Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.


  1. Advanced Patent Search
Publication numberUS3112271 A
Publication typeGrant
Publication dateNov 26, 1963
Filing dateApr 13, 1959
Priority dateApr 13, 1959
Publication numberUS 3112271 A, US 3112271A, US-A-3112271, US3112271 A, US3112271A
InventorsGeorge M Calhoun
Original AssigneeShell Oil Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Liquid hydrocarbon composition
US 3112271 A
Abstract  available in
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,112,271 LIQUID HYDROCARBON COMPOSITION George M. Calhoun, Berkeley, Calif., assignor to Shell Oil Company, New York, N'.Y;, a corporation of Delaware No Drawing. Filed Apr. 13, 1959, Ser. No. 805,686 5 Claims. (Cl. 25246.6)

acids and polyhydric alcohols or alkyl or aryl pho-sphites or phosphates, or free fatty acids and sulfur derivatives thereof such as C1043 fatty acids (oleic or stearic acids) and sulfurized unsaturated fatty acids, e.g., sulfun'zed oleic acid. However, these compounds when used in liquid hydrocarbons, such as lubricating oil compositions which are subjected to high temperatures and pressures break down and fail to impart their expected desired properties under these extreme conditions.

It has now been discovered that liquid hydrocarbon compositions are improved with respect to stability, wear inhibition and extreme pressure properties and contribute to minimizing octane requirement increase when used in an internal combustion engine, and the like by incorporating therein a minor amount of an oil-soluble Z-thiaalkyl phosphorus-containing compound having the general formula:

XRI (I) wherein R is an oil-soluble hydrocarbyl group, such as an alkyl, aryl, aralkyl, alkaryl or cycloalkyl radical having at least 6 and preferably a straight-chain alkyl radical having from to 18 carbon atoms, the Rfs are thesame or different groups selected from hydrogen, hydrocarbyl,

or amine, preferably an alkylamine and the Xs are independently chalcogen atoms having an atomic number of from 8 to 16, such as oxygen or sulfur. Preferred compounds of the general Formula I have the following formula:

0 OH 10-18 alkyl-s-om-i or the amine sals thereof represented-by 0 OH-(A) 010-18 a1kyl-SCHr--P 011 (III) 0 OH-(A) Cloalkyl-SCH2-i and of the above formulas it is preferred that the alkyl portion of the molecule be C1048 alkyl CHR -S-CH and wherein R is hydrogen or a short alkyl radical of 1-4 carbon atoms, A is an aliphatic amine, preferably a primary or secondary amine, such as C primary straight chain amines, e.g., octylamine, laurylamine,

3,112,271 Patented Nov. 26, 1963 stearylamine, etc., or branched chain primary aliphatic amines, e.g., t-C alkylamine, such as t-C H N'l-l t-C1 H 5NH t0 t-C 5H3LNH2 01' t-C12H 5NH2 t0 t-C H LNH or C 1 secondary aliphatic amines, such as diamylamine, di-Z-ethylhexylamine, didecylamine, etc.

The Z-thiaalkylphosphonic compounds are prepared by reacting a mercaptan or mercaptide having at least 6 carbon atoms with a halomethylphosphono compound such as chloromethylphosphonic acid or chloromethylphosphonate or their thioderivatives in a suitable solvent, such as an aqueous alcoholic solution, at reflux temperature and under inert conditions until the reaction is completed which normally requires from 1 to about 5 days. The mercaptans include aliphatic mercaptans, such as hexyl, octyl, decyl, dodecyl, octadecyl mercaptans, cycloalkyl mercaptans, such as cyclohexyl mercaptan, dicyclohexyl mercaptan, aralkyl mercaptan; such as phenyldecyl mercaptan, benzyl mercaptan and the like. Instead. of the mercaptans, the mercaptides can be used such as the alkali metal (Na or K) mercaptides of the above compounds. Suitable halomethylphosphonic compounds inelude chloromethylphosphonic acid, mono or dihydrocarbyl chloromethylphosphonates, e.g., mono or dibutyl chloromethylphosphonate, mono or di-Z-ethylhexyl chloromethylphosphonate, mono or dilauryl ohloromethylphosphonate, mono or diphenyl :chloromethylphosphonate, mono or dicyclohexyl chloromethylphosphonate, mono or dibenzyl chloromethylphosphonate, dibutyl dithiochloromethylphosphonate, diphenyl chloromethyl dithiophosphonate, dibutyl chloromethyl-trithiophosphonate, alkali metal salts such as Na and K salts of chloromethylphosphonic acid, Na and K salts of monobutyl chloromethylphosphonic acid, Na and K salt of monodecyl chloromethylphosphonic acid and the like.

A preferred method of making the Z-thiaalkylphosphonates is to react a suitable mercapto compound, such as an alkali metal (Na or K) C1048 alkyl mercaptide with an alkali metal (Na or K) salt of chloromethylphosphonic acid in an alcoholic solution under reflux conditions and under an inert atmosphere to form the alkali metal salt of an a1kylmercaptomethylphosphonic acid. The salt is then treated with a strong acid such as hydrochloric acid to spring the free alkylmercaptomethylphosphonic acid, which can be converted into desired partial or full esters or polyvalent metal salts or amine salts for use as oil, fuel and grease additives as well as other uses.

The following examples illustrate the preparation of additives for use in accordance with the present invention.

EXAMPLE I Per- Per- Per- Per- Equiv Equiv.

cent cent cent cent Wt. 1st Wt. Both 0 H S P Hydrogen Hydrogens Found 49.1 9.4 12.0 11.2 261 132 Expected.-. 49.2 9.4 11.94 11.54 268.3 134.1

EXAMPLE -II The procedure of Example I was followed except'that potassium salt of phenylmercaptan was used instead of potassium salt of decylmercaptan and the final product was phenylmercaptomethylphosphonic acid.

3 EXAMPLE III The dibutyl ester of decylmercaptomethylphosphonic acid of Example I was prepared by treating decylmercaptomethylphosphonic acid with butyl alcohol in an alcoholic solution at about 60 and extracting the ester with ether.

EXAMPLE IV Di-Z-ethylhexylamine salt of decylmercaptomethylphosphonic acid (Z-thiadodecylphosphonic acid) was prepared by reacting the product of Example I with di-2-ethylhexylamine in an amount sufficient to completely neutralize both acid groups, at about 50 C. in an alcoholic solution and thereafter recovering the amine salt from the alcoholic solution.

EXAMPLE V Following the procedure of Example IV, the tert-octadecylamine salt of decylmercaptomethylphosphonic acid was prepared using tertoctadecylamine, available commercially under the trade-name of Primene IM-R, instead of di-2-ethylhexylamine.

The following additional compounds were prepared: octylmercaptomethylphosphonic acid, dodecylmercaptomethylphosphonic acid, cyclohexylmercaptomethylphosphonic acid, benzylmercaptomethylphosphonic acid, phenylmercaptomethylphosphonic acid, dibutyl decylmercaptomethylphosphonate, phenyldecylmercaptomethyl acid phosphonate, dithiobutyl dodecylmercaptomethylphosphonate, dibutyl phenylmercaptomethylphosphonate, dithiooctyl cyclohexylmercaptomethylthiophosphonate, dioctylamine dodecylmercaptomethylphosphonate, dioctadecylamine phenylmercaptomethylphosphonate, tert-octa decylamine dodecylmercaptomethylphosphonate and mixtures thereof.

The additives of this invention are believed to be novel compounds. They are oil-soluble and can be used in amounts of from about 0.1% to about 25%, preferably from about 0.5% to about 5.0% by weight.

Mercaptomethylphosphono compounds of this invention are outstanding additives for various liquid hydrocarbon products, such as natural and synthetic hydrocarbon lubricating oils, greases, fuels (gasoline, kerosene, gas oil, burner fuel oil), asphalts, waxes, slushing oils, industrial oils, e.g., metal working and drawing oils, quenching oils, textile oils, hydraulic oils, dielectric compositions and other industrial oils. They are particularly outstanding when added in small amounts to lubricating oils and lubricating compositions to impart extreme pressure and anti-wear properties to such materials. Also, these additives are useful additives for gasoline, fuel oils, and other light oil products.

Lubricating oils useful for the preparation of compositions of this invention can be one or more of a variety of synthetic oils or natural hydrocarbon oils having a viscosity range of from 50 SUS at 100 F. to 250 SUS at 210 F. (SAE viscosity number ranging from SAE W to SAE 90). The natural hydrocarbon oils can be obtained from parafiinic naphthenic, asphaltic or mixed base crudes, and/or mixtures thereof. Synthetic oils include polymerized olefins, alkylated aromatics, isomerized waxes, copolymers of alkylene glycols and alkylene oxides (Ucon fluids) which are described in U.S. Patents 2,425,755, 2,425,845 and 2,774,733 such as Ucon 50HB170, Ucon 50HB660 or Ucon LB550X and which are copolymers of ethylene and 1,2-propylene oxides, the mono and diols, as well as their ester derivatives; organic esters of aliphatic dibasic acids such as di-2-ethylhexyl sebacate or di-Z-ethylhexyl adipate and the like. The hydrocarbon oils may be blended with fixed oils such as castor oil, lard oil and the like and/or synthetic oils as mentioned or silicone polymers and the like. Two typical oils A and B are paratfinic and naphthenic in character, respectively, having the following properties:

Other suitable oils are the gas turbine lube oils having the following properties:

Grade 1010 1065 Flash, 000, F 300 465 Four, F -10 0 Viscosity, SUS at 100 F 59. 4 530 Neutral Number 0. 02 0. 01. A h None None The following compositions are illustrative of the invention, the percentages being by weight, of the indicated additive or additives with the remainder being essentially the base.

Percent Composition A:

Example I additive 2 1010 mineral oil Balance Composition B:

Example II additive 2 1010 mineral oil Balance Composition C:

Example III additive 2 1010 mineral oil Balance Composition D:

Example IV additive 2 1010 mineral oil Balance Composition E:

Example II additive 1 SAE 30 mineral oil Balance Composition F:

Example I additive 2 SAE mineral oil Balance Composition G:

Example I additive 2 Laurie acid 2 SAE 90 mineral oil Balance Composition H:

Example I additive 5 Ucon 50HB660 (polyethylene-propylene glycol having a SUS viscosity at F. of 660) Balance Composition 1:

Example I additive 2 Di-Z-ethylhexyl sebacate Balance Composition J Example I additive 1 Leaded gasoline (3 cc. of TEL) Balance Composition K:

Example I additive 01 Fuel oil (No. 2) Balance were:

Speed .p.m 3200 Oil temperature C 100 Oil flow-rate cc./scc 10 Load in increments 5 min. at each setting.

Results of the evaluations are given in Table I and for the purpose of comparison, the results obtained from the use of the base oil alone and with other known extreme pressure compositions are also given.

The following compositions were also tested for stability in the Dornt oxidation test described in the Natural Petroleum News, September 17, 1941, pages 2946, under the following conditions: 302 F., iron catalyst, mineral white oil base and additive amount in each example was about 1% by weight and the results are shown in Table II.

Table II Additive Induction period (hrs) (1) n-Decylmercaptomethylphosphonic acid 140 (n-C ioH21SCH2 1 (OH) 2) (2) 2-Ethylhexylmercaptomethylphosphonic acid 80 O (CHaC1-I2CH2CH2CHCH2SCH2%-(OH)2) (52H!) (3) n-Decylmercaptoethylphosphonic acid 14 The mercaptomethylphosphono compounds of this invention are useful also for providing superior load-carrying properties for lubricating oils which contain minor amounts of other agents, such as silicone anti-foaming agents, alkylphenol anti-oxidants, polyacrylate ester viscosity-index improvers, long chain fatty acids such as lauric and oleic acids, oiliness agents and the like.

I claim as my invention:

1. A lubricating oil composition comprising a major amount of lubricating oil and a minor amount, sufiicient to impart extreme pressure properties to the lubricating oil, of an oil-soluble alkylmercaptomethylphosphono compound having the general formula wherein R is a C -C saturated alkyl radical, the R s are selected independently from the group consisting of hydrogen, and C -C saturated alkyl radical.

2. A lubricating oil composition consisting essentially of a major amount of mineral lubricating oil and from about 0.1% to about 5% of a C1048 alkylmercaptomethylphosphonic acid.

3. A lubricating oil composition consisting essentially of a major amount of mineral lubricating oil and from about 0.1% to about 5% of an ester of C1048 alkylmercaptomethylphosphonic acid.

4. A lubricating oil composition consisting essentially of a major amount of mineral lubricating oil and from about 0.1% to about 5% of decylmercaptomethylphosphonic acid.

5. A lubricating oil composition consisting essentially a major amount of mineral lubricating oil and from about 0.1% to about 5% of an ester of decylmercaptomethylphosphonic acid.

References Cited in the file of this patent UNITED STATES PATENTS 2,346,155 Denison et al Apr. 11, 1944 2,391,099 McNab et al Dec. 18, 1945 2,535,174 Tawney Dec. 26, 1950 2,689,220 Mulvany Sept. 14, 1954 2,724,718 Stiles et al Nov. 22, 1955 2,737,492 Beegle et a1. Mar. 6, 1956 2,857,305 Birum Oct. 21, 1958 2,881,201 Schrader Apr. 7, 1959 2,971,019 Ladd et a1. Feb. 7, 1961 FOREIGN PATENTS 751,755 Great Britain July 4, 1956 804,141 Great Britain Nov. 12, 1958 OTHER REFERENCES Arbuzov et al.: Syntheses of Some Phosphone Sulfides and Phosphone Silfones, in J. Gen. Chem, U.S.S.R. 27, pages 2419-21, September 1957.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2346155 *Feb 23, 1942Apr 11, 1944Standard Oil CoCompounded oil
US2391099 *Dec 31, 1941Dec 18, 1945Standard Oil Dev CoLubricating oil composition
US2535174 *Apr 7, 1949Dec 26, 1950Us Rubber CoMercaptoethanephosphonates
US2689220 *Mar 29, 1951Sep 14, 1954California Research CorpLubricating oil compositions of mixed diester dithiophosphates
US2724718 *Apr 12, 1948Nov 22, 1955Shell DevPreparation of phosphorus-containing organic compounds
US2737492 *Mar 26, 1952Mar 6, 1956American Cyanamid CoLubricating oil compositions
US2857305 *Dec 30, 1955Oct 21, 1958Monsanto ChemicalsPhosphonate esters
US2881201 *Dec 1, 1955Apr 7, 1959Bayer AgSubstituted mercaptoalkyl esters of phosphoric acids and their derivatives
US2971019 *Mar 17, 1953Feb 7, 1961Us Rubber CoOrgano-phosphorus compounds
GB751755A * Title not available
GB804141A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3197497 *Mar 16, 1962Jul 27, 1965Monsanto CoAllenic phosphorus derivatives
US3205252 *Mar 26, 1963Sep 7, 1965Socony Mobil Oil Co IncThiophosphonous acid ester insecticides
US3223754 *Nov 29, 1960Dec 14, 1965Bayer AgAlkyl mercapto alkyl esters of substituted phosphonic acids
US3226322 *Dec 28, 1961Dec 28, 1965Shell Oil CoLiquid hydrocarbon composition and additives therefor
US3235628 *Jul 8, 1964Feb 15, 1966Shell Oil Co2-thiaphosphono compounds
US3305610 *Jul 2, 1963Feb 21, 1967Stauffer Chemical CoPhosphonodithioates as pesticides
US3326749 *Jul 5, 1963Jun 20, 1967Monsanto CoAlkylphosphonothioates
US3485918 *Jun 24, 1966Dec 23, 1969Chemagro CorpNematocidal method using alkylthioalkylphosphonodithioates
US5244591 *Mar 23, 1992Sep 14, 1993Chevron Research And Technology CompanyLubricating oil compositions for internal combustion engines having silver bearing parts
U.S. Classification558/183, 987/160, 987/168, 508/431
International ClassificationC07F9/40, C07F9/38, C10L1/26, A01N57/18, C10M141/10, C10M137/14
Cooperative ClassificationC10M2207/282, C10M2211/08, C10M2205/026, C10N2240/402, C10N2240/404, C10M2217/06, C07F9/3808, C10M141/10, C10N2240/046, C10M2209/108, C10M2219/087, C10M2219/089, C10N2240/40, C10M2205/00, C10M2217/028, C10L1/2616, C10M2223/042, C10M2223/04, C10N2240/12, C10N2210/03, C10N2240/401, C10M2205/16, C10N2240/14, C10N2210/08, C10M2203/10, C10M2205/14, C10N2240/62, C10M2209/105, C10M2207/404, C10M2219/082, C10M2219/044, C10L1/2625, C10M2207/34, C10N2240/202, C10M2207/402, C10N2240/044, C10N2240/409, C10N2230/08, C10M2207/046, C10M2207/023, C10M2223/063, C10M2207/125, C10M2203/108, C10M2209/084, C10N2240/042, C10N2240/08, C10N2240/04, C10N2240/406, C10M2207/129, C10N2240/407, C10M2227/082, C10M2223/041, C10M2203/102, C10N2240/02, C10M2215/062, C10M137/14, C10M2205/22, C10M2203/104, C10M2203/106, C10M2223/121, C10M2205/18, C10N2240/201, C10M2207/40, C10M2209/103, C10M2205/17, C10N2240/403, C10M2209/109, C10M2225/04, C10N2210/02, C10M2207/04, C10M2209/107, C10N2220/02, C10N2230/12, C10M2207/024, C10M2219/084, C10M2229/05, C10N2240/408, C10L1/2608, C10N2240/121, A01N57/18, C10M2219/088, C10M2209/104, C10N2250/10, C10N2210/04, C10M2203/06, C10M2219/046, C10M2229/02, C10M2223/065, C10M2201/102, C07F9/4006, C10M2223/047, C10N2240/405
European ClassificationC07F9/40A1, C07F9/38A1, C10M141/10, C10M137/14, C10L1/26A, A01N57/18