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Thermal Degradation of
Poly(Vinyl Chloride) Plastigels
KC
SE
H. ISMET GO
EL and DEVRIM BALKO
Faculty of Engineering, Department of Chemical Engineering, Ege University, 35100 Bornova, Izmir,
Turkey
Received: November 22, 1996
Accepted revised: July 15, 1997

ABSTRACT: An emulsion, poly(vinyl chloride) (PVC), was analyzed for its


components and was used in the preparation of flexible PVC plates utilizing
sol-gel processing technology. PVC contained an ether-soluble fraction having
carboxylic acid carbonyl groups, a tetrahydrofurane (THF)-insoluble fraction
having COO2 groups, and 0.15% aluminum. PVC was mixed with dioctyl
phthalate (DOP) in a 0.3 0.8 DOP/PVC weight ratio and heated at 1807C for
gelation. The yellowness index (YI) and tensile strength of the plastigels were
increased with both heating time and DOP concentration. Infrared (IR)
spectroscopy showed that the thermal oxidation and volatilization of DOP
occurred simultaneously with dehydrochlorination of PVC upon heating of the
plastigels. Agglomeration of PVC particles on mixing with DOP at low DOP
levels caused longer gelation times than expected. q 1998 John Wiley & Sons,
Inc. Adv in Polymer Techn 17: 63 71, 1998

Introduction

plastisol is a dispersion of a fine-particle-size


PVC resin in a plasticizer. When a plastisol is
heated the plasticizer solvates the PVC particles and
causes them to swell until all of the plasticizer is
absorbed. The time and temperature necessary for
this process depend on many variables, such as molecular weight, particle size of PVC, and concentration and type of plasticizers and heat stabilizers.1

Correspondence to: H. I. Gokcel; e-mail:


baldev@textil.ege.edu.tr

Advances in Polymer Technology, Vol. 17, No. 1, 63 71, 1998


Q 1998 by John Wiley & Sons, Inc.

Large agglomerates (20 30 mm) from small PVC


emulsion particles (1.5 mm) are formed by mixing
them with dioctyl phthalate (DOP). More than 40
min was necessary for complete penetration of DOP
into all primary particles in the agglomerates.2,3
PVC undergoes a dehydrochlorination reaction
when heated. Structural defects such as unsaturation, branching, allylic chlorines, initiator endgroups, and oxygen-containing defects effect dehydrochlorination of PVC.4 HCl and Lewis acids such
as ZnCl2 are known to be accelerators of the dehydrochlorination reaction.5
Swelling of PVC particles and gelation of plastisols by heating are all unsteady state processes and
they have an effect on dehydrochlorination of PVC.

CCC 0730-6679/98/010063-09

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THERMAL DEGRADATION OF POLY(VINYL CHLORIDE) PLASTIGELS


Controversial data exist regarding the effect of
plasticizers on the thermal stability of PVC. Incorporating plasticizers into PVC tends to inhibit thermal degradation and offset darkening and stiffening
of the plastic. Increased lubricity and separation of
PVC polymer chains from each other are physical
factors that increase the thermal stability of PVC.6
On the other hand, polymer and plasticizer degradation occur simultaneously with loss of plasticizer
above 1207C.7 Fast-gelling plasticizers have a detrimental effect on the PVC degradation rate, due to
more difficult diffusion of HCl and products of the
stabilizer reaction that catalyze dehydrochlorination.8
Emulsion type PVC, used in making flexible articles from PVC plastisols, is not a pure substance.
It contains additives originating from the emulsion
polymerization process, lubricants, and heat stabilizers for ease in processing. Characterization of
emulsion PVC is required for the description of
quantitative effects of plasticizers and heat stabilizers on PVC.
Patel and Gilbert9 studied the effect of concentration of plasticizer on the behavior of PVC. Plastics
were produced by mixing in a Banbury mixer at
1607C and two-roll milling at 1407C, followed by
compression molding at 1707C. Thorough mixing of
PVC and plasticizer was obtained by this method.
Ultimate tensile strength (UTS) of the plastics containing diisoocthyl phthalate (DIOP) was 32, 22, and
15 MNm22 for plasticizer levels of 30, 50, and 70
parts per hundred parts resin (phr), respectively.

Elongation-at-break values, of the same samples


were 320%, 430%, and 590%, respectively.
The present work investigates and characterizes
emulsion type PVC and studies the gelation behavior of PVC plastisols having increasing DOP concentration. While tensile tests were carried out to
measure the degree of gelation, visible and infrared
spectroscopic studies were done to study the thermal degradation of plastic plates.

Experimental
PVC (Petvinil E 36/71, Petkim, Turkey), having
a viscosity average molecular weight of 100,000,
was used in preparing the plastisol. It was obtained
by emulsion polymerization and spray drying.
Thus, it contained all the ingredients present in the
emulsion medium.

PVC CHARACTERIZATION
The X-ray fluorescence spectrum of PVC was
taken by using a Jeol JS DX-100 S X-ray fluorescence
spectrometer.
One gram of PVC was treated with 100 mL of 1N
HCl solution for 24 h and HCl soluble fraction was
analyzed for metal ions using a Varian 10BQ atomic
absorption spectrophotometer (AAS). The HCl-insoluble fraction was dried and treated with boiling
ethanol. PVC, acid treated PVC followed by al-

FIGURE 1. X-ray fluorescence spectrum of PVC. The lines labeled W indicate W light source.

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FIGURE 2. IR spectrum of PVC: 5% KBr disk.

cohol-treated PVC samples were analyzed with the


KBr technique using a Shimadzu 470 infrared spectrophotometer.
One gram of PVC was extracted for 6 h with 250
mL of ether. The ether-soluble part was obtained by
completely evaporating the ether in a water bath
and maintaining it in a desiccator. The ether-insoluble part was mixed with 100 mL of tetrahydrofurane (THF) for 2 h at 207C and the mixture was centrifuged at 1000 rpm to separate THF-soluble and
-insoluble phases. While a PVC film was obtained
from the THF-soluble phase by solvent casting, the
THF-insoluble phase was kept at 207C until THF
was completely evaporated. PVC, its ether-soluble,
THF-soluble, and THF-insoluble fractions, were
studied by calorimetric and spectroscopic methods.
Using a Setaram 92 differential scanning calorimeter
(DSC), traces of samples were obtained in air by
heating at 107C min21 up to 2007C. The IR spectrum
of each sample was obtained either using the KBr
technique or directly from films.

PREPARATION AND CASTING OF


PLASTISOLS

FIGURE 3. DSC curve of: (a) PVC; (b) ether extract;


and (c) ether and THF-insoluble phase.

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Plastisols containing DOP in the range of 30 80


phr were prepared by mixing PVC and DOP in a
mechanical mixer for 1 h at 257C and maintaining
in vacuum conditions to remove air bubbles
trapped between PVC particles. Plastisols were cast
to plates with 100 mm 3 100 mm 3 2 mm dimen-

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FIGURE 4. IR spectra of: (a) KBr; (b) PVC; (c) HClinsoluble fraction; and (d) HCl followed by ethanoltreated PVC.

FIGURE 5. IR spectra of: (a) film from the THF-soluble


fraction; (b) film from THF-insoluble fraction; and (c) KBr
disk of the ether extract of PVC.

PROPERTIES OF PLASTIC PLATES


sions by using a flat-plate mold prepared from a
glass plate and a stainless-steel frame.

GELATION OF PLASTISOLS
Plastisols in flat-plate molds were heated in air at
180 6 27C in a laboratory-type oven from 10 to 40
min to obtain plastic plates.

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The yellowness index (YI) of the plates was measured using a Muruyama CM-25 color machine.
The stress strain diagrams of plastic plates were
obtained according to BS 903 with an Instron 1114
tensile tester by using a strain rate of 5 cm min21
and a recorder rate of 10 cm min21. DSC curves and
dispersive infrared spectra of the samples heated for
10 min and 40 min were also obtained. A dispersive
infrared spectrum of spectroscopic-grade KBr single

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FIGURE 6. IR spectrum of ether-soluble fraction of PVC.

crystal was obtained for testing the spectrophotometer in dispersion mode.

Results and Discussion


PVC CHARACTERIZATION

FIGURE 7. UTS of the plates with: 30 (s); 50 (n); 60


(u); 70 (d); and 80 (,) phr DOP vs. gelation time at
180&C.

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X-ray fluorescence spectroscopy indicated the


presence of Al and Fe elements besides Cl in PVC
(Fig. 1). Analysis of the acid (1N HCl) extract using
AAS indicated the existence of 0.15% Al in PVC.
The IR spectrum of PVC (Fig. 2) showed bands
related with CH2 stretch at approx. 2910 cm21 and
CH stretching vibration at 2965 cm21, CH2 bending
vibration at 1425 cm21, CH bending in CHCl vibrations at 1250 cm21 and 1333 cm21, C C vibration
at 1098 cm21, CH2 bending (rocking) vibration at 970
cm21, and C Cl stretch vibration in isotactic chains
at 690 cm21 and syndiotactic chains at 603 638
cm21.10,11 There were additional bands at 3400 cm21,
1700 cm21, 1600 cm21, and 1560 cm21, indicating the
presence of additives in the sample. On the other
hand, because the relative intensity of C Cl (at 630
cm21) to C H stretching band (at 2965 cm21) for
the sample was found to be 0.5, which is close to
the value (0.38 0.45) found for commercial PVC
types,12 the additives apparently were present in
small quantities. The DSC curve of PVC (Fig. 3a)
shows a glass transition temperature of 807C.

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The disappearance of the band at 1560 cm21 and
increase in band intensity at 1700 cm21 after acid
treatment (Fig. 4b, c) indicated the presence of
COO2 ion PVC, transformed into COOH
groups with acid treatment. The COOH group
containing species were soluble in hot ethanol as
can be seen from the disappearance of the 1700 cm21
peak in acid followed by ethanol-treated PVC (Fig.
4d).
The components of emulsion PVC were identified by DSC and IR spectroscopy. Emulsion PVC
contained an ether-soluble fraction with carboxylic
acid carbonyl groups (1700 cm21 peak in IR spectrum) (Fig. 5c). The full spectrum of the sample in
Figure 6 had a peak at 3450 cm21 due to OH stretching of the carboxylic acid. The ether-soluble fraction

FIGURE 9. Change of elongation percent at break with


gelation time at 180&C for plates with: 30 (s); 50 (n); 60
(u); 70 (d); and 80 (,) phr DOP.

melted at 547C (DSC curve, Fig. 3b). The THF-insoluble fraction isolated as a film contained
COO2 groups (1560 cm21 peak in its IR spectrum;
Fig. 5b) and did not have a definite melting point
(DSC curve, Fig. 3c).
Informal communication with a PVC producer
indicated the presence of ammonium myristate and
ethoxylated fatty acids in PVC obtained by direct
spray drying of the emulsion. The bands in the
3500 3300 cm21 and 1650 1580 cm21 regions in the
IR spectrum of PVC (Fig. 2) could be attributed to
the presence of NH41 groups in PVC.

GELATION OF PVC

FIGURE 8. DSC curves of plastigels: (a) heated for 10


min; or (b) heated for 40 min. They contain: 30 (1); 50
(2); 60 (3); 70 (4); 80 (5) phr DOP. Sample weights:
22.30 mg (a1); 38.40 mg (a2); 34.00 mg (a3); 33.90 mg
(a4); 32.10 mg (a5); 21.20 mg (b1); 27.80 mg (b2);
33.00 mg (b3); 33.00 mg (b4); and 26.00 mg (b5).

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UTS, which is a measure of extent of fusion of


plastic plates, shown in Figure 7 are at the same
order with UTS of plasticized PVC.9 The scattering
of experimental points in Figure 7 is due to the manual preparation technique of the plates. At 30 phr,
DOP-level plastic plates with the lowest mechanical
strength were obtained. Mechanical strengths of the
plates were higher and close to each other in the 50
70-phr DOP range. At 80 phr, DOP-level transpar-

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FIGURE 10. Change of yellowness index with DOP


concentration for plates heated at 180&C for: 10 (s); 20
(n); 30 (u); and 40 (d) min.

ent plates with the highest mechanical strength


were produced. At lower DOP levels, the plates
were not transparent due to unfused PVC particles.
Although UTS was lowered in flexible PVC obtained by conventional processing methods,9 it increased in plastic prepared by sol-gel technology
with increasing plasticizer concentration. Lower
UTS of plates obtained with the sol-gel method indicated incomplete dissolution of PVC in plasticizer
DOP and an absence of crosslinks between PVC
molecules. On the other hand, absence of a glass
transition point of PVC on DSC traces of plates
heated for 10 and 40 min indicated that DOP penetrated into all PVC particles (Fig. 8).
The elongation at break of the plates (Fig. 9) increased with both time and plasticizer content, as
expected.9 Agglomerate formation during mixing of
PVC and plasticizer and diffusion of plasticizers in
the agglomerates and cohesion of the surface of the
agglomerates created a bulk solid in sol-gel processing. For small plasticizer contents efficient mixing was not possible, due to the high viscosity of the
mixture, causing the formation of large agglomer-

ADVANCES IN POLYMER TECHNOLOGY

FIGURE 11. Dispersive IR spectra of: (1) KBr crystal


and plates containing 30 (2); 50 (3); 60 (4); 70 (5); and
80 (6) phr DOP, and heated for 10 min at 180&C.

ates. On the other hand, for high plasticizer contents


it was possible to break the agglomerates by mixing
because the viscosity was low. Thus, higher tensile
strength and elongation at break at higher plasticizer contents could be justified in terms of the size
of agglomerates.

THERMAL STABILITY OF PLASTIC


PLATES
Thermal stability of the plates was studied by
measuring their YI. As seen in Figure 10, YI of the
plates increased both with time of heating and with
DOP concentration. Because emulsion PVC is not a
pure substance, diluting with the plasticizer caused
a decrease in concentration of the additives that may
act as heat stabilizers. On the other hand, at the
1807C fusion temperature, plasticizer and PVC underwent simultaneous degradation while some of

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FIGURE 12. Dispersion IR spectra of plates


containing: 30 (1); 50 (2); 60 (3); 70 (4); and 80 (5) phr
DOP, and heated for 40 min at 180&C.

the plasticizer was lost as vapor from the system.7


Lowered diffusivity of the dehydrochlorination
product (HCl) in plasticized PVC could also cause
faster degradation because HCl itself is a dehydrochlorination catalyst. The faster yellowing of the
plates when the DOP fraction increased indicated
faster dehydrochlorination, confirming Wypchs
suggestions.8
The main peaks in the dispersive IR spectra of
the plates heated for 40 min and 10 min at 1807C
(Figs. 11 and 12) were brought to the same transmittance scale and are shown in Figure 13. The 3700
cm21 peak, which represents free (isolated) OH
stretching vibrations,13 increased in intensity with
DOP concentration faster at the 40-min heating time
than at the 10-min heating time (Fig. 13a). More
OH groups, which can be attributed to hydroperoxides14 or carboxylic acids, formed by heating
longer in air. The 2965 cm21 peak, which represented C H stretching vibrations, decreased with
DOP concentration in a similar manner for both
short and long heating times (Fig. 13b). This may
have been due to decrease of C H groups in plastigels upon dehydrochlorination. The sharp peak
present at 2400 cm21 in IR spectra of all plastigels
was due to instrumental error, because it was also

FIGURE 13. Normalized peak height (nT) vs. DOP concentration of IR peaks at: (a) 3700 cm21; (b) 2940 cm21; (c)
1730 cm21; (d) 1560 cm21, for 10-min (s) and 40-min (n) heating times.

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observed in the IR spectrum of pure KBr (Fig. 11,
area 1). The 1730 cm21 peak, which can be attributed
to the ester carbonyl group of the plasticizer,10 lost
its intensity in the same manner with DOP concentration for short and long heating times (Fig. 13c).
Because dispersive IR spectroscopy gave information about the functional groups at the surface of
the samples, it can be concluded that DOP concentration at the surface of the plates decreased,
whereas the average concentration of DOP in plates
increased. The agglomerate formation during plastisol mixing created heterogeneous distribution of
DOP in PVC. Viscosity of plastisols with low DOP
concentration was very high, causing difficulty of
homogeneous mixing by the low shear method employed in the present study. Large agglomerates of
PVC particles form at low DOP levels, as is also understood from the low tensile strength of the plastigels. Although DOP concentration was high at the
surface of the agglomerates, it was low in their
cores. At high DOP concentrations, smaller aggregates formed due to easier mixing of the low viscosity mixture. DOP can penetrate into the center of
the small aggregates in a shorter time than that of
large aggregates upon heating the plastisols. Thus,
the surface of large aggregates would be richer in
DOP compared with the surface of the small ones.
Thus, higher concentration of DOP at the surface
than in the bulk can be observed for plastigels with
low plasticizer contents.
The 1560 cm21 peak attributed to COO2
groups decreased in intensity faster at the 40-min
heating time than at the 10-min heating time as DOP
concentration was increased (Fig. 13d). The conversion of COO2 groups to COOH or COOR
groups1 with HCl formed from PVC degradation
(Fig. 9) was higher for the longer heating period.

Conclusion
The presence of additives in emulsion polymerized and spray-dried PVC can not be avoided. Even
if complete analysis of the additives was not made
in the present study, they have been identified as
organic acids, ammonium soaps, and an acid-solu-

ble aluminum compound. These additives act as


heat stabilizers and prevent the dehydrochlorination of PVC on heating.
Plastigels having low DOP concentration have
low tensile strength due to incomplete dissolution
of large PVC agglomerates. Although 10 15-min
gelation times were recommended for sol-gel transition in the literature,1 longer times are required
due to agglomeration in plastisols. This brings out
the problem of higher levels of thermal degradation
with longer times required for complete gelation.
High intensity shear mixing and using processing aids could be recommended to prevent agglomeration in PVC plastisols having low plasticizer content. On the other hand, the behavior of the DOP
PVC system showed that plasticizers have a detrimental effect on the thermal stability of PVC confirming the observations of Audounin et al.7

References
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York, 1968, pp. 77 81.
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3. D. Balkose, Doga, Turkish J. Eng. Environ. Sci. 14, 303 (1990).
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Encyclopaedia of Polymer Science and Technology, H. F. Mark
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Polym. Sci. 45, 2097 (1992).
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10. J. Haslam and H. A. Willis, Identification and Analysis of Plastics, Van Nostrand, New Jersey, 1967, pp. 46 61.
11. W. F. Maddams and D. D. Owen (Eds.), in Degradation and
Stabilization of PVC, Elsevier, Essex, 1984, p. 144.
12. A. M. S. Al Ghamdi and S. S. Al Diab, J. Appl. Polym. Sci. 42,
2233 (1991).
13. R. A. Alberty, Physical Chemistry, Wiley, New York, 1987, p.
512.
14. D. Braun and E. Bezdadea, Angewandte Makromolekulare
Chemie. 99, 57 (1981).

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