ISSN 1517-7076 artigos e13183, 2022

Influence of alternative polymeric

plasticizer to DOP in thermal and
dynamic-mechanical properties of PVC

Rafael Domingos Dalagnol1, Edson Luis Francisquetti2,

Ruth Marlene Campomanes Santana1

1
Universidade Federal do Rio Grande do Sul, UFRGS, Av. Bento Gonçalves, 9500, Bairro Agronomia, ZIP 91501-970,
Porto Alegre, RS, Brazil.
2
Instituto Federal do Rio Grande do Sul, Campus Farroupilha, Av. São Vicente, 785, B. Cinquentenário, ZIP 95174-274,
Farroupilha, RS, Brazil.
e-mail: [email protected], [email protected], [email protected]

ABSTRACT
Polyvinyl chloride (PVC) is a very versatile polymer with many applications. Due to the easy incorporation of additives
and plasticizers in this resin. The most used plasticizer for PVC is dioctyl phthalate (DOP), however its use has been
restricted by several organizations because it presents potential toxicity. In this way, the objective of this work is to
evaluate thermal, physical and dynamic-mechanical characteristics for a polymeric plasticizer alternative to DOP,
polyisobutene base. As a method of comparison, the contents of the materials were kept constant, and only the plasticizer
content of the samples was altered. Results indicated that the PVC compounds obtained satisfactory plasticizing results
and that don’t have chemical transformations. In addition, the plasticizer evaluated has a higher thermal stability when
compared to the compound with DOP, proving to be a promising result.
Keywords: Polyvynil chloride, polymeric plasticizer, dioctyl phtalate.

1. INTRODUCTION
Polyvinyl chloride (PVC) is a polymer that stands out increasingly in the world market. Currently, PVC is the
second most consumed thermoplastic in the world, with a consumption of over 33 million tons per year [1].
In flexible PVC compounds the main additive used is plasticizer as the PVC resin is naturally rigid due to its
high glass transition temperature. The use of plasticizers in PVC is essential in order to be able to change
certain properties of the resin, and thereby to obtain a material that can be applied in several flexible products.
The most common industrial plasticizers, called phthalates are used in various consumer product
applications. Dioctyl phthalate (DOP) is a plasticizer used specifically for PVC, having a great cost-benefit
ratio and excellent properties for general applications [2]. The Institute for Technological Research states that
the phthalactic plasticizer class is being regulated due to the fact that some plasticizers (DOP, for example)
have potentially harmful health [3, 4]. Phthalates are considered hazardous waste and are classified as
pollutants when industries release them into the environment. The European Union has banned the use of
some phthalates in cosmetics and other consumer products in response to concerns about exposure and
toxicity [2, 5]. In Brazil, there is only one restriction on its use as a plasticizer in reusable materials that are
not in contact with fatty foods and as a process agent in a concentration of up to 0.1% in the final product [6].
All plasticizers can be separated into two groups: monomeric and polymeric [7]. According to their
molecular weight plasticizers are classified as monomeric those having less than 500g.mol -1. The polymers
have a broader molecular weight range, ranging from 500 to 2000g.mol -1. According to Gottesman,
polymeric plasticizers are not as efficient compared to monomeric ones, however, polymerics significantly
reduce migration, extraction and volatility [8]. They can be easily incorporated into products that offer high
plasticity, low temperature resistance and glossy surface [9].
Thus, in view of the potential toxicity of DOP, this work aimed to investigate the influence of a
polymeric plasticizer (polyisobutene base) alternative to the use of phthalates in the thermal and dynamic
mechanical properties. In this way, it becomes possible to study a plasticizer in order to replace DOP.

Autor Responsável: Rafael Domingos Dalagnol Data de envio: 03/08/2020 Data de aceite: 31/01/2022

10.1590/S1517-707620220002.1383
 DALAGNOL, R. D.; FRANCISQUETTI, E. L.; SANTANA, R. M. C., revista Matéria, v.22, n.2, 2022

2. EXPERIMENTAL

3.1 Materials
The materials used to prepare the compounds were: PVC resin obtained by the process polymerization in
suspension and plasticizing oils. PVC was purchased from BRASKEM (Norvic® SP1000) containing a K
value of 65 ± 1 and a volume density of 0.52 ± 0.03 g.cm-3. Dioctyl phthalate (DOP) was purchased from
Elekeiroz (EKFLEX® 8815), with a density of 0.983 g.cm-3, with a molar mass of 390 g.mol-1. A polymeric
plasticizer polyisobutene (PIB) with a molar mass of 1300 g.mol -1 was used, and this was dissolved in a
solvent carboxylic acid Bis (2-ethylhexyl) cyclohexane1,2-dicarboxylate (DOCH), which acted as a
secondary plasticizer. This solvent is a carboxylic acid based with a molar mass of 397 g.mol -1 and density
(20°C) of 0.95 g.cm-3. Thermal stabilizer CaZn and stearin were also used. The contents of the remaining
elements in the formulations were kept constant, as reported in Table 1.

Table 1: Formulation of the compounds in per hundred PVC resin

Material Compound 1 (phr) Compound 2 (phr)
PVC Resin SP1000 100 100
Polymeric Plasticizer (PIB/DOCH) 50 0
DOP 0 50
CaZn Thermal Stabilizer 3 3
External Lubricant 0.1 0.1

The resin and additives were blended in the formulations described in Table 1 in an intensive mixer
for PVC compounds, under the conditions of 1500 RPM and ambient temperature, with addition temperature
of 100°C. At the end of this step, the homogenized material, designated as reported Nunes et. al. of PVC
compound (dry-blend), was cooled to 60°C under stirring in the cooler of the mixing equipment [10].
After this process, the samples were extruded in a twin-screw extruder with a length-by-diameter ratio
(L/D) of 32, and the thread rotation was maintained at 260 RPM. The temperatures of the heating zones (feed
direction to the nozzle) were stored at 145, 145, 150, 150, 155, 155, 150 °C.

3.1 Characterization
For the analysis of the chemical structure of the material, Fourier Transform Infrared Spectroscopy (FTIR)
analysis was used. The tests were examined by spectroscopy Perkin Elmer FTIR Frontier in the range of
4000 to 600 cm-1. In this test the standard was adopted ASTM D2124-99 [11]. Six scans were performed.
Due to the characteristics of the samples, the analysis was carried out using in ATR (Attenuated Total Reflec-
tion) mode, which provides a superficial analysis of the material by means of infrared ray reflection [12].
For TGA analysis, the standard ASTM E1131-08 [13] was used, and the samples were examined by
Perkin Elmer TGA 4000 equipment. The analysis parameters used were a heating ramp from 30 °C to 900 °C,
with a heating rate of 20 °C.min-1, conducted in an inert atmosphere (nitrogen). The initial mass of the
samples was 5.500 mg ± 1 mg.
For DSC analysis, the standard ASTM D3418-15 was used, and was realized in a Perkin Elmer DSC
6000 equipment. The amount of material used in this analysis was 9.0 mg ± 1 mg. These samples were sealed
in airtight pots with the assistance of an encapsulating press. For the resin and PVC compounds, a first run
was conducted in order to erase the thermal history of the material, so that the samples were heated from
30°C to 170°C at a rate of 30°C.min-1, and an isotherm was maintained at this temperature for one minute. It
was then cooled at a rate of 30°C.min-1 until -70°C, maintaining this temperature for ten minutes. Finally, a
second heating was carried out at a rate of 30°C.min-1 until 180°C. For the pure plasticizers the same process
was performed, but the first heating was not carried out since the materials are already in the liquid state.
In order to obtain information regarding the viscoelastic properties of the material, the dynamic
mechanical analysis (DMA) technique was used. This assay was performed using Perkin Elmer DMA 8000
equipment. The test was conducted at a heating rate of 2 °C.min-1 using 0.010 mm amplitude and a frequency
of 1.0 Hz. For determination of the behavior viscoelastic was obeyed the standard ASTM D4065.The glass
transition of the material can be analyzed by this method. Second Menard and Menard [14], through the
DMA test, the Tg of the material can be obtained in a number of ways. The method chosen for the
determination of the glass transition of the material was through the peak of the tan δ curve, and the values
obtained will be compared with those obtained in the DSC test. For the determination of T g the standard
 DALAGNOL, R. D.; FRANCISQUETTI, E. L.; SANTANA, R. M. C., revista Matéria, v.22, n.2, 2022

ASTM E1640 was followed.

3. RESULTS AND DISCUSSION

The FTIR spectra of PVC resin, plasticizers (polymeric and DOP) and plasticized PVC compounds are
shown in Figure 1.

Figure 1: Spectrum obtained by FTIR-ATR assay of sample of: (a) PVC Resin; (b) Polymeric Plasticizer (c) DOP
Plasticizer; (d) PVC Compound with Polymeric Plasticizer; (e) PVC Compound with DOP.

Figure 1 (a) represents the spectrum of the PVC resin and it is possible to observe the 2910 cm-1 band,
which corresponds to the axial deformation of the C-H group of -CH2 [15]. The 1430 cm-1 band corresponds
to the angular deformation of the C-H group. At 1330 cm-1 is related to the deformation of the C-H group
 DALAGNOL, R. D.; FRANCISQUETTI, E. L.; SANTANA, R. M. C., revista Matéria, v.22, n.2, 2022

from -CH2-Cl. The 1250 cm-1 band corresponds to the axial vibration of the C-H group. At 960 cm-1 it refers
to the axial vibration of the C-C group. The presence of chlorine can be observed through the 689 and 60cm-1
bands, which refer to the C-Cl group [16-19].
According to Figure 1 (b), which represents the spectrum of the polymeric plasticizer, the band pairs
are observed at 2950 and 2930 cm-1 and at 2900 and 2870 cm-1, which represent the axial vibrations of -CH3
[16]. At 1730 cm-1 is related to the axial deformation of the carbonyl group C=O from ester present in the
structure [20]. For the use of this polymer as plasticizer, it was necessary to use a solvent that acted as a
secondary plasticizer, which has ester in its structure. Therefore the ester bands are due to this solvent. The
1465 cm-1 band refers to the angular deformation of -CH3 and -CH2 [17]. The pair of bands at 1390 and
1365cm-1 is equivalent to the angular deformation CH3 of C- (CH3)n [21]. The axial vibration of the C-C
group of C- (CH3)n is observed in the 1230 and 1170 cm-1 bands [21]. At 1130 cm-1, the C-O axial
deformation of the ester group occurs. Reis et. al. reports that the 1030 cm-1 band refers to the C-O
asymmetric deformation of the ester group, which, according to the authors, ester bands are stronger in this
region [22]. These characteristic bands are also corroborated by the evaluation of PVC compounds with
application in the footwear industry, showing no significant band differences [23].
Figure 1 (c) shows the DOP plasticizer spectrum, where the bands 2970, 2920 cm-1 and 2880,
2860cm-1 correspond to the axial vibration of the -CH3 group [16]. The 1720 cm-1 band refers to the axial
deformation of the carbonyl group C=O from ester [24, 25]. In addition, the 1720, 1265 cm-1 and 1125,
1065cm-1 bands correspond to the C-O axial deformation of the ester group [20]. In the 730 cm-1 band the
aromatic ring present in the DOP structure is observed [16].
The spectrum of the compound with polymeric plasticizer can be seen in Figure 1 (d). A result was
obtained in which the spectra of PVC resin and plasticizer overlapped. Thus, it is possible to observe that
there was no chemical change of the resin with the plasticizer. The band corresponding to chlorine in the
605cm-1 resin was changed to 630 cm-1 in the PVC compound. This is because the polymeric plasticizer has
in its composition much more hydrogen than the DOP. This feature causes a deformation to occur in the
molecules of the material, since chlorine and hydrogen have high attraction forces, and this can result in the
chlorine band change.
Figure 1 (e) corresponds to the spectrum of the plasticized PVC with DOP, in which the peaks of both
the resin and the plasticizer are observed. This reinforces the claim made by Larsson et. al. that phthalates
such as DOP are not chemically bound to PVC, so that the spectrum of the plasticized material is an overlap
of the spectra of the resin and the plasticizer [4].
The TGA analyzes of the pure components and the plasticized PVC compounds correspond to the
thermograms shown in Figure 2, which it is possible to observe that the PVC resin is more thermally stable
than plasticized compound in the first thermal stage of decomposition. Data obtained from the decomposition
intervals are presented in Table 2.

Figure 2: TGA overlapping curves of PVC, plasticizer and PVC compounds with: (a) Polymeric Plasticizer PIB; (b)
DOP;

The thermogram of the PVC resin presented two different weight loss processes. The first one was
63.9% in the range of 225 to 388 °C. In this process, according to del Carpio et. al. [26] and Shah et. al. [27],
 DALAGNOL, R. D.; FRANCISQUETTI, E. L.; SANTANA, R. M. C., revista Matéria, v.22, n.2, 2022

the dehydrochlorination of PVC occurs. This percentage corresponds to the loss of stoichiometric mass of
58.4%, however, it is estimated that this difference is attributed to the fact that a drying process was not
performed on the PVC, so that the resin contained retained moisture. The second weight loss process of
26.4% in the range of 388°C to 549 °C, occurs due to the formation of aromatic and allylic compounds, and
the degradation of hydrocarbons [28]. After loss of hydrogen chloride and breakage of the double bonds,
cross-linking formations can occur in the polymer chain, called cross-linking [29]. This explains the residue
of approximately 10% of the initial mass of the PVC resin, since the formation of self crosslinking occurred
due to the formation of double bonds (-C=C-), with the degradation of C-Cl.

Table 2: Results obtained by TGA analyzes of the samples evaluated.

Decomposition Temperature / PVC with

Polymeric DOP PVC with DOP
stage Weight loss PVC Resin Polymeric
Plasticizer Plasticizer Plasticizer
Plasticizer
T3%(ºC) 275 209 193 235 224
1st Tonset (ºC) 225 126 130 180 180
% weight 63.9 40 3 69 71
2nd Tonset (ºC) 388 340 202 382 385
% weight 26.4 60 97 20 15
3rd Tonset (ºC) - - - 560 565
% weight - - - 8 4.7
Ash % weight 9.7 - - 3 9.3

It is possible to note a weight loss of 40% in the range of 126 to 340°C, as observed in the
thermogram of the polymeric plasticizer in Figure 2 (a). This loss corresponds to the degradation of the
solvent (secondary plasticizer) present in the plasticizer, the second loss process of 60% in the range of 340
to 442 °C, corresponds to the decomposition of the constituent polymer of the plasticizer. In Figure 2 (b) it is
possible to observe the DOP thermogram, which also presented two mass loss stages. The first loss of 3%
between 130 and 202 °C, corresponds to the degradation of the solvent alcohol present in the plasticizer. The
remaining 97% is degraded in the range of 202 to 337 °C with a mean point of 318 °C, is attributed to the
decomposition of dioctyl phthalate.
The thermograms of the plasticized compounds presented an overlapping behavior of the curves of
PVC resin and plasticizers. However they presented three stages of mass loss as verified by Pita and
Monteiro [30], the first referring to PVC dehydrochlorination, the second associated with
dehydrohalogenation, and the third stage the decomposition of the main chain structure. According to the
Institute for Occupational Safety and Health (IFA), the temperature of decomposition of plasticized PVC is
around 180 °C, at which temperature both plasticized materials began the decomposition process [31]. In the
case of Figure 2 (b), it is observed that the degradation of the plasticized material with DOP of 71%, in the
range of 180 and 385 °C. That corresponds to the beginning of degradation of the plasticizer with the
dehydrochlorination of PVC. In the second stage of mass loss of 15% between 385 and 565 °C, there is no
longer the presence of DOP in the material, since it has already been totally degraded in this temperature
range. Thus, as the initial process temperature is close to the final dehydrochlorination temperature of the
PVC, the formation of crosslinks occurs during the ends of the hydrocarbon degradation present in the
material. At the end of the third mass loss process of 4.7% from 565 to 900 °C, a percentage of
approximately 10% of inorganic load is observed due to the formation of crosslinks, a behavior similar to
pure PVC resin. This behavior was also obtained by Mattana et. al. [32], which suggests that the behavior is
initiates in the defects of the chain, that is, in the weak bonds. These results are corroborated by the
evaluation of PVC compounds with similar content of plasticizers, which showed three stages of degradation
and ash [33].
The compound with polymeric plasticizer presented a distinct behavior of the plasticized material with
DOP. As observed in Figure 2 (a), the thermogram of the material was also presented as an intermediate
behavior of the curves of the resin and plasticizer. During the first mass loss of 69% in the range of 180 and
382 °C, the degradation onset of the solvent of the plasticizer occurred along with the dehydrochlorination of
the PVC. However, unlike PVC compound with DOP, during the second mass loss (20%) between 382 and
560 °C and inflection point at 458 °C, there is still a presence of plasticizer in the material. This characteristic,
during the second stage of mass loss, influences the formation of crosslinking. Polymeric plasticizers are
 DALAGNOL, R. D.; FRANCISQUETTI, E. L.; SANTANA, R. M. C., revista Matéria, v.22, n.2, 2022

defined as substances with high molecular weight, which decrease migration, extraction and volatility.
Studies conducted by Bueno-Ferrer et. al. conclude that polymeric plasticizers increase the thermal stability
of PVC. [34]. Based in the results, after the dehydrochlorination, the plasticizer molecules present in the
material make it difficult to form double bonds (-C=C-). Thus, at the end of the third process of mass loss of
the material with polymeric plasticizer, there is only one residue of 3%, since the presence of plasticizer after
dehydrochlorination prevented the formation of crosslinks in the material. It is noteworthy that the
decomposition kinetics of the compound PVC plasticized with polymer was slower, as observed by the larger
DTG peaks.
Differential scanning calorimetry (DSC) analyzes of the pure components and the plasticized
compounds are shown in Figure 3. Transitions such as Tg and Tm are related to the gain or loss of energy by
the molecules, in the case of use of plasticizers, they reduce the interactions between the polymer chains and
consequently reduce Tg. As the chain spacing of the polymer is increased, the properties of T g and Tm also
decrease [35]. It can be seen from Figure 3 that the PVC resin and the plasticized materials during the second
heating, and for the plasticizers in the first heating.

Figure 3: DSC curves of second heating of PVC plasticized with: (a) Polymeric plasticizer PIB; (b) DOP.

According to Wilkes et. al. PVC has Tg close to 80 °C, and as expected the PVC resin showed a T g at
77 °C, which can be observed in Figure 3 [36]. Madaleno et. al. also confirms this value obtained from the
same method around 83.3 °C [37]. The PVC resin also showed an endothermic event at 105 °C (ΔH=0.36 J.g-
1
), which can be attributed to a relaxation peak [38, 39].
An evaluation of the polymeric plasticizer in Figure 3 (a) shows that there was a chemical interaction
in the solution of the polymer with its solvent DOCH, but no chemical reaction occurs. This interaction is
responsible for the formation of a gel point, at about 73°C, of the polymer and its solvent, that is, below this
temperature the plasticizer has the behavior of a gel. The DOP plasticizer also presented a gel point, however
 DALAGNOL, R. D.; FRANCISQUETTI, E. L.; SANTANA, R. M. C., revista Matéria, v.22, n.2, 2022

softer, at approximately 0.5 °C [40, 41].

When PVC is plasticized, a decrease in T g is expected due to the separation of chains and an increase
in the overall mobility of the material, causing a weakening of the intermolecular interactions [35, 42]. It is
observed that the plasticized material with DOP showed, as observed in Figure 3 (b), a transition at -50.5 °C
and another at 75.3 °C. This large reduction in T g was also observed by Perito [43], which suggests that the
chains spacing reduces the forces of secondary intermolecular attraction, reducing the energy level necessary
to give mobility to the entire chain, consequently reducing the T g of the polymer. This variation of Tg occurs
because, as the plasticizer content is increased in its formulation, a reduction of the glass transition is caused
[10].
It is possible to observe that the material with polymeric plasticizer shows no indication of thermal
events. This behavior can be attributed to the fact that the plasticizer acted in order to separate the PVC
chains, hindering the crystalline formation, even if it is relatively low in the PVC compounds, making the
material amorphous. The material also did not present a glass transition, this can occur due to the method
being ineffective for the determination of Tg in PVC compounds [44]. Therefore, the determination of T g of
the material should be done by DMA, since it is around 10-100 times more accurate and sensitive when
evaluating the glass transition, which may be undetectable in the DSC test [14].
The DMA analyzes of the pure compounds and the plasticized materials are shown in Figure 4 and
Figure 5. The storage modulus (E’) and loss modulus (E”) of PVC compounds are shown in Figure 4.

Figure 4: Results obtained by DMA (a) Storage Modulus of plasticized PVC; (b) Loss Modulus of plasticized PVC.

Observing the storage modulus in the Figure 4 (a), at very low temperatures the compound with
polymeric plasticizer shows a much more elastic behavior than the DOP reference. That can be attributed to
the fact that at low temperatures the elastic behavior of the polymeric plasticizer is predominant compared to
the reference. This indicates that at low temperatures, PVC with DOP shows a greater distance from the
chains. When compared to the material with polymeric plasticizer, the reference manages to store a smaller
amount of energy, since it has a larger free volume.
Comparing the storage modulus (E’) shown in Figure 4 (a), it is noted that the behavior at low
temperatures corresponds to a material with a greater capacity to store energy. This character to store remains
throughout the test, however as temperature is increased the difference between the modules is decreased, so
that at the end of the test the storage and loss modules of both materials are closer, than at the beginning of
the test. However, even with this decrease, the materials still have a higher elastic energy when compared to
the loss modulus.
From the results shown in Figure 4 (a), the storage modulus of the plasticized PVC composite showed
higher elastic modulus and higher temperature stability, since the decay is slower when compared to the DOP
compound. In relation to the loss modulus Figure 4 (b), the viscous dissipation of the plasticized PVC
compound with DOP was more pronounced, exhibiting a shift of the temperature from the peak to the left
(lower Tg) when compared to the compound with the polymer plasticized compound.
The tan δ curves of the plasticized materials are shown in Figure 5. The PVC compound with DOP
showed a glass transition at around -10 °C. When comparing this result with that obtained by DSC, a
variation of about 40 °C is observed. This variation is attributed to the fact that the DMA assay is more
 DALAGNOL, R. D.; FRANCISQUETTI, E. L.; SANTANA, R. M. C., revista Matéria, v.22, n.2, 2022

sensitive for Tg evaluation [14]. In addition, the DSC method uses a much lower amount of material than that
used in DMA, and if the material does not have a good homogenization, it may influence the test result.
Mattana obtained a result of T g of PVC plasticized with DOP close to the value obtained in this work,
determined by the DMA method [45].

Figure 5: Tan δ curves of the PVC compounds obtained by DMA.

The PVC compound with polymeric plasticizer presented a glass transition at approximately 7°C, as
observed in Figure 5. This result can not be detected by DSC, which indicates a better efficacy of the test for
the determination of Tg. Further reduction of T g was expected since the polymeric plasticizer has a molar
mass much higher than DOP. A study by Ferruti et. al. indicates that the molar mass influences in a greater
reduction of Tg, since a larger spacing occurs in the main chains of PVC [46]. In addition, the author further
notes that the longer the plasticizer chains, the greater the entanglement of the PVC material. It is possible to
note that the plasticized material had a higher temperature range when compared to the reference with DOP.
This behavior was also verified by Madaleno et. al. [37], which conclude that this temperature range suggests
that there is a microheterogeneity between the PVC and the plasticizing polymer.

4. CONCLUSIONS
A polymeric plasticizer polyisobutene (PIB) dissolved in a solvent carboxylic acid Bis (2-ethylhexyl)
cyclohexane1,2-dicarboxylate (DOCH) was used in substitution to DOP plasticizer (50PHR) were add to
PVC resin and their properties evaluated. The presence of polymeric plasticizer had a direct influence on the
degradation temperature of PVC, resulting a higher thermal stability.
The results obtained in this work contributed to an aid in the selection of alternative plasticizers to
dioctyl phthalate. Based on these results, there is a strong tendency for applications in flexible follow-ups,
such as footwear industry.
In addition to this evaluation of alternative use of plasticizer, it is suggested that studies of chemical
stability. It is concluded that the plasticizer evaluated does not directly replace the DOP, and for some
applications the material already presents better performance than this one. It is evident the increased study
of plasticizers alternative to DOP, with thermal stability being one of the main desired factors due to the low
stability of the PVC resin.

5. ACKNOWLEDGMENTS
To the institutions UFRGS - LAPOL and IFRS Campus Farroupilha. To the companies Grendene S/A and
Mantova Ltda.
 DALAGNOL, R. D.; FRANCISQUETTI, E. L.; SANTANA, R. M. C., revista Matéria, v.22, n.2, 2022

6. REFERENCES
[1] BRASKEM. Braskem divulga hoje os resultados do 4T17. 2018 [cited 2018 18/04/2018]; Available from:
http://www.braskem-ri.com.br/detalhe-noticia/braskem-divulga-hoje-os-resultados-do-4t17-e-2017-e-convida-para-
teleconferencia.
[2] ENVIRONMENTAL WORKING GROUP. Down the Drain: Phthalates. 2007 [cited 2018 11/04/2018]; Available
from: https://www.ewg.org/research/down-drain/»-phthalates#.Ws6AMUxFxzk.
[3] INSTITUTO DE PESQUISAS TECNOLÓGICAS (IPT). Análise de plastificantes em brinquedos. 2018 [cited 2018
09/04/2018]; Available from: www.ipt.br/solucoes/34analise_de_plastificantes_em_brinquedos.htm.
[4] LARSSON, K., et al., Phthalates, non-phthalate plasticizers and bisphenols in Swedish preschool dust in relation to
children's exposure. Environment International. 102: pp. 114-124. 2017.
[5] LAJQI-MAKOLLI, V., et al., Migration of di-(2-ethylhexyl)adipate (DEHA) and acetyl tributyl citrate (ATBC)
plasticizers from PVC film into the food stimulant of isooctane. Materialwissenschaft und Werkstofftechnik. 46(1): pp.
16-23. 2015.
[6] ANVISA, Resolução RDC nº 17, de 17 de março de 2008, ANVISA 2017.
[7] WICKSON, E. J., Handbook of polyvinyl chloride formulating. Wiley. 1993.
[8] GOTTESMAN, R. T., GOODMAN, D. Poly (vinyl chloride). ACS Publications.
[9] MURPHY, J., Additives for plastics handbook. Elsevier. 2001.
[10] NUNES, L. R., et al., Tecnologia do PVC. São Paulo: ProEditores/Braskem. 2002.
[11] ASTM D2124-99, Standard Test Method for Analysis of Components in Poly(Vinyl Chloride). Compounds Using
an Infrared Spectrophotometric Technique. ASTM International, West Conshohocken, PA. 2011.
[12] SMITH, B. C., Fundamentals of Fourier transform infrared spectroscopy. CRC press. 2011.
[13] ASTM E1131-08, Standard Test Method for Compositional Analysis by Thermogravimetry. ASTM International,
West Conshohocken, PA. 2014.
[14] MENARD, K. P., MENARD, N. R. Dynamic Mechanical Analysis in the Analysis of Polymers and Rubbers.
Encyclopedia of Polymer Science and Technology. 2015.
[15] FRANCISQUETTI, E. L., Obtenção e propriedades de misturas poliméricas a partir de POE/EVA/PVC. Tese,
Engenharia e Ciência dos Materiais, UFRGS. 2012.
[16] MARCILLA, A., et al., Fusion behavior of plastisols of PVC studied by ATR‐FTIR. Journal of Vinyl and Additive
Technology. 1(1): pp. 10-14. 1995.
[17] WYPYCH, G., PVC degradation and stabilization. Elsevier. 2015.
[18] HONG, C. K., et al., Thermal behaviors of heat shrinkable poly (vinyl chloride) film. Journal of applied polymer
science. 112(2): pp. 886-895. 2009.
[19] PURCAR, V., et al., Preparation and characterization of some sol-gel modified silica coatings deposited on
polyvinyl chloride (PVC) substrates. Coatings. 11(1): p. 11. 2021.
[20] FUZAIL, M., et al., Effectiveness of DOP mobilizer on the radiolysis of a semi-crystalline ethylene–propylene
copolymer. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and
Atoms. 265(1): pp. 285-289. 2007.
[21] SILVERSTEIN, R., WEBSTER, F. Identificação espectrométrica de compostos Orgânicos, 6 edição. LTC, RJ. 2000.
[22] DOS REIS, J. H., et al., Síntese, purificação e caracterização estrutural de monômeros derivados do metacrilato de
glicidila para utilização em resinas compostas dentais. 8º Congresso Brasileiro de Polímeros, Águas de Lindóia. 2005.
[23] DREGER, A. A., et al., Caracterização mecânica e morfológica de solados produzidos com resíduos de laminados de
PVC da indústria calçadista. Matéria (Rio de Janeiro). 23. 2018.
[24] KUMAR, R., et al., Ion beam modification of CR-39 (DOP) and polyamide nylon-6 polymers. Nuclear Instruments
and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms. 212: pp. 221-227. 2003.
[25] WYPYCH, G., Handbook of plasticizers. ChemTec Publishing. 2004.
[26] DEL CARPIO, D., D’ALMEIDA, J. Avaliação da influência da absorção de água e de derivados de petróleo em
tubulações de PVC. 19º Congresso Brasileiro de Engenharia e Ciência dos Materiais – CBECiMat. 2011.
[27] SHAH, B.. SHERTUKDE, V. Effect of plasticizers on mechanical, electrical, permanence, and thermal properties of
poly (vinyl chloride). Journal of applied polymer science. 90(12): pp. 3278-3284. 2003.
[28] SEVERGNINI, V. L. S., Estudo da degradação térmica do poli (cloreto de viníla-co-acetato de viníla-co-2-
hidróxipropil acrilato) e seus homopolímeros. Dissertação, Departamento de Quimica, UFSC. 2002.
[29] FARIA, E. C., Blendas de poli (cloreto de vinila) e do elastomero termoplastico poli [estireno-g-(etileno-co-
propileno-co-dieno)-g-acrilonitrila]. Dissertação, Instituto de Química, Universidade Estadual de Campinas. 2008.
[30] PITA, V., MONTEIRO, E. E. Estudos térmicos de misturas PVC/plastificantes: caracterização por DSC e TG.
Polímeros: Ciência e Tecnologia. 6(1): pp. 50-56. 1996.
[31] GESTIS-IFA, Registro de CAS RN 9002-86-2 na Base de Dados de Substâncias GESTIS do IFA. 2017
[32] MATTANA, M., et al., Influência do tipo de plastificante e das condições de processamento na estabilidade térmica e
processabilidade do poli (cloreto de vinila). 22º CBECiMat. 2016.
 DALAGNOL, R. D.; FRANCISQUETTI, E. L.; SANTANA, R. M. C., revista Matéria, v.22, n.2, 2022

[33] SOUZA, L. D. A., et al., PVC plasticizer from trimethylolpropane trioleate: synthesis, properties, and application.
Polímeros. 31. 2021.
[34] BUENO-FERRER, C., et al., Characterization and thermal stability of poly (vinyl chloride) plasticized with
epoxidized soybean oil for food packaging. Polymer degradation and stability. 95(11): pp. 2207-2212. 2010.
[35] COWIE, J. M. G., ARRIGHI, V. Polymers: chemistry and physics of modern materials. CRC press. 2007.
[36] WILKES, C. E., et al., PVC Handbook 2005. 2005, Hanser Verlag.
[37] MADALENO, E., et al., Estudo do uso de plastificantes de fontes renovável em composições de PVC. Polímeros:
Ciência e Tecnologia. 19(4). 2009
[38] ALVES, J. P. D., RODOLFO JR., A. Análise do processo de gelificação de resinas e compostos de PVC suspensão.
Polímeros: Ciência e Tecnologia. 16(2): pp. 165-173. 2006.
[39] GILBERT, M., Crystallinity in poly (vinyl chloride). Journal of Macromolecular Science, Part C: Polymer Reviews.
34(1): pp. 77-135. 1994.
[40] AKCELRUD, L., Fundamentos da ciência dos polímeros. Editora Manole Ltda. 2007.
[41] RABELLO, M. S., Aditivos de Polímeros. São Paulo: Editora Artliber. 2000.
[42] RABELLO, M., DE PAOLI, M. Aditivação de termoplásticos. São Paulo: Artliber. 2013.
[43] PERITO, E.D., Estudo de plastificantes alternativos ao dioctilftalato (DOP) para um composto de poli (cloreto de
vinila)(PVC), in Dissertação, Engenharia e Ciência dos Materiais, UCS. 2014.
[44] MONTEIRO, E., et al., Caracterização de Polímeros: Determinação de Peso Molecular e Análise Térmica. Rio de
Janeiro, E-Papers. p. 366. 2001.
[45] MATTANA, M., Plastificantes alternativos ao dioctil ftalato nas propriedades de compostos de poli(cloreto de
vinila). Dissertação, Engenharia e Ciência dos Materiais, UFRGS. 2017.
[46] FERRUTI, P., et al., Polycaprolactone− Poly (ethylene glycol) Multiblock Copolymers as Potential Substitutes for
Di (ethylhexyl) Phthalate in Flexible Poly (vinyl chloride) Formulations. Biomacromolecules. 4(1): pp. 181-188. 2003.

ORCID
Rafael Domingos Dalagnol https://orcid.org/0000-0003-0019-9518
Edson Luis Francisquetti https://orcid.org/0000-0002-1055-3317
Ruth Marlene Campomanes Satana https://orcid.org/0000-0001-6843-9915