FI68056C - HYDRAZINE NITROPHENOL REACTION PRODUCT FOR ANALYZING SOM BRENSLE- ELLER SMOERJMEDELTILLSATS - Google Patents

Description

rgl ADVERTISEMENT 68056

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C ^ 45) Γ.; - ::. til 'y - J7 19-. 5 (51) Kv.lk. * / Int.ci. 'C 07 G 17/00, C 10 M 1/34, 3/28 // C 07 c 91/44 SUO MI - FI N LAN D (21) Patent application - Patenunsökning 772350 (22) Filing date - Ansökningsdag 03 08 77 fFh * f (23) Starting date - Giltighetsdag 03.08.77 (41) Published public - Blivit offendig ^ jj Q2 ^ g

National Board of Patents and Registration Date of publication and publication. - 2q Q, 8ς

Patent- and Register-Register '' Ansökan utlagd och utl.skriften publlcerad ^ *> (32) (33) (31) Claim claimed privilege - Begärd priority Box 17100, Euclid Station, Cleveland,

Ohio 44117, USA (72) Kirk Emerson Davis, Euclid, Ohio, USA (74) Oy Jalo Ant-Wuorinen Ab (54) Hydrazine-nitro-phenol reaction products used as fuel and butter additive - Hydrazin This invention relates to reaction products which can be used as additives in lubricants based on oils having a lubricating viscosity and in normal liquid fuels. This invention also relates to fuels, lubricants and additive concentrates containing these reaction products.

It is known to reduce certain aromatic nitro compounds to aromatic amino compounds using hydrazine or hydrazine hydrate in the presence or absence of metal-containing catalysts such as platinum, nickel and palladium, cf. for example, Chemical Reviews, Vol. 6_5, p. 51 et seq., (1 965), entitled "Hydrazine as a Reducing Agent for Organic Compounds"; Huang-Minlon, Journal of the American Chemical Society, Vol. 7C>, pp. 2802-2805 (1948) and P.N.R.Bavin, "Canadian Journal of Chemistry", Vol. 36, pp. 238-241 (1958).

U.S. Patent No. 2,868,844 discloses a process for preparing 4-nitro-2,6-dialkylphenols in which the corresponding dialkylphenol is nitrated with nitric acid in the presence of an inert hydrocarbon solvent. Examples 1-14 of the patent describe the preparation of several 4-nitro-2,6-dialkylphenols and Example 15 the hydrogenation-reduction of a 4-nitro group to a 4-amino group. The reduction is carried out using a comminuted platinum-silica gel catalyst in the presence of ethanol. However, the use of a hydrazine source is not mentioned in the reference.

U.S. Patent 3,737,465 describes compounds having two terminal hydroxymethyl-5-alkylbenzyl substituents obtained by condensing 4-alkylphenol with formaldehyde using concentrated alkali as a reaction promoter. The reference describes the reaction of bis-hydroxyalkyl compounds with other compounds such as ammonia and polyamines to form complex oil-soluble amines.

It has been known for several decades that the performance of lubricants based on lubricating viscosities (e.g. oils and greases) and normal liquid fuels (especially fuels used in internal combustion engines) can be improved by using additives. However, due to scarcity of raw materials and rising equipment costs, politically sensitive petroleum resources, inflation, new types of engines, fuels and lubricants, and awareness of environmental issues, research to find new, efficient, alternative lubricants and fuels has continued unabated.

It is therefore an object of the present invention to provide novel hydrazine-nitrophenol reaction products which provide useful and advantageous properties to oil-based lubricants and normal liquid fuels containing said reaction products as an additive.

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

The coward reaction products of this invention are prepared by subjecting (A) at least one nitrophenol of formula (° H) to c

'I

(R) a - AR - (NO 2) b wherein R is a hydrocarbon-based substituent having 30 to 700 aliphatic carbon atoms; a, b and c are independently 3 68056 female numbers 1 to 3, provided that the sum of the numbers a, b and c does not exceed the number of unsaturated valencies of the groups Ar; and Ar is a benzene group having 0 to 3 alternative substituents selected from lower alkyl, lower alkoxy or halogen to react (B) with at least one hydrazine source, optionally in the presence of at least one metal-containing hydrazine decomposition catalyst.

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.

According to a preferred embodiment of the present invention, the reaction between (A) and (B) takes place without the use of a metal-containing hydrazine decomposition catalyst. This means that the reaction of (A) and (B) takes place in a reaction mass which does not contain sufficient catalyst to substantially or significantly affect the rate or direction of decomposition or reaction of the hydrazine source present. This does not mean that the reaction takes place completely without all the metals explained below. These metals may be present in pure, alloyed or chemically bonded form as part of metallic devices such as agitators, tubes, vessels, probes, etc., and in this form they may communicate with the reaction mass without substantially affecting the decomposition of the hydrazine source present in the mass! direction or speed of reaction. In such cases, the reaction is said to take place in the absence of a decomposition catalyst for the metal-containing hydrazine.

Thus, hydrazine is used as a reducing agent in the manufacture of the products of the invention, which allows the products to be prepared at atmospheric pressure, whereas according to the aforementioned prior art patent U.S. Pat. No. 2,868,844, elevated pressures are used. Reduction with hydrazine can also be performed without a metal catalyst, while according to said U.S. patent, a metal catalyst must be used at elevated pressure. The fact that the reaction can be carried out without a metal catalyst, if desired, is a clear advantage over the prior art, since the process is less expensive and there is no risk that the product will contain the metal catalyst as an impurity.

When prepared according to the invention, the products obtained are also lighter in color than when reduced with hydrogen according to the prior art 4 68056. A lighter and better color is a clear commercial advantage associated with the products of the invention.

Also within the scope of this invention are lubricants based on oils having a lubricating viscosity, normal fuels and additive concentrates containing the aforementioned reaction products.

The monocyclic aromatic ring which may form a group Ar can be represented by the general formula ar <Q) m wherein ar represents benzene, and each group Q independently represents a lower alkyl group, a lower alkoxy 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 alkoxy groups. Halogen atoms include fluorine, chlorine, bromine and iodine atoms; halogen atoms are usually fluorine or chlorine atoms.

Examples of such Ar groups are as follows: H --------- -Me

H ----------- H H ------- H --- H

H '—-Ατ- Ι 1

Me - H H Y ° Pr H ΊΓ ~ C1

H Y — Cl H— H

68056 5, etc., in which

Me is methyl, Et is ethyl, Pr is n-propyl.

A typical Ar group is a benzene nucleus having 3-5 unsaturated valencies, so that one or two of these valences 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 nitrophenols of this invention contain, directly attached, a substituent R of the benzene group Ar having from about 30 to 700 aliphatic carbon atoms. This R is generally aliphatic in nature, but in some cases may be substantially aliphatic and contains one carbocyclic group (e.g., an aromatic or alicyclic group) for each 10 carbon atoms present. Typically, however, R is purely aliphatic. More than one such group may be present, but generally no more than 2 or 3 such groups per benzene core Ar are present. Often, but not necessarily, there is one R group for each benzene group. The number "a" in formula I indicates the number R of groups present.

The group R generally contains at least about 30 carbon atoms and up to about 500, typically about 50 to about 500 aliphatic carbon atoms. When only one R group and the -OH substituent are present in the benzene group Ar, the R group is generally in the ortho or para position relative to the -OH substituent. The aliphatic substituent R is generally a hydrocarbyl group in nature; however, it may also be hydrocarbon-based in nature and contain, in addition to carbon and hydrogen, not more than 10% by weight of other elements such as oxygen (usually in the form of ether or hydroxyl groups), sulfur (usually in the form of sulphide or thiol groups) and halogen (especially chlorine); or bromine). The R group is predominantly saturated, which means that it may contain up to one carbon-carbon double bond for every 10 simple carbon-carbon bonds. However, R is preferably completely saturated and does not contain 68056 6 ττ ~ any double bonds.

Aliphatic R substituents are generally prepared from homo- or interpolymers of mono- and di-olefins having 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, isobutene, butadiene, isoprene, 1-hexene, 1-octene, etc. (e.g. copolymers, terpolymers). These olefins are generally 1-mono-olefins.

A preferred source of the substituent R is poly (butenes) obtained by polymerizing a C 1-6 refining stream having a total butene content of 30-75% by weight and an isobutene content of 20-60% 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 J

- CH ~ C - ---

1 J

CH3

The addition of an aliphatic R substituent to the benzene group Ar of the nitrophenols 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 chloride, 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 a benzene group Ar are well known to those skilled in the art.

As shown in formula I, the nitrophenols of this invention contain at least one of the following substituents: a hydroxyl group, an R group as defined above and a primary nitro group, -NO 2 · 68056 7

According to a preferred embodiment, the nitrophenols used according to the present invention contain one or two of the above-mentioned substituents. This preferred class of nitrophenols can be illustrated by the formula <? H> 1-2 R 'f' '' f -..... IN ° 2> 1-22 (R ") z wherein the R 'group is an aliphatic substituent wherein has an average of about 30 to about 700 aliphatic carbon atoms, generally about 50 to about 500 carbon atoms ortho or para to the hydroxyl group, R "is a lower alkyl, lower alkoxy or halogen atom, and z is 0 or 1. The substituent R ' is of the same general nature as R and what has been said above about the nature of R applies equally well to R '. R 'is generally an alkyl or alkenyl group, and z is 0.

According to an even more preferred embodiment of the invention, the formula of the nitrophenol used is m> i-2 Ί

(R "') z —ij- ~ j-- no2 III

R + wherein R + is an alkyl or alkenyl group derived from homopolymerized or interpolymerized 1-olefins, and is in the para-position to the -OH group and contains on average about 50 to about 500 carbon atoms and R "'is lower alkyl, lower alkoxy, nitro or halogen and z is 0 or 1.

In general, R + is derived from polymerized ethylene, propylene, butylene, or mixtures thereof. Typically, it is derived from polymerized propylene or butylene. In one embodiment z is zero, in another embodiment z is 1, R "'is nitro.

8 68056 only one OH group is present and the nitro group R "'is ortho to this.

The nitrophenols used in 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 of the reaction steps. 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, for example to prepare a polynitro intermediate, and one nitro group of this intermediate can be converted to a hydroxyl group by melting with a base to produce the desired nitrophenol.

Another useful method for preparing the nitrophenols used in the invention involves alkylating the phenol with an olefinic alkylating agent to an alkylated phenol. This alkylated phenol can then be nitrated to nitrophenol.

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, 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, NO 2, N 2 O 2, N 2 O 4, N 2 O 4 -, NC 2 Cl 2, NO 2 Br, mixtures of alkali and alkaline earth metal nitrides (mineral acids e.g. with H 2 SO 4), alkanoyl nitrates (e.g. acetyl nitrate) and a combination of two or more such nitrating agents. A suitable nitration reagent is generally nitric acid at a concentration of, for example, about 30-90%. The reaction can be aided by the use of predominantly inert liquid diluents and solvents, such as acetic or butyric acid, which enhance the contact between the reagents and the heat transfer properties.

The conditions and methods for nitroxy of the 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 of alkylphenols 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 generally used per mole of nitroxy-aromatic intermediate to be nitrated. When nitric acid is used as the nitrating agent, it is generally used in an amount of about 1.0 to about 3.0 moles per mole of the aromatic compound. It is always possible to use an excess of about 5 molar nitrating agent when it is desired to promote or carry out the reaction rapidly.

Nitration of the phenol generally takes 0.25-24 hours, although it may be appropriate to react the nitration mixture for longer periods of time, such as 96 hours.

A typical process for preparing the nitrophenols for use in this invention may be summarized to include nitration of at least one phenol with at least one nitrating agent of the formula (R) Ar '(OH), wherein each R is an aliphatic substituent having at least 30 , typically from about 30 to about 700 carbon atoms, wherein at least one of R is in the ortho or para position to at least one OH group directly attached to Ar '; a and c are independently integers from 1 to 3, but their sum does not exceed the number of unsaturated valencies in the group Ar ', and Ar' is a Bentene group having at least one hydrogen atom attached to the carbon atom of the benzene ring, and 0 to 3 alternative substituents which are Lower alkyl, lower alkoxy, halogen, nitro or combinations of said alternative substituents. R contains an average of about 50 to about 500 carbon atoms and is typically derived from homopolymerized or interpolymerized C 2 -C 10 olefins and mixtures thereof.

Such nitrated phenols are typically prepared by nitrating at least one compound of the formula with a nitrating agent

OH

- R '1V

wherein R 'and R "are as defined above and R' is generally ortho or para to the hydroxyl group, and z is 0 or 1. Typically, R 'is para to the hydroxyl group and z is zero.

The hydrazine source (B) compound used in this invention or a mixture of compounds capable of forming hydrazine under the conditions of reaction (A) + (3) in an amount sufficient to react with the nitrophenol (A) present. Several such sources of hydrazine are known, cf. for example, Hydrazine, Charles C. Clark, Mathieson Chemical Corporation, Baltimore, Maryland (1953), especially pages 31-71 and 120-124; and records "The Chemistry of Hydrazine", L.F.Audrieth and B.A.Ogg, John Wiley and Son, New York (1951), especially pages 209-223.

10 68056

The most common and thus most preferred sources of hydrazine are hydrazine itself, hydrazine hydrate and solutions of hydrazine and water, as well as hydrazinium salts, semi-carbazides and thiosemicarbazides of sulfuric and hydrochloric acid and their analogous salts; hydrazine dicarboxylates of lower alkanols (e.g. ROOCNHNHCOOR) and their dimers, as well as aminoguanidines and their -NHNH-sulfuric and hydrochloric acid salts and benzenesulfonyl hydrazides and their bisoxy analogues. Mixtures of hydrazine sources can also be used. This list is not exhaustive and does not limit the invention in any way, as there are numerous other sources similar to the listed hydrazine sources and known to those skilled in the art.

For cost and handling reasons, hydrazine and its solutions with water and other solvent diluents are preferably used. A typical hydrazine source is a mixture of water and hydrazine containing about 64% hydrazine, although mixtures of the same type containing more or less hydrazine (about 20-80%, and most often 30-70% hydrazine) may be used.

The use of these hydrazine sources in chemical reactions is known to those skilled in the art, as is apparent, for example, from the above-mentioned books and from the article "Hydrazine", Kirk-Othmer Encyclopedia of Chemical Technology, second edition, Vol. 11, pp. 164-196, Interscience Publishers, New York, New York (1966). These publications are presented herein only as relevant reference publications on the use of hydrazine sources.

Reaction of Nitrophenol (A) with Hydrazine Source (B) To prepare the reaction products of this invention, about 1.5 to about 5 moles of hydrazine source (B) are used for each nitrophenol equivalent (A) present. One mole of hydrazine source is the amount that forms one mole of hydrazine (NH 2 NH 2) under the reaction conditions. One equivalent of nitrophenol is the amount containing one mole of nitro group. For example, one mole of mono-nitrophenol contains one mole of nitro groups, while one mole of dinitrophenol contains two moles of nitro groups. Thus, the equivalent of dinitrophenol is half a mole of phenol.

For each equivalent of nitrophenol (A), about 1.5-2.5 moles of hydrazine source are preferably present. The hydrazine source need not be present in its entirety at the beginning of reaction (A) + (B) but may be added continuously or gradually as the reaction proceeds. The only condition is that at the end of the reaction, the above-mentioned amount is added to the reaction mass.

li 68056

From an economic and practical point of view, it is advantageous for a stoichiometric amount of hydrazine source to react with nitrophenol. However, as will be apparent to those skilled in the art, organic reactions do not always proceed until a stoichiometric amount has reacted, and in the present invention it is sufficient that about 50 mole percent of the nitro groups present in nitrophenol (A) have reacted with a hydrazine source.

The reaction between (A) and (B) generally takes place at a temperature above 50 ° C. The reaction generally takes place at a temperature above about 100 ° C and below about 350 ° C.

The reaction between (A) and (B) generally takes about 2 to about 24 hours; can be used for longer periods such as 96 hours. Typically, the reaction takes about 4 to 8 hours, often about 6 hours.

Nitrogen-containing organic compositions can be isolated using isolation and purification methods known to those skilled in the art, such as distillation, extraction, crystallization, centrifugation, etc. However, it is generally possible to use nitrogen-containing compositions directly. without further purification or isolation of their mixtures. In terms of appearance and / or storage stability, the reaction mass is treated only by simple purification methods, such as filtering the reaction mass with known filter aids such as diatomaceous earth, carbon powder, etc. Experts are able to easily select the appropriate methods in each case. according to the situation.

As mentioned above, the reaction between (A) and (B) may alternatively take place in the presence of at least one decomposition catalyst for metal-containing hydrazine. Numerous such catalysts are known to those skilled in the art and the following description is given by way of example only and is in no way limiting. The reactions of hydrazine and hydrazine sources with such catalysts have been discussed generally in "Hydrazine" and "The Chemistry of Hydrazine" and in the article "Hydrazine", Kirk-Othmer Encyclopedia of Chemical Technology, which has been referred to once before. Suitable metals included in the hydrazine decomposition catalysts useful in the invention include platinum, palladium, nickel, copper, iron, ruthenium, cobalt, rhodium, osmium, and mixtures of two or more thereof. The catalyst may be an elemental metal, an alloy of various metals, a metal compound such as an inorganic salt, oxide, etc., metal salts with organic acids such as carboxylates or sulfonates, and coordination complexes with suitable ligands. Catalysts can be used in any of their well-known forms, such as finely divided metals without support, thin metal films deposited on active or inactive substrates or electrodes, and in a variety of forms, such as granules, spirals, etc., which are generally used in large areas. Particularly preferred are finely divided metals commonly known as hydrogenation catalysts, e.g. palladium, platinum and nickel. Metals that have been chemically and / or physically treated to modify their activity (e.g., Raney nickel) are often used. See. for example, the article "Hydrazine as a Reducing Agent for Organic Compounds" in "Chemical Reviews", which has been referred to previously.

The reaction between the nitrophenols (A) and the hydrazine source (B) probably yields mainly aminophenols in which the amino group replaces one or more of the nitro groups (A). It is known (i) that the hydrazine source is consumed in the reaction, (ii) the infrared absorption bands associated with the nitro groups in the spectrum of (A) are reduced or eliminated, (iii) nitrogen is present in the final product and (iv) water is generally formed in the reaction. All of these findings are consistent with the assumption that the hydrazine source reduces the nitro groups of (A), probably to amino groups. However, this assumption does not limit the invention, but the invention is limited only by this explanation in its entirety.

The following examples illustrate the present invention. In the examples of this specification and elsewhere, parts and percentages refer to parts by weight and percentages by weight, and all temperatures are in degrees Celsius unless otherwise indicated.

Example 1:

The alkylated phenol is prepared by reacting the phenol with polybutene having an average molecular weight of about 1000 (vapor phase osmometry) in the presence of a boron trifluoride / phenol catalyst. The catalyst is neutralized and removed by filtration. Distillation of the product filtrate first to 230 ° / 760 torr (vapor temperature), then to 205 ° / 50 torr (vapor temperature) gives a sufficiently pure alkylated phenol as a residue.

To a mixture of 265 parts of purified alkylphenol, 176 parts of mixed mineral oil and 42 parts of solvent gasoline having a boiling point of about 20 ° is slowly added 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 (vapor temperature) and filtered to give an oily solution of the desired nitrophenol intermediate.

13 68056

Example 2:

A mineral oil solution (1900 parts) of the alkylated nitrated phenol of Example 1 containing 43% of mineral oil is heated to 145 ° under a nitrogen atmosphere. 70 parts of hydrazine hydrate are then added to the mixture over a period of 5 hours while maintaining the temperature at 145 °. The mixture is heated at 160 ° for one hour while collecting 56 parts of aqueous distillate. An additional 7 parts of hydrazine hydrate are added and the mixture is heated at 140 ° for a further hour. Filtration at 130 ° gives an oil solution of the desired product containing 0.5% nitrogen.

Example 3:

To a mixture of 800 parts of substantially polybutene-substituted phenol prepared according to Example 1 and 944 parts of a diluent mineral oil at a temperature of 59 ° is added 72 parts of concentrated nitric acid. The reaction is monitored so that the reaction temperature remains at 59-68 °. The reaction mixture is stirred for two hours at 69-73 ° and then heated to 140 ° while nitrogen is slowly passed through it and the water is removed by distillation. Hydrazine hydrate (90 parts) is then slowly added to the mixture at 130-137 ° over three hours. The mixture is stirred for 0.5 hours at this temperature and then heated to 160 ° while nitrogen is slowly passed through it and the aqueous distillate is collected. An oily solution of the desired product is obtained as a residue.

Example 4:

A mixture of 609 parts of a polybutene-substituted phenol prepared mainly according to Example 1 and 454 parts of a mineral oil diluent is stirred at 57 °. To this mixture is added 46.5 parts of nitric acid (66.3%) within 8 hours. The mixture is stirred for 1.5 hours at 58-63 ° and then heated at 142 ° for 1.7 hours while slowly passing nitrogen through it. The mixture is kept at 143-145 ° for 0.5 hours and then cooled to 114 °. During the reaction, 23 parts of distillate are collected. Filtration of the mixture at 113-126 ° gives an oil solution of the desired nitro intermediate with a nitrogen content of 0.64%.

Example 5: 320 parts of the oily solution of polybutene-substituted nitrated phenol described in Example 4 are added 12 parts of aqueous hydrazine (64% hydrazine) over 6.25 hours at 160 °. Filtration gives an oil solution of the desired product with a nitrogen content of 0.59%.

14 68056

Example 6:

To a mixture of mainly alkylated phenol prepared according to Example 1 having a polybutylene substituent containing about 70 carbon atoms and 3,000 parts of glacial acetic acid is added at 51 ° 540 parts of concentrated nitric acid over three hours. During the addition, the temperature is maintained at 51-63 °. The mixture is stored at room temperature for 18 hours and then heated at 120 ° for 6 hours while slowly passing nitrogen through it. The aqueous distillate is collected. The reaction is then distilled to 140 ° / 28 torr (vapor temperature) and the residue is filtered at 120 ° to give the desired final product with a nitrogen content of 2.55%. Based on this, it is calculated that the product contains an average of two nitro groups per alkylated phenol. Example 7:

To a mixture of 545 parts of the alkylated dinitrophenol described in Example 6 and 340 parts of a dilution mineral oil at 125 ° are added 100 parts of hydrazine hydrate. The addition is carried out under a nitrogen atmosphere for 2.5 hours while maintaining the temperature at 122-125 °. The reaction mixture is then refluxed at 123 ° for 2.5 hours and heated at 155 ° for a further 2 hours while collecting the aqueous distillate. A weak stream of nitrogen is passed through the reaction mixture at 150-155 ° for a further 2 hours and the residue is filtered to give an oily solution of the desired product with a nitrogen content of 1.16%. Example 8:

To a mixture of 361 parts of tetrapropenyl-substituted phenol and 271 parts of glacial acetic acid at 7-17 ° is added a mixture of 90 parts of nitric acid (70% HNO 2) and 90 parts of glacial acetic acid. The addition is carried out for 1.5 hours while the reaction mixture is externally cooled to 7-17 °. The cooling bath is removed and the reaction mixture is stirred for 2 hours at room temperature. Distillation to 134 ° / 35 torr (steam temperature) and filtration affords the desired nitrated intermediate with a nitrogen content of 65%.

Example 9: 303 parts of the nitrated intermediate described in Example 8 are added at 125 ° under a nitrogen atmosphere to 100 parts of hydrazine hydrate for 2.4 hours. The mixture is refluxed for 2.5 hours and then distilled to a steam temperature of 155 °. A weak stream of nitrogen is passed through the reaction mixture while maintaining its temperature at 155-190 °. Filtration of the residue gives the desired final product with a nitrogen content of 4.89%.

1 5 68056

As mentioned above, the nitrogen-containing compositions of this invention are useful additives in the preparation of lubricant compositions based on oils of lubricating viscosity which are used, e.g., for lubricating internal combustion engines. The additives act as detergents and dispersants in the engine sludge formed in the oil during its use. They are particularly useful in cases where the oil is exposed to high temperatures or repeated stresses such as intermittent or high power engines.

The lubricating oil compositions of this invention include, for example, crankcase lubricants for spark and compression ignition internal combustion engines such as automobile and truck, diesel, positive ignition and two stroke engines, boat and locomotive engines, etc. Wankel engines are considered in this specification to be two stroke engines. The lubricant compositions of the invention can also be used in garden machines, sawmills and similar equipment. The nitrogen-containing compositions of this invention may also be advantageous in automatic transmission fluids, transmission and transmission lubricants, industrial oils such as metalworking lubricants, hydraulic fluids and other oil and grease compositions.

The lubricant compositions of this invention may be based on natural oils, synthetic oils, natural oil blends, synthetic oil blends, and blends of natural oil and synthetic oil. Natural oils include animal and vegetable oils (e.g., castor oil, lard oil) and mineral lubricating oils, such as 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 homopolymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.); poly (1-hexenes), poly (1-octenes), poly (i-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.

16 68056

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

Another suitable class of synthetic lubricating oils are dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azalic acid, malonic acid, cinnamic acid, sebacic acid, fumaric acid, adipic acid, adipic acid, adipic acid, adipic acid, esters with a variety of 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, di-isooctyl acelate, diisodecyl acelate, 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 with two moles of 2-ethyl and hexane.

Esters useful as synthetic oils also include those prepared from C 1 -C 4 oncarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripenta-tert-tritol, etc.

Silicone-based oils such as polyalkyl, polyaryl, polyalkoxy or polyaryloxy-siloxane oils and silicate oils form another useful class of synthetic lubricants (e.g. tetraethylsilicate, tetraisopropylsilicate, tetra- (2-ethylhexyl) silyl) silyl silicate, tetra- (p-tert-butylphenyl) silicate, hexyl- (4-methyl-2-pentyl-68056 toxin) -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 of the invention. Unrefined oils are obtained directly from a natural or synthetic source without further purification. For example, the unrefined oil may be a shale oil obtained directly from distillation processes, a petroleum oil obtained directly from 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 treated 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 as starting material. Such refined oils are also known as regenerated oils and are often further treated to remove used additives and oil decomposition products.

Generally, about 0.05 to 30, usually about 0.1 to 15 parts (by weight) of at least one nitrogen-containing composition of this invention is permanently dissolved or dispersed in 100 parts of an oil to produce a satisfactory lubricant. Other additives may also be used in accordance with the invention in conjunction with the composition of this invention. Such additives include, for example, additional detergents and dispersants, which may be of the ash-forming or non-ash-type type, antioxidants, pour point depressants, high-pressure agents, color stabilizers and antifoams.

As used in this specification and claims, the phrase "stable dispersed" means a composition (e.g., a single additive or compound, a mixture of two or more additives or compounds, etc.) dispersed in a particular medium in an amount in which it acts as intended. Thus, when the composition of the present invention is used as an oil, the composition must be sufficiently suspended in the oil to give the oil one or more of the properties of the composition suspended therein. Such a suspension can be obtained in a number of different ways, such as by continuously circulating the oil or by injecting it into different types of lubricant systems. Conventional dispersants (such as the acylated nitrogen dispersants described in U.S. Patent 3,219,666) may be used in lubricants and fuels to provide a stable dispersion or suspension of the composition. However, the compositions of this invention are always "soluble" or "stably dispersed" in a normally liquid medium in which they are used elsewhere in the minimum amounts mentioned elsewhere in this specification, thus using the terms "soluble" and "stably dispersed" in a conventional manner known to those skilled in the art.

In the specification, the phrase "substantially inert" with solvents, diluents, base oils and the like means that the solvent, diluent or the like is inert to chemical or physical change under the conditions of use and does not substantially adversely affect the preparation of nitrogenous compositions, oils, fuels, concentrates, concentrates, concentrates, concentrates or concentrates. and / or activities. For example, a small amount of solvent, diluent, etc. may react or decompose to a small extent, however, adversely affecting the application of the invention. In other words, such a reaction or decomposition, although technically detectable, is not sufficient to prevent a skilled worker from practicing the present invention. The saying "primarily inert" is thus perfectly clear to the expert.

The hydrazine-nitrophenol reaction products according to the invention can also be used in fuels in which they act as detergent dispersants, gas detergents and demulsifiers for motor sludge.

The fuel compositions of this invention generally comprise predominantly normal liquid fuel, such as hydrocarbonaceous petroleum distillate (e.g., gasoline according to ASTM D-439-73 and diesel and fuel oil according to ASTM D 396). Also within the scope of this invention are normal liquid fuel compositions containing non-hydrocarbonaceous substances such as alcohols, ethers, organon-nitro compounds and the like (e.g., methanol, ethanol, diethyl ether, methyl ether, nitromethane), and liquid fuels. obtained from plant or mineral sources such as maize, alpha-alpha, shale and coal.

Also within the scope of the invention are normal liquid fuels which are mixtures of one or more hydrocarbonaceous fuels with one or more non-hydrocarbonaceous substances. Examples of such mixtures are mixtures of gasoline and ethanol, diesel oil and ether, gasoline and nitromethane, etc. A particularly preferred fuel is gasoline, i.e., a mixture of hydrocarbons having an ASTM boiling point of 60 ° at a 10% distillation point to about 205 ° at a 90% distillation point.

These fuel compositions generally contain an amount of at least one reaction product of this invention sufficient to impart dispersing, detergent or demulsifying properties to the fuel; this amount is generally about 1 to about 10,000, preferably 4 to 1,000 parts by weight of the reaction product per 1 million parts by weight of fuel. Gasoline-based fuel compositions having engine oil sludge dispersing and detergent properties as well as gas detergent detergent properties are preferred.

The fuel compositions of this invention may contain, in addition to the reaction products of the invention, other additives well known to those skilled in the art. These may be anti-knocking 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 trieryl phosphates, colorants, cetane solvents agents such as 2,6-di-tert-butyl-4-methylphenol, anti-corrosion agents such as alkylated succinic acids and anhydrides, bacteriostatic agents, resin inhibitors, metal deactivators, de-emulsifiers, antifreeze agents and the like.

Refined mineral oils, especially "bright stock" and oily homo- and interpolymerized lower olefins such as ethylene / propylene copolymers, polypropylene and polybutenes, etc., are often used in fuel compositions (especially gasoline) to reduce the formation of deposits inducing such fuels.

In certain preferred detergent compositions of the invention, the aforementioned reaction products of the invention are combined with other non-ash dispersants in gasoline. Such non-ash dispersants are preferably mono- or polyol esters with a high molecular weight mono- or polycarboxylic acid acylating agent containing at least 30 carbon atoms in the acyl group. Such esters are well known to those skilled in the art, cf. e.g., FR patents 1,396,645, GB patents 981,850 and 1,055,337, and U.S. patents 3,255,108; 3,311,558; 3,331,776; 3,346,354; 3,522,179; 3,579,450; 3,542,680; 3,381,022; 3,639,242; 3,697,428; 3,708,522; and GB Patent 1,306,529. These patents are included in this specification because they disclose suitable esters and methods for their preparation. In general, the weight ratio of the reaction products of the invention to the above-mentioned non-ash dispersants is from about 0.1 to about 10.1, preferably from about 1 to about 10 parts of the reaction product of the invention per part of the dispersant.

According to another embodiment of the invention, the reaction products according to the invention can be combined with Mannich condensation products obtained from substituted phenols, aldehydes, polyamines and aminopyridines for the preparation of lubricating and / or fuel additives. Such condensation products are described in U.S. Patents 3,649,659; 3,558,743; 3,539,633; 3,704,308; and 3,725,277.

The reaction products of this invention may be added directly to a fuel or lubricating oil to prepare the fuel or lubricant compositions of the invention or may be diluted with at least one substantially inert normally liquid organic solvent / diluent such as mineral oil, xylene, alcohol, nitro lower alkane, as described above, to form an additive concentrate which is then added to the fuel or lubricating oil in an amount sufficient to prepare the fuel and / or lubricant composition of the invention. These concentrates generally contain from about 30% to about 90% of the reaction product of the invention and may additionally contain any of the above-mentioned customary additives, in particular the above-mentioned ash-free dispersants in the above-mentioned proportions. The remainder of the concentrate consists of solvent / diluent.

The present invention also relates to two-stroke engine lubricants containing the reaction products defined above.

These two-stroke engine lubricant compositions generally contain from about 98% to about 55% oil or a mixture of oils having a lubricating viscosity. A typical composition contains from about 90% to about 70% oil. Preferred oils are mineral oils and mixtures of mineral oils and synthetic polymers and / or ester oils. Typical useful synthetic oils include oily polybutene fractions having a molecular weight of about 250 to about 1000 (measured by vaporase osmometry) and fatty acid ester oils of polyols such as pentaerythritol and trimethylol.

These oil compositions contain from about 2% to about 30%, typically from about 5% to about 20%, of at least one of the reaction products described above. Other additives may also be present, such as additional detergents and dispersants, which may be of the ash-forming or non-ash type, antioxidant, coupling agents, pour point depressants, high pressure agents, color stabilizers and defoamers.

Detergent dispersants of the non-ash or ash-forming metallic type are used to prevent the piston ring from sticking and to keep the engine clean. Suitable high ash-free dispersants must be used in high-performance two-stroke lubricants because ash-forming detergents tend to form fuel cell deposits that cause premature ignition. Compositions for use under less severe conditions may contain calcium, barium or magnesium sulfonates or phenates, either alone or in combination, or in combination with non-ash dispersants. Antioxidants can be included to promote the thermal stability of the lubricant.

Polymeric viscosity index improvers have been and are being used in two-stroke oils to improve lubricant film strength and engine cleanliness. Dyes can be used for identification purposes and to indicate whether or not the two-stroke fuel mixture contains a lubricant. Coupling agents are added to some products to provide better component solubility and improved fuel / lubricant mixture water tolerances.

Anti-wear and lubricity enhancers, especially sulfurized whale oil or sulfurized whale oil substitutes, and other fatty acid and vegetable oils such as castor oil are used in two-stroke engine oils for certain applications such as racing and very high fuel / lubrication. Scavengers and fuel cell deposit modifiers are used in some cases to extend the life of spark plugs and to remove carbon deposits. Halogenated compounds and / or phosphorus-containing substances can be used for this purpose.

All types of anti-corrosion and anti-corrosion agents can and will be included in two-stroke oil compositions. For aesthetic reasons, odorants or deodorants are sometimes used.

Lubricants such as synthetic polymers (e.g., polyisobutene having an average molecular weight of about 750 to about 15,000 as measured by vapor phase osmometry or gel permeation chromatography (polyol chromatography), polyol chromatography (e.g.), polyol (e.g.)) can be used in the two-stroke engine oil compositions of this invention. oxoethylene-oxypropylene) ether) and ester oils (e.g. ester oils as described above). Natural oil fractions such as "bright stocks" (compared to viscous products obtained from conventional lubricant production from crude oil) can also be used for this purpose. These are generally used in amounts of about 3 to about 20% in two-stroke oils based on the total amount of the oil composition.

The two-stroke oils of this invention 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., iso-stearic acid and mixtures of isostearic and stearic acid) with 2 to about 10 amino groups and an alkylene polyamine of 2 to about 20 carbon atoms, with diethylenetriamine, 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 solvent gasoline-type substances boiling in the range of about 38-90 ° (e.g., Stoddard solvent), may also be included in the oil compositions of this invention, typically using 5-25%.

A typical two-stroke engine oil lubricant composition contains 2-10% of one or more of the nitrogen lubricants described in Example 2.

II

23,68056, 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 solvent.

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 mixtures 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 percentages

Base oil ^ 60.0

Bright Stock ^ 10.0

Stoddard solvent 15.0 3)

Hydrazine Nitrophenol Additive 15.0 1) Solvent-refined neutral oil having a viscosity of 650 SUS at 98.8 ° 2) Viscosity of 150 SUS at 98.8 ° 3) Mineral oil solution containing the reaction product described in Example 7.

Claims (11)

A reaction product for use as a fuel or lubricant additive, characterized in that it is obtained by reacting (A) at least one nitrophenol with the formula <? Hlc (R) a-Ar - (NO2) b where R is a hydrocarbon-based substituent having 30-700 aliphatic carbon atoms; a, b and c are each and independently of one another, from 1 to 3, with the proviso that the sum of a, b and c does not exceed the unsaturated valences of Ar; and Ar is a benzene group having from 0 to 3 optional substituents which are lower alkyl, lower alkoxy or halogen, or combinations of two or more of said optional substituents, with (B) at least one hydrazine source, optionally in the presence of at least one metal-containing substituent. hydrazinsönderdelningskatalysator. Reaction product according to claim 1, characterized in that the reaction between (A) and (B) is carried out in the absence of said metallic catalyst. 3. A reaction product according to claim 1, characterized in that the reaction between (A) and (B) is carried out in the presence of a metal-containing hydrazine decomposition catalyst wherein the metal is platinum, palladium, nickel, copper, iron, ruthenium, cobalt, rhodium or a combination of two or more of these metals. 4. A reaction product according to claim 1, 2 or 3, characterized in that the hydrazine source is hydrazine, a semicarbazide, a hydrazine dicarboxylate of a lower alkanol, a mixture of two or more of these or a mixture of one or more of these with water. . A reaction product according to any one of the preceding claims, characterized in that a, b and c are each and independently of each other 1 or 2 and at least one