Polymerin Alkyd Resinha-1204

FileNo:NA/673April1999

NATIONALINDUSTRIALCHEMICALSNOTIFICATIONANDASSESSMENTSCHEME

FULLPUBLICREPORT

Polymerin Alkyd ResinHA-1204

ThisAssessmenthasbeencompiledinaccordancewiththeprovisionsoftheIndustrialChemicals(NotificationandAssessment)Act1989(theAct)andRegulations.ThislegislationisanActoftheCommonwealthofAustralia.TheNationalIndustrialChemicalsNotificationandAssessmentScheme(NICNAS)isadministeredbytheNationalOccupationalHealthandSafetyCommissionwhich alsoconductstheoccupationalhealth safety assessment.TheassessmentofenvironmentalhazardisconductedbytheDepartmentoftheEnvironmentandtheassessmentofpublichealthisconductedbytheDepartmentofHealthandAgedCare.

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Director

ChemicalsNotificationandAssessment

NA/673

FULLPUBLICREPORT

Polymerin Alkyd ResinHA-1204

1.APPLICANT

PPGIndustriesAustraliaPtyLtdofMcNaughtonRoad,Clayton,Victoria3168hassubmitted a limitednotification statementin support of theirapplication foranassessmentcertificateforthePolymerinAlkydResinHA-1204.ThemonomersareinacombinationnotpreviouslylistedintheAustralianInventoryofChemicalSubstances.

2.IDENTITYOFTHECHEMICAL

Thechemicalname,CASnumber,molecularandstructuralformulae,molecularweight,spectraldataanddetailsofthepolymercompositionhavebeenexemptedfrompublicationintheFullPublicReportandtheSummaryReport.

TradeName:AlkydResin HA-1204

1. PHYSICALANDCHEMICALPROPERTIES

Thefollowingdataareforthe50%solutionofpolymerinlightaromatichydrocarbonsolvent,denotedasAlkydResinHA-1204.

Appearance at 20°Cand101.3 kPa:

AlkydResinHA-1204isaclear,viscousliquid

BoilingPoint:155°C;seecommentsbelow

SpecificGravity:polymersolution=1.04polymer=1.21(calculated)

VapourPressure:nodatapresented;seecommentsbelow

WaterSolubility:nodatapresented;seecommentsbelow

PartitionCo-efficient(n-octanol/water):

nodatapresented

HydrolysisasaFunctionofpH:

nodatapresented,seecommentsbelow

Adsorption/Desorption:nodatapresented

DissociationConstant:nodatapresented

FlashPoint:43°C(polymersolution)

FlammabilityLimits:UpperExplosiveLimit=7%

LowerExplosiveLimit=0.8%;seecommentsbelow

AutoignitionTemperature:450°C;seecommentsbelow

ExplosiveProperties:nodatapresented

Reactivity/Stability:stableatambient/roomtemperatures;willreactwithoxidisingagents

CommentsonPhysico-ChemicalProperties

According to thenotifier,the polymeritself is never isolatedfromthein situmanufacturedpolymersolution.

Theboilingpointofthepolymersolutionwasnotdetermined.Itisexpectedtoboilat155°C,whichistheboilingpointoftheconstituentsolvent(lightaromaticnaphthafraction).

No vapour pressure data were presented for thenotified polymer.The polymer isexpectedtobeoflowvapourpressure,byanalogywithsimilarpolymers,andexhibitnegligiblereleaseto theatmosphere. For thepolymersolutionthe vapourpressurewould besimilartothat ofthesolvent(0.2kPaat20°C).

Thewatersolubilityofthe polymerwasnotdetermined.The polymeris expected tobe oflowsolubility inwaterbecauseitisnon-ionic,ofhighmolecularweightandcontainsa highlevelofhydrophobic(aliphaticandaromatic)groups.

No hydrolysisdata wereavailable forthenotified polymer.Asthepolymer contains estergroupsthereispotentialforhydrolysis,butthisisunlikelyatenvironmentalpHs(4-9) duetoitsexpectedlowwatersolubility.

Noadsorption/desorptiondatawereavailableforthenotifiedpolymer.Assolventevaporatesfromthepolymersolutionitbecomesmoreviscousandstickyandshouldreadilybindtosoilandsediment.

Thedeterminationofapartitioncoefficientcouldnotbeundertakenasthenotifiedpolymeris

expectedtobeinsolubleinwaterandwilllargelypartitioninton-octanolratherthanwater.

Due toits verylowwater solubility,the notifiedpolymer isexpected to become associatedwiththeorganiccomponentof soilsandsediments.Sinceitisofhigh molecularweightitisnotexpectedtocrossbiologicalmembranesandwillnotbioaccumulate.

Flammabilitylimits,autoignitiontemperatureandexplosivepropertieswerenotavailableforthe polymer.Datapresentedabovecorrespondtothe polymeric solution,whichwereassumed tobesimilarto those forthesolvent.Thepolymersolutionisaflammableliquidbutexpectedtobestableundernormaluseconditions.

The polymer crosslinkswithother paint components to form avery stable,high molecularweightpaintfilmthatfirmlyadherestotheprimerlayertowhichitisapplied.Thereis nolossofmonomers,additivesorimpuritiesduringthelifeofthecoating.

4.PURITYOFTHECHEMICAL

AlkydResinHA-1204isasolutionthatcontains50%byweightofthenotifiedpolymer.Theremainderisanaromatichydrocarbonsolvent(i.e.lightaromaticnaphthafraction).Thepolymeritselfisneverisolatedfromtheinsitumanufacturedpolymersolution.Anyimpurities,includingtheresidualmonomers,areatnegligibleconcentrations.Itisreformulatedintopaintcontainingthepolymeratconcentrationsofupto15%byweight.

5.USE,VOLUMEANDFORMULATION

Thenotified polymer istobeused asaresin inautomotiverefinish coatings.It will initially(2 years)beimported asacomponent ofpaintsolutionsat concentrations ofup to15% byweight.Itis expectedthatbothpolymer solution (i.e.AlkydResin HA-1204)andpaintwillinfuturebemanufacturedatthePPGAustraliaresinplant inClayton,Victoria.PaintscontainingthepolymerwillthenbeexportedintotheAsiaPacificregion.

The estimatedimportvolumeis 1-10tonnesforthefirst yearand10-100tonnes foreach ofthenextfouryears. Exportofupto80%ofthepolymeraspaintisanticipatedbeyond year2.

Solutionsofthenotifiedpolymerandreformulatedpaintproducts containingthenotifiedpolymerwillbe storedatthePPG warehousein Clayton, before distributionto customers.Polymersolutionwillbestoredin200litresteeldrumsandpaintwillbestoredin tinplatepaint cans and pailsof 5 and 15litre capacities.Transportation of paint cans to distributorsthroughoutAustraliawillbeviaroad.

6.OCCUPATIONALEXPOSURE

Accordingtothenotifier,fourmaingroupsofworkerswillbeexposedtothepolymer:

1.thoseinvolvedinlaboratorydevelopment;

2.thoseinvolvedinresinmanufacture;

3.thoseinvolvedinpaintmanufacture;

4.thoseinvolvedinpaintapplication.

Foreachgroup,themostlikelymeansofexposuretothepolymeranditssolutionswill beskincontactandinhalationofsolventvapours.

Laboratorydevelopment

Group1workers(approximately6)willbeinvolvedinsmallscalemanufacturingofpolymerand paint, as wellas producttesting.The maximumextent of exposure for anindividual isexpectedtobe8hoursperdayfor10-20dayseachyear.

Paint testing is to be performed in a ventilated spraybooth equipped witha fume extractionsystem.Anyspillsthat occurduringthemixing,gunfillingandsprayingstages,whileunlikely withgood workpractices, willresult inminimal exposure tothe userif the workerwearsthespecified protectiveclothing.Theminimumprotectiveclothingissuedtoworkersinvolvedinthehandlingofpolymersolutionandpaint,includesimperviousgloves,coverallsandgoggles.

Resinmanufacture

Group2workers(approximately9)willbeinvolvedinsamplingandtestingofpolymerfromthereactionvessel,aswellasthefillingofpolymerdrums,postsynthesis.The maximumextentofexposureforanindividualisexpectedtobe8hoursperdayfor10dayseachyear.

Paintmanufacture

Group3workers (approximately9) willbeinvolvedinpaint preparation,QCtesting andthefillingofpaintdrums.Themaximumextentofexposureforanindividualisexpectedtobe8 hoursper day for 30days each year.

AtthePPGfacilitythereare proceduresforminimisingtheexposureof workers(Groups2and3)tothepolymeranditssolutions.Fortheresinsynthesis,reactantsandsolventsarechargedtoaclosedreactorsystem.Paintmanufactureemploystheuseofhighspeedmixersfittedwithexhaustventilationtocapturevolatilesat the source.A regularmaintenanceprogramiscarriedoutandincludesmeasurementofairflowsatdeterminedintervals.Spillsthatoccurduringtheblendingandbatchingstagesarecontainedtotheplantthroughexistingbunding.Despitetheseprecautions,however,skincontaminationmayoccurintheeventofanyspillageduringtransferofresinsolutiontothehighspeedmixerandduringanyadjustmentofthepaintformulationinthemixer.

Bothpolymersolutionandpaintarefilledintocontainersunderexhaustventilationthatcapturesvapours.Anyspillsthatoccurduringthefillingstagearecontainedtotheplantthroughexistingbunding.However, skincontaminationmayoccurduringcleanupofspills(e.g.fromoverfillingofcontainers).

Wasteresinandpaint (upto2000 kg/year) aredissolvedandconvertedto aninertsolid thatcanbelandfilled.Theprocessmeetsallcurrentlocalenvironmentalstatutoryrequirements.Disposalcanalsobeperformedbyincineration.

Paintapplication

Group4workers(approximately6000)willbeinvolvedintheactivation,thinningandapplication of the paintproducts. Thecleaning of spray equipment willalso beperformed.Themaximum extent of exposure for an individual is expected to be 4 hours per day for 220dayseachyear.Trainingcoursesarerunforendusersonthecorrectwaytohandle,applyanddisposeofthecoatingsystem.

Skincontaminationmayoccurduringpaintmixingpriortosprayingandwhilstcleaningthespray equipmentafter application. Bothinhalation of vapoursandskincontaminationmayoccurduringsprayapplication.

Preventionofexposureduringpaintapplicationisachievedthroughacombinationofengineeringcontrols,personnelprotectiveequipmentandtrainingcourses.Cansofpaintarehandledby operatorsprotectedby anti-staticflameretardantoveralls,anti-staticfootware,imperviousglovesandeyeprotectionconformingtoAustralianStandardAS/NZS1337(StandardsAustralia/StandardsNewZealand,1992;StandardsAustralia,1994).Paintmixingandsprayingisperformedinawellventilated,downdraftsprayboothwithaminimumvolumeoffourairchangesperminute.Solventintheventilationsystemisventedviaastacktotheatmosphere. Oversprayistrapped inthesprayboothoronmasking materials such askraftandnewspaper.Thespraypainterwearsanair-fedbreathingmaskconformingtoAS/NZS1715andAS/NZS1716(StandardsAustralia/Standards NewZealand,1994a,b),inadditiontotheclothingspecifiedabove.

Paintwastes,generatedfromcleaningofthespraygunandmixing equipment,willbecollectedanddisposedofinthesamemanneraswastewaterisfromthespraybooth.Anestimate of the wasteisup to 7000kg ofpolymer over the firstyear and 14000kg of polymerforthesubsequentfouryears.Cleaningofwastefromsprayboothsistobecarriedoutbylicensedwastedisposalcontractors.The wasteisthen treatedandsenttotradewastelandfill.

7.PUBLICEXPOSURE

Thenotifierhasstated that paintcontainingthenotifiedpolymer willbeappliedinanindustrialenvironment;noreferenceismaderegardingsaletothepublic.Onceapplied,thenotifiedpolymerisincorporatedinacoatingformulationthatisintendedforuseontheexteriorofcarbodies.

8.ENVIRONMENTALEXPOSURERelease

There is potential for release ofthe notified chemical during the polymer manufacture,thepaintformulationandthe paint application.The manufacturing andformulation processeswilltakeplaceatthePPGplantandanyspillsthatoccurwillbecontainedbytheplantbunding.Polymerwastewillbecollectedatthesite,treatedanddisposedofasaninertresidue.Thenotifierestimatesthatupto2000kgperyearofwastepolymerwouldbegeneratedattheproductionsite.

Paint is applied to motor vehicles withapproximately30% efficiency ina spraybooth withcontrol measures,suchasfilters andpapermaskinginplace.Theresultingsurfacecoat isheatcured.Cleaningofthespraygunandmixingequipmentwillgeneratewastethatwillbecollectedanddisposedofinthesamemanneraswastewaterfromthespraybooth.

Duringpaintapplicationitisexpectedthat7000kgofwastepolymerwill begeneratedinthefirstyearand14000kgofwastewillbegeneratedinsubsequentyears.Someresiduewillalsoremaininthe‘empty’containersafter use.Forthefirstyearitisestimated that200kgwillremainasresidueinthecontainers and400kginthesubsequentyears(2%ofthe containercontents).

Fate

Thenotifiedpolymer,aspartoftheautomotivesurfacecoating,willsharethefateofthevehiclepanel, potentially beingrecycled asscrap.Incinerationofthepaintfilm would emitnoxiousfumes,includingoxidesofcarbon.

Thesolid wastegenerated fromthemanufacturing,formulation andapplicationofthepaintwillbedisposedoftolandfill(althoughincinerationisanoption).Presumablythepolymerisrecoveredasaninsolublesolidfromthewastewaterusedforcleaningandalsodisposedtolandfill.Thecontainersandtheirresiduewillalsobedisposedinthismanner.Leachingofthepolymerfromlandfillsitesisunlikely,giventhelowsolubilityofthesubstance.

Hydrolysis,althoughtheoreticallypossiblebecauseofthepresenceofestergroupsinthepolymer,isalsounlikelygiventhemildenvironmentalpHrange(4-9)ofnaturalwaters.Thepolymer isnot expected to cross biological membranes, duetoitslow watersolubility andhighmolecularweight,andassuchshouldnotbioaccumulate(Connell,1989).

9.EVALUATIONOFTOXICOLOGICALDATA

Notoxicologicaldatawereprovidedforthenotifiedpolymer.Thisisacceptableforpolymersofnumber-averagemolecularweight(NAMW)ofgreaterthan1000daltons.

The MSDSincludedtoxicologicalandhealthhazard informationonthesolventinAlkydResin HA-1204 (i.e. lightaromatic naphtha fraction).Itis likely thatthis solventwould betheprincipaltoxicagentinthispolymericsolution.

10.ASSESSMENTOFENVIRONMENTALEFFECTS

Noecotoxicologicaldatawereprovidedforthenotifiedpolymer.ThisisacceptableforpolymersofNAMWofgreaterthan1000daltons.

11.ASSESSMENTOFENVIRONMENTALHAZARD

Thenotified polymercrosslinkswithother paintcomponents toform a very highmolecularweightandstablepaintfilmthatadheresfirmlytotheprimerlayertowhichitisapplied.Thepolymer,aspartofthissurfacecoating,willthereforesharethefateofthevehiclepanel.ThepaintfilmwillslowlydeteriorateundertheactionofUVlight,butthisisnegligibleoverthelifeofthemotorvehicle.Whenthevehiclepanelisrecycled,thepolymerwouldbedestroyedthroughincineration.

The majority ofnotified polymerassociatedwith wastefrom theapplication of thepaint totheautomotivesurfaceshouldnotentertheenvironmentuntilitisdisposedtolandfill.Movementofthepolymerbyleachingfromlandfillsitesisnotexpectedbecauseofitslackofmobility,duetoeitheritslowwatersolubilityandhighbindingaffinitytosoilorcross-linkinginthecuredpaint.

If accidental spillageofthe polymer solution(orpaint) into waterways doesoccur,thenotifiedpolymer is not expected to disperse into the water,but settle out onto sediments. Ifspillageoccursonland,eitherduringtransportorusage,itisexpectedthatthepolymerwould becomeimmobilisedinthesoillayer.Contaminatedsoilcanthenbecollectedanddisposedtolandfill.

Given the aboveconsiderations, the notifiedpolymer isnot expectedto displaysignificantenvironmentalexposure,norpresentahazardtotheenvironment,whenitisstored,transportedandusedinthetypicalmanner.

12.ASSESSMENTOFPUBLICANDOCCUPATIONALHEALTHANDSAFETYEFFECTS

The notifiedpolymer itselfisneitherahazardoussubstance(accordingtotheNationalOccupationalHealthandSafetyCommissionApprovedCriteriaforClassifyingHazardousSubstances(NOHSC,1994b)),noradangerousgood.Duetoitshighmolecular weight andlowresidualmonomercontent,itisunlikelytotraversebiologicalmembranes.However,thepolymericsolutionisbothhazardous(e.g.harmfulbyinhalation[R20]andirritatingtorespiratory system andskin [R37/38]) andflammable (Class 3Dangerous Good), dueto theorganicsolvent(i.e.lightaromaticnaphthafraction)present.Therefore,appropriateprecautionsshouldbetakeninthehandlingandstorageofAlkydResinHA-1204solution.

Thetypesandprevalence ofinjuriesanddiseasesrelating toworkers exposedtothenotifiedpolymeranditssolutionwerenot available.Itisexpected thatpotentialhealtheffects aresimilar tothose ofthe solvent, whichare welldocumented andpresented ontheMSDS.Noadverse health effects (symptoms)areknownforthepolymeritself. When partofan inertfullycuredpaint film,thenotified polymerwillnot be availablefor exposure or absorptionand,therefore,isnotconsideredtobearisktohumanhealth.

OccupationalHealthandSafety

Thegreatestoccupationalexposureassociatedwiththenotifiedpolymerwillcomefromtheuseanddisposalofthepaintscontaining AlkydResinHA-1204solution.Thepresence ofhazardoussubstancesinsuchformulationsrequirestheuseofstringentengineeringcontrols,suchasacorrectlyconstructed andmaintained spraybooth,andofahighlevelof personalprotectiveequipment,suchasimpermeableoverallsandglovesandafullfaceshieldandrespirator.TheuseofanypaintcontainingAlkydResinHA-1204solutionshouldbeinaccordancewith theNational OccupationalHealth and Safety CommissionDraftNationalCodeofPracticeforSprayPainting(NOHSC,1991).

Thenotifierhasindicatedthatallpaintapplicationswillinvolvesprayinginawellventilated,downdraftspraybooth,withaminimumfourairchangesperminute.Paintover-spray,accountingfor70%ofpaintused,willbetrappedontosprayboothmaskingmaterialsandsolventwill be ventilated viaa stack into the atmosphere. Given these measures, standardpersonalprotectiveequipmentwillprovideanadequatelevelofprotectionfromthenotifiedpolymer,whichislikelytobelessintrinsicallytoxicthanmostofthesolvents,pigmentsandotherpaintresins.Healthrisks frominhalationandskincontactarethereforeexpectedtobeminimalduetothelowtoxicityandvapourpressureofthenotifiedpolymer,aswellastheinfrequencyofexposure.

Intheeventofanaccidentalspillofresinsolution orpaintformulation,thenotifiedpolymerwillremainpartoftheresinorpaintandbecomeattachedtoasolidabsorbent(e.g.soil,sandorotherinertmaterial).Thematerialcanbecollectedandsealedin asuitablevesselfordisposal.TheMSDSexplainstherecommendedclean-upprocedures.Careshouldbetaken,however,asspills willbeslippery andinhaledvapoursmaybeharmful.Allignitionsourcesshouldbeextinguished.

PublicHealth

Aspartofafullycuredpaintfilm,thenotifiedpolymerisofnegligiblerisktohumans.Hence, basedonthe intended usepatternofAlkydResinHA-1204,itisconsidered that thepolymerwillnotposeasignificanthazardtopublichealth.

13.RECOMMENDATIONS

Tominimise occupational exposure tothe Polymer in Alkyd Resin HA-1204, the followingguidelinesandprecautionsshouldbeobserved:

• SafetygogglesshouldbeselectedandfittedinaccordancewithAustralianStandardAS1336(StandardsAustralia, 1994) to complywithAustralian/NewZealandStandardAS/NZS1337(StandardsAustralia/StandardsNewZealand,1992);

• Industrial clothing should conform to the specifications detailed in AS 2919(StandardsAustralia,1987)andAS3765.1(StandardsAustralia,1990);

• ImpermeableglovesshouldconformtoAS/NZS2161.2(StandardsAustralia/StandardsNewZealand,1998);

• AlloccupationalfootwearshouldconformtoAS/NZS2210(StandardsAustralia/StandardsNewZealand,1994c);

• RespiratorsshouldconformtoAS1715andAS1716(StandardsAustralia/StandardsNewZealand,1994a,b);

• Spillage of thenotifiedchemicalshould beavoided;spillages should becleaneduppromptlywithabsorbentswhichshouldbeputintocontainersfordisposal;

• Goodpersonalhygieneshouldbepractisedtominimisethepotentialforingestion;

• AcopyoftheMSDSshouldbeeasilyaccessibletoemployees.

14.MATERIALSAFETYDATASHEET

TheMSDSforthenotifiedpolymer solution(Alkyd ResinHA-1204)wasprovidedinaccordancewiththeNationalCode of Practice forthe Preparation of MaterialSafety DataSheets(NOHSC,1994c).

ThisMSDSwasprovidedbytheapplicantaspartofthenotificationstatement.Itisreproducedhere asamatter of public record.The accuracy of thisinformationremains theresponsibilityoftheapplicant.

15.REQUIREMENTSFORSECONDARYNOTIFICATION

Under the Act, secondarynotification of the notified polymer shallbe required if any of thecircumstancesstipulatedundersubsection64(2)oftheActarise.Nootherspecificconditionsareprescribed.

16.REFERENCES

ConnellDW(1989)Generalcharacteristicsoforganiccompoundswhichexhibitbioaccumulation.InConnellDW(ed.),BioaccumulationofXenobioticCompounds.CRCPress,BocaRaton,USA.

NationalOccupationalHealthandSafetyCommission(NOHSC,1991)DraftNationalCodeofPracticeforSprayPainting.AustralianGovernmentPublishingService,Canberra.

NationalOccupational Health andSafetyCommission(NOHSC,1994a)ListofDesignatedHazardousSubstances[NOHSC:10005(1994)].AustralianGovernmentPublishingService,Canberra.

NationalOccupational HealthandSafetyCommission(NOHSC,1994b)ApprovedCriteriaforClassifyingHazardousSubstances[NOHSC:1008(1994)].AustralianGovernmentPublishingService,Canberra.

National OccupationalHealth and SafetyCommission (NOHSC,1994c) National Code ofPracticeforthePreparationofMaterialSafetyDataSheets [NOHSC:2011(1994)].AustralianGovernmentPublishingService,Canberra.

Standards Australia (1987) Australian Standard2919-1987,AustralianStandardIndustrialClothing.StandardsAustralia,Sydney.

StandardsAustralia(1990)AustralianStandard3765.1-1990,AustralianStandardClothingforProtectionAgainstHazardousChemicalsPart1:ProtectionAgainstGeneralorSpecificChemicals.StandardsAustralia,Sydney.

StandardsAustralia(1994)AustralianStandard1336-1994,AustralianStandardEyeProtectionintheIndustrialEnvironment.StandardsAustralia,Sydney.

StandardsAustralia/StandardsNewZealand(1992)Australian/NewZealandStandard1337-1992,Australian/NewZealandStandardEyeProtectorsforIndustrialApplications.StandardsAustraliaandStandardsNewZealand,Sydney/Wellington.

StandardsAustralia/StandardsNewZealand(1994a)Australian/NewZealandStandard1715- 1994,Australian/NewZealandStandardsfortheSelection,UseandMaintenanceofRespiratoryProtective Devices.StandardsAustraliaandStandardsNewZealand,Sydney/Wellington.

StandardsAustralia/StandardsNewZealand(1994b)Australian/NewZealandStandard1716- 1994,Australian/NewZealandStandardRespiratoryProtectiveDevices.StandardsAustraliaandStandardsNewZealand,Sydney/Wellington.

StandardsAustralia/StandardsNewZealand(1994c)Australian/NewZealandStandard2210- 1994,Australian/NewZealandStandardOccupationalProtectiveFootwear.StandardsAustraliaandStandardsNewZealand,Sydney/Wellington.

StandardsAustralia/StandardsNewZealand(1998)Australian/NewZealandStandard2161.2-1998, Australian/NewZealand Standard OccupationalProtective GlovesPart2:GeneralRequirements.StandardsAustraliaandStandardsNewZealand,Sydney/Wellington.