Influence of Rubber Process Oils on EPDM Compound Properties Dr. Markus Hoffmann SGF Meeting Huskvarna, Sweden November 24, 2016
About Nynas AB 2 Nynas is the largest specialty oil producer in Europe Offices in more than 30 countries around the globe Net Sales: 2 Billion USD Average number of employees: 1000 Refineries in Nynäshamn (SE), Gothenburg (SE), Harburg (DE), Eastham JV (UK), Isla JV (Curacao) Nynas AB, Technical Development and Market Support
Rubber Process Oils: Products and Market
Rubber Process Oil Types HN: Heavy Naphthenic NBO: Naphthenic Black Oil RAE: Refined Aromatic Extract TRAE: Treated Refined Aromatic Extract SRAE: Special Refined Aromatic Extract DAE: Distilled Aromatic Extract (carcinogenic!) TDAE: Treated Distilled Aromatic Extract MES: Mildly Extracted Solvate SN 500/600: Solvent Neutral Paraffinic Base Oils BS: Bright Stock (SN 2500) Gr II/III: API Group II/III Paraffinic Oil GTL: Gas-To-Liquid Fluid (Fischer-Tropsch) Vegetable Oils
Ongoing Changes in the Oil Industry Naphthenic; 8% 2007 Gr. III; 4% Gr. II; 20% Gr. I ; 68% incl. TDAE, MES, (T)RAE, DAE, SN500, SN600, Brightstock Driver: Higher quality engine oils and fuels Gr.III ; 13% Naphthenics; 9% Gr. II; 37% 2016 Gr. I ; 42% incl. TDAE, MES, (T)RAE, DAE, SN500, SN600, Brightstock Fuels correspond to 81% of the total global oil consumption Engine oils correspond to 0.5% of the total global oil consumption Rubber process oils correspond to ca. 0.082% of the total global oil consumption Tire oils correspond to ca. 0.035% of the total global oil consumption Supply Prediction 2020 Naphthenics 9% Gr. III 14% Gr. II 48% Gr. I ; 29% incl. TDAE, MES, (T)RAE, DAE, SN500, SN600, Brightstock
Rubber Process Oil Market Demand by product type Demand by Region MES TRAE South America RoW RAE Paraffinics (SN500, SN600, BS) Naphthenics Europe Asia TDAE DAE North America Total Volume: ca. 3 000 000 MT Source: Kline, 2013
Viscosity Range of Rubber Process Oils Viscosities at 40 C / 100 F 100 200 400 800 1500 3000 6000 12000 cst RAE DAE NBO TDAE Heavy Naphthenic BS MES SN 500/600 Naphthenics
Hydrocarbon Distribution (ASTM D 2140) C N C P C A 8
9 Rubber Oil Compatibility NBR CR SBR NR EPDM Paraffinic Oil Polarity Naphthenic Oil Aromatic Oil Esters
10 Oil Compatibility with EPDM
Volatility Evaporation Loss Nynas AB, Technical Development and Market Support 2016-11-29
Ageing Behaviour of Rubber Process Oils 2016-11-29
RapidOxy Test The following test procedure was developed by Nynas: 4.5 grams of the base fluid is charged into a sample cup of Teflon. Temperature: 150 C Oxygen pressure: 700 kpa The program is terminated at a pressure drop of 10% of the maximum pressure in the chamber 13
Which oil gets more easily oxidized? GTL Oil T = 150 C p (O 2 ): 7 bar Heavy Naphthenic Oil T = 150 C p (O 2 ): 7 bar 14
Induction Times - O 2 Pressure Drop of 10% 15
Acidification Rates GTL oils age 10 times faster as compared to a naphthenic oil 16
Health, Safety and Environmental Legislations
Commission Regulation (EU) No 1272/2013 amending 1907/2006/EC (REACH) Articles shall not be placed on the market for supply to the general public, if any of their rubber or plastic components that come into direct as well as prolonged or short-term repetitive contact with the human skin or the oral cavity, under normal or reasonably foreseeable conditions of use, contain more than 1 mg/kg (0.5 mg/kg for toys) of any of the listed PAHs. 18 Nynas AB, Technical Development and Market Support 2016-11-29
Oil Performance in EPDM Compounds
Plasticising Oil Properties Nyflex 3120 Nyflex 3185 Nytex 3250 Nytex 840 Gr II SN 600 BS Density. 15 C kg/dm 3 ASTM D 4052 0.876 0.894 0.907 0.922 0.868 885.8 901.4 Viscosity. 40 C mm 2 /s (cst) ASTM D 445 120 185 250 372 104 112.1 494.8 Viscosity. 100 C mm 2 /s (cst) ASTM D 445 12.6 14.6 16.0 18.0 12.0 12.12 32.16 Flash Point. PM C ASTM D 93A 250 251 250 252 250 246 274 Flash Point. COC C ASTM D 92 268 263 267 273 275 271 304 Sulfur % ASTM D 2622 0.02 0.06 0.09 0.12 <0.01 0.49 0.74 Aniline Point C ASTM D 611 123 113 106 98 128 113 122 Viscosity-Gravity-Constant (VGC) ASTM D 2501 0.803 0.820 0.831 0.848 0.791 0.814 0.811 Refractive Index. 20 C ASTM D 1747 1.481 1.491 1.498 1.507 1.476 1.486 1.495 Colour ASTM D 1500 <1.5 <1.5 <2.0 <2.5 <0.5 1.0 4.5 Total Acid Number mg KOH/g ASTM D 974 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 CA % ASTM D 2140 1 6 10 12 1 3 5 CN % ASTM D 2140 30 29 30 33 28 33 28 CP % ASTM D 2140 69 65 60 55 71 64 67 DMSO Extractible Compounds % IP346 <3 <3 <3 <3 <3 Benzo(a)Pyrene mg/kg EN16143 <1 <1 <1 <1 <1 Σ 8 PAH (REACH) mg/kg EN16143 <10 <10 <10 <10 <10
Window Gasket - 70 Shore A: Formulation
Window Gasket - 70 Shore A: Mixing Process
23 OOH-cured, 70 Shore A: Processing characteristics Highest dev torque for Nyflex 3120 and Gr II oil SN 600 showed lowest torque
24 OOH-cured, 70 Shore A: Cross-linking Density
25 OOH-cured, 70 Shore A: Tensile properties Nyflex 3120 and Gr II oil give higher crosslinked networks Nyflex 3185 & Nytex 3250 show a higher moduli compared to SN 600
26 OOH-cured, 70 Shore A: Hardness & Abrasion Hardness close to design target Nyflex 3120 & GrII oil show lowest abrasion
27 OOH-cured, 70 Shore A: Compression Set Lowest compression set by Gr II oil followed by Nyflex 3120 Naphthenic oils show a lower compression set compared to SN600
Automotive Wheather Strip - 65 Shore A: Formulation
Wheather Strip - 65 Shore A: Mixing Process
30 S-cured, 65 Shore A: Processing Characteristics Gr I oils (SN600 and BS) show a lower developed torque
31 S-cured, 65 Shore A: Tensile properties Naphthenic oils show high tensile properties
32 S-cured, 65 Shore A: Hardness & Abrasion Hardness close to design target SN600 somewhat lower Lowest abrasion for Gr II oil followed by Nytex 3250 & Nyflex 3120
33 S-cured, 65 Shore A: Compression Set SN600 showed lowest set at 70 C Brightstock highest low-temperature set Higher impact of ageing compared to OOH-cured compounds
Summary Many different types of rubber process oils are available on the market (paraffinic, naphthenic, aromatic) Big changes are ongoing in the refining industry; Gr I closures and shift to Gr II and naphthenics New requirements in many countries to limit polyaromatic hydrocabons (PAHs) in tires and technical rubber goods; trend to low-pah oils continues Rubber process oils can significantly alter physical properties and dynamic mechanical behavior Naphthenic oils are less susceptible to oxidation compared to aromatic and highly refined paraffinic oils 34 29 November, 2016
markus.hoffmann@nynas.com TAKING OIL FURTHER We take oil further to bring lasting value to customers and the world we live in.