Studies on the Mechanism of Thermal Decomposition of Unsaturated Polyester Resins with Reduced Flammability

Studies on the Mechanism of Thermal Decomposition of

Unsaturated Polyester Resins with Reduced Flammability

Dr Ewa Kicko-Walczak
Industrial Chemistry Research Institute, Warsaw, Poland
e-mail ewa.kicko-walczak@ichp.pl

Paper presented at Addcon World 2003

SUMMARY

The thermal decomposition of halogenated unsaturated polyester resins (UPRs), flame

retarded by zinc hydroxystannate and cross-linked with styrene, has been investigated by
thermogravimetry (TG) in both dynamic and isothermal mode, and by TG coupled on-line
with Fourier transform infra red spectroscopy (TG-FTIR) or mass spectroscopy (TG-MS).
The data from TG analysis show that degradation proceeds in two steps for unmodified as
well as modified UPR, but the char residue at 500°C was considerably higher for flame-
retarded resins. Analysis of the volatile decomposition products by FT-IR and MS
spectrocopy revealed that during controlled heating, the emission of phthalic anhydride
takes place at ca. 330°C, followed by styrene at ca. 380°C., and a complex mixture of other
aromatic compounds are evolved. Further studies by TG-FTIR revealed that evolution of
CO2 is considerably lowered by zinc hydroxystannate, andat a later stage of decomposition
the evolution of H2O and HBr (traces) can be identified. On the basis of the results obtained
a mechanism of decomposition was proposed that takes into account the reaction of tin
compounds with the products of ester linkage rupture processes.

INTRODUCTION At higher temperatures, a number of low molecular

Unsaturated polyester resins are a class of
thermosetting resins widely used in ship and boat
construction, offshore applications, water piping and
building construction [1, 2]. They have stable
structures and display good mechanical properties,
but there is still a need for better thermal and fire
performance. Results of decomposition studies can
be applied to thermal stabilisation as well as being
useful for the proposal of novel flame retardants with
a controlled mode of action.
The mechanism of thermal degradation of polyesters
has been studied for many years on the basis of model
compounds [3, 4]. It has been found that a β-CH
hydrogen transfer is involved, leading to the formation
of oligomers with olefinic and carboxylic end groups.
Under thermo-oxidative conditions, the
decomposition process starts by the formation of a
hydroperoxide at a methylene group [5]. The
exothermic effects observed by differential thermal
analysis (DTA) prior to the melting endotherm may
confirm that the thermo-oxidative reaction occurs
even in the solid state [6].
mass volatile products, including acetaldehyde,
formaldehyde and acetone, have been detected by
pyrolysis-gas chromatography (Py-GC) [7] or direct
pyrolysis mass spectrometry (Py-MS) [8]. The other
technique used in studies of polyester thermal
decomposition is thermal volatilisation analysis
(TVA) [9] .The results obtained by this method show
that ester decomposition occurs almost exclusively
when the number of β hydrogen atoms in the alkyl
group is high, as in poly(tert-butyl methacrylate) in
which there are nine such atoms, and in the isopropyl
and sec-butyl esters in which there are six and five
respectively [10]. The reaction proceeds through a
six membered ring intermediate involving these β
hydrogen atoms. When there are no β hydrogen
atoms, as in the methyl and neo-pentyl esters, ester
decompositions cannot occur and monomer is
formed exclusively. With only three β hydrogen
atoms, as in the ethyl ester, or two as in all the other
normal esters, depolymerisation and ester
decomposition occur in competition. Even when a
quite small amount of ester decomposition occurs,
the residual acid or the corresponding anhydride
units tend to block the passage of the

Polymers & Polymer Composites, Vol. 12, No. 2, 2004 127

 Ewa Kicko-Walczak
depolymerisation along the polymer chains, so that
monomer production tends to be retarded [11].
In an another study, Anderson and Freeman used
TGA and DTA to study the decomposition behaviour
of a polyester resin made from propylene glycol -
maleic anhydride - phthalic anhydride and cross-
linked with styrene [12]. A thermo-oxidative
degradation mechanism was proposed, involving
oxidative attack at the α-carbon of the styrene, followed
by rearrangement. Cleavage was then said to occur
between the carbonyl and the α-carbon, followed by
hydrogen transfer from the β-carbon to the benzoyl
radical. In another study, four halogenated polyester
thermosets based on 1,2-propanediol or
dibromoneopentyl glycol, maleic anhydride and
phthalic-, chlorendic acid- or tetrabromophthalic
anhydride were analysed by TGA and DSC [13]. It
wasfound that a general purpose resin made from a
glycol, phthalic anhydride and maleic anhydride
decomposed in air in three stages. The first stage,
occurring around 200°C was due to the elimination of
phthalic anhydride. The second stage, around 350°C,
was caused by the release of styrene and a complex
mixture of other materials, while the third stage
above 500°C involved the loss of high-boiling tars and
the oxidation of the char formed. The influence of
inorganic tin additives on the decomposition course
was also ascertained; both condensed and vapour
phase mode of actions appeared to be operating.
The present investigation deals with the thermal
decomposition of halogenated unsaturated polyester
resins, flame retarded by zinc hydroxystannate, by
using thermal analysis methods, either alone or
coupled on-line with spectroscopic methods.
EXPERIMENTAL
Materials
Unsaturated polyester resin (UPR) (commercial
reference P163-53, produced by “Organika-Sarzyna”
Table 1. Description of the samples
Sample No. Amount of ZHS [wt. %]
1 0
2 2
3 5
4 10
5 40
128
Co., Poland) was of the maleate/phthalate/
brominated glycol type. Cross-linking of the final
polyester formulations was carried out using 35%
by weight of styrene with methyl ethyl ketone
peroxide as catalyst, cobalt naphthenate as
accelerator and zinc hydroxystannate (ZHS) (Alcan
Co., UK) as flame retardant.
Techniques
Thermogravimetric analysis
Thermogravimetric analysis was performed on a
Netzsch TG 209 thermal analyser, operating in either
(i) a dynamic mode at a heating rate of 10 K/min or (ii)
an isothermal mode for 150 min. The conditions
were: sample weight - ~ 5 mg, atmosphere - air, open
α-Al2O3 pan.
Thermogravimetric analysis coupled
with Fourier Transform infra-red
spectroscopy
Thermogravimetric analysis coupled with Fourier
transform infra-red spectroscopy was carried out
using a Mettler-Toledo TGA/SDTA 851 thermal
analyser (heating rate = 20 Kmin-1, sample weight
~2 mg, air flow = 50 cm3/min) and a JASCO 610
FT-IR spectrometer. The thermogravimetric analyser
and spectrometer were suitably coupled to enable the
passage of evolved products from the furnace to the
gas cell over a short path, to minimise secondary
reactions or condensation on the cell walls. Moreover,
the experimental conditions were chosen to ensure
that the condensable products formed a submicron
aerosol mist. This size of aerosol has two advantages:
(i) the particles follow the gas stream lines, thus
minimising condensation, and (ii) the particles
produce little scattering in the mid-range IR, so the
condensable products can be analysed online in the
FT-IR cell.
Thermogravimetric analysis coupled with
mass spectroscopy
TG-MS measurements were made on a TA Instruments
DTA-TGA (SDT 2960) coupled with a Balzers
Thermostar quadropole mass spectrometer. The
quadrupole mass spectrometer was connected to the
thermobalance via a capillary coupling. The ionising
voltage of the cross-beam electron impact ionisation
source amounted to 70 eV, mass of the sample was ca.
4 mg and the heating rate was 20 K/min.
Polymers & Polymer Composites, Vol. 12, No. 2, 2004
Studies on the Mechanism of Thermal Decomposition of Unsaturated Polyester Resins with Reduced Flammability

RESULTS AND DISCUSSION operational in the temperature range of 240-340°C,

Results of thermogravimetric analysis of samples 1-5
are shown in Figure 1
The thermal decomposition of an unmodified
polyester resin starts to decompose slowly above
about 150°C and proceeds in one step up to ca.
420°C. The maximum decomposition rate occurred
at 360°C, as evidenced by the DTG profile. Samples
containing zinc hydroxystannate underwent a two-
step degradation; the first step was found to be
while the second one occurred at 340-420°C. It
should be noted that the char residue at 500°C
accounted for 9% of the unmodified resin weight
and for 20, 25, 29 and 43% in the case of samples
with 2, 5, 10 and 40% additives, respectively.
Thermogravimetric analysis under isothermal
conditions, displayed in Figure 2, showed that there
were no thermal effects related to a “time of induction”,
so that the thermal process can be further investigated
by dynamic methods (Figure 2).

Figure 1. Thermogravimetric curves of samples 1-5 at 10 deg/min under air atmosphere

1 – UPR
2 – UPR + 2% ZnSn(OH)6
3 - UPR + 10% ZnSn(OH)6
4 - UPR + 5% ZnSn(OH)6
5 - UPR + 40% ZnSn(OH)6

Figure 2. Thermogravimetric curves of samples 1-3 under isothermal conditions (150 min, air)

Polymers & Polymer Composites, Vol. 12, No. 2, 2004 129

 Ewa Kicko-Walczak
To achieve an additional insight into the mechanism
of decomposition, cupled methods were used. The
results of TG-FTIR (Thermogravimetric analysis
cupled with Fourier Transform infra-red
spectroscopy) studies of sample 1 revealed that several
characteristic absorption bands at ~2470, ~1750 and
~1200 cm-1, were present, which corresponded to the
vibrational frequencies of CO2, C=O and C-O groups,
respectively (Figure 3).
Analysis of the TG-MS (Thermogravimetric analysis
cupled with mass spectroscopy) data yielded
additional information about the emission of volatiles
(Figure 4).
It has been found that the elimination of phthalic
anhydride takes place at ca. 330°C, then, at ca. 380°C
styrene, benzoic acid and a complex mixture of other
aromatic compounds are evolved.
The TG-FTIR data for sample 3 (with 5 % of additive)
showed that evolution of CO2 was considerably
lowered, whereby at a higher stage of decomposition
the evolution of H2O and HBr in traces could be
identified (Figures 5 and 6).
Figure 3. Stacked plot of FT-IR spectra of the decomposition process of sample 1 at a heating rate of 20 K/min
(Tinitial = 30°C)
130
It should be noted that in the case of the heating rate
of 20 deg/min, all the thermal events are slightly
shifted towards higher temperatures. Such a high
heating rate was necessary to produce volatiles at
concentrations high enough to be detected on-line in
the FT-IR measuring cell, and to provide continuous
monitoring of the i.r./mass spectra of the evolving
products, as well as a quantitative analysis of the
gases [14] . In contrast to pyrolysis GC, in which all
the gases produced by heating to a given temperature
are separated and analysed as a batch, TG-FT/IR/MS
offers the great advantage of sequentially identifying
the gases for a comprehensive vapour-phase analysis.
On the basis of the results obtained, the proposed
mechanism for the action of zinc hydroxystannate
additive in a halogenated resin involves the following
sequence:
1. The resin degrades below 200°C to yield
predominately phthalic anhydride and styrene
with theelimination of a hydrocarbon - CH2Br
species.
Resin → Phthalic anhydride, styrene + Y - CH2 - Br
where Y is a hydrocarbon.
Polymers & Polymer Composites, Vol. 12, No. 2, 2004
Studies on the Mechanism of Thermal Decomposition of Unsaturated Polyester Resins with Reduced Flammability

Figure 4. Intensity of m/e signals for the decomposition of sample 1 followed by TG-MS at heating rate of
20 K/min (Tinitial = 30°C)

Figure 5. FT-IR spectra taken at different temperatures during the decomposition of sample 3 at a heating rate of
20 K/min (Tinitial = 30°C)

Polymers & Polymer Composites, Vol. 12, No. 2, 2004 131

 Ewa Kicko-Walczak
Figure 6. Stacked plot of FT-IR spectra of the decomposition process of sample 3 at a heating rate of 20 K/min
(Tinitial = 30°C)
2. Interaction of the Hydrocarbon - CH2Br species
with the Zn/Sn additives to give SnBrx
Y - CH2 - Br + (ZnSn(OH)6 → ZnSnO3 + H2O) →
Zn2SnO6 + SnBrx
where x = 2 or 4
Evidence for this reaction includes the fact that
both tin and bromine are lost in the same
temperature range.
3. Finally the tin bromide in the flame is hydrolysed
to yield HBr and tin oxide. The HBr acts as an
eliminator of free radicals, which inhibits the
flame reactions.
SnBr2 + H2O → SnO2 + HBr
Generally, two independent mechanisms are possible:
1. promotion, leading to a reduction in the supply of
flammable volatiles to the flame,
2. gas phase oxidation of the soot and aromatic tars
produced during polymer pyrolysis.
This mechanism is also supported by X-ray powder
diffraction analysis, which showed that when heated
to 300°C, the product from ZHS gave a featureless
pattern with no peaks, showing that the ZS formed
132
was in an amorphous state. Further heating to 1000°C
gave a product showing peaks consistent with
Zn2SnO4 and SnO2.
The literature data on the thermal degradation
mechanisms of UPRs, mentions
- random scission
- intramolecular transfer during unzipping (e.g.
degradation of the polystyrene phase in the UP
network), and
- secondary reactions of primary products,
corresponding with decomposition caused by
radical species, such as RO. products coming
from ester linkage rupture reactions.
The following group of reactions seems to be
responsible for the final degradation of UPR under
investigation in the higher temperature range that
corresponds to the combustion processes in the
presence of tin compounds [15]:
SnO + H·
SnOH·
SnOH· + H·
SnO + H2
SnO2 + H2
SnO + H2O
Other characteristic temperatures of decomposition
and char residue at 500°C of samples 1-3 also
considerably differ, indicating the influence of
Polymers & Polymer Composites, Vol. 12, No. 2, 2004
Studies on the Mechanism of Thermal Decomposition of Unsaturated Polyester Resins with Reduced Flammability
chemical structure on the degradation pathway.
Generally, at elevated temperature and in air,
macroradicals react with oxygen to form
hydroperoxides, which are themselves unstable and
will break down rapidly, forming more free radicals.
According to the Bolland-Gee mechanism a
macroradical is initially formed, which will then
react with oxygen to to form a peroxy radical. The
peroxy radicals are reactive and will abstract a
hydrogen atom, either by an intra- or intermolecular
process, to generate a hydroperoxide group and
another macroradical site. The hydroperoxides will
then decompose, resulting in the formation of alkoxy
and hydroxy radicals, which in turn can react with
the polymer backbone giving water molecules -
Scheme 1 [14]:
Scheme 1
POLYMER → P· (Initiation)
P· + O2 → PO2·
PO2 + PH → PO2H + P·
2 PO2H → PO· + PO2· + H20 (Chain Branching)
PO2H → PO· + OH·
PH + OH· → P · + H2O
2PO2· → Inert Products (Termination)
PO2· + P· → PO2P
2P· → P-P
On the other hand, the course of thermal
decomposition depends not only on the basic chemical
structure of a polymer, but also on many internal and
external factors, often located on other microstructural
levels. An advanced kinetic analysis of the degradation
process of flame-retarded UPRs showed that the
activation energy barrier is higher for flame-retarded
samples for α>0.8, which corresponds to a temperature
of ca. 400°C.
Basically, three stages of decomposition can be
observed; the beginning of thermal degradation has
an activation energy of ca. 130 kJ/mol. This value of
E may correspond to depolymerisation of styrene
micronodules formed at the gelation phase. The
second step,with an activation energy of ca.150-170
kJ/mol, may be attributed to the decomposition of
polyester network, whereby the third step (E>200 kJ/
mol) can be associated with random scission reactions
that lead to the formation of low-molecular weight
products [16].
Polymers & Polymer Composites, Vol. 12, No. 2, 2004
The flammability suppressant action of tin
compounds should be considered in the context of
three main approaches towards polymer combustion,
namely vapour phase, condensed phase and
miscellaneous. A valuable way of distinguishing
between these mechanisms is offered in the TG
method [17]. For the samples studied in the course
of this work, the amount of char residue indicates
that there is not just one definite mechanism
operating – a similar complexity of the nature of the
reaction between, for example, tin(IV) oxide and
zinc stannate and the halogen-containing polyesters
has been described.
It should be noted that for the heating rate of 20 deg/
min, all the thermal events are slightly shifted towards
higher temperatures. Such a high heating rate was
necessary to produce volatiles at concentrations high
enough to be detected on-line in the FT-IR measuring
cell and to provide continuous monitoring of the i.r./
mass spectra of evolving products, as well as the
quantitative analysis of gases [18] .
On the other hand, during the thermal decomposition
the stabilising action of zinc hydroxystannate
additives may be explained by the formation of
surface-localised spherical barriers, which are growing
according to the nucleation growth mechanism and
which attenuate the transfer of heat from the
decomposition zone to the substrate. An additional
role may be attributed to the interaction of metal ion-
polymer functional groups that should lead to the
formation of the long-range structural regularities.
These, in turn, thermally stabilise the whole system
(‘strong interactions model’) [19].
CONCLUSIONS
In this work, results of studies of the thermal
degradation of halogenated unsaturated polyester
resin (UPR), flame retarded by zinc hydroxystannate
and cross-linked with styrene, showed that
elimination of phthalic anhydride takes place at ca.
330°C, and then at ca. 380°C., styrene and a complex
mixture of other aromatic compounds are evolved.
Further studies using TG-FTIR have revealed that
the evolution of CO2 is considerably reduced by zinc
hydroxystannate, whereby at a later stage of
decomposition the evolution of H2O and HBr (traces)
can be identified. On the basis of the results obtained,
a mechanism of decomposition was formulated that
takes into account the reactions of tin compounds
with the products coming from ester linkage rupture
processes.
133
 Ewa Kicko-Walczak

REFERENCES 10. N. Grassie and D. H. Grant, Polymer, 1960, 1, 445.

1. E. Kicko-Walczak, J. Appl. Polym. Sci., 1999,
74, 379.
2. E. Kicko-Walczak, Polimery, 2000, 45, 808.
3. L.H. Buxbaum, Angew. Chem. Int. Ed., 1968, 7,
182.
4. F. Pilati, P. Manaresi, B. Fortunato, A. Munari
and V. Passalaqua, Polymer, 1981, 22, 799.
5. H. Zimmermann and in: N. Grassie (Ed.),
Developments in Polymer Degradation, London,
Applied Science,1984 vol. 4, 427.
6. S. J. Evans, P. J. Haines and G. A. Skinner,
Thermochim. Acta, 1996, 278, 77.
7. M. Dzieciol and J. Trzeszczynski, J. Appl. Polym.
Sci., 1998, 69, 2377.
8. A. Baudry, J. Dufay, N. Regnier and B. Mortaigne,
Polym. Degrad. Stab., 1998, 61, 441.
9. I. C. McNeill and S. Basan, Polym. Degrad,
Stab., 1993, 41, 311.
11. N. Grassie, A. Johnston and A. Scotney, Eur.
Polym. J., 1981, 17, 589.
12. D. A. Anderson and E. S. Freeman, J. Appl.
Polym. Sci., 1959, 1, 192.
13. P. A. Atkinson, P. J. Haines and G. A. Skinner,
Thermochim. Acta, 2000, 360, 29.
14. N. S. Allen and M. Edge, ‘Fundamentals of
Polymer Degradation and S t a b i l i s a t i o n ’ ,
Elsevier Applied Science, London, 1992, 3, 128.
15. R.S. Bains, P.A. Cusack and A.W. Monk, Eur.
Polym. J., 1990, 11, 1221.
16. P. A. Cusack, M. S. Heer and A. W. Monk,
Polym. Degrad. Stab., 1997, 58, 229.
17. P. A. Atkinson, P. J. Haines and G. A. Skinner,
Polym. Degrad. Stab., 2001, 71, 351.
18. K. Pielichowski and I. Hamerton, Eur. Polym. J.,
2000, 36, 171.
19. E.Kicko-Walczak, J.Appl. Polym. Sci., 2003, 88,
(13) 2851.

134 Polymers & Polymer Composites, Vol. 12, No. 2, 2004