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Publication numberUS3846449 A
Publication typeGrant
Publication dateNov 5, 1974
Filing dateApr 6, 1973
Priority dateAug 31, 1971
Publication numberUS 3846449 A, US 3846449A, US-A-3846449, US3846449 A, US3846449A
InventorsF Magne, R Mod, W Parker, G Sumrell
Original AssigneeUs Agriculture
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
N-substituted fatty acid amide lubricants
US 3846449 A
Abstract
This invention relates to N-acylmorpholines and N-mono and N,N-disubstituted fatty acid amides and to similar derivatives of epithioamides which are useful as base and extreme pressure lubricants and additives.
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United States Patent Magne et al.

[ Nov. 5, 1974 N-SUBSTITUTED FATTY ACID AMIDE LUBRICANTS Inventors: Frank C. Magne; Robert R. Mod;

Gene Sumrell, all of New Orleans, La.; Winfred E. Parker, Philadelphia, Pa.

Assignee: The United States of America as represented by the Secretary of Agriculture, Washington, DC.

Filed: Apr. 6, 1973 Appl. No.: 348,823

9 Related U.S. Application Data Division of Ser. No. l76.734, Aug. 31. 1971 Pat. No 3,746,644.

U.S. c1..... 260/327 E [51] Int. Cl C07d 59/00 [58] Field of Search 260/327 E, 399

References Cited UNITED STATES PATENTS Primary Examiner-John D. Randolph Assistant Examiner -C. M. S. Jaisle 5 7 1 ABSTRACT 3 Claims, N0 Drawings 7/1973 Magne et al. 252/475 9 N-SUBSTITUTED FATTY ACID AMIDE LUBRICANTS This is a division, of application Ser. No. 176,734 filed Aug. 31, 1971, now U.S. Pat. No. 3,746,644, issued July 17, 1973.

A non-exclusive, irrevocable, royalty-free license in the invention herein descrlbed, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to certain compounds which are N-fatty acyl derivatives of primary and secondary amine and N-substituted acyl derivatives of primary and secondary amines which have exhibited utility as base lubricants, extreme pressure lubricants or lube additives. More particularly, this invention relates to N- and NN- disubstituted long chain aliphatic amides the acyl componentofwhich is a normal, branched, or substituted alkenoic or alkanoic acyl groupcontaining from 16 to 22 carbon atoms the amide nitrogen of which may be derived from an alkyl amine, dialkyl amine, alkylalkoxyalkylamine, dialkoxyalkylamine or nitrogen heteroalicylic. Typical amines are butylamines, dibutylamines, N-methyl-alkoxyethyl amine, diethoxyethyl amine, and morpholine. The acyl substituent referred to may be divalent sulfur or pentavalent phosphorus.

We have discovered that many of the simple N-alkyl I and N,N-dialky1 or N-alkyl-N-alkoxyalkyl amides of the C to C alkeneoic or alkanoic fatty acids are good base lubricants. We have further discovered that the introduction ofdivalent sulfur into the fatty acid moiety-imparts excellent extreme pressure lubricant characteristics to such compounds. In particular we have foundthe epithio group to be most effective. We have also observed that the introduction of both hydr oxy and alkyl phosphato groupings alpha to each other also imparts extreme pressure lubricant characteristics to the compound.

In addition it was noted that the above hydroxyphosphato compound and its mercapto analog N- [9( 10)-mercapto-(9) lO-dibutylphosphato]stearamide were effective antiwear compounds and additives.

Included among the'specific compounds operable as base lubricants are N-methyl-N-butyloleamide, N-ethoxyethoxyethoxy propyloleamide, N- ethoxyethoxy propyloleamide,- N-

[9( 10)mercapto-(9) 10-dibutylphosphatostearoyl]morpholine.

EXAMPLE 1 N-Methyl-N-butyloleamide 100 grams (0.33 mole) of oleoyl chloride was added dropwise and with stirring to a mixture of 29 grams (0.33 mole) of N-methyl-N-butylamine and 27 grams (0.33 mole) of pyridine. Stirring was continued until the heat of reaction subsided. The solid pyridine hydrochloride was filtered off and the filtrate was washed successively with aqueous l-lCl and water until acid free. It was dried stripped, percolated through an activated alumina column, and the product removed from the percolate by'stripping off the solvent. Analysis of the product: Percent C, 78.87 (theory 78.63; percent H, 13.02 (theory 12.82); percent N, 3.96 (theory 3.99).

EXAMPLE 2 N,N-dibutyloleamide This material was prepared bythe procedure of Example 1 from 100 grams (0.33 mole) of oleoy lghloride 42.5 grams 0.33 mole of (Tin-b utylamine and 27 grams (0.33 mole) pyridine. Analysis of the product: Percent C, 78.94 (theory 79.25); percent H, 13.16 (theory 13.06); percent N, 3.44

(theory 3.56) confirm the preparation.

Example 3 Ethoxyethoxyethoxy .Propyloleamide This material was prepared by the procedure of Example 1 from 100 grams (0.33 mole) of oleoyl chloride, 73.0 grams (0.33 mole) cthoxyethoxyethoxypropylamine and 27.0 grams (0.33 mole) pyridine. Analysis of percent C, 71,84 (theory 72.04); H, 11.80 (theory 11.80), and N, 2.96 (theory 2.90) confirm the preparation.

Example 4 Ethoxyethoxypropyloleamide This material was prepared by the procedure of Example 1 from 100 grams (0.33 mole) of oleoyl chloride, 58.3 grams (0.33 mole) ethoxyethoxypropylamine and 27.0 grams (0.33 mole) of pyridine. Analyses of percent C, 71.45 (theory 73.80); percentl-l, 11.87 (theory 12.07); and percent N, 2.92 (theory 3.18) confirm the preparation- Example 5 Example 6 Methoxyethyloleamide This material was prepared by the procedure of Example 1 from 100 grams (0.33 mo1e)of oleoyl chloride, 24.4 grams (0.33 mole) of methoxyethylamine and "27.0 grams (0.33 mole) Pyridine. Analysis of percent C, 73.08 (theory 74.55); Percentl-l, 11.98 (theory 11.83); and percent N, 3.31 (theory 4.14) confirm the preparation.

Example 7 Oleoylmorpholine This material was prepared by the procedure of Example 1 from 100 grams (0.33 mole) of oleoyl chloride, 28.7 grams (0.33 mole) of morpholine and 27.0 grams (0.33 mole) of pyridine.

Example8 N,N-dibutyilinol'efiy This product was prepared following the exact procedure of Example 2 except for the substitution of oleoyl chloride by linoleoyl chloride.

Example 9 a small amount of a 10 percent solution of Na SO The metachlorobenzoic acid was removed by a NaHCO wash, followed by water washing. The CHCl solution was then dried with anhydrous Na SO and the CHCl stripped off to recover the product N,N-dibutyl-9,10- epoxystearamide, oxirane content 3.45 percent (theory 3.91 percent). 100 grams (0.24 mole) oflhisproduct was added to a we ll stirred slurry of 55 .7 g (0.73 mole) of thiourea and 89.5 g (0.73 mole) of benzoic acid in acetone. Stirring was continued for 3 hours beyond the terminal addition whereupon the benzoic acid was washed out with 38.8 g (0.36 mole) of Na CO 3 and the organic product extracted with hexanejThe organic phase extract was dried and stripped to recover the product N,N-dibutyl-9,l0 epithiostearamide containing 6.41 percent sulfur (theory 6.67 percent).

Example 10 Example 1 1 N,N-dibytl-9,10-l2,l3-diepithiostearamide This product was prepared following the procedure described in Example 9 except for the replacement of the N,N-dibutyloleamide of Example 9 by N,N- dibutyllinoleamide, and a doubling of the molar ratios of all reagents. The product analyzed as follows: peroxide was added dropwise to a slurry of 56 g thiourea in 1000 ml of acetone and the concurrent addition of 43.4 g of glacial acetic acid and the reaction mixture stirred for 3 hours. The glacial acetic acid was neutralized with Na CO and the episulfide, N- ethoxyethoxyethoxypropyl-9, 1 O-epithiostearamide, extracted with Skellysolve B and washed, dried, and stripped. Its elemental analysis was C 67.1 (66.52),

H 11.42 (10.88), N 2.67 (2.87), S 2.29 (6.57). Y

Example 13 N-Ethoxyethoxyethoxypropyl-9( 10)mercaptostearamide 173 g of N-ethoxyethoxyethoxypropyloleamide in CC], was treated in the cold with a CCl, soltuion containing 60.9 g of bromine. Any unreacted bromine was removed by a thiosulfate wash. 140 g of the resulting dibromo compound was added dropwise to a well stirred solution of 72 g of Na S'9H O in dimethylsulfoxide maintained at 80C.'Stirring was containued at 80Cfor 3 hours. Water was added and the reaction product was extracted with hexane; washed, dried, and stripped. Elemental analysis of the product was C 66.3 (66.5); H =11.1 (10.9), N 2.7 (2.9), S 4.4 (6.8).

' Example 14 N,N-Dibutyl-9( l0)[dibutylphosphono]stearamide 100 g of N,N-dibutyloleamide, Example 2, 148 g of dibutyl phosphite, and 1.29 of benzoyl peroxide catalyst were heated at 115C for 3% hours. Additional units of 1.29 g'of benzoyl peroxide was added after the cent C, 69.64 (theory 68,57); percent H, 10.93 (theory 10.76; percent N, 3.10 (theory 3.07); percent S, 11.7 (theory 14.06).

- by drying and stripping off the CHCl 171 g of this epfirst and second hours of reaction time. The excess dibutyl phosphite was then removed by distillation at reduced pressure, 0.45 mmHg. The stillpot contents showed strong adsorption bonds at 8, 9.3, and 9.7 microns characteristics of the phosphonate' group. The elemental analysis was C obs 71.46 (69.50), H obs 12.42 (11.92), N obs 2.20 (2.38), P obs 4.24 (5.28) percent respectively.

Example 15 N-9,10-l2,13-diepithiostearoylmorpholine This product was prepared-by the same procedure described in Example 9 except for the substitution of linoleoyl morpholine for the N,N-dibutyloleamide of Example 8 and the doubling of molar proportions of the m-chloroperbenzoic acid in the epoxidation step and the thiourea andbenzoic acid in the epithioation step. The elemental analysis was C obs 68.89

obs 4.00 (15.49) percent respectively.

Example 16 N,N Dibutyl-[9(10) phato]stearamide 44.7 g of dibutylhydrogen phosphate was added to 182.2 g of N,N-dibutyl-9,IO-epoxystearamide at 95C with stirring. Reaction conditions were continued for 3% hours after termination of the addition.

The reaction product was dissolved in commercial hex- -hydroxy-(9)10-dibutylphos- 5 drying and stripping, yielded the product. Elemental analysis was, C= obs 66.56 (65.91),H =obs11.04 (11.30). N=obs 2.90 (2.26), P=obs 3.04 (4.20).

Example 17 N-[9( 10) mercapto-(9)10-dibutylphosphatostearoyl]- morpholine 12 g of dibutylhydrogen phosphate was added drop- I wise with stirring to 51.0 g of (9,10-epithiostearoyl)- morpholine, the preparation of Example 10, at 8590C and the heating and stirring continued for 3 hours beyond the terminal addition. The reaction prodact was dissolved in commercial hexane and any excess or unreacted 7 1 IIO (0 04119):

was neutralized and washed out with aqueous 10 percent Nal-lCO The hexane extract was washed several 'times with water dried and stripped. The elemental analysis of the product was C obs 66.74 (69.36), H =obs 10.69 (1 1.05), N obs 2.89 (3.32), S =obs 3.27 (2.17), P obs 1.68 (2.10) percent respectively.

Example 18 rpm for 1 hour at 120C and 50 kg load were compared.

with the scars obtained using commercial lubricants such as Aeroshell Mil-L-708 (Di-Z-ethylhexyl sebacate and additive), Gulfpride, single G, MS, multiviscosity,

and 100 sec. paraffin oil. The results of these tests are reported in Table 1. i

TABLE I ANTIWEAR LUBRICANT PROPERTlES OF FATTY ACID AMIDES Avg Wear Scar. mm

COMPOUND without With additive additive Additive 1 N,N-Bis(2-ethoxy- N,N-Di-butyl-9,10-epicthyl)oleamide 0.597 0.735 thiostearamide 2 N,N-Di-n-hutyl-9.l0-

epilhiostearamide 0.842 none 3 Oleoylmorpholine 0.623 0.658 do. 4 N,N-Dimethyloleamidc 0.797 0.987 do. 5 N,N-Di-n-propyloleamide 0.908 0.885 do. 6 N,N-Di-n-hexyloleamide 0.893 0.898 do. 7 N,N-Di-n-butylerucamide 0.758 0.798 do. 8 N,N-Di-n-buty1 amide of Sel. hydrogenated cottonseed fatty acids 0.798 0.958 do. 9 N,N-Bis(2-Methoxyethyl)o1eamide 0.626 0.725 do.

10 N.N-Dibutyloleamide 0.710

11 N-O1eoy1-4-propyl- K/ilperidine 0.847 l2 orpholide of. sel.

hydrogenated cottonseed fatty acids 0.642 1.3 N-Methyl-N-butyloleamide 0.607 l4 N-Ethoxycthoxyethoxy- '5 Ring) loeantikilde I 0.503

- ox e ox ro olcamide W W 0.526 16 N-methoxylsopropyloleamide 0.705 17 N-Methoxyethyloleamide 0.420 18 102 sec Paraffin Oil 0.902 N-methoxyethyloleamide 19 D.O.S. 0.906 do. 20 N,N-Dibuty1-9(10)- carbobutoxyoctadecanamide 0.610

21 102 sec Paraffin Oil 0.818 N,N-Dibutyl-9( l0)- carbobutoxyoctadecanam ide 22 D.O.S. 0.945 do.

23 N-[9(10)mercapto- (9)10-dibutylphosphatostearoyl] 0.615 morpholine 24 102 sec Paraffin Oil 0.552 N-[9(10)mercapto- (9)10-dibuty1phosphatostearoyllmorpholine 25 D.O.S. 0.535 do.

hydroxy-(9)l0-dihutylphosphato] steuramide 0,498

27 102 sec Paraffin 011 0.498 N.N-Dibutyl-[9(10)- hydrox -(9)10-dibutylp ospljato] stearami e 28 D.O.S. 0.498

[dibutylphosphono] stearamrde 0,530

TABLE l-Continued AN'l'lWliAR LUBRICANT PROl'liR'llES ()F FATTY A('ll) AMlDliS Av Wear Scar. mm

COMPOUND without With 5% additive additive Additive 30 N-Ethoxyethoxyethoxypropyl-9,l-epithiostearamide 0.707 3 l N-Ethoxyethoxyethoxypropyl-9( l0)mercaptostearamidc 0.690 32 N-(9,l0-l2,l3-dicpithiostearoyhmorpholine 0.665 33 Bis(2-ethylhexyl)sebacute 0.872 34 100 sec Paraffin Oil 0.803

35 "Acre Shell (Mil- 7808) I 0.587 36 Gulf Pride, Single G. MS, multiviscosity 0.447 37 100 sec Paraffin Oil 0.813 N,N-Dibutyl-9,l0-

. l2,l3-Diepithiostearamide 38 Bis(2-ethylhexyl) sebacate 0.836 do. 39 lOO sec Paraffin Oil 0.723 N-9,l0-epithiostearoyl morpholine 40 Bis(2-ethylhexyl) sebucate 0.9l do. 41 100 sec Paraffin Oil 0.9l7 N,N-Dibutyl-9,l0- dichlorostearamide 42 Bis(2-ethylhexyl) sebacate 0.848 do.

It can be seen from the data presented that the N-' alkoxyalkyl and N,N-di(alkoxyalkyl)oleamides, withlubricants.

Example 19 The various amides were evaluated as extreme pressure lubricants or additives a Shell 4:ball extreme pressure tester at 1440 RPM following ASTM Procedure D 2596-67T. Loads were increased in increments of 20 Kg to weld point and the test run for'l minute or to weld whichever occured first. Commercial hypoid fluid SAE No. 90 was employed as the control E.P. lubricant. The performance of the amides tested is given in Tables II, III, and IV.

TABLE ll EXTREME PRESSURE TESTS (ASTM D2596-67T) Weld Point Wcld Point COMPOUND (No (with 5% additive) No. 2)

l N,N-Bis(2-ethoxyethyl) oleamide 120 170 2 N,N-Di-n-butyl-9,lO-epithiostearamide 300 3 Oleoylmorpholine 120 I 4 N,N-Dimethyloleamide 5 N,N-Di-n-propyloleamide 120 6 N,N-Di-n-hexyloleamide 120 l80 7 N,N-Di-n-butylerucamide 120 200 8 N,N-Di-n-butyl amide of hydrogenated cottonseed fatty acids l20 170 9 N,N-Bis(2-Methoxyethyl)oleamide 120 10 N-Methyl-N-butyloleamide l00 ll N.N-Dibutyl-9.lO-epithiosteal-amide 300 I2 N.N-Dibutyl-9.l0-l2.l3-diepithiostearamide 440 l 3 N-Ethoxyethoxyethoxypropyoleamide 120 14 N-Ethoxyethoxypropyloleamide l2 l5 N-Melhoxyisopropyloleamide 100 lb N-lvlethoxyethyloleamide 100 l7 N-9.l0-epithiostearoylmorpholine 380 I8 Bis(Z-ethylhcxyhsebacate 120 l9 l00 sec Paraffin Oil [00 20 2x0 SAE No. 90 Commercial hypoid fluid TABLE I11 EVALUATION OF N,N- DlBUTYL-9,10-l2,13-D1EP1TH1OSTEAR-' AM1DE AS AN ADDlTlVE AND AS A BASE O1L1N EXTREME PRESSURE TESTS. (ASTM D2596 -67T) BASE OIL ADD1T1VE LOAD, Kg WEAR SCAR I mm 100 sec Paraffin Oil v 140 1.90 do. do. 200 2.35 do. do. 220 2.75 do. do. 240 We1d5 scc.

Bis(Z-cthylhexyhsehacale (5%) 120 1.51 do. do. 180 1.59 do. do. 190(1.S.) 2.47 do. do. 200 We1d-4 sec. do. 240 2.88 do. do. 260 3.55 do. do. 270 Weld-10 sec.

N,N-Dibuty1-9,10-12.l3-

dicpithiostcurumide None 1.38 do. do. 160 1.61 do. do. 200 1.89 do. do. 280 2.13 do. do. 320 2.47 do. do. 360 2.70 do. do. 400 2.88 do. do. 440 Weld-46 sec.

- "'lncipicn! seizure EXTREME PRESSURE TESTS 0N N-ETHOXYETHYOXYETHOXYPROPYL-9.10-EP1- THIOSTEARAMIDE (PC-O-No. 7682) BASE OIL ADDITIVE APPLIED AVE. SCAR LOAD 7682 None 120 1.05 do. do. 160 1.75 do. do. 240 2.35 do. do. 300 2.19 do. do. 340 2.55 do. do. 360 2.62 do. do. 380 weld 102 sec Paraffin 011 7682 (5%) 120 2.28 do. do. '140 2.46 do. do. 150 weld D.0.S. 7682 (5%) 120 2.23 do. do. 2.44 do. do. weld EXTREME PRESSURE TESTS ON N-ETHOXYETHOXYETHOXYPROPYL-9(10)- MERCAPTOSTEARAMIDE (PC-O-No. 7683) BASE 01L ADDITIVE APPLIED AVE. SCAR.

LOAD

Kg mm 7683 None 200 1.54 do. do. 300 2.26 d0. do. 400 2.25 do. do. 450 2.15

do. do. 500 2.15

111: sec Paraffin Oil 7683 (5%) 120 1.97 do. do. 140 2.35 do. do. 150 2.54 do. do. weld D.O.S. 7683 (571) 120 1.68 do. do. 140 2.18 do. do. 160 2.59 do. do. 2.72 do. do. weld "Test sxopped because of extreme decomposition. Did not we ld.

EXTREME PRESSURE '1ES'1'S ()N N-(LlO-IZJ3-1)1EP1'1'HIOSTEAROY1.)M()R1HO1.1N1 (PC-O-No. 7684) BASE OIL ADD1T1VE APPLIED AVG. SCAR.

LOAD

Kg mm 7684 None 200 2.21 do. do. 260 2.38 do. do. 340 2.43 do. do. 400 2.75 do. do. 460 2.90 do. do. 500 2.98"

102 sec Paraffin 011 7684 2.23 do. do. 2.61 do. do. 2.74 do. do. weld DDS 7684 (5%) 120 2.54 do. do. 140 2.58 do. do. weld N-Methoxyethyl oleamide 7684 (5%) 140 2.53 do. do. 2.77 do. do. weld Test stopped because of extreme decomposition. Did not weld.

EXTREME iREssURE TESTS oN N,N-DlBUTYL-9(10)-(D1BUTYLPHOSPHONO)STEAR- AM1DE(PC-O-No. 7685) APPLIED AVE. SCAR.

LOAD BASE OIL ADD1T1VE Kg mm 7685 None 120 3.05 do. do. 140 4.50 do. do. 150 weld EXTREME PRESSURE TESTS ON N.N-DlBUTYL-[9(10)-HYDROXY-9(1 0)- DIBUTYLPHOSPHATOlSTEARAMIDE (PC-O-No. 7686) 7686 None 200 0.887 do. do. 300 2.78 do. do. 340 4.32 do. do. 350 4.50 do. do. 360 weld 100 sec Paraffin Oil 7686 (5%) 120 2.28 do. do. 140 2.80 do. do. 150 3.01 do. do. 160 we1d D.O.S 7686 (5%) 120 1.95 do. do. 140 2.85 do. do. 150 3.03 do. do. 160 weld EXTREME PRESSURE TESTS ON N-[9(10)-MERCAPTO-9(10)-BUTYLPHOSPHATO- STEAROYLIMORPHOLINE (OC-O-No. 7687) APPLIED AVE. SCAR,

LOAD BASE .OlL ADDITIVE Kg mm 08 None 120 0.608 do. do. 160 1.45 do. do. 200 1.40 do. do. 240 1.70 \10 do. 280 3.36"

EXTREME PRESSL'RE TESTS ON N.N-D1BUTYL-9( 101-CARBOBL'TYOXYOCTN DECANAMIDE (PC-O-No. 7688) 7688 None 80 1.92 do. do. 90 2.18 do. do. 100 2.45 do. do. 120 weld "Tcsx smpped because of extreme decomposition and noxious fumes. Did not weld.

TABLEIV EVALUATION OF N-JJO-EPITHIOSTEAROYL MORPHOLINE AS AN ADDlTlVE AND AS A BASE OIL IN EXTREME PRESSURE TESTS (ASTM D 2596-671") LOAD WEAR SCAR BASE OIL ADDlTlVE Kg mm I sec Paraffin Oil 120 2.00 do. do. 140 2.80 do. do. I60 3.25

do. do. I80 weld, sec.

Bis(2-ethylhexyl) (5%) 80 1.57 sebacate do. 120 2.03 do. do. 140 2.4] do. do. 160 2.94 do. do. 180 3.00

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3746644 *Aug 31, 1971Jul 17, 1973Us AgricultureN-substituted fatty acid amide lubricants
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3991079 *Oct 31, 1975Nov 9, 1976The Lubrizol CorporationDispersants, antistatic agents and corrosion inhibitors for fuels and lubricants
US6706670Aug 29, 1997Mar 16, 2004Solutia, Inc.Carboxylic acids and salts and phosphates, borates, phosphonates, phosphites and hypophosphites
DE2945851A1 *Nov 13, 1979May 14, 1980Ethyl CorpSchmieroel-zubereitung
WO1997019909A1 *Nov 26, 1996Jun 5, 1997Boehringer Mannheim GmbhAmino alcohol derivatives, methods of producing said derivatives and medicaments containing them
WO1998008919A2 *Aug 29, 1997Mar 5, 1998Winsor R ChoNovel water soluble metal working fluids