US2063629A - Esters of the thio acids of phosphorus - Google Patents

Esters of the thio acids of phosphorus Download PDF

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US2063629A
US2063629A US7216A US721635A US2063629A US 2063629 A US2063629 A US 2063629A US 7216 A US7216 A US 7216A US 721635 A US721635 A US 721635A US 2063629 A US2063629 A US 2063629A
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phosphorus
thio
esters
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aliphatic
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Paul L Salzberg
James H Werntz
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids

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  • This invention relates to new esters of the thio acids of phosphorus and more particularly to the long chain aliphatic esters of such acids.
  • the aliphatic esters of orthophosphoric acids are known.
  • the orthophosphor'ic esters of the vlow molecular weight alcohols have not proved to be entirely satisfactory for commercial use for the reason that they do not have the marked surface active eflect desired in compounds of this type in the uses for which they are intended.
  • the orthophosphoric esters of the longer chain aliphatic alcohols have the desired surface active eflect but are generally solids at ordinary room temperatures and are insufllciently soluble in oils and hydrocarbon solvents to enable full advantage to be taken of their desirable properties.
  • An object of the present invention is to pro- .vide new chemical compounds having the advantageous features of prior compounds but without all of their disadvantages.
  • a further object of this invention is to provide long chain aliphatic esters of the thio acids of phosphorus which are new chemical compounds.
  • a still further object is to provide methods for preparing such new chemical compounds.
  • Other objects are to provide new compositions of matter and to advance the art. Still other objects will appear hereinafter.
  • an esterifying derivative of a thio acid of phosphorus with at least one molecular propor- 'tion of an aliphatic alcohol containing at least ten carbon atoms or'reacting an esteriiying de- 45 intend to include the mono, di, tri and tetra thio ortho-phosphoric acids, the thio-meta-phosphoric acids, the thio-pyrophosphoric acids, the thiohypophosphoric acids and also the thio phosphorus acids including the ortho, pyro and hypo acids.
  • the thiophosphoric acids are generally the cheapest to manufacture and have the most desirable properties and of these the thio ortho-phosphoric acids are preferred both for ease and cheapness of manufacture and for 55 their unusually desirable properties.
  • the esters of our invention contain "at least one aliphatic chain of at least ten carbon atoms. They may contain 2, 3 or 4 of such chains. They may contain aliphatic chains of a lesser number of carbon atoms. These aliphatic chains may be derived from either saturated or unsaturated aliphatic alcohols and are preferably hydrocarbon chains. nolic radicals. In other words, the esters of our invention may be either neutral or acid esters and may be homogeneous or mixed esters.
  • the esters of dithio ortho-phosphorlc acid may be prepared by reacting at least one molecular proportion of the desired alcohol with a mixture of phosphorus and sulphur or with Pass.
  • a mixture of phosphorus and sulphur or with Pass For example, two molecular proportions of dodecyl alcohol, when reacted with P285, forms didodecyl dithiophosphate.
  • An inert organic solvent such as benzene or toluene may be employed to better
  • the reaction will generally be carried out under a reflux condenser at refluxing temperatures and under a slight vacuum in order to remove hydrogen sulfide which is formed.
  • the alcohol may be first reacted with sodium to form the corresponding alcoholate before reacting with the phosphorus pentasuli'lde.
  • the monothio ortho-phosphates may be prepared by reacting one or more molecular proportions of the alcohol or alcoholate with phosphorus sulfochloride PSCls. For example, when three molecular proportions of sodium dodecyloxlde were reacted with PSCla, tridodecyl monothio ortho-phosphate was obtained. When one molecular proportion of decyl alcohol was reacted with PSCla, the mono decyl monothio phosphate was obtained.
  • esters of thio ortho-phosphoric acids may be prepared by reacting mercaptans such as tetradecyl mercaptan with'phosphorus oxychloride POCh.
  • the compounds produced by this method have each alkyl chain connected to the phosphorus through a sulphur atom.
  • the resulting product will be a mono, di or tri-thio phosphate, depending upon the molecular proportions of the mercaptan to the phosphorus oxychloride. If the phosphorus oxychloride is substituted by phosphorus penta sulphide the tetra thio phosphate will be produced.
  • a dithio phosphate produced by this method will be isomeric with that obtained by reacting the alcohol with phosphorus pentasulflde. It will be apparent that a variety of esters of the thio acids of phosphorus may be obtained by employing other esterifying derivatives of the acids of phosphorus in place 0! They may also contain pheflux condenser for 18 hours.
  • Example 1 Twenty-two and two-tenths parts by weight of phosphorus pentasulflde were suspended in 258 parts by weight of toluene. To this. 74.4 parts by weight of dodecyl alcohol were added slowly. The mixture was heated at 725 mm. under a re- The resulting reaction product forms stable emulsions when mixed with water.
  • This reaction product was treated with the calculated amount of aniline and-heated under a vacuum to remove most of the toluene.
  • the thick syrup which remained crystallized when chilled in ice water.
  • the salt was recrystallized from toluene in which it is soluble at room temperatures.
  • the White crystals were then dissolved in ether and aniline hydrochloride was precipitated by passing in dry hydrogen chloride.
  • the aniline hydrochloride was filtered off and the filtrate evaporated.
  • the oily residue became solid when chilled to about 50 C. but melted to an oil when warmed up to 20 C. It did not crystallize in an ice-salt mixture.
  • the oil was heated under a vacuum to remove residual solvents. This oil analyzed 6.3% of phosphorus. (Theory for didodecyl dithiophosphate is 6.6% phosphorus.)
  • the didodecyl dithio phosphate when added to water was sufliciently soluble to render. the water acid in reaction.
  • the p-nitroaniline salt of the dithiophosphate was prepared by dissolving it in toluene and treating with p-nitroaniline. This salt was quite soluble in toluene and alcohol at ordinary temperatures.
  • the pyridine salt was prepared by adding the calculated amount of pyridine to a water suspension of the didodecyl dithio phosphate and the solution shaken. The resulting solution foamed and exhibited a cleansing action when applied to the skin.
  • the sodium salt of didodecyl dithio phosphate made by treating didodecyl dithiophosphate with an aqueous solution of sodium carbonate, is not soluble in water.
  • Example 2 When four molecular proportions of 9,10-octa- .decenyl alcohol were reacted with one molecular proportion of phosphorus pentasulfide in accordance with the procedure of Example 1, dioctadecenyl dithio o'rtho-phosphate was produced.
  • This compound has the formula Example 3 -When five molecular proportions of octadecyl alcohol were reacted with one molecular proportion of phosphorus pentasulfide, trioctadecyl dithio ortho-phosphate was obtained.
  • This compound has the following formula Example 4 When three molecular proportions of tetradecyl alcohol yvere reacted with one molecular proportion of phosphorus sulphur chloride, tritetradecyl monothio ortho-phosphate having the formula CuHnO CuHu was obtained.
  • Example 5 Monotetradecyl thiometaphosphate having the formula 0 CnHaO-P was obtained by treating tritetradecyl monothio ,ortho-phosphate with concentrated sulphuric acid.
  • Example 6 Monocetyl monothio o-phosphate having the formula Cie aO S P 110/ on was prepared by reacting one mol. of cetyl a1- cohol with one mol. of PSCla in accordance with the procedure of Example 4, .followed by hydrolysis.
  • Tridodecyl trithio ortho-phosphate having the formula uas ⁇ % may be made by reacting three mols of dodecyl mercaptan with one mol. of phosphorus oxychloride.
  • Tridodecyl trithio phosphate CuHuS P--S u u CuHuS may be obtained by reacting one mol. Pas: with three mols of dodecyl alcohol. This compound is preferably obtained by reacting three mols oi dodecyl mercaptan with phosphorus trichloride
  • Example 9 The 0,0-dicetyl monothio ortho-phosphate CuHaS OH maple 10
  • the tetracetyl dithiopflophowhate can-o ocunu CnHaO (Julia I may be obtained by treating tricetyl monothiophosphate with concentrated sulphuric acid.
  • Example 11 dodecyl mercaptan with one mol. oi phosphorus pentasulflde.
  • Emmple 12 'Ietratetradecyl trithiopyrophosphate uHnO O C Ha may be obtained by, reacting four mols oi tetradecyl alcohol with one mol. oi! phosphorus trisuliotetrabromide PaSaBn.
  • Example 13 lietraeicosyl penta-thiopyrophosphate CnHuO ⁇ %S S ⁇ /S CmHn CsvHnO S CsoHn may be obtained by reacting two mols oi eicosyl alcohol and two mols of eicosyl mercaptan with one mol. of phosphorus trisuliotetrabromide.
  • Example 14 One gram molecular weight of phosphorus pentasulrlde was suspended in 2580 parts by weight of toluene. To this four gram molecular weights of the mixture 01 alcohols obtained by the carboxylic reduction of coconut ofl were added slowly. The mixture was heated at 125 mm. at the reflux temperature under a reflux condenser for 18 hours. The resulting mixture of esters and mixed esters oi dithio phosphoric acid was an oil which formed stable emulsions when mixed with water. This oil blends readily with lubricating oil and in this respect oflers an advantage over a pure didodecyl dithio phosphate which blends less readily with lubricating oil.
  • mixtures When such mixtures are employed, it will, in general, be desirable to employ such a mixture obtainable from the alcohols obtained by the carboxylic reduction of a natural fatty oil such as sperm oil and coconut-oil or the acids present therein.
  • Other mixtures of esters comprising mixed esters may be I from the olefins obtained by cracking paraflin wax hydrocarbons.
  • pure mixed esters are desired. They may be obtained by reacting one or two mols of an alcohol or mixture of alcohols containing at least ten carbon atoms with the esterifying derivative of a thio acid of phosphorus or their corresponding mercaptans with an esteriiying derivative of an acid 01' phosphorus and then reacting the resulting product with one or more mols of a different alcohol, a phenol or mercaptan.
  • our invention embraces the acid esters and their salts such as the alkali, alkaline earth, calcium, zinc, lead or ammonium salts.
  • ammonium salts we intend to include the salts of amines such as, for example, monododecyl amine, diethyl amine, cyclohexylamine, triethanolamine, aniline, nitroaniline, pyridine, naphthylamine, o-toluidine, diphenyl guanidine and the like as well as the salts of ammonia.
  • toluene as a diluent for the reaction.
  • solvents which is effective tor the solution of both the alcohol and the resulting thiophosphate but which is a non-solvent for impurities in the reagents.
  • solvents as chlorobenzene, carbon tetrachloride, benzene and the like or mixtures of such solvents such as a mixture 01 carbon tetrachloride and toluene will be found to be satisfactory.
  • the compounds of our invention may be employed as flotation agents for the separation of various types of minerals, or as parasiticides or as acid inhibitors in metal pickling baths or as corrosion inhibitors to retard the attack of metals by oxygen in aqueous solutions or in lubricants for bearings which operate under high pressures or as accelerators for the vulcanization of rubber.
  • Our compounds will have advantages over similar compounds for these purposes.
  • didodecyl dithiophosphate has the advantage over diai'nyl dithiophosphate in that the aniline salt oi. didodecyl dithiophosphate is more soluble in hydrocarbon solvents than the aniline salt of diamyl dithiophosphate.
  • the sodium salt of didodecyl is substantially insoluble in water, whereas the sodium salt of diamyldithiophosphate is readily soluble in water.
  • the dithiophosphates are generally oils at ordinary temperatures, whereas, the corresponding phosphates, such as didodecyl o-phosphate, are solids.
  • the sulphur content of our compounds renders them more eflective for many technical applications than the corresponding phosphates containing no sulphur; for example, when employed as parasiticides, flotation agents, or as acid inhibitors.
  • our compounds are more desirable as assistants for use in extreme pressure lubricants over the corresponding phosphates containing no sulphur and the lower molecular weight dithiophosphates because of their great solubility in the oils and their higher degree of oiliness.
  • An aliphatic ester of dithio orthophosphoric acid in which at least one aliphatic radical contains at least 10 carbon atoms.
  • a dialiphatic ester of a thio-acid of phosphorus each aliphatic group containing at least 10 carbon atoms.
  • a dialiphatic ester of a thio o-phosphoric acid each aliphatic group containing at least 10 carbon atoms.
  • a dialiphatic ester oi. a dithio-acid of phosphorus, each aliphatic group containing at least 10 carbon atoms.
  • a dialiphatio ester of dithio o-phosphoric acid each aliphatic group containing at least 10 carbon atoms.
  • a dodecyl ester of a thio-acid of phosphorus 14.
  • a dodecyl ester a thio o-phosphoric acid.
  • a dodecyl ester of a dithio-acid 0i phosphorus 16.
  • a dodecyl ester of dithio o-phosphoric acid 17.
  • a didodecyl ester of a thio-acid of phosphorus 18.
  • a didodecyl ester of a thio o-phosphoric acid 19.

Description

Patented Dec. 8, 1936 UNITED STATES PATENT OFFICE ES'IEBS OF THE 'IHIO ACIDS OF PHOSPHORUS No Drawinl.
22 Claims.
This invention relates to new esters of the thio acids of phosphorus and more particularly to the long chain aliphatic esters of such acids.
The aliphatic esters of orthophosphoric acids are known. The orthophosphor'ic esters of the vlow molecular weight alcohols have not proved to be entirely satisfactory for commercial use for the reason that they do not have the marked surface active eflect desired in compounds of this type in the uses for which they are intended.
to be employed. The orthophosphoric esters of the longer chain aliphatic alcohols have the desired surface active eflect but are generally solids at ordinary room temperatures and are insufllciently soluble in oils and hydrocarbon solvents to enable full advantage to be taken of their desirable properties.
An object of the present invention is to pro- .vide new chemical compounds having the advantageous features of prior compounds but without all of their disadvantages. A further object of this invention is to provide long chain aliphatic esters of the thio acids of phosphorus which are new chemical compounds. A still further object is to provide methods for preparing such new chemical compounds. Other objects are to provide new compositions of matter and to advance the art. Still other objects will appear hereinafter.
These objects may be accomplished in accordance with our invention which comprises reacting an esterifying derivative of a thio acid of phosphorus with at least one molecular propor- 'tion of an aliphatic alcohol containing at least ten carbon atoms or'reacting an esteriiying de- 45 intend to include the mono, di, tri and tetra thio ortho-phosphoric acids, the thio-meta-phosphoric acids, the thio-pyrophosphoric acids, the thiohypophosphoric acids and also the thio phosphorus acids including the ortho, pyro and hypo acids. However. the thiophosphoric acids are generally the cheapest to manufacture and have the most desirable properties and of these the thio ortho-phosphoric acids are preferred both for ease and cheapness of manufacture and for 55 their unusually desirable properties.
. control the reaction.
Application February 19, 1935,
Serial No. 7,216
The esters of our invention contain "at least one aliphatic chain of at least ten carbon atoms. They may contain 2, 3 or 4 of such chains. They may contain aliphatic chains of a lesser number of carbon atoms. These aliphatic chains may be derived from either saturated or unsaturated aliphatic alcohols and are preferably hydrocarbon chains. nolic radicals. In other words, the esters of our invention may be either neutral or acid esters and may be homogeneous or mixed esters.
The esters of dithio ortho-phosphorlc acid may be prepared by reacting at least one molecular proportion of the desired alcohol with a mixture of phosphorus and sulphur or with Pass. For example, two molecular proportions of dodecyl alcohol, when reacted with P285, forms didodecyl dithiophosphate. An inert organic solvent such as benzene or toluene may be employed to better The reaction will generally be carried out under a reflux condenser at refluxing temperatures and under a slight vacuum in order to remove hydrogen sulfide which is formed. If desired, the alcohol may be first reacted with sodium to form the corresponding alcoholate before reacting with the phosphorus pentasuli'lde.
The monothio ortho-phosphates may be prepared by reacting one or more molecular proportions of the alcohol or alcoholate with phosphorus sulfochloride PSCls. For example, when three molecular proportions of sodium dodecyloxlde were reacted with PSCla, tridodecyl monothio ortho-phosphate was obtained. When one molecular proportion of decyl alcohol was reacted with PSCla, the mono decyl monothio phosphate was obtained.
Still other esters of thio ortho-phosphoric acids may be prepared by reacting mercaptans such as tetradecyl mercaptan with'phosphorus oxychloride POCh. The compounds produced by this method have each alkyl chain connected to the phosphorus through a sulphur atom. The resulting product will be a mono, di or tri-thio phosphate, depending upon the molecular proportions of the mercaptan to the phosphorus oxychloride. If the phosphorus oxychloride is substituted by phosphorus penta sulphide the tetra thio phosphate will be produced. A dithio phosphate produced by this method will be isomeric with that obtained by reacting the alcohol with phosphorus pentasulflde. It will be apparent that a variety of esters of the thio acids of phosphorus may be obtained by employing other esterifying derivatives of the acids of phosphorus in place 0! They may also contain pheflux condenser for 18 hours.
In order to more clearly illustrate our invention and the preferred modes of carrying the same into eflfect, the following examples are given Example 1 Twenty-two and two-tenths parts by weight of phosphorus pentasulflde were suspended in 258 parts by weight of toluene. To this. 74.4 parts by weight of dodecyl alcohol were added slowly. The mixture was heated at 725 mm. under a re- The resulting reaction product forms stable emulsions when mixed with water.
This reaction product was treated with the calculated amount of aniline and-heated under a vacuum to remove most of the toluene. The thick syrup which remained crystallized when chilled in ice water. The salt was recrystallized from toluene in which it is soluble at room temperatures. The White crystals were then dissolved in ether and aniline hydrochloride was precipitated by passing in dry hydrogen chloride.
The aniline hydrochloride was filtered off and the filtrate evaporated. The oily residue became solid when chilled to about 50 C. but melted to an oil when warmed up to 20 C. It did not crystallize in an ice-salt mixture. The oil was heated under a vacuum to remove residual solvents. This oil analyzed 6.3% of phosphorus. (Theory for didodecyl dithiophosphate is 6.6% phosphorus.) The didodecyl dithio phosphate when added to water was sufliciently soluble to render. the water acid in reaction.
The p-nitroaniline salt of the dithiophosphate was prepared by dissolving it in toluene and treating with p-nitroaniline. This salt was quite soluble in toluene and alcohol at ordinary temperatures.
The pyridine salt was prepared by adding the calculated amount of pyridine to a water suspension of the didodecyl dithio phosphate and the solution shaken. The resulting solution foamed and exhibited a cleansing action when applied to the skin.
, The sodium salt of didodecyl dithio phosphate, made by treating didodecyl dithiophosphate with an aqueous solution of sodium carbonate, is not soluble in water.
Example 2 When four molecular proportions of 9,10-octa- .decenyl alcohol were reacted with one molecular proportion of phosphorus pentasulfide in accordance with the procedure of Example 1, dioctadecenyl dithio o'rtho-phosphate was produced. This compound has the formula Example 3 -When five molecular proportions of octadecyl alcohol were reacted with one molecular proportion of phosphorus pentasulfide, trioctadecyl dithio ortho-phosphate was obtained. This compound has the following formula Example 4 When three molecular proportions of tetradecyl alcohol yvere reacted with one molecular proportion of phosphorus sulphur chloride, tritetradecyl monothio ortho-phosphate having the formula CuHnO CuHu was obtained.
Example 5 Monotetradecyl thiometaphosphate having the formula 0 CnHaO-P was obtained by treating tritetradecyl monothio ,ortho-phosphate with concentrated sulphuric acid.
Example 6 Monocetyl monothio o-phosphate having the formula Cie aO S P 110/ on was prepared by reacting one mol. of cetyl a1- cohol with one mol. of PSCla in accordance with the procedure of Example 4, .followed by hydrolysis.
Example 7 Tridodecyl trithio ortho-phosphate having the formula uas\% may be made by reacting three mols of dodecyl mercaptan with one mol. of phosphorus oxychloride.
CnHu S I Example 8 Tridodecyl trithio phosphate CuHuS P--S u u CuHuS may be obtained by reacting one mol. Pas: with three mols of dodecyl alcohol. This compound is preferably obtained by reacting three mols oi dodecyl mercaptan with phosphorus trichloride Example 9 The 0,0-dicetyl monothio ortho-phosphate CuHaS OH maple 10 The tetracetyl dithiopflophowhate can-o ocunu CnHaO (Julia I may be obtained by treating tricetyl monothiophosphate with concentrated sulphuric acid.
Example 11 dodecyl mercaptan with one mol. oi phosphorus pentasulflde.
Emmple 12 'Ietratetradecyl trithiopyrophosphate uHnO O C Ha may be obtained by, reacting four mols oi tetradecyl alcohol with one mol. oi! phosphorus trisuliotetrabromide PaSaBn.
Example 13 'lietraeicosyl penta-thiopyrophosphate CnHuO\ %S S\ /S CmHn CsvHnO S CsoHn may be obtained by reacting two mols oi eicosyl alcohol and two mols of eicosyl mercaptan with one mol. of phosphorus trisuliotetrabromide.
Example 14 One gram molecular weight of phosphorus pentasulrlde was suspended in 2580 parts by weight of toluene. To this four gram molecular weights of the mixture 01 alcohols obtained by the carboxylic reduction of coconut ofl were added slowly. The mixture was heated at 125 mm. at the reflux temperature under a reflux condenser for 18 hours. The resulting mixture of esters and mixed esters oi dithio phosphoric acid was an oil which formed stable emulsions when mixed with water. This oil blends readily with lubricating oil and in this respect oflers an advantage over a pure didodecyl dithio phosphate which blends less readily with lubricating oil.
The above examples are merely illustrative of some of the compounds embraced within our invention and the preierred modes of preparing such compounds. Other similar compounds may be prepared from other alcohols such as decyl, undecenyl, hexacosyl, eleostearyl, linoleyl, ricinoleyl, abietyl and the like alcohols and mercaptans. Also, mixtures of esters containing mixed esters may be prepared by reacting a mixture 01' such alcohols with an esteriiying derivative of a thio acid 01' phosphorus or a mixture of the corresponding mercaptans with an esterifying derivative of an acid of phosphorus. When such mixtures are employed, it will, in general, be desirable to employ such a mixture obtainable from the alcohols obtained by the carboxylic reduction of a natural fatty oil such as sperm oil and coconut-oil or the acids present therein. Other mixtures of esters comprising mixed esters may be I from the olefins obtained by cracking paraflin wax hydrocarbons.
1! pure mixed esters are desired. they may be obtained by reacting one or two mols of an alcohol or mixture of alcohols containing at least ten carbon atoms with the esterifying derivative of a thio acid of phosphorus or their corresponding mercaptans with an esteriiying derivative of an acid 01' phosphorus and then reacting the resulting product with one or more mols of a different alcohol, a phenol or mercaptan.
Our invention embraces the acid esters and their salts such as the alkali, alkaline earth, calcium, zinc, lead or ammonium salts. By "ammonium salts, we intend to include the salts of amines such as, for example, monododecyl amine, diethyl amine, cyclohexylamine, triethanolamine, aniline, nitroaniline, pyridine, naphthylamine, o-toluidine, diphenyl guanidine and the like as well as the salts of ammonia.
In the above examples, we have disclosed toluene as a diluent for the reaction. We may use other inert solvents or no solvents at all. We prefer to use a solvent which is effective tor the solution of both the alcohol and the resulting thiophosphate but which is a non-solvent for impurities in the reagents. For example, such solvents as chlorobenzene, carbon tetrachloride, benzene and the like or mixtures of such solvents such as a mixture 01 carbon tetrachloride and toluene will be found to be satisfactory.
The compounds of our invention may be employed as flotation agents for the separation of various types of minerals, or as parasiticides or as acid inhibitors in metal pickling baths or as corrosion inhibitors to retard the attack of metals by oxygen in aqueous solutions or in lubricants for bearings which operate under high pressures or as accelerators for the vulcanization of rubber. Our compounds will have advantages over similar compounds for these purposes. For example, didodecyl dithiophosphate has the advantage over diai'nyl dithiophosphate in that the aniline salt oi. didodecyl dithiophosphate is more soluble in hydrocarbon solvents than the aniline salt of diamyl dithiophosphate. Also, the sodium salt of didodecyl is substantially insoluble in water, whereas the sodium salt of diamyldithiophosphate is readily soluble in water. The dithiophosphates are generally oils at ordinary temperatures, whereas, the corresponding phosphates, such as didodecyl o-phosphate, are solids. advantage for many technical applications such as their use as flotation agents, in pharmaceuticals and as acid corrosion inhibitors. Furthermore, the sulphur content of our compounds renders them more eflective for many technical applications than the corresponding phosphates containing no sulphur; for example, when employed as parasiticides, flotation agents, or as acid inhibitors. Furthermore, our compounds are more desirable as assistants for use in extreme pressure lubricants over the corresponding phosphates containing no sulphur and the lower molecular weight dithiophosphates because of their great solubility in the oils and their higher degree of oiliness.
While we have disclosed the preferred embodiments '0! our invention, it will be readily apparent that many variations and modifications may be This is an made therein without departing from the spirit of our invention. Accordingly, the scope of our invention is to be limited solely by the appended claims construed as broadly as is permissible in view of the prior art.
We claim: 7
1. An aliphatic ester of a thio-acid of phosphorus in which at least one aliphatic radical contains at least 10 carbon atoms.
2. An aliphatic ester of a thio phosphoric acid in which at least one aliphatic radical contains at least 10 carbon atoms.
3. An aliphatic ester of a thio o-phosphoric acid in which at least one aliphatic radical contains at least 10 carbon atoms.
4. An alkyl ester of a thio-acid of phosphorus in which at least one alkyl radical contains at least 10 carbon atoms.
5. An alkyl ester of a thio phosphoric acid in which at least one alkyl radical contains at least 10 carbon atoms.
6. An alkyi ester of a thio-o-phosphorlc acid in which at least one alkyl radical contains at least 10 carbon atoms.
7. An aliphatic ester of a dithio-acid of phosphbrus in which at least one aliphatic radical contains at least 10 carbon atoms.
8. An aliphatic ester of'a dithio phosphoric acid in which at least one aliphatic radical contains at least 10 carbon atoms.
9. An aliphatic ester of dithio orthophosphoric acid in which at least one aliphatic radical contains at least 10 carbon atoms.
10. A dialiphatic ester of a thio-acid of phosphorus, each aliphatic group containing at least 10 carbon atoms.
11. A dialiphatic ester of a thio o-phosphoric acid, each aliphatic group containing at least 10 carbon atoms.
12. A dialiphatic ester oi. a dithio-acid of phosphorus, each aliphatic group containing at least 10 carbon atoms.
13. A dialiphatio ester of dithio o-phosphoric acid, each aliphatic group containing at least 10 carbon atoms.
14. A dodecyl ester of a thio-acid of phosphorus.
15. A dodecyl ester a thio o-phosphoric acid.
16. A dodecyl ester of a dithio-acid 0i phosphorus.
17. A dodecyl ester of dithio o-phosphoric acid.
18. A didodecyl ester of a thio-acid of phosphorus.
19. A didodecyl ester of a thio o-phosphoric acid.
20. A"didodecyl ester of a dithio acid of phosphorus.
21. Didodecyl dithio o-phosphoric acid.
22. Di-(9,10-octadecenyl) dithio ortho-phosphate.
PAUL L. SALZBERG. JAMES H. WERNTZ.
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Cited By (74)

* Cited by examiner, † Cited by third party
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US2434357A (en) * 1943-09-27 1948-01-13 Minerec Corp Tetra-alkyl carbonyl tetrathio diphosphates and process for their preparation
US2442915A (en) * 1944-06-22 1948-06-08 Socony Vacuum Oil Co Inc Mineral oil composition
US2447288A (en) * 1946-03-06 1948-08-17 Gulf Oil Corp Primary aliphatic amine salts of dialiphatic substituted mono-thiophosphoric acids
US2471115A (en) * 1946-09-19 1949-05-24 Standard Oil Dev Co Lubricating oil
US2480873A (en) * 1944-12-18 1949-09-06 Standard Oil Co Lubricants
US2502400A (en) * 1947-06-14 1950-03-28 California Spray Chemical Corp Method of making diphosphoric esters
US2502401A (en) * 1947-06-18 1950-03-28 California Spray Chemical Corp Manufacture of diphosphoric esters
US2506310A (en) * 1946-12-28 1950-05-02 Standard Oil Dev Co Lubricating oil composition
US2506570A (en) * 1945-10-05 1950-05-09 Socony Vacuum Oil Co Inc Lubricating oil compositions
US2508431A (en) * 1949-02-17 1950-05-23 California Research Corp Bitumen-treating agent
US2511731A (en) * 1947-01-22 1950-06-13 Standard Oil Dev Co Extreme pressure lubricants
US2514150A (en) * 1946-12-26 1950-07-04 Eastman Kodak Co Insecticides produced by reacting trialkyl phosphates with thiophosphoryl halides and their preparation
US2516119A (en) * 1945-08-09 1950-07-25 Continental Oil Co Metal, phosphorus, and sulfur-containing organic compounds
US2528732A (en) * 1947-01-31 1950-11-07 Socony Vacuum Oil Co Inc Reaction products of diesters of dithiophosphoric acid and mineral oil compositions containing the same
US2531129A (en) * 1948-03-26 1950-11-21 American Cyanamid Co Mineral lubricating oil compositions containing dialkyldithio-phosphoric acid-formaldehyde condensation products
US2545158A (en) * 1947-10-22 1951-03-13 Standard Oil Dev Co Oxidation resisting hydrocarbon products
US2565920A (en) * 1948-03-26 1951-08-28 American Cyanamid Co Triesters of dithiophosphoric acid
US2566397A (en) * 1947-06-07 1951-09-04 Standard Oil Co Lubricants and lubricant additives
US2577966A (en) * 1948-03-26 1951-12-11 American Cyanamid Co Dialkyldithiophosphoric acid formaldehyde condensation products
US2582204A (en) * 1947-11-12 1952-01-08 Monsanto Chemicals Tetraalkyl monothiopyrophosphate as an insecticide
DE767153C (en) * 1938-08-02 1952-01-31 Bayer Ag Combating animal pests
US2586655A (en) * 1948-03-26 1952-02-19 American Cyanamid Co S-alkoxymethyl-o, o'-dialkyldithiophosphates
US2596076A (en) * 1948-03-26 1952-05-06 American Cyanamid Co Dithiophosphate esters as insecticides
US2606182A (en) * 1947-06-07 1952-08-05 Standard Oil Co Lubricating oil additive
US2611728A (en) * 1949-11-01 1952-09-23 Standard Oil Dev Co Insecticidal compositions containing substituted aliphatic esters of diethyl dithiophosphoric acid
US2611729A (en) * 1949-11-01 1952-09-23 Standard Oil Dev Co Insecticidal compositions containing hydrocarbon esters of diethyl dithiophosphoric acid
US2614948A (en) * 1947-03-27 1952-10-21 Michael W Freeman Producing modified machine elements
US2614988A (en) * 1948-03-26 1952-10-21 American Cyanamid Co Hydrocarbon oils containing salkoxymethyl - o,o' - dialkyldithiophosphates
US2630450A (en) * 1949-10-17 1953-03-03 Shell Dev Tetraesters of thiodiphosphonic acid
US2640847A (en) * 1949-05-07 1953-06-02 Bayer Ag Production of neutral esters of thiolphosphoric acid
US2663722A (en) * 1950-03-24 1953-12-22 Victor Chemical Works Method of preparing tetraalkyl dithionopyrophosphates
US2689258A (en) * 1948-04-21 1954-09-14 Standard Oil Dev Co Reaction of terpenes with thiophosphorous acid esters and products thereof
US2694084A (en) * 1950-06-29 1954-11-09 Standard Oil Dev Co Reaction product of a diorganic ester of dithiophosphoric acid with a sulfonating agent and the process for making same
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US2705694A (en) * 1952-06-24 1955-04-05 Exxon Research Engineering Co Insecticidal compositions comprising diethyl thiophosphoric acid disulfide
US2757118A (en) * 1951-11-20 1956-07-31 Monsanto Chemicals Method for controlling mollusks with diethyl thiophosphoryl bis (dimethylamido) phosphate
US2786009A (en) * 1953-09-04 1957-03-19 Fmc Corp Insecticidal compositions comprising carbonyl bisdithiophosphate compounds and method of applying the same
US2809138A (en) * 1954-03-18 1957-10-08 Hoechst Ag Bath solution and a process of treating metal surfaces
US2820723A (en) * 1957-01-17 1958-01-21 Lubrizol Corp Inhibition of corrosion of phosphated metal surfaces
US2836534A (en) * 1954-02-11 1958-05-27 Monsanto Chemicals Phosphorus-sulfur compounds
US2841486A (en) * 1953-06-22 1958-07-01 Phillips Petroleum Co Plant defoliating method employing di-, tri-, and tetrathiophosphoric acid derivatives
US2849475A (en) * 1956-04-04 1958-08-26 American Cyanamid Co Diesters of dithiophosphoric acid
US2861907A (en) * 1956-09-28 1958-11-25 Lubrizol Corp Inhibition of corrosion of metal surfaces by salt of phosphorodithioic acid
DE1073481B (en) * 1960-01-21
US2965467A (en) * 1956-10-16 1960-12-20 Pittsburgh Coke And Chemical C Method of defoliating plants
DE1097606B (en) * 1951-03-29 1961-01-19 California Research Corp Lubricating oils
US2976122A (en) * 1955-12-07 1961-03-21 Exxon Research Engineering Co Analysis of heavy metal ions and metal chelates of dialkyl dithiophosphoric acids
US3210244A (en) * 1962-06-05 1965-10-05 Socony Mobil Oil Co Inc Method for controlling insects with organophosphorus compounds
US3259579A (en) * 1954-11-29 1966-07-05 Exxon Research Engineering Co Esters of dithiophosphoric acids and lubricating oil compositions containing same
US3494900A (en) * 1967-03-06 1970-02-10 Monsanto Co Synergistic combinations of a thiazole accelerator and certain phosphorodithioates for epdm rubbers
US3496152A (en) * 1967-03-06 1970-02-17 Monsanto Co Synergistic accelerator combinations of phosphorodithioates and thiurams or dithiocarbonates for epdm rubbers
US3844960A (en) * 1970-11-06 1974-10-29 Shell Oil Co Lubricant compositions
US3971836A (en) * 1974-08-16 1976-07-27 Minerec Corporation Amine-stabilized dialkyl dithiophosphates
US4036746A (en) * 1974-08-16 1977-07-19 Minerec Corporation Flotation with amine-stabilized dialkyl dithiophosphates
US4496683A (en) * 1982-08-11 1985-01-29 Monsanto Company Rubber compositions containing a vulcanization system alterative
US4755311A (en) * 1986-08-14 1988-07-05 The Lubrizol Corporation Phosphorus-, sulfur- and boron-containing compositions, and lubricant and functional fluid compositions containing same
US4879022A (en) * 1987-07-14 1989-11-07 The Lubrizol Corporation Ore flotation process and use of mixed hydrocarbyl dithiophosphoric acids and salts thereof
US5830817A (en) * 1994-07-13 1998-11-03 Rhein Chemie Rheinau Gmbh Accelerator combinations
US20070078066A1 (en) * 2005-10-03 2007-04-05 Milner Jeffrey L Lubricant formulations containing extreme pressure agents
US20070105728A1 (en) * 2005-11-09 2007-05-10 Phillips Ronald L Lubricant composition
US20070142660A1 (en) * 2005-11-09 2007-06-21 Degonia David J Salt of a sulfur-containing, phosphorus-containing compound, and methods thereof
US20070142237A1 (en) * 2005-11-09 2007-06-21 Degonia David J Lubricant composition
US20070142659A1 (en) * 2005-11-09 2007-06-21 Degonia David J Sulfur-containing, phosphorus-containing compound, its salt, and methods thereof
US20070225182A1 (en) * 2006-03-22 2007-09-27 Chip Hewette Gear fluids
US20080280794A1 (en) * 2007-05-09 2008-11-13 Chip Hewette Compositions comprising at least one friction modifying compound, and methods of use thereof
EP2025739A1 (en) 2007-08-16 2009-02-18 Afton Chemical Corporation Lubrication compositions having improved friction properties
US7833953B2 (en) 2006-08-28 2010-11-16 Afton Chemical Corporation Lubricant composition
US7879775B2 (en) 2006-07-14 2011-02-01 Afton Chemical Corporation Lubricant compositions
US8299003B2 (en) 2005-11-09 2012-10-30 Afton Chemical Corporation Composition comprising a sulfur-containing, phosphorus-containing compound, and/or its salt, and uses thereof
US9302273B2 (en) 2011-10-18 2016-04-05 Cytec Technology Corp. Froth flotation processes
US9302272B2 (en) 2011-10-18 2016-04-05 Cytec Technology Corp. Froth flotation processes
US9302274B2 (en) 2011-10-18 2016-04-05 Cytec Technology Corp. Collector compositions and methods of using the same
EP3546550A1 (en) 2018-03-16 2019-10-02 Afton Chemical Corporation Lubricants containing amine salt of acid phosphate and hydrocarbyl borate
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Cited By (83)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1073481B (en) * 1960-01-21
DE767153C (en) * 1938-08-02 1952-01-31 Bayer Ag Combating animal pests
DE767930C (en) * 1938-08-04 1955-01-10 Bayer Ag Pest repellants
US2434357A (en) * 1943-09-27 1948-01-13 Minerec Corp Tetra-alkyl carbonyl tetrathio diphosphates and process for their preparation
US2442915A (en) * 1944-06-22 1948-06-08 Socony Vacuum Oil Co Inc Mineral oil composition
US2480873A (en) * 1944-12-18 1949-09-06 Standard Oil Co Lubricants
US2516119A (en) * 1945-08-09 1950-07-25 Continental Oil Co Metal, phosphorus, and sulfur-containing organic compounds
US2506570A (en) * 1945-10-05 1950-05-09 Socony Vacuum Oil Co Inc Lubricating oil compositions
US2447288A (en) * 1946-03-06 1948-08-17 Gulf Oil Corp Primary aliphatic amine salts of dialiphatic substituted mono-thiophosphoric acids
US2471115A (en) * 1946-09-19 1949-05-24 Standard Oil Dev Co Lubricating oil
US2514150A (en) * 1946-12-26 1950-07-04 Eastman Kodak Co Insecticides produced by reacting trialkyl phosphates with thiophosphoryl halides and their preparation
US2506310A (en) * 1946-12-28 1950-05-02 Standard Oil Dev Co Lubricating oil composition
US2511731A (en) * 1947-01-22 1950-06-13 Standard Oil Dev Co Extreme pressure lubricants
US2528732A (en) * 1947-01-31 1950-11-07 Socony Vacuum Oil Co Inc Reaction products of diesters of dithiophosphoric acid and mineral oil compositions containing the same
US2614948A (en) * 1947-03-27 1952-10-21 Michael W Freeman Producing modified machine elements
US2606182A (en) * 1947-06-07 1952-08-05 Standard Oil Co Lubricating oil additive
US2566397A (en) * 1947-06-07 1951-09-04 Standard Oil Co Lubricants and lubricant additives
US2502400A (en) * 1947-06-14 1950-03-28 California Spray Chemical Corp Method of making diphosphoric esters
US2502401A (en) * 1947-06-18 1950-03-28 California Spray Chemical Corp Manufacture of diphosphoric esters
US2545158A (en) * 1947-10-22 1951-03-13 Standard Oil Dev Co Oxidation resisting hydrocarbon products
US2582204A (en) * 1947-11-12 1952-01-08 Monsanto Chemicals Tetraalkyl monothiopyrophosphate as an insecticide
US2565920A (en) * 1948-03-26 1951-08-28 American Cyanamid Co Triesters of dithiophosphoric acid
US2596076A (en) * 1948-03-26 1952-05-06 American Cyanamid Co Dithiophosphate esters as insecticides
US2586655A (en) * 1948-03-26 1952-02-19 American Cyanamid Co S-alkoxymethyl-o, o'-dialkyldithiophosphates
US2577966A (en) * 1948-03-26 1951-12-11 American Cyanamid Co Dialkyldithiophosphoric acid formaldehyde condensation products
US2614988A (en) * 1948-03-26 1952-10-21 American Cyanamid Co Hydrocarbon oils containing salkoxymethyl - o,o' - dialkyldithiophosphates
US2531129A (en) * 1948-03-26 1950-11-21 American Cyanamid Co Mineral lubricating oil compositions containing dialkyldithio-phosphoric acid-formaldehyde condensation products
US2689258A (en) * 1948-04-21 1954-09-14 Standard Oil Dev Co Reaction of terpenes with thiophosphorous acid esters and products thereof
US2508431A (en) * 1949-02-17 1950-05-23 California Research Corp Bitumen-treating agent
US2640847A (en) * 1949-05-07 1953-06-02 Bayer Ag Production of neutral esters of thiolphosphoric acid
US2630450A (en) * 1949-10-17 1953-03-03 Shell Dev Tetraesters of thiodiphosphonic acid
US2611729A (en) * 1949-11-01 1952-09-23 Standard Oil Dev Co Insecticidal compositions containing hydrocarbon esters of diethyl dithiophosphoric acid
US2611728A (en) * 1949-11-01 1952-09-23 Standard Oil Dev Co Insecticidal compositions containing substituted aliphatic esters of diethyl dithiophosphoric acid
US2663722A (en) * 1950-03-24 1953-12-22 Victor Chemical Works Method of preparing tetraalkyl dithionopyrophosphates
US2694084A (en) * 1950-06-29 1954-11-09 Standard Oil Dev Co Reaction product of a diorganic ester of dithiophosphoric acid with a sulfonating agent and the process for making same
DE1097606B (en) * 1951-03-29 1961-01-19 California Research Corp Lubricating oils
US2757118A (en) * 1951-11-20 1956-07-31 Monsanto Chemicals Method for controlling mollusks with diethyl thiophosphoryl bis (dimethylamido) phosphate
US2705694A (en) * 1952-06-24 1955-04-05 Exxon Research Engineering Co Insecticidal compositions comprising diethyl thiophosphoric acid disulfide
US2841486A (en) * 1953-06-22 1958-07-01 Phillips Petroleum Co Plant defoliating method employing di-, tri-, and tetrathiophosphoric acid derivatives
US2786009A (en) * 1953-09-04 1957-03-19 Fmc Corp Insecticidal compositions comprising carbonyl bisdithiophosphate compounds and method of applying the same
US2836534A (en) * 1954-02-11 1958-05-27 Monsanto Chemicals Phosphorus-sulfur compounds
US2809138A (en) * 1954-03-18 1957-10-08 Hoechst Ag Bath solution and a process of treating metal surfaces
US3259579A (en) * 1954-11-29 1966-07-05 Exxon Research Engineering Co Esters of dithiophosphoric acids and lubricating oil compositions containing same
US2976122A (en) * 1955-12-07 1961-03-21 Exxon Research Engineering Co Analysis of heavy metal ions and metal chelates of dialkyl dithiophosphoric acids
US2849475A (en) * 1956-04-04 1958-08-26 American Cyanamid Co Diesters of dithiophosphoric acid
US2861907A (en) * 1956-09-28 1958-11-25 Lubrizol Corp Inhibition of corrosion of metal surfaces by salt of phosphorodithioic acid
US2965467A (en) * 1956-10-16 1960-12-20 Pittsburgh Coke And Chemical C Method of defoliating plants
US2820723A (en) * 1957-01-17 1958-01-21 Lubrizol Corp Inhibition of corrosion of phosphated metal surfaces
US3210244A (en) * 1962-06-05 1965-10-05 Socony Mobil Oil Co Inc Method for controlling insects with organophosphorus compounds
US3494900A (en) * 1967-03-06 1970-02-10 Monsanto Co Synergistic combinations of a thiazole accelerator and certain phosphorodithioates for epdm rubbers
US3496152A (en) * 1967-03-06 1970-02-17 Monsanto Co Synergistic accelerator combinations of phosphorodithioates and thiurams or dithiocarbonates for epdm rubbers
US3844960A (en) * 1970-11-06 1974-10-29 Shell Oil Co Lubricant compositions
US3971836A (en) * 1974-08-16 1976-07-27 Minerec Corporation Amine-stabilized dialkyl dithiophosphates
US4036746A (en) * 1974-08-16 1977-07-19 Minerec Corporation Flotation with amine-stabilized dialkyl dithiophosphates
US4496683A (en) * 1982-08-11 1985-01-29 Monsanto Company Rubber compositions containing a vulcanization system alterative
US4755311A (en) * 1986-08-14 1988-07-05 The Lubrizol Corporation Phosphorus-, sulfur- and boron-containing compositions, and lubricant and functional fluid compositions containing same
US4879022A (en) * 1987-07-14 1989-11-07 The Lubrizol Corporation Ore flotation process and use of mixed hydrocarbyl dithiophosphoric acids and salts thereof
US5830817A (en) * 1994-07-13 1998-11-03 Rhein Chemie Rheinau Gmbh Accelerator combinations
US20070078066A1 (en) * 2005-10-03 2007-04-05 Milner Jeffrey L Lubricant formulations containing extreme pressure agents
US20070142237A1 (en) * 2005-11-09 2007-06-21 Degonia David J Lubricant composition
EP2270120A1 (en) 2005-11-09 2011-01-05 Afton Chemical Corporation A salt of sulfur-containing, phosphorus-containing compound, and method of preparation thereof
US20070105728A1 (en) * 2005-11-09 2007-05-10 Phillips Ronald L Lubricant composition
US20070142659A1 (en) * 2005-11-09 2007-06-21 Degonia David J Sulfur-containing, phosphorus-containing compound, its salt, and methods thereof
US20070142660A1 (en) * 2005-11-09 2007-06-21 Degonia David J Salt of a sulfur-containing, phosphorus-containing compound, and methods thereof
US8299003B2 (en) 2005-11-09 2012-10-30 Afton Chemical Corporation Composition comprising a sulfur-containing, phosphorus-containing compound, and/or its salt, and uses thereof
US20080319216A1 (en) * 2005-11-09 2008-12-25 Degonia David J Salt of a Sulfur-Containing, Phosphorus-Containing Compound, And Methods Thereof
US7928260B2 (en) 2005-11-09 2011-04-19 Afton Chemical Corporation Salt of a sulfur-containing, phosphorus-containing compound, and methods thereof
US20070225182A1 (en) * 2006-03-22 2007-09-27 Chip Hewette Gear fluids
US7410935B2 (en) 2006-03-22 2008-08-12 Afton Chemical Corporation Gear fluids
US7879775B2 (en) 2006-07-14 2011-02-01 Afton Chemical Corporation Lubricant compositions
US7833953B2 (en) 2006-08-28 2010-11-16 Afton Chemical Corporation Lubricant composition
US20080280794A1 (en) * 2007-05-09 2008-11-13 Chip Hewette Compositions comprising at least one friction modifying compound, and methods of use thereof
DE102008019662A1 (en) 2007-05-09 2008-11-13 Afton Chemical Corp. Compositions comprising at least one friction modifier compound, and methods of use thereof
US20090048131A1 (en) * 2007-08-16 2009-02-19 Guinther Gregory H Lubricating compositions having improved friction properties
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US8349778B2 (en) 2007-08-16 2013-01-08 Afton Chemical Corporation Lubricating compositions having improved friction properties
US9302273B2 (en) 2011-10-18 2016-04-05 Cytec Technology Corp. Froth flotation processes
US9302272B2 (en) 2011-10-18 2016-04-05 Cytec Technology Corp. Froth flotation processes
US9302274B2 (en) 2011-10-18 2016-04-05 Cytec Technology Corp. Collector compositions and methods of using the same
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