CA1223274A

CA1223274A - Boron-containing compositions and lubricants containing them

Info

Publication number: CA1223274A
Application number: CA000419514A
Authority: CA
Inventors: Frederick W. Koch
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1982-01-21
Filing date: 1983-01-14
Publication date: 1987-06-23
Also published as: GB8300753D0; FR2520363B1; GB2114116A; MX163037B; DE3301104A1; DE3301104C2; JPH0429717B2; GB2114116B; JPS58129099A; FR2520363A1; IN158265B

Abstract

NOVEL BORON-CONTAINING COMPOSITIONS
AND LUBRICANTS CONTAINING THEM

Abstract Boron-containing compositions are prepared by the reaction of boric acid, boron trioxide, a boron halide or an ester of boric acid with the condensation product (which may be formed in situ) of a hydroxyaromatic compound (preferably an alkylphenol) with an aliphatic aldehyde (preferably formaldehyde). They are useful as lubricant additives to inhibit oxidation, improve extreme pressure properties and decrease fuel consumption. They are especially useful as oxidation inhibitors in gear and bearing lubricants con-taining substantial amounts of sulfur and phosphorus com-pounds.

Description

~.~23~

NOVEL BORON-CONTAINING COMPOSITIONS AND LUBRICANTS
CONTAINING THEM

This invention relates to compositions useful as additives for lubricants, especially industrial gear oils to a method for the preparation of such compositions; and to additive concentrates and lubricants containing them. In their most general sense, the compositions of this invention are boron-containing compositions prepared by reacting, at a temperature within the range of about 70-250C.:
(A at least one compound of the formula Al H
(I) / C \
HO awry, I

wherein Al is hydrogen or a lower alkyl-based radical, R2 is hydrogen or an aliphatic hydrocarbon-based radical free from acetylenic unsaturation and An is an aromatic hydrocarbon-based radical; and (~) at least one of boric acid, boron trioxide,boron halides and esters of boric acid.
Recent developments in the area of machinery operation have materially increased the demands made on lubricants for use in such machinery. For example, in-creases in the price of gasoline and other fuels and sport adic shortages of such fuels have increased the necessity for lubricant additives which promote fuel economy. In the area of gear lubricants, it has been necessary to develop additives which improve operation under conditions of extreme pressure.
A further area of increasing demand on gear and bearing lubricants, particularly for industrial use, relates to formation of deposits through oxidation. Such deposits frequently form, especially in lubricants containing sub-staunchly amounts of phosphorus and sulfur compounds of the type commonly used as gear lubricant additives. The de-posits increase the susceptibility of the machinery to damage and decrease the efficiency of the lubricant. It is therefore of interest to develop improved oxidation inhibit ions which decrease deposit formation in lubricants, en-specially gear lubricants for industrial use.
A principal object of the present invention therefore is to provide novel boron-containing compost-lions.
A further object is to provide compositions useful to improve fuel economy and extreme pressure properties and to inhibit oxidation.
A further object is to provide lubricant additives particularly adapted for use in industrial gear and bearing lubricants.
A still further object is to provide a method for preparing boron-containing compositions useful for the above-described purposes.
Other objects will in part be obvious and will in part appear hereinafter.
As will be apparent from the brief description hereinabove, the boron-containing compositions of this invention are prepared from two reagents. Reagent A is at least one compound having Formula I. Such compounds may conveniently be prepared by the reaction of (A-l) at least one aliphatic aldehyde-releasing compound corresponding to an alluded having the formula RlCHO with (A-2) at least one hydroxyaromatic compound having the formula Wrier.

As used in the description of these compounds, the term "hydrocarbon-based radical" denotes a radical having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character within the context of this invention. Such radicals include the following:
(1) Hydrocarbon radicals; that is, aliphatic (e.g., alkyd or alkenyl), alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic- and alicyclic-substitu-10 ted aromatic, aroma~ic-substituted aliphatic and alicyclic radicals, and the like. Such radicals are known to those skilled in the art; examples are methyl, ethyl, propel, Huxley, decal, octadecyl, phenol, toll, naphthyl, hexenyl, dodecenyl and octadecenyl (all isomers being included).

(2) Substituted hydrocarbon radicals; that is, radicals containing non-hydrocarbon substituents which, in the context of this invention, do not alter the predomin-aptly hydrocarbon character of the radical. Those skilled in the art will be aware of suitable substituents; examples 20 are halo (especially sheller and broom), hydroxy, alkoxy, alkylthio, vitro and carbalkoxyO

(3) Hotter radicals; that is, radicals which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon 25 present in a chain or ring otherwise composed of carbon atoms. Suitable hotter atoms will be apparent to those skilled in the art and include, for example, nitrogen, oxygen and sulfur.
In general, no more than about three substituents 30 or hotter atoms, and preferably no more than one, will be present for each 10 carbon atoms in the hydrocarbon-based radical.
Terms such as "alkyl-based radical" and the like have meanings analogous to the above with respect to alkyd radicals and the like.
Preferably, the hydrocarbon-based radicals in the compounds of this invention are free from acetylenic and usually also from ethylenic unsaturationO The radicals are 2 3 ~,~

usually hydrocarbon and certain of them may be lower hydra-carbon, the work "lower" denoting radicals containing up to seven carbon atoms.
Reagent A-l, the aliphatic aldehyde-releasing compound, may be either a free alluded (e.g., formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde), an acutely thereof (e.g., formal, acetaldehyde deathly acutely), or a reversible polymer thereof (e.g., traction, paraformaldehyde, paraldehyde). Preferred as reagent A-l 10 are aldehyde-releasing compounds corresponding to aldehydes in which R2 is hydrogen or methyl and especially hydrogen.
Thus, the preferred aldehydes are formaldehyde and act-alluded, especially the former.
Reagent A-2 is at least one hydroxyaromatic 15 compound having the formula Wrier, in which R2 may be hydrogen or an aliphatic hydrocarbon-based radical free from acetylenic unsaturation. Most often, R2 is a hydrocarbon-based radical containing about 4-~00 and especially about 6-lo carton atoms. It is preferably an alkyd radical con-20 twining about 10-100 and most desirably about 10-40 carbon atoms. From the standpoint of availability and particular suitability to the purposes of this invention, compounds in which R2 is an alkyd radical containing about 15-30 carbon atoms are particularly contemplated The An radical is an aromatic hydrocarbon-based radical, typically derived from such aromatic compounds as Bunsen, naphthalene, biphenyl, diphenylmethane and diphenyl sulfide. Thus, the hydroxyaromatic compound may be, for example, phenol, a naphthol, an alkylphenol or alkylnaphthol, 30 or a sulfur- and/or methylene-bridged phenol or alkylphenol.
Suitable sulfur-bridged phenols may be prepared by the reaction of sulfur dichlorides with the corresponding phenol or alkylphenol. Methylene-bridged phenols may be prepared by a similar reaction with a formaldehyde-releasing reagent, 35 which may be at the same time as the reaction with Ryan A-l (which is, of course, preferably also a formaldehyde-releasing Regina or before or after that reaction.

The alkylphenols are preferred for use as reagent A-2, and especially those containing at least one unsub-sti-tuted ortho or pane carbon atom, preferably ortho.
Especially preferred are compounds in which An is a pen-5 ylene radical (i.e., -C6H~-) and most desirably o-phenylene.
Such compounds are typically prepared by the known alkali-lion of phenols with various olefins, alkyd halides and the like, including commercial mixtures of such olefins and allele halides.
By convention, thy "An" radical includes within its structure all hydrogen atoms bonded directly to an aromatic ring. Thus, all aromatic carbon atoms not bonded to some other part of the molecule or to a substituent, specified or unspecified, are understood to be bonded to 15 hydrogen atoms.
The reaction of reagents A-l and A-2 is a known reaction; it is frequently effected in the presence of an acidic or basic catalyst. Reactions of this type are disclosed, for example, in US. Patent 4,147r643.
Reagent B in the method of this invention is at least one of boric acid, boron trioxides (BYWAY), boron halides (especially boron trichloride, BC13) and esters of boric acid. Boron trioxides will react first with water formed in the reaction of reagents A-l and A-2 to form boric 25 acid, which then reacts further. Any of the various forms of boric acid may be used, including metabolic acid (HBO2), orthoboric acid (H3BO3) and tetraboric acid (H2B4O7). The esters of these acids include, for example, the methyl, ethyl and propel esters, with the methyl esters being most 30 readily available and -therefore most often used. Boric acid, and especially orthoboric acid, is preferred for use as reagent B.
The method of this invention involves reacting reagents A and B at a temperature within the range of about 35 70-250C, preferably about 90-150 and most often about 90-130C . It is often preferred to form reagent A in situ by heating a mixture of reagents A-l, A-2 and B. The reaction is frequently effected in the presence of a substantially inert, normally liquid organic delineate, typically . I

an aromatic hydrocarbon such as Tulane or zillion, a sheller-noted aromatic hydrocarbon such as chlorobenzene or an ether such as ethylene glycol dim ethyl ether.
When formaldehyde or a formaldehyde-releasing compound is used as reagent A-l, a portion thereof is sometimes lost by volatilization during the reaction. It is therefore preferred to use reagent A-l in excess. Most often, about 1.5-8.0 moles of reagent A-l and about 1.0-2.5 moles of reagent A-2 are used per mole of reagent B.
The reaction is frequently effected in the pros-once of (C) an acidic catalyst. Suitable acidic catalysts include acid-form anion exchange resins, sulfonic acids such as ben2enesulfonic and p-toluenesulfonic acids, and alkanoic acids such as acetic, prop ionic, butyric and Valerie acids.
The lower alkanoic acids and especially prop ionic acid are preferred. The amount of reagent C is typically less than 0.5 mole, most often about 0.1-0.3 mole, per mole or reagent A-l The molecular structures of the boron-containing compositions prepared by the method of this invention are not known with certainty. Most likely, they are mixtures of compounds having a number of molecular structures. However, there is strong evidence of the presence therein of come pounds having the formula Al H
t > t R2 _ Argo O - An - R2 wherein Al, I and An are as previously defined. Therefore, the present invention also includes boron-containing combo-sessions comprising at least one compound having formula II.
The preparation of the boron-containing compost-lions of this invention is illustrated by the following examples. All parts are my weight unless otherwise indict ted.

I

Example 1 A mixture of 485.7 grams (1 mole) of an alkyd phenol prepared by alkylation of phenol with a commercial mixture of C24-2 3 ~-olefins, 10 grams (1 mole) of purifier-molded, 30.9 grams (0.5 mole) of boric acid, 22.2 grooms mole) of prop ionic acid and 600 ml. of Tulane is heated under reflex for 3 hours, as water is removed by distillation. An additional 10 grams of paraformaldehyde is added and refluxing is continued for 2 hours; a third 10-gram portion ox paraformaldehyde (total 3 moles) is then added and refluxing is continued as water and excess pane-formaldehyde are removed A total of 45 ml. of water is obtained. The mixture is filtered and vacuum stripped to yield the desired product, which contains 1.19% boron.
Example 2 _ A product similar to that of Example 1 is obtained from 1,094 grams (I moles) of the alkylphenol of Example 1, 120 grams (4 moles) of paraformaldehyde added in two 60-gram increments, 123.6 grams (2 moles) of boric acid, 44.4 grams (0.6 mole) of prop ionic acid and 700 ml. of Tulane. It contains 1.32% boron.
Example 3 A mixture of 1,094 parts (2 moles) of the alkyd-phenol of Example 1, 60 parts (2 moles) of paraformaldehyde, 61.8 parts (1 mole) of boric acid, 44.4 parts (0.6 mole) of prop ionic acid and 200 parts of Tulane is heated under reflex for about 6 hours as water (about 70 parts) is removed by distillation. The mixture is then vacuum strip-pod and filtered at Luke. to yield the desired product;
it contains 0.73% boron.
Example 4 A mixture of 536 parts I mole) of the alk~lphenol of Example 1, 30 parts (1 mole) of paraformaldehyde, 30.9 parts (0.5 mole) of boric acid and 100 parts of Tulane is heated under reflex for 3 hours as waxer is removed by distillation. A second 30-part increment of paraformaldehyde ~2~3Z~

(total 2 moles) is added and heating under reflex is con-tinted for 5 hours. A total of US ml. of water is removed.
The mixture is then vacuum stripped and filtered while hot to yield the desired product; it contains 0.89% boron.
Example 5 following the procedure of Example 1, a product containing 1.75~ boron is obtained by the reaction of 792 grams (3 moles) of tetrapropenylphenol, 270 grams (9 moles, added in three 3-mole increments) of paraformaldehyde, 92.7 10 parts (1.5 moles) of boric acid, 66.6 parts (0.9 mole) of prop ionic acid and 1,000 ml. of Tulane Example 6 A mixture of 430 parts (1 mole) of an alkylphenol prepared by alkylation of phenol with a commercial mixture 15 of Clue ~-olefins, 30 parts (1 mole) of paraformaldehyde, 30.9 parts (0.5 mole) of boric acid, 22.2 parts (0.3 mole) of prop ionic acid and 100 parts of Tulane is heated under reflex as water is removed by distillation. After 33 my of water have been removed, an additional 30 parts of pyre 20 formaldehyde is added (total 2 moles) and refluxing is continued as water (total I ml.) and paraformaldehyde are removed by distillation. The mixture is vacuum stripped and filtered to yield the desired product; it contains 1.14%
boron.
25 Example 7 A mixture of 1,945 parts (5 moles) of an alkyd-phenol prepared by alkylation of phenol with a decent diver, 150 parts (5 moles) of paraformaldehyde, 154 parts (2.5 moles) of boric acid, ~8.8 parts (1.2 moles) of prop ionic 30 acid and 300 parts of Tulane is heated under reflex as water is removed by distillation. When 157 parts of water has been removed, an additional 150 parts of paraformalde-Hyde is added (total 10 moles) and heating is continued until water evolution is complete. The mixture is vacuum 35 stripped and filtered while hot. The filtrate is the desired product; it contains 1.44% boron.

~2~3~
g Example 8 A boron-containing composition is prepared by a method similar to that of Example 1 except that trim ethyl borate is substituted, on an equimolar basis, for the boric acid.
Example 9 A boron-containing composition is prepared by a method similar to that of Example 1 except that paraldehyde and acetic acid are respectively substituted, on an equip molar basis, for the paraformaldehyde and prop ionic acid.
As previously indicated, the boron-containing compositions of this invention are useful as additives for lubricants. They are particularly useful as oxidation inhibitors and extreme pressure agents in gear an bearing lubricants; however, they may also be used in internal combustion engine lubricants to reduce fuel consumption.
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, In add-20 lion to gear and bearing lubricants, the boron-containing compositions may be used in 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 25 engines, and the like. The boron-containing compositions can also be used in gas engines, stationary power engines and turbines and the like. Automatic transmission fluids, transsexual lubricants, metalworking lubricants, hydraulic fluids and other lubricating oil and grease compositions can 30 also benefit from the incorporation therein of the boron-containing compositions.
Natural oils include liquid petroleum oils and solvent-treated, acid treated and/or hydrorefined mineral lubricating oils of the paraffinic, naphthenic and mixed 35 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 polyp merited and inter polymerized olefins [e.g., polybutylenes, polypropylene, propylene-isobutylene copolymers, chlorine S axed polybutylenes, poly(l-hexenes), poly(l-octenes), poly(l-decenes)]; alkylbenzenes [erg., dodecylbenzenes, tetradecylbenzenes, dinonylben2enes, di(2-ethylhexyl)ben-zones]; polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); and alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homology thereof.
Alkaline oxide polymers and inter polymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., 15 constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyd and aureole ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1003, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, deathly ether of polypropylene glycol having a molecular weight of 1000-1500); and moo- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3-C B
fatty acid esters and Of 3 Ox acid divester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyd succinic acids and 30 alkenyl succinic acids, malefic acid, azelaic acid, sub Eric acid, sebacic acid, fumaric acid, adipic acid, linoleic acid diver, Masonic acid, alkyd Masonic acids, alkenyl Masonic acids) with a variety of alcohols (e.g., bottle alcohol, Huxley alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethyl-35 one glycol, diethylene glycol monoether, propylene glycol).Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) subacute, di-n-hexyl fumarate, ductile subacute, disquietly assault, deciduously assault, ductile I

phthalate, didecyl phthalate, dieicosyl subacute, the 2-ethylhexyl divester of linoleic acid diver, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethyl-hexanoic acid.
Esters useful as synthetic oils also include those made from Us to Of 2 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
Silicon-based oils such as the polyalkyl-, polyp aureole-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic lubricants;
they include tetraethyl silicate, tetraisopropyl silicate, tetra-(2~ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hooks-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, deathly 20 ester of decylphosphonic acid) and polymeric tetrahydro-furriness.
Unrefined, refined and redefined oils can be used in the lubricants 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 distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil.
30 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. Man such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art. Redefined 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 redefined oils are also known as reclaimed or I

reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
Generally, the lubricants of the present invention contain an amount of the boron-containing composition sufficient to inhibit oxidation, improve extreme pressure properties or decrease fuel consumption. Normally this amount will be about 0.1-5.0~, preferably about 0.5-2.5% and most often about 0.5-1.5% by weight.
The invention also contemplates the use of other additives in combination with the boron-containing compost-lions. Suitable additives for internal combustion engine lubricants include, for example, detergents and dispersants of the ash-producing or cashless type, corrosion-inhibiting 15 and auxiliary oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, color stabile-zero and anti-foam agents.
The ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline 20 earth metals with sul~onic acids, carboxylic acids, and organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage including those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing 25 agent such as phosphorus trichloride, phosphorus Hyatt-sulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphor-thwack chloride. The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, 30 strontium and barium.
The term "basic salt" is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. The commonly employed methods for preparing the basic salts involve heat-35 in a mineral oil solution of an acid with a stoichiometricexcess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50C. and filtering the resulting mass.

I

The use of a "promoter" in thy neutralization step to aid the incorporation of a large excess of metal likewise is known Examples of compounds useful as the promoter include finlike substances such as phenol, naphthol, alkylphenols, thiophenol, sulfurized alkylphenols, and condensation pro-ducts of formaldehyde with finlike substances; alcohols such as methanol, ~-propanol, octal alcohol, Cello solve*
Carbitol* ethylene glycol, stroll alcohol and cyclohexyl alcohol and amine such as aniline phenylenediamine, 10 phenothiazine, phenyl-~-naphthylamine and dodecylamine. A
particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonating the mixture at an elevated them-15 portray such as 60-200C.
Cashless detergents and dispersants are so called despite the fact that, depending on its constitution, the dispersant may upon combustion yield a non-volatile material such as boric oxide or phosphorus pent oxide; however, it 20 does not ordinarily contain metal and therefore does not yield a metal-containing ash on combustion. Many types are known in the art, and any of them are suitable for use in the lubricants of this invention. The following are thus-trative:
I Reaction products of carboxylic acids (or derivatives thereof) containing at least about 34 and pro-fireball at least about 54 carbon atoms with nitrosen-con-twining compounds such as amine, organic hydroxy compounds such as phenols and alcohols, and/or basic inorganic mater-30 tats. Examples of these "carboxylic dispersants" are described in many US. patents including 3,272,746; 3,381,022;
and 4,234,435.
(2) Reaction products of relatively high Milwaukee-far weight aliphatic or alicyclic halides with amine, pro-fireball polyalkylene polyamides. These may be characterized as "amine dispersants" and examples thereof are described for example, in US. patents 3,275,554; 3,438,757; 3,454,555;
and 3,565,804.

* trade marks (3) Reaction products of alkyd phenols in which the alkyd group contains at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amine (especially polyalkylene polyamides), which may be characterized as "Mannish dispersants". The materials described in US.
patents 3,368,972; 3,413,347; and 3,980,569 are illustrative.

(4) Products obtained by post-treating the car-boxlike, amine or Mannish dispersants with such reagents as urea, Thor, carbon disulfide, aldehydes, kittens, car-boxlike acids, hydrocarbon-substituted succinic arJhydrides, nitrites, epoxies, boron compounds, phosphorus compounds or the like. Exemplary materials of this kind are described in a number of US. patents.

(5) Inter polymers of oil-solubilizing monomers such as decal methacrylate, vinyl decal ether and high molecular weight olefins with monomers containing polar substituents, e.g., aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substitued acrylates. These may be characterized as "polymeric dispersants" and examples there-of are disclosed in US. patents 3,329,658; 3,449,250;
3,519,565; 3,666,730; 3,687,849; and 3,702,300.
Extreme pressure agents and corrosion-inhibiting and auxiliary oxidation-inhibiting agents are exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wax;
organic sulfides and polysulfides such as bouncily disulfide, bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized methyl owlet, sulfurized alkylphenols, sulfurized dipentene, and sulfurized terrapins; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turn pontoon or methyl owlet; phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphates such as dibutyl phosphate, doughtily phosphate, dicyclohexyl phosphate, pen-tylphenyl phosphate, dipentylphenyl phosphate, tridecyl phosphate, distearyl phosphate, dim ethyl naphthyl I

phosphate, oilily ~-pentylphenyl phosphate, polypropylene (molecular weight substituted phenol phosphate and diisobutyl-substituted phenol phosphate; metal thiocarba-mates such as zinc dioctyldithiocarbamate and barium hop-tylphenyl dithiocarbamate; Group II metal phosphorodithi-orates such as zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium di(heptylphenyl)phos-phorodithioate, cadmium dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic acid produced by tune reaction of phosphorus pentasulfide with an equimolar mixture of isopropyl alcohol and n-hexyl alcohol.
Gear and bearing lubricants according to this invention may contain the boron-containing composition in combination with known gear lubricant additive packages.
These packages frequently contain substantial amounts, effective to improve the extreme pressure properties thereof, of sulfur and phosphorus compounds. Many suitable gear lubricant additive packages of this type are known tug those skilled in the art. The boron-containing compositions are 20 particularly effective as oxidation inhibitors in such lubricants containing relatively high sulfur and phosphorus levels.
The boron-containing compositions of this invent lion may be, and frequently are, added directly to the 25 otherwise sully formulated lubricant prior to use. over, they may also be diluted with a substantially inert, nor-molly liquid organic delineate such as mineral oil, naphtha~
Bunsen, Tulane or ~ylene to form an additive concentrate These concentrates may contain prom about 10~ to about 90%
30 by the weight of the boron-containing composition and may contain, in addition, one or more other additives known in the art or described hereinabove.
The following is illustrative of a gear and bearing lubricant of this invention. All parts are by 35 weight.

I

Mineral oil 97.89 parts Product of Example l 0.75 part Soybean oil 0.25 part Sulfurized isobutene 0.62 part Amine-neutralized phosphate ester of hydroxyalkyl dialkylphosphorodithioate 0.40 part Polyoxyalkylene emulsifier 0.005 part N~Tridecyltrimethylenediamine 0.05 part lo Tolyltriazole 0.015 part Silicone anti-foam agent 0.02 part I

Supplementary Disclosure It has been discovered that, in a broader sense, the compositions of the present invention are boron-con-twining compositions prepared by reaction, at a temperature within the range of about 70-250C:
(A') at least one compound of the formula Al / H
/ C Formula IV
HO \ Awry ( R2 I/
wherein R is hydrogen, a lower alkyl-based radical or an aromatic hydrocarbon-based radical, R is hydrogen or an aliphatic hydrocarbon-based radical free from acetylenic unsaturation, n is a number from l to 4, and An is an art-matte hydrocarbon-based radical; and (B) at least one of boric acid, boron trioxides boron halides and esters of boric acid.
A method for preparing the aforesaid boron-containing compositions comprises reacting, at a tetnperature within the range of about 70-250C:
(A') at least one compound of the formula Al H
> Formula IV
HO Awry (R2)/
wherein Al is hydrogen, a lower alkyl-based radical or an aromatic hydrocarbon-based radical, R2 is hydrogen or an elf-phatic hydrocarbon-based radical free from acetylenic unswept-ration, n is a number from l to 4, and An is an aromatic hydrocarbon-based radical; and (B) at least one of boric acid, boron trioxides boron halides and esters of boric acid is described.

fly As set forth in the principal disclosure, the boron-containing compositions of this invention are prepared from two reagents. Reagent A' is at least one compound having Formula IV. Such compounds may conveniently be prepared by the reaction of (A-l) at least one aliphatic or aromatic aldehyde-releasing compound corresponding to an alluded having the formula RlCHO with (Aye) at least one hydroxy-aromatic compound having the formula (R ) -An OH.
Reagent A-l, the aliphatic or aromatic alluded-releasing compound, may be either a free alluded (e.g. for-molded, acetaldehyde, propionaldehyde, benzaldehyde, butyraldehyde, valeraldehyde), an acutely thereof (e.g., formal, acetaldehyde deathly acutely), or a reversible polyp men there of (e.g., traction, paraformaldehyde, paraldehyde).
As set forth in the principal disclosure, preferred as a reagent A-l are aldehyde-releasing compounds corresponding to aldehydes in which R is hydrogen or methyl and especially hydrogen. Thus, the preferred ald~hydes are formaldehyde and acetaldehyde, especially the former.
Reagent Aye is at least one hydroxyaromatic come pound having the formula (R Norway, in which R may be hydrogen or an aliphatic hydrocarbon-based radical free from acetylenic unsaturation and n is a number from 1 to 4, generally 1 or 2. Most often, when n is 2 or more, each R
is an alkyd group containing up to 20 carbon atoms. When n is 1, R is a hydrocarbon-based radical containing about 4-200 and especially about 6-100 carbon atoms. More particularly, when n is 1, R is preferably an alkyd radical containing about 4-100 or 10-100 and most desirably about 6-40 or 10-40 carbon atoms. From the standpoint of availability and particular suitability to the purposes of this invention, two types of hydroxyaromatic compounds are preferred; when n is 1, R is preferably an alkyd group containing from about ~,~

7-30 or 15-30 carbon atoms; when n is 2 or more, each R2 may contain up to 12 carbon atoms. Mixtures of the above-identified hydroxy aromatic compounds also can be used as reagent Aye. Very often commercially available alkyd phenols are mixtures of the Monday- and tri-alkyl phenols.
Some typical examples of commercial mixtures of alkyd phenols which are useful include a mixture comprising Detroit-bottle phenol (97.5% wt.), para-tert-butyl phenol (2.0% wt.) and 2,4,6-tri-tert-butyl phenol (0.5% wt.) available from Ferry Corporation under the trade designation "2,4-di-tertiary bottle phenol, 97%". Another mixture comprises 80% wt. of 2,4-di-tert-butyl phenol, 7-8% wt. of 2,4,6-tri-tert-butyl phenol, 7-8% wt. of para-tert-butyl phenol, 1% of ortho left-bottle phenol, and 1% wt. Max of phenol.
The alkylphenols represented by the formula OH

Formula V

and mixtures thereof are preferred for use as reagent Aye, and especially those containing at least one unsubstituted ortho or pane carbon atom, preferably ortho. As set forth in the principal disclosure especially preferred are compounds in which An is a phenylene radical (i.e. -C6H4-) and most desirably o-phenylene. Such compounds are typically prepared by the known alkylation of phenols with various oiliness, alkyd halides and the like, including commercial mixtures of such olefins and alkyd halides.
The reaction of reagents A-l and Aye is a known reaction; it is frequently effected in the presence of an acidic or basic catalyst As afore-described, reactions of this type are disclosed, for example, in US. Patent 4,147,643.
Reagent B in the method of this invention is at least one of boric acid, boron trioxides (BYWAY), boron halides I

(especially boron trichloride, BC13), boron halides (espy-Shelley boron trichloride, BC13) and esters of boric acid.
Boron trioxides will react first with water formed in the reaction of reagents A-l and Aye to form boric acid, which then reacts further. As set forth in the principal disclosure, and exemplified therein, any of the various forms of boric acid may be used.
The method of this invention involves reacting reagents A' and B at a temperature within the range of about 70-250C, preferably about 90-150C and most often about 90-130C. It is often preferred to form reagent A' in situ by heating a mixture of reagents A-l, Aye and B. The reaction is frequently effected in the presence of a substantially inert, normally liquid organic delineate, typically an aromatic hydrocarbon such as Tulane or zillion, a chlorinated aromatic hydrocarbon such as chlorobenzene or an ether such as ethyl tone glycol dim ethyl ether.
When formaldehyde or a formaldehyde-releasing come pound is used as reagent A-l, a portion thereof is sometimes lost by volatilization during the reaction. It is therefore preferred to use reagent A-l in excess. Most often, about 1.5 8.0 moles of reagent A-l and about 1.0-2.5 moles of reagent Aye are used per mole of reagent B.
The reaction of A-l, Aye and B is frequently effected in the presence of (C), a catalyst. It has been observed, however, that the reaction will proceed without a catalyst.
Suitable acidic catalysts include acid-form anion exchange resins, sulfonic acids such as benzene-sulfonic and Tulane sulfonic acids, and alkanoic acids such as acetic, prop ionic, butyric and Valerie acids. The lower alkanoic acids and en-specially prop ionic acid are preferred. The amount of reagent C is typically less than 0.5 mole, most often about 0.1-0.3 mole, per mole or reagent A-l. Examples of bases useful as catalysts include inorganic bases such as the alkali metal hydroxides.

, - I -The molecular structures of the boron-containiny compositions prepared by the method of this invention are not known with certainty. Most likely, they are mixtures of compounds having a number of molecular structures. How-ever there is strong evidence of the presence therein of compounds having the formula Al H Al H owe O - _ H
2 > < Formula VI

(R awry O o An _ (R on wherein R , R2, n and An are as previously defined. There-fore, the present invention also includes boron-containing compositions comprising at least one compound having Formula VI.
The preparation of the boron-containing compositions of this invention is further illustrated by the following examples, all parts and percentages being by weight unless otherwise indicated.
Example 10 A mixture of 206.3 grams of 2,4-di-tert-butyl phenol (1 mole), 30.9 grams (0.5 mole) of boric acid, 22.2 grams (0.3 mole) of prop ionic acid, 150 ml. of Tulane and 30 grams (1 mole) of paraformaldehyde is charged to a reaction flask and heated to reflex with collection of 28 ml. of water. A
second 30 grams of paraformaldehyde is added and refluxing continued with removal of a small amount of water and a larger amount of paraformaldehyde. The reaction mixture is filtered through filter acid and the filtrate is stripped at 200C/
25 mm. Hug. to yield the desired product containing 2.17%
boron.
Example 11 A mixture of 824 grams (4 moles) of 2,4-di-tert-butyl I

phenol, 80% (Ferry Corporation), 180 grams (6 moles) of paraformaldehyde, 123.6 grams (2 moles) of boric acid and 300 grams of Tulane is charged to a reactor and heated to reflex with removal of water (191 grams of water removed).
Delineate oil (960 grams) is added and the mixture is stripped at 150C/25 mm. Hug. The residue is filtered, and the lit-irate is the desired product containing 1.24% boron.
Example 12 A mixture of 619 grams (3 moles) of Detroit-bottle phenol, 97% (Ferry Corporation), 90 grams (3 moles) of paraformaldehyde, 92.7 grams (1.5 moles) of boric, 33.3 grams of prop ionic acid and 250 grams of Tulane are charged to a reactor and heated to xeflux while removing water (88 ml. collected). A second 90 grams of paraformaldehyde is added and refluxing was continued up to 140C with removal of solid paraformaldehyde. Delineate oil (720 grams) is added and the mixture is stripped at 175C/30 mm. The residue is filtered warm and the filtrate is the desired product con-twining 1.23% boron.
Example 13 -A mixture of 619 grams (3 moles) of -the Detroit-bottle phenol used in Example 12, 135 grams (4.5 moles) of paraformaldehyde, 92.7 grams (1.5 moles) of boric acid and 250 grams of Tulane are charged to a reactor and heated to reflex while removing water (139 ml. of water recovered).
Delineate oil (720 grams) is added to the reactor, and the mix-lure is stripped at aspirator to 150C. The residue is the desired product containing 1.23% of boron.
Example 14 A mixture of 1030 parts of 2,6-di-t-butyl phenol and 1145 parts of a mixture of alpha-olefins containing 15 to 18 carbon atoms is charged to a reactor and 109 parts of Super-filtrol is added at 40C. The reaction mixture is heated to ~2~3~7~

85-90C and maintained at that temperature for about 2.5 hours followed by heating at 130-140C for an additional two to five hours. The mixture then is filtered through a filtered, and the filtrate is returned to the reaction flask where volatile are stripped at 140C/5 mm. Hug. The residue is filtered, and the filtrate is the desired alkylated, t-butyl phenol.
A mixture of 920 parts of the above-prepared alkylated, t-butyl phenol product, 90 of paraformaldehyde, 62 parts of boric acid, 45 parts of prop ionic acid, and 500 parts of Tulane is charged to a reactor and the mixture is heated to reflex for three hours to a temperature of 130-135C. Water, excess paraformaldehyde and Tulane is removed in a side-arm trap. The crude material is stripped at 135-140C/10 mm. Hug. and filtered. The filtrate is the desired product.
Example 15 A mixture of 1030 parts of 2,6-di-t-butyl phenol and 725 parts of a polypropylene tetramer (molecular weight of 145) is charged to a reactor and heated to about 40C
whereupon 88 parts of Suprafiltrol is added. The reaction is conducted in a nitrogen atmosphere. The temperature of the reaction is raised to 145-150C and thereafter maintained at 90-95C at 5 mm. Hug. for about 3.5-4 hours while collecting water in a side-arm trap. The reaction mixture is filtered, and the filtrate is the desired alkylated -t-butyl phenol.
A mixture of 600 parts of the above-prepared alkyd fated t-butyl phenol, 120 parts of paraformaldehyde, 62 parts of boric acid, 22 parts of prop ionic acid and 500 parts of Tulane is charged to a reactor and heated to reflex for three hours to a temperature of about 130-135C while got-looting a mixture of water, excess paraformaldehyde and Tulane.
The crude mixture is stripped to 140C/10 mm. Hug. and filtered.
The filtrate is the desired boron-containiny product.

I`" 3L2~3~
- I -Example 16 A mixture of 206 parts of 2,4-di-t-butyl phenol, 30 parts of paraformaldehyde and 0.5 parts of sodium hydroxide is heated to 130C, and 31 parts of boric acid is added while sparring with nitrogen. The mixture then is heated at ll0-170C for one hour while removing water.
The mixture is vacuum stripped to 160C at 30-40 mm. Ho., 241 parts of mineral oil are added, and the mixture is filtered. The filtrate is the desired product containing 0.94~ of boron.
The following table contains examples of gear and bearing lubricants of this invention. All parts being by weight.

Lubricant Examples 2 3 Mineral Oil 97.83 98.06 Product of Example 10 0.75 Product of Example 11 - 0.50 Polyisobutenyl succinic android-ethylene polyamide reaction product - 0.05 Oleamide/linoleamide mixture - 0.03 Soybean Oil 0.25 Sulfurized isobutene 0.687 0.95 Amine neutralized phosphate ester of hydroxylalkyl dialkylphosphorodithioate 0.40 0.26 Polyoxyalkylene emulsifier 0.005 0.005 N-Tridecyltrimethylenediamine 0.05 0.05 Tolyltriazole 0.015 Mixed tertiary alcoholically) aliphatic primary amine - -Reaction product of alkyd phenol, formaldehyde and demarcate thiadiazole - 0.04 Silicone anti-foam agent 0.02 0.02

Claims

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

1. A method for preparing a boron-containing composition which comprises reacting, at a temperature within the range of about 70-250°C.:
(A) at least one compound of the formula wherein R1 is hydrogen or a lower alkyl-based radical, R2 is hydrogen or an aliphatic hydrocarbon-based radical free from acetylenic unsaturation and Ar is an aromatic hydro-carbon-based radical wherein the -OH radical is 1, 2 or 1, 3 with respect to the methylol group; and (B) at least one of boric acid, boron trioxide, boron halides and esters of boric acid.

2. A method according to claim 1 wherein reagent A is formed in situ by the reaction of (A-1) at least one aliphatic aldehyde-releasing compound corresponding to an aldehyde having the formula R1CHO with (A-2) at least one hydroxyaromatic compound having the formula R2-Ar-OH.

3. A method according to claim 2 wherein Ar contains at least one unsubstituted ortho or para carbon atom.

4. A method according to claim 3 wherein Ar con-tains at least one unsubstituted ortho carbon atom.

5. A method according to claim 3 wherein Ar is a phenylene radical.

6. A method according to claim 5 wherein Ar is an o-phenylene radical.

7. A method according to claim 6 wherein R1 is hydrogen or methyl.

8. A method according to claim 7 wherein R2 is a hydrocarbon-based radical containing about 4-200 carbon atoms.

9. A method according to claim 8 wherein R2 is an alkyl radical containing about 6-100 carbon atoms.

10. A method according to claim 9 wherein R2 is an alkyl radical containing about 10-100 carbon atoms.

11. A method according to claim 10 wherein R2 contains about 10-40 carbon atoms.

12. A method according to claim 11 wherein R1 is hydrogen.

13. A method according to claim 12 wherein reagent B is orthoboric acid and the reaction temperature is in the range of about 90-150°C.

14. A method according to claim 13 wherein R2 contains about 15-30 carbon atoms.

15. A method according to claim 1, 2 or 8 wherein the reaction is effected in the presence of (C) an acidic catalyst.

16. A method according to claim 1, 2 or 8 wherein the reaction is effected in the presence of an alkanoic acid.

17. A method according to claim 1, 2 or 8 wherein the reaction is effected in the presence of a lower alkanoic acid.

18. A method according to claim 1, 2 or 8 wherein the reaction is effected in the presence of propionic acid.

19. A method according to claim 2, 4 or 8 wherein about 1.5-8.0 moles of reagent A-1 and about 1.0-2.5 moles of reagent A-2 are used per mole of reagent B.

20. A method according to claim 1, 2 or 8 wherein the reaction is effected in the presence of (C) an acidic catalyst and about 1.5-8.0 moles of reagent A-1 and about 1.0-2.5 moles of reagent A-2 are used per mole of reagent B.

21. A method according to claim 1, 2 or 8 wherein the reaction is effected in the presence of an alkanoic acid and about 1.5-8.0 moles of reagent A-1 and about 1.0-2.5 moles of reagent A-2 are used per mole of reagent B.

22. A composition prepared by the method of claim 1, 2 or 8.

23. A boron-containing composition comprising at least one compound having the formula wherein R1 is hydrogen or a lower alkyl-based radical, R2 is hydrogen or an aliphatic hydrocarbon-based radical free from acetylenic unsaturation, and Ar is an aromatic hydro-carbon-based radical wherein Ar is bonded to the rest of the molecule through ortho or meta positions.

24. A composition according to claim 23 wherein Ar is bonded to the rest of the molecule through ortho positions.

25. A composition according to claim 23 wherein Ar is a phenylene radical.

26. A composition according to claim 25 wherein Ar is an o-phenylene radical.

27. A composition according to claim 26 wherein R1 is a hydrogen or methyl.

28. A composition according to claim 27 wherein R2 is a hydrocarbon-based radical containing about 4-200 carbon atoms.

29. A composition according to claim 28 wherein R2 contains about 6-100 carbon atoms.

30. A composition according to claim 29 wherein R2 is an alkyl radical containing about 10-100 carbon atoms.

31. A composition according to claim 30 wherein R2 contains about 10-40 carbon atoms.

32. A composition according to claim 31 wherein R1 is hydrogen.

33. A composition according to-claim 32 wherein R2 contains about 15-30 carbon atoms.

34. An additive concentrate comprising a sub-stantially inert, normally liquid organic diluent and about 20-90% by weight of a composition prepared by the method of claim 1, 2 or 8.

35. An additive concentrate comprising a sub-stantially inert, normally liquid organic diluent and about 20-90% by weight of a composition according to claim 23.

36. A lubricating composition comprising a major amount of a lubricating oil and about 0.1-5.0% by weight of a composition prepared by the method of claim 1, 2 or 8.

37. A lubricating composition comprising a major amount of a lubricating oil and about 0.1-5.0% by weight of a composition prepared by the method of claim 1, 2 or 8 and which also contains minor amounts, effective to improve the extreme pressure properties thereof, of sulfur and phosphorus compounds.

38. A lubricating composition comprising a major amount of a lubricating oil and about 0.1-5.0% by weight of a composition according to claim 23.

39. A composition according to claim 38 which also contains minor amounts, effective to improve the extreme pressure properties thereof, of sulfur and phos-phorus compounds.

CLAIMS BASED ON THE SUPPLEMENTARY DISCLOSURE:

40. A method for preparing a boron-containing composition which comprises reaction, at a temperature within the range of about 70-250°C:
(A') at least one compound of the formula wherein R1 is hydrogen, a lower alkyl-based radical or an aromatic hydrocarbon-based radical, R2 is hydrogen or an aliphatic hydrocarbon-based radical free from acetylenic unsaturation, n is a number from 1 to 4, and Ar is an aromatic hydrocarbon-based radical wherein the -OH radical is 1, 2 or 1, 3 with respect to the methylol group; and (B) at least one of boric acid, boron trioxide, boron halides and esters of boric acid.

41. A method according to claim 40 wherein reagent A' is formed in situ by the reaction of (A-1) at least one aromatic or aliphatic aldehyde-releasing compound corres-ponding to an aldehyde having the formula R1CHO with (A'-2) at least one hydroxyaromatic compound having the formula (R2)n-Ar-OH.

42. A method according to claim 41 wherein Ar contains at least one unsubstituted ortho or para carbon atom.

43. A method according to claim 42 wherein Ar contains at least one unsubstituted ortho carbon atom.

44. A method according to claim 42 wherein Ar is a phenylene radical.

45. A method according to claim 44 wherein Ar is an o-phenylene radical.

46. A method according to claim 45 wherein R1 is hydrogen or methyl.

47. A method according to claim 46 wherein R2 is a hydrocarbon-based radical containing about 1-200 carbon atoms.

48. A method according to claim 47 wherein n is 2 to 4 and each R2 is an alkyl radical containing up to 20 carbon atoms.

49. A method according to claim 48 wherein R2 is a tert-butyl group.

50. A method according to claim 47 wherein n is 1 and R2 is an alkyl radical containing about 4-100 carbon atoms.

51. A method according to claim 50 wherein R2 contains about 6-40 carbon atoms.

52. A method according to claim 40 wherein reagent B is orthoboric acid and the reaction temperature is in the range of about 90-150°C.

53. A method for preparing a boron-containing composition which comprises reacting, at a temperature with-in the range of about 70-250°C:
(A') at least one compound of the formula wherein R1 is hydrogen, a lower alkyl-based radical or an aromatic hydrocarbon-based radical, R2 is hydrogen or an aliphatic hydrocarbon-based radical free from acetylenic unsaturation, n is a number from 1 to 4, and Ar is an aromatic hydrocarbon-based radical wherein the -OH radical is 1, 2 or 1, 3 with respect to the methylol group; and (B) at least one of boric acid, boron trioxide, boron halides and esters of boric, in the presence of (C) an acidic or basic catalyst.

54. A method according to claim 53 wherein reagent A' is formed in situ by the reaction of (A-1) at least one aromatic or aliphatic aldehyde-releasing compound corres-ponding to an aldehyde having the formula R1CHO with (A'-2) at least one hydroxyaromatic compound having the formula (R2)n-Ar-OH.

55. A method according to claim 53 wherein Ar contains at least one unsubstituted ortho carbon atom.

56. A method according to claim 53 wherein R2 is a hydrocarbon-based radical containing about 1-200 carbon atoms.

57. A method according to claim 53 wherein n is at least one number from 2 to 4 and each R2 is an alkyl radical containing up to 20 carbon atoms.

58. A method according to claim 57 wherein R2 is a t-butyl group.

59. A method according to claim 56 wherein n is 1 and R2 contains 6-40 carbon atoms.

60. A method according to claim 59 wherein R2 contains about 10-40 carbon atoms.

61. A method according to claim 53 wherein reagent B is orthoboric acid and the reaction temperature is in the range of about 90-150°C.

62. A method according to claim 53 wherein C
is an acid catalyst.

63. A method according to claim 61 wherein C
is an alkanoic acid.

64. A method according to claim 53 wherein C
is a base.

65. A method according to claims 40 or 53 wherein about 1.5-g.0 moles of reagent A-1 and about 1.0-2.5 moles of reagent A'-2 are used per mole of reagent B.

66. A composition prepared by the method of claims 40, 48 or 49.

67. An additive concentrate comprising a sub-stantially inert, normally liquid organic diluent and about 20-90% by weight of a composition prepared by the method of claims 40, 48 or 49.

68. A lubricating composition comprising a major amount of a lubricating oil and about 0.1-5.0% by weight of a composition prepared by the method of claims 40, 48 or 49.

69. A lubricating composition comprising a major amount of a lubricating oil, about 0.1-5.0% by weight of a composition prepared by the method of claims 40, 48 or 49, and a minor amount, effective to improve the extreme pressure properties thereof, of compounds containing sulfur or phosphorus or a combination of sulfur and phosphorus.