Petroleum Oils for Rubber Refining, Properties, Polymer Compatibility Jude Abia, PhD AEQ Technical Session Nov 8, 2017 @ Bromont, Quebec
HollyFrontier Overview Inland Merchant Refiner 5 refineries in Mid Continent USA and 1 refinery in Ontario, Canada Integrated Specialty Lubricants Producer Operate Crude and Product Pipelines, loading racks, terminals and tanks in and around refining assests ~500,000 barrels per day combined refining capacity Combined 12.1 Nelson complexity index Rubber process oils are produced at the HollyFrontier Lubes plant in Tulsa, Oklahoma and Petro- Canada Lubricants in Mississauga, Ontario 59 % interest in Holly Energy Partners, L.P. (HEP), a logistics MLP
HollyFrontier Lubricants & PCLI provide the broadest and purest slate of Base and Process Oils for finished products and end customers
Oil Refinery Process Flow Lube Oil Refinery Process Flow Light Neutral Light Neutral Base Oil Vacuum Gas Oil Atmospheric Tower Residue Vacuum Distillation Medium Neutral Heavy Neutral PDA DAO Oil Solvent extraction & Dewaxing Furfural Extraction MEK Dewaxing DWO Finishing Hydro- Finishing Catalytic dewaxing Medium Neutral Base Oil Heavy Neutral Base Oil Bright Stock Vac Tower Residue Asphalt Propane Deasphalting extraction (PDA) PDA Tar Wax Aromatic Oils Bitumen Slack Wax Furfural Extracts Bitumen blendstocks
Composition of Rubber Process Oil
Composition of Rubber Process Oil Compositional information about rubber oils can be obtained by: ASTM D2007 clay gel analysis Saturates Aromatics Polars Asphaltenes ASTM D2140 Carbon type distribution
Process Oil Classification Oil type ASTM D2501 VGC range Paraffinic 104 0.790-0.819 35% max. ASTM D2007* Aromatic wt% Naphthenic 103 0.850-0.899 35-65% Relatively Aromatic 102 0.900-0.939 65-80% Aromatic 101 0.940-0.999 80% min.
Key Properties for Rubber Process Oil Rubber Oil Properties Sundex 8000 EU Sundex 165 2000 SUS Naphthenic Sunpar 2280 Viscosity, cst @ 100C 68 50.1 19.8 31.2 Density KG/L @ 15C 0961 0.956 0.923 0.891 Aniline Point, C 77 81 99 129 Viscosity-Gravity Constant 0.872 0.871 0.849 0.792 Saturates 24 33 56 76 Polar Compounds 13 12 4 4 Aromatics 63 55 40 20 Molecular weight 590 588 500 690 Polycyclic aromatic compounds (PAH) Pass Pass Pass Pass Higher density means more oil mass available to interact with polymer for the same oil volume Higher aromatic content means greater compatibility for most polymer applications such as SBR, NR, IR, BR, CR Sundex 8000 EU and Sundex 165 are Residual Aromatic Oils and meet the EU REACH restriction on PAH Sundex 165 has lower viscosity and could be easier to handle in regions where cold weather presents a challenge.
Oil Compatibility with Elastomer One of most important characteristics of oil is compatibility with the rubber. Due to amount and migration capabilities, oil need to have good compatibility with polymer system to mitigate blooming Oil advantages are negated if oil blooms out during rubber processing or after vulcanization Rule: Use non-polar oils with non-polar polymers; Use polar oils with polar polymers
Oil Compatibility with Rubber Rubber Type Aromatic Naphthenic Paraffinic NR Very good Good fair SBR Very good Good Fair EPDM Fair Good Very good BR Very good Good Fair IR Very good Good Fair IIR, CIIR, BIIR Poor Fair Good CR Very good Good Fair NBR Good Fair Poor
Oil Processability Ease with which an oil incorporates into rubber Greatest compatibility; Most efficient in reducing viscosity; Only small amount is required Partial compatibility; Most efficient in reducing viscosity; Higher amount is required Non-compatible; least efficient in reducing viscosity; Large amount is required
Oil Takeup Time, Minutes Oil Take-up Time for 100 SUS Oils in SBR Less take-up time means lesser time to process batch and higher through-put 68 Aromatic region Naphthenic region Paraffinic region 58 48 38 28 18 58 68 78 88 98 108 118 128 138 Aniline Point of Oil, deg. C
Effect of Oil Compatibility on Rubber Physical Properties Rubber Formulation First Pass phr Solution SBR 4602 75.00 CV60 NR 25.00 Proaid AC-31 Process Aid 2.00 N234 10.00 Ultrasil 7000 GR Silica 60.00 Si69 Coupling Agent 4.80 Process Oil 10 or 20 Second Pass Zinc Oxide 1.90 Stearic Acid 1.50 Microcrystalline Wax 2.00 6PPD 2.00 TMQ 0.50 Final Pass TBBS 1.30 DPG 1.50 Sulfur 1.50
Crack Growth, DeMattia, Cycles to 1/2 inch Growth Tear Strength, psi 90000 80000 70000 Paraffinic region Naphthenic region Aromatic region Best performance obtained with aromatic 320 oils 300 60000 280 50000 40000 260 30000 20000 240 10000 220 0 20 40 60 80 100 Aromatics, wt % Tear Strength at 10 phr Tear Strength at 20 phr Crack Growth at 10 phr Crack Growth at 20 phr
Tensile Strength, psi 3900 Paraffinic region Naphthenic region Aromatic region Best performance obtained with aromatic oils 3700 3500 3300 10 phr 20 phr 3100 2900 16.5 20 30 40 50 60 70 82 Aromatics, wt %
Oil Compatibility Effect on Carbon Black Dispersion Rubber Formulation First Pass phr Solution SBR 4602 75.00 CV60 Natural Rubber 25.00 Proaid AC-31 Process Aid 2.00 N330 or N220 or N110 10.00 Ultrasil 7000 GR Silica 60.00 Si69 Coupling Agent 4.80 100 SUS Process Oil 10 or 20 Second Pass Zinc Oxide, Activator 1.90 Stearic Acid, Activator 1.50 Microcrystalline Wax, 2.00 6PPD, Antiozonant 2.00 TMQ, AgeRite Resin D 0.50 Final Pass TBBS Accelerator 1.30 DPG, accelerator 1.50 Sulfur, Curative 1.50 Properties Oil Type Aromatic Naphthenic Paraffinic Density, g/ml 0.976 0.946 0.883 VGC 0.929 0.890 0.806 Aromatic content, wt% Aromatic Carbon % Naphthenic Carbon % Paraffinic Carbon % 60 40 20 34 22 4 32 40 28 34 38 68
% Dispersion Effect of Oil on Carbon Black Dispersion 100 90 Aromatic oil showed 6% better dispersion than naphthenic oil Aromatic oil showed 13% better dispersion than naphthenic oil Aromatic oil showed 16% better dispersion than naphthenic oil 80 Aromatic Naphthenic Paraffinic 70 60 HAF (N330) ISAF (N220) SAF (N110)
Summary Oil effect on rubber properties is governed by the composition of the oils Most elastomers are polar and aromatic in nature and hence most compatible with aromatic oils Types of aromatic oils are Residual Aromatic Extract (RAE), Treated Distillate Aromatic Extract (TDAE) and Distillate Aromatic Extract (DAE) RAE and TDAE satisfy the EU REACH restriction on PAH limit Sundex 8000 EU and Sundex 165 are RAE oils Uniformity of a processing oil from batch to batch is necessary once a compound has been designed and standardized HollyFrontier s rubber oils are distilled products with close control of the properties important in rubber compounding to ensure consistency in each batch
Technical Support Fully equipped with $2,000,000 in rubber compounding and testing equipment
Rubber Mixing Lab Banbury Mixer Two-roll lab mill Hydraulic Compression Press Cold Feed Extruder Mixing rubber compounds Mixing rubber compounds Curing rubber compounds Lab-scale extrusions Hydraulic clicker press Bale cutter Die cut rubber test specimens Cutting bales of rubber
Rubber Testing Lab Rubber Process Analyzer Dynamic Mechanical Analyzer Materials Testing Machine Rebound Resilience Tester Abrasion Tester Fatigue to Failure Tester Moving Die Rheometer Mooney Viscometer Durometer Horizon Fog Testing System Dynamic properties before, during and after curing in a single test Dynamic mechanical properties as a function of stress, temperature, time, frequency, atmosphere Tensile stress-strain properties Rebound resilience Abrasive resistance Fatigue life in tension Cure characteristics Viscosity and scotch properties Hardness Automotive interior out-gassing
http://www.hollyfrontierlsp.com Jude Abia, PhD Product Development Specialist Process Oils Jude.Abia@hollyfrontier.com