Polymer Degradation and Stability 72 (2001) 345±351

www.elsevier.nl/locate/polydegstab

Thermal degradation of monodisperse polystyrene in bean oil

Dewen Dong *, Shigeru Tasaka, Norihiro Inagaki
Satellite Venture Business Laboratory (SVBL), Shizuoka University, 3-5-1 Johoku, Hamamatsu 432-8561, Japan

Received 29 September 2000; accepted 7 November 2000

Abstract
Thermal degradation of monodisperse polystyrene (PS) in bean oil was investigated in the temperature range of 305±350 C. The
degradation products were identi®ed by means of gel permeation chromatography (GPC) and Fourier transform infrared spectro-
metry (FTIR). A signi®cant feature for the investigated system was that PS in the presence of bean oil thermally degraded into larger
fragments of the polymer chain instead of monomer or oligomers which are usually generated in the direct thermal degradation. The
average molecular weights of degradation products of PS decreased and the polydispersity indexes (Mw/Mn) increased but did not
exceed 2 as the reaction time increased. The kinetics of the degradation reaction was also examined based on the GPC measurements.
The results revealed that the degradation of PS in bean oil was a ®rst order reaction and the energy of activation for chain scission was
215 kJ mol 1. The thermal degradation of PS in bean oil is believed to be a random chain scission process involving radical inter-
molecular transfer between bean oil and intermediate macroradicals of PS. # 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Bean oil; Gel permeation chromatography (GPC); Polystyrene; Thermal degradation

1. Introduction be due, at least in part, to the fact that the experimental

As an important aspect of polymer science, degrada-
tion of polymers has been widely investigated in the past
decades [1±3]. This stems from both academic interests
and practical goals, such as characterizing polymer
structures, developing anti-degradants or stabilizers to
extend polymer durability, designing new polymer struc-
tures which are stable to severe service conditions, and
exploring the feasibility of polymer recycling. The thermal
degradation of polystyrene (PS) was studied even a half
century ago [4] and later reviewed by Cameron [5], and
Stivala [6]. Jellinek [4] initially proposed the existence of
``weak links'' in PS prepared by radical polymerization.
The concept was adopted by many researchers [7,8] to
interpret the rapid drop in molecular weight at low
reaction time. Chiantore et al. [9] later found some
direct evidence for the theory. Unfortunately, despite
the considerable amount of work the degradation
kinetics and mechanism of PS still remain under inquiry
and discussion, and there are even contradictions
between the conclusions of di€erent authors. This might
* Corresponding author. Fax: +81-53-4781419.
E-mail address: dewend@yahoo.com (D. Dong).
0141-3910/01/$ - see front matter # 2001 Elsevier Science Ltd. All rights reserved.
PII: S0141-3910(01)00031-3
conditions varied considerably from one work to
another.
On the other hand, most of above investigations are
limited to the direct thermal degradation. Thus, the
higher viscosity and lower transfer rate of mass and
heat make the degradation behavior of PS complicated.
To eliminate the problems Sato et al. [10] and Madras
et al. [11] recently investigated the degradation behavior
of PS in organic solvents and mineral oil, respectively.
Meanwhile some researchers applied various plant oils
to recycle waste plastics including polystyrene foams
[12±15]. However, so far there are only a few studies on
such thermal degradation and most of these reports can
only be found in some patents. With the aim of a bet-
ter understanding of thermal degradation behavior of
polymers in plant oil and to develop the novel recycling
technique, we have undertaken a pyrolysis study of
monodisperse PS in bean oil. Bean oil is used since it is
a natural plant oil and increasingly used frying bean oil
accumulates nowadays with almost no use in daily life.
The degradation products were examined by gel per-
meation chromatography (GPC) and Fourier trans-
form infrared spectrosmetry (FTIR), and the kinetics
and mechanism of the degradation reaction are also
discussed.
346 D. Dong et al. / Polymer Degradation and Stability 72 (2001) 345±351
2. Experimental
2.1. Materials
Polystyrene was purchased from Mitsubishi Chemical
Co. with molecular weight Mw: 3.9105 and poly-
dispersity index Mw/Mn=1.1. Bean oil was provided by
Nikka Oil Co. Ltd. (iodine value=133, peroxide value=5
meq/kg).
2.2. Degradation of PS
The degradations of PS within and without bean oil
were carried out by programmed heating at 50 C/min to a
desired temperature, i.e. 305, 320, 335 or 350 C, and then
isothermal heating at the temperature ( 0.5 C) for dif-
ferent times. The sample was placed on the round-bottom
of a vertical cylindrical vessel (10.51.4 cm I.D.), the
lower part of which was introduced into an oven. The
temperature was measured using a TX-K12D thermo-
couple connected to a TX-570 digital thermometer ( 50±
700 C) and controlled with an Omron E5BX temperature
controller. Thus the temperatures quoted in this paper are
sample temperatures. The reaction time was recorded
from the moment when the sample temperature reached
the desired value. At the end of the heating period, the
vessel, together with the sample, was taken out of the
heating system and cooled under ambient atmosphere.
The extents of volatilization were evaluated by measuring
the mass loss of the sample. The nonvolatile degradation
products were investigated by means of GPC and FTIR.
2.3. Measurements
The molecular weight distribution of degradation resi-
due of PS was analyzed at 40 C with a Tosoh HPLC-8020
gel permeation chromatography (GPC), equipped with
two separation columns of TSK gel GMHXL (7.8 mm
I.D.30 cm2) (TOSOH Co.) and a di€erential refract-
ometer. Tetrahydrofuran (THF) was used as eluent at a
¯ow rate of 1.0 ml/min. Molecular weights were cali-
brated with standard PS samples (TOSOH Co.) ranging
from 5.0102 to 1.1106. Infrared (IR) spectroscopy
measurements were conducted with a HORIBA FT 300.
3. Results and discussion
3.1. Direct thermal degradation of PS
Direct thermal degradation was performed on mono-
diperse PS (40 mg) by heating to 350 C at the rate of
50 C/min, and keeping it at 350 C for di€erent times,
i.e. 0, 5, 10, 20, 30, 45 or 60 min.
Previous work on the pyrolysis of PS has been repor-
ted by many researchers [16±18]. These early studies
revealed that the thermal degradation of PS is a radical
process through both end-chain and random scissions.
The main volatile products are styrene monomer toge-
ther with a certain amount of benzene and toluene, and
a small cold-ring fraction that consists of oligomer parts
such as dimer, trimer, tetramer and pentamer.
In our study, the evolution of volatile substances was
observed throughout the whole process. After being
pyrolyzed for about 1 h at 350 C, PS decomposed com-
pletely without residue. Fig. 1 shows the GPC measure-
ments of the nonvolatile degradation products at
di€erent reaction times. As has been noted the average
molecular weight of PS decreases rapidly within a short
period, i.e. several minutes, then the trend slows up to
half an hour, later followed by an accelerating decrease
in molecular weight. The molecular weight distribution
curve shift suggests that the larger fragments of PS
chains are generated due to random scission. The dis-
tinguishable peak at low molecular weight is attributed
to a combination of oligomers, especially dimer at
Mw=206, due to speci®c scission, i.e. end-chain scis-
sion. The monomer (Mw=162) is also detectable on the
GPC measurement. However, most of the monomer left
the reaction system as a volatile product, therefore, the
peak for the monomer in the GPC curve is not strong.
No evidence for repolymerization or cross-link reactions
is observed. Apparently, the resulting nonvolatile
degradation material is composed of styrene monomer,
Fig. 1. GPC curves of original PS (a) and degradation residue of PS
degraded at 350 C for di€erent time (min.): b: 0, c: 5, d: 10, e: 20, f: 30,
g:45, h: liquid fraction (30 min).
 D. Dong et al. / Polymer Degradation and Stability 72 (2001) 345±351
oligomer (dimer), and larger fragments of PS chain. The
rapid decrease in molecular weight at the initial stage
might result from the existence of weak-links along the PS
chain, whereas in the ®nal stage it results from the auto-
accelerating oxidation of hydrocarbons. All the results
suggest that both random and speci®c scissions occur at
350 C during the degradation of PS which is consistent
with the conclusion of previous literatures [16±18].
Fig. 2 shows the FTIR spectra of degradation pro-
ducts of PS. Compared with the original PS, the liquid
fraction which chie¯y consists of a dimer of PS exhib-
ited obvious absorption at about 1650±1750 cm 1,
whereas the residue products exhibit very similar spectra
to that of original PS. The absorption in the region
1650±1750 cm 1 is generally assigned to a composite
absorbance in which aldehydes (1735 cm 1) and ketones
(1720 cm 1) are the main species formed during the
early stages of degradation but carboxylic acids (1710
cm 1) predominate in the later stages. Undoubtedly,
oxygen of air participated in the thermal degradation
reaction at high temperature and led to the formation of
the carbonyl groups, which ®nally remained in the
degradation products, especially those cold-ring fraction
with small molecular weight.
3.2. Thermal degradation of PS in bean oil
In this section, the thermal degradation of PS was
performed in bean oil. Seventy-seven miligrams of PS
and 700 mg of bean oil were added into the glass vessel,
then the mixture was heated to and kept at a desired
temperature, i.e. 350 C, for di€erent times. Bubbles
were observed when the temperature reached 300 C, but
PS was only melted and swollen by bean oil even at
Fig. 2. IR spectra for original PS (a), residue (b) and liquid fraction
(c) of PS degraded at 350 C for 30 min.
347
350 C. That was to say, PS could not dissolve into bean
oil at degradation temperature. After being cooled down
to room temperature, a yellowish solid phase separated
immediately from the liquid system.
Both the two parts of the nonvolatile products were
analysed by GPC measurements. Fig. 3 shows the GPC
curves of the liquid fraction produced at 350 C for dif-
ferent reaction times. It is obvious that the average
molecular weight of the liquid fraction increased gradu-
ally as the reaction time increased (from a to e). How-
ever, the degradation products with small molecular
weight, such as monomer and dimer, are not detected by
the GPC measurements. Moreover, the liquid fraction
of PS/oil mixture, especially that produced at 350 C for 0
min, has a very similar GPC curve to that of the original
bean oil.
Fig. 4 illustrates the GPC elution curves of the solid
fraction obtained at 350 C and di€erent reaction times.
Fig. 3. GPC curves of liquid degradation fraction of PS/oil mixture
degraded at 350 C for di€erent time (min): a: 0, b: 10, c: 30, d: 45, e: 60.
Fig. 4. GPC curves of PS (a) and solid degradation fraction of PS/oil
mixture degraded at 350 C for di€erent time (min): b: 0, c: 10, d: 20,
e: 30, f: 45, g: 60, h: 90, i: 120 (a±i: from left to right).
348 D. Dong et al. / Polymer Degradation and Stability 72 (2001) 345±351

The symmetric peak at the short elution time of the polydispersity index value does not exceed 2 in our
curves is assigned to the larger fragments of PS molecular investigations. The relationship between the Mw and
chains, whereas a group of peaks at the longer elution reaction time is further illustrated in Fig. 5. As has been
times are attributed to the bean oil since their changes are noted, the average molecular weight of solid nonvolatile
consistent with that of liquid fraction. Consequently, the degradation products of PS/oil decreases rapidly in the
solid nonvolatile degradation product is predominantly initial stage, which is followed by a gradual decrease.
comprised of bean oil and fragments of PS chain rather
than monomer or oligomer. Moreover, the average mole- 3.3. Kinetics and mechanism of PS degradation in bean oil
cular weight of the resulting fragments decreases gradu-
ally as the reaction time increases. Comparing to the direct By measuring the decrease in Mn as a function of time
thermal degradation, the thermal degradation of PS in under isothermal conditions in the range 305±350 C, the
bean oil is obviously slowed. Meanwhile, it is interesting kinetics were investigated. In a polymer undergoing a
that the amount of bean oil in the solid fraction depended chain scission reaction with negligible volatilisation, the
on the reaction time, i.e. the longer the reaction time, the number of scissions per polymer chain (s) and the frac-
less the amount of bean oil in the solid fraction. This tion of bonds broken between the structural units ( )
might be attributed both to the increase in the average can be given by:
molecular weight of bean oil and to the decrease in the
average molecular weight of fragments of PS. s ˆ Mno Mn †=Mn 1†
The volatile products were generated throughout the
degradation and the amount increased with the reaction ˆ ms=Mno 2†
time. The contrasting experiments on bean oil and PS/
oil revealed that the volatile products were determined
by the amount of added bean oil and the experimental
conditions such as reaction temperature and reaction
time. For example, when PS/oil mixture (containing 700
mg bean oil) and bean oil (700 mg) were treated at 350 C
for 60 min, 70 and 67 mg of volatile products were
obtained, respectively. The investigations suggest that
the volatile products are almost entirely from bean oil
and further con®rmed that only fragments of PS chains
rather than monomer or oligomer are generated in the
thermal degradation of PS in the presence of bean oil.
From the GPC measurements, average molecular
weights and molecular weight distribution for the degra-
dation products are obtained and listed in Table 1.
Apparently, the average molecular weights of degradation
products of PS are lowered and the polydispersity indexes Fig. 5. Average molecular weight (Mw) of solid degradation fraction
(Mw/Mn) increase with the reaction time. However, the of PS/oil mixture degraded at 350 C as a function of reaction time.

Table 1
The experimental conditions and results of thermal degradation of PS/oil

Sample PS Bean oil Temperature Timea Peakb Mwb Mw/Mnb

(%) (%) ( C) (min) (min) (10 5)

PS1 10 90 350 0 12.55 2.61 1.69

PS2 10 90 350 10 12.97 2.12 1.74
PS3 10 90 350 20 13.10 1.99 1.79
PS4 10 90 350 30 13.24 1.75 1.83
PS5 10 90 350 45 13.33 1.60 1.85
PS6 10 90 350 60 13.49 1.36 1.92
PS7 10 90 350 90 13.74 1.02 1.94
PS8 10 90 350 120 14.01 0.85 1.98
PS9 10 90 305 60 12.58 2.50 1.73
PS10 10 90 320 60 12.76 2.25 1.82
PS11 10 90 335 60 13.37 1.66 1.89
a
The reaction time was recorded from the moment when sample temperature reached the desired value.
b
Elution time, Mw and Mw/Mn were measured by GPC for the solid degradation fraction of PS/oil mixture degraded under di€erent conditions.
 D. Dong et al. / Polymer Degradation and Stability 72 (2001) 345±351
where Mno and Mn are the number average molecular
weights of polymer before and after degradation, respec-
tively and m is the molecular weight of the structural unit.
The values of Mn were obtained from GPC measurements
on the non-volatile degradation products derived under
varied conditions. Fig. 6 shows the changes of s at 350 C
as a function of reaction time. It seems that the number of
scissions per polymer molecule follows a regular varia-
tion relating to reaction time since all the experimental
points ®t onto a single straight line. The results suggest
that the degradation of PS in bean oil is a ®rst order
process. They also imply that the ``weak link'' scission can
be negligible compared with the ``normal'' chain scission
under our investigation conditions. However, the fraction
Fig. 6. Number of scissions (s) for the solid degradation fraction of
PS/oil mixture degraded at 350 C as a function of reaction time.
Fig. 7. Arrhenius plot of initial rate of chain scission as a function of reciprocal of temperatures.
349
of bonds broken between the structural units is lower
under our investigation. For example, at 350 C the value
of is of the order of about 5 in every 10,000 structural
units in the initial stage. These data suggest that the
mechanism of the scission is complex and involves more
than one rate determining step.
If ®rst order kinetics is assumed for the chain scission,
the initial rate equation is:
dc=dt†t ! 0 ˆ k 3†
where c is the fraction of total bonds broken per minute.
The initial rates at di€erent temperatures were calcu-
lated based on the GPC measurements. Fig. 7 shows the
values of ln(dc/dt)t!0 as a function of the reciprocal of
temperature. The experimental points ®t onto a straight
line. This further con®rms that the chain scission reac-
tion is a ®rst order process. Based on the Arrhenius
equation, the energy of activation can be calculated
through the slope of the straight line. The result reveals
that the energy of activation for the chain scission reac-
tion of PS in bean oil is 215 kJ mol 1 which is in
accordance with the energy of activation (205±226 kJ
mol 1) for the ``normal'' PS chain scission reaction
occurring at a higher temperature [8,19].
Fig. 8 shows IR spectra of the degradation products
for PS/oil degraded at 350 C for 30 min as well as that
of the original PS and bean oil. Bean oil is composed of
glycerides of fatty acids with the general structure:
R1 COOCH2 CH OOCR2 † CH2 OOCR3
350 D. Dong et al. / Polymer Degradation and Stability 72 (2001) 345±351
Fig. 8. IR spectra for original PS (a), solid (b) and liquid fraction (c) of
PS/oil mixture degraded at 350 C for 30 min, and original bean oil (d).
where R1, R2 and R3 stand for the hydrocarbon por-
tions of the fatty acid chains. As a drying oil, bean oil,
i.e. the unsaturated fatty acid components, can absorb
oxygen from atmosphere and lead to formation of
radicals and then cross-linking reaction [20,21]. Grassie
previously investigated the degradation mechanism of
the glycerides of fatty acids and revealed that the ester
yielded carbonic acids and ole®ns by b-cis elimination at
high temperature, e.g. 300 C, and radicals further gen-
erated from the unsaturated compounds [3]. As shown
in Fig. 8, the original bean oil exhibited a characteristic
ester absorption at 1746 cm 1, and the absorption at
3009 cm 1 represents the double bond absorption of the
unsaturated fatty acids. On the spectra of both liquid and
solid fraction degradation products of PS/oil, a new
absorption at 1715 cm 1 appear indicating the formation
of carbonic acids. Meanwhile, the disappearance of
absorption at 3009 cm 1 suggests that the unsaturated
groups, double bonds, of bean oil participate in reactions
during the degradation, which also make a contribution
to the average molecular weight increase of the liquid
fraction. The IR spectra further con®rm that the low
molecular weight compounds in solid fraction are made
up of bean oil, and higher molecular weight products
are larger fragments of PS chains. In addition, the liquid
fraction contains various products of bean oil but does
not include any product from PS.
In spite of the fact that there are so many di€erent
theories on degradation behavior of PS, the mechanism
may be described in term of a general radical depoly-
merization. The degradation of PS at high temperature
is associated with initiation by scission of polymer
chains to form radicals. The radicals then undergo
depropagation which is accompanied by intramolecular
or intermolecular transfer of radicals. Therefore, there is
no doubt that the degradation of PS in bean oil also
involves in a radical process. However, the addition of
bean oil makes it a little more complicated. The result
that no monomer or oligomer degradation products are
yielded in the studied system shows that bean oil plays a
very important role in the degradation process. Unlike
the direct thermal degradation, the degradation of PS in
bean oil occurs in a swollen melt. Relatively small mole-
cules of bean oil di€use into PS melt and swell the PS.
In the initial stage, the radicals are formed by polymer
chain scission. Bearing in mind the bean oil is involved
in the system, it can generate radicals (R ) at high tem-
perature as mentioned above. Of course, it can induce
polymer chain scission as described below:
R ‡  CH2 Ph†CH CH2 CH Ph† CH2 
!  CH2 Ph†HC CH2 CH Ph† CH2 
‡R 4†
 CH2 Ph†HC CH2 CH Ph† CH2 
!  CH2 Ph†HC ‡ CH2 ˆ CH Ph† CH2 
5†
If chain scission occurs through a radical mechanism,
the radical pairs could be mutually deactivate within the
``cage'' in which they are formed. The ``cage e€ect'' was
proposed by Grassie and Kerr to account for the kinetics
of PS degradation at volatilisation temperature [7,22].
They considered the majority of radical pairs formed by
scissions of internal bonds would recombine since the high
viscosity hindered their di€usion. In fact, in our studied
system, bean oil may introduce another ``cage e€ect'' for
macroradicals, especially terminal ones. Molecules of
bean oil isolate polymer chains, to some extent, decrease
the possibility of intermolecular transfer of macro-
radicals. Meanwhile at high viscosity the chain entan-
glements would hinder intramolecular transfer of
macroradicals. We consider that intermolecular transfer
of terminal macroradicals occurring between macro-
radical and bean oil molecule (hydrogen atom of a-
methylene to double bond or hydrogen atom of carboxy
group) is of importance under such conditions, as shown
in Eqs. (6) and (7). Therefore, random-chain scission
reaction was predominant and end-chain scission reac-
tion nearly does not occur in the studied system.
 CH2 Ph†HC ‡ R CH ˆ CH CH2 
!  CH2 Ph†CH2 ‡ R CH ˆ CH HC 
6†
 D. Dong et al. / Polymer Degradation and Stability 72 (2001) 345±351
 CH2 Ph†HC ‡ R COOH

!  CH2 Ph†CH2 ‡ R COO
In summary, PS thermally degraded in bean oil into
larger fragments of polymer chain rather than monomer
or oligomers. The average molecular weights of degra-
dation products of PS were lowered and the poly-
dispersity indexes (Mw/Mn) increased but did not exceed
2 as the reaction time increased. The analysis results
revealed that the degradation of PS in bean oil was a
®rst order process and the energy of activation for the
chain scission reaction was 215 kJ mol 1. The thermal
degradation of PS in bean oil is believed to be a random
chain scission process involving radical intermolecular
transfer between bean oil and intermediate macroradical
of PS. Everyone can easily understand that regenerating
the monomer from the waste polystyrene is a good recy-
cling method. However, generation of the larger frag-
ment of polystyrene is important, too. For example, it
can be applied in recycling polystyrene foams, namely to
reduce the volume of waste expanded polymers with a
slight and controlled lowering of molecular weight. The
resulting mixture might be applied in modelling, gar-
dening materials, plates etc. Further investigations on
the thermal degradation behavior of the system, the
property, structure and application of the degradation
products are in progress.
351
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