Mixed phosphorous- and sulfur- containing reaction products useful in power transmitting compositions

A composition comprising reaction product recovered from a top phase of a reaction product mixture prepared by a process comprising:

• (A) providing an admixture comprising:
• (1) at least one beta-hydroxy thioether reactant represented by the formula:
• R--(SCH.sub.2 CH.sub.2 OH ).sub.x I
• wherein R represents an unsubstituted or substituted hydrocarbyl group, and wherein x is a number from 1 to about 3 and identifies the number of --SCH.sub.2 CH.sub.2 OH groups attached to R;
• (2) an amount of phosphorous-containing reactant selected from the group consisting of dihydrocarbyl hydrogen phosphite, trihydrocarbyl phosphite, and mixtures thereof, sufficient to provide at least about ten mole percent of phosphorous containing reactant based on the total moles of reactants in said reaction mixture;
• and optionally
• (3) nucleophilic reactant containing at least one reactive hydroxy group and being free from any reactive mercapto or --SCH.sub.2 CH.sub.2 OH groups;
• (B) heating the admixture prepared in accordance with Step (A) in a manner and under conditions sufficient to:
• (1) cause the beta-hydroxy thioether to react with the components of the reaction mixture to form a product mixture comprising:
• (i) non-phosphorous containing compounds having within their structure at least one group represented by the formula:
• --S--CH.sub.2 CH.sub.2 --Q-- I"
• wherein Q is independently selected from the group consisting of oxygen or sulfur, said Q constituting a portion of the residue derived from:
• (1) beta-hydroxy thioether reactant, (2) the hydrocarbyl portion of the organic phosphite reactant, (3) when present, the nucleophilic reactant, and (4) mixtures of (1) to (3);
• and wherein the remainder of Structure I" exclusive of Q, contains residue of beta-hydroxy thioether reactant;
• and
• (ii ) phosphorous compounds comprising phosphorous acid and organic phosphites having within their structure at least one group represented by the formula:
• R--SCH.sub.2 CH.sub.2 Q-- I'
• bonded directly to the phosphorous atom of the organic phosphite, said R--SCH.sub.2 CH.sub.2 O-- group representing residue of beta-hydroxy thioether;
• and
• (2) cause the product mixture to separate into a top phase and a bottom phase, with said top phase comprising a major amount of said non-phosphorous containing compounds and said bottom phase comprising a major amount of said phosphorous containing compounds;
• and
• (c) separating the top phase from the bottom phase.

A composition comprising reaction product recovered from a bottom phase of a reaction product mixture prepared by a process comprising:

• (A) providing an admixture comprising:
• (1) at least one beta-hydroxy thioether reactant represented by the formula:
• R--(SCH.sub.2 CH.sub.2 OH).sub.x I
• wherein R represents an unsubstituted or substituted hydrocarbyl group, and wherein x is a number from 1 to about 3 and identifies the number of --SCH.sub.2 CH.sub.2 OH groups attached to R;
• (2) an amount of phosphorous-containing reactant selected from the group consisting of dihydrocarbyl hydrogen phosphite, trihydrocarbyl phosphite, and mixtures thereof, sufficient to provide at least about ten mole percent of phosphorous containing reactant based on the total moles of reactants in said admixture;
• and optionally
• (3) nucleophilic reactant containing at least one reactive hydroxy group and be free from any reactive mercapto or --SCH.sub.2 CH.sub.2 OH groups;
• (B) heating the admixture prepared in accordance with Step (A) in a manner and under conditions sufficient to:
• (1) cause the beta-hydroxy thioether to react with at least the phosphorous containing reactant to form a product mixture comprising:
• (i) non-phosphorous containing compounds having within their structure at least one group represented by the formula:
• --S--CH.sub.2 CH.sub.2 --Q-- I"
• wherein Q is independently selected from the group consisting of oxygen or sulfur, said Q constituting a portion of the residue derived from:
• (1) beta-hydroxy thioether reactant, (2) the hydrocarbyl portion of the organic phosphite reactant, (3) when present, the nucleophilic reactant, and (4) mixtures of (1) to (3);
• and wherein the remainder of Structure I"exclusive of Q, contains residue of beta-hydroxy thioether reactant;
• (ii) phosphorous containing compounds comprising phosphorous acid and organic phosphites having within their structure at least one group represented by the formula:
• R--SCH.sub.2 CH.sub.2 O-- I'
• bonded directly to the phosphorous atom of the organic phosphite, said R--SCH.sub.2 CH.sub.2 OH-- group representing a residue of beta-hydroxy thioether;
• and
• (2) cause the product mixture to separate into a top phase and a bottom phase with said bottom phase comprising a major amount of said phosphorous containing compounds;
• and
• (C) separating the bottom phase from the top phase to recover the bottom phase.

A hydrocarbon soluble or dispersible mixture of compounds comprising phosphorous- and sulfur-containing reaction products prepared by reacting in admixture:

• (a) organic phosphite ester having the formula:
• P(OR.sub.5).sub.3 II
• wherein R.sub.5, independently, represents the same or different C.sub.1 -C.sub.30 saturated or unsaturated, straight or branched chain aliphatic hydrocarbyl radical or the aromatic radical:
• ##STR57## wherein R.sub.6, independently, represents H or the same or different C.sub.1 -C.sub.24 hydrocarbyl radical;
• n is a number from 1 to 3;
• and wherein R.sub.5 and R.sub.6 may be inertly substituted, wherein said organic phosphite ester comprises at least about ten mole percent of the reactants in said admixture;
• and
• (b) organic sulfur containing reactant comprising beta-hydroxy thioether represented by at least one of the structural formulas:
• ##STR58## wherein R.sub.11 represents a C.sub.8 -C.sub.20 saturated or unsaturated, straight or branched chain hydrocarbyl radical having not greater than about two unsaturated linkages;
• and wherein R.sub.8 and R.sub.9, each independently represent H or C.sub.1 -C.sub.12 alkyl;
• a, b, c and d each, independently represent the same or different number 1--3 with the proviso that a, b, c, d, R.sub.8 and R.sub.9 are selected to provide at least one --SCH.sub.2 CH.sub.2 OH group in formula V and Z is --S-- or --S--S--.

A lubricating oil composition adaptable for use as an automatic transmission fluid which comprises mineral oil and an amount of an additive mixture effective to impart at least one of the properties of anti-wear and anti-oxidation to said fluid relative to the absence of said additive mixture, said additive mixture comprising the phosphorous- and sulfur-containing reaction products prepared by reacting in admixture:

• (1) at least one beta-hydroxy thioether reactant represented by the formula:
• R--(SCH.sub.2 CH.sub.2 OH).sub.x I
• wherein R represents an unsubstituted or substituted hydrocarbyl group, and wherein x is a number of from to about 3 and identifies the number of --SCH.sub.2 CH.sub.2 OH groups attached to R;
• (2) an Mount of phosphorous-containing reactant selected from the group consisting of dihydrocarbyl hydrogen phosphite, trihydrocarbyl phosphite, and mixtures thereof, sufficient to provide at least about ten mole percent of phosphorous-containing reactant, based on the total moles of reactants in said admixture;
• and optionally
• (3) nucleophilic reactant containing at least one reactive hydroxy group and being free from any reactive mercapto or --SCH.sub.2 H.sub.2 OH groups;
• wherein said reactants are admixed in a manner and under conditions sufficient to form a one or two phase mixture comprising:
• (i) non-phosphorous containing compounds having within their structure at least one group represented by the formula:
• --S--CH.sub.2 CH.sub.2 --Q-- I"
• wherein Q is independently selected from the group consisting of oxygen or sulfur, said Q constituting a portion of the residue derived from:
• (1) beta-hydroxy thioether reactant, (2) the hydrocarbyl portion of the organic phosphite reactant, (3) when present, the nucleophilic reactant, and (4) mixtures of (1) to (3);
• and wherein the remainder of Structure I" exclusive of Q, contains residue of beta-hydroxy thioether reactant;
• and;
• (ii) phosphorous containing compounds comprising phosphorous acid and organic phosphites having within their structure at least one group represented by the formula:
• R--SCH.sub.2 CH.sub.2 O-- I'
• bonded directly to the phosphorous atom of the organic phosphite said R--SCH.sub.2 CH.sub.2 O-- group representing a residue of beta-hydroxy thioether.

An additive concentrate comprising a base oil in an amount up to about 75 wt. % and from about 25 wt. % up to about 100 wt. % of said concentrate of an additive mixture comprised of the phosphorous- and sulfur-containing reaction products formed by reacting in admixture:

• (1) at least one beta-hydroxy thioether reactant represented by the formula:
• R--(SCH.sub.2 CH.sub.2 OH).sub.x I
• wherein R represents an unsubstituted or inertly substituted hydrocarbyl group having present in its structure one or more hydroxy, oxy, thio, oxyalkylene and oxyalkylenethio groups and wherein x is a number from 1 to 3 and which identifies the number of --SCH.sub.2 CH.sub.2 OH groups attached to R;
• (2) an amount of phosphorous-containing reactant selected from the group consisting of dihydrocarbyl hydrogen phosphite, trihydrocarbyl phosphite, and mixtures thereof, sufficient to provide at least about ten mole percent of phosphorous containing reactant based on the total moles of reactants in said reaction mixture;
• and optionally
• (3) nucleophllic reactant containing at least one reactive hydroxy group and being free from any reactive mercapto or --SCH.sub.2 CH.sub.2 OH groups;
• wherein said reaction mixture is admixed in a manner and under conditions sufficient to form either a one or two phase product mixture comprising:
• (i) non-phosphorous containing compounds having within their structure at least one group represented by the formula:
• --S--CH.sub.2 CH.sub.2 --Q-- I"
• wherein Q is independently selected from the group consisting of oxygen or sulfur, said Q constituting a portion of the residue derived from:
• (1) beta-hydroxy thioether reactant, (2) the hydrocarbyl portion of the organic phosphite reactant, (3) when present, the nucleophilic reactant, and (4) mixtures of (1) to (3);
• and wherein the remainder of Structure I" exclusive of Q, contains residue of beta-hydroxy thioether reactant;
• and
• (ii ) phosphorous-containing compounds comprising phosphorous acid and organic phosphites having within their structure at least one group represented by the formula:
• R--SCH.sub.2 CH.sub.2 O-- I'
• bonded directly to the phosphorous atom of the organic phosphite said R--SCH.sub.2 CH.sub.2 O-- group representing a residue of beta-hydroxy thioether.

A process for improving at least one of the anti-wear and anti-oxidation properties of an oleaginous composition which comprises admixing a phosphorous- and sulfur-containing additive with an oleaginous material selected from the group consisting of fuels and lubricating oils, said phosphorous- and sulfur- containing additive having been prepared by reacting in admixture:

• (1) at least one beta-hydroxy thioether reactant represented by the formula:
• R--(SCH.sub.2 CH.sub.2 OH).sub.x I
• wherein R represents an unsubstituted or substituted hydrocarbyl group, and wherein x is a number from 1 to about 3 and which identifies the number of --SCH.sub.2 CH.sub.2 OH groups attached to R;
• (2) an amount of phosphorous-containing reactant selected from the group consisting of dihydrocarbyl hydrogen phosphite, trihydrocarbyl phosphite, and mixtures thereof, sufficient to provide at least about ten mole percent of phosphorous containing reactant based on the total moles of reactants in said reaction mixture;
• and optionally
• (3) nucleophilic reactant containing at least one reactive hydroxy group and being free from any reactive mercapto or --SCH.sub.2 CH.sub.2 OH groups;
• wherein said reaction mixture is admixed in a manner and under conditions sufficient to form a one or two phase product mixture comprising:
• (i) non-phosphorous containing compounds having within their structure at least one group represented by the formula:
• --S--CH.sub.2 CH.sub.2 --Q-- I"
• wherein Q is independently selected from the group consisting of oxygen or sulfur, said Q constituting a portion of the residue derived from:
• (1) beta-hydroxy thioether reactant, (2) the hydrocarbyl portion of the organic phosphite reactant, (3) when present, the nucleophilic reactant, and (4) mixtures of (1) to (3);
• and wherein the remainder of Structure I" exclusive of Q, contains residue of beta-hydroxy thioether reactant;
• and
• (ii) phosphorous containing compounds comprising phosphorous acid and organic phosphites having within their structure at least one group represented by the formula:
• R--SCH.sub.2 CH.sub.2 O-- I'
• bonded directly to the phosphorous atom of the organic phosphite, said R--SCH.sub.2 CH.sub.2 O-- group representing a residue of beta-hydroxy thioether.