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US3927104A - Polybutenyl-alkylene polyamine-polyalkanol lubricant additive - Google Patents

Polybutenyl-alkylene polyamine-polyalkanol lubricant additive Download PDF

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Publication number
US3927104A
US3927104A US533910A US53391074A US3927104A US 3927104 A US3927104 A US 3927104A US 533910 A US533910 A US 533910A US 53391074 A US53391074 A US 53391074A US 3927104 A US3927104 A US 3927104A
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Prior art keywords
polybutenyl
dispersant
polyalkanol
alkylene polyamine
lubricating oil
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US533910A
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Edward F Miller
Walter W Hellmuth
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Texaco Inc
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Texaco Inc
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Priority claimed from US408226A external-priority patent/US3884821A/en
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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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/54—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/108—Residual fractions, e.g. bright stocks
    • 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
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B1/00—Engines characterised by fuel-air mixture compression
    • F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
    • F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder

Definitions

  • R is a polybutenyl radical having a molecular weight from 900 to 10,000 and a mineral lubricating oil composition containing said polybutenyl-alkylene polyamine polyalkanol.
  • a copending patent application Ser. No. 208,978 filed Dec. 16, 1971 discloses a lubricating oil composition containing a polyisobutenyl-substituted N-aminoethylethanolarnine as an ashless dispersant.
  • An oil-soluble ashless dispersant for a mineral lubricating oil composition comprising a polybutenyl-alkylene polyamine-polyalkanol is provided as well as a mineral lubricating oil composition containing same.
  • the polybutenyl-alkylene polyamine-polyalkanol is represented by the general formula:
  • R is a polybutenyl radical having a molecular weight from 900 to 10,000
  • X and Y represent H or (R"O) I-I at least one of X or Y being (RO) I-I
  • R is a divalent hydrocarbyl radical having from 2 to 8 carbon atoms
  • R" is a divalent hydrocarbyl radical having from 2 to 4 carbon atoms
  • x has a value from 1 to 6
  • y has a value from 1 to 5.
  • the polyisobutenyl radical R will consist of from about 70 to 700 carbon atoms.
  • a formulated mineral lubricating oil composition will generally contain the dispersant in a concentration ranging from about 0.1 to 10 weight percent with the preferred concentration being from about 0.2 to 5 percent.
  • R is a polybutenyl radical having a molecular weight from 900 to 10,000
  • X and Y represent H or (R"O),,H at least one of X or Y being (R"O),,H
  • R is a divalent hydrocarbyl radical having from 2 to 4 carbon atoms
  • x has'a value from 1 to 6
  • y has a value from 1 to 5.
  • a preferred class of compounds are those in which R is a polybutenyl radical having a molecular weight from 1,000 to 5,000, with a more preferred class being those in which R is a polybutenyl radical of 1,200 to 2,500 moleweight.
  • X and Y represent hydrogen or the radical (R"O), ,I-I withat least one of X or Y being (R"O),,H.
  • the dispersants of this invention thus can be represented by the formulas? and where R, R R" x and y have the values noted above.
  • Highly effective compounds for lubricating oil compositions are those in which R and R are divalent ethylene and propylene radicals and x and y are 1 or 2. Certain classes of these compounds are represented by the formulas:
  • the compound of the invention contains at least two hydrooxyalkyl radicals per mole of the compound attached to the same or different nitrogen atoms in the compounds. It will be appreciated that a substantially larger number of hydrooxyalkyl groups can be present in the compounds hereinabove defined.
  • the prescribed polybutenyl-alkylene polyaminepolyalkanol can be prepared in two steps involving a reaction between a polybutenyl polymer and an alkylene polyamine in the first step to form an intermediate compound followed by a reaction with an alkylene oxide in the second step.
  • the polybutenyl component for the above reactions is a polymer of isobutylene which can be prepared by known polymerization methods. This polymer will have an average molecular weight ranging from 900 to 10,000.
  • a preferred polybutenyl polymer is one having an average molecular weight ranging from 1,000 to 5,000 with the most preferred having a molecular weight from 1,200 to 2,500.
  • the alkylene polyamine component employed can be a straight or branched chain diamine or a polyalkylene polyamine of mixture thereof.
  • suitable diamines include ethylene diamine, propylene diamine, 1,4-butane diamine, 1,4-pentane diamine and 1,6-hexane diamine.
  • suitable polyalkylene polyamines include diethylene triamine, piperazine, triethylene tetramine, N-aminoethylpiperazine, tetraethylene pentamine and pentaethylene hexamine.
  • One method of reacting the polybutenyl polymer with the alkylene polyamine is to first prepare a halogen derivative, i.e. a chloride or bromide derivative of the polybutenyl polymer containing from 0.5 to 10 percent of the halogen according to known methods as set forth in US. Pat. No. 3 275,554 which disclosure is incorporated herein.
  • This halogenated polybutenyl polymer is then reacted with the prescribed alkylene polyamine.
  • 1 to 2 moles of the alkylene polyamine is reacted with the halogenated polybutenyl polymer.
  • This reaction is preferable conducted in the presence of an alkaline material to facilitate the reaction. However, the reaction can be conducted without employing alkaline material and in the absence of a solvent.
  • the reaction is generally conducted at a temperature ranging from about 250 to 500F.
  • the intermediate compound is then reacted with an alkylene oxide to form the dispersant of the invention.
  • the preferred alkylene oxides for this reaction include ethylene oxide, propylene oxide and butylene oxide although higher alkylene oxides and alkyl substituted alkylene oxides are also suitable.
  • This reaction is generally conducted by dissolving the intermediate compound in a hydrocarbon solvent and gradually adding the alkylene oxide reactant to the reaction mixture over a period of time.
  • the reaction is conveniently conducted at room temperature although higher and lower temperatures generally ranging from about to 100C. can be employed.
  • the ratio of alkylene oxide to alkylated alkylene polyamine is at least 2:1 and is generally in the range of 2:1 to :1 with the preferred range being 2:1 to 5:1. These ranges effect alkoxylation of the primary and secondary nitrogen atoms as well as for polyalkoxylation at these points.
  • the reaction mixture is then filtered and the solvent stripped off under a vacuum.
  • N-polyisobutenyl(C )-N,N ',N"-tetrakis-Z-hydroxyethyl diethylenetriamine N-polyisobutenyl(C )-N,N ',N"-tetrakis-Z-hydroxyethyl diethylenetriamine.
  • the hydrocarbon mineral base oil employed in preparing the lubricating oil compositions of the invention can be a parafiinic base, naphthene base or mixed parafi'm-naphthene base distillate or residual oil. Paraffin base distillate lubricating oil fractions are preferred for the formulation of the highest quality engine or motor oils.
  • the lubricating oil base generally will have been subjected to solvent refining to improve its lubricity and viscosity temperature relationship as well as to solvent dewaxing to remove waxy components and to improve the pour of the oil.
  • mineral lubricating oils having an SUS viscosity at 100F between 50 and 1,000 may be used in the formulation of the improved lubricants of this-invention with the preferred oils having a viscosity range from 70 to 300 SUS at 100F.
  • a blend of base oils can be employedto provide a suitable base oil for either a single or multigrade motor oil.
  • the following example illustrates a method for preparing the ashless dispersants of the invention.
  • EXAMPLE I 4,620 grams of chlorinated polybutene having a molecular weight of about 1300 and containing 2.76 percent of chlorine was mixed with 500 grams (4.3 moles) of hexamethylene diamine and 191 grams (1.8 moles) of sodium carbonate. The reaction mixture was cooled, diluted with four liters of hexane, filtered and the filtrate extracted with methanol. The hexane layer was stripped under vacuum at 200F. yeilding an intermediate product containing 0.8 percent nitrogen. 2,340 grams of the above intermediate product was dissolved in 800 milliliters of toluene and 334 milliliters of isopropyl alcohol.
  • the effectiveness of the dispersant of the invention was determined in the Caterpillar l-H Diesel Engine Test. This is a standard industry test which is run on a 1Y73 single cylinder Caterpillar Diesel Lubricant Test Engine as described in FTMS 79la-346T. This test is used to qualify lubricants for MIL-L-2l04B.
  • the engine is operated at a speed of 1,800 RPM and a fuel input of 4,950 BTU/min for a test duration of 480 hours. Performance is judged by examination of the power section of the engine for ring sticking, piston deposits and ring, piston and liner wear.
  • Example H The procedure of Example I is repeated using 2,000 grams of a chlorinated polybutene containing 2.76% chlorine, 209 g (1.6 mole) iminobispropylamine, and 85 g (0.80 mole) of sodium carbonate.
  • the intermediate product contains 1.2% nitrogen.
  • EXAMPLE Ill CATERPILLAR l-I-I TEST The lubricating oil composition employed in this example was fully formulated motor oil composition containing an alkaline detergent, a zinc dithiophosphate and a pour depressant in a paraffinic mineral oil having an SUS viscosity at 100F. of 535.
  • the detergent of Example I was added to the fully formulated base oil in an amount to give 0.28% nitrogen in the finished oil.
  • the detergent of the invention was also treated for its effectiveness in motor oil compositions for a gasoline engine.
  • the formulated oils were evaluated in laboratory bench tests (Bench Sludge I and Bench Sludge II tests) designed to discriminate between oils of differing light duty deposits control characteristics.
  • the bench Sludge tests are a measure of the ability of a dispersant formulation to retain particulate foreign materials.
  • the numbers obtained indicate the depth of sediment (in millimeters) obtained at the end of the test procedure. In general, the lower the values in the Bench Sludge I and H tests are, the more highly dispersant the formulations are.
  • the base oil employed was a paraffinic hydrocarbon oil having an SUS at 100F of about 125.
  • Three fully formulated oils were prepared containing an alkaline deterge nt, zinc dithiophosphate and a polymethacrylate pour depressant in addition to the dispersants described above.
  • Lubricating oil A contained the dispersant of Example I to give a fully formulated oil containing 0.028 percent nitrogen.
  • Lubricating oil B contained the dispersant of Example II to give a fully formulated oil containing 0.036 percent nitrogen.
  • Lubricating oil C contained the dispersant of Example III to give a fully formulated oil containing 0.081% nitrogen.
  • Lubricating oil D contained no ashless dispersant.
  • a dispersant according to claim 1 represented by the formula:
  • a dispersant according to claim 1 represented by the formula: l5
  • a dispersant according to claim 1 represented by the formula:
  • a dispersant according to claim 1 represented by the formula:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Lubricants (AREA)

Abstract

in which R is a polybutenyl radical having a molecular weight from 900 to 10,000 and a mineral lubricating oil composition containing said polybutenyl-alkylene polyamine polyalkanol.

Polybutenyl-alkylene polyamine-polyalkanol ashless dispersant lubricant additive represented by the general formula:

Description

United States Patent [191 Miller et al.
[ 1 Dec. 16, 1975 Walter W. Hellmuth, Hopewell Junction, both of NY.
[73] Assignee: Texaco Inc., New York, NY.
[22] Filed: Dec. 18, 1974 [21] Appl, No.: 533,910
Related US. Application Data [60] Division of Ser. No. 408,226, Oct. 19, l973, which is a continuation-in-part of Ser. No. 155,286, June 2l, 1971, abandoned.
[52] US. Cl. 260/584 B; 260/584 C [51] Int. Cl. C07C 87/20 [58] Field of Search 260/583 P, 584 B, 584 C [56] References Cited UNITED STATES PATENTS 2,952,707 9/l960 Nikawitz 260/584 B Crowe et a] 260/584 B X Cyba 260/584 R l/l965 7/l965 Primary ExaminerAllen B. Curtis Attorney, Agent, or Firm-TJH. Whaley; C. G. Ries; J. J. OLoughlin [57] ABSTRACT Polybutenyl-alkylene polyamine-polyalkanol ashless dispersant lubricant additive represented by the general formula:
in which R is a polybutenyl radical having a molecular weight from 900 to 10,000 and a mineral lubricating oil composition containing said polybutenyl-alkylene polyamine polyalkanol.
8 Claims, N0 Drawings POLYBUTENYL-ALKYLENE POLYAMINE-POLYALKANOL LUBRICANT ADDITIVE CROSS REFERENCE TO RELATED APPLICATIONS This is a divisional application of application Ser. No. 408,226 filed on Oct. 19, 1973 which in turn is a continuation-in-part of application Ser. No. 155,286, filed on June 21, 1971, now abandoned.
BACKGROUND OF THE INVENTION Straight mineral lubricating oils cannot meet the lubricating needs of modern internal combustion engines and it is customary to incorporate additives in the base oil giving a formulated lubricating composition having enhanced dispersant, detergent, corrosion inhibiting and antiwear properties. The problem of providing a satisfactory motor oil is compounded because these lubricants are subjected to a wide range of operating conditions. In particular, it is rather difficult to formulate a motor oil composition which will be effective under both continuous, high temperature, high speed operating conditions as well as under low-temperature stop and go driving conditions. This problem is further aggravated when the motor oil is intended for service in different type engines, i.e. diesel and gasoline engines, both of which put very severe but different stresses on the motor oil composition.
PRIOR ART Motor oil compositions for internal combustion engines' containing polyolefin-substituted polyamines have been disclosed in US. Pat. No. 3,275,554.
A copending patent application Ser. No. 208,978 filed Dec. 16, 1971 discloses a lubricating oil composition containing a polyisobutenyl-substituted N-aminoethylethanolarnine as an ashless dispersant.
SUMMARY OF THE INVENTION An oil-soluble ashless dispersant for a mineral lubricating oil composition comprising a polybutenyl-alkylene polyamine-polyalkanol is provided as well as a mineral lubricating oil composition containing same. The polybutenyl-alkylene polyamine-polyalkanol is represented by the general formula:
in which R is a polybutenyl radical having a molecular weight from 900 to 10,000, X and Y represent H or (R"O) I-I at least one of X or Y being (RO) I-I, R is a divalent hydrocarbyl radical having from 2 to 8 carbon atoms, R" is a divalent hydrocarbyl radical having from 2 to 4 carbon atoms, x has a value from 1 to 6 and y has a value from 1 to 5. Alternatively, the polyisobutenyl radical R will consist of from about 70 to 700 carbon atoms.
A formulated mineral lubricating oil composition will generally contain the dispersant in a concentration ranging from about 0.1 to 10 weight percent with the preferred concentration being from about 0.2 to 5 percent.
in which R is a polybutenyl radical having a molecular weight from 900 to 10,000, X and Y represent H or (R"O),,H at least one of X or Y being (R"O),,H, R is a divalent hydrocarbyl radical having from 2 to 4 carbon atoms, x has'a value from 1 to 6 and y has a value from 1 to 5.
A preferred class of compounds are those in which R is a polybutenyl radical having a molecular weight from 1,000 to 5,000, with a more preferred class being those in which R is a polybutenyl radical of 1,200 to 2,500 moleweight.
The symbols X and Y represent hydrogen or the radical (R"O), ,I-I withat least one of X or Y being (R"O),,H. The dispersants of this invention thus can be represented by the formulas? and where R, R R" x and y have the values noted above.
Highly effective compounds for lubricating oil compositions are those in which R and R are divalent ethylene and propylene radicals and x and y are 1 or 2. Certain classes of these compounds are represented by the formulas:
and
in which R has the values noted hereinabove.
The compound of the invention contains at least two hydrooxyalkyl radicals per mole of the compound attached to the same or different nitrogen atoms in the compounds. It will be appreciated that a substantially larger number of hydrooxyalkyl groups can be present in the compounds hereinabove defined.
The prescribed polybutenyl-alkylene polyaminepolyalkanol can be prepared in two steps involving a reaction between a polybutenyl polymer and an alkylene polyamine in the first step to form an intermediate compound followed by a reaction with an alkylene oxide in the second step.
3 The polybutenyl component for the above reactions is a polymer of isobutylene which can be prepared by known polymerization methods. This polymer will have an average molecular weight ranging from 900 to 10,000. A preferred polybutenyl polymer is one having an average molecular weight ranging from 1,000 to 5,000 with the most preferred having a molecular weight from 1,200 to 2,500.
The alkylene polyamine component employed can be a straight or branched chain diamine or a polyalkylene polyamine of mixture thereof. Examples of suitable diamines include ethylene diamine, propylene diamine, 1,4-butane diamine, 1,4-pentane diamine and 1,6-hexane diamine. Examples of suitable polyalkylene polyamines include diethylene triamine, piperazine, triethylene tetramine, N-aminoethylpiperazine, tetraethylene pentamine and pentaethylene hexamine.
One method of reacting the polybutenyl polymer with the alkylene polyamine is to first prepare a halogen derivative, i.e. a chloride or bromide derivative of the polybutenyl polymer containing from 0.5 to 10 percent of the halogen according to known methods as set forth in US. Pat. No. 3 275,554 which disclosure is incorporated herein. This halogenated polybutenyl polymer is then reacted with the prescribed alkylene polyamine. In general, 1 to 2 moles of the alkylene polyamine is reacted with the halogenated polybutenyl polymer. This reaction is preferable conducted in the presence of an alkaline material to facilitate the reaction. However, the reaction can be conducted without employing alkaline material and in the absence of a solvent. The reaction is generally conducted at a temperature ranging from about 250 to 500F.
The intermediate compound is then reacted with an alkylene oxide to form the dispersant of the invention. The preferred alkylene oxides for this reaction include ethylene oxide, propylene oxide and butylene oxide although higher alkylene oxides and alkyl substituted alkylene oxides are also suitable. This reaction is generally conducted by dissolving the intermediate compound in a hydrocarbon solvent and gradually adding the alkylene oxide reactant to the reaction mixture over a period of time. The reaction is conveniently conducted at room temperature although higher and lower temperatures generally ranging from about to 100C. can be employed. The ratio of alkylene oxide to alkylated alkylene polyamine is at least 2:1 and is generally in the range of 2:1 to :1 with the preferred range being 2:1 to 5:1. These ranges effect alkoxylation of the primary and secondary nitrogen atoms as well as for polyalkoxylation at these points. The reaction mixture is then filtered and the solvent stripped off under a vacuum.
CHz-CH 0H N-polyisobutenyl-C -N,N-bis-2-hydroxyethyl trithylene tetramine N-polyisobutenyl-C -NN-bis-2-hydroxyethylethylenediamine N-polyisobutenyl-C -N ,hydroxypropyl,
yethyl-ehtylenediamine. N-polyisobutenyl-C -N,N-bis-2-hydroxyethyl-diethylenetriamine.
N-polyisobutenyl(C )-N,N ',N"-tetrakis-Z-hydroxyethyl diethylenetriamine.
N-polyiso butenyl (C )-N 'bis-2-hydroxyethyl-die- N-polyiso butenyl( C )-N,N ,N '-tetrakis-2-hydroxypropyl-diethylene triamine CH-CH2-OH N-polyiso butenyl(C )-N',N"bis-Z-hydroxypropyldiethyle netriamine N-polyisobutenyl(C )-N,N '-bis-2-hydroxyethyl-triethylenetetramine I N-polyisobutenyl(C )-N,N',N",N" -pentakis-2- hydroxyethyl-triethylene tetramine.
The hydrocarbon mineral base oil employed in preparing the lubricating oil compositions of the invention can be a parafiinic base, naphthene base or mixed parafi'm-naphthene base distillate or residual oil. Paraffin base distillate lubricating oil fractions are preferred for the formulation of the highest quality engine or motor oils. The lubricating oil base generally will have been subjected to solvent refining to improve its lubricity and viscosity temperature relationship as well as to solvent dewaxing to remove waxy components and to improve the pour of the oil. Generally, mineral lubricating oils having an SUS viscosity at 100F between 50 and 1,000 may be used in the formulation of the improved lubricants of this-invention with the preferred oils having a viscosity range from 70 to 300 SUS at 100F. A blend of base oils can be employedto provide a suitable base oil for either a single or multigrade motor oil.
The following example illustrates a method for preparing the ashless dispersants of the invention.
EXAMPLE I 4,620 grams of chlorinated polybutene having a molecular weight of about 1300 and containing 2.76 percent of chlorine was mixed with 500 grams (4.3 moles) of hexamethylene diamine and 191 grams (1.8 moles) of sodium carbonate. The reaction mixture was cooled, diluted with four liters of hexane, filtered and the filtrate extracted with methanol. The hexane layer was stripped under vacuum at 200F. yeilding an intermediate product containing 0.8 percent nitrogen. 2,340 grams of the above intermediate product was dissolved in 800 milliliters of toluene and 334 milliliters of isopropyl alcohol. 232 grams (4 moles) of propylene oxide was added dropwise to the solution of the intermediate product over a 30 min. period. The mixture was then heated to reflux for 4 hours, filtered and the solvents stripped off under vacuum at 200F. The dispersant product contained 0.8 percent nitrogen.
The effectiveness of the dispersant of the invention was determined in the Caterpillar l-H Diesel Engine Test. This is a standard industry test which is run on a 1Y73 single cylinder Caterpillar Diesel Lubricant Test Engine as described in FTMS 79la-346T. This test is used to qualify lubricants for MIL-L-2l04B.
The engine is operated at a speed of 1,800 RPM and a fuel input of 4,950 BTU/min for a test duration of 480 hours. Performance is judged by examination of the power section of the engine for ring sticking, piston deposits and ring, piston and liner wear.
EXAMPLE H The procedure of Example I is repeated using 2,000 grams of a chlorinated polybutene containing 2.76% chlorine, 209 g (1.6 mole) iminobispropylamine, and 85 g (0.80 mole) of sodium carbonate. The intermediate product contains 1.2% nitrogen.
mt -cu d! l 17 grams of the above intermediate was dissolved in ml of hexane, and together with 15.5 g (0.27 mole) of propylene oxide, charged to a reaction flask and heated at reflux for seven hours. The reaction mixture was filtered and solvent stripped under vacuum to F..The dispersant product contained 0.97% nitrogen.
EXAMPLE Ill CATERPILLAR l-I-I TEST The lubricating oil composition employed in this example was fully formulated motor oil composition containing an alkaline detergent, a zinc dithiophosphate and a pour depressant in a paraffinic mineral oil having an SUS viscosity at 100F. of 535. The detergent of Example I was added to the fully formulated base oil in an amount to give 0.28% nitrogen in the finished oil.
The'foregoing oil composition was tested in the Caterpillar l-I-I Test for the full test duration of 480 hours. Inspection of the piston showed 5% TGF, and 100% light lacquer on the first land and no deposits below. These results demonstrate the effectiveness of the dispersant for controlling both carbonaceous and lacquer deposits in diesel engine operation.
The detergent of the invention was also treated for its effectiveness in motor oil compositions for a gasoline engine. The formulated oils were evaluated in laboratory bench tests (Bench Sludge I and Bench Sludge II tests) designed to discriminate between oils of differing light duty deposits control characteristics. The bench Sludge tests are a measure of the ability of a dispersant formulation to retain particulate foreign materials. The numbers obtained indicate the depth of sediment (in millimeters) obtained at the end of the test procedure. In general, the lower the values in the Bench Sludge I and H tests are, the more highly dispersant the formulations are.
The base oil employed was a paraffinic hydrocarbon oil having an SUS at 100F of about 125. Three fully formulated oils were prepared containing an alkaline deterge nt, zinc dithiophosphate and a polymethacrylate pour depressant in addition to the dispersants described above. Lubricating oil A contained the dispersant of Example I to give a fully formulated oil containing 0.028 percent nitrogen. Lubricating oil B contained the dispersant of Example II to give a fully formulated oil containing 0.036 percent nitrogen. Lubricating oil C contained the dispersant of Example III to give a fully formulated oil containing 0.081% nitrogen. Lubricating oil D contained no ashless dispersant.
The results of the Bench Sludge Tests are given in Table 1 below.
TABLE 1 BENCH SLUDGE TESTS Bench Sludge l Bench Sludge ll (mm Sediment) (mm Sediment) l. Lubricating Oil A 0.1 0.5 2. Lubricating Oil B 0.3 0.7 3. Lubricating Oil C 0.1 0.4 4. Lubricating Oil D 0.5 3.8
(no dispersant) The foregoing tests show that the dispersant and the lubricating oil composition of the invention are highly effective for controlling deposits in four cycle gasoline engine type operation which this test simulates.
We claim:
1. An oil-soluble, ashless polybutenyl-alkylene polyamine-polyalkanol dispersant represented by the formula:
8 3. A dispersant according to claim 1 in which said polybutenyl radical has a molecular weight ranging from about 1,200 to 2,500.
4. A dispersant according to claim 1 in which x and y each have a value of 1.
5. A dispersant according to claim 1 represented by the formula:
in which the symbols have the values given in Claim 1. 6. A dispersant according to claim 1 represented by the formula: l5
in which the symbols have the values given in claim 1.
7. A dispersant according to claim 1 represented by the formula:
" on -on in which R, x and y have the values given in claim 1.
8. A dispersant according to claim 1 represented by the formula:
in which R, x and y have the values given in claim 1.

Claims (8)

1. AN OIL-SOLUBLE ASHLESS POLYBUTENYL-ALKYLENE POLAMINEPOLYALKANOL DISPERANT REPRESENTED BY THE FORMULA:
2. A dispersant according to claim 1 in which said polybutenyl radical has a molecular weight ranging from 1,000 to 5,000.
3. A dispersant according to claim 1 in which said polybutenyl radical has a molecular weight ranging from about 1,200 to 2,500.
4. A dispersant according to claim 1 in which x and y each have a value of 1.
5. A dispersant according to claim 1 represented by the formula:
6. A dispersant according to claim 1 represented by the formula:
7. A dispersant according to claim 1 represented by the formula:
8. A dispersant according to claim 1 represented by the formula:
US533910A 1971-06-21 1974-12-18 Polybutenyl-alkylene polyamine-polyalkanol lubricant additive Expired - Lifetime US3927104A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0061889A1 (en) * 1981-03-23 1982-10-06 Edwin Cooper Inc. Dispersant substances, a process for making dispersant substances, dispersant formulations and lubricating oil compositions containing said substances, and a method of imparting dispersancy to a lubricating oil
US4433120A (en) * 1981-09-30 1984-02-21 The Borden Chemical Company (Canada) Limited Liquid phenolic resin composition and method for waferboard manufacture
US4465858A (en) * 1983-07-20 1984-08-14 Texaco Inc. Procedure for the partial alkoxylation of polyoxyalkyleneamines
US4479010A (en) * 1983-07-20 1984-10-23 Texaco Inc. Procedure for the alkoxylation of polyoxyalkyleneamines
DE19516435A1 (en) * 1994-05-11 1995-11-16 Air Prod & Chem Synthesis of amine-functional copolymers and terpolymers
WO1995035329A1 (en) * 1994-06-17 1995-12-28 Exxon Chemical Patents Inc. Derivatives of polyamines with one primary amine group and secondary or tertiary amines groups

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2952707A (en) * 1955-01-31 1960-09-13 Givaudan Corp Germicidal polyamino ether alcohols
US3165477A (en) * 1962-01-10 1965-01-12 Dow Chemical Co Process for inhibiting foaming in an aqueous fluid
US3197510A (en) * 1962-03-01 1965-07-27 Universal Oil Prod Co N1-secondary-alkyl-aminoalkyl alkanolamines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2952707A (en) * 1955-01-31 1960-09-13 Givaudan Corp Germicidal polyamino ether alcohols
US3165477A (en) * 1962-01-10 1965-01-12 Dow Chemical Co Process for inhibiting foaming in an aqueous fluid
US3197510A (en) * 1962-03-01 1965-07-27 Universal Oil Prod Co N1-secondary-alkyl-aminoalkyl alkanolamines

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0061889A1 (en) * 1981-03-23 1982-10-06 Edwin Cooper Inc. Dispersant substances, a process for making dispersant substances, dispersant formulations and lubricating oil compositions containing said substances, and a method of imparting dispersancy to a lubricating oil
US4433120A (en) * 1981-09-30 1984-02-21 The Borden Chemical Company (Canada) Limited Liquid phenolic resin composition and method for waferboard manufacture
US4465858A (en) * 1983-07-20 1984-08-14 Texaco Inc. Procedure for the partial alkoxylation of polyoxyalkyleneamines
US4479010A (en) * 1983-07-20 1984-10-23 Texaco Inc. Procedure for the alkoxylation of polyoxyalkyleneamines
US5643859A (en) * 1992-12-17 1997-07-01 Exxon Chemical Patents Inc. Derivatives of polyamines with one primary amine and secondary of tertiary amines
DE19516435A1 (en) * 1994-05-11 1995-11-16 Air Prod & Chem Synthesis of amine-functional copolymers and terpolymers
WO1995035329A1 (en) * 1994-06-17 1995-12-28 Exxon Chemical Patents Inc. Derivatives of polyamines with one primary amine group and secondary or tertiary amines groups

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