Multimodal Polymers with Supported Catalysts: Design and Production PDF
Preview Multimodal Polymers with Supported Catalysts: Design and Production
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 ©SpringerNatureSwitzerlandAG2019 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartofthe materialisconcerned,specificallytherightsoftranslation,reprinting,reuseofillustrations,recitation, broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionorinformation storageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilarmethodology nowknownorhereafterdeveloped. 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ThisSpringerimprintispublishedbytheregisteredcompanySpringerNatureSwitzerlandAG Theregisteredcompanyaddressis:Gewerbestrasse11,6330Cham,Switzerland 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
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