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A studv of the aroducts of PVC thermal
Polymer Degradation and Stability 49 (1995) 181-191
0 1995 Elsevier Science Limited
Ian C. McNeil& Livia Memetea & William J . Cole
Polymer Research, Chemistry Department, University of Glasgow, Glasgow G12 8QQ, UK
(Received 3 January 1995; accepted 3 February 1995)
PVC thermal degradation in vacuum up to 500C has been followed by
recording the relative rate of volatile product formation by thermal volatilisa-
tion analysis while monitoring by mass spectrometry the formation of the main
products: HCl, aromatic and aliphatic hydrocarbons, and non-condensable
gases (CH,, HZ). The material balance after pyrolysis has been evaluated. The
liquid fraction collected during pyrolysis was analysed by GC-MS and its
composition determined by the integration of the ion current under the peaks
due to different compounds. After HCl (53% of the PVC sample), the tar is
the major fraction (24%). The liquid fraction (of which 80% is benzene)
accounts for 7% of the original polymer. The other fractions are the char
(9.5%) and gas fraction (6.6%). 10% of the Cl remained trapped in the
polymer until higher degradation temperatures giving rise then to the
chlorinated compounds which account for 1.75% of the liquid fraction and
0.14% of the polymer.
PVC shows two stages of degradation: during the first stage, between 200
and 360C mainly HCl and benzene and very little alkyl aromatic or
condensed ring aromatic hydrocarbons are formed. It was evaluated that 15%
of the polyene generates benzene, the main part accumulating in the polymer
and being active in intermolecular and intramolecular condensation reactions
by which cyclohexene and cyclohexadiene rings embedded in an aliphatic
matrix are formed. Alkyl aromatic and condensed ring aromatic hydrocarbons
are formed in the second stage of degradation, between 360 and 500C when
very little HCl and benzene are formed. In this stage the polymeric network
formed by polyene condensation breaks down in the process of aromatisation
of the above C, rings. The mechanism of benzene formation at different
temperatures was considered.
1 INTRODUCTION
The present investigation is a study of PVC
pyrolysis which has relevance to waste disposal
by incineration and the environmental problem it
poses. The work is part of a larger project which
aims at: (i) identification and quantitative
determination of the pyrolysis products of PVC
as a reference material and of its formulations
with additives such as plasticisers, stabilisers and
flame-retardants; (ii) better understanding of the
pyrolysis mechanism; and (iii) intervention into
the pyrolysis mechanism in order to minimize
toxic product formation, offering thereby a less
polluting solution to disposal of PVC scrap by
incineration.
The present paper, the second in the series, is
concerned with the separation, identification and
quantitative determination of the pyrolysis
products of PVC.
2 EXPERIMENTAL
The PVC used was a typical industrial,
suspension grade sample from European Vinyls
Corporation with molecular weight (A4,) 40,000
as determined by GPC. The pyrolysis was
conducted under continuous evacuation (initial
vacuum 10v5 mm Hg) at a heating rate of
lOC/min up to SWC, when a hold time of 20
min was allowed. PVC samples (powder) of
182 I. C. McNeil1 et al.
20-200 mg, spread as a thin layer at the bottom
of a silica cell, were subjected to pyrolysis. The
pyrolysis products were collected, separated and
analysed according to the procedures of thermal
volatilisation analysis (TVA).. An account of
this technique has been presented in the first
paper of the series.
The products evolved through pyrolysis were
collected in fractions: the cold ring or tar
fraction, the liquid fraction, the residue or char,
and the gas fraction. The tar contains condensed
ring aromatic hydrocarbons (MW 128-250) and
scission fragments of the network formed
through the crosslinking of polyene. The tar has
been qualitatively analysed in the earlier study.
The liquid fraction is made up of compounds
which condense at room temperature. The gas
fraction consists of HCl together with noncon-
densable gases (CH,, H,) and C,-C, hydrocar-
bons. The fractions (apart from the gases) were
weighed for material balance after pyrolysis. The
gases were determined by difference. HCl was
determined in a separate experiment in which it
was retained on a short column containing CaO
mixed with glass wool which allowed for the free
passage of the other gases.
The liquid fraction containing products up to a
molecular weight of 150 was analysed by CC-MS
using a Hewlett-Packard 5971 mass selective
detector interfaced to a 5890 series 11 gas
chromatograph and computer (Vectra QS/16s).
Separations were effected with an HP1 fused
silica capillary column (12.5m X 0.2mm X 0.33
pm) temperature-programmed from 50C (5 min
hold) to 220C (1 min hold) at SC/min. The
Grob-type injector (225C) was operated in split
mode (5O:l) and the He carrier gas flow rate was
1 ml/min. Mass spectra (70 eV) were recorded in
continuous scanning mode. The concentration of
the components in the analysed fraction was
determined by the integration of the ion current
under the peaks.
In other experiments, the evolution of the
volatile pyrolysis products was monitored during
heating in vacuum to 500C by means of Pirani
gauges using the conventional four parallel line
TVA experimental arrangement. The pyrolysis
products were then condensed on a liquid
nitrogen trap. Another Pirani gauge placed after
a liquid nitrogen trap recorded the non-
condensable gases (H, and CH, in this case). The
Pirani output was recorded as a function of time
or temperature. For temperature measurement,
two thermocouples were used, one placed in the
combustion tube just above the sample, the other
in the oven, in order to assess the temperature
lag between the sample and the oven, which is a
common phenomenon in dynamic heating.
Typically, at the beginning of the experiment the
temperature lag was lo-15C, it decreased to
5-6C at 200C and then was steadily reduced to
I-2C towards 500C as shown in the corres-
ponding diagrams. The Pirani recording gives a
measure of the relative rate of evolution of
volatile products and is useful in identifying the
degradation stages of the polymer, which
together with the identification of the nature of
the products can provide valuable information on
the degradation mechanism.
A bleed to a Leda-Mass quadrupole mass
spectrometer placed on line with the TVA system
enabled the mass spectra of the products to be
recorded in continuous scan mode (3.3
scans/min). The stored MS scans were subse-
quently further analysed for the identification of
the evolved products. The lines in the mass
spectra produced by ions of m/e which are
characteristic of certain products and which are
not subject to interference from other products
were identified and their intensity plotted against
time (temperature) using Microsoft Excel. The
intensity of the above lines is expressed as partial
pressure produced in the mass spectrometer by
ions of specific m/e.
3 RESULTS
3.1 Main product frictions
Table 1 presents the material balance of the
products obtained through the pyrolysis of PVC
in vacuum up to 500C. As can be seen, apart
from HCl (53%), the cold ring products form the
major fraction (24%). Of the polymer remaining
Table 1. Material balance after PVC pyrolysis
NO FrXiKCl %
I MCI (2 6
2 Cold (tar) f radm nng 24 3
3 Lquld fncttal 7.0
4 Gas fmdim (apart fim HCI) 66
5 Char 9s
A study of the products of PVC thermal degradation 183
after HCl emission, 50% degrades to tar, 20% to
char, 30% to gas fraction and 30% to liquid
fraction. The amount of Cl in the evolved HCl
compared to the theoretical Cl content of the
PVC shows that 10% of the original Cl remains
in the polymer to higher temperatures than those
involved in dehydrochlorination.
Table 2 presents the composition of the liquid
fraction obtained through the pyrolysis of PVC,
expressed as main classes of compounds. The
following features can be noted.
Aromatic hydrocarbons are the main class
(88%), of which the major part is benzene
(80%). Aliphatic hydrocarbons account for 5.2%
of theliquid fraction. These have been identified
in the previous paper. Chlorinated hydrocarbons
make up 1.75% of the liquid fraction and
correspond to 0.14% of the original polymer.
Table 3 presents the main aromatic con-
stituents of the liquid fraction obtained through
the pyrolysis of PVC alone. Benzene accounts for
80% of the mixture, as already shown (and for
5.6% of the PVC). It is followed by toluene
(1*8%), o&o-xylene (l-3%), ethylbenzene (1%)
and 1,2 methylethylbenzene (l%), the percen-
tage being relative to the liquid fraction. A
surprising feature is that among the alkyl
benzenes, the ortho-derivatives are formed in a
higher concentration than metu- and paru-
derivatives: ortho-xylene accounts for l-3%,
me&- and puru-xylene for O-6%, 1,2-methylethyl
benzene for l%, while 1,3- plus 1,4- derivatives
make up 0.3%. This trend reflects a higher
probability for the ortho-derivatives to be formed.
Table 4 presents the constituents of the class of
chlorinated hydrocarbons produced through the
pyrolysis of PVC. The main chlorinated com-
pounds are chlorinated alkenes and chlorinated
aromatics, all regarded as hazardous to health.
Table 2. The composition of the liquid fraction
(classes of compounds) collected during the pyrolysis
of the PVC sample
c- % 96
Bmrsns 19.14
Alkyl amna,c 5.22
Alkenyl .mmat,c 0 83
Cc.l&nd rmg alonlatic 2.40
T&al .-t,c 88 20
AlhO 2.47
C!yClWlkNWS 0 80
Alkmes I .52
cyckmkmm 0.40
Total aliphraic 5 19
Chlorinated hydmxbms I IS
others 4.87
Total IOOGQ
Table 3. Quantitative determination of the main aromatic
products in the liquid fraction
No PWdW %
1 796
/ \
5 -o- 06
-
3.2 Thermal volatilisation analysis
The evolution of the volatile compounds
constituting fractions l-4 of Table 1 was followed
by TVA and the results are presented in Fig. 1,
which shows the response of five Pirani gauges
and two thermocouple outputs as a function of
temperature. The evolution of non-condensable
by the response
placed after the
gases (HZ and U-L,) is indicated
in the trace for the Pirani gauge
-196C trap (curve 5).
T&le 4. Chlorinated hydrocarbons
pyrolysis of PVC
NO Crnpamd % NO
Cl
16
+
01
25
Cl CI
20
+,a
SO1 26
Cl
21
II
02 27
Cl
22
?I
01 26
23 /t/ o-2
Cl
24
w 02
formed in the
%
o-15
01
02
016
02
036
184 1. C. McNeil1 et al.
500
5
01 : :
04 120 1.30 200 240 230 320 300 4w 440 480
Temperature (C)
Fig. 1. TVA diagram recorded as Pirani gauge output
(relative rate) vs temperature for PVC thermal degradation.
Key to traces: 1-4, volatile products (condensable) recorded
with four Pirani gauges placed on parallel lines: 5,
noncondensable gases (Hz, CH,); 6,7, thermocouples output.
Figure 1 shows that the volatile compounds are
evolved in two degradation stages: between 200
and 360C and between 360 and 500C. These
have already been identified by TVA. HCl and
benzene are the major degradation products in
the first stage. During the second stage,
breakdown products of the crosslinked polyene
are formed which were qualitatively analysed as
components of the tar, liquid and gas fractions.
The amounts of volatile products at the second
stage are smaller, as can be seen in Fig. 1. A
small amount of non-condensable gases is formed
(4
1 WE.03
P.w3m
O.OOE-03
7 WE.00
g
o.ocEm
E 5.cQE-m
j 4.OOE-09
3OoE-08
2wE-05
1OOE-a
O.OOE+W
30
E
@I
0 50 loo 150 200 250 300 350 4Ou 450 5OQ
Tempemtun (C)
I OOE-08
3OOE-00
2wE-09
1 .JOEJm
82
OOOE+OO _s
0 50 KM 150 200 250 300 350 UXI 450 5al
Tsmperalum (C)
Fig. 2. Ion monitoring during PVC thermal degradation: (a)
benzene (78) HCI (36-38); (b) toluene (91,92).
towards the end of the second stage and very
little if any, in the first stage.
3.3 Evolution of individual products
3.3.1 Hydrogen chloride and benzene
The evolution of the individual products with
temperature was followed by plotting the
intensity of the lines produced in the mass
spectra by their characteristic ions vs tempera-
ture. Figure 2(a) shows the evolution of benzene
(m/e 78) and HCl (m/e 36, 38). It is evident that
these are evolved mainly during the first
degradation stage and only to a minor extent
during the second stage. However, Fig. 2(a)
shows that although HCl is produced at the same
time as benzene (at 200C) it appears that the
HCI curve (m/e 36) initially lags behind the
benzene curve, which was a reproducible trend in
all the present experiments. Although the delay
is expressed in terms of temperature, it is
believed that time and not temperature governs
the phenomenon, which may possibly
anomaly due to initial HCl adsorption
glassware. The effect is being
investigated.
be an
on the
further
3.3.2 Toluene and other aromatics
Toluene formation as a function of temperature
was followed using its ions at m/e 91 and 92 (Fig.
2(b)). While in the first degradation stage there
are no other compounds contributing to the 91
line, in the second stage this is no longer valid.
Compounds such as xylene, ethylbenzene,
propylbenzene, butylbenzene and their isomers
are the main sources of the 91 line in the second
stage. However, the 92 line can be safely
regarded as characteristic only of toluene, since
other substances giving the same ion (especially
C,-alkylbenzenes) are formed in very low
concentrations. Figure 2(b) shows that a small
part of the toluene is formed in the same process
as benzene. The major part of the toluene is
formed in a different process in the second stage.
This conclusion has been also verified by the GC
analysis of the liquid fractions collected separ-
ately for each degradation stage. Styrene
formation was followed by its molecular ion (104)
and so was ethylbenzene and the isomers of
xylene (106), all presented in Fig. 3(a). They are
all formed in a minor amount during the first
stage and almost entirely during the second stage.
A study of the products of PVC thermal degradation 185
(4
3.wE-00
3. OcE- w
2. sOE- OQ
F
~2. OE- 00
j 1. sOE- 09
l . WE- OQ
0 s 10 1s m 25 30 35 40 45 50
Temmml umrC) x0. 1
. m
.
: ?I
I ;
0 5 l o 15 m 25 30 35 40 45 50
Tanpentun CC) xO. l
Fig. 3. Ion monitoring during PVC thermal degradation: (a)
styrene (NM), C3-C5 alkyl benzene (105), ethylbenzene and
xylene isomers (106); (b) indene (115, 116).
Figure 3(a) shows also the intensity for evolution
of the ion with m/e 105 characteristic of C,-C,
alkyl benzenes which are present in this system.
These products are also formed mainly in the
(4
ZOOE- OQ-
. d
l ml E- o~-
.
: .
.
l . eE- OS . .
1. 4E- 00
8 ;
0
-
12oE- O~-
S
I l . OEoo . .
1 8. OOE- 10 . .
' cs
117
. - a .
e. OE- 10
4. Oms10
:
z. OOE- 10
_*pQ?,,,
__...yy : ,
' 4Al 8
O. OOEI oo
L, . : . 118
0 5 l o 15 m 25 30 35 40 45 50
Temmrmum~~I xO. 1
(b) T
o. ooE- 10
moE- 10
7oOE. 10
I
0 s 10 is m 25 30 35 40 45 50
T. mpeml um~C) xO. ~
Fi g. 4. Ion monitoring during PVC thermal degradation: (a)
indane, methylindane and C,-alkenylbenzenes (117, 118);
(b) naphthalene (128).
second degradation stage. The same observation
is valid for indene (ions 115, 116, Fig. 3(b)) and
also for indane and methyl indanes (structures 15
and 16, Table 3) and C,-alkenylbenzenes
(structures 7 and 8, Table 3) having contributions
to the ions 117 and 118, the formation of which
during degradation is presented in Fig. 4(a).
Naphthalene (128, Fig. 4(b)) is formed only
during the second degradation stage.
In the case of indene, indane (and other
compounds) and naphthalene, the curves are
very noisy due to the low amount in which these
compounds are formed. In Figs 3(b), 4(a) and
4(b), which show their formation as a function of
temperature, the experimental data are displayed
in two curves representing the upper and lower
levels within which the experimental results are
scattered. Nevertheless, the trend in the intensity
variation is clear.
3.3.3 Aliphatic hydrocarbons
Figures 5(a) and 5(b) show
aliphatic hydrocarbons through
the evolution of
their lines at m/e
67 (cyclopentene), 55-57 (C,,-C,, alkenes) and
57 (C,,,C,, alkanes). As can be seen, they all
have small peaks situated towards the higher
1 .la5oo
I\ _,_ l
o.OOE*w
: _ ,_--,
0 SO 100 150 200 2x) 3aO 350 4Oa 450 SaJ
50 100150 200 250 MO 350 400 *50 500
T- W)
Fig. 5. Ion monitoring during PVC thermal degradation: (a)
cyclopentene (67); (b) C,0-C,3 alkenes (55-57) and C,,-C,,
alkanes (57).
186 I. C. McNeil1 et al.
5mE-10-~
2
,j>
0ooE.M).
0 so 1w 150 xl0 25n c?m 350 400 450 !m
Tempermum CC)
Fig. 6. Ion monitoring during PVC thermal degradation:
methane (16) and H, (2).
temperatures of the first degradation stage,
between 300 and 37oC, which develop into
important peaks in the second stage.
3.3.4 Non-condensable gases
Figure 6 illustrates the evolution of HZ (m/e 2)
and CH, (m/e 16) with temperature. The amount
of H, might be underestimated due to the low
sensitivity of the quadrupole mass spectrometer
for m/e under 10 amu. However, the general
tendency of H, evolution can be observed. H,
and CH, are formed only in minor amount, if
any, in the first degradation stage. They are
evolved in detectable amounts in the second
stage, at temperatures above 400C.
4 DISCUSSION
4.1 Aspects of PVC degradation fromprevious
work
It is known that the thermal degradation of PVC
begins at a relatively low temperature, soon after
T. (8OoC).4 The initiation of the dehydrochlorina-
tion (DHC) was correlated with the labile
sites-defects-of the chemical structure: the
allylic chlorine atom of the internal unsaturation,
the tertiary chlorine atom of the butyl branches
and the head-to-head units formed in the course
of synthesis. The head-to-head structures have an
increased tendency of splitting Cl, but do not
propagate the DHC more readily than PVC, as
shown by studies on model compounds prepared
by chlorinating cis-l,4-polybutadiene.s The con-
centration of the above defects was evaluated as
Oel-O-2/1000, 0*5-l/1000, and under 0.2/1000
vinyl chloride (VC) units, respectively.h Although
the rate of degradation has been clearly
correlated with the concentration of allylic and
tertiary Cl, there is no definite evidence on the
nature of the initiation act at low temperatures
(SO-120C).
At the same time, it is possibile that physical
defects contribute to DHC. A certain confor-
mation of syndiotactic segments of chains in
which the Cl atoms are tram relative to a double
bond makes the DHC very easy, while the
presence of a Cl atom gauche to the unsaturation
favours the termination of polyene growth.
Syndiotactic chains of up to 13 VC units are
present in commercial suspension PVC samples,
as part of very small imperfect crystallites
dispersed in the polymer matrix. Overall, the
conformation responsible has a concentration of
the same order of magnitude as the defects of the
chemical structure and it is likewise dispersed.
At high temperatures, the initiation of DHC
takes place in the whole mass of the polymer by
the random scission of the secondary chlorine
atoms. At intermediate temperatures, chain ends
can have an important contribution in DHC, if
proved to have labile structure. It is largely
accepted in the literature that chain ends
contribute to the formation of mononuclear
hydrocarbons, as reviewed below.
Benzene formation begins at low temperatures
(soon after T,) as soon as polyenes of suitable
length are formed through DHC. Polyenes are
very active in crosslinking and molecular
enlargement has been observed at a very low
degree of DHC (0.5% at lSOC). Several
mechanisms for benzene formation in the early
stages of thermal degradation have been
advanced: the cyclisation of a triene radical
situated at a chain end and formed through
DHC followed by the scission of the macro-
molecular chain, the thermal condensation of a
triene within the chain, or the reaction of a
triene in the triplet state easily achievable by
thermal excitation. The last hypothesis is still
very appealing though it did not gain experimen-
tal support with the passing of the years.
It is considered that at higher temperatures
benzene and alkyl benzenes are formed by an
intramolecular process (cyclisation) which starts
at the chain ends of the macromolecules, while
the inner part of the macromolecules is bound
into a crosslinked network. The network is
formed through: (i) Diels-Alder condensation of
double bonds belonging to different chains
generating cyclohexene rings and within the
chain generating cyclohexadiene rings, which
then become aromatic: and (ii) crosslinking
A study of the products of PVC thermal degradation 187
through free radical attack on unsaturation. The
extent to which either of these processes takes
place is not known, but both crosslinked and
conjugated structures have been identified.13 The
Diels-Alder condensation, however, is considered
a major process, for the use of a dienophile
strongly reduces PVC crosslinking.14 The present
picture of PVC as it degrades at temperatures
above 250C is that of a crosslinked internal
core to which loose branches are attached. The
branches or chain ends produce benzene and
other aromatic hydrocarbons by the cyclisation of
the free ends.
The breakdown of the crosslinked network
produces condensed ring aromatic hydrocarbons
with or without aliphatic substituents and
aliphatic hydrocarbons.
4.2 The chain ends in suspension PVC
In the framework of the above picture and since
we are concerned with the degradation at all
temperature levels it is worth examining the
structure of chain ends. The most probable
structure of the PVC macromolecule obtained by
suspension has been the object of an excellent
review.6
In suspension polymerisation, the major
termination path is by chain transfer to the
monomer. This is a complex process consisting of
several reactions by which one Cl atom is
expulsed and chain ends of the type a (1-chloro,
2-alkene) - Scheme 1 - are created. Chain end
a is referred to as pseudoterminal unsaturation.
The Cl atom reinitiates the polymerisation
producing chain ends of type b (1,2-
dichloroalkane). This is a very efficient process,
reinitiation by Cl becoming the main way of
initiation: four-five polymer molecules per
initiator residue are formed. Towards very high
conversions, under conditions of monomer
starvation, the termination is by chain transfer to
?
CICHZ - y - CH2 - ~t +--C , - C - CH2 - CHCI - CH2 - C 2C,
Cl Cl L
Hz
b
L
C
1
6
7 a
CH2CI
Scheme 1. The structure of the suspension PVC
macromolecule.
the polymer and polymer branching starts. The
most frequent branches are C, (type c, Scheme 1)
which shows that backbiting is the most probable
transfer process. The termination at high
conversions can also take place by H abstraction
from any chain, hence, a number of normal
(1,3-dichloroalkane) chain ends, -CH( Cl)-CH,-
CH,Cl, are formed.
Let us consider the C, branches among chain
ends. On average, in suspension PVC the
concentration of chain ends is: 0.8-0.9 chain ends
of the type b, 0.7 chain ends of type a and O-2
normal chain ends per molecule, 0.20-0.25
initiator fragments units and 0.5-l C, branches
per 1000 VC units. Considering the molecular
weight of the present PVC sample, 40,000, one
can calculate the proportion of chain ends (Table
5). As already known6 and presented here in
Table 5, structures a and b are the most frequent
chain ends. Another observation is that C,
branches (hence tertiary Cl atoms) are quite
numerous.
Considering the structure of the PVC molecule
with three chain ends as in Scheme 1 (including
the C, branches), the MW of our PVC sample
and the amount of benzene being formed
through pyrolysis (5.6%), one can estimate that
9.5 molecules of benzene are formed per chain
end.
Little is known about the tendency to DHC of
chain ends of a particular structure. Table 6
shows the activation energy (E,) for HCl
elimination of model compounds. Long chains
ending in the structures shown in Table 6 are
expected to have lower E, than the mic-
romolecular compounds in the same table. As
one can see, 1-chloro, 2-alkene chain ends have
the highest tendency to DHC, followed by
1,2-dichloroalkane and finally by normal chain-
ends. For comparison, Table 6 also includes the
E, for the elimination of an allylic Cl associated
with a terminal double bond (compound No. 4)
which, if substituted at both ends (compound No.
5)
is a model for internal unsaturation and is
Table 5. The percentage of chain ends of different
structures in a typical suspension PVC sample
Type
b
St NCt UW %
CI CHr CHCHr 40-32
Cl
a Cl CHr CH=CHCH>- m-28
c Ter t i ar y Cl at G br anc hes 14-2s
l l l f ut or t er mi nat ed 8-7 s
NW& CI CHr CHr 8-7 5
Table 6. Activation energies for HCI eliminations
from model compounds [Ref. 151
Model w mpound
H,C-CHJ Ti KI
HC-CHCHKI
Cl
H,CCH=CH-CH>CI
H,C-CHCH=CHz
Cl
-HK-CH-CH=CH-
Cl
E. (k al hol e)
55 I
54 9(-ZHCI )
52 2
48 5
<48 5
expected to have a lower E, for DHC. Table 7
presents the C-Cl bond energies for model
compounds. Allylic Cl has a lower bond energy
than tertiary Cl. Allylic Cl associated to internal
unsaturation is expected to have even lower bond
energy.
The data presented in Tables 6 and 7 can be
interpreted in terms of higher probability for
DHC to start at the internal allylic Cl (of lower
concentration) and the tertiary Cl of butyl
branches (of higher concentration). As the
temperature increases, the pseudo-unsaturated
chain ends start DHC. They are followed by
1,2-chloroalkane, normal chain ends and, at
higher temperatures, mass dehydrochlorination
at secondary Cl atoms.
4.3 Degradation aspects of the present study
The evolution of the pyrolysis products suggest
two degradation stages triggered by thermal
energy (temperature). In the first stage, HCl and
benzene are formed in the same process and very
little of other hydrocarbons such as toluene,
styrene, indane, indene, naphthalene and alkyl
aromatic hydrocarbons. HCl is evolved at the
same time (temperature) as benzene (2OOC),
although the experimental curves show the
apparent anomaly referred to above of a delay in
HCl evolution. The retention of a small amount
of the HCl by the polymer once polyenes are
present could be explained by the hypothesis of
chemical reaction of HCl with polyene which
already has experimental support,h but such an
effect would not be expected so early in the
dehydrochlorination. Further experiments are
being carried out to clarify this phenomenon,
which may possibly be due to initial adsorption of
HCl on the glassware of the apparatus.
Table 7. C-Cl bond energy (kcal/mol)*
RCH,-Cl 81
R,CH-Cl a2
Rl CCl 79
CH,=CHCH,-CI 71
__ _ - _ . _
- P,emJlcm *I kamol , BUnI ner. LS.
188 1. C. McNeil1 et al.
It can be calculated from the data in Tables 1
and 2 that 15% of the double bonds formed
through DHC give benzene, hence most of these
structures accumulate in the polymer. The
process of HCl re-addition could explain why a
fraction of the original chlorine (about 10%)
remains in the polymer and gives rise to
chlorinated hydrocarbons.
The most abundant of the labile sites is the
tertiary Cl atom which is considered by many
authors the main site of initiation.6 Scheme 2
features the DHC initiated by tertiary Cl atom
scission and benzene formation at lower tem-
peratures (the beginning of the first degradation
stage).
Cl
- CH- CH2 - c - CH*- CHCl4* - CH2CI
b +*
i
-CI
i
(1)
-CH2-y-CH- H+CHZ-?H-W-y-.-
F
Cl Cl Cl Cl
---. Q +
(61
Cti-CH-
Cl
v
Scheme 2. Benzene formation initiated by tertiary Cl
scission.
A study of the products of PVC thermal degradation 189
The macroradical I formed through tertiary Cl
scission (reaction 1) would usually split in
position d with the formation of macroradical II
and macromolecule III (reaction 2). Macroradical
II has the structure of the growing chain in the
polymerisation and it is not known to promote
zip dehydrochlorination. Its main reaction route
in the absence of monomer is likely to be H atom
abstraction from another chain or from its own
chain (backbiting at the fifth C atom). Hence, it
is improbable that radical II has a direct role in
benzene formation which has to be sought in
another reaction.
The Cl atom expelled in reaction (1) will give a
random attack on any macromolecule. The
affinity of Cl atom for the CH, group6 would lead
to H abstraction through which radical IV is
formed. Radical IV can split (reaction 3) leading
to radical V which has a structure more
favourable to zip DHC. The electron withdraw-
ing effect of Cl polarizes the bonds in radical V as
shown in Scheme 2 favouring zip DHC by which
radical VI results after three double bonds have
been fomed (reaction 4). Radical VI has a
resonance form VII. It is proposed that radical
VII attacks the double bond at the sixth C atom
closing a cyclohexadiene ring and forming radical
VIII (reaction 6) which can then split the bond to
the ring as this bond is weakened by the
withdrawing effect exerted by the Cl atom on the
radical. The scission is followed by aromatisation
and H atom rearrangement so that no H transfer
from other molecules is needed. Benzene
formation has been shown to be intramolecular
not only with respect to C, but also to H.
Aromatic ring formation takes place after
scission and does not infringe the orbital
symmetry interdiction which operates with the
aromatisation of substituted rings. Moreover,
reaction (6) regenerates radical V which can
resume the cycle producing several benzene
molecules per radical chain end.
The alternative formation of toluene in
reaction (6) from radical VIII would imply the
scission of the bond between the C atom bearing
the radical and that bearing the Cl atom. Though
this is possible, it is not highly probable due to
the withdrawing effect of the Cl which shortens
and reinforces the bond. The repeated formation
of benzene at the radical chain-end apparently
prevents the formation of polyenes containing
more than three double bonds in this particular
place. Consequently, the formation of condensed
rings like naphthalene, indene etc., from radical
chain ends is of lower probability, a fact which
has the support of our experimental data since
very little of these compounds are formed in the
same stage as benzene. Our findings do not agree
with the conclusions of a previous study in which
it was conclued that condensed ring aromatic
hydrocarbons and alkyl aromatic hydrocarbons
are formed by the same mechanism as benzene.
The C, branch has a small, but finite
probability of being eliminated by the scission of
bond e. The chlorobutene isomers identified in
Table 4 (Nos 19 and 20) in low concentration can
be formed in this process (reactions 7 and 8). It is
not clear at this stage whether the saturated
homologue (chlorobutane, No. 21 in Table 4) is
formed in the same process or not.
The formation of macromolecule structure III
with vinylidene groups close to chain ends could
explain the crosslinking observed at very low
degrees of DHC (O-3%)8 through Cl atom attack
on this pendant unsaturation.
The formation of benzene at higher tempera-
tures through DHC of loose chain ends
followed by cyclisation starts with 1-chloro,
2-alkene type chain ends (pseudoterminal un-
saturation). Scheme 3 explains the formation of
benzene and other aromatic hydrocarbons from
chain-ends of this type.
The mechanism proposed in Scheme 3
accounts for benzene being formed through
repetitive scission of the chain ends of pseudoter-
minal unsaturation and for the main identified
alkyl aromatics being formed at smaller yields.
In Scheme 3, the 1-chloro, 2-alkene chain end
is polarised as shown, which makes the
dissociation of Cl atom easier (reaction 9).
Radical XI is formed in which the bonds are
polarised by the electron withdrawing Cl atoms
and the tendency to conjugation between the
double bond and the radical. This will render
DHC easier by which radical XII (reaction 10) is
formed. Radical XII has an alternative resonance
form XIII which would be expected to be
somewhat more stable. Both radicals, XII and
XIII, can explain the formation of aromatic
hydrocarbons. This process will be illustrated
here with radical XIII which can split in positions
a, b and c. Though route a is still most probable
due to the maximum gain in free energy for
benzene formation, routes b (leading to toluene)
and c (leading to styrene, ethylbenzene and
o&o-xylene) have increased probability com-
I . C. McNeil1 et al.
- CH - CH* - CH - ;H* - CHtCH2-CH = CH - &I2 + a
I I
Cl Cl
I
Cl
XI
- 3HCI
-..-~y2- i - - CH CH CH-CH-CH.CH_-CH*
XII
1
-~-c*-cH-cH=CH-cH.CH-cH=CH~
XIII
c ba
__t
!I
%
$ t dH CH=CH-CH.CH-CHCCH*
a
(-:
cCH - a$- CH = CH - iH2 + C&
Cl
1 tic,
XI
b
- y - CH2 + CH3- C&
c,
Scheme 3. Aromatic hydrocarbon formation from pseudo-
unsaturated chain ends.
pared to the formation of the same compounds
from macroradical VIII in Scheme 2. Scheme 3 is
also consistent with benzene being generated
repeatedly through the regeneration of radical XI
(reaction 12).
The formation of me&- and para- isomers of
xylene cannot be explained as arising from
radicals formed at marginal, loose branches of
the structures in Scheme 1. Their formation can
only be explained by the scission of the
crosslinked network containing benzenoid str-
uctures formed by Diels-Alder condensation.
5 CONCLUSIONS
PVC thermal degradation in vacuum up to 500C
has been studied by following the relative rate of
volatile product evolution in thermal volatilisa-
tion analysis experiments and by monitoring the
formation of the main products by mass
spectrometry. The material balance after pyroly-
sis combined with the GC-MS analysis of the
liquid fraction shows that HCl is the major
fraction (53% of the polymer), followed by tar
(24%), char (9.5%), liquid fraction (7%) and gas
fraction (6.6%). 10% of the Cl atoms remain in
the polymer after HCl evolution ceases. The
quantitative evaluation of the products in the
liquid fraction shows that benzene accounts for
80% of the liquid fraction and for 5.6% of the
polymer. The chlorinated hydrocarbons (mainly
chlorinated alkenes and chlorinated aromatics)
account for 1.75% of the liquid fraction and for
0.14% of the polymer.
PVC shows two degradation stages. During the
first one, between 200 and 360C HCl and
benzene are evolved but very little alkyl aromatic
hydrocarbons (toluene, xylene isomers, ethylben-
zene, etc.) or condensed ring aromatics (naph-
thalene, indene, indane, etc.). The molar ratio of
benzene and HCl shows that only 15% of the
double bonds produced through dehydroch-
lorination generate benzene. Most of the double
bonds accumulate in the polymer and are active
in crosslinking through intramolecular Diels-
Alder condensation and through free radical
attack. As a result, a crosslinked network is
created which contains cyclohexene and cyclohe-
xadiene rings embedded in an aliphatic matrix. In
the second degradation stage (360-5ooC), the
aromatisation of the above rings takes place with
much scission. As already suggested in the
literature, the aromatisation of the substituted
rings cannot occur if it necessitates orbital
overlapping of the substituted C atoms, due to
orbital symmetry interdictions. Hence scission is
a prerequisite for aromatisation. Scission gener-
ates an important amount of alkyl aromatic and
condensed ring aromatic hydrocarbons, as well as
C,-C,,
aliphatic hydrocarbons and a small
amount of hydrogen.
The mechanism of benzene formation thro-
ughout the temperature range has been con-
sidered beginning with scission at the tertiary Cl
(the most abundant labile site) and continuing
with the formation of benzene through the
cyclisation of chain ends, of which the pseudoter-
minal unsaturation is the most labile structure to
dehydrochlorination.
ACKNOWLEDGEMENT
Support from SERC for the work reported is
acknowledged with thanks.
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