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
  • 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
  • C10M159/126—Reaction products obtained by phosphorus or phosphorus-containing compounds, e.g. P x S x with organic compounds with hydrocarbon polymers
• • 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
  • C07F9/04—Reaction products of phosphorus sulfur compounds with hydrocarbons
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/046—Overbased sulfonic acid salts
• • 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
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
  • C10M2225/041—Hydrocarbon polymers
• • 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
• • 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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
• • 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
  • C10N2070/00—Specific manufacturing methods for lubricant compositions
  • C10N2070/02—Concentrating of additives

Definitions

• This invention relates to an ashless lubricant additive, and more particularly to the product of an amine and a phosphosulfurized olefin terpolymer.
• Ashless lubricant additives comprising the reaction product obtained by (a) treating polyisobutylene or polypropylene, with P 8 (b) hydrolyzing the olefin-P 5 product, and (c) treating the hydrolyzed product with an aliphatic amine or an alkylene polyamine have been found useful in improving the dispersancy of lubricating oils and in improving thedetergent properties of the lubricating oil (see US. 3,143,506).
• an ashless lubricant additive was prepared comprising the reaction product obtained by (a) treating a low-molecular-weight polyisobutylene (mol.- wt. 250l500) with P 3 and (b) reacting the phosphosulfurized polyisobutylene with an amine of the formula CH2CHzNI-I wherein x is l-9 (see US. 3,329,612).
• a low-molecular-weight polyisobutylene mol.- wt. 250l500
• P 3 low-molecular-weight polyisobutylene
• x l-9
• an object of this invention to provide an ashless lubricant additive which improves the viscosity index of the lubricating oil as well as improving the detergent, anti-corrosion, anti-oxidant and anti-wear properties.
• the additives of this invention have been found to unexpectedly improve the performance of ex- 3,560,384 Patented Feb. 2, 1971 treme pressure additives in a compounded lubricating oil, even though they do not possess extreme pressure properties themselves. Moreover, the additives of this invention possess exceptionally high shear stability.
• This invention is directed to a lubricant additive comprising the product obtained by reacting (A) A phosphosulfurized ethylene/propylene/ 1,4- hexadiene terpolymer having an average molecular Weight of between about 3,500 and about 65,000 and containing about 35-70 weight percent propylene, about l6 Weight percent 1,4-hexadiene and the remainder being ethylene; with (B) An amine of the formula wherein x is an integer of 2 or 3, and R and R are alkyl groups of l-4 carbon atoms.
• the invention is also directed to a lubricant composition of a mineral lubricating oil and from about 0.1 to about 4 percent by weight of the oil of the additive defined in the preceding paragraph.
• the invention is further directed to a lubricant additive concentrate comprising a neutral lubricating oil and about 5 to about 50 percent by weight of the oil of the additive defined in the first paragraph of this summary.
• the lubricant additive of this invention is conveniently prepared by a two-step process.
• the first step comprises reacting the ethylene/propylene/ 1,4-hexadiene terpolymer with P 8 in the substantial absence of oxygen and under essentially anhydrous conditions, e.g., in an atmosphere of nitrogen or other inert gases, at a temperature of between about 200 F. and 500 F.
• the amount of P 8 employed is ordinarily between about 0.25 to about 5 moles per mole of 1,4- hexadiene in the terpolymer. Preferably 0.5 to 1.5 moles of P 8 are used.
• the time of reaction is normally be tween about 4 and about 30 hours.
• an inert solvent e.g., a hydrocarbon such as hexane, octane, or a halocarbon such as 1,2,4-trichlorobenzene is desirable.
• a halocarbon such as a chloroaromatic compound is preferred.
• the second step comprises reacting the phosphosulfurized terpolymer, which can be used after merely decanting or filtering the reaction mass of the first step to remove insoluble byproducts and unreacted reactants, with the amine.
• the second step is carried out at a temperature of between about 200 F. and about 500 F. for a period of about 4 to about 30 hours.
• the amount of the amine employed can range between about 2 to about 6 moles of amine per atom of phosphorus employed in the first step.
• the preferred amount of amine used is between 2 and 4 moles per atom of phosphorus.
• the same or a different solvent as used in the first step can be employed in this second step. When the same solvent is used in both steps the reaction mass of the first step can be employed directly.
• the final product is ordinarily isolated by usual methods, as for example by precipitating with methanol. However, if the solvent employed in the reaction sequence is compatible with the lubricating oil, the final mixture need only be filtered, or at most, needs only a water wash followed by drying.
• the product, if isolated, may be purified by extraction with methanol, followed by drying.
• the pressure employed in the reaction is preferably atmospheric, although superor subatmospheric pressures may be used.
• the terpolymers employed in the composition of this invention are amorphous polymers which can contain 35-70 weight percent propylene, 16 weight percent 1,4-hexadiene with the remainder ethylene. Preferred weight percent ranges are 42-55 weight percent propylene, 1-4 weight percent 1,4-hexadiene with the remainder ethylene. Preferably the terpolymers should have a relatively narrow molecular weight distribution. The molecular weight distribution, which is determined by dividing the weight average molecular weight by the number average molecular weight, should be less than 8.
• Suitable copolymers are the essentially amorphous, oil soluble copolymers of ethylene which are prepared by polymerization in the presence of coordination catalysts. Polymerization with these catalysts is well known, as described, for example, in U.S. 2,799,668, 2,975,159 and 2,933,480. Since the utilization of these catalysts can produce a variety of polymers from ethylene and propylene, it is important to control the conditions of the reaction in order to obtain the specific amorphous polymers useful in the invention having specified molecular weights and a narrow molecular weight distribution.
• a hydrocarbon soluble vanadium compound e.g. VOCl or vanadium triacetylacetonate
• an alkyl aluminum chloride as described by Natta et al. in U.S. 3,300,459 and in J. Polymer Sci, 51, 411ff and 429ff (1961).
• Use of this catalyst system results in essentially amorphous copolymers soluble in a mineral lubricating oil. Such copolymers exhibit substantially no crystallinity as evidenced by X-ray examination.
• the effectiveness of the subject copolymers as viscosity index improvers lies also in the controlled molecular weight range and narrow distribution of the molecular Weight. This can be achieved by methods described by Natta in J. Polymer Sci, 34, 5411f (1959), e.g. by the use of chain transfer agents such as metal alkyls, esp. Zinc alkyls, and by use of hydrogen pressure, U.S. 3,051,690.
• the article by Natta above cited, J. Polymer Sci., 51, 411 (1961) also described the operative conditions for the preparation of such polymers, such as time, temperature, catalyst concentration and monomer concentration.
• these catalysts must be used in strict absence of oxygen, water or other material with which they react. For this reason the solvents in which they are used are greatly limited, the preferred ones being the saturated aliphatic and hydroaromatic hydrocarbons and certain nonreactive halogen compounds such as tetrachloroethylene and chlorobenzenes. These compounds conveniently serve as solvents for the polymerization which ,is usually carried out in a dilute suspension of the catalyst. The polymerization is normally carried out at ordinary temperatures and pressures. The inherent viscosity range of the terpolymer is between about 0.1 and 1 as measured as a 0.1 weight percent solution in tetrachloroethylene at 30 C.
• the range of 0.1 to 1.0 corresponds to about 3,500 to 65,000 weight average molecular weight as determined by light scattering.
• Preferred terpolymers have an inherent viscosity of 0.1 to 0.6, correspond to 3,500 to 35,000 weight average molecular weight.
• Amines suitable for use in this invention are those of the formula wherein x is 2 or 3 and R and R are the same or different alkyl groups of 1-4 carbon atoms. Preferably R and R are the same.
• Representative suitable amines include N,N- dimethyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethyl-1,3-propanediamine, N,N-diethylethylenediamine, N,N-dipropyl-1,3-propanediamine, N,N-di- 4 propylethylenediamine, N,N-dibutyl-1,3-propanediamine, N,N-dibutylethylenediamine, and the like.
• reaction product formed as described previously does not have a definite stoichiometric relationship between the phosphorus, sulfur and nitrogen atoms present. Hence the reaction product of this invention is believed to be a mixture of products.
• the reaction product is useful, as stated previously, as an additive for improving the properties of mineral or neutral lubricating oils, such as crankcase oils, automotive transmission fluid base oils or hydraulic fluid base oils.
• Lubricating oils and transmission fluids are predominantly parafiinic, solvent-refined neutral oils having Saybolt Universal Seconds (S.U.S.) viscosities of about to 220 at 100 F. and viscosity indices of about to 110.
• preferred lubricating oils should have S.U.S. viscosities of about to 160, while preferred transmission fluids should have S.U.S. viscosities of about 60 to 110.
• Hydraulic fluid base oils are predominantly naphthenic, solven-refined neutral oils having S.U.S. viscosities of not greater than about 50 and pour points not over 65 F.
• Effective amounts of the additive of this invention are employed with the mineral or neutral oils, usually between about 0.1 to 4 percent by weight of the oil and preferably 5 viscosity at F. If desired, solution time may be decreased by preheating the oil to -210 F. before milling or blending.
• EXAMPLE A A typical terpolymer preparation is as follows: Ethylene, propylene and 1,4-hexadiene are polymerized in an evaporatively cooled, continuous flow, stirred reactor operated at 30 C. The partial pressures and flow rates of the monomers are adjusted to obtain the desired composition.
• the terpolymers used in the examples which follow were made in hexane solution in the presence of a coordination catalyst formed in situ by combining diisobutyl aluminum monochloride with vanadium tris(acetylacetonate). The partial pressure of hydrogen in the reactor was 15.6 lb./sq. in. (absolute) and the residence time was 36.3 minutes.
• EXAMPLE 1 Preparation of additive In 1800 ml. of 1,2,4-trichlorobenzene with a dry nitrogen atmosphere about it were reacted 100 g. (0.043 mole as 1,4-hexadiene) of an ethylene, propylene, 1,4-hexadiene terpolymer having a wt. ratio of E61.7/P34.9/ HD-3.4 and an inherent viscosity of 0.44 (as measured on a 0.1 wt. percent solution in tetrachloroethylene at 30, about 23,000 mol. wt.) and 20 g. (0.09 mole) P 5 at a temperature of 200-210 C. for a period of 6 hours.
• reaction mixture was cooled and the insoluble residue was removed by decanting the solution.
• To the solution was added 51 g. (0.5 mole) N,N-dimethyl-1,3-propanediamine.
• the temperature was raised slowly to 205- 210 C. over a 4-hour period and the mixture was allowed to stir at that temperature for 6 hours.
• the reaction mixture was poured into 23 times its volume of methanol to precipitate the reaction product.
• the precipitated reaction product was repeatedly extracted with methanol in a high-speed blender until trichlorobenzene was completely removed and was finally vacuum dried.
• the reaction product contained 1.8 weight percent phosphorus, 2.8 weight percent sulfur, and 1.1 weight percent nitrogen.
• p. (poise) at 0 F. was measured using a cold cranking simulator.
• a universal motor run at constant voltage, drives a rotor which is closely fitted inside a stator.
• a small portion of the oil/additive composition fills the space between the rotor and stator which are maintained at 0 F.
• the speed of the rotor is a function of, and is calibrated to determine the viscosity of the oil/additive composition in poises.
• Table A shows that the additives of this invention, in an amount of 1 weight percent, increase the viscosity of the oil as measured in cs. at 210 F. by about 30 percent; while an amount of 3 weight percent increases the viscosity by about 170 percent.
• Shear stability The shear stabilities of oil compositions containing the same base oil as in the viscosity index test of Example 5 and the amount of various ethylene teipolymers necessary to increase the viscosity of the oil composition to 11.5:t0.1 centistokes at 210 F. were determined using a 250 W., 10 kc. magnetostrictive sonic oscillator in accordance with the technique described in Proposed Method of Test for Shear Stability of Polymer-Containing Oils, in ASTM Standards, vol. I, page 1160 (October 1961). The procedure was modified by shearing a 50 ml. sample for 60 minutes at F. at 0.6 r.f. amps. Shear stability is expressed as the average percent retention of viscosity in Table B shows that the shear stability of the additives of this invention is substantially maintained.
• EXAMPLE 7 Dispersancy power Low temperature deposition tests in a single cylinder CLR engine for 180 hours according to the procedure of FTM-79la Method 348 Modified were carried out.
• Lubricating oil compositions labeled A, B, and C were tested. Each composition contained lubricating oil, zinc dialkyldithiophosphate and a high-base calcium sulfonate (each added to provide rust-inhibition and antioxidant properties to the oil).
• the ingredients of compositions A, B, and C are listed as follows:
• a Ingredients (control) B C SAE-BO base oil (618.8 S.U.S. at 100 F.) Zinc dialkyldithiophosphate, wt., percent- 1 1 1 1 High-base calcium sulfonate, wt., percent 2 2 2 Additive of Example 1, wt. percent... 2 Additive of Example 4, wt, percent. 2
• EXAMPLE 8 Anti-rusting properties The anti-rust properties of the additives of this invention were determined by placing 30 ml. of an oil blend of compositions A-C, described below, in 4-02. jars along with 3 ml. of synthetic exhaust condensate and a SAE 1020 carbon steel billet. The mixture was heated for 24 hours at F. The billet was removed, rinsed with a hydrocarbon solvent and examined for the percent area rusted.
• the MacCoull Test is a method of determining the oxidation stability and corrosive effect of lubricating oils on a copper-lead bearing.
• the test a modification of the method originally developed by The Texas Co. (Method SP148-48, Feb. 1, 1948), is carried out so as to reproduce the oil-bearing conditions which actually exist in an engine, namely, circulation of the oil through a rotating bearing, contact with other metal surfaces and air, and recirculation through the bearing.
• the oil sample being tested is oxidized at a temperature of 350 F.
• each bearing weight is subtracted from its corresponding original weight.
• the difference, reported in milligrams, is known as the bearing weight loss.
• the degree of bearing corrosion by the oil is indicated by the amount of bearing weight loss, a non-corrosive oil showing little or no bearing weight loss and, conversely, a highly corrosive oil showing a much greater bearing weight loss.
• the antioxidant properties were measured by the change in the total acid number before and after the test.
• Total Acid Number, Total Base Number, and Viscosity tests are run on the oil in order to obtain a measure of its resistance to oxidation.
• the relative increase in total acid number and viscosity, and the decrease in total base number are indicative of oxidation of the oil.
• the products of this invention caused a decrease in the amount of oxidation of the oil, over the amount occurring in the oil with no additives in it. In the presence of other commercial anti-oxidants, the level is decreased even further, showing that there are no incompatibility problems to be concerned with.
• Another feature of the additives of this invention is that, in combination with a commercial antioxidant, zinc dialkyldithiophosphate and a high-base calcium petroleum sulfonate, a high percent of the basicity is retained. This indicates that the additives of this invention possess long detergent life.
• the additives of this invention impart superior antiwear properties to the oil.
• terpolymer-P S -diamine additives of this invention were evaluated in a four-ball extreme pressure test. Since these additives exhibited very good antiwear properties, it was expected that they would also possess some Extreme Pressure properties. Frequently these two properties are found in the same additive. That was not the case with these products. The results of this test (Table G) show that they do no possess any Extreme Pressure properties in themselves. Surprisingly, however, when tested in com bination with a commercial zinc dithiophosphate-type Extreme Pressure additive, the additives of this invention greatly enhance the Extreme Pressure properties of the zinc dithiophosphate additive, as shown by an increase in the Mean Hertz Load from 38 to 54 kilograms (in Table G). This synergistic effect was dependent upon the concentration of the zinc dithiophosphate. When the zinc dithiophosphate concentration was decreased from 1 to 0.5 percent, the Extreme Pressure properties decreased as well.
• the test was carried out with a 10-second test duration at each applied load.
• the Mean Hertz Load is calculated from the series of scar diameters.
• the Point of Incipient Seizure is the highest load at which the scar diameter in- TABLE E.M.- ⁇ CCOULL OXIDATION TEST (10 HOURS AT 350F.)
• Oil A Solvent refined neuztral oil 131 SUS at 100 F
• Oil B 0i1
• the table shows that the presence of additives of this invention retards oxidation of the oil and reduces corrosion on bearings.
• the terpolymer-P S -amine additives of this invention are truly multifunctional additives. They possess surprisingly good Vis cosity Index improving properties. They also show an unexpected synergistic eifect on extreme pressure properties when used with a commercial zinc dialkyldithiophosphate additive. In addition they have excellent lowtemperature detergent, antioxidant, bearing corrosion inhibition, antirusting and antiwear properties. At an average use concentration of 2 wt. percent in the lubricating oil, the desired level of performance in each of the above properties can be achieved with only the single additive of the invention. This results in simplification for the refiner in formulating a complete crankcase lubricating oil. In addition, the additive is ashless.
• a lubricant additive consisting essentially of the product obtained by reacting (A) a phosphosulfurized ethylene/propylene/1,4hexadiene terpolymer having an average molecular weight of between about 3,500 and about 65,000 and containing about 35-70 weight percent propylene, about 1-6 weight percent 1,4-hexadiene and the remainder being ethylene; with (B) an amine of the formula H N(CH NRR wherein x is an integer of 2 or 3, and R and R are alkyl groups of 1-4 carbon atoms.
• the additive of claim 1 in which the terpolymer contains 42-55 weight percent propylene, 1-4 weight percent 1,4-hexadiene with the remainder ethylene and in which the molecular weight is between about 3,500 and 35,000.
• a lubricant additive concentrate comprising a lubricating amount of a neutral lubricating oil and about 5 to about 50% by weight of the additive of claim 1.
• a lubricant composition comprising a lubricating amount of a mineral lubricating oil and from about 0.1

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Biochemistry (AREA)
• General Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Lubricants (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=25079637

Family Applications (1)

Country Status (7)

Cited By (1)

• 0
  • NL NL137461D patent/NL137461C/xx active
• 1968
  • 1968-10-14 US US767486A patent/US3560384A/en not_active Expired - Lifetime
• 1969
  • 1969-07-22 GB GB36716/69A patent/GB1212656A/en not_active Expired
  • 1969-08-21 DE DE19691942654 patent/DE1942654B2/de active Pending
  • 1969-09-17 BE BE738975D patent/BE738975A/xx unknown
  • 1969-10-13 FR FR6935017A patent/FR2020645A1/fr not_active Withdrawn
  • 1969-10-13 JP JP44081229A patent/JPS491603B1/ja active Pending
  • 1969-10-14 NL NL6915533A patent/NL6915533A/xx unknown

Also Published As

Similar Documents