JPS6252000B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to a lubricant composition useful for two-stroke internal combustion engines comprising a large amount of an oil having a lubricating viscosity and a small amount of at least one aminophenol. More particularly, this invention relates to compositions comprising aminophenols having at least one hydrocarbon group having at least about 30 aliphatic carbon atoms. Since two-stroke engine oils are often mixed with fuel before or during use, this invention also relates to fuel-lubricant mixtures for two-stroke engines. US Pat. No. 2,197,835 discloses a method for preparing metal salts of aromatic amines produced by nitration and reduction of wax-substituted hydroxyaromatic hydrocarbons. This metal salt can be added to mineral oil to lower the pour point of the mineral oil or to improve the viscosity index of the mineral oil. US Pat. Nos. 2,502,708 and 2,571,092 describe a process for producing amines of cardanol by nitration and subsequent reduction of cardanol. The aminocardanol is said to be useful as an antioxidant for mineral oils, fats and petroleum. Cardanol, also known as anacardol, is 3-pentadecylphenol, 3-(8'-pentadecenyl)phenol, 3-(8':11'pentadecadienyl)phenol and 3-(8:11:14'- It is also described as a mixture of (pentadecatrienyl) phenols. The structural formulas described in the above two patent publications as well as the literature (The Dictionary of Organic Compounds, Volume 1, Oxford University Press (1965), Vol.
(see page 229) shows that the C ₁₅ substituent in cardanol is in the meta position relative to the hydroxyl group. U.S. Pat. No. 2,859,251 discloses that ortho-, para-, and meta-aminophenols are mixed with 6 to 18 molecules per molecule in the presence of a complex catalyst obtained by mixing hydrogen fluoride with boron trifluoride and a fluoride of an iron metal. A method of alkylation with an olefin polymer having carbon atoms is described. It is not clear from this patent publication whether the alkyl groups in the product mixture are bonded to carbon, nitrogen and/or oxygen atoms. Over the past few decades, spark ignition engines, including rotary engines such as the Wankel type
The use of cycle (two-stroke) internal combustion engines is steadily increasing. Such internal combustion engines are currently found in power lawn mowers and other power landscaping machines, power chain saws, pumps, generators, outboard motors, snowmobiles, and the like. Nowadays, as the use of two-cycle engines gradually increases and the operating conditions thereof become more and more severe, there is an increasing demand for oils that can adequately lubricate such engines. Problems with lubrication of two-stroke engines include sticking of piston rings, formation of rust,
Lubrication stoppage of connecting rods and main bearings and deposits of carbon and varnish on engine internal surfaces. This varnish formation is a particularly problematic problem. This is because if varnish forms on the piston and cylinder walls, the rings will eventually become stuck, and as a result, the sealing function of the piston rings will stop. Such failure of the sealing function causes loss of cylinder compression. This loss is particularly damaging because the engine relies on drawing in fresh fuel and feeding it to the exhaust cylinder. Thus, ring sticking is a problem that leads to reduced engine performance and unnecessary consumption of fuel and/or lubricant. In addition, the above-mentioned deposits also cause contamination of the spark plug and blockage of the engine port. Problems and techniques in the lubrication of two-stroke engines have been recognized by those skilled in the art of two-stroke engine lubricants as those of the lubricants themselves. For example, U.S. Patent No. 3085975;
See 3004837 and 3753905. The present invention alleviates the above problems by providing effective additives for two-stroke engine oils and oil-fuel mixtures that can eliminate or reduce engine varnish deposits and piston ring seal failures. is the issue. It is therefore an object of the invention to provide new lubricants and fuel lubricant mixtures for two-stroke engines. Another object of the invention is to provide a new method of lubricating a two-stroke engine. Other objects will become apparent from the description hereinafter. This invention includes a large part by weight of at least one oil having lubricating viscosity, and the formula (In the above formula, R is a substantially saturated hydrocarbon substituent having at least 30 to 72 aliphatic carbon atoms, and a, b and c are each independently 1
or an integer up to three times the number of aromatic nuclei present in Ar, and the sum of a, b, and c does not exceed the effective valence number of Ar, and Ar is a lower alkyl group, lower alkoxyl group, or nitro group. , a benzene nucleus having 0 to 3 substituents selected from the group consisting of a halo group and a combination of two or more of these, provided that when Ar has only one hydroxyl group and one R group, the R group is The lubricant composition for a two-stroke engine comprises a small amount of at least one aminophenol represented by the aminophenol (located at the ortho or para position of the hydroxyl group). As used herein, the term "phenol" has a generic meaning recognized in the art and refers to hydroxyaromatic compounds having at least one hydroxyl group directly bonded to the carbon of the aromatic ring. . Lubricating oil-fuel mixtures for two-stroke engines, as well as methods of lubricating two-stroke engines, including Wankel engines, are within the scope of this invention. The two-stroke engine oil composition of this invention contains a large amount of oil having lubricating viscosity. Typically, the viscosity is about 2.0 to about 150 cst at 98.9°C;
More typically from about 5.0 to about 130 cst at 98.9°C. The oil having the above-mentioned lubricating viscosity may be a natural oil or a synthetic oil. Mixtures of these are also often useful. Natural oils include animal and vegetable oils (e.g. castor oil and lard oil), as well as liquid petroleum or paraffinic, naphthenic or mixed paraffinic-naphthenic, solvent-treated or acid-treated mineral lubricating oils. . Oils with lubricating viscosities derived from coal or shale are also useful base oils. Synthetic lubricating oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.) and halo-substituted hydrocarbon oils, poly(1- hexene), poly(1-octene), poly(1-decene), etc. or mixtures thereof, alkylbenzenes (e.g.
dodecylbenzenes, tetradecylbenzenes,
Dinonylbenzenes, di(2-ethylhexyl)
-benzenes, etc.), polyphenyls (eg, biphenyls, terphenyls, alkylated polyphenyls), alkylated diphenyl ethers, alkylated diphenyl sulfides, and their derivatives, analogs, and congeners. Oils obtained by polymerizing olefins having up to 5 carbon atoms, such as ethylene, propylene, butylenes, isobutene, pentene, and mixtures thereof, are typical synthetic polymer oils. US Patent No. 2278445
No. 2301052, No. 2318719, No. 2318719, No. 2301052, No. 2318719, No.
Methods for producing such polymer oils are well known to those skilled in the art, as shown in US Pat. Polymers and interpolymers of alkylene oxide, as well as derivatives thereof whose terminal hydroxyl groups have been modified by esterification, etherification, etc., also constitute another group of known synthetic lubricating oils. Examples of this include oils obtained by polymerizing ethylene oxide and propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (e.g.
Methyl polyisopropylene glycol ether with average molecular weight 1000, diphenyl ether of polyethylene glycol with molecular weight 500-1000, molecular weight 1000
-1500 polypropylene glycol), or their mono- and polycarboxylic acid esters, such as acetic acid esters, mixed _C3 - _C8 fatty acid esters or _C13 oxoacid diesters of tetraethylene glycol. Other suitable groups of synthetic lubricating oils include dicarboxylic acids (e.g. phthalic acid, succinic acid, alkylsuccinic acid, alkenylsuccinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid) dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid, etc.) and various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Consists of esters. Specific examples of these esters are as follows.
Namely, dibutyl adipate, di(2-ethylhexyl) sebacate, dinormalhexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, and linoleic acid dimer. 2-ethylhexyl diester, a complex ester of 1 mole of sebacic acid, 2 moles of tetraethylene glycol, and 2 moles of 2-ethylcaproic acid, etc. Esters useful as synthetic oils also include:
There are those made from _C5 - _C12 monocarboxylic acids and polyols, and polyol ethers such as trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Silicone-based oils such as polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils also constitute another useful group of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, , tetra(2-ethylhexyl) silicate, tetra(4-methyl-hexyl) silicate, tetra(para-tert-butylphenyl) silicate, hexyl-(4-methyl-
2-pentoxy)-disiloxane, poly(methyl)siloxanes, poly(methylphenyl)siloxanes, etc.). Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid, etc.), polymerized tetrahydrofurans, and the like. Any of the above-mentioned types of unrefined, refined and rerefined oils, whether natural or synthetic (and mixtures of two or more of any of these), may be used in the lubricant compositions of this invention. It will be done. Unrefined oils are those obtained directly from natural or synthetic sources without additional refining treatment. For example, sierre oil obtained directly by retorting, petroleum oil obtained directly by distillation, or ester oil obtained directly by esterification and used without further treatment are unrefined oils. be. Refined oils are similar to unrefined oils except that they have been treated with one or more refining steps to improve one or more properties. Such purification methods are well known to those skilled in the art. For example, solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by applying the processes used to obtain refined oils to already used refined oils. Such rerefined oils are also known as reclaimed oils and are often further processed by methods to remove spent additives and oil breakdown products. The aromatic moiety Ar in the aminophenol used in the lubricant composition of this invention is a benzene nucleus. The number of aromatic nuclei (condensed type, crosslinked type, or both) in Ar is a, b in the above formula ()
and determine the numerical value of c. for example,
When Ar is a mononuclear aromatic nucleus, each of a, b and c is independently 1 to 3. Typically, the Ar moieties are unsubstituted except for the R, -OH and _-NH2 groups (and bridging groups). A typical Ar moiety is a benzene with 3 to 5 available valencies, one or two of which are filled by hydroxyl groups, and the remaining available valencies are filled with as many hydroxyl groups as possible. It can be located in the ortho or para position. Preferably, Ar has three or four available valences, such that one available valence is filled by a hydroxyl group and the remaining two or three available valences may be located in ortho or para positions with respect to the hydroxyl group. It is a benzene nucleus with valence. The aminophenol used in the two-stroke engine lubricant composition of this invention has an aromatic moiety.
It contains a substantially saturated monovalent hydrocarbon group R having at least about 10 aliphatic carbon atoms directly bonded to Ar. The R group can have at least 30 to 72 aliphatic carbon atoms. Two or more such R groups may exist, but
Usually there are no more than two or three for each aromatic nucleus in the aromatic moiety Ar. The total number of R groups is indicated by the numerical value of "a" in the above formula (). Usually, the hydrocarbon group has at least about 30, more typically at least about 50, and typically up to about 300 aliphatic carbon atoms. Generally, the hydrocarbon group R is a mono- and diolefin homopolymer or Derived from interpolymers (eg, dipolymers, terpolymers). Typically, these olefins are 1-monoolefins. The R group may also be a halide of the above homopolymer or interpolymer (e.g.
chloride or bromide). This R group refers to high molecular weight alkene monomers (e.g. 1-tetracontene) and their chlorides and hydrochlorides, aliphatic petroleum distillates, paraffin waxes and their chlorides and hydrochlorides, and white oils. , synthetic alkenes such as alkenes obtained by the Ziegler-Natsuta process (eg, poly(ethylene) grease), and other sources known in the art. Any unsaturation present in R may be reduced or removed by hydrogenation according to methods known in the art prior to the nitration step described below. A "hydrocarbon group" as used herein means a group having a carbon atom directly bonded to the remainder of the molecule and having primarily hydrocarbon character within the meaning of this invention. Thus, a hydrocarbon group can contain up to one non-hydrocarbon group for every ten carbon atoms. However, this non-hydrocarbon group must not significantly change the main hydrocarbon properties of the hydrocarbon group. Such non-hydrocarbon groups will be apparent to those skilled in the art. Examples include hydroxyl group, halo group (particularly chloro group and fluoro group), alkyl group, alkylmercapto group, alkylsulfoxy group, and the like. However, usually the hydrocarbon group R is purely hydrocarbyl and does not contain the above-mentioned non-hydrocarbon groups. The hydrocarbon group R is substantially saturated, ie, contains at most one carbon-carbon unsaturated bond for every ten carbon-carbon double bonds present. Typically, R will contain no more than one carbon-carbon non-aromatic unsaturated bond for every 50 carbon-carbon bonds present. The hydrocarbon group of the aminophenol used in the two-stroke engine oil of this invention is also substantially aliphatic in nature. That is, at most one non-aliphatic group (cycloalkyl group, cycloalkenyl group, or aromatic group) having 6 or fewer carbon atoms is present for every 10 carbon atoms in the R group. It usually contains no more than one such non-aliphatic group per 50 carbon atoms, and often no such non-aliphatic group at all. That is, typical R groups are purely aliphatic. Typically, these purely aliphatic R groups are alkyl or alkenyl groups. Specific examples of the substantially saturated hydrocarbon group R are listed below. Tetra (propylene), tri (isobutene), tetracontanyl, hempentacontanyl, mixtures of poly(ethylene/propylene) groups having from about 35 to about 70 carbon atoms, from about 35 to about 70 carbon atoms Mixtures of oxidatively or mechanically modified poly(ethylene/propylene) groups, mixtures of poly(isobutene) groups having an average of 50 to 75 carbon atoms. A preferred source of R groups is a _C4 fraction with a butene content of 35 to 75% by weight and an isobutene content of 30 to 60% by weight in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. It is a poly(isobutene) obtained by polymerizing. These polybutenes are primarily (i.e., total repeat units
80% or more) formula Contains an isobutene repeating unit represented by The hydrocarbon group R is an aromatic moiety of the aminophenol used in the two-stroke engine oil of this invention.
Many methods known to those skilled in the art can be used to attach Ar. One particularly suitable method is the Friedel-Crafts reaction, in which olefins (for example polymers with olefinic bonds) or their halides or hydrohalides are reacted with phenols. This reaction is carried out using Lewis acid catalysts (for example, boron trifluoride and its complexes with ethers, phenols, hydrogen fluoride, etc., aluminum chloride,
aluminum bromide, zinc dichloride, etc.). Procedures and conditions for carrying out this reaction are well known to those skilled in the art. For example, the ``Alkylation of Phenols'' described in ``Encyclopedia of Chemical Technology'' by Kirk Osmer, 2nd edition, Volume 1, pp. 894-895 (1963), published by Interscience Publications. ” section. Equally suitable and convenient methods for attaching the hydrocarbon group R to the aromatic moiety Ar will be apparent to those skilled in the art. As can be easily seen from the above formula (), the aminophenol used in the two-cycle engine oil of the present invention has at least one substituent of a hydroxyl group, the above-mentioned R group, and a primary amine group _-NH2 . ing. Each of these groups is bonded to a carbon atom that is part of the aromatic nucleus in the Ar moiety. In a preferred embodiment, the aminophenol used in the two-cycle engine oil of the present invention contains only one of each of the above substituents and a mononuclear aromatic ring, preferably benzene. This preferred aminophenol has the formula (In the above formula, R' is a hydrocarbon group containing about 30 to about 400 aliphatic carbon atoms located at the ortho or para position of the hydroxyl group, R is a lower alkyl group, a lower alkoxyl group, a nitro group, or a halogen group. atoms, and z is 0 or 1). Usually z is 0, and
R' is a substantially saturated pure aliphatic group. Often R' is an alkyl or alkenyl group located para to the --OH group. In a further preferred embodiment of the invention, the aminophenol has the formula (In the above formula, R″ is a group derived from a C ₂ -C ₁₀ 1-olefin homopolymer or interpolymer and having an average of about 30 to about 300 aliphatic carbon atoms, and R and z are as defined above. Typically, R'' is derived from ethylene, propylene, butylene and mixtures thereof. Typically R'' is a polymer of isobutene. Often R'' has at least about 50 aliphatic carbon atoms and z is zero. The aminophenols used in the two-stroke engine oil of this invention can be produced by a number of synthetic techniques. The techniques vary in the type of reactions used and their order. For example, an aromatic hydrocarbon such as benzene is alkylated with an alkylating agent such as a polymerized olefin to produce an alkylated aromatic intermediate. This intermediate is nitrated to produce, for example, a polynitro intermediate. Then,
This polynitro intermediate is reduced to a diamine, which is diazotized and reacted with water to convert one of the amino groups to a hydroxyl group, thus yielding the desired aminophenol. Alternatively, converting one of the nitro groups in the polynitro intermediate to a hydroxyl group by melting with caustic to obtain a hydroxy-nitroalkylated aromatic intermediate, which is then reduced to obtain the desired aminophenol. You can also do it. Another useful means for producing the aminophenols involves alkylating an olefin with an olefinic alkylating agent to produce an alkylated phenol. The desired aminophenol is obtained by nitrating the alkylated phenol to produce a nitrophenol intermediate and then reducing at least some of its nitro groups. Methods for alkylating phenols are well known to those skilled in the art, as set forth in the Encyclopedia of Chemical Technology, supra. Nitration of phenols is also well known. For example, the aforementioned Encyclopedia of Chemical Technology, 2nd edition, Volume 13, 888
See the ``Nitrophenols'' section below, as well as ``Aromatic Substances; Nitration and
"Nitration and Aromatic Reactivity" by JG Hoggett, published by Cambridge University Press in 1961, and "The Chemistry of the See Nitro and Nitroso Group. Aromatic hydroxy compounds can be nitrated with nitric acid, mixtures of nitric acid with sulfuric acid or boron trifluoride, nitrogen tetroxide, nitronium tetrafluoroborate or acyl nitrate. Generally, nitric acid at a concentration of, for example, about 60-90% is a convenient nitrating agent. Substantially inert liquid diluents and solvents, such as acetic acid and butyric acid, aid in the progress of the reaction by promoting contact between the reactants. Conditions and concentrations for nitrating hydroxyaromatic compounds are well known in the art. For example, the reaction can be carried out at a temperature of about -15°C to about 150°C. Usually, nitration is conveniently carried out at about 25 to 75°C. Generally, depending on the nitrating agent used, about 0.5 to 4 moles of nitrating agent are used for each mole of aromatic nuclei present in the hydroxyaromatic compound to be nitrated. When nitric acid is used as the nitrating agent, it is used in an amount of about 1.0 to about 3.0 moles per mole of aromatic nuclei. Up to about a 5 molar excess (per "monocyclic" aromatic nucleus) of nitrating agent may be used if the reaction is to be carried out quickly. For the nitration of hydroxyaromatic intermediates, generally
It takes 0.25 to 24 hours. However, it is advantageous to react the nitration mixture for a long time, for example 96 hours. The reduction of aromatic nitro compounds to the corresponding amines is well known. For example, see the section ``Amination by Reduction'' in the aforementioned ``Encyclopedia of Chemical Technology,'' 2nd edition, Volume 2, pages 76-99. Generally, this reaction can be carried out with, for example, hydrogen, carbon monoxide or hydrazine (or mixtures thereof) in the presence of a metal based catalyst such as palladium, platinum and its oxides, copper chromite. Cocatalysts such as alkali metal or alkaline earth metal hydroxides or amines (including aminophenols) can also be used in this catalytic reduction. Reduction can also be carried out using a reducing metal in the presence of an acid such as hydrochloric acid. Typical reducing metals are zinc, iron and tin, and salts of these metals can also be used. The nitro group can also be reduced by the ginine reaction described in "Organic Reactions", John Willey & Sons, 1973, Vol. 20, pp. 455 et seq. Generally, the ginine reaction involves the reduction of a nitro group by divalent negative compounds such as alkali metal sulfides, polysulfides, and hydrosulfides. Nitro groups can also be reduced by electrolysis. See, for example, "Amination by Reduction" above. Typically, aminophenols are obtained by reducing nitrophenol with hydrogen in the presence of the metal-based catalysts described above. This reduction is generally around 15-250
°C, typically temperatures between about 50 and 150 °C, between about 0 and
It is carried out under hydrogen pressure of 2000 psig, typically about 50-250 psig. The reduction reaction time varies between about 0.5 and 50 hours. Substantially inert liquid diluents and solvents such as ethanol, cyclohexane, and the like can be used to facilitate this reaction. The aminophenol product can be recovered by distillation, filtration, extraction, or other well known means. The reduction is carried out until at least about 50%, and usually about 80%, of the nitro groups present in the nitro intermediate are converted to amino groups. A typical method for obtaining the aminophenols just mentioned is summarized below. ()formula (In the above formula, R is at least 30 to 72
a substantially saturated hydrocarbon group having aliphatic carbon atoms, a and c each independently from 1 to Ar;
an integer up to three times the number of aromatic nuclei present in the group, and the sum of a, b and c does not exceed the effective valence number of Ar', Ar' is a lower alkyl group, a lower alkoxyl group, a nitro group, Halo group and two of these groups
A benzene nucleus having 0 to 3 substituents selected from the group consisting of a combination of species or more, provided that (a)
Ar′ has at least one hydrogen atom directly bonded to a carbon atom that is part of the aromatic nucleus, and (b)
When Ar' is benzene having only one hydroxyl group and one R group, the R group is located at the ortho or para position of the hydroxyl group). nitration with a oxidizing agent to produce a first reaction mixture containing a nitro intermediate, and () reducing at least about 50% of the nitro groups in the first reaction mixture to amino groups. Typically, this means that the formula (In the above formula, R is a substantially saturated hydrocarbon group having at least 30 to 72 aliphatic carbon atoms, and a, b and c are each independently 1 to the number of aromatic nuclei present in Ar. up to 3 times the number, and the sum of a, b and c does not exceed the effective valence number of Ar. Ar is a group consisting of lower alkyl groups, lower alkoxyl groups, halo groups, and combinations of two or more of these. A benzene nucleus having 0 to 3 substituents selected from among them, provided that in the case of a benzene nucleus in which Ar has only one hydroxyl group and an R group,
(the R group is located in the ortho or para position of the hydroxyl group) is meant to reduce at least about 50% of the nitro groups present in the compound to amino groups. The experimental examples described below are examples of the production of typical aminophenols used in the two-stroke engine composition of the present invention. It will be obvious that aminophenols obtained by methods other than those shown in the following experimental examples can also be used in the present invention. As in this specification and claims, all "parts" and "%" are used in the following experimental examples.
are by weight unless otherwise indicated. Experimental Example 1A Alkylated phenol was produced by reacting phenol with polyisobutene having a number average molecular weight of approximately 1000 (vapor phase osmotic pressure method) in the presence of a boron trifluoride phenol complex catalyst. This was first stripped to 230°C/760 Torr (steam temperature) and then stripped to 205°C/50 Torr to obtain purified alkylated phenol. A mixture of 18.4 parts of concentrated nitric acid (69-70%) and 35 parts of water was slowly added to a mixture of 265 parts of the purified alkylated phenol, 176 parts of blended oil, and 42 parts of petroleum naphtha having a boiling point of about 20°C. The reaction mixture was stirred at 30-45°C for 3 hours and then at 120°C/20°C.
An oil solution of the desired nitrophenol intermediate was obtained by stripping and filtration. Experimental Example 1B 1500 parts of the oil solution obtained in Experimental Example 1A, 642 parts of 2-propanol and 7.5 parts of diatomaceous earth supported nickel catalyst
The mixture consisting of 1.5 parts was charged into an autoclave under nitrogen atmosphere. After nitrogen bubbling and degassing three times, the autoclave was pressurized to 100 psig with hydrogen and stirring was started. The reaction mixture was heated to 96 °C for a total of 14.5
A total of 1.66 moles of hydrogen were supplied during this period. After three cycles of nitrogen bubbling and degassing, the reaction mixture was filtered and the filtrate was stripped to 120°C/18 Torr. Filtration gave an oil solution of the desired product containing 0.54% nitrogen. Experimental Example 1B A mixture of 400 parts of polyisobutene-substituted phenol (the polyisobutene substituent contained approximately 100 carbon atoms), 125 parts of textile benzine and 266 parts of diluted mineral oil was heated at 28°C for 0.33 hours. 22.83 parts of nitric acid (70%) in 50 parts of water were added slowly. This mixture was stirred at 28-34°C for 2 hours,
Stripping to 158°C/30 Torr and filtration gave a 40% oil solution of the desired intermediate containing 0.88% nitrogen. Experimental Example 2B 93 parts of the oil solution obtained in Experimental Example 2A and a mixture of toluene and 2-propanol (50/50 weight ratio)93
The mixture consisting of 1.5 parts was charged to an appropriately sized hydrogenation vessel. This mixture was degassed and sparged with nitrogen,
0.31 part of a commercially available platinum oxide catalyst (86.4% _PtO2 ) was added. The reaction vessel was pressurized to 57 psig and held at 50-60°C for 21 hours. A total of 0.6 moles of hydrogen was fed to the reaction vessel. The reaction mixture was then filtered and the filtrate was stripped to obtain an oil solution of the desired product containing 0.44% nitrogen. Experimental Example 3A A mixture consisting of 2160 parts of the polyisobutene-substituted phenol used in Experimental Example 2A and 1440 parts of diluted mineral oil was heated to 60°C. Then 25 parts of paraformaldehyde and then 15 parts of hydrochloric acid were added to this mixture. The mixture was heated to 115°C for 1 hour. After standing at room temperature for 16 hours, the reaction mixture was heated to 160°C for 1 hour.
During this time, 20 parts of distillate were removed. reaction mixture
Stripping to 160°C/15 Torr yielded the desired methylene-bridged polyisobutene-substituted phenol solution in oil. Experimental Example 3B To a mixture consisting of 2406 parts of the oil solution obtained in Experimental Example 3A and 600 parts of textile benzene, 90 parts of nitric acid (70%) was added over 1.5 hours. The reaction mixture was stirred for 1.5 hours, left at room temperature for 63 hours, then heated to 90°C for 8 hours.
The time was hot. Stripping to 160°C/18 Torr yielded an oil solution of the desired nitrated intermediate containing 0.79% nitrogen. Experimental Example 3C 800 parts of the oil solution obtained in Experimental Example 3B and toluene/
A mixture consisting of 720 parts of a 2-propanol mixture (60/40 weight ratio) was charged into an autoclave. After nitrogen blowing, 4 parts of nickel catalyst supported on diatomaceous earth were added. The nitrogen bubbling was repeated three times and the autoclave was pressurized with hydrogen to 60 psig at 25°C. Slowly increase the reaction temperature to 96°C and increase the pressure to 100 psig.
It was kept for 5.5 hours. The autoclave was then opened and an additional 4 parts of nickel on diatomaceous earth catalyst were added. The autoclave was again pressurized to 100 psig hydrogen and held at 96° C. and 100 psig for 6 hours. The autoclave was cooled, opened, and 0.8 parts of platinum oxide catalyst was added. The autoclave was pressurized with hydrogen to 90 psig and maintained at this pressure for an additional 8 hours. The reaction mixture was filtered and stripped to 150°C/18 Torr to obtain an oil solution of the desired product containing 0.41% nitrogen. Experimental Example 4A 1962 parts of polyisobutene-substituted phenol obtained in Experimental Example 1A, 49.5 parts of paraformaldehyde, 15 parts of hydrochloric acid
and 1372 parts of diluted mineral oil at 115°C.
It was heated for 7 hours. The reaction temperature was increased to 160-165°C and held at that temperature for an additional 7 hours. 400 parts of benzene for textiles was added to this mixture, and the mixture was cooled to 30°C. Then 136.95 parts of nitric acid (70%) in 140 parts of water were slowly added. The reaction mixture was stirred at 30-35°C for 1.5 hours and stripped to 170°C/28 Torr to obtain an oil solution of the desired intermediate, which was clarified by filtration. Experimental Example 4B 96 parts of the oil solution obtained in Experimental Example 4A and toluene/
96 parts of a 2-propanol (50/50 weight ratio) mixture was charged to an appropriately sized hydrogenation reaction vessel. After nitrogen blowing, 0.32 parts of platinum oxide catalyst was added. After bubbling the reaction vessel with nitrogen, it was pressurized to 57 psig with hydrogen at 25°C. Hydrogen pressure 57 and 50 psig
The reaction mixture is kept at 50 to 60℃ for 60 hours between
It was heated to. The reaction mixture was filtered and stripped to obtain an oil solution of the desired product with a nitrogen content of 0.353%. Experimental Example 5A 27 to 31 consisting of 654 parts of polyisobutene-substituted phenol obtained in Experimental Example 1A and 654 parts of isobutyric acid.
90 parts of 16M nitric acid was added to the mixture at 0.degree. C. over 0.5 hour. The reaction mixture was kept at 50° C. for 3 hours and then left at room temperature for 63 hours. This reaction mixture
Stripping to 160°C/26 Torr and filtration through filter aid yielded the desired nitro intermediate with a nitrogen content of 1.8%. Experimental example 5B Experimental example using diatomaceous earth supported nickel catalyst
Experimental example following substantially the same method as method 1B
The nitro intermediate obtained in 5A was hydrogenated. Experimental Example 6A 4578 parts of polyisobutene-substituted phenol obtained in Experimental Example 1A, 3052 parts of diluted mineral oil, and textile benzene
The mixture consisting of 725 parts was homogenized and heated to 60°C. 16 mol nitric acid in 600 parts of water after cooling to 30°C
Added 320 copies. Cooling was necessary to keep the mixture below 40°C. After stirring the reaction mixture for an additional 2 hours, 3710 parts thereof were transferred to a second reaction vessel. 3710 parts of this were treated with 128 parts of 16 molar nitric acid in 130 parts of water at 25-30°C. The reaction mixture was stirred for 1.5 hours and then stripped to 220°C/30 Torr. Filtration gave an oil solution of the desired intermediate. Experimental Example 6B Using a platinum oxide catalyst, the intermediate in the oil solution obtained in Experimental Example 6A was hydrogenated in substantially the same manner as Experimental Example 1B. Experimental Example 7 Dinitro C ₂₅ obtained by almost the same method as Experimental Example 6A
543 parts of alkylated phenol, isopropanol
A mixture of 543 parts and 200 parts of toluene was heated at 19°C.
A total of 42 parts of ammonia gas was used for 0.75 hours. The reaction mixture was then flushed with H ₂ S gas.
Processed in 147 copies. Ammonia and hydrogen sulfide treatments were carried out by introducing gas into the stirred reaction mixture. Ammonia treatment was repeated with 82 parts of ammonia gas, followed by a final treatment with 102 parts of hydrogen sulfide. The reaction mixture was stripped to 40°C/60 Torr and the residue was mixed with 161 parts of diluent oil and stripped again to 70°C/18 Torr. An additional 161 parts of the diluted oil and 35 parts of filter aid were added and filtered to obtain a viscous filtrate that was a 40% oil solution of diaminophenol. Generally, the two-stroke engine lubricant compositions of this invention contain from about 98 to about 55% oil or mixtures thereof having lubricating viscosity. Typical compositions contain about 90 to about 70% oil. Presently preferred oils are mineral oils and mineral oil-synthetic polymer and/or ester oil mixtures. Polyisobutene and fatty acid ester oils, such as pentaerythritol and trimethylolpropane, with molecular weights from about 250 to about 1000 (by gas phase osmometry) are typical useful synthetic oils. The compositions contain from about 2% to about 30%, typically from about 5% to about 20%, of at least one of the aforementioned aminophenols. Additives such as auxiliary detergents and dispersants of the ash-forming or ashless type, coupling agents, pour point depressants, extreme pressure agents, color stabilizers and antifoaming agents may be present. Ashless or ash-forming metal type detergents and dispersants are used to control piston ring sticking and general engine cleaning. Suitable ashless dispersants are required for high-duty two-stroke engine lubricants. This is because such engines tend to induce pre-ignition. Other compositions use calcium, barium or magnesium sulfonates alone, in mixtures thereof, or with ashless dispersants. Antioxidants may be added to improve the thermal stability of the lubricant. Polymeric viscosity index improvers have been used to replace bright stocks to improve lubricant film strength and lubricity and improve engine cleanliness. Dyes can be used for identification purposes and to determine whether a two-stroke engine fuel mixture contains lubricant. Coupling agents are added to some products to improve component solubility and improve the water solubility of the fuel/lubricant mixture. For special applications, such as in competition or where fuel/lubricant ratios are very high, antiwear and lubricity improvers are used, especially sulfurized whale oil and other fatty acids and vegetable oils such as castor oil. Lead scavengers and fuel chamber deposit modifiers are sometimes used to promote spark plug life and remove carbon deposits. Halogenated compounds and/or phosphorus-containing materials can be used in this application. Two-stroke engine oils may contain any type of anti-rust or preservative. Fragrance agents and deodorizers are sometimes used for aesthetic reasons. Synthetic polymers (e.g., with a number average molecular weight by gas phase osmometry or gel permeation chromatography of approximately
Lubricating agents such as polyisobutene (within the range of 750 to about 15,000), polyol ethers (e.g., poly(oxyethylene-oxypropylene) ether), and ester oils (e.g., the ester oils described above) may also be used in the compositions of this invention. used for things Natural oil fractions such as bright stock (a relatively viscous product obtained during the normal process for obtaining lubricating oils from petroleum) can also be used for this purpose. Typically, they are present from about 3 to about 20% of the two-stroke engine oil composition. As previously mentioned, the lubricant compositions of the present invention may also include auxiliary detergent and dispersants. A typical example is a fatty acid containing 5 to 22 carbon atoms (e.g., isostearic acid or a mixture of isostearic acid and stearic acid) with 2 to about 2 amino groups.
Amides, amine salts and/or amidines obtained by reacting with alkylene polyamines having 10, 2 to 20 carbon atoms (e.g. ethylene diamine, tetraethylene pentamine, etc., as well as commercial mixtures of these alkylene polyamines) It is a thing. Such auxiliary cleaning and dispersing agents are shown in US Pat. No. 3,169,980. A diluent such as petroleum naphtha (e.g. Stoddard Solvent) having a boiling point of about 38 DEG to 90 DEG C. may also be included in the compositions of the invention, typically from 5 to 25%. The lubricant composition for two-stroke engines of the present invention contains 2 to 10% of one or more aminophenols as shown in Experimental Example 1B, and
The base oil comprises approximately 70 to 80 parts by volume of 650 neutral oil, 8 to 12 parts by volume of Brightstock, and 10 to 20 parts by volume of Stoddard Solvent. (This is an example.) In some two-stroke engines, lubricating oil is injected into the combustion chamber along with the fuel or into the fuel before the fuel is delivered to the combustion chamber. The two-stroke engine lubricant composition of the present invention is intended for use in such two-stroke engines. As is well known to those skilled in the art, two-cycle engine lubricating oils can be added directly to fuel to create an oil and fuel mixture that is then introduced into the engine cylinder. Such lubricant-fuel oil mixtures are within the scope of this invention. Such lubricant-fuel blends generally include one part oil and one part oil.
Each part contains about 15 to 250 parts of fuel, typically about 50 to 100 parts. Typical specific examples of the two-stroke engine oil of the present invention are described below.

[Table] Experimental Example 15A Alkylated phenol was produced by reacting phenol with polybutene having a number average molecular weight of approximately 1000 (vapor phase osmotic pressure method) in the presence of a boron trifluoride-phenol complex catalyst. After neutralizing the catalyst and filtering it out,
The filtrate was stripped first to 230°C/760 Torr (steam temperature) and then to 205°C/50 Torr (steam temperature) to yield purified alkylated phenols as a residue. 260 parts of the resulting refined alkylated phenol, 176 parts of blended mineral oil and petroleum naphtha with a boiling point of approximately 200°C
Concentrated nitric acid (69-70%) to a mixture of 42 parts 18.4
and 35 parts of water were slowly added.
The reaction mixture was stirred at 30-45°C for 3 hours and then heated to 120°C.
Stripping to °C/20 Torr (steam temperature),
Filtration yielded an oil solution of the desired nitrophenol intermediate. Experimental Example 15B 1900 parts of a mineral oil solution (containing 43% mineral oil) of the nitrophenol intermediate obtained in Experimental Example 15A was heated to 145° C. under a nitrogen atmosphere. 70 parts of hydrated hydrazine were then added slowly to this solution over a period of 5 hours while maintaining the temperature at about 145°C. The mixture was heated to 160° C. for 1 hour, during which time 56 parts of aqueous distillate were collected. An additional 7 parts of hydrated hydrazine were added and the mixture was held at 140°C for an additional hour. This is 130
Filtration at 0C yielded an oil solution of the desired aminophenol containing 0.3% nitrogen. Experimental Example 16 Experimental example except that the polybutene used was polybutene with a molecular weight of approximately 500 obtained from n-butene.
The desired aminophenol was obtained by performing the same operation as 15A and 15B. Experimental Example 17 Tetrapropenylaminophenol was obtained in the same manner as in Experimental Examples 15A and 15B, except that the same molar amount of propylene tetramer was used instead of polybutene. Example 1 An additive concentrate was prepared by blending the ingredients listed in the table below in the proportions shown in the table.

[Table] The above compositions and were blended with gasoline {gasoline 50:composition 1 (weight ratio)} and this fuel mixture was tested in a Chrysler-West Bend engine to evaluate the piston varnish status.
The test was carried out for 10 hours, with the engine running at 5000 rpm.
The oil to be tested flowed at 60 cm ³ /min and operated at approximately 4.7 BHP. A score of 10.0 indicates cleanliness. The results are shown below. Fuel mixture piston varnish evaluation score Contains composition 8.94 (average of 4 times) Contains composition 9.2 Contains composition 6.81 Although the added amount of aminophenol used in Example 1 is different, in terms of aminophenol functionality Almost the same. Fuels used in two-stroke engines are well known to those skilled in the art and are typically liquid fuels such as hydrocarbonaceous petroleum distillate fuels (e.g. motor gasoline as specified in ASTM-D-439-73). Contains large amounts of. Such fuels may include non-hydrocarbons such as alcohols, ethers, organic nitro compounds, etc. (eg, methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane). So are liquid fuels derived from plant and mineral sources such as corn, corn, shale, and coal. Examples of such fuel mixtures are gasoline and ethanol, diesel fuel and ether, gasoline and nitromethane, etc. Particularly preferred are gasolines (i.e., ASTM with a boiling point of 60°C at 10% distillation and about 205°C at 90% distillation).
It is a mixture of hydrocarbons with a boiling point. Two-stroke engine fuels may contain other additives that are well known to those skilled in the art. Such additives include anti-knock agents such as tetraalkyl lead compounds, lead scavengers such as haloalkanes (such as ethylene dichloride and ethylene dibromide), anti-deposition agents and modifiers such as trialkyl phosphates, and dyes. , cetane number improver, 2,6-di-tert-butyl-
Antioxidants such as 4-methylphenol, rust inhibitors such as alkylated succinic acids and their anhydrides, bacterial growth inhibitors, gum inhibitors, metal deactivators,
Includes emulsifiers, upper cylinder lubricants, anti-icing agents, etc.

Claims (1)

[Claims] 1. A large amount of at least one oil having lubricating viscosity, and a formula (In the above formula, R is a substantially saturated hydrocarbon substituent having at least 30 to 72 aliphatic carbon atoms, and a, b and c are each independently 1
or an integer up to three times the number of aromatic nuclei present in Ar, and the sum of a, b and c does not exceed the effective valence of Ar, and Ar is a lower alkyl group, a lower alkoxy group, a nitro group, a benzene nucleus having 0 to 3 substituents selected from the group consisting of a halo group and a combination of two or more thereof;
However, when Ar has only one hydroxyl group and one R group, the R group is located at the ortho or para position of the hydroxyl group.
Lubricant composition for cycle engines. 2. A composition according to claim 1, wherein R is a pure hydrocarbyl group. 3. The composition according to claim 2, wherein R is an alkyl group or an alkenyl group. 4. The composition of claim 1, wherein R is a group derived from a homopolymer or interpolymer of _C2 to _C10 olefins. 5. The composition according to claim 4, wherein the _C2 - _C10 olefin is a _C2 - _C101 -olefin. 6. The composition of claim 5, wherein the 1-olefin is selected from the group consisting of ethylene, propylene, butylene and mixtures thereof.