The Effect of Oligomeric Terminal Group Balance On Catalyzed Polycondensation of Poly (Ethylene Terephthalate) - Patel

The Effect of Oligomeric Terminal Group Balance on
Catalyzed Polycondensation of Poly(Ethylene Terephthalate)
von
Himanshu Patel
aus Vallabh Vidyanagar, Indien
von der Faukultt II Mathematik und Naturwissenschaften

der Technischen Universitt Berlin
zur Erlangung des akademischen Grades
Doktor der Naturwissenschaften
- Dr. rer. nat.
genehmigte Dissertation
Promotionsausschuss:
Vorsitzender: Prof. Dr. T. Ressler, TU Berlin
1. Berichter: Prof. Dr. R. Schomcker, TU Berlin
2. Berichter: Dr. habil. G. Feix, Equipolymers GmbH
Tag der wissenschaftlichen Aussprache: 23. Juli 2008
Berlin, 2008
D 83
Acknowledgement
ThisworkwasmadeduringmytimeasaPh.D.studentattheR&DdepartmentforPET/PTA,
EquipolymersGmbH,Schkopau.ItakethisopportunitytoexpressmygratitudetoDr.habil.G.
Feix, my research supervisor, mentor, for his invaluable guidance, teaching and advice
throughout the course of this investigation. I have learnt from him to interpret, concise and
correctmyapproachtosciencefromformulationtothepresentationofmyresults.
IwishtothankProfessorDr.R.Schomcker,forhistrustingivingmethisresponsibilityand
for his motivation and support in numerous ways during the discussions with him. It is my
honortoacknowledgeProfessorDr.K.H.Reichert,whowasmysourceofinspirationtochoose
thiscareer.IshallbegratefultohimfortheencouragementIgotfromhimduringmyresearch
work.
I am grateful to Dr. habil. V. Voerckel, Dr. U. Pfannmller and H. Stuber for taking keen
interest and giving remarks for my work. I would like to thank Equipolymers GmbH for an
excitingprojectandfinancialsupport.
MyspecialthanksgoestoDr.S.Hillerwhogavememuchtechnicalassistanceduringthefirst
steps of my project. I would like to thank Silvia Hubold for helping me in carrying out
experimentsatallstages,IamalsothankfultoManuelaLauteandClaudiaBunkforproviding
expressanalyticalresultsofmyexperiments.
Iwouldliketothankallmypastandpresentcolleagues(inalphabeticalorder)Dr.R.Eckert,
Dr.F.Kller,M.Nagel,Dr.A.Rastogi,I.Ritter,D.Runkel,H.Schaarschmidt,K.Scheibe,M.Sela,
Dr.M.StolpandJ.P.Wiegnerforallthescientificandsocialsupport.Iconsideritaprivilegeto
have been a member of this group for the past 4 years. We have had countless productive
discussioninthelaboratoryaswellasmemorableexperienceduringthehikingtripswithJ.P.
Wiegner.Thankyouforyourimmenseunderstandingandcontributiontothissuccess.
Myendlessthankstomypastandpresentuniversitycolleagues:Mohammed,FaissalAliand
Fatemehforeverythingtheyhavedone.IwishtothankmyfriendsinGermanyandabroadfor
theirconstantsupportandencouragement.
I dedicate this thesis to my parents and I am deeply and thoroughly indebted to them.
ThereafterIamthankfultoallmyfamilymembersforallthefreedomandmoralsupportthey
havegiventochoiceofmycareerandlifestyle.
My last but not least goes to my beloved wife Dharti. Thank you for your love, support and
patienceduringthelongprocesstowardsthisgoal.
AbstractofDissertation
Theeffectofoligomericterminalgroupbalanceoncatalyzedpolycondensationof
Poly(ethyleneterephthalate)

By

HimanshuPatel

Poly(ethylene terephthalate) commonly known as PET has been a commercially
importantpolymersinceitsintroductionin1950sanditismainlyusedinfiberandpackaging
industries. It is mainly produced by synthesis of terephthalic acid (TPA) and ethylene glycol
(EG). For PET synthesis, at first, primary esterification of TPA with EG takes place. The chain
prolongation is furtherobtained by the reaction betweencarboxylgroups (COOH) and ester
end groups (OH) of the oligomers (secondary esterification) and simultaneously through the
reactionbetweenesterendgroups(transesterification).
The major factors influencing the overall reaction rate include the catalyst,
temperature, pressure, diffusion rate of volatile byproducts but also the reactant balance
which means the end group balance COOH/(COOH+OH). The effects of first four factors are
readily understood. However, the influence of the end group balance in the melt phase
polycondensation has not been studied extensively. This is of utmost importance since the
batch reactor and continuous reactor cascade generate different oligomeric structure
consequently it becomes difficult to transfer the kinetic data of the melt phase
polycondensationfromlaboratorytothecontinuousplant.
Theprimarygoalofthisprojectwastostudytheinfluenceofendgroupbalanceonthe
reactionratesofsecondaryesterificationandtransesterificationreactions.Anothertaskwasto
study the influence of end group balance on the reaction rates in the presence of different
catalysts.Anessentialprerequisiteofthesestudieswastoproduceoligomerswithdefinedend
group balance in the primary esterification, which acts as a starting point of the melt phase
polycondensation.
The esterification phase was performed with specific EG/TPA feed mol ratio under
differentreactionpressuretoproduceoligomerswithvariedendgroupbalancebyremoving
waterasabyproductandEGasanexcessreactantinasemibatchreactor.Theproducedwater
was distilledoff and the remaining EG was managed by pressure and its reflux from the
column.BycontrollingoftheEGcontentintheliquidphasealongwiththereaction,oligomers
with broad range of end group balance can be produced. Such oligomers could also be
producedbyprimaryesterificationincontinuousreactorcascade,whichfurtheractsastarting
pointofthecontinuousmeltpolycondensationphase.
ThefirststepoftheprimaryesterificationinvolvesthedissolutionofTPAinEGandin
theesterifiedproduct(oligomers).Consequently,theTPAdissolutionrateisalsoinfluencedby
thespecificsurfaceofTPAcrystalsandtheactualparticlesizedistribution.
The influence of TPA particle size distribution on the primary esterification rate was
simulatedbyusingnewlydevelopedmodelforprimaryesterification.Esterificationmodelwas
developed by considering esterification reactions and solidliquid mass transport of TPA in
liquidphaseandliquidvapormasstransfereffectforEGandwater.Itwasobservedthatthe
esterificationratebecamemoresensitivetowardsTPAparticlesizedistributionastheEG/TPA
feedratiowaslowered.
Theesterifiedoligomerwerefurtherreactedunderhighvacuum(~0.1mbar)toobtain
amorphous PET as observed in continuous melt polycondensation (Mn: ~ 20000 g/mol) by
effective removal of reaction condensate EG and water due to constant regeneration of
specificsurface(Helixstirrer).
Twocatalystssystemwerestudied:AntimonyandTitaniumcomplexes.Themaximum
overall reaction rate of the Antimony catalyzed polycondensation was observed with
oligomeric end group balance (COOH/(COOH+OH)) in the range of 0.2 to 0.3; while titanium
basedcatalysthaveshownoptimalreactionratewithdecreasing(COOH/(COOH+OH))balance
and optimum towards zero, which means oligomers with only esterend groups exhibits
maximumreactionrate.
The polycondensation model was developed by considering esterification and
transesterificationreactions,sidereactionssuchasformationofvinylesterandacetaldehyde,
coupled with antimony inhibition factor considered from literature and liquidvapor mass
transfer effect of EG and water. Using the model, the kinetics of the PET polymerization
including the side reactions, the chain length of the produced polymers with respect to
terminalgroupbalancewerewellmodeled.

ZusammenfassungderDissertation
DerEinflussdesVerhltnissesderOligomerEndgruppenaufdiekatalysierte
PolykondensationvonPoly(ethylenterephthalat)

Von
HimanshuPatel

Poly(ethylenterephthalat) im folgenden PET ist seit seiner Einfhrung in den 50er
Jahren des vorigen Jahrhunderts ein weit genutzter Kunststoff fr die Faser und
Verpackungsindustrie geworden. Heute wird es vornehmlich aus Terephthalsure (TPA) und
Ethylenglykol(EG)hergestellt.BeiderPETSyntheseerfolgtzunchstdieprimreVeresterung
derTPAmitEG.DarauffolgtderKettenaufbausowohldurchdieReaktionzwischenCarboxyl
Gruppen (COOH) und EsterEndgruppen (OH) der Oligomeren (sekundre Veresterung) und
simultandurchdieReaktionderEsterEndgruppenmiteinander(Umesterung).
Die Hauptfaktoren, welche die Gesamtreaktionsgeschwindigkeit beeinflussen, sind
neben den Katalysatoren die Temperatur, der Druck, die Diffusionsgeschwindigkeit der
flchtigenReationsprodukte,aberauchdasVerhltnisderReaktanten,d.h.dasVerhltnisder
Endgruppen COOH/(COOH + OH). Der Einfluss der vier erstgenannten Faktoren ist in der
Literaturvielfachbeschrieben,wenigerjedochderEffektdeso.g.EndgruppenVerhltnissesin
derSchmelzphasenPolykondensation.DieseristinsofernvonBedeutung,daBatchReaktoren
undkontinuierlicharbeitendeAnlagenunterschiedlicheOligomerstrukturenerzeugen.Insofern
istdiebertragungvonkinetischenInformationzurderSchmelzepolykondensationvomLabor
aufGroanlagenzustzlicherschwert.
Das Ziel dieser Arbeit war es, den Einflu dieses EndgruppenVerhltnisses auf die
Reaktionsgeschwindigkeiten der sekundren Veresterung und Umesterung, aber auch des
Gesamtumsatzes bei der Verwendung verschiedener Katalysatoren zu messen und zu
berechnen.EinewesentlicheVoraussetzungdieserStudienwardieHerstellungvonOligomeren
mit definierten Endgruppenverhltnissen in der primren Veresterung als Ausgangspunkt der
SchmelzphasenPolykondensation.
Um die Endgruppenverhltnisse der Oligomeren definiert einzustellen, wurde die
primre Veresterung bei verschiedenen EG/TPAMolverhltnissen und bei verschiedenen
Drcken in einem SemiBatchReaktor durchgefhrt. Das entstehende Wasser wurde
abdestilliert, die im Reaktionssystem verbleibende Menge EG wurde durch den Druck und
somit vom Rckfluss der Kolonne gesteuert. Dadurch konnte die Menge EG in der flssigen
Phase auch whrend der Reaktion gesteuert und eine breitere Variation der Oligomeren
Endgruppen erzielt werden. Auf diese Weise konnte auch solche Oligomerstrukturen
hergestelltwerden,wiesiebeiderprimrenVerseterunginkontinuierlichenAnlagenerzeugt
undalsAusgangspunktfrdiekontinuierlicheSchmelzphasenPolykondensationdienen.
DerersteSchrittderpimrenVeresterungistdieAuflsungderfestenTPAinEG.bzw.
indengebildetenVeresterungsprodukten.DadurchsinddieweiterenReaktionsschrittevonder
Auflsungsgeschwindigkeit der TPA beeinflut. Diese wiederum hngt von der spezifischen
OberflchederTPA,d.h.vonderaktuellenKorngrenverteilungderTPAKristalleunddamit
vomGradderAuflsungderTPAab.
Aus diesem Grunde wurde der Einfluss der Korngrenverteilung auf die
GeschwindigkeitderprimrenVeresterungdurcheinneuentwickeltesModellfrdieprimre
Veresterung simuliert. Dieses Modell bercksichtigt neben der spezifischen Oberflche die
einzelnen Veresterungsreaktionen und die Massenbergnge festflssig fr die TPA und
flssiggasfrEGundWasser.Eskonntegezeigtwerden,dadieKorngrenverteilungeinen
steigenden Einflu auf die Veresterungsgeschwindigkeit besitzt, wenn das Molverhltnis
EG/TPAkleinerwird.
Die gezielt synthetisierten Oligomere wurden im Vakuum bis zu einem
Molekulargewichtpolykondensiert,wieesinkontinuierlichenAnlageninderSchmelzphasen
Polykondensation blich ist (ca. 20000 g/mol). Dies gelang durch eine effektive berfhrung
von EG und Wasser in die Gasphase mit Hilfe von Vakuum (ca. 0,1 mbar) und der stndigen
ErneuerungderOberflche(Spiralrhrer).
Es wurden zwei Katalysatorsysteme untersucht: Antimon und Titanverbindungen. Die
maximale Gesamtreaktionsgeschwindigkeit der Antimonkatalysierten Polykondensation
erzieltmanmitCOOH/(COOH+OH)VerhltnissenderOligomerenzwischen0,2bis0,3.Beider
hier verwendeten Titanverbindung steigt die Reaktionsgeschwindigkeit mit abnehmendem
COOH/(COOH+OH)Verhltnis an, das Optimum liegt bei Null. Das heit, das Oligomer sollte
nurEsterEndgruppenbesitzen.
Das in der Arbeit vorgestellte Modell zur Beschreibung der Polykondensation enthlt
die Veresterungs und UmsterungsReaktionen, Zerfallsreaktionen zu Vinylester und
Acetaldehyd, einen von der Literatur bereits eingefhrten AntimonInhibitionFaktor und die
Massenbergnge flssiggas fr EG und Wasser. Die Kinetik der PETPolykondensation,
einschlielich der Teilreaktionen, die Kettenlnge und das Endgruppenverhltnis des APET
konntendurchdasModellgutbeschriebenwerden.
Contents
AbstractofDissertation.................................................................................................................................III
AbstractofDissertation(Deutsch)............................................................................................................V
Chapter1:Poly(EthyleneTerephthalate)ChemistryandProduction
Technology....4
Historyandeconomicalimportance...................................................................................................4
Chemistry...............................................................................................................................................................4
Esterification/Hydrolysis...................................................................................................................5
Transesterification/Glycolysis.........................................................................................................6
Etherification..........................................................................................................................................6
ThermalDegradation..........................................................................................................................7
AcetaldehydeGeneration...................................................................................................................8
PETproductionbymeltpolymerization...................................................................................9
References............................................................................................................................................19
Chapter2:ExperimentalDetails..........................................................................................................21
Materials...............................................................................................................................................21
Reactorspecificationandexperimentalprocedure...........................................................21
Experimentoptimization...............................................................................................................23
Esterificationphase............................................................................................................23
Polycondensationphase....................................................................................................24
Evaluationofexperimentalresults...........................................................................................26
Determinationofintrinsicviscosity............................................................................26
Determinationofcarboxylendgroupsoftheresin................................................27
Determinationofdiethyleneglycol(DEG).27
Determinationofwaterinreactionbyproductmixture..27
Chapter3:SemibatchEsterificationProcessforPETSynthesis...28
Abstract.................................................................................................................................................28
Introduction........................................................................................................................................29
Experimentalmethod......................................................................................................................31
Resultsanddiscussion....................................................................................................................32
Mathematicalmodel..........................................................................................................32
Influenceofmonomerfeedratioonwatergenerationrate..40
Influenceofmonomerfeedratiooncarboxylfraction.....41
Influenceofmonomerfeedratioonchainlengthandmolecularweight......42
Influenceofmonomerfeedratioonconversion.......44
Differentfunctionalgroupconcentrationprofileduringesterification
phase...45
InfluenceofTPAparticlesizeonconversion..46
InfluenceofmonomerfeedratioonDEGformation..48
Conclusion............................................................................................................................................48
Nomenclature.....................................................................................................................................49
Appendix...............................................................................................................................................50
References............................................................................................................................................51
Chapter4:InfluenceofReactionPressureonSemibatchEsterificationProcessof
PETSynthesis..................................................................................................................................................53
Abstract.................................................................................................................................................53
Introduction........................................................................................................................................54
Conclusion............................................................................................................................................68
Nomenclature.....................................................................................................................................69
References............................................................................................................................................70
ii
Chapter5:InfluenceofOligomericCarboxylandHydroxylGroupBalanceon
CatalyzedPolycondensationofPETSynthesis.............................................................................71
Abstract.................................................................................................................................................71
Introduction........................................................................................................................................72
Conclusion............................................................................................................................................86
Nomenclature.....................................................................................................................................87
References............................................................................................................................................88
Appendix............................................................................................................................................................89
CurriculumVitae....................................................................................................................................93
iii
Chapter1:Poly(ethyleneterephthalate)ChemistryandProduction
Technology
Historyandeconomicalimportance
Polyestersarenowoneoftheeconomicallymostimportantclassofpolymersinusetoday
and one of the widely applied polyester is PET. In the last century, pioneering work of
Carothers and his research group elucidated the fundamental principle of condensation
process and synthesized true aliphatic polyesters in 1930.1 However, the development of
aliphatic polyester did not earn him the commercial success due to their melting points
being too low for their practical utility. In 1940, Whinfield initiated research on making
polyesterfromterephthalicacidandethyleneglycolatCalicoPrintersAssociation(CPA)in
UK and came with success and filed the patent.2,3,4 DuPont acquired the Whinfield and
DicksonpatentofpolyesterfiberintheUSAwhileICIpossessedthepatentlicenseforthe
rest of the world. Initially, DuPont commercialized the process for continuous
polymerizationofPETin1952.5However,until1963mostPETwasmadebyadiscontinuous
polymerization process. In 1962, Zimmer developed an integrated continuous ester
interchange and polycondensation process.6 Excellent properties and reasonable price of
PET fibers attracted fast development of the resin production technology. With a global
production of >40 million tones per annum, PET is considered as a one of the leading
polymerresinsintherecenttimes.About63%ofPETisusedasfibersinstaple,filamentand
wovenformswhiletheremaining37%isusedasapackagingresinforbottles,containers,
sheet and film. Global growth rates for PET usage in fibers and packaging are estimated
around4%and8%peryear,respectively.7Thegrowthforpackagingapplicationisduetoa
very favorable image of environmentally friendly and recyclable polymers in western
countries, while for textile applications is due to a strong demand in the fareast area to
meettheneedsofanincreasingeconomyandpopulation.8
Chemistry
Polyestersaredefinedaspolymerscontainingatleastoneesterlinkinggroupperrepeating
unit.8PETformationinvolvestwomainreactions,esterificationofcarboxylendgroupswith
hydroxyl end groups and transesterification of glycolesters with terminal hydroxyl group.
4
Additionally,esterinterchangereactionofestergroupsandreactionofcarboxylgroupswith
boundestergroups(acidolysis)alsotakesplace.However,thequalityofthepolymerisalso
affected by several side reactions such as diethylene glycol (DEG) formation, thermal
scissionofdiestergroup,acetaldehydeandcyclicoligomersformationreactions.
Esterification/Hydrolysis
Esterification reaction is the key reaction and occurs at all stages in PET synthesis. It is
coupled with reverse reaction being hydrolysis. Esterification/hydrolysis reactions have an
equilibriumconstantabout1.25andproceedviaAAC2mechanism(scheme1.1andscheme
1.2).Thisreactionisaprotoncatalyzedreactionwithanoverallorderof3(2withrespectto
acidand1withrespecttoalcohol).9Althoughacidisanefficientcatalystforesterification
reaction,Titaniumbasedcatalystsarealsofoundtobeveryactiveforthesame.Ottonand
Ratton10studiedtheinfluenceofthenatureofthecarboxylicacidonthereactionrateand
concluded that the different reactivity of carboxylic acid among terephthalic acid (TPA),
isopthalic acid (IPA) and oligomers is influenced by steric and electronic conditions of the
carboxylgroups.TheesterificationrateconstantisdependentonthepKaofthecarboxylic
acid.
COOH + HOC2H4OH COOC2H4OH + H2O

Scheme1.1Generationofprepolymerwithterminalhydroxylbyesterificationofacidwith
EG.
COOH + HOC2H4OOC
COOC2H4OOC + H2O

Scheme1.2Chainpropagationbyesterificationofacidwithhydroxylterminated
prepolymer.

5
Transesterification/Glycolysis
2 COOC2H4OH
COOC2H4OOC + HOC2H4OH

Scheme1.3Chainpropagationbytransesterificationreactionofterminalhydroxylwith
estergroup.
Transesterificationwhichisoftentermedaspolycondensationreaction,isthemainreaction
of PET synthesis particularly in melt and solid phase. It is an equilibrium reaction and the
reversereactionistermedasglycolysis(scheme1.3).Sincetheequilibriumconstantisclose
to 0.5, the removal of EG as a byproduct is rate determining step. This reaction is
accelerated by the use of the metal catalysts such as antimony, titanium or germanium
based compounds. Antimony or titanium compounds catalyze the polycondensation by
ligandexchange reaction. Otton and Ratton10 observed that acid also catalyzes the
polycondensation reaction; however, it is about three times slower than acid catalyzed
esterification. The overall reaction order of polycondensation is assumed to be 3, being 1
eachforester,alcoholandcatalyst.11
Etherification
Theformationofdiethyleneglycol(DEG)isanimportantsidereactioninPETsynthesis.The
quantity of DEG in PET chains affects the properties of the polymer; for instance thermal
andlightstability.MeltingpointofthePETresindecreasesbyabout5Cforeachpercent
increase in DEG concentration. Most DEG is formed during esterification stage, since the
etherificationreactionsareknowntobeacidcatalyzed(scheme1.4).12Activationenergies
are estimated between 38 and 181 kJ/mol, which suggests that DEG formation is very
sensitive towards chemical environment regarding the changing functional groups
concentrationandthepresenceofprotonandmetalcatalysts.
6
COOC2H4OH + HOC2H4OH
COOH + HOC2H4OC2H4OH
COOC2H4OH + HOC2H4OOC
COOH + HOC2H4OC2H4OOC
COOC2H4OH + HOC2H4OC2H4OOC
COOC2H4OOC + HOC2H4OC2H4OH

Scheme1.4DifferentmechanismsfortheDEGformation.
ThermalDegradation
Thermal degradation of PET has major influence on the PET quality by affecting the
molecular weight, formation of acid end groups and acetaldehyde, and yellowing of the
polymer. Thermal degradation becomes more visible at temperatures above the melting
point, which is inevitable during synthesis and processing. These reactions are mainly
influencedbymetalcatalystsuchaszinc,cobaltandnickel.However,degradationreactions
could be reduced by addition of triarylphosphites or triarylphosphates blocking the metal
ions. Any small traces of oxygen can also accelerate the thermooxidative degradation.
Thermalesterdegradationisafirstorderreaction.
7
COOC2H4OOC
COOH + CH2=CHOOC

Scheme1.5Thermaldegradationofinternalesterlink.
AcetaldehydeGeneration
Acetaldehydemigrationevenintheconcentrationaslowasfewppm causesflavorinthe
PET bottled soft drinks.13 Thermal scission of ester bond generates terminal vinyl group
and/oracid(scheme1.5andscheme1.6).However,thetransesterificationofterminalvinyl
group liberates acetaldehyde (scheme 1.7). Sufficient amounts of hydroxyl groups will
esterifytheacidgroupsaswellastransesterifythevinylgroupsandthatreformsthebroken
estergroupwithadditionalacetaldehydegeneration.Asthehydroxylconcentrationdrops,
the molecular weight will begin to fall due to excess of carboxyl and vinyl group
accumulation.
COOC2H4OH COOH + CH3CHO

Scheme1.6Acetaldehydegenerationbythermaldegradationofterminalhydroxylgroup.
COOCH=CH2 + HOC2H4OOC
COOC2H4OOC + CH3CHO

Scheme1.7Acetaldehydegenerationbythermaldegradationofterminalhydroxylgroup.

8
PETproductionbymeltpolymerization
PET is polyester formed by stepgrowth polycondensation mainly from terephthalic acid
(TPA)andethyleneglycol(EG).Morethan90%ofPETproductionisbasedonTPAandEG
route because of the economical benefits. The rest of the PET production is based on
dimethylterephthalate(DMT)andEG.SinceTPAofsufficientpuritywasnotavailableinthe
early days, the DMT route was the only process used in commercial production of PET.
However, the process based on TPA became popular since late 1960s due to possible
purification of TPA by recrystallization. Process based on TPA and EG offers several
advantagesovertheDMTandEGroute.ProcessbasedonTPAoffershigherreactionrates,
lowerstorageandtransportcostofTPAcomparedtoDMTduetoTPAbeinginpowderform
whileDMTisstoredmoltenininsulatedheatedtanksandisshippedalsoinmoltenform,
lower treatment cost due to water produced as byproduct instead of methanol, self
catalyzed esterification reaction which reduces the needs for external esterification
catalyst.16
AbasicdifferencebetweenthepreparationofPETfromDMTandEG,orfromTPAandEG,
consists in that TPA does not melt by itself at the temperatures used throughout the
polymerization path. Esterification of TPA with EG is required to homogenize the reaction
mixtureinthefirstesterificationreactor.TheprocessbasedonTPAandEGrouteconsistsof
twostages.Inthefirststage,TPAisesterifiedwithexcessEGunderpressureat230270C
with elimination of water, yielding prepolymer consisting bis2 hydroxy ethylene
terephthalate(BHET)andshortchainoligomers.Inthesecondstage,theprepolymeristhen
heated to 270 290 C under progressively reduced pressure until excess EG is eliminated
andhighmolmassPETisobtained.TheformationofPETinvolvestwomainreactions,(1)
esterificationofcarboxylendgroupsofTPAwiththehydroxylendgroupsofEGorofesters
and(2)polycondensationofesterswithterminalhydroxylgroups.Fortheapplicationssuch
as bottles or technical yarns where the high strength properties are required, further
polymerization in solid state (SSP) is performed under vacuum or in an inert gas
atmosphere.TheglobalmarketofPETismostlydominatedbythetwocommongrades,i.e.
fibergrade PET and bottlegrade PET. These grades differ mainly in molecular weight and
aredescribedintheTable1.1.14
9
plications15
Table1.1:MolecularweightsoffPETresinssaccordingtotheirapp
Bottlle
Technical
application
appliccation
Textile
applicationn
Melt Chips Chip
ps
HighViiscosity
Mn <25000
0 finissher Mn ~20000 Mn ~20
0000
Melt
Mn <2100
00
Solidstate Solidstateepoly.
Technical Me
elt
poly. Mn ~250
000to
yarns Mn <4
40000
Mn <40000 280000
Filament Fiber
Technical Bottlegrad
dechips
yarns,tyree ortechnicaalyarns
cord

A(purified)166
Table1.2::SpecificationandanalysisofTPA
Propeerty Specificcation Typicalvalue

Acidnumber,mggKOHg1 6752
2 673675
Ash,p
ppm 15 <3
Metaals,ppm 9 <2
Wateer,wt% 0.2 0.1
4Forrmylbenzoiccacid,ppm 25 15
pToluicacid,pp
pm 1254
45 125
urified)16
Table1.3:PhysicalpropertiessofTPA(pu
Crystaldensiity,gcm3,2
25C 1.58
8
pecificheatt,Jg1K1,to
Sp o100C 1.2
mation,kJmol1
Heatofform 816
6
Heatofcombustion,kJmol1,25C
C 3189
9
Iggnitiontemp
peratureinair,C 680
10
Table1.4:QualityandphysicalspecificationofEG16
Purity,% >99.80
Density,gcm3,20C 1.11351.1140
Boilingrange(at101.3kPa),C 196199
Diethyleneglycolcontent,wt% <0.5
Watercontent,wt% <0.10
Acidnumber,mgKOHg1 <0.005
SincethePETisasemicrystallinepolymer,introductionofcompatiblemolecularrepeatunit
such as diethylene glycol (DEG), isopthalic acid (IPA) and cyclohexane dimethanol (CHDM)
areaddedtoimprovisetheclarityoftheproduct.Comonomersaddedatlessthan5mol%
levels,suppressthecrystallizationrateandpostponespolymercrystallizationuntilinjection
molded preform of above glass transition temperature are blow molded into the desired
shapes.Suchadelayinthecrystallizationpromotestheproductionofclearandtransparent
productswiththesamecrystallinitylevelasPEThomopolymer.14
COOH
CH2OH
HOCH2CH2OCH2CH2OH
HOCH2 HOOC
CHDM IPA DEG

Figure1.1:ComonomerstoproduceamorphouscopolymersofPET
Theconventionalmeltphasecontinuousprocessinvolvespastepreparationvessel,threeto
fivereactors,distillationunit,comprehensivevacuumsystem,alargefinisherandpelletizer.
ThetypicalfeedmolratioofEGandTPAdiffersbetweenbatchandcontinuousprocess.In
thebatchprocess,thefeedmolratioiskeptbetween1.1and1.3whileinthecontinuous
process; it is adjusted between 1.05 and 1.15 in a paste preparation vessel. Due to
thixotropic nature of the paste, the preparation vessel is generally equipped with stirrer
suchasIntermig.Inthecontinuousprocess,themolratioiscontrolledbymeasuringthe
paste density. The paste is then fed to primary esterifier vessel, which is operated in the
pressurerangeof14barandatemperatureof255280C.LimitedsolubilityofTPAinEG
causesthereactorperformancetobeafunctionoftemperatureandathightemperature;
11
the reactor performance is limited by the solidliquid mass transfer rate. Under these
conditions,thereactorperformancedependsontheTPAparticlesize.17Theaveragechain
length of the esterified oligomers and carboxyl content are mainly controlled by the feed
molratioandtemperature.Oligomersarefurtherpassedthroughsecondaryesterifierthat
normally runs at atmospheric pressure and at high temperature compare to primary
esterifier.ThemajortaskofthesecondaryesterifieristocompletethedissolutionofTPA
andtohavethehomogeneousslurry.Theproductofsecondaryesterifierisfedbygravityto
theprepolymerizer,whichoperatesatamediumvacuumpressure.ExcessofEGandwater
remainedinthepolymerareremovedinthisstage.Prepolymerwithintrinsicviscosityof
about0.2dl/gispumpedbygearpumpsthroughafilterintotheintermediatepolymerizer
and finally to the finisher. Both reactors operate under low vacuum pressure close to 1
mbar. Horizontal stirrer is installed in these reactors to generate a large polymer surface
area. Engineering companies uses different sitter types on their proprietary bases (Figure
1.9).However,cage(Figure1.3)ordisctype(Figure1.4)reactorsarethemostcommonand
provideplugflowtransportwithlittlebackmixingwhichfurtherfacilitatenarrowresidence
timedistributionandhigheraveragechainlength.Thecagetypefinisherisbuiltonshaftless
design, which is claimed to improve the product quality by avoiding polymer sticking to a
shaft. It is heated by heattransfer medium flowing through a jacket, which causes higher
temperatureatthereactorwallthanthetemperatureofthepolymermelt.Afewmillimeter
ofclearancebetweenthecagestirrerandthereactorwallprovidesagoodheattransfer.18
The disctype finisher is heated mainly by stirring through shearing of the highviscosity
melt. The temperature of the reactor wall is lower than the temperature of the polymer
melt,whichisclaimedtoimprovetheproductqualitybyavoidingthepolymeroverheating
atthereactorwall.Themeltintrinsicviscosityismeasuredbytheviscometerattheoutlet
ofthepolymerdischargepumpandthedesireddegreeofpolycondensationcanbesetby
adjustingthevacuum,reactiontemperatureandtheaverageresidencetimeinthefinisher.
Themeltviscosityinthepolycondensationphaseincreasesfromapproximately0.8to400
Pa s. Such a high melt viscosity and degradation reactions overtake the polycondensation
reaction and limit the molecular weight. For this reason, solidstate polycondensation is
commonlyused.
12

17
Figure1.2:ContinuoussPETprocessbasedon
nTPAwithffivereactorsinseries.

18
Fiigure1.3:C
Cagetypefin
nisher(DISC
CAGE,FischerProcess).
13

14
Figure1.4:Disctypefinisher(ZimmerProcess).
ThemajorproductionofPETresinintheworldisbasedoncontinuousunitswithalarge
scale capacities ranging from 200 and 600 t/d. However, smallscale batch plants with
capacities ranging from 20 to 60 t/d are also used to produce specialty products. The
increasing demand of PET and energy intensive process has given rise to largescale
continuous plants and the capacities have been scaled up from 20 t/d to 600 t/d. Further
highcapacitycontinuousplantsarebeingofferedbycompaniessuchasInvista(1500t/d),
Zimmer (1320 t/d) and Uhde Inventa Fischer (1200 t/d). Based on the resin application,
different plant modules are being offered. For textile application Mn < 21000 is required,
which can be met with melt polycondensation modules alone. However, for the bottle
applicationMnof25000to28000isrequired.Afterthemeltphasepolycondensation,the
amorphous PET granulate contains about 30 to 150 ppm acetaldehyde (AA) which is not
suitable for the bottle application. To minimize the generation of AA and yellowing, a
furtherpolycondensationisperformedinthesolidstate(SSP)atlowerreactiontemperature
(Dependingontheamountofcomonomers,themaximumSSPtemperatureisbetween200
and 220 C), either in a high vacuum or in hot inert gas flow to remove effectively the
reactionbyproductsuchaswaterandEG.TheAAcontentcanbereducedto<1ppm.Prior
toSSP,amorphouspolymerchipsarefurthercrystallizedtopreventstickingtothereactor
wall. Melt and solid phase process consists same chemistry however different reaction
temperature. Due to lower reaction temperature and mass transfer limitation in SSP,
residence time requirement increases to about 824 hours in comparison to 13 hours
requiredinmeltphase.
14
Thepresentstudyaimstounderstandtheinfluenceofterminalfunctionalgroupsonmelt
phasepolymerization.Themeltphasecontinuousplantscanbecategorizedinthreeparts
(basedontotalresidencetimeandtheprocesstemperature.19
Table1.5:MeltphasecontinuousPETprocesscategories
Totalresidencetime Temperaturerange[C] Esterificationpressure
[h] Esterification Polycondensation [bar]
35 275290 280290 35
68 255275 280 13
812 250265 270285 11.5
In late 70s, DuPont introduced 3reactor PET process (Figure 1.5) which has much
similaritieswithpresentInvistaprocess.Invistacomprises3vesseldesign(Figure1.6)with
minimal moving parts. This design uses high temperature and lower residence time and
claimstohavethecapacitiesinexcessof1300t/d.Suchahighcapacitieshavebeenrealized
by bifurcated stream offering from the esterification reactor to the prepolymerizers. The
esterifier incorporates a heat exchanger and vapor separation and connected by a
recirculation loop, which has no moving parts such as pumps, motors or agitators. The
streamofoligomersfromtheesterifierisbifurcatedintwoprepolymerizers,whichcontains
upflow design known as UpFlow PrePolymerizer (UFPP) reactors. Series of trays are
installedinsidetheUFPPandthepressuregradientalongthereactorallowstheprepolymer
slurrytoboilandtobetransferredinupwarddirection.ExcessofEGisaddedatthebottom
tray to provide sufficient gas flow and acts as carrier to promote upward flow of the
prepolymer. Finally, the prepolymer from UFPP are passed through cage type reactor
(finisher)toobtainAPETresinquality.20
15

21
Figure1.5:Continuo
ousPETpro
ocessfromD
DuPont

Figure1
1.6:Continu ocessfromInvista20
uousPETpro
UhdeIn
nventaFisch
herofferstthe2reacto
orprocess((Figure1.7))basedonp
proprietaryyreactor
design ofESPREEaandDISCAG
GE.Initially theEGand
dTPAareessterifiedin thelower reaction
16
chambeerofESPREEtower(Figgure1.8).P
Producedolligomersareedirectedttotopofth
hetower
underp
pressurean
ndwithdeffinedresideencetimetiilltheirreleeaseinthe topreactio
oncups.
Oligomers flows down
d the sequence
s o the reacttion cups by
of b continuo
ously releassing the
pressurre and with
h steady teemperature increase. Pressure reelease is efffected by reaction
gases as
a well as additional
a in
nert gas, which
w furthe
er facilitatees intense b
back mixingg of low
boiling pointoligo
omers.The productis thenledto
otheflash zonewhereelowerpre
essureis
achieveed.Inthefo
ollowingfilm
mchamberss,feedcylin
ndersdistributestheo
oligomersevenlyto
vertical tubes which form deefined filmss on the inner tube su
urface and obtains he
eat from
outsidee.Steadyinccreaseofth
hepolycond
densationrreactionisaachievedbyysuchhighsurface
generattion and heeat exchangge. The pro
oduct is led
d to second m zone wh
d falling film here the
similar conditions likepreviou
uszoneisaachieved.Prrepolymerw
withdegreeeofpolyme
erization
ofabou
ut40istran
nsformedbyyapumpin
ntoDISCAGEEreactorto
oobtainfurttherhighde
egreeof
polymeerization.

18
8
Figure1.7:Tworeacto
orssinglesttreamPETp
processbyU
UhdeInventtaFischer
17

22
Figure1.8:Espreetower
Thereareincreasingeffortstoprovidemelttopreformormelttoresinprocessesfrom
several engineering companies by offering the benefits of reduced production costs and
conversion costs by eliminating the needs for SSP unit. Furthermore, the trend for
connectingthePETprocesstotherawmaterialproductionisalsobecomingappealingwhile
itoffersthesavingsintheprocessingcost.IntegRexprocessfromEastmanofferspolyester
production directly from paraxylene without separation of TPA as an intermediate and
withouttheneedsforSSP.19
18

Figure1.9:Examplesofvariousstirringdiscgeometries23
References
[1] W.H.Carothers,E.I.duPontdeNemoursandCompany,USPat2,071,250,1937;
USPat2,071,251,1937.
[2] J.R.Whinfield,J.T.Dickson,Br.Pat578,079,1946.
[3] J.R.Whinfield,Nature,1946,158,930.
[4] J.R.Whinfield,Text.Res.J.,1953,23,290.
[5] E.I.duPontdeNemoursandCompany,USPat2,727,882,1959;USPat2,833,816,
1958,USPat3,089,906,1963.
[6] U.Hummel,J.H.Oxley,ACSDiv.Petrol.Chem.Prepr.,1969,13,61.
19
[7] S.Beury,ChemicalMarketAssociatesInc.,2006WorldTerephthalatesandPolyester
Analysis,August31,2005,http://www.cmaiglobal.com.
[8] M.E.Rogers,T.E.Long,Syntheticmethodsinstepgrowthpolymers,JohnWiley&
Sons,2003.
[9] A.Fradet,E.Marechal,Adv.Polym.Sci.,1982,43,51.
[10] J.Otton,S.Ratton,J.Polym.Sci.,PartA:Polym.Chem.1991,29,377.
[11] C.M.Fontana,J.Polym.Sci.,PartA1,1968,6,2343.
[12] J.W.Chen,L.W.Chen,J.Polym.Sci.,PartA:Polym.Chem.,1998,36,3073.
[13] J.S.Schaul,PolymerPlast.Technol.Engng.,1981,41,209.
[14] J.ScheirsandT.E.Long,ModernPolyesters:ChemistryandTechnologyofPolyesters
andCopolyesters,JohnWiley&Sons,2003.
[15] E.VanEndert,Manmadefiberyearbook(CTI),1986.
[16] R.J.Sheehan,UllmannEncyclopaedia,WileyVCHVerlagGmbH&Co.KgaA,2005.
[17] D.Tremblay,paperpresentedattheAIChEannualmeeting,HoustonTexas,March
1419,1999.
[18] www.uhdeinventafishcer.com
[19] U.Thiele,PolyesterBottleResinsProduction,Processing,PropertiesandRecycling,
Vol.5,PETplanetprint,2007.
[20] http://ipt.invista.com
[21] E.I.duPontdeNemoursandCompany,USPat4,110,316,1978.
[22] UhdeInventaFischerGmbH&Co.KG,PatDE101,554,19A1,2003.
[23] F.WilhemandF.Finkeldei,Patentapplicationpublication,US2003/0139543A1,
2003.
20
Chapter2:ExperimentalDetails
Materials
Thefollowingmaterialsareusedintheexperimentsaswellasinanalysisofthesamples.
Reactants: Terephthalic Acid (Equipolymers), Ethylene Glycol (Equipolymers), Diethylene

Glycol(CGChemikalien)andIsophthalicAcid(Merck,purity>99%)wereusedasreceived.
Catalysts:AntimonyTriacetate(Atofina),TitaniumButalate(Fluka,purity>97%gravimetric)
Tibasedchealtedcatalyst(Equipolymers),Hydrotalcite(Sasol)
Additives: Tetramethylene Ammonium Hydroxide (Fluka), Cobalt Acetate (Equipolymers),

PhosphoricAcid(Merck,85%aqueoussolution)
Chemicalsusedformeasuringcarboxylendgroupconcentration:
Ocresol(Merck),Chloroform(Merck),PotassiumHydroxideinEthanol(Merck),Ethanolfor
dilution (J.T. Baker, absolute), Bromophenol Blue (Merck, pH 3.04.6) were used to titrate
carboxylvalueofsamples.
Chemicalsusedmeasuringintrinsicviscosity(IV):
1:1mixtureofPhenolandOdichloroBenzene(OSCOrganoSpezialChemieGmbH,Water<
200ppm)
Reactorspecificationsandexperimentalprocedure
Volume:1000ml
Innerdiameter:101.6mm
Innerdepth:137.16mm
Maximumpressure:70bar
Maximumvacuum:0.1mbar
Maximumtemperature:350C
SplitringconnectorwithPTFEgasket.
Magneticdrive:Maximumtorque:13Nm;Stirringspeed:0180rotation/min
21
Condenser
PIC
PIC Column
PI PI N2
P S
TIC
N2 P
Additives
Vacuum charge
Cold traps
pump
Cold trap
Byproducts
PET
KW Cooler Thermo-
stat

Legends
N2:Nitrogeninlet
Esterificationline
P:Pressureindicator
PPIC:Pressureindicatorcontroller Polycondensationline
S:Stirrer
TIC:Temperatureindicatorcontroller
Figure2.1:Parrreactorflowchart
1literstainlesssteelreactor(Parr)wasusedforbothesterificationandpolycondensation
experiments. The reactor temperature was controlled by a thermostat equipped with PID
temperature controller (Lauda USH 400/6). Column and condenser temperatures were
regulatedbythermostats(LaudaRE204)and(LaudaRE105)respectively.Magneticstirring
drive(Parr)wasinstalledwithhelicalbladeimpeller.Thepressureaboveatmosphericlevel
was measured by analogue as well as digital sensor installed at top of the reactor. The
pressure was regulated with PID controller. The pressure below atmospheric level was
measuredbyaseparatePIDcontroller(Vacuubrand).Vacuumwasprovidedbyrotarypump
(Vacuubrand). The reactor outlet valve was equipped with electrical heating jacket. To
determine the esterification rate constants, several experiments were performed in
22
Juchheim semibatch reactor of 5liter reaction volume. Details of the equipment and the
experimentalprocedurearepresentedinChapter3.

Figure2.2:Experimentalsetup
Experimentoptimization
Esterificationphase
Esterificationphasegenerallyincludesthreephases.SolidTPAisdissolvedinEGandliquid
reactionmasstobefurtherreactedtoformoligomers.Atthesametime,byproductwater
is evaporated from melt to vapor phase. Reactor performance can be affected by mass
transferlimitationifthesolidTPAparticlesarerelativelylarge,pooragitationinthereactor,
shorter residence time, reaction temperature and pressure. Influence of TPA particle size
and reaction pressure is discussed in chapter 3 and 4 respectively. Residence time of 95
minutes for the given esterification conditions was obtained since the resulted oligomers
23
werefreefromsolidTPA.RotationspeedalsodeterminesthemasstransferofthesolidTPA
into liquid phase. However, rotation speeds from 60 to 140 have not been observed to
influence the esterification conversion significantly in the given set of experiments (Figure
2.3).Consequently,constantstirrerspeedof140rpmwasconsideredfortheesterification
phase.
Esterficationconversion,
0.968
0.966
0.964
40 60 80 100 120 140 160
Rotationperminute[1/min]

Figure2.3:Influenceofrotationspeedonesterificationconversion(esterificationphase)
Polycondensationphase
Transesterification reaction is a main reaction during polycondensation phase. Due to

reversiblenatureofthereactionandincreasingviscosityofthereactionmelt,itisimportant
to have optimal mass transfer of the volatiles to obtain maximum conversion in a shorter
reactiontime.Tooptimizethemasstransferofthevolatiles,polycondensationphasewas
carriedunderdifferentstirringspeedtoinfluencethespecificmasstransferinterfacialarea
andunderdifferentvacuumconditionstoinfluencetheequilibriumconcentrationofEGon
themeltvaporphase.Figure2.4showstheinfluenceofvacuumontheintrinsicviscosityof
thepolymer.Itcanbeseenthatvacuumof0.1mbarfromthebeginningoftheexperiments
leadstooptimalpolymericIVincomparisontothemoderatevacuumrangeof2to1mbar.
Thus, optimum vacuum profile of 0.1 mbar was considered to minimize the EG diffusion
limitationfromthereactionmelt.
Themeltviscosityincreasesrapidlywithprogressingpolycondensationbyabout24orders
of magnitude which affects the diffusion of volatiles. For example, in industrial
polycondensationreactorsthemeltviscosityincreasesfrom=0.05to350PaS(at290C,
24
IV=0.64 dl/g). Therefore, the effect of change in the rpm of the stirrer on the IV was
elucidatedfortheprepolymerizationandfinalpolycondensationphase.FromFigure2.5,itis
seenthatmaximumspeedintheprepolymerizationandmoderatespeedinthefinalphase
polycondensation gives optimum reaction rate. In the prepolymerization phase, very high
rpm facilitates the removal of excess of unreacted EG, which has been left over after the
completion of esterification phase. However, as the melt viscosity builds up, the reaction
temperaturealsoincreases.Thus,byloweringthestirringspeed,theshearingeffectcanbe
loweredandthetemperaturecanbemaintainedasdesired.Alsolowstirringspeedallows
thehighviscousmelttoformthinfilmswhichfurtherincreasestheinterfacialareaandthe
removalofEGcanbeintensified.
Ampere (High Vacuum) Ampere (Low Vacuum)

High Vacuum Low Vacuum
1.0 2.5
IV: 0.51 dl/g 2

0.8
Stirrer power [amp]
Vacuum [mbar]
1.5
0.6
1
0.4
0.5
IV: 0.76 dl/g
0.2 0
100 120 140 160 180 200 220
Time [min]

Figure2.4:Influenceofvacuumonintrinsicviscosityinpolycondensationphase.Sb:200
ppm,PolycondensationRPM:30
25
2.10
Overallpolycondensation
2.05
rate,n/t(1/min)
2.00
1.95
1.90
1.85
1.80
140/70 120/40 120/50 100/50 140/40 140/40 140/50
Stirringspeedcombination(rpm)
Figure2.5:Influenceofstirringspeedonoverallpolycondensationrate(prepolymerization/
finalphasepolycondensation).Sb:200ppm
0.75
y=0.952x+0.015
0.70 R=0.861
Intrinsicviscosity(dl/g)
0.65
0.60
0.55
0.50
0.45
0.40
0.5 0.55 0.6 0.65 0.7 0.75
Stirrerpower(amp)

Figure2.6:Correlationoffinalstirrerpowerandobtainedintrinsicviscosity
Evaluationofexperimentalresults
Determinationofintrinsicviscosity(IV)
10 grams of oligomers were sampled in a strainer and cooled by liquid nitrogen. The
oligomers were immediately ground to a powder in a centrifugal mill (RETZSCH MZ 100)
typewith0.5mmmeshbottom.Thegroundoligomersweredriedatconstanttemperature
26
of100CinahalogenmoistureanalyzeroftheMETTLERHG53type.Thedriedsamplewas
then dissolved in solvent mixture of phenol and 1,2dichlorobenzene with a phenol
concentration of 50 weight%. Clear solutions were filled in an auto sampler of the IV
measurement instrument (SCHOTT AVSPro). The capillary temperature was maintained at
25C.Thedroptimeofthedissolvedsamplesandsolventwasmeasuredautomaticallyand
theevaluationprogramgavetheintrinsicviscosityindl/g.
Determinationofcarboxylendgroupsoftheresin
1gramofcrystallineresinwasaddedaspowderinatitrationflaskalongwith35mlsolvent
mixture (ocresol/chloroform). The sample was dissolved for 15 minutes at 170 C in a
heatingblocksystemandlateritwascooleddowntoroomtemperature.Theresincarboxyl
groups were titrated against 0.05 N potassium hydroxide using Bromophenol Blue in
ethanol as an indicator (electrode: Phototrode DP 550 (Mettler Toledo)). The titration of
resin carboxyl end groups was corrected by running a blank titration of solvent without
resin.
DeterminationofDiEthyleneglycol(DEG)
About1goftheresinsamplewasaddedtogetherwith30mlmethanolandzincacetateas
catalyst and tetra ethylene glycol dimethyl ether as internal standard into a pressure
container.Thecontainerwasheatedfortwohoursat220Cinanoventodecomposethe
resin to the DEG and methyl isophthalate. The sample mixture was cooled to the room
temperature and analyzed by gas chromatography (PERKIN ELMER GC Autosystem XL).
TheDEGcontentswerecalculatedfromtheareasoftheDEGpeakinrelationtotheinternal
standardpeak.
Determinationofwaterinreactionbyproductmixture
The weight fraction of EG and water in distillate were analyzed by gas chromatographic
analysis.
27
Chapter3:SemibatchEsterificationProcessforPoly(ethyleneterephthalate)
Synthesis
Abstract
Esterification kinetics in poly(ethylene terephthalate) (PET) synthesis has been studied by
usingasemibatchreactor.Terephthalicacid(TPA)wasesterifiedwithethyleneglycol(EG)in
absence of external catalysts to study the kinetics of this acid catalyzed reaction. A
comprehensive mathematical model for esterification in a semibatch reactor has been
developed by considering functional group approach. The model was validated using a
series of experimental data for different monomer feed ratios. Rate constants were
optimized by data fitting with final oligomeric chain length and fraction of oligomeric
carboxylgroupsintotalterminalgroups,.SolidliquidequilibriumofTPAwasconsidered
byintroducingTPAparticlesizedistributionandvaryingTPAsolubilityinEGandoligomers.
TPA particle size was tracked with time as a function of monomer feed ratio. It was also
observed that conversion became more sensitive towards TPA particle size as the EG/TPA
feedratiowaslowered.ItisadvantageoustousethemodelbasedonTPAparticlesizefor
mass transfer limited esterification reactions. The effect of monomer feed ratio on
conversion, degree of polymerization, functional group concentration and system
heterogeneitycanbepredictedwiththismodel.

28
Introduction
Withaglobalproductionof35milliontonesperannum,Poly(ethyleneterephthalate)(PET)
isconsideredasaoneoftheleadingpolymerresinsintherecenttimes.About63%ofPETis
used as fibers in staple, filament and woven forms while the remaining 37% is used as a
packagingresinforbottles,containers,sheetandfilm.GlobalgrowthratesforPETusagein
fibers and packaging are around 4% and 8% per year, respectively.1 PET is a polyester
formedbystepgrowthpolycondensationmainlyfromTerephthalicacid(TPA)andethylene
glycol(EG).TheformationofPETinvolvestwomainreactions,(1)esterificationofcarboxyl
endgroupsofTPAwiththehydroxylendgroupsofEGand(2)polycondensationofesters
withterminalhydroxylgroups.
Direct esterification reaction between TPA and EG is considered as a key process. During
esterification,TPAreactswithEGyieldinglowmolecularweightoligomersandwaterwhere
thelatteriscontinuouslyremovedtofavortheforwardreaction.Theesterificationreaction
is accompanied by the reverse hydrolysis reaction. The polycondensation is also an
equilibrium reaction, it is accompanied by the reverse glycolysis reaction. During
polycondensation,terminalhydroxylgroupreactwithglycolesterinthepresenceofcatalyst
suchasantimony(Sb)toproducepolymerandEGwherethelatterisremovedbyvacuumto
promotepolymerization.Thepolycondensationiscoupledwithmasstransferlimitationat
high degree of polymerization because nonremoval of EG promote the reverse glycolysis
reaction. In an industrial PET process, esterification and polycondensation proceed
simultaneously. It is important to have the optimum ratio of reactive end groups
(COOH/OH) during each step to allow esterification and polycondensation to proceed in
parallel.2
The esterification process involves three phases, i.e. a solid phase containing undissolved
TPA;ahomogeneousliquidphasecontainingoligomers,EGanddissolvedTPA;agasphase
containing volatiles such as water, EG, diethylene glycol (DEG) and other reaction
byproducts. Kinetic analysis becomes difficult due to the very low solubility of TPA in the
reaction medium.7 It is important to understand the effect of process variables on the
esterificationprocessinordertoimprovetheproductivityofexistingplants.
Kineticsoftheesterificationprocesshasbeenstudiedmostlybyusingmodelcompoundsto
simplify the evaluationof the experimental data. Reimschuessel3 studied the kinetics with
29
model molecules such as esterification of benzoic acid with EG and TPA with 2(2
methoxyethoxy) ethanol. Otton et al.4 studied different carboxylic acids. However,
simplification with model compounds does not address the TPA solubility in the reaction
mass as the TPA dissolution and its consumption by reaction proceeds simultaneously.
RavindranathandMashelkar5,Yamada6andKangetal.7havestudiedesterificationofTPA
with EG and proposed a mathematical model for a three phase continuous esterification
process.RavindranathandMashelkarassumedfortheirsimulationthattotalconversion,p
obtained from the esterification phase is close to zero (chain length, n=1) but in reality it
changesfromzeroto0.9(n=10)incontinuousesterificationreactors.6Also,theyassumed
thatthecarboxylgroupsconcentrationinliquidphaseremainsconstantuntilthereaction
mixture becomes homogeneous. However, the concentration of liquid carboxyl groups
changesduetothefactthatTPAsolubilitydependsontheavailabilityofEGandoligomers
andalsoonTPAparticlesizewhichreduceswithTPAdissolution.6Yamadaobtainedhigher
solubility of TPA in EG than in the oligomers, which is in contrast with the solubility data
givenbyKumarandGupta8.Kangetal.consideredtheTPAsolubilityaccordingtoYamada
and have assumed the process to be controlled by the reaction rate, they introduced
characteristicdissolutiontime()whichisafunctionofshapeandsizeofsolidTPAparticles
andmixingcharacteristicofreactor.9However,thevalidityofwasnotgiven.
In the current work, we have introduced the influence of TPA particle size distribution on
the dissolution of TPA. Influence of other process variables such as monomer feed ratio,
temperatureandacidcatalystconcentrationwerestudied.Acomprehensivekineticmodel
isdevelopedbyusingasmallscalesemibatchreactortodeterminetheesterificationrates
inPETprocessbasedonafunctionalgroupapproach.Theeffectofmonomerfeedratioon
conversion, degree of polymerization, functional group concentration, DEG formation and
system heterogeneity was investigated. The results obtained were treated with multi
parameterkineticsandgoodagreementwasfoundbetweenexperimentandsimulation.

30
ExperimentalMethod
ThedirectesterificationexperimentswerecarriedoutinaJuchheimbatchreactorwith5
liter reaction volume. Four different experimental conditions were chosen with EG0/TPA0
feedratio(MRI)of1.2,1.3,1.4and1.6.ThesamegradeofTPAwasusedinordertohave
the same dissolution behavior in all measured experiments with respect to the specific
surfaceoftheTPAparticles.Thereactorwasequippedwithspiralagitatorandthereaction
mixturewasstirredwith230rpm.Inallexperiments,themixturewasheatedfrom50Cto
240Cwithin25minutesandthenthereactiontemperaturewasincreasedtoabout255C
within 150 minutes. Initially, the reactor was pressurizedwith nitrogen at 2.5 bar and the
pressure was allowed to increase up to 4 bar with the vapor pressure of the reaction
mixture.After75minutes,thepressurewasgraduallyreducedtoatmosphericpressureto
allow the oligomers to grow further via the esterification route and to complete the
esterification. Byproduct formation such as water was distilled off continuously via
distillation column attached to the reactor. The column was maintained at room
temperature(25C)bycirculatingwater.Vaporswerecondensedandcollectedwithtime.
EGpercentagesweresubtractedfromtotalcondensatetoobtaintheamountofwater.As
alltheexperimentscarriedundersameconditions,atypicaltemperaturepressureprofilein
areactorisgiveninFigure3.1.Esterificationwascompletedafter150minutesandobtained
oligomers were characterized by measuring the carboxyl value and intrinsic viscosity
(chapter2).
ExprimentalTemperature SimulatedTemperature Pressure
300 6
250 5
Temperature[C]
Pressure[bar]
200 4
150 MainEsterification Prepolymerisation 3
100 2
50 1
0 0
0 30 60 90 120 150
Time[min]

Figure3.1:TemperaturepressureprofileusedforesterificationphaseinJuchheim
semibatchreactor
31
ResultsandDiscussion
Mathematicalmodel
Reactionscheme
Table3.1:Molecularstructuresofcomponentsconsidered
Symbol Description Molecularstructure
carboxylgroupin
aF HOOC COOH
terephthalicacid

carboxylgroupattachedto
aT HOOC CO
esterchainend

hydroxylgroupinethylene
bF HOCH2CH2OH
glycol
hydroxylgroupattachedto
bT HOCH2CH2O
esterchainend
w water H 2O

diethyleneglycolboundat
dT HOCH2CH2OCH2CH2O
esterchainend
ei internalesterlink OOC COO

y bT or aT
Esterification reactions are known to be catalyzed by protons dissociated from carboxyl

groupswhilethepolycondensationreactionsarecatalyzedbyexternalcatalysti.e.Sb(III)in
the form of oxide or acetate.10 The polyester process involves side step reactions at all
stages.Acetaldehyde,vinylendgroupandacidendgroupareformedgenerallyinthefinal
stagesofpolycondensation.11Incurrentwork,thesesidestepreactionsareignoredasthe
experimental work is carried out only for the esterification phase. However, diethylene
glycol (DEG) is mainly formed in the esterification process.12 For simplicity, two main
reactions are considered for DEG formation. Since the reaction temperature remains high
during esterification, it is assumed that water will evaporate as soon as it is formed. The
overall kinetic scheme can be simplified by selecting a functional group model which is
32
helpful to determine end groups and byproduct concentrations. Functional group
descriptionandreactionsschemearegiveninTable3.1andTable3.2,respectively.Inthis
study, the fourth order RungeKutta method was used to solve differential equations
numericallyapplyingBerkeleyMadonnasoftwarepackage.
Table3.2:Reactionschemeoftheesterificationprocess
Reactions Rateconstants(forward,
reverse)
kE1
aF aF + bF bF aT bT +w kE 1 , k E 1 K 1
kE1/K1

kE2
aF aF + bT y aT ei y +w kE 2 , k E 2 K 2
kE2/K2

kE1
bF bF + aT y bT y +w kE 1 , k E 1 K 1
kE1/K1

kE2
y aT + bT y y ei y +w kE 2 , k E 2 K 2
kE2/K2

kE3
y bT + bT y y ei y+ bF bF kE 3 , k E 3 K 3
kE3/K3
kE4
y bT + bT y y y +w kE 4

kE4 kE4
bF bF + bT y dT y +w

Assumptionsformodelingare,
1. Reactionsoccuronlyinliquidphase.TPAispartiallydissolvedinthereactionmixture
andonlydissolvedTPAtakespartinthereaction.
2. TPA dissolution rate depends on TPA particle size (i.e. specific surface) and particles
areassumedtobesphericalforsimplifications.
33
3. SolubilityofTPAinwaterisnegligible.
4. OnlyundissolvedTPAformssolidphaseofheterogeneoussystem.
5. Esterificationreactionsarecatalyzedbyprotonswhicharegeneratedbydissociation
ofterminalcarboxylgroupsofdissolvedTPA,( a F ,D )andcarboxylgroupsatesterend
groups( aT ).
6. EqualreactivityisconsideredforcarboxylgroupsboundtoTPAandtopolymerchain
whilehydroxylgroupsboundtoEGandtoestershavedifferentreactivity.13,14
ReactionratelawsforeachcomponentbasedonreactionschemegiveninTable3.2isgiven
inTable3.3.TPAandEGhavetwocarboxylandhydroxylgroupsrespectively.Bimolecular
reactionofthesereactantsconvertsoneofthecarboxylgroups( aF )ofTPAintotheinternal
esterlinkandtheotherintheterminalcarboxylgroup( aT ).ThesameistrueforEG,where
oneofthehydroxylgroups(bF)isconvertedintointernalesterlink(ei)andtheotherinthe
terminalhydroxylgroup(bT).Consequently,factoroftwoisusedfor aF and bFinTable3.4
tobalancethereactions.
Table3.3:Reactionratelaws
Reactionratelaws
R 1 = k E1 a F bF ( k E1 K 1 ) bT w
R 2 = k E2 a F bT 2( k E2 K 2 ) e i w
R 3 = k E1 bF a T ( k E1 K 1 ) bT w
R 4 = k E2 a T bT 2( k E2 K 2 ) e i w
R 5 = k E3 bT bT 2( k E3 K 3 ) e i bF
R 6 = k E4 bT bT
R7 = kE4 bF bT
Note:Reactions R 6 and R7 produceDEGlink
34
Table3.4:Massbalanceequations
d [aF ]
= 2 R1 2 R2
dt
d [bF ]
= 2 R1 2 R3 + 2 R 5 2 R7
dt
d [aT ]
= + R1 + R 2 R 3 R 4
dt
d [bT ]
= + R 1 R 2 + R 3 R 4 2 R 5 2 R 6 R 7
dt
d [w ]
= +R1 + R2 + R3 + R4 + R6 + R7
dt
d[dT ]
= +R6 + R7
dt
Phaseequilibrium
ThesolubilityofTPAinEGisreportedtobeextremelylowandesterificationisoccurringin
liquid phase only. Thus, the solidliquid equilibrium should be considered to calculate the
composition of the reaction mass in the liquid phase and the concentration of functional
groups. The liquid reaction mass increases by the continuous dissolution of TPA until the
reactionmediumbecomeshomogeneousandsimultaneouslydecreaseswiththeremovalof
water.Insimulation,TPAsolubilityinEGandoligomersisconsideredaccordingtoYamada
etal.15
TPAsolubilityinEGisgivenas,
1
TPA ,EG =9062exp(4877/(273+T))molkg (1)
TPAsolubilityinoligomersisgivenas,
1
TPA ,OLG =374exp(3831/(273+T))molkg (2)
Where: T=temperature,C
TPAcarboxylgroupconcentrationatphaseequilibrium aF * canbecalculatedbyusing
equation(1),(2),(4),(5)andesterificationconversion,(definitionseeequation(25)).
aF * = [ EG + ( OLG EG ) ] molkg1 (3)
ThesolubilityofTPAintermsofcarboxylgroupsinEG,
1
EG = 2 TPA ,EG molkg (4)
35
ThesolubilityofTPAintermsofcarboxylgroupsinoligomers,
1
OLG = 2 TPA ,OLG molkg (5)
Reactionratefortotalcarboxylgroups(a)canbegivenas,
d [a ] d [a F ,S ] d [a F ,D ] d [aT ]
= + + (6)
dt dt dt dt
Where, a F ,S representsthecarboxylgroupsattachedtoundissolvedTPA.Carboxylgroups
becomeavailablebyTPAdissolutionintheliquidphase.Simultaneously,availablecarboxyl
groupsareconsumedbyesterificationreaction.TPAdissolutionconstantandesterification
rateconstantaregivenas kDand kErespectively.Itisassumedthatthechangeincarboxyl
groupsconcentrationundersolidliquidphaseequilibriumisclosetozero.
d[aF ,D ]
= kD ( aF * aF ,D ) 2 kE aF ,D b 0 (7)
dt 144244 3 14243
dissolution consumption
The mass transfer coefficient kD is inversely related to the TPA particle radius. As the
particlesbecomesmallerduetotheirdissolution, kDincreases.Bydissolution,particlesmay
reach a critical point where they dissolve completely. It is important to consider such
situations for simulation to minimize errors. kD is calculated by using algebraic equations
giveninTPAdissolutioncalculations.
VaporliquidphaseequilibriumisconsideredbasedonpolymerNRTLparametersobtained
fromASPENdatabank16.EGandwaterareconsideredtobetheonlyvolatilecomponentsof
thereactivemixtures.Thevaporphaseisassumedtofollowtheidealgaslaw.Oligomersare
assumedtobenonvolatile.Themolefractionsandactivitycoefficientarecalculatedbased
on apparent concentration of water, EG and oligomers in liquid phase. Water is removed
continuouslytopromoteforwardreactions.Thereby,theconcentrationofwatershouldbe
updatedbysubtractingtheequalmolenumberoftheremovedcondensedwaterfromthe
total generated water. The vapor phase mole fractions of EG and water are given by the
followingequations.
x EG EG PEG = y EG P (8)
x H2O H2O PH2O = y H2O P (9)
x EG + x H2O + x OLG = 1 (10)
y EG + y H2O = 1 (11)
Where,
36
x EG , x H2O , x OLG = liquidphaseapparentmolefractionofEG,waterandoligomers.
y EG , y H2O = vaporphasemolefractionsofEGandwater
PEG ,PH2O = vaporpressureofEGandwater,bar
P = totalpressure,bar
EG , H O = activitycoefficientofEGandwater
2
VaporpressuresarecalculatedfromYamadaetal17.
PEG = 1.33 10 4.8808 1957 /( T +193 .8 ) (12)
PH2O = 1.33 10 4.96681668.2 /( T +228 ) (13)
Where,T=reactiontemperature,C
TPAdissolutioncalculations
TPAusedintheexperimentswasanalyzedforparticlesizebylaserdiffractionmethod.
0.10 1.0
Instantaneousdistribution
Cumulativedistribution
0.08 0.8
0.06 0.6
0.04 0.4
0.02 0.2
0.00 0.0
0 50 100 150 200
ParticleSize(micrometer)

Figure3.2:TypicalTPAparticlesizedistribution.
This method gives the particle size distribution based on particle volume average as per
Figure3.2.TPAparticlefractionofeachsizeisgivenas,
3 d i V0
n p ,i = (14)
4 ri ,0 3
Where,
di=volumefractionofparticlefraction,i.
V0=initialvolumeofTPA
ri,0=initialparticleradiusofparticlefraction,i.
37
Weassumethatallparticlesaredissolvedwithequaldissolutionrate, q. Byusingthisrate,
residualparticlesizeforeachfraction,icanbegivenas,
1 Vi
ri = ri ,0 + log (15)
q V0
Where,Viistheapparentvolumeoftheparticlesinallfractions,iattime,t.
Byusingequation(14)and(15),specificinterfaceofallparticlesisgivenas,
A 4 np ,i ri
2
= = (16)
V 4 n r 3
3
p ,i i
Masstransferconstantoptedforthecurrentworkis k s = 2 10 5 mmin1.18
Basedonthespecificinterfaceandthemasstransferconstant,themasstransfercoefficient
basedonparticlesizecanbegivenas,
1
k D = k s min (17)
Catalysis
Esterificationreactionsinvolveacidcatalysismechanism.Thecatalyticinfluenceofanacid
depends on the degree of dissociation of the acid. The concentration of protons is
calculatedbasedontheaciditycarboxylendgroups.19
[H ] [a
+
F ,D ] [ ]
103.51 + aT 103.51 (18)
Effectiverateconstantforesterification,polycondensationandDEGformationreactionscan
begivenby,
kE,i = [ H + ] k ,i (19)
Where,k,iisamicrokineticrateconstant
Challa[13]andOttonetal.14haveconsidereddifferentreactivityofhydroxylgroupsatEGand
at terminal ester; consequently, in our study, we have used the rate constant, kE1 for the
reactionofEGwithcarboxylgroups,i.e. bF with a F ,D or aT ;while,therateconstant kE2for
thereactionofterminalhydroxylgroupwithcarboxylgroupsi.e. bTwith a F ,D or aT .Otton
et al.20 observed that acid catalyzed esterification is about three times faster than acid
catalyzed polycondensation. This relationship is used for the polycondensation rate
constant,kE3=kE1/3.
38
InallesterificationexperimentssomefractionofEGalsoevaporatedalongwiththewater
during removal of byproducts, consequently EG concentration was corrected according to
real EG concentration in the reaction mixture. Therefore, kinetic simulations were
performed with the monomer feed ratio determined at the end of the reaction
(MRF=EGresidual/TPA0) which accounts for the loss of EG. Calculations for MRF are given in
Table3.5,EGresidualwascalculatedbysubtractingevaporatedEGduringesterificationphase
fromtheinitialamountofthefeed.EGbalancecanbeexpressedas,
EG0 = EG V
+ EG
{ + EG
L
{
R
(20)
{ { Vapor Liquid
Feed 1 42Re4
acted
3
EGresidual
Table3.5:CalculationsforEG/TPAfinalfeedratio
MRI EG0,mol EGresidual,mol TPA0,mol MRF

1.6 9.6 8.64 6 1.44
1.4 8.4 7.74 6 1.29
1.3 7.8 7.2 6 1.2
1.2 7.2 6.78 6 1.13
Inthesimulation,thetemperaturewasdescribedwithfivedifferentheatingratesof8.7,2,
0.067,1.8,0C/minfor021,2124,2469,6973,73150minutesrespectivelyasshownin
Figure3.1.
In presented work, reactions were carried out in absence of Sb catalyst. Therefore,

acetaldehyde generation was neglected. Activation energies for the esterification,
polycondensationandDEGformationreactionsweretakenfromKangetal.7Inourstudy,
preexponential factors were fitted to experimental data. Rate constant kE1 was fitted for
eachmonomerfeedratiotocarboxylvalueofoligomersandwatergenerationcurvewith
higher weighting on the carboxyl value. Rate constant kE2 was fitted to oligomeric chain
length,n.RateconstantkE3forDEGformationwasattunedfortheoptimalfittingofnand
(definitionseeequation(21)).
39
Table3.6
6:Kineticpaarametersusedinthessimulation
Kiineticconsttants Activation
nenergy Frequencyfactor Equilibrium
m
k ,i = A i exp(( E i / RT ) Ei[kcalmol1] Ai[kg2mol2min1] constant
k ,1 18 4.60 10 8 K1:2.50
k ,2 18 1.06 10 10 K2:1.25
k ,3 = k ,1 /3 K3:0.5
k ,4 29.8 4.59 10 122
Influencceofmonom
merfeedratio
oonwaterg
generationrate
FromFigure3.3,o
onecanseeethatwatergeneratio
onrateincreeaseswith anincrease
einMRI
duetoenhancedd
dissolutiono
ofsolidTPA
Aintothere
eactionmasss.Thedeviationbetw
weenthe
experim
mentaldataandsimulaationcanbejustifiedd
duetovariaationinEG//waterreflu
uxratio,
manuall pressure release during
d thee experime
ent to capture the condensaate and
experim
mentallimitationssuch
haswatercondensatio
oninconveyyingpipes.
Figure3.3:W
Watergenerationbased
donmonom
merfeedrattio
40
Influenceofmonomerfeedratiooncarboxylfraction,
Weintroduceaparameter,,thatrepresentsthefractionofcarboxylgroups( a = aF + aT )in
totalterminalgroups.
a
= (21)
a + bT
Duringesterificationphase,carboxylgroupsareconsumedmostlybytheirreactionwithEG
andterminalhydroxylgroups.IncreasedconcentrationofEGpromotesthecarboxylgroup
consumption and simultaneously it increases the terminal hydroxyl groups concentration.
Thus, the value decreases dramatically at high monomer feed ratio during the
esterification (Figure 3.4). The actual final feed ratio in the reactor may be varied due to
some residual EG in the column and in the reactor line. This might cause deviations to
simulation.
model data
0.25
0.20
0.15
()
0.10
0.05
0.00
1.0 1.1 1.2 1.3 1.4 1.5
MRF(EG/PTA)

Figure3.4:Fractionofcarboxylgroupsinterminalgroups,asafunctionofmonomerfeed
ratio
41
Influenceofmonomerfeedratioonchainlengthandmolecularweight
The monomer feed ratio is an important operating parameter to obtain optimum chain
length (n) from esterification. By increasing the monomer feed ratio, n was found to
decrease. Oligomeric chain length was calculated from the measured intrinsic viscosity by
equation(22).
n = (Mn 62 + 88 ) / 192 (22)
Where, Mn = 3.27 10 4 IV 1.4706

Equation(22)canbederivedfromfollowingequation,
MPET = n MTPA + (n + 1 2 ) MEG 2 (n ) MH2O gmol1
(23)
123 144 42444 3 1442443
TPAFeed ConsumedEG Generatedwater
Simulatedchainlength,nSIMhasbeencalculatedfromequation(24)
a0
nSIM = (24)
a + bT
Where,a0isasaponificationnumber.
Thechainlengthdecreaseswithanincreaseinmoleratio,whichcanbejustifiedfurtherby
simulationresultsgiveninFigure3.5. Fromsimulation,optimalfeedratiocanbepredicted
foroptimumdegreeofpolymerizationduringesterificationphaseinabatchreactor.Atvery
lowfeedratios(MRF<1.04), ndropsstrongly.Underthiscondition,thepolymergroupsare
terminated mostly by acid ends, which can not react with each other. While at very high
feed ratios, the polymer end groups are terminated by mostly hydroxyl groups. At
intermediatefeedratios,polymerchainsgrowbyesterification.Theesterificationreactionis
favored since the equilibrium constant is higher than one. Therefore, the reaction is less
limitedbychemicalequilibrium.Inaddition,esterificationreactiongenerateswaterinstead
ofEG.Waterisfarmorevolatilethanglycol,thusitiseasiertoremovefromthereaction
melt.Thisalsofavorstheforwardreaction.21
42
model data
12
10
8
n()
6
4
2
0
1.0 1.1 1.2 1.3 1.4 1.5
MRF(EG/PTA)

Figure3.5:Effectofmonomerfeedratioonchainlength
FromFigure3.6,itisseenthatatlowermonomerfeedratio,thereislowerconcentrationof
bFcomparedtohighermonomerfeedratio;thus, bTgetacompetitiveadvantageover bF to
reactfurtherwith a F ,D or aT whichisresponsibleforadvancementofchainlength.
12 A
MRF
10 A=1.13
B
B=1.20
8 C=1.29
D=1.44
n()
6
4
C D
2
0
0 25 50 75 100 125 150
Time(min)

Figure3.6:Effectofmonomerfeedratioonchainlength
43
Influenceofmonomerfeedratioonconversion
Esterificationconversion,representstheconversionofTPAintoesters.
a
=1 (25)
a0
Byincreasingthemonomerfeedratio,theTPAdissolutionratewasimprovedwhichhelped
tobeincreased.Whiletotalconversion,pthatisresponsiblefortheadvancementofchain
length was found to decrease with an increase in monomer feed ratio as shown in
1.00
0.95
Conversion()
0.90
p
0.85
0.80
0.75
0.70
1.0 1.1 1.2 1.3 1.4 1.5
MRF(EG/PTA)

Figure3.7.
1.00
0.95
Conversion()
0.90
p
0.85
0.80
0.75
0.70
1.0 1.1 1.2 1.3 1.4 1.5
MRF(EG/PTA)

Figure3.7:Effectofmonomerfeedratioonconversions;
Symbols:Experimentalvalues;Line:Calculated
Totalconversionofterminalgroupsisgivenas,
44
a + bT
p =1 (26)
a0
An increase in the monomer feed ratio shifts the balance of carboxyl to hydroxyl groups
away from unity. Based on this, we assume that a decrease in number average of chain
lengthwithanincreaseinEGconcentrationisduetoimbalanceinthecarboxyltohydroxyl
ratiobutnotduetohindranceinthepolycondensationcausedbyhigherEGconcentration.
Figure 3.8 shows the effect of monomer feed ratio on esterification () and overall (p)
conversionsimulatedatthesamereactiontemperature.LoweringoftheEGconcentration
causes prolonged time for complete dissolution of TPA in the system due to its lower
solubilityreactionmedia;consequentlyittakeslongertimeforesterificationconversionto
reachmaximum.
B
1
A
0.8
Conversion()
0.6 D MRF
C
A=1.44,
0.4
B=1.20,
0.2 C=1.20,p
D=1.44,p
0
0 25 50 75 100 125 150
Time(min)

Figure3.8:Conversionasafunctionoftimeandmonomerfeedratio
Differentfunctionalgroupconcentrationprofileduringesterificationphase
The simulation was performed with the monomer feed ratio of 1.13; the reaction
temperaturewasconsideredasactualexperimentaltemperature.From
Figure 3.9, it can be seen that aF,S which represents solid TPA, acts as a reservoir for the
carboxyl groups in liquid phase. The concentration of aF ,D was increased at first due to
temperatureincreaseinthereactorfrom50Cto240Cinthefirst20minutes.Thereafter,
itsconcentrationdroppedsteadilywiththereactiontimetillclearingpoint(tc),wheresolid
TPA just disappeared in the reaction mixture. After the clearing point, the liquid carboxyl
45
groupconcentrationdroppedquickly.Besidethis,onecanfollowthe changein bF,bTand
waterconcentration.
12
Concentration(mol/kg)
bF
10
8
6 a F,S w
4
a F,D tc bT
2
0
0 25 50 75 100 125 150
Time(min)

Figure3.9:FunctionalgroupandwaterconcentrationprofileinEsterificationphase;MRF1.2
InfluenceofTPAparticlesizeonconversion
According to the stationary state, the carboxyl group concentration in the liquid phase
depends on the TPA particle size along with reactor geometryand agitator speed.9 In this
work, mass transfer coefficient, ks was considered to be 2 10 5 mmin1 for semibatch
reactor. In Figure 3.10, we compared the conversion for the model based on TPA particle
size and independent on particle size. Mass transfer rate depending on particle size gave
slightly optimized conversion curve compared to model based constant mass transfer
coefficient.Thedifferenceinconversioncouldbecomelargerforthemasstransferlimited
esterification reactors. Figure 3.11 shows the effect of initial particle size on esterification
conversionfordifferentmonomerfeedratio.ForFigure3.11,TPAparticlesizedistributionis
ignored and all particle are considered of equal size. It can be seen that TPA dissoultion
basedonparticlesizebecomesmoreimportantatlowmonomerfeedratio,becauselarger
particlesizecanleadtomasstransferlimitationduetodeficiencyofexcessEG.Thus,the
model based on TPA particle size is advantageous for mass transfer limited esterification
reactions.
46
1
0.8
A
0.6
()
B
0.4
0.2
0
0 25 50 75 100 125 150
Time(min)

A:MasstransferrateindependentonTPAparticlesize
B:MasstransferratedependentonTPAparticlesize
Figure3.10:Effectofmasstransfercoefficientonconversion;MRF1.2
1.00 D
MRF
0.99
A=1.13
C
B=1.20
()
0.98 C=1.29
B
D=1.44
0.97 A
0.96
1 10 100 1000
Surfaceaverageparticleradius(micrometer)

Figure3.11:EsterificationconversionasafunctionofTPAparticlesizeandmonomerfeed
ratio
Figure 3.12 shows TPA particle size reduction as a function of reaction time and
temperature.Smallerparticlesdissolvepreferentiallyastheyhavehighersurfacetovolume
ratio. The dissolution rate depends on temperature and particle size, consequentely the
particles were observed to be decreased at faster rate due to higher temperature as the
particlesapproachedtoclearingpoint.
47
200 300
180
Particlesize(micrometer)
160 250
Temperature(C)
140 200
120
100 150
80
60 100
40 50
20
0 0
0 25 50 75 100 125 150
Time(min)

Figure3.12:TPAparticlesizereductionasafunctionoftimeandmonomerfeedratio;MRF
1.2
InfluenceofmonomerfeedratioonDEGformation
Figure 3.13 shows the increase in DEG concentration with an increase in monomer feed
ratioinabatchreactor.Itisknownthattheetherificationreactionsareacidcatalyzed.12In
the case of high monomer feed ratio, concentration of hydroxyl groups remains high
compare to low monomer feed ratio, which increases the formation of DEG (based on
equation R 5 and R 6 fromTable3.3)
0.2
MRF A
B
0.16 A=1.20 C
B=1.29
DEG(mol)
0.12 C=1.44
0.08
0.04
0
0 25 50 75 100 125 150
Time(min)

Figure3.13:EffectofmonomerfeedratioonDEGformation
48
Conclusion
The aim of this work was to study the influence of EG/TPA molar feed ratio on various
aspects of esterification process and to simulate esterification reactions with solidliquid
phaseequilibriumforareliablepredictionofthegeneratedoligomersproperties.Atlower
monomerfeedratio,degreeofpolymerizationwasobservedtobeincreasedduetohigher
concentrationofterminalhydroxylgroupsincomparisontofreehydroxylendgroupsofEG.
However,loweringofthemonomerfeedratioincreasedtheTPAdissolutiontime.Influence
of TPA particle size and its distribution has been checked on reaction heterogeneity by
simulation. Esterification conversion and oligomeric chain length became more sensitive
towardsTPAparticlesizeastheEG/TPAfeedratiowaslowered.Itisadvantageoustouse
the model based on TPA particle size for mass transfer limited esterification reactions.
Simulation carried out with help of the given kinetic model agrees to a good extent with
experimentaldata.
Nomenclature
a F ,D carboxylgroupsofdissolvedTPA [molkg1]
a = aF + aT totalcarboxylgroups [molkg1]
a0 saponificationnumber [molkg1]
b = bF + bT totalhydroxylgroups [molkg1]
DEG diethyleneglycol
EG ethyleneglycol
H+ dissociatedprotonsfromcarboxylgroups [molkg1]
IV intrinsicviscosity [dlg1]
kE,i rateconstant [kgmol1min1]
kD masstransfercoefficientbasedonparticlesize [min1]
ks masstransfercoefficient [mmin1]
mEG massofethyleneglycol [kg]
mL massofliquidphase [kg]
MEG molemassofEG [gmol1]
MPET molemassofPEToligomers [gmol1]
Mn numberaveragemolecularweight [gmol1]
MTPA molemassofTPA [gmol1]
49
mTPA,S massofsolidTPA [kg]
MRI EG/TPAfeedratio,initial []
MRF EG/TPAfeedratio,final []
Mw molemassofwater [gmol1]
n degreeofpolymerizationorchainlength []
np,i numberofTPAparticles []
p overallconversion []
pKa acidityofcarboxylgroupinTPA []
TPA terephthalicacid
ri TPAparticleradiusofparticlefraction,i [m]
Sb antimonyion
V0 initialvolumeofTPA solidphase [m3]
w water [mol]
GreekLetters
fractionofcarboxylgroupsinterminalgroups []
specificsurfaceareaperunitvolume [m1]
esterificationconversion []
Appendix
Massofliquidphase,mLiscalculatedas,
Totalinitialmassm0inkgisgivenas,
m 0 = m PTA ,0 + m EG ,0 (27)
Initialmassofliquidphaseinkgisgivenas,
m L , 0 = m EG , 0 + (m EG , 0 TPA ,EG 0.166 ) (28)
Massofliquidphaseinkgatanygiventimeisgivenas,
( m 2 N 0.018) mL ,0
mL = mL ,0 1 + 0 (29)
mL ,0
Derivationofequations(22)and(23):
MolemassofPETisgivenas,
50
M PET = n [M SRN ] (30)
Where, MSRN isthestatisticalrepeatingunit.
O O H

HO CH2 CH2 O C C O
n CH2 CH2 OH
StatisticalRepeatingUnit
M SRN = MTPA + (2 p) MEG 2 MH2O (31)
Fromequation(24)and(25)esterificationconversioncanalsobegiveninformofandnas
below,

=1 (32)
n
Substitutionofequation(26)and(32)intoequation(31)gives,
M SRN =
1
n
[
MTPA + (n + 1 2 ) MEG 2 (n ) MH2O ] (33)
Substitutionofequation(33)intoequation(30)givesequation(23).
SubstitutionofmolemassofTPA,EGandwaterinequation(23)gives,
M PET = n 166 + ( n + 1 2 ) 62 2 ( n ) 18 (34)
Rearrangementofequation(34)givesequation(22)
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[13] G.Challa,J.Polym.Sci.,Makromol.Chem.1959,38,105.
[15] T.Yamada,Y.Imamura,O.Makimura,Polym.Eng.Sci.1985,25(12),788.
[16] ASPENdatabank,AspenTechnology,Inc.
[17] T.Yamada,J.Appl.Polym.Sci.1990,41,565.
[18] ASPENpolyestertechnologymanual,Chapter1,Unitoperationmodels,ASPEN
Technology,Inc.2004,12.1,26.
[19] H.C.Brownetal.,inE.A.Braude,andF.C.NachodDeterminationofOrganic
Structuresby PhysicalMethods,AcademicPress,NewYork,1955.
[21] D. Tremblay, Using simulation technology to improve profitability in the polymer
industry,PaperpresentedatAIChEAnnualmeeting,1999.
52
Chapter4:InfluenceofReactionPressureonSemibatchEsterificationProcess
ofPoly(ethyleneterephthalate)Synthesis
Abstract
Influence of esterification pressure on oligomeric properties was studied by using a
semibatch reactor. Esterification model for semibatch process was further improved by
consideringEGrefluxinthecolumn.Itwasobservedthatincreasingthereactionpressure
decreases EG/water ratio in the column while increasing the EG/TPA feed ratio increases
EG/water ratio in the column. By controlling the EG reflux in a semibatch reactor, it is
possible to generate oligomers with similar oligomeric properties observed at different
stagesofcontinuousprocess.
53
Introduction
Poly(ethyleneterephthalate)(PET)isconsideredasaveryimportantpolymerincommodity
polymers after polyolefin. PET is mostly used for fibers, bottles, and films. PET is mainly
synthesizedfromterephthalicacid(TPA)andethyleneglycol(EG)andtheproductionofPET
essentially involves three steps: direct esterification, prepolymerization, melt
polycondensation. During the esterification process, water is continuously removed as a
byproducttoformlowmolecularweightoligomerswherethelatter(chainlengthof110)
are conveyed to the prepolymerization step and subsequently to the final melt
polymerization. In the semibatch esterification process, reaction temperature is increased
gradually with the formation of oligomers and the vapors emerging from the reactor are
passed through distillation column to separate water from EG and mainly EG is refluxed
back to the reactor. In the presented work, we have studied the influence of reaction
pressureonEGrefluxandsubsequentlyitseffectonoligomericpropertiessuchascarboxyl
group,EGconsumption,chainlength(n),esterificationconversion()anddiethyleneglycol
(DEG) formation. Although, several mathematical models1,2,3 for continuous esterification
process have been published, in which influence of esterification pressure on oligomeric
properties have been presented; however, a little has been reported for the influence of
reaction pressure on a semibatch esterification process. Patel et al.4 have studied the
influence of TPA particle size and EG/TPA feed ratio on the oligomeric properties by
simulation for a semibatch reactor. In the current work, influence of pressure above
atmosphereareestimatedbysimulationusingthemodel4whosevaliditywasconfirmedby
severalexperimentsinasemibatchrector.
Experimentalmethod
ThedirectesterificationwascarriedoutinaParrsemibatchreactorofa1literreaction
volume and equipped with magnetic stirrer drive. EG (1.82 mol) and TPA (1.3 mol) were
mixed thoroughly to make paste and charged to the reactor. Reactor line and the slurry
weremadeoxygenfreebyapplyingnitrogenflushandvacuumsimultaneously.Reactorwas
pressurizedwithnitrogenupto2.5bar.Installedcolumnwasofastraightrefluxtypewith
helix inner packing. The column temperature was maintained at 150 C throughout the
reactiontoseparatewaterandEGandtopreventthetemperaturedropduetoEGreflux.
54
Thecondensertemperatureandstirrerspeedwassetto4Cand140rpmrespectively.Oil
temperaturewassetto290C.Withtheincreaseofthereactiontemperature,thepressure
was increased simultaneously and controlled with magnetic pressure valve. Pressure was
maintainedconstantthroughouttheexperimentatdesiredsetvalue.Attheearlyphaseof
esterification, the reaction temperature increased to the boiling point of EG at given
pressure and as the reaction progressed, oligomers were being formed and reaction
temperature increased due to increase of the boiling point of reaction phase. Resulting
reaction temperature increased from 230 to 260 C. After 90 minutes, the pressure was
gradually reduced to the atmospheric pressure in 5 minutes and the condensate mixture
(water+EG) was collected and analyzed. At the same time, the esterified oligomers were
removed from the reactor and quenched in dry ice. Oligomers were analyzed for their
molecularweightandcarboxylgroupsconcentration.Severalexperimentswerecarriedout
with different set pressure in the range between 3 to 3.75 bar to study its influence on
oligomericproperties.
Intrinsic viscosity of oligomers, carboxyl groups, water in reaction byproduct mixture and
DEGweredeterminedbytheanalyticalmethodsgiveninchapter2.

55
Resultsanddiscussion
MathematicalModel
ReactionScheme
Proton catalyzed esterification, polycondensation and etherification reactions are
considered in this study. Functional group approach is considered for the simulation to
determine end groups and byproducts effectively. Functional group description and
reactionsschemearegiveninTable4.1andTable4.2,respectively.Inthisstudy,thefourth
order RungeKutta method was used to solve differential equations numerically applying
BerkeleyMadonnasoftwarepackage.
Table4.1:Molecularstructuresofcomponentsconsidered.
Symbol Description Molecularstructure

aF Carboxylgroupinterephthalicacid
HOOC COOH

aT Carboxylgroupattachedtoester
HOOC CO
chainend

bF Hydroxylgroupinethyleneglycol HOCH2CH2OH

bT Hydroxylgroupattachedtoester
HOCH2CH2O
chainend
w Water H 2O

dT Diethyleneglycolboundatester
HOCH2CH2OCH2CH2O
chainend
di Internaletherlink COOCH2CH2OCH2CH2OOC

ei Internalestergroup
COO

y bT or aT
56
Reactions Rateconstants(forward,
reverse)
kE1
aF aF + bF bF aT bT +w kE 1 , k E 1 K 1
kE1/K1
kE2
aF aF + bT y aT ei y +w kE 2 , k E 2 K 2
kE2/K2
kE1
bF bF + aT y bT y +w kE 1 , k E 1 K 1
kE1/K1
kE2
y aT + bT y y ei y +w kE 2 , k E 2 K 2
kE2/K2
kT
y bT + bT y y ei y+ bF bF kT , kT K T
kT/KT
kET kET
y bT + bT y y di y +w
kET kET
bF b F + bT y dT y +w
Theassumptionsformodelingwere:(1)Reactionsoccuronlyinliquidphase.TPAispartially
dissolvedinthereactionmixtureandonlydissolvedTPAtakespartinthereaction.(2)TPA
dissolutionratedependsonTPAparticlesize(i.e.specificsurface)andparticlesareassumed
to be spherical for simplifications. (3) Solubility of TPA in water is negligible. (4) Only
undissolvedTPAformssolidphaseofheterogeneoussystem.(5)Esterificationreactionsare
catalyzed by protons which are generated by dissociation of terminal carboxyl groups of
dissolved TPA ( aF ,D ) and carboxyl groups at ester ends ( aT ). (6) Equal reactivity is
consideredforcarboxylgroupsboundtoTPAandtopolymerchainwhilehydroxylgroups
boundtoEGandtoterminalestershavedifferentreactivity.5,6
57
ReactionRate
ReactionratelawforeachcomponentbasedonreactionschemegiveninTable4.2isgiven
inTable4.3.BimolecularreactionofTPAandEGconvertsoneofthecarboxylgroups( aF )of
TPA into the terminal ester group and the other in the terminal carboxyl group ( aT ). The
sameistrueforEG,whereoneofthehydroxylgroups(bF)isconvertedintoterminalester
groupandtheotherintheterminalhydroxylgroup(bT).Consequently,factoroftwoisused
for aF and bF in Table 4.4 to balance the reactions. Furthermore, esterification reactions
between aF and bT, aT and bT and polycondensation reaction between bT and bT produce
internalesterlink(ei).Thesepropertiesaremolalities(mol/kgsolvent)whereasthemassof
total liquid phase can be represented as the solvent mass. Therefore, the use of the unit
mol/kg means: moles of terminal or internal functional groups per mass of total liquid
phase.
Table4.3:Reactionratelaws.(Reactions R6 and R7 produceDEGlink)
Reactionratelaws
R1 = kE1 aF bF ( kE1 K 1 ) bT w
R 2 = k E2 aF bT ( kE2 K 2 ) e i w
R 3 = kE1 bF aT ( kE1 K 1 ) bT w
R 4 = kE2 aT bT ( kE2 K 2 ) e i w
R 5 = kT bT bT ( kT K T ) e i bF
R6 = kET bT bT
R7 = kET bF bT
58
Equations
d aF
= 2 R 1 2 R 2
dt
y EG ( z ) N L

d bF mL
= 2 R1 2 R 3 + 2 R 5 2 R7 k v ,EG bF ,L 2 z +1
dt PEG z

P

EG
*
EG( z )
z =0
d aT
= +R 1 + R 2 R 3 R 4
dt
d bT
= +R 1 R 2 + R 3 R 4 2 R 5 2 R 6 R 7
dt
yW ( z ) N L*

dw mL
= +R1 + R2 + R 3 + R 4 + R 6 + R 7 k v ,w w L z +1
dt Pw z

w* w ( z )
P z =0
d (d T + d i )
= +R 6 + R 7
dt

Phaseequilibrium
DuetothelimitedsolubilityofTPAinEGandtheesterificationisoccurringinliquidphase
only; the solidliquid equilibrium is considered to calculate the functional groups
concentration.Insimulation,TPAsolubilityinEGandinoligomersisconsideredaccordingto
Yamadaetal.2TPAsolubilityinEGisgivenas:
TPA ,EG =9062exp[4877/T]molkg1 (1)
TPAsolubilityinoligomersisgivenas:
TPA ,OLG =374exp[3831/T]molkg1 (2)
whereTisthetemperatureinK
Maximum TPA solubility in the EG and in the oligomers, aF * can be calculated by using
Equations (1), (2), (4), (5) and the esterification conversion, (for definition see equation
(26)).
a F * = EG + ( OLG EG ) molkg1 (3)
59
ThesolubilityofTPAintermsofcarboxylgroupsinEG,
EG 2 TPA ,EG molkg1 (4)
ThesolubilityofTPAintermsofcarboxylgroupsinoligomers,
OLG 2 TPA ,OLG molkg1 (5)
Reactionratefortotalcarboxylgroups(a)canbegivenas,
da da F ,S da F ,D da T
= + + (6)
dt dt dt dt
Where, aF ,S represents thecarboxyl groups attached to undissolved TPA. Carboxyl groups
become available by TPA dissolution in the liquid phase and consumed by esterification
reaction.TPAdissolutionandesterificationrateconstantaregivenaskDandkErespectively.
Itisassumedthatthechangeof aF ,D inthepresenceof aF ,S isclosetozero.
da F ,D da F ,S
= R1 R 2 = k D ( a F * a F ,D ) R1 R 2 0 (7)
dt dt 1442443 123
dissolution consumption
ThemasstransfercoefficientkDdependsontheTPAparticlespecificsurface.kDiscalculated
basedonTPAparticlesizedistributionandparticlespecificsurfaceaccordingtoPateletal.4
VaporliquidphaseequilibriumisconsideredbasedonpolymerNRTLparametersobtained
from ASPEN databank.7 EG and water are considered only volatile components while
oligomers and DEG are considered to be non volatile under used reaction conditions. The
molefractionsandactivitycoefficientarecalculatedbasedonapparentamount ofwater,
EGandoligomersintheliquidphase.ThevaporphasemolefractionsofEGandwaterare
givenbythefollowingequations.
x EG EG PEG = y EG P (8)
x w w Pw =y w P (9)
x DEG + x EG + x w + x OLG = 1 (10)
y EG + y w = 1 (11)
where, x DEG , x EG , x w and x OLG are the liquid phase apparent mole fraction of DEG, EG,
waterandoligomers, y EG and y w arethevaporphasemolefractionsofEGandwater, PEG
and Pw arethevaporpressureofpureEGandpurewaterinbar,Pisthetotalpressurein
bar,and EG and w aretheactivitycoefficientofEGandwater.Vaporpressuresofpure
componentsarecalculatedfromYamadaetal.2
60
log PEG = 7.8808 + log (1 / 750 ) 1957 /( + 193.8 ) (12)
log Pw = 7.9668 + log(1 / 750) 1668.2 / ( + 228) (13)

where, isthereactiontemperatureinC
InTable4.4,asimpleapproachhasbeenconsideredforthemassbalanceequationsforEG
andwater.ThetermsforwaterandEGremovalascondensatewerederivedbyconsidering
thewaterandEGseparationwithoutcolumn,withincolumnandwithcolumn.Themodel
equationsforeachsituationaregivenasfollow,
EGandwaterseparationwithoutcolumn
NL* * NL* P
w L* = xw = yw
(14)
mL mL Pw w
wL*isamolalityofwaterinthemeltatboundarylayer.NL*isthetotalmolesofthereactive
components in the melt at boundary layer. The total number of moles at this position
shouldbecomparableasthetotalnumberofmolesinthebulkphaseNL.
NL * NL = mL (w L + (bF ,L / 2 ) + (a / 2n )) (15)
where wLand bF,Lrepresentsthemolesofwaterand bFinliquidphase. mListhemassof

liquidphasewhichcanbegivenas,
m L = n a ( 0 ) / a (16)
where na(0) are the initial moles of carboxylic acid groups and a is the saponification
number. x w* isthemolfractionofwaterinthemeltatboundarylayerand w* istheactivity
coefficientofwaterinthemeltatboundarylayer.(calculatedasperASPENPNRTLmodel)
EGandwaterseparationwithincolumn
Forthecolumnhavingzstages,EGandwaterseparationwithincolumncanbegivenas,
yw ( z ) 1 yEG( z ) Pw z z
= = w ( at (17)
xw ( z = 0 ) 1 xEG( z = 0 ) P z =0
z)
whereyw(z)isthemolefractionofwaterinvaporphaseatstagez,xEG(z=0)isthemolefraction
ofEGintheliquidphaseatbottomofthecolumn, yEG(z)isthemolefractionofEGinvapor
phase at stage z, xw(z=0) is the mole fraction of water in the liquid phase at bottom of the
61
column.
EGandwaterseparationwithcolumn,
Bycombiningequation(14)and(17)andconsideringtheoreticalnumberofcolumnstagez
=2.2(measuredbyEGwaterVLEdata);EGandwaterseparationwithcolumncanbegiven
as,

N y w( z )
wL *
= L
m L Pw * Pw z z
w w ( at z)
(18)
P P z =0
Itmeans,therelationbetweenthemolalityofthewaterinthemeltatboundarylayer(wL*)
andthemolefractionofwaterinthetotalcondensatephase(yw(z))canbegivenas,

N yw( z )
wL = L
*
(19)
m L Pw z +1 * Z
w w ( at z)
P z =0
Masstransfercoefficientofwater(kv,w)andEG(kv,EG)istakenfromRafleretal.8Byusingthe
mass transfer coefficient in equation (19), the total transfer of water and EG from the
respectivebulkphaseswLandbF,Lintothecondensate(yw(z),yEG(z))isgivenby,
y w( z ) N L*

(
k v ,w w L w L * ) = k v ,w w L z +1
mL
(20)
Pw z

P
w
*
w ( at z )
z =0
y EG ( z ) N L

k v ,EG (bF ,L bF* ,L ) = k v ,EG bF ,L 2
mL
z +1 (21)
PEG z

P

*
EG EG ( z )
z =0
Catalysis
Inthepresentstudy,theesterificationreactionswerestudiedwithoutanymetalcatalysts.
Esterificationreactionsinvolveacidcatalysismechanism.Thecatalyticinfluenceofanacid
depends on the degree of dissociation of the acid. Acid strength (pKa) of dissolved TPA
carboxyl group and oligomeric terminal carboxyl group are considered to be the same.9,10
ThepKavalueofcarboxylgroupofTPAandterminalcarboxylgroupsisgiveninmol/L.From
62
our experience, the density of the melt esterification phase is close to 1 kg/L. Therefore
given equation (22) can be used for the calculations where the molality has been
considered.
H + (a F ,D + a T ) 10 pKa (22)
The effective rate constant for esterification, polycondensation and DEG formation
reactionscanbegivenby,
k i = H + k ,i (23)
where,k,iisamicrokineticrateconstant
Otton et al.10 observed that acid catalyzed esterification is about three times faster than
acid catalyzed polycondensation. This relationship is used for the polycondensation rate
constant,kT=kE1/3.
Table4.5:Kineticparametersusedforthesimulation
Kineticconstants Activationenergy Frequencyfactor Equilibrium

k ,i = Ai exp( E i / RT ) Ei[kcalmol1] Ai[kg2mol2min1] constant
k ,1 18 4.60 108 K1:2.50
k ,2 18 1.06 1010 K2:1.25
k ,3 = k ,1 /3 K3:0.5
k ,4 29.8 4.59 1012

Table4.6:Numericalvaluesusedforthesimulation
k v ,w = 0.438min1
k v ,EG = 0.156min1
Theoreticalnumberofstages(z)inthecolumn=2.2
pKa=3.51
In semibatch or continuous PET process, the degree of polymerization advances by

esterificationandpolycondensationreactionssimultaneously.Therefore,itisimportantto
havetheoptimumbalanceofcarboxylandhydroxylgrouptoattainoptimumconversion.An
excess or deficiency of one or the other reactant will cause quality deviations and the
63
changesinthereactionrate.11
Insemibatchprocess,esterificationphaseisnearlycompletedbeforeapplyingfullvacuum
toinitiatepolycondensationphase.Therefore,atthebeginningofbatchpolycondensation,
oligomeric fraction of carboxyl groups in total terminal groups () remains significantly
lower than in continuous process. While, in continuous process, the carboxyl group
concentration changes at different stages due to their consumption via esterification and
formationviaesterlinkdegradationreactions.Inmostindustrialcontinuousprocesses,the
meltphasereactionisperformedinthreetofivecontinuousreactorsinseries.12Therefore,
itisdesirabletohavespecificoligomericateverystagetofulfilltherequirementofnext
stageincontinuousprocess.
Yokoyama13 and Duh et al.14 studied the effect of carboxyl group concentration on
polycondensation rate in melt and solid phase respectively. However, the formation of
oligomerswithhavingbroadvaluesanditseffectonesterificationandpolycondensation
rate has not been studied extensively. As far as we know, there has not been a paper
narratingthegenerationofoligomersofdifferentbyasemibatchprocessthatresembles
the oligomers observed at the different stages of a continuous process. In this paper, we
have made an attempt to simulate continuous process functional group profile by using
semi batch process. In our previous studies4, we generated the oligomers of different
valuesbyvaryingtheEG/TPAfeedratio.However,theobtainedvaluewasobservedtobe
lower than in continuous process. The feed ratio could not be lowered further due to
extremelylowsolubilityofTPAinEG.Inpresentedwork,wehavegeneratedoligomersof
differentbyvaryingtheesterificationpressureatconstantEG/TPAfeedratio.
Figure 4.1 shows the influence of esterification pressure on fraction of unreacted EG to

initialEGfeed.Thisfractioncanbecalculatedas,
a ( 2 p ) mL
EG L + EG V = EG 0 EG R = EG 0 (24)
2
where, EGLand EGVarethemolesofunreactedEGinliquidandvaporphaserespectively.

EG0 and EGR are the moles of initial and reacted EG respectively. and p are the
esterificationconversionandconversionbychainpropagationrespectively.
64

0.32
0.28
(EG0EGR)/EG0 ()
0.24
0.20
0.16
3 3.2 3.4 3.6 3.8
P(bar)

Figure4.1:EffectofesterificationpressureonunreactedEGinvapourandliquidphase.
Symbols:experimentalvalues;Line:calculated
Unreacted EG at the end of esterification phase can be calculated by using equation (24)
which simplifies the influence of pressure on EG reflux. As can be seen in Figure 4.1, an
increase in esterification pressure boosts EG consumption and thus lowers unreacted EG.
Furthermore, to investigate the influence of pressure and EG/TPA feed ratio on vapour
phasecomposition,condensatewascollectedattheendofesterificationandanalysedfor
EG and w content. From Figure 4.2, it can be seen that increasing pressure reduces EG/w
ratiointhevapourphasebyincreasingtheEGreflux.FromFigure4.3,itisseenthatEG/w
ratio in the vapour phase exhibits some opposite behaviour with increasing EG/TPA feed
ratio.ThisisduetotheincreasingEGmolfractioninliquidphaseenhancesEGmolfraction
invapourphase.
65
0.20
EG/winvaporphase(mol/mol)
0.16
0.12
0.08
0.04
0.00
3 3.2 3.4 3.6 3.8
P(bar)

Figure4.2:EffectofesterificationpressureonEG/Winvaporphase.
0.09
EG/winvaporphase(mol/mol)
0.08
0.07
0.06
0.05
0.04
0.03
1 1.2 1.4 1.6 1.8
EG/TPA(mol/mol)

Figure4.3:EffectofEG/TPAfeedratioonEG/Winvaporphase.Pressure:4bar
FromFigure4.4itcanbeseenthatloweringthepressureinesterificationphasedecreases
theEGrefluxandreducestheEGconcentrationinliquidphase.ReductionofexcessEGin
liquid phase promotes further esterification of aT with bT and also lowers reverse
polycondensationreactionwhichisresponsibletoincreasenand.Figure4.4suggeststhat
itispossibletoprepareoligomershavingvalueofabroadrangebyvaryingtheEGreflux
orthereactionpressureinsteadofvaryingtheEG/TPAfeedratio.nwascalculatedfromthe
measuredintrinsicviscosityusingEquation(25).4
n = (Mn 62 + 88 )/ 192 (25)
where M n = 3.27 10 4 IV 1.4706
66
8 0.8
7
n 0.6
6
()
n()
5 0.4
4
0.2
3
2 0.0
3 3.2 3.4 3.6 3.8
P(bar)

Figure4.4:Effectofesterificationpressureonnand.
Figure 4.5 supports that higher reaction pressure increases the EG concentration in liquid
phase which promotes both esterification and etherification and thus overall EG
consumptionwasobservedtobeenhanced.DEGformationwasobservedmuchhigherthan
commercial continuous process. This was expected due to higher reaction pressure and
reactionscarriedwithoutanyDEGsuppressant.
5
DEG(wt%)
2
3 3.2 3.4 3.6 3.8
P(bar)

Figure4.5:InfluenceofreactionpressureonDEGformation.
Esterification conversion , which represents conversion of TPA into esters, can be
expressedas,
a
=1 (26)
a
67
Whileconversionbychainpropagation(p)canbegivenas,
E a + bT
p = 1
= 1 (27)
a a
where,Eistotalterminalgroups.
From Figure 4.6 it is seen that higher reaction pressure increases the esterification
conversion due to higher concentration of EG in liquid phase which enhances the TPA
dissolutionandconsequentlyitsconversionthroughesterificationreaction.While,pressure
has significant effect on EG reflux which influence the carboxyl to hydroxyl ratio in the
reactionliquidphase.Thus,deviationfromoptimumfunctionalgroupbalancereducesp.
1.00
0.95

Conversion()
0.90
0.85 p
0.80
0.75
0.70
3 3.2 3.4 3.6 3.8
P(bar)

Figure4.6:Influenceofreactionpressureonconversion.
Conclusion
EsterificationpressurehassimilarinfluenceastheEG/TPAfeedratiooncertainoligomeric
properties. An increase in both variables enhances esterification conversion () and
decreases the chain propagation conversion (p). However, it was observed that by
increasing the reaction pressure, EG/w ratio in the vapor phase was observed to be
decreased while by increasing the EG/TPA feed ratio, EG/w ratio in the vapor phase was
observed to be increased. It has been shown that by varying the reaction pressure in a
semibatch esterification process, it is possible to produce oligomers of having a broad
range that observed in continuous process. Semibatch process can be utilized to study
different additives and catalysts in the presence of functional groups profile observed in
continuousprocess.
68
Nomenclature
a F ,D carboxylgroupsofdissolvedTPA [molkg1]
a = a F + aT totalcarboxylgroups [molkg1]
a saponificationnumber [molkg1]
DEG diethyleneglycol
E totalterminalgroup [molkg1]
EG ethyleneglycol
k,i effectiverateconstant [kgmol1min1]
kD masstransfercoefficientbasedonparticlesize [min1]
kv,i masstransfercoefficientofcomponenti [min1]
mL massofliquidphase [kg]
MRI EG/TPAfeedratio []
n chainlength []
P pressure [bar]
p conversionbychainpropagation []
pKa acidityofcarboxylgroups []
TPA terephthalicacid
z numberofstagesinthecolumn []
GreekLetters
fractionofcarboxylgroupsinterminalgroups []

69
References
[1] K.Ravindranath,R.Mashelkar,Polym.Eng.Sci.,1982,22,10.
[2] T.Yamada,Polym.J.,1992,24(1),43.
[3] C.K.Kang,B.C.Lee,D.W.Ihm,D.A.Tremblay,J.App.Polym.Sci.,1997, 63,163.
[4] H.Patel,G.Feix,R.Schomaecker,Macromol.React.Eng.,2007,1,502.
[5] G.Challa,J.Polym.Sci.,Makromol.Chem.1959,38,105.
[7] ASPENdatabank,AspenTechnology,Inc.
[8] G. Rafler, F. Herfurth, B.Otto, J. Marth, H. Gajewski, K. Zacharias, Acta
Polymerica,1989,40(1),44.
[9] H. C. Brown, Determination of Organic Structures by Physical Methods, E. A.
Braude,F.C.Nachod,Eds.,AcademicPress,NewYork1955.
[10] J.Otton,S.Ratton,J.Polym.Sci.PartA:Polym.Chem.1988,26,2183.
[11] E.vanEndert,R.Hagen,Chemiefasern/Textilindustrie(CTI),1993,42/95,480.
[12] Th. Rieckmann and S. Voelker, Modern Polyesters, J. Wiley & Sons, Ltd., 93,
2003.
[13] H. Yokoyama, T. Sano, T. Chijiwa, R. Kajiya, Kobunshi Ronbunshu, 1979, 36(8),
557.
[14] B.Duh,J.App.Polym.Sci.,2002,83,1288.
70
Chapter5:InfluenceofOligomericCarboxylandHydroxylGroupBalanceon
CatalyzedPolycondensationofPETSynthesis
Abstract
Continuous Poly(ethylene terephthalate) (PET) process contains different carboxyl to
hydroxyl end group balance profiles for each of the reactors within the reactor cascade.
Such a different functional group balance profile is generated in lab scale experiments by
usingasemibatchreactor.Severalsetsofexperimentsareperformedtochecktheinfluence
of oligomeric carboxyl and hydroxyl group balance on antimony and titanium catalyzed
polycondensation phase of PET synthesis with respect to reaction rates and molecular
weight. Ratio of esterification and transesterification rate coupled with antimony catalyst
inhibition by hydroxyl groups leads to strong dependency of overall reaction rate on
functional group balance. Optimal functional group composition is investigated by
simulationsbasedonacomprehensivekineticmodel.
71
Introduction
ThekineticsofmeltphasepolycondensationofPoly(ethyleneterephthalate)(PET)process
hasbeenstudiedbyseveralgroupsmainlyinthinfilms,1batchorcontinuousreactorsandit
isgenerallyacceptedthatthepolycondensationrateismostlyaffectedbythecatalysttype
andconcentration,temperature,diffusionofvolatilesfromreactionmeltandthecarboxyl
content.2 First three parameters have been widely studied. However, only a few authors
havediscussedtheinfluenceofcarboxylgroupcontentontheoverallreactionrate.Duhet
al.3andYokoyamaetal.4havestudiedtheinfluenceofcarboxylgroupcontentinasolid
phaseandincontinuousmeltphase,respectively.Duhetal.proposedanoptimalcarboxyl
group concentration for pelletized solid state polycondensation. Yokoyama proposed
optimalcarboxylgroupconcentrationinoligomersforthemeltphasepolycondensation,but
detailed reasons for the optimal carboxyl content were missing. Berkau et al.5 proposed
preferred carboxyl group concentration region for optimal reaction rate during melt
polycondensationandpredictedduetocriticalnatureofcarboxyl/hydroxylgroupratioand
varieddiffusivitiesofvolatilesinthemelt.Rafleretal.6presentedthedetailedcomparison
of reaction model based on the reactiondiffusion convection and reactionmass transfer
and suggested that the reactionmass transfer model proves to be more suitable for the
stirred polycondensation systems. Therefore, only the mass transfer coefficient has to be
estimated.
In two previous contributions,7,8 we have developed mathematical models for the
semibatchesterificationprocessforPETsynthesis.Inthisinvestigation,wehavestudiedthe
influenceofcarboxylgroupfraction(,carboxylgroupcontentintotalendgroups)inthe
semibatch melt polycondensation process by taking mass transfer of ethylene glycol (EG)
andwaterintoaccount.Wehaveusedtheavailableexperimentaldatatoverifythemodel.
Primarily, low molecular weight oligomers are produced from esterification reaction of
terephthalic acid (TPA) and EG. These low molecular weight oligomers were further
polymerizedatcomparativelyhighertemperatureandundervacuumtoobtainprepolymer
withfiberorfilmgrademolecularweight.
72
ExperimentalMethod
To study the effect of oligomeric carboxyl to hydroxyl balance on antimony and titanium
catalyzedpolycondensation,esterificationphasewascarriedaccordingtothemethodgiven
in Patel et al.8 with added catalyst Sb (230 ppm, Atofina) or Ti (15 ppm, Equipolymers
GmbH)and2wt.%isophthalicacid(purity99%,FlukaChemie).Esterificationwascompleted
after90minutesandoligomericsamplewascollectedbyopeningthereactorbottomvalve
under nitrogen pressure slightly above atmospheric pressure to avoid oxygen penetration
intothereactor.Aftersampling,theoligomericmeltlevelinthereactorwasmaintainedat
about 25% of the reactor volume. Oil temperature was increased to 295 C. Pressure was
reduced gradually in the span of 5 minutes and later full vacuum was applied to favour
polycondensation. The reactor was equipped with helical ribbon type of stirrer and the
initial rotational speed was kept at 140 rpm in the prepolymerization phase. As the
oligomeric molecular weight increased, reaction temperature also increased due to shear.
Once the reaction temperature reached 280 C, stirrer speed was reduced to 50 rpm and
kept constant throughout the remaining polycondensation phase. Several screening tests
were performed under different rotational speed to check its influence on overall
conversion.Optimalconversionwasobtainedwithstirringspeedcombinationof140rpmin
prepolymerization and 50 rpm in the final polymerization phase. However, it should be
noted here that such an optimal stirring speed depends on reactor geometry and stirrer
type. Each experiment was concluded after 45 minutes for Sb catalyzed polymerization.
While,forexperimentscontainingTicatalyst,reactiontimewasvariedbasedonobtained
molecularweight.Finally,thepolymerswereremovedundernitrogenpressureinawater
bathandpelletized.Collectedsampleswerecharacterizedbymeasuringthecarboxylvalue
andintrinsicviscosity.
Frommeasuredintrinsicviscosity(IV),molecularweightcanbegivenas,
Mn = 3.27 104 IV 1.4706
(1)
Totalendgroupconcentration(E)inmol/kgisgivenas,
E = 2000 / Mn (2)
Where Mn is in g/mol. Carboxyl concentration (aT) is determined by the KarlFischer
titrationmethod.Hydroxylgroupconcentrationofterminalesters(bT)canbedeterminedby
subtractingacidgroupconcentrationfromE.
73
Thecarboxylfraction()isgivenas,
= aT E (3)
TheinterfacialconcentrationofvolatilespeciessuchasEGandwaterarecalculatedbyusing
theFloryHugginsmodel.ThevaporpressureofEG( PEG )andwater( PW )arecalculatedusing
theequationsgiveninTable5.1.TheequilibriummolefractionofEGandwaterinthebulk
phasecanbegivenas,
P y EG P yW
*
X EG = and X W* = (4)
EG PEGo W PWo
WherePisthereactorpressure;yEGandyWarethemolefractionofEGandwaterinvapor
phaserespectively;EGandWaretheactivitycoefficientsoftheEGandwater,respectively,
andcalculatedasfollow,
1 1
j = exp 1 + j (5)
mj mj

wheremjistheratioofmolarvolumesofpolymertovolatilespeciesj(j=EG,W)andjisthe
Flory interaction parameter. Melt phase volume of the volatile species per volume of
reactionmixture(V)isgivenby
Mjc j
V = p (6)
j j
where Mj is the mole mass of the component j, j is the density and cj is the molar
concentration.pisthepolymermeltdensity.Thetotalconcentrationofpolymericspecies
isgivenas,
1
c poly = (aT + bT + E V ) p (7)
2
Fromequation(6)and(7),themolarvolumeofthepolymerisgivenby,
1 v
p = (8)
c poly
Theequilibriumconcentrationofthevolatilecomponentisgivenby,

cpoly *
cj =
*
* j
x (9)
1 x j
j
74
Initially, values of yj were assumed and calculations were further followed to obtain new
value of yj and vapor phase mole fraction were corrected until the initial and obtained
valueswerefoundtobeascloseaspossible.
Table5.1:Experimentalparametersandvariablesusedforcalculations
Sb=230ppm
Ti=15ppm
P=0.1mbar
log Pw = 7.9668 + log(1 / 750) 1668.2 / ( + 228)
log PEG = 7.8808 + log(1 / 750) 1957 /( + 193.8 )
H+=aT103.5111molkg1
InhibitionfactorforSbcatalysis,=1kgmol1
Masstransfercoefficient, k L = 6.0 10 3 cms1(Rafleretal.6)

Specificsurface,a=70cm2cm3
Floryinteractionparameter,=1.3
PhysicalconstantsEG=1.1135,W=1.0,P=1.14gcm3
75
ResultsandDiscussion
InTPAandEGbasedPETprocess,esterificationandpolycondensationreactionstakesplace
simultaneouslyduringthemeltpolycondensationphaseduetothepresenceofcarboxyland
hydroxyl groups. Kinetics become more complex because of main reactions coupled with
back and side reactions and increasing mass transfer limitation due to increasing melt
viscosity at higher conversion. In the present study, antimony acetate and titanium based
chelatedcatalyst(suppliedbyEquipolymersGmbH)areusedaspolycondensationcatalysts.
ElToufaili et al.9 has observed that relative activity of antimony (Sb) in polycondensation
was enhanced strongly with a decreasing hydroxyl end group concentration of oligomers.
AccordingtoElToufailietal.,Sbinhibitionintheinitialpolycondensationphaseisobserved
duetohindranceofSbesterchainendchelationcausedbycompetitionbetweenhydroxyl
groupsofEGandoligomers.Hovenkamp10alsosuggestedtheinhibitionofSbcompoundsby
EG. While Ti does not show such inhibition by hydroxyl groups instead Ti is in a favorable
neighborhoodinthepresenceofexcesshydroxylgroups.Basedonthesestudies,wehave
usedaninhibitionparameter()asafunctionofhydroxylgroupconcentration(1/1+[OH])
forthesimulationstudywhereSbwasusedascatalyst.SbandTicatalyzedsidereactions
are also considered in the present study. Chen and Chen11 observed that most of the
diethyleneglycol(DEG)isformedinesterificationphasewheretheconcentrationofEGand
carboxylgrouparesignificantlyhigh,thuswehaveignoredtheDEGformationreactionsfor
meltpolycondensationphasewhileconsideringonlytheacetaldehydeandthermalscission
reactions.Thefunctionalgroupapproachisconsideredtodeterminetheconcentrationsof
endgroupsandbyproductseffectively.Majorreactionsconsideredforsimulationaregiven
inTable5.2.

76
Reactions Rateconstants
(forward,reverse)
Esterinterchangereaction(mainpolycondensation)

k1
y bT + bT y y ei y + bF bF k 1 ,k 1 K 1
k1/K1
Polycondensationreactionthroughesterification

k2
y aT + b T y y ei y +w k 2 ,k 2 K 2
k2/K2
Esterificationreaction

k3
bF b F + aT y bT y +w k 3 ,k 3 K 3
k3/K3
Degradationofinternalesterlink

k4
y ei y y aT + V y k4

Acetaldehydeformation

k5
y bT + v y y ei y+ z k5

k6 k6
y bT y aT + z
WhereaTistheterminalcarboxylgroup,bTistheterminalhydroxylgroup,bFisthehydroxyl
group in EG, ei is the internal ester link, w is water, v is the vinyl end group and z is
acetaldehyde. The concentrations of these species are given in molality (mol/kg solvent)
whereasthemassoftotalliquidphasecanberepresentedasthesolventmass.Therefore
the use of the unit mol/kg can be interpreted as moles of terminal or internal functional
groups permass of total liquid phase. The reaction rate laws and mass balance equations
aregiveninTable5.3andTable5.4,respectively.
77
Table5.3:Reactionratelaws.
R1 = k 1 bT bT ( k 1 K 1 ) e i bF
R 2 = k 2 aT bT ( k 2 K 2 ) ei w
R 3 = k 3 bF aT ( k 3 K 3 ) bT w
R4 = k4 ei
R 5 = k 5 bT v
R6 = k6 bT
TheoverallrateconstantforSbandTicatalysiscanbegivenas,
k ,i [Sb]
ki =
1 + [OH]
[ ] [ ]
+ k ,iC H + and k i = k ,i [Ti ] + k ,iC H + (10)
where, k,i and k,iC are micro kinetic rate constants for metal and proton catalysis
respectively. is an inhibition factor as a function of hydroxyl group concentration in
antimony catalyzed polycondensation phase. H+ is the proton concentration in mol/kg. Ti
catalyzed equation does not contain such an inhibition factor. In simulation, only metal
catalyzed side reactions are considered. In this study, differential equations were solved
usingBerkeleyMadonnasoftwarepackage.

78
dbT
= 2 R 1 R 2 + R 3 R 5 R 6
dt
da T
= R 2 R 3 + R 4 + R 6
dt
de i
= R1 + R 2 R4 + R5
dt
dbF
dt
( )
= 2 R 1 2 R 3 k L ,a bF ,L bF *
= R 2 + R 3 k L ,a (w L w * )
dw
dt
dz
= R 5 + R6
dt
dv
= R4 R5
dt
We have investigated the influence of oligomeric (fraction of carboxyl groups in total

terminal groups), reaction pressure and mass transfer coefficient for Sb and Ti catalyzed
polycondensationphasethroughexperimentalandmodelingstudies.
Generally,kineticdataevaluationisperformedwithdatacollectedatspecifictimeintervals
for a given experiment. However, we carried out each experiment for a constant time
without disturbing the experimental conditions which can be affected by continuous
sampling of the reaction mass. Consequently, we obtained two data points for each
experiment i.e. start and end points. Furthermore, several experiments were performed
withdifferentinitialoligomericcarboxylfractionandobtaineddatapointswereconsidered
tofitthemodelparameters.InFigure5.1,apparentpolycondensationrate(n/dt)isplotted
against oligomeric for Sb and Ti catalysis. For Sb catalysis, with increasing oligomeric
from0.05to0.3,thepolycondensationrateisobservedtobeincreased,furtherincreaseof
leadsagaintoadropinoverallpolycondensationrate.Thus,thereexistsanoptimalfor
Sb catalyzed melt polycondensation. For Ti catalysis, meltpolycondensation rate does not
exhibit a maximum however further extrapolation of the to zero, highest rate can be
observed.
79
Ti TiModel Sb SbModel
4
n/t(1/min)
3
1
0.0 0.1 0.2 0.3 0.4 0.5
Oligomeric

Figure5.1:EffectoftheoligomericontheAPETchainlength(n)forTiandSbcatalyzed
polycondensation.(reactiontimeforSbcatalysis:45minutes;
reactiontimeforTicatalysis:30,35,40and45minutes)
This phenomenon can be explained by a combination of catalyst inhibition and proton

catalysis;whichplaysanimportantroleonoverallreactionrate.Modelparametersmainly,
rateconstantsk1,k2,masstransfercoefficientkLaandSbinhibitionfactorareadjustedfor
the optimal fitting of the experimental data. Mass transfer and inhibition parameter are
giveninTable5.1andkineticconstantsaregiveninTable5.5.

80
Table5.5:Kineticparametersusedforthesimulation
Kineticconstants Activation Frequencyfactor Equilibrium
k ,i = A i exp( E i / RT ) energy Ai[kg2mol2min1] constant
Ei[kcalmol1]
Sb Ti Sb Ti
k ,1 18.5 18.3 1.80 109 1.60 10 10 K1:0.5
k ,1 C = k ,2 C /3
k ,2 18.0 18.0 2.40 10 9 2.4 10 10 K2:1.25
k ,2 C 18.0 18.0 2.70 10 9 2.70 10 9
k ,3 = k ,2 K3:2.50
k ,3 C = k ,2 C
k ,4 37.8 44.1 3.51 10 12 4.34 10 13
k ,5 = k ,1
k ,6 29.8 29.8 4.05 10 10 4.05 10 10

Theoverallpolycondensationratecanbedividedintoesterificationandtransesterification
rates.
Esterificationrate,RE=(aT0aT)/t (11)
Transesterificationrate,RT=((bT0bT)/t)RE)/2 (12)
FromFigure5.2,itcanbeseenthatesterificationrateisincreasedwithincreasingfrom0
to 0.4. However further increase in above 0.4, lowers the esterification rate due to
depletionofbTincomparisontoaT,whichfinallylowerstheoverallpolycondensationrate.
FromFigure5.3,itisobviousthattransesterificationratedecreaseswithincreasingsince
RT = ki bT 2 .Atlow,TicatalysisexhibitshighertransesterificationrateincomparisontoSb
catalysissincethetitaniumcatalyzedrateconstantishigherwithrespecttothatofSb.In
additionSbcatalyzedtransesterificationratedropsduetoinhibitionbyexcessofbTandbF.
81
0.016
Esterificatnionrate
0.012
(mol/kgmin)
0.008
0.004
0
0.0 0.1 0.2 0.3 0.4 0.5
Oligomeric

Figure5.2:Effectofoligomericonesterificationrateduringpolycondensationphase.
0.04
Transesterificationrate
(mol/kgmin)
0.03
0.02
0.01
0
0.0 0.1 0.2 0.3 0.4 0.5
Oligomeric

Figure5.3:Effectofoligomericonthetransesterificationrateduringpolycondensation
phase.
In Figure 5.4 and Figure 5.5, the overall rate constants k1 and k2 obtained from the data
fittingareplottedagainsttimetochecktheinfluenceofprotoncatalysisandSb.Itcanbe
seen that particularly at low , Sb catalyzed transesterification and esterification rate
constants exhibit low values at initial polycondensation phase and increases with reaction
time. This can be explained due to Sb inhibition by excess of hydroxyl group of EG and
oligomers which contributes in lowering of the rate constants. However at high , the
contribution from proton catalyzed transesterification actually compensates the low rate
82
induced by Sb inhibition in early polycondensation phase. Since the carboxyl group

concentration drops with time, the reaction rate decreases and becomes equal to metal
catalyzed reaction rate. Interestingly, Ti catalysis does not have such an inhibition from
hydroxyl groups and exhibits optimum activity from the very beginning of the
polycondensationphase.
0.4
Ti,=0.27
k1 (kg/molmin)
0.3
Ti,=0.04 Sb,=0.27
0.2
0.1
Sb,=0.04
0
0 5 10 15 20 25 30 35 40 45
Time(min)

Figure5.4:Overalltransesterificationrateconstants,k1forTiandSbcatalysis
(at=0.04,aT=0.1mol/kg;at=0.27,aT=0.5mol/kg)
0.8 Ti,=0.27
k2 (kg/molmin)
0.6
Ti,=0.04 Sb,=0.27
0.4
0.2
Sb,=0.04
0
0 5 10 15 20 25 30 35 40 45
Time(min)

Figure5.5:Overallesterificationrateconstants,k2forTiandSbcatalysis
(at=0.04,aT=0.1mol/kg;at=0.27,aT=0.5mol/kg)
83
Figure5.6showstheinfluenceofreactionpressureonoptimaloligomericforSbcatalyzed
reaction. Vapour pressure of EG is much lower than of water, thus as the pressure is
increased, the overall reaction rate drops due to reverse reactions, mainly glycolysis
reaction by EG. Also the equilibrium constant for transesterification is about 0.5 in
comparisontoesterificationequilibriumconstantof1.25.Asaresultofthat,esterification
reaction is less retarded in comparison to transesterification. Under moderate vacuum,
esterification is more favoured and consequently optimum is observed to be shifted to
highvalueswithincreasingpressure.
P=0 P=0.1 P=0.5

P=1 P=2
110
100
Chainlength,n
90
80
70
60
50
40
0.0 0.1 0.2 0.3 0.4 0.5
Oligomeric

Figure5.6:Influenceofoligomericonthechainlengthatdifferentpressuresinmbar.
(Sbcatalysis;simulatedreactiontime:45minutes)
In PET polycondensation phase, mass transport limitation between the phases plays an
essentialrole.Forsemibatchpolymerization,helicalribbontypestirrersarecommonlyused
duetotheircapacitytogeneratelargeinterfacialareaatlowspeedofagitation.12Veryhigh
speedofagitationdoesnotleadautomaticallytothinnerfilmsorshorterdiffusionpaths.In
thiscase,thestirrerefficiencydropsandthestirrerbladescutthemeltbutdonotgenerate
effective specific interface. Based on this, we optimized the agitation profile for the melt
polycondensation phase in our reactor. Mass transfer coefficient kLa depends strongly on
hydrodynamics of the reaction melt. As a consequence, it becomes more difficult to
evaluatetheapproximateorderofmagnitudeofkLaduetohighviscosityandlargebubble
formation at high conversion. As a result of mixing and bubble formation, the specific
84
interfacegeneratedinthestirredreactorismorethanoneorderofmagnitudelargerthan
theareacalculatedfromthereactionmeltvolumeandreactordimensions.6Rafleretal.also
found that the specific mass transfer area generated by both stirring and evaporation
dependsonthereactivityofthereactantsinthesystem,catalystandtemperature.Cheong
et al.13 observed that the enhanced interfacial area exerted by EG bubbles accounts for
about 3050% of the total available interfacial mass transfer area. Based on these
assumptions, we have adjusted the specific interfacial area for optimal fitting of our
experimental data (25.2 min1). From Figure 5.7 and Figure 5.8, it can be seen that
decreasing mass transfer coefficient lowers the chain length and shifts the optimal to
higher value. However at value of 0.35 and higher, the influence of mass transfer on
polycondensation rate diminishes. This can be further explained due to principle reaction
being esterification in comparison to transesterification and mass transfer resistance
becomeslowerduetowaterisproducedlargelyasabyproductinsteadofEG.
72 36 25.2 21.6 14.4

140 kLa(1/min)
120
Chainlength,n
100
80
60
40
0.0 0.1 0.2 0.3 0.4 0.5
Oligomeric

Figure5.7:InfluenceofoligomericonthechainlengthatdifferentkLavalues
(Sbcatalysis;simulatedreactiontime:45minutes)
85
=0.1 =0.2 =0.3 =0.4

120
Chainlength,n
80
40
0
0 5 10 15 20 25 30 35 40 45
kLa(1/min)

Figure5.8:InfluenceofmasstransfercoefficientkLaonchainlengthatdifferentoligomeric
values(Sbcatalysis;simulatedreactiontime:45minutes)
Conclusion
To study the influence of functional group balance on the reaction rate, well designed
oligomershavingdifferentfunctionalgroupbalanceweregeneratedbyspecialesterification
conditionsinasemibatchreactor.Thesedesignedoligomerswerefurtherreactedinamelt
polycondensation phase in the presence of metal catalysts. For the antimony catalyzed
polycondensation, maximum rate was obtained at carboxyl fraction, = 0.25 while Ti
catalyzedoptimumpolycondensationratewasobtainedattowardszero.Oursimulation
study indicates that the optimum rate profile for antimony is observed due to the
combination of esterification and transesterification rates affected by proton and metal
catalysis together with antimony inhibition effect in the initial polycondensation phase
where oligomeric is extremely low. However, Ti catalysis is not inhibited by functional
groups and exhibit maximum rate due to combination of transesterification and
esterificationrates.Withthehelpofproposedmodel,optimumfunctionalgroupbalancefor
agivencatalystcanbestudiedforanyreactorgeometrybyoptimalfittingofmasstransfer
parameterkLa.Theagreementbetweenthemodelpredictionandexperimentaldataseems
reasonableandingoodaccordancewiththepublishedliteratures.

86
Nomenclature
aT terminalcarboxylgroupsofoligomers [molkg1]
a0 saponificationnumber [molkg1]
bF hydroxylgroupsofEG [molkg1]
bT terminalhydroxylgroupsofoligomers [molkg1]
ei internalestergroups [molkg1]
E totalterminalgroupsofoligomers [molkg1]
k,i rateconstant [kgmol1min1]
kL masstransfercoefficient [cmsec1]
a specificinterfacialarea [cmcm]
n degreeofpolymerizationorchainlength []
p overallconversion []
Sb antimonyion
Ti titaniumion
v vinylendgroupofoligomers [molkg1]
z acetaldehyde [molkg1]
GreekLetters
carboxylfractionintotalterminalgroups []
inhibitionfactor [kgmol1]
87
References
[1] G.Rafler,E.Bonatz,H.D.SparingandB.Otto,Acta.Polym.1987,38,6.
[2] T.Sano,H.Yokoyama,HitachiReview1979,28(2),83.
[3] B.Duh,J.Appl.Polym.Sci.2002,83,1288.
[4] H.Yokoyama,T.Sano,T.Chijiwa,R.Kajiya,KobunshiRonbunshu1979,36(8),557.
[5] E.Berkau,Durham,W.R.Hocutt,USpatent3,551,386,1970.
[6] G.Rafler,G.Reinisch,E.Bonatz,H.Versaeumer,J.Macromol.Sci.Chem.1985,A22,
1413.
[7] H.Patel,G.Feix,R.Schomaecker,Macromol.React.Eng.2007,1,502.
[8] H.Patel,G.Feix,R.Schomaecker,Macromol.Symp.2007,259,65.
[9] F.A.ElToufaili,G.Feix,K.H.Reichert,J.Appl.Polym.Sci.PartA,2006,44,1049.
[10] S.G.Hovenkamp,J.Polym.Sci.PartA1,1971,9,479.
[11] J.W.Chen,L.W.Chen,J.Polym.Sci.Polym.Chem.Ed.,1998,36,3073.
[12] K.RavindranathandR.A.Mashelkar,J.Appl.Polym.Sci.1982,27,2625.
[13] S.I.Cheong,K.Y.Choi,J.Appl.Polym.Sci.1995,58,1473.
88
Appendix
Chapter3:
Table1:Experimentalresultsandevaluatedparameters
MRF IV Mn n p
() (dl/g) (g/mol) () () () ()
1.44 0.091 1013 4.97 0.035 0.993 0.799
1.29 0.109 1321 6.59 0.071 0.989 0.848
1.20 0.129 1682 8.50 0.125 0.985 0.882
1.13 0.141 1913 9.74 0.208 0.978 0.897
Table2:TPAparticlesizedistribution
Instantaneous Instantaneous
r(m) Distribution(%) r(m) Distribution(%)
2.25 0.023 22.50 0.063
2.75 0.022 26.25 0.069
3.25 0.022 31.25 0.073
3.75 0.024 37.50 0.075
4.50 0.024 45.00 0.072
5.50 0.027 52.50 0.065
6.50 0.030 62.50 0.053
7.75 0.033 75.00 0.039
9.25 0.037 90.00 0.026
10.75 0.041 107.50 0.015
12.50 0.045 127.50 0.009
15.00 0.051 152.50 0.005
18.75 0.057 182.50 0.002

89
Table3:Experimentalwatercollectedwithtimefordifferentfeedratio.
Time MRF1.44 MRF1.36 MRF1.29 MRF1.2

(min) w(mol) w(mol) w(mol) w(mol)
0 0.00 0.00 0.01 0.08

20 0.00 0.00 0.01 0.08
25 0.53 0.90 0.32 0.62
30 1.76 1.86 1.42 1.71
35 2.97 3.25 2.85 2.76
40 4.29 4.33 4.02 3.84
45 5.67 5.70 5.22 4.97
50 7.05 6.99 6.45 6.05
55 8.26 8.31 7.46 6.98
60 9.29 9.20 8.37 7.70
65 10.05 9.77 9.14 8.43
70 10.17 9.97 9.48 8.72
75 10.17 10.05 9.60 8.72
80 10.17 10.15 9.60 8.72
85 10.17 10.18 9.60 8.72
125 11.45 11.91 10.97 10.67
Chapter4:
Table4:Experimentalresultsofesterifiedoligomersundervariedpressure.
P t EG/TPA (EG0EGR)/ aT bT Mn n p DEG

EG
(bar) (min) (mol/mol) ()

(mol/kg) (mol/kg) (g/mol) () () () () (wt.%)
3.13 95 1.4 0.28 0.70 0.77 1355 6.95 0.48 0.962 0.790 3.1
3.13 95 1.4 0.29 0.75 0.68 1401 7.21 0.52 0.897 0.840
3.22 95 1.4 0.28 0.68 0.80 1346 6.90 0.46 0.932 0.856
3.22 95 1.4 0.27 0.64 0.86 1335 6.82 0.43 0.954 0.842 3.4
3.34 95 1.4 0.24 0.47 1.13 1250 6.32 0.29 0.961 0.821 3.7
3.50 95 1.4 0.20 0.43 1.68 948 4.71 0.20 0.933 0.855
3.55 95 1.4 0.21 0.39 1.40 1116 5.59 0.22 0.938 0.853 4.5
3.55 95 1.4 0.19 0.31 1.58 1060 5.27 0.16 0.927 0.861
3.75 95 1.4 0.19 0.37 1.71 959 4.76 0.18 0.969 0.810 4.9
90
Chapter5:
Table5:ExperimentalresultsofesterifiedoligomersandamorphousPETresin(Sbcatalysis)
APETresinpropertiesofSbcatalyzedpolycondensationat45
EsterifiedOligomericpropertiesat90minutes minutes
IV aT Mn n OH p IV aT Mn n OH p
mol/ g/ mol/ dl/ mol/ g/ mol/

dl/g kg mol kg g kg mol kg
0.086 0.10 923 4.50 2.06 0.05 0.989 0.778 0.60 0.005 16069 83 0.119 0.042 0.999 0.988
0.083 0.29 875 4.29 2.00 0.13 0.971 0.767 0.65 0.012 18282 95 0.097 0.112 0.999 0.989
0.083 0.29 879 4.31 1.98 0.13 0.970 0.768 0.62 0.014 17162 89 0.103 0.119 0.999 0.989
0.102 0.68 1194 6.08 1.00 0.40 0.934 0.836 0.50 0.094 12338 64 0.068 0.582 0.991 0.984
0.084 0.28 889 4.37 1.97 0.12 0.971 0.771 0.64 0.013 17980 93 0.098 0.117 0.999 0.989
0.102 0.67 1194 6.08 1.00 0.40 0.934 0.835 0.49 0.098 12130 63 0.067 0.594 0.991 0.984
0.084 0.31 893 4.39 1.93 0.14 0.969 0.772 0.67 0.014 18879 98 0.092 0.133 0.999 0.990
0.083 0.30 879 4.31 1.98 0.13 0.970 0.177 0.65 0.013 18311 95 0.096 0.119 0.999 0.989
0.102 0.65 1187 6.04 1.03 0.39 0.936 0.834 0.54 0.081 13659 71 0.065 0.555 0.992 0.986
0.099 0.55 1139 5.75 1.21 0.31 0.946 0.826 0.61 0.053 16566 86 0.068 0.436 0.995 0.988
0.099 0.60 1143 5.79 1.15 0.34 0.941 0.827 0.57 0.065 14839 77 0.070 0.482 0.994 0.987
0.089 0.41 971 4.82 1.65 0.20 0.959 0.793 0.68 0.025 19532 102 0.078 0.240 0.998 0.990
0.086 0.11 921 4.50 2.06 0.05 0.989 0.778 0.64 0.005 17659 92 0.108 0.047 0.999 0.989
0.085 0.31 911 4.49 1.88 0.14 0.968 0.777 0.66 0.017 18489 96 0.091 0.155 0.998 0.990
91
Table6:ExperimentalresultsofesterifiedoligomersandamorphousPETresin(Ticatalysis)
EsterifiedOligomericpropertiesat90minutes TicatalyzedAmorphousPETresinpropertiesatdifferentreactiontime
IV aT Mn n OH p t IV aT Mn n OH p
mol g/ mol dl/ mol/ g/ mol

dl/g min
/kg mol /kg g kg mol /kg
0.086 0.32 932 4.60 1.83 0.15 0.968 0.783 40 0.71 0.008 20847 108 0.09 0.085 0.999 0.991
0.098 0.52 1131 5.70 1.25 0.29 0.948 0.825 45 0.74 0.019 21965 114 0.07 0.204 0.998 0.991
0.098 0.57 1126 5.69 1.21 0.32 0.944 0.824 45 0.72 0.023 20980 109 0.07 0.238 0.998 0.991
0.088 0.29 964 4.76 1.78 0.14 0.971 0.790 30 0.62 0.011 17128 89 0.11 0.097 0.999 0.989
0.091 0.38 1009 5.02 1.60 0.19 0.962 0.801 40 0.71 0.008 20645 107 0.09 0.082 0.999 0.991
0.087 0.28 937 4.62 1.86 0.13 0.972 0.783 35 0.69 0.012 20002 104 0.09 0.122 0.999 0.990
0.087 0.30 938 4.63 1.83 0.14 0.970 0.784 35 0.70 0.009 20329 106 0.09 0.087 0.999 0.991
0.081 0.08 849 4.12 2.27 0.04 0.991 0.757 30 0.72 0.006 21248 110 0.09 0.059 0.999 0.991
0.081 0.08 849 4.11 2.28 0.03 0.992 0.757 30 0.66 0.005 18518 96 0.10 0.046 1.000 0.990
0.083 0.06 885 4.30 2.20 0.02 0.994 0.767 30 0.64 0.012 17870 93 0.10 0.105 0.999 0.989
0.086 0.08 927 4.52 2.07 0.04 0.991 0.779 30 0.68 0.006 19549 102 0.10 0.053 0.999 0.990
92
CurriculumVitae
PATEL,Himanshu
bornonJanuary19th,1976inVallabhVidyanagar,India
Education
December2004July2008
PhD,PolymerScience
Technical University of Berlin, Germany. In cooperation with Equipolymers
GmbH,ADowandPICJointVentureCompany,Schkopau,Germany
Advisors:Prof.R.Schomcker(TUBerlin)andDr.G.Feix(EquipolymersGmbH)
April2002May2004
MasterofScience,PolymerScience
AjointprogrambyFreeUniversity,HumboldtUniversity,TechnicalUniversityof
BerlinandUniversityofPotsdam,Germany
ThesisAdvisor:Prof.K.H.Reichert(TUBerlin)
June1996April1998
MasterofScience,PlasticProcessing&Testing
SardarPatelUniversity,VallabhVidyanagar,Gujarat,India
June1993May1996
BachelorofScience,Chemistry
C.U.ShahScienceCollege,GujaratUniversity,Ahmedabad,Gujarat,India
Publications
[1] Influence of Carboxyl and Hydroxyl Groups Balance on Catalyzed
PolycondensationofPoly(ethyleneterephthalate).H.Patel,G.Feix,J.P.Wiegner,
R.Schomcker,submitted.
[2] Influence of Reaction Pressure on Semibatch Esterification Process of
Poly(ethylene terephthalate) Synthesis. H. Patel, G. Feix, R. Schomcker,
MacromolecularSymposia,2007,259,65.
[3] Modeling of Semibatch Esterification Process for Poly(ethylene terephthalate)
Synthesis.H.Patel,G.Feix,R.Schomcker,MacromolecularReactionEngineering,
2007,1,502.
93

The Effect of Oligomeric Terminal Group Balance On Catalyzed Polycondensation of Poly (Ethylene Terephthalate) - Patel

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The Effect of Oligomeric Terminal Group Balance on

Catalyzed Polycondensation of Poly(Ethylene Terephthalate)

aus Vallabh Vidyanagar, Indien

von der Faukultt II Mathematik und Naturwissenschaften

- Dr. rer. nat.

Vorsitzender: Prof. Dr. T. Ressler, TU Berlin

1. Berichter: Prof. Dr. R. Schomcker, TU Berlin

2. Berichter: Dr. habil. G. Feix, Equipolymers GmbH

Tag der wissenschaftlichen Aussprache: 23. Juli 2008

COOH + HOC2H4OH COOC2H4OH + H2O

COOC2H4OH COOH + CH3CHO

Propeerty Specificcation Typicalvalue

CHDM IPA DEG

Reactants: Terephthalic Acid (Equipolymers), Ethylene Glycol (Equipolymers), Diethylene

Additives: Tetramethylene Ammonium Hydroxide (Fluka), Cobalt Acetate (Equipolymers),

Transesterification reaction is a main reaction during polycondensation phase. Due to

Ampere (High Vacuum) Ampere (Low Vacuum)

IV: 0.51 dl/g 2

ExprimentalTemperature SimulatedTemperature Pressure

Symbol Description Molecularstructure

ei internalesterlink OOC COO

Esterification reactions are known to be catalyzed by protons dissociated from carboxyl

x H2O H2O PH2O = y H2O P (9)

x EG + x H2O + x OLG = 1 (10)

PEG ,PH2O = vaporpressureofEGandwater,bar

PH2O = 1.33 10 4.96681668.2 /( T +228 ) (13)

thereactionofterminalhydroxylgroupwithcarboxylgroupsi.e. bTwith a F ,D or aT .Otton

MRI EG0,mol EGresidual,mol TPA0,mol MRF

In presented work, reactions were carried out in absence of Sb catalyst. Therefore,

n = (Mn 62 + 88 ) / 192 (22)

Where, Mn = 3.27 10 4 IV 1.4706

Where, MSRN isthestatisticalrepeatingunit.

[21] D. Tremblay, Using simulation technology to improve profitability in the polymer

Symbol Description Molecularstructure

Table4.3:Reactionratelaws.(Reactions R6 and R7 produceDEGlink)

waterandoligomers, y EG and y w arethevaporphasemolefractionsofEGandwater, PEG

log Pw = 7.9668 + log(1 / 750) 1668.2 / ( + 228) (13)

where wLand bF,Lrepresentsthemolesofwaterand bFinliquidphase. mListhemassof

Kineticconstants Activationenergy Frequencyfactor Equilibrium

In semibatch or continuous PET process, the degree of polymerization advances by

Figure 4.1 shows the influence of esterification pressure on fraction of unreacted EG to

where, EGLand EGVarethemolesofunreactedEGinliquidandvaporphaserespectively.

where M n = 3.27 10 4 IV 1.4706

theFloryHugginsmodel.ThevaporpressureofEG( PEG )andwater( PW )arecalculatedusing

Masstransfercoefficient, k L = 6.0 10 3 cms1(Rafleretal.6)

We have investigated the influence of oligomeric (fraction of carboxyl groups in total

This phenomenon can be explained by a combination of catalyst inhibition and proton

induced by Sb inhibition in early polycondensation phase. Since the carboxyl group

P=0 P=0.1 P=0.5

72 36 25.2 21.6 14.4

=0.1 =0.2 =0.3 =0.4

Time MRF1.44 MRF1.36 MRF1.29 MRF1.2

0 0.00 0.00 0.01 0.08

P t EG/TPA (EG0EGR)/ aT bT Mn n p DEG

(bar) (min) (mol/mol) ()

mol/ g/ mol/ dl/ mol/ g/ mol/

mol g/ mol dl/ mol/ g/ mol

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