Ketjenlube Polymer Esters Dithiocarbamates Di-esters

Transcription

1 Akzo Nobel, headquartered in Arnhem, The Netherlands, is a worldwide operating company with activities in more than 50 countries and about 68,000 employees. Consolidated sales aggregated 14 billions Euro in The product range includes chemicals, coatings and health care products. The production and marketing of the Ketjenlube Polymer Ester range is concentrated in Arese, a Sub-Business Unit within Akzo Nobel Chemicals. The Arese product portfolio includes fatty acid esters, chlorides and amides, phosphorous acid and lubricating oil additives (antioxidants, friction modifiers) in addition to the range of Ketjenlube Polymer Esters. A significant part of the Arese activities is toll production for third parties both inside and outside of Akzo Nobel. Arese has a strong international presence with 90% of its production being exported. The Arese site is located in northern Italy near Milan. Various reactors (glass lined; stainless steel) of different sizes with an overall capacitiy of approx. 12,000 mt/year are available. A consistent and high product quality is ensured by a team of experienced and skilled people. The Arese site is certified according to ISO 9002 and ISO For more information please call the Marketing Center Arese (see address list inside of the back cover of this brochure). Ketjenlube Polymer Esters Dithiocarbamates Di-esters Polyol Esters Amides

2 CONTENTS Ketjenlube Polymers Esters Chemistry, properties, Product range Automotive applications Industrial applications Other applications 2 6 Ketjen-Ox Dithiocarbamates Chemistry, properties, applications Product range 15 Di-esters, Polyol Esters, Amides Properties, product range 17 General Information HSE-data, regulatory status, food approval information Address list Sales Offices 18 Lubricant Chemicals 1

3 GENERAL INFORMATION Ketjenlube Polymer Esters Ketjenlube Polymer Esters are unique, patented specialty components used in the formulation of synthetic and semi-synthetic high performance lubricants and industrial fluids. They reduce wear much more effectively than other conventional synthetic base fluids. This feature has made Ketjenlube Polymer Esters an important tool in the lubricating oil market during the last 15 years. Currently more than 15 different Ketjenlube Polymer Ester types are commercially available, ranging in viscosity from 5 mm 2 /s to 700 mm 2 /s and varying in polarity from compatible with unpolar fluids like Polyalphaolefins to completely watersoluble. All Ketjenlube Polymer Esters are produced in dedicated reactors which guarantees a consistent high product quality and product availability. Chemistry View on a Ketjenlube reactor Ketjenlube Polymer Esters are copolymers of alpha-olefins and dicarboxylic acids which are esterified with short or medium chain length alcohols. The Ketjenlube molecules have a unique, patented double-comb structure in which the ester and hydrocarbon groups are present in the side chains with the main polymer chain consisting of carbon atoms only. Despite viscosities of up to 700 mm 2 /s at 100 C the average molecular weights (Mw) range from 600 to about 7,000. Consequently even the high viscous Ketjenlube Polymer Ester types are completely shear stable. Ketjenlube Polymer Ester Structure (idealized) Carbon side chain Carbon back bone Ester side groups 2

4 Inherent Lubricity of base fluids Reichert test; standard conditions Reichert wear scar (150 N oil = 100) Ketjenlube mineral oils conventional esters Polyalphaolefins Properties Viscosity 100 C (mm 2 /s) The polymeric nature and special structure of the Ketjenlube Polymer Esters contribute to some outstanding features compared to conventional esters: ZDDP-Synergy of Ketjenlube Polymer Esters demonstrated in the Falex Pin & Vee Wear test ASTM D Mineral oil solutions of various ZDDP types were tested with and without 5% Ketjenlube Polymer Ester addition. Superior hydrolytic stability (stable for more than six months in aqueous emulsions at ph 9). This makes Ketjenlube Polymer Esters for example a valuable tool in metal working fluids (e.g. in soluble oils). Outstanding inherent lubricity. Ketjenlube Polymer Esters exhibit the highest load carrying capacity compared to all other lubricating oil base fluids of comparable viscosities available in the market. This feature helps to keep the engine wear low under cold starting conditions (cf. page 6). wear teeth fail! safety pin break A B C D A B C D without Ketjenlube 135 with 5 % Ketjenlube 135 Powerful synergy with EP/AW-additives. This makes it possible to replace e.g. chloroparaffins in metal working fluids by a combination of Ketjenlube Polymer Esters and Sulfur/Phosphorus additives without losing EP-performance (cf. page 10). ZDDP-Level adjusted to 0.1% Phosphorus ZDDP-Type: A: prim. B: Prim/sec. C: sec. D: aryl Clean burning, clean evaporation (no smoke, no fumes). Ketjenlube Polymer Esters burn or evaporate at high temperatures without giving rise to smoke or hazardous fumes. This favourable property allows the formulation of low-smoke two-stroke engine oils (cf. page 8) or industral oils for high temperature applications (cf. page 12). Applications Ketjenlube Polymer Esters are approved and used commercially in: Crankcase oils for Gasoline and Diesel engines (semi-synthetic and synthetic; viscosity grades from SAE 0W-30 to 20W-50) Two-stroke engine lubricants (air cooled, water cooled engines) Automotive and Industrial gear oils Fluids for metal cutting and metal forming operations (both neat oils and emulsion systems). Greases Special applications (shock absorber fluids, spin finishing lubricants, drilling fluids) 3

5 KETJENLUBE POLYMER ESTERS Product Range Physical and applicational properties Ketjenlube type Method KL 115 KL 135 KL 165 KL 1300 KL 215 Physical and Chemical Characteristics Viscosity at 100 C (mm 2 /s) ASTM D Viscosity at 40 C (mm 2 /s) ASTM D Viscosity index ASTM D Pour point ( C) ASTM D Flash point ( C) ASTM D Acid number (mgkoh/g) ASTM D < Density 20 C (g/cm 3 ) ASTM D Colour Gardner ASTM D-1500 < 1 < 1 < 1 < 1 < 1 Applicational properties Volatility Noack (%) DIN Hydrolytic stability ASTM D-2619 Acid number (mgkoh/g) after 48 h oil phase water phase Thermo-oxidative stability IP 48 (200 C; 15 liter air/hour) Weight loss (%) Viscosity increase (%) Lubricity Reichert (% wear volume; 150 N oil = 100 %) pure Ketjenlube % Ketjenlube in 150 N oil Compatibility 10 % in PAO 6 (48 h at 25 C) + ± + 10 % in 150 N oil (48 h at 10 C) ± + 10 % in water Seal compatibility (for details refer to the corresponding data leaflets Major applicational areas CEC L-39-X-95 neutral behaviour two-stroke; four stroke (gasoline and gear oils, hydraulic oils, greases, MWF (neat oils, Nomenclature: first digit: 1 = polar version subsequent digits: Viscosity at 100 C 2 = low polar version (except KL 502; KL 522; KL 6300) 3 = unsaturated product 4,5 = metal working applications 4

6 KL 230 KL 250 KL 2300 KL 2700 KL 19 KL 207 KL 305 KL 445 KL < < 0.1 < ca. 10 ca < 1 < 1 < 1 < 1 < 1 2 < < % in water: ± + neutral behaviour slightly swelling Diesel); gear oils soluble oils) (automotive; 4-stroke, two-stroke; MWF MWF (soluble oils) industrial) For details about a specific product please refer to the corresponding technical data sheet 5

7 KETJENLUBE POLYMER ESTERS Performance in four-stroke applications Ketjenlube Polymer Esters are used commercially both in Diesel and Gasoline engine oils of all major viscosity grades as a means of achieving improved performance, especially from the point of view of wear reduction. Wear-reducing effect The wear reduction due to Ketjenlube Polymer Esters in four stroke oils is a function of its inherently high affinity to metal surfaces: This helps on the one hand to maintain a strong oil film at high oil temperatures, whilst permitting the start of a cold engine without excessive wear after longer periods of engine shut-down. its strong synergy with zinc-dialkyl-dithiophosphates (ZDDP). Ketjenlube Polymer Esters are able to lower the activation temperature of ZDDP which results in an efficient EP-protection over a wider temperature range. This synergistic effect is illustrated for example on page 3. In the field these features result in reduced engine wear (especially cam wear) which has been proven and demonstrated by a series of engine tests. As an example here are the summarized comparative test results of two oils (with and without a Ketjenlube Polymer Ester) in the Nissan KA 24E valve train wear test which is an ILSAC GF 3 specification test (Sequence IVA). Oil A no Ketjenlube Oil B 8% Ketjenlube Scuffing area on rocker arm pads intake (average) 62.2 % 13.4 % exhaust (average) 58.5 % 5.5 % Wear of rocker arm pads intake (average) 4.0 µm 2.0 µm exhaust (average) 5.5 µm 1.0 µm Wear of cam lobes intake (average) 34.5 µm 5.2 µm exhaust (average) 28.5 µm 3.5 µm Table 1: Nissan KA 24E valve train wear test results of an API/SH oil with and without Ketjenlube Polymer Ester Composition of the test oils: Oil A Oil B API/SH ad-pac 12.0 % 12.0 % VI-improver (OCP) 8.5 % 8.2 % Pour point depressant 0.1 % 0.1 % Ketjenlube % Polyalphaolefin 20.0 % 15.0 % 150 N mineral oil 59.4 % 56.7 % Viscosity 100 C 14.1 mm 2 /s 13.6 mm 2 /s Viscosity 20 C 3300 mpas 3300 mpas 6

8 VW Cam & Tappet results of a low ZDDP 10W-40 oil (500 ppm Phosphorus) with and without Ketjenlube 135 Cam wear (µm) average cam wear maximum cam wear Trial oils: 500 ppm Phosphorus Reference oil: 1100 ppm Phosphorus fail pass 40 With Ketjenlube Polymer Esters it is even possible to formulate low ZDDP oils without losing anti-wear performance no Polymer Ester 5% Polymer Ester 10% Polymer Ester reference For further performance data of Ketjenlube Polymer Esters in four-stroke engine oils please refer to the data leaflet Ketjenlube Polymer Esters in four-stroke applications. Other benefits of using in 4T-oils Fuel efficiency Ketjenlube Polymer Esters assist in reducing the internal friction between engine parts and thus help to reduce the fuel consumption. One customer reported a 5W-30 engine oil passing the US fuel efficiency limit upon addition of 3% of Ketjenlube Oil C Oil D Oil E description no friction modifier; no friction modifier; with commercial friction modifier; no Ketjenlube 3% Ketjenlube 1300 no Ketjenlube EFEI (%) Table 2: Sequence VI engine test results of API/SH 5W-30 oils with and without Ketjenlube Polymer Esters Clean engines Ketjenlube Polymer Esters are not classical dispersants, however due to their double-comb -structure they exhibit an inherent dispersancy power which often acts synergistically with ash-containing and ash-free dispersants. This results in exceptionally clean engines and low piston deposits as demonstrated in a Daimler Benz OM 602 A and other engine tests. For detailed results please refer to the data leaflet Ketjenlube Polymer Esters in four-stroke applications. Typical treat rates in 4T-oils To achieve an optimum wear reducing effect in semi-synthetic 5W or 10W oils Ketjenlube Polymer Ester treat rates of 6 % to 12 % are recommended. In fully synthetic premium oils Ketjenlube concentrations up to 33 % are commercially used; a typical example for a semi-synthetic 10W-40 oil is the oil B given in table 1. Both the low and high temperature thickening effect of the Ketjenlube Polymer Esters is unexpectedly low compared to other base fluids of similar viscosity. This phenomenon allows the formulation of both 5W and 10W oils including substantial quantities of Ketjenlube 115 or Ketjenlube 135, the two most widely used Ketjenlube types in the four-stroke area. 7

9 KETJENLUBE POLYMER ESTERS Performance in two-stroke engine oils The high inherent lubricity together with their clean burning make the Ketjenlube Polymer Esters an ideal base fluid for two-stroke motor bike engine oils. In table 3 the ISO-L-EGD results of four different formulation examples (semi-synthetic, synthetic, high solvent oils) containing Ketjenlube Polymer Esters as ester component are summarized. Table 3: Ketjenlube Polymer Esters in two-stroke engine oils Oil Type synthetic; semi semi high solvent synthetic synthetic synthetic Composition (wt %) Ad-pac A 5.2 Ad-pac B Ad-pac C 5.2 Polyisobutylene Ketjenlube Ketjenlube Ketjenlube SN mineral oil SN mineral oil Solvent Viscosity 100 C (mm 2 /s) ISO-L-EGD-engine test results: Exhaust smoke index (FC limit: 85 min) Lubricity index (FC limit: 95 min Torque index (FC limit: 98 min) Detergency index 1 hour not not (FC limit: 95 min) determined determined Detergency index 3 hours not (GD limit: 125 min) determined Exhaust port blocking index (FC limit: 90 min) As a top-of-the-line product the Ketjenlube Polymer Esters are commonly used for racing purposes. Several customers also have run Ketjenlube based oils in the Piaggio Hexagon test with outstanding lubricity results. For further engine test results please refer to the data leaflet Ketjenlube Polymer Esters in two-stroke applications. Biodegradable two-stroke engine oils Due to their limited biodegradability Ketjenlube Polymer Esters are not recommended for use in biodegradable two-stroke engine oils. 8

10 Performance in automotive gear oils One lubricating oil area where synthetic base fluids are becoming more and more predominantly used instead of mineral oil base stocks is that of automotive and industrial gear oils. The two high viscous Ketjenlube types Ketjenlube 2300 and Ketjenlube 2700 are tailormade for applications in gear oils and are a cost effective alternative to high viscosity polyalphaolefins. In principle the lower viscous Ketjenlube Polymer Esters can be used, too (and in fact are commercially used). Besides their superior load carrying capacity they exhibit Excellent thermo-oxidative and hydrolytic stability (similar to high viscous PAO); Absolute temporary as well as permanent shear stability; Compatibility both with non polar base stocks and with polar additives; Neutral seal behaviour; Superior viscosity characteristics at low temperature. Automotive gear oils It is in particular the shear stability and low temperature behaviour of the Ketjenlube Polymer Esters which allow the formulation of outstanding high performance multi-grade automotive gear oils. As an example in table 4 both a 75W-90 and a 75W-140 synthetic gear oil is given based on Ketjenlube 2300 and Ketjenlube 2700 respectively. Viscosity grade 75W-90 75W-140 Composition (wt%) Ketjenlube Ketjenlube Polyalphaolefin 4/ Di-ester Commercial API GL-5 ad-pac Performance data Viscosity 100 C (mm 2 /s) Brookfield viscosity 40 C (mpas) 64, ,500 Shear loss after 20 h (%); CEC L-45-T-93 < 1 < 1 Elastomer swell (Viton); DIN neutral neutral GFC oxidation test (160 C, 192 h); CEC L-48-A-95 acid no. after test (mgkoh/g) viscosity increase (%) Table 4: Automotive gear oil examples with Ketjenlube Polymer Esters as base fluids The 75W-90 gear oil of table 4 was also tested in the CRC L-60 gear oil test. Besides a very low viscosity increase it achieved an excellent carbon/varnish and sludge merit rating which clearly outperformed comparable oils based on high viscous polyalphaolefins. 9

11 KETJENLUBE POLYMER ESTERS Performance in metalworking fluids Ketjenlube Polymer Esters are used commercially in a wide range of metal working applications at average treat levels of 3 % to 25 % depending on the application in neat oils in emulsion systems for metal cutting operations (e.g. broaching, tapping, milling) for metal forming operations (e.g. hot and cold rolling, drawing, stamping) The performance of Ketjenlube Polymer Ester containing fluids is increased even further when combined with antiwear/ep agents, so enabling high performance formulations to be made which are entirely chloroparaffin-free. Major achievements in overall performance are extended tool life; increased productivity; improved tolerance and surface finish of machined parts. Soluble oils (emulsions) All Ketjenlube Polymer Esters can be emulsified using state-of-the-art emulsifiers, enabling high performance soluble oils to be formulated. Various guideline formulations are available for fine-tuning; examples are given in table 5: Table 5: Guideline formulations for metal working concentrates using Ketjenlube Polymer Esters as anti-wear additive. Concentrate A B C Concentrate type amine/boron boron free amine free/ containing boron free Composition (wt%) Mineral oil (paraffinic or naphthenic) Oleyl/cetylalcohol + 2 EO (emulsifier) Glycole derivate Vegetable oil fatty acids Carboxy-4-hexyl-2-cyclohexen-1- octanoic acid ( Di-acid ) Amine borate 9.0 Biocide 3.0 * * Diglycolamine 3.75 Potassium hydroxide 50% in water 3.75 Ketjenlube * biocide to be included as necessary 10

12 A 10% emulsion of the amine and boron free concentrate in table 5 has been tested on a CNC cutting machine. The chosen operations were face turning and grooving of hardened steel (17 CrNiMo 6). In both cases the tool wear was considerably lower (up to 50%) compared to the same emulsion without Ketjenlube Polymer Ester. µm Tool wear vs. running time: Face turning (constant revolution speed) no KL 135 KL µm Tool wear vs. running time: Grooving no KL 135 KL 135 running time (m) Performance of a 10% emulsion (concentrate C in table 5) with and without Ketjenlube 135 in face turning and grooving of hardened steel (17CrNiMo 6) running time (m) More formulation examples (including detailed composition) and test results can be found in the data leaflet Ketjenlube Polymer Esters in soluble oils. Synthetic concentrates With Ketjenlube Polymer Esters it is also possible to formulate aqueous solutions, using Ketjenlube 445 or Ketjenlube 522. Ketjenlube 445 is not truly watersoluble, but is easily emulsifiable due to its ethoxylated side chains which give the product an HLB-value of Ketjenlube 445 improves the surface finish in metal processing, for example in aluminium or copper metal working. The effect on the tool wear of the addition of 0.5% Ketjenlube 445 to an aqueous cutting formulation is shown in the subsequent graphs: µm Tool wear vs. running time: Face turning (constant revolution speed) no KL KL µm no KL KL 445 Tool wear vs. running time: Grooving Performance of an aqueous cutting formulation with and without 0.5% Ketjenlube 445 in face turning and grooving of aluminium alloy (AlMgSi 1). running time (m) running time (m) In addition to ethoxylated side chains Ketjenlube 522 contains free acid groups which can react with amines. Aqueous solutions of Ketjenlube 522 show an outstanding lubricity which still is unsurpassed in the area of synthetic aqueous solutions, however, without careful formulation Ketjenlube 522 can exhibit a foaming tendency in line with its degree of ethoxylation, which may restrict its application to low agitation operations. For more detailed information about the use of Ketjenlube 445 and Ketjenlube 522 please refer to the corresponding data leaflets. 11

13 KETJENLUBE POLYMER ESTERS Neat oils The performance improvement of neat oils with Ketjenlube Polymer Esters for instance is demonstrated in the Falex tapping torque test 1) which is designed to evaluate cutting oils: In cutting operations one of the major functions of the oil is to minimize wear on the cutting edge of the tool. This tool wear can be determined indirectly by measuring the torque generated during the tapping operation in the so-called tapping torque machine. High torques are an indication of poor lubrication and thus accelerated wear. Several neat oils with and without added Ketjenlube Polymer Ester were tested. The performance differences are expressed in terms of the torque difference T q between the reference oil (chloroparaffin based; T q = 0) and the test oils. A positive T q means less torque than the reference and therefore less wear. The results are summarized in table 6. Table 6: Falex Tapping torque test results T q ISO VG 46 mineral oil approx. 3 Mineral oil + 2 % TNPS* 0.50 Mineral oil + 25 % Ketjenlube Chloroparaffin based reference oil 0 Mineral oil + 2 % TNPS* + 25 % Ketjenlube * Di-tert.nonylpolysulfide These results clearly demonstrate the lubricity improvement which can be achieved by the addition of Ketjenlube Polymer Esters. Comparable formulations containing conventional esters do not exhibit this superior level of performance. Hot drawing oils Ketjenlube 6300 has been specially developed to lubricate hardened-steel forming dies in the drawing of non-ferrous tubes. The use of Ketjenlube 6300 results in longer tool life and high surface finish with a concomitant low fume emission. 1) a detailed description of the Falex Tapping Torque Test is given for instance in Lubr. Eng. 52, 1, (1996). 12

14 Performance in other applications Industrial gear oils For industrial gear oils the thermo-oxidative stability is of paramount importance, consequently there are a variety of specification tests dealing with this performance criterium. Industrial gear oils based on Ketjenlube Polymer Esters exhibit an excellent stability performance as is demonstrated for a synthetic ISO VG 220 oil (table 7): Composition Ketjenlube % Polyalphaolefin % Trimellitate ester 10.0 % Additive package 1.8 % Test results Table 7: Performance data of an ISO VG 220 gear oil based on Ketjenlube 2300 Oxidation test ASTM D 2893 (121 C; 312 h) precipitation number 0 acid number increase 1 % viscosity increase 6 % GFC oxidation test (150 C; 192 h) acid number after test 1.51 mgkoh/g viscosity increase 5 % Panel Coker deposits (250 C; 6 h) 5 mg FZG-test (16.6 m/s; 140 C) pass load stage 12 The outstanding load carrying capacity of the ISO VG 220 gear oil described in table 7 is demonstrated in the FZG test; even in the severe mode (gear speed 16.6 m/s; oil temperature 140 C) the oil reached the final load stage 12. For more detailed information on automotive and industrial gear oils please refer to the corresponding Ketjenlube Polymer Ester data leaflets. 13

15 Greases Ketjenlube Polymer Esters are used commercially in semi-synthetic and synthetic greases. They do significantly improve the AW/EP-properties without disturbing the grease texture. Greases with Ketjenlube Polymer Esters also show significantly increased ageing resistance in the presence of iron. Four-ball endurance test of a lithium soap grease with and without Ketjenlube 135 (load: 2000 Newton) temperature ( C) Grease without KL 135 Grease with KL time (min) For more detailed information and test results about the use of Ketjenlube Polymer Esters please refer to the data-leaflet Ketjenlube Polymer Esters in Greases. Drilling fluids Recent investigations into the use of Ketjenlube Polymer Esters as an additive for environmentally safe, water based drilling muds have provided promising results which also have been confirmed by field tests in the Gulf of Mexico: The use of Ketjenlube Polymer Esters as a rate of penetration (ROP) enhancer resulted in a dramatic increase of about 8.5 times ROP compared to a state-of-the-art water based mud. In a silicate mud system the addition of small amounts of Ketjenlube Polymer Esters reduced the internal friction by more than 50%. In bentonite drilling slurries Ketjenlube Polymer Esters improved the lubricity by up to 40%. For further information about the use of Ketjenlube Polymer Esters please refer to our specialists in our Denver Sales Office (cf. address list on page 20). 14

16 KETJEN-OX DITHIOCARBAMATES Ketjen-Ox Dithiocarbamates Metal dithiocarbamates are versatile additives for automotive and industrial lubricants as well as for rubber processing. The production of solid and liquid dithiocarbamates is a core technology within Akzo Nobel. The Akzo Nobel dithiocarbamates produced for lubricant applications are either of a unique composition or are offered as high quality products (high purity) at a very competitive price. Currently Akzo Nobel is the only Europebased producer of these components. Products which are currently available are summarized in table 8. Molybdenum dithiocarbamates as friction modifiers in engine oils: Molybdenum dithiocarbamate complexes belong to the most powerful friction reducing agents available for four-stroke engine oils. They are able to lower the internal friction in an engine by more than 50 per cent. Whereas Ketjen-Ox 77M is very cost-efficient but dark coloured, the molybdenum dithiocarbamate complex Ketjen-Ox 77TS displays a light colour in the final formulation and is fully compatible even with very low polar Group 3 and Group 4 base oils. Ketjen-Ox 77TS furthermore shows a better thermo-oxidative stability than other molybdenum dithiocarbamates. Friction properties of a 10W-30 engine oil with and without Ketjen-Ox 77TS Friction no Molybdenum dithiocarbamate with 1% Ketjen-Ox 77TS Test conditions: High frequency reciprocating rig; load increasing in 6 steps from 10 N to 150 N. Oil temperature:100 C Compatibility of Ketjen-Ox 77TS in PAO 6 (left) compared to other commercial Molybdenum dithiocarbamates (500 ppm Mo) 15

17 Appearance of 1% Ketjen-Ox 77TS in mineral oil (right) after ageing in the CEC L-39-T-96 elastomer test compared to a conventional Mo-dtc (left) After Elastomer-Swell Test 168 h/150 C Competitive Molybdenum dithiocarbamate Ketjen-Ox 77TS Type zinc-dithiocarbamates antimony- dithiocarbamate molybdenum-dithiocarbamates Product name Ketjen-Ox 71 Ketjen-Ox-71 S Ketjen-Ox 7458 Ketjen-Ox 77M Ketjen-Ox 77TS mixture of antimony molybdenum sulfurized molybdenum Composition zinc diamyldithiocarbamate diamyl- and diisooctyl diisooctyldithio- diisotridecyl dithiodithiocarbamates carbamate complex carbamate complex Purity 100% pure 55% in mineral oil 55% in mineral oil 80% in mineral oil 50% in mineral oil Appearance yellow liquid orange-brown liquid dark liquid reddish liquid Product viscosity 4,500 cst 75 cst 120cSt 1,500 cst 90 cst (40 C) Metal content Zn: 11.0 % Zn: 6.1 % Sb: 6.9 % Mo:10.5 % Mo: 5.0 % Sulfur content S: 22.0 % S: 12.0 % S: 11.5 % S: 15.0 % S: 6.6 % Specialty unique: free of state-of-the-art very low crystal- state-of-the-art solvent, but liquid product lization point product unique: light colour, compatible with low polar oils Main multi-purpose additives friction modifiers for engine oils; applications (antioxidants, AW/EP-additives) for greases AW/EP-additives for greases Table 8: Metal dithiocarbamates; product range Dithiocarbamates for grease applications: Metal dithiocarbamates are multi-functional additives for greases which help to keep the additive level low and thus limit the interferance with the grease texture (no oil bleeding ). Zinc-, antimony- and molybdenum dithiocarbamates are efficient antioxidants as well as AW/EP-additives. The friction modifying properties of the molybdenum dithiocarbamate complexes are also displayed in greases. Although antimony compounds usually are reputed as toxic and harmful to the environment, the antimony-dithiocarbamate Ketjen-Ox 7458 is not toxic (neither to rats, rabbits or fish) or irritating, as was proven by appropriate testing. 16

18 DI-ESTERS, POLYOL ESTERS, AMIDES Di-esters, Polyol Esters, Amides Di-esters, Polyol Esters Akzo Nobel Chemicals is one of the leading ester manufacturers worldwide. The site Arese is specialized in the production of high quality/high performance esters for various markets. The ester range comprises fatty acid esters, di-esters, hindered esters, sorbitane esters and many more. A selection of esters offered for the lubricant area is given in table 9. Trade name Ester kinematic Acid pour flash type viscosity value point point 100 C (mm 2 /s) (mgkoh/g) ( C) ( C) Ketjenlube 09 dimeric acid ester 13.2 < 0.1 < Ketjenlube10 hindered ester 5.0 < 0.1 < 40 > 240 Ketjenlube 15 di-ester 5.2 < 0.2 < 50 > 240 Ketjenlube 16 di-ester 4.0 < 0.2 < 50 > 230 Table 9: Examples of conventional esters manufactured for the use in lubricants Special ester types can be tailored according to customer demands. For further information please refer to the Marketing Center in Arese (cf. address list on page 20). Amides Trade name Armid O Armid E Armid HT In addition to ester derivatives the Arese product range comprises also various fatty acid amides which are used among others as fuel additives for lubricants (friction modifiers). The amides commercially available are summarized in table 10. Chemical Melting Flash Appearance description point point oleylamide erucamide stearylamide pellets, flakes, hot molten liquid pellets, flakes pellets, flakes 70 C 210 C 79 C 230 C 100 C 225 C Table 10: Fatty acid amides 17

19 GENERAL INFORMATION General Information Health, safety, environment, regulatory status A representative number of Ketjenlube types have been tested for various toxicological and ecotoxicological properties. The test data show that Ketjenlube Polymer Esters can be considered safe to man and friendly to the environment, concurrent with its chemistry being a polymer of carbon, hydrogen and oxygen only. Ketjenlube type KL 305 KL 115 KL 135 KL 165 KL 1300 KL 2300 KL 502 KL 445 KL 215 KL 230 KL 250 KL 2700 KL 522 Test procedure Skin irritation (rabbit) Eye irritation non irritating to skin non irritating to eyes Acute oral toxicity (rat) > 15 g/kg > 2 g/kg > 15 g/kg > 5 g/kg Mutagenicity (Ames test) no mutagenic activity Biodegradability (CEC L-33-A-94) 65 % 27 % 14 % 32 % Bacterial toxity (EC 10; Robra-Test) >10 g/l >10 g/l 7.75 g/l Acute toxity to fish (zebra fish) >200 mg/l >100 mg/l > 1 g/l Skin sensitization (Magnusson/Kligmann test) German Water Hazardous Class non sensitizing one (very slightly water hazardous) FDA Food approval of Ketjenlube Polymer Esters Some Ketjenlube Polymer Ester types are approved by FDA for the use as a component in lubricants for food packaging equipment like can seaming lubricants. The general approval for the use in lubricants with incidental food contact (FDA H1 lubricants) is currently under way. For detailed information please refer to the Marketing Center in Arese. Registration status of Ketjenlube Polymer Esters Ketjenlube type KL 115, KL 135 KL 165 KL 2300 KL 207 KL 19 KL 445 KL 522 KL 215, KL 230 KL 305 KL 2700 KL 250 KL 1300 CAS-Registry Number EINECS no no no no no no no (Europe) (polymer)* (polymer)* (polymer)* (polymer)* (polymer)* (polymer)* (polymer)* TSCA (USA) yes yes yes yes yes yes yes DSL (Canada) yes no no no no no yes AICS (Australia) yes yes yes yes yes yes no MITI (Japan) yes yes yes yes yes no no China yes yes yes yes yes no no Thailand ** ** ** ** ** ** ** Korea yes no no no no no no * Polymers cannot be registered in EINECS. All Ketjenlube Polymer Esters are free to sell in Europe. ** Only hazardous products need to be registered. All Ketjenlube Polymer Esters are free to commercialize. 18

20 HSE-Data for Ketjen-Ox Dithiocarbamates Ketjen-Ox type Ketjen-Ox 71 Ketjen-Ox 71S Test procedure Skin irritation (rabbit) Eye irritation (rabbit) Biodegradability Ketjen-Ox 7458 Ketjen-Ox 77M Ketjen-Ox 77TS practically non irritating minimally irritating inherently biodegradable Oral LD 50 (rat) > 14,000 mg/kg > 5,000 mg/kg > 2,000 mg/kg > 2,000 mg/kg Dermal LD 50 (rabbit) > 2,000 mg/kg > 5,000 mg/kg > 2,000 mg/kg > 2,000 mg/kg Fish toxicity (zebra fish) German water hazardous class > 1,000 mg/kg two (slightly water hazardous) Registration status of Ketjen-Ox Dithiocarbamates Ketjen-Ox type Ketjen-Ox 71 Ketjen-Ox 71S Ketjen-Ox 7458 Ketjen-Ox 77M Ketjen-Ox 77TS CAS-Registry Number ; EINECS (Europe) yes (EC-number: yes (EC-numbers: yes (EC-number: yes (EC-number: ) ; ) ) TSCA (USA) yes yes yes yes DSL (Canada) yes yes yes yes AICS (Australia) yes yes no yes MITI (Japan) yes (ENCS-number: yes yes (ISHL-number: (2)-2886) 1-(1)-524) China yes yes yes yes PICCS (Philippines) yes yes yes yes Korea yes (KE-35526) yes (KE-25429) yes (KE-03103) For further information please refer to the material safety data sheets available for these products. 19