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TheLatestinPVCAdditivesandCompoundsHighTechSolutions!
SpecialChem|DonRosato Feb20,2012
NovelPVCTechnologies
PVCStabilizerDevelopment
NanoscaledMg(OH)
2
FlameRetardantAdditive
MultifunctionalAntioxidantAdvances
PVCAdditivesandCompoundsTechnologySources
PolyvinylChlorideLandscape
Polyvinylchloride(PVC)isathermoplasticpreparedbyfreeradicalpolymerizationofvinylchlorideviadispersion(emulsion),bulkor
suspension processes. A small amount of comonomer is sometimes added to enhance adhesion or other properties. Unmodified
PVCsarerigidsotheyrequireplasticizerstomakethemflexible.Themanufactureofawiderangeofplasticsispossiblebecauseof
PVC'smiscibilitywithavarietyofplasticizers.
Global consumptionof PVC has reached a level of about 35 million tons in 2011. PVCis an established polymerwith an average
growth rate less than World GDP (Gross Domestic Product), but is seeing good expansion in Asia due to more emphasis on
infrastructure and construction. In fact, markets indicate that the power of business in PVC and related sectors is shifting to Asia,
where PVC is growing atabout 7% or almostat the samerate asAsia'sGDP growth. NorthAmerica and Europeareboth mature
marketsforPVC.Theseregionsareexpectedtogrowatlessthan3%inthecomingfiveyears.Theplasticsadditivesglobalmarket
of$35.5Bisexpectedtoincreaseto$46.3Bby2015foracompoundedannualgrowthrateof4.5%.PVCcompoundsconsumemore
than65%ofthetotalvolumeof10milliontonnesofadditives,withmajorportionofthisvolumearisingfromplasticizers.Theglobal
plasticizermarketisan$11 Billionindustry.Plasticizersare thelargestcategoryofadditivesaccountingfor54%ofthe totaloverall
marketvolume.AdditivesforPVCexcludingplasticizers,amounttoavolumeofover1.5milliontons.
Heatstabilizerscontributemorethan30%oftheremaining35%oftheglobalPVCadditivedemand.Heavymetalbasedstabilizers
likeleadbasedproducts verywidelyusedforstabilizationofpipeinEuropeandAsia(exceptJapan),areresponsibleforverylarge
proportionoftheseproductsintheheatstabilizergroup.Pipeconstitutesalmost40%oftheglobalPVCconsumption.Inpipes,lead
content is about 11.5 %. PVC wire and cable sector also consumes lead stabilizers and will continue to use them because of
inherentadvantagesofferedbyleadintermsofsuperiorelectricalresistance.Whilethewireandcablesectorconstitutesonlyabout
23% of the total PVC resin consumption, it requires a heavy dosage of lead stabilizer at about a 23% level. Lead stabilizers are
beingdramaticallyphasedoutinEurope.Leadisbeingreplacedbylightermetalslikecalciumorzinc,aswellasorganicstabilizers.
Mostofthereplacementofleadwilltakeplaceinthepipesector.Thewireandcablesectorisexpectedtostay withleadstabilizer
longeruntilasuitablealternativeisdevelopedmatchingthefulltechnicalperformanceoflead.
Anothergroupofadditivescalledimpactmodifierprocessingaidsconstituteanother30%oftheremaining35%ofthePVCadditive
spectrum. More than 60% of compounded PVC is in the form of unplasticized or rigid products. They are not soft and flexible
becauseoftheabsenceofplasticizers.Toimpartbetterflexibilityandimpactstrengthwithoutaffectingrigidity,agroupofpolymeric
additives called impact modifiers are used. They are used at the level of 210% depending upon the impact strength requirement.
The MBS(MethylButadiene Styrene)copolymer acrylatesretaininherentPVC clarity and is usedfor packagingfilms and sheets.
There are other impact modifiers (predominately acrylates and chlorinated polyethylene) that also help in providing weather
resistanceduetobetterretentionofimpactstrengthoveralongperiodoftimeandareusedforwindowprofilesandothersimilarend
use applications. Rigid PVC is quite difficult to process since it has high viscosity. To improve its processability without reducing
mechanicalpropertiesappreciably,agroupofpolymericadditives(PMMA,orpolymethylmethacrylate,acrylic,ofspecificmolecular
weightandparticlesizedistribution)areused.Whilepipemayormaynotuseprocessingaids(onlylargerpipesrequireprocessing
aids), profile, rigid film and sheet need processing aid for ease of processability. Higher dosing and larger volumes of PVC are
responsibleforhigherusageofimpactmodifierprocessingaidandheatstabilizer.
PVC, with its chlorine content, is inherently more flame retardant (FR) than the other commodity polymers. However, addition of
plasticizers reduces flame resistance. For instance, limiting oxygen index of unplasticized PVC is 40 but plasticized PVC
compositions can have oxygen index as low as 22 to as high as 28. These compositions therefore arerequired to be made more
resistanttoflamebyincorporationofflameretardantadditives.Theflameretardantadditivesusedareantimonytrioxide,zincborate
ormolybdenumoxide.Whileantimonytrioxideincreasesoxygenindex,bothzincborateandmolybdenumoxidehelpinsuppression
ofsmokeafterthefireiscaughtbyPVCproduct.Tofurtherreducesmoke,additives(morelikefillers)suchasaluminumhydroxide
areincorporated.Theseadditivesarerequiredtobeincorporatedatmuchhigherdosagecomparedtoheatstabilizer,processingaid,
andotheradditiveconstituents.FRadditivesconstitute15%oftheremaining35%ofPVCadditives.PVCcompoundmeltgetsstuck
onhotmetalequipmentsurfacesduringprocessing.ItthereforerequiresahigherleveloflubricantstopreventstickingofPVCmelt
tohotmetal.Also,flowisimprovedbytheadditionofPVCcompatibleadditivescalledinternallubricants.Lubricantsofalltypesare
addedatabout0.51%levels.Approximately15%oftheremaining35%ofPVCadditivesarelubricants.
Antioxidantisgenerallyusedbypolyolefins,butPVCisquiteresistanttooxidativedegradation.Howeverthedosageofantioxidantis
lowerthan0.2%comparedtoaverage23%ofheatstabilizerusedinPVC.Antioxidantsmakeuponly3%oftheremaining35%of
PVCadditivesbyvolume,leaving7%35%inotherPVCadditivecombinations(i.e.,processingaids,antistaticadditives,andother
specialtyrubberimpactmodifiers).
NovelPVCTechnologies
PhthalatePlasticizersCovalentlyBondedtoPVC
Researchers at the Institute of Polymer Science & Technology in Madrid are developing technology to prevent potentially harmful
plasticizers such as DEHP (DOP) from migratingfromPVC.The advancecould lead to anew generation of PVCplastics that are
potentially safer than those now used in packaging, medical tubing, toys, and other products. The permanent plasticizer effect will
alsoensurePVCflexibilityismaintainedwiththepossibilityofextendingusefulproductlife.ThefunctionalizedplasticizerDOPSH[di
0 2 More
Figure1:PolyvinylChloride(PVC)Structure
(Source:PlasticsInstituteofAmerica)
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Pgina1de4 TheLatestinPVCAdditivesandCompoundsHighTechSolutions! Article
04/08/2012 http://www.specialchem4polymers.com/resources/articles/article.aspx?id=6896&lr=m...
(2ethylhexyl) 4mercaptophthalate]wasdevelopedwithphysiochemicalpropertiessimilartothoseofcommercialDOP,butwithan
additionalfunctionalgroupabletoestablishacovalentbondtothepolymericbackbone.Thepercentageofplasticizerthatcouldbe
covalentlylinkedtothePVCbackbonewassimilartoplasticizeramountsusuallycommerciallyemployed.Theapproachcompletely
suppressedplasticizermigration.WhiletheplasticizerefficiencyofthenovelplasticizersislessthanconventionalDEHP(DOP) the
glasstransitiontemperatureofmodifiedPVCislargelyreducedandisaround0Cforthehighestmodifiedsamples.Thisapproach
mayopennewwaystoprepareflexiblePVCwithpermanentplasticizereffectandzeromigration.
RigidandFlexiblePVCRequirements
PVC, an economic, high volume compounded material is one of the most important thermoplastics available, as a result of its
processability,adaptability,usefulproperties,andcapacitytoacceptmanydifferentadditives.Ingeneralthematerialismarketedas
unplasticizedorrigidPVCusedinpipe,sidingandwindowdoor profiles,andplasticizedorflexiblePVCusedinsuchapplications
asflooring,wallcovering,coatedfilmsfabricandtoysaswellaswireandcablejacketing.
PVC,whichisunstableatprocessingtemperatures,willdegraderapidlyintheabsenceofaheatstabilizer.Toperformsatisfactorily,
bothrigidandflexiblePVCcallforanefficientadditivepackagethatincludesheatstabilizers,andnumerousotheradditivesthatmay
potentiallyinteract,andalsomustbeoptimizedforgoodcostperformanceinagivenapplication.Heatstabilizers,whichareessential
componentsofaPVCformulationprotectthepolymerduringelevatedprocessingtemperatures,aswellaspreventlongertermheat
degradation in the ultimate enduse. They also prevent dehydrochlorination of the PVC and neutralize hydrochloric acid that may
have formed as well as prevent the plastic's discoloration. Rigid PVC is processed at higher temperatures and higher shear rates
thanflexiblePVCandasaresultrequiresmoreeffectiveheatstabilizers.Severalfamiliesofheatstabilizers(basedonsaltsoflead,
mixedmetals[calciumzinc,bariumzinc],organotinandorganicmaterials)arecompetingintherigidandorflexiblePVCmarkets
with stabilizer development beingdriven by both regulatory andcostperformance issues. Cadmium based heat stabilizers have in
generalbeeneliminatedandinEuropeleadbasedheatstabilizersarealsobeingphasedout.
PVCStabilizerDevelopment
CalciumBasedStabilizerSystems
In Europe, leadbased heat stabilizers have traditionally been used to protect rigid PVC for the construction industry as well as
flexiblePVCusedinwireandcablejackets.LeadstabilizedPVChasabroadprocessingrangeallowingPVCgoodstobeproduced
on a range of converting equipment. These formulations offer excellent performance versus cost and high heat stability, with less
wear on manufacturing equipment and permit inhouse scrap material recycling however lead use is becoming increasingly
controversial or outright banned. The leadbased stabilizers are therefore being replaced primarily by solid mixed metal stabilizer
systems (mainly calcium zinc based systems) for rigid PVC applications and liquid mixed metal stabilizer systems (essentially
calciumzinc,orbariumzinc)forflexiblePVCsystemssuchaswireandcablePVCjackets.
Incomparisontoleadbasedstabilizers,calciumbasedstabilizersystemsarecostperformancecomparableandhaveadvantagesin
handlingandproductpropertiessuchasoutdoorweatheringbutaremoreproductspecific,oftencallingforcustomformulation.Asa
resultreplacementofleadbasedstabilizersaroundtheworldisoccurringatdifferentrates,dependingontheapplication.InEurope,
theELV(EndofLife)Vehicledirectivemadeitdifficulttodisposeofleadcontainingmaterialsandasaresulttheautomotiveindustry
hasmovedmorerapidlytowardscalciumbasedstabilizers.
ManufacturershaverespondedtoincreaseddemandforCabasedstabilizers.BaerlocherGmbHhascommercializedBaerostabNT
3521P, asolid Cabased stabilizer for rigid PVC films and sheets.The stabilizer featuresexcellent heat stability,has approvalfor
FDA,EC200272andwithitslowemissionvolatilesissuitableforodorlessformulations.
Figure2:PlasticationwithSuppressedMigration
ExtractionofPlasticizedPVCSheetswithHeptaneatRoomTemperature
(Source:InstituteofPolymerScience&TechnologyMadrid)
Experttipstobetterchooseplasticizers&optimizecompetitivenessofyourPVC
compounds:
PVCPlasticizerSelectionStrategies
OnlineshortcourseonWed.September12,2012
Figure3:RigidandFlexiblePVCApplications
(Source:GrandorthSpecialtyChemicals)
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Also in response togrowingmarketdemand fornonleadadditives,Halstab,a division ofHammond GroupInc.addedafull lineof
calciumzincpowderstabilizerstoitsPlastiStabproductlineforPVCwireandcableapplications.Thedivisionalsocustomformulates
calciumzincstabilizersaroundspecificcompoundstomeetUL(UnderwritersLaboratories)specifications.
TinBasedStabilizerSystems
While much of the world has used leadbased heat stabilizers to protect rigid PVC and are transitioning to calcium zinc and even
organicalternatives,tinbasedheatstabilizersareusedinNorthAmericawhereitisexpectedtoremaintheprincipleheatstabilizer
of choice, with mixed metal and organic stabilizer systems finding certain niche applications. There are two main groups of tin
stabilizers. Members of the first group, with tinsulfur bonds, are referred to as tin mercaptide stabilizers. These sulfur containing
organotincompounds arehighly efficient and allowproduction of rigid PVC under themost demanding processingconditions. The
mostcommonlyusedareusuallymixturesofdialkylandmonoalkyltincompoundswiththealkylgroupsbeingmethyl,butyl,octylor
lauryl.While tin mercaptide stabilizers have very goodheat stability,they show moderate light stability which is often offsetby the
use of titanium dioxide,a whitepigment.As aresult,tinmercaptide stabilizers are notsuitedfor darkcoloredapplications suchas
dark coloredsidingandprofiles. Theyalso have a characteristicodor whichmaybeofconcern in certainapplications.The second
groupoftinbasedheatstabilizerscontainstinoxygen bonds.Membersof thisgroup includetin maleateandtincarboxylatebased
stabilizers. While not as good in terms of heat stability in comparison to tinmercaptide stabilizers, these heat stabilizers provide
excellent light stability and are finding growing use especially in outdoor applications such as transparent and translucent double
walledpanelsforgreenhouses,andsiding/windowprofiles.
ArkemahasaddednewcosteffectivebutyltinmercaptidestabilizerstoitsestablishedThermoliteproductrange.Thermolite130and
Thermolite 135 tinstabilizerscanbeused asasinglestabilizer,permitting loweroverall tincontentwithoutimpactingthequalityof
rigidPVCpipeextrusionsusedinsuchdemandingpipeapplicationsasthinwallagricultural,largediameter,andsewerpipe.These
stabilizerscanalsobeusedinextrusionofelectricalconduitandtelephoneducts.Inadditiontoreducingmaterialcosts,theuseofa
single stabilizer can decrease inventory costs and cut blending errors. A third new cost effective grade of butyltin mercaptide
stabilizersisThermolite150designedforhighoutputextrusionofwindowprofilesandotherdemandingrigidapplications.
Addressingthetypical'sulfurlike'odorofmanyorganotinsduetothepresenceoffreemercaptans,AkcrosChemicalshasdeveloped
anewlowodorreverseesterorganotinmercaptidestabilizerforthePVCsiding,fencingandprofileextrusionmarkets.AkcrostabT
5311containsamercaptanchemicaltrapdesignedtocreateauniquelylowodororganotinmercaptideheatstabilizer.
NanoscaledMg(OH)
2
FlameRetardantAdditive
Aqueous colloidal chemistry is also being successfully applied to the development of nanoscaled flame retardants. Headwaters
Technology Innovation Group (HTIG) develops and deploys a range of breakthrough technologies that improve natural resource
utilizationthrough the application of nanotechnology. One such material is a nanoscaled magnesium hydroxide,'NxCat' Mg(OH)
2
,
which is primarily used as a flame retardant additive and is PVC compounding applicable. As halogenated flame retardants are
graduallyphasedoutforenvironmentalandlegislativereasonsnew'greener'FRsarebeingsought.EnvironmentallyfriendlyMg(OH)
2
hasbeenused asalternative however,upto 60%loading isrequiredas aresultofthelowefficiencyofthe microsize Mg(OH)
2
.
Suchhighloadinglevelsontheotherhandimpairthemechanicalperformanceofplastic.Inordertomaximizethewaterreleaseand
flame extinguishing effect of Mg(OH)
2
, HTIG is using its manufacturing process which allows very small crystallites (~3 nm) of Mg
(OH)
2
toformandresultsinaverylargesurfaceareaandsuperiordispersionofthenanoscaledMg(OH)
2
inthepolymer/composite
materials.
MultifunctionalAntioxidantAdvances
Irgatec NC 66 is proprietary antioxidant system developed by BASF to address the unique stabilizing requirements of nanoclay
basednanocomposites.Thematerialisspecificallydevelopedtoenhancetheheatstabilityofnanoclaycompositeswhileprocessing,
to permit faster, hotter processing conditions. The additive package also reduces odor upon processing, retards yellowing during
aging, and improves longterm heat and light stability. This patented blend of phenolic and other antioxidant functionalities, plus
calcium organic salts, and metal oxides works on the different elements of a nanocomposite that are known to increase risk of
degradation,includingthenanoclay,compatibilizer,andimpactmodifier.
Multifunctional antioxidants are a relatively recent advance that beneficially combines both primary and secondary antioxidant
functionsinonecompound.Combiningmultiplestabilizingfunctionsinonemoleculeeliminatestherequirementforcostabilizersto
be used (i.e., phosphites, thioesters) greatly simplifying antioxidant storage, handling, and formulation. Irganox 1520 and Irganox
1726fromBASFaretwoprincipalantioxidantproductsinthisnewclassofstabilizers.Thesetypeantioxidantsareusedinpolyvinyl
chloride(PVC),aswellaslinearlowdensitypolyethylene(LLDPE),highdensitypolyethylene(HDPE),andstyrenebutadienerubber
(SBR).
Figure4:BaerostabNT3521PStaticHeatStability
(Source:BaerlocherGmbH)
Figure5:NanoscaledMg(OH)
2
(Source:HeadwatersTechnology
InnovationGroup)
Pgina3de4 TheLatestinPVCAdditivesandCompoundsHighTechSolutions! Article
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PVCAdditivesandCompoundsTechnologySources
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SpecialChem4PolymersMembersReactions
Jul11,2012
postedbyAbdulKarimQasim,Production/ManufacturingatNationalCo.forSponge&PlasticIND
Jun13,2012
postedbyMichaelWorns,R&DApplied/Formulation/ProductdevelopmentatDampingTechnologies,Inc.
Figure6:MultifunctionalAntioxidant
(Source:BASF)
Table1:PVCAdditivesandCompoundsTechnologySources
Company Website
PlasticsInstituteofAmerica www.plasticsinstitute.org
InstituteofPolymerScience&Technology www.ictp.csic.es
GrandorthSpecialtyChemicals www.grandorth.com
Baerlocher www.baerlocher.com
Arkema www.arkemainc.com
AkcrosChemicals www.akcros.com
ArchnowpartofLonza
http://www.specialchem4polymers.com/tc/biocides
solutions/index.aspx
LearnmoreaboutLonza'sSolutions:
http://www.specialchem4polymers.com/tc/antioxidant/index.aspx?
id=productselection
HeadwatersTechnologyInnovationGroup www.headwaters.com
BASFPerformanceProducts
http://www.basf.com/group/corporate/en/aboutbasf/profile/performance
products
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Pgina4de4 TheLatestinPVCAdditivesandCompoundsHighTechSolutions! Article
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