JPS6017779B2 - Method for producing nitrogen-containing composition - Google Patents

Description

[Detailed description of the invention]

This invention relates to compositions useful as oil-based lubricants of lubricating viscosity and as additives for normally liquid fuels, in particular compositions containing a hydrazine source and at least one substituent having at least one hard carbon atom. The present invention relates to a composition obtained by reaction with a substituted nitrophenol. Processes for making this composition, as well as fuel or lubricant compositions and additive concentrates comprising this composition, are within the scope of this invention. It is known to use hydrazine or hydrated hydrazine to convert certain aromatic nitro compounds into aromatic amino compounds in the presence or absence of metal-based catalysts such as platinum, nickel or palladium. . For example, "Chemical Reviews" (1963 edition) No. 6
5 Lid, page 51 et seq., ``Hydrazine as a Reducing Aged Research Organic Compounds,'' Huang I. Minion, ``Journal of the American Chemical Society'' (1948) No. 70. Volume 2802-2805 and P. N. T. Babin, “Canadian Journal of Chemistry” (1958), No. 3, 238-241
See page. Over the past few decades, oils with lubricating viscosity (
For example, certain additives have been added to improve the performance characteristics of lubricants based on so-called oils and greases and normally liquid fuels. However, raw materials become increasingly scarce, equipment replacement costs spiral upward, politically sensitive oil supply issues, inflation, new types of engines, fuels and lubricants are developed, and In today's world of environmental concerns, there is still a need to develop effective additives that can be used in both lubricants and fuels. It is an object of this invention to provide new nitrogen-containing compositions capable of imparting useful and desirable properties to oil-based lubricants and normally liquid fuels. A further object of the invention is to provide a method for the preparation of said nitrogen-containing compositions, as well as additive concentrates, lubricant or fuel compositions comprising said compositions. The nitrogen-containing composition of the present invention has the general formula (〇H〉C (R KimrfNo2) b formula (1) (in the above formula, R is a hydrocarbon substituent having at least 10 aliphatic carbon atoms, a , b and c are each independently 1 or less, and are integers up to three times the aromatic number in Ar, and the sum of a + b + c does not exceed the effective valence of ~, and Ar is a lower alkyl group, At least one nitrophenol represented by an aromatic moiety having zero to three substituents selected from the group consisting of a lower alkoxyl group, a halo group, and any combination thereof. obtained by reacting the leg with at least one hydrazine source in the presence of one metal-containing hydrazine decomposition catalyst. As used herein, the term "phenol" has its art-accepted general meaning. It refers to a hydroxy aromatic compound having at least one hydroxyl group directly bonded to a carbon atom of an aromatic ring.

[
The reaction with B' is carried out in the absence of a metal-containing hydrazine decomposition catalyst. This means that the reaction between reactant ① and [B-] does not involve the decomposition of the hydrazine source present or the presence of an amount of catalyst that would significantly or substantially affect the rate or course of the reaction. This means that it is carried out within the system. Furthermore, this does not mean that the reaction can be carried out in the absence of any of the metals described below. These metals exist in pure, alloyed or combined states as part of metal equipment such as ropes, tubes, containers, probes, etc. In these conditions, such metals are not present in the reaction system. can be contacted with the reaction system without appreciably affecting the decomposition or process of the hydrazine source present. In such cases, this specification refers to the reaction being carried out in the absence of a metal-containing hydrazine decomposition catalyst. Also within the scope of this invention are lubricant compositions based on oils of lubricating viscosity, normally liquid fuel compositions, and additive concentrates in combination with the nitrogen-containing compositions described above. This invention will be described in detail below. The aromatic moiety ~ can be a mononuclear aromatic nucleus such as a benzene nucleus, a pyridine nucleus, a thiophene nucleus, a 1,2,3,5-tetrahydronaphthalene nucleus, etc., or a polynuclear aromatic site. It doesn't matter. This polynuclear aromatic moiety may be of the condensation type, that is, the aromatic nucleus is condensed with other nuclei at two positions, as seen in naphthalene, anthracene, azanaphthalenes, and the like. In addition, the above polynuclear aromatic moiety is a crosslinked type,
i.e. at least two nuclei (mononuclear or polynuclear)
may be bonded to each other by cross-linking. Such cross-linking bonds include carbon-carbon-poly bonds, ether bonds, keto bonds, tosulfide bonds, polysulfide bonds having 2 to 6 sulfur atoms, sulfinyl bonds, sulfonyl bonds, alkylene bonds, alkylidene bonds, and lower alkylene ether bonds. , alkylene keto bond, lower alkylene sulfur bond, lower alkylene polysulfide bond having 2 to 6 sulfur atoms, amino bond,
It can be selected from the group consisting of polyamino bonds and combinations of these divalent bonds. In some cases,
One or more crosslinks may exist between two aromatic nuclei in Ar. For example, the fluorene nucleus has 2
Two benzene nuclei are linked by methylene bonds and covalent bonds. Heterocyclic nuclei exist in certain Ar moieties, such as pyridyl, chenyl, and furanyl nuclei, but usually Ar contains only carbon atoms in the aromatic nucleus itself. The number of aromatic nuclei (condensed type, crosslinked type, or both) in Ar is a, b, and c in the formula (1) above.
This is to determine the numerical value of . For example, when Fu contains a mononuclear aromatic nucleus, each of a, b and c is independently 1 and 3. ~ is 2
aromatic nuclei, each of a, b and c is an integer between 1 and 6, ie up to three times the number of aromatic nuclei present (2 in naphthalene). For the trinuclear ~ moiety, each of a, b and c is 1 and 9. *For example, when Ar is a triphenyl moiety, each of a, b and c is independently an integer of 1 to 9. It goes without saying that the numerical values of a, b and c are limited by the fact that they do not exceed the total effective valence number of ~. The monocyclic aromatic nucleus which can be a moiety has the general formula ar(Q)m (in the above formula, ar is a monocyclic aromatic nucleus having 4 to 6 carbon atoms (e.g. benzene, pyridine or thiophene),
Each Q can be independently represented by a lower alkyl group, a lower alkoxy group, or a halogen atom, and m can be 0 or 3). In this specification and claims, the term "lower" as used in reference to groups such as lower alkyl and lower alkoxyl refers to groups having 7 or less carbon atoms. Also,
Halogen atoms include fluorine, chlorine, bromine and iodine atoms. Typically, halogen atoms are fluorine and chlorine atoms. Specific examples of the above monocyclic moieties are listed below. etc. In the above formula, Me is methyl, Et is ethyl, and Pr is normal propyl. Ar is a polynuclear fused aromatic moiety. (indicates a pair of fused bonds in which two carbon atoms are part of each of two adjacent rings). Specific examples of the fused ring type aromatic moiety are listed below.
etc. In the case of a crosslinked type polynuclear aromatic moiety,
This can be expressed as the general formula artLng-arnaW(Q)mW [In the above formula, w is not 1, but is an integer of about 20, and ar is as described above, with the proviso that at least three effective (free) Q and m where valence is present
is as described above, and each Lng is a carbon-carbon single bond, an ether bond (e.g. 10-), a keto bond sulfide bond (e.g. -6-), sulfinyl bonds (e.g. -S(○)-), sulfonyl bonds (e.g. -S(0)2-), alkylene bonds (e.g. -C ratio -
-, 1CH2-CH2-, etc.), alkylidene bonds (e.g., 1CR base-), alkylene ether bonds (e.g., 1CH20-, 1CH20-CH2-, 1C-C ratio ○-, 1 (CH2C, OCH2CH2, etc.), alkylene keto bonds (e.g., "alkylene sulfide bonds (e.g., those in which one or more of -○- in the above alkylene ether bonds are replaced with -S- atoms) ), alkylene polysulfide bonds (e.g., one or more of 10- in the above alkylene ether bond is replaced with 1S2-6- group), amino bonds (e.g. -N-, 1C ratio], 1CH2NCH2
-, alk-N-, alk is alkylene, etc.), polyamino bonds (e.g. *-N(alkN), ~,, where the valence of free N is satisfied by H or Ro group) {the above each Ro is a lower alkyl group)
It is a cross-linked bond selected from among the following. Specific examples of the crosslinked type polynuclear aromatic moiety Ar are listed below. Normally, all these Ar sites are R
The groups are unsubstituted except for the monoOH group and the -N02 group (and any bridging groups present). Due to reasons such as price, availability, performance, etc., ~ parts are
Typically, it is a benzene nucleus, a lower alkylene bridged benzene nucleus, or a naphthalene nucleus. That is, a typical Ar moiety is a benzene or naphthalene having 3 to 5 available valences, one or two of which are filled with hydroxyl groups, and the remaining available valences are filled with hydroxyl groups whenever possible. It is located in the ortho or para position relative to the Usually, Ar has three or four available valences, such that one available valence is filled by a hydroxyl group and the remaining two or three available valences can be located in ortho or rose positions with respect to the hydroxyl group. It has a benzene nucleus. Aliphatic substituent R The nitrophenol used in this invention has an aromatic moiety
contains a substituent R having at least about 1 solid carbon atom directly bonded to . The R group can have up to about 700 carbon atoms. This R group is usually aliphatic in character, but in some cases it may be substantially aliphatic, with each aliphatic carbon atom present having one carbocyclic ring. It may contain a group (for example, an aromatic group or an alicyclic group). However, typically the R group is a purely aliphatic group. One or more such R groups may be present, but
Usually there are no more than two or three for each aromatic nucleus in the aromatic moieties. Finally, although not required, one R group is present at each aromatic moiety. The total number of R groups is indicated by the numerical value of "a" in the above formula (1). usually,
The R groups are from at least about 3 to about 500;
More typically it has about 5 to about 50 carbon atoms. Only one R group and one OH per aromatic moiety
If a group is present, the R group is typically located para to the 10H group. Usually this aliphatic substituent R is hydrocarbyl in character. However, it may also be hydrocarbyl in nature, containing, in addition to carbon and hydrogen, oxygen (usually in the form of ether or hydroxyl groups), sulfur (usually in the form of sulfide or thiol groups) and halogens (usually in the form of sulfide or thiol groups). It is also possible to contain up to about 1% by weight of other elements, such as in particular chlorine and bromine. This R group is substantially saturated. This means that the R group can contain up to one carbon-carbon double bond with a carbon-carbon single bond IN style. However, preferably R is saturated. In general, the hydrocarbon group R is monopolymerized mono- and diolefins having 2 or 1 hard carbon atoms, such as ethylene, propylene, butene-1, isobutene, butadiene, isoprene, 1-hexene, 1-octene, etc. Derived from polymers or interpolymers (e.g. dipolymers, terpolymers). Typically, these olefins are aliphatic hydrocarbons.
- Monoolefins. A preferred source of R groups is
A C4 fraction with a total butene content of 30% to 75% by weight and an isoptene content of 20 to 60% by weight was polymerized in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. They are poly(butetanes). These polybutenes are primarily (i.e., 8 of the total repeating units)
Contains 0% or more of isobutene repeating units represented by the formula. A number of methods familiar to those skilled in the art can be used to attach the aliphatic substituent R to the aromatic moiety Ar of the nitrophenol used in this invention. One particularly suitable method is the Friedel-Klaff reaction, in which olefins (for example polymers with olefinic bonds) or their halides or hydrohalides are reacted with phenol. This reaction is carried out in the presence of a Lewis acid catalyst (for example, boron trifluoride and its rust form with ethers, phenols, hydrogen fluoride, etc., aluminum chloride, aluminum bromide, zinc dichloride, etc.). Procedures and conditions for carrying out this reaction are well known to those skilled in the art. for example,
"Alkylation of Phenols" described in "Encyclopedia of Chemical Technology", 2nd edition, Vol. 1, pages 894-895 (King, 1962) published by Interscience Publishers, Kirk-Osmer. See section. Equally suitable and convenient methods for attaching the hydrocarbon group R to the aromatic moiety Ar will be apparent to those skilled in the art. As can be easily seen from the above formula (1), the nitrophenol used in the present invention contains at least one of each of the following substituents. The substituents are a hydroxyl group, the above-mentioned R group, and a nitro group -N02. Each of these groups is bonded to a carbon atom that is part of the aromatic nucleus in the Ar moiety. However, when two or more aromatic nuclei are present in the ~ site, each of the substituents does not need to be bonded to the same aromatic ring. In a preferred embodiment, the nitrophenol used in this invention contains one or two of each of the above-mentioned direct substituents and only one mononuclear aromatic ring, preferably benzene. This preferred nit. Phenol is a fatty acid of the formula (in which R' is a fatty acid having an average of from about 30 to about 70, usually from about 50 to about 50, carbon atoms located ortho or para to the hydroxyl group). group substituent, R″ is a substituent selected from the group consisting of lower alkyl group, lower alkoxyl group and hao group, and z
is 0 or 1). The above substituent R' is of the same general nature as the substituent R described above, and what has been said about the R group also applies to the R' group. Usually R' is an alkyl or alkenyl group and z is zero. In a further preferred embodiment of the present invention, the nitrophenol is of the formula (in the above formula, R* is an alkyl group located at the bala position of the alkenyl groups having an average of about 50 to about 500 carbon atoms, R''
' is a substituent selected from the group consisting of a lower alkyl group, a lower alkoxyl group, a nitro group and a halo group, and z is 0 or 1). Typically R* is derived from a polymer of ethylene, propylene, butylene or mixtures thereof. Typically, R* is derived from a propylene or butylene polymer. In some embodiments, z is 0, and in other embodiments, z is 1 and R''' is a nitro group, and only one monoOH group is present, and the nitro group and the R group are Located in the ortho position of the group. The nitrophenol used in this invention can be produced by a number of synthetic techniques. The techniques vary in the type of reactions used and their order. For example, an aromatic hydrocarbon such as benzene is alkylated with an alkylating agent such as a polymeric olefin to produce an alkylated aromatic intermediate. This intermediate can be nitrated to produce, for example, a polynitro intermediate, and one of the nitro groups in the polynitro intermediate can be converted to a hydroxyl group by melting with caustic to yield the desired nitrophenol. Another useful means for producing the nitrophenol of this invention involves alkylating phenol with an olefinic alkylating agent to produce alkylated phenol. This alkylated phenol can be nitrated to obtain nitrophenol. Methods for the alkylation of phenols are well known to those skilled in the art, as described in Encyclopedia of Chemical Technology, supra. Processes for nitration of phenol are also well known. For example, the ``Nitrophenols'' section of the ``Encyclopidia of Chemical Technology,'' 2nd edition, 1st edition, and the section on ``Nitrophenols,'' published by Academic Press, 195
$year P. B. D. de la Mare and J. Day. Aromatic Supplements: Nitration and Aromatic Reactivities by J. G. Hoggett, Cambridge University Press, 1961, and Interscience Publishing See ``The Chemistry of the Nitro and Nitroso Groups'' by King Henry Fuel, 196. Aromatic hydroxy compounds are acids such as nitric acid, nitric acid and sulfuric acid or boron trifluoride, N02, N203
, N204, N2Q, N02CI, N02Br, a mixture of an alkali metal salt or alkali metal salt of sulfuric acid with a mineral acid (e.g., S04), an alkanoyl nitrate (e.g., acetyl nitrate), or a mixture of two or more of these. It can be nitrated by Generally, nitric acid at a concentration of, for example, about 30-90% is a convenient nitrating agent. Substantially inert liquid diluents and solvents, such as acetic acid and butyric acid, aid in the progress of the reaction by improving contact and heat transfer of the reactants. nitrates hydroxyaromatic compounds. Conditions and procedures for this are well known in the art. For example, the reaction may be carried out at temperatures ranging from about -15°C to about 150°C.
It can be carried out at a temperature of oo. Usually, the nitration of alkylphenols is conveniently carried out at about 25°C to 75°C. Generally, from about 0.5 to 4 moles of nitrating agent are used for each mole of aromatic nuclei present in the hydroxyaromatic compound to be nitrated, depending on the nitrating agent used. If more than one aromatic nucleus is present in the Ar site, the amount of nitrating agent can be increased proportionally depending on the number of aromatic nuclei. For example, since one mole of naphthalene-based aromatic intermediate has two "monocyclic" aromatic nuclei for purposes of this invention, about 1 to 4 moles of nitrating agent are generally used. When using nitric acid as a nitrating agent,
About 1.0 to about 3.0 moles are used per mole of aromatic nuclei. If the reaction is to be carried out quickly, the nitrating agent may be used in an excess of about 5 moles (per aromatic nucleus). Nitration of phenol generally takes 0.25 to 24 hours. However, it may be advantageous to react the nitration mixture for a longer time, for example 9 hours. A typical method for producing the nitrophenol of the present invention described above can be summarized as follows. That is, the general formula (R)aAr'(OH)C (wherein each R is an aliphatic substituent having at least about 30, typically from about 30 to about 700 carbon atoms, and at least One of them is located in the ortho or para position to at least one of the -OH groups directly bonded to the center. a and c are each independently 1, and 3 of the number of aromatic nuclei in Ar'. Ar'' has at least one hydrogen bonded to a carbon atom of an aromatic ring, and the sum of these does not exceed the effective valence number in ~'. At least one phenol having 0 to 3 substituents selected from the group consisting of an alkoxyl group, a halo group, a nitro group, and any combination thereof; This method involves nitration using a nitration agent. Regarding the points other than the above, ~' is the same as Ar, and what has been said about Ar also applies to Ar'. Typically, A is benzene, and R has on average from about 5N up to about 500 carbon atoms, and is typically C2 to C, a monomer of olefins or mixtures thereof. Such nitrophenols typically have the formula (above formula, where R' and R'' are as previously described and R' is usually in the ortho or para position of the hydroxyl group. and z is 0 or 1)
It is obtained by nitrating a species of compound with at least one nitrating agent. In formula (W) above, R' is typically located at the para position of the hydroxyl group, and z is 0. Certain nitrophenols with aromatic nuclei used in this invention can be synthesized by several procedures. For example, a hydrocarbon-substituted phenolic compound as described above is first reacted with a crosslinking agent such as an aldehyde or ketone (e.g. formaldehyde) to produce a product having, for example, methylene bridges between the aromatic nuclei. can do. This crosslinked product can then be nitrated by the steps described above to obtain the desired crosslinked nitrophenol. This procedure can be shown as follows. Alternatively, the desired crosslinked nitrophenol can be obtained, for example, by reacting the nitrophenol having a monocyclic or fused polycyclic aromatic moiety prepared as described above with a crosslinking agent such as aldehyde or formaldehyde. This procedure can be shown as follows. Still another method for producing the crosslinked nitrophenol having a crosslinked aromatic nucleus used in the present invention is a method of condensing a hydrocarbon-substituted phenol with a hydrocarbon-substituted or unsubstituted nitrophenol using a crosslinking agent such as sulfur or formaldehyde. . This method can be shown as follows. The above formula (V)
In (skin), R and R''' are as described above. Hydradiso source {B - The hydrazine source used in this invention is a compound or compound capable of producing a sufficient amount of hydrazine to react with the nitrophenol ■ present under the reaction conditions of the reactant ■ and the leg. It is a mixture of Many such sources of hydrazine will be apparent to the practitioner. For example, Charles C. "Hydrazine" by Clark
(Machieson Chemical Corporation, 195
3 King), especially pages 31 to 71 and pages 120 to 124, and L. F. Audreys and B. A.
“The Chemistry of Hydrazine” by Otsugu (John Willey & Son, 1951), especially 2.
See pages 09-223. Preferred sources of hydrazine are hydrazine itself, hydrated hydrazine and solutions of hydrazine and water, as well as hydrazine salts and similar salts of, for example, semicarbazide sulfate and thiosemicarbazide sulfate or semicarbazide hydrochloride and thiosemicarbazide hydrochloride, hydrazine dihydrazine of lower alkanols, etc. Carboxylates (e.g. ROOCNHNHCOOR) and their dimers, and also aminoguanidine and its monoNHCOOR
NH-sulfate/hydrochloride, benzenesulfonyl hydrazide and its bisoxy analogues. Mixtures of hydrazine sources may also be used. The examples listed here do not mean that they are the only sources of hydrazine. Many other useful sources of hydrazine will be apparent to those skilled in the art. For reasons of economy and ease of handling, hydrazine and especially its solutions with water or other solvents/diluents are preferred. A typical source of hydrazine is a mixture of water and hydrazine containing about 64% hydrazine. However, mixtures containing greater or lesser amounts of hydrazine (approximately 20-80% hydrazine, currently approximately 30-70% hydrazine) may also be used. For example, the above-mentioned documents and "Cyclopedia of Chemical Technology" by Kirk Osmer published by Interscience Publishers, Vol. 11, 2nd edition, Volume 1.
See the "Hydrazine" section on pages 64 to 196 (page 196). Reaction of nitrophenol with hydrazine source 'B' In the process for making nitrogen-containing compositions of this invention, from about 1.5 to about 5 moles of hydrazine source 'B' are present per equivalent of nitrophenol. One mole of the hydrazine source corresponds to the amount that produces one mole of hydrazine (NH2N ratio) under the reaction conditions as described above. One equivalent of nitrophenol corresponds to the amount of nitrophenol having 1 mole of nitro groups. For example,
One mole of nitrophenol contains one mole of nitro groups, and one mole of dinitrophenol contains two moles of nitro groups. Therefore, dinito 0 phenol 1
The equivalent amount is half the amount of 1 mole of dinitrophenol. Preferably, from about 1.5 to about 2.5 moles of hydrazine source are present per equivalent of nitrophenol. The hydrazine source does not need to be present entirely from the beginning of the reaction between the reactants and the reactants, and may be added continuously or in increasing amounts as the reaction progresses. What is necessary is that the said amount be introduced into the reaction system before the end of the reaction. For reasons of economy and convenience, it is desirable to react a stoichiometric amount of the hydrazine source with the nitrophenol. However, as is clear to those skilled in the art,
Finally, the organic reaction does not proceed until the stoichiometric amount of the reactants has been consumed. In this invention, it is sufficient that only about 50 mole percent of the nitro groups present in the nitrophenol have reacted with the hydrazine source. The reaction of the reactants with 'B' generally occurs at temperatures above 50 qo. Typically, this reaction occurs at a temperature of about 100° C. or more and about 350 qo or less. Generally, the reaction between reactant 1 and the leg is carried out for about 2 to about 2 hours, although longer times, such as about 9 hours, can be used. Typically the reaction occurs in about 4 to 8 hours, currently about 6 hours. The nitrogen-containing composition of this invention can be recovered by isolation and purification methods well known to those skilled in the art, such as distillation, extraction, crystallization, and centrifugation. However, the nitrogen-containing composition can usually be used for its intended purpose without purification from the mixture from which it is produced. Occasionally, appearance and/or
From the point of view of storage stability, it is treated by simple purification means such as filtering using well-known filter aids such as diaphragm or charcoal powder. As mentioned above, the reactants and [B
The reaction with at least one metal-containing hydrazine decomposition catalyst
Can be carried out in the presence of seeds. Many such catalysts are known to those skilled in the art and the following description is exemplary only. For a general discussion of the reactions of hydrazine and hydrazine sources with the above catalysts, see ``Hydrazine'' and ``The Chemistry of Hydrazine'', supra, as well as ``Encyclopedia of Chemical Technology'', supra. Reference to "Hydrazine".
Examples of metals that can be contained in the hydrazide decomposition catalyst useful in this invention include platinum, palladium, nickel, copper,
Examples include iron, ruthenium, cobalt, rhodium, osmium, and mixtures of two or more of these. These catalysts can be pure metals, alloys of various metals, metal compounds such as inorganic salts or oxides, metal salts with organic acids such as carboxylates or sulfonates, or combinations with suitable ligands. It doesn't matter if it's in place. These catalysts are commonly used in mass production such as unsupported metal powders, thin metal films deposited on active or inactive substrates or electrodes, and in berets, spiral windings, etc. It can be used in any shape. Particularly preferred are finely divided metals commonly known as hydrogenation catalysts, such as palladium,
There is platinum and nickel. Metals that have been chemically or physically treated to modify their activity (eg Raney nickel) are increasingly used. See, for example, the literature cited in ``Hydrazine as a Reducing Agent for Organic Compounds'' in ``Chemical Reviews,'' cited above. at present,
It is believed that the reaction between nitrophenol and hydrazine source 'B' primarily produces aminophenol in which one or more of the nitro groups in the nitrophenol are replaced with amino groups. (i) the hydrazine source is consumed during the reaction; (ii)
) the reduction or disappearance of the infrared absorption band attributed to the nitro group in the spectrum of the nitrophenol wind, the presence of nitrogen in the final product, and the formation of water, usually during the reaction of G. It is known. These observations are compatible with the assumption that the hydrazine source is reducing the nitro group of nitrophenol, possibly to the amino group. However, the invention should not be limited by such assumptions, but rather is defined as set forth in the specification. Examples of this invention will be described below. All "parts" and "%" are by weight unless otherwise indicated. Example 1 Alkylphenol was produced by reacting phenol with polybutene having a number average molecular weight of about 1000 (gas phase triosmotic pressure method) in the presence of a boron trifluoride/phenol catalyst. The catalyst was neutralized and removed by filtration. The product was first heated to 230°C/76°C (vapor phase temperature) and then to 205°C.
The purified alkylphenol was obtained as a shallow thin layer by stripping to ℃/5℃ or (gas phase temperature). A mixture of 265 parts of this refined alkylphenol, 176 parts of mixed mineral oil, and 42 parts of petroleum naphtha having a boiling point of about 2.
~70%) A mixture of 18.4 parts of nitric acid and 35 parts of water was slowly added. The reaction mixture was heated at about 30-45°C for 3 hours, and
It was stripped to 0°C/2°C (gas phase temperature) and filtered to obtain an oil solution of the desired alkylated nitrophenol. Example 2 190 parts of the alkylated nitrophenol solution of Example 1 in natural oil containing 43% mineral oil was heated to 1460 parts under a nitrogen atmosphere.
It was heated to Then, 7 parts of hydrated hydrazine was slowly added to this over 5 hours while maintaining the temperature at 145,000°C. The mixture was then heated to 160 qo for 1 hour, during which time 56 parts of aqueous distillate were collected. An additional 7 parts of hydrated hydrazine were added and the mixture was held at 140°C for an additional hour.
Filtration through 130 mm gave an oil solution of the desired product containing 0.5% nitrogen. Example 3 72 parts of concentrated nitric acid was added to a mixture of polyptene-substituted phenol 80 produced in the same manner as in Example 1 and 944 parts of diluted mineral oil at 59°C. The reaction was controlled to maintain the reaction temperature between 59 and 68°C. The reaction mixture was heated at 69-7yo for 2 hours and then heated to 140qo while nitrogen was slowly passed through and water was removed by distillation. To this mixture was added 90% of hydrated hydrazine at 130-1370°C over 3 hours. The reaction mixture was heated at the above temperature to 0. It was heated for an hour and then heated to 160°C while nitrogen was slowly passed through and the aqueous distillate was collected. The residue was an oil solution of the desired product. Example 4 60 parts of polybutene-substituted phenol produced in the same manner as in Example 1 and 454 parts of diluted mineral oil were mixed at 570 g. To this mixture was added 46.5 parts of 66.3% nitric acid over 8 hours. The resulting mixture was stirred at ~63 qo for 1.5 hours, then 1. The reactor was heated to 142° C. for a short period of time, and nitrogen was slowly passed through the reactor during that time. This mixture is 143-14
It was held at 5°C for 0.5 hour and then cooled to 114°C.
During this reaction, 2 parts of distillate were collected. 1 of this mixture
An oil solution of the desired nitrophenol containing 0.64% nitrogen was obtained by filtration at 13-126°C.
Example 5 The nitrophenol oil solution of Example 4 was mixed with 12 hydrazine aqueous solutions containing 64% of hydrazine.
Addition took place over 6.25 hours at 0°C. Filtration gave an oil solution of the desired product with a nitrogen content of 0.59%. Example 6 A mixture of 300 parts of an alkylphenol having a polybutene substituent containing about 7 solid carbon atoms, obtained as in Example 1, and 300 parts of glacial acetic acid was
540 parts of concentrated nitric acid was added over 3 hours. The mixture was kept at 51-6yo during this addition. The resulting mixture was left at room temperature for 18 hours, then 6 hours at 12 hours.
The mixture was heated to 0°C while nitrogen was slowly passed through. Aqueous distillate was also collected. The reaction mixture was then stripped to 140 pm or 2 oz (vapor phase temperature) and heated to 12 ml.
The desired final product with a nitrogen content of 2.55% was obtained by filtration at 0°C. On this basis, the product was calculated to contain on average 2 nitro groups per alkylphenol. Example 7 To a mixture of 545 parts of the alkylated dinitrophenol of Example 6 and 34 parts of diluted mineral oil was added 10 parts of hydrated hydrazine at 125°C. This addition was carried out for 2.5 hours under a nitrogen atmosphere while maintaining the temperature at 122-12yo. This reaction mixture was then treated with 123 qo for 2. It was refluxed for an hour and heated to 155° C. for an additional 2 hours, during which time the aqueous distillate was collected. The reaction mixture was slowly bubbled with nitrogen for an additional 2 hours at 150-155 qC and the retentate was filtered to a nitrogen content of 1.16.
% of the desired product was obtained. Example 8 361 parts of tetraprobenyl-substituted phenol and 27 parts of glacial acetic acid
Nitric acid (70% HN03) at 7-17 °C in a mixture with 1 part
A mixture of 9 parts and 9 parts of glacial acetic acid was added. This addition is carried out while externally cooling the reaction mixture by means of a cooling bath to 7-170 mL. It took me a long time to do it. The cooling rack was removed and the reaction mixture was allowed to stand at room temperature for 2 hours. This was stripped to 134oo/35tor (gas phase temperature) and filtered to yield the desired nitrophenol with a nitrogen content of 65% as a residue. Example 9 To 303 parts of the nitrophenol of Example 8 was added 125 parts of nitrophenol under nitrogen.
00, 100 parts of hydrazine hydrate was added over 2.4 hours. Add this mixture to 2. The mixture was refluxed for a lifetime and distilled to a gas phase temperature of 155°C. The temperature of this reaction mixture was set to 155 to 190 qo.
Nitrogen was slowly passed through while maintaining the temperature. The retentate was filtered to obtain the desired final product with a nitrogen content of 4.89%. Example 10 A solution of the alkylated nitrophenol of Example 1 in mineral oil (200 parts) (43% Shigeru oil) was dissolved in a nitrogen atmosphere for 1 hour.
Ripened at 50°C. 135 parts of semicarbazide were then slowly added to the mixture over 6 hours while maintaining the temperature at about 150°C. It was incubated at this temperature for 1 hour, then heated to 175°C while slowly introducing nitrogen, and the water fraction was collected. The residue was an oil solution of the desired product. Example 11 Alkylated nitrophenol of Example 1 in mineral oil (111
1 part) solution (containing 43% mineral oil) under nitrogen atmosphere at 150%
It was heated to qo. To this mixture, maintaining its temperature at about 160 qo,
264 parts of hydrazoformate (hydrazodicarboxylic acid ester) was slowly added over 3 hours. The mixture was heated at the same temperature for about 2 hours, then heated to 18,000 ℃ while nitrogen was introduced, and the water fraction was collected. The residue was an oil solution of the desired product. As previously stated, the nitrogen-containing compositions of this invention are useful as additives for oil-based lubricating compositions having lubricating viscosity. This lubricating composition is used in a variety of applications such as lubricating internal combustion engines. The compositions of this invention act as detergents and dispersants for engine sludge that accumulates in oil during use. The compositions of this invention are particularly useful in oils that are subjected to high temperature and cyclic operations, such as those found in on-off and heavy duty engine operation. The lubricating compositions of this invention include Otto cycle and 2 cycle (2 cycle)
There are crankcase lubricants for spark-ignition and compression-ignition internal combustion engines, such as (stroke) automobile and truck engines, marine and railroad diesel engines, etc. In this regard, the Wankel engine is considered to be a two-stroke engine. The lubricating composition of the present invention can also be used in engines used for power landscaping machines, saws, and other uses. Additionally, the compositions of this invention are useful in automatic transmission fluids, transmission shaft lubricants, gear lubricants, industrial oils such as metalworking lubricants, pressure fluids, and other lubricating oil and grease compositions. . The lubricating compositions of the invention can be based on natural oils, synthetic oils, natural oil mixtures, synthetic oil mixtures, natural oil-synthetic oil mixtures. Natural oils include animal oils and vegetable flours (e.g. castor oil and lard oil), as well as liquid petroleum or paraffinic oils.
Examples include naphthenic or mixed paraffinic-naphthenic solvent-treated or acid-treated mineral lubricating oils. Oils of lubricating viscosity derived from coal or tribute rock are also useful base oils. Synthetic lubricating oils include hydrocarbon oils such as homopolymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.) and halo-substituted hydrocarbon oils, poly(1 -hexene), poly(1-octene),
Poly(1-decene) etc. or mixtures thereof, alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)-benzenes etc.), polyphenyls (e.g. biphenyls, terphenyls, alkylated polyphenyls, etc.), alkylated diphenyl ethers, alkylated diphenyl sulfides, and derivatives, analogs, and congeners thereof. Homopolymers and interpolymers of alkylene oxide, as well as derivatives thereof whose terminal hydroxyl groups have been modified by esterification, etherification, etc., also constitute another group of known synthetic lubricating oils. Examples of this include oils obtained by polymerizing ethylene oxide and propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (e.g. methylpolyisopropylene glycol ether with an average molecular weight of 1000, polyethylene glycol with a molecular weight of 500-1000). diphenyl ether, molecular weight 1000-1500
(such as diethyl ether of polypropylene glycol) or their mo/and polycarboxylic acid esters, such as acetate esters, mixed C3-C8 fatty acid esters or C3 oxoacid esters of tetraethylene glycol. Other suitable groups of synthetic lubricating oils include dicarboxylic acids (e.g. phthalic acid, succinic acid, alkylsuccinic acid,
Alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid diamic acid, malonic acid, alkylmalonic acid, alkenylmaic acid. esters of various alcohols (eg, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters are as follows. That is, dibutyl adipate, di(2-ethylhexyl) sebacate,
Dinormalhexyl fumarate, dioctyl sebacate,
Diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, jaicosyl sebacate, 2-ethylhexyl gester of linoleic acid dimer, 1 mole of sebacic acid, 2 moles of tetraethylene glycol, and 2 moles of 2-ethylcaproic acid. It is a compound ester etc. Esters useful as synthetic bottles include C5-C,2 monocarboxylic acids and polyols and polyol ethers, such as trimethylolpropane, bentaerythritate, diventaerythritate, and tribentaerythritol. There is something manufactured. polyalkyl, polyaryl, polyalkoxy,
Alternatively, silicone-based oils such as polyaryloxysiloxane oils and silicate oils constitute another useful group of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra(2-ethylhexyl silicate)).
, tetra(4-methylhexyl) silicate, tetra(para-tertiary butylphenyl) silicate, hexyl-(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes, poly(methylphenyl)siloxanes, etc.) .
Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid, etc.), polymerized tetrahydrofurans, and the like. The natural and synthetic types mentioned above (
unrefined oil (including mixtures of two or more of these),
Both refined and rerefined oils may be used in the lubricating compositions of this invention. Unrefined oils are those obtained directly from natural or synthetic sources without additional refining treatment. For example, shale oil obtained directly by retorting, petroleum oil obtained directly by primary distillation, or ester oil obtained directly by esterification and used without further treatment are unrefined oils. Refined oils are similar to refined oils except that they have been treated in one or more refining steps to improve one or more properties. The above purification methods are well known to those skilled in the art. For example, solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by applying the processes used to obtain refined oils to already used refined oils. Such rerefined oils are also known as reclaimed oils and are then further processed by methods to release spent additives and oil breakdown products. Generally, to obtain a satisfactory lubricant composition, about 0.05 to 3 parts by weight of at least one nitrogen-containing composition of this invention, usually about 0.1 to 1 part by weight, should be added to 10 parts by weight of oil.
Dissolve or stably disperse in a proportion of 5 parts by weight. The lubricant composition may contain, in addition to the composition of the invention, other additives commonly used in lubricants. Such additives include, for example, ash-forming and ashless auxiliary detergents and dispersants, antioxidants, pour point depressants,
There are defoamers, extreme pressure agents and color stabilizers. As used in this specification and claims, the term "stably dispersed" means that a composition (e.g., a single additive or compound, or a mixture of two or more thereof) is It means that it can be dispersed in a certain medium to the extent that it can function. Thus, for example, when a composition of the invention is used in an oil, the dispersed composition may be sufficiently dispersed or suspended in the oil to cause the oil to have one or more desired properties. good. Such dispersion or suspension can be accomplished by conventional methods such as, for example, constant oil circulation or splashing in various lubricating systems. Additionally, conventional dispersants often used in lubricating oils and fuels (e.g., U.S. Pat. No. 3,219,966
Stable dispersion or suspension of the composition of the present invention can be promoted by the acylated nitrogen-based dispersant described in No. 6).
In any event, the compositions of this invention are "dissolved" or "stably dispersed" in the normally liquid medium to which they are added, to at least the minimum concentrations mentioned herein. That is, the terms "dissolve" and "stably disperse" are used in their usual meanings and will be readily understood by those skilled in the art. The term "substantially inert" as used with stocks, etc. means that the solvent, diluent, etc. is inert to chemical or physical changes under the conditions under which it is used. It is used in the sense that it does not substantially adversely affect the preparation, storage, incorporation and/or operation of the nitrogen-containing composition, additives, etc. of the present invention when used. For example, a small amount of solvent, diluent, etc. may react or deteriorate slightly as long as it does not impede the implementation of the present invention. In other words, such reactions and deterioration, although understandable from a purely technical point of view, do not impede the practice of this invention. The nitrogen-containing compositions of this invention can also be used in fuels, where they act as engine sludge cleaners and dispersants, carburetor cleaners, and demulsifiers. The fuel composition of the present invention is a hydrocarbonaceous petroleum distillate fuel (e.g., motor gasoline as specified in ASTM Specification D-439-73, diesel fuel or fuel oil as specified in ASTM Specification D-396). It usually contains a large amount of liquid fuel such as. Normally liquid fuel compositions consisting of non-hydrocarbons such as alcohols, ethers, and organic nitro compounds (e.g. methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) can also be used in combination with corn, purple corn, tributary coal, and coal. Also within the scope of this invention are fuel oils derived from vegetable and mineral sources such as. Fuel oil consisting of any of the above mixtures can be used. Examples of such mixtures include:
There are gasoline and ethanol, diesel fuel and ether, gasoline and nitromethane, etc. Particularly preferred is gasoline, with a 10% distillation point of 60° according to ASTM.
It is a mixture of hydrocarbons with a 90% distillation point of about 205 qo. Generally, the fuel composition will contain at least one of the compositions of this invention in an amount sufficient to impart dispersing and cleaning or emulsifying properties to the fuel. In general, this amount is from about 1 to about 1000 parts by weight, preferably from 4 to 100 parts by weight, per million parts by weight of fuel. Preferred are gasoline-based fuel compositions that exhibit engine sludge dispersion and cleaning properties as well as carburetor cleaning properties. The fuel compositions of this invention may contain, in addition to the products of this invention, other additives known in the art. Such additives include anti-knock agents such as tetraalkyl lead compounds, lead scavengers such as haloalkanes (e.g. ethylene dichloride, ethylene dibromide), and anti-settling agents such as triaryl phosphates/modifiers. agents, dyes, cetane improvers, antioxidants such as 2,6-di-tert-butyl-4-methylphenol, rust inhibitors such as alkylated succinic acids and their anhydrides, bacterial growth inhibitors, guminhibirs. In addition, there are metal deactivators, scale emulsifiers, ice quenching agents, etc. Refined oils, especially bright stocks, or oily homopolymerized or interpolymerized lower olefins, such as ethylenenopropylene copolymers, polypropylene, and polybutene, are used as fuels to reduce deposit formation in the induction systems of engines using such fuels. Currently used in compositions. In a preferred fuel composition of this invention, the nitrophenol of this invention is used in conjunction with an ashless dispersant of the pond type in gasoline. Such ashless dispersants are preferably esters of mono- or polyols and high molecular weight mono- or polycarboxylic acylating agents in which the acyl moiety has at least 3 hard carbon atoms. Such wastes are well known in the art. For example, French Patent No. 1396645,
UK Patent Nos. 98195 and 1055337, as well as US Patent Nos. 3255108 and 3311.
No. 5, No. 3331776, No. 3346354, No. 3522179, No. 3579450, No. 3542680, No. 3381022, No. 363
No. 9242, No. 3697428, No. 370852
No. 2, see also British Patent No. 130652y. in general,
from about 0.1 to about 10.0% per part of the above ashless dispersant. Anchor, preferably from about 1 to about 1 part of the composition of this invention is used. In another embodiment of this invention, the nitrogen-containing compositions of this invention are used in conjunction with Mannitz condensation products made from substituted phenols, aldehydes, polyamines, and aminopyridines to provide lubricants and/or
A fuel additive is obtained. Such condensation products are described in U.S. Pat.
No. 704308 and No. 3724277. The nitrogen-containing composition of this invention may be added directly to the above-mentioned fuels or lubricants to form fuel or lubricant compositions, or may be added to shark oil, xylene, alcohol, nitro-lower alkanes, chloro-lower alkanes. Alternatively, the normally liquid fuels described above may be diluted with at least one substantially inert normally liquid organic solvent/diluent to form a concentrate, and the concentrate may then be used in sufficient quantities to form a fuel or lubricant. Additionally, the fuel and lubricant compositions described above may be made. The concentrates generally contain from about 30% to about 9% by weight of the nitrogen-containing composition of this invention. The concentrate may also contain the usual additives mentioned above, in particular ashless dispersants, in the proportions mentioned above. The remainder of this concentrate is solvent/diluent. This invention includes 2 containing the nitrogen-containing composition.
Also includes lubricating oil for cycle engines. Generally, the two-stroke engine lubricating oil composition contains an oil or mixture thereof having a lubricating viscosity of about 98% to about 5%
Contains 5%. Typical compositions range from about 90% to about 7%
Contains 0% oil. Presently preferred oils are key oils and key oil-synthetic polymer and/or ester oil mixtures. Oily polybutenes and fatty acid ester oils of polyols such as pentaerythritol and trimethylolpropane with molecular weights from about 250 to about 1000 (by gas phase osmometry) are typical useful synthetic oils. The compositions contain from about 2 to about 30%, typically from about 5 to about 20%, of at least one of the previously mentioned nitrogen-containing compositions. Additives such as ash-forming or bran-type auxiliary cleaning and dispersing agents, antioxidants, coupling agents, pour point depressants, extreme pressure agents, color stabilizers and antifoaming agents may be present. . Bran or ash-forming metal type detergents and dispersants are used to control piston ring sticking and general engine cleaning. Heavy duty two-stroke engine lubricants require suitable ashless dispersants. This is because ash-forming detergents tend to create combustion chamber deposits that compromise pre-ignition. Other compositions used in less severe conditions employ calcium, barium or magnesium sulfonates or phenoxides alone, in mixtures, or with ashless dispersants. Antioxidants may be added to improve the thermal stability of the lubricant. Polymeric viscosity index improvers have been used to improve lubricant film strength and lubricity and improve engine cleanliness. Dyes can be used for identification purposes and to determine whether a two-stroke engine fuel mixture contains lubricant. Coupling agents are added to some products to improve component solubility and improve the water solubility of the fuel/lubricant mixture. For special applications such as competition or where fuel/lubricant ratios are very high, anti-wear and lubricity improvers, especially sulfurized whale oil and its substitutes and other fatty acids and vegetable oils such as castor oil, may be used in two-stroke engine oils. used inside. Lead scavengers and combustion chamber deposit modifiers are sometimes used to promote spark plug life and remove carbon deposits. Halogenated compounds and/or phosphorus-containing materials can be used in this application. Two-stroke engine oils may contain any type of anti-rust or preservative. Fragrance agents and deodorizers are sometimes used for aesthetic reasons. Synthetic polymers (e.g., those with a number average molecular weight of about 750 by gas phase osmometry or gel permeation chromatography)
polyisobutene), polyol ethers (e.g. poly(oxyethylene-oxypropylene) ether) and ester oils (e.g.
Lubricating agents such as ester oil (as described above) are also used in the two-stroke engine oil compositions of this invention. Natural oil fractions such as bright stock (a relatively viscous product obtained during the normal process for obtaining lubricating oils from petroleum) can also be used for this purpose. Typically, they are present at about 3% to about 20% of the total two-stroke engine oil composition. As previously mentioned, the two-stroke engine oil compositions of the present invention may also include auxiliary detergent and dispersants. Typical examples thereof include fatty acids having 5 to 22 carbon atoms (e.g., isostearic acid or a mixture of isostearic acid and stearic acid), 2 to about 1 amino group, and alkylene groups having 2 to 20 carbon atoms. Amides, amine salts and/or amidine products obtained by reacting with polyamines such as ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenebentaamine, as well as commercial mixtures of these alkylene polyamines. Such auxiliary cleaning and dispersing agents are shown in U.S. Pat. No. 3,169,989.
Diluents such as petroleum naphtha (e.g. Stoddard Solvent) having a boiling point of about 38 to 90 qo may also be present in the oil compositions of this invention, typically from 5% to 25%. One example of a two-stroke engine lubricant composition of the present invention includes 2 to 10% of one or more nitrogen-containing compositions as shown in Example 2, and about 70 to 8 parts by volume of 650 neutral oil. It contains a base oil consisting of 8 to 12 parts by volume of Brightstock and 10 to 2 parts by volume of Stoddard Solvent. As is well known to those skilled in the art, two-stroke engine lubricating oils can be added directly to fuel to create an oil and fuel mixture that is then introduced into the engine cylinder. Such lubricant-fuel oil mixtures are within the scope of this invention. Such lubricant-fuel blends generally contain about 15 to 25 anchor cities of fuel per part of oil, typically about 50 to 10 anchor cities. Other typical examples of the two-stroke engine lubricating oil of the present invention are described below. Ingredients Weight % '11 Solvent refined neutral oil with a viscosity of 65$US at 98.8oo [viscosity 15$US at 2'98.800

Claims (1)

[Claims] 1 (A) General formula ▲ Numerical formulas, chemical formulas, tables, etc. R″ is a substituent selected from the group consisting of a lower alkyl group, a lower alkoxyl group, and a halo group, and z is at least one type of substituent represented by 0 or 1) Nitrophenol at a temperature of about 50° C. or higher (B) selected from the group consisting of hydrazine, semicarbazide, hydrazine dicarboxylate of a lower alkanol, a mixture of two or more of these, and a mixture of one or more of these with water. A nitrogen-containing composition useful as a fuel or lubricant additive, characterized in that the hydrazine source is reacted with a hydrazine source in a proportion of about 1.5 to about 5.0 moles per equivalent of the nitrophenol. 2. The method of claim 1, wherein z is 0 and R' is an alkyl or alkenyl group. 3. R' has an average of about 50 to about 500 carbon atoms. The manufacturing method according to claim 2, characterized in that 4 R' is a polybutene-derived group located at the para position of the -OH group.