GB2113242A

GB2113242A - Lubricating oil composition containing a metal carbamate

Info

Publication number: GB2113242A
Application number: GB08226858A
Authority: GB
Inventors: Ronald J Vaughan
Original assignee: Chevron Research and Technology Co; Chevron Research Co
Current assignee: Chevron USA Inc
Priority date: 1978-12-26
Filing date: 1982-09-21
Publication date: 1983-08-03
Also published as: IT1127292B; NL185356B; SE8502737L; SE445464B; AU5251179A; AU532696B2; GB2113242B; BR7908403A; NL7909087A; FR2453891B1; FR2445369A1; IT7928195A0; SE8502737D0; GB2039291A; CA1143719A; DE2950647A1; FR2445369B1; NL185356C; DE2950647C2; FR2453890A1

Abstract

Lubricating oil compositions having good acid-neutralizing properties and relatively low ash content contain dispersant metal carbamates selected from those of the general formulae: <IMAGE> wherein M is an alkali or alkaline earth metal, X is sulfur or oxygen, R is an aliphatic hydrocarbyl group containing 1 to 50 carbon atoms, R' is hydrogen or an aliphatic hydrocarbyl group containing 1 to 50 carbon atoms, x is an integer from 1 to 10, y is 1 or 2 and is equal to the valence of M, and z is zero or an integer between 1 and 10.

Description

1 GB 2 113 242 A 1

SPECIFICATION Lubricating oil composition containing a metal salt

This invention relates to lubricating oil compositions containing a metal salt. More specifically, it relates to a lubricating oil composition containing a metal salt of a carbamate.

Engines are now being operated under increasingly severe conditions caused, in part, by the deteriorating quality of fuels. High-sulfur fuels produce large quantities of acid which must be neutralized by additives in the lubricating oil. Conventional lubricating oil additives used to neutralize acid are ordinarily metallic salts. These salts, when subjected to high engine-operating temperatures form non-volatile compounds (ash). As increasing amounts of the acid- neutralizing components are used in oil formulations, the amount of ash formed during engine operation can exceed the amount of 10 ash for which the engine is designed.

One preparation of conventional additives which are overbased to obtain additional acidneutralizing efficiency is taught to U.S. 3,126,340. The additive described in this patent is prepared by treating a lubricating oil suifonate dispersant with an alkaline earth metal oxide and hydroxide and then introducing carbon dioxide and ammonia into the mixture followed by heating the mixture in the presence of water to convert the ammonium carbamate formed from the carbon dioxide and ammonia to an alkaline earth metal carbonate. The alkaline earth metal carbonate is the acidneutralizing portion of the composition.

U.S. Patent 3,524,814 teaches the preparation of an overbased alkaline earth metal sulfonate by introducing a mixture of carbon dioxide and ammonia, in an amount sufficient to form a catalytic amount of ammonium carbamate, into a lubricating oil having in suspension a neutral alkaline earth metal sulfonate containing an alkaline earth oxide. After the catalytic amount of ammonium carbamate is preformed, carbon dioxide is continuously introduced into the reaction mixture until substantially all of the alkaline earth oxide is converted to alkaline earth metal carbonate. The metallic carbonate provides the reserve alkalinity in the sulfonate. As a post-treatment step, water is added to the reaction mixture. The addition of water decomposes any ammonium carbamate still present in the reaction mixture.

U.S. Patent 4,034,037 teaches the production of metal carboxylates or Norganic substituted carbamates by reaction of a carboxylic acid or carbon dioxide with an amine in the presence of a soluble metal salt. These salts are disclosed to be useful as lubricating oil additives.

Katchalski et al, J. Am. Chem. Soc. 73, 1829-1831 (1951) describe the preparation of the calcium salt of ethylene dicarbamate.

U.S. Patents 2,957,826 and 3,056,820 show the use of certain carbamate salts as gelling agents for greases.

It has now been found that a lubricant, capable of neutralizing acids formed during the operation 35 of an engine, is prepared by dispersing therein a carbamate of the formula R x 11 (R N-C- m X 11 (H N-C-X3 -- M 2 Y X VY (CR, NR] Z 2 + ---x 1 (CR v 2)x 1 (R'N-C-X--M 11 1/Y X (ii) (M) (1) wherein M is an alkali or alkaline earth metal, X is suifur or oxygen, R is an aliphatic hydrocarbyl group 40 containing 1 to 50 carbon atoms, R' is hydrogen or an aliphatic hydrocarbyl group containing 1 to 50 carbon atoms, x is an integer from 1 to 10, y is 1 or 2 and is equal to the valence of M, and z is zero or an integer between 1 and 10.

The method of dispersing the carbamate is not critical. It could, for example, be finely ground using a Manton-Gaulin Mill, and then be held in fine dispersion using a dispersant. Or it can be 45 prepared as taught in our copending Application No. 7943457. Maintaining a fine dispersion of the carbamate is critical to the effectiveness of the lubricating oil.

2 GB 2 113 242 A 2 The carbamates employed in this invention can be prepared using conventional techniques that are well known in the art. It is preferred to prepare them directly in lubricating oil using the novel process described fully herein. The preferred method of preparation comprises combining an amine or ammonia, a dispersant, a group 1 or group 11 metal oxide or hydroxide, carbon dioxide or carbon 5 disuifide and a promoter.

Preferred carbamates are those wherein M is barium, magnesium, or calcium. Magnesium and calcium are particularly preferred.

Referring to Formulae 1, 11 and lit, R is an aliphatic hydrocarbyl group containing 1-50 carbon atoms. For those groups having at least 3 carbon atoms, the aliphatic portion may be straight or branched-chain and may contain one or more sites of olefinic or acetylenic unsaturation. Preferred are 10 straight or branched-chain alkyl groups of 1-20 carbons, such as methyl, ethyl, propy], decyi, octy], or those derived from tallow amine or cocoamine. Most preferred are alkyl of 1 to 4 carbon atoms. R' is hydrogen or an aliphatic hydrocarbyl group as defined for R. R and R' need not be identical hydrocarbyl groups. Also preferred are those carbamates wherein R' is hydrogen. Preferred compositions of Formula Ill are those derived from ethylene amines and propylene amines, i.e. those for which x is 2 or 3 and z is zero or 1-4. The amines for use in preparing these carbamates are well known.

Typical dispersing agents that may be used to keep the carbamate in solution include alkali metal or alkaline earth metal hydrocarbyl sulfonates, hydrocarbyl succinimides, hydrocarbyl succinates, hydrocarbyl succinic anhydrides, alkali metal or alkaline earth metal alkylphenates, alkylphenol-type Mannich bases and alkaline earth metal salts of such Mannich bases. Mixtures of suspending agents 20 are also useful in carrying out the process of this invention.

The alkali metal and alkaline earth metal hydrocarbyl sulfonates useful in the process of this invention as dispersing agents are well known in the art. The hydrocarbyl group must have a sufficient number of carbon atoms to render the sulfonate molecule oil soluble. Ordinarily, the hydrocarbyl portion has at least 20 carbon atoms and may be aromatic or aliphatic, but is usually alkylaromatic.

Certain suifonates are typically prepared by sulfonating a petroleum fraction having aromatic groups usually mono- or dialkylbenzene groups, and then forming the metal salt of the sulfonic acid material.

Other feedstocks used for preparing these sulfonates include synthetically alkylated benzenes and allphatic hydrocarbons prepared by polymerizing a mono- or diolefin, for example a polyisobutenyl group prepared by polymerizing isobutene. The metallic salts are formed directly or by metathesis using well-known procedures.

Succinimides dispersants are also well known in the art, and a general method for their preparation is found in U.S. Patents 3,219,666, 3,172,892 and 3,272,746. These compositions are prepared by reading an oil-soluble alkyl or alkenyl succinic acid or anhydride with a nitrogen containing compound. The succinimide may be of the type commonly known as a mono- or bis succinimide. Preferred nitrogen compounds used in making the succinimides are those known as the ethyleneamines, and particularly preferred are triethylenetetraamine and tetraethylenepentamine. The preferred alkyl or alkenyl groups contain from 50 to 300 carbon atoms, and the most preferred compositions are prepared from polyisobutylene. When this type of suspending agent is employed, the amine portion will contribute to the alkalinity value.

The oil-soluble alkyl or alkenyl succinic anhydrides used in preparing the succinimides are themselves useful as suspending agents; however, they are most preferred for use as co-suspending agents, particularly in combination with a sulfonate suspending agent. Preferably the alkyl or alkenyl portion contains from 50 to 300 carbon atoms.

The succinate esters are prepared by reacting an alcohol with an alkenyl or alkyl succinic 45 anhydride as described above, using a procedure such as that described in U.S. Patents 3,381,022 and 3,522,179. Ordinarily the alkyl or alkenyl group contains from 50 to 300 carbon atoms.

Alkali metal and alkaline earth metal phenates are well known in the art and are the alkali metal or alkaline earth metal salt of an oil-soluble alkyl-substituted phenol. The composition may be sulfurized. Typical phenates are prepared by neutralizing a C,-,, alkylphenol with calcium hydroxide or 50 oxide.

Mannich bases are useful suspending agents. Mannich bases are prepared by reacting an oilsoluble phenolic or alcoholic material, such as alkylphenol, with an aldehyde, such as formaldehyde or acetaidehyde, and a nitrogen-containing compound. Typical Mannich bases contain from about 8 to 128 or more carbon atoms in the alkyl group. If desired, the alkaline earth metal salt of the phenolictype Mannich base may be used as a suspending agent.

If the carbamate is to be prepared in situ, a mixture is formed of the appropriate amine or ammonia, a dispersant as described above, an alkali metal or alkaline earth metal oxide or hydroxide, and a C,-, aikanol promoter. Carbon dioxide or carbon disuifide is then added to form the carbamate or thiocarbamate. This process is preferably carried out under anhydrous conditions. The aliphatic amine- 60 based carbamate, when prepared as above, can be dispersed in a fluid, non-gelled lubricating oil, since the workability of the product is adversely affected by water, the process if preferably carried out under anhydrous conditions. If the basically reacting metal compound is one which generates water as a result of the reaction of this invention, sufficient promoter should be used to keep the water in solution.

C i 0 Y 3 GB 2 113 242 A 3 Water not in solution leads to gel formation and the irreversible formation of metal carbonate, which prevents efficient filtering.

The compositions prepared by this invention provide a 1 sigh alkalinity value at a lower ash content than is present in most convention dispersants and/or acid neutralizers used as lubricating oil additives.

Alkalinity value is one method of specifying the degree of overbasing of the lubricating oil 5 composition. It is also a measure of the acid-neutralizing properties of the composition. The method for determining the alkalinity value commonly used for a composition is set forth in ASTM Method D 2896. Briefly, the alkalinity value is the total base number given as milligrams of potassium hydroxide per gram of sample. It is the quantity of potassium hydroxide required to neutralize the same amount of perchloric acid that 1 gram of the sample neutralizes. For example, if a composition has the same acid- 10 neutralizing capacity per gram as 10 mg of potassium hydroxide, the composition is given an alkalinity value of 10. The lower limit of alkalinity value is 0 for a neutral composition. Values of 200 or more are especially desirable for use in lubricants which are exposed to the decomposition products of sulfur containing diesel fuels. Typical alkalinity values for additive compositions of this invention range from about 30 to 400 or more.

Lubricant compositions containing the additives of this invention are prepared by admixing through conventional admixing techniques the appropriate amount of the additive of this invention with a lubricating oil. The selection of a particular base oil depends on the contemplated application of the lubricant and on the presence of other additives. Generally, the amount of additive of this invention used in the lubricating oil will vary from 0.1 to 40% by weight, and preferably from 2 to 35% by weight. 20 The resulting lubricating oil will usually have an alkalinity value in the range of 1 to 120, preferably 2.5 to 100.

The lubricating oils which may be used in this invention include a wide variety of hydrocarbon oils such as naphthenic bases, paraffin bases and mixed-base oils. The lubricating oils may be used individually or in combination and generally have a viscosity which ranges from 50 to 5000 SUS 25 (Saybolt Universal Seconds) and usually from 100 to 1500 SUS at 381C.

In many instances it may be advantageous to form concentrates of the additives of this invention within a carrier liquid. These concentrates provide a convenient method of handling and transporting the additives of this invention before their subsequent dilution and use. The concentration of the additives of this invention within the concentrates may vary from 85 to 40% by weight, although it is 30 preferred to maintain the concentration between about 50 and 70% by weight. The preferred method of obtaining concentrates is to carry out the preparation of the additive in a limited amount of the lubricating oil that will be used in making the final dilute lubricant composition. Alternatively, the additive may be prepared in a low-boiling hydrocarbon which is removed by distillation after adding a limited amount of lubricating oil.

As desired, other additives may be included in the lubricating oil compositions of this invention.

These additives include antioxidants or oxidation inhibitors, dispersants, rust inhibitors, anticorrosive agents, and so forth. Other types of lubricating oil additives which may be employed include antifoam agents, stabilizers, antistain agents, tackiness agents, antichatter agents, dropping point improvers, anti-squawk, extreme-pressure agents, odor control agent, and the like.

Examples

The following examples are presented to illustrate this invention, and are not in any way to be interpreted as limiting the scope of the invention.

Example 1

To a 5-litre, 3-neck flask was charged 700 g of a 67% concentrate of a calcium alkylated 45 aromatic sulfonate in hydrocarbon thinner, 350 g of a polyisobutenyl succinimide prepared from polyisobutenyl succinic anhydride having a number average molecular weight for the polyisobutenyl group of 1050, and tetra ethyl enepenta mine as a 57% concentrate in lubricating oil and containing 2.13% nitrogen, 2 100 mI of hydrocarbon thinner and 140 m] of 95% ethanol. The mixture was stirred at room temperature for 10 minutes and then 9 g of carbon dioxide was added over a 35-minute period at a temperature of from 251 to 281C. Then 140 g of ethylenediamine and 180.5 9 of calcium hydroxide were added to the mixture. An additional 206 g of carbon dioxide was added over a period of 2 hours, 17 minutes at a temperature of from 250 to 320C. 50 g of diatomaceous earth was added to the mixture, which was then filtered through a pad of diatomaceous earth. The filtrate was stripped at 25 inches Hg vacuum. Then 250 g of neutral lubricating oil was added, and this product was stripped 55 to 1051C at 40 mm Hg pressure. The mixture yielded 1441 g of product having an alkalinity value of 329.4, and containing 6.2 1 % calcium and 4.47% nitrogen.

Example 2

To a 5-litre, 3-neck flask was added 440 g of the calcium sulfonate described in Example 1, 2000 mi of hydrocarbon thinner and 92 mi of methanol. This mixture was stirred 73.2 g ethylenediamine and 60 68.4 g calcium oxide were added. To this mixture was added 10 1 g of carbon dioxide over a period of 1 hour, 4 minutes at a temperature of from 35 to 500C. The product was stripped to 11 51C at - -I W 4 GB 2 113 242 A atmospheric pressure and 2 50 mi of hydrocarbon thinner and 40 g of diatomaceous earth were added. The mixture was then filtered through filter aid and the filtrate was stripped after addition of 500 g of neutral lubricating oil to 1 OOIC at 200 mm of Hg pressure to yield 865 g of product as a 52% concentrate in oil having an alkalinity value of 184. 6, containing 3.55% calcium and 2.43% nitrogen.

Example 3

To a 1 -litre, 3-neck flask was added 110 g of the calcium sulfonate described in Example 1, 200 m[ of hydrocarbon thinner and 25 m[ of methanol. This mixture was stirred and to it was added 18.3 g ethylenediamine and 17.1 g of calcium oxide. This mixture was heated to 50,1C and then 26 g of carbon dioxide was introduced over a period of 1 hour. The mixture was stripped to 751C at atmospheric pressure and 5 m] water was added. The product set up into a gel. After addition of 15 mi 10 of water, the gel broke. The mixture was heated to 751C and 10 g of diatomaceous earth was added. The mixture was filtered through diatomaceous earth and then stripped to 901C at 20 mm of Hg pressure to yield 63 g of product having an alkalinity value 404.3 and containing a 4. 76% nitrogen and 28.65% suifated ash.

Example 4

To a 2-litre, 3-neck flask was added 184 g of the calcium suifonate described in Example 1, 420 m] of hydrocarbon thinner and 23 m[ of methanol. This mixture was stirred and to it was added 9.3 g of ethylenediamine and 33.9 g of calcium hydroxide. The mixture was heated to 451C and 29 g of carbon dioxide was added at a temperature of 45-480C. The product was stripped to 1320C under atmospheric pressure. The product was then filtered through diatomaceous earth and was stripped to 20 1600C at atmospheric pressure and then to 2041C at 20 mm Hg pressure to yield 133 g of product having an alkalinity value of 275.1, a sulfated ash of 29.5% and containing 1.7% nitrogen.

Example 5

To a 5-litre, 3-neck flask was added 700 g of the calcium sulfonate described in Example 1, 350 g of the succinimide described in Example 1, 2100 mi of hydrocarbon thinner and 140 mi of 95% ethanol. The reaction mixture was stirred at room temperature for 10 minutes and then 6 g of carbon dioxide was added at 251C over a 28 minute period. To the mixture was then added 140 g ethylenediamine and 180.5 g of calcium hydroxide. To this mixture was added 203 g of carbon dioxide over a period of 2 hours, 20 minutes at a temperature of 321C. The product was stripped to 11 OOC and 50 g of diatomaceous earth was added. The product was filtered through diatomaceous earth and then 30 250 g of 100 neutral lubricating oil was added and the mixture was stripped to 11 OIC at 20 mm Hg pressure to yield 1316 of product having an alkalinity value of 299.5 and containing 3.7% nitrogen and 6.54% calcium. The alkalinity value as measured by ASTM Method D-664 was 327.

Example 6

To a 5-litre, 3-neck flask was added 440 g of the calcium sulfonate described in Example 1, 2000 35 m] of hydrocarbon thinner and 150 mi of isopropyl alcohol. This mixture was stirred and to it was added 73.2 g ethylenediamine and 68.4 g of calcium oxide. Then, 99 g of carbon dioxide was introduced at a temperature of from 351 to 471C over a period of 1 hour, 18 minutes. The product was then stripped to 11 50C (bottoms) and 60 g of diatomaceous earth was added. The mixture was stirred for 20 minutes while cooling and then filtered through diatomaceous earth. The filtrate was treated with 40 g diatomaceous earth and filtered again through diatomaceous earth. To the filtrate was added 400 9 of 100 neutral lubricating oil and the mixture was stripped to 951C at 20 mm Hq pressure to yield 819 9 of product as a 49% concentrate in oil and having an alkalinity value of 207, and containing 3.66% calcium and 2.89% nitrogen.

Example 7 45

To a 5-litre, 3-neck flask was added 560 g of the calcium sulfonate described in Example 1, 280 g of polylsobutenyl succinic anhydride wherein the polyisobutenyl group had a number average molecular weight of 1050, 140 g ethylenediamine and 2100 m[ of hydrocarbon thinner. The mixture was stirred for 15 minutes at room temperature and then 140 m] of ethanol and 169 g of calcium hydroxide were added. To this mixture, 188 g of carbon dioxide was introduced at a temperature of 50 from 251 to 381C over a period of 2 hours, 12 minutes. The mixture was then stripped to 1 501C and 9 of diatomaceous earth was added. The mixture was cooled with stirring to 401C and then filtered through diatomaceous earth. The product was stripped to 11 OIC at 40 mm Hg pressure to yield 938 g of product having an alkalinity value of 374.3 and containing 4.20% nitrogen and 27.34% suffated ash.

The alkalinity value by ASTM Method D-664 was 407.

Example 8

To a 1 -litre, 3-neck flask was added 150 g of the calcium suifonate described in Example 1, 30 g of the succinimide described in Example 1, 350 mi of hydrocarbon thinner, 25 mi of 95% ethanol and 22.6 g of calcium hydroxide. The reaction mixture was cooled to 5IC and 20 g of monomethylamine il W X GB 2 113 242 A 5 was added. A dry-ice condenser was placed on the reaction flask to avoid loss of methylamine during the addition. The reaction system was sparged with nitrogen before beginning carbonation and the 26 g of carbon dioxide was added at a temperature of 171 to 251C over a period of 5 minutes. The product was centrifuged for hour at 11,000 revolutions per minute. The solids from centrifugation were isolated by washing with mixed hexanes, centrifuging and drying in a vacuum oven. The alkalinity value 5 of the solids was 1008.4.

Example 9

To a 1 -litre, 3-neckflask was added 90 g of sodium sulfonate prepared by sulfonating 60 weight percent of petroleum fraction and 40 weight percent of a synthetic alkylbenzene, 300 mi hydrocarbon thinner, 15 ml of 100% ethanol, 9.2 g of 98% ethylenediamine and 12.0 of sodium hydroxide. To the 10 reaction mixture was added 13 g of carbon dioxide at a temperature from 250 to 300C over a period of 1 hour, 6 minutes. The mixture was stripped to 11 5IC (bottoms), cooled to room temperature and then g of diatomaceous earth added. The mixture was filtered through diatomaceous earth and the filtrate was then stripped 11 OIC at 15 mm Hg pressure to yield 82 g of product having an alkalinity value of 30.6 and containing 2.87% sodium and 0.28% nitrogen.

Example 10

To a 5-litre, 3-neck flask was added 880 g of the calcium sulfonate described in Example 1, 2000 mi of hydrocarbon thinner, 140 m] of 95% ethanol, 140 9 of 98% ethylenediamine and 118.5 g of aluminum hydroxide. To this mixture was added 101 9 of carbon dioxide at a temperature of from 251 to 350C over a period of 1 hour, 15 minutes after which 84 g of calcium hydroxide was added. The 20 mixture was stripped to 11 51C and the product centrifuged at 11,000 rpm for 30 minutes. The mixture was filtered through diatomaceous earth and the filtrate stripped to 11 50C at 20 mm Hg pressure to yield 579 g of product having an alkalinity value of 61.7 and containing 0.0002% aluminium, 0.1361 % calcium and 1.88% nitrogen.

Example 11

To a 1 -litre, 3-neck flask was added 1918 g sodium bicarbonate, 5 m] water, 20 m] methanol, 10.3 g magnesium oxide, 170 g of the sulfonate described in Example 1, and 400 mi of hydrocarbon thinner. This mixture was stirred and to it was added 15.3 g of ethyl enedia mine. To this mixture at a temperature of 30-351C was added 23 g carbon dioxide over a period of 3 hours. The mixture was then stripped to 11 WC (bottoms). Diatomaceous earth was added to the product which was then filtered, centrifuged for 0.5 hour at 11,000 RPM, and filtered again through diatomaceous earth. The filtrate was stripped to 11 5-120c1C at 4 mm Hg pressure to yield 159 g of product having an alkalinity value of 208.

Example 12

To a 2-litre, 3-neck flask was added 120 g of the calcium sulfonate described in Example 1, 600 35 mi of hydrocarbon thinner, 50 m] of ethanol, 80 g of the succinimide described in Example 1 and 22.6 g of calcium hydroxide. The reaction mixture was cooled to -51C. Ammonia gas was introduced at a rate of 500 mi per minute for a period of 432 minutes. During the last 28 minutes of ammonia introduction, 28 g of carbon dioxide was simultaneously introduced. During the addition of the ammonia and the carbon dioxide, the temperature of the reaction mixture rose from -50C to 261C. 40 The reaction mixture was then stripped to 11 50C (bottoms) at atmospheric pressure, cooled to 250C and then 25 g of diatomaceous earth was added. The product was filtered through diatomaceous earth and the filtrate was stripped to 11 OOC at 20 mm Hg pressure to yield 116 g of product having a alkalinity value of 144.8 and containing 4.82% calcium and 1.00% nitrogen.

Example 13

A 3-litre, 3-neck flask was charged with 250 g of the calcium sulfonate used described in Example 1 and 600 mi of hydrocarbon thinner. This mixture was stirred while 50 ml liquid ammonia and 38 g carbon dioxide were introduced at room temperature. The reaction mixture was maintained at 250C throughout the reaction. To this mixture was added 40 mi methanol and 25.2 g calcium oxide.

This mixture was stirred at room temperature, then heated to 450C and 100 mi methanol was added. 50 The product was stripped to 1301C (bottoms), centrifuged for 30 minutes at 11,000 RPM and then stripped to 950C at 20 mm Hg pressure to yield 147 g of product having an alkalinity value of 53.3 and containing 9.74% sulfated ash and 0.43% nitrogen.

Example 14

To a 2-litre, 3-neckflask was added 160 g of the calcium sulfonate described in Example 1 and 55 420 mi of hydrocarbon thinner. This mixture was stirred while 17 mi liquid ammonia and 28 g carbon dioxide were introduced at room temperature. The reaction mixture was maintained at 251C throughout the reaction. To this mixture was added 40 mi methanol and 25. 2 g calcium oxide. The mixture was stirred at room temperature, then heated to 451C and 100 mi methanol was added. The 6 GB 2 113 242 A 6 product was stripped to 1300C (bottoms), centrifuged for 30 minutes at 11, 000 RPM and then stripped to 951C at 20 mm Hg pressure to yield 147 g of product having an alkalinity value of 185.3 and containing 6.9% calcium and 0.73% nitrogen.

Example 15

To a 1 -litre, 3-neck flask was added 120 g of the calcium suifonate described in Example 1, 200 m] hexane and 25 mi methanol. The mixture was stirred and then 18.3 g ethylenediamine and 12.3 g magnesium oxide were added. The mixture was heated under reflux for 1 hour at 56-580C. Carbon dioxide was added at a flow rate of 100 mi/min and at a temperature of 530C over a period of 1 hour. The mixture was heated to reflux for -1 hour and then stripped to 751C at atmospheric pressure. 5 g of diatomaceous earth was added while cooling to 400C, the mixture was filtered through diatomaceous 10 earth and then stripped to 750C at 20 mm Hg pressure to yield 37 g of product having an alkalinity value of 101.6 and containing 0.0629% magnesium, 0.4050% calcium and 3.13% nitrogen.

Example 16

To a 1-litre, 3-neckflask was added 90 g of sodium sulfonate as used in Example 9,300 mi hydrocarbon thinner, 15 mi 100% ethanol, 9.2 g ethylenediamine, and 16.2 g sodium methoxide. Then, 8 g of carbon dioxide was added at a temperature of 301C over a period of 1 hour, 8 minutes. The mixture was stripped to 1 501C (bottoms); then it was cooled to 401 C and 10 diatomaceous earth was added. The mixture was centrifuged at 11,000 RPM for 30 minutes and then filtered through diatomaceous earth. The filtrate was stripped to 11 5IC at 20 mm Hg pressure to yield 73 9 of product having an alkalinity value of 153.3 and containing 6.6% sodium and 1.05% nitrogen.

Example 17

To a 1 -litre, 3-neck flask were added 90 g of sodium sulfonate as described in Example 9, 300 mi hydrocarbon thinner, 15 mi 100% ethanol, 9.2 g ethylenediamine and 12.0 g sodium hydroxide. Then, 13 g of carbon dioxide were added over a period of 1 hour, 44 minutes at a temperature of from 250- 25 301)C. The mixture was stripped to 11 50C (bottoms), cooled to room temperature and then 15 g of diatomaceous earth was added. The mixture was filtered through diatomaceous earth and then the filtrate was stripped to 1 OOOC at 15 mm Hg to yield 82 g of product having an alkalinity value of 30.6 and containing 0.28% nitrogen.

Example 18

To a 5-litre, 3-neck flask was added 880 g of the calcium sulfonate described in Example 1, 280 g of the succinimide described in Example 1, 2100 mi hydrocarbon thinner and 140 mI ethanol. To this mixture was added 6 g of sulfur dioxide at room temperature over a period of 45 minutes. 140 g ethylenediamine and 180.5 9 calcium hydroxide were added to the mixture, then 194 g carbon dioxide and 21 g of sulfur dioxide were added over a period of 2 hours, 20 minutes. The reaction mixture was 35 then stripped to 11 OOC (bottoms), centrifuged at 11,000 RPM for -1 hour and thenfiltered through diatomaceous earth and stripped to 11 OOC at 20 mm Hg pressure. Then, 150 g of 100 neutral lubricating oil was added to yield 1035 g of product having an alkalinity value of 234.3 and containing 1.26% sulfur, 2.77% nitrogen, and 5.17% calcium.

Example 19

To a 5-litre, 3-neck flask was added 880 g of the calcium sulfonate described in Example 1, 280 g of succinimide described in Example 1, 2100 m] of hydrocarbon thinner and 140 mi of 95% ethanol. Over a period of 35 minutes, 3 g of sulfur dioxide and 4 g of carbon dioxide were added to the mixture. Then 140 g ethylenediamine and 180.5 g calcium hydroxide were added and 186 g of carbon dioxide and 35 g of sulfur dioxide were added over a period of 2 hours, 50 minutes at a temperature from 301-421C. The reaction mixture was stripped to 11 51C (bottoms), centrifuged at 11,000 RPM for 30 minutes and then filtered through diatomaceous earth. The filtrate was stripped to 11 5IC at 20 mm Hg pressure and 150 9 of 100 neutral lubricating oil was added. The final product weighed 1288 g, had an alkalinity value of 318.3 and contained 2.10% sulfur, 6.81 % calcium, and 3.75% nitrogen. The alkalinity value based on the ASTM D-664 titration was 342.

Example 20

To a 5-litre, 3-neck flask was added 560 g of the calcium sulfinate described in Example 1, 280 g of the succinic anhydride described in Example 7, 140 g ethylenediamine and 2100 mi of hydrocarbon thinner. The mixture stood for 15 minutes at room temperature after which 140 mi 95% ethanol and 169 g calcium hydroxide were added. Then, 183 9 of carbon dioxide and 10 mi of carbon disuifide 55 were added over a period of 2 hours, 25 minutes at a temperature of from 301-350C. The product was stripped to 11 50C, filtered through diatomaceous earth and then stripped to 11 OOC at 40 mm Hg pressure to yield a product having an alkalinity value of 352.6 and containing 4.41 % nitrogen, 7.72% calcium and 1.53% sulfur.

Q 1 h 11 7 GB 2 113 242 A 7 Example 21

To a 5-litre, 3-neck flask was added 600 9 of the succinimide described in Example 1, 2500 mi hydrocarbon thinner and 150 mi 95% ethanol. The mixture was stirred and 100 g ethylenediamine and 158 g calcium hydroxide were added. 175 g of carbon dioxide was added over a period of 2 hours, 9 minutes at a temperature of from 301-380C. The mixture was stripped to 11 OOC (bottoms), centrifuged at 11,000 RPM for 30 minutes and then filtered through diatomaceous earth. The filtrate was treated with 50 g of diatomaceous earth and stripped to 1051C at 20 mm Hg pressure to yield 647 g of product having an alkalinity value of 385.3 and containing 5.58% nitrogen and 23.19% sulfated ash.

Example 22

To a 2-litre, 3-neck flask was added 200 g of the succinic anhydride described in Example 9, dissolved in 1000 mi of hydrocarbon thinner and 43.6 g of ethylenediamine. The mixture was heated to 1 001C and then cooled to room temperature and 48.5 g of calcium hydroxide and 50 mi of 95% ethanol were added. Then, 40 g of carbon dioxide was added over a period of 41 minutes at a temperature of from 301 to 451C. The mixture was then stripped to 11 51C (bottoms) and filtered 15 through diatomaceous earth. The filtrate was stripped to 1051C at 20 mm Hg pressure to yield 214 g of product having an alkalinity value of 344.1 and containing 4.85% nitrogen and 6.76% calcium.

Example 23

To a 2-litre, 3-neck flask was added 36 g of the succinic anhydride described in Example 9, 18.4 9 of ethylenediamine and 500 mi hydrocarbon thinner. This mixture was heated to 501C for"' hour. It 20 was then cooled to room temperature and 110 g of the calcium sulfonate described in Example 1 were added along with 25 m[ of ethanol and 22.2 g of calcium hydroxide. The mixture was stirred and then g sulfur dioxide was added. An additional 200 mi of hydrocarbon thinner was added and the product was then stripped to 1201 C (bottoms). The product was centrifuged and a portion of the precipitate was taken up in hexanes and allowed to stand. This portion was then centrifuged at 18,000 25 RPM for 30 minutes. The product was dried in a vacuum desiccator. Upon analysis it contained 8.48% nitrogen and 37.0 sulfated ash.

Example 24

To a 2-litre, 3-neck flask was added 250 g of the succinimide described in Example 1 and 1000 mi of hydrocarbon thinner. This mixture was stirred and then 50 mi of ethanol, 45.2 g of calcium hydroxide and 37 g ethylenediamine were added. This mixture was stirred at room temperature and then 50 g of carbon dioxide was added over a period of 1.2 hours. An additional 6 g of calcium hydroxide was added and another 3 g of carbon dioxide was introduced. The temperature of the reaction mixture rose to 421C during the addition of the carbon dioxide. The mixture was stripped to 11 51C (bottoms). The product was centrifuged at 11,000 RPM for 1 hour, then filtered twice through 35 T diatomaceous earth and stripped to 1050C (bottoms) at 20 mm Hg pressure to yield 299 g of product having an alkalinity value of 297.1 and containing 5.22% calcium and 4.71 % nitrogen.

Example 25 The compositions of the Examples noted in Table 1 were tested in a Caterpillar 1 -G-2 test in which a single-cylinder diesel engine having a 5-1/8" bore by 61 " stroke is operated under the f 40 following conditions: timing, degrees BTDC, 8; brake mean effective pressure, psi 141; brake horsepower 42; Btu's per minute 5850; speed 1800 RPM; air boost, 5W Hg absolute; air temperature in, 2250F; water temperature out, 1 90OF; and sulfur in fuel 0.4% w. At the end of each 12 hours of operation, sufficient oil is drained from the crankcase to allow addition of 1 quart of new oil. In the test on the lubricating oil compositions of this invention, the 1 -G test is run for 60 hours. At the end of the 45 60-hour period, the engine is dismantled and rated for cleanliness using the Institute of Petroleum Test Number 247/69 merit rating for engine wear and cleanliness, accepted by ASTM, API and SAE as a rating system for engines. The over-all cleanliness of the engine is noted as WTD, which is the summation of the above numbers. Lower values represent cleaner engines.

The base oil used in these tests is a Citcon 350 neutral oil containing the noted amount of additive. Each oil was formulated to have an alkalinity value of 10.

Table 1

Example Grooves Lands Underhead WTD 2 82.0-250.0-99.05-161.0 90.58-191.6-263.6 4.48 1137 7 83.0250.0-318.5-182.0 105.0-413.5-250.3 12.18 1602 55 21 66.0-238.8-90.1-44 110.5-178.5-218.8 10.18 947

Claims

1. A fluid lubricating oil composition comprising an oil of lubricating viscosity having dispersed therein from 0.1 to 40% by weight of a carbamate of the general formula:

8 GB 2 113 242 A 8 X 11 (.R c R (I) wherein M is an alkali metal or alkaline earth metal, X is sulfur or oxygen, R is an allphatic hydrocarbyl group containing 1 to 50 carbon atoms, R' is hydrogen or an aliphatic hydrocarbyl group containing 1-50 carbon atoms, and y is 1 or 2 and is equal to the valence of M.

2. A composition as claimed in Claim 1 and containing a dispersant selected from an alkali metal or alkaline earth metal hydrocarbyisuifonate, a hydrocarbyisuccinimide, a hydrocarbyisu cci n ate, a hydrocarbyisuccinic anhydride, an alkali metal or alkaline earth metal alkylphenate, a Mannich base or an alkaline earth metal salt of a Mannich base, or a mixture of two or more thereof.

3. A composition as claimed in Claim 1 to 2, wherein M is barium, magnesium or calcium, X is oxygen, R contains 1-20 carbon atoms, and R' is hydrogen.

4. A composition as claimed in Claim 2, wherein M is magnesium or calcium, R is alkyl of 1-4 carbon atoms, and the dispersant is an alkali metal or alkaline earth metal hydrocarbyisuifonate, a hydrocarbyl succinimide or a hydrocarbyisuccinic anhydride, or a mixture of at least two thereof.

5. A lubricating oil composition comprising an oil of lubricating viscosity having dispersed therein from 0. 1 to 40% by weight of a carbamate selected from those represented by the general formulae: 15 X 11 (H N-C-M- M 2 y and (I1) X 17y [1 CRY ±-NR 2 Xl]z (CRY 2)x 1 (WN-C-X±M 11 1/Y X (M) wherein M is an alkali or alkaline earth metal, X is oxygen or sulfur, R' is hydrogen or an aliphatic hydrocarbyl group of 1 to 50 carbon atoms, x is an integer from 1 to 10, y is 1 or 2 and is equal to the 20 valence of M, and z is zero or an integer from 1 to 10.

6. A composition as claimed in Claim 5 and containing a dispersant selected from an alkali metal or akkaline earth metal hydrocarbyisuifonate, a hydrocarbyisuccinimide, a hydrocarbyisuccinate, a hydrocarbyisuccinic anhydride, an alkali metal or alkaline earth metal alkylphenate, a Mannich base or an alkaline earth metal salt of a Mannich base, or a mixture of two or more thereof.

7. A composition as claimed in Claim 5 or 6, wherein M is barium, magnesium or calcium X is oxygen, R' is hydrogen, x is 2-3, and z is zero or 1-4.

8. A composition as claimed in Claim 7, wherein the carbamate is a carbamate of formula 11.

9. A composition as claimed in Claim 7, wherein the carbamate is a carbamate of formula Ill.

10. A composition as claimed in Claim 9, wherein M is magnesium or calcium and the dispersant 30 is an alkali metal or alkaline earth metal hydrocarbyisuifonate, a hydrocarbyisuccinimide or a hydrocarbyisuccinic anhydride, or a mixture of at least two thereof.

11. A composition as claimed in Claim 10, wherein z is zero, 1, 2, or 3 and x is 2.

12. A lubricating oil composition concentrate comprising an oil of lubricating viscosity having dispersed therein from 40to 85% by weight of a carbamate selected from those of the general 35 formulae:

c (R X R 11 N-C- X 0 (H N-C-M -- M 2 y c L (1) (I1) 9 GB 2 113 242 A 9 X lly (CR' 2-txN, R] (CR I 2)x 1 (R'N-C-X-)-- M1/Y 11 X (M) wherein M is an alkali or alkaline earth metal, X is sulfur or oxygen, R is an aliphatic hydrocarbyl group containing 1 to 50 carbon atoms, R' is hydrogen or an aliphatic hydrocarbyl group containing 1 to 50 carbon atoms, x is an integer from 1 to 10, y is 1 or 2 and is equal to the valence of M, and z is zero or 5 an integer between 1 and 10.

13. The concentrate as claimed in Claim 12 and containing a dispersant selected from an alkali metal or alkaline earth metal hydroca rbyisu Ifon ate, a hydrocarbyisuccinimide, a hydrocarbyisuccinate, a hydrocarbyisuccinic anhydride, an alkali metal or alkaline earth metal alkylphenate, a Mannich base or an alkaline earth metal salt of a Mannich base, or a mixture of two or more thereof.

14. A concentrate as claimed in Claim 12 or 13 containing a carbamate of formula 1, wherein M is 10 barium, magnesium or calcium, X is oxygen, R contains 1-20 carbon atoms and R' is hydrogen.

15. A concentrate as claimed in Claim 14, wherein M is magnesium or calcium, R is alkyl of 1-4 carbon atoms, and the dispersant is an alkali metal or alkaline earth metal hydrocarbyisuifonate, a hydrocarbylsucc'inimide, or a hydrocarbyisuccinic anhydride, or a mixture of at least two thereof.

16. A concentrate as claimed in Claim 12 or 13 containing a carbamate of formula 11, wherein M 15 is barium, calcium or magnesium.

17. A concentrate as claimed in Claim 16, wherein M is magnesium or calcium and the dispersant is an alkali metal or alkaline earth metal hydrocarbyisuifonate, a hydrocarbyisuccinimide, or a hydrocarbyisuceinic anhydride, or a mixture of at least two thereof.

18. A concentrate as claimed in Claim 12 or 13 containing a carbamate of formula Ill, wherein M is barium, magnesium or calcium, X is oxygen, R' is hydrogen, x is 2-3, and z is zero or 1-4.

Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1983. Published by the Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained

18. A concentrate as claimed in Claim 12 or 13 containing a carbamate of formula Ill, wherein M 20 is barium, magnesium or calcium, X is oxygen, R' is hydrogen, x is 2-3, and z is zero or 1-4.

19. A lubricating oil composition concentrate in accordance with Claim 12, substantially as described in the foregoing Example 2 or 6.

New claims or amendments to claims filed on 12 Jan 1983 Superseded claims 1 to 19 New or amended claims:- 1. A fluid lubricating oil composition comprising an oil of lubricating viscosity having dispersed therein from 0. 1 to 40% by weight of a carbamate of the general formula:

(R X N-C- M (1) wherein M is an alkali metal or alkaline earth metal, X is sulfur or oxygen, R is an aliphatic hydrocarbyl 30 group containing 1 to 50 carbon atoms, R' is hydrogen or an aliphatic hydrocarbyl group containing 1-50 carbon atoms, and y is 1 or 2 and is equal to the valence of M.

2. A composition as claimed in Claim 1 and containing a dispersant selected from an alkali metal or alkaline earth metal hydrocarbyisuifonate, a hydrocarbyisuceinimide, a hydrocarbyisuccinate, a hydrocarbyisuccinic anhydride, an alkali metal or alkaline earth metal alkylphenate, an alkylphenol-type 35 Mannich base or an alkaline earth metal salt of a Mannich base, or a mixture of two or more thereof.

4. A composition as claimed in Claim 2, wherein M is magnesium or calcium, R is alkyl of 1-4 carbon atoms, and the dispersant is an alkali metal or alkaline earth metal hydrocarbyIsulfonate, a hydrocarbyl succinimide or a hydrocarbyisuccinic anhydride, or a mixture of at least two thereof.

5. A lubricating oil composition comprising an oil of lubricating viscosity having dispersed therein from 0. 1 to 40% by weight of a carbamate selected from those represented by the general formulae:

GB 2 113 242 A 10 X M2N-C-X+y M and X MY CRY 2 X-NR 1 jZ (CRY 2)-X 1 (Iii) (R'N-C-X--M,,y 91 X wherein M is an alkali or alkaline earth metal, X is oxygen or sulfur, R' is hydrogen or an aliphatic hydrocarbyl group of 1 to 50 carbon atoms, x is an integer from 1 to 10, y is 1 or 2 and is equal to the 5 valence of M, and z is zero or an integer from 1 to 10.

6. A composition as claimed in Claim 5 and containing a dispersant selected from an alkali metal or alkaline earth metal hydrocarbyisuifonate, a hydrocarbyisuccinimide, a hydrocarbyisuccinate, a hydrocarbyisuccinic anhydride, an alkali metal or alkaline earth metal alkylphenate, an alkylphenol-type Mannich base or an alkaline earth metal salt of a Mannich base, or a mixture of two or more thereof. 10 7. A composition as claimed in Claim 5 or 6, wherein M is barium, magnesium or calcium X is oxygen, R' is hydrogen, x is 2-3, and z is zero or 1-4.

10. A composition as claimed in Claim 9, wherein M is magnesium or calcium and the dispersant 15 is an alkali metal or alkaline earth metal hydroca rbyisu Ifon ate, a hydrocarbyisuccinimide or a hydrocarbyIsuccinic anhydride, or a mixture of at least two thereof.

12. A lubricating oil composition concentrate comprising an oil of lubricating viscosity having dispersed therein from 40 to 85% by weight of a carbamate selected from those of the general 20 formulae:

R X 11 N-C- M X 11 (H N-C-X) -- M 2 y X y CRY iNR 2t, 11 Z 2)jc (R'N-C-X±-M,_,y 11 X (II) (M) (I) wherein M is an alkali or alkaline earth metal, X is sulfur or oxygen, R is an aliphatic hydrocarbyl group 25 containing 1 to 50 carbon atoms, R' is hydrogen or an aliphatic hydrocarbyl group containing 1 to 50 carbon atoms, x is an integer from 1 to 10, y is 1 or 2 and is equal to the valence of M, and z is zero or an integer between 1 and 10.

13. The concentrate as claimed in Claim 12 and containing a dispersant selected from an alkali metal or alkaline earth metal hydrocarbyisuifonate, a hydrocarbyisuceinimide, a hydroca rbyisucci n ate, 30 a hydrocarbyIsuccinic anhydride, an alkali metal or alkaline earth metal alkylphenate, an alkylphenol type Mannich base or an alkaline earth metal salt of a Mannich base, or a mixture of two or more thereof.

11 GB 2 113 242 A 11 14. A concentrate as claimed in Claim 12 or 13 containing a carbamate of formula 1, wherein M is barium, magnesium or calcium, X is oxygen, R contains 1-20 carbon atoms and R' is hydrogen.

15. A concentrate as claimed in Claim 14, wherein M is magnesium or calcium, R is alkyl of 1-4 carbon atoms, and the dispersant is an alkali metal or alkaline earth metal hydrocarbyisuifonate, a 5 hydrocarbyisuccinimide, or a hydrocarbyisuccinic anhydride, or a mixture of at least two thereof.

16. A concentrate as claimed in Claim 12 or 13 containing a carbamate of formula 11, wherein M is barium, calcium or magnesium.

17. A concentrate as claimed in Claim 16, wherein M is magnesium or calcium and the dispersant is an alkali metal or alkaline earth metal hydrocarbyisuifonate, a hydrocarbyisuccinimide, or a 10 hydrocarbyisuccinic anhydride, or a mixture of at least two thereof.