Artigo reação PET HCl (1)

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Abstract Recycling of poly(vinyl chloride) (PVC) waste is
a serious problem because of its high chlorine content.
Dehydrochlorination of PVC-containing polymer waste
produces solid residue char, for which conversion to 
pyrolysis oil in a petrochemical plant seems to be an attrac-
tive way of recycling PVC waste. Unfortunately, some
polymer admixtures react with HCl and cause formation of
chloroorganic compounds in a char. This article describes
the influence of polycarbonates and poly(ethylene tereph-
thalate) on thermal feedstock recycling of PVC wastes using
a two-stage method. It was found that the presence of 
polycarbonate causes the formation of small amounts of 
benzyl chloride and other chloroaryl or chloroalkylaryl
compounds. Poly(ethylene terephthalate) interacts with
HCl forming significant amounts of various chlorocom-
pounds – mainly chloroethyl esters of terephthalic and
benzoic acids, but derivatives possessing chlorine directly
connected to the aromatic ring are also formed.
Key words PVC · BPA-based PC · PET · Recycling · 
Pyrolysis
Introduction
The disposal of plastic wastes will become an important part
of the chemical industry because of the large quantities of
plastics produced and their environmental impact.Chlorine-
containing polymers cause problems during material or
energetic recycling because of their decomposition with the
evolution of HCl. The most commonly used chlorine-
containing polymer is poly(vinyl chloride) (PVC), the
decomposition of which considerably limits material 
recycling due to the deterioration of its properties:
–CH2–CHCl– mers eliminate HCl under the influence of
heat (or light) and the PVC becomes yellowish or even
blackish and loses its plasticity. Such waste can be used as a
raw material for pyrolysis or for gasification. The choice
between these two methods depends on the amount of chlo-
rine in the char residue derived from a mixture of plastics
after HCl elimination from PVC. In this article we present
gas chromatography (GC) results after the thermal treat-
ment of pure PVC and of PVC mixtures with poly(ethylene
terephthalate) (PET) and with polycarbonate (PC).
Two main, mostly nonoverlapping, stages of mass loss are
observed during the thermal analysis of PVC.1,2 In one
series of experiments 0.5g samples of pure PVC underwent
a dehydrochlorination (DHC) reaction at temperatures of
up to 400°C. DHC was dicontinued when the char was free
of chlorine (to the accuracy of conductometric analysis of
eliminated HCl). DHC was followed by pyrolysis, which
mainly formed aromatic hydrocarbons – chloroorganic
compounds were not found by gas chromatography coupled
with mass detector (GC-MS) analysis.2 In contrast, Tromp
et al.3 found chlorobenzene and methylchlorobenzene 
after pyrolysis; however, it is not clear whether formation
of these compounds resulted from admixtures present in the
sample.
Segregation methods for plastic wastes that are accept-
able from the economical point of view do not guarantee
100% selectivity. If density difference is applied as the seg-
regation factor, PET remains in the PVC plastic fraction
(Table 1). Other polymers having a lower density will also
be present in this fraction; such polymers are usually filled
with inorganic additives (e.g., polycarbonates). Both the
polymers PET and PC can react with HCl to form
chloroderivatives, which then contaminate the pyrolysis
products of the char residue. The aim of our investigations
is the identification of such compounds.
J Mater Cycles Waste Manag (2006) 8:116–121 © Springer 2006
DOI 10.1007/s10163-006-0154-9
Krzysztof German · Kamil Kulesza · Miriam Florack
Influence of poly(bisphenol A carbonate) and poly(ethylene terephthalate)
on poly(vinyl chloride) dehydrochlorination
SPECIAL FEATURE: ORIGINAL ARTICLE
K. German1 (*) · M. Florack
Department of Chemistry and Technology of Polymers, Cracow
University of Technology, Kraków, Poland
K. Kulesza
Blachownia Institute of Heavy Organic Synthesis, Ke˛dzierzyn-Koz´le,
Poland
Present address:
1 Politechnika Krakowska, Samodzielna Katedra Chemii i Technologii
Tworzyw Sztucznych, ul. Warszawska 24, 31–155 Kraków, Poland
Tel. +48-12-628-21-14; Fax +48-12-628-20-38
e-mail: kfgerm@chemia.pk.edu.pl
Received: December 29, 2005 / Accepted: May 22, 2006
3rd International Symposium on Feedstock Recycling of
Plastics & Other Innovative Plastics Recycling Techniques
(ISFR 2005)
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117
in one of our previous papers,23 but our knowledge con-
cerning this process has increased since that time.The inter-
action between PVC and PET was also taken into account
in an article in which the pyrolysis of a selected mixture 
of plastics [intended to simulate municipal plastic waste
(MPW)] was described8. The article describes the results of
gas chromatography coupled with atomic emission detector
(GC-AED) analysis, as well as showing C-NP grams based
on gas chromatography coupled with flame ionization
detecter (GC-FID) results and selected results of the GC-
MS analysis, which agree with the results of our model
experiments. In the above work,8 Bhaskar, with coworkers
from the Sakata group, also reported the presence of some
chloroalkyl esters; however, identification of the particular
halogen compounds was not the goal of that work and
detailed results were not given. Complex plastic mixtures,
which also contain other halogen-containing polymers,
for example high impact polystyrene flame retarded with
bromine compounds (HIPS-Br) or chlorinated PVC and
poly(vinylidene dichloride) (PVDC) have been intensively
investigated (e.g., by Bhaskar et al.9 and Jakab et al.24). In
our opinion, apart from the very important general experi-
ments as described above, there is still a requirement for
basic studies that seek for an explanation of the formation
pathways of halogen-containing compounds in more com-
plex mixtures of plastic waste.
Fast degradation of PET starts at temperatures around
350°C. No volatile products of thermal degradation of
bisphenol A-based polycarbonate (BPA–PC) in an inert
atmosphere were obtained up to 400°C.17,18 It was found
that product composition depended on the reaction
medium – alkali media catalyze rearrangement reactions,
whereas acids and other substances with active hydrogen
atoms induce depolymerization.19 Investigations of the
pyrolysis of PVC–PC mixtures have not so far been
reported. It is expected that the thermochemical de-
Table 1. Density of selected polymers
Polymer Abbreviation Density (g/cm3)
Polyolefines PE, PP 0.89–0.97
Polystyrene PS 1.04–1.08
Polyamide PA 1.03–1.15
Polyurethane elastomers PU 1.10
Poly(methyl methacrylate) PMMA 1.18
Polycarbonate PC 1.20
(filled with glass fibers) 1.42
Poly(vinyl chloride) PVC 1.38–1.55
(plastificated) 1.19–1.38
Poly(ethylene terephthalate) PET 1.38–1.41
Polytetrafluorethylene PTFE 2.20
-5
-4
-3
-2
-1
0
M
a
s
s
 
lo
ss
 o
f 
PV
C 
sa
mp
le
-2.6
-2.4
-2.2
-2.0
-1.8
-1.6
1s
t
 
de
ri
va
ti
ve
 [
mg
/m
in
]
TG - curve
DTG - curve
0 100 200 300 400 5000 100 200 300 400 500
Temperature [°C]Temperature [°C]
-9
-8
-7
-6
-5
-4
-3
-2
-1
0
M
a
s
s
 
lo
ss
 o
f 
PE
T 
sa
mp
le
 [
mg
]
-6
-5
-4
-3
-2
-1
0
1s
t
 
de
ri
va
ti
ve
 [
m
g
/m
in
]
TG - curve
DTG - curve
Fig. 1. Thermogravimetric (TG) and derivative thermogravimetric (DTG) curves of poly(vinyl chloride) (PVC) and poly(ethylene terephtha-
late) (PET) degradation in an inert atmosphere
Over the past decade, considerable progress has been
reported in the development of methods of dechlorination
of pyrolysis oil,4–13 but not all the problems have been 
solved as yet. Complete dechlorination is hard to realize if
the dehydrochlorinated mixture also contains polyesters
(e.g., PET). Some of the consecutive HCl reactions that
occur during the heating of these mixtures are yet to be elu-
cidated. The goal of this work is to make progress in this
area.
The thermal degradation of PVC has already been the
subject of numerous investigations. Some attention has also
been paid to the thermal degradation of PET14–16 and
PC,17–22 but the behavior of PVC–PET mixtures and espe-
cially the interaction of PVC with PC have been less
studied. The dehydrochlorination of PVC starts at temper-
atures of about 100°C lower than for PET and, if the poly-
mers are degraded separately, PVC is almost completely
degraded before the temperature is reached at which PET
starts to degrade (Fig. 1); however, the presence of HCl
accelerates PET degradation if the polymers are mixed.
The influence of PVC (mainly HCl from PVC) on the
composition of the products of PET pyrolysis was discussed
118
gradation of BPA–PC should be observed in the presence
of HCl.
Experimental
Materials
Poly(vinyl chloride) (PVC S-70) was acquired from Anwil
(Wl′ocl′awek, Poland), the BPA-based polycarbonate
LEXAN was provided as waste plastic by Telkom-
Telos (Kraków, Poland), analytical grade carbon disulfide
was from Riedel-de Haën (Seelze, Germany), HPLC-grade
dichloromethane was from Aldrich (Steinheim, Germany),
and active carbon samples from SKC (Dorset, UK).
Techniques
Dehydrochlorination and pyrolysis were conducted in a
purpose-built pyrolysis setup, as shown in Fig. 2. Samples
weighed between 10 and 50g and the temperature was mea-
sured by a NiCr–NiAl thermocouple. Pyrolysisproducts
were transported by nitrogen as a carrier gas into a glass
condenser system (air and water cooler) with an active
carbon adsorber and water scrubber located at the
polypropylene off-gas pipe. Dehydrochlorination was per-
formed at 350°C for 90min and was followed by pyrolysis
at 500°C for 90min.The pyrolysis of PC and PET separately
was performed for comparison under the same conditions
(90min at 350°C followed by 90min at 500°C). Condensed
pyrolysis products were dissolved in CH2Cl2; products
adsorbed on active carbon were extracted by 4cm3 of CS2.
The solutions were analyzed by gas chromatography
coupled with a quadruple mass detector (GC-MS, HP 8590
Series 2 equipped with 30m HP-1 column) using helium as
the carrier gas.
Results and discussion
Our early work on PVC dehydrochlorination and pyrolysis
gave us much information about contaminations of the
derived oil (Table 2); however, when pure polymer was
used, we detected no chloroorganic compounds. The oil
fraction from the pyrolysis of PET contains mainly benzoic
Table 2. Pyrolysis products of PVC char residue at 550°C
Pyrolysis product; R = H, alkyl Molar ratio C/H Peak area (%)
1 2
<1 16
<1 5
<1 4
>1 4
>1 to 1 29
>1 3
>1 1
>1 to 1 11
>1 2
>1 4
>1 2
>1 2
Unidentified 15
R
R
R
R
R
R
R
R
R
Fig. 2. Experimental setup for pyrolysis
14.00 16.00 18.00 20.00 22.00 24.00 26.00
0
500000
1000000
1500000
2000000
2500000
3000000
3500000
4000000
Time-->
Abundance
TIC: MF6.D
COOH
COOH
COOH
O
O
CH
o-terphenyl
C18H14C14H10
C18H14
Fig. 3. Result of GC-MS analysis of liquid products formed during
PET pyrolysis
acid and biphenyl. Moreover, small amounts of other com-
pounds were identified, as shown in Fig. 3. The retention
time of acetaldehyde was less than 14min.
The product composition of the pyrolysis of PET
changed radically in the presence of PVC (HCl), which
caused the formation of a great number of organic
chloroderivatives. It is clear that the amount of these com-
pounds produced depends on the proportion of PVC to
PET in the dehydrochlorinated and then pyrolyzed samples.
High chlorine content was the goal of our work because it
makes for easier product identification, so we used 1 :1
(w/w) PVC–PET mixtures. In real-life waste mixtures there
will be less PET than PVC.
119
Some of the chlorine compounds derived are specified in
Table 3. Identification of these compounds was described 
in an earlier paper.23 A possible formation pathway of
chloroderivatives from PET in reaction with HCl is 
presented in Fig. 4. HCl attacks the ester bond and a 
transesterification reaction leads to formation of the
–COOC2H4Cl group. The atypical structure of
–COOC2H4Cl and the relatively high probability of its for-
mation are sources of the problems with dechlorination of
pyrolysis oil derived from PVC-containing PET. It is note-
worthy that chloroorganic derivatives (for example 3-
chlorobenzoic acid and 4-chlorobenzoic acid) are formed
not only in the transesterification reaction of polyester and
HCl; compounds that include the formyl group, the alkyl
group, or chlorine connected to an aromatic ring can be
formed by consecutive reactions after decarboxylation of
terephthalic acid mono-2-chloroethyl ester.
A chromatogram of the oil fraction obtained during
pyrolysis of PC is presented in Fig. 5. We did not find fluo-
renone or xanthone derivatives – in contrast to the results
described in other works19,21 – and this fact can be explained
by the absence of basic catalysts in the reaction medium.
A chromatogram of the oil fraction produced by pyro-
lysis of a 1 :1 (w/w) PC–PVC mixture is shown in Fig. 6.
The main products of pyrolysis of a dehydrochlorinated
PVC–PC mixture are phenol, 4-isopropylphenol, and 1-
isopropyl-4-phenoxybenzene. Our results confirm the find-
ings regarding the influence of an acidic medium on the
mechanism of thermal degradation of PC.
Among the pyrolysis products condensed in oil fractions
derived under the previously described DHC and pyrolysis
conditions, we did not find the chlorine derivatives 
predicted by the reaction scheme shown in Fig. 7. We did
find a number of these compounds among the products
Table 3. Chloroorganic products of PVC–PET 1 : 1 (w/w) mixture pyrolyzed at 450°C
Chloroorganic compounds Peak area share (%)
Chlorine in an aliphatic moiety
Methane, bis(2-chloroethoxy) 0.8
Chlorine in an aliphatic moiety of benzoic acid esters
Benzoic acid, 2-chloroethyl ester 11.2
4-Methyl and 4-formyl benzoic acid, 2-chloroethyl esters 8.5
Chlorine in an aliphatic moiety of 1,4-benzenedicarboxylic acid esters
1,4-Benzenedicarboxylic acid, mono-2-chloroethyl esters 18.8
1,4-Benzenedicarboxylic acid, bis-(2-chloroethyl ester) 30.6
Chlorine in an aromatic ring
3- and 4-Chlorobenzoic acid, ethyl ester 0.3
Chlorine in an aromatic ring and in an aliphatic moiety
4-Chlorobenzoic acid, 2-chloroethyl ester 0.4
COOCH2CH2OOC COOCH2CH2OHCH2CH2OOC
HCl
CH2CH2OOC COOH + ClCH2CH2OOC COOCH2CH2OH
HCl
CH2CH2Cl + HOOC COOH
COOCH2CH2OOC COOCH2CH2Cl
ClCH2CH2OOC COOCH2CH2Cl
HCl
+COOH
ClCH2CH2OOC COOCH2CH2Cl
+ HCl
- H2O
Fig. 4. Formation of chloroderivatives from PET in the presence of
HCl
5.00 10.00 15.00 20.00 25.00 30.00
0
1000000
2000000
3000000
4000000
5000000
6000000
7000000
8000000
9000000
1e+07
1.1e+07
1.2e+07
1.3e+07
1.4e+07
1.5e+07
Time-->
Abundance
TIC: [BSB1]MF5.D
Fig. 5. Chromatogram of the products of polycarbonate (PC) 
pyrolysis
5.00 10.00 15.00 20.00 25.00 30.00
0
500000
1000000
1500000
2000000
2500000
3000000
3500000
4000000
4500000
5000000
5500000
Time-->
Abundance
TIC: MF7.D
OH
OH
O
Fig. 6. GC-MS result of analysis of pyrolysis products of dehy-
drochlorinated PVC-PC (1:1 w/w) mixture
120
of the total area, but based on this it is not possible to say
whether the ratio of chlorine in the oil fraction from pyrol-
ysis of PVC–PC mixtures exceeds the technological thresh-
old of 10ppm, even though the amount of PC in waste
mixtures is much lower than in our mixture. Identification
of chlorine derivatives by means of GC-MS requires 
close attention because of the masking effect of Cl-isotopes
by signals resulting from other fragmentation paths,
especially when some compounds are not separated in the
GC column. For example, it was not possible to detect 
the presence of 4-chlorophenol using only analytical stan-
dards because signals of this chloroderivative were masked
by the signals of naphthalene. We did not separate 
these substances in our chromatograph column. Benzene
dichloride and benzyl chloride were also not separated
because of their similar vapor pressures, but they give 
characteristic signals at slightly different retention times
(Fig. 9).
Pyrolysis of PVC–PET–PC (1 :1 :1) mixtures did not
reveal new chlorine-containing compounds, but the analy-
sis has not yet been completed because of its complexity.
Conclusions
PET interacts with HCl forming large amounts of
chloroderivatives, mainly chloroethyl esters of terephthalic
acid and of benzoic acid but also compounds with chlorine
in the benzene ring. Pyrolysis of BPA-based polycarbonate
produced 4-methylphenol, 4-ethylphenol, 4-isopropylphe-
nol, 4-(1-methyl-1-phenylethyl) phenol, 1-isopropyl-4-
phenoxybenzene, BPA, and small amounts of other 
compounds. HCl evolved during the dehydrochlorination of
PVC–PC mixtures changes the composition of PC degra-
dation products – mainly phenol, isopropylphenol, and 
1-isopropyl-4-phenoxy-benzene are produced. Polyesters
OC
O
O C
HCl
HCl
O CH
C
O
O Cl
+
CClO H + CO2 +
HCl
O CH Cl +
HCl
OH Cl
C+
- CO2
HCl
Cl
Cl
+
Cl
+
CClHCl
HCl
CCl
HCl
OH
A
+ A
Fig. 7. Potential pathways for chloroderivative formation during the
interaction of PC and HCl
5.00 10.00 15.00 20.00 25.00 30.00
0
1000000
2000000
3000000
4000000
5000000
6000000
7000000
8000000
9000000
1e+07
1.1e+07
1.2e+07
1.3e+07
1.4e+07
1.5e+07
Time-->
Abundance
TIC: MF9G1.D
OH+
Cl
Cl
Cl
Cl
Cl
(treaces)
Cl
CH2
+
Fig. 8. Chromatogram of products formed during pyrolysis of PVC–PC
(1 : 1 w/w mixture) adsorbed on active carbon
10.30 10.40 10.50 10.60 10.70 10.80
0
50000
100000
Time-->
Abundance Ion 146.00 (145.70 to 146.70): MF9G1.D
10.30 10.40 10.50 10.60 10.70 10.80
0
50000
100000
Time-->
Abundance Ion 148.00 (147.70 to 148.70): MF9G1.D
10.30 10.40 10.50 10.60 10.70 10.80
0
50000
100000
Time-->
Abundance Ion 126.00 (125.70 to 126.70): MF9G1.D
10.30 10.40 10.50 10.60 10.70 10.80
0
50000
100000
Time-->
Abundance Ion 128.00 (127.70 to 128.70): MF9G1.D
Fig. 9. Profile of characteristic
fragmentation signals of
benzene dichloride and benzyl
chloride
adsorbed on active carbon, but some of them were in 
isomerized form. A chromatogram of these products is pre-
sented in Fig. 8. The area of the peaks of all chlorocom-
pounds that were identified by GC analysis is about 2%–3%
121
show interaction with HCl at temperatures below 350°C.
These secondary reactions during thermal degradation of
PVC–PC mixtures produce small amounts of halogen deriv-
atives such as chlorobenzene, 1,4-dichlorobenzene, benzyl
chloride, 4-chlorophenol, and isopropylchlorobenzene. The
diversity of these substances proves that a universal method
is necessary to eliminate the chlorine content from char
residue or from pyrolysis oil.
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