Problems of ageing and stabilization of

poly(viny1 chloride)

K. 2. Gumargalieva, V. B. Ivanov, G. E. Zaikov, Ju. V. Moiseev & T. V. Pokholok

Institlrte c),fChemical Physics. 4 Kosygin Str., Moscow I 17334, Russitr

(Received 19 January 1995)

We have investigated plasticized poly(vinyl chloride) (PVC) samples aged in

natural and artificial conditions, and samples recovered after use for a long
time (15-30 years) at 253-301 K. The predominant process in dark. low
temperature ageing of plasticized PVC is loss of plasticizer by desorption. In
photo-ageing the main process is degradation of both polymer and plasticizer.
proceeding generally on the irradiated side of the sample and depending on
the spectral distribution of the light. Washing off of stabilizers from the
polymer occurs in contact with water. With consideration of the experimen-
tally determined empirical kinetic equations for mass loss or degradation
during use or artificial exposure we can determine the conditions of ageing.
Based on an analysis of the use conditions, one can deduce predictive
equations for the description of degradation. @) 1996 Elsevier Science Limited

1 INTRODUCTION properties with time and ageing factors.’ -I In this

case the selection of an ageing model does not
The main factors influncing the degradation of allow conclusions about the complete ageing
PVC include temperature, presence of oxygen, mechanism but is adequate for a description of
humidity, mechanical stresses, aggressive media the kinetics of ageing in particular use conditions.
and ionizing radiation, all leading to changes in It is necessary to use characteristic ageing
initial properties as a result of simultaneous indexes which reflect fundamental material
chemical and physical processes which change the properties (chemical composition, molecular
chemical composition and the structure of the weight distribution, physical structure), indepen-
material. In general, published investigations dent of the surrounding conditions, in order to
relate to the study of one of the processes, for differentiate ageing from changes in properties
example high-temperature degradation.’ ’ The caused by changes in external conditions
complex of processes is reduced to dehydro- (temperature, humidity). From this point of view,
chlorination reactions, leading to the formation the main process of PVC ageing at room
of polyene sequences whose amount and length temperature is plasticizer desorption. At temp-
determine the material colour. Other studies eratures over 60°C thermo-oxidative degradation
consider oxidative degradation with the formation is probable and accompanied by dehydro-
of carbonyl groups, or the diffusional desorption chlorination. The first process can be monitored
of plasticizer or sorption of water. In a real PVC by the residual amount of plasticizer. The
or any other polymer, not all of these processes occurrence of thermo-oxidative degradation and
will proceed. Moreover the occurrence of only dehydrochlorination may be monitored by the
a part of them will lead to changes in properties. changes in molecular weight distribution and the
For these reasons. in the study of ageing of any accumulation of double bonds.
polymer material it is necessary to determine an
ageing model representing the totality of the
2 EXPERIMENTAL
kinetic data for ail ageing processes established
as proceeding in the polymer, and to obtain We have investigated wire insulation produced
formal kinetic equations connecting the desired from plasticized PVC type M64 (USSR), used for
a long time (up to 28 years) in aircraft engines
and received from industry after 1 or 2 years
storage, together with PVC films of thickness
0.1-0.35 cm, with various contents of dioctyl- or
other dialkyl-phthalates.
Plasticizer loss was fitted to the empirical
equation:’
nl, = kt”
where m, is the amount of plasticiser lost in time t
and II and k are parameters (0.5 <M < 1).
Residual plasticizer was determined by thermo-
gravimetry, chromatography or UV-spectro-
photometry. Thermogravimetric analysis was ma\\ part DOPh
performed using DuPont 1090 or Mettler TA
3000 instruments. Analyses were performed in
isothermal or dynamic modes at heating rates in
the range 0.1-100 K min ‘.
Fig. 1. (a) Thermogravimetric curves of mass losses of PVC
UV spectra of PVC specimens in solution in with different contents of dioctylphtalate (DOPh),
tetrahydrofuran were obtained using a Pye lO”C/min: l-10; 2-20; 3-30; 4-40: S-50: 6-60 parts
Unicam PS 800 instrument over the range per 100 parts of PVC. (b) Relation between weight loss and
18.5700 nm. content of DOPh at heating up to 400°C.
Chromatographic analyses were performed
using a gas-liquid chromatograph of the ‘colour’
loss corresponds to loss of plasticizer plus
series. Columns 3 mm in diameter and 100 mm
dehydrochlorination and depends linearly upon
length, filled with chromaton were used for
the plasticizer concentration.
plasticizer analysis. Figure 2 shows typical chromatograms of three
High pressure liquid chromatography was
plasticizers, together with the calibration curves
performed on a DuPont instrument using
which relate the peak areas to the amount of
adsorption and gel-permeation modes with
plasticizer.
Zorbax and SE-100 columns. Plasticizer contents were calculated from UV
Plasticizer extraction was performed with absorption spectra using the Beer-Lambert
diethyl ether at 45°C for 6 days. relation with an extinction coefficient of 19.3 f
Molecular weight distributions were deter-
0.2 1mg ’ cm-_’ at 230 nm for DOPh in
mined by conventional GPC. tetrahydrofuran.
IR spectra were obtained using a Digilab Residual plasticizer concentrations were also
Qualimatic instrument. For analysis of plasticizer
contents we used the absorption bands in the
1720-1726 cm- ’ range (C=O vibrations) and at
around 1020 cm-’ (C-O-C vibrations).
The microporous structure of the polymer was
measured with a Quantichrome Autoscan 33
mercury porosimeter.

3 RESULTS AND DISCUSSION

A number of methods were used for determina-

tion of the decrease of plasticizer concentration
in PVC, including TGA, chromatographic analy-
t (min)
sis of extracts and direct UV spectrophotometry.
Fig. 2. Typical chromatograms of three plasticizers (a) and
Figure 1 shows the mass loss curves by TGA peak areas versus their amount in specimen (b):
for PVC containing various amounts of dioctyl DDPh-diisodecylephtyalate: DOPh-dioctylphthalate:
phthalate (DOPh), heated to 400°C. The mass DOS-dioctylsebacate.
 Problems of ageing and stabilization of’pol~(vi~zyl chloride) 7s

Fig. 5. The change of mass (1) and linear dimensions

(2-length) and (3-width) of PVC films at 150°C (air).

Fig. 3. Relative optical density of plasticizer to polymer It is natural to expect that the dimensions of
versus their relative content.
PVC samples will also change as a result of
determined from IR absorption spectra obtained plasticizer desorption. Linear and volumetric
by ATR (KRSS crystal) on films of polymer. changes were determined for films using the
Figure 3 shows the experimental dependence of relations:
the ratio fIJII,,,, on X,,,/X,,,,,, where D,, and D,,,,, Al = (I,, - 1,)/l,, and AV = (V,, - V,)/ [,
are the optical densities of bands due to the
plasticizer and the polymer, respectively, and X,, where I,, and V,, are the initial values of length or
and X,,,,, are the corresponding volume volume, and I, and V, are the corresponding
concentrations. dimensions at ageing time t.
Experimental data for the loss of plasticizer as Shrinkage of wire insulation was determined
measured by UV spectroscopy are shown in Fig. from the length or diameter of the insulation.
4 for desorption at five temperatures. All of the For thermal ageing of film at 150°C we found
data can be described by the empirical equation: that the total mass change was 27.0 f 0.2% (Fig.
5) and that the mass loss followed eqn (1). The
In m, = ~[o.h2*:“.“’
linear size changes were accurately fitted by the
m,>
equation:
where k is the desorption constant.
N = A/,( 1 - exp( 1 - kr))
The common dependence of the data suggests
that the process probably involves the same where the rate constant was found to be
mechanism at all temperatures studied. (5.5 f 0.2) x 10 hS ‘.
We found that chromatographic data do not fit The corresponding dimension changes for wire
this equation so well, because of the poor insulation were smaller than for films, because
precision of the method of analysis. the contraction is resisted by adhesion to the
wire.
The molecular weight distributions (MWD) of
the initial PVC samples and of samples after
ageing were bimodal, with peak maxima
corresponding to viscosity-average molecular
weights of 4.8 X 10’ (A) and 3.6 X 103 (B),
respectively. Table 1 shows the changes in these
two components with ageing under different
temperature conditions. The content of the high
molecular weight component (A) increases
steadily with ageing at 140°C. After ageing for
2.5 h the peak at low molecular weight
Fig. 4. Generalized kinetic curve of diffusional DOPh
desorption from PVC: (A) 135°C: (X) 120°C: (0) 105°C:
disappears.
(0) 90°C: (0) 47°C. Despite these changes. we observed no
76 K. Z. Gwnarplirvrr et al.

Table 1. Correlation of PVC MWD components for various

time-temperature ageing regimes

Ageing time. Temperature, PVC MWD component

h “C part, %

A B

0 20 70.8 29.2
4.4 x 10 20 70.6 29.4
100 70 70.5 29.5
50 80 70.4 29.6
100 100 72.5 27.5
100 110 74.5 25.1
100 120 88.0 12.1
2.5 140 97.3 -

significant changes in the MWD of PVC samples

used for periods of 20-28 years. It seems likely
that the changes seen at high temperatures are
due to the cross-linking of low molecular weight
fractions, resulting in a shift in MWD to high Fig. 6. Initial dehydrochlorination rates in arbitrary units
molecular weights. according to accumulation of polyene fragments in the
For investigation of the concentration of 120-180°C temperature range.

polyene fragments formed on dehdrochlorina-

tion, we used liquid chromatography (0.05% Cable insulation from articles dismantled after
polymer solution in THF). On ageing there 15 and 30 years of use was studied in order to
appears a new peak (A) with a retention time of understand the nature and relative contribution
1.76 f 0.01 min, corresponding to polyene frag- of the physical and chemical processes occurring
ments with sequence lengths equal to or greater in low temperature ageing. The samples had been
than five units (the retention time for the original used in darkness at an equivalent temperature of
polymer (B) was 2.12 f 0.01 min). around 20°C. The minimum temperature was
Table 2 shows the relative contributions of the -20°C and the maximum +28”C. The main
two peaks for different conditions of ageing. results are shown in Table 3.
Figure 6 shows the rates of dehydrochlorination We observed no significant formation of
measured by the accumulation of polyene products of oxidation or of dehydrochlorination,
fragments in the range 120-180°C. The activation using IR spectroscopy or liquid chromatography.
energy determined from these data was 113 f MWD data were not recorded.
5 kJ mall’, which is the value for the dehydro- Based on these data we can assert that the
chlorination in the presence of oxygen. main process in ageing of plasticized PVC at low
temperatures is diffusional desorption of the
Table 2. Correlation of peaks of initial and polyene frag plasticizer. This process can be monitored
ments containing PVC for various time-temperature reg- sufficiently precisely by two indices, the loss of
imes of ageing and makes of PVC
plasticizer and the increase of porosity of the
Ageing Temperature, PVC- Peak part, % polymer as measured by mercury porosimetry.
duration, “C plasticate For studies of light ageing of PVC, we began
months trade-mark A B
with the assumption that the ageing begins on the
0 I-40-13 100 surface of the material and depends upon the
14 70 __ 97.2 2.8 spectral composition of the light. PVC films of
305 17 96.4 3.6
various thicknesses were obtained by slow
0 I-40- 12 100 -
14 70 __ 97.6 2.4 evaporation of solvent (dichloroethane) from 5%
305 17 __ 97.2 2.8 polymer solution and were exposed to light with
0 c-70 100 - A = 254 nm (bacteriocidal lamp DB-60) and
I4 70 __ 97.8 2.2
30s 17 _- 97.6 2.4 A > 300 nm (DB-120). Oxidation was monitored
by the accumulation of carbonyl groups from the
 Problems of ageing and stabilization of poly(vinyl chloride) 77

Table 3
____.~
Exploitation Dioctyl- Shrinkage. Elongation q. “C Pore volume.
time, years phthalate % at break. % cm’/g
amount.
mass %

0 35 f 1 - 600 f 40 -40 0.017

15 27 *2 5*2 480 + 60 -20 0.050
30 l5*6 151th 300 f 80 -20 0.065

optical density at 1720cm- determined by IR oxidation and dehydrochlorination depend sig-

spectroscopy. Dehydrochlorination was moni- nificantly upon sample thickness but in this case,
tored by polyene formation determined by degradation proceeds irregularly in bulk polymer
changes in the UV/visible absorption spectra. because the kinetic curves do not transform into
Figure 7 shows the kinetic curves for a general d ependence on D/l,t co-ordinates
accumulation of carbonyl peaks and polyenes (D = optical density, 1 = film thickness, t =
after irradiation at 254 nm. Oxidation does not irradiation time). Thus in these conditions
depend upon film thickness, whereas the oxidation must take place in deep layers of the
dehydrochlorination rate is strongly thickness polymer. Differences in oxidation after irradia-
dependent. tion at A > 300 nm and h = 254 nm are qualitative
These results are consistent with the view that rather than quantitative.
photo-oxidation of PVC takes place in a thin
( < 20pm) surface layer, whereas dehydroch-
lorination is a bulk process.
(a) n
Kinetic curves were significantly different for
irradiation with A >300 nm (Fig. 8). Both

t(h)

0.x

0.6

0.1

(I.1

0 x00 I100 I ho0

f (h) Fig. 8. Kinetic curves of accumulation of carbonyl groups

Fig. 7. Kinetic curves of accumulation of carbonyl groups (a) and polyenes (b). after light irradiation with h > 300 nm.
(a) and polyenes (b). after irradiation with A = 254 nm, of of PVC films of different thicknesses in air at ambient
PVC films of different thicknesses at 20°C. temperature.
78 K. Z. Gunzargnliruo et al.

Table 4. Coefficients of lead salts diffusion in PVC-

plasticate (30 mass% of dioctylphthalate) at different
temperatures

Stabilizer content. Film thickness. 7‘. “C /I x I 0”.

mass ‘XI cm cm‘/\
__ ~ .~
Lead sulphate 0.7 0. IO 20 0.59
45 (MY
Lead stearate 0.4 70 0.86
Lead sulphate 2.0 0.20 45 6.10
70 6.30
Lead sulphate 1.6 0.30 20 7.20
45 7.70
70 8.30
Lead sulphate 1.S 0.35 20 5.00
4s x.30
Fig. 9. Absorption spectra of the PVC films after light Lead sterate 2.5 70 I 1.oo
irradiation with A = 254 nm (1): h >300 nm (2) and total
light Hg lamp high pressure irradiation (3).

described satisfactorily by Fick’s equations, in the

A further important feature found experimen- form:
tally was the dependence of the absorption 7
C, (?ij ___
spectrum of the irradiated samples on the -=I$exp
co , I’
wavelength of the irradiating light (Fig. 9), which
is connected with differences in the composition and calculated diffusion coefficients are shown in
of the polyenes formed. The sensitivity of PVC Table 4. The different stabilizers have different
samples to the composition of the light can be mobilities in water saturated PVC and the
used in practice to determine the place of dependence of diffusion coefficient on
exposure, because the spectral composition of temperature is surprisingly small.
sunlight at the earth’s surface depends upon the Since contact of plasticized PVC with flowing
latitude and the ozone layer thickness. water leads to a relatively fast washing out of the
Another desorbing component of plasticized easily desorbed parts of the lead salts, control
PVC is the stabilizer which can diffuse to the tests on lead salt desorption from aged samples
surface on prolonged contact with water and may give some indication of the conditions of
dissolve in it. We investigated the desorption of exposure. For example, fast extraction of 5-7%
lead salts from PVC films containing lead sulfate of the lead salt may indicate previous exposure in
or lead stearate, at 20, 45, and 70°C over 10 days. dry conditions, whereas the absence of such
Salt contents in the contacting water were desorption may indicate previous exposure in a
analysed by atomic absorption spectroscopy. humid environment.
The desorption curves (Fig. 10) have two We also investigated a series of PVC samples
characteristic parts, an initial, rapid exponential which had been used in the open air in two
desorption and a linear part corresponding to health resorts, in the Batumi (hot) and Jakutsk
slow extraction. (cold) regions, during the three years 1987-1990.
The exponential part of the desorption curve is Testing was based on measurements of mechani-
cal properties and plasticizer content. The data
are shown in Table 5. The most informative are
data on plasticizer loss, which is significant over
the ageing period.

4 CONCLUSIONS

The main indications of ageing of plasticized

r(h)
PVC for film samples, aged in model conditions
Fig. 10. Desorption of lead salt from PVC-plasticate in
and in climatic ageing have been established and
water at 45°C and,WC. compared with those for real materials after long
 Problems of ageing and stabilization of poly(viny1 chloride) 79

Table 5. The change of plasticizer content and mechanical properties of PVC-PlaStiCate

films during ageing in different climate zones

Material Ageing a,,. MPa” E,> %” C I,)()\, mass%’

conditions
_~~ _ ~~~
PVC-DOS Initial 39 f 3 280 f 30 17 f 1.0
(17 mass%) Jakutsk
6 months 35 +6 180 f. 100 I5 * 1.0
12 months 23 + 2 44 + 30 IO * 0.5
24 months 27 f 2 42 f 35 IO f 0.5
36 months 32 f 2 23 f 20 IO f 0.7
Batumi
6 months 34 f 5 170 f 80 1s f 1.0
12 months 25 f 2 60 + 20 12 f 1.0
24 months 28 * 2 40 f 2s IO f 0.7
36 months 30 i 2 2si 10 10 i 0.7

1 2 3 4 5

PVC-DOS Initial 32 *2 400 f 40 23 f 1.0

(23 mass%) Jakutsk
6 months 28 f 4 240 * 40 21 f 1.0
12 months 22 * 2 260 f 80 171 1.0
24 months 20 f 2 56 f 27 10 * 0.7
Batumi
6 months 27 f 3 280 f 50 20 f 1.o
12 months 23 + 2 220 f 40 16 f 1.0
24 months 20 f 2 100 * 30 1 I f 1.o

” &-Breaking stress, MPa.

” l,--Ultimate elongation. %.
’ DOS-dioctylsebacinate.

use. It is shown that the main loss of useful plasticized PVC, without proper knowledge of
properties occurs because of loss of plasticizer or the conditions of use or exposure.
other additives.
One can form an opinion as to the conditions REFERENCES
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