CA1078374A

CA1078374A - Phosphorus- and sulfur-containing compositions

Info

Publication number: CA1078374A
Application number: CA243,487A
Authority: CA
Inventors: John S. Staral; Frederick W. Koch
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1975-02-24
Filing date: 1976-01-12
Publication date: 1980-05-27
Also published as: DE2606083A1; JPS51109001A; FR2301591A1

Abstract

ABSTRACT OF DISCLOSURE
The disclosure herein is concerned with phosphorus- and sulfur-containing compositions obtained as the reaction product of a phosphonodithioic anhydride and an olefin.
Lubricating compositions containing these compositions are disclosed.

Description

~078374 The invention herein is concerned with a novel, useful series of phosphorus- and sulfur-containing compositions and with the method for their preparation. The invention is also concerned with lubricating compositions comprising the subject phosphorus- and sulfur-containing compositions as an additive therein.
The exact structure of the subject phosphorus- and sulfur-containing compositions is not known, consequently, they are best described by the process of their preparation.
In essence, the novel phosphorus- and sulfur-containing compositions are obtained by the reaction of a phosphonodithioic anhydride with certain olefins. The subject compositions have the properties of being oxidation inhibitors, anti-wear agents, and extreme pressure agents, and accordingly, are useful as additives for lubricating oils to improve these properties in formulated lubricating compositions. The subject compositions are also useful as stabilizers (antioxidant) for various resins, such as polyolefin resins.
These phosphorus- and sulfur-containing compositions are effectively employed in lubricating compositions designed for a variety of uses. Likewise, the subject phosphorus- and sulfur- compositions are effective in lubricating compositions based upon both natural and synthetic oils of lubricating viscosity. Also, they are effective in lubricating compositions containing additional additives.
The subject phosphorus- and sulfur-containing compositions are prepared by the reaction, under suitable reaction conditions, of a phosphonodithioic anhydride, with an appropriate amount of an olefin corresponding to the formula . ~
. . _., , . -- 1 --~078374 RlR2C--CR3R4 to produce the desired products. In the above formula, Rl, R2, R3 and R4 are defined as follows:
Rl is selected from the group consisting of hydrogen, alkyl, aromatic, substituted alkyl or substituted aromatic:
R2 is selected from the group consisting of hydrogen, alkyl, aromatic, substituted alkyl, substituted aromatic, or -COR5, wherein R5 is selected from the group consisting of hydroxy, -OR6 wherein R6 is a hydrocarbon-based radical, or R5 together with R7 forms -0-;
R3 is selected from the group consisting of hydrogan, alkyl, aromatic, substituted alkyl, substituted aromatic, or -CH2(-CH2)m-COOR8, wherein m is an integer having a value of 0 to 10, and R8 is selected from the group consisting of hydrogen or hydrocarbon-based; or any two of Rl, R2 and R3, together fonm an alkylene or substituted alkylene;
R4 is selected from the group consisting of hydrogen, aromatic, substituted aromatic, halogen, -COR7, -CN, -CONHRg, -ORlo, CRll' or -CR12R13R14~ wherein R7 is selected from the group consisting of hydroxyl, hydrocarbon-based oxy radicals or together with Rs forms -0-, each Rg, R12, R13 and R14 is independently selected from the group consisting of hydrogen and hydrocarbon-based radicals, and each Rlo and Rll is a hydrocarbon-based radical.
~n accordance with the above, the olefinic reactant of the subject process includes within its scope a variety of compounds containing several types of substantially inert non-reactive functional groups.

Thus, olefinic reactants useful in the process of the present invention include olefinic aliphatic hydrocarbons, vinyl aromatic hydrocarbons, and cycloalkenes. Also, this reactant includes olefinic aliphatic acids and derivatives of the acid funct;on, such as esters, amides, and anhydrides;
vinyl-type halides; vinyl-type nitriles; vinyl-type ethers;
and esters of unsaturated alcohols.
The phosphonodithioic anhydrides are known in the prior art and several methods are available for their preparation.
These compounds correspond to a dimeric formula of (APS2) .
In regard to their structure, the available data indicates that these anhydrides are dimeric and contain a four-member ring of a two sulfur and two phosphorus atoms. It has been proposed that the anhydrides correspond to a structural ~`
formula of `
S S
11,~1 - A - ~ / P - A

' wherein A represents a hydro~arbon-based radical or group. A discussion of the structure of these anhydrides is given in TOPICS IN PHOSRHORUS CHEMISTRY, Vol. 2, M. Grayson, et al, Ed. (1965), Chapter 2, by L.~aier, pages 43-124, and the ;~ references cited therein. However, in view of the fact that there are doubts concerning the exact structure of these anhydrides, applicant does not wish to be bound to identi-fying the aahydrides on a structural basis.
Prior art methods for the preparation of the phos-phonodithioic anhydrides useful in the process of the present invention are discussed in the above Grayson et al 107~337~

publication, and the references cited therein. In general, these preparative methods include: (1) the reaction of the appropriate phosphorus sulfide, such as P4Slo, with a hydro-carbon, such as aromatic hydrocarbon, cycloalkene, alkene, etc.; (2) by the reaction of alkyl- or aryl-phosphonothioic dichloxide, with hydrogen sulfide; and (3) by the reaction of primary phosphines and sulfur, or sulfur monochloride.
Patents of interest for their teachings of the preparation of the subject anhydrides include: U.S. Patent 2,841,553 issued to Darling et al; 3,291,734 issued to Liao et al;
3,520,808 issued to Light British Patent 889,085 and German Patent 1,806,105 and 1,911,329. These patents and the other above discussed publications may be referred to for their disclosure of suitable methods to prepare and identify the phosphonodithioic anhydride reactants and other information concerning them.
The phosphonodithioic anhydrides useful in the process of the present invention are the hydrocarbon-based phosphonodithioic anhydrides, wherein the hydrocarbon-based radical is selected from the group consisting of hydrocarbyl and substituted hydrocarbyl. For example, suitable anhydrides include: phenylphosphonodithioic anhydride, p-anisylphosphono-dithioic anhydride, 3,4-dimethylphenylphosphonodithioic anhydride, cyclohexylphosphonodithioic anhydride, and decylphosphonodithioic anhydride.
~ lore specifically, the preparative process for the novel phosphorus- and sulfur-containing compositions of the present invention involves the reaction of the anhydride with the o]efin compound in a molar ratio of about two (2) ~ j - 4 -. .

1078374 ~ ~
moles of the olefin ~er mole of the anhydride. Of course, if desired, mixtures of the various reactants can be used, i.e., one or more anhydrides, and/or one or more of the olefin reactants may be used. Acco~dingly, the use of such mixtures comprising one or more of these reactants is con- -templated as being within the scope of the present invention as set forth in the specification and appended claims.
The r~actîon may be conducted in either the presence or absence of added solvent or dilaent as a reaction medium One convenient method for e~fecting the reaction is to use a stoichiometric excess of the olefin reactant and utilize this excess as a reaction medium. When an excess of olefin reactant is used, the amount of excess is not critical.
Usually, the excess will range from about one (1) mole excess over the stoichiometric requirement up to about a ten (10) mole excess.
When the reaction is conducted in the presence of an added reaction medium, i.e., one or more substantially inert, normally liquid organic diluents or solvents, the total amount of the diluent or solvent used is not critical.
Ordinarily, this added reaction medium will comprise from about 10~ to about 80%, preferably, abo~t 30% to about 70 by weight of the reaction mixture based upon the total weight of the reaction and reaction media in the reaction mixture. By "substantially inert" is meant a material which does not materially interfere with the reaction or react in any significant amount under the conditions of the reaction as described and exemplified herein.
Su~table diluents or solvents include aliphatic hydro-carbons, chlorinated hydrocarbons, ethers, and the like, such as heptane, octane, dodecane, cyclohexane, methylcyclo-hexane, mineral oil, kerosene, heptyl chloride, 1,4-dioxane, n-propyl ether, methyl n-amyl ether and m~xtures of two or more of these. Selection of specific suitable reaction media is within the skill of the art.
The reac-ion is conducted within a temperature range which is high enough to promote a reasonable reaction rate, but not so h~-gh as to cause reactant or product decomposi-tion. A useful temperature range is from about 25C to about 350C. A preferred temperature range is from about 50C. to about 200C. While the reaction is conveniently conducted at atmospheric pressure, it may be conducted at subatmospheric or superatmospheric pressure if desirdd.
The terminology "hydrocarbon-based" or "hydrocarbon-based ~adical" as used herein and in the appended claims, is used to define a substantially saturated monovalent radical derived from a hydrocarbon by removal of a hydrogen atom from a carbon atom of thehhydrocarbon. These hydrocarbon-based radicals are derived from aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons, mixed aliphatic-cycloaliphatic hydrocarbons, mixed aliphatic-aromatic hydrocarbons and mixed cycloaliphatic-aromatic hydrocarbons. As is discuss~d more fully below, the base hydrocarbon from which these radicals are derived, ~ay contain certain p~ar substituents. Thus, the "hydrocarbon-based" terminology is a generic expression for (1) hydro-carbyl and t2) substituted hydrocarbyl radicals.
The terminology "substantially saturated" as used herein and in the appended claims is intended to define radicals which are free from acet~lenic unsaturation (-C C-l) 107~3374 and in which there is not more than one ethylenic linkage t__ - c c _) for every eight (8) carbon-to-carbon covalent bonds, if any. The so-called double bonds in an aromatic ring, i.e., benzene, are not considered as contributing to unsaturation with respect to the termin~logy "substantially saturatedn. Usually there will be no more than an average of one (1) ethylenic linkage per substantially saturated mono valent radical as ~escribed hereinbefore. Preferably, all the carbon-to-carbon bonds in a substantially saturated radical will be saturated linkages, i.e., the radical will be free from acetylenic or ethylenic unsaturation In a similar manner, the terminology "hydrocarbon-based oxy" or "hydrocarbon-based oxy radical' as used herein and in the appended claims is used to define a substantially saturated mono valent radical derived from a hydrocarbon by ;~
the replacement of a hydrogen from the carbon atom of the hydrocarbon by an oxy group (-0-). Exemplary base hydro-carbons are listed above, and the base hydrocarbons from which these radicals are derived may contain ce~tain polar substituents. Thus, the "hydrocarbon-based oxy" terminology is a generic expression for (1) ~ydrocarbyloxy and (2~ su~
stituted hydrocarbyloxy radicals.
In general~ the hydrocarbon-based or hydrocarbon-based oxy radicals may contain up to about thirty (30) carbon atoms with a preferred range of carbon atoms being from one (1) ~p to about twenty (20). The subject radicals may con-tain certain non-reactive polar or non-hydrocarbon substi-tuents. As a general rule, and p~rticularly when the com-pounds of this invention are to be used as lubricant addi-tives, the degree of substitution and the nature of the lo78374 substituent on the hydrocarbon-based radicals is such th~t the essentially hydrocarbon character of the radical is not destroyed. Thus, in view of this requirement, these radicals that have substituents normally have no more than four (4) substituents per radical, and usually, no more than one (1) substituent for every ten (10) carbon atoms in the radical.
As used herein and in the appended claims, the term-inology "hydrocarbylt', and t'hydrocarbyloxy" is used to define those radicals containing no polar or non-hydrocarbon substituent derived from the above described hydrocarbon-based and hydrocarbon-based oxy radicals. Similarly, the terminology 'tsubstituted hydrocarbyl" and "substituted hydrocarbyloxy't is used to define those radicals containing ; a polar or n~n-hydrocarbon substituent derived from the above described based radica.s. Thus, the following are representative examples of hydrocarbyl radicals: (1) alkyl, such as ethyl, t-butyl, isooctyl, dodecyl and eicosyl; (2) cycloalkyl, such as cyclooctyl, and cyclobutyl; (3) aryl, such as phenyl, naphthyl, and diphenyl; ~4) cycloalkylalkyl, such as cyclopropylethyl, and cyclooctylbutyl; (5) aryl-alkyl, such as benzyl, phenylethyl, tolyldecyl, and naphthyl-ethyl; (6) alkylcycloalk~l, such as trimethylcyclododecyl, : and butylcycloheptyl; t7) arylcycloalkyl such as xylylcy-clodecyl, and naphthylcyclohexy; (8) alkylaryl, such as ; tolyl, xylyl, dodecylphenyl, and didodecylphenyl; and (9) cycloalkylaryl~ such as cyclobutylphenyl, and cyclohexyl- :
naphthyl. When a named radical has several isomeric forms, all such forms are inclu~ed.
The preferred hydrocarbyl radicals are those selected from the group consisting of alkyl, phenyl, naphthyl, alkyl-:~

~078374 ,i , phenyl, alkylnaphthyl, phenylalkyl, naphthylalkyl, al~yl-phenylalkyl, and alkylnaphthylalkyl. The alkyl, phenyl, alkylphenyl, phenylalkyl and alkylphenylalkyl radicals are the most preferred hydrocarbyl radicals.
Repreeentative non-hydrocarbon or polar substituents for the substituted hydrocarbyl, and substituted hydro-carbyloxy r~dicals include halo substituents, such as chlori, fluoro, bromo and iodo; lower alkoxy, such as butoxy, and hexylo~y; and lower alkylthio, such as pentyl-thio and he~tylthibo. The terminology "lower alkoxy" and"lower alkylthio" is intended to described such radicals having straight and branched chain alkyl groups of up to seven (7) carbon atoms.
Exemplary hydrocarbyloxy and substituted hydrocarbyloxy radicals ~nclude dodecylphenoxy, isooctyloxy, tolyldecyloxy,

2-chlorobutyoxy, 4-ethoxyph~nyloxy and trifluoromethylphenoxy.
In accordance with the above discussion of hydrocarbon-based radicalsS the "alkyl" radicals may contain up to about thirty ~30) carbon atoms with a preferred range of carbon atoms being from one ~1~ up to about twenty (20). These alkyl radicals may con~a~n non-reactive polar or non-hydrocarbon substituents, i.e., substituted alkyl. Addi-tional exemplary alkyl radicals include nonadecyl, methyl, heptadecyl, isopropyl, tricosyl, n-butyl, pentadecyl, 3-methylbutyl and 2-ethylhexyl.
The terminology "alkylene" and "~ubstituted alkylene"
is used herein and in the appended claims to define a divalent radical derived from the above defined alkyl or substituted alkyl radicals and, preferably, containing up to about ~enty (20~ carbon atoms. Representative al~ylene and . :

~0783'74 substitut~d al~ylene radicals include ethylene, 1,3-butylene, 2-butylethylene, dodecylene, hexamethylene, 2-chloro-1,3-propylene, 3-ethoxy-1,4-butylene and 2-pentylthio-1,4-hexylene.
The terminology "lower ~ 1" and "halo" as used herein and in the appended claims is used within the commonly accepted meaning of theaart. Thus, lower alkyl refers to a straight or branched chain alkyl radical or group containing up to seven (7) carbon atoms. Accordingly, this terminolo~y includes alkyl radicals such as methyl, ethyl, tertiary butyl, ~soamyl and heptyl. The halo radical or group 10 includes fluoro, chloro, bromo and iodo. The preferred halo radicals are selected from the group consisting of chloro and bromo. Subs~ituted lower alkyl radicals define alkyl radicals containing non-hydrocarbon substituents as defined above and in the same degree of substitution.
A clearer understanding of phosphorus- and sulfur-containing compositions of the present invention, processes for their preparation, and lubricant compositions containing 20 these compositions may be obtained from the examples given below.
Example 1 o-Xylene t795 grams, 7.5 molesD and 333 grams tO.75 mole) of phosphorus pentasulf~de are charged to a one gallon mechanically-stirred autoclave. The autoclave is equipd with a nitrogen inlet line, reflux condenser, and pressure relief valve. The pressure relief valve is ad-justed to maintain an internal pressure in the range of from 26-28 psig tpounds per square inch gauge) and the stirred 30 reaction mixture is heated to about 2006. The pressure relief valve is adjusted to maintain the temperature of the r .:
~' 1C3'78374 reaction mixture în the range of from about 195C. to about 205C. at a pressure in the range of about 26-36 psig. This t~mperature range is maintained, with a moderate refluxing of the o-xylene ~or a period of about 7 hours. At the end of this period of time, the mixture is allowed to cool, with stirring, to room temperature. The cooled mixture is fil- -tered to yield 485 grams ~80.9% yield) of crysta-line o-xylylphosphonodithioic anhydride. ;
When the o-xylene in the above process is replaced with anisole or phenetole or benzene or naphthalene or cyclo-hexene or l-decene, the corresponding phosphonodithioic anhydride is formed. `-Example 2 A mixture of 24 parts (0.07 mole) of phenylphosphono-dithioic anhydride and 235 parts (1.4 moles) of a commercial mixture of C12 ~-olefins is heated under nitrogen at 95-105C. for 17.5 hours, cooled to room temperature and filtered. The filtrate is stripped under vacuum and the residue is the product which contains 7.41% phosphorus and 13.93% sulfur.
ExamPle 3 ~ Following the general procedure of Example 2, when the mixture of olefins is replaced with cyclooctene or cyclo-decene or trimethylcyclododecene the corresponding phosphorus-and sulfur-containing compositions are obtained.
Example 4 A mixture of 398 parts (3.75 moles) of o-xylene and 167 parts (0.75 mole) of phosphorus pentasulfide is heated under pressure for 7.0 hours at 195-205OC. in an autoclave.
'' ~, \~ ~

The reaction mixture is cooled to room temperature and an additional 398 parts (3.75 moles~ of o-xylene is added. Te autoclave is sealed at atmospheric pressure, evacuated and cooled in an acetone/dry ice bath. Propene, 252 parts (6.0 moles), i8 added and the m;xture is heated at 125-135(~C. and 325-380 paig for 23.9 hours.
The reaction mixture if filtered and stripped under vacuum. The residue is the desired product and contains ,-12.59% phosphorus and 26.27% sulfur.
Example 5 Following the general procedure of Example 4, when the propene is replaced wihh acrylonitrile or a-hexylacryloni-trile or vinyl chloride or diethyl methylenemalonate or dibenzyl methylenemalonate the corresponding phosphorus- and s~lfur-containing compositions are formed.
Example 6 A mixture of 300 parts tO.75 mole) of o-xylylphosphono-dithioic anhydride and 672 parts ~6.0 moles) of l-octene is heated under nitrogen at 95-105C. for about 51 hours. It is then cooled to room tcmperature, stripped under vacuum and filtered. The filtrate (515 parts) is the desired product containing 8.18% phosphorus and 16.12~ sulfur.
Exa~ple 7 ; Following the procedure of Example 6, when the l-octene is replaced with allyl acetate or methyl vinyl ether or N-octylacrylamide or dodecylmaleic anhydride, the corres-ponding phosphorus- and sulfur-containing compositions are formed.
Example 8 A mixture of 1272 parts (12 moles)~,of o-xylene and 1200 , , ~ -12-~078374 parts of o-dichlorobenzene is heated to reflux under nitro-gen and water is removed by the use of a Dean-Stark trap.
The mixture is cooled to 85C. and 666 parts (3 moles) of phosphorus pentasulfide is added. The resulting mixture is heated under nitrogen for 96 hours with the temperature increasing graduallyffrom 156 to 172C.
; The mixture i8 cooled to ~oom temperature and 2690 parts (24 moles) of l-octene is added. The resulting ;
mixture is heated at 125-135C. for 24 hours under nitrogen.
It i9 th~n vacuum stripped and filtered to yield the desired product (1764 parts) containing 8.76% phosphorus and 17.9%
su~fur.
ExamPle 9 ~' Following the procedure of Example 8, when the l-octene is replaced with 2-hexylacrylamide or fumaric acid or cyclo-hexyl vinyl ether or vinyl laurate the corresponding phos-phorus- and sulfur-containing compositions are formed.
Example 10 A mixture of 400 parts (1.0 mole) of o-xylylphosphono- , d~ithioic anh~dride and 448 parts ~4.0 moles) of 2-octene is heated under nitrogen at 115-130C. for 40 hours, cooled to room temperature and vacuum stripped. The residue is fil-tered to yield the desired product (510 parts) containing 10.22% phosphorus and 19.97% sulfur.
Example 11 ` Following the procedureoof Example 10, when the 2-octene is replaced with 2eehloroallyl stearate or ethyl methallyl ether or cis-4-cyclohexene-1,2-dicarboxylic acid ` anhydride or N-cyclopentylmethacrylamîde the corresponding phosphorus- and sulfur-containing compositions are formed.
`.~
~',', :' . . . . . . .

Example 12 A mixture of 22 parts (0.055 mole) of o-xylylphosphono-dithioic anhydride and 93 parts (0.55 mole) of a commercial mixture of cl2 c-olefins is heated at 105-115C. for 36 hours under nitrogen, cooled to room temperature and fil-tered. The filtrate is stripped under vacuum, co~led to room temperature and filtered again, yielding the desired product which conta~ns 13.27% sulfur and 7.21% phosphorus.
Example 13 A mixture of 1960 parts (3.5 moles) of crude o-xylyl-phosphonodithioic anhydride and 6524 parts (28 moles) of a commercial mixture of C15-18 ~-ole~ins is heated at 125-135C. for 24hhours under nitrogen, stripped under vacuum and filtered. The filtrate ~4615 parts) i9 the desired product containing 4.18% phosphorus and 8.74% sulfur.
Example 14 A mixture of 464 parts (4.38 moles) of o-xylene and 194 parts (0.875 mole) of phosphorus pentasulfide is heated under pressure for 7 houPs at 195-20~C. in an autoclave.
It is then cooled to room temperature and 1750 parts (1.75 moles) of a polyisobutene having a moledular weight (Mn) of about 940 is added. The reaction mixture is heated under ; pressure at 220-230C. for 24.1 hours, cooled under nitro-gen, stripped under vacuum and filtered. The filtrate (1759 parts) is the desired product and contains 2,68% phosphorus and 5.31% s~lfur.
. Example 15 ~, .
Following the general procedure of Example 14, when the polyisobutene is replaced with N-benzylcinnamamide or lino-lenic acid or benzyl allyl ether or cinnamyl butyrate the - . . ~ . ~ . . . . -~0783'74 ~

corresponding phosphorus- and sulfur-containing composi~ions are obtained.
Example 16 A mixture of 1183 parts (2.31 moles) of crude 0-xylyl-phosphonodîthioic anhydride and 7400 parts ~4.62 moles) of a polyisohutadiene having an approximate molecular weight (Mn) of 1600 is heated at 220-230C. for 30 hours undernnitrogen.
The rcaction mixture is stripped under vacuum at 150C and filtered at 130-150C. The filtrate (7120 parts) is the desired product containing 1.64~ phosphorus and 2.97%
sulfur.
Example 17 ~ ~ -A mixture of 200 parts (0.5 mole) of o-xylylphosphono-dithioic anhydride and 432 parts (4.0 moles) of 4-vinyl-cyc~ohexene is heated at 95-105C. for 35 hours under nitro-gen, cooled to room temperature and stripped under vacuum.
The residue is the desired product and contains 9.80% phos-phorus and 17.76% sulfur.
Example 18 A mixture of 100 parts (0.25 mole) of o-xylylphosphono-dithioic anhydride and 300 parts of toluene is heated under nitrogen, and 106 parts (0.5 mole~ of isodecyl acrylate is added over one hour at 105-115C. On completion of the .
isodecyl acrylate addition, the reaction mixture is heated at 105-115 C. for 2~.5 hours. It is then cooled to room ; temperature, stripped under vacuum and filtered. The fil-trate (197 parts) is the desired product containing 7.59%
phosphorus and 1~.36% sulfur.
Example 19 A mixture of 352 parts ~0.8 mole) of crude p-anisyl~

~078374 ~
phosphonodithioic anhydride and 897 parts (8.0 moles) of 1-octene is heated at 105-115C. for 28.5 hours under nitro-gen, stripped under vacuum, cooled to room temperature an filtered. The filtrate is the desired product which con-tains 17.07% sulfru and 8.31% phosphorus.
Example 20 A mixture of 202 parts (0.5 mole) of p-anisylphos-phonodithioic anhydride, 672 parts (4.0 moles) of a com~er-cial mixture of C12 ~-olefins and 100 parts of toluene is treated as described in Example 19. The product contains 6.93% phosphorus and 14.14% sulfur.
Example 21 A mixture of 150 parts (0.32 mole) of crude p-anisyl-phosphonodit~ioic anhydride and 430 parts (2.55 moles) of propene tetramer is heated at 105-185C. for 53 hours under nitrogen, cooled to room temperature, stripped under vacuum and filtered. The filtrate is the desired product con-~
' taining 18.95% sulfur and 11.26% phosphorus.
s Example 22 A mixture of 1175 parts ~2.68 moles) of crude p-anisyl-- phosphonodithioic anhydride and 5000 parts (5.0 moles) of a ,.i~
;~ polyisobutene having a moledular weight of approximately 940 ~Mn) is heated at 195-205C. for 14.5 hours under nitrogen, cooled to 100C. and filtered. The filtrate (5661 parts ) is the desired product and contains 4.63% sulfur and 2.76%
phosphorus.
Example 23 , .
A mixture of 59 parts (0.125 mole) of crude p-anisyl-,, ` phosphonodithioic anhydride, 275 parts (0.275 mole) of a polyisobutene having a molecular weight (Mn) of approxi-:

~078374 mately 940 and 100 parts of toluene is heated at 105-220C.
for about 50 hours under nitrogen. The mixture is stripped under vacuum and cooled to room temperature. The residue (300 parts) is the desired produ~t containing 2.71% phos-phorus and 4.55% sulfur.
Example 24 Following the general procedure of Example 23, when the ~ , polyisobutene is replaced with l-phenylallyl valerate or cinaamyl decyl ether or vinylacetic acid or N-naphthyl-cinnamamide the corresponding phosphorus- and sulfur-con-taining compositions are obtàined.
Example 25 A mixture of 220 parts (0.5 mole) of crude o-anisyl-phosphonodithioic anhydride and 472 parts (4.0 moles) of d-methylstyrene is heated at 95-105C. for 52.5 hours u~der nitrogen, cooled to ~oom temperature and stripped under r vacuum. To the residue i5 a~ded lOO,prrts of benzene and 200 parts of toluene, The resulting solution i9 ~iltered and stripped of volatile~, the residue is the desired ~.
product containing 8.19~ phos~horus and 17.0~ sulfur.
~', Example 26 '~ Following the general procedure of Example 25, when the ~`, c-methylstyrene is replaced with p-chlorostyrene or tri-;` bromostyrene or dicyanostyrene or p-dodecylstyrene or vinyl-.
,~ naphthalene the corresponding phosphorus- and sulfur-con-taining compositions are formed.
` Example 27 A mixture of 23.5 parts (0.05 mole) of crude p-anisyl-phosphonodithioic anhydride, 29.6 parts (0.15 mole) of 2-~)78374 ethylhexyl methacrylate and 100 parts of toluene is heated at 105-115C. for 15.~ hours under nitrogs~, cooled to room temperature under vacuum and fîltered. The filtrate (38 parts~ is the desired product; it contains 7.07% phosphorus and 15.63~ sulfur.
Example 28 Following the general procedure of Example 27, when the 2-ethylhexyl methacrylate i~ replaced with ethyl q-phenyl-acrylate or cyclohexyl undecylenate or benzyl methacrylate 10 or phenyl oleate or monohexadecyl maleate, the corresponding ~;
phosphorus- and sulfur-containing compositi~ns are formed.
; As waC briefly discussed above, the phosphorus- and ; sulfur-containing compositions of the present invention are particularly useful as additives ~or lubricating oil in the formation of ~ubricating compositions. It i8 well known in the art that when lubricating oils are sub;ected to extended periods of use, particularly at high operating temperatures, they tend to decompose with the formation of various oxi-.~, dation products, such as acidic materials, peroxides, etc., and other decomposition products. These products havemmany adverse effects upon both the base lubricating oil and upon the various materials which come into contact with the lubricating composition. Thus, these products promote the ,~, corrosion of various metallic surfaces, such as engine parts, gears, etc., contacted with compositions containing the various oxidation and other decomposition products.
i Corrosion of these metallic surfaces promotes among other adverse effects, excessive wear of the surfaces. It is common practice to incorporate in a lubricating oil com-107837~
pounds capable of increasing the resistance of these oils to oxidation, i.e., oxidation inhibitors, anti-oxidants, as well as improving many other properties of the ba~e lubri-cating oil by the addition of other additives for various other functions. Thus, the compounds of the present inven-tion are particularly useful as additives for lubricating oils where they function primarily as oxidation-inhibitors, antioxidants, an~i-wear agents and as an extreme pressure agent.
Lubricating compositions containing the subject phos-phorus- and sulfur-containing compositions as an additive therein comprises a major proportion of a lubricating oil and a minor porportion of at least one of the subject phos-phorus- and sulfur-containing compositions. These phos-. phorus- and sulfur-containing compositions are present in amounts sufficient to improve the oxîdation stability or the oxidation inhibiting properties or anti-wear or extreme pressure properties of the lubricating composition.
~; In general, the subject additive compositions are used in amounts of from about 0.01% to about 20% by weight based upon the total weight of lubricating composition. The optimum concentration for a particular additive will depend to a large measure upon the type of service the lubricating composition is to be subjected. In most applications, lubricating compositions containing from about 0.1% to about 10% by weight of the phosphorus- and sulfur-containing additive composition are useful, although for certain appli-cations, such as in gear lubricants a~d diesel engines, compositions containing up to 20~ or more may be preferred.

-19- , 10783~74 The subject phosphorus- and sulfur-containing additive composition can be effectively employed in a variety of lubricating compositions formulated for a variety of uses.
Thus, lubricating compositions contaning the subject additive are effective as crankcase lub M cating oils for spark-ignited and compression-ignited internal combustion eng~ne~, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and low-load diesel engines and the like. Also, automatic transmission lfluids~
transaxle lubricants, gear lubricants, metal-working lubri-cants, hydraulic fluids and other lubricating oil and grease compositions can benefit from the incorporation of the subject additive therein.
The lubricating compositions of the present invention may, of course, be prepared by a variety of methods known in ` the art. One convenient method is to add the phosphorus-and sulfur-containing additive in the form of a concentrated solution or substantially stable suspension to a sufficient amount of the basellubricant to form the final subject lubricating compositions. This additive concentrate con-tains the phosphorus- and sulfur-containing additive in the proper amount to provide the proper ratio of additive in the O final lubricating composition when added to a predetermined amount of base lubricant. The concentrate may also contain appropriate amounts of any additional additive which it is desired to incorporate in the final lubricating composition.
Generally, the concentrate will comprise from about 20%
to about 90% of the phosphorus- and sulfur-containing addi-tive with the balance being a substantially ine~t normally liquid solvent or diluent, plus any additional additives used. Suitable solvents and diluents include any of the herein discussed natural or synthetic oils, kerosene, xylene, benzene, mixtures of two or more of these and other solvents and diluents known in the art. Normally the solvents or diluents are oil-soluble at least to the extent of their concentration in the final lubricating compositions prepared from them.
The phosphorus- and sulfur-containing additives of the present invention are effectively employed using base oils of lubricating viscosity derived from a variety of sources. Thus, base oil derived from both natural and synthetic sources are useful for the preparation of lubricating compositions of the present invention.
The natural oils include animal oils, such as lard oil; vegetable oils, such as castor oil; and mineral oils, such as solvent-treated or acid-treated mineral oils of the paraffinic, napthenic or mixed paraffinic-naphthenic types.
,.;
; Also useful are oils of lubricating viscosity derived from coal or shale.
Many synthetic lubricants are known in the art and these are useful as a base lubricating oil for lubricating compositions containing the subject additive concent~ates.
Surveys of synthetic lubricants are contained in the publications, SYNTHETIC LUBRICANTS by R.C. Gunderson and A.W.
Hart, published by Reinhold (N.Y., 1962), LUBRICATION AND
LUBRICANTS, E.R. Braithwaite, ed., published by Elseiver Publishing Co., (N.Y., 1967), Chapter 4, pages 166 through ~ ~ - 21 -.~
t~ . .. .

1~7837~

196, "Synthetic Lubricants", and SYNTHETIC LUBRICANTS by M.
W. Ranney, published by Noyes Data Corp., (Park Ridge, N.J., 1972). Reference may be made to these publications for further details of general and specific types of synthetic lubricants which can be used in conjunction with the additive of the present invention.
Thus, useful synthetic lubricating base oils include hydrocarbon oils derived from the polymerization or copolymerization of olefins, such as polypropylene, polyisobutylene and propylene-isobutylene copolymers; and - the halo-hydrocarbon oils, such as chlorinated polybutylene.
Other useful synthetic base oils include those based upon alkyl benzenes, such as dodecylbenzene, tetra-decylbenzene, and those based upon polyphenyls, such as biphenyls and terphenyls. -~
,, Another known class of synthetic oils useful as base oils for the subject lubricant compositions are those based upon alkylene oxide polymers and interpolymers, and those oils obtained by the modification of the terminal ,......... .
hydroxy groups of these polymers, (i.e., by the esterification or etherification of the hydroxy groups). Thus, useful base ~
oils are obtained from polymerized ethylene oxide or propy- -lene oxide or from the copolymers of ethylene oxide and propylene oxide. Useful oils include the alkyl and aryl ethers of the polymerized alkylene oxides, such as methyl-polyisopropylene glycol ether, diphenyl ether of polyethylene glycol and diethyl ether of propylene glycol. Another useful series of synthetic base oils is derived from the esterification of the terminal hydroxy group of the polymer-~ - 22 -. l ~o7837~

ized alkylene oxides with mono- or polycarboxylic acids.
Exemplary of this series is the acetic acid esters or mixed C3-C8 fatty acid esters or the C13Oxo acid diester of tetraethylene glycol. -.^
Another suitable class of synthetic lubricating oil comprise the esters of dicarboxylic acids, such as phthalic acid, succinic acid, oleic acid, azelaic acid, suberic acid, sebacic acid, with a variety of alcohols. Specific èxamples of these esters include dibutyl adipate, di(2-ethylhexyl)-sebacate and the like. Complex esters of saturated fatty acids and a dihydroxy compound, such as 3-hydroxy-2,2-dimethylpropyl 2,2-dimethylhydracry~ate (U.S. patent

3,759,862), are also useful. Silicone based oils such as polyalkyl-,ppolyaryl~,polyalkoxy-, or polyaryloxy-siloxane oils and the silicate oils, i.e., tetraethyl silicate, comprise another useful class of s~nthetic lubricants.
Other synthetic lubricating oils include liquid esters of phosphorus -containing ac~d, such as tricresyl phosphate, polymerized tetrahydrofurans, and the li~e.
Unrefined, refined and re-refined oils of the type described above are useful as base oil for the p~eparation of lubricant compositions of the present invention. Unre-fined oils are those obtained directly form a natural or synthetic source without further purification or treatment.
For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from~a natural or tillation, or an ester oil obtained directly from an esteri-fication process, and used without further treatment are unrefined oils. Refined olls are similar to the unrefined oils, exceps they have been further treated in one or more purification steps, to improve one or more properties. Many such purification techniques are known in the art, such as solvent extraction, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by a variety of processes similar to those used to obtain refined oils.
The rerefined oils are also known as reclaimed or reprocessed oils and have been treated by additional techniques directed to the removal of spent additives and oil breakdown products.
The subject additive can be used alone or in combination with other lubricant additives known in the prior art. A brief survey of conventional additives for lubricating compositions is contained in the publications, LUBRICANT
ADDITIVES, by C.V. Smalheer and R. Kennedy Smith, published by the Lezius-Hiles Co., Cleveland, Ohio (1967) and LUBRICANT
. . .
ADDITIVES, by M. W. Ranney, published by Noyes Data Corp., ~ -Park Ridge, New Jersey (1973). Reference may be made to these publications for more details of both general and specific types of other additives which can be used in conjunction with the additives of the present invention.
In general, these additional additives include detergents of the ash-containing type, ashless dispersants, additional viscosity index improvers, pour point depressants, anti-foam agents, extreme pressure agents, anti-wear agents, rust-inhibiting agents, oxidation inhibitors and corrosion inhibitors.
The ash-containing detergents are the well known neutral basic alkali or alkaline earth metal salts of sulfonic acids, carboxylic acids or organo-phosphorus-, containing acids. The most commonly used salts of these -acids are the sodium, potassium, lithium, calcium, mag-nesium, strontium and barium salts. The calcium and barium salts are used more extensively than the others. The "basic -salts" are those metal salts known to the art whe~ei-n the ;
metal is present in a stoichiometrically larger amount than that necessary to neutralize the acid. The calcium- and - barium-overbased petrosulfonic acids are typical examples of such basic balts.
The extreme pressure agents, corrosion-inhibiting ; agents and oxidation-inhibiting agents are exemplified by chlorinated aliph~tic hydrocarbons, such as chlorinated was;
organic sulf~des and polysulfides, such as benzyl-disulfide, bis-(chlorobenzyl)disulfide, dibutyl tetras~lfide, sul-furized sperm oil, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosul-furized hydrocarbons, such as the reaction product of phos-phorus sulf~de with turpentine or methyloleate; phosphorus esters such as the dih~drocarbon and trihydrocarbon phos-phites, i.e., dibutyl phosphite, diheptyl phosphite, di-cyclohexyl phosphite, pentylphenyl phosphite, dipcntylphenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene substituted phenol phosphite; metal thiocar-bamates, such as zinc dioctyldithiocarbamate and barium heptylphenol dithiocarbamate; and Group II metal salts of phosphorodithioic acid, such as zinc dicy~lohexyl phos-phorodithioate, and the zinc salts of a phosphorodithioic sacid.

~078374 The ashless detergents or dispersants are a well known class of lubricant additives and are extensively discussed and exemplified in the above-cited publications by Smalheer ~ ' et al and Ranney and the references cited therein. Pnr-ticularly useful types of ashless dispersants are based upon the reaction products of hydrocarbon-substituted succinic acid compounds and polyamines or polyhydric alcohols. These reac~ion products may~be post-treated with materials, such as alkylene oxides, carboxylic acids, boron compounds, carbon disulfide and alkenyl cyanides to produce further useful a8hless dispersants.
,Pour point depressing agents are illustrated by the ipolymers of ethylene, propylene, isobutylene, and poly(alkyl methacrylate). Anti-foam agents include polymeric alkyl siloxanes, poly(alkyl methacrylates), terpolymers of di-acetone acrylamide and alkyl acrylates or methacrylate, and the condensation products of alkyl phenols with formaldehyde and an amine. Additional viscosity index improvers include polymerized and copolymerized alkyl methacrylates and poly-isobutylenes.
When additional additives are formulated in ~ubricating compositions contain~ng the subject additive, they are used in concentrations sufficient to provide in the final lubri-cating composition concentrations in which they are normally employed in the art. Thus, they generally are used in a concentration of from about 0.001% up to about 25% by weight of total lubricating composition, depending of course, upon the nature of the additive and the nature of the lubricant composition. For example, ashless dispersants can be em-ployed in~maunts from about 0.1~ to about 10~ and metal-10783'74 containing detergents can be employed in amounts from about 0.1% to about 20~ by weight. Other additives, su~h as pour point depressants, extreme pressure additives, viscosity index improving agents, anti-foaming agents, and the lik~, are normally employed in amounts of from about 0.001% to about 10% by ~ weight of the total composition, depending upon the nature and purpose of the particular additive.
The fo~lowing lubricant compositions exemplify the incorporation of the additives of the present invention into these type~-compositions.
ExamPle A
A lubricating composition suitable for use as a crank-case lubricant is prepared using a SAE 10W-30 base mineral lubricating oil and as additives: 5.41% of a polyisodecyl-acrylate viscosity index improver; 4.25% of a dispersant which is the reaction product of a polyisobutenyl succinic anhydride and pentaerythritol in a 1:1 equivalent ratio;
1.57~ of an overbased calcium sulfonate detergent; 0.95% of a zinc isobutylamyl phosphorodithioate oxidation inhibitor;
1.0% of the reaction product obtained in Example 20; and 40 ppm of a congentional anti-foaming agent.
Example B
A lubricating composition suitable for use as a crank-case lubricaht is prepared using a SAE 10~-30 base mineral lubricating oil and as additives: 5.41% of the pohr point depressant of Example A; 0.95% of the oxidation inhibitoroof Example A; 0.50% of a combination oxidation inhibitor and anti-wear agent based upon a sulfurized Diels-Alder adduct of a conjugated diene and an alkyl acr~late; 2.0% of the dispersant of Example A; 1.57% of an overbased calcium .
sulfonate detergent; 1.125% of the reaction product obtained in Example 14; and 40 ppm of a conventional anti-foaming agent.
Exam~le C
A lubricating composition suitable for use as a crank-case lubricant is prepareduusing a SAE lOW-40 base mineral lubricating oil and as additives: 8.8% of the viscosity index improver of Example A; 6.3% of a dispersant based upon the reaction product of polyisobutenyl succinic anhydride 10 and tetraethylene pentamine in a ratio of 1:1.5 equivalent; ~.
1.1~ of a corrosion inhibitor which is the reactionproduct of polyisobutenyl æuccinic anhydride, tetraethylene penta- -mine and boric acid as described in U.S.Patent 3,254,025; .
0.95% of a commercial anti oxidant based upon a hindered phenol; 1.57% of the product of Ex~mple 20; 40 ppm of a commercial ant~ foaming-agent ExamPle D
A lubricating composition useful as an automatic transmission fluid is prepared using as the base oil, a ;
mixture of 90% by volume of a 110 neutral mineral lubri-cating oil and 10~ by volume of a 210 neutral lubricating oil, and as additives: 11.13% of a mineral oil based con-centrate containing, 3.36% of an oil based mixture of a viscosîty improver derived from mixed esters of a styrene-maleic acid interpolymer as disclosed in U.S. Patent 3,702S300 and the reaction product in a ratio of 4:3 equiva-lents of a polyisobutenyl succinic anhydride and ethylene polyamine; 2.98~ of a commercially available seal sweller;
3-0~ of an ashless dispersant, which is the reaction product (1:1 eq.) of polyisobutenyl succinic an~`d~ide and tetra-`- ~078374 ethylene pentamine prepared according to the procedure of U.S. Patent 3,172,892; 1.0% of a corros;on inhibitor which is the reaction product of polyisobutenyl ~uccinic anhy-dride, tetraethylene pentamine and boric acid as described in U.S. Patent 3,254,025; 0.54% of the reaction product of Example 20; and 200 ppm of a conventional anti-foaming agent.
Example E
A lubricating composit~Dn suitable for use as a turbine lubricating oil is prepared us;ng 350 neutral mineral lubricating base oil and as additives: 0.05% of an oil solution ~37% oil) of a partially esterified (about 5%) reaction product of dodecenyl succinic acid and propylene oxide, as a rust ~nhibitor; and 2.39~ ~0.1% P) of the reaction product of Example 13. -~
:
Example F
A lubricating composition is prepared using a synthetic lubricating base oil consisting essentially of the diethyl- -~
ether or propylene glycol having an average molecular weight - 20 of about 15,000 and 1% of the product of Example 2.
In all of the above examples, as well as other portions of the specification and c~aims, all percentages are ex-; pressed as percentages by weight, and all parts are ex-pressed as parts by weight, unless otherwise indicat~d.
Likewise, all temperatures, are expressed in degrees centi-grade (C.), unless otherwise indicated. All molecular weights are expressed as number average molecular weights (Mn) determined by vapor pressure osmometry (VP0), unless otherwise indicated. Also, the singular forms of "a", "an", and "the" include the plural, unless the context clearly dictates otherw~se.

;

~ .

Claims

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

1. A lubricating composition comprising a major pro-portion of a lubricating oil and a minor effective proportion of an additive which is a phosphorus- and sulfur-containing composition of matter prepared by a process which comprises re-acting a phosphonodithioic anhydride with an olefin correspon-ding to the formula:

wherein R1 is selected from the group consisting of hydrogen, alkyl, aromatic, substituted alkyl or substituted aromatic; R2 is selected from the group consisting of hydrogen, alkyl, aro-matic, substituted alkyl, substituted aromatic, or -COR5, where-in R5 is selected from the group consisting of hydroxy, -OR6 wherein R6 is a hydrocarbon-based radical, or R5 together with R7 forms -O-; R3 is selected from the group consisting of hydro-gen, alkyl, aromatic, substituted alkyl, substituted aromatic, or -CH2(-CH2)m-COOR8, wherein m is an integer having a value of 0 to 10, and R8 is selected from the group consisting of hydro-gen or hydrocarbon-based; or any two of R1, R2 and R3, together form an alkylene or substituted alkylene;
R4 is selected from the group consisting of hydrogen, aromatic, substituted aromatic, halogen, -COR7, -CN, -CONHR9, OR10, -OCOR11 or -CR12R13R14, wherein R7 group consisting of hydroxyl, hydrocarbon-based oxy radicals or together with R5 forms -O-, each R9, R12, R13 and R14 is inde-pendently selected from the group consisting of hydrogen and hydrocarbon-based radicals, and each R10 and R11 is a hydro-carbon-based radical; and wherein the reactants are present in amounts such that there is at least about two moles of the olefin for each mole of the phosphonodithioic anhydride.

2. The lubricating composition of Claim 1, wherein the phosphonodithioic anhydride is a hydrocarbon-based phosphonodi-thioic anhydride.

3. The lubricating composition of Claim 1, wherein R
and R2 are hydrogen and R3 and R4 are selected from the group consisting of alkyl and aromatic.

4. The lubricating composition of Claim 1, wherein R
and R4 are alkyl radicals and R2 and R3 are hydrogen.

5. The lubricating composition of Claim 1, wherein R1, R2 and R3 are hydrogen, and R4 is a -CR12R13R14.

6. The lubricating composition of Claim 1, wherein R1 is selected from the group consisting of aromatic and substituted aromatic radicals, and R2, R3, and R4 are hydrogen.

7. The lubricating composition of Claim 1, wherein R
and R2 are hydrogen, R4 is -CONHR9, and R3 is selected from the group consisting of hydrogen and alkyl.

8. The lubricating composition of Claim 1, wherein R
and R2 are hydrogen, R4 is -COR7, and R3 is selected from the group consisting of hydrogen and alkyl.

9. The lubricating composition of Claim 1, wherein R1, R2 and R3 are hydrogen and R4 is -OCOR11.

10. The lubricating composition of Claim 1, wherein R1 and R4 are hydrogen and R2 and R3 taken together are alkylene.

11. The lubricating composition of Claim 1, wherein R1, R2 and R4 are hydrogen, and R3 is -CH2(-CH2)m-COOR8.

12. The lubricating composition of Claim 1, wherein R1 and R2 are hydrogen, R4 is -CN, and R3 is selected from the group consisting of hydrogen and alkyl.

13. The lubricating composition of Claim 1, wherein R1, R2 and R3 are hydrogen and R4 is halogen.

14. The lubricating composition of Claim 1, wherein R1, R2 and R3 are hydrogen, and R4 is -OR10.

15. The lubricating composition of Claim 1, wherein R1 and R3 are hydrogen, R2 is -COR5, and R4 is -COR7.

16. A phosphorus- and sulfur-containing composition of matter prepared by a process which comprises reacting a phos-phonodithioic anhydride with an olefin corresponding to the formula:

wherein R1 is selected from the group consisting of hydrogen, alkyl, aromatic, substituted alkyl or substituted aromatic; R2 is selected from the group consisting of hydrogen, alkyl, aroma-tic, substituted alkyl, substituted aromatic, or -COR5, wherein R5 is selected from the group consisting of hydroxy, -OR6 where-in R6 is a hydrocarbon-based radical, or R5 together with R7 form -0-;
R3 is selected from the group consisting of hydrogen, alkyl, aromatic, substituted alkyl, substituted aromatic, or -CH2(-CH2)m-COOR8, wherein m is an integer having a value of 0 to 10, and R8 is selected from the group consisting of hydrogen or hydrocarbon-based; or any two of R1, R2 and R3 together form an alkylene or substituted alkylene;
R4 is selected from the group consisting of hydrogen, aromatic substituted aromatic, halogen, -COR7, -CN, -CONHR9, -OR10, -OCOR11, or -CR12R13R14, wherein R7 is selected from the group consisting of hydroxyl, hydrocarbon-based oxy radicals or together with R5 forms -0-, each R9, R12 R13 and R14 is inde-pendently selected from the group consisting of hydrogen and hydrocarbon-based radicals, and each R10 and R11 is a hydrocar-bon-based radical; and wherein the reactants are present in amounts such that there is at least about two moles of the olefin for each mole of the phosphonodithioic anhydride.

17. A process for the preparation of a phosphorus-and sulfur-containing composition of matter which comprises re-acting a phosphonodithioic anhydride with an olefin correspon-ding to the formula:

wherein R1 is selected from the group consisting of hydrogen, alkyl, aromatic, substituted alkyl or substituted aromatic; R2 is selected from the group consisting of hydrogen, alkyl, aro-matic, substituted alkyl, substituted aromatic, or -COR5, where-in R5 is selected from the group consisting of hydroxy, -OR6 wherein R6 is a hydrocarbon-based radical, or R5 together with R7 forms -0-;
R3 is selected from the group consisting of hydrogen, alkyl, aromatic, substituted alkyl, substituted aromatic, or -CH2(-CH2)m-COOR8, wherein m is an integer having a value of 0 to 10, and R8 is selected from the group consisting of hydrogen or hydrocarbon-based; or any two of R1, R2 and R3, together form an alkylene or substituted alkylene;
R4 is selected from the group consisting of hydrogen, aromatic, substituted aromatic, halogen, -COR7, -CN, -CONHR9, OR -OCOR11, or -CR12R13R14, wherein R7 group consisting of hydroxyl, hydrocarbon-based oxy radicals or together with R5 forms -0-, each R9, R12, R13 and R14 is inde-pendently selected from the group consisting of hydrogen and hydrocarbon-based radicals, and each R10 and R11 is a hydrocar-bon-based radical, in amounts such that there is at least about two (2) moles of the olefin for each mole of the phosphonodi-thioic anhydride.