DE2625468A1 - OIL SOLUBLE COMPOUNDS AND THEIR USE IN LUBRICATING OILS - Google Patents

Description

The present invention relates to new lubricating oil additives,
Process for their production, as well as concentrates and lubricating oils containing these additives. The invention relates in particular to oil-soluble, nitrogen-containing compounds which are produced from sulfonate esters or sulfonyl chlorides and primary or secondary amines »

Lubricants, especially for use in internal combustion engines, serve not only to lubricate moving parts, but also

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dern have numerous other punctures. Modern, complicated formulated lubricating oils act against wear, as antioxi = dation agents, at high pressures and against rust formation, they also hold because of their detergent and dispersing properties keep the engine clean «. Numerous lubricating oil additives are known to exercise the effects mentioned A well-known class of ashless detergents, namely the amine reaction products, proved particularly useful in keeping the engine hydroearbyl-substituted succinic acids, i.e. the well-known succinimides

TJS-PS 2 236 168 teaches the use of compounds of the formula R (SO ₂ ) NR ¹ R "where R is an acyclic, alicyclic or aromatic radical and R ¹ and R" are hydrogen or alicyclic, aliphatic, heterocyclic or aromatic radicals mean as detergents for lubricating oils. The compounds mentioned are prepared by subjecting, for example, colorless paraffin oil, naphthenes, paraffin wax or the like to conventional processes, for example reacting with sulfur dioxide and chlorine, the radical R being sulfonated at arbitrary locations, whereupon the sulfon groups are converted into the sulfonamide in a conventional manner ·

US Pat. No. 2,683,161 teaches the stabilization of arylalkane * sulfonates of the formula RVS0p-ORo7x, which are prepared from a saturated aliphatic hydrocarbon by reaction with (1) chlorine and sulfur dioxide and (2) a phenol, the stabilization being achieved by heating 110 to 300 C. In the above formula, R ₁ denotes an aliphatic radical of a petroleum hydrocarbon which contains saturated-branched-chain hydrocarbons, preferably having 6 to 24 carbon atoms, and R ₂ denotes the phenyl radical. The compounds described serve as plasticizers and functional fluids «

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rie

US Pat. No. 3,133,948 describes a method of manufacture of vinyl sulfonates of aromatic hydroxyl compounds. This The process consists in the reaction of carbyl sulfate with an aromatic hydroxyl compound in an aqueous-alkaline solution Medium at a pH value between 7.5 and 11.5 »whereby a phenyl vinyl sulfonate is obtained. Suitable aromatic hydro = xy! compounds are, for example, o- and p-chlorophenol. Car = Byl sulfate is made by reacting ethylene with sulfur trioxide or oleum.

U.S. Patent 3,158,639 mentions that carbyl sulfate has been known since 1836 and teaches that this compound can be made by reacting ethylene with sulfur trioxide in a molar ratio of 1: 2, both in solution and in the vapor phase, and usually at room temperature or lower temperature to avoid charring to avoid.

Aryl esters of unsaturated sulfonic acids are known from US Pat. No. 3,205,249. These esters are prepared by adjacent with at least one methyl and / or methyl ester * reacting an olefin to the double bond with a Vinylsulfonsäurearyl at temperatures between 100 and 300 ⁰ C. Suitable olefins contain 3 to 20 carbon atoms. The products should be useful as plasticizers and textile auxiliaries.

US Pat. No. 3,238,257 describes N-tert-alkyl-alkanesulfonamides of the formula R-SO ₂ -NH-E ¹ , which are used in petroleum distillate fuels as additives against freezing, against corrosion and as carburetor detergents. In the above formula, R denotes a saturated alkyl radical having 12 to 30 carbon atoms and R denotes a tertiary alkyl radical having 8 to 22 carbon atoms. Preferred compounds contain a total of 25 to 35 carbon atoms between R and R · These sulfonamides

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are made by. Implementation of an aliphatic hydrocarbon with gaseous sulfur dioxide and chlorine in the presence of actinic light, being a hydrocarbon sulfonyl chloride, which is then combined with the appropriate Amine is implemented. According to a preferred embodiment the aliphatic hydrocarbon is produced by sulfochlorination of white paraffin No. 40, a highly acidic wash paraffinic petroleum fraction with average 16 to 20 carbon atoms «

U.S. Patent 3,325,418 discloses a polysulfonamide substituted one Polyolefin of molecular weight 200,000 to 1,000,000, which is produced by treating the polyolefin with sulfur dioxide and chlorine gas treated to form a product useful for viscosity index improvement and as a detergent is used in lubricating oils "

U.S. Patent 3,352,728 describes amidosulfates of the formula

• J

ι 2 R ²

1 2

where R is an organic radical, R is hydrogen or an organic radical and R and R are hydrogen, among others or interpret a polyamide. These connections made by implementation an olefin polymer with chlorosulfonic acid and then with an amine serve as detergents in lubricating oils.

According to the invention, oil-soluble, nitrogen-containing products are made provided which are obtained by reacting (a) an aryl ester of a substantially saturated Hy =

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drocarbylethylsulfonic acid or (b) an essentially saturated one Hydrocarbylsulfonyl chloride with a nitrogenous Compound which has at least one amine hydrogen, that is to say an -NH- group, the substantially saturated Hydrocarbyl substituent has at least 35 aliphatic carbon atoms. These products. own in Lubricating oils have excellent cleaning and dispersing properties.

The invention also relates to new sulfonamides of the formula

wherein

(a) R has an essentially saturated hydrocarbyl radical about 35 to 350 carbon atoms and 0 to 3 olefinic

Double bonds,

(b) Q is a nitrogenous residue that is formed upon removal of one or more V / ass only of fat omen on

or several nitrogen atoms of ammonia or one having at least one primary or secondary amino group Hydrocarbylamine, aminohydrocarbylamine, alkoxyhydrocarbylamine, alicyclic hydrocarbylamine, alkylenepolyamine or hetero = cyclic amine, and

(c) m represent a positive integer

The invention also relates to a process for the production of these oil-soluble nitrogen-containing products. which is characterized in that the aryl ester of a substantially saturated Hydrocairbyläthylsulfonsäure with about 0.1 to 15 mol per equivalent of the ester of a nitrogen-containing compound which has at least one amine hydrogen, that is a group -NH, at a temperature of 50 to about 25O ⁰ C converts.

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The invention also relates to a further process for the preparation of these oil-soluble nitrogen-containing products, which is characterized in that a substantially saturated hydrocarbylsulfonyl chloride with about 0.1 to 15 moles per equivalent of the chloride of a nitrogen-containing compound with at least one amine hydrogen, that is to say one Grouping -NH, at a temperature of 10 to about 100 ⁰ G converts »

The invention further relates to lubricating oil additive concentrates which contain 90 to 10 wt. Fo of an oil of lubricating viscosity and 10 to 90 wt (b) a substantially saturated hydrocarbylsulfonyl chloride with a nitrogen-containing compound having at least one amine hydrogen, i.e. an -NH- group, the substantially saturated hydrocarbyl substituent having at least 20 aliphatic carbon atoms.

The invention also relates to lubricating oils, characterized by

(a) a major portion of an oil of lubricating viscosity and

(b) an amount of an oil-soluble one sufficient for the dispersing effect nitrogen-containing compound obtained by reacting (1) an aryl ester of an essentially saturated hydrocarbylethylsulfonic acid or (2) a substantially saturated hydrocarbylsulfonyl chloride with a nitrogen-containing compound which at least one amine = Hydrogen, that is to say an -NH- group, where the im substantial saturated hydrocarbyl substituent has at least 20 aliphatic carbon atoms *

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It is assumed that the predominant organic group between the sulfonate ester or sulfonyl chloride group and Ami = forms no group, which is sulfonamide residue. In the further description the reaction products obtained in the above manner are generally described as sulfonamides, although the .Reaktionsprodukte, as can be seen from the above description, from a mixture of sulfonamides and other reaction products exist.

The sulfonamides provided according to the invention lead to lubricating oils with excellent cleaning and dispersing properties.

The sulfonamides according to the invention are made from sulfonate esters or sulfonyl chlorides. which in turn are synthesized from readily available and cheap raw materials can.

The invention relates primarily to oil-soluble, nitrogen-containing products, which are obtained by (a) at a temperature of about 50 to about 250 ⁰ C an aryl ester of an essentially saturated hydrocarbylethyl sulfonic acid or (b) at a temperature of 10 to ^{10O 0} G of an essentially saturated hydrocarbylsulfonyl chloride, the essentially saturated hydrocarbyl substituent having at least 35 aliphatic carbon atoms, with 0.1 to 15 mol per equivalent of ester or chloride of a nitrogen-containing compound which has at least one amine hydrogen, i.e. an -NH -Group, contains. The product usually contains 0.1 to 1.0 moles of the amine-derived portion of the product per equivalent portion of the sulfonate-derived portion.

According to a preferred embodiment, the oil-soluble nitrogen-containing products made from an aryl ester of an essentially saturated hydrocarbylethyl sulfonic acid,

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whose hydrocarbyl substituent is on the alpha or beta carbon atom of the ethyl radical, or mixtures thereof, according to the following formulas

E ¹

IH “C-CH ₉ -SO ₉ -O-aryl and

R ¹

II H, C-CH-SO ₂ -O-aryl

where R is an essentially saturated hydrocarbyl radical, the number of aliphatic carbon atoms of which is sufficient, to make the sulfonamide oil soluble.

Generally R has at least 35 and usually no more than 350 carbon atoms, preferably from about 35 to ■ about 250 and particularly preferably about 50 to about 150 carbon atoms.

According to a further preferred embodiment, the oil-soluble nitrogen-containing products are prepared from an essentially saturated hydrocarbylsulfonyl chloride of the formula R-SO ₂ -Cl, in which R has the meaning given above.

The hydrocarbyl substituent is preferably substantially saturated. "Essentially saturated" is understood to mean that at least about 95 $ of the total C-C covalent bonds are saturated. An excess of unsaturated bonds makes the molecule susceptible to oxidation, degradation and polymerization and leads to products that are unsuitable for numerous uses in the hydrocarbon oils.

The substantially saturated hydrocarbyl substituent may have polar substituents provided, however, that

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the polar substituents are not present in such large quantities that the hydrocarbon-like character of the remainder was essential is changed. Such polar substituents are, for example, chlorine, the keto group, alkoxy groups and the like.

The presence of these polar groups is not preferred, and the upper limit of the proportion of polar substituents the remainder is about $ 10 based on the weight of the hydrocarbon portion of the rest.

Among the sources of essentially saturated hydrocarbyl = Substituents include the high molecular weight, essentially saturated petroleum fractions and essentially saturated ones Olefin polymers, especially polymers of monoolefins with up to about 30 carbon atoms. The polymers of 1-monoolefins such as ethylene, propene, 1-butene, Isobutene, 1-hexene, 1-octene, 2-methyl-1-heptene, 3-cyclohexyl-1-butene and 2-methyl ~ 5-propyl-1-hexene. The polymers of Cp-Cc olefins are preferred. Polymers of olefins, whose double bond is not terminal can be used. These olefins include, for example, 2-butene, 3-pentene and 4-octene.

Interpolymers of olefins are also useful, for example of the above olefins with other interpolymerizable olefinic ones Substances such as other 1-olefins, aromatic olefins, cyclic olefins and polyolefins. To this Interpolymers include, for example, products obtained by polymerizing isobutene with styrene Isobutene with butadiene, propene with isoprene, ethylene with piperylene, isobutene with chloroprene, isobutene with p-methylstyrene, of 1-hexene with 1,3-hexadiene, of 1-octene with 1-hexene, from 1-heptene with 1-pentene, 3-methyl-1-butene with 1-octene, 3 »3 ~ dimethyl-1-pentene with 1-hexene, isobutene with Styrene and piperylene and the like.

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The relative. Amounts of monoolefins to other monomers in the interpolates affect the stability and oil solubility of the final product made from such interpolymers. Y / egen the oil solubility and stability should the intended for purposes of the invention interpolymers in be substantially aliphatic and substantially saturated, that is, should be at least about 80, and preferably about 95 weight units from aliphatic a ~ tiscb. monoolefins and no more than about 5 $ olefin linkages based on the total of the covalent C-C bonds. In most cases the percentage of olefinic bonds should be less than about $ 3 of the total number of covalent C- Make C-bonds.

Specific examples of such inter-polymers are copolymers of 95 wt _o $ isobutene and 5 $ styrene, terpolymers of 98 $ isobutene and 1 $ piperylene and 1 $ chloroprene, terpolymer of 95 $ isobutene and 2 $ 1-butene and 3 $ 1-hexene terpolymers from 60 $ isobutene, 20 $ 1-pentene and 20 $ 1-octene, copolymers from 80 $ 1-hexene and 20 $ 1-heptene, terpolymers from 90 $ isobutene, 2 $ cyclohexene and 8 $ propene and copolymers from 80 $ ethylene and $ 20 propene.

The aryl hydrocarbyl ethyl sulfonates

The hydrocarbon from any of those mentioned above Swelling can be used in a conventional manner to form adducts be brought to the aryl vinyl sulfonate, for example by methods that are used for the addition of hydrocarbon residues of maleic anhydride in the manufacture of hydrocarbyl succinic anhydrides. A fully satisfying one The process consists in introducing the source of the hydrocarbyl substituent into the reaction vessel and with stirring heated. The aryl vinyl sulfonate is added to the reaction vessel and the reaction mixture is brought to the reaction temperature

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door heated and kept at this temperature for the duration of the reaction. In general, the reaction temperatures are for annealing at about 100 to 500, and preferably at 150 to 25O ⁰ C. In general, the reaction is conducted for about 1 to about 48 hours, and preferably for about 2 to about 24 hours at the preferred reaction temperatures. In general, it is found that the reactivity of the source of the hydrocarbyl substituent in the adduct formation can be increased by first chlorinating it. An excellent source of the hydrocarbyl substituent is, for example, chlorinated polyisobutene. In the adduc reaction, polyisobutenyl reacts faster and at lower temperatures. Most of the chlorine is removed from the hydrocarbyl portion during the reaction. After the reaction, the adduct can be purified in a conventional manner, for example by extraction with a lower alkanol (for example methanol) and subsequent vacuum distillation to remove volatile components.

The crude reaction mixture can also be purified by codistillation with a hydrocarbon solvent of medium boiling range, for example a solvent-rarinized neutral oil. Preferably, such a codistillation is conducted at reduced pressure, for example at 100 ⁰ C and 2 mm Hg. A further method consists in the precipitation of insoluble components by dilution with a nieder_siedenden hydrocarbon solvents such as hexane and then decanting and stripping.

In the above formulas I and II "aryl" means an aryl or substituted aryl radical, the aryl substituent is derived from aromatic hydroxyl compounds which are reacted with the carbyl sulfate to form the aryl vinyl sulfonate ester mentioned. This Ester is then added to the hydrocarbon, whereby one

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the hydrocarbyl-substituted ethyl sulfonic acid ester is obtained. The aryl substituent is not displaced during the addition reaction.

Aromatic Hy = suitable for reaction with the carbyl sulfate Hydroxyl compounds contain at least one carbocyclic aromatic ring and at least one directly attached to a carbo = cyclic aromatic ring bonded hydroxyl group. According to one embodiment is the aromatic ring through mild substituted electron withdrawing groups, which increase the reactivity with the carbyl sulfate as well as the reactivity of the adduct (Hydrocarbyläthylsulfonat) opposite Amines. Suitable electron withdrawing groups are Ha = logene, for example chlorine or bromine. A particularly suitable one The remainder is a single chlorine atom ortho or para to the hydroxyl group. The aromatic ring can also be made by mild Electron donors can be substituted, for example by methyl or ethyl groups and the like.

Preferred aromatic hydroxy compounds are those with 1 to 3 carbocyclic aromatic rings and 1 to 3 hydroxyl groups. The aromatic hydroxyl compound knows more as an aromatic ring, the rings can be condensed (as with naphthol) by a single bond be connected (as in 4 »4'-dihydroxyldiphenyl) or by be connected by a short-chain bridge (as in 4> 4 '-dihydroxy = dipheny! methane).

Suitable aromatic hydroxy compounds include Phenol, the cresols, the xylenols, p-tert.-butylphenol, Ronylphenol, the dodecylphenols, o-chlorophenol, p-chlorophenol, 4-chloro-2-methylphenol, 2,2'- or 3,3'-dimethy1-4,4 '~ dihy = droxybiphenyl, 4,4-dihydroxydiphenylmethane, 2,2-bis- (4'-hy = droxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, resorcinol,

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3-cyanophenol, 4,4'-di-hydroxydiphenyl sulfoxide, 3-iodophenol, Octadecylphenol, 4-Cyclohexylphenol, 4-Cyclododecylphenol, 4-dibutylaminophenol, 4- (N-methyl ~ N-ethyl) aminophenol, 3-methoxyphenol and 4-butoxyphenol.

The aryl esters of vinyl sulfonic acid can be according to various known processes are produced. The process of US Pat. No. 3,121,730 consists in the implementation of β ~ chloroethane sulfide Phonic acid chloride with phenol in an aqueous medium at a pH between 7.5 and 11.5 · The reaction takes place with loss of 2 moles of hydrogen chloride and formation of phenyl vinyl sulfonate. The method of U.S. Patent No. 3,133,948 is Reaction of carbyl sulfate with an aromatic hydroxyl compound in an aqueous-alkaline medium at a pH between 7.5 and 11.5} it leads to a phenyl vinyl sulfonate.

In another, more convenient process, the carbyl sulfate once produced must not solidify. This is particularly useful because solid carbyl sulfate is difficult to use. In this process, the carbyl sulfate is made by reacting ethylene oxide with sulfur trioxide at temperatures above the melting point of the carbyl sulfate, that is to say at about 110 to 180 and. preferably about 160 to 170 ⁰ C produced. The molten carbyl sulfate is immediately introduced into an aqueous-alkaline solution of the aromatic hydroxyl compound. The carbyl sulfate reacts with the aromatic hydroxyl compound to form the aryl ester of vinyl sulfonic acid plus sodium sulfate. The aqueous solution is preferably kept ^{between 0 and 25 ° C.} After the sulfonate ester has been isolated from the aqueous solution, it can be converted into the adduct as described. The sulfonate testers are toxic and should be handled with care.

Carbyl sulfate and aromatic hydroxyl compounds react

comfortable, in equivalent amounts, that is, in the molar ratio of about 1: 1 for monohydric phenols and about 1: 2 for dihydric phenols »Since the carbyl sulfate is in aqueous solution tends to hydrolysis, one must use an excess in order to maintain the molar ratio 1: 1 with respect to the aromatic hydroxyl = maintain connection.

The hydrocarbyl sulfonyl chloride

The hydrocarbon from the above sources can be converted into the corresponding sulfonic acid or a salt thereof by two processes be convicted.

In the first process, the hydrocarbon is reacted with a sulfonating agent, preferably chlorosulfonic acid. In the remainder of the description, the sulfonating agent is referred to as chlorosulfonic acid for the sake of simplicity.

In the reaction between hydrocarbon and chlorosulfone = acid can be used under pressure, normal pressure or overpressure. The pressure is not critical and his choice is his Area of Expertise. For convenience normal pressure is usually used. The chlorosulfonic acid and the hydrocarbon are preferably used in the presence a complex-forming diluent, for example in the presence of an aliphatic ether or amide such as for Example diethyl ether, dibutyl ether, dimethylformamide, Di = butylformamide or hexamethylphosphoramide, which preferably has 2 to 8 carbon atoms. Complex these compounds the chlorosulfonic acid and give a reagent which is particularly preferred in terms of yields. In addition to the coicplexing Diluents can be non-complexing solvents like a mineral oil or non-reacting organic solvents like heptane, hexane, nitrobenzene, dichloro = Ethane or the various dichlorobenzenes can be used «

6 0: = R S? / 1 0 7 9

The purpose of these non-complexing diluents is that the handling of the various reactants and the formation of a homogeneous reaction mixture be relieved. Benzene is not suitable as a diluent because it tends to undergo side reactions.

If desired, the diluent can be omitted, although its use is preferred. The reaction mixture is expediently agitated. It is often advisable to use a small molar excess of chlorosulfonic acid (based on 1 mol of polymer) in order to ensure that the reaction between the hydrocarbon and chlorosulfonic acid is fully. Trlund expires. If the olefin polymer contains more than one un- {/ ■■ -. saturated bond, more than one sulfonic acid group can be introduced into the polymer. In this case, a molar excess should be used (ie more than 1 mol ^Su-! Funierungsmittel double bond). The amount of excess chlorosulfonic acid can vary widely; it is a function of the amount of diluent and the desired rate of action. It has been found, for example, that essentially equimolar amounts of chlorosulfonic acid and hydrocarbon (for example polyisobutylene) can be used and essentially complete conversion can be achieved Procedure preferred. However, 0.5 to 1.5 or 2 or 3 or even higher ratios between chlorosulphonic acid and hydrocarbon can also be used. Substantially equimolar ratios between acid and polymer (on the Ba'.is one double bond per polymer molecule) _o the Reaktionstomperatur is generally below 100 ⁰ C and usually at 0 his 50, in particular at et v / a 15 to about 30 ⁰ C. Preferably, the reaction temperature is maintained below about 30 C, because the implementation is exothermic and quite stormy «

R 0 9 8 5 2/1 Π 7 9

This measure is useful, but not critical. The reaction is accompanied by the evolution of hydrogen chloride, which soon ceases, especially if excess is used Chlorosulfonic acid. The reaction times are usually 0.5 to 12 and for example 1 to 4 hours.

After the reaction has ended, it may be advisable to neutralize excess chlorosulfonic acid (for example with sodium = bicarbonate) and remove the neutralized acid in a conventional manner, for example by filtration. Were however essentially equimolar amounts of acid and olefin = used polymer, it is often expedient to continue the process without such neutralization and separation stages.

In a further process for the preparation of hydrocarbyl sulfonic acid, the hydrocarbon is first reacted with an alkyl chlorosulfonate, expediently in the presence of a solvent such as 1,2-dichloroethane, ether or the like. The reaction proceeds satisfactorily at temperatures from 40 to 120 and preferably from 70 to 90 ^° C., but below the decomposition temperature of the reactants and products. It can take place under reduced pressure, normal pressure or overpressure. For reasons of convenience, normal pressure is usually used.

Hydrocarbons and alkyl chlorosulfonates are used in the generally using a small molar excess of the sulfonate, based on the hydrocarbon, reacted. It is preferred to use 1.1 to 2 mol of alkyl chlorosulfonate per mole of hydrocarbon. The reaction is preferably carried out with a molar ratio of ester to olefin of 1.5 to 1 to ensure the most effective utilization of the reaction participants. The implementation takes place in counter-

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wart a high-boiling solvent, preferably a chlorinated hydrocarbon, compared to chlorosulfonic acid esters is inert, for example 1,2-dichloroethane, chlorine = benzene, dichlorobenzene or the like.

The alkyl component of the chlorosulfonic acid alkyl ester contains 1 up to 4 carbon atoms. Ethyl = chlorosulfonate is preferably used, as it is easy to prepare and with hydrocarbons easily reacts to hydrocarbyl sulfonic acid alkyl esters «

The alkyl chlorosulfonate is reacted with an olefin to give the alkyl hydrocarbylsulfonate, which is then approximately equimolar amounts and in a lower alkanol (1 to 6 carbon atoms) as a solvent with a strong base such as sodium methylate, potassium methylate, potassium hydroxide or the like treated at a temperature of 25 to 150 and preferably 50 to 100 G and a pressure of 1 to 10 atmospheres will. This process leads to a metal salt of hydrocarbyl sulfonic acid, for example sodium hydrocarbyl = sulfonate.

The hydrocarbylsulfonic acid or salt obtained by one of the above processes is then treated with a Vilsmeyer-Haack reagent, i.e. with a 1: 1 complex of a di-C ₁ -C. -alkylformamide such as dimethylformamide and a inorganic chloride such as phosphorus oxychloride, thionyl chloride or the like to obtain the corresponding hydrocarbylsulfonyl chloride. It is often advisable to have a slight stoichiometric excess

to use. Preferably, however, hydrocarbyl sulfonic acid and Vilsmeyer-Haack reagent are used in a molar ratio of about 1: 1 a.

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The amine

According to a first embodiment, the sulfonamides are obtained, by (a) the aryl ester of the essentially saturated hydrocarbylethylsulfonic acid or (b) an essentially saturated Hydrocarbylsulfonylchlorid reacts with a nitrogen-containing compound, which at least one Amine hydrogen, that is, an -NH-G group, has ο Der Amine hydrogen must be present so that the nitrogenous Compound can react with the aryl ester or sulfonyl chloride to form the sulfonamide. For the production of the invention Many nitrogenous sulfonamides are suitable Compounds with at least one amine hydrogen, that is an -ETH group. Suitable compounds are for example Ammonia, aliphatic amines and heterocyclic amines. the for the preparation of the above sulfonamides suitable amines correspond to the formula

HNR ⁵ 'R ²

wherein R and R ^ (A) independently of one another are hydrogen or an organic radical bonded to nitrogen via a C-N bond, such as a hydrocarbyl radical, for example a unsubstituted hydrocarbyl, aminohydrocarbyl, alkoxy = hydrocarbyl, alicyclic hydrocarbyl or alkylene poly = amine-substituted hydrocarbyl radical or (B) together the Represent the residue of a heterocyclic amine.

The preferred aliphatic amines used are hydrocarbyl = amines, alkoxy-substituted hydrocarbylamines or alkylenepoly = amines. Specific examples of hydrocarbylamines are methyl = amine, propylamine, butylamine, pentylamine, hexylamine, heptyl = amine, octylamine, di-n-butylamine, di-n-hexylamine, decylamine,

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Dodecylamine, hexadecylamine, octadecylamine and the like. Specific examples of alkoxy-substituted hydrocarbylamines are methoxyethylamine, butoxyhexylamine, propoxypropylamine, Heptoxyethylamine and the like, as well as the polyalkoxyamines such as poly (ethoxy) ethylamine, poly (propoxy) ethylamine, poly (propoxy) propylamine and the same.

Suitable alkylene polyamines are in most cases Alky = lenpolyamines of the formula

IV H-N ^ -alkylene-N ^ -R * ι ι «·

R ¹ R ¹

wherein (A) η is an integer, preferably less than about 10, (B) each R 'radical, independently of the others, is hydrogen or a substantially saturated hydrocarbon radical, and (G) each alkylene radical is a lower alkylene radical having 8 or fewer carbon atoms represent, wherein several alkylene radicals can be identical or different and wherein, if "alkylene" denotes the ethylene radical, the two radicals R ¹ on adjacent nitrogen atoms can together form an ethylene group, a piperazine ring being obtained.

According to a preferred embodiment, R ^{1 is} hydrogen, methyl or ethyl. The alkylenamines include, in particular, methylenamine ^ ethylenamine propyleneamines, butyleneamines, pentyleneamines, hexylenamines, heptyleneamines, octyleneamines, other polymethylenamines, and also the cyclic and higher homologues of such amines such as piperazines and aminoalkyl-substituted piperazines. Examples of these amines may be mentioned; Ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, octamethylenediamine, di (heptamethylene) triamine,

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Tripropylenetetramine, tetraethylene pentamine, triethylenediamine, Pentaethylene hexamine, di (trimethylene) triamine, 2-heptyl ~ 5- (2-aminopropyl) imidazoline, 4-methylimidazoline, 1,3-bis (2 ~ aminoethyl) imidazoline, 1- (2-aminopropyl) piperazine, 1,4-bis (2-aminoethyl) piperazine and 2-methy1-1- (2-aminobutyl) piperazine » Also higher homologs obtained by condensation of two or more of the above alkyleneamines, are useful.

The ethylene amines are particularly suitable. These are discussed in detail under the title "Ethylene Amines" in Encyclopedia of Chemical Technology, Kirk and Othmer, Vol. 5, pp. 898-905, Interscience Publishers, New York (1950). Such Compounds are best made by reacting an alkylene chloride with ammonia. The implementation leads to somewhat complex mixtures of alkyleneamines, including cyclic condensation products such as piperazines. These Mixtures can be used according to the invention. On the other hand, satisfactory products are also obtained when used pure alkyleneamines. One for cost reasons as well as because of The alkylenamine which is particularly suitable for the effectiveness of the products obtainable therefrom is a mixture of ethyleneamines which is obtained by reacting ethylene chloride with ammonia and its composition corresponds to that of tetraethylene pentamine.

To further, for the preparation of the sulfonamides according to the invention Suitable alkylene polyamines include those of the following formulas:

R R

VI (HN-alkylene ^ N-alkylene-NfAikylen-NH) RR ¹

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■ - • 21 -

wherein

(a) η 'the number 0 or an integer, preferably less than about 10,

(b) the radicals R ¹ independently of one another are hydrogen or an essentially saturated hydrocarbon radical and

(c) the alkylene radicals, which can be identical or different, preferably represent lower alkylene radicals with 8 or fewer carbon atoms and, if "alkylene" means ethylene, two radicals R ¹ on adjacent nitrogen atoms in formula IV can together form an ethylene group.

Examples of these amines are tris (aminoethyl) amine, Ν, Ν, Ν ', Ν Tetra (aminoethyl) ethylenediamine and the like.

Suitable heterocyclic amines are, in addition to those above in connection with the alkylenepolyamines mentioned piperazinetidie morpholines, imidazolines, aminoalkyl-substituted Morpholines and pyrrolidones such as aminoethylpyrrolidone.

The products of aryl esters of the essentially saturated hydrocarbyl-substituted ethylene sulfonic acid and a primary or secondary amine, which are also provided according to the invention, are assumed to consist mainly of compounds of the formulas VII and VIII ₁ R ¹ R ¹

VII (H ₂ C-CH ₂ -SO- ^ Q VIII

while of the products of the essentially saturated hydrocarbylsulfonyl chloride and a primary or secondary Amin is believed to be primarily compounds of the formula

are where

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(a) R has an essentially saturated hydrocarbyl radical about 35 to 350 carbon atoms and 0 to 3 olefinic Double bonds,

(b) Q is a nitrogen-containing radical that is formed when one or more hydrogen atoms are removed from one or more several nitrogen atoms of ammonia or a hydro = containing at least one primary or secondary amino group carbylamine, aminohydrocarbylamine, alkoxyhydrocarbylamine, alicyclic hydrocarbylamine, alkylenepolyamine or hetero = cyclic amine, and

(c) m represent a positive integer.

The radical Q can be an amino, hydrocarbylamino, aminohydro = carbylamino, alkoxyhydrocarbylamino, alicyclic hydro = carbylamino-, alkylenepolyamine-hydrocarbylamino- or hetero = be cycloamino group. If the amine is a monoamine, it is formed mainly a monosulfonamide (m = 1) or sulfon = imid (m = 2). If the amine is a polyamine, each is primary Amino group to react with two aryl-hydrocarbylethyl = sulfonate groups are available, and any secondary amino group is available for reaction with an arylhydrocarbylethylsulfonate group available, so that a mixture of monosulfonamides, Bis-sulfonamides, tris-sulfonamides and the like obtained, depending on the relative molar amounts of amine and SuIfonat. Preferred compounds are those in which m the number 1 or 2 means.

The radical R is preferably a branch on the o (- or ß-carbon atom on.

If a sulfonamide product with fully saturated Hydro = carbyl radical, one has to use the sulfonamide with hydrogen and a conventional precious metal or precious metal =

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oxide hydrogenation catalyst, for example platinum or platinum = oxide, hydrogenate.

Furthermore, according to the invention oil-soluble nitrogen-containing products are prepared by reacting at a temperature of about 50 to 250 ⁰ C a aryl ester of a substantially saturated Hydrocarbyläthylsulfonsäure with a nitrogen containing compound having at least one amine hydrogen, i.e., a -NH-G roup.

Y / eiterhin according to the invention oil-soluble nitrogen-containing products are prepared by reacting at a temperature of about 0 to 100 ⁰ C, a substantially saturated Hydrocarbylsulf0 = nylchlorid with a nitrogen containing compound having at least one amine hydrogen, that is a HH-Bunktion, _o

Aryl ester, sulfonyl chloride and nitrogen-containing compound have been described above. The oil soluble sulfonamide product usually contains from about 0.1 to about 1 mole of amine in the product per equivalent of sulfonyl radicals in the product.

An excess of amine, generally about 1.1, is usually used in order for the reaction to proceed to completion up to 15 moles of amine per equivalent of sulfonate ester or sulfonyl = chloride. The excess amine can later be recovered. When using excess amine you can get up to to about 1 mole of monoamine with the sulfonate ester or the sulfo = react nyl chloride. However, up to about 1.5 moles of polyamine per equivalent of sulfonate ester, possibly in solution, incorporated into the sulfonamide product.

As already mentioned, the implementation takes place between Hydrocar =

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byläthylsulfonsäurearylester and amine at a temperature of about 50 to about 25O ⁰ C and preferably from about 100 to about 200 ⁰ C, particularly preferably at about 125 to about 175 C. The reaction between SuIfonylchlorid and amine is carried out at a temperature of 10 to 100 ⁰ C.

Typically the aryl ester, sulfonyl chloride and the nitrogenous compound liquids. The procedure can therefore be carried out without a solvent, but suitable inert solvents can also be used. to suitable solvents include hydrocarbons such as refined mineral oil and low-boiling aliphatic and aromatic hydrocarbons, especially those with boiling points near the maximum temperature suitable for the reaction mixture.

The process is preferably carried out in an inert atmosphere, with nitrogen being the cheapest and most easily accessible.

The process is usually carried out by stirring throughout the reaction time. Typically they will be heating and stirring continued until the small molar amount of the reactant used is complete is used up. Generally, the reaction occurs in about 1 to about 24 hours, and usually in about 2 hours up to about 8 hours.

The excess of the reactants and the hydrogen chloride released during the reaction and low-boiling solvents are washed with bases such as aqueous metal carbonate solutions, fflethanolic bases and the like removed.

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If the sulfonamide is made from the hydrocarbylethylsulfonic acid aryl ether excess reactants and the aromatic hydroxyl compound are removed by distillation.

Before this distillation, it is often advisable to flush the reaction product with an inert gas such as nitrogen at elevated temperatures of, for example, about 150 to about 200 ^° C., generally for several, for example 1 to 8, hours in order to reduce the amounts of aromatic hydroxyl compound and to reduce excess amine in the reaction product. Rinsing can take place at reduced pressure. Furthermore, undesired products can also be removed by codistillation with a hydrocarbon solvent in the medium boiling range such as, for example, a solvent-mineralized neutral oil. Such co-distillation is preferably carried out under reduced pressure.

After rinsing or. the code distillation, it is often expedient to treat the reaction product with a suitable diluent to be diluted in order to facilitate its handling. Typically, about 25 to 50 wt. Diluents are used added. Suitable diluents are, among others Solvent-refined neutral oils, especially those with a low viscosity of around 100 SUS at 37 »8 ° C.

The invention also relates to lubricating oil additive concentrates containing about 90 to about 10 weight <> $ an oil of lubricating viscosity and from about 10 to about 90 wt. <? O of the oil soluble, nitrogen-containing product, which was prepared by reacting (a) an aryl ester essentially saturated hydrocarbylethyl sulfonic acid or (b) an essentially saturated hydrocarbyl sulfonyl chloride with a nitrogen-containing compound.

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which has at least one amine hydrogen, that is to say an -NH function, the essentially saturated hydrocarbyl substituent having at least 20 aliphatic carbon atoms. The concentrates should contain as much of the oil-soluble nitrogenous product as practically possible since these concentrates are made to save shipping costs, storage facilities and the like. Typically, these concentrates contain only enough diluent to be easily handled during shipping and storage. Suitable diluents for the concentrate are any inert diluent. An oil of lubricating viscosity is preferably used as the diluent so that the concentrate can easily be mixed with the lubricating oils in the manufacture of lubricants. The lubricating oils suitable as diluents typically have viscosities in the range from about 35 to about 1000 Saybolt Universal Seconds (SUS) at 37 »8 ⁰ O; however, any other oils of lubricating viscosity can also be used.

Furthermore, lubricants are provided according to the invention which contain (a) an oil of lubricating viscosity and (b) a dispersing one effective amount of the oil-soluble nitrogen-containing products obtained by reacting (1) one Aryl ester of an essentially saturated hydrocarbyl = ethyl sulfonic acid or (2) an essentially saturated hydrocarbyl sulfonyl chloride with a nitrogen-containing compound, which has at least one amine-hydrogen, that is to say an -NH-]?

Saturated hydrocarbyl substituent at least 'al'iphatic carbon atoms owns »

For the production of a lubricating oil according to the invention or con

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Lubricating oils suitable for centrat are oils with a lubricating viscosity from petroleum or synthetic oils. The oils can be paraffinic, naphthenic, or halogen-substituted hydrocarbons, synthetic esters, or mixtures thereof. Oils of lubricating viscosity have viscosities in the range from 35 to 50,000 SUS at 37.8 ⁰ G and usually from about 50 to 10,000 SUS at 37.8 ⁰ G. The amount of the oil-soluble nitrogen-containing product according to the invention that is effective in dispersing into the lubricating oil is incorporated varies greatly depending on the particular sulfonamide and the intended use of the lubricating oil. Further conventional additives which can be used in combination with the sulfonamides are, for example, ashless dispersants such as those of US Pat. No. 3,172,892, 3,219,666 and 3,381,022, neutral and basic calcium, barium and magnesium petrosulfonates or -alkylphenates, oxidation inhibitors, antifoams, agents for improving the viscosity index, pour point depressants and the like, for example chlorinated waxes, benzyl disulphide, sulphurised spermacet oil, sulphurised terpenes, phosphoric esters such as trihydrocarbyl phosphites and phosphates, metal thiocarbamates such as zinc phosphorodithamioctylates such as zinc phosphorodithoctylate dioates such as zinc phosphorodithioctylates Polyisobutene having an average molecular weight of 100,000 and the like.

Generally, lubricating oils contain from about 0.1 to about 20 weight ^c / o of the oil soluble nitrogenous product. More usually the level is from about 0.5 to about 10 weight percent, and usually from about 1 to about 8 weight percent.

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The lubricating oil can also be prepared by (a) a Mixture of a main component of an oil of lubricating viscosity and a dispersing effective J-: narrow of the oil-soluble nitrogenous product and (b) a concentrated lubricating oil additive from an oil of lubricating viscosity and up to 90 GeWo? i, but at least a dispersing effective length of the oil-soluble nitrogen-containing product ^ combined with one another.

The lubricating oils according to the invention are suitable for lubricating internal combustion engines. They don't just lubricate the engine, but support due to their dispersing properties maintaining a high level of purity of the lubricated Parts.

Lubricating oils which contain sulfonamides according to the invention, in which R 20 to about 35 carbons
especially in two-stroke engines.

wherein R has 20 to about 35 carbon atoms are suitable

The sulfonamides according to the invention can also be used as fuel additives serve, v / o with man. 0.00001 to 5% by weight of suifonamide used. When used in common volatile petroleum distillate fuels, for example, fuel oils, diesel oils, gasoline, aviation fuel, jet fuels, and the like they promote the cleanliness of the engine, especially the fuel system such as the fuel lines, "carburettor, Injectors, pumps and the like. In heating oils, for example, they serve as gowns that prevent the filters from clogging.

Example 1A: Preparation of o-chlorophenyl vinyl sulfonate

A 5 liter four neck flask comes with an electric motor powered stirrer, thermometer and Y-tube. A water cooler turns into a. Branch of the Y-tube inserted. That The end of the cooler is connected to a scrubber. In the other

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whose branch of the Y-tube becomes a pressure-compensated dropping funnel built in, which is a 25 Ge \ v "^ ige solution of sodium = contains hydroxide in water. A 500 ml four-necked flask will be used provided with a bottom opening. This opening is in the fourth neck of the 5 liter flask by means of a 38 cn long Connection piece introduced. The connecting piece is with electric Apparent heating tape is wrapped around it, which heats the outlet to about 115 to 125 ° C. The 500 ml flask comes with an electric powered stirrer, a thermometer, a feed tube for ethylene gas and a Y-tube. In a branch of the A thermometer is plugged into the Y-tube, the other branch is provided with a pressure-compensated dropping funnel. The top opening of the dropping funnel is provided with an inlet tube equipped for nitrogen gas. This pipe is in connection with a V / äseher, which in turn with a Nitrogen betrayal under pressure.

The 5 liter flask becomes wet with 1280 ml, 64O ml 1,2-Di = chloroethane, 150 ml 25% sodium hydroxide solution in water and 350 g (2.72 moles) of o-chlorophenol are charged. This mixture is cooled to 0 C while stirring in a dry ice-acetone bath « The dropping funnel of the 500 ml flask is filled with the contents A 903 g ampoule of sulfur trioxide is charged, although the sulfur trioxide contains an inhibitor, are in commercially available Ampoules typically have small amounts of polymerized Sulfur trioxide. A 908 g ampoule of good quality State usually contains 850 to 860 grams of liquid sulfur trioxide. The heating bath for the connection piece and the stirrer for the 500 ffil flask is switched on and the entire reaction system is flushed with nitrogen, which is fed through the sulfur trioxide dropping funnel from the nitrogen washer will. After the reaction system has been filled with nitrogen, ethylene is introduced into the 500 ml

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Piston inserted. As soon as the flow of ethylene has stabilized, sulfur trioxide is introduced into the .Reaktionsgefä ^ from the feed funnel. The stirrer in the 500 ml flask causes the ethylene and sulfur trioxide to be intimately mixed. The conversion between ethylene and sulfur trioxide to form orbyl sulfate takes place rapidly with poor development. The heat of reaction quickly warms the reaction vessel to about 150 to 170 Ο »At these temperatures the carbyl sulfate (about 109 to 110 ^° C) remains liquid and runs off in the heated bottom outlet pipe and then drips into the sodium chlorophenate solution in the 5 liter flask, which is stirred.

Carbyl sulfate and sodium chlorophenate react under alkaline conditions Conditions (pH 9 to 11) for o-chlorophenyl vinyl sulfonate and sodium sulfate.

The flow rate of the ethylene is adjusted so that that there is a slight excess over the amount required for reaction with that flowing in from the dropping funnel • Sulfur trioxide is required. L '; an it determines easily, by measuring the nasal velocity in the sulfur trioxide addition funnel connected scrubber respectively. Bubble counter and in the «escher respectively. . nozzle counter at the outlet of the cooler compares on the 5 l> iter flask. There is a slight excess of ethylene when the .Slase velocity is at the end of the cooler is larger than at the entrance of the sulfur trioxide feed hopper. The reaction continues until all of the sulfur trioxide is consumed. Periodically becomes during the implementation of the pH of the reaction mass in the 5 liter flask checked. The corresponding feed funnel becomes Sodium hydroxide added continuously to keep the pH between 9 and 11.

After the sulfur trioxide has been consumed, the reac-

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tion mixture irr. The 5 liter flask was stirred for about 30 minutes and then neutralized to pH 5 with concentrated hydrochloric acid. Then, the mixture is heated to 40 ⁰ G and transferred to a separatory funnel. The organic phase is drained off, a through "Celite" -Ji ¹ ilterhilfs edium ^ filtered and. Rotary evaporator stripped to an endpoint of 1C0 ° C at 2 to 5 mm Hg. Typical crude yields of o-chlorophenyl vinyl sulfonate are 550 to 615 g when charged with 350 g of o-uhlor = phenol.Typically, the crude product contains less than 1 $ unreacted o-chlorophenol, the sulfur content is 15.3 to 16.4 $ and the chlorine content $ 15.0 to $ 15.6.

Example 13: Preparation of phenyl vinyl sulfonate

Using the apparatus and method according to the example 1A is phenyl vinyl sulfonate from 253 g of phenol in a 5-1 iter flask manufactured; Sulfur content $ 14.3 to $ 15.4.

Example 2: Addition of o-chlorophenyl vinyl sulfonate to polybutene.

A Reaktionsgefätf is moelernent with stirrer, dip tube for a Ther = a ^e ffit cold water jacketed · endpiece and condenser, a gas inlet and a charging port provided.

9.37 kg (10.39 gram-moles) of a polybutenes with a number average molecular weight of 950 are introduced into the vessel under a nitrogen blanket. While stirring, the Beschikkung is heated to 120 ⁰ C. Then 2.73 kg (12.47 gram-moles) of o-chlorophenyl vinyl sulfonate are introduced from an addition funnel through the charge port. The reaction mixture is ^{heated to 220 °} C. with stirring and kept at this temperature for 24 hours while the nitrogen atmosphere and

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keeps the cooler running.

After · 24 hours the reaction mixture becomes less than 65 C cooled and mixed with 15 liters of methanol. The mixture is applied while stirring and in a nitrogen atmosphere The reflux temperature ν on about 65 ° C and 45 minutes on Boiled to reflux, then cooled to room temperature. The emotion is switched off and phase separation is allowed to take place. If the phase separation does not take place quickly, others can 4 to 8 liters of methanol are added.

The lower layer is withdrawn from the reaction vessel and saved. The top layer is transferred to a storage tank. The lower layer is returned to the reaction vessel and a further 15 liters of methanol are added. Then the mixture is refluxed for 45 minutes while stirring, cooled to room temperature and brought to separation. The lower layer is again withdrawn from the reaction vessel and the upper layer is passed into the storage vessel. The lower layer is returned to the reaction vessel again. The container in which this phase was temporarily stored is rinsed with 4 liters of hydrocarbon thinner and the mixture is also added to the reaction vessel. The attachment to the cooler is ^{heated to 82 °} G, while the flow of cold water is maintained in the heat exchanger. A vacuum is then applied to the vessel and the contents are heated to a maximum of 165 ° C. in order to distill off the thinner and the methanol. The residue is cooled to room temperature and transferred to a storage container. The polybutene-substituted ethyl = sulfonic acid-o-chlorophenyl ester obtained in this way can be used in a satisfactory manner for the preparation of the sulfonamides according to the invention without further purification. Typical analysis values lukewarm

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th: 1.46 to 1.54-5 »sulfur, 1.49 to 1.5690 chlorine.

Example 3 '> Addition product of polyisobutenyl chloride

and o-chlorophenyl vinyl sulfonate Example 5A

512 g (0.357 KoI) of a polyisobutenyl chloride (4 ü-ew, ^ chlorine), prepared from a polyisobutene with a number average molecular weight of 1400, and 94 g (0.43 mol) of o-chlorophenyl vinyl sulfonate are in a with ituhrer, thermometer and 1 liter four-necked flask equipped with nitrogen inlet. Under a nitrogen atmosphere, the reaction mixture is ^{heated to 200 °} C. with stirring and kept at this temperature for 7 hours. 16 al samples are taken after 2, 4 and 7 hours for hyamin titration.

Hyamin titration is used to determine the amount of anionic detergent in a sample. A known weight sir.enge is dissolved in chloroform and titrated with a dilute aqueous solution of Hyamin 1622. One uses as an indicator acid methylene blue. The Hyamin solution is added in suitable portions, 2 minutes after each addition shakes vigorously. The blue color is initially concentrated in the lower chlorofluid layer, but gradually appears in the course of the addition of hyamin in the upper aqueous layer. The end point is the same coloration of the two Layers ahead. The millimoles of sulfonate / g sample are calculated from millimoles sulfonate / g = VM / W, where V = the volume of the Hya Redemption in ml, M the holarity of the hyamin solution and W the Mean sample amount in grams.

After 7 hours the remaining reaction mixture (532 g) cooled and transferred to a 2-liter three-necked flask equipped with a stirrer and thermometer, with one being used for

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Flushing the reaction flask uses 50 ml of a hydrocarbon diluent. To the mixture of the product and diluent SOO ml of methanol are added and the mixture is stirred for 45 minutes at Rückfluidtsmperatur (64 ⁰ C). An emulsion is obtained which is not broken on standing. Another 200 ml of methanol and 200 ml of hydrocarbon diluent are added and the mixture is stirred for 2 minutes. The mixture is then allowed to settle at room temperature for 1 1/2 hours, after which the supernatant liquid (about 1100 ml) is decanted off. To the remaining mixture 800 ml of methanol are added, then 45 minutes at reflux temperature (63 ⁰ C) is stirred. An emulsion is again obtained, to which 200 ml of hydrocarbon diluent are added and the mixture is stirred for 2 minutes. The mixture is then allowed to settle at room temperature for 1 1/2 hours and the supernatant liquid (about 300 ml) is decanted off. The extracted product remaining in the flask is dissolved in the hydrocarbon diluent and transferred with a little solvent to a 1 liter three-necked flask. The solvent is stripped off to the end point of 165 ^° C. at 5 mm Hg, 466 g of product being obtained; Sulfur content 0.38 wt, #, chlorine content 1.19 Gev /.#.

Example 3B

The apparatus of Example 3A is used. 512 g (0.357 Lioi) of a Polyisobutenylchlorids (4 wt _o ^ chlorine, prepared from a polyisobutene having a number average molecular weight of 1400) and 97 g (0.43 mol) of o-chlorophenyl-vinylsulfO = nat be in the flask were charged. This reaction mixture "is heated with stirring 10 hours at 180 ⁰ C, with a nitrogen flow is maintained through the flask. The exhaust gas is a sparger in an Erlenmeyer flask

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Washed out with 200 tablespoons of Yvasser. After 2, 4, 6 and 10 hours 16 ml samples are taken for hyamin titration. The water trap for the exhaust gas is renewed every time a sample is taken =, The water is mixed with sodium hydroxide solution until it is methyl Orange end point titrated. The 4 titrations require 100, 32.3 ,. 19 and 20.4 el, - that means a total of 171.7 ml, correspondingly 0.515 moles of sodium hydroxide.

The remaining reaction mixture (530 g) is transferred to a 2 liter three neck flask using about 50 ml of hydrocarbon diluent to flush the reaction flask. 800 ml of methanol are placed in the three-necked flask and the mixture is refluxed with stirring for 3/4 hours. After switching off the agitator, there is no complete separation. 200 ml of η-hexane are added and the mixture is stirred for a further 2 minutes. After standing for 1 hour at room temperature, the mixture has settled and about 800 ml of the supernatant liquid is decanted off. Then 800 ml of methanol are added to the 2 liter flask and the mixture is refluxed for 3/4 hours. After standing for 1 1/2 hours at room temperature, about 900 ml of the supernatant liquid are decanted off. The mixture remaining in the flask is dissolved in the hydrocarbon diluent and transferred to a 1 liter three-necked flask. The solvent is then stripped off to an end point of 165 ^° C. at 5 mm Hg, 460 g of product being obtained; Sulfur content 0.99 wt. $, Chlorine content 1.84 wt. ⁰ Jo.

Example 3Q

In a 1 liter four-necked flask (see Example 3A) 506 g (0.5 luene) of polybutene chloride (4 wt.% Chlorine) made of a polyisobutene with a number average molecular weight of 950, filled in under a nitrogen atmosphere. then

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142 g (0.65 Hol) of o-chlorophenyl vinyl sulfonate are added. The reaction mixture is heated 7 hours to 210 ⁰ G under stirring in a nitrogen atmosphere in the flask. After 2, 4 and 7 hours, 16 cl samples are taken for hyamin titration in order to follow the course of the reaction. After the 7 hour reaction time, the reaction mixture (569 g) is transferred to a 2 liter three-necked flask, using about 50 ml of the hydrocarbon diluent to rinse out the reaction flask. Then 800 ml of methanol are added and the mixture is stirred at reflux temperature (64 ° C.) for about 45 minutes. The mixture is then left to stand at room temperature for about 3 1/2 hours. The separation is quick, but only about 700 ml of supernatant liquid can be decanted off. Are added to 300 ml of methanol and the mixture is stirred for about 45 minutes at reflux temperature (64 ⁰ C), then allowed to stand 1 3/4 hours at room temperature. Again, the separation takes place quickly, but only about 500 ml of the overflowing liquid can be decanted off. The mixture is mixed with 600 ml of η-hexane and stirred for 2 minutes. After settling for 1/4 hour, about 550 ml of the supernatant liquid are sucked off. The mixture remaining in the flask is transferred to a 1 liter three-necked flask, a small amount of η-hexane being used to rinse the flask. The solvent is ^{removed by stripping at 190 °} C. and 5 ram Hg, 475 g of product being obtained ; Sulfur content 1.80 wt. ^, Chlorine content 2.16 wt. ^.

Example A · General Procedure for the Synthesis of Sulfonamides

A flask equipped with a thermometer, stirrer and reflux condenser is filled with the aryl ester of the hydrocarbyl-substituted Ethyl sulfonic acid charged. Then the amine is added and the mixture is placed under a nitrogen atmosphere and under

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Stirring heated to the temperature given below. The heating time is also listed below. Excess anine. and the aromatic hydroxyl compound which is liberated during the reaction are distilled off at reduced pressure (generally about 1 to 2 is.mHg) to an end point of about 170 ⁰ C. The residue is then flushed with nitrogen at ⁰ C 17U, typically about 6 to 8 otunden to the amounts of entrained aromatic hydroxyl compound to prevent =. The final product is diluted with neutral solvent-refined lubricating oil having a viscosity of 100 SUS at 37.8 ° C to improve its handling (typically 25 to 33% by weight diluting oil is used).

In the following examples A to V / sulfonamides are prepared from the o-chlorophenyl ester of a polyisobutenylethylsulfonic acid. The number average molecular weight of the PoJy = isobutenyl group is about 950 »

Example A: From n ~ hexylamine

25 g of chlorophenyl polyisobutenylethylsulfonate (1.69 GeWo $ sulfur) are reacted with 12.7 g (equivalent ratio of 9 »5) n-hexylamine for A hours at 115 ^° C. The product is stripped off in vacuo and ^{flushed with nitrogen for 8 hours at 170 °} C., 23.4 g of product being obtained. This product is diluted with 7.8 g of neutral solvent-rarified lubricating oil of viscosity 100 SUS; Chlorine content 0.07% by weight, sulfur content 1.17% by weight, nitrogen content 0.53% by weight <fo.

Example B: From n-heptylamine

25.1 g Polyisobutenyläthylsulfonsäure-chlorophenyl ester (1.77 wt. ° / o sulfur) are reacted with 8.20 g (equivalent ratio 5.1)

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n-Heptylaiuin reacted for 4 hours at 166 ⁰ G (reflux temperature). The sulfonate had previously been dried using an -öenzene azeotrope, the amine with calcium hydride. The reaction product is vacuum stripped and flushed with nitrogen, giving rr.an 24.0 g of product which is diluted with 300 g of neutral solvent-refined lubricating oil of 100 SUS; Chlorine content U, 24% by weight, sulfur content 1.29% by weight, nitrogen content 0.51% by weight.

Example C: From n-octylamine

409/9 g of chlorophenyl polyisobutenylethylsulfonate (1.62 % by weight of sulfur) and 230.1 g (equivalent ratio of 10.5) of n-octylamine are reacted at 160 ° C. for 3 hours. The reaction product is stripped off in vacuo and flushed with nitrogen, 400.3 g of product being obtained. This product is diluted with 133> 6 g of a neutral, solvent-refined lubricating oil of 100 SUS; Chlorine content 0.07% by weight , sulfur content 1.25% by weight, nitrogen content 0.53% by weight.

Example D: From di-n-butylamine

25 »0 g of the sulfonate used in Example 3 and 14 ₉ 0 g (equivalents ratio 7.9) di-n-butylamine are reacted at 170 ° C. (reflux temperature) for 4 hours. The product is stripped off in vacuo and ^{flushed with nitrogen for 10 hours at 170 °} C., 22.3 g of a product being obtained which is diluted with 7 »6 g of a neutral solvent-refined lubricating oil of 100 SUS; Chlorine content 0.12% by weight, sulfur content 1.03% by weight ^ ₁ nitrogen content 0.32% by weight.

Example E; From di-n-hexylamine

25.1 g of sulfonates as described in Example B and 7.5 g (equivalent ratio of 2.9) of di-n-hexylamine are 22 hours at 130 ⁰ C.

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(Reflux temperature) implemented. The reaction mixture is im Stripped vacuum and flushed with nitrogen, whereby one 22.5 g of product is obtained, which is refined with 7.5 g of a neutral solvent Lubricating oil is diluted by 1UÜ SUS; Nitrogen content 0.33 wt. #.

Example ff; Made of Korpholin

25.0 g of the sulfonate used in Example B and 5.4 g (equivalent ratio 4.5) of morpholine are ^{reacted with one another at 150 °} C. for 28 hours. The sulfonate had previously been dried using a benzene azeotrope. The reaction mixture is stripped in vacuo to give 23.6 g of product which is diluted with 7.9 g of a neutral solvent-refined lubricating oil of 100 SUS; Chlorine content 0.42% by weight, sulfur content 1.41% by weight, nitrogen content 0.46

Example G: From piperazine

2055 g of polyisobutene; yläthylsulfonsäure-chlorophenyl ester (1.56 Gevf.fo sulfur), prepared according to Example 2, and 257 g (molar ratio 3) piperazine at 130 ⁰ C (fs refluxed temperature). 4 hours implemented together. The reaction mixture is then diluted with 0.5 volume / »hexane mixture, suction filtered through Gelite 545, the filtrate is stripped off in vacuo and. Flushed with nitrogen for 18 hours, 1927 g of pro. product which is diluted with a neutral solvent-refined lubricating oil of 100 SUS; Chlorine content 0.084% by weight, sulfur content 1.52% by weight, nitrogen content 1.08% by weight.

Example H; Made from 1,3-propanediamine

2055 sulfonates used in Example G 371 g (molar ratio 5) g 1,3-propanediamine are reacted for 4 hours at 152 ^J C (reflux temperature). Then the reaction

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Mixture with 0.5 volume? «Hexane mixture, diluted over gelite 5 * 4-5 sucked off, the piltrate is stripped off in a vacuum and Flushed with nitrogen for 6 hours, wc obtained at 1934 g of product will. This product is refined with neutral solvent Lubricating oil diluted by 1U) SIi3; Chlorine content C, 03 Wt.? ', Sulfur content 1.43 wt., Nitrogen content 2.31 wt.

Example I: From 1,6-hexanediamine

30 g of the sulfonate used in Example H and 16.5 g (molar ratio 10) 1,6-hexanediamine are reacted for 2 hours at 14O ⁰ G, then it is stripped off in vacuo and the mixture is flushed with nitrogen for 4 hours, with 29? 2 g of product result. This product is diluted with 9) 7 g of a neutral, solvent-refined lubricating oil of 100 SUS; Chlorine content 0.024% by weight, sulfur content 1.03% by weight, nitrogen content 0.88% by weight.

■ Example J: From dimethylaminopropylamine

25.0 g of the sulfonate used in r-example H and 12.0 g (Llolverheltnis 9 »9) Dimethylsminopropylamine are at 125 ° C (Reflux temperature) reacted for 2 hours, then the reaction mixture Stripped off in vacuo and flushed with nitrogen, v / o at 24 g product are obtained. This product is made with 8.0 g of neutral solvent-refined lubricating oil diluted by 100 SUS; Chlorine content 0.12% by weight, sulfur content 1.14% by weight, nitrogen content 0.89% by weight.

• Example K: From tris (2-aminoethyl) aKin

50 g of the sulfonate used in Example H 40 g (11.6 mol ratio) of tris (2-aminoethyl) amine are reacted for 2 hours at 13O ⁰ C, then the reaction mixture is stripped in vacuo and flushed with nitrogen, 46 , 5 g of product are obtained. This product is 15 »5 g of one

6 0 9 8 5 2/1 0 7 9

neutral, solvent-refined lubricating oil diluted by 100 3U13; Chlorine content 0.036 wt. ', O ₁ öchvefelgehalt 1.25 Gev. ^:,:, Nitrogen content 1.21 percent _o $ i.

3 Example L: Made from ethylene diairine

1530 g Polyisobutenyläthylsulfonsäure-chlorphenylcster (1 »52 wt. ° 'a sulfur), prepared according to Example 2, and 453 g (Liolverhältnis 12) Ethyl end iansin be reacted for 4 hours at 12O ⁰ C (hückfluütemperatur). Then, the Reaktionsgercisch is stripped in vacuo and flushed with nitrogen for 5 hours to obtain 1522 g ^r roduct. This product is diluted with a neutral solvent-modified lubricating oil of 100 SUS; Chlorine content 0.02 aew.js, sulfur content 1.24 wt%, nitrogen content 1.15 #

Example Hz Made of ethylenediamine

The sulfonate is dried by Serizol-Assotrop and the ethylenediamine is dried over Kalium hydro: -: id. 400.3 g Polyisobutenyläthylsulf cnsäure-o-clilcrphenylester (1, 5 ^υ G-ew;. J sulfur) and 120.8 g (10.7 molar ratio) Äthylendiainin weroen reacted for 4 hours at 124 C (Kückflußtenperatur). The heating product is then stripped off in vacuo and flushed with nitrogen for 5 hours at 175 ° C., 354.9 g of product being obtained. This product is mixed with 113.3 g of a neutral, solvent-refined lubricating oil. diluted by 100 SUS; Chlorine content 0.086 C-ev / .fi, sulfur content 1.21% by weight, nitrogen content 0.95% by weight.

Example N: Made from diethylenetriamine

2105 g of the sulfonate used in Example 41 from right to 309 g (Lol ratio 3) Diethylenetriamine will 6 3tun.:;or at 160 ° C implemented, then the -teaktionsge ^ isoa in the Vaki,:; T .: stripped, Flushed with nitrogen for 6 hours, rait C, 5 volume ^

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Diluted hexane mixture and sucked off through Gelite 545. The filtrate becomes Ir. Vacuum stripped to yield 1952 grams of product which is diluted with a neutral, solvent-refined lubricating oil of 100 SUS; Chlorine content 0.36 C-ew "^, sulfur content 1.13 wt. ^ ₁ nitrogen content 1.60 Gew.f>.

Example 0: From triethylenetetramine

65.3 g (30 I ^ illimol) of Pclyisobutenyläthylsulfonsäure-o-chloro = phenyl ester and 2.2 g (15 iviillimol) of 'iriethylent et ramin'"earth reacted at 200 ⁰ C Stripped end point of 20 ° G at 1.5 m Hg and held at these conditions for 1/2 hour, resulting in 64.0 g of product 100 StJS diluted; chlorine content 0.24% by weight; - ',

Example P: From i'riäthyleritetraniin

2,050 g of the sulfonate used in Example 4L 71 g (! Colverhältnis 0.5) triethylenetetramine are reacted for 6 hours at 130 ⁰ C. Then v. ^: Ill the rieaktionsgenisch'ί volume with 0.5 Hexanger.isch diluted sucked through Gelite 545, · stripped in vacuo and flushed with nitrogen for 6 hours, whereby 1939 g of product resulting. The product is diluted with a neutral solvent-refined lubricating oil of 100%; Chlorine content υ, ϋβΐ 'ieiv.fi, Schv / efel content 1.13 aew.fi, nitrogen content 1.13 wt. <.

Example ^: From 'ietraäthylenpentamin

2411 g rolyisobutene / ethyl sulfonic acid chlorophenyl ester (1.33 Se · / · .- / * och .'.- fel) and 373 ζ (molar ratio 2) Setraäth / 1 ^ - = pentasiin v; earth 8 ^ ΐυηά · ϊη at 100 '"'.? - implemented, then" vlri the sijeEisch diluted with \, K volumes ilerositi, 6 cage

1 079

Allowed to settle, stripped in vacuo, diluted to 50fi <-e (weight) concentration with a neutral, solvent-refined lubricating oil of 100 SUS and suctioned off through Gelite 545, 4811 g of product being obtained. This product is diluted with a neutral solvent-conditioned lubricating oil of .100 SUS; 3CI content 0.62% by weight, nitrogen content 1.79% by weight.

Example R; Made from iCetraethylene pentamine

2055 g of the sulfonates used in Example 4G and 379 g (molar ratio 2) tetraethylene pentamine are 6 hours at 200 G reacted, then the reaction mixture with 0.5 "volume ^ Diluted hexane mixture, suctioned off through Gelite 545, in vacuo. stripped and flushed with nitrogen for 5 1/2 hours, 2037 g of product being obtained. This product is made with a neutral solvent-refined lubricating oil 100 SUS diluted; Chlorine content 0.04% by weight, 3% by weight 1.03 wt. ^, Nitrogen content 3.11 wt. ^.

Example S: Made of ammonia

1262 g of a sulfonate corresponding to the sulfonate from example 2 are introduced into a 3-8 liter autoclave at room temperature. A total of 864 g of liquid ammonia are added under 10.2 kg / cm of pressure. The reaction mixture is heated under stirring for 1 1/2 hours under 1Ou kg / cm to 125 ⁰ C and then cooled to room temperature. Excess ammonia is drained, the crude product (1187 g) is cleaned, heated and flushed with nitrogen for 24 hours ... It is then diluted with a neutral solvent-refined lubricating oil of 100 SUS; Chlorine content 0.07 wt. ^, Sulfur content 1.91 wt. ^ ^1, nitrogen content of 0.76 wt.. "5

R fl 'RR ? / 1 Π 7 9

Example ? : From bis-Ν, Ν'-aminopropylethylenediamine

1446 g of the sulfonate used in Example 4Q and 23S g (lCol ratio 3) bis-Ν, ίΤ'-aminopropylethylenediamine 8 hours at 1üü ° C implemented. The reaction mixture is Diluted with 2.5 volumes of hexane mixture, settle for 2 days left, aspirated through Gelite 545, vacuum stripped, diluted with 1.5 volumes of kerosene, vacuum stripped and diluted with a neutral solvent-refined lubricating oil to a concentration of 50 Ge \ ". £; sulfur content 0.60 Ge \ v.f.i, nitrogen content 1.35

Example U: Made from piperazine monosulfonamide

16.45 g of the sulfonate used in Example 4B are with 13.26 g (mol ratio 1.14) of piperazine monosulfonamide reacted. The reaction is carried out for 22 hours at 150 C, then the keakticnsger: is stripped off in a vacuum and flushed with nitrogen, v.-c with 315 2 g of product obtained will. This product is r.it 10.4 g of a neutral solvent-refined Lubricating oil diluted by 100 SUS; Chlorine content, 24% by weight,, Schvef elge'nalt 1.06% by weight, nitrogen content 0.57 &

Example V; Made from 1,6-hexanediamine monosulfonamide

13 »95 g of the sulfonate used in Example 4H and 14» 68 g (oil ratio 1.06) 1,6-hexanediamine monosulfonamide, prepared according to Example 41, are reacted at 165 ° C. for 44 hours. The reaction mixture is stripped in vacuo and flushed with nitrogen, to give 25 g of product ₅ 43 »This product is reacted with 8.48 g of a neutral solvent refined lubricating oil of 100 SXJS diluted; Chlorine content 0.96 wt. ^, Sulfur content 0.97 txew.fS, nitrogen content 0.47 ^ ew. #.

609852/1079

Example W; From Iris ^ 2-aminoethyl) amine - monosulfQnamide

23 »75 g of polyisobutenylethylsulfonic acid-o-chlorophenyl ester and 25» 0 g (molar ratio 1.04) tris ~ (2-aminoethyl) amine-monosulfonamide, prepared according to Example 4K, are reacted for 30 hours at 175 ° C., then the reaction product is reacted stripped in vacuo and flushed with nitrogen. The product thus obtained is diluted with a neutral solvent-refined lubricating oil of 100 SUS; Chlorine content 0.12% by weight , sulfur content 0.88% by weight, nitrogen content 0.56

Example 5: Preparation of the sulfonamides of tetraethylene pentamine

(a) 200 ml of ether are poured into a reaction vessel which corresponds to the device of Example 2, then im 30 ml of chlorosulfonic acid were added dropwise over the course of 10 minutes. The mixture is flushed with nitrogen, then 300 g a solution of a polybutenes with a number average molecular weight of 950 in 150 ml of ether in a rapid stream added to a feed funnel. »The reaction mixture is 5 Boiled under reflux for hours, then most of the - ^ ether solvent is removed by passing nitrogen through it. far away.

The reaction mixture becomes quite viscous and is diluted to a volume of 2 liters with pentane. The solvent is removed under vacuum at a W'asserbadtemperatur of 40 to 45 ⁰ C and the residue is redissolved in 2 liters of entan ^. The solution is filtered through diatomaceous earth and the filtrate is placed in a 3 liter three neck flask. While stirring, 20 ml of dimethylformamide and then 27.2 ml of thionyl chloride (density 1.655) are added dropwise over the course of 3 minutes at room temperature. The reaction mixture is stirred for 21 hours, then 10 ml of dimethyl = are added

609852/1079

formamide and 27 | 2 ml of thionyl chloride. The mixture is then ^{stripped off in vacuo at 80 °} C. and diluted to 900 ml with xylene, followed by flushing with nitrogen. The product contains $ 1.58 sulfur and $ 3.33 chlorine. According to titration with potassium hydroxide, the equivalent molecular weight is about 2117 «

(b) 60 ml of pentane and 0.6 g of tetraethylene pentamine are added to 14 »6 g of the polyisobutene nylsulfonyl chloride prepared in accordance with part (a). The reaction mixture is stirred at room temperature, diluted with pentane and filtered through diatomaceous earth. The mixture is then washed twice with 10 ml of a 10% sodium hydroxide solution and once with 10 ml of water. Then the mixture at 1QO ⁰ C and 0.1 mm Hg is stripped off to give a sulfonamide product is obtained having the following analytical values: sulfur 1.72, 1.65 $ (theoretical value 1.36 $)} nitrogen 1.33, 1> 37 $ (theoretical value 1.48 $) τ

Example 6? Production of sulfonamides from ethyl chlorosulfonate, polyisobutylene and tetraethylene pentamine

(a) A 3 liter reaction flask is charged with 750 ml of chlorosulfonic acid. The flask is equipped with a stirrer, condenser and gas inlet tube and placed in a water bath. The reaction mixture is stirred while ethylene is introduced via a flow meter. At the beginning of the ethylene supply, small bubbles form, then the gas stops escaping. The reaction vessel is kept at these conditions until exhaust gas escapes very quickly. The ethylene supply is throttled until the exhaust gas emission ceases. During the reaction of ethylene with chlorosulfonic acid exceeds the temperature of the reaction mixture for 3 1/2 hours of the total Re = Action Time 40 ⁰ C.

609852/1079

The reaction mixture is through. Purified vacuum distillation to obtain 1355 g Chlorsulfonsäureäthylester, the 20 mm Hg at between 52 and 54 ° C transitions (.Topf temperature 70 to 75 ⁰ C).

(b) To 164 ^{μg of} polyisobutylene with a number average molecular weight of 950, 700 ml of hexane are added in a 5 liter three-necked flask with stirring in a nitrogen atmosphere. The temperature being kept below 4O ⁰ C. To this mixture is then 357 g of the under part (a) Chlorsulfonsäureäthylesters produced added * The reaction mixture is for 19 hours at 78 boiled to 80 ⁰ C at the reflux of, then volatile components on a rotary evaporator stripped, and then a Srdölkohlenwasaerstoff-solvent is added and the mixture is stripped again at 90 ⁰ C and 10 mm Hg. 184O g of ethyl polyisobutenylsulforate are obtained.

(c) To 1800 g of polyisobutenylsulfonic acid ethyl ester in one

Add 1 liter of hexane to 5 liter four-necked flasks with stirring. 176.7 g of sodium methylate in 800 ml of methanol in a nitrogen atmosphere at 25 to 30 ^° C. are added to this solution. The reaction mixture is refluxed for 5 hours, then the methanol phase is removed. 20 ml of 4,4n-ethanolic hydrochloric acid are added to the resulting solution. The volatile components are removed by rotary evaporation, 1827.4 g of sodium polyisobutenylsulfonate being obtained.

(d) 1,827.4 g of sodium polyisobutylene sulfonate in 600 ml of hexane are poured into a 5 liter flask. Wherein the temperature is maintained below 30 ⁰ C. The reaction mixture is added with stirring 209 g of dimethylformamide, d§nn 189 ml of thionyl chloride was added dropwise. Then the reaction mixture

609852/1079

Stirred for 2 hours at room temperature and then diluted with 400 ml of hexane and left to stand for 4 hours. The lower phase is discarded and the upper phase is filtered through Celite 512 and stripped on a rotary evaporator to obtain 161 g ^Ü Polyisobutenylsulfonylchlorid be obtained.

(e) To a mixture of 68.80 g of tetraethylene pentamine and 120 ml of methylene chloride in a 2 liter flask, a solution of 482.9 g of polyisobutenylsulfonyl chloride in 300 ml of methylene chloride is added with stirring, the temperature being kept at 25 using a Y / water bath to 3O ⁰ C is held. The reaction mixture is stirred for 1 hour at this temperature and then for 16 hours at room temperature, then i / heated for 2 hour under reflux to 40 ⁰ C. Then, hexane was added and the reaction mixture is heated for 2 hours under reflux at 60 ⁰ C.

The reaction mixture is then allowed to cool to room temperature, whereupon a saturated aqueous potassium carbonate solution is added. The mixture is stirred for 1 hour, then becomes Isopropyl alcohol was added and the mixture was stirred for a further 1/2 hour.

The supernatant hexane phase is decanted from some sludge-like material and washed once with water / water, then filtered through Celite 512 and stripped on a rotary evaporator. Toluene is then added so that remaining water can be distilled off azeotropically. The reaction product of tetraethylene pentamine and polyisobutenyl = sulfonyl chloride, mainly from Tetraäthylenpentamin.- sulfonamide of Polyisobutenylsulfonylchlorids, rafünierten solvent to a neutral hydrocarbon oil having a viscosity at 37.8 ⁰ C of 100 SUS in such an amount is added that a 50 ^c A sodium Concentrate of the sulfonamides im

η π 9 L-; 2 ί ' : ·

Get oil; Sulfur content $ 1.43, $ 1.50, chlorine content $ 0.026, Nitrogen content 2.09, $ 2.08.

Example 7: Oxidation Test

The resistance of a Ulformulierung against oxidative changes is measured by the time that 100 g of the test oil at 141 ⁰ C for consumption of 1 liter of oxygen need. For convenience, the present test uses 25 grams of oil and the results are corrected to a 100 gram sample. A catalyst containing a mixture of soluble iron, copper, lead, tin and manganese salts is added to the oil. The test is carried out for 10 hours and the number of liters of oxygen absorbed within this period is also reported. The viscosity of the oil is also measured at the beginning and end of the 10-hour test period. The increase appears as a percentage of the initial value. Table I shows the values obtained with various lubricating oils according to the invention in the oxidation test. The base oil used in this test is a solvent-rajfiniertes per kg of a zinc dialkyl dithiophosphate contains a neutral hydrocarbon oil having a viscosity at 38 ⁰ C of 480 SUS containing 9 millimoles ($ phosphorus 8.5 wt.). The test oil also contains 2.5% by weight nominally sulfonamide active ingredient, the sulfonamide being identified by both the example in question and the amine from which it was prepared. An oil is used for comparison, which contains a commercially available succinimide made from tetraethylene pentamine (TEPA) and a polyisobutenyl succinic anhydride (PIBSA) with a nitrogen content of 2.1 $.

The values in Table I show that the viscosity increases with the oils containing the sulfonamides is noticeably lower than with the 01 with commercially available succinimide · Es is

609852/1079

Note that despite roughly the same amount of oxygen taken up by all tested oils according to the invention this much lower Viscosity increase is achieved

4 amine Table I. 8: engine tests entire op VIS ₁₀₀ -Zu- Oxidation steate Record
Liters / 10 hours I \ J \ J
would take $ Piperazine Number of hours for 5.0 PDA Recording of 1 liter
O ₂ 4.4 29 Sulfonamide BAPEDA 3.2 5.0 17th example EDA 3.1 5.4 30th DETA 2.2 5.1 32 G TETA 2.4 4.6 37 H TEPA 2.2 5.2 30th I. Comparison PIBSA / TEPA 2.8 6.1 74 M. example 2.7 190 N 3.1 P. R.

Several of the above sulfonamides have been tested in internal combustion engines to demonstrate their usefulness as lubricating oil additives.

One of these engine tests is the Ford V-8 piston resin

3 test. In this test, a Ford V-8 engine is operated with 4950 cm in idle, cold and warm with 500/2500/2500 revolutions and at Y / water temperatures of 46/52/77 ⁰ C, with a tunnel temperature of 49/77 / 96 ⁰ C, the operating times were 45/120/75 minutes. In this test procedure, the engine is dismantled every 20 hours and the resin on the pistons is rated on a scale from 0 to 10, with 10 meaning completely clean »

609852/1079

A Central American SAE 30-01 was used as the base oil, which is 30 millimoles / kg carbonated, sulfurized CaI = cium polypropylene phenate, 30 millimoles / kg of a carbonated Calcium sulfonate and 15 millimoles / kg mixed zinc dithio = contained phosphates. From this base oil, lubricating oils were made by adding the various sulfonamides, the in the same manner as in Example 7.

Table II shows the results of these tests. An oil without a dispersant and an oil that contains the already used in Example 7 contains succinimide.

Amine Table II in the oil Milli
mol / kg S Piston resin coating after
60 80 p lot GeWo / N 40 6.9 Sulfonamide BAPEDA Weight / 9 7.2 8.5 7.7 Example 4 EDA ■ _ 0.81 9 9.5 7.2 - without DETA 3.0 0.025 9 7.9 8.2 7.8 T TEPA 2.2 0.034 11 9.2 9.4 9.2 L. TEPA 2.2 0.093 9 9.6 8.5 8.3 N - PIB3A /
TEPA 3.0 0.083 9.3 7.9 7.3 R ¹ PIBSA /
TEPA 4.6 0.063 8.7 9.2 8.9 Q 3.0 0.126 9.6 Comparison' 6.0 comparison

Average value from 2 attempts.

Average value from 8 attempts.

From the above data it can be seen that the sulfonamide made from tetraethylene = pentamine is a better dispersant is than the succinimide formed from the same amine. Man

609852/107 &

can also be seen that all are derived from the various amines The sulfonamides formed are good dispersants in this resinification test works.

Example 9 x 1-G Tracked Tractor Test

Another suitable test is the well-known 1-G caterpillar tractor test, in which a single-cylinder diesel engine with an internal cylinder diameter of 13 cm and a piston stroke of 16.5 cm is operated under the following conditions: control 8 degrees BTDOj mean effective brake pressure 9.9 kg / cm; Braking power 42 HP; 1475 kcal / min, (or 5850 B.Th.U./min.); Speed 1800 rpm; Air pressure rise 135 cm Hg abs .; Air temperature a 124 ° C; Water temperature from 88 ⁰ C; Sulfur content in the oil 0.4 wt. ^, After every 12 hours of operation, enough oil is drained from the crankcase so that 0.95 liters of fresh oil can be added. When testing the lubricating oils of the present invention, the 1-G test is carried out for 60 hours. After these 60 hours, the engine is taken apart and its cleanliness is assessed. The ring ridges are rated on a scale from 0 to 800, where 0 means clean and 800 means black deposits. The piston grooves are rated on a scale from groove filling 0 to 100, where 0 means clean. The underside of the piston is rated on a scale from 0 to 10, with 0 meaning dirty and 10 meaning clean.

A Central American SAE 30-01 was used as the base oil in these tests, which contains 12 millimoles / kg of a zinc bis (al = kylaryl) dithiophosphate and the sulfonamide, which is identified in Table III in the same manner as in Example 8 is. For comparison, oils without dispersants and oils with the commercially available succinimide according to Example 8 were used tested.

609852/1 079

As with the resinification test, this test shows that the sulfonic amides produced from various amines are good dispersants. Note that several Sulphonamides are used with about half the nitrogen concentration compared to the commercially available succinimide, and still show a comparable dispersing effect.

609852/1079

Table III

60-hour 1-G caterpillar sole paper test

cn σ co

Sulfonamide

example

without

At in

Piperazine

PDA

EDA

EDA

DETA

TETA

Comparison PIBSA / 1 IESPA '

Mean from 3 tests.

2.2

2.4 2.8

2.5 2.5 6.2

3.5

Amount in the oil

$ Wt.? S N millimoles /. kg S

0.024 0.027 0.035 0.026 0.040 0.074

0.74

11 11 14 10 10 24 bars

750-780-765

477-84-20

275-30-20

39Ο-25-2Ο

460-45-20

435-70-35
220-160-60

390-50-35

Grooves

81-16-7-8
73-16-1-1
38-12-1-1

4O-9-IO
48-4-1-1
42-5-1-1

40-8-1-0

Piston bottom

5.7 1.4

2.8 4.5 1.9 2.3 0.8

3.1

Claims (1)

Claims R is an essentially saturated hydrocarbyl radical about 35 to 350 carbon atoms and 0 to 3 olefinic Double bonds, Q is a nitrogenous residue that is formed Removal of one or more hydrogen atoms on one or more nitrogen atoms from ammonia or one Hydrocarbylamine, aminohydrocarbylamine, alkoxy = at least one primary or secondary amino group hydrocarbylamine, alicyclic hydrocarbylamine, alkylene = polyamine or heterocyclic amine and m represent an integer. 2. Compounds according to claim 1, characterized in that R is a polymeric hydrocarbyl group derived from a 1-olefin with about 35 to 250 carbon atoms, Q is the remainder of morpholine, piperazine, aminoethylpiperazine or aminoethylpyrrolidine and
m represent the number 1 or 2. 3. Compounds according to claim 2, characterized in that R represents the polyisobutylene radical. en / 4. A compound according to claim 1, characterized in that R is a polymeric hydrocar derived from a 1-olefin byl group having about 35 to 250 carbon atoms and Q from ammonia or an amine of the following formulas s comes from: 609852/1079 IV HN ^ alkylene-N ^ -R « ι ι ⁿ R ¹ R ¹ VI (H-N R ¹ R ¹ wherein η is an integer from 1 to 10, n ¹ O or an integer from 1 to 10, the radicals R ^f each independently represent hydrogen or an essentially saturated hydrocarbon radical, the alkylene radicals each independently have 1 to 8 carbon atoms and, when alkylene denotes the ethylene radical, 2 radicals R ¹ on adjacent nitrogen atoms can together form an ethylene radical, and m denotes the number 1 or 2. 5. Compounds according to claim 4, characterized in that R represents the polyisobutylene radical. 6. Compounds according to claim 4 »characterized in that R ^{1 has} 50 to 150 carbon atoms and the alkylene radical has 2 to 4 carbon atoms and η is a number from 1 to 7 and n ^{1 is} 0 or a number from 1 to 7. 7. Compounds according to claim 6, characterized in that the alkylene radical is an ethylene radical, η is a number from 1 to 5 and n ^{f is} the number 0 or a number from 1 to 5. 609852/1079 8. A compound according to claim 7 »characterized in that
the remainder Q is from ammonia or one of the amines
Ethylenediamine, diethylenetriamine, triethylenetetramine,
Tetraethylene pentamine, tris (amino-ethyl) amine or N, N, N ¹ , N ¹ tetra (amino-ethyl) amine or mixtures thereof. 9. Compounds according to claim 8, characterized in that the remainder is derived from diethylenetriamine. 10. Compounds according to claim 8, that the remainder differs from Tri = Ethylenetetramine derived. 11. Compounds according to claim 8, characterized in that the remainder is derived from ethylenediamine. 12. Compounds according to claim 8, characterized in that the remainder is derived from tetraethylene pentamine. 13 · Connections according to claim 8, characterized in that the rest is derived from ammonia. 14 Oil-soluble nitrogen-containing reaction product from (A)
an aryl ester of a substituted ethylsulfonic acid of the lOrmula B ¹ H ₂ C-CH ₂ ~ S0 ₂ -0-aryl or B ¹ H ₅ C-CH-SO ₂ -O-aryl or (A ¹ ) a hydrocarbylsulfonyl chloride of the formula R ¹ -SO ₉ Cl, wherein R is an essentially saturated hydrocarbyl radical 609852/1079 about 35 to 350 carbon atoms and 0 to 3 olefinic Double bonds, .Aryl represent an aryl radical or substituted aryl radical and
(B) a nitrogenous compound of the jarmel HNR ³ R ² 2 3 wherein R and R independently of one another 'are hydrogen or represent an organic radical which is bound to the nitrogen via a carbon / nitrogen bond. 15 · Product according to claim 14 »characterized» that R is a polymeric hydrocar derived from a 1-olefin byl group with about 50 to 150 carbon atoms and 0 to 2 olefinic double bonds and 2 3 R and R ^ independently of one another are hydrogen, a Hydro = carbyl, alkoxyhydrocarbyl, aminohydrocarbyl, alicyclic Represent hydroearbyl- or alkylenepolyamine-substituted hydrocarbyl radical or together represent the radical of one form heterocyclic amine. 16. Product according to claim 15, characterized in that R represents the polyisobutylene radical * 17. Product according to claim 16, characterized in that R Hydrogen and Ir represents the aminoethyl radical. 18. Product according to claim 14, characterized in that R Hydrogen and R ^ represents the remainder of diethylenetriamine. 2 19 · Product according to claim 16, characterized in that R represents hydrogen and Ή / represents the remainder of triethylenetetramine. 609 8 5 2/1079 20. Product according to claim 16, characterized in that R ² Wasserst
represent. 2 3 R is hydrogen and R is the remainder of tetraethylene pentamine 21. Product according to claim 16, characterized in that 2 3 -R and R represent the remainder of the morpholine. 22. Product according to claim 16, characterized in that 2 3 R and R represent the remainder of the piperazine. 23. Product according to claim 16, characterized in that 2 3 R is hydrogen and R "^ the remainder of bis-l ^ N'-aminopropyl = represents ethylenediamine. 24 · Product according to claim 16, characterized in that R ^{2 is} hydrogen
amine represents. 2 3 R is hydrogen and R ^ the remainder of dimethylaminopropyl = 25 · Lubricating oil, characterized by (A) an oil of lubricating viscosity and (B) an effective dispersing amount of at least one oil-soluble nitrogen-containing compound according to claim 1. 26 «A lubricating oil according to claim 25, characterized by 0.1 to 20 wt. Io the oil-soluble compound. 27 · Lubricating oil according to claim 25> characterized in that R is a polymeric hydrocar derived from a 1-olefin is byl group having about 20 to 250 carbon atoms and Q is derived from morpholine, piperazine, aminoethylpiperazine or aminoethylpyrrolidine. 609852/1079 28 · Lubricating oil according to claim 27, characterized in that R represents the polyisobutylene group. 29 · Lubricating oil additive, characterized by (A) 90 to 10 wt. <P of an oil of lubricating viscosity and. (B) 10 to 90 wt. ^ B an oil-soluble compound according to
Claim 1 30. Lubricating oil additive according to claim 29 »characterized in that R is a polymeric hydrocarbyl group derived from a 1-olefin with about 20 to 25 carbon atoms
and Q is derived from morpholine, piperazine, aminoethylpiperazine or aminoethylpyrrolidine. 31. Lubricating oil additive according to claim 30, characterized in that net that R is the polyisobutylene radical. 32. Lubricating oil according to claim 26, characterized in that R is a polyisobutenyl radical having about 20 to 250 carbon atoms means and Q comes from an amine of the following formulas: IV H-y ι ι R ¹ R R ¹ : R ¹ VI (H-N-Alkylen ^ N-Alkylen-N ^ Alkylea-N-H) ι ^ i R ^f R ¹ wherein η is an integer from 1 to 10, ή »0 or an integer from 1 to 10 and 609852/1 079 R ¹ each independently represent hydrogen or an essentially branched hydrocarbon radical, the alkylene groups each independently have and from 1 to 8 carbon atoms when alkylene represents the ethylene radical, two groups R ¹ at adjacent nitrogen atom may form an ethylene group together, una the number 1 or 2. 53 · Lubricating oil additive according to claim 29, characterized in that R ¹ denotes a polyisobutenyl radical with about 20 to 250 carbon atoms and
Q comes from an amine of the following formulas: IV H-H ^ alkylene-N -) - R ' t · ι D. R 'R ¹ Y / HN ^ alkylene-N ^ - ^ - alkylene ^ - ^ N R ¹ R ¹ VI (HN-alkylene- ^ N-alkyl en-li ^ alkyl en-tf ~ H) ₀ R ¹ R ¹ wherein η is an integer from 1 to 10, n ¹ 0 or an integer from 1 to 10, the radicals R 'each independently represent hydrogen or an essentially saturated hydrocarbon radical, the alkylene radicals each independently have 1 to 8 carbon atoms and, if alkylene denotes the ethylene = ■ radical, 2 radicals R ¹ located on adjacent nitrogen atoms can together form an ethylene group, 609852/1079 and m means the number 1 or 2. 34 · Lubricating oil additive according to. Claim 31 »characterized in that R ^{1 has} 50 to 150 carbon atoms and the alkylene radical • has 2 to 4 carbon atoms, η represents a number from 1 to 7 and n 'represents 0 or a number from 1 to 7. 35 · Lubricating oil additive according to claim 33 »characterized in that H ^{1 has} 50 to 150 carbon atoms and the alkylene radical has 2 to 4 carbon atoms, η denotes a number from 1 to 7 and n 'denotes 0 or a number from 1 to 7. 36 · Lubricating oil additive according to claim 34, characterized in that the alkylene radical is the ethylene radical, η denotes a number from 1 to 5 and n ¹ denotes 0 or a number from 1 to 5. 37 · Lubricating oil additive according to claim 35 »characterized in that the alkylene radical is the ethylene radical, η denotes a number from 1 to 5 and n ^f denotes 0 or a number from 1 to 5. 38 * lubricating oil additive according to claim 36, characterized in that the amine radical of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tris (amino = ethyl) amine or H, N ¹ , K "', H ^r -letra (aminoethyl) ethylenediamine or Mixtures of these originates. 39 · Lubricating oil additive according to claim 37 »characterized in that the amine residue is derived from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine, tris (aminoethyl) amine or N, N, N ¹ , N'-tetra (aminoethyl) ethylenediamine or mixtures thereof . 609852/1079 40 _o Lubricating oil additive according to claim 38, characterized in that the amine residue is derived from tetraethylene pentamine. 41. Lubricating oil additive according to claim 39i, characterized in that that the amine residue comes from tetraethylene pentamine. 42. Lubricating oil, characterized by (a) an oil of lubricating viscosity and (b) an effective dispersing amount of an oil-soluble nitrogen-containing reaction product according to claim 14 from (A) an aryl ester of a hydrocarbyl-substituted ethylsulfonic acid of the formulas: H ¹ H ₂ C-CH ₂ ~ S0 ₂ -0-aryl or R ¹ . H ₃ C-CH-SO ₂ -0-aryl or (A ¹ ) a hydrocarbylsulfonyl chloride of the formula R SO ₉ Cl, in which R is an essentially saturated hydrocarbyl radical with about 20 to 250 carbon atoms and 0 to 3 olefinic double bonds and aryl is an aryl or substituted aryl radical, and (B) a nitrogen containing compound of the formula HNR ⁵ R ² 2 3 wherein R and R ^y independently represent hydrogen or an organic radical which is bonded to the nitrogen via a carbon / nitrogen bond. 43. Lubricating oil according to claim 42, characterized in that 609852/1079 B. a. Polyisobutenyl radical with 50 to 150 carbon atoms and 0 to 2 olefinic double bonds and 2 3 . R and R independently of one another are hydrogen, a Hy = drocarbyl, alkoxyhydrocarbyl, aminohydrocarbyl, ali = cyclic hydrocarbyl- or alkylenepolyainine-substituted Represent hydrocarbyl radical or together form the radical of a heterocyclic amine. 44. Lubricating oil additive, characterized by (a) 90 to 10% by weight of an oil of lubricating viscosity and (B) 10 to 9 ^U G-ew. ^ o of an oil-soluble nitrogen-containing reaction product according to claim 14 from (A) an aryl ester of a hydrocarbyl-substituted ethyl sulfonic acid of the formulas R ¹ H ₅ C-CH ₂ -SO ₂ -O-aryl or R ¹
ι H ₃ C-CH-SO ₂ -0-aryl or (A ¹ ) a hydrocarbylsulfonyl chloride of the formula 1 1 R SO ₂ Cl, in which R is an essentially saturated hydrocarbyl radical having about 20 to 250 carbon atoms and 0 to 3 olefinic double bonds and aryl is an aryl or substituted aryl radical, and (B) a nitrogen-containing compound of the formula HNR ⁵
R ² wherein R and R ^ independently of one another are hydrogen or represent an organic radical which is bound to the nitrogen via a carbon / nitrogen bond. 609852/1079 45 · Lubricating oil additive according to claim 44 »characterized in that
R is a polyisobutenyl radical with 50 to 150 carbon atoms and 0 to 2 olefinic double bonds and 2 3 R and Ir independently of one another are hydrogen, a hydrocarbyl, Alkoxyhydrocarbyl-, aminohydrocarbyl-, ali = cyclic hydrocarbyl- or alkylenepolyamine-substituted Represent hydrocarbyl radical or together form the radical of a heterocyclic amine. 46 · The method for producing an oil soluble nitrogen-containing reaction product according to claim 14, characterized in that, to about 25O ⁰ C an aryl ester of a substantially saturated Hydrocarbyläthylsulfonsäuren whose Hydrocar = bylsubstituent at a temperature of about 50 has at least 20 aliphatic carbon atoms, with 0.1 to 15 mol / equivalent of the ester of a nitrogen-containing compound which has at least one -NH- group. 47 · Process according to claim 46, characterized in that an aryl ester of one of the formulas R ¹ t H ₂ C-CH ₂ -SO ₂ -0-aryl or R ¹ H ₅ C-CH-SO ₂ -0-aryl used where R is an essentially saturated hydrocarbyl radical having about 20 to 350 carbon atoms and 0 to 3 olefinic atoms Double bonds and Aryl represent an aryl radical or substituted aryl radical, 609852/1079 and an amine of the formula HNR ⁵ R ² 2 3 used, in which R and R independently of one another are hydrogen, represent a hydrocarbyl, alicyclic hydrocarbyl or alkylenepolyamine hydrocarbyl radical or together form the remainder of a heterocyclic amine. 48 · Yerfanrea, ". 'Characterized for producing a öllösuchen nitrogen-containing reaction product that is at a temperature of 0 to 50 ⁰ C an olefinically unsaturated hydrocarbon compound having at least 20 carbon atoms with about 1 ■ moles of chlorosulfonic acid are reacted to form a substantially saturated hydrocarbyl sulfonic acid, this treated at 0 to 80 ⁰ C with an inorganic acid chloride to form the sulfonyl chloride and this combined at 0 to 100 ⁰ C with 0.1 to 15 mol / equivalent of the saturated hydrocarbyl sulfonyl chloride of a nitrogen compound which has at least one -NH-G group . 49 · Process for the preparation of an oil-soluble nitrogen-containing Reaction product,.,. . characterized in that one uses an alkyl chlorosulfonate, whose alkyl radical has 1 to 4 carbon atoms, with an olefinically unsaturated hydrocarbon with at least Converts 20 carbon atoms to form one Hydrocarbylsulfonic acid alkyl ester, these with an aiko = holic solution of an alkyl metal hydroxide reacts under Formation of the alkali metal hydrocarbyl sulfonate, the alkali metal hydrocarbyl sulfonate, with a chlorinating agent reacts to form the hydrocarbylsulfonylchloride and this with 0.1 to 15 mol / mol Hydrocarbylsulfo = reacts nyl chloride of a nitrogen-containing compound, which has at least one -NH-G group. For: Chevron Research Company / San Rjtenci / afeo, CaI., V.St.A. 60 9 852/1079 U * / Ä Dr.H.JKWolff Lawyer