TECHNICAL NOTE: TABLE - Antidegradants & Antioxidants

Antidegradants&Antioxidants
Chemicals Structure Staining Protectionagainst or Heat& Ozone Flex Non Oxidation Fatigue Staining Notes

ASTMD4676 Class1 PPD Anti degradants Paraphenylenediamines(PPDs) (GeneralStructure)

ST

Type1 DialkylPPD Antidegradant 77PD

ST

N,NBis(1,4dimethylpentyl)p phenylenediamine

Excellent Excellent Excellent PrimaryAntioxidants.DonatereactiveHydrogen(NH) tothepolymerperoxyfree radicals (RCOO.)during thepropagation stage of polymer degradation. All PPDs migratetothesurfaceoftherubberproductandreactdirectlyandcompetitively with ozone. Migratory losses can occur to adjacent compounds. Effectiveness of PPDs can be improved by incorporation of waxes and synergistic antioxidants. PPDsdecreasetherateofcutgrowthofrubbervulcanizates.Useofantioxidants alongwithPPDsprotectsthePPDsfromdirectoxidation.Dialkyl&AlkylArylPPDs increasepolymerscriticalstressnecessaryforozonecrackinitiation.TheDialkyl PPDsareinitiallythemostactiveantiozonantsfollowedbyAlkylArylPPDs&then the DiArylPPDs. Order of activity reverses as the ageing progresses due to oxidationandexposureofPPDs.ThesolubilityofPPDsantiozonantsdependson the solubility parameter of the rubber itself. (Example, Diaryl PPDs have low solubilityinNRandbloomabove1.0phrdosage.)AllPPDsexhibithighsolubilityin NBR based compounds and hence do not migrate easily to the surface to offer ozone protection. DiarylPPDs are more effective and persistent compared to otherPPDsinpolychloroprene(CR)compounds.However,PPDantiozonantscan crosslinkCRorotherhalogenatedpolymerscausingbincure.PPDantiozonants are easily oxidized by oxidizing agents (e.g. Lead Oxide) or even during storage. PPD antiozonants are not added in the RubberCarbon black master batch as oxidationofthisblenddestroystheactivityofPPDs. Excellent Excellent Fair Aliquidatroomtemperature.Excellentstaticozoneresistance.Offerslongterm staticozoneprotection.Notveryeffectiveunderdynamicconditions.Highlybasic nature& hence scorchy. Does not leach out in water. High volatility at elevated temperatures.Moresensitivetooxygenandheathencepoorpersistency&shelf life. A metal ion (Cu, Mn, Fe) deactivator. Causes severe contact & migration staining.UsedwithalkylarylPPDstoobtainstaticanddynamicozoneprotection forNRbasedtirecompounds. Dosage:1.0to2.0phr.


Chemicals

Structure

Staining Protectionagainst or Heat& Ozone Flex Non Fatigue Staining Oxidation

Notes

Type2 AlkylArylPPD Antidegradant 6PPD N(1,3Dimethylbutyl)N'phenyl pphenylenediamine Type2 AlkylArylPPD Antidegradant IPPD Type3 DiarylPPD Antidegradant DPPD Type3 DiarylPPD Antidegradant DTPD+DPPD

ST

ST

NphenylNisopropylp phenylenediamine

ST ST

N,Ndiphenylppd

Excellent Excellent Excellent Offer excellent antioxidant, static & dynamic ozone resistance and antiflex crackingproperties.Exhibitoptimummigrationrate.Arelessvolatilethandialkyl PPDs.Lowerlossesduringstorage,processing&cure.Offerlongtermprotection torubbervulcanizates. IPPDishighlybasicinnatureandinfluencescorch&cure.IPPDiseasilyleached outinwaterbut6PPDdoesnot.6PPDismuchlessvolatile&basicthanIPPD.If thelossesofIPPDduetovolatility&waterleachingaretakenintoaccount,then Excellent Excellent Excellent at equal dosages 6PPD shows better performance than IPPD. 6PPD exhibits high solubilityinrubberhencenoblooming.IPPDisaskinirritanthenceissubstituted by6PPDinmostpartsoftheworld.IPPD&6PPDarestable&havegoodshelf life.Dosages:1.0phrto4.0phr. EffectivenessofthesePPDsincreasesasthedosagesareincreased. Very Very Excellent Slower migration rate hence persistent, nonextractable by fuels & solvents and Good Good retained in the compound to offer long term protection. Limited solubility in rubberhencebloomover0.7phrinNR&1.0phrinSRs.Goodantioxidant,static &dynamicozoneresistanceandantiflexcrackingproperties.Doesnotinfluence scorch or cure rate. Used in combination with alkylaryl PPDs. Resume activity Very Very Very whenotherPPDsgetdepleted.Dosage:0.3to1.0phr. Good Good Good

ASTMD4676 Class2 Polymerized Trimethyl Quinoline Antioxidant TMQ Polymerized2,2,4Trimethyl1,2 dihydroquinoline

Mild Excellent Modest Modest Discolor (Static) ation No Contact staining

TMQis widelyusedintheRubberIndustryasgeneralpurpose,highactivityamine classantioxidant.TMQishighlypersistent,nonbloomingantioxidantandhas minimaleffectsonprocessingandcuringcharacteristicsofrubbercompounds. TMQoffersexcellentresistancetothermooxidativeageingofelastomers.Itslow volatility(duetopolymericnature)ensuresmaximumretention,lowmobility,and minimizedlossesthroughdiffusionandextractionbysolvents/fuels/oils.Dueto VeryhighactivityTMQiseffectiveevenatlowerdosages.TMQantioxidantalong with6PPDoffersimprovedoxidativeheatageingresistanceproportionaltothe dosagesof6PPDandTMQ.TMQisonlymildlydiscoloringanddoesnotcause contactstaining.TMQalsoexhibitsaweakantiozonantactivity.Thecomposition andperformanceofTMQvariesfromsuppliertosupplier. Dosage:0.72.0phr.


Chemicals

Staining Protectionagainst or Heat& Ozone Flex Non Fatigue Staining Oxidation

Structure

Notes

ASTMD4676 Class2 Antidegradant ETMQ

ST Excellent Excellent Discolor

Very good

6Ethoxy2,2,4trimethyl1,2 dihydroquinoline Non Staining Pale Yellow Orpink Discolor ation Non Staining Pale Yellow Discolor ation Non Staining Pale Yellow Discolor ation Good Modest (Static) Fair

Aliquidatroomtemperature. ETMQ is used in the Rubber Industry as Antiozonant & Antioxidant for general purpose rubber based compounds (e.g. Tire side walls, cushion gums etc. & Beltings).ParticularlyeffectiveinSBRcompounds.Nonblooming.Causessevere contactstaining.Alsousedasanantioxidantforanimalfeeds. Dosage:2.03.0orhigher(alone),Or2:1ratiowith6PPD/IPPD.

ASTMD4676 Class3 Phenolic Type1

Monofunctional

GeneralStructure Type1
Monofunctional

Good

Modest (Static)

Fair

Antioxidant SPH n=13 StyrenatedPhenol Type1

Monofunctional

Phenolic antioxidants are primary antioxidants. Classified by the number of phenolic groups in the molecule. More Sterically hindered antioxidants are less discoloringbuthavelowerantioxidantactivityinrubberapplication.ThePhenolic Antioxidants are NonStaining type and are used for the manufacture of white/colored rubber products and as stabilizers of raw Synthetic Rubbers. The Phenol radical can cause polymer degradation but this is prevented by the hinderedphysicalstructure(e.g.substitutionbystyrene)at2,6position.Sterically . . Hindered phenols act by scavenging RO And ROO Radicals via Hydrogen atom transferfromtheOHgrouptoformhydroperoxidesandphenoxylradicals. Low cost, comparatively weaker, less persistent antioxidant. Slight discoloration tendency on long term ageing of the rubber vulcanizates. Styrenated Phenol is muchlessvolatile&provideslongtermprotectionandiswidelyusedinwhite/ coloured latex based goods, general mechanical goods and footwear products. Dosage:1.02.0phr.

Good

Antioxidant BHT Butylatedhydroxytoluene

BHTismorevolatileandprovidesonlyshorttermprotection.Itismostlyusedas in process stabiliser for synthetic polymers to impart raw polymer storage stability.BHTalsofindsnonrubberapplications(e.g.Food)andisusedaspolymer stabilizerat0.5to1.5phrdosage. Dosage:1.0to2.0phrforrubberproductsmanufacture.


Chemicals

Staining Protectionagainst or Heat& Ozone Flex Non Fatigue Staining Oxidation

Structure

Notes

ASTMD4676 Class3 Phenolic Type2

Bifunctional

GeneralStructure Type2
Bifunctional

Non V.Good Staining Pale Pink Discolor ation Non V.Good Staining Pale Pink Discolor ation

Theseantioxidantshavelowvolatility,goodantioxidantactivityandexhibit minimaldiscolorationtorubbervulcanizates. Dependinguponthepositionoflinkages,bisphenolsaresubdividedintoortho orparabridgedbisphenolicantioxidants.

Antioxidant 22M46 2.2methylenebis(6tbutyl 4methylphenol)

Type2
Bifunctional Thiobisphenols

Antioxidant TBMC ASTMD4676 Class3 Phenolic Type3

Multifunctional

Orthobridged

Non V.Good Staining Pale Pink Discolor ation 4,4thiobis6(tbutylmetacresol Non V.Good Staining Pale Pink Discolor ation GeneralStructure

22M46isahighlypotentandismosteffectiveantioxidantforsulfurcuredrubber products. 22M46 is also an effective antioxidant for polychloroprene based products. 22M46 has a very low volatility and is most suitable for high temperature processing or product performance. 22M46 does not bloom on uncuredstocksandgivesprotectionagainstCopperandManganeseioncatalyzed oxidative ageing. These properties of 22M46 make it an interesting antioxidant even for critical carbon black reinforced rubber compounds! 22M46 is used in colored compounds; however; white colored products may show slight pink coloration on prolonged exposure to light. 22M46 is an excellent polymer stabilizerandisalsousedasanantioxidantforHotMeltAdhesivesbasedonEAM, EVAetc.Dosage:0.52.0phr Thiobisphenolsexhibithighantioxidantactivitycomparedtosimilarbisphenols. Thiobisphenols generate sulphur compounds which react with polymers during antioxidant protection reaction and compliment antioxidant activities of thiobisphenols.Thiobisphenolscausecomparativelyhigherdiscolorationofrubber vulcanizatesthanbisphenols. Dosage:0.52.0phr Multifunctional phenolic antioxidants are very high performance antioxidants, exhibit extremely low volatility anddo notcause contact/ migratory staining or discolorationsoftherubberproducts. Highermolecularweightofmultifunctionalphenolicantioxidantsalsocontributes to practically no leaching and extraction from rubber products by water or solventsandensuringlongtermprotectionagainstoxidation. The ortho bridged bisphenolic antioxidants exhibit excellent antioxidant performancebutshowdiscoloration(pinking)tendencytorubbervulcanizates.


Chemicals

Staining Protectionagainst or Heat& Ozone Flex Non Fatigue Staining Oxidation

Structure

Notes

Type3
Multifunctional

Polyphenol Antioxidant WingstayL (Goodyear)

Non V.Good Staining No Discolor ReactionproductofButylatedp ation cresol&dicyclopentadiene. Non V.Good Staining No Discolor ation V.Good

ASTMD4676 Class3 Phenolic Type3

Multifunctional

Butylatedreactionproductofparacresolanddicyclopentadiene(WingstayL)Is the most popular multifunctional phenolic antioxidant used both in dry rubber and latex based products where color stability, low volatility and long term protection against heat and oxidative degradation is desired. The resistance to oxidativedegradationisduetoaparticularlyfavorablepatternofsubstitutionon thephenolicgroup.Colorstabilityisduetothestearicimpossibilitytoformhighly conjugatedandcoloredbyproductslikequinones. Dosage:12phr. The para bridged bis phenolic antioxidants show slightly lower antioxidant performancebutdonotexhibitdiscolorationeffectonrubbervulcanizates.

Parabridged GeneralStructure Type3

Multifunctional

Parabridged Antioxidant Irganox1010 (Ciba) Tetrakis[Methylene3(3,5dit butyl4hydroxyphenyl) propionate]methane ASTMD4676 ST Class4 Discolor AlkylatedDPAs (Antioxidant) Diphenylamines (GeneralStructure)

Irganox anti-oxidants are phenolic based anti-oxidants that hinder thermally induced oxidation of polymers where high temperature applications are used. Unlike hindered amines, anti-oxidants are consumed - and not regenerated in the stabilization process. Irganox 1010 offers excellent protection against over bake yellowing by terminating free radicals in conventional solventbased and powder coating systems. The major usage of Iraganox 1010 is in Thermoplastics rather than rubbers. Dosage: 0.5-1.0 phr

Good

This class of antioxidants represents Substituted Amine Antioxidants which are complexreactionproductsofdiphenylamineandvariousalkylatingagents. The substituents are selected to achieve a desired balance of cost and performancecharacteristics.AlkylatedDiphenylAminesaremoderatelystaining and discoloring. These antioxidants are generally used as stabilizers of raw syntheticpolymersandasgeneralpurposeantioxidantsforrubbervulcanizates.


Chemicals

Staining Protectionagainst or Heat& Ozone Flex Non Fatigue Staining Oxidation

Structure

Notes

Diphenyl Amines (DPAs) (Antioxidant)

NST Discolor Alkylateddiphenylamines (Styrenated,Octylated, Heptylated,Nonylated)

Good

Styrenated Diphenyl amine a straw coloredamber liquid. Is highly active, low volatilityantioxidantandprotectsrubbersagainstdegradationduetoheat,light and oxygen. It is non blooming, non hydrolysable, non staining but discoloring type antioxidant and does not influence the cure rate of the rubber compound. Styrenated Diphenyl amine is widely used as a polymer stabilizer for the manufactureofstainingtypesyntheticrubbers.Itisusedinsomenoncriticaltire compounds,automotive&mechanicalmoldedgoods.Dosage:1.03.0phr. Darktanliquid.Mostlydisubstitutedwithsomemono&trisubstitution.Some orthosubstitution.Highlyactivenonstaining&mildlydiscoloringantioxidantfor NR&SyntheticRubbers.Lowvolatility.Offersverygoodheatresistancetorubber vulcanizates.Nonblooming.SuitableforCRbasedcompounds.Dosage:1.02.0phr 4,4Bis(,dimethylbenzyl)diphenylamine(DCDPA)isagrayishwhitepowder withmeltingpointof90degC.DCDPAisaslightlystainingtypeantioxidantwhich offersgoodheatandflexcrackingresistancetorubbervulcanizatesandisusedin therubberproductsbasedonNR,IR,BR,SBR,NBR,CR&ACM.DCDPAisless discoloringthanODPAandisespeciallyeffectiveagainstheatforACMbased compounds.Dosage:1.04.0phr. Octylateddiphenylamine(ODP)isabrownishtopurplecoloredantioxidant (Flakes)withmeltingpointof75degC.Octylateddiphenylamine(ODP)isusedas astabilizerinthemanufactureofsyntheticrubbers.Octylateddiphenylamine (ODP)isastainingandbloomingtypeantioxidantwhichoffersgoodheatandflex crackingresistancetorubbervulcanizatesandisusedintherubberproducts basedonNR,IR,BR,SBR,NBR,&CR.ItismostwidelyusedantioxidantinCR basedrubbercompoundssinceitdoesnotinfluencethebinstorageproperties. Dosages:1.02.0phr. Phosphiteantioxidantsarehydroperoxide(ROOH)decomposersandarealways usedincombinationwithHdonorse.g.hinderedphenols.Thephosphitesare oxidizedtophosphatesandRO.&ROO.Radicalsarereducedbythereactionwith theformationoftrivalentphosphoruscompounds. Thephosphitesarehydrolyzedeasilyinpresenceofacidicmaterials.Theyarealso destroyedduringsulphurvulcanizationandhencearenoteffectivewithsulphur curedproducts.

Antioxidant SDPA Wingstay29 (Goodyear) Antioxidant DCDPA Naudard445 (Chemtura)

porientedStyrenatedDiphenyl amine

NST Discolor

Good

4,4,bis(,domethylbenzyl) diphenylamine

ST Discolor

Good

ODPA (Antioxidant) OctylatedDiphenylamine

ST

Good

Good

ASTMD4676 Class5 Aromatic Phosphites

NST

Good

GeneralStructure


Chemicals

Staining Protectionagainst or Heat& Ozone Flex Non Fatigue Staining Oxidation

Structure

Notes

Antioxidant TNPP

NST

Good

Trinonylphosphate ASTMD4676 Class6

Diphenylamine Ketone Condensates

ST Modest Modest Modest

Phosphiteantioxidantsareusedasinprocessstabilizersandasstabilizersduring SyntheticRubbere.g.SBRmanufacture. Phosphitescanbeusedwithnonsulphurcuredproducts. Phosphitesgiveexcellentcolorretentionpropertiesbecausetheyactasreducing agents. Phosphiteantioxidantsarealsowidelyusedinthemanufactureofadhesivesfor tackretention. Therecommendeddosagesare1.02.0phr. Theseantioxidantsarecomplexreactionproductsofdiphenylamineandalkyl ketones(primarilyacetone),someofwhicharefurthercondensedwith formaldehydetoproduceproductsofhighmolecularweight.Theseantioxidants arelowmeltingpointresinsorliquids. TherearetwodifferenttypesofADPAcondensatesviz.lowtemperature reactionproductsandhightemperaturereactionproducts.Thehigh temperaturereactionproductsarereactivetowardsoxygenandprovidesome flexcrackingresistancebutareseverelystaininganddiscoloring.Theyarealso volatileanddonotprovidelongtermprotectionagainstthedegradativeforces thatconstantlyactonrubberproducts.Theseproductsaremostlyusedin mechanicalrubberproducts,somenoncriticaltyreapplicationsandasa stabilizerforemulsionSBR.Theseantioxidantsreducethebuildingtackof uncuredrubbercompoundsmakingproduct(e.g.tyres,conveyorbeltingsetc) buildingprocessmoredifficult. Thelowtemperaturecondensationproductsarenotveryreactivetowards oxygenbutarelessstaininganddiscoloring.Thesearecomparativelylessvolatile andcanprovidemediumtermprotectiontotherubbervulcanizates.Thesetypes ofADPAshavelowsolubilityinoilandhencesuitableforoilresistantcompounds basedonNBR.Dosages:1.02.0phr.

(Antioxidant)

AcetoneDiphenylamine condensates(ADPA)


Chemicals

Staining Protectionagainst or Heat& Ozone Flex Non Fatigue Staining Oxidation

Structure

Notes

Other Antioxidants Napthyl Amines PAN (Antioxidant) PBN (Antioxidant)

ST

Good

Highlyeffectiveantioxidants,buttoxicologicalrisk!(Carcinogenic). UsagediscontinuedintheRubberIndustry.

Phenylnapthylamine ST Very Good

Phenylnapthylamine MMBI &ZMMBI Antioxidants NST Very Good

TheseareheterocyclicSHcompoundsandaredifferentfromtheusualphenol/amine
antioxidants. Theseareusedwithotherantioxidantsforsynergisticeffectonheatresistanceproperties &metalasmetaldeactivators.Thiseffectdependsonthevulcanizationsystem.xMMBIis moreeffectiveinvulcanizatesproducedwithThiuramandDithiocarbamateaccelerators thaninsulfenamideorthiazoleaccelerators. Thecombinationsareparticularlysuitableforcompoundswhichcontainlowlevelsofsulfur andhighlevelsofaccelerators. Theseproductsoffernoprotectionfromcracking,whethercausedbyflexing,ozoneorthe actionoflightandoxygen. MMBIandZMMBIgivelittleprotectionfromheavymetalpoisoningwhenused individually.However,theprotectionisenhancedbyusingcombinationswithother antioxidantslike22M46.TMQ&MMBIandZMMBIcombinationsoresuitableantioxidants forrubberproductsbasedonperoxidecuredrubberproducts. Dosage:1:1incombinationwithphenolicantioxidants/amineantioxidants.

and

1,2Mercapto4(5) methylbenzimidazole

Zincsaltof1,2Mercapto4(5) methylbenzimidazole


Chemicals

Staining Protectionagainst or Heat& Ozone Flex Non Fatigue Staining Oxidation

Structure

Notes

Other Antioxidants Thioesters TDPEtype DIdodecyl3.3thiodipropionate

NST

Good

NST Good

TheThioestersareestersofthiodipropionicacid.Thesearesecondary antioxidantsandareusedwithphenolicoramineantioxidants. Thioestersarehighlyeffectiveperoxidedecomposersforlongtermheat resistancewhenusedincombinationwithphenolicantioxidants. Thioestersaredestroyedduringsulphurvulcanization.Hence,notusedfor Sulphurvulcanizedrubberproducts.Thioesterantioxidantsfindapplicationsin PlasticsandTPEs.Exhibitbloomingtendencyathigherdosages.

DIoctadecyl3.3thiodipropionate Other Antioxidants Dithio Carbamates ZDBC NiDBC (NBC) NST Good Dithiocarbamatesaremoderateantioxidantsbuttheiruseislimitedduetothe activatingeffectonsulphurbasedcuresystems. OneofthewidelyuseddithiocarbamateisNickelDibutyldithiocarbamate(NBC). ItisusedasanantiozonantforSBR,BR,NBR,ECOandCRbasedcompounds.Itis alsousedasanantioxidantandheatageresistorforCSMandEPDM. NickelDibutyldithiocarbamateshouldnotbeusedwithNRsinceitisapro oxidantwithNR. AnotherdithiocarbamateisZincdibutyldithiocarbamate.Thisproductisusedasa stabiliserforButylrubberproductionandasanantioxidantforrubberbased adhesives.

Zincdibutyldithiocarbamate NST Good

Nickeldibutyldithiocarbamate

Forselectingaproperantioxidants/antidegradantsforspecificenduserequirementsfollowingfactorsareconsideredtobeimportantforthechoice. a)Discoloration&Staining b)Volatility c)Solubility d)ChemicalStability e)Physicalform f)Antioxidant/Antidegradantconcentration g)Cost h)Health&Toxicityconcerns 9