Accepted Manuscript

Application of waste poly(ethylene terephthalate) in the synthesis of new oligomeric

plasticizers
Ewa Langer, Sylwia Wakiewicz, Marta Lenartowicz-Klik, Krzysztof Bortel
PII:

S0141-3910(15)00168-8

DOI:

10.1016/j.polymdegradstab.2015.04.031

Reference:

PDST 7645

To appear in:

Polymer Degradation and Stability

Received Date: 27 January 2015

Revised Date:

24 April 2015

Accepted Date: 29 April 2015

Please cite this article as: Langer E, Wakiewicz S, Lenartowicz-Klik M, Bortel K, Application of waste
poly(ethylene terephthalate) in the synthesis of new oligomeric plasticizers, Polymer Degradation and
Stability (2015), doi: 10.1016/j.polymdegradstab.2015.04.031.
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Application of waste poly(ethylene terephthalate) in the synthesis of new

oligomeric plasticizers
Ewa Langera, Sylwia Wakiewiczb, Marta Lenartowicz-Klika, Krzysztof Bortela
Institute for Engineering of Polymer Materials and Dyes, 87-100 Toru, ul. M.

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Skodowskiej-Curie 55, Poland, e-mail: e.langer@impib.pl

Silesian University of Technology, Faculty of Chemistry, 44-100 Gliwice, ul. Strzody 9,

Poland

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Keywords: chemical recycling, poly(ethylene terephthalate) waste, oligomeric plasticizer

ABSTRACT

New method of trensesterification of waste poly(ethylene terephthalate) (PET) with aliphatic

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oligoesters was developed. The structures of obtained oligoesters were identified by NMR,
ESI-MS and SEC methods, and then correlated with physical properties determined by DSC
and TGA analyses. Physico-chemical properties of synthesized plasticizers were compared

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with monomeric and polymeric commercial products. Products of the reaction of PET with
oligoesters based on azelaic acid with 1.4-butanediol and adipic acid with triethylene glycol

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occurred to be remarkable substitutes of commercial plasticizers. They possessed lower

volatility and much higher thermal stability. Insertion of glycerol unit into aliphatic oligoester
and using it for the process of PET depolymerization resulted in obtaining of plasticizers of
branching structure with glycerol unit as a core. They possessed lower viscosity and higher
molecular mass in comparison with their linear equivalents.
1. Introduction

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Poly(ethylene terephthalate) (PET) is one of the most commonly used engineering plastics
which owes its popularity to its mechanical properties, chemical resistance, clarity, low O2
and H2O permeability, and good rigidity/weight ratio. The use of poly(ethylene terephthalate)
has increased significantly in recent years since its introduction as a material for the

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production of beverage packaging. Moreover, it is widely used in the textile industry, high
strength fibres and photographic films. PET itself is not directly hazardous for the natural
environment but it does make up a considerable volume of all the municipal waste ending up

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in landfills. It does not erode due to its high resistance to weathering and biological agents.
PET is a non-degradable plastic in normal conditions, as there is no known organism that can

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consume its relatively large molecules [1]. However PET is one of the most extensively
recycled polymeric materials.

There are three distinct approaches to the recycling of post-consumer plastic packaging
materials. The Environmental Protection Agency (EPA) has adopted a new extensive

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nomenclature that refers to physical reprocessing as secondary recycling (2) and chemical
processing as tertiary recycling (3). The EPA primary recycling (1) refers to the use of pre-

[2].

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consumer industrial scrap and salvage to form new packaging, a common product in industry

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There are numerous chemical ways of recycling PET, which include: hydrolysis, alcoholysis,
aminolysis, acidolysis, glycolysis and transesterification. PET is chemically re-processed by
its total depolymerization into monomers or partial depolymerization into oligomers and other
products [3]. Table 1 presents the chemical methods of chemical recycling of PET, the main
reactants and the products obtained [4-8].
Table 1. Methods of chemical recycling of PET
Method

Reactant

Reaction products

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Hydrolysis

Water

Terephthalic acid and ethylene

glycol

Alcoholysis

Methanol

Dimethyl terephthalate and

ethylene glycol (1.2-ethane diol)

Amine

Terephthalamide

Glycolysis

Ethylene glycol

Bishydroxyethyl terephthalate

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Aminolysis

and ethylene glycol

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The utilization of PET waste generates value-added products such as unsaturated polyester
resins, oligo- or polyester plasticizers, acrylate/methacrylate terminated oligoesters and raw

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materials for polyurethanes [5-8]. Our study focused on oligoester plasticizers obtained by
means of the chemical recycling of PET.

The most commonly used plasticizers are monomeric plasticizers, such as: phthalates,
adipates and benzoates. Their disadvantages include lower resistance of the bond line to heat

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and possible migration. However, the use of phthalic plasticizers has been on the decrease due
to their toxicity and tendency to sweat out. Some companies and sectors have looked for safer
materials as alternatives to certain phthalates. While oligomeric plasticizers have smaller

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plasticizing ability compared to monomeric plasticizers, they exhibit limited volatility and
migration and do not undergo extraction, which is essential in many applications [9].

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There are many publications in the literature on obtaining dioctyl terephthalate (DOTP) in the
process of PET alcoholysis. There are few studies, however, that describe the synthesis of
oligomeric plasticizers based on the products of PET waste depolymerisation. For instance,
Dupont et al. [10] reported on the alcoholysis of PET scrap using 2-ethyl-1-hexanol (EH) at
reflux temperature for the purpose of synthesizing DOTP plasticizers for flexible poly(vinyl
chloride) (PVC). The DOTP produced by this method was equivalent to commercial grades in
terms of its plasticization efficiency for PVC.

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Dutt and Soni, on the other hand, synthesized an oligomeric plasticizer with an average
molecular mass in the range of 450-900 g/mol from PET waste also through alcoholysis using
EH. They used it in nitrile rubber and nitryle-PVC blends [11].
The boiling point of EH at atmospheric pressure is about 180 C and the efficiency of

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alcoholysis is very low. Three methods for improving the efficiency of alcoholysis are known:
use of sub- and supercritical EH, use of transesterification catalyst and/or addition of some
cosolvents [12].

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The use of a cosolvent is a new way to accelerate the chemical reaction and it also improves
reaction efficiency. The imidazole ionic liquid assisted in the process of PET alcoholysis with

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EH, as a cosolvent in obtaining DOTP. This process was catalyzed by the addition of 1.2%
(w/w) of zinc acetate. The yield of DOTP reached 93% at reflux temperature and a reaction
time of 5 h, while the weight ratio of the ionic liquid:EH:PET was 2:2:1. The reaction time of
traditional reflux temperature alcoholysis of PET without ionic liquid as a cosolvent should be

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at least 10 h.

Oligoester plasticizers, with hydroxyl end-groups and an average molecular mass of 2500
g/mol, were also obtained by the degradation of PET waste by polyethylene glycol 400 and

EP

adipic acid in the presence of a transesterification catalyst. These compounds were tested as
plasticizers in a poly(vinyl acetate) dispersion adhesives for flooring applications. The

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samples containing synthesized plasticizers were more flexible and had a higher thermal
stability in comparison to commercial plasticizer 1.2.3-triacetoxypropane [13].
In recent years, the following compounds have been used as catalysts for the glycolysis or
transesterification of PET: metal acetates [14-15], phosphates [16], solid super-acid, metal
oxide [17-18], carbonate [19], sulfate [20] and ionic liquids.
In chemical synthesis organotin compounds are used expecially in the esterification and
transesterification reactions of mono- and polyesters. Organotin compounds such as

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butylstannoic acid are used as catalyst to reduce the formation of unwanted by-products and
also provide the required colour properties [21].
The aim of the presented work was the full replacement of the low molecular weight toxic

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phthalate-based plasticizers for PVC, which have been used so far, with environmentally
friendly materials. The paper presents a new, previously unexplored method for obtaining
oligomeric plasticisers in a reaction of PET waste transesterification by means of oligoesters.

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2. Experimental

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2.1. Materials

A sample of PET flakes was acquired from Industrie Maurizio Peruzzo POLOWAT Sp. z o.o.
(average molecular weight 50000 g/mol). Anhydrous 2-ethylhexanol, adipic acid (Ad), azelaic
acid (Az), diethylene glycol (DE), dipropylene glycol (DP), 1.4-butandiol (BD), triethylene
glycol (TE) and glycerine (Gl) were purchased from Brenntag Polska. All reagents were used

catalyst.

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as purchased without further purification. Fascat 4100, butylstannoic acid, was used as a

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2.2. Transesterification of PET

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Waste PET-based plasticiser synthesis was conducted in two stages. A 1000 ml glass reactor
equipped with an agitator, a splash-head, a thermometer and an azeotropic cap was filled with
dicarboxylic acid, glycol and monohydroxyl alcohol (Table 2). The reaction was carried out in
a temperature range of 140160 C under atmospheric pressure. The reaction was carried out
until an acid value of less than 10 mgKOH/g was achieved. PET waste and 0.06% w/w of the
Fascat 4100 esterification catalyst was added in situ to the oligoester obtained. The
temperature of the reaction was increased to 190-210 C. The total time of the synthesis was
10-12 hours.

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The following plasticisers were obtained in the oligoester degradation of PET waste:
azelaic acid with diethylene glycol and a 2-ethylhexanol end-group (designated as
PETDEAz);
adipic acid with dipropylene glycol and a 2-ethylhexanol end-group (designated as

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PETDPAd);

azelaic acid with dipropylene glycol and a 2-ethylhexanol end-group (designated as

PETDPAz);

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adipic acid with 1.4-butanediol and a 2-ethylhexanol end-group (designated as

PETBDAd);

PETBDAz);

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azelaic acid with 1.4-butanediol and a 2-ethylhexanol end-group (designated as

adipic acid with glycerine and dipropylene glycol and a 2-ethylhexanol end-group
(designated as PETDPAdGl);

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azelaic acid with glycerine and dipropylene glycol and a 2-ethylhexanol end-group
(designated as PETDPAzGl);

azelaic acid with glycerine and glycol and a 2-ethylhexanol end-group (designated as

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PETDEAzGl);

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The obtained products were characterized using NMR spectroscopy, ESI-MS and SEC
spectrometry techniques, thermal analyses (DSC, TGA) and were checked for volatility.
Table 2. Composition of synthesized plasticizers*
Symbol

PETD

PETD

PETD

PETB

PETB

PETD

PETD

PETD

Composition

EAz

PAd

PAz

DAd

DAz

PAdGl

PAzGl

EAzGl

PET (g)

30.20

31.61

28.90

34.08

31.00

24.64

22.24

23.00

2-ethylhexanol (g)

13.70

14.27

13.10

15.39

13.99

16.69

15.07

15.58

Adipic acid (g)

32.05

34.55

37.52

Azelaic acid (g)

39.40

37.80

40.47

43.59

45.05
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Dipropylene glycol
(g)
Diethylene glycol
(g)
1.4-butanediol (g)

3.94

3.55

3.67

22.06

20.20

17.22

15.54

16.70

12.70

15.98

14.53

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Glycerine (g)

* the reactant amounts provided have been calculated per 100g of reactant load
2.3. Characterization of the transesterification products

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Nuclear Magnetic Resonance (NMR) spectra were recorded using a UNITY/INOVA 300
MHz (Varian Associates Inc.) multinuclear NMR spectrometer. 1H and

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C NMR spectra

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were run in deuterated chloroform (CDCl3) using tetramethylsilane (TMS) as an internal

standard.

Differential scanning calorimetry (DSC) analyses were carried out using a DSC 2010 Thermal
Analysis Calorimeter. Measurements and calibration were carried out at a heating rate of 10

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C/min in a nitrogen atmosphere.

The decomposition temperature of the plasticisers was determined on the basis of the TGA
(Thermogravimetry)

analysis

according

to

EN

ISO

11358:2004Plastics

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Thermogravimetry (TG) of polymers - General principles. Samples were heated at a rate of

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20 C/min from 25 C to 900 C under nitrogen atmosphere.

Electrospray ionisation mass spectrometry (ESI-MS) experiments were performed using an
AmaZon (Bruker-Daltonics, Brema, Germany) mass spectrometer

equipped with an

electrospray ionisation source. Samples were dissolved in a solution of CHCl3/methanol ((v/v)

1:1). The mass spectrum was acquired over the range of m/z 503000 in the positive ion
mode.
Molecular weight was measured by means of size exclusion chromatography analysis (SEC)
using a Waters system equipped with refractive index detector. Two 300x7.5 mm (Polymer

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Laboratories VARIAN) Pl-gel m Mixed C columns were used and maintained at 40 C.
Fisher Chemicals tetrahydrofuran (THF) was used as eluent at a flow rate of 1 mL/min.
Polystyrene standards (Polymer Laboratories) were used to calibrate the system.
The viscosity of the plasticizers was determined in accordance with ISO 2555.

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The volatility of the plasticizers was determined by the authors own method. Volatility was
determined by placing the samples of the tested plasticisers in petri dishes in a drier without
air circulation for 2 h at temperatures of 160 to 180 C, and the obtained values (expressed in

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%) were calculated on the basis of the mass loss of the sample.

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3. Results and discussion

Oligoester plasticizers were obtained in a 2-step reaction. The first stage consisted of the
synthesis of oligoesters from dicarboxylic acid (adipic or azelaic acid), glycol (diethylene,
dipropylene or 1.4-butanediol glycol) and 2-ethylhexanol. It was conducted until an acid
value of less than 10 mgKOH/g was achieved. The second stage, on the other hand, involved

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the transesterification of waste PET using the previously synthesised oligoester using the
Fascat 4100 catalyst (Fig. 1) until a hydroxyl and acid value of less than 10 mg KOH/g was

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achieved. This made it possible to assume that the oligoesters obtained had 2-ethylhexanol
ends on both sides.

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Fascat 4100 (butylstannoic acid, BuSn(O)OH) is insoluble solid in a series of solvents and is
categorized as stable oligomeric structure at room temperature. However, on increasing the
temperature these particular arrangements can be destabilized, resulting in more active
molecular species [22]. One of the main advantages of this catalyst is lack of necessity of
neutralization or filtration at the end of reaction. Besides it provides energy savings with
lower reaction temperatures.

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According to literature data, transesterification mechanism using Lewis acid catalysts, the
acid site (in this case free tin orbital) is joining the oxygen of the carbonyl group, increasing
the electrophilicity of the adjoining carbon atom and making it more susceptible to nucleofilic
attack [23]. For this reason depolymerisation of PET chains via transesterification reaction

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using oligoesters tipped with 2-ethylhexanol takes place.

stage 1
O O
4 HOCRCOH + 3 HOR'OH + 2

stage 2

O O
CRCO
3

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O O
O CRCOR'O

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OH

O
C

O
COCH2CH2O

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Fascat 4100

products of transesterification

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Fig. 1. Scheme of obtaining of linear oligoesters of PET

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stage 1
O O
12 HOCRCOH + 9 HOR'OH + HO

OH + 3

OH

OH

O
C O
R
C O
O
R'
O

C O
R
C O
O

stage 2

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O O
O O
O CRCOR'O CRCO
3

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O O
O O
OCRC OR'OCRC O

O
C

O
COCH2CH2O

Fascat 4100

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products of transesterification

Fig. 2. Scheme of obtaining of branched oligoesters of PET

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On the basis of an analysis of 1H NMR (Fig. 3-4) and

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C NMR (Fig. 5-6) spectra it is

confirmed that both the anticipated reactions, i.e. the synthesis of oligoesters and

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transesterification, occurred. This is revealed by the fact that no free function groups, i.e.
neither hydroxyl nor carboxyl groups, were present. In plasticisers, glycols can connect on
both sides with dicarboxylic acid, on both sides with terephthalic acid (TA) or simultaneously
with dicarboxylic and terephthalic acid. All these combinations were observed in 1H NMR
spectra in the range of 3.25-5.50 ppm and in

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C NMR spectra in the range of 60-75 ppm

which were characteristic for the protons and atoms of the carbons of groups -CH2-O-, >CHO- respectively in different chemical environments. In addition, the structures of the

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compounds found in the mixture created in the reaction were confirmed through an ESI-MS
analysis. The NMR analysis is an important tool in the study of the structure of the oligomer
chain but only an ESI-MS investigation can determine the subtle differences in the chemical
structure. These spectra clearly indicate that a statistically significant transesterification

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reaction took place, where the PET chains have chemically degraded into fragments of

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different lengths.

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Fig. 3. 1H NMR (CDCl3, 300 MHz) spectra of a) oligoester DPAz and b) products of
transesterification of PET with DPAz (PETDPAz)

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Fig. 4. 1H NMR (CDCl3, 300 MHz) spectra of a) oligoester DEAzGl and b) products of

77.16 Chloroform-d

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EP

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transesterification of PET with DEAzGl (PETDEAzGl)

Fig. 5. 13C NMR (CDCl3, 75 MHz) spectrum of products of transesterification of PET with
DPAz (PETDPAz)
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Fig. 6. 13C NMR (CDCl3, 75 MHz) spectrum of products of transesterification of PET with

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DEAzGl (PETDEAzGl)

On the basis of an analysis of a sample ESI-MS spectrum of a PETDPAz specimen (Fig. 7), it

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was found that the plasticizers had 2-ethylhexanol connected with azelaic acid at their ends
(m/z= 721.3, 961.5, 1100.7, 1261.1, 1699.6 and 1999.8) or longer fragments of oligoester (-

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Az-DP-) obtained in the first stage of the synthesis (m/z = 1482.3, 2156.6 and 2306.4), where
a -TA-GE-TA- fragment constituted the core. The presence of DE (m/z = 1261.1 and 1699.6)
is the result of an ethylene glycol (EG) reaction taking place, an important side reaction in
PET synthesis [24].

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Fig. 7. ESI-MS spectra of PETDPAz

In the case of the introduction of glycerine, i.e. an additional reactant into the esterification
reaction, a regularity was observed, which differentiated these branched out plasticiser
molecules from the previously discussed linear molecules (Fig. 8). Namely, one glycerine unit

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constituted the core of a plasticizer molecule, which connected directly with a unit of TA. The
further structure of the individual arms of the oligoester branching out from the glycerine

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molecule is akin to forms created in the linear plasticisers.

Fig. 8. ESI-MS spectra of PETDEAzGl

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Table 3. The results of a gel chromatography analysis of the plasticizers obtained

Number average

Weight average

molecular weight

molecular weight

Mn (g/mol)

Mw (g/mol)

PETDEAz

1430

2500

PETDPAd

1530

2780

PETDPAz

1420

2600

PETBDAd

1610

2730

PETBDAz

1900

3400

1.80

PETDPAdGl

1590

3830

2.41

PETDPAzGl

1650

3950

2.39

PETDEAzGl

1670

3920

2.34

PETTEAd

1520

2780

1.83

H-1

2270

4230

1.87

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Dispersity

1.75

1.82

1.83

1.70

TE
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Symbol

The SEC analysis also leads to the conclusion that the degradation of waste PET occurred by
transesterification reaction, leading to the formation of the anticipated products - oligoesters

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with TA-EG- units embedded in their structure. In weight terms, the average molecular
weight in the case of linear oligoesters ranged from 2500 to 3400 g/mol, and their dispersity

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ranged from 1.70 to 1.83. However, in the case of branched oligoesters, these values ranged
from 3830 to 3950 g/mol and 2.34 to 2.41 respectively. It was found that adding glycerine to
the synthesis as a reactant caused adverse effects as it led to a significant increase in the
dispersion of the product in each and every case.
In Table 4, the viscosity designations of the synthesised plasticisers and commercial,
polymeric plasticizer (H1) are presented. The viscosity of plasticizers does not depend only
on the molecular weight, but to a large extent also on the structure of the compound obtained
and the raw materials used in the synthesis. Lower viscosity levels are observed in products
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having a branched structure, which were synthesised using glycerine. Longer aliphatic chains
produce a lower viscosity. By using the same glycols, a lower viscosity was observed in
plasticizers with azelaic acid than with adipic acid.

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Table 4. Viscosities of the plasticizers obtained

Viscosity (mPas)

PETDEAz

13 000

PETDPAd

23 500

PETDPAz

10 700

PETBDAd

30 500

PETBDAz

27 500

PETDPAdGl

9 000

PETDPAzGl

9 500

PETDEAzGl

8 750

PETTEAd

9 600

H-1

6 750

TE
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Symbol

The volatility of oligoesters at temperatures of 160, 170, 180 C was determined. In

characterising plasticisers, their volatility, particularly at higher temperatures, is an important

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parameter. Taking into account the processing temperature of plasticised PVC compositions,
it is required that the plasticizers present as low a volatility as possible, due to the possible

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loss of the plasticizer during the process as well as its escape into the environment. In
addition, the high volatility of the plasticiser makes plasticised products lose their properties
during use particularly in high temperature environments. For all the synthesised oligoesters,
the volatility values were lower compared to the volatility of the monomeric DEHP
plasticiser. At a temperature of 180 C in particular, the difference between the synthesised
products and a monomeric commercial product is significant. PETTEAd and PETBDAz
oligoesters have a volatility of 1% at this temperature. The higher volatility values of

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branched oligoesters containing glycerine correspond to higher dispersion values compared to
linear products. It is observed that the dispersion value also has an influence on the thermal
stability of oligoesters. This general tendency, along with an increase in dispersion, leads to a
decrease in thermal stability, which corresponds to a lower temperature at which a given mass

TE
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loss occurs (Fig. 9).

Fig. 9. Plasticiser mass loss versus temperature

plasticisers

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Table 5. Decomposition temperature and glass transition temperature (Tg) of the obtained

Decomposition temperature (C)

Tg (C)

PETDEAz

431.0

-44.6

PETDPAd

444.1

-47.3

PETDPAz

381.2

-45.8

PETBDAd

423.6

-46.2

PETBDAz

421.1

-51.1

PETDPAdGl

418.6

-45.5

PETDPAzGl

410.3

-48.2

PETDEAzGl

445.8

-43.6

PETTEAd

398.9

-45.3

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Composition

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H1

379.3

-49.4

The glass transition temperatures of the obtained plasticisers compared to the commercial
varieties are similar and range from -43.6 to -51.1 C.

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When comparing the decomposition temperatures of the obtained oligoesters with those of the
commercial plasticiser it was found that these compounds have a much higher thermal
stability. Only PETDPAz has a decomposition temperature which is similar to that of the

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polymeric commercial plasticiser. As shown in the diagram (Fig. 10) the mass loss curve is
also similar. The plasticiser samples containing glycerine revealed a much higher

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EP

TE
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decomposition temperature compared to its analogue varieties without glycerine.

Fig. 10. Volatility of synthesised oligoesters compared to that of commercial plasticisers

4. Conclusions

The research results proved that it is possible to use waste PET for the synthesis of new
oligoesters, which can be used as plasticisers. Taking into consideration the general
characteristics of each sample of the synthesised plasticiser and comparing them with
monomeric and polymeric commercial products, PETBDAz and PETTEAd seem to be the
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most promising. Mentioned plasticizers possessed lower volatility and much higher thermal
stability in comparison with commercial products.
It was proved that in spite of relatively high molecular mass of obtained plasticizers of
branching structure they possess lower viscosity in comparison with synthesized oligoester
However the disadvantage of these products is their high

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products of linear structure.

molecular-weight dispersity (above 2.3) what results in higher volatility.

The results of tests of the useability of the synthesised plasticisers in obtaining plasticised

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PVC compositions will be presented in a later article.

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AC
C

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bis(2-hydroxyethyl)

terephthalate

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