OVERBASEDALKYLOXYBENZENE SULFONATESAS DETERGENTS

The present invention relates to an additive especially useful in a marine lubricating oil.

BACKGROUND OF THE INVENTION

U.S. 3,523,898 teaches that overbased alkyl phenol sulfonic acids are useful as detergents in lubricating oils. The alkyl groups appear to be attached at either the 1- or 2- position of the alkyl groups, and the TBN appears to limited to 150 or less.

British 1 ,372,532 teaches that mixtures of overbased, alkyl hydroxy benzene sulfonates and alkylsalicylic acids are useful in lubricating oils. The alkyl groups of the sulfonates appear to be attached at either the .- op¬ position of the alkyl groups. The TBN appears to be about 200.

British 1 ,332,473 teaches that overbased, alkyl hydroxy benzene sulfonates are useful as an oil-soluble dispersant in lubricating oils. The patent is silent as to where the alkyl groups are attached. The TBN appears to be about 400, with a very high base ratio.

U.S. 4,751 ,010 teaches that partial sulfonation of alkylphenol results in the formation of an alkyl hydroxy benzene sulfonate that can be overbased using sulfurization and carbonation. The patent is silent as to where the alkyl groups are attached. The TBN appears to be in the range of from 200 to 250.

U.S. 5,330,663 and 5,330,664 teach overbased alkylphenoxy sulfonates that have alkyl groups derived from substantially straight-chained olefins that are either internal or alpha. It does not teach using olefins that are partially internal olefins.

U.S. Patent Nos. 3,523,898; 4,751 ,010; 5,330,663; and 5,330,664 are all hereby incorporated by reference for all purposes.

SUMMARY OF THE INVENTION

The present invention provides a lubricating oil having a major amount of base oil of lubricating viscosity, and a minor amount of an overbased, alkyl oxy benzene sulfonate having a TBN of at least 200, preferably at least 250, between 40 wt % and 80 wt % of the alkyl group is attached at the 4- position and higher positions of the alkyl group Preferably, between 45 wt % and 70 wt % of the alkyl group is attached at the 4- position and higher positions of the alkyl group This lubricating oil is especially useful as a marine lubricating oil

The oxy group can be either hydroxy, methoxy, ethoxy, propoxy, butoxy, pentoxy, or hexoxy Preferably, it is hydroxy

Preferably, the alkyl group of the overbased, alkyl oxy benzene sulfonate has from eighteen to thirty carbon atoms per alkyl group More preferably, it has from twenty to twenty-four carbon atoms per alkyl group

One process for making this overbased, alkyl oxy benzene sulfonate comprises alkylating an oxy benzene with an olefin between 40 wt % and 80 wt % internal olefins to produce an alkyl oxy benzene, then sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene sulfonic acid, and overbasing the alkyl oxy benzene sulfonic acid to produce the overbased, alkyl oxy benzene sulfonate Preferably, the internal olefin is produced by isomeπzing an olefin using an iron pentacarbonyl catalyst

In an alternative embodiment of the present invention, an additive is produced by alkylating an oxy benzene with a polyalpha olefin having an activity of at least 80% to produce an alkyl oxy benzene, sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene sulfonic acid, and overbasing the alkyl oxy benzene sulfonic acid to produce an overbased, alkyl oxy benzene sulfonate having a TBN of at least 200, preferably at least 250

DETAILED DESCRIPTION OF THE INVENTION

In its broadest aspect, the present invention involves highly overbased, alkyl oxy benzene sulfonate detergents where at least 40 wt % of the alkyl groups are attached at the 4- position and higher positions of the

alkyl group. When at least 40 wt.% of the alkyl groups are attached at the 4- position and higher position, the viscosity is lowered significantly.

On the other hand, at least 20 wt.% of the alkyl groups should be attached at the 1-, 2-, and 3- position in order to reduce high temperature deposit formation. While Applicants do not wish to be bound by any particular theory of operation, it is believed that too high of internal attachment leads to structures that are similar to materials derived from branched olefins. Such materials tend to decompose readily at the branching.

In one embodiment, between 40 wt.% and 80 wt. % (preferably between 45 wt.% and 70 wt. %) of the alkyl group is attached at the 4- position and higher positions of the alkyl group. This type of additive can be produced by alkylating an oxy benzene with an olefin containing between between 40 wt.% and 80 wt. % internal olefins to produce an alkyl oxy benzene, sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene sulfonic acid; and overbasing the alkyl oxy benzene sulfonic acid to produce the overbased, alkyl oxy benzene sulfonate. An olefin containing between 20 wt.% and 60 wt. % internal olefins can be formed by isomerizing an alpha olefin using an iron pentacarbonyl catalyst.

In another embodiment, the additive is produced by alkylating an oxy benzene with a polyalpha olefin having an activity of at least 80% to produce an alkyl oxy benzene, sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene sulfonic acid; and overbasing the alkyl oxy benzene sulfonic acid to produce an overbased, alkyl oxy benzene sulfonate having a TBN of at least 250.

The present invention comes out of work in trying to find an inexpensive alternative to the use of salicylates in lube oils for marine applications. That alternative should have a TBN of over 250, have a viscosity of less than 600 cSt, and have comparative properties with commercial salicylates.

The initial attempts were with an overbased oxy benzene sulfonate having a linear C ₂₀ -C ₂₈ alkyl group. That material turned out to be so viscous

that its viscosity could not be measured. It was so viscous that it didn't flow from a beaker even when left overturned for over a weekend.

We overcame this problem by using an overbased alkyl oxy benzene sulfonate having alkyl groups that were isomerized prior to alkylation of the benzene. It is essential that alkyl groups of the overbased alkyl oxy benzene sulfonate be predominately attached at the 4- position and higher positions of the alkyl group.

THEOVERBASEDALKYL

OXYBENZENESULFONATE

The lubricating oil has a minor amount of an overbased, alkyl oxy benzene sulfonate having a TBN of at least 200, preferably at least 250, wherein at least 40 wt.% of the alkyl group of the sulfonate is attached at the 4- position and higher positions of the alkyl group. The oxy group can be either hydroxy, methoxy, ethoxy, propoxy, butoxy, pentoxy, or hexoxy. Preferably, it is hydroxy.

By "TBN," we mean "Total Base Number," which refers to the amount of base equivalent to one milligram of KOH in one gram of additive. Thus, higher TBN numbers reflect more alkaline products and therefore a greater alkalinity reserve. The Total Base Number for an additive composition is readily determined by ASTM test method D664 or other equivalent methods.

By "internal olefins," we mean an olefin wherein the double bond is at the 4- position and higher positions of the alkene, instead of at the 1-, 2-, or

3- position.

Preferably, the alkyl group of the overbased, alkyl oxy benzene sulfonate has from eighteen to thirty carbon atoms per alkyl group. More preferably, the alkyl group has from twenty to twenty-four carbon atoms per alkyl group.

The additive of the present invention can be produced by alkylating an oxy benzene with an olefin containing between 40 wt.% and 80 wt. % internal olefins to produce an alkyl oxy benzene, sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene sulfonic acid; and overbasing the alkyl oxy

benzene sulfonic acid to produce the overbased, alkyl oxy benzene sulfonate. An olefin containing between 40 wt.% and 80 wt. % internal olefins can be formed by isome zing an alpha olefin using an iron pentacarbonyl catalyst.

The processes of alkylating an alkyl oxy benzene with an olefin to produce an alkyl oxy benzene, and sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene sulfonic acid are both discussed in detail in

U.S. Patent Nos. 5,330,663 and 5,330,664, which have been incorporated by reference for all purposes. Our alkylation and sulfonation processes differ only in the olefins used and reaction time. In our batch alkylation reaction, we need only about six to eight hours. The preferred sulfonation process is a falling film process using a charge mole ratio of sulfur trioxide to alkylphenol of 1.1 :1 and a reaction temperature in the range of from 70° to 100° C, followed by immediate neutralization.

A neutralized slurry of alkyl oxy benzene sulfonic acid is added to a slurry of xylenes, methanol, and calcium hydroxide. The resulting slurry is then carbonated during which a second slurry of alkyl oxy benzene sulfonic acid and a second slurry of xylenes, methanol, and calcium hydroxide are added. After the carbonation, the material is stripped to remove methanol and water. Lube oil is then added and the solids removed. The remainder of the solvents are then stripped off and additional lube oil added to adjust the product to the final base number.

THE LUBRICATING OIL PRODUCT

The oil-soluble, highly overbased, alkyl oxy benzene sulfonate additive compositions produced by the process of this invention are useful lubricating oil additives imparting detergency and dispersency properties when added to the lubricating oil composition employed in the crank case of an internal combustion engine. Such lubricating oil compositions comprise a major amount of base oil of lubricating viscosity; and a minor amount of oil-soluble, highly overbased, alkyl oxy benzene sulfonate additive compositions. These lubricating oil compositions are useful in diesel engines, gasoline engines, as well as in marine engines.

Such lubricating oil compositions employ a finished lubricating base oil oil of lubricating viscosity which may be single or multigrade. Multigrade lubricating base oils are prepared by adding viscosity index (VI) improvers.

Typical viscosity index improvers are polyalkyl methacrylates, ethylene and propylene copolymers, styrene-diene copolymers, and the like.

The lubricating base oils used in such compositions may be mineral oils or synthetic oils of viscosity suitable for use in the crank case of an internal combustion engine such as gasoline engines and diesel engines which include marine engines. Crank case lubricating oils ordinarily have a viscosity of about 1300 cSt at 0° F to 24 cSt at 210° F (99° C). The lubricating base oils may be derived from synthetic or natural sources. Mineral oils for use as the base oil in the invention includes paraffinic, naphthenic and other oils that are ordinarily used in lubricating oil compositions. Synthetic oils include both hydrocarbon synthetic oils and synthetic esters. Useful synthetic hydrocarbon oils include liquid polymers of α-olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of C ₆ to C, ₂ α-olefins such as 1-decene trimer. Likewise, alkylbenzenes of proper viscosity such as didodecyl benzene, can be used. Useful synthetic esters include esters of both monocarboxylic acids and polycarboxylic acids as well as monohydroxy alkenols and polyols. Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate and the like. Complex esters prepared from mixtures of mono and dicarboxylic acid and mono and dihydroxy alkanols can also be used,

Blends of hydrocarbon oils with synthetic oils are also useful. For example, blends of 10 to 25 wt. % hydrogenated 1 -decene trimer with 75 to 90 wt. % 150 SUS (100° F) mineral oil gives an excellent lubricating base oil.

In one embodiment, the lubricating oil also has an ashless dispersant and a zinc dialkyldithiophosphate.

In another embodiment, the lubricating oil also has a detergent selected from the group consisting of metal phenates, metal sulfonates, and metal salicylates.

Other additives which may be present in the formulation include rust inhibitors, foam inhibitors, corrosion inhibitors, metal deactivators, pour point depressants, anti-oxidants, and a variety of other well-known additives

More specifically, the following additive components examples of components that can be favorably employed in combination with the overbased, alkyl oxy benzene sulfonate of the present invention

(1 ) Metallic detergents: overbased sulfurized alkylphenates, overbased sulfonates, and overbased salicylates. (2) Ashless dispersants: alkenyl succinimides, alkenyl succinimides modified with other organic compounds, and alkenyl succinimides modified with boric acid, alkenyl succinic ester.

(3) Oxidation inhibitors

1 ) Phenol type phenolic) oxidation inhibitors: 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-bis(2,6-di-tert-butylphenol),

4,4'-bis(2-methyl-6-tert-butylphenol), 2,2'-(methylenebis(4- methyl-6-tert-butyl-phenol), 4,4'-butylidenebis(3-methyl-6- tert-butylphenol), 4,4'-isopropylidenebis(2,6-di-tert- butylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol), 2,2'- methylenebis(4-methyl-6-cyclohexylphenol), 2,6-di-tert- butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4- dimethyl-6-tert-butyl-phenol, 2,6-di-tert-α-dimethylamino-p- cresol, 2,6-di-tert-4-(N.N" dimethylaminomethylphenol), 4,4'- thiobis(2-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6- tert-butylphenol), bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)- sulfide, and bis (3,5-di-tert-butyl-4-hydroxybenzyl).

2) Diphenylamine type oxidation inhibitor: alkylated diphenylamine, phenyl-α-naphthylamine, and alkylated α- naphthylamine.

3) Other types: metal dithiocarbamate (e.g., zinc dithiocarbamate), and methylenebis (dibutyldithiocarbamate).

(4) Rust inhibitors (Anti-rust agents) 1 ) Nonionic polyoxyethylene surface active agents: polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether,

polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol mono-oleate, and polyethylene glycol monooleate.

2) Other compounds: stearic acid and other fatty acids, dicarboxilic acids, metal soaps, fatty acid amine salts, metal salts of heavy sulfonic acid, partial carboxylic acid ester of polyhydric alcohol, and phosphoric ester.

(5) Demulsifiers: addition product of alkylphenol and ethyleneoxide, poloxyethylene alkyl ether, and polyoxyethylene sorbitane ester. (6) Extreme pressure agents (EP agents): zinc dialkyldithiophosphate (Zn-DTP, primary alkyl type & secondary alkyl type), sulfurized oils, diphenyl sulfide, methyl trichlorostearate, chlorinated naphthalene, benzyl iodide, fluoroalkylpolysiloxane, and lead naphthenate. (7) Friction modifiers: fatty alcohol, fatty acid, amine, borated ester, and other esters

(8) Multifunctional additives: sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum organo phosphoro dithioate, oxymolybdenum monoglyceride, oxymolybdenum diethylate amide, amine-molybdenum complex compound, and sulfur-containing molybdeπym complex compound

(9) Viscosity index improvers: polymethacrylate type polymers, ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polyisobutylene, and dispersant type viscosity index improvers.

(10) Pour point depressants: polymethyl methacrylate

EXAMPLES

The invention will be further illustrated by following examples, which set forth particularly advantageous method embodiments. While the Examples are provided to illustrate the present invention, they are not intended to limit it.

COMPARATIVE EXAMPLE

ALKYLATION USING NORMAL α-OLEFINS

A. Preparation of Alkylated Phenols

High overbased alkyl hydroxy benzene sulfonates were prepared using an alkylphenol derived by contacting 3.0 moles of phenol per each mole of a normal C ₂₀ to C ₂₄ α-olefin mixture using Amberlyst-36 catalyst [a polystyrene cross-linked sulfonic acid resin having a Hammett acid function (^ _o ) of less than -2.2 and an acid number of 5.4 milliequivalents per gram].

Amberlyst-36 resin catalyst is commercially available from Rohm & Haas,

Philadelphia, PA.

The olefin mixture had the following olefinic positions, determined by using a macro program using Nuclear Magnetic Resonance Spectroscopy (NMR).

wt. % Alpha wt. % Beta wt. % Internal wt. % Tri- substituted 89.1 0.5 1.4 0.3

The alkylation reactions were conducted at 100° C using a batch alkylation unit. The reaction time was six hours. Afterwards, the alkylated phenol was recovered by filtering and then stripping the excess phenol from the product stream at 400° F and 1 torr. The recovered alkylphenol products were analyzed for monoalkyl and dialkyl content and ortho/para substitution by superfluid chromatography (SFC) and fourier transform infrared spectroscopy (FT-IR) respectively.

The results of the SFC analysis are set forth in the table below:

% olefin/parrafin 0.3 wt. %

% monoalkylate 86.7 wt. % % dialkylate 12.6 wt. %

% phenol 0.1 wt. %

The results of the FT-IR analysis for the monoalkylate are set forth in the table below:

% ortho 50.3 wt. %

% para 49.7 wt. %

The alkylphenol was analyzed using gas chromatography and mass spectrometry. Average positional attachment results for the C ₂₂ carbon are as follows:

P- Ps P< Ps Pe P7 Pβ P ₉ P.o P11

49.84 17.80 9.99 4.65 4.47 3.47 2.95 2.61 2.17 2.04

B. Sulfonation of Alkylated Phenols

The alkylated phenol was sulfonated using a falling film reactor.

Reaction conditions were as follows:

Feed rate of alkylphenol was 4.26 gms/min

Charge mole ratio of sulfur trioxide to alkylphenol was 1.03:1

Air to sulfur trioxide ratio was 4:1 Reaction temperature was 90° C

Cyclohexamine analysis for this product indicates that a sulfonate as Ca value of 3.79 wt. % was obtained.

C. Neutralization

380 grams of alkylphenol sulfonic acids produced above were immediately neutralized in a stirred beaker containing 320 grams xylenes, 16 grams methanol, and 32 grams calcium hydroxide.

D. Overbasing

450 grams of xylenes, 90 grams of methanol, and 138.5 grams of calcium hydroxide were added to a reactor and stirred for five minutes. A slurry made up of 190.0 grams of alkylhydroxy benzene sulfonic acid at 3.80 wt. % Ca as sulfonate, 160 grams xylenes, 8 grams methanol, and 16 grams calcium hydroxide, were then added to the reactor and stirred for 20 minutes. The slurry was heated to 90° F during the 20 minute stir period. 79 grams of

carbon dioxide was charged to the reactor over 130 minutes. The rate of addition of the carbon dioxide was gradually reduced from 0.76 grams per minute to 0.25 grams per minute over the carbonation period. At 75% of the carbon dioxide charge, a second slurry made up of 190.0 grams of alkylhydroxy benezene sulfonic acid at 3.80 wt. % Ca as sulfonate, 160 grams xylenes, 8 grams methanol, and 16 grams calcium hydroxide was added. At 80% of the carbon dioxide charge, a slurry of 56 grams xylenes,

13 grams methanol, and 35.5 grams calcium hydroxide was added.

At the end of carbonation, the reactor was equipped with a condenser for stripping and the temperature was ramped to 200° F over two hours. At 200° F, the temperature was then ramped to 270° F over 30 minutes. At 270° F, 215 grams of 100 Neutral oil was added and the entire batch was then filtered through a Buchner filter. The filtrate was then stripped to 400° F at 40mm Hg vacuum. The base number was then measured with a resulting number of 318. An additional 45 grams of 100 Neutral oil was added to adjust the base number to 312.5.

The final product had a viscosity that was too viscous to measure at 00° C at a TBN of 312.5. It had 22.37% of the alkyl group of the sulfonate attached at the 4- position and higher positions of the alkyl group.

EXAMPLE 1

ALKYLATION USING ISOMERIZED OLEFINS

The procedures of the Comparative Example were repeated using a

C ₂₀ to C ₂₄ olefin mixture isomerized by using iron pentacarbonyl isomehzation. This isomerization process is known in the literature, and is disclosed in T. A. Manuel, Journal of Organic Chemistry, 27, 3941 (1962). The olefin mixture had the following olefinic positions, determined by using a macro program using NMR.

wt. % Alpha wt. % Beta wt. % Internal wt. % Tri-substituted

0.6 13.6 97 2.4

The alkylphenol was analyzed using gas chromatography and mass spectrometry. Average positional attachment results for the C ₂₂ carbon are as follows:

P ₂ Pa P, Ps Pe p ₇ Pβ p ₉ Pio P11

30.23 12.52 7.92 7.57 8.05 7.05 6.74 6.18 6.61 7.11

The final product had a viscosity of 581 cSt at 100° C at a TBN of 300. It had 49.33 % of the alkyl group of the sulfonate attached at 4- position and higher positions of the alkyl group.

EXAMPLE 2

ALKYLATION USING POLYALPHA OLEFINS

The procedures of the Comparative Example were repeated using a polyalpha olefin derived from Cι ₀ dimer. The polyalpha olefin had the following olefinic positions, determined by using a macro program using NMR.

wt. % Alpha wt. % Beta wt. % Internal wt. % Tri-substituted

14.0 13.4 29.8 56.0

The alkylphenol was analyzed using gas chromatography and mass spectrometry. Average positional attachment results for the C ₂₂ carbon are as follows:

p ₂ Pa P4 Ps Pe p ₇ Pβ p ₉ Pio P11

48.0 16.0 7.6 7.2 5.9 5.2 4.5 3.4 2.3 0.0

The final product had a viscosity of 109 cSt at 100° C at a TBN of 296.

It had 28.45 % of the alkyl group of the sulfonate attached at 4- position and higher positions of the alkyl group.

COMPARISON TO COMMERCIAL METAL-CONTAINING DETERGENTS

Results of experiments for comparing the overbased phenoxy sulfonate of the invention with commercially available metal-containing detergents are shown below

Oxidation stability

Test method according to JIS K-2514

Tested detergents

Example 10verbased phenoxy sulfonate of invention which is described in Example 1 of Specification

Phenate I. Commercially available overbased phenate Phenate ILAnother commercially available overbased phenate Sulfonate: Commercially available overbased sulfonate Salicylate I: Commercially available overbased salicylate Salicylate 11: Another commercially available overbased salicylate

Oil for test: TBN 33 in SAE #40

Test conditions heated at 165.5°C for 72 hours

Results: set forth in the following table

Metal-Containing Ratio of Viscosity (40")C) Detergent (Heated/Unheated)

Example 1 1.06

Phenate I 1.25

Phenate II 1.22 Sulfonate 1.39

Salicylate I 1.09 Salicylate II __2

The above results show the improved oxidation stability of the phenoxy sulfonate of the invention

Detergency at elevated temperature

Test method Hot tube test Oil for test TBN 33 in SAE #40 Test conditions 330°C, 16 hours

Results- set forth in the following table

Metal-Containing Detergent Laquer rating (10 = Clear))

Example 1 6.0

Phenate I 0

Phenate II 6.0

Sulfonate 0

Salicylate I 6.0

Salicylate II 6.0

The above results show the improved detergency of the phenoxy sulfonate of the invention at an elevated temperature

Thermal stability

Test method: Panel coker test Oil for test: TBN 33 in SAE #40 Test conditions: 320°C, 3 hours

Results: set forth in the following table

Metal-Containing Detergent Deposit (mg)

Example 1 40 Phenate I 10

Phenate II

Sulfonate 430

Salicylate I 155 Salicylate II 55

The above results show the improved thermal stability of the penoxy sulfonate of the invention.

Friction Coefficient Oil for test:

SAE 10W30 oil is prepared by compounding a succinimide ashless dispersant, a low overbased calcium sulfonate, zinc dialkyldithiophosphate, and a viscosity index improver into 150 neutral oil. To the compounded oil is added the metal-containing detergent in an amount corresponding to TBN 10. Results: set forth in the following table

Metal-Containing Fricti on Coefficient

Detergent

80°C 120

Example 1 0.100 0.087 Phenate I 0.163 0.157

Phenate II — —

Sulfonate 0.137 0.132

Salicylate I — —

Salicylate II — —

The above results show the reduction of friction coefficient proved by the phenoxy sulfonate of the invention.

Stability in Water Test method: ASTM D-2619 (modified)

Oil for test: TBN 33 in SAE #40

Test conditions: 100 g of the test oil (its TBN is previously determined) and 5 g of distilled water are placed in a pressure-resistant bottle. The bottle is placed in an air thermostat at 93°C, for 24 hrs. under the condition that the bottle is rotated with upside down at 5 r.p.m., for hydrolyzing the test oil.

The hydrolyzed test oil is then determined for its TBN. Decrease of TBN per the original TBN is calculated.

Results: set forth in the following table.

Metal-Containing Detergent Decrease of TBN (%)

Example 1 1

Phenate I 70

Phenate II 20

Sulfonate 30 Salicylate I 1 Salicylate II 6

The above results show the stability in water of the phenoxy sulfonate of the invention.

EXAMPLES OF ADDITIVE PACKAGES

The following wt.% is based on the amount of an active component, namely, with neither process oil nor diluent oil. The phenoxy sulfonate employed is that described in Example 1

I. Marine Diesel Engine Oils

1 ) Phenoxy sulfonate 65.0 wt.% Primary alkyl Zn-DTP 5.9 wt.% Diluent oil 29.1 wt.%

2) Phenoxy sulfonate 64.0 wt.%

Alkenylsuccinimide ashless dispersant 6.3 wt % Diluent oil 29 7 wt.%

3) Phenoxy sulfonate 59.0 wt.%

Primary alkyl Zn-DTP 5.4 wt.%

Alkenylsuccinimide ashless dispersant 5 9 wt.%

Diluent oil 29.7 wt.%

4) Phenoxy sulfonate 63.6 wt.%

Phenol type oxidation inhibitor 9 1 wt.% Diluent oil 27.3 wt.%

5) Phenoxy sulfonate 53.5 wt.% Alkylated diphenylamine-type oxidation inhibitor 16.3 wt % Diluent oil 30.2 wt %

6) Phenoxy sulfonate 63.6 wt.% Phenol-type oxidationinhibitor 4 5 wt.% Alkylated diphenylamine-type oxidation inhibitor 4.6 wt.% Diluent oil 27.3 wt.%

7) Phenoxy sulfonate 59.5 wt.%

Primary alkyl Zn-DTP 5.4 wt.%

Phenol-type oxidation inhibitor 5.0 wt.%

Diluent oil 30.0 wt.%

8) Phenoxy sulfonate 58.3 wt.%

Alkenylsuccinimide ashless dispersant 5.8 wt.% Alkylated diphenylamine-type oxidation inhibitor 8.3 wt.% Diluent oil 27.5 wt.%

9) Phenoxy sulfonate 57.0 wt.% Primary alkyl Zn-DTP 5.2 wt.% Alkenylsuccinic ester ashless dispersant 5.7 wt.% Phenol-type oxidation inhibitor 2.1 wt.%

Alkylated diphenylamine-type oxidation inhibitor 2.0 wt.%

Diluent oil 28.0 wt.%

10) Phenoxy sulfonate 46.2 wt.%

Overbased sulfurized alkylphenate 20.8 wt.%

Diluent oil 44.0 wt.%

11 ) Phenoxy sulfonate 37.0 wt.% Overbased sulfurized alkylsalicylate 28.0 wt.%

Diluent oil 35.0 wt.%

12) Phenoxy sulfonate 58.9 wt.% Overbased sulfonate 4.7 wt.% Primary alkyl Zn-DTP 6.5 wt.%

Diluent oil 29.9 wt.%

13) Phenoxy sulfonate 48.3 wt.% Overbased sulfurized alkylphenate 14.7 wt.% Primary alkyl Zn-DTP 6.0 wt.%

Diluent oil 31.0 wt.%

14) Phenoxy sulfonate 40.8 wt.%

Overbased sulfurized phenate 17.5 wt.% Alkenylsuccinimide ashless dispersant 6.7 wt.%

Diluent oil 35.0 wt.%

15) Phenoxy sulfonate 45.9 wt.%

Overbased sulfurized phenate 11.5 wt.%

Alkenylsuccinic ester ashless disersant 4.9 wt.%

Primary alkyl Zn-DTP 4.9 wt.% Diluent oil 32.8 wt.%

16) Phenoxy sulfonate 63.9 wt.% Overbased sulfurized alkylphenate 3.3 wt.% Phenol type oxidation inhibitor 1 1 wt.% Alkylated diphenylamine-type oxidation inhibitor 1.0 wt.%

Diluent oil 30.7 wt.%

17) Phenoxy sulfonate 51.6 wt.% Overbased sulfurized alkylphenate 5.7 wt.%

Primary alkyl Zn-DTP 3.3 wt.% Alkenylsuccinimide ashless dispersant 4.1 wt.% Alkylated diphenylamine-type oxidation inhibitor 1.6 wt.% Diluent oil 33.7 wt.%

18) Phenoxy sulfonate 53.4 wt.% Primary alkyl Zn-DTP 3.4 wt.% Alkenylsuccinimide ashless dispersant 5.7 wt.% Demulsifier 5.7 wt.%

Diluent oil 31.8 wt.%

19) Phenoxy sulfonate 47.0 wt.% Overbased sulfurized alkylphenate 16.0 wt.% Primary alkyl Zn-DTP 2.5 wt.%

Alkenylsuccinimide ashless dispersant 3.4 wt.%

Demulsifier 2.5 wt.%

Diluent oil 28.6 wt.%

Motor Car Engine Oils

1 ) Phenoxy sulfonate 25.3 wt.% Alkenylsuccinimide ashless dispersant 35.9 wt.% Primary alkyl Zn-DTP 11.2 wt.%

Diluent oil 27.6 wt.%

2) Phenoxy sulfonate 21.1 wt.% Overbased sulfonate 8.6 wt.% Alkenylsuccinimide ashless dispersant 30.1 wt.%

Primary alkyl Zn-DTP 9.7 wt.%

Diluent oil 30.5 wt.%

3) Phenoxy sulfonate 18.9 wt.% Alkenylsuccinimide ashless dispersant 39.6 wt.%

Secondary alkyl Zn-DTP 6.3 wt.% Dithiocarbamate type oxidation inhibitor 4.2 wt.%

Diluent oil 31.0 wt.%

4) Phenoxy sulfonate 14.9 wt.%

Overbased sulfurized alkylphenate 3.8 wt.%

Alkenylsuccinimide ashless dispersant 35.1 wt.%

Secondary alkyl Zn-DTP 6.4 wt.% Phenol type oxidation inhibitor 4.3 wt.%

Diluent oil 35.5 wt.%

5) Phenoxy sulfonate 20.0 wt.% Alkenylsuccinimide ashless dispersant 32.1 wt.% Secondary alkyl Zn-DTP 7.1 wt.%

Dithiocarbamate type anti-wear agent 3.6 wt.%

Diluent oil 37.2 wt.%

6) Phenoxy sulfonate 7 4 wt %

Overbased sulfurized alkylphenate 8 4 wt %

Basic sulfonate 3 7 wt %

Succinimide ashless dispersant 31.6 wt.% Secondary alkyl Zn-DTP 5 8 wt.%

Molybdenum-containing anti-wear agent 3 7 wt.%

Diluent oil 39 4 wt %

7) Phenoxy sulfonate 17.7 wt.% Alkenylsuccinimide ashless dispersant 28 7 wt.%

Primary alkyl Zn-DTP 3 4 wt.%

Secondary alkyl Zn-DTP 5 0 wt %

Alkylated diphenylamine-type oxidation inhibitor 5 7 wt %

Dithiocarbamate type anti-wear agent 0 9 wt %

Diluent oil 38 6 wt %

8) Phenoxy sulfonate 12 9 wt %

Alkenylsuccinimide ashless dispersant 37 9 wt %

Secondary alkyl Zn-DTP 8 2 wt %

Phenol type oxidation inhibitor 1 0 wt %

Alkylated diphenylamine-type oxidation inhibitor 4 1 wt %

Dithiocarbamate type anti-wear agent 1 0 wt %

Demulsifier 0 9 wt %

Boron-containing friction modifier 2 1 wt %

Diluent 31 9 wt %

111. Hydraulic Oils

1 ) Phenoxy sulfonate 4.6 wt.% Primary alkyl Zn-DTP 64.5 wt.% Phenol type oxidation inhibitor 6.6 wt.%

Phosphorous-containing extreme pressure agent 4.9 wt.%

Triazol type corrosion inhibitor 3.8 wt.%

Demulsifier 3.3 wt.% Nonionic anti-rust agent 3.3 wt.%

Diluent oil 9.0 wt.%

2) Phenoxy sulfonate 2.3 wt.% Basic sulfurized alkylphenate 2.5 wt.% Primary alkyl Zn-DTP 49.6 wt.%

Phenol type oxidation inhibitor 7.3 wt.% Sulfur-containing extreme pressure agent 6.0 wt.%

Triazol type corrosion inhibitor 3.4 wt.% Demulsifier 5.0 wt.%

Nonionic anti-rust agent 3.0 wt.%

Diluent oil 13.9 wt.%

3) Pehonoxy sulfonate 12.2 wt.% Phenol type oxidation inhibitor 14.8 wt.%

Diphenylamine type oxidation inhibitor 7.4 wt.% Sulfur-containing extreme pressure agent 4.5 wt.% Phosphorous-containing extreme pressure agent 39.2 wt.%

Triazol type corrosion inhibitor 1.0 wt.%

Demulsifier 7.0 wt.%

Nonionic anti-rust agent 4.5 wt.% Diluent oil 9.4 wt.%

4) Phenoxy sulfonate 8.5 wt.%

Overbased salicylate 3.7 wt.%

Phenol type oxidation inhibitor 13.5 wt.%

Diphenylamine type oxidation inhibitor 8.2 wt.%

Sulfur-containing extreme pressure agent 4.5 wt.% Phosphorous-containing extreme pressure agent 42.7 wt.% Triazol type corrosion inhibitor 1.2 wt.%

Demulsifier 6.5 wt.%

Nonionic anti-rust agent 4.3 wt.%

Diluent oil 6.9 wt.%

IV. Transmission Hydraulic Fluids

1 ) Phenoxy sulfonate 35.9 wt.%

Primary alkyl Zn-DTP 20.9 wt.%

Polyol type friction modifier 17.9 wt.% Sulfur-containing extreme pressure agent 5.8 wt.%

Diluent oil 19.5 wt.%

2) Phenoxy sulfonate 28.8 wt.%

Basic sulfonate 11.3 wt.%

Primary alkyl Zn-DTP 16.7 wt.%

Amide type friction modifier 13.9 wt.% Sulfur-containing extreme pressure agent 6.0 wt.%

Diluent oil 23.3 wt.%

3) Phenoxy sulfonate 32.2 wt.%

Primary alkyl Zn-DTP 18.9 wt.%

Alkenylsuccinimide ashless dispersant 0.5 wt.%

Amide type friction modifier 10.4 wt.%

Ester type friction modifier 13.9 wt.%

Phosphorous, Sulfur-containing extreme pressure agent 6.3 wt.%

Diluent oil 17.8 wt.%

4) Phenoxy sulfonate 23.6 wt.% Basic sulfonate 10.1 wt.% Overbased salicylate 2.4 wt.% Primary alkyl Zn-DTP 15.2 wt.% Polyol type friction modifier 0.4 wt.% Amide type friction modifier 8.4 wt.% Phosphorous, Sulfur-containing extreme pressure agent 5.1 wt.% Diluent oil 23.6 wt.%

While the present invention has been described with reference to specific embodiments, this application is intended to cover those various changes and substitutions that may be made by those skilled in the art without departing from the spirit and scope of the appended claims.