US3280034A - Alkenylsuccinimido alkyl-substituted imidazolidines and related materials - Google Patents

Alkenylsuccinimido alkyl-substituted imidazolidines and related materials Download PDF

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US3280034A
US3280034A US31229263A US3280034A US 3280034 A US3280034 A US 3280034A US 31229263 A US31229263 A US 31229263A US 3280034 A US3280034 A US 3280034A
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Joseph F Anzenberger
James B Davis
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Monsanto Co
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Description

United States Patent 0 3,280,034 ALKENYLSUCCINIMIDO ALKYL-SUBSTITUTED IMHDAZOLIDINES AND RELATED MATERIALS Joseph F. Anzenherger, St. Louis and James B. Davis, Kirkwood, Mo., assignors to Monsanto Company, a

corporation of Delaware No Drawing. Filed Sept. 30, 1963, Ser. No. 312,292 2t) Claims. (Cl. 252-515) This application is a continuation-in-part of application Serial No. 296,489, filed July 22, 1963 and now aban doned.

This invention relates to certain new imidazolidines, bis-imidazolidines and related products which are useful as detergents in lubricating oil compositions.

Under the conditions encountered in a large percentage of present-day automobile driving (i.e., the so-called stopand-go driving), automobile engines do not attain their most desirable and efiicient operation temperatures. As a result, large quantities of oil-insoluble oxidation products are formed which eventually find their way into the crankcase by flowing past the piston rings. Since most of these products are oil insoluble, they tend to deposit on the internal parts of the engine, resulting in further inefiicient engine operation.

In present-day practice, deposition of the oxidation products is minimized by incorporating into lubricating where R is an alkenyl radical having a molecular weight of from about 500 to about 2500, preferably about 800 to about 1500, R is hydrogen or a lower alkyl radical; R and R are each selected from hydrogen, alkyl, alkenyl and haloalkyl; R is selected from hydrogen and lower alkyl; x is a whole number from 0 to 3; and Z is selected from alkylene and alkenylene containing one to sixteen carbon atoms. For convenience imidazolidines, as used herein, is intended to include both the monoand bisimidazolidines.

'ice

The imidazolidines of this invention can be prepared by reacting (a) An alkenylsuccinic anhydride represented by the structure or the acid thereof,

(b) A polyethylene amine, represented by the structure and (c) A carbonyl-containing compound, that is,

(i) an aldehyde or ketone represented by the structure m-ii aa (ii) a dialdehyde or diketone represented by the structure 0 O R4J I}Z-(UJR4 where R, R R R R X and Z have their aforedescribed significance. The mol ratios of (a) (b) :(c) used will be about 1:121, respectively, to prepare mono-imidazolidines .and about 2:2: 1, respectively, to prepare bisimidazolidines. Normally (b) and (c) are reacted to prepare an intermediate imidazolidine which is reacted with (a) to prepare the compounds of this invention. To provide a reaction medium and facilitate the removal of the water of reaction, a hydrocarbon solvent can be used, e.g., toluene or xylene. Also mineral oil can be used as a reaction medium, either alone or in combination with a hydrocarbon solvent. Suitable temperatures for preparing the imidazolidines at atmospheric pressure are of the order of 100-175 C. and vacuum can be used in the case of a mineral oil reaction medium to operate at about the same temperatures.

The alkenylsuccinic anhydrides useful in preparing the imidazolidines of this invention can be prepared from an olefin or olefin polymer and maleic anhydride. Preferably a polymer of a lower olefin, or copolymer of lower olefins, is used, for example, polymers of ethylene, propylene, butylene, isobutylene and mixtures thereof. Since the reaction between the olefin and maleic anhydride may not go to completion, the resulting alkenylsuccinic anhydride can contain some unreacted olefin which can be allowed to remain as a diluent with no harmful effects upon the performance of the compounds of this invention.

Typical examples of polyethylene amines which can be used in preparing the compounds of this invention are di-ethylene triamine, -di(methylethylene)triamine, triethylene tetrarnine, tri(methylethylene) tetramine, tri (ethylethylene) tetramine, tetraethylene pentamine, and pentaethylene hexamine.

In the case of the carbonyland dicarbonyl-containing compounds useful in preparing the imidazolidines and bis-imidazolidines of this invention, the following are representative.

Mono-carbonyl containing: (a) Aldehydes.Formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valer-aldehyde, isovaleraldehyde, pivaldehyde, alpha-methyl- (5T. agitator running, carbonyl-containing compound is slowly added. The resulting mixture is then heated at reflux for about two hours while removing water formed by the reaction. The reaction mixture is then cooled and polybutyraldehyde, caproaldehyde, tert. butylacetaldehyde, 5 alkenylsuccinic anhydride in a solvent is added and the heptaldehyde, pelagonaldehyde, nonanal, capraldehyde, resulting mixture is heated at reflux for a suflicient time lauraldehyde, tridecanal, myristaldehyde, pentadecanal, to complete the reaction while simultaneously removing palmitaldehyde, heptodecanal, stearaldehyde, and the Water formed by the reaction. Thereafter the solvent is like; substituted aldehydes such as chloroacetaldehyde, stripped to leave an imidazolidine, which will be a clear, chloral, butylchloral, trifluoroacetaldehyde, aldol, 2-hymedium-amber colored, viscous oil. droxypropionaldehyde and the like; and unsaturated alde- The preparation of a specific imidazolidine of this inhydes such as, methacrolein acrolein, crotonaldehyde, 3- vention using the above described procedure is illustrated butenal, 3- and 4- pentenal, 3-, 4- and 4-hexenal, 4- in the following example:

octenal, 2-ethyl-3-hexenal, 3-decenal, and the like. E l 1 (b) Ket0nes.-Acetone, methyl ethyl ketone, methyl xamp e propyl ketone, methyl isopropyl ketone, methyl butyl Into a conventional glass reactor fitted as described ketone, methyl isobutyl ketone, methyl sec-butyl ketone, above, there was charged 23.3 grams of tetraet-hylene methyl tert.-butyl ketone, methyl cyclobutyl ketone, pentamine (0.1234 mol) and about 80 ml. toluene. With methyl neopentyl ketone, methyl tert.-amyl ketone, the agitator running 8.9 grams of n-butyraldehyde (0.1234 methyl n-amyl ketone, methyl hexyl ketone, methyl cymol) was then slowly charged and the resulting mixture clohexyl ketone, methyl n-heptyl ketone, methyl n-octyl heated at reflux for about two hours while removing water ketone, methyl nonyl ketone, methyl decyl ketone, diformed by the reaction. ethyl ketone, di-n-propyl ketone, diisopropyl ketone, ethyl After cooling the reaction mixture from above, 169 isopropyl ketone, ethyl n-propyl ketone, ethyl tert.-butyl parts (0.1234 mol), of a polybutenylsuccinic anhydride, ketone, ethyl n-butyl ketone, tert.-butyl isopropyl ketone, in which the alkenyl group had an average molecular n-propyl isopropyl ketone, n-propyl tert.-butyl ketone, weight of about 980, in 100 m1. of toluene, Was slowly diisobutyl ketone, Z-decanone, and the like; substituted charged after which the resulting mixture was heated at ketones such as 3- and 4-methyl-2-hexanone, 3,4-direflux for about two hours while removing Water formed methyl-Z-pentanone, 3-ethyl-2-pentanone, and the like; by the reaction. unsaturated ketones such as allylacetone, 2- and S-methyl- The toluene was then stripped, using vacuum, to leave l-penten-4-one, 1-hepten-4-one, 3-methyl-1-hexen-5-one, 197 parts of 1-[8-(polybutenylsuccinimido)-3,6diaza- S-methyl-5-hexen-2-one, and the like. octyl]-2-propylimidazolidine which analyzed 3.54% nitro- Di-carbonyl containing: gen and had a base number of 2.03.

(a) Aldehydes.Glyoxal, malonaldehyde, succinalde- Additional examples of other imidazolidines of this inhyde, glutaraldehyde, adipaldehyde, pimelaldehyde, suvention and the materials used for their preparation are beraldeyhde, azelaldehyde, sebacaldehyde, brassaldegiven in Table I, below. In the table only the alkenyl, hyde, brassylaldehyde, rocellaldehyde, and the like; unor polyalkenyl, portion of the polyalkenylsuccinic anhysaturated di-aldehydes such as malealdehyde, glutaconaldride and the average molecular weight of such portion dehyde, and the like. are given, DETA- means diethylene triamine, TETA means (11) Keto-nes.Diacetyl, acetylacetone, acetonylacetriethylene tetramine and TEPA means tetraethylene penttone, 2,3-hexanedione, 2,4-heptanedione, 3-methyl-2,4- amine.

TABLE I Alkenyl portion of Alkenylsuccinie Polyethylene CarbonylContaining Molar ratio Example Anhydride (mol wt. of Amine Compound Product N o. alkenyl group) Polybutenyl (980)--." TEPA Formaldehyde 1:1:1 1-[8-(polybutenylsuccinimido)-3,6-diazaoctyl]imidado TEPA Acetaldehyde 1:1:1 1-[8-(i)ols butenylsuccinirnido)-3,6-diazaocty1]-Lmethylimidazolidine.

do TEPA Isodecylaldehyde 1:1:1 l-L8-(%olyb}g: enylsucci11in1id0)-3,6-diaza0ctyl]-2-11onyl- Polybutenyl (1190) DETA Glutaraldehyde 2:2:1 Triiiiethylene bis[1-(8-(polybutenylsuccinimido)-3,6-

diazaoetyl)-2-imidazolidine Polybuteny1(980)- TEPA Acetone 1:1:1 l-[8-(polybutenylsuceinimido)-3,6-diazaoctyl]-2-dimethylimidazolidine.

do TEPA Cyclohexanone 121:1 1-[8-(polybutenylsuccinimido)-3,6-diazaoctyl]-1,4-

diazaspiro[4.5]decane.

do DETA Acetylacetone 2:2:1 2,2-methy1ene bis[1-((8-polybutenylsuccinilnido)-3,6-

diazaoctybhnidazolidine].

Polybutenyl (l315) DTEA Glutaraldehyde 2:2:1 Trimethylenebis[1-(2-(polybutenylsueclnimido)ethy1)- 2-imidazolidine].

do TEPA n-Butyraldehyde 1:1:1 1-[8-(polybutenylsuceinirnido)-3,6-diaza0ctyl[-2- ropylimidazolidine.

Polybutenyl (980)- DETA do 1:1:1 1- g-fpolybutenylsuccinimido)ethyl1-2-propylimidazolido DETA 2-propena1 1:1:1 Hg:(polybutenylsuccinimido)ethyl1-Zvinyllmidazoli- TETA 2 methyl-2propenal 1:1:1 1-[5 i golybutenylsuceinimido)-3-azapentyl]-2-(betaallyl)irnjdazolidine.

do. 2-butenal 1:1:1 1-[8-(polybutenylsuceinimido)-3,6-diazaoctyl]-2-propenylimldazolidine.

Lubricating oils which can be used as the base oils to which the new compounds of this invention are added are not limited as far as detergent elfects are concerned, and, accordingly, can be lubricating oils which are of a naphthenic base, paratfinic base, and other hydrocarbon bases, as well as lubricating oil-s derived from coal prodnets and synthetic oils, such as alkylene polymers, alkylene oxide polymers, dicarboxylic acid esters, alkylated benzenes, silicate esters, silicon polymers, and the like,

are suitable.

The imidazolidines and bis-imidazolidines of this invention can be used in lubricating oils in amounts of from about 0.05% to about 25% by weight. Additive concentrates of 60-95% are also contemplated. It has been found, however, that in finished formulations, for most applications, amounts of from about 0.25% to about 10% by weight are sufficient. In addition, the compounds of this invention can be used in fuel oils and in various light products, such as gasoline, wherein they also function as detergents or dispersants.

The eifectiveness of the imidazolidines of this invention to impart low temperature detergent properties is illustrated by the results of a detergency test, referred to as the Lacquer Deposition Test, which involves passing burned gasoline fumes through a sample of a formulation in a suitable container under controlled conditions after which the sample is aged in an over. The amount of deposit is then determined by washing away the oil with hexane. A control formulation is run simultaneously. The amount of deposits present when the test detergent is used as compared to the amount of deposits present when no test detergent is used is reported as the percent reduction in deposition. Utilizing the above test, the results presented in Table II, below, were observed. This particular test is quite useful since it correlates quite well with the results obtained in the Lincoln MS and L-SS (CRC) tests.

TABLE II LDT, percent Additive-percent by weight: reduction Product of Example 12 100 Product of Example 2--2 92 Product of Example 32 94 Product of Example 4-2 100 Product of Example 52 69 Product of Example 62 2 90 Product of Example 72 94 Product of Example 82 98 Product of Example 92 69 Product of Example 10-1 99 Product of Example 112 98 Although the imidazolidines of this invention are excellent ashless detergents, as shown by the foregoing results, it has been found that .in the presence of high sulfur content fuels of the type commonly used in diesel engines, in which lubricant temperatures are relatively high, their functionality as detergents suffers to the extent that good L-l or L-l, Supplement I, tests are not generally obtainable. It has been found, however, that utilizing the same reactants as are used to prepare the imidazolidines of this invention, but in molar ratios other than 1:1:1, or 222:1 in the case of the bis-imidazolidines, products can be prepared which not only possess essentially the same low-temperature detergent properties exhibited by the imidazolidines of this invention but which also possess improved high-temperature detergent properties. Thus, it has been found that by interacting (a) an alkenyl-suocinic anhydride, (b) a polyethylene amine and (c) a carbonyl-containing compound, as aforedescribed, in mol ratios for monocarbonyl-containing compounds of (b):(c) of from about 1:0.75 to 111.2, preferably about 1:1, and mol ratios of (a).:(b) of from above 1: 1, respectively, to about 1.6: 1, respectively, preferably from about 1.1:1 to 1.4:1, respectively, and for bis-carbonyl compounds of mol ratios of (b) (c) of from about 21075 to 2:1.2, respectively, and of (a):(b) of from above 1:1 to about 1.6:1, respectively, preferably from about 1.1:1 to 1.4:1, respectively, products are formed whose structures are unknown, but which can be used as ashless detergent additives in all types of engines and even in the presence of high-sulfur content fuels at fairly high operating temperatures.

The amount of excess alkenylsuccinic anhydride used (relative to the polyethylene amine) is important since large excesses above about 60% cause an increase in lacquer deposits on the piston in the L-1 test resulting in a product which ,is therefore unacceptable. Accordingly, the amount of excess a-lkenylsuccinic anhydride should range from more than 0% up to about 60%. Engine test experience with the various products encompassed by this part of our invention has shown that the amount of such excess is preferably from about 10% to about 40%.

The amount of excess on deficiency of carbony-cont aining compound (relative to the polyethylene amine) can vary from a mol ratio of 1:12 to 120.75, respectively, as mentioned above. However, mol ratios of about 1:1 are preferred since a loss of detergency is experienced at ratios significantly different than 1:1 and, beyond the range of ratios mentioned, the resulting products are commercially unsatisfactory detergents. In general the temperatures used for preparing the reaction products of this invention should be in the range of to 175 C. and preferably 150 C. at atmospheric pressure. Lower temperatures can be used if the .reaction is conucted under vacuum. As in preparing the imidazolidines, a hydrocarbon solvent or mineral oil or a combination thereof can be used as reaction medium. The raw materials (a), (b) and (0) can be reacted in indifferent order and in portions as is more fully illustrated in the following examples. The preparation of products using (a) an alkenylsuccinic anhydride, (b) polyethylene amine and (c) carbonyl-containing compound in various mol ratios is illustrated in the following non-limiting examples wherein parts are parts by weight. In carrying out the reaction refluxing of reactants is continued until the formation of by-product water stops.

Example 15 In this example the mol ratio of reactants (a) (b) (c) was 1.1: 1 1, respectively.

Into a suitable reaction vessel, fitted as previously described, and containing 32.9 parts of tetraethylene pentamine (0.1738 mol) in toluene, there was charged 6.25 parts of n-butyra-ldehyde (0.0869 mol). A slight tempperature rise was noted 262 parts of polybutenylsuccinic anhydride in toluene was then slowly added (the average molecular weight of the alkenyl group was 980 and therefore 0.1912 mol was added). Again some heat evolution was noted. After completing the anhydride addition, an additional 6.25 parts of n-butyraldehyde was charged and the resulting mixture was then heated at reflux (about -135 C.) for about three hours while continuously removing water formed in the reaction.

The reaction system was then placed under vacuum and the toluene stripped (maximum temperature was about C.) to leave 301 parts of product which Example 16 In this example the reactants and mol ratio of reactants was the same as in Example 15, but a different preparation procedure was used.

Into the reaction vessel containing 32.7 parts of tetraethylene pentamine (0.173 mol) there was slowly added 12.48 parts of n-butyraldehyde (0.173 mol) followed by the slow addition of 259 parts of polybutenylsuccinic anhydride (0.189 mol) in toluene. The resulting mixture was then heated at reflux for about two hours while removing water formed in the reaction. After removal of toluene there remained 300 parts of product which analyzed 3.19% nitrogen and had a base number of 1.84.

Example 17 In this example the mol ratio of reactants (a) (b) (c) was 1.1:1:1, respectively.

Into the reaction vessel containing 7.6 parts of tetraethylene pentarnine (0.146 mol) and 70 ml. of toluene a there was slowly added 5.26 parts of n-butyraldehyde (0.073 mol) followed by the slow addition of 277 parts of polybutenylsuccinic anhydride in toluene (the alkenyl group had an average molecular weight of 1315 and therefore 0.1607 mol was added) and an additional 5.26 par-ts of n-butyraldehyde. The resulting mixture was then heated at reflux for about three hours while removin water formed in the reaction. Thereafter the toluene was stripped to leave 309 parts of product which analyzed 2.22% nitrogen and had a base number of 1.39.

Example 18 In this example the same procedure was followed and the same reactants were used as in Example 17, but the mol ratio of (a):(b):(c) was changed to 1.2:121, respectively.

Into the reaction vessel containing 26.8 parts of tetraethylene pentamine (0.1415 mol) in toluene was slowly added 5.1 parts of n-butyrialdehyde, followed by 293 parts of polybutenylsuccinic anhydride in toluene (0.1698 mol) and then 5.1 parts of n-butyraldehyde. The resulting mixture was then heated at reflux for three hours while removing water formed in the reaction. Thereafter the toluene was stripped to leave 325 parts of product which analyzed 2.76% nitrogen and had a base number of 1.31.

Example 19 In this example the reactants were used in a mol ratio of (a):(b):(c) of 1.2:1z1, respectively.

Into the reaction vessel containing 28.3 parts of tetnaethylene pentamine (0.1493 mol) in toluene was slowly added 3.28 parts of acetaldehyde (0.0746 mol), followed by 309 parts of polybutenylsuccinic anhydride in toluene (the average molecular weight of the alkenyl group was 1315, and therefore 0.1792 mol was added) and then an additional 3.28 parts of acetaldehyde. The resulting mixture was then heated at reflux (123 C.) for three hours while removing water formed in the reaction. Thereafter the toluene was removed to leave 337 parts of a product, which after dilution with 168 parts of mineral oil, analyzed 1.57% nitrogen.

In Example 20 through 25, following, the same reactants were used and the mole ratio of reactants was the same but different procedures were used. The re actants were (a) polybutenylsuccinic anhydride in which the alkenyl group had an average molecular weight of 980, (b) tetrathylene pentamine and (c) n-butyraldehyde. The mol ratio of reactants (a):(b):(c) was 1.2:111, respectively.

Example 20 Into a reaction vessel containing 35.5 parts of (b) (0.188 mol) in toluene there was slowly added 6.75 parts of (c) (0.094 mol), then 309 parts of (a) in toluene (0.2254 mol), and finally an additional 6.75 parts of (c). The resulting mixture was then heated at reflux for about three hours while removing water formed in the reaction. After removal of the toluene there remained 351 parts of a product which analyzed 3.23% nitrogen and had a base number of 1.63.

Example 21 Into a reaction vessel containing 17.7 parts of (b) (0.0937) mol) there was slowly added 154 parts of (a) in toluene (0.1125 mol) followed by the addition of 6.75 parts of (0) (0.0937 mol). The resulting mixture was then heated at reflux for three hours after which toluene was removed to leave 140 parts of product. After dilution with 70 parts of mineral oil the product analyzed 1.96% nitrogen and had a base number of 0.96.

Example 22 Into a reaction vessel containing 17.0 parts of (b) in toluene there was slowly added 3.24 parts of (c) and the resulting mixture was then heated at reflux for two hours while removing water formed in the reaction. The

8 reaction mixture was then cooled to 30 C. and 148 parts of (a) in toluene (0.1080 mol) was added followed by the slow addition of 3.24 parts of (c). The resulting mixture was then heated at reflux for two hours while removing water formed in the reaction. Thereafter the toluene was removed to leave 168 parts of product which analyzed 3.18% nitrogen and had a base number of 1.64.

Example 23 Into a reaction vessel containing 20.1 parts of (b) in toluene (0.1065 mol) there was slowly added 175 parts of (a) in toluene (0.1278 mol) and the resulting mixture was then heated at reflux for two hours while removing water formed in the reaction. The reaction mixture was then cooled to 20 (3., 7.68 parts of (0) (0.1065 mol) was then added and the resulting mixture heated at reflux for two and one-half hours while removing water of reaction. Thereafter the toluene was removed to leave 199 parts of product which analyzed 2.95% nitrogen and had a base number of 1.68.

Example 24 Into a reaction vessel containing 18.75 parts of (b) in toluene (0.09925 mol) there was slowly added 7.15 parts of (c) (0.09925 mol) and the resulting mixture was then heated at reflux for two hours while removing water formed in the reaction. After cooling the reaction mixture to C., 163 parts of (a) .in toluene (0.1190 mol) was added and the resulting mixture heated at reflux for two hours while removing water formed in the reaction. Thereafter, toluene was removed to leave 186 parts of product which analyzed 1.69% nitrogen.

Example 25 Into a reaction vessel containing 18.9 parts of (b) in toluene (0.10 mol) there was slowly added 7.21 parts of (c) in benzene (0.10 mol), followed by the slow addition of 164 parts of (a) in toluene (0.12 mol). The resulting mixture was then refluxed for three hours while removing water formed in the reaction. Thereafter the benzene and toluene were removed to leave 187 parts of product which analyzed 3.25% nitrogen and had a base number of 1.68.

Example 26 In this example the reactants and procedure were the same as in Example 15 but the mole ratio of (a) :(b) :(c) was 1.4: 1 1, respectively.

Into a reaction vessel containing 26.5 parts of (b) in toluene there was slowly added 5.0 parts of (0) (0.0701 mol) followed by the addition of 269 parts of (a) in toluene (0.1964 mol) and then 5.0 parts of (c). The resulting mixture was then heated at reflux for four hours while removing water of reaction (5.5 mol). Thereafter the toluene was removed to leave 299 parts of product, which after dilution with 149 parts of mineral oil, analyzed 1.78% nitrogen and had a base number of 0.92.

Example 27 In this example, Example 26 was repeated except that the mol ratio of (a):(b):(c) was 1.52121, respectively. Thus 3.1 parts of (0) (0.0423 mol), 16.0 parts of (b) (0.0846 mol), 174 parts of (a) (0.127 mol) and 3.1 parts of (c) were added to the reaction vessel, in that order, and heated to provide 193 parts of product which analyzed 2.60% nitrogen and had a base number of 1.30.

Example 28 In this example the mol ratio of reactants (a) :(b) (c) was 1.2: 1: 1, respectively.

Into a reaction vessel containing 11.72 parts of tetraethylene pentamine (b) in toluene (0.0619 mol) there was added 2.23 parts of n-butyraldehyde (0), followed by the addition of 84.7 parts of polybutenylsuccinic anhydride (a) in toluene (the alkenyl group had an average molecular weight of 1368 and therefore 0.0619 mol was added) 9 and 2.23 parts of n-butyraldehyde (c). The resulting mixture was then heated at reflux for three hours while removing water formed in the reaction and cooled to 80 C. 21 parts of the same polybutenylsuccinic anhydride in toluene (0.0122 mol) was then added and the resulting mixture heated at reflux for one and one-half hours while removing water formed in the raction. Thereafter the toluene was removed to provide 117 parts of product which, after diluted with mineral oil to give a 66% solution, analyzed 2.0% nitrogen.

Example 29 In this example the mol ratio of (a):(b):(c) was 24:24 1, respectively.

Into a reaction vessel containing 22.8 parts of tetraethylene pentamine (b) in toluene (0.1205 mol) there was slowly charged 12.1 parts of glutaraldehyde (0.0301. mol) followed by the addition of 245 parts of polybutenylsuccinic anhydride (the alkenyl group had an average molecular weight of 1368 and therefore 0.1447 mol was added) in toluene (a) and then an additional 12.1 parts of glutaraldehyde. The resulting mixture was then heated at reflux for three hours, while removing water formed in the reaction. Thereafter toluene was removed to provide 269 parts of product which analyzed 1.76% nitrogen.

Example 30 In this example the mol ratio of reactants (a) :(b) (c) was 1.2: 1:08, respectively.

Into a suitable reaction vessel containing 31.3 parts of tetraethylene pentamine (0.1655 mol), there was added 5.9 parts of n-butyraldehyde (0.0827 mol) after which 272 parts of polybutenylsuccinic anhydride in toluene was added (the alkenyl group had an average molecular weight of 980 and therefore 0.1985 mol was added) followed by 3.98. parts of n-butylaldehyde (0.0551 mol). The resulting mixture was then heated at reflux for three hours while removing water formed in the reaction. Thereafter the toluene was removed to leave 309 parts of product which, after dilution with 154 parts of mineral oil, analyzed 1.94% nitrogen and had a base number of 1.12.

Example 31 In this example the mol ratio of reactants (a) (b) 1 (c) was 1.2: 1: 1, respectively.

Into a suitable reaction vessel containing 14.2 parts of tetraethylene pentamine (0.0749 mol) in 70 ml. of toluene, there was added, with stirring, 4.35 parts of acetone (0.0749 mol). No temperature increase was noted. Af-

ter heating the reaction mixture to about 100 C., 150

parts of polybutenylsuccinic anhydride in toluene were added (the alkenyl group had an average molecular weight of 1368 and, therefore, 0.090 mol was added). The resulting mixture was refluxed for about 2 /2 hours while removing water formed in the reaction. Thereafter the toluene was removed to leave 166 parts of product, which after dilution with 83 parts of mineral oil, analyzed 1.79% nitrogen and had a base number of 0.95.

Example 32 In this example the mol ratio of reactants (a) :(b) :(c) was 1.2: l :0.5, respectively.

Into a suitable reaction vessel containing 13.98 parts of tetraethyl pentamine (0.0738 mol) in 70 ml. of toluene, there was slowly charged 7.14 parts of glyoxal (0.0369 mol) and the temperature of the resulting mixture slowly rose to about 51 C. 150 parts of the same polybutenylsuccinic anhydride used in Example 28 (0.0885 mol) was then added and the resulting mixture heated at reflux for several hours. After removal of the solvent, the residue was blended with mineral oil and filtered. The blended product analyzed 1.27% nitrogen and had a base number of 0.50.

Example 33 In this example the mol ratio of reactants (a) (b) (c) was 1.2: 1:1, respectively.

Into a suitable reaction vessel containing 13.98 parts of tetraethylene pentamine (0.0738 mol) in toluene, there was slowly added 10.85 parts of chloral (0.0738 mol) which was followed by the addition of 150 parts of the same polybutenylsuccinic anhydride used in Example 28 (0.0885 mol) in toluene and the resulting mixture heated at reflux until no additional water of reaction could be removed. The toluene was then stripped under vacuum and the product diluted with sufiicient oil to give 66.6% solution. The diluted product analyzed 1.75% nitrogen and had a base number of 0.69.

Example 34 In this example the mol ratio of reactants (a) (b) :(c) was 1.2: 1 0.5, respectively.

Into a suitable reaction vessel containing 13.98 parts of tetraethylene pentamine (0.0738 mol) in toluene, there was slowly added 3.17 parts of 2,3-butanedione (9.9369 mol) followed by the rapid addition of 150 parts of a polybutenylsuccinic anhydride in which the alkenyl group had an average molecular weight of 1368 (0.0885 mol) in toluene. The reaction mixture darkened slightly but remained clear. After refluxing the reaction mixture for 2 /2 hours to remove by-product water, the toluene was stripped and the product diluted with suflflcient mineral oil to give a 66.6% solution. The diluted product analyzed 1.56% nitrogen and had a base number of 0.174.

Example 35 In this example the mol ratio of reactants (a) (b):(c) was 1.2:1:0.5; respectively.

In the manner of Example 34, 13.98 parts of tetraethylene pentamine (0.0738 mol), 4.2 parts of 2,5-hexanedione (0.0369 mol) and 150 parts of polybutenylsuccinic anhydride (0.0885 mol) were heated together to form the desired reaction product.

, Example 36 In this example the mol ratio of reactants (a):(b):(c)

TABLE III LDT,

Additive percent reduction Product of Example 15 98 Product of Example 16 98 Product of Example 17 97 Product of Example 18 96 Product of Example 19 91 Product of Example 20 98 Product of Example 21 95 Product of Example 22 98 Product of Example 23 Product of Example 24 97 Product of Example 25 96 Product of Example 26 97 Product of Example 27 97 Product of Example 28 91 Product of Example 29 93 Product of Example 30 67 Product of Example 31 98 Product of Example 32 89 Product of Example 33 90 Product of Example 34 89 Product of Example 35 90 Product of Example 36 97 It is evident from the foregoing results that the products prepared by the interaction of (a) polyalkenylsuccinic anhydride, ([2) polyethylene amine and (c) carbony1-containing compound are efiicient and outstanding detergents for use in lubricating oil compositions. As evidence of the fact that the amount of excess polyalkenylsuccinic anhydride should not be over about 60%, various different products prepared by the interaction of reactants (a), (b) and were evaluated in a test, referred to as a Thin Film Oxidation Test, which is a high temperature test designed to measure, among other things, stability and oxidation resistance of a lubricating oil formulation. This test, which correlates with the results obtained in the L-1 and L1, Supplement I, tests as to stability and oxidation resistance of a lubricating oil formulation is run as follows:

An aluminum cylinder is dipped in and out of a sample of the test oil fourteen times a minute. The aluminum cylinder has a specially prepared surface to insure uniformity and repeatability of deposit formation. The test cylinder, 2.75 inches long, is dipped 1.5 inches into the oil sample. The sample of test oil is maintained at a temperature of 100 C. During the course of the test the surface temperature of the aluminum cylinder is raised from 100 to 360 C. in 30 minutes by means of an internal heater. The test is terminated as soon as the aluminum cylinder reaches the maximum temperature. The cylinder is allowed to cool, washed with a light hydrocarbon solvent and rated for deposits of carbon and lacquer. These ratings are combined and a series of test samples rated, on a relative basis, from 1 to 7, with 1 being the best rating (least deposits).

The average results obtained for products prepared from varying the ratio of alkenylsuccinic anhydride to polyethylene amine, i.e., (a):(b) from 1:1 (imidazolidine) to 1.5: 1, respectively are presented in Table IV, below. The ratio of polyethylene amine to carbonyl-containing compound, (b) (c) was held at 1:1. The same reactants were used for each preparation in this series.

TABLE IV Mol ratio of alkenylsuccinic anhydride to polyethylene amine (a) (b): Rating 1:1 6.3 1 1:1 5 5 12:1 3.6 1.521 6.0

By comparison of the results presented in Tables II, III and IV, it is evident that the products prepared by the interaction of an (a) alkenylsuccinic anhydride, (b) polyethylene amine and (c) carbonyl-containing compound, within the prescribed mol ratios, are not only outstanding detergents for low temperature operations, but are also useful as detergents under high temperature conditions as typified by the conditions prevalent in diesel engines.

The present invention contemplates also the use of the imidazolidines and reaction products in combination with each other and with other additives in finished lubricating oil formulations. Such other additives include, for example, other non-metallic detergents, viscosity index improvers, pour point depressants, anti-foam agents, oxidation and corrosion inhibitors, and the like. It is also contemplated that metal-containing detergents, such as zinc dialkyl phosphorodithioates, and alkaline earth metal salts of sulfonic or olefin-P 8 reaction products can be in icluded in formulations containing the products of this invention.

While this invention has been described with respect to various specific examples and embodiments, it is understood that the invention is not limited thereto and that it can be variously practiced within the scope of the following claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound selected from the group consisting of (a) a 1-polyalkenylsuccinimidoimidazolidine represented by the structure if t ROIIC (em-(I715; I \N(OHZ(IJH-NH)X-CHTLFHN\ NH CH -C R1 R1 0 I] 0 R2 R3 and (b) an alkylene bis( l-polyalkenylsuccini-midoimidazolidine) represented by the structure 0 R1 [I A RCHC\ err H I N(OII2 CHNI'I)X CHZ CH'N NH I CHz-C R1 R1 (|3R4 t) Z 2 where R is an olefinic hydrocarbon polymer having a molecular weight of from about 500 to about 2500; R is selected from the group consisting of hydrogen and a lower alkyl radical; R and R are each selected from the group consisting of hydrogen, alkyl, alkenyl and haloalkyl said alkyl, alkenyl or haloalkyl each having from 1 to 18 carbon atoms; R; is selected from the group consisting of hydrogen and lower alkyl; x is a whole number from 0 to 3; and Z is selected from the group consisting of alkylene and alkenylene and contains from one to sixteen carbon atoms.

2. A 1-polyalkenylsuccinimidoimidazolidine of claim 1 where R is polybutenyl of an average molecular weight of from about 800 to about 1500.

3. A 1-polyalkenylsuccinimidoimidazolidine of claim 1 where R is polybutenyl of an average molecular weight of from about 800 to about 1500, R is hydrogen and R is alkyl having 1 to 18 carbon atoms.

4. A 1-polyalkenylsuccinimidoimidazolidine of claim 11 where R is polybutenyl of an average molecular weight of from about 800 to about 1500, and R and R are alkyl having 1 to 18 carbon atoms.

5. A 1-polyalkenylsuccinimidoimidazolidine of claim 1 where R is polybutenyl of an average molecular weight of from about 800 to about 1500, R is hydrogen, at is 2, R is hydrogen and R is alkyl having 1 to 18 carbon atoms.

6. 1-[8-(polybutenylsuccinimido)-3,6-diazaoctyl] imidazolidine in which the polybutenyl group has an average molecular weight of about 980.

7. 1-[8-(polybutenylsuccinirnido)-3,6-diazaoctyl] imidazolidine in which the polybutenyl group has an average molecular weight of about 1350.

8. An alkylene bis(1-polyalkenylsuccinimidoimidazolidine) of claim 1 where R is polybutenyl of an average molecular weight of from about 800 to about 1500, R is hydrogen and Z is alkylene.

9. An alkylene bis(1-polyalkenylsuccinimidoimidazolidine) of claim 8 where x is 2 and R is hydrogen.

10. The product prepared by the interaction, at temperatures of the order of C. to C., of

(a) an olefinic hydrocarbon polymer-substituted succinic anhydride in which said polymer has an average molecular Weight of from about 500 to about 2500; (b) a polyethylene amine, represented by the structure I-I N-(OHzC HNII) XO H CNH-O H2C HNH,

it. 1'1. in

where R is hydrogen or a lower alkyl radical and x is a whole number from 0 to 3; and

(c) a carbonyl-containing compound having from 1 to about 18 carbon atoms selected from the group consisting of an aldehyde and a ketone represented by the structure and a dialdehyde and a diketone represented by the structure O R Z( J-R4 Where R and R are each selected from the group consisting of hydrogen, alkyl, alkenyl and haloalkyl,

R is selected from the group consisting of hydrogen and lower alkyl, and Z is selected from the group consisting of alkylene and alkenylene; the mol ratio of (a) (b) being from above 1:1, respectively, to about 1.621, respectively, and the mol ratio of (b):(c) being, in the case of said aldehyde and ketone, from about 1:0.75, respectively, to about 1:12, respectively, and in the case of said dialdehyde and diketone, being from about 2:0.75, respectively, to about 211.2, respectively.

11. The product of claim where the olefinic hydrocarbon polymer has an average molecular Weight of from about 800 to about 1500.

12. The product of claim 10 where the olefinic hydrocarbon poiymer is a butylene polymer of an average molecular Weight of from about 800 to about 1500, x is 3 and the carbonyl-containing compound is an aldehyde.

13. The product prepared by the interaction, at temperatures of the order of 100 C. to 175 C., of

(a) a butylene polymer-substituted succinic anhydride in which the butylene polymer has an average molecular weight of from about 800 to about 1500; (b) tetraethylene pentamine; and (c) an aldehyde represented by the structure R2("1H Where R is alkyl having 1 to 18 carbon atoms; the mol ratio of (a):(b):(c) being from about 1.1-1.4: 1 z 1, respectively.

14. The product of claim 13 where R is propyl.

15. The product of claim 14 where the mol ratio of (a) (b):(c) is about 1.2:1z1, respectively.

16. A composition comprising a major amount of a lubricating oil and from about 0.05 to about 25% by Weight of a compound of claim 1.

17. A composition comprising a major amount of a lubricating oil and from about 0.05% to about 25 by weight of a compound of claim 5.

18. A composition comprising a major amount of a lubricating oil and from about 0.05 to about 25% by weight of a product of claim 10.

1.9. A composition comprising a major amount of a lubricating oil and from about 0.05% to about 25% by weight of the product of claim 15.

20. The product prepared by the interaction, at temperatures of the order of C. to C., of

(a) a butylene polymer-substituted succinic anhydride in which the butylene polymer has an average molecular Weight of about 1350;

(b) tetraethylene pentamine; and

(c) butyraldehyde; the mol ratio of (a):(b):(c) being about 1.2:1z1, respectively.

References Cited by the Examiner UNITED STATES PATENTS 2,877,179 3/1959 Hughes 260-309.7X 3,087,936 4/1963 Le Suer 252 51.5 X 3,131,150 4/1964 Stuart a a1 252 -51.5 X

FOREIGN PATENTS 1,265,086 5/1961 France.

DANIEL E. WYMAN, Primary Examiner. P. P. GARVIN, Assistant Examiner.

Claims (2)

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (A) A 1-POLYALKYLENYLSUCCINIMIDOIMIDAZOLIDINE REPRESENTED BY THE STRUCTURE
16. A COMPOSITION COMPRISING A MAJOR AMOUNT OF A LUBRICATING OIL AND FROM ABOUT 0.05% TO ABOUT 25% BY WEIGHT OF A COMPOUND OF CLAIM 1.
US3280034A 1963-07-22 1963-09-30 Alkenylsuccinimido alkyl-substituted imidazolidines and related materials Expired - Lifetime US3280034A (en)

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DE1964M0061680 DE1284014B (en) 1963-07-22 1964-07-10 oil we
FR981840A FR1406730A (en) 1963-07-22 1964-07-16 Imidazolidines, bisimidazolidines and compositions containing them
NL6408242A NL6408242A (en) 1963-07-22 1964-07-17
BE650770A BE650770A (en) 1963-07-22 1964-07-20
SE887664A SE317083B (en) 1963-07-22 1964-07-21
IL2174664A IL21746A (en) 1963-07-22 1964-07-22 Imidazolidines,bisimidazolidines and related products
GB3077364A GB1065595A (en) 1963-07-22 1964-08-04 Imidazolines and imidazolidines and oil compositions containing the same
GB3652064A GB1083712A (en) 1963-07-22 1964-09-07 Schiff bases and related compounds, their production and use

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US3369021A (en) * 1966-03-07 1968-02-13 Lubrizol Corp Preparation of lubricant additives with reduced odor
US3390086A (en) * 1964-12-29 1968-06-25 Exxon Research Engineering Co Sulfur containing ashless disperant
US3415750A (en) * 1963-10-04 1968-12-10 Monsanto Co Imidazolines having polyalkenylsuccinimido-containing substituents
US3445386A (en) * 1967-01-13 1969-05-20 Mobil Oil Corp Detergent compositions
US3497334A (en) * 1963-12-16 1970-02-24 Mobil Oil Corp Liquid hydrocarbon combustion fuels
US4579675A (en) * 1983-11-09 1986-04-01 Texaco Inc. N-substituted enaminones and oleaginous compositions containing same
EP0295789A2 (en) * 1987-05-18 1988-12-21 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adduct dispersants
US4839071A (en) * 1987-05-18 1989-06-13 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adducts as dispersants in lubricating oil compositions
US4839070A (en) * 1987-05-18 1989-06-13 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adduct dispersants
US4839072A (en) * 1987-05-18 1989-06-13 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adducts
US4839073A (en) * 1987-05-18 1989-06-13 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate and substituted acetate adducts as compatibilizer additives in lubricating oil compositions
US4906252A (en) * 1987-05-18 1990-03-06 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adducts as dispersants in fuel oil compositions
EP0399764A1 (en) 1989-05-22 1990-11-28 Ethyl Petroleum Additives Limited Lubricant compositions
US5158696A (en) * 1989-01-30 1992-10-27 Exxon Chemical Patents Inc. Oil soluble dispersant additives modified with bis-keto/thioketo compounds
US5273668A (en) * 1989-01-30 1993-12-28 Exxon Chemical Patents Inc. Oil soluble dispersant additives modified with bis-keto/thioketo compounds
US5629434A (en) * 1992-12-17 1997-05-13 Exxon Chemical Patents Inc Functionalization of polymers based on Koch chemistry and derivatives thereof
US5643859A (en) * 1992-12-17 1997-07-01 Exxon Chemical Patents Inc. Derivatives of polyamines with one primary amine and secondary of tertiary amines
US5646332A (en) * 1992-12-17 1997-07-08 Exxon Chemical Patents Inc. Batch Koch carbonylation process
US5650536A (en) * 1992-12-17 1997-07-22 Exxon Chemical Patents Inc. Continuous process for production of functionalized olefins
US5767046A (en) * 1994-06-17 1998-06-16 Exxon Chemical Company Functionalized additives useful in two-cycle engines
US6043199A (en) * 1997-08-26 2000-03-28 Exxon Research And Engineering Co. Corrosion inhibiting additive combination for turbine oils
US20060187416A1 (en) * 2000-03-17 2006-08-24 Satoshi Ouchi Image display device
US20070119340A1 (en) * 2005-11-30 2007-05-31 Xerox Corporation Ink carriers containing nanoparticles, phase change inks including same and methods for making same
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US7947636B2 (en) 2004-02-27 2011-05-24 Afton Chemical Corporation Power transmission fluids

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FR1265086A (en) * 1959-08-24 1961-06-23 California Research Corp Lubricating oil compositions containing alkenyl succinimide of tetraethylenepentamine
US3131150A (en) * 1961-04-12 1964-04-28 California Research Corp Lubricating oil compositions containing n-substituted alkenyl succinimides in combination with polyamines
US3087936A (en) * 1961-08-18 1963-04-30 Lubrizol Corp Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415750A (en) * 1963-10-04 1968-12-10 Monsanto Co Imidazolines having polyalkenylsuccinimido-containing substituents
US3497334A (en) * 1963-12-16 1970-02-24 Mobil Oil Corp Liquid hydrocarbon combustion fuels
US3390086A (en) * 1964-12-29 1968-06-25 Exxon Research Engineering Co Sulfur containing ashless disperant
US3369021A (en) * 1966-03-07 1968-02-13 Lubrizol Corp Preparation of lubricant additives with reduced odor
US3445386A (en) * 1967-01-13 1969-05-20 Mobil Oil Corp Detergent compositions
US4579675A (en) * 1983-11-09 1986-04-01 Texaco Inc. N-substituted enaminones and oleaginous compositions containing same
US4839070A (en) * 1987-05-18 1989-06-13 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adduct dispersants
US4839071A (en) * 1987-05-18 1989-06-13 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adducts as dispersants in lubricating oil compositions
EP0295789A2 (en) * 1987-05-18 1988-12-21 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adduct dispersants
US4839072A (en) * 1987-05-18 1989-06-13 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adducts
US4839073A (en) * 1987-05-18 1989-06-13 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate and substituted acetate adducts as compatibilizer additives in lubricating oil compositions
US4906252A (en) * 1987-05-18 1990-03-06 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adducts as dispersants in fuel oil compositions
EP0295789A3 (en) * 1987-05-18 1990-11-07 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adduct dispersants
US5158696A (en) * 1989-01-30 1992-10-27 Exxon Chemical Patents Inc. Oil soluble dispersant additives modified with bis-keto/thioketo compounds
US5273668A (en) * 1989-01-30 1993-12-28 Exxon Chemical Patents Inc. Oil soluble dispersant additives modified with bis-keto/thioketo compounds
US5399273A (en) * 1989-01-30 1995-03-21 Exxon Chemical Patents Inc. Oil soluble dispersant additives modified with bis-keto/thioketo compounds
EP0399764A1 (en) 1989-05-22 1990-11-28 Ethyl Petroleum Additives Limited Lubricant compositions
US5717039A (en) * 1992-12-17 1998-02-10 Exxon Chemical Patents Inc. Functionalization of polymers based on Koch chemistry and derivatives thereof
US5643859A (en) * 1992-12-17 1997-07-01 Exxon Chemical Patents Inc. Derivatives of polyamines with one primary amine and secondary of tertiary amines
US5646332A (en) * 1992-12-17 1997-07-08 Exxon Chemical Patents Inc. Batch Koch carbonylation process
US5650536A (en) * 1992-12-17 1997-07-22 Exxon Chemical Patents Inc. Continuous process for production of functionalized olefins
US5629434A (en) * 1992-12-17 1997-05-13 Exxon Chemical Patents Inc Functionalization of polymers based on Koch chemistry and derivatives thereof
US5698722A (en) * 1992-12-17 1997-12-16 Exxon Chemical Patents Inc. Functionalization of polymers based on Koch chemistry and derivatives thereof
US5703256A (en) * 1992-12-17 1997-12-30 Exxon Chemical Patents Inc. Functionalization of polymers based on Koch chemistry and derivatives thereof
US5696064A (en) * 1992-12-17 1997-12-09 Exxon Chemical Patents Inc. Functionalization of polymers based on Koch chemistry and derivatives thereof
US5767046A (en) * 1994-06-17 1998-06-16 Exxon Chemical Company Functionalized additives useful in two-cycle engines
US6043199A (en) * 1997-08-26 2000-03-28 Exxon Research And Engineering Co. Corrosion inhibiting additive combination for turbine oils
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BE650770A (en) 1964-11-16 grant
DE1284014B (en) 1968-11-28 application
NL6408242A (en) 1965-01-25 application

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