US3791804A - Fuel and lubricating oil additives transition metal complexes - Google Patents

Fuel and lubricating oil additives transition metal complexes Download PDF

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US3791804A
US3791804A US00865496A US3791804DA US3791804A US 3791804 A US3791804 A US 3791804A US 00865496 A US00865496 A US 00865496A US 3791804D A US3791804D A US 3791804DA US 3791804 A US3791804 A US 3791804A
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fuel
alkyl
acid
transition metal
lubricating oil
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W Brannen
R Watson
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BP Corp North America Inc
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Standard Oil Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/18—Complexes with metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26—Amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/30—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/08—Groups 4 or 14
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/10—Groups 5 or 15
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/14—Group 7
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/16—Groups 8, 9, or 10

Definitions

  • antistatic agents it is desirable in formulating antistatic agents to find one which is multifunctional. That is, it is desirable to have an antistatic agent which may inhibit oxidation, enhance lubricating properties of the fuel or lubricant to which it is added and/or suspend foreign material to prevent accumulation and deposits on metal surfaces.
  • multifunctional agents have been discovered but have been too expensive to incorporate as antistatic agents.
  • induction system as used herein is intended to mean the path that the incoming air follows in an automobile engine through the air cleaner, carburetor and intake manifold into the cylinders. This air is of course an air-gasoline mixture after passing through the carburetor.
  • the problem is then to find an inexpensive antistatic agent that will be multifunctional and will not itself deposit further along the induction system of the engine.
  • antistatic agents Another important property of antistatic agents is incrtness to other additives which may be incorporated into the hydrocarbon fuel or lubricating oil. Reaction would of course deplete the effective additive in the fuel or lubricating oil and tend to reduce its overall efficiency as well as increase the need for additional additive. Most desirable, then, is an antistatic agent which readily disperses into the hydrocarbon fuel or lubricating oil and serves as a conductive agent, yet remains inert to other active additives in such fuel or lubricating oil.
  • Designation Average Molecular Weight fuel or lubricating oil additive It would be used in hydrocarbon fuels in a concentration of from about 0.0001 percent to about 0.5 percent based upon the weight of hydrocarbon fuel.
  • the reaction product acts as an antistatic agent, reducing the build up of static electricity during the loading or unloading of fuel.
  • the reaction product can be added in amounts ranging from about 0.1 percent to about 10 percent based on the weight of oil of lubricating viscosity.
  • the reaction product acts as an antistatic agent and inhibits oxidation and wear of metal surfaces as well.
  • Transition metal complexes useful in the invention of this disclosure are described in The Journal of the American Chemical Society in volume 88 at pages 2156 through 2162 (I966), hereby incorporated by reference.
  • metal salts useful in forming transition metal complexes are the transition metal chlorides, perchloroates, nitrates, thiocyanates, oxalates, bromides and fluoborates.
  • Nonlimiting examples of the transition metals are those selected from the group consisting of cadmium, chromium, cobalt, copper, iron, manganese, molybdenum, mercury, nickel, rhodium, silver, titanium, tungsten, vanadium and zinc.
  • Suitable polyamines generally come within the formula H N (-alkylene-NH),.I-I, in which n is an integer from about 1 to about 12, and alkylene is a saturated divalent hydrocarbon containing from about 1 to about 10 carbon atoms.
  • Suitable polyamines include, for example, butylene polyamines, and cyclic homologues of such polyamines, for example, piperazines.
  • alkylene polyamines are: ethylene diamine, hexamethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, hexaethyleneheptamine and N-2-aminoethylpiperazine.
  • Polyethylene polyamines are generally preferred, pentaethylenehexamine being particularly preferred since the transition metals generally form hexacoordinate complexes.
  • the invention can be described as the reaction product produced by the reaction between about equal molar portions of (1) an alkyl benzene sulfonic acid, an alkyl sulfonic acid, an alkyl phosphoric acid or an alkyl carboxylic acid having an average molecular weight between about 200 and about 1,600, and (2) a transition metal complex of a polyamine.
  • reaction product is proposed as a hydrocarbon EXAMPLE I exemplified in The Journal of the American Chemical Society (previously cited).
  • the alkyl benzene sulfonic acid is preferably one wherein the alkyl substituent is a branched chain hydrocarbon having an average molecular weight in the range of from about 50 to about 1,450, thereby giving the acid an average molecular weight of from about 200 to about 1,600.
  • Specific examples of such acids are L-4 benzene sulfonic acid, L-l benzene sulfonic acid, L-50 benzene sulfonic acid and l-l-l00 benzene sulfonic acid.
  • the alkyl sulfonic acid is preferably one wherein the alkyl substituent is a branched chain hydrocarbon having an average molecular weight in the range of from about 100 to about 1,500, thereby giving the acid an average molecular weight of from about 200 to about 1,600.
  • Specific examples of such acids are L-4 sulfonic acid, L-l0 sulfonic acid, L 50 sulfonic acid and 11-100 sulfonic acid.
  • the alkyl phosphorus acid is preferably one wherein the alkyl substituent is a branched chain hydrocarbon having .an average molecular weight in the range of from about 100 to about 1,500, thereby giving the acid an average molecular weight of from about 200 to about 1600.
  • Specific examples of such acids are L-4 phosphorus acid, L-10 phosphorus acid, L-50 phosphorus acid and H-lOO phosphorus acid.
  • the alkyl carboxylic acid is preferably one wherein the alkyl substituent is a branched chain hydrocarbon having an average molecular weight in the range of from about 150 to about 1550, thereby giving the acid an average'molecular weight of from about 200 to about 1,600.
  • Specific examples of such acids are L-4 carboxylic acid, L-lO carboxylic acid, L-50 carboxylic acid, H-l00 carboxylic acid, oleic acid, linoleic acid, eluidic acid and eleostearic acid.
  • Gasoline containing 0.0001 to 0.5 weight percent of a metal complex consisting essentially of the reaction product of equimolar amounts of (a) an alkylbenzene sulfonic acid having an average molecular weight of from about 200 to about 1,600 and containing only alkyl substituents, and (b) the equimolar complex of chromium chloride and pentaethylenehexamine, wherein said reaction product being formed at from about 100F. to about 350F. and said complex being formed at from about F. to about 300F.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

The disclosure describes the reaction product produced by the reaction of about equal molar portions of (1) an alkyl benzene sulfonic acid, an alkyl sulfonic acid, an alkyl phosphorus acid or an alkyl carboxylic acid having an average molecular weight between about 200 and about 1600 and (2) a transition metal complexed with a polyamine.

Description

United States Patent [191 Brannen et al.
[ FUEL AND LUBRICATING OIL ADDITIVES TRANSITION METAL COMPLEXES [75] Inventors: William T. Brannen, West Lake,
Ohio; Roger W. Watson, Highland,
Ill.
[73] Assignee: Standard Oil Company, Chicago, Ill.
[22] Filed: Oct. 10, 1969 21 Appl. No.: 865,496
[52] US. Cl. 44/68, 252/33 [51] Int. Cl C101 1/24 [58] Field of Search..... 252/18, 33, 32.5, 34; 44/68, 44/DlG. 2
[56] References Cited UNlTED STATES PATENTS 3,535,241 lO/l970 Revukas 252/32.5 2,851,417 9/1958 Andress 252/25 R26,433 8/1968 Le Suer 252/34 [451 Feb. 12, 1974 2,464,497 3/1949 Giammaria 252/34 3,306,908 2/1967 Le Suer 252/35 3,351,647 ll/l967 Butler et al. 252/34 2,294,525 9/l942 Waugh 252/34 2,976,238 3/1961 Elliott et al. 252/33 3,649,661 3/1972 Otto et al 252/33 Primary ExaminerPatrick P. Garvin Assistant ExaminerL. Vaughn Attorney, Agent, or Firm--Arthur G. Gilkes; William T. McClain [5 7 ABSTRACT 1 Claim, No Drawings 1 FUEL AND LUBRICATING OIL ADDITIVES TRANSITION METAL COMPLEXES BACKGROUND OF THE INVENTION In many cases it is desirable to have an additive for hydrocarbon fuels which conducts static electricity from the fuel to ground. Such a fuel additive is termed an antistatic agent. These agents are commonly employed by hydrocarbon fuel manufacturers to prevent static charge build up in fuels while they are in transit and thereby reduce the possibility of explosions. The main considerations in formulating an antistatic agent are finding the minimum concentration, the least expensive .components and the most inert formula possible. The purpose of such considerations is to minimize possible undesirable effects of the antistatic agent and produce a low cost antistatic agent.
Alternatively, it is desirable in formulating antistatic agents to find one which is multifunctional. That is, it is desirable to have an antistatic agent which may inhibit oxidation, enhance lubricating properties of the fuel or lubricant to which it is added and/or suspend foreign material to prevent accumulation and deposits on metal surfaces. Frequently, it is the case that multifunctional agents have been discovered but have been too expensive to incorporate as antistatic agents. Also many times such antistatic agents tend to deposit in the induction system of the engine and build up to effect engine performance (the term induction system as used herein is intended to mean the path that the incoming air follows in an automobile engine through the air cleaner, carburetor and intake manifold into the cylinders. This air is of course an air-gasoline mixture after passing through the carburetor.) The problem is then to find an inexpensive antistatic agent that will be multifunctional and will not itself deposit further along the induction system of the engine.
Another important property of antistatic agents is incrtness to other additives which may be incorporated into the hydrocarbon fuel or lubricating oil. Reaction would of course deplete the effective additive in the fuel or lubricating oil and tend to reduce its overall efficiency as well as increase the need for additional additive. Most desirable, then, is an antistatic agent which readily disperses into the hydrocarbon fuel or lubricating oil and serves as a conductive agent, yet remains inert to other active additives in such fuel or lubricating oil.
Designation Average Molecular Weight fuel or lubricating oil additive. It would be used in hydrocarbon fuels in a concentration of from about 0.0001 percent to about 0.5 percent based upon the weight of hydrocarbon fuel. As a fuel additive, the reaction product acts as an antistatic agent, reducing the build up of static electricity during the loading or unloading of fuel. In lubricating oils the reaction product can be added in amounts ranging from about 0.1 percent to about 10 percent based on the weight of oil of lubricating viscosity. As a lubricating oil additive, the reaction product acts as an antistatic agent and inhibits oxidation and wear of metal surfaces as well.
Transition metal complexes useful in the invention of this disclosure are described in The Journal of the American Chemical Society in volume 88 at pages 2156 through 2162 (I966), hereby incorporated by reference. Nonlimiting examples of metal salts useful in forming transition metal complexes are the transition metal chlorides, perchloroates, nitrates, thiocyanates, oxalates, bromides and fluoborates. Nonlimiting examples of the transition metals are those selected from the group consisting of cadmium, chromium, cobalt, copper, iron, manganese, molybdenum, mercury, nickel, rhodium, silver, titanium, tungsten, vanadium and zinc.
Any polyamine can be complexed with the various transition metals. Suitable polyamines generally come within the formula H N (-alkylene-NH),.I-I, in which n is an integer from about 1 to about 12, and alkylene is a saturated divalent hydrocarbon containing from about 1 to about 10 carbon atoms. Suitable polyamines include, for example, butylene polyamines, and cyclic homologues of such polyamines, for example, piperazines. Specific examples of alkylene polyamines are: ethylene diamine, hexamethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, hexaethyleneheptamine and N-2-aminoethylpiperazine. Polyethylene polyamines are generally preferred, pentaethylenehexamine being particularly preferred since the transition metals generally form hexacoordinate complexes.
PREFERRED EMBODIMENTS For simplicity in the following examples, the designations below shall mean an alkyl substituent attached to an alkyl benzene sulfonic acid, alkyl sulfonic acid, alkyl phosphorus acid or alkyl carboxylic acid having an average molecular weight and an average number of carbon atoms as follows:
Average Number of Carbon Atoms SUMMARY OF THE INVENTION Briefly, the invention can be described as the reaction product produced by the reaction between about equal molar portions of (1) an alkyl benzene sulfonic acid, an alkyl sulfonic acid, an alkyl phosphoric acid or an alkyl carboxylic acid having an average molecular weight between about 200 and about 1,600, and (2) a transition metal complex of a polyamine.
The reaction product is proposed as a hydrocarbon EXAMPLE I exemplified in The Journal of the American Chemical Society (previously cited).
The alkyl benzene sulfonic acid is preferably one wherein the alkyl substituent is a branched chain hydrocarbon having an average molecular weight in the range of from about 50 to about 1,450, thereby giving the acid an average molecular weight of from about 200 to about 1,600. Specific examples of such acids are L-4 benzene sulfonic acid, L-l benzene sulfonic acid, L-50 benzene sulfonic acid and l-l-l00 benzene sulfonic acid.
The alkyl sulfonic acid is preferably one wherein the alkyl substituent is a branched chain hydrocarbon having an average molecular weight in the range of from about 100 to about 1,500, thereby giving the acid an average molecular weight of from about 200 to about 1,600. Specific examples of such acids are L-4 sulfonic acid, L-l0 sulfonic acid, L 50 sulfonic acid and 11-100 sulfonic acid.
The alkyl phosphorus acid is preferably one wherein the alkyl substituent is a branched chain hydrocarbon having .an average molecular weight in the range of from about 100 to about 1,500, thereby giving the acid an average molecular weight of from about 200 to about 1600. Specific examples of such acids are L-4 phosphorus acid, L-10 phosphorus acid, L-50 phosphorus acid and H-lOO phosphorus acid.
The alkyl carboxylic acid is preferably one wherein the alkyl substituent is a branched chain hydrocarbon having an average molecular weight in the range of from about 150 to about 1550, thereby giving the acid an average'molecular weight of from about 200 to about 1,600. Specific examples of such acids are L-4 carboxylic acid, L-lO carboxylic acid, L-50 carboxylic acid, H-l00 carboxylic acid, oleic acid, linoleic acid, eluidic acid and eleostearic acid.
What is claimed is:
1. Gasoline containing 0.0001 to 0.5 weight percent of a metal complex consisting essentially of the reaction product of equimolar amounts of (a) an alkylbenzene sulfonic acid having an average molecular weight of from about 200 to about 1,600 and containing only alkyl substituents, and (b) the equimolar complex of chromium chloride and pentaethylenehexamine, wherein said reaction product being formed at from about 100F. to about 350F. and said complex being formed at from about F. to about 300F.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991018075A1 (en) * 1990-05-16 1991-11-28 N.V. Bekaert S.A. Additive for lubricants containing a metal complex
US5650382A (en) * 1993-01-14 1997-07-22 N.V. Bekaert S.A. Additive for lubricants containing a metal complex
US20100292113A1 (en) * 2009-05-15 2010-11-18 Afton Chemical Corporation Lubricant formulations and methods

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US26433A (en) * 1859-12-13 John b
US2294525A (en) * 1940-12-23 1942-09-01 Tide Water Associated Oil Comp Inhibitor
US2464497A (en) * 1946-03-12 1949-03-15 Socony Vacuum Oil Co Inc Mineral oil composition
US2851417A (en) * 1953-04-10 1958-09-09 Socony Mobil Oil Co Inc Complex alkoxy metal salts of organic acids and lubricating and fuel compositions thereof
US2976238A (en) * 1956-12-24 1961-03-21 Castrol Ltd Oil-based compositions
US3306908A (en) * 1963-12-26 1967-02-28 Lubrizol Corp Reaction products of high molecular weight hydrocarbon succinic compounds, amines and heavy metal compounds
US3351647A (en) * 1963-05-14 1967-11-07 Lubrizol Corp Nitrogen, phosphorus and metal containing composition
US3535241A (en) * 1965-05-26 1970-10-20 Cities Service Oil Co Lubricating oils containing polyvalent metal hydrocarbyl pyrophosphate salts and amine adducts thereof
US3649661A (en) * 1970-03-24 1972-03-14 Mobil Oil Corp Coordinated complexes of nitrogenous compounds

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US26433A (en) * 1859-12-13 John b
US2294525A (en) * 1940-12-23 1942-09-01 Tide Water Associated Oil Comp Inhibitor
US2464497A (en) * 1946-03-12 1949-03-15 Socony Vacuum Oil Co Inc Mineral oil composition
US2851417A (en) * 1953-04-10 1958-09-09 Socony Mobil Oil Co Inc Complex alkoxy metal salts of organic acids and lubricating and fuel compositions thereof
US2976238A (en) * 1956-12-24 1961-03-21 Castrol Ltd Oil-based compositions
US3351647A (en) * 1963-05-14 1967-11-07 Lubrizol Corp Nitrogen, phosphorus and metal containing composition
US3306908A (en) * 1963-12-26 1967-02-28 Lubrizol Corp Reaction products of high molecular weight hydrocarbon succinic compounds, amines and heavy metal compounds
US3535241A (en) * 1965-05-26 1970-10-20 Cities Service Oil Co Lubricating oils containing polyvalent metal hydrocarbyl pyrophosphate salts and amine adducts thereof
US3649661A (en) * 1970-03-24 1972-03-14 Mobil Oil Corp Coordinated complexes of nitrogenous compounds

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991018075A1 (en) * 1990-05-16 1991-11-28 N.V. Bekaert S.A. Additive for lubricants containing a metal complex
BE1004265A3 (en) * 1990-05-16 1992-10-20 Bekaert Sa Nv Additive lubricants comprising metal complex.
TR25289A (en) * 1990-05-16 1993-01-01 Bekaert Sa Nv ADDITIVES WITH A METAL COMPLEX FOR LUBRICANTS
AU653522B2 (en) * 1990-05-16 1994-10-06 N.V. Bekaert S.A. Additive for lubricants containing a metal complex
US6150308A (en) * 1990-05-16 2000-11-21 Deruyck; Frank Additive for lubricants containing a metal complex
US5650382A (en) * 1993-01-14 1997-07-22 N.V. Bekaert S.A. Additive for lubricants containing a metal complex
US20100292113A1 (en) * 2009-05-15 2010-11-18 Afton Chemical Corporation Lubricant formulations and methods

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