–O breakage is heterolytic and
as well. A separate review has been prepared on the flame that the a-carbon atom develops some carbonium-ion
retardancy of thermoplastic polyesters. character in the transition state. It appears that for a given
ester at a fixed temperature, the rate of decomposition is
determined more by the stability of the breaking alkoxy C–
O bond than by the breaking C–H bond or the forming C C
bond.4
*Correspondence to: S. V. Levchik, Akzo Nobel Chemicals, 1
Livingstone Ave., Dobbs Ferry, NY 10522, USA. Six poly[alkyl-4,40 (terephthaloyldioxy)dibenzoate]s, with
E-mail: [email protected] linear (3, 6, 7 and 10) and branched (dimethyl and

Copyright # 2004 John Wiley & Sons, Ltd.

692 S. V. Levchik and E. D. Weil

If 2-hydroxyethyl end groups are present in the polymer

the reactions in Scheme 3 take place as well. Thus, as long as
free hydroxyl end groups exist in a PET melt, every broken
polymer link can be reformed. When most of the hydroxyl
Scheme 1. end groups have been consumed, the molecular weight can
begin to fall.
Edge et al.9 attempted to characterize yellowing in PET and
diethyl)methylene spacers were studied by TGA and infra- noted that ‘‘the initiation mechanism of thermal degradation
red spectroscopy.5 of PET is still a subject for debate’’. Thermal cleavage of the
The activation energy found for linear aliphatic chain ester bond initially results in the formation of a vinyl ester
polyesters (n ¼ 3–10) was very similar to those found for end-group and a carboxyl end-group. Reactions in Scheme 4
other aromatic polyesters, such as PET and PBT. Infrared can occur to some extent with vinyl ester end-groups.
spectroscopy shows that aliphatic polyester groups decom- Because end-groups in PET are predominantly hydroxye-
pose first. The mechanism related to the b-elimination should sters, trans-esterification of the vinyl esters formed on
be excluded in the case of 2,2-dialkyl-substituted spacers. As degradation can take place to give vinyl alcohol which
a result the ester groups did not participate in the first stages transforms to acetaldehyde. Essentially, hydroxyl end-
of the degradation which implies significant stabilization of groups would be replaced by carboxylic acid groups
the polymer. producing an equivalent quantity of acetaldehyde. This
process would regenerate the polymeric chains and maintain
the average degree of polymerization. This may be one reason
why, after an initial reduction of rheological and mechanical
properties, little further change occurs with more reproces-
sing of PET. The process was also found to be temperature
dependent with acetaldehyde production reaching a max-
Similar to model compounds, the principal point of imum at 2808C and resulting principally from chain-ends,
weakness in PET chain is the b-methylene group.3,6 –8 The whereas at 3008C significantly more acetaldehyde arose from
main reactions in the thermal degradation of PET are 2-methyl-1,3-dioxolane. How these degradation mechanisms
summarized in Scheme 2. may account for the discoloration (yellowing) of PET is

Scheme 2.

Scheme 3.

Copyright # 2004 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2004; 15: 691–700
 Thermal decomposition and combustion of thermoplastic polyesters 693

Scheme 4.

Scheme 5.

Scheme 6.

Scheme 7.

debatable. It may be that accumulation of vinyl ester groups Khemani11 studied the thermal degradation of PET at
allows crosslinking leading to the formation of polyene 2808C over an extended period of time and found a gradual
segments or self-condensation of retained acetaldehyde decrease in the amount of acetaldehyde evolved with time.
produces aldol products which condense and dehydrate to Three different routes generating acetaldehyde: (a) the HO-
form color bodies. end groups; (b) the vinyl end groups; (c) the mid-polymer
Vijaykumar and coworkers10 suggested the formation of chain scission which also generates vinyl end groups were
acetaldehyde, the major pyrolysis product of PET, through discussed. The mechanism of thermal decomposition of
recombination of vinyl-terminated carboxylate and car- chain ends is shown in Scheme 7. Evolution of dioxane in the
boxylic acid-terminated units (Scheme 5). This reaction may low temperature decomposition of PET was also reported by
proceed by the intra- or intermolecular H shift to form vinyl Hovenkamp and Munting.12
alcohol, which isomerizes to give acetaldehyde. The homolytic scission of ester bonds was suggested by
Apart from the formation of acetaldehyde, a considerable Bounekhel and McNeill13 based on their thermal decomposi-
amount of ethylene is also formed. It was suggested that the tion study in vacuum of polyester made from poly(ethylene
vinyl-terminated carboxylate units and the PET units form an glycol) and terephthalic acid. They suggested that initial
eight-membered cyclic transition state to give C2H4 and homolysis can occur in two possible ways, involving either
carboxylic acid-terminated units (Scheme 6). alkyl-oxygen (a) or acyl-oxygen (b) scission (Scheme 8). These

Copyright # 2004 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2004; 15: 691–700
694 S. V. Levchik and E. D. Weil

Scheme 8.
authors suggest that homolytic reactions can explain the
whole range of observed degradation products. Authors
argued that products such as CO and CO2 are formed
throughout the main temperature range of decomposition,
whereas by a non-homolytic route, such products would only
be found at the highest degradation temperatures (in the Scheme 9.
range up to 5008C). They also suggested that radical-trapping
agents would only inhibit a chain-reaction mechanism and reaction of the formed terephthalic acid. (Scheme 10) This
would be ineffective in the proposed decomposition because mechanism was supported by the fact that terephthalic acid
homolysis takes place in a cage in which the pair of radicals yields biphenyl as well as benzene at elevated temperatures
then undergo disproportionation. above 5008C. It is interesting to notice that the formation of
Day et al.14 studied the thermal decomposition of model both benzene and biphenyl decreased as the number of
n-propyl pyrene-1-carboxylate and found propylene and methylene groups in the polymer chain rose.
pyrene-1-carboxylic acid as the major reaction products,
presumably formed via a six-centered intramolecular transi- Poly(1,4-butylene terephthalate) (PBT)
tion state. However, some n-propanol was formed as a result The initiation of the thermal decomposition of PBT is similar
of a radical cleavage, but the contribution of this reaction to to that of PET, however the products of decomposition are
the overall decomposition appeared to be insignificant. somewhat different because of longer aliphatic fragments
Divinyl terephthalate (I) was considered to be a primary in the chain. Several authors10,16,17 report initial polymer scis-
scission product, as found in another study run by Day and sion occurring via the six-membered cyclic transition state.
coworkers.15 Vinyl acid terephthalate and terephthalic acid According to the actual geometry of the chains, the major
were not detected but were not ruled out since the products of degradation route in PBT would lead to the formation of
decarboxylation of these two acids were detected, namely butadiene (Scheme 11).
vinyl benzoate, benzoic acid, and benzene (Scheme 9). Apart from butadiene a considerable amount of tetrahy-
drofuran (THF) is also obtained in the degradation products
of PBT. When the well-known acyl-oxygen cleavage of the
ester linkages proceeds in the PBT chains intra- or inter-
molecular H shifts can occur, leading to the formation of
hydroxyl-terminated units, which in turn undergo further
degradation to yield THF and the carboxylic acid-terminated
At elevated temperatures the acids from terminal groups chain10 (Scheme 12).
rapidly became converted to the more stable phenyl Another less feasible mechanism for the formation of THF
terminals by elimination of carbon dioxide.16 Detected and butadiene from PBT by the intra- or intermolecular H
biphenyl was most likely formed through the bimolecular shift can form a diol which eliminates a molecule of water to

Scheme 10.

Copyright # 2004 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2004; 15: 691–700
 Thermal decomposition and combustion of thermoplastic polyesters 695

Scheme 11.

The composition of the volatile products depends strongly

on the degradation temperature. At lower temperatures,
acetaldehyde, formaldehyde, and carbon monoxide are the
main degradation products. The concentrations of carbon
monoxide, aromatic and aliphatic hydrocarbons, and methyl
acetate increased with temperature. The maximum yields of
formaldehyde, methyl alcohol, and dioxane were observed at
5008C, and that of acetaldehyde, at 4008C.
Buxbaum3,19 studied the degradation of PET in the
presence of oxygen and proposed Scheme 14 for the
thermooxidative degradation.
PET undergoes gelation by heating at 230–3008C in air,
whereas under nitrogen crosslinks are scarcely formed.20
Scheme 12.
Crosslinking was accelerated by purging to remove sublim-
able degradation products from the system with a stream of
air. Thermooxidative degradation of linear polyesters other
than PET was also studied. Poly(ethylene isophthalate) and
poly(ethylene sebacate) were easily gelled. However, poly
(trimethylene terephthalate) and poly(neopentyl terephtha-
late) were scarcely gelled. It was proposed that the crosslinks
Scheme 13.
are generated in the aliphatic part of the polyester. In the first
form THF and two molecules of water to form butadiene. place, vinyl esters may be taken into consideration. There are
Because of the presence of water in the decomposition three possible mechanisms for the crosslinking reaction
products, acid-catalyzed hydrolysis of the butylene ester involving vinyl esters (Scheme 15). Thus, the main reactions
chain end-groups may also be important in THF production17 leading to crosslinking are proposed as follows: first, random
(Scheme 13). scission of polyester chains may take place, forming
carboxylic acids, vinyl esters, aldehydes, carbon dioxide,
Thermal oxidation and so on. After the vinyl esters accumulate to some
Studies of the thermal degradation of PET in a tubular fur- concentration, the vinyl esters react with the polymer chain,
nace with an air flow have shown18 that the main evolved and network structures are formed. At this point, the role of
compounds are carbon monoxide, acetaldehyde, formalde- oxygen may be the acceleration of chain scission, and the
hyde, benzene, styrene, and aliphatic C1 –C4 hydrocarbons. purge of the degradation products out of the system

Scheme 14.

Copyright # 2004 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2004; 15: 691–700
696 S. V. Levchik and E. D. Weil

Scheme 15.

Scheme 16.

decreases the reverse reactions which consume the vinyl

esters formed and thus the purging accelerates the cross-
linking reaction.
In contrast, Nearly21 and Spanniger22 believed that
aromatic fragments are mostly responsible for the cross-
linking and coloration. They had separated gelled PET from
ungelled polymer and methanolyzed the gelled part. Based
on the products found by gas chromatography in the filtrate
the mechanism leading to crosslinking was suggested
(Scheme 16). Such a mechanism depends on the generation
of a phenyl radical which is probably formed after initial
oxidation at a methylene position. After chain scission and
decarboxylation, the phenyl radical arylates an adjacent
benzene ring to form a crosslink. Scheme 17.
Scheme 17 illustrates how the additional components
found using gas chromatography support the intermediacy
of the phenyl radical.22 All biphenyl compounds may be flame retardant additives normally modify the mechanism of
produced by the same phenyl radical. thermal decomposition of polyesters and this effect is a part
Instead of chain scission via alkyl oxygen bond cleavage, of the flame retardant action of these additives.
cleavage could occur at the acyl oxygen bond (Scheme 18). An Sato et al.23 studied the thermal degradation of a flame-
acyl radical would be generated which could substitute on an retarded PBT containing a synergistic flame-retardant system
adjacent benzene ring to form a crosslink. This is also an based on brominated polycarbonate and antimony trioxide
alternate mechanism for the generation of a phenyl (Sb2O3) using various temperature-programmed analytical
radical end-group, since the acyl radical could lose carbon pyrolysis techniques. It was found that in this flame-
monoxide. retardant system, brominated phenols are first evolved at
slightly lower temperatures than those of the flammable
Thermal decomposition in the presence of fire product evolution from the substrate polymer, thus causing
retardants the initial flame-retarding effect. In addition, HBr should
Thermal decomposition of polyesters could be affected either then be evolved over the whole degradation temperature
by acidic or basic species present in the polymer. Therefore range of PBT to introduce a free radical trap into the gas phase

Copyright # 2004 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2004; 15: 691–700
 Thermal decomposition and combustion of thermoplastic polyesters 697

Scheme 18.

and accompanied by char formation to decrease flammable evolution of a large amount of carbon dioxide (incombustible
products. The observed initial temperature of the evolution of gas), which might be a decomposition product of polycarbo-
SbBr3 and its flame-poisoning effect nearly coincides with nate, dominated in the extinguishment stage.
that of HBr evolution. PET fibers containing commercial flame retardants,
A FT-IR gas cell was used for comparison of thermal namely Dacron 900F (containing ethoxylated tetrabromobi-
decomposition of plain PBT and two formulations containing sphenol A comonomer), TRIS (containing the now-
different highly brominated aromatic compounds as flame discontinued tris(2,3-dibromopropyl) phosphate), AB19
retardants.24 Samples with brominated flame retardant (containing cyclic phosphonate ester, Antiblaze 19, now
degrade primarily to CO2, butadiene and PBT chain Amgard CU), and Trevira T271 (containing phosphonic acid
fragments. One formulation was found to degrade at a comonomer) were compared with non-flame-retarded fibers
significantly higher temperature than another, the first one Dacron T54 and MICH using thermogravimetry.26 It was
only started degrading at 2958C whereas another one concluded that the presence of phosphorus-only flame
released PBT oligomers at 2258C. The thermal stability of retardants (AB19 and T271) caused no large differences in
the stable flame retardant formulation was similar to non- the measured interval of thermal decomposition. In the case
fire-retardant PBT. Plain PBT started to degrade at around of the bromine-containing polyesters (i.e. 900F and TRIS)
3008C, while the gas spectra of the even less stable flame some changes were noted. With the 900F compound the
retardant additive showed degradation above 3608C. The degradation was apparently retarded, whereas with the TRIS
authors concluded that it is unlikely that the stable flame polyester system, the volatilization of gaseous fuel proceeded
retardants have any great influence on the decomposition of at an earlier stage than was encountered with the untreated
PBT. PET.
The model ester n-propyl pyrene-1-carboxylate (II) was Furthermore, the TRIS material at 9008C gave higher
decomposed under pyrolysis conditions reflective of the fire concentrations of highly volatile products, especially
situation to give propylene and pyrene-1-carboxylic acid as methane whose concentration was almost a factor of 10
the major reaction products, presumably via a six-centered larger than obtained with the untreated material.15 The
intramolecular transition state.14 While some n-propanol was formation of radicals helps to explain such minor products of
formed, the contribution of this reaction to the overall pyrolysis as ethane, propylene, acetone, ethanol, toluene,
decomposition was insignificant. The addition of decabro- benzaldehyde, methyl benzoate, p-methylacetophenone,
modiphenyl oxide to the model ester appeared to have no vinyl p-methylbenzoate, biphenyl and diphenylmethane.
significant effect on the solid phase pyrolysis process. Thus, it The 900F polyester system also produces higher concentra-
was concluded that for bromine-containing compounds of tions of the more volatile species than obtained with the
this type to have an influence on reducing the flammability standard polyester.
characteristics of polyesters, they must influence the gas Granzow et al.27 studied the thermal degradation of PET in
phase reactions. the presence of red phosphorus. They assumed that pyrolysis
of PET occurs in two stages: the first step involves the primary
bond breaking of the polymer chain, while the second step
represents the further decomposition of the primary degra-
dation products into volatile species. The close agreement of
the kinetic parameters with and without phosphorus
indicated no inhibition of the initial chain cleavage. There-
fore, it was assumed that the inhibition by phosphorus is
exclusively due to the decrease in the velocity of the second
step. The effect of phosphorus on the degradation of low
molecular products is possibly due to the formation of
Nagasawa et al.25 studied the decomposition gases from a thermally stable phosphorus-oxygen bonds in the pyrolyzing
fire retardant PBT, which was prepared by combining PBT PET, thus preventing the formation of gaseous pyrolysis
mechanically with brominated polycarbonate and antimony products. This explanation is supported by the fact that
oxide. Using a fast thermolysis/FT-IR spectroscopy techni- elemental phosphorus has been shown to be an inefficient
que gaseous antimony tribromide was not observed. The flame retardant for oxygen-free polymers.

Copyright # 2004 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2004; 15: 691–700
698 S. V. Levchik and E. D. Weil

Phosphorus containing flame retardants used in a study by PBT were found in the presence of ammonium polypho-
Bednas et al.15 were Antiblaze 19 (cyclic phosphonate, AB19, sphate.30
Albright & Wilson, now Albemarle Amgard CU) and Trevira Balabanovich and Engelmann31 flame retarded PBT by
271 (reacted-in phosphinate, Hoecsht). When considering the addition of poly(sulfonyldiphenylene phenylphosphonate).
role of the flame-retardant systems on the pyrolysis data Using infrared, it was shown that the polyphosphonate
obtained at 9008C, it was obvious that both phosphorus- changes the degradation pathways of PBT resulting in
containing polyesters behave very similarly to the standard formation of polyarylates (Scheme 20). It was believed that
untreated polyester in terms of the products formed and their polyarylates are formed due to recombination of carbox-
concentrations. In another study28 it was found that yphenylene and phenylene radicals appearing from thermo-
phosphorus- and phosphorus-halogen-containing additives lysis of PBT.
increased the amount of acetaldehyde formed. Significant The presence of phenolic species and associated
decomposition of CH3CHO occurring at 7008C resulted in aromatic ketones was explained by Fries type isomerization
increased amounts of CH4 and CO formed. Phosphorus was (Scheme 21). In the presence of the phosphonate the
considered as promoting larger quantities of gaseous phenolic groups react with the P–O–C bond by a trans-
products compared to those produced by plain PET. esterification mechanism, which is proposed to be a part of
However, it was also shown that phosphorus promotes char the flame retardant effect.
formation and increases the aromaticity of the residue.
Combustion and thermal decomposition of PBT was Kinetics of thermal decomposition
studied in the presence of cyclic phosphonate (Antiblaze Since the mechanism of thermal decomposition of polyesters
1045, a higher molecular weight relative of Antiblaze 19) and is complex, this leads to complexity of kinetics, which depend
melamine.29 Infrared provided evidences that the cyclic on the detection method, heating regimes and atmosphere.
phosphonate with melamine modifies the mechanism of The presence of flame retardant additives affect the kinetics
thermal decomposition of PBT towards formation of amides of the thermal decomposition as well as the composition of
instead of acids (Scheme 19). Dehydration of aromatic the products.
amides, which cools the flame, and fast formation of For example, Lum17 postulated a multistage decomposi-
benzonitriles contributed to the flame retardancy. Similar tion mechanism for PBT involving two major reaction
alterations in the mechanism of thermal decomposition of pathways: initial degradation by an ionic decomposition

Scheme 19.

Scheme 20.

Scheme 21.

Copyright # 2004 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2004; 15: 691–700
 Thermal decomposition and combustion of thermoplastic polyesters 699

with evolution of THF and then concerted ester pyrolysis with the conversion. The activation energy of the second
involving an intermediate cyclic transition state and yielding stage was also slightly increasing with conversion, and only
1,3-butadiene. Activation energies of formation for the main the third stage showed a constant activation energy. The
pyrolysis products were determined from the dynamic phosphorus-containing additives did not greatly affect the
measurements of the major ion species in mass spectrometry values of the activation energies, whereas bromine-contain-
and indicated values of 117 kJ/mol for the production of THF ing Dacron 900F increased and phosphorus-bromine contain-
and 208 kJ/mol for the production of butadiene. ing TRIS decreased the activation energy.
Buxbaum3 surveyed early publications on the kinetics of Based on the TGA data in inert atmosphere, Granzow
thermal degradation of PET, the rates being measured in et al.27 measured the activation energy of 155 kJ/mol for plain
terms of products formed, rate of change of molecular weight PET and of 163 kJ/mol for PET with 2 wt% red phosphorus. It
(as measured by the melt viscosity or the intrinsic viscosity) is evident that the activation energy for the decomposition of
or rate of change in concentration of end groups. Activation PET is only slightly increased in the presence of phosphorus.
energy calculated based on intrinsic viscosity change was However, in air, an activation energy of 126 kJ/mol was
261 kJ/mol, whereas activation energies calculated from found for pure PET and 151 kJ/mol for PETþ2% phosphorus
change of melt viscosity were 134 and 201 kJ/mol (two was obtained. Contrary to the results obtained in an inert
different sources). The activation energy found from the atmosphere, the activation energy for thermal oxidation
kinetics of total gas evolution was 160 kJ/mol. The kinetics strongly increased in the presence of phosphorus. The
based on increase of carboxyl end groups revealed an Arrhenius plots for decomposition in an inert atmosphere
activation energy of 175 kJ/mol and based on total end and in air intersect at temperatures of 4708C, indicating that
groups, 246 kJ/mol. above this temperature, the thermal oxidation is accelerated
Later the rates of degradation of PET were measured in in the presence of phosphorus.
terms of weight loss of volatile degradation products,
decrease of inherent viscosity and increase in concentration Combustion
of carboxyl end groups.32 Thermal-oxidative degradation Although polyesters have aromatic structures in the polymer
was investigated by differential scanning calorimetry (DSC). chain they are very combustible materials. The ease of release
Calorimetric results showed that thermal-oxidative degrada- of highly combustible aliphatic gases, e.g. acetaldehyde,
tion of PET is an exothermic reaction, with an apparent ethylene, dioxane, THF, butadiene, and the low tendency to
activation energy of 117 kJ/mol. Melt temperature, melt crosslink and char are the main reasons for the high flamm-
residence time, melt environment, and drying environment ability. The rate of heat release measured at 300 sec combus-
have all been found to affect the degradation of PET. Based on tion time in cone calorimetry at a heat flux of 50 kW/m2 for
decrease of inherent viscosity, activation energies of 117 and PET was 270 kW/m2 and for PBT was 470 kW/m2.36 The oxy-
159 kJ/mol have been calculated for air-dried and vacuum- gen index of PET is 25, whereas PBT has an oxygen index of
dried samples respectively. 22.36 The logarithm of the oxygen index for PET was propor-
A kinetic study of the thermal decomposition of PET and tional to the reciprocal of the concentration of carboxylic
PBT has been performed by controlled-rate thermogravime- chain ends.37 This was related to the idea that the main step
try (CRTG) and measurement of evolved gas components, of PET thermal degradation was hydrolytic and that this was
obtained from a simultaneous TG-MS system.33 Significant carboxylic acid catalyzed.
advantages of CRTG were found for studying the thermal Stuetz et al.38 used oxygen index apparatus and graded the
decomposition of polymers, because of better separation of flammability of various polymers based on the time interval
overlapping decomposition steps. For PBT the activation during which a sample continued to burn at a given oxygen
energy for the main step of weight loss was found at the level concentration (OC) after removal of the ignition flame. This
of 160 kJ/mol, and for PET at the level of 200 kJ/mol. time interval was called the self-quenching time (SQT). The
Based on the thermal decomposition of PET under resulting data were combined in SQT versus OC plots in
isothermal conditions, it was shown34 that the degradation order to find the critical oxygen concentration (COC) at which
in nitrogen probably occurs by a random chain scission the sample does not ignite. It was shown that COC depends
mechanism, while the degradation in air is more complex. In on the sample diameter, but burning in the presence of glass
the latter case, the exothermic character of the process wick after bottom ignition begins at an OC of 15.3%,
suggested that the chain degradation reaction is overlapped independent of specimen diameter. This COC for the onset
by oxidative processes. of geometry-independent burning in the presence of a wick
The thermal oxidative decomposition of PET has been was referred to as COC-BW. The similar value for the top
studied using thermogravimetry at several heating rates ignition was referred as COC-TW. PBT gives the following
between 0.1 and 1008C/min.35 The degradation was found to values COC-BW ¼ 15.4, COC-TW ¼ 17.5 and PET COC-
be a complex process composed of at least three overlapping BW ¼ 15.8, COC-TW ¼ 18.8. Although PET is less flammable
stages with the apparent activation energies 100–120, 185– than PBT both polymers need to be flame retarded, especially
200, and 140–145 kJ/mol. Phosphorus-containing flame for electrical and electronic applications.
retardant also showed these three stages, although the very Day et al.39 studied the flammability limits of pyrolysate
early stage had a lower activation energy and the second gases generated from polyester fabric and polyester/cotton
stage was displaced to higher conversions.26 The halogen- blend using an infrared heating system with 13.27 kW/m2
containing additives did not show the uniform first stage but heat flux. Every 30 sec a spark was discharged to test for
instead, the apparent activation energy increases steadily ignitability. The polyester spun woven fabric showed the

Copyright # 2004 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2004; 15: 691–700
700 S. V. Levchik and E. D. Weil

following results: heating time to ignition ¼ 9 min, flamm- aromatic hydrocarbons. Because of high flammability hazard
ability limits (weight loss %) lower ¼ 10, higher ¼ 42, flamm- both PET and PBT need to be flame retarded in some textile as
ability range (weight loss %) ¼ 31. Polyester/cotton blend well as electrical and electronic applications.
50/50 showed the following results: heating time to
ignition ¼ 4.75 min, flammability limits (weight loss %) low-
er ¼ 47, higher ¼ 73, flammability range (weight loss %) ¼ 26.
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