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Publication numberUS3328297 A
Publication typeGrant
Publication dateJun 27, 1967
Filing dateOct 1, 1964
Priority dateOct 1, 1964
Publication numberUS 3328297 A, US 3328297A, US-A-3328297, US3328297 A, US3328297A
InventorsDonald J Anderson
Original AssigneeChevron Res
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
High molecular weight aliphatic sulfamides of alkylene polyamines and polyalkylene polyamines
US 3328297 A
Abstract  available in
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Description  (OCR text may contain errors)

United States Patent 3,328,297 HIGH MOLECULAR WEIGHT ALIPHATIC SULF- AMIDES OF ALKYLENE POLYAMINES AND POLYALKYLENE POLYAMINES Donald J. Anderson, San Anselmo, Calif., assignor to Chevron Research Company, a corporation of Delaware No Drawing. Filed Get. 1, 1964, Ser. No. 400,948 9 Claims. (Cl. 25232.7)

This invention concerns novel high molecular weight amino-substituted sulfamides and their use in lubricating oil as ashless detergents. More particularly, this invention concerns high molecular weight acyl-substituted aminohydrocarbyl-substituted sulfamides and their use in lubricating oil as ashless detergents.

The prime objective of any lubricating oil additive Is to increase engine life and extend the operating period between engine overhauls. Excepting mechanical failures, overhaul is required because of failure of a part of the engine due to wear or the accumulation of deposits. While oxidation inhibitors aid in minimizing the formation of varnish and sludge deposits, it has generally been found necessary to add detergents to the lubricating oil to further prevent deposition. Particularly, in low temperature gasoline engine operation encountered in stop-an-d-go passenger car service, where fuel oxidation products are the major source of deposits, detergent additives find wide use.

A large variety of metal salts of organic compounds are used as detergents in oils. The most popular are metal phenates, sufonates and salts of acids of phosphorus. However, the metal salts have the disadvantage of forming an ash on decomposition. Also, for some applications their detergency is not entirely satisfactory. More recently, a number of improved detergents have been provided of various basic organic compounds which are not salts and therefore do not leave an ash; these have been classified as ashless detergents. With increasing demands for improved stability of detergents and better detergency, efforts have continued to find new and improved deterents.

g It has now been found that high molecular weight N-acyl N'-alkylene amine or polyalkylene polyamine sulfamides find use as detergents in lubricating oils. The sulfamides range in molecular weight from about 400 to 6000, more usually from about 600 to 5000, have a poly(aliphatic olefin) side chain bonded through a carbonyl to one of the sulfamide nitrogens and an alkylene amine or polyalkylene polyamine bonded to the other of the sulfamide nitrogens.

The sulfamides have the following generic formula:

it RCNHS OzY wherein R is an aliphatic group of from about 300 to 5000 molecular weight-about 20 to 300 carbon atoms and Y is a monovalent alkylene amine or polyalkylene polyamine radical, wherein the nitrogens of the alkylene amine and polyalkylene polyamine radicals may have from 1 to 2 alkylene bridges; i.e., piperazine. Y will generally be of from about 2 to 50 carbon atoms and from about 2 to 6 nitrogens.

The compounds of this invention will generally have the following formula:

wherein R is an aliphatic hydrocarbon radical of from about 20 to 300 car-hon atoms, m and m are integers of from 2 to 6, p is a cardinal number of from 0 to 5, q is a cardinal number of from 0 to 3, and the sum of p and q is of from 1 to 5, with the proviso that the number of nitrogens does not exceed 6, i.e., p+2q 6.

The sulfonyl radical and the hydrogen radical may be bonded to any of the nitrogens between the large brackets which still have a free valence. The nitrogens with a free valance are: the nitrogen between the first set of brackets; the first nitrogen between the second set of brackets and the nitrogen which appears outside the parentheses.

The order in which the formulae are written between the brackets does not indicate the order in which they may appear in the compound. That is, a piperazine radical may be followed by a number of alkylene amines, be between a series of alkylene amines or follow a series of alkylene amines, being the terminal group.

The above formula could just as well be written as follows:

wherein the symbols are as defined above. The order of the bracketed radicals is evidently one of convenience.

A preferred group of compounds is indicated by the following formula:

wherein m" is an integer of from 2 to 6, p is an integer of from 1 to 5, preferably 3 to 5, R R and R are either hydrogen or aliphatic hydrocarbon radicals, the sum of R being from about 25 to 200 carbon atoms. Usually, R will be either hydrogen or lower alkyl and either R or R will be from about 25 to 200 carbon atoms and the other either hydrogen or lower alkyl. More usually, R and R will be hydrogen.

Illustrative of compounds of the above formula are the following compounds: N-polyisobutenyl carbonyl N-tetraethylene tetramine, N-polyisobutenyl carbonyl Ntriethylene triamine, N-polyisobuteny carbonyl N'-di (hexamethylene) diamine, N-poly(alkenyl C carbonyl Ntetraethylene tetramine, N-polyethyleuyl carbonyl N'-tri(trimethylene) triamine, etc.

The alkylene polyamine and polyalkylene polyamines which find use in this invention are illustrated by the following formula:

wherein m, m', p and q are as defined previously.

As already indicated, the alkylene polyamine and polyalkylene polyamine can be of from 2 to 50 carbon atoms and from 2 to 6 nitrogens. Preferably, there will be from 2 to 20 carbon atoms. Generally, not more than 1 piperazine ring will be present in the molecule, i.e., q=0l. While the alkylene groups may have branching, particularly methyl groups as in 1,2-propeylene diamine, the polymethylenes (free of branching) are preferred as the bridging group.

Illustrative of alkylene amines and polyalkylene polyamines are ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, di(tn'methylene) triamine, trimethylene diamine, hexamethylene diamine, tetramethylene diamine, di(hexamethylene) triamine, N-(2-aminoethyl)piperazine, N,N-di(2-aminoethyl)piperazine, etc.

The polyolefins which are used in the preparation of the acylarnino sulfonyl chloride can be prepared by a variety of means known in the art and from a variety of aliphatic l-olefins. The polyolefins may be prepared from only one olefin (h-omopolymer) or a multiplicity of olefins (copolymer). Depending on the particular olefin, the polyolefin may be prepared from Lewis acid catalysts, e.g., aluminum chloride, HF, sulfuric acid, antimony hexafluoride, tin tetrachloride, etc., or Zeigler- J type catalysts, e.g., titanium trichloride-aluminum triethyl, titanium tetrachloride-aluminum triethyl, vanadium oxychloridediethyl aluminum chloride, etc.

The olefins which find use in this invention will generally be of from about 2 to 20 carbon atoms, more usually of from 2 to 16 carbons. As already indicated, they are l-olefins, such as ethylene, propylene, butene-l, isobutylene, 4-methylpentene-1, hexene-l, octene-l, decene-l, hexadccene-l, eicosene-l, etc.

Depending on the catalyst, the polymer may be isotactic, syndiotactic, atactic, amorphous, crystalline, etc. Illustrative of the various polyolefins are polyethylene, polypropylene, polyisobutylene, polyolefins derived from mixtures of olefins of from 9 to 12 carbons, polyolefins derived from mixtures of olefins of from 12 to 16 carbons, polyolefins derived from mixtures of olefins of from 6 to 16 carbons, polyolefins derived from olefins obtained from cracked wax, etc.

As is evidenced from the illustrative polyolefins, the olefins may be straight or branched chain The polyolefins will be referred to as an aliphatic alkenc. As already indicated, the aliphatic alkene will generally be of from about 300 to 5000 molecular weight and more usually of from about 400 to 2000 molecular weight. The aliphatic alkene is contacted with the hydrocyanic acid, anhydride of chlorosulfonic acid (OCNSO Cl) The reaction is described in German Patent No. 941,847. The resulting N-chlorosulfonyl carboxamide may then be contacted with an alkylene polyamine or polyalkylene polyamine to provide the desired sulfamide.

In the reaction of the hydrocyanic acid, anhydride of chlorosulfonic acid with the aliphatic alkene, some of the product may form the N-chlorosulfonyl azetidinone of the following formula:

SO Y

wherein Y is as defined previously.

Such compounds should only be present in minor amounts and would not signficantly affect the reported results.

In those instances when it may be desirable to have more than one sulfamide group in the molecule, a diolefin may be included with the l-olefins, e.g., isoprene, butadiene, piperylene, 1,7-octadiene, in order to provide more than one site of unsaturation in the molecule. In this manner, more than one sulfamide may be introduced in the molecule. The equivalent weight per sulfamide group will generally be in the range of about 200 to 2000, more usually in the range of about 300 to 1000.

The hydrocyanic acid, anhydride of chlorosulfonic acid, is contacted with the polyolefin either neat or in the presence of a polar solvent. Illustrative of such solvents are diethyl ether, sulfur dioxide, etc.

Usually, room temperature (20 C.) is satisfactory, although higher or lower temperatures may be used. After standing for as ufiicient length of time for the reaction to occur, the reaction mixture may be worked up by removing the excess reactants and isolating the desired sulfonyl chloride roduct.

The acylaminosulfonyl chloride may then be contacted with the desired alkylene polyamine or polyalkylene polyamine. (If desired, the sulfonate ester (sulfamate) may be prepared from the sulfonyl chloride, which may then be used to prepare the sulfamide.) Preferably, elevated temperatures are used, generally in the range of from about 100 to 300 C. An inert solvent may be used if desired, i.e., hydrocarbon of from 6 to 12 carbon atoms, but the reaction may also be carried out neat. Generally, a small mole exces of the amine moiety will be used in order to insure a 1:1 mole relation between the sulfonyl chloride and the amine moiety. That is, the mole ratio of. sulfonyl chloride to the amine moiety. That is, the mole ratio of sulfonyl chloride to the amine moiety will be about 1:12. After suflicient time for the reaction to occur, the reaction mixture may be worked up to remove any unreacted reactants and the product isolated.

The compounds of this invention can be used with various base oils which find use as lubricating oils, such as petroleum oils: naphthenic base, parafiin base and mixedbase lubricating oils; synthetic oils, e.g., alkylene polymers (such as polymers of butylene, l-decene, etc., and mixtures thereof); alkylene oxide-type polymers (e.g., propylene oxide polymers); dicarboxylic acid esters (such as those which are prepared by esterifying such dicarboxylic acids as adipic acid, azelaic acid, suberic acid, sebacic acid, alkenyl succinic acid, fumaric acid, maleic acid, etc.; with alcohols, such as butyl alcohol, hexyl alcohol, Z-ethylhexyl alcohol, dodecyl alcohol, etc); liquid esters of acids of phosphorus; alkyl benzenes; alkyl ibiphenyl ethers; alkyl or aryl silicon compounds; etc.

The above base oils may be used individually or in combination whenever miscible or made so by the use of mutual solvents.

The sulfamides of this invention may be used in oils of lubricating viscosity in amounts of from about 0.1 to pencent by weight, by virtue of their compatibility with oils over a broad range. When the oil is to be used in an engine, usually the amount of the sulfamide will be in the range of from about 0.1 to 10 weight percent, more usually about 0.25 to 5 weight percent. However, the oil compositions may be prepared as concentrates and diluted prior to use. As concentrates, the amount of the sulfamide may range from about 10 to 80 weight percent.

The sulfamide detergents of this invention are preferably used in conjunction with a metal salt of a phosphorodithioate, particularly zinc 0,0-di-(hydrocarbyl) phosphorodithioate, wherein the hydrocarbyl group is of from 4 to 36 carbon atoms. (By hydrocarbyl is intended a monovalent organic radical composed only of carbon and hydrogen, which may be aliphatic, aromatic, alicyclic, or combinations thereof, e.g., alkaryl.) Usually about 6 to 50 mM./kg. of the metal thiophosphate is used in the engine oil.

The following examples are oflered by way of illustration and not by way of limitation.

Example I Into a reaction flask was introduced 1500 gms. of polyisobutylene (molecular weight-915), 2 l. of diethyl ether, 435 gms. of OCNSO Cl, 5 guns. of potassium chloride and 300 ml. of liquid sulfur dioxide, while maintaining a nitrogen atmosphere. The mixture was allowed to stand overnight. The following morning, the solution was filtered through Celite and the ether stripped on a steam plate under nitrogen, while maintaining the solution at a temperature below 50 C. When it appeared that all the ether had evaporated, the mixture was dissolved in 3 l. of hexane, the hexane solution was then washed with 50 percent aqueous ethanol, followed by drying with anhydrous sodium sulfate, filtering and removing the hexanes at 50 C. at 20 mm. Hg. The residue weighed 2057 gms. (some residual solvent was present).

(A) The above product (200 gms.) was mixed with 74.4 gms. of tetraethylene pentamine and the mixture heated at 200 C. with stirring. The mixture was then cooled and sufficient hexane added to bring the total volume to 500 ml. The hexane solution was washed with about 450 ml. of approximately 50 percent aqueous ethanol and then with 200 ml. of approximately 50 percent aqueous ethanol. The solvent was removed at 150 C. at 0.5 mm. of Hg, leaving a residue weighing 152 gms. Analysis: Nitrogen--2.10, 2.09 weight percent; basic nitrogen-0.88, 0.88 weight percent. The product having the same formula as indicated in LB.

(B) Into a reaction flask was introduced 100 gms. of the chlorosulfonyl compound prepared above and 5.7 gms. of tetraethylene pentamine, the mixture stirred and heated to 150 C. at 0.5 mm. Hg, the solvents being stripped off. The residue weighed 83 gms. and was primarily a compound having the following formula:

0 R NHsOzNHwHroEnNHhH wherein R is polyisobutenyl. Analysis: Nitrogen-2.37, 2.33 weight percent; basic nitrogen-1.00, 0.99 weight percent.

(C) Into a reaction flask was introduced 100 gms. of the sulfonyl chloride prepared above, gms. of ethylene diamine and hexane, and the mixture heated to 150 C. at 0.5 mm. Hg. The residue weighed 80 gms. and was primarily a compound of the following formula:

0 RiiNHSOQNHCHQCHZNHz wherein R is polyisobutenyl. Analysis: Nitrogen-2.07, 2.08 weight percent; basic nitrogen-08, 0:84 weight percent.

(D) Into a reaction flask was introduced 1 kg. of the sulfonyl chloride prepared above, 31.1 gms. of diethylene triamine a-nd hexane and the mixture heated to 150 C. at 0.5 mm. Hg. The remaining residue weighed 802 gms. and was primarily a compound of the following formula:

wherein R is polyisobutenyl. Analysis: Nitrogen1.73, 1.67 weight percent; basic nitrogen-0.69, 0.72 weight percent.

Example II (A) Into a reaction flask was introduced a mixture of C1540 l-olefins obtained by cracking wax (bromine number=68, molecular weight=241, 4.5 weight percent paraflin) and the mixture stirred and cooled in an ice bath maintained at a temperature at about 10 C. To this mixture was added aluminum chloride at a rate of 1 gm./ 30 sec. for 5 min., after which time the addition was slowed to 0.5 gm./2 min. until a total of gms. had been added. The ice bath was removed and the mixture allowed to warm to C. The temperature was maintained for another two hours.

At the end of this time, 60 ml. conc. ammonium hydroxide and 200 ml. isopropanol was added and the mixture stirred for 30 min. and then filtered through Celite. Volatile materials were removed by first heating the mixture at atmospheric pressure and then lowering the pressure to about 1 mm. Hg, while heating the flask to about 200 C. The residue weighed 1825 gms. (molecular weight=1357, determined by thermonam).

(B) Into a reaction flask was introduced 679 gms. of the above polymeric product and 1 l. of anhydrous ether. The mixture was cooled to about 0 C. and hydrocyanic acid, anhydride of chlorosulfonic acid, added over a period of 30 min., while maintaining the temperature below about 5 C. When the addition was complete, the reaction was allowed to stand for 5 days, intermittently drawing samples from the reaction mixture.

To the stirred mixture was added 500 ml. of methanol followed by 10 gms. of potassium iodide and 30 ml. of water. While maintaining the temperature at about 25 to 30 C., 124 ml. of a 5.75 normal aqueous sodium hydroxide solution was slowly added. The mixture was allowed to stir overnight, the pH being maintained at 6. The following morning hexane and Water was added, the layers separated, the hexane layer washed twice with alcohol, followed by removing the volatile materials at a temperature 160 C. at 5 mm. Hg. The residue weighed 1686 gms. (Saponitication number-46, 17; percent nitrogen=0.41, 0.39.)

(C) Into a reaction flask was introduced 662 gms. (0.195 mole) of the above product and 30.2 gms. of tetraethylene pentamine and the mixture stirred at a temperature of about C. under nitrogen for 30 min. The mixture was allowed to stand overnight without heating, the following day being heated for 1 hour at 150 C. followed by 4 hours at 180 C. The product was then filtered through Celite. Analysis: percent nitrogen- 1.04, 1.01. The product was predominantly a compound of the following formula:

wherein R is a poly(cracked wax) olefin of from C1540 olefins.

In order to test the detergency of the compounds of this invention, the compounds were tested both under L-l Supp. 1 conditions (MIL-L-2-1048, Supp. 1) as described in Coordinating Research Council Handbook, January 1946, and under the Caterpillar l-G test, MIL- 14-45199 conditions. In the former test (L-1 Supp. 1) is used a Mid-Continent SAE 30 base oil, containing 0.75 weight percent of the candidate detergent and 8 mM./kg. of Zn 0,0-di(alkyl)phosphorodithioate (alkyl is of from 4 to 6 carbon atoms). In the latter test (1-G) was used a Mid-Continent SAE base oil containing about 1.6 weight percent of the candidate detergent and 12 mM./kg. of Zn 0,0-di(alkylphenyl)phosphorodithioates (alkyl is polypropylene of 12 to 15 carbon atoms). The following table indicates the results obtained.

TAB LE Compound Test Time Grooves Lands I-A 120 3-0. 1-0-0 5-3-0 supp- 8. 2-00 ses-o 120 4-0. 3-0. 1-0. 1 20-0-15 160 9-1-0. 2-0. 1 125-1-0 60 38-9-2-1 710-315- 60 38-10-10-10 800-800-800 60 93-15-15-1 500-800-370 1 The less severe L-1 conditions (MIL-L-ZlotA) were used.

It is evident from the above table that the ashless detergents of this invention significantly enhance the operation of an engine by reducing deposits on the pistons, even under the severe conditions of the above tests. Not only are the compounds of this invention good detergents, but they maintain their detergency for long periods of time under severe testing conditions.

As will be evident to those skilled in the art, various modifications on this process can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.

What is claimed is:

1. Compound of the formula:

wherein R is an aliphatic hydrocarbon radical of from 300 to 5000 molecular weight and Y is an alkylene amine radical of from 2 to 50 carbon atoms and from 2 to 6 nitrogens, and bonded to the sulfonyl by nitrogen.

7 2. Compound of the formula:

RdNHs02[ [NH oH2)m],.[NH(CHZOHMMC QMM I wherein R is an aliphatic hydrocarbon radical of from about 20 to 300 carbon atoms, m and m are integers of from 2 to 6, p is a cardinal number of from 0 to 5, q is a cardinal number of from 0 to 3, the sum of p and 2q being from 1 to 6.

3. Compound of the formula:

wherein R R and R are selected from the group consisting of hydrogen and aliphatic hydrocarbon radicals, at least one of the group, R and R being an aliphatic hydrocarbon radical of from about 25 to 200 carbon atoms, In" is an integer of from 2 to 6, and p is an integer of from 1 to 5.

4. A compound of the formula:

wherein R is polyisobutenyl of from about 25 to 200 carbon atoms.

5. A compound of the formula:

i RCNHSOzNHCHsCHzNHz wherein R is polyisobutenyl of from about 25 to 200 carbon atoms.

6. A compound of the formula:

wherein R is polyisobutenyl of from about 25 to 200 carbon atoms.

7. A compound of the formula:

wherein R is a poly(cracked wax) olefin of C1540 olefins.

References Cited UNITED STATES PATENTS 2,236,168 3/1941 Dietrich 252-47.5 3,041,336 6/1962 Teufel 260556 FOREIGN PATENTS 735,765 9/1932 France. 940,529 3 195 6 Germany. 941,847 4/ 1956 Germany. 1,004,189 3/1957 Germany.

DANIEL E. WYMAN, Primary Examiner.

L. G. XIARHOS, W. H. CANNON, Assistant Examiners.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2236168 *Feb 27, 1940Mar 25, 1941Du PontLubricant
US3041336 *Sep 23, 1959Jun 26, 1962Geigy Chem Corp3-oxo-1.2.6-thiadiazine-1.1-dioxides
*DE94529C Title not available
DE941847C *Dec 19, 1953Apr 19, 1956Hoechst AgVerfahren zur Herstellung am Stickstoff sulfochlorierter organischer Verbindungen
DE1004189B *Mar 19, 1954Mar 14, 1957Hoechst AgVerfahren zur Herstellung von -Sulfamido-carbonsaeureamiden
FR735765A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4292185 *Dec 31, 1979Sep 29, 1981Rohm And Haas CompanyPolymeric additive for lubricants and fuels
US4410437 *Mar 13, 1981Oct 18, 1983Chevron Research CompanyReaction with sulfur dioxide
US4548722 *Nov 9, 1984Oct 22, 1985Chevron Research CompanyReacting a polyamine with sulfur dioxide
Classifications
U.S. Classification508/376, 508/554, 564/79, 508/555, 554/43
International ClassificationC08F8/32, C08F26/00
Cooperative ClassificationC10M2223/042, C10M2219/04, C10M2207/34, C10M2205/026, C10M2205/02, C10M2223/04, C10M2223/045, C10N2210/02, C10M2207/04, C08F8/32, C10M2203/06, C10M1/08, C10N2270/02, C10M2207/282, C10M2209/105, C10M2209/103, C10M2205/028
European ClassificationC08F8/32, C10M1/08