US3872019A

US3872019A - Oil-soluble lubricant bi-functional additives from mannich condensation products of oxidized olefin copolymers, amines and aldehydes

Info

Publication number: US3872019A
Application number: US278719A
Authority: US
Inventors: George S Culbertson; Gary R Chipman; Robert E Karll
Original assignee: Standard Oil Co
Current assignee: BP Corp North America Inc
Priority date: 1972-08-08
Filing date: 1972-08-08
Publication date: 1975-03-18
Anticipated expiration: 1992-03-18
Also published as: DE2339510A1; DD109662A5; CS169845B2; JPS49132102A; YU213573A; GB1425089A; NL180109B; NL7310932A; ZA734861B; FR2195652B1; BG21864A3; DE2339510C2; AU5861073A; FR2195652A1; JPS5945036B2; BE803316A; JPS5681396A; YU35371B; HU174376B; CA1012672A

Abstract

Bi-functional lubricant additives exhibiting dispersant and V.I. improving properties are obtained by the Mannich Condensation of an oxidized long-chain high molecular weight amorphous copolymer of essentially ethylene and propylene having a number average molecular weight of at least about 10,000 and at least 140 pendant methyl groups per 1,000 chain carbon atoms, with a formaldehyde yielding reactant and a primary or secondary amine or polyamine, said reactants being employed in the molar ratio of from about 1:2:2 to about 1:20:20, respectively.

Description

Uited States atent 91 Culbertson et a1.

[11] 3,872,019 Mar. 18, 1975 1 OIL-SOLUBLE LUBRICANT Bl-FUNCTIONAL ADDITIVES FROM MANNICH CONDENSATION PRODUCTS OF OXIDIZED OLEFIN COPOLYMERS, AMINES AND ALDEHYDES [75] Inventors: George S. Culbertson, Downers Grove; Gary R. Chipman, Naperville; Robert E. Karll, Batavia,

all of Ill.

[73] Assignee: Standard Oil Company, Chicago, Ill.

[22] Filed: Aug. 8, 1972 [21] Appl. No.: 278,719

[52] US. Cl....llI....I..f..f7fl5i. A, 252/515 R.

260/33.6 UA, 260/72 R, 260/854 [51] Int. Cl C08g 9/04, C08g 37/32, ClOm 1/32 [58] Field ofs'ar'tii...26o/72 R; 252/515 R, 51.5 A, 252/854 [56] 9 References Cited UNITED STATES PATENTS 3,316,177 4/1967 Dorer 252/515 12/1970 Culbertson et a1. 260/72 3,647,692 3/1972 Lee 252/515 Primary E.raminerHoward E. Schain Attorney, Agent, or Firm-Fred R. Ahlers; Arthur G. Gilkes; William T. McClain [57] ABSTRACT lecular weight of at least about 10,000 and at least 140 pendant methyl groups per 1,000 chain carbon atoms, with a formaldehyde yielding reactant and a primary or secondary amine or polyamine, said reactants being employed in the molar ratio of from about 1:222 to about 1:20:20, respectively.

13 Claims, N0 Drawings BACKGROUND OF THE INVENTION Lubricant deterioration in high speed engines causes the formation of lacquer, sludge and carbon deposits on the interior surfaces of the engines which accelerates wear and reduces engine efficiency. To reduce the tendency for such deleterious products to deposit on the surfaces of the engine it is known to incorporate in the lubricating oil additives having dispersancy and/or detergency properties.

The continuing search for and the necessity of having available ashless dispersants and/or detergents additives for motor oils is well known. Since the development of the positive crankcase ventilation system (PCV) there is a greater demand than ever for improved additives of such types.

It is also well known that lubricating oils have a tendency to become thin at elevated temperatures while becoming thick at low temperatures, and thus it is generally necessary to add additives to such lubricants which improve their viscosity-temperature relationships. For example, in the case of a crankcase lubricating oil in a cold engine, it is desirable that the oil not become so thick that it is difficult to start the engine; while, when the engine is hot it is necessary that the oil remain sufficiently viscous that an oil film is maintained between the moving parts.

Various products have been developed for the purpose of providing the dispersant and/or detergent function. Neutral and overbased metallo-organic compounds, such as the alkaline earth salts of sulfonic acids, and hydrocarbon-P 5 reaction products were among the first addition agents used for this purpose. Their in-service drawbacks include the formation of undesirable metal-ash thermal decomposition products. Other proposed additives were amine salts, amides, imides and amidines of polybutenyl-substituted polycarboxylic acids. Still other proposed additives were combinations of alkaline earth sulfonates and Mannich condensation products of low molecular weight alkyl-substituted hydroxyaromatic compounds, amines having at least one replaceable hydrogen on a nitrogen, and aldehydes; alkaline earth salts of such Mannich condensation products have also been suggested.

Mannich condensation products derived from alkylsubstituted hydroxyaromatic compounds having a relatively low molecular weight alkyl substituent, i.e., 2 to carbon atoms in the alkyl substituent are described in U.S. Pat. Nos. 2,403,453;.2,353,49l; 2,363,134; 2,459,112; 2,984,550 and 3,036,003. U.S. Pat. No. 3,368,972 describes as dispersant and/or detergent addition agents for lubricating oils high molecular weight Mannich condensation products from high molecular weight alkyl-substituted hydroxyaromatic compounds, in which the alkyl-substituent has a molecular weight in the range of 600-3,000; an amine and an aldehyde. However, such condensation products do not exhibit bi-functional dispersancy and V.l. improving properties.

Culbertson et a1. U.S. Pat. No. 3.544,5 20 issued Dec. 1, 1970, discloses and claims as ashless dispersants the products prepared by subjecting an olefin polymer hav- LII ing a molecular weight of about ZOO-2,000; such as a polybutene or polypropylene to oxidation in the presence of a catalyst such as manganous carbonate, and the oxidized polymer then condensed with formaldehyde and a polyalkylene polyamine. Such condensation products while effective as ashless dispersants, do not impart V.I. improving properties to lubricating oils.

Additives, imparting sludge inhibiting and detergent properties to lubricating oils, prepared by reacting,oxidized degraded interpolymers of propylene and ethylene having a molecular weight of at least about 1,000. with maleic anhydride, and neutralizing the acidic intermediate with an alkylene polyamine, is described in U.S. Pat. No. 3,316,177.

We have discovered a product prepared as hereinafter described which is useful as a lubricant additive possessing both dispersant and V.I. improving properties, which bifunctional properties are not exhibited by the additives described in the above prior art patents.

SUMMARY OF THE INVENTION In accordance with the present invention, the bifunctional additive is prepared by reacting simultaneously, at a temperature of about 250-350F., an oxidized copolymer (as hereinafter defined) of ethylene and propylene with a formaldehyde-yielding reactant, and an aliphatic amine or polyamine, and recovering the resultant reaction product; said reactants being employed in the molar ratio of from 1:212 to about 1:20:20.

In the preparation of the additive of this invention it is desirable to conduct the Mannich condensation in the presence of a non-reactive organic solvent or diluent, such as, for example, an aromatic hydrocarbon solvent e.g. benzene, xylene, toluene etc., or an aliphatic hydrocarbon solvent, such as hexane, for example. Particularly suitable as a solventor diluent is a low viscosity hydrocarbon oil, such as a solvent-extracted SAE 5W mineral oil. The use ofa solvent or diluent is particularly advantageous to facilitate the mixing of the reactants, and the control of the reaction temperatures.

THE COPOLYMER' The term copolymer as used herein and in the appended claims, refers to amorphous copolymers derived from essentially ethylene and propylene; however, such copolymers may contain minor amounts, i.e., up to 10 percent, based on the molar amounts of the monomeric ethylene and propylene units in the copolymer, of polymerized units derived from other olefin monomers. Such other olefin monomers include olefins of the general formula RCH=CH in which R is an aliphatic or cycloaliphatic radical of from 2 to about 20 carbon atoms, for example, butenel,hexene-l, 4-methy1-l-pentene, decene-l, vinylidene norbornene, S-methylene-Z-norborene, etc. Other olefin monomers having a plurality of double bonds may be used, in particular diolefins containing from about 4 to about 25 carbon atoms, e.g., 1,4-butadiene, 1,3- hexadiene, l,4-pentadiene, 2-methyl-1,5-hexadiene, 1,7-octadiene etc.

Suitable ethylene-propylene copolymers contain from about 30 to about 65, preferably from about 35 to about 45 mole percent propylene, have a number average molecular weight of at least about 20,000, i.e., from about 20,000 to about 200,000 or more, and preferably from about 25,000 to about 40,000, and contain at least 150 pendant methyl groups per 1,000 chain carbon atoms.

A particularly suitable ethylene-propylene copolymer is one having the following characteristics:

Number Average Molecular Weight Percent (Molar) Propylene Monomer Pendant Methyl Groups per L000 Chain Carbon Atoms Inherent Viscosity Gardner Viscosity Mooney Viscosity (A) O.I gram copolymer in I cc dccnlin .il I3SC. (B) 3.0% copolymer in toluene at 25C. (C) ASTM D4646 U-V (B) -35 (C) OXIDATION OF THE COPOLYMER The oxidation can be accomplished by contacting the copolymer under suitable conditions of temperature and at atmospheric or elevated pressures, with an oxidizing agent such as air or free oxygen, or any oxygencontaining material capable of releasing oxygen under the oxidation conditions. If desired, the oxidation can be conducted in the presence of known oxidation catalysts, such as platinum or a platinum group metal, and compounds containing metals such as copper, iron, cobalt, cadmium, manganese,vanadium etc. The oxidation can be carried out by methods described in US. Pat. Nos. 2,982,728; 3,316,177; 3,153,025; 3,365,499; and 3,544,520.

Generally, the oxidation can be carried out over a wide temperature range, depending upon the oxidizing agent used; for example, with an active oxidizing agent,

e.g., S0 temperatures in the range of -F. to 400F. have been used, while with less active oxidizing agents, e.g., air, temperatures in the range of l00800F. have been used. Further, depending upon the rate desired, the oxidation can be conducted at sub-atmospheric, atmospheric or super-atmospheric pressures, and in the presence or absence of oxidation catalysts. The conditions of temperature, pressure, oxygen content of the oxidizing agent, the rate of introducing the oxidizing agent, the catalyst employed, if any, etc., are correlated and controlled, by those skilled in the art, so as to obtain the desired optimum results.

The following will illustrate one method of oxidizing the copolymer; to a copolymer of ethylene and propylene (1 part), having a number average molecular weight of about 28,000, was added a solvent-extracted SAE 5W mineral oil(9 parts) in an open reaction vessel, and the mixture slowly stirred and heated at a temperature of 360F., under an inert gas atmosphere, until solution of the rubber-like polymer in the solvent was effected. Maintaining the 360F. temperature, the mixture was rapidly agitated in an atmosphere composed of 50 percent air and 50 percent nitrogen, to promote the oxidation of the copolymer. A 50:50 air-nitrogen ratio was used to preclude the possibility of an explosive mixture being formed. Reaction in the described manner was continued for 2.5-4.0 hours. About 550 oxygen atoms per molecule of the copolymer were introduced under such oxidation conditions.

THE AMINE REACTANT The amine reactant used in the preparation of the products of the present invention are primary or secondary aliphatic amines and diamines of the general formula H N(CH ),,NH wherein y is an integer 3 to 10, said amines and diamines containing up to about 10 carbon atoms in the alkyl group, and polyalkylcne polyamines of the general formula wherein A is a divalent alkylene radical of about 2 to about 6 carbon atoms, and x is an integer from I to about 10. Illustrative of suitable amines are: methylamine, dibutylamine, cyclohexylamine, propylamine, decylamine, ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, tripropylene tetramine, tetrapropylene pentamine, and other polyalkylene polyamines in which the alkylene groups contain suitably up to about 10 carbon atoms.

THE ALDEHYDE REACTANT Illustrative of aldehydes suitable for use in accordance with the present invention are aliphatic aldehydes such as, for example, formaldehyde, acetaldehyde, b-hydroxybutyraldehyde. We prefer to use formaldehyde or a formaldehyde-yielding compound such as paraformaldehyde and formalin.

The chemical composition of the reaction product of this invention cannot be characterized with preciseness by chemical structural formula. While it is believed that the oxidation of the copolymer produces predominately ketones, it is known that minor amounts of aldehydes, acids and perhaps esters may also be present. In view of the complex nature of the oxidized reaction product, the precise composition of such product cannot be defined by its chemical structure, but rather must be defined by its method of preparation.

The herein described reaction products of the present invention are effective bifunctional dispersant and V.I. improving additives in oleaginous lubricant compositions when used in amounts of from about 0.1 to about 10 percent..Suitable lubricating base oils are mineral oils, i.e., petroleum oils, synthetic lubricating oils, such as those obtained by the polymerization of hydrocarbons, and other well-known synthetic lubricating oils, and lubricating oils of animal or vegetable orgin. Concentrates of a suitable oil base containing more than 10, i.e., from about 10 percent to about percent or more, of the additive of the present invention, alone or in combination with other well-known additives, can be used for blending with lubricating oils in proportions desired for particular conditions or use to give a finished product containing from about 0.1 to about 10 percent of bifunctional additive of this invention.

PREFERRED EMBODIMENTS OF THE INVENTION The following examples are illustrative of preferred embodiments of the present invention.

EXAMPLE 1 Part A Preparation of the Copolymer An amorphous ethylene-propylene copolymer was prepared by solution polymerization using a Ziegler- Natta type catalyst, vanadium oxytrichloride solution in combination with an ethylaluminum sesquichloride solution. Dry n-heptane (1200 ml.) was saturated at 86F. and 30 p.s.i.g. with a gas mixture consisting of 50 mole percent ethylene, 35 mole percent propylene and 15 mole percent hydrogen. The gas mixture was introduced at the rate of 100 liters per hour, circulated through the heptane, and then passed out of the system. When saturation was complete, the addition of the catalyst components, in heptane solution was started. The vanadium oxytrichloride solution (0.370 percent by weight) was introduced into the olefin mixture at the rate of 13 ml/hr., and the ethylaluminum sesquichloride solution (0.459 percent-wt.) at the rate of 60 ml/hr; the molar ratio of Al/V was 8.06. When polymerization began the inflow of the propylene and of the ethylene was adjusted to compensate for the greater reactivity of the latter. The average ratio of propylene- /ethylene by weight was 2.3 (as determined by periodic gas chromatographic analyses). After 1.25 hours polymerization was stopped by displacing the gas mixture with nitrogen and stopping the catalyst addition. The reaction mixture was then washed twice with methanol to deactivate and remove the catalyst. The yield based on the amount of vanadium catalyst used was 1680 grams of polymer per gram of VOC1 The recovered opolymer had a number average molecular weight (M,,) of 28,000 (determined by vapor pressure osmometry); 159 pendant methyl groups per 1000 chain carbon atoms (determined by infrared spectroscopy), and an inherent viscosity of 2.28 dl/g. (measured in decalin at 135C. and 0.1 g./100 ml.).

Part B Oxidation of the Copolymer A solution of 70 grams ofthe copolymer, obtained in Part A, above, in 1000 grams of heptane was heated to 250F. while blowing with nitrogen to remove the heptane. 280 grams ofa SAE 5W mineral oil was gradually added as the heptane was removed, and the viscous oil copolymer mixture brought to 430F. with vigorous stirring. Blowing with nitrogen was discontinued at this point, to allow atmospheric oxygen to diffuse into the reaction vessel. After 0.5 hour, thermal and oxidative degradations reduced the viscosity of the mixture such that vigorous stirring could be maintained at the optimum oxidation temperature of 310F. Heating with stirring was continued at such temperature for a total of 2.5 hours. Conversion, as measured by silica gel chromatography, was 100 percent.

Part C Condensation of Oxidized Copolymer with Aldehyde and amine To 665 grams of the oil solution of the oxidized copolymer from Part B, above, (20.0 percent active oxidized copolymer) were added 900 grams of benzene, and the solution heated to 120F. Solid paraformaldehydc (0.69 grams; 0.52 percent by weight on oxidized copolymer) was then added, and the mixture heated to a temperature of 140F. over a 0.5 hour period. Hexamethylene diamine (2.66 grams; 2.0 percent by weight on the oxidized copolymer) was then added I and the solution refluxed vigorously for three hours at 176F.

The resultant condensation product was then heated at 300F., with nitrogen blowing, for one hour to remove the benzene solvent. The activity of the solventfree product was adjusted to 13 percent by the addition of the SAE 5W oil.

The recovered condensation product was crystal clear, had a color of 6.70 (ASTM color scale), and contained 0.06 percent nitrogen and 0.1 percent oxygen.

EXAMPLE 2 Part A Oxidation of the Copolymer A solution of grams of the copolymer, obtained in Part A of Example 1, above, in 1,000 grams of heptane was heated to 250F., while blowing with nitrogen to remove the heptane. 630 grams of a solvent-extracted SAE 5W mineral oil was gradually added as the heptane was removed, and the viscous oil-polymer mixture heated to a temperature of 360F. with vigorous stirring and nitrogen blowing. These conditions were maintained for 0.5 hour to remove the last traces of the heptane solvent. Blowing with pure nitrogen was discontinued at this point, and a gas atmosphere composed of 50 percent air and 50 percent nitrogen was introduced. Heating at 360F. with vigorous stirring was continued for a total of three hours. Conversion, as measured by silica gel chromatography, was percent. Carbonyl content of the oxidized product, as measured by the infrared absorbance band at 5.8 microns, was 7.5 absorbance units, (0.002 inch cell thickness). Oxygen analysis of the product gave 0.89 percent oxygen.

Part B -Condensati0n Product of Oxidized Copolymer with Aldehyde and Amine Two hundred grams of the oxidized copolymer, obtained in Part A, above, (10 percent active oxidized c0- polymer in SAE 5W mineral oil diluent), was heated to 320F. under a nitrogen blanket. Solid paraformaldehyde (0.38 grams; 1.9 wt. percent on the oxidized copolymer) and molten anhydrous hexamethylene diamine (1.5 grams; 7.5 wt. percent on the oxidized copolymer) were added simultaneously to the stirred reaction mixture maintained at a temperature of 320F. under a nitrogen blanket. Stirring and heating at said temperature were continued for two hours, during which time the Mannich condensation was effected with the evolution of water.

At the end of the two hour reaction period, the resultant condensation product was blown vigorously with nitrogen for 0.5 hour to remove any remaining volatile by-products. The reaction product was filtered, yielding a crystal-clear product having the following inspections:

Percent Active Condensation Product 10.0 Percent nitrogen 0.185 Percent oxygen 0.45 Color (ASTM) 7.0 Viscosity (SSU at 210F.) 3200 EXAMPLE 3 Part A Oxidation of the Copolymer A solution of grams of the copolymer obtained in Part A of Example 1, above, in 1745 grams of heptane was heated to 250F. under a stream of nitrogen to remove the heptane. A solvent-extracted SAE W mineraloil (770 grams) was gradually added as the heptane was being removed. After complete removal of the heptane by heating to 350F. under a stream of nitrogen, 885 grams of an oil-copolymer solution, containing 13 percent copolymer, was obtained.

Oxidation of the copolymer was effected by heating the above mixture to 400F., and removing the nitrogen blanket so as to diffuse air into the reaction vessel. Stirring, at this point, was increased to effect sufficient splashing of the viscous liquid to insure intimate airliquid contact. After 0.5 hour of reaction in this manner, oxidation of the copolymer and attendant degradation had begun to take place, resulting in a viscosity decrease in the reaction medium. Agitation and reaction temperature were gradually decreased while maintaining the desired gas-liquid contact, until a temperature of 310F. was reached. This reaction temperature maintains a desired balance between a convenient oxidation rate, and undesirable excessive polymer degradation. After a total reaction time of 2.5 hours, Silica Gel Chromatography indicated a recovered product containing 17 percent active oxidized products, corresponding to theoretical conversion of the copolymer to oxygenated species (allowing for the typical 5-6 percent oxidation of the diluent oil).

Part B Condensation Product of the Oxidized Copolymer with Aldehyde and Amine To 885 grams of the oxidized copolymer product, obtained in Part A, above, were added 900 grams benzene, and the temperature of the solution brought to 120F. under a nitrogen blanket, the nitrogen being introduced at the rate of 1.0 CFH. Powdered, anhydrous paraformaldehyde (0.62 grams, 0.0207 mole) was added in one lot, and the temperature increased to 140F. over a 0.5 hour period. Then molten anhydrous hexamethylene diamine (2.4 grams, 0.02107 mole) was added in one lot, and the resultant mixture rapidly brought to the reflux temperature of benzene (176F.). Molar ratios of the reactants were 1:4:4, respectively.

Maintaining a nitrogen blanket, benzene and water (formed as a by-product in the condensation reaction) were distilled from the reaction mass. After one hour, at a moderate distillation rate, the distillate in the receiver was clear, indicating the'absence of residual water; at this point the Mannich condensation was considered to be completed. The residual benzene was removed by increasing the temperature to 320F., and introducing nitrogen, at the rate of 6 CFH, into the reaction vessel. Heating and nitrogen blowing were continued for one hour'longer to remove the last traces of volatile impurities. A yield of 99.4 percent (880 grams) of a haze-free Mannich Condensation product having the following inspection was obtained:

0.058% (found) 0.063% (calculated) 2100 Activity Nitrogen Viscosity (SSU at 210F.)

EXAMPLE 4 Part B of Example 3, above. However, in this example the molar ratios of oxidized copolymer, paraformaldehyde, and hexamethylene diamine employed were l:8.6:8.6, respectively, on the basis, as in Example 3, above, of the oxidized copolymer having a number average molecular weight of 22,200. Reaction conditions and procedures for effecting the Mannich condensation were the same as those used in Part B of Example 3, above. A yield of 99.5 percent of a clear Mannich Condensation product having the following product inspection was obtained:

Activity 8.0% Nitrogen 0.084% (found) 0.086% (Calculated) Viscosity (SSU at 210F.) 1125 EXAMPLE 4 A copolymer of 55 mole percent ethylene, 35 mole percent propylene and 10 mole percent l-decene was prepared as in Part A of Example 1, above, and then oxidized as described in Part B of said Example 1. The oxidized copolymer was then reacted with paraformaldehyde and hexamethylene diamine under Mannich Condensation conditions, as described in Part C of Example 1, above; said reactants being used in the molar ratios of 114:4, respectively. The recovered Mannich Condensation product had an activity of 13 percent and contained 0.06 percent nitrogen.

The V.1. imparting property of the herein described Mannich Condensation products of the present invention is demonstrated by the data in the following TABLE 1, in which the following oil samples were employed:

Sample A Neutral Base Oil Sample Sample A plus 1.1% neat (i.e., undiluted) Mannich B Condensation product Example 1, Part C.

Sample A plus 1.5% neat Oxidized Polyisobutylene (number average molecular weight 1500), Mannich Condensation product.

Sample A plus 1.5% neat Oxidized Ethylene-Propylene Copolymer (number average molecular weight 2000), Mannich Condensation product.

Sample Sample The above data demonstrate that the Mannich Condensation products of the present invention are highly efficient in imparting the desired V.I. property to a low V.1. base oil stock.

The effectiveness of the additives of the present invention is demonstrated by the so-called Spot Dispersancy Test. In this test, a measured amount of the additive to be tested is mixed with a measured volume of crankcase lubricant oil formulation which has been used in a Ford Sequence V C Engine Test for 192 hours (twice the time of the standard test time). This composition is heated and stirred at about 300F. for about 16 hours, and an aliquot is transferred to blotting paper. A control is made at the same time by stirring and heat- Sample A:

ing at 300F. for 16 hours a second oil from the 192 hour Ford Sequence V C Engine Test, and depositing an aliquot on blotting paper. At the same time, a readily available commercial ashless dispersant is mixed in the same manner as above, for comparison purposes. The deposits on the blotting paper are measured to obtain the average diameter of the outer oil ring (Do), and the average diameter of the inner sludge ring (Da). The ratio of Da/Do is an indication of the detergent-dispersant property of the addition agent.

The data in TABLE 11 below compare the dispersancy properties of the additive of the present invention with a commercial dispersant additive. The following samples were employed in this test:

Sample A Control Oil no dispersent Sample B Control Oil plus 1.0% Mannich Condensation product Example 3, Part B, supra. Sample C Control Oil plus 1.0% commercial dispersant-Vl additive.

TABLE II SAMPLE PERCENT DISPERSANCY A 45 B 93 C 66 Solvent-extracted SAE Oil 49.8% (vol.) Solvenbextracted SAE Oil 36.8% do. Zinc dialkyl dithiophosphate 1.2% do. High-base Magnesium sulfonate 1.2% do. Mannich Product. Example 3. Part B l 1.0% do.

(13% active; 1.4% [vol.] active ingredient) Sample B:

Solvent-extracted SAE 5 Oil 25.1% (vol.) Solventextracted SAE 10 Oil 60.0% do. Zinc dialkyl dithiophosphate 1.2% do. High-base Magnesium sulfonate 1.2% do. Pour point depressant 0.5% do. Mannich Product. bland of Example 3. 12.0% do. Part B and Example 4 (10% active; 1.2% [vol.] active ingredient) Sample C:

Solventextracted SAE 5 Oil 30.0% (vol.) Solvent-extracted SAE 10 Oil 56.93% do. Zinc dialkyl dithiophosphate 1.1% do. High-base Magnesium sulfonate 2.0% do. Commercial Vl lmprover 5.2% do. Silicone Anti-foam Agent 500 ppm Commercial Ashless Dispersant 4.77% do.

(42% active: 2.0% [\ol.] active ingredient) The data obtained in these tests are given in TABLE 111, below:

TABLE III ENGINE RATINGS SAMPLE Sludge Varnish Piston Varnish A 8.4 8.5 7.3 B 9.5 8.6 7.5 C 9.0 8.5 8.2

The data presented in TABLES I, 11 and 111, above, demonstrate that the Mannich Condensation products prepared in accordance with the present invention exhibit a unique combination of high level dispersancy and excellent Vl properties.

Percentages given herein and in the appended claims are weight percentages unless otherwise stated.

Although the present invention has been described with reference to certain specific preferred embodiments thereof, the invention is not limited thereto, but includes within its scope such modifications and variations as come within the scope and spirit of the appended claims.

We claim:

1. The oil-soluble condensation product prepared by the process comprising, reacting simultaneously at a temperature of from about 250F. to about 350F. (1) an oxidized high molecular weight amorphous copolymer of essentially ethylene and propylene, said copolymer having a number average molecular weight of at least about 10,000 and at least pendant methyl groups per 1,000 chain carbon atoms, (2) a formaldehyde-yielding reactant and (3) a primary or secondary aliphatic amine selected from the group consisting of an alkyl amine having from about 2 to about 12 carbon atoms, an aliphatic diamine of the general formula H N(CH ),,NH wherein y is an integer of from about 3 to about 10, and a polyalkylene polyamine ofthe general formula wherein A is a divalent alkylene radical of from about 2 to 6 carbon atoms, and x is an integer of from 1 to about 10, wherein said reactants are used in the respective reactant molar ratio of from about 112:2 to about 1:20:20.

2. The oil-soluble condensation. product of claim 1, wherein said copolymer comprises essentially ethylene and from about 30 to about 65 mole percent propylene.

3. The oil-soluble condensation product of claim 1, wherein said copolymer comprises essentially ethylene, from about 30 to about 65 mole percent propylene, and up to about 20 mole percent of a third olefinic monomer selected from the group having the general formula RCHH wherein R is an aliphatic or cycloaliphatic radical of from 2 to about 20 carbon atoms, and diolefinic monomers having from about 4 to about 25 carbon atoms.

4. The oil-soluble condensation product of claim 3, in which the third olefinic monomer is l-decene.

5. The oil-soluble condensation product of claim 1, in which the formaldehyde-yielding reactant is paraformaldehyde, and the aliphatic diamine is hexamethylene diamine.

6. The oil-soluble condensation product of claim 1, in which the formaldehyde-yielding reactant is paraformaldehyde, and the polyalkylene polyamine is tetraethylene pentamine.

7. The oil-soluble condensation product of claim 1,

in which the copolymer comprises essentially and about 38-42 mole percent propylene, said copolymer having a number average molecular weight of from about 25,000 to about 35,000, and from about 160 to about 170 pendant methyl groups per 1,000 chain carbon atoms, said formaldehyde-yielding reactant is paraformaldehyde, and said aliphatic diamine'is hexamethylene diamine, said reactants being employed in the molar ratio of about l:l4.5:l4.5, respectively.

8. A lubricant composition comprising a major proportion of a normally liquid oleaginous lubricant, and from about 0.1 to about percent of the oil-soluble condensation product defined in claim 1.

9. A lubricant composition comprising a major proportion of a normally liquid oleaginous lubricant, and from about 0.1 to about 10 percent of the oil-soluble condensation product defined in claim 2.

10. A lubricant composition comprising, a major proportion of a normally liquid oleaginous lubricant, and from about 0.1 to about 10 percent of the oil-soluble condensation product defined in claim 3.

11. A lubricant composition comprising, a major proportion of a normally liquid oleaginous lubricant, and from about 0.1 to about 10 percent of the oil-soluble condensation defined in claim 4.

12. A lubricant composition comprising, a major proportion of a normally liquid oleaginous lubricant, and from about 0.1 to about 10 percent of the oil-soluble condensation product defined in claim 6.

13. An addition agent concentrate for lubricating oils, comprising a lubricating oil containing from about 10 to about percent of the oil-soluble condensation product defined in claim 1.

UNITED STATES PATENT OFFICE r CERTIFICATE OF PATENT NO. 3,872,019

DATED I :March 18, 1975 INVENTOR(S) 1 George S. Culbertson, Gary R. Chipman, and Robert E. Karll It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. Line r 55 "10," should be 10%, 5 5 "oil" should be oil- T 38 0.02107" should be 0.0207 7 6 "ethylenepropylene" should be ethylene-propylene 9 55 "bland" should be "blend" 11 Following "essentially" insert ethylene Signed and sealed this 24th day of June 1975.

(SEAL) Attest:

C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks

Claims

1. THE OIL-SOLUBLE CONDENSATION PRODUCT PREPARED BY THE PROCESS COMPRISING, REACTING SIMULTANEOUSLY AT A TEMPERATURE OF FROM ABOUT 250*F. TO ABOUT 350*F. (1) AN OXIDIZED HIGH MOLECULAR WEIGHT AMORPHOUS COPOLYMER OF ESSENTIALLY ETHYLENE AND PRPROPYLENE, SAID COPOLYMER HAVING A NUMBER AVERAGE MOLECULAR WEIGHT OF AT LEAST ABOUT 10,000 AND AT LEAST 140 PENDANT METHYL GROUPS PER 1,000 CHAIN CARBON ATOMS, (2) A FORMALDEHYDE-YIELDING REACTANT AND (3) A PRIMARY OR SECONDARY ALIPHATIC AMINE SELECTED FRM THE GROUP CONSISTING OF AN ALALKYL AMINE HAVING FROM BOUT 2 TO ABOUT 12 CARBON ATOMS, AN ALIPHATIC DIAMINE OF THE GENERAL FORMULA H2N(CH2)YNH2 WHEREIN Y IS AN INTEGER OF FROM ABOUT 3 TO ABOUT 10, AND A POLYALKYLENE POLYAMINE OF THE GENERAL FORMULA

2. The oil-soluble condensation product of claim 1, wherein said copolymer comprises essentially ethylene and from about 30 to about 65 mole percent propylene.

3. The oil-soluble condensation product of claim 1, wherein said copolymer comprises essentially ethylene, from about 30 to about 65 mole percent propylene, and up to about 20 mole percent of a third olefinic monomer selected from the group having the general formula RCH CH2 wherein R is an aliphatic or cycloaliphatic radical of from 2 to about 20 carbon atoms, and diolefinic monomers having from about 4 to about 25 carbon atoms.

4. The oil-soluble condensation product of claim 3, in which the third olefinic monomer is 1-decene.

7. The oil-soluble condensation product of claim 1, in which the copolymer comprises essentially and about 38-42 mole percent propylene, said copolymer having a number average molecular weight of from about 25,000 to about 35,000, and from about 160 to about 170 pendant methyl groups per 1,000 chain carbon atoms, said formaldehyde-yielding reactant is paraformaldehyde, and said aliphatic diamine is hexamethylene diamine, said reactants being employed in the molar ratio of about 1:14.5:14.5, respectively.

8. A lubricant composition comprising a major proportion of a normally liquid oleaginous lubricant, and from about 0.1 to about 10 percent of the oil-soluble condensation product defined in claim 1.

13. An addition agent concentrate for lubricating oils, comprising a lubricating oil containing from about 10 to about 75 percent of the oil-soluble condensation product defined in claim