CA1075265A

CA1075265A - Hydrocarbon-substituted methylol phenols

Info

Publication number: CA1075265A
Application number: CA260,788A
Authority: CA
Inventors: John F. Pindar; Jerome M. Cohen; Charles P. Bryant
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1975-09-15
Filing date: 1976-09-08
Publication date: 1980-04-08
Also published as: IT1066451B; MX147062A; JPS6247860B2; JPS5236639A; ES451559A1; DE2641315A1; FR2323755B1; IN144604B; ZA765444B; FR2323755A1; GB1519743A; BR7605958A

Abstract

ABSTRACT OF THE DISCLOSURE
Hydroxy aromatic compositions containing (a) a hydroxyl group bonded directly to a carbon of an aromatic nucleus, (b) a hydrocarbon-based substituent of at least about 50 aliphatic carbon atoms bonded directly to a carbon atom of an aromatic nucleus, (c) at least one methylol or lower hydrocarbyl substituted methylol substituent bonded directly to a carbon atom of an aromatic nucleus, and not having any alkylene linkages between carbon atoms of two aromatic nuclei are useful as additives for normally liquid fuels and lubricating oils. These hydroxy aromatic compositions are also useful as intermediates for preparing other additives for fuels and lubricants. Typical hydroxy aromatic compositions of the prevent invention are formed by reaction of formaldehyde with an alkenyl- or alkyl-substituted phenol wherein the alkyl or alkenyl substituent contains an average of about 50 carbon atoms.

Description

1075;~iS
Background of the Invention (1) Field of the Invention This invention relates to aromatic hydroxy compositions useful as additives for lubricants based on oils of lubri-cating viscosity and normally liquid fuels. More parti-cularly, it relates to hydroxy aromatic compositions bearing a substituent of at least about 50 aliphatic carbon atoms and a methylol or substituted methylol group.

(2) Prior Art Hydrocarbon-substituted phenols containing methylol or substituted methylol groups are known in the art. See, for example, U.S. Patents 3,306,938; 2,912,395; and 3,127,251 as well as British Patent Specification 634,960.
The reaction of alkyl phenols containing alkyl sub-sti~uents o~ 400 to 5,000 molecular weight with formaldehvde has been reported to give bis(methylol-hydroxy-alkylbenzyl) compounds which afford detergency/dispersancy properties to oils containing them; see for example, U.S. Patent 3,737,465.
The '465 patent also points out that many resinous phenol formaldehyde condensation products of high molecular weight ahd complex structure are also known.

(3) General Background Over the past several decades, a number of additive compositions have been developed which improve the per-formance characteristics of lubricants and normally liquidfuels to which they are added. Still, increasingly severe operating conditions as well as raw material shortages, environmental consciousness and increasing costs has spurred the search for and development of novel additives for fuels and lubricants. Therefore, it is an object of this inven-:~075Z65 tion to provide novel lubricant and fuel additives. A
further object is to provide novel lubricants and fuels.
A still further object is to provide novel concentrates of such additives.
It is also an object of this invention to provide novel intermediates for fuel and lubricant additives.
Other objects will be apparent to those skilled in the art upon review of the present specification.
Summary of the Invention The objects of this invention are achieved by providing compositions comprising at least one hydroxy aromatic com-pound having:
(a) at least one hydroxyl substituent bonded directly to a carbon atom of an aromatic moiety, Ar, (b) at least one hydrocarbon-based substituent of at least about 50 aliphatic carbon atoms and less than about 300 carbon atoms bonded directly to a carbon atom of the aromatic moiety, Ar, and (c) at least one methylol or lower hydrocarbon-based substituted methylol substituent bonded directly to a carbon atom of the aromatic moiety Ar, said compound not having any alkylene linkages between carbon atoms of two aromatic nuclei. Lubricants based on oils of lubxicating viscosity, normally liquid fuels and additive concentrates containing the above-described compo-sitions are also within the scope of this invention.
Detailed Description of the Invention -The aromatic moiety, Ar, can be a single ring nucleus such as a benzene ring, pyridine ring, thiophene ring, etc., or a polynuclear aromatic moiety. Such polynuclear 10752~iS

moieties can be o~ the fused type (e.g., wherein two rings are ~fused at two points to another ring, such as found in naphthalene, anthracene, etc.) or they can be of the linked type, wherein individual aromatic rings (of either the mono-or fused polynuclear type) are linked through divalentbridging linkages. Such bridging linkages can be chosen from the group consisting of carbon-to-carbon single bonds;
ether linkages (such as -CH20CHz-); sulfide linkages (such as -S-); polysulfide linkages of 2 to 6 sulfur atoms (such as -S2- 6-); sulfinyl linkages (such as -S(O)-); sulfonyl linkages (such as -S(O) 2-); lower alkylene sulfur linkages (such as -CH2CH2 S-); lower alkylene polysulfide linkages of 2 to 6 carbon atoms (such as -CH2 S2-6 -); amino linkages ~such as -NH-); polyamino linkages (such as -(CH2CH2N) 1 - 1 o-);
and mixtures of such divalent bridging linkages. When Ar is a linked polynuclear aromatic moiety, generally there are not more than about 20 individual nuclei present and thus no more than 19 linkages. As stated above, the hydroxy aromatic compounds of this invention do not contain any alkylene linkages (e.g., methylene, -CH2-) between aromatic rings.
When Ar is polynuclear the hydroxyl substituents, aliphatic substituents, and methylol substituents can be bonded to different nuclei.
Generally Ar is a ring nucleus or a fused double ring nucleus which can be represented by the general formula Ar' wherein Ar' is a benzene, naphthalene, X-substituted benzene or X-substituted naphthalene nucleus, X being selected from the group consisting of lower alkyl substituents, lower alkoxy substituents, lower mercapto substituents, fluorine atoms, chlorine atoms and nitro substituents. There may be two or more X substituents per Ar' and such X substituents 1(~75;~5 ``

may be thc same or different. When such X substituents are present in Ar' they are not present to such an extent as to prevent attachment of at least one Cso+ hydrocarbon substi-tuent, at least one hydroxyl substituent and at least one methylol or substituted methylol substituent on Ar'. Usually, no more than two X substituents are present in Ar'. Typically, Ar' is a benzene or naphthalene nucieus not having any X
substituents.
Exemplary of Ar' nuclei are: benzene, toluene, xylene, anisole, fluorobenzene, chlorobenzene, nitrobenzene, methoxy-anisole, ethylbenzene, heptylmethylbenzene, methylmercapto-benzene nuclei. A benzene nucleus is preferred because of the ready availability of compounds providing such a nucleus.
As used in this specification, the term "lower" in conjunction with, for example, alkyl and alkoxy, refers to groups having 7 or less carbon atoms such as alkyl and alkoxy groups.
The hydroxy aromatic compounds of the present invention have at least one hydrocarbon-based substituent of at least about 50 aliphatic carbon atoms which can be conveniently represented by R. Generally R has less than about 300 carbon atoms and usually it has between about 70 and about 200 carbon atoms. Although R is aliphatic in nature it can contain small amounts of carbocyclic groups (e.g., cyclo-alkyl or aromatic), such as one group for every 20 non-cyclic aliphatic carbons, which do not significantly alter its aliphatic character. Usually, however, R is purely aliphatic and contains only aliphatic carbon atoms.
As used herein, the term "hydrocarbon-based substi-tuent" denotes a substituent having a carbon atom directly 1075'~5 bonded to the remainder of the molecule and having pre-dominantly hydrocarbyl character within the context of this invention. Such substituents include the following:
(1) Purely hydrocarbon substituents, that is aliphatie (e.g., alkyl or alkenyl) substituents containing only earbon and hydrogen.
(2) Substituted hydrocarbon substituents, that is, those containing non-hydrocarbon radicals whieh, in the eontext of this invention, do not alter the predominantly hydrocarbyl eharaeter of the substituent. Those skilled in the art wil~ be aware of suitable radieals (e.g., halo, (especially chloro and fluoro), lower alkoxyl, lower alkyl mercapto, nitro, sulfoxy, etc. radicals). The main hydro-earbon chain can also contain a small number of hetero atoms such as oxygen or sulfur in the form of ether and sulfide linkages. In general, no more than about three radicals or hetero atoms, and usually no more than one, will be present for eaeh 20 earbon atoms in the hydrocarbon-based substituent.
Generally, the hydrocarbon-based substituent, R, in the compositions of this invention are free from acetylenic unsaturation. Ethylenic unsaturation, when present, usually will be such that no more than one ethylenie linkage is present for every 10 carbon-to-carbon bonds in the substi-tuent. The substituents, R, are usually purel~ hydrocarbon in nature and are typically saturated hydrocarbon.
Examples of the hydrocarbon-based substituents, R, are substituents derived from the homopolymerization or inter-polymerization of olefins such as ethylene, propylene, 1-butene, 2-butene, isobutene, pentenes, hexenes, and similar monoolefins up to C20. Usually C2_l0 l-monoolefins are ~075;~6S

used. Substituents derived from poly~ers of ethylene, propylene, l-butene and isobutene are preferred, especially those containin~ at least about 70 and usually not more than about 200 aliphatic carbon atoms. An exemplary class of such preferred polymers are those formed by Lewis Acid - catalyzed polymerization of olefin mixtures c~ntaining predominantly (i.e., greater than 50%) isobutene. Another preferred class of polymers is those which contain predominantly (i.e., greater than 50 mole %) isobutene repeat units, i.e., fH3 -CH2f- repeat units.

The production of olefin polymers and halogenated and hydrohalogenated analogs which serve as intermediates for such R substituents is well known to those skilled in the art; see, for example, the article entitled "Olefin-Polymers-Higher Polyolefins" in Vol. 14, pages 309-313 of the below-mentioned Kirk-Othmer "Encyclopedia of Chemical Technology".
These R substituents can be attached to the aromatic nuclei, Ar, by techniques discussed hereinbelow.
The hydroxy aromatic compounds of this invention also have at least one methylol or lower hydrocarbon-based substituted methylol substitutent directly bonded to a carbon of the aromatic nucleus, Ar. The lower hydrocarbon-based substitutents have up to seven carbon atoms and can be alkyl (e.g., methyl, ethyl, etc.), alkenyl (propenyl, etc.), aryl (e.g., phenyl, tolyl), and alkaryl (e.g., benzyl~.
They can be represented by "hyd" and the methylol substi-tuents thus can be represented by -CH20H (methylol), -CHOH, and -COH. Usually the substituent is methylol it-hyd (hyd) 2 self or an alkyl-substituted methylol or phenyl- substituted 1075;~5 methylol substituent, e.g., -CHOH, -COH or -CHOH.
CH3 ( 3)2 C6H5 While the specific su~stituents of the hydroxy aromatic compounds of this invention (i.e., the hydroxyl substituent, hydrocarbon-based substituent, R, and the methylol substi-tuent) can be attached to the aromatic nucleus, Ar, in any sequence of reactions, it is generally optimal to attach them in the order OH, R, methylol. This can be done, for example, when Ar is a benzene nucleus, by first alkylating a phenol and then reacting the alkylated product with an aldehyde or ketone or functional equivalent thereof.
The introduction of R substituents onto hydroxy aromatic compounds is usually affected by mixing an intermediate such asan olefin homopolymer, interpolymer or a halogenat~d analog thereof and, for example, a phenol at a tempera-ture at about 10-200C in the presence of a suitable catalyst such as aluminum trichloride, boron trifluoride, zinc chloride, or the like; see, for example, U.S. Patent 3,368,972. A substituent can also be introduced by other alkylation processes known to the art; see, for example, the article entitled "Alkylation of Phenols" in Kirk-Othmer "Encyclopedia of Chemical Technology", Second Edition, Vol. L, Pages 894-895, Interscience Publishers, a division of John Wiley & Sons, New York, 1963.
To be useful for the production of the hydroxy aromatic compounds of this invention, the intermediate thus produced must be a hydroxy aromatic intermediate having at least one hydrocarbon-based substituent of at least 50 aliphatic carbon atoms and, in addition, at least one unsubstituted aromatic ring carbon usually located in an alpha or gamma ,i ` ',' 1~75;~i5 position to an aromatic carbon bearing a hydroxyl group.
This~unsubstituted aromatic ring carbon is necessary to pro-vide a site for the subsequent attachment of the methylol or substituted methylol substituent. These intermediates can be represented by the formula (HO)xAr(H)y(R)z wherein x, y and z are each at least one and their sum does not exceed the available valences of Ar.
The methylol or substituted methylol group can be introduced by reaction of the hydroxy aromatic intermediate with a hydrocarbon-based aldehyde or functional equivalent thereof. Suitable aldehydes include formaldehyde, benz-aldehyde, acetaldehyde, butyraldehyde, hydroxy butyralde-hyde, hexanals, etc. "Functional equivalents" are materials (e.g., solutions, polvmers, hydrates, etc.) which react as aldehydes under the conditions of the reaction and include such materials as paraformaldehyde, hexamethylenete-tramine, paraldehyde, formalin and methylal. Should di-substituted methylol groups be desired, the aldehyde is replaced with an appropriate ketone, such as acetone, methyl ethyl ketone, acetophenone, benzophenone, and the like. Mixtures of aldehydes and/or ketones can also be used to produce compounds having mixtures of methylol groups.
Formaldehyde and functional equivalents are generally preferred, since they yield the preferred methylol groups.
Introduction of the methylol groups usually takes place by reacting the hydroxy aromatic intermediate with an aldehyde, ketone or functional equivalent thereof in the presence or absence of an acidic or alkaline reagent. When the reaction takes place in the absence of such reagent, 10752~5 usually a portion of the mixture becomes acidic or alkaline by insitu degradation of the aldehyde or ketone; excess hydroxy aromatic intermediate can also fulfill this function.
Generally, however, the reaction of the aldehyde, ketone or functional equivalent thereof takes place in the presence of an alkaline reagent such as an alka]i metal or alkaline earth metal oxide, hydroxide or lower alkoxide, at a tempera-ture up to about 160C. Other alkaline reagents which can be used include sodium carbonate, sodium bicarbonate, sodium acetate, sodium propionate, pyridine, and hydrocar-bon-based amines such as methyl amine and aniline; naturally, mixtures of two or more bases can be used. Preferably, the reaction takes place in the temperature range of about 30 to about 125C.; more usually, it is carried out between 70 and 100~C.
The relative proportions of hydroxy aromatic inter-mediates, and aldehyde, ketone or functional equivalent thereof are not critical. It is generally satisfactory to use 0.1-5 equivalents of aldehyde and about 0.05-10.0 eguiva-lents of alkaline reagent per equivalent of hydroxy aromaticcompound. As used herein, the term "equivalent" when applied to a hydroxy aromatic compound indicates the weight of such compound equal to the molecular weight thereof divided by the number of unsubstituted aromatic carbons bearing hydrogen atoms. As applied to the aldehyde, ketone or functional equivalent thereof, an "equivalent"
is the weight required to produce one mole of monomeric aldehyde. An equivalent of alkaline reagent is that weight of reagent which when dissolved in one liter of solvent (e.g., water) will give a one normal solution. One equiva-lent of alkaline reagent will therefore neutralize, i.e., bring to pH7 a one normal solution of, for example, hydro-chloric or sulfuric acid.

107~'~65 It is generally convenient to carry out the reaction or the hydroxy aromatic intermediate in the presence of a substantially inert, organic liquid diluent which may be volatile or non-volatile. This diluent may dissolve all the reactants, or it may not, hut in any event, it does not substantially effect the course of the reaction under the prevailing conditions though, in ce~tain cases, it may promote the speed of the reaction by increasing the contact of the reagents. Suitable diluents include hydrocarbons such as naphtha, textile spirits, benzene, toluene, xylene;
mineral oils (which are among the preferred); synthetic oils (as described hereinbelow); alcohols, such as isopropanol, butanol, isobutanol, amyl alcohol, ethyl hexanols and the like; ethers, such as triethylene or diethylene glycol mono- or di-ethyl ether and the like, as well as mixtures of two or more o~ these.
The reaction of the hydroxy aromatic intermediate with aldehyde or ketone generally takes place in 0.5 to 8 hours, depending on such factors as the reaction temperature, amount and nature of alkaline catalyst used, etc. The control of such factors is well within the skill of the art and the effect of these factors is apparent. After the reaction has been completed to the desired extent, it can be substan-tially stopped by neutralization of the reaction mixture when an alkaline reagent is present. This neutralization can be effected with any suitable acidic materi~l, typically a mineral acid or an organic acid or anhydride; an acidic gas such as carbon dioxide, hydrogen sulfide, sulfur dioxide and the like, can also be used. Generally neutralization is accomplished with a carboxylic acid, especially a lower alkanoic carboxylic acid such as formic acid, acetic or propionic acid; mixtures of two or more acids can, of 1075'~65 course, be used to accomplish the neutralization. The neutralization is carried out at a temperature of about 30 to 150C. An amount of neutralizing a~ent sufficient to substantially neutralize the reaction mixture is used.
Substantial neutralization means that the reaction mixture is brought to a pH ranging between 4.5 and 8Ø Usually the reaction mixture is brought to a minimum pH of about 6 or a maximum pH of about 7.5.
The reaction product, i.e., the hydroxy aromatic compositions of this invention, can be recovered from the reaction mixture by such techniques as filtration ~for example, to remove the product of the neutralization of the alkaline reagent) followed by distillation, evaporation, etc. Such techniques are well known to those skilled in the art.
These compositions contain at least one compound which can be represented by the general formula ~HO)xAr(H)y,(R)z(COH)g (R') 2 wherein x, z and g are each at least one; y' is O or at least one, the sum of x, y', z and g does not exceed the available valences of Ar; each R' is hydrogen or a "hyd" substituent as described above, and R is as described above. Often, however, it is not necessary to isolate the hydroxy aromatic compound formed from the reaction solvent, especially if it is to be blended in a fuel or lubricant or to be used as an inter-mediate for further reactions. In the latter case, the reagents for further reaction (such as those discussed here-inbelow) can be added directly to the product mixture;

alternatively, the reaction mixture can be filtered to remove any solids present and the filtrate thus obtained used in further reactions.

1075~65 When the reaction temperature is in the higher range, i.e., above about 100C.,substantial amounts of ether con-densation products can be formed. It is believed that these condensates have the general formula OH
HO- ~CR'2-Ar'- CR'2 ~ H
q wherein q is a number ranging from 2 to about 10. These condensates thus contain alkylene ether linkages, i.e., -CR'2O- linkages. Thus, for example, in the case of the reaction of an alkyl phenol with formaldehyde, ether con-densates are formed having the general formula OH
HO- - CH2 ~ CH2O - H
_ R" q wherein q is a number ranging from 2 to about 10 and R" is an alkyl group of at least 50 carbon atoms. It is possible that small amounts of such ether condensates accompany the predominantly largely uncondensed hydroxy aromatic compounds produced at lower temperatures.
If a strong acid, such as a mineral acid, is used for the neutralization, it is important to control the amount thereof present so as not to bring the reaction mixture to a lower pH than specified hereinabove. For example, at lower pH's, over-condensation occurs to form methylene-bridged phenols. Such methylene-bridged phenols are not within the scope of the present invention. The use, how-ever, of carboxylic acids avoids this problem since they are of sufficiently low acidity they do not promote over-con-densation and it is not necessary to regulate so closely the amount of carboxylic acid used.

107~ 5 The typical phenol or naphthol/formaldehyde-based hydroxy aromatic compounds of this invention have the general formula OH
Ar~(cH2oH)n R

wherein Ar' is a benzene, naphthalene, X-substituted benzene or X-substituted naphthalene nucleus, n is 1 or 2, and R is a hydrocarbon-based substituent of at least about 50 ali-phatic carbon atoms, and X is selected from the group con-sisting of lower alkyl groups, lower alkoxy groups, lower mercapto groups, fluorine atoms, chlorine atoms and nitro groups. An especially preferred class of hydroxy aromatic compounds are those made from phenols and have the general formula OH
(HOCH2)m- ~ CH2OH

R
wherein R~ is an alkyl substituent of about 50 to about 300 carbon atoms derived from polymerization or interpolymeriza-tion of at least one monoolefin of 2 to 10 carbon atoms, and m is 1 or 0.
The following are specific illustrative examples of the hydroxy aromatic compounds of the present invention and include the best mode presently known. All parts and per-centages in the examples and elsewhere herein are by weight unless it is expressly stated to the contrary. All tempera-tures are in degrees centigrade (C) unless expressly stated to the contrary. Molecular weights are determined by vapor phase osmometry (VPO) or gel permeation chromatography (GPC).

1075;~f~S

The textile spirits used in these examples is an aliphatic petroleum naphtha with a boiling range of about 63-79 at 760 torr.
Example lA
Polyisobutenyl chloride (4885 parts) having a viscosity at 99 of 1306 SUS and containing 4.7% chlorine is added to a mixture of 1700 parts phenol, 118 parts of a sulfuric acid-treated clay and 141 parts zinc chloride at 110-155 during a 4-hour period. The mixture is then kept at 155-185 for 3 hours before being filtered through diatomaceous earth. The filtrate is vacuum stripped to 165/0.5 torr.
The residue is again filtered through diatomaceous earth.
The filtrate is a su~bstituted phenol having an OH content of 1~88%.
Example lB
Sodium hydroxide (42 parts of a 20% aqueous sodium hydroxide solution) is added to a mixture of 453 parts of the substituted phenol described in Example lA and 450 parts isopropanol at 30 over 0.5 hour. Textile spirits (60 parts) and 112 parts of a 37.7~ formalin solution are added at 20 over a 0.8 hour period and the reaction mixture is held at 4-25 for 92 hours. Additional textile spirits (50 parts), 50 parts isopropanol and acetic acid (58 parts of a 50~ aqueous acetic acid solution) are added. The pH of the mixture is 5.5 (as determined by ASTM procedure D-974). The mixture is dried over 20 parts magnesium sulfate and then filtered through diatomaceous earth. The filtrate is vacuum stripped to 25/10 torr. The residue is the desired methylol-substituted product having an OH content of 3.29~.
Example 2A
Aluminum chloride (76 parts) is slowly added to a 1075~65 mixture o 4220 parts polyisobutenyl chloride having a number average molecular weight, Mn, of 1000 (VPO) and containing 4.2% chlorine, 1516 parts phenol, and 2500 parts toluene at 60. The reaction mixture is kept at 95 under a below~the-surface nitrogen gas purge for 1.5 hours. Hydro-chloric acid (50 parts of a 37.5% aqueous hydrochloric acid solution) is added at room temperature and the mixture stored for 1.5 hours. The mixture is washed five times with a total of 2500 parts water and then vacuum stripped to 215/1 torr. The residue is filtered at 150 through diato-maceous earth to improve its clarity. The filtrate is a substituted phenol having an OH content of 1.39~, a Cl content of 0.46~ and a Mn of 898 (VPO).
Example 2B
Paraformaldehyde (38 parts) is added to a mixture of 1399 parts of the substituted phenol described in Example 2A, 200 parts toluene, 50 parts water and 2 parts of a 37.5~
aqueous hydrochloric acid solution at 50 and held for one hour. The mixture is then vacuum stripped to 150/15 torr and the residue is filtered through diatomaceous earth.
The f iltrate is the desired product having an O~ content of 1.60%, Mn of 1688 (GPC) and a weight number average molecular weight, Mw, of 2934 (GPC).
Example 3A
Boron trifluoride gas (3.8 parts) is introduced via a sparger underneath the surface into 168 parts phenol at 49-53 during a 0.42 hour period. A solution t519 parts) containing 678 parts polyisobutene having an Mn of 1600 (VPO) and 133 parts benzene is added at 54-57 during a 1.7 hour period and held at 57 for 2.3 hours. A 26% aqueous ammonia solution ~6.5 parts) is added to the reaction iO7SZ~iS

mixture at 56-58 during a l-hour period and then the mix-ture is kept at 69 for 0.67 hour. The mixture is filtered through diatomaceous earth and the filtrate is vacuum stripped to 228/15 torr~ The residue is a substituted S phenol having an OH content of 0.91~ and a Mn of 1439 (VPO).
Example 3B
Sodium hydroxide (352 parts of~a 25~ aqueous sodium hydroxide solution) is added to a mixture of 3740 parts of a substituted phenol prepared as described in Example 3A, 1250 parts textile spirits and 2000 parts isopropanol at 34C.
Formaldehyde (480 parts of a 37.7~ formalin solution) is added over a 0.75 hour period at 34. The reaction mixture is held at 30-34 for 114 hours. Acetic acid (150 parts of a commercially available glacial acetic acid) and 3663 parts diluent oil is added at 30. The mixture is then vacuum stripped to ~U~ torr. ~l~he residue is filtered through diatomaceous earth and the filtrate is a 49~ oil solution of the desired product having an OH content of 1.33%.
Exam~le 4 Sodium hydroxide (842 parts of a 25~ aqueous sodium hydroxide solution) is added to a mixture of 5200 parts of a substituted phenol, prepared as described in Example 3A
except the polyisobutene used has a Mn of 940 (VPO), 1200 parts toluene and 1200 parts isopropanol at 35. Formalde-hyde (600 parts of a 37.7~ formalin solution) is added to the mixture at 35 during a 0.33 hour period and the mixture is kept at 35-30 for a 15-hour period. Additional formalde-hyde (400 parts of a 37.7% formalin solution) is added and the reaction mixture is held a'c 30 for a 20-hour period.
Hydrochloric acid (416 parts of a commercially available 37.5% aqueous hydrochloric acid solution) is added. The pH

1075;~j5 of the mixture is 6. Ben~ene (2000 parts) and 1500 parts additional toluenc are added and the mixture is azeotroped to 95 under a partial vacuum. Diluent oil (2000 parts) is added and the mixture is then vacuum stripped to 95/30 torr.
The residue is filtered through diatomaceous earth and the filtrate is a 30~ oil solution of the desired product having an OH content of 1.69%.
Example 5 Benzene (200 parts) is added to 1110 parts of the azeotroped to 95 under a partial vacuum mixture as described in Example 4 and the reaction temperature is raised to 160 and kept there for 3 hours. The mixture is then filtered through diatomaceous earth at 150 and the filtrate is vacuum stripped to 150/10 torr. The residue is the desired product having an OH content of 1.73% and a Mn of 5252 (GPC) and a Mw of 2171 (G~C3.
Example 6 Sodium hydroxide t8 parts of a 50~ aqueous sodium hydroxide solution) and 145 parts paraformaldehyde are added to a mixture of 2240 parts of a substituted phenol prepared as described in Example 2A except the polyisobutene used has a Mn of 940 (VPO), and 1271 parts diluent oil at 60 and the mixture kept at 80 for 22 hours. Acetic acid (6 parts of glacial acetic acid) is added and the mixture is held at 150 for 2 hours and then filtered through diatomaceous earth. The filtrate is a 35% oil solution of the desired product having an OH content of 1.10%.
Example 7 .
Sodium hydroxide (32 parts of a 50% aqueous sodium hydroxide solution) and 290 parts paraformaldehyde are added to a mixture of 4480 parts of the substituted phenol used in lO~S'~S

Example 6 and 3099 parts diluent oil at 40-50; the mixture is kept at 80-85 for a 14-hour period. ~cetic acid (36 parts of glacial acetic acid) is added at 60. The mixture is held at 110-130 for a period of 12 hours and then is filtered through diatomaceous earth. The filtrate is a 40~
oil solution of the desired product having an OH content of 1.05%.
Example 8 Sodium hydroxide (8 parts of a 50% aqueous sodium hydroxide solution) and 145 parts paraformaldehyde are added to a mixture of 2080 parts of the substituted phenol de-scribed in Example 4 and 1400 parts diluent oil at 55 and the mixture is held at 70-78 for a 7-hour period. Acetic acid (9 parts glacial acetic acid) is added at 60 and then i5 the r.ixture is he~d at 13~ f~r a ~-hour p2riod. The resi-due is a 40~ oil solution of the desired product having an OH content of 1.28% and a viscosity at 99 of 884 SUS.
The compositions of this invention are useful in and of themselves as anti-rust and anti-corrosion agents for fuels and lubricants. They are also useful as intermediates for the production of compositions that function in fuels and lubricants as detergents and dispersants for sludge formed in internal combustion engines.
The compositions of this invention can be employed in a variety of lubricants based on diverse oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. These lubricants include crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, such as automobile and truck 1075;~S

engines, two-cycle engines, marine and railroad diesel engines, and the like. They can also be used in gas en-gines, stationary power engines, turbines and the like.
Automatic transmission fluids, transaxle lubricants, gear lubricants, metal-working lubricants, hydraulic fluids and other lubricating oil and grease compositions can also benefit from the incorporation therein of the compositions of the present invention.
Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base olls. Synthetic lubricatiilg Gils include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., poly-butylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.); poly(l-hexenes), poly(l-octenes), poly(l-decenes), etc. and mixtures thereof;
alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes, etc.); poly-phenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like.
Alkylene oxide polymers and interpolymers and deri-vatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These 107S2~5 are exemplified by the oils prepared throu~h polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropy-lene glycol having a molecular weight of 1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C 8 fatty acid esters, or the 0 Cl 30Xo acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid and the like.
Esters useful as synthetic oils also include those made from Cs to C~ 2 monocarboxylic acids and polyols and polyol 10752f~5 ethers such as neopentyl glycol, trimethylol propane, pent-aerythritol, dipentaerythritol, tripentaerythritol, etc.
Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another useful class of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-hexyl)silicate, tetra-(p-tert-butylphenyl)silicate, hexyl-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)siloxanes, poly~methylphenyl)siloxanes, etc.). Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid, etc.), polymeric tetrahydrofurans and the like.
Unrefined, refined and rerefined oils, either natural or synthetic (as well as mixtures of two or more of any of these) of the type disclosed hereinabove can be used in the lubricant compositions of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such puri-fication techniques are known to those of skill in the art such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Rerefined iO75;~:iS

oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent addi-tives and oil breakdown products.
In general, about 0.05-20.0, preferably 0.1-10 parts (by weight) of a composition of this invention is dissolved or stably dispersed in 100 parts of oil to produce a satis-factory lubricant. The invention also contemplates the use of other additives in combination with the composition of this invention. Such additives include, for example, auxi-liary detergents and dispersants of the ash-producing or ashless type, oxidation inhibiting agents, pour point depressing agents, extreme pressure agents, color stabilizers and anti-foam agents.
The fuel compositions of the present invention contain a major proportion of a normally liquid fuel, usually a hydrocarbonaceous petroleum distillate fuel such as motor gasoline as defined by ASTM Specification D-439-73 and diesel fuel or fuel oil as defined by ASTM Specification D-396. Normally liquid fuel compositions comprising non-hydrocarbonaceous materials such as alcohols, ethers, organo-nitro compounds and the like (e.g., methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) are also within the scope of this invention as are liquid fuels derived from vegetable or mineral sources such as corn, alfalfa, shale and coal. Normally liquid fuels which are mixtures of one or more hydrocarbonaceous fuels and one or more non-hydrocarbonaceous materials are also contemplated.
Examples of such mixtures are combinations of gasoline and 107S2~;S

ethanol, diesel fuel and ether, gasoline and nitromethane, etc. Particularly preferred is gasoline, that is, a mixture of hydrocarbons having an ASTM boiling point of 60~C. at the 10% distillation point to about 205C. at the 90~ distilla-tion point.
Generally, these fuel composit~ons contain an amount of the compound of this invention sufficient to impart anti-oxidant and/or dispersant and detergent properties to the fuel; usually this amount is about 1 to about 10,000, preferably 4 to 1,000, parts by weight of the reaction product per million parts by weight of fuel. The preferred gasoline-based fuel compositions generally exhibit excellent engine oil sludge dispersancy and detergency properties. In addition, they resist oxidation.
The fuel compositions of this invention can contain, in addition to the compositions of this invention, other addi-tives which are well known to those of skill in the art.
These can include anti-knock agents such as tetra-alkyl lead compounds, lead scavengers such as halo-alkanes (e.g., ethylene dichloride and ethylene dibromide), deposit pre-ventors or modifiers such as triaryl phosphates, dyes, cetane improvers, anti-oxidants such as 2,6-di-tertiary-butyl-4-methylphenol, rust inhibitors, such as alkylated succinic acids and anhydrides, bacteriostatic agents, gum inhibitors, metal deactivators, demulsifiers, upper cylinder lubricants, anti-icing agents and the like.
In certain preferred fuel compositions of the present invention, the afore-described compositions of this inven-1~75;~S

tion are combined with other ashless dispersants in gaso-line. Such ashless dispersants are prefereably esters of a mono- or polyol and a high molecular weight mono- or poly-carboxylic acid acylating agent containing at least 30 carbon atoms in the acyl moiety. SUch esters are well known to those of skill in the art. See, for example, French Patent 1,396,645, British 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 British Patent Specification 1,306,529. Generally, the weight ratio of the compositions of this invention to the aforesaid ashless dispersants is about 0.1 to about 10.0; preferably about 1 to about 10 parts of composition of this invention to 1 part ashless dispersant.
In still another embodiment of this invention, the compositions are combined with Mannich condensation products formed from substituted phenols, aldehydes, polyamines, and amino pyridines to make lubricants 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 compositions of this invention can be added di-rectly to the fuel or lubricating oil to form the fuel and lubricant compositions of this invention or they can be diluted with at least one substantially inert, normally liquid organic solvent/diluent such as mineral oil, xylene, or a normally liquid fuel as described above, to form an additive concentrate which is then added to the fuel or 1075'~S

lubricating oil in sufficient amounts to form the inventive fuel and lubricant composition described herein. These concentrates generally contain about 20 to about 90 percent of the composition of this invention and can contain in addition any of the above-described conventional additives, particularly the afore-aescribed ashless dispersants in the aforesaid proportions. The remainder of the ~oncentrate is the solvent/diluent.
As well as serving as additives in and of themselves, the compounds of this invention can be used as inter-mediates to form compositions which are also useful as additives in the afore-described fuels and lubricants.
For example, the methylol-substituted phenols of this invention can be condensed with amines-and polyamines having at least one~ NH group to form useful engine sludge dis-persan~/detergent compositions. -Such condensation can be conveniently carried out by heating the phenol/amine mixture in the presence of benzene or toluene while removing the by-product water by azeotropic distillation. Further details of such condensations can be found in French Patent 75 07709, filed March 12, 1975.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A composition comprising at least one hydroxy aromatic compound having:
(a) at least one hydroxyl substituent bonded directly to a carbon atom of an aromatic moiety, Ar, (b) at least one hydrocarbon-based substituent of at least about 50 aliphatic carbon atoms and less than about 300 carbon atoms bonded directly to a carbon atom of the aromatic moiety, Ar, and (c) at least one methylol or lower hydrocarbon-based substituted methylol substituent bonded directly to a carbon atom of the aromatic moiety, Ar, said compound containing no alkylene linkages between carbon atoms of two aromatic nuclei.

2. A composition as claimed in claim 1 wherein the substituent (c) is a methylol substituent, CH2OH.

3. A composition as claimed in claim 1 wherein the hydrocarbon-based substituent (b) is derived from homopoly-merization or interpolymerization of at least one l-mono-olefin of 2 to 10 carbon atoms.

4. A composition as claimed in claim 3 wherein said monoolefin contains predominantly isobutene and the sub-stituent (c) is at least one methylol substituent.

5. A composition as claimed in claim 1 of the general formula wherein Ar' is a benzene, naphthalene, X-substituted benzene or X-substituted naphthalene nucleus, n is 1 or 2, and R is a hydrocarbon-based substituent of at least about 50 ali-phatic carbon atoms and less than about 300 carbon atoms, X
being selected from the group consisting of lower alkyl subs-tituents, lower alkoxy substituents, lower mercapto substituents, fluorine atoms, chlorine atoms and nitro substituents.

6. A composition as claimed in claim 5 wherein R has up to about 300 carbon atoms and is derived from homopoly-merization or interpolymerization of at least one 1-mono-olefin of 2 to 10 carbon atoms.

7. A composition as claimed in claim 6 of the general formula wherein R° is an alkyl substituent of about 50 to about 300 carbon atoms derived from polymerization or interpolymeriza-tion of at least one monoolefin of 2 to 10 carbon atoms, and m is 1 or 0.

8. A composition as claimed in claim 1 made by reacting at a temperature up to about 160°C. at least one hydroxy aromatic compound having a hydrocarbon-based substituent of at least 50 aliphatic carbon atoms and less than about 300 carbon atoms, and at least one unsubstituted aromatic ring carbon, with formaldehyde or a lower hydrocarbon substituted formaldehyde or functional equivalent thereof in the presence of an alkaline reagent.

9. A composition as claimed in claim 8 wherein formalde-hyde or a functional equivalent thereof is used and the alkaline reagent is selected from the group consisting of alkali metal and alkaline earth metal oxides, hydroxides and lower alkoxides.

10. A composition as claimed in claim 9 wherein the hydroxy aromatic compound is phenol, naphthol, X-substituted phenol or X-substituted naphthol and X is selected from the group consisting of lower alkyl substituents, lower alkoxy substituents, lower alkyl mercapto substituents, fluorine atoms, chlorine atoms and nitro substituents.

11. A fuel or lubricant composition containing a major proportion of a normally liquid fuel or a lubricating oil of lubricating viscosity and a minor proportion of the composi-tion claimed in claim 1.

12. A fuel or lubricant composition containing a major proportion of a normally liquid fuel or a lubricating oil of lubricating viscosity and a minor proportion of the composi-tion claimed in claim 2.

13. A fuel or lubricant composition containing a major proportion of a normally liquid fuel or a lubricating oil of lubricating viscosity and a minor proportion of the composition claimed in claim 4.

14. A fuel or lubricant composition containing a major proportion of a normally liquid fuel or a lubricating oil of lubricating viscosity and a minor proportion of the composition claimed in claim 7.

15. A fuel or lubricant composition containing a major proportion of a normally liquid fuel or a lubricating oil of lubricating viscosity and a minor proportion of the composition claimed in claim 10.

16. An additive concentrate comprising at least one substantially inert, normally liquid organic solvent/diluent and about 20 to about 90 percent of the composition claimed in claim 1.

17. An additive concentrate comprising at least one substantially inert, normally liquid organic solvent/diluent and about 20 to about 90 percent of the composition claimed in claim 2.

18. An additive concentrate comprising at least one substantially inert, normally liquid organic solvent/diluent and about 20 to about 90 percent of the composition claimed in claim 4.

19. An additive concentrate comprising at least one substantially inert, normally liquid organic solvent/diluent and about 20 to about 90 percent of the composition claimed in claim 7.

20. An additive concentrate comprising at least one substantially inert, normally liquid organic solvent/diluent and about 20 to about 90 percent of the composition claimed in claim 10.

21. A process for preparing a-composition as claimed in claim 1 comprising reacting an intermediate of the general formula (HO)xAR(H)y(R)z wherein Ar is an aromatic moiety containing no alkylene linkages between carbon atoms of two aromatic nuclei, R is a hydrocarbon-based substituent of at least about 50 aliphatic carbon atoms and less than about 300 carbon atoms, and x, y, and z are each at least one and their sum does not exceed the available valences of Ar, with a lower aldehyde, ketone, or functional equivalent thereof in the presence or absence of an acidic or alkaline catalyst and at a temperature of up to about 160°C, and obtaining a composition as claimed in claim 1.

22. A process as claimed in claim 21 wherein the reaction takes place in the presence of an alkaline catalyst.

23. A process as claimed in claim 21 or 22 wherein the reaction takes place at a temperature of from about 30 to about 125°C.

24. A process as claimed in claim 21 or 22 wherein the reaction takes place at a temperature of from about 70 to 100°C.

25. A process as claimed in claim 21 wherein R has up to about 300 carbon atoms.

26. A process as claimed in claim 21 or 25 wherein R is an alkyl substituent of about 50 to about 300 carbons.

27. A process as claimed in claim 21 wherein formaldehyde, a lower hydrocarbon substituted formaldehyde, or a functional equivalent thereof is used as the aldehyde in the presence of an alkaline catalyst.

28. A process as claimed in claim 27 wherein formaldehyde or a functional equivalent is used in the presence of an alkali metal or alkaline earth metal oxide, hydroxide or lower alkoxide as the alkaline catalyst.