FI63053C - ANALYZING AV EN SMOERJMEDELSKOMPOSITION FOER SMOERJNING AV EN TVAOTAKTSFOERBRAENNINGSMOTOR - Google Patents

Description

- · ί ^ Τ '· 1, Β, .... ADVERTISEMENT _ _ J ^ STa ^ 11 ^ UTLÄCGNINGSSKRIFT 6 3053 C (45) r yc Lty 11 Cl 1903 ^ (51) Kv.ik.3 / int.a .3 C 10 M 1/32 ENGLISH — Fl N LAN D pi) ρμμοιιη ^ -νιμμιΜι 762915 (22) Hakamlsptlvl - Anaöknlnpd «g 13 * 10.76 (23) AlkupUvi - Gllti | h« t * da | 13.10.76 (41) Became slipped - kiwis effwtlig 15.0U .77 fWtt ^ and registry controlled NlhUvllulp ™, |. ku «LJuUc * and date - 31.12.82

Patent and regenerative legislation Ansukin utltgd odi utUkrtfkM publlcanrf (32) (33) (31) Prydftty «tuolkuut — luflnJ prtorttut 1 ^ .10.75 USA (US) 622357 (71) The Lubrizol Corporation, P.0. Box 17100 Euclid Station, Cleveland,

Ohio 1 + 1 + 117, USA (72) Kirk Emerson Davis, Euclid, Ohio, USA (7I +) Oy Jalo Ant-Wuorinen Ab (5M Use of a lubricant composition for lubrication of two-stroke internal combustion engines - Användning av en smörjmedelskomposition för smörjning av en This invention relates to the use of lubricant compositions having a higher lubricating viscosity oil and less at least one aminophenol in two-stroke internal combustion engines, and more particularly to the use of such oils containing aminophenols having at least one hydrocarbon-based group of 30 to 400 aliphatics. Because two-stroke engine oils are often blended with fuels before or after use, this invention also relates to the use of fuel and lubricant blends for two-stroke engines.

U.S. Patent 2,197,835 describes the preparation of metal salts of aromatic amines which are formed by nitration followed by reduction of paraffin-substituted hydroxyaromatic hydrocarbons. These metal salts can be added to mineral oils to lower their pour point and increase their viscosity indices.

U.S. Patents 2,502,708 and 2,571,092 describe nitration followed by hydrogenation to produce cardanolamine. This amino-cardanol has been considered a useful antioxidant for mineral oils, fats and crude oil products. Cardanol, also known as anacardol, is said to be 3-pentadecylphenol, 3- (81-pentadecenyl) phenol, 3- (8 ': 11'-pentadecadienyl) phenol 2,63053 and 3- (8: 11: 14'- a mixture of pentadecatrienyl) -phenol. The formulas disclosed in Patents 2,502,708 and 2,571,092, as well as the chemical literature (cf. Dictionary of Organic Compounds, Vol. 1, Oxford University Press, NY, 1965, p. 229), show that the C 1-4 substituent on cardanol is in the meta position relative to the hydroxy group.

U.S. Patent 2,859,251 describes the alkylation of ortho-, para- and meta-aminophenols with olefin polymers having 6 to 18 carbon atoms in the molecule in the presence of a catalytic complex obtained by mixing hydrogen fluoride with boron trifluoride and an iron group metal fluoride. U.S. Patent 2,859,251 does not mention whether the alkyl groups in the product are attached to a carbon, nitrogen and / or oxygen atom.

Over the last decades, the use of spark-ignition two-stroke internal combustion engines, including rotary piston engines such as Wankel-type engines, has steadily increased. They are now used in power-driven lawn mowers and other power-driven garden tools, chainsaws, pumps, electric generators, outboards, snowmobiles, and the like.

The ever-increasing use of two-stroke engines and their increasingly difficult operating conditions have placed increasing demands on oils that satisfactorily lubricate these engines. Problems associated with the lubrication of two-stroke engines include entrapment of the piston ring, rusting, unsatisfactory lubrication of the connecting rod and crankshaft bearings, and the formation of carbon and lacquer deposits on the inner surfaces of the engine. Varnish formation is a particularly difficult problem because the formation of varnish on the walls of the piston and cylinder is believed to cause the ring to stick, which in turn makes the sealing of the piston rings unsatisfactory. Such a weak seal causes a reduction in the compression pressure of the cylinder, which has a detrimental effect, especially in two-stroke engines, since their operation is based on the absorption of new fuel into the emptied cylinder. Thus, entrapment of the piston can result in reduced engine power and unnecessary fuel and / or lubricant consumption. These additives can also reduce fouling of the spark plug and clogging of the engine inlets.

The specific problems and technology associated with the lubrication of two-stroke engines have led to the fact that two-stroke engine lubricants are now considered by experts in the field to be a clearly separate type of lubricant, cf. e.g., U.S. Patents 3,085,975, 3,004,837, and 6,3053 to 3,753,905.

The object of the present invention is to eliminate these problems by means of effective additives for two-stroke engine oils and oil-fuel combinations which eliminate or reduce the formation of engine lacquer deposits and promote the sealing of the piston ring.

The invention thus relates to the use of new lubricants and fuel-lubricant mixtures for two-stroke engines, including Wankel engines.

Other objects of the invention will become apparent from the following description.

This invention relates to the use of lubricant compositions for lubricating two-stroke engines of the formula <? H, c (R) a-Ar - (NVb where R is a predominantly saturated hydrocarbon-based substituent having 30 to 400 aliphatic carbon atoms; a, b and c are each and independently an integer from 1 to 3 times the number of aromatic rings in the group Ar, wherein the sum of the numbers a, b and c does not exceed the number of unsaturated valencies in the group Ar, and Ar is an aromatic group having 0 to 3 possible substituents which are lower alkyl , lower alkoxyl, nitro, halogen, or a combination of two or more of said possible substituents, wherein when Ar is a benzene nucleus having only one hydroxyl and only one R substituent, the R substituent is in the ortho or para position relative to the hydroxyl substituent.

The term "phenol" is used in this specification, in accordance with general practice in the art, to mean hydroxyaromatic compounds having at least one hydroxyl group attached directly to the carbon of the aromatic ring.

The 4,63053 amonophenols used in manual stroke engine oils in accordance with the invention do not fall within the scope of this invention but within the scope of our patent application No. 76 2916.

Two-stroke engine oil compositions contain a higher proportion of oil with a lubricating viscosity. This viscosity is typically from about 2.0 to about 150 cst at 98.9 ° C, especially from about 5.0 to about 130 cst at 98.9 ° C.

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

Natural Oils are animal and vegetable oils (eg castor oil, lard oil) as well as mineral lubricating oils, weft liquid petroleum oils and solvent-treated or acid-treated paraffinic, naphthenic or mixed-paraffinic-naphthenic mineral lubricating oils. Useful base oils also include oils having a lubricating viscosity derived from coal or shale.

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 (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di- (2-ethylhexyl) benzenes, etc.); polyphenyls (e.g. biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives, analogs and homologues, and the like.

Oils prepared by polymerizing olefins having less than 5 carbon atoms, such as ethylene, propylene, butylenes, isobutene, pentene, and mixtures thereof, are typical synthetic polymeric oils. Methods for preparing such polymer oils are well known to those skilled in the art, cf. U.S. Patents 2,278,445, 2,301,052, 2,318,719, 2,329,714, 2,345,574 and 2,422,443.

Another class of known synthetic lubricating oils are alkyleneoxy homopolymers and interpolymers and their derivatives in which the terminal hydroxyl groups have been modified by esterification, etherification, etc., etc. having an average molecular weight of 1000, polyethylene glycol diphenyl ether having a molecular weight of 500 to 1000, polypropylene diethyl ether having a molecular weight of 1000 to 1500, etc.) or mono- and polycarboxylic esters thereof, for example acetic acid esters, mixed C8-C8 fatty acid esters or the C13 oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils are dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acids, alkenylsuccinic acids, maleic acid, azealic acid, malic acid, malic acid, sebacic acid, fumaric acid, fatty acid, adipic acid, adipic acid, adipic acid, with alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Examples of such esters are dibutyl adipate, di- (2-ethylhexyl) sebacate, di-n-hexyl fumarate, di'-octyl sebacate, diisooctyl azelate, diisodecyl azelate, di-octyl phthalate, di-Decyl phthalate, di-eicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, complex ester obtained by reacting 1 mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid,

Esters useful as synthetic oils also include those prepared from C 8 -C 20 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylololpropane, pentaerythritol, dipentaerythritol, tri-pentaers.

Silicone-based oils, such as polyalkyl, polyaryl, polyalkoxy or polyaryloxy siloxane oils, and silicate oils form another useful class of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra * (2-ethylhexyl) silicate) silicate. silicate, tetra- (p-tert-butylphenyl) silicate, hexyl- (4-methyl-2-pentoxy) disiloxane, poly (methyl) siloxanes, poly (methylphenyl) siloxanes, etc. Other synthetic lubricants include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid, etc.), polymeric tetrahydrofurans, and the like.

Unrefined, refined, and refined oils, either natural or synthetic, of the type described above (as well as mixtures of two or more of these) may be used in the lubricant compositions. Unrefined oils are obtained directly from a natural or synthetic source 63053 6 without further purification. For example, the unrefined oil may be a shale oil obtained directly from distillation processes, a petroleum oil obtained directly from a pre-distillation, or an ester oil obtained directly from an esterification process and used without further processing. Refined oils correspond to unrefined oils except that they have been further processed in one or more refining steps to improve one or more properties. Such purification procedures are known to those skilled in the art and include, for example, solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. The refined oils are obtained according to the methods used to prepare refined oils using refined oils that have already been used. Such refined oils are also known as regenerated oils and are often further treated to remove used additives and oil decomposition products.

Aromatic group Ar may be a simple aromatic core such as a benzene nucleus, a pyridine nucleus, a thiophene nucleus, a 1,2,3,4-tetrahydronaphthalene nucleus, etc., or a polynuclear aromatic group.

These polynuclear groups may be of the fused type, i.e., those in which at least two aromatic nuclei are fused from two points to the other nucleus, such as naphthalene, anthracene, azonaphthalenes, etc. These polynuclear aromatic groups may also be of the fused type, where at least two mono- or polynuclear) by bridging bonds. Such bridging bonds may be simple carbon-carbon bonds, ether bonds, keto bonds, sulfide bonds, polysulfide bonds having 2 to 6 sulfur atoms, sulfinyl bonds, sulfonyl bonds, methylene bonds, alkylene bonds, di- (lower alkyl) methylene bonds, lower alkylene-alkylene-alkylene-ethylene niketos bonds, lower alkylene sulfur bonds, lower alkylene polysulfide bonds having 2 to 6 carbon atoms, amino bonds, polyamino bonds, and combinations of such divalent bridging bonds. In some cases, more than one bridging bond between aromatic rings may be present in the Ar group. For example, a fluorine nucleus may have two benzene nuclei bonded by both a methylene bond and a covalent bond. Such a group can be considered to contain three nuclei, but only two of them are aromatic. Normally, Ar contains only carbon atoms in the aromatic nucleus per se.

The number of aromatic rings in group Ar, whether 7,63053 fused, bonded or combined in both ways, can affect the numerical values a, b and c in formula I. When Ar contains, for example, a simple aromatic core, a, b and c are each independently 1- 3. When Ar contains two aromatic nuclei, a, b and c may each be an integer from 1 to 6, that is, from 1 to a number 3 times the number of aromatic nuclei present (e.g. 2 nuclei in naphthalene). When the group Ar has three cores, a, b and c can be an integer from 1 to 9.

Thus, when Ar is, for example, a biphenyl group, a, b and c may independently be an integer from 1 to 6. The values of a, b and c are, of course, limited by the fact that their sum cannot be greater than the sum of the unsaturated valencies of the group Ar.

The monocyclic aromatic ring which may form a group Ar can be represented by the general formula ar (Q) m where ar represents a monocyclic aromatic ring (e.g. benzene) having 4 to 10 carbon atoms, each group Q independently representing a lower alkyl group, a lower alkoxyl group , a nitro group or a halogen atom, and m is 0-3. As used in this specification and claims, "lower" means groups having up to 7 carbon atoms, such as lower alkyl and lower alkoxyl groups. Halogen atoms include fluorine, chlorine, bromine and iodine atoms; halogen atoms are generally fluorine and chlorine atoms.

Examples of such monocyclic Ar groups are the following: H-fV f \ as

H H H h H

B

yV f'V t'V

Me — OPr HH

63053 8 H — r ^ N— Nit h-L ^^ Lh H ~ I ^ CH, "CH,

Vn-W *. ΊίΤ <I I Λ A ch2 "ch2 H —H2 H 'H2, etc., where

Me is methyl, Et is ethyl, Pr is n-propyl and Nit is nitro.

When Ar is a polynuclear aromatic fused ring group, it may have the general formula ar ^ arf m · (Q> nm · where ar, Q and m have the same meaning as above, m 'are 1-4 and means a fusing bond pair fusing two rings such that two carbon atoms belong to each of adjacent rings.Examples of different fused ring aromatic groups Ar are:

B

I rH I

H - H H H

H H

I Me9 I

Μβ_ ^ ΑγΛ ^ _ Me Nit

H H H

H H

H H H

H if ^? !

I 1 Λ- H / -k. / K. / k— H

Η_γίίίΧ | ^^ Χρ MeO - ^

H YY

H H H

63053 9 etc.

When the aromatic group Ar is a polynuclear aromatic group, it can be represented by the general formula ar — f— Lng-ar -4—- (Q) w mw where w is an integer from 1 to about 20, ar has the same meaning as above, provided that it has at least 3 unsaturated (i.e., free) valence in all ar groups together, Q and m have the same meaning as above, and each Lng is a bridging bond that can be independently

single carbon-carbon bond, ether bond (e.g., -O-), keto bond O

II

(e.g. -C-), sulfide bond (e.g. -S-), polysulfide bond containing 2-6 sulfur bonds (e.g. ~ S2-6-6'sulfinyl bond (e.g. -S (O) -), sulfonyl bond) (e.g. -S (O) 2 -) / lower alkylene bond (e.g. -C 1-4, -CH-CH-, etc.), di- (lower alkyl) methylene bond (e.g.

R 0 -CR 2 -), lower alkylene ether bond (e.g. -Cl 2 O-, -Cl 2 O-CH 3 "-ch 2 -ch 2 -, -ch 2 ch 2 o 2 CH 2 -, -ch 2 choch 2ch-, -ch 2 chochch 2", etc.), R 0 R ° OR ° R °

Il II

a lower alkylene ketoside bond (e.g. -CH 2 C-, -CH 2 CCH 3 -), a lower alkylene sulfide bond (e.g. where one or more of the -O- in the lower alkylene ether bond is replaced by an -S atom), a lower alkylene polysulfide bond (e.g. where one or more -O- substituted with -S2-g), an amino bond (e.g., -N-, -N-, -CH9N-, -CHINCH, -, -alk-N-, where alk HR ° is lower alkylene, etc.), a polyamino bond ( e.g., -N (alkN) .n, where 1 to 1 n unsaturated free N-valences contain H atoms or R groups) and combinations of such bridging bonds (each R 0 is a lower alkyl group).

Examples in which Ar is a bridged polynuclear aromatic group include the following: 10 63053

H H H H

_ι Fji T J Γ1

H H H H

H H

- [f ^ S-CH2 i2 H-r ^ Sr r ^ v

H 1 I

~ H

-p ^ N_ / s —V

HxHe ^^ Y ^ H / Γιο ** Me ** 1 j '1 μθΛν ^ “

J H H J

iTtn

MvV J, - „.

63053 11

Lime these Ar groups are generally unsubstituted except for the R, -OH and -NHj groups (and the bridging group).

For reasons of cost, availability, and utility, the group Ar is normally a benzene nucleus, a lower alkylene bridged benzene nucleus, or a naphthalene nucleus. Thus, a typical Ar group is a benzene or naphthalene nucleus having 3-5 unsaturated valencies, so that one or two of these valencies may be saturated with a hydroxyl group, the remaining unsaturated valencies being, if possible, in either the ortho or para position relative to the hydroxyl group. Ar is preferably a benzene nucleus having 3-4 unsaturated valencies, one of which may be saturated with a hydroxyl group and the remaining two or three are either ortho or para to the hydroxyl group.

The aminophenols used in two-stroke engine oils according to the invention, when directly bound to the aromatic group Ar, contain a predominantly saturated monovalent hydrocarbon-based group R having 30 to 400 aliphatic carbon atoms. More than one such group may be present, but generally no more than two or three such groups are present per aromatic nucleus in the aromatic group Ar. The number "a" denotes the total number of R groups present in formula I. In particular, the hydrocarbon-based group has at least 50 aliphatic carbon atoms and in particular up to about 300 aliphatic carbon atoms.

Hydrocarbon-based groups R are generally prepared from homo- or mono- and di-olefins having 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, isobutene, butadiene, isoprene, 1-hexene, 1-octene, etc. interpolymers (e.g. copolymers, terpolymers). These olefins are generally 1-mono-olefins. R groups may also be derived from halogenated (e.g., chlorinated or brominated) analogs of such homo- or interpolymers. However, R groups may be derived from other sources, such as monomeric high molecular weight alkenes (e.g.

1-tetraconates) and its chlorinated and hydrochlorinated analogues, aliphatic petroleum fractions, in particular paraffin waxes and its cracked and chlorinated and hydrochlorinated analogues, white oils, polyethylene-synthetic alkenes, such as those prepared according to Ziegler-N. fats) and other sources known to those skilled in the art. The unsaturated moiety in R-63053 12 groups can be reduced or eliminated by hydrogenation according to methods known in the art prior to the nitration step described below.

Here, the phrase "hydrocarbon-based" means a group in which a carbon atom is directly attached to the remainder of the molecule and has a predominantly hydrocarbon nature. Thus, hydrocarbon-based groups may always contain one radical having no hydrocarbon character for every 10 carbon atoms, provided that this radical does not substantially alter the predominant hydrocarbon character of the group. It will be apparent to those skilled in the art that such radicals include, for example, hydroxyl, halogen (especially chlorine and fluorine), alkoxyl, alkyl mercapto, alkyl sulfoxy, etc. However, these hydrocarbon-based groups R are generally pure hydrocarbyls and do not contain any non-hydrocarbyl radicals.

The hydrocarbon-based groups R are predominantly saturated, i.e., they contain at most one unsaturated carbon-carbon bond for every ten simple carbon-carbon bonds. In general, they contain at most one non-aromatic unsaturated carbon-carbon bond for every 50 carbon-carbon bonds present.

The hydrocarbon-based groups of aminophenols used in two-stroke engine oils according to the invention are also predominantly aliphatic, i.e. they contain at most one non-aliphatic group (cycloalkyl, cycloalkenyl or aromatic) having up to 6 carbon atoms for every 10 carbon atoms in group R. These R- however, the groups generally contain no more than one such non-aliphatic group for every 50 carbon atoms, and in many cases do not contain any such non-aliphatic groups; i.e., typical R groups are purely aliphatic. These purely aliphatic groups R are preferably alkyl or alkenyl groups.

Examples of predominantly saturated hydrocarbon-based R groups are: tetracontanyl group, henpentacontanyl group, a mixture of poly (ethylene / propylene) groups having from about 35 to about 70 carbon atoms, oxidatively or mechanically decomposed poly (from about 35 to about 70 carbon atoms) ethylene / propylene), 13 63053 a mixture of poly (propylene / 1-hexene) groups having about 80 to about 150 carbon atoms, a mixture of poly (isobutyl) groups, especially poly (isobutylene) groups having an average of 50 to 75 carbon atoms mixture.

A preferred source of group R are poly (isobutenes) obtained by polymerizing a C 1-6 refining stream having a butene content of 35-75% by weight and an isobutene content of 30-60% by weight in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes contain mainly (more than 80% of the total number of repeating units) repeating isobutylene units of the formula CH ·, I 3

- CH ~ - C

2 I

CH3

The incorporation of the hydrocarbon-based group R into the aromatic group Ar of the aminophenols used in the two-stroke engine oils of the invention can be accomplished by a number of methods well known to those skilled in the art. One particularly suitable technique is the Friedel-Crafts reaction in which an olefin (e.g., an olefin-bonded polymer) or a halogenated or hydrohalogenated analog thereof is reacted with a phenol. This reaction takes place in the presence of a Lewis acid catalyst (e.g. boron trifluoride and its ethers, phenols, complexes with hydrogen fluoride, etc., aluminum chloride, aluminum bromide, zinc dichloride, etc.). Methods and conditions for carrying out such reactions are well known to those skilled in the art, cf. for example, the article "Alkylation of Phenols", Kirk-Othmer's "Encyclopedia of Chemical Technology", second edition, Vol. 1, pages 894-895, Interscience Publishers, John Wiley and Company, N.Y., 1963. Other equally well-known suitable and simple methods for attaching a hydrocarbon-based group R to an aromatic group Ar are well known to those skilled in the art.

As shown in formula I, the aminophenols used in the two-stroke engine oils of this invention contain at least one of the following substituents: a hydroxyl group, an R group as defined above and a primary amino group, -N 2 · Each of the above groups is attached to a carbon atom having an ar group of 63053 part of the kernel. However, they need not be attached to the same aromatic ring if there is more than one aromatic ring in the Ar group.

According to a preferred embodiment, the aminophenols used in the two-stroke engine oils according to the invention contain one of the abovementioned substituents but only one aromatic ring, preferably a benzene ring. This preferred class of aminophenols can be illustrated by the formula

OH

R 1 - (R 2, 2) wherein the R 'group is a hydrocarbon-based group having from about 30 to about 400 aliphatic carbon atoms ortho or para to the hydroxyl group, R' '' is lower alkyl, lower alkoxyl -, a nitro group or a halogen tower, and z is 0 or 1. In general, z is 0 and R 'is a predominantly saturated, purely aliphatic group. It is often an alkyl or alkenyl group in the para position relative to the OH substituent.

According to an even more preferred embodiment of the invention, the amino phenols have the formula

OH

(Rt 1 ') - I-R "wherein R" is derived from homopolymerized or copolymerized C2-1010 olefins and contains an average of about 30 to about 300 aliphatic carbon atoms and R "1 and z have the same meaning as above.

R "is generally derived from ethylene, propylene, butylene, or mixtures thereof. Typically, it is derived from polymerized iso-butene. The group R" generally contains at least about 50 aliphatic carbon atoms and z is 0.

63053 15

The amino-phenols used in two-stroke engine oils according to the invention can be prepared by a number of different synthetic methods. These methods may vary depending on the type of reaction used and the relative order. 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, for example to prepare a polynitro intermediate. The polynitro intermediate, in turn, can be reduced to the diamine, which can then be diazotized and reacted with water to convert the amino groups to a hydroxyl group and produce the desired aminophenol. Alternatively, one nitro group of the polynitro intermediate can be converted to a hydroxyl group by melting with a base to produce a hydroxy-nitroalkylated aromatic compound, which can then be reduced to produce the desired aminophenol.

Another useful method for preparing aminophenols involves alkylating a phenol with an olefinic alkylating agent to an alkylated phenol. This alkylated phenol can then be nitrated to mono- or polynitrophenol, which can be converted to the desired aminophenols by reducing at least a portion of the nitro groups of the intermediate to amino groups.

Methods for alkylating phenols are well known to those skilled in the art, cf. for example, the aforementioned Kirk-Othmer "Encyclopedia of Chemical Technology". Methods for nitrating phenols are also known, cf. for example, Kirk-Othmer, "Encyclopedia of Chemical Technology," Second Edition, Vol. 13, an article entitled "Nitrophenols", p. 888 et seq., And "Aromatic Substitution; Nitration and Halogenation", P.B. De La Mare and J.H. Ridd, N.Y., Academic Press, 1959; "Nitration and Aromatic Reactivity", J.G. Hogget, London, Cambridge University Press, 1961; and "The Chemistry of the Nitro and Nitroso Groups," Henry Feuer, Editor, Interscience Publishers, N.Y., 1969.

Aromatic hydroxy compounds can be nitrated with nitric acid, mixtures of nitric acid with acids such as sulfuric acid or boron trifluoride, nitrogen tetroxide, nitronium tetrafluoroborates and acyl nitrates. A suitable nitration reagent is generally a nitric acid concentration of, for example, about 60-90%. The reaction may be facilitated by the use of predominantly inert liquid diluents and solvents, such as acetic or butyric acid, which enhance the contact between the reagents.

63053 16

Conditions and concentrations for nitration of hydroxyaromatic compounds are also well known in the art. For example, the reaction can be carried out at a temperature of about -15 to about 150 ° C. In general, the nitration is suitably performed at about 25 to about 75 ° C.

Depending on the particular nitrating agent used, about 0.5 to 4 moles of nitrating agent are usually used per mole of aromatic core in the nitroxy-aromatic intermediate to be nitrated. If the Ar group has more than one aromatic nucleus, the amount of nitrating agent can be increased corresponding to the number of such nuclei present. For example, one mole of a naphthalene-based aromatic intermediate in this invention corresponds to two "monocyclic" aromatic nuclei, so that in this case about 1 to 4 moles of nitrating agent are generally used. When nitric acid is used as the nitrating agent, it is generally used in an amount of about 1.0 to 3.0 moles, per mole of aromatic nucleus. It is always possible to use an excess of about 5 molar nitrating agent (per "monocyclic" aromatic core) when it is desired to promote or carry out the reaction rapidly.

The nitration of the hydroxy-aromatic intermediate generally takes 0.25-24 hours depending on parameters such as temperature, the amount, type and quality of the intermediate and the nitrating agent, although it may be appropriate to react the nitration mixture for longer periods, such as 96 hours.

The reduction of aromatic nitro compounds to the corresponding amines is also known, cf. for example, the article "Amination by Reduction", Kirk-Othmer's "Encyclopedia of Chemical Technology", second edition, Vol. 2, pp. 76-99. Such reductions can generally be carried out, for example, with hydrogen, carbon monoxide or hydrazine (or mixtures thereof) in the presence 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) can also be used in these catalyzed reductions.

The reduction can also be performed using reducing metals in the presence of acids such as hydrochloric acid. Typical reducing metals include zinc, iron and tin; salts of these metals can also be used.

Nitro groups can also be reduced in the Zinin reaction, cf. "Organic Reactions," Vol. 20, John Wiley & Sons, N.Y., 1973, pp. 455 et seq. The zinin reaction generally involves reduction of the nitro group with divalent negative sulfur compounds such as alkali metal 63053 17 sulfides, polysulfides and hydrosulfides.

Nitro groups can be reduced electrolytically cf. for example, the aforementioned article "Amination by Reduction."

Aminophenols are typically obtained by reducing nitrophenols with hydrogen in the presence of a metal catalyst such as one of the aforementioned catalysts. This reduction is generally performed at a temperature of about 15-250 ° C, typically about 50-150 ° C at a pressure of about 0-140 bar (0-2000 psig), typically about 4.5-18.3 bar (50-50 psig). 250 psig). The reduction reaction time is generally about 0.5 to 50 hours. The reactions can be promoted by using mainly inert liquid diluents and solvents such as ethanol, cyclohexane, etc. The aminophenol product is obtained by well-known methods such as distillation, filtration, extraction, etc.

The reduction is continued until at least about 50%, generally about 80% of the total number of nitro groups in the nitro medium mixture has been converted to amino groups. The above typical process for the preparation of aminophenols can be summarized as follows: (I) nitrating with at least one nitrating agent at least one compound of the formula <° H> c (R> 5-Ar · wherein R is a predominantly saturated hydrocarbon-based group of 30 to 400 aliphatic a and c are independently an integer from 1 to 3 times the number of aromatic rings in the group Ar, provided that the sum of the numbers a, b and c does not exceed the number of unsaturated valences in the group Ar *, and Ar 'is an aromatic group having 0 -3 possible substituents such as lower alkyl, lower alkoxyl, nitro and halogen or a combination of two or more such possible substituents, provided that (a) Ar 'contains at least one hydrogen atom directly attached to a carbon atom which forms part of the aromatic nucleus, and ( b) when Ar 'is benzene with only one hydroxyl and only one R substituent, the R substituent tti is in the ortho or para position relative to said hydroxyl substituent to form a first reaction mixture containing a nitro intermediate, and (II) at least about 50% of all nitro groups in said first reaction mixture are reduced to amino groups.

63053 18 This generally means reducing at least about 50% of the nitro groups to amino groups in a compound or mixture of compounds of the formula (f> c (R> --Ar- (NO 2) b where R is a predominantly saturated hydrocarbon-based substituent having - 400 aliphatic carbon atoms, a, b and c are each independently an integer from 1 to 3 times the number of aromatic nuclei present in the Ar group, provided that the sum of a, b and c does not exceed the number of unsaturated valencies in the Ar group, and Ar is an aromatic group having 0 to 3 possible substituents such as lower alkyl, lower alkoxyl, nitro, halogen or a combination of two or more such possible substituents, provided that when Ar is a benzene nucleus having only one hydroxyl and only one R substituent, the R substituent is in the ortho or para position relative to said hydroxyl substituent.

The following examples illustrate exemplary compositions of typical aminophenols that may be used in the two-stroke engine oils of this invention. As will be appreciated by those skilled in the art, aminophenols prepared by other methods may also be used. All parts and percentages are by weight, and all temperatures are in degrees Celsius (° C) in these examples and elsewhere in the specification, unless otherwise indicated.

Example IA;

An alkylated phenol is prepared by reacting the phenol with a polyisobutylene having an average molecular weight of about 1000 (vapor phase osmometry) in the presence of a boron trifluoride-phenol complex catalyst. The product thus formed is first distilled to 230 ° / 760 torr (vapor temperature) and then to a vapor temperature of 205 ° / 50 torr to give purified alkylated phenol.

To a mixture of 265 parts of purified alkylphenol, 176 parts of mixed oil and 42 parts of solvent gasoline having a boiling point of about 20 ° is slowly added to 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 about 30-45 °, distilled to 120 ° / 20 torr and filtered to give an oily solution of the desired nitrophenol intermediate.

63053 19

Example IB;

A mixture of 1500 parts of the product solution of Example IA, 642 parts of 2-propanol and 7.5 parts of nickel-diatomaceous earth catalyst is charged to the autoclave under a nitrogen atmosphere. Nitrogen is blown into it and evacuated three times, after which the autoclave is pressurized to 100 psig with hydrogen and stirring is started. The reaction mixture is maintained at 96 ° for a total of 14.5 hours while being fed a total of 1.66 moles of hydrogen. Nitrogen is blown in and evacuated three times, after which the reaction mixture is filtered and the filtrate is distilled to 120 ° / 18 torr. Filtration gives the desired product as a solution containing 0.54% nitrogen.

Example 2A;

To a mixture of 400 parts of polyisobutylene-substituted phenol (in which the polyisobutylene substituent contains about 100 carbon atoms), 125 parts of textile spirit and 266 parts of diluent mineral oil at 28 ° is slowly added 22.83 parts of nitric acid (70%) in 50 parts of water 0.33 within an hour. The mixture is stirred at 28-34 ° for 2 hours and distilled at 158 ° / 30 torr, filtered to give an oily solution of the desired intermediate (40%) with a nitrogen content of 0.88%. Example 2B:

A mixture of 93 parts of the product solution of Example 2A and 93 parts of a mixture of toluene and 2-propanol (50/50 by weight) is charged to a suitably sized hydrogenation vessel. The mixture is degassed and nitrogen is blown into it; 0.31 part of a commercial platinum oxide catalyst (86.4% PtCl 2) is added. The pressure in the reaction vessel is raised to about 4.9 bar (57 psig) and kept at 50-60 ° for 21 hours. A total of 0.6 moles of hydrogen is fed to the reaction vessel. The reaction mixture is then filtered and the filtrate is distilled to give the desired product as a solution containing 0.44% nitrogen.

Example 3A:

A mixture of 2160 parts of the polyisobutylene-substituted phenol of Example 2A and 1440 parts of mineral oil as diluent is heated to 60 °. 25 parts of paraformaldehyde are then added to the mixture, followed by 15 parts of aqueous hydrochloric acid. The mixture is heated at 115 ° for 1 hour. After 16 hours at room temperature, the reaction mixture is heated at 160 ° for one hour while removing 20 parts of distillate. The reaction mixture is distilled at 160 ° / 15 torr to give an oil solution of the desired methylene-linked polyisobutylene-substituted phenol.

Example 3B: To 2406 parts of the oil solution described in Example 3A and 600 parts of 63053 textile spirit, 90 parts of nitric acid (70%) are added over 1.5 hours. The reaction mixture is stirred for 1.5 hours, kept at room temperature for 63 hours and then heated at 90 ° for 8 hours. Distill to 160 ° / 18 torr to give 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 charged to the autoclave. Flush with nitrogen, then add 4 parts of nickel-diatomaceous earth catalyst. The nitrogen purges are repeated three times and the autoclave pressure is raised to 60 psig with hydrogen at 25 °. The reaction temperature is slowly raised to 96 ° and the pressure is maintained at about 7.9 bar (100 psig) for 5.5 hours. The autoclave is then opened and a further 4 parts by weight of nickel-diatomaceous earth catalyst are added. The autoclave pressure is raised again to about 7.9 bar of hydrogen and maintained at 96 ° / 7.9 bar for 6 hours. The autoclave is cooled and reopened; an additional 0.8 parts of platinum oxide catalyst is added. The autoclave pressure is then raised again to about 7.2 bar (90 psig) with hydrogen and maintained at this pressure for a further 8 hours. The reaction mixture is filtered and distilled to 150 ° / 18 torr to give an oil solution of the product with a nitrogen content of 0.41%.

Example 4A:

A mixture of 1962 parts of the polyisobutylene-substituted phenol of Example IA, 49.5 parts of paraformaldehyde, 15 parts of aqueous hydrochloric acid and 1372 parts of mineral oil diluent is heated at 115 ° for 7 hours. The reaction temperature is then raised to 160-165 ° and maintained at this temperature for a further 7 hours. An additional 400 parts of textile spirit is then added to the mixture and cooled to 30 °. 136.95 parts of nitric acid (70%) in 140 parts of water are then slowly added. The reaction mixture is stirred for 1.5 hours at 30-35 ° and then distilled to 170 ° / 28 torr to give an oil solution of the intermediate which is clarified by filtration. Example 4B: 96 parts of the oil solution described in Example 4A and 96 parts of a toluene / 2-propanol mixture (50/50 by weight) are charged to a suitably sized hydrogenation vessel. Flush with nitrogen, then add 0.32 parts of platinum oxide catalyst. The reaction vessel is flushed again, after which its pressure is raised to about 4.9 bar (57 psig) at 25 ° with hydrogen. The hydrogen pressure is maintained between about 4.9-4.5 bar (57-50 psig) for 60 hours while heating the reaction mixture at 50-60 °. The resulting reaction mixture 63053 21 is filtered and distilled to give an oil solution of the product with a nitrogen content of 0.353%.

Example 5A:

To a mixture of 654 parts of the polyisobutylene-substituted phenol of Example IA and 654 parts of isobutyric acid at 27-31 ° is added 90 parts of 16 molar nitric acid over 0.5 hours. The reaction mixture is kept at 50 ° for 3 hours and then stored at room temperature for 63 hours. Distill to 160 ° / 26 torr and filter to give the desired nitro intermediate with a nitrogen content of 1.8%.

Example 5B:

The nitro product of Example 5A is hydrogenated using a nickel-diatomaceous earth catalyst mainly according to the method described in Example IB.

Example 6At

A mixture of 4578 parts of the polyisobutylene-substituted phenol of Example IA, 3052 parts of mineral oil diluent and 725 parts of textile spirit is heated to 60 ° until homogeneous. After cooling to 30 °, 320 parts of 16 molar nitric acid in 600 parts of water are added to the mixture. Cool to keep the temperature below 40 °. The reaction mixture is stirred for a further 2 hours, after which 3710 parts of the mixture are transferred to another reaction vessel. These 3710 parts are treated with a further 128 parts of 16 molar nitric acid in 130 parts of water at 25-30 °. The reaction mixture is stirred for 1.5 hours and then distilled to 220 ° / 30 torr. Filtration gives an oil solution of the intermediate.

Example 6B;

The oil solution of the product obtained in Example 6A is hydrogenated using a platinum oxide catalyst mainly as described in Example IB.

Example 7;

A mixture of 543 parts of dinitro-C25-alkylated phenol (prepared mainly as described in Example 6A), 543 parts of isopropanol and 200 parts of toluene is treated at 19 ° with a total of 42 parts of gaseous ammonia over 0.75 hours. The reaction mixture is then treated with 147 parts of gaseous hydrogen sulfide. Both ammonia and sulfur carbon treatment are performed by feeding a gas below the surface of the stirred mixture. The ammonia treatment is repeated using 82 parts of gaseous ammonia and then finally treated with 102 parts of carbon disulphide. Distillation of the reaction mixture at 40 ° / 63053 22 60 torr gives a residue which is combined with 161 parts of dilution oil and distilled again to 70 ° / 18 torr. An additional 161 parts of oil diluent and 35 parts of filter aid are added; filtration of this mixture gives a viscous filtrate which is a 40% solution of diaminophenol.

The nitrations of Examples 8-14 are filtered primarily as described in Example IA using the hydroxy aromatic compounds and amounts of nitric acid listed in Table A. In these examples, the reduction of nitro intermediates is performed using the technique mentioned in the examples in Table A.

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The two-stroke engine lubricating oil compositions of the invention contain about 98-55% oil or an oil mixture having a lubricating viscosity. The compositions typically contain about 90-70% oil, preferably the oils are mineral oils and mineral oil-synthetic polymer and / or ester-oil blends. Typical useful synthetic oils include polybutenes having molecular weights of about 250-1000 (as measured by vapor phase osmometry) and fatty acid ester oils of polyols such as pentaerythritol and trimethylolpropane.

These oil preferences contain from about 2% to about 30%, preferably from about 5% to about 20%, of at least one of the aforementioned aminophenols. Other additives may also be present, such as additional detergents and dispersants, which may be of the ash-forming or non-ash type, antioxidants, coupling agents, pour point depressants, high pressure agents, color stabilizers and antifoams.

Non-ash-forming and ash-forming metal-type detergent dispersants are used to prevent sticking to the piston ring and to promote the overall cleanliness of the engine. High-performance two-stroke lubricants must use suitable, ash-free dispersants due to the tendency of such an engine to induce premature ignition. In other compositions, calcium, barium or magnesium sulfonates may be used, either alone, in admixture with each other or in combination with ashless dispersants. They may include antioxidants to improve the thermal stability of the lubricant.

Polymeric viscosity index improvers have been and are being used as a substitute for bright-stock oil to improve lubricant film strength and lubrication properties as well as engine cleanliness. The dye can be used for identification purposes and to indicate whether or not the two-stroke fuel mixture contains a lubricant.

Coupling agents may be included in some products to provide better component solubility and better water / lubricant mixture water tolerance.

Anti-wear and lubrication enhancers, especially sulfurized whale fat substitutes and other fatty acid and vegetable oils such as castor oil, are used in special compositions such as for racing purposes and in the case of very high fuel / lubricant ratios. In some cases, flushing agents or combustion chamber deposit modifiers are used to improve the life of the spark plugs and to remove carbon deposits. Halogenated compounds and / or phosphorus-containing substances can be used for this purpose.

All types of rust and corrosion inhibitors can and will be incorporated into two-stroke engine oil compositions. For aesthetic reasons, odorants or deodorants are sometimes used.

Lubricants such as synthetic polymers (e.g., polyisobutylene having an average molecular weight of about 750 to about 15,000 as measured by vapor phase osmometry or gel permeation chromatography), polyol ethers (e.g., poly (oxyethylene) ethylene-ethylene) may also be used in the compositions of the invention. ) ethers) and ester oils (e.g. ester oils as described above). Natural oil fractions such as "bright stock" oils (compared to viscous products formed from crude oil during normal lubricating oil production) can also be used for this purpose. They are generally used in two-stroke engine oils from about 3% to about 20% of the total oil composition.

As mentioned above, the oils may also contain additional detergent dispersants. Typical examples are amides, amine salts and / or amidine products formed by reacting fatty acids having 5 to 22 carbon atoms (e.g., isostearic acid and mixtures of isostearic and stearic acid) with 2 to about 10 amino groups and an ethylene polyamine of 2 to about 20 carbon atoms, such as ethylene polyamine, , triethylenetetramine, tetraethylenepentamine, etc., and commercially available mixtures of such alkylene polyamines. Such additional detergent dispersants are described in U.S. Patent 3,169,980.

diluents, such as gasoline-type substances boiling in the range of about 38-90 ° (e.g., Stoddard solvent), may also be included in the oil compositions, typically 5-25%.

A typical two-stroke engine oil lubricant composition contains 2-10% of any of the aminophenols described above in Example IB, and a base oil consisting of about 70-80 parts by volume of 650 neutral oils, 8-12 parts by volume of "bright stock" and 10-20 parts by volume of Stoddard. -liuotinta.

In some two-stroke engines, lubricating oil may be injected into the combustion chamber together with the fuel or into the fuel immediately before the fuel enters the combustion chamber. The two-stroke engine lubricants of this invention are intended to be used in such two-stroke engines.

As will be appreciated by those skilled in the art, lubricating oil for two-stroke engines can be added directly to the fuel to form a mixture of oil and fuel, which is then fed to the engine cylinder. These lubricant and fuel oil blends are within the scope of this invention. Such lubricant-fuel blends generally contain 1 part oil to about 15-250 parts fuel, generally they contain 1 part oil to about 50-100 parts fuel.

Typical two-stroke engine oils of this invention include:

Component Weight percent __Example A Example B_

Base oil ^ 58.6 67.0 bright stock ^ 9.4 9.4

Stoddard solvent 17.9 17.8 aminophenol additive3 ^ 14.1 4) aminophenol additive - 5.8 1) Solvent-refined neutral oil with a viscosity of 650 SUS at 98.8 ° 2) Viscosity 150 SUS 98, At 8 ° 3) Mineral oil solution containing 60% of the aminophenol described in Example 3C 4) Mineral oil solution containing 60% of the aminophenol described in Example IB.

Fuels used in two-stroke engines are also known to those skilled in the art and generally contain primarily normal liquid fuel, such as hydrocarbonaceous petroleum distillate (e.g., gasoline according to ASTM standard D-439-73). Such fuels may also contain non-hydrocarbonaceous substances such as alcohols, ethers, organo-nitro compounds and the like (e.g. methanol, ethanol, diethyl ether, methylethyl ether, nitromethane) and are also within the scope of this invention, as are liquid fuels obtained from vegetable plants. or from mineral sources such as corn, alpha-alpha, shale and coal. Examples of such fuel blends are blends of gasoline and ethanol, diesel and ether, gasoline and nitromethane, and the like. A particularly preferred fuel is gasoline, i.e., a mixture of hydrocarbons having an ASTM boiling point of 60 ° to 63053 27 at a 10% distillation point up to about 205 ° at a 90% distillation point.

Two-stroke rotor fuels also contain other additives known to those skilled in the art. These may be anti-knock agents such as tetraalkyl-lead compounds, lead scavengers such as haloalkanes (e.g. ethylene dichloride and ethylene dibromide), anti-fouling agents or modifiers such as triaryl phosphates, colorants, cetane antioxidants such as 2,6-di-tert-butyl-4-methylphenol, anti-corrosive agents such as alkylated succinic anhydrides, bacteriostatic agents, resin inhibitors, metal deactivators, de-emulsifiers, lubricating agents , antifreeze and the like.

Claims (31)

63053 28 Use of a lubricant composition for lubricating a two-stroke internal combustion engine, wherein the lubricant composition comprises 55-98, preferably 70-90% by weight of oil having a lubricating viscosity and 2-30, preferably 5-20% by weight of at least one amino additive of formula (a) »C (k); - Ar- <NH2> b wherein R is a predominantly saturated hydrocarbon-based substituent having 30 to 400 aliphatic carbon atoms} a, b and c are each and independently an integer from 1 to 3 times the number of the number of aromatic nuclei, the sum of the numbers a, b and c not exceeding the number of unsaturated valencies of the group Ar; and Ar is an aromatic group having 0 to 3 possible substituents selected from lower alkyl, lower alkoxyl, nitro, halogen, or a combination of two or more of said possible substituents; wherein when Ar is a benzene nucleus having only one hydroxyl and only one R-bust substituent, the R-substituent is in the ortho or para position relative to the hydroxyl substituent, or (b) prepared by (I) nitration with at least one nitrating agent of at least one compound of the formula <? H) c (R) j -Ar 'wherein R is a predominantly saturated hydrocarbon-based substituent having 30 to 400 aliphatic carbon atoms; a and c are each and independently an integer from 1 to 3 times the number of aromatic nuclei present in the Ar group, provided that the sum of a, b and c does not exceed the number of unsaturated valencies in the Ar 'group; and Ar 'is an aromatic group having 0 to 3 possible substituents selected from lower alkyl, lower alkoxyl, nitro or halogen, or a combination of two or more such possible substituents; wherein (a) Ar 'contains at least one hydrogen atom 63053 29 directly attached to a carbon atom which forms part of the aromatic ring, and (b) when Ar is benzene having only one hydroxyl group and only one R substituent, R the substituent is ortho or para to said hydroxyl group to form a first reaction mixture containing a nitro intermediate, and (II) reducing at least about 50% of the nitro groups in said first reaction mixture to amino groups; or (c) prepared by reducing at least about 50% of the nitro groups to amino groups in a compound or mixture thereof having the formula <° H) c <R>; -Är - <NO2> b wherein R is a predominantly saturated hydrocarbon-based substituent -ti having 30 to 400 aliphatic carbon atoms; a, b and c are each and independently an integer from 1 to 3 times the number of aromatic nuclei present in the Ar group, the sum of the numbers a, b and c not exceeding the number of unsaturated valences in the Ar group; and Ar is an aromatic group having 0 to 3 possible substituents such as lower alkyl, lower alkoxyl, nitro, halogen, or a combination of two or more such possible substituents; wherein when Ar is a benzene nucleus having only one hydroxyl group and only one R substituent, the R substituent is ortho or para to said hydroxyl group, the remainder of the composition being any other additives known per se. Use according to Claim 1, characterized in that R is a purely hydrocarbyl substituent. Use according to Claim 2, characterized in that R is alkyl or alkenyl. Use according to one of Claims 1 to 3, characterized in that R is a substituent made from homopolymerized or interpolymerized Q-olefins. Use according to Claim 4, characterized in that the o "° lefins are C2" - | q-1 olefins or mixtures thereof. 63053 Use according to Claim 5, characterized in that the 1-olefin is ethylene, propylene, butylene or a mixture thereof. Use according to one of Claims 1 to 6, characterized in that Ar contains at least two bridged and / or fused polynuclear aromatic nuclei. Use according to Claim 7, characterized in that Ar is a naphthalene ring. Use according to Claim 7, characterized in that the aromatic ring Ar corresponds to the formula ar -f-Lng-ar - in which ar is a single ring or a fused ring core having 4 to 10 carbon atoms, it having at least 3 unsaturated valencies in all ar in groups, w is an integer from 1 to 20 and each Lng is a bridging bond which may independently be a single carbon-carbon bond, an ether bond, a sulfide bond, a polysulfide bond containing 2-6 sulfur atoms, a sulfinyl bond, a sulfonyl bond, a lower alkylene bond, a di- (lower alkyl ) methylene bond, lower alkylene ether bond, lower alkylene sulfide bond, lower alkylene polysulfide bond, amino bond, and a combination of these bridging bonds, Q is a lower alkyl group, a lower alkoxyl group, a nitro group, or a halogen atom, and m is 0-3. Use according to one of Claims 1 to 6, characterized in that Ar is a benzene nucleus having 0 to 3 alternative substituents and a, b and c are each 1. Use according to one of Claims 1 to 6, characterized in that the formula of the amino-containing additive is OH JL R'-H v (R ,,,) z has an average of about 30 to about 400 aliphatic carbon atoms (63053 in the ortho or para position to the hydroxyl group; R '' 'is lower alkyl, lower alkoxyl, nitro or halogen; and z is 0 or 1. Use according to Claim 11, characterized in that R * contains at least 50 aliphatic carbon atoms. Use according to Claim 11 or 12, characterized in that R 'is a substantially saturated, purely aliphatic group. Use according to one of Claims 11 to 13, characterized in that R 'is in the para position with respect to the OH substituent and z is 0. Use according to one of Claims 11 to 14, characterized in that R 'is an alkyl or alkenyl substituent. Use according to one of Claims 11 to 15, characterized in that R 'is a substituent derived from homopolymerized or copolymerized C 2 -C 10 olefins. Use according to Claim 16, characterized in that the C 2 -C 10 olefins. are C2-, J-1-olefins or mixtures thereof. Use according to Claim 17, characterized in that the 1-olefin is ethylene, propylene, butylene or a mixture thereof. Use according to any one of claims 1 to 6 or 10 to 18, characterized in that the amino-containing additive has the formula OH (R "-f-TR" wherein R "is derived from homopolymerized or copolymerized C2-10Q-1 olefins and contains on average about 30 to about 300 aliphatic carbon atoms, R "" is lower alkyl, lower alkoxyl, nitro or halogen, and z is 0 or 1. Use according to Claim 19, characterized in that the 1-olefin is ethylene, propylene, butylene or a mixture thereof. Use according to Claim 20, characterized in that R "is derived from polymerized isobutene. Use according to any one of claims 19 to 21, characterized in that R "is an alkyl or alkenyl group containing on average at least about 50 aliphatic carbon atoms. Use according to one of Claims 19 to 22, characterized in that z is 0. Use according to one of the preceding claims, characterized in that R contains on average at most about 300 carbon atoms. Use according to one of the preceding claims, characterized in that Ar 'contains at least one hydrogen atom which is directly bonded to the carbon atom of the aromatic ring which is in the α- or γ-position relative to the aromatic carbon atom containing the hydroxyl group. Use according to Claim 25, characterized in that Ar * is a benzene ring. Use according to one of the preceding claims, characterized in that the nitrating agent is nitric acid. Use according to one of the preceding claims, characterized in that the nitro intermediate is reduced with hydrogen in the presence of a metal hydrogenation catalyst. Use according to one of Claims 1 to 6 or 10 to 28, characterized in that the amino-containing additive is prepared (I) by nitration with a nitrating agent of at least one compound of the formula OH Λ (R '' ') -— | -fR' in which R 'is a predominantly saturated hydrocarbon-based substituent having an average of about 30 to about 400 aliphatic carbon atoms 63053 33 and ortho or para to the hydroxyl group; R'1 'is lower alkyl, lower alkoxyl, nitro or halogen; z is 0 or 1 to form a first reaction mixture containing a nitro intermediate, (II) by reducing at least about 50% of the nitro groups in the first reaction mixture to amino groups. Use according to Claim 29, characterized in that R 'is in the para position with respect to the hydroxyl group and is derived from homopolymerized isobutylene and z is 0. Use according to one of the preceding claims, characterized in that the at least one nitro substituent is reduced with hydrogen in the presence of a metallic hydrogenation catalyst. claim;