Polyolefins: 50 years after Ziegler and Natta I: Polyethylene and Polypropylene

261 Pages·2013·11.888 MB·English

by  Gerhard Fink (auth.), Walter Kaminsky (eds.)

Advances in Polymer Science 257
Walter Kaminsky Editor
Polyolefins: 50
years after Ziegler
and Natta I
Polyethylene and Polypropylene
257
Advances in Polymer Science
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Walter Kaminsky
Editor
Polyolefins: 50 years after
Ziegler and Natta I
Polyethylene and Polypropylene
With contributions by
L.L. Bo¨hm (cid:1) V. Busico (cid:1) R. Cheng (cid:1) M.S. Eisen (cid:1)
(cid:1) (cid:1) (cid:1) (cid:1) (cid:1)
G. Fink X. He B. Liu Z. Liu B. Monrabal
(cid:1) (cid:1) (cid:1) (cid:1)
L.A. Novokshonova P. Qiu S.L. Scott T. Taniike
(cid:1) (cid:1)
M. Terano V.A. Zakharov L. Zhong
Editor
WalterKaminsky
Dept.ofChemistry
Inst.forTechn.andMacromol.Chemistry
UniversityofHamburg
Hamburg
Germany
ISSN0065-3195 ISSN1436-5030(electronic)
ISBN978-3-642-40807-6 ISBN978-3-642-40808-3(eBook)
DOI10.1007/978-3-642-40808-3
SpringerHeidelbergNewYorkDordrechtLondon
LibraryofCongressControlNumber:2013957181
#Springer-VerlagBerlinHeidelberg2013
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Preface
Fifty years after the NobelPrize was awarded toKarl Ziegler andGiulioNattain
1963,thepolymerizationofolefinsbymetallorganiccatalystshasgrowntooneof
themostfascinatingareasinacademicandindustrialpolymerscienceandnowhas
thelargestuseinpolymerproduction.Zieglerhaddiscovered10yearsearlierthata
mixtureoftransitionmetalcompounds,especiallytitaniumchloridesandaluminum
alkyls, was able to polymerize ethene by an insertion reaction. This spectacular
milestone was expanded a year later when Natta prepared and characterized
isotactic polypropylene and introduced stereospecific polymerization. In contrast
to the high-pressure ethene polymerization invented in 1935 by ICI (Imperial
Chemical Industries, Great Britain), the catalyzed olefin polymerization requires
onlylowpressureandlowtemperature.
Today, more than 130 million tons of polyolefins are produced worldwide per
year, the major part with the help of Ziegler–Natta catalysts. Polyolefins have
changed the world! They are not only the polymers with the highest production
volume, but they also show an unbroken production increase. Containing only
carbonandhydrogenatoms,polyolefinsare sustainablematerials, lightinweight,
andofferawidevarietyofproperties.Theproductionrequiresonlyeasilyavailable
andnontoxicmonomersandproceedswithalmostnolossesorsidereactions.After
theirendofuse,polyolefinscaneasilyberecycledthroughmechanicalprocedures
tosimplearticles,bypyrolysistogasandoil,orbyincinerationtoenergy.
In recent decades, new generations of catalysts with higher activities and
stereospecificitiesandmodernproductionprocesseshavebeeninventedtoproduce
a great variety of polyolefins ranging from high density polyethylene (HDPE) to
linearlowdensitypolyethylene(LLDPE),highmeltingpolypropylene,highmod-
uluspolyolefinfibers,ethene–propenerubber(EPR),ethene–propene–dienemono-
merrubber(EPDM).Thechromium-basedPhillipscatalystsopenedthefieldofgas
phase polymerization for HDPE. New supported Ziegler–Natta catalysts make it
possibletoincreasetheactivity,tocontrolthemorphology,andforpolypropylene
toincreasetheisotacticitybyaddingdifferentkindsofdonors.
Agreatdevelopmentinthisresearchfieldwasthediscoveryofmetalloceneand
othertransitionmetalcomplexesactivatedbymethylaluminoxane.Thesecatalysts
v
vi Preface
are up to 10 times more active than Ziegler–Natta catalysts, are soluble in hydro-
carbons,showonlyonetypeofactivesite(singlesitecatalysts),andcaneasilybe
modifiedintheirchemicalstructure.Thesepropertiesmakeitpossibletopredictthe
properties of the resulting polyolefins very accurately from the knowledge of the
structure of the catalyst, and thus to control molecular weight and distribution,
comonomer content, and tacticity by careful selection of the appropriate reactor
conditions.Thesinglesitecharacterofmetallocene-basedcatalystsleadstoabetter
understandingofthemechanismofolefinpolymerizationandtotheintroductionof
otherbulkycocatalysts.
Thedifferentchaptersinthisbookdealwiththedevelopmentofolefinpolymer-
ization 50 years after the pioneering work of Ziegler and Natta. Academic and
industrial developments of ethene and propene polymerizations are presented,
including short biographies of Ziegler and Natta, research on Phillips catalysts,
kinetic and active site measurements, and polyolefin characterization. Review
chaptersalsodescribethelatestresultsofolefinhomo-,living-,andcopolymeriza-
tions by metallocene and other single site catalysts, such as the synthesis of ansa
metallocenes, supported iron catalysts, syndiotactic polypropylene, long chain
branchedpolyolefins,andcyclicandfunctionalcopolymers.Remarkableprogress
has been achieved in the synthesis of polyolefin nanocomposites by an in-situ
polymerization process using clay, layered silicates, carbon fibers, and carbon
nanotubesasfillers.
I thank all the authors very much for giving their time to write these exciting
chapters.
Hamburg,Germany WalterKaminsky
Contents
ContributionstotheZiegler–NattaCatalysis:AnAnthology .............. 1
GerhardFink
GiulioNattaandtheDevelopmentofStereoselectivePropene
Polymerization ................................................................. 37
VincenzoBusico
TheSlurryPolymerizationProcesswithSuper-Active
Ziegler-TypeCatalystSystems:Fromthe2LGlass
Autoclavetothe200m3StirredTankReactor ............................. 59
L.L.Bo¨hm
TheUseofDonorstoIncreasetheIsotacticityofPolypropylene ......... 81
ToshiakiTaniikeandMinoruTerano
KineticsofOlefinPolymerizationandActiveSites
ofHeterogeneousZiegler–NattaCatalysts .................................. 99
LyudmilaA.NovokshonovaandVladimirA.Zakharov
PhillipsCr/SilicaCatalystforEthylenePolymerization .................. 135
RuihuaCheng,ZhenLiu,LeiZhong,XuelianHe,PengyuanQiu,
MinoruTerano,MorisS.Eisen,SusannahL.Scott,andBopingLiu
PolyolefinCharacterization:RecentAdvancesinSeparation
Techniques .................................................................... 203
Benjam´ınMonrabal
vii
viii Contents
Erratumto:PhillipsCr/SilicaCatalystforEthylene
Polymerization ................................................................ 253
RuihuaCheng,ZhenLiu,LeiZhong,XuelianHe,PengyuanQiu,
MinoruTerano,MorisS.Eisen,SusannahL.Scott,andBopingLiu
Index .......................................................................... 255
AdvPolymSci(2013)257:1–36
DOI:10.1007/12_2013_225
©Springer-VerlagBerlinHeidelberg2013
Publishedonline:14June2013
Contributions to the Ziegler–Natta Catalysis:
An Anthology
GerhardFink
Abstract ThisanthologysummarizescontributionstoZiegler–Nattacatalysisthat
haveledthroughnovelexperimentalmethodstowell-foundedresults,tocontinuing
conclusions, and to increasing knowledge about the course of this catalysis. The
complexandmanifoldmechanismhasbeenelucidatedinextensivekineticstudies
inahalfcontinuoustankreactor,inaplugflowreactorwitholigomerdistribution
analysisasanadditional“measuringinstrument,”bydynamicNMRspectroscopy
with line shape analysis, through use of 13C-enriched reacting ethylene as a
molecular surveyor, and by observation of the individual behavior of a large
number of particles with supported catalysts by transmission electron microscopy
and video microscopy. The synopsis of the results of the different experimental
methodsgivesassurancethatwearesafelyontherightpath.
Keywords Catalysis (cid:1) Kinetic analysis (cid:1) Mechanistic detail (cid:1) Stereospecific
polymerization(cid:1)Silica-supportedMetallocene/MAOcatalysts(cid:1)Videomicroscopy
Contents
1 Introduction................................................................................... 2
1.1 BiographicalData...................................................................... 3
2 EarlySolubleUnbridgedMetalloceneCatalystsinConnectionwithAlkylAluminum
Chlorides...................................................................................... 6
2.1 KineticAnalysisbyMeansofaHalfContinuousStirredTankReactor:Ethylene
PolymerizationwithanInSituStart[11]............................................. 7
StudieswithW.Zoller,R.Rottler,D.Schnell,W.Fenzl,R.Mynott,N.Herfert,J.vanderLeek,
M. Reffke, R. Kleinschmidt, R. Goretzki, K Angermund, V. Jensen, W. Thiel, B. Tesche,
B. Steinmetz, C. Przybyla, J. Zechlin, B. Weimann, K. Hauschild, F. Korber, S. Knoke,
A.Alexiades,andD.Ferrari.
G.Fink(*)
Max-Planck-Institutfu¨rKohlenforschung,Kaiser-Wilhelm-Platz1,Mu¨lheimanderRuhr,
Germany
e-mail:fi[email protected]