CA1137517A - Oxidatively coupled hydroxyaromatic compounds and fuels and lubricants containing them - Google Patents

Abstract

Mixtures of (A) hydroxyaromatic compounds (e.g., phenols) having no aliphatic substituents of more than 4 carbon atoms and (B) hydroxyaromatic compounds having at least one aliphatic substituent with at least about 12 carbon atoms may be oxidatively coupled to yield products useful as lubricant and fuel additives.

Description

- ~37~ LF-2010-Ca OXIDATIVELY COUPLED HYDROXYAROMATIC COMPOUNDS
AND FUELS AND LUBRICANTS CONTAINING THEM
..

This invention relates to new compositions of matter suit-able for oxidative coupling, to oxidatively coupled products prepared from such compositions and a method for their preparation, and to additive concentrat~s, lubricants and fuels containing such products. More specifically, the oxidatively coupled products of this invention are prepared from a reaction mixture comprising:
~ A) At least one hydroxyaromatic compound containing no aliphatic substituent having more than 4 carbon atoms; and (B) At least one hydroxyaromatic compound containing at least one aliphatic substituent having at least about 12 carbon atoms;
at least one position ortho to a hydroxy group in each of reagents A and B being unsubstituted.
Metho.d~. and reagents for oxidative coupling of hydroxyaro-matic compounds are disclosed in Taylor et al., Oxidative Coupling of Phenols (Marcel Dekker, Inc., 1967); in Patai, The Chemistry of the Hydroxyl Group, chapters 10 and 16 (Interscience Publishers, 1971); and in many U.S. patents including the following:

~l~l 3'~7 3,306,875 3,873,627 3,630,900 3,876,709 3,631,208 3,928,355 3,772,373 3,959,2~3 3,819,579 3,970,640 In general, this reaction comprises the oxidation of hy-droxyaromatic compounds in the presence of reagents which promote the formation of carbon-to-carbon or carbon-to-oxygen bonds linking aromatic rings. The precise molecular structure of the resulting products may not be readily identifiable and it is often most convenient to define the products in terms of the process for their preparation.

The products of this invention are prepared by oxidative coupling of a mixture of at least two different types of hydroxyaromatic compounds. The first type, frequently refer-red to herein as "reagent A", contains one or more aromatic rings and no aliphatic substituent having more than 4 carbon atoms. If any aliphatic substituents are present, they are generally alkyl groups. If more than one aromatic ring is present, the rings may be fused, linked by direct carbon-to-carbon bonds, or linked through other atoms such as oxygen or carbon. Compounds conkaining more than one hydroxy group attached to the aromatic moieties are included, as are com-pounds containing other substituents such as halogen, alkyl, hydroxyalkyl, alkoxy or alkylthio (so long as any alkyl groups therein contain no more than 4 carbon atoms). It is essential, however, that the hydroxyaromatic compounds contain at least one unsubstituted position ortho to a hydroxy group. Suitable hydroxaromatic compounds include phenol, m-cresol, p-cresol, p-ethylphenol, a-naphthol, ~-naphthol, 4-methyl-a-naphthol, p-chlorophenol, o-methoxyphenol, catechol, resorcinol, hydro-quinone, hydorxybiphenyl and bisphenol A.

~37~

A preferred subgenus of compounds useful as reagent A has the formula -a (OH)a wherein a is l or 2, usually 1; each Y is individually hydrogen, halo, alkyl or hydroxyalkyl or haloalkyl of up to 4 carbon atoms, or alkoxy or alkylthio of up to ~ carbon atoms; and at least one and preferably two positions ortho to a hydroxy group are unsubstituted. Most often, up to two Y's (preferably none) are alkyl or hydroxyalkyl radi-cals having up to 2 carbon atoms and all others are hydro-gen. It is also preferred that the positions adjacent to the previously mentioned unsubstitutad ortho positions not contain bulky substituents such as t-butyl or phenyl groups which would tend to inhibit oxidative coupling in those positions.
The second type of hydroxyaromatic compound, fre-quently referred to herein as "reagent B", is in most re-spects similar to reagent A but differs therefrom in that its molecules contain at least one (usually only one) aliphatic substituent ha~ing at least about 12 carbon atoms. The aliphatic substituent may be bound to the aromatic radical through a direct carbon-to-carbon bond or through a hetero atom such as oxygen or sulfur; the direct carbon-to-carbon bond is preferred.
The aliphatic substituent in reagent B is usually substantially saturated. By "substantially saturated" is meant that it is free of acetylenic unsaturation and has no more than one olefinic bond for each 12 carbon atoms, usually no more than one olefinic bond for each 25 ali-phatic carbon atoms. It is ordinarily an aliphatic hydro-carbon radical, but it may also contain non-aliphatic hydrocarbon substituents such as phenyl, hydroxy, nitro, carbalkoxy, alkoxy, cyano, halo and the like. In general, no more than one such substituent is present for every 5 and usually for every 25 carbon atoms.
A preferred subgenus of compounds useful as reagent B has the formula 37~ 7 ..

[~ ( OH ) b wherein b is 1 or 2, usually 1; each X is individually hydrogen, halo, alkyl or hydroxyalkyl or haloalkyl of up to 4 carbon atoms, or alkoxy or alkylthio of up to 4 carbon atoms, R is an aliphatic radical having at least about 12 carbon atoms; and at least one and preferably two posi-tions ortho to a hydroxy group are unsubstituted. As will be apparent, this subgenus of preferred compounds differs from the subgenus preferred as reagent A in the presence of the aliphatic raaical R. The R group is most desirably para to the hydroxy group. Most often, up to two X's (prefer-ably none) are alkyl or hydroxyalkyl radicals having up to 2 carbon atoms and all others are hydrogen; also, the preference expressed with reference to reagent A for the absence of bulky substituents applies equally to reagent B.
Illustrative aliphatic substituents on reagent B, and present as R in the formula for the preferred subgenus, _ are n-dodecyl, tetrapropenyl, n-octadecyl, oleyl, chloro-octadecyl, triacontanyl and the like. The R radical pre-ferably contains at least about 40 carbon atoms, in which case it is most often derived from an olefin polymer such as polypropylene, polybutene, ethylene-propylene copolymer, butene-isoprene copolymer and the like. These polymers usually have a number average molecular weight between about 500 and about lS,000, preferably between about 600 and about 5,000 and most desirably between about 800 and about 3,000, as determined by vapor phase osmometry. Es-pecially preferred aliphatic radicals are those derived from polybutenes containing predominantly isobutene units.
Referring to the preferred structural formula for component B, compounds of this type may be readily prepared from hydroxyaromatic compounds containing no R substituents by alkylation by known methods. The invention also con-templates the use as reagent B of the product of a previous oxidative coupling reaction according to the invention.

~l375~
.

The ratio of reagent A to reagent B can vary widely; for example, about 0.1-20 moles of reagent A per mole of reagent B. Tha preferred range is from about 0.2 to about 20 moles, most desirably ~xom about 0.33 to about 15 moles, of reagent A per mole o~ reagent B.
The oxidatively coupled products of this inven-tion are prepared by reacting the above-described mixtures of hydroxyaromatic compounds with an oxidative coupling agent. Suitable oxidative coupling agents are known to 10 those skilled in the art. They include, for example, molecular oxygen in combination with copper salts and amines; ferric iron compounds such as potassium ferricya-nide and ferric chloride; tetravalent lead compounds such as lead tetraacetate and lead dioxide; peroxy compounds 15 such as hydrogen peroxide, alkyl peroxide, acyl peroxide and persulfates; periodates; Fremy's salt; silver oxide;
nickel dioxide; halogens such as ~hlorine and bromine;
potassium permanganate and other permanganates; and mix-tures of potassium dichromate and manganese acetate.
20 Other suitable oxidative coupling agents and methods for their use are described in the textbooks and patents pre-viously incorporated by reference.
For the purposes of this invention, it is pre-ferred to use as an oxidative coupling agent molecular 25 oxygen or air in the presence of a catalyst prepared by combining a copper salt with an amine. The amine used in the preparation of the catalyst may be primary, secondary or tertiary, and may be a monoamine or a polyamine. Ali-phatic (including arylaliphatic), alicyclic and heterocy-30 clic amine~ are preferred; these include trimethylamine,triethylamine, tripropylamine, benzyldiamylamine, ethyl-isopropylamine, 4-pentenyldimethylamine, methyl(cyclohexyl)-amine, octyl(chlorobenzyl)amine, methyl(phenethyl)amine, l-ethylamino-2-phenylheptane, benzyl(dihexyl)amine, 2-35 methyloctyldiethylamine, pyridine, pyrrole, pyrrolidine,piperidine, isoquinoline, morpholine, and substituted de-rivatives of the above-named heterocyclic amines. Ter-tiary amines and especially tertiary heterocyclic amines such as the pyridines are preferred.

l3~5:17 ~ -The copper salt component of the catalyst may be any copper salt which forms a soluble or dispersible complex with the amine. Suitable copper salts include cuprous and cupric halides and sulfates. The cuprous salts, and es-pecially cuprous chloride, are preferred.
The copper salt-amine catalyst is normally pre-pared as a complex either prior to addition to the mixture to be oxidatively coupled, or in situ in said mixture by adding the copper salt and amine separately thereto. The relative proportions of copper salt and amine in the cata-lyst complex are known to those skilled in the art and are disclosed, for example, in the aforementioned U.S. Patents 3,306,875; 3,630,900; 3,631,208; and 3,959,223.
Compositions suitable for oxidati~e coupling are contemplated as one aspect of the present invention. These compositions comprise the hydroxyaromatic compounds pre-viously identified as reagent A and reagent B in combination with the solid and liquid components of the oxidative coupling agent. (Gaseous components of the oxidative coupling agent, such as molecular oxygen, must be supplied separately when it is desired to initiate the coupling reaction.) These compositions may also contain a substan-tially inert, normally li~uid organic diluent such as an aliphatic or aromatic hydrocarbon, a chlorinated or nitra-ted aliphatic or aromatic compound, an ether or the like.Suitable diluents include benzene, toluene, xylene, chloro-benzene, o-dichlorobenzene, nitrobenzene, nonane, dodecane, mineral oil, chloroform and dibutyl ether. Aromatic com-pounds are especially preferred as diluents. It is also within the scope of the invention to use as a diluent an excess of the amine component of the oxidative coupling catalyst (e.g., pyridine).
The oxidative coupling reaction may be effected by contacting the hydroxyaromatic compounds with the oxidative coupling agent at a temperature high enough to initiate the reaction but not high enough to cause degradation of the reactants or product. Normally this temperature will be 3~517 ,, .

between about 20C. and about 300C., most often between about 75C. and about 250C. In cases where the oxidative coupling reaction is initiated at relatively low tempera-tures, it may be desirable to store the mixture comprising the hydroxyaromatic compounds and the oxidative coupling agent at low temperatures, such as under refrigeration.
When the oxidative coupling agent comprises at least one gaseous reagent such as molecular oxygen, the mixture of the hydroxyaromatic compounds and the solid and liquid com-ponents of the oxidative coupling agent may be stored undernormal ambient conditions until it is desired to initiate the reaction, whereupon air or oxygen is blown through the mixture in known manner.
The progress of the oxidative coupling reaction may often be monitored by measuring the viscosity of the reaction mixture, which generally increases as the reac-tion continues. When the reaction has progressed to the desired extent, the catalyst may be removed and the pro-duct isolated by removal of diluents (e.g., by vacuum - 20 stripping). If the diluent is a relatively non-volatile material such as mineral oil, its removal may be unneces-sary and the product may be employed in solution as an additive for lubricants or fuels.
The preparation of the oxidatively coupled pro-duc~s of this invention is illustrated by the followingexamples. All parts are by weight; molecular weights are number average molecular weights and are determined by vapor phase osmometry. Polybutenyl moieties, where used, contain predominantly isobutene units.

Example 1 A mixture of 1,665 parts of o-dichlorobenzene, 273 parts o a p-poly~utenyl phenol (molecular weight 1200), 91 parts of phenol, 43 parts of magnesium sulfate, 71 parts of pyridine and 0.94 part of cuprous chloride is blown beneath the surface with air for 8 hours at 140C.
The reQulting composition is cooled to room temperature, 3~ q filtered and stripped to yield the desired oxidative coupling product.

Example 2 A mixture of 3100 parts of o-dichlorobenzene, 48 parts of magnesium sulfate, 80 parts of pyridine and 1 part of cuprous chloride is heated to 75C. as air is bubbled beneath the surface. A solution of 300 parts of p-polybutenyl phenol (molecular weight 1200) and 100 parts of phenol in 780 parts of o-dichlorobenzene is added and the mixture is heated at 140-150C. for 13 hours as air blowing is continued. Mineral oil, 500 parts, is added and the solution is filtered and stripped at 210C. under vacuum to yield an oil solution of the desired oxidative coupling product.
, . .
Example 3 A mixture of 1300 parts of o-dichlorobenzene, 39.5 parts of pyridine, 24 parts of magnesium sulfate and 0.495 part of cuprous chloride-is heated to 70C. as air is bubbled beneath the surface. To the mixture is added 64 parts of o-hexadecyl phenol and 3.2 parts of p-cresol.
The mixture is heated at 70C. for 4 hours a air blowing is continued. Diatomaceous earth, 40 parts, is added and the composition is filtered and stripped at 160C. under vacuum. The residue i5 washed with a solution of 10 parts of concentrated hydrochloric acid in 1000 parts of methanol, filtered and stripped to yield the desired oxi-dative coupling product.

a~
The procedure of Example 1 is repeated except the air blowing period is increased from 8 hours to 18 hours.

^" 1137517 Example 5 A mixture of 910 parts of o-dichlorobenzene, 24 par~s of magnesium sulate, 40 parts of pyridine and O.S part of cuprous chloride is heated to 75C. A solu-tion of 100 parts of p-polybutenyl phenol (molecular weight 860) and 9.4 paxts of phenol in 390 parts of o-dichloro-benzene is added and the mixture is heated at 140-150C.
for 7 hours as air is bubbled beneath the surface. The mixture is filtexed and stripped at 210C. under vacuum.
Xylene, 100 parts, is added to the filtrate to yield a xylene solution of the desired oxidative coupling product.

Example 6 The procedure of Example 2 is repeated except the amount of phenol is increased to 200 parts.

15 Example 7 To a mixture o~ 100 parts of sodium carbonate, 400 parts of water, loO parts of ethanol and 165 parts of potassium ferricyanide is added a mixture of 300 parts of p-polybutenyl phenol (molecular weight 1200), 25 parts of phenol and 325 parts of mineral oil. The mixture is heated at 70C. under nitrogen for 2 hours. Toluene, 1000 parts, i8 added and the solution is washed three times with water, stripped at 210C. under vacuum and filtered to yield an oil solution of the desired oxidative coupling product.

ExamP'le' 8 A mixture of 300 parts of p-polybutenyl phenol ~molecular weight 1200), 3100 parts of o-dichlorobenzene, 48 parts of magnesium sulfate, 80 parts of pyridine and 1 part of cuprous chloride is heated to 75C. A solution of 100 parts of phenol in 780 parts of o-dichlorobenzene is added over 1 hour as the mixture is blown with air; air blowing i8 continued for 17 hours at 140-160C. Mineral oil, 500 parts, is added and the composition is filtered and stripped at 210C. under vacuum to yield an oil solu-tion o the desired oxidative coupling product.

' ~ 3751~ ~

Example 9 A mixture of 510 parts of o-dichlorobenzene, 24 parts of magnesium sulfate (a drying agent used to remove water as it is formed), 40 parts of pyridine and 1 part o~ cuprous chloride is heated to 75C. as air is bubbled beneath the surface. A solution of 105 parts of the oxidative coupling product of Example 6 and 25 parts of phenol in 300 parts of o-dichlorobenzene is added and the reaction mixture is heated at 140-150C. for 13 hours as air blowing is continued. Mineral oil, 50 parts, is added and the composition is filtered and stripped at 210C. under vacuum to yield a xylene solution of the desired oxidati~e coupling product.

Example 10 The procedure of Example 9 is repeated except the product of Example 6 is replaced with 232 parts of the product of Example 2,-Example 11 _ .
The procedure of Example 1 is repeated except the '~
o-dichlorobenzene is replaced with xylene on an equal weight basis.

Examples 12-21 Oxidatively coupled compositions are prepared from the reaction mixtures listed in the following table accoraing to the general procedure of Example 1.

3~17 ., .

.,~
.
h m .. .. .. .. .. .. .. .. .. .. ..

,, o~
.,.
~o .,, s ~ , ~X o ~-~1 tn aJ , ~ ~
'a O h ~, s~

m ~1 oQI ~ ~ h ~
O ~-rl ~ ~1 0 a~: .c ~1 o :1 S o u~
O O . ~ X O ~~ O
a~ oQ-0 ' ~ ~ ~-- Z
: C~ ~ O ~L X O ~ S; m P.
.

. O O O O O O O OO rl . ~ o O o O U~ O ~ O
~1 ~ o a~ ~o a~ _~
~; o o _/
o o o ~ o o ~ o .c a) ~o ~: ~1 0 J S ~
a) o ~>~
rl ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
l o ~ ~ a) o ~ a q) ~ IJ ~ h ~ ~ O IJ
,, .4 o o .4 ~ la ,4 .
~ ~ C~ h O Q,C O O O O O O O ~ 3 ~ ~ O
,~
~i Q~
o _l o X ~

~375~

As previously indicated, the oxidatively coupled products of this lnvention are useful as additives for lubricants, in which they function primarily as dispersants, oxidation inhibitors and viscosity modifiers. They 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, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad diesel engines, and the like. They can also be used in gas engines, stationary power engines and turbines and the like. Automatic trans-mission fluids, transaxle lubricants, gear lubricants, metal-working lubricants, hydraulic fluids and other lubri-cating oil and grea~e compositions can also benefit from the incorporation therein of the compositions of the pre-sent invention.
Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as liquid petro-leum 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 oils.
Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins le.g., polybutylenes, polypro-pylenes, propylene-isobutylene copolymers, chlorinated poly-butylenes, poly(l-hexenes), poly(l-octenes), poly(l-decenes), etc. and mixtures thereof]; alkylbenzenes (e.g.,dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.), alkylated di-phenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like.
Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have 3l~;37~17 been modified by esterification, etherification, etc. con-stitute another class of known synthetic lubricating oils.
These are exemplified by the oils prepared through poly-merization of ethylene oxide or propylene oxide, the alkyl and aryl ethers o~ 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-lO00, diethyl ether of polypropylene glycol having a molecular weight of 1000-lO 1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-Ca fatty acid esters, or the C~ 3 OXO acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., 15 phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumarlc acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alco-20 hol, 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 25 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.
E~ters useful as synthetic oils also include those made from Cs to Cl 2 monocarboxylic acids and polyols and polyol ethers such neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
Silicon-based oils such as the polyalkyl-, poly-35 aryl-, polyalkoxy-, or polyaryloxy-siloxane oils and sili-cate oils comprise another useful class of synthetic lubri-cants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-t2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) . ' , ~ 37~i17 .

silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(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, trioctylphosphate, diethyl ester of decylphosphonic acid, etc.), polymeric tetrahydrofurans and the like.
Unrefined, refined and rerefined oils (and mix-tures of each with each other) of the type disclosed here-10 inabove can be used in the lubricant compositions of thepresent invention. Unreined 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 15 directly from 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 20 more properties. Many such purification techniques are known to those of skill in the art such as solvent extrac-tion, acid or base extraction, filtration, percolation, etc.
Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which 25 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~ additives and oil breakdown products.
Generally, the lubricants of the present inven-30 tion contain an amount of the composition of this invention sufficient to provide dispersancy, oxidation inhibiting or viscosity modifying propexties. Normally this amount will be from about 0.05% to about 20~, preferably from about 0.1% to about 10%, of the total weight of the lubricant.
The invention also contemplates the use of other additives in combination with the oxidative coupling pro-ducts of this invention. Such additives include, for ~375~ ~
,. . .

example, ash-producing detergents, auxiliary ashless dis-persants, corrosion- and oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, color stabilizers and anti-foam agents.
The ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared 10 by the treatment of an olefin polymer ~e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus hepta-sulfide, phosphorus pentasulfiae, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or 15 phosphorothioic chloride. The most commonly used salts of such acids are those of sodium, potassium, lithium, cal-cium, magnesium, strontium and barium.
The term "basic salt" is used to designate metal salts wherein the metal is present in stoichiometrically 20 larger amounts than the organic acid radical. The commonly employed methods for preparing the basic salts involve heat-ing a mineral oil solution o~ an acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a 25 temperature above 50C. and filtering the resulting mass.
The use of a "promoter" in the neutralization step to aid the incorporation of a large excess of metal likewise is known. Examples of compounds useful as the promoter in-clude phenolic substances such as phenol, naphthol, alkyl-30 phenol, thiophenol, sulfurized alkylphenol, and condensa-tion products of formaldehyde with a phenolic substance;
alcohols such as methanol, ~-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, 35 and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-~-naphthylamine, and dodecylamine. A particularly effective method for preparing the basic salts comprises mixing an acid with an 3~517 excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonating the mixture at an elevated temperature such as 60-200C.
Auxiliary ashless detergents and dispersants are so called despite the fact that, depending on its constitu-tion, the dispersant may upon combustion yield a non-volatile material s~ch as boric oxide or phosphorus pen-toxide: however, it does not ordinarily contain metal and therefore does not yield a metal-containing ash on com-10 bustion. ~any types are known in the art, and any of themare suitable for use in the lubricants of this invention.
The ~ollowing are illustrative:
(1) Reaction products of carboxylic acids (or derivatives thereof) containing at least about 34 and pre-15 ferably at lèa~t about 54 carbon atoms with nitrogen-containing compounds such as amine, organic hydroxy com-pounds such as phenols and alcohols, and/or basic inorganic materials. Examples of these "carboxylic dispersants1' are described in British Patent 1,306,529 and in many U.S.
20 patents including the following:
~ 3,163,603 3,351,552 3,541,01~
3,184,474 3,381,022 3,542,678 3,215,707 3,399,141 3,542,680 3,219,666 3,415,750 3,567,637 3,271,310 3,433,744 3,574,101 3,272,746 3,444,170 3,576,743 3,281,357 3,448,048 3,630,904 3,306,908 3,448,049 3,632,~10 3,311,558 3,451,933 3,632,511 3,316,177 3,454,607 3,697,428 3f340,2al 3,467,668 3,725,441 3,341,542 3,501,405 Re 26,433 3,346,493 3,522,17g

(2) Reaction products of relatively high molecu-35 lar weight aliphatic or alicyclic halides with amines, pre-ferably polyalkylene polyamines. These may be character-ized as "amine dispersants" and examples thereof are described for example, in the following U.S. patents:

37~17 ~ -

3,275,554 3,454,555 3,438,757 3,565,804 (3) Reaction products of alkyl phenols in which ~he alkyl group contains at least about 30 carbon atoms with aldehydes (especially formaldehyde~ and amines (es-pecially polyalkylene polyamines), which may be charac-terized as "Mannich dispersants". The materials described in the following U.S. patents are illustrative:
3,413,347 3,725,480 3,697,574 3,726,882 3,725,277

(4) Products obtained by post-treating the car-boxylic, amine or Mannich dispersants with such reagents as urea, thiourea, carbon disulfide, aldehydes, ketones, car-15 boxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, pho~phorus compounds or the like. Exemplary materials of this kind are described in the following U.S. patents:
3,036,003 3,282,955 3,493,520 3,639,242 20 3,087,936 3,312,619 3,502,677 3,649,229 3,200,107 3,366,569 3,513,093 3,649,~59 3,216,936 3,367,943 3,533,945 3,658,836 3,254,025 3,373,111 3,539,633 3,697,574 3,256,185 3,403,102 3,573,010 3,702,757 25 3,278,550 3,442,808 3,579,450 3,703,536 3,280,234 3,455,83~ 3,591,598 3,704,308 3,281,428 3,455,832 3,600,372 3,708,522

(5) Interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high 30 molecular weight olefins with monomers containing polar substituents, e.g., aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates. These may be characterized as "polymeric dispersants" and examples thereof are disclosed in the following U.S. patents:
3,329,658 3,666,730 3,449,250 3,687,849 3,519,565 3,702,300 , .~

37~17 Extreme pressure agents and corrosion- and oxidation-in-hibiting agents are exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wax; organic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl)di-sulfide, dibutyl tetrasulfide, sulfurized methyl ester ofoleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene; phosphosulfurized hydrocarons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate; phosphorus esters including principally di-hydrocarbon and trihydrocarbon phosphites such as dibutylphosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl-phenyl phosphite, dipentylphenyl phosphite, tridecyl phos-phite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500)-substituted phenyl phosphite, diisobutyl-substi-tuted phenyl phosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate, and barium heptylphenyl dithiocarba-mate; Group II metal phosphorodithioates such as zinc dicy-clohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium di(heptylphenyl)-phosphorodithioate, cadmium dinonyl-phosphorodithioate, and the zinc salt of a phosphorodithioic acid produced by the reaction of phosphorus pentasulfide with an equimolar mixture of isopropyl alcohol and n-hexyl alcohol.

The oxidative coupling products of this invention can also be used as dispersant and antioxidant additives in fuels. The fuel compositions of the invention contain a ma-jor proportion of a normally liquid fuel, ususally a hydro-carbonaceous 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 nonhydrocarbonaceous 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 contem-plated. Such mixtures include combinations of gasoline and ethanol, diesel fuel and ether, and the like. Particu-larly preferred is gasoline, that is, a mixture of hydro-10 carbons having an ASTM boiling point of about 60C. at the10% distillation point to about 205C. at the 90% distilla-tion point.
Generally, these fuel compositions contain an amount of the oxidative coupling product of this in~ention 15 sufficient to impart dispersancy and oxidation resistant properties thereto; usually this amount is ~rom about 1 to about 10,000, preferably from about 10 to about 5000, parts by weight of the oxidative coupling product per million parts of fuel.
The fuel compositions of this invention can con-tain, in addition to the oxidative coupling product, other additives which are well known to those of skill in the art.
These can include antiknock agents such as tetra-alkyl lead compounds, lead scavengers such as halo-alkanes (e.g., 25 ethylene dichloride and ethylene dibromide), deposit pre-ventors or modifiers such as triaryl phosphates, dyes, cetane improvers, antioxidants such as 2,6-di-tertiary-butyl-4-methylphenol, rust inhibitors such as alkylated succinic acid~ and anhydrides, bacteriostatic agents, gum 30 inhibitors, metal deactivators, demulsifiers, upper cylin-der lubricants, anti-icing agents and the like.
The oxidative coupling products of this invention can be added directly to the fuel or lubricant. Prefer-ably, however, they are diluted with a substantially inert, 35 normally li~uid organic diluent such as mineral oil, naphtha, benzene, toluene or xylene, to form an additive concentrate. These concentrates usually contain from about . ~
' .AJ

20% to about 90% by weight of the oxidative coupling pro-duct of this invention and may contain, in addition, one or more other additives known in the art or described hereinabove.
The following are illustrative of lubricant and fuel compositions of this invention. All parts are by weight unless otherwise indicated.

Composition A (Crankcase lubricant) Mineral oil 81.45 parts Product of Example 1 6.5 parts Borated polybutenyl succinic anhydride-ethylene polyamine reaction product 1 part Sulfurizèd lower alkyl cyclohexenyl-carboxylate 1.3 parts Tetrapropenyl succinic acid 0.5 part Poly-tisodecyl acrylate) 7.75 parts Hindered phenol oxidation inhibitox 1.5 parts Silicone anti-foam agent 0.006 par~
.
Composition B (Automatic transmission fluid) Alkylaromatic synthetic oil 89.3 parts Mineral oil 0.3 part Product of Example 9 6 parts Borated polybutenyl succinic anhydride-ethylene polyamine reaction product 3 parts Zinc dialkylphosphorodithioate0.5 part Di-(lower alkyl) hydrogen phosphite 0.1 part Sulfurized fatty oil-fatty acid-olefin mixture O.S part Hindered amine antioxidant 0.1 part Ethoxylated alkylamine friction modifier 0.2 part ~ ~.37~7 Composition C (Middle distillate fuel) Middle distillate fuel oil containing 50 parts per million of the product of Example 3.

Composition D (Gasoline fuel) S Gasoline containing 2 g. per gallon of lead as tetraethyl lead and 20 parts per million of the pro-duct of Example 5.

Composition E (Diesel fuel) Diesel fuel oil containing 40 parts per million of the composition o~ Example 2.

Claims (30)

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

1. A method for preparing an oxidatively coupled product which comprises reacting an oxidative coupling agent with a reaction mixture comprising:
(A) At least one hydroxyaromatic compound con-taining no aliphatic substituent having more than 4 carbon atoms; and (B) at least one hydroxyaromatic compound con-taining at least one aliphatic substituent having at least about 12 carbon atoms;
at least one position ortho to a hydroxy group in each of reagents A and B being unsubstituted.

2. A method according to claim 1 wherein reagents A and B have the formulas (A) (B) wherein R is an aliphatic radical having at least about 12 carbon atoms; each X and each Y is individually hydro-gen, halo, alkyl or hydroxyalkyl or haloalkyl of up to 4 carbon atoms, or alkoxy or alkylthio of up to 4 carbon atoms; and each of a and b is 1 or 2.

3. A method according to claim 2 wherein R has at least about 40 carbon atoms.

4. A method according to claim 3 wherein R has a number average molecular weight between about 600 and about 5000.

5. A method according to claim 4 wherein R is a hydrocarbon radical having a number average molecular weight between about 800 and about 3000.

6. A method according to claim 5 wherein a and b are each 1.

7. A method according to claim 6 wherein both positions ortho to the hydroxy groups in reagents A and B are unsubsti-tuted.

8. A method according to claim 7 wherein R is para to the hydroxy group.

9. A method according to claim 8 wherein up to two X's and up to two Y's are alkyl or hydroxyalkyl radicals having up to 2 carbon atoms and all other X's and Y's are hydrogen.

10. A method according to claim 8 wherein all X's and Y's are hydrogen.

11. A method according to claim 10 wherein the oxidative coupling agent comprises oxygen in combination with a cata-lyst prepared by combining a copper salt with an amine.

12. A method according to claim 11 wherein the copper salt is a cuprous salt and the amine is a tertiary amine.

13. A method according to claim 12 wherein the amine is pyridine and the cuprous salt is cuprous chloride.

14. An oxidatively coupled product prepared by the method of claim 1.

15. A composition comprising the solid and liquid components of an oxidative coupling agent in combination with:
(A) At least one hydroxyaromatic compound contain-ing no aliphatic substituent having more than 4 carbon atoms;
and (B) at least one hydroxyaromatic compound contain-ing at least one aliphatic substituent having at least about 12 carbon atoms;
at least one position ortho to a hydroxy group in each of reagents A and B being unsubstituted.

16. A composition according to claim 15 wherein reagents A and B have the formulas (A) (B) wherein R is an aliphatic radical having at least about 12 carbon atoms; each X and each Y is individually hydrogen, halo, alkyl or hydroxyalkyl or haloalkyl of up to 4 carbon atoms, or alkoxy or alkylthio or up to 4 carbon atoms; and each of a and b is 1 or 2.

17. A composition according to claim 16 wherein R has at least about 40 carbon atoms.

18. A composition according to claim 17 wherein R has a number average molecular weight between about 600 and about 5000.

19. A composition according to claim 18 wherein R is a hydrocarbon radical having a number average molecular weight between about 800 and about 3000.

20. A composition according to claim 19 wherein a and b are each 1.

21. A composition according to claim 20 wherein both positions ortho to the hydroxy groups in reagents A
and B are unsubstituted.

22. A composition according to claim 21 wherein R is para to the hydroxy group.

23. A composition according to claim 22 wherein up to two X's and up to two Y's are alkyl or hydroxyalkyl radicals having up to 2 carbon atoms and all other X's and Y's are hydrogen.

24. A composition according to claim 22 wherein all X's and Y's are hydrogen.

25. A composition according to claim 24 wherein the solid and liquid components of the oxidative coupling agent comprise a catalyst prepared by combining a copper salt with an amine.

26. A composition according to claim 25 wherein the copper salt is a cuprous salt and the amine is a ter-tiary amine.

27. A composition according to claim 26 wherein the amine is pyridine and the cuprous salt is cuprous chloride.

28. An additive concentrate comprising a sub-stantially inert, normally liquid organic diluent and from about 20% to about 90% by weight of an oxidatively coupled product according to claim 14.

29. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of an oxidatively coupled product according to claim 14.

30. A fuel composition comprising a major amount of a nor-mally liquid fuel and a minor amount of an oxidatively coup-led product according to claim 14.