Progress in Organic Coatings 65 (2009) 362–365

Contents lists available at ScienceDirect

Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Alkyd resins synthesized from postconsumer PET bottles

G. Güçlü ∗ , M. Orbay
Department of Chemical Engineering, Faculty of Engineering, Istanbul University, 34320 Avcılar, Istanbul, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: Simultaneous glycolysis and neutral hydrolysis of waste PET flakes obtained from grinding postconsumer
Received 1 November 2008 bottles was carried out in the presence of xylene and an emulsifier at 180 ◦ C. The product was sepa-
Received in revised form 23 January 2009 rated from EG, water and xylene by filtration and was extracted by water at boiling point three times.
Accepted 27 February 2009
The remaining solid was named water insoluble fraction (WIF). The filtrate was cooled to 4 ◦ C and the
crystallized solid obtained by filtration was named water-soluble crystallizable fraction (WSCF). These
Keywords:
fractions were characterized by acid value (AV), hydroxyl value (HV) determinations. WSCF and WIF were
Alkyd resin
used for preparation of the alkyd resins. Three long oil alkyd resins were prepared from phthalic anhy-
Polyethylene terephthalate
Glycolysis
dride (PA) (reference alkyd resin) or depolymerization product of the waste PET (PET-based alkyd resin),
Hydrolysis glycerin (G), sunflower oil fatty acids (SOFA) and glycol (EG) (reference alkyd resin) or depolymerization
Chemical recycling product of the waste PET (PET-based alkyd resin). Film properties and thermal degradation stabilities of
these alkyd resins were investigated. Physical properties (drying times, hardness and abrasion resistance)
and thermal degradation stabilities of the PET-based alkyd resins are better than these properties of the
reference alkyd resin.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction ethylene glycol (EG), and bis(2-hydroxyethyl) terephthalate (BHET).

Polyethylene terephthalate (PET) is widely used in packaging
applications, especially in water and soft drink bottles industries
due to its clarity, light weight and selective gas permeability [1]. The
global growth in consumption of PET during the years 2001–2004
was estimated to be 2.3 million tons. Consumption in Western
Europe alone was reported to be 3.8 million tons (2003) represent-
ing to 10% of the total thermoplastic consumption [2]. PET is one
of the extensively recycled polymeric materials. The main moti-
vation for the widespread recycling of PET is its extensive use in
plastic packaging applications, especially in the beverage industry
[3]. Since PET bottles do not decompose in the nature readily, the
disposal of a large amount of PET bottles has caused serious environ-
mental problems. Today, PET bottles have become one of the most
valuable and successfully recyclable materials [4]. PET bottle col-
lection in Europe is growing steadily. Postconsumer PET collection
rates reach 796.000 tons in 2005, a 15.1% increase over the previous
year [2]. There are four main methods for recycling of waste PET,
namely primary, secondary, tertiary or chemical and quaternary
recycling [5]. The chemical recycling of waste PET can be carried out
in many ways such as glycolysis, hydrolysis, alkolysis and simulta-
neous hydrolysis and glycolysis. The aim of most chemical recycling
procedures is obtaining monomers such as terephthalic acid (TPA),
∗ Corresponding author. Fax: +90 212 473 71 80.
E-mail address: gguclu@istanbul.edu.tr (G. Güçlü).
The first two can be obtained by hydrolysis under neutral [6],
acidic [7] or alkaline [5,8,9] conditions and the last by glycolysis
[4,10] of waste PET. All these methods have recently been reviewed
by Karayannidis and Achilias [2]. In addition, BHET and monohy-
droxyethyl terephthalate (MHT) were obtained by simultaneous
application of glycolysis and hydrolysis [11].
Waste PET can be depolymerized by glycolysis to obtain
oligomeric diols such as BHET dependent on process conditions.
The PET glycolysis products were used for the synthesis of saturated
and unsaturated polyesters [12–14], polyurethanes [15,16], coating
materials [17,18], and additives [17]. But there is no report on using
of simultaneous hydrolysis and glycolysis products of waste PET for
synthesis of different polymers such as coating materials, polyesters
and additives.
In the present work, we report the results from our investi-
gations on the possibility for using simultaneous hydrolysis and
glycolysis products of waste PET in alkyd resins manufacturing.
2. Experimental
2.1. Materials
Waste PET flakes obtained from grinding postconsumer bottles
were sieved to obtain a 10–20 mesh fraction. This viscosity average
molecular weight (Mv ) was found to be 3.7 × 104 [6,11]. Sunflower
oil (SOFA) was used in the preparation of alkyd resins. Other mate-
rials were obtained from Merck.

0300-9440/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2009.02.004
 G. Güçlü, M. Orbay / Progress in Organic Coatings 65 (2009) 362–365
Table 1
Alkyd resins.
Symbol of the alkyd resins Raw materials
Fatty acid
A-WSCF SOFA
A-WIF SOFA
A-REF SOFA
2.2. Simultaneous hydrolysis and glycolysis reactions
In previous work, simultaneous glycolysis and neutral hydrolysis
of waste PET with constant amount of EG and increasing amounts
of water (1 mol EG, 0–13 mol H2 O per mole PET) was carried out at
170 and 190 ◦ C. The oligomeric intermediates products from waste
PET were obtained by application of simultaneous glycolysis and
hydrolysis [11]. In this work, simultaneous glycolysis and neutral
hydrolysis of waste PET was carried out in the presence of xylene
and an emulsifier at 180 ◦ C. Reaction conditions were determined
according to the required properties [acid value (AV) and hydroxyl
value (HV)] of the product. The procedure of the application of
simultaneous glycolysis and hydrolysis was given below:
The reactions were carried out in 1 L stainless steel pressure
reactor equipped with a stirrer, temperature control system and
cooling coil. The temperatures of 180 ◦ C were attained in 1 h and
the reaction was continued for three hours. The charges consisted
of 100 g of PET and 31 g EG (corresponding to a molar ratio of 1/1
based on the molecular weights of the repeating unit of PET and
EG), 250 mL xylene, 0.5 g of Tween-60 surfactant, 1 g of zinc acetate
catalyst and 60 g water (approximate molar ratio of H2 O/PET of
7/1). After the reaction, the reactor was cooled to room temper-
ature in 15–20 min by circulating water through the cooling coils
and immersion in running water. The powder product was sepa-
rated from EG, water and xylene by filtration and was extracted
by 1 L water at boiling point three times. The remaining solid was
named water insoluble fraction (WIF). The filtrate was cooled to 4 ◦ C
and the crystallized solid obtained by filtration was named water-
soluble crystallizable fraction (WSCF). WIF and WSCF were dried
under vacuum at 30–40 ◦ C.
The reaction products, when extracted with boiling water,
yielded a WSCF and a WIF. These fractions were characterized by
AV, HV determinations. HV was determined by acetylation of sam-
ples dissolved in pyridine by acetic anhydride, followed by back
titration of excess reagent with 1 N NaOH solution [6,11]. AV was
determined by titration of samples dissolved in pyridine with 0.1N
KOH solution. The Mn value of depolymerization product was calcu-
lated from HV and AV by the known formula of end group analysis
method [19,20]. The Mn value (number-average molecular weight)
is calculated from Eq. (1):
2 × 56.1 × 1000
Mn =
HV + AV
2.3. Preparation of alkyd resins
Alkyds formulated to have oil content 60% were prepared with
phthalic anhydride (PA) or simultaneous hydrolysis and glycolysis
products, glycerine (G), sunflower oil fatty acid (SOFA) and EG. The
Table 2
Conditions of simultaneous glycolysis and hydrolysis reactions and properties of reaction products.
Product Temperature (◦ C) PETa /H2 O (molar ratio) PETa /EG (molar ratio)
WIF 180 1/7 1/1
WSCF
a
Based on the molecular weights of the repeating unit of PET.
b
Calculated from HV and AV.
363
AV (mg KOH/g)
Polyol Diol Dicarboxylic acid
G WSCF PA + WSCF 6
G WIF + EG WIF 6.5
G EG PA 7.5
combinations and AV of alkyd resins are shown in Table 1. “K alkyd
constant system” was used for the formulation calculations of the
alkyd resins [21]. The K constant was 1.15 and the ratio of basic
equivalents to acid equivalents (R) was 1.2. The reaction was carried
out in a round bottom flask equipping with a Dean–Stark piece,
gas bubbler, contact thermometer and mechanical stirrer system.
The temperature of the reaction was kept constant at 220–240 ◦ C.
The reactions were followed with acid value (AV). Condensation
reaction was allowed to continue until the acid value of the resin
was approximately 6–7 mgKOH/g. The acid values were determined
by titration of samples dissolved in ethanol–toluene with 0.1 N KOH
solution. After the reaction the resins were dissolved in xylene (60%
solution).
2.4. Testing of alkyd resin films
For alkyd tests, 60% solutions of the resins in xylene, containing
1% Pb and 0.1% Co (based on non-volatile) were prepared. Films cast
by 50 ␮m applicators from the solutions were dried at 25 ± 1 ◦ C for
72 h.
Drying time was determined by an Ericsen 415/E apparatus,
which gave results according to DIN 53150. For hardness, a Konig
Pendulum, which gave results according DIN 53157 was used. Adhe-
sion strength of the films was determined by the cross-cut method
according to ASTM D 3359-76.
Abrasion resistance is usually performed with a falling sand
abrasion test. Sand is dropped down a vertical tube onto the panel
that is mounted at a 45o angle. The results are given as the amount
of sand required removing a certain thickness of coating [22]. Abra-
sion resistance was determined by an Ericsen Send Abrasion Tester,
type 2511-11, which gave results according to ASTM 9685.
The effect of water immersion was determined according to
ASTMD1647-59 by immersion in water for 18 h.
All tests were repeated three times to confirm the repeatability
of the tests.
2.5. Thermogravimetric analysis (TGA)
Thermogravimetric analysis (TGA) was carried out by Linseis L81
under air at a rate of 5 ◦ C/min with 20 mg of alkyd resins.
(1)
3. Results and discussion
3.1. Simultaneous hydrolysis and glycolysis of waste PET
The simultaneous hydrolysis and glycolysis of waste PET was
carried out by using EG and H2 O in the presence of xylene and an
emulsifier at 180 ◦ C. After the reaction, the product was separated
AV (mg KOH/g) HV (mg KOH/g) Yield (w/w) (%) Mn b
365 70 50 258
190 350 50 208
364 G. Güçlü, M. Orbay / Progress in Organic Coatings 65 (2009) 362–365
Table 3
Physical properties of the alkyd resin films.
Alkyd resins Drying degreea
A-WSCF 3 13
A-WIF 3 12
A-REF 1 10
a
Drying degree of the alkyd films after 24 h.
from EG, water and xylene by filtration and was extracted by boil-
ing water three times. The remaining solid was named WIF. The
filtrate was cooled to 4 ◦ C and the crystallized solid obtained by
filtration was named WSCF. HV and AV of the WIF and WSCF were
determined and these data were used for the calculation of number-
average molecular weight (Mn ) of these products. The properties
of the products and reaction conditions are given in Table 2. With
application of simultaneous glycolysis and hydrolysis, WSCF was
found to be mainly composed of BHET and MHT. In case of WIF, the
product consist of the higher oligomers and the amount of carboxyl
ended oligomers in the product increase [11]. As shown in Table 2,
AV of the WIF is higher than AV of the WSCF and WIF (%), WSCF (%)
yields of the product are 50–50%.
3.2. Alkyd resins
WSCF and WIF were used for preparation of the alkyd resins
Three long oil alkyd resins were prepared from PA (reference alkyd
resin) or WIF/WSCF (PET-based alkyd resin), glycerin (G), sun-
flower oil fatty acids (SOFA) and glycol (EG) (reference alkyd resin)
or WIF/WSCF (PET-based alkyd resin). The combinations of alkyd
resins are shown in Table 1. The alkyd reactions were followed with
AV determinations. Changes in the AV with an increasing time of
reaction for the alkyd samples are shown in Fig. 1. These plots show
that as the reaction progressed, the AV decreased. The decreased
in AV is more rapid during the early stages of the reaction than
the later stages of reaction. This pattern of changes in AV during
polycondensation reaction has been explained on the basis of the
different reactivities of primary and secondary groups of polyol.
Because a primary hydroxyl group reacts faster than a secondary
hydroxyl group, it is believed that the rapid decrease in AV at the
early stages of reaction corresponds to the period when primary
hydroxyl groups react, whereas the later stage represents the period
when secondary hydroxyl groups react [23]. As shown in Fig. 1,
there are no differences between the reaction rate of the PET-based
resins and the reference resins and the final acid value of the alkyds
fell to considerable low values.
Fig. 1. The change of the acid value with reaction time.
Hardness (Konig s) Abrasion resistance (mL sand)
8000
9000
3750
3.3. Film properties of the alkyd resins
For alkyd tests, 60% solutions of the resins in xylene, containing
1% Pb and 0.1% Co (based on non-volatile) were prepared by using
50 ␮m applicators. Determination of drying time of the resins is
estimated by adherence or non-adherence of paper or glass beads.
There are seven drying stages of this method, and the maximum
drying degree is 7. Stage 1 is determined with glass beads and the
remaining stages are determined with disks of typewriter paper
(loads range from 5 to 5000 g/cm2 ). The glass beads are allowed to
remain on the film for 10 s, and the loads on the disks remain for 60 s.
As shown in Table 3, physical properties (drying times, hardness
and abrasion resistance) of the PET-based alkyd resins are better
than physical properties of the reference alkyd resin (A-REF). PA
was used as dicarboxylic acid in the production of A-REF. Since the
carboxyl groups of PA are located in orthoposition, steric hindrance
is observed so the reaction occurs more difficult. On the other hand,
in PET-based alkyd resins, end groups of the oligomeric intermedi-
ates are located in paraposition so the reactions proceed easier and
the films that have better physical properties are obtained from
these alkyds. The percentages of the adhesion strength of the alkyd
resin films are 100%. The effect of water immersion (18 h) was deter-
mined by a water resistance test; the films were not affected by the
water after 18 h. Both of the PET-based resins and reference resins
have the same water resistance values.
3.4. Thermogravimetric analysis
Thermal oxidative degradations of the alkyd resins were investi-
gated by TGA under an air atmosphere at a heating rate of 5 ◦ C/min.
Results are presented in Fig. 2. The TGA curves indicate that all
resins show almost the same degradation behaviors. The A-REF
resin showed the worst resistance to thermal oxidative degrada-
tion with 75 and 100% weight losses at 375 and 475 ◦ C, respectively.
Weight losses of 75% at 425 ◦ C and 100% at 500 ◦ C show that PET-
based alkyd resins were more stable than reference resin. This
can be attributed to the presence of oligomeric intermediates,
which are bigger aromatic molecules, instead of the PA and EG
Fig. 2. TGA curves of alkyd resins.
 G. Güçlü, M. Orbay / Progress in Organic Coatings 65 (2009) 362–365 365

in the alkyd structure that improve the thermal stability of alkyd Acknowledgement
resins.
This work was financially supported by the Research Fund of
4. Conclusions Istanbul University, Project No. 594/171193.

Waste PET flakes obtained from postconsumer PET bottles were References
depolymerized by using EG and water in the presence of zinc acetate [1] V. Pimpan, R. Sirisook, S. Chuayjuljit, J. Appl. Polym. Sci. 8 (2003) 788.
as catalyst. Depolymerization products (WIF and WSCF) were used [2] G.P. Karayannidis, D.S. Achilias, Macromol. Mater. Eng. 292 (2007) 128.
for the preparation of PET-based alkyd resin. In this work, three long [3] D.E. Nikles, M.S. Farahat, Macromol. Mater. Eng. 290 (2005) 13.
[4] H.C. Chen, J. Appl. Polym. Sci. 87 (2003) 2004.
oil alkyd resins were prepared (A-WSCF, A-WIF and A-REF). The
[5] G.P. Karayannidis, A.P. Chatziavgoustis, D.S. Achilias, Adv. Polym. Technol. 21
film properties and thermal stability of these resins were inves- (2002) 250.
tigated. Physical properties (drying times, hardness and abrasion [6] G. Güçlü, T. Yalçınyuva, S. Özgümuş¸, M. Orbay, Thermochim. Acta 404 (2003)
resistance) of the PET-based alkyd resins (A-WIF and A-WSCF) are 193.
[7] T. Yoshioka, T. Motoki, A. Okuwaki, Ind. Eng. Chem. Res. 40 (2001) 75.
better than physical properties of the reference alkyd resin (A-REF). [8] B. Wan, C. Kao, W. Cheng, Ind. Eng. Chem. Res. 40 (2001) 509.
Both of the PET-based resins and reference resins have the same [9] C. Kao, W. Cheng, B. Wan, J. Appl. Polym. Sci. 70 (1998) 1939.
water resistance values. The percentages of the adhesion strength [10] G. Güçlü, A. Kaşgöz, S. Özbudak, S. Özgümüş¸, M. Orbay, J. Appl. Polym. Sci. 69
(1998) 2311.
of the alkyd resin films are 100%. Thermal oxidative degradations [11] G. Güçlü, T. Yalçınyuva, S. Özgümuş¸, M. Orbay, Polymer 44 (2003) 7609.
of the alkyd resins were investigated by TGA under an air atmo- [12] U.R. Vaidya, V.M. Nadkarni, J. Appl. Polym. Sci. 34 (1987) 235.
sphere at a heating rate of 5 ◦ C/min. The reference resin showed [13] Y. Öztürk, G. Güçlü, Polym. Plast. Technol. Eng. 43 (2004) 1539.
[14] D.J. Suh, O.O. Park, K.H. Yoon, Polymer 41 (2000) 461.
the worst resistance to thermal oxidative degradation. PET-based [15] N. Halacheva, P. Novakov, Polymer 36 (1995) 867.
alkyd resins were more stable than reference resin. The main pur- [16] M. Billiau-Loreau, G. Durand, G. Tersac, Polymer 43 (2002) 21.
pose of this work is investigations on the possibility for using [17] D. Paszun, T. Spychaj, Ind. Eng. Chem. Res. 36 (1997) 1373.
[18] A. Torlakoğlu, G. Güçlü, Waste Manage. 29 (2009) 350.
hydrolysis glycolysis products of waste PET in alkyd resins man- [19] B.H. Stuart, Polymer Analysis, Wiley, England, 2002.
ufacturing. The results show that the thermal stability and physical [20] M.S. Farahat, A.A. Abdel-Azim, M.E. Abdel-Raowf, Macromol. Mater. Eng. 283
film properties of PET-based alkyd resins were better than reference (2000) 1.
[21] T.C. Patton, Alkyd Resin Technology, John Wiley and Sons, New York, USA, 1962.
alkyd resin (phthalic anhydride-based resin). As a result, depoly-
[22] E. Küçükoğlu, I. Acar, T.B. İyim, S. Özgümüş, J. Appl. Polym. Sci. 104 (2007) 3324.
merization products of waste PET (WIF and WSCF) are suitable for [23] C. Kawamura, K. Ito, R. Nishida, I. Yoshihara, N. Numa, Prog. Org. Coat. 45 (2004)
manufacturing of alkyd resins. 185.