US3706763A - Polyalkylene glycol mercaptosuccinimides dispersants for lubricant fluids - Google Patents
Polyalkylene glycol mercaptosuccinimides dispersants for lubricant fluids Download PDFInfo
- Publication number
- US3706763A US3706763A US69094A US3706763DA US3706763A US 3706763 A US3706763 A US 3706763A US 69094 A US69094 A US 69094A US 3706763D A US3706763D A US 3706763DA US 3706763 A US3706763 A US 3706763A
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- US
- United States
- Prior art keywords
- lubricant
- polyalkylene glycol
- dispersants
- mercaptosuccinimides
- fluid
- 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
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Classifications
-
- 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/20—Thiols; Sulfides; Polysulfides
- C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M135/26—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
-
- 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
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl 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
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
- C10M2215/065—Phenyl-Naphthyl 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
- C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
-
- 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
- C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2221/02—Macromolecular compounds obtained by reactions of monomers involving only carbon-to-carbon unsaturated bonds
-
- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
Definitions
- This invention relates to chemical compositions and, more particularly, to chemical compositions useful as lubricating fluid additives and to lubricating fluid compositions. Still more particularly, this invention relates to polyalkylene glycol mercaptosuccinimide lubricant additives and lubricant compounds.
- Motor fuel lubricants such as conventional automobile motor oil or oils designed for special applications, e.g., marine, aircraft and stationary engines, conventionally include oxidation inhibitors and dispersant additives. Viscosity improvers, etc. are also conventionally added to the basic lubricant fluid to provide particular characteristics desired in the end lubricating compound.
- hydrocarbon-based or hydrocarboncontaining additives are commercially available for use in conventional hydrocarbon lubricating fluids. It is, of course, essential that any successful additive be soluble -in the lubricating fluid at all potential operating or handling conditions.
- Long chain aliphatic hydrocarbon substituted succinic acid-amine derivatives have been proposed as dispersant additives for hydrocarbon-based lubricant fluids, see U.S. Pat. No. 3,172,892, LeSuer and Norman, for example.
- the basic fluid in the preferred embodiment, is a polypropylene glycol diether polymer identified hereinafter as Ucon fluid DLB-200E. It has been found that while many oxidation inhibitors useful in petroleum derived hydrocarbon lubricant fluids may be used with the synthetic crankcase oils of this invention, none of the dispersant additives previously known are sufliciently soluble and are otherwise successful as dispersants in the synthetic crankcase oil compositions of this invention. It is, accordingly, a principal object of this invention to provide a new and improved dispersant additive for use in propylene glycol diether polymer synthetic lubricating fluids.
- a principal object of the invention is to provide improved synthetic lubricant fluids for use as crankcase oils and as lubricants generally, which comprise polypropylene glycol diether as a base fluid and an improved sludge dispersant additive.
- a more specific object of the invention is to provide an improved dispersant additive comprising polyalkylene glycol mercaptosuccinimides.
- An additional and more specific object of the invention is to provide a lubricating composition including a polyalkylene glycol diether lubricant base fluid in combination with a sludge dispersant additive comprising polyalkylene glycol mercaptosuccinimides.
- a further and more specific object of the invention is to provide a class of polyalkylene glycol mercaptosuccinimides for use as lubricant additives.
- a process for preparing lubricant additives and lubricant fluids constitutes an additional and still more specific object if the invention.
- the dispersant additives of this invention are prepared, in general, by refluxing mercaptosuccinic acid or mercaptosuccinic anhydride with a polyalkylene glycol, then refluxing the product of the foregoing reaction with an amine, preferably a polyalkylene polyamine, at a temperature sufliciently high to initiate the reaction and remove water.
- a solvent such as toluene, xylene, etc., may
- the first step of the reaction the formation of the polyalkylene glycol derivative of mercaptosuccinic acid is carried out under atmospheric pressure, with or without the addition of solvent, at a temperature of from about 50 C. to about 250 C., and preferably in the range of about C. to 250 C. for from about 1 to about 500 hours, preferably from about 10 to about hours.
- the second step of the reaction the formation of the succinimide by reaction of the polyalkylene glycol derivative of mercaptosuccinic acid with a polyalkylene polyamine is also preferably carried out at atmospheric pressure preferably in the presence of a solvent which is inert to the reaction, such as paraflinic and cycloparaflinic hydrocarbons, benzene, alkylbenzenes, etc., e.g., toluene and xylene.
- the reaction may be carried out from about 50 C. to about 300 C., preferably in the range of from about 80 C. to 150 C. for reaction times of between about one-half hour and 40 hours, preferably from 1 hour to 8 hours.
- Ucon fluid LB-385 0.1 mole
- mercaptosuccinic acid 0.1 mole
- Ucon LB-385 has an apparent specific gravity at C. of 0.995, a viscosity index (ASTM D-567) of 144, a viscosity, Saybolt seconds at 210 F. of 75, at 100 F. of 385 and at 0 F. of 15,000, a viscosity in centistokes at 210 F. of 14.3, at 100 F. of 83.3, and at 0 F. of 4,700 with a pour point (ASTM D-97) of F. and a fire point (ASTM D-92) of 500 F.
- the molecular Weight of the polypropylene glycol is about 1500. This fluid is produced by Union Carbide Plastics and Chemicals Department, New York.
- the reaction mixture was heated to 100 C. with stirring. The temperature increased to 120 C. with moisture coming off. 100 mls. of benzene was added and the reaction was continued. The temperature continued to increase to about 200 C. as benzene was partially removed (ca. ml.). At this point, the reaction vessel was cooled down to 45 C. and reheated to C. The temperature increased to 96 C. and the reaction was allowed to continue for a total running time of 136 hours.
- Tetraethylenepentamine (0.04 mole) and mls. of toluene was added and the reaction mixture was refluxed at C. for 6 hours. Moisture coming off from the reaction mixture was collected as the color of the reactive to used Ucon DLB-20OE obtained from engines used in dynamometer tests.
- the dispersant additive product of the aforementioned process was mixed with the material to be tested in a Waring Blendor for 5 minutes. The sample was observed for sludge separation and paper chromatographic spot tests were made to determine dispersant effectiveness. Data showing the relative effectiveness of the composition of this invention are given in Table I along with comparative data using other known and experimental dispersant additives.
- Standard #1 100 Used Ucon from chassis dynamometer test on Chevrolet 19 72 Standard #2..
- 100 Used Ucon from chassis dynamometer test on Ford 4 58 640-42-2 5 Mercaptosuecinic acid plus Ucon LB-385 plus tetraethylenepentamine 1 3 CH3 ⁇ R ⁇ O CHzH S-CHC O N- CHZCHZNH -H and/or ornoo CH HS-CHCOr-CHCHzO R CHzC0(NHCH-. CHz NH2 6493l-6 5 CH3 CH3 4 43 CrzHza-CHC O2HCHz ⁇ O HCHZ, O R
- compositions of this invention compared with other dispersant compounds are immediately apparent.
- the significantly greater effectiveness as a dispersant additive of the inventive compounds, as compared with structurally similar compounds, is quite unexpected.
- n and m are positive integers.
- a polyalkylene glycol wherein n was 25 and a polyalkylene amine wherein m was 4 were used; however, n may be a positive integer from 1 to 100 and m may be a positive integer from 1 to 10.
- n should be greater than 10 and, within broad ranges, n. should be at least about 5 times m and preferably from 5 to 15 times m.
- 'R is a lower alkyl group or hydrogen, preferably methyl.
- the compounds of this invention in addition to being effective as a dispersant additive for lubricants, also serve as anti-wear agents and are effective as corrosion and oxidation inhibitors, thereby reducing the required concentration of specially compounded corrosion and oxidation inhibitors.
- the lubricating compositions of this invention are preferably formed by blending the mercaptosuccinimide compounds heretofore described with end-blocked polyalkylene glycol ether lubricating fluids, for example the endblocked polypropylene glycol ether identified as Ucon fluid DLB-200E available from Union Carbide Plastics and Chemicals Department, New York.
- the dispersant additive concentration level is from 0.1 to percent generally, preferably from about 1 percent to about 5 per cent, by weight.
- Oxidation inhibitors are also added in the 0.1 percent to 5 percent range, preferably in the range of from 0.5 percent to 3 percent.
- 3 percent Oronite 254 is the preferred additive but 1 percent concentration of 4,4-methylene, bis-2,6- ditertiary butyl phenol (Ethyl 702), an alkylated phenol (Lubrizol 814), phenyl alpha-naphthylamine, and an alkylated diphenylamine (VanLube SL) were found to be successful oxidation inhibiting additives.
- Ucon DLE-200 fluid is amber in color, has a viscosity at 210 F. of 58.3 (SUS), at F. of 201 (SUS) and at 0 F. of 5660 (SUS).
- the viscosity, in centistokes, is 9.70 at 210 F., 43.2 at 100 F., 1230 at 0 'F., 4140 at 20 RF. and 23,800 at 40 F.
- the viscosity index is 161, the pour point is 50 F., the flash point is 520 F. and the fire point is 565 F. This product is described in Union Carbide Chemicals Company Advance Technical Information publication F-40400, June 1959.
- Double endblocked lubricants of this class generally may be used in the compositions of this invention, the primary consideration being the desired viscosity and viscosity index.
- the manufacture and properties of these compounds is dis cussed by Gunderson and Millet, Synthetic Lubricants, Reinhold, New York, 1962, chapter on Polyglycols. Reference is made to this work and the publications and patents cited therein for a complete discussion of the lubricant base stocks used in the inventive composition.
- lubricating fluid dispersant additive, and oxidation inhibitor.
- fluids of the present invention e.g., an end-blocked polyalkylene glycol ether lubricating base fluid, a mercaptosuccinimide dispersant additive of the type described, and an oxidation inhibitor, e.g., Oronite 254, there is provided a potential lifetime motor lubricant.
- the lubricating properties of the base fluid are not diminished under normal operating conditions; however, over long periods of time the base fluid may be oxidized to form volatile components which are discharged from the crankcase.
- An effective oxidation inhibitor is, therefore, necessary to prevent too rapid decomposition of the base lubricating fluid resulting in the necessity for continual addition of lubricant.
- Sludge is formed in every internal combustion engine from combustion products, Wear products, etc. It is essential that this sludge be maintained in the lubricant and carried to an effective filter. Therefore, an effective dispersant additive is required to provide an essentially homogeneous circulating lubricant fluid in which the sludge forming materials are maintained in dispersion. As the homogeneous fluid is circulated through the oil filter, the sludge components are removed and the clean lubricating fluid is returned to the crankcase. Except for occasional addition of lubricating fluid, no additional attention need be given to a vehicles engine lubricating system. The convenience and economy of this type of fluid are immediately apparent.
- n is from 5 to 15 times the value of m.
- a process comprising the steps of reacting (a) a compound selected from the group consisting of mercaptosuccinic acid and mercaptosuccinic anhydride with (-b) a polypropylene glycol having the formula CH3 R 0c1i2011 I1 wherein n is a positive integer from 1 to 100 and R is lower alkyl or hydrogen and further reacting the product of (a) and (b) with a polyalkylene polyamine having the formula i wherein m is a positive integer from 1 to 10 with the proviso that n is at least 3 times the value of m, at a temperature of from about C. to about 300 C. for from about /2 hour to about 500 hours.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
Description
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US76599468A | 1968-10-08 | 1968-10-08 | |
US6909470A | 1970-09-02 | 1970-09-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3706763A true US3706763A (en) | 1972-12-19 |
Family
ID=26749680
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US765994A Expired - Lifetime US3598735A (en) | 1968-10-08 | 1968-10-08 | Polyalkylene glycol mercaptosuccinimides dispersants for lubricant fluids |
US69094A Expired - Lifetime US3706763A (en) | 1968-10-08 | 1970-09-02 | Polyalkylene glycol mercaptosuccinimides dispersants for lubricant fluids |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US765994A Expired - Lifetime US3598735A (en) | 1968-10-08 | 1968-10-08 | Polyalkylene glycol mercaptosuccinimides dispersants for lubricant fluids |
Country Status (1)
Country | Link |
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US (2) | US3598735A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3852205A (en) * | 1973-11-05 | 1974-12-03 | Texaco Inc | Transmission fluid compositions and method |
GB8921382D0 (en) * | 1989-09-21 | 1989-11-08 | Bp Chemicals Additives | Chemical compounds |
-
1968
- 1968-10-08 US US765994A patent/US3598735A/en not_active Expired - Lifetime
-
1970
- 1970-09-02 US US69094A patent/US3706763A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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US3598735A (en) | 1971-08-10 |
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Legal Events
Date | Code | Title | Description |
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AS | Assignment |
Owner name: ATLANTIC RICHFIELD COMPANY Free format text: MERGER AND CHANGE OF NAME;ASSIGNORS:ATLANTIC RICHFIELD COMPANY (MERGED INTO);ATLANTIC RICHFIELD DELAWARE CORPORATION (CHANGED TO);REEL/FRAME:004911/0380 Effective date: 19850314 Owner name: ARCO CHEMICAL COMPANY,PENNSYLVANIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ATLANTIC RICHFIELD COMPANY;REEL/FRAME:004911/0448 Effective date: 19870831 Owner name: ARCO CHEMICAL COMPANY, 1500 MARKET STREET, PHILADE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ATLANTIC RICHFIELD COMPANY;REEL/FRAME:004911/0448 Effective date: 19870831 |
|
AS | Assignment |
Owner name: ARCO CHEMICAL TECHNOLOGY, INC., A CORP. OF DE, DEL Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ARCO CHEMICAL COMPANY;REEL/FRAME:005010/0113 Effective date: 19880831 |