Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS2777874 A
Publication typeGrant
Publication dateJan 15, 1957
Filing dateNov 3, 1952
Priority dateNov 3, 1952
Publication numberUS 2777874 A, US 2777874A, US-A-2777874, US2777874 A, US2777874A
InventorsRhodes Alan, Peter A Asseff, Thomas W Mastin
Original AssigneeLubrizol Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Metal complexes and methods of making same
US 2777874 A
Abstract  available in
Images(19)
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

United States Pat ent METAL COMPLEXES AND METHODS OF MAKING SAME No Drawing. Application November 3, 1952, Serial No. 318,528

26 Claims. (Cl. 260-504) This application is a continuation-in-part of our co- I pending application Serial No. 216,101, filed March 16,

1951, and is a continuation-in-part also of our related I co-pending applications Serial No. 216,102, now Patent No. 2,617,049; 216,103, now Patent No. 2,616,924; 224,458, now Patent No. 2,695,910; 263,961, now Patent No. 2,616,925; 263,962, now Patent No. 2,616,911; 263,963, now Patent No. 2,616,904; 276,461, now abandoned; and 276,462, now Patent No. 2,616,905.

In our aforesaid parent application Serial No. 216,101, there is disclosed the process of producing certain novel organic salt complexes and the novel products resulting from such processes.

The present invention is concerned with the use of certain features of the process to which our said parent applications relate for the production of complexes which have particular properties which suit them for particular uses.

From the processes contemplated by our said parent applications, it is possible to produce organic metal complexes in which the metal content thereof is derived at least in part from the metal present in the normal salt of the starting acid, and metal contributed to the complex by an inorganic basically reacting material; and, optionally, according to the processes of our said parent applications, metal in the complex may be derived from the so-called promoter material.

The present invention is concerned with a process wherein the metal is der'ved from only two sources: specifically, (1) from the normal salt of the starting acid; and (2) from the so-called promoter material. The present process is characterized further in that the reaction mass which thus includes the starting acid, or, more particularly, its normal salt, and the metal containing promoter material is subjected to an acid treatment step utilizing for that purpose an acidic material which has 2,777,874 Patented Jan. 15, 1957 tion there will be given numerous examples of starting acids and numerous examples of metals. As indicated above, it is within the contemplation of our invention to utilize mixtures of diiferent acids as well as mixtures of different metals. The various combinations of reaction mass components which may thus be utilized include, for example, the following:

1. A single acid entirely neutralized with a single metal employed in conjunction with a promoter containing the same metal;

2. A single acid in which different portions thereof are neutralized by different metals employed in conjunction with a promoter material w ch may contain one or more metals, as by having a plurality of different metals associated with the same kind of anions, or a plurality of different kinds of anions associated with the same type cation.

From the foregoing, it will be apparent that there are many possible ways in which a plurality of starting acid anions and a plurality of metals may be included in the resultant complex. At this point, it should be observed also that, whereas all of the metal in the complex other than that derived from the normal salt of the starting acid is contributed to the complex by the promoter material used, it is nevertheless within the contemplation of our inventionto use along with such metal containing promoter materials, promoters which are metal free. It is also within the contemplation of our invention to use, in lieu of the metal containing promoter, an admixture of metal-free promoter plus an amount of free inorganic metal base up to but not greater than that amount required stoichiometrically to form the salt of the metalan ionization constant greater than the ionization constant of the organic acid reacting compound from which the anion of the promoter material is derived.

Where reference is made throughout this specification and in the attendant claims to the starting acid, or the acidic material, we shall presently give examples. We intend to include in the product of a single complex material, or product, one or more of different such acids or the'normal salts, since as will be presently explained, there are unusual advantages to be derived from the use of an admixture of different starting acids.

When we refer to the fact that the entire metal content of the complexes of this invention are derived from the normal salt of the starting acids and from the promoter material, it is to be understood that in confecting the reaction mass, we may use either the starting acid, as such, together with an amount of basically reacting material substantially equal to that required stoichiometrical- 1y to neutralize the amount of acids used, or we may utilize the normal metal salt with no free base present in the reaction mass. Throughout the following descripfree promoter. This refinement finds particular utility when the inorganic metal base is highly alkaline in nature, for example, the alkali and alkaline earth oxides and hydroxides, particularly barium oxide and barium hydroxide. The use of some metal-free promoter material is highly desirable for certain purposes since the complex produced thereby tends to be more truly homogeneous, and the behavior of the reaction mass during the processing is such that the processing is easier when some metal-free promoter is used.

In the following section of the specification, we shall first list the acidic materials which may thus be used in providing the anion of the normal metal salt, it being understood, as indicated above, that various combinations of such acidic starting metals may be used or their salts.

THE OIL SOLUBLE ACIDIC ORGANIC COM- POUNDS AND/ OR THE SALTS THEREOF as the aliphatic or aromatic organic acids e. g.', thesulfur acids, the carboxylic acids, acids of phosphorus, etc.,or the salts of such acids, including the corresponding thio acids of any of the foregoing as well as mixtures of the same. The aromatic compounds include the monoor polynuclear typesof the benzenoid and heterocyclic classes; whereas the aliphatic compounds are for example the acyclic and cyloaliphatic compounds. It is intended that all such compounds be oil soluble for this invention, and in the preferred instance oil solubility is meant that the salt of the acidic organic compound will possess a solubility of at least about 10% in Pennsylvania conventionally refined mineral oil having a viscosity of about 150 SUS at F., or what is commonly known as Pennsylvania neutral oil.

More specific illustrations of the types of oil-soluble acidic organic compounds or the salts thereof which can be employed are, for example,

(1) Organic acids in which:

" (alsullur is the acidforming element,'for example:

Organic acids containing the SO:H radical, e. g.:

Sulionic acids Sulfamic acids Thiosulfonic acids Organic acids containing the r-S02 radical, e. g.:

Sulfinic acids Thionamic acids Sulienic acids Partial esters of polybasic inorganic sulfur acids, e. g.:

Mono-esters of sulfuric acid Mono-esters of sulfurous acid Mono-esters of thiosuliuric acid (b) Selenium is the acid-forming element, for example:

Selenonic acids Seleninic acids Partial esters of polybasic inorganic selenium acids, e. 3.:

Mono-esters oi selenic acid Mono-esters of selenious acid Tellurim isthe acid forming element, for example:

Telluronic acids Tellurinic acids Partial esters of polybasic inorganic tellurium acids, 6. g.:

Mono-esters of telluric acid Mono-esters of tellurous acid (d) Carbon is the acid-forming element for example:

Organic acids containing the G0zl1 radical, e. g.:

Carboxylic acids N-substituted carbamic acid Organic acids containing the -OXzH radical, where X is either 0 or S and at least one X is sulfur, c. g.:

Thiocarboxylic acids N-substituted thiocarbamic acid Seleno-carboxylic acids Telluro-carboxylic acids (e) Nitrogen is the acid-forming element, for example:

Nitrolic acids: R-C (:NOH)NO Nitrosolic acids: R-C (:NOH)NO Nitronic acids: RzCINOOH Nitroic acids: RNO (0H 2 Carbazyllc acids: B-O 2NH)NH2 (f) Phosphorus is the acid-forming element, for example: Phosphinic acids; RXP(OH)3-z where z is 1 or 2 Phosphonic acids; RxPO(0H)3-= Where a: is 1 or 2 Throphosphinic acids; Rx]? (ZH) where a: is 1 or 2, and where Z is either O or Sand at least one Z is sulfur Thlophosphomc acids; RXPZ(ZH) where a: is 1 or 2, and where Z is either 0 or S and at least one Z is sulfur Partial1 esters of polybasic inorganic phosphorus acids, for exarnp e:

Mono-esters of phosphorous acid Mono-esters of thiophosphorous acids Monoand di-esters of phosphoric acid Monoand di-esters of thiophosphorlc acids Partial esters of pyrophos'phoric acid Partial esters of pyrophosphorous acid Partial esters of polyphosphoric acids Partial esters of polyphosphorous acids Partial esters of pyrothiophosphoric acids Partial esters of pyrothiophosphorous acids Partial esters of thlopolyphosphoric acids Partial esters of thiopolyphosphorous acids (0) Arsenlc is the acid-forming element, for example:

Arslnlc acids Arsonic acids Partial esters of polybasic, inorganic, arsenic-derived acids, e. g.:

Mono-esters of arsenious acid Monoand di-esters of arsenic acid (It) Antimony is the acid'iorming element, for example:

Strbonlc acids Partial esters of polybaslc inorganic antimony acids, e. g.:

Mono-esters of antimonous acid Monoand di-esters of antimonic acid (1) Silicon is the acid-forming element, for example:

Sllleonic acids: RSiO 0H Partial esters of sllicic acid Tm rs the acid-forming element, for example: stannonic acids;

n (1:) Lead is the acid-forming element for exam 1e: lurnb sermon), and RPbOOH p 9 mm acids (2) Salts of the organic acids listed under (1).

The salts included under (2) are metal salts and organic salts. The metal salts include the mono or polyvalent metals, such as the light or heavy metals, or the alkali and alkaline earth metals such as sodium, lithium, potassium, calcium, barium, strontium, magnesium, and other Mahogany sull'onio acids Pctrolatu'm 'sulfonlc 'aclds Substituted aromatic sulionic acids, e. g.:

Monoand poly-wax substituted naphthalene sulfonic acids MOIIO- 811d P y-wax substituted phenol sulfcnic acids Monoand poly-wax substituted dlphenyl ether sulfonlc acids Monoand poly-wax substituted naphthalene disulflde sultonic acids Monoand poly-wax substituted 'diphenyl amine sulionlc acids Monoand polyvwax substituted thiophene sulfonic acids Mongand poly-wax substituted alpha-chloronapbthalene sulicnic sex 5 N,N-di-wax aniline sullonic acids Fuel oil substitutedlnaphthalcne sullonic acids Fuel oil substituted diphenyl ether sulionic acids Kerosene substituted diphenyl ether sulfonic acids Pctrolatum substituted naphthalene sulfonic acids 'Petrolatum substituted phenol sulfonic acids Pctrolatum substituted anthracene sulionlc acids Petrolatum substituted naphthalene disulfide sulfomcacids Ceryl-diphenylene sulfonic acids Cetyl chloro-benzene sulfonic acids Oetyl-phenol sulfonic acids Cetyl-phcnol disulfide sulfonic acids Octyl-phenol monosulfide sulfonic acids Di-cetyl thianthrcne sulfouic acids Cetoxy capryl benzene sulfonic acids Di-lauryl chlorophenol sulionic acids Di-lauryl betanaphthol sulfonic acids Trl-lauryl phenothioxlne sulfonic acids Di-lauryl rncnohloro diphcnyl ether sulfonio acids Bis-(di-lsobutyl-carbinyl) naphthalene sulionic acids Dl-capryl ultra-naphthalene sullonic acids Tri-capryl benzene sulfonic acids 7 Tri-capryl dlpbenyl sulfide sulionic acids Dl-capryl methyl naphthalene sulfonic acids Di-capryl ortho-phenylphenol sulfonic acids Tetra-capryl meta-terphenyl-sullonlc acids Dl-capryl thiophene sullonic acids Diisobutyl (2,4,5-trichlorobenzyloxy) benzene suliomcaclds p-Oapryl-o-cyclohcxyl phenol sulionic acids Bis-(diisobutyl) naphthalene sulfonic acids Tris-(diisobutyl) anthracene sulfonic acids Bis-(diisobutyl) diphenylcne sulfide sulfonic acids Aliphatic sulfonic acids (acyclic), e. g.:

Parafiin wax sulfonic acids Unsaturated parafiin wax sulfonic acids Hydroxyl-substitutcd parafiin wax sullomc acids Nitroso-substituted parathn wax sulionic acids Ghloro-substituted parafin wax sulfonicaclds Unsaturated sulfonic acids derived from polyalkylcnos contaming at least 15 carbon atoms, e. g.: A

Tetraisobutylcne sulionlc acids Tetra-amylene sullonic acids Cycloaliphatic sulionic acids, e. g;

Petroleum naph henc sulfonlc acids Cetyl-eyclopentyl sulfonic acids Lauryl-cyclohexyl sulfonic acids Bls-(diisobutyl) cyclohexyl sullomc acids Monoand poly-wax substituted cyclohexyl sullonic acids Additional examples of sulphonic acids and/or salts thereof which can be employed as starting materials are disclosed in the following U. S. patents: 2,174,110; 2,174,506; 2,174,508; 2,193,824; 2,197,800; 2,202,791; 2,212,786; 2,213,360; 2,228,598; 2,233,676; 2,239,974; 2,263,312;'2,276,090; 2,276,097; 2,315,514; 2,319,121; 2,321,022; 2,333,568; 2,333,788; 2,335,259; 2,337,552; 2,346,568; 2,366,027; 2,374,193; and 2,383,319.

However, preferably, is intended to use as starting materials, the products derived in accordance with the processes of the above enumerated patents on the following initial materials:

Lubricating oil fractions Petrolatnm Paraflin wax Petroleum naphthenes White oil Gas oil Abietane The higher alkylatedcyclohexanes, e. 3.:

Getyl'cyclohexane Bls-(diisobutyl) cyclohexanes v The higher alkylated cyclopentanes, e. g: paraflln wax" sub tituted cyclopentane The higher alkylated decahydro-naphthalenes, e. g.: dl-lauryl de cahydronaphthalenes The higher alkylated benzencs, e. g.:

Parafiln wax substituted benzene Monoand poly-(triisobutyl) benzenes Moncand poly-(tetraisobutyl) bentenes The higher alkylated naphthalenes, e. g.: Petrclatum substituted naphthalene Paraflin was: substituted naphthalene Ter. one polymers, e. g.:

, olymerized turpentine Polymerlzed ruenthenes ,alkylene and alkadiene polymers, e. g.:

Polyethylenes Polypropylenes Polybutenes Polyisoprenes, ,e.g. natural r bber .Polybutadlenes r Polycaprylenes (Jo-polymers, e. g.:

Styrene-butadiene co-polymers Styrene-methyl acrylate co-polymers p-Methyl-alpha-methyl-styrene-vinyl chloride tic-polymers The higher aliphatic hydrocarbons, e. g.:

ctadecane Elcosane Tetracosane Pentacosane Heptacosane Triacontane For the purposes of this specification and appended claims, it should be understood that petroleum sulphonic acids or salts thereof are intended to cover those compounds derived from petroleum.

It has been found that metal complexes of considerable utility may be produced When using as the starting material a mixture of at least two difiei'ent sulfonic acid compounds.

Highly useful in this respect are mixtures containing (a) at least one petroleum derived sulfonic acid compound, and (b) at least one alkyl aromatic sulfonic acid compound. Particularly preferred are mixtures of mahogany sulfonic acids or salts with alkyl-benzene sulfonic acids or salts. The ratio of equivalents of a/b is preferably between 0.1 and 10.

The following examples illustrate a number of specific combinations of different sulfonic acid compounds which may be used as starting materials for the production of our metal complexes. In each instance, the corresponding salts of the sulfonic acids are also contemplated.

chemical equivalents Mixture No. Components {Mahogany sulfonic acid Di-isododecyl benzene sulfonic acid- {White oil sulfonic acid Mahogany sulionic acid Di-isododecyl benzene sulfonic acid.. {White oil sulionic acid Di-isododecyl benzene sulionic acid {Mahogany sulfonic acid Wax-substituted phenol sulionic acid. {Mahogany sulfonic acid Wax-substituted naphthalene sulionic acid- {Mahogany sulionic acid Wax-substitut ed benzene sulfonlc acid {P etrolatum sulionic acid White oil sulfonic acid..- lMahogany sulionic acid.

Petrolatum sulfonic acid Mahogany sult'onic acid. White oil sulfonic acid. {Polybutene sulionic acid. Mahogany sulionic acid. {Wax sulfonic acid Mahogany sulfonic acid {Eicosyl diphenyl ether sulionic acid. Mahogany sulfonic acid {Tri-capryl diphenyl ether sulfonic acid- Mahogany sulfonic acid tBis- (diisobutyD-phenol sulfonic acid White oil sulfonic acid Cetyl-chlorobenzene sulfonic acid.- Mahogany sulionic acid {Di-cetyl naphthalene sulionic acid.

Mahogany sulfonic acid. [Mahogany sulfonic acid.

White oil sulfonic acid.

{White oil disulionic acid.

Di-isooctadecyl benzene suli Petroleum naphthene suhonic acids.. Mahogany sul ionic acid Polybutene-substituted benzene suhonic aci 2O {Di-keryl benzene sulfonic acid. Mahogany sulfonic acid- {Fuel oil substituted benzene sulfoni c1 Mahogany sulionic acid {Stearyl naphthalene sulionic acid.

White oil sulfonic acid t, {Wax-substituted phenothioxine sulionic acid. a Mahogany sulionic acid Organic acids in which:

(n) Sulfur is the acid-forming element, for example:

Organic acids containing the SO3H radical, c. g;

Sulfonic acids (prior lists give specific examples) Sulfamic acids, e. g.:

Di-lauryl sulfainic acid Di- 3,9'diethyl-tridecyI-6) suiiamicacid Dicetyl-phenyl) suliamic acids Din-cctylcyclohexyl) suliamic acids Thicsuliouic acids, e. g.:

Eicosane thiosulionic acids Paraflin wax thicsulronic acids Parafiin wax substituted benzene sulionic acids Oetyl-cyclohexane thiosulfonie acids Organic acids containing the S 0 H radical, c. g.:

ulflnic acids, e. g.:

n-Octadecanc sulflnic acids Paraflin wax suliinic acids Petroleum sulfinic acids Paratiin wax substituted naphthalene sulfinic acids Petroleum naphthene sulfinic acids Di-capryl-cyclohexane sulfinic acids Thionamic acids, e. g.:

Myricyl thionarnie acid Di-cctyl thionamic acid Di-(lauryl-phenyl) thior amic acids Earaflin wax substituted cyclohoxyl thionamie acids Partial esters of polybasic inorganic sulfur acids, e. g.

Mono-esters of sulfuric acid, e. g.

Mono-docosyl sulfate Mono-(dlisobutyl-phenyl) sulfates Mono-(cetyl-cyclohexyl) sulfates Mono-esters of suliurous acid, e. g.:

Mono-octadecyl sufites Mono-(eicosyl-phenyl) sulfites Mono-(hydroabietyl) sulfites Miono-estel's oi thiosulfuric acid, e. g.:

Mono-pentacosyl thiosulfate Mono-Edi-capryl naphtheyl) thiosull'ates Monomyristyl-cyclopentyl) thiosulfates (b) Selenium IS the acid-forming element, for example:

Selcnonic acids, e. g.:

Paraflin wax selenonic acids Di-lauryl-benzene sclenonic acids Getylyclohexane selen onic acids Scleninlc acids, e. 11.:

Heneicosane seleninic acids '1rr-capryl-nephthalone seleninic acids laratfiu wax substituted cyclohexane seleninic acids Partial esters oi polybasic inorganic selenium acids, e. g.:

Mono-esters 0t selenic acid, e. g.:

Mono-tricosyl selenate Mono-(n onadecyl-phenyl) seleuatcs Mono-(di-n-octyl-cyclohexyl) selenatos Mono-esters oiselenious acid, e. g.:

Mono-myricyl sclenite Mono-(eicosyl-naphthyl) selenites Mono-(cetyl-cyclopentyl) selenites (c) Tellurium IS the acid-forming element, for example:

Telluronic acids, e. g;

Paratiin wax telluronic acids Di-capryl-anthracene telluronic acids Pcntacosyl-cyclohexane telluronic acids Tellurinic acids, e. g.:

Heptacosane tellurinic acids Di-nonyl-benzene tellurinic acids Di-lauryl-cyclohexyl tellurinic acids Partial esters of polybasic inorganic tellurium acids, e. g.:

Mono-esters of tclluric acid, e. g.: Mono-henelcosyl tellurate Mono-(docosyl-phcnyl) tellurates Mono-(tetracosyl-cyclohexyl) tellurates Mono-esters of tellurous acid, e. g.:

Mono-octadecyl tellurites Mono-(di-octyl-phenyl) tellurites Mono-(cetyl-cyclohcxyl) tellurites (:1) Carbon 15 the acid-forming element, for example:

Organic acids containing the OOaH radical, e. g.:

Carboxylic acids, e. g.:

Stearlc acid Behenic acid Carnaubic acid Oerotic acid ig mo ec ar wcig t aci s from t e oxidation of a wax and other petroleum fractions par fin Olcic acid Erucic acid Cetoleic acid Cetyl-benzoio acids Eicosyl-naphthoic acids Paratiin wax substituted hydroxy-benzoic acids Di-lauryl-enthracene carboxylic acids Petroleum naphthenic acids Abietic acid Hydroabietic acid fletraeosyl-cyclohexane carboxylic acids N-substituted carbamic acid, a. g.:

Di-octyl-carbamic acids Mono-cetyl carbamic acids Di-(hexyl-phenyl) carbamic acids Mono-(lauryl-phenyl) carbamic acids Di-(amyl-cyclohexyl) carbamic acids Mono-(lauryl-cyclohexyl) carbamic acids Organic acids containing the OX:EL radical, where X is oxygen, sulfur, selenium, or tellurium, and at least one X is other than oxygen, e. g.:

Thiocarboxylic acids, e. g.:

Monoand di-thio stearic acids Moncand di-thio oleic acids Monoand di-thio mellissic acids Moncand d -thio parafiin wax substituted henzoic acid Monoand di-thio eicosyl-naphthoic acids Monoand di-thio octadecyl-cyclohexane carboxylic acids Monoand di-thio petroleum naphthenic acids N-substituted thiocarbamic acids, e. g.:

etyl monoand di-thio carbamic acids Di-capryl monoand di-thio carbamic acids Lauryl-phenyl monoand di-thio carbamic acids Di-(octyl-phenyl) monoand dl-thio carbamic acids Npnadecyl-cyclohexyl monoand di-thio carbamic acids Di-(heptyl-cyclohexyl) monoand di-tbio carbamic acids Selenocarboxyllo acids, e. g.:

Monoand dl-seleno staeric acids Monoand di-seleno oleic acids Monoand dl-seleno tetracosyl-benzoie acids Monoand di-seleno petroleum naphthenic acids Tellurocarboxyhc acids, e. g.:

Monoand di-telluro oleic acids Monoand di-telluro cetyl naphthoic acids Monoand di-telluro hydroabietic acid Partial esters of polybasic inorganic carbon acids, e. g.:

Mono-esters of carbonic acid, c. g.:

Mono-ercosyl carbonate Mono-(cetyl-phenyl) carbonates Mono-(lauryl-cyclohexyl) carbonates Mono-esters ot thiocarbonic acids, e. g.:

Monggdocosyl esters of mono, di-, and tri-thio carbonic ac1 Mono-(myristyl-phcnyl) esters of mono, di-, and tri-thio carbonic acids Mono-esters of selenocarbonic acids, e. g.:

Mouo-pentacosyl esters of mono-, di-, and tri-seleno carbonic ds Mono-ceryl-phenyl esters oi mono-, di-, and tri-scleno carbonic acids Mono-(lauryl-eyclohexyl) esters i mono-, di-, and trl-seleno carbonic acids Mono-esters of tellurocarbonic acids, e. g.:

Mono-octadecyl esters of mono-, di-, and tri-telluro carbonic a s Mono-(parafiin wax substituted phenyl) esters of mono,

di, and tri-telluro carbonic acids Mono-(cetyl-cyclopentyl) esters of mono-, dr-, and trr-telluro carbonic acids.

It is also intended to employ as starting materials those high molecular weight acids which are prepared from the well-known 0x0 and Fischer-Tropsch proc- (e) Nitrogen is the acid-forming element, for example:

Nltrollc acids, e. g.:

Docosyl mtrolic acid Oetadccyl-naphthyl nitrolie acids Parafiln wax substituted cyclohcxyl nitrolic acids Nltrosolic acids, 0. g.:

Hexacosyl nitrosolic acid Nonadecyl-phenyl nitrosolic acids Dl-octyl-cyclohexyl nitrosolic acids Nitronic acids, e. g;

Heneicosane mtronic acids Phenyl-cetane nitronic acids Cyclohexyl-octadecane nltromc acids Nitroic acids e. g.:

Octacosyl nitroic acid Getylhenyl nitroic acids Laury -cyclohexy1nitroic acids Carbazy lic acids, e. g.:

Eicosane carbazylic acid Cetyl-benzene carbazylic acids Lauryl-cyclohexane carbazylrc acids Also useful as starting materials for the production of metal complexes are the pentavalent organic acids of phosphorus which contain at least one carbon te-phosphorus bond; i. e., those acids of the general formula:

wherein X and X are oxygen or sulfur, R is an organic radical bonded to phosphorus through a carbon atom, is is 1 or 2, and R11. contains a total of at least 12 carbon atoms.

When n is 2, there are of course two organic radicals present. Such radicals may be the same or dilferent; for example, R2 may represent two octyl radicals or a decyl radical and a hexyl radical.

Qther useful carbon-to-phosphorus bonded pentavalent organic acids of phosphorus, but whose exact structures have not yet been ascertained, are those acids prepared from aliphatic, cycloaliphatic and/or aromatic compounds which are devoid of hydroxyl, sulfhydryl, and keto groups by treating such compounds with at least one sulfurizing and phosphorizing reagent such as PSCls, P285, P437, P483, P485, P285 plus sulfur, PCla plus sulfur, elemental phosphorus plus sulfur, and the like, and optionally further treating with a hydrolyzing agent such .as water, steam, and/or metallic base. The preporation of such materials is disclosed in U. S. Patents Nos. 2,316,085; 2,316,086; 2,316,087; 2,316,088; 2,316,- 089; 2,316,091; 2,316,078; 2,316,079;,2,316,080; 2,316,- 081; 2,316,082; 2,316,083; 2,316,084; and 2,367,468.

Typical organic starting materials for the production of these-acids are given hereinbelow:

Lubricating oil fractions, especially those 01 high aromaticity Petrolatum Paraflln wax Paraflin oil Petroleum naphthcnes White oil Gas oil Abietane Oycloali hatie hydrocarbons and their alkylatcd derivatives, e. g.:

Oyc ohexane Methyl-eyclohexane Di-methyl-cyclohexanes Ethyl-cyclohexanc Butyl-cyclohexanes Hexyl-cyclohexanes Decahydronaphthalenc Cetyl-cylcohexane B1s-(diisobutyl) cyclohexanes The alkylated cyclopentaues, e. g.:

Ethyl-cyclopentane Pararfin wax substituted 'cyclopentane The alkylated decahydro-napthalenes, e. g.:

Di-ethyl decahydronaphthalene Di-lauryl decahydronaphthalenes Aliphatic hydrocarbons, e. g.:

Hexanes Heptanes Octanes, e. g.:

n-Octane Diisobutane Deeanes Dodeeanes Mixtures of the lower aliphatic hydrocarbons such as those found in e. a: Gasoline Kerosene Naphtha Octcdecane Eicosane 'letracosane Pentacosane Heptacosane Triacontnne Aromatic hydrocarbons and their alkylated derivatives, c. g.:

Benzene Toluene Xylenes Ethyl-benzene Amyl-benzenes Octyl-benzenes Naphthalene Methyl-naphthalenes Ethyl-naphtbalencs Butyl-naphthalencs Anthracene Methyl-anthracenes Diphenyl Terphenyl The Higher alkylated benzcnes, e. g.: Paraffin wax substituted benzene Monoand poly-(triisobutyl) benzenes Monoand poly-(tetraisobutyl) benzencs The higher alkylated naphthalenes, e. g.:

Petroleum substituted naphthalene Paraflin wax substituted naphthalene Terpene polymers, e. g.:

Polymerized turpentine Polymerized menthenes Alkylene and alkadiene polymers, e. g.:

Polyethylenes Polypropylenes Polybutenes Polyisoprenes, e. g. natural rubber Polybutadienes Polyeaprylenes Go-polyrners, e. g.:

Styrene-butadiene co'polymers Styrene-methyl acrylate err-polymers p-Methyl-alpha-methyl-styrene-vmyl chloride (ac-polymers Acids of phosphorus having at least one carbon-tophosphorus bond, when used in admixture with at least one oil-soluble sulfonic acid compound, have been found to provide highly useful starting materials for producing our metal complexes. Particularly valuable metal complexes for, some uses, as for example in lubricants, are obtained when using as a starting material a combination of petroleum sulfonate and the carbon-to-phosphorus bonded acid obtained by treating polyhutylenes in the molecular Weight range of 300 to 5000 with a mixture of P255 and sulfur.

(1') Phosphorus is the acid-forming element, for example:

Phosphinic acids; RxP(OH)3 wheres is 1 or 2, c. g.:

Pentacosyl phosphinic acid Di-lauryl phosphinic acid Cetyl-phenyl phosphinic acids Di-(octyl-phenyl) phosphinic acids Octadecylcyclohexyl phosphinic acids Di-(nonyl-eyclohexyl) phosphinic acids Phosphonic acids; RxP(0H)a-= where a: is 1 or 2, e. g.:

Octadecyl phosphonic acid Di-lauryl phosphonlc acid Ceryl-naphthyl phospbonic acid Dl-(capryl-naphthyl) phosphonic acid Oet(yl-cyclohexyl phosphonic acid 131- decyl-cyclohexyl) phosphonlc acid Thiophosphinic acids; RxP(ZH)a-, where: is l or 2 and Z is either or S with at least one Z being sulfur, e. g.: Monoand di-thio cetyl phosphinic acid Di-lauryl thiophosphinic acid Monoand di-thio eicosyl-phenyl phosphinic acids Di-capryl-phenyl thiophosphim'c acid Monoand di-thio octadecyl-cyclohexyl phosphinic acids Di-(nonyl-cyclohexyl) thiophosphinic acids Thiophosphonic acids; RxPZ(ZH)a-=, where x is 1 or 2 and Z is either 0 or S with at least one Z being sulfur, e. g.:

Mono-, di-, and tri-thio octadecyl phosphonic acids Di-decyl thiolphosphonic acids Di-deeyl thionophosphonic acids Mono-, di-, and tri-thio docosyl-phenyl phosphonic acids Di-(amyl-phenyl) dithiophosphonic acid Mono-, di-, and tri-thio cetyl-cyclohexyl phosphonic acids Di-(nonyl-cyclohexyl) dithiophosphonic acid Partial esters of polybasic inorganic phosphorus acids, e. g.:

Mono-esters of phosphorous acid, e. g.:

Mono-cicosyl phosphite Mono-(lauryl-phenyl) phosphites Mono-(cetyl-cyelohexyl) phosphites Mono-esters of thiophosphorous acids, e. g.:

Mono-S-docosyl thiophosphite Mono-O-docosyl dithiophosphite Mono-(O-cetyl-phenyl) clithiophosphites Mono-(octyl-cyclohexyl) trithiophosphites Monoand di-esters of phosphoric acid, e. g;

Monoand di-lauryl phosphates Monoand di-(dodecyl-phenyl) phosphates Monoand di-(nonyl-cyclohexyl) phosphates Monoand di-esters of thiophosphoric acids, e. g.:

0,0-di-n-hcxyl thiolthionophosphate 0,0-di-n-hexyl thionophosphate 0,0-di-(s-methyl-sec-arnyl) thiolthionophosphatc O,S-di-n-heptyl dithiolthionophosphate 0,0-di-(2-ethyl-hexyl) thiolthionophosphate 0,0-di-capryl thiolthionophosphate 0,0-di-(2,4,4-trimethyl-amyl) thiolthionophosphate O,S-d.i-n-nonyl dithiolphosphate 0,0-di(3,5,5-trimethyl-hexyl) thiolthionophosphate 0,0-di-n-decyl thiolthionophosphate S,S-di-n-undecyl dithiolphosphate 0,0-di-lauryl thiolthionophosphatc S-cetyl dithiolphosphate 0,0-di-cctyl thiolthionophosphate 'ihiolthionophosphates of the general formula (CnHIn'H' 0)zPSSH, where n is a number of from 20 to 50, e. g.: O-odi-(paraiiin wax) thilthionophosphates 0,0-di-myricyl thiolthionophosphate 0,0-di-carnaubyl thiolthionophosphate 0,0-di-(tert-amyl-phenyl) thiolthionophosphates 0,0-bis-(diisobutyl-phenyl) thiolthionophosphate 0,0-di-(decyl-phenyl) thionophosphates O-cetyl-phcnyl-O-napthyi thiolthionophosphates 0,0-di-(methyl-cyclohexyl) thiolthionophosphates 0,0-di-(amyl-cyclohexyl) thiolthionophosphates Pentacosyl-cyclohexyi tetrathiophosphates O,S-di-(heptyl-cyclohexyl) dithiolthionophosphates Partial esters of pyrophosphoric acid Mono-, di-, and tri-eicosyl pyrophosphates Mon0-, di-, and tri-(ceryl-phenyl) pyrophosphate Mono-, di-, and tri-(cetyl-cyclohexyl) pyrophosphates Partial esters of pyrophosphorus acid Mono-, di-, and tri-octadecyl pyrophosphites Mono-, di-, and tri-(myricyl-phenyl) pyrophosphites Monc-, di-, and tri-(cetyl-cyclopentyl) pyrophosphites Partial esters of polyphosphoric acids, e. g.:

Mono-, di-, tri-, and tetra-ceryl triphosphates Molilio, di-, tri-, tetra-, and penta-(dilaurylphenyl) tetraphosp a es Mono-, di-, tri', tetra-, and penta-, and hexa-(docosyl-cyclohexyl) pentaphosphates Partial esters of polyphosphorous acids, e. g.:

Mono, di-, tri-, and tetra-ceryl triphosphites Mono-, di-, tri-, tetra-, and penta-(stearylphenyl) tetraphosphites Mono-, di-, tri-, tetra-, penta-, and hexa-(paraflin wax substituted cyclohexyl) pentaphosphites Partial esters of pyrothiophosphoric acids, e. g.:

Mono-, di-, and tri-eicosyl pyrodithionophosphates Mono-, di-, and tri-(cetyl-naphthyl) pyrcheptathiophospbates Mono-, di-, and tri-(hydroabietyl) pyrothionophosphates Partial esters oi pyrothiophosphorus acids, e. g.:

Mono-, di-, and tri-ceryl S-pyro thiophosphites Mono-, di-, and tri-(docosyl-phenyl) O-pyrotetrathiolphosphites Mono-, di-, and tri-(lauryl-cyclohexyl) pyropentathiophosphites Partial esters of thiopolyphosphoric acids, e. g.:

Mono-, di-, tri-, and tetra-ceryl decathiotriphosphates Mono-, di-, tri-, tetra-, and penta-(di-caprylphenyl) tetrathionotetraphosphates Mono-, di-, tri-, tetra-, penta-, end hexahydroabietyl pentathionopentaphosphates Partial esters of thiopolyphosphorous acids, e. g.:

Mono-, di-, tri-, and tetra-myricyl heptathiotrlphosphites Moire tri-, tetra-, and penta-(laurylphenyl) trithiotetrap osp es LIOI1O3 di-, tri-, tetra-, penta-, and hexa- (petroleum naphthenyl) tetrathiopentaphosphites Arsenic is the acid-forming element, for example: Arsinic acids, e. g.:

Mono-cetyl arsinic acid Di-(lauryl-phenyl) arsinie acids Mono-hydroabietyl arsinie acid Arsonic acids, e. g.:

Mono-ceryl arsenic acid Di-(octyl-naphthyl) arsonic acids Mono-(myricyl-cyclohexyl) arsenic acids Partial esters of polybasic, inorganic, arsenic-derived acids, e. g.:

Mono-esters oi arsemous acids, e. g.:

Mono-ceryl arsenite Mono-(stearyl-naphthyl) arsenltes Mono-(petroleum naphthenyl) arsenites Monoand di-esters oi arsenic acid, e.g.:

Monoand di-eicosyl arsenates Monoand dl-(lauryl-naphthyl) arsenates Monoand di-(cetyl-cyclopeutyl) arsenates (h) Antimony is the acid forming element, for example? Stibonic acids, e.g.:

Di-lauryl stibonic acid Di-(ceryl-phenyl) stibonic acids Di-(octyl=cyclohexyl) stibonic acids J Partial esters of polybasic inorganic antimony acids, e.g.:

Mono-esters of antimonous acid, e.g.:

Mono-ce'ryl antimonite Mono-(eicosyl-phenyl) antimonites Mono-(lauryl-cyclohexyl) antimonites Monoand dl-esters of antimonic acid, e.g.: Monoand di-cetyl antimonic acids Monoand di-(tetradecyl-naphthyl) antimonic acids (2') Silicon is the acid-forming element, for example:

Siliconic acids; R-SiOOH, e.g.:

Oeryl siliconic acid Myristyl-phenyl siliconic acids Hydroabietyl siliconic acid Partial esters of silicic acids, e.g.:

Mono-myricyl metasilicate .Di-(lauryl-naphthyl) orthosilicate Mono-(petroleum-naphthenyl) orthosllicatc (j) 'iin is the acid-forming element, for example:

Staunonic acids; R-SnOOH, e. g;

Eicosyl stannonic acid Cetyl-phenyl stannonic acids Di-capryl-cyclohexyl atannonic acids (1:) Lead is the acid-forming element, for example:

Plumbonic acids; R-PbOOH, e. g.:

Ceryl plumbonic acid Di-lauryl-phenyl piumbonic acid Hydroabietyl plumbonic acid While the above compounds and classes thereof are useful for the purposes of this mvention, 1t should be: understood that they are not all equivalent, but that under certain conditions some are more desirable or effective than others.

THE PROMOTER The materials useful in the present process as so-called promoters have a function which is somewhat diiierent from the function of the materials referred to as pro meters in our co-pcnding parent applications. In certain of the processes contemplated in said parent applications, the promoter material has a function of assisting, to a certain extent at least, in bringing at least some of the so-called basing material into the complex. In the present case the promoter does not have that function in that no free basing material is present in the reaction mass. In the present case, therefore, the so-called promoter material serves first as the source for the metal present in the complex which is in excess of that present as the metal of the normal salt of the starting acid. The anion of the promoter liberated from the promoter material by the subsequent acid treatment may, of course, have an efiect upon the nature of the ultimate complex formed between the normal salt of the starting acid and a compound formed from the metal derived from the promoter, and it is possible that this last-named effect may be similar to the eifcct of the promoter in those processes of our parent applications wherein the promoter material is employed in conjunction with added inorganic basing material.

The promoter materials which have been found most useful in the present processes are compounds of the phenols and enols. The phenolic and enolic organic compounds are such that the anions thereof may be readily liberated from the metal compounds thereof by a simple acid treating process, as utilizing, for example, CO2 and S02, as well as HzS and CS2. While promoter materials formed from acid-reacting compounds having ionlzations constants higher than phenols and enols might be useful under certain circumstances, they would require the use of such a strongly acidic material in the subsequent acid treating step that great care would need to be exercised during such step to prevent unfavorable effects on the metal complex which is desired as the end product. Therefore, in the present case, we are concerned only with the use as promoter materials of phenolic and enolic compounds, since by the use of these together with the type of acid treating materials mentioned above, it is possible to very easily .and economically produce complexes which have great utility. The phenolic compounds acids Naphithol sulfinie acids, e. g.: beta-naphthol al ha-sulfinic c Phenols and alkylated-pherols having a sulfur-bearing substituent group other than SO;H or -S0,H, for example:

Phenol sulfides, e. g.: di-(p-hydroxy-phenyl) sulfide Naphthol sulfides, e. g.:

Alpha-naghthol sulfides Beta-nap thol sulfides Anthrol sulfides Poly-hydroxy-aryl sulfides, e. g.:

Hydroquinone sulfide Oatechol sulfides Resoreinol sulfides Pyrogallol sulfides Phloroglucinol sulfide Naghthoresorcinol sulfides Diydroxy-anthracene sulfides, e. g.:

Rufol sulfides Ohrysazol sulfides Propyl-phenol sulfides, e. g.: p-iso-propyl-phenol sulfides Butyl-phenol sulfides, e. g.:

p-t-Butyl-phenol sulfides o-sec-butyl-phenol sulfides Ethyl-naphthol sulfides, e. g.:

Ethyl alpha-naphthol sulfides Di-ethyl-beta-naphthol sulfides Amyl-resorcinol sulfides Methyl-cyclohexyl-eatechol sulfides Phenol disulfides, e. g.: di-(p-hydroxy-phenyl) disulfide N aphthol disulfides Anthrol disulfides Poly-hydroxy-aryl disulfides, e. g.:

Hydroquinone disulfide Resorcinol disulfides Na hthoresorcinol disulfides Diydroxy-anthracene disulfides, e. g.:

Rulol disulfides Ohrysazol disulfides Cresol disulfides, e. g.: p-Oresol disulfides o-Cresol disulfides Butyl-phenol disulfides, e. g.: p-t-butyl-phenol disulfid es Amyl-naphthol disulfides, e. g.: t-amyl-alpha-naphthol disulfides Hexyl-cateehol disulfides rropyl-naphthohydroquinoue disulfides Amyl-dihydroxy-phenanthrene disulfides Phenol sulfoxides, e. g.: di-(-hydroxy-phenyl) sulioxide Naphthol sulfoxides Anthrol sulfoxides Resoreinol sulfoxides Naphthoresorcin ol sulfoxides Ethyl-phenol sulloxides, e. g.: -Ethyl-phenol sulfoxides i-ethyl-phenol sulfoxides Butyl-phenol sulfoxides, e. g.: p-t-butyl-phenol sulfoxides Oetyl-eateohol sulfoxides, e. g.:

Oapryl-eateohol sulloxides Diisobutyl-catechol sulfoxides Amyl-naphthcl sulloxides Methyl-cyclohexyl-naphthohydroqui:one suh'oxides Phenol sullones, e. g.: di-(p-hydroxy-phenyl) sulfonc Naphthol sultones Phloroglucinol sulfones Naphthohydroqumone suliones Rulol sulfones Butyl-phenol suliones, e. g.: p-t-butyl-phenol sulfones Propyl-naphthol suhones, e. g.: iso-propyl-beta-naphthol sullones Hexyl-catechol sulfones Ethyl-uaphthohydroquinone sulfones Sulfur analogs of phenolic compounds, for example:

hi0 enol p-Et yl-thiophenol so-propyl-thiophenol p-t-Butyl-thiophencl p-t-Amyl-thiophencl bec-hexyl-thiophenols Oyelo-hexyl-throphenols n-Heptyl-thiophencls Diisobutyl-thiophenols 3,5.5-trimethyl-n-hexyl-thiophenol n-Decyhphenols Hexadecyl-thiophenols o-Chloro-thiophenol p-Nitro-thiophenol p-Amino-thiophenol Thiosalicylic acid t-Mercapto-l-naphthoic acid From the examples of phenohc compounds given above, it will be observed that throughout the specification and its claims when use 1s made of the term a phenol, we intend to include all those orgamc compounds which contain in their molecule a benzene ring containing at least one hydroxyl or sulphydroxyl group irrespective of what other substituents may be contained in the molecule. Thus, this term is 1nclus1ve not only of the oxy-phenols but the thio-phenols as well as the substituted derivatives thereof. Llkewise, throughout the specification and in the dams where use is made of the term a phenolic compound we intend to include not only compounds WhlCh can be referred to as a phenol as above defined,

14 but also all derivatives thereof including the metal salts. It should be noted also that from the examples given above, the term a phenol is inclusive of those compounds in which the 6-membered ring to which the characterizing hydroxyl group is attached may have one or more other ring structures connected thereto or fused therewith.

THE ENOLIC COMPOUNDS The term enolic organic compounds as used in the specification and appended claims refers to tautomeric organic compounds of the established type, for example, as illustrated in Advanced Organic Chemistry, by G. W. Wheland, John Wiley & Sons, New York, 1949, chap. 14, pp. 580 to 646.

Generally, the enolic organic compounds include a variety of classes of compounds such as aliphatic nitro compounds (i. e. aci-nitro compounds), oximes, imines, imides, amides, keto-esters, polyesters, and polyketones. It will be noted that the term enolic carbonyl includes keto-esters, polyesters, and polyketones.

The aliphatic nitro compounds (aci-nitro compounds) useful as promoters include, for example, l-(para-nitrophenyl)-2-nitrobutane; gamma-nitro methyl hexoate, lchloro l-nitropropane, l-nitropropane, etc.

The oximes useful as promoters include, for example, benzalacetone oxime, quinone mono-oxime, isophorone oxime, etc.

The amides useful as promoters include, for example,

-ethyl benzamide, ortho-chlorobenzamide, benzamide, acetanilide, thiodiglycolic acid diamide, acatamide, etc.

The enolic carbonyl compounds useful as promoters include, for example: keto-esters, such as, phenyl acetoacetate, ethyl acetoacetate, benzyl acetoacetate, chloronaphthol acetoacetate, etc.; polyesters, such as, dibenzyl malonate, diethyl malonate, triethylcarballyate, etc.; and polyketones, such as, benzoyl acetone, acetyl acetone, etc.

THE ACIDIC MATERIAL As previously indicated, one form of the process of the present invention includes the step of treating the immediate product with an acidic material for the purpose of liberating therefrom at least a portion of the material previously referred to as the promoter. A particularly elfective acidic material which has been utilized for this purpose is carbon dioxide. We are aware of the fact that Mertes in his above-identified Patent No. 2,501,731 suggested transforming a sodium hydroxide-caleium sulphonate complex into the sodium carbonate-calcium sulphonate complex or the corresponding bicarbonate complex by blowing the hydroxide complex with carbon dioxide at elevated temperatures.

In our process, the step of treating with an acidic material such as carbon dioxide or even with air has the effect of liberating from the immediate product formed a part at least of the anionic radical of the compound used as the promoter material. Thus the presence in the immediate product of the promoter material, in combined form, clearly distinguishes the immediate product from any'organic salt complex type material heretofore produced. Moreover, the nature of the product formed by regenerating from the immediate product at least a portion of the anionic radical of the promoter material leaves that product with a composition which is quite different from prior art organic complexes. It is recognized that in accordance with the present invention, the salt form of promoter can be employed in forming the salt complex. However, notwithstanding this fact, upon treating the salt complex with the acidic material to be more particularly defined below, this salt compound is released or liberated from association in the salt complex as the ionizable compound and not the salt.

The acidic material employed for this purpose can be either a liquid, gas, or solid just so long as the material when present in the mass containing the salt complex will possess an ionization constant greater than the promoter which is released or liberated from association in the salt complex. Thus, for the purpose of this specification and the appended claims, it is to be understood that the acidic material includes a liquid, gas, or solid prior to being incorporated in the mass which contains the salt complex.

In the present invention, the acidic material usually employed is an acid or a gas. The acids can include the strong or weak types, such as, for example, hydrochloric, sulphuric, nitric, carbonic, acetic acids, etc., Whereas the gas is for the most part an anhydride or an acid or an acid anhydride gas.

The large number and variety of acidic materials can be best illustrated by the following specific examples, viz. HCl, S02, S03, CO2, air, N02, H28, N203, PCls, SOClz, C102, HzSe, BFs, CS2, COS, etc.

From the above examples of compounds and classes of compounds which can be used as acidic materials, it should be understood that all of them are not equivalent for this invention because under certain conditions some are more desirable or etfective than others.

Generally, the complex formed is prepared by heating the components, at a superatmospheric temperature while insuring thorough mixing and then further heating said mixture to substantially remove all free water or alcohol, including water and alcohol of hydration which may be present. The following methods illustrate the manner by which the complex can be formed, namely:

(a) The compound AH or the salt thereof, is added to the oil-soluble salt of an acidic organic compound, followed by addition of an aqueous solution or suspension the salt or base thereto. The mixture is held at a superatmospheric temperature for a reasonable length of time while insuring thorough mixing, and then the total mixture is further heated to substantially remove all free water or alcohol including water or alcohol of hydration which may be present.

(1')) The salt or base in a dry state is added to a mixture of oil-soluble acidic organic compound or salt thereof, the compound AH or the salt thereof and either water, alcohol, or mixtures of alcohols or water and alcohol; heated to a superatmospheric temperature while insuring thorough mixing and then further heated to remove substantially all free water or alcohol including water or alcohol of hydration which may be present;

(c) The acidic organic compound is mixed with the compound AH or the salt thereof, when an aqueous solution or suspension or an alcoholic solution or suspension of the salt or base is added thereto. The mixture is heated and agitated at a superatmospheric temperature for a time sulficient to insure thorough mixing and followed by subjecting the total mixture to dehydration conditions in order to remove substantially all free water or alcohol including water or alcohol of hydration which may be present.

(d) A mixture of the oil-soluble acidic organic compound or the salt thereof, the compound AH or the salt thereof, and the salt or base is heated and agitated at a superatmospheric temperature for a time suficient to insure thorough mixing, and followed by heating the total mixture in order to remove substantially all free water or water of hydration which may be present.

(:2) The sediment when formed from any of the aforementioned methods can be employed either alone or with an additional amount of compound AH or the salt thereof in any of the three methods given above.

(f) In any of the methods discussed herein for preparing a salt complex, a substantial increase in cationic salt-forming radical content is efiected by treating the mass with an acidic material just after substantial amounts of water or alcohol or both, are driven off and just before the mass is filtered.

In all of the methods described above for preparing the salt complex, the step of removing substantially all free water or alcohol including water or alcohol of hydration which may be present is accomplished at a temperature not substantially in excess of 350 0, preferably about to 200 C. The technique employed to remove the alcohol or water includes, for example, a conventional flash operation, heating under subatmospheric, atmospheric, or superatmospheric pressures. It can, therefore, be seen that the temperature as well as the time for eifecting the substantial removal of the alcohol of water will generally vary considerably depending on the technique employed therefor. Generally, the time required to effect substantial removal of water or alcohol when employing drying other than flash techniques is about 15 minutes or less, and can be as high as 10-15 hours. Usually, however, atmospheric pressures will be employed for such an operation, and consequently it will usually require about 1 to 5 hours to remove substantially all water or alcohol which may be present. At a later stage of the process, the acidic material when used in gaseous form may be used to remove the last portion of water.

For the purposes of this specification and the appended claims, the relative amounts of (1) the oil-soluble acidic organic compounds or salts thereof, and (2) the promoter is expressed as the ratio of equivalents" of the former (l) to the latter (2). In accordance therewith, the ratio of equivalents is from about 1 to 10 to about 10 to 1, preferably from about 3 to 2 to about 7 to 2. The amount of salt or base employed in the process will be sufiicient to have present in the total mass at least more than about one equivalent of cationic salt-forming radicals including those present in the oil-soluble acidic organic compound or the salt thereof and the promoter per equivalent of oil-soluble acidic organic compound or salt thereof plus the promoter.

The treatment of the salt complex with an acidic material is employed when it is desirable to lower the basic number of the salt complex and/ or partially or substantially recover the promoter. This treatment is efiected at a temperature of about 25 to 250 C., preferably about to C., and by employing about 0.5 to 20% of acidic material based on the weight of salt complex. The time of treatment with the acidic material can vary considerably depending on the desired result. As would be expected, short periods of treatment might cause only partial liberation or release of the promoter or relatively small decreases in the basic number of the salt complex; however, in general, periods of treatment will range from about 0.25 to 30 hours. In most cases, and particularly where it is desired to recover the promotor, the amount of acidic material used should be at least equivalent to the amount of cationic salt forming radicals present as the salt of the ionizable form of promoter. When it is desired to produce a product having substantially neutral reaction, the amount of acidic material used should be at least equivalent to the total cationic salt forming radicals in excess of that present as the normal salt of the oil soluble organic acid.

In those instances where salts or bases containing metal are employed as the basing agent the metal content of the complex will be defined as the ratio of the total metal in the salt complex to the amount of metal which is in the form of a normal salt of the oil-soluble acidic organic compound. In accordance therewith the present invention includes salt complexes containing metal ratios greater than 1, and up to about 10 or more. As for those complexes which are treated with an acidic material, it is to be noted that the metal ratio is substantially the same as in the complex prior to treating. Consequently, for acidic material treated complexes, the same metal ratios will apply as given above. Likewise, when the salt complex is treated with an acidic material and the promoter is removed from the resultant product by distillation or otherwise, it is found that the metal ratio will be substantially the same as in the salt complex before treating with the acidic material.

Since the present invention includes complexes which do not contain metal in combination therewith, it'is con venient, therefore, as a means of designating the amount of overbasing to employ the ratio of total cationic saltforming radicals in the salt complex to the amount of cationic salt-forming radicals which are in the form of a normal salt of the oil-soluble acidic organic compound. Hereinafter, this ratio will be referred to as the cationic salt-forming radical ratio. In accordance therewith, the cationic salt-forming radical ratio of the salt complex will be in the same range as given hereinabove for the metal ratio.

It has been found that the salt complex can be prepared by using small quantities of water, alcohol, or mixtures of both, such as about 1 mole of same per mole of salt or base which is employed as the basing agent. However, more usually about 5 to 50 moles of water, alcohol or mixtures of both per mole of salt or base used, and preferably about 15 to 30 moles per mole.

To substantially increase the metal content of the salt complex, the total mass is treated withan acidic material just prior to filtering same to separate the desired salt complex. This treatment is effected at a temperature of about 25 to 250 C., preferably about 120 to 170 C., using about 0.5 to 20% of acidic material, based on the total mass, and for a period of about 0.25 to 30 hours. Treatment with an acid anhydride gas may be accelerated by superatmospheric pressure.

In order to better understand the present invention, the following specific examples thereof are given; however it should be understood that no undue limitations or restrictions should be imposed by reason thereof.

The following examples give the preparation of a plurality of products which range in cationic salt forming radical content from about that of the normal salt up to many times that amount.

We have found that sulphate ash and/ or metal content values, and the metal ratio values calculated therefrom, are one of the most reliable means for characterizing certain of the salt complexes. As the description of the invention proceeds, it will become apparent that the neutralization number of a salt complex is in certain instances an unreliable index of the amount of excess cationic salt forming radicals in such complex, since it is greatly affected by the type of basing agent employed and can be varied within wide limits without significantly changing the cationic salt forming radical content of the product by treatment of the mass with air, CO2, or the like.

The above is not to be construed as a statement that the neutralization number is not an important property of a salt complex. For some uses, for example in lubricants, it is advantageous in certain instances to employ a salt complex of a substantially neutral character, whereas in other instances a salt complex of high alkalinity has been found to produce the desired results.

Example 1 3408 grams of polymerized isobutylene having an average molecular weight of about 750 were heated to 210 C. and an intimate mixture of 672 grams of Pass and 84 grams of sulfur flowers was added thereto over a period of 1.75 hours. After all of the PzS5% mixture had been added, the whole was heated for 1.5 hours at 210 C., diluted with 2600 grams of low viscosity mineral oil, and blown with steam for 5 hours at 210215 C. The filtered material, a high molecular weight organophosphorus acid of undetermined structure, had an acid no. of 68 and contained 0.9% sulfur and 2.14% phosphorus.

820 grams (1.0 equivalent) of this organo-phosphorus acid, 56 grams (1.5 equivalents) of Ca(OH)2, and 200 ml. of water were refluxed for 2 hours and then elevated to 150 C. to remove substantially all of the water (2 hours at 150 C. required). The filtered process mass comprises an oil solution of the calcium salt of the organophosphorus acid. 1

In a separate vessel, 488 ml. of water, 458 grams (4.88 equivalents) of phenol, and grams (2.44 equivalents) of Ca(OH)2 were refluxed for 2 hours to prepare calcium phenate in situ and in the presence of an excess of phenol. To this vessel were added 333 grams (0.5 equivalent) of the above-described calcium salt of organo-phosphorus acid and 525 grams (0.5 equivalent) of a 45% oil solu tion of calcium petroleum sulfonate (6.5% sulfate ash content). The process mass was refluxed for 2 hours at -110 C. and then heated to C. where it was blown with CO2 for one hour. The substantially neutral process mass was then heated to 200 C. under reduced pressure. Phenol, freed from calcium phenate by the carbonation step, was recovered to the extent of 91% in the distillate. The residue was diluted with 300 grams of low viscosity mineral oil and filtered. The filtrate,

the desired end-product, was a brown, oil-soluble liquid having the following analyses:

Percent sulfur 1.16 Percent phosphorus 0.50 Percent calcium 4.18 Percent sulfate ash (calculated) 14.2 Basic no 16.2 Metal ratio 2.57

Example 2 738 grams of the organo-phosphorus acid described in Example 1, 902 grams of low viscosity mineral oil, and 800 ml. of water were stirred at 70 C. Then 111 grams (3.0 equivalents) of Ca(OH)2 were added and the mass was refluxed for 0.5 hour. Thereafter, grams (5.0 equivalents) of Ca(OH)2, 1050 grams (1.0 equivalent) of a 45 oil solution of calcium petroleum sulfonate, and 1315 grams (14.0 equivalents) of phenol were added and the process mass was refluxed for 3 hours to prepare calcium phenate in situ and in the presence of an excess of phenol. Substantially all of the water was removed by heating to 150 C., at which temperature CO2 was blown through the mass for 2 hours to render it substantially neutral on titre. A vacuum was then applied and the temperature of the mass was raised to 200 C. to remove substantially all of the original phenol used. The phenol was liberated from the calcium phenate in the process mass by the carbonation step.

After substantially all of the phenol had been removed, the residue was filtered. The filtered end product was a brown, oil-soluble liquid having the following analyses:

Percent sulfur 1.32 Percent phosphorus 0.47

Percent calcium 4 7 Percent sulfate ash (calculated) 15.2 Basic no 115 Metal ratio 3.22

Example 3 The experiment described in Example 2, was repeated using 590 grams 1.0 equivalent) of a 65% oil solution of di-isododecyl benzene sulfonic acid in lieu of the 1.0 equivalent of calcium petroleum sulfonate specified therein. The filtered end product in this instance was a brown,

Example 4 1046 grams (1.0 equivalent) of a 45 oil solution of calcium petroleum sulfonate of 6.5% sulfate ash content swarm were i'fii5redwith 2'28 ;(2.44 'e c' uivalnts) de t renal and h e'ated to TOD "Cf'Wl iile ziddirfg 124 assess 2244 equivalents) of calcium me'thoxide to forin alciuin gilinateirr'situ. fifter the fbcessfiass had ben s'tirred-for 2' hours at '100-120 C., 22" grams of H were aclded "andihe 'Whole was' stirred for 'o'ne-houbat 105 C. The temperature was then elevated to 120 C.-arid-GOz =Was blownthi'ough the mass asthete'mperatu're wasegai'n ele- "rated to 150 C. Thereafter, the -mass '-''was maintained for 1 hour at 150' C.,"stripp'ed of phnol libe'rzite'd by -the carbonation-ste at- 210" cxane zo "mfiLjI-Ig absolute p'ressure, "and filtered. (Apiirofiirfia fely 90% of the phenol'was' recovered.)

"The filteredend-product was 'abr'own, oiI-sohible l'iquid 'haviiig'thefollowifig analysesz ra es: sorta-..

Basic no 923 Metal ratio 3.03

Exdrir'plefi .459' grams (4.88 equivalerit's) 'of phenolflofi grams (2.44 equivalents) of Ca ("OH=)2, imd- 2Z4 grams of" water were refiuxedfor'l hours to form calcium phenate 'in' situ and in thepresence' of' excess phenol. "1'046i grams (1 .0 equivalent) of" a 45 oilsolfitibn "of calcium petroleum sulfonate were -then addedund the whole w'as heatea-= to 125 C. to-rernove-the bulk of the'water a'hd about 32 grams of phenol. Thetemperature'was therfelevated to 150 C. and- Coi-was blown tlirouglf themass forlj hours. u P -distillate was-colleeted "wiiieh Wes found to consist of 18 grams of water and 42 grains of phenol. The prdcess'masswas 'thewfieeted to'"200 Cgjijidei iediled Pressure," "removing, as distillateffib'out 375 'fgrfinhs'iof phenol. "Total "phenolrecoveryw'as Anagrams bf 98 of starting-amount. I

The -residue omfiltration yielded" a "brown; oil-soluble liquid having-the "following analyses Percent sulfate ash 18.3 Basic 1 Metabra'tio "3:07

\ "282- grams-(3.0eduivalritsy bfibheholf'trins 1 .0

iiiiiral" o l -he residueonifiltration, wielded arbmwnmilzselixble liquid havirrg flmifollowing anaiyses:

'1'046 grains (1J0"equivalezit) of a"45% oil solution-rot calcium etrolenmsfilfonate, 229 "grams (2:4 equivalents) ofphenolj9u5 grams (2;44"equiva1ent's) 'bftaCMOHh, and 244"g'i'ains ofwater' were stirred at 100lO'5'C.f0r 2 hours to form calcium phenate in situ and in'theabsence of an excess'fshenbl. The process'mass'was'heated'slowly to 126 CQto remove the bulk r-or the water "and some iahenol. "cbz was thenblo'wn through themass and the temperaturewasraise'd to 156 C; while 'CO'blowing was continued. 4 After the whole had been' maintained'lfor 2 henrsat 15-0 "C.-wifl1' C02 blowing; it was heated to f2 1 5 C. under reducedfpressure'toremove'substantialiy'all"of "the phenol liberatedbythe carbonation step. "Totarphenol reeever was wm.

"The" residue was filtered 'to yield a. "brown; oil=solnble 'liquid having the following analyses:

Percent :sulfate ashs 18.2 Acid -no-; 2.8 Metel ration 3.06

'Per'ceht siilfate ash -s 18:2 "Basic -m r -10.3 Metal satio "4102 Example 10 mage-ems (1 .0 equivalerity'bra 35%" oil 'sblution of cerium rol'eum siilfona'tef' 2'6 l'gramsbf low viscosity 'rld'iiOO-mlI-bf"waterwerestirrd-togtherat 'C. 301 rams "(3:94" equivalentsybf 'Bo mid 94 grams (11F equivaleiit} ofbhenbl' were addedand' 'thc whole' was reflux'ed for 3 hours. The temperature of the process mass was therr elev'a'ted td 1 '5 0""C:- andbwwas blown through the reactants until a substantially neutral titre was obtained on thehiass'fabout 2 hours required). The--process-mass-ivas them-elevated' to 200"- C- and a vacuum was-applied. I Substantially all-of the'phenol used was recovered irr the distillate.

The residue on filtration. yielded a brown; :oil soluble liquid having the-following analyses *Pefeenfisulfateash 27.6 Basic -no.- 7 '10.].

TatiO- Example 40a -A fdi1ct similar 'tothatdesci'ibed irrExample I'may be prepared by following the process described'th'erein butoifiittihg' the"-step wherein thep'ro'cess' is heat'ed' to abu e; underreduced "pressure"ro remove henol.

ln' this ifi'stanc the slid-product retains zi"substantial 'erepbrtiow 'oe me*pheriorerigixiiny-usd.

21 1 Example b A product similar to that described in Example 10 may be prepared by following the process described therein but omitting the step wherein the process mass is heated to 200 C. under reduced pressure to remove phenol.

In this instance the end-product retains a substantial proportion of the phenol originally used.

Example 100 A product similar to that described in Example 4 may be prepared using 2.44 equivalents of para-cresol in lieu of the 2.44 equivalents of phenol specified therein.

Example 10d A product similar to that described in Example 4 may be prepared by using 2.44 equivalents of diisobutyl-phenol in lieu of the 2.44 equivalents of phenol specified therein. Example Me A product similar to that described in Example 4 may be prepared by using 2.44 equivalents of I-nitro-propane (an enolic compound) in lieu of the 2.44 equivalents of phenol specified therein.

Example 10f Example 10g A product similar to that described in Example 9 may be prepared by using 1.0 equivalent of a 45% oil solution of mixture of equal molecular parts of calcium petroleum sulfonate and calcium di-isododecyl benzene sulfonate in lieu of the 1.0 equivalent of calcium petroleum sulfonate specified therein.

The salt complexes produced in accordance with the present invention can be employed in lubricants including oils and greases, and for such purposes as in crankcases, transmissions, gears, etc. as well as in torque converter oils. Other suitable uses for such complexes are in asphalt emulsions, insecticidal compositions, fire-proofing and stabilizing agents in plasticizers and plastics, paint driers, rust inhibiting compositions, pesticides, foaming compositions, cutting oils, metal-drawing compositions, flushing oils, textile treatment compositions, tanning assistants, metal cleaning compositions, emulsifying agents, antiseptic cleansing compositions, penetrating agents, gum solvent compositions, fat splitting agents, bonding agent for ceramics and asbestos, asphalt improving agents, flotation agents, improving agents for hydrocarbon fuels such as e. g., gasoline and fuel oil, etc.

More particularly, especially adapted for the preparation of lubricants, paint driers and plastics, particularly the halogen bearing plastics. In these respects, the salt complex can be employed in the following concentrations based upon the weight of the total composition.

LUBRICANT CONTAINING ORGANIC METAL COMPLEXES While the metal complexes of the present invention are useful per se as improving agents for lubricating greases and oils, especially mineral lubricating oils intended for the complexes of this invention are 3 use in the crankcases of internal combustion engines, they are most advantageously employed in combination with one or more additional improving agents of the prior art such as, for example, the numerous prior art oxidation inhibitors, detergents, extreme pressure agents, rust inhibitors, and oiliness agents.

In addition to the above-named types of cooperating improving agents,the present invention also contemplates the inclusion, in the finished lubricant, of materials intended to modify the physical characteristics of the mineral lubricating oil base. Examples of such materials are foam inhibitors, pour point depressants, viscosity index improving agents, and odor improving agents. Since the types of materials useful as physical property improving agents are well known to those versed in the lubricant art, it is deemed unnecessary to lengthen the specification unduly by a recitation of the same.

Particularly eifective lubricating oils for the crankcases of internal combustion engines can be made by in corporating, in suitable mineral lubricating oils, thiophosphate salt-esters and/or phosphorus sulfide treated unsaturated organic materials along with the metal complexes of the present invention. From the viewpoint of cost, effectiveness, and commercial utility, the most desirable thiophosphate salt-esters for use as oxidation and corrosion inhibitors along with materials of the present invention in lubricating oils are dithiophosphate salt-esters of the general formula R20/ SM wherein R1 and R2 are the same or radicals and M is one equivalent of a metal selected from Group II of the Table and most desirably either zinc or barium. In this connection reference may be made to the dithiophosphate salt-esters disclosed in U. S. Patents 2,261,047; 2,329,436; 2,344,392; 2,344,393; 2,344,394; 2,344,395; 2,342,572; 2,347,592; 2,361,746; 2,358,305; 2,364,283; 2,364,284; 2,365,938; 2,382,775; 2,386,207; 2,373,811; 2,410,650; 2,417,562; and 2,438,876.

Particularly useful in this respect are dithiophosphate salt-esters wherein R1 and R2 of the above formula are different organic radicals, which materials are the subject of pending applications Serial No. 250,959, filed October 10, 1951, and Serial No. 251,139, filed October 11, 1951, by Fred C. Goldsmith, and which applications have an assignee common to the instant application.

Where such salt ester materials, viz. those which contain dissimilar organic radicals, are used it is necessary only that the average number of carbon atoms per atom of phosphorus in the salt ester material be 7.6 or more. Thus it is not only possible, but entirely feasible to utilize such inexpensive alcohols as ethyl, propyl and butyl alcohols in the preparation of these dithiophosphate salt ester materials. The use of dithiophosphate salt ester materials in which R1 and R2 of the above general formula are the same requires the utilization of organic radicals containing a minium of six carbon atoms. Oil-solubility considerations govern the above minimum carbon atom contents.

Phosphorus sulfide treated unsaturated organic materials useful in conjunction with the metal complexes of the present invention include, for example, phosphorus sulfide treated acyclic and cyclic unsaturated hydrocarbons and phosphorus sulfide treated unsaturated esters, acids and ketones. Particularly valuable products may be obtained by reacting from 2 to 6 molds of at least one terpene hydrocarbon with at least one mole of phosphorus sulfide, especially P285. Particularly good results are secured by the employment of the products obtained by reacting about 3 to 5 moles of pinene and/or turpentine with one mole of P285 for about 1 to 6 hours, preferably about 4 hours, at about C. to (3., preferably diflerent organic metal, especially a Mendeleef Periodic (e) Compounds in which the C=S group is included in a ring structure, e. g. a

Thio-qumone Thio-naphthaquinones Thio-anthraquinone Thio-phthalic anhydride Thio-diphenic anhydride Diphenylene thioketone (thio-fluorenone) Thio-camphor (1') Carbon bisulfide 4. Compounds in which the -S radicle forms a part an organic 5. Sulfur atom attached in the form of an inorganic radicla, e. g.

Thio-arsenite Thio-phosphite Tri-thio-Iauryl phosphite Thio-phosphate Thio-sulionic acid, and esters and salts Thio-sulfinic acid, and esters and salts B Sulfur attached to molecule through means of some other atom, i. e.,

the form of an inorganic radicle, e. g.

Thio-arsenate Thio-phosphate Thio-suliate Thio-sulfite Sulfate Sulfite Thio-sulionate Of the organic sulfur compounds which do not have stable analogous oxygen counter parts are those included in the following table:

Sulionic acids, and esters and salts of them Sulfinic acids, and esters and salts of them Bulienic acids, and esters and salts of them Polysulfides, containing the Sn radlcle, notably 1.

Alkyl polysulfides, e. g.,

Dioutyl disulfide Dibutyl trisulfide Dibutyl tetrasulfide Diamyl disulfide Diamyl trisulflde Dilauryl disulfide Dilauryl trisulfide Cyclohexyl disulfide 2. Aryl polysulfides, e. g.

Diphenyl disulfide Diphenyl tnsulfide Chlor diphenyl trisulfide Dinaphthyl disulfide 3. Aromatic substituted aliphatic polysulfides, e. g.

4. Mixed alkyl-aryl polysulfides, e. g.

5. Higher polysulfides, e. g. those formed from the above (or from Amyl benzyl disulfid Amyl benzyl trisulfide sulfides) by the addition of an S- group or groups.

Organic halogen compounds Halogenated aliphatic hydrocarbons Pentachloroethane Heptachloropropane Hexachlorobutadiene Chlorinated neohexane containing 75% chlorine Chlorinated diisobutylene containing 60% chlorine Chlorinated kerosene containing 45% chlorine Chlorinated hexadecane containing 55% chlorine Chlorinated octadecane containing 50% chlorine Chlorinated eicosane containing 50% chlorine Chlorinated docosane containing 50% chlorine Chlorinated ioots oil containing 40% chlorine Chlorinated mineral oil containing 40% chlorine Chlorinated parafiin wax containing 40% chlorine Chlorinated petrolatum containing 40% chlorine Halogenated aliphatic acids Dichlorostearic acid Dichlorolauric acid Dichloropalmitic acid Halogenated aliphatic esters Alkyl dichlorolaurates Alkyl dichloropalmitates Alkyl dichlorostearates Halogenated aromatic compounds Dichlorobenzene Trichlorobenzene Dichloronaphthalene lrichloronaphthalene Polychloronaphthalenoa Hexachlorodiphenyl other Hexachlorodiphenyl sulfide Hexachlorohenzophenone Specific examples of oil-soluble organic phosphorus acids which may be used in the practice of this invention include the following:

Organic phosphorus compounds Dithiophosphoric acids Diamyl dithiophosphoric acid Dihexyl dithiophosphoric acid Diheptyl dithiophosphoric acid Dioctyl dithiophosphoric acid Dinonyl dithiophosphorlc acid Didecyl dithiophosphoric acid Didodecyl dithiophosphoric acid Ditetradecyl dithiophosphoric acid Dihexadecyl dithiophosphoric acid Dioctadecyl dithiophosphorlc acid Di(parafiin wax) dithiophosphoric acid D1e1cosyl dithiophosphoric acid Dipentenyl dithiophosphoric acid Dioctenyl dithiophosphoric acid Didecenyl dithiophosphoric acid Dihexadecenyl dithiophosphoric acid Di(methyl-benzyl) dithiophosphoric acid Di-Eoctylbenzyl) dithiophosphoric acid Diphenyloctadecyl) dithiophosphoric acid Di-(xenylhexyl) dithiophosphoric acid Di-(phenoxyoctyl) dithiophosphoric acid D i-(butoxy-ethyl) dithiophosphoric acid B s-(3,5-dichloro-n-octyl) dithiophosphoric acid B1s-(2,6-dibromo-n-decyl) dithiophosphoric acid Dicyclopentyl dithiophosphoric acid Bis-(dnncthylcyclopentyl) dithiophosphoric acid Dicyclohexyl dithiophosphoric acid Di-(methyl-cyclohexyl) dithiophosphoric acid Di-(isopropylcyclohexyl) dithiophosphoric acid Bis-(dnsobutylcyclohexyl) dithiophosphoric acid Dmaphthenyl dithiophosphoric acid di (hydroabietyl) dithiophosphoric acid Dicyclopentenyl dithiophosphoric acid Di-(methylcyclohexenyl) dithiophosphoric acid Diabietyl dithiophosphoric acid Di -(tert-amyl-phenyl) dithiophosphoric acid Di-(2,4-di-tert-amyl-phenyl) dithiophosphoric acid Di-(paraffin wax-phenyl) dithiophosphoric acid Di-(lauroxyphenyl) dithiophosphoric acid Di-(caprylxenyl) dithiophosphoric acid Methyl octadecyl dithiophosphoric acid Butyl hexyl dithiophosphorlc acid Isopropyl sec-amyl dithiophosphoric acid Monothiophosphoric acids Diheptyl thiophosphoric acid Dioctyl thiophosphoric acid Dinonyl thiophosphoric acid Didodecyl thiophosphoric acid Dihexadecyl thiophosphoric acid Dioctadecyl thiophosphoric acid Di-(parafiin wax) thiophosphoric acid Dihexenyl thiophosphcric acid Didecenyl thiophosphoric acid Dihexadccenyl thiophosphoric acid Diphenethyl thiophosphoric acid Di-(butyl-benzyl) thiophosphoric acid Di-(octadecylphenyl) thiophosphoric acid Diphenoxydecyl thiophosphoric acid Di-(butoxyphenyl) thiophosphoric acid Di-(nitrophenyloctyl) thiophosphate acid Dicyclopentyl thiophosphoric acid Dicyclohexyl thiophosphoric acid Di-(mcthyl-cyclohexyl) thiophosphoric acid Thiophosphoric acid Dinaphthenyl thiophosphoric acid Dicyclohexenyl thiophosphorlc acid Butyl hexyl thiophosphoric acid Amyl cyclohexyl thiophosphate acid Isopropyl cyclohexyl thiophosphoric acid Phosphoric acids Dihexyl phosphoric acid Dioctyl phosphoric acid Didecyl phosphoric acid Diundecyl phosphoric acid Didodecyl phosphoric acid Dloctadecyl phosphoric acid Dihexonyl phosphoric acid Dioctenyl phosphoric acid Didecenyl phosphoric acid Dioctadecenyl phosphoric acid Dicyclopentyl phosphoric acid Dicyclohexyl phosphoric acid Di-(methylcyclohexyl) phosphoric acid Dicyclopentenyl hosphoric acid Dlcyclohexenyl p osphoric acid Di-(methyl-cyclohexenyl) phosphoric acid Di-(phenylbutyl) phosphoric acid Di-(naphthylethyl) phosphoric acid Di-(chlorophenyloctyl) phosphoric acid Di-(propylphenyl) phosphoric acid Di-(methyl-naphthyl) phosphoric acid Methyl decyl phosphoric acid Ethyl dodccyl phosphoric acid Ethyl methylcyclohoxyl phosphoric acid Dithio hosphinic acids Di exyl dithiophosphinic acid Dioctyl dithiophosphinic acid Dinonyl dithlophcsphinic acid Ditetradecyl dithiophosphinic acid Didecenyl dithiophosphinic acid Dihexadecenyl dithiophosgillixilnlc acid Dicyclohexyl dlthiophosp 0 acid In addition to the abovespecificexamplesof phosphorus acids, the metal salts of .eachsuc'hiacid maybe regarded also as further specificexarnp-les ofmaterials wbich may be used as starting materialsin the,praeticeto'f this invention.

While the metal complexes of the present invention find their widest application in the;preparation ofllubricants intended for usein'fthe .crankcases roflintern'al com- 2gv bustion engines, they are also useful-in the preparation, as above indicated, of improveduextremegpressurellubricants. In addition to :these particular applications,' 'theamet-al complexes of this inventionlmay also be use'clin thepreparation of improved'lubricants forspecialized uses, such 5 as jet aviation, topcylinder, steamzcylinden-steam locomotivumihaymarggasengine,:refrigeratingmachine, hydraulic, compressor, turbine, spindle, and torque converter lubricants.

The lubricating oil base in :which the metal complexes t of the present invention and, optionally, certain additional improving agents "are incorporated may be of synthetic, vegetable, animal, or mineral origin. Because of their low cost, availability, and desirable properties,.the mineral oils, i. e, those derived from petroleum, find the widest application intlre 'Itibticantfield.

This invention as heretofore described also relates to various types .of-fllubricant improving agents and lubrieating compositions. There is, at the present time, sundry mineral "oils, .each .best .suited from the standpoint of viscosity and other properties for-different uses and environments. The oil base oftatlubricating composition of the present invention designedvfor'a particular use and enviornment will preferably tcontpriselallubricating oil having the characteristics now-Well recognized as bestsuitedfor such useand environment.

In the following tables, particular characteristics of refined mineral lubricating oils best suited for 'many types of use and climate aredisclosed.

[The -.-actual Mpper limit of preferred viscosity index is infinite for most uses. The values given-in'the following tables indicate the present commercial maximum-values.

: Grankcase Typeiotf Climate Jet Aviation Top Cylinder :Steam .Gyltnder Gasoline .Dlesel Aviation Arctic k Preferred viscosity range 1 GHOFIO" F-... 5045g/100" 'F i 80120/2l0F. Flash pt. preferably no lower the. 300 F 340 275 400 F. Pour pt. preferably no higher than 50 F -50 F .0 F

Temperate Preferred viscosity range 1 Flash pt. preferably no lower than Four pt. preferably no higher than--.

Tropical l Expressed in Sayboltzflntverselsecohds at indicated temperature.

50150/100 F. i100-190/210 F. 300 F i500 -F su F.

man o 210 F. I =500 1*.

I Refrigerating Compressor Type of Climate Steam'Loeomo Gas Engine tive I Machine Temperate Preferred viscosity range 1 "+00/210:F '50-'70/210 F- -801210" F-.." BG ISgJ-IOOQ'E "125 300/l00F 200-600/100 F. Flash pt. preferably no lower than- :375 Fm- 350 is 375 F- 325 325? 350 l Pour pt. preferably no higher-than--- 0F "0 F 0 F 25 F .i =-0 F' 10F.

Tropical Preferred viscosity range L..- 3560 210-'F..--. '50-70/210" FL--- 40-80 210 F-.. -180/100" F 200l.000/ F..- 300-600/100 F. Flash pt. preferably no lowerthan- 375?. "3509i 375 350 F 360 F 350" 1. Pour pt. preferably no higher than 20F '15? E F --25 F Preferred V. I. (Dean and Davis) 35-120 354.20 I

1 Expressed in Saybolt Universal seconds'at; indicated temperature.

Klein. Type oi Climate Turbine Spindle Torque Converter Automotive Industrial Arctic Preferred viscosity range 1 120-500/100" F...-- 35-100I100 F 20-80%;100 F 30-1,000/210 F. Flash pt. preferably no lower than. 375 F 275 F 275 30 300 F. Pon. pt. preferably no higher than 20 F. 50 F -50 F 10 F.

Temperate I Preferred viscosity range 1 125500/100 F.---. 7040101100" F 30-250/100 F 50140/210 F 502,000/210 F. Flash pt. preferably no lower than 400 F 275 300 F 325 F 325 F. Pour pt. preferably no higher than F F -30 F 0 F 20 F.

Tropical Prz'ferred viscosity range 1 125-500/100 F....- 150300/100 F-...- 30 -301100 F 80 2001210 F 80-2,000/210 F. Flash pt. preferably no lower than 400 300 F 300 350 F 326 F. Pour pt. preferably no higher than 20 F F 0 F F Preferred V. I. (Dean and Davis)-- 85-120 75-120 100-160 75-120 -120.

1 Expressed in Saybolt Universal seconds at indicated temperature.

As indicated earlier, our metal complexes find their widest application in the preparation of lubricants intended for use in the crankcases of internal combustion engines, particularly in combination with other improving agents such as, in the preferred instance, dithiophosphate salt-esters and/or phosphorussulfide treated unsaturated organic materials.

It is common practice in the lubricant additive industry to prepare a liquid, homogeneous concentrate containing one or more separate improving agents and, optionally, a minor proportion of a mineral oil, preferably one of low viscosity. Such liquid concentrates dissolve more readily in lubricating oil bases than do solid improving agents and, in addition, minimize the problems usually associated with the processing, handling, and transportation of solid materials.

Thus the present invention contemplates not only the preparation of finished lubricants containing the metal complexes of our invention, but also the preparation of lubricant improving agents, i. e. concentrates, which when dissolved in suitable lubricating oil bases will yield finished lubricants containing our metal complexes, and,

optionally, such other improving agents as are desired.

From an examination of the specification it will be noticed that our metal complexes vary widely in metal content, such metal content usually being expressed, for convenience, as percent metal sulfate ash. As a matter of actual practice in the compounding of lubricants from our metal complexes, we have found that the amount of metal in combined form in the lubricant due to the presence of our complex is the critical factor to be considered. Since it has been shown that our metal complexes may differ very substantially in metal content, it follows that in the preparation of a lubricant having a certain fixed proportion of metal due to our complex, one would use less of a metal complex of high metal content than a similar metal complex of lower metal content. To illustrate this point more specifically, 10 parts by weight of a complex of sulfate ash content dissolved in,90 parts by weight of lubrieating oil would yield a lubricant having the same metal content as one prepared by dissolving 40 parts by weight of a complex of 10% sulfate ash content in 60 parts by weight of lubricating oil.

It becomes apparent then that we can properly define the amounts of our metal complexes desirably present in lubricant improving agents, and lubricants only in terms of metal content or a proportional equivalent thereof, for example, metal sulfate ash content. Furthermore, it should be pointed out that the desirable range of such metal or metal sulfate ash content will difier substantially in going from one metal complex to a complex of'a difierent metal. This situation exists because different metals have different chemical combining weights,

saturated organic materials and are perforce present in different weight percentages in complexes of our invention wherein the organic acid and promoter material have been fixed both as to identity and amount.

As a consequence of a large number of tests performed on lubricants containing metal complexes of our invention, we have been able to determine the operable ranges of metal content and metal sulfate ash content (due to the presence of our complexes) for both lubricant improving agents and finished lubricants.

RANGES FOR WEIGHT PERCENT OF METAL SULFATE A wide variety of oil-soluble, phosphorusand sulfurbearing organic materials are available and are preferred for use in combination with our oil-soluble, metal complexes in preparing lubricant improving agents and lubricants.

By this statement we do not mean that all oil-soluble, phosphorus-and-sulfur-bearing organic materials are of equal eflicacy for use in lubricant compositions. Some are more effective than others; for example, dithiophosphate salt-diesters and phosphorus sulfide treated un (especially Pass-treated terpene hydrocarbons) have been found to be of particular utility.

By way of illustration, a numberof oil-soluble, phosphorus-and-sulfur-bearing organic materials are given, one or more of which may be used along with our metal complexes in producing lubricant compositions:

I. Esters and salt-esters of inorganic thioacids of phosphorus, for example (1) Esters of thiophosphorus acids, e. g.:

S-n-octyl monothiophosphite S S-dl-n-hexyi dithiophosphlte Tri-amyl trithiophosphite Laury] dicthyi trithiophosphite 0,0-di-n-hexyl monothiopbosphlte 0,S-di-n'octyldithiophosphlte Di-lauryl trithiophosphlto S-cetyl monothiophosphito (2 Salt-esters of thiophosphorons acids, a. g.:

Barium S-oetyi monothiophosphite Strontium 0,S- dilauryl dithiophosphlte Calcium di-lauryl trithiophosphite Zinc S-octadccyl monothiophosphite Copper 8,8-dl-decyl dithiophosphite ALCOHOLS AND MERCAPTANS Analysis of Reaction Product Example No. Organic Material Mols Additional Reaotant Mols Reagent Mols Percent Percent Sulfur Phosphotons Capryl Alcohol 6 OleioAcid 2 P481 1 12.2 6.4 4 1 1.7 2.5 6 1 8.7 6.2 do 8 1 5.4 4.6 Sulfurized Oleyl Alcohol 3 1 9.1 2.0 Amyl Mercaptan 3 1 29.2 9.5

ACIDS AND ESTERS Oleic Acid 8 P481 1 5.9 4.4

do 8 P483 1 0.9 0.93

4 P451 1 8.5 3.6 8 P487 1 3.9 1.6 8 P451 1 6.9 3.6

SPECIFIC EXAMPLES OF LUBRICANT IMPROV- ING AGENTS AND EMPLOYING METAL COM- 25 Composition (weightpemm) Lubricant PLEXES OF THE PRESENT INVENTION Number Certain oil-soluble phosphorus-and-snlfur-bearing or- Percent ponent ganic materials used in many of the lubricant compositions illustrated herein are designated as follows (unless 3g: 61) 2 25 9 g ng r ag o i l I 2 otherwise stated, percentages given are in weight-percent 4 0:23 improving agent A. p e of total improving agent): 8: 8g ig gg j fig 25832 97. i3 SAt 130 mirlleral oliil.

Improving Description 5 (022) ir n ios in g ag n t Af Agent 1. improving agent B. 96. 3g. (0 sA E so mn iemi g.

. 1. .25 me a comp ex 0 xample 2.

A product prepared by reacting about 4 moles of turpentine with 1 mole of P255 for about 4 hours at about 140 C; 6 gg fi igzg 2 2E:

61% solution in low viscosity mineral oil. 44 ilngrovin a ent D B zinc di-(fi-methyl-see-amyl) dilthliirphosphate; 44% solu- 9200 SAE 30 i ion in ow viscosi y minera 0' O mixture of 60 mole-percent zinc di (4-methyl-sec-amyl) 7 (0-82) fi i'igg g i f dithiophosphate and mole-percent zinc di-isopropyl 4O 98 improving dithiophosphate; 40% solution in low viscosity numeral 92 imgroving ggg D ba ir iiim salt of the mixed dithiophosphate diester obzg g tained by treating a mixture of l-methyl-sec-amyl, im g g g i p n-hexyl, and capryl alcohols (3, 2, and3 parts by weight, 98 nt respectively) with P185; 39% solution in low-viscosity imgroving aggnt D mum] 94. a2 sea 30 mineral oil.

1. 47 prigrlart viscositfy index improver. m. i t For each of the specific lubricants shown hereinafter, 9 5 (0 38) ini pi 'osiiig n i ixampled the composition of the corresponding lubricant improving 2i l agent can be discerned by considering the weight percent- 95:28 .5; 30

ages of the separate improving agents as parts by weight. g; (0 32) g gg g ggg ll engl'ovel.

For example, the lubricant improving agent correspond- 0 improving agent p ing to lubricant No. 1 would consist of 1 part by Weight 8.22 32 B of improving aglent B, plus 5 paiits by weight 02 the corltli- 95:79 sa ilzotmineraltoil; d

p 6X Of Examp 6 1 (01 0.71 SU fate ash part y weig t 0. 99 pr1or ar VlSCOSl yin ex improver.

1.75 0.31 metal com 1 x of E 4, thereof). If the separate improving agents do not them- 55 11 improving agent A.

selves contain a proportion of mineral oil, some may be 822 gggigzlgg 352% 8- added, if necessary, to secure a fully liquid, multi-com- 96:35 SAE 40 mineraloi]:

ponent concentrate as discussed earlier 1n the section H2 (0-33) figasg g e g f a ple 4.

regarding improving agent concentrates. improving agent The values in parentheses in the percent column 2-32 iiz zg ggsg gbelow give the percent of metal sulfate ash present in 3115 0,45 metal complex of Example 5.

the lubricant imparted by the amount and kind of metal lggggzi gg igcomplex employed therein. improving agent 1 96. 08 SAE 40 mineral oil.

2. 12 (0. 3) metal complex of Example 5.

Lub t Composition (weight percent) 14 $4 35333; 3.523% g.

H 8.11 Num ber 0. 46 impiigoving agent D. Percent Component 94. 97 SA 30 mineral oil.

3. 4 (0. 48) metal complex of Example 5. 0.49 improving agent A. 94. 0 SAE 30 mineral oil. 1.14 improving agent 0.

1 ?.g (0.71) metal complex oillsixample 1. 94 44 s ll ugr fi p t i -g og rn gent.

. LID T0 in 8 8D 90 0 S153 5 0 u lin etal oil. 3. 38 (0. 62) metal complex of Example 6.

2 8.8 (1.14) metal cp m plex (ifgxample 1. 8. 2 35 225 kgg e r t t.

9 52 83E133?) m iiigg l 011: i 0: 92 improving agent I): 3 338 fi iii i nt f iii (1 83) ii i ofitiii tii'm e o 0: 98 imgroving agent 0: 0.5 zinc di-lauryl dithiophosphate.

0. 92 improving agent D. 0. 6 P and 8 bearing product of Example 11.

Composition (weight percent) Number Percent Component SAE 10 mineral oil.

metal complex of Example 6. magnesium di-n-octyl dithiophosphatc... P and S bearing product, of Exzimplo 33. SAE 10 mineral oil.

metal'compl x of Example 7.

trinrnyl trithiophosphite.

P and S bearinc product of Exznrple l5. SAE 20 mineral oil.

metal complex of Example 7.

metal complex of Example 6.

trilauryl trithiophosphate.

P and S bearing product of Example 27. SAE 20 mineral oil.

metal complex of Example 7.

calcium di-rnrlecyl dithiophosphatc.

P and S hem-inc product of Example SAE 20 mineral oil.

metal complex of Example 8.

zinc di-(lauryl-phenyl't dithiophosphii P and S nearing product of Example 3.3. SAE 20 mineral oil.

metal complex of Example 8.

barium carbonate complex of Example 7 cobalt di-capryl dithiophosphnte.

SAE 20 mineral oil.

metal complex of Example 8.

P and S bearing product of Example 38. SAE 30 mineral oil.

metal complex of Example 9.

improving agent 0.

SAE 30 mineral oil.

metal complex of Example 9.

nickel di-octadecyl dithiophosphate.

P and S bearing product of Example 19. SAE 30 mineral oil.

metal complex of Example 9. tri-(tert-butyl-phenyl) dithiophosphate. P and S bearing product of Example 24. SAE 30 mineral oil.

metal complex of Example 10.

P and S bearing product of Example 39. SAE 30 mineral oil.

metal complex of Example 10. improving agent A.

SAE 30 mineral oil.

metal complex of Example 10. improving agent 0.

SAE 30 mineral oil.

metal complex of Example 10. zinc di-(methyl-cyclohexyl) :0 co pulpoowgppucaccpaonc H H N! v v 0.2 (0.055) 1.5 81.0 15.0 (4.1) 31 2.0 dithiophosphate. 2.0 P and S bearing product of Example 28.

1 2 parts per million.

Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated in any of the following claims, or the equivalent of such, be employed.

I therefore particularly point out and distinctly claim as my invention:

1. A process which comprises preparing and mixing a mass in which, 211250 0., at least 50% of the total mass is in the liquid state, and in which mass the active componcnts consist of: A, at least one oil-soluble organic acid compound; B, at least one organic metal compound derived from a metal-free organic compound having: (a) an ionization constant in Water of at least about 1X10- at about 25 C.; (b) a Water solubility at 50C. of at least about 0.0005%;'and (c) in saturated aqueous solutions at about 25 C. a pH of not greater than about 7, the relative amounts of A and B used being in the range of from about one equivalent of A to about 10 equivalents of B to about 10 equivalents of A to about one equivalent of B; C, Water, in an amount equal to at least about onetcnth mole per mole of B; maintaining the mass at a tempcraturo and for a period of time sufllcient to drive off substantially all free water and water of hydration which may be present; and then treating the mass with an acidic material of which the ionization constant is higher than the ionization constant of the organic compound from 3. The proccss'of claim 1 further characterized in that component A is a. phosphorus acid compound.

4. The process of claim 1 further characterized in that component A is a thiophosphorus acid compound.

5. The process of claim 1 further characterized in that component A is at least 1 sulphur acid compound and at least 1 phosphorus acid compound.

6. The process of claim 1 further characterized in that component A is at least 1 sulphur acid compound and at least 1 thiophosphorus acid compound.

7. The process of claim 1 further characterized in that component A is at last lsulph'onic' acidcompound.

8. The process of claim 1 further characterized in that component A is at least 1 barium salt of an oil-soluble organic acid.

9. The process of claim 1 further characterized in that component A is'thc barium salt of at least 1 sulphur acid.

10. The process of claim 1 further characterized inthat component A is the barium salt of atlcast 1 phosphorus acid.

11. The process of claim 1 further characterized in that component A i's the barium-salt of at least l'thiophos phorus acid.-

12. The process of claim 1 further characterized in that component A is a mixture of the barium salts of at least 1 sulfur acid and the barium salts of at least one phos phorus acid.

13. The process of claim 1 further characterized in that component A is a mixture of the barium salts of at least one sulfur acid and the barium Salts of at least one thiophosphorus acid.

14. T he process of claim 1 further characterized in that component A is at least one barium sulfonate.

15 The process of claim 1 further characterized in that component A is a mixture of at least one barium sulfonatc and the barium salts of at least one phosphorus acid.

16. The process of claim 1 further characterized in that component A is a mixture of at least one barium sulfonatc and the barium salts of at least one thiophosphorus acid.

17. The process of claim 1 further characterized in that component B is the metal salt of a phenolic compound.

18. The process of claim 1 further characterized in that component B is the metal salt of a phenol.

19. The process of claim 1 furtherchar'actc'rizcd in that component B is the metal salt of a hydrocarbon substituted phenol in which the hydrocarbon substituents have not more than 16 carbon atoms.

2.0. The process of claim 1 further characterized in that component B is the metal salt of an alkyl phenol.

21. The process of claim 1 furthcr'charactcrizcd in that component B is the rntal sa'lt ofan cnolic compound.

22. The process ofclaim '1 further characterized in that the process istrcated with C02 in amounts sufilcicnt to liberate a substantial proportion of said organic compound of componnt BJ 23. The process'of claim 1 further characterized in that the component A is a mixture of petroleum mahogany sulphonic acid compounds and oil soluble alkyl aromatic sulphonic acid compounds. 7

24. The process of claim 1 furthcrcharac tcriz ed in that the process mass is strippcd'of said liberated organic compound of component B.

25. The process of claim 1 further characterized in that said process mass is treated with CO2 in amounts sufficient to libcratea subst'antialproportion of said organic compound of component'B, and said liberated portions of said organic cornpoundofcomponent B a'rcs'trippcd from the process mass. V

26. A product in accordance with the process of claim 1..

(References on following page) References Cited in the file of this patent UNITED STATES PATENTS 4 v. 38 Assefi? et 211. Nov. 4, 1952 Assefl? et a1 Nov. 4, 1952 Asseff et a1 Nov. 4, 1952 Asseff et a1. Nov. 4, 1952

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2616905 *Mar 13, 1952Nov 4, 1952Lubrizol CorpOrganic alkaline earth metal complexes and methods of making same
US2616906 *Mar 28, 1952Nov 4, 1952Lubrizol CorpOrganic alkaline earth metal complexes and method of making same
US2616911 *Dec 28, 1951Nov 4, 1952Lubrizol CorpOrganic alkaline earth metal complexes formed by use of sulfonic promoters
US2616924 *Mar 16, 1951Nov 4, 1952Lubrizol CorpOrganic alkaline earth metal complexes and method of making same
US2616925 *Dec 28, 1951Nov 4, 1952Lubrizol CorpOrganic alkaline earth metal complexes formed by use of thiophosphoric promoters
US2617049 *Mar 16, 1951Nov 4, 1952Lubrizol CorpOrganic barium complexes and method of making same
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2862847 *May 4, 1956Dec 2, 1958Rohm & HaasPesticidal arenethiosulfonates
US2915517 *May 8, 1957Dec 1, 1959Lubrizol CorpOil-soluble metal sulfonates and process for the preparation thereof
US2921910 *Sep 7, 1955Jan 19, 1960Pure Oil CoNeutralization of crude dry-cleaning soaps
US2957908 *Dec 13, 1957Oct 25, 1960Texaco IncStabilization of hyperbasic magnesium sulfonates
US3050538 *Apr 16, 1958Aug 21, 1962Inst Francais Du PetroleMolybdenum blue complexes
US3061466 *Aug 16, 1957Oct 30, 1962Dow Chemical CoMagnesium salts of coal acid coatings
US3223720 *Jun 7, 1963Dec 14, 1965Angeli Inst SpaAluminum pamoate
US3224873 *Feb 25, 1963Dec 21, 1965Gen Mills IncLiquid-liquid recovery of copper values using alpha-hydroxy oximes
US3354189 *May 26, 1965Nov 21, 1967Cities Service Oil CoMetal (hydrocarbyl and acid hydrocarbyl pyrophosphates) and amine adducts
US3358006 *Aug 28, 1962Dec 12, 1967Stauffer Chemical CoOrganotin dithiophosphates
US3461132 *Aug 11, 1965Aug 12, 1969Boehringer Sohn IngelheimNovel tin complexes
US3481718 *Jan 15, 1969Dec 2, 1969Sinclair Research IncGasoline fuel composition
US3533762 *Aug 17, 1967Oct 13, 1970Cities Service Oil CoHydrocarbon fuels containing polyvalent metal hydrocarbyl pyrophosphate salts and amine adducts thereof
US3535241 *Aug 17, 1967Oct 20, 1970Cities Service Oil CoLubricating oils containing polyvalent metal hydrocarbyl pyrophosphate salts and amine adducts thereof
US3764571 *Feb 18, 1971Oct 9, 1973Dart Ind IncOrganotin stabilizer systems
US3779922 *Jun 19, 1972Dec 18, 1973Lubrizol CorpBarium-containing dispersions and process
US3976439 *Sep 24, 1975Aug 24, 1976Standard Oil CompanyNon-leaded gasoline having improved anti-knock quality
US3976440 *Sep 24, 1975Aug 24, 1976Standard Oil CompanyNon-leaded gasoline having improved anti-knock quality
US4209453 *Jul 25, 1978Jun 24, 1980Phillips Petroleum CompanyAntimony tris(dihydrocarbyl phosphite) and preparation thereof
US4371471 *Jul 22, 1980Feb 1, 1983Rhone-Poulenc IndustriesHydrocarbon stock solutions of Cr+6 compounds storage-stabilized by a soluble partial ester of a phosphoric acid
US4443577 *May 12, 1982Apr 17, 1984The Lubrizol CorporationOne-component moisture curable urethane coating system
US4468339 *Jan 21, 1982Aug 28, 1984The Lubrizol CorporationAqueous compositions containing overbased materials
US4532080 *Oct 11, 1983Jul 30, 1985Monsanto Europe, S.A.Adhesion promoters
US4557872 *Oct 11, 1983Dec 10, 1985Exxon Research & Engineering Co.Basic alkaline earth metal sulphonates
US5047566 *Jul 7, 1987Sep 10, 1991Minnesota Mining And Manufacturing CompanyColorless ferric alkylphosphates
US5322872 *Apr 14, 1993Jun 21, 1994The Lubrizol CorporationStabilized compositions of mixed metal carboxylates
US5858208 *Feb 25, 1997Jan 12, 1999Baker Hughes IncorporatedMethods for improving conversion in fluidized catalytic cracking units
US6617287Oct 22, 2001Sep 9, 2003The Lubrizol CorporationManual transmission lubricants with improved synchromesh performance
US7329772Apr 29, 2004Feb 12, 2008Crompton CorporationMethod for the preparation of a hydroxyalkyl hindered phenolic antioxidant
US8796192Oct 29, 2010Aug 5, 2014Chevron Oronite Company LlcNatural gas engine lubricating oil compositions
US8841243Mar 31, 2010Sep 23, 2014Chevron Oronite Company LlcNatural gas engine lubricating oil compositions
US8969273Feb 18, 2009Mar 3, 2015Chevron Oronite Company LlcLubricating oil compositions
US9045574Sep 28, 2009Jun 2, 2015Mitsui Chemicals, Inc.Viscosity modifier for lubricating oils, additive composition for lubricating oils, and lubricating oil composition
US20050242328 *Apr 29, 2004Nov 3, 2005Crompton CorporationMethod for the preparation of a hydroxyalkyl hindered phenolic antioxidant
US20080064616 *Oct 14, 2005Mar 13, 2008Huntsman Petrochemical CorporationFuel And Oil Detergents
US20090093384 *Oct 3, 2007Apr 9, 2009The Lubrizol CorporationLubricants That Decrease Micropitting for Industrial Gears
EP0679638A1Apr 24, 1995Nov 2, 1995The Lubrizol CorporationSulphur-coupled saligenin salts as additives for lubricating oils
EP0695798A2Aug 2, 1995Feb 7, 1996The Lubrizol CorporationLubricating compositions, concentrates, and greases containing the combination of an organic polysulfide and an overbased composition or a phosphorus or boron compound
EP0712923A1Nov 9, 1995May 22, 1996The Lubrizol CorporationLubricants and fluids containing thiocarbamates and phosphorus esters
EP0769546A2Oct 17, 1996Apr 23, 1997The Lubrizol CorporationAntiwear enhancing composition for lubricants and functional fluids
EP0779356A2Dec 12, 1996Jun 18, 1997The Lubrizol CorporationCondensation product of alkylphenols and aldehydes, and derivatives thereof
EP1652910A2Oct 12, 1995May 3, 2006The Lubrizol CorporationOverbased metal salts useful as additives for fuels and lubricants
EP2290044A1Mar 27, 2006Mar 2, 2011The Lubrizol CorporationTitanium compounds and complexes as additives in lubricants
WO2003035810A1Oct 7, 2002May 1, 2003Lubrizol CorpManual transmission lubricants with improved synchromesh performance
WO2003099972A1May 14, 2003Dec 4, 2003Lubrizol CorpLow ash stationary gas engine lubricant
WO2010107882A1Mar 17, 2010Sep 23, 2010The Lubrizol CorporationAnthranilic esters as additives in lubricants
WO2011031659A1Sep 7, 2010Mar 17, 2011The Lubrizol CorporationFarm tractor lubricating composition with good water tolerance
WO2011038331A1Sep 27, 2010Mar 31, 2011Mitsui Chemicals, Inc.Viscosity modifier for lubricating oils, additive composition for lubricating oils, and lubricating oil composition
WO2011066059A1Nov 1, 2010Jun 3, 2011The Lubrizol CorporationMethods of controlling sulfur trioxide levels in internal combustion engines
WO2011066141A2Nov 17, 2010Jun 3, 2011The Lubrizol CorporationStabilized blends containing friction modifiers
WO2011066142A1Nov 17, 2010Jun 3, 2011The Lubrizol CorporationStabilized blends containing friction modifiers
WO2011066144A1Nov 17, 2010Jun 3, 2011The Lubrizol CorporationStabilized blends containing friction modifiers
WO2011066145A1Nov 17, 2010Jun 3, 2011The Lubrizol CorporationStabilized blends containing friction modifiers
WO2011112372A1Feb 28, 2011Sep 15, 2011The Lubrizol CorporationTitanium and molybdenum compounds and complexes as additives in lubricants
WO2011126736A1Mar 23, 2011Oct 13, 2011The Lubrizol CorporationZinc salicylates for rust inhibition in lubricants
WO2011130142A1Apr 11, 2011Oct 20, 2011The Lubrizol CorporationLow-ash lubricating oils for diesel engines
WO2011146456A1May 17, 2011Nov 24, 2011The Lubrizol CorporationLow ash lubricants with improved seal and corrosion performance
WO2012018655A2Jul 27, 2011Feb 9, 2012The Lubrizol CorporationAmmonium nitrate fuel oil mixtures
WO2012027254A1Aug 22, 2011Mar 1, 2012The Lubrizol CorporationLubricants containing aromatic dispersants and titanium
WO2012033668A1Aug 30, 2011Mar 15, 2012The Lubrizol CorporationHydroxychroman derivatives as engine oil antioxidants
WO2012040021A1Sep 15, 2011Mar 29, 2012The Lubrizol CorporationAminobenzoic acid derivatives
WO2012071305A1Nov 21, 2011May 31, 2012The Lubrizol CorporationPolyester quaternary ammonium salts
WO2012071313A1Nov 21, 2011May 31, 2012The Lubrizol CorporationPolyester quaternary ammonium salts
WO2012087775A1Dec 16, 2011Jun 28, 2012The Lubrizol CorporationLubricating composition containing a detergent
WO2012094275A1Jan 3, 2012Jul 12, 2012The Lubrizol CorporationContinuously variable transmission fluid with extended anti-shudder durability
WO2012097026A1Jan 11, 2012Jul 19, 2012The Lubrizol CorporationEngine lubricants containing a polyether
WO2012112635A1Feb 15, 2012Aug 23, 2012The Lubrizol CorporationLubricating composition and method of lubricating driveline device
WO2012112658A1Feb 15, 2012Aug 23, 2012The Lubrzol CorporationLubricants with good tbn retention
WO2012166781A1May 30, 2012Dec 6, 2012The Lubrizol CorporationLubricating composition with improved tbn retention
WO2012170242A1May 30, 2012Dec 13, 2012Dow Global Technologies LlcMethod t0 make an aqueous pour point depressant dispersion composition
WO2013006303A1Jun 26, 2012Jan 10, 2013The Lubrizol CorporationLubricant providing improved cleanliness for two-stroke cycle engines
WO2013119623A1Feb 6, 2013Aug 15, 2013The Lubrizol CorporationMethod of preparing a sulfurized alkaline earth metal dodecylphenate
WO2014078083A1Oct 31, 2013May 22, 2014The Lubrizol CorporationCoupled phenols for use in biodiesel engines
WO2014124187A1Feb 7, 2014Aug 14, 2014The Lubrizol CorporationBridged alkaline earth metal alkylphenates
WO2014158435A1Feb 17, 2014Oct 2, 2014The Lubrizol CorporationEngine lubricants containing a polyether
WO2015088769A2Nov 25, 2014Jun 18, 2015The Lubrizol CorporationMethod for preparing functionalized graft polymers
WO2015094942A1Dec 12, 2014Jun 25, 2015The Lubrizol CorporationHydrogenated natural oils in rust preventive coatings
WO2015142482A1Feb 24, 2015Sep 24, 2015The Lubrizol CorporationLubricants containing blends of polymers
WO2015148889A1Mar 27, 2015Oct 1, 2015Mitsui Chemicals, Inc.Viscosity modifier for lubricating oils, additive composition for lubricating oils, and lubricating oil composition
WO2015153160A1Mar 23, 2015Oct 8, 2015The Lubrizol CorporationMethod for preparing a sulfurized alkaline earth metal dodecylphenate
WO2015171364A1Apr 28, 2015Nov 12, 2015The Lubrizol CorporationAnti-corrosion additives
WO2015183908A1May 27, 2015Dec 3, 2015The Lubrizol CorporationLow molecular weight imide containing quaternary ammonium salts
WO2015183916A1May 27, 2015Dec 3, 2015The Lubrizol CorporationLow molecular weight amide/ester containing quaternary ammonium salts
WO2015184247A1May 29, 2015Dec 3, 2015The Lubrizol CorporationHigh molecular weight imide containing quaternary ammonium salts
WO2015184251A1May 29, 2015Dec 3, 2015The Lubrizol CorporationBranched amine containing quaternary ammonium salts
WO2015184254A1May 29, 2015Dec 3, 2015The Lubrizol CorporationHigh molecular weight amide/ester containing quaternary ammonium salts
WO2015184276A1May 29, 2015Dec 3, 2015The Lubrizol CorporationEpoxide quaternized quaternary ammonium salts
WO2015184280A1May 29, 2015Dec 3, 2015The Lubrizol CorporationImidazole containing quaternary ammonium salts
WO2015184301A2May 29, 2015Dec 3, 2015The Lubrizol CorporationCoupled quaternary ammonium salts