Thiadiazole Technology: Thiadiazole Technology: -Motor Oil Antiwear-Motor Oil Antiwear-Grease Extreme Pressure-Grease Extreme Pressure

Tom Karol, Ph.D.

Research Director

1,3,4-Thiadiazole Chemistry1,3,4-Thiadiazole Chemistry

– Physical /Performance Properties• Liquid• Wear/EP performance equivalent to or better than

heavy metal technology• Environmentally friendly wear/EP agent

• Ashless• Biodegradable preferred• Cost effective

– Commercially viable process

Theory of Thiadiazoles as Theory of Thiadiazoles as EP additivesEP additives

Theory of simple thiadiazole coordination

Theory of dimer thiadiazole complexation

Theory of poly thiadiazole coordination

Simple Thiadiazole CoordinationSimple Thiadiazole Coordination

SEQUENCE VD WEAR RESULTSSEQUENCE VD WEAR RESULTSconducted in the same prototype conducted in the same prototype motor oil base formulationmotor oil base formulation ____Wear____

Max. Avg. 0.08P ZnDTP fail fail 0.09P ZnDTP pass pass

0.1% thiadiazole technology plus 0.08P ZnDTP 0.0040 0.0029Sequence VD limits 0.0080 0.0040

Dimer Thiadiazole ComplexationDimer Thiadiazole Complexation

Bidentate Coordination

Theory of Poly-Thiadiazole Theory of Poly-Thiadiazole CoordinationCoordinationPolydentate association

Introduction ofIntroduction of VANLUBE 972 VANLUBE 972

-Achieves polydentate -Achieves polydentate propertiesproperties through poly-through poly-thiadiazole coordinationthiadiazole coordination

-Useful as a Grease Extreme -Useful as a Grease Extreme PressurePressure additiveadditive

2,5-Dimercapto-1,3,4-2,5-Dimercapto-1,3,4-Thiadiazole Disulfide DimerThiadiazole Disulfide Dimer

SS

NN

S S SS

NNH H

VANLUBE 972 VANLUBE 972 Metal CoordinationMetal CoordinationPolydentate association

IR ABSORPTIONIR ABSORPTION

Major shifts in peaks are further evidence for the complex formation:

Compound Absorption Peaks (cm-1)DMTD disulfide bis-dimer1487, 1435, 1406, 1262, 1212Triethylene glycol monobutyl ether

1460, 1351, 1297, 1248Complex, 40% monosulfide bis-dimer1510, 1433, 1350, 1244

SATURATION POINTSATURATION POINT

SOLVENT % DIMERTHF 16.6

Acetone 2.4

Acetonitrile <0.04

Triethylene Glycol Monobutyl Ether 48

Triethylene Glycol Dimethyl Ether 56

Polyethylene Glycol (MW 400) 45

Modified ASTM D 4048 Cu Corrosion Modified ASTM D 4048 Cu Corrosion

24h @ 100°CVANLUBE 972

mass percent1 2 3 5

Li-12 OH Grease 99 98 97 95Heptane and towel rub

Wt Change, mg +5.8 +8.4 +14.8 +22.1

DMK Towel Rubbing,

Wt Change, mg +1.9 +0.1 +1.6 +5.8

Rating 2e 2e 2e 2e

DMK = dimethylketone (acetone)

Effect of VANLUBE 972Effect of VANLUBE 972

VANLUBE 972 1%Molybdenum Dithiophosphate, mass 1% 1%Li-12OH Stearate Grease, mass 99% 98%Copper Strip Weight Before, g 25.4175 27.0688

Weight Change, mg -2.1 +4.0Heptane & Paper Towel,

Weight Change, mg-2.8 +4.2

Acetone & Paper Towel,

Weight Change, mg-3.1 +3.2

Rating, ASTM D 4048 4a 2e

Modified ASTM D 4048 Modified ASTM D 4048 Copper Corrosion TestCopper Corrosion Testmass percent

VANLUBE 972 and VANLUBE 972 and

Fe Corrosion InhibitorsFe Corrosion Inhibitors Grease VL 972

Mass %Timken, lb 4- Ball

Weld,kgf 4-Ball Wear,

mm

 Aluminum Complex #2 0.00 - -

1.00 40 - 0.50, 0.49, 0.43

1.25 Failed 50 - -

1.50 Failed 50 - -

1.75 60 315 0.96, 0.71, 0.73

2.00 80 - -

Aluminum Complex #2 With 0.5% OD-9316

1.00 Failed 50 315  0.60, 0.67

1.75 60 - 0.60, 0.67

  Aluminum Complex #2 With 1.0% OD-9316

1.00 50 250 0.63, 0.67

Biodegradation Biodegradation Study of VANLUBE 972:Study of VANLUBE 972:

CO2 + Ba(OH)2

BaCO3+ H2O

Biodegradation Study of Biodegradation Study of

VANLUBE 972:VANLUBE 972:

Material Mass (mg) % Degradation

 

VANLUBE 972 18.2 78.0

23.1 46.5

Sodium Benzoate 36.0 78.4

Canola Oil 30.1 38.5