FR2512458A1 - COMPOSITIONS, CONCENTRATES, LUBRICATING COMPOSITIONS AND METHODS FOR INCREASING FUEL SAVINGS IN INTERNAL COMBUSTION ENGINES - Google Patents

Abstract

THE INVENTION RELATES TO THE SAVINGS OF FUEL IN INTERNAL COMBUSTION ENGINES. THESE SAVINGS ARE IMPROVED BY LUBRICATING THESE ENGINES WITH LUBRICATING COMPOSITIONS INCLUDING AT LEAST ONE TARTRATE OF THE FORMULA: (CF DRAWING IN BOPI) IN WHICH EACH R IS INDEPENDENTLY A GROUP BASED ON HYDROCARBON AND SUM OF CARBON IN ATOMES THE TWO R GROUPS ARE AT LEAST ABOUT 8; AND B. AT LEAST ONE OIL SOLUBLE DETERGENT OR DISPERSANT. APPLICATION TO PETROL ENGINES.

Description

The present invention relates to compositions and methods for

  improve the operation of internal combustion engines, especially by reducing the amount

  of fuel consumed by these engines More particularly

  the invention comprises lubricating compositions which can be used in these engines to reduce fuel consumption and a method of using

  these lubricating compositions to achieve this goal.

  Efforts to reduce the amount of fuel consumed by internal combustion engines such as automobile engines have increased in recent years as a result of oil scarcity, increased cost of petroleum products and the desire to conserve natural resources such as oil will understand

  that a situation in which the consumption of

  tible is reduced to a minimum is advantageous, both because of the conservation factor and because such a situation

  is economical for the engine user.

  Many of the solutions to the problem of fuel conservation have been mechanical, such as tuning the engine to burn a leaner mixture or simply constructing smaller automobiles and smaller engines. concerned the development of friction-reducing lubricants in engines to reduce energy requirements Some synthetic lubricants have been developed and blended for use in engines

  to reduce fuel consumption.

  Considerable effort has gone into the development of additives for use in mineral lubricating oils and greases to reduce the properties of

  friction of oils and greases.

  Oil-soluble aliphatic polycarboxylic acids, including those in which the aliphatic group contains one or more hydroxyl groups, have been suggested as additives for use in lubricating oils.

  minerals and fuels in order to improve

  BACKGROUND OF THE INVENTION US Patent Nos. 2,370,299 and 2,370,300 disclose compound lubricants comprising a lubricating oil containing organic esters which comprise an aliphatic alcohol having from 10 to 30 carbon atoms esterified with a hydroxy-aliphatic acid. having at least one hydroxyl group The presence of the organic ester reduces the coefficient of friction between the metal surfaces subjected to

  friction at low friction rates.

  Lubricating oils and fuels containing tartaric acid derivatives with various amines and amino alcohols are described in US Pat. Nos. 2,977,309, 2,865,723, 2,811,429, 3,183,069 and 4,237,022. , the antirust and antioxidant properties of lubricants and fuels are improved by these

amino derivatives.

  U.S. Patent No. 2,715,108 discloses a lubricating oil, particularly a turbine oil, which

  contains an additive amount of a mixture of a poly-

  aliphatic carboxylic acid or a partial ester of such an acid and an oil-soluble phenolic compound or

  of its thio analogs or an aromatic carboxylic acid.

  This mixture added to a turbine oil gives

  improved antirust and anti-corrosion properties and a

  better resistance to emulsification in the presence of water.

  Mineral oils containing a small amount of an acid trialkylammonium acid salt ester of an acid

  hydroxylated aliphatic dicarboxylic acid and a mono-

  In addition to the beneficial effects of rust inhibition, the additive improves the properties of the aliphatic hydride, as described in US Pat. No. 2,585,877.

  anti-wear and cutting efficiencies of mineral oils.

  Extreme pressure lubricants containing compounds -3-

  obtained by reacting aliphatic carboxylic acids with

  Hydroxylated silicones and lower aliphatic polyhydric alcohols are described in US Pat. No. 2,755,250. Mineral oils for transformers are described in US Pat. No. 2,397,332, which comprise a small amount of a diacid ester.

  tartaric of a cyclic alcohol Extreme properties

  Lubricant pressure is said to be improved in US Pat. No. 2,628,941 by incorporating into a lubricating composition a reaction product obtained by reacting a polyacid compound containing from 1 to 3 free carboxylic acid groups and at least one hydroxy group. with an alkylene oxide, an alkylene sulfide

or an alkylene imine.

  In its broadest sense, the present invention relates to a composition of multiple constituents comprising: A at least one tartrate of the formula

HO-CHCO 2 R

HO-CHCO 2 R

  wherein each R independently is a hydrocarbon group and the sum of the carbon atoms in both R groups is at least about 8; and B at least one oil-soluble detergent or dispersant; and the use of such compositions in lubricating oils for internal combustion engines Lubricating oils containing the compositions according to the invention are effective in reducing the amount of fuel consumed by internal combustion engines The invention

  also relates to a process for reducing the amount of

  Fuel consumed by an internal combustion engine Lubricants may also contain other additives such as corrosion and oxidation inhibitors, pour point depressants, viscosity improvers, color and antifoam agents.

  As mentioned above, composition compositions

  Multiple components of the present invention include, in the broadest sense, a component A which is at least one tartrate and a component B which is a detergent.

  or oil soluble dispersant, or mixtures thereof.

  Component A of the compositions according to the invention is at least one tartrate of the formula

HO-CHCO 2 R

2

HO-CHCO 2 R

  wherein each R independently is a hydrocarbon-based group and the sum of the carbon atoms in the

  two groups R is at least about 8.

  A process for preparing the tartrates represented.

  by the above formula includes the esterification of tartaric acid with an alcohol or a mixture of alcohols that are

  preferably monohydric alcohols.

  The monohydric alcohols that can be used to give the desired R groups the tartrates are well known and may include, for example, primary and secondary aliphatic alcohols. Preferred monohydric alcohols,

  however, are primary aliphatic alcohols, especially

  Aliphatic hydrocarbon alcohols such as alkenols and alkanols having from about 4 to about 40 carbon atoms and preferably from about 8 to about 40 carbon atoms can be used. Mixtures of alcohols can be used as long as the total number of atoms of

  carbon in both groups R is at least about 8.

  Particularly preferably, each R group is derived from a monohydric alcohol containing at least 8 carbon atoms. Accordingly, examples of the preferred monohydric alcohols from which the R group is derived include 1-octanol, 1-decanol, 1-dodecanol, 1tetradecanol, 1-hexadecanol, 1-octadecanol, alcohol

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  Oleyl alcohol, linoleyl alcohol, linolenyl alcohol, phytol, myricyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, alcohol

  stearyl and behenyl alcohol.

  Of course, commercial alcohols (mixtures) are contemplated herein, and such commercial alcohols may include minor amounts of alcohols which, although not specified herein, do not preclude achieving the major objects of the present invention. Alcohols synthetic monohydric compounds of the type formed by the Oxo process (for example 2-ethylhexyl alcohol), by the condensation of aldols

  or by oligomerization catalyzed by an organo-

  alpha-olefin aluminum (especially ethylene)

  followed by oxidation are useful too.

  Examples of alcohols and monohydric alcohol mixtures

  Preferred hydric compounds useful in forming the tartrates useful in the compositions according to the invention include the commercially available "Alfol" alcohols marketed by Continental Oil Corporation. Alfol 810 is a mixture containing alcohols consisting essentially of primary chain alcohols. straight line having 8 to 10 carbon atoms Alfol 20 + alcohols are mixtures of C 18 -C 28 primary alcohols having mainly, on the basis of

  alcohols, C 20 alcohols as determined by chromato-

  gas-liquid graphing Alfol 22 + alcohols are C 18 -C 28 primary alcohols mainly based on alcohols with C 22 alcohols. These alcohols can contain a fairly high percentage (up to 40% by weight ) of paraffinic compounds that can be removed before

esterification if desired.

  Another example of a commercially available alcohol mixture is that of Ad Qa L 60 which comprises about 75% by weight of a straight chain C 22 primary alcohol, about 15% of a primary C 20 and about 8% 2 of alcohols C 18 and C 24 Adol 60 is marketed by

Ashland Chemical.

  Various mixtures of naturally occurring triglyceride-derived monohydric fatty alcohols having chain lengths of C 8 to C 18 are available from Procter and Gamble Company. These mixtures contain various amounts of fatty alcohols containing primarily 12 to 20 carbon atoms. , 14, 16 or 18 carbon atoms For example, CO-1214 is a mixture of fatty alcohols containing 0.5% C 10 alcohol, 66.0% C 12 alcohol, 26.0%

  of alcohol in C 14 and 6.5% of alcohol in C 16.

  Another group of commercially available blends includes "Neodol" products available from Shell Chemical Co. For example, Neodol 23 is a mixture of C 12 and C 13 alcohols; Neodol 25 is a mixture of C 12 and C 15 alcohols; and Neodol 45 is a

mixture of C 14 and C 15 alcohols.

  Vicinal fatty diols are also useful, and include those available from Ashland Oil under the general trade designation Adol 114 and Adol

  158 The first product is derived from a fraction of alpha-

  -olefins to straight chain in C 11-C 14 and the second is

derived from a C 15 -C 18 fraction.

  Examples of preferred branched chain monohydric alcohols useful in forming the tartrates useful in the present invention include, for example, commercial tridecyl alcohol substantially substantially in the form of:

  CH 3 CH 2 CH (CH 3) CH (CH 3) CH (CH 3) CH (CH 3) CH 2 CH 2 CH 2 OH

  prepared by the Oxo process and which is available from

  Exxon Corporation, hexadecyl alcohol prepared by the Oxo process, 12-methylpentadecyl alcohol, 6-methylldecyl alcohol, 8-ethyltetradecyl alcohol, 5,6-dipropyldecyl alcohol, and mixtures of Such alcohols Branched chain alcohols having 12 to 14 carbon atoms with one or more branched chain alcohols are particularly preferred.

several branches methyl.

  The tartrates represented by the above formula can be obtained by esterification of tartaric acid with one or more of the alcohols described above in

  conditions that are typical for performing the ester-

  These conditions include, for example, a temperature up to the reflux temperature of the mixture as long as this temperature is maintained below the decomposition temperature of the reaction mixture or any reaction products. Water is normally removed. during the esterification These conditions may possibly include the use

  of excess alcohol in relation to stoichiometric requirements

  for complete esterification with the alcohols of

  to facilitate the esterification reaction.

  Generally, the esterification reaction is conducted in a substantially liquid, substantially inert organic solvent or diluent such as mineral oil, toluene, benzene, xylene, etc. Esterification catalysts are included in the mixture, and these catalysts include toluenesulphonic acid, sulfuric acid, aluminum chloride, a boron trifluoride-triethylamine combination, methanesulphonic acid, hydrochloric acid, ammonium sulfate, phosphoric acid, methylate sodium, etc.

  The following examples illustrate the method of preparation

  Tartarates useful as component A in the compositions according to the invention Unless otherwise indicated, all parts and percentages

are by weight.

Example 1-A

  A mixture of 153 parts of tartaric acid hydrate, 400 parts of Procter and Gamble CO-1214, a mixture of alcohols containing mainly alcohols

  C 12 and C 14 aliphatics, of a part of toluene

  sulfonic acid and 500 parts of toluene is heated to the

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  The reflux temperature of the mixture is blown with nitrogen below the surface of the liquid and the water is removed when the temperature reaches 190 ° C. A total of 35 parts of water is collected. using a filter aid and the filtrate is the desired product.

Example 2-A

  A mixture of 95 parts of meso-tartaric acid, 226 parts of the alcohol mixture used in Example 1 and 0.5 part of toluenesulphonic acid is refluxed with nitrogen injection at a temperature of 160.degree. WC, 25 parts of water are collected. The mixture is cooled to

  -1550 C and heated for another two hours

  The reaction mixture is filtered with the aid of a

  filter aid and the filtrate is the desired product.

Example 3-A

  A mixture of 800 parts of the mixture of alcohols of Example 1 and 14 parts of water is heated to 50 ° C., whereupon sulfuric acid is added dropwise.

  (107 parts) over a period of two hours and the temperature

  The mixture reaches 60 WC. Potassium bitartrate (376 parts) is added in ten minutes using high speed stirring, after which the mixture is heated to a temperature of about 940 C for one hour. Xylene (500 cm 3) is added. The temperature of the reaction mixture reaches 165.degree. C. towards the end of the esterification. Parts of water are collected. The residue is stripped at 1400.degree. C. and 30.degree. mm Hg The residue is filtered using a

  filter aid and the filtrate is the desired product.

Example 4-A

  A mixture of 150 parts of tartaric acid, 288

  parts of Alfol 8-10 (a commercial mixture of alcoholic alcohols

  phage at C 8 and C 10), 1.12 parts of para-

  toluenesulfonic acid and 400 parts of toluene is heated to reflux while collecting the water in a trap of

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  Lateral branch A total of 34 parts of water were collected. The mixture was stripped at 1500 ° C. under mm Hg. Calcium hydroxide (0.44 part) was added with stirring for 10 minutes at 800.degree. C and the mixture is filtered using a filter aid The

filtrate is the desired product.

Example 5-A

  A mixture of 75 parts of tartaric acid is prepared,

  of 468 parts of Alfol 22 + S P and 1 part of para-

  The mixture is refluxed for a total of thirteen hours and a total of 16 parts of water are collected. The residue is stripped at 1200 ° C. at 25 mmHg and filtered off. using a filter aid The

  filtrate is the desired product having a saponification

  cation of 96.3 (the theoretical index is 107).

Example 6-A

  A mixture of 199 parts of tartaric acid, 718 parts of a commercially available mixture of commercial alcohols from Procter and Gamble under the general designation "CO 1895 F" containing about 2% C-fatty alcohols is prepared. 16 and 96% of fatty alcohols in C 18 and 1.1 parts of acid

  para-toluenesulfonic acid and 500 parts of toluene are added.

  This mixture is heated under reflux for a total heating period of about thirteen hours and 47 parts of water are collected in a side branch trap. The residue is stripped at 1350 ° C. under 25 mmHg. using a filter aid and the

  filtrate is the desired product having a saponification

  of 171 (the theoretical index is 172) and a melting point of 80-81 C.

Example 7-A

  A mixture of 150 parts of tartaric acid, 590

  parts of Aldol 158 (a mixture of commercially available diols

  from Ashland Chemicals), 500 parts of

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  The toluene and para-toluenesulfonic acid portions are heated to reflux while 33 parts of water are collected in a side branch trap. The reaction mixture is stripped at 1000 ° C. under 25 mm. The filtrate is the desired product having a saponification number of 168 (by repeating the test on

  find 157; the theoretical index is 159).

Example 8-A

  A mixture of 150 parts of tartaric acid, 414 parts of Neodol 23 (a commercial mixture of C 12 and C 13 alcohols), 1 part of para-toluenesulphonic acid is prepared.

  and 500 parts of toluene and heated to reflux.

  The water (36 parts) is collected in a side branch trap. The mixture is then stripped at 1350 ° C. at 27 mm Hg and filtered with a filter aid. The filtrate is the product of the invention. longed for

  having a saponification number of 218 (theo-

  212) and a melting point of 55-560 ° C.

Example 9-A

  A mixture of 150 parts of tartaric acid, 436 parts of Neodol 45 (a commercial mixture of C 14 and C 15 alcohols), 1 part of para-toluenesulfonic acid and 500 parts of toluene is heated to reflux. Water (35 parts) was collected in a side branch trap. The reaction mixture was then stripped at 1100 C under 21 mm Hg and filtered using a filter aid. is the desired product having a saponification number of 189

(theoretical index 204).

Example 10-A

  A mixture of 112.5 parts of tartaric acid, 480 parts of Adol 60 (a commercially available alcohol containing about 75% by weight of primary C 22 straight chain alkanol, about 15% was refluxed. of a C 20 alcohol and about 8% of a mixture of C 18 and C 24 alcohols, 400 parts of toluene and 1 part of paratoluenesulfonic acid. The water (25, 5 parts) in a side branch trap The mixture is stripped at 115 ° C at 22 mm Hg and filtered with a filter aid The filtrate is the desired product having a saponification number of

139 (theoretical index 149).

Example II-A

  A mixture comprising 163 parts (2.2 moles) of n-butanol, 400 parts (2 moles) of the commercial mixture of alcohols of Example 1, 150 parts of tartaric acid (2 moles), 1 part of Paratoluenesulfonic acid and 1000 parts of toluene This mixture is refluxed while collecting water (76 parts) in a side branch trap. The mixture is subjected to stripping at 1000 ° C. at 17 mm Hg and filtered at room temperature. Using a filter aid The filtrate is the desired product having a saponification number of 260 (index

theoretical 283).

  Example 12 A A mixture of 1500 parts of tartaric acid, 4000 parts of the commercial alcohol mixture of Example 1, 2000 parts of toluene and parts of paratoluenesulphonic acid was refluxed with 360 parts. parts of water (theoretical amount 360 parts) The reaction mixture was stripped at 1050 ° C. under 23 mm Hg. Calcium hydroxide (4 parts) was added at 1000 ° C. with stirring for 15 minutes. reaction mixture using a filter aid

  and the filtrate is the desired product.

Example 13-A

  A mixture of 150 parts of tartaric acid is prepared,

  484 parts of a mixture of alcohols available from

  Procter and Gamble under the designation CO-1418 (comprising 1-4% of C 12 alcohols, 35-47% of alcohols

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  C 14 '15 -27% C 16 alcohols and 30-40% C 8 alcohols),

  400 parts of toluene and 2 parts of para-

  toluenesulfonic acid and heated to reflux while

  eliminating water by means of a side branch trap.

  The mixture is then subjected to stripping at 1220 ° C. under 16 mm Hg. The residue is filtered while hot using a

  filter aid and the filtrate is the desired product.

Example 14-A

  A mixture of 1020 parts of potassium bitartrate and 2000 parts of the alcohol mixture of Example 1 is prepared and 737 parts of hydrochloric acid (37%) are added dropwise over a period of about twenty minutes. The mixture is heated while purging with nitrogen and the water is collected for one hour of heating at about 105-115 o C. The heating is continued at 1400 C for a period of seven hours while removing the additional water After cooling overnight, the mixture is again heated to about 1550 C and maintained at this temperature for

  about two hours while eliminating additional water.

  The mixture is then filtered at about 90 ° C with a filter aid and the filtrate is the desired product.

Example 15-A

  To a mixture of 2000 parts of the alcohol mixture of Example 1 and 49 parts of water, 383 parts of sulfuric acid (96%) are added over a period of 20 minutes, followed by addition of 1020 parts of potassium bitartrate in a period of ten minutes The mixture is heated while purging with nitrogen and the water is removed starting at about 1200 C and up to a temperature of about 1550 C. After cooling overnight, the mixture is again heated to a temperature of about -165 ° C while removing additional water. The total heating time at the esterification temperature is seven hours. at about 90 ° C using a filter aid and the filtrate is

the desired product.

Example 16-A

  A mixture of 882 parts of maleic anhydride, 819 parts of water and 21.78 parts of anhydrous sodium molybdate is prepared and gently heated until the maleic anhydride is dissolved. The mixture is heated to about 750.degree. Under a vacuum of approximately 50.8 cm of mercury so as to allow moderate reflux. While maintaining the vacuum at approximately 48.3-53.3 cm of mercury, 1525 parts of 30% aqueous hydrogen peroxide are added. in a period of 3.75 hours at 73-780 C by applying external heating as needed to maintain the temperature within this range Yellow solution becomes red

  orange, indicating the absence of peroxide and the trans-

  formation of maleic anhydride tartaric acid.

  A mixture of 2828 parts of the tartaric acid solution prepared above, 2994 parts of the mixture of alcohols of Example 1 and 41 parts of phosphoric acid (85%) is prepared and heated under flow of nitrogen at 1650 ° C. for several hours while distilling off the water. The mixture was maintained at 1650 ° C. for a total of twelve hours and, after cooling to 500 ° C., 30 parts of hydroxide were added all at once. Calcium is applied Vacuum and the mixture is heated to 1450 ° C. under 20 mmHg. The reaction mixture is filtered with the aid of a filter aid and the filtrate is the

desired product.

  CONSTITUTING B DETERGENT OR DISPERSANT

  The terms "detergent" and "dispersant" as used in the lubricant art generally refer, respectively, to a composition which is capable of

  detach the engine organ deposits and a

  which is able to maintain these suspended deposits

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  After detaching, detergents most often comprise basic metal salts or complexes of various organic (normally acidic) compositions containing both a polar and a non-polar group, while the dispersants include compositions also containing a polar group and a non-polar group, but which are free of metals or, if they contain a metal, contain at most

  about 1.1 equivalents per equivalent of acid portions.

  Both detergents and dispersants will be characterized more fully hereinafter, although their general nature is well known to chemists with experience

concerning lubricants.

  Detergents As noted above, most detergents are basic metal salts or complexes of a phenol, a sulfonic acid, a carboxylic acid or a phosphorus acid. Metals are usually alkali metals or alkaline earth metals, i.e. they are members of Group IA and Group IIA, respectively, of the Periodic Table of Elements. For purposes of the present invention, alkaline earth metal salts are Preferred alkaline earth metals are magnesium, calcium, strontium and barium, especially calcium or barium, and any

especially calcium.

  The nonmetallic portion of the salt or complex is usually the anion of an acidic organic compound. Examples of such compounds are phenols, sulfonic acids, carboxylic acids and phosphorus acids. The word "phenol" as used herein refers to any hydroxyaromatic compound, including hydroxy compounds derived from condensed ring hydrocarbons (eg

  for example, naphthols and similar compounds).

  Especially preferred in the preparation of component B are phenols substituted with aliphatic or cycloaliphatic groups having at least 6 carbon atoms.

  approximately and may have up to 7000 carbon atoms.

  Examples of such groups are hexyl, cyclohexyl, heptyl, decyl, eicosyl and groups derived from the polymerization of olefins such as ethylene, propylene, 1-butene, 2-butene, isobutene, etc. Groups derived from propylene polymers and commercial butene mixtures (mainly comprising isobutene), especially those having a mean molecular weight (as determined, for example,

  by gel permeation chromatography) of about 150-

  1750 (containing about 10-125 carbon atoms aliphatic

  The substituent and the aryl ring of the phenol may contain other groups such as hydroxy groups,

nitro, nitroso and sulfo.

  The introduction of the aliphatic substituent

  or cyclo-aliphatic on phenol by mixing the hydrocarbon (or a halogenated derivative of the hydrocarbon, or the equivalent) and the phenol at a temperature of about -2000 C in the presence of a suitable catalyst, such as aluminum trichloride, boron trifluoride, zinc chloride, etc. The substituent can also be introduced by

  other alkylation processes known in the art.

  The position of the substituent on the phenolic nucleus does not matter; Any single isomer or a mixture of isomers may be used. Polysubstituted materials such as dialkyl and trialkyl phenols may also be present, singly or in combination.

  mixture with monoalkyl phenols.

  Additional usable phenols are poly-

  phenols containing bridges of sulfur and bridges of

  ethene, typically prepared by reacting a single phenol with sulfur, a sulfur halide such as monochloride or sulfur dichloride or an aldehyde

  lower aliphatic (preferably formaldehyde).

  Polyphenols containing both bridges of sulfur and

  alkylene bridges are also usable.

  The equivalent weight of a phenol for the purposes of the present invention is its molecular weight divided by the number of phenolic hydroxyls it contains. Thus, the equivalent weight of an alkylated phenol is equal to its molecular weight and that of an alkylated resorcinol is half

of its molecular weight.

  The phosphorus acids useful in the preparation of component B may contain pentavalent or trivalent phosphorus. The preferred pentavalent phosphorus acids may be represented by the formula: ## STR2 ## wherein R 1 independently is hydrogen or a hydrocarbon-based group, at least one of

  they being a hydrocarbon group; each X inde-

  in the meantime there is oxygen or sulfur; and each independently is 0 or 1. Thus, it will be understood that the phosphorus acid may be an organophosphoric, phosphonic or phosphinic acid, or a thio analog of one.

any of them.

  The term "hydrocarbon-based" as used

  here denotes a group having a carbon atom bound directly

  to the rest of the molecule and having a

  In the context of the present invention, such groups include: (1) hydrocarbon groups, ie, aliphatic (eg, alkyl or alkenyl), alicyclic (eg, cycloalkyl or cycloalkenyl) groups; ), aromatic, aliphatic or alicyclic-substituted aliphatic and aromatic-substituted alicyclic, etc., as well as cyclic groups in which the ring is completed by another part of the molecule (i.e. any two groups

  indicated can together form an alicyclic group.

  (2) Substituted hydrocarbon groups, i.e. hydrocarbon-based groups as defined above also containing non-hydrocarbyl substituents which, in the context of the present invention, do not alter

  not the predominantly hydrocarbon character of the group.

  Such substituents are well known to those skilled in the art; examples include halo, nitro,

  hydroxy, alkoxy, alkylthio, carbalkoxy and acyl.

  (3) "h 6 tero" groups, that is groups which, although predominantly hydrocarbon in the context of the present invention, contain non-carbon atoms present in a chain or a

  also composed of carbon atoms hetero-

  suitable atoms will be apparent to those skilled in the art and include, for example, those of nitrogen, oxygen and

sulfur.

  In general, no more than about three substituents or hetero atoms, and preferably not more than one, will be present per 10 carbon atoms in the hydrocarbon-based group. Among the phosphorus acids which can be used are those prepared by the treatment of an olefin polymer (for example a polybutene having a molecular weight of about 1000) with a phosphoric agent such as phosphorus trichloride. Phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide or

phosphorothioic chloride.

  The equivalent weight of a phosphorus acid is its molecular weight divided by the number of hydroxy groups bound

to phosphorus in this acid.

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  The carboxylic acids that can be used in the preparation

  constituent B include carboxylic acid

  mono and polybasic aliphatic, cycloaliphatic

  and aromatic compounds free from acetylenic unsaturation, including naphthenic acids, alkyl acids or

  alkenylcyclopentanoic acids, alkyl or alkenyl

  cyclohexanoic acids and alkyl or alkenyl

  Aromatic (including salicylic acids) The aliphatic acids generally contain at least 8 and preferably at least 12 carbon atoms. The cycloaliphatic and aliphatic carboxylic acids may be saturated or unsaturated. Particular examples include 2-ethylhexanoic acid, linolenic acid, maleic acid substituted by propylene tetramer, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid,

  undecylic acid, dioctylcyclopentane

  carboxylic acid, myristic acid, dilauryldecahydro-

  naphthalenecarboxylic acid, stearyl-octahydroindene-

carboxylic acid, palmitic acid, acids formed by oxidation of petrolatum or hydrocarbon waxes and commercially available mixtures of two or more carboxylic acids such as talldl acids, rosin acids, etc. The equivalent weight of any of these acids is its divided molecular weight

  by the number of carboxy groups present there.

  The sulphonic acids useful in the preparation of detergents usable as component B include the "mahogany" sulfonic acids, the sulphonic acids of

  petrolatum, mono- and poly-naphthalenesulphonic acids

  substituted by paraffin, cetyl chlorobenzene acids

  sulphonic acids, cetylphenol sulphonic acids, cetyl

  phenol disulfide sulfonic acids, cetoxy capryl acids

  benzenesulphonic acids, diketyl thianthrene sulpho

  n-lauryl beta-naphthol sulphonic acids, dicapryl nitro-naphthalene sulphonic

  sulfonic acids of paraffin wax, sulpho

  unsaturated paraffin wax, sulphate

  hydroxyl paraffin wax, tetrahydroxy

  isobutylene sulfonic acids, tetraamylene sulfonic acids, chlorinated paraffin wax sulfonic acids, nitrosated paraffin wax sulfonic acids, petroleum naphthalenesulfonic acids, cetylcyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic acids, mono cyclohexyl sulfonic acids and

  polysubstituted by paraffin, postdodecyl

  benzene sulfonic acids, "dimeric alkyl" sulfonic acids, etc. These sulfonic acids are well known in the art and it is not necessary to describe them.

more here.

  For purposes of the present invention, the equivalent weight of a sulfonic acid or a sulfonic acid derivative is its molecular weight divided by the number of sulfonic acid groups or acid derivative groups.

  sulfonic acid which are present In this way, for a mono-

  the equivalent weight is equal to the molecular weight

  lar. The basic salts and complexes useful as component B are well known in the art and are described in numerous UAU patents, the following of which are

examples:

2,616,904 3,031,284 3,410,671

2,616,905 3,256,186 3,437,465

2,695,910 3,312,618 3,629,109

2,723,234 3,342,733 3,746,643

2,777,874 3,350,308 3,764,533

2,781,403 3,410,670

  The above patents as well as the published German Patent Application No. 1,243,915 are incorporated herein by

  reference for their salt and complex descriptions

  The salts and complexes useful in the present invention are

  invention are those described in these patents, both generic and

  only in the examples of implementation and

  include those described simply as international products

  mediates for transformation into salts and complexes more

strongly basic.

  The commonly used method for the preparation of these basic salts and complexes comprises heating a solution of the organic acid in a normally liquid, substantially inert organic diluent, such as mineral oil, with a stoichiometric excess of an agent. of metal neutralization such as oxide, sulphide, carbonate, bicarbonate or sulphide at a temperature

  more than 50 ° C and the filtration of the resulting mass.

  A "promoter" is often used in the necrosis stage.

  The examples of compounds useful as promoters include phenol compounds such as phenol,

  naphthol, alkylphenols, thiophenols, alkylamines,

  sulfurized phenols and condensation products of phenols with formaldehyde; alcohols such as methanol, 2-propanol, octyl alcohol, Cellosolve, Carbitol,

  ethylene glycol, stearyl alcohol and cycloalkyl alcohol

  hexyl; and amines such as aniline, phenylene diamine, phenothiazine, phenyl-beta-naphthylamine and dodecylamine It is also frequently preferred to further treat the basic compound prepared as described above.

  above by an acid gas, especially carbon dioxide.

  This treatment can be intermittent and followed by successive treatments with the metal neutralization agent, and often allows the incorporation of quantities.

  even larger basic metal in the complex.

  Preferred acidic organic compounds for use in

  The sulfonic acid and carboxylic acids described above, especially those having an equivalent weight of about 300-500, are used in the preparation of the detergents.

  Alkyl sulfonic acids are particularly preferred.

  aromatic compounds and more particularly alkyl acids

  benzene sulfonic. The preferred detergents are the alkali metal or alkaline earth metal basic salts of carboxylic and sulphonic acids. Particularly useful as detergents are soluble basic calcium sulphonates.

in the oil.

dispersants

  Dispersible dispersants in the oil are

  As previously indicated, these dispersants are generally free of metals or contain relatively small amounts of metal relative to the

  detergents described above.

  The molecular structure is the presence of an aliphatic hydrocarbon group having a solubilizing effect in oil containing at least about 40 aliphatic carbon atoms directly to a polar group. The dispersant may contain more than one of each of these groups per molecule, as will be seen

according to the description below.

  Many such dispersants are known in the art and are described in various patents.

  which of these dispersants are suitable for use in

  Examples of the present invention are: (1) Reaction products of carboxylic acids (or derivatives thereof) containing at least about 44 and

  preferably at least about 54 aliphatic carbon atoms.

  with nitrogen-containing compounds having at least one = NH group such as amines, ureas and hydrazines, with hydroxylated organic compounds such as phenols and alcohols and / or with basic inorganic materials Examples of these products, referred to herein as "carboxylic dispersants", are described in British Patent No. 1,306,529 and in numerous US patents including the following

3,163,603 3,351,552 3,541,012

3,184,474 3,381,022 3,542,678

3,215,707 3,399,141 3,542,680

3 219 666 3 415 750 3 567 637

3,271,310 3,433,744 3,574,101

3,272,746 3,444,170 3,576,743

3 281 357 3 448 048 3 630 904

3,306,908 3,448,049 3,632,510

3,311,558 3,451,933 3,632,511

3,316,177 3,454,607 3,697,428

3,340,281 3,467,668 3,725,441

3,341,542 3,501,405 Re 26,433

3,346,493 3,522,179

  (2) Reaction products of aliphatic or alicyclic halides containing at least about 40 carbon atoms with amines, preferably polyalkylene polyamines They can be characterized as "amine dispersants" and examples are described, for example , in the following US patents

3,275,554 3,454,555

3 438 757 3 565 804

  (3) Alkylphenol reaction products in which the alkyl group contains at least about 40 carbon atoms with aliphatic aldehydes containing

  at most 7 carbon atoms (especially formaldehyde

  Dehyde) and amines (especially alkylene polyamines which can be characterized as "Mannich dispersants". Examples of the materials described in the following U.S. Patents are:

2,459,112 3,442,808 3,591,598

2,962,442 3,448,047 3,600,372

2,984,550 3,454,497 3,634,515

3 036 003 3 459 661 3 649 229

3,166,516 3,461,172 3,697,574

3,236,770 3,493,520 3,725,277

3,355,270 3,539,633 3,725,480

3,368,972 3,558,743 3,726,882

3,413,347 3,586,629 3,980,569

  (4) Polymers containing a group having an effect of solubilization in oil (for example a pendant alkyl group having at least about 8 carbon atoms) and a polar group Examples are interpolymers of decyl methacrylate, oxide vinyl and decyl or an olefin of relatively high molecular weight

  with aminoalkyl acrylates, aminoalkyl acrylates,

  amides or poly-substituted alkyl acrylates

  (oxyalkylene), as well as copolymers of styrene,

  alkyl maleates and amides or imides of maleic acid.

  They can be characterized as "polymeric dispersants" and examples are described in the following U A patents:

3,329,658 3,666,730

3,449,250 3,687,849

3,519,565 3,702,300

  (5) Products obtained by subjecting the carboxylic, amine, Mannich or polymeric dispersants to further processing by reagents such as sulfur, urea, thiourea, guanidine, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbyl succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds, etc. Products of these types are described in German Published Patent Application (OLS) No. 2,551,256. and in the following US Patents: -24-

  3 036 003 3 282 955 3 493 520 3 639 242

  3 087 936 3 312 619 3 502 677 3 649 229

  3 200 107 3 366 569 3 513 093 3 649 659

  3,216,936 3,367,943 3,533,945 3,658,836

  3 254 025 3 373 111 3 539 633 3 697 574

  3 256 185 3 403 102 3 573 010 3 702 757

  3 278 550 3 442 808 3 579 450 3 703 536

  3,280,234 3,455,831 3,591,598 3,704,308

  3,281,428 3,455,832 3,600,372 3,708,522

4,161,475

  Descriptions of all patents and application

  patent cited above are incorporated herein by reference.

  Carboxylic dispersants and Mannich dispersants are preferred. The carboxylic dispersants can be very conveniently and precisely described by the groups (B1 and B-2) present therein. The B1 group is usually an acyl, acyloxy or acylimidoyl group containing at least about carbon atoms The structures of these groups, as defined by the International Union of Pure and Applied Chemistry, are as follows (each R 2 individually representing a hydrocarbon group or a similar group) or 2 _

Acyl R -C-

o 2 "

Acyloxy R -C-O-

NR 2 2 "

Acylimidoyl R -C-

  Group B-2 is preferably at least one group

  wherein a nitrogen or oxygen atom is directly

  The carboxylic dispersants are conveniently classified as "nitrogen-bridge dispersants" and "oxygen-bridge dispersants" in the preferred embodiment of the invention, wherein the nitrogen atom is also attached to a hydrocarbon-based group. which the atom directly linked to the radical Bi is

  nitrogen or oxygen, respectively.

  The nitrogen bridge carboxylic dispersants, which will be described first, are those described (for example) in the aforementioned US Pat. Nos. 3,219,666 and 3,272,746, which also disclose a large number of processes for their preparation. The B1 group source in the nitrogen bridge dispersants is an acylating agent comprising a carboxylic acid generating compound containing a hydrocarbyl or substituted hydrocarbyl substituent which has at least about 40 and preferably at least about 50 carbon atoms. "Carboxylic acid generating compound" means an acid, an anhydride, an acid halide, an ester, an amide, an imide, an amidine, etc .; the acids

and anhydrides are preferred.

  The carboxylic acid generating compound is usually

  prepared by the reaction (described more fully

  hereinafter) of a relatively low molecular weight carboxylic acid such as maleic acid, fumaric acid, maleic anhydride, etc., or a derivative of such an acid with a source of hydrocarbon containing at least about 40 and preferably at least about 50 carbon atoms The hydrocarbon source is usually aliphatic and should be substantially saturated, i.e., at least about 95% of the total number of bonds Covalent carbon-carbon bonds must be saturated bonds It must also be substantially free of pendant groups containing more than

  aliphatic carbon These can be sources of hydro-

  substituted carbides; we call "substituted"

  sources containing substituents which do not alter

  Characteristics are halide, hydroxy, ether, keto, carboxy, ester (especially lower carbalkoxy), amide, nitro, cyano, sulfoxy and sulfone radicals. Substituents, if present, generally do not constitute more than about 10%

  by weight of the hydrocarbon source.

12458

  The preferred hydrocarbon sources are those derived from substantially saturated petroleum fractions and olefin polymers, in particular polymers of monoolefins having from 2 to about 30 carbon atoms and more particularly from 2 to 16 carbon atoms. Thus, the hydrocarbon source can be derived from a polymer of ethylene, propene, 1-butene, isobutene,

  1-octene, 3-cyclohexyl-1-butene, 2-butene, 3-

  pentene, etc. Also useful are interpolymers of olefins such as those illustrated above with other polymerizable olefinic substances such as styrene, chloroprene, isoprene, pmethylstyrene,

  piperylene and dienes such as 1,3-hexadiene, iso-

  In general, these interpolymers should contain at least about 80%, preferably at least about 95%, by weight.

  of meshes derived from aliphatic monoolefins.

  Another suitable hydrocarbon source comprises saturated aliphatic hydrocarbons such as highly refined high molecular weight white oils or

synthetic alkanes.

  In many cases, the hydrocarbon source must contain an activating polar group to facilitate its

  reaction with the acid generating compound of molecular weight

  The preferred activating groups are halogen atoms, especially chlorine, but others

  appropriate groups include sulphide groups, disul-

  fure, nitro, mercaptan, ketone and aldehyde.

  As already mentioned, hydrocarbon sources

  generally contain at least about 40 and preferably

  At least about 50 carbon atoms are present among the olefin polymers. Those having an average molecular weight of more than about 600 are useful, and those of about 1300 to about 1500 (as determined by gel permeation chromatography) are useful. favorite, -27-

  although higher polymers with molecular weights

  The ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) can be about 1.5-6.0 and is preferably from about 10,000 to about 100,000 or higher.

usually 1.5-4.0.

  A preferred first class of polymers include those of terminal olefins such as propylene, 1-butene, isobutene and 1-hexene. Especially preferred in this class are polybutenes comprising predominantly isobutene meshes. ethylene terpolymers, a C 3-8 alpha-monoolefin and a polyene selected from non-conjugated dienes (which are especially preferred) and trienes An example of these terpolymers is that called "Ortholeum 2052" product

  by I of Pont de Nemours and Company, which is a

  polymer containing about 48 mole percent ethylene groups, 48 mole percent propylene groups and 4 mole percent 1,4-hexadiene groups and having an inherent viscosity of 1.35 (8.2 grams of polymer in

  cm 3 carbon tetrachloride at 30 ° C).

  Any one of a number can be used

  known reactions for the preparation of the general compound

  Thus, an alcohol of the desired molecular weight can be oxidized by potassium permanganate, nitric acid or a similar oxidizing agent; a halogenated olefin polymer can be reacted with a ketone; an ester of an acid containing active hydrogen, such as acetoacetic acid, can be converted into its sodium derivative and the sodium derivative

  can be reacted with a hydrocarbon of molecular weight

  high halogenated ring such as brominated paraffin or brominated polyisobutene; a high molecular weight olefin may be ozonized; a methyl ketone of the desired molecular weight can be oxidized by means of the haloform reaction; an organometallic derivative of a halogenated hydrocarbon or an olefin polymer can be converted into a nitrile, which is then hydrolysed; or an olefin polymer or its halogenated derivative can be reacted with an unsaturated carboxylic acid or a derivative of such an acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid,

  itaconic anhydride, mesaconic acid, glutamic acid

  conical, chloromaleic acid, aconitic acid, crotonic acid, methylcrotonic acid, sorbic acid, 3-hexenoic acid, 10-decenoic acid, 2-pentene-1 acid, 3,5-tricarboxylic, etc., or with a

  halogenated carboxylic acid or a derivative of such an acid.

  This latter reaction is preferred, especially when the acid generating compound is unsaturated and preferably when it is maleic acid or anhydride. The resulting product is then a hydrocarbylsuccinic acid or a

  derived from such an acid The reaction leading to its formation

  The reaction mixture merely comprises heating the two reactants at a temperature of from about 100 ° C. to about 10 ° C. The molar ratio of the polymer to the maleic acid or anhydride may be equal to, greater than or equal to

  less than 1, depending on the type of dispersant product desired.

  It is often preferred, however, to use

  portions such that the dispersant contains an average of at least 1.3 succinic portion per polymer portion;

  such dispersants are called "polysuccinic dispersants".

  Polysuccinic dispersants are especially preferred.

  containing about 1.4-3.5 succinic groups and very

  approximately 1.5-2.5 succinic groups per polymer group The substituted succinic acid or anhydride

  obtained can, if desired, be transformed into the halo

  corresponding acid genide by reaction with known halogenating agents such as phosphorus trichloride,

  phosphorus pentachloride or thionyl chloride.

  The nitrogen bridge catboxylic dispersants are prepared by reacting the acylating agent such as the substituted succinic acids or anhydrides with at least one nitrogen compound having the NH structure wherein the two remaining valences of the nitrogen are satisfied by hydrogen or amino or organic radicals linked to

  the nitrogen atom by direct carbon-nitrogen bonds.

  These compounds include aromatic amines, heteroarines,

  cyclic and carbocyclic as well as substituted ureas, thioureas, hydrazines, guanidines, amidines, amides, thioamides, cyanamides, etc. Among the amines useful for preparing the nitrogen bridge dispersant, are monoamines These monoamines may be secondary, that is to say those containing only a hydrogen atom directly attached to an amino group nitrogen atom Preferably, however, they contain at least one primary amino group, i.e. a group in which an amino group nitrogen atom is directly bonded to two hydrogen atoms. Monoamines are generally substituted by groups These hydrocarbon-based groups are preferably aliphatic in nature and free from acetylenic unsaturation and contain from about 1 to about 10 carbon atoms.

  saturated aliphatics are particularly preferred. Among the preferred monoamines are those of the general formula

  NHR 3 R 4 wherein R 3 is an alkyl group having up to ten carbon atoms Other preferred monoamines are aromatic monoamines of the

  general formula NHR 5 R 6 wherein R 5 is a phenol group

  alkyl, alkylated phenyl, naphthyl or alkylated naphthyl having up to 10 carbon atoms and R 6 is a hydrogen atom, an alkyl group having up to 10 carbon atoms or a group similar to R 5 Examples of usable monoamines are ethylamine, diethylamine, n-butylamine, -30-

  di-n-butylamine, allylamine, isobutylamine, coconut.

  amine, stearylamine, laurylamine, methyl lauryl-

  amine, oleylamine, aniline, methylaniline, N-

  methylaniline, diphenylamine, benzylamine, tolylamine and methyl-2-cyclohexylamine. Hydroxyamines are also included in the class of useful mono-amines.

  hydroxyhydrocarbyl-substituted analogues of mono-

  amines described above Hydroxy monoamines

  R 7 is hydrogen or a hydroxyl group having up to carbon atoms, R 8 is hydrogen or a group similar to R 7, R 9 is a hydroxylated phenyl, alkylated phenyl, naphthyl or alkylated naphthyl group having up to 10 carbon atoms and R 10 is hydrogen or a group similar to R 9, at least one of the substituents R 7 and R 8 and

  at least one of the substituents R 9 and R 10 being hydroxylated.

  Useful hydroxyl monoamines include

  ethanolamine, di-3-propanolamine, 4-hydroxybutyl-

  amine, diethenolamine, N-methyl-2-propylamine, 3-hydroxyaniline, N-hydroxyethylethylenediamine,

  N, N-di (hydroxypropyl) propylene diamine and tris (hydroxyl)

  Although hydroxy-amines containing only one hydroxy group are generally used as reactants, those containing

also be used.

  Heterocyclic amines are also useful for preparing the nitrogen bridge dispersant, as long as they contain a primary or secondary amine group. The heterocyclic ring may also contain unsaturation and may be substituted by hydrocarbon groups such as In addition, the ring may also contain other hetero atoms such as oxygen, sulfur, or other nitrogen atoms, including those having no further hetero atoms, such as oxygen, alkenyl, aryl, alkaryl or aralkyl. Hydrogen atoms linked to them Generally, these nuclei have -31-

  from about 3 to about 10, preferably 5 or 6 members.

  Among these heterocycles are aziridines, azetidines, azolidines, pyridines, pyrroles, piperidines, imidazoles, indoles, piperazines, isoindoles, purines, morpholines, thiamorpholines, N-aminoalkyl morpholines. , Naminoalkyl thiamorpholines, azepines, azocines, azonines, azecines and tetrahydro, dihydro and perhydro derivatives of each of the above compounds Preferred heterocyclic amines are those which are

  saturated and have 5- and 6-membered rings, especially

  piperidines, piperazines and morpholines

described above.

  Polyamines are preferred for preparing the nitrogen bridge dispersant. Among the polyamines are alkylene polyamines (and mixtures thereof), including those having the formula:

A -ll-

A N - * RL N) -

A A

  wherein N is an integer from about 1 to about 10, preferably from 2 to 8; each

  A independently is hydrogen or a group of hydro-

  carbide or hydroxy hydrocarbon having up to about carbon atoms; and Ril is a hydrocarbon group

  divalent having from about 1 to about 18 carbon atoms.

  Preferably, A is an aliphatic group having up to about 10 carbon atoms which may be substituted by one or two hydroxy groups and R 1 is a lower alkylene group having 1 to 10, preferably 2 to 6 carbon atoms. especially the alkylene polyamines wherein each A is hydrogen These alkylene polyamines include methylene polyamines, ethylene polyamines, butylene polyamines, propylene

  polyamines, pentylenes polyamines, hexylene poly-

  amines and heptylene polyamines. Also included are the higher homologs of these amines and the related aminoalkyl piperazines.

  these polyamines include ethylenediamine, triethylamine,

  ethylenetetramine, tris (2-aminoethyl) amine,

  propylenediamine, trimethylenediamine, hexamethylene

  diamine, decamethylenediamine, octamethylenediamine, di (heptamethylene) triamine, tripropylenetetramine,

  tetraethylenepentamine, trimethylenediamine, penta

  ethylenehexamine, di (trimethylene) triamine, 2-heptyl-

  3- (2-aminopropyl) imidazoline, 1,3-bis- (2-aminoethyl) -

  imidazoline, 1- (2-aminopropyl) -piperazine, 1,4-

  bis (2-aminoethyl) piperazine and 2-methyl- (2-aminobutyl) -

  Piperazine Superior homologs, obtained in

  densing two or more of the alkylene amines illustrated

  above, are also useful, as are polyoxy-

  alkylene polyamines (for example the "Jeffamines" available

  available from Jefferson Chemical Co).

  Ethylene polyamines, examples of which are mentioned above, are especially useful for reasons of cost and effectiveness. These polyamines are described in detail under the title "Diamines and Higher Amines" in the Kirk-Kirk Encyclopedia of Technical Technology. Othmer, second edition, Vol 7, pages 22 to 39 They are very conveniently prepared by the reaction of an alkylene chloride with ammonia or by reaction of an ethylene imine with a ring-cleaving agent such as ammonia These reactions result in the production of relatively complex mixtures of alkylene polyamines, including cyclic condensation products such as Piperazines.

  Because of their availability, these mixtures are particularly

  Useful in the preparation of the nitrogen bridge dispersant Satisfactory products can be obtained

  also by use of alkylene polyamines pure.

  Hydroxy polyamines, for example, alkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atoms, are also useful in the preparation of the nitrogen bridge dispersant. Preferred hydroxyalkylated alkylene polyamines are those in which the hydroxyalkyl group is present. Examples of such hydroxyalkyl polyamines include N- (2-hydroxyethyl) ethylene diamine, N, N'-bis (2-hydroxyethyl) ethylenediamine,

  1- (2-hydroxyethyl) -piperazine, diethylenetriamine mono-

  hydroxypropyl, dihydroxypropyltetraethylene pentamine

  and N- (3-hydroxybutyl) tetramethylene diamine homo-

  higher logues obtained by condensation of alkylene hydroxyalkyl amines via groups

  amino or hydroxy groups are also useful.

  The dispersant may also be prepared from hydrazine or an organic hydrazine of the general formula:

R 12 12

N-N Ra 2 _ R 1 2

  wherein each R 12 is, independently, hydro-

A gene or a C 1 -C 30 hydrocarbon radical, at least one R 12 radical being hydrogen. Preferably, the others are C 1 -C 10 aliphatic groups. Preferably at least two radicals are present.

  R 12 are hydrogen and in a specially preferred manner

  At least two such groups linked to the same nitrogen atom are hydrogen and the others are alkyl groups.

  with up to 10 carbon atoms Examples of hydra-

  substituted zines which can be used are methylhydrazine, N, N-dimethylhydrazine, N, N'-dimethylhydrazine, phenylhydrazine, N-phenyl-N'-ethylhydrazine,

  N- (p-tolyl) -N '(n-butyl) hydrazine, N- (p-nitrophenyl) -

  N-methylhydrazine, N, N'-di (p-chlorophenyl) hydrazine

  and N-phenyl-N'-cyclohexylhydrazine.

  For the formation of the nitrogen bridge dispersant, the anhydride or hydrocarbyl succinic acid, or the other carboxylic acid generating compound and the alkylene polyamine or the other nitrogen-containing reagent are heated to a temperature above about 80 ° C, preferably from about 1000 ° C to about 250 ° C. The product thus obtained has mainly amide linkages,

  imide and / or amidine (containing acyl or acyl

  amidoyl) The process can be carried out in some cases at a temperature below 800 C to give a product having mainly salt bonds (containing acyloxy groups). The use of a diluent such as mineral oil, benzene, toluene, naphtha, etc., is often advantageous for

  adjustment of the reaction temperature.

  The relative proportions of the carboxylic acid generating compound and the alkylene polyamine or the like compound are such that at least about half of the steochiometrically equivalent amount of polyamine is used for each equivalent of carboxylic acid generating compound. In this regard, it should be noted that the equivalent weight of the alkylene polyamine is based on the number of amine radicals present therein, and the equivalent weight of the carboxylic acid generating compound is based on the number of radicals

  Potentially acidic or basic (For example,

  The value of a hydrocarbyl succinic acid or anhydride is half of its molecular weight. Although a minimum of one-half equivalent of polyamine per equivalent of acylating agent should be used, there does not appear to be any limit. greater than the amount of polyamine If an excess is used, this excess simply remains in the product without reacting and without any adverse effect

  Normally, about 1-2 equivalents

  polyamine equivalents per equivalent of acylating agent.

  In an alternative process for the production of the nitrogen bridge dispersant, the reaction is first reacted.

  alkylene polyamine with a non-carboxylic acid

  saturated or halogenated low molecular weight or a derivative of such an acid (such as maleic anhydride or a

  others mentioned above) and the product

  resulting mediation is then reacted with the

  hydrocarbon source as previously described.

  The oxygen-bridge carboxylic dispersants include the esters of the carboxylic acids described above, as described (for example) in US Pat.

  No. 3,381,022 and 3,542,678 mentioned above.

  Thus, they contain acyl groups or, sometimes, acylimidoyl as group B-1 (An oxygen bridge dispersant containing an acyloxy group as group B-1 would be a peroxide, which would probably not be stable under all conditions. The esters are preferably prepared by conventional methods, usually the reaction (frequently in the presence of an acid catalyst) of the carboxylic acid generating compound with a hydrocarbon-based monohydric or polyhydric alcohol. or with

  a hydroxylated aromatic compound such as a phenol or naphthol.

  Hydroxyl compounds are usually alcohols

  containing up to about 40 aliphatic carbon atoms.

  These may be monohydric alcohols such as methanol, ethanol, propanols, butanols, pentanols, isooctanol, dodecanol, cyclohexanol, neopentyl alcohol, ethylene glycol monomethyl ether and so-called fatty alcohols such as lauryl, myristyl, cetyl, stearyl alcohol

  and behenyl and mixtures thereof, or polyhydric alcohols

  including ethylene glycol, diethylene

  glycol, dipropylene glycol, tetramethylene glycol, pentaerythritol, glycerol, etc. Fatty alcohols containing minor amounts of unsaturated bonds (e.g. not more than about two unsaturated bonds

22458

  The examples are palmitoleyl (C 16 H 300), oleyl (C 18 H 360) and eicosenyl (C 20 H 400) alcohols. Another class of useful hydroxyl compounds include the following: polyoxyalkylenes of the type commonly sold as demulsifier They include "Ethomeens", "Ethoduomeens", "Pluronics", "Tergitols", "Tetronics", "Dow Polyglycols", etc. Carbohydrates (eg sugars, starches, cellulose) are also useful as well as partially esterified derivatives of polyhydric alcohols having at least three hydroxyl radicals. Aliphatic polyols containing up to 10 carbon atoms and at least 3 hydroxy groups, especially those with up to 6 atoms, are preferred.

carbon and 3-6 hydroxy groups.

  The esterification reaction is usually carried out

  The esters may be neutral or acidic, or may contain non-esterified hydroxy groups, depending on whether the ratio of the equivalents of the acid-generating compound to the acid-generating compound is at least about 100 ° C. and typically about 150 ° C. to about 300 ° C. compound

  hydroxyl is equal to, greater than or less than 1: 1.

  It is possible to prepare mixed oxygen bridge and nitrogen bridge dispersants by reacting the acylating agent simultaneously or, preferably, successively with nitrogen and hydroxylated reagents such as those described above. nitrogen reagent and hydroxylated reagent may be included between

  : 1 and 1:10 approximately, based on equivalent weights.

  The methods of preparation of the mixed oxygen bridge and nitrogen bridge dispersants are generally the same as for the individual dispersants described, except that

  uses two sources of group B-2 Mixtures of dis-

  independently prepared persists are usable too.

  Mixed dispersants of these types are frequently -37-

  preferred for the purposes of the present invention.

  Examples of reactive metal compounds which can be reacted with the carboxylic acids described above to produce dispersants include lithium oxide, lithium hydroxide, lithium carbonate, lithium pentoxide, sodium oxide, sodium hydroxide, sodium carbonate, sodium methoxide, sodium propoxide, potassium oxide, potassium hydroxide, potassium carbonate, potassium methoxide, sodium magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium methoxide, magnesium propylate, magnesium salt of ethylene glycol monomethyl ether, calcium oxide, magnesium oxide, magnesium calcium hydroxide, calcium carbonate, calcium methoxide, calcium propylate, calcium pentoxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc propylate, strontium, strontium hydroxide, cadmium oxide, calcium hydroxide admium, cadmium carbonate, cadmium ethoxide, barium oxide, barium hydroxide, barium carbonate, barium ethoxide, barium pentoxide, aluminum oxide, aluminum isopropoxide, cupric acetate, lead oxide, lead hydroxide, lead carbonate, tin oxide, tin butylate, cobalt oxide, cobalt, cobalt carbonate, cobalt pentoxide, nickel oxide, nickel hydroxide, nickel chloride,

  nickel carbonate and chromium (II) acetate.

  Typical carboxylic dispersants usable as component B are shown in Table I. "Reagent B-1" and "Reagent B-2" are the sources of groups B-1 and B-2, respectively, as defined above.

TABLE I

  Carboxylic dispersants Reagent B-1 Reagent B-2 Ratio of equivalents B-1: B-2 Reaction temperature α-B Polybutenyl anhydride (about 900 molar weight) succinic prepared from polybutene

chlorinated

  isobutene mesh 2-B The same as in

example 1-B

  3-B As Example 1-B, except that the soft weight of the polybutene is about 1050 4-B As Example 1-B, except that the mol weight of the polybutene is about 850 -B The same that in

example 4-B

6-B The same as in

example 4-B

7-B The same as in

example 4-B

  Mixture of polyethylene amines containing about 3-7 amino groups per molecule Pentaethylene hexamine Pentaethylene hexamine Diethylenetriamine Ethylene diamine

Di- (1,2-propylene) -

  triamine N- (2-hydroxyethyl) trimethylene diamine 0.48 0.41 0.61 1.0 O 1.0 1.06 Mineral oil Mineral oil Mineral oil Mineral oil Mineral oil -190 Oil

minérale-

toluene -155 Mineral oil

Example

Thinner i oo ula on Ln Co

TABLE I

  Carboxylic Dispersants Reagent B-1 Reagent B-2 Equivalent Ratio

B-1: B-2

  Reaction temperature Oc 8-B The same as in

example 1-B

9-B The same as in

example 1-B

-B The same as in

example 1-B

  11-B As Example 1-B, except that the soft weight of the polybutene is about Penta-erythritol, followed by the polyethylene amine of Example 1B (equivalent ratio of 3.4: 1) The same as in

example 1-B

The same as in

example 1-B

  Pentaerythritol, followed by the polyethylene amine of Example 1-B (equivalent ratio 7.7: 1) 0.79 205-215 Xylene 0.67 1.33 Mineral oil Mineral oil 0.44 150-210 Oil mineral 12-B Acid produced by reaction Ethylene diamine

polybutene (mol.

  750) chlorinated (3.6% Cl) with KCN followed by hydrolysis 13-B Methyl ester product Triethylene tetramine by reaction of chlorinated polybutene (mol 1000) with methyl methacrylate (4.7% Cl)

Example

  Thinner I% O I 2.0 1.0 Xylene -220 K) Ln _, r 4 Co

TABLE I

Carboxylic dispersants

Example

  14-B Reagent B-1 Ester Reaction Product

sodiomalonic with paraf-

  C 75 -B bromine reaction product of chlorinated polybutene (850 mol) (4.5% Cl) with 16-B acrylic acid Reaction product haloform with methyl heptacontanyl ketone 17-B The same as in

Example II-B

  18-B As Example 1-B, except that the soft weight of polybutene is about 19-B The same as in

example 18-B

-B The same as in

example 18-B

  Reagent B-2 Equivalent Ratio B-i 1: B-2 The same as in 0.4

example 1-B

  Pentaethylene hexamine 0.8 The same as in

example 1-B

  Penta-erythritol Neopentyl Glycol Methano 11 Polyethylene Glycol (Mw approx. 600) 0.8 0.5 1.0 Excess Methanol 2.0 Reaction Temperature C Thinner Xylene -100 -210 -210 Mineral Oil

240-250

-65 Toluene

240-250

l o CD

TABLE I

  Carboxylic Dispersants Reagent B-1 Reagent B-2 Equivalent Ratio

B-1: B-2

  Temperature of reaction Oc 21-B The same as in

example 18-B

  22-B As Example 15-B, except that the

soft weight of poly-

  butene is about 23-B The same as in

example 22-B

  24-B Polybutene reaction product (1500 mol) with

chloride of chlorine

  Acetyl Oleyl alcohol ** Sorbitol Penta-erythritol 1.0 0.48 1.0 Mannitol 0.33 -173 Xylene -205 Mineral oil -205 -205 Mineral oil Catalyst hydrochloric acid catalyst Catalyst p-toluenesulphonic acid ro-I 1 uar C

Example

Diluent I-

12458

  In the preparation of carboxylic dispersants such as those described in Examples 1 B-24 B, reagent B-1 is normally prepared by reacting approximately equimolar amounts of the hydrocarbon source and the carboxylic acid of low molecular weight or its derivative It is also included in the

  general principle of the invention, however, to use as

  B, a nitrogen bridge or oxygen bridge or mixed nitrogen and oxygen bridge dispersant prepared by initially reacting more than one mole of acid or

  acid derivative with one mole of hydrocarbon source.

  In the preferred dispersants of this type, such as those described hereinabove, the hydrocarbon source is an olefin polymer such as polybutene and the carboxylic acid derivative is maleic anhydride. Dispersants of this type usually contain at about 3.5 and

  most often from about 1.5 to about 2.5

  for each group derived from the source of hydro-

  carbide. The method of preparation of dispersants of this type

  is essentially the same as for the dispersants

  Boxylics already described Reagent B-1, in particular, may be prepared by a one-step process in which the hydrocarbon source is reacted with maleic anhydride; by a two-step process wherein the hydrocarbon source is chlorinated and the chlorinated intermediate is reacted with maleic anhydride; or by various combinations of these two methods. Example 25-B

  A mixture of 1000 parts (0.495 mole) of a poly-

  butene comprising mainly isobutene meshes and having a number average molecular weight of 2020 and a weight average molecular weight of 6049 and 115 parts (1.17 mol) of maleic anhydride is heated to 1840 ° C.

255 '245

  6 hours while 85 parts (1.2 moles) of chlorine are added below the surface A 184-1890 C, an additional amount of 59 parts (0.83 mole) of chlorine is added in 4 hours. stripping the reaction mixture by passing nitrogen to 186-1900 ° C

  for 26 hours to obtain a polybutene anhydride

  succinic having a saponification number of 87 as

  determined by the method of ASTM D 94.

  893 parts (1.38 equivalents) of this anhydride

  substituted succinic acid, 1067 parts of mineral oil

  and 57 parts (1.38 equivalents) of a mixture of commercial ethylene polyamines containing from about 3 to about 10

  Nitrogen atoms per molecule The mixture is heated to 140-

   C for 3 hours and then subjected to a

  page through the nitrogen The stripped liquid is filtered and the filtrate is the dispersant

  desired (approximately 50% solution in the oil).

Example 26-B

  A mixture of 334 parts (0.52 equivalents) of the polybutenylsuccinic anhydride of Example 25-B,

  548 parts of mineral oil, of 30 parts (0.88 equi-

  penta-erythritol and 8.6 parts (0.0057 eq) of Polyglycol 112-2 dememulsion from Dow Chemical Company is heated to 150-210 ° C for about 11 hours. The mixture is cooled to 1900 ° C and 8.5 parts (0.2 equivalents) of the ethylene polyamine mixture of Example 25-B are added. The mixture is stripped by passing nitrogen therethrough for 3 hours at 2050 ° C and filtered for 20 hours. get the desired dispersant

  in the form of an approximately 40% solution in the oil.

Example 27-B

  A substituted succinic anhydride was prepared according to the mole of Example 26-B using a similar polybutene having a number average molecular weight of 1457 and a weight average molecular weight of 5808. A mixture of 5500 parts thereof anhydride, 3000 parts of oil

  mineral and 236 parts of the mixture of ethylene poly-

  amines of Example 26-B is heated at 155-1650 C for 2 hours, stripped by passing nitrogen at 1650 C for 1 hour and filtered to give a solution

  in the oil of the desired dispersant.

Example 28-B

  A product according to the procedure of Example 26-B is prepared from 1 equivalent of the substituted succinic anhydride of Example 25-B, 1-8 equivalents of pentaerythritol, 0.2 equivalent of mixture of ethylene polyamines of Example 26-B and mineral oil in an amount suitable to give a 30% solution of

produced in oil.

  Example 29-B A product is prepared according to the procedure of

  Example 25-B-using a succinic anhydride

  prepared by the reaction of 98 parts of maleic anhydride with 5670 parts of a 10% solution

  "Ortholeum 2052" in mineral oil.

  Soluble metal salts in the polyethylene oil

  aliphatic amines acylated with succinic acids

  substitutes are also useful as detergents in

  Examples of the present invention are the alkali metal, alkaline earth metal, lead, cadmium, zinc, nickel and alkylene cobalt salts.

  polyamines acylated with hydrocarbyl succinic acids.

  The main sources of the hydrocarbyl substituent

  take the high molecular weight oil fractions and olefin polymers described above, and the substituent must be substantially saturated, i.e. at least about 95% of the total number of bonds

  Covalent carbon-carbon are saturated bonds.

  The size of the hydrocarbyl substituent of the succinic compound appears to determine the effectiveness of the additive.

  It is important, therefore, that the

  which is large in size, that is to say

  has at least about 50 aliphatic carbon atoms.

  The molecular weight of the hydrocarbyl substituent should be between about 700 and about 100,000. The most common sources of the hydrocarbyl substituents essentially

  aliphatics are polyolefins such as poly-

  ethylene, polypropylene, polybutene, etc. A poly-

  Particularly preferred olefin is a polyisobutene

  having a molecular weight of about 1000.

  The basic metal compound used as a body in

  reaction can be an oxide, hydroxide, carbonate or alcohol

  lower alkali metal, alkaline earth metal, lead, cadmium or zinc or a combination of an alkali metal hydroxide and an inorganic metal salt

  selected from alkali metal halides and nitrates

  earth, lead, cadmium, zinc, nickel and cobalt Illustrative examples of basic metal compounds include sodium oxide, sodium methoxide, potassium hydroxide, potassium carbonate,

  lithium hydroxide, calcium hydroxide, carbohydrate

  Calcium Nate, Calcium Chloride, Barium Oxide, Barium Fluoride, Magnesium Ethylate, Magnesium Bromide, Magnesium Phenate, Zinc Hydroxide, Zinc Nitrate Trihydrate cadmium oxide, lead oxide, lead chloride, nickel hydroxide, nickel carbonate, cobalt hydroxide, cobaltous bromide, etc .; Amines which are useful in the preparation of these detergents include alkaline polyamines and

  hydroxyalkylated alkaline polyamines of the types described above.

  above about carboxylic dispersants.

  These aliphatic polyamine metal salts acylated with substituted succinic acids can be prepared either (1) by first preparing the acylated amine of the hydrocarbyl succinic compound and then reacting the amine -46-

  acylated with the basic metal compound, ie (2) in

  firstly, the monometallic salt of the hydrocarbyl compound

  succinic acid and then reacting this monometal salt with

  In the first process, it is preferred that the succinic compound be succinic anhydride and trace amounts of water, i.e. at about 2.5% by weight, are present when the basic metal compound is an oxide. In the second process, it is preferred that the succinic compound be succinic acid. In all cases, it is preferred to bubble the nitrogen or an inert gas through the reaction mixtures to remove any water

  formed as a result of the acylation reaction.

  The soluble metal salts in the polyethylene oil

  aliphatic amines acylated by substituted succinic acids and processes for their preparation are described in detail in U.S. Patent Re 26,433, and

  the description of this reissued patent is incorporated here

  by reference The following examples illustrate the preparation

  of the oil-soluble metal salts of aliphatic polyamines acylated with substituted succinic acids.

Example 30-B

  A polyisobutenyl succinic anhydride is prepared by the reaction of a chlorinated polyisobutylene (having an average chlorine content of 4.3% by weight and an average of 70 carbon atoms) with maleic anhydride at about 200 ° C. resulting polyisobutenyl succinic acid has an acid value of 103 A of a mixture of 3264

  grams (6 equivalents) of this polyiosbutenyl

  succinic, 2,420 grams of mineral oil and 75

  grams of water, 122.1 grams (3 equivalents)

  The addition is carried out in portions over a period of 30 minutes. The mixture is maintained at a temperature of 90 ° -100 ° C. for a period of 3 hours. The mixture is then heated to 1500 ° C. and we

  keep it at that temperature until it feels

  The mixture is cooled to 1000 ° C. and 245 grams (6 equivalents) of a mixture of ethylene polyamines having an average composition corresponding to that of tetraethylene pentamine and an equivalent weight of 40.8 are added. in portions over a period of 30 minutes, after which the mixture is heated to a

  temperature of 150-160 o C and maintained at this temperature.

  During the entire 5 hour period, nitrogen is bubbled through the mixture

  in order to remove the water formed as a result of the acylation.

  The residue is filtered. The resulting filtrate has a content of

  zinc of 1.63% and a nitrogen content of 1.39%.

Example 31-B

  To a mixture of 3750 grams (6 equivalents) of a polyisobutenyl succinic anhydride (having an acid number of 89.8 and prepared, as in Example 30-B, from maleic anhydride and polyisobutylene chlorine having an average chlorine content of 4.3% by weight and an average of 81 carbon atoms), 2632 grams of mineral oil and 75 grams of water are added at 80-100 ° C. grams (3 equivalents) of magnesium oxide. The addition is carried out in portions over a period of 10 minutes. The mixture is maintained at a temperature of 100.degree.-1050.degree. C. for 3 hours. During the first part of this period of 3 hours, 50 grams of water are then added. 113 grams (3 equivalents) of a mixture of amines as described in Example 30-B (but with an equivalent weight of 37.8) are added in portions over a period of 30 minutes. 30 minutes while the temperature of the mixture is maintained at 98-1000 ° C. The mixture is heated to 210-2150 ° C. and is maintained this temperature for 4 hours During the entire 4 hour period, nitrogen is bubbled through the mixture in order to remove the water resulting from the acylation. The residue is filtered. The filtrate has a magnesium content. 0.55%, based on sulphate ash, and a

nitrogen of 0.64%.

  Example 32-BA a mixture of 1028 grams (2 equivalents) of a polyisobutenyl succinic anhydride (having an acid number of 109 and prepared, as in Example 30-B, from maleic anhydride and a chlorinated polyisobutylene having an average chlorine content of 4.3% by weight and an average of 65 carbon atoms), 707 grams of mineral oil and 1500 grams of benzene are added at 600 ° C. grams (1 equivalent) of a mixture of amines

  described in Example 30-B (but with a balanced weight

  Values of 41). The addition is carried out in portions over a period of 30 minutes. The mixture is maintained at a temperature of 85-900 C for 7 hours. During this entire period of 7 hours, nitrogen is bubbled through

  the mixture so as to remove the water resulting from the acylation

  At 1034 grams of the above mixture and 52 grams of water, 52 grams (0.67 equivalents) of barium oxide are added at 80-900 C. The addition is carried out in portions over a period of 30 days. The mixture is maintained at a temperature of 80-90 ° C. for 2 hours. The mixture is then heated to 1500 ° C. and the last traces of water are stripped off. The residue is filtered off.

  barium of 3.9% and a nitrogen content of 0.76%.

Example 33-B

  To a mixture of 4200 grams (6 equivalents) of a polyisobutenyl succinic anhydride (having an acid number of 80 and prepared, as in Example 30-B, from maleic anhydride and chlorinated polyisobutylene having an average chlorine content of 4.3% by weight and an average of 92 carbon atoms) and 2 930 grams of oil

  at 390 ° C, 390 grams of 1- (2-hydroxyethyl)

  ethyl) piperazine The addition is carried out in portions in one portion.

  period of 30 minutes and the resulting mixture is now

  held at a temperature of 180-205 C for 5 hours.

  Throughout the 5 hour period, nitrogen was bubbled through the mixture so as to remove the water resulting from the acylation. To the above mixture, combined with 35 grams of water, was added at 300.degree. C, 159 grams (3 equivalents) of sodium carbonate The addition is carried out in portions over a period of 45 minutes. The temperature is maintained at 70-800 ° C. for 3 hours, after which the mixture is heated to 1500 ° C. and stripped for the last traces of water The residue is filtered The filtrate has a sodium content of 0.88% and a

nitrogen content of 1.1%.

Example 34-B

  To a mixture of 1,244 grams (2 equivalents) of a polyisobutenyl succinic anhydride (having an acid number of 90 and prepared, as in Example 30-B, from maleic anhydride and polyisobutylene chlorine having an average chlorine content of 4.3% by weight and an average of 81 carbon atoms), 871 grams of mineral oil and 25 grams of water are added at 80 ° C, 56 grams ( 1 equivalent) of potassium hydroxide The addition is carried out in portions over a period of 30 minutes, after which the mixture is maintained at 85-95 ° C for 1 hour and then dried by heating at 135-140 ° C. After 1 hour 104.2 grams (1 equivalent) of barium chloride were then added in portions over a period of 30 minutes at a temperature of 80 ° -90 ° C. The mixture was then heated to 130-140 ° C. for 9 minutes. hour and filtering 41 grams (1 equivalent) of a mixture of amines as described in Example 30-B (but with one ids equivalent to 41) The addition is carried out in portions over a period of 30 minutes, at a temperature of 110-140 ° C. The mixture is then heated at 160-1650 ° C. for 4 hours, during which time the mixture is bubbled.

12458

  The filtrate has a barium content of 2.7% and a content of the nitrogen content of the mixture.

in nitrogen of 0.61%.

  It is also preferred as component B, alternatively

  compared to the carboxylic dispersants described above.

  Mannich dispersants are, as previously indicated, reaction products of certain alkyl phenols with aldehydes (usually lower aliphatic aldehydes and especially formaldehyde) and amino compounds. The structure of the alkyl substituent on the phenol is the subject of the present invention. the same preferences with respect to the source, structure, molecular weight, etc., as indicated above with respect to the carboxylic dispersant. The amino compounds are the

  same as those described with respect to the carboxy dispersants

  nitrogen bridges and are subject to the same preferences.

  Mannich dispersants which can be used as

  Examples B are illustrated in the examples illustrating U.S. Patent No. 3,980,569 and German Patent Application No. 2,551,256 mentioned above.

  following are also illustrations.

Example 35-B

  A mixture of 3740 parts (2 equivalents) of a polybutenyl phenol in which the polybutene substituent comprises mainly isobutene meshes and has a molecular weight of about 1600, 1250 parts of textile gasoline and 2000 parts of Isopropyl alcohol is stirred while 352 parts (2.2 equivalents) of 38% aqueous formaldehyde solution are added. The mixture is stirred for 2 hours, left for 2 days and then stirred again for 17 hours. hours Acetic acid, 150 parts (2.5 equivalents) and the

* mixture is stripped of volatile matter under vacuum.

? 512458

  Remaining water is removed by adding benzene and

  performing azeotropic distillation; during the

  tillation, 1000 parts of mineral oil are added

  two portions The distillation residue is filtered.

  To 430 parts (0.115 equivalents) of the filtrate, 14.1 parts (0.345 equivalents) of the polyethylene amine mixture containing about 3 to 7 amino groups per molecule are added with stirring at 900.degree. C. The mixture is heated at -1200.degree. 2 hours and then at 150-1600 C for 4 hours, passing nitrogen therethrough for removal of volatiles. The resulting solution is filtered to obtain the desired Mannich dispersant (52% solution in mineral oil). ) which contains

1.03% nitrogen.

  Example 36-B A mixture of 564 parts (0.25 equivalents) of polybutenyl phenol in which the polybutene substituent comprises mainly isobutene and has a molecular weight of about 2020, 400 parts of mineral oil and 16 parts of 5 parts of isobutyl alcohol is heated to 65 ° C while stirring and 2.15 parts (0.025 equivalents) of 50% aqueous solution are added.

  sodium hydroxide, and then 16.5 parts (0.5 equiva-

  The mixture is stirred at 80.degree.-880.degree. C. for 6 hours and then 5 parts (0.025 equivalent) of 18.5% aqueous hydrochloric acid are added slowly, followed by stirring, and then 36 parts (0.875.degree. equivalent) of a mixture of polyethylene amines containing from about 3 to 7 amino groups per molecule at 880 C. The mixing operation is continued at 88-91 o C for 30 minutes The mixture is then heated to about 1580 ° C. passing nitrogen for removal of volatiles. 16 parts (0.5 mole) of sulfur and 25 parts of filter aid are slowly added at 1500 ° C. with stirring and nitrogen is passed through the mixture at 150 ° C. for 3 hours. then cooled to 1320 ° C and filtered to obtain the desired Mannich product as a 60% solution in mineral oil; it contains about 0.63% sulfur. In general, the compositions of the present invention comprise about 0.2-3.0 parts by weight of Component A per part of Component B. These proportions are those of the active chemicals, i.e. not counting any diluent such as mineral oil Preferred proportions are about 0.3-1.0 parts of component A per component B.

  Specific examples of composition compositions

  According to the invention, mixtures of constituents A and B are as follows:

Table II

  Compositions with multiple constituents

Example of

  Composition Constituent A Constituent B Weight ratio

A 1-A 3-B 1: 2

B 12-A 26-B 0.3: 1

C 12-A 2-B: 4-B 0.3: 0.5: 0.5

D 13-A 30-B 0.4: 1

E 6-A 3-B: 32-B 0.3: 0.4: 0.4

F 8-A 36-B 1: 1

  As indicated above, the compositions according to the present invention are also useful as additives for lubricants. They are particularly useful for lubricating machines which operate at temperatures

  relatively high, and are effective in a wide

  In addition, they lead to frequent

  a reduction in the amount of oxidation inhibiting additives (examples of which are given below) which must be incorporated into the lubricant and a reduction in

fuel consumption.

  The compositions can be used in various lubricants based on various lubricating viscosity oils, including natural lubricating oils.

  and synthetic and their blends These lubricants com-

  take internal spark ignition and compression ignition internal combustion engine lubricating oils, including automobile and truck engines, two-stroke engines, air piston engines, marine diesel engines and for railways, etc. They can also be used in gas engines, stationary generators and

  turbines, etc. Fluids for automatic transmissions

  tics, lubricants for combined rear axle gearbox assembly, gear lubricants,

  lubricants for metal working, hydraulic fluids

  and other lubricating oil compositions and

  fat can also be improved by incorporating

  ration of the compositions according to the present invention.

  Natural oils include animal oils and vegetable oils (eg castor oil, lard oil) as well as mineral lubricating oils such as

  that liquid petroleum oils and lubricating oils

  solvent-refined or paraffinic, naphthenic and mixed acid-refined minerals

  paraffinic-naphthenic Oils of lubricating viscosity

  coal-based or shale-derived oils are also useful base oils Synthetic lubricating oils include hydrocarbon oils and oils

  halogenated hydrocarbons such as polymeric olefins

  and interpolymerized (eg polybutylenes, polypropylenes, propylene-isobutylene copolymers,

  chlorinated polybutylenes, poly (1-hexenes), poly-

  (1-octenes), poly (1-decenes), etc., and mixtures thereof); alkylbenzenes (for example dodecylbenzenes,

  tetradecylbenzenes, dinonylbenzenes, di- (2-ethyl-

  hexyl) benzenes, etc); polyphenyls (e.g., biphenyls, terphenyls, etc.); Alkylated diphenyl oxides and alkylated diphenyl sulfides

  and their derivatives, analogs and homologues.

  Polymers and interpolymers of alkylene oxides and their derivatives whose terminal hydroxyl groups have been modified by esterification, etherification, etc.,

  constitute another class of synthetic lubricating oils

  known theories are examples of these are the oils

  prepared by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (for example polyisopropylene glycol methyl ether having an average molecular weight of 1000, polyethylene diphenyl ether). glycol having a molecular weight of 500-1000, the diethyl ether of

  polypropylene glycol having a molecular weight of 1000-

  1500, etc.) or their mono and polycarboxylic esters, for example the acetic acid esters, the mixed C 3 -C 8 fatty acid esters or the C 13 oxo acid esters.

tetraethylene glycol.

  Another suitable class of synthetic lubricating oils includes the esters of dicarboxylic acids (eg, phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, etc.) with various alcohols (for example butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, fumarate

  di-n-hexyl, dioctyl sebacate, diisopropyl azela-

  octyl, diisodecyl azela- late, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, linoleic acid dimer 2-ethylhexyl diester, complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.

  Esters useful as synthetic oils

  also take those formed from monocarboxylic acids

  C 5 to C 12 and polyols and polyol ethers such as trimethylolpropane, pentaerythritol, dipentaerythritol and the like. Silicon-based oils such as

  polyalkyl, polyaryl, polyalkoxy or polyaryloxy

  siloxanes and silicate oils are another useful class of synthetic lubricants (eg tetraethyl silicate, tetraisopropyl silicate,

  tetra (2-ethylhexyl) silicate, tetrasilicate silicate

  (4-methyl-2-tetraethyl), tetra- (p-tert-) silicate

  butylphenyl), hexyl- (4-methyl-2-pentoxy) -disiloxane,

  poly (methyl) -siloxanes, poly (methylphenyl) -siloxanes, etc.).

  Other synthetic lubricating oils include

  liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, decane phosphonic acid diethyl ester, etc.), polymeric tetrahydrofurans, etc. Unrefined, refined and re-refined oils, natural or synthetic (as well as mixtures of two or more of any of them) of the type

  described above may be used in the

  According to the present invention, unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from distillation operations on the basis of

  retort, a petroleum oil obtained directly from distillate

  or an ester oil obtained directly from

  of an esterification process and used without further

  treatment would be an unrefined oil.

  Finished products are similar to unrefined oils, except that they have been further processed in one or more purification steps to improve one or more

  properties of many such purification techniques

  cation are known to those skilled in the art, as the former

  solvent extraction, secondary distillation, acid or basic extraction, filtration, percolation, etc. Rerefined oils are obtained by processes similar to those used for obtaining refined oils applied to refined oils which have already been used in service These re-refined oils are also referred to as regenerated or reprocessed oils and are often further processed by techniques for the removal of used additives and / or

  of decomposition products of the oil.

  Generally, the lubricants according to the present invention will contain a quantity of the composition according to

  effective invention to reduce the consumption of

  of engines lubricated with the lubricants of the in-

  This amount will normally be from about 0.05% to about 10%, but from 0.1% to 5% per 100 parts by weight of the total finished lubricant.

are preferred.

  The compositions according to the present invention can

  contain, in addition to constituents A and B, other

  additives that are normally used in lubricants.

  These additives include, for example, ash-type and ashless type auxiliary detergents, viscosity index improvers, pour point depressants, antifoaming agents, extreme pressure agents. , rust inhibitors,

  oxidation and corrosion inhibitors.

  Examples of the ash-producing detergents are neutral and basic salts of alkali and alkaline earth metals with sulfonic acids, carboxylic acids or phosphorus-containing organic acids characterized by at least one direct carbon-phosphorus bond such as those prepared by the treatment of an olefin polymer (for example a polyisobutene

  having a molecular weight of 1000) by a phosphoric acid

  such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, trichloride

  of phosphorus and sulfur, white phosphorus and a halo-

  sulfuric acid or phosphorothioic chloride The salts of these acids that are most commonly used are those of sodium, potassium, lithium, calcium, magnesium,

strontium and barium.

  The term "basic salt" is used to refer to metal salts in which the metal is present in stoichiometrically larger amounts than the organic acid radical. The methods commonly used to prepare basic salts include heating a solution in the mineral oil of an acid with a stoichiometric excess of a metal neutralizing agent such as oxide, hydroxide, carbonate, bicarbonate or sulphide of the metal at a temperature above 50 C and filtration of the resultant mass The use of a "promoter" in the neutralization step to assist in the incorporation of a large excess of metal is known

  Examples of compounds useful as

  engine include phenolic substances such as phenol, naphthol, alkylphenols, thiophenol, sulfurized alkylphenols and condensation products of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, Cellosolve, carbitol, ethylene glycol, stearyl alcohol and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-beta-naphthylamine and dodecylamine. A particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic neutralization agent derived from it. alkaline earth metal and at least one alcohol promoter and the carbonation of the

  mixing at a high temperature such as 60-200 C.

  Auxiliary detergents and dispersants without ash are so called despite the fact that, according to its constitution, the dispersant can give by combustion a

  non-volatile material such as boric oxide or anhy-

  phosphoric acid; however, it usually does not contain metal and therefore does not burn ash containing metal Many types are known

  in the art and are described in

  taking those listed above about Constituent B.

  Also useful as auxiliary dispersants are

  monomer polymers having an oil solubilizing effect such as decyl methacrylate, vinyl decyl oxide and high molecular weight olefins with monomers containing polar substituents, for example, aminoalkyl acrylates or acrylamides and poly (oxyethylene) acrylates. They can be characterized as "polymeric dispersants" and examples are described in the following US patents which are incorporated by reference:

3,329,658 3,666,730

3,449,250 3,687,849

3,519,565 3,702,300

  Examples of extreme pressure agents and agents

  Corrosion and oxidation inhibitors are hydro-

  chlorinated aliphatic carbides such as chlorinated paraffin; organic sulfides and polysulfides such as benzyl disulfide, bis (chlorobenzyl) disulfide, dibutyl tetrasulfide, oleic acid sulfide methyl ester, sulfurized dipentene and sulfurized terpene; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate; phosphorus esters comprising mainly dihydrocarbyl phosphites and

  trihydrocarbyl such as dibutyl phosphite, phosphorus

  diheptyl phite, dicyclohexyl phosphite,

  pentylphenyl phosphite, dipentylphosphite

  phenyl, tridecyl phosphite, phosphite di-

  stearyl, dimethyl and naphthyl phosphite, oleyl and 4-pentylphenyl phosphite, polypropylene phosphite (500 → -phenyl molecular weight, diisobutyl-phenyl phosphite, metal thiocarbamates, such as zinc dioctyldithiocarbamate) and

  barium heptylphenyl dithiocarbamate; phosphoro-

  Group II dithioates such as dicyclohexyl-

  zinc phosphorodithioate, zinc dioctylphosphorodithioate, barium di (heptylphenyl) phosphorodithioate, cadmium dinonylphosphorodithioate and the zinc salt of a phosphorodithioic acid produced by the reaction of phosphorus pentasulfide with an equimolar mixture

  isopropyl alcohol and n-hexyl alcohol.

  The compositions according to the present invention can

  also contain at least one component improving the vis-

  cosité; i.e. at least one constituent capable

  to substantially improve their viscosity properties.

  For the purposes of the present invention, a substance

  is regarded as substantially improving the

  viscosity properties of a composition if its incorporation

  in the composition in useful quantities causes an increase in its viscosity number (as determined by the

  method of ASTM D 2270) of at least 6 units.

  A number of types of viscosity improvers are known in the art and many of them are described by Ranney in Lubricant Additives (Noyes Data Corporation, 1973), pages 93-119. Examples of viscosity improvers are polymers of olefins such as polybutenes (especially containing mainly isobutene meshes); ethylene-propylene copolymers; copolymers of ethylene and

2 D-2458

-60-

  other low molecular weight olefins (especially

  alpha-olefins); terpolymers of ethylene, propylene and various dienes (especially non-conjugated dienes); polybutadiene; hydrogenated styrene-butadiene copolymers; alkylated polystyrenes; polymers of alkyl methacrylates; alkylene polyethers; and polyesters prepared from polyols, short chain dicarboxylic acids and

  mono carboxylic acid chain blockers

  basic (useful mainly in lubricants in

  which lubricating oil is a synthetic ester.

  It is also included in the general framework of the

  present invention to use as component B a

  position which improves the viscosity properties while serving as a dispersant or detergent When component B also improves the viscosity properties, it may be possible to reduce the amount of viscosity enhancing auxiliary agent used, or

eliminate it entirely.

  The present invention contemplates two materials as being particularly useful as a combination of agents

  improving the viscosity and detergents or dispersants.

  The first includes dispersants containing more than one

  succinic portion per molecule, particularly those

  prepared from a hydrocarbon source having a number average molecular weight (Mn) of at least about 1300 and usually about 1300-5000 as determined by

  gel permeation chromatography Examples 25 B-

  B above illustrate suitable dispersants of this type which also have viscosity improving properties. The second type of preferred agent for improving

  the viscosity having dispersant or detergent properties

  gents comprises interpolymers substantially free of titratable acidity and containing carboxylic ester groups

12458

  Wherein a portion of the alcohol portions have at least 8 aliphatic carbon atoms and another portion has not more than 7 aliphatic carbon atoms, and also contain carbonyl-polyamino groups in which the polyamino group is derived from A compound having a primary or secondary amino group. These polymers are described in US Pat. No. 3,702,300, which is incorporated herein by reference.

  by reference for this description.

  polymers prepared by first copolymerizing styrene with maleic anhydride and then esterifying a portion of the carboxylic acid groups with a mixture of primary alcohols having the carbon number indicated above, and neutralizing the groups remaining carboxylic acid with an appropriate amine The useful examples of US Pat. No. 3,702,300 illustrate

  particular suitable polymers.

  Another constituent in the phosphorus acid salt compositions according to the present invention may be at least one compound of the formula

13 S.

King

14-SM

  wherein R 13 and R 14 each independently represent a hydrocarbon-based group having about 3 to about carbon atoms and M is a Group I metal, a Group II metal, aluminum, tin, iron, cobalt, lead, arsenic, molybdenum, manganese, nickel or a mixture of any of these metals These phosphorus acid salts, when present, give rise to

  lubricant of load bearing and inhibiting properties

oxidation.

  Each of the substituents R 13 and R 14 is preferably an alkyl group, but it may be an aryl group or a substituted aryl group (eg phenyl, tolyl, chlorophenyl). The usable alkyl groups include propyl, butyl, octyl, decyl, hexadecyl, octadecyl, eicosyl and mixtures thereof R and R 14 are each an alkyl group containing from about 6 to about 20 and preferably about 6 to about 10 carbon atoms. Branched groups (e.g.

  isooctyl, 2-ethylhexyl) are especially preferred.

  The metal (M) of the phosphorus acid salt is preferably zinc or molybdenum and especially zinc. As indicated previously, it is within the general scope of the invention to use salts of more than one metal. or to use a mixed salt of two or more metals (eg zinc and arsenic, zinc and

  nickel, molybdenum and manganese.

  The compositions according to the present invention can be added directly to the lubricant.

  however, they are diluted with an organic diluent

  normally liquid, substantially inert, such as mineral oil, naphtha, benzene, toluene or

  xylene, to form an additive concentrate.

  concentrates usually contain about 20-90% by weight of the composition according to the present invention and may contain, in addition, one or more other known additives

  in the art or described above.

  Examples of concentrates according to the present invention are shown in Table III and examples of lubricants according to the present invention are shown in Table IV. All quantities, except those relating to the products of the examples, are amounts not including

  not diluents such as mineral oil.

TABLE III

  Concentrate Examples Ingredient Concentrate Mineral Oil (100 Neutral) Mineral Oil (200 Neutral) Mineral Oil (200 Neutral 45% Neutral Vol 55% Aerial) Mineral Oil Thinner Product of Example 1-A Product of Example 12 A Product of Example 2-B Product of Example 32-B Basic Sulfide of Calcium and Alkylphenol Hydroxypropyl Tetrapropenylsuccinic Acidic Dialkylphosphorodithioate Zinc Containing Alkyl C 3 -C 6 Branched Chain Silicone Antifoam Agent ABC, 0, 0, 0 13.0 82.34 7.18

, 0 1.99

0.41

2.72

D E

, 0 m, 0, 0, 0, 0

0.72 -

0.35 0.43

0.005 0.05

0.005 I u Ln co. Co

TABLE IV

  Examples of Lubricants Ingredient Lubricant A Mineral Oil 92.92 9 Product of Example 1-A 1.50

Product of Example 8-A -

Product of Example 3-B 2.50

Product of Example 25-B -

  Reaction product of polybutenyl anhydride (about 1,000 mol) succinic with pentaerythritol and a mixture of ethylene

polyamines -

  Basic Petroleum Sulphonic Acid Calcium Salt 0.67 Basic Petroleum Sulphonic Acid Magnesium Salt 0.59 Acidic Zinc Dialcoylphosphorodithioate 1.18 Alkyl Acetate-Acetate Terpolymer

vibyle-vinyl oxide -

  Polybutenyl (mol. Mol. 2000) phenol bridged with sulfur and methylene broth 0.54 "Ortholeum 2052"

  Cyclohexenecarboxylate of sulphurized alkyl -

  Tetrapropenyl succinic anhydride -

  Demulsifier poly (alkylene oxide) 0.10

Antioxidant phenol prevented -

  B 1.75 1.17 2.50 C 88.25 1.09 7.14 D 98.0 0.5 1.5 E 98.0 1.0 1.0 1.38 l o 1% i

0.53 1.32

0.49 1.16 1.19

0.21 0.14

  0.80 0.01 0.52 0.27 0.27 0.01 Silicone antifoam agent R L Mi ulo Ut Ln CO

0.011 0.01 0.007

-65-

  The fuel consumption of engines with

  Internal combustion is reduced when the engines are lubricated with the compositions according to the present invention. This is shown by the so-called Pinto Frictiop Horsepower Test, in which a Ford Pinto engine is driven by a constant temperature dynamometer while the speed and torque The horsepower absorbed by the friction, as calculated from these values, is approximately proportional to the fuel consumed and thus decreases with a greater economy of operation. combustible. -66-

Claims (1)

1 multi-component composition, characterized in that it comprises: (A) at least one tartrate of the formula HO-CHCO 2 R wherein each R is independently a hydrocarbon-based group and the sum of the atoms carbon in both groups R is at least about 8; and (B) at least one oil-soluble detergent or dispersant. Composition according to Claim 1, characterized in that each R group is about 8-20 carbon atoms. 3. Composition according to claim 1, characterized in that at least one R group contains an uninterrupted chain of at least about eight -CH 2- meshes. 4. Composition according to claim 1, characterized in that the detergent is a salt or basic complex of alkali metal or alkaline earth metal of a phenol, a sulfonic acid, a carboxylic acid or a phosphorus acid. Composition according to Claim 4, characterized in that the detergent is a basic salt of an alkaline or alkaline earth metal. 6. Composition according to claim 5, characterized in that the detergent is a basic calcium sulphonate. The composition of claim 1, wherein the dispersant is characterized by the presence of a group having an oil solubilizing effect containing at least about 40 aliphatic carbon atoms directly attached to a polar group. 8. Composition according to claim 7, characterized in that the dispersant is a carboxylic dispersant, a Mannich dispersant, an amine dispersant, a polymeric dispersant or a post-treatment product of any of the foregoing. A composition according to claim 8, wherein the dispersant is a carboxylic dispersant characterized by the presence in its molecular structure of an acyl, acyloxy or acylimidoyl group containing at least about 44 carbon atoms and a group in which a hydrogen atom is present. nitrogen or oxygen is directly attached to the acyl, acyloxy or acylimidoyl group, this nitrogen or oxygen atom being also bonded to a hydrocarbon-based group. A composition according to claim 9, characterized in that the dispersant is prepared by reacting a substantially saturated hydrocarbyl succinic or halohydrocarbyl succinic acid with at least one alcohol or alkylene polyamine. A composition according to claim 10, characterized in that the substantially saturated hydrocarbyl succinic acid is prepared by reacting more than one mole of maleic anhydride with one mole of an olefin polymer. Composition according to claim 11, characterized in that the substituted succinic acid contains an average of 1.3 to 3.5 succinic acid groups for each olefin polymer derived group. A composition according to claim 10, characterized in that the hydrocarbyl substituent on the succinic acid generating compound contains at least about 50 aliphatic carbon atoms and the dispersant is prepared by the reaction of this succinic acid generating compound with at least one alcohol. Composition according to Claim 13, characterized in that the alcohol is pentaerythritol. A composition according to claim 10, characterized in that the substituent on the succinic acid generating compound 251: 2458 contains at least about 50 aliphatic carbon atoms and the dispersant is prepared by the reaction of this succinic acid with at least one alkylene polyamine. Composition according to Claim 15, characterized in that the alkylene polyamine is an ethylene polyamine. Composition according to claim 8, characterized in that the dispersant is a Mannich dispersant comprising the reaction product of an alkyl phenol in which the alkyl group contains at least about 40 carbon atoms with an aliphatic aldehyde containing at least about 7 carbon atoms and an amine. Composition according to Claim 17, characterized in that the aldehyde is formaldehyde and the amine is an alkylene polyamine. Composition according to Claim 18, characterized in that the amine is an ethylene polyamine. Composition according to Claim 1, characterized in that both a detergent and a dispersant are present. A composition according to claim 20, characterized in that the detergent is a basic alkali or alkaline earth metal sulfonate and the dispersant is prepared by reacting a hydrocarbyl succinic acid generating compound with at least one alcohol or an alkylene polyamine. An additive concentrate comprising 10 to 80 parts of an inert liquid solvent or diluent and 20 to 90 parts of the composition according to one of claims 1 to 21. 23 Lubricant comprising a major proportion of oil and a proportion The process for reducing the fuel consumption of an internal combustion engine, wherein said engine is lubricated in use with a lubricant comprising a composition according to one of claims 1 to 21. one of the claims 1 to 21.