JPH0260718B2 - - Google Patents

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION 1 Field of the Invention The present invention provides antioxidant properties when added to lubricating oils.
The present invention relates to a normally liquid lubricating oil additive that is a multifunctional additive that provides diesel fuel deposition control and friction modification properties. In particular, the present invention provides _C14 to _C18 additives for lubricating oils that are normally liquid at typical storage temperatures.
Concerning alkylcatechols. The alkylcatechols of the present invention are multifunctional lubricant additives useful in lubricating oils that provide anti-oxidant diesel fuel deposit control and boundary friction properties. 2. Prior Art Certain alkylcatechols are known in the art as antioxidant additives for lubricating oils. In particular, Wright U.S. Patent No. 2,429,905
No. 2 states that para-substituted stearyl catechols and other para-substituted lower alkyl catechols have antioxidant properties. Similarly, Andress
U.S. Pat. No. 3,554,945 to et al. discloses polyhydroxybenzenoid compounds as useful antioxidant additives in lubricating oils. Although _the Andres et al _{. patent discloses alkylated products synthesized from C15-C20 mixed olefin} fractions, Andres et al. It is not explicitly stated that it will have modifying properties. Thomas et al. U.S. Patent No.
No. 2795548 is another prior art document disclosing alkylcatechols. Thomas et al. specifically disclose alkylcatechols containing 2 to 18 carbon atoms in the alkyl group, which are used as intermediates in the synthesis of borate-esterified alkylcatechols. Long chain monoalkyl catechols with 14 or more carbon atoms have improved antioxidant and diesel fuel deposit control properties over those of short chain monoalkyl catechols (those with fewer than 14 carbon atoms). It was discovered here that it has a boundary lubricity property. Therefore, when using alkylcatechol additives in lubricating oils, it is desirable to use long-chain alkylcatechols. However, there are problems with the use of long chain alkyl catechols as their synthesis often results in some degree of solidification or haze in the product. The extent of this problem ranges from alkylcatechols that are solid waxes at room temperature to liquid alkylcatechols that contain wax particles at room temperature. In any case, if such solidification or clouding occurs, heating the alkylcatechol prior to compounding would add an additional step to the overall process, or the alkylcatechol would increase transportation costs. It is necessary that solid particles or haze must be removed either by the addition of a sufficient amount of diluent oil to the solution. For short chain alkyl catechols, this caking problem appears to be less severe, but the use of these short chain alkyl catechols may come at the expense of improvements in interfacial friction. Therefore, it is normally liquid at typical storage temperatures while having sufficient alkyl chain length to impart multifunctionality to the lubricating oil, such as antioxidant properties, diesel fuel deposit control properties, and antifriction properties. It is necessary to develop alkylcatechols. At least three types of C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ and C ₁₈
20 synthesized from a mixture of linear α-olefins of
It has now been found that _C14 - _C18 monoalkyl catechols having a _C18 alkyl content of less than % are normally liquid at typical storage temperatures. moreover,
The _C14 to _C18 alkyl chain length imparts multifunctionality to the lubricating oil. The liquid properties of the C ₁₄ -C ₁₈ monoalkyl catechols of the present invention are similar to those of the monoalkyl catechols synthesized from a mixture of C ₁₈ , C ₁₉ , C ₂₀ and C ₂₁ linear α-olefins, as well as the C 14 -C ₁₈ monoalkyl catechols of the present invention. This is a particularly surprising property in view of the fact that monoalkylcatechols with a C ₁₈ content greater than 20% synthesized from a mixture of ₁₆ , and C ₁₈ linear α-olefins solidify slightly. SUMMARY OF THE INVENTION The present invention relates to normally liquid _C14 - _C18 monoalkyl catechols that are useful lubricating oil additives. In particular, the present invention provides that the alkyl substituents are C ₁₄ , C ₁₅ , C ₁₆ ,
Derived from _C17 and _C18 linear α-olefins
A mixture of at least three of C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ and C ₁₈ alkyl groups, consisting of monoalkylcatechols, in which the content of C ₁₈ alkyl groups is not more than 20% of the total alkyl content Concerning normally liquid alkylcatechols. Monoalkylcatechol has the formula (wherein R is derived from a linear α-olefin
It is a mixture of at least three of C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ and C ₁₈ alkyl groups. ) can be expressed as In any case, the _C18 alkyl content must be kept below 20% of the total alkyl groups to be a liquid product. Preferably, the _C18 alkyl content is kept below 15%. A particularly preferred group of _C14 - _C18 alkylcatechols are _C14 - _C18 alkylcatechols derived from pyrolized, ie cracked, wax alpha-olefins. _C14 - _C18 pyrolytic wax alpha-olefins are easily synthesized as described in U.S. Pat. No. 3,883,417. This patent is incorporated herein by reference as teaching the synthesis of olefins in pyrolytic waxes. Another preferred linear α-olefin for use in the synthesis of the alkylcatechols of the present invention is one derived from an ethylene propagation process.
This ethylene growth process can be accomplished by high temperature oligomerization of ethylene using a nickel chelate catalyst. Another method is described in U.S. Pat. No. 2,889,385, which is also incorporated herein by reference as teaching the "ethylene propagation" synthesis of olefins. Blends of C ₁₄ , C ₁₆ and C ₁₈ linear α-olefins are available from Shell Chemicals, Houston, Texas.
It is commercially available under the registered trade name Neodene (Neodene®) from Biochemistry Chemicals. The C ₁₄ to C ₁₈ monoalkyl catechol of the present invention not only has antioxidant properties and diesel fuel deposition inhibiting properties, but also has boundary friction modifying properties. Thus, another aspect of the invention relates to a lubricating oil composition comprising an oil of lubricating viscosity and an effective amount of a _C14 - _C18 monoalkylcatechol of formula I above. Other additives are also present in the lubricating oil to obtain the right balance of properties critical for the proper operation of the internal combustion engine, such as dispersibility, anti-corrosion, anti-wear and anti-oxidation properties. You may do so. Thus, yet another aspect of the invention comprises: (a) a majority amount of an oil having a lubricating viscosity, and (b) an effective amount of each of the following additives: 1 an alkenylsuccinimide, 2 a Group metal of dihydrocarbyl dithiophosphate; 3 neutral or overbased alkali or alkaline earth metal hydrocarbylsulfonates or mixtures thereof; 4 neutral or overbased alkali or alkaline earth alkylated phenates or mixtures thereof;
and 5 _C14 to _C18 monoalkyl catechol friction modifiers for improving the fuel consumption of internal combustion engines.
The present invention relates to lubricating oil compositions particularly useful in internal combustion engine crankcases. Further in accordance with the present invention, there is provided a method of treating a moving surface with the lubricating oil composition to reduce fuel consumption in an internal combustion engine. The term "monoalkylcatechol" as used in the present invention means the product obtained by reacting an essentially stoichiometric mixture of _C14 - _C18 alpha-olefins with pyrocatechol. . Such products generally contain some amount of dialkylcatechol. The stoichiometric ratio of C ₁₄ to C ₁₈ α-olefin to pyrocatechol is generally 0.9:1 to 1.2:1, preferably 1:1 to 1.1:1. As used in the present invention, the term "at least three C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ and C ₁₈ alkyl groups derived from linear α-olefins" refers to alkylating catechols. used for
The mixture of _C14 - _C18 linear alpha-olefins contains at least 1% each of the three components, preferably at least 5%, most preferably at least 10%.
This means that it must contain. The term “linear α-olefin” refers to α-
While the olefins are primarily linear, less than 10%, preferably less than 5%, of the alpha-olefins in the alpha-olefin mixture are branched, e.g. (wherein R is alkyl having 8 to 12 carbon atoms). The term "normally liquid" as used in the present invention also means that the C ₁₄ -C ₁₈ monoalkyl catechol is liquid at typical storage temperatures and atmospheric pressures without the presence of any wax or haze. It means something. DETAILED DESCRIPTION OF THE INVENTION The normally liquid _C14 - _C18 monoalkylcatechol of formula I is a mixture of pyrocatechol and at least three of _C14 - _C18 linear alpha-olefins, the _C18 content being It is synthesized by alkylation with a mixture thereof that is not more than 20%. For example, the alkylcatechol of formula I can be prepared by converting a straight-chain alpha-olefin containing 14 to 18 carbon atoms in an essentially inert solvent in the presence of an alkylation catalyst to about 60 to 18 carbon atoms. 200℃, preferably 125~
It can be synthesized by reaction with pyrocatechol at a temperature of 180°C and atmospheric pressure. Preferred alkylation catalysts are sulfonic acid catalysts, such as those from Pennsylvania
Amberlyst 15 is available from Rohm and Haas, Philadelphia. Although the reactants can be used in various molar ratios, linear α with a 10% molar excess of catechol
- Preference is given to using olefins. Examples of inert solvents are benzene, toluene, chlorobenzene, and 250 Thinner, which is a mixture of aromatics, paraffins, and naphthenes. The alkylcatechols of the present invention generally have the formula (wherein R is a mixture of at least three of C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ and C ₁₈ alkyl groups). Also, up to 25% by weight, preferably
Up to 15% by weight of alkylcatechol can be present at a position adjacent to one of the hydroxyl groups or at one of the hydroxyl groups.
The catechol has a group R in the ortho position to (wherein R is the same as defined above). Although the applicant does not wish to be limited by any theory, at least three _C14 - _C18
Alkylcatechol products containing mixtures of linear alpha-olefins with a _C18 content of less than 20% are believed to break up their crystals to yield liquid products. However, when the C ₁₈ alkyl group content exceeds about 20%, the ability of the resulting mixed alkyl groups to inhibit crystallization of alkylcatechol is impaired. Therefore, the α-olefin mixture used in synthesizing the alkyl catechols of the present invention is prepared from a mixture of at least three C ₁₄ to _{C 18} linear α-olefins, where the C ₁₈ content is 20%. Below, it is necessary to keep it preferably below 15%. The liquid properties of C _{14 -C 18} alkyl catechol mixtures with a C 18 alkyl content of 20% or less are such that when a single linear α-olefin (e.g. C ₁₆ ) is used to alkylate the catechol, the resultant alkyl This is particularly surprising in view of the fact that catechol is nevertheless a mixture. These mixtures are derived from the isomerization of olefin bonds with acidic alkylation catalysts, as shown in reactions (I) and () below. In addition, in the following reaction formula, _C16 alpha-olefin is used only for explanation. However, m and n can each independently take an integer value from 0 to 14 on the condition that the sum m+n is equal to 14. As is readily apparent, the alkylation of pyrocatechol with a single linear α-olefin species results in a mixture of products with different m and n values. However, as shown in Table I, the corresponding C ₁₆ and C ₁₈ alkyl catechols synthesized from a single linear α-olefin solidify. Considering the isomerization of olefin bonds in alpha-olefins by acidic alkylation catalysts, the term "alpha-olefin" as used in the present invention also encompasses isomerized olefins from the corresponding alpha-olefins. Also included within the scope of the present invention are fully formulated lubricating oils containing about 0.5 to 5% by weight of the _C14 to _C18 alkyl catechols of the present invention. The fully formulated composition includes the following ingredients: 1. an alkenyl succinimide, 2. a Group metal salt of dihydrocarbyl dithiophosphoric acid, 3. a neutral or overbased alkali or alkaline earth metal hydrocarbyl sulfonate or mixture thereof, and 4. natural or overbased alkali or alkaline earth metal alkylated phenates or mixtures thereof. The alkenyl succinimide is present to act as a dispersant and prevent deposits from forming during engine operation. Alkenyl succinimides are well known in the art.
Alkenyl succinimides are the reaction products of polyolefin polymer-substituted succinic anhydrides and amines, preferably polyalkylene polyamines. Polyolefin polymer-substituted succinic anhydride is obtained by reacting a polyolefin polymer or a derivative thereof with maleic anhydride. The succinic anhydride thus obtained is reacted with an amine compound. The synthesis of this alkenyl succinimide has been described many times in the art. See, for example, US Pat. No. 3,390,082, US Pat. No. 3,219,666 and US Pat. The disclosures of these US patents are incorporated herein by reference. Reduction of this alkenyl-substituted succinic anhydride produces the corresponding alkyl derivative. This alkylsuccinimide is also intended to be included within the scope of the term "alkenylsuccinimide". Products consisting primarily of mono- or bis-succinimide can be prepared by controlling the molar ratios of the reactants. Thus, for example, when one mole of amine is reacted with one mole of alkenyl or alkyl substituted succinic anhydride, a predominantly monosuccinimide product is formed. Also,
When two moles of succinic anhydride are reacted per mole of polyamine, bis-succinimide is formed. Particularly good results are obtained with the lubricating oil compositions of the invention when the alkenylsuccinimide is a polyisobutene-substituted succinic anhydride of a polyalkylene polyamine. Obtained by polymerizing isobutene,
The composition of the polyisobutene used to produce polyisobutene-substituted succinic anhydride can vary widely. Average number of carbon atoms from 30 or less
can range up to 250 pieces or more;
This range provides number average molecular weights from about 400 or less to 3000 or more. Preferably,
Average number of carbon atoms per polyisobutene molecule is approximately 50
to about 100, within which the polyisobutene has a number average molecular weight of about 600 to about 1500. More preferably, the average number of carbon atoms per polyisobutene molecule ranges from about 60 to about 90, and the number average molecular weight ranges from about 800 to 1300. Polyisobutene is reacted with maleic anhydride according to well-known procedures to yield polyisobutene-substituted succinic anhydride. In synthesizing alkenyl succinimides, substituted succinic anhydrides are reacted with polyalkylene polyamines to form the corresponding succinimides. Each alkylene group of the polyalkylene polyamine usually has up to about 8 carbon atoms. The number of alkylene groups can range up to about 8.
Examples of the alkylene group include ethylene, propylene, butylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and octamethylene. The number of amino groups is generally, but not necessarily, one greater than the number of alkylene groups present in the amine, i.e. if the polyalkylene polyamine contains three alkylene groups, the number of amino groups is Usually there are 4 pieces. The number of amino groups can range up to about 9. Preferably, alkylene groups have about 2 to about 4 carbon atoms and all amine groups are primary or secondary. In this case, the number of amino groups is one more than the number of alkylene groups. Preferably, the polyalkylene polyamine contains 3 to 5 amine groups. Specific examples of polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, tripropylenetetramine, tetraethylenepentamine, trimethylenediamine, pentaethylenehexamine, di-(trimethylene)triamine, and tri(hexamethylene)tetramine. and so on. Other amines suitable for synthesizing alkenyl succinimides useful in this invention include cyclic amines such as piperazine, morpholine, and dipiperazines. Preferably, the alkenyl succinimide used in the compositions of the invention has the formula: provided that (a) R ₁ is a substantially saturated hydrocarbon prepared by polymerizing an alkenyl group, preferably an aliphatic monoolefin, and preferably R ₁ is prepared from isobutene; and has the average number of carbon atoms and number average molecular weight as described above. (b) An "alkylene" group is essentially a hydrocarbyl group containing up to about 8, preferably about 2 to 4 carbon atoms, as described above. (c) A is a hydrocarbyl group, an amine-substituted hydrocarbyl group, or hydrogen. Hydrocarbyl groups and amine-substituted hydrocarbyl groups are generally alkyl and amino-substituted alkyl congeners of the aforementioned alkylene groups. Preferably A is hydrogen. (d) n is an integer from about 1 to 10, preferably from about 3 to 5; The alkenyl succinimide is present in the lubricating oil composition of the present invention in an amount effective to act as a dispersant and to inhibit the deposition of contaminants formed in the oil during engine operation. The amount of alkenyl succinimide can range from about 1 to about 20% by weight of the total lubricating oil composition. Preferably, the amount of alkenyl succinimide present in the lubricating oil compositions of the present invention ranges from about 1 to about 10% by weight, based on the total composition. The alkali or alkaline earth metal hydrocarbyl sulfonates may be petroleum sulfonates, synthetically alkylated aromatic sulfonates, or aliphatic sulfonates, such as those derived from polyisobutylene. One of the more important functions of these sulfonates is to act as detergents and dispersants. These sulfonates are well known in the art. The hydrocarbyl group must have a sufficient number of carbon atoms to render the sulfonate molecule oil-soluble.
Preferably, the hydrocarbyl moiety has at least 20 carbon atoms and can be aromatic or aliphatic, but is usually alkylaromatic. Aromatic calcium, magnesium or barium sulfonates are most preferred for use. Certain sulfonates are typically synthesized by sulfonating petroleum distillates having aromatic groups, usually mono- or dialkylbenzene groups, and then forming metal salts of the sulfonic acid material. Other raw materials used to synthesize these sulfonates include synthetically alkylated benzene, and by polymerizing aliphatic hydrocarbons such as isobutene, which are synthesized by polymerizing mono- or diolefins. There are polyisobutenyl groups that are synthesized. Metal salts are formed directly or by metathesis using well known procedures. These sulfonates can be neutral or have base numbers up to about 400 or more.
may be overbased with numbcr). Carbon dioxide and calcium hydroxide or calcium oxide are the most commonly used materials to produce basic or overbased sulfonates. Mixtures of neutral and overbased sulfonates can also be used. Sulfonates are normally used to provide 0.3 to 10% by weight of the total composition. Preferably, the neutral sulfonate is present in a proportion of 0.4 to 5% by weight, based on the total composition, and the overbased sulfonate is present in a proportion of 0.3 to 3% by weight, based on the total composition. Phenates for use in the present invention are conventional products that are alkali or alkaline earth metal salts of alkylated phenols. One of the functions of phenates is to act as detergents and dispersants.
Among other things, phenates prevent the deposition of contaminants produced during high-temperature operation of the engine. The phenols may be mono- or polyalkylated. The alkyl portion of the alkyl phenate is present to impart oil solubility to the phenate. Alkyl moieties can be obtained from natural or synthetic sources. Natural sources include petroleum hydrocarbons such as white oil and waxes. The hydrocarbon component derived from petroleum is a mixture of various hydrocarbyl groups, the specific composition of which depends on the particular oil feedstock used as a starting material. Suitable synthetic sources include a variety of commercially available alkene and alkane derivatives that provide alkylphenols when reacted with phenols. Suitable groups that may be obtained include butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, eicosyl, tricontyl and similar groups. Other suitable synthetic sources of alkyl groups include polypropylene, polybutylene,
There are olefin polymers such as polyisobutylene and similar polymers. The alkyl group can be a straight-chain or branched saturated or unsaturated group (if unsaturated it preferably contains no more than 2 and generally no more than 1 site of olefin unsaturation). ). Alkyl groups generally contain 4 to 30 carbon atoms. in general,
When the phenol is monoalkyl substituted, the alkyl group must contain at least 8 carbon atoms. The phenate may be sulfurized if desired. The phenates can be either neutral or overbased and, if overbased, have a base number of up to 200 to 300 or more. Mixtures of neutral and overbased phenates can also be used. Phenates are normally present in the oil to give a proportion of 0.2 to 27% by weight of the total composition. Neutral phenates in amounts of 0.2-9% by weight and overbased phenates in amounts of 0.2-13% by weight, based on the total composition.
Each is preferably present in an amount of . Most preferably, the overbased phenate is present in an amount of 0.2 to 5% by weight of the total composition. Preferred metals are calcium, magnesium, strontium or barium. Sulfurized alkaline earth metal phenates are preferred. These salts can be obtained in various ways, such as by treating the neutralization product of an alkaline earth metal base with an alkylphenol with sulfur. Sulfur is conveniently added to the neutralization product in elemental form and reacts at elevated temperatures to form the sulfurized alkaline earth metal alkyl phenate. If more alkaline earth metal base is added during the neutralization reaction than is required to neutralize the phenol,
A basic sulfurized alkaline earth metal alkyl phenate is obtained. For example, Walker
See the method described in US Pat. No. 2,680,096 by et al. Additional basicity can be obtained by adding carbon dioxide to the basic sulfurized alkaline earth metal alkyl phenate. Although an excess of alkaline earth metal base can be added following the sulfidation step, it is convenient to add it at the same time as the alkaline earth metal base is added to neutralize the phenol. Carbon dioxide and calcium hydroxide or oxide are the materials most commonly used to make basic or overbased phenates. A method for producing basic sulfurized alkaline earth metal alkyl phenates by adding carbon dioxide is described by Hanneman.
No. 3,178,368. Group metal salts of dihydrocarbyl dithiophosphoric acids exhibit wear resistance, antioxidant properties, and thermal stability. Group II metal salts of phosphorodithioic acids have been known for some time. See, eg, US Pat. No. 3,390,080. Columns 6 and 7 thereof generally describe these compounds and their synthesis. Group metal salts of dihydrocarbyl dithiophosphoric acids useful in the lubricating oil compositions of this invention suitably contain from about 4 to about 12 carbon atoms in each hydrocarbyl group. The hydrocarbyl groups may be the same or different and may be aromatic, alkyl or cycloalkyl. Preferred hydrocarbyl groups are alkyl groups having 4 to 8 carbon atoms, including butyl, isobutyl, sec.-butyl, hexyl, isohexyl, octyl, 2-ethylhexyl and similar alkyl groups. Suitable metals for forming these salts include barium, calcium, strontium, zinc and calcium, with zinc being preferred. Preferably, the Group metal salt of dihydrocarbyl dithiophosphoric acid has the formula: (e) R ₂ and R ₃ each independently represent a hydrocarbyl group as described above, and (f) M ₁ represents a Group metal cation as described above. The dithiophosphate is present in the lubricating oil compositions of the present invention in an amount effective to inhibit wear and oxidation of the lubricating oil. The amount is about 0.1 to about 4 for the total composition.
% by weight. Preferably, the salt is present in an amount ranging from about 0.2% to about 2.5% by weight of the total lubricating oil composition. The final lubricant composition typically ranges from 0.025 to
It contains 0.25% by weight of phosphorus, preferably 0.05-0.15% by weight. Finishing lubricants can be single grade or multigrade. Multigrade lubricating oils are prepared by adding viscosity index improvers (). Typical viscosity index improvers are polyalkyl methacrylates, ethylene-propylene copolymers, styrene-diene copolymers and similar polymers. So-called modified improvers having both viscosity index properties and dispersibility properties are also suitable for use in the formulations of the invention. The lubricating oil used in the compositions of the present invention can be a mineral or synthetic oil of a viscosity suitable for use in the crankcase of an internal combustion engine.
Crankcase lubricating oil is usually about 0%
It has a viscosity of 22.7 cst at 1300 cst to 210°C (99°C). These lubricating oils can be derived from synthetic or natural sources. Mineral oils used as base oils in this invention include paraffinic base oils, naphthenic base oils and other oils commonly used in lubricating oil compositions. Synthetic oils include both synthetic hydrocarbon oils and synthetic ester oils. Useful synthetic hydrocarbon oils include liquid alpha-olefin polymers of suitable viscosity. C6 _~ 12α- like 1-decene trimer
Hydrogenated liquid oligomers of olefins are particularly effective. Similarly, alkylbenzenes of appropriate viscosity, such as didocylbenzene, can also be used. Useful synthetic esters include esters of both monocarboxylic and polycarboxylic acids and of monohydroxyalkanols and polyols. Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2
- ethylhexyl adipate, dilauryl sebacate and similar esters. Complex esters synthesized from mixtures of mono- and dicarboxylic acids and mono- and dihydroxyalkanols can also be used. Blends of hydrocarbon and synthetic oils are also useful. For example, a blend of 10-25% by weight hydrogenated 1-decene trimer with 75-90% by weight 150SUS (100〓) mineral oil provides an excellent lubricant base. Additive concentrates are also within the scope of this invention. In this concentration additive dosage form, the C ₁₅ of the invention
The ~ _C18 alkylcatechol is present in a concentration ranging from 5 to 50% by weight. Other additives that may be present in this formulation include anti-rust additives, foam inhibitors, corrosion inhibitors, metal deactivators, pour point depressants, antioxidants and various other well known additives. be. The following examples are presented to specifically illustrate the invention. These examples and descriptions should not be construed as limiting the scope of the invention in any way. EXAMPLES Example 1 In three flasks equipped with a stirrer, a Dean-Stark trap, a condenser, and a nitrogen inlet and outlet, 759 g of _C15 - _C18 alpha-olefin mixture, 330 g of pyrocatechol, 165 g of sulfonic acid cation exchange resin ( Charge a divinylbenzene crosslinked polystyrene catalyst (Amberlyst 15, commercially available from Rohm and Haas, Philadelphia, Pa.) and 240 ml of toluene.
The reaction mixture was stirred under a nitrogen atmosphere.
Heat to 150-160°C for 7 hours. The reaction mixture is stripped by heating to 160°C under vacuum (0.4 mmHg). Filter the hot product through a super cell (SCC) to reduce 930g of liquid _C15.
~ _C18 alkyl substituted pyrocatechol is obtained. The hydroxyl number of the product was 259. Example 2 759 g C ₁₄ , C ₁₆ , and C ₁₈ α-olefin mixture, 330 g pyrocatechol, 165 g sulfonic acid cation exchange in 3 flasks equipped with stirrer, Dean-Stark trap, condenser, and nitrogen inlet/outlet. Add a resin (polystyrene crosslinked with divinylbenzene) catalyst (Amberlyst 15, commercially available from Rohm and Haas, Philadelphia, Pa.) and 220 ml of toluene. The reaction mixture is heated to 150 DEG-160 DEG C. for about 1/2 hour with stirring under a nitrogen atmosphere.
Add another 45ml of toluene. The reaction mixture is continued to be heated at 150-160° C. for an additional 3 hours under a nitrogen atmosphere. The reaction mixture (~75°C) is filtered through Super Cell (SCC). Vacuum the filtrate (0.4mmHg)
stripping by heating to 160° C. to obtain liquid C ₁₄ , C ₁₆ , and C ₁₈ alkyl-substituted pyrocatechols. By carrying out the method of the above example,
The following alkylcatechols were synthesized. The results are shown in Table I below.

[Table] The purpose is to quickly determine the physical properties of alkylcatechols that are likely to be used.
Example 11 The monoalkylcatechol of Example 1 was tested in the Catapillar 1-G2 test. In this test, the inner diameter 5-1/8" x stroke 6-1/
A 2″ single cylinder diesel engine is operated under the following conditions: Timing 8° BTDC; Average effective brake pressure 141 psi; Brakes 42 hp;
5850Btu's/min; Speed 1800RPM; Air Boost
53″ Absolute Hg; Air temperature (in) 255〓; Water temperature (out)
190〓; and sulfur in fuel 0.4%W. At the end of each 12 hour run, enough oil is drained from the crankcase to add one quart of new oil.
In tests on lubricating compositions of the invention, 1
- G2 test is conducted for 60 hours. At the end of this test period, the engine is disassembled and evaluated for cleanliness.
The Institute of Petroleum Test is a highly regarded engine wear and cleanliness evaluation system and is accepted by ASTM, API and SAE.
Petroleum Test) No. 247/69 is the evaluation system used to evaluate engines. The overall cleanliness is expressed as WTD, which is the sum of the above numbers. A smaller value indicates a cleaner engine. The base oils used in this test were 1.63% isobutenyl succinimide 50% concentrate in oil, 1% isobutenyl bis-succinimide 50% concentrate in oil, calcium sulfonate 9 mmol/Kg, and overbased calcium sulfonate. CIT-CON 350N base oil containing 10 mmol/Kg, calcium sulfide phenate 10 mmol/Kg, zinc dialkyldithiophosphate 8.25 mmol/Kg and 0.05% sulfated polyglycol. The results of this test are shown in Table 1.

[Table] Noalkylcatechol 2%
Example 12 1% by weight of monoalkylcatechol from Example 1
Formulated oils were prepared and tested using the Sequence D test method (per ASTM Special Technical Publication 315H). In each test, the compounded base oil, and polyisobutenyl succinimide of triethylenetetramine.
3.5%, overbased magnesium hydrocarbylsulfonate 30 mmol/Kg, overbased sulfurized alkylphenol 20 mmol/Kg, zinc di(2-ethylhexyl) dithiophosphate 18 mmol/Kg and viscosity index improver for polymethacrylate beads 5.5% A comparison was made using RPM10W30, which contains Sequence D Test The objective of this test was to determine the oxidation rate of the oil and the effects of additives at relatively high temperatures (oil internal temperature during the test approximately 149°C) on the wear of cams and lifters in the valve train of an internal combustion engine. The goal is to quantify the effect. In this test, an Oldsmobile 350 CID engine was operated under the following conditions: 3000 RPM/64 hours maximum run time and 100 lb load; air/fuel ratio ^* = 16.5/1, GMR reference fuel (added). Timing = 31゜BTDC; Oil temperature = 300〓 Cooling water temperature (in) = 235〓 - (out) 245〓: Back pressure water for exhaust = 30''; Flow rate of jacket cooling water = 60 gallons/minute; Rocker cover cooling water flow rate = 3 gallons/minute
minutes; humidity must be kept at 80 grams of H ₂ O; air temperature controlled equal to inlet temperature equal to 80〓; blowby the breather heat exchanger at 100〓. Additive effectiveness is determined after 64 hours in terms of camshaft and lifter wear and % viscosity increase. The results are shown in the table below. Table Sequence D Test Viscosity formulation increase over 64 hours, % basis Too viscous to measure Base + 1% of compound synthesized according to Example 1 (a) 250 Example 13 Alkylcatechol of the invention Tests were conducted to demonstrate the reduction in boundary friction obtained by its addition to lubricating oil compositions. The test was conducted by adding a blended oil containing a friction modifier to a tabletop tester that measures friction. Reference oil, MPG-1, is succinimide 3.5
%, 20 mmol overbased phenate, 30 mmol magnesium sulfonate, 18 mmol zinc dithiophosphate and 8% improver. Add 25 mmol/friction modifier to this formulation.
Added at a concentration of 100g. The table shows several formulations each containing one friction modifier. The friction tabletop tester consists of a cast iron "bullet" resting on an A247 cast iron disk. This assembly is placed in a cap where test oil is added. Trial runs were started for 10 minutes of operation at 100 rpm and low load. Friction data at a temperature of 100℃,
Recordings were made at 150°C and 300°C, a speed of 0.8 rpm and a load of 1 kg. All tests were performed twice. The results are shown in Table 1.

[Table] In the above table, the number below the temperature value is the coefficient of friction of the oil at the specified temperature, and the smaller the number, the better the result.

Claims (1)

[Claims] 1. The alkyl substituents are C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ and
A mixture of at least three alkyl groups of _C18 alkyl groups, the alkyl groups being derived from linear α-olefins, and from monoalkylcatechols with a _C18 alkyl group content of not more than 20%. A lubricating oil additive characterized by: 2. The lubricating oil additive of claim 1, wherein the alkyl substituent is a mixture of _C14 , _C16 , and _C18 alkyl groups. 3 Alkyl substituents are C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ and
The lubricating oil additive of claim 1 which is a mixture of _C18 alkyl groups. 4 Oil with lubricating viscosity and alkyl substituents
a mixture of at least three alkyl groups of C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ and C ₁₈ alkyl groups, the alkyl groups being derived from a linear α-olefin, and C ₁₈ alkyl 1. A lubricating oil composition comprising 0.5% to 5% by weight of a normally liquid alkylcatechol comprising monoalkylcatechols having a group content of 20% or less. 5 Oils with lubricating viscosity and alkyl substituents
a mixture of at least three alkyl groups of C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ and C ₁₈ alkyl groups, the alkyl groups being derived from a linear α-olefin, and C ₁₈ Contains from 0.5% to 5% by weight of a normally liquid alkylcatechol consisting of monoalkylcatechols having an alkyl group content of 20% or less, and (a) from 1% to 20% by weight of an alkenyl succinimide or alkenyl succinate or a mixture of both.
Weight %, (b) Group metal salt of dihydrocarbyldithiophosphoric acid
0.1% to 4% by weight, (c) 0.3% to 10% by weight of a neutral or overbased alkali or alkaline earth metal hydrocarbylsulfonate or mixture thereof, and (d) a neutral or overbased alkali or Alkaline earth metal alkylated phenates or mixtures thereof
A lubricating oil composition containing 0.2% to 27% by weight.