US3609078A

US3609078A - Corrosion inhibited grease composition

Info

Publication number: US3609078A
Application number: US752188A
Authority: US
Inventors: Donald D Carlos; Robert H Jordan; Thomas H Webb
Original assignee: Atlantic Richfield Co
Current assignee: Atlantic Richfield Co
Priority date: 1968-08-13
Filing date: 1968-08-13
Publication date: 1971-09-28
Anticipated expiration: 1988-09-28

Abstract

Corrosion and rust inhibitors for lubricating greases are prepared by Friedel-Crafts-catalyzed interpolymerization of a mono-1-alkene, an olefinically unsaturated carboxylic acid (or ester thereof) wherein the olefinic bond is at least 2 carbon atoms away from the carboxyl group and, optionally, a conjugated diene hydrocarbon. Preferably, the mono-1-alkene is normal and has about 14 to 21 carbon atoms, the unsaturated acid has about 10 to 21 carbon atoms and, if the ester is used, is esterified with a lower alkanol, and the diene has 4 to 5 carbon atoms. The corrosion and rust inhibitors for lubricating greases are prepared by condensation of these polymers with an essentially aliphatic polyamine having up to about 11 amino groups, at least one of which is primary, e.g., pentaethylene hexamine.

Description

United States Patent [72] Inventors Donald D. Carlos Crown Point, 1nd.; Robert 11. Jordan, Chicago Heights; Thomas H. Webb, Haul Crest, [11. [21 Appl. No. 752,188

22 Filed Aug. 13, 1968 [45] Patented Sept. 28,1971 [73] Assignee Atlantic Richiield Company [54] CORROSION INHIBITED GREASE COMPOSITION 19 Claims, No Drawings [52] US. Cl 252/40.7, 252/421, 252/515 R, 252/392 [51] Int. Cl Cl0m 1/54, C09k 3/00 501 Field of Search 252 42.1, 51.5 A, 392, 40.7, 51.5 R

[56] References Cited UNITED STATES PATENTS 2,991,249 7/1961 Andress, Jr. et a1. 252/421 X 3,282,970 11/1966 Riggs,.lr.

ABSTRACT: Corrosion and rust inhibitors for lubricating greases are prepared by Friedel-Crafts-catalyzed interpolymerization of a mono-l-alkene, an olefinically unsaturated carboxylic acid (or ester thereof) wherein the olefinic bond is at least 2 carbon atoms away from the carboxyl group and, optionally, a conjugated diene hydrocarbon. Preferably, the mono-l-alkene is normal and has about 14 to 21 carbon atoms, the unsaturated acid has about 10 to 21 carbon atoms and, if the ester is used, is esterified with a lower alkanol, and the diene has 4 to 5 carbon atoms. The corrosion and rust inhibitors for lubricating greases are prepared by condensation of these polymers with an essentially aliphatic polyamine having up to about 1 1 amino groups, at least one of which is primary, e.g., pentaethylenc hexamine.

CORROSION INHIBITED GREASE COMPOSITION This invention relates to polymers and to novel corrosion and rust inhibitors for lubricating greases formed from the polymers. More specifically, the present invention is directed to a Friedel-Crafts-polymerized polymer of an unsaturated monocarboxylic acid (or ester thereof), an alpha-olefin and, optionally, a conjugated diene, and to corrosion and rust inhibited lubricating greases which contain these polymers.

Metal surfaces in contact with lubricating greases may be corroded either by a component present in or formed in the lubricant during service, or by an external material. For example, lubricating greases are susceptible to oxidation to acidic materials, particularly low molecular weight organic acids and mineral acids, which materials may contribute to corrosion of metal surfaces. Moreover, the presence in greases of water and oxygen, or of water containing certain salts, such as sea water, can result in rusting or corrosion of the metal.

Corrosion and rust inhibitors have long been utilized in lubricating greases to circumvent the corrosion and rust problems. For example, the prior art has utilized such materi als as sulfonates and naphthenates of various metals, amines and amine salts, and metal soaps of long chain fatty acids or other high molecular weight acids. Such materials are, however, often susceptible to oxidation to corrosive or otherwise deleterious materials, and may also cause other significant problems, such as, for example, a tendency to weaken or break the gel of the grease.

It has now been found that a grease-compatible, addition polymer of defined olefinically unsaturated carboxylic acid or ester, mono-l-alkene of about 3 to 25, preferably about 14 to 21 carbon atoms, and (optionally) conjugated, diolefinically unsaturated, aliphatic hydrocarbon of 4 to 12, preferably 4 to 5, carbon atoms can be reacted with organic amines to give a grease-compatible polymer product effective as a corrosion and rust inhibitor.

Generally, the polymers of the present invention will be formed by addition polymerization of about 15-95, preferably about 20-90, mol percent of the mono-l-alkene, about 3-85, preferably about 5-40, mol percent of the unsaturated acid or ester, and about 70, or even 80, mol percent of the diene hydrocarbon. Often, when it is desired to exclude the diene hydrocarbon, it is preferred that the polymers contain about 95-15, more preferably about 90-60, mol percent of the mono-l-alkene and about 5-85, more preferably about -40, mol percent of the unsaturated acid or ester. When the inclusion of the diene hydrocarbon is desired, it will often be preferred to prepare polymers of about 92-15, more preferably about 85-20, mol percent of the alkene, about 3-55, more preferably about 5-25, mol percent of the unsaturated acid or ester, and about 5-80, more preferably about 10-70, mol percent of the diene.

The unsaturated acids or esters polymerized with the monol-alkenes to form the novel, base oil-soluble extreme pressure additive of this invention are the acids or esters of the formula wherein R is an olefinically unsaturated, substituted or unsubstituted, hydrocarbon radical of 3 to about 25, preferably about 9 to 20, carbon atoms. The R group, which may be substituted with, for example, acetylenic, aromatic, or other noninterfering groups, contains 1 or more, preferably 1 to 2, olefinic bonds. The carboxylic group is separated, however, from the olefinic bond, or bonds, in R by at least 2 aliphatic, including cycloaliphatic, carbon atoms, preferably at least about 6 or even at least about 8 of such carbon atoms. That is, while the R group is olefinically unsaturated, the carboxyl carbon atom is, however, attached to a nonolefinic carbon atom, and preferably the carboxyl carbon atom is at least about 6, or even at least about 8, aliphatic carbon atoms removed from the first olefinic bond (i.e., at least 5 or 7 carbon atoms removed from the first olefinic carbon atom). The nonolefinically unsaturated carbon-to-carbon 5 chain separating the olefinic bond, or bonds, from the carboxylic group is preferably paraffinic. R in the above formula is hydrogen or alkyl of 1 to carbon atoms, preferably lower alkyl, say of l to 3 carbon atoms. When R' is alkyl, salt formation of the acid with the catalyst used for the polymerization is prevented, and alcohol which is formed later in the reaction with an organic amine can often be readily distilled from the product. Examples of acids which may be used in this polymer are oleic, linoleic, undecylenic, linolenic, ricinoleic, vinyl acetic, etc. The lower alkyl esters of these acids, including the glycerides, *may also be employed, especially the methyl esters. Essentially the same polymer products are, of course, formed from the anhydrides of the acids, as well as from other acid forms, such as the acid amides, which give a condensation type reaction with the aliphatic polyamine. Thus the acid reactant serves to supply the acyl group,

to the corrosion and rust inhibiting additives.

The mono-l-alkenes employed in the present invention can be represented by the formula V wherein R" and R' are selected from the group consisting of hydrogen and alkyl, including cycloalkyl, and the total number of carbon atoms is from about 3 to 25, preferably about 12 to 21, carbon atoms. Preferably, one of R" and R' is hydrogen and the other is a straight chain alkyl to give a normal olefin. The mono-l-alkenes are often used as a mixture and may contain minor amounts, usually less than 10 percent by weight, of other hydrocarbons such as other olefins, diolefins, saturated hydrocarbons and aromatics. The monol alkene may be substituted with, e.g., halogen, etc., so long as the substituent does not interfere with the polymerization or have any other significant deleterious effect.

The conjugated, diethylenically or diolefinically unsaturated, aliphatic hydrocarbons which may be used in making the polymer include the polymerizable, conjugated, diethylenically unsaturated alkenes having from 4 to 12 carbon atoms, preferably 4 to 5 carbons, e.g., conjugated diolefins with a terminal double bond such as 1,3-butadiene, isoprene, etc. The diolefin may be substituted with, e.g., halogen, etc., so long as the substituent does not interfere with the polymerization or have any other significant deleterious effect. An example of a substituted, conjugated diolefin is chloroprene.

The choice of unsaturated acid, conjugated, diethylenically unsaturated aliphatic hydrocarbon (if employed) and monol alkene, their ratios and the extent of reaction are such as to give a grease compatible polymer, and usually the total number of carbon atoms in the acid and mono-l-alkene reactants is at least about 12, preferably at least about 18. Also, more than one acid, conjugated diethylenically unsaturated aliphatic hydrocarbon or mono-l-alkene can be used in forming a given polymer, and minor amounts of other polymerizable monomers may be present.

The polymer employed in preparing the compositions of the present invention can be prepared by subjecting the mono-lalkene, the diethylenically unsaturated, conjugated, aliphatic hydrocarbon (if employed) and the unsaturated acid or ester to a polymerization temperature of about 0 to 50 C., preferably about 0 to 25 C., in the presence of a strong Friedel-Crafts catalyst, such as aluminum chloride or boron trifluoride. A preferred catalyst is aluminum chloride, and it is also preferred to add the unsaturated acid or ester, and any conjugated, diethylenically unsaturated, aliphatic hydrocarbon to be included, to the mono-l-alkene. A coeatalyst may also be employed and will generally be present in an amount of about 0.5 to volumes of eoeatalyst per volume of acidalpha olefin-diene feed. A suitable eocatalyst may also be a solvent for the Friedel-Crafts catalyst. Examples of appropriate cocatalysts are the lower alkyl halides, especially ethyl chloride, methyl chloride and the like.

The strong Friedel-Crafts catalyst will generally be present in the cocatalyst solution in a concentration of about 0.01 to percent, preferably about 0.5 to 7 percent, by weight, and the amount of the Friedel-Crafts catalyst employed is generally about 0.1 to percent by weight, preferably about 2 to 15 percent by weight, of the polymer formed, over and above that portion of the catalyst if any which reacts with the carboxyl group of the acid. The proportions of reactants (diene, unsaturated acid and mono-l-alkene) to catalyst solution employed may often be about 1:2 to 1:10 or even about 7 1:4 to 1:5 moles of reactants per mole of catalyst solution. At least 0.5 mole of catalyst is generally used for every mole of acid in the reactants mixture, when the acid form is reacted. The polymer may be formed by simultaneous addition of the catalyst solution and the monomers to a reaction vessel. The volumetric ratio of catalyst solution to the monomer reactants in a given unit of time is often about 2:1 to about 4:1, preferably about 3 to 1.

After the addition of catalyst and reactants has been completed, the polymerization may be permitted to continue for a short period of time, generally about 5 to 45 minutes, to insure polymerization to a base oil-soluble copolymer product, for instance, a normally liquid material which may have a kinematic viscosity at 210 F. of, say, about 'up to about 1,000 centistokes, preferably about to 150 or even up to about 300 centistokes. The polymerization reaction can then be quenched using, for instance, a lower alkanol, e.g., of 1 to 4 carbon atoms, in solution in a lower alkane. The resulting copolymer can be separated from residual catalyst as by washing with water, alcohol, dilute aqueous caustic soda, hydrochloric acid or other suitable hydrolyzing and washing methods.

The novel corrosion and rust inhibitor of the present invention can be prepared by the condensation reaction of the copolymer of mono-l-alkene, unsaturated acid (or ester) and diene (if employed) with an essentially aliphatic polyamine. Suitable polyamines may be represented by the general formula:

wherein R is an alkylene radical of 2 to 14 or more carbon atoms, preferably 2 to about 7 carbon atoms; R is selected from hydrogen and hydrocarbon radicals such as alkyl, including cycloalkyl, and the radicals may have, for instance, 1 to 30 or more carbon atoms, preferably 1 to about 7 carbon atoms; and n is a number from l to about 10, preferably about 2 to 6. R may extend between two N-atoms, for instance, the two to which R is attached, and, in this case, these nitrogen atoms will have only one other bond for further attachment. The R and R substituents are preferably saturated, but may be unsaturated, and may be substituted with nondeleterious substituents, especially lower alkyl. Thus, for imidazoline formation, a 1,2-diumine, one amine group of which is primary, can he used; and suitable amines may be represented by the following general formula:

wherein R is selected from hydrogen and hydrocarbon radicals such as alkyl, as noted above, or is amino alkylof about 30, preferably 1 to about 7 carbon atoms, and R" is selected from H and alkyl of l to about 12 or more carbon atoms, preferably 1 to about 5 carbon atoms. R may also be a hydroxy-alkyl, alkoxy-alkyl or aromatic radical.

Thus, useful polyamines include, for instance, monoalkylenediamines, dialkylaminoalkylamines, polyalkylenepolyamines, N-(p-aminoalkyl)piperazines, etc. illustrative of suitable monoalkylene diamines are ethylene diamine, propylene diamine, butylene diamine, octylene diamine, etc. Examples of suitable dialkylaminoalkylamines are dimethylaminoethylamine, dimethylaminopropylamine, dimethylaminobutylamine, diethylaminopropylamine, diethylaminoamylamine, dipropylaminopropylamine, methylpropylaminoamylamine, propylbutylaminoethylamine, etc. Examples of polyallgylenepolyamines are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexapropyleneheptamine, tetrabutylene pentamine, polyamine D (a mixture of aliphatic and cyclic.polyethyleneamines boiling above 340 C. and having an average molecular weight nearly the same as pentaethylene hexamine and having as principal components pentaethylene hexamine, symmetrical and unsymmetrical diaminoethyl triaminoethylamine, symmetrical diaminoethyl triethylenetetramine, symmetrical and unsymmetrical diaminoethyl, diaminoethyl piperazine, piperazinoethyl triethylenetetramine, 4-(N-piperazinoethyl) triethylenetetramine, bis-piperazinoethylamine, and aminoethyl (dipiperazinoethane), polyamine H (bottoms from manufacturing tetraethylene pentamine) etc. Suitable N-(B- aminoalkyl) piperazines include N-methyl-N'-(B-aminocthyl) piperazine, N-(B-aminoisopropyl) piperazine, etc.

In the reaction of the copolymer with an organic polyamine to prepare the corrosion and rust inhibitor of the invention, the polyamine is generally reacted in an amount sufiieient to provide about 0.1, or even about 0.6, to about 14 gram atoms of hydrogen-bonded nitrogen per mole equivalent of carboxyl groups in the polymer; preferably, about 1.5 to 4 gram atoms of hydrogen-bonded nitrogen per mole equivalent of carboxyl groups will be provided. By hydrogen-bonded nitrogen is meant nitrogen of a primary or secondary amine group of the polyamine, which nitrogen may or may not still be bonded to hydrogen after the polyamine is condensed with the polymer. By carboxyl group" is meant the group which may, depending on the monomer employed, be supplied either by a carboxylic acid or ester. Often, to provide the above nitrogen-to-carboxyl ratio, there will be used about 0.3 to 1.5, or even 2, moles of the polyamine per mole equivalent of carboxyl groups in the polymer. However, a slight excess of amine can be advantageous to insure essentially complete reaction of the carboxyl groups of the polymer and avoid undue cross-linking, and a large excess of amine may be present. if desired.

The condensation reaction is usually conducted at a temperature of about 60 to 320 C. depending upon whether amide or imidazoline formation is desired. Preferably, the reaction temperature for amide formation is about to 180 C. and that for imidazoline formation is about 200 to 300 C. The reaction is conducted to give a base oil-soluble product and often the reaction takes about 0.25 to 5 hours, preferably about 0.5 to 3 hours, and water or alcohol is removed as formed. The resulting condensation product is compatible with the base greases and ordinarily has a kinematic viscosity at F. of from about 1,000 to 20,000, preferably about 3,000 to about 15,000 centistokes, and a kinematic viscosity at 210 F. of at least about 50 to 1,000, preferably about to 750, centistokes. The condensation product is added to the lubricating greases in minor amounts, usually in the range of about 0.1 to 5 percent or more, preferably about 0.5 to 2 percent, by weight of the grease. The grease constituent of our new compositions can be any known grease covering the entire range of N.L.G.l. classifications. For instance, the thickening component of the grease can be a metal salt or soap of any of the fatty'acids having from about to 32 carbon atoms, which acids can be saturated or unsaturated and substituted, as with other polar groups. These acids include palmitic, stearic, oleic, linoleic, ricinoleic, palm oil fatty acids, cottonseed oil fatty acids, hydrogenated fish oil fatty acids, lard oil fatty acids, rape seed oil fatty acids, etc., and their mixtures. Other acids, the soaps of which can be employed, are those derived from petroleum such as naphthenic acids, petroleum oil and wax oxidates. The preferred thickeners are the soaps of hydroxy carboxylic acids in which the hydroxyl group is at least 12 carbon atoms removed from the carboxyl group, e.g., l2-hydroxy stearic acid and hydrogenated castor oil.

Among the salt or soap-forming bases which can be used in preparing the soap thickeners are the alkali metal bases such as those of lithium, sodium and potassium, and the alkaline earth metal bases such as those of barium, calcium and strontium. Mixtures of these soaps can be utilized as well. The soap content of the grease compositions of the present invention will usually be a minor amount sufficient to give the desired grease consistency and will often vary within therange of about 5 to percent, most advantageously between about 5 and 15 percent, by weight of the total grease composition.

Greases employed in the present invention can be oil base greases having a mineral oil or synthetic oil base (e.g., a synthetic diester base such as di(2-ethylhexyl) adipate). The mineral oils which can be used are of wide viscosity range, for instance, including those having viscosities from about 50 SUS at 100 F. to about 2,000 SUS at 210 F. The mineral oil can be highly refined and solvent treated, or otherwise refined, e.g. by hydrogenation, if desired, by known means. Among the synthetic oil bases, which can be employed are polymerized olefins, alkylated aromatics, silicone polymers, polyalkylene glycols and their partial or complete ethers and esters.

Grease compositions to be used in the present invention can be prepared from preformed soaps, or the soaps can be formed in situ in a grease-forming base. In general, it is 40 preferred to thicken a base material, such as a mineral oil, with a soap formed in situ and then dehydrate and adjust the viscosity and other properties of the grease to the desired range by incorporating additional base oil.

Materials normally incorporated in lubricating oils to impart special characteristics can also be added to the compositions of this invention. These include extreme pressure agents, antiwear agents, etc. The amount of such additives included in the composition usually ranges from about 0.01 weight percent up to about 20 or more weight percent, and in general they can be employed in any amounts desired, provided the composition is not unduly deleteriously affected.

The following example is included to further illustrate the present invention.

EXAMPLE I 5 To a mixture of oleflns (predominantly normal mono-l-alkenes) of the following approximate composition:

petroleum sulfonic acids, and l0 was added 1,3 butadiene and methyl oleate in a mole ratio of alpha-olefin to butadiene to methyl oleate of l to 3 to 4, based on the average molecular weight (243) of the alpha-olefin mixture. A one liter flask was equipped with a Dean Starlgtrap and two addition funnels. A Dry lee trap was mounted on,the Dean Stark trap to remove and condense thevolatile solvent, ethyl chloride, used in the polymerization. One funnel was charged with the polymerization feed, and to the remaining funnel was charged a catalyst solution consisting of 5.2 grams aluminum chloride per 100 ml. of ethyl chloride at 12C.

Both the polymerization feed and the catalyst solution were introduced into the reaction flask simultaneously, the polymerization mixture at a rate of 19.6 ml. per minute, the catalyst solution at a rate of 49.4 ml. per minute. The total time for the addition of olefin-linoleic acid and catalyst solution was 12 minutes and the polymerization mixture was stirred for an additional l2 minutes. The temperature during the polymerization was 15.5 C. and 340 ml. of ethyl chloride was trapped out of the polymerization system. Hexane, 400 ml., and 400 ml. of isopropanol were added to quench the catalyst.

The copolymer was washed three times with water. The polymer was stripped of solvents and had a KV at 100 F. of 131.7 cs., acid number of 38.0 and an iodine number of 32.0.

To a reaction flask was charged 200 grns. of the copolymer made as noted above and 26 grams tetraethylene-pentamine. The system was purged with nitrogen over a 15 minute period as the temperature was increased to C. The temperature was increased to 270 C. over a 50 minute period and a 19 cm. vacuum was applied at 270 C. for a period of minutes to facilitate the removal of water. The temperature was allowed to reach room temperature under this reduced pressure. The polymer analyzed 3.69 percent nitrogen. The product was tested as a corrosion and rust inhibitor in a lithium roller bearing grease in the ASTM D-l743 Bearing Corrosion Test, in comparison with the base grease itself, and with the base grease containing commercially available rust inhibitor Amine T," an imidazoline-tall oil derivative. The results appear below as table I.

1.57 Amine T." I 0.75 a oi product of Example I.

The results in table l indicate that the polymer additive of example i is highly effective as a corrosion and rust inhibitor. in particular, it is apparent from the F. water spray test that the additive of the present invention is far superior in water resistance at elevated temperatures than either the base grease or the grease with the Amine T rust and corrosion inhibitor. Rust inhibition properties would, consequently, be retained a much longer time for greases formulated with the additive of the present example.

EXAMPLE ll The same type of reaction equipment is used as in example i. To a mixture of the alpha-olefin feed as in example I are added isoprene and methyl oleate to produce a mole ratio of alpha olefin-isoprene-methyl oleate of 6.05 to 2.05 to 1.00, based on the average molecular weight of the alpha-olefin mixture. The same polymerization equipment is used as in ex- 1 75 ample l. One funnel is charged with the reactant feed, and to the remaining funnel is charged a catalyst solution consisting of 5.2 grams aluminum chloride per 100 ml. of ethyl chloride. Both the olefin feed and the catalyst solution are introduced into the reaction flash simultaneously, the olefin mixture at a rate of 20.8 ml. per minute (0.0525 moles per minute alphaolefin, 0.0173 moles per minute isoprene, 0.00860 moles per minute methyl oleate), the catalyst solution at a rate of 39.5 ml. per minute (0.0154 moles per minute aluminum chloride). The total time for addition is 12 minutes and the polymerization is continued for an additional 28 minutes. The temperature during polymerization is 16 C. and 280 ml. (59 percent) of ethyl chloride are trapped out of the polymerization system. Hexane, 400 ml. and 400 ml. of isopropanol are added to quench the catalyst. The copolymer is washed with water and after topping of solvents, has the following properties: KV at 100 F. of 1,190 cs; KV at 210 F. of 94.54 cs; lodine number, 30.7; Saponification number, 24.3; Specific gravity, 0.8780.

To a 500 ml. reaction flask are charged 110 grams of the copolymer and grams of tetraethylene pentamine. The system is purged with nitrogen over a minute period as the temperature is increased to 65 C. The temperature is increased to 270 C. over a 25 minute period and a 15 cm. vacuum is applied at 270 C. These conditions are maintained for a period of 67 minutes, after which the reaction product is allowed to reach room temperature under this reduced pressure. The polymer is washed with water and stripped of solvents. The polymer has the following properties: KV at 100 F. of 5,082 cs; KV at 210 F. of 198.85 cs; Specific gravity, 0.8852; Iodine number 28.7; percent Nitrogen, 2.00.

lnfrared detects the SiNbond and determines the structure to be an imidazoline with some amide present.

The polymer is tested as corrosion and rust inhibitor as described in example 1 and the polymeric product of example 11 proves to have similarly excellent properties.

EXAMPLE 111 The same type of reaction equipment is used as in example 1. To a mixture of the normal alpha-olefin feed as used in example l are added isoprene and linoleic acid in a mole ratio of alpha-olefin to isoprene to linoleic acid of 6.65/2.45/1.0, based on the average molecular weight (243) of the alphaolefin mixture. The olefin intake is charged with the olefinlinoleic acid-diethylenically unsaturated alkene feed, and the catalyst intake is charged with a catalyst solution consisting of 5.2 grams aluminum chloride per 100 ml. of ethyl chloride at 1 2 C.

Both the reactant feed and the catalyst solution are introduced into the reaction flask simultaneously, the olefiniclinoleic acid-diethylenically unsaturated alkene-mixture at a rate of 24.2 ml. per minute (0.0615 moles per minute C l4-C2 1 alpha-olefin, 0.026 moles per minute isoprene, 0.00923 moles per minute linoleic acid), the catalyst solution at a rate of 49 ml. per minute (0.0192 moles per minute aluminum chloride). The total time for the addition is 10 minutes and the polymerization mixture is stirred for an additional minutes. The temperature during the polymerization is 16 C. and 320 ml. (61 percent) of ethyl chloride are trapped out of the polymerization system. Hexane, 400 ml., and 400 ml. of isopropanol are added to quench the catalyst.

The copolymer is washed with dilute hydrochloric acid and washed three additional times with water. The polymer is stripped of solvents and had a KV at 100 F of 3,603 cs; KV at 210 F. of 199.54 cs; acid number of 25.44 and an iodine number of43.9; and a specific gravity of 0.8778.

To a 500 ml. reaction flask are charged 100 grams of the copolymer made as noted above and 8.0 grams tetraethylenepentamine. The system is purged with nitrogen over a 15 minute period as the temperature is increased to 65 C. The temperature is increased to 270 C. over a 20 minute period and a 15 cm. vacuum is applied at 270 C. for a period of 75 minutes to facilitate the removal of water. The temperature is allowed to reach room temperature under this reduced pressure. The product is washed and stripped of solvents. The polymer has a specific gravity of 0.8933; KV at 100 F., 13,500 cs; KV at 210 F., 550.63 cs; iodine number, 47.4; and 2.51 percent nitrogen. Infrared detects the C=N bond and confirms the imidazoline ring structure with a trace of amide present. The polymer is tested as a corrosion and rust inhibitor a in example I, with similarly good properties being indicated.

It is claimed:

l. A lubricating grease composition consisting essentially of a major amount of a base oil of lubricating viscosity and sufficient fatty acid alkaline metal salt to provide a composition of grease consistency and a small amount, sufficient to enhance the corrosion and rust inhibiting characteristics of the grease, of a grease-compatible condensation reaction product of (A) a grease-compatible copolymer fonned by use of a strong Friedel-Crafts catalyst, of about 5 to mole percent of material having the formula:

R--H1OR wherein R is an olefinically unsaturated hydrocarbon radical of 3 to about 25 carbon atoms, the carboxyl carbon atom being separated from all olefinic bonds in R by at least 2 aliphatic carbon atoms, and R is selected from the group consisting of hydrogen and alkyl of 1 to 15 carbon atoms, and about 95 to 15 mole percent of mono-l-alkene of 3 to 25 carbon atoms, said material and said monol-alkene being selected so that the total number of carbon atoms in these components is at least about 12, and (B) polyamine having the formula:

wherein R is an alkylene radical of 2 to 14 carbon atoms, R is selected from the group consisting of hydrogen and hydrocarbon radicals of 1 to 30 carbon atoms, and n is a number from 1 to about 10, said (A) and (B) being reacted in amounts sufficient to provide about 0.1 to 14 gram atoms of hydrogenbonded nitrogen per mole equivalent of carboxyl groups in (A).

2. The composition of claim 1 wherein the grease is lithium soap-thickened mineral lubricating oil.

3. The composition of claim 1 wherein the condensation reaction product is present in amounts of about 0.1 'to 10 percent, by weight of the grease.

4. The composition of claim 1 wherein the condensation reaction product is present in amounts of about 0.25 to 7.5 percent, by weight of the grease.

5. A lubricating grease composition consisting essentially of a major amount of fatty acid alkaline metal salt thickened mineral oil-base lubricating grease and a small amount, sufficient to enhance the rust and corrosion inhibiting characteristics of the grease, of a mineral oil-base-grease-compatible condensation reaction product of (A) a grease-compatible copolymer, formed by use of a strong FriedelCrafts catalyst, of about 10 to 40 mole percent of material having the formula:

wherein R is an olefinically unsaturated hydrocarbon radical of about 9 to 20 carbon atoms, the carboxyl carbon atom being separated from all olefinic bonds in R by at least about 6 paraffinic carbon atoms and R' is selected from the group consisting of hydrogen and lower alkyl, and about to 60 mole percent of normal mono-l-alkene of about 12 to 21 carbon atoms, and (B) polyamine having the formula:

wherein R is an alkylene radical of 2 to 7 carbon atoms, R is selected from the group consisting of hydrogen and alkyl radicals of l to about 7 carbon atoms, and n is a number from about 2 to 6, said (A) and (B) being reacted in amounts sufficient to provide about 0.6 to 14 gram atoms of hydrogenbonded nitrogen per mole equivalent of carboxyl groups in (A).

6. The composition of claim 5 wherein R in the polyamine is hydrogen and R in the polyamine has 2 carbon atoms.

7. The composition of claim 6 wherein the material is methyl oleate.

8. The composition of claim 7 wherein component (B) is tetraethylenepentamine and said (A) and (B) are reacted in amounts sufficient to provide about 0.3 to 2 moles of (B) per mole equivalent of methyl oleate in (A).

9. A lubricating grease composition consisting essentially of a major amount of a lubricating grease and a small amount, sufficient to enhance the corrosion and rust inhibiting characteristics of the grease, of a grease-compatible condensation reaction product of (A) a grease-compatible copolymer, formed by use of a strong Friedel-Crafts catalyst, of about 3 to 55 mole percent of material having the formula:

wherein R is an olefinically unsaturated hydrocarbon radical of 3 to about 25 carbon atoms, the carboxyl carbon atom being separated from all olefinic bonds in R by at least 2 aliphatic carbon atoms and R is selected from the group consisting of hydrogen and alkyl of l to 15 carbon atoms, about to 80 mole percent of conjugated, diolefmically unsaturated, aliphatic hydrocarbon of 4 to 12 carbon atoms and about 92 to 15 mole percent of mono-l-alkene of 3 to carbon atoms, said material and said mono-l-alkene being selected so that the total number of carbon atoms in these components is at least about 12 and (B) polyamine having the formula:

wherein R is an alkylene radical of 2 to 14 carbon atoms, R is selected from the group consisting of hydrogen and hydrocarbon radicals of 1 to carbon atoms, and n is a number from 1 to about 10, said (A) and (B) being reacted in amounts sufficient to provide about 0.1 to 14 gram atoms of hydrogenbonded nitrogen per mole equivalent of carboxyl groups in (A).

10. The composition of claim 9 wherein the grease is a lithium soap-thickened mineral lubricating oil.

11. The composition of claim 9 wherein the condensation reaction product is present in amounts of about 0.1 to 10 per cent, by weight of the grease.

12. The composition of claim 9 wherein the condensation reaction product is present in amounts of about 0.25 to 7.5 percent, by weight of the grease.

13. The composition of claim 12 wherein the conjugated, diolefinically unsaturated, aliphatic hydrocarbon is butadienel, 3.

14. The composition of claim 13 wherein the material is methyl oleate.

15. A lubricating grease composition consisting essentially ofa major amount of mineral oil-base lubricating grease and a small amount, sufficient to enhance the corrosion and rust inhibiting characteristics of the grease, of a grease-compatible condensation reaction product of (A) a grease-compatible copolymer formed by use of a strong Friedel-Crafts Catalyst of about 5 to 25 mole percent of material having the formula:

wherein R is an olefinically unsaturated hydrocarbon radical of about 9 to 20 carbon atoms, the carboxyl carbon atom being separated from all olefinic bonds in R by at least about 6 paraffmic carbon atoms and R is selected from the group consisting of hydrogen and lower alkyl, about 10 to 70 mole percent of conjugated, diolefinically unsaturated, aliphatic hydrocarbon of 4 to 5 carbon atoms and about to 20 mole percent of normal mono-l-alkene of about 12 to 21 carbon atoms and (B) polyamine having the formula:

wherein R is an alkylene radical of2 to about 7 carbon atoms, R is selected from the group consisting of hydrogen and alkyl radicals of l to about 7 carbon atoms, and n is a number from about 2 to 6, said (A) and (B) being reacted in amounts sufficient to provide about 0.6 to 14 gram atoms of hydrogenbonded nitrogen per mole equivalent of carboxyl groups in (A).

16. The composition of claim 15 wherein R in the polyamine is hydrogen and R in the polyamine has 2 carbon atoms.

17. The composition of claim 16 wherein the carboxyl group containing material is methyl oleate.

18. The composition of claim 17 wherein component (B) is tetraethylenepentamine and said (A) and (B) are reacted in amounts sufficient to provide about 0.3 to 2 moles of(B) per mole equivalent of methyl oleate in (A)v 19. The composition of claim 18 wherein the conjugated, diolefinically unsaturated, aliphatic hydrocarbon is butadiene- 1, 3.

Claims

2. The composition of claim 1 wherein the grease is lithium soap-thickened mineral lubricating oil.
3. The composition of claim 1 wherein the condensation reaction product is present in amounts of about 0.1 to 10 percent, by weight of the grease.
4. The composition of claim 1 wherein the condensation reaction product is present in amounts of about 0.25 to 7.5 percent, by weight of the grease.
5. A lubricating grease composition consisting essentially of a major amount of fatty acid alkaline metal salt thickened mineral oil-base lubricating grease and a small amount, sufficient to enhance the rust and corrosion inhibiting characteristics of the grease, of a mineral oil-base-grease-compatible condensation reaction product of (A) a grease-compatible copolymer, formed by use of a strong Friedel-Crafts catalyst, of about 10 to 40 mole percent of material having the formula: wherein R is an olefinically unsaturated hydrocarbon radical of about 9 to 20 carbon atoms, the carboxyl carbon atom being separated from all olefinic bonds in R by at least about 6 paraffinic carbon atoms and R'' is selected from the group consisting of hydrogen and lower alkyl, and about 90 to 60 mole percent of normal mono-1-alkene of about 12 to 21 carbon atoms, and (B) polyamine having the formula: wherein R'' is an alkylene radical of 2 to 7 carbon atoms, R is selected from the group consisting of hydrogen and alkyl radicals of 1 to about 7 carbon atoms, and n is a number from about 2 to 6, said (A) and (B) being reacted in amounts sufficient to provide about 0.6 to 14 gram atoms of hydrogen-bonded nitrogen per mole equivalent of carboxyl groups in (A).
6. The composition of claim 5 wherein R in the polyamine is hydrogen and R'' in the polyamine has 2 carbon atoms.
7. The composition of claim 6 wherein the material is methyl oleate.
8. The composition of claim 7 wherein component (B) is tetraethylenepentamine and said (A) and (B) are reacted in amounts sufficient to provide about 0.3 to 2 moles of (B) per mole equivalent of methyl oleate in (A).
9. A lubricating grease composition consisting essentially of a major amount of a lubricating grease and a small amount, sufficient to enhance the corrosion and rust inhibiting characteristics of the grease, of a grease-compatible condensation reaction product of (A) a grease-compatible copolymer, formed by use of a strong Friedel-Crafts catalyst, of about 3 to 55 mole percent of material having the formula: wherein R is an olefinically unsaturated hydrocarbon radical of 3 to about 25 carbon atoms, the carboxyl carbon atom being separated from all olefinic bonds in R by at least 2 aliphatic carbon atoms and R'' is selected from the group consisting of hydrogen and alkyl of 1 to 15 carbon atoms, about 5 to 80 mole percent of conjugated, diolefinically unsaturated, aliphatic hydrocarbon of 4 to 12 carbon atoms and about 92 to 15 mole percent of mono-1-alkene of 3 to 25 carbon atoms, said material and said mono-1-alkene being selected so that the total number of carbon atoms in these components is at least about 12 and (B) polyamine having the formula: wherein R'' is an alkylene radical of 2 to 14 carbon atoms, R is selected from the group consisting of hydrogen and hydrocarbon radicals of 1 to 30 carbon atoms, and n is a number from 1 to about 10, said (A) and (B) being reacted in amounts sufficient to provide about 0.1 to 14 gram atoms of hydrogen-bonded nitrogen per mole equivalent of carboxyl groups in (A).
10. The composition of claim 9 wherein the grease is a lithium soap-thickened mineral lubricating oil.
11. The composition of claim 9 wherein the condensation reaction product is present in amounts of about 0.1 to 10 percent, bY weight of the grease.
12. The composition of claim 9 wherein the condensation reaction product is present in amounts of about 0.25 to 7.5 percent, by weight of the grease.
13. The composition of claim 12 wherein the conjugated, diolefinically unsaturated, aliphatic hydrocarbon is butadiene-1, 3.
14. The composition of claim 13 wherein the material is methyl oleate.
15. A lubricating grease composition consisting essentially of a major amount of mineral oil-base lubricating grease and a small amount, sufficient to enhance the corrosion and rust inhibiting characteristics of the grease, of a grease-compatible condensation reaction product of (A) a grease-compatible copolymer formed by use of a strong Friedel-Crafts catalyst of about 5 to 25 mole percent of material having the formula: wherein R is an olefinically unsaturated hydrocarbon radical of about 9 to 20 carbon atoms, the carboxyl carbon atom being separated from all olefinic bonds in R by at least about 6 paraffinic carbon atoms and R'' is selected from the group consisting of hydrogen and lower alkyl, about 10 to 70 mole percent of conjugated, diolefinically unsaturated, aliphatic hydrocarbon of 4 to 5 carbon atoms and about 85 to 20 mole percent of normal mono-1-alkene of about 12 to 21 carbon atoms and (B) polyamine having the formula: wherein R'' is an alkylene radical of 2 to about 7 carbon atoms, R is selected from the group consisting of hydrogen and alkyl radicals of 1 to about 7 carbon atoms, and n is a number from about 2 to 6, said (A) and (B) being reacted in amounts sufficient to provide about 0.6 to 14 gram atoms of hydrogen-bonded nitrogen per mole equivalent of carboxyl groups in (A).
16. The composition of claim 15 wherein R in the polyamine is hydrogen and R'' in the polyamine has 2 carbon atoms.
17. The composition of claim 16 wherein the carboxyl group containing material is methyl oleate.
18. The composition of claim 17 wherein component (B) is tetraethylenepentamine and said (A) and (B) are reacted in amounts sufficient to provide about 0.3 to 2 moles of (B) per mole equivalent of methyl oleate in (A).
19. The composition of claim 18 wherein the conjugated, diolefinically unsaturated, aliphatic hydrocarbon is butadiene-1, 3.