DE1745150A1 - Nitrogen containing detergents - Google Patents

Description

DR. EUUE DR. BERG DIPL.-iNG. STAPF "; _{/ K1Cft} PktttKMWC & LTC V (.11 I? V

8 MUNICH 2nd HILBLESTRASSE

Dr, EuIa Dr. Berg Dipl.-Ing. Stapf, 8 Monchen 2, HilblesiraB »20 ·

Monsanto Company, St. Louis, Missouri 63166 / ÜSA

.Your sign Un, .r Z «ch.n ^ m 2 ^, NOV, 196?

Attorney file 16 325 Be / Son

"Nitrogen-containing detergents"

This invention relates to certain new nitrogen-containing compounds which can be used as detergents in US Pat

Oasis 0-2311 <| 0S831 / 1896 '. ■■■ -. ² r.

Lubricating oil formulations are useful.

Under the conditions that occur in a very large percentage of motor vehicle use today, the engines do not reach their most desirable and effective operating temperatures. As a result, v / ground Large amounts of oxidation products are formed, which eventually find their way into the crankcase on the piston rings reach past. Sludge formation in general can therefore result from the polymerisation of those products which pass from the combustion cylinders into the crankcase when there is incomplete combustion of the fuel he follows. Many types of products are pumped through the flask, such as acids, aldehydes, ketones, and amines Oxidation products, whereby the combustion products in turn become part of the lubricating oil preparations. These sponsored By-products can form sludge, with the sludge in turn on the surfaces of parts in one Internal combustion engine is deposited.

It has now been found that the problems associated with what is termed stop-and-go driving, i.e., education of sludge, can be controlled by adding to the lubricating oils of

109831/1696

(A) an oxathiazine of the formula

Il

R-O-C-R.

It '

N SO ₂ ■ CO
R ₄

in which R and R ^ hydrogen and / or a carbon *

Are hydrogen containing groups provided that the sum of the number of carbon atoms present in R and R 1 is at least about 50 carbon atoms and provided that at least one of R and R is a hydrocarbon containing group which is at least about 40 carbon atoms contains, R ₂ and R, are hydrogen and / or a hydrocarbyl group with from 1 to 50 carbon atoms, R ^, hydrogen, a hydrocarbyl group and / or a heterocyclic group with the content of 1 to 10 atoms, optionally by 1 ^

up to 4 heteroatoms such as oxygen, nitrogen and / or Sulfur are interrupted is

(B) a sulfonyl containing compound of the formula

^K 2 ^K 3 ■

I. I '

R - G - C - R. r ι '

H-N SO-X

■■■ '■ ■■' ■ ^E 5 ■ _ ₄ -_. '.' ■■ ■ "

109831/1696

wherein R and R ^ are hydrogen and / or a hydrocarbon containing group, provided that the sum of the number of those in R and R ,. existing carbon atoms is at least 50 carbon atoms and provided • that at least one of R and R ,. a hydrocarbon containing group having at least 40 carbon atoms, Rp and R, hydrogen and / or a hydrocarbyl group having from 1 to $ 0 carbon atoms, Rc are hydrogen and / or C-R ^, R ^ is hydrogen, a hydrocarbyl group and / or a heterocyclic group containing 1 to 10 atoms, optionally interrupted by 1 to 4 heteroatoms, such as oxygen, nitrogen and / or sulfur are, and X is halogen and / or -OM, where M is hydrogen and / or a metal-containing cation, or

(G) a product that. By the reaction of a nitrogen containing compound with an oxothiazine represented by (A), a sulfonyl-containing compound by the formula (B), and mixtures of (A) and (B).

It is therefore critical in the present invention that the sum of the carbon atoms in R ^ and Rg have at least about 50 carbon atoms and additionally at least one of Rxj and R _{2 is} a hydrocarbon-containing group

-5-109831 / 1696

_ 5 -

is of at least about 40 carbon atoms. the critical atomic number of 50 carbon atoms was established because it was found to be about 50 carbon atoms is the minimum number of carbon atoms that enables a material to function as an ashless detergent works. A lower number of carbon atoms does not give the detergent molecule sufficient oil solubility, which is required for the detergent molecule to ' after inhibiting sludge formation and dispersing of the mud to remain soluble. In addition, it was found that slightly lower molecular weight products can act as sludge coagulants, whereby even larger amounts of sludge are precipitated.

The oxathiazine compounds represented by (A) can produced by converting

(d) a hydrocarbon containing material

R - G = G - R ₁
with

(e) a 6c hwef eltrbxide-yielding substance and (f.) an i-iibril of the formula

H ,, GK ■■■■ -

where R, R ,,, Hp, R ^ and R ^, those given above Have meanings.

In carrying out the process for producing a compound represented by (A), the hydrocarbon containing material (d) which yields sulfur trioxide Substance (e) and the nitrile (f) in more indifferent Order are added, the order of addition of (d), (e) and (f) is not critical. It will however, it is preferred that the sulfur trioxide yielding substance (e) is mixed with (d) in the presence of (f), i.e. it is always preferred to have (f) present when (e) is mixed with (d) regardless of the order of addition of (d), (e) and (f).

To carry out the manufacturing process of the compound represented by (A), a temperature is maintained for a period of time necessary to cause the reaction of (d), (e) and (f), with the temperature being constant and / or variable Temperature is to be understood. The process may be carried out at atmospheric pressure or it may over- or subatmospheric pressure may be used depending on the particular eaktionspartnerri ^ used, nei carrying out preparation process of the compound represented by (A) comparison

10 9831/1698

bond, the temperature is generally maintained at from about -5O ⁰ C to about 50 ⁰ C, preferably from about -5O ⁰ C to about 25 ° 0. The time during which the reaction is carried out can vary over a wide range and is dependent on the particular starting reactants represented by (d), (e) and (f) and is the time used to complete the reaction of (i.e. ), (e) and (f). A hydrocarbon solvent such as an aliphatic solvent, mineral and distillate oils can be used as diluents alone or together in a manufacturing process of the oxathiazine compounds. The molar ratios of (d) :( e) :( f) can vary within a wide range and in general the molar ratio of (d) :( e) :( f) will be from about 1: 0.5: 0.5 to about 1: 10: 200, preferably from about 1: 1: 1 to about 1: 5: 100.

The compounds represented by (B) can be prepared, for example, by hydrolyzing a represented by (A) Oxathiazines are produced. The hydrolyzed oxathiazine can in turn be reacted with a compound such as phosphorus pentachloride to form a through (B) wherein X is chlorine. The sulfonyl-containing compound represented by (B), wherein

10983-1 / 16 * 6-. " ⁸ "

M is a metal-containing cation can be produced by subjecting the hydrolysis of one represented by (A) Compound in the presence of a metal compound such as the oxide, hydroxide, alkoxide, carbonate, bicarbonate or sulfide of sodium, potassium, lithium, magnesium, barium, strontium, calcium, nickel, zinc or mixtures thereof. It is also within the scope of the present invention that the metal-containing compounds represented by (B), i.e., when X is -OM, can be a compound that is a basic salt.

The term "basic salt" is used to denote metal salts in which the metal is present in stoichiometrically larger amounts than the organic acid residue of a compound represented by (B). A commonly used method for preparing basic salts comprises heating a mineral oil solution of an organic acid compound represented by (B) with a stoichiometric excess of a metal neutralizing agent such as metal oxide, hydroxide, alkoxide, carbonate, bicarbonate or sulfide at a temperature above about 50 ⁰ C and filtering off the resulting mass. The use of a "promoter" in the neutralization step to aid in the incorporation of a large excess of metal is also known. Examples of

109831/1696

Compounds known as promoters include phenolic substances such as phenol, naphthol, alkyl phenol, thiophenols, sulfurized alkylphenol and the condensation products of formaldehyde with a phenolic substance, alcohols such as methanol, 2-propanol, ceryl alcohol, cellosolve, carbitol, ethylene glycol stearyl alcohol and amine-cyclohexyl alcohol such as aniline, phenylenediamine, phenothiazine, phenylß-naphthylamine, ammonia, primary and secondary amines such as octylamine, dodecylamine and dihexylamine. A particularly effective method for preparing the basic salts comprises mixing a compound represented by (A) with an excess of a basic alkaline earth metal neutralizing agent, a phenolic promoters compound and a small amount of water and carbonating the mixture at an elevated temperature such as from about 60 ⁰ O to 200 ° 0.

The sulfonyl-containing compound represented by (B) can also be used in many known hydrolysis processes be prepared, such as by hydrolyzing -the oxathiazine ring in the presence of water, water and an alcohol such as methanol, or a base such as sodium or Calcium hydroxide. It can therefore be hydrolyzed e Qxathiazine easily by simply mixing one Get water per mole of qxathiazine ring and by heating the

■ ■ ■ ■ ■ -10-

109831 / 1S98

- ίο -

resulting mixtures at a temperature of about 50 ⁰ O to about 150 ⁰ C are prepared.

While the through (A) or. (B) compounds shown have detergency activity are preferred ashless detergent compounds those compounds which by the reaction of an oxathiazine, a sulfonyl containing compound, or mixtures thereof with a Nitrogen-containing compound can be prepared.

The nitrogen-containing compound wild, by the pre

H presence of at least one represented by -N- Group marked. It is therefore believed that the reaction of a nitrogen-containing compound with a compound represented by (A) takes place with the formation of a salt with subsequent cleavage of the oxathiazine ring, while it is believed that the reaction of a nitrogen-containing compound with a by (B) compound shown leads to the formation of a salt or sulfonamide. By reacting a nitrogen containing compound with one represented by (A) or (B) Compound produced products have opposite the intermediate products, i.e. the compounds (A) and (B) superior detergency, although the through (A) and (B) shown compounds detergent effectiveness have and fall within the scope of this invention.

109831/1696

be closed. It can, therefore, a compound, or mixtures represented by (A) or (B) are mixed these compounds with a nitrogen-containing compound and heated at a temperature im'Bereich of about 25 0 to about 275 G ^0. The molar ratio of a nitrogen-containing compound to the compound represented by (A) and (± 0) can vary within a wide range The minimum ratio of a compound represented by (A) and (xi) or mixtures of these compounds per equivalent in the nitrogen-containing compound nitrogen present is generally about 0.10: 1. Thus, for example, an amine such as etraethylene pentamine would have 5 equivalents of nitrogen and a compound such as diethylene triamine would have 3 equivalents of nitrogen. There is actually no upper limit on the ratio of the number of moles of a compound represented by (A) and (B) per equivalent of nitrogen present in a nitrogenous compound, although (a preferred upper limit based on the incorporation of at least a minimal amount of nitrogen in a compound represented by (C) is about 2: 1. ·

It is also within the scope of the present invention, that the above contained by the reaction of nitrogen-

-12- 109831/1696

the connection with one represented by (A) and (B) Compound produced products can be further reacted with a boron, zinc or nickel compound, such as for example a boron oxide, boron halide, a boric acid and an ester of a boric acid, zinc acetate and Nickel acetate in an amount around an atomic ratio of about 0.1 boron, nickel or zinc, for per mole of the through k (C) up to about 10 boron, nickel or zinc for each atom of nitrogen contained in a given by (G) represented product exists.

The hydrocarbon-containing material represented by (d) can be, for example, a high molecular weight, substantially saturated petroleum fraction product and olefin polymer, particularly polymers of raono-olefins having from 2 to about 30 carbon atoms. Particularly useful polymers are the polymers ) of 1-mono-olefins 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. Polymers of middle olefins, ie olefins in which the olefinic bond is not in the position, can be used in the same way; they are illustrated by 2-butene, 2-pentene and 4-octene.

The hydrocarbon-containing group can be polar-

109831/1696 -13-

contain dubstituenten, provided, however, that the polar substituents not in sufficiently large proportions are present to significantly change the hydrocarbon character of the remainder. Typical examples polar substituents are halogen, keto, ethereal, aldehyde, carboxy, amino, nitro and the like. The upper Limit in terms of the ratio of such polar Bubstituenten in the hydrocarbon-containing group is about 15 ° based on the weight of the Hydrocarbon containing group.

The copolymers of the olefins, as explained above with others which can be copolymerized, can also be used olefinic substances such as aromatic olefins, cyclic olefins and polyolefins. Such Copolymers include, for example, those which are prepared by polymerizing isobutene with otyröl, isobutene with butadiene, propene with isoprene, ethylene with piperylene, isobutene with chloroprene, isobutene with p-methylstyrene, 1-hexene with 1,3-hexadiene, 1-octene with 1-hexene, 1-heptene with 1-pentene, 3-methyl-l-butene with 1-octene, 3,3 ~ dimethyl-1-pentene with 1-hexene, isobutene with Styrene and piperylene and the like.

Typical examples of such copolymers include

■ -14-

109831/1686

(Percentages based on weight) Copolymers of 95 ^ 4 isobutene with 5 # / styrene, terpolymers of isobutene with 1 # piperylene and Λ% chloroprene, terpolymers of 95 # isobutene with 2% 1-butene and 3 # 1-hexene, terpolymers of 60 # isobutene with 20 # 1-pentene and 20 # 1-octene, copolymers of 8Q # 1-hexene and 20 # 1-heptene, terpolymers of 90 # isobutene with 2 # cyclohexene and 8 # propene and copolymers of 80 # ethylene and 20 # propene.

The use of olefin polymers with a molecular weight from about 700-5000 is preferred. It it was found that olefin polymers of higher molecular weight, i.e., having molecular weights of from about 10,000 to about 100,000 or higher, also those of the invention Compounds viscosity index improving properties to lend.

The nitrogen-containing compounds which react with a compound or mixtures represented by (A) or (β) the same can be implemented, for example ammonia, aliphatic amines, aromatic amines, heterocyclic Amines, carbocyclic amines, polyamines such as alkylene amines, arylene amines, cyclic polyamines and hydroxy substituted Be derivatives of such polyamines. The amines

- 15 109831/1696

can be primary, secondary or tertiary amines.

Typical examples of amines are methylamine, N-methylethylamine, N-methyloctylamine, N-cyclohexylaniline, dibutylamine, Cyclohexylamine, aniline, di (p-methy! Phenyl) -amine, Dodecylamine, octadecylamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, alkyl-substituted-, m-, and p-phenylenediamine, dimethylaminomethylamine, dimethylaminoethylamine, Dimethylaminopropylamine, dimethylaminobutylamine, Dimethylaminoheptylamine, diethylaminoethylamine, diethylaminopropylamine, diethylaminoamylamine, dipropylaminopropylamine, Methylpropylaminoamylamine, propylbutylaminoethylamine, Diraethylene trianiline, methylenedianiline, Polymethylene aniline and polyalkylmethylene aniline made by the reaction of an aldehyde with aniline

in the presence of an acidic catalyst, such as polymethylene aniline, NjN'-di-n-butyl-p-phenylenediamine, morpholine, Piperazine, tetrahydropyrazine, indole, hexahydro-1-3,5-triazine, l-H-1,2,4-triazole, melamine, bis (p-aminophenyl) methane, Phenylmethyleneimine, methanediamine «i, like 2,3-» 7j9 ~ » 7,10- and 9i10-hethandiamine, cyclohexamine, pyrrolidine, 3-amino ~ 5,6-diphenyl-1,2,4-triazine, ghinodiimine, 1,3-indanediamine, 2-octadcylimidazoline, 2-phenyl-4-methylimidazolidine, Oxazolidine, ethanolamine, diethanolamine and 2-heptyloxazolidine.

109831/1696 " ¹⁶ "

The nitrogen-containing group preferably consists of polyamines, particular alkylenamines, which essentially the formula

H-N - / - alkylene N-J-H

Il if A \ AI

correspond, where in the formula η is an integer, preferably less than about 10, A is essentially one

w is a hydrocarbon group or hydrogen and the alkylene group is preferably a lower alkylene group having less than about 8 carbon atoms. The alkylene amines mainly include methylene amines, ethylene amines, butylene amine, propylene amines, pentylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines, the cyclo-containing alkylene amines, and the higher homologues of such amines. Typical examples of alkylenamines are ethylenediamine, triethylenetetramine, propylenediamine,

I decamethylene diamine, octamethylene diamine, di (heptarnethylene) triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di (trimethylene) triamine, 2-heptyl-5- (2-aminopropyl) -imidazoline, 4-methylimidazoline bis, 1, 3 (2-aminoethyl) imidazoline, pyrimidine, 1- (2-aminopropyl) -piperazine, 1,4-bis (2-aminoethyl) -piperazine and 2-methyl-1- (2-aminobutyl) -piperazine, piperazines and aminoalkyl-substituted piperazines, N-benzylidene-5 -amino-5-azapentylamine, N-benzylidene-7-amino-4-azaheptyl-

109831/1696 _ _1? ^

ORIGINAL INSPECTPO

amine, N-furfurylidene-y-amino - ^ - azaheptylamine, N-benzylidene-8-amino ~ 3,6-diazaoctylamine, N- (3-isopropylbenzylidene) -. 8-amino-316-diazaoctylamine, N ~ benzylidene-II -amino-3 »6,9-triazaundecylamine, N-naphthylidene-II-amino-3» 6,9-triazaundecylamine, NI "urfuryliden-II-amino-I, 6,9-triazaundecylamine, N- (3-methyl- 4-hydroxybenzylidene) -ll-amino-3,6,9-triazaundecylamine, N- (2-chlorobenzylidene) -ll-amino-3,6,9-triazaundecylamine, N-diphenylmethyl-5-amino-3- 'azapentylamine, N-phenylethylmethylene-7-amino-4-azab.eptylamine, N-naphthylpropylmethylene-5-amino-3-azapentylamine, N-naphthylphenylmethylene-7-aminoazaheptylamine, 1- (2-aminoethyl) -2-propylimidazolidine _i l- (2 ~ Aminoethyl) -2-imidazolidinone, 1- (5-amino-3 _{-azapentyl) -2-imidazolidinori, 1- (8-amino-3}} 6-diazaoctyl) -2-imidazolidinone, 1- (11-amino-3 , 6,9-triazaundecyl) -2-imidazolidinone ₁ l- (2-aminoethyl) -2-imidazolidinthione, 1- (8-amino ~ 3,6-diazaoctyl) -2-imidazolidinthione, 1- (ll ~ amino- 3,6,9-triazaundecyl) -2-imidazolidinthione, 2 ~ imino-1- (aminoethyl) -imidazolidine, 2-imino-1- (8-amino-3,6-diazaoctyl) -imidazolidine, 1- (8-amino-3,6-diazaoctyl) -imidazolidine, l ~ (8-amino-3,6-diazaoctyl) - 2-methylimidazolidine, 1- (8-amino-3,6-diazaoctyl) -2-nonyliraidazolidine, j? Rimethylene-bis ^ - (8-iunino-3,6-diazaoctyl) -2-imidazolidine7 l- (8- Amino-3,6-diazaoctyl) -2-dimetliyliraidazolidine, 1- (8-Amino-3,6-diazaoctyl) -l _f 4-diazaspiro ^ r, ^ 7-deoan, 2,2'-methylene-bis ^ I - (8-amino-3,6-diazaoctyl) -iraidazolidin7, tyimethylene-bis / T- (2-aminoethyl) -2-imi- 109831/1698

"· ΊΟ" ·

dazolidin7, l- _(8-amino-3-t 6 diazaoctyl) -2-propylimidazolidin, l- (2-aminoethyl) -2-propyli "idazolidin, l- (2-aminoethyl) -2-vinylimidazolidine, l- (£ -Amino-3-azapentyl) -2- (ß-allyl) -imidazolidine, 1- (8-amino ~ 2,6-diazaoctyl) -2-propenylimidazolidine, l ~ (8-amino-2,6-diazaoctyl) - imidazoline, 1- (8-amino-3 »6-diazaoctyl-2-methylimidazoline, 1- (8-amino-3» 6-diazaoctyl) -2-nonylimidazoline, trimethylene

Bis / I- (8-amino-3 »6-diazaoctyl) -2-dimethylimidazoline, 1- (8-amino-3,6-diazaoctyl) -1, 4-diazaspiro ^ f _{l (} £ 7-decane, 2 , 2'-methylene-bis / r- (8-aiBino-3,6-diazaoctyl) -iinidazoline7, trimethylene-bis / T- (2-aminoethyl) -2-imidazoline7,1- (8-amino-3,6 -diazao ctyl) -2-propylimidazoline, 1- ( 2- aminoethyl) -2-propylimidazoline, 1- (2-aminoethyl) -2-vinylimidazoline, 1- (5-amino-3-azapentyX) -2- (fl- allyl) imidazoline, l- (8-amino- 3 _t 6-diazaoctyl) -2-propenylimidazoline and similar · higher

the )

Homologues such as the / by condensing two or more

of the above-mentioned alkyleneamines are obtained 'usable in the same way.

Additional examples of mixtures of alkyleneamines are those that are on the market under the names Polyamine M, Polyamine H and Polyamine D by the Union Carbide Chemical Company. The easiest way to produce these polyamines is to react ethylene chloride with ammonia. This procedure has

109831/1686 -19-

result in the preparation of somewhat complex mixtures of ethylene amines, including cyclic condensation products such as piperazines, and these mixtures find use in the process of this invention. On the other hand, fully satisfactory products can also be obtained by using pure ethylene amines as described above. A particularly useful ethylene amine, both in terms of economy and effectiveness as a dispersant, is a mixture of polyethylene amines made by the reaction of ethylene dichloride and ammonia with a composition similar to that of tetraethylene pentamine. These mixtures are available under the trade names "Polyamin H" and "Polyamin M". Pdlyamin M has the following properties: 34-, 1 # nitrogen, 14.7 # primary amine, average molecular weight of 212 and a distillation distribution at 5 mm Hg of 1OJlS at 137 ° C, 50 # at 200 ° G and (80 # at 217 ^O C. Polyamine D has an average molecular weight of 255 and 51.55 ^ nitrogen. It is believed that the major components of Polyamine D have the following formulas:

NH ₂ -GH ₂ -CH ₂ -NH-CH ₂ -GH ₂ -NH-CH ₂ -CH ₂ -NH-CH ₂ -GH ₂ -NH-CH ₂ -Ch ₂ -

- 20 -

1 09831/1696

5,6,9 »12-Tetraea-1,14-tetradecanediamine NHg-CH ₂ -CHg-NH-CHg-CHg-N-OH ₂ -CHg-NH-CHg-CHg-NHg

CH ₀

NHg

6- (2-Aminoethyl) -3,6,9-triaza-1,11-undecanediamine NHg-CHg-CHg-N-CHg-CHg-NH-CHg-CHg-NH-OHg-CHg-NHg CH ₂
0H ₀
NHg

3- (2-Aminoethyl) -3,6,9-triaza-1,11-undecanediamine

NHg-CHg-CH ₂ OHg-CHg-NHg

NICHCHN

gg NHgTCHg-CHg CHg-CHg-NHg

3,6-bis (2-aminoethyl) -3,6-diaza-1,8-octanediamine

0H ₀ -OH ₀

^^ Ii-CHg-CHg-NH-CHg-CHg-NHg

1,4-L3 (3-aza-5-aeinopentyl) piperazine

-CHg-OHg-NH-CHg-CHg-NH-CHg-OHg-NHg

CHg- (
1- (2-Aminoethyl) -4- (8-amino-3 $ 5-diazaoctyl) piperazine

^ N- (CHg-OH ₂ -NH) ₅ -CHg-CHg-NHg OHg-CHg

1- (II-amino-3 »6,9-triazaundecyl) piperazine 109831/1696

NH ₂ -CH ₂ -GH ₂ -N-Oh ₂ -OH ₂ -NH-GH ₂ -OH ₂ -NH ₂

OH ₂ CH ₀

OH ₀

I I: 2

^V NH

-3- (2-aminoethyl) -3 »6-diazaootyl7-piperazine

GH ₂ GHo OH ₂ -GHp

^ N-OH ₂ -OH ₂ -NH-OH ₂ -OH ₂ -Ir "^ SiH

OOH ^0Η0Η

1 '- (3-azapentamethylene) dipiptraain Hp-

li-OHg-OHg-N ^^ «

4 ~ (2-Aminoethyl) -1, 1'-ethylenedipiperazine

These components are marketed as a mixture, but this invention also encompasses the fact that the individual compounds can be used as such as amine reactants. Polyalkyleneimines are also suitable amines and may be prepared by the polymerization of compounds such as ethyleneimine, 1,2-propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 2-methyl-l, 2 _T propylene imine and 1,2-Hexylenijain using known polymer

- 22 -

109831/1696

tion process can be produced. A typical one The polymerization process is given in U.S. Patent 3 2CX) 088.

Hydroxyalkyl-substituted alkyleneamines, ie alkylenamines with one or more hydroxyalkyl substituents on the nitrogen atoms, are also intended for use. The hydroxyalkyl substrate. Alkylene amines are preferably amines in which the alkyl group is a lower alkyl group, that is, having less than about 6 carbon atoms. Examples of such amines include N- (2-hydroxyethyl) -äthylendiaatin, N _l ^l N-bis (2-hydroxyethyl) -ethylenediamine, l- (2-hydroxyethyl) piperazine ~, mono-Hydroxypropylaubst. Diethylenetriamine, 1,4-Bie (2-hydroxypropyl) -piperazine, Dihydroxypropylsubet. Tetraethylene pentamine, N- (3-hydroxypropyl) -tetramethylene diamine and 2-H0ptadecyl-1- (2-hydroxyethyl) -imidazoline.

Higher homologs such as those obtained by condensation of the alkyleneamines or hydroxyalkylsubsts explained above. Alkylenamines obtained through amino groups or through hydroxyl groups are usable in the same way. It is note that the condensation through amino groups gives a higher amine, accompanied by the excretion of Ammonia and that condensation through the hydroxyl groups

100831/1896

Results in products that contain ether bonds from the excretion of water.

.Line further basis for the nitrogen-containing group includes the ureas, thioureas, hydrazines, guanidines, amidines, cyanamides and the like. Typical examples are hydrazine, j ^ henylhydrazin, H K'-diphenylhydrazine, Octadecylhydrazin, benzoylhydrazine, urea, thiourea, etc., H-butylurea, guanidine, 1,3-diphenylguanidine, 1,2,3-Tributylguanidin, benzamidine, Qctadecamidin, cyanamide , Dicyandiamide, guanylurea, aminoguanidine

and similar.

Typical examples of substances containing sulfur trioxide are sulfur trioxide, concentrated or fuming sulfuric acid, chlorine, sulfonic acid, sulfur trioxide in complex with pyridine, dioxane, thioxane, alkyl phosphate complexes and the like. In addition, sulfur trioxide can be used in a dilute or less reactive form such as a mixture with liquid or gaseous SO ₂ or with dry air.

Typical examples of nitriles represented by R ^ ON, i.e. (f) which can be used to prepare compounds represented by (A) and (B) Acetonitrile, Acrylonitrile, Pluoroacetnitrile, Trichloroacet-.

109831/1696

-24-

nitrile, α-methylacrylonitrile, propionitrile, isobutyrnitrile, a-ivbhylacrylonitril, α-chloroisobutyronitrile, butyronitrile, Crotonnitrile, Allylcyanid, Methoxyacetnitril, ot-Hydroxyisobutyrnitril, Chloroacetnitrile, oc-bromoisobutyrnitrile, Diethyl acetonitrile, ß-methoxypropionitrile, benzonitrile, Ethyl cyanoacetate, cyanogen, chlorocyanogen, ß-hydroxybutyrnitrile, Dodecandinitrile, 2-nonyldecandinitrile, benzonitrile, Oleonitrile, grotonitrile, glycine nitrile, 2-aminopropionitrile, 5-pyramidine carbonitrile, 4-i'iorpholinacetnitril, 4-pyridinbutyrnitril, 2-Gyanoacetamid, 2-Cyanopropionylchlorid, N- (Cyanometh ^ l) -phthalimid, 4-Gyanohexaic acid and 4-Gyanobutenylsuccinic acid anhydride.

Typical examples of one represented by ILj, R ^ and R ^ Hydrocarbyl groups are AlK: yl, such as methyl, It hy]., Propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, octadecyl, 10-carboxyoctadecyl, 11-cyanooctadecyl, mono- and polyhalogenous dodecyl, alkenyl such as propenyl, butenyl, Heptenyl, dodecenyl and similar, cycloaliphatic compounds such as cyclopropyl, cyclobutyl, cyclohexyl, mono- and polymethylcyclohexyl, mono- and polyisopropylcyclohexyl, Naphthenyl, Oyclopentenyl, Honylcyclohexenyl and similar, aryl explained here to include the mono-, di- and polynuclear hydrocarbons, such as Phenyl, naphthyl and anthryl, typical examples of aryl being phenyl, alkylphenyl, xenyl, tert. Amylnaphthyl, Tolyl, Cresylfc lia ^ seme ^ gs. Phenol, carboxyphenyl, cyano

ORIGINAL INSPECTED

phenyl »alkylhydroxyphenyl, alkylchlorophenyl, alkylnitrophenyl, Butylnitronaphthyl, cyclohexylphenyl, .Phenoxyphenyl, tert. Butylphenoxyphenyl, aminophenyl and are similar, aralkyl such as Benzyli methylbenzyl, Phenylethyl and similar, oxy-containing aliphatic, cycloaliphatic and aromatic radicals such as Alkoxysub.st. Alkyl radicals, cycloalkoxy subst. Alkyl radicals, Alkenoxy-subst. Alkyl radicals, carboalkoxyalkyl radicals, '| Aroxy-subst. Alkyl radicals, alkoxy subst. Cyclohexyl, Aroxy-subst. Cyclohexyl, oboalkoxycycloalkyl and the like.

In addition, the heteroeyeIdhen groups represented by R ^, can contain from 4 to 10 atoms, optionally interrupted by from 1 to 4 heteroatoms, which can be nitrogen, sulfur and oxygen or combinations thereof, for example substituted or unsubstituted pyridyl and (

be similar.

In addition, that represented by Eg, R, and R ^ Hydrocarbyl group and the heterocyclic group represented by R ^ Group can be substituted with groups such as oxo, nitrile, nitro, carboxy, amide, hydrosulfide, amino, alkoxy, Halogen and the like. These groups may contain any of the above examples of substituents or

109831 / IiBi ■ - 26 - ·

they can contain more than one of the same or different substituents.

The invention is illustrated in more detail by the following, non-limiting examples.

example 1

In a 1 liter reaction flask, acetonitrile JOO
Grams (7.31 moles) and sulfur trioxide 5.85 grams (0.0731 moles) were added. Under repeated stirring a solution of polybutene 100 grams (0.0731 moles) in 250 ml of hexane at a temperature of -20 ⁰ G. The response was at
a temperature of about -15 ° 0 continued for a period of 5 hours. The reaction mass was taking
Vacuum distilled, with removal of the excess acetonitrile and the residue, 4-polybutyl (1368) -4-, 6-dimethyl- ) 2-dioxo-1,2,5-oxathiazine was mixed with 50 g of processing oil. It contained $ 0.96 sulfur, $ 0.33 total nitrogen, and had an acid number of 0.38 milliaquivalents each
Gram.

Example 2

The procedure of Example 1 was repeated except that the polybutene of Example 1 was replaced by a polypropylene

109831/1696

; - 27 -

Molecular weight 787 was replaced. The product, 4-polybutyl (787) -4-, 6-dimethyl-2_-dioxo-1,2,5-oxathiazine contained $ 1.33 sulfur, 0.33 ^ nitrogen and had an acid number of 0.50 Milliaquivalents per gram.

Example 3

A solution of 218 grams (0.231 hol) polybutene, molecular weight 94-3, 4-00 ml N- | Hexane and 94.8 grams (2.31 moles) acetonitrile. The solution was cooled to -40 ° C, then 18.5 grams (0.231 mole) of sulfur trioxide were added dropwise during a 15 minutes period while maintaining the reaction temperature between -35 ° C and -40 ⁰ C. After the addition of the sulfur trioxide, the temperature was increased to -5 ° G and this temperature was maintained for a period of approximately 4 hours. Stickst; ■ - £ Σ - was the reaction mixture bubbled through for an additional two hours _? while the temperature of the reaction mixture was increased to ambient temperature. The reaction mixture was vacuum distilled to remove excess acetonitrile and hexane and was then diluted with 120 grams of processing oil. The product, 4-polybutyl (943) -4,6-dimethyl-2-dioxo-1,2,5-oxathiazine, contained 0.27 ^ nitrogen, 1.37 ^ sulfur and had an acid number of 0.62 milliaquivalents per gram .

"" ■■. "... ■ - ■■ .-. ■■■■. '- 28 - · ■■■■. <.

109831/1696

17451

Example 4

The procedure of Example 1 was repeated except that a 10 molar excess of sulfur trioxide was used became. The product, 4-polybutyl (1368) -4,6-dimethyl-2-dioxo-1,2,5-oxathiazine Contained $ 1.16 sulfur, $ 0.29 nitrogen_ and had an acid number of 0.41 milliequivalents per gram.

Example 5

Contained in a round bottom flask containing 300 grams (7.31 mole) of acetonitrile at -25 ⁰ O, 5.85 grams (0.0731 moles) of sulfur trioxide were added. 100 grams (0.073 mol) of polyisobutylene, dissolved in 250 ml of n-hexane, were then added to the mixture given above. The temperature was warmed to -5 ⁰ C and this temperature was then maintained voi} (5 hours during a period of time. Nitrogen was bubbled at a temperature of about O ⁰ O during a period of 45 minutes at the end of this time, a 30 ml aqueous. A solution of 2.59 grams (0.0731 mol) of sodium hydroxide was added to the reaction mixture. The temperature was increased to 10 0 and the reaction continued for an additional 40 minutes. Processing oil, 50 grams, was then added. The reaction mixture was distilled under vacuum and 'the product (residue) was the sodium salt of 2-ethylidene

- 29 109831/1696

amino-1-polybutyl (1368) sulfonic acid and contained $ 0.93 Sulfur and $ 0.72 nitrogen.

Example 6

To a reaction flask, 60 grams (0.0208 mole) of 4-polybutyl-4,6-dimethyl-2-dioxo-1,2,5-oxathiazine and 70 ml of toluene were added. 2 ml of concentrated ammonium hydroxide (0.0416 mol) were then added to this mixture. The temperature was raised to 75 ° C over a period of 30 minutes and the reaction mixture was then used to unloading, the water fernung under reflux (118 ⁰ O) taken. The product was filtered and vacuum distilled. The product residue, the ammonium salt of 2-ethylideneamino-1-polybutylsulfonic acid, contained 0.93 $ sulfur and 0.68 $ nitrogen.

Example 7

In a reaction flask, 4-0 grams (0.014-4 moles) 4-polybutyl (1356) -4,6-dimethyl-2-dioxo-1,2,5-oxathiazine, 60 ml of soluene and 0.58 grams (0.014 mole) sodium hydroxide dissolved, added in 10 ml of distilled water. The reaction mixture was refluxed for 30 minutes. The reaction mixture was then cooled and 1.2 ml of concentrated hydrochloric acid solution was added and then for 1 hour ' taken under reflux. Contained after vacuum distillation

•. ■ ..- 30 - '

1 0 9 8 3 1/1 6 9 6

the residue product, 2-acetamido-1-polybutyl (1356) sulfonic acid, 0.220 nitrogen and 1.010 sulfur.

Example 8

To the oxathiazine prepared in Example 5, 100 ml of toluene was added. To this mixture was then added an aqueous solution of zinc acetate dihydrate, 1.4 grams (0.007 moles) in 8 ml of water. The temperature was increased to 80 ⁰ O and this temperature was maintained for a period of about 1 hour. After filtering and vacuum distillation of the product, the product residue contained zinc 2-acetamido-1-polybutyl (1368) sulfonate, 1,120 zinc, 0, W sulfur and $ 0.25 nitrogen.

Example 9

Following the same procedure as in Example 8, a nickel salt using an aqueous solution of Nickel acetate tetrahydrate. The product, nickel 2-acetamido-1-polybutyl (1368) sulfonate contained 1.020 nickel, 1.020 sulfur and 0.260 nitrogen.

Example 10

Using the procedure of Example 8, an oaloium sulfonate was made using calcium oxide in water

- 31 109831/1696

manufactured. The product, calcium 2-acetamido-i-polybutylsulfonate contained 1.08 # sulfur, $ 0.20 nitrogen and $ 0.64 calcium. -

Example 11

A dog bottom flask was filled with calcium oxide, 9j9 grams, ammonium hydroxide, 0.7 ml, methanol, 25 ml and 100 ml heptane | loaded. To this mixture, 90 grams of 4-polybutyl-4,6-dimethyl-2-dioxo-1,2,5-oxathiazine were added. After the addition, the temperature was increased to 50 ^° C. and carbon dioxide was bubbled through for a period of approximately 50 minutes. A total of 6.6 grams of carbon dioxide was added. The product was filtered and vacuum distilled, after which the product residue, overbased calcium - ^ - acetamido-i-polybutylsulfonate, contained $ 4.09 calcium, $ 0.91 sulfur and had a base number of 95.

Example 12

Following the procedure of Example 11, a overbased calcium sulfonate produced, the product being calcium overbased-2-acetamido-i-polybutylsulfonate, Contained 2.08 / 6 sulfur, 0.36 # nitrogen, 1.58 # calcium and had a base number of 12.

The following examples explain the production of 10983171696 " ⁵² "

products represented by (G), i.e. the reaction of a nitrogen-containing compound with a product represented by (A) or (B). or mixtures of the same compounds shown.

Example 13

To a solution of 4 ~ polybutyl (1368) -4-, 6-dimethyl-2-dioxo-1,2,5-oxathiazin in 150 ml of toluene at 24 ⁰ O ammonia gas was added. The temperature was increased to 100 ^° C. over approximately 5 minutes, after which nitrogen was bubbled through. After vacuum distillation, the product residue contained $ 0.93 sulfur and $ 0.74 nitrogen.

Example 14

To the 4-polybutyl-4,6-dimethyl-2-dioxo-1,2,5-oxathiazine (0.01827 mol) in toluene were Ν, Ν-dimethylaminopropylamine, 1.87 grams (0.01827 moles) were added. The reaction mixture was heated to reflux. And this temperature during maintained for a period of approximately 1 hour. The product residue contained after filtration and vacuum distillation 0.91 # sulfur and 0.93 # nitrogen.

The following table, Table I, explains additional preparations of the products represented by (C). That is the method used to make the compound

- - 33 -109831/1896

The same procedure as that of Examples 13 and 14. The temperature during the preparation of the products represented by (C) was generally in the range of about 75 ⁰ C to about 140 ° C. The duration of the reaction within the temperature range given above was generally from about 1 to about 2 hours. The products prepared in the examples below, 'λ were vacuum distilled to remove volatile solvent, such as toluene, and the residue was analyzed in each example to determine the physical properties. In the examples below, Rp and R, of starting reactant (A) are hydrogen or lower alkyl having from 1 to 4 carbon atoms and R ^ is methyl.

831/1898

Table I.

R -r

CR ₁

U SO,

π C t

CAT

Koh- Mol.Gew.ν «represented by R or R ₁

Nitrogen-containing compound
Reaction partner (B)

Mol. Ratio "
(AWAY) {

analysis

Sulfur # · Stickst

₁
Hydrogen-containing group R +

<o

«

**

Γ *

20th
21
12th

23

27

28

(O

Polybutyl

Polybutyl Polybutyl Polybutyl Polybutyl Polybutyl Polybutyl Polybutyl Polybutyl

Polybutyl polybutyl polybutyl

Polybutyl polybutyl 1- (2-aminoethyl) -2-propylimi- 1

dazolidine

Diethylenetriamine
Ethylenediamine O,

Tetraethylene pentamine
Pentaethylene hexamine
Thiourea
urea
Diethanol amine
1- (5-Amino-3 - azapentyl) succin ~

imid
1- (5-amino-3-azapentyl) -male-

imid
1- (5 ~ amino-3 ~ azapentyl) ~ 3-poly-

butenyl (Ml 642) succinimide
1- (2-aminoethyl) -2 ~ methylimi-

dazolin

Pentaethylenehezamine
Diethylenetriamine

, 4: 1

0.73

1: 1 0.93 88: 1 0.99 1: 1 0.90 1: 1 0.92 1: 1 1.65 1: 1 0.77 1: 1 1.09 1: 1 0.86 1: 1 0.84 1: 1 0.60 1: 1 0.91 2: 1 0.91 2: 1 .1.03

1.69

1.32 0.70 2.17 2.57 1.13 1.29 0.63

0.98 1.27 0.97

1.29 .e-2.26 cn

0.77 - ^ to-

Example 29

To a mixture of 80 grams (0.0554 moles) of 4-polybutyl ~ (1325) -4 _J 6-dimethyl-2-dioxo-1,2,5-oxathiazin and 100 ml of toluene were added 5 »7 grams (0, 0554 mol) of diethyl triamine in 40 ml of toluene was added. The reaction mixture was taken for a period of about 1 ötunde under reflux, after which the Jäeaktionsgemisch was vakuumdestil- lines g to remove unreacted amine. The product was cooled to 70 ° C and 60 ml of toluene was added. Boric acid was then added to the product residue and toluene 10.3 grams (0 ^ 1662 moles). The temperature was increased to approximately 100 ⁰ O over a period of approximately 1 hour. After vacuum distillation and filtration, the product residue contained 1.01% nitrogen, 0.82% sulfur and 0.22% boron.

Example 30 ^

The procedure of Example 29 was repeated except that boric acid by zinc sulfate atheptahydrate water solution was replaced. The product residue containing zinc and nitrogen contained 0.96 # sulfur, 0.93 ^ 6 nitrogen and Zinc.

Example 31
An aqueous solution of zinc acetate, 1.62 grams (0.0074 moles)

109831/1696 - 36 -

in 8 ml of distilled water was added to 40 grams (0.0148 mol) of 4-polybutyl (1568) -4,6-dimethyl-2-dioxo-1,2,5-oxathiazine in 100 ml of toluene. The reaction was refluxed for a period of approximately 1 1/2 hours. After filtering off the product, 1.52 grams (0.0148 mol) of diethylenetriamine was added. The reaction was continued for a period of about 1 hour at a temperature of about 11O ⁰ O. After vacuum distillation, the product residue contained $ 0.75 sulfur, # nitrogen and 0.96 # zinc.

The lubricating oils that can be used as base oils are the novel compounds and products of this invention not restricted as far as their detergent effects are concerned and accordingly, naphthenic, paraffinic and other hydrocarbon-based lubricating oils can be used as well Lubricating oil ^ originating from carbon products and synthetic oils such as alkylene polymers, alkylene oxide polymers, Di-, tri- and polycarboxylic acid esters, alkylated benzenes, bilicate esters, silicone polymers and the like are used will.

The compounds and products of the invention can be used in lubricating oils in amounts of about 0.05. until about 25 'Weight percent are used. Additive concentrates from

- 37 -109831/1696

$ 60-95 are also provided. It was found that that in, for consumption, intended, preparations the most. Applications Amounts from about 0.25 to about 10 percent by weight are sufficient. In addition, you can the compounds according to the invention in heating oils and in various light products, such as gasoline, as detergents or dispersants can be used. '

The effectiveness of the compounds and products according to the invention for imparting low-temperature detergent properties is illustrated by the results of a detergent test called the Lacquer Deposition Test (LDI) which involves the passage of burned Gasoline gases through a sample of a preparation in a suitable container under controlled conditions which the sample is aged in a heating oven. the

* ■ '■■■ ■■■■' ■■ ..

The amount of deposit is then determined by washing out the oil with hexane. The control preparation is run through in a similar manner. The amount of scale present when the tested detergent is used compared to the amounts of scale present when no tested detergent is used is referred to as the percent scale reduction. This particular 'feast is fully usable because it fully reflects the results obtained in the Lincoln Mti öequene © 5

- 38

- 58 -

nissen corresponds. Using the studies identified above, the following were set out in Table II Get results. In each experiment there was 1.0 weight percent of compounds of this invention used.

109831/1696

- 39 -

Table II

Additive LDT
% Reduction; Product of example1 42 Product of example 5 38 Product of example 6 96 Product of Example 7 53 Product of Example 8 91 Product of example 10 98 Product of Example 11 85 Product of example 12 95 Product of Example 13 71 Product of Example 14 73 Product of example 15 82 Product of example 16 86 Product of Example 17 82 Product of Example 18 90 Product of Example 19 92 Product of example 20 90 Product of Example 21 90 Product of Example 22 72 Product of Example 23 88 ^:::
Product of Example 24 84 Product of Example 25 80 Product of Example 26 90 Product of Example 27 96 Product of Example 28 87 Product of example29 92 Product of example 30 85 Product of Example 31 83

1098317189 $

- 40 -

The results shown in Table II show that the compounds according to the invention are effective in an effective manner and products as detergents. In particular, Examples 1, 5 and 7 demonstrate the detergency activity of the compounds which are represented by (A) and (B). The excellent increase in effectiveness in detergent activity of the products »those resulting from the interaction of a compound represented by (A) and (B) or mixtures thereof with a nitrogen-containing compound are well illustrated by Examples 15 to 28, the products represented by (C) exhibiting excellent detergency in lubricating oil formulations. In addition, Examples 29 and 50 illustrate that the boron and zinc derivatives of the products represented by (C), have excellent detergency in lubricating oil preparations.

Because the greater part of the oils available on the market is the subject matter a large number of uses, it is generally necessary to have more than one type of additive in one Use final lubricant preparation. Therefore, although the reaction products prepared above, it is more effective Detergents are often necessary to use such products in combination with other types of additives, such as metal-containing detergents and / or dispersants

- 41 109831/1686

Corrosion inhibitors, extreme pressure agents, oxidation inhibitors, viscosity index improvers, dropping point depressants, Anti-foaming agents and the like.

'Typical examples of corrosion inhibitors, extreme pressure agents and oxidation inhibitors are exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wax, organic sulfides and polysulfides such as benzyl disulfide, bis · g (chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized choice oil (sperm oil), sulfurized Methylester of oleic acid , sulphurised alkylphenol, sulphurised dipentene and sulphurised terpene, phosphosulphurised hydrocarbons, such as the reaction product of a phosphorus sulphide with serpentine or methyl oleate, phosphoric esters including primarily dihydrocarbon and trihydrocarbon phosphites, such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, dipylphenyl phosphite

phosphite, tridecyl phosphite, distearyl phosphite, dimethyl- '

naphthyl phosphite, oleyl-4-pentylphenyl phosphite, polypropylene (Molecular weight 500) r-substituted phenyl phosphite, diisobutyl subst. Phenyl phosphite, metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenyldithiocarbamate, Metal (group II) phosphorodithioates, such as zinc dicyclohexyl phosphorodithioate, Zinc dioctyl phosphorodifchioate, ßariumdi (heptylphenyl) ~ phosphorodithioate, Gadmium dinonyl phosphorodithioate and the zinc sala of a phosphor ci.it m ο acid, the

109831/1696

by the reaction of phosphorus pentasulfide with an equimolar mixture of isopropyl alcohol and n-hexyl alcohol was produced.

- 43 -109831/1696

Claims (26)

Patent claims: wherein in the formulas R and R ^ is hydrogen and / or a hydrocarbon-containing group, provided that the sum of the number of those in R and R ^. carbon atoms present is at least 50 carbon atoms and provided that at least one of R and R ^ is a hydrocarbon-containing group having at least 40 carbon atoms, Rp and R, hydrogen and / or a hydrocarbyl group having from Λ to 30 carbon atoms, Rr is hydrogen and / or GR ^ is where R ^ is hydrogen - 44 - 109831/1686 is a hydrocarbyl and / or a heterocyclic group, containing from 1 to 10 atoms, optionally are interrupted by from 1 to 4 heteroatoms of oxygen, nitrogen and / or sulfur and X is halogen and / or -OM, where M is hydrogen and / or a metal-containing cation. 2. A compound according to claim 1, characterized in that one of the groups represented by R and R _x , is a hydrocarbon-containing group having a molecular weight of about 700 to about 5000, R ~ and R ^ are hydrogen, alkyl and / or aryl and K ^ is an alkyl, substituted alkyl, aryl, substituted aryl and / or heterocyclic and substituted heterocyclic group, the heterocyclic group containing from 1 to 10 atoms, optionally by from 1 to 4 heteroatoms of oxygen, nitrogen and / or sulfur is interrupted and the * substituents are halogen, carboxy, hydroxy, cyano and / or amino. 3. A compound according to claim 2, characterized in that at least one of the groups represented by R and R ^ Is hydrogen and / or alkyl having from 1 to 10 carbon atoms. 109831/1696 _ zj.5 - 4. A compound according to claim 2, characterized in that Kp and R _{5 are} hydrogen and / or alkyl having from 1 to carbon atoms and R ^ is alkyl having from 1 to 10 carbon atoms. 5. Compound according to claim 4, characterized in that that at least one of the groups represented by R and R ,, a hydrocarbon-containing group selected from polybutyl and / or polypropyl and Rp and R, hydrogen and / or methyl and R 1 are alkyl of 1 to 6 carbon atoms is. 6. sulfonyl-containing compound according to claim 2, characterized in that X is SOYM. 7. A compound according to claim 6, characterized in that M is a metal-containing cation. 8. A compound according to claim 7, characterized in that the metal is one of groups IA, HA and / or XIB is. 9. A compound according to claim 8, characterized in that the metal is one of the group HA. 10. Compound according to claim 6, characterized in that - 46 - 109831/1696 that the metal belongs to the group HA and X is a basic, metal-containing cation. 11. Product according to claim 1, which by the reaction of (A) a material of a compound according to claim 1 (A), a compound according to claim 1 (B) and / or mixtures same with (B) a nitrogen-containing compound is prepared, the nitrogen-containing compound being characterized is through the presence of at least one H
-N- represented group. 12. Product according to claim 11, characterized in that the ratio of the number of moles of (A) per equivalents (B) nitrogen present ranges from about 0.10: 1 to about 2: 1. 13. Product according to claim 12, characterized in that the nitrogen-containing compound of ammonia, a aliphatic amine, an aromatic amine, a heterocyclic Aroin, a carbocyclic amine, a polyamine, a hydroxy-substituted polyamine, urea, Thiourea, guanidine, dicyandiamide, guanylurea and / or aminoguanidine. 14. Product according to claim 1, characterized in that - 47 - 109831/1696 represents: polyamine, an alkylene amine, an arylene amine and / or is a cyclic amine. 15. Product according to claim 14, characterized in that the polyamine is an alkylene araine. 1b. Connection according to claim 15, characterized in that that the alkylene amine has from 2 to about 7 nitrogen atoms, contains from 2 to about 30 carbon atoms and from O to about 4 heterocyclic hinge consisting of imidazoline, Imidazolidine, piperazine and / or imidazolidinone exist. 17. Product according to claim 11, characterized in that it is produced by the reaction of (A) a product of claim 11 and (ß) a boron compound. 18. Product according to claim 17, characterized in that the boron compound are boron oxide, boron halide, a boric acid, a boric acid ester and / or mixtures thereof. 19. Product according to claim 18, characterized in that the boron is boron in a ratio of approximately 0.1 atomic fraction there is up to about 10 atomic parts per mole of product for each atomic part of nitrogen present in the product. - 48 - 109931/1999 20..Product according to claim 11, produced by Reaction from (A) a product of claim 11 and (B) a zinc and / or nickel compound. 21. Preparation characterized in that it contains a larger amount of lubricating oil and a smaller amount of compound according to claim 1 contains. 22. Preparation gekennzeiclinet that it contains a larger amount of lubricating oil and a smaller amount of compound according to claim 9 contains. 23. Preparation characterized in that it is a larger amount of lubricating oil and a smaller amount of compound according to claim 11 contains. . Preparation characterized in that it contains a larger amount of lubricating oil and a small amount of compound according to claim 1J. 25 · The preparation is identified by the fact that it is a larger amount of lubricating oil and a smaller amount of Ver connection according to claim 17 contains. 26. Preparation characterized in that it contains as a major amount of lubricating oil and a minor amount connection claim 20th