Journal of Analytical and Applied Pyrolysis

65 (2002) 71–90
www.elsevier.com/locate/jaap

Basic study on a continuous flow reactor for

thermal degradation of polymers
Katsuhide Murata a,*, Y. Hirano a, Y. Sakata b,
Md. Azhar Uddin b
a
Chiba Laboratory, Mitsui Engineering & Shipbuilding Co. Ltd., Ichihara-City, Chiba 290 -8601, Japan
b
Department of Applied Chemistry, Okayama Uni6ersity, Tsushima Naka, Okayama 700 -8530, Japan
Received 29 June 2001; accepted 31 August 2001

Abstract

A continuous flow reactor for thermal degradation of polymer such as polyethylene (PE),
polypropylene (PP) and polystyrene (PS) was operated at the feed rate of 0 – 1.5 kg h − 1 in
order to investigate the characteristics of the continuous flow operation and the thermal
degradation behavior of polymers. Rate studies on thermal degradation of polymers were
made at various temperatures and under a steady state. The activation energies, calculated
on the basis of the rate of volatilization, were 221, 216 and 208 kJ mol − 1 for thermal
degradation of PE, PP and PS, respectively. These activation energies indicate that a
chemical reaction takes a role of rate controlling step in this reactor system. By continuous
flow operation, polymers were converted to the liquid product with high yield of 93.6– 96.2,
96.1–99.1 and 99.9 wt.% for PE, PP and PS. The liquid products consisted of a wide
spectrum of hydrocarbons distributed C4 –C30. Thermal degradation by continuous flow
operation is a suitable technique for converting plastic polymers into liquid hydrocarbons
which could be used as feed stock materials. Based on the observed information, a
macroscopic mechanism was proposed. The thermal degradation of polymers consists of two
distinct reactions which simultaneously occur in the reactor. One is a random scission of
links which causes a molecular weight reduction of the raw polymer, and the other is a
chain-end scission of CC bonds, which causes the generation of the volatile product. The
chain-end scission takes a place at the gas–liquid interface in the working reactor. © 2002
Elsevier Science B.V. All rights reserved.

Keywords: Polyethylene; Polypropylene; Polystyrene; Thermal degradation; Continuous flow operation;

Macroscopic mechanism

* Corresponding author. Present address: 3-2-2 Wakamiya, Ichihara-City, Chiba 290-0006, Japan.
Tel./fax.: + 81-436-41-6943
E-mail address: ay5k-mrt@asahi-net.or.jp (K. Murata).

0165-2370/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 5 - 2 3 7 0 ( 0 1 ) 0 0 1 8 1 - 4
72 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90

1. Introduction

Recently, the thermal degradation of polymers is becoming an increasingly

important method for the conversion of waste plastics into valuable chemicals
and fuel oil. In order to develop an industrial scale waste plastics treatment
plant, it is necessary to process large amounts of polymer in a continuous flow
reactor. Most of the previous researches on the thermal degradation of polymers
have studied batch reactor systems mostly in order to investigate the stability
and/or the degradation mechanism of synthesized polymers. However, so far only
a few researches on the thermal degradation of polymers has been carried out
using a continuous flow reactor [1– 3].
When the thermal degradation of polymers is carried out in a continuous flow
type operation, the experimental data are obtained at a steady state, that is, at a
constant temperature, a constant pressure and a constant amount of reactor
contents. Therefore, a continuous flow reactor rather than by a batch one is
optimum for the thermal degradation of polymers.
In the present study, the author carried out the thermal degradation of
polyethylene (PE), polypropylene (PP) and polystyrene (PS) in a stirred tank
reactor by continuous flow operation. Thus the data on the rate and the product
from thermal degradation of those polymers were obtained in a steady state. The
characteristics of the continuous flow reactor and the thermal degradation mech-
anism of those polymers will be discussed.

2. Experimental

2.1. Materials

PE (high density), PP and PS were obtained from Mitsui Chemicals, Inc. The
physicochemical properties of the polymers are shown in Table 1.

Table 1
Properties of original polymers

Property PE PP PS

Density (g cm−3) 0.968 0.906 1.050

Ash (wt.%) 0.03 0.04 0.02
Conradson carbon (wt.%) 0.10 0.10 0.06
Higher calorific value (J g−1) 48 950 46 400 43 300
Average molecular weight (Mw) 1.12E+05 2.17E+05 1.35E+05
 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90 73

Fig. 1. Continuous flow stirred tank reactor for thermal degradation of polymers.

2.2. Experimental procedure

Fig. 1 shows a schematic diagram of the experimental apparatus used for the
continuous flow operation of polymer degradation in the present study. The
principal part of the apparatus consisted of an extruder with variable feed rates of
0 – 1.5 kg h − 1, a stainless steel vessel reactor having a volume of 5 l installed with
a rotating agitator, a water cooled vent condenser, a liquid product receiver having
a glass level gauge, a seal pot, and a gas meter.
The molten polymer was continuously sent into the reactor by the extruder in
which the raw material (polymer pellets) was heated and melted in a temperature
range of 200–220 °C. Firstly, about 1 kg of polymer was fed into the reactor. Then
the reactor was heated up to a reaction temperature at which the raw polymer
thermally decomposes. It took 30–60 min for the liquid product to exit the reactor
after the destined degradation temperature is attained for a given polymer.
When a volatile product began to be observed, an aliquot amount of raw
polymer corresponding to the output was continuously fed into the reactor by the
extruder. The rate of feed input was gradually adjusted to that of product output
in order to keep the amount of reactor contents constant. Eventually, not only the
amount of reactor contents becomes constant under fixed temperature and pressure,
but also the concentration of CC double bonds in the reactor contents attains a
steady state [4].
As the raw polymers (their properties are shown in Table 1) contain only a small
amount of ash and Conradson carbon, this reactor system can attain a steady state
without any appreciable accumulation of residues [1].
74 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90

When the accumulation of residues in reactor is too large to be ignored, it is

necessary to periodically remove the accumulation from the bottom of the reactor
in order to accomplish a steady state for the system. The effect of pressure on
thermal degradation of polymers has been previously reported by the authors [2,3].
However, the experimental results in this paper were obtained at atmospheric
pressure and a condition of negligible accumulation of residues in the reactor.
In this paper, ‘volatile product’ refers to gaseous and liquid products, and
‘degradation product’ refers to volatile product and reactor contents. The gaseous
product consisted of low molecular weight hydrocarbons which are not condensable
at water cooling temperature; the liquid product was a condensate which consists of
a series of hydrocarbons; and the reactor contents were intermediate products
which were never removed from the reactor while the reaction was in progress.
Fig. 2 shows a plot of cumulative weight of the volatile product (gas+ liquid)
obtained from the thermal degradation of PE by continuous flow operation. The
cumulative curve gradually approaches a straight line, which indicates a steady
state attained by this continuous flow operation. The slope of cumulative curve
corresponds to the rate of degradation. Likewise a plot of cumulative weight of
input material reveals a similar curve having the same slope as the volatile product.
The weight of reactor contents (Dw) is equal to the difference between cumulative
input (win) and cumulative output (wout). That is:

Dw =win − wout (1)

The continuous flow operation was carried out until the cumulative weight of
volatile product exceeded three times the amount of reactor contents. A sample of
gaseous product was collected in a teflon bag before passing through a water seal
pot. After finishing the operation, the reactor was cooled down and the reactor
contents were withdrawn from the reactor bottom. The observed amount of reactor
contents agreed with the calculated value Dw within a range of 9 1.0% throughout
the experimental run.

Fig. 2. Cumulative weight of volatile product derived from thermal degradation of PE by continuous
flow operation.
 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90 75

It is necessary to know the specific gravity of liquid product and the average
molecular weight of the gaseous product before calculation of the weight of volatile
product on the basis of the observed volumetric data. These indispensable values
have been previously estimated on the basis of the author’s thesis [5].

2.3. Analytical methods

Gaseous products were analyzed using a gas chromatograph with a Molecular

Sieve 13× column and a TCD detector at 40 °C under a argon carrier for
hydrogen; and a diatom Earth with di-n-butyl maleate column and a TCD detector
at 40 °C under a hydrogen carrier for hydrocarbon gases.
Liquid products were analyzed by a gas chromatograph with a DB-1 capillary
column (60 m×0.252 mm i.d., 0.25 mm film thickness) using a temperature
program from 40 to 280 °C at a heating rate of 5 °C min − 1 and a FID detector.
Kinematic viscosity was determined using a Canon–Fenske capillary column
viscometer. Specific gravity was determined by float method. Average molecular
weight was determined by freezing point depression of benzene. Average carbon
number was calculated based on Normal Paraffin gram (Npgram) (a carbon
number distribution).
Reactor contents were analyzed with a gel permeation chromatograph (Waters
150C ALC/GPC) with two Shodex AT-806M/S columns (250× 8 mm i.d.) in
ODCB (0.1 ml min − 1) at 140 °C and a RI detector calibrated by styrene oligomers.
Viscosity of the reactor contents was determined with a cone and plate viscometer.
Average molecular weight of the reactor contents was calculated based on GPC
data. Toluene insoluble was determined by Soxhlet extraction method.

3. Results and discussion

3.1. Rate of degradation

Fig. 3a shows the effect of degradation temperature on the rate of volatilization

and the residence time of PE, PP and PS. The definitions of the rate of volatiliza-
tion and the residence time are given by Eqs. (2) and (3).
Production rate (kg h − 1)
Rate of volatilization (h − 1) = (2)
Amount of reactor contents (kg)
Amount of reactor contents (kg)
Residence time (h)= (3)
Feed rate (kg h − 1)
The production rate and the feed rate correspond to the slope of cumulative
weight of volatile product, as shown in Fig. 2.
The rate of volatilization defined by Eq. (2) is substantially equivalent to the rate
constant k in Eq. (4), which is usually used in thermogravimetric analysis of
polymers [6,7].
76 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90

Fig. 3. (a) Effect of temperature on the rate of volatilization and the residence time. (b) Effect of
temperature on the rate of double bonds formation.

dm
− =km (4)
dt

m, weight of residual polymer; dm/dt, rate of weight increase; k, rate constant

(h − 1).
 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90 77

Eq. (2) shows the average rate of volatilization in thermal degradation of

polymers. On the other hand, the rate constant k in Eq. (4) corresponds to the
volatilization rate at a point in degradation process.
In the meantime Fig. 3b shows the effect of temperature on the rate of double
bonds formation in the thermal degradation of PE, PP and PS. As the raw polymer
contain a negligible few amount of double bonds, the rate of double bonds
formation is given by Eq. (5) under a steady state.
Rate of double bonds formation (mol kg − 1 h − 1)
CC bonds in volatile (mol h − 1)
= (5)
Amount of reactor contents (kg)
The amount of CC bonds in volatile was determined based on the bromine
number of liquid product and the gas chromatography data of gaseous product.
The double bond in degradation product is a direct measure for the breakage of
polymer links, because there exist a one to one correspondence between the
breakage of CC links and the formation of double bonds [8]. Based on the both
rates of volatilization and double bonds formation, the activation energies of
thermal degradation of PE, PP and PS were calculated. Table 2 shows the observed
activation energies for the thermal degradation of polymers.
Generally speaking, when a physicochemical process has an activation energy of
less than 40 kJ mol − 1, a physical process takes a role of rate controlling step. On
the contrary, when the activation energy is greater than 120 kJ mol − 1, we conclude
that a chemical reaction plays the role of rate controlling step in that process [9].
As the both of activation energies of PE, PP and PS are much higher than 120
kJ mol − 1, as shown in Table 2, it is evident that the thermal degradation of
polymers in this reactor system is a chemical reaction dominant process. All of the
activation energies calculated from thermogravimetric analysis in the literature
support this conclusion [6,7,10,11].

3.2. Degradation products

3.2.1. O6er6iew of degradation products

Figs. 4–6 show molecular weight distributions of degradation products obtained
from the thermal degradation of PE, PP and PS in contrast with those of the

Table 2
Activation energies of thermal degradation of PE, PP and PS

Polymer Activation energy (kJ mol−1)

Volatilization Double bonds formation

PE 221 244
PP 216 288
PS 208 166
78 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90

Fig. 4. Molecular weight distribution of products obtained by thermal degradation of PE.

original polymers. As the raw polymer was fed into the reactor contents before
degrading into a volatile product, so the reactor contents represents an intermediate
product in the thermal degradation of polymers.

Fig. 5. Molecular weight distribution of products obtained by thermal degradation of PP.

 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90 79

Fig. 6. Molecular weight distribution of products obtained by thermal degradation of PS.

Fig. 4 shows that the reactor contents obtained from the degradation of PE have
undergone about 70 scissions of the CC bond in the original polymer. The volatile
products have undergone a further seven to eight scissions. The scission numbers
were estimated based on the molecular weight data, e.g. (the average molecular
weight of reactant/the one of product)− 1.
For PP, the reactor contents had undergone 300 scissions and the volatile
products a further four (Fig. 5). The reactor contents for PS degradation had
undergone 55 scissions, and the volatile products another 18–19 (Fig. 6). These
differences in thermal degradation behavior among polymers suggest some mecha-
nistic consideration that involve a random breaking of polymer links and a
chain-end scission.
All of the molecular weight distributions of volatile product and reactor content
are shifted to higher molecular weight with increasing degradation temperature.
Consequently, the average molecular weights of both components increase with
temperature, as shown in Table 3.

3.2.2. Gaseous product

Effect of degradation temperature on the yields of gaseous products for PE, PP
and PS degradation are shown in Fig. 7. Fig. 8 shows the carbon number
distributions of gaseous products derived from PE (decomposed at 420 °C), PP
(380 °C) and PS (350 °C).
As shown in Fig. 7, the degradation temperature has an opposite effect on the
yield of gaseous product for the thermal degradation of PE and PP. The gaseous
product of PE decreases with degradation temperature, while that of PP increases
 80
Table 3
Properties of liquid product obtained by thermal degradation of PE, PP and PS

Polymer Degradation temperature Specific gravity Kinematic viscosity (cSt at Average molecular weight Average carbon
(°C) (15/4 °C) 50 °C) number

PE 420 0.783 1.71 188 14.5

430 0.788 2.40 214 15.4
440 0.792 3.94a 245 15.9
PP 380 0.770 1.18 162 12.3
390 0.776 1.24 165 12.5
400 0.781 1.54 165 13.3
PS 350 0.910 0.83 109 11.0
360 0.926 0.94 120 11.5
370 0.935 1.10 129 12.3

a
At 55 °C.
K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90
 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90 81

Fig. 7. Yield of gaseous product, gas/(gas+liquid).

with temperature. This unexpected phenomenon has not been reported in the
literature.
PS degradation provided a small amount of gaseous products that is less than
0.15 wt.% of volatile product.
For PE and PP degradation, the gaseous products were mainly, C2 (ethane,
ethylene); C3 (propane, propylene); C4 (butane, butene); and a small amount of
hydrogen and C5 components. For PS, gaseous product was mainly hydrogen.

3.2.3. Liquid product

Based on the assumption that the input rate of raw polymer is equal to the
output rate of volatile product, the yield of liquid product in this continuous flow
operation is given by Eq. (6):

Yield of liquid product (wt.%)=100 − yield of gaseous product (wt.%)

(6)

Fig. 8. Carbon number distributions of gaseous products from thermal degradation of PE, PP and PS.
82 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90

Fig. 9. Carbon number distributions of liquid products obtained by thermal degradation of PE, PP and
PS.

From the yield of gaseous product shown in Fig. 7 and Eq. (6), the liquid
product yield of 93.9– 96.2, 96.1– 99.0 and 99.9 wt.% were obtained for PE, PP and
PS degradation, respectively.
Physicochemical properties of the PE, PP and PS derived liquid products are
shown in Table 3. Fig. 9 shows the carbon number distributions of the liquid
products. The liquid products obtained from thermal degradation of polymers can
be characterized by a NPgram demonstrated by Murata and Makino [12].
The NPgram is a carbon number distribution of hydrocarbons derived from the
gas-chromatogram on the basis of boiling points of a series of normal paraffins. We
can find out the peak positions of a series of normal paraffins on a gas-chro-
matogram of the liquid product obtained by thermal degradation of polymers by
using a PE derived oil which contains a series of normal paraffins as a index
material. NPgram is constructed by plotting the weight fraction of hydrocarbons,
which are located within the range of retention values of two successive normal
paraffins, Cn −1 and Cn, against the carbon number, n.
Since the carbon number, n, corresponds to the boiling point range (see Table 4)
of a certain group of hydrocarbons, the NPgram actually represents a volatility
distribution of the liquid product. Fig. 9 shows the NPgrams of the liquid products
obtained from the thermal degradation of PE, PP and PS.
As shown in Fig. 9 and Table 4, the hydrocarbons in liquid product of PE are
distributed in a wide range of carbon numbers, nC4 –nC30, which is equivalent to a
boiling point range of −0.5 to 455.9 °C.
As illustrated in Fig. 9, peaks on NPgram of the liquid product of PP do not
always appear at a multiple of three carbon numbers, e.g. at 6, 9, 11, 14, 16 and 18.
Table 5 shows the boiling point data, estimated by Wiener’s method [13], of
propylene oligomers derived from the thermal degradation of PP and their corre-
sponding carbon numbers for NPgram. As shown in Fig. 9, the corresponding
 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90 83

Table 4
Boiling point range corresponding to the carbon number on NPgram

Carbon number Boiling point range (°C)

Cn-1 to Cn

5 −0.5 to 36.1
6 36.1–68.7
7 68.7–98.4
8 98.4–125.7
9 125.7–150.8
10 150.8–174.0
11 174.0–195.8
12 195.8–216.2
13 216.2–235.3
14 235.3–252.5
15 252.5–270.6
16 270.6–286.8
17 286.8–302.2
18 302.2–317.0
19 317.0–331.1
20 331.1–344.7
21 344.7–357.7
22 357.7–370.2
23 370.2–382.3
24 382.3–393.8
25 393.8–405.1
26 405.1–415.9
27 415.9–426.3
28 426.3–436.6
29 436.6–446.4
30 446.4–455.9
31 455.9–465.2

carbon numbers of propylene oligomers exactly coincide with the peak components
on the NPgram. That is, propylene oligomers are the major products in the thermal
degradation of PP.

Table 5
Boiling points of propylene oligomers and their corresponding carbon numbers on NPgram

Propylene oligomer Boiling point (°C) Corresponding carbon number

Dimer 62.2 6
Trimer 136.2 9
Tetramer 192.0 11
Pentamer 236.4 14
Hexamer 272.7 16
Heptamer 302.9 18
84 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90

Table 6
Main components in liquid product derived from PS and their corresponding carbon numbers on
NPgram

Carbon number on Npgram Component

7 Benzene
8 Toluene
Ethyle benzene
9 Styrene monomer
Cumene
Aryl benzene
10 a-Methyl styrene
17 Styrene dimer components
25 Styrene trimer components

The NPgram of the liquid product of PS has peaks at 9, 17 and 25. Table 6
reveals the main components contained in the liquid product of PS and their
corresponding carbon numbers on the NPgram. It also shows that the peak
components on the NPgram involve the styrene oligomers, such as monomer, dimer
and trimer, respectively. Similarly, styrene oligomers are the major products in the
thermal degradation of PS.
The authors has extended the application of NPgram for various hydrocarbon
oils, such as waste plastics derived oil, petroleum fractions and coal derived oil [14].

3.2.4. Reactor contents

The properties of the reactor contents of PE, PP and PS are shown in Table 7
and the molecular weight distributions in Figs. 4–6.
The reactor content of PE have a molecular weight of 1500–1700 which
corresponds to 54– 61 monomeric unit of ethylene. It is a brown solid at ambient
temperature, but melts at temperatures above150 °C. Physical observation of the
reactor content of PE during thermal degradation reveals a liquid generating a

Table 7
Properties of reactor contents obtained by thermal degradation of PE, PP and PS

Polymer Degradation Viscosity (cp at Average molecular Toluene insoluble

temperature (°C) 200 °C) weight (wt.%)

PE 420 20 1500 0.67

430 21 1700 0.53
440 22 1700 0.40
PP 380 19 700 0.56
390 20 700 0.54
400 20 800 0.45
PS 350 1045 6400 0.73
360 1210 6800 0.67
370 1250 6900 0.64
 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90 85

great deal of small bubbles in a similar manner to the distillation of kerosene [15].
The reactor contents of PP showed a similar behavior to that of PE. On the other
hand, the reactor contents of PS are more viscous than those of PE and PP. At
degradation temperature it looked like boiling rice gruel.
The toluene insoluble in reactor contents, shown in Table 7, is the only property
which does not reach a steady state in this continuous operation. It increases with
elapsed time. Since the amount of toluene insoluble portion in the reactor contents
is very small, as shown in Table 7, it did not appreciably affect the thermal
degradation of polymers in this work.

3.3. Continuous flow operation for thermal degradation of polymers

Most reactors, which have been used for the thermal degradation of waste
plastics into liquid product in industrial processes can be reduced to the same
scheme as shown in Fig. 1. From now on we will refer to it as a ‘Degradation and
Volatilization Reactor (DVR)’. The DVR is a continuous flow stirred tank reactor
in which thermal degradation of polymers and volatilization of products simulta-
neously occur under steady state conditions.
In the DVR system, the input polymer is continuously melted into a viscous
liquid while mixing with the reactor contents. At degradation temperature the
reactor contents decompose into small molecules which are convertible to hydrocar-
bon vapor under reaction conditions and leave the reactor. Needless to say, all of
the volatile products vaporize in the reactor before coming out as the output
product of DVR.
The volatile products consist of a lot of hydrocarbons, which enter into the
condenser where they separate into the gaseous products and liquid products. Both
the gaseous and liquid products consist of a series of hydrocarbons corresponding
to the input polymer. Their composition varies with the degradation temperature
and pressure [1– 3].
On the other hand, the reactor contents are liquid under degradation conditions.
They are degradation products of the original polymer, but the molecular weight is
not small enough to exit the reactor during volatilization. They could be intermedi-
ates that establish a dynamic equilibrium in the DVR system. The reactor contents
also consist of a lot of hydrocarbon compounds, such as oligomers and polymers,
even though their molecular weights are lower than that of the original polymer.
Thus it is clear that there is a gas– liquid interface in the reactor, because, the
volatile products and the reactor contents co-exist together in the DVR system.
A visual inspection of the inside of the reactor made by Sakata et al. [15] revealed
that the reactor contents were decomposed at degradation temperature into hydro-
carbon vapor with the generation of small bubbles in a similar manner to a
distillation of petroleum fractions, such as kerosene and gas oil. Therefore the
gas –liquid interface mentioned here is distributed in the whole liquid phase of the
reactor.
The fact that there is a gas– liquid interface in the reactor leads to an important
conclusion that residence time in the DVR is not an independent operation
86 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90

variable. Once we choose a temperature and a pressure for a degradation run, the
whole behavior on thermal degradation of a given polymer, such as degradation
rate, product compositions and so on, must be determined in the DVR system.
In DVR, the feed rate of raw polymer is equal to the production rate of volatile
products. Depending on this condition, Eqs. (2) and (3) make Eq. (7). That is:
1
Average residence time= (7)
Rate of volatilization
Eq. (7) indicates the residence time in DVR is the reciprocal of the rate of
volatilization (see Fig. 3a). Moreover the residence time is not an independent
variable in DVR, but an observed value which is to be determined at a fixed
temperature and a pressure.
Therefore, the significance of residence time in DVR is different from that in a
continuous flow reactor for homogeneous reaction in which the retention value is
independently chosen as an operation variable. A question in DVR, ‘How does the
residence time affect the thermal degradation of a polymer?’, is equivalent to one,
‘How does the temperature affect it?’. Since there exists a one to one correspon-
dence between the residence time and the degradation temperature in DVR, as
shown in Fig. 3a.
The following thermodynamic considerations leads to the same conclusion,
depending on the phase rule, the degree of freedom (F) of a reaction system is given
by Eq. (8):

F =n−p+ 2 (8)

The number of component (n) is 2 for DVR, because, there are two components,
volatile products; and reactor contents, present in the reactor. The number of phase
(p) is also 2, because there co-exist a gas and a liquid. Substituting these numbers
to Eq. (8) makes F = 2. That is why we can not share any freedom for the DVR
system other than temperature and pressure.
DVR is a system which gives intrinsic properties of a polymer on thermal
degradation, as there are no independent variable other than temperature and
pressure in the system.

3.4. Mechanistic considerations

A lot of mechanistic researches have been carried out on thermal degradation of

polymers [16–23]. Formerly, a random scission mechanism was proposed to explain
the process of thermal degradation of polyolefins and other polymers [16,17].
Recently, however, Tsuchiya and Sumi for PE, PP and polyisobutylene [18–20],
Kiran and Gillham for PE [21] and Lattimer for five polyolefins [22] reported a
chain-end scission caused by an intramolecular radical transfer plays an important
role for the production of volatile. Furthermore, Grimbley and Lehrle proposed
that polyisobutylene thermally degraded by parallel depropagation with random
scission [23].
 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90 87

Fig. 10. Macroscopic model for thermal degradation of polymers.

These recent researchers seem to recognize the two distinct mechanisms in

thermal degradation of polymers. One is a random scission of polymer links, that
causes a reduction in molecular weight of macromolecules and an increase of the
number of fragmentary molecules; and the other is a chain-end scission caused by
an intramolecular radical transfer (a back biting) which subsequently generates
volatile products. In this paper, the authors describe the phenomenon in a more
macroscopic manner.
As previously mentioned, the thermal degradation of polymers in DVR is a rate
process, in which a chemical reaction plays the role of a rate controlling step; and
there exists a gas– liquid interface which separates the reactant (the reactor con-
tents) and the product (the volatile product) in the working reactor.
It thus follows that the volatilization process must be a reaction step in the
thermal degradation of polymers. Consequently, the generation of the volatile
product in thermal degradation of polymers is a heterogeneous reaction in which
the reactant is in a liquid phase and the product is in a gaseous phase.
Meanwhile, there is no doubt that the raw polymer decomposes into the reactor
contents in liquid phase by a random scission mechanism. Therefore, the thermal
degradation of polymers consists of two distinct mechanisms, which simultaneously
occur in the reactor, as shown in Fig. 10. One is a random scission of links which
causes a decomposition of macromolecules into the reactor contents, and the other
is a chain-end scission which causes a conversion of the reactor contents into the
volatile product in a heterogeneous manner.
The random scission of polymer links causes a reduction in molecular weight of
macromolecules and an increase of the number of oligomer molecules. The chain-
end scission causes a dissipation of oligomer molecules and a generation of volatile
products. The reactor contents stand for the intermediates, which establish a
dynamic equilibrium between the random scission and the chain-end scission.
Figs. 4–6 show that the decomposition of the raw polymer into the reactor
contents corresponds to the random scission, whose rate is proportional to the
number of CC bonds, and the generation of volatile products from the reactor
88 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90

contents corresponds to the chain-end scission, whose rate is proportional to the

number of molecules. The chain-end scission occurs at the gas–liquid interface, as
mentioned above.
Fig. 10 and Tables 8 and 9 summarize the macroscopic mechanisms mentioned in
this paper.

4. Conclusions

In this paper the author has reported ‘DVR’ and the thermal degradation
behavior of PE, PP and PS in DVR. Based on the observed information, a
macroscopic mechanism of thermal degradation of polymers was discussed.
Thermal degradation by continuous flow operation is a suitable technique for
converting plastics polymers into liquid hydrocarbons which could be used as feed
stock material. And the study on thermal degradation of polymers by continuous
flow operation provides important information about the rate controlling step and
the formation of volatile products.
The information obtained from a steady state operation of the thermal degrada-
tion of PE, PP and PS leads to the macroscopic degradation mechanism shown in
Fig. 10. Hereafter, it is required to investigate the consistency between the macro-
scopic mechanism mentioned in this paper and the microscopic mechanism men-
tioned in the literature that is composed of initiation, depolymerization, back
biting, radical transfer and termination.

Acknowledgements

The authors gratefully acknowledge that a part of this work was supported by
the Original Industrial R&D Program from the New Energy and Industrial
Technology Development (NEDO) through Grant 8G-010-2.

Table 8
Changes that simultaneously occur in the reactor for thermal degradation of polymers

Substance Molecule Degree of polymerization State in process

Raw Polymer Macromolecule 102–105 Solid

¡ ¡ ¡ ¡
Reactor Contents Oligomer 10–103 Liquid
¡ ¡ ¡ ¡
Volatile Product Gas and Liquid 1–10 Gas
Table 9
Feature of the reactions that occur in the reactor for thermal degradation of polymers

Reaction Function Intensive Reaction mode Reaction field Reactant Product

measure of rate

Random Molecular weight reduction and increase Number of Homogenuous Liquid phase Polymer Reactor contents
scission of the number of molecules CC bonds reaction
Chain-end Dissipation of molecules and generation Number of Heterogenuous Gas–liquid Reactor contents Volatile product
scission of volatile product molecules reaction interface
K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90
89
90 K. Murata et al. / J. Anal. Appl. Pyrolysis 65 (2002) 71–90

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