RU2023003C1 - Internal engine lubricating oil - Google Patents

Abstract

FIELD: preparation of lubricating agents. SUBSTANCE: lubricating oil includes 2-15 % by weight of the reaction product of polyisobutylene-succinic acid having 1.3-4 succinic groups per equivalent weight of polyisobutylene that has an average molecular weight of 1300-5000 and the ratio of number-average-to average molecular weight of 1.5-4.5, with 1 equivalent of polyisobutylene-succinic acid being added to the reaction together with 0.7-0.95 equivalent of polyamine; 0.01-2.00 % by weight of a basic alkali metal sulfonate or carboxylate; and mineral oil or additive oils up to 100 % balance. EFFECT: improved quality. 3 cl, 11 tbl

Description

 The invention relates to a lubricating oil composition comprising an oil with a viscosity of a lubricating oil, a carboxylic derivative exhibiting both viscous and dispersing properties, and a basic salt of an alkali metal and sulfonic or carboxylic acid.

 The lubricating oils used in internal combustion engines, and in particular in spark ignition engines and diesel engines, are constantly being modified and improved to provide improved performance. Various organizations, including SAE (Society of Automotive Engineers), ASTM (formerly the American Society for Testing and Materials), and API (American Petroleum Institute), as well as car manufacturers, are constantly striving to improve the performance of lubricating oils. Various standards have been set and are being modified over the years by the efforts of these organizations. As the output power and complexity of the engines increased, performance requirements were increased to provide lubricating oils that have a reduced tendency to deteriorate under conditions of use, thereby reducing wear and the formation of unwanted deposits such as carbon deposits, sludge, carbonaceous and tar-like materials that tend to adhere to different parts of the engine and reduce engine efficiency.

 In general, various oil classifications and performance requirements have been established for crankcase lubricants used in spark ignition engines and diesel engines due to differences and lubricating oil requirements for these applications. Commercially available quality oils intended for spark ignition engines have been identified and previously labeled as “SF” oils, as oils capable of meeting the performance requirements of the SF Servicing Classification API. The new SG Service Classification API has recently been installed and this oil has been labeled “SG”. Oils designated as SG must meet the performance requirements of the SG Service Classification API, which have been established so that these new oils have additional desirable properties and higher performance than SF oils. SG oils are designed to minimize wear and deposits and to minimize thickening during operation. SG oils are designed to improve engine performance and reliability compared to all previous engine oils sold for spark ignition engines. An additional characteristic of SG oils is the inclusion of SS category requirements (diesel) in the SG specification.

 In order to meet the performance requirements of SG oils, oils must successfully pass the following tests for gasoline and diesel engines, which have been set as industry standards: Ford VE sequence test; Buick IIIE sequence test; Oldsmobile Sequence Test IID; CRCL-38 test; and Caterpillar Single Cylinder Engine Test. The Caterpillar test is included in the performance requirements to also qualify the oil for use in a low-power diesel (diesel operation category "SS"). If it is desirable to have an SG classification oil that is also qualified for use with high power diesel engines (diesel engines of category "SD"), the oil formulation must meet the more stringent performance requirements of the Caterpillar IG2 Single Cylinder Engine Test. The requirements for all of these tests have been established by the industry and these tests are described in more detail below.

 When it is desired that SG classification lubricating oils also show improved fuel economy, the oil should meet the requirements of the Sequence VI Dynamometer test for efficient fuel oil engines.

 The new diesel engine oil classification was also established by the joint efforts of SAE, ASTM and API and the new diesel oils were labeled “CE”. Oils that meet the new CE diesel classification must meet additional performance requirements not available in the existing SD category, including the Mask-T-6 Test, Mask T-7 and Cummins NTS-400.

 An ideal lubricating oil should have the same viscosity at all temperatures. However, the available greases do not meet this ideal. Additives that are added to lubricants to minimize changes in viscosity as a function of temperature are called viscosity modifiers. Typically, additives that are used to improve viscosity index (VI) are oil-soluble and organic polymers and these polymers include polyisobutylenes, polymethacrylates (e.g., methacrylate copolymers with different alkyl chain lengths, ethylene-propylene copolymers, hydrogenated block copolymers of styrene and isoprene and polyacrylates ( for example, copolymers of acrylates with different chain lengths).

 Known lubricating oils used in internal combustion engines, based on petroleum oils, containing as a dispersing additive alkenyl succinimide, acetate, sulfonate, calcium or magnesium carbonate, dialkyl dithiophosphate zinc, dialkyl diphenylamine and sulfonated olefin as antioxidants, ethylene acrylate propylene copolymer and as additives to improve the viscosity index (1).

 Other materials are included in the lubricating oil compositions to make the oil compositions meet various operational requirements and are dispersants, detergents, modifiers, friction modifiers, corrosion inhibitors, and the like. Dispersants are used in lubricants to maintain impurities, especially those formed during operation of the internal combustion engine, in the form of a suspension, not allowing them to precipitate in the form of sludge. Materials that are both viscous additives and dispersants have been described in the art. One type of compound having both properties is a polymer chain to which one or more monomers having polar groups are attached. Such compounds are often vaccinated, wherein the polymer chain is directly reacted with a suitable monomer.

 Dispersant additives for lubricants, which are the reaction products of hydroxyl compounds or amines with substituted succinic acids or their derivatives, have also been described in the prior art (2). When introduced into lubricating oils, these additives work primarily as dispersant detergents and additives to improve the viscosity index.

Oils for internal combustion engines based on petroleum oils are also known, containing metal dialkyl dithiophosphates as antioxidant and anti-wear additives, in which the alkyls are C ₂ -C ₄ alkyls, with at least one of the alkyls being butyl and the total number of carbon atoms per one phosphorus atom is less than 8. The metals are zinc, copper and iron. The oil also contains the product of the interaction of polyisobutylene succinic acid with a polyamine, neutral or basic salts of alkali or alkaline earth metals, sulfonic or carboxylic acids (3). However, the known oil has an insufficient level of viscosity.

 The aim of the invention is to increase the viscosity of the oil.

The oil according to the invention contains the following components, wt.%:
interaction product
polyisobutylene amber
acids with alkylene polyamine (component B) 2-15
basic alkaline salt
metal sulfonic acid or carboxylic acid 0.01-2.00
mineral oil or oil with additives up to 100.

 Petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffin-naphthenic types are used as the base of the lubricating oil.

Polyisobutylene succinic acid (B-1) contains an average of 1.3 to 4.0 succinic acid groups per equivalent mass of polyisobutylene. Polyisobutylene has a number average molecular weight of 1300-5000, the ratio of the weight average mol. mass M _w to the number average molar mass M _n is 1.5-4.0. 0.70-0.95 equivalents of polyalkylene polyamine (B-2) are produced per equivalent acid (B-1).

The abbreviation M _w is a traditional symbol denoting a weight average molecular weight. Gel Permeation Chromatography (GPC) is a method that provides determination of both number average and weight average molecular weights, as well as the complete molecular weight distribution of polymers. For the purposes of the present invention, a series of fractionated polymers of isobutylene, polyisobutene was used to calibrate the standard curve in the GPC.

 Alkylene polyamines used to prepare the carboxyl derivative (B) compositions include ethylene diamine, triethylenetetramine, propylene diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, di (heptamethylene) triamine, tripropylenetetramine, tetraethylene ethylene diamine, tripropylene diamine, tripropylene diamine, tripropylene diamine, triethylene diene diamine, triethylene ethylene dientene aminoethyl) piperazine, 1,4-bis (2-aminoethyl) piperazine and the like. Higher homologues obtained by condensation of two or more of the above alkyleneamines, as well as mixtures of two or more of the described polyamines, can also be used.

 Due to cost and effectiveness, the ethylene polyamines mentioned above are particularly useful.

Other useful types of polyamine mixtures are mixtures obtained by steaming the polyamine mixtures described above. In this case, low molecular weight polyamines and volatile impurities are removed from the alkylene polyamine mixture, leaving a residue, which is often referred to as “polyamine residues”. Typically, alkylene polyamine bottoms can be characterized as containing at least 2, usually less than 1 wt.% Material boiling below about 200 ° ^C. In the case etilenpoliaminovyh residues which are readily available and can be advantageously used, such residues contain less than 2 wt.% diethylenetriamine (DETA) or triethylenetriamine (TETA). A typical sample of such ethylene polyamine residues, manufactured by the company Dow Chemical Freeport, Texas under the name "E-100" has a specific gravity of 15.6 ^about 1.0168, nitrogen content of 33.15 wt. % And a viscosity at 40 C ^of 121 centistokes. Gas chromatographic analysis of such a sample showed that it contains about 0.93% "light fractions" (probably DETA), 0.72% TETA, 21.74% tetraethylene pentamine and 76.61% pentaethylene hexamine and higher homologs. Such polyamine residues include cyclic condensation products such as piperazine and higher analogs of diethylene triamine, triethylenetetramine and the like.

 Such alkylene polyamine residues can themselves react with an acylating agent, in which case the amine reagent consists mainly of alkylene polyamine residues, or they can be used with other amines and polyamines, or with alcohols and mixtures thereof. In the latter case, at least one amino reactant includes alkylene polyamine residues.

Compositions of carboxyl derivatives (B) obtained from acylating reagents (B-1) and amine compounds (B-2) described above encompass acylated amines, which include amine salts, amides, imides and imidazolines, as well as mixtures thereof. For carboxyl derivatives from the acylating reagents and the amino compounds, one or more acylating reagents and one or more amine compounds are heated at temperatures ranging from 80 ^° C to ^the decomposition point (in the case previously found that such decomposition point available), but normally at temperatures in the range 100-300 ^{° C} provided that the temperature is 300 ^{° C} does not exceed the decomposition point. Typically, the temperature used in the range of 125-250 ^C. The acylating reagent and the amine compound are reacted in amounts sufficient to provide from 0.5 equivalent to not less than 1 equivalent of amine compound per equivalent of acylating reagent.

 In order to obtain a composition of carboxylic derivatives having the ability to improve the viscosity index, it was found that it is necessary to carry out the reaction of acylating reagents with polyfunctional reagents. Thus, for example, polyamines containing two or more primary and / or secondary amino groups are preferred for these purposes. However, it is obvious that there is no need for all amino compounds reacting with acylating reagents to be multifunctional. Compositions of mono- and polyfunctional amine compounds may be used.

 The relative amounts of the acylating agent (B-1) and the amine compound (B-2) used to formulate the carboxyl derivative (B) compositions used in the lubricating oil compositions of the present invention are a decisive feature. It is essential that the acylating agent (B-1) reacts with less than one equivalent of the amine compound (B-2) based on the equivalent of the acylating agent. It was found that the introduction of carboxyl derivatives obtained at the indicated ratios in the lubricating oil composition of the present invention improves viscosity-index characteristics compared to lubricating oil compositions containing carboxyl derivatives obtained by the reaction of the same acylating agent with one or more equivalents amine compounds based on the equivalent of an acylating agent.

The drawing shows a graph showing the dependence of the viscosity of the polymer on the ratio of the acylating agent-nitrogen in two dispersants in the formulation SAE 5 V-30. For all contents dispersant viscosity of the mixture at ¹⁰⁰ ° C of 10.2 cSt, a viscosity at ^-25 ° C is 330 cps in the presence of 4% dispersant. The solid line indicates the relative level of viscosity improver required for various concentrations of the known dispersant. The dashed line shows the relative level of viscosity improver required for the various dispersant concentrations of the present invention (component B). A known dispersant was prepared by reacting one equivalent of polyamine with one equivalent of an amber acylating agent having the characteristics of acylating agents used to prepare component (B) of the present invention. The dispersant of the invention was obtained by reaction of 0.833 equivalents of the same polyamine with one equivalent of the same acylating agent.

 It can be seen from the graph that oils containing the dispersant used in the present invention require a lower amount of polymer viscosity additive to maintain this viscosity than in the case of the known dispersant, while improving the viscosity is higher at higher levels of dispersant, for example, with higher amounts of dispersant 2%

 In one embodiment, the acylating agent reacts with 0.70-0.95 equivalents of the amine compound, based on the equivalent of the acylating agent. The narrowed range of ratios of the number of equivalents of the acylating agent (B-1) to the number of equivalents of the amine compound (B-2) can be 0.70-0.90, or 0.75-0.90, or 0.75-0.85. In some cases, it was found that if the equivalent of the amine compound was 0.75 or less, based on the equivalent of the acylating agent, the effectiveness of the carbon derivatives as dispersants decreased. According to one embodiment, the relative amounts of the acylating agent and the amine are such that the carboxylic derivative preferably does not contain free carboxyl groups.

In addition to the relative amounts of the acylating agent and the amine compound used to produce the carboxylic derivative composition (B), other distinctive features of the carboxylic derivative composition (B) are the values of M _n and M _w / M _{n of} polyalkene, as well as the average presence in acylating agents of at least 1.3 amber groups for each equivalent weight of substituent groups. In the case where the compositions of the carbon derivatives (B) possess all of these distinguishing features, the lubricating oil compositions of the present invention exhibit new and improved properties, and these compositions are characterized by improved performance in internal combustion engines.

Скорректированное число омыления получают делением числа омыления на процентное количество прореагировавшего полиалкена. Так например, если не прореагировало 10% полиалкена и число омыления фильтрата или остатка составляет 95, то скорректированное число омыления составит 95:0,90=105,5.The ratio of the number of amber groups to the equivalent weight of substituent groups present in the acylating agent can be determined from the saponification of the reaction mixture, adjusted for the amount of unreacted polyalkene present in the reaction mixture at the end of the reaction (referred to in the following examples as filtrate or balance). The saponification number is determined according to ASTM D-94. The formula for calculating this ratio from the saponification number is as follows:
Ratio =

The corrected saponification number is obtained by dividing the saponification number by the percentage of reacted polyalkene. For example, if 10% of the polyalkene has not reacted and the saponification number of the filtrate or residue is 95, then the adjusted saponification number will be 95: 0.90 = 105.5.

 The preparation of acylating agents and compositions of carboxyl derivatives (B) is illustrated by the following examples. These examples illustrate preferred options. In the following examples and in the text of the description, unless otherwise indicated, all percentages and parts are massive.

 Acylating agents.

EXAMPLES EXAMPLE 1 A mixture of 510 hours. (0.28 mole) of polyisobutene (M _n = 1845, M _w = 532,5), and 59 hours. (0.59 mole) of maleic anhydride is heated to 110 ° ^C. This mixture is heated to 190 ^° C. in 7 hours, during which 43 parts (0.6 mol) of chlorine gas are introduced under the surface of the mixture. At 190-192 ^{° C} was added further 11 hours. (0.16 mole) of chlorine over 3.5 hours. The reaction mixture is stripped by heating at 190-193 ^{° C} while blowing the mixture for 10 hours. The residue is polyisobutylene salt substituted amber acylating agent having an equivalent saponification number of 37, found according to ASTM D-94.

Example 2. A mixture of 1000 parts (0.495 mol) of polyisobutylene (M _n = 2020, M _w = 6049) and 115 parts (1.17 mol) of maleic anhydride are heated to 110 ^° C. This mixture is heated to 184 ^{° C} for 6 hours, during which is introduced under the surface of 85 hours. (1.2 mole) of gaseous chlorine. At 184-189 ^{° C} is introduced additionally 59 h. (0.83 mole) of chlorine for 4 hours. The reaction mixture is stripped by heating at 186-190 ^{° C} while blowing the mixture with nitrogen for 26 hours. The residue is a polyisobutene-substituted slit an amber acylating agent having an equivalent saponification number of 87, found according to ASTM-D-94.

EXAMPLE C Example 3 A mixture of 3251 parts poliizobutilenhlorida prepared by adding 251 hours. Gaseous chlorine to 3000 parts of polyisobutene (M _n = 1696, M _w = 6594) at 80 ° ^C for 4.66 hours and 345 hours. The maleic anhydride is heated to 200 ^about With in 0.5 hours. The reaction mixture was kept at 200-224 ^{° C} for 6.33 hours, stripped ^at 210 ° C under vacuum and filtered. The filtrate is the desired polyisobutene-substituted succinic acylating agent having an equivalent soap number of 94, found by ASTM D-94.

EXAMPLE EXAMPLE 4 A mixture of 3000 hours. (1.63 mole) of polyisobutene (M _n = 1845, M _w = 5325) and 344 hours. (3.51 mole) of maleic anhydride is heated to 140 ° ^C. The mixture heated to 201 ^about With for 5.5 hours, during which 312 hours (4.39 mol) of chlorine gas was passed under the surface. The reaction mixture was heated at 201-236 ^{° C} with nitrogen blowing for 2 hours and stripped under vacuum at 203 ^C. The reaction mixture was filtered to obtain the filtrate as the desired polyisobutene-substituted succinic acylating agent having a saponification equivalent number of 92 found by the ASTM D-94

EXAMPLE EXAMPLE 5 A mixture of 3000 hours. (1.49 mole) of polyisobutene (M _n = 2020, M _w = = 6049) and 364 hours. (3.71 mole) of maleic anhydride is heated at ²²⁰ ° C. for 8 hours. The reaction mixture was cooled to ^about 170 C. At ^about 170-190 C under the surface for 8 h, 105 h. (1.48 mole) of gaseous chlorine. The reaction mixture was filtered to obtain the filtrate as the desired polyisobutylene-substituted succinic acylating agent.

EXAMPLE EXAMPLE 6 A mixture of 800 parts. Polyisobutene falling within the scope of protection of the present invention and having a number average molecular weight (Mn about 2,000, 646 h. Of mineral oil and 87 hours. The maleic anhydride is heated to 179 ^{° C} for 2.3 o'clock at 176-180 ^about With under the surface add 100 parts of gaseous chlorine over a period of 19 hours the Reaction mixture is steamed by blowing it with nitrogen for 0.5 hours at 180 ^about C. the Residue is an oil-containing solution of the target polyisobutylene-substituted succinic acylating agent.

Example 7. The procedure of example 1 is repeated except that the polyisobutylene (M _n = 1845, M _w = 5325) is replaced with an equimolecular amount of polyisobutylene with M _n = 1457, M _w = 58.08.

Example 8. The procedure of example 1 is repeated except that the polyisobutylene (M _n = 1845, M _w = 5325) is replaced with an equimolecular amount of polyisobutylene with M _n = 2510 and M _w = 5660.

 Compositions of carboxyl derivatives (B).

PRI me R B-1. The mixture is prepared by adding 8.16 parts (0.20 equivalent) of an industrial mixture of ethylene polyamines having from about 3 to 10 nitrogen atoms in the molecule to 113 parts of mineral oil and 161 parts (0.25 equivalent) of a substituted succinic acylating agent prepared in example 1, at 138 ^about C. The reaction mixture is heated to 150 ^about C for 2 hours and evaporated by blowing with nitrogen. The reaction mixture is filtered to obtain a filtrate in the form of a solution of the target product in oil.

PRI me R B-2. The mixture is prepared by adding 45.6 parts (1.10 equivalents) of an industrial mixture of ethylene polyamines having from about 3 to 10 nitrogen atoms in the molecule to 1067 parts of mineral oil and 893 parts (1.38 equivalents) of a substituted succinic acylating agent prepared in example 2, at 140-145 ^about C. the Reaction mixture is heated to 155 ^about C for 3 hours and evaporated by blowing with nitrogen. The reaction mixture is filtered to obtain a filtrate in the form of a solution of the target product in oil.

PRI me R B-3. The mixture is prepared by adding 18.2 parts (0.433 equivalents) of an industrial mixture of ethylene polyamines having from about 3 to 10 carbon atoms in the molecule to 392 parts of mineral oil and 348 parts (0.52 equivalents) of a substituted amber acylating agent, prepared in example 2, at 140 ^about C. The reaction mixture is heated to 150 ^about With for 1.8 hours and evaporated by purging with nitrogen. The reaction mixture was filtered to obtain the filtrate in the form of a solution of the target product in oil (55%) oil.

 The products of examples B-4 to B-17 are prepared following the general procedure described in Example B-1 (see Table A).

PRI me R B-18. A mixture of 2483 parts of an acylating agent (4.2 equivalents), which is described in Example 3, and 1104 parts of oil are loaded into a flask of a suitable size, equipped with a stirrer, a nitrogen inlet tube, a boiling funnel and a Dean-Stark condenser trap. This mixture was heated to 210 ^C under a slow bubbling nitrogen through the mixture. At this temperature, a bottom residue of ethylene polyamine (134 parts, 3.14 equivalents) is slowly added to the mixture over about 1 hour. The temperature was maintained at about 210 ^{° C} for 3 hr. And then added to 36888 hours. Oil to increase the temperature to 125 ^C. After storage at 138 ^{° C} for 17.5 h the mixture was filtered through diatomaceous earth to obtain 65 % oily solution of the desired acylated amine residues.

PRI me R B-19. A mixture of 3660 hours. (6 equivalents) of a substituted succinic acylating agent prepared as in Example 1, at 4664 hours. Diluent oil is prepared and heated at about ¹¹⁰ ° C whereupon nitrogen is purged through the mixture. And then the mixture was added 210 hours. (5.25 equivalents) of a commercial mixture of ethylene polyamines having from 3 to 10 atomovazota per molecule over a period of 1 hour and the mixture was kept at ¹¹⁰ ° C for an additional 0.5 hours. After heating 6 hours at 155 ^{° C} with removal of water filtrate was added and the reaction mixture was filtered at about 150 ° ^C. The filtrate is an oil solution of the desired product.

 PRI me R B-20. The general procedure of Example B-19 is repeated with the exception that 0.8 equivalents of the substituted succinic acylating agent from Example 1 are reacted with 0.67 equivalents of an industrial mixture of ethylene polyamines. The product thus obtained is an oily solution of a product containing 55% dilution oil.

 PRI me R B-21. The general procedure of Example B-19 is repeated with the exception that the polyamides used in this example are an equivalent amount of an alkylene polyamine mixture comprising 80% of Union Carbide ethylene polyamine distillation residues and a 20% industrial mixture of ethylene polyamine corresponding to the empirical formula diethylene triamine. This polyamine mixture is characterized by an inherent equivalent weight of about 43.3.

PRI me R B-22. A mixture of 414 hours. (0.71 eq.) Of a substituted acylating agent prepared in Example 1 and 183 hours. The mineral oil and heated to 210 ^{° C,} followed by the addition of 18.3 hours. (0.44 eq.) Etilenaminovyh residues (f. Dow) for a period of 1 h, while purging the mixture with nitrogen. The mixture was heated to about 218-217 ^C for about 15 minutes and maintained at this temperature for 34 hours, added another 608. Macla mineral and cmec maintained at about 135 ^{° C} for 17 hours. The mixture is filtered at ¹³⁵ ° C in a filter, the filtrate being an oil solution of the target product (65% oil).

PRI me R B-23. A mixture of 468 hours. (0.8 eq.) Substituted succinic acylating agent of Example 1 and 903.1 hours. The mineral oil is heated to 142 ^{° C,} after which 20.63 doblyayut hr. (0.7 eq.) Etilenaminovyh residues (f . Zhou) over a period of 1.5-2 hours. The mixture was stirred for an additional 4 hours at about 142 ^{° C} and filtered. The filtrate is an oily solution of the product (65% oil).

(C) Alkali metal salt
Component (C) of the lubricating oil compositions of this invention is at least one basic alkali metal salt of at least one sulfonic or carboxylic acid. This component is also called the "superbasic" and "superbasic" salt or complex. The method of their preparation is usually called "leaching." The term "metal ratio" is often used to determine the amount of metal in these salts or complexes relative to the amount of organic anion, and is defined as the ratio of the number of metal equivalents and the number of metal equivalents that would be present in a normal salt based on the usual stoichiometry of the compounds under discussion.

 Alkali metals that are present in the basic alkali metal salts (C) mainly include lithium, sodium and potassium, with sodium and potassium being preferred.

Sulfonic acids that are used in the preparation of component (C) include the following formulas:
RxT (SO ₃ H) _y
and
R ¹ (SO ₃ H) _r
In these formulas, R ¹ is an aliphatic or aliphatically substituted cycloaliphatic hydrocarbon or actually a hydrocarbon group that does not contain acetylene unsaturation and contains up to about 60 carbon atoms. When R ¹ is an aliphatic group, it usually contains at least 15 carbon atoms; when it is an aliphatically substituted cycloaliphatic group, then aliphatic substituents usually contain a total of at least about 12 carbon atoms. Examples of R ¹ are alkyl, alkenyl and alkoxyalkyl radicals and aliphatic substituted cycloaliphatic groups in which the aliphatic substituents are alkyl, alkenyl, alkoxy, alkoxy-allyl, carboxyalkyl and the like. Typically, the aliphatic core is derived from a cycloalkane or cycloalkene, such as cyclopentane cyclohexane or cyclopentene. Specific examples of R ¹ are cetylcyclohexyl, laurylcyclohexyl, cetyloxyethyl, octadecenyl and groups derived from petroleum, saturated and unsaturated paraffin waxes and olefin polymers, including polymerized monoolefins and diolefins containing about 2-8 carbon atoms in the olefin monomer.

 R is usually a hydrocarbon or substantially hydrocarbon group containing no acetylene unsaturation and containing about 4 to 60 aliphatic carbon atoms, preferably an aliphatic hydrocarbon group, such as alkyl or alkenyl.

 T is an aromatic hydrocarbon such as benzene, naphthalene. Index x is at least I and is usually 1-3. The subscripts r and y have average values of about 1-2 per molecule and are usually also 1.

 These sulfonic acids are usually petroleum sulfonic acids or prepared synthetic alkylsulfonic acids. Among petroleum sulfonic acids, the most suitable are those obtained by sulfonation of suitable petroleum fractions, followed by removal of acid sludge and purification. Synthetic alkarylsulfonic acids are usually prepared from alkylated benzenes such as Friedel-Crafts reaction products from benzene and polymers such as tetrapropylene. The following are specific examples of sulfonic acids that are used in the preparation of salts (C). Such sulfonic acids include petroleum sulfonic acids, petrolatum sulfonic acids, mono- and polyparaffin-substituted sulfonic acids of naphthalene, cetylphenol sulfonic acids, cetyl chlorobenzene sulfonic acids, cetyl phenol disulfide sulfonic acids, cetyl caprylbenzenesulfonic acids, dimethyl nitrile dimethyl nitrides, saturated sulfonic acids, solid paraffin, sulfonic acids unsaturated solid paraffins, sulfonic acids of hydroxy-substituted solid paraffin, tetraisobutylene sulfonic acids, tetraamylene sulfonic acids, chlorinated substituted sulfonic acids of solid paraffin, sulfonic acids of nitro-substituted solid paraffin, sulfonic acids of petroleum naphthenes, cetylcyclopentyl sulfonic acids, mono-aryl-acyl-polycyloxy paraffinic substituted cyclohexyl sulfonic acids, dodecylbenzenesulfonic acids, dimeric alkylate sulfonic acids, and the like.

Alkyl substituted benzenesulfonic acids in which the alkyl group contains at least 8 carbon atoms, including dodecylbenzene “bottom residues” —sulphonic acids, are particularly useful. The latter are acids derived from benzene which has been alkylated with propylene tetramers or isobutylene trimers in order to introduce 1, 2, 3 or more C ₁₂ branched substituents into the benzene ring. Bottom dodecylbenzene residues, mainly mixtures of mono- and didodecylbenzenes, are available as by-products in the production of household detergents. Similar products obtained from the bottom alkylation residues formed in the production of linear alkyl sulfonates (LAS) are also suitable for the production of sulfonates used in this invention.

 Suitable carboxylic acids from which useful alkali metal salts can be prepared include aliphatic, cycloaliphatic and aromatic mono- and polybasic carboxylic acids that do not contain acetylene unsaturation, including naphthenic acids, alkyl or alkenyl substituted cyclohexanoic acids, and alkyl or alkenyl carboxylic acids. Typically, aliphatic acids contain from about 8 to 50 and preferably from 12 to 25 carbon atoms. Preferred are cycloaliphatic and aliphatic carboxylic acids, which may be saturated or unsaturated. Konkretnymi examples yavlyayutcya 2-etilgekcanovaya kiclota, linolenic kiclota, propylene tetramer-substituted maleic kiclota, behenic kiclota, izoctearinovaya kiclota, pelargonic kiclota, kaprenovaya kiclota, palmitolenovaya kiclota, linodenovaya kiclota, lauric kiclota, oleic kiclota, ratsioleinovaya kiclota, undotsilovaya kiclota, dioktiltsiklopentankarbonovaya kiclota , maristine acid, dilauryl decanidronaphthalene carboxylic acid, stearyl octahydroindene carboxylic acid, palmitic acid, alkyl and alkenylate acids, Slot obtained by okicleniya petrolatum or solid parafenov and doctupnyh industrially cmecey of two or more carboxylic kiclot such as tallow kicloty macla, cmolictye kicloty etc.

 The equivalent mass of acidic organic compounds is its molecular weight divided by the number of acid groups (e.g. sulfonic acid or carboxy groups) present in the molecule.

 In a preferred embodiment, the alkali metal salts (C) are basic alkali metal salts which have a metal ratio of from about 4 to 40, preferably from 6 to 30, and particularly preferably from about 8 to 25.

In another and preferred embodiment, the basic salts (C) are oil-soluble dispersions obtained by contacting for a period of time sufficient to form a stable dispersion, at a temperature between the solidification temperature of the reaction mixture and its decomposition temperature:
(C-1) at least one acidic gaseous material selected from the group consisting of carbon dioxide, hydrogen sulfide and sulfur dioxide, s
(C-2) a reaction mixture comprising:
(C-2a) at least one oil-soluble sulfonic acid or its derivative,
(C-2b) at least one alkali metal or basic alkali metal compound;
(C-2c) at least one lower aliphatic alcohol, alkyl phenol or sulfonated alkyl phenol; and
(C-2d) of at least one oil-soluble carboxylic acid or a functional derivative thereof. When (C-2c) is alkyl phenol or sulfonated alkyl phenol, component (C-2d) is optional. A satisfactory basic sulfonic acid salt can be prepared with or without carboxylic acid in mixture (C-2).

 Component (C-2b) is at least one alkali metal or its basic compound. Examples of basic alkali metal compounds are hydroxides, alkoxides (usually those in which the alkoxide group contains up to 10 and preferably up to 7 carbon atoms), hydrides and amides. Thus, applicable basic alkali metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium propoxide, lithium methoxide, potassium ethoxide, sodium butoxide, lithium hydride, sodium hydride, potassium hydride, lithium amide, sodium amide and potassium amide. Particularly preferred is sodium hydroxide and lower sodium alkoxides (for example, those containing up to 7 carbon atoms). The equivalent mass of the component (C-2-b) for the purposes of this invention is equal to its molecular weight, since the alkali metal is monovalent.

 Component (C-2-c) may be at least one lower aliphatic alcohol, preferably a monohydric or dihydric alcohol. Illustrated alcohols are methanol, ethanol, 1-propanol, 1-hexanol, isopropanol, isobutanol, 2-pentanol, 2,2-dimethyl-1-propanol, ethylene glycol, 1,3-propanediol and 1,5-pentadiol. This alcohol may also be a glycol ether, such as methyl cellulosolve. Of these, preferred alcohols are methanol, ethanol and propanol, with methanol being particularly preferred.

 The component (C-2-c) may also be at least one alkyl phenol or sulfonated alkyl phenol. Sulfonated alkyl phenols are preferred, especially when (C-2-b) is potassium or one of its basic compounds, such as potassium hydroxide. As used herein, the term “phenol” includes compounds having more than one hydroxy group attached to an aromatic nucleus, which aromatic nucleus may be a benzyl or naphthyl nucleus. The term “alkyl phenol” includes mono- and dialkylated phenols in which each alkyl substituent contains from about 6 to 100 carbon atoms, preferably from 6 to 50 carbon atoms.

Examples of alkyl phenols are heptyl phenols, octyl phenols, depyl phenols, dodecyl phenols, polypropylene (M _n about 150) - substituted phenols, polyisobutylene (M _n about 1200) - substituted phenols, cyclohexyl phenols.

 Condensation products of the phenols described above with at least one lower aldehyde or ketone are also applicable, the term “lower” means aldehydes and ketones containing not more than 7 carbon atoms. Formaldehyde and formaldehyde-releasing reagents are particularly preferred.

 Sulfur alkyl phenols include phenolsulfides, disulfides or polysulfides. Sulfur phenols can be obtained from any suitable alkyl phenol according to methods known to those skilled in the art of chemistry, many sulfur phenols being commercially available. These sulfurized alkyl phenols can be prepared by reacting alkyl phenol with elemental sulfur and / or sulfur monohalide (e.g., sulfur monochloride). This reaction can be carried out in the presence of an excess of base to form salts of a mixture of sulfides, disulfides or polysulfides, which can be obtained depending on the reaction conditions. The final product of this interaction is used in the preparation of component (C-2) in the present invention.

 The following non-limiting examples illustrate the preparation of alkyl phenols and sulphide alkyl phenols used as component (C-2-e).

PRI me R 1-C. Maintaining a temperature of 55 ^{° C,} 100 h. Of phenol and 68 parts sulfonated polystyrene catalyst (marketed by Ros and Haas Co. as Amberlyst-15) were charged into a reactor equipped with a stirrer, condenser, thermometer and gas inlet tube below the surface of the liquid. Then the contents of the reactor are heated to 120 ^about With a purge with nitrogen for 2 hours. Charged propylene tetramer (1232 hr.) And the reaction mixture was stirred at ¹²⁰ ° C for 4 hours. Stirring was stopped and the boot allowed to settle for 0.5 hours. The crude upper phase of the reaction mixture is filtered and stripped under vacuum until until no more than 0.5% of the residual propylene tetramer remains.

PRI me R 2-C. Benzene (217 hr.) Is added to phenol (324 hr., 3.45 mole) at 38 ^{° C,} and the mixture was heated to 47 ^C. The mixture is blown boron trifluoride (8.8 hr., 0.13 mol) in for 0.5 h. at 38-52 ^C. to the mixture was added polyisobutylene (1000 h., 1.0 mole) obtained at ₄ C. polymerization of the monomers enriched in isobutene, at a temperature of 52-58 ^{° C} for a period of 3.5 h. The mixture was kept at 52 ^{° C} for a further 1 hour. a 26% strength aqueous ammonia solution (15 hr.), and the mixture was heated to ⁷⁰ ° C for 2 hours. The mixture was filtered and the filtrate is the desired crude polyisobutylene substituted phenol. This intermediate is stripped by heating (1465 h.) To 167 ^{° C,} at a pressure reduced to 10 mm Hg, the material was heated to 218 ^C for the period of 6 hours. The residue obtained in a yield of 64% of stripped polyisobutene substituted phenol (M _n = 885).

PRI me R 3-C. 1000 parts of the reaction product of Example 1-C are charged into a reactor equipped with a stirrer, a refrigerator, a thermometer and a dropping funnel for subsurface addition. The temperature was set at 48-49 ^{° C} and added to 319 hr. Sulfur dichloride, keeping the temperature below 60 ^C. Then the load is heated to 88-93 ^{° C} by blowing it with nitrogen until the acid value becomes greater than 4.0 ( using the indicator - bromphenol blue). Then 400 parts of dilution oil are added and the mixture is thoroughly mixed.

 PRI me R 4-C. Following the procedure of Example 3-C, 1000 parts of the reaction product of Example 1-C are reacted with 175 parts of sulfur dichloride. The reaction product is diluted with 400 parts of oil.

 PRI me R 5-C. Following the procedure of Example 3-C, 1000 parts of the reaction product of Example 1-C are reacted with 319 parts of sulfur dichloride. 788 parts of dilution oil was added to the reaction product, and the material was thoroughly mixed.

 PRI me R 6-C. Following the procedure of Example 4-C, 1000 parts of the reaction product of Example 2-C were reacted with 44 parts of sulfur dichloride to obtain sulfonated phenol.

 PRI me R 7-C. Following the procedure of Example 5-C, 1000 parts of the reaction product of Example 2-C are reacted with 80 parts of sulfur dichloride.

 The equivalent weight of the component (C-2-a) is equal to its molecular weight divided by the number of hydroxyl groups in the molecule.

Component (C-2-d) is at least one oil-soluble carboxylic acid as described above, one oil-soluble carboxylic acid as described above, or a functional derivative thereof. Particularly suitable are carboxylic acids of the formula R ⁵ (COOH) _n , in which n is an integer from 1 to 6 and preferably 1 or 2, and R ⁵ is a saturated or substantially saturated aliphatic radical (preferably hydrocarbon) having at least 8 aliphatic carbon atoms. Depending on the value of n, R ⁵ may be a monovalent to hexavalent radical.

 Examples of such acids are caprylic, caproic, palmitic, stearic, isostearic, linoleic and behenic acids. The preparation of oil-soluble dispersions of alkali metal sulfonates used as component (C) in the lubricating oil compositions of this invention is illustrated in the following examples.

PRI me R C-1. To a solution of 790 parts (1 equivalent) of alkylated benzenesulfonic acid and 71 parts of polybutenyl succinic anhydride (equivalent weight of about 560), containing predominantly isobutylene blocks, 320 parts (6 equivalents) of sodium hydroxide and 640 parts are added to 176 parts of mineral oil . (20 equiv.) Of methanol. The temperature of the mixture rises to 89 ^about C (boiling) for 10 min due to the exothermic reaction. During this period, the mixture is purged with carbon dioxide at a speed of 4 cubic meters. ft / h (1 ft = 0.308 m.). The carbonation was continued for about 30 minutes while the temperature gradually decreases to 74 ° ^C. The methanol and other volatile materials are stripped from the carbonated material by blowing the mixture with nitrogen at 2 cubic meters. ft / hr, while the temperature slowly rises to 150 not ^C for 90 min. After completion of stripping the remaining mixture is held at 155-165 ^{° C} for about 30 minutes and filtered to obtain an oil solution of the desired basic sodium sulfonate having a metal ratio of about 7.75. This solution contains 12.4% oil.

PRI me R C-2. Following the procedure of Example C-1, a solution of 780 parts (1 equivalent) of alkyl benzenesulfonic acid and 119 parts of polybutenyl succinic anhydride in 442 parts of mineral oil was mixed with 800 parts (20 equivalents) of sodium hydroxide and 704 parts (22 equivalents) .) methanol. The mixture is purged with carbon dioxide at a speed of 7 cubic meters. ft / h for 11 min, when the temperature slowly rises to 97 ^about C. The flow rate of carbon dioxide decreases to 6 cubic meters. ft / hr, and the temperature slowly decreases to 88 ^{° C} for about 40 min. The flow rate of carbon dioxide decreases to 5 cubic feet per hour for about 35 minutes, and the temperature of the mixture is slowly lowered to 73 ^about C. Volatile materials are distilled off by blowing nitrogen through a carbonated mixture at a speed of 2 cubic feet per hour for 105 minutes while the temperature is raised slowly to 160 ° ^C. After stripping is complete the mixture is held at 160 ^{° C} for an additional 45 minutes and then filtered to obtain an oil solution of the desired basic sodium sulfonate having a metal ratio of about 19.75. This solution contains 18.7% oil.

PRI me R C-3. Following the procedure of Example C-1, a solution of 3200 parts (4 equivalents) of alkyl benzenesulfonic acid and 284 parts of polybutenyl succinic anhydride in 623 parts of mineral oil was mixed with 1280 parts (32 equivalents) of sodium hydroxide and 2560 parts (80 equivalents) methanol. This mixture was purged with carbon dioxide at a rate of 10 cubic feet / h for about 77 minutes. During this time the temperature increases to 92 ^{° C} and then gradually decreases to 73 ° ^C. The volatile materials are stripped by blowing with nitrogen gas at 2 scf / hr for about 2 hours, when the temperature of the reaction mixture slowly increases to 160 ^C. . The final traces of volatile materials are stripped in vacuo and the residues kept at ¹⁷⁰ ° C and then filtered to obtain a clear oil solution of the target sodium salt having a metal ratio of about 7.72. This solution has an oil content of 11%.

PRI me R C-4. Following the procedure of Example C-1, a solution of 780 parts (1 equivalent) of alkyl benzenesulfonic acid and 86 parts of polybutenyl succinic anhydride in 254 parts of mineral oil was mixed with 480 parts (12 equivalents) of sodium hydroxide and 640 parts (20 square meters). ) methanol. The reaction mixture is purged with carbon dioxide at a rate of 6 cubic meters. ft / h for approximately 45 minutes During this time the temperature increases to 95 ^{° C} and then gradually decreases to 74 ° ^C. The volatile material is stripped by blowing with nitrogen gas at 2 scf / hr for about 1 hour, when the temperature increases to 160 ^C. After completion of the the steaming mixture is kept at 160 ^about C for 0.5 h and then filtered to obtain an oily solution of the target sodium salt having a metal ratio of 11.8. The oil content in this solution is 14.7%.

PSS

M в которой R^I и R^II каждый независимо является углеводородной группой, содержащей от 3 до 13 атомов углерода, М - это металл и n целое число, равное валентности металла М.(D) Metal Dialkyldithiophosphate
In another embodiment, the oil compositions of the present invention also comprise (D) at least one metal dihydrocarbyl dithiophosphate of the formula

Pss

M in which R ^I and R ^II each independently is a hydrocarbon group containing from 3 to 13 carbon atoms, M is a metal and n is an integer equal to the valency of metal M.

 In general, the oil compositions of the present invention may contain various amounts of one or more of the metals indicated above with dithiophosphate, such as from about 0.01 to 2% by weight, and more often from 0.01 to 1% by weight, based on the total weight of the oil composition. Metal dithiophosphates are added to the lubricating oil compositions of the invention in order to improve the antiwear and antioxidant properties of the oil compositions.

The hydrocarbon groups R ^I and R ^II in the dithiophosphate of formula XI may be alkyl, cycloalkyl, aralkyl or alkaryl groups or a substantially hydrocarbon group of a similar structure. By “substantially hydrocarbon” is meant hydrocarbons that contain substituent groups, such as an ester, ester, nitro group or halogen, which do not actually affect the hydrocarbon nature of this group.

 Examples of alkyl groups include isopropyl, isobutyl, n-butyl, sec-butyl, various amyl groups, n-hexyl, methylisobutylcarbinyl, heptyl, 2-ethylhexyl, diisobutyl, isooctyl, nonyl, behenyl, decyl, dodecyl, tridecyl and others. Examples of lower alkylphenyl groups include butylphenyl, amylphenyl, heptylphenyl, etc. Cycloalkyl groups are also used, and they mainly include cyclohexyl and lower alkyl cyclohexyl radicals. Many substituted hydrocarbon groups can also be used, for example, chloropentyl, dichlorophenyl and dichlorodecyl.

Dithiophosphoric acids are prepared by reacting phosphorus pentasulfide with alcohol or phenol or mixtures of alcohols. This reaction involves four moles of the alcohol or phenol per 1 mole of phosphorous pentasulfide and may be carried out within the temperature range from about 50 ^o C to 200 ^o C. Thus, the preparation of 0,0-di-n-geksilditiofosfornoy acid comprises reacting phosphorus pentasulfide with four moles of n-hexyl alcohol at about 100 ^C for about 2 h. Provided hydrogen sulfide, and the residue is the defined acid. The preparation of a metal salt of this acid can be carried out by reaction with a metal oxide. Simple mixing and heating of these two reagents is sufficient to cause a reaction to occur, the resulting product being pure enough for the purposes of the present invention.

 The metal salts of dihydrocarbon dithiophosphates that are used in this invention include those salts which contain Group I, Group II metals, aluminum, lead, tin, molybdenum, manganese, cobalt and nickel. Metals of the second group, aluminum, tin, iron, cobalt, lead, molybdenum, manganese, nickel and copper are among the preferred metals. Especially useful metals are zinc and copper. Examples of metal compounds that can interact with an acid include lithium oxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, silver oxide, magnesium oxide, magnesium hydroxide, calcium oxide, zinc hydroxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, barium oxide, aluminum oxide, iron carbonate, copper hydroxide, lead hydroxide, tin butylate, cobalt hydroxide, nickel hydroxide, nickel carbonate, etc.

 In some cases, the introduction of certain components, such as small amounts of metal acetate or acetic acid in combination with a metal reagent, can facilitate the reaction and lead to an improved product. For example, the use of up to 5% zinc acetate in combination with the required amount of zinc oxide promotes the formation of zinc dithiophosphate.

In one preferred embodiment, the alkyl groups R ^I and R ^{II are} derived from secondary alcohols, such as isopropyl alcohol, secondary butyl alcohol, 2-pentanol, 2-methyl-4-pentanol, 2-hexanol, 3-hexanol, etc.

 Especially useful metal dithiophosphates can be obtained from dithiophosphoric acids, which, in turn, are prepared by reacting phosphorus pentasulfide with mixtures of alcohols. In addition, the use of such mixtures makes it possible to use cheaper alcohols, which themselves may not form oil-soluble dithiophosphoric acids. Thus, a mixture of isopropyl and hexyl alcohols can be used to obtain a very effective oil-soluble metal dithiophosphate. For the same reasons, mixtures of dithiophosphoric acids can interact with metal compounds to form less expensive oil-soluble salts.

 Alcohol mixtures may be mixtures of various primary alcohols, mixtures of various secondary alcohols, or mixtures of primary and secondary alcohols. Examples of mixtures used include: n-butanol and n-octanol; n-pentanol and 2-ethyl-1-hexanol; isobutanol and isoamyl alcohol; isopropanol and 2-methyl-4-pentanol; isopropanol and secondary butyl alcohol; isopropanol and isooctyl alcohol, etc. Mixtures of alcohols from secondary alcohols containing at least about 20 mol% of isopropyl alcohol, and in a preferred embodiment at least 40 mol% of isopropyl alcohol, are particularly suitable.

 The following examples illustrate the preparation of metal dithiophosphates obtained from mixtures of alcohols.

 PRI me R D-1. Dithiophosphoric acid is obtained by reacting a mixture of alcohols, including 6 moles of 4-methyl-2-pentanol and 4 moles of isopropyl alcohol, with phosphorus pentasulfide. Then dithiophosphoric acid reacts with a suspension of zinc oxide in oil. The amount of zinc oxide in the suspension is approximately 1.08 times greater than that required by stoichiometry in order to completely neutralize dithiophosphoric acid. Thus obtained zinc dithiophosphate in oil (10% oil) contains 9.5% phosphorus, 20.0% sulfur and 10.5% zinc.

 PRI me R D-2. Dithiophosphoric acid is prepared by reacting finely ground phosphorus pentasulfide with a mixture of alcohols containing 11.53 moles (692 parts by weight) of isopropyl alcohol and 7.69 moles (1000 parts by weight) of isooctanol. The dithiophosphoric acid thus obtained had an acid number of about 178-186 and contained 18.0% phosphorus and 21.0% sulfur. This dithiophosphoric acid then interacts with a suspension of zinc oxide in oil. The amount of zinc oxide introduced into the oil suspension is 110% of the theoretical equivalent of the acid number of dithiophosphoric acid. The solution of zinc salt in oil thus obtained contains 12% oil, 8.6% phosphorus, 18.5% sulfur and 9.5% zinc.

PRI me R D-3. The reactor was charged with isopropyl alcohol (396 hr., 6.6 mole) and 1287 hours. (9.9 moles) of isooctyl alcohol and heated with stirring to 59 ^C. Then, the nitrogen flow was added phosphorus pentasulfide (833 parts. 3, 75 mol). Addition of the phosphorus pentasulfide is completed in about 2 hours at a reaction temperature between 59 and 63 ^C. The mixture was then stirred at 45-63 ^{° C} for about 1.45 hours and filtered. The filtrate is the target dithiophosphoric acid.

312 parts (7.7 equivalents) of zinc oxide and 580 parts of mineral oil are charged to the reactor. Under stirring at room temperature was added the previously prepared phosphorodithioic acid (2287 hr., 6.97 eq.) For 1.26 hours at the exothermic heating to 54 ^C. The mixture was heated to 78 ^{° C} and maintained at 78-85 ^C. for 3 hours. The reaction mixture was stripped in vacuo at ¹⁰⁰ ° C and a pressure of 19 mm Hg The residue is filtered through a filter, the filtrate being an oil solution (19.2% oil) of the target zinc salt containing 7.86% zinc, 7.76 phosphorus and 14.8% sulfur.

 PRI me R D-4. Dithiophosphoric acid is prepared in accordance with the general procedure of Example D-3 using a mixture of alcohols containing 520 parts (4 mol) of isooctyl alcohol and 360 parts (6 moles) of isopropyl alcohol with 504 parts (2.27 mol) of phosphorus pentasulfide . Zinc salt is prepared by reacting an oil suspension of 116.5 parts of mineral oil and 142.5 parts (3.44 mol) of zinc oxide with 950.9 parts (3.20 mol) of dithiophosphoric acid prepared above. The product thus obtained is an oil solution (10% mineral oil) of the target zinc salt, wherein the oil solution contains 9.36% zinc, 8.81% phosphorus and 18.65% sulfur.

 Additional examples of metal dithiophosphates used as component (D) in the lubricating oils of the present invention are listed in the following table B. In Examples D-5 to D-10, salts are obtained from individual alcohols, and in Examples D-11 to D- 15 they are obtained from a mixture of alcohols by the General method of example D-1.

 (E) Compositions of esters of carboxylic acids.

 The lubricating oil compositions of the present invention may also contain (E) at least one carboxylic acid ester derivative composition obtained by reacting (E-1 at least one substituted succinic acylating agent with (E-2) at least one alcohol or phenol.

Substituted succinic acylating agents (E-1) that interact with alcohols or phenols to produce carboxylic acid ester derivatives (E) are identical to the acylating agents (B-1) used in the preparation of the carboxyl derivatives (B) described above, with one an exception. The polyalkene from which the substituent is derived is characterized in that it has a number average molecular weight of at least about 700. Preferred are number average molecular weights from about 700 to 5000. In one preferred embodiment, the substitution of the acylating agent group is obtained from polyalkers which are characterized by a value of M _n from about 1300 to 5000 and a ratio of M _w / M _n from about 1.5 to 4.5. The acylating agents of this embodiment are identical to the previously described acylating agents in connection with the preparation of component (B). Thus, any acylating agents described in connection with the preparation of component (B) above can be used in the preparation of ester derivative carboxylic acid compositions used as component (E). When the acylating agents used to produce the carboxylic acid ester (E) are the same as the acylating agents used in the preparation of component (B), the carboxylic ether component (E) will also be characterized as a dispersant to improve viscosity index. In addition, combinations of component (B) and these preferred types of component (E) provide excellent anti-depressant properties to the oils of the invention. However, other substituted succinic acylating agents can also be used in the preparation of ester derivative carboxylic acid compositions which are used as component (E) in the present invention.

 The following examples illustrate esters (E) and methods for preparing such esters.

PRI me R E-1. Hydrocarbon substituted succinic anhydride is obtained by chlorination of polyisobutylene having a number average molecular weight of about 1000 to a chlorine content of 4.5%. Then, chlorinated polyisobutylene is heated with 1.2 molar parts of maleic anhydride at a temperature of 150-220 ^о С. A mixture of 874 g (1 mol) of succinic anhydride and 104 g (1 mol) of neopentyl glycol is maintained at 240-250 ^о С, pressure 30 mm Hg for 12 hours. The residue is a mixture of esters formed during the esterification of one or both hydroxyl groups of glycol.

PRI me R E-2. The hydrocarbon-substituted succinic anhydride of Example 1 is partially esterified with ether alcohol as follows. A mixture of 550 g (0.63 mol) of anhydride and 190 g (0.32 mol) of commercial polyethylene glycol having a molecular weight of 600 is heated at 250-240 ^C for 8 hrs. At atmospheric pressure and 12 hr. At 30 mmHg. until the acid number of the reaction mixture drops to about 28. The residue is the target acid ester.

PRI me R E-3. A mixture of 926 g of polyisobutylene-substituted succinic anhydride having an acid number of 121, 1023 grams of mineral oil and 124 grams (2 moles per mole of the anhydride) of ethylene glycol is heated at 50-170 ^{° C,} while hydrogen chloride was bubbled through the reaction mixture for 1.5 hours. The mixture was then heated to 250 ° ^C under a pressure of 30 mm Hg and the remainder was purified by washing with aqueous sodium hydroxide followed by washing with water, then dried and filtered. The filtrate is a 50% oily solution of the desired ester.

 The carboxyl ether derivatives described above are formed by the interaction of an acylating agent with a hydroxide-containing compound, such as alcohol or phenol, and can additionally react with an amine (E-3) and in particular with a polyamine according to the method described previously for the reaction of an acylating agent ( B-1) with amines (B-2) preparation of component (B). Any of the above designated (B-2) amines can be used as the amine (E-3). In one embodiment, the amount of amine (E-3) that interacts with the ester in such an amount that there is at least about 0.01 equivalents of amine for every 1 equivalent. an acylating agent that is initially used in reaction with alcohol. When the acylating agent interacts with the alcohol in such an amount that there is at least one equivalent of alcohol for each equivalent of the acylating agent, then this small amount of amine is sufficient to react with the smaller amounts of unesterified carboxyl groups that may be present. In one preferred embodiment, the amino-modified carboxylic acid esters used as component (E) are prepared by reacting about 1.0 to 2.0 equivalents, preferably from 1.0 to 1.8 equivalents. hydroxy compounds and up to 0.3 equiv., preferably from 0.02 to 0.25 equiv. polyamine at 1 equiv. acylating agent.

 In another embodiment, the acylating agent (E-1) of the carboxylic acid may react simultaneously with the alcohol (E-2) and the amine (E-3). Usually there is at least about 0.01 equiv. alcohol and at least almost 0.01 equiv. alcohol and at least 0.01 equiv. amine, although the total number of equivalents of this combination should be at least 0.5 equiv. by 1 equiv. acylating agent.

 The lubricating oil compositions of the present invention may also contain, and preferably indeed contain, at least one friction modifier to give the lubricating oil proper frictional characteristics. Various amines, especially tertiary amines, are effective friction modifiers. Examples of such tertiary amines include: N-fatty alkyl-N, N-diethanolamine, N-fatty alkyl-N, N-diethoxyethanolamines, etc. Such tertiary amines can be prepared by reacting a fatty alkylamine with an appropriate number of moles of ethylene oxide. Tertiary amines derived from naturally occurring substances such as coconut oil and oleoamine are available from Armbur Chemical Co., under the trademark Etomin. Specific examples are the Etomin-C and Etomin-O series.

 Sulfur-containing compounds such as C12-C24 sulphurous fats, alkyl sulphides and polysulphides in which the alkyl groups contain from 1 to 8 carbon atoms, and sulphurous polyolefins can also serve as friction modifiers in the lubricating oil compositions of the invention.

(G) Neutral and basic salts of alkaline earth metals
The lubricating oil compositions of the present invention may also contain at least one neutral or basic alkaline earth metal salt and at least one acidic organic compound. Such salts are commonly referred to as ash containing detergents. The acidic organic compound may be at least one sulfuric acid, carboxylic acid, phosphoric acid or phenol, or a mixture thereof.

 Preferred alkaline earth metals are calcium, magnesium, barium and strontium. Salts containing a mixture of ions of two or more of these alkaline earth metals may be used.

 Salts that are used as component (G) may be neutral or basic. Neutral salts contain an amount of alkaline earth metal that is sufficient only to neutralize the acid groups present in the salt anion, and the basic salts contain an excess of alkaline earth metal cation. Usually preferred are basic or superbasic (alkalized) salts. These basic or displaced salts can have metal ratios of up to about 40, and more particularly from about 2 to 30 or 40.

Usually used process for the preparation of basic (or superbasic) salts comprises heating a mineral oil solution of the acid with a stoichiometric excess of a metal neutralizing agent such metal oxide, hydroxide, carbonate, bicarbonate, sulfide, etc.. At temperatures above about 50 ° ^C. Furthermore, there may be used various promoters in the neutralization process to facilitate the introduction of a large excess of metal. These promoters include compounds such as phenolic substances, for example phenol, naphthol, alkyl phenol, thiophenol, sulphide alkyl phenols, and various products of the condensation of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve - carbitol, ethylene glycol, stearyl alcohol and cyclohexyl alcohol; amines such as aniline, phenylenediamine, phenothiazine, phenyl-beta-naphthylamine, dodecylamine, phenothiazine, phenyl-beta-naphthylamine, dodecylamine, etc. A particularly effective method for preparing basic salts involves mixing the acid with an excess of basic alkaline-earth metal in the presence of a phenolic promoter and a small amount of water and carbonization of the mixture at elevated temperature, for example from 60 to 200 ^about C.

 The amount of component (G) included in the lubricating oils of the present invention can vary over a wide range, and the amounts used in each case can easily be determined by a person skilled in the art. Component (G) acts as an auxiliary or additional detergent. The amount of component (G) contained in the lubricating oil of this invention can be changed from about 0% to 5% or more.

 The following examples illustrate the preparation of neutral and basic alkaline earth metal salts used as component (G).

PRI me R G-1. A mixture of 906 hours. Oily solution alkilfenilsulfonovoy acid (having a number average molecular weight 450), 564 hours. The mineral oil of 600 hr. Of toluene, 98.7 h. Magnesium oxide and 120 hours. The water was purged with carbon dioxide at a temperature of ^about 78-85 C. for 7 hours at a rate of about 3 cubic foot per hour of CO ₂ (1 cubic foot = 28.3 l). The reaction mixture is constantly stirred during carbonation. After carbonation, the reaction mixture was stripped at 165 ^{° C} - 20 mmHg the residue is filtered. The filtrate is an oily solution (34% oil) of the desired re-alkalized magnesium sulfonate having a metal ratio of about 3.

PRI me R G-2. Poliizobutilyantarny anhydride is prepared by reacting a chlorinated poly (isobutene) (having an average chlorine content of 4.3% and derived from polyisobutylene having a number average molecular weight of about 1150) with maleic anhydride at about 200 ^° C to a mixture of 1246 hours. This succinic anhydride and 1000 hours. toluene is added at ²⁵ ° C, 7.66 hours. The barium oxide. The mixture was heated to 115 ^C and added dropwise to 125 hours. The water for 1 h period. The mixture was then brought to reflux (reflux) at ¹⁵⁰ ° C until all the barium oxide is consumed. After steaming and filtering, the desired product is obtained.

 PRI me R G-3. basic calcium sulfonate having a metal ratio of about 15 is obtained by carbonation, in parts, of a mixture of calcium hydroxide, neutral petroleum sodium sulfonate, calcium chloride, methanol and alkyl phenol.

(H) Neutral and basic salts of phenolsulfi
In one embodiment, the oils of the invention may comprise at least one neutral or basic alkaline earth metal salt and an alkyl phenol sulfide. Oils may contain from about 0 to 2 or 3% of the indicated phenolsulfide. More often, the oil may contain from about 0.01 to 2 wt.% Of the basic salts of phenolsulfides. The term "main" is used here in the same sense as in the definition of the other components above, i.e. it refers to salts having a metal ratio higher than 1. Neutral and basic salts of phenolsulfides are detergents and antioxidants in oil compositions, and also can usually improve the performance of oils in a Caterpillar test.

 (1) Sulfurized olefins.

 The oil compositions of the present invention may also contain (1) one or more sulfur-containing compositions used to improve the antiwear, antioxidant properties of the ultimate pressure of the lubricating oil compositions. Oil compositions may include from about 0.01 to 2 wt. % sulfurized olefins. Sulfur-containing compositions prepared by sulfonation of various organic materials, including olefins, are useful. These olefins can be any aliphatic, arylaliphatic or alicyclic olefinic hydrocarbon containing from about 3 to 30 carbon atoms.

 Particularly preferred olefin compounds are propylene, isobutylene and their diameters, trimers and tetramers, and mixtures thereof. Of these compounds, isobutylene and diisobutylene are particularly desirable, due to their availability and the fact that high sulfur compositions can be obtained from them.

 The sulfonating agent may be, for example, sulfur, a sulfur halide such as sulfur monochloride or sulfur dichloride, a mixture of hydrogen sulfide and sulfur or sulfur dioxide, or the like. Mixtures of sulfur and hydrogen sulfide are often preferred.

 The amounts of sulfur and hydrogen sulfide per 1 mol of olefin compound are usually, respectively, about 0.3-3.0 gram atom and about 0.1-1.5 mol. Preferred ranges are about 0.5-2.0 g-at and about 0.5-1.25 mol, respectively, and the most preferred ranges are 1.2-1.9 g-at and 0.4-0.8 mol respectively.

Normally the temperature range in which the sulfurization reaction is carried out is about 50-350 ° ^C preferred range is about 100-200 ^{° C,} with particularly suitable interval of 120-180 ° ^C.

 The following examples illustrate the preparation of two such components.

PRI me R 1-1. Sulfur (629 parts, 19.6 mol) is loaded into a high pressure reactor with a jacket, which is equipped with a stirrer and an internal cooling coil. A cooling brine circulates through the coil in order to cool the reactor before introducing gaseous reactants. After the reactor was sealed, pumped to about 6 mmHg, and cooled, 1100 parts (9.6 mol) of isobutene, 334 parts (9.8 mol) of hydrogen sulfide and 7 parts of n-butylamine were charged into it. The reactor is heated using steam in the external jacket, to a temperature of about 171 ^{° C} for 1.5 hours. The maximum pressure is reached 720 pounds / square inch (50.6 atmospheres) at 138 ^{° C} during the heating. Until the peak reaction temperature is reached, the pressure begins to decrease and continues to decrease continuously, since gaseous reactants are consumed. After about 4.75 hours at 171 ^{° C,} unreacted hydrogen sulfide and isobutylene are discharged into recovery system. After reducing the pressure in the reactor to atmospheric, the sulfonated product is released as a liquid.

PRI me R 1-2. (and). A mixture containing 400 g of toluene and 66.7 g of aluminum chloride was charged into a two liter flask equipped with a stirrer, a nitrogen inlet tube and a reflux condenser cooled by solid carbon dioxide. A second mixture comprising 640 grams (5 moles) of butylacrylate and 240.8 grams of toluene is added to a suspension of aluminum chloride over 15 minutes while maintaining the temperature between 37-58 ^C. After this suspension was added to 313 g (5.8 moles butadiene for 2.75 hours while maintaining the reaction mixture temperature at 60-61 ^{° C} by external cooling. The reaction mixture was purged with nitrogen about 20 minutes and then transferred to a four-liter separatory funnel and washed with a solution of 150 g of concentrated hydrochloric acid in 1100 g of water, after which the reaction product after edovatelno distilled to remove unreacted butylacrylate and toluene. The residue of this first distillation step is subjected to further distillation at a pressure of 9-10 mm Hg, resulting in 785 g of the title is collected adduct at a temperature of 105-115 ° ^C.

(b). The above-prepared adduct of butadiene and butyl acrylate (4550 g, 25 mol) and 1600 g (50 mol) of sulfur color are charged into a 12-liter flask equipped with a stirrer, reflux condenser and tube or nitrogen supply. The reaction mixture was heated at a temperature within the range 150-155 ^{° C} for 7 hours while passing nitrogen therethrough at a rate of 0.5 cubic feet / hour (14.2 l / h). After heating, the mass is allowed to cool to room temperature and filtered, the filtrate being a sulfur-containing product.

 The composition of the oil according to the invention may include other extreme pressure agents and agents that inhibit oxidation and corrosion. Examples thereof are chlorinated aliphatic hydrocarbons, such as chlorinated paraffin wax; organic sulfides and polysulfides such as benzyl disulfide, bis (chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized oleic acid methyl ester, sulfonated alkyl phenol, sulfonated dipentene, and sulfonated terpene; phosphorus-sulfur hydrocarbons, such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphorus esters including mainly diuglevodorodnye triuglevodorodnye and phosphates such as dibutyl phosphate, pentilfenilfosfit, dipentilfenilfosfit, tridecyl, distearilfosfit, dimetilnaftilfosfit, oleyl-4-pentilfenilfosfit, polypropylene - (molecular weight 500) -substituted phenyl phosphite, diisobutyl-substituted phenyl phosphite; metal thiocarbonates such as zinc dioctyl dithiocarbamate and barium heptyl phenyl dithiocarbamate.

 Particularly useful additives in the oil according to the invention are additives that lower the pour point.

 Examples of additives used to lower the pour point are polymethacrylates, polyacrylates, polyacrylamides, condensation products of halogenated paraffins and aromatic compounds, vinyl carboxylate polymers; and ternary polymers of dialkyl fumarates, vinyl esters of complex acids and alkyl vinyl ethers.

 Anti-foaming agents are used to reduce or prevent the formation of stable foam. Typical anti-foaming agents include silicones or organic polymers.

 The lubricating oil compositions of the present invention may also contain one or more industrially available viscosity modifiers. Typically, viscosity modifiers are polymeric materials characterized as hydrocarbon-based polymers, typically having a number average molecular weight of between 25,000 and 500,000, more often between 50,000 and 200,000.

 Polyisobutylene can be used as a viscosity modifier in lubricating oils. Polymethacrylates (PMA) are obtained from mixtures of methacrylate monomers having various alkyl groups. Most PMA are viscosity modifiers, as well as additives that lower the pour point.

 When a small amount of a nitrogen-containing monomer is copolymerized with alkyl methacrylates, the product also acquires dispersing properties. Thus, such a product has the multiple function of a viscosity modifier that disperses and lowers the pour point of the additive. Such products relate in the prior art to dispersant-type viscosity modifiers, or simply to dispersant-viscous modifiers. Examples of nitrogen-containing monomers are vinyl pyridine, N-vinyl pyrrolidone and N, N-dimethylaminoethyl methacrylate. Polyacrylates obtained by polymerization or copolymerization of one or more acrylates are also used as viscosity modifiers.

 Ethylene propyl copolymers, commonly called SSRs, are prepared by copolymerizing ethylene and propylene in a hydrocarbon solvent using a Ziegler-Natta initiator. The ratio of ethylene to propylene in the polymer affects the solubility in oil, the ability to thicken, low temperature viscosity, the ability to lower the pour point and product performance. The usual range of ethylene content is 45-60 wt. % and usually from 50% to about 55 wt.%. Some industrial SSRs are ternary polymers of ethylene, propylene and a small amount of a non-conjugated diene such as hexadiene-1,4. In the rubber industry, such ternary polymers are called EPDM (ethylene-propylene-diene monomer).

 Esters obtained by copolymerization of styrene and maleic anhydride in the presence of a free radical initiator followed by esterification of the copolymer with a mixture of С4-С18 alcohols are also used as viscosity modifiers for motor oils. Typically, styrene esters are considered multifunctional first-class viscosity modifiers. In addition to their viscous-modifying properties, styrene esters are also additives that lower the pour point and exhibit dispersing properties when the esterification is incomplete and the anhydride or carboxylic acid groups are left unreacted. These acid groups can then be converted to imides by reaction with a primary amine.

 Hydrogenated copolymers of styrene and conjugated dienes are another class of industrially available viscosity modifiers for motor oils. Examples of styrenes are styrene, alpha-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, para-tert-butylstyrene and others. Preferably, conjugated dienes contain from 4 to 6 carbon atoms. Examples of conjugated dienes include piparylene, 2,3-dimethyl-1,3-butadiene, chloroprene, isoprene and 1,3-butadiene, chloroprene, isorene and 1,3-butadiene, with isoprene and butadiene being particularly preferred. Mixtures of such conjugated dienes are also used.

 Typically, these copolymers have a number average molecular weight in the range of from about 30,000 to 500,000, preferably from 50,000 to 200,000. Usually, the weight average molecular weight of these copolymers is in the range of from about 50,000 to 500,000, preferably from 50,000 to 300,000.

 The amounts of the polymer viscosity modifier incorporated in the lubricating oil composition of the present invention can vary widely, although smaller amounts are used compared to those known in connection with the ability of component (B), a carboxylic acid derivative (and some carboxylic acid ester derivatives (E), to act as a viscosity modifier in addition to its dispersant function, In general, the amount of polymer additive that improves viscosity can be up to 10 wt.%, based on oil. its often polymeric viscosity improvers are used in concentrations of about 0.2 to 8%, and more particularly in amounts of about 0.5 to 6% by weight.

 The lubricating oils of the present invention can be obtained by dissolving or suspending various components introduced into the base oil along with other additives that can be used. More often, the chemical components of the present invention are diluted with a substantially inert, usually liquid, organic diluent, such as mineral oil, to form an additive concentrate. Typically, these concentrates include from about 0.01 to 80 wt.% Additives. Concentrations such as 15%, 20%, 30%, or 50% or higher may be used.

 Typical lubricating oil compositions of the present invention are listed in the following lubricating oil examples (see Tables 1-3).

 In the following examples of I-XV lubricants, percentages indicate the amount of the usually diluted oil solutions of these additives that are used to form the lubricating oil composition. For example, lubricating oil 1 contains 6.5% by volume of a product of approximately B-20, which is an oil solution of said carboxyl derivative (B) containing 55% diluted oil.

 The lubricating oil compositions of the present invention exhibit a reduced tendency to deteriorate under operating conditions, and therefore wear and deposits of unwanted deposits such as carbon deposits, sludge, carbon materials and tar materials that tend to adhere to different parts of the engine and reduce its efficiency are reduced. Lubricating oils can also be formulated in accordance with this invention, which leads to improved fuel economy when used in a car crankcase. In one embodiment of the invention, lubricating oils can be formulated that can pass all the tests required to classify them as SG oil.

The performance of the lubricating oil compositions of the present invention is evaluated by subjecting the lubricating oil compositions to a series of engine oil tests, which are intended to evaluate various performance characteristics of engine oils. As mentioned above, in order to qualify lubricating oil according to the Servinsky classification API SG it must pass certain special tests. However, for certain applications, lubricating oil compositions that have passed one or more individual tests are also used. Example XI% Product of example B-1 6.2 Product of example C-1 0.50 Neutral paraffin oil remaining Example XII Product of example B-23 6.8 Product of example C-2 0.50 Neutral paraffin oil remaining Example XIII Product of example B -23 5.5 Product of example C-2 0.40 Product of example D-1 0.80 Neutral paraffin oil other Example XIV Product example B-22 4.8 Product of example C-4 0.4 Product of example D-1 0, 75 Product of example G-1 0.45 Product of example G-3 0.30 Neutral paraffin oil remaining Example XV Product of example B-21 4.7 Product of example C-3 0.3 Product of example D-4 0.8 Product of example G-1 0.5 Product of example G-3 0.2 Neutral paraffin oil remaining
The SHE ASTM lubricating oil test sequence has been developed as a means of determining high temperature wear, oil thickening, and anti-scale ability of SG engine oils. The CW test, which replaces the BW test sequence, provides an improved distinction in respect of the high temperature cam shaft and protection of the wear of the elevator and the control of oil thickening. The SHE test uses a 3.8-liter Buick engine, model B-6, which is powered by leaded gasoline with an effective power of 67.8 hp. and a speed of 3000 rpm with a maximum test duration of 64 hours. A load of 230 lbs (104 kg) on the valve spring was used. Due to the high operating temperatures used a 100% glycol coolant temperature at the outlet of which was maintained at 118 ^{° C,} and the temperature and pressure oil - equal to 149 ^{° C} and 2.1 atm. The air / fuel ratio was 16.5, and the purge rate was 45.3 l / min, initial oil loading of 146 ounces (1 ounce = 28.3 g).

The test was interrupted when the oil level dropped by 28 ounces at any 8-hour control interval. When the tests were completed before 64 hours because of low oil level, this was mainly due to an unresponsive deeply oxidized oil throughout the engine and its inability to drain to the oil pan oil temperature control at 49 ° ^C. The viscosities were measured at 8-hour oil samples, and from these data were built curves of viscosity increase (in%) versus engine operating time (hours). For the API SG classification required maximum viscosity increase by 375%, measured ^at 40 ° C after 64 hours of operation. The minimum amount of motor sludge is 9.2, the deposit on the piston is at least 8.9, and the deposit on the annular chamfer is at least 3.5 based on the CRC quality assessment system.

 The results of the SEE ASTM test performed on lubricant IX are summarized in Table 4.

The Ford VE test uses a 2.3-liter (140 CID) 4-cylinder air cam engine equipped with a multi-point electronic fuel injection system, with a compression ratio of 9.5: 1. The test procedure uses the same format as the VD test sequence with a four-hour cycle consisting of 3 different stages. Oil temperature (in ^about F) in stages I, II and III are 155/210/115, and the water temperature ^(o F) in three stages are 125/185/115, respectively. The test oil had a loading volume of 106 ounces, with the jacket cover having a jacket to control the highest engine temperature. The speeds and loads in the three stages were the same as in the VD test. The purge rate in Stage 1 increased to 57 l / min from 51 l / min, and the test duration was 12 days. DCS valves were replaced in this test every 48 hours.

 At the end of the test, motor sludge, sludge in the casing cover, piston deposits and exhaust valve wear are evaluated.

 The results of the Ford VE test sequence conducted with the lubricating oil W of the present invention are shown in Table 5. The operational requirements for the SG classification are as follows: motor sludge - 9.0 minimum, sludge in the connecting rod casing - 7.0 minimum, average carbon formation - 5.0 minimum, piston carbon - 6.5 minimum, VTW - maximum 15/5.

The CRCL-38 trial was developed by the Coordinating Research Council. This test method is used to determine the following characteristics of crankcase lubricants: antioxidability, tendency to corrosion, tendency to form sludge and soot, and viscosity stability under high temperature conditions. The CRL engine is characterized by a rigid structure and is a single-cylinder engine with spark ignition and liquid cooling, operating at a fixed speed and fuel flow. This engine has 1/4 crankcase capacity. According to the requirements techniques CRL cylinder engine running at a speed of 3150 rev / min, the effective power of about 5 hp, the temperature of the oil channel 143 ^C and temperature discharged refrigerant 93 ^{° C} for 40 hours. The test is interrupted every 10 h. For sampling oils and distillation of light fractions. The viscosity of these oil samples is determined and these values are noted as part of the test results.

 A special copper-lead bearing for testing is weighed before and after the test to determine weight loss due to corrosion. After testing, the engine is evaluated for sludge and carbon deposits. The most important of the indicators is the soot of the piston skirt. The primary quality criterion for the API SG Service Classification is the loss of bearing weight (maximum 40 mg) and the estimated carbon deposits of the piston skirt (minimum 9.0).

 In the table. 6 summarizes the results of the L-38 test using the two lubricants of the invention.

 The Oldmobil test sequence 11D is used to evaluate rust and corrosion characteristics of motor oils.

Tests and their conditions are described in special technical publication ASTM 315H (part 1). In the 11D sequence, a 5.7-liter Oldmobile (350 CID) Y-8 engine is used, operating at low speed (1500 rpm) under light load (25 hp) for 28 hours at a coolant temperature of 41 ^о С and outlet 43 ^о С. According to this, the test was run for 2 hours at a speed of 1500 rpm and a coolant temperature inlet 47 ^о С and outlet 49 ^о С. After replacing the carburetor and spark plug, the engine worked for the last 2 hours at high speed (3600 rpm) under moderate load (100 hp) at a refrigerant inlet temperature е 88 ^о С and at the outlet 93 ^о С. After completion of the tests (32 h), the engine was examined for rusting using the CRC assessment technique. The number of stuck lift valves was also noted, which gives an estimate of the amount of rust. The minimum average rust rating for an 11D test is 8.5. When used in the sequence 11D test of the lubricating oil composition, designated above as oil X, the average rating of CRC rust is 8.5.

 The Caterpillar 1H2 test, described in Special Technical Publication ASTM 509A, Part II, is used to determine the effect of lubricating oils on sticking of rings, wear on rings and cylinder, and on accumulation of deposits on the Caterpillar engine piston. The test includes the operation of a special overloaded single-cylinder diesel engine for 480 hours at a fixed speed of 1800 rpm and a fixed heat input. The highest heat input through the valve was 4950 btu / min (1250 kcal / min). As a lubricant, the test oil is washed, and diesel fuel was ordinary, refined diesel fuel containing from 0.37 to 0.43% natural sulfur.

 After completion of the test, the diesel engine was examined to determine if there were adhering rings, the degree of wear of the cylinder, liner and piston rings, and the amount and nature of deposits on the piston. In particular, in this test, the filling of the upper groove (TGF) and the weight total wear (WTD) per coating and location of deposits are recorded as the primary quality criterion for diesel lubricants. The target values for the IN2 test are the EGF value of a maximum of 45 vol.% And the maximum WTD score is 140 after 480 hours.

 The test results of IN2 company Caterpillar, conducted on several compositions of the lubricating oils of the present invention, are summarized in table 7.

While the IN2 test of Caterpillar is considered suitable for use with lightly loaded diesels (API CC Service Classification), the Caterpillar IG2 test described in Special Technical Publication ASTM509A, Part 1, is for severe applications (Service Classification API CD) The IG2 Test similar to the Caterpillar IH2 test, except that the conditions are more responsible The higher heat input through the valve was 5850 btu / min (1474 kcal / min) and the lowest heat input was 5490 btu / min (1580 kcal / min). The engine is operated at an effective power of 42 hp. Operating temperature: water from the cylinder head 83 has a ^C temperature, and the oil in the bearings - about 96 ° ^C. The temperature of the air entering the engine is maintained near 124 ^{° C} and an exhaust temperature of - 594 ^C. Due to rigid conditions of the diesel the test setpoints were higher than for IH2. The maximum allowable filling of the upper groove is 80 and the maximum value of the WTD-300.

 The results of the Caterpillar IC2 test conducted using composition YII of the present invention are summarized in Table 8.

 Test sequence VI is used to qualify the passenger car and light truck in the energy efficiency category API SAE / ASTM. In this test, the General Motors Y-6 3.8-liter engine operates under strictly controlled conditions, providing accurate measurements of Special Brake Fuel Consumption (BSFC) to detect lubricant-related friction present in the engine. To achieve maximum accuracy, microprocessor-based monitoring of equipment status and a data acquisition / processing system are used.

Each test is preceded by an ASTM engine calibration system using the following special ASTM oils: SAE 20 W-30 Friction Modifying Polyamine (FM), SAE 50 (LR) and SAE 20 W-30 High Reference (HR). After confirming the proper accuracy and calibration, the selected oil is poured into the engine without stopping it in order to withstand a 40-hour aging period at a moderate temperature, light load in stationary conditions. The aging was collected replicate BSFC measurements on each of the two stages with temperatures ranging from low ⁽¹⁵⁰ ° F, 65.5 ° ^C) to high ⁽²⁷⁵ F, 135 ^C), all at a speed of 1500 rev / min and effective power 8 hp These VSFC data are compared with the corresponding measurements obtained with fresh standard HR oil, which was poured into the engine immediately after recording the measurements for the aged selected oil.

 To reduce the effects of additives transferred from the selected oil to HR oil, the engine was operated multiple times with flushing oil (FO) with an abnormally high detergent content. Flushing oil was also used during calibration prior to engine testing. The test duration was 3.5 days., 65 working hours.

Reducing fuel consumption, provide a selected oil, but the average of the percentage change in the individual stages (delta) (at 150 and ²⁷⁵ F). Based on the general correlation of weighted test results with test results for 5 cars, the conversion equation is used to express the results in an equivalent improvement in fuel economy (EFEI).

Например, если на стадии 150^оФ наблюдается 3%-ное улучшение и 6%-ное улучшение на стадии 275^оФ, то с использованием указанного выше уравнения преобразования величина EFEI равно 2,49%.The equation used was:
EFEI =

For example, if in step ¹⁵⁰ there F 3% improvement and a 6% improvement at stage ²⁷⁵ F, then using the above equation conversion value is equal to 2.49% EFEI.

 The results of the sequence VI of the dynamometric test of the fuel efficiency of engine oil carried out using the lubricating oil compositions of the present invention (oils IV, VIII) are summarized in table 8. A target of 1.5% is the set minimum rating to indicate fuel economy, and a target of 2.7% is the minimum improvement in fuel economy required for the API / SAE / ASTM energy conservation category.

In the table. 10 and 11 indicate the compositions and data on the kinematic viscosity at 100 ^about With various lubricants obtained by varying the amount or composition of additives. Examples 1-4 illustrate the effect of the maximum, minimum and optimal amount of additives in the composition.

In the table. 11 illustrates the composition of 4 different lubricants used for comparative experiments. Lubricant 1 was obtained in accordance with the present invention and it includes, as component (B), 2.0 wt.% Of a carboxyl derivative obtained by reacting 1 equivalent of a polyisobutene-substituted succinic acylating agent with 0.83 equivalents of a polyamine compound, the polyisobutenyl substituent being has an Mn of about 1900 and an Mw / Mn of about 3, while the acylating agent contains about 1.8 amber groups for each equivalent mass of the polybutenyl group. Lubricating material II was obtained in accordance with a known method: by reacting I equivalent of the same substituted succinic acylating agent with I equivalent of the same polyamine. Lubricant III is obtained so that it has a composition similar to lubricant I, but contains 2.5 wt.% Component (B). Lubricant IV was obtained by analogy with lubricant II, but it should include 2 wt.% Component (B). The kinematic viscosity at 100 ^about is 11, 17 for lubricant 1; 10.92 for lubricant 11, 11.75 for lubricant III and 11.43 for lubricant IV. Obviously, the kinematic viscosity characteristics of lubricants obtained by known methods are significantly worse than the characteristics of lubricants obtained in accordance with the present invention. An increase in the viscosity of the lubricating compositions according to the present invention, which is obtained economically, since it is now possible to obtain lubricating oil compositions having the necessary increased viscosity without the need to use additional amounts of known viscosity index modifiers, which are much more expensive compared to carboxylic derivatives component (B).

Claims (3)

LUBRICANT OIL FOR INTERNAL COMBUSTION ENGINES based on mineral oil or oil with additives, containing a basic alkali metal salt of sulfonic acid or carboxylic acid and a product of the interaction of polyisobutylene succinic acid with an amine, characterized in that, in order to increase the viscosity, the oil contains a product as an interaction product obtained on the basis of polyisobutylene succinic acid containing 1.3 to 4 groups of succinic acid per equivalent mass of polyisobutylene having a number average mol.m. 1300 - 5000 and the ratio of the weight average to the number average molecular weight of 1.5 - 4.5, and in which 1 equivalent of polyisobutylene succinic acid accounts for 0.7 - 0.95 equivalent of amine, in the following ratio of components, wt.%:
The specified interaction product 2 - 15
Base alkali metal salt of sulfonic acid or carboxylic acid 0.01 - 2.00
Mineral oil or oil with additives Up to 100
2. The oil according to claim 1, characterized in that in the reaction product, the amine has the general formula
R-

-

U-

R
where n = 1 to 10;
each R is independently hydrogen, a hydrocarbon group, an oxy- or amino-substituted hydrocarbon group having no more than 30 carbon atoms, provided that one or more R groups is hydrogen;
U - C ₂ - C ₁₀ - alkylene group.  3. The oil according to claim 1, characterized in that the basic alkali metal salt has a ratio of equivalents of alkali metal and equivalents of sulfonic acid or carboxylic acid of at least 2: 1. 4. The oil according to claim 1, characterized in that as the basic alkali metal salt contains a sulfonic acid salt of the general formula
R _x - T - (SO ₃ H) _y or R ¹ - (SO ₃ H) _r ,
where R, R ¹ independently from each other, is an aliphatic group containing not more than 60 carbon atoms;
T is an aromatic hydrocarbon;
x is 1 to 3;
r, y = 1 - 2.

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