CN1049679A - Lubricating oil compositions and concentrates - Google Patents

Abstract

The present invention provides lubricating oil composition, can be used in internal combustion engine, its oxygen Chemical and wear properties are improved. More specifically, the lubricant combination The product includes three groups (A), (B) and (C) described in the detailed description point. The lubricating oil composition can also contain other additives as required, wherein Including (D), (E) and (F) set forth in the specification. in the implementation plan One, the lubricating oil composition contains the above-mentioned additives and the instructions indicate other additives in an amount sufficient for the oil to meet the API service classification All performance requirements of "SG".

Description

The present invention relates to lubricating oil compositions, and more particularly, the present invention relates to lubricating oil compositions having improved oxidation resistance and wear resistance.

Lubricating oils used in internal combustion engines, especially spark ignition diesel engines, are being continuously modified and upgraded to improve operating performance. There are many organizations, including SAE (American Society of Automatic Engineers), ASTM (formerly American Society for Testing and Materials) and API (American Petroleum Institute), as well as automated machinery manufacturers, who are constantly looking for ways to improve the performance of lubricants. Over the years, these institutional forces have promulgated and revised many standards. Due to the increasing output power and structural complexity of the above machines, the performance requirements are also increasing in order to obtain high-quality lubricating oils, which are less likely to deteriorate due to the application conditions of the lubricating oil, thus reducing wear and stains, The formation of harmful deposits such as dirt, carbonaceous materials and resinous materials, which can stick to many parts and reduce the efficiency of the machine.

In general, many classifications and requirements have been established for crankcase lubricating oils for spark ignition diesel engines, since the lubricating oils used in such applications vary widely and require different requirements. But it was only recently that commercially available high quality lubricating oils for spark ignition internal combustion engines were identified and labeled as "SF" oils. These oils are capable of meeting the performance requirements of API Application Classification SF. A new API application classification SG has now been established, and such oils will be marked "SG". SG oils must meet the operational performance requirements of API Application Classification SG, which were established to ensure that new oils of this class possess advantageous additional characteristics and operational performance beyond the performance requirements of SF oils. The SG design calls for minimizing machine wear and deposits and also minimizing the tendency of the lubricant to thicken when applied. SG oils attempt to improve operating performance and prolong life compared to all existing types of engine oils for spark ignition internal combustion engines. An additional feature of SG oils is the consideration of the requirements of the API Application Classification CC Series (Diesel Engines) into the SG index.

In order to meet the operating performance requirements of SG oil, this type of oil must successfully pass the following gasoline and diesel engine tests, which have been promulgated as standards in the industry: Ford sequence VE test; Buick sequence IIIE test; Oldsmobile sequence IID test; CRCL-38 test ; and Caterpillar single cylinder test, model 1H2. Caterpillar tests are also included in the performance requirements for lubricating oils for light duty diesel engines ("CC" series diesel engine operating performance series). If the SG classification oil is also required to meet the application requirements of heavy-duty diesel engines ("CD" series diesel engines), the oil formulation must pass the performance requirements of the more stringent Caterpillar single cylinder test, model 1G2. Procedures and performance evaluation criteria for all of these tests have been established in the industry and these tests are described in detail below.

Where fuel economy is required for SG classified lubricants, these oils must also meet Sequence IV valid oil dynamic test requirements.

Through the joint efforts of SAE, ASTM and API, a new class of diesel engine oil has also been established, and this new diesel engine oil is marked as "CE". Oils meeting the requirements of the new diesel classification CE meet additional performance requirements not found in the existing CD series, including the MackT-6, MackT-7, and CuminsNTC-400 tests.

An ideal lubricant for most applications has the same viscosity at all temperatures. Commercially available lubricants, however, differ from this ideal. Materials added to lubricants to minimize the change in viscosity with temperature are called viscosity modifiers, viscosity improvers, viscosity index improvers or VI improvers. Generally speaking, the materials that can improve the VI characteristics of lubricating oil are oil-soluble organic polymers, and these polymers include polyisobutylene, polymethacrylate (that is, copolymers of alkyl methacrylates with different chain lengths); ethylene and Copolymers of propylene; hydrogenated block copolymers of styrene and isoprene; and polyacrylates (i.e., copolymers of alkyl acrylates of different chain lengths).

Other materials have been added to lubricating oil compositions to enable the oil composition to meet various performance requirements, including dispersants, detergents, friction modifiers and corrosion inhibitors, among others. Dispersants in lubricants are used to suspend impurities, especially impurities formed during the operation of internal combustion engines, without depositing the impurities as sludge. These materials have been described in the existing literature and all exhibit viscosity-modifying and dispersing effects. One of the compounds with these two properties consists of a polymer with one or more polar groups in its main chain. These compounds are commonly prepared by grafting techniques, in which the backbone polymer reacts directly with suitable monomers.

Lubricant dispersants comprising reaction products of hydroxyl compounds or amines with substituted succinic acids or derivatives thereof have been described in the prior art literature and typical dispersants of this type are found in, for example, US Pat. When added to lubricating oils, the compositions described in the '435 patent act as dispersant/detergents and viscosity index improvers.

Lubricating oil compositions containing oil-soluble transition metal compounds are described in the prior art. Transition metal compounds are often acidic substances, such as carboxylic acids, sulfonic acids, or salts of their mixtures. For example, US4162986 (ALkaitis et al) describes transition metal salts of mixed organic carboxylic and sulfonic acids or second carboxylic acids and their use as lubricant additives. These transition metal compounds are also suggested as catalysts, anti-knock agents, combustion accelerants, smoke suppressants, curing agents, desiccants, trace element nutrient sources, and more. The hydrolyzable manganese soap stabilized by propionic acid can be used as grease, lubricating oil, fuel, etc. according to US3762890 (Collins).

Other patents and publications suggesting the use of various manganese salts and compounds as additives to lubricating oil compositions include, for example, US2364283 (Freuler), 2378820 (Amott), 2389527 (McClearY), 3346493 (LeSuer), 3827979 (Piotrowski et al), 4252659 (Ali), 4505718 (Dorer), 4633001 (Cells), 4664677 (Dorer et al), EP0271363 and EP0290457. US3941606 (Collins et al) describes hydrocarbon soluble compositions comprising polyvalent metals (such as Mn, Co and Ni) or polyvalent metal derivatives (such as MnO, CoO and NiO) together with at least one acidic compound (such as fatty acid ) and the reaction product of a mixture of at least one polyol. These compositions are said to be useful as siccatives for paint and similar coating drier compositions, fuel additives, and plastic stabilizers.

US4505718 and EP0290457 describe hydrocarbon soluble compositions comprising one or more transition metal salts of at least one organic carboxylic acid and at least one hydrocarbon soluble ashless dispersant. The transition metal salts described in these patents include manganese salts of organic acids, among them carboxylic acids, sulfonic acids and phosphoric acids. The use of overbased transition metal salts, including manganese salts of organic acids, is said to be preferred. Overbased metal salts are defined in this prior art and herein as salts in which the metal is present in excess of the stoichiometric amount required for reaction with organic acid radicals. This patent also discloses a large number of inert dispersants that can be used in combination with transition metal salts. Therein reference is made to a number of patents and certain textbook publications which describe non-inhibited dispersants. Typical dispersants used in lubricating compositions include acylated nitrogen-containing dispersants. US4505718 describes lubricating oil compositions containing from 1 to about 500 ppm transition metal (metal) and from about 5 to about 1000 ppm by weight of no dispersants.

US4664677 describes compositions comprising a mixture of manganese and copper salts. These compositions are said to be useful in fuel compositions. Compositions containing copper and manganese components are also said to serve to reduce the ignition temperature of the exhausted pellets from diesel engines when operating on said fuel.

EP 271363 describes oil soluble compositions comprising a dispersing material, a scrubbing material, a zinc dihydrocarbyl dithiophosphate anticorrosion material, and a compatibilizing material which includes a hydrocarbyl substituted metal salt of a mono- or dicarboxylic acid. A large number of dispersants have been described, including materials based on long chain hydrocarbyl substituted mono- or dicarboxylic acids, such as alpha- or beta-unsaturated carboxylic acids, generally polyolefins. Dispersants generally contain at least about 1.05 moles (eg, 1.05-1.2 moles, or more) of acid per mole of polyolefin. The number average molecular weight of the olefin polymer is usually above 700, and its range is 1500-5000. Polyisobutene is said to be a particularly suitable starting material. The dispersant can be obtained by reacting dibasic carboxylic acid materials with amines, alcohols, amino alcohols, etc. Metal salts suitable as compatibilizing materials include metal salts of Groups Ib, IIb, IIIb, IVb, Vb, VIb, VIIb and VIII of the Periodic Table of the Elements. Group Ib and IIb metals are preferred, and copper is most preferred. The salts can be basic, neutral and acidic and can be formed by reacting the reactive metal compound with any material which has at least one free carboxylate group which can act as a dispersant. Specific examples of compatible materials include copper and zinc salts of polyisobutenyl succinic anhydride.

Lubricating oil compositions for internal combustion engines having improved oxidation and wear properties are proposed herein. More specifically, the lubricating oil composition includes:

(A) a major amount of oil of lubricating viscosity;

(B) at least about 1.0% by weight of at least one carboxylic acid derivative composition prepared by mixing

(B-1) at least one substituted succinic acylating agent with

基团，其中所说琥珀酰化剂由取代基和琥珀酰基构成，而取代基衍生自聚链烯烃，所说聚链烯烃特征是Mn值为1300-约5000，Mw/Mn值为约1.5至约4.5，所说酰化剂的特征是其结构中存在平均至少1.3个琥珀酰基/当量取代基;以及(B-2) Reaction of at least one amine compound characterized by the presence in its structure of at least one

Group wherein said succinic acylating agent consists of a substituent and a succinyl group, and the substituent is derived from a polyalkene characterized by an Mn value of 1300 to about 5000 and a Mw/Mn value of about 1.5 to about 4.5, said acylating agent being characterized by the presence of an average of at least 1.3 succinyl groups per equivalent of substituents in its structure; and

(C) At least one manganese compound in an amount to provide 1 to about 500 ppm manganese metal, with the proviso that the manganese compound is not a neutral manganese dihydrocarbyl dithiophosphate.

The oil composition may also contain other desirable additives, including:

(D) at least one metal dihydrocarbyl dithiophosphate;

(E) a detergent effective amount of at least one neutral or basic alkali metal sulfonate or carboxylate; and/or

(F) at least one carboxylate derivative as defined herein.

In one embodiment, the oil compositions of the present invention contain the additives described above and other additives described in this specification in amounts such that the oil meets all of the performance requirements of API Service Classification SG.

Unless otherwise stated, in the specification and claims, the weight % of each component mentioned is calculated on a chemical basis, except for the oil component (A). For example, where it is stated that the oil composition of the present invention contains at least 2% by weight of (B), then the oil composition comprises at least 2% by weight of (B), on a chemical basis. Therefore, if component (B) is in the state of a 50 wt% oil solution, the oil composition contains at least 4 wt% oil solution.

The number of acylating agent equivalents depends on the total number of carboxylic acid functional groups present. In determining the number of equivalents of the acylating agent, those carboxyl functional groups that cannot react with the carboxylic acylating agent are excluded. In general, however, there will be one equivalent of acylating agent per hydroxyl group in these acylating agents. For example, there are two equivalents in the anhydride obtained by reacting 1 mol of olefin polymer with 1 mol of maleic anhydride. At present, it is easy to adopt conventional techniques to determine the number of carboxyl functional groups (such as acid value, saponification value), so it is easy for professionals to determine the equivalent number of acylating agent.

The equivalent weight of an amine or polyamine is the molecular weight of the amine or polyamine divided by the total number of nitrogen atoms in the molecule. Thus, ethylenediamine has an equivalent weight of half its molecular weight; diethylenetriamine has an equivalent weight of one-third its molecular weight. The equivalent weight of a commercially available polyalkenyl polyamine mixture is the %N contained in the polyamine divided by the atomic weight of nitrogen (14) and multiplied by 100; thus, the equivalent weight of a polyamine mixture containing 34% nitrogen is 41.2. Ammonia or monoamine equivalents are molecular weights.

The equivalent weight of hydroxy-substituted amine reacted with the acylating agent to form the carboxylic acid derivative (B) is its molecular weight divided by the total number of nitrogen-containing groups present in the molecule. In the present invention, in the process of preparing component (B), the hydroxyl group is ignored when calculating the equivalent weight. Thus, the ethanolamine equivalent is its molecular weight, and the diethanolamine equivalent (on a nitrogen basis) is equal to its molecular weight.

The hydroxyl-substituted amine equivalent used to form the carboxylic acid derivative (F) used in the present invention is its molecular weight divided by the number of hydroxyl groups present, ignoring nitrogen atoms. Therefore, when preparing esters such as diethanolamine, the equivalent weight is half of the molecular weight of diethanolamine.

"Substituent", "acylating agent" and "substituted succinic acylating agent" are to be understood in their ordinary sense. For example, a substituent is an atom or group of atoms that reacts to replace another atom or group in a molecule. Acylating agent or substituted succinic acylating agent refers to the compound itself, excluding unreacted reactants used to form the acylating agent or substituted succinic acylating agent.

(A) Lubricating viscous oil

The oils used to make the lubricants of the present invention may be based on natural oils, synthetic oils, or mixtures thereof.

Natural oils include animal and vegetable oils (eg, castor oil, lard) and mineral lubricating oils, such as liquid petroleum and solvent-treated or acid-treated mineral oils, of the paraffinic, naphthenic or mixed paraffinic-naphthenic type. Oils of lubricating viscosity from coal and shale can also be used. Synthetic lubricating oils include hydrocarbon oils and halogenated hydrocarbon oils, such as polymerized and copolymerized olefins (such as polybutene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutene, etc.); poly(1-hexene), poly( 1-octene), poly(1-decene), etc. and mixtures thereof; alkylbenzenes (such as dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl )-benzene, etc.), polyphenylenes (such as biphenyltriphenyl, alkylated polyphenylenes, etc.); alkylated diphenyl esters and alkylated diphenyl sulfides and their derivatives, analogs and Homologues and others.

Alkylene oxide polymers and copolymers and derivatives thereof modified by esterification, etherification, etc. of terminal hydroxyl groups constitute another class of known synthetic lubricating oils which can be used in the present invention. Examples can be given of polymerization with ethylene oxide or propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (such as methyl polyisopropylene glycol ether with an average molecular weight of about 1000, polyisopropylene glycol ether with a molecular weight of about 500-1000 Diphenyl ether of polyethylene glycol, diethyl ether of polypropylene glycol with a molecular weight of about 1000-1500, etc.) or their mono- or polycarboxylic acid esters, such as acetate, combined 3-8 carbon fatty acid esters, or tetraethyl An oil made from the 13-carbon oxyacid diester of a diol.

Another class of synthetic lubricating oils that can be used includes dicarboxylic acids (such as phthalic, succinic, alkylsuccinic, alkenylsuccinic, maleic, azelaic, suberic, sebacic, rich Malonic acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid, etc.) with various alcohols (such as butanol, hexanol, dodecanol, 2-Ethylhexanol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, azelaic acid Diisodecyl phthalate, dioctyl phthalate, didecyl phthalate, 2-eicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, 1mol decane A coordination ester formed by the reaction of acid with 2mol tetraethylene glycol and 2mol 2-ethylhexanoic acid and the like.

Esters that can be used as synthetic oils also include esters made of 5-12 carbon monocarboxylic acids and polyols and polyol ethers, such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.

Silicone oils, such as polyalkyl, polyaryl, polyalkoxy, or polyaryloxy-siloxane oils and silicate oils constitute another class of useful synthetic lubricating oils (e.g., tetraethyl silicate, silicon tetraisopropyl silicate, tetra(2-ethylhexyl) silicate, tetra(4-methylhexyl) silicate, tetra(p-tert-butylphenyl) silicate, hexyl(4-methyl- 2-pentyloxy)disiloxane, poly(methyl)siloxane, poly(methylphenyl)siloxane, etc.). Other synthetic lubricating oils include liquid esters of phosphoric acid (such as triscresyl phosphate, trioctyl phosphate, diethyl decane phosphonate, etc.), polymerized tetrahydrofuran, and the like.

The above-mentioned unrefined, refined and re-refined oils, whether natural or synthetic (and any mixture of two or more thereof), may be used in the concentrates of the present invention. Unrefined oils are oils derived directly from natural or synthetic sources without purification treatment. For example, shale oils obtained directly from dry distillation operations, petroleum oils obtained directly from first distillation or ester oils obtained directly from esterification processes without further treatment are all unrefined oils. Refined oils are similar to unrefined oils except that they have been further treated in one or more purification steps to improve one or more of their properties. Many such purification procedures are known to those skilled in the art, such as solvent extraction, hydrotreatment, second distillation, acid or base extraction, filtration, percolation and the like. Re-refined oil is obtained by refining the refined oil that has been put into use by a method similar to that of refined oil. Such re-refined oils are also known as reclaimed oils, cycle oils or reprocessed oils and often undergo additional processing to remove spent additives and oil degradation products.

(B) Carboxylic acid derivatives

Component (B) used in the lubricating oils of the present invention is at least one carboxylic acid derivative composition prepared by combining (B-1) at least one substituted succinic acylating agent with (B-2) at least Reaction of an amine compound containing at least one HN<group, wherein said succinic acylating agent consists of a substituent and a succinyl group, wherein the substituent is derived from a polyalkene characterized by an Mn value of about 1300 to about 5000 and a Mw/Mn ratio of about 1.5 to about 4.5, said acylating agents are characterized by the presence of an average of at least about 1.3 succinyl groups per equivalent of substituents in their structure. Generally, about 0.5 equivalents to about 2 moles of amine compound per equivalent of acylating agent are required for the reaction.

The carboxylic acid derivative (B) is included in the oil composition to improve its dispersibility and VI properties. Generally, about 1 to about 10 or 15 wt. % component (B) may be included in the oil composition, although the oil composition preferably contains at least 2 wt. %, and in some cases 3 wt. % or more, of component (B). .

The substituted succinic acylating agent (B-1) used to prepare the carboxylic acid derivative (B) is characterized by the presence of two groups or residues in its structure. The first group or residue, hereinafter referred to simply as "substituent group", is derived from a polyalkene. The polyalkene from which the substituents are derived is characterized by an Mn (number average molecular weight) value of from about 1300 to about 5000 and a Mw/Mn value of at least about 1.5 and higher, typically from about 1.5 to about 4.5 or from about 1.5 to about 4.0. The symbol Mw is a common code. Indicates the weight average molecular weight. Gel Permeation Chromatography (GPC) is a molecular sizing method in which the weight-average and number-average molecular weight and overall molecular weight distribution state of a polymer can be determined. In the present invention, a series of graded polymers of isobutylene and polyisobutylene are used as standards in GPC.

Techniques for determining Mn and Mw of polymers are well known and described in many books and literature. For example, polymer Mn and molecular weight distribution determinations have been described in W.W. Yan, J.J. Kirkland and D.D. Bly, "Modern Size Exclusion Liquid Chromatographs", J. Wiley & Sons, Inc., 1979.

The second group or residue in the acylating agent is hereinafter referred to as "succinyl". The structural characteristics of the succinyl group are as follows:

wherein X and X' are the same or different, provided that at least one of X and X' renders the substituted succinic acylating agent useful as a carboxylic acid acylating agent. That is, at least one of X and X' must be such that the substituted acylating agent can form an amide or amine salt with an amino compound and otherwise act as a conventional carboxylic acid acylating agent. Conventional acylation reactions in the present invention may be considered transesterification and transamidation reactions.

Thus, X and/or X' are generally -OH, -O-hydrocarbyl, -OM ⁺ , where M ⁺ represents -equivalent metal, ammonium or amine cation, -NH ₂ , -Cl, -Br, and X and X' Both are -O- to form anhydrides. The specific instance of any X or X' that is not one of the above is not critical so long as its presence does not prevent the remaining groups from entering the acylation reaction. However, it is preferred that each of X and X' should render the two carboxyl functional groups in the succinyl group (i.e. both -C(O)X and -C(O)X') accessible for acylation.

One of the unsaturated valence bonds in the group of formula I below forms a carbon-carbon bond with a carbon atom in the substituent:

All but one of such linkages are generally saturated with hydrogen, ie -H, although other types of unsaturated linkages may be saturated via similar linkages with the same or different substituents.

Substituted succinylating agents are characterized by the presence in their structure of an average of at least 1.3 succinyl groups (that is, groups corresponding to formula (I)) per equivalent of substituents. In the present invention, substituent equivalent weight is considered to be the Mn value of the polyolefin from which the substituent is derived divided by the total weight of substituents present in the substituted succinic acylating agent. Thus, if a substituted succinic acylating agent is characterized by a total weight of substituents of 40,000, and the polyalkene from which the substituents are derived has an Mn value of 2,000, then the substituted succinic acylating agent is characterized by a total equivalent weight of substituents of 20 ( 40,000/2000=20). Therefore, a particular succinylating agent must also be characterized by the presence of at least 26 succinyl groups in its structure to satisfy one of the requirements for succinylating agents used in the present invention.

Another requirement for the substituted succinic acylating agents is that the substituents must be derived from a polyolefin having a Mw/Mn value of at least about 1.5, with an upper limit generally of about 4.5, particularly suitably 1.5 to about 4.5.

Polyolefins having Mn and Mw values as described above are known in the art and can be prepared conventionally. For example, some of these polyalkenes are described and exemplified in US 4,234,435 the disclosure of which is incorporated herein by reference. Several of these polyalkenes, especially polybutene, are commercially available.

In a preferred embodiment, the succinyl group is generally of the formula:

Wherein R and R' are independently selected from -OH, -Cl, -O-lower alkyl, and together, R and R' are -O-. In the latter case, the succinyl group is a succinic anhydride group. All succinyl groups in a particular succinylating agent need not be the same, but can be. Preferably, the succinyl group is of the formula

and mixed bases of (III(A)) and (III(B)). It is within the knowledge of the skilled artisan to provide substituted succinic acylating agents in which the succinyl groups are the same or different and can be obtained by conventional techniques, such as treating the substituted succinic acylating agent itself (e.g., hydrolyzing the anhydride to the free acid or converting the free acid to Conversion to acid chlorides employing thionyl (di)chloride) and/or selection of appropriate maleoyl or fumaryl reactants.

As stated above, the minimum number of succinyl groups present is 1.3 per equivalent of substituent. The maximum number generally does not exceed 4.5. Generally, this minimum is about 1.4 succinyl groups per equivalent of substituents. Based on this minimum, the range formed is at least 1.4 to about 3.5, more specifically about 1.4 to about 2.5 succinyl groups per equivalent substituent.

In addition to the preference for substituted succinyl groups, where preference depends on the number and type of succinyl groups present per equivalent of substituent, there is another preference which depends on the type and character of the polyalkene from which the substituent is derived.

For example, with respect to Mn values, a minimum value of about 1300 and a maximum value of about 5000 are preferred, while Mn values ranging from about 1500 to about 5000 are also preferred. More preferably the Mn value is between about 1500 and about 2800. Most preferably the Mn value ranges from about 1500 to about 2400.

Before further discussion of the polyalkenes from which the substituents are derived, it should be noted that these preferred properties of the succinic acylating agent are intended to be understood both independently and interrelatedly. This is understood independently in the sense that eg a preference for a minimum of 1.4 or 1.5 succinyl groups/equivalent of substituents is not limited to the preferred Mn or Mw/Mn values. What is understood to be relevant is that, for example, when a minimum of 1.4 or 1.5 succinyl groups is preferred in combination with more preferred values of Mn and/or Mw/Mn, this combination of preferred ranges does in fact show that this A more preferred embodiment of the invention. Thus, each parameter is intended to stand alone when considering a specific parameter, but may also be considered in combination with other parameters to indicate a more preferred solution. Therefore, unless otherwise expressly or explicitly stated to the contrary, descriptions herein of preferred values, ranges, ratios, reactants, etc., adopt this same concept throughout.

In one embodiment, when the Mn of the polyalkene is at the low end of the range, such as about 1300, then the ratio of succinyl groups to substituents derived from the polyalkene in the acylating agent is preferably above the Mn of, for example, 1500 time ratio. On the contrary, where the Mn of the polyolefin is high, such as 2000, the ratio may be lower than that of the polyolefin having an Mn of, for example, 1500.

Polyolefins from which substituents can be derived are homopolymers and copolymers of 2 to about 16 carbon, typically 2 to about 6 carbon, polymerizable olefin monomers. Two or more olefin monomers in the copolymer are copolymerized according to known conventional methods to form units derived from the two or more olefin monomers in the structure. Thus, "copolymer" herein includes di-copolymers, ter-copolymers, tetra-copolymers, and the like. It will be clear to those skilled in the art that polyalkenes from which substituents are derived are generally referred to as "polyolefins".

Olefin monomers forming polyalkenes are polymerizable olefin monomers characterized by the presence of one or more ethylenically unsaturated groups (ie >C=C<), that is to say monoolefin monomers such as ethylene, Propylene, 1-butene, isobutene, and 1-octene or polyene monomers (typically diene monomers), such as 1,3-butadiene and isoprene.

These olefin monomers are generally polymerizable terminal olefins, that is to say olefins are characterized by the presence of the group >C═CH ₂ in their structure. However, polymerizable internal olefin monomers (sometimes referred to in the literature as mesoolefins) are characterized by the presence of the following groups in their structure:

Polyalkenes can also be formed from these monomers. When internal olefin monomers are used, they are generally used with terminal olefins to form copolymerized polyolefins. In the present invention, when a specific polymerized olefin monomer is classified into both terminal olefin and internal olefin, it will be considered as terminal olefin. Thus, 1,3-pentadiene (i.e., piperylene) is considered a terminal olefin in the present invention.

Certain substituted succinic acylating agents (B-1) for use in preparing carboxylate (B) are known in the art and are described, for example, in US 4,234,435, the disclosure of which is incorporated herein by reference. The acylating agents described in '435 are characterized as having substituents derived from polyalkenes having Mn values of from about 1300 to about 5000 and Mw/Mn values of from about 1.5 to about 4.

Generally preferred are aliphatic polyolefins free of aromatic ring groups and cycloaliphatic groups. Within this general preferred range, more preferred are polyolefins derived from homopolymers and copolymers of terminal olefins of 2 to about 16 carbon atoms. This more preferred range is limited by the proviso that, while generally preferred are interpolymers of terminal olefins, optionally containing from about up to 40% interpolymers of polymer monomers derived from internal olefins of up to about 16 carbon atoms. Polymers are also preferred. A more preferred group of polyolefins are selected from homopolymers and copolymers of terminal olefins containing 2 to about 6 carbon atoms, more preferably 2 to 4 carbon atoms. However, another group of preferred polyolefins are the latter group of more preferred polyolefins which optionally contain up to about 25% of polymer monomers derived from internal olefins containing up to about 6 carbon atoms.

Although, the preparation of polyolefins meeting the various Mn and Mw/Mn requirements as described above is well known to those of ordinary skill in the art and does not form part of the present invention. Techniques known to those skilled in the art are employed including control of polymerization temperature, selection of the amount and type of polymerization initiator and/or catalyst, use of chain terminating groups during polymerization, and the like. Other conventional techniques such as stripping (including vacuum stripping) of very light components and/or oxidative or mechanical degradation of high molecular weight polyolefins to produce low molecular weight polyolefins can also be used.

In preparing the substituted succinic acylating agent of the present invention, one or more of the above polyolefins are reacted with one or more of the maleyl or fumaryl reactants of the following general formula,

X(O)C-CH=CH-C(O)X' (Ⅳ)

wherein, X and X' are as defined in Formula I above. Preferred maleoyl and fumaryl reactants are one or more compounds corresponding to the following formulae,

RC(O)-CH=CH-C(O)R' (Ⅴ)

wherein, R and R' are as defined in Formula II above. Generally speaking, said maleyl or fumaryl reactant is maleic acid, fumaric acid, maleic anhydride or a mixture of two or more thereof. Maleyl reactants are generally preferred over fumaryl reactants because the former are more readily available and are generally easier to react with the polyolefin (or derivative thereof) to prepare the substituted succinic acylating agents of this invention. Particularly preferred reactants are maleic acid, maleic anhydride and mixtures thereof. Maleic anhydride is typically used due to its availability and ease of reaction.

Examples of patents describing various methods of preparing useful acylating agents include US 3,215,707 (Rense); US 3,219,666 (Norman et al); US 3,231,587 (Rense); US 3,912,764 ( Palmer); US 4,110,349 (Cohen); and US 4,234,435 (Meinhardt et al); and U.K. 1,440,219. The disclosures of these patents are incorporated herein by reference.

For simplicity, the term "maleyl reactant" is used below. When used, the term should generally be understood as being selected from the group consisting of maleoyl and fumaryl acidic reactants corresponding to formulas (IV) and (V), including mixtures of these reactants.

基的氨基化合物反应。The above-mentioned acylating agent is an intermediate in the process of preparing the carboxylic acid derivative composition (B), and said preparation process includes making (B-1) one or more acylating agents and (B-2) at least one other characterized by the presence in its structure of at least one

base amino compound reaction.

基的氨基化合物（B-2）可以是一种单胺或多胺化合物。两种或多种氨基化合物的混合物可以用于与一种或多种本发明的酰化剂的反应中。优选的是所说的氨基化合物含有至少一个伯氨基（即，-HN₂），更优选的是所说的胺为一种多胺，特别是含有至少两个-NH-基的多胺，其中之一或两者为伯胺或仲胺。所说的胺可以是脂族的、环脂族的、芳香族的或杂环的胺。这种多胺不仅可以使羧酸衍生组合物相对于由单胺衍生的衍生组合物而言作为分散剂/去垢添加剂更有效，而且这些优选的多胺还可以羧酸衍生组合物显示出更加突出的V.I.改进性能。characterized by the presence in its structure of at least one

The base amino compound (B-2) may be a monoamine or polyamine compound. Mixtures of two or more amino compounds may be used in the reaction with one or more acylating agents of the invention. Preferably said amino compound contains at least one primary amino group (i.e. _-HN2 ), more preferably said amine is a polyamine, especially a polyamine containing at least two -NH- groups, wherein One or both are primary or secondary amines. The amines may be aliphatic, cycloaliphatic, aromatic or heterocyclic amines. Not only do such polyamines allow carboxylic acid-derived compositions to be more effective as dispersant/detergency additives relative to monoamine-derived compositions, but these preferred polyamines also exhibit more effective carboxylic acid-derived compositions. Prominent VI improved performance.

The alkylenepolyamines among the preferred amines include polyalkylenepolyamines. Said alkylene polyamines include compounds corresponding to the following formula (VI),

Wherein, n is 1 to 10; each ^R3 is independently a hydrogen atom, a hydrocarbon group, or a hydroxyl-substituted or amine-substituted hydrocarbon group having up to about 30 atoms, or two ^R3 groups on different nitrogen atoms can be connected together form a U group, provided that at least one ^R3 group is a hydrogen atom and U is an alkylene group of about 2 to 10 carbon atoms. Preferred U is ethylene or propylene. Particularly preferred are alkylenepolyamines wherein each ^R3 is hydrogen or an amino substituted hydrocarbyl group, with ethylenepolyamines and mixtures thereof being most preferred. Typically n will have an average value from about 2 to about 7. Such alkylene polyamines include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines, heptylene polyamines, and the like. Also included are higher homologues of these amines and related aminoalkyl-substituted piperazines.

Alkylene polyamines useful in the preparation of said carboxylic acid derivative composition (B) include ethylenediamine, triethylenetetramine, propylenediamine, trimethylenediamine, hexamethylenediamine Amine, Decamethylenediamine, Octamethylenediamine, Bis(heptamethylene)triamine, Tripropylenetetramine, Tetraethylenepentamine, Trimethylenediamine, Pentaethylenehexaamine Amines, bis(trimethylene)triamine, N-(2-aminoethyl)piperazine, 1,4-bis(2-aminoethyl)piperazine, etc. Higher homologues obtained by condensation of two or more of the aforementioned alkylene amines are useful as well as mixtures of two or more of any of the aforementioned polyamines.

For reasons of cost and efficiency, the ethylene polyamines described above are most useful. This polyamine is described in detail in "Diamines and Higher Amlnes" in The Encyclopedia of Chemical Technology, Second Edition, Kink and Othmer, Volume 7, Pages 27-39, Interscience Publishers, Division of John Wiley and Sons, 1965, will The disclosure of useful polyamines therein is incorporated herein by reference.

Such compounds are most conveniently prepared by reacting an alkyl chloride with ammonia or ethyleneimine with a ring opener such as ammonia, or the like. These reactions produce somewhat complex mixtures of alkylene polyamines, including cyclic condensates such as piperazine. Said mixtures are particularly useful in the preparation of carboxylic acid derivative compositions (B) useful in the present invention. On the other hand, quite satisfactory products can also be obtained by using pure alkylene polyamines.

Other useful polyamine mixtures are those obtained by stripping the polyamine mixtures described above. In this case, after removal of low molecular weight polyamines and volatile contaminants from the alkylenepolyamine mixture, the residue remaining is often referred to as "polyamine substrate". In general, the alkylenepolyamine substrates are characterized as containing less than 2%, usually less than 1%, by weight, of materials boiling below about 200°C. In the case of ethylene polyamine substrates, which are readily available and have been found to be very useful, such substrates contain less than about 2% by weight of total diethylenetriamine (DETA) or triethylene Tetramine (TETA). A typical sample of this ethylene polyamine substrate is obtained from the Dow Chemical Company under the trademark "E-100", which has a specific gravity of 1.0168 at 15.6°C, contains 33.15% nitrogen by weight, and has a viscosity of 121 centistokes at 40°C. Gas chromatographic analysis of this sample indicated that it contained approximately 0.93% "light components" (most likely DETA), 0.72% TETA, 21.74% tetraethylenepentamine and 76.61% pentaethylenehexamine and higher homologues (by weight). These alkylenepolyamine substrates include cyclic condensates such as piperazine and higher homologues such as diethylenetriamine, triethylenetetramine, and the like.

Other polyamines which can be reacted with the acylating agent (B-1) according to the invention are described, for example, in U.S. 3,219,666 and U.S. 4,234,435, referring to those patents which can be reacted with the acylating agent to form the present invention. The disclosure of the amines of the inventive carboxylic acid derivatives (B) is incorporated herein by reference.

The carboxylic acid derivative composition (B) formed from the above-mentioned acylating agent (B-1) and amino compound (B-2) includes acylated amines including amine salts, amides, imines and imidazolines and their mixture. In order to prepare carboxylic acid derivatives from said acylating agent and amino compound, one or more acylating agents and one or more amino compounds are heated, if necessary, in a usually liquid, relatively inert organic liquid solvent/ Heating in the presence of a diluent, the heating temperature ranges from about 80°C to the decomposition point (wherein the decomposition point is as defined above), but usually from about 100°C to about 300°C (if the decomposition point is not exceeded at 300°C if). Typically temperatures from about 125°C to about 250°C are used. The acylating agent is reacted with the amino compound in an amount sufficient to provide from about half an equivalent to about 2 moles of the amino compound per equivalent of the acylating agent.

Since the acylating agent (B-1) can react with the amino compound (B-2) in the same manner as the high molecular weight acylating agent in the prior art reacts with the amine, US3,172,892, US3,219, 666, U.S. 3,272,746 and U.S. 4,234,435 are incorporated herein by reference for their disclosures concerning the reaction of acylating agents with the above amino compounds.

In order to produce carboxylic acid-derived compositions with viscosity-modifying capabilities, it is generally necessary to react an acylating agent with a polyfunctional amine reactant. For example, polyamines having two or more primary and/or secondary amino groups are preferred. However, it is clear that not all amino compounds reactive with acylating agents are necessarily polyfunctional. Combinations of monofunctional and polyfunctional amino compounds can therefore be used.

In one embodiment, the acylating agent is reacted with from about 0.70 equivalents to less than 1 equivalent (eg, about 0.95 equivalents) of the amino compound per equivalent of acylating agent. The lower limit may be 0.75 or even 0.80 to about 0.90 or 0.95 equivalents of amino compound per equivalent of acylating agent. Thus, a narrower range of equivalents of acylating agent (B-1) to amino compound (B-2) may be from about 0.70 to about 0.90, or about 0.75 to about 0.90, or about 0.85. It appears that, at least in some cases, when the equivalent of amino compound per equivalent of acylating agent is about 0.75 or less, the effectiveness of the carboxylic acid derivative as a dispersant is reduced. In one embodiment, the relative amounts of acylating agent and amine are preferably such that the carboxylic acid derivative contains no free carboxyl groups.

In another embodiment, about 1.0 to about 1.1 or up to about 1.5 equivalents of the amino compound are reacted per equivalent of acylating agent. Increased amounts of amino compounds may also be used.

The amount of the amino compound (B-2) reacted with the acylating agent within the above range also depends partly on the number and kind of nitrogen atoms present. For example, a polyamine containing one or more _-NH2 groups reacts with a given amount of acylating agent in a smaller amount than a polyamine having the same number of hydrogen atoms and containing fewer or no _-NH2 groups . One _-NH2 group can react with two -COOH groups to form an imide. If only secondary nitrogen is present in the amine compound, each >NH group can react with only one -COOH group. Accordingly, the amount of polyamine to be reacted with the acylating agent to form the carboxylic acid derivative of the present invention within the above range can be determined by the number and type of nitrogen atoms in the polyamine (i.e., _-NH2 , >NH, and >N-). Decide.

In addition to the relative amounts of acylating agent and amino compound used to form the carboxylic acid derivative composition (B), other characteristics of the carboxylic acid derivative composition used in the present invention are the Mn and Mw/ The Mn value and the presence of at least 1.3 succinyl groups per equivalent weight of substituents in the acylating agent. When all these properties are present in the carboxylic acid derivative composition (B), the lubricating oil composition of the present invention exhibits new and improved properties, and this lubricating oil composition is characterized by improved performance in internal combustion engines performance.

The ratio of succinyl groups to the equivalent weight of substituents present in the acylating agent can be determined from the saponification value of the reaction mixture at the end of the reaction, which has been corrected to take into account The unreacted polyalkylene in the embodiment generally refers to the filtrate or the residue) and asks for the saponification value with the ASTM D-94 method. The formula for calculating the above ratio from the saponification value is as follows:

Ratio = ((Mn) (corrected saponification value))/(112, 200-98 (corrected saponification value))

The corrected saponification value is obtained by dividing the saponification value by the percent polyalkylene reacted. For example, if 10% of the polyalkylene is unreacted and the filtrate or residue has a saponification value of 95, the corrected saponification value is 95 divided by 0.90 or 105.5.

The preparation of the acylating agent is described in the following Examples 1 to 3, and the preparation of the carboxylic acid derivative composition (B) is described in the following Examples B-1 to B-26. In the following examples, as well as everywhere in the specification and claims, all percentages and parts are by weight, temperatures are in degrees Celsius, and pressures are at or near atmospheric unless otherwise indicated.

Acylating agent

Example 1

A mixture of 510 parts (0.28 mol) of polyisobutene (Mn=1845; Mw=5325) and 59 parts (0.59 mol) of maleic anhydride was heated to 110°C. The mixture was heated to 190°C over 7 hours, during which time 43 parts (0.6 moles) of gaseous chlorine were added subsurface. An additional 11 parts (0.16 moles) of chlorine were added over a period of 3.5 hours at 190-192°C. The reaction mixture was stripped by heating at 190-193°C with nitrogen blowing for 10 hours. The residue was the desired polyisobutylene-substituted succinic acylating agent having a saponification equivalent weight of 87 (as determined by ASTM D-94).

Example 2

A mixture of 1000 parts (0.495 moles) of polyisobutene (Mn=2020; Mw=6049) and 115 parts (1.17 moles) of maleic anhydride was heated to 110°C. The mixture was heated to 184°C over 6 hours, during which time 85 parts (1.2 moles) of gaseous chlorine were added subsurface. An additional 59 parts (0.83 moles) of chlorine were added over 4 hours at 184-189°C. The reaction mixture was stripped by heating and blowing nitrogen at 186-190° C. for 26 hours. The resulting residue was the desired polyisobutylene-substituted succinic acylating agent having a saponification equivalent weight of 87 (as determined by ASTM D-94).

Example 3

A mixture of parts of polyisobutylene chloride and 345 parts of maleic anhydride was heated to 200°C within 0.5 hours, wherein polyisobutylene chloride was prepared by adding 3000 parts of polyisobutylene (Mn=1696; Mw=6594) was prepared by adding 251 parts of gaseous chlorine. The resulting reaction mixture was maintained at 200-224°C for 6.33 hours, then stripped at 210°C under vacuum and filtered. The filtrate obtained was the desired polyisobutylene-substituted succinic acylating agent with a saponification equivalent value of 94, (measured by ASTM D-94 method).

Carboxylic acid derivative composition (B)

Example B-1

By adding 10.2 parts (0.25 equivalents) of 10.2 parts (0.25 equivalents) of the substituted succinic acylating agent prepared in Example 1 to 113 parts of mineral oil and 161 parts (0.25 equivalents) at 138 ° C, each molecule has about 3 to 10 A mixture was prepared from a commercial mixture of ethylene polyamines containing nitrogen atoms. The resulting reaction mixture was heated to 150° C. over 2 hours and stripped with nitrogen bubbles. Filtration of the reaction mixture gave the product as an oily liquid.

Example B-2

To 1067 parts of mineral oil and 893 parts (1.38 equivalents) of the substituted succinic acylating agent prepared in Example 2 at 140-145°C was added 57 parts (1.38 equivalents) of Atomic commercial mixtures of ethylene polyamines were used to prepare a mixture. The resulting reaction mixture was heated to 155° C. over 3 hours and stripped by bubbling nitrogen. The resulting reaction mixture was filtered and the filtrate obtained was the desired product.

Example B-3

A mixture containing 1132 parts of mineral oil and 709 parts (1.2 equivalents) of the substituted succinic acylating agent prepared in Example 1 was prepared, and then slowly heated from a dropping funnel at 130-140° C. for nearly 4 hours. To the above mixture was added slowly 56.8 parts of piperazine (1.32 eq) in 200 parts of water. Allow it to continue heating to 160°C to remove the water. The resulting mixture was maintained at 160-165°C for an additional hour and then cooled overnight. After reheating the mixture to 160° C., the mixture was kept at this temperature for 4 hours. 270 parts of mineral oil are added and the mixture is filtered through a filter aid at 150°C. The resulting filtrate was the desired product containing 65% oil and 0.65% nitrogen (0.86% theoretical).

Example B-4

A mixture of 1968 parts of mineral oil and 1508 parts (2.5 equivalents) of a substituted succinic acylating agent prepared in Example 1 was heated to 145°C) and then 125.6 parts (3.0 equivalents) of A commercial mixture of ethylene polyamines was used as in Example B-1 while maintaining the temperature of the reaction mixture at 145-150°C. The resulting reaction mixture was stirred at 150-152°C for 5.5 hours while bubbling nitrogen. The resulting mixture was filtered at 150°C with a filter aid. The filtrate obtained was the desired product containing 55% oil and 1.2% nitrogen (1.17% theoretical).

Example B-5

A mixture of 1503 parts of mineral oil and 1220 parts (2 equivalents) of a substituted succinic acylating agent as prepared in Example 1 was heated to 110°C and 120 parts (3 equivalents) were added over a period of about 50 minutes. A commercial mixture of ethylene polyamines of the type used in Example B-1. The resulting mixture was stirred at 110°C for an additional 30 minutes, then the temperature was increased to about 151°C and maintained at this temperature for 4 hours. A filter aid is added and the mixture is filtered. The filtrate obtained was the desired product containing 53.2% oil and 1.44% nitrogen (1.49% theoretical).

Example B-6

A mixture of 3111 parts of mineral oil and 844 parts (21 equivalents) of a commercial mixture of ethylene polyamines as used in Example B-1 was heated to 140°C and then when the temperature was raised to about 150°C , 3885 parts (7.0 equivalents) of a substituted succinic acylating agent prepared in Example 1 were added over about 1.75 hours. While bubbling nitrogen gas, the reaction mixture was maintained at 150-155°C for about 6 hours, then the reaction mixture was filtered at 130°C using a filter aid. The filtrate obtained was the desired product containing 40% oil and 3.5% nitrogen (3.78% theoretical).

Example B-7

By adding 18.2 parts (0.433 equivalents) of the substituted succinic acylating agent prepared in Example 2 to 392 parts of mineral oil and 348 parts (0.52 equivalents) at 140°C, containing about 3 to 10 nitrogens per molecule Atomic commercial mixtures of ethylene polyamines were used to prepare a mixture. The reaction mixture was heated to 150° C. over 1.8 hours and stripped by bubbling nitrogen. The reaction mixture was filtered to give a filtrate which was the desired product containing 55% oil.

Example B-8

To an appropriately sized flask equipped with a stirrer, nitrogen inlet tube, addition funnel, and Dean-stark collector/condenser, were charged 2483 parts (4.2 equivalents) of the acylating agent as described in Example 3 and 1104 parts oil mixture. The mixture was heated to 210°C while slowly bubbling nitrogen gas through the mixture. At this temperature, 134 parts (3.14 equivalents) of ethylene polyamine substrate were added slowly over a period of about 1 hour. The temperature was maintained at about 210°C for 3 hours, then 3688 parts of oil were added to bring the temperature down to 125°C. After standing at 138°C for 17.5 hours, the mixture was filtered through celite to provide the desired acylated amine substrate containing 65% oil.

Example B-9

A mixture of 3660 parts (6 equivalents) of the substituted succinic acylating agent as prepared in Example 1 in 4664 parts of diluent oil was prepared and the mixture was heated at about 110°C and nitrogen gas was bubbled through the mixture . To this mixture was then added over a period of 1 hour 210 parts (5.25 equivalents) of a commercial mixture of ethylene polyamines containing about 3 to 10 nitrogen atoms per molecule and the mixture was maintained at 110°C for 0.5 hour. After heating at 155°C for 6 hours while removing water, a filtrate was added and the reaction mixture was filtered at about 150°C. The filtrate obtained was the desired product.

Example B-10

The general procedure of Examples B-9 was repeated except that 0.8 equivalents of the substituted succinic acylating agent prepared in Example 1 was reacted with 0.67 equivalents of a commercial mixture of ethylene polyamines. The product obtained in this way was an oily liquid containing 55% diluent oil.

Example-11

The general procedure of Example B-9 was repeated except that the polyamine used in this example was a mixture of one equivalent of alkylene polyamines comprising 80% ethylene oxide from Union Carbide. based polyamine substrate and 20% of a commercial mixture of ethylene polyamines of the empirical formula corresponding to diethylenetriamine. The polyamine blend is characterized by an equivalent weight of about 43.3.

Example B-12

The general procedure of Example B-9 was repeated, except that the polyamine used in this example included a mixture containing 80 parts of ethylene polyamine substrate from Dow Chemical Company and 20 parts of diethylenetriamine. This mixture of amines has an equivalent weight of about 41.3.

Example B-13

A mixture of 444 parts (0.7 equivalents) of the substituted succinic acylating agent prepared in Example 1 and 563 parts of mineral oil was prepared, and the mixture was heated to 140°C and then kept at 140°C for 1 22.2 parts (0.58 equivalents) of an ethylene polyamine mixture of the empirical formula corresponding to triethylenetetramine were added in 1 hour. Nitrogen gas was blown into the mixture while it was heated to 150°C, and the temperature was maintained at that temperature for 4 hours while removing water. The mixture is then filtered through a filter aid at about 135°C to give a filtrate of the desired product containing about 55% mineral oil.

Example B-14

A mixture of 422 parts (0.7 equivalents) of the substituted succinic acylating agent prepared in Example 1 and 188 parts of mineral oil was prepared and heated to 210°C, then 22.1 parts (0.53 equivalents) of The Dow Chemical Company's commercial mixture of ethylene polyamine substrates (E-100) was sparged with nitrogen. Its temperature was then increased to about 210-216°C and maintained at this temperature for 3 hours. 625 parts of mineral oil are added and the mixture is maintained at 135°C for about 17 hours. The mixture is then filtered to give a filtrate of the desired product containing 65% oil.

Example B-15

A mixture of 414 parts (0.71 equivalents) of the substituted succinic acylating agent prepared in Example 1 and 184 parts of mineral oil was prepared and the mixture was heated to about 80°C, and 22.4 parts (0.534 equivalents) of honey amine. The mixture was heated to 160°C over about 2 hours and maintained at this temperature for 5 hours. After cooling overnight, the mixture was heated to 170°C over 2.5 hours and to 215°C over 1.5 hours. The mixture was maintained at about 215°C for 4 hours and at about 220°C for 6 hours. After cooling overnight, the reaction mixture was filtered through a filter aid at 150°C. The resulting filtrate was the desired product containing 30% mineral oil.

Example B-16

A mixture of 414 parts (0.71 equivalents) of the substituted acylating agent prepared in Example 1 and 184 parts of mineral oil was heated to 210°C and then 21 parts were added over 0.5 hours while maintaining the temperature at about 210-217°C. (0.53 equivalents) of the empirical formula corresponds to the commercial mixture of ethylene polyamines of tetraethylenepentamine. After the polyamine addition was complete, the mixture was maintained at 217°C for 3 hours while bubbling nitrogen. 613 parts of mineral oil were added and the mixture was maintained at about 135°C for 17 hours and allowed to filter. The resulting filtrate was the desired product containing 65% mineral oil.

(C) Manganese compounds

Lubricating oil compositions of the present invention contain at least one manganese compound in an amount sufficient to provide from 1 to about 500 ppm manganese metal, provided that said manganese compound is not a neutral manganese dihydrocarbyl dithiophosphate. In one embodiment, the manganese compound is soluble in the lubricating oil compositions of the present invention. Said manganese compounds (C) are generally salts of acidic substances, especially salts of carboxylic acids, sulfonic acids and phenols. In another embodiment, the amount of manganese compound in the oil provides from about 50 to about 300 ppm manganese metal. The manganese compound may be a neutral manganese compound or an "overbased" manganese compound, and overbased manganese compounds are generally preferred. As used in the present invention, the term "overbased" means that the manganese compound contains more manganese than is required to neutralize the acid. Thus, overbased basic manganese salts contain more than 1 equivalent of metal per equivalent of acid. Overbased manganese salts of acids such as carboxylic acids, sulfonic acids, phenols and phosphoric acids are well known and described in the prior art. See, for example, US 4,162,986 (Alkaitis); US 3,827,979 (Piotrowski et al); US 3,312,618 (Lesuer et al); US 2,616,904 and 2,616,905 (Aseff et al); and US4,252,659 (Ali). It should be noted that although neutral manganese dihydrocarbyl dithiophosphates are not included in the lubricating oil compositions of the present invention, overbased manganese dihydrocarbyl dithiophosphates may serve as useful manganese compounds.

Overbased manganese salts are preferred because they provide high manganese content while maintaining solubility. Therefore, overbased manganese salts are useful for introducing high amounts of metal while allowing only metallic manganese to be introduced into the lubricating oil. Minimizing the amount of acidic compounds that act as a carrier is advantageous. It should be noted that overbased manganese compounds have a metal to acid molar ratio greater than 1:1, and generally greater than 2:1. The molar ratio of metal to acid in an overbased compound is generally referred to as the metal ratio.

The organic acids used in the preparation of said manganese salts contain carbon atoms and include carboxylic acids, especially carboxylic acids containing 1 to about 30 carbon atoms, sulfonic acids, especially those containing one or more carbon atoms having 4 to about 22 sulfonic acids, phenolic compounds, especially hydrocarbon-substituted phenols with alkyl-substituted aromatic ring structures of 3 carbon atoms; and when said manganese compound is an overbased compound, its structure contains one or more Phosphorous compounds having an organic radical of 1 to about 30 or more carbon atoms. All such acidic substances are well known in the art.

The carboxylic acids may be aliphatic or aromatic mono- or polycarboxylic acids. Monocarboxylic acids include C _1-7 lower acids (acetic acid, propionic acid, etc.) and C ₈₊ higher acids (for example, octanoic acid, capric acid, etc.) and known fatty acids with about 12 to 30 carbon atoms. The fatty acids are usually a mixture of straight chain and branched chain acids, for example, the mixture contains from 5% to about 30% straight chain acids and from about 70% to about 95% by mole branched chain acids. Other commercially available fatty acids containing higher proportions of straight chain acids are also useful. Mixtures resulting from the dimerization of unsaturated fatty acids may also be used.

Higher carboxylic acids include known dicarboxylic acids obtained by alkylating maleic anhydride or its derivatives. The products of these reactions are hydrocarbon substituted succinic acids, anhydrides, and the like. Low molecular weight dicarboxylic acids, such as polymethylene bridging acids (glutaric acid, adipic acid, etc.) can also be used to produce the salts of the invention as well as low molecular weight substituted succinic acids, e.g., tetrapropenylsuccinic acid Acids and their homologues of acids up to about C ₃₀ substituted.

High molecular weight substituted succinic anhydrides, acids and homologues as described in the preparation of dispersants (B) are also useful in producing the manganese salts of this invention.

The aliphatic acids generally contain at least 8 carbon atoms, preferably at least 12 carbon atoms. Typically they have no greater than about 400 carbon atoms. In general, the acid is more soluble in oil for any given carbon atom content if the aliphatic carbon chain of the acid is branched. The cycloaliphatic and aliphatic carboxylic acids may be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, alpha-linolenic acid, propylene-tetramer substituted succinic acid, behenic acid, isostearic acid, nonanoic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, acid, oleic acid, ricinoleic acid, undecanoic acid, dioctylcyclopentane carboxylic acid, myristic acid, dilauryl decalin carboxylic acid, stearyl-octahydroindane carboxylic acid, palmitic acid, ammonium Commercially available mixtures of one or more carboxylic acids such as tall oil acid, abietic acid and the like.

Said manganese salts may also be oil-soluble organic sulfuric acids such as sulfonic acid, sulfamic acid, thiosulfonic acid, sulfenic acid, sulfinic acid, partial ester sulfuric acid, sulfurous acid and thiosulfuric acid. Typically they are salts of carboxylic or aliphatic sulfonic acids.

Examples of such carbocyclic or aliphatic sulfonic acids are petroleum sulfonic acid, bright stock sulfonic acid; from lubricating oil components (Saykolt viscosity is about 100 seconds at 100°F, about 200 seconds at 210°F ) derived from sulfonic acids; petrolatum sulfonic acids; mono- or polywax-substituted sulfonic acids or Sulfonic acids; other substituted sulfonic acids such as alkylbenzenesulfonic acids (wherein the alkyl group has at least 8 carbon atoms), hexadecylphenylmonosulfuric acid, bis(hexadecyl)thianthracene disulfonic acid acids, dilauryl-β-naphthylsulfonic acid, didecanoylnitronaphthalenesulfonic acid and alkarylsulfonic acids such as dodecylbenzene (substrate)sulfonic acid. Dodecylbenzene (substrate) is primarily a mixture of mono- and didodecanylbenzene.

Said aliphatic sulfonic acid includes paraffin sulfonic acid, unsaturated paraffin sulfonic acid, hydroxyl substituted paraffin sulfonic acid, hexapropylene sulfonic acid, tetrapentamethylene sulfonic acid, polyisobutylene sulfonic acid (wherein polyisobutylene Containing 20 to 7000 or more carbon atoms), chlorine-substituted paraffin sulfonic acid, nitroparaffin sulfonic acid, etc.; cycloaliphatic sulfonic acids, for example, petroleum naphthenic sulfonic acid, hexadecyl cyclopentyl sulfonic acid , lauryl cyclohexylsulfonic acid, bis(di-isobutyl)cyclohexylsulfonic acid, single or polywax substituted cyclohexylsulfonic acid, etc.

More details about the sulfonic acids used here can be found in US2,616,905; US3,027,325; US3,312,618; US3,350,308; US3,471,403; , 595,790; US3,798,012; US3,829,381; US4,100,083; and US4,326,972. The relevant contents of these patents are incorporated herein by reference.

Neutral and overbased manganese salts of phenolic compounds (phenates) are also useful in the lubricating oils of the present invention. Hydrocarbon substituted phenols, sulfurized phenols, and alkylene (eg, methylene) coupled phenols are also useful. Mixtures of phenols may be used to prepare the manganese salts, or mixtures of separately prepared manganese phenoxides may be included in the lubricating oils of this invention.

Typically, the organic acids used to prepare the manganese salts of the present invention are carboxylic acids, sulfonic acids or mixtures thereof. Particularly useful manganese salts are described in U.S. Patent 4,162,986 to Alkaitis et al., which is hereby incorporated by reference for its disclosure of manganese compounds, particularly manganese salts of organic acids, useful in the compositions of the present invention .

It should be noted that the manganese salts used in the present invention are preferably overbased. Such salts are well known. See, for example, just cited US 4,162,986 and the following US patents, US 3,827,979; US 4,252,659; US 4,505,718 and US 4,664,677. The teachings of these patents concerning overbased manganese salts of organic acids are hereby incorporated by reference.

Particularly useful overbased manganese salts of organic acids are very strongly overbased manganese metalloorganic compositions comprising manganese oxide-manganese hydroxide-manganese carboxylate complexes in which the metal is oxidized as a nuclear metal The crystallite core of the substance is chemically bound partly to oxygen and partly to at least two different monocarboxylic acids or to a mixture of one or more monocarboxylic acids and monosulfonic acids containing at least two carbon atoms, Forming carboxyl-metal-carboxylate groups and hydroxyl-metal-sulfonate groups, at least one acid is a monocarboxylic acid containing at least 7 carbon atoms, and when the second acid is also a monocarboxylic acid, the second An acid containing a number of carbon atoms in its longest chain differing by at least two from the total number of carbon atoms in the carbon chain of another acid, at least a portion of the carboxylate and sulfonate groups being hydrogen bonded to the oxygen atoms of the core , the remaining carboxylate and sulfonate groups are unbonded and in equilibrium with the bonded acid group, the ratio of total moles of metal to total moles of organic acid is greater than 1.

These preferred compositions and their preparation are described in more detail in US 4,162,986, especially columns 8-14 of that patent. The disclosure of this patent regarding this manganese salt is hereby incorporated by reference.

Suitable overbased manganese salts high in manganese are commercially available from Mooney Chemical Company: FOA 910 ^TM Liquid Carboxylate, which contains 40% manganese metal; and CEM-ALL, which contains 12% magnesium .

Overbased manganese salts derived from phosphoric acid are also suitable for use in the lubricants of the present invention. Phosphoric acid can be represented by

Wherein R ¹ and R ² are independently hydrocarbon groups;

X ¹ , X ² , X ³ and X ⁴ are each independently oxygen or sulfur; and

a and b are both 0 or 1.

The preparation of such overbased manganese salts of phosphoric acid is described in the prior art, e.g., U.S. Patent 2,695,910 (Asseff et al). The overbased manganese salts disclosed in this patent are incorporated herein by reference.

In addition to the above-mentioned required carboxylic acid derivative dispersant (B) and manganese compound (C), the lubricant can (and usually does) contain other additives to make the lubricating oil have other satisfactory requirements in gasoline and diesel engines. performance used. These additives include antiwear additives such as metal salts of dithiophosphoric acid, detergents, other dispersants including carboxylate derivatives, and the like.

(D) Metal salts of dihydrocarbyl dithiophosphoric acid

In another embodiment, the oil composition of the present invention also contains (D) at least one metal dihydrocarbyl dithiophosphate represented by the formula

Wherein R ¹ and R ² independently represent a hydrocarbon group containing 3 to about 13 carbon atoms, M is a metal, and n is an integer whose value is equal to the valence of M.

Typically, the oil compositions of the present invention will contain varying amounts of one or more of the aforementioned metal dithiophosphates, for example about 0.01-5% or about 0.01-2%, based on the total weight of the oil composition, More usually about 0.01-1% by weight. Metal dithiophosphates are added to the lubricating oil compositions of the present invention to improve the antiwear and antioxidative properties of the oil compositions.

The hydrocarbyl groups ^R1 and ^R2 in the metal dithiophosphates of Formula VIII may be alkyl, cycloalkyl, aralkyl or alkaryl, or substantially hydrocarbyl groups of similar structure. "Substantially hydrocarbyl" means a hydrocarbyl group having substituents thereon such as ether, ester, nitro or halogen which do not materially affect the character of the hydrocarbyl group.

Examples of alkyl groups include isopropyl, isobutyl, n-butyl, sec-butyl, various pentyls, n-hexyl, methylisobutylcarbinyl, heptyl, 2-ethylhexyl, diisobutyl, Isooctyl, nonyl, behenyl, decyl, dodecyl, tridecyl, etc. Examples of lower alkylphenyl groups include xylyl, tolyl, butylphenyl, pentylphenyl, heptylphenyl and the like. Cycloalkyl groups are also suitable and they mainly include cyclohexyl and lower alkyl substituted cyclohexyl. Many substituted hydrocarbyl groups are also available, such as chloropentyl, dichlorophenyl and dichlorodecyl.

Dithiophosphoric acids from which metal salts suitable for use in the present invention are obtained are known. Examples of dihydrocarbyl dithiophosphoric acids and their metal salts, and methods for preparing such acids and salts are found, for example, in U.S. Patents 4,263,150; 4,289,635; 4,308,154 and 4,417,990. The relevant contents of these patents are hereby incorporated by reference.

Dithiophosphoric acid can be prepared by reacting phosphorus pentasulfide with an alcohol or a mixture of phenols, a mixture of phenols, or a mixture of alcohols and phenols. In the reaction, four moles of alcohol or phenol are used per mole of phosphorus pentasulfide, and the reaction is carried out at a temperature of about 50-200°C, preferably about 50-150°C. Thus, the preparation of 0,0-di-n-hexyldithiophosphoric acid involves the reaction of phosphorus pentasulfide with four moles of n-hexanol at about 100°C for about 2 hours. Hydrogen sulfide is liberated and the defined acid remains. The preparation of metal salts of the acids can be accomplished by reaction with metal oxides. Simply mixing and heating the two reactants is sufficient to initiate the reaction while obtaining a product of sufficient purity for the application of the present invention.

Metal salts of dihydrocarbyl dithiophosphoric acids suitable for use in the present invention include those containing Group I metals, Group II metals, aluminum, lead, tin, manganese, cobalt and nickel. Among the Group II metals, tin, iron, cobalt, lead, manganese, nickel and copper are preferred metals. Zinc and copper are particularly suitable metals. Examples of metal compounds that can react with the above acids include lithium oxide, lithium hydroxide, sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, silver oxide, magnesium oxide, calcium oxide, zinc hydroxide, copper oxide, hydroxide Strontium, cadmium oxide, cadmium hydroxide, barium oxide, iron carbonate, copper hydroxide, lead hydroxide, butyl tin, cobalt hydroxide, nickel hydroxide, nickel carbonate, etc.

In some instances, the incorporation of certain additives such as small amounts of metal acetate salts or acetic acid added with the metal reactants will enhance the reaction and result in improved products. For example, the formation of zinc dithiophosphate can be enhanced by using up to about 5% zinc acetate together with the required amount of zinc oxide.

In a preferred embodiment, alkyl groups ^R and ^R are selected from secondary alcohols such as isopropanol, sec-butanol, 2-pentanol, 4-methyl-2-pentanol, 2-hexanol, 3- Derived from hexanol, etc.

Particularly useful metal dithiophosphates can be prepared from dithiophosphoric acids which are themselves prepared by the reaction of phosphorus pentasulfide with mixed alcohols. In addition, using this mixture allows us to utilize less expensive alcohols that do not by themselves form oil-soluble dithiophosphoric acids. Thus, a mixture of isopropanol and hexanol can be used to prepare very effective, oil-soluble metal dithiophosphates. For the same reason, mixtures of dithiophosphoric acids can be reacted with metal compounds to form inexpensive oil-soluble salts.

The mixture of alcohols may be a mixture of different primary alcohols, a mixture of different secondary alcohols or a mixture of primary and secondary alcohols. Examples of suitable mixed alcohols include: n-butanol and n-octanol; n-pentanol and 2-ethyl-1-hexanol; isobutanol and n-hexanol; isobutanol and isoamyl alcohol; isopropanol and 4-methyl-1-hexanol; 2-pentanol; isopropanol and sec-butanol; isopropanol and isooctyl alcohol, etc. Particularly suitable mixed alcohols are secondary alcohol mixtures containing at least about 20 mole percent isopropanol, and in preferred embodiments at least 40 mole percent isopropanol.

In another embodiment, the lubricating oil composition of the present invention contains a mixture of metal dihydrocarbyl dithiophosphates in which at least one dihydrocarbyl dithiophosphoric acid, one hydrocarbyl group (D-1) is Isopropyl or sec-butyl, another hydrocarbyl group (D-2) containing at least 5 carbon atoms and at least about 20 mole percent of all hydrocarbyl groups present in (D) are isopropyl, sec-butyl or their mixtures.

In yet another embodiment, the lubricating oil composition contains a mixture of metal dihydrocarbyl dithiophosphates in which at least one of the dithiophosphoric acid one of the hydrocarbyl groups (D-1) is isopropyl or sec-butyl and the other hydrocarbyl group (D-2) contains at least 5 carbon atoms, and the lubricating oil composition contains at least about 0.05% by weight of isopropyl, sec-butyl, or mixture. In another embodiment. The lubricating oil compositions of the present invention may contain at least about 0.08% by weight of isopropyl and/or sec-butyl groups derived from (D).

The amount of isopropyl or sec-butyl in the oil or to be added to the oil can be calculated as follows:

× (2(43 ^* or 57 ^* ))/(31 ^* ) × (mol% of isopropyl or sec-butyl in the mixed hydrocarbon of (D))/100

^* 43 is the molecular weight of isopropyl.

^* 57 is the molecular weight of sec-butyl.

^* 31 is the atomic weight of phosphorus.

The mixed alcohol used in the preparation of the dithiophosphoric acid of this last embodiment comprises isopropanol, a mixture of sec-butanol or isopropanol and sec-butanol and at least one primary alcohol containing about 5 to 13 carbon atoms or a mixture of fatty alcohols. In particular, the alcohol mixture contains at least 20, 25 or 30 mole percent isopropanol and/or sec-butanol, usually about 20-90 mole percent isopropanol or sec-butanol. In a preferred embodiment, the alcohol mixture contains about 30-70 mole percent isopropanol with the balance being one or more primary fatty alcohols.

Primary alcohols that can be included in the alcohol mix are n-pentanol, isoamyl alcohol, n-hexanol, 2-ethyl-1-hexanol, isooctyl alcohol, nonanol, isodecyl alcohol, dodecanol, tridecanol wait. Primary alcohols may also contain various substituents such as halogens. For example, specific examples of suitable mixed alcohols include isopropanol/2-ethyl-1-hexanol; isopropanol/isooctanol; isopropanol/isodecyl alcohol; isopropanol/dodecanol; and isopropanol/tridecanol. In a preferred embodiment, the primary alcohol contains 6-13 carbon atoms, while the total number of carbon atoms per phosphorus atom in the desired dithiophosphate is at least 9.

The composition of dithiophosphoric acids prepared by reacting mixed alcohols (such as iproH and ^R2OH ) with phosphorus pentasulfide is actually a statistically significant mixture of dithiophosphoric acids represented by the formula:

In the present invention, the amount of two or more alcohols used to react with P ₂ S' is preferably selected so as to obtain a mixture in which the main dithiophosphoric acid is a monoisopropyl or a sec-butyl , and containing another primary or secondary alkyl group containing at least 5 carbon atoms or a mixed acid. The relative amounts of these three dithiophosphoric acids in the mixture depend in part on the relative amounts of alcohol in the mixture, steric effects, and the like.

Examples D-1 to D-6 below describe the preparation of metal dithiophosphates from mixed alcohols.

Example D-1

Dithiophosphoric acid is prepared by reacting a mixed alcohol containing 6 moles of 4-methyl-2-pentanol and 4 moles of isopropanol with phosphorus pentasulfide. The dithiophosphoric acid is then reacted with a slurry of zinc oxide. The amount of zinc oxide in the slurry was about 1.08 times the theoretical amount required to completely neutralize the dithiophosphoric acid. The oil solution (10% oil) of zinc dithiophosphate thus obtained contained 9.5% phosphorus, 20.0% sulfur and 10.5% zinc.

Example D-2

Finely divided phosphorus pentasulfide was reacted with an alcohol mixture containing 11.53 moles (692 parts by weight) of isopropanol and 7.69 moles (1000 parts by weight) of isooctyl alcohol. The dithiophosphoric acid thus obtained has an acid number of about 178-186 and contains 10.0% phosphorus and 21.0% sulfur. The dithiophosphoric acid is then reacted with a slurry of zinc oxide. The amount of zinc oxide contained in the oil slurry is 1.10 times the theoretical equivalent of the acid value of dithiophosphoric acid. The zinc salt oil solution thus obtained contained 12% oil, 8.6% phosphorus, 18.5% sulfur and 9.5% zinc.

Example D-3

A dithiophosphoric acid is obtained by reacting a mixed alcohol containing 1560 parts (12 mol) of isooctyl alcohol and 180 parts (3 mol) of isopropanol with 756 parts (3.4 mol) of phosphorus pentasulfide. The reaction is carried out by heating the alcohol mixture to about 55°C and then adding phosphorus pentasulfide over 1.5 hours while maintaining the reaction temperature at about 60-75°C. After all the phosphorus pentasulfide has been added, the reaction mixture is heated and stirred at 70-75°C for an additional 1 hour, then filtered through a filter aid.

Zinc oxide (282 parts, 6.87 mol) was charged to a reactor containing 278 parts of mineral oil. The above-prepared dithiophosphoric acid (2305 parts, 6.28 mol) was put into the zinc oxide oil slurry over a period of 30 minutes, during which the heat was released and the temperature rose to 60°C. The mixture was heated to 80°C and maintained at this temperature for 3 hours. After stripping to 100℃/6mm.Hg, the mixture is filtered twice through a filter aid, and the filtrate is the oil solution of the required zinc salt, which contains 10% oil, 7.97% zinc (theoretical value 7.40), 7.21% phosphorus (theoretical value 7.06), and 15.64% sulfur (theoretical value 14.57).

Example D-4

Isopropanol (396 parts, 6.6 mol) and 1287 parts (99 mol) of isooctanol were charged into the reactor, which was then heated to 59°C with stirring. Phosphorus pentasulfide (833 parts, 3.75 mol) was then added under a nitrogen purge. Phosphorus pentasulfide was added over a period of 2 hours at a reaction temperature of 59-63°C. The reaction mixture was stirred at 45-63°C for 1.45 hours and filtered. The filtrate was the desired phosphoric acid disulfide.

312 parts (7.7 equivalents) of zinc oxide and 580 parts of mineral oil were charged to the reactor. Under stirring at room temperature, the above-prepared dithiophosphoric acid (2287 parts, 6.97 equivalents) was added to the reactor over 1.26 hours, during which time the temperature was exothermic and raised to 54°C. The mixture was heated to 78°C and maintained at 78-85°C for 3 hours. The reaction mixture was vacuum stripped to 100°C/19 mm. Hg. The remaining liquid was filtered through a filter aid and the filtrate was the desired oil solution of zinc salts (19.2% oil) containing 7.86% zinc, 7.76% phosphorus and 14.8% sulfur.

Example D-5

The procedure of Example D-4 was repeated except that the molar ratio of isopropanol to isooctyl alcohol was changed to 1:1. The product thus obtained was an oil solution (10% oil) of zinc dithiophosphate containing 8.96% zinc, 8.49% phosphorus and 18.05% sulfur.

Example D-6

Using a mixed alcohol containing 520 parts (4mol) of isooctyl alcohol and 360 parts (6mol) of isopropanol, the mixed alcohol was reacted with 504 parts (2.27mol) of phosphorus pentasulfide according to the process described in Example D-4, thereby producing A dithiophosphoric acid, the zinc salt of which was prepared by reacting a slurry of 116.3 parts of mineral oil and 141.5 parts (3.44 mol) of zinc oxide with 950.8 parts (3.20 mol) of the above-prepared dithiophosphoric acid. The product thus obtained was an oil solution (10% mineral oil) of the desired zinc salt containing 9.36% zinc, 8.81% phosphorus and 18.65% sulfur.

Other specific examples of metal dithiophosphates suitable for use as component (D) in the lubricating oils of the present invention are listed in the following table. Examples D-7 to D-11 were prepared from single alcohols, and Examples D-12 to D-15 were prepared from mixed alcohols according to the procedure described in Example 1.

Table I

Component D: metal dithiophosphate

Example R ¹ R ² M n

D-7 n-nonyl n-nonyl B _a 2

D-8 Cyclohexylcyclohexyl Z _n 2

D-9 Isobutyl Isobutyl Z _n 2

D-10 Hexylhexyl C _a 2

D-11 Isodecyl Isodecyl Z _n 2

D-12 (n-butyl + dodecyl) (1:1) _w Z _n 2

D-13 (isopropyl + isooctyl) (1:1) _w B _a 2

D-14 (isobutyl + isopentyl) (65:35) _m Z _n 2

D-15 (isopropyl + sec-butyl) (40:60) _m Z _n 2

Another class of dithiophosphate additives useful in the lubricating oil compositions of the present invention are the adducts of the metal dithiophosphates described above with an epoxide. Metal dithiophosphates suitable for use in the preparation of these adducts are generally zinc dithiophosphates. The epoxides may be alkylene oxides or epoxyaryl alkanes. Representative examples of epoxyaryl alkanes are styrene oxide, p-ethylstyrene oxide, α-methylstyrene oxide, 3-β-naphthyl-1,1,3-epoxy butane, m-dodecyl styrene oxide and p-chlorostyrene oxide. Alkylene oxides mainly include lower alkylene oxides in which the alkylene group has 8 or fewer carbon atoms. Examples of such lower alkylene oxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,3-propylene oxide, 1,4-butylene oxide, monoepoxidized butane alkenes, 1,2-epoxyhexane and epichlorohydrin. Examples of other epoxides suitable for use herein include 9,10-epoxybutyl stearate, epoxidized soybean oil, epoxidized tung oil, and epoxidized copolymers of styrene and butadiene.

Adducts of dithiophosphate metal salts and epoxides can be prepared by simple mixing. The reaction is generally exothermic and can be carried out over a wide temperature range of about 0-300°C. Since the reaction is exothermic, it is best to use one reactant. Usually an epoxide, added in small batches to the other reactant to facilitate control of the reaction temperature. The reaction can be carried out in a solvent such as benzene, mineral oil, naphtha or n-hexene.

The chemical structure of this adduct is unknown. It has now been found that the adduct produced by reacting 1 mole of dithiophosphate with about 0.25 to 5 moles, usually up to about 0.75 moles or about 0.5 moles of lower alkylene oxides, especially ethylene oxide and propylene oxide Compounds are particularly suitable for use in the present invention and are therefore preferred.

The following examples describe more specifically the preparation of the adducts.

Example D-16

2365 parts (3.33mol) of zinc dithiophosphate obtained in Example D-2 were dropped into a reactor, and stirred at room temperature, 38.6 parts (0.67mol) of propylene oxide were added therein, during which from 24- 31°C exotherm and temperature rise. The mixture was held at 80-90°C for 3 hours and then vacuum stripped to 101°C/7mm.Hg. The residue was filtered using a filter aid and the filtrate was an oil solution (11.8% oil) of the desired salt containing 17.1% sulfur, 8.71% zinc and 7.44% phosphorus.

Example D-17

At 75-85°C, add 13 parts of propylene oxide (0.5 moles of propylene oxide per mole of zinc dithiophosphate) to 394 parts (by weight) of dioctyl zinc dithiophosphate containing 7% phosphorus for 20 minute. The reaction mixture was heated at 82-85°C for 1 hour and filtered. The filtrate (399 parts) was found to contain 6.7% phosphorus, 7.4% zinc and 4.1% sulfur.

Another class of dithiophosphate additives (D) suitable for use in the lubricating oil compositions of the present invention are (a) at least one dithiophosphoric acid of formula VIII as defined and described above, and (b) at least one aliphatic Or mixed metal salts of cycloaliphatic carboxylic acids. The carboxylic acid may be monocarboxylic or polycarboxylic and generally contains 1 to 3 carboxyl groups and preferably only 1. It may contain about 2-40, preferably about 2-20, most preferably about 5-20 carbon atoms. Preferred are those carboxylic acids represented by the formula ^R3COOH , wherein ^R3 is an aliphatic or cycloaliphatic hydrocarbyl group, preferably free of acetylenic unsaturation. Suitable carboxylic acids include butanoic, pentanoic, caproic, octanoic, nonanoic, decanoic, dodecanoic, octadecanoic and eicosanoic acids, and also enoic acids such as oleic, linoleic, and Linolenic acid and dimerized linoleic acid. ^R3 is usually a saturated aliphatic group and especially a branched chain alkyl group such as isopropyl or 3-heptyl. Examples of polycarboxylic acids are succinic acid, alkyl and alkenyl succinic acids, adipic acid, sebacic acid and citric acid.

Mixed metal salts are prepared simply by mixing a metal dithiophosphate salt with a metal carboxylate salt in the desired ratio. The equivalent ratio of dithiophosphate to carboxylate is about 0.5:1 to 400:1. Preferably the ratio is from about 0.5:1 to 200:1. Advantageously the ratio may be from about 0.5:1 to 100:1, preferably from about 0.5:1 to 50:1, more preferably from about 0.5:1 to 20:1. More preferably the ratio may be from about 0.5:1 to 4.5:1, preferably from about 2.5:1 to 4.25:1. In calculating this ratio, the equivalent weight of a dithiophosphoric acid is its molecular weight divided by the number of -PSSH groups in the molecule, and the equivalent weight of a carboxylic acid is its molecular weight divided by the number of carboxyl groups.

Another and preferred method of mixing metal salts for use in the present invention is to make a mixed acid in the desired ratio and react it with a suitable metal base. When this method of preparation is employed, it is often possible to obtain a salt containing an excess of metal, relative to the number of equivalents of acid present; thus, containing up to 2 equivalents of metal per equivalent of acid, and especially containing as much as Mixed metal salts with 1.5 equivalents of metal can be obtained. The equivalent weight of a metal here is its atomic weight divided by its valence.

Variations of the methods described above may also be used to prepare mixed metal salts suitable for use in the present invention. For example, a metal salt of one acid can be mixed with another acid, and the resulting mixture reacted with additional metal base.

Suitable metal bases for the preparation of mixed metal salts include the previously listed metals and their oxides, hydroxides, alkoxides and basic salts thereof. Examples thereof are sodium hydroxide, potassium hydroxide, magnesium oxide, calcium hydroxide, zinc oxide, lead oxide, nickel oxide and the like.

The temperature at which the mixed metal salts are prepared is generally from about 30°C to about 150°C, preferably up to about 125°C. If the mixed salt is prepared by neutralization of a mixed acid with a metal base, temperatures above about 50°C and especially above about 75°C are recommended. It is often advantageous to carry out the reaction in the presence of an essentially inert, usually liquid, organic diluent such as naphtha, benzene, xylene, mineral oil, and the like. If the diluent is mineral oil or has similar physical and chemical properties to mineral oil, it is usually not necessary to remove the diluent before using the mixed metal salt as an additive in a lubricant or functional fluid.

USP 4,308,154 and 4,417,990 describe the preparation of these mixed metal salts and disclose many examples of such mixed salts. The foregoing disclosures of these two patents are incorporated herein by reference.

The following examples describe the preparation of mixed salts.

Example D-18

A mixture of 67 parts (1.63 equivalents) of zinc oxide and 48 parts of mineral oil was stirred at room temperature, then mixed with 401 parts (1 equivalent) of di(2-ethylhexyl) dithiophosphoric acid and 36 parts (0.25 equivalents) The resulting mixture of 2-ethylhexanoic acid was added over a period of 10 minutes, during which time the temperature rose to 40°C. After the addition was complete, the temperature was allowed to rise to 80°C over 3 hours. The mixture was vacuum stripped at 100°C to give the desired mixed metal salt as a 91% solution in mineral oil.

Example D-19

According to the process of Example D-18, by 383 parts (1.2 equivalents) containing 65% isobutyl and 35% amyl dialkyl dithiophosphoric acid, 43 parts (0.3 equivalents) 2-ethylhexanoic acid, 71 One part (1.73 equivalents) of zinc oxide and 47 parts of mineral oil gave a product. The mixed metal salt was obtained as a solution in 90% mineral oil containing 11.07% zinc.

(E) Neutral or basic alkali metal salts

The lubricating oil compositions of the present invention may also contain at least one neutral or basic alkali metal salt of at least one sulfonic acid or carboxylic acid. The amount of alkali metal salt in the lubricating oil is effective to provide the desired detergency properties to the oil. Typically, the lubricant contains about 0.01-5% alkali metal salt, more usually about 0.01-3%. A general description of some alkali metal salts suitable for use as component (E) is found in U.S. Patent 4,326,972 (Chamberlin). The disclosure of these suitable alkali metal salts and methods for their preparation in this patent is incorporated herein by reference.

The alkali metals in the basic alkali metal salts are primarily lithium, sodium and potassium, with sodium and potassium being preferred.

The equivalent weight of an acidic organic compound is its molecular weight divided by the number of acid groups (ie sulfonic or carboxylic acid groups) present in the molecule.

In a preferred embodiment, the alkali metal salt (E) is an alkaline base having a metal ratio of at least 2 and more typically 4-40, preferably about 6-30 and especially about 8-25 metal salts.

The acidic organic compound from which the salt of component (E) is obtained may be at least one containing sulfuric acid, carboxylic acid, phosphoric acid or phenol or a mixture thereof. Sulfuric acid includes sulfonic acid, thiosulfonic acid, sulfinic acid, sulfenic acid; partial esters of sulfuric acid, sulfurous acid and thiosulfuric acid.

Sulfonic acids suitable for use in the preparation of component (E) include those represented by the formula

R _x T (SO ₃ H) _y (Ⅸ)

and R′(SO ₃ H) _r (X)

In the above two formulas, R' is an aliphatic, substituted cycloaliphatic or substantially hydrocarbyl group free of acetylenic unsaturation, which may contain up to about 60 carbon atoms. When R' is an aliphatic hydrocarbyl, it will generally contain at least 15 carbon atoms; when it is an aliphatically substituted cycloaliphatic hydrocarbyl, the aliphatic substituents will generally contain a total of at least 12 carbon atoms. Examples of R' are alkyl, alkenyl, and alkoxyalkyl, and aliphatic hydrocarbon-substituted groups whose aliphatic substituents are alkyl, alkenyl, alkoxy, alkoxyalkyl, carboxyalkyl, etc. Cycloaliphatic group. Typically, cycloaliphatic rings are derived from cycloalkanes or cycloalkenes such as cyclopentane, cyclohexane, cyclohexene or cyclopentene. Specific examples of R' are cetylcyclohexyl, laurylcyclohexyl, cetyloxyethyl, octadecenyl, and groups derived from petroleum, saturated and unsaturated paraffinic and olefinic polymers, The olefin polymers include monoolefins having about 2 to 8 carbon atoms per olefin monomer unit and diolefins having 4 to 8 carbon atoms per monomer unit. R' may also contain other substituents such as phenyl, cycloalkyl, hydroxyl, mercapto, halo, nitro, amino, nitroso, lower alkoxy, lower alkyl mercapto, carboxyl, alkyl ester, oxo or Thio group, or as long as it does not destroy the essential properties of the hydrocarbon, it can also contain an interrupting group such as -NH-, -O- or -S-.

R in formula IX is generally a hydrocarbyl group containing from about 4 to 60 aliphatic carbon atoms or substantially free of acetylenic unsaturation, preferably an aliphatic hydrocarbyl group such as an alkyl or alkenyl group. However, the hydrocarbyl group may also contain substituents or successor groups such as those enumerated above, provided that the substantial hydrocarbyl character is retained. Generally, no more than 10% of the total weight of any non-carbon atoms in R' or R will be present.

T is a ring nucleus which may be derived from an aromatic hydrocarbon such as benzene, naphthalene, anthracene or biphenyl, or from a heterocyclic compound such as pyridine, indole or isoindole. Typically, T is an aromatic nucleus, especially a benzene or naphthalene nucleus.

The subscript X is at least 1 and usually 1-3. The subscripts r and y have an average value of about 1-2 and usually 1 per molecule.

The sulfonic acids are usually petroleum sulfonic acids or synthetically produced alkaryl sulfonic acids. Among petroleum sulfonic acids, the most suitable are the products obtained by sulfonating the appropriate petroleum fractions, followed by removal of acid residues and purification. Synthetic alkaryl sulfonic acids are usually prepared from the Friedel-Crafts reaction of alkylated benzenes such as benzene with polymers such as tetrapropylene. The following are specific examples of sulfonic acids suitable for the preparation of salts (E). These examples also serve to describe those sulfonates suitable for use as component (E). In other words, for each sulfonic acid listed, the corresponding basic alkali metal salt is also considered to be described (the same applies to the other acidic substances listed in the table below). These sulfonic acids include petroleum sulfonic acid, bright stock sulfonic acid, petrolatum sulfonic acid, mono- or polywax-substituted naphthalene sulfonic acid, cetyl chlorobenzene sulfonic acid, cetylphenol sulfonic acid, cetyl disulfide Cetyl phenol sulfonic acid (cetyphenol disulfide sulfonic acids), cetyloxyoctylbenzene sulfonic acid, two (hexadecyl) sulfur anthene sulfonic acid, dilauryl B-naphthol sulfonic acid, dioctyl nitronaphthalene sulfonic acid Acid, saturated paraffin sulfonic acid, unsaturated paraffin sulfonic acid, hydroxyl substituted paraffin sulfonic acid, tetraisobutylene sulfonic acid, tetrapentamethylene sulfonic acid, chloroparaffin sulfonic acid, nitroso paraffin sulfonic acid, petroleum Naphthalenesulfonic acid, cetylcyclopentylsulfonic acid, laurylcyclohexylsulfonic acid, mono- or polywaxycyclohexylsulfonic acid, dodecylbenzenesulfonic acid, "dimer alkylationsulfonic acid" and the like.

Alkyl substituted benzene sulfonic acids, including dodecylbenzene "bottom" sulfonic acids, the alkyl groups of which contain at least 8 carbon atoms are particularly suitable. The latter are derived from benzene that has been alkylated with propylene tetramer or isobutylene trimer to introduce 1, 2, 3 or more branched _C12 substituents on the benzene ring. Dodecylbenzene bases, mainly mono- and didodecylbenzene, are obtained as by-products of the manufacture of household detergents. Similar products from alkylation substrates formed in the production of LAS are also suitable for use in the preparation of the sulfonates used in the present invention.

The production of sulfonates from by-products of detergent production by reaction with e.g. _SO3 is known to the skilled person. See, for example, the article "Sulphonates" in "Encyclopedia of Chemical Technology" edited by Kirk-Oer, 2nd Edition, Vol. 19, pp. 291ff., John Wiley & Sons Co., New York (1969).

Other descriptions of basic sulfonates which may be incorporated as component (E) into the lubricating oil compositions of the present invention, and techniques for preparing them, can be found in the following U.S. Patents: USP 2,174,110; 2,202, 781; 2,239,974; 2,319,121; 2,337,552; 3,488,284; 3,595,790; and 3,798,012. The relevant contents of these patent publications are incorporated herein by reference.

Suitable carboxylic acids for the preparation of suitable alkaline earth metal salts (E) include aliphatic, cycloaliphatic and aromatic mono- and polybasic carboxylic acids, including naphthenic acids, alkyl or alkenyl substituted cyclopentanoic acids , alkyl or alkenyl substituted cyclohexanoic acid and alkyl or alkenyl substituted aryl carboxylic acid. The aliphatic acids generally contain about 8-50, preferably about 12-25 carbon atoms. Cycloaliphatic acids and aliphatic carboxylic acids are preferred, which may be saturated or unsaturated. Specific examples include 2-ethylcyclohexanoic acid, linolenic acid, propylene tetramer substituted maleic acid, behenic acid, isostearic acid, nonanoic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, Oleic acid, ricinoleic acid, undecanoic acid, dioctylcyclopentane carboxylic acid, myristic acid, dilauryl decahydronaphthalene monocarboxylic acid, stearyl octahydroindene carboxylic acid, palmitic acid, alkyl and Alkenyl succinic acid, acids produced by oxidation of petrolatum or hydrocarbon wax, commercially available mixed acids of two or more carboxylic acids such as tall oil acid, abietic acid, etc.

In a preferred embodiment, the basic sulfonate salt (E) is an oil-soluble dispersion obtained by contacting the following materials between the salt-forming temperature of the reaction mixture and its decomposition temperature for a period sufficient to form a stable dispersion made over time.

(E-1) at least one acidic gaseous substance selected from carbon dioxide, hydrogen sulfide, and sulfur dioxide, and

(E-2) Reaction mixtures containing

(E-2-a) at least one oil-soluble sulfonic acid, or derivatives thereof susceptible to overbasing;

(E-2-b) at least one alkali metal or basic alkali metal compound;

(E-2-c) at least one lower aliphatic alcohol, alkylphenol, or sulfurized alkylphenol; and

(E-2-d) at least one oil-soluble carboxylic acid or a functional derivative thereof.

Component (E-2-d) is optional when (E-2-c) is an alkylphenol or a sulfurized alkylphenol. Satisfactory basic sulfonates can be obtained with or without carboxylic acids in the mixture (E-2).

The reactant (E-1) is at least one acidic gaseous substance which may be carbon dioxide, hydrogen sulphide or sulfur dioxide; mixtures of these gases are also suitable, preferably carbon dioxide.

As mentioned above, component (E-2) is usually a mixture of at least four components, of which component (E-2-a) is at least one oil-soluble sulfonic acid as defined above, or its susceptible to overbasing derivative. It is also possible to use mixtures of sulfonic acids and/or derivatives thereof. Sulfonic acid derivatives sensitive to overbase include their metal salts, especially alkaline earth metal, zinc and aluminum salts; ammonium and amine salts (such as ethylamine, butylamine and ethylene polyamine salts); and esters such as Ethyl, Butyl and Glycerides.

Component (E-2-b) is preferably at least one basic alkali metal compound. Illustrative examples of basic alkali metal compounds include hydroxides, alkoxides (typically those in which the alkoxy group contains up to 10 and preferably up to 7 carbon atoms), hydrides and amides. Thus, useful 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, amido sodium and potassium amide. Particularly preferred are sodium hydroxide and sodium lower alkanolates (ie containing up to 7 carbon atoms). The equivalent weight of component (E-2-b) suitable for the purpose of the present invention is equal to its molecular weight because alkali metals are monovalent.

Component (E-2-c) may be at least one lower aliphatic alcohol, preferably monohydric or dihydric alcohol. Illustrative examples of alcohols are methanol, ethanol, 1-propanol, 1-hexanol, isopropanol, isobutanol, 2-pentanol, 2,2-dimethyl-1-propanol, 1,2-ethylene Ethylene glycol, 1,3-propanediol and 1,5-pentanediol. Alcohols can also be glycol ethers such as methyl cellosolve. Of these, methanol, ethanol and propanol are preferred, with methanol being most preferred.

Ingredient (E-2-c) may also be at least one alkylphenol or sulfurized alkylphenol, preferably a sulfurized alkylphenol, especially when ingredient (E-2-b) is potassium or one of its bases active compounds such as potassium hydroxide. The term "phenol" as used herein includes compounds having more than one hydroxyl group on an aromatic ring which may be benzyl or naphthalene. "Alkylphenol" includes mono- or dialkylated phenols wherein each alkyl substituent contains about 6-100 carbon atoms, preferably about 6-50 carbon atoms.

Illustrative examples of alkylphenols include heptylphenol, octylphenol, decylphenol, dodecylphenol, polypropylene (Mn about 150) substituted phenols, polyisobutylene (Mn about 1200) substituted phenols, cyclohexylphenol .

It is also possible to use condensation products of the abovementioned phenols with at least one lower aldehyde or ketone. "Low carbon" refers to aldehydes and ketones containing not more than 7 carbon atoms. Suitable aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde and benzaldehyde. Aldehyde-generating reagents such as paraformaldehyde, trioxane, hydroxymethyl, Methyl Formcel and paraacetaldehyde are also suitable. Formaldehyde and formaldehyde-generating agents are particularly preferred.

Sulfurized alkylphenols include sulfurized phenols, disulfides or polysulfides. The sulfurized phenols can be derived from suitable alkylphenols by techniques known in the art, and many sulfurized phenols are commercially available. Sulfurized alkylphenols are prepared by reacting the alkylphenol with elemental sulfur and/or sulfur monohalides such as sulfur monochloride. This reaction can be carried out in the presence of an excess of base to form a salt of a mixture of sulfides, disulfides or polysulfides depending on the reaction conditions. The product obtained by this reaction is used to prepare the component (E-2) of the present invention. U.S. Patents 2,971,940 and 4,309,293 disclose various sulfurized phenols which are illustrative of component (E-2-c), the disclosures of which are incorporated herein by reference.

The equivalent weight of ingredient (E-2-c) is its molecular weight divided by the number of hydroxyl groups per molecule.

Ingredient (E-2-d) is at least one of the aforementioned oil-soluble carboxylic acids or functional derivatives thereof. Particularly suitable carboxylic acids are those of the formula ^R5 (COOH) _n , wherein n is an integer from 1 to 6, more preferably 1 or 2, and ^R5 is a saturated or substantially saturated compound having at least 8 aliphatic carbon atoms. The aliphatic group (preferably a hydrocarbon group). Depending on the value of n, R ⁵ may be a monovalent to hexavalent group.

^R5 may contain non-hydrocarbon substituents provided that such substituents do not alter its hydrocarbon character. Such substituents are preferably present in an amount not greater than 20% by weight, examples of which include the non-hydrocarbon substituents listed above in relation to ingredient (E-2-a). Based on the total number of carbon-carbon covalent bonds present, R can also contain up to about ⁵ %, preferably not more than 2%, of ethylenically unsaturated bonds. The number of carbon atoms in ^R is usually about 8-700, depending on its source. As described below, preferred carboxy Acids and their derivatives are prepared by reacting olefin polymers or halogenated olefin polymers with α, β-unsaturated acids or their anhydrides such as acrylic acid, methacrylic acid, maleic acid or fumaric acid or maleic anhydride to form Correspondingly substituted acids or derivatives thereof. The number average molecular weight of the ^R5 group in these products is from about 150 to 10,000, usually from about 700 to 5000, for example as determined by gel permeation chromatography.

Monocarboxylic acids useful as component (E-2-d) have the formula R ⁵ COOH and are exemplified by caprylic acid, capric acid, palmitic acid, stearic acid, isostearic acid, linoleic acid and behenic acid. Particularly preferred monocarboxylic acids are prepared by reacting a halogenated olefin polymer such as chlorinated butene with acrylic or methacrylic acid.

Suitable dicarboxylic acids include the formula The substituted succinic acid shown, wherein ^R6 is the same as ^R5 defined above. ^R6 may be a radical derived from an olefin polymer formed by polymerization of monomers such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-pentene, 1-hexene and 3-hexene alkene. ^R6 can also be derived from high molecular weight substantially saturated petroleum fractions. Hydrocarbon substituted succinic acids and their derivatives constitute the most preferred class of carboxylic acids for use as component (E-2-d).

The aforementioned olefin polymer derived carboxylic acids and their derivatives are well known in the art and their preparation and representative examples useful in the present invention are described in detail in several US patents.

Functional derivatives of the above acids useful as component (E-2-d) include anhydride esters, amides, imides, amidines and metal or ammonium salts. The reaction products of olefinic polymer-substituted succinic acids with one or more amines, especially polyalkylene polyamines having up to 10 amino nitrogens, are particularly preferred. These reaction products usually contain a mixture of one or more amides, imides and amidines. The reaction products of polyvinylamines containing up to 10 nitrogen atoms and polybutene-substituted succinic anhydrides in which the polybutenyl group consists predominantly of isobutene units are particularly useful. This group of functional derivatives includes compositions prepared by post-treating amine-anhydride reaction products with carbon disulfide, boron compounds, nitriles, ureas, thioureas, guanidines, alkylene oxides, and the like. Half amides, half metal salts and half ester, half metal salt derivatives of the above substituted succinic acids are also useful.

Esters prepared by reacting substituted acids or anhydrides with one or more hydroxyl compounds such as aliphatic alcohols or phenols are also useful. Preferred are the esters of olefinic polymer-substituted succinic acids or anhydrides with polyhydric aliphatic alcohols containing from 2 to 10 hydroxyl groups and up to 40 aliphatic carbon atoms. Such alcohols include ethylene glycol, glycol, sorbitol, pentaerythritol, polyethylene glycol, diethanolamine, triethanolamine, N,N'-di(hydroxyethyl)ethylenediamine, etc. . When the alcohol contains a reactive amino group, the reaction product may include the product formed by the reaction of the acid with both hydroxyl and amino functional groups. Thus, the reaction mixture may include half-esters, half-amides, esters, amides and imides.

The equivalent ratio of the components of the reagent (E-2) can have a wide range. Usually, the ratio of components (E-2-b) to (E-2-a) is at least about 4:1, generally not more than 40:1, preferably 6:1-30:1, more preferably 8:1 -25:1. Although this ratio can sometimes exceed 40:1, such an excess is usually not necessarily beneficial.

The equivalent ratio of components (E-2-c) to (E-2-a) is about 1:20-80:1, preferably about 2:1-50:1. As mentioned above, when the component (E-2-c) is an alkylphenol or a sulfurized alkylphenol, the carboxylic acid (E-2-d) is optional. When present in the mixture, the equivalent ratio of components (E-2-d) to (E-2-a) is usually about 1:1-1:20, preferably about 1:2-1:10.

Up to stoichiometric amounts of acidic material (E-1) react with (E-2). In one embodiment, the acidic material is metered into the (E-2) mixture and the reaction occurs rapidly. The rate of addition of (E-1) is not critical, but can be reduced if the reaction mixture warms up too rapidly due to the exotherm of the reaction.

When (E-2-c) is an alcohol, the reaction temperature is not critical and is usually between the solidification temperature and the decomposition temperature (ie, the lowest decomposition temperature of either component) of the reaction mixture. Generally, the reaction temperature is about 25-200°C, preferably 50-150°C. Reagents (E-1) and (E-2) are conveniently brought into contact at the reflux temperature of the mixture. This temperature will obviously depend on the boiling points of the various ingredients; thus, when methanol is used as ingredient (E-2-c), the contacting temperature will be at or below the reflux temperature of the methanol.

When the reagent (E-2-c) is an alkylphenol or a sulfurized alkylphenol, the reaction temperature must be at or above the azeotropic temperature of water in order to escape the water formed in the reaction.

The reaction is usually carried out at atmospheric pressure, although superatmospheric pressure generally accelerates the reaction and facilitates optimal utilization of the reagents (E-1). The reaction can also be performed under reduced pressure, but this is rarely used for obvious practical reasons.

The reaction is generally carried out in the presence of an essentially inert, usually liquid, organic diluent. The function of the organic diluent is both a dispersion medium and a reaction medium. Such diluents constitute at least about 10% of the total weight of the reaction mixture.

Once the reaction is complete, any solids in the mixture are preferably removed by filtration or other conventional means. Easily removable diluents, alcohol promoters and water formed in the reaction can be removed if necessary by conventional techniques such as distillation. It is generally desirable to remove all water from the reaction mixture, since its presence can lead to filtration difficulties and the formation of undesirable emulsions in fuels and lubricants. The water present is readily removed by heating or azeotropic distillation at atmospheric or reduced pressure. In a preferred embodiment, when basic potassium sulfonate is desired as component (E), the potassium salt is prepared using carbon dioxide and sulfurized alkylphenol as component (E-2-c). The use of sulfurized phenols produces high metal ratio basic salts and produces more uniform and stable salts.

The basic salt or complex of component (E) may be a solution, or more likely a stable dispersion. In addition, they can also be considered as "polymeric salts" formed by the reaction of acidic materials (overbased oil-soluble acids) and metal compounds. In view of the foregoing, these compositions are more readily defined by the method by which they are formed.

Canadian Patent 1,055,700 (corresponding to British Patent 1,481,553) describes in detail the above-mentioned preparation of alkali metal sulphonic acid having a metal ratio of at least 2, preferably about 4-40, using an alcohol as component (E-2-c). salt method. The disclosures of these patents for this method are incorporated herein by reference. The following examples further illustrate the preparation of dispersions of alkali metal sulfonate salts as component (E) of the lubricating oil compositions of the present invention.

Example E-1

To a solution of 790 parts (1 equivalent) of alkylated benzenesulfonic acid and 71 parts of polyisobutylsuccinic anhydride (equivalent weight about 560) mainly containing isobutylene units (in 176 parts of mineral oil) was added 320 parts (8 equivalents) ) sodium hydroxide and 640 parts (20 equivalents) of methanol. Due to the exotherm of the reaction, the reaction mixture warmed to 89°C (reflux) within 10 minutes. During this period, carbon dioxide was bubbled into the reaction mixture at 4 cfh (cubic feet per hour). Carbonization lasted for about 30 minutes, and the temperature gradually dropped to 74 °C. Methanol and other volatiles were stripped from the carbonized mixture by blowing in nitrogen at 2 cfh while the temperature was slowly raised to 150°C over 90 minutes. After the extraction was complete, the remaining mixture was maintained at 155-165°C for about 30 minutes and filtered to obtain an oily solution of the desired basic sodium sulfonate with a metal ratio of about 7.75. The solution contained 12.4% oil.

Example E-2

Following the procedure of Example E-1, 780 parts (1 equivalent) of alkylated benzenesulfonic acid and 119 parts of polybutenyl succinic anhydride (in 442 parts of mineral oil) were mixed with 800 parts (20 equivalents) of sodium hydroxide and 704 parts (22 equivalents) of methanol are mixed. Carbon dioxide was bubbled into the mixture at 7 cfh for 11 minutes while the temperature was slowly raised to 97°C. The flow rate of carbon dioxide was reduced to 6 cfh and the temperature was slowly lowered to 88°C over about 40 minutes. The carbon dioxide flow rate was reduced to 5 cfh and continued for about 35 minutes, the temperature was slowly lowered to 73°C. Nitrogen was blown into the carbonized mixture at 2 cfh for 105 minutes to remove volatile matter, and the temperature was slowly raised to 160°C. After the extraction was complete, the mixture was maintained at 160°C for an additional 45 minutes and then filtered to obtain an oil solution of the desired basic sodium sulfonate with a metal ratio of about 19.75, which contained 18.7% oil.

(F) Carboxylate derivative composition

The lubricating oil composition of the present invention may also contain and often must contain (F), which is composed of (F-1) at least one substituted succinic acylating agent and (F-2) formula R ³ (OH) _m (XI) At least one carboxylate derivative composition resulting from the reaction of at least one alcohol or phenol as shown. In formula (Ⅺ), R ³ is a monovalent or multivalent organic group connected to -OH group through a carbon bond, and m is an integer of 1-10. The carboxylate derivative (F) is present in the oil composition in an amount of up to 10% by weight, usually about 1-10% by weight, based on the total weight of the lubricating oil. Carboxylate (F) provides additional dispersibility. In some applications, the ratio of carboxylic acid derivative (B) to carboxylate (F) in the oil affects the properties of the oil composition, such as antiwear properties. The amount of the carboxylate derivative in the lubricating oil composition may vary from about 0.1% to about 10% by weight.

The substituted succinic acylating agent (F-1) that reacts with alcohols or phenols to form carboxylate derivatives is the same as the above-mentioned acylating agent (B-1) for the preparation of carboxylic acid derivatives (B), except that the derivative The polyalkylene of the substituent is characterized as having a number average molecular weight of at least about 700.

Molecular weights (M _n ) of about 700-5000 are preferred. In a preferred embodiment, the substituents of the acylating agent are derived from polyalkylenes characterized by _Mn values of about 1300-5000 and Mw/Mn values of about 1.5-4.5. The acylating agent for this embodiment is the same as the acylating agent involved in the aforementioned preparation of the carboxylic acid derivative used as component (B). Accordingly, any of the acylating agents mentioned above for the preparation of component (B) may be used in the preparation of the carboxylate derivative composition used as component (F). When the acylating agent used to prepare the carboxylate (F) is the same as that used to prepare the component (B), the carboxylate component (F) is also characterized as a dispersant having VI properties. The combination of component (B) and the preferred type of component (F) in the oils of the invention also provides the oils of the invention with excellent antiwear properties. However, other substituted succinic acylating agents can also be used in the present invention to prepare carboxylate derivative compositions useful as component (F). For example, succinic acylating agents in which the substituents are derived from polyalkylenes having a number average molecular weight of about 800-1200 are useful.

The carboxylate derivative composition (F) is a product of the above-mentioned succinic acylating agent and a hydroxy compound. The hydroxy compounds may be aliphatic compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols. Aromatic hydroxy compounds from which esters can be derived include the following specific examples: phenol, β-naphthol, α-naphthol, cresol, resorcinol, p-phenol, P,P′-dihydroxybiphenyl, 2- Chloro-phenol, 2,4-dibutylphenol, etc.

The alcohol (F-2) from which the ester is derived preferably contains up to about 40 aliphatic carbon atoms. It can be a monohydric alcohol such as methanol, ethanol, isooctyl alcohol, dodecanol, cyclohexanol, etc. Polyhydric alcohols preferably contain 2-10 hydroxyl groups, examples are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol and Other alkanediols having 2 to 8 carbon atoms in the alkylene moiety.

A particularly preferred class of polyhydric alcohols are those having at least three hydroxyl groups, some of which have been replaced with carboxylic acids having from about 8 to 30 carbon atoms such as caprylic acid, oleic acid, stearic acid, linoleic acid, dodecane Alcohol esterified with acid or tall oil. Examples of such partially esterified polyhydric alcohols are sorbitol monooleate, sorbitol distearate, glycerol monooleate, glycerol monostearate and pentaerythritol di-dodecyl Alkanoates.

Esters (F) can be prepared by any of several known methods. A preferred method, due to convenience and the excellent properties of the resulting esters, involves the reaction of the appropriate alcohol or phenol with a hydrocarbon-substituted succinic anhydride. Esterification is usually carried out at a temperature higher than 100°C, preferably 150°-300°C. The by-product water formed is distilled off as the esterification proceeds.

The relative proportions of amber reactant and hydroxyl reactant employed depend largely on the type of product desired and the number of hydroxyl groups present in the hydroxyl reactant molecule. For example, to form a half-ester of succinic acid (i.e., to esterify one of the two acid groups), for each mole of substituted succinic acid reactant, one mole of the -hydroxyl alcohol is required; whereas to form a diester of succinic acid, for each mole of acid, Two moles of alcohol are required. Alternatively, one mole of hexahydric alcohol can be combined with up to six moles of succinic acid to form an ester in which each of the six hydroxyl groups of the alcohol is esterified with one of the two acid groups of succinic acid. Therefore, the maximum proportion of succinic acid used with polyhydric alcohols is determined by the number of hydroxyl groups present in the hydroxyl reactant molecule. In one approach, esters prepared by reacting equimolar amounts of a succinic acid reactant and a hydroxyl reactant are preferred.

The methods for preparing carboxylate esters (F) are well known in the art and need not be described in detail here. See, for example, U.S. Patent 3,522,179 which is incorporated herein by reference for its disclosure of the preparation of carboxylate compositions useful as component (F). A method for preparing carboxylate derivative compositions from an acylating agent wherein the substituents are derived from a polyalkene characterized by an Mn of at least about 1300 up to 5000 and a Mw _{/ Mn} ratio of 1.5 to about 4 is described in USP 4,234,435, which was previously incorporated herein by reference. As previously stated, the acylating agents described in USP 4,234,435 are characterized by having an average number of at least 1.3 succinic groups per equivalent of heavy substituents in their structure.

The following examples describe the esters (F) and their preparation.

Example F-1

Substantially hydrocarbon-substituted succinic anhydride is prepared by chlorinating polyisobutene having a number average molecular weight of 1000 to a chlorine content of 4.5%, then heating the chlorinated polyisobutene with 1.2 molar proportion of maleic anhydride at 150-200°C. The acid value of the resulting succinic anhydride was 130. A mixture of 874 g (1 mole) of succinic anhydride and 104 g (1 mole) of neopentyl alcohol was maintained at 240-250°C/30 mm for 12 hours. The residue is a mixture of esters obtained by esterification of one and two hydroxyl groups in the diol. Its saponification value is 101, and its alcoholic hydroxyl content is 0.2%.

Example F-2

The substantially hydrocarbon substituted succinic acid of Example F-1 was prepared by heating a mixture of 2185 g of the succinic anhydride of Example F-1, 480 g of methanol and 1000 ml of toluene at 50-65°C while bubbling hydrogen chloride into the reaction mixture for 3 hours Dimethyl ester of anhydride. The mixture was then heated at 60-65°C for 2 hours, dissolved in benzene, washed with water, dried and filtered. The filtrate was heated at 150°C/60 mm to remove volatile components. The residue was the desired dimethyl ester.

The above-mentioned carboxylate derivatives obtained by reacting an acylating agent with a hydroxyl-containing compound such as alcohol or phenol can be further combined with (F-3) amines, especially polyamines, to prepare the acylating agent (B) in the aforementioned component (B). -1) The reaction is carried out by reacting with the amine (B-2). In one embodiment, the amount of amine reacted with the ester is such that there is at least about 0.01 equivalents of amine per equivalent of acylating agent initially employed in the reaction with the alcohol. Because the acylating agent has reacted with the alcohol, ie, at least one equivalent of alcohol per equivalent of acylating agent, the small amount of amine is sufficient to react with the traces of unesterified carboxyl groups that may be present. In a preferred embodiment, the preparation of the amine-modified carboxylic acid ester used as component (F) is to make about 1.0-2.0 equivalents, preferably about 1.0-1.8 equivalents, of hydroxyl compound and at most Up to 0.3 equivalents, preferably about 0.02-0.25 equivalents, of polyamines are reacted.

In another approach, the carboxylic acylating agent can be reacted simultaneously with the alcohol and the amine. The combined amount of alcohol and amine should be at least 0.5 equivalents per equivalent of acylating agent, but generally there should be about at least 0.01 equivalents of alcohol and at least 0.01 equivalents of amine. Compositions of these carboxylate derivatives useful as component (F) are known in the art, for example, the preparation of many such derivatives is described in USP 3,957,854 and 4,234,435 , these two patents have been incorporated herein by reference. The following specific example describes the preparation of this ester in which both an alcohol and an amine are reacted with an acylating agent.

Example F-3

334 parts (0.52 equivalents) of the polyisobutylene-substituted succinic acylating agent prepared in Example F-2, 548 parts of mineral oil, 30 parts (0.88 equivalents) of pentaerythritol and 8.6 parts (0.0057 equivalents) of polyethylene glycol 112-2 demulsifier (Dow Chemical Company) mixture was heated at 150°C for 2.5 hours. The reaction mixture was heated to 210°C over 5 hours and held at 210°C for 3.2 hours. The reaction mixture was cooled to 190°C and 8.5 parts (0.2 equivalents) of a commercial ethylene polyamine mixture having an average of about 3-10 nitrogen atoms per molecule were added. The reaction mixture was heated at 205°C, extracted by blowing nitrogen gas for 3 hours, and then filtered to obtain the filtrate as an oil solution of the desired product.

Example F-4

322 parts (0.5 equivalents) of the polyisobutylene-substituted succinic acylating agent of Example F-2, 68 parts (2.0 equivalents) of pentaerythritol and 508 parts of mineral oil were heated at 204-227°C for 5 hours. The reaction mixture was cooled to 162°C and 5.3 parts (0.13 equivalents) of a commercial ethylene polyamine mixture having an average of about 3-10 nitrogen atoms per molecule were added. The reaction mixture was heated at 162-163°C for 1 hour, then cooled to 130°C, filtered, and the filtrate was an oily solution of the desired product.

Example F-5

A mixture of 1000 parts (0.495mol) of polyisobutylene with a number average molecular weight of 2020 and a weight average molecular weight of 6049 and 115 parts (1.17mol) of maleic anhydride was heated to 184°C for 6 hours, during which 85 parts ( 1.2mol) chlorine. An additional 59 parts (0.83 mol) of chlorine were added over 4 hours at 184-189°C. Nitrogen was blown through the mixture at 186-190°C for 26 hours and the residue was a polyisobutylene substituted succinic anhydride with a total acid value of 95.3.

A solution of 409 parts (0.66 equivalents) of substituted succinic anhydride in 191 parts of mineral oil was heated to 150°C and 42.5 parts (1.19 equivalents) of pentaerythritol were added over 10 minutes at 145-150°C with stirring. Nitrogen was bubbled through the mixture and it was heated to 205-210° C. for about 14 hours to obtain an oil solution of the desired ester intermediate.

4.74 parts (0.138 equivalents) of diethylenetriamine were added to 988 parts of polyester intermediate (containing 0.69 equivalents of substituted succinic acylating agent and 1.24 equivalents of pentaerythritol) under stirring at 160°C for half an hour. Stirring was continued at 160° C. for 1 hour, then 289 parts of mineral oil were added. The mixture was heated at 135°C for 16 hours and filtered using a filter aid at the same temperature. The filtrate was 35% of the desired amine-modified polyester in mineral oil. It has a nitrogen content of 0.16% and a residual acid value of 2.0.

Example F-6

(a) A mixture of 1000 parts of polyisobutylene having a number average molecular weight of about 1000 and 108 parts (1.1 mol) of maleic anhydride is heated to about 190°C, and 100 parts (1.43 mol) of chlorine are added to the liquid surface over about 4 hours, At the same time, the temperature is maintained at 185-190°C. Nitrogen was then blown through the mixture at this temperature for several hours and the residue was a polyisobutylene substituted succinic acylating agent.

(b) A solution of 1000 parts of the acylating agent prepared in (a) in 857 parts of mineral oil is heated to about 150°C while stirring and 109 parts (3.2 equivalents) of pentaerythritol are added with stirring. Nitrogen was blown into the mixture and the mixture was heated to about 200°C for 14 hours to form an oil solution of the desired carboxylate intermediate. To the intermediate was added 19.25 parts (0.46 equivalents) of a commercial mixture of ethylene polyamines containing an average of about 3-10 nitrogen atoms per molecule. The reaction mixture was extracted by heating at 205°C with nitrogen blowing for 3 hours, then filtered. The filtrate was an oil solution (45% oil) of the desired amine-modified carboxylate containing 0.35% nitrogen.

Example F-7

(a) Heat a mixture of 1000 parts (0.495mol) of polyisobutylene with a number average molecular weight of 2020 and a weight average molecular weight of 6049 and 115 parts (1.17mol) of maleic anhydride to 184°C in 6 hours, and add 85 parts (1.2 mol) chlorine. At 184-189°C, an additional 59 parts (0.83 mol) of chlorine were added over 4 hours. Chlorine gas was blown into the mixture at 186-190°C for 26 hours. The residue was polyisobutylene substituted succinic anhydride with a total acid number of 95.3.

(b) A solution of 409 parts (0.66 equivalents) of the above substituted succinic anhydride in 191 parts of mineral oil was heated to 150°C, and 42.5 parts (1.19 equivalents) of pentaerythritol was added over 10 minutes under stirring at 145-150°C. The mixture was sparged with nitrogen and heated to 205-210°C for 14 hours to obtain an oil solution of the desired polyester intermediate.

4.74 parts (0.138 equivalents) of diethylenetriamine were added to 988 parts of polyester intermediate (containing 0.69 equivalents of substituted succinic acylating agent and 1.24 equivalents of pentaerythritol) over half an hour at 160°C with stirring. Stirring was continued at 160° C. for 1 hour, then 289 parts of mineral oil were added. The mixture was heated at 135°C for 16 hours and filtered using a filter aid at the same temperature. The filtrate was a 35% solution of the desired amine-modified polyester in mineral oil. It has a nitrogen content of 0.16% and a residual acid value of 2.0.

The lubricating oil compositions of the present invention may also contain, and preferably contain, other additives to impart certain desired properties to the lubricant. For example, at least one friction modifier may be included to impart suitable friction properties to the lubricating oil. Various amines, especially tertiary amines, are effective friction modifiers. Examples of tertiary amine friction modifiers include N-aliphatic alkyl-N,N-diethanolamine, N-aliphatic alkyl-N,N-diethoxyethanolamine, and the like. Such tertiary amines can be prepared by reacting an aliphatic alkylamine with an appropriate mole of ethylene oxide. Tertiary amines derived from natural sources such as coconut oil and oleylamine are available from Armor Chemical Company under the trade designation "Ethomeen". Particularly preferred are the Ethomeen-C and Ethomeen-O series.

Sulfur-containing compounds such as sulfurized _C12-24 fats, alkyl sulfides and polysulfides (wherein the alkyl group contains 1-8 carbon atoms) and sulfurized polyolefins can also be used as friction modifiers in the lubricating oil compositions of the present invention .

In one aspect, the preferred friction modifier for inclusion in the lubricating oil compositions of the present invention is at least one partial fatty acid ester of a polyhydric alcohol, typically up to 1% by weight of the partial fatty acid ester to enable Provides desired friction modifying properties. The hydroxy fatty acid esters are selected from hydroxy fatty acid esters of dihydric or polyhydric alcohols or their oxyalkylene derivatives.

Suitable partial fatty acid esters of polyhydric alcohols include, for example, glycol-esters, mono- and diglycerides and pentaerythritol di- and/or triesters. Partial fatty acid esters of glycerol are preferred, and among glycerol esters, monoesters or mixtures of monoesters and diesters are generally employed. Partial fatty acid esters of polyhydric alcohols can be prepared by methods known in the art, such as direct esterification of an acid with a polyol, reaction of a fatty acid with an epoxide, and the like.

It is generally desirable that the partial fatty acid esters contain ethylenic unsaturation, and often this ethylenic unsaturation is present in the acid groups of the ester. In addition to natural fatty acids containing ethylenically unsaturated moieties such as oleic acid, octenoic acid, tetradecenoic acid, etc. can also be used to form the esters.

The partial fatty acid ester used as a friction modifier in the lubricating oil composition of the present invention may be in the form of a mixed component containing various other components such as unreacted fatty acid, fully esterified polyhydric alcohol and others. Commercially available partial fatty acid esters generally contain mixtures of one or more of these components as well as mixtures of mono- and di-glycerides.

Commercially available mixtures of glycerides containing: at least about 30% by weight monoesters (usually about 35% to 65% by weight monoesters), about 30% to about 50% by weight diesters , the remainder are aggregates, usually a mixture of less than about 15% triesters, free fatty acids and other components. Specific examples of commercially available substances including glycerol fatty acid esters are Emery 2421 (Emery Industries, Inc.), Cap City GMO (Capital), DUR-EM 114, DUR-EM GMO etc. (Durkee Industries Foods Inc.) and Other trademarks are MAZOLGMO substances (Mazer Chemicals, Inc.). Other examples of partial fatty acid esters of polyhydric alcohols can be found in K.S. Markley ed.: "Fatty Acids", Second Edition, Parts I and V, (Interscience Press (1968)). "Emulsifiers and Detergents" by Mc Cutcheons (North American and International Combined Editions (1981)) lists a number of commercially available polyhydric alcohol fatty acid esters bearing trade names and manufacturers.

The lubricating oil composition of the present invention may also contain at least one neutral or basic alkaline earth metal salt of at least one acidic organic compound. The salt compounds mentioned above generally refer to ash-containing detergents. The acidic organic compound may be at least one of sulfuric acid, carboxylic acid, phosphoric acid or phenol or mixtures thereof. Typically, basic or overbased salts are preferred. The metal ratio of the basic or overbased salt can be up to about 40, more specifically from about 2 to about 30 or 40.

Calcium, magnesium, barium and strontium are preferred alkaline earth metals. Salts containing mixtures of two or more alkaline earth metal ions may be used.

A common method for preparing basic (or overbased) salts involves heating an acid and a stoichiometric excess of a metal neutralizing agent (e.g., metal oxide, hydroxide, carbonate, bicarbonate, salts, sulphides, etc.) in mineral oil. Additionally, various accelerators can be used in the neutralization process to aid in the incorporation of large excess metals. These accelerators include compounds such as phenolic substances (e.g., phenol, naphthol, alkylphenols, thiophenols, sulfurized alkylphenols, and various condensation products of formaldehyde with phenolic substances); alcohols (e.g., methanol, 2-propanol, octanol, cellosolve carbitol, ethylene glycol, stearyl alcohol, and cyclohexanol); amines (such as aniline, phenylenediamine, phenothiazine, phenyl-beta-naphthylamine, and dodecylamine) . A particularly efficient method of preparing basic salts involves mixing an acid with an excess of a basic alkaline earth metal in the presence of a phenolic promoter and a small amount of water and carbonating the mixture at elevated temperatures, such as from 60°C to about 200°C change.

As stated above, the acidic organic compound from which the alkaline earth metal salt can be derived is at least one containing sulfuric acid, carboxylic acid, phosphoric acid or phenol, or mixtures thereof. Some of the above-mentioned acidic organic compounds (sulfonic and carboxylic acids) have been described in relation to the preparation of alkali metal salts (component (E)), and all of the above-mentioned acidic organic compounds can be used in the preparation of alkaline earth metal salts. In addition to sulfonic acids, sulfuric acid includes thiosulfonic acids, sulfinic acids, sulfenic acids, partially esterified sulfuric acids, sulfurous acids and thiosulfuric acids.

The pentavalent phosphoric acid may be an organic phosphoric acid, a phosphonic acid or a phosphonous acid or a thio analog of the above acids.

Alkaline earth metal salts can also be prepared starting from phenols, ie, compounds containing hydroxyl groups directly attached to aromatic rings. The term "phenol" as used herein includes compounds having more than one hydroxyl group attached to an aromatic ring such as catechol, resorcinol and hydroquinone. Alkylphenols such as cresol and ethylphenol, and alkenylphenols may also be included. Preferred phenols contain at least one alkyl substituent having about 3-100, especially about 6-50 carbon atoms, for example, heptylphenol, octylphenol, dodecylphenol, tetrapropylene-alkylated phenol, Octadecylphenol and polybutenylphenol. Phenols containing more than one alkyl substituent can be used, but monoalkylphenols are preferred due to their availability and ease of manufacture.

Condensation products of the aforementioned phenols and at least one lower aldehyde or ketone are also useful. The term "lower" indicates that aldehydes and ketones contain not more than 7 carbon atoms. Suitable aldehydes include formaldehyde, acetaldehyde, propionaldehyde, and the like.

The amount of alkaline earth metal salts included in the lubricating oils of the present invention can also vary widely and can be readily determined by one skilled in the art in any particular lubricating oil composition. The role of the salt is as a builder or supplementary detergent. The amount included in the lubricants of the present invention can vary from about 0% to about 5% or more.

The lubricating oils of the present invention may contain at least one alkaline earth metal salt of a neutral or basic alkylphenol sulfide. The oil may contain from about 0 to about 2 or 3% of the phenolic sulfides. More often, the oil will contain from about 0.01 to about 2% by weight of the salt of the basic phenolic sulfide. The term "basic" as used herein has the same meaning as defined above for other compounds. The neutral and basic salts of phenolic sulfides provide antioxidant and detergency properties to the oil compositions of the present invention.

The oil composition of the present invention may also contain one or more sulfur-containing compounds to improve the wear resistance, extreme pressure and oxidation resistance of the lubricating oil composition. Sulfur-containing compositions prepared by sulfurizing various organic materials, including alkenes, are beneficial. The alkenes can be aliphatic, araliphatic or cycloaliphatic alkenes containing from about 3 to about 30 carbon atoms.

U.S. Patents 4,119,549, 4,505,830 and Re 37,331, incorporated herein by reference, disclose suitable sulfurized olefins for use in the lubricating oils of the present invention. Several specific vulcanizing compositions are described in the working examples of the aforementioned patents.

Other extreme pressure agents and anti-corrosion agents and antioxidants may also be included, examples of which are chlorinated aliphatic hydrocarbons such as chlorinated paraffins; organic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl) Disulfides, dibutyl tetrasulfide, sulfurized methyl oleate and sulfurized alkylphenols; reaction products of phosphorus sulfurized hydrocarbons such as phosphorus sulfide and turpentine or methyl oleate; phosphorous esters including dihydrocarbon and trihydrocarbon phosphites Such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, amylphenyl phosphite, dipentylphenyl phosphite, tridecyl phosphite, di- Octadecyl ester, dimethylnaphthyl phosphite, oleoyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500)-substituted phenyl phosphite, diisopropyl-substituted phenyl phosphite base esters, metal thiocarbamate salts such as zinc dioctyldithiocarbamate and barium heptylphenyldithiocarbamate.

Pour point depressants are particularly useful additives for use in such lubricating oils. The use of pour point depressants in oil-based compositions to improve the low temperature performance of oil-based compositions is well known in the art. See for example: C.V. Smalheer and R. Kennedy Smith "Lubricant Additives" p. 8, Lezius-Hiles Co. Press, Cleveland, Ohio, 1967.

Examples of suitable pour point depressants are polymethacrylates; polyacrylates; polyacrylamides; condensation products of halogenated paraffins and aromatic compounds; vinyl carboxylate polymers; Terpolymer of fatty acid vinyl esters and alkyl vinyl ethers. Pour point depressants for use in the present invention, their preparation and their use are described in: US 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498 2,666,746; 2,721,877; 2,721,878 and 3,250,715, the relevant disclosures of which are incorporated herein by reference.

Antifoam agents can be used to reduce or prevent the formation of stable foam. Typical defoamers are polysiloxanes or organic polymers. Other antifoam compositions are described in Henry T. Kerner: "Foam Control Agents" (Noyes Data Corporation, 1976) pp. 125-162.

The lubricating oil compositions of the present invention, especially when the lubricating oil compositions are to be formulated as thickened lubricating oils, may also contain one or more commercially available viscosity modifiers. Viscosity modifiers are generally polymeric materials characterized by hydrocarbon-based polymers having a number average molecular weight generally between about 25,000 and 500,000, preferably between 50,000 and 200,000.

Polyisobutylene has been used in lubricating oils as a viscosity modifier. Polymethacrylate (PMA) is prepared from methacrylate monomers with different alkyl groups. Most PMAs are both viscosity modifiers and pour point depressants. Alkyl groups can be straight or branched chain groups containing 1 to about 18 carbon atoms.

When a small amount of nitrogen-containing monomers are copolymerized with methyl methacrylate, the product can also have dispersion properties. Therefore, this product has various properties of adjusting viscosity, suppressing pour point and dispersing. Such products have been referred to in the art as dispersion-type viscosity modifiers or simply dispersion-viscosity modifiers. Vinylpyridine, N-vinylpyrrolidone and (N,N'-dimethylaminoethyl)methacrylate are examples of nitrogen-containing monomers. Polyacrylates prepared by polymerization or copolymerization of one or more alkyl acrylates are also useful as viscosity modifiers.

Ethylene-propylene copolymers (commonly referred to as OCP) can be prepared by copolymerization of ethylene and propylene, usually in a solvent, using a catalyst such as a Ziegler-Natta initiator. The ratio of ethylene to propylene in the polymer affects the product's oil solubility, oil thickening, low temperature viscosity, pour point depressant and engine operability. Typical ethylene contents are in the range of 45-60% by weight, typically 50% to about 55% by weight. Some commercial OCPs are terpolymers of ethylene, propylene, and small amounts of non-conjugated dienes such as 1,4-hexadiene. In the rubber industry, the above-mentioned terpolymers are known as EPDM (ethylene propylene diene monomer). The use of OCP as a viscosity modifier in lubricating oils has grown rapidly since 1970, and OCP is currently one of the most widely used motor oil viscosity modifiers.

Esters obtained by copolymerizing styrene and maleic anhydride in the presence of a free radical initiator and then esterifying the resulting copolymer with a C ₁₄ -C ₁₈ alcohol can also be used as motor oil viscosity modifiers. Styryl esters are generally considered to be versatile, advanced viscosity modifiers. If the reaction is terminated before the end of the esterification reaction and some unreacted anhydride or carboxylate remains, the styrene ester has pour point depressant and dispersant properties in addition to its viscosity regulating properties. These acid groups can then be converted to imides by reaction with primary amines. Hydrogenated styrene-conjugated diene copolymers are another class of commercially available motor oil viscosity modifiers.

The above-mentioned hydrogenated copolymers have been described in the prior art, see US 3,551,336; 3,598,738; 3,554,911; 3,607,749; 3,687,849 and 4,181, 618, the above-mentioned U.S. Patent, incorporated herein by reference, discloses polymers and copolymers useful as viscosity modifiers in the oil compositions of the present invention. Hydrogenated styrene-butadiene copolymers useful as viscosity modifiers in the lubricating oil compositions of the present invention are commercially available, for example, from BASF under the general trade designation "Glissoviscal". A specific example is the hydrogenated styrene-butadiene copolymer labeled Glissoviscal 5260, which has a molecular weight (determined by gel permeation chromatography) of about 120,000. Hydrogenated styrene-isoprene copolymers useful as viscosity modifiers are commercially available, for example, from The Shell Chemical Co. under the general trade designation "Shellvis". Shellvis 40 from Shell Chemical Co. is considered to be a diblock copolymer of styrene-isoprene with a number average molecular weight of about 155,000, a styrene content of about 19 mole percent, and an isoprene content of about 81% (mole). Shellvis 50 of Shell Chemical Co. is a diblock copolymer of styrene and isoprene, with a number average molecular weight of about 100,000, a styrene content of about 28% (mole), and an isoprene content of about 72% ( Moore). Generally, polymeric viscosity modifiers are used in concentrations of from about 0.2% to 8%, more preferably from about 0.5% to about 6% by weight of the finished lubricating oil.

The lubricating oils of the present invention may be prepared by dissolving or suspending the various components together with other optional additives in a base oil. More commonly, the chemical components of the present invention are diluted with a substantially inert, usually liquid, organic diluent such as mineral oil, naphtha, benzene, and the like to form an additive concentrate. The above-mentioned concentrate usually includes one or more of the above-mentioned additive components (A)-(C), in addition to that, it may also contain one or more of the above-mentioned other additives. Chemical concentrations of 15%, 20%, 30% or 50% or higher may be used.

For example, on a chemical basis, the concentrate may contain from about 10 to about 50% by weight of the carboxylic acid derivative composition (B) and from about 10 to about 5000 ppm manganese metal. The concentrate may also contain from 0.01% to 15% metal dithiophosphate (D), from about 1% to about 30% by weight of carboxylate (F) and/or from about 1% to about 20% by weight of At least one neutral or basic alkali metal salt (F).

A typical lubricating oil composition of the present invention can be illustrated by the following lubricating oil examples, wherein the percentages are on a volume basis and the percentages indicate the amount of a solution diluted with a conventional oil to form the specified additives of the lubricating oil composition. For example, Lubricant I contains 3.5% by volume of the product of Example B-10, which is an oil solution of the designated carboxylic acid derivative (B) containing 55% diluent oil.

Lubricant Example I

Component Percentage

Embodiment B-10 product 3.5

Embodiment D-1 product 0.4

Zinc dithiophosphate 0.47

(from amyl and isobutyl alcohol mixture

(35:65) m preparation)

Embodiment E-1 product 0.25

Alkaline magnesium benzenesulfonate 0.33

Basic calcium alkylated benzenesulfonate 0.41

Overbased manganese carboxylate

(40%Mn) (Mooney FOA-910) 250ppm

Amide-based friction modifier 0.1

C ₉ mono- and C ₉ -di-p-alkylated diphenylamine 0.1

Sulfurized butyl acrylate-butadiene product 0.15

Polysiloxane defoamer 0.006

mineral oil the remainder

Lubricant Example II

Component Percentage

Embodiment B-10 product 3.0

Diisooctyl dithiophosphate zinc salt 1.07

Embodiment F-6 product 2.8

Basic magnesium sulfonate 0.35

Basic calcium sulfonate 0.92

Nonylphenoxy poly(ethyleneoxy)ethanol 0.1

Overbased manganese carboxylate

(40%Mn)-Mooney FOA-910 250ppm

Propylene tetrapolyphenol reacted with sulfur dichloride 0.3

Polysiloxane defoamer 0.001

mineral oil the remainder

The lubricating oil composition of the present invention has low deterioration under application conditions, thereby reducing consumption and formation of unwanted deposits such as stains, dirt, carbonaceous substances and resinous substances that are easy to adhere to various engine parts, due to reduced the efficiency of the engine. In one embodiment, lubricating oils formulated in accordance with the present invention pass all test requirements as SG oil grades.

The lubricating oils of the present invention can also be used in diesel engines, and lubricating oil compositions can be prepared according to the present invention to meet the new diesel engine class CE requirements.

The performance parameters of the lubricating oil composition of the present invention can be evaluated by subjecting the lubricating oil composition to various engine oil tests which have been used to evaluate various performance parameters of engine oils.

The ASTM procedure IIID engine oil test simulates high-speed, high-load operation and is a rigorous test of the lubricating performance of an oil under application conditions. The test employed a 5.7 liter working volume, 2-cylinder 8.5:1 compression Oldsmobile V-8 gasoline engine. Each test requires the design of the engine as specified in ASTM STP 315H. The test was carried out in two parts: a 4 hour braking period followed by a 64 hour steady state test period. The engine was operated at 100bhp/74.6kw and was run at 3000rpm during the 64 hour test period. The test was monitored by taking samples and analyzing the lubricant every 8 hours. Add new oil to replace oil lost due to sampling and spills.

The performance criteria (SF quality) for the procedure IIID test are as follows: maximum viscosity increase measured at 45°C after 64 hours = 375%; average engine fouling rate 9.2 minimum; average engine piston velocity 9.2 minimum; average oil surface deposit 4.8 minimum; and tappet wear (inches), mean = 0.0040, max = 0.0080; oil consumption, quarts = 6.38.

The results of the Procedure IIID tests modified for use with non-phosphated camshafts and conducted with Lubricants I and II and Control Lubricants I and II are summarized in the table below. Control lubricants I and II were identical to lubricants I and II, respectively, except that the control lubricants did not contain manganese. (Regular Program IIID camshafts are manganese phosphated to improve seizure resistance and provide lubricant accumulation in the contact zone). The following table gives the test results.

As mentioned above, in order for a lubricating oil to achieve API service grade SG, the lubricating oil must pass certain specific engine oil tests. However, lubricating oil compositions that pass one or more of the individual tests may also be used for a particular application.

In recent years, the ASTM procedure IIIE engine oil test has been established as a means of determining the high temperature consumption, oil thickening and anti-sedimentation properties of SG engine oils. The IIIE test replaces the Program IIID test and provides improved discrimination in high temperature camshaft and tappet wear protection and oil thickening control. The IIIE test employed a Buick 3.8L V-6 engine operating at 67.8bhp on leaded fuel and running at 3000rpm for a maximum test time of 64 hours. Due to high engine operating temperatures, 100% ethylene glycol coolant is used. The output temperature of the coolant is maintained at 118°C, the oil temperature is maintained at 149°C, and the oil pressure is 30psi. The air to fuel ratio is 16.5 and the leak rate is 1.6 cfm. The initial oil charge was 146 oz.

The test was stopped when the oil level reached as low as 28 ounces during any 8-hour inspection interval. If the test was stopped before 64 hours due to low oil quantity, the low oil quantity is due to the increase of heavily oxidized oil in the engine, resulting in the oil not being able to drain into the fuel tank at the oil test temperature of 49°C. The viscosity of the 8 hour oil sample was obtained and from this data the viscosity increase was plotted as a percentage of engine hours. To meet API Class SG requirements, a maximum viscosity increase of 375% measured at 40°C at 64 hours is required. Engine fouling requirements are a minimum of 9.2, a minimum of 8.9 for piston fouling, and a minimum of 3.5 for annular deposits (based on the CRC standard rate system). Details of the currently used Procedure IIIE test are found in "Sequence IIID Surveillance Panel Report on Sequence III Test to the ASTM Oil Classification Panel", November 30, 1987, adapted January 11, 1988.

The results of the Procedure IIIE tests conducted with Lubricants I and II are summarized in Table III. For comparison, the results for Control Oil I and Control Oil II are also summarized in the table. Control Oils I and II correspond to Lubricating Oils I and II, respectively, except that the Control Oils do not contain the manganese additive.

While the invention has been described with reference to preferred embodiments, it is to be understood that various modifications will be apparent to those skilled in the art from the reading of the description. Therefore, it should be understood that the invention disclosed herein will include such modifications as fall within the scope of the appended claims.

Claims (30)

1, a kind of lubricant composition for internal combustion engine comprises:

(A) the lubricant viscosity oil of main amount;

(B) at least about at least a carboxylic acid derivatives compositions of 1.0% (weight), described carboxylic acid derivative preparation of compositions is to make

(B-1) amber acylation agent of at least a replacement with

(B-2) at least a amine compound reaction, the feature of wherein said amine is at least a HN＜group at its structure memory, the agent of described replacement amber is made up of substituted radical and amber group, described substituted radical is derived from polyene, the feature of described polyene is that the Mn value is 1300-about 5000, the Mw/Mn value is that 1.5-is about 4.5, and the feature of described acylating agent is for whenever the heavy substituting group of amount, at its structure memory at average at least 1.3 amber bases; With

(C) its consumption is enough to provide at least a manganic compound of the about 500ppm manganese metal of 1-, and condition is that described manganic compound is not a neutral dialkyl phosphorodithioic acid manganese.

2, the lubricating oil composition of claim 1, wherein cupric not substantially in the composition.

3, the lubricating oil composition of claim 1, wherein manganic compound (C) is the high alkalinity manganic compound.

4, the lubricating oil composition of claim 1 wherein also contains the about 5%(weight of (D) about 0.05%-) at least a by the dialkyl phosphorodithioic acid metal-salt shown in the formula (VIII),

R in the formula ¹And R ²Representative contains the alkyl of about 13 carbon atoms of 3-respectively, and M is a metal, and n is the integer identical with the M valence mumber.

5, the lubricating oil composition of claim 4, wherein at least one R ¹And R ²(D) link to each other with Sauerstoffatom by secondary carbon(atom).

6, the lubricating oil composition of claim 1 wherein also contains at least a neutrality of (E) washing significant quantity or sulfonic acid or carboxy acid alkali's metal-salt of alkalescence.

7, the lubricating oil composition of claim 1, manganic compound wherein (C) is selected from the salt of the acidic substance of carboxylic acid, sulfonic acid and phenol.

8, the lubricating oil composition of claim 1, manganic compound wherein (C) are overbasic mixed carboxylic acid's manganese salt.

9, the lubricating oil composition of claim 1, the manganese that wherein contains the about 300ppm of 50-that has an appointment is as metal.

10, the lubricating oil composition of claim 1, wherein the M value in (B) is at least about 1500.

11, the lubricating oil composition of claim 1, wherein the Mw/Mn in (B) is at least about 2.0.

12, the lubricating oil composition of claim 1, wherein in (B), about 0.5 equivalent-Yue 2 moles amine (B-2) reacts with every normal acylating agent (B-1).

13, the lubricating oil composition of claim 1, wherein the feature of acylating agent (B-1) is for whenever the amount substituting group, at its structure memory at least about about 2.5 amber bases of 1.5-.

14, a kind of lubricant composition for internal combustion engine comprises:

(A) the lubricant viscosity oil of main amount;

(B) at least about 1.0%(weight) at least a carboxylic acid derivatives compositions, described carboxylic acid derivative preparation of compositions is to make

(B-1) amber acylation agent of at least a replacement with

(B-2) at least a amine compound reaction, the feature of wherein said amine is at least a HN＜group at its structure memory, the agent of described replacement amber is made up of substituted radical and amber group, described substituted radical is derived from polyene, the feature of described polyene is that the Mn value is 1300-about 5000, the Mw/Mn value is that 1.5-is about 4.5, and the feature of described acylating agent is for whenever the heavy substituting group of amount, at its structure memory at average at least 1.3 amber bases; With

(C) its consumption is enough to provide at least a overbasic carboxylic acid or the azochlorosulfonate acid manganese salt of the about 500ppm manganese of about 1-metal.

15, the lubricating oil composition of claim 14 does not wherein contain copper substantially in the composition.

16, the lubricating oil composition of claim 14, wherein said magnesium compound (C) is overbasic manganese carboxylate.

17, the lubricating oil composition of claim 14 wherein also contains the about 5%(weight of (D) about 0.01%-) formula (VIII) shown at least a dialkyl phosphorodithioic acid metal-salt.

R in the formula ¹And R ²Representative contains the alkyl of about 13 carbon atoms of 3-respectively, and M is a metal, and n is the integer identical with the M valence mumber.

18, the lubricating oil composition of claim 17, wherein at least one R ¹And R ²(D) link to each other with Sauerstoffatom by secondary carbon(atom).

19, the lubricating oil composition of claim 17, wherein (D) comprises the mixture of dialkyl phosphorodithioic acid metal-salt, wherein at least one dialkyl phosphorodithioic acid, an alkyl (D-1) is sec.-propyl or sec-butyl, other alkyl (D-2) contain at least 5 carbon atoms, and in (D) at least about the 10%(mole) alkyl be sec.-propyl, sec-butyl or its mixture.

20, the lubricating oil composition of claim 14 wherein also contains at least a neutrality of (E) washing significant quantity or the sulfonic acid or the carboxylic metallic salt of alkalescence.

21, the lubricating oil composition of claim 20, wherein the feature of an alkali metal salt (E) is that the equivalence ratio of basic metal p-sulfonic acid or carboxylic acid was at least about 2: 1.

22, the lubricating oil composition of claim 14, wherein also contain:

(F) at least a carboxylates derivatives composition, its preparation is to make

(F-1) the amber agent of at least a replacement with

(F-2) alcohol of at least a general formula (XI) reaction:

R ³（OH）m （Ⅺ）

R in the formula ³Be unit price or the multivalence organic group that is connected in the OH base by carbon bond, m is the integer of 1-about 10.

23, the lubricating oil composition of claim 22, wherein m is at least 2.

24, the lubricating oil composition of claim 22, wherein by acylating agent (F-1) and the composition that obtains of alcohol (F-2) reaction further with

(F-3) at least a amine reaction that contains at least one HN＜group.

25, a kind of lubricant composition for internal combustion engine comprises:

(A) the lubricant viscosity oil of main amount;

(B) at least about 1.0%(weight) at least a carboxylic acid derivatives compositions, described carboxylic acid derivative preparation of compositions is to make

(B-1) amber acylation agent of at least a replacement with

(B-2) at least a amine compound reaction, the feature of wherein said amine is at least a HN＜group at its structure memory, the agent of described replacement amber is made up of substituted radical and amber group, described substituted radical is derived from polyene, the feature of described polyene is that the Mn value is 1300-about 5000, the Mw/Mn value is that 1.5-is about 4.5, and the feature of described acylating agent is for whenever the heavy substituting group of amount, at its structure memory at average at least 1.3 amber bases; With

(C) consumption enough provides at least a overbasic at least a manganese carboxylate salt of the about 300ppm manganese of about 50-as metal.

(D) the about 5%(weight of about 0.05%-) dialkyl phosphorodithioic acid metal-salt shown at least a formula (VIII)

R in the formula ¹And R ²Representative contains the alkyl of about 13 carbon atoms of 3-, R at least respectively ¹And R ²One of link to each other with Sauerstoffatom by secondary carbon(atom), M is the metal that is selected from II main group metal, aluminium, tin, iron, cobalt, lead, molybdenum, manganese, nickel or copper, and n is the integer identical with the M valence mumber.

26, the lubricating oil composition of claim 25 wherein also comprises

Sulfonic acid or carboxy acid alkali's metal-salt of at least a neutral (E) the about 3%(weight of about 0.01%-) or alkalescence.

27, the lubricating oil composition of claim 25 wherein also comprises

(F) at least a carboxylates derivatives composition about 0.1%-10%(weight), its preparation is to make

(F-1) amber acylation agent of at least a replacement with

(F-2) reaction of alcohol shown at least a general formula (XI),

R ³（OH）m （Ⅺ）

R in the formula ³Be unit price or the multivalence organic group that links to each other with the OH group by carbon atom, m is the integer of 1-about 10.

28, a kind ofly prepare the enriched material that lubricating oil composition is used, comprise

(A) the common liq about 90%(weight of about 20%-) is inert organic thinner/solvent basically;

(B) at least about 1.0%(weight) at least a carboxylic acid derivatives compositions, described carboxylic acid derivative preparation of compositions is to make

(B-1) amber acylation agent of at least a replacement with

(B-2) at least a amine compound reaction, the feature of wherein said amine is at least a HN＜group at its structure memory, the agent of described replacement amber is made up of substituted radical and amber group, described substituted radical is derived from polyene, the feature of described polyene is that the Mn value is 1300-about 5000, the Mw/Mn value is that 1.5-is about 4.5, and the feature of described acylating agent is for whenever the heavy substituting group of amount, at its structure memory at average at least 1.3 amber bases; With

(C) consumption is enough to provide at least a manganic compound of the manganese metal of the about 5000ppm of about 10-, and condition is that described manganic compound is not a neutral dialkyl phosphorodithioic acid manganese.

29, the enriched material of claim 28 wherein also contains the about 15%(weight of 0.05%-)

(D) at least a dialkyl phosphorodithioic acid metal-salt shown in the formula (VIII) the about 5%(weight of about 0.05%-):

R in the formula ¹And R ²Be respectively the alkyl that contains about 13 carbon atoms of 3-, M is a metal, and n is the integer identical with the m valence mumber.

30, the enriched material of claim 28 wherein also contains the 1%-20%(weight of having an appointment)

(E) sulfonic acid or carboxy acid alkali's metal-salt of at least a neutral or alkalescence.