US3164580A - Phosphosulfurized esters of amino acids - Google Patents
Phosphosulfurized esters of amino acids Download PDFInfo
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- US3164580A US3164580A US258096A US25809663A US3164580A US 3164580 A US3164580 A US 3164580A US 258096 A US258096 A US 258096A US 25809663 A US25809663 A US 25809663A US 3164580 A US3164580 A US 3164580A
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- US
- United States
- Prior art keywords
- phosphosulfurized
- tetraester
- oil
- product
- extreme pressure
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- 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
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- 150000002148 esters Chemical class 0.000 title description 8
- 150000001413 amino acids Chemical class 0.000 title 1
- -1 PHOSPHORUSSULFUR COMPOUND Chemical class 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical class C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000000654 additive Substances 0.000 description 10
- 239000000314 lubricant Substances 0.000 description 8
- 239000010687 lubricating oil Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002199 base oil Substances 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000005069 Extreme pressure additive Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229960001484 edetic acid Drugs 0.000 description 4
- 229960005082 etohexadiol Drugs 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000158728 Meliaceae Species 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OTYNBGDFCPCPOU-UHFFFAOYSA-N phosphane sulfane Chemical compound S.P[H] OTYNBGDFCPCPOU-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- 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 Table
- C07F9/02—Phosphorus 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
-
- 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
- C10M159/123—Reaction products obtained by phosphorus or phosphorus-containing compounds, e.g. P x S x with organic 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/12—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
Definitions
- Certain classes of compounds can be used to improve specific properties of base lubricants.
- compounds containing sulfur, chlorine, phosphorus or lead or combinations of these elements may improve the extreme pressure properties of a lubricant.
- the simple presence of these elements does not guarantee extreme pressure properties and various compounds that do have these properties can vary considerably in theireifectiv'eness.
- the effectiveness of an extreme pressure additive is related to its ability to reactv with and form a protective coating on a bearing surface to be lubricated. To be most effective, however, the additive must be present in sufficient concentration at the surfaces to form an adequate film.
- One method of realizing this surface concentration is the use of polar'or other type molecules which have an afiinity or attraction for surfaces. Thus, as opposed to the use of a non-polar.
- a polar type molecule will tend to give 'a greater concentration of additive at the metal surface where it is needed.
- a strongly polar material which is not an extreme pressure additive can interfere with the function of a less polar extreme pressure additive.
- a strongly polar non-extreme pressure molecule may be preferentially deposited from its admixture withan extreme pressure additive andprevent the extreme pressure additive from forming its protective extreme pressure film.
- My invention is directed to a lubricating oil composition containing essentially a major amount of a mineral lubricating base oil and an oil-soluble tetraester of a complex acid and an unsaturated'aliphatic alcohol, which ester has been phosphosulfun'zed.
- This tetraester additive has been found to improve pour point, load-carrying and anti-wear properties of lubricating oils.
- theester reaction product of a complex acid such as ethylene diamine tetraacetic acid, which contains sulfur and phosphorus and several polar groupings in the same molecule, has been found to provide a lubricant additive having advantageous anti-wear and extreme pressure characteristics.
- the ,tetraester is formed from carboxylic acid groups preferably of lower aliphatic acids such as acetic, propionic, ,butyric, and the C and C aliphatic acids and an unsaturated aliphatic alcohol generally having about five carbon atoms or more.
- the acid has the molecular structure:
- the ethylene diamine tetraacetic acid used in forming the reaction products in an efiicient chelating agent that is, a chemical which complexes polyvalent metallic ions with a multi-ringstructure that inactivates the metal. This property has been used in a variety of applications'
- the unsaturated aliphatic alcohols of the present invention generally have about 4 to 22, preferably about 8 to 20, carbon atoms and include unsaturated cycloaliphatic alcohols such as cycloalkenols and less desirably aromatics having unsaturated acylic or cycloaliphatic substituents.
- These alcohols have an unsaturated or double bond between acylic or cycloaliphatic carbon atoms with the alcohol hydroxyl group also being'attached to the same acylic or cycloaliphatic carbon chain.
- the preferred alcohols are the unsaturated acylic aliphatic alcohols as, for example, trimethyl pentenol-Z, 2-ethyl hexenol-l, zoomaryl alcohol, etc. It should be emphasized that saturated alcohols are unsuitable for use in the present invention since phosphosulfurization of the tetraester produced from the acids of the present invention and saturated alcohols results in a reaction product which is unstable in lubricating oils, effecting cloudy blends that eventually form voluminous precipitates.
- the appropriate acid and methanol are mixed, and the solution is refluxed and heated for the necessary period of time to obtain esterification.
- the time of refluxing is related to the particular constituents employed and is not considered critical. The period of time will generally range from about 2 to 14 hours.
- a catalyst such as tetra octylene glycol titanate is added to facilitate transesterification.
- the constituents are heated for approximately 5 to 8 hours at a temperature of about to about'140" C.
- the product thus obtained is added to a higher molecular weight unsaturated aliphatic alcohol and a solvent such as xylene, and a catalyst such as octylene glycol titanate is added to facilitate ester interchange.
- the reaction is now maintained at a temperature from about to 160 C. for a period of from about 5 to 10 hours.
- the solvent is then removed by distillation.
- the tetraester of the acid thus obtained is phosphosulfurized by the addition of phosphorus and sulfur compounds such as P 5 P 8 P 8 and the like.
- the subsequent heating and filtering completes the reaction and facilitates the recovery of the final product.
- the temperature for phosphosulfurizing can vary from about to 450: F. with the preferred temperature being about 250 to 300 F.
- a particularly suitable base oil used. in the'preparation of the compositions described hereinafter is a solvent treated Mid-Continent neutral having a viscosity index of about 95.
- the amount of reaction product added to the lubricating oil is suflicient to impart extreme pressure and anti-wear properties to said oil.
- the amount of ester added can vary in amount depending upon the par,- ticular characteristics of lubricating oil utilized. In general from about 0.1 percent of the phosphosulfurized reaction product by weight to about 10 percent of the final composition by weight is utilized in my lubricating oil composition withva preferred amountof from about 1 to 5%. 7
- my additive has been described as the tetraester it may contain portions of lessesterified materials such as di and tri-esters 7 My composition can also contain other additives'such as anti-oxidants, anti-foaming agents, etc.
- Example I 73 grams of ethylene diamine tetraacetic acid are added to 320 grams of methyl alcohol and refluxed with stirring for a period of about 3 hours. HCl is then added and the mixture is refluxed for about 8 hours and then the reaction product is recovered and the excess alcohol is distilled off. The light amber, viscous product is found to be insoluble in mineral oil, di-Z-ethylhexyl)-sebacate, toluene and 2-ethylhexanol, but soluble in iso-butanol. 225 grams of iso-butanol and 1 gram oftetra-octylene glycol titanateyare added to the above product to facilitate ester interchange.
- the reaction is maintained at approximately 130 C. :for a period of about 6 hours. This is accomplished by gradually removing reflux as distillate during the above period.
- the product is analyzed to be 3.87% nitrogen;
- 255 grams of the tetrabutyl ester of ethylene diamine tetraacetic acid is added to 530 grams of an unsaturated alcohol known as Makanol 8 (Makanol 8 is described as an alcohol resulting from the sodium reduction of soybean oil and consists of 12% saturated and 88% unsaturated fatty alcohols having an average molecular weight of about 265).
- 500 ml. of xylene solvent and 5 grams of tetra-octylene glycol titanate were added to facilitate ester interchange.
- the temperature is then maintained at about 150 C. for about 8 hours.
- the solvent is then removed by vacuum distillation at a temperature of about 13160" C.
- the product thus formed can be called Product Example 11
- About 264 grams of Product A is added to about 36 grams of sulfur and then reacted *for about 24 hours at an approximate temperature of 320 F.
- the product thusobtained is called Product B.
- Timken L-20 Test which is run using the Timken machine described in CRC Ll8545. The test block is continuously moved back and forth beneath the test cup in a direction paralleling the level arm for a distance for about 0.13 inch at an approximate rate of about 4 times per minute. Conditions for load, speed, time and temperature may be varied and are noted for each given test.
- The/following table reveals results and comparisons between similar tests on a base oil, a conventional motor oil additive and my products.
- the base oil is a Vi solvent refined Mid-Continent neutral oil having a viscosity of about 33 SUS at F.
- the motor oil additives included about 3 percent of a solution of 15 weight percent basic barium mahogany sulfonate in petroleum oil along with 1.8 percent of 50 percent Zinc dithiophosphate diester in petroleum oil. Products C and'D were readily soluble in the base oil and each produced clear blends.
- R is a divalent hydrocarbon radical of 1 to 5 of an unsaturated aliphatic alcohol of 8 to 20 carbon carbon atoms and R is a divalent hydrocarbon radical atoms having carbon to carbon double bond unsaturation 2 to 6 carbon atoms said phosphosulfurized tetraester y and ethylene diamine tetfaacetic acid
- P p being the reaction product of said tetraester and about 1 Sulfurized tetraestel' being the reaction Pmdllct Of Said to 10% by Weight of a phosphosulfurizing phosphorus- 5 tetra-es te r and about 1 to 10% b Wight of a P p sulfur compoun sulfunzing phosphorus-sulfur compound.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Lubricants (AREA)
Description
Un i S s P w 3 164 580 PHOSPHOSULFURIZEIhETERS 0F AMINO A CID S Howard J. Matson, Harvey, 11]., assignor to Sinclair Research, Inc., Wilmington, Del., a corporation of This invention relates to additives for mineral oil compositions and more particularly to oil-soluble agents which impart improved pour point, extreme pressure or loadcarrying characteristics and anti-wear properties to the lubricant.
With the advent of higher compression internal combustion engines, much difiiculty has been experienced in formulating a suitable lubricating oil composition capable of operating under severe conditions to protect-effectively metal surfaces which come in contact with the oil. 7 It is well known that the high pressure occurring in certain types of gears and bearings may cause a film of lubricant to rupture with subsequent damage to the machinery. It has been shown that base lubricants such as mineral oil and/ or synthetic oil can be improved with regard to their protective effect on rubbing surfaces by the addition of certain substances so that excessive wear, scuifing and seizure which normally follow a break in the film of lubricant can be prevented even under the most unfavorable pressure and speed conditions. Lubricants possessing this highly desirable property are called extreme pressure lubricants.
Certain classes of compounds can be used to improve specific properties of base lubricants. Thus, compounds containing sulfur, chlorine, phosphorus or lead or combinations of these elements may improve the extreme pressure properties of a lubricant. However, the simple presence of these elements does not guarantee extreme pressure properties and various compounds that do have these properties can vary considerably in theireifectiv'eness. Itis generally believed that the effectiveness of an extreme pressure additive is related to its ability to reactv with and form a protective coating on a bearing surface to be lubricated. To be most effective, however, the additive must be present in sufficient concentration at the surfaces to form an adequate film. One method of realizing this surface concentration is the use of polar'or other type molecules which have an afiinity or attraction for surfaces. Thus, as opposed to the use of a non-polar.
molecule which will be present in more or less equal concentration throughout the bulk of thelubricant, a polar type molecule will tend to give 'a greater concentration of additive at the metal surface where it is needed.
- In a similar manner a strongly polar material which is not an extreme pressure additive can interfere with the function of a less polar extreme pressure additive. Thus, a strongly polar non-extreme pressure molecule may be preferentially deposited from its admixture withan extreme pressure additive andprevent the extreme pressure additive from forming its protective extreme pressure film.
My invention is directed to a lubricating oil composition containing essentially a major amount of a mineral lubricating base oil and an oil-soluble tetraester of a complex acid and an unsaturated'aliphatic alcohol, which ester has been phosphosulfun'zed. This tetraester additive has been found to improve pour point, load-carrying and anti-wear properties of lubricating oils. Thus, theester reaction product of a complex acid such as ethylene diamine tetraacetic acid, which contains sulfur and phosphorus and several polar groupings in the same molecule, has been found to provide a lubricant additive having advantageous anti-wear and extreme pressure characteristics.
The ,tetraester is formed from carboxylic acid groups preferably of lower aliphatic acids such as acetic, propionic, ,butyric, and the C and C aliphatic acids and an unsaturated aliphatic alcohol generally having about five carbon atoms or more. In general the acid has the molecular structure:
HOOC-R HO 0 0-K N-CHg-QHr-N n0oo om CHr-COOH CH2COOH The ethylene diamine tetraacetic acid used in forming the reaction products in an efiicient chelating agent; that is, a chemical which complexes polyvalent metallic ions with a multi-ringstructure that inactivates the metal. This property has been used in a variety of applications' The unsaturated aliphatic alcohols of the present invention generally have about 4 to 22, preferably about 8 to 20, carbon atoms and include unsaturated cycloaliphatic alcohols such as cycloalkenols and less desirably aromatics having unsaturated acylic or cycloaliphatic substituents. These alcohols have an unsaturated or double bond between acylic or cycloaliphatic carbon atoms with the alcohol hydroxyl group also being'attached to the same acylic or cycloaliphatic carbon chain. The preferred alcohols are the unsaturated acylic aliphatic alcohols as, for example, trimethyl pentenol-Z, 2-ethyl hexenol-l, zoomaryl alcohol, etc. It should be emphasized that saturated alcohols are unsuitable for use in the present invention since phosphosulfurization of the tetraester produced from the acids of the present invention and saturated alcohols results in a reaction product which is unstable in lubricating oils, effecting cloudy blends that eventually form voluminous precipitates.
In making the ester the appropriate acid and methanol are mixed, and the solution is refluxed and heated for the necessary period of time to obtain esterification. The time of refluxing is related to the particular constituents employed and is not considered critical. The period of time will generally range from about 2 to 14 hours. After such as iso-butanol along with a catalyst such as tetra octylene glycol titanate is added to facilitate transesterification. The constituents are heated for approximately 5 to 8 hours at a temperature of about to about'140" C. The product thus obtained is added to a higher molecular weight unsaturated aliphatic alcohol and a solvent such as xylene, and a catalyst such as octylene glycol titanate is added to facilitate ester interchange. The reaction is now maintained at a temperature from about to 160 C. for a period of from about 5 to 10 hours. The solvent is then removed by distillation.
The tetraester of the acid thus obtained is phosphosulfurized by the addition of phosphorus and sulfur compounds such as P 5 P 8 P 8 and the like. The subsequent heating and filtering completes the reaction and facilitates the recovery of the final product. The temperature for phosphosulfurizing can vary from about to 450: F. with the preferred temperature being about 250 to 300 F. Generally in preparing the additive I may be employed. A particularly suitable base oil used. in the'preparation of the compositions described hereinafter is a solvent treated Mid-Continent neutral having a viscosity index of about 95.
The amount of reaction product added to the lubricating oil is suflicient to impart extreme pressure and anti-wear properties to said oil. Thus, the amount of ester added can vary in amount depending upon the par,- ticular characteristics of lubricating oil utilized. In general from about 0.1 percent of the phosphosulfurized reaction product by weight to about 10 percent of the final composition by weight is utilized in my lubricating oil composition withva preferred amountof from about 1 to 5%. 7 Although my additive has been described as the tetraester it may contain portions of lessesterified materials such as di and tri-esters 7 My composition can also contain other additives'such as anti-oxidants, anti-foaming agents, etc.
The following examples, not to be construed as limiting,
are ordered to further illustrate the novel additive and" lubricating oil composition of my present invention.
Example I 73 grams of ethylene diamine tetraacetic acid are added to 320 grams of methyl alcohol and refluxed with stirring for a period of about 3 hours. HCl is then added and the mixture is refluxed for about 8 hours and then the reaction product is recovered and the excess alcohol is distilled off. The light amber, viscous product is found to be insoluble in mineral oil, di-Z-ethylhexyl)-sebacate, toluene and 2-ethylhexanol, but soluble in iso-butanol. 225 grams of iso-butanol and 1 gram oftetra-octylene glycol titanateyare added to the above product to facilitate ester interchange. The reaction is maintained at approximately 130 C. :for a period of about 6 hours. This is accomplished by gradually removing reflux as distillate during the above period. The product is analyzed to be 3.87% nitrogen; Next 255 grams of the tetrabutyl ester of ethylene diamine tetraacetic acid is added to 530 grams of an unsaturated alcohol known as Makanol 8 (Makanol 8 is described as an alcohol resulting from the sodium reduction of soybean oil and consists of 12% saturated and 88% unsaturated fatty alcohols having an average molecular weight of about 265). Then 500 ml. of xylene solvent and 5 grams of tetra-octylene glycol titanate were added to facilitate ester interchange. The temperature is then maintained at about 150 C. for about 8 hours. The solvent is then removed by vacuum distillation at a temperature of about 13160" C. The product thus formed can be called Product Example 11 About 264 grams of Product A is added to about 36 grams of sulfur and then reacted *for about 24 hours at an approximate temperature of 320 F. The product thusobtained is called Product B.
Example III grams of concentrated.
300 F. for about 16 hours. The reaction mixture is then filtered to yield approximately 418 grams of a bright yellow viscous liquid analyzed as containing sulfur, 0.92%; phosphorus, 1.07%. This product is called Prodnot C.
' Example IV Shell 4-Ball Wear Test Mean Hertz Load SAE Load Test Falex Load Test Timken L-20 Test These tests have been fully described in literature under the subject of anti-wear and extreme pressure testing. Thus, I will not attempt to go into any detail concerning the procedures of each. The possible exception to the above is the Timken L-20 Test which is run using the Timken machine described in CRC Ll8545. The test block is continuously moved back and forth beneath the test cup in a direction paralleling the level arm for a distance for about 0.13 inch at an approximate rate of about 4 times per minute. Conditions for load, speed, time and temperature may be varied and are noted for each given test.
The/following table reveals results and comparisons between similar tests on a base oil, a conventional motor oil additive and my products. The base oil is a Vi solvent refined Mid-Continent neutral oil having a viscosity of about 33 SUS at F. The motor oil additives included about 3 percent of a solution of 15 weight percent basic barium mahogany sulfonate in petroleum oil along with 1.8 percent of 50 percent Zinc dithiophosphate diester in petroleum oil. Products C and'D were readily soluble in the base oil and each produced clear blends.
Blend No -1 2 3 4 Base Oil, Wt. percent 100 95. 2 98 98 Motor Oil Additiv 4.8 .1 Product 0. 2.0 Product D 2; 0 Shell d-Ball Wear Test, Sear Diam., mm. (7 kg, 2 hrs, 0., 640 r. .rn) 0, 687 0. 247 0. 290 0. 280 Mean Hertz Load 13. 7 26. 9 33.8 40. 7 SAE at 300 r.p.rn., l 67 121 132 Falex Breakdown, lbs Fails 1, 600 4, 500 3, 750 Tilnken L-20 Test, Total wear, mg: at
(100 lbs. 200 F., 200 r.p.m., 16 Start hrs.) of 254 14.1 12.5 lbs. 200 F., 200 r.p.rn. 16 Test hrs. 14. 3 Pour Point of Blend, F 10 10 15 10 The above data demonstrate the improved pour point, the increased load carrying capacity and extreme pressure properties of my compositions.
This'application is a division of serial No. 207,807, now Patent No. 3,097,170, a continuation-in-part of my now abandoned application Serial No. 752,409 filed August 1,-1958.
- I claim:
, 1. A phosphosulfurized mineral oil-soluble tetraester of an unsaturated aliphatic alcohol of from 4 to 22 carbon atoms having carbon to carbon double bond unsaturation only and a carboxylic acid of the formula:
5 wherein R is a divalent hydrocarbon radical of 1 to 5 of an unsaturated aliphatic alcohol of 8 to 20 carbon carbon atoms and R is a divalent hydrocarbon radical atoms having carbon to carbon double bond unsaturation 2 to 6 carbon atoms said phosphosulfurized tetraester y and ethylene diamine tetfaacetic acid Said P p being the reaction product of said tetraester and about 1 Sulfurized tetraestel' being the reaction Pmdllct Of Said to 10% by Weight of a phosphosulfurizing phosphorus- 5 tetra-es te r and about 1 to 10% b Wight of a P p sulfur compoun sulfunzing phosphorus-sulfur compound.
2. A phosphosulfurized mineral oil-soluble tetraester No references cited.
Claims (1)
1. A PHOSPHOSULFURIZED MINERAL OIL-SOLUBLE TETRAESTER OF AN UNSATURATED ALIPHATIC ALCOHOL OF FROM 4 TO 22 CARBON ATOMS HAVING CARBON TO CARBON DOUBLE BOND UNSATURATION ONLY AND A CARBOXYLIC ACID OF THE FORMULA: ((HOOC-R)2-N)2-R'' WHEREIN R IS A DIVALENT HYDROCARBON RADICAL OF 1 TO 5 CARBON ATOMS AND R'' IS A DIVALENT HYDROCARBON RADICAL 2 TO 6 CARBON ATOMS SAID PHOSPHOSULFURIZED TETRAESTER BEING THE REACTION PRODUCT OF SAID TETRAESTER AND ABOUT 1 TO 10% BY WEIGHT OF A PHOSPHOSULFURIZING PHOSPHORUSSULFUR COMPOUND.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US258096A US3164580A (en) | 1962-07-05 | 1963-01-25 | Phosphosulfurized esters of amino acids |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US207807A US3097170A (en) | 1962-07-05 | 1962-07-05 | Phosphosulfurized material and extreme pressure lubricant containing the same |
US258096A US3164580A (en) | 1962-07-05 | 1963-01-25 | Phosphosulfurized esters of amino acids |
Publications (1)
Publication Number | Publication Date |
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US3164580A true US3164580A (en) | 1965-01-05 |
Family
ID=26902610
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US258096A Expired - Lifetime US3164580A (en) | 1962-07-05 | 1963-01-25 | Phosphosulfurized esters of amino acids |
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US (1) | US3164580A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4755619A (en) * | 1985-04-01 | 1988-07-05 | National Research Development Corporation | Pharmaceutical compositions |
US5149710A (en) * | 1985-04-01 | 1992-09-22 | National Research Development Corporation | Pharmaceutical compositions for treating psoriasis |
US5162372A (en) * | 1985-04-01 | 1992-11-10 | National Research Development Corporation | Pharmaceutical compositions for treating certain cancers |
US5278187A (en) * | 1985-04-01 | 1994-01-11 | British Technology Group Ltd. | Pharmaceutical compositions |
US5438057A (en) * | 1991-07-12 | 1995-08-01 | British Technology Group Limited | Pharmaceutical compositions |
-
1963
- 1963-01-25 US US258096A patent/US3164580A/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
None * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4755619A (en) * | 1985-04-01 | 1988-07-05 | National Research Development Corporation | Pharmaceutical compositions |
US4902714A (en) * | 1985-04-01 | 1990-02-20 | National Research Development Corporation | Pharmaceutical compositions |
US5149710A (en) * | 1985-04-01 | 1992-09-22 | National Research Development Corporation | Pharmaceutical compositions for treating psoriasis |
US5162372A (en) * | 1985-04-01 | 1992-11-10 | National Research Development Corporation | Pharmaceutical compositions for treating certain cancers |
US5278187A (en) * | 1985-04-01 | 1994-01-11 | British Technology Group Ltd. | Pharmaceutical compositions |
US5438057A (en) * | 1991-07-12 | 1995-08-01 | British Technology Group Limited | Pharmaceutical compositions |
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