Multimodal Polymers with Supported Catalysts: Design and Production

280 Pages·2019·13.312 MB·English

by  Alexandra Romina Albunia, Floran Prades, Dusan Jeremic

Alexandra Romina Albunia 
Floran Prades · Dusan Jeremic Editors
Multimodal
Polymers with
Supported
Catalysts
Design and Production
Multimodal Polymers with Supported Catalysts
(cid:129)
Alexandra Romina Albunia Floran Prades
Dusan Jeremic
Editors
Multimodal Polymers with
Supported Catalysts
Design and Production
Editors
AlexandraRominaAlbunia FloranPrades
BorealisPolyolefineGmbH BorealisPolyolefineGmbH
Linz,Austria Linz,Austria
DusanJeremic
BorealisPolyolefineGmbH
Linz,Austria
ISBN978-3-030-03474-0 ISBN978-3-030-03476-4 (eBook)
https://doi.org/10.1007/978-3-030-03476-4
LibraryofCongressControlNumber:2018966813
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fi fi
Overview of Polyole ns - Role of Polyole ns
in Our Daily Lives
Polyethylene, or, more accurately, low-density polyethylene, LDPE, was the first
syntheticpolyolefindiscovered intheearly 1930sbytheICIscientists Gibson and
Fawcett[1].Thehighlybranchedthermoplasticmaterial,apurehydrocarbon,found
itsapplicationimmediatelyafterthediscovery.Itremainsoneofthemostsignificant
synthetic materials ever used. LDPE is produced under a high-pressure process in
bulk ethylene under 2000–3500 bar pressure and at temperatures that are above
200(cid:1)C.Polymerisationundertheseconditionsisinitiatedbyfreeradicals,whichare
productsofthermaldecompositionofaddedperoxides.
The discovery of the catalytic polymerisation processes in the early 1950s,
Ziegler catalyst by Ziegler et al. [2] and chromium catalyst by two independent
groups at Standard Oil and Phillips Petroleum [3], presented a steep change in the
availability of polyethylene. The sheer fact that the catalytic process operates at
pressures that are two orders of magnitude lower than the high pressure process
needed for manufacturing LDPE simplified the construction and operation of the
manufacturingplants.
Fundamental differences between the radical polymerisation and coordinative
polymerisation,thatis,themechanismofacatalyticprocess,arecausedbystructural
differences in the produced polymer. While LDPE molecules are highly branched
and cross-linked, material made in a catalytic process is mostly linear, with few
branches in the polymer chain that are not deliberatively and carefully introduced.
Such a linear material crystallises faster and to a higher degree, consequently
increasingthedensityofthepolymer.Thecatalyticprocessintroducedhigh-density
polyethylene,HDPE.
Intheearlydaysofthelow-pressurepolyethylene,thedevelopmentmovedrather
fast by discovering new ways to introduce, use and control additional degrees of
freedomfortailoringtheprimarystructureofpolymerchains,whichinfluencesthe
mechanicalandchemicalperformanceofthematerial.
Themolecularweightofthepolymercanbecontrolledfromthestatbyregulating
thetemperatureatwhichthechromium catalyst isbeing usedandbyapplyingand
v
vi OverviewofPolyolefins-RoleofPolyolefinsinOurDailyLives
controlling the concentration of a chain transfer agent, usually hydrogen, in the
reactorduringpolymerisationwithZieglercatalysts.
Branching,leadingtochangingthedensityofthematerial,isreintroducedtothe
linear polyethylene made with Ziegler catalysts by copolymerising α-olefins [4].
Similarly to controlling molecular weight, the concentration of the comonomer
duringpolymerisationdirectlyinfluencesanumberofincorporatedbranches,crys-
tallinity and density of the polymer. The ability to control molecular weight and
densityofthematerialsallowsthephysicalperformancetobetailored.
Soonafterthelow-pressurecatalyticpolymerisationofethylenewasdiscovered,
Natta etal.[4]found outthatthesamecatalystclass,Zieglercatalysts,canalsobe
used for polymerising propylene. This discovery, as well as the ground-breaking
bodyofworkdoneandpublishedbyNattaetal.,introducedandestablishedanother
thermoplastic polyolefin that started being industrially manufactured and used in a
globallysignificantamounts.
Pushing the performance boundaries with the significantly higher melting point
and stiffness, polypropylene, more precisely syndiotactic polypropylene, rapidly
becameandhasremainedoneofthemostusedthermoplasticsintheworld.
Similarly to the development of polyethylene, polypropylene development fur-
therimprovedthephysicalandchemicalperformanceofthematerialand,therefore,
theusabilityforvariousapplications.
Oneoftheprincipleapproachesinmodifyingthephysicalandchemicalperfor-
manceofpolypropyleneisdesigningtheprimarystructureofthepolymerchain.For
example, increased stereoregularity, and therefore crystallinity, of the material
increasesthestiffnessofthemanufacturedobjects.
Creating random and block copolymers by combining propylene with ethylene
polymerisation in one or more reactors, as well as more sophisticated designs of
both matrix and amorphous components of the overall polypropylene material,
brings further features such as impact resistance, softness combined with thermal
stability,etc.
Polyethylene and polypropylene are two materials that are being manufactured
and used inthe amountof approximately 160 million tonnes peryearglobally.PE
andPP,togetherwithother,smallerplayerssuchaspolybutene,aresomeofthemost
utilized materials, and represent more than half of the total plastic materials used
eachyear.
Almostacenturysincetheirdiscovery,polyolefinshavealargepresenceinour
daily lives. Compared to other synthetic and natural materials, they are simpler to
obtain and manufacture, light, with a density lower than 1 g/cm3, chemically
resistant,andnotsolubleatcommonambienttemperatures.Theyarealsorecyclable
andrelativelyenvironmentallyfriendlyanddurable.Incombinationwiththevariety
of physical performance features that can be obtained through the grade of the
material, it is clear why polyolefins are chosen for material manufacturing for a
widerangeofproducts.
Polyolefins can be seen in almost all aspect of our lives. They are most readily
found in packaging. The features that make them suitable for the application are
OverviewofPolyolefins-RoleofPolyolefinsinOurDailyLives vii
predominantly desired and tailorable stiffness/softness, cleanliness, barrier proper-
ties, durability, chemical inertia, simplicity in processing, and low cost, among
others.
Thenextlargestapplicationofpolyolefinsisintheconstructionindustry.Oneof
themostdemandingapplicationofpolyopefinsisinmanufacturingpipesthatwillbe
usedforthetransportofliquidsandgases.Pressureresistanceanddurabilityarethe
requiredfeatures,sothatthepressurepipesusedinbuildingscanlastformorethan
50yearsinservice.
Due to its light weight, tailorable stiffness and impact resistance at different
temperaturesandpaintability,polypropyleneisincreasinglyusedintheautoindus-
try.ManypartsofautomobilesarebeingmanufacturedfromcompoundswherePP
is the principle polymer, often combined with PE, fillers and potentially other
materials.
A significant and important application of polyolefins is in the energy transfer
andstoring.Usedforinsulation,ultra-cleanLDPEcanimprovethequalityofcables
to the extent that large amounts of energy can be transmitted over long distances.
This sort of energy transfer is essential in implementing and exploiting renewable
sourcesofenergy,i.e.wind-poweredgenerators.
Theabove-mentionedapplicationsaresomeofthemoredemandinghigh-volume
applications that are impacting the society. However, by no means they are even
close to represent all the ways polyolefins influence our lives. Examples include
usingUHMWPEforthemanufactureofartificialhumanjoints,andasareplacement
ofPVCinmedicalapplicationssuchasbloodbagsandtubes. Itisalsoincludedas
corrosion protection for metal objects such as steel pipleines; these are only a few
examplesofthemyriadofapplications.
Taking into account the variety of functions that materials based on polyolefins
needtofulfil,itisobviousthattheabove-mentionedabilitytotailorphysical,mostly
mechanical,andchemicalperformanceofthepolymerisessentialforindustry.The
primarystructureofpolymerchainsandtheircompositionwithsimilarordifferent
primary structuresaresomeoftheprincipleparametersthatarethedecidingfactor
regardingtheperformanceofthematerial.
So, for example, molecular weight distribution is directly connected with the
processability of the material. Broader MWD lowers the energy demand when the
polymer is being extruded and vice versa. High molecular weight component in a
flexiblepackagingmaterialcontributestothetoughnessofthepackagingneededto
maintain the integrity of the package. Low molecular weight component, on the
otherhand,enableseffectiveandfastmanufacturing,whichlowerstheoverallcost
ofthepackage.
The amount and location of the comonomer incorporated in the polymer chain
also has an important role in the quality of the polymer. Comonomer-rich long
polymerchainscreateveryhighimpactresistancetofilmmaterial.
The structure property and processing relationships and correlations are under-
stoodatahighlevelbyresearchersinbothindustryandacademia.
viii OverviewofPolyolefins-RoleofPolyolefinsinOurDailyLives
During the century in which various polyolefins have been developed, several
approachestocontrollingandtailoringtheprimarystructurehavebeentaken.Most
ofthemcanbegroupedintothreeprinciplecategories:
(cid:129) Creation and the use of sets of multiple polymerisation conditions zones where
differentpolymerchainsaregeneratedandcombinedinsitu,ofteninoneparticle.
This approach is represented mostly by the use of multiple polymerisation
reactorsinseriesorparallel.
(cid:129) The use of specifically designed initiators, catalysts or a combination thereof.
This approaches uses multiple types of active sites in a polymerisation catalyst
that performdifferentlyand therefore generate the compositionof desired poly-
merchains.Thecombinationofactivesitescanbeaconsequenceoftheinherited
catalyst nature; it can be also tailored by combining the catalyst with different
initiatorsbeforethepolymerisationreactor.
(cid:129) Blendingofpolymersintheafter-reactorprocess.
Selectedcontributionsinthebookdescribetheroleandperformanceofcatalysts
in the processes used for manufacturing multimodal polymers. The catalyst con-
struction,recentdevelopmentsandtrendsinpolymerformationaredescribedinthe
earlier chapters. Subsequentarticles describe theparticle growththeory, modelling
and consequences of the growth. Finally, the effects of the catalyst performance
undervariouspolymerisationconditionsontheproductperformancearediscussed.
References
1. TCE Today, http://www.tcetoday.com//media/Documents/TCE/Articles/2011/845/845cewctw.
pdf(accessedFebruary10,2014).
2. G.Wilke:50JahreZiegler-Katalysatoren,Angew.Chem.115(2003)5150–5159.
3. H.A. Wittcoff, B.G. Reuben, J.S. Plotkin: Industrial Organic Chemicals, J. Wiley & Sons,
NewYork2012.
4. D.B.Malpass:IntroductiontoIndustrialPolyethylene,J.Wiley&Sons,NewYork2010.
Contents
1 RecentDevelopmentsinSupportedPolyolefin
Catalysts:AReview. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
JohnR.Severn
2 SupportDesignedforPolymerizationProcesses. . . . . . . . . . . . . . 55
JonasAlvesFernandesandAnne-LiseGirard
3 Fragmentation,ParticleGrowthandSingle
ParticleModelling. .. . . .. . .. . . .. . . .. . . .. . . .. . . .. . .. . . .. 81
TimothyF.L.McKennaandMuhammadAhsanBashir
4 PolymerizationKineticsandtheEffectofReactor
ResidenceTimeonPolymerMicrostructure. . . . . . . . . . . . . . . . . 115
JoãoB.P.SoaresandVasileiosTouloupidis
5 IndustrialMultimodalProcesses. . . . . . . . . . . . . . . . . . . . . . . . . . 155
VasileiosKanellopoulosandCostasKiparissides
6 MultimodalPolypropylenes:TheCloseInterplay
BetweenCatalysts,ProcessesandPolymerDesign. . . . . . . . . . . . 205
ChristelleGrein
7 BimodalPolyethylene:ControllingPolymerProperties
byMolecularDesign. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
ChristianPaulik,GunnarSpiegel,andDusanJeremic
SummaryandPerspectives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
ix
Chapter 1
Recent Developments in Supported
fi
Polyole n Catalysts: A Review
JohnR.Severn
1.1 Overview
Over the last 60 years the ability to reduce olefinic refinery gases or liquids into a
metastable solid in a controlled manner has created the colossal business of poly-
olefinmaterials.Theircontinuedsuccessisthankstoadeepunderstandingofhowto
meet and predict a customer’s needs in terms of a price/performance package and
translatethatbackthroughthechainofknowledge(Fig.1.1).Thisdemandhasledto
constantevolutionswithinallareasofthebusiness,punctuatedbymorethanitsfair
shareofrevolutionarybreakthroughsintheareasofcatalyst,polymerizationprocess,
andpolymerprocessingtechnology.
One only has to consider the range of applications where a polyolefin solution
finds itself as the preferred option. It is employed in such areas as infrastructure
(pipingandenergytransmission)allowingforthesafeconsistentsupplyofwaterand
energy(electricityandgas,etc.)andremovalofsewage;advancedpackaging,light
and reliable packaging that reduces transport emissions (reduced petroleum con-
sumption) and increased shelf life of perishable goods, reducing waste and further
reducing transport emissions; automotive application replacing metal with light
material allows for lighter automobiles and again further contributes to reduced
transportemissions.Examplesoftheextremelydiverseapplicationsofthematerial
can even be found within very niche areas. For example, UHMWPE fibers can be
usedinsecuringsupertankers,stoppingbullets,andsurgicalsutures.
Polymersynthesisroleinthissuccesshascomebytheabilitytocontrolhowthe
macromoleculesareputtogetherbysequentiallylinkingα-olefins:thechainlength
and distribution, skew, and branching present handles by which properties can be
J.R.Severn(*)
DSMAhead,Geleen,TheNetherlands
SFDGroup,TechnicalUniversityofEindhoven,Eindhoven,TheNetherlands
e-mail:[email protected]
©SpringerNatureSwitzerlandAG2019 1
A.R.Albuniaetal.(eds.),MultimodalPolymerswithSupportedCatalysts,
https://doi.org/10.1007/978-3-030-03476-4_1