Patent WO2014093017A1 - Polymerization Process For Production of Polymer Blends - Google Patents

6/15/2015
PatentWO2014093017A1PolymerizationprocessforproductionofpolymerblendsGooglePatents
Raj
Patents
English
French
Polymerizationprocessforproductionof
polymerblends
WO2014093017A1
ABSTRACT
Aprocesscomprisingcontactingacatalystsystemwithoneormoreolefinsina
bubblecolumnreactor.Also,apolyolefincopolymercompositioncomprising
ethylene,propyleneandoptionallyaC4toC20alphaolefinsaidcomposition
havingabimodaldistributionwithrespecttocompositiondistribution,molecular
weightdistributionoracombinationthereofanMwof10,000g/molormore
and/oratleasttwomeltingpeaksinaDSCheatingcyclewithadifferencein
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WO2014093017A1
Application
PCT/US2013/071937
Jun19,2014
Nov26,2013
Dec10,2012
Inventors
PeijunJiang,KeithE.Jolibois,RonaldR.
Thackston
Applicant
ExxonmobilChemicalPatentsInc.
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BiBTeX,EndNote,RefMan
PatentCitations(5),Classifications(5),LegalEvents(1)
ExternalLinks:Patentscope,Espacenet
meltingtemperaturesofatleast5C.
DESCRIPTION(OCRtextmaycontainerrors)
CLAIMS(OCRtextmaycontainerrors)
POLYMERIZATIONPROCESSFORPRODUCTIONOFPOLYMERBLENDS
1.Aprocesscomprisingcontactingacatalystsystemwithoneormoreolefinsin
CROSSREFERENCETORELATEDAPPLICATIONS
abubblecolumnreactortoformapolyolefinhavingabimodaldistributionwith
ThisapplicationclaimsthebenefitofProvisionalApplicationNo.61/735,130,
filedDecember10,2012andEP13159125.7filedMarch14,2013.
respecttocompositiondistribution,molecularweightdistributionora
combinationthereof.
FIELDOFTHEINVENTION
2.Theprocessofclaim1,whereinthepolyolefincomprisesanMwof10,000
Thisinventionrelatestoamethodofmakingpolymerblends.
g/molormore.
BACKGROUNDOFTHEINVENTION
Formanyapplicationsindividualpolymersdonotpossessafullrangeof
3.Theprocessofclaims1or2,whereinthepolyolefincomprisesatleasttwo
performancecharacteristicsrequired.Individualpolyolefinshavingcertain
meltingpeaksinaDSCheatingcyclewithadifferenceinmeltingtemperatures
characteristicsareoftenblendedtogetherinthehopesthatthepolymerblend
ofatleast5C.
willexhibitthebestcharacteristicsofitscomponentpolymers.Typicallythe
resultisablendwhichdisplaysanaverageoftheindividualpropertiesofthe
individualresins.Physicalblendsalsofaceproblemsofenergyconsumption,
4.Theprocessofanyoneofthepreviousclaims,whereintheoneormore
operationalcosts,andmiscibilitylimitations.Unlessthecomponentsare
olefinscompriseethylene,propylene,C4toC20alphaolefin,oracombination
selectedfortheircompatibilitytheycanphaseseparateorsmallercomponents
thereof.
canmigratetothesurface.Reactorblends,alsocalledintimateblends(a
compositioncomprisingtwoormorepolymersmadeinthesamereactororina
seriesofreactors)areoftenusedtoaddresstheseissuesalongwiththeuseof
multiplecatalystsystems.However,multiplecatalystsystemsthatwilloperate
underthesamereactiveenvironmentstoproducedifferentpolymerswith
5.Theprocessofanyoneofthepreviousclaims,whereinthecatalystsystem
comprisesametallocenecatalyst.
desiredpropertiesremainproblematic.Reactorpolymerblendshavealsobeen
producedinmultiplestageprocessormultiplereactorsystemshowever,
certainlimitstotheknownmethodsofpreparingreactorblendslimitthe
suitabilityofthisapproach.Accordingly,thereiscontinuedinterestindeveloping
efficientand/oreconomicalmethodstoproducedesiredreactorblends.
comprisesahomogenouscatalystandthebubblecolumnreactorcomprisesa
polymersolutionreactor.
SUMMARYOFTHEINVENTION
Thisinventionrelatestoaprocesscomprisingcontactingacatalystsystemwith
comprisesasupportedcatalystandthebubblecolumnreactorcomprisesa
oneormoreolefinsinabubblecolumnreactortoformapolyolefinhavinga
polymerslurryreactor.
bimodaldistributionwithrespecttocompositiondistribution,molecularweight
distributionoracombinationthereof.
Preferably,thisinventionrelatestoaprocesscomprisingcontactingacatalyst
8.Theprocessofanyoneofthepreviousclaims,comprisingsparginga
gaseousolefinfeedstreamintoabulkliquidphaseinthebubblecolumnreactor.
http://www.google.com/patents/WO2014093017A1?cl=en
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systemwithoneormoreolefinsinabubblecolumnreactortoformapolyolefin
havingabimodaldistributionwithrespecttocompositiondistribution,and
molecularweightdistribution.
9.Theprocessofanyoneofthepreviousclaims,comprisingintroducingfirst
andsecondolefinfeedstreamsintoabulkliquidphaseinthebubblecolumn
Preferably,thisinventionalsorelatestoapolyolefincopolymercomposition
reactor,whereinthefirstolefinfeedstreamisliquidandthesecondolefin
comprisingethylene,propyleneandoptionallyaC4toC20alphaolefinhaving:
feedstreamisgaseous.
abimodaldistributionwithrespecttocompositiondistribution,molecularweight
distribution,oracombinationthereofanMwof10,000g/molormoreandat
leasttwomeltingpeaksinaDSCheatingcyclewithadifferenceinmelting
10.Theprocessofclaim9,whereinthefirstolefinfeedstreamcomprises
temperaturesofatleast5C.Preferably,thecopolymerisobtainedasaproduct
propyleneandthesecondolefinfeedstreamcomprisesethylene.
streamfromabubblecolumnreactor.
BRIEFDESCRIPTIONOFTHEDRAWINGS
FIG.1showsanembodimentofabubblecolumnreactoraccordingtothe
11.Theprocessofclaim10,whereinthesecondolefinfeedstreamfurther
comprisespropylene.
instantdisclosure
FIG.2showsanembodimentofaslurrybubblecolumnreactoraccordingtothe
instantdisclosure
FIG.3istheDSCtraceshowingthepresenceofmultiplemeltingpeaksand
12.Theprocessofanyoneofclaims911,whereinthesecondolefin
feedstreamfurthercomprisesagaseousdiluent,hydrogen,oracombination
thereof.
multiplecrystallizationpeaksofapolyolefinproducedinExample2accordingto
anembodimentoftheinstantdisclosure.
13.Theprocessofanyoneofclaims912,furthercomprisingrecycling
DETAILEDDESCRIPTION
Thisinventionrelatesinsomeembodimentstoapolymerizationprocess
overheadvaporfromthebubblecolumnreactortothesecondolefin
feedstream.
comprisingabubblecolumn,whichmaybeasolutionbubblecolumnoraslurry
bubblecolumntypeofreactor.Abubblecolumnreactorcomprisesagas
bubblephaseandaliquidsolutionphase.Aslurrycolumntypealsohasasolid
14.Theprocessofanyoneofclaims913,furthercomprisingrecoveringa
phasewheretheliquidandsolidaremixedinaslurryorsuspensionform.The
polyolefinproductstreamfromthebulkliquidphase,recoveringpolyolefinfrom
individualgasbubblesinthesetypesofreactorsareembeddedintheliquid
thepolyolefinproductstreamtoformapolyolefinleanstream,andrecyclingat
solutionorslurryphaseandactasmicroreactors.Polymerizationtakesplacein
leastaportionofthepolyolefinleanstreamtothebubblecolumnreactor.
oratthesebubblesinadditiontothepolymerizationintheliquidorliquidslurry
phase.Duetoadifferenceinmonomerconcentrationbetweenthegasbubbles
andliquidphases,thepolymersproducedinthebubblephaseandliquidphase
15.Theprocessofanyoneofclaims914,furthercomprisingmaintaininga
typicallyhavedifferentcompositionandmolecularweight.Theoverallproduct
heterogeneousregime(churnturbulentregime)inthebulkphase.
fromthereactormayhavebimodaldistributionsinmolecularweightdistribution
(MWD)aswellascompositiondistribution(CD),andthelike.Extensive
exchangesbetweenthebubblesandliquidphasesalsotakeplaceinthistype
16.Theprocessofanyoneofthepreviousclaims,furthercomprisingsupplying
ofreactorduetobubblebreakupand/orcoalescence.Polymerswithablocky
aliquiddiluenttoabulkphaseinthebubblecolumnreactor.
structureorbranchedcrossproductsarealsopossibleinsomeembodiments.
Preferably,thisinventionrelatestoaprocesscomprisingcontactingacatalyst
systemwithoneormoreolefinsinabubblecolumnreactoratbimodal
polymerizationconditionstoformapolyolefinhavingabimodaldistributionwith
respecttocompositiondistributionand/ormolecularweightdistributionora
combinationthereof.Preferably,thepolyolefinhasanMwof10,000g/molor
more.Preferably,thepolyolefincomprisesatleasttwomeltingpeaksinaDSC
heatingcyclewithadifferenceinmeltingtemperaturesofatleast5C.
Preferably,theoneormoreolefinscompriseethylene,propylene,C4toC20
17.Apolyolefincopolymercompositioncomprisingethylene,propylene,and,
optionally,aC4toC20alphaolefinsaidcompositionhavingabimodal
distributionwithrespecttocompositiondistribution,molecularweight
distributionoracombinationthereofanMwof10,000g/molormoreandat
leasttwomeltingpeaksinaDSCheatingcyclewithadifferenceinmelting
temperaturesofatleast5Cwhereinthecopolymerisobtainedasaproduct
streamfromabubblecolumnreactor.
alphaolefin,oracombinationthereof.Bybimodalpolymerizationconditionsis
meantpolymerizationcondition,suchas,butnotlimitedto,pressure,bubble
quantity,bubblesize,concentrationsofmonomer,comonomer,catalyst,
activator,scavenger,temperature,etc.,thatcontributetothebimodal/multi
18.Thepolyolefincopolymerofclaim17,whereinthedifferenceinmelting
temperatureisatleast30C.
modalpolymerpropertiesdescribedherein.Molecularweightdistributionis
definedtobeMw/Mn.Compositiondistributionisdeterminedusinga
TemperatureRisingElutionFractionationchromatogramcurvegeneratedasdescribedbelow.
Preferably,thecatalystsystemcomprisesametallocenecatalyst.Preferably,thecatalystsystemcomprisesa
homogenouscatalystandthebubblecolumnreactorcomprisesapolymersolutionreactor.Preferably,thecatalystsystem
comprisesasupportedcatalystandthebubblecolumnreactorcomprisesapolymerslurryreactor.Preferably,theprocess
comprisesspargingagaseousolefinfeedstreamintothebubblecolumnreactor.
Preferably,theprocesscomprisesintroducingfirstandsecondolefinfeedstreamsintothebubblecolumnreactor,wherein
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thefirstolefinfeedstreamisliquidandthesecondolefinfeedstreamisgaseous.Preferably,thefirstolefinfeedstream
comprisespropyleneandthesecondolefinfeedstreamcomprisesethylene.Preferably,thesecondolefinfeedstream
furthercomprisespropylene.Preferably,thesecondolefinfeedstreamfurthercomprisesagaseousdiluent,hydrogen,ora
combinationthereof.
Preferably,theprocessfurthercomprisesrecyclingoverheadvaporfromthebubblecolumnreactortothesecondolefin
feedstream.Preferably,theprocessfurthercomprisesrecoveringapolyolefinproductstreamfromthebulkliquidphase,
recoveringpolyolefinfromthepolyolefinproductstreamtoformapolyolefinleanstream,andrecyclingatleastaportionof
thepolyolefinleanstreamtothebubblecolumnreactor.Preferably,theprocessfurthercomprisesmaintaininga
heterogeneousregime(churnturbulentregime)inthebubblecolumn.Preferably,theprocessfurthercomprisessupplying
aliquiddiluenttoabulkphaseinthebubblecolumnreactor.
Preferably,apolyolefincopolymercompositioncomprisesethylene,propyleneandoptionallyaC4toC20alphaolefina
bimodaldistributionwithrespecttocompositiondistribution,and/ormolecularweightdistributionoracombinationthereof
anMwof10,000g/molormoreandatleasttwomeltingpeaksinaDSCheatingcyclewithadifferenceinmelting
temperaturesofatleast5C.Preferably,thedifferenceinmeltingtemperaturesisatleast10C,oratleast15C,orat
least20C,oratleast30C.
Preferably,thecopolymerisobtainedasaproductstreamfromabubblecolumnreactor.Preferably,thecopolymeris
obtainedastheproductofthebubblecolumnreactorprocessaccordingtoanyoneoftheprocessembodimentsdescribed
herein.
Preferably,aprocesscomprisesprovidingabulkliquidphasecomprisingafirstolefinandapolymerizationcatalyst
systeminabubblecolumnreactorsystemdirectingagaseousstreamcomprisingasecondolefinatleastpartially
throughthebulkliquidphaseatagasvelocitysufficienttoproduceastreamofbubblestherebycontactingthefirstolefin
andthesecondolefinwiththecatalystsystematatemperatureandapressuresufficienttoproduceaproductpolyolefin
havingamultimodalmolecularweightdistribution.Preferably,thefirstolefinandthesecondolefinaredifferent,and
whereinthegaseousstreamcomprisesthefirstolefinandthesecondolefin.Preferably,thefirstolefinisidenticaltothe
secondolefin.Preferably,thebulkliquidphasecomprisesadiluentwhichisaliquidatthetemperatureandpressureofthe
bubblecolumnreactorsystem.Preferably,thegaseousstreamcomprisesagaseousdiluent,hydrogen,oracombination
thereof.Preferably,atleastaportionofolefininaheadspaceofthebubblecolumnreactorsystemisrecycledbackinto
thebubblecolumnreactorsystemasthegaseousstream.Preferably,atleastaportionofmaterialinaheadspaceofthe
bubblecolumnisremovedfromthereactorsystem,followedbycondensingatleastaportionoftheremovedheadspace
materialtoproducealiquidrecyclestream,andrecyclingatleastaportionoftheliquidrecyclestreambackintothe
bubblecolumnreactorsystem,whichmayincluderecycletothebulkliquidphase.Preferably,atleastaportionofthebulk
liquidphaseisremoved,followedbyremovingatleastaportionoftheproductpolyolefintherefromtoproduceabulkliquid
phaserecyclestream,andrecyclingatleastaportionofthebulkliquidphaserecyclestreambackintothebubblecolumn
reactorsystem.Preferably,thegasvelocityissufficienttoproduceaturbulentflowregimeinthebubblecolumnreactor
system.Preferably,thefirstolefincomprisesaC4toC20alphaolefin.Preferably,thesecondolefincomprisesethylene,
propylene,oracombinationthereof.Preferably,thepressureandtemperatureareselectedsuchthatthebulkliquidphase
isasolution.Preferably,thepressureandtemperatureareselectedsuchthatthebulkliquidphaseisaslurry.Preferably,
thepolymerizationcatalystsystemcomprisesasupportedolefinpolymerizationcatalyst,asupportedactivator,ora
combinationthereof.Preferably,thepolymerizationcatalystsystemcomprisesahomogeneousolefinpolymerization
catalyst.
Preferably,theproductpolyolefinhasabimodalcompositiondistributionasreflectedbythepresenceofmultiplepeaksin
aDSCheatingcycle.Preferably,theproductpolyolefinhasafirstmeltingtemperaturewhichisatleast30Chigherthana
secondmeltingtemperatureasdeterminedusingDSCaccordingtotheproceduredescribedintheExperimentalsection,
oranequivalentthereof,asreadilyunderstoodbyonehavingordinaryskillintheart.Preferably,theproductpolyolefinhas
amultimodalcompositionaldistributionwithrespecttotheincorporationofthesecondolefin,themolecularweight
distribution,thepercentcrystallinityinthepolymerspeciespresent,oracombinationthereof.Preferably,thegaseous
streamhasanaverageresidencetimefrom0.1minutesto30minutes.Preferably,thepolymerizationcatalystsystem
comprisesapluralityofcatalysts,activators,oracombinationthereof.Preferably,thebubblecolumnreactorsystem
comprisesapluralityofbubblecolumnsarrangedinserialcommunication,parallelcommunication,oracombination
thereof.
DEFINITIONS
Forpurposesherein,thenewnumberingschemeforthePeriodicTableGroupsisusedasinChem.Eng.News,1985,63,
27.Therefore,a"Group4metal"isanelementfromGroup4ofthePeriodicTable.
Theterm"substituted"meansthatahydrogengrouphasbeenreplacedwithahydrocarbylgroup,aheteroatom,ora
heteroatomcontaininggroup.Forexample,methylcyclopentadiene(Cp)isaCpgroupsubstitutedwithamethylgroup
andethylalcoholisanethylgroupsubstitutedwithanOHgroup.
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Theterms"hydrocarbylradical,""hydrocarbyl,"and"hydrocarbylgroup"areusedinterchangeablythroughoutthis
document.Likewise,theterms"functionalgroup,""group,"and"substituent"arealsousedinterchangeablyinthis
document.Forpurposesofthisdisclosure,"hydrocarbylradical"isdefinedtobetoC20radicals,thatmaybelinear,
branched,orcyclic(aromaticornonaromatic),andmayincludesubstitutedhydrocarbylradicalsasdefinedherein.
Preferably,afunctionalgroupmaycompriseahydrocarbylradical,asubstitutedhydrocarbylradical,oracombination
thereof.
Substitutedhydrocarbylradicalsareradicalsinwhichatleastonehydrogenatomhasbeensubstitutedwithaheteroatom
orheteroatomcontaininggroup,orwithatomsfromGroups13,14,15,16,and17ofthePeriodicTableofElements,ora
combinationthereof,orwithatleastonefunctionalgroup,suchashalogen(CI,Br,I,F),R*2,OR*,SeR*,TeR*,PR*2,
AsR*2,SbR*2,SR*,BR*2,SiR*3,GeR*3,SnR*3,PbR*3,andthelikeorwhereatleastoneheteroatomhasbeeninserted
withinthehydrocarbylradical,suchashalogen(CI,Br,I,F),O,S,Se,Te,NR*,PR*,AsR*,SbR*,BR*,SiR*2,GeR*2,
SnR*2,PbR*2,andthelike,whereR*is,independently,hydrogenorahydrocarbylradical,oranycombinationthereof.
Inthestructuresdepictedthroughoutthisspecificationandtheclaims,asolidlineindicatesabond,anarrowindicatesthat
thebondmaybedative,andeachdashedlinerepresentsabondhavingvaryingdegreesofcovalencyandavarying
degreeofcoordination.
Forpurposesherein,asupportedcatalystand/oractivatorreferstoacatalystcompound,anactivator,oracombination
thereoflocatedon,inorincommunicationwithasupportwhereintheactivator,thecatalystcompound,oracombination
thereofaredepositedon,vaporizedwith,bondedto,incorporatedwithin,adsorbedorabsorbedin,adsorbedorabsorbed
on,thesupport.
Forpurposeshereinan"olefin,"alternativelyreferredtoas"alkene,"isalinear,branched,orcycliccompoundcomprising
carbonandhydrogenhavingatleastonedoublebond.Forpurposesofthisspecificationandtheclaimsappendedthereto,
whenapolymerorcopolymerisreferredtoascomprisinganolefin,theolefinpresentinsuchpolymerorcopolymeristhe
polymerizedformoftheolefin.Forexample,whenacopolymerissaidtohavean"ethylene"contentof35wt%to55wt%,
itisunderstoodthatthemerunitinthecopolymerisderivedfromethyleneinthepolymerizationreactionandsaidderived
unitsarepresentat35wt%to55wt%,basedupontheweightofthecopolymer.
Forpurposesherein,apolymerorpolymericchaincomprisesaconcatenationofcarbonatomsbondedtoeachotherina
linearorabranchedchain,whichisreferredtohereinasthebackboneofthepolymer(e.g.,polyethylene).Thepolymeric
chainmayfurthercomprisevariouspendentgroupsattachedtothepolymerbackbonewhichwerepresentonthe
monomersfromwhichthepolymerwasproduced.Thesependentgroupsarenottobeconfusedwithbranchingofthe
polymerbackbone,thedifferencebetweenpendentsidechainsandbothshortandlongchainbranchingbeingreadily
understoodbyoneofskillintheart.
Forpurposesherein,theterm"polymer"and"polyolefin"areusedinterchangeabletorefertomoleculehavingtwoormore
ofthesameordifferent"mer"units.A"homopolymer"isapolymerhavingmerunitsthatarethesame.A"copolymer"isa
polymerhavingtwoormoremerunitsthataredifferentfromeachother.A"terpolymer"isapolymerhavingthreemer
unitsthataredifferentfromeachother."Different"inreferencetomerunitsindicatesthatthemerunitsdifferfromeach
otherbyatleastoneatomoraredifferentisomerically.Accordingly,thedefinitionofcopolymer,asusedherein,includes
terpolymersandthelike.Anoligomeristypicallyapolymerhavingalowmolecularweight,suchasanMnoflessthan
25,000g/mol,orinanembodiment,lessthan2,500g/mol,oralownumberofmerunits,suchas75merunitsorless.An
"ethylenepolymer"or"ethylenecopolymer"isapolymerorcopolymercomprisingatleast50mole%ethylenederived
units,a"propylenepolymer"or"propylenecopolymer"isapolymerorcopolymercomprisingatleast50mol%propylene
derivedunits,andsoon.
Forthepurposesofthisdisclosure,theterm"aolefin,"oralphaolefinincludesC2toC22olefins.Nonlimitingexamples
ofaolefinsincludeethylene,propylene,1butene,1pentene,1hexene,1heptene,1octene,1nonene,1decene,1
undecene,1dodecene,1tridecene,1tetradecene,1pentadecene,1hexadecene,1heptadecene,1octadecene,1
nonadecene,1eicosene,1heneicosene,1docosene,1tricosene,1tetracosene,
1pentacosene,1hexacosene,1heptacosene,1octacosene,1nonacosene,1triacontene,4methyl1pentene,3
methyl1pentene,5methyl1nonene,3,5,5trimethyllhexene,vinylcyclohexane,andvinylnorbornane.Nonlimiting
examplesofcyclicolefinsanddiolefinsincludecyclopropene,cyclobutene,cyclopentene,cyclohexene,cycloheptene,
cyclooctene,cyclononene,cyclodecene,norbornene,4methylnorbornene,
2methylcyclopentene,4methylcyclopentene,vinylcyclohexane,norbornadiene,dicyclopentadiene,5ethylidene2
norbornene,vinylcyclohexene,5vinyl2norbornene,
1.3divinylcyclopentane,1,2divinylcyclohexane,1,3divinylcyclohexane,
1.4divinylcyclohexane,1,5divinylcyclooctane,1allyl4vinylcyclohexane,1,4diallylcyclohexane,lallyl5
vinylcyclooctane,and1,5diallylcyclooctane.
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Theterms"catalyst,""catalystcompound,"and"transitionmetalcompound"aredefinedtomeanacompoundcapableof
initiatingpolymerizationcatalysisundertheappropriateconditions.Inthedescriptionherein,thecatalystmaybedescribed
asacatalystprecursor,aprecatalystcompound,oratransitionmetalcompound,andthesetermsareused
interchangeably.Acatalystcompoundmaybeusedbyitselftoinitiatecatalysisormaybeusedincombinationwithan
activatortoinitiatecatalysis.Whenthecatalystcompoundiscombinedwithanactivatortoinitiatecatalysis,thecatalyst
compoundisoftenreferredtoasaprecatalystorcatalystprecursor.A"catalystsystem"iscombinationofatleastone
catalystcompound,atleastoneactivator,anoptionalcoactivator,andanoptionalsupportmaterial,wherethesystemcan
polymerizemonomerstopolymer.Forthepurposesofthisinventionandtheclaimsthereto,whencatalystsystemsare
describedascomprisingneutralstableformsofthecomponents,itiswellunderstoodbyoneofordinaryskillintheartthat
theionicformofthecomponentistheformthatreactswiththemonomerstoproducepolymers.An"anionicligand"isa
negativelychargedligandwhichdonatesoneormorepairsofelectronstoametalion.A"neutraldonorligand"isa
neutrallychargedligandwhichdonatesoneormorepairsofelectronstoametalion.
Ascavengerisacompoundthatistypicallyaddedtofacilitateoligomerizationorpolymerizationbyscavengingimpurities.
Somescavengersmayalsoactasactivatorsandmaybereferredtoascoactivators.Acoactivator,thatisnota
scavenger,mayalsobeusedinconjunctionwithanactivatorinordertoformanactivecatalyst.Preferably,acoactivator
canbepremixedwiththecatalystcompoundtoformanalkylatedcatalystcompound.
Anethylenepolymerisapolymerhavingatleast50mol%ofethylene,apropylenepolymerisapolymerhavingatleast
50mol%ofpropylene,andsoon.Asusedherein,Mnisnumberaveragemolecularweight,Mwisweightaverage
molecularweight,Mziszaveragemolecularweight,wt%isweightpercent,andmol%ismolepercent.Molecularweight
distribution(MWD)isdefinedtobeMwdividedbyMn.Unlessotherwisenoted,allmolecularweightunits,e.g.,Mw,Mn,
Mz,areg/mol.
Forpurposesherein,RTisroomtemperature,whichisdefinedas25Cunlessotherwisespecified.Allpercentagesare
weightpercent(wt%)unlessotherwisespecified.
Asusedherein,theterms"productpolyolefin"and"reactorblend"areusedinterchangeablytorefertoamixtureof
polymersproducedinoneormorepolymerizationzonesinthesamepolymerizationprocess/systemwithouttheneedfor
postpolymerizationblending.However,thisisnotintendedtolimittheproductpolyolefinaccordingtotheinstant
disclosuresincetheresultantproductpolyolefinmayundergopostpolymerizationblending,forexample,toincorporate
additionalpolymericspecies,modifiers,additives,and/orthelike.Eachpolymercomponentinthemixturepossessesa
uniquemolecularstructuresuchaspercentcomonomercontent,molecularweightdistribution,amountofcrystallinity,
and/ormoleculararchitecturessuchasbranchedblockcopolymerproducts.
Apolymerizationzoneisdefinedasanareawhereolefinsarecontactedwithpolymerizationcatalystssystemsunder
conditionssufficienttoproduceapolyolefin.Forpurposesherein,multiplereactorsmaybedimensionedandarrangedin
seriesconfigurations,parallelconfiguration,oracombinationthereofwhereineachreactorisconsideredasaseparate
polymerizationzone.Foramultistagepolymerizationinbothabatchreactorandacontinuousreactor,each
polymerizationstageisconsideredasaseparatepolymerizationzone.Forabubblecolumntypeofreactor,thebubble
regionandliquidregionareconsideredasaseparatepolymerizationzone.Asusedherein,asolutionreferstoaclear
singlephaseliquidincontrasttoaslurry,whichreferstoaturbidmultiplephasecombinationofasolidandaliquid.A
solutionpolymerizationreferstoconditionswhereintheproductpolymerandtheolefins,arepresentasasolution,orare
presentbelowacloudpointsuchthataclearsolutionispresent.Aslurrypolymerizationreferstoaconditionwhereinthe
polymerstartstosolidifyandisphaseseparatedfromaliquidmedium.Thecloudpointofapolymersolutionisthe
temperature(atagivenpressure)orthepressure(atagiventemperature)atwhichdissolvedpolymersarenolonger
completelysoluble,phaseseparatedasasecondphase,givingthepolymersolutionacloudyappearance.Thecloud
pointisthepressurebelowwhich,atagiventemperature,thepolymerizationsystembecomesturbidasdescribedinJ.
VladimirOliveira,C.Dariva,andJ.C.Pinto,Ind.Eng,Chem.Res.39,2000,4627.Forpurposesofthisinventionandthe
claimsthereto,thecloudpointismeasuredbyshiningaheliumlaserthroughtheselectedpolymerizationsystemina
cloudpointcellontoaphotocellandrecordingthepressureattheonsetofrapidincreaseinlightscatteringforagiven
temperature.Cloudpointpressureisthepointatwhichatagiventemperature,thepolymerizationsystembecomesturbid.
Cloudpointtemperatureisthepointatwhichatagivenpressure,thepolymerizationsystembecomesturbid.
Foraliquidmixturecomprisingtwoormorecomponents,thebubblepointisdefinedasthepressureataconstant
temperatureorthetemperatureataconstantpressurewhereafirstbubbleofvaporisformed.Likewise,dewpointofa
solutionisthesetofconditions(eitheratemperatureatconstantpressureorapressureatconstanttemperature)atwhich
thefirstdropsofavapormixturebegintocondense.Themixtureisintheliquidphasewhenthepressureishigherthan
thebubblepointpressure.Theboilingpointofapuresubstanceorelementisthetemperatureatwhichthevaporpressure
ofaliquidequalsthesurroundingenvironmentalpressure.
Asusedhereintheterm"branchedblockcopolymer"isdefinedasthecrossproductobtainedwhenafirstpolymerchain
(alsoreferredasmacromonomer)withreactivepolymerizablechainendsisincorporatedintoasecondpolymerchain
duringthepolymerizationofthelattertoformastructurecomprisingabackbonedefinedbyoneofthepolymerchainswith
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branchesoftheotherpolymerchainsextendingfromthebackbone.Backboneandbranchespossessdifferentandunique
molecularstructures,suchaschemicalcompositionand/orcrystallinity.Forexample,apolypropylenehomopolymerwith
vinylchainendscanbeincorporatedintoapropylenecopolymerchaintoformabranchedcrossproductwithapropylene
copolymerbackboneandpolypropylenesidebranches.Sincethemolecularstructure/compositioninthebackboneand
branchesaredifferent,thebranchedblockcompositionhascharacteristicsfromboththebackboneandthebranches.The
branchedblockproductsarealsoreferredtoasbranchedcrossproducts.
Preferably,theinventiveprocesscomprisesprovidingabulkliquidphasecomprisingafirstolefinandapolymerization
catalystsysteminabubblecolumnreactorsystemdirectingagaseousstreamcomprisingasecondolefinatleast
partiallythroughthebulkliquidphaseatagasvelocitysufficienttoproduceastreamofbubblestherebycontactingthe
firstolefinandthesecondolefinwiththecatalystsystematatemperatureandapressuresufficienttoproduceaproduct
polyolefinhavingamultimodalmolecularweightdistribution.
Forpurposesherein,abubblecolumnreactorsystemreferstoacylindricalvesselwithagasdistributoratthebottom.The
gasisintroducedintothecolumnthroughthedistributor,anddispersedinaliquidinformsofbubbles.Theliquideither
staysinthecolumninabatchmodeofoperation,oriscontinuouslyfedintoanddischargedfromthecolumnina
continuousprocessthroughassociatedpiping,valves,heatexchangers,andthelike.Abubblecolumnreactorsystem
mayalsobereferredtoasaslurrycolumn,whereinsolidparticlesaresuspendedinthebulkliquidphasetoformaliquid
solidsuspension(orliquidsolidslurry).Thedifferencebetweenabubblecolumnandaslurrycolumnlieinthatslurry
columnhasaliquidsolidphaseinsteadofaliquidphaseasthebulkliquidphaseofthebubblecolumn.Bothbubble
columnandslurrycolumnhavesimilarcharacteristicsandsharethesametypeofdesignsandoperations.Bubblecolumn
reactorshavebeenbuiltinnumerousformsofconstruction.Themixingisdonebythegassparginganditrequiresless
energythanmechanicalstirring.Theliquidcanbeinparallelfloworcountercurrentflow.Thefeaturesandcharacteristics
ofbubblecolumntypeofreactorsarewelldocumentedintheliterature(e.g.,BubbleColumnReactions,byWolfDieter
Deckwer,publishedbyJohnWiley&SonsinDecember1991).
Forpurposesherein,abubblecolumnreactororabubblecolumnreactorsystemcomprisesagasbubblephaseanda
bulkliquidsolutionphase.Abubblecolumnmaybeutilizedasahomogeneouscolumnoraheterogeneouscolumn.A
slurrycolumntypeofreactorcomprisesagasbubblephase,andabulkliquidphasewhichisaslurryincludingasolid
phase.Theliquidandsolidaremixedtogetherandarepresentinaslurry(orsuspension)form.Forpurposesherein,a
bubblecolumnreferstoeitherahomogeneous(i.e.,asolutionorliquid)column,oraheterogeneous(i.e.,aslurry)column.
Accordingly,forsimplicity,unlessotherwisespecified,thetermsbubblecolumn,bubblecolumnreactor,bubblecolumn
reactorsystem,liquidbubblecolumn,solutionbubblecolumn,slurrycolumn,slurrycolumnreactor,andslurrycolumn
reactorsystemareusedinterchangeably.
ReferringtoFIG.1ofthedrawings,referencenumeral10generallyindicatesabubblecolumnreactorinaccordancewith
anembodimentoftheinstantdisclosureforpolymerizinganolefin.Thereactor10includesabulkliquidphase12,which
mayincludeoneormorepolymerizationcatalysts,optionallyasolvent,and/oroneormorepolymerizationreagents
includingchainterminationreagents,scavengers,cocatalysts,and/orthelike.Avaporizedorgaseousolefinfeedstream
14entersabottomofreactor10throughoneormorespargers26suchthatthevaporizedorgaseousolefinfeedstream
14entersthebottomofthebubblingcolumnofbulkliquidphase12asapluralityofbubbleswhereintheolefinsare
contactedwiththecatalystunderpolymerizationconditions.
Agaseousoverhead28leavesfromatopofreactor10throughoneormoregaseousrecycleorventlines24,whichmay
bearrangedtorecycleatleastaportionofthevaporizedoverheadbackintothegaseousfeed14.
Preferably,anolefinisfedasgaseousfeed14whichformsbubbles16whereinthegaseousfeed14contactsthebulk
liquidphase12inthepresenceofacatalyst,toproducepolyolefinsaccordingtotheinstantdisclosure,whichmaybe
subsequentlyremovedfromthereactorbyoneormoreproductremovallines18.Thebulkliquidphase12maybe
refreshed,additionalcatalyst,solvent,and/orreagentsadded,and/oroneormoreofthevariousstreamsrecycledbackto
thereactorbyoneormorerecyclelines20.AsshowninFIG.2,thebulkliquidphase12ofthebubblingcolumnreactor10
maycompriseanadmixtureofproductsandasolventwhichmayincludeaslurriedcatalystsystem22,withfastrising
bubbles16ofvaporizedolefinfeed14passingupwardlythroughthebubblingcolumn10ofbulkliquidphase12.Thefast
risinggasbubbles16maybeintroducedintoreactor10tocreatevigorousmixinginsidethebulkliquidphase12,turning
thebulkliquidphase12intoabubblingcolumn.Thisisimportantandadvantageous,asitmayallowthereactor10to
operatewithoutastirreroragitator,which,ifpresent,maybesusceptibletofouling.Unreactedgaseousolefinstream24
mayberecycledbacktothereactor10togetherwithfresholefinfeed14,and/orhydrogenorotherpolymerization
reagents,and/orthelike.
Superficialgasvelocityisdefinedasthegasthroughputsperunitcrosssectionalareaofthebubblecolumn.Gasholdup
isdefinedasthevolumefractionofgasphaseoccupiedbythegasbubbles.Likewisetheliquidandsolidphaseholdupis
definedasthevolumefractionofliquidandsolidphases,respectively.Superficialliquidvelocityisdefinedastheliquid
throughputsperunitcrosssectionalareaofthebubblecolumn.
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Thefluiddynamiccharacterizationofbubblecolumnreactorshasasignificanteffectontheoperationandperformanceof
bubblecolumnreactorsystems.Operationofbubblecolumnreactorsistypicallyclassifiedintothreeflowregimes
accordingtoitsflowcharacteristics.Thesethreeregimesarethehomogeneous(alsoreferredtoasabubblyflowor
dispersed)regimetheheterogeneous(alsoreferredtoasachurnturbulent)regimeandslugflowregime.Theflow
regimesinbubblecolumnsareclassifiedandmaintainedaccordingtothesuperficialgasvelocityemployedinthecolumn.
Thebubbleflowregime,alsocalledthehomogeneousflowregimeisobtainedatlowsuperficialgasvelocities.Thisflow
regimeischaracterizedbybubblesofrelativelyuniformsmallsizesandlowrisingvelocities,andisconsideredfor
purposeshereintorepresentnonturbulentflow.Auniformbubbledistributionandrelativelygentlemixingisobservedover
theentirecrosssectionalareaofthecolumn.Thereispracticallynobubblecoalescenceorbreakup,thusbubblesizein
thisregimeisalmostcompletelydictatedbythespargerdesignandthephysicalpropertiesoftheliquidorliquidsolid.The
gasholdupinthebubblyflowregimeincreasesalmostlinearlywithincreasingsuperficialgasvelocity.Masstransfer
betweenthebubblesandliquidmediumoccursattheinterfacesmainlythroughdiffusion.
Achurnturbulentregime,alsocalledtheheterogeneousregime,referstoconditionsinvolvingturbulentflowmaintainedat
highersuperficialgasvelocities.Thisregimeischaracterizedbythedisturbedformofthehomogeneousgasliquidsystem
duetoenhancedturbulentmotionofgasbubblesandliquidrecirculationinthereactor.Asaresultofunsteadyflowpattern
andhighgasthroughputslargebubbleswithshortresidencetimesareformedbybubblecoalescence.Thisflowregimeis
thussometimesreferredtoascoalescedbubbleflowregime,indicatingthemuchdifferentsizesofthebubblesand
frequentbubblebreakupandcoalescence.Bubblecoalescenceandbreakupresultinawidebubblesizedistribution
characteristicofachurnturbulentregime.Theaveragebubblesizeisgovernedbycoalescenceandbreakupwhichis
controlledbytheenergydissipationrateinthebulk.Vigorousmixingormassexchangebetweenbubblephaseandliquid
phasetakesplaceinthisregime.Churnturbulentflowisfrequentlyobservedinindustrialsize,largediametercolumns.
Aslugflowregimehasbeenonlyobservedinsmalldiametercolumnsathighgasflowrates.Thisregimetakesitsname
fromtheformationofbubbleslugswhenlargerbubblesarestabilizedbythecolumnwall.
Preferably,eachindividualbubbleintheprocessdisclosedhereinisconsideredtoformanindividualreactorembeddedin
theliquidsolutionorslurryphase,eachactingasamicroreactor.Polymerizationisthoughttotakeplaceinsidethe
bubblesinadditiontothepolymerizationinthebulkliquidphaseinabubblecolumnreactororintheliquidsolidslurry
phaseinaslurrycolumn.Duetothedifferenceinmonomerconcentrationbetweenthegasbubblesandliquidphases,the
polymerproducedinthebubblephaseandliquidphasehasbeendiscoveredtohavedifferentcompositionandmolecular
weightdistributions.Theoverallproductfromthebubblecolumnreactorsystemdisclosedhereinisapolymerproduct
havingamultimodal,orabimodaldistributioninmolecularweightdistribution(MWD),compositiondistribution(CD),
crystallinity,and/oracombinationthereof.Extensiveexchangebetweenthebubblesandliquidphasesisthoughttotake
placeinthistypeofreactorduetobubblebreakupandcoalescence.Preferably,polymerswithablockystructureor
branchedcrossproductscanalsobeproduced.Thereactorblendsarederivedfromthecomponentsproducedfromthe
bubblephaseandthebulkliquid(orslurry)phase.
Preferably,hydrodynamiccharacteristicsofabubblecolumnreactororaslurrycolumnreactorareachievedbymeansof
upwardflowinggasinandthroughthebulkliquidphasepresentinthecolumn.Preferably,thegasphaseisintroduced
intothereactorthroughanarrangementoffeednozzles.Thefeednozzlearrangementisknownbyvariousnamesinthe
artsuchasdistributor,sparger,gasdistributorplate,gasdistributinggrid,perforatedplate,gasdispersiongrid,orthelike.
Afeednozzleatthebottomsectionofthereactorisusedtodistributethegasacrossthereactorcrosssectionandto
preventthereactorcontentfromenteringthegassupplyplenum.Preferably,thefeednozzleparametersmaybe
dimensioned,arranged,andalteredtoproduceparticularbubblecharacteristicswhichinturnaffectgasholdupandthus
manyotherparameterscharacterizingbubblecolumnreactors.
Preferably,thefeednozzlemayincludeadownwardpointingnozzle,whichpreventscloggingofthespargerwithpolymer
ifthegasflowisstoppedandwhicharegenerallyconsideredtobemoreeffectivefordispersingacatalyst.Inaddition,
downwardgasejectionhasbeendiscoveredtoproduceimprovedbubbleformationforpurposeshereinrelativetoupward
injectionnozzles.Preferably,thefeednozzlesaredimensionedandarrangedtoproduceauniformdistributionofgasfeed
acrossthereactorcrosssection,whichisthoughttobeusefultoachievemixingbetweentherisinggasbubblesandthe
bulkliquidmedium.Preferably,nonuniformgasdistributionmaybeusedtoaltertheliquidflowpatterninsidethecolumn.
Preferably,agasdistributormaycompriseorificesorporousmetalspargers.Preferably,orificesofthegasdistributormay
bearrangedanddimensionedtoproducenonuniformgasdistribution,aswellasbeplacedfacingupwards,downwards
orboth.
Theprocessdisclosedhereincanbeusedtoproducepolymerblendswithawidevarietyofcompositions.Preferably,a
blendcomponentisprimarilyproducedintheliquidphaseinabubblecolumnorintheliquidsolidsuspensionphaseina
slurrycolumntypeofreactorsthroughthecontactofcatalystandmonomersinaliquidregionofthebubblecolumn
reactor,andanothercomponentisprimarilyproducedinabubbleregionofthebubblecolumnreactor.Preferably,polymer
producedinthebubbleregionismixedwithpolymerproducedintheliquidregionthroughbubblebreakupand
coalescenceaswellasbulkliquidrecirculation.Preferably,anintimatepolymerblendisformedduetotheintensive
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mixingofthedisparatepolymericspeciesproducedinthereactor.Preferably,thecompositionsofthepolymer
componentscanbeadjustedthroughthemonomerconcentrationineachregionofthereactor,whichmaybecontrolled
throughavarietyofmeansdisclosedherein.
Preferably,thesolventsordiluentsutilizedintheprocessareselectedsuchthatthethermodynamicpropertiesofthe
solventsandmonomersaredifferent.Preferably,theselectionisdirectedtotheconcentrationofamonomerwithlower
boilingpointbeinghigherinthebubbleregionthanintheliquidorslurryregion.Preferably,theselectionmayberelativeto
thecontentoflowerboilingpointmonomerinthepolymersproducedinthebubbleregionbeinghigherthanthatinthe
polymerproducedintheliquidorslurryregion.Preferably,theratioofthetwoormorecomponentsdependsonthegas
holdupinareactor,whichisalsoeffectedbytheselectionofthesolvents.
Preferably,thecompositiondistributionsineachregionmaybecontrolledbyselectionofthetemperatureand/orpressure
aswellasthecompositionoftheparticulargaseousfeed,bulkliquidmedium,orboth.Preferably,thegaseousstream
directedintothebulkliquidphasemaycompriseaninertgasordiluent,suchasnitrogen,tocontroltheflowregimeand
changethechemicalcompositioninthegasbubbles.Preferably,thegaseousstreammayincludereactivesubstances,
suchashydrogen,tofurthercontrolthepropertiesofthepolymersproducedtherein.Preferably,additionalinertgasmay
beprovidedtoincreasetheoverallgasflowrateandsuperficialgasvelocity.
Preferably,theinstantpolymerizationprocessisoperatedinthechurnturbulentregime.Preferably,theinertgascanbe
mixedwithothermaterialssuchasmonomersandintroducedintothereactorasamixtureorfedintothereactorasa
separatedstream.
Preferably,thegasvelocityissufficienttoproduceaturbulentflowofgasbubblesthroughthebubblecolumnreactor
system.Preferably,thesuperficialgasvelocityisgreaterthan0.05m/second,orfrom0.05m/secondto0.3m/second,or
from0.05m/secondto0.6m/second,orfrom0.05m/secondto1m/second,orfrom0.1m/secondto1.5msecond.
Preferably,theamountofthefirstolefin,alsoreferredtoasthefirstpolymercomponent,relativetothesecondolefin,also
referredtoasthesecondpolymercomponent,mayvarywidelydependingonthenatureofthecomponentpolymersand
intendedendusesofthepolymerblend.Accordingly,oneadvantageoftheinstantprocessistheabilitytobeableto
produceapolymerblendinwhichalowercrystallinitypolymercomprisesmorethan20%,suchasmorethan50%,for
example,morethan70%ofthetotalreactorpolymerblend.
Ithasbeendiscoveredthattheamountofthefirstpolymerrelativetothesecondpolymercomponentmainlydependson
thegasholdup.Gasholdupislowinthehomogeneousregime.Gasholdupdependsmainlyonsuperficialgasvelocity.
Forbothbubblecolumnsandslurrybubblecolumns,gasholduphasbeenfoundtoincreasewithincreasingsuperficial
gasvelocity.Thisincreasehasbeenfoundtobeproportionaltosuperficialgasvelocityinthebubblyflowregime.Forthe
churnturbulentregime,theeffectofsuperficialvelocityongasholdupislesspronounced.Preferably,thebubblecolumn
reactorhasagasholdupof10%ormore,or15%ormore.Inanotherembodiment,thegasholdupisinarangeof20%to
35%forbothbubblecolumnandslurrycolumnprocesses.
Preferably,themolecularweightofeachcomponentinthereactorpolymerblendcanbeoptimizedforaspecific
application.Generally,themolecularweightofthehighcrystallinecomponentshouldbegreaterthantheentanglement
molecularlength,whilethemolecularweightofthelesscrystallineoramorphouscomponentshouldbelongenoughso
thecrystallinecomponentcanbindthepolymersegmentstogetherintoaphysicalnetworkinthesolidstate.Whenthe
molecularweightofthefirstpolymerislow,thesecondpolymershouldhavehighermolecularweighttoattaingood
mechanicalstrength.Highermolecularweightcomponentcanbeproducedineitherthebubblingregionortheliquid/slurry
region.Formostcatalyst,thepropagationrateinthepolymerizationincreaseswithmonomerconcentration.Higher
molecularweightcomponentcanbeproducedinaregionwithhighermonomerconcentration.
Preferably,hydrogen,ifpresentinthepolymerizationreactor,ispresentatanylevelthatwillachievethedesiredmelt
index(MIor12)ormeltflowrate(MFR)andmolecularweightsofthehighandthelowmolecularweightcomponent.Due
topreferentialdistributionofH2betweentheliquidorslurryregionandbubbleregion,theeffectsofH2onmolecular
weightaremoresignificantinthebubbleregion.AdditionofH2furtherenhancesthedifferenceofmolecularweightof
polymersproducedinthebubbleregionandliquidregion.MolecularweightorMIorMFRcanthusbeinfluencedbythe
hydrogenconcentration.Theamountofhydrogeninthepolymerizationcanbeexpressedasamolarratiorelativetothe
totalpolymerizablemonomer,forexample,ethylene,orablendofethyleneandanotheralphaolefin.Theamountof
hydrogenusedinthepolymerizationprocessesofthepresentdisclosureisanamountnecessarytoachievethedesired
molecularweightofthefinalpolyolefinresin.
Preferably,theratioofhydrogentototalethylenemonomer(molppmH2:mol%ethylene)inthecirculatinggasstreamisin
arangeoffrom0to100,inarangeoffrom0.05to50inanotherembodiment,inarangeoffrom0.10to40ineven
anotherembodiment,andinarangeoffrom0.15to35instillanotherembodiment.Circulatinggasstreamincludesgas
fromthefreshfeedandgasfromtherecyclestream.
Preferably,theinventivepolymerizationprocessisoperatedinasolutionprocess.Asolutionpolymerizationisdefinedas
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aprocessinwhichthepolymersproducedremaindissolvedinaliquidpolymerizationmediumsuchasaninertsolventor
monomer(s)ortheirmixtures.Asolutionpolymerizationistypicallyahomogeneousliquidpolymerizationsystem.Fora
bubblecolumntypeofreactor,asolutionprocessmeansthatthepolymerproducedisdissolvedintheliquidphaseunder
thepolymerizationcondition.Often,thecatalystandmonomerarealsodissolvedinthepolymerizationmedium,butthatis
notarequirementofa"solution"process.Intypicalsolutionprocesses,thepolymerizationtemperatureand/orpressureis
abovethecloudypoint.
Preferably,thepolymerizationprocessconditionsaresufficienttomaintainthepolymerizationsysteminasolutionstate.
Forexample,theminimumreactiontemperatureandpressureareselectedsothatthepolymersproducedaredissolvedin
theliquidmedium,i.e.,abovethepolymerizationsystem'scloudpointandaboveitssolidfluidphasetransition
temperatureandpressurewiththatpolymer.Furthermore,forsolutionpolymerizationprocesses,thelowerlimitsof
reactiontemperaturecanalsobedeterminedbythesolidfluidphasetransitiontemperature.Reactorsoperatedbelowthe
solidfluidphasetransitiontemperatureofthereactionmixturecanleadtooperationproblemsduetofouling.The
applicationofcertaininertsolventscanfurtherreducetheminimumoperationtemperatureofthefoulingfreeoperation
regime,althoughthesubstantialpresenceofinertsolventscanreducepolymerizationrateandproductmolecularweight.
Theupperlimitfortemperaturecanbedeterminedbytheproductpropertiesthatarestronglyinfluencedbythereaction
temperature.Sinceoftenpolymerswithhighermolecularweightsand/orhighermeltingtemperaturesaredesired,high
polymerizationtemperatures(>200C)aregenerallynotadvantageous.Increasedtemperaturescanalsodegrademany
catalyticsystems,providinganotherreasonforavoidingexcessivepolymerizationtemperatures.Fromthisperspective,
temperaturesbelow250Careuseful.Usefulreactorconditionsareinfluencedbytheproductspecificationsandreactor
operationissuesasoutlinedabove.Advantageously,thepolymerizationtemperaturesforhighcrystallinepolymersare
typicallybetween90Cand200C,orbetween90Cand180C,orbetween90Cand150C,orbetween90Cand
140C,orbetween95Cand140C.Forlowcrystallineoramorphouspolymers,thereactiontemperaturescanbemuch
lower.
Polymerswithlowcrystallinityorlowmeltingtemperatureareoftenproducedinasolutionprocessduetotheselected
operatingwindowsoptimizedforcatalystandprocesseconomics.Inthecourseoffinishing,unreactedmonomersand
solventareremovedfromthepolymerizationmixtureuntilpolymercanformsolidpelletsorbales.Theunreacted
monomersandsolventcanberecycledbacktothereactor.
Anyformofcatalystincludinghomogenouscatalystsandsupportedcatalystscanbeusedinthesolutionprocess.
Preferably,homogenouscatalystsareemployedinthesolutionprocess.
Manypolymersareinsolubleinthereactionmediumfromwhichtheyareformed.Uponsignificantpolymerization,polymer
chainsreachacrystallizablelengthandpolymernucleationandcrystallizationbegin.Thecrystallizationofpolymersleads
topolymersolventphaseseparation.Aslurryprocess,inanembodiment,isconductedinadiluentinwhichthecatalystis
affixedtosupport,andthepolymerformedduringproductionremainssuspendedintheliquidmedium,neverdissolving.
Thediluentcanbeaninertsolvent(diluent),monomer(s),ortheirmixture.Preferably,polymersolventphaseseparation
canbealsoinducedthroughmismatchofsolvencyofthereactionmediumwithrespecttothepolymerproduced.Forthe
purposeofthisinventionandtheclaimsthereto,theslurryprocessincludesthepolymerizationinwhichthepolymer
producedisphaseseparatedfromtheliquidmediumandissuspendedintheliquidmediuminaformofdropletsorsolid
particles.Aslurryprocessincludesalsothesuspensionprocess.Foraslurrycolumntypeofreactor,aslurryprocess
meansthatatleastpartofthepolymersproducedisinaformofparticulate,solidformsembeddedintheliquid
polymerizationmedium.Inslurry(suspension)polymerizationprocessmonomers,suchasethyleneorpropylene,are
partiallydissolvedinanorganicreactionmediumandthencontactedwithacatalyst.Thepolyethyleneorpolypropylene
formedresidesintheliquidmediuminaformofparticulateorsuspension.Polymersproducedinthebubbleregionare
intimatelymixedwiththepolymersformedintheliquidmediumduetointeractionsbetweenbubblesandslurrymedium.In
anotherembodiment,theinventedpolymerizationprocessisoperatedinaslurryprocess.
Preferably,thepolymerizationoccursbelowthecrystallizationtemperatureofthepolymerproducedinthehydrocarbon
diluent.
Inoneormoreembodiments,thereactiontemperatureand/orpressureareselectedsothatthepolymerizationsystem
remainsatapressureand/oratemperaturebelowthepolymer'scloudpointinaparticularpolymerizationsystem,
resultinginatwophasepolymerizationsystemformingapolymerrichphaseandapolymerleanphase.Thepolymerrich
phase(alsoreferredastosuspension)containsmostofpolymerproduced,whilethepolymerleanphasecomprisesmost
ofthesolventandmonomers.
Anyformofcatalyst,includinghomogenouscatalystsandsupportedcatalysts,canbeusedintheslurryprocess.
Preferably,supportedcatalystsareemployedinthesolutionprocess.
Theinventiveprocessrelatestothehomopolymerizationofethyleneorthecopolymerizationofethylenewithatleastone
comonomerhavingfrom3to12carbonatoms,or4to8carbonatoms.Particularly,thecomonomersarepropylene,
butene1,4methylpentene1,3methylpentenel,hexene1andoctene1,themorepreferredbeinghexene1,butene1
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andoctene1.Preferably,thecomonomer(s)arepresentintheethylenecopolymeratfrom0.1to50mol%,moreor1to
30mol%,or1to20mol%.Theinventiveprocessmayalternativelyrelatetothehomopolymerizationofpropyleneorthe
copolymerizationofpropylene.Inthecaseofcopolymerization,thecomonomerofthecopolymerisethyleneand/oraC4
toC20linear,branched,orcyclicmonomer,and,inoneembodiment,isaC4toC12linearorbranchedalphaolefin,or
butene1,pentene1,hexene1,heptene1,octene1,nonene,decene,dodecene,4methylpentenel,3methylpentene
1,3,5,5trimethylhexene1,andthelike.Preferably,thecomonomerispresentfrom0.5to99mol%,orfrom1to60
mol%,orfrom1to50mol%,orfrom1to35mol%,orfrom2to30mol%,orfrom2to25mol%,orfrom2to15mol%,
basedontheentirepolymer.
Preferably,thepolymerproducedhereinisahomopolymerorcopolymerofoneormorelinearorbranchedC3toC30
prochiralalphaolefinsorC5toC30ringcontainingolefinsorcombinationsthereofcapableofbeingpolymerizedbyeither
stereospecificandnonstereospecificcatalysts.Prochiral,asusedherein,referstomonomersthatfavortheformationof
isotacticorsyndiotacticpolymerwhenpolymerizedusingstereospecificcatalyst(s).
Themonomertobepolymerizedcomprisesaromaticgroupcontainingmonomerscontainingupto30carbonatoms.
Suitablearomaticgroupcontainingmonomerscompriseatleastonearomaticstructure,orfromonetothree,oraphenyl,
indenyl,fluorenyl,ornaphthylmoiety.Thearomaticgroupcontainingmonomerfurthercomprisesatleastone
polymerizabledoublebondsuchthatafterpolymerization,thearomaticstructurewillbependantfromthepolymer
backbone.Thearomaticgroupcontainingmonomermayfurtherbesubstitutedwithoneormorehydrocarbylgroups
includingbutnotlimitedtotoalkylgroups.Additionally,twoadjacentsubstitutionsmaybejoinedtoformaringstructure.
Preferredaromaticgroupcontainingmonomerscontainatleastonearomaticstructureappendedtoapolymerizable
olefinicmoiety.Particularlypreferredaromaticmonomersincludestyrene,alphamethylstyrene,paraalkylstyrenes,
vinyltoluenes,vinylnaphthalene,allylbenzene,andindene,especiallystyrene,paramethylstyrene,4phenyllbutene,and
allylbenzene.
Nonaromaticcyclicgroupcontainingmonomersarealsousefulmonomersherein.Thesemonomerscancontainupto30
carbonatoms.Suitablenonaromaticcyclicgroupcontainingmonomershaveatleastonepolymerizableolefinicgroup
thatiseitherpendantonthecyclicstructureorispartofthecyclicstructure.Thecyclicstructuremayalsobefurther
substitutedbyoneormorehydrocarbylgroupssuchas,butnotlimitedto,toalkylgroups.Preferably,nonaromaticcyclic
groupcontainingmonomersincludevinylcyclohexane,vinylcyclohexene,vinylnorbornene,ethylidenenorbornene,
cyclopentadiene,cyclopentene,cyclohexene,cyclobutene,vinyladamantane,andthelike.
Diolefinmonomersusefulinthisinventionincludeanyhydrocarbonstructure,orC4toC30,havingatleasttwo
unsaturatedbonds,whereinatleasttwooftheunsaturatedbondsarereadilyincorporatedintoapolymer.Itisfurther
preferredthatthediolefinmonomersbeselectedfromalpha,omegadienemonomers(i.e.,divinylmonomers).
Preferably,thediolefinmonomersarelineardivinylmonomers,orthosecontainingfrom4to30carbonatoms.Examples
ofdienesincludebutadiene,pentadiene,hexadiene,heptadiene,octadiene,nonadiene,decadiene,undecadiene,
dodecadiene,tridecadiene,tetradecadiene,pentadecadiene,hexadecadiene,heptadecadiene,octadecadiene,
nonadecadiene,icosadiene,heneicosadiene,docosadiene,tricosadiene,tetracosadiene,pentacosadiene,hexacosadiene,
heptacosadiene,octacosadiene,nonacosadiene,triacontadiene,particularlypreferreddienesinclude1,6heptadiene,1,7
octadiene,1,8nonadiene,1,9decadiene,1,10undecadiene,1,11dodecadiene,1,12tridecadiene,1,13
tetradecadiene,andlowmolecularweightpolybutadienes(Mwlessthan1000g/mol).Cyclicdienesinclude
cyclopentadiene,vinylnorbornene,norbornadiene,ethylidenenorbornene,divinylbenzene,dicyclopentadiene,orhigher
ringcontainingdiolefinswithorwithoutsubstituentsatvariousringpositions.
Oneormoredienesmaybepresentintheethyleneand/orpropylenebasedpolymerproducedhereinatupto10wt%,or
at0.00001wt%to1.0wt%,or0.002wt%to0.5wt%,or0.003wt%to0.2wt%,baseduponthetotalweightofthepolymer.
Preferably,500ppmorlessofdieneisaddedtothepolymerization,or400ppmorless,or300ppmorless,basedupon
thetotalweightofthepolymer.Preferably,atleast50ppmofdieneisaddedtothepolymerization,or100ppmormore,or
150ppmormore,baseduponthetotalweightofthepolymer.
Ethyleneand/orpropylenemaybepolymerizedwithatleasttwodifferentcomonomerstoformaterpolymer.Suitable
comonomersincludeacombinationofalphaolefinmonomershaving4to10carbonatoms,or4to8carbonatoms,
optionallywithatleastonedienemonomer.Preferably,terpolymersincludeethylene/butenel/hexene1,
ethylene/propylene/butene1,propylene/ethylene/hexene1,ethylene/propylene/octene1,
ethylene/propylene/norbornene,andthelike.
Anyknownsolventforthereactionmixturethatiseffectiveforthepurposecanbeusedinconductingpolymerizationsin
accordancewiththepresentinvention.Forexample,suitablesolventswouldbehydrocarbonsolventssuchasaliphatic,
cycloaliphaticandaromatichydrocarbonsolvents,orhalogenatedversionsofsuchsolvents.Preferably,solventsareor
lower,straightchainorbranchedchain,saturatedhydrocarbons,C5toC9saturatedalicyclicoraromatichydrocarbonsor
C2tohalogenatedhydrocarbons.Preferably,solventsincludeorlower,linearchainorbranchedchainhydrocarbons,
hexane,andmethylcyclopentane.Nonlimitingillustrativeexamplesofsolventsarebutane,pentane,hexane,heptane,
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cyclopentane,cyclohexane,cycloheptane,methylcyclopentane,methylcyclohexane,isooctane,benzene,toluene,
xylene,chloroform,chlorobenzenes,tetrachloroethylene,dichloroethane,andtrichloroethane.
Optimizedpolymerizationsystemsincludeproperselectionofsolvent(ordiluents)andmonomersunderaspecific
pressureandtemperaturefordesiredproducts.Combinationsofhighboilingpointsolventwithalowboilingpoint
monomerallowthesystemtohavehighgasthroughputandwiderangeselectionofsystempressureandtemperature.
Forasystemwithselectedsolventandmonomers,temperatureandpressureofpolymerizationsystemdeterminesthe
concentrationoflowboilingmonomerintheliquidorliquidsolidregionaswellasthebubbleregion.
Temperatureemployedinthereactorisnotlimited,providedthatitissuitableforthepolymerizationwithagiventypeof
catalystssystem.Theselectionoftemperaturedependsonthereactantsandsolventsemployed,andmonomer
concentration,amongotherfactors.Temperaturehasinfluenceonthesolubilityofreactantintheliquidphaseand
reactantconcentrationinthegasbubblephase.Ingeneral,thesolubilityishigheratlowertemperature.Thus,thechoices
ofsolventandtemperaturearenotindependent.
Operatingtemperatureandpressureneedtobeinarangesothatatleastthelowestboilingcomponentisingasphase
andpresencepartiallyinthebubbleregion.Theboilingpointofmosthydrocarbonsisreadilyavailableinliterature.In
anotherembodiment,theoperatingtemperatureandpressureneedtobeinarangesothatthetemperatureneedstobe
abovethebubblingpointandthepressureneedstobelowerthanthebubblingpointoftheliquidmixture.Formost
hydrocarbonmixtures,thebubblingpointanddewpointcanbecalculatedusingthethermodynamicprincipleormeasured
directly.
Theprocessmaybeusedtoproduceethylenepolymerblends.Thereactorblends,inanembodiment,canbeproduced
bycontactingethyleneandoneormoremonomersselectedfromC3toC20alphaolefins.Undercertainoperating
conditions,partofethylenemaybedissolvedinaninertsolventordiluentwiththeremainingethylenebeingpresentinthe
gasbubbleregion.Ethyleneconcentrationinthebubbleregionmayberelativelyhigherthanthatintheliquidregion.
Polymersproducedinthegasbubbleregionhavehigherethylenecontentthanthatpolymerizedintheliquidregion,
dependingonthecatalystemployed.Higherdensitypolymerismainlyproducedinthebubbleregion.Preferably,the
polymerproducedinthegasbubbleregionhasadensityof0.91g/cm3orhigherandthepolymerproducedintheliquid
(orliquidsolid)regionhasadensityof0.90g/cm3orless.Preferably,thedensitiesofthetwopolymercomponentsdiffer
atleastby1%,orbyatleast2%,orbyatleast3%,basedonthedensityofthehigherdensitycomponent.Inanother
embodiment,thepolymerproducedinthegasbubbleregionhasadensityof0.93g/cm3orhigherandthepolymer
producedintheliquid(orliquidsolid)regionhasadensityof0.92g/cm3orless,whereinthedensityisdetermined
accordingtoASTMD1505.
Preferably,thedifferenceinethylenecontentbetweenthetwocomponentsissuchthatthecomponentproducedinthe
gasbubbleshasadensityinarangefrom0.91to0.96g/cm3andthecomponentformedintheliquidorliquidslurryregion
hasadensityinarangeof0.86to0.92g/cm3,and/orthepolymerblendhasatleasttwomeltingpeaksonthesame
heatingcycleofDSCmeasurementusingtheproceduredescribedblow.Preferably,thedifferencebetweenthetwopeak
meltingtemperaturesis20Cormore,or30Cormore,or35Cormore.
Preferably,thecontentofcomonomersuchasbutene1,hexene1,oroctene1inthepolymerproducedintheliquidor
liquidsolidslurryregionishigherthanthatforpolymerproducedinthegasbubbleregion.Preferably,thepolymer
producedintheliquidregionhascomonomercontentinarangefrom4wt%to25wt%.Inanotherembodiment,the
comonomercontentsofthepolymersproducedinthegasbubbleregionandintheliquidregiondifferatleastby1wt%,or
byatleast2wt%,orbyatleast3wt%,basedonthewt%comonomerinthehighercomonomercontentpolymer.
Inethylenepolymerizationaccordingtooneormoreembodimentsdisclosedherein,ethyleneconcentrationemployedin
theliquidregioncanreachtothemaximumconcentrationatsaturationconditionascomparedto4wt%to7wt%inthe
knownslurryorsolutionprocesswheretheethylenemustbecompletelydissolvedintheliquidmediumundergiven
operatingpressuresandtemperatures.Formostcatalystsystemsinembodiments,highermonomerconcentrationmeans
higherpolymerizationrateperunitreactorvolumeandhighermolecularweightofthepolymerproduced.
Formostcatalystsinembodiments,thepolymermolecularweightdependsatleastinpartontheconcentrationof
monomerand!,whenpresent.IthasbeendiscoveredthatpreferentialdistributionofH2andethylenebetweentheliquid
regionandgasbubbleregionmayleadtogreaterdifferenceinmolecularweightforthepolymersproducedintheliquid(or
liquidslurry)regionandgasbubbleregion.Underoperatingconditionsaccordingtotheinstantdisclosure,theincreasein
molecularweightduetotheincreaseinethyleneconcentrationinthebubbleregionmaybebalancedoutbythedecrease
inmolecularweightduetotheincreaseofconcentrationinthegasbubbleregion.
Ethylenepolymerscanbeproducedintheslurryprocessinembodiments.Solventwithlowsolvencytopolyethyleneis
preferredasadiluent.Differentdiluentshavedifferentsolvencyabilitytotheethylenepolymerproduced.Ithasbeen
discoveredthatthelowermolecularweightofalinearalkanediluentinembodiments,theloweristhesolvencyfor
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polyethylene.Branchingoflinearalkanemayalsoreduceitssolvencypower.Ithasfurtherbeendiscoveredthatthelower
themolecularweightofadiluent,thelowertheboilingpoint.Choiceofdiluentalsoaffectsthecompositioninthegas
bubblesandthecompositionofpolymerproducedinthebubbleregion.Preferably,diluentssuitableforusehereininclude
CitoC20alkanes,orisobutane,pentanes,hexanes,and/orheptanes.ForethylenecopolymerproductionwithC3toC20
alphaolefins,ithasbeendiscoveredthathigherdensitypolymerisproducedinthebubbleregionthanthatproducedin
theslurryregion.
Forpolymerizationofethyleneinaslurryprocess,preferably,thetemperatureisinarangefrom50Cto120C,orfrom
70Cto110C,orfrom70Cto100C,whereinthetemperatureandpressureareselectedtobebelowthecloudpoint.
Preferably,polymerizationofethyleneiscarriedoutatatemperaturerangedfrom70Cto90Candapressurebelow40
MPaintheslurryreactor.Isobutanecanbeusedasthediluent.Thereactiontemperatureiscontrolledbyremovingthe
heatofpolymerizationthroughthecoolingjacket.Aslurryproductiscontinuouslyremovedfromthereactor(e.g.,through
apressurecontrolvalve).Theslurrycontains55wt%orlessofsolidpolymerproduced.
Theinventiveprocessmayalsobeusedforethylenepolymerizationinasolutionprocess.Choiceoftemperatureand
pressuredependsonthetypeofsolventanddensityofpolymerproduced.Highdensitypolyethylene(HDPE)hasa
meltingpointofabove135C.Atambientcondition,HDPEdoesnotdissolveinmostofthehydrocarbonsolvents.HDPE
doesdissolveinhydrocarbonofsufficientmolecularweightatthesolubilitypoint.Forasolutionprocess,thetemperature
mustbehighenoughtopreventpolymerfromcrystallizingintheliquidregion.Forexample,intypicalsolutionpolyethylene
processes,polymerizationtakesplaceinahydrocarbonsolventattemperaturesabovethemeltingpointofthepolymer
producedandthepolymeristypicallyrecoveredbyvaporizationofthesolventandanyunreactedmonomer.Preferably,
thetemperatureis100Cormore,or120Cormore,or150Cormore.ForHDPE,polymerizationtemperaturemaybein
arangefrom150CtoEthylenepolymerizationcanbecarriedoutinacontinuousprocess.Ethyleneandcomonomersuch
as1butene,1hexeneand1octenecanbeintroducedintothereactorineithergasphaseorliquidform.Thereactorcan
beoperatedatatemperaturerangedfrom100Cto250Candapressurebelow3MPa.Suitablesolventsinclude
isoparaffinsolvent(amixtureofCgandC9isoparaffins),cyclohexaneand/ormethylpentane.Gasbubblesareintroduced
tocreategoodmixinginthereactor.Useofmechanicalmixingandbafflesmayfurtherenhancethemixingofreaction
medium.Preferably,thereactorincludesmechanicalmixingdevicesand/orbaffles.Goodmixingandrapidreactionmake
itpossibletouseshortresidencetimesuchthatreactorsoperateatrelativelyhighproductionratesandefficiencies.
Preferably,thereactorconfigurationmayincludeasinglereactorormultiplereactorsinseriesand/orinparallel.
Preferably,theaverageresidencetimeineachreactorisinarangefrom2to60minutes.
Theinventiveprocessdisclosedhereinmaybeusedtoproducepropylenepolymers.Thereactorblendscanbeproduced
bycontactingpropyleneandoneormoremonomersselectedfromethyleneorC4toC20alphaolefins.Preferably,
operatingconditionsareselectedsuchthataportionofthepropyleneisdissolvedinaninertsolventordiluentandthe
remainingpropyleneispresentinthegasbubbleregion.Theconcentrationofethylene(ifpresent)andpropyleneinthe
bubbleregionisdifferentfromthatintheliquidorliquidslurryregion.Polymersproducedinthegasbubbleregionhave
differentpropylenecontentfromthatpolymerizedintheliquidregion,dependingonthecatalystemployed.For
ethylene/propylenecopolymers,higherethylenecontentpolymerismainlyproducedinthebubbleregion.For
propylene/butaneandpropylene/hexenecopolymers,thepolymerproducedinthebubbleregionhashigherpropylene
contentthanthatproducedintheliquidregion.Molecularweightofthepolymersproducedinthebubbleregionisdifferent
fromthatproducedintheliquidorliquidsolidslurryregionduetothedifferenceinreactionenvironment.Forhomo
polypropylene,theblendmaycomprisetwopolypropylenecomponentswithdifferentmolecularweightdistributions.
Propylenepolymerizationmaybeeffectedinacontinuousslurryprocess.Thepolymerizationtemperatureisbelowthe
cloudpointofthepolymerizationsystem,and/orthetemperatureisbelowthemeltingpoint,and/orthetemperatureis
belowthecrystallizationpointofthepolymersothatthepolymerformsassolidparticlessuspendedinthehydrocarbon
diluent.Polymerizationpressuredependsonthechemicalcompositionsinthepolymerizationmedium.Preferably,the
pressureisselectedtobelowenoughsothatatleastoneofthemonomersispresentinthebubbleregion.Theinstant
processcanalsobeusedforpropylenepolymerizationinasolutionprocess.Fortheproductionofhighlycrystalline
polypropylenes(meltingpeaktemperatures>150C)insolutionpolymerizationprocesses,theminimumoperating
temperatureis100C.
Semicrystallinepropylenecopolymersareproducedinasolutionprocessaccordingtooneormoreembodiments
disclosedherein.Semicrystallinepropylenecopolymersmayhaveacomonomercontentrangingfrom2wt%to20wt%.
Amorphouspropylenecopolymermayalsobeproducedinasolutionprocessaccordingtooneormoreembodiments
disclosedherein.Ethylenepropylenecopolymersaregenerallyamorphousatethylenecontentsbetween20wt%and70
wt%whenthepolymerisproducedinahomogeneouspolymerizationconditionusingasinglecatalyst.Ifapolymer
componentwithethylenecrystallinityisdesiredintheblend,itmaycompriseinexcessof60wt%ethylene.Ifacomponent
isdesiredwithpropylenecrystallinity,itmayhavelessthan30wt%ethyleneinanembodiment.Furthermore,inthiscase,
inanembodiment,onemayuseacatalystsystemthatiscapableofpolymerizingpropylenestereospecifically.Catalyst
systemsthatproduceisotacticpropylenesequencesmaybesuitableforuse.
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Theprocessdisclosedhereinmayalsobeusedtoproduceoligomersofanyofthemonomerslistedabove.Suitable
oligomersincludeoligomersofanyC2toC20olefins,orC2toC12alphaolefins,orethylene,propyleneand/orbutene.
Preferably,thefeedstockfortheoligomerizationprocessisethylene.Inanalternativeembodiment,otheralphaolefins
including,butnotlimitedto,propyleneand1butene,mayalsobeusedaloneorcombinedwithethylene.For
oligomerizationaccordingtotheinstantdisclosure,ethylenemaybefedintothebubblecolumnreactorinthegasphase.
Oligomerizationreactiontakesplaceinboththebubbleregionandtheliquidregiondependingonthecatalystemployed.
Inertgascanalsobeusedinthebubblephasetoadjusttheflowpatternforanoptimizedreactioncondition.
Thepolymerizationprocessofthisinventioncanbeappliedtoanyappropriatepolymerizationknowninart.These
processescanbeoperatedineitheracontinuousprocessorinabatchprocess.Inacontinuoussolutionoperation
process,bothgasandsolution(containingsolventandpolymerproduced)flowconcurrentlyupwardinthecolumn.The
superficialvelocityofthesolutionphaseislowerthanthegassuperficialvelocity.Preferably,thesuperficialvelocityofthe
solutionphaseislowerthanthegassuperficialvelocitybyatleastanorderofmagnitude.Likewise,foracontinuousslurry
operationprocess,bothgasandliquiddiluentflowconcurrentlyupwardinthecolumn.Thediluentsuperficialvelocityis
lowerthanthegassuperficialvelocity.Preferably,thediluentsuperficialvelocityislowerthanthegassuperficialvelocity
byatleastanorderofmagnitude.Thepolymerparticlesproducedaresuspendedinthediluentandcanbeeither
stationaryorflowconcurrentlyupwardwithdiluent.Polymerproducedalonewithpolymerizationmediumisdischarged
fromthecolumn.Inabatchmodeoperation,theslurrysuspensionorthesolutionisstationary,meaningnocontinuous
flowintoordischargefromthereactor.Thegaseouscomponentsarebubbledupwardintothereactor.Preferably,the
lengthtodiameterratio,oraspectratio,ofthecolumnisatleast5.
Thepolymerproductcanberecoveredfromsolutionatthecompletionofthepolymerizationbyanyofthetechniqueswell
knownintheartsuchassteamstrippingfollowedbyextrusiondryingorbydevolatilizingextrusion.Separated
solvent/diluentandmonomerscanberecycledbackinthereactor.
Thepolymerizationprocessesdisclosedhereinmayhaveresidencetimesinthereactorsasshortas0.1minutesor5
minutesandaslongasseveralhours,alternativelyfrom5minutesto120minutes,alternativelyfrom10to60minutes,
alternativelyfrom15to30minutes.
Temperaturecontrolinthereactorisgenerallyobtainedbybalancingtheheatofpolymerizationwithreactorcooling.
Reactorscanbecooledbyreactorjacketsorcoolingcoils,autorefrigeration,prechilledfeeds,orcombinationsofall
three.Carefulselectionofsolventordiluentisrequiredtomatchwiththeoperatingpressureandtemperatureforanauto
refrigeratedreactorcoolingsystem.Gaseouscomponentsfromthevaporizationwillalsoalterthecompositionprofilein
thebubbleregion.Adiabaticreactorswithprechilledfeedsaresuitableforuseherein.
Polymerizationscanbecarriedouteitherinasinglereactor,orintwoormorereactorsconfiguredinseriesorparallel.In
anyoperationmode,thecatalystsystemmaycompriseoneormorethanonecatalystprecursorandoneormore
activator.Inbothsingleandmultireactoroperations,theoneormorecatalystsystemsmaybeintroducedatonepointor
atmultiplepointstotheoneormorepolymerizationreactors.Variousfeedconfigurationscanbeuseddependingonsuch
factorsasthedesiredproductproperties,suchas,forexample,molecularweightdistribution,orcatalyststability.Such
feedconfigurationsarewellknownintheartofchemicalengineeringandcanbereadilyoptimizedforthedesired
productionscaleandproductpropertiesusingknownengineeringtechniques.Accordingly,inanembodiment,thebubble
columnreactorsystemcomprisesapluralityofbubblecolumnsarrangedinserialcommunication,parallelcommunication,
oracombinationthereof.Eachmayoperateunderthesameoperationalconditions(e.g.,temperature,pressure,bubble
rate,agitation,residencetime,andthelike),differentoperationalconditions,utilizingthesameordifferentcatalysts,
monomers,comonomers,and/orthelike.
Allpolymerizationcatalystsincludingconventionaltypetransitionmetalcatalystsaresuitableforuseinthepolymerization
processoftheinvention.Thefollowingisanonlimitingdiscussionofthevariouspolymerizationcatalystsusefulinthe
processoftheinvention.
ConventionaltypetransitionmetalcatalystsarethosetraditionalZieglerNattacatalystsandPhillipstypechromium
catalystwellknownintheart.ExamplesofconventionaltypetransitionmetalcatalystsarediscussedinUS4,115,639
US4,077,904US4,482,687US4,564,605US4,721,763US4,879,359andUS4,960,741.Theconventionaltype
transitionmetalcatalystcompoundsthatmaybeusedinthepresentinventionincludetransitionmetalcompoundsfrom
Groups3to10,or4to6ofthePeriodicTableofElements.
Theseconventionaltypetransitionmetalcatalystsmayberepresentedbytheformula:
MRX(I)
whereMisametalfromGroups3to10,orGroup4,ortitaniumRisahalogenorahydrocarbyloxygroupandxisthe
valenceofthemetalM,orxis1,2,3,or4,orxis4.NonlimitingexamplesofRincludealkoxy,phenoxy,bromide,
chlorideandfluoride.NonlimitingexamplesofconventionaltypetransitionmetalcatalystswhereMistitaniuminclude
TiCl3>TiCl4,TiBr4,Ti(OC2H5)3Cl,Ti(OC2H5)Cl3,Ti(OC4H9)3Cl,Ti(OC3H7)2Cl2,Ti(OC2H5)2Br2,TiCl3.l/3AlCl3,and
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Ti(OC12H25)Cl3.
Conventionaltypetransitionmetalcatalystcompoundsbasedonmagnesium/titaniumelectrondonorcomplexesthatare
usefulintheinventionaredescribedin,forexample,U.S.US4,302,565andUS4,302,566,whicharehereinfully
incorporatebyreference.TheMgTiCl^(ethylacetate)4derivativeisparticularlypreferred.GB2,105,355,describesvarious
conventionaltypevanadiumcatalystcompounds.Nonlimitingexamplesofconventionaltypevanadiumcatalyst
compoundsincludevanadyltrihalide,alkoxyhalidesandalkoxidessuchasVOCl3,VOCl2(OBu)whereBuisbutyland
VO(OC2H5)3vanadiumtetrahalideandvanadiumalkoxyhalidessuchasVC14andVC^fOBu)vanadiumandvanadyl
acetylacetonatesandchloroacetylacetonatessuchasV(AcAc)3andVOCl2(AcAc)where(AcAc)isanacetylacetonate.
ThepreferredconventionaltypevanadiumcatalystcompoundsareVOCI3,VCI4,andVOCI2ORwhereRisa
hydrocarbonradical,oraCitoQoaliphaticoraromatichydrocarbonradicalsuchasethyl,phenyl,isopropyl,butyl,propyl,
nbutyl,isobutyl,tertiarybutyl,hexyl,cyclohexyl,naphthyl,etc.,andvanadiumacetylacetonates.
Conventionaltypechromiumcatalystcompounds,oftenreferredtoasPhillipstypecatalysts,suitableforuseinthe
presentinventionincludeC1O3,chromocene,silylchromate,chromylchloride(Cr02Cl2),chromium2ethylhexanoate,
chromiumacetylacetonate
(Cr(AcAc)3),andthelike.NonlimitingexamplesaredisclosedinUS2,285,721US
3,242,099andUS3,231,550.
Stillotherconventionaltypetransitionmetalcatalystcompoundsandcatalystsystemssuitableforuseinthepresent
inventionaredisclosedinUS4,124,5324,302,5654,302,566
A20416815andEPA10420436.
whereM'isMg,Mnand/orCatisanumberfrom0.5to2M"isatransitionmetalsuchasTi,V,and/orZrXisahalogen,
orCI,Br,orIYmaybethesameordifferentandishalogen,aloneorincombinationwithoxygen,NR2,OR,SR,
COOR,orOSOOR,whereRisahydrocarbylradical,inparticularanalkyl,aryl,cycloalkylorarylalkylradical,
acetylacetonateanioninanamountthatsatisfiesthevalencestateofM'uisanumberfrom0.5to20Eisanelectron
donorcompoundselectedfromthefollowingclassesofcompounds:(a)estersoforganiccarboxylicacids,(b)alcohols,(c)
ethers,(d)amines,(e)estersofcarbonicacid,(f)nitriles,(g)phosphoramides,(h)estersofphosphoricandphosphorus
acid,and(i)phosphorusoxychloride.Nonlimitingexamplesofcomplexessatisfyingtheaboveformulainclude:
MgTiCl52CH3COOC2H5,Mg3Ti2.
Cl127CH3COOC2H5,MgTiCl56C2H5OH,MgTiCl5IOOCH3OH,MgTiCl5tetrahydrofuran,MgTi2Cl127C6H5CN,MggT^Cl^
eQHjCOO^Hj,MgTiCl62CH3COOC2H5,
MgTiCl66C5H5N,MnTiCl54C2H5OH,MgTiCl5(OCH3)2CH3COOC2H5,MgTiCl5(C6H5)23CH3COOC2H5,MgTiBr2Ci4
2(C2H5)20,Mg3V2Cl127CH3COOC2H5,MgZrCl^tetrahydrofuran.Othercatalystsmayincludecationiccatalystssuchas
AICI3andothercobaltandironcatalystswellknownintheart.
Typically,theseconventionaltypetransitionmetalcatalystcompounds(excludingsomeconventionaltypechromium
catalystcompounds)areactivatedwithoneormoreoftheconventionaltypecocatalystsdescribedbelow.
Conventionaltypecocatalystcompoundsfortheaboveconventionaltypetransitionmetalcatalystcompoundsmaybe
representedbytheformula:
M3M4vX2cR3b_c(HI)
whereinM3isametalfromGroup1,2,12,and13ofthePeriodicTableofElementsM4isametalofGroupIAofthe
PeriodicTableofElementsvisanumberfrom0to1eachX2isanyhalogencisanumberfrom0to3eachR3isa
monovalenthydrocarbonradicalorhydrogenbisanumberfrom1to4andwhereinbminuscisatleast1.
Otherconventionaltypeorganometalliccocatalystcompoundsfortheaboveconventionaltypetransitionmetalcatalysts
havetheformula:
M3R3k(IV)
whereM3isaGroup1,2,12,or13metal,suchaslithium,sodium,beryllium,barium,boron,aluminum,zinc,cadmium,
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andgalliumkequals1,2,or3dependinguponthevalencyofM3whichvalencyinturnnormallydependsuponthe
particularGrouptowhichM3belongsandeachR3maybeanymonovalenthydrocarbonradical.
NonlimitingexamplesofconventionaltypeorganometalliccocatalystcompoundsofGroups1,2,12,and13usefulwith
theconventionaltypecatalystcompoundsdescribedaboveincludemethyllithium,butyllithium,dihexylmercury,
butylmagnesium,diethylcadmium,benzylpotassium,diethylzinc,trinbutylaluminum,diisobutylethylboron,
diethylcadmium,dinbutylzinc,andtrinamylboron,and,inparticular,thealuminumalkyls,suchastrihexylaluminum,
triethylaluminum,trimethylaluminum,andtriisobutylaluminum.Otherconventionaltypecocatalystcompoundsinclude
monoorganohalidesandhydridesofGroup2metals,andmonoordiorganohalidesandhydridesofGroup13metals.
Nonlimitingexamplesofsuchconventionaltypecocatalystcompoundsincludediisobutylaluminumbromide,
isobutylborondichloride,methylmagnesiumchloride,ethylberylliumchloride,ethylcalciumbromide,diisobutylaluminum
hydride,methylcadmiumhydride,diethylboronhydride,hexylberylliumhydride,dipropylboronhydride,octylmagnesium
hydride,butylzinchydride,dichloroboronhydride,dibromoaluminumhydride,andbromocadmiumhydride.Conventional
typeorganometalliccocatalystcompoundsareknowntothoseintheart,andamorecompletediscussionofthese
compoundsmaybefoundinUS3,221,002andUS5,093,415.
Generally,polymerizationcatalystsusefulintheinventionincludeoneormorebulkyligandmetallocenecompounds(also
referredtohereinasmetallocenes).Typicalbulkyligandmetallocenecompoundsaregenerallydescribedascontaining
oneormorebulkyligand(s)andoneormoreleavinggroup(s)bondedtoatleastonemetalatom.Thebulkyligandsare
generallyrepresentedbyoneormoreopen,acyclic,orfusedring(s)orringsystem(s)oracombinationthereof.These
bulkyligands,orthering(s)orringsystem(s)aretypicallycomposedofatomsselectedfromGroups13to16atomsofthe
PeriodicTableofElementsortheatomsareselectedfromthegroupconsistingofcarbon,nitrogen,oxygen,silicon,
sulfur,phosphorous,germanium,boronandaluminumoracombinationthereof.Mostofthering(s)orringsystem(s)are
composedofcarbonatomssuchas,butnotlimitedto,thosecyclopentadienylligandsorcyclopentadienyltypeligand
structuresorothersimilarfunctioningligandstructuresuchasapentadiene,acyclooctatetraendiyloranimideligand.The
metalatomisselectedfromGroups3through15andthelanthanideoractinideseriesofthePeriodicTableofElements.
Preferably,themetalisatransitionmetalfromGroups4through12,orGroups4,5,and6,orthetransitionmetalisfrom
Group4.
Preferably,thecatalystcompositionoftheinventionincludesoneormorebulkyligandmetallocenecatalystcompounds
representedbytheformula:
LALBMQn(V)
whereMisametalatomfromthePeriodicTableoftheElementsandmaybeaGroup3to12metalorfromthelanthanide
oractinideseriesofthePeriodicTableofElements,orMisaGroup4,5,or6transitionmetal,orMisaGroup4transition
metal,evenorMiszirconium,hafniumortitanium.Thebulkyligands,LAandLB,areopen,acyclicorfusedring(s)orring
system(s)andareanyancillaryligandsystem,includingunsubstitutedorsubstituted,cyclopentadienylligandsor
cyclopentadienyltypeligands,heteroatomsubstitutedand/orheteroatomcontainingcyclopentadienyltypeligands.Non
limitingexamplesofbulkyligandsincludecyclopentadienylligands,cyclopentaphenanthreneylligands,indenylligands,
benzindenylligands,fluorenylligands,octahydrofluorenylligands,cyclooctatetraendiylligands,cyclopentacyclododecene
ligands,azenylligands,azuleneligands,pentaleneligands,phosphoylligands,phosphinimine(WO99/40125),pyrrolyl
ligands,pyrozolylligands,carbazolylligands,borabenzeneligandsandthelike,includinghydrogenatedversionsthereof,
forexampletetrahydroindenylligands.Preferably,LAandLBmaybeanyotherligandstructurecapableofbondingtoM.
Inyetanotherembodiment,theatomicmolecularweight(MW)ofLAorLBexceeds60a.m.u.,orgreaterthan65a.m.u.In
anotherembodiment,LAandLBmaycompriseoneormoreheteroatoms,forexample,nitrogen,silicon,boron,
germanium,sulfur,andphosphorous,incombinationwithcarbonatomstoformanopen,acyclic,orafused,ringorring
system,forexample,aheterocyclopentadienylancillaryligand.OtherLAandLBbulkyligandsincludebutarenotlimited
tobulkyamides,phosphides,alkoxides,aryloxides,imides,carbolides,borollides,porphyrins,phthalocyanines,corrins,
andotherpolyazomacrocycles.Independently,eachLAandLBmaybethesameordifferenttypeofbulkyligandthatis
bondedtoM.Preferably,ofFormulaIIIonlyoneofeitherLAorLBispresent.
Independently,eachLAandLBmaybeunsubstitutedorsubstitutedwithacombinationofsubstituentgroupsR.Non
limitingexamplesofsubstituentgroupsRincludeoneormorefromthegroupselectedfromhydrogen,orlinear,branched
alkylradicals,oralkenylradicals,alkynylradicals,cycloalkylradicalsorarylradicals,acylradicals,aroylradicals,alkoxy
radicals,aryloxyradicals,alkylthioradicals,dialkylaminoradicals,alkoxycarbonylradicals,aryloxycarbonylradicals,
carbomoylradicals,alkylordialkylcarbamoylradicals,acyloxyradicals,acylaminoradicals,aroylaminoradicals,straight,
branchedorcyclic,alkyleneradicals,orcombinationthereof.Preferably,substituentgroupsRhaveupto50nonhydrogen
atoms,orfrom1to30carbons,thatcanalsobesubstitutedwithhalogensorheteroatoms,orthelike.Nonlimiting
examplesofalkylsubstituentsRincludemethyl,ethyl,propyl,butyl,pentyl,hexyl,cyclopentyl,cyclohexyl,benzylorphenyl
groups,andthelike,includingalltheirisomers,forexampletertiarybutyl,isopropyl,andthelike.Otherhydrocarbyl
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radicalsincludefluoromethyl,fluoroethyl,difluoroethyl,iodopropyl,bromohexyl,chlorobenzyl,andhydrocarbylsubstituted
organometalloidradicalsincludingtrimethylsilyl,trimethylgermyl,methyldiethylsilyl,andthelikehalocarbylsubstituted
organometalloidradicalsincludingtris(trifluoromethyl)silyl,methylbis(difluoromethyl)silyl,bromomethyldimethylgermyl,
andthelikedisubstitutedboronradicalsincludingdimethylboron,forexampleanddisubstitutedpnictogenradicals
includingdimethylamine,dimethylphosphine,diphenylamine,methylphenylphosphine,chalcogenradicalsincluding
methoxy,ethoxy,propoxy,phenoxy,methylsulfide,andethylsulfide.NonhydrogensubstituentsRincludetheatoms
carbon,silicon,boron,aluminum,nitrogen,phosphorous,oxygen,tin,sulfur,germanium,andthelike,includingolefins
suchas,butnotlimitedto,olefinicallyunsaturatedsubstituentsincludingvinylterminatedligands,forexamplebut3enyl,
prop2enyl,hex5enyl,andthelike.Also,atleasttwoRgroups,ortwoadjacentRgroups,arejoinedtoformaring
structurehavingfrom3to30atomsselectedfromcarbon,nitrogen,oxygen,phosphorous,silicon,germanium,aluminum,
boron,oracombinationthereof.
Also,asubstituentgroupRgroupsuchas1butanylmayformacarbonsigmabondtothemetalM.
OtherligandsmaybebondedtothemetalM,suchasatleastoneleavinggroupQ.Preferably,Qisamonoanioniclabile
ligandhavingasigmabondtoM.Dependingontheoxidationstateofthemetal,thevaluefornis0,1,or2suchthat
FormulaVaboverepresentsaneutralbulkyligandmetallocenecatalystcompound.
NonlimitingexamplesofQligandsincludeweakbasessuchasamines,phosphines,ethers,carboxylates,dienes,
hydrocarbylradicalshavingfrom1to20carbonatoms,hydridesorhalogensandthelikeoracombinationthereof.In
anotherembodiment,twoormoreQ'sformapartofafusedringorringsystem.OtherexamplesofQligandsinclude
thosesubstituentsforRasdescribedaboveandincludingcyclobutyl,cyclohexyl,heptyl,tolyl,trifluoromethyl,
tetramethylene,pentamethylene,methylidene,methyoxy,ethyoxy,propoxy,phenoxy,bis(Nmethylanilide),dimethylamide,
dimethylphosphideradicals,andthelike.
Inanotherembodiment,thecatalystcompositionoftheinventionmayincludeoneormorebulkyligandmetallocene
catalystcompoundswhereLAandLBofFormulaVarebridgedtoeachotherbyatleastonebridginggroup,A,as
representedby:
LAALBMQn(VI)
whereinLA,LB,M,Q,andnareasdefinedabove.ThesecompoundsofFormulaVIareknownasbridged,bulkyligand
metallocenecatalystcompounds.NonlimitingexamplesofbridginggroupAincludebridginggroupscontainingatleast
oneGroup13to16atom,oftenreferredtoasadivalentmoietysuchas,butnotlimitedto,atleastoneofacarbon,
oxygen,nitrogen,silicon,aluminum,boron,germaniumandtinatom,oracombinationthereof.Preferably,bridginggroup
Acontainsacarbon,siliconorgermaniumatom,orAcontainsatleastonesiliconatomoratleastonecarbonatom.The
bridginggroupAmayalsocontainsubstituentgroupsRasdefinedaboveincludinghalogensandiron.Nonlimiting
examplesofbridginggroupAmayberepresentedby2C,R^Si,R^SiR^Si,R^Ge,R'P,whereR'isindependently,aradical
groupwhichishydride,hydrocarbyl,substitutedhydrocarbyl,halocarbyl,substitutedhalocarbyl,hydrocarbylsubstituted
organometalloid,halocarbylsubstitutedorganometalloid,disubstitutedboron,disubstitutedpnictogen,substituted
chalcogen,orhalogenortwoormoreR'maybejoinedtoformaringorringsystem.Preferably,thebridged,bulkyligand
metallocenecatalystcompoundsofFormulaVIhavetwoormorebridginggroupsA(EP664301B1).
Inanotherembodiment,thebulkyligandmetallocenecatalystcompoundsarethosewheretheRsubstituentsonthebulky
ligandsLAandLBofFormulasVandVIaresubstitutedwiththesameordifferentnumberofsubstituentsoneachofthe
bulkyligands.Inanotherembodiment,thebulkyligandsLAandLBofFormulasVandVIaredifferentfromeachother.
Inanotherembodiment,thecatalystcompositionsoftheinventionmayincludebridgedheteroatom,monobulkyligand
metallocenecompounds.Thesetypesofcatalystsandcatalystsystemsaredescribedin,forexample,WO92/00333WO
94/07928WO91/04257WO94/03506WO96/00244WO97/15602WO99/20637US5,057,475US5,096,867US
5,055,438US5,198,401US5,227,4405US,264,405andEPA0420436.
Theabovedescribedpolymerizationcatalyst,particularlybulkyligandmetallocenetypecatalystcompounds,aretypically
activatedinvariouswaystoyieldcatalystcompoundshavingavacantcoordinationsitethatwillcoordinate,insert,and
polymerizeolefin(s).
Forthepurposesofthisinvention,theterm"activator"isdefinedtobeanycompoundwhichcanactivateanyoneofthe
catalystcompoundsdescribedhereinbyconvertingtheneutralcatalystcompoundtoacatalyticallyactivecatalystcation
compound.Nonlimitingactivators,forexample,includealumoxanes,aluminumalkyls,ionizingactivators,whichmaybe
neutralorionic,andconventionaltypecocatalysts.
Preferably,alumoxaneactivatorsareutilizedasanactivatorinthecatalystcompositionoftheinvention.Alumoxanesare
generallyoligomericcompoundscontainingAl(R)0subunits,whereRisanalkylgroup.Nonlimitingexamplesof
alumoxanesincludemethylalumoxane(MAO),modifiedmethylalumoxane(MMAO),ethylalumoxaneand
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isobutylalumoxane.Alumoxanesmaybeproducedbythehydrolysisoftherespectivetrialkylaluminumcompound.MMAO
maybeproducedbythehydrolysisoftrimethylaluminumandahighertrialkylaluminumsuchastriisobutylaluminum.
MMAO'saregenerallymoresolubleinaliphaticsolventsandmorestableduringstorage.Thereareavarietyofmethods
forpreparingalumoxaneandmodifiedalumoxanes.Anotheralumoxaneisamodifiedmethylalumoxane(MMAO)
cocatalysttype3A(commerciallyavailablefromAkzoChemicals,Inc.underthetradenameModifiedMethylalumoxane
type3A).AluminumAlkylororganoaluminumcompoundswhichmaybeutilizedasactivatorsincludetrimethylaluminum,
triethylaluminum,triisobutylaluminum,trinhexylaluminum,trinoctylaluminum,andthelike.
Itiswithinthescopeofthisinventiontouseanionizingorstoichiometricactivator,neutralorionic,suchastri(nbutyl)
ammoniumtetrakis(pentafluorophenyl)boron,atrisperfluorophenylboronmetalloidprecursororatrisperfluoronaphthyl
boronmetalloidprecursor,polyhalogenatedheteroboraneanions(WO98/43983),boricacid(US5,942,459),or
combinationthereof.Itisalsowithinthescopeofthisinventiontouseneutralorionicactivatorsaloneorincombination
withalumoxaneormodifiedalumoxaneactivators.
Nonlimitingexamplesofneutralstoichiometricactivatorsincludetrisubstitutedboron,tellurium,aluminum,galliumand
indiumormixturesthereof.Thethreesubstituentgroupsareeachindependentlyselectedfromalkyls,alkenyls,halogen,
substitutedalkyls,aryls,arylhalides,alkoxy,andhalides.Or,thethreegroupsareindependentlyselectedfromhalogen,
monoormulticyclic(includinghalosubstituted)aryls,alkyls,alkenylcompounds,andmixturesthereof,preferredare
alkenylgroupshaving1to20carbonatoms,alkylgroupshaving1to20carbonatoms,alkoxygroupshaving1to20
carbonatomsandarylgroupshaving3to20carbonatoms(includingsubstitutedaryls).Or,thethreegroupsarealkyls
having1to4carbongroups,phenyl,naphthylormixturesthereof.Evenor,thethreegroupsarehalogenated,or
fluorinated,arylgroups.Or,theneutralstoichiometricactivatoristrisperfluorophenylboronortrisperfluoronaphthylboron.
"Substitutedalkyl"referstoanalkylasdescribedinwhichoneormorehydrogenatomsofthealkylisreplacedbyanother
groupsuchasahalogen,aryl,substitutedaryl,cycloalkyl,substitutedcycloalkyl,andcombinationsthereof.Examplesof
substitutedalkylsinclude,forexample,benzyl,trifluoromethyl,andthelike.
Ionicstoichiometricactivatorcompoundsmaycontainanactiveproton,orsomeothercationassociatedwith,butnot
coordinatedto,oronlylooselycoordinatedto,theremainingionoftheionizingcompound.Suchcompoundsandthelike
aredescribedinEuropeanpublicationsEPA0570982EPA0520732EPA0495375EPBl0500944EPA0277
003EPA0277004US5,153,157US5,198,401US5,066,741US5,206,197US5,241,025US5,384,299US
5,502,124.
Preferably,thestoichiometricactivatorsincludeacationandananioncomponent,andmayberepresentedbythe
followingformula:
(LH)d+.(Ad)(VII)
wherein:LisaneutralLewisbaseHishydrogen(LH)+isaBronstedacidAd"isanoncoordinatinganionhavingthe
chargedanddisanintegerfrom1to3.Thecationcomponent,(LH)d+mayincludeBronstedacidssuchasprotonsor
protonatedLewisbasesorreduciblecatalystscapableofprotonatingorabstractingamoiety,suchasanakyloraryl,from
thebulkyligandmetalloceneorGroup15containingtransitionmetalcatalystprecursor,resultinginacationictransition
metalspecies.
Theactivatingcation(LH)^"1"maybeaBronstedacid,capableofdonatingaprotontothetransitionmetalcatalytic
precursorresultinginatransitionmetalcation,includingammoniums,oxoniums,phosphoniums,silyliumsandmixtures
thereof,orammoniumsofmethylamine,aniline,dimethylamine,diethylamine,Nmethylaniline,diphenylamine,
trimethylamine,triethylamine,,dimethylaniline,methyldiphenylamine,pyridine,pbromo,dimethylaniline,pnitro
N,Ndimethylaniline,phosphoniumsfromtriethylphosphine,triphenylphosphine,anddiphenylphosphine,oxomiunsfrom
etherssuchasdimethyletherdiethylether,tetrahydrofurananddioxane,sulfoniumsfromthioethers,suchasdiethyl
thioethersandtetrahydrothiophene,andmixturesthereof.Theactivatingcation(LH)d+mayalsobeanabstractingmoiety
suchassilver,carboniums,tropylium,carbeniums,ferroceniumsandmixtures,orcarboniumsandferroceniums.
Preferably,(L)^+istriphenylcarbonium.
TheanioncomponentAd"includesthosehavingtheformula[Mk+Qn]d_whereinkisanintegerfrom1to3nisaninteger
from26nk=dMisanelementselectedfromGroup13ofthePeriodicTableoftheElements,orboronoraluminum,
andQisindependentlyahydride,bridgedorunbridgeddialkylamido,halide,alkoxide,aryloxide,hydrocarbyl,substituted
hydrocarbyl,halocarbyl,substitutedhalocarbyl,andhalosubstitutedhydrocarbylradicals,saidQhavingupto20carbon
atomswiththeprovisothatinnotmorethan1occurrenceisQahalide.Preferably,eachQisafluorinatedhydrocarbyl
grouphaving1to20carbonatoms,oreachQisafluorinatedarylgroup,oreachQisapentafluorylarylgroup.Examples
ofsuitableAd"alsoincludediboroncompoundsasdisclosedinUS5,447,895.
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Or,theionicstoichiometricactivator(LH)cj+(Ad")isN,Ndimethylaniliniumtetra(perfluorophenyl)borateor
triphenylcarbeniumtetra(perfluorophenyl)borate.Inapreferredembodiment,theactivatorsarerepresentedbythe
followingformula:
(Z)d+Ad(IX)
wherein()^+isthecationcomponentandAd"istheanioncomponentwhereZis(LH)orareducibleLewisAcid,Lisan
neutralLewisbaseHishydrogen(LH)+isaBronstedacidAd_isanoncoordinatinganionhavingthechargedandd
isanintegerfrom1to3.Preferably,whenZisareducibleLewisacid,(Z)d+isrepresentedbytheformula:(Ar3C)+,where
Arisarylorarylsubstitutedwithaheteroatom,aCjtoC4Qhydrocarbyl,orasubstitutedtoC4Qhydrocarbyl,preferably
(Z)d+isrepresentedbytheformula:(Ph3C)+,wherePhisphenylorphenylsubstitutedwithaheteroatom,atoC4Q
hydrocarbyl,orasubstitutedQtoC4Qhydrocarbyl.Inapreferredembodiment,thereducibleLewisacidistriphenyl
carbenium.
Inanotherembodiment,theactivatorcomprisesa"Bulkyactivator"whichisdefinedtobeionicstoichiometricactivators
representedbythefmula:
where:
eachR1is,independently,ahalide,preferablyafluoride
eachR2is,independently,ahalide,atoC20substitutedaromatichydrocarbylgrouporasiloxygroupoftheformula0Si
Ra,whereRaisatoC20substitutedorunsubstitutedhydrocarbylorhydrocarbylsilylgroup(preferablyR2isafluorideora
perfluorinatedphenylgroup)
eachR3isahalide,toC20substitutedaromatichydrocarbylgrouporasiloxygroupoftheformula0SiRa,whereRaisa
CjtoC20substitutedorunsubstitutedhydrocarbylorhydrocarbylsilylgroup(preferablyR3isafluorideoraperfluorinated
aromatichydrocarbylgroup)whereinR2andR3canformoneormoresaturatedorunsaturated,substitutedor
unsubstitutedrings(preferablyR2andR3formaperfluorinatedphenylring)(Z)d+isthecationcomponentwhereZis(L
H)orareducibleLewisAcid,LisaneutralLewisbaseHishydrogen(LH)+isaBronstedacidanddisanintegerfrom1
to3whereintheboronanioncomponenthasamolecularweightofgreaterthan1020g/molandwhereinatleastthreeof
thesubstituentsontheBatomeachhaveamolecularvolumeofgreaterthan250cubicA,alternatelygreaterthan300
cubicA,oralternatelygreaterthan500cubicA.
"Molecularvolume"isusedhereinasanapproximationofspatialstericbulkofanactivatormoleculeinsolution.
Comparisonofsubstituentswithdifferingmolecularvolumesallowsthesubstituentwiththesmallermolecularvolumeto
beconsidered"lessbulky"incomparisontothesubstituentwiththelargermolecularvolume.Conversely,asubstituent
withalargermolecularvolumemaybeconsidered"morebulky"thanasubstituentwithasmallermolecularvolume.
Preferably,anactivationmethodusingionizingioniccompoundsnotcontaininganactiveprotonbutcapableofproducing
abulkyligandmetallocenecatalystcationandtheirnoncoordinatinganionarealsocontemplated,andaredescribedin
EPA0426637EPA0573403andUS5,387,568.
OtheractivatorsincludethosedescribedinPCTpublicationWO98/07515suchastris
(2,2',2"nonafluorobiphenyl)fluoroaluminate,whichpublicationisfullyincorporatedhereinbyreference.Combinationsof
activatorsarealsocontemplatedbytheinvention,forexample,alumoxanesandionizingactivatorsincombinations,see
forexample,EPB10573120WO94/07928WO95/14044US5,153,157and5,453,410.
OthersuitableactivatorsaredisclosedinWO98/09996,incorporatedhereinbyreference,whichdescribesactivating
bulkyligandmetallocenecatalystcompoundswithperchlorates,periodates,andiodatesincludingtheirhydrates.
Otheractivatorsormethodsforactivatingabulkyligandmetallocenecatalystcompoundaredescribedin,forexample,US
5,849,8525,859,6535,869,723PCTpublicationsWO98/32775andWO99/42467(dioctadecylmethylammonium
bis(tris(pentafluorophenyl)borane)benzimidazolide).
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Itiswithinthescopeofthisinventionthatcatalystcompoundscanbecombinedwithoneormoreactivatorsoractivation
methodsdescribedabove.Forexample,acombinationofactivatorshavebeendescribedinUS5,153,1575,453,410
EuropeanpublicationEPB10573120PCTpublicationsWO94/07928andWO95/14044.Thesedocumentsalldiscuss
theuseofanalumoxaneandanionizingactivatorwithabulkyligandmetallocenecatalystcompound.
Thecatalystsystemsusedtoproducethepresentcopolymermayalsoincludeasupportmaterialorcarrier.Forexample,
theoneormorecatalystcomponentsand/oroneormoreactivatorsmaybedepositedon,contactedwith,vaporizedwith,
bondedto,orincorporatedwithin,adsorbedorabsorbedin,oron,oneormoresupportsorcarriers.Thesupportmaterial
maybeanyoftheconventionalsupportmaterials.Preferably,thesupportmaterialisaporoussupportmaterial,for
example,talc,inorganicoxidesandinorganicchlorides.Othersupportmaterialsincluderesinoussupportmaterialssuch
aspolystyrene,functionalizedorcrosslinkedorganicsupports,suchaspolystyrenedivinylbenzenepolyolefinsor
polymericcompounds,zeolites,clays,oranyotherorganicorinorganicsupportmaterialandthelike,ormixturesthereof.
TypicalsupportmaterialsareinorganicoxidesthatincludeGroup2,3,4,5,13,or14metaloxides,suchassilica,which
mayormaynotbedehydrated,fumedsilica,alumina(WO99/60033),silicaalumina,andmixturesthereof.Otheruseful
supportsincludemagnesia,titania,zirconia,magnesiumchloride,montmorillonite,phyllosilicate,zeolites,talc,clays,and
thelike.Also,combinationsofthesesupportmaterialsmaybeused,forexample,silicachromium,silicaalumina,silica
titania,andthelike.AdditionalsupportmaterialsmayincludethoseporousacrylicpolymersdescribedinEP0767184Bl,
whichisincorporatedhereinbyreference.OthersupportmaterialsincludenanocompositesasdescribedinWO99/47598,
aerogelsasdescribedinWO99/48605,spherulitesasdescribedinUS5,972,510andpolymericbeadsasdescribedin
WO99/50311.
Whenpresent,thesupportmaterialtypicallyhasasurfaceareaintherangeoffrom10to700m2/g,porevolumeinthe
rangeoffrom0.1to4.0cc/gandaverageparticlesizeintherangeoffrom5to500.Or,thesurfaceareaofthesupport
materialisintherangeoffrom50to500m2/g,porevolumeoffrom0.5to3.5cc/gandaverageparticlesizeoffrom10to
200.Orthesurfaceareaofthesupportmaterialisintherangeoffrom100to400m2/g,porevolumefrom0.8to3.0
cc/gandaverageparticlesizeisfrom5to100.Theaverageporesizeofthesupportmaterialistypicallyintherange
offrom10to1000A,or50to500A,or75to350A.
Preferably,apolyolefincomprisingamultimodalcompositionaldistributionwithrespecttotheincorporationofasecond
olefinwithinafirstolefin,apercentcrystallinityinthepolymerspeciespresent,oracombinationthereof,whereinthe
polymerisproducedbyaprocesscomprisingprovidingabulkliquidphasecomprisingafirstolefinandapolymerization
catalystsysteminabubblecolumnreactorsystemdirectingagaseousstreamcomprisingasecondolefinatleast
partiallythroughthebulkliquidphaseatagasvelocitysufficienttoproduceastreamofbubblestherebycontactingthe
firstolefinandthesecondolefinwiththecatalystsystematatemperatureandapressuresufficienttoproducethe
polyolefin.
Preferably,thefirstmeltingtemperatureofthepolymerisatleast30Chigher,or40Chigher,or50Chigher,or60C
higher,or70Chigher,or80Chigher,or90Chigher,or100Chigherthanasecondmeltingtemperatureasdetermined
accordingtoDSC.Conveniently,thereactorpolymerblendtypicallyhasameltingtemperatureof60Cormore,and
generally70Cormore,suchas80Cormore,forexample90Cormore.Theterm"meltingpoint,"asusedherein,for
thereactorpolymerblend,isthehighesttemperaturepeakamongprincipalandsecondarymeltingpeaksasdetermined
byDSC.Preferably,thereactorpolymerblendmayhaveameltingpointbyDSCrangingfromanupperlimitof130C,
120C,110C,100C,or90C,toalowerlimitof5C,10C,20C,30C,40C,or50C.
Preferably,thereactorblendhasacrystallizationtemperatureof130Corless.Theterm"peakcrystallization
temperature"or"crystallizationtemperature"asusedherein,forthereactorpolymerblend,isthehighesttemperature
peakamongprincipalandsecondarycrystallizationpeaksasdeterminedbyDSC.Preferably,thecrystallinityofthefirst
andthesecondpolymercomponentsinthereactorblendisfarapart,thepolymerblendwillshowtwoindividualpeaksfor
eachcomponent.ThereactorpolymerblendhasacrystallizationtemperaturebyDSCrangingfromanupperlimitof
120C,100C,90C,70C,or40C,toalowerlimitof0C,10C,30C,40C,or70C.
Themeltingtemperaturesofthereactorpolymerblendproduceddirectlyreflectthedegreeofcrystallinityofthecrystalline
polymercomponentintheblend.Thepolymerblendcanhaveahighmeltingtemperatureinawiderangeofdensities.
Preferably,thepolymerproducedhasameltingtemperatureof100Corhigherandadensityof0.920g/cm3orless,or1
10Corhigherandadensityof0.930g/cm3orless,or115Corhigherandadensityof0.880g/cm3orless.Lowervalue
ofdensitymeanssoftermaterials.Alternatively,theinventivepolymerblendshaveshorehardnessfrom30Ato40Das
determinedaccordingtoISO868andameltingtemperatureof110Corhigher.
Preferably,theinreactorpolymerblendshavehighmeltingtemperatureoverawiderangeofdensityfrom0.84to0.95
g/cm3.Themeltingtemperatureoftraditionalrandomcopolymersofethylene/alphaolefinsorpropylene/alphaolefin
decreaseswithdecreasingdensities.Incontrast,theinreactorpolymerblendsexhibitmeltingpointssubstantially
independentofthedensity,particularlywhendensityisbetween0.84to0.95g/cm3.Forexample,themeltingpointsof
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ethylenecopolymerblendsareintherangeof100Cto130Cwhendensityrangesfrom0.84to0.92g/cm3.Preferably,
themeltingpointsofpolymerblendsareintherangeof100Cto125Cwhendensityrangesfrom0.84to0.92g/cm3.
Dependingonthecrystallinitylevelofthesemicrystallinecomponentandthecompositiondifferencebetweenthe
components,thetwocomponentsmaybeimmiscibleandformaphaseseparatedmixturefollowingrecoveryofthe
productfromthereactor.Thepresenceofmultiplephasescanreadilybemeasuredbystandardpolymercharacterization
techniquessuchaslightmicroscopy,electronmicroscopy,oratomicforcemicroscopy(AFM).Twophasepolymerblends
oftenhaveadvantageousproperties,anditisaparticularobjectiveofthisinventiontoproducesuchtwophaseblendsby
directpolymerization.
Alternatively,theinreactorblendsaremiscible.Theinreactorproducedpolymerblendthenhashomogeneous
morphology.Whenalltheindividualcomponentsarecapableofcrystallizingtoalimitedextent,theyareatleastpartially
cocrystallized.
Incontrast,a"homogeneousblend"isacompositionhavingsubstantiallyonemorphologicalphaseinthesamestate.For
example,ablendoftwopolymers,whereonepolymerismisciblewithanotherpolymer,issaidtobehomogeneousinthe
solidstate.SuchmorphologyisdeterminedusingAFM.Bymiscibleitismeantthattheblendoftwoormorepolymers
exhibitssinglephasebehaviorfortheglasstransitiontemperature,e.g.,theTgwouldexistasasingle,sharptransition
temperatureonadynamicmechanicalthermalanalyzer(DMTA)traceoftan(i.e.,theratioofthelossmodulustothe
storagemodulus)versustemperature.Bycontrast,twoseparatetransitiontemperatureswouldbeobservedforan
immiscibleblend,typicallycorrespondingtothetemperaturesforeachoftheindividualcomponentsoftheblend.Thus,a
polymerblendismisciblewhenthereisoneTgindicatedontheDMTAtrace.Amiscibleblendishomogeneous,whilean
immiscibleblendisheterogeneous.
Generally,thereactorblendhasacrystallinityof80%orless,typically70%orless,ascalculatedusingheatoffusion
obtainedfromDSCanalysis.Asumoftheheatoffusionfromallmeltingpeaksisusedwhenmultiplemeltingpeaksare
present.Theheatoffusionfor100%crystallinityisselectedfromthehomopolymeroftheprimarycompositioninthe
reactorpolymerblend.Forexample,whenthepolymerblendismadeofanethylenehomopolymerandethylene/hexene
copolymer,ethyleneistheprimarycomposition,andtheheatoffusionof100%crystallinepolyethyleneisused(e.g.,290
J/g).Preferably,thereactorproducedpolymerblendhasaheatoffusionbetween10and270J/g,forexamplebetween
30and200J/g,suchasbetween40and200J/g.
Preferably,thereactorblendhasaweightaveragemolecularweightofbetween10,000and2,000,000g/mol,suchas
between20,000and1,500,000g/molwithapolydispersityindex(PDI=Mw/Mn)intherangeof1.5to40.The
polydispersityindexispartiallydependentonthecatalystsandprocessconditionemployedinthepolymerizationprocess.
Forexample,polymerizationinvolvingmultiplecatalystsmayproduceacopolymerwithbroaderormultimodalmolecular
weightdistribution.Multiplereactorswithdifferentpolymerizationconditionsmayproducepolymerblendwithmultimodal
molecularweightdistributions.Preferably,thepolymerblendproducedmayhaveabimodal,ormultimodalmolecular
weightdistribution.Bybimodalormultimodalismeantthatapolymermayhavetwoormoremodes,whichmaybe
manifestbyadifferentialscanningcalorimetry(DSC)tracehavingmorethanonepeakorinflectionpoints,asizeexclusion
chromatogram(SEC)havingmorethanonepeakorinflectionpoints,and/orthelike.Aninflectionpointisthatpointwhere
thesecondderivativeofthecurvechangesinsign(e.g.,fromnegativetopositiveorviceversa).
Inanotherembodiment,thedifferenceinpropylenecontentbetweenthetwocomponentsissuchthatoneissemi
crystallineandtheotherisamorphous.SemicrystallineisdefinedashavingameltingpointasmeasuredbyDSCanda
crystallinityofleast5%whileamorphousisdefinedaseithertheabsenceofaDSCmeltingpointoracrystallinityofless
than5%.Thesemicrystallinepolymersofthisinventiongenerallyhavemeltingpointsof40Cto140C,dependingonthe
polymercomposition.DSCmeasurementsaremadebytheproceduredescribedintheExamplessection.Propylene
copolymersaregenerallyamorphousatethylenecontentsbetween20wt%and70wt%withthecatalystsofthisinvention.
Ifapolymercomponentwithethylenecrystallinityisdesiredintheblend,thisshouldhaveinexcessof60wt%ethylene.
Ontheotherhand,ifacomponentisdesiredwithpropylenecrystallinity,itshouldhavelessthan20wt%ethylene.
Furthermore,inthiscase,itmaybenecessarytouseacatalystsystemthatiscapableofpolymerizingpropylene
stereospecifically.Catalystsystemsthatproduceisotacticpropylenesequencesaresuitableforuseherein.Inapreferred
embodiment,thecatalystsystemcomprisesabridgedbisindenylhafnium(orzirconium)dialkylordihalogencompound
havinghydrocarbyl(Qto
C20)substitutionsatthe2and4positions,suchasdimethylsilylbis(2methyl,4phenylindenyl)hafniumdimethylor
dimethylsilylbis(2methyl,4phenylindenyl)hafniumdichloride.EXAMPLES
TheinventionwillnowbemoreparticularlydescribedwithreferencetotheaccompanyingnonlimitingExamples.
Peakmeltingpoint,Tm,(alsoreferredtoasmeltingpoint),peakcrystallizationtemperature,Tc,(alsoreferredtoas
crystallizationtemperature),glasstransitiontemperature(Tg),heatoffusion(AHforHf),andpercentcrystallinitywere
determinedusingthefollowingDSCprocedureaccordingtoASTMD341803.Differentialscanningcalorimetric(DSC)
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datawereobtainedusingaTAInstrumentsmodelQ100machine.Samplesweighingapproximately5to10mgwere
sealedinanaluminumhermeticsamplepan.TheDSCdatawererecordedbyfirstgraduallyheatingthesampleto200C
atarateof10C/minute.Thesamplewaskeptat200Cfor2minutes,thencooledto90Catarateof10C/minute,
followedbyanisothermalfor2minutesandheatingto200Cat10C/minute.Boththefirstandsecondcyclethermal
eventswererecorded.Areasundertheendothermicpeaksweremeasuredandusedtodeterminetheheatoffusionand
thepercentofcrystallinity.Thepercentcrystallinityiscalculatedusingtheformula,[areaunderthemeltingpeak
(Joules/gram)/B(Joules/gram)]*100,whereBistheheatoffusionforthe100%crystallinehomopolymerofthemajor
monomercomponent.ThesevaluesforBaretobeobtainedfromthePolymerHandbook,FourthEdition,publishedby
JohnWileyandSons,NewYork1999,providedhowever,thatavalueof189J/g(B)isusedastheheatoffusionfor
100%crystallinepolypropylene,avalueof290J/gisusedfortheheatoffusionfor100%crystallinepolyethylene.The
meltingandcrystallizationtemperaturesreportedherewereobtainedduringthesecondheating/coolingcycleunless
otherwisenoted.
Forpolymersdisplayingmultipleendothermicandexothermicpeaks,allthepeakcrystallizationtemperaturesandpeak
meltingtemperatureswerereported.Theheatoffusionforeachendothermicpeakwascalculatedindividually.The
percentcrystallinityiscalculatedusingthesumofheatoffusionsfromallendothermicpeaks.Someofthepolymerblends
producedshowasecondarymelting/coolingpeakoverlappingwiththeprincipalpeak,whichpeaksareconsidered
togetherasasinglemelting/coolingpeak.Thehighestofthesepeaksisconsideredthepeakmelting
temperature/crystallizationpoint.Fortheamorphouspolymers,havingcomparativelylowlevelsofcrystallinity,themelting
temperatureistypicallymeasuredandreportedduringthefirstheatingcycle.PriortotheDSCmeasurement,thesample
wasaged(typicallybyholdingitatambienttemperatureforaperiodof2days)orannealedtomaximizethelevelof
crystallinity.MorphologydatawereobtainedusinganAtomicForceMicroscope(AFM)intappingphase.Allspecimens
wereanalyzedwithin8hoursaftercryofacingtopreventspecimenrelaxation.Duringcryofacing,thespecimenswere
cooledto130CandcutwithdiamondknivesinaReichertcryogenicmicrotome.Theywerethenstoredinadissector
underflowingdrynitrogengastowarmuptoambienttemperatureswithoutcondensationbeingformed.Finally,thefaced
specimensweremountedinaminiaturesteelviseforAFManalysis.TheAFMmeasurementswereperformedinairona
NanoScopeDimension3000scanningprobemicroscope(DigitalInstrument)usingarectangular225mmSicantilever.
Thestiffnessofthecantileverwas~4N/mwitharesonancefrequencyof~70kHz.Thefreevibrationamplitudewashigh,
intherangeof80nmto100nm,withaRMSsettingof3.8volts.Whilethesetpointratiowasmaintainedatavalueequal
toorlowerthan0.5,thecontactsetpointwasadjustedroutinelytoensurerepulsivecontactswithpositivephaseshifts.
Thecantileverwasrunningatorslightlybelowitsresonancefrequency.
Themorphologiesofthevarioussampleswerealsoexaminedusingascanningelectronmicroscope(SEM,JSM840).For
theblends,thesampleswerefirstmicrotomedinliquidnitrogen,thenthesurfaceswereetchedinheptaneatroom
temperaturefordifferenttimerangingfrom30sto48hdependingontheblendcompositiontoremovetheelastomer
phaseforSEMobservation.Forthefoams,theinspectedsurfaceswerefreezefracturedinliquidnitrogen,andthen
directlyobservedbySEM.
TransmissionElectronMicroscopy(TEM)wasusedtostudydetailsoftheinterfacebetweentheethylene/propylene
copolymerandthesemicrystallinepolypropylenephases.TEMsampleswerepreparedbystainingthesampleswithRu04
andthencutting~80nmthicksectioninanultracryomicrotome.TheinstrumentusedwasFEITecnaiG2F20STFEG
TEMoperatedat200kV.ImageswererecordedinScanningTEM(STEM)modeusingtheHighAngleAnnularDarkField
(HAADF)detector.Lowerdensityandamorphouspolymerstakeupmorestainthandohigherdensityandmorecrystalline
components.TheSTEMHAADFimagesarepresentedininvertedcontrastsothatareaswithlowerdensityappearbright
andareaswithhigherdensityappeardark.
Theethylenecontentofethylene/propylenecopolymerswasdeterminedusingFTIRaccordingtothefollowingtechnique.
Athinhomogeneousfilmofpolymer,pressedatatemperatureof150C,wasmountedonaPerkinElmerSpectrum2000
infraredspectrophotometer.Afullspectrumofthesamplefrom600cm1to4000cm1wasrecordedandtheareaunder
propylenebandat~1165cm1andtheareaofethylenebandat732cm1inthespectrumwerecalculated.Thebaseline
integrationrangeforthemethylenerockingbandisnominallyfrom695cm1totheminimumbetween745and775cm1.
Forthepolypropylenebandthebaselineandintegrationrangeisnominallyfrom1195to1126cm1.Theethylenecontent
inwt%wascalculatedaccordingtothefollowingequation:
ethylenecontent(wt%)=72.69886.495+13.6962(XI)whereX=AR/(AR+1)andARistheratiooftheareaforthepeak
at~1165cm1totheareaofthepeakat732cm1.
Molecularweights(numberaveragemolecularweight(Mn),weightaveragemolecularweight(Mw),andzaverage
molecularweight(Mz))weredeterminedusingaPolymerLaboratoriesModel220hightemperatureSECwithonline
differentialrefractiveindex(DRI),lightscattering,andviscometerdetectors.ItusedthreePolymerLaboratoriesPLgel10
mMixedBcolumnsforseparationusingaflowrateof0.54ml/minandanominalinjectionvolumeof300^.The
detectorsandcolumnsarecontainedinanovenmaintainedat135C.Thelightscatteringdetectorisahightemperature
miniDAWN(WyattTechnology,Inc.).Theprimarycomponentsareanopticalflowcell,a30mW,690nmlaserdiodelight
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source,andanarrayofthreephotodiodesplacedatcollectionanglesof45,90,and135.Thestreamemergingfromthe
SECcolumnsisdirectedintotheminiDAWNopticalflowcellandthenintotheDRIdetector.TheDRIdetectorisan
integralpartofthePolymerLaboratoriesSEC.TheviscometerisahightemperatureviscometerpurchasedfromViscotek
CorporationandcomprisingfourcapillariesarrangedinaWheatstonebridgeconfigurationwithtwopressuretransducers.
Onetransducermeasuresthetotalpressuredropacrossthedetector,andtheother,positionedbetweenthetwosidesof
thebridge,measuresadifferentialpressure.TheviscometerisinsidetheSECoven,positionedaftertheDRIdetector.
Thedetailsofthesedetectorsaswellastheircalibrationshavebeendescribedby,forexample,T.Sun,P.Brant,R.R.
Chance,andW.W.Graessley,inMacromolecules,Volume34,Number19,pp.68126820,(2001),incorporatedhereinby
reference.
SolventfortheSECexperimentwaspreparedbyadding6gramsofbutylatedhydroxytoluene(BHT)asanantioxidantto
a4literbottleof1,2,4trichlorobenzene(TCB)(AldrichReagentgrade)andwaitingfortheBHTtosolubilize.TheTCB
mixturewasthenfilteredthrougha0.7micronglassprefilterandsubsequentlythrougha0.1micronTeflonfilter.There
wasanadditionalonline0.7micronglassprefilter/0.22micronTeflonfilterassemblybetweenthehighpressurepumpand
SECcolumns.TheTCBwasthendegassedwithanonlinedegasser(Phenomenex,ModelDG4000)beforeenteringthe
SEC.Polymersolutionswerepreparedbyplacingdrypolymerinaglasscontainer,addingthedesiredamountofTCB,
thenheatingthemixtureat160Cwithcontinuousagitationfor2hours.Allquantitiesweremeasuredgravimetrically.The
TCBdensitiesusedtoexpressthepolymerconcentrationinmass/volumeunitswere1.463g/mlatroomtemperatureand
1.324g/mlat135C.Theinjectionconcentrationrangedfrom1.0to2.0mg/ml,withlowerconcentrationsbeingusedfor
highermolecularweightsamples.Theaveragedmolecularweightreportedinthefollowingtheexampleswereobtained
fromlightscatteringdetectorunlessotherwisenoted.
Temperaturerisingelutionfractionation(TREF)analysisisconductedusingPolymerCharTREF200(PolymerChar,
Valencia,Spain)equippedwithaninfrareddetectoraccordingtothemethoddescribedbyL.Wilde,T.R.Ryle,D.C.
Knobeloch,I.R.Peat,DeterminationofBranchingDistributionsinPolyethyleneandEthyleneCopolymers,J.Polymer
Science,1982,20,pp.441455.Thepolymersampleisfirstdissolvedin1,2dichlorobenzenewith400ppmofbutylated
hydroxytoluene(BHT)at160Cfor60minutesatapolymerconcentrationof2to6mg/mL.Theresultingsolutionisthen
introducedintoapackedcolumnandstabilizedat140Cfor45minutes.Thepolymersampleisthenallowedtocrystallize
inthepackedcolumnbyslowlyreducingthetemperatureto30Cor0CatacoolingrateoflC/min.Thesampleisthen
firstelutedfromthecolumnbypumpingthesolventthroughthecolumnataflowrateof1.0ml/minfor10minutesat0C
or30C.ATREFchromatogramcurveisthengeneratedbyelutingthecrystallizedpolymersamplefromthecolumnby
slowlyincreasingthetemperatureoftheelutingsolventfrom0Cor30Cto140Catarateof2C/minandelutingsolvent
flowrateof1.0ml/min.Theconcentrationofelutedpolymerismeasuredusingtheinfrareddetector.
Crystallizationanalysisfractionation(CRYSTAF)wasconductedusingaCRYSTAF200unitcommerciallyavailablefrom
PolymerChar,Valencia,Spain.Thesampleisdissolvedin1,2dichlorobenzeneat160Catapolymerconcentrationof0.2
to1.0mg/mlfor1hourandstabilizedat95Cfor45minutes.Thesamplingtemperaturesrangefrom95Cto30Cor
95Cto0Catacoolingrateof0.2C/min.Aninfrareddetectorisusedtomeasurethepolymersolutionconcentrations.
Thecumulativesolubleconcentrationismeasuredasthepolymercrystallizeswhilethetemperatureisdecreased.The
analyticalderivativeofthecumulativeprofilereflectsthecrystallinitydistributionofeachofthepolymercomponentsofthe
reactorpolymerblends.TheCRYSTAFpeaktemperatureandareaareidentifiedbythepeakanalysismoduleincludedin
theCRYSTAFSoftware.TheCRYSTAFpeakfindingroutineidentifiesapeaktemperatureasamaximuminthedw/dT
curveandtheareabetweenthelargestpositiveinflectionsoneithersideoftheidentifiedpeakinthederivativecurve.
BrookfieldviscositywasmeasuredaccordingtheASTMD3236usingaBrookfielddigitalviscometerat190C.
Meltflowrate(MFR)wasdeterminedaccordingtoASTMD1238usingaloadof
2.16kgandatatemperatureof230C.
DynamicMechanicalThermalAnalysis(DMTA)examinesthebehaviorofviscoelasticmaterialsaccordingtotemperature
andfrequencydependentbehavior.Theapplicationofasmallstressproducesadeformation(strain)inthematerial.The
amountofdeformationresultingfromtheappliedstressyieldsinformationconcerningthemoduliofthematerialits
stiffnessanddampingproperties.TheDMTAisacontrolledstressinstrumentappliedinasinusoidalfashionandgivesa
sinusoidalresponseversustime.Asaconsequenceoftheappliedsinusoidalstressthematerialrespondsinanelastic
(storesenergy)andviscous(dissipatesenergy)manner.DMTAseparatestheseresponsesintotwodifferentmoduli
values:ElasticModulus(')andthelossmodulus(E")andinatemperaturesweepthesemoduliaremeasuredfromthe
glassyregion,theplateauregiontotheterminalregion.Theresponseofviscoelasticmaterialsisoutofphasewiththe
inputsignalbyanangledelta().ThetangentofthisangleisequaltotheratioE"/E'anditisavaluableindicatorofthe
relativedampingabilityofthematerial.Anypeakinthetancorrespondstoaregionwherethematerialpropertiesare
changingveryrapidlythematerialisundergoingatransitionorrelaxationsuchasTg(glasstransitiontemperature)and
otherrelaxations.Forpurposeofthisinventionandtheclaimsthereto,TgisdeterminedbyDSC,unlessDSCcannot
determineaTg,thenDMTAshallbeused.
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Examples1to3
Theseexamplesdemonstratethepolymerizationofinreactorblendsinacontinuousstirredtanksolutionprocessto
produceethylene/propylenecopolymers.Allpolymerizationswereperformedinaliquidfilled,singlestagecontinuous
reactorsystem.Thereactorwasa0.5literstainlesssteelautoclavereactorandwasequippedwithastirrer,awater
cooling/steamheatingelementwithatemperaturecontroller,andapressurecontroller.Solvents,ethylene,propyleneand
comonomerswerefirstpurifiedbypassingthroughathreecolumnpurificationsystem.Thepurifiedsolventsand
monomerswerethenchilledto15Cbypassingthroughachillerbeforebeingfedintothereactorthroughamanifold.
Solventandmonomersweremixedinthemanifoldandfedintothereactorthroughasingletube.Allliquidflowrateswere
measuredusingBrooksfieldmassflowmetersorMicroMotionCoriolistypeflowmeters.Atthetemperatureandpressure
conditionsdescribedbelow,theethylenepresentinthereactorisingaseous"bubble"form.
Asanimpurityscavenger,250mloftrinoctylaluminum(TNOA)(25wt%inhexane,SigmaAldrich)wasdilutedin22.83
kilogramofisohexane.TheTNOAsolutionwasstoredina37.9litercylinderundernitrogenblanket.Thesolutionwas
usedforallpolymerizationrunsuntil90%ofconsumption,andthenanewbatchwasprepared.Thefeedratesofthe
TNOAsolutionwereadjustedinarangefrom0(noscavenger)to4mlperminutetoachieveamaximumcatalystactivity.
ThereactorwasfirstpreparedbycontinuouslyN2purgingatamaximumallowedtemperature,thenpumpingisohexane
andscavengersolutionthroughthereactorsystemforatleastonehour.Monomersandcatalystsolutionswerethenfed
intothereactorforpolymerization.Oncetheactivitywasestablishedandthesystemreachedequilibrium,thereactorwas
linedoutbycontinuingoperationofthesystemundertheestablishedconditionforatimeperiodofatleastfivetimesof
meanresidencetimepriortosamplecollection.Theresultingmixture,containingmostlysolvent,polymerandunreacted
monomers,wascollectedinacollectionbox.Thecollectedsampleswerefirstairdriedinahoodtoevaporatemostofthe
solvent,andthendriedinavacuumovenatatemperatureof90Cfor12hours.Thevacuumovendriedsampleswere
weighedtoobtainyields.
Catalystusedwas[di(ptriethylsilylphenyl)methylene](cyclopentadienyl)(3,8ditbutylfluorenyl)hafniumdimethylcatalyst
(obtainedfromAlbemarle).Thecatalystwaspreactivatedwith,dimethylaniliniumtetrakis(pentafluorophenyl)borateat
amolarratioof1:1in900mloftoluene.Thedetailedrunconditionsandsomeoftheanalyticaldataformaterials
producedinthesepolymerizationexamplesarelistedinTable1.Thescavengerfeedrateandcatalystfeedratewere
adjustedtoreachthetargetedconversionlistedinTable1foreachexample.Molecularweightvalueslistedinthistable
wereresultsbasedonlightscatteringdetector.
Standardcubiccentimeterperminute
AllthepolymersproducedinExamples13havetwomeltingpeaksonthesecondheatingcycleandtwocrystallization
peaksonthesamecoolingcycle.Thisindicatesthepresenceofpolymerblendsfrominreactorproducts.TheDSCtrace
ofthepolymerblendproducedinExample2isshowninFIG.3.
Examples4to6
Examples46demonstratethepolymerizationofpropylene/ethylenecopolymerusingracdimethylsilylbis(indenyl)hafnium
dimethyl.ThemetallocenewaspreactivatedwithMe3Htetrakis(pentafluorophenyl)borateatamolarratioof1:1in
toluene.ThepolymerizationprocedurewasthesameasthatemployedinExample13.Thescavengerfeedrateand
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catalystfeedratewereadjustedtoreachthetargetedconversionlistedinTable2foreachexample.Thedetailed
polymerizationconditionsandsomeofanalyticaldataformaterialsproducedinthesepolymerizationexamplesarelisted
inTable2.Atthetemperatureandpressureconditionsdescribed,theethylenepresentinthereactorisingaseous
"bubble"form.
Examples7to9
Examples79demonstratethepolymerizationofpropylene/ethylenecopolymerusingracdimethylsilylbis(indenyl)hafnium
dimethyl.ThemetallocenewaspreactivatedwithMe3Htetrakis(pentafluorophenyl)borateatamolarratioof1:1in
toluene.Thedetailedpolymerizationconditionsandsomeoftheanalyticaldataformaterialsproducedinthese
polymerizationexamplesarelistedinTable3.Thescavengerfeedrateandcatalystfeedratewereadjustedtoreachthe
targetedconversionlistedinTable3foreachexample.Atthetemperatureandpressureconditionsdescribedbelow,the
ethylenepresentinthereactorisingaseous"bubble"form.
Examples10to12
Examples1012demonstratethepolymerizationofpropylene/ethylenecopolymerusingracdimethylsilylbis(indenyl)
hafniumdimethyl.Themetallocenewaspreactivatedwith,dimethylaniliniumtetrakis(pentafluorophenyl)borateata
molarratioof1:1intoluene.ThepolymerizationprocedurewasthesameasthatemployedinExamples13.The
detailedpolymerizationconditionsandsomeoftheanalyticaldataformaterialsproducedinthesepolymerization
examplesarelistedinTable4.Thecatalystfeedratewasadjustedtoreachtheconversionlistedinthistableforeach
polymerizationrun.
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PATENTCITATIONS
CitedPatent
Filingdate
Publicationdate
Applicant
Processforproducingpolyolefinsandpolyolefincatalysts
KR100999555B1*
Title
Titlenotavailable
US5064797*
Mar6,1990
Nov12,1991
PhillipsPetroleum
Company
US20040192861*
Mar25,2003
Sep30,2004
Equistar
ChemicalsL.P.
Cascadedpolyolefinslurrypolymerizationemployingdisengagement
vesselbetweenreactors
US20100152390*
Dec15,2009
Jun17,2010
DeGraciaCarlos
U
HeterogeneousInReactorPolymerBlends
Mar15,2012
Sumitomo
Chemical
Company,
Limited
Ethylenealphaolefincopolymer,moldedarticle,catalystfor
copolymerization,andmethodforproducinganethylenealphaolefin
copolymer
US20120065346*
May27,2010
*Citedbyexaminer
CLASSIFICATIONS
InternationalClassification
C08F2/01,C08F4/64,C08F10/00,C08F210/16
CooperativeClassification
C08F210/16
LEGALEVENTS
Date
Code
Event
Description
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Aug6,2014
121
Refdocumentnumber:13862335
Kindcodeofrefdocument:A1
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