Innovations in Polyalkylene Glycol Based Lubricants STLE National Meeting

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1 Innovations in Polyalkylene Glycol Based Lubricants STLE National Meeting May 2011 Richard Butler & Dr. Govindlal Khemchandani Chemtool, Inc. Dow Chemical

2 PAG New Technology Polyalkylene glycols (PAG) have been around for years a brake fluids, automotive AC compressor lubes, water based hydraulic fluids and water based quench fluids. New PAG have OTMOL (oil tolerant) and OSMOL (oil soluble) technology. OTMOL and OSMOL greatly expand PAG applications.

3 Innovation Dow oil miscible and soluble PAG are products that will produce discontinuous innovations. PAG Structure - EO only These polyalkylene glycols are once in a generation technology leaps.

4 PAG Structure Polyalkylene glycols: O R OH + n H 2 C CH R O CH 2 HC O H n alcohol starter R' alkylene oxide R' polyalkylene glycol R, R' = H, CH 3, alkyl, aryl

5 Mineral Oil Soluble Polyalkylene glycols Octene oxide: - Lowest O/C ratio - Fully oil soluble - Low pour point - Liquid products Butylene oxide: - Water insoluble - Oil soluble - Liquid products Mineral Oil Solubility Design Space Oxides Ethylene oxide: - Highest O/C ratio - Water soluble - Solid products - High MW Propylene oxide: - Limited oil solubility - Low pour point - Liquid products

6 Inherent Lubrication Shell 4 Ball Wear gives an average of 0.5 mm wear scar for base PAG fluid without any additives In contrast, mineral oils and PAO have 4 Ball Wear scars of greater 1.3 mm if no additives are present

7 PAG Greatest Benefits Greatly reduced varnish Mineral Oil Can be blended 50:50 with mineral oil to practically eliminate varnish clean gears Polyalkylene glycol Blends are lower cost; only ~3X over conventional base stocks compared to full PAO synthetics at 5X Rotary Screw Compressor

8 Varnish is the Enemy Cascade of Failure Oils polymerize under heat and pressure in air. Polymerized varnish is sticky and attracts dirt The dirt imbedded in varnish causes wear much like abrasive glued to paper.

9 Polyalkylene Glycols PAG hold great promise. Will not form sheen on water Superior oxidation stability. Best pour points, very high VI etc. Inherently superior lubrication before additives

10 Bio-Based Metal Working Fluids Fastest growth area in MWF for 2009 Popular in Germany and Scandinavian countries Very good inherent lubricity Soy Beans

11 Synergies with Renewable and Biodegradable Vegetable Oils Vegetable oils have very poor oxidative stability and form heavy varnish. They also have high pour points and are limited in arctic applications. However, vegetable oils are renewable resources and they are also readily biodegradable. PAG are very good in oxidative conditions and do not form varnish. They also have good pour points and high viscosity indexes. PAG are NOT renewable but they do slowly biodegrade better than PAO and mineral oils. Solution to both draw material s drawbacks is 50:50* blend to produce renewable and readily biodegrable lubricants with low pour points and high VI.

12 MEHF MOBILE ISO 46 HYDRAULIC OIL TYPE MEHF PAG BIO DESCRIPTION GROUP II NEXGEN 60% CANOLA 40% PAG 40 C VIS@ 100 C VISCOSITY INDEX SPECIFIC 60 F POUR POINT C < -30 <-30 <-30

13 HIGH TEMP HD GEAR OIL TYPE CURRENT POLYSYN BIO SYNTHETIC DESCRIPTION GROUP II Polyalkylene Glycol 60% CANOLA 40% PAG 40 C VIS@ 100 C VISCOSITY INDEX SPECIFIC 60 F POUR POINT C < -20 <-30 <-30

14 SAE 75W-140 GEAR OIL TYPE PAO SYN GO SPECS POLYALKYLENE GLYCOL PAG-SYN BLEND BIO SYNTHETIC FLASH POINT C COC POUR POINT C < -46 <-46 <-46 NA VIS@ 40 C VIS@ 100 C VISCOSITY INDEX SPECIFIC 60 F BALL LWI ASTM 75 C mm NA WELD: 315 KG LWI: 59 WELD: 315 KG LWI: 55.1 WELD: 315 KG LWI: BALL WEAR SCAR in mm (ASTM 4172) NA

15 Typical Traditional Synthetic Fluid Formulation Using Water Soluble PAG Component Amount (wt %) Polyalkylene glycol 5-15 Phosphate ester (or fatty acid) 0-7 Borate corrosion inhibitor 0-5 Carboxylate corrosion inhibitor Triethanolamine Biocide 2-4 Water 45-60

16 Cloud Point of 1% Water Soluble PAG in Water

17 PAG in MWF Water soluble PAG have been the active lubricant in synthetic metal working fluids since the early 1960 s. PAG synthetic coolants run very trouble free at 10% - far less maintenance than soluble oils. Synthetics popularity peaked in mid 1980 s and sharply declined by mid 1990 s Problem was STICKY RESIDUE caused by rust preventatives used as part of synthetic coolants.

18 PAG EMULSION Used in water based metal working fluids PAG Emulsion 5% EMULSION FALEX AT 1750 LBS 60 LBS TORQUE BREAK. IRON CHIP TEST 1% CONCENTRATION NO RUST AL STAIN TEST: NO STAIN AFTER 24 HOURS.

19 PAG Dynatorque Way cover cleanliness improved Washes away smut Superior graphite smut control over both mineral oils and PAO -Solves synthetic lubricant residue problem!-

20 New PAG Lubricants Polyalkylene Glycol based Diesel engine oil * Polyalkylene Glycol TO-4 TDTO and Bio-synthetic TO-4 TDTO Polyalkylene Glycol and Bio-synthetic mobile hydraulics Polyalkylene Glycol and Bio-synthetic greases No-sheen marine dockside, forestry and wetland mobile hydraulics Polyalkylene Glycol and Bio-synthetic heavy duty industrial and automotive gear oils * Dow Chemical

21 Base Stock Differences and Solvent Properties Petroleum oil and closely related synthetic polyalphaolefins (PAO) are non-polar All additives such as detergents, pour point depressants, anti-wear and antioxidants are polar Like dissolves like rule for solubility Polyalkylene Glycols (PAG) are much more polar than oils. Oil VHVI Paraffinic oil Naphthenic PAO TMP Ester OSP (Oil Soluble PAG) Aniline Point C < -30 Table 1: Solvating Power of OSP: Aniline Point ASTM D 611

22 PAG Based Engine Oils

23 Property Base Fluid Eco Summary Fluid Type Petroleum Oils PAO Synthetic Vegetable Oils PAG PAG / Vegetable Blend Biodegradation Poor Poor * Excellent Very Good Very Good Renewability Poor Poor Excellent ** Poor Good Eco-Toxicity Poor Poor Excellent Very Good Very Good Water Solubility Poor Poor Poor Varies * Poor

24 Base Fluid Performance Summary Property Fluid Type Petroleum Oils PAO Synthetic Vegetable Oils PAG PAG / Vegetable Blend Low Temperature Poor Very Good Very Poor Very Good Very Good Viscosity Index Poor Very Good Very Good Very Good Very Good Additive Solubility Poor Very Poor Excellent Very Good Excellent Oxidation Resistance Poor Good Very Poor Excellent Fair Polyalkylene Glycols (PAG) are best in overall performance

25 Soot Deposit and Control PAG have superior soot control Will not oxidize to form varnish No varnish means no soot in the varnish - no sticky sludge Much cleaner crank case and oil passages

26 ATF Possibilities Anti-sludging properties are even more important than required in DEO Automatic transmission cases and valve bodies have strict mirror like micro-inch finish requirements for reamed holes

27 Goal Avoid This Automatic Transmission Diesel Engine

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29 Turbine Oils Extremely high temps Why would anyone use anything other than a non-varnishing PAG in this environment? Current group II and III oils with antioxidants have reached a plateau!

30 OTMOL PAG only new base oil technology in a generation Too Important to ignore