US2908648A

US2908648A - Corrosion-inhibited compositions containing n-(alkylarylsulfonyl) amino acids and salts thereof

Info

Publication number: US2908648A
Application number: US463842A
Authority: US
Inventors: John D Spivack; Janet B Peterson; Kroll Harry
Original assignee: Geigy Chemical Corp
Current assignee: Novartis Corp
Priority date: 1954-10-21
Filing date: 1954-10-21
Publication date: 1959-10-13
Anticipated expiration: 1976-10-13
Also published as: CH344886A; BE542184A

Description

United States Patd i 2,968,648 l'tl t t99213 29 CORRQSION-INHIBIIED coMPosrnoNs com 'lAlNING N-(ALKYLARYLSULFONYL) AMINO V ACIDS AND SALTS THEREOF John D. Spiva'ck and Janet a. Petersen; Cian'stiiii; and Harry Kroll, Warwick; 12.1., assign'o'i's to Gei Chemical Corporation, New' York, N.Y., a corporation of Delaware I j No Drawing. Application (lictober 21, 1954 Si'ial No. 463,842 12 Claims. Gian-47.5

This invention relates to compositions having corrosion inhibited, and especially" rust-inhibited properties, which contain alkylarylsulfonyl derivatives. More particularly the present invention relates to organic compositions, especially oleag'inous compositions containing an alkyl-arylsul'fonyl derivative, which compositions have the property of preventing or inhibiting corrosion and/0r, rusting; especially in sy'ste'rhsem'ploying water or steam or which may be contaminated with water or steam. V In various equipment in which water and/ or steam is used, or which may become contaminated with water or steam during service orstorag'e, corrosion and/orrustirrg of the metal parts, particularly'the ferrous metalparts, is encountered causing material damage to such equipment. The prevention of rust formation is particularly impore taut in the protection of metal surfaces where such surfaces are to be lubricated in the presenee ofmoisture. Moisture may enter lubricating systems of land or marine turbines, for example, by leakage through steamglands and through water-cooled heat exchangers or :by, condensation fromqthe amesphere. ,The reseeceorma is injurious because it causes excessivev wear of gears and bearing surfacesand may also clog the hydraulic governor system, leading to dangerous operating speeds. Furthermore, the presence of rust has been'shown to increase th e rate' of roxidative, breakdown of the lubricantitself.

The present'inventiqn is also applicable to anti-ruster slu'shin'g compositions employed for the protection of metals against atmospheric corrosion vand/ or Such compositions are applied to metallic articles, includipg fabricated metallic artieles and finished of semi-fin v ished riiet'al stock to be stored or for shipment by rail or water, to p'r'eveliq r'u'stiiig arid/or corrosion thereo f. r The aim in the use' of protective orslushirig; compositions is tofprot ect fobiec s against Q attack by moisture by coat in'gthem'. Important industrial a'plication's' of the corrosion this invention may be added to awide of vehicles to produce compositions having corrosion-inhibited properties, including acidic. aqueousliquids, suchas used in V amidoalk ue ca y i -a f the. general fopmula' R SO ','-NH --R C O OR (wherein R is a saturated hyd-roca'r bfon of ,C C k is'either aliphatic C H m or aryl or aromatic radicals and R is H or an alkalim'etal; or amn'aoni-u'm') to alcohols, ketones and mixtures thereof. The alkanes'ul'fonamidoalkane .carboxylic acids used for that purpose are described in U.S. Patent No. 2,225,960 granted December 24, 1940. A specific example is hexadecanesulfonamidoacetic acid of the formula:

C H sQgNH cH eoo Ii-l I The compounds which utilize as potent corrosive and/ or rust inhibiting agents according to the present in vention are broadly alkylarylsulfonyl derivatives of air amino acid. The sulfonyl group is attached directly to the aromatic nucleus. T hose which are suitable for our purpose are alkylarylsulfonyl amino acids having the empirical formula:v

wherein R represents one or two alkyl groups of 8-24 carbon atoms inclusiveg Ar representsan aryl group. which may bephehyl, naphtHyL-arithracyl, plienanth'ryl, chrysyl (Beilstein; vol. V,- p. 718)", etcJ;"R represents a substituent selectedfrom the group consisting of hydrogen, allgyl; lrjydroxyalkyl, carboxyalkyl and phenyl; R represents a substituent selected from the group consist- 1 ing of hydrogen, alkyl and czirboxyalkyl; n represents l" or 2; Y represents hydrogen or a-salt forming group; The above type compounds are added to a liquid or semi-solid vehicle iii a quantity sufiicient to confer corrosion and/or rust prevention to the composition which otherwise tends to permit corrosion of metal when brought and/or rust preventing compounds of the present invenr-;1

tionva'r'y over a widera'nge. They afio'rd excellent" piotection when incorporated intothe following lubricating oils and :dielectn'c'oils': motor oils, dies'e'loils," aviation engine oils, marine engjne lubricants, gear oils, oil field V machinery iubncamsic'e-maenine ens, steam cylinder lubricants, transmission oils; soluble oils,textiletoils, achrtinlg' oils both soluble; containing water and the straight oils, turbine oils;- insulatingoils, lubricatifig greases; stable gel-like or solid dispersions of metal soapsin hydrocarbonpils; protective coatings; preservative com pounds, slushing oils and greases in which part orall ref in surface contact therewith.

t v More particularly and important we have found that graph. Suoh compounds, when used in small amounts in I oleaginous vehicles, it has been determined by scientifically acceptable tests andby other means, efiectively prevent the rusting oi metal s urfaces, particularly those of ferrous metal, upon'exposure to water or steam. These additives, =moreover, prevent rusting without influeneing the hydrocarbon oil may berepl -aced by metal soaps; and. other constituents; flushing; oils. These. have v -vehicle'swould beelassed in whole or part as oleaginous. he T Y1 F E Y' mi e-a ids a dvt r: lt lot i therproperties oftthe lubricant disadvantageousl'y.

members of, this; class" of corrosion" 'preve uial synthetic amino: acids,*fforfiexample, of glycine, whose the structural formula of which are CH CH(NH )COOH and CH (NH )CH COOH respectively, sarcosine or methyl glycocoll, whose structural formula is CH NHCH COOH iminodiacetic acid, whose structural formula is HOCOCH NHCH COOH aspartic acid whose structural formula is HOCO.CH(NH )CH COOH v glutamic acid whose structural formula is HOICT?H(CH2)2000H NH:

Non-limiting examples of the new type of compounds which are useful asrust and/or corrosion preventives are: N-(dodecylbenzenesulfonyl) glycine, N-(dodecylbenzenesulfonyl) sarcosine, N-(dodecylbenzenesulfonyl) irnin'odiacetic acid, N-(dodecylbenzenesulfonyl) glutamic' acid, N-(dodecylbenzenesulfonyl) alanine, N'-(dinonylnapha thalenesulfonyl) glycine, N-(dinonylnaphthalenesulfonyl) sarcosine, N-(dinonylnaphthalenesulfonyl)-iminodiacetic acid, N-(dinonylnaphthalenesulfonyl) glutamic acid, N- (dinonylnaphthalenesulfonyl) alanine, N-(octadecyl anthracenesulfonyl)-sarcosine, N-(octyl xylyl) sarcosine and the like.

The sulfonylated amino acids of the general type of the corrosion preventative agents of our'invention can be prepared in a number of ways, forexample, as out- Ssponification Saponification 2 Acidification RArSaNR1(CHz),-CHC00H R-Ar- SO2NH+Cl(CH2)n-(i7HGOONa '-v .1 R," v v R-A'r-s0mr21(o11,)..-on'o ooNa e ifi n .7 n-ar-soirmaomn onooon V ,1 2 Thereactants in the process of manufacture maybe re atrvelypure single compounds, for example, pure allgylarylsulfonyl, chloride or :thesulfon yl a'mide (see empir cal: formula of respective first; mentioned reactant 1n .l'Tiq1 lt10l1S'A and D), and pure arriin'o z cid"Sal s, @313;

compounds.

or nitrile conforming to the second respective reactant in the empirical formula set forth in equations of processes (A), (B) and (C), and the pure chlorocarboxylic acid salt which is the second reactant in the process of equation D. Or the reactants may be mixtures resulting in a product consisting of a mixture of compounds, all represented by the formula the symbols in which are defined above.

In further explanation, it may be stated that the RA1' grouping set forth above may be derived from straightchain or branched-chain octyl, decyl, dodecyl, tetradecyl, hexadecyl, or octadecyl derivatives of either benzene, naphthalene, anthacene or chrysene or from mixtures thereof. The R-Ar grouping may also be derived from the reduction of fatty acylated or alkenylated aromatic The products obtained by processes (B) and (C) outlined above may also have more or less unsaponified ester or nitrile groupings present therein in addition to free carboxyl groups or salts thereof.

One of the major uses of the additives of the present invention is in the industrial field of lubrication of metal surfaces employing both oils and greases. Another use is the protection of metals, such as iron or broader the ferrous type metal, in humid atmospheres by preservative oils and slushing oils or greases. The members of the class of compounds of this invention can be used alone in an oleaginous vehicle or solvent. Used thus these additives which function as corrosion inhibitors, may be used in a variety of physical states, e.g., as a dispersion, emulsion or solution. When employed in an oleaginous vehicle, the compounds should be soluble, miscible or dispersible in said vehicle. It should be noted that the term oleaginous vehicle is employed in the broader sense and to include hydrocarbon oils, fatty oils, fats, the synthetic lubricants such as those of the polyester, poly siloxane, polyalkylene glycols and polyolefine types, and rustproof bases, etc., which may be used as the medium of application of rust-preventive additive to the metal surface. V I a The N-(alkylarylsulfonyl) amino acids may be incor-' porated in the oleaginous vehicle in varying proportions being governed by specific use to which the rust preven tive compositionis to be put, the degree of rust prevention desired, as well as economic considerations, and on the specific alkylarylsulfonyl amino. acid selected. Generally it is suificient to use an amount between 0.005 and a 10% by weight, although greater or lesser amounts may be used.

As indicated supra, the general type of alkylarylsulfonyl amino acids and their salts, which are the corrosion inhibitors of the'present inventors, are believed to have the rust tests and emulsion tests.

i EXAMPLES OF OUR CORROSION INHIBITORS Example 1 of corrosion'inhibitor 1T N-(n-dodecylbertzenesulfonyl) sarco'sine 1 (A) AND (B) PREPARATION OF N-DODE CYLQ I BENZENESULFONYL Seventy-four grams (74 g.) (0.30 mole) of n d decyI- benzene (N 1.483,' boilingat 4.2 mm. Hg pressure at l65170 C.) was dissolved in- 200 millilitersof methylene chloride in a 1-liter flask fitted with a mechanical stirrer, an air condensen'thermorneter and dropping funnel; the entire apparatus wasprotected from moisture -by calcium chloride drying tubes on thecondenser and the dropping funnel. The solutionwas cooled to"10 C.

by an externalbath. Chlorsulfonic acid (73 g) (0.63

minutes while its temperature was kept at -10 C. to -7 C. The reaction mixture became dark brown in color. It was stirred and additional two hours while maintaining its temperature at C., followed by two more hours at 20 C., whereupon it was let stand at room temperature overnight, i.e., for about'fifteen hours. The reaction mixture was'poured into 300 grams of ice, and 300 milliliters of diethyl ether were added, intimately mixed therewith, whereupon after Stratification the water layer was separated from the upper or ether layer. The water layer was extracted with anadditional 300 milliliters of ether. The combined ether extracts were extracted with 300 milliliters of a aqueous solution of sodium bicarbonate also containing 10% by weight of sodium chloride to remove residual inorganic acids. The ether in the purified ether layer was removed by distillation at atmospheric pressure followed by reduced pressure. The residue was taken up in 500 milliliters of acetone and filtered free of inorganic salts. Analysis of the residue (A) from the acetone distillation indicated that product (A) contained about 8.3% of n-dodecylbenzene sulfonyl chloride, the remainder being n-dodecylbenzene sulfonic acid.

Phosphorus pentachloride (19.3 grams) was added gradually with occasional shaking to product (A) amounting to 28 grams, in an Erlenmeyer flask fitted with a drying tube. After eifervescence stopped, the reaction mixture was warmed on a water bath for about 30 minutes. The product was then poured into ice, and extracted with 200 milliliters of ether. The ether extract was thereupon washed with water' and then dried over anhydrous sodium sulfate. After being separated, ether was removed by evaporation. The residue, which was product (B), was a viscous, reddish oil, the analysis of which indicated that it consisted of 96%-97% of ndodecylbenzenesulfonyl chloride.

(C) PREPARATION OF N-(n-DODECYLBENZENESULFO- NYL) SARCOSINE FROM PRODUCT (B) SUPRA.

Sarcosine (3.6 grams) (0.041 mole) was dissolved in 41 milliliters of 1.0 N solution of sodium hydroxide in water to form its sodium salt, and cooled to 15 .C. A

dioxane solution on n-dodecylbenzenesulfonyl chloride (14.0 grams of product (B) described :above dissolved in 50 milliliters of dioxane) and 41 'milliliters' of 1.0 N aqueous sodiumhydroxide were added dropwise simultaneously to the aqueous sarcosine solution of the sodium salt of sarcosine over a period of 20 minutes. The reaction mixture was stirred an additional two hours at room temperature; this contained thesodium salt' of N- (n-dodecylbenzenesulfonyl) sarcosinewith by-products of the. reaction. It was then made acid to pH 2.. with 6 N aqueous hydrochloric acid, after whichjit was extracted with ether. This extract was heatedto distill off, the ether. The residue (12.8 grams) wascrystallized from n hexane, and there was obtained-a white crystalline product! melting at 110-111 C. (uncorrected)=.' The crystalline product was: substantially pure N-(n-dodecyl benzenesulfonyl) sarcosine having; a neutralization equivalentv weight of 400.- The calculated neutralization equivalent: weight for. N-(n-dodecylbenzenesulfonyl) sarcosine is 397.

Example 2 of corrosion inhib'it0r--1\l'-(rua bdecyl-l' benzenesulfonyl') iminodiac'eticjacid Dimethyl. iminodiacetate. hydrochloride. (7.7

(0.039 mole) was dissolved in 100' millilitersoffchloroform contained in a 300 milliliter capacity. flask which was fitted with a condenser, stirrerf'and dropping funnel suitably fittedwith calcium chloride drying tubes to protect the reaction mixture from moisture; Triethylamine (852 grams) (0:082'inole) was addediall'at once; and" the reaction mixture cooled to room temperature A dioxane solution ofn-dodecylbenzenesulfonyl chloride (14 grams) (0.041-mo1e) dissolved in 50 milliliters-of dioxane was added dropwise to the reaction mixture while undergoing stirring, overa period of 25 minutes, and this mixture was stirred at room temperature for an hour; it was then heated at reflux for an additional hour. The chloroform solution of the reaction product was washed successively with water and 5% aqueous sodium chloride solution, and then dried over anhydrous sodium sulfate. It was then decanted from the drying agent. The residue, after evaporation of chloroform was heated on a steam bath with milliliters of 1 N sodium hydroxide solution in water for two hours.' The product was the sodium salt of N-'(n dodecylbenzenesulfonyl) iminocliace'tic acid in solution. The alkaline solution was extracted with 100 milliliters of ether to remove uns'aponified material. The aqueous solution was then made acid to pH 1 and extracted with 150 milliliters of ether, after which the other layer was separated and dried over anhydrous sodium sulfate. After separation from the dehydrating agent, ether was distilled on. The residue I Example 3 of corrosion inhibitor-(N-dodecylbenzenesulfonyl) sarcosine technical (A) PREPARATION OF DODECYLBENZENESULFON'YL CHLORIDE This compound was prepared in the following manner from a commercial grade of dodecylbenzene.

One-half mole of dodccylbenzene (123 grams) was dissolved in 200 milliliters of methylene chloride in a 1-liter flask fitted with a mechanical stirrer, an air-condenser, thermometer and dropping funnel; theentire apparatus was protected from moisture by calcium chloride drying tubes onthecondenser and dropping funnel. After cooling the methylene chloride solution to 8 C. by an external bath, chlorsulfonic acid (145.5 g.) (1.2- moles) was added thereto, dropwise, over a period of one hour and fifty minutes while the temperature of the reaction mixture was maintained between 9 and 2 C. The reaction mixture became increasinglydark brown in color as the addition of chlorsulfonic acid proceeded. It was stirred an additional two hours while maintaining its temperature at 0 C., whereupon it was allowed to stand at room temperature for about 16 hours.- It was then poured into a mixture of 500 milliliters of 15% aqueous sodium chloride and about 300 grams of 'ice,

in water; it Weighed grams. Thevyield ofcrudeipi'od not was thereforeabout' 70%" of theory.

Analysis of the crude sulfonyl chloride gave the 61 lowing results:

V V percent Dodecylbenzenesulfonylchloride 87.1' Dodecylbenzenesulfonic acid 14.8

The analytical results indicated, that the producf as described above could be useda's a reactant in'tliis and the next-example.

(B) PREPARATIONDF N-DODECVYLBENZENESULFONYL v I SARCOSINE FROM PRODUCT (A) SUPRA Nine and two-tenths. grams (9.2 g.) '.(0.10,mole) of sarcosincewhich was96.6% pure was dissolved in 100 milliliters of water containing 4.1 grams (0.10 mole) of sodium hydroxide. Dodecylbenzenesulfonyl chloride described in (A) above (39.2 grams) (0.10 mole) was dissolved in dioxane so that a volume of .70 milliliters ,was obtained. The dioxane solution of it and 70. milliliters of aqueous alkali (containing 4.7 grams of sodium hydroxide) were added simultaneously tofthe stirred sarcosine solution'over a period of 30 minutes,.the temperature of the reaction varying from 28 C. to 37 C. The reaction mixture was stirred at 45 C. for one hour and then let stand at room temperature for about sixteen hours. This contained the sodium salt of N-dodecylbenzenesulfonyl chloride sacrosine-technical. It was then made acid to pH 3 with 6 N aqueous hydrochloric acid after which it was extracted with two 200, milliliter portions'o-f diethyl ether. The ether'layer was dried over anhydrous sodium sulfate. After this dehydrationstep and separation from the sodium sulfate, ether was removed by distillation. The residue was an amber-like gummy mass having a neutralization equivalent of 485. The theoretical neutralization equivalent for N-(dodecylbenzenesulfonyl) sarcosine is 397. The reaction product thus has anianalysis which varies quite appreciably from that expected for (N-dodecylbenzenesulfonyl) sarcosine.

Example 4 of corrosion inhibitor.Reactin product of technical dodecylbenzenesulfonyl chloride with iminodiacetic acid Iminodiacetic acid (2 g.) (0.015 mole) and triethylamine (4.55 g.) (0.045 mole) were mixed in boiling chloroform, and after cooling to room-temperature the 90% dodecylbenzenesulfonyl chloride, prepared by Example 3(A) supra, in an amount of 5.15 grams (0.0105

mole) was added. The mixture was shaken vigorously for 20 minutes, then allowed to stand at room temperature overnight (about 16 hours). It was then refluxed for an hour before filtering the insoluble material. The chloroform was'removed by distillation in vacuo. The residue, which represented the triethylamine salt of'technical (N-dodecylbenzenesulfonyl) iminodiacetic acid, was acidified to pH 1 with aqueous 6 N hydrochloric acid after which the solution was extracted several times with ether. The ether extracts were washed with dilute hydrochloric acid and water and thereafter dried over anhydrous sodium sulfate. 'After decantation from the dehydrating agent, the ether was removed by distillation.

The residue was an amber colored, semi-hardened mass,

weighing 1.4 grams. It has a neutralization equivalent of 548. The reaction product thus has an analysis which varies quite appreciably from that expected for (N-dodecylbenzenesulfonyl) iminodiacetic acid.

Example of corrosion inhibitor.Reaction product of dodecylbenzenesulfonyl chloride with dimethyliminodiacetate hydrochloride Dimethyliminodiacetate hydrochloride (20.0 grams) (0.10 mole) was dispersed in 200 milliliters of chloroform, and 24.3 grams of triethylamine (0.24 mole) was added rapidly while the chloroform dispersion was stirred.

Dodecylbenzenesulfonyl chloride was dissolved in 125 milliliters of chloroform and added dropwise over a period of one hour to the stirred chloroform solution of dimethyliminodiacetate. The turbid reaction mixture was stirred at room temperature for an additional hour, then washed o us methanol containing 17 grams of potassium hydroxide and'warmed on the steam bath for one hour with decasional stirring. The reaction solution of the potassium salt of (N-dodecylbenzenesulfonyl)iminodiacetic acid was diluted'with an equal volume of water, made acid to pHl with 6 'Naqueous hydrochloricfacid and. extracted with two 200 milliliter portions of ether. The ether solution of the'fre'e (N-dodecylbenzenesulfonyl) iminodiacetio acid was then driedover anhydrous sodium sulfate. After decantation from the drying agent the ether was distilled otff The residuefrom ether weighed 32.9 grams and had a neutralizationequivalent of 415. The theoretical neutralization equivalent for '(N-dodecylbenzenesulfonyl) iminodiacetic acid is 220.5 indicating that the product is a mixture of (N-dodecylbenzenesulfonyl) -iminodiacetic acid and its methyl esters;

In order to demonstrate the outstanding properties of the N-(alkylarylsulfonyl) amino acids and their salts, which are the corrosion inhibitors of the present invention, rust test data and emulsion test data were obtained for a selected mineral oil containing the respective products synthesized in Examples 1, 2, 3, 4 and 5 described above. The oil used in these was a solvent-refined and filtered non-additive turbine-grade lubricating mineral oil of 150 Saybolt Universal Seconds viscosity at F.

The rust test which was selected because it'has been widely used was the Static Water Drop Corrosion Test developed by Zisman et al. and described in Industrial and Engineering Chemistry, vol. 41, page 137 it (1949). Briefly, the test consists essentially of observing rusting at 140 F. in the presence of liquid water in the dimple of a triangular cold-rolled steel specimen immersed in the test oil, An effective rust preventive ,oil will prevent rusting for several days while straight mineral oils permit rusting to occur within'2 hours. of test. Solubilization of these 'N-(alkylarylsulfonyl) amino acids of these examples was effected by the addition of a solubilization agent which per se in oil solution had little, if any, rust preventive properties. The specific agent used was a commercially available tertiary alkyl primary'amine, the tertiary alkyl groups having'from 18 to 24 carbon atoms, known as Primene JMR, which is descn'bedmore' exactly in a footnote-in Table I.

The test used for determining the demulsibility properties of lubricating oils is to be found in the Federal Standard Stock Catalogue method 320.1.5 dated November 15, 1948, and entitled Emulsion (Lubricating Oils). Briefly, this test involves mixin 40 milliliters of water and 40 milliliters of test oil at 130 F. or Fpunder standard conditions and observing the separation of oil and water phases at the test temperature. The test temperature selected is usually 130 F. for light viscosity turbine oils up' to about 500 SayboltUniversal seconds viscosity at 100 F., andthat'was the temperature which was selected for the tests reported. Thefigures in the table show the number of minutes at which thereis no continuous layer of emulsion between the oil and the emulsant (water). The US. Navy specifies'that 2190-T grade turbine oils separate from water in this test within thirty minutes and have not more than 3 milliliters of an intermediate oil-and-water phase at this time in order to comply with MIL-D1733? (Ships) Specification of September '30, 1952. This criterion of demulsibility is widely adopted by turbine oil producers and consumers.

For comparison, in order to determine quantitatively the effect of other additives to the mineral lubricatingoil, both on rust preventionand imparting different emulsification characteristics, the corrosion test and the emulsion test were run on the base oil as'a check, the tertiaryalkyl primary amine- (2 concentrations) in the oil, stearic acid in the oil, and mixtureof stearic acid with the tertiaryallgyl primary amine in the oil, as well as the oil containingi the investigated N-(alkyl aryls'ulfonyl) amino acids in the compositions given in the appended table.

- The Pertinent test results; are set forth in Table I,

TABLE I.RUST PREVENTIVE AND DEMULSIBILITY PROPERTIES O F (N JQLKYLARYLSULFON YL) AMINO I ACIDS :IN LUBRIOATING OIL Emulsion V Wt. pcr- TestTime "Static Water Example Wt. percent of for 'Oom- Drop orrosion Additive (X) i No. of (X) Primene iplete Sepa- Test Time to JMR ration Rust (Hours) (Minutes) Base Oil None None Less than 16. fPrinieneJMR 1 None 0. Do. Primene J MR. None 0. 0125 Stearic Acid Do. Btearic Acid andTrimene .TMR" Less than 2. N -(n-dodecylbenzenesulfonyl) sarcosine I More than 300 hrs. N-(n-dodecylbenzenesulfonyl)iminodiacetic acid. II Do. (N -dodecylbenzenesulfonyl)sarcosine (technical) III Do.

Do. v III Do. Reaction Product of technical dodecylbenzenesuljfonyl IV Do.

chlorideand iminodiacetic acid.

(N-dodecylbenzenesulfony1)iminodiacetic acid (technical) V 6 Do. D0.. V 12 D0.

1 "Primene JMR is a mixture of branched, primary amines in which the a tertiary carbon atom, and being composed of amines from eighteen to twent primary amino nitrogen group is directly attached to y-four carbon atoms; the predominant portion may be represented by the formula t= OwnHa qNHg. It contains about 840% non-amine material. This trademarked product is marketed V by Rohm & Haas Company of Philadelphia, Pennsylvania.

From the data set forth in this table it is apparent that a much improved rust preventive effectiveness is imparted to lubricating oil which contains the N- (alkylarylsulfonyl) amino acids of the present invention, whether the comparison is made on the base oil alone or with the solubilizer in the oil. It is also evidentthat the .N-(alkylarylsulfonyl) amino acids are qualitativelysuperior in rust preventive eifectiveness than a typical high molecular weight fatty acid, such as stearic acid, or the latter admixed with the identical solubiliz er It is apparent from the emulsion test data given in the table that the alkylarylsulfonyl amino acids tested do not impart undesirable emulsion characteristics to the turbineoil.

. The vehicle can be aqueous which includes aqueous solutions of liquids, such as alcohol-water mixtures, or the like, Non-limiting examples of suitable vehicles for the corrosive inhibitor additives of this invention are mineral lubricating oils of all grades; gasolines and otherlight petroleum products, such as fuel oil; water, alcohols, such as ethanol, isopropanoL'butanol; cyclohexanol, methylcyclohexanol, octanol, decanol, dodecanol, hexadecanol, octadecanoh-oleyl alcohol, benzyl alcohol, ctc.; glycols, such as ethylene glycol, propylene glycol, butylene glycol; glycerol, etc.; ketones, such as acetone, methyl ethyl ketone, dipropyl ketone, cyclohexanone, etc. keto alcohols, such as benzoin; others, such as diethyl ether, dipropyl ether, dichloro diethyl ether, diphenyl oxide, polyethylene glycols as diethylene glycol and triethylene glycol, ethy1 ene glycol monobutyl ether, etc.; neutral esters, such as ethyl acetate, butyl propionate, cresyl acetate, dodecyl acetate, ethyl maleate, butyl stearate, tridecyl phosphate, tributyl trithiophosphate, triamyl phosphite, dibutyl sebacate and dioctyl sebacate, etc.; petroleumwaxes, such as slack wax and paraffin wax; natural waxes, such as carnauba wax, japan Wax, beeswax, etc.; natural fats and oils, such as sperm oil, tallow, cottonseed oil, castor oil, linseed oil, tung oil, soybean oil, oiticica oil, tar oil, oleo oil, etc.; hydrocarbons; greases; asphalts; and chlorinated petroleum fractions, such as chlo'rowvax.

The order of amount of corrosive inhibitor additive set out previously as to oleaginous vehicles.

. Acidic aqueous solutions for metal pickling baths cananti-freezes include Water, water-alcoho1, glycols, glycolwater, etc.

Other substances in addition to the reaction products, the corrosion inhibitors of this invention can be added to compositions contemplated herein to impart other desirable properties thereto, such as anti-oxidants, pour point depressants, V.I. improver's, etc.

Some members of this class of compounds will be preferred for specific applications While other members will be preferred for other applications whererust prevention is desired. Some members of this class of compounds are particularly applicable for turbine lubrication, because lubricant compositions containing them permit ready separation of entrained water. It is essential that Water be easily separable from turbine lubricants by auxiliary oil purification equipment such as settling tanks, filters, blotter presses, centrifuges, etc., because ,Water in addition to causing rusting accelerates oil breakdown, causes excessive foaming and facilitates the dispersion of other contaminants which accelerate oil breakdown and are injurious to the lubricating system in other ways.

Although the present invention has been described with preferred embodiments, it is to he understood that modifications may be made without departing from the spirit and scope thereof, as those skilled Will readily understand. Such variations and modifications are considered to be within the purview and scope of the appended claims;

We claim as our invention:

1. A corrosion-inhibiting composition which comprises a liquid vehicle which tends to permit the corrosion of metalin the service to which said vehicle is put, containing a member selected from the group consisting of N-(n-dodecylbenzenesulfonyl) sarcosine and N-(n-dodecylbenzenesulfonyl) iminoacetic acid, said member being present in said liquid vehicle in amounts of as little as a fraction of 1% by Weight but in a sulficient quantity to inhibit corrosion of said vehicle.

2. A corrosion-inhibiting composition which comprises a liquid vehicle which tends to permit the corrosion of metal in the service to Which said vehicle is put, containing N-(n-dodecylbenzenesulfonyl) sarcosine, said latter component being present in said liquid vehicle in amounts of as little as a fraction of 1% by weight but in a sufficient quantity to inhibit corrosion of said metal.

3. A corrosion inhibiting composition which comprises a liquid vehicle which tends to permit the corrosion of metal in the service to which said vehicle is put, containing N-(n-dodccylbenzenesulfonyl) iminodiacetic acid, said latter component being present in said liquid vehicle in amounts of as little as a fraction of 1% by weight but in a suflicient quantity to inhibit corrosion of said metal.

4. A rust-inhibited oleaginous composition adapted for use in the presence of water in systems containing metal susceptible to corrosion by said water, comprising an oleaginous vehicle and a member selected from the group consisting of N-(n-dodecylbenzenesulfonyl) sarcosine and N-(n-dodecylbenzenesulfonyl) iminoacetic acid, said member being present in said oleaginous vehicle in amounts of as little as a fraction of 1% by weight but in a sufiicient quantity to inhibit corrosion of said vehicle.

5. A rust-inhibited oleaginous composition adapted foruse in the presence of water in systems containing metal susceptible to corrosion by said water comprising an oleaginous vehicle and N-(n-dedocylbenzenesulfonyl) sarcosine, said latter component being present in said oleaginous vehicle in amounts of as little as a fraction of 1% by weight but in a sufficient quantity to inhibit corrosion of said metal.

6. A rust-inhibited oleaginous composition adapted for use in the presence of water in systems containing metal susceptible to corrosion by said water comprising an oleaginous vehicle and N-(n-dodecylbenzenesulfonyl) iminodiacetic acid, said latter component being present in said oleaginous vehicle in amounts of as little as a fraction of 1% by Weight but in a suflicient quantity to inhibit corrosion of said metal. I

7. A rust-inhibited oleaginous composition adapted for use in the presence of water in systems containing metal susceptible to corrosion by said water, comprising an oleaginous vehicle, a member selected from the group consisting of N-(n-dodecylbenzenesulfonyl) sarcosine and N--(n-dodecylbenzenesulfony1) iminoacetic acid in amounts of as little as a fraction of 1% but in suflicient quantity'to inhibit corrosion of said metal, and an alkyl primary amine having 18-24 carbon atoms in sufiicient amount to solubilize said member in the oleaginous vehicle.

8. A rust-inhibited oleaginous composition adapted for use in the presence of water in systems containing metal susceptible to corrosion by said water, comprising an oleaginous vehicle, N-(n-dodecylbenzenesulfonyl) sarcosine in amounts of as little as a fraction of 1% but in sufiicient quantity to inhibit corrosion of said metal,

and an alkyl primary amine having 18-24carbonatoms in suflicient amount to solubilize said N-(n-dodecylbenzenesulfonyl) sarcosine in the oleaginous vehicle.

9. A rust-inhibited oleaginous composition adapted for use in the presence of water in systems containing metal susceptible to corrosion by said water, comprising an oleaginous vehicle, N-(n'dodecylbenzenesulfonyl) iminodiacetic acid in amounts of as little as a fraction of 1% but in suificient quantity to inhibit corrosion of said 12 metal, and an alkyl primary amine having 18-24 carbon atoms in suflicient amount to solubilize said N-(n-dodecylbenzenesulfonyl) iminodiacetic acid.-

10. A rust-inhibited oleaginous composition adapted for use in the presence of water in systems containing metal susceptible to corrosion bysaid Water, comprising an oleaginous vehicle, a member selected from the group consisting of N-(n-dodecylbenzenesulfonyl) sarcosine and N-(n-dodecylbenzenesulfonyl) iminoacetic acid in amounts to between substantially 0.005 to about 10% by weight, and an alkyl primary amine having 18-24 carbon atoms in suflicient amount to solubilize said member in the oleaginous vehicle.

11. A rust-inhibited oleaginous composition adapted for use in the presence of water in systems containing metal susceptible to corrosion by said Water, comprising an oleaginous vehicle, N-(n-dodecylbenzenesulfonyl) sar cosine in amounts between substantially 0.005% to about 10% by weight, and an alkyl primary amine having 18-24 carbon atoms in suflicient amount to solubilize said N-(n-dodecylbenzenesulfonyl) sarcosine in the oleaginous vehicle. Y

12. A rust-inhibited oleaginous composition adapted for use in the presence of water in systems containing metal susceptible to corrosion by said water, comprising an oleaginous vehicle, N-(n-dodecylbenzenesulfonyl) iminodiacetic'acid in amounts between substantially 0.005% to about 10% by weight, and an alkyl primary amine having 18-24 carbon atoms insufficient amount to solubilize said N-(n-dodecylbenzenesulfonyl) iminodiacetic acid.

References Cited in the fileof this patent UNITED STATES PATENTS 2,142,847 Hultquist Jan. 3, 1939 2,225,960 Orthner et al. Dec. 24, 1940 2,578,725 Michel et al. Dec. 18, 1951 2,602,760 Michel et al. "July 8, 1952 2,656,381 Sprague Oct. 20, 1953 2,660,562 Axe et al Nov. 24, 1953 2,692,857 Michel et al. Oct. 26, 1954 2,694,045 Jones et al. Nov. 9, 1954 2,704,264 Michel et al. Mar. 15, 1955 FOREIGN PATENTS 900,041 Germany Dec. 17, 1953 OTHER REFERENCES Tertiary-alkyl Primary Amines, Rohm & Haas, Septem- 9 her 1954, pp. 1 and 17. 7

Claims

1. A CORROSION-INHIBITING COMPOSITION WHICH COMPRISES A LIQUID VEHICLE WHICH TENDS TO PERMIT THE CORROSION OF METAL IN THE SERVICE TO WHICH SAID VEHICLE IS PUT, CONTAINING A MEMBER SELECTED FROM THE GROUP CONSISTING OF N-(N-DODECYLBENZENESULFONYL) SARCOSINE AND N-(N-DODECYLBENZENESULFONYL) IMINOACETIC ACID, SAID MEMBER BEING PRESENT IN SAID LIQUID VEHICLE IN AMOUNT OF AS LITTLE AS A FRACTION OF 1% BY WEIGHT BUT IN ASUFFICIENT QUANTITY TO INHIBIT CORROSION OF SAID VEHICLE.

7. A RUST-INHIBITED OLEAGINOUS COMPOSITION ADAPTED FOR USE IN THE PRESENCE OF WATER IN SYSTEMS CONTAINING METAL SUSCEPTIBLE TO CORROSION BY SAID WATER, COMPRISING AN OLEAGINOUS VEHICLE, A MEMBER SELECTED FROM THE GROUP CONSISTING OF N-(N-DODECYLBENZENESULFONYL) SARCOSINE AND N-(N-DODECYLBENZENESULFONYL) IMINOACETIC ACID IN AMOUNTS OF AS LITTLE AS A FRACTION OF 1% BUT IN SUFFICIENT QUANTITY TO INHIBIT CORROSION OF SAID METAL, AND AN ALKYL PRIMARY AMINE HAVING 18-24 CARBON ATOMS IN SUFFICIENT AMOUNT TO SOLUBILIZE SAID MEMBER IN THE OLEAGINOUS VEHICLE.