Macromol. Symp.

115,27-40 (1997) 27

PVC PHOTO-OXIDATIVE DEGRADATION: IDENTIFICATION OF

VOLATILES

Marek E. Krzymien, Michael Day, D. James Worsfold and David J .

Carlsson.*

National Research Council of Canada

Institute for Chemical Process and Environmental Technology
Ottawa, Ontario CANADA K1A OR6

Abstract: Volatile products present in poly(viny1chloride), PVC, .after

outdoor weathering have been compared with volatiles from laboratory,
UV exposed PVC surfaces. Compounds both present in the photo-
degraded polymer surface layer and directly emitted from the polymer
were measured in the laboratory experiments. The hydrocarbons,
oxygenated compounds and chloro-organic species were measured and
identified by capillary gas chromatography with a mass spectrometer
detector.

INTRODUCTION

Most mechanistic studies of polymer photo-oxidative degradation have focussed

on the early stages of reaction. This resulted from the need to correlate the
chemistry with loss in physical properties such as embrittlement, which occur
after quite low extents of reaction in thin, transparent samples (Ref. 1,2). In
thicker and heavily pigmented samples, especially if the polymer has a low oxygen
permeability such as poly(viny1 chloride), PVC, photooxidative degradation has
been shown t o be very non-uniform, reaction being concentrated close to the
irradiated surface (Ref. 3,4). Polymer loss from such surfaces by erosion and
volatization can be expected to result from accumulated chain scissions. This will

0 1997 Huthig & Wepf Verlag, Zug CCC 1022-1360/97/$04.00

2a

be promoted by the photocatalytic effects of pigments such as titanium dioxide

(TiO,) (Ref. 5).

For many years, degrading polymers have been known to emit volatile products.
For example, polyolefins can give off-odours after oxidative degradation which can
lead to product rejection in medical products. Gas chromatography (GC), in some
cases combined with mass spectrometry (MS) detection, has been used to identify
breakdown products from oxidized polypropylene and polyethylene, (Refs. 7-10).
Kwei has used GC-MS to examine volatiles from photo-oxidized PVC, but detected
only very small molecules (CO,, CO, HC1, etc.) from unpigmented, unstabilized
samples (Ref. 11).

In this paper, we examine the ability of GC and GC-MS to detect and identify
species which volatilise from pigmented PVC formulations and which result from
the photo oxidative breakdown of the polymer itself. In addition, residual volatiles
which can be desorbed from outdoor weathered PVC are compared with products
from controlled, laboratory irradiation experiments.

EXPERIMENTAL

Rigid PVC panelling (commercial house siding) was examined after outdoor
exposure (Ottawa, Canada, 11y. south facing, vertical installation) and also after
exposure in the laboratory to Pyrex filtered (> 280 nm) ultra violet (UV)from a 550
watt high pressure Hanovia arc or in a xenon arc Weatherometer (2500 watt,
Model 25-WR, Atlas Electric Devices, Chicago USA, Pyrex inner and outer filters).
The latter simulates noon summer sunlight and was operated a t a constant
incident intensity of 0.96 w/m2/nm at 420 nm.

In order to measure residual volatilisable products in outdoor exposed samples,

surface PVC was removed as a fine powder by abrading away a thin surface layer
(- 15 pm) with a scrupulously clean file. For each sample, this powder was
aspirated into a clean Pyrex transfer tube (6 cm x 4 cm ID), capped with silane -
 29

treated glass wool. The PVC powder-packed tube was heated to 80" or 120°C for
3 min. in the inlet system of a gas chromatograph (GC) to desorb volatiles into a
Tenax TA trap [poly (2,6-diphenyl-p-phenylene
oxide), Chrompack Inc.] at -20°C
as described previously (12). The trapped material was then flash desorbed (at
220°C) into the capillary GC column (30 m x 0.32 mm ID column, with a 1.8 pm
coating of siloxane (DB-624, Chromatographic Specialties Inc.) which was
temperature programmed from -20" to 220°C at 5"C/min after a 5.5 min. hold at
-20°C.

To trap volatiles directly emitted during irradiation, PVC samples exposed in the
laboratory irradiation experiments were housed in Pyrex vessels. In the passive
adsorption mode, a porcelain boat of Carbopack and a separate boat of Carbosieve
S adsorbents (Supelco Inc., - 40 mg in each case) were located adjacent to the PVC
sample (8.4 x 4.6 cm2) in the 250 cdi , closed cylindrical cell. In the dynamic
system, a rectangular cell was constantly swept by a flow (10 ml/min) of ultrapure
air throughout the W exposure. The air passed over the PVC sample (13.7 x 3.7
cm2)contained in the rectangular cell and then exited through an adsorbent train
consisting of two glass tubes (6 mm x 4 mm ID each) connected with compression
fittings, the first tube packed with Carbopack (- 200 mg, 1.6 ml) and the second
packed with Carbosieve S (- 200 mg, 1.6ml).

The granular carbon adsorbents (Carbopack and Carbosieve S) are extensively

used in atmospheric sampling analysis (Ref. 12,13). Carbosieve S adsorbs all
species down to very volatile gases, but does not readily release compounds above
about C, during desorption at 220°C. In contrast Carbopack adsorbs small
molecules only weakly yet desorbs most species at 220°C. Consequently the two
adsorbents can be used to give complementary information on the species in the
atmospheres of the two cells.

After exposure, the products trapped in the granular carbon adsorbents were
desorbed at 220°C in the GC inlet, cryofocussed and analysed by GC as before.
The UV exposed surfaces of PVC samples, both from the passive and dynamic
systems were also sampled by abrasion and analysed as described for the outdoor
30

exposed PVC.

Preliminary studies were conducted using a Varian 4600 GC equipped with an

electron capture detector (ECD) in parallel with a flame ionization detector (FID).
The high sensitivity of the ECD allowed small samples (5-10mg) t o be analysed.

For detailed identification, larger samples were analysed by GC-MS (Hewlett-

Packard 5790 GC with a mass selective detector (Hewlett-Packard 5970A MS)
which gives a total ion chromatogram and records the mass spectrum of each peak.
Mass spectra were then automatically searched using Hewlett-Packard
Chemstation software (Version 3.2) which compares the mass spectra of each
resolved peak with the 76,000 standard spectra in the NBS library (Revision F)
using a probability based matching system.

RESULTS AND DISCUSSION

The commercial PVC samples studied (stabilized, pigmented siding material, 1.5
mm thick) were characterized by gel permeation chromatography (initial
molecular weights all 155 000 * 5 000 Daltons) and analysed for metal content
(pigments and stabilizers). All samples produced 10%ash, following ashing in air
at up to 5OO0C,composed of metal oxides. Inductively coupled plasma atomic
emission spectroscopy (ICP-AES)of the ash dissolved in aqua regia indicated that
it was predominantly TiO,, with 0.2 wt% calcium, based on the initial PVC weight.
Cadmium, barium and lead were at or below 0.005 wt% of the initial PVC weight.
To analyse for frequently used tin additives, PVC was digested in conc. sulfuric
acid and then dissolved in 2M hydrochloric acid. ICP-AES indicated 0.18 wt% of
tin based on the initial PVC weight.

Two stock PVC materials were studied after outdoor exposure: a grey and a pale
yellow sample, both exposed 11 years. In order to determine the volatilizable
compounds remaining in the surface layers, 4-5 mg powder samples were abraded
from the top surface layer of the UV exposed material and volatiles desorbed from
 31

the powder for GC analysis. Both PVC samples gave very similar chromatograms
of desorbed species from each powder sample using ECD and FID detectors
whereas the non-UV exposed material desorbed very little.

To identify the desorbed species detected in these survey chromatograms (not

shown), areas of the grey PVC material were examined by GC-MS necessitating
much larger samples (130-170 mg) (Figure 1). Peak intensities (MS total ion
chromatogram) and MS identification (> 80% confidence from the search software)
are collected in Table 1. Under the desorption conditions (80°C or 120°C) used,
non-UV exposed PVC surfaces did release some volatiles (Figure 1B). Only small
peaks from chlorine containing compounds were detected and the stronger peaks
may be attributed to componentsin the formulation (such as impact modifiers) and
residues of process intermediates. Desorbed species that were detected at similar
quantities from all samples (UV irradiated or obverse control) include butanal, 1-
butanol, di-n-butyl ether and butyl propionate. The UV exposed surface of the
PVC sample showed an extremely rich GC with many chloro- or dichloro-
compounds overlaid on the species desorbed from the non-degraded, control surface
(cf. Figures 1A and B).

Thermal desorption of species from the PVC surface materials was performed at
80°C or 120°C. The former is a more reasonable approximation of what a PVC
panel will experience in normal summer outdoor exposure. At 120"C, a quite
similar range of products was found but absolute quantities were about 10 times
higher. This made MS identification much more reliable and the 120°C condition
was used for the remainder of the study (all data in Tables 1and 2 and Figures 1,
2 and 3). Some of the observed species may be the result of thermal cracking of
PVC oxidation products rather than scission products present in the surface. A
detailed study of product distribution as a function of progressively lower
desorption temperatures is obviously required. Nevertheless the observed
products can reasonably be expected to desorb from PVC surfaces during their
outdoor exposure lifetime.

It is possible that some of the detected emissions might result from surface
32

18
A

17

Retention Time (min)

Fimre 1 Volatiles desorbed from PVC surfaces a t 120°C

A. From PVC powder (158 mg) abraded from the outdoor exposed surface (11
years, south facing).
B. From PVC powder (143 mg) abraded from the obverse (non-irradiated)
surface of the same sample. (For peak identification see Table 1)
 33

Products thermally desorbed from PVC powder samples

Peak etention Compound' - Zlative A idancel106

Number Time ontrolb 11 y sun. -14h Ih
(mid .43 mg) 157 mg) Cenon Arc' ercury Arcd
160 mg) 48 mg)

1 9.8 n-Butane 0.8 0.8 2.4 2.5

2 10.8 ketaldehyde 0 0.05 0.3 0.7
3 12.4 Chloroethane 0 0.05 0.3 0.4
4 16.0 2-Chloropropane 0 0.15 0.6 0.6
5 16.6 Propan-2-one 0.12 0.95 3.4 4.4
6 18.2 1-Chloropropane 0 0.80 1.5 2.4
7 20.2 1,l-Dichloroethane 0.3 0.4 0.8 0.6
8 21.7 Butanal 1.7 4.6 5.0 6.0
9 22.2 Butan-2-one 0.2 2.0 2.7 4.5
10 23.1 Trichloromethane 0 0.5 0 0
11 23.7 1-Chlorobutane 0.1 3.0 9.8 10.1
12 24.7 2,2,4-Trimethylpentane 1.5 0.9 1.8 2.0
13 26.4 1-Butanol 5.8 5.4 4.1 6.8
14 26.7 l,2-Dichloropropane 0 1.3 1.5 2.0
15 27.7 Butyl formate 0.2 1.2 7.4 6.4
16 29.0 1-Chloropentane 0 1.0 1.2 1.4
17 29.2 l,l-Dichloropropan-2-on 0 3.8 0.8 0
18 32.0 1,2-Dichlorobutane 0.8 5.8 1.7 3.5
19 32.1 Butyl acetate 0.8 1.8 4.4 3.6
20 32.2 1-Chlorobutan-2-one 0 1.8 0.3 0
21 33.5 1-Chlorohexane 0 1.1 2.3 0
22 34.0 Di-n-butyl ether 5.3 3.4 4.6 6.0
23 35.8 Butyl propionate 1.5 1.6 2.2 3.1
24 37.8 1-Chloroheptane 0.2 1.0 1.2 0.8

a) Identification by MS
b) Non UV exposed or after 88 h a t 66'C
c) Static adsorption system
d) Dynamic adsorption system

contamination of the panel during its outdoor exposure. To examine this

possibility, 150-200 pm was ground from both surfaces of an outdoor exposed
sample. Emissions from subsequent powder samples abraded &om the surface of
this "cleaned" sample were very similar to those in Figure 1B except for the
absence of the two (unidentified)peaks at 40.0 and 42.0 minutes. These could be
surface contaminants or compounds surface concentrated during extrusion.
Samples subsequently studied in the laboratory irradiation (mercury or xenon
arcs) were ground in this way prior to irradiation (Figures 2 and 3).
34

The outdoor exposed panels can obviously only give information on relatively
involatile species remaining in the degraded surface layer. Laboratory simulation
experiments were performed in an attempt to reproduce the outdoor exposure
products under controlled, accelerated tests, and, above all, to allow the sampling
of the species directly desorbed from the PVC surfaces during W exposure. A
PVC sample was exposed to xenon arc irradiation in the closed cell equipped with
a granular carbon adsorbent (Carbopack). GC traces of the species desorbed
directly during exposure of the PVC to the Pyrex filtered xenon arc (> 280 nm) and
collected in the carbon adsorbent are shown in Figure 2 together with compounds
which could be thermally desorbed from the abraded PVC surface. Very similar
species are found from this PVC surface and the sunlight exposed surface (Table
1). The GC analysis of the adsorbent trapped volatiles indicated the evolution of
numerous chlorinated species into the atmosphere during the photoxidizing of the
sample (Table 2).

In experiments performed with the flow through cell and adsorption from the air
exiting the cell, both the photooxodized surface sample and the carbon adsorbent
sample indicated products and product distribution similar to these from closed,
passive absorption system (cf. Figures 2 and 3). Provided that break through of
adsorbed species (i.e. products swept completely through the adsorbent tube
during the flow experiment) did not occur, the adsorbents should give a more
quantitative measure of total emissions as compared to the static system where
only part of the volatile emissions will be adsorbed on the carbon granules during
irradiation. The remainder will adsorb onto the glass walls and the dark side of

the PVC sample.

Both laboratory W systems caused sample heating. It is possible that the

identified compounds could be products of surface photo-oxidation and heat
degradation, as well as thermal desorption. To explore this possibility, volatiles
were collected in the dynamic system from a PVC sample heated by infrared
heaters to the same temperature (66°C)as measured by a thermocouple embedded
in the xenon arc exposed PVC sample. Volatiles detected from the Carbopack are
shown in Table 2.
 35

11 A

8 1
3 1922
4

2
L
0 ,
T 15

-
g1.24
.i

15 19

30 410 50
Retention Time ( m i d
Fipure 2 Volatiles from a xenon arc irradiated PVC surface
A. Desorbed from PVC powder (169 mg at 120°C) abraded from the U V
exposed surface (414h.), passive system. (For peak identification see Table
1).
B. Volatiles desorbed from Carbopack adsorbent boat. (For peak identification
see Table 2)
36

Trapped Volatile Products from PVC samples'

Peak Retention Compound ive Abundancd106

Number Time 89h i
(min.) Xenon Arcb

30 8.2 Sulfur dioxide 0.90 0

2 10.8 Acetaldehyde 0.47 0.08
31 16.2 1,2-DichIoroethane 0.15 0
5 16.6 Propan-2-one 0.24 0
32 21.7 3-Butene-%one 0.82 0
10 23.0 Trichloromethane 0.85 0.08
33 23.3 Formic acid 0 0.20
11 23.6 1-Chloro-butane 0.78 0.28 0.10
34 24.0 Benzene 0.12 0
35 25.5 Acetic Acid 1.3 1.38
15 27.8 Butyl formate 0.58 0.26 0.15
36 29.0 Acetyl Chloride 0 0.15
37 30.1 2-Propenoic Acid 0.46 0
19 31.8 Butyl acetate 0.65 1.1 0.22
20 32.0 1-Chlorobutan-2-one 0.20 0
38 33.5 Butanoic acid 0.48 0
22 34.0 Di-n-butyl ether 0.48 0.67 2.0
23 36.0 Butyl propionate 0 0.65 0.4
21 37.8 1-Chlorohexane 0 0.35
39 38.5 1,3-Dichloropropan-2-ol 0 0.30
40 39.5 Chloroacetic acid 0.6 0.85
41 41.1 Butyl Chloroacetate 0.33 0
42 42.3 1,4-Dichloro-but-1-ene 0 0.10

a) Carbopack granular carbon adsorbent

b) Static system (adsorbent in boat, closed sample chamber)
c ) Dynamic system (adsorbent in tube; all volatiles in sample chamber swept through tube)

Not surprisingly, greater levels of volatile species (retention times i25 min.) were
found in the surface PVC removed from laboratory irradiated panels as compared
to sunlight exposed siding. These products would be most readily lost during the
11years outdoor exposure. Laboratory exposed samples gave 1-chlorobutane as
the dominant product &om the removed PVC surface whereas the sun-exposed
samples gave 1-chlorobutane, l,l-dichloropropan-2-one,and 1,2-dichlorobutane.

From previous mechanistic studies (although on pigment and stabilizer &ee PVC)
PVC is believed to photooxidize through the formation of hydroperoxidic species
which photolyse or thermally decompose further to alkoxyl radicals (reaction 1)
(Refs. 14-16).
 37

1 A

l1 L..
8 22

35
' 19

36
11
33 15
O0.4
o81 1 q
WI

o l Retention
e 20 . 30Time (min) " " 40
' ' ' - - 50
I -

Figure 3 Volatiles from a mercury arc irradiated PVC surface.

A. Desorbed from PVC powder (148 mg at 120°C) abraded from the UV
exposed surface (89 h), dynamic system.
B. Volatiles desorbed from Carbopack adsorbent train. Peak identification as
in Fig. 2.
 H OOH
I hv I
-CH,-C- -CH,-C- la
I 0 2 I
c1 c1
I
hv or A

0.
I
-CH, - C - + *OH lb
I
c1

Alkoxyl radicals readily p-scission at room temperature to give carbonyl products,

or hydrogen abstract to give alcohols (reaction 2).

0. 0
I II
-CH, - C - CH, - -CH, - C + *CH, - 2a
I I
Cl c1

\PVC OH
I '
c1
I
-CH,-C- + -C-C- 2b
I I I
c1 H H

Hydrogen chloride emission is normal from thermal decomposition of PVC, but

published data is contradictory as to its release during photooxidation (Ref. 11,14).

A few preliminary experiments using Carbosieve S (not shown) indicated 1-

chloroethane as a dominant product, at levels comparable to the 1-chlorobutane,
from both mercury and xenon arc exposed PVC surfaces.

Total ion chromatogram (TIC) abundance values from MS are not simply related
t o the quantity of each species present, TIC abundance being dependent on
fragmentation characteristics and ionization potential. However, preliminary
calibration, with about a dozen chloro-organic standards, indicated that 1 pg of
 39

most compounds gave a TIC abundances of 1.0 to 2.0 x lo6 in our GC-MS system.
This leads to a total yield of about 25 pg of chloroorganics from the xenon arc
irradiated PVC surface (40 cm', 414 h. exposure). Chlorine-free photooxidation
products total about half of this level.

The volatiles released by photooxidation (other than the background emissions

from the formulation) include ketones and chloroketones, acids and acid chlorides
and chlorinated alkanes which are consistent with multiple backbone scission
reactions in the highly photooxidized surface layer. The detection of longer chain
chloroalkanes and 1,l- or 1,2-dichloroalkanes is surprising because short
monochloroalkanes or 1,3-dichloroproductswould be logically expected from the
PVC structure. Further studies of the kinetic accumulation of products and
titanium dioxide photosensitized reaction are obviously required. The influence
of PVC formulation differences will be particularly pertinent.

CONCLUSIONS

1) Ketones, alcohols, aldehydes and chloro-organic compounds desorb from

outdoor exposed PVC as a result of a modest heat cycle.
2) Very similar products and product distributions are desorbed from the
surface of mercury or xenon arc Weatherometer exposed PVC (wavelengths
> 280 nm).
3) By the use of granular carbon adsorbents, off-gassing of a variety of
products can be detected during the laboratory exposure t o simulated
sunlight.
4) GC-MS and GC with ECD can be used to monitor the photooxidative
breakdown of the surface of pigmented, stabilized PVC samples.
40

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