influence of rubber process oils on epdm compound · pdf filerubber process oil types hn:...
TRANSCRIPT
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
M. Hoffmann, Nynas AB, Technical Development and Market Support
Naphth
enic
s
Hydrocarbon Distribution (ASTM D 2140)
8
CA
CP
CN
M. Hoffmann, Nynas AB, Technical Development and Market Support
Rubber – Oil Compatibility
9
EPDM
NR
SBR
CR
NBR
Paraffinic Oil
Naphthenic Oil
Aromatic Oil
Esters
Polarity
M. Hoffmann, Nynas AB, Technical Development and Market Support
Oil Compatibility with EPDM
10
M. Hoffmann, Nynas AB, Technical Development and Market Support
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
M. Hoffmann, Nynas AB, Technical Development and Market Support
Window Gasket - 70 Shore A: Mixing Process
M. Hoffmann, Nynas AB, Technical Development and Market Support
OOH-cured, 70 Shore A:Processing characteristics
23
Highest dev torque for Nyflex 3120 and Gr II oil
SN 600 showed lowest torque
M. Hoffmann, Nynas AB, Technical Development and Market Support
OOH-cured, 70 Shore A:Cross-linking Density
24
M. Hoffmann, Nynas AB, Technical Development and Market Support
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
M. Hoffmann, Nynas AB, Technical Development and Market Support
OOH-cured, 70 Shore A:Hardness & Abrasion
26
Hardness close to design target
Nyflex 3120 & GrII oil show lowest abrasion
M. Hoffmann, Nynas AB, Technical Development and Market Support
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
M. Hoffmann, Nynas AB, Technical Development and Market Support
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.