[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

US3073853A - Trimethyl lead methyl sulfide - Google Patents

Trimethyl lead methyl sulfide Download PDF

Info

Publication number
US3073853A
US3073853A US59519A US5951960A US3073853A US 3073853 A US3073853 A US 3073853A US 59519 A US59519 A US 59519A US 5951960 A US5951960 A US 5951960A US 3073853 A US3073853 A US 3073853A
Authority
US
United States
Prior art keywords
lead
methyl sulfide
gasoline
trimethyl
percent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US59519A
Inventor
Ballinger Peter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
California Research LLC
Original Assignee
California Research LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by California Research LLC filed Critical California Research LLC
Priority to US59519A priority Critical patent/US3073853A/en
Priority to US141637A priority patent/US3116127A/en
Application granted granted Critical
Publication of US3073853A publication Critical patent/US3073853A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/24Lead compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/30Organic compounds compounds not mentioned before (complexes)
    • C10L1/305Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
    • C10L1/306Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond) organo Pb compounds

Definitions

  • This invention relates to a novel organometal compound. More particularly, the invention is concerned with a superior new lead sulfide antiknock compound for hydrocarbon fuels of the gasoline boiling range.
  • Gasoline compositions of high octane number are commonly required for modern spark ignition internal combustion automobile and aircraft engines. Engines of these types in general use today are designed with high compression ratios for more efiicient operation. Since the present trend is toward engines of still higher compression ratios for increased power and improved performance, there is a constant demand for gasoline compositions of even higher octane number.
  • a superior new gasoline composition of high octane number is provided by a hydrocarbon base fuel boiling in the gasoline boiling range, containing trimethyl lead methyl sulfide, a novel lead compound, in amounts sutficient to improve the octane number, preferably, at least 0.5 milliliter per gallon of base fuel.
  • the improved gasoline compositions containing the new antiknock compound of the invention show unexpectedly high octane numbers.
  • Hydrocarbon base fuels, together with trimethyl lead methyl sulfide and mixtures thereof in accordance with the invention have octane numbers which are practically equivalent to similar base fuels employing the conventional lead tetraethyl additive in the same lead content. This is surprising since it has been generally accepted heretofore that other lead compounds are distinctly less efficient than lead tetraethyl with respect to octane number improvement. Furthermore, it has been widely recognized that sulfur is ordinarily antagonistic to lead antidetonants.
  • the hydrocarbon base fuel of the composition, according to the invention is prepared by conventional refining and blending processes. It normally contains straightchain parafiins, branched-chain paraffins, olefins, aromatics and naphthenes. Since straight-chain parafiins have a tendency to adversely affect octane number, the content of such hydrocarbons is ordinarily low.
  • the base fuel is a hydrocarbon fuel boiling in the gasoline boiling range.
  • such fuels have an ASTM (13-86) distillation with an initial boiling point of about 100 F. and a final boiling point of about 425 F.
  • the unleaded base fuel has a research octane number of at least 85 as determined by the accepted CFR engine test method.
  • the base fuel preferably contains at least 20 percent by volume of aromatic hydrocarbons. Less than 30 percent by volume of olefinic hydrocarbons are present in the fuel.
  • the total paraffin and naphthene hydrocarbon content of the preferred fuel may be as much as 80 percent by volume. For best over-all engine performance,
  • a gasoline having all-around desirable characteristics has a clear octane number of at least and contains about 50 to 60 percent by volume of paraffin and naphthene hydrocarbons, about 30 to 40 percent aromatic hydro carbons and about 5 to 15 percent olefinic hydrocarbons.
  • the trimethyl lead methyl sulfide is illustrated by the general formula OH; CHa-PlL-S-CH:
  • octane-improving additives may be employed in addition to trimethyl lead methyl sulfide.
  • lead compounds such as lead tetraethyl, carbonyl derivatives of iron and cyclopentadienyl derivatives of metals such as manganese or iron.
  • Other gasoline additives such as scavengers like ethylene chloride or bromide, oxidation inhibitors, corrosion inhibitors, surface ignition suppressants like phosphorus compounds, detergents, and the like may be prescut.
  • EMMPLE I This example shows the preparation of trimethyl lead methyl sulfide. Twenty-four grams (0.5 mole) of methyl mercaptan are cooled to 0 C. and dissolved in 500 ml. of 4 N sodium hydroxide at 0 C. To this solution is added with stirring a solution of 144.0 g. (0.5 mole) of trimethyl lead chloride in water. On standing for onehalf hour, a heavy liquid separates and is removed in a separatory funnel, dried with calcium chloride, and fractionated to a pat temperature of 70 C. at a pressure of 1 mm. of mercury. The boiling point is found to be 43 C. at a pressure of 0.75 mm. of mercury. The refractive index 11 is 1.6116. The infrared spectrum checks that of the predicted compound by comparison with the spectra of known alkyl lead compounds, alkyl sulfides, and mercaptides.
  • the hydrocarbon base fuel contains 51 percent by volume of the parafiins and naphthenes, 25 percent olefins, and 24 percent aromatics.
  • the fuel has a sulfur content of about 0.06 percent by weight.
  • the table shows the effect on octane number by the addition of trimethyl lead methyl sulfide compared with lead tetraethyl. The octane numbers in this comparison are based on the Research Method D-908 and the Motor Method D-357 of the ASTM Manual of Engine Test.
  • the organolead compounds of this invention are also useful Wherever oil-soluble lead compounds are desired.
  • fine particle dispersions of lead may be obtained by thermal decomposition of the trialkyl lead sulfide dissolved in liquid hydrocarbon, such as isooctane.
  • Such fine metal dispersions of lead are useful as catalysts for certain reactions.
  • the fine lead particles may be converted to lead oxides which are useful as lubrication agents.
  • the lead compound of the invention may also be used as a free radical initiator in polymerization reactions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

" nited "1 t ration of Delaware No Drawing. Filed Sept. 30, 1960, Ser. No. 59,519 1 Claim. (Cl. 260437) This invention relates to a novel organometal compound. More particularly, the invention is concerned with a superior new lead sulfide antiknock compound for hydrocarbon fuels of the gasoline boiling range.
Gasoline compositions of high octane number are commonly required for modern spark ignition internal combustion automobile and aircraft engines. Engines of these types in general use today are designed with high compression ratios for more efiicient operation. Since the present trend is toward engines of still higher compression ratios for increased power and improved performance, there is a constant demand for gasoline compositions of even higher octane number.
Improved methods of refining and blending gasoline base stocks, and additives such as lead tetraethyl, have been employed to meet the demands for higher octane number gasoline compositions. However, it has been generally realized that there is at present a limit to the improvement in octane number that can be obtained by such conventional methods and additives. New gasoline base stocks with the combination of different additives are greatly needed, therefore, to avoid present limitations and provide gasoline compositions of high octane number for future use in automobile and aircraft engines.
It has now been found that a superior new gasoline composition of high octane number is provided by a hydrocarbon base fuel boiling in the gasoline boiling range, containing trimethyl lead methyl sulfide, a novel lead compound, in amounts sutficient to improve the octane number, preferably, at least 0.5 milliliter per gallon of base fuel.
The improved gasoline compositions containing the new antiknock compound of the invention show unexpectedly high octane numbers. Hydrocarbon base fuels, together with trimethyl lead methyl sulfide and mixtures thereof in accordance with the invention, have octane numbers which are practically equivalent to similar base fuels employing the conventional lead tetraethyl additive in the same lead content. This is surprising since it has been generally accepted heretofore that other lead compounds are distinctly less efficient than lead tetraethyl with respect to octane number improvement. Furthermore, it has been widely recognized that sulfur is ordinarily antagonistic to lead antidetonants.
The hydrocarbon base fuel of the composition, according to the invention is prepared by conventional refining and blending processes. it normally contains straightchain parafiins, branched-chain paraffins, olefins, aromatics and naphthenes. Since straight-chain parafiins have a tendency to adversely affect octane number, the content of such hydrocarbons is ordinarily low.
As already mentioned, the base fuel is a hydrocarbon fuel boiling in the gasoline boiling range. Generally described, such fuels have an ASTM (13-86) distillation with an initial boiling point of about 100 F. and a final boiling point of about 425 F. Preferably, the unleaded base fuel has a research octane number of at least 85 as determined by the accepted CFR engine test method. Also, the base fuel preferably contains at least 20 percent by volume of aromatic hydrocarbons. Less than 30 percent by volume of olefinic hydrocarbons are present in the fuel. The total paraffin and naphthene hydrocarbon content of the preferred fuel may be as much as 80 percent by volume. For best over-all engine performance,
ates Patent Patented Jan. 15, 1963 fuels containing in the range of 20 to 60 percent by volume of parafiinic and naphthenic hydrocarbons are preferred for volatility and other desirable gasoline characteristics. The more preferred hydrocarbon base fuels are also those which contain from 20 to 60 percent by volume aromatic hydrocarbons and from 0 to 30 percent by volume of olefinic hydrocarbons. Most preferably, a gasoline having all-around desirable characteristics has a clear octane number of at least and contains about 50 to 60 percent by volume of paraffin and naphthene hydrocarbons, about 30 to 40 percent aromatic hydro carbons and about 5 to 15 percent olefinic hydrocarbons.
The trimethyl lead methyl sulfide is illustrated by the general formula OH; CHa-PlL-S-CH:
For practical purposes, not more than about 4 milliliters of lead compounds per gallon is ordinarily used in the compositions. If desired, other octane-improving additives may be employed in addition to trimethyl lead methyl sulfide. These include other lead compounds such as lead tetraethyl, carbonyl derivatives of iron and cyclopentadienyl derivatives of metals such as manganese or iron. Other gasoline additives, such as scavengers like ethylene chloride or bromide, oxidation inhibitors, corrosion inhibitors, surface ignition suppressants like phosphorus compounds, detergents, and the like may be prescut.
The following examples illustrate the composition of trimethyl lead methyl sulfide in accordance with this invention. Unless otherwise specified the proportions are on a weight basis.
EMMPLE I This example shows the preparation of trimethyl lead methyl sulfide. Twenty-four grams (0.5 mole) of methyl mercaptan are cooled to 0 C. and dissolved in 500 ml. of 4 N sodium hydroxide at 0 C. To this solution is added with stirring a solution of 144.0 g. (0.5 mole) of trimethyl lead chloride in water. On standing for onehalf hour, a heavy liquid separates and is removed in a separatory funnel, dried with calcium chloride, and fractionated to a pat temperature of 70 C. at a pressure of 1 mm. of mercury. The boiling point is found to be 43 C. at a pressure of 0.75 mm. of mercury. The refractive index 11 is 1.6116. The infrared spectrum checks that of the predicted compound by comparison with the spectra of known alkyl lead compounds, alkyl sulfides, and mercaptides.
In further illustration of the superior new gasoline antiknock compound of the invention, several compositions and tests thereon are given in the following examples. These tests show the improved effect of the combination of particular hydrocarbon base fuels with trimethyl lead methyl sulfide.
The following table is a summary of the pertinent data of the examples. The hydrocarbon base fuel contains 51 percent by volume of the parafiins and naphthenes, 25 percent olefins, and 24 percent aromatics. The fuel has a sulfur content of about 0.06 percent by weight. The table shows the effect on octane number by the addition of trimethyl lead methyl sulfide compared with lead tetraethyl. The octane numbers in this comparison are based on the Research Method D-908 and the Motor Method D-357 of the ASTM Manual of Engine Test.
Methods for Rating Fuels. The latter method, which is more stringent than the research method, illustrates more accurately the desirable qualities of the improved gasoline composition of the invention.
In the table, the effect of trimethyl lead methyl sulfide and lead tetraethyl is based on gasoline compositions containing an equal lead concentration. For the purpose of practical comparison this is 3.17 grams of lead per gallon. Such amounts are equivalent to the 3 cc. of tetraethyl lead per gallon employed in many gasolines. The gasolines containing the trimethyl lead methyl sulfide have approximately 0.02 percent of leadbound sulfur in addition to the sulfur already present.
The examples summarized in the above table show that the improved gasoline composition of the invention containing the novel triznethyl lead methyl sulfide of the invention is surprisingly comparable on the basis of octane number rating to gasoline compositions of the type preferred heretofore.
The organolead compounds of this invention are also useful Wherever oil-soluble lead compounds are desired. For example, fine particle dispersions of lead may be obtained by thermal decomposition of the trialkyl lead sulfide dissolved in liquid hydrocarbon, such as isooctane. Such fine metal dispersions of lead are useful as catalysts for certain reactions. The fine lead particles may be converted to lead oxides which are useful as lubrication agents. The lead compound of the invention may also be used as a free radical initiator in polymerization reactions.
I claim:
Trimethyl lead methyl sulfide.
References Cited in the file of this patent UNITED STATES PATENTS 1,949,948 Alleman Mar. 6, 1934 2,936,224 Fontana May 10, 1960 2,938,776 Hamer May 31, 1960 2,955,124 Blitzer et a1. Oct. 4, 1960 OTHER REFERENCES Chem. Reviews, vol. 54, No. 1, p. 143, 260-437.
US59519A 1960-09-30 1960-09-30 Trimethyl lead methyl sulfide Expired - Lifetime US3073853A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US59519A US3073853A (en) 1960-09-30 1960-09-30 Trimethyl lead methyl sulfide
US141637A US3116127A (en) 1960-09-30 1961-09-29 Gasoline containing organometal compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US59519A US3073853A (en) 1960-09-30 1960-09-30 Trimethyl lead methyl sulfide

Publications (1)

Publication Number Publication Date
US3073853A true US3073853A (en) 1963-01-15

Family

ID=22023486

Family Applications (1)

Application Number Title Priority Date Filing Date
US59519A Expired - Lifetime US3073853A (en) 1960-09-30 1960-09-30 Trimethyl lead methyl sulfide

Country Status (1)

Country Link
US (1) US3073853A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3287265A (en) * 1963-04-01 1966-11-22 Int Lead Zinc Res Lubricating oil and additive
US3322779A (en) * 1963-04-01 1967-05-30 Int Lead Zinc Res Di- and triphenyllead sulfides having substituent radicals joined to the sulfur atom
US3683090A (en) * 1970-06-15 1972-08-08 Malcolm C Henry Methods of repelling rodents using tetravalent organo-lead compounds

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1949948A (en) * 1929-01-18 1934-03-06 Sun Oil Co Hydrocarbon derivatives of lead and their preparation
US2936224A (en) * 1957-09-06 1960-05-10 California Research Corp Gasoline composition
US2938776A (en) * 1955-04-26 1960-05-31 Standard Oil Co Distillate fuel composition
US2955124A (en) * 1957-02-27 1960-10-04 Ethyl Corp Manufacture of organolead compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1949948A (en) * 1929-01-18 1934-03-06 Sun Oil Co Hydrocarbon derivatives of lead and their preparation
US2938776A (en) * 1955-04-26 1960-05-31 Standard Oil Co Distillate fuel composition
US2955124A (en) * 1957-02-27 1960-10-04 Ethyl Corp Manufacture of organolead compounds
US2936224A (en) * 1957-09-06 1960-05-10 California Research Corp Gasoline composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3287265A (en) * 1963-04-01 1966-11-22 Int Lead Zinc Res Lubricating oil and additive
US3322779A (en) * 1963-04-01 1967-05-30 Int Lead Zinc Res Di- and triphenyllead sulfides having substituent radicals joined to the sulfur atom
US3683090A (en) * 1970-06-15 1972-08-08 Malcolm C Henry Methods of repelling rodents using tetravalent organo-lead compounds

Similar Documents

Publication Publication Date Title
US3224848A (en) Gasoline composition
US4294587A (en) Motor fuel
US2860958A (en) Antiknock compositions
US3073854A (en) Trimethyllead methyl thioglycolate
US3073853A (en) Trimethyl lead methyl sulfide
US4339245A (en) Motor fuel
US2819953A (en) Fuel composition
US2324779A (en) Motor fuel
US3009793A (en) Motor fuel containing synergistic anti-knock additive
US3010980A (en) Trialkyl lead selenides
US3303007A (en) Motor fuel composition
US2560602A (en) Fuel composition
US4295861A (en) Motor fuel
US3116127A (en) Gasoline containing organometal compound
US3222146A (en) Glycerol esters in leaded gasoline
US3083086A (en) N-propyl n-butyrate in leaded gasoline
US2901336A (en) Antiknock compositions
US3073852A (en) Bis (trimethyllead) sulfide
US3143399A (en) Gasoline containing organometal antiknock compound
US3015547A (en) Motor fuel containing octane improver
US4341529A (en) Motor fuel
US4387257A (en) Motor fuel
US3143400A (en) Gasoline containing organolead compound
US4321063A (en) Motor fuel
US3116126A (en) Antiknock gasoline