influence of rubber process oils on epdm compound · pdf filerubber process oil types hn:...

Dr. Markus Hoffmann

SGF Meeting

Huskvarna, Sweden

November 24, 2016

Influence of Rubber Process Oils

on EPDM Compound Properties

2 Nynas AB, Technical Development and Market Support

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)

About Nynas AB

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

M. Hoffmann, Nynas AB, Technical Development and Market Support

Ongoing Changes in the Oil Industry

Driver: Higher

quality engine

oils and fuels

Gr. I ; 68%

Gr. II; 20%

Gr. III; 4%

Naphthenic; 8%

2007

incl. TDAE, MES, (T)RAE, DAE,

SN500, SN600, Brightstock

Gr. I ; 42%

Gr. II; 37%

Gr.III ; 13%

Naphthenics; 9%

2016

incl. TDAE, MES, (T)RAE, DAE,SN500, SN600, Brightstock

Gr. I ;29%

Gr. II48%

Gr. III14%

Naphthenics9%

Supply Prediction 2020

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

Source: Kline, 2013

Asia

North America

Europe

South America

RoW

Demand by Region

Naphthenics

DAE

TDAE

Paraffinics(SN500, SN600,

BS)

RAE

MES TRAE

Demand by product type

Total Volume:

ca. 3 000 000 MT

Rubber Process Oil Market

M. Hoffmann, Nynas AB, Technical Development and Market Support

Viscosity Range of Rubber Process Oils

12000600030001500200 800100

ME

S

TD

AE

RA

EDA

E

Heavy

Naphth

enic

Viscosities at 40 °C / 100 °F

400

NB

O

cSt

SN

50

0/6

00

BS

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Naphth

enic

s

Hydrocarbon Distribution (ASTM D 2140)

8

CA

CP

CN

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Rubber – Oil Compatibility

9

EPDM

NR

SBR

CR

NBR

Paraffinic Oil

Naphthenic Oil

Aromatic Oil

Esters

Polarity

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Oil Compatibility with EPDM

10

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Volatility – Evaporation Loss

Nynas AB, Technical Development and Market Support 2016-11-29

2016-11-29

Ageing Behaviour of Rubber Process Oils

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 M. Hoffmann, Nynas AB, Technical Development and Market Support

Which oil gets more easily oxidized?

T = 150 ˚C

p (O2): 7 bar

T = 150 ˚C

p (O2): 7 bar

GTL Oil

Heavy Naphthenic Oil

14 M. Hoffmann, Nynas AB, Technical Development and Market Support

Induction Times - O2 Pressure Drop of 10%

15 M. Hoffmann, Nynas AB, Technical Development and Market Support

Acidification Rates

GTL oils age 10 times faster as

compared to a naphthenic oil

16 M. Hoffmann, Nynas AB, Technical Development and Market Support

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.

Nynas AB, Technical Development and Market Support18 2016-11-29

Oil Performance in EPDM

Compounds

Plasticising Oil Properties

Nyflex3120

Nyflex3185

Nytex3250

Nytex 840 Gr II SN 600 BS

Density. 15°C kg/dm3 ASTM D 4052 0.876 0.894 0.907 0.922 0.868 885.8 901.4

Viscosity. 40°C mm2/s (cSt) ASTM D 445 120 185 250 372 104 112.1 494.8

Viscosity. 100°C mm2/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

M. Hoffmann, Nynas AB, Technical Development and Market Support

Window Gasket - 70 Shore A: Formulation

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Window Gasket - 70 Shore A: Mixing Process

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OOH-cured, 70 Shore A:Processing characteristics

23

Highest dev torque for Nyflex 3120 and Gr II oil

SN 600 showed lowest torque

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OOH-cured, 70 Shore A:Cross-linking Density

24

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OOH-cured, 70 Shore A:Tensile properties

25

Nyflex 3120 and Gr II oil give higher crosslinked networks

Nyflex 3185 & Nytex 3250 show a higher moduli compared to SN 600

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OOH-cured, 70 Shore A:Hardness & Abrasion

26

Hardness close to design target

Nyflex 3120 & GrII oil show lowest abrasion

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OOH-cured, 70 Shore A:Compression Set

27

Lowest compression set by Gr II oil followed by Nyflex 3120

Naphthenic oils show a lower compression set compared to SN600

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Automotive Wheather Strip - 65 Shore A: Formulation

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Wheather Strip - 65 Shore A: Mixing Process

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S-cured, 65 Shore A:Processing Characteristics

30

Gr I oils (SN600 and BS) show a lower developed torque

M. Hoffmann, Nynas AB, Technical Development and Market Support

S-cured, 65 Shore A:Tensile properties

31

Naphthenic oils show high tensile properties

M. Hoffmann, Nynas AB, Technical Development and Market Support

S-cured, 65 Shore A:Hardness & Abrasion

32

Hardness close to design targetSN600 somewhat lower

Lowest abrasion for Gr II oil followed by Nytex 3250 & Nyflex 3120

M. Hoffmann, Nynas AB, Technical Development and Market Support

S-cured, 65 Shore A:Compression Set

33

SN600 showed lowest set at 70 °C

Brightstock highest low-temperature set

Higher impact of ageing compared to OOH-cured compounds

M. Hoffmann, Nynas AB, Technical Development and Market Support

Summary

34 29 November, 2016

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

TAKING OIL FURTHER

We take oil further to bring lasting value to

customers and the world we live in.

markus.hoffmann@nynas.com