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This article was downloaded by [Lulea University of Technology]On 14 September 2013 At 1752Publisher Taylor amp FrancisInforma Ltd Registered in England and Wales Registered Number 1072954 Registered office MortimerHouse 37-41 Mortimer Street London W1T 3JH UK
Polymer-Plastics Technology and EngineeringPublication details including instructions for authors and subscription informationhttpwwwtandfonlinecomloilpte20
Unsaturated Polyester Resins Obtained fromGlycolysis Products of Waste PETYeliz Oumlztuumlrk a amp Gamze Guumlccedilluuml aa Department of Chemical Engineering Faculty of Engineering Istanbul UniversityAvcılar Istanbul TurkeyPublished online 14 Feb 2007
To cite this article Yeliz Oumlztuumlrk amp Gamze Guumlccedilluuml (2005) Unsaturated Polyester Resins Obtained from Glycolysis Products ofWaste PET Polymer-Plastics Technology and Engineering 435 1539-1552 DOI 101081PPT-200030272
To link to this article httpdxdoiorg101081PPT-200030272
PLEASE SCROLL DOWN FOR ARTICLE
Taylor amp Francis makes every effort to ensure the accuracy of all the information (the ldquoContentrdquo) containedin the publications on our platform However Taylor amp Francis our agents and our licensors make norepresentations or warranties whatsoever as to the accuracy completeness or suitability for any purpose ofthe Content Any opinions and views expressed in this publication are the opinions and views of the authorsand are not the views of or endorsed by Taylor amp Francis The accuracy of the Content should not be reliedupon and should be independently verified with primary sources of information Taylor and Francis shallnot be liable for any losses actions claims proceedings demands costs expenses damages and otherliabilities whatsoever or howsoever caused arising directly or indirectly in connection with in relation to orarising out of the use of the Content
This article may be used for research teaching and private study purposes Any substantial or systematicreproduction redistribution reselling loan sub-licensing systematic supply or distribution in anyform to anyone is expressly forbidden Terms amp Conditions of access and use can be found at httpwwwtandfonlinecompageterms-and-conditions
POLYMERndashPLASTICS TECHNOLOGY AND ENGINEERING
Vol 43 No 5 pp 1539ndash1552 2004
Unsaturated Polyester Resins Obtained from
Glycolysis Products of Waste PET
Yeliz Ozturk and Gamze Guclu
Department of Chemical Engineering Faculty of Engineering
Istanbul University Avcilar Istanbul Turkey
ABSTRACT
Waste polyethylene terephthalate (PET) flakes were depolymerized
by using ethylene glycol (EG) propylene glycol (PG) diethylene
glycol (DEG) and triethylene glycol (TEG) in the presence of zinc
acetate as catalyst All glycolysis products were reacted with maleic
anhydride and mixed with styrene monomer to get unsaturated
polyester (UP) resins Molecular weights of all synthesized UP resins
were determined by end-group analysis The curing characteristics
such as gel time and maximum curing temperatures and mechanical
properties such as hardness tensile strength and elastic module of
these resins were investigated The waste PET resins were compared
with the reference resins prepared with the same glycols and the
Correspondence Gamze Guclu Department of Chemical Engineering Faculty
of Engineering Istanbul University Avcilar Istanbul 34320 Turkey Fax thorn90
212 591 19 97 E-mail ggucluistanbuledutr
1539
DOI 101081PPT-200030272 0360-2559 (Print) 1525-6111 (Online)
Copyright amp 2004 by Marcel Dekker Inc wwwdekkercom
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properties of the resins were found to be compatible with the
properties of the reference resins
Key Words Unsaturated polyester resin Polyethylene terephtha-
late Glycolysis Chemical recycling
INTRODUCTION
Recycling of plastics has been widely investigated in recent yearsPolyethylene terephthalate (PET) is a thermoplastic polymer which isproduced in considerable amounts The PET is widely used in themanufacture of high strength fibers audio and video tapes and varioustypes of packaging mainly bottles and jars[1] The overall worldconsumption of PET amounts to about 13 million tons of which 15million tons is used in the manufacture of various types of packaging[2]
In recent years the effective utilization of PET wastes became veryimportant Globally around 17 of PET bottle consumption wascollected for recycling in 1999[3] During the last eight years an almost10-fold increase in the amount of bottles collected for recycling in Europehas been observed (450000 tons in 2003 compared to 45000 tons in1995)[34]
The aim of most chemical recycling procedures for waste PET isobtaining monomers such as terephthalic acid (TPA) ethylene glycol(EG) and bis(2-hydroxy ethyl) terephthalate (BHET) The first twocompounds can be obtained by hydrolysis under neutral acidic oralkaline conditions and the last by glycolysis of waste PET A reviewsummarizes the research and applications up to 1997[2] After 1997papers involved alkaline[5ndash7] and acidic[8] hydrolysis and glycolysis[910] ofwaste PET
Vaidya et al[11ndash13] suggested the synthesis of unsaturated polyester(UP) resins from waste PET Aslan et al[14] compared the compositesheet containing unsaturated polyester developed in recycled PET tothe analogous composite made of virgin UP resin Farahat et al[15]
investigated the capability of modifying the properties of synthesized UPresins by incorporation of p-hydroxybenzoic acid as an ingredient insynthesizing these polyester resins Suh et al[16] compared the propertiesof UP resins prepared by glycolysis of PET with propylene glycol (PG)and diethylene glycol (DEG) and their mixture
In this work we tried to compare the curing and mechanicalproperties of UP resins prepared from glycolysis products of waste PETobtained by using various glycol compounds and their mixture
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EXPERIMENTAL
Materials
Waste PET flake obtained from grinding postconsumer bottles wassieved to obtain a 10ndash20 mesh fraction The viscosity average molecularweight ethMV THORN was found to be 37 104[17] Distilled water was used forextractions The rest of the materials were Merck synthesis or analyticalgrade
Glycolysis Reactions
The waste PET was depolymerized in EG (PETEG molar ratio 16)PG DEG triethylene glycol (TEG) and PGndashTEG mixture (PGTEGmolar ratio 11) [(PETglycol molar ratio (125)] using 1 (ww) zincacetate based on weight of PET as catalyst The glycolysis reactionswere carried out at 190ndash220C for 6 h in a round-bottom flask equippedwith a reflux system gas bubblier contact thermometer and mechanicalstirrer system
After the reaction hydroxyl value (HV) of the reaction mixture wasdetermined without removal of free glycol compound Then the reactionmixture was extracted with boiling water three times and filtrated forseparation of the solid fraction The water soluble crystallizable fraction(WSCF) was obtained by cooling to 4C for only glycolysis productwhich was obtained by using EG in the reaction The water insolublefraction (WIF) and WSCF were dried under vacuum at 30ndash40C Thehydroxyl values of the glycolysis products after glycol removal weredetermined
The HV of products was determined by the acetylation method[18]
A differential scanning coloumetry (DSC) scan of WSCF wasobtained with a Seteram DSC 131 calorimeter with 30mg samples with arate of 5Cmin in nitrogen atmosphere
Preparation of Unsaturated Polyester Resins
The unsaturated polyester (UP) resins which were prepared byreacting the glycolysis products with maleic anhydride at an OHCOOHmolar ratio of 111HV of the glycolysis products without separationof free glycol were used to determine the amount of maleic anhydride
Unsaturated Polyester Resins 1541
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Only one of the UP resins was prepared by reacting the WSCF and PGmixture with maleic anhydride
The polyesterification reactions were carried out in a round-bottomflask equipped with a reflux system Dean-Stark equipment gas bubbliercontact thermometer and mechanical stirrer system The reactants wereheated from room temperature to 190C in nitrogen atmosphere in about1 h The temperature was held at 190C and maintained until the acidvalue of the reaction mixture reached about 30ndash60mg KOHg Waterformed during the reaction was removed by using xylene as a solvent
The acid values (AV) were determined by the volumetric method[19]
Molecular weight determinations of all UP resins were carried outby end-group analysis[15]
The UP resins were added to styrene monomer at 80C to get 35(ww) styrene in the resins The curing characteristics such as gel time andmaximum curing temperature of all the resins were investigated The geltime and maximum curing temperature were determined using methyl-ethylketone peroxide (MEKP) [15 (ww) of resins] as the initiator andcobalt naphthenate [1 (ww) of the resins] as the accelerator
In order to compare the properties of UP resins reference resins wereprepared from maleic anhydride phthalic anhydride and one of theglycol compounds such as PG DEG TEG or PG-TEG mixture
Tensile strength and elastic module of UP resins were determinedwith Hounsfield H10KS Universal Testing Machine and hardness of UPresins was determined by using Barcol 934-1 and Shoremeter HardnessTesting Machines
RESULTS AND DISCUSSION
The glycolysis of waste PET was carried out by using EG PG DEGTEG and PG-TEG mixtures as glycol compounds in the presence of zincacetate as catalyst at 190ndash220C The HVs of the glycolysis products weredetermined and are given in Table 1
The glycolysis reaction product of waste PET obtained by using thePETEG molar ratio 16 was extracted by 250mL water at the boilingpoint three times The solid fraction was named water insoluble fraction(WIF) The filtrates were collected and cooled to 4C and crystallizedsolids obtained by filtration were named water soluble crystallizablefraction (WSCF) (the weight ratio of WSCF in total product is 85)The HV of the WSCF is comparable to that of BHET implying that theextent of depolymerization is quite significant (Table 1) This product(GP1) consists mainly of BHET monomer A DSC scan of the WSCF of
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GP1 is presented in Fig 1 There is an endothermic peak at 110C thatindicated the melting point of BHET When PET is depolymerized byusing EG and the glycolysis products are used for the preparation ofunsaturated polyester the resins are not compatible with styrene[11]
In order to prepare G-UPR1 the WSCF of GP1 and PG mixturewas polyesterified with maleic anhydride (MA) at a 11 molar ratio ofOHCOOH
In the case of glycols the compounds were PG DEG TEG andPGndashTEG mixtures The molar ratio of PETglycol was 125 The HV ofthese products changes between 250 and 300 according to type of glycolcompound (Table 1) This indicates that there is a considerable extent of
0
5
10
15
70 90 110 130 150Temp (degC)
End
o
Figure 1 DSC scan of WSCF of GP1
Table 1 HV of glycolysis products
Symbol of
product
Glycol
compound
Analysis of glycolyzed products
Before free
glycol removal
After free
glycol removal
HV (mgKOHg) HV (mg KOHg)
GP1 EG 750 440
GP2 PG 550 300
GP3 DEG 480 270
GP4 TEG 400 250
GP5 PGndashTEG 470 260
Unsaturated Polyester Resins 1543
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depolymerization and the glycolysis products mainly contained hydroxyl-terminated monomer and dimer mixtures The UP resins were preparedby reacting the glycolysis products (GP2 GP3 GP4 GP5) with MAThe resins formed were referred to as G-UPR2 G-UPR3 G-UPR4 andG-UPR5 respectively
Reference resins R-UPR1 R-UPR2 R-UPR3 and R-UPR4 wereprepared from MA phthalic anhydride (PA) and PG DEG TEG orPG-TEG mixture respectively at the same molar ratio of MAPA andOHCOOH as previously indicated
Figures 2ndash5 show the change of AV of resins based on waste PETand reference resins with the reaction time It is clear that polycondensa-tion of glycolysis products with maleic anhydride was faster than those ofthe reference resins It also means that the extent of depolymerizationincreases with the reaction time in the first stage and finally reaches anequilibrium value in approximately three hours which is a generalcharacteristic of condensation reactions
The HV and AV of UP resins were determined and these data wereused for the calculation of number average molecular weight ethMnTHORN ofthese resins[15] The ethMnTHORN is calculated from Eq (1) The AV HV andcalculated ethMnTHORN of the UP resins are presented in Table 2
Mn frac142 561 1000
AVthornHVeth1THORN
The UP resins were added in styrene monomer at 80C to get 35(ww) styrene in the resins Gel times maximum curing temperatures
0
50
100
150
200
250
300
350
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR1
G-UPR2
R-UPR1
Figure 2 The change of acid value with reaction time for G-UPR1 G-UPR2
and R-UPR1
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and time required to reach this temperatures of the resins (peak time)were determined by using 15 (ww) MEKP and 1 (ww) cobaltnaphthanate to resins The results are reported in Fig 6 and Table 3Each set of UP resins prepared from the different glycolysis products iscollected in one graph in order to study the effect of the different glycols
0
50
100
150
200
250
300
0 100 200 300 400Time (min)
AV
(mg
KO
Hg
)
G-UPR3
R-UPR2
Figure 3 The change of acid value with reaction time for G-UPR3 and
R-UPR2
0
50
100
150
200
250
300
0 100 200 300Time (min)
AV
(mg
KO
Hg
)
G-UPR4
R-UPR3
Figure 4 The change of acid value with reaction time for G-UPR4 and
R-UPR3
Unsaturated Polyester Resins 1545
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on the curing behavior in Fig 6 Maximum curing temperatures ofG-UPR1 and G-UPR2 (UP resins based on PG glycolyzed product) arehigher than they are for G-UPR3 and G-UPR4 (UP resins based onDEG and TEG glycolysis products) Time required to reach thistemperature and gel time of G-UPR1 and G-UPR2 are shorter thanare those of G-UPR3 and G-UPR4 These properties of G-UPR5 (UPresin based on PG-TEG glycolysis product) were seen to be nearly in themiddle of the other resins (Fig 6) Curing properties of waste PET-basedresins are comparable with the reference resins (Table 3 and Figs 7ndash10)
0
50
100
150
200
250
300
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR5
R-UPR4
Figure 5 The change of acid value with reaction time for G-UPR5 and
R-UPR4
Table 2 AV HV and calculated ethMnTHORN of the UP resins
Symbol of resins AV (mgKOHg) HV (mgKOHg) Calculated ethMnTHORN
G-UPR1 40 75 975
G-UPR2 30 85 975
G-UPR3 30 90 950
G-UPR4 35 85 950
G-UPR5 30 85 950
R-UPR1 60 85 975
R-UPR2 60 85 800
R-UPR3 60 85 800
R-UPR4 60 85 800
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The mechanical properties of the UP resins are presented in Table 4As seen hardness tensile strength and the elastic module of the G-UPR1and G-UPR2 are higher than are those of the other UP resins Butelongation at break percent values of these resins are lower than the otherresins The DEG and TEG units are more flexible than the PG unit dueto the ether linkage The mechanical properties of the PET based resinsare comparable with the reference resins (Table 4)
0
20
40
60
80
100
120
140
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
G-UPR3
G-UPR4
G-UPR5
Figure 6 Maximum curing temperatures of waste PET-based UP resins
Table 3 Curing properties of the UP resins
Symbol
of resins
Gel
time (min)
Max curing
temperature (C)
Peak
time (min)
G-UPR1 10 128 18
G-UPR2 13 103 23
G-UPR3 28 60 50
G-UPR4 33 53 60
G-UPR5 18 75 37
R-UPR1 9 130 17
R-UPR2 33 63 57
R-UPR3 32 65 54
R-UPR4 17 99 32
Unsaturated Polyester Resins 1547
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CONCLUSION
The PET-based unsaturated polyester resins were prepared byreacting the glycolysis products of waste PET with maleic anhydrideReference resins were prepared from maleic anhydride phthalicanhydride and one of the glycol compounds such as PG DEG TEG
0
20
40
60
80
100
120
140
0 10 20 30 40Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
R-UPR1
Figure 7 Maximum curing temperatures of G-UPR1 G-UPR2 and R-UPR1
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR3
R-UPR2
Figure 8 Maximum curing temperatures of G-UPR3 and R-UPR2
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or PGndashTEG mixture at the same OHCOOH molar ratio with the wastePET based resins
The mechanical properties and curing behaviors of the waste PET-based UP resins are comparable with the reference resins The DEG- andTEG-based resins are more flexible than are PG-based resins due to theether linkage But PG-based resins have higher tensile strength andhardness than do DEG- and TEG-based resins It appears that it isfeasible to recycle waste PET as UP resins by glycolysis reactions usingdifferent glycol compounds and glycol compounds mixtures
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR4
R-UPR3
Figure 9 Maximum curing temperatures of G-UPR4 and R-UPR3
0
20
40
60
80
100
120
0 10 20 30 40 50Time (min)
Tem
p (
degC)
G-UPR5
R-UPR4
Figure 10 Maximum curing temperatures of G-UPR5 and R-UPR4
Unsaturated Polyester Resins 1549
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ACKNOWLEDGMENTS
This work was financially supported by the Research Foundation of
Istanbul University Project Number T-14706032003
REFERENCES
1 Mansour SH Ikladious NE Depolymerization of poly(ethylene
terephthalate) wastes using 14-butandiol and triethylene glycol
Polymer Testing 2002 21 (5) 497ndash5052 Paszun D Spychaj T Chemical recycling of poly(ethylene
terephthalate) Ind Eng Chem Res 1997 36 1373ndash13833 Kosmidis VA Achilias DS Karayannidis GP Poly(ethylene
terephthalate) recycling and recovery of pure terephthalic acid
Kinetics of a phase transfer catalyzed alkaline hydrolysis Macromol
Mater Eng 2001 286 640ndash6474 Petcore News No 1 April 2003 PET Container Recycling Europe
(Petcore) Belgium5 Wan B Kao C Cheng W Kinetics of depolymerization of
poly(ethylene terephthalate) in potassium hydroxide solution Ind
Eng Chem Res 2001 40 509ndash5146 Kao C Cheng W Wan B Investigation of alkaline hydrolysis of
polyethylene terephthalate by differential scannig calorimetry and
thermogravimetric analysis J Appl Polym Sci 1998 70 1939ndash1945
Table 4 Mechanical properties of the UP resins
Symbol
of resins
Hardness
(ShoreBarkol)
Tensile
strength (MPa)
Elastic
module (MPa)
Elongation at
break point ()
G-UPR1 30 (Barkol) 12 40 14
G-UPR2 10 (Barkol) 10 35 16
G-UPR3 95 (Shore) 25 5 69
G-UPR4 80 (Shore) 15 25 72
G-UPR5 99 (Shore) 10 50 19
R-UPR1 45 (Barkol) 15 90 10
R-UPR2 92 (Shore) 35 5 69
R-UPR3 85 (Shore) 17 35 70
R-UPR4 99 (Shore) 99 65 15
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7 Karayannidis GP Chatziavgoustis AP Achilias DS
Poly(ethylene terephthalate) recycling and recovery of pure
terphthalic acid by alkaline hydrolysis Adv Polym Technol
2002 21 (4) 250ndash2598 Yoshioka T Motoki T Okuwaki A Kinetics of hydrolysis of
poly(ethylene terephthalate) powder in sulfuric acid by a modified
shrinking-core model Ind Eng Chem Res 2001 40 75ndash799 Guclu G Kas goz A Ozbudak S Ozgumus S Orbay M
Glycolysis of poly(ethylene terephthalate) wastes in xylene J Appl
Polym Sci 1998 69 2311ndash231910 Chen CH Chen CY Lo YW Mao CF Liao WT Studies
of glycolysis of poly(ethylene terephthalate) recycled from post-
consumer soft-drink bottles I influences of glycolysis conditions
J Appl Polym Sci 2001 80 943ndash94811 Vaidya UR Nadkarni VM Unsaturated polyester resins from
poly(ethylene terephthalate) waste 1 Synthesis and characteriza-
tion Ind Eng Chem Res 1987 26 194ndash19812 Vaidya UR Nadkarni VM Unsaturated polyester resins
from poly(ethylene terephthalate) waste 2 Mechanical and
dynamic mechanical properties Ind Eng Chem Res 1988 27
2056ndash206013 Vaidya UR Nadkarni VM Unsaturated polyester resins from
PET waste kinetics of polycondensation J Appl Polym Sci 1987
34 235ndash24514 Aslan S Immirzi B Laurienzo P Malinconico M Martuscelli
E Volpe MG Pelino M Savini L Unsaturated polyester resins
from glycolysed waste polyethylene terephthalate synthesis and
comparison of properties and performance with virgin resin
J Mater Sci 1997 32 2329ndash233615 Farahat MS Abdel-Azim AA Abdel-Raowf ME Modified
unsaturated polyester resins synthesized from poly(ethylene
terephthalate) waste 1 Synthesis and curing characteristics
Macromol Mater Eng 2000 283 1ndash616 Suh DJ Park OO Yoon KH The properties of unsaturated
polyester based on the glycolyzed poly(ethylene terephthalate) with
various glycol compositions Polymer 2000 41 461ndash46617 Guclu G Yalcinyuva T Ozgumus S Orbay M Hydrolysis of
waste polyethylene terephthalate and characterization of products
by differential scanning calorimetry Thermochimica Acta 2003
404 (1ndash2) 193ndash205
Unsaturated Polyester Resins 1551
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18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
1552 Ozturk and Guclu
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POLYMERndashPLASTICS TECHNOLOGY AND ENGINEERING
Vol 43 No 5 pp 1539ndash1552 2004
Unsaturated Polyester Resins Obtained from
Glycolysis Products of Waste PET
Yeliz Ozturk and Gamze Guclu
Department of Chemical Engineering Faculty of Engineering
Istanbul University Avcilar Istanbul Turkey
ABSTRACT
Waste polyethylene terephthalate (PET) flakes were depolymerized
by using ethylene glycol (EG) propylene glycol (PG) diethylene
glycol (DEG) and triethylene glycol (TEG) in the presence of zinc
acetate as catalyst All glycolysis products were reacted with maleic
anhydride and mixed with styrene monomer to get unsaturated
polyester (UP) resins Molecular weights of all synthesized UP resins
were determined by end-group analysis The curing characteristics
such as gel time and maximum curing temperatures and mechanical
properties such as hardness tensile strength and elastic module of
these resins were investigated The waste PET resins were compared
with the reference resins prepared with the same glycols and the
Correspondence Gamze Guclu Department of Chemical Engineering Faculty
of Engineering Istanbul University Avcilar Istanbul 34320 Turkey Fax thorn90
212 591 19 97 E-mail ggucluistanbuledutr
1539
DOI 101081PPT-200030272 0360-2559 (Print) 1525-6111 (Online)
Copyright amp 2004 by Marcel Dekker Inc wwwdekkercom
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properties of the resins were found to be compatible with the
properties of the reference resins
Key Words Unsaturated polyester resin Polyethylene terephtha-
late Glycolysis Chemical recycling
INTRODUCTION
Recycling of plastics has been widely investigated in recent yearsPolyethylene terephthalate (PET) is a thermoplastic polymer which isproduced in considerable amounts The PET is widely used in themanufacture of high strength fibers audio and video tapes and varioustypes of packaging mainly bottles and jars[1] The overall worldconsumption of PET amounts to about 13 million tons of which 15million tons is used in the manufacture of various types of packaging[2]
In recent years the effective utilization of PET wastes became veryimportant Globally around 17 of PET bottle consumption wascollected for recycling in 1999[3] During the last eight years an almost10-fold increase in the amount of bottles collected for recycling in Europehas been observed (450000 tons in 2003 compared to 45000 tons in1995)[34]
The aim of most chemical recycling procedures for waste PET isobtaining monomers such as terephthalic acid (TPA) ethylene glycol(EG) and bis(2-hydroxy ethyl) terephthalate (BHET) The first twocompounds can be obtained by hydrolysis under neutral acidic oralkaline conditions and the last by glycolysis of waste PET A reviewsummarizes the research and applications up to 1997[2] After 1997papers involved alkaline[5ndash7] and acidic[8] hydrolysis and glycolysis[910] ofwaste PET
Vaidya et al[11ndash13] suggested the synthesis of unsaturated polyester(UP) resins from waste PET Aslan et al[14] compared the compositesheet containing unsaturated polyester developed in recycled PET tothe analogous composite made of virgin UP resin Farahat et al[15]
investigated the capability of modifying the properties of synthesized UPresins by incorporation of p-hydroxybenzoic acid as an ingredient insynthesizing these polyester resins Suh et al[16] compared the propertiesof UP resins prepared by glycolysis of PET with propylene glycol (PG)and diethylene glycol (DEG) and their mixture
In this work we tried to compare the curing and mechanicalproperties of UP resins prepared from glycolysis products of waste PETobtained by using various glycol compounds and their mixture
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EXPERIMENTAL
Materials
Waste PET flake obtained from grinding postconsumer bottles wassieved to obtain a 10ndash20 mesh fraction The viscosity average molecularweight ethMV THORN was found to be 37 104[17] Distilled water was used forextractions The rest of the materials were Merck synthesis or analyticalgrade
Glycolysis Reactions
The waste PET was depolymerized in EG (PETEG molar ratio 16)PG DEG triethylene glycol (TEG) and PGndashTEG mixture (PGTEGmolar ratio 11) [(PETglycol molar ratio (125)] using 1 (ww) zincacetate based on weight of PET as catalyst The glycolysis reactionswere carried out at 190ndash220C for 6 h in a round-bottom flask equippedwith a reflux system gas bubblier contact thermometer and mechanicalstirrer system
After the reaction hydroxyl value (HV) of the reaction mixture wasdetermined without removal of free glycol compound Then the reactionmixture was extracted with boiling water three times and filtrated forseparation of the solid fraction The water soluble crystallizable fraction(WSCF) was obtained by cooling to 4C for only glycolysis productwhich was obtained by using EG in the reaction The water insolublefraction (WIF) and WSCF were dried under vacuum at 30ndash40C Thehydroxyl values of the glycolysis products after glycol removal weredetermined
The HV of products was determined by the acetylation method[18]
A differential scanning coloumetry (DSC) scan of WSCF wasobtained with a Seteram DSC 131 calorimeter with 30mg samples with arate of 5Cmin in nitrogen atmosphere
Preparation of Unsaturated Polyester Resins
The unsaturated polyester (UP) resins which were prepared byreacting the glycolysis products with maleic anhydride at an OHCOOHmolar ratio of 111HV of the glycolysis products without separationof free glycol were used to determine the amount of maleic anhydride
Unsaturated Polyester Resins 1541
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Only one of the UP resins was prepared by reacting the WSCF and PGmixture with maleic anhydride
The polyesterification reactions were carried out in a round-bottomflask equipped with a reflux system Dean-Stark equipment gas bubbliercontact thermometer and mechanical stirrer system The reactants wereheated from room temperature to 190C in nitrogen atmosphere in about1 h The temperature was held at 190C and maintained until the acidvalue of the reaction mixture reached about 30ndash60mg KOHg Waterformed during the reaction was removed by using xylene as a solvent
The acid values (AV) were determined by the volumetric method[19]
Molecular weight determinations of all UP resins were carried outby end-group analysis[15]
The UP resins were added to styrene monomer at 80C to get 35(ww) styrene in the resins The curing characteristics such as gel time andmaximum curing temperature of all the resins were investigated The geltime and maximum curing temperature were determined using methyl-ethylketone peroxide (MEKP) [15 (ww) of resins] as the initiator andcobalt naphthenate [1 (ww) of the resins] as the accelerator
In order to compare the properties of UP resins reference resins wereprepared from maleic anhydride phthalic anhydride and one of theglycol compounds such as PG DEG TEG or PG-TEG mixture
Tensile strength and elastic module of UP resins were determinedwith Hounsfield H10KS Universal Testing Machine and hardness of UPresins was determined by using Barcol 934-1 and Shoremeter HardnessTesting Machines
RESULTS AND DISCUSSION
The glycolysis of waste PET was carried out by using EG PG DEGTEG and PG-TEG mixtures as glycol compounds in the presence of zincacetate as catalyst at 190ndash220C The HVs of the glycolysis products weredetermined and are given in Table 1
The glycolysis reaction product of waste PET obtained by using thePETEG molar ratio 16 was extracted by 250mL water at the boilingpoint three times The solid fraction was named water insoluble fraction(WIF) The filtrates were collected and cooled to 4C and crystallizedsolids obtained by filtration were named water soluble crystallizablefraction (WSCF) (the weight ratio of WSCF in total product is 85)The HV of the WSCF is comparable to that of BHET implying that theextent of depolymerization is quite significant (Table 1) This product(GP1) consists mainly of BHET monomer A DSC scan of the WSCF of
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GP1 is presented in Fig 1 There is an endothermic peak at 110C thatindicated the melting point of BHET When PET is depolymerized byusing EG and the glycolysis products are used for the preparation ofunsaturated polyester the resins are not compatible with styrene[11]
In order to prepare G-UPR1 the WSCF of GP1 and PG mixturewas polyesterified with maleic anhydride (MA) at a 11 molar ratio ofOHCOOH
In the case of glycols the compounds were PG DEG TEG andPGndashTEG mixtures The molar ratio of PETglycol was 125 The HV ofthese products changes between 250 and 300 according to type of glycolcompound (Table 1) This indicates that there is a considerable extent of
0
5
10
15
70 90 110 130 150Temp (degC)
End
o
Figure 1 DSC scan of WSCF of GP1
Table 1 HV of glycolysis products
Symbol of
product
Glycol
compound
Analysis of glycolyzed products
Before free
glycol removal
After free
glycol removal
HV (mgKOHg) HV (mg KOHg)
GP1 EG 750 440
GP2 PG 550 300
GP3 DEG 480 270
GP4 TEG 400 250
GP5 PGndashTEG 470 260
Unsaturated Polyester Resins 1543
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depolymerization and the glycolysis products mainly contained hydroxyl-terminated monomer and dimer mixtures The UP resins were preparedby reacting the glycolysis products (GP2 GP3 GP4 GP5) with MAThe resins formed were referred to as G-UPR2 G-UPR3 G-UPR4 andG-UPR5 respectively
Reference resins R-UPR1 R-UPR2 R-UPR3 and R-UPR4 wereprepared from MA phthalic anhydride (PA) and PG DEG TEG orPG-TEG mixture respectively at the same molar ratio of MAPA andOHCOOH as previously indicated
Figures 2ndash5 show the change of AV of resins based on waste PETand reference resins with the reaction time It is clear that polycondensa-tion of glycolysis products with maleic anhydride was faster than those ofthe reference resins It also means that the extent of depolymerizationincreases with the reaction time in the first stage and finally reaches anequilibrium value in approximately three hours which is a generalcharacteristic of condensation reactions
The HV and AV of UP resins were determined and these data wereused for the calculation of number average molecular weight ethMnTHORN ofthese resins[15] The ethMnTHORN is calculated from Eq (1) The AV HV andcalculated ethMnTHORN of the UP resins are presented in Table 2
Mn frac142 561 1000
AVthornHVeth1THORN
The UP resins were added in styrene monomer at 80C to get 35(ww) styrene in the resins Gel times maximum curing temperatures
0
50
100
150
200
250
300
350
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR1
G-UPR2
R-UPR1
Figure 2 The change of acid value with reaction time for G-UPR1 G-UPR2
and R-UPR1
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and time required to reach this temperatures of the resins (peak time)were determined by using 15 (ww) MEKP and 1 (ww) cobaltnaphthanate to resins The results are reported in Fig 6 and Table 3Each set of UP resins prepared from the different glycolysis products iscollected in one graph in order to study the effect of the different glycols
0
50
100
150
200
250
300
0 100 200 300 400Time (min)
AV
(mg
KO
Hg
)
G-UPR3
R-UPR2
Figure 3 The change of acid value with reaction time for G-UPR3 and
R-UPR2
0
50
100
150
200
250
300
0 100 200 300Time (min)
AV
(mg
KO
Hg
)
G-UPR4
R-UPR3
Figure 4 The change of acid value with reaction time for G-UPR4 and
R-UPR3
Unsaturated Polyester Resins 1545
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on the curing behavior in Fig 6 Maximum curing temperatures ofG-UPR1 and G-UPR2 (UP resins based on PG glycolyzed product) arehigher than they are for G-UPR3 and G-UPR4 (UP resins based onDEG and TEG glycolysis products) Time required to reach thistemperature and gel time of G-UPR1 and G-UPR2 are shorter thanare those of G-UPR3 and G-UPR4 These properties of G-UPR5 (UPresin based on PG-TEG glycolysis product) were seen to be nearly in themiddle of the other resins (Fig 6) Curing properties of waste PET-basedresins are comparable with the reference resins (Table 3 and Figs 7ndash10)
0
50
100
150
200
250
300
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR5
R-UPR4
Figure 5 The change of acid value with reaction time for G-UPR5 and
R-UPR4
Table 2 AV HV and calculated ethMnTHORN of the UP resins
Symbol of resins AV (mgKOHg) HV (mgKOHg) Calculated ethMnTHORN
G-UPR1 40 75 975
G-UPR2 30 85 975
G-UPR3 30 90 950
G-UPR4 35 85 950
G-UPR5 30 85 950
R-UPR1 60 85 975
R-UPR2 60 85 800
R-UPR3 60 85 800
R-UPR4 60 85 800
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The mechanical properties of the UP resins are presented in Table 4As seen hardness tensile strength and the elastic module of the G-UPR1and G-UPR2 are higher than are those of the other UP resins Butelongation at break percent values of these resins are lower than the otherresins The DEG and TEG units are more flexible than the PG unit dueto the ether linkage The mechanical properties of the PET based resinsare comparable with the reference resins (Table 4)
0
20
40
60
80
100
120
140
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
G-UPR3
G-UPR4
G-UPR5
Figure 6 Maximum curing temperatures of waste PET-based UP resins
Table 3 Curing properties of the UP resins
Symbol
of resins
Gel
time (min)
Max curing
temperature (C)
Peak
time (min)
G-UPR1 10 128 18
G-UPR2 13 103 23
G-UPR3 28 60 50
G-UPR4 33 53 60
G-UPR5 18 75 37
R-UPR1 9 130 17
R-UPR2 33 63 57
R-UPR3 32 65 54
R-UPR4 17 99 32
Unsaturated Polyester Resins 1547
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CONCLUSION
The PET-based unsaturated polyester resins were prepared byreacting the glycolysis products of waste PET with maleic anhydrideReference resins were prepared from maleic anhydride phthalicanhydride and one of the glycol compounds such as PG DEG TEG
0
20
40
60
80
100
120
140
0 10 20 30 40Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
R-UPR1
Figure 7 Maximum curing temperatures of G-UPR1 G-UPR2 and R-UPR1
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR3
R-UPR2
Figure 8 Maximum curing temperatures of G-UPR3 and R-UPR2
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or PGndashTEG mixture at the same OHCOOH molar ratio with the wastePET based resins
The mechanical properties and curing behaviors of the waste PET-based UP resins are comparable with the reference resins The DEG- andTEG-based resins are more flexible than are PG-based resins due to theether linkage But PG-based resins have higher tensile strength andhardness than do DEG- and TEG-based resins It appears that it isfeasible to recycle waste PET as UP resins by glycolysis reactions usingdifferent glycol compounds and glycol compounds mixtures
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR4
R-UPR3
Figure 9 Maximum curing temperatures of G-UPR4 and R-UPR3
0
20
40
60
80
100
120
0 10 20 30 40 50Time (min)
Tem
p (
degC)
G-UPR5
R-UPR4
Figure 10 Maximum curing temperatures of G-UPR5 and R-UPR4
Unsaturated Polyester Resins 1549
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ACKNOWLEDGMENTS
This work was financially supported by the Research Foundation of
Istanbul University Project Number T-14706032003
REFERENCES
1 Mansour SH Ikladious NE Depolymerization of poly(ethylene
terephthalate) wastes using 14-butandiol and triethylene glycol
Polymer Testing 2002 21 (5) 497ndash5052 Paszun D Spychaj T Chemical recycling of poly(ethylene
terephthalate) Ind Eng Chem Res 1997 36 1373ndash13833 Kosmidis VA Achilias DS Karayannidis GP Poly(ethylene
terephthalate) recycling and recovery of pure terephthalic acid
Kinetics of a phase transfer catalyzed alkaline hydrolysis Macromol
Mater Eng 2001 286 640ndash6474 Petcore News No 1 April 2003 PET Container Recycling Europe
(Petcore) Belgium5 Wan B Kao C Cheng W Kinetics of depolymerization of
poly(ethylene terephthalate) in potassium hydroxide solution Ind
Eng Chem Res 2001 40 509ndash5146 Kao C Cheng W Wan B Investigation of alkaline hydrolysis of
polyethylene terephthalate by differential scannig calorimetry and
thermogravimetric analysis J Appl Polym Sci 1998 70 1939ndash1945
Table 4 Mechanical properties of the UP resins
Symbol
of resins
Hardness
(ShoreBarkol)
Tensile
strength (MPa)
Elastic
module (MPa)
Elongation at
break point ()
G-UPR1 30 (Barkol) 12 40 14
G-UPR2 10 (Barkol) 10 35 16
G-UPR3 95 (Shore) 25 5 69
G-UPR4 80 (Shore) 15 25 72
G-UPR5 99 (Shore) 10 50 19
R-UPR1 45 (Barkol) 15 90 10
R-UPR2 92 (Shore) 35 5 69
R-UPR3 85 (Shore) 17 35 70
R-UPR4 99 (Shore) 99 65 15
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7 Karayannidis GP Chatziavgoustis AP Achilias DS
Poly(ethylene terephthalate) recycling and recovery of pure
terphthalic acid by alkaline hydrolysis Adv Polym Technol
2002 21 (4) 250ndash2598 Yoshioka T Motoki T Okuwaki A Kinetics of hydrolysis of
poly(ethylene terephthalate) powder in sulfuric acid by a modified
shrinking-core model Ind Eng Chem Res 2001 40 75ndash799 Guclu G Kas goz A Ozbudak S Ozgumus S Orbay M
Glycolysis of poly(ethylene terephthalate) wastes in xylene J Appl
Polym Sci 1998 69 2311ndash231910 Chen CH Chen CY Lo YW Mao CF Liao WT Studies
of glycolysis of poly(ethylene terephthalate) recycled from post-
consumer soft-drink bottles I influences of glycolysis conditions
J Appl Polym Sci 2001 80 943ndash94811 Vaidya UR Nadkarni VM Unsaturated polyester resins from
poly(ethylene terephthalate) waste 1 Synthesis and characteriza-
tion Ind Eng Chem Res 1987 26 194ndash19812 Vaidya UR Nadkarni VM Unsaturated polyester resins
from poly(ethylene terephthalate) waste 2 Mechanical and
dynamic mechanical properties Ind Eng Chem Res 1988 27
2056ndash206013 Vaidya UR Nadkarni VM Unsaturated polyester resins from
PET waste kinetics of polycondensation J Appl Polym Sci 1987
34 235ndash24514 Aslan S Immirzi B Laurienzo P Malinconico M Martuscelli
E Volpe MG Pelino M Savini L Unsaturated polyester resins
from glycolysed waste polyethylene terephthalate synthesis and
comparison of properties and performance with virgin resin
J Mater Sci 1997 32 2329ndash233615 Farahat MS Abdel-Azim AA Abdel-Raowf ME Modified
unsaturated polyester resins synthesized from poly(ethylene
terephthalate) waste 1 Synthesis and curing characteristics
Macromol Mater Eng 2000 283 1ndash616 Suh DJ Park OO Yoon KH The properties of unsaturated
polyester based on the glycolyzed poly(ethylene terephthalate) with
various glycol compositions Polymer 2000 41 461ndash46617 Guclu G Yalcinyuva T Ozgumus S Orbay M Hydrolysis of
waste polyethylene terephthalate and characterization of products
by differential scanning calorimetry Thermochimica Acta 2003
404 (1ndash2) 193ndash205
Unsaturated Polyester Resins 1551
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18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
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properties of the resins were found to be compatible with the
properties of the reference resins
Key Words Unsaturated polyester resin Polyethylene terephtha-
late Glycolysis Chemical recycling
INTRODUCTION
Recycling of plastics has been widely investigated in recent yearsPolyethylene terephthalate (PET) is a thermoplastic polymer which isproduced in considerable amounts The PET is widely used in themanufacture of high strength fibers audio and video tapes and varioustypes of packaging mainly bottles and jars[1] The overall worldconsumption of PET amounts to about 13 million tons of which 15million tons is used in the manufacture of various types of packaging[2]
In recent years the effective utilization of PET wastes became veryimportant Globally around 17 of PET bottle consumption wascollected for recycling in 1999[3] During the last eight years an almost10-fold increase in the amount of bottles collected for recycling in Europehas been observed (450000 tons in 2003 compared to 45000 tons in1995)[34]
The aim of most chemical recycling procedures for waste PET isobtaining monomers such as terephthalic acid (TPA) ethylene glycol(EG) and bis(2-hydroxy ethyl) terephthalate (BHET) The first twocompounds can be obtained by hydrolysis under neutral acidic oralkaline conditions and the last by glycolysis of waste PET A reviewsummarizes the research and applications up to 1997[2] After 1997papers involved alkaline[5ndash7] and acidic[8] hydrolysis and glycolysis[910] ofwaste PET
Vaidya et al[11ndash13] suggested the synthesis of unsaturated polyester(UP) resins from waste PET Aslan et al[14] compared the compositesheet containing unsaturated polyester developed in recycled PET tothe analogous composite made of virgin UP resin Farahat et al[15]
investigated the capability of modifying the properties of synthesized UPresins by incorporation of p-hydroxybenzoic acid as an ingredient insynthesizing these polyester resins Suh et al[16] compared the propertiesof UP resins prepared by glycolysis of PET with propylene glycol (PG)and diethylene glycol (DEG) and their mixture
In this work we tried to compare the curing and mechanicalproperties of UP resins prepared from glycolysis products of waste PETobtained by using various glycol compounds and their mixture
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EXPERIMENTAL
Materials
Waste PET flake obtained from grinding postconsumer bottles wassieved to obtain a 10ndash20 mesh fraction The viscosity average molecularweight ethMV THORN was found to be 37 104[17] Distilled water was used forextractions The rest of the materials were Merck synthesis or analyticalgrade
Glycolysis Reactions
The waste PET was depolymerized in EG (PETEG molar ratio 16)PG DEG triethylene glycol (TEG) and PGndashTEG mixture (PGTEGmolar ratio 11) [(PETglycol molar ratio (125)] using 1 (ww) zincacetate based on weight of PET as catalyst The glycolysis reactionswere carried out at 190ndash220C for 6 h in a round-bottom flask equippedwith a reflux system gas bubblier contact thermometer and mechanicalstirrer system
After the reaction hydroxyl value (HV) of the reaction mixture wasdetermined without removal of free glycol compound Then the reactionmixture was extracted with boiling water three times and filtrated forseparation of the solid fraction The water soluble crystallizable fraction(WSCF) was obtained by cooling to 4C for only glycolysis productwhich was obtained by using EG in the reaction The water insolublefraction (WIF) and WSCF were dried under vacuum at 30ndash40C Thehydroxyl values of the glycolysis products after glycol removal weredetermined
The HV of products was determined by the acetylation method[18]
A differential scanning coloumetry (DSC) scan of WSCF wasobtained with a Seteram DSC 131 calorimeter with 30mg samples with arate of 5Cmin in nitrogen atmosphere
Preparation of Unsaturated Polyester Resins
The unsaturated polyester (UP) resins which were prepared byreacting the glycolysis products with maleic anhydride at an OHCOOHmolar ratio of 111HV of the glycolysis products without separationof free glycol were used to determine the amount of maleic anhydride
Unsaturated Polyester Resins 1541
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Only one of the UP resins was prepared by reacting the WSCF and PGmixture with maleic anhydride
The polyesterification reactions were carried out in a round-bottomflask equipped with a reflux system Dean-Stark equipment gas bubbliercontact thermometer and mechanical stirrer system The reactants wereheated from room temperature to 190C in nitrogen atmosphere in about1 h The temperature was held at 190C and maintained until the acidvalue of the reaction mixture reached about 30ndash60mg KOHg Waterformed during the reaction was removed by using xylene as a solvent
The acid values (AV) were determined by the volumetric method[19]
Molecular weight determinations of all UP resins were carried outby end-group analysis[15]
The UP resins were added to styrene monomer at 80C to get 35(ww) styrene in the resins The curing characteristics such as gel time andmaximum curing temperature of all the resins were investigated The geltime and maximum curing temperature were determined using methyl-ethylketone peroxide (MEKP) [15 (ww) of resins] as the initiator andcobalt naphthenate [1 (ww) of the resins] as the accelerator
In order to compare the properties of UP resins reference resins wereprepared from maleic anhydride phthalic anhydride and one of theglycol compounds such as PG DEG TEG or PG-TEG mixture
Tensile strength and elastic module of UP resins were determinedwith Hounsfield H10KS Universal Testing Machine and hardness of UPresins was determined by using Barcol 934-1 and Shoremeter HardnessTesting Machines
RESULTS AND DISCUSSION
The glycolysis of waste PET was carried out by using EG PG DEGTEG and PG-TEG mixtures as glycol compounds in the presence of zincacetate as catalyst at 190ndash220C The HVs of the glycolysis products weredetermined and are given in Table 1
The glycolysis reaction product of waste PET obtained by using thePETEG molar ratio 16 was extracted by 250mL water at the boilingpoint three times The solid fraction was named water insoluble fraction(WIF) The filtrates were collected and cooled to 4C and crystallizedsolids obtained by filtration were named water soluble crystallizablefraction (WSCF) (the weight ratio of WSCF in total product is 85)The HV of the WSCF is comparable to that of BHET implying that theextent of depolymerization is quite significant (Table 1) This product(GP1) consists mainly of BHET monomer A DSC scan of the WSCF of
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GP1 is presented in Fig 1 There is an endothermic peak at 110C thatindicated the melting point of BHET When PET is depolymerized byusing EG and the glycolysis products are used for the preparation ofunsaturated polyester the resins are not compatible with styrene[11]
In order to prepare G-UPR1 the WSCF of GP1 and PG mixturewas polyesterified with maleic anhydride (MA) at a 11 molar ratio ofOHCOOH
In the case of glycols the compounds were PG DEG TEG andPGndashTEG mixtures The molar ratio of PETglycol was 125 The HV ofthese products changes between 250 and 300 according to type of glycolcompound (Table 1) This indicates that there is a considerable extent of
0
5
10
15
70 90 110 130 150Temp (degC)
End
o
Figure 1 DSC scan of WSCF of GP1
Table 1 HV of glycolysis products
Symbol of
product
Glycol
compound
Analysis of glycolyzed products
Before free
glycol removal
After free
glycol removal
HV (mgKOHg) HV (mg KOHg)
GP1 EG 750 440
GP2 PG 550 300
GP3 DEG 480 270
GP4 TEG 400 250
GP5 PGndashTEG 470 260
Unsaturated Polyester Resins 1543
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depolymerization and the glycolysis products mainly contained hydroxyl-terminated monomer and dimer mixtures The UP resins were preparedby reacting the glycolysis products (GP2 GP3 GP4 GP5) with MAThe resins formed were referred to as G-UPR2 G-UPR3 G-UPR4 andG-UPR5 respectively
Reference resins R-UPR1 R-UPR2 R-UPR3 and R-UPR4 wereprepared from MA phthalic anhydride (PA) and PG DEG TEG orPG-TEG mixture respectively at the same molar ratio of MAPA andOHCOOH as previously indicated
Figures 2ndash5 show the change of AV of resins based on waste PETand reference resins with the reaction time It is clear that polycondensa-tion of glycolysis products with maleic anhydride was faster than those ofthe reference resins It also means that the extent of depolymerizationincreases with the reaction time in the first stage and finally reaches anequilibrium value in approximately three hours which is a generalcharacteristic of condensation reactions
The HV and AV of UP resins were determined and these data wereused for the calculation of number average molecular weight ethMnTHORN ofthese resins[15] The ethMnTHORN is calculated from Eq (1) The AV HV andcalculated ethMnTHORN of the UP resins are presented in Table 2
Mn frac142 561 1000
AVthornHVeth1THORN
The UP resins were added in styrene monomer at 80C to get 35(ww) styrene in the resins Gel times maximum curing temperatures
0
50
100
150
200
250
300
350
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR1
G-UPR2
R-UPR1
Figure 2 The change of acid value with reaction time for G-UPR1 G-UPR2
and R-UPR1
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and time required to reach this temperatures of the resins (peak time)were determined by using 15 (ww) MEKP and 1 (ww) cobaltnaphthanate to resins The results are reported in Fig 6 and Table 3Each set of UP resins prepared from the different glycolysis products iscollected in one graph in order to study the effect of the different glycols
0
50
100
150
200
250
300
0 100 200 300 400Time (min)
AV
(mg
KO
Hg
)
G-UPR3
R-UPR2
Figure 3 The change of acid value with reaction time for G-UPR3 and
R-UPR2
0
50
100
150
200
250
300
0 100 200 300Time (min)
AV
(mg
KO
Hg
)
G-UPR4
R-UPR3
Figure 4 The change of acid value with reaction time for G-UPR4 and
R-UPR3
Unsaturated Polyester Resins 1545
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on the curing behavior in Fig 6 Maximum curing temperatures ofG-UPR1 and G-UPR2 (UP resins based on PG glycolyzed product) arehigher than they are for G-UPR3 and G-UPR4 (UP resins based onDEG and TEG glycolysis products) Time required to reach thistemperature and gel time of G-UPR1 and G-UPR2 are shorter thanare those of G-UPR3 and G-UPR4 These properties of G-UPR5 (UPresin based on PG-TEG glycolysis product) were seen to be nearly in themiddle of the other resins (Fig 6) Curing properties of waste PET-basedresins are comparable with the reference resins (Table 3 and Figs 7ndash10)
0
50
100
150
200
250
300
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR5
R-UPR4
Figure 5 The change of acid value with reaction time for G-UPR5 and
R-UPR4
Table 2 AV HV and calculated ethMnTHORN of the UP resins
Symbol of resins AV (mgKOHg) HV (mgKOHg) Calculated ethMnTHORN
G-UPR1 40 75 975
G-UPR2 30 85 975
G-UPR3 30 90 950
G-UPR4 35 85 950
G-UPR5 30 85 950
R-UPR1 60 85 975
R-UPR2 60 85 800
R-UPR3 60 85 800
R-UPR4 60 85 800
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The mechanical properties of the UP resins are presented in Table 4As seen hardness tensile strength and the elastic module of the G-UPR1and G-UPR2 are higher than are those of the other UP resins Butelongation at break percent values of these resins are lower than the otherresins The DEG and TEG units are more flexible than the PG unit dueto the ether linkage The mechanical properties of the PET based resinsare comparable with the reference resins (Table 4)
0
20
40
60
80
100
120
140
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
G-UPR3
G-UPR4
G-UPR5
Figure 6 Maximum curing temperatures of waste PET-based UP resins
Table 3 Curing properties of the UP resins
Symbol
of resins
Gel
time (min)
Max curing
temperature (C)
Peak
time (min)
G-UPR1 10 128 18
G-UPR2 13 103 23
G-UPR3 28 60 50
G-UPR4 33 53 60
G-UPR5 18 75 37
R-UPR1 9 130 17
R-UPR2 33 63 57
R-UPR3 32 65 54
R-UPR4 17 99 32
Unsaturated Polyester Resins 1547
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CONCLUSION
The PET-based unsaturated polyester resins were prepared byreacting the glycolysis products of waste PET with maleic anhydrideReference resins were prepared from maleic anhydride phthalicanhydride and one of the glycol compounds such as PG DEG TEG
0
20
40
60
80
100
120
140
0 10 20 30 40Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
R-UPR1
Figure 7 Maximum curing temperatures of G-UPR1 G-UPR2 and R-UPR1
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR3
R-UPR2
Figure 8 Maximum curing temperatures of G-UPR3 and R-UPR2
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or PGndashTEG mixture at the same OHCOOH molar ratio with the wastePET based resins
The mechanical properties and curing behaviors of the waste PET-based UP resins are comparable with the reference resins The DEG- andTEG-based resins are more flexible than are PG-based resins due to theether linkage But PG-based resins have higher tensile strength andhardness than do DEG- and TEG-based resins It appears that it isfeasible to recycle waste PET as UP resins by glycolysis reactions usingdifferent glycol compounds and glycol compounds mixtures
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR4
R-UPR3
Figure 9 Maximum curing temperatures of G-UPR4 and R-UPR3
0
20
40
60
80
100
120
0 10 20 30 40 50Time (min)
Tem
p (
degC)
G-UPR5
R-UPR4
Figure 10 Maximum curing temperatures of G-UPR5 and R-UPR4
Unsaturated Polyester Resins 1549
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ACKNOWLEDGMENTS
This work was financially supported by the Research Foundation of
Istanbul University Project Number T-14706032003
REFERENCES
1 Mansour SH Ikladious NE Depolymerization of poly(ethylene
terephthalate) wastes using 14-butandiol and triethylene glycol
Polymer Testing 2002 21 (5) 497ndash5052 Paszun D Spychaj T Chemical recycling of poly(ethylene
terephthalate) Ind Eng Chem Res 1997 36 1373ndash13833 Kosmidis VA Achilias DS Karayannidis GP Poly(ethylene
terephthalate) recycling and recovery of pure terephthalic acid
Kinetics of a phase transfer catalyzed alkaline hydrolysis Macromol
Mater Eng 2001 286 640ndash6474 Petcore News No 1 April 2003 PET Container Recycling Europe
(Petcore) Belgium5 Wan B Kao C Cheng W Kinetics of depolymerization of
poly(ethylene terephthalate) in potassium hydroxide solution Ind
Eng Chem Res 2001 40 509ndash5146 Kao C Cheng W Wan B Investigation of alkaline hydrolysis of
polyethylene terephthalate by differential scannig calorimetry and
thermogravimetric analysis J Appl Polym Sci 1998 70 1939ndash1945
Table 4 Mechanical properties of the UP resins
Symbol
of resins
Hardness
(ShoreBarkol)
Tensile
strength (MPa)
Elastic
module (MPa)
Elongation at
break point ()
G-UPR1 30 (Barkol) 12 40 14
G-UPR2 10 (Barkol) 10 35 16
G-UPR3 95 (Shore) 25 5 69
G-UPR4 80 (Shore) 15 25 72
G-UPR5 99 (Shore) 10 50 19
R-UPR1 45 (Barkol) 15 90 10
R-UPR2 92 (Shore) 35 5 69
R-UPR3 85 (Shore) 17 35 70
R-UPR4 99 (Shore) 99 65 15
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7 Karayannidis GP Chatziavgoustis AP Achilias DS
Poly(ethylene terephthalate) recycling and recovery of pure
terphthalic acid by alkaline hydrolysis Adv Polym Technol
2002 21 (4) 250ndash2598 Yoshioka T Motoki T Okuwaki A Kinetics of hydrolysis of
poly(ethylene terephthalate) powder in sulfuric acid by a modified
shrinking-core model Ind Eng Chem Res 2001 40 75ndash799 Guclu G Kas goz A Ozbudak S Ozgumus S Orbay M
Glycolysis of poly(ethylene terephthalate) wastes in xylene J Appl
Polym Sci 1998 69 2311ndash231910 Chen CH Chen CY Lo YW Mao CF Liao WT Studies
of glycolysis of poly(ethylene terephthalate) recycled from post-
consumer soft-drink bottles I influences of glycolysis conditions
J Appl Polym Sci 2001 80 943ndash94811 Vaidya UR Nadkarni VM Unsaturated polyester resins from
poly(ethylene terephthalate) waste 1 Synthesis and characteriza-
tion Ind Eng Chem Res 1987 26 194ndash19812 Vaidya UR Nadkarni VM Unsaturated polyester resins
from poly(ethylene terephthalate) waste 2 Mechanical and
dynamic mechanical properties Ind Eng Chem Res 1988 27
2056ndash206013 Vaidya UR Nadkarni VM Unsaturated polyester resins from
PET waste kinetics of polycondensation J Appl Polym Sci 1987
34 235ndash24514 Aslan S Immirzi B Laurienzo P Malinconico M Martuscelli
E Volpe MG Pelino M Savini L Unsaturated polyester resins
from glycolysed waste polyethylene terephthalate synthesis and
comparison of properties and performance with virgin resin
J Mater Sci 1997 32 2329ndash233615 Farahat MS Abdel-Azim AA Abdel-Raowf ME Modified
unsaturated polyester resins synthesized from poly(ethylene
terephthalate) waste 1 Synthesis and curing characteristics
Macromol Mater Eng 2000 283 1ndash616 Suh DJ Park OO Yoon KH The properties of unsaturated
polyester based on the glycolyzed poly(ethylene terephthalate) with
various glycol compositions Polymer 2000 41 461ndash46617 Guclu G Yalcinyuva T Ozgumus S Orbay M Hydrolysis of
waste polyethylene terephthalate and characterization of products
by differential scanning calorimetry Thermochimica Acta 2003
404 (1ndash2) 193ndash205
Unsaturated Polyester Resins 1551
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18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
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EXPERIMENTAL
Materials
Waste PET flake obtained from grinding postconsumer bottles wassieved to obtain a 10ndash20 mesh fraction The viscosity average molecularweight ethMV THORN was found to be 37 104[17] Distilled water was used forextractions The rest of the materials were Merck synthesis or analyticalgrade
Glycolysis Reactions
The waste PET was depolymerized in EG (PETEG molar ratio 16)PG DEG triethylene glycol (TEG) and PGndashTEG mixture (PGTEGmolar ratio 11) [(PETglycol molar ratio (125)] using 1 (ww) zincacetate based on weight of PET as catalyst The glycolysis reactionswere carried out at 190ndash220C for 6 h in a round-bottom flask equippedwith a reflux system gas bubblier contact thermometer and mechanicalstirrer system
After the reaction hydroxyl value (HV) of the reaction mixture wasdetermined without removal of free glycol compound Then the reactionmixture was extracted with boiling water three times and filtrated forseparation of the solid fraction The water soluble crystallizable fraction(WSCF) was obtained by cooling to 4C for only glycolysis productwhich was obtained by using EG in the reaction The water insolublefraction (WIF) and WSCF were dried under vacuum at 30ndash40C Thehydroxyl values of the glycolysis products after glycol removal weredetermined
The HV of products was determined by the acetylation method[18]
A differential scanning coloumetry (DSC) scan of WSCF wasobtained with a Seteram DSC 131 calorimeter with 30mg samples with arate of 5Cmin in nitrogen atmosphere
Preparation of Unsaturated Polyester Resins
The unsaturated polyester (UP) resins which were prepared byreacting the glycolysis products with maleic anhydride at an OHCOOHmolar ratio of 111HV of the glycolysis products without separationof free glycol were used to determine the amount of maleic anhydride
Unsaturated Polyester Resins 1541
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Only one of the UP resins was prepared by reacting the WSCF and PGmixture with maleic anhydride
The polyesterification reactions were carried out in a round-bottomflask equipped with a reflux system Dean-Stark equipment gas bubbliercontact thermometer and mechanical stirrer system The reactants wereheated from room temperature to 190C in nitrogen atmosphere in about1 h The temperature was held at 190C and maintained until the acidvalue of the reaction mixture reached about 30ndash60mg KOHg Waterformed during the reaction was removed by using xylene as a solvent
The acid values (AV) were determined by the volumetric method[19]
Molecular weight determinations of all UP resins were carried outby end-group analysis[15]
The UP resins were added to styrene monomer at 80C to get 35(ww) styrene in the resins The curing characteristics such as gel time andmaximum curing temperature of all the resins were investigated The geltime and maximum curing temperature were determined using methyl-ethylketone peroxide (MEKP) [15 (ww) of resins] as the initiator andcobalt naphthenate [1 (ww) of the resins] as the accelerator
In order to compare the properties of UP resins reference resins wereprepared from maleic anhydride phthalic anhydride and one of theglycol compounds such as PG DEG TEG or PG-TEG mixture
Tensile strength and elastic module of UP resins were determinedwith Hounsfield H10KS Universal Testing Machine and hardness of UPresins was determined by using Barcol 934-1 and Shoremeter HardnessTesting Machines
RESULTS AND DISCUSSION
The glycolysis of waste PET was carried out by using EG PG DEGTEG and PG-TEG mixtures as glycol compounds in the presence of zincacetate as catalyst at 190ndash220C The HVs of the glycolysis products weredetermined and are given in Table 1
The glycolysis reaction product of waste PET obtained by using thePETEG molar ratio 16 was extracted by 250mL water at the boilingpoint three times The solid fraction was named water insoluble fraction(WIF) The filtrates were collected and cooled to 4C and crystallizedsolids obtained by filtration were named water soluble crystallizablefraction (WSCF) (the weight ratio of WSCF in total product is 85)The HV of the WSCF is comparable to that of BHET implying that theextent of depolymerization is quite significant (Table 1) This product(GP1) consists mainly of BHET monomer A DSC scan of the WSCF of
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GP1 is presented in Fig 1 There is an endothermic peak at 110C thatindicated the melting point of BHET When PET is depolymerized byusing EG and the glycolysis products are used for the preparation ofunsaturated polyester the resins are not compatible with styrene[11]
In order to prepare G-UPR1 the WSCF of GP1 and PG mixturewas polyesterified with maleic anhydride (MA) at a 11 molar ratio ofOHCOOH
In the case of glycols the compounds were PG DEG TEG andPGndashTEG mixtures The molar ratio of PETglycol was 125 The HV ofthese products changes between 250 and 300 according to type of glycolcompound (Table 1) This indicates that there is a considerable extent of
0
5
10
15
70 90 110 130 150Temp (degC)
End
o
Figure 1 DSC scan of WSCF of GP1
Table 1 HV of glycolysis products
Symbol of
product
Glycol
compound
Analysis of glycolyzed products
Before free
glycol removal
After free
glycol removal
HV (mgKOHg) HV (mg KOHg)
GP1 EG 750 440
GP2 PG 550 300
GP3 DEG 480 270
GP4 TEG 400 250
GP5 PGndashTEG 470 260
Unsaturated Polyester Resins 1543
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depolymerization and the glycolysis products mainly contained hydroxyl-terminated monomer and dimer mixtures The UP resins were preparedby reacting the glycolysis products (GP2 GP3 GP4 GP5) with MAThe resins formed were referred to as G-UPR2 G-UPR3 G-UPR4 andG-UPR5 respectively
Reference resins R-UPR1 R-UPR2 R-UPR3 and R-UPR4 wereprepared from MA phthalic anhydride (PA) and PG DEG TEG orPG-TEG mixture respectively at the same molar ratio of MAPA andOHCOOH as previously indicated
Figures 2ndash5 show the change of AV of resins based on waste PETand reference resins with the reaction time It is clear that polycondensa-tion of glycolysis products with maleic anhydride was faster than those ofthe reference resins It also means that the extent of depolymerizationincreases with the reaction time in the first stage and finally reaches anequilibrium value in approximately three hours which is a generalcharacteristic of condensation reactions
The HV and AV of UP resins were determined and these data wereused for the calculation of number average molecular weight ethMnTHORN ofthese resins[15] The ethMnTHORN is calculated from Eq (1) The AV HV andcalculated ethMnTHORN of the UP resins are presented in Table 2
Mn frac142 561 1000
AVthornHVeth1THORN
The UP resins were added in styrene monomer at 80C to get 35(ww) styrene in the resins Gel times maximum curing temperatures
0
50
100
150
200
250
300
350
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR1
G-UPR2
R-UPR1
Figure 2 The change of acid value with reaction time for G-UPR1 G-UPR2
and R-UPR1
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ORDER REPRINTS
and time required to reach this temperatures of the resins (peak time)were determined by using 15 (ww) MEKP and 1 (ww) cobaltnaphthanate to resins The results are reported in Fig 6 and Table 3Each set of UP resins prepared from the different glycolysis products iscollected in one graph in order to study the effect of the different glycols
0
50
100
150
200
250
300
0 100 200 300 400Time (min)
AV
(mg
KO
Hg
)
G-UPR3
R-UPR2
Figure 3 The change of acid value with reaction time for G-UPR3 and
R-UPR2
0
50
100
150
200
250
300
0 100 200 300Time (min)
AV
(mg
KO
Hg
)
G-UPR4
R-UPR3
Figure 4 The change of acid value with reaction time for G-UPR4 and
R-UPR3
Unsaturated Polyester Resins 1545
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on the curing behavior in Fig 6 Maximum curing temperatures ofG-UPR1 and G-UPR2 (UP resins based on PG glycolyzed product) arehigher than they are for G-UPR3 and G-UPR4 (UP resins based onDEG and TEG glycolysis products) Time required to reach thistemperature and gel time of G-UPR1 and G-UPR2 are shorter thanare those of G-UPR3 and G-UPR4 These properties of G-UPR5 (UPresin based on PG-TEG glycolysis product) were seen to be nearly in themiddle of the other resins (Fig 6) Curing properties of waste PET-basedresins are comparable with the reference resins (Table 3 and Figs 7ndash10)
0
50
100
150
200
250
300
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR5
R-UPR4
Figure 5 The change of acid value with reaction time for G-UPR5 and
R-UPR4
Table 2 AV HV and calculated ethMnTHORN of the UP resins
Symbol of resins AV (mgKOHg) HV (mgKOHg) Calculated ethMnTHORN
G-UPR1 40 75 975
G-UPR2 30 85 975
G-UPR3 30 90 950
G-UPR4 35 85 950
G-UPR5 30 85 950
R-UPR1 60 85 975
R-UPR2 60 85 800
R-UPR3 60 85 800
R-UPR4 60 85 800
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The mechanical properties of the UP resins are presented in Table 4As seen hardness tensile strength and the elastic module of the G-UPR1and G-UPR2 are higher than are those of the other UP resins Butelongation at break percent values of these resins are lower than the otherresins The DEG and TEG units are more flexible than the PG unit dueto the ether linkage The mechanical properties of the PET based resinsare comparable with the reference resins (Table 4)
0
20
40
60
80
100
120
140
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
G-UPR3
G-UPR4
G-UPR5
Figure 6 Maximum curing temperatures of waste PET-based UP resins
Table 3 Curing properties of the UP resins
Symbol
of resins
Gel
time (min)
Max curing
temperature (C)
Peak
time (min)
G-UPR1 10 128 18
G-UPR2 13 103 23
G-UPR3 28 60 50
G-UPR4 33 53 60
G-UPR5 18 75 37
R-UPR1 9 130 17
R-UPR2 33 63 57
R-UPR3 32 65 54
R-UPR4 17 99 32
Unsaturated Polyester Resins 1547
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CONCLUSION
The PET-based unsaturated polyester resins were prepared byreacting the glycolysis products of waste PET with maleic anhydrideReference resins were prepared from maleic anhydride phthalicanhydride and one of the glycol compounds such as PG DEG TEG
0
20
40
60
80
100
120
140
0 10 20 30 40Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
R-UPR1
Figure 7 Maximum curing temperatures of G-UPR1 G-UPR2 and R-UPR1
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR3
R-UPR2
Figure 8 Maximum curing temperatures of G-UPR3 and R-UPR2
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or PGndashTEG mixture at the same OHCOOH molar ratio with the wastePET based resins
The mechanical properties and curing behaviors of the waste PET-based UP resins are comparable with the reference resins The DEG- andTEG-based resins are more flexible than are PG-based resins due to theether linkage But PG-based resins have higher tensile strength andhardness than do DEG- and TEG-based resins It appears that it isfeasible to recycle waste PET as UP resins by glycolysis reactions usingdifferent glycol compounds and glycol compounds mixtures
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR4
R-UPR3
Figure 9 Maximum curing temperatures of G-UPR4 and R-UPR3
0
20
40
60
80
100
120
0 10 20 30 40 50Time (min)
Tem
p (
degC)
G-UPR5
R-UPR4
Figure 10 Maximum curing temperatures of G-UPR5 and R-UPR4
Unsaturated Polyester Resins 1549
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ACKNOWLEDGMENTS
This work was financially supported by the Research Foundation of
Istanbul University Project Number T-14706032003
REFERENCES
1 Mansour SH Ikladious NE Depolymerization of poly(ethylene
terephthalate) wastes using 14-butandiol and triethylene glycol
Polymer Testing 2002 21 (5) 497ndash5052 Paszun D Spychaj T Chemical recycling of poly(ethylene
terephthalate) Ind Eng Chem Res 1997 36 1373ndash13833 Kosmidis VA Achilias DS Karayannidis GP Poly(ethylene
terephthalate) recycling and recovery of pure terephthalic acid
Kinetics of a phase transfer catalyzed alkaline hydrolysis Macromol
Mater Eng 2001 286 640ndash6474 Petcore News No 1 April 2003 PET Container Recycling Europe
(Petcore) Belgium5 Wan B Kao C Cheng W Kinetics of depolymerization of
poly(ethylene terephthalate) in potassium hydroxide solution Ind
Eng Chem Res 2001 40 509ndash5146 Kao C Cheng W Wan B Investigation of alkaline hydrolysis of
polyethylene terephthalate by differential scannig calorimetry and
thermogravimetric analysis J Appl Polym Sci 1998 70 1939ndash1945
Table 4 Mechanical properties of the UP resins
Symbol
of resins
Hardness
(ShoreBarkol)
Tensile
strength (MPa)
Elastic
module (MPa)
Elongation at
break point ()
G-UPR1 30 (Barkol) 12 40 14
G-UPR2 10 (Barkol) 10 35 16
G-UPR3 95 (Shore) 25 5 69
G-UPR4 80 (Shore) 15 25 72
G-UPR5 99 (Shore) 10 50 19
R-UPR1 45 (Barkol) 15 90 10
R-UPR2 92 (Shore) 35 5 69
R-UPR3 85 (Shore) 17 35 70
R-UPR4 99 (Shore) 99 65 15
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7 Karayannidis GP Chatziavgoustis AP Achilias DS
Poly(ethylene terephthalate) recycling and recovery of pure
terphthalic acid by alkaline hydrolysis Adv Polym Technol
2002 21 (4) 250ndash2598 Yoshioka T Motoki T Okuwaki A Kinetics of hydrolysis of
poly(ethylene terephthalate) powder in sulfuric acid by a modified
shrinking-core model Ind Eng Chem Res 2001 40 75ndash799 Guclu G Kas goz A Ozbudak S Ozgumus S Orbay M
Glycolysis of poly(ethylene terephthalate) wastes in xylene J Appl
Polym Sci 1998 69 2311ndash231910 Chen CH Chen CY Lo YW Mao CF Liao WT Studies
of glycolysis of poly(ethylene terephthalate) recycled from post-
consumer soft-drink bottles I influences of glycolysis conditions
J Appl Polym Sci 2001 80 943ndash94811 Vaidya UR Nadkarni VM Unsaturated polyester resins from
poly(ethylene terephthalate) waste 1 Synthesis and characteriza-
tion Ind Eng Chem Res 1987 26 194ndash19812 Vaidya UR Nadkarni VM Unsaturated polyester resins
from poly(ethylene terephthalate) waste 2 Mechanical and
dynamic mechanical properties Ind Eng Chem Res 1988 27
2056ndash206013 Vaidya UR Nadkarni VM Unsaturated polyester resins from
PET waste kinetics of polycondensation J Appl Polym Sci 1987
34 235ndash24514 Aslan S Immirzi B Laurienzo P Malinconico M Martuscelli
E Volpe MG Pelino M Savini L Unsaturated polyester resins
from glycolysed waste polyethylene terephthalate synthesis and
comparison of properties and performance with virgin resin
J Mater Sci 1997 32 2329ndash233615 Farahat MS Abdel-Azim AA Abdel-Raowf ME Modified
unsaturated polyester resins synthesized from poly(ethylene
terephthalate) waste 1 Synthesis and curing characteristics
Macromol Mater Eng 2000 283 1ndash616 Suh DJ Park OO Yoon KH The properties of unsaturated
polyester based on the glycolyzed poly(ethylene terephthalate) with
various glycol compositions Polymer 2000 41 461ndash46617 Guclu G Yalcinyuva T Ozgumus S Orbay M Hydrolysis of
waste polyethylene terephthalate and characterization of products
by differential scanning calorimetry Thermochimica Acta 2003
404 (1ndash2) 193ndash205
Unsaturated Polyester Resins 1551
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18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
1552 Ozturk and Guclu
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embe
r 20
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Request PermissionOrder Reprints
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httpwwwdekkercomservletproductDOI101081PPT200030272
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All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request Permission Order Reprints link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
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Only one of the UP resins was prepared by reacting the WSCF and PGmixture with maleic anhydride
The polyesterification reactions were carried out in a round-bottomflask equipped with a reflux system Dean-Stark equipment gas bubbliercontact thermometer and mechanical stirrer system The reactants wereheated from room temperature to 190C in nitrogen atmosphere in about1 h The temperature was held at 190C and maintained until the acidvalue of the reaction mixture reached about 30ndash60mg KOHg Waterformed during the reaction was removed by using xylene as a solvent
The acid values (AV) were determined by the volumetric method[19]
Molecular weight determinations of all UP resins were carried outby end-group analysis[15]
The UP resins were added to styrene monomer at 80C to get 35(ww) styrene in the resins The curing characteristics such as gel time andmaximum curing temperature of all the resins were investigated The geltime and maximum curing temperature were determined using methyl-ethylketone peroxide (MEKP) [15 (ww) of resins] as the initiator andcobalt naphthenate [1 (ww) of the resins] as the accelerator
In order to compare the properties of UP resins reference resins wereprepared from maleic anhydride phthalic anhydride and one of theglycol compounds such as PG DEG TEG or PG-TEG mixture
Tensile strength and elastic module of UP resins were determinedwith Hounsfield H10KS Universal Testing Machine and hardness of UPresins was determined by using Barcol 934-1 and Shoremeter HardnessTesting Machines
RESULTS AND DISCUSSION
The glycolysis of waste PET was carried out by using EG PG DEGTEG and PG-TEG mixtures as glycol compounds in the presence of zincacetate as catalyst at 190ndash220C The HVs of the glycolysis products weredetermined and are given in Table 1
The glycolysis reaction product of waste PET obtained by using thePETEG molar ratio 16 was extracted by 250mL water at the boilingpoint three times The solid fraction was named water insoluble fraction(WIF) The filtrates were collected and cooled to 4C and crystallizedsolids obtained by filtration were named water soluble crystallizablefraction (WSCF) (the weight ratio of WSCF in total product is 85)The HV of the WSCF is comparable to that of BHET implying that theextent of depolymerization is quite significant (Table 1) This product(GP1) consists mainly of BHET monomer A DSC scan of the WSCF of
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GP1 is presented in Fig 1 There is an endothermic peak at 110C thatindicated the melting point of BHET When PET is depolymerized byusing EG and the glycolysis products are used for the preparation ofunsaturated polyester the resins are not compatible with styrene[11]
In order to prepare G-UPR1 the WSCF of GP1 and PG mixturewas polyesterified with maleic anhydride (MA) at a 11 molar ratio ofOHCOOH
In the case of glycols the compounds were PG DEG TEG andPGndashTEG mixtures The molar ratio of PETglycol was 125 The HV ofthese products changes between 250 and 300 according to type of glycolcompound (Table 1) This indicates that there is a considerable extent of
0
5
10
15
70 90 110 130 150Temp (degC)
End
o
Figure 1 DSC scan of WSCF of GP1
Table 1 HV of glycolysis products
Symbol of
product
Glycol
compound
Analysis of glycolyzed products
Before free
glycol removal
After free
glycol removal
HV (mgKOHg) HV (mg KOHg)
GP1 EG 750 440
GP2 PG 550 300
GP3 DEG 480 270
GP4 TEG 400 250
GP5 PGndashTEG 470 260
Unsaturated Polyester Resins 1543
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depolymerization and the glycolysis products mainly contained hydroxyl-terminated monomer and dimer mixtures The UP resins were preparedby reacting the glycolysis products (GP2 GP3 GP4 GP5) with MAThe resins formed were referred to as G-UPR2 G-UPR3 G-UPR4 andG-UPR5 respectively
Reference resins R-UPR1 R-UPR2 R-UPR3 and R-UPR4 wereprepared from MA phthalic anhydride (PA) and PG DEG TEG orPG-TEG mixture respectively at the same molar ratio of MAPA andOHCOOH as previously indicated
Figures 2ndash5 show the change of AV of resins based on waste PETand reference resins with the reaction time It is clear that polycondensa-tion of glycolysis products with maleic anhydride was faster than those ofthe reference resins It also means that the extent of depolymerizationincreases with the reaction time in the first stage and finally reaches anequilibrium value in approximately three hours which is a generalcharacteristic of condensation reactions
The HV and AV of UP resins were determined and these data wereused for the calculation of number average molecular weight ethMnTHORN ofthese resins[15] The ethMnTHORN is calculated from Eq (1) The AV HV andcalculated ethMnTHORN of the UP resins are presented in Table 2
Mn frac142 561 1000
AVthornHVeth1THORN
The UP resins were added in styrene monomer at 80C to get 35(ww) styrene in the resins Gel times maximum curing temperatures
0
50
100
150
200
250
300
350
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR1
G-UPR2
R-UPR1
Figure 2 The change of acid value with reaction time for G-UPR1 G-UPR2
and R-UPR1
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and time required to reach this temperatures of the resins (peak time)were determined by using 15 (ww) MEKP and 1 (ww) cobaltnaphthanate to resins The results are reported in Fig 6 and Table 3Each set of UP resins prepared from the different glycolysis products iscollected in one graph in order to study the effect of the different glycols
0
50
100
150
200
250
300
0 100 200 300 400Time (min)
AV
(mg
KO
Hg
)
G-UPR3
R-UPR2
Figure 3 The change of acid value with reaction time for G-UPR3 and
R-UPR2
0
50
100
150
200
250
300
0 100 200 300Time (min)
AV
(mg
KO
Hg
)
G-UPR4
R-UPR3
Figure 4 The change of acid value with reaction time for G-UPR4 and
R-UPR3
Unsaturated Polyester Resins 1545
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on the curing behavior in Fig 6 Maximum curing temperatures ofG-UPR1 and G-UPR2 (UP resins based on PG glycolyzed product) arehigher than they are for G-UPR3 and G-UPR4 (UP resins based onDEG and TEG glycolysis products) Time required to reach thistemperature and gel time of G-UPR1 and G-UPR2 are shorter thanare those of G-UPR3 and G-UPR4 These properties of G-UPR5 (UPresin based on PG-TEG glycolysis product) were seen to be nearly in themiddle of the other resins (Fig 6) Curing properties of waste PET-basedresins are comparable with the reference resins (Table 3 and Figs 7ndash10)
0
50
100
150
200
250
300
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR5
R-UPR4
Figure 5 The change of acid value with reaction time for G-UPR5 and
R-UPR4
Table 2 AV HV and calculated ethMnTHORN of the UP resins
Symbol of resins AV (mgKOHg) HV (mgKOHg) Calculated ethMnTHORN
G-UPR1 40 75 975
G-UPR2 30 85 975
G-UPR3 30 90 950
G-UPR4 35 85 950
G-UPR5 30 85 950
R-UPR1 60 85 975
R-UPR2 60 85 800
R-UPR3 60 85 800
R-UPR4 60 85 800
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The mechanical properties of the UP resins are presented in Table 4As seen hardness tensile strength and the elastic module of the G-UPR1and G-UPR2 are higher than are those of the other UP resins Butelongation at break percent values of these resins are lower than the otherresins The DEG and TEG units are more flexible than the PG unit dueto the ether linkage The mechanical properties of the PET based resinsare comparable with the reference resins (Table 4)
0
20
40
60
80
100
120
140
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
G-UPR3
G-UPR4
G-UPR5
Figure 6 Maximum curing temperatures of waste PET-based UP resins
Table 3 Curing properties of the UP resins
Symbol
of resins
Gel
time (min)
Max curing
temperature (C)
Peak
time (min)
G-UPR1 10 128 18
G-UPR2 13 103 23
G-UPR3 28 60 50
G-UPR4 33 53 60
G-UPR5 18 75 37
R-UPR1 9 130 17
R-UPR2 33 63 57
R-UPR3 32 65 54
R-UPR4 17 99 32
Unsaturated Polyester Resins 1547
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CONCLUSION
The PET-based unsaturated polyester resins were prepared byreacting the glycolysis products of waste PET with maleic anhydrideReference resins were prepared from maleic anhydride phthalicanhydride and one of the glycol compounds such as PG DEG TEG
0
20
40
60
80
100
120
140
0 10 20 30 40Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
R-UPR1
Figure 7 Maximum curing temperatures of G-UPR1 G-UPR2 and R-UPR1
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR3
R-UPR2
Figure 8 Maximum curing temperatures of G-UPR3 and R-UPR2
1548 Ozturk and Guclu
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or PGndashTEG mixture at the same OHCOOH molar ratio with the wastePET based resins
The mechanical properties and curing behaviors of the waste PET-based UP resins are comparable with the reference resins The DEG- andTEG-based resins are more flexible than are PG-based resins due to theether linkage But PG-based resins have higher tensile strength andhardness than do DEG- and TEG-based resins It appears that it isfeasible to recycle waste PET as UP resins by glycolysis reactions usingdifferent glycol compounds and glycol compounds mixtures
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR4
R-UPR3
Figure 9 Maximum curing temperatures of G-UPR4 and R-UPR3
0
20
40
60
80
100
120
0 10 20 30 40 50Time (min)
Tem
p (
degC)
G-UPR5
R-UPR4
Figure 10 Maximum curing temperatures of G-UPR5 and R-UPR4
Unsaturated Polyester Resins 1549
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ACKNOWLEDGMENTS
This work was financially supported by the Research Foundation of
Istanbul University Project Number T-14706032003
REFERENCES
1 Mansour SH Ikladious NE Depolymerization of poly(ethylene
terephthalate) wastes using 14-butandiol and triethylene glycol
Polymer Testing 2002 21 (5) 497ndash5052 Paszun D Spychaj T Chemical recycling of poly(ethylene
terephthalate) Ind Eng Chem Res 1997 36 1373ndash13833 Kosmidis VA Achilias DS Karayannidis GP Poly(ethylene
terephthalate) recycling and recovery of pure terephthalic acid
Kinetics of a phase transfer catalyzed alkaline hydrolysis Macromol
Mater Eng 2001 286 640ndash6474 Petcore News No 1 April 2003 PET Container Recycling Europe
(Petcore) Belgium5 Wan B Kao C Cheng W Kinetics of depolymerization of
poly(ethylene terephthalate) in potassium hydroxide solution Ind
Eng Chem Res 2001 40 509ndash5146 Kao C Cheng W Wan B Investigation of alkaline hydrolysis of
polyethylene terephthalate by differential scannig calorimetry and
thermogravimetric analysis J Appl Polym Sci 1998 70 1939ndash1945
Table 4 Mechanical properties of the UP resins
Symbol
of resins
Hardness
(ShoreBarkol)
Tensile
strength (MPa)
Elastic
module (MPa)
Elongation at
break point ()
G-UPR1 30 (Barkol) 12 40 14
G-UPR2 10 (Barkol) 10 35 16
G-UPR3 95 (Shore) 25 5 69
G-UPR4 80 (Shore) 15 25 72
G-UPR5 99 (Shore) 10 50 19
R-UPR1 45 (Barkol) 15 90 10
R-UPR2 92 (Shore) 35 5 69
R-UPR3 85 (Shore) 17 35 70
R-UPR4 99 (Shore) 99 65 15
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7 Karayannidis GP Chatziavgoustis AP Achilias DS
Poly(ethylene terephthalate) recycling and recovery of pure
terphthalic acid by alkaline hydrolysis Adv Polym Technol
2002 21 (4) 250ndash2598 Yoshioka T Motoki T Okuwaki A Kinetics of hydrolysis of
poly(ethylene terephthalate) powder in sulfuric acid by a modified
shrinking-core model Ind Eng Chem Res 2001 40 75ndash799 Guclu G Kas goz A Ozbudak S Ozgumus S Orbay M
Glycolysis of poly(ethylene terephthalate) wastes in xylene J Appl
Polym Sci 1998 69 2311ndash231910 Chen CH Chen CY Lo YW Mao CF Liao WT Studies
of glycolysis of poly(ethylene terephthalate) recycled from post-
consumer soft-drink bottles I influences of glycolysis conditions
J Appl Polym Sci 2001 80 943ndash94811 Vaidya UR Nadkarni VM Unsaturated polyester resins from
poly(ethylene terephthalate) waste 1 Synthesis and characteriza-
tion Ind Eng Chem Res 1987 26 194ndash19812 Vaidya UR Nadkarni VM Unsaturated polyester resins
from poly(ethylene terephthalate) waste 2 Mechanical and
dynamic mechanical properties Ind Eng Chem Res 1988 27
2056ndash206013 Vaidya UR Nadkarni VM Unsaturated polyester resins from
PET waste kinetics of polycondensation J Appl Polym Sci 1987
34 235ndash24514 Aslan S Immirzi B Laurienzo P Malinconico M Martuscelli
E Volpe MG Pelino M Savini L Unsaturated polyester resins
from glycolysed waste polyethylene terephthalate synthesis and
comparison of properties and performance with virgin resin
J Mater Sci 1997 32 2329ndash233615 Farahat MS Abdel-Azim AA Abdel-Raowf ME Modified
unsaturated polyester resins synthesized from poly(ethylene
terephthalate) waste 1 Synthesis and curing characteristics
Macromol Mater Eng 2000 283 1ndash616 Suh DJ Park OO Yoon KH The properties of unsaturated
polyester based on the glycolyzed poly(ethylene terephthalate) with
various glycol compositions Polymer 2000 41 461ndash46617 Guclu G Yalcinyuva T Ozgumus S Orbay M Hydrolysis of
waste polyethylene terephthalate and characterization of products
by differential scanning calorimetry Thermochimica Acta 2003
404 (1ndash2) 193ndash205
Unsaturated Polyester Resins 1551
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ORDER REPRINTS
18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
1552 Ozturk and Guclu
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
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hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
Request PermissionOrder Reprints
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081PPT200030272
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request Permission Order Reprints link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
Dow
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ORDER REPRINTS
GP1 is presented in Fig 1 There is an endothermic peak at 110C thatindicated the melting point of BHET When PET is depolymerized byusing EG and the glycolysis products are used for the preparation ofunsaturated polyester the resins are not compatible with styrene[11]
In order to prepare G-UPR1 the WSCF of GP1 and PG mixturewas polyesterified with maleic anhydride (MA) at a 11 molar ratio ofOHCOOH
In the case of glycols the compounds were PG DEG TEG andPGndashTEG mixtures The molar ratio of PETglycol was 125 The HV ofthese products changes between 250 and 300 according to type of glycolcompound (Table 1) This indicates that there is a considerable extent of
0
5
10
15
70 90 110 130 150Temp (degC)
End
o
Figure 1 DSC scan of WSCF of GP1
Table 1 HV of glycolysis products
Symbol of
product
Glycol
compound
Analysis of glycolyzed products
Before free
glycol removal
After free
glycol removal
HV (mgKOHg) HV (mg KOHg)
GP1 EG 750 440
GP2 PG 550 300
GP3 DEG 480 270
GP4 TEG 400 250
GP5 PGndashTEG 470 260
Unsaturated Polyester Resins 1543
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depolymerization and the glycolysis products mainly contained hydroxyl-terminated monomer and dimer mixtures The UP resins were preparedby reacting the glycolysis products (GP2 GP3 GP4 GP5) with MAThe resins formed were referred to as G-UPR2 G-UPR3 G-UPR4 andG-UPR5 respectively
Reference resins R-UPR1 R-UPR2 R-UPR3 and R-UPR4 wereprepared from MA phthalic anhydride (PA) and PG DEG TEG orPG-TEG mixture respectively at the same molar ratio of MAPA andOHCOOH as previously indicated
Figures 2ndash5 show the change of AV of resins based on waste PETand reference resins with the reaction time It is clear that polycondensa-tion of glycolysis products with maleic anhydride was faster than those ofthe reference resins It also means that the extent of depolymerizationincreases with the reaction time in the first stage and finally reaches anequilibrium value in approximately three hours which is a generalcharacteristic of condensation reactions
The HV and AV of UP resins were determined and these data wereused for the calculation of number average molecular weight ethMnTHORN ofthese resins[15] The ethMnTHORN is calculated from Eq (1) The AV HV andcalculated ethMnTHORN of the UP resins are presented in Table 2
Mn frac142 561 1000
AVthornHVeth1THORN
The UP resins were added in styrene monomer at 80C to get 35(ww) styrene in the resins Gel times maximum curing temperatures
0
50
100
150
200
250
300
350
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR1
G-UPR2
R-UPR1
Figure 2 The change of acid value with reaction time for G-UPR1 G-UPR2
and R-UPR1
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and time required to reach this temperatures of the resins (peak time)were determined by using 15 (ww) MEKP and 1 (ww) cobaltnaphthanate to resins The results are reported in Fig 6 and Table 3Each set of UP resins prepared from the different glycolysis products iscollected in one graph in order to study the effect of the different glycols
0
50
100
150
200
250
300
0 100 200 300 400Time (min)
AV
(mg
KO
Hg
)
G-UPR3
R-UPR2
Figure 3 The change of acid value with reaction time for G-UPR3 and
R-UPR2
0
50
100
150
200
250
300
0 100 200 300Time (min)
AV
(mg
KO
Hg
)
G-UPR4
R-UPR3
Figure 4 The change of acid value with reaction time for G-UPR4 and
R-UPR3
Unsaturated Polyester Resins 1545
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on the curing behavior in Fig 6 Maximum curing temperatures ofG-UPR1 and G-UPR2 (UP resins based on PG glycolyzed product) arehigher than they are for G-UPR3 and G-UPR4 (UP resins based onDEG and TEG glycolysis products) Time required to reach thistemperature and gel time of G-UPR1 and G-UPR2 are shorter thanare those of G-UPR3 and G-UPR4 These properties of G-UPR5 (UPresin based on PG-TEG glycolysis product) were seen to be nearly in themiddle of the other resins (Fig 6) Curing properties of waste PET-basedresins are comparable with the reference resins (Table 3 and Figs 7ndash10)
0
50
100
150
200
250
300
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR5
R-UPR4
Figure 5 The change of acid value with reaction time for G-UPR5 and
R-UPR4
Table 2 AV HV and calculated ethMnTHORN of the UP resins
Symbol of resins AV (mgKOHg) HV (mgKOHg) Calculated ethMnTHORN
G-UPR1 40 75 975
G-UPR2 30 85 975
G-UPR3 30 90 950
G-UPR4 35 85 950
G-UPR5 30 85 950
R-UPR1 60 85 975
R-UPR2 60 85 800
R-UPR3 60 85 800
R-UPR4 60 85 800
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The mechanical properties of the UP resins are presented in Table 4As seen hardness tensile strength and the elastic module of the G-UPR1and G-UPR2 are higher than are those of the other UP resins Butelongation at break percent values of these resins are lower than the otherresins The DEG and TEG units are more flexible than the PG unit dueto the ether linkage The mechanical properties of the PET based resinsare comparable with the reference resins (Table 4)
0
20
40
60
80
100
120
140
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
G-UPR3
G-UPR4
G-UPR5
Figure 6 Maximum curing temperatures of waste PET-based UP resins
Table 3 Curing properties of the UP resins
Symbol
of resins
Gel
time (min)
Max curing
temperature (C)
Peak
time (min)
G-UPR1 10 128 18
G-UPR2 13 103 23
G-UPR3 28 60 50
G-UPR4 33 53 60
G-UPR5 18 75 37
R-UPR1 9 130 17
R-UPR2 33 63 57
R-UPR3 32 65 54
R-UPR4 17 99 32
Unsaturated Polyester Resins 1547
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CONCLUSION
The PET-based unsaturated polyester resins were prepared byreacting the glycolysis products of waste PET with maleic anhydrideReference resins were prepared from maleic anhydride phthalicanhydride and one of the glycol compounds such as PG DEG TEG
0
20
40
60
80
100
120
140
0 10 20 30 40Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
R-UPR1
Figure 7 Maximum curing temperatures of G-UPR1 G-UPR2 and R-UPR1
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR3
R-UPR2
Figure 8 Maximum curing temperatures of G-UPR3 and R-UPR2
1548 Ozturk and Guclu
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ORDER REPRINTS
or PGndashTEG mixture at the same OHCOOH molar ratio with the wastePET based resins
The mechanical properties and curing behaviors of the waste PET-based UP resins are comparable with the reference resins The DEG- andTEG-based resins are more flexible than are PG-based resins due to theether linkage But PG-based resins have higher tensile strength andhardness than do DEG- and TEG-based resins It appears that it isfeasible to recycle waste PET as UP resins by glycolysis reactions usingdifferent glycol compounds and glycol compounds mixtures
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR4
R-UPR3
Figure 9 Maximum curing temperatures of G-UPR4 and R-UPR3
0
20
40
60
80
100
120
0 10 20 30 40 50Time (min)
Tem
p (
degC)
G-UPR5
R-UPR4
Figure 10 Maximum curing temperatures of G-UPR5 and R-UPR4
Unsaturated Polyester Resins 1549
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embe
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ACKNOWLEDGMENTS
This work was financially supported by the Research Foundation of
Istanbul University Project Number T-14706032003
REFERENCES
1 Mansour SH Ikladious NE Depolymerization of poly(ethylene
terephthalate) wastes using 14-butandiol and triethylene glycol
Polymer Testing 2002 21 (5) 497ndash5052 Paszun D Spychaj T Chemical recycling of poly(ethylene
terephthalate) Ind Eng Chem Res 1997 36 1373ndash13833 Kosmidis VA Achilias DS Karayannidis GP Poly(ethylene
terephthalate) recycling and recovery of pure terephthalic acid
Kinetics of a phase transfer catalyzed alkaline hydrolysis Macromol
Mater Eng 2001 286 640ndash6474 Petcore News No 1 April 2003 PET Container Recycling Europe
(Petcore) Belgium5 Wan B Kao C Cheng W Kinetics of depolymerization of
poly(ethylene terephthalate) in potassium hydroxide solution Ind
Eng Chem Res 2001 40 509ndash5146 Kao C Cheng W Wan B Investigation of alkaline hydrolysis of
polyethylene terephthalate by differential scannig calorimetry and
thermogravimetric analysis J Appl Polym Sci 1998 70 1939ndash1945
Table 4 Mechanical properties of the UP resins
Symbol
of resins
Hardness
(ShoreBarkol)
Tensile
strength (MPa)
Elastic
module (MPa)
Elongation at
break point ()
G-UPR1 30 (Barkol) 12 40 14
G-UPR2 10 (Barkol) 10 35 16
G-UPR3 95 (Shore) 25 5 69
G-UPR4 80 (Shore) 15 25 72
G-UPR5 99 (Shore) 10 50 19
R-UPR1 45 (Barkol) 15 90 10
R-UPR2 92 (Shore) 35 5 69
R-UPR3 85 (Shore) 17 35 70
R-UPR4 99 (Shore) 99 65 15
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ogy]
at 1
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embe
r 20
13
ORDER REPRINTS
7 Karayannidis GP Chatziavgoustis AP Achilias DS
Poly(ethylene terephthalate) recycling and recovery of pure
terphthalic acid by alkaline hydrolysis Adv Polym Technol
2002 21 (4) 250ndash2598 Yoshioka T Motoki T Okuwaki A Kinetics of hydrolysis of
poly(ethylene terephthalate) powder in sulfuric acid by a modified
shrinking-core model Ind Eng Chem Res 2001 40 75ndash799 Guclu G Kas goz A Ozbudak S Ozgumus S Orbay M
Glycolysis of poly(ethylene terephthalate) wastes in xylene J Appl
Polym Sci 1998 69 2311ndash231910 Chen CH Chen CY Lo YW Mao CF Liao WT Studies
of glycolysis of poly(ethylene terephthalate) recycled from post-
consumer soft-drink bottles I influences of glycolysis conditions
J Appl Polym Sci 2001 80 943ndash94811 Vaidya UR Nadkarni VM Unsaturated polyester resins from
poly(ethylene terephthalate) waste 1 Synthesis and characteriza-
tion Ind Eng Chem Res 1987 26 194ndash19812 Vaidya UR Nadkarni VM Unsaturated polyester resins
from poly(ethylene terephthalate) waste 2 Mechanical and
dynamic mechanical properties Ind Eng Chem Res 1988 27
2056ndash206013 Vaidya UR Nadkarni VM Unsaturated polyester resins from
PET waste kinetics of polycondensation J Appl Polym Sci 1987
34 235ndash24514 Aslan S Immirzi B Laurienzo P Malinconico M Martuscelli
E Volpe MG Pelino M Savini L Unsaturated polyester resins
from glycolysed waste polyethylene terephthalate synthesis and
comparison of properties and performance with virgin resin
J Mater Sci 1997 32 2329ndash233615 Farahat MS Abdel-Azim AA Abdel-Raowf ME Modified
unsaturated polyester resins synthesized from poly(ethylene
terephthalate) waste 1 Synthesis and curing characteristics
Macromol Mater Eng 2000 283 1ndash616 Suh DJ Park OO Yoon KH The properties of unsaturated
polyester based on the glycolyzed poly(ethylene terephthalate) with
various glycol compositions Polymer 2000 41 461ndash46617 Guclu G Yalcinyuva T Ozgumus S Orbay M Hydrolysis of
waste polyethylene terephthalate and characterization of products
by differential scanning calorimetry Thermochimica Acta 2003
404 (1ndash2) 193ndash205
Unsaturated Polyester Resins 1551
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18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
1552 Ozturk and Guclu
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Request PermissionOrder Reprints
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ORDER REPRINTS
depolymerization and the glycolysis products mainly contained hydroxyl-terminated monomer and dimer mixtures The UP resins were preparedby reacting the glycolysis products (GP2 GP3 GP4 GP5) with MAThe resins formed were referred to as G-UPR2 G-UPR3 G-UPR4 andG-UPR5 respectively
Reference resins R-UPR1 R-UPR2 R-UPR3 and R-UPR4 wereprepared from MA phthalic anhydride (PA) and PG DEG TEG orPG-TEG mixture respectively at the same molar ratio of MAPA andOHCOOH as previously indicated
Figures 2ndash5 show the change of AV of resins based on waste PETand reference resins with the reaction time It is clear that polycondensa-tion of glycolysis products with maleic anhydride was faster than those ofthe reference resins It also means that the extent of depolymerizationincreases with the reaction time in the first stage and finally reaches anequilibrium value in approximately three hours which is a generalcharacteristic of condensation reactions
The HV and AV of UP resins were determined and these data wereused for the calculation of number average molecular weight ethMnTHORN ofthese resins[15] The ethMnTHORN is calculated from Eq (1) The AV HV andcalculated ethMnTHORN of the UP resins are presented in Table 2
Mn frac142 561 1000
AVthornHVeth1THORN
The UP resins were added in styrene monomer at 80C to get 35(ww) styrene in the resins Gel times maximum curing temperatures
0
50
100
150
200
250
300
350
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR1
G-UPR2
R-UPR1
Figure 2 The change of acid value with reaction time for G-UPR1 G-UPR2
and R-UPR1
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ORDER REPRINTS
and time required to reach this temperatures of the resins (peak time)were determined by using 15 (ww) MEKP and 1 (ww) cobaltnaphthanate to resins The results are reported in Fig 6 and Table 3Each set of UP resins prepared from the different glycolysis products iscollected in one graph in order to study the effect of the different glycols
0
50
100
150
200
250
300
0 100 200 300 400Time (min)
AV
(mg
KO
Hg
)
G-UPR3
R-UPR2
Figure 3 The change of acid value with reaction time for G-UPR3 and
R-UPR2
0
50
100
150
200
250
300
0 100 200 300Time (min)
AV
(mg
KO
Hg
)
G-UPR4
R-UPR3
Figure 4 The change of acid value with reaction time for G-UPR4 and
R-UPR3
Unsaturated Polyester Resins 1545
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on the curing behavior in Fig 6 Maximum curing temperatures ofG-UPR1 and G-UPR2 (UP resins based on PG glycolyzed product) arehigher than they are for G-UPR3 and G-UPR4 (UP resins based onDEG and TEG glycolysis products) Time required to reach thistemperature and gel time of G-UPR1 and G-UPR2 are shorter thanare those of G-UPR3 and G-UPR4 These properties of G-UPR5 (UPresin based on PG-TEG glycolysis product) were seen to be nearly in themiddle of the other resins (Fig 6) Curing properties of waste PET-basedresins are comparable with the reference resins (Table 3 and Figs 7ndash10)
0
50
100
150
200
250
300
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR5
R-UPR4
Figure 5 The change of acid value with reaction time for G-UPR5 and
R-UPR4
Table 2 AV HV and calculated ethMnTHORN of the UP resins
Symbol of resins AV (mgKOHg) HV (mgKOHg) Calculated ethMnTHORN
G-UPR1 40 75 975
G-UPR2 30 85 975
G-UPR3 30 90 950
G-UPR4 35 85 950
G-UPR5 30 85 950
R-UPR1 60 85 975
R-UPR2 60 85 800
R-UPR3 60 85 800
R-UPR4 60 85 800
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The mechanical properties of the UP resins are presented in Table 4As seen hardness tensile strength and the elastic module of the G-UPR1and G-UPR2 are higher than are those of the other UP resins Butelongation at break percent values of these resins are lower than the otherresins The DEG and TEG units are more flexible than the PG unit dueto the ether linkage The mechanical properties of the PET based resinsare comparable with the reference resins (Table 4)
0
20
40
60
80
100
120
140
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
G-UPR3
G-UPR4
G-UPR5
Figure 6 Maximum curing temperatures of waste PET-based UP resins
Table 3 Curing properties of the UP resins
Symbol
of resins
Gel
time (min)
Max curing
temperature (C)
Peak
time (min)
G-UPR1 10 128 18
G-UPR2 13 103 23
G-UPR3 28 60 50
G-UPR4 33 53 60
G-UPR5 18 75 37
R-UPR1 9 130 17
R-UPR2 33 63 57
R-UPR3 32 65 54
R-UPR4 17 99 32
Unsaturated Polyester Resins 1547
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CONCLUSION
The PET-based unsaturated polyester resins were prepared byreacting the glycolysis products of waste PET with maleic anhydrideReference resins were prepared from maleic anhydride phthalicanhydride and one of the glycol compounds such as PG DEG TEG
0
20
40
60
80
100
120
140
0 10 20 30 40Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
R-UPR1
Figure 7 Maximum curing temperatures of G-UPR1 G-UPR2 and R-UPR1
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR3
R-UPR2
Figure 8 Maximum curing temperatures of G-UPR3 and R-UPR2
1548 Ozturk and Guclu
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ORDER REPRINTS
or PGndashTEG mixture at the same OHCOOH molar ratio with the wastePET based resins
The mechanical properties and curing behaviors of the waste PET-based UP resins are comparable with the reference resins The DEG- andTEG-based resins are more flexible than are PG-based resins due to theether linkage But PG-based resins have higher tensile strength andhardness than do DEG- and TEG-based resins It appears that it isfeasible to recycle waste PET as UP resins by glycolysis reactions usingdifferent glycol compounds and glycol compounds mixtures
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR4
R-UPR3
Figure 9 Maximum curing temperatures of G-UPR4 and R-UPR3
0
20
40
60
80
100
120
0 10 20 30 40 50Time (min)
Tem
p (
degC)
G-UPR5
R-UPR4
Figure 10 Maximum curing temperatures of G-UPR5 and R-UPR4
Unsaturated Polyester Resins 1549
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embe
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ORDER REPRINTS
ACKNOWLEDGMENTS
This work was financially supported by the Research Foundation of
Istanbul University Project Number T-14706032003
REFERENCES
1 Mansour SH Ikladious NE Depolymerization of poly(ethylene
terephthalate) wastes using 14-butandiol and triethylene glycol
Polymer Testing 2002 21 (5) 497ndash5052 Paszun D Spychaj T Chemical recycling of poly(ethylene
terephthalate) Ind Eng Chem Res 1997 36 1373ndash13833 Kosmidis VA Achilias DS Karayannidis GP Poly(ethylene
terephthalate) recycling and recovery of pure terephthalic acid
Kinetics of a phase transfer catalyzed alkaline hydrolysis Macromol
Mater Eng 2001 286 640ndash6474 Petcore News No 1 April 2003 PET Container Recycling Europe
(Petcore) Belgium5 Wan B Kao C Cheng W Kinetics of depolymerization of
poly(ethylene terephthalate) in potassium hydroxide solution Ind
Eng Chem Res 2001 40 509ndash5146 Kao C Cheng W Wan B Investigation of alkaline hydrolysis of
polyethylene terephthalate by differential scannig calorimetry and
thermogravimetric analysis J Appl Polym Sci 1998 70 1939ndash1945
Table 4 Mechanical properties of the UP resins
Symbol
of resins
Hardness
(ShoreBarkol)
Tensile
strength (MPa)
Elastic
module (MPa)
Elongation at
break point ()
G-UPR1 30 (Barkol) 12 40 14
G-UPR2 10 (Barkol) 10 35 16
G-UPR3 95 (Shore) 25 5 69
G-UPR4 80 (Shore) 15 25 72
G-UPR5 99 (Shore) 10 50 19
R-UPR1 45 (Barkol) 15 90 10
R-UPR2 92 (Shore) 35 5 69
R-UPR3 85 (Shore) 17 35 70
R-UPR4 99 (Shore) 99 65 15
1550 Ozturk and Guclu
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of
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ogy]
at 1
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embe
r 20
13
ORDER REPRINTS
7 Karayannidis GP Chatziavgoustis AP Achilias DS
Poly(ethylene terephthalate) recycling and recovery of pure
terphthalic acid by alkaline hydrolysis Adv Polym Technol
2002 21 (4) 250ndash2598 Yoshioka T Motoki T Okuwaki A Kinetics of hydrolysis of
poly(ethylene terephthalate) powder in sulfuric acid by a modified
shrinking-core model Ind Eng Chem Res 2001 40 75ndash799 Guclu G Kas goz A Ozbudak S Ozgumus S Orbay M
Glycolysis of poly(ethylene terephthalate) wastes in xylene J Appl
Polym Sci 1998 69 2311ndash231910 Chen CH Chen CY Lo YW Mao CF Liao WT Studies
of glycolysis of poly(ethylene terephthalate) recycled from post-
consumer soft-drink bottles I influences of glycolysis conditions
J Appl Polym Sci 2001 80 943ndash94811 Vaidya UR Nadkarni VM Unsaturated polyester resins from
poly(ethylene terephthalate) waste 1 Synthesis and characteriza-
tion Ind Eng Chem Res 1987 26 194ndash19812 Vaidya UR Nadkarni VM Unsaturated polyester resins
from poly(ethylene terephthalate) waste 2 Mechanical and
dynamic mechanical properties Ind Eng Chem Res 1988 27
2056ndash206013 Vaidya UR Nadkarni VM Unsaturated polyester resins from
PET waste kinetics of polycondensation J Appl Polym Sci 1987
34 235ndash24514 Aslan S Immirzi B Laurienzo P Malinconico M Martuscelli
E Volpe MG Pelino M Savini L Unsaturated polyester resins
from glycolysed waste polyethylene terephthalate synthesis and
comparison of properties and performance with virgin resin
J Mater Sci 1997 32 2329ndash233615 Farahat MS Abdel-Azim AA Abdel-Raowf ME Modified
unsaturated polyester resins synthesized from poly(ethylene
terephthalate) waste 1 Synthesis and curing characteristics
Macromol Mater Eng 2000 283 1ndash616 Suh DJ Park OO Yoon KH The properties of unsaturated
polyester based on the glycolyzed poly(ethylene terephthalate) with
various glycol compositions Polymer 2000 41 461ndash46617 Guclu G Yalcinyuva T Ozgumus S Orbay M Hydrolysis of
waste polyethylene terephthalate and characterization of products
by differential scanning calorimetry Thermochimica Acta 2003
404 (1ndash2) 193ndash205
Unsaturated Polyester Resins 1551
Dow
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Lul
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rsity
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ogy]
at 1
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ORDER REPRINTS
18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
1552 Ozturk and Guclu
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nloa
ded
by [
Lul
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rsity
of
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ogy]
at 1
752
14
Sept
embe
r 20
13
Request PermissionOrder Reprints
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081PPT200030272
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request Permission Order Reprints link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
Dow
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ogy]
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r 20
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ORDER REPRINTS
and time required to reach this temperatures of the resins (peak time)were determined by using 15 (ww) MEKP and 1 (ww) cobaltnaphthanate to resins The results are reported in Fig 6 and Table 3Each set of UP resins prepared from the different glycolysis products iscollected in one graph in order to study the effect of the different glycols
0
50
100
150
200
250
300
0 100 200 300 400Time (min)
AV
(mg
KO
Hg
)
G-UPR3
R-UPR2
Figure 3 The change of acid value with reaction time for G-UPR3 and
R-UPR2
0
50
100
150
200
250
300
0 100 200 300Time (min)
AV
(mg
KO
Hg
)
G-UPR4
R-UPR3
Figure 4 The change of acid value with reaction time for G-UPR4 and
R-UPR3
Unsaturated Polyester Resins 1545
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on the curing behavior in Fig 6 Maximum curing temperatures ofG-UPR1 and G-UPR2 (UP resins based on PG glycolyzed product) arehigher than they are for G-UPR3 and G-UPR4 (UP resins based onDEG and TEG glycolysis products) Time required to reach thistemperature and gel time of G-UPR1 and G-UPR2 are shorter thanare those of G-UPR3 and G-UPR4 These properties of G-UPR5 (UPresin based on PG-TEG glycolysis product) were seen to be nearly in themiddle of the other resins (Fig 6) Curing properties of waste PET-basedresins are comparable with the reference resins (Table 3 and Figs 7ndash10)
0
50
100
150
200
250
300
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR5
R-UPR4
Figure 5 The change of acid value with reaction time for G-UPR5 and
R-UPR4
Table 2 AV HV and calculated ethMnTHORN of the UP resins
Symbol of resins AV (mgKOHg) HV (mgKOHg) Calculated ethMnTHORN
G-UPR1 40 75 975
G-UPR2 30 85 975
G-UPR3 30 90 950
G-UPR4 35 85 950
G-UPR5 30 85 950
R-UPR1 60 85 975
R-UPR2 60 85 800
R-UPR3 60 85 800
R-UPR4 60 85 800
1546 Ozturk and Guclu
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by [
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rsity
of
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ogy]
at 1
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embe
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The mechanical properties of the UP resins are presented in Table 4As seen hardness tensile strength and the elastic module of the G-UPR1and G-UPR2 are higher than are those of the other UP resins Butelongation at break percent values of these resins are lower than the otherresins The DEG and TEG units are more flexible than the PG unit dueto the ether linkage The mechanical properties of the PET based resinsare comparable with the reference resins (Table 4)
0
20
40
60
80
100
120
140
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
G-UPR3
G-UPR4
G-UPR5
Figure 6 Maximum curing temperatures of waste PET-based UP resins
Table 3 Curing properties of the UP resins
Symbol
of resins
Gel
time (min)
Max curing
temperature (C)
Peak
time (min)
G-UPR1 10 128 18
G-UPR2 13 103 23
G-UPR3 28 60 50
G-UPR4 33 53 60
G-UPR5 18 75 37
R-UPR1 9 130 17
R-UPR2 33 63 57
R-UPR3 32 65 54
R-UPR4 17 99 32
Unsaturated Polyester Resins 1547
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ogy]
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embe
r 20
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CONCLUSION
The PET-based unsaturated polyester resins were prepared byreacting the glycolysis products of waste PET with maleic anhydrideReference resins were prepared from maleic anhydride phthalicanhydride and one of the glycol compounds such as PG DEG TEG
0
20
40
60
80
100
120
140
0 10 20 30 40Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
R-UPR1
Figure 7 Maximum curing temperatures of G-UPR1 G-UPR2 and R-UPR1
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR3
R-UPR2
Figure 8 Maximum curing temperatures of G-UPR3 and R-UPR2
1548 Ozturk and Guclu
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ogy]
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ORDER REPRINTS
or PGndashTEG mixture at the same OHCOOH molar ratio with the wastePET based resins
The mechanical properties and curing behaviors of the waste PET-based UP resins are comparable with the reference resins The DEG- andTEG-based resins are more flexible than are PG-based resins due to theether linkage But PG-based resins have higher tensile strength andhardness than do DEG- and TEG-based resins It appears that it isfeasible to recycle waste PET as UP resins by glycolysis reactions usingdifferent glycol compounds and glycol compounds mixtures
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR4
R-UPR3
Figure 9 Maximum curing temperatures of G-UPR4 and R-UPR3
0
20
40
60
80
100
120
0 10 20 30 40 50Time (min)
Tem
p (
degC)
G-UPR5
R-UPR4
Figure 10 Maximum curing temperatures of G-UPR5 and R-UPR4
Unsaturated Polyester Resins 1549
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ACKNOWLEDGMENTS
This work was financially supported by the Research Foundation of
Istanbul University Project Number T-14706032003
REFERENCES
1 Mansour SH Ikladious NE Depolymerization of poly(ethylene
terephthalate) wastes using 14-butandiol and triethylene glycol
Polymer Testing 2002 21 (5) 497ndash5052 Paszun D Spychaj T Chemical recycling of poly(ethylene
terephthalate) Ind Eng Chem Res 1997 36 1373ndash13833 Kosmidis VA Achilias DS Karayannidis GP Poly(ethylene
terephthalate) recycling and recovery of pure terephthalic acid
Kinetics of a phase transfer catalyzed alkaline hydrolysis Macromol
Mater Eng 2001 286 640ndash6474 Petcore News No 1 April 2003 PET Container Recycling Europe
(Petcore) Belgium5 Wan B Kao C Cheng W Kinetics of depolymerization of
poly(ethylene terephthalate) in potassium hydroxide solution Ind
Eng Chem Res 2001 40 509ndash5146 Kao C Cheng W Wan B Investigation of alkaline hydrolysis of
polyethylene terephthalate by differential scannig calorimetry and
thermogravimetric analysis J Appl Polym Sci 1998 70 1939ndash1945
Table 4 Mechanical properties of the UP resins
Symbol
of resins
Hardness
(ShoreBarkol)
Tensile
strength (MPa)
Elastic
module (MPa)
Elongation at
break point ()
G-UPR1 30 (Barkol) 12 40 14
G-UPR2 10 (Barkol) 10 35 16
G-UPR3 95 (Shore) 25 5 69
G-UPR4 80 (Shore) 15 25 72
G-UPR5 99 (Shore) 10 50 19
R-UPR1 45 (Barkol) 15 90 10
R-UPR2 92 (Shore) 35 5 69
R-UPR3 85 (Shore) 17 35 70
R-UPR4 99 (Shore) 99 65 15
1550 Ozturk and Guclu
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by [
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rsity
of
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ogy]
at 1
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embe
r 20
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7 Karayannidis GP Chatziavgoustis AP Achilias DS
Poly(ethylene terephthalate) recycling and recovery of pure
terphthalic acid by alkaline hydrolysis Adv Polym Technol
2002 21 (4) 250ndash2598 Yoshioka T Motoki T Okuwaki A Kinetics of hydrolysis of
poly(ethylene terephthalate) powder in sulfuric acid by a modified
shrinking-core model Ind Eng Chem Res 2001 40 75ndash799 Guclu G Kas goz A Ozbudak S Ozgumus S Orbay M
Glycolysis of poly(ethylene terephthalate) wastes in xylene J Appl
Polym Sci 1998 69 2311ndash231910 Chen CH Chen CY Lo YW Mao CF Liao WT Studies
of glycolysis of poly(ethylene terephthalate) recycled from post-
consumer soft-drink bottles I influences of glycolysis conditions
J Appl Polym Sci 2001 80 943ndash94811 Vaidya UR Nadkarni VM Unsaturated polyester resins from
poly(ethylene terephthalate) waste 1 Synthesis and characteriza-
tion Ind Eng Chem Res 1987 26 194ndash19812 Vaidya UR Nadkarni VM Unsaturated polyester resins
from poly(ethylene terephthalate) waste 2 Mechanical and
dynamic mechanical properties Ind Eng Chem Res 1988 27
2056ndash206013 Vaidya UR Nadkarni VM Unsaturated polyester resins from
PET waste kinetics of polycondensation J Appl Polym Sci 1987
34 235ndash24514 Aslan S Immirzi B Laurienzo P Malinconico M Martuscelli
E Volpe MG Pelino M Savini L Unsaturated polyester resins
from glycolysed waste polyethylene terephthalate synthesis and
comparison of properties and performance with virgin resin
J Mater Sci 1997 32 2329ndash233615 Farahat MS Abdel-Azim AA Abdel-Raowf ME Modified
unsaturated polyester resins synthesized from poly(ethylene
terephthalate) waste 1 Synthesis and curing characteristics
Macromol Mater Eng 2000 283 1ndash616 Suh DJ Park OO Yoon KH The properties of unsaturated
polyester based on the glycolyzed poly(ethylene terephthalate) with
various glycol compositions Polymer 2000 41 461ndash46617 Guclu G Yalcinyuva T Ozgumus S Orbay M Hydrolysis of
waste polyethylene terephthalate and characterization of products
by differential scanning calorimetry Thermochimica Acta 2003
404 (1ndash2) 193ndash205
Unsaturated Polyester Resins 1551
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18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
1552 Ozturk and Guclu
Dow
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ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
Request PermissionOrder Reprints
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081PPT200030272
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request Permission Order Reprints link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
Dow
nloa
ded
by [
Lul
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rsity
of
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hnol
ogy]
at 1
752
14
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embe
r 20
13
ORDER REPRINTS
on the curing behavior in Fig 6 Maximum curing temperatures ofG-UPR1 and G-UPR2 (UP resins based on PG glycolyzed product) arehigher than they are for G-UPR3 and G-UPR4 (UP resins based onDEG and TEG glycolysis products) Time required to reach thistemperature and gel time of G-UPR1 and G-UPR2 are shorter thanare those of G-UPR3 and G-UPR4 These properties of G-UPR5 (UPresin based on PG-TEG glycolysis product) were seen to be nearly in themiddle of the other resins (Fig 6) Curing properties of waste PET-basedresins are comparable with the reference resins (Table 3 and Figs 7ndash10)
0
50
100
150
200
250
300
0 50 100 150 200 250 300Time (min)
AV
(mg
KO
Hg
)
G-UPR5
R-UPR4
Figure 5 The change of acid value with reaction time for G-UPR5 and
R-UPR4
Table 2 AV HV and calculated ethMnTHORN of the UP resins
Symbol of resins AV (mgKOHg) HV (mgKOHg) Calculated ethMnTHORN
G-UPR1 40 75 975
G-UPR2 30 85 975
G-UPR3 30 90 950
G-UPR4 35 85 950
G-UPR5 30 85 950
R-UPR1 60 85 975
R-UPR2 60 85 800
R-UPR3 60 85 800
R-UPR4 60 85 800
1546 Ozturk and Guclu
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ogy]
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embe
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ORDER REPRINTS
The mechanical properties of the UP resins are presented in Table 4As seen hardness tensile strength and the elastic module of the G-UPR1and G-UPR2 are higher than are those of the other UP resins Butelongation at break percent values of these resins are lower than the otherresins The DEG and TEG units are more flexible than the PG unit dueto the ether linkage The mechanical properties of the PET based resinsare comparable with the reference resins (Table 4)
0
20
40
60
80
100
120
140
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
G-UPR3
G-UPR4
G-UPR5
Figure 6 Maximum curing temperatures of waste PET-based UP resins
Table 3 Curing properties of the UP resins
Symbol
of resins
Gel
time (min)
Max curing
temperature (C)
Peak
time (min)
G-UPR1 10 128 18
G-UPR2 13 103 23
G-UPR3 28 60 50
G-UPR4 33 53 60
G-UPR5 18 75 37
R-UPR1 9 130 17
R-UPR2 33 63 57
R-UPR3 32 65 54
R-UPR4 17 99 32
Unsaturated Polyester Resins 1547
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rsity
of
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ogy]
at 1
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14
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embe
r 20
13
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CONCLUSION
The PET-based unsaturated polyester resins were prepared byreacting the glycolysis products of waste PET with maleic anhydrideReference resins were prepared from maleic anhydride phthalicanhydride and one of the glycol compounds such as PG DEG TEG
0
20
40
60
80
100
120
140
0 10 20 30 40Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
R-UPR1
Figure 7 Maximum curing temperatures of G-UPR1 G-UPR2 and R-UPR1
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR3
R-UPR2
Figure 8 Maximum curing temperatures of G-UPR3 and R-UPR2
1548 Ozturk and Guclu
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by [
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rsity
of
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ogy]
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embe
r 20
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ORDER REPRINTS
or PGndashTEG mixture at the same OHCOOH molar ratio with the wastePET based resins
The mechanical properties and curing behaviors of the waste PET-based UP resins are comparable with the reference resins The DEG- andTEG-based resins are more flexible than are PG-based resins due to theether linkage But PG-based resins have higher tensile strength andhardness than do DEG- and TEG-based resins It appears that it isfeasible to recycle waste PET as UP resins by glycolysis reactions usingdifferent glycol compounds and glycol compounds mixtures
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR4
R-UPR3
Figure 9 Maximum curing temperatures of G-UPR4 and R-UPR3
0
20
40
60
80
100
120
0 10 20 30 40 50Time (min)
Tem
p (
degC)
G-UPR5
R-UPR4
Figure 10 Maximum curing temperatures of G-UPR5 and R-UPR4
Unsaturated Polyester Resins 1549
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rsity
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ogy]
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embe
r 20
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ORDER REPRINTS
ACKNOWLEDGMENTS
This work was financially supported by the Research Foundation of
Istanbul University Project Number T-14706032003
REFERENCES
1 Mansour SH Ikladious NE Depolymerization of poly(ethylene
terephthalate) wastes using 14-butandiol and triethylene glycol
Polymer Testing 2002 21 (5) 497ndash5052 Paszun D Spychaj T Chemical recycling of poly(ethylene
terephthalate) Ind Eng Chem Res 1997 36 1373ndash13833 Kosmidis VA Achilias DS Karayannidis GP Poly(ethylene
terephthalate) recycling and recovery of pure terephthalic acid
Kinetics of a phase transfer catalyzed alkaline hydrolysis Macromol
Mater Eng 2001 286 640ndash6474 Petcore News No 1 April 2003 PET Container Recycling Europe
(Petcore) Belgium5 Wan B Kao C Cheng W Kinetics of depolymerization of
poly(ethylene terephthalate) in potassium hydroxide solution Ind
Eng Chem Res 2001 40 509ndash5146 Kao C Cheng W Wan B Investigation of alkaline hydrolysis of
polyethylene terephthalate by differential scannig calorimetry and
thermogravimetric analysis J Appl Polym Sci 1998 70 1939ndash1945
Table 4 Mechanical properties of the UP resins
Symbol
of resins
Hardness
(ShoreBarkol)
Tensile
strength (MPa)
Elastic
module (MPa)
Elongation at
break point ()
G-UPR1 30 (Barkol) 12 40 14
G-UPR2 10 (Barkol) 10 35 16
G-UPR3 95 (Shore) 25 5 69
G-UPR4 80 (Shore) 15 25 72
G-UPR5 99 (Shore) 10 50 19
R-UPR1 45 (Barkol) 15 90 10
R-UPR2 92 (Shore) 35 5 69
R-UPR3 85 (Shore) 17 35 70
R-UPR4 99 (Shore) 99 65 15
1550 Ozturk and Guclu
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by [
Lul
ea U
nive
rsity
of
Tec
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ogy]
at 1
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embe
r 20
13
ORDER REPRINTS
7 Karayannidis GP Chatziavgoustis AP Achilias DS
Poly(ethylene terephthalate) recycling and recovery of pure
terphthalic acid by alkaline hydrolysis Adv Polym Technol
2002 21 (4) 250ndash2598 Yoshioka T Motoki T Okuwaki A Kinetics of hydrolysis of
poly(ethylene terephthalate) powder in sulfuric acid by a modified
shrinking-core model Ind Eng Chem Res 2001 40 75ndash799 Guclu G Kas goz A Ozbudak S Ozgumus S Orbay M
Glycolysis of poly(ethylene terephthalate) wastes in xylene J Appl
Polym Sci 1998 69 2311ndash231910 Chen CH Chen CY Lo YW Mao CF Liao WT Studies
of glycolysis of poly(ethylene terephthalate) recycled from post-
consumer soft-drink bottles I influences of glycolysis conditions
J Appl Polym Sci 2001 80 943ndash94811 Vaidya UR Nadkarni VM Unsaturated polyester resins from
poly(ethylene terephthalate) waste 1 Synthesis and characteriza-
tion Ind Eng Chem Res 1987 26 194ndash19812 Vaidya UR Nadkarni VM Unsaturated polyester resins
from poly(ethylene terephthalate) waste 2 Mechanical and
dynamic mechanical properties Ind Eng Chem Res 1988 27
2056ndash206013 Vaidya UR Nadkarni VM Unsaturated polyester resins from
PET waste kinetics of polycondensation J Appl Polym Sci 1987
34 235ndash24514 Aslan S Immirzi B Laurienzo P Malinconico M Martuscelli
E Volpe MG Pelino M Savini L Unsaturated polyester resins
from glycolysed waste polyethylene terephthalate synthesis and
comparison of properties and performance with virgin resin
J Mater Sci 1997 32 2329ndash233615 Farahat MS Abdel-Azim AA Abdel-Raowf ME Modified
unsaturated polyester resins synthesized from poly(ethylene
terephthalate) waste 1 Synthesis and curing characteristics
Macromol Mater Eng 2000 283 1ndash616 Suh DJ Park OO Yoon KH The properties of unsaturated
polyester based on the glycolyzed poly(ethylene terephthalate) with
various glycol compositions Polymer 2000 41 461ndash46617 Guclu G Yalcinyuva T Ozgumus S Orbay M Hydrolysis of
waste polyethylene terephthalate and characterization of products
by differential scanning calorimetry Thermochimica Acta 2003
404 (1ndash2) 193ndash205
Unsaturated Polyester Resins 1551
Dow
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ded
by [
Lul
ea U
nive
rsity
of
Tec
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ogy]
at 1
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embe
r 20
13
ORDER REPRINTS
18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
1552 Ozturk and Guclu
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
Request PermissionOrder Reprints
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081PPT200030272
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request Permission Order Reprints link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
The mechanical properties of the UP resins are presented in Table 4As seen hardness tensile strength and the elastic module of the G-UPR1and G-UPR2 are higher than are those of the other UP resins Butelongation at break percent values of these resins are lower than the otherresins The DEG and TEG units are more flexible than the PG unit dueto the ether linkage The mechanical properties of the PET based resinsare comparable with the reference resins (Table 4)
0
20
40
60
80
100
120
140
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
G-UPR3
G-UPR4
G-UPR5
Figure 6 Maximum curing temperatures of waste PET-based UP resins
Table 3 Curing properties of the UP resins
Symbol
of resins
Gel
time (min)
Max curing
temperature (C)
Peak
time (min)
G-UPR1 10 128 18
G-UPR2 13 103 23
G-UPR3 28 60 50
G-UPR4 33 53 60
G-UPR5 18 75 37
R-UPR1 9 130 17
R-UPR2 33 63 57
R-UPR3 32 65 54
R-UPR4 17 99 32
Unsaturated Polyester Resins 1547
Dow
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rsity
of
Tec
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ogy]
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embe
r 20
13
ORDER REPRINTS
CONCLUSION
The PET-based unsaturated polyester resins were prepared byreacting the glycolysis products of waste PET with maleic anhydrideReference resins were prepared from maleic anhydride phthalicanhydride and one of the glycol compounds such as PG DEG TEG
0
20
40
60
80
100
120
140
0 10 20 30 40Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
R-UPR1
Figure 7 Maximum curing temperatures of G-UPR1 G-UPR2 and R-UPR1
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR3
R-UPR2
Figure 8 Maximum curing temperatures of G-UPR3 and R-UPR2
1548 Ozturk and Guclu
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
or PGndashTEG mixture at the same OHCOOH molar ratio with the wastePET based resins
The mechanical properties and curing behaviors of the waste PET-based UP resins are comparable with the reference resins The DEG- andTEG-based resins are more flexible than are PG-based resins due to theether linkage But PG-based resins have higher tensile strength andhardness than do DEG- and TEG-based resins It appears that it isfeasible to recycle waste PET as UP resins by glycolysis reactions usingdifferent glycol compounds and glycol compounds mixtures
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR4
R-UPR3
Figure 9 Maximum curing temperatures of G-UPR4 and R-UPR3
0
20
40
60
80
100
120
0 10 20 30 40 50Time (min)
Tem
p (
degC)
G-UPR5
R-UPR4
Figure 10 Maximum curing temperatures of G-UPR5 and R-UPR4
Unsaturated Polyester Resins 1549
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
ACKNOWLEDGMENTS
This work was financially supported by the Research Foundation of
Istanbul University Project Number T-14706032003
REFERENCES
1 Mansour SH Ikladious NE Depolymerization of poly(ethylene
terephthalate) wastes using 14-butandiol and triethylene glycol
Polymer Testing 2002 21 (5) 497ndash5052 Paszun D Spychaj T Chemical recycling of poly(ethylene
terephthalate) Ind Eng Chem Res 1997 36 1373ndash13833 Kosmidis VA Achilias DS Karayannidis GP Poly(ethylene
terephthalate) recycling and recovery of pure terephthalic acid
Kinetics of a phase transfer catalyzed alkaline hydrolysis Macromol
Mater Eng 2001 286 640ndash6474 Petcore News No 1 April 2003 PET Container Recycling Europe
(Petcore) Belgium5 Wan B Kao C Cheng W Kinetics of depolymerization of
poly(ethylene terephthalate) in potassium hydroxide solution Ind
Eng Chem Res 2001 40 509ndash5146 Kao C Cheng W Wan B Investigation of alkaline hydrolysis of
polyethylene terephthalate by differential scannig calorimetry and
thermogravimetric analysis J Appl Polym Sci 1998 70 1939ndash1945
Table 4 Mechanical properties of the UP resins
Symbol
of resins
Hardness
(ShoreBarkol)
Tensile
strength (MPa)
Elastic
module (MPa)
Elongation at
break point ()
G-UPR1 30 (Barkol) 12 40 14
G-UPR2 10 (Barkol) 10 35 16
G-UPR3 95 (Shore) 25 5 69
G-UPR4 80 (Shore) 15 25 72
G-UPR5 99 (Shore) 10 50 19
R-UPR1 45 (Barkol) 15 90 10
R-UPR2 92 (Shore) 35 5 69
R-UPR3 85 (Shore) 17 35 70
R-UPR4 99 (Shore) 99 65 15
1550 Ozturk and Guclu
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
7 Karayannidis GP Chatziavgoustis AP Achilias DS
Poly(ethylene terephthalate) recycling and recovery of pure
terphthalic acid by alkaline hydrolysis Adv Polym Technol
2002 21 (4) 250ndash2598 Yoshioka T Motoki T Okuwaki A Kinetics of hydrolysis of
poly(ethylene terephthalate) powder in sulfuric acid by a modified
shrinking-core model Ind Eng Chem Res 2001 40 75ndash799 Guclu G Kas goz A Ozbudak S Ozgumus S Orbay M
Glycolysis of poly(ethylene terephthalate) wastes in xylene J Appl
Polym Sci 1998 69 2311ndash231910 Chen CH Chen CY Lo YW Mao CF Liao WT Studies
of glycolysis of poly(ethylene terephthalate) recycled from post-
consumer soft-drink bottles I influences of glycolysis conditions
J Appl Polym Sci 2001 80 943ndash94811 Vaidya UR Nadkarni VM Unsaturated polyester resins from
poly(ethylene terephthalate) waste 1 Synthesis and characteriza-
tion Ind Eng Chem Res 1987 26 194ndash19812 Vaidya UR Nadkarni VM Unsaturated polyester resins
from poly(ethylene terephthalate) waste 2 Mechanical and
dynamic mechanical properties Ind Eng Chem Res 1988 27
2056ndash206013 Vaidya UR Nadkarni VM Unsaturated polyester resins from
PET waste kinetics of polycondensation J Appl Polym Sci 1987
34 235ndash24514 Aslan S Immirzi B Laurienzo P Malinconico M Martuscelli
E Volpe MG Pelino M Savini L Unsaturated polyester resins
from glycolysed waste polyethylene terephthalate synthesis and
comparison of properties and performance with virgin resin
J Mater Sci 1997 32 2329ndash233615 Farahat MS Abdel-Azim AA Abdel-Raowf ME Modified
unsaturated polyester resins synthesized from poly(ethylene
terephthalate) waste 1 Synthesis and curing characteristics
Macromol Mater Eng 2000 283 1ndash616 Suh DJ Park OO Yoon KH The properties of unsaturated
polyester based on the glycolyzed poly(ethylene terephthalate) with
various glycol compositions Polymer 2000 41 461ndash46617 Guclu G Yalcinyuva T Ozgumus S Orbay M Hydrolysis of
waste polyethylene terephthalate and characterization of products
by differential scanning calorimetry Thermochimica Acta 2003
404 (1ndash2) 193ndash205
Unsaturated Polyester Resins 1551
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
1552 Ozturk and Guclu
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
Request PermissionOrder Reprints
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081PPT200030272
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request Permission Order Reprints link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
CONCLUSION
The PET-based unsaturated polyester resins were prepared byreacting the glycolysis products of waste PET with maleic anhydrideReference resins were prepared from maleic anhydride phthalicanhydride and one of the glycol compounds such as PG DEG TEG
0
20
40
60
80
100
120
140
0 10 20 30 40Time (min)
Tem
p (
degC)
G-UPR1
G-UPR2
R-UPR1
Figure 7 Maximum curing temperatures of G-UPR1 G-UPR2 and R-UPR1
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR3
R-UPR2
Figure 8 Maximum curing temperatures of G-UPR3 and R-UPR2
1548 Ozturk and Guclu
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
or PGndashTEG mixture at the same OHCOOH molar ratio with the wastePET based resins
The mechanical properties and curing behaviors of the waste PET-based UP resins are comparable with the reference resins The DEG- andTEG-based resins are more flexible than are PG-based resins due to theether linkage But PG-based resins have higher tensile strength andhardness than do DEG- and TEG-based resins It appears that it isfeasible to recycle waste PET as UP resins by glycolysis reactions usingdifferent glycol compounds and glycol compounds mixtures
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR4
R-UPR3
Figure 9 Maximum curing temperatures of G-UPR4 and R-UPR3
0
20
40
60
80
100
120
0 10 20 30 40 50Time (min)
Tem
p (
degC)
G-UPR5
R-UPR4
Figure 10 Maximum curing temperatures of G-UPR5 and R-UPR4
Unsaturated Polyester Resins 1549
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
ACKNOWLEDGMENTS
This work was financially supported by the Research Foundation of
Istanbul University Project Number T-14706032003
REFERENCES
1 Mansour SH Ikladious NE Depolymerization of poly(ethylene
terephthalate) wastes using 14-butandiol and triethylene glycol
Polymer Testing 2002 21 (5) 497ndash5052 Paszun D Spychaj T Chemical recycling of poly(ethylene
terephthalate) Ind Eng Chem Res 1997 36 1373ndash13833 Kosmidis VA Achilias DS Karayannidis GP Poly(ethylene
terephthalate) recycling and recovery of pure terephthalic acid
Kinetics of a phase transfer catalyzed alkaline hydrolysis Macromol
Mater Eng 2001 286 640ndash6474 Petcore News No 1 April 2003 PET Container Recycling Europe
(Petcore) Belgium5 Wan B Kao C Cheng W Kinetics of depolymerization of
poly(ethylene terephthalate) in potassium hydroxide solution Ind
Eng Chem Res 2001 40 509ndash5146 Kao C Cheng W Wan B Investigation of alkaline hydrolysis of
polyethylene terephthalate by differential scannig calorimetry and
thermogravimetric analysis J Appl Polym Sci 1998 70 1939ndash1945
Table 4 Mechanical properties of the UP resins
Symbol
of resins
Hardness
(ShoreBarkol)
Tensile
strength (MPa)
Elastic
module (MPa)
Elongation at
break point ()
G-UPR1 30 (Barkol) 12 40 14
G-UPR2 10 (Barkol) 10 35 16
G-UPR3 95 (Shore) 25 5 69
G-UPR4 80 (Shore) 15 25 72
G-UPR5 99 (Shore) 10 50 19
R-UPR1 45 (Barkol) 15 90 10
R-UPR2 92 (Shore) 35 5 69
R-UPR3 85 (Shore) 17 35 70
R-UPR4 99 (Shore) 99 65 15
1550 Ozturk and Guclu
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
7 Karayannidis GP Chatziavgoustis AP Achilias DS
Poly(ethylene terephthalate) recycling and recovery of pure
terphthalic acid by alkaline hydrolysis Adv Polym Technol
2002 21 (4) 250ndash2598 Yoshioka T Motoki T Okuwaki A Kinetics of hydrolysis of
poly(ethylene terephthalate) powder in sulfuric acid by a modified
shrinking-core model Ind Eng Chem Res 2001 40 75ndash799 Guclu G Kas goz A Ozbudak S Ozgumus S Orbay M
Glycolysis of poly(ethylene terephthalate) wastes in xylene J Appl
Polym Sci 1998 69 2311ndash231910 Chen CH Chen CY Lo YW Mao CF Liao WT Studies
of glycolysis of poly(ethylene terephthalate) recycled from post-
consumer soft-drink bottles I influences of glycolysis conditions
J Appl Polym Sci 2001 80 943ndash94811 Vaidya UR Nadkarni VM Unsaturated polyester resins from
poly(ethylene terephthalate) waste 1 Synthesis and characteriza-
tion Ind Eng Chem Res 1987 26 194ndash19812 Vaidya UR Nadkarni VM Unsaturated polyester resins
from poly(ethylene terephthalate) waste 2 Mechanical and
dynamic mechanical properties Ind Eng Chem Res 1988 27
2056ndash206013 Vaidya UR Nadkarni VM Unsaturated polyester resins from
PET waste kinetics of polycondensation J Appl Polym Sci 1987
34 235ndash24514 Aslan S Immirzi B Laurienzo P Malinconico M Martuscelli
E Volpe MG Pelino M Savini L Unsaturated polyester resins
from glycolysed waste polyethylene terephthalate synthesis and
comparison of properties and performance with virgin resin
J Mater Sci 1997 32 2329ndash233615 Farahat MS Abdel-Azim AA Abdel-Raowf ME Modified
unsaturated polyester resins synthesized from poly(ethylene
terephthalate) waste 1 Synthesis and curing characteristics
Macromol Mater Eng 2000 283 1ndash616 Suh DJ Park OO Yoon KH The properties of unsaturated
polyester based on the glycolyzed poly(ethylene terephthalate) with
various glycol compositions Polymer 2000 41 461ndash46617 Guclu G Yalcinyuva T Ozgumus S Orbay M Hydrolysis of
waste polyethylene terephthalate and characterization of products
by differential scanning calorimetry Thermochimica Acta 2003
404 (1ndash2) 193ndash205
Unsaturated Polyester Resins 1551
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
1552 Ozturk and Guclu
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
Request PermissionOrder Reprints
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081PPT200030272
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request Permission Order Reprints link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
or PGndashTEG mixture at the same OHCOOH molar ratio with the wastePET based resins
The mechanical properties and curing behaviors of the waste PET-based UP resins are comparable with the reference resins The DEG- andTEG-based resins are more flexible than are PG-based resins due to theether linkage But PG-based resins have higher tensile strength andhardness than do DEG- and TEG-based resins It appears that it isfeasible to recycle waste PET as UP resins by glycolysis reactions usingdifferent glycol compounds and glycol compounds mixtures
0
10
20
30
40
50
60
70
80
0 20 40 60 80Time (min)
Tem
p (
degC)
G-UPR4
R-UPR3
Figure 9 Maximum curing temperatures of G-UPR4 and R-UPR3
0
20
40
60
80
100
120
0 10 20 30 40 50Time (min)
Tem
p (
degC)
G-UPR5
R-UPR4
Figure 10 Maximum curing temperatures of G-UPR5 and R-UPR4
Unsaturated Polyester Resins 1549
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
ACKNOWLEDGMENTS
This work was financially supported by the Research Foundation of
Istanbul University Project Number T-14706032003
REFERENCES
1 Mansour SH Ikladious NE Depolymerization of poly(ethylene
terephthalate) wastes using 14-butandiol and triethylene glycol
Polymer Testing 2002 21 (5) 497ndash5052 Paszun D Spychaj T Chemical recycling of poly(ethylene
terephthalate) Ind Eng Chem Res 1997 36 1373ndash13833 Kosmidis VA Achilias DS Karayannidis GP Poly(ethylene
terephthalate) recycling and recovery of pure terephthalic acid
Kinetics of a phase transfer catalyzed alkaline hydrolysis Macromol
Mater Eng 2001 286 640ndash6474 Petcore News No 1 April 2003 PET Container Recycling Europe
(Petcore) Belgium5 Wan B Kao C Cheng W Kinetics of depolymerization of
poly(ethylene terephthalate) in potassium hydroxide solution Ind
Eng Chem Res 2001 40 509ndash5146 Kao C Cheng W Wan B Investigation of alkaline hydrolysis of
polyethylene terephthalate by differential scannig calorimetry and
thermogravimetric analysis J Appl Polym Sci 1998 70 1939ndash1945
Table 4 Mechanical properties of the UP resins
Symbol
of resins
Hardness
(ShoreBarkol)
Tensile
strength (MPa)
Elastic
module (MPa)
Elongation at
break point ()
G-UPR1 30 (Barkol) 12 40 14
G-UPR2 10 (Barkol) 10 35 16
G-UPR3 95 (Shore) 25 5 69
G-UPR4 80 (Shore) 15 25 72
G-UPR5 99 (Shore) 10 50 19
R-UPR1 45 (Barkol) 15 90 10
R-UPR2 92 (Shore) 35 5 69
R-UPR3 85 (Shore) 17 35 70
R-UPR4 99 (Shore) 99 65 15
1550 Ozturk and Guclu
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
7 Karayannidis GP Chatziavgoustis AP Achilias DS
Poly(ethylene terephthalate) recycling and recovery of pure
terphthalic acid by alkaline hydrolysis Adv Polym Technol
2002 21 (4) 250ndash2598 Yoshioka T Motoki T Okuwaki A Kinetics of hydrolysis of
poly(ethylene terephthalate) powder in sulfuric acid by a modified
shrinking-core model Ind Eng Chem Res 2001 40 75ndash799 Guclu G Kas goz A Ozbudak S Ozgumus S Orbay M
Glycolysis of poly(ethylene terephthalate) wastes in xylene J Appl
Polym Sci 1998 69 2311ndash231910 Chen CH Chen CY Lo YW Mao CF Liao WT Studies
of glycolysis of poly(ethylene terephthalate) recycled from post-
consumer soft-drink bottles I influences of glycolysis conditions
J Appl Polym Sci 2001 80 943ndash94811 Vaidya UR Nadkarni VM Unsaturated polyester resins from
poly(ethylene terephthalate) waste 1 Synthesis and characteriza-
tion Ind Eng Chem Res 1987 26 194ndash19812 Vaidya UR Nadkarni VM Unsaturated polyester resins
from poly(ethylene terephthalate) waste 2 Mechanical and
dynamic mechanical properties Ind Eng Chem Res 1988 27
2056ndash206013 Vaidya UR Nadkarni VM Unsaturated polyester resins from
PET waste kinetics of polycondensation J Appl Polym Sci 1987
34 235ndash24514 Aslan S Immirzi B Laurienzo P Malinconico M Martuscelli
E Volpe MG Pelino M Savini L Unsaturated polyester resins
from glycolysed waste polyethylene terephthalate synthesis and
comparison of properties and performance with virgin resin
J Mater Sci 1997 32 2329ndash233615 Farahat MS Abdel-Azim AA Abdel-Raowf ME Modified
unsaturated polyester resins synthesized from poly(ethylene
terephthalate) waste 1 Synthesis and curing characteristics
Macromol Mater Eng 2000 283 1ndash616 Suh DJ Park OO Yoon KH The properties of unsaturated
polyester based on the glycolyzed poly(ethylene terephthalate) with
various glycol compositions Polymer 2000 41 461ndash46617 Guclu G Yalcinyuva T Ozgumus S Orbay M Hydrolysis of
waste polyethylene terephthalate and characterization of products
by differential scanning calorimetry Thermochimica Acta 2003
404 (1ndash2) 193ndash205
Unsaturated Polyester Resins 1551
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
1552 Ozturk and Guclu
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
Request PermissionOrder Reprints
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081PPT200030272
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request Permission Order Reprints link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
ACKNOWLEDGMENTS
This work was financially supported by the Research Foundation of
Istanbul University Project Number T-14706032003
REFERENCES
1 Mansour SH Ikladious NE Depolymerization of poly(ethylene
terephthalate) wastes using 14-butandiol and triethylene glycol
Polymer Testing 2002 21 (5) 497ndash5052 Paszun D Spychaj T Chemical recycling of poly(ethylene
terephthalate) Ind Eng Chem Res 1997 36 1373ndash13833 Kosmidis VA Achilias DS Karayannidis GP Poly(ethylene
terephthalate) recycling and recovery of pure terephthalic acid
Kinetics of a phase transfer catalyzed alkaline hydrolysis Macromol
Mater Eng 2001 286 640ndash6474 Petcore News No 1 April 2003 PET Container Recycling Europe
(Petcore) Belgium5 Wan B Kao C Cheng W Kinetics of depolymerization of
poly(ethylene terephthalate) in potassium hydroxide solution Ind
Eng Chem Res 2001 40 509ndash5146 Kao C Cheng W Wan B Investigation of alkaline hydrolysis of
polyethylene terephthalate by differential scannig calorimetry and
thermogravimetric analysis J Appl Polym Sci 1998 70 1939ndash1945
Table 4 Mechanical properties of the UP resins
Symbol
of resins
Hardness
(ShoreBarkol)
Tensile
strength (MPa)
Elastic
module (MPa)
Elongation at
break point ()
G-UPR1 30 (Barkol) 12 40 14
G-UPR2 10 (Barkol) 10 35 16
G-UPR3 95 (Shore) 25 5 69
G-UPR4 80 (Shore) 15 25 72
G-UPR5 99 (Shore) 10 50 19
R-UPR1 45 (Barkol) 15 90 10
R-UPR2 92 (Shore) 35 5 69
R-UPR3 85 (Shore) 17 35 70
R-UPR4 99 (Shore) 99 65 15
1550 Ozturk and Guclu
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
7 Karayannidis GP Chatziavgoustis AP Achilias DS
Poly(ethylene terephthalate) recycling and recovery of pure
terphthalic acid by alkaline hydrolysis Adv Polym Technol
2002 21 (4) 250ndash2598 Yoshioka T Motoki T Okuwaki A Kinetics of hydrolysis of
poly(ethylene terephthalate) powder in sulfuric acid by a modified
shrinking-core model Ind Eng Chem Res 2001 40 75ndash799 Guclu G Kas goz A Ozbudak S Ozgumus S Orbay M
Glycolysis of poly(ethylene terephthalate) wastes in xylene J Appl
Polym Sci 1998 69 2311ndash231910 Chen CH Chen CY Lo YW Mao CF Liao WT Studies
of glycolysis of poly(ethylene terephthalate) recycled from post-
consumer soft-drink bottles I influences of glycolysis conditions
J Appl Polym Sci 2001 80 943ndash94811 Vaidya UR Nadkarni VM Unsaturated polyester resins from
poly(ethylene terephthalate) waste 1 Synthesis and characteriza-
tion Ind Eng Chem Res 1987 26 194ndash19812 Vaidya UR Nadkarni VM Unsaturated polyester resins
from poly(ethylene terephthalate) waste 2 Mechanical and
dynamic mechanical properties Ind Eng Chem Res 1988 27
2056ndash206013 Vaidya UR Nadkarni VM Unsaturated polyester resins from
PET waste kinetics of polycondensation J Appl Polym Sci 1987
34 235ndash24514 Aslan S Immirzi B Laurienzo P Malinconico M Martuscelli
E Volpe MG Pelino M Savini L Unsaturated polyester resins
from glycolysed waste polyethylene terephthalate synthesis and
comparison of properties and performance with virgin resin
J Mater Sci 1997 32 2329ndash233615 Farahat MS Abdel-Azim AA Abdel-Raowf ME Modified
unsaturated polyester resins synthesized from poly(ethylene
terephthalate) waste 1 Synthesis and curing characteristics
Macromol Mater Eng 2000 283 1ndash616 Suh DJ Park OO Yoon KH The properties of unsaturated
polyester based on the glycolyzed poly(ethylene terephthalate) with
various glycol compositions Polymer 2000 41 461ndash46617 Guclu G Yalcinyuva T Ozgumus S Orbay M Hydrolysis of
waste polyethylene terephthalate and characterization of products
by differential scanning calorimetry Thermochimica Acta 2003
404 (1ndash2) 193ndash205
Unsaturated Polyester Resins 1551
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ogy]
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752
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18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
1552 Ozturk and Guclu
Dow
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ded
by [
Lul
ea U
nive
rsity
of
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hnol
ogy]
at 1
752
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Sept
embe
r 20
13
Request PermissionOrder Reprints
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081PPT200030272
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request Permission Order Reprints link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
Dow
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rsity
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7 Karayannidis GP Chatziavgoustis AP Achilias DS
Poly(ethylene terephthalate) recycling and recovery of pure
terphthalic acid by alkaline hydrolysis Adv Polym Technol
2002 21 (4) 250ndash2598 Yoshioka T Motoki T Okuwaki A Kinetics of hydrolysis of
poly(ethylene terephthalate) powder in sulfuric acid by a modified
shrinking-core model Ind Eng Chem Res 2001 40 75ndash799 Guclu G Kas goz A Ozbudak S Ozgumus S Orbay M
Glycolysis of poly(ethylene terephthalate) wastes in xylene J Appl
Polym Sci 1998 69 2311ndash231910 Chen CH Chen CY Lo YW Mao CF Liao WT Studies
of glycolysis of poly(ethylene terephthalate) recycled from post-
consumer soft-drink bottles I influences of glycolysis conditions
J Appl Polym Sci 2001 80 943ndash94811 Vaidya UR Nadkarni VM Unsaturated polyester resins from
poly(ethylene terephthalate) waste 1 Synthesis and characteriza-
tion Ind Eng Chem Res 1987 26 194ndash19812 Vaidya UR Nadkarni VM Unsaturated polyester resins
from poly(ethylene terephthalate) waste 2 Mechanical and
dynamic mechanical properties Ind Eng Chem Res 1988 27
2056ndash206013 Vaidya UR Nadkarni VM Unsaturated polyester resins from
PET waste kinetics of polycondensation J Appl Polym Sci 1987
34 235ndash24514 Aslan S Immirzi B Laurienzo P Malinconico M Martuscelli
E Volpe MG Pelino M Savini L Unsaturated polyester resins
from glycolysed waste polyethylene terephthalate synthesis and
comparison of properties and performance with virgin resin
J Mater Sci 1997 32 2329ndash233615 Farahat MS Abdel-Azim AA Abdel-Raowf ME Modified
unsaturated polyester resins synthesized from poly(ethylene
terephthalate) waste 1 Synthesis and curing characteristics
Macromol Mater Eng 2000 283 1ndash616 Suh DJ Park OO Yoon KH The properties of unsaturated
polyester based on the glycolyzed poly(ethylene terephthalate) with
various glycol compositions Polymer 2000 41 461ndash46617 Guclu G Yalcinyuva T Ozgumus S Orbay M Hydrolysis of
waste polyethylene terephthalate and characterization of products
by differential scanning calorimetry Thermochimica Acta 2003
404 (1ndash2) 193ndash205
Unsaturated Polyester Resins 1551
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
1552 Ozturk and Guclu
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
Request PermissionOrder Reprints
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081PPT200030272
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request Permission Order Reprints link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
ORDER REPRINTS
18 Pierson RH In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 32
19 Lucchesi CA In Standart Method of Chemical Analysis WecherFC Roberts E Eds Krieger Publishing Company IncNew York 1975 Chapter 37
1552 Ozturk and Guclu
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
Request PermissionOrder Reprints
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081PPT200030272
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request Permission Order Reprints link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13
Request PermissionOrder Reprints
Reprints of this article can also be ordered at
httpwwwdekkercomservletproductDOI101081PPT200030272
Request Permission or Order Reprints Instantly
Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content
All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved
Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request Permission Order Reprints link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom
The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details
Dow
nloa
ded
by [
Lul
ea U
nive
rsity
of
Tec
hnol
ogy]
at 1
752
14
Sept
embe
r 20
13