6/16/2015

Poly(propene)(Polypropylene)

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Introduction
Industrialprocesses
Materialsandapplications

Polymers

Poly(propene)(Polypropylene)

Polypropene Polypropylene

Propeneundergoesadditionpolymerizationtoproducepoly(propene),oftenknownaspolypropylene,whichisoneofth
mostversatilethermoplasticpolymersavailablecommercially.Mixturesofpropeneandothermonomersformawide
rangeofimportantcopolymers.

Basicchemicals

Polymers

Usesofpoly(propene)(polypropylene)

Polymers:anoverview
Degradableplastics

Poly(propene)isprocessedintofilm,forpackagingandintofibresforcarpetsandclothing.Itisalsousedfor
injectionmouldedarticlesrangingfromcarbumperstowashingupbowls,andcanbeextrudedintopipe(Figure1).

Methanalplastics
(Formaldehydeplastics)
Polyamides
Polycarbonates
Poly(chloroethene)(Polyvinyl
chloride)
Polyesters
Poly(ethene)(Polyethylene)
Poly(methyl2
methylpropenoate)(Polymethyl
methacrylate)
Poly(phenylethene)
(Polystyrene)
Poly(propene)(Polypropylene)
Poly(propenoicacid)
(Polyacrylicacid)

Figure1Usesofpoly(propene).

Poly(propenonitrile)
(Polyacrylonitrile)
Poly(tetrafluoroethene)
(Polytetrafluoroethylene)

Materialssuitableforamuchwiderrangeofapplicationscanbemadebycompoundingpoly(propene)with,for
example,fillersandpigments,andelastomers.
Poly(propene)hasremarkableproperties,makingitsuitabletoreplaceglass,metals,cartonsandotherpolymers.
Thesepropertiesinclude:

Polyurethanes
Silicones

Metals

lowdensity(weightsaving)
highstiffness
heatresistance
chemicalinertness
steambarrierproperties(foodprotection)
goodtransparency
goodimpact/rigiditybalance
stretchability(filmandfibreapplications)
goodhingeproperty(forexamplewherealidandboxaremadetogether,forDVDboxes)
highgloss(appearance)
easytoweld(design)
recyclabililty

Themajority(ca60%ofthetotalproduced)ofpoly(propene)isproducedasahomopolymer.Copolymersare
discussedbelow.
Poly(propene)isoneofthelightestthermoplastics(density0.905gcm3).Ithasameltingpointof440Kanda
crystallinityofca5060%.Thepolymer,unlikepoly(ethene),istransparent.

Structureofthepolymer
Thepropenemoleculeisasymmetrical,

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and,whenpolymerized,canformthreebasicchainstructuresdependentonthepositionofthemethylgroups:two
arestereoregular(isotacticandsyndiotactic)andthethirddoesnothavearegularstructureandistermedatactic
asshowndiagrammaticallybelow:

Figure2Molecularstructuresofpoly(propene).
The'onehanded'structureofisotacticpoly(propene)causesthemoleculestoformhelices.Thisregularform
permitsthemoleculestocrystallizetoahard,relativelyrigidmaterial,which,initspureform,meltsat440K.
Thesyndiotacticpolymer,becauseofitsregularstructure,isalsocrystalline.
Atacticchainsarecompletelyrandominstructureandconsequentlytheydonotcrystallize.Highmolecularmass
atacticpoly(propene)isarubberlikematerial.
Commercialpoly(propene)isapredominantlyisotacticpolymercontaining15%bymassofatacticmaterial.

Annualproductionofpoly(propene)(polypropylene)
World

52.2milliontonnes

Europe 13.1milliontonnes
Russia

0.64milliontonnes1

Datafrom:
1.FederalStateStatisticsService:RussianFederation2011

Manufactureofpoly(propene)(polypropylene)
Poly(propene)isproducedfrompropene.Propeneisproducedinlargequantitiesfromgasoil,naphtha,ethane
andpropane.

(a)UsingaZieglerNattacatalyst
ZieglerNattacatalystsareusedinthepolymerizationprocess.Theseareproducedbyinteractionoftitanium(IV)
chlorideandanaluminiumalkyl,suchastriethylaluminium.
Twomainprocessesareusedformakingthepolymerwiththesecatalysts,althoughtheslurrymethodisusedas
well.

(i)Thebulkprocess
Polymerizationtakesplaceinliquidpropene,intheabsenceofasolventatatemperatureof340360Kand
pressuresof3040atm(tokeepthepropeneasaliquid).Afterpolymerization,solidpolymerparticlesare
separatedfromliquidpropene,whichisthenrecycled.
Theuseofliquidpropeneasasolventforthepolymerasitisformedmeansthatthereisnoneedtouse
hydrocarbonssuchastheC4C8alkaneswhichareusedintheparallelmanufactureofpoly(ethene).

Figure3Aloop
reactorissometimes
usedinthe

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manufactureof
poly(propene)aswell
asinthemanufacture
ofpoly(ethene).
BykindpermissionofTotal.

(ii)Thegasphaseprocess
AmixtureofpropeneandhydrogenispassedoverabedcontainingtheZieglerNattacatalystattemperaturesof
320360Kandapressureof835atm.

Figure4Lowpressuregasphaseprocess
Thepolymerisseparatedfromthegaseouspropeneandhydrogenusingcyclonesandtheunreactedgasis
recycled.
Bothprocessescanbeoperatedcontinuouslyanduse'stereospecific'ZieglerNattacatalyststoeffectthe
polymerization.Thecatalystremainsintheproductandneedstobedestroyedusingwateroralcohols,beforethe
polymerisconvertedintopellets.
Bothbulkandgasphaseprocesseshavevirtuallyeliminatedgaseousandaqueouseffluentsbytheuseofhigh
activitycatalysts,resultinginlowresiduesinthefinalpolymer.

(b)Usingametalloceneascatalyst
Metallocenesarebeingincreasinglyusedascatalystsfortheproductionofpoly(ethene)(mLLDPE)and
poly(propene).
Metallocenesarestrictlydefinedasmoleculeswhichhaveatransitionmetalatombondedbetweentwo
cyclopentadienylligandswhichareinparallelplanes.Ferroceneisaparticularlywellknownexample:

However,thetermisnowusedmorewidelytoincludeotherligandsrelatedtocyclopentadienyl.Onesuch
metalloceneisbasedonzirconium:

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Zirconiumhasanoxidationstateof4andisbondedtotwoindenylligands(acyclopentadienylligandfusedtoa
benzenering).TheyarejoinedbytwoCH2groups.Inconjunctionwithanorganoaluminiumcompound,itactsasa
catalystforthepolymerizationofalkenessuchasetheneandpropene.Thespecificorientationofthezirconium
compoundmeansthateachpropenemolecule,forexample,asitaddsontothegrowingpolymerchainisinthe
sameorientationandanisotacticpolymerisproduced.
Whenadifferentzirconiumcompoundisused,

thesyndiotacticformofpoly(propene)isproduced.Thisistheonlywayofmakingsyndiotacticpoly(propene)
commercially.
AswiththeZieglerNattacatalysts,thebulkorgasphase(describedabove)canbeused.Alternativelytheslurry
processisused.
Poly(propenes)madeinthisway,mPP,areusedinparticulartomakenonwovenfibresandheatsealfilms.
Metallocenesalsocatalysetheproductionofcopolymersofpropeneandethene.

Copolymers
Therearetwomaintypesofcopolymer.Thesimplestaretherandomcopolymers,producedbypolymerizing
togetheretheneandpropene.Etheneunits,usuallyupto6%bymass,areincorporatedrandomlyinthe
poly(propene)chains(Figure5).

Figure5Illustratinganalternatingcopolymerformedfrompropeneandasmallamountofethene.
Thecrystallinityandmeltingpointarereducedandtheproductsaremoreflexibleandareopticallymuchclearer.
Majorusesfortheserandomcopolymersareformedicalproducts(pouches,vialsandothercontainers)and
packaging(forexample,bottles,CDandvideoboxes).
Manyothercopolymersofetheneandpropene,withhigheralkenessuchashexene,arebeingdevelopedwhich
willproducepolymerssimilartoLLDPEbutwhichhavebettermechanicalandopticalproperties.
Thesecondtypeofcopolymersisthesocalled'block'copolymers.Thesearemadebyfollowingthe
poly(propene)homopolymerizationwithafurther,separatestage,inwhichetheneandpropenearecopolymerized
inthegasphase.Thusthesetwoprocessesareinseries(Figure6).

Figure6lllustratingthehomopolymerandtheblockcopolymerformedfrompropeneandethene.
Theproductsofthesetwoprocessesformacompositeinwhichnodulesoftheblockcopolymeraredistributed
withthehomopolymer(Figure7).

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Figure7Thepropeneetheneblockcopolymernodulesdissipateimpactenergyandpreventcracking.
Theethenecontentoftheblockcopolymerislarger(between5and15%)thanusedinrandomlyalternatingco
polymers.Ithasrubberlikepropertiesandistougherandlessbrittlethantherandomcopolymer.Consequently,
thecompositeisparticularlyusefulinmakingcrates,pipes,furnitureandtoys,wheretoughnessisrequired.
Whenethene,propeneandathirdmonomer,adiene,arepolymerized,arubberisformed,knownasEPDM
(Ethene,Propene,Diene,polyMethylene.Theetheneandpropenemoleculespolymerizetoformverylong
molecularchains,withseveralthousandmonomermoleculesinachain.
ThepolymerizationisusuallyeffectedinsolutionusingaZeiglerNattacatalystbutmorerecently,metallocenes
havebeenusedverysuccessfully.Usuallytheethenecontentisabout60%andthatofthedienevariesbetween2
and7%.Thepolymerchainhasthestructure,

whereRcontainsonecarboncarbondoublebond.
Ascanbeseenfromtheformula,itisablockcopolymer.
Asthediene(usuallyENBethylidenenorbornene)hastwodoublebonds,oneisusedinthechainandtheotheris
usedtoformathreedimensionalstructure.Thereactivesitesarependant(notpartofthebackboneofthechain)
andarejoinedtogetherinthenextpartoftheprocesswhenthepolymerisheatedwithsulfur,theprocessusedto
vulcanizerubber.Thetwodimensionalstructureshownabovebecomesthreedimensional.

Datelastamended:2ndJanuary2014

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