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Polymers

1.Introduction
Priortotheearly1920's,chemistsdoubtedtheexistenceofmoleculeshavingmolecularweightsgreaterthanafewthousand.This
limitingviewwaschallengedbyHermannStaudinger,aGermanchemistwithexperienceinstudyingnaturalcompoundssuchas
rubberandcellulose.Incontrasttotheprevailingrationalizationofthesesubstancesasaggregatesofsmallmolecules,Staudinger
proposedtheyweremadeupofmacromoleculescomposedof10,000ormoreatoms.Heformulatedapolymericstructurefor
rubber,basedonarepeatingisopreneunit(referredtoasamonomer).Forhiscontributionstochemistry,Staudingerreceivedthe
1953NobelPrize.ThetermspolymerandmonomerwerederivedfromtheGreekrootspoly(many),mono(one)andmeros(part).
Recognitionthatpolymericmacromoleculesmakeupmanyimportantnaturalmaterialswasfollowedbythecreationofsynthetic
analogshavingavarietyofproperties.Indeed,applicationsofthesematerialsasfibers,flexiblefilms,adhesives,resistantpaintsand
toughbutlightsolidshavetransformedmodernsociety.Someimportantexamplesofthesesubstancesarediscussedinthefollowing
sections.

2.WritingFormulasforPolymericMacromolecules
Therepeatingstructuralunitofmostsimplepolymersnotonlyreflectsthemonomer(s)fromwhichthepolymersareconstructed,but
alsoprovidesaconcisemeansfordrawingstructurestorepresentthesemacromolecules.Forpolyethylene,arguablythesimplest
polymer,thisisdemonstratedbythefollowingequation.Hereethylene(ethene)isthemonomer,andthecorrespondinglinear
polymeriscalledhighdensitypolyethylene(HDPE).HDPEiscomposedofmacromoleculesinwhichnrangesfrom10,000to
100,000(molecularweight2*105to3*106).

IfYandZrepresentmolesofmonomerandpolymerrespectively,Zisapproximately105Y.Thispolymeriscalledpolyethylene
ratherthanpolymethylene,(CH2)n,becauseethyleneisastablecompound(methyleneisnot),anditalsoservesasthesynthetic
precursorofthepolymer.Thetwoopenbondsremainingattheendsofthelongchainofcarbons(coloredmagenta)arenormallynot
specified,becausetheatomsorgroupsfoundtheredependonthechemicalprocessusedforpolymerization.Thesyntheticmethods
usedtopreparethisandotherpolymerswillbedescribedlaterinthischapter.
Unlikesimplerpurecompounds,mostpolymersarenotcomposedofidenticalmolecules.TheHDPEmolecules,forexample,areall
longcarbonchains,butthelengthsmayvarybythousandsofmonomerunits.Becauseofthis,polymermolecularweightsareusually
givenasaverages.Twoexperimentallydeterminedvaluesarecommon:Mn,thenumberaveragemolecularweight,iscalculated
fromthemolefractiondistributionofdifferentsizedmoleculesinasample,andMw,theweightaveragemolecularweight,is
calculatedfromtheweightfractiondistributionofdifferentsizedmolecules.Thesearedefinedbelow.Sincelargermoleculesina
sampleweighmorethansmallermolecules,theweightaverageMwisnecessarilyskewedtohighervalues,andisalwaysgreater
thanMn.Astheweightdispersionofmoleculesinasamplenarrows,MwapproachesMn,andintheunlikelycasethatallthepolymer
moleculeshaveidenticalweights(apuremonodispersesample),theratioMw/Mnbecomesunity.

TheinfluenceofdifferentmassdistributionsonMnandMwmaybeexaminedwiththeaidofasimplemasscalculator.
TousethisdeviceClickHere.

Manypolymericmaterialshavingchainlikestructuressimilartopolyethyleneareknown.Polymersformedbyastraightforwardlinking
togetherofmonomerunits,withnolossorgainofmaterial,arecalledadditionpolymersorchaingrowthpolymers.Alistingof

someimportantadditionpolymersandtheirmonomerprecursorsispresentedinthefollowingtable.

SomeCommonAdditionPolymers
Name(s)

Formula

Monomer

Properties

Uses

Polyethylene
lowdensity(LDPE)

(CH2CH2)n

ethylene
CH2=CH2

soft,waxysolid

filmwrap,plasticbags

Polyethylene
highdensity(HDPE)

(CH2CH2)n

ethylene
CH2=CH2

rigid,translucentsolid

electricalinsulation
bottles,toys

Polypropylene
(PP)differentgrades

[CH2CH(CH3)]n

propylene
CH2=CHCH3

atactic:soft,elasticsolid
similartoLDPE
isotactic:hard,strongsolid carpet,upholstery

Poly(vinylchloride)
(PVC)

(CH2CHCl)n

vinylchloride
CH2=CHCl

strongrigidsolid

pipes,siding,flooring

Poly(vinylidenechloride)
(SaranA)

(CH2CCl2)n

vinylidenechloride
CH2=CCl2

dense,highmeltingsolid

seatcovers,films

Polystyrene
(PS)

[CH2CH(C6H5)]n

styrene
CH2=CHC6H5

hard,rigid,clearsolid
toys,cabinets
solubleinorganicsolvents packaging(foamed)

Polyacrylonitrile
(PAN,Orlon,Acrilan)

(CH2CHCN)n

acrylonitrile
CH2=CHCN

highmeltingsolid
rugs,blankets
solubleinorganicsolvents clothing

Polytetrafluoroethylene
(PTFE,Teflon)

(CF2CF2)n

tetrafluoroethylene
CF2=CF2

resistant,smoothsolid

Poly(methyl
methacrylate)
(PMMA,Lucite,Plexiglas)

[CH2

Poly(vinylacetate)
(PVAc)

(CH2

cisPolyisoprene
naturalrubber

[CH2CH=C(CH3)

Polychloroprene(cis+
trans)
(Neoprene)

[CH2CH=CCl

C(CH3)CO2CH3]n

CHOCOCH3)n

CH2]n

CH2]n

nonsticksurfaces
electricalinsulation

methylmethacrylate
hard,transparentsolid
CH2=C(CH3)CO2CH3

lightingcovers,signs
skylights

vinylacetate
CH2=CHOCOCH3

soft,stickysolid

latexpaints,adhesives

soft,stickysolid

requiresvulcanization
forpracticaluse

tough,rubberysolid

syntheticrubber
oilresistant

isoprene
CH2=CH
C(CH3)=CH2
chloroprene
CH2=CHCCl=CH2

3.PropertiesofMacromolecules
Acomparisonofthepropertiesofpolyethylene(bothLDPE&HDPE)withthenaturalpolymersrubberandcelluloseisinstructive.As
notedabove,syntheticHDPEmacromoleculeshavemassesrangingfrom105to106amu(LDPEmoleculesaremorethana
hundredtimessmaller).Rubberandcellulosemoleculeshavesimilarmassranges,butfewermonomerunitsbecauseofthe
monomer'slargersize.Thephysicalpropertiesofthesethreepolymericsubstancesdifferfromeachother,andofcoursefromtheir
monomers.
HDPEisarigidtranslucentsolidwhichsoftensonheatingabove100C,andcanbefashionedintovariousformsincluding
films.ItisnotaseasilystretchedanddeformedasisLDPE.HDPEisinsolubleinwaterandmostorganicsolvents,although
someswellingmayoccuronimmersioninthelatter.HDPEisanexcellentelectricalinsulator.
LDPEisasofttranslucentsolidwhichdeformsbadlyabove75C.FilmsmadefromLDPEstretcheasilyandarecommonly
usedforwrapping.LDPEisinsolubleinwater,butsoftensandswellsonexposuretohydrocarbonsolvents.BothLDPEand
HDPEbecomebrittleatverylowtemperatures(below80C).Ethylene,thecommonmonomerforthesepolymers,isalow
boiling(104C)gas.
Natural(latex)rubberisanopaque,soft,easilydeformablesolidthatbecomesstickywhenheated(above.60C),andbrittle
whencooledbelow50C.Itswellstomorethandoubleitssizeinnonpolarorganicsolventsliketoluene,eventuallydissolving,
butisimpermeabletowater.TheC5H8monomerisopreneisavolatileliquid(b.p.34C).
Purecellulose,intheformofcotton,isasoftflexiblefiber,essentiallyunchangedbyvariationsintemperaturerangingfrom
70to80C.Cottonabsorbswaterreadily,butisunaffectedbyimmersionintolueneormostotherorganicsolvents.Cellulose

fibersmaybebentandtwisted,butdonotstretchmuchbeforebreaking.ThemonomerofcelluloseistheC6H12O6aldohexose
Dglucose.Glucoseisawatersolublesolidmeltingbelow150C.
Toaccountforthedifferencesnotedhereweneedtoconsiderthenatureoftheaggregate
macromolecularstructure,ormorphology,ofeachsubstance.Becausepolymermoleculesare
solarge,theygenerallypacktogetherinanonuniformfashion,withorderedorcrystallinelike
regionsmixedtogetherwithdisorderedoramorphousdomains.Insomecasestheentiresolid
maybeamorphous,composedentirelyofcoiledandtangledmacromolecularchains.Crystallinity
occurswhenlinearpolymerchainsarestructurallyorientedinauniformthreedimensionalmatrix.
Inthediagramontheright,crystallinedomainsarecoloredblue.
Increasedcrystallinityisassociatedwithanincreaseinrigidity,tensilestrengthandopacity(dueto
lightscattering).Amorphouspolymersareusuallylessrigid,weakerandmoreeasilydeformed.Theyareoftentransparent.
Threefactorsthatinfluencethedegreeofcrystallinityare:
i)Chainlength
ii)Chainbranching
iii)Interchainbonding
TheimportanceofthefirsttwofactorsisnicelyillustratedbythedifferencesbetweenLDPEandHDPE.Asnotedearlier,HDPEis
composedofverylongunbranchedhydrocarbonchains.Thesepacktogethereasilyincrystallinedomainsthatalternatewith
amorphoussegments,andtheresultingmaterial,whilerelativelystrongandstiff,retainsadegreeofflexibility.Incontrast,LDPEis
composedofsmallerandmorehighlybranchedchainswhichdonoteasilyadoptcrystallinestructures.Thismaterialistherefore
softer,weaker,lessdenseandmoreeasilydeformedthanHDPE.Asarule,mechanicalpropertiessuchasductility,tensilestrength,
andhardnessriseandeventuallyleveloffwithincreasingchainlength.
Thenatureofcellulosesupportstheaboveanalysisanddemonstratestheimportanceofthethirdfactor(iii).Tobeginwith,cellulose
chainseasilyadoptastablerodlikeconformation.Thesemoleculesalignthemselvessidebysideintofibersthatarestabilizedby
interchainhydrogenbondingbetweenthethreehydroxylgroupsoneachmonomerunit.Consequently,crystallinityishighandthe
cellulosemoleculesdonotmoveorsliprelativetoeachother.Thehighconcentrationofhydroxylgroupsalsoaccountsforthefacile
absorptionofwaterthatischaracteristicofcotton.
Naturalrubberisacompletelyamorphouspolymer.Unfortunately,thepotentiallyusefulpropertiesofrawlatexrubberarelimitedby
temperaturedependencehowever,thesepropertiescanbemodifiedbychemicalchange.Thecisdoublebondsinthehydrocarbon
chainprovideplanarsegmentsthatstiffen,butdonotstraightenthechain.Iftheserigidsegmentsarecompletelyremovedby
hydrogenation(H2&Ptcatalyst),thechainsloseallconstrainment,andtheproductisalowmeltingparaffinlikesemisolidoflittle
value.Ifinstead,thechainsofrubbermoleculesareslightlycrosslinkedbysulfuratoms,aprocesscalledvulcanizationwhichwas
discoveredbyCharlesGoodyearin1839,thedesirableelastomericpropertiesofrubberaresubstantiallyimproved.At2to3%
crosslinkingausefulsoftrubber,thatnolongersuffersstickinessandbrittlenessproblemsonheatingandcooling,isobtained.At25
to35%crosslinkingarigidhardrubberproductisformed.Thefollowingillustrationshowsacrosslinkedsectionofamorphousrubber.
Byclickingonthediagramitwillchangetoadisplayofthecorrespondingstretchedsection.Themorehighlyorderedchainsinthe
stretchedconformationareentropicallyunstableandreturntotheiroriginalcoiledstatewhenallowedtorelax(clickasecondtime).


Onheatingorcoolingmostpolymersundergothermaltransitionsthatprovideinsightintotheirmorphology.Thesearedefinedasthe
melttransition,Tm,andtheglasstransition,Tg.
Tmisthetemperatureatwhichcrystallinedomainslosetheirstructure,ormelt.Ascrystallinityincreases,sodoesTm.
Tgisthetemperaturebelowwhichamorphousdomainslosethestructuralmobilityofthepolymerchainsandbecomerigidglasses.
Tgoftendependsonthehistoryofthesample,particularlypreviousheattreatment,mechanicalmanipulationandannealing.Itis
sometimesinterpretedasthetemperatureabovewhichsignificantportionsofpolymerchainsareabletoslidepasteachotherin
responsetoanappliedforce.Theintroductionofrelativelylargeandstiffsubstituents(suchasbenzenerings)willinterferewiththis
chainmovement,thusincreasingTg(notepolystyrenebelow).Theintroductionofsmallmolecularcompoundscalledplasticizersinto
thepolymermatrixincreasestheinterchainspacing,allowingchainmovementatlowertemperatures.witharesultingdecreaseinTg.
Theoutgassingofplasticizersusedtomodifyinteriorplasticcomponentsofautomobilesproducesthe"newcarsmell"towhichwe
areaccustomed.
TmandTgvaluesforsomecommonadditionpolymersarelistedbelow.NotethatcellulosehasneitheraTmnoraTg.
Polymer

LDPE

HDPE

PP

PVC

PS

PAN

PTFE

PMMA

Rubber

Tm(C)

110

130

175

180

175

>200

330

180

30

Tg(C)

_110

_100

_10

80

90

95

_110

105

_70

Rubberisamemberofanimportantgroupofpolymerscalledelastomers.Elastomersareamorphouspolymersthathavetheability
tostretchandthenreturntotheiroriginalshapeattemperaturesaboveTg.Thispropertyisimportantinapplicationssuchasgaskets
andOrings,sothedevelopmentofsyntheticelastomersthatcanfunctionunderharshordemandingconditionsremainsapractical
goal.AttemperaturesbelowTgelastomersbecomerigidglassysolidsandloseallelasticity.Atragicexampleofthiscausedthespace
shuttleChallengerdisaster.TheheatandchemicalresistantOringsusedtosealsectionsofthesolidboosterrocketshadan
unfortunatelyhighTgnear0C.TheunexpectedlylowtemperaturesonthemorningofthelaunchwerebelowthisTg,allowinghot
rocketgasestoescapetheseals.

4.RegioandStereoisomerizationinMacromolecules
Symmetricalmonomerssuchasethyleneandtetrafluoroethylenecanjointogetherinonlyoneway.Monosubstitutedmonomers,on
theotherhand,mayjointogetherintwoorganizedways,describedinthefollowingdiagram,orinathirdrandommanner.Most
monomersofthiskind,includingpropylene,vinylchloride,styrene,acrylonitrileandacrylicesters,prefertojoininaheadtotail
fashion,withsomerandomnessoccurringfromtimetotime.Thereasonsforthisregioselectivitywillbediscussedinthesynthetic
methodssection.

Ifthepolymerchainisdrawninazigzagfashion,asshownabove,eachofthesubstituentgroups(Z)willnecessarilybelocated
aboveorbelowtheplanedefinedbythecarbonchain.Consequentlywecanidentifythreeconfigurationalisomersofsuchpolymers.
Ifallthesubstituentslieononesideofthechaintheconfigurationiscalledisotactic.Ifthesubstituentsalternatefromonesideto
anotherinaregularmannertheconfigurationistermedsyndiotactic.Finally,arandomarrangementofsubstituentgroupsisreferred
toasatactic.Examplesoftheseconfigurationsareshownhere.

Manycommonandusefulpolymers,suchaspolystyrene,polyacrylonitrileandpoly(vinylchloride)areatacticasnormallyprepared.
Customizedcatalyststhateffectstereoregularpolymerizationofpolypropyleneandsomeothermonomershavebeendeveloped,and
theimprovedpropertiesassociatedwiththeincreasedcrystallinityoftheseproductshasmadethisanimportantfieldofinvestigation.
ThefollowingvaluesofTghavebeenreported.
Polymer Tgatactic Tgisotactic Tgsyndiotactic
PP

20C

0C

8C

PMMA

100C

130C

120C

Thepropertiesofagivenpolymerwillvaryconsiderablywithitstacticity.Thus,atacticpolypropyleneisuselessasasolidconstruction
material,andisemployedmainlyasacomponentofadhesivesorasasoftmatrixforcompositematerials.Incontrast,isotactic
polypropyleneisahighmeltingsolid(ca.170C)whichcanbemoldedormachinedintostructuralcomponents.

SynthesisofAdditionPolymers
Allthemonomersfromwhichadditionpolymersaremadearealkenesorfunctionallysubstitutedalkenes.Themostcommonand
thermodynamicallyfavoredchemicaltransformationsofalkenesareadditionreactions.Manyoftheseadditionreactionsareknownto
proceedinastepwisefashionbywayofreactiveintermediates,andthisisthemechanismfollowedbymostpolymerizations.A
generaldiagramillustratingthisassemblyoflinearmacromolecules,whichsupportsthenamechaingrowthpolymers,ispresented
here.Sinceapibondinthemonomerisconvertedtoasigmabondinthepolymer,thepolymerizationreactionisusuallyexothermic
by8to20kcal/mol.Indeed,casesofexplosivelyuncontrolledpolymerizationshavebeenreported.

Itisusefultodistinguishfourpolymerizationproceduresfittingthisgeneraldescription.
RadicalPolymerizationTheinitiatorisaradical,andthepropagatingsiteofreactivity(*)isacarbonradical.
CationicPolymerizationTheinitiatorisanacid,andthepropagatingsiteofreactivity(*)isacarbocation.
AnionicPolymerizationTheinitiatorisanucleophile,andthepropagatingsiteofreactivity(*)isacarbanion.
CoordinationCatalyticPolymerizationTheinitiatorisatransitionmetalcomplex,andthepropagatingsiteofreactivity(*)
isaterminalcatalyticcomplex.

1.RadicalChainGrowthPolymerization
Virtuallyallofthemonomersdescribedabovearesubjecttoradicalpolymerization.Sincethiscanbeinitiatedbytracesofoxygenor
otherminorimpurities,puresamplesofthesecompoundsareoften"stabilized"bysmallamountsofradicalinhibitorstoavoid
unwantedreaction.Whenradicalpolymerizationisdesired,itmustbestartedbyusingaradicalinitiator,suchasaperoxideor
certainazocompounds.Theformulasofsomecommoninitiators,andequationsshowingtheformationofradicalspeciesfromthese
initiatorsarepresentedbelow.

Byusingsmallamountsofinitiators,awidevarietyofmonomerscanbepolymerized.Oneexampleofthisradicalpolymerizationis

theconversionofstyrenetopolystyrene,showninthefollowingdiagram.Thefirsttwoequationsillustratetheinitiationprocess,and
thelasttwoequationsareexamplesofchainpropagation.Eachmonomerunitaddstothegrowingchaininamannerthat
generatesthemoststableradical.Sincecarbonradicalsarestabilizedbysubstituentsofmanykinds,thepreferenceforheadtotail
regioselectivityinmostadditionpolymerizationsisunderstandable.Becauseradicalsaretolerantofmanyfunctionalgroupsand
solvents(includingwater),radicalpolymerizationsarewidelyusedinthechemicalindustry.

Toseeananimatedmodeloftheradicalchaingrowthpolymerizationofvinylchloride ClickHere
Inprinciple,oncestartedaradicalpolymerizationmightbeexpectedtocontinueunchecked,producingafewextremelylongchain
polymers.Inpractice,largernumbersofmoderatelysizedchainsareformed,indicatingthatchainterminatingreactionsmustbe
takingplace.ThemostcommonterminationprocessesareRadicalCombinationandDisproportionation.Thesereactionsare
illustratedbythefollowingequations.Thegrowingpolymerchainsarecoloredblueandred,andthehydrogenatomtransferredin
disproportionationiscoloredgreen.Notethatinbothtypesofterminationtworeactiveradicalsitesareremovedbysimultaneous
conversiontostableproduct(s).Sincetheconcentrationofradicalspeciesinapolymerizationreactionissmallrelativetoother
reactants(e.g.monomers,solventsandterminatedchains),therateatwhichtheseradicalradicalterminationreactionsoccursisvery
small,andmostgrowingchainsachievemoderatelengthbeforetermination.

Therelativeimportanceoftheseterminationsvarieswiththenatureofthemonomerundergoingpolymerization.Foracrylonitrileand
styrenecombinationisthemajorprocess.However,methylmethacrylateandvinylacetateareterminatedchieflyby
disproportionation.
Anotherreactionthatdivertsradicalchaingrowthpolymerizationsfromproducinglinearmacromoleculesiscalledchaintransfer.As
thenameimplies,thisreactionmovesacarbonradicalfromonelocationtoanotherbyanintermolecularorintramolecularhydrogen
atomtransfer(coloredgreen).Thesepossibilitiesaredemonstratedbythefollowingequations

Chaintransferreactionsareespeciallyprevalentinthehighpressureradicalpolymerizationofethylene,whichisthemethodusedto
makeLDPE(lowdensitypolyethylene).The1radicalattheendofagrowingchainisconvertedtoamorestable2radicalby
hydrogenatomtransfer.Furtherpolymerizationatthenewradicalsitegeneratesasidechainradical,andthismayinturnleadto
creationofothersidechainsbychaintransferreactions.Asaresult,themorphologyofLDPEisanamorphousnetworkofhighly
branchedmacromolecules.

2.CationicChainGrowthPolymerization
Polymerizationofisobutylene(2methylpropene)bytracesofstrongacidsisanexampleofcationicpolymerization.The
polyisobutyleneproductisasoftrubberysolid,Tg=_70C,whichisusedforinnertubes.Thisprocessissimilartoradical
polymerization,asdemonstratedbythefollowingequations.Chaingrowthceaseswhentheterminalcarbocationcombineswitha
nucleophileorlosesaproton,givingaterminalalkene(asshownhere).

Monomersbearingcationstabilizinggroups,suchasalkyl,phenylorvinylcanbepolymerizedbycationicprocesses.Theseare
normallyinitiatedatlowtemperatureinmethylenechloridesolution.Strongacids,suchasHClO4,orLewisacidscontainingtracesof
water(asshownabove)serveasinitiatingreagents.Atlowtemperatures,chaintransferreactionsarerareinsuchpolymerizations,
sotheresultingpolymersarecleanlylinear(unbranched).

3.AnionicChainGrowthPolymerization
TreatmentofacoldTHFsolutionofstyrenewith0.001equivalentsofnbutyllithiumcausesanimmediatepolymerization.Thisisan
exampleofanionicpolymerization,thecourseofwhichisdescribedbythefollowingequations.Chaingrowthmaybeterminatedby
waterorcarbondioxide,andchaintransferseldomoccurs.Onlymonomershavinganionstabilizingsubstituents,suchasphenyl,
cyanoorcarbonylaregoodsubstratesforthispolymerizationtechnique.Manyoftheresultingpolymersarelargelyisotacticin
configuration,andhavehighdegreesofcrystallinity.

Speciesthathavebeenusedtoinitiateanionicpolymerizationincludealkalimetals,alkaliamides,alkyllithiumsandvariouselectron
sources.Apracticalapplicationofanionicpolymerizationoccursintheuseofsuperglue.Thismaterialismethyl2cyanoacrylate,
CH2=C(CN)CO2CH3.Whenexposedtowater,aminesorothernucleophiles,arapidpolymerizationofthismonomertakesplace.

4.ZieglerNattaCatalyticPolymerization
AnefficientandstereospecificcatalyticpolymerizationprocedurewasdevelopedbyKarlZiegler(Germany)andGiulioNatta(Italy)in
the1950's.Theirfindingspermitted,forthefirsttime,thesynthesisofunbranched,highmolecularweightpolyethylene(HDPE),
laboratorysynthesisofnaturalrubberfromisoprene,andconfigurationalcontrolofpolymersfromterminalalkeneslikepropene(e.g.
pureisotacticandsyndiotacticpolymers).Inthecaseofethylene,rapidpolymerizationoccurredatatmosphericpressureand
moderatetolowtemperature,givingastronger(morecrystalline)product(HDPE)thanthatfromradicalpolymerization(LDPE).For
thisimportantdiscoverythesechemistsreceivedthe1963NobelPrizeinchemistry.
ZieglerNattacatalystsarepreparedbyreactingcertaintransitionmetalhalideswithorganometallicreagentssuchasalkylaluminum,
lithiumandzincreagents.Thecatalystformedbyreactionoftriethylaluminumwithtitaniumtetrachloridehasbeenwidelystudied,but
othermetals(e.g.V&Zr)havealsoproveneffective.Thefollowingdiagrampresentsonemechanismforthisusefulreaction.Others
havebeensuggested,withchangestoaccommodatetheheterogeneityorhomogeneityofthecatalyst.Polymerizationofpropylene
throughactionofthetitaniumcatalystgivesanisotacticproductwhereas,avanadiumbasedcatalystgivesasyndiotacticproduct.

Copolymers
Thesynthesisofmacromoleculescomposedofmorethanonemonomericrepeatingunithasbeenexploredasameansofcontrolling
thepropertiesoftheresultingmaterial.Inthisrespect,itisusefultodistinguishseveralwaysinwhichdifferentmonomericunitsmight
beincorporatedinapolymericmolecule.Thefollowingexamplesrefertoatwocomponentsystem,inwhichonemonomeris
designatedAandtheotherB.
StatisticalCopolymers

Alsocalledrandomcopolymers.Herethemonomericunitsaredistributedrandomly,and
sometimesunevenly,inthepolymerchain:~ABBAAABAABBBABAABA~.

AlternatingCopolymers Herethemonomericunitsaredistributedinaregularalternatingfashion,withnearlyequimolar
amountsofeachinthechain:~ABABABABABABABAB~.
BlockCopolymers

Insteadofamixeddistributionofmonomericunits,alongsequenceorblockofonemonomeris
joinedtoablockofthesecondmonomer:~AAAAABBBBBBB~AAAAAAA~BBB~.

GraftCopolymers

Asthenamesuggests,sidechainsofagivenmonomerareattachedtothemainchainofthe
secondmonomer:~AAAAAAA(BBBBBBB~)AAAAAAA(BBBB~)AAA~.

1.AdditionCopolymerization
Mostdirectcopolymerizationsofequimolarmixturesofdifferentmonomersgivestatisticalcopolymers,orifonemonomerismuch
morereactiveanearlyhomopolymerofthatmonomer.Thecopolymerizationofstyrenewithmethylmethacrylate,forexample,
proceedsdifferentlydependingonthemechanism.Radicalpolymerizationgivesastatisticalcopolymer.However,theproductof
cationicpolymerizationislargelypolystyrene,andanionicpolymerizationfavorsformationofpoly(methylmethacrylate).Incases
wheretherelativereactivitiesaredifferent,thecopolymercompositioncansometimesbecontrolledbycontinuousintroductionofa
biasedmixtureofmonomersintothereaction.
Formationofalternatingcopolymersisfavoredwhenthemonomershavedifferentpolarsubstituents(e.g.oneelectronwithdrawing
andtheotherelectrondonating),andbothhavesimilarreactivitiestowardradicals.Forexample,styreneandacrylonitrile
copolymerizeinalargelyalternatingfashion.

SomeUsefulCopolymers
MonomerA

MonomerB

Copolymer

Uses

H2C=CHCl

H2C=CCl2

Saran

films&fibers

H2C=CHC6H5

H2C=CCH=CH2

SBR
styrenebutadienerubber

tires

H2C=CHCN

H2C=CCH=CH2

NitrileRubber

adhesives
hoses

H2C=C(CH3)2

H2C=CCH=CH2

ButylRubber

innertubes

F2C=CF(CF3)

H2C=CHF

Viton

gaskets

Aterpolymerofacrylonitrile,butadieneandstyrene,calledABSrubber,isusedforhighimpactcontainers,pipesandgaskets.

2.BlockCopolymerization
Severaldifferenttechniquesforpreparingblockcopolymershavebeendeveloped,manyofwhichusecondensationreactions(next
section).Atthispoint,ourdiscussionwillbelimitedtoanapplicationofanionicpolymerization.Intheanionicpolymerizationofstyrene
describedabove,areactivesiteremainsattheendofthechainuntilitisquenched.Theunquenchedpolymerhasbeentermeda
livingpolymer,andifadditionalstyreneoradifferentsuitablemonomerisaddedablockpolymerwillform.Thisisillustratedfor
methylmethacrylateinthefollowingdiagram.

CondensationPolymers
Alargenumberofimportantandusefulpolymericmaterialsarenotformedbychaingrowthprocessesinvolvingreactivespeciessuch
asradicals,butproceedinsteadbyconventionalfunctionalgrouptransformationsofpolyfunctionalreactants.Thesepolymerizations
often(butnotalways)occurwithlossofasmallbyproduct,suchaswater,andgenerally(butnotalways)combinetwodifferent
componentsinanalternatingstructure.ThepolyesterDacronandthepolyamideNylon66,shownhere,aretwoexamplesof
syntheticcondensationpolymers,alsoknownasstepgrowthpolymers.Incontrasttochaingrowthpolymers,mostofwhichgrowby
carboncarbonbondformation,stepgrowthpolymersgenerallygrowbycarbonheteroatombondformation(CO&CNinDacron&
Nylonrespectively).Althoughpolymersofthiskindmightbeconsideredtobealternatingcopolymers,therepeatingmonomericunitis
usuallydefinedasacombinedmoiety.
Examplesofnaturallyoccurringcondensationpolymersarecellulose,thepolypeptidechainsofproteins,andpoly(hydroxybutyric
acid),apolyestersynthesizedinlargequantitybycertainsoilandwaterbacteria.Formulasforthesewillbedisplayedbelowby
clickingonthediagram.

1.CharacteristicsofCondensationPolymers
Condensationpolymersformmoreslowlythanadditionpolymers,oftenrequiringheat,andtheyaregenerallylowerinmolecular
weight.Theterminalfunctionalgroupsonachainremainactive,sothatgroupsofshorterchainscombineintolongerchainsinthe
latestagesofpolymerization.Thepresenceofpolarfunctionalgroupsonthechainsoftenenhanceschainchainattractions,
particularlyiftheseinvolvehydrogenbonding,andtherebycrystallinityandtensilestrength.Thefollowingexamplesofcondensation
polymersareillustrative.
Notethatforcommercialsynthesisthecarboxylicacidcomponentsmayactuallybeemployedintheformofderivativessuchassimple
esters.Also,thepolymerizationreactionsforNylon6andSpandexdonotproceedbyeliminationofwaterorothersmallmolecules.
Nevertheless,thepolymerclearlyformsbyastepgrowthprocess.

SomeCondensationPolymers
Formula

Type

Components

TgC

TmC

~[CO(CH2)4COOCH2CH2O]n~

polyester

HO2C(CH2)4CO2H

<0

50

70

265

50

240

150

267

45

265

53

223

500

273

390

52

HOCH2CH2

OH

polyester
Dacron
Mylar

paraHO2CC6H4CO2H

polyester

metaHO2CC6H4CO2H

HOCH2CH2

HOCH2CH2
polycarbonate
Lexan

OH

OH

(HOC6H4)2C(CH3)2
(BisphenolA)
X2C=O
(X=OCH3orCl)

~[CO(CH2)4CONH(CH2)6NH]n~

~[CO(CH2)5NH]n~

polyamide
Nylon66

HO2C(CH2)4CO2H
H2N(CH2)6NH2

polyamide
Nylon6
Perlon
polyamide
Kevlar

paraHO2CC6H4CO2H

polyamide
Nomex

metaHO2CC6H4CO2H

polyurethane
Spandex

HOCH2CH2OH

paraH2NC6H4NH2

metaH2NC6H4NH2

ThedifferenceinTgandTmbetweenthefirstpolyester(completelyaliphatic)andthetwonylonpolyamides(5th&6thentries)shows
theeffectofintrachainhydrogenbondingoncrystallinity.Thereplacementofflexiblealkylidenelinkswithrigidbenzeneringsalso
stiffensthepolymerchain,leadingtoincreasedcrystallinecharacter,asdemonstratedforpolyesters(entries1,2&3)andpolyamides
(entries5,6,7&8).ThehighTgandTmvaluesfortheamorphouspolymerLexanareconsistentwithitsbrillianttransparencyand
glasslikerigidity.KevlarandNomexareextremelytoughandresistantmaterials,whichfinduseinbulletproofvestsandfireresistant
clothing.

Manypolymers,bothadditionandcondensation,areusedasfibersThechiefmethodsofspinningsyntheticpolymersintofibersare
frommeltsorviscoussolutions.Polyesters,polyamidesandpolyolefinsareusuallyspunfrommelts,providedtheTmisnottoohigh.
Polyacrylatessufferthermaldegradationandarethereforespunfromsolutioninavolatilesolvent.Colddrawingisanimportant
physicaltreatmentthatimprovesthestrengthandappearanceofthesepolymerfibers.AttemperaturesaboveTg,athickerthan
desiredfibercanbeforciblystretchedtomanytimesitslengthandinsodoingthepolymerchainsbecomeuntangled,andtendto
aligninaparallelfashion.Thiscolddrawingprocedureorganizesrandomlyorientedcrystallinedomains,andalsoalignsamorphous
domainssotheybecomemorecrystalline.Inthesecases,thephysicallyorientedmorphologyisstabilizedandretainedinthefinal
product.Thiscontrastswithelastomericpolymers,forwhichthestretchedoralignedmorphologyisunstablerelativetothe
amorphousrandomcoilmorphology.
Byclickingonthefollowingdiagram,acartoonofthesechangeswilltogglefromoneextremetotheother.Thiscolddrawing
treatmentmayalsobeusedtotreatpolymerfilms(e.g.Mylar&Saran)aswellasfibers.

Stepgrowthpolymerizationisalsousedforpreparingaclassofadhesivesandamorphoussolidscalledepoxyresins.Herethe
covalentbondingoccursbyanSN2reactionbetweenanucleophile,usuallyanamine,andaterminalepoxide.Inthefollowing
example,thesamebisphenolAintermediateusedasamonomerforLexanservesasadifunctionalscaffoldtowhichtheepoxide
ringsareattached.BisphenolAispreparedbytheacidcatalyzedcondensationofacetonewithphenol.

2.Thermosettingvs.ThermoplasticPolymers
Mostofthepolymersdescribedaboveareclassifiedasthermoplastic.ThisreflectsthefactthataboveTgtheymaybeshapedor
pressedintomolds,spunorcastfrommeltsordissolvedinsuitablesolventsforlaterfashioning.Becauseoftheirhighmeltingpoint
andpoorsolubilityinmostsolvents,KevlarandNomexprovedtobeachallenge,butthiswaseventuallysolved.
Anothergroupofpolymers,characterizedbyahighdegreeofcrosslinking,resistdeformationandsolutiononcetheirfinal
morphologyisachieved.Suchpolymersareusuallypreparedinmoldsthatyieldthedesiredobject.Becausethesepolymers,once
formed,cannotbereshapedbyheating,theyarecalledthermosets.Partialformulasforfourofthesewillbeshownbelowbyclicking
theappropriatebutton.TheinitialdisplayisofBakelite,oneofthefirstcompletelysyntheticplasticstoseecommercialuse(circa
1910).

PhenolFormaldehyde

UreaFormaldehyde

MelamineFormaldehyde

GlyptalResins

Anaturalresinouspolymercalledligninhasacrosslinkedstructuresimilartobakelite.Ligninistheamorphousmatrixinwhichthe
cellulosefibersofwoodareoriented.Woodisanaturalcompositematerial,nature'sequivalentoffiberglassandcarbonfiber
composites.Apartialstructureforligninisshownhere

TheAgeofPlastics
Historically,manyeraswerecharacterizedbythematerialsthatwerethenimportanttohumansociety(e.g.stoneage,bronzeage
andironage).The20thcenturyhasacquiredseverallabelsofthissort,includingthenuclearageandtheoilagehowever,thebest
nameislikelytheplasticage.Duringthisperiodnotechnologicaladvancement,otherthanthedeliveryofelectricalpowertoevery
home,hasimpactedourlivesmorethanthewidespreaduseofsyntheticplasticsinourclothes,dishes,constructionmaterials,
automobiles,packaging,andtoys,tonameafew.Thedevelopmentofmaterialsthatwenowcallplasticsbeganwithrayonin1891,
continuingwithBakelitein1907,polyethylenein1933,NylonandTeflonin1938,polypropylenein1954,Kevlarin1965,andis
continuing.
Themanytypesofpolymersthatwelumptogetherasplasticsare,ingeneral,inexpensive,lightweight,strong,durableand,when
desired,flexible.Plasticsmaybeprocessedbyextrusion,injectionmoulding,vacuumforming,andcompression,emergingasfibers,
thinsheetsorobjectsofaspecificshape.Theymaybecoloredasdesiredandreinforcedbyglassorcarbonfibers,andsomemaybe
expandedintolowdensityfoams.Manymodernadhesivesinvolvetheformationofaplasticbondingsubstance.Plasticshave
replacedanincreasingnumberofnaturalsubstances.Inthemanufactureofpianokeysandbilliardballsplasticshavereplacedivory,
assistingthesurvivaloftheelephant.Itisnoteworthythatasyntheticfibermanufacturingfacilityoccupiesamuchsmallerareaof
groundthanwouldbeneededtoproduceanequalquantityofnaturalfibers,suchascotton,woolorsilk.Withalltheseadvantagesit
isnotsurprisingthatmuchofwhatyouseearoundyouisplastic.Indeed,thelowcost,lightweight,strengthanddesignadaptabilityof
plasticstomeetavarietyofapplicationshaveresultedinstrongyearafteryeargrowthintheirproductionanduse,whichislikelyto
continue.Indeed,manyplasticsareemployedindisposableproductsmeantonlyforasingleuse.

TheLawofUnintendedConsequences
Successfulsolutionstotechnologicalprojectsareoftenachievedbyfocusingonalimitedsetofvariablesthataredirectlylinkedtoa

desiredoutcome.However,natureoftenhasawayofrewardingsuch
successbyexposingunexpectedproblemsgenerated"outsidethe
box"ofthedefinedproject.Inthecaseofplastics,theiradvantageous
durabilityandrelativelowcosthaveresultedinseriousenvironmental
pollutionasuseditemsandwrappingsarecasuallydiscardedand
replacedinaneverendingcycle.Weseethiseverydayonthestreets
andfieldsofourneighborhoods,buttheproblemisfarmoredire.
CharlesMoore,anAmericanoceanographer,in1997discoveredan
enormousstewoftrash,estimatedatnearly100milliontons,floating
inthePacificOceanbetweenSanFranciscoandHawaii.Namedthe
"GreatPacificGarbagePatch",thisstewoftrashiscomposedlargely
(80%)ofbitsandpiecesofplasticthatoutweightheplankton6:1,in
aregionovertwicethesizeofTexas.Althoughsomeofthisflotsam
originatesfromshipsatsea,atleast80%comesfromlandgenerated
trash.Theinformationprovidedhere,andtheillustrationontheleft,
comefromanarticlebySusanCaseyinBestLife
Clockwisecirculationofcurrentsdrivenbytheglobalwindsystem
andconstrainedbysurroundingcontinentsformavortexorgyre
comparabletoalargewhirlpool.Eachmajoroceanbasinhasalarge
gyreinthesubtropicalregion,centeredaround30northandsouth
latitude.TheNorthAtlanticSubtropicalGyreisknownasthe
SargassoSea.ThelargerNorthPacificSubtropicalGyre,referredto
asthedoldrums,istheconvergencezonewhereplasticandother
wastemixestogether.TherearesimilarareasintheSouthPacific,the
NorthandSouthAtlantic,andtheIndianOcean.
Asidefromitsdisgustingaestheticpresence,thegarbagepatchis
representativeofseriousenvironmentalandhealthproblems.Noone
knowshowlongitwilltakeforsomeoftheseplasticstobiodegrade,
orreturntotheircomponentmolecules.Persistentobjectssuchassix
packringsanddiscardednetstrapseaanimals.Smallerplasticscraps
aremistakenforfoodbyseabirdsandareoftenfoundundigestedin
thegutofdeadbirds.Nurdles,lentilsizepelletsofplastic,foundin
abundancewhereplasticsaremanufacturedanddistributed,are
dispersedbywindthroughoutthebiosphere.They'relightenoughto
blowaroundlikedustandtowashintoharbors,stormdrains,and
creeks.Escapednurdlesandotherplasticlittermigratetotheocean
gyrelargelyfromland.AtplacesasremoteasRarotonga,intheCook
Islandsthey'recommonlyfoundmixedwithbeachsand.Onceinthe
ocean,nurdlesmayabsorbuptoamilliontimesthelevelofanyorganicpollutantsfoundinsurroundingwaters.Nurdlesintheseaare
easilymistakenforfisheggsbycreaturesthatwouldverymuchliketohavesuchasnack.Onceinsidethebodyofabigeyetunaora
kingsalmon,theybecomepartofourfoodchain.

RecyclingandDisposal
Mostplasticscrumbleintoevertinierfragmentsastheyareexposedtosunlightandtheelements.Exceptforthesmallamountthat's
beenincineratedandit'saverysmallamounteverybitofplasticevermadestillexists,unlessthematerial'smolecularstructureis
designedtofavorbiodegradation.Unfortunately,cleaningupthegarbagepatchisnotarealisticoption,andunlesswechangeour
disposalandrecyclinghabits,itwillundoubtedlygetbigger.Onesensiblesolutionwouldrequiremanufacturerstousenatural
biodegradablepackagingmaterialswheneverpossible,andconsumerstoconscientiouslydisposeoftheirplasticwaste.Thus,instead
ofconsigningallplastictrashtoalandfill,someofitmayprovideenergybydirectcombustion,andsomeconvertedforreuseasa
substituteforvirginplastics.Thelatterisparticularlyattractivesinceamajorityofplasticsaremadefrompetroleum,adiminishing
resourcewithavolatileprice.
Theenergypotentialofplasticwasteisrelativelysignificant,rangingfrom10.2to30.7MJkg1,suggestingapplicationasanenergy
sourceandtemperaturestabilizerinmunicipalincinerators,thermalpowerplantsandcementkilns.Theuseofplasticwasteasafuel
sourcewouldbeaneffectivemeansofreducinglandfillrequirementswhilerecoveringenergy.This,however,dependsonusing
appropriatematerials.Inadequatecontrolofcombustion,especiallyforplasticscontainingchlorine,fluorineandbromine,constitutesa
riskofemittingtoxicpollutants.
Whetherusedasfuelsorasourceofrecycledplastic,plasticwastemustbeseparatedintodifferentcategories.Tothisend,an
identificationcodingsystemwasdevelopedbytheSocietyofthePlasticsIndustry(SPI)in1988,andisusedinternationally.This
code,shownontheright,isasetofsymbolsplacedonplasticstoidentifythepolymertype,forthepurposeofallowingefficient
separationofdifferentpolymertypesforrecycling.Theabbreviationsofthecodeareexplainedinthefollowingtable.

PETE

HDPE

LDPE

polyethylene
terephthalate

highdensity
polyethylene

polyvinyl
chloride

lowdensity
polyethylene

PP

PS

OTHER

polypropylene

polystyrene

polyesters,acrylics
polyamides,teflonetc.

Despiteuseoftherecyclingsymbolinthecodingofplastics,thereisconsumerconfusionaboutwhichplasticsarereadilyrecyclable.
InmostcommunitiesthroughouttheUnitedStates,PETEandHDPEaretheonlyplasticscollectedinmunicipalrecyclingprograms.
However,someregionsareexpandingtherangeofplasticscollectedasmarketsbecomeavailable.(LosAngeles,forexample,
recyclesallcleanplasticsnumbered1through7)Intheory,mostplasticsarerecyclableandsometypescanbeusedincombination
withothers.Inmanyinstances,however,thereisanincompatibilitybetweendifferenttypesthatnecessitatestheireffective
separation.Sincetheplasticsutilizedinagivenmanufacturingsector(e.g.electronics,automotive,etc.)isgenerallylimitedtoafew
types,effectiverecyclingisoftenbestachievedwithtargetedwastestreams.
Theplastictrashfrommosthouseholds,evenwithsomeuserseparation,isamixtureofunidentifiedpieces.Recyclingofsuch
mixturesisachallengingproblem.Afloat/sinkprocesshasprovenusefulasafirststep.Whenplacedinamediumofintermediate
density,particlesofdifferentdensitiesseparatelowerdensityparticlesfloatwhilethoseofhigherdensitysink.Variousseparation
mediahavebeenused,includingwaterorwatersolutionsofknowndensity(alcohol,NaCl,CaCl2orZnCl2).Asshowninthe
followingtable,thedensitiesofcommonplasticsdiffersufficientlytopermitthemtobediscriminatedinthisfashion.The
cylindroconicalcyclonedevice,shownontheright,providesacontinuousfeedprocedureinwhichthematerialtobeseparatedis
pumpedintothevesselatthesametimeastheseparatingmedia.Somepolymers,suchaspolystyreneandpolyurethane,are
commonlyformedintofoamedsolidsthathaveamuchlowerdensitythanthesolidmaterial.
DensitiesofTypicalPlastics
PE&PP
0.900.99

ABS&SAN PMM&acrylics PETE&PVC


&nylons &polycarbonates &Bakelite
1.051.09

1.101.25

1.31.6

PE=polyethylene&PP=polypropylene
ABS=acrylonitrilebutadienestyrenecopolymer
SAN=acrylonitrilestyrenecopolymer
PMM=polymethylmethacrylate
PETE=polyethyleneterephthalate
PVC=polyvinylchloride(rigid)

Oneseriousprobleminrecyclingisposedbythemanyadditivesfoundinplasticwaste.Theseincludepigmentsforcoloring,solid
fibersincomposites,stabilizersandplasticizers.InthecaseofPETE(orPET),whichiscommonlyusedforbottles,somewastemay
bemechanicallyandthermallytreatedtoproducelowgradepackagingmaterialsandfibers.ToincreasethevalueofrecoveredPETE
itmaybedepolymerizedbysuperheatedmethanolintodimethylterephthalateandethyleneglycol.Thesechemicalsarethenpurified
andusedtomakevirginPETE.Hydrocarbonpolymerssuchaspolyethyleneandpolypropylenemaybemeltedandextrudedinto
pelletsforreuse.However,thepresenceofdyesorpigmentslimitsthevalueofthisproduct.

BiodegradablePolymers
Plasticsderivedfromnaturalmaterials,suchascellulose,starchandhydroxycarboxylicacidsaremoreeasilydecomposedwhen
exposedtooxygen,water,soilorganismsandsunlightthanaremostpetroleumbasedpolymers.Theglycosidelinkagesin
polysaccharidesandtheestergroupsinpolyestersrepresentpointsofattackbytheenzymesofmicroorganismsthatfacilitatetheir
decomposition.Suchbiodegradablematerialscanbecomposted,brokendownandreturnedtotheearthasusefulnutrients.
However,itisimportanttorecognizethatpropercompostingisnecessary.Placingsuchmaterialsinalandfillresultsinaslower
anaerobicdecomposition,whichproducesmethane,agreenhousegas.
Derivativesofcellulose,suchascelluloseacetate,havelongservedforthemanufactureoffilmsandfibers.Themostusefulacetate
materialisthediacetate,inwhichtwothirdsofthecellulosehydroxylgroupshavebeenesterified.Acetatefibersloosestrengthwhen
wet,andacetateclothingmustbedrycleaned.Theothermajorpolysaccharide,starch,islessrobustthancellulose,butinpelletized
formitisnowreplacingpolystyreneasapackingmaterial.
Thetwonaturalpolyestersthatarefindingincreasinguseasreplacementsforpetroleumbasedplasticsarepolylactide(PLA)and
polyhydroxyalkanoates(PHA),thelattermostcommonlyascopolymerswithpolyhydroxybutyrate(PHB).Structuresforthethese
polymersandtheirmonomerprecursorsareshownbelow.

PLAisactuallyapolymeroflacticacid,butthedimericlactideisusedastheprecursortoavoidthewaterthatwouldbeformedina
directpolyesterification.Bacterialfermentationisusedtoproducelacticacidfromcornstarchorcanesugar.Afterdimerizationtothe
lactide,ringopeningpolymerizationofthepurifiedlactideiseffectedusingstannouscompoundsascatalysts.PLAcanbeprocessed
likemostthermoplasticsintofibersandfilms.Insituationsthatrequireahighlevelofimpactstrength,thetoughnessofPLAinits
pristinestateisofteninsufficient.BlendsofPLAwithpolymerssuchasABShavegoodformstabilityandvisualtransparency,making
themusefulforlowendpackagingapplications.PLAmaterialsarecurrentlyusedinanumberofbiomedicalapplications,suchas
sutures,stents,dialysismediaanddrugdeliverydevices.However,oneofthedrawbacksofpolylactidesforbiomedicalapplicationsis
theirbrittleness.
Lacticacidhasachiralcenter,the(S)(+)enantiomerbeingtheabundantnaturalform(Llacticacid).Duetothechiralnatureoflactic
acid,severaldistinctformsofpolylactideexist.PolyLlactide(PLLA)istheproductresultingfrompolymerizationof(S,S)lactide.
PLLAhasacrystallinityofaround37%,aglasstransitiontemperaturebetween5080Candameltingtemperaturebetween173
178C.ThemeltingtemperatureofPLLAcanbeincreased4050Canditsheatdeformationtemperaturecanbeincreasedfrom
approximately60Ctoupto190CbyphysicallyblendingthepolymerwithPDLA(polyDlactide).PDLAandPLLAformahighly
regularstereocomplexwithincreasedcrystallinity.
PHA(polyhydroxyalkanoates)aresynthesizedbymicroorganismssuchasAlcaligeneseutrophus,growninasuitablemediumand
fedappropriatenutrientssothatitmultipliesrapidly.Oncethepopulationhasincreased,thenutrientcompositionischanged,forcing
themicroorganismtosynthesizePHA.HarvestedamountsofPHAfromtheorganismcanbeashighas80%oftheorganism'sdry
weight.ThesimplestandmostcommonlyoccurringformofPHAispoly(R3hydroxybutyrate),PHBorP(3HB)).PurePHB,
consistingof1000to30000hydroxyacidunits,isrelativelybrittleandstiff.Dependinguponthemicroorganism,manyofwhichare
geneticallyengineeredforthispurpose,andthecultivationconditions,homoorcopolyesterswithdifferenthydroxyalkanicacidsmay
begenerated.SuchcopolymersmayhaveimprovedphysicalpropertiescomparedwithhomoP(3HB).Presently,thesePHAscost
abouttwiceasmuchaspetroleumbasedplastics.AnengineeredswitchgrassthatgrowsPHAinsideitsleavesandstemshasalso
beencreated,offeringthepossibilityofavoidingsomeofthecostsassociatedwithlargescalebacterialfermentation.
IncontrasttoP(3HB),thepolymerof4hydroxybutyrate,P(4HB),iselasticandflexiblewithahighertensilestrength.Copolymersof
P(3HB)andP(4HB)aresynthesizedbyComamonasacidovarans.Themolecularweighremainsroughlythesame(400,000700,000
Da),butthermalpropertiescorrelatewiththeratioofthesemonomerunits.Thempdecreasesfrom179to130(orlower)withan
increasein4HB,andas4HBincreasesfrom0%to100%theTgdecreasesfrom4to46.4Hydroxybutyrate(4HB)isproducedfrom
1,4butanediolbymicroorganismssuchasAeromonashydrophila,Escherichiacoli,orPseudomonasputida.Fermentationbroth
containing4HBhasthenbeenusedfortheproductionofthehomopolymerP(4HB),aswellascopolymerswithP(3HB),[P(3HB
4HB)].Thefollowingtablelistssomeofthepropertiesofthesehomopolymersandcopolymers.
PropertiesofSomePolymers
Polymer

TmC

TgC

%Crystallinity

Tensile
Strength

P(3HB)

179

70

40MPa

P(4HB)

53

47

53

100

coPolymer
3HB20%3HV

145

50

32

coPolymer
3HB7%3HD

133

>50

17

isotacticPP

176

>50

40

LDPE

110

100

<50

10

3HV=3hydroxyvalerate,3HD=3hydroxydecanoate
Itremainsanopenquestionwhetherit'smoreenergyandcostefficienttousebiodegradableplasticortorecyclepetroleumbased
plastic.Thereislittledoubt,however,thatbiodegradablematerialsleadtolessenvironmentalpollutionwhenrandomlydiscardedafter
use,asisoftenthecase.

Problems

Thefollowingproblemsfocusonconceptsandfactsassociatedwiththetreatmentofpolymerchemistryinthistext.
ChooseaProblem

ReturntoTableofContents
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