FR2520363A1 - NOVEL BORON-CONTAINING COMPOSITIONS AND LUBRICANTS CONTAINING SAME - Google Patents

Abstract

THE INVENTION RELATES TO NEW COMPOSITIONS CONTAINING BORON AND LUBRICANTS CONTAINING THEM. COMPOSITIONS CONTAINING BORON ARE PREPARED BY THE REACTION OF BORIC ACID, BORON TRIOXIDE, A BORON HALOGENIDE OR A BORIC ACID ESTER WITH THE CONDENSING PRODUCT (WHICH MAY BE FORMED IN SITU) OF A HYDROXY-AROMATIC COMPOUND (PREFERREDLY AN ALCOYLPHENOL) WITH AN ALIPHATIC ALDEHYDE (PREFERREDLY FORMALDEHYDE). THEY ARE USEFUL AS LUBRICANT ADDITIVES TO INHIBIT OXIDATION, IMPROVE EXTREME PRESSURE PROPERTIES AND REDUCE FUEL CONSUMPTION. THEY ARE ESPECIALLY USEFUL AS OXIDIZATION INHIBITORS IN GEAR AND BEARING LUBRICANTS CONTAINING LARGE QUANTITIES OF SULFUR AND PHOSPHORUS COMPOUNDS.

Description

The present invention relates to compositions useful as additives

  for lubricants, especially for industrial gear oils; a process for the preparation of these compositions; and additive concentrates and lubricants containing them In their most general sense, the compositions according to the present invention are boron-containing compositions prepared by reacting, at a temperature between about 70 and 250 ° C (a) at less a compound of the formula

R 1 H

HO -OH,

  R 2 in which R is hydrogen or a lower alkyl radical, R is hydrogen or a radical to

  aliphatic hydrocarbon base free from unsaturated

  tylenic and Ar is an aromatic hydrocarbon-based radical

  matic; and (B) at least one compound selected from boric acid, boron trioxide, boron halides and esters

boric acid.

  Recent developments in the field of

  machinery have significantly increased the requirements

  concerning lubricants for use in these machines.

  For example, increases in the price of gasoline and other fuels and periodic shortages of these fuels have increased the need for

  lubricants that promote fuel savings.

  In the field of gear lubricants, it has been necessary to develop lubricants which improve the

  operating under extreme pressure conditions.

  Another area in which there are increasing requirements for gear and bearing lubricants relates to the formation of deposits by

  oxidation Such deposits are frequently formed, especially

  in lubricants containing significant amounts of phosphorus and sulfur compounds of the type commonly used as additives in gear lubricants Deposits increase the sensitivity of machines to damage and reduce the effectiveness of the lubricant. interesting to develop improved oxidation inhibitors that reduce the formation of deposits in lubricants, especially in

  Gear lubricants for use in industry.

  A main object of the present invention is therefore to

  provide new compositions containing boron.

  Another goal is to provide useful compositions

  to improve fuel savings and

  Extreme pressure properties and to inhibit oxidation.

  Another aim is to provide additives for

  especially suitable for use in industrial lubricants for gears and bearings. Yet another object is to provide a process for preparing boron-containing compositions useful for

the goals described above.

  Other aims and advantages of the invention will result

again from the description below.

  As will be understood from the brief description

  above, compositions containing boron according to the

  The present invention is prepared from two reagents.

  Reagent A is at least one compound having Formula I. Such compounds can be conveniently prepared by the reaction of (A1) at least one aliphatic aldehyde-releasing compound corresponding to an aldehyde having the formula R 1 CHO with (A-2) at least one hydroxy-aromatic compound -3-

having the formula R 2 -Ar OH.

  As used in the description of these compounds,

  the term "hydrocarbon-based radical" refers to a radical having a carbon atom directly attached to the rest of the molecule and having a predominantly

  hydrocarbon in the context of the present invention.

  Such radicals include the following: (1) hydrocarbon radicals, ie, aliphatic (eg alkyl or alkenyl), alicyclic (eg cycloalkyl or cycloalkenyl), aromatic, aliphatic or alicyclic-substituted aromatic radicals; aliphatic and alicyclic aromatic-substituted, etc. Such radicals are known to those skilled in the art; examples are the methyl, ethyl, propyl, hexyl, decyl, octadecyl, phenyl, tolyl, naphthyl, hexenyl, dodecenyl and octadecenyl radicals (all

isomers being included).

  (2) Substituted hydrocarbon radicals, i.e.

  say radicals containing non-hydrocarbon substituents

  Bye which, in the context of the present invention, do not alter the predominantly hydrocarbon character of the radical. Suitable substituents will be apparent to those skilled in the art; examples are halogens (especially chlorine and bromine) and radicals

  hydroxy, alkoxy, alkylthio, nitro and carbalkoxy.

  (3) Straight radicals, i.e. radicals which, although predominantly hydrocarbon in the context of the present invention, contain non-carbon atoms in a chain or ring

  compounds also of carbon atoms hetero-

  appropriate atoms will be obvious to the skilled person and

  include, for example, nitrogen, oxygen and sulfur.

  In general, no more than about three substituents or hetero atoms, and preferably not more than one, will be present per 10 carbon atoms in the hydrocarbon-based radical. Expressions such as "alkyl-based radical" and expressions of the same kind have similar meanings to what is said above about alkyl radicals, etc. Preferably, the hydrocarbon-based radicals in the compounds according to the present invention are exempt.

  acetylenic unsaturation and usually also

  The radicals are usually hydrocarbon radicals and some of them may be lower hydrocarbon radicals, the term "lower" denoting radicals containing up to seven

carbon atoms.

  Reagent A-1, the aldehyde-releasing compound

  phage, can be either a free aldehyde (eg formaldehyde, acetaldehyde, propionaldehyde,

  butyraldehyde, valeraldehyde), an acetal of these aldehydes

  hydes (eg formaldehyde, acetaldehyde diethyl acetal), or a reversible polymer of these aldehydes

  <for example trioxane, paraformaldehyde, paraldehyde

  hyde) Aldehyde releasing compounds corresponding to aldehydes in which R 2 is hydrogen or a methyl radical and especially hydrogen are preferably used as reagent A-1. Thus, the preferred aldehydes are

  formaldehyde and acetaldehyde, especially the first.

  Reagent A-2 is at least one hydroxy compound

  aromatic compound having the formula R-Ar OH, wherein R may be hydrogen or an aliphatic hydrocarbon-based radical free of acetylenic unsaturation Most often, R 2 is a hydrocarbon radical containing about 4- 200 and especially about 6-100 carbon atoms. It is preferably an alkyl radical containing about 10-100 and most preferably about 10-40 carbon atoms. From the point of view of the availability and the particular suitability for the purposes of the invention. In the present invention, compounds in which R 2 is an alkyl radical containing about 15-30 carbon atoms are

particularly considered.

  The Ar radical is an aromatic hydrocarbon-based radical, typically derived from aromatic compounds such as benzene, naphthalene, biphenyl, diphenylmethane and diphenyl sulfide. Thus, the hydroxy-aromatic compound may be, for example, the phenol, a naphthol, an alkyl phenol or alkyl naphthol or a

  phenol or alkyl phenol bridged with sulfur and / or methylene.

  Useful bridged phenols can be prepared by the reaction of sulfur dichloride with the corresponding phenol or alkyl phenol.

  methylene can be prepared by a similar reaction.

  with a formaldehyde releasing reagent which can take place at the same time as the reaction with reagent A-1 (which is, of course, preferably also a reagent).

  releasing formaldehyde) or before or after this reaction.

  Alkylphenols are preferred for use as reagent A-2, and especially those containing at least one unsubstituted carbon atom at the ortho or para position, preferably ortho. Especially preferred are compounds wherein Ar is a phenylene radical (ie to say

  -C 6 H 4) and very advantageously o-phenylene Such compounds

  are typically prepared by the known alkylation of phenols with various olefins, alkyl halides, etc., including commercial mixtures of these olefins and

alkyl halides.

  By convention, the radical "Ar" includes in its structure all the hydrogen atoms directly attached to a

  aromatic nucleus Thus, all aromatic carbon atoms

  ticks not linked to another part of the molecule or to a substitute, specified or not, must be understood as

  being linked to hydrogen atoms.

  The reaction of reagents A-1 and A-2 is a known reaction; it is frequently conducted in the presence of an acidic or basic catalyst. Such reactions are described, for example, in US Pat. No. 4,147,643, which is hereby incorporated by reference for this purpose.

description.

  The reagent B in the process of the present invention is at least one compound selected from boric acid,

  boron trioxide (B 203), boron halides (especially

  Boron trioxide, BC 13) and boric acid esters will be reacted first. Boron trioxide will react first with the water formed in the reaction of reagents A 1 and A 2 to form boric acid, which then reacts. Still any of the various forms of boric acid can be used, including metaboric acid (HBO 2), orthoboric acid (H 3 B 03) and tetraboric acid (H 2 B 407). of these acids include, for example, the methyl, ethyl and propyl esters, the methyl esters being very readily available and therefore very often

  boric acid, and especially orthoacid

  boric acid is preferred for use as reagent B. The process according to the present invention involves the reaction of reagents A and B at a temperature in the range of about 70-250 ° C, preferably about 90-150 ° C and very often about 90-1300 ° C. It is often preferred to form reagent A in situ by heating a mixture of reagents Al, A-2 and B. The reaction is frequently carried out in the presence of a substantially inert, normally liquid organic diluent, typically a aromatic hydrocarbon such as toluene or xylene, a chlorinated hydrocarbon such as chlorobenzene or an ether

  such as dimethyl ether of ethylene glycol.

  When formaldehyde or a compound liberating

  Maldehyde is used as the Al reagent, a portion is sometimes lost through volatilization during the reaction. It is therefore preferred to use the excess reagent Al. Most often, about 1.5-8.0 moles of reagent Al are used and about 1.0-2.5 moles of reagent A-1 per mole of reagent B. The reaction is frequently conducted in the presence of (C) an acid catalyst. Useful acid catalysts include ion exchange resins in the form of

  acid, sulfonic acids such as benzene

  sulfonic and p-toluenesulfonic and alkanoic acids such as acetic, propionic, butyric

  and valeric acid Lower and higher alkanoic acids

  Propionic acid is preferred. The amount of reagent C is typically less than 0.5 mole, very preferably

  often about 0.1-0.3 moles per mole of reagent A-1.

  The molecular structures of the boron-containing compositions prepared by the process according to the present invention

  invention are not known with certainty.

  These are mixtures of compounds with a number of molecular structures. However, there is convincing evidence of the presence of compounds having the formula

R 1 H R

H O O -H

(II) B R 2 Ar-O / Ar R 2

  wherein R 1, R 2 and Ar are as defined above.

  The present invention therefore comprises composites

  containing boron comprising at least one compound

having formula II.

  The preparation of the compositions containing boron according to the present invention is illustrated by the examples

  All parts are by weight, unless indicated otherwise

contrary cation.

Example 1

  A mixture of 485.7 grams (1 mole) of an alkyl phenol prepared by alkylation of phenol with a commercial mixture of C 24-28 alpha-olefins, 10 grams (1 mole) of paraformaldehyde, 30.9 grams (0.5 mole) of boric acid, 22.2 grams (0.3 mole) of propionic acid and 600 cm of toluene is refluxed for 3 hours, and the water is removed. by distillation An additional 10 grams of paraformaldehyde is added and heating is continued at reflux for 2 hours; a third portion of 10 grams of paraformaldehyde (total 3 moles) is then added and refluxing is continued while the excess water and paraformaldehyde are removed. A total of 45 cm 3 of water is obtained. mixture and stripped under vacuum to obtain the desired product, which contains

1.19% boron.

Example 2

  A product similar to that of Example 1 is obtained from 1 094 grams (2 moles) of the alkylphenol of Example 1, 120 grams (4 moles) of paraformaldehyde added in two portions of 60 grams, 123, 6 grams (2 moles) of boric acid, 44.4 grams (0.6 mole) of propionic acid and 700 cm 3 of toluene. It contains 1.32%

of boron.

Example 3

  A mixture of 1094 parts (2 moles) of the alkyl

  phenol of Example 1, 60 parts (2 moles) of

  formaldehyde, 61.8 parts (1 mole) of boric acid, 44.4 parts (0.6 mole) of propionic acid and 200 parts of toluene is refluxed for about 6 hours while the water (about 70 parts) is distilled off. The mixture is then stripped in vacuo and filtered at 110-120 ° C to give

  desired product; it contains 0.73% boron.

Example 4

  A mixture of 536 parts (1 mole) of the alkylphenol of Example 1, 30 parts (1 mole) of paraformaldehyde, 30.9 parts (0.5 mole) of boric acid and 100 parts of The toluene is refluxed for 3 hours while the water is distilled off. A second portion of 30 parts paraformaldehyde (total 2 moles) is added.

  and heating under reflux for 5 hours.

  A total of 48 cm 3 of water is removed. The mixture is then subjected to vacuum stripping and filtered hot.

  to give the desired product; it contains 0.89% boron.

Example 5

  According to 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 portions of 3 moles) of

  formaldehyde, 92.7 parts (1.5 moles) of boric acid, 66.6 parts (0.9 moles) of propionic acid and 1000 cm

toluene.

Example 6

  A mixture of 430 parts (1 mole) of an alkyl phenol prepared by alkylation of phenol with a commercial mixture

  of C 18 to 24 'alpha-olefins of 30 parts (1 mole) of

  30.9 parts (0.5 mole) of boric acid, 22.2 parts (0.3 mole) of propionic acid and 100 parts of toluene are heated to reflux while the water is distilled off After the removal of 33 cm 3 of water, a further 30 parts of paraformaldehyde (total 2 moles) are added and heating is continued at reflux while water (total 41 cm 3) and paraformaldehyde are added. The mixture is stripped off under vacuum and filtered to give

  the desired product; it contains 1.14% boron.

Example 7

  A mixture of 1,945 parts (5 moles) of an alkyl

  phenol prepared by alkylation of phenol with a decene dimer, 150 parts (5 moles) of paraformaldehyde, 154 parts (2.5 moles) of boric acid, 88.8 parts (1.2 moles) of acid propionic and 300 parts of toluene is heated under reflux while the water is distilled off. When 157 parts of water have been removed,

  an additional 150 moles of

  formaldehyde (total 10 moles) and heating continued until the evolution of water was complete. The mixture was stripped under vacuum and filtered hot. The filtrate was the desired product; it contains 1.44%

of boron.

Example 8

  A boron-containing composition is prepared by a method similar to that of Example 1, except that trimethyl borate is substituted on a

equimolar, with boric acid.

Example 9

  A composition containing boron is prepared by a method similar to that of Example 1 except that paraldehyde and acetic acid are substituted.

  respectively on an equimolar basis, paraformal-

hyde and propionic acid.

  As indicated above, the boron-containing compositions according to the present invention are useful as additives for lubricants.

  useful as oxidation inhibitors and agents of extreme

  pressure in lubricants for gears and bearings; however, they can also be used in internal combustion engine lubricants to reduce fuel consumption. They can be used in various lubricants based on various oils of lubricating viscosity, including natural and synthetic lubricating oils and their In addition to gear and bearing lubricants, boron-containing compositions may be used in lubricating oils for the lubrication of spark ignition internal combustion engines and

  compression ignition, comprising self-propelled

  and engines, two-stroke engines, air piston engines, marine and railroad diesel engines, etc. Boron-containing compositions may also be used in gas engines, stationary generators and turbines, etc. Fluids for automatic transmissions; lubricants for combined rear axle gearbox assembly,

  lubricants for metal working, hydraulic fluids

  and other lubricating oil and grease compositions can also be improved by incorporation.

compositions containing boron.

  Natural oils include petroleum liquid oils and solvent-treated, acid-treated and / or hydrorefined mineral lubricating oils

  types paraffinic, naphthenic and mixed paraffinic-

  Naphthenic Oils of lubricating viscosity derived from coal or shale are also oils

basic useful.

  Synthetic lubricating oils include hydrocarbon oils and hydrocarbon oils

  halogenated products such as polymerized olefins and

  polymerized for example polybutylenes, poly-

  propylenes, propylene-isobutylene copolymers,

  chlorinated polybutylenes, poly (1-hexenes), poly-

  (1-octenes), poly (1-decenes) 7; aloylbenzenes, e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di (2-ethylhexyl) benzenes; polyphenyls (for example biphenyls, terphenyls, alkylated polyphenyls); and alkylated diphenyl oxides and alkylated diphenyl sulfides and their

derivatives, analogs and homologues.

  Polymers and interpolymers of alkylene oxides and their derivatives in which the terminal hydroxyl groups have been modified by esterification, etherification, etc.,

  constitute another class of synthetic lubricating oils

  Known examples are polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyl or aryl ethers of these polyoxyalkylene polymers, for example polyisopropylene glycol methyl ether having a weight average molecular weight of 1000, polyethylene glycol diphenyl ether having a molecular weight of 500-1000, polypropylene glycol diethyl ether having a molecular weight of 1000-1500); and their mono and polycarboxylic esters, for example the acetic acid esters, the mixed C 3 -C 8 fatty acid esters and

  the oxo acid C 13 diester of tatraethylene glycol.

  Another suitable class of synthetic lubricating oils includes esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids) with various alcohols (eg

  example butyl alcohol, hexyl alcohol, dodecyl alcohol

  cyclic, 2-ethylhexyl alcohol, ethylene glycol, mono-

  diethylene glycol ether, propylene glycol) Examples

  of these esters include di-adipate

  butyl, di (2-ethylhexyl) sebacate, fumarate

  di-n-hexyl, dioctyl sebacate, diisopropyl azela-

  octyl, diisodecyl azeleate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, 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 prepared from monocarboxylic acids of

  C 5 C 12 and polyols and polyol ethers such as neopentyl-

  glycol, trimethylolpropane, pentaerythritol,

  dipenta-erythritol and tripenta-erythritol.

  Silicon-based oils such as polyalkyl, polyaryl, polyalkoxy or polyaryloxysiloxane and silicate oils are another useful class of synthetic lubricants; they include tetraethyl silicate, tetraisopropyl silicate,

  tetra- (2-ethylhexyl) silicate, the tetra-

  (4-methyl-2-ethylhexyl), the tetra- (p-tert-) silicate

  butylphenyl), hexa- (4-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, diethyl ester of decylphosphonic acid) and

polymeric tetrahydrofurans.

  Unrefined, refined and re-refined 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.

  example, a shale oil obtained directly from

  In the case of retort distillation operations, a petroleum oil obtained directly from distillation or an ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. The refined oils are similar. with unrefined oils, except that they have been treated again in one or more stages of

  purification to improve one or more properties.

  Many such purification techniques, such as distillation, solvent extraction, acidic or basic extraction, filtration and percolation, are known to those skilled in the art. Rerefined oils are obtained by similar methods. to those used to obtain refined oils applied to refined oils which have already been used in service. These re-refined oils are also referred to as regenerated oils which are further processed and often further treated by removal of spent additives and decomposition products from the oil. Generally, the lubricants of the present invention contain an amount of the boron-containing composition sufficient to inhibit oxidation, improve the extreme-pressure properties or reduce fuel consumption. Normally, this amount will be about 0.1- 5.0%, preferably about 0.5-2.5% and the most

often about 0.5-1.5% by weight.

  The invention also contemplates the use of other additives in combination with the boron-containing compositions. The additives for use in lubricants for internal combustion engines include, for example, ash-type or ashless type detergents and dispersants, corrosion inhibiting agents and oxidation inhibiting auxiliary agents,

  pour point depressants, agents of extreme

  pressure, color stabilizers and

antifoam agents.

  Examples of ash-producing detergents are neutral and basic salts soluble in

  alkali or alkaline earth metals with sulpho

  carboxylic acids and phosphorus-containing organic acids characterized by at least one direct carbon-phosphorus linkage, including those prepared by the treatment of an olefin polymer (eg polyisobutene).

  having a molecular weight of 1000) by a phosphoric acid

  such as phosphorus trichloride, hepta-

  phosphorus sulphide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide or phosphorothioic chloride The most commonly used salts of these acids are those of sodium, potassium, lithium , calcium, magnesium,

strontium and barium.

  The term "basic salt" is used to refer to metal salts in which the metal is present in stoichiometrically larger amounts than the organic acid radical. The methods commonly used to prepare the basic salts include heating a solution in the mineral oil of an acid with a

  stoichiometric excess of a metal-metal

  like oxide, hydroxide, carbonate, bicarbo-.

  nate or sulphide metal at a temperature above 500 C and filtration of the resulting mass The use of a "promoter" in the neutralization step to assist in the incorporation of a large excess of metal is known Examples of compounds useful as a promoter

  take phenolic substances such as phenol,

  naphthol, alkyl phenols, thiophenol, alkyls,

  sulfurized phenols and condensation products of

  maldehyde with phenolic substances; alcohols such as methanol, 2-propanol, octyl alcohol, Cellosolve, Carbitol, ethylene glycol, stearyl alcohol and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-betanaphthylamine and dodecylamine. A particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic neutralizing agent derived from an alkaline earth metal and at least one alcohol promoter and the carbonation of the

  mixing at a high temperature, as at 60-200 ° C.

  Ashless detergents and dispersants are thus called despite the fact that, according to its constitution, the

  dispersant may give by combustion-a non-combustible

  as boric oxide or phosphoric anhydride

  America; however, it does not ordinarily contain any metal and therefore does not burn metal containing ash. Many types are known in the art and any of them are useful in the lubricants of the present invention. Examples thereof are: (1) Reaction products of carboxylic acids (or derivatives thereof) containing at least about 34 and preferably at least about 54 carbon atoms with nitrogen-containing compounds such as an amine Hydroxylated organic compounds such as phenols and alcohols and / or basic inorganic materials Examples of such "carboxylic dispersants" are described in numerous US patents including those of US Pat. Nos. 3,272,746, 3,381,022 and US Pat.

and 4,234,435 -

  (2) Reaction products of aliphatic halides

  These can be characterized as "amine dispersants" and examples are described, for example, in US Pat. Nos. 3,275,554, 3,438,757, US Pat. 3,454,555

and 3,565,804.

  (3) Alkylphenol reaction products in which the alkyl group contains at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines), which can be characterized as "dispersants" The materials described in US Pat. Nos. 3,368,972, 3,413,347 and 3,980,569 to

are examples.

  (4) Products obtained by subjecting the carboxylic, amine or Mannich dispersants to further processing with reagents such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbyl succinic anhydrides,

  nitriles, epoxides, boron compounds,

  Examples of materials of this type are described in a number of US Pat. No. 5,617,033. (5) Interpolymers of monomers having an oil solubilizing effect such as decyl methacrylate, vinyl and decyl oxide and high molecular weight olefins with monomers containing polar substituents, for example, aminoalkyl acrylates or acrylamides and poly (oxyethylene) -substituted acrylates. They can be characterized as being "polymeric dispersants" and examples of which are described in US patents 3,329,658,

  3,449,250, 3,519,565, 3,666,730, 3,687,849 and 3,702,300.

  All patents listed above are incorporated

  here by reference for their dispersant descriptions

without ash.

  Examples of extreme pressure agents and corrosion inhibiting agents and oxidation inhibiting auxiliaries are chlorinated aliphatic hydrocarbons

  like chlorinated paraffin; sulphides and poly-

  organic sulphides such as benzyl disulfide,

  bis (chlorobenzyl) disulfide, di-tetrasulphide

  butyl, sulphurated methyl oleate, sulfurized alkylphenols, sulphurated dipentene and sulphurated terpenes; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate; phosphorus esters comprising

  mainly dihydrocarbyl phosphites and tri-

  hydrocarbyl such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, phosphite

  pentylphenyl, dipentylphenyl phosphite, phos-

  tridecyl phite, distearyl phosphite, dimethyl and naphthyl phosphite, oleyl phosphite and

  4-pentylphenyl, polypropylene phosphite (molecular weight

  500) -phenyl and diisobutyl-phenyl phosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptyltriphenyl dithiocarbamate; phosphorodithioates of Group II metals such as

  zinc dicyclohexylphosphorodithioate, dioctyl-

  zinc phosphorodithioate, di (heptylphenyl) phosphoro-

  barium dithioate, cadmium dinonylphosphorodithioate 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. Lubricants for gears and bearings

  according to the present invention may contain the

  containing boron in combination with known packages of gear lubricant additives These packages frequently contain significant amounts, effective for improving extreme pressure properties

* lubricants, sulfur compounds and phosphorus.

  Many suitable packages of lubricant additives

  such gears are known to those skilled in the art.

  Boron-containing compositions are particularly effective as oxidation inhibitors in such lubricants containing relatively high proportions

sulfur and phosphorus.

  The compositions containing boron according to the present

  invention can be and are frequently added direc-

  otherwise fully prepared lubricant before use. However, they can also be diluted

  medium of a normally liquid organic diluent, sensi-

  Inert, such as mineral oil, naphtha, benzene, toluene, or xylene, to form an additive concentrate. These concentrates may contain from about 10% to about 90% by weight of the boron-containing composition. and may contain, in addition, one or more

  additives known in the art as described below.

  The following is an example of a lubricant for

  gears and bearings according to the present invention.

All parts are by weight.

  Mineral oil Product of Example 1 Soybean oil Isobutene sulfide Phosphoric acid ester neutralized with hydroxyalkyl dialkylphosphorodithioate amine Demulsifier polyoxyalkylene N-tridecyltrimethylenediamine Tolyltriazole Silicone antifoam agent 97.89 0.75 0.25 0.62 parts part-part part 0.40 part 0.005 part 0.05 part 0.015 part 0.02 part -20-

Claims (27)

  Process for the preparation of a composition containing   boron, characterized in that at a temperature of   in the range of about 70-250 ° C (A) at least one compound of the formula R 1 H \ C /   Wherein R 1 is hydrogen or a lower alkyl radical, R is hydrogen or a radical to   aliphatic hydrocarbon base free from acetylated unsaturation   lenic and Ar is an aromatic hydrocarbon radical; and (B) at least one compound selected from boric acid, boron trioxide, boron halides and esters boric acid.   Process according to Claim 1, characterized in that the reagent A is formed in situ by the reaction of (A-1) with at least one aliphatic aldehyde-releasing compound corresponding to an aldehyde having the formula R 1 CHO with (A-1) 2) at least one hydroxy aromatic compound having the formula R 2 -Ar-OH.   Process according to Claim 2, characterized in that Ar contains at least one unsubstituted carbon atom in ortho or para position.   4 Process according to claim 3, characterized in that Ar contains at least one ortho carbon atom unsubstituted.   Method according to claim 3, characterized in that that Ar is a phenylene radical.   The method of claim 5, characterized in that   that Ar is an o-phenylene radical.   Method according to claim 6, characterized in   that R 1 is hydrogen or a methyl group.   Process according to Claim 7, characterized in that R 2 is a hydrocarbon-based radical containing about 4-200 carbon atoms.   Process according to Claim 8, characterized in that R 2 is an alkyl radical containing approximately 10-100 carbon atoms.   Process according to Claim 9, characterized in that R is an alkyl radical containing approximately 10-100 carbon atoms.   Method according to Claim 10, characterized in that   that R 2 contains about 10-40 carbon atoms.   Process according to claim 11, characterized in what R 1 is hydrogen.   Process according to Claim 12, characterized in that reagent B is orthoboric acid and the reaction temperature is in the range about 90-150C.   Process according to claim 13, characterized in   that R 2 contains about 15-30 carbon atoms.   Method according to one of claims 1, 2, 4, 6,   8, 11, 13 or 14, characterized in that the reaction is   conducted in the presence of (C) an acid catalyst.   Method according to claim 15, characterized in   that reagent C is an alkanoic acid.   Method according to claim 16, characterized in   that reagent C is a lower alkanic acid.   Process according to claim 17, characterized in   that reagent C is propionic acid.   Method according to one of claims 2, 4, 6,   8, 11, 13 or 14, characterized in that about 1.5-8.0 moles of reagent Al and about 1.0-2.5 moles of reagent A-2 are used per mole of reagent B. -22 - Process according to claim 15, characterized in that 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 Process according to claim 17, characterized in that 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 Composition prepared by a process according to one   Claims 1, 2, 4, 6, 8, 11, 13 or 14.   Boron-containing composition, characterized in that it comprises at least one compound having the formula ## STR1 ## in which R 1 is hydrogen or a radical based on lower alkyl, R 2 is hydrogen or an aliphatic hydrocarbon-based radical free from acetylenic unsaturation and Ar 2 is an aromatic hydrocarbon-based radical. 24 Composition according to laughing in that Ar is bound ortho or para positions   25 according to the composition in which Ar is bound ortho positions.   26 Composition according to risée in that Ar is a 27 Composition according to laughed in that Ar is a 28. risée en claim 23, characterized to the rest of the molecule by claim 23, characterized   to the rest of the molecule by claim 24, phenylene radical. claim 26 o-phenylene radical. character- character-   Composition according to Claim 27, characterized   that R 1 is hydrogen or a methyl radical. -23-   29. Composition according to claim 28, characterized   in that R 2 is a hydrocarbon-based radical   containing about 4-200 carbon atoms.   Composition according to Claim 28, characterized   in that R 2 contains about 6-100 carbon atoms.   31. Composition according to claim 30, characterized   in that R 2 is an alkyl radical containing about 10-100 carbon atoms.   32 Composition according to claim 31, characterized   in that R 2 contains about 10-40 carbon atoms.   33 Composition according to claim 32, characterized   in that R 1 is hydrogen.   34 Composition according to claim 33, characterized   in that R 2 contains about 15-30 carbon atoms.   35 additive concentrate, characterized in that   includes a normally liquid organic diluent, sensi-   inert and approximately 20-90% by weight of a according to claim 22.   36 Additive concentrate, characterized in that   includes a normally liquid organic diluent, sensi-   inert and about 20-90% by weight of a composition   according to one of claims 21-34.   Lubricating composition, characterized in that it comprises a major amount of a lubricating oil and about 0.1-5.0% by weight of a composition according to claim 22.   38. The composition according to claim 37, characterized   ridged in that it also contains minor amounts, effective to improve its extreme-pressure properties,   of sulfur and phosphorus compounds.   39 Lubricating composition, characterized in that   it includes a major quantity of a lubricating oil   and about 0.1-5.0% by weight of a composition   according to one of claims 23-34. -24-   Composition according to claim 39, characteristics 4-   ridged in that it also contains minor amounts, effective to improve its extreme-pressure properties,   of sulfur and phosphorus compounds.