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ThePolymerizationofEthyleneunderHighPressureusingSemiconductor

ThePolymerizationofEthyleneunderHighPressureusingthe
SemiconductorModel
ZeljkoPrebeg,Lermanova12a,10000Zagreb,Croatia

Abstract:ByexaminingtheprocessofheattransferattubularreactorforLDPEsynthesis,itcanbe
concludedthatfreeelectronsexistsduringpolymerization.Additionally,nofreeelectronsoccurinthe
absenceofpolymerization.Amodelthatcanexplainanddescribethisbehaviorofethyleneunderhigh
pressureisthesemiconductormodel.
Keywords:highpressure,polymerization,ethylene,semiconductor,Pauliexclusionprinciple,molecular
interaction.

Methods:
Forexaminationofphysicalandchemicalstatesofethyleneundersynthesescondition,heattransferina
reactorforLDPEsynthesisisused.Polymerizationofethyleneishighlyexothermicreaction.Theheatof
polymerization(94.5kJmol1)iscontinuallyremovedbyconductiontroughreactionmediumorby
convectionthroughthereactor'swall.Inahighpressuretubularreactor,about50%heatofpolymerization
iscarriedoutthroughthereactor'swall.Theresistancetoheattransferissignificant.Commonopinion1is
thatpolymer'sdepositisolatesthewallofthereactor.

Figure1.ReactorforLDPEsynthesis.

Theshapeofthereactoristubularwhere50%offreshethyleneisinjectedatseveralplacesdownreactors
length(figure1).Thereactorisdividedintoseveralheatingandcoolingzones.Thefirstzoneisusedforthe
heatingofethylenetothereactiontemperatureandwhileinotherzoneswherethereactionstakeplace,heat
isbeingremoved.Tocalculatetheheattransfercoefficient,thetemperatureandflowofcoolingwateralong
withthetemperaturewithinthereactionmediumarecontinuallymeasuredasshowninfigure2below.

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Figure2.Measuringoftemperature,coolingwaterflowandtemperatureofreaction'smediumintubularreactor
forLDPEsynthesis.

Flowismeasuredwiththeorifice,whiletemperaturesaremeasuredbyathermocouple.Duringthemeasuringof
temperaturesinreactor,highfluctuationshaveoccurred(+/0.55.00C).Thesefluctuationsareproperand
arecausedbydissipationofthehighlocalenergyfromtheheatofpolymerization.Inabsenceof
polymerization,thesefluctuationsdonotexist.Heattransferredintothecoolingwaterperunitoftimeis
calculatedbyfollowingequation:
Q=G*Cp*(tintout)
Where:Q(kJs1)isheattransferredintothecoolingwater
G(kgs1)isthewaterflow
Cpisspecificheatcapacityofwateratconstantpressure(4.19kJ/kg/K)
t(K)isthetemperatureofcoolingwater.

Thetransitivityofheatthroughthewallofthereactoriscalculatedbyequation:
K*A=Q/Dtavg
Where:K(kWm2K1)istheheattransfercoefficient
A(m2)isthesurfaceareaforthetransferofheat
Dtavg(K)isaveragelogarithm'sdifferenceoftemperature
K*A(kWK 1)isthetransitivityofheat2throughthewallofreactor.

Theaveragelog(temperature)iscalculatedbytheequation,Dtavg=(Dt1Dt2)/log(Dt1/Dt2),withtheterms
forDt1andDt2beingshowninfigure3below.
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Figure3.Dt1,Dt2fora)countercurrent,b)concurrentheatexchanger.

Results:
Table1.Flow,input,andoutputtemperatureofcoolingwaterandtransferredheatinreactorforLDPE
synthesis.

Table2.Transitivityofheattroughthewallofreactor

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Figure4.Transitivityofheatthroughthewallofthereactor(accordingtable2).

Discussion:
Table2andmoreoverfigure4,showthetransitivityofheatthroughthewallofthereactor.Thebehaviorof
secondzoneisunusual.Heat,liberatedbypolymerizationreaction,heatreactionofthemediumitself.Noneof
heatistransferredthroughthewallofreactor.Otherzonesshowalargeresistanceforheattransferthrough
thewall,butthisresistancedecreasesalongthereactor.Ifthepolymerfilmisolateswithinthereactor,then
accordingtocommoninterpretation,thelargestconcentrationofpolymerwouldbeontheendofreactor
causingthelargestresistance.Inrealityitistheopposite.Alongtheendofreactor,resistancetoheat
transferthroughthewallofreactordecreases(figure4,table2).ItespeciallyoccurredinALDzonewhere
concentrationofpolymerisgreatest,whilethetransitivityofheatissameasinfirstzone.Fromthis
observationitcanbeconcludedthatthepolymerdoesnotrepresentresistanceintheheattransferduring
polymerization.SimilarresultsarepresentedbyMolen3intheinvestigationoftwodifferentconfigurations
ofheaterreactorsystem(figure5).InaTTconfiguration,heattransferandconversioninthesecond
reactorislowerthaninthefirstreactor.InaVTconfiguration,conversioninthetubularreactorisnot
undersignificantinfluencefrompolymerthatisformedinthevesselreactor.Inotherwords,ifthroughthe
secondreactorpassesthesamequantityofpolymerformedatthevesselortubularheater,theheattransfer
troughthewallofthereactorishigherintheVTconfiguration.Thisfactshowsthatthedepositofpolymersis
notthecauseofheattransferresistancethroughthewallofthetubularreactor.

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Figure5.Configurationofheaterreactorsystem.(a)TT(b)VT

Figure6.Showstheratioofheattransferredthroughthewallofreactorandautothermicsheat.Atconversion
of13%atfirstreactor,secondreactor(configurationTT)worksadiabatic.(Hw/Ha=0).Atsame
conversionof13%,configurationVTshowsheattransferthroughthewallofreactor(Hw/Ha=1/2).Thisfact
showsthatdepositofpolymersarenotcauseofautothermicheattransfer.

But,iftheheattransferisexaminedastransferofheatbythelowestresistance,thenitcannextbeconcluded
thatduringthepolymerization,heatistransferredthroughthereactionmedium(conduction)betterthen
throughthereactor'swall(convection).Intheabsenceofpolymerization,thereactionmediumshows
resistance.Heatistransferredthroughthereactor'swall.Itiswellknownthatfreeelectronscauseconduction's
heattransferandsinceheatcanbetransferredbyconduction,itcanthereforebeconcludedthatduringthe
polymerization,freeelectronsexist.Themodelwhichdescribesthisbehaviorofmatter,isknown,anditis
usedfortheinterpretationofsemiconductorproperties.Beforedeductionofthesemiconductormodel,the
chemicalbondwillbediscussed.
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Thechemicalbondisformedbetweentwoatomsbyvalenceelectrons.Threekindsofchemicalbondsare
known.Covalentbondsareformedbetweenatomsofsimilarelectronegativity(figure7a)whereeachatom
givesoneelectrontoformthebond.Anionicbondhasformedbetweenatomsofdifferentelectronegativity
(figure7b).Inthiscase,thebondingorbithasmovedinthedirectionoftheelectronegativeatom.Theionic
bondcanbeviewedasaspecialcaseofthecovalentbond.Thethirdkindofchemicalbondisthemetallic
bond(figure7c).Itisformedbetweenagroupofatomswherecommonorbitsareconnectedandforma
commonband.Itwillbeshowedthatthemetallicbondisakindofsuperbondingofthecovalentorionic
bondandstronglydependsonthestateofthematter.

Figure7.Chemicalbonda)covalent,b)ionic,c)metallic
Theethylenemoleculehassixchemicalbonds.Fourofthebondsareformedbetweencarbonandhydrogen
(E=411kJ/mol).Twootherbondsareformedbetweenthecarbonatoms(Esigma=335kJ/mol,Epi=607
kJ/molasshowninfigure8below).

Figure8.Theenergyofbondsoftheethylenemolecule.
Valenceelectronsofmoleculeofethyleneareelectronsonhighestenergylevel.Theyareformingoutersphere
forinteraction(figure9below).

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Figure9.Interaction

Accordingtothepresentedknowledgeaboutbehaviorofethyleneundersynthesisconditionsandonthebase
ofthesemiconductortheory,thefollowingmodeloforganizationforethyleneisproposed.Thedeductionof
thesemiconductormodelisbaseduponanorganizedsystemcalledabimolecule.

Figure10.Bimoleculeforming(Pauliexclusionprinciple).

Thebimoleculeofethyleneisformedbetweentwomoleculesbytheexcitationofthepiboundelectrons
(figure10).Commonorbitsareformedatthehighestenergylevels,whileotherpiboundelectronsstay
unpaired.Thistransformation,resultsfromthetransferofthepiboundelectronsfromthebasetoexcited
stateusingtheenergyobtainedthroughcompression.Proposalfortheexistenceofbimoleculeisnotanew.
EvenPease4in1931,duringinvestigationofthermallyinitiatedpolymerizationatlowpressure,proposedthat
thestepbeforethechemicalreactionistheformationofadimmerofethylene.Onthebasisofexperimental
measurementsoftheenergyofactivationandorderofreaction,Buback5concludesthatthroughthethermally
initiatedpolymerization,abiradicaldimmerisformed.Thisauthorsdidnotexaminethedimmerasastable
form.Stoiljkovic6,hadtheopinionthatbimoleculeisastableparticleandthatisbaseoftheorganizationof
ethylene.Thismodelissimilartohisinterpretationofthebimolecule,whilethesemiconductormodelexamines
energetictransformation.

Figure11.Valencebandformation.

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Inanorganizedsystem,thevalencebandisformingbyapartialcrossingofouterorbitsofbimolecules(figure
11).Electronsaredislocated,buttheyarestillbondedtothebimolecule.Thisbondisthenweaklybondedin
theisolatedbimolecule.
Theanalogytothesemiconductormodelproposesthatforbiddenzonealsoexists.Theenergyofthis
forbiddenzoneishigherthanthevalencebandbutlowerthanthatoftheconductionband(asshowninfigure
12).Inaddition,asubvalencezoneexiststoo.Thesubvalencezoneisformedbyunpairedelectrons.Itis
viathesedefinitionsthatthesemiconductormodelofethyleneisdefined(asillustratedinfigure12).

Figure12.Thesemiconductormodelofethyleneorganization.

ThesemiconductormodeldiffersfromStoiljkovicsmodel,whichproposesexistentofoligomoleculesin
Sr<1(gammaphase)andbimoleculesinSr>1(betaphase).Accordingtothesemiconductormodel,thebeta
phaseisorderedbytheprobabletransferofelectronsfromvalencebandtotheconductionband.
Theinitiationofpolymerizationcanoccurindifferentways(thermally,chemically,bygammaray,UV).
Understandingthethermalactivationofpolymerizationhelpsinunderstandingtheanalogybetweenthe
behaviorofanidealsemiconductorandthatofethyleneunderhighpressure.Forinstance,itiswell
knownthatinlowertemperatures,theidealsemiconductorbehavesasanisolator,(i.e.freeelectronsdonot
exist).Increasingofthetemperature,someelectronsfromthevalencebandgetenoughenergyto
transferfromthevalencebandtoconductionband.Inthevalenceband,aholeisformedwhilethefree
electronbeingdislocatedintheconductionband.

Figure13.Theinitiationofpolymerization.

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Aftertheexcitationoftheelectronintheconductionband(figure13a),anunpairedelectronfromthevalence
zonecanstayinthevalencezone(figure13b)oritcanbetransferredtothesubvalencelevel(becauseholes
existinsubvalencelevel)..Inthelattercaseanelectronholecupisformed.Theelectronisdislocatedat
conductionband,whileaholeisrelocatedatsubvalencezone.Thispairplaysaspecificroleinthechemical
reactionandmaybedescribedasaprimaryradicalterminatorpair.Primaryradicalplaysaroleinstarting
polymerchaingrowth,whileterminatorplaysaroleattheendofthepolymerchaingrowth.Thesecupsare
connectedwithbetaphasewhilecupsarenotformedinthegammaphase.Thereisthereforeasignificant
differencebetweentheradicalandterminator.Whiletheradicalisbeingdislocated(beingputinmotion),the
terminatorisbeinglocated,(becomingmotionless).
Accordingtotheclassicalexplanation,polymergrowthisoccurringbychainreaction.Theheatof
polymerizationishigh,andonceitpolymerizes23moleculesofethylene,thebreakingoftheCCboundis
possible.Ifefficientlyheattransferdoesnotexistthentheformedpolymerwillbeoflowmolecularweight.It
canbeshown7thatfora50%probabilityofgettingapolymerchainof1000monomerunits,probabilityfor
eachstepofpolymergrowthmustbehigherthen1400/1.Thisshowsthatanefficientmechanismfor
stabilizationofaradicalmustexist.Thegrowingofapolymerchainoccursbythefillingofholesinthe
subvalencezone.Afterthefirstholeofbimolecule(figure14a)isfilled,acommonelectroncuphas
unformed.Oneelectronfillseachparticularbimolecule,(figure14b)whiletheotherisfreetotransferto
holeofnearestbimolecule(figure14b,c).

Figure14.Polymerchaingrowth.
Thebimoleculeispolymerizedinthebasicgrowthreaction.Theelectronsaretransferredfromthehighesttothe
lowestenergystate,causingtheliberationofenergy.Polymerizationisanexothermicreaction.Unpaired
electronsinvalencebandarepartiallydislocated,butstillconnectedtoaparticularbimolecule.Itcan
thereforebereasonedthatanexternalforceisnecessaryforthismovementtooccur.Growinga
polymerchainisadiffusioncontrolledreaction,andtheradicalisstable,whilebeingpartiallydislocatedat
thevalenceband.
Accordingtoclassicalmodel,areactionofendchaingrowthismadebytheinteractionoftworadicals.This
reactionisconnectedtothefreeholeinthesubvalencelevel(i.e.terminator).Thefreeelectronfromvalence
bandfillsthefreeholesinsubvalencezoneandthepolymerchaingrowthisthenfinished.(figure15).Ifa
terminatordoesnotexistthenthegrowthofthepolymerchainswillcontinueandthepolymerchainwillhave
highmolecularweight.

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Figure15.Endofchaingrowing

Conclusion:
Theheattransferbyconvectioninabsenceofpolymerizationandheattransferbyconductionthroughthe
reactionmediumduringpolymerizationshowsthatfreeelectronsexistduringthepolymerizationofethylene
underhighpressure.Thesefactsindicatethatethyleneunderhighpressureissemiconductor.Existenceofa
valenceandconductionzonemakespossibleefficienttransferoftheheatofpolymerization,withoutthe
breakingofthepolymerchain.Thelonglifeofradicalsshowsthatamechanismforhisstabilizationexistsand
onewayisthedislocationoffreeelectronsinthevalenceorconductionband.Duringtheinitiationof
polymerization,aprimaryradicalterminatorpairisformed.Primaryradicalplaysaroleinstarting
polymerchaingrowth,whileterminatorplaysaroleattheendofthepolymerchaingrowth.Ifaterminator
doesnotexistthenthegrowthofthepolymerchainswillcontinueandthepolymerchainwillhavehigh
molecularweight.Futuredirectmeasurementoftheelectricalpropertieswouldbethebestwaytoprovingthis
semiconductormodelofethylenepolymerization.

References:
1.HwuM.C.,FosterR.D.,Chem.Eng.Prog.,78,62(1982)
2.DordevicB,ValentV,SerbanovicS,Termodinamikaitermotehnika,IRO"Gradevinskaknjiga",Beograd,
1987
3.MolenWD,VIIthInt.AIRAPTConf.,leCreusot,Franse(1979)
4.PeaseRN,J.Am.Chem.Soc.,53,613(1931)
5.BubackM,Macromol.Chem.,181,373(1980)
6.StoiljkovicD,JovanovicS.,ActaPolym.,39,670(1988)
7.HunterE,Chemistry&Industry,396(1955)

IwishtoacknowledgeProf.MitsuoSawamotoforhisusefulsuggestionsinthepreparationofthismanuscript.
Also,manythankstoVictoriaattheJournalofTheoretics.

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