Fusion Behavior of Plastisols of PVC Studied by

ATR-FTIR
A. MARCILLA, M. BELT&, J. C. GARCh, and D. MANG
Departarnento de Ingenieha Quirnica
Uniuersidad de Alicante
Apartado 99, Alicante, Spain
The behavior of PVC plastisols during gelation and fusion was studied by the
ATR-FTIR technique (Attenuated Total Reflectance-Fourier Transform Infrared
Spectroscopy). DBP, DOP, and DIDP, three common phthalate plasticizers for
PVC, were used in plastisols formulations. Three heating rates-5, 10 and 15
"C/min-and formulations with different plasticizer concentrations were studied.
The IR spectra of a plastisol coincides with the IR spectra of the plasticizer except
for the bands at 1435 and 613 cm-' from the PVC (CH, wagging and C-CI
stretching, respectively). When the plastisol is heated, a progressive decrease of
the plasticizer bands areas can be observed, while bands from PVC increase their
intensity, probably because of the adsorption of the plasticizer by the resin. On
cooling, the area of all bands follows the same path as when heating, but the
paths separate at a certain temperature, showing the irreversible nature of this
'
process. The analysis of the band at 1280 cm- (C(0)- 0 from plasticizer) during
heating and cooling, shows that the temperature of separation areas (T,)takes
place at temperatures coherent with plasticizer compatibility. Studies at different
heating rates and different plasticizer content are in good agreement with results
using other techniques, available in the literature.

INTRODUCTION gelation cannot be detected. Solid-gel transition mi-

T e expression PVC plastisol is commonly used for
a fine particle suspension of PVC in plasticizers.
The particle size of the PVC is between 0.2 and 15
pm. The small particles are the polymerization prod-
uct and the larger ones are agglomerates of the pri-
mary particles (1). In common applications of PVC
plastisols (coatings, films, foams and rotational cast-
ing) the plasticizer/PVC mixture is heated to its fu-
sion temperature, and the characteristics of the fin-
ished products depend mainly on the process condi-
tions during the heating stage.
During heating of a PVC plastisol, the plasticizer
penetrates into the PVC grains, swelling them with
different rates at the beginning and the end of the
process. This process is called gelation. In a tempera-
ture range between 150 and 170°C, the process of
gelation is complete, and a dissolution of the polymer
in the plasticizer is obtained. The termination of the
process is known a s fusion. After cooling down, the
finished plastic reaches its full physical integrity.
Different methods for the detenhnation of gelation
and fusion of plastisols are known, i.e., the hot-bench
method used by Greenhoe (21, solid-gel transition
microscopy (3). scanning electron microscopy (41,
rheometry (1, 5, 6) and small angle light scattering
(7) and dielectrometry (8).The hot-bench method is
quite fast and simple in application but details of the
croscopy is used mainly for comparison of different
PVC/plasticizer systems, but the disadvantage is that
real PVC/plasticizer formulations cannot be tested.
The SEM technique is very useful for studying the
morphological changes of the plastisol during the
gelation, but very rapid cooling is necessary, which
may alter the morphology of the sample. The most
common method used is rheometry, and modem
technology allows the plastisols to be tested using
very low external shear forces, which may affect the
plasticizer adsorption.
FTIR-spectrophotometry has been used by several
researchers to determine the curing degree of differ-
ent polymers (91, the compatibility of composites (10,
1l), the crystallinity of PVC (12), and mechanisms of
degradation of plastics (13). In our work we have used
this powerful technique to study different states of
the gelation and the fusion process. With in-situ mea-
surements, we can study the process of different
PVC/plasticizer systems.
EXPERIMENTAL
Materials
A typical commercial PVC resin, Etinox 450 from
Aiscondel, was employed for plastisol preparation.
The molecular weights Mu, Mu are 104,000 and

10 JOURNAL OF VINYL & ADDITIVE TECHNOLOGY,MARCH 1995, Vol. 1, No. 7

 Fusion Behavior of Plastisols of PVC Studied by ATR-FTIR
1- from IR source
110,000, respectively, measured by GPC in THF.
Three phthalate plasticizers with different solvent 2- KRSd Crystal
power were employed: DBP (di-isobutil phthalate), 3- thermocouple
DOP (di-2-ethylhexyl phthalate), a n d DIDP 1 4- resistance
(di-isodecylphthalate). The plastisol formulation is 5 plastisol sample
given in Table 1.The plasticizer content was varied in
one case to 40 and 90 phr (parts per hundred of 6-ATR mirrors
- -
resin). 7- supports
5 8- to the detector
Method
Q. 1 . ATR s y s t e m resistance and thermocouple arrange
A Nicolet 510 ETIR was used, coupled with a n ATR ment.
Spectratech model 300 with the KRS-5 crystal. The
equipment was controlled by a 680 spectral worksta-
tion from Nicolet. Spectrometer conditions were elec- creases the amount of free plasticizer (14). and conse-
tronic gain 8, mirror velocity 30, and 3 scans by quently, it would diminish their bands.
interferogram were obtained. The system was p r e The results of two successive heating-cooling cycles
grammed to take one interferogram each 14 seconds. (heating up to 150°C and 170°C respectively) of a
In this way, detailed information of sample modifica- DIDP-plastisol are shown in Flg. 4 , where the absorp
tion with the temperature can be obtained. The heat- tion at 1280 cm-' is represented vs. temperature.
ing rate was 10"C/min, except in two cases when 5 The above-mentioned decrease of the area, owing to
and 15"C/min were used. The maximum tempera- the disappearance of free plasticizer and the gradual
ture in each case depends on the formulation in phase conversion liquid-gel-solid, can be observed
order to prevent plasticizer evaporation. Cooling rates from the first heating curve. In the first cooling step,
were the same as when heating. The plastisol sample
was placed between the KRS-5 crystal and the ther-
mocouple coupled with the resistance, as shown in
Fig. 1.
RESULTS AND DISCUSSION
The spectra of the PVC resin, the plasticizer (DIDP),
and the plastisol (DIDP, 65 phr) are shown in the
Figs. 2% 2b, and 2c. The plastisol spectrum is very
close to that of the plasticizer. The most characteris
tic absorption bands of a typical plastisol spectrum
can be observed in the ranges 3100-2850 cm-' 4000 3500 3000 2500 2000 1500 1000 500
(C-H stretching), 1730 cm-' (C=O stretching), Wavenumbers (cm-1)
1600 cm-' (Arc-C stretching), 1280 cm-' (C-0
stretching) and 743 cm- (Arc-H , ortho-position).
The bands at 1435 cm-' and 613 cm-' are due to
-CHz- and -C-Cl groups from the PVC resin.
Even at elevated temperatures of the plastisol
(> 100°C), no significant band shifts were observed,
indicating a very weak resin-plasticizer interaction
(physical interaction).
At increasing temperature, a continuous decrease
of the plasticizer band areas and a simultaneous
intensification of the areas corresponding to the PVC
4000 3500 3000 2500 2000 I500 1000 500
resin were detected, as shown in Figs. 3a and 3b. Wavenumbers (cm-I)
This feature can be explained by the adsorption of the
plasticizer by the PVC grains, swelling the PVC parti-
cles and increasing the mobility of the PVC molecules,
leading to the enhancement of the related areas. Si-
multaneously, this interaction PVC-plasticizer de-

Table 1. Plastisol Formulation.

Component Part by Weight
PVC resin 100 4wo 3500 Moo 25w Moo 1500 1wo 500
Plasticizer 65 wavcnumbsrs ( C r n l )
Ca-Zn stabilizer 6.5 Fig. 2. IR spectra of resin Etinox 450, plasticizer (DIDP), and
Expoxidized soybean oil 2 plastisol(65 phr, DIDP).

JOURNAL OF VINYL i? ADDITIVE TECHNOLOGY, MARCH 1995, Vol. 1, No. 1 11

 A. Marcilla, M. Beltrbn,J . C. Garcia,and D. Mang
NormalizedArea plete plastisol conversion is reached, there is no
1.2
longer any difference between the heating and the
Plasticizerbands
cooling step.
In a second experiment (Fg.5) the plastisol was
heated in the first stage only, up to 110°C. The T,
observed during the cooling step was lower than in
-
the first experiment ( 100°C,temperature very close
to the maximum temperature reached). In the second
cycle, the heating curve (up to 170°C) runs nearly
0.4 I I 1
1 .
1 parallel to that of the first cooling stage (with slight
0 50 100 150 200 differences in the zone at -SO-lOO"C), but the sec-
ond cooling stage shows a large difference. The T, is
Temperature (gC) now detected at 130°C. indicating the incomplete
743 cm-1 A 1280 c m l 0 1730 cm-1 * 2850-3100 cm-1 conversion obtained during the first heating-cooling
cycle.
NormalizedArea The deviations that may be observed in Figs. 4 and
4 5 between the first cooling and the second heating
1
A ' 2 steps might be due to the temperature difference
Resin Bands
A A between the thermocouple and the plastisol film.
A
A During the heating step, the thermocouple tempera-
ture is higher than the real temperature of the plasti-
A A
sol film, and during the cooling step the situation is
reversed. Both curves could be matched, displacing
the temperature axis.
04 I I I Figures 6, 7b, and 8b show the modifications in the
0 50 100 150 200 normalized area with the temperature for the three
plasticizers. Clear differences between the three sys-
Temperature (QC)
tems can be observed. The experimental results dur-
613 cm-1 A 1435cm-1 ing heating and cooling were fitted to polynomials of
Fig. 3. Modijications in plasticizer and resin band areas with the adequate degree. The intersection of the polyno-
temperature in a 65 phr DIDP plastisol. mial was taken as T' (separation temperature). Re-
sults obtained for DBP, DOP, and DIDP in Table 2 are
compared with the solid-gel transition temperature
the normalized areas are similar to the areas of the (T,) obtained by Gilbert ( 15) and the gelation temper-
first heating step, until a temperature of approxi- ature (Tf) obtained by Daniels (6) with a dynamic
mately 140°C is reached. This temperature is called rheometer. Results obtained with the ATR-FTIR tech-
T,,i.e., temperature of areas separation. At tempera- nique are in good agreement with those obtained with
tures below Ts, the separation heating-cooling b e the other commonly used techniques.
comes much more pronounced, indicating a different Gelation and fusion temperatures of a plastisol,
behavior of the plastisol during the heating and the and the rate of transformations involved in the pro-
cooling stage, showing the irreversible nature of the cess, depend mainly on the nature of the plasticizer
gelation process. The areas obtained in the second and the resin and the resultant interaction between
heating-cooling cycle match with the areas of the first them (16). Plasticizer concentration is a secondary
cooling cycle, making it evident that once the com-

1.2 ,
Normalized Area

. 1.2 I
NormalizedArea

. ..*.ow
I

0.6 0.6
0.4

- + 0
0.4
0.2 +
0 50 100 150 20(

Temperature (%)
first heating A first cooling 0 second heating * second cooling
Q. 5. 1280 cm- band area modijication in two successive
heating-cooling cycles (heating to 110 and 170"C, respec-
tively).

12 JOURNAL OF VINYL & ADDITIVE TECHNOLOGY, MARCH 1995, Vol. 1, No. 1

 Fusion Behavior of Plastisols of PVC Studied by ATR-FTIR

NormalizedArea NormalizedArea
1.2
1
DBP 65 phr

l t
0.8 i *- .r..

O6 t
0 50 loo 150 200 DlDP lWC/min
Temperature (QC)
heatingding A Q.8
Fcg. 6. 1280 cm-
at 1 O"C/ rnin.
band area modificationsfor DBP plastisol
0.6 t
factor in determining the gelation and fusion temper-
ature. Nevertheless, there is no agreement in the DIDP 5%/min
results obtained by different authors (and different
methods) with different plasticizer concentration (6,
17). Figure 7 and Table 3 show the results obtained
with the ATR-FTIR technique at 40, 65 and 90 phr
employing DOP as plasticizer. There is a slight shift in 0.6
T' obtained with varying plasticizer content. Differ-
ences are not very significant and might be due to 0.4 ! I I 1

external factors. Larger differences can be observed in 0 50 100 150 200

Temperature (QC)
NormalizedArea heating A cooling
'
Fig. 8. 1280 cm- band area modi$catwnsfor DIDP plastc
1 sol at different heating rates.

0.8 the separation areas between heating and cooling

(see Aarea,,o, from Table 3).The change undergone
0.6 in the initial plastisol with low plasticizer concentra-
tion seems to be greater than that of high plasticizer
concentration.
0.4 I The gelation process involves diffusion of plasticizer
into the resin particles, and is obviously dependent
on time and temperature. Plasticizer diffusion will be
greater when the temperature increases slowly (5).
Consequently, the gelation temperature will be lower
with low heating than with the fast heating. The last
experiment was carried out with the DIDP plastisol at
5, 10 and 15"C/min. Results obtained are shown in
0.4 I Fig. 8. The results are coherent with the comments
mentioned above. The greater heating rate gives the
greater T, (Table 3). It can be observed that the
separation areas between heating and cooling
(Aarea,,,) decrease with the increase of the heating
rate. Interactions between plasticizer and resin are

o.6
0.4
t
0
! . I

50 100
I

150 200
Table 2. Comparison Between Solid-Gel Transition
Temperature (T,,), Gelation Temperature by a Rheometer
(Tf) and Gelation Temperature by ATR-FTIR (Ts).
Temperature (QC) Plasticizer T,,W TfPC) TsPC)
heating A cooling DBP 92 - 109
m. 7. 1280 cm- band area modi$cations for DOP plastC DOP
DlDP
118
136
127
146
122
153
sols with dGerent plasticizer content at 1 o"C/ rnin.

JOURNAL OF VINYL & ADDITIVE TECHNOLOGY, MARCH 1995, Vol. 1, No. 1 13

 A. Marcilla, M. Beltran,J. C. Garcia, and D. Mang
Table 3. Results Obtained at Different Contents in Changes during heating and cooling can be ob-
Plasticizer and at Different Heating Rates. served.
Plasticizer phr "C/min T,("C) Aarea,,.,
DOP 40 10 122 0.39 REFERENCES
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-
each experiment ( 1 @.
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14 JOURNAL OF VlNYL & ADDlTlVE TECHNOLOGY, MARCH 1995, Vol. 1, No. 1