DK159932B - PROCEDURE FOR LUBRICATING A 2-STATCH ENGINE - Google Patents

Description

in

DK 159932B

The present invention relates to a method for lubricating a 2-stroke internal combustion engine which is characterized in that a lubricant composition containing 55-98, preferably 70-90, weight% of at least one lubricating viscosity oil and 2-30 is used. preferably from 5 to 20% by weight of at least one amino-containing additive which (a) has the general formula: (OH) c10 <R) a-Ar - <NH2) b wherein R represents a substantially saturated hydrocarbon-based substituent having 30-400 aliphatic carbon atoms; a, b and c each independently of one another are an integer from 1 up to 3 times the number of aromatic cores found in Ar, provided that the sum of a, b and c does not exceed the number of unfulfilled valences on Ar ; and Ar represents an aromatic moiety having 0 to 3 optional substituents in the form of lower alkyl, lower alkoxyl, nitro, halogen or combinations of two or more of the 20 optional substituents; with the proviso that when Ar represents a benzene nucleus having only one hydroxyl and one R substituent, the R substituent is in ortho or para position to the hydroxyl substituent, or which (b) is produced by reduction of at least approx. 50% of the nitro groups to amino groups in a compound or mixture of compounds of formula:

(° H) C

(R) - Ar '30 wherein R represents a substantially saturated hydrocarbon-based substituent having 30-400 aliphatic carbon atoms; a, b and c are each independently an integer from 1 up to 3 times the number of aromatic cores found in Ar, provided that the sum of a, b and c does not exceed the number of unfulfilled valences on Ar ; and Ar represents an aromatic moiety having 0 to 3 optional substituents in the form of lower alkyl, lower alkoxyl, halogen or combinations of two or more of the optional substituents; with the condition that when Ar represents a benzene nucleus

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2 with only one hydroxyl and one R substituent, the R substituent is in ortho or para position to the hydroxyl substituent, the remainder of the composition being any other additives known per se.

US Patent No. 2,197,835 describes the formation of metal salts of aromatic amines which have been formed by nitration and subsequent reduction of wax-substituted hydroxyaromatic hydrocarbons. These metal salts can be incorporated into mineral oils to lower their melting point and increase their viscosity index.

U.S. Patent Nos. 2,502,708 and 2,571,092 both disclose nitration and subsequent hydrogenation to an amine of cardanol. This aminocardanol is said to be useful as an antioxidant for mineral oils, fats and petroleum oils. Cardanol, also known as anacardol, is also said to be a mixture of 3-pentadecylphenol, 3- (8'-pentadecenyl) phenol, 3-15 (8 ': H'-pentadecadienyl) phenol and 3- (8: 11: 14 '-pentadecatrienyl) phenol. The formulas presented in both of these patents as well as in the chemical literature (Dictionary of Organic Compounds, Vol. 1, Oxford University Press, NY, 1965, p. 229) show that the Cjg substituent in cardanol is in the meta position. to the hydroxy group.

U.S. Patent No. 2,859,251 discloses alkylation of ortho-, para-, and meta-aminophenols with olefin polymers having from 6 to 18 carbon atoms per molecule in the presence of a catalytic complex formed by mixing hydrogen fluoride with boron trifluoride and an iron group metal fluoride. This patent lacks information on whether the alkyl groups in the product mixture are bound to a carbon, nitrogen and / or oxygen atom.

U.S. Patent No. 2,868,844 relates to a process for the preparation of 4-nitro-2,6-dialkylphenols, wherein both alkyl groups are branched on the α-carbon atom. The patent mentions quite briefly that these 30 compounds can be reduced to the corresponding amino compounds which can be used to stabilize various materials, including fuels and lubricating oils. In column 2, lines 29-31, it is mentioned that the alkyl group preferably has at most 12 carbon atoms and the examples show all alkyl = tert-butyl, isopropyl, 2-decyl and tert-amyl.

U.S. Patent No. 3,149,933 discloses liquid antioxidants having the following general formula:

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3

OH

I »i 111 | j * ~ 11 *

Nine./

At 5 in this formula, Rg represents either a hydrocarbon radical of up to 16 carbon atoms or a complex amino hydrocarbon radical shown in formulas 2 and 3. In neither case does the compound contain a free amino group. Nor does the list of compounds found in column 1 and 2 mention any unsubstituted amino groups.

U.S. Patent 2,618,538 discloses diesel fuel additives in the form of nitroanilines or nitrophenols. Nowhere in the patent is there any description of aminophenols. The nitroanilines shown in column 2 do not have any hydroxy groups and thus are not phenolic, and the phenol shown in column 3 does not have any amino groups. In addition, the patent does not show a substantially saturated hydrocarbon-based substituent having 30-400 aliphatic carbon atoms. In column 3, lines 4-6 of the patent, it is mentioned that the hydrocarbon groups may be all cooling groups having 3-15 carbon atoms, which is noted that the only nitro compound mentioned in the claims in the patent is 2,4-dinitrohydrocarbon. 6-cyclohexylphenol.

Thus, the amino-containing additives used in the process of the invention for lubricating a 2-stroke internal combustion engine are clearly different from the amine phenols and nitro compounds known from the above-mentioned United States Patents. In addition, there is nothing in these United States patents which can lead one to suppose that by increasing the size of the hydrocarbon substituent, an additive could be obtained which can advantageously be used in a process for lubricating a 2- stroke internal combustion engine.

30 For several decades, the use of spark-ignited 2-stroke (2-cycle) internal combustion engines, including rotary engines such as Wankel-type engines, has been constantly increasing. They are currently on lawn mowers and other power tools, garden chainsaws, pumps, electric generators, boat outboard motors, snowmobiles and the like.

35 The growing use of 2-stroke engines coupled with increased demands on their operating conditions has led to an increasing need for oils for the appropriate lubrication of such engines. Among the problems associated with lubrication of 2-stroke engines are piston ring attachment,

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4 rust formation, lubrication failure of connecting rod and main bearings and the general formation of soot and varnish-like deposits on the internal surfaces of the engine. The formation of varnish-like deposits is a particularly tedious problem, as the build-up of these deposits on piston and cylinder walls 5 is ultimately believed to result in ring attachment, leading to the failure of the sealing function of the piston rings. Such seal failure causes loss of cylinder compression, which is particularly damaging to 2-stroke engines because they depend on the suction effect to draw the new fuel supply into the emptied cylinder. Thus, ring attachment can lead to disruption in engine performance and unnecessary fuel and / or lubricant consumption. These additives can also reduce spark plug saturation and door clogging problems.

The particular problems and techniques associated with the lubrication of 2-stroke engines have led to the recognition that lubricants for 2-15-stroke engines constitute a particular type of lubricant. Reference is made, e.g. U.S. Patent Nos. 3,085,975, 3,004,837 and 3,753,905.

The invention described herein is intended to alleviate these problems by providing effective additives for 2-stroke engine oils and oil-fuel combinations which eliminate or reduce the varnish-like engine deposits and piston ring seal failure.

The term "phenol" is used in this specification in its generic accepted sense in the art, so as to refer to hydroxy-aromatic compounds having at least one hydroxyl group linked directly to a carbon atom in an aromatic ring.

The aminophenols used in the lubricant composition used in the process of the invention are disclosed in the applicant's Danish Patent Application No. 4615/76, filed simultaneously with the present application. The lubricant composition contains 55-98% by weight of at least one lubricating viscosity oil. This viscosity is typically in the range of approx. 2.0 to approx. 150 cst at 98.9 ° C, and more typically in the range of ca. 5.0 to approx. 130 cst at 98.9 ° C.

These lubricating viscosity oils can be natural or synthetic oils. Mixtures of such oils are also often useful.

Natural oils include animal and vegetable oils (e.g.

35 and castor oil) as well as mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of paraffinic, naphthenic or mixed paraffinic-naphthenic type. Also oils with lubricating viscosity extracted from

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5 coal or shale, are useful as base oils.

The synthetic lubricating oils include hydrocarbon oils and halogen-substituted hydrocarbon oils, such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene isobutylene copolymers, chlorinated polybutylenes, etc.); poly (1-hexenes), poly- (1-octenes), poly (1-decenes), etc., and mixtures thereof; alkylbenzenes (eg dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di- (2-ethylhexyl) -benzenes, etc.); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated di phenyl ethers and alkylated diphenyl sulfides as well as derivatives, analogs and homologs thereof and the like.

Oils produced by the polymerization of olefins having less than 5 carbon atoms, such as ethylene, propylene, butylene, isobutene, pentene and mixtures thereof, are typical synthetic polymer oils. Methods for preparing such polymer oils are well known to those skilled in the art and are disclosed in U.S. Patent Nos. 2,278,445, 2,301,052, 2,318,719, 2,329,714, 2,345,574 and 2,422,443.

Alkylene oxide homopolymers and interpolymers, as well as derivatives thereof, wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another category of known synthetic lubricating oils. These are exemplified by the oils produced by the polymerization of ethylene oxide or propylene oxide, all the coolers and aryl ethers of these polyoxyalene polymers (e.g. methyl polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ethers of polyethylene glycol having a molecular weight of 500-1000, polypropylene glycol diethyl ethers having a molecular weight of 1000-1500, etc.) or mono- and polycarboxylic acid esters thereof, e.g. acetic acid esters, mixed C 1 -C 6 fatty acid esters, or the C 13 oxo acid diester of tetraethylene glycol.

Another suitable category of synthetic lubricating oils comprises the esters of di carboxylic acids (e.g., phthalic acid, succinic acid, all alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimeric acid, malonic acid, malonic acid, -erols, etc.) with numerous different alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethyl hexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include di butyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, di octyl sebacate, diisooctylazelate, diisodecyllazate, dioctyl phthalate, didecyl phthalate, dieicosylsebacate

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6 µl of nole acid dimer, the complex ester formed by reacting one mole of sebacetic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid and the like.

Esters useful as synthetic oils also include esters prepared from Cg to CJ2 monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.

The silicone based oils such as the polyalkyl, polyaryl, polyalkoxy or polyaryloxy siloxane oils and silicate oils form another useful category of synthetic lubricants (e.g. tetraethyl silicate, tetra-i sopropyl silica, tetra (2-ethylhexyl) si 1 in cat, tetra- (4-methyl-hexyl) si-1 in cat, tetra- (p-tert-butylphenyl) si 1 in cat, hexyl- (4-methyl-2-pentoxy) -di-siloxane, poly (methyl) siloxanes, poly (methylphenyl) siloxanes, etc.). Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decanphosphonic acid, etc.), polymeric tetrahydrofurans and the like.

Unrefined, refined and refined oils, either natural or synthetic (as well as mixtures of two or more of any of these) of the type described above can be used in the lubricants 20 of the present invention. Unrefined oils are oils that are obtained directly from a natural or synthetic source without further purification treatment. Eg. a shale oil obtained directly from retort operations, a petroleum oil obtained directly from primary distillation, or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. The refined oils are similar to the unrefined oils, except that they have been further processed in one or more purification steps to improve one or more properties. Many such purification techniques such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. are known to those skilled in the art. Refined oils are obtained by processes similar to those used "to produce refined oils, applied to refined oils which have already been used in operation. Such refined oils are also known as recycled or re-treated oils and are often further treated by techniques, 35 which is aimed at removing used additives and oil degradation products.

In the aminophenols, the aromatic moiety, Ar, may be a single aromatic core, such as a benzene core, a pyridine core, a thiophene core, a

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7 1,2,3,4-tetrahydronaphthalene core, etc. or a polynuclear aromatic moiety. Such polynuclear parts may be of the fused type, i. wherein at least two aromatic nuclei at two points are fused to another nucleus as found in the naphthalene, anthracene, aza-naphthalene, etc. Such polynuclear aromatic moieties may also be of the linked type, wherein at least two cores (either mono- or polynuclear) are linked to each other through bridging bonds. Such bridging bonds can be selected from the group consisting of carbon-to-carbon single bonds, ether bonds, keto bonds, 10 sulfide bonds, polysulfide bonds of 2 to 6 sulfur atoms, sulfinyl bonds, sulfonyl bonds, methylene bonds, all alkylene bonds, di- (lower alkyl) methylene bonds, lower alkylene-ether bonds, alkylene-keto bonds, lower alkylene-sulfur bonds, lower alkylene polysulfide bonds of 2 to 6 carbon atoms, amino bonds, polyamino bonds, and 15 mixtures of such divalent bridge-building bonds. In some cases, more than one bridge-building bond can be found in Ar between aromatic nuclei. Eg. a fluorine core has two benzene cores linked to both a methylene bond and a covalent bond. Such a core can be considered as having three cores, but only two of them are aromatic. Usually, Ar will only contain carbon atoms in the aromatic core itself.

The number of aromatic nuclei, whether fused, linked, or both, in Ar may play a role in determining the values of a, b and c in formula I. When e.g. Ar contains a single aromatic core, a, b and c are independently 1 to 3. When Ar contains two 25 aromatic cores, a, b and c can each be an integer of from 1 to 6, ie. from 1 up to 3 times the number of aromatic cores present (for example, in the naphthalene 2 cores). At a trinuclear Ar moiety, a, b and c can again each be an integer of from 1 to 9. Thus, for example, Ar. is a biphenyl moiety, a, b and c can each independently be an integer of from 1 30 to 6. The values of a, b and c are obviously limited by the fact that their sum cannot exceed the total number of unfulfilled valences. on Ar.

The single ring aromatic core, which may be the Ar moiety, may be denoted by the general formula: 35 sc (Q) m wherein sc is a single ring aromatic core (e.g. benzene) of

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s 4 to 10 carbon atoms, each Q independently represents a lower alkyl group, a lower alkoxyl group, a nitro group or a halogen atom, and m is 0 to 3. The term "lower", as used in this specification and claims, refers to groups having 7 or fewer carbon atoms, such as lower alkyl and lower alkoxyl groups. Halogen atoms include fluorine, chlorine, bromine and iodine atoms, the halogen atoms being usually fluorine and chlorine atoms.

As specific examples of such single-ring Ar moieties may be mentioned: f ~ Me h- ^ J-h 'J-h h Y T ^ T · i [i

H β — OPr H -1¾¾. J-H

T T N

-Me H Cl H - H2 ^ ch2- ch2 „i T KA CH2

Η \ Λη Ha-W-Ha H ^ H

30, wherein Me represents methyl, Et represents ethyl, Pr represents n-propyl and Nit represents nitro.

When Ar represents an aromatic moiety with polynuclear fused ring, it may be denoted by the general formula: wherein ar, Q and m have the meanings defined above, m 'is 1 to 4,

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9, and denotes a pair of fusing bonds which fuse two rings so that two carbon atoms are made part of the rings for each of two adjacent rings. Specific examples of aromatic moieties Ar with fused rings are:

5 I H

H Ih 10 il Me0

Η \ Αγ * ~ α H

H 'H

; T I »r X e.g. 20« -kJLJ- --vJL ^ A * etc.

10

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When the aromatic moiety Ar is a linked polynuclear aromatic moiety, it may be denoted by the general formula: ar - {- Lng-ar -} - (Q) 5 wherein w is an integer of from 1 to ca. 20, scars have the meaning described above, assuming that there are at least 3 unfulfilled (i.e. free) valences on the total number of scars groups, Q and m have the meaning defined above, and each Lng represents a bridge-building bond individually selected from the group consisting of carbon-to-carbon single bonds, ether linkages (e.g. -O-), keto bonds (e.g.

0

II

-C-), sulfide bonds (eg -S-), polysulfide bonds with 2 to 6 sulfur bonds (eg -Sg.g-) sulfinyl bonds (eg -S (O) -), sul- 15 phonyl bonds (e.g. -S (O) 2-), lower alkylene bonds (e.g.

-CH2-, -CH2 -CH2-, -CH-CH-, etc.), di (lower alkyl) methylene bonds R ° (e.g. -CR2), lower alkylene ether bonds (e.g. -CH2O-, CH20-CH2-, CH9-CH90-, -CH9COCH9CH, -, -ch9choch9ch-, -CHoCHOCHCH9-, 2 2 '2 2 2 2' 2, 2, '2, 2' 20 R ° R ° R ° R ° O 0 η 1, etc.), lower alkylene keto bonds (e.g., -CH 2 -C, -CH 2 CCH 2 -), lower alkylene sulfide bonds (e.g., wherein one or more of the the alkylene-ether bonds are replaced by an -S atom), lower alkylene polysulfide bonds (e.g., wherein one or more of the -Os are replaced by an -S2_g group), amino bonds (e.g. -N-, -N-, -CH2N- HR ° -CH2NCH2-, -alk-N-, wherein alk is lower alkyl, etc.), polyamino bonds (e.g. -N (alkN)) wherein the unfulfilled free N valences are taken up by H atoms or R ° groups) and mixtures of such bridging bonds (each R ° represents a lower alkyl group).

Specific examples of Ar when it denotes a linked polynuclear aromatic moiety include:

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11

H Η Η H

5 tVfr π ^ οίγ \

HH HH

10 1 f I

_CH 2 H

* H

H2

C

20 H-T ^ J V_ ^ ~ M

—ΊΓ ^ 5 ^ \ i} / 25 hV Me '^ - ^ HJ rio

Η H

J * Me X

30 \ i i "1l I

-KA MejL ^ ”

H

I h

35 i / I \ - j ^ X - 4- Η / γ ^ Β \ J> - »· -etc-

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12

These Ar moieties are usually all unsubstituted, except for the R, -OH and -NHg groups (and any bridging groups).

For reasons such as cost, availability, performance, etc., the part is usually a benzene core, a lower alkylene bridge benzene core or a naphthalene core. Thus, a typical Ar moiety is a benzene or naphthalene monomer having 3 to 5 unfulfilled valences, so that one or two of these valences can be satisfied with a hydroxyl group, while the remaining unfulfilled valences are in either ortho- or para position to a hydroxyl group. It is preferred that Ar is a benzene core having 3 to 4 unfulfilled valences so that one can be satisfied with a hydroxyl group while the remaining 2 or 3 are either in ortho or para position to the hydroxyl group.

The aminophenols used in the lubricant composition used in the process of the invention contain directly bonded to the aromatic moiety Ar a substantially saturated monovalent hydrocarbon-based group R having 30-400 aliphatic carbon atoms. More than one such group can be found, but usually no more than 2 or 3 such groups exist for each aromatic core of the aromatic moiety Ar. The total number of R groups present is indicated by the value of "a" in Formula I. More typically, the hydrocarbon-based group contains at least approx. 50 aliphatic carbon atoms and up to approx. 300 aliphatic carbon atoms.

The hydrocarbon-based groups R are usually formed from homo- or interpolymers (e.g. copolymers and terpolymers) of mono- and 25-olefins having 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, isobutene, butadiene, soprene, 1-hexene, 1-octene, etc. These olefins are typically 1-mono-olefins. The R groups may also be derived from the halogenated (e.g., chlorinated or brominated) analogs of such homo- or interpolymers. However, the R groups may be formed from other sources, such as high molecular weight monomeric alkenes (e.g., the 1-tetracontene) and chlorinated analogs, and hydrochlorated analogs thereof, aliphatic petroleum fractions, preferably paraffin waxes and cracked and chlorinated analogs and hydrochlorinated analogues thereof, white oils, synthetic alkenes such as alkenes produced by the Ziegler-Natta process (e.g., poly (ethylene) lubricant) and other sources known to those skilled in the art. Any unsaturation in the R groups can be reduced or eliminated by hydrogenation according to methods known in the art prior to the nitration step described hereinafter.

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13

The term "hydrocarbon based" as used herein refers to a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly hydrocarbon-like character within the meaning of the invention. Hydrocarbon-based groups may therefore contain 5 up to one non-hydrocarbon radical for every 10 carbon atoms, provided that this non-hydrocarbon radical does not significantly alter the predominantly hydrocarbon-like nature of the group. Those skilled in the art will be familiar with such radicals as e.g. include hydroxyl, halogen (especially chlorine and fluorine), alkoxyl, alkylmercapto, alkylsulfoxy, etc.

However, usually the hydrocarbon-based groups R are pure hydrocarbon radicals and do not contain any such non-hydrocarbon radicals.

The hydrocarbon-based groups R are substantially saturated, i.e. that they contain no more than one unsaturated carbon-to-carbon bond for every 15 carbon-to-carbon single bonds present. Usually, they contain no more than one non-aromatic unsaturated carbon-to-carbon bond for every 50 carbon-to-carbon bonds present.

The hydrocarbon-based groups in the aminophenols used in the process of the invention are also essentially aliphatic in nature, i.e. that they contain no more than one in non-aliphatic (cycloalkyl, cycloalkenyl or aromatic) group of 6 or fewer carbon atoms for every 10 carbon atoms in the R group. However, the R groups usually do not contain more than one such non-aliphatic group for every 50 carbon atoms, and in many cases they do not contain such non-aliphatic groups at all, i.e. that the typical R groups are purely aliphatic. These purely aliphatic R groups are typically alkyl or alkenyl groups.

The following groups are specific examples of the substantially saturated hydrocarbon-based R groups: 30 - tetra (propylene) groups - tri (isobutene) groups - tetracontanyl groups - henpentacontanyl groups 35 - mixtures of poly (ethylene / propylene) groups of approx. 35 to approx.

70 carbon atoms - mixtures of oxidatively or mechanically degraded poly (ethylene / propylene) groups of approx. 35 to approx. 70 carbon atoms

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14 - mixtures of poly (propylene / 1-hexene) groups of approx. 80 to approx.

150 carbon atoms - mixtures of poly (isobutyl) groups with between 30 and 32 carbon atoms 5 - mixtures of poly (isobutyl) groups with an average of 50 to 75 carbon atoms.

A preferred source for the R group is poly (isobutylene), which is obtained by polymerizing a refinery stream with a butene content of 10 to 35% to 75% by weight and an isobutylene content of 30 to 60% by weight in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutzenes contain predominantly (more than 80% of the total repeating units) isobuten repeating units of the configuration: 15 CHt in -CH - C- ch3 20

The attachment of the hydrocarbon-based group R to the aromatic moiety Ar of the aminophenols used in the process of the invention can be accomplished by a variety of techniques known to those skilled in the art. A particularly suitable technique is the Friedel-Crafts reaction in which an olefin (e.g., a polymer containing an olefin bond) or a halogenated or hydrohalogenated analog thereof is reacted with a phenol. The reaction occurs in the presence of a Lewis acid catalyst (e.g. boron trifluoride and its complexes with ethers, phenols, hydrogen fluoride, etc., aluminum chloride, aluminum bromide, zinc dichloride, etc.) The methods and conditions for carrying out such reactions are known to those skilled in the art. Reference is made e.g. for the discussion in the article "Alkylation of Phenols" in Kirk-Othmer's "Encyclopedia of Chemical Technology", 2nd Edition, Vol. 1, pp. 894-895, Interscience Publishers,

Div. of John Wiley and Company, N.Y., 1963. Other equally well-known and convenient techniques for attaching the hydrocarbon-based group R to the aromatic moiety Ar will be apparent to those skilled in the art.

As will be seen from observing Formula 1, amino acids contain

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The phenols used in the process of the invention include at least one of each of the following substituents: hydroxyl group, R group as defined above and primary amine group, -NHg. Each of the aforementioned groups must be attached to a carbon atom which is part of an aromatic nucleus of the Ar moiety. However, they do not all need to be attached to the same aromatic ring if more than one aromatic core is present in the Ar moiety.

In a preferred embodiment, the aminophenols used in the process of the invention contain one of each of the foregoing substituents and only a single aromatic ring, particularly preferably benzene. This preferred category of aminophenols may be denoted by the general formula:

OH

is (R 1, z) wherein the R 1 group is a hydrocarbon based group of about 30 to approx. 400 represents aliphatic carbon atoms which are in ortho or para position to the hydroxyl group, R "represents a lower alkyl group, lower alkoxyl group, nitro group or a halogen atom, and z is 0 or 1. Usually z is 0 and R7 represents a substantially saturated, pure aliphatic group, often an alkyl or alkenyl group which is in a para position to the -OH substituent.

In an even more preferred embodiment of the invention, the aminophenol has the formula:

OH

30 'R' "> zC J 2 R" wherein R "is derived from homopolymerized or interpolymerized Cg.jQ 35 1 olefins and contains an average of from about 30 to about 300 aliphatic carbon atoms, and R777 and z have the above defined meaning.

R "is usually derived from ethylene, propylene, butylene or mixtures thereof and is typically derived from polymerized isobutene. Often R"

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16 at least approx. 50 aliphatic carbon atoms and z is 0.

The aminophenols used in the process of the present invention can be prepared by a variety of synthetic routes.

These routes may vary in the type of turnover used and the order in which they are used. Eg. For example, an aromatic hydrocarbon such as benzene can be alkylated with an alkylating agent such as a polymeric olefin to form an alkylated aromatic intermediate. This intermediate can then be nitrated, e.g. to form a polynitro intermediate. The polynitro intermediate can then be reduced to a diamine which can then be diazotized and reacted with water to convert one of the amino groups to a hydroxyl group and provide the desired aminophenol. Alternatively, one of the nitro groups in the polynitro intermediate can be converted to a hydroxyl group by melting with alkali to produce an alkylated aromatic hydroxynitro compound which can then be reduced to produce the desired aminophenol.

Another useful reaction pathway for aminophenols includes alkylation of a phenol with an olefinic alkylating agent to form an alkylated phenol. This alkylated phenol can then be nitrated to form a mono- or polynitrophenol which can be converted to the desired 20 aminophenols by reducing at least a portion of the nitro groups in the intermediate to amino groups.

Phenol alkylation techniques are well known to those skilled in the art, as will be apparent from the above-mentioned article in Kirk-Othmer "Encyclopedia of Chemical Technology". Techniques for nitrating 25 phenols are also known. For example, reference is made to the article "Nitrophenols", p.

888 et seq., In Kirk-Othmer's "Encyclopedia of Chemical Technology, 2nd ed., Vol. 13, as well as the theses" Aromatic Substitution;

Nitration and Halogenation "by P.B.D. De La Mare and J.H. Ridd, N.Y.,

Academic Press, 1959; "Nitration and Aromatic Reactivity" by J.G.

30 Hogget, London, Cambridge University Press, 1961, as well as "The Chemistry of the Nitro and Nitroso Groups", Henry Feuer, publisher of Interscience Publishers, N.Y., 1969.

Aromatic hydroxy compounds can be nitrated with nitric acid, mixtures of nitric acid and with acids such as sulfuric acid or boron trifluoride, nitrogen tetraoxide, nitronium tetrafluoroborate and acyl nitrates. Usually nitric acid is in a concentration of e.g. 60-90% a convenient nine trating reagent. Essentially inert liquid diluents and solvents such as acetic or butyric acid may help

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17 during the reaction by improving the reagent contact.

Conditions and concentrations for nitriding hydroxyaromatic compounds are also well known to those skilled in the art. Eg. the reaction can be carried out at temperatures of approx. -15 ° C to approx. 150 ° C. Nitration is usually conveniently carried out between ca. 25 and approx. 75 ° C.

Usually, depending on the particular nitrating agent, approx. 0.5 to 4 moles of nitrating agent for each mole of aromatic core present in the hydroxyaromatic intermediate to be nitrated.

If more than one aromatic core is present in the Ar moiety, the amount of nitrating agent may be increased proportionally to the number of such nuclei present. Eg. For example, a mole of naphthalene-based aromatic intermediate for the purpose of the invention has an equivalence of two "single-ring" aromatic cores, such that about 1-4 moles of nitrating agent will usually be used. When nitric acid is used as a nitrating agent, about 10% is usually used. 1.0 to approx. 3.0 moles per moles of aromatic core. Up to approx. a 5-molar excess of nitrating agent (per "single-ring" aromatic core) when it is desired to drive the reaction forward or complete it rapidly.

Nitration of a hydroxy aromatic intermediate usually lasts 20 0.25 to 24 hours, depending on such variables as the temperature, amount, type and quality of the intermediate and the nitrating agent, although it may be convenient to react the nitration reaction for extended periods, such as 96 hours.

Also, reduction of aromatic nine faith compounds to corresponding amines is well known. Reference is made e.g. to the article "Amination City

Reduction "in Kirk-Othmer" Encyclopedia of Chemical Technology ", 2nd edition, vol. 2, pp. 76-99. Generally, such reductions can be carried out with, for example, hydrogen, carbon monoxide or hydrazine (or mixtures of the same) in the presence of of metal catalysts such as palladium, platinum and its oxides, nickel, copper chromite, etc. Cocatalysts such as alkali or alkaline earth metal hydroxides or amines (including aminophenols) may be used in these catalyzed reductions.

Reduction can also be accomplished using reducing metals in the presence of acids such as hydrochloric acid. Typical reducing metals are 35 zinc, iron and tin; salts of these metals can also be used.

Nitro groups can also be reduced by the Zinin reaction discussed in "Organic Reactions", vol. 20, John Wiley & Sons, N.Y., 1973, p.

455 et seq. The zinin reaction usually includes reduction of

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18 is a nitro group with divalent negative sulfur compounds such as alkali metal sulfides, polysulfides and hydrosulfides.

The nitro groups can be reduced by electrolytic action, see e.g. "Amination by Reduction" referred to above.

5- Aminophenols are typically obtained by reducing nitrophenols with hydrogen in the presence of a metal catalyst, as discussed above. This reduction is usually carried out at temperatures of about 15 to approx. 250 ° C, typically approx. 50 - approx. 150 ° C and overpressure of approx. 0 to approx. 13,800 kPa, typically approx. 345 to approx. 1725 kPa. The turnover time for reduction 10 usually varies between approx. 0.5 to approx. 50 hours. To facilitate the reaction, substantially inert liquid diluents and solvents such as ethanol, cyclohexane, etc. may be used.

The aminophenol product is obtained by well-known techniques such as distillation, filtration, extraction, etc.

15 The reduction is carried out until at least approx. 50%, usually approx.

80% of the total number of nitro groups in the nitro intermediate mixture is converted to amino groups. The typical reaction pathway just described for aminophenols can be summarized as follows: (I) nitration with at least one nitrating agent of at least one compound of the formula: (OH) c in (R) -Ar '

Cl 25 wherein R represents a substantially saturated hydrocarbon-based group of 30-400 aliphatic carbon atoms; a and c are each independently an integer of 1 up to 3 times the number of aromatic cores found in Ar, provided that the sum of a, b and c does not exceed the number of unfulfilled valences on Ar '; and Ar 'represents an aromatic moiety having 0 to 3 optional substituents selected from lower alkyl, lower alkoxyl, nitro and halogen, or combinations of two or more optional substituents with the conditions that (a) Ar' has at least one hydrogen atom, which is directly bonded to a carbon atom which is part of an aromatic core, and (b) when Ar 'represents a benzene nucleus having only one hydroxyl and one R substituent, the R substituent is in ortho or para-position to the hydroxyl substituent to form a first reaction mixture containing a nitro intermediate, and (II) reducing at least approx. 50% of the nitro groups in the first reaction mixture for amino groups.

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19 Usually this means that at least approx. 50% of the nitro groups are reduced to amino groups in a compound or mixture of compounds of formula: r (OH) c

5 I

(R) - Ar- (N ° 2) b wherein R represents a substantially saturated hydrocarbon-based substituent having 30-400 aliphatic carbon atoms; a, b and c are each independently an integer from 1 up to 3 times the number of aromatic cores found in Ar, provided that the sum of a, b and c does not exceed the number of unfulfilled valences on Ar; and Ar represents an aromatic moiety having 0 to 3 optional substituents in the form of lower alkyl, lower alkoxyl, halogen or combinations of two or more of the optional substituents; with the proviso that when Ar represents a benzene nucleus having only one hydroxyl and one R substituent, the R substituent is in ortho or para position to the hydroxyl substituent.

The following examples describe examples of the preparation of 20 typical aminophenols for use in the process of the invention.

As will be appreciated by those skilled in the art, aminophenols prepared by other techniques may also be used. All parts and percentages are by weight, and all temperatures are in degrees Celsius (° C) in the Examples and elsewhere in the specification, unless expressly stated otherwise.

Example 1A

An alkylated phenol is prepared by reacting phenol with polyisobutene having a number average molecular weight of about 1000 (vapor phase osmometry) in the presence of a boron trifluoride phenol complex catalyst. Stripping the product thus formed first to 230 ° / 760 tor (vapor temperature) and then to 205® vapor temperature / 50 tor produces purified alkylated phenol.

For a mixture of 265 parts of purified alkyl phenol, 176 parts of mixed oil and 42 parts of a petroleum naphtha with a boiling point of approx. 20 ° slowly add a mixture of 18.4 parts of concentrated nitric acid (69-70%) and 35 parts of water. The reaction mixture is stirred for 3 hours at ca. 30-45 °, stripped to 120 ° / 20 tor and filtered to give an oil solution.

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Of the desired nitrophenol intermediate.

Example IB

A mixture of 1500 parts of the product solution according to 1A, 642 parts of 5-propanol and 7.5 parts of nickel on diatomaceous earth catalyst is introduced into an autoclave under nitrogen atmosphere. After cleaning with nitrogen and evacuating 3 times, the autoclave is put under an excess pressure of 690 kPa with hydrogen and stirring is started. The reaction mixture is maintained at 96 ° C for a total of 14 1/2 hours, while a total of 1.66 moles of hydrogen is indigenous. After cleaning with the hydrogen and evacuating 3 times, the reaction mixture is filtered and the filtrate stripped to 120 µ / 18 tor. Filtration gives the desired product in an oil solution containing 0.54% nitrogen.

Example 2A

To a mixture of 400 parts of polyisobutene-substituted phenol (in which the polyisobutyl substituent contains about 100 carbon atoms), 125 parts of so-called "textile spirits" and 266 parts of a dilute mineral oil at 28 ° are slowly added 22.83 parts of nitric acid (70%). 50 parts water over 0.33 hours. The mixture is stirred at 28-34 ° for 2 hours and stripped to 158 ° / 30 tor; filtration gives an oil solution (40%) of the desired intermediate with a nine trogen content of 0.88%.

Example 2B

A mixture of 93 parts of the product solution of Examples 2A and 93 parts of a mixture of toluene and 2-propanol (50/50 by weight) is introduced into an appropriate size hydrogenation container. The mixture is degassed and nitrogen purified; 0.31 parts of a commercial platinum oxide catalyst (86.4% PtOg) is added. The reaction vessel is put under a pressure of 393 kPa and maintained at 50-60 ° for 21 hours. A total of 0.6 mole of hydrogen is introduced into the reaction vessel. The reaction mixture is then filtered and the filtrate is stripped to give the desired product in an oil solution containing 0.44% nitrogen.

Example 3A

A mixture of 2160 parts of the polyisobutene-substituted phenol of Examples 2A and 1440 parts of a dilute mineral oil is heated to 60 °. Then 25 parts of paraformaldehyde are added to the mixture followed by 15 parts of aqueous hydrochloric acid. The mixture is heated to 115 ° for 1 hour. After

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After standing for 16 hours at room temperature, the reaction mixture is heated to 160 ° for 1 hour, while 20 parts of distillate are removed. Stripping the reaction mixture to 160 ° / 15 tor gives an oil solution of the desired methylene-bound polyisobutene-substituted phenol.

5

Example 3B

To 2406 parts of the oil solution described in Example 3A and 600 parts of textile spirits, 90 parts of nitric acid (70%) are added over 1 1/2 hours. The reaction mixture is stirred for 1 1/2 hours, allowed to stand at room temperature for 63 hours and then heated for 90 hours at 90 °. Striping to 160 ° / 18 tor gives an oil solution of the desired nitrated intermediate containing 0.79% nitrogen.

Example 3C

A mixture of 800 parts of the oil solution of Example 3B and 720 parts of a toluene / 2-propanol mixture (60/40 by weight) is introduced into an autoclave. After nitrogen purification, 4 parts of nickel-on-silica-gum catalyst are added. Nitrogen purification is repeated 3 times and the autoclave is pressurized with hydrogen to 414 kPa at 25 °. The reaction temperature 20 is slowly raised to 96 ° and the overpressure is maintained at 690 kPa for 5 1/2 hours. Then the autoclave opens and another 4 parts nickel-on-diatomaceous earth catalyst is added. The autoclave is again put under a pressure of 690 kPa hydrogen and maintained at 96 ° and 690 kPa for 6 hours. Then, the autoclave is cooled and reopened and an additional 0.8 parts platinum oxide catalyst is added.

The autoclave is then brought back to an excess pressure of 621 kPa with hydrogen and held at this pressure for an additional 8 hours. The reaction mixture is filtered and stripped to 150 ° / 18 tor to give an oil solution of the product with a nitrogen content of 0.41%.

Example 4A

A mixture of 1962 parts of the polyisobutene-substituted phenol of Example 1A, 49.5 parts of paraformaldehyde, 15 parts of aqueous hydrochloric acid and 1372 parts of dilute mineral oil is heated for 7 hours at 115 °. Then the reaction temperature is increased to 160-165 ° and maintained for a further 7 to -35 hours. Add 400 parts of textile spirits to the mixture and cool to 30 °. Then 136.95 parts of nitric acid (70%) are slowly added in 140 parts of water. The reaction mixture is stirred for 1 1/2 hours at 30-35 ° and then stripped to 170 ° / 28 tor to give an oil solution of medium.

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22 which is cleared by filtration.

Example 4B

96 parts of the oil solution described in Example 4A and 96 parts of 5 a toluene / 2-propanol mixture (50/50 by weight) are introduced into a suitable sized hydrogenation vessel. After nitrogen purification, 0.32 parts of platinum oxide catalyst is added. After the reaction vessel is again purified, it is brought to an overpressure of 393 kPa at 25 ° with hydrogen. The hydrogen pressure is maintained between 393 and 345 kPa for 60 hours, while the reaction mixture is heated to 50 to 60 °. The resulting reaction mixture is filtered and stripped to give an oil solution of the product having a nitrogen content of 0.353%.

Example 5A

15 To a mixture of 654 parts of the polyisobutene-substituted phenol of Example 1A and 654 parts in succinic acid at 27 to 31 °, 90 parts of 16 molar nitric acid are added over half an hour. The frection mixture is kept at 50 ° for 3 hours and then stored at room temperature for 63 hours. Stripping to 160 ° / 26 tor and filtering through filter aid yields the desired nitro intermediate, which has a nitrogen content of 1.8%.

Example 5B

The nitro product of Example 5A is hydrogenated using a nickel-on-diatomaceous earth catalyst, following essentially the same procedure as described in Example 1B.

Example 6A

A mixture of 4578 parts of the polyisobutene-substituted phenol of Example 1A, 3052 parts of dilute mineral oil and 725 parts of 30 "textile spirits" is heated to 60 ° to obtain homogeneity. After cooling to 30 °, 320 parts of 16 molar nitric acid in 600 parts of water are added to the mixture. Cooling is required to keep the mixture below 40 °.

After stirring the reaction mixture for a further 2 hours, 3710 parts are transferred to another reaction vessel. These 3710 parts are treated with 35 additional 128 parts 16 molar nitric acid in 130 parts water at 25-30 °. The reaction mixture is stirred for 1 1/2 hours and then stripped to 220 ° / 30 tor. Filtration provides an oil solution of the intermediate.

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23

Example 6B

The oil solution of the product formed in Example 6A is hydrogenated using a platinum oxide catalyst in substantially the same manner as described in Example 1B.

5

Example 7

A mixture of 543 parts of a dinitrogen-alkylated phenol (prepared essentially in the same manner as described in Example 6A), 543 parts of isopropanol and 200 parts of toluene is treated at 19 ° C with a total of 42 parts of 10 gaseous ammonia over for a period of 3/4 hour. The reaction mixture is then treated with 147 parts of gaseous HgS. Both ammonia and hydrogen sulphide treatment are not effected by introducing the gas into the stirred mixture below its surface. Ammonia treatment is repeated with 82 parts of gaseous ammonia followed by a final treatment with 102 parts of hydrogen sulfide. Stripping the reaction mixture to 40 ° / 60 tor gives a residue which is combined with 161 parts of diluting oil and stripped again to 70 ° C / 18 tor. An additional 161 parts of diluent oil and 35 parts of filter aid are added; filtration of this mixture yields a vicostate filtrate which is a 40% oil solution of the diaminophenol.

The nine rings of Examples 8-14 are carried out in substantially the same manner as described in Example 1A using the hydroxyaromatic compounds and the amounts of nitric acid shown in Table A. Reduction of the nitromell intermediates in these examples is performed using the techniques described in the 25 examples shown in Table A.

30 35

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24

Table A

Example Hydroxyaromatic Mol HN032 Reduction compound technique3 5 Name Mol weight1

2,2'-dipoly (isobutene) yl-4,4'-2500 '2,2 IB

d in hydroxybi phenyl 11 8-hydroxy-2-poly (propenyl) yl-900 1.0 7 10 1-azanaphthalene

12 4-poly (isobutyl) yl-1-naphthol 1700 1.1 IB

13 2-poly (propylene / butene-1) yl 3200 2.4 IB

4.4m sopropyl 1 in denbi sphenol 4 14 4-tetra (propenyl) yl-2-hydroxy- 1.0 7 anthracene

4-Octadecyl-1,3-dihydroxy- 2.2 IB

benzene 16 4-poly (isobutene) -3-hydroxy-1300 1.0 7 pyridine 20 _ 1 Number average molecular weight by vapor phase osmometry.

2 times HNO mole of hydroxyaromatic compound.

3 Ie. essentially the same technique as described in the above example.

4 The molar ratio of propylene-to-butene-1 in the substituent is 2: 3.

The lubricant compositions for use in the process of the invention for lubricating a 2 stroke engine include 98 to 55% oil or 30 blend of oils of lubricating viscosity. Typical compositions contain approx. 90 to approx. 70% oil. The currently preferred oils are mineral oils and mineral oil synthetic polymer and / or ester oil blends. Polybutenes with molecular weights of approx. 250 to approx. 1000 (as measured by vapor phase osmometry) and polyol fatty acid esters such as pentaerythritol and trimethylol propane are typical useful synthetic oils.

These oil compositions contain from 2 to 30%, typically approx. 5 to approx.

20%, of at least one aminophenol as described above. Other additives such as auxiliary detergents and dispersants of the ash

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25 generating or ashless type, antioxidants, coupling agents, floating point lowering agents, extreme pressure agents, color stabilizers and anti-foaming agents may be present.

Detergent dispersants are of ash-free types and ash-producing metal types are used for checking piston ring attachment and ordinary engine cleaning, the 2-stroke lubricants for heavier loads necessitate the use of suitable ash-free dispersants due to the reference engine's propensity for deposition-induced ignition. For other compositions, calcium, barium or magnesium sulfonates are used, either alone, in combination with each other or in combination with ashless dispersants. Antioxidants can be added to promote the thermal stability of the lubricant.

Polymer VI enhancers have been used and are still being used as so-called "bright stock" replacements in the hope of improving lubricant film strength and lubrication and engine cleaning efficiency. Dyes can be used for identification purposes and to mark whether a 2-stroke fuel breath contains lubricant. Coupling agents are incorporated into some products to produce better component solubility and improved fuel / lubricant water tolerance.

Anti-ID and lubricant enhancers, preferably sulfur-treated spermacet oil substituents and other fatty acid and vegetable oils, such as castor oil, are used in particular applications, such as racing driving and at very high fuel / lubricant ratios. Propellants and combustion chamber deposition modifiers are sometimes used to promote better spark plug life and to remove soot deposits. Halogenated compounds and / or phosphorus-containing materials can be used for this purpose.

Rust and corrosion inhibitors of all types are incorporated and can be incorporated into 2-stroke sun in formulations. Odorants and deodorants are sometimes used for aesthetic reasons.

Also lubricating agents such as synthetic polymers (e.g., polyisobutene having a number average molecular weight in the range of from about 750 to about 300).

15,000), as measured by vapor phase osmometry or gel chromatography, polyol ether (e.g., poly (oxyethylene-oxypropylene) ethers) and esteryls (e.g., the esteryls described above) can be used in the present lubricant compositions. Natural oil fractions such as "bright stocks" (the relatively viscous products formed during conventional lubricating oil production from petroleum) can also be used for this purpose. They are usually found

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26 in the 2-stroke oil in an amount of approx. 3 to approx. 20% of the total oil composition.

As stated above, the lubricant compositions may also contain auxiliary detergent dispersants. Typical examples are the amide, amine salt-5 and / or amidine products formed by reacting fatty acids with 5 to 22 carbon atoms (eg isostearic acid and mixtures of in sostearic and stearic acid) with an alkylene polyamine having from 2 to approx. 10 amino groups and 2 to 20 carbon atoms such as ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, etc., including commercially available 10 mixtures of such alkylene polyamines. Such auxiliary detergent dispersants are represented by those disclosed in U.S. Patent No. 3,169,980, which patent is expressly incorporated herein by reference for such disclosure.

Diluents such as petroleum naphthas boiling in the range of 15 38-90 ° (e.g. "Stoddard Solvent") may also be included in the oil compositions, typically in an amount of 5 to 25%.

An illustrative 2-stroke engine lubricant composition contains 2-10% of one or more of the aminophenols previously described herein, such as the one described in Example 1B and a base oil composed of ca. 70-80 parts 20 by volume of 650 neutral oil, 8-12 parts by volume "bright stock" and 10-20 parts by volume "Stoddard Solvent".

In some 2-stroke engines, the lubricating oil can be injected into the combustion chamber along with the fuel or into the fuel immediately prior to the time the fuel enters the combustion chamber.

The process according to the invention is contemplated for the lubrication of such 2-stroke engines.

As is known to those skilled in the art, 2-stroke engine lubricating oils can be added directly to the fuel to form a mixture of oil and fuel, which is then introduced into the engine cylinder. Such lubricant-fuel oil mixtures are within the scope of the invention. Such lubricant-fuel mixtures usually contain, for each part of oil, about

15 - 250 parts fuel and they typically contain 1 part oil for approx. 50-100 parts fuel.

Typical specific examples of the 2-stroke engine oils of the invention are as follows:

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27

Component Weight percent

Example A Example B

Base oil1 58.6 67.0 5 "Bright Stock" 2 9.4 9.4 "Stoddard Solvent" 17.9 17.8

Aminophenol Additive 3 3 14.1

Aminophenol additive 1 4 - 5.8 10 1 A solvent refined neutral oil with a viscosity of 650 SUS at 98.8 ° C.

2 With a viscosity of 150 SUS at 98.8 ° C.

3 A mineral oil solution containing 60% of the aminophenol described in Example 3C.

4 A mineral oil solution containing 60% of the aminophenol described in Example 1B.

The fuels used in 2-stroke engines are well known to those skilled in the art and usually contain a greater proportion of a normal liquid fuel such as a hydrocarbon petroleum distillate fuel (e.g., engine gasoline as defined by ASTM Specification D-439-73). Such fuels may also contain non-hydrocarbon materials such as alcohols, ethers, organic nitro compounds and the like (e.g. methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) and also within the scope of the invention are liquid fuels derived from vegetable oils. or mineral sources, such as corn, alfalfa, shale and coal. Examples of such fuel supplements are combinations of gasoline and ethanol, diesel fuel and ether, gasoline and nitromethane, etc. Particularly preferred is gasoline, ie. a mixture of hydrocarbons having an ASTM boiling point of 60 ° C at 10% distillation point to ca. 205 ° C at the 90% distillation point.

The 2-stroke fuels also contain other additives well known to those skilled in the art. These may include antibanking agents, such as tetraal Kyl lead compounds, lead expelling agents such as halogenal cans (e.g. ethylene dichloride and ethylene dibromide), deposition preventive or modifying agents such as triaryl phosphates, dyes, cetane enhancers, antioxidants such as 2.6 -ditertiær-butyl-4-methylphenol,

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28 rust inhibitors such as alkylated succinic acids and anhydrides, bacteriostatic agents, rubber nanotubes, metal deactivators, demulsifiers, cylinder top lubricants, anti-icing agents and the like.

Claims (22)

A method of lubricating a 2-stroke internal combustion engine, characterized in that a lubricant composition containing 55-98, 5, preferably 70-90, wt% of at least one lubricating viscosity oil and 2-30, preferably 5-20, is used. % by weight of at least one amino-containing additive which (a) has the general formula: (OH) c10 (R) --- Ar - (NH2) b wherein R represents a substantially saturated hydrocarbon-based substituent having 30- 400 aliphatic carbon atoms; a, b and c are each independently an integer from 1 up to 3 times the number of aromatic cores found in Ar, provided that the sum of a, b and c does not exceed the number of unfulfilled valences on Ar; and Ar represents an aromatic moiety having 0 to 3 optional substituents in the form of lower alkyl, lower alkoxyl, nitro, halogen or combinations of two or more of the optional substituents; with the proviso that when Ar represents a benzene nucleus having only one hydroxyl and one R substituent, the R substituent is in the ortho or para position to the hydroxyl substituent, or which (b) is produced by reduction of at least approx. 50% of the nitro groups for amino groups in a compound or mixture of compounds of the formula: '(OH) c 30 (R) - Ar' wherein R represents a substantially saturated hydrocarbon-based substituent having 30-400 aliphatic carbon atoms; a, b and c are each independently an integer from 1 up to 3 times the number of aromatic nuclei found in Ar, provided that the sum of a, b and c does not exceed the number of unfulfilled valences on Ar; and Ar represents an aromatic moiety having 0 to 3 optional substituents in the form of lower alkyl, lower alkoxyl, halogen or combinations of two or more of the optional substituents; with the proviso that when Ar represents a benzene nucleus having only one hydroxyl and one R substituent, the R substituent is in ortho or para position to the hydroxyl substituent, the remainder of the composition being possibly present in itself 5 known additives, 2. A process according to claim 1, characterized in that R is all alkyl or alkenyl. 3. A process according to claim 1 or 2, characterized in that R is a substituent prepared from homopolymerized or interpolymerized C210 olefins selected from C2-1 olefins and mixtures thereof. 4. A process according to claim 3, characterized in that the 1-olefins are selected from ethyl one, propyl one, butyl ones and mixtures thereof. 5. A process according to any one of claims 1-4, characterized in that Ar contains two or more linked and / or condensed polynuclear aromatic cores. 6. A process according to any one of claims 1-4, characterized in that Ar represents a benzene nucleus having 0 to 3 of the optional substituents and a, b and c each being 1. 25 Process according to any one of claims 1-4, characterized in that the amino-containing additive has the formula OH nh 2 Wherein R 'represents a substantially saturated hydrocarbon-based substituent having an average of from about 30 to about 400 aliphatic carbon atoms located in ortho or para position for the hydroxyl group; R "is selected from lower alkyl, lower alkoxyl, nitro and halogen, and z is 0 or 1. DK 159932 B 8. A method according to claim 7, characterized in that R 'contains at least approx. 50 aliphatic carbon atoms. 9. A process according to claim 7 or 8, characterized in that R 'is in para position to the -OH substituent and z is 0. A process according to any one of claims 7-9, characterized in that R 'represents a substituent derived from homopolymerized or interpolymerized 1-olefins. 11. A process according to claim 10, characterized in that the 1-olefins are selected from ethyl one, propyl one, butyl ones and mixtures thereof. Process according to any one of claims 1-4 or 6-11, characterized in that the amino-containing additive has the formula OH 20 (R1 '1) -j-R "wherein R" is derived from homopolymerized or interpolymerized 25 C2_jq 1-olefins and on average contain from approx. 30 to approx. 300 aliphatic carbon atoms; Is selected from lower alkyl, lower alkoxyl, nitro and halogen; and z is 0 or 1. Process according to claim 12, characterized in that the 1-olefins 30 are selected from ethylene, propylene, butylene and mixtures thereof. A process according to claim 12 or 13, characterized in that R "represents an all cooling or alkenyl group containing on average at least about 50 aliphatic carbon atoms. Method according to any of claims 12-14, characterized in that z is 0. DK 1599 * 52 B Process according to any one of the preceding claims, characterized in that R contains on average up to approx. 300 carbon atoms. A process according to any one of the preceding claims, characterized in that Ar7 represents a benzene core. A process according to any one of the preceding claims, characterized in that the nitro intermediate is reduced with hydrogen in the presence of a metallic hydrogenation catalyst. Process according to any one of the preceding claims, characterized in that the amino-containing additive is prepared by (I) nitriding with at least one nitrating agent of at least one compound of formula (OH) c 20 (R) Ar 'wherein R represents a substantially saturated hydrocarbon-based group of 30-400 aliphatic carbon atoms; a and c each independently represent an integer of 1 up to 3 times the number of aromatic cores found in Ar, provided that the sum of a, b and c does not exceed the number of unfulfilled valences on Ar7; and Ar7 represents an aromatic moiety having 0 to 3 optional substituents selected from lower alkyl, lower 30 alkoxyl, nitro and halogen or combinations of two or more optional substituents, provided that (a) Ar7 has at least one hydrogen atom which is directly bonded to a carbon atom which is part of an aromatic core, and (b) when Ar represents a benzene nucleus, having only one hydroxyl and one R substituent, the R substituent is at ortho or para position 35 to the hydroxyl substituent , to form a first reaction mixture containing a nitro intermediate, and (II) reducing at least approx. 50% of the nitro groups in the first reaction mixture for amino groups. DK 159932 B A process according to any one of claims 1-4 or 6-18, characterized in that the amino-containing additive is prepared by (I) nitriding with at least one nitrating agent of at least one compound of the formula 5 OH (R "-h - S-R '10 wherein R' has a substantially saturated hydrocarbon-based substituent having an average of from about 30 to about 400 aliphatic carbon atoms located in the ortho or para position of the hydroxyl group; R '"is selected of lower alkyl, lower alkoxyl, nitro and halogen, and z is 0 or 1 to form a first reaction mixture containing a sodium intermediate and (II) reducing at least about 50% of the nitro groups in the first reaction mixture to amino groups. A process according to claim 20, characterized in that R 'is in para position to the hydroxyl group and is derived from homopolymerized isobutylene and z is o. A process according to any one of the preceding claims, characterized in that at least one nitro substituent is reduced with hydrogen in the presence of a metallic hydrogenation catalyst. 30 35