Metallocene Technology in Commercial Applications

307 Pages·1999·8.899 MB·307\307

by  Benedikt, G.M., Dr.(Eds.)

METALLOCENE
TECHNOLOGY
in Commercial Applications
Dr. George M. Benedikt, Editor
SocietyofPlasticsEngineers
PlasticsDesignLibrary
Copyright©1999,PlasticsDesignLibrary.Allrightsreserved.
ISBN1-884207-76-6
LibraryofCongressCardNumber98-89319
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Preface
Therevolutioninpolyolefintechnologystartedduringthelastdecadeofthe20thcenturycon-
tinuestodayatanever-fasterpace.Wearetalkingaboutthemetalloceneandsinglesitecata-
lyst based homo and copolyolefins (mPOs) with their well-defined structures and closely
controlledmoleculararchitectures.Theircapabilitiestocompete,onthebasisoftheirtailored
propertiesagainsttraditionalpolymerssuchasABS,PVC,thermoplasticelastomers(TPEs)
and others combined with a favorable cost structure constitutes a fertile resource for im-
provedmaterials.
Since the publication last year of “Metallocene Catalyzed Polymers”, where the ad-
vancesincatalysisandpolymerizationtechniqueswherediscussedindetailtogetherwiththe
polymer properties, processing and the initial markets, we have witnessed a tremendous
growthinthecommercialdevelopmentofthesenovelmaterials.Theyaremoreandmoretar-
getedonanimprovedcost/performancebasisatreplacingorcomplementingthetraditional
materials.Wehavealsowitnessedsomeinroadsofthenovelmaterialsinotherareasnotcon-
templatedinitiallysuchaselastomers,adhesivesandengineeringthermoplastics.
Oneoftheinevitablebutexpectedaspectsofthenewproduct/processdevelopmentina
freemarketeconomyistheprotectionofintellectualproperty.Inmanycasesthisleadstolong
drawnandexpensivelitigationbetweenmajororminorplayerswithadverseeffectsontimely
commercialdevelopment.Thereforetherecentlyannounced(seeC&ENewsJune21st,1999)
agreementbetweenDowChemicalCo.,ExxonandUnivationTechnologies(alicensingjoint
venture between Exxon and Union Carbide Corp.) to settle rather than litigate their patent
rights constitutes certainly a step in the right direction of an increased competitive market
growth for metallocene polyolefins. This is important since besides the two major players,
DowChemicalCo.andExxon,manymorecompanieshaveannouncestheircommercialef-
forts for metallocene polyolefins. (BASF, DSM, TOTALFINA, MITSUI, BOREALIS,
EQUISTAR,UnionCarbide,etc)
The present book is based on 40 papers presented at the ANTEC 98 and 99 and other
conferences.Asageneralobservation,thecenterofgravityhasshiftedfrompolymermanu-
facturingtoapplicationdevelopment.Asaconsequencethereareonlytwocatalysisrelated
papersinthechapteronCatalyticSystems.Theydealwiththepolymerizationresultsusing
supportedsinglesitecatalysts(formPEs),aswellaswiththedetrimentaleffectoftheresidual
triethylaluminumonthemolecularweightofelastomericPP.
viii MetalloceneTechnology
Thebulkofthebookdescribes,inthechapterofProcessing,thedevelopmentworkin
adapting these new, now commercial materials into specific applications, using appropriate
processingmethodsandtechniques.
Insomecasesmetallocenepolyolefinscanbeusedinapplicationsdirectly.Forinstance
the second-generation metallocene PEs (EZP-mPE) presented by Univation Technologies
exhibitcontrolledMWD(comparedwiththefirstgenerationthatwasverynarrow,andthus
hardertoprocess),compositionaldistribution,longchainbranchinganddistribution.These
structural properties lead to a much tougher film in comparison with the typical blends of
Ziegler-NattaZN-LL/LDPEs.Consequentlythinnerfilmsarepossible,thisdowngaugingre-
sultingincostsavings.Additionally,theheatsealabilityofmPEsisalsosuperior.
Inmanyothercasesoneuniquematerialcannotprovidetheentirerangeofdesiredprop-
erties. In this case blends are preferred, and this is no different for mPOs. Blends can be
formulatedtotargetexistingapplications,whiletakingadvantageofthepropertiesafforded
totheblendbythemPOs.Whenevertheuseofblendsisnecessaryonehastotackletheissues
ofmiscibilityandcompatibility.It’sworthdirectingthereader’sattentionatanewconceptin
polymerblend,presentedbyagroupfromExxon,namelythespheruliteboundarystrength-
ening. This is achieved by a copolymer that migrates to the spherulite boundary and
cocrystallizescreatingadditionalinterspheruliticlinks.Thestrengtheningagentstudiedwas
anisotacticPP-atacticPPmadebysinglesitecatalysis,containingadditionallysodiumbenzo-
ate as nucleating agent. Another interesting blend application presented by Dow Chemical
Co. workers uses an ethylene-styrene interpolymer made using INSITE technology. This
product could be blended with either atactic PS, or PP, giving unique properties. Uses as
moldings,filmsandfoamsarecontemplated.
AllmajorprocessingtechniqueshavebeenimpactedbythenovelmPOs:extrusion,film
blowing,injectionmolding,foamproduction,fiberspinningandcompositemanufacturing.
Effortsinprocessparameteroptimization,usingthenewmPOsandtheirblendsandreported
inseveralofthepapers,areincludedintheProcessingchapter.Theyencompassfilmapplica-
tionsforfreshfoodpackaging,heatsealing,coextrusion,PPfilmsandapplications,nitrogen
autoclavefoamingandothers.
Separately we grouped the papers studying Structure-Property relationships, includ-
ingrheology,instrumentalanalysis,studyofcrystallization,crystalgrowthkinetics.
InafinalchapterwegroupedthepapersdealingwithpolymerMarkets,marketoutlook
formPOs,theavailabilityandpricingofmonomers,projectedworlddemandforPPaswell
asalongtermlookatPVCmarketsinthenexttwodecades.ThePVCstudyisincludedbe-
cause of the expected future market pressure on the flexible PVC applications from the
metallocenepolyolefins.
Preface ix
We do expect indeed to see in the future a continuation of the metallocene polyolefin
revolution.Today’stechnologyappearstobeonlyina“transitionstate”.Ascompetitionin
themarketplacewillaccelerateand,inturn,asthemarketplacewillexertmorestringentper-
formance demands, novel, higher productivity catalytic systems will temporarily win the
popularitycontest.Weexpecttoseetheintroductionofsomeproductscontainingfunctional
groups,wealsoexpectcompetitionfromcatalyticsystemsbasedonNi,FePd,ratherthanZr,
Ti,Hf.
GeorgeM.Benedikt
TheBFGoodrichCompany
Brecksville,Ohio
August,1999
Table of Contents
Preface vii
GeorgeM.Benedikt
CatalyticSystems
Single-SiteSupportedCatalystsforEthylene 1
A.Mu(cid:1)oz-Escalona,L.Mendez,B.Pe(cid:1)a,P.Lafuente,JSancho,
W.Michiels,G.HidalgoandMa.Fca.Martinez-Nu(cid:1)ez
SynthesisofHigh-Molecular-WeightElastomericPolypropylenewith
Half-Titanocene/MAOCatalysts 9
OingWu,BenhengXie,MeiranXie,RuiChen
PrecessingMethods
Blending
IsMetallocenePolyethyleneBlendwithHDPEMoreCompatibleThanwithPP? 17
D.Rana,K.Cho,B.H.LeeandS.Choe
SpheruliteBoundaryStrengthening:ANewConceptinPolymerBlends 23
A.Lustiger,CN.MarzinskyandR.R.Mueller
ModificationofSyndiotacticPolystyrene 29
J(cid:2)rgKressler,RalfThomann
BlendsofEthylene/StyreneInterpolymersandOtherPolymers:Benefitsin
Applications 37
C.F.Diehl,M.J.Guest,B.I.Chaudhary,Y.W.Cheung,
W.R.VanVolkenburgh,B.W.Walther
Extrusion
EasyProcessingMetallocenePolyethylene 47
Ching-TaiLue
EffectofMetallocenePolyethyleneonHeatSealingPropertiesofLow
DensityPolyethyleneBlends 53
JuanD.Sierra,Mar(cid:3)adelPilarNoriegaandTimA.Osswald
ExtrusionOperationWindowforFilledMetallocenePolyethylenes 61
Mar(cid:3)adelPilarNoriegaandTimA.Osswald,OmarA.Estrada
ProcessingTrendsofMetalloceneLinearLowDensityPolyethylenesand
TheirInfluenceonSingleScrewDesign 69
iv MetalloceneTechnology
K.R.Slusarz,C.A.Ronaghan,andJ.P.Christiano
InfluenceofmPEGradesontheDynamicPropertiesofPP/mPE-Blends 77
FrankRaueandGottfriedW.Ehrenstein
“Single-Site”CatalyzedPolyolefinforFresh-CutProducePackaging.
AComparisonBetweenMonoextrudedBlendsandCoextrudedFilm 85
V.Patel,S.Mehta,S.A.OrrothandS.P.McCarthy
RheologyandProcessingExperienceofNewMetallocenePolyolefins 93
AtulKhare,ChuanQin,MichaelT.K.Ling,andL.Woo
FilmForming
PropertiesandFilmApplicationsofMetallocene-BasedIsotacticPolypropylenes 101
AikoHanyuandRustyWheat
PhaseStructureCharacterizationandProcessing-Structure-PropertyRelationships
inLinearLow-DensityPolyethyleneBlownFilms 111
JianjunLu,BaiyiZhaoandHung-JueSue
TheRelativeInfluencesofProcessandResinTime-ScalesontheMDTear
StrengthofPolyethyleneBlownFilms 121
RajendraK.KrishnaswamyandAshishM.Sukhadia
MetalloceneCatalyzedPolyethyleneinBlownFilmApplications.AComparison
BetweenMonoextrudedBlendedFilmsandCoextrudedFilms 129
C.M.Beagan,G.M.McNally&W.R.Murphy
Trade-offsinBlownFilmProcessing-Structure-PropertyBehaviorofLLDPE
TypeResinsfromChromium,MetalloceneandZiegler-NattaCatalysts 137
AshishM.Sukhadia
InjectionMolding
TransparentMetallocene-PolypropyleneforInjectionMolding 147
J.R(cid:2)sch,J.R.Grasmeder
EquipmentDesignConsiderationsforProcessingwithMetalloceneResins 153
AndrewW.Christie
OtherProcessingMethods
ProductandProcessDevelopmentsintheNitrogenAutoclaveProcessfor
PolyolefinFoamManufacture 157
D.E.EavesandN.Witten
PropertiesofSyndiotacticPolypropyleneFibersProducedfromMeltSpinning 167
MohanGownder
TableofContents v
MeltSpinningofSyndiotacticPolypropylene:StructureDevelopmentand
ImplicationsforOrientedCrystallization 177
RaviK.Sura,PrashantDesaiandA.S.Abhiraman
Properties
NewPolyolefinsCharacterizationbyInstrumentalAnalysis 183
CarminaGartnerandJuanD.Sierra,RogerAvakian
DynamicMeltRheometryUsedtoStudyDegradationofMetallocene
Polyethylene 193
ScottH.Wasserman,GeorgeN.Foster,DouglasJ.Yacka
MeltRheologyandProcessabilityofConventionalandMetallocene
Polyethylenes 201
ChoonK.Chai
RheologyofMetallocene-CatalyzedPolyethylenes.TheEffectsofBranching 209
SujanE.BinWadudandDonaldG.Baird
ExtensionalandShearRheologyofMetallocene-CatalyzedPolyethylenes 217
SujanE.BinWadudandDonaldG.Baird
ACriterionfortheOnsetofGrossPolyolefins:MolecularStructureEffect 223
SeungohKimandJohn.M.Dealy
RelationshipBetweenStructureandRheologyofConstrainedGeometry
CatalyzedandMetallocenePolyethylenes 231
PaulaWood-AdamsandJohnM.Dealy
TheInfluenceofSequenceLengthDistributionontheLinearCrystalGrowth
ofEthylene-OcteneCopolymers 239
JohnE.Wagner,SamirAbu-Iqyas,KennethMonarandPaulJ.Phillips
CrystallizationandMicrostructureofZiegler-NattaandMetalloceneBased
IsotacticPolypropylenes:SimulationandExperiment 247
Y.ChurdpuntandA.I.Isayev
CrystallizationofEthylene-OcteneCopolymersatHighCoolingRates 257
PaulJ.PhillipsandJohnWagner
KineticsofNon-IsothermalCrystallizationSyndiotacticPolypropylene:
Avrami,Ozawa,andKissingerApproaches 263
PittSupapholandJosephE.Spruiell
HighTemperatureFlexiblePolyolefinsaUser’sPerspective 275
AtulKhare,SamuelYDing,MichaelT.K.Ling,andL.Woo
vi MetalloceneTechnology
Markets
AnOutlookforMetalloceneandSingleSiteCatalystTechnologyinto
the21stCentury 283
KurtW.Swogger
WorldOlefinsMarkets:IssuesInfluencingAvailabilityandPricing 293
RobinG.Harvan
WorldPolypropyleneDemand 299
RussDeLuca
PVCMarkets,Todayandin2020 303
DonaldGoodman
Index 307
Single-Site Supported Catalysts for Ethylene
A.Mu(cid:1)oz-Escalona,L.Mendez,B.Pe(cid:1)a,P.Lafuente,JSancho,W.Michiels,
G.HidalgoandMa.Fca.Martinez-Nu(cid:1)ez
Repsol,S.A.c/Embajadores,183,24085Madrid,Spain
INTRODUCTION
Single-site catalysts emerged in the polymers field with the discovery of metallocene cata-
lystsbySinnandKaminskyl basedonearlytransitionmetals(Zr,Ti,Hf).Soonaftertheirap-
pearance in 1980 their advantages over the conventional multi-site Ziegler-Natta and
chromium catalysts were recognized. Thus, they are high active catalysts exhibiting an ex-
ceptionalabilitytopolymerizeolefinmonomers,producingextremelyuniformpolymersand
copolymersofnarrowmolecularweightdistribution(polydispersityofabout2)andnarrow
chemicalcompositionaldistribution,controllingatsametimetheresultingpolymerchainar-
chitectures.Theevolutionofsingle-sitecoordinativecatalysiscontinuewiththeappearance
in 1995 of new Ni and Pd diimine complexes capable of producing hyper-branched and
functionalizedpolyolefins2andmorerecentlyin1998withthesynthesisofhighlyactivecat-
alystsforethylenepolymerizationbasedonsubstitutedtridentedpyridinebis-imineligands
attachedtoFeandCometals.3
Topreparesupportedsingle-sitecatalystsdifferentmethodscanbeemployed.4,5Among
them,themostinvestigatedmethodsarebasedondirectadsorptionoverinorganicsupports
(Method 1) or on previously passivated supports by treatment with methylaluminoxane,
MAO, (Method II). A different method, based on the synthesis of metallocenes with func-
tional chemical groups and supporting them by reaction with the chemical groups of the
carriers, has been recently published.5 The reactivity between the functional groups of the
carriersandthemetallocenearecarefullycontrolledsothatthereactionisveryselective,al-
lowingauniformdistributionoftheactivesitesacrossthecatalystsparticles.
Wepresentresultsonsupportedmetallocenesingle-sitecatalystsusingtheabovemen-
tioned methods as well as results obtained with unsupported and supported single-site
catalystsbasedonNiandFemetalsusingmethodII.