Sie sind auf Seite 1von 7

J. Anal. Appl.

Pyrolysis 71 (2004) 457463

Study of the migration of PVC plasticizers


A. Marcilla , S. Garca, J.C. Garca-Quesada
Chemical Engineering Department, University of Alicante, S. Vicente del Raspeig,
03690 Alicante, Spain
Received 15 April 2003; received in revised form 29 May 2003; accepted 16 July 2003

Abstract
An accelerated method has been set up in order to study the capacity of migration of different
commercial plasticizers from flexible PVC parts towards other media kept in contact with it; in this
case, polystyrene (PS) has been used as example. This process may occur during the storing or
shipping of this type products and could modify their properties or their aesthetic appearance. The
test consists in maintaining during 1 week the flexible PVC item in contact, under a given pressure,
with a polystyrene sheet at 50 C. After this time, the PVC and the PS are separated and the thermal
degradation of the PS is then studied in a thermobalance under nitrogen atmosphere, using Curie
metals as internal standards. The study of the pyrolysis behaviour can be used in order to evaluate
the amount of plasticizer migrated. Several samples must be analysed in order to obtain reliable
results. The behaviour of plasticizers of different chemical families (i.e. phthalates and citrates) and
molecular weights, has been studied. Although the plasticizer loss is not observed as a sharp process
in the loss weight versus temperature curve (due to the existence of plasticizer fractions which seem
to interact differently with the polymer), clear conclusions can be obtained regarding the amount of
migrated plasticizer and the temperature of the process, which increases with the molecular weight
of the plasticizer. The type of the plasticizer has also a significant effect and the citrates have higher
migration capacity than phthalates.
2003 Elsevier B.V. All rights reserved.
Keywords: Migration; Plasticizer; PVC; Pyrolysis

Abbreviations: ATBC, acetyl tributyl citrate; ATEC, acetyl triethyl citrate; ATHC, acetyl trihexyl citrate;
DEHP, di(2-ethylhexyl) phthalate; DHP, diheptyl phthalate; DINP, diisononyl phthalate
Corresponding author.
E-mail address: antonio.marcilla@ua.es (A. Marcilla).
0165-2370/$ see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0165-2370(03)00131-1

458

A. Marcilla et al. / J. Anal. Appl. Pyrolysis 71 (2004) 457463

1. Introduction
PVC is one of the most used polymers, because it is easily processed and compounded,
the raw materials involved in its formulation have a relative low cost and because a wide
range of properties can be obtained.
The most widely used primary plasticizers have a low molecular weight (known as
monomeric plasticizers), in contrast to polymeric plasticizers, which are generally saturated
polyesters. The most common monomeric plasticizers are esters derived from phthalic acid,
although other derived from different organic acids can be used, as phosphates, trimetillates,
citrates, sebacates, adipates, etc. [1,2].
In many applications, the migration of the plasticizer from a PVC item towards the
medium in contact with it (gas, liquid or solid) may occur. Migration process may depend
on the polymer properties (i.e. molecular weight), the nature and amount of the plasticizer,
the plasticization process and the homogeneity of the compound and the surrounding media,
i.e. nature, compatibility with the plasticizer, and effect on polymer, and obviously on the
temperature, contact area and other conditions.
Under given conditions, the permanence of a plasticizer in a flexible PVC compound
depends upon three major factors which include structure, molecular weight/viscosity, and
polarity. Branched plasticizers are more permanent than the equivalent but linear plasticizers, since branching tends to hinder movement or entangle the plasticizer within the
polymer matrix making it more difficult to migrate or to be removed by volatilization or
extraction. However, linear structures provide less permanence, but they do yield better low
temperature properties.
Thus, migration could difficult the utilization or commercialization of plasticized PVC
items, due to the appearance, for example, of environmental problems, food contamination and difficulties in toys applications. For example, in the latter field, it is possible to
observe different problems related to plasticizer migration, such as plasticizer extraction
from PVC if the item is sucked or chewed by a child or plasticizer migration towards other
polymeric items employed in the same toy, as, for example, polystyrene (PS) insertions
used in artificial eyes of dollies.
Phthalates, more concretely diisononyl phthalate (DINP) and di(2-ethylhexyl) phthalate
(DEHP), have been usually employed during the latest decades for PVC plasticization
(including toy manufacturing), due to their low cost, good flexibility properties of the
product, good permanence, etc. However, in the latter years, their substitution by citrates
or aliphatic diesters in items susceptible to be in contact with food or sucken by children
has been suggested. Phthalates were shown to be the responsible of cancer proliferation
in mice and rats [3]; although the risk for humans was not evaluated, different Consumers
Associations and Ecologist Groups asked the elimination of phthalates in PVC, mainly in
those applications were PVC items are designed to be used orally. Thus, toy and child-care
applications, specially those items susceptible to be chewed or sucked by children, started
to be seriously questioned.
In 1998, the Scientific Committee on Toxicity, Ecotoxicity and the Environment (CSTEE)
of the European Union suggested different guideline values [4] for extractable phthalates
in toys, which ought be respected. However, in the absence of a reproducible test able to
determine migration levels for regulatory purposes, phthalates were eventually banned in

A. Marcilla et al. / J. Anal. Appl. Pyrolysis 71 (2004) 457463

459

European Community in 1999 [5], in those applications intended for children under the age
of 3 years and which can be put in the mouth.
In conclusion, the permanence of a plasticizer, in addition to its toxicity and processability,
is one of the most important characteristics to be considered. Thus, the aim of the present
work is to set up a comparative method to evaluate the migrability of PVC plasticizers
towards other polymeric materials, PS in this case, and compare the behaviour of some of
the most used phthalates with some of the most common citrate plasticizers.

2. Experimental
2.1. Materials
The emulsion PVC resin ETINOX 450, from Rio Rodano was employed; it is a standard
PVC resin for rotational moulding purposes, with a K value of 67. The ASUA 656-T2, a
calcium zinc stabilizer from Industrias Qumicas Asua, was employed as thermal stabilizer.
Plasticizer employed were the phthalates, diheptyl phthalate (DHP), DEHP and DINP, from
BASF and the citrates, acetyl triethyl citrate (ATEC) and acetyl tributyl citrate (ATBC), from
Chemical S.P.A. and acetyl trihexyl citrate (ATHC) from Reilly Industries. Polystyrene
employed was 143E from BASF.
2.2. Sample preparation
The PVC resin was dispersed into the plasticizer and the thermal stabilizer in a high-speed
mixer in the following proportions: 55.3% of PVC, 41.4% of plasticizer and 3.3% of the
thermal stabilizer; mixing operation was carried out under vacuum in order to avoid the
presence of air bubbles in the final product. One hundred grams of PVC plastisols hereby
obtained by pouring and gelling the PVC plastisol at 185 C in a flat mould during 20 min,
obtaining plasticized PVC sheets of 2 mm of thickness.
Polystyrene sheets of 1 mm of thickness were obtained by compression moulding of the
polymer at a temperature of 190 C.
2.3. Migration test
Small squared strips of polystyrene (3 mm3 mm) with approximately 1 mm of thickness
were placed between two PVC sheets of 2 mm of thickness, and kept under mild pressure
(217 kPa) in a oven at 50 C for 1 week.
Plasticizer migrated after this time, was determined by thermogravimetric analysis, in a
Perkin-Elmer thermobalance, by heating the sample from 25 to 600 C at 10 C/min under
a 20 ml (STP)/min flow of nitrogen.

3. Results and discussion


Thermogravimetric study of different polystyrene samples reveals marked differences in
the degradation process. Fig. 1 shows the behaviour of a blank polystyrene sample, and

460

A. Marcilla et al. / J. Anal. Appl. Pyrolysis 71 (2004) 457463


100

Temperature (C)
100

60
40
20
0
100

200

300

Temperature (C)

400

500

Weight loss Derivative (K -1)

Weight Loss (%)

80

200

300

400

0.0

-0.5

-1.0

Fig. 1. Behaviour of weight loss and weight loss derivative for: () blank polystyrene; () polystyrene + DEHP;
() polystyrene + ATBC.

others aged in contact with DEHP and ATBC specimens, as example. While the blank
polystyrene sample shows one unique step in the weight loss and the weight loss derivative curves, attributed to the degradation of the polymer, aged samples show at least one
additional step. An earlier and slow weight loss process (i.e. a broad peak) can be observed at temperatures close to the boiling point of the plasticizer (for example, 173 C
for ATBC and 230 C for DEHP), which clearly correspond to plasticizer release from
the polystyrene sample. However, at higher temperatures (around 300 C) an intermediate process between the first plasticizer release and the polystyrene degradation can be
clearly observed in the case of ATBC, a relatively sharp peak (also present in the rest of
citrates as shown in Fig. 4). This additional process could be attributed to different reasons: the likely presence of PVC adhered to polystyrene, the decomposition of a fraction
of polystyrene which has interacted with the plasticizer or to the release of a fraction of
plasticizer which interacts stronger with the polystyrene and is released at higher temperatures. In order to clarify its origin, an experiment where the thermal decomposition
behaviour of a mixture of 20 parts in weight of ATEC and 80 parts in weight of PS was
studied, after ageing the sample at 50 C during 2 days. The same intermediate step between the plasticizer loss and the PS degradation was also present, as shown in Fig. 2. The
observed weight loss corresponding to the two first processes exactly match with the plasticizer content in the PS mixture (20% in weight), thus it can be concluded that the first two
peaks correspond to two fractions of the ATEC plasticizer which differently interact with
the PS.
The weight loss curves corresponding to the samples aged in contact with phthalates
plasticized PVC specimens are shown in Fig. 3, and those corresponding to the citrates
in Fig. 4. The plasticizers belonging to the same family exhibit similar behaviour. Thus,
all phthalates show only one broad peak corresponding to the plasticizer release, whereas
all the citrates show the presence of the second process, ascribable to a second plasticizer releasing step. Another important aspect is the much higher amount of plasticizer
released, and consequently migrated into the polystyrene, in the case of the citrates.
This is a very important aspect to be considered since this plasticizer may

100

Temperature (C)

150

200

250

300

350

400
80

-0.4

-0.6

Weight Loss Derivative (K-1)

Weight Loss Derivative (K-1)

-0.2

60

40

20

-0.8

-1.0

0
100

150

200

250
300
350
Temperature (C)

400

450

500

Fig. 2. Weight loss and weight loss derivatives for a mixture (aged at 50 C) of 20% in weight of ATEC in PS (Fig. 1). Behaviour of weight loss (%) for: () blank
polystyrene; () polystyrene + 20% ATEC aged at 50 C; () pure ATEC.

A. Marcilla et al. / J. Anal. Appl. Pyrolysis 71 (2004) 457463

100
0.0

461

462

A. Marcilla et al. / J. Anal. Appl. Pyrolysis 71 (2004) 457463

Temperature (C)
Weight Loss Derivative (K-1)

100

200

300

400

0.0

-0.2

-0.4

-0.6

Fig. 3. Behaviour of weight loss derivative for polystyrenes aged in contact with samples containing: () DHP;
() DEHP; () DINP.

modify the properties of the final parts or even lead to their rejection in the final
application.
A deeper analysis of the behaviour of the plasticizers corresponding to the same family
reveals a clear correlation between their molecular weight and the amount of plasticizer
released or migrated. Fig. 5 shows the cumulative weight percentage lost up to 370 C
(temperature where the plasticizer loss has concluded) versus the molecular weight of the
plasticizer (in g/mol). In both cases, almost a linear behaviour can be observed, where
phthalates show a lower slope than citrates.

Weight Loss Derivative (K-1)

Temperature (C)
100
0.0

200

300

400

-0.2
-0.4
-0.6
-0.8
-1.0

Fig. 4. Behaviour of weight loss derivative for polystyrenes aged in contact with samples containing: () ATEC;
() ATBC; () ATHC.

Wieght percentage lost at 370C

A. Marcilla et al. / J. Anal. Appl. Pyrolysis 71 (2004) 457463

463

35
30
25
20
15
10
5
0
300

350

400

450

500

550

Molecular weight (grams per mol)

Fig. 5. Weight percentage lost at 370 C for acetyl citrates () and phthalates () of different molecular weights.

4. Conclusions
In the present work, an experimental method has been developed and applied to evaluate
the capacity of migration of plasticizers from plasticized PVC typical in rotational moulding
applications.
Phthalates have shown a single but broad process of plasticizer evolution when heated in
a thermobalance under nitrogen atmosphere. Citrates have shown two distinct processes of
plasticizer evolution, the first one very similar to that observed in the case of the phthalates
and a sharper one at higher temperatures.
The use of the suggested method has shown that both types of plasticizers migrates in an
inverse way to their molecular weights, and that the phthalates have a higher permanence
capacity in the plasticized PVC than the citrates. This is a very important feature to be
considered in their practical application, specially for parts designed to be in contact with
PS and probably other plastics.

Acknowledgements
The authors wish to thank Generalitat Valenciana for the economical support of the
project GV01-42.

References
[1] W.V. Titow, PVC Plastics. Properties Processing and Applications, Elsevier, London, 1990.
[2] J. Wickson, Handbook of Polyvinyl Chloride Formulating, Wiley, New York, 1993.
[3] National Toxicology Program (NTP), Carcinogenesis bioassay of di-(2-ethylhexyl)phthalate (CAS no.
117-81-7) in F344 rats and B6C3F mice (feed study), NTP Tech. Rep. Ser. TR no. 217, 1982.
[4] Phthalate migration from soft PVC toys and children care articles, in: Proceedings of the Third Plenary
Meeting of CSTEE, Brussels, 24 April 1998.
[5] Official Journal of the European Communities, L 315/46, 9 December 1999.

Das könnte Ihnen auch gefallen