EXTENDING THE APPLICATIONSFOR POLYALKYLENE GLYCOLSUSING NEW TECHNOLOGY CONCEPTSMartin Greaves, Ph.DThe Dow Chemical CompanyThe UEIL Annual Congress 2008"Lubricant raw materials - Technology and Supply"23-24 October 2008, Warsaw,The Dow Chemical CompanyOverview•Diversified chemical company with annual sales of $54 billion and 46,000employees worldwide serving customers in 160 countries•Connecting chemistry and innovation with the principles ofsustainability to helpprovide everything from fresh water, food and pharmaceuticals to paints,packaging and personal care products•Combines the power of science and technology with the “Human element” toconstantly improve what is essential to human progressPresentation Key Highlights & Desired Outcome•Highlight the opportunities polyalkylene glycols (PAG) offer in solvingmany of today’s lubrication challenges•Share the enormous technology design options for developing PAGsolutions•Propose how PAGs can “upgrade” the performance of hydrocarbonand vegetable oil technologies•Demonstrate how more environmentally friendly solutions can beachieved through improving friction control and energy efficiency aswell as providing biodegradable solutions that canminimizeenvironmental impact•Show four examples where PAG application expansionis occurring•Summarize how REACH impacts PAGsEquipmentEnvironmentalWater GlycolFluidsTextile &MetalworkingFluidsCompressorand Gear OilsAnhydrousHydraulic FluidsFUTUREHistorical Application Expansion of Polyalkylene Glycols&Energy EfficiencyApplication growthFire safetyProductionEfficienciesReduced fiber wasteImproved fiber qualityMWF cooling andlubrication efficienciesLong lifesyntheticlubricantsHeavy dutyindustrial gearsExtended lifeair compressorlubricantsEquipmentReliabilityAnhydrous fireresistant fluidsas ester alternativesFluids& QuenchantsExtending PAGs forWind TurbinesSpecialty MarineAuto-Engine oilsHydraulicsFood processingEnergy EfficiencyTimeChemistry & Versatility of PAGsPAG Polymerization TechnologiesBlockPolymerisationRandomPolymerisationInverse blockPolymerisationGeneral reaction scheme formanufacturing PAGsPolymer DesignPolymerisationPolymerisationPolymerisationInitiatorEO blockPO blockEO blockPO blockInitiatorInitiator....POEOMONOLSn-Butanol2-Ethyl hexanolAlkyl phenolsFatty aminesDIOLSWaterEthylene glycolPropylene glycol1,4-ButanediolTRIOLSGlycerolTrimethylolpropaneInitiatorsUnderstanding Design Principles – Impact of EO/PO ratioEO/POratioEO/POratioEO/POratioEO/POratioViscosity IndexPour PointOxidation rateFriction (control) coefficientFunctional Performance of Conventional EO/PO PAGsCompared To Alternative Base Oils↑∆↑Synthetic esterMineral oilPAGPAODiagram provides relative ratings between baseoils↑↑↑∆Clear benefit of PAGsDisadvantage of PAGsSpider diagram∆Functional Performance of Conventional EO/PO PAGsCompared To Alternative Base OilsSynthetic esterPAGPAOMineral oilsDiagram provides relative ratings between base oils↑↑∆Clear benefit of PAGsDisadvantage of PAGsSpider diagramRotary Screw Compressors•Widely used in air, natural gas andrefrigeration (R-134a and R-152a)compression.•PAGs eliminate sludge and varnishApplying the Benefits of PAGsApplying the Benefits of PAGs ––Deposit ControlDeposit Control•PAGs eliminate sludge and varnishformation•Thermo-oxidatively stable but anyoxidation products are soluble in thePAG base oil•Technology used in more than 100,000air compressors world-wide. Typicalservice life >8000 hours. Manyexceeded 50,000 hoursMineral oilcompressor lubricant•Prone to varnishformation•Short fluid lifePAG syntheticcompressor lubricant•Deposit free and clean•Long service intervalsOxidation of PAGsOxidation of PAGs ––Ether OxidationEther OxidationO CH2CHCH3O CH2CHCH3OO CH2CCH3O CH2CHCH3OOOHCHPeroxideLike all organics, PAG’scan oxidize under hightemp. operationsOxidation by-productsOOHO CH2CCH3O+O CH2CHCH3O+OHCCHOHCH3O+H2OPeroxideAldehydeketoneOxidation by-productsinclude aldehydes,ketones, low mol weightacidsOxidation byOxidation by--products areproducts areSOLUBLEin the base oil & unlike mineral oilsDO NOT FORM DEPOSITS AND VARNISH––key benefit of PAGskey benefit of PAGsApplying the Benefits of PAGsApplying the Benefits of PAGs ––Water SolubilityWater SolubilityHydraulic FluidsPlay a major role in the use of fire resistant water glycolhydraulic fluids (HF-C)Extending applications for water based lubricants mayhelp minimize ourdependency on oilPAGs –only major class ofonly major class of water soluble base oilwater soluble base oilhydraulic fluids (HF-C)PAGs used as viscosity builders to provide hydrodynamiclubricationMetalworking FluidsPAGs used in premium water based cutting fluidsFunction by unique inverse solubility mechanism (cloudpoint) forming thin film at cutting interfaceWind Turbine LubricantsTrends•Growth rates 15Growth rates 15--30 % per annum to 201430 % per annum to 2014•Demand for higher energy output and larger turbines•Increased loading on gears and higher operatingtemperatures•Off-shore turbines requiring longer service intervalsshore turbines requiring longer service intervalsLubrication Challenges•Eliminate microEliminate micro--pitting and scuffing oftenpitting and scuffing oftenseen with PAOs and mineral oils•Eliminate sludging•Improve corrosion performance in offImprove corrosion performance in off--shorewind turbines•Extend fluid life, drain and service intervalsTraction Measurements at 40oCContact Pressure of 1.25GPa, speed 1m/secComparison of ISO-VG320 for PAG and PAO Wind Turbine Lubricants0.060.070.080.09

Traction CoefficientPAOPAG-1 (100% PO)PAG-2 (60/40 EO/PO)PAG-3 (50/50 EO/POMini-traction Machine - Steel ball on steel disk0 20 40 60 80 100Slide Roll Ratio in %00.010.020.030.040.050.06

Traction CoefficientTraction Measurements at 80oCContact Pressure of 1.25GPa, speed 1m/secComparison of ISO-VG320 for PAG and PAO Wind Turbine Lubricants0.040.050.06

Traction CoefficientPAOPAG-1 (100%PO)PAG-2 (60/40 EO/PO)PAG-3 (50/50 EO/PO)Mini-traction Machine Steel ball on steel disk0 20 40 60 80 100Slide Roll Ratio in %00.010.020.03

Traction Coefficient0.030.04

Traction CoefficientPAOPAG-1 (100% PO)PAG-2 (60/40 EO/PO)PAG-3 (50/50 EO/PO)Traction Measurements at 120oCContact Pressure of 1.25GPa, speed 1m/secComparison of ISO-VG320 for PAG and PAO Wind Turbine Lubricants0 20 40 60 80 100Slide Roll Ratio in %00.010.02

Traction CoefficientMini-traction Machine - Steel ball on steel diskWind Turbine Lubricants•Industry has been reticent in using PAGs•Small percentage of turbines converted to PAGs•Provide excellent high load carrying capacity•Excellent friction control•EO-rich PAG’s offer high VI and low frictionrich PAG’s offer high VI and low frictionvalues across a wide operating temperature•PAGs offer improved thermoPAGs offer improved thermo--physical propertiesphysical propertiesthan hydrocarbonthan hydrocarbon productsproducts•Offer an alternative to PAO and mineral oilsApplications For Polyalkylene Glycols InAutomotive Fluids And Lubricants•Intrinsic tribological properties of PAGs are excellent•ThermoThermo--physical aspects are attractivephysical aspects are attractive•Ecologically more favourable than hydrocarbon oils•However conventional PAGs areNOT hydrocarbon compatibleApplication Development By Polymer DesignEO/POEOSolder assist fluidsTextile lubricantsGear lubricantsBearing oilsSurfactantsWater glycol fluidsRefrigeration oilsQuenchantswater soluble PAGsPAGs today arepredominantly usedin the IndustrialLubricants segmentPOPO/BOBO/EOBOAir Compressor fluidsHydraulic oilsApplicationexpansionBase fluid or co-basefluid for crankcase oils.Auto & Industrial gear oil.Transmission fluids.Metal rolling oils.Surfactants.Polymer designspaceoil soluble PAGsIntroducing BO for OILSOLUBLE PAGs could open the“application envelope” toinclude automotivePAGs As Future Base Oil Components Of Engine OilsPAGor PAG blendsBio-renewablesHigh performance synthetics,simplified technology andoffering biodegradabilityRenewable, sustainableEnvironmentalsustainabilityModern syntheticsIncrementalmprovement

PerformanceAdvances inFuel economy&EmissionMineral oilsSyntheticse.g. PAOWell established but limited fluid longevityHigher performance and highly engineered complex productsLonger drain intervals but weak environmental profileBreakthrough technologyoffering biodegradability(BIO-NO-TOX)Investment(development costs)time

PerformanceEmissionControl?Engines Oils – Options in using PAGsPAG Base OilAnti-oxidantA/W additivesFriction modifiersCorrosion inhibitorsHydrocarbon base oilDispersantModern engine oil formulations are highlycomplexCan the fundamental tribological and thermoCan the fundamental tribological and thermo--physical properties of PAGs eliminate thatcomplexity?DispersantAnti-oxidantZinc A/W additiveVI ImproverDetergentsFriction modifiersCorrosion inhibitorsMineral oilPAG Base OilAnti-oxidantA/W additivesFriction modifiersCorrosion inhibitorsBase oil using PAGBase oil of Mineral oil and PAGTechnology Options for Engine OilsUtilize PAG as the primary base oilUtilize PAG as the primary base oil ––option to use water solubleoption to use water soluble(EO/PO), water insoluble (PO) and oil soluble (BO) PAGs• Thermal conductivity of PAGs > mineral oils• Eliminate need for VI Improvers• Reduce detergent and dispersant treat levels•Reduce A/W and friction modifier treat levelsUtilize oil soluble PAGs (OSP) based on, for example, butylene oxidehomo-polymerspolymers• Incorporate OSP’s in formulations at levels of 10-30% to upgradethe performance of hydrocarbon oil containing productsValidation of Technical Concept for PAGs in EngineOilsPhase IPhase I ––Technical Validation of Hypothesis (Near Completion)Technical Validation of Hypothesis (Near Completion)• Vehicle studies ongoing• Primarily monitoring fluid condition, reliabilityand fuel efficiency• Exceeded expectations so farPhase II–Next phase/ R&D ongoingPhase IINext phase/ R&D ongoing• Defining application needs per market segment• Optimization of thermo-physical properties• Building structure properties maps based on chemistry variables.• Confirm initial research showing unique tribo-filmformation with PAGsPhase III• To work with industry partners to implement technologySpecialty Marine Lubricants1. Cost2. Performance3. Environmental acceptabilityDo PAGs have the functionality to serve the challenges of themarine market?Application for PAGs as specialtymarine lubricantsSub-sea Motion Compensatorssea Motion CompensatorsHydraulicsGearsStern Tube LubricantsExpanding PAGs into Specialty Marine LubricantsKnown PAG Benefits for Marine LubricantsWater solubleNon-sheeningBiodegradableLow eco-toxicityHydrolytic stabilityPreferred Additional Benefits.......•Constant rheology (viscosity) control at high water contamination levels (especiallyfor sub-sea systems)• Minimum loss of friction control and lubrication with watercontaminationEO/POratioWater solubilityM.W.BiodegradabilityPAG Base Oil Formulation Design – Controlling RheologyRandom Copolymers - Water Impact on Viscosity02040608010001020304050

V is c o s ity a t 4 0 o C , c S tNew Biodegradable PAGs - Water Impact on Viscosity0200400600800100001020304050

Viscosity at 40oC , cSt01020304050% Water in PAG01020304050% Water in PAGCombining the rheology propertiesof PAGs to optimize base oil designand provide fluids which are:• readily biodegradable• non-sheening• thermo-oxidatively stableNovel blends - Impact of Water on Viscosity0204060801001201400 10 20 30 40 50% Water in PAG blend

Viscosity at 40oCStable rheology control in sea waterTraction Performance of New PAG Marine Lubricant Base Oil(e.g. ISO-100 viscosity grade)0.040.050.060.070.080.09

Traction CoefficentNeatwith 20% sea waterTraction experiments at40oC, 1.25GPa and slideroll ratio 100% using steelball on disk configuration0501001502002503003504004505005506006507007508008509009501000Mean Speed - mm/s00.010.020.03

Traction CoefficentAt high speeds traction coefficients are improved with water contaminationAt lower speeds traction increases in the mixed EHLregimeEnvironmentally Friendly Hydraulic FluidsAgricultureEquipment reliabilityand operability in coldclimatesMarineBiodegradability andeco-toxicityFoodSafety when in contactConstructionEquipment reliabilitySteel &Die-castingFire resistanceSafety when in contactwith foodForestryBiodegradability(especially in Nordiccountries)Equipment reliabilityand operability in coldclimatesEnvironmentally Friendly Hydraulic Fluids in EuropeEurope offers a diverse range of technologies mostly basedon vegetable oils or synthetic esters.New Accreditations have emerged(European Eco-label)Eco-label- Renewable carbon content >50%- Fulfill hydraulic specificationrequirements (ISO-15380)What options are available with PAGs for use in environmentally sensitiveareas?PAG Based Anhydrous Fluids•Excellent hydrolytic and oxidation stability•Wide operating temp range. All season performanceduedue to high VI >200 and low pour pointsto high VI >200 and low pour points•Excellent lubrication and wearExcellent lubrication and wear performanceperformance•Increasing use in mobile and stationary equipment•BiodegradablePAGs as Environmentally Friendly Fluids•Biodegradable•Not derived from renewable resourcesPAG & Natural Ester Blends•Improved oxidation stability compared to naturalesters•Excellent intrinsic lubrication performance•Clean and deposit free•Biodegradable and based on renewable resourcesBenefits of PAG and H.O. Vegetable Oil BlendsPAGPAG + H.O. Veg oilH.O Veg oil507090110

K V 4 0, cS tH.O. Veg. oilPAG +H.O. Veg oilAccelerated oxidation test – ASTM D2893 (95oC)300 10 20 30 40 50Time, daysbeforebeforeafterafter•PAGs offer excellent thermoPAGs offer excellent thermo--oxidative stabilityoxidative stability•ThermoThermo--oxidative stability of vegetable oils can be improed andoxidative stability of vegetable oils can be improvupgraded inupgraded in combination with PAGscombination with PAGs•Decomposition products of vegetable oils are soluble in thePAGs providing less varnish formation and valve stickingcking ––hence greater equipment reliabilitySupply of PAGsSupply of PAGs --Manufacture beyond lubricantsManufacture beyond lubricantsHuge global infraHuge global infra--structure existing todaystructure existing todayfor manufacturing PAGs, polyethers,polyglycols for wide variety of applicationsand industries:and industries:--PolyurethanesFuel additivesSurfactantsPharmaceuticalsPersonal careDrilling fluidsas well asLubricantsBack integration into key oxidesBack integration into key oxides ––EO, PO and BOEO, PO and BOEO, PO and BO -can offer improved security of supplyREACHREACH --registration timeline took effect on June 1, 2007registration timeline took effect on June 1, 2007REACH & Polymers•Polymers are exempted from registration under REACH•REACH does require registration of raw materials, other substancesand additives that are used in the manufacture of polymers as follows:-•Monomers as well as other substances which have been reacted into thepolymer backbone must be registered if a polymer produced in orimported into the EU consists of 2% or more by weight of such monomersor other substances in reacted form exceed one metric tonne per annum.•Polymer additives need to be registered if they aremanufactured orimported on their own or in compounded form in volumes of one metrictonne or more per annum.Conclusions•PAG innovation will continue in solving problems which hydrocarbonoils can not•Upgrading hydrocarbon oils using oil solubleUpgrading hydrocarbon oils using oil soluble PAGs opens upPAGs opens up theapplication envelope•Application expansion is possible in new industrial applications (e.g.wind turbine and marine) as well as new automotive fluids•Application expansion is possible in new industrial applications (e.g.wind turbine and marine) as well as new automotive fluids•Environmental and energy efficient solutions are possible using PAGswhich can offer better friction control and improved thermo-physicalphysicalproperties than alternative options.•Back integration into EO, PO and BO can offer improvedsecurity ofsupply from your PAG partnerTHANK YOU