United States Patent (19) 11) 4,406,802 Horodysky et al. 45) Sep. 27, 1983 (54) FRICTION REDUCING ADDITIVES AND 56) References Cited COMPOSITIONS THEREOF U.S. PATENT DOCUMENTS 3,009,791 ll/1961 Emrick ............................... 44/76 X (75) Inventors: Andrew G. Horodysky, Cherry Hill; 3,303,208 2/1967 Liao .................................... 44/76 X Joan M. Kaminski, Clementon, both 3,445,498 5/1969 Cyba. 252/49.6 X of N.J. 3,505,226 4/1970 Cyba. ... .252/49.6 3,533,945 10/1970 Vogel ..... ... 252/49.6 3,544,614 12/1970 Schwartz 252/49.6 X 73 Assignee: Mobil Oil Corporation, New York, 3,560,386 2/1971 Cyba. .................................. 252/49.6 N.Y. 4,022,713 5/1977 Waldstein ....................... 252/389 R Primary Examiner-W. J. Shine Attorney, Agent, or Firm-Alexander J. McKillop; (21) Appl. No.: 259,219 Michael G. Gilman; Howard M. Flournoy (57) ABSTRACT Filed: Apr. 30, 1981 (22) Mixed borated alcohol-amines, alcohol-amides, alcohol ethoxylated amines, alcohol-ethoxylated amides, al (51) Int. Cl. ........................ C10M 1/20; C10M 1/32; cohol-hydroxyester, alcohol-imidazolines and alcohol ClOM 1/54 hydrolyzed imidazolines and mixtures thereof are effec (52) U.S. C. ....................................... 252/49.6; 44/76; tive multifunctional additives when incorporated into 252/389 R; 252/400 R various organic media. 58 Field of Search .............. 252/49.6, 389 R, 400 R; 44/76; 568/1 12 Claims, No Drawings 4,406,802 FRCTION REDUCING ADDITIVES AND ROH COMPOSITIONS THEREOF where R may contain any desirable number of carbon BACKGROUND OF THE INVENTION 5 atoms based on such factors as oil solubility; however, R usually will contain from about 10 to about 30 carbon 1. Field of the Invention atoms and is an alkyl or substituted alkyl group which This invention relates to lubricant additives and com may be primary, secondary or tertiary, straight-chain, positions thereof and, more particularly, to lubricant compositions comprising oils of lubricating viscosity or branched or cyclic, it may contain one or more double greases prepared therefrom containing a minor friction 10 bonds, halogen or one or more sulfur atoms or an aro reducing amount of certain borated mixed alcohols, matic ring. Examples include such as decyl alcohol, amides, amines and esters. dodecyl alcohol, oleyl alcohol, stearyl alcohol, p-nitro 2. Description of the Prior Art benzyl alcohol, ethyl-octyl alcohol and mixed C12-C1s Many means have been employed to reduce overall linear alkanols. Alcohols having from about 12 to 24 friction in modern internal combustion engines, particu 15 carbon atoms are particularly useful. Particularly pre larly automobile engines. The primary reasons are to ferred are C10-C15 linear alkanols and C10-C12 branched reduce engine wear, thereby prolonging engine life and alkanols such as 2-ethyl-octanol and C15 alcohols such to reduce the amount of fuel consumed by the engine. as oleyl alcohol and stearyl alcohol. Many of the solutions to reducing fuel consumption The generalized structure of the hydroxyalkyl or have been strictly mechanical, as for example, setting 20 hydroxyalkenyl hydrocarbyl amides useful herein is: the engines for a leaner burn or building smaller cars O and smaller engines. However, considerable work has 2 been done with lubricants, mineral and synthetic, to R-C N / enhance their friction properties by modifying them 25 N with friction reducing additives. N Certain alcohols, mixtures of alcohols and other or (CH2CH2O).H ganic compounds have been used as intermediates in the manufacture of a variety of lubricant additives. How where R is as described above. Examples include bis(2- ever, the use of alcohols themselves, for example, has 30 hydroxyethyl) oleamide, bis(2-hydroxyethyl) cocoa not been widespread as engine oil additives because of mide, bis(2-hydroxyethyl) soyamide, bis(2-hydrox potential oxidative and thermal instability and volatility yethyl) octadecylamide, polyoxyethylene (5) oleamide, difficulties. It has now been found that certain borated polyoxyethylene (4) cocoamide, polyoxyethylene (5) mixed alcohols, amides, amines and hydroxy esters pro soyamide, etc. x and y may be the same or different and vide friction reducing characteristics that non-borated 35 each is from 1 to about 10, however, the sum of x and y compositions lack; in addition, the borated mixed deriv must always be 2 or greater. Propoxylated amides could atives improve oxidative and thermal stability, volatility also be used. and bearing corrosion inhibiting properties. These bo The generalized structure of the amines before bora rated mixed compositions are, to the best of applicants' tion is: knowledge, novel and have not been used as friction 40 reducing or multifunctional additives suitable for use in lubricating compositions and in fuels such as in gasoline, diesel fuel, jet fuel, etc. to improve fuel economy. The subject mixed borated compositions perform better than where R is as described above. Both saturated and un mixtures of individual borated materials, e.g., borated 45 saturated amines can be used; diamines and polyamines mixed oleyl amine and oleyl alcohol outperforms a are also useful. Examples include stearyl amine, cocoa mixture of borated oley alcohol and borated oley mine, laurylamine, soyamine, N-oleyl. 1,3-propylenedia a1e. mine, oleyl amine, aniline and dinitrophenylamine. R as SUMMARY OF THE INVENTION 50 stated hereinabove with respect to both the amides and This invention is directed to novel additive com the amines disclosed herein is as defined herein above. pounds, i.e., borates of mixed alcohols, amides, amines, The generalized structure of the hydroxyalkyl or and hydroxy esters, ethoxylated amines, and ethoxyl hydroxyalkenyl hydrocarbyl amines suitable for use in ated amides and mixtures thereof such as mixed alcohol, the present invention is: amine borates, mixed alcohol, and ethoxylated amine 55 borates. In addition to these novel compounds the in vention is also directed to lubricant compositions hav ing reduced friction containing such compounds and to a method of reducing fuel consumption in internal com bustion engines by treating the moving surfaces thereof 60 with said compositions. Further, as noted hereinabove and as stated hereinabove x and y may be the same or the novel compounds referred to also possess significant different and each is from 1 to about 10 and the sum of antioxidant characteristics and bearing corrosion inhib x and y must be 2 or greater. iting properties. Examples are bis(2-hydroxyethyl) oleylamine, bis(2- 65 hydroxyethyl) soyamine, bis(2-hydroxyethyl) cocoa DESCRIPTION OF SPECIFIC EMBODIMENTS mine, bis(2-hydroxyethyl) octadecylamine, polyoxyeth The generalized structure of the alcohols before bora ylene (5) oleylamine, polyoxyethylene (5) soyaamine, tion is: polyoxyethylene (4) cocoamine, etc. - 4,406,802 3 4 The generalized structure of the hydroxyesters are erally found in the non-mixed borated materials and to exemplified by the following general structure: an even greater degree than the individual borated ma terials. That is, the borated mixed materials perform in R O N a far superior manner to an equivalent physical mixture C-O-C-R of each specific borated material. Further, the higher 1 molecular weight borates have increased resistant to R (HoH), hydrolysis and retain their friction reducing characteris O tics even in the presence of water at elevated tempera where R is a hydrocarbyl group having from about 10 tures. to about 30 carbon atoms; said hydrocarby moiety may be alkyl, straight or branched, cyclic or substituted and Exemplary mixed borates so prepared are mixed al may contain one or more double bonds, halogen or one cohol-amine borates such as: or more sulfur atoms or aromatics rings; R = CH2OH, 15 CH3 or H; R = CH2OH or H and y is from i to about 5. The hydroxy esters may be made by the reaction of polyhydroxy alcohols with organic acids. For example, glycerol and oleic acid are used in the preparation of N R" / glycerol monooleate. Thioglycerol hydroxyesters can 20 also be used. The hydroxy esters must contain at least one free where a and b = 1 or 2 c = 0, or 1, R'' and R' have from hydroxyl group but may contain two or more. The about 10 to about 24 carbon atoms or can be H. hydroxy esters may also contain one ester group (as in glycerol monooleate) or more (as in glycerol dioleate). The structure of mixed alcohol-ethoxylated amide The esters can be used in pure form, or preferably in 25 borates can be generalized as follows: mixtures such as mixtures of glycerol mono- and diole ate. Sorbitan hydroxyesters and hydroyesters prepared (O-CH2CH2) O from trimethylolpropane and pentaerythritol are also useful, e.g., sorbitan monooleate, trimethylolpropane 30 monooleate, trimethylolpropane dioleate, pentaerythri (O-CH2CH2) tol dioleate monolaurate and the like. Also useful are hydroxyalkyl or hydroxyalkenylalkyl and various similar or related ring-opened borate struc or alkenylimidazolines and/or hydrolysis products of tures where R, R', x, y are as defined above or mixed the imidazoline. The general structure of such com alcohol-ethoxylated amines borates such as: pounds can be as described below: (O-CH2CH2). 40 and various ring-opened structures where x, y, R and where R has from about 10-30 carbon atoms and may 45 R" are as defined above. be alkyl or alkenyl, arylalkyl, alkyl aryl, etc. and X is The structure of mixed alcohol-hydroxyester borates from 1 to about 5. Their respective ring-opened hydro can have the general structures: lysis products are made by treatment of the above described imidazolines with at least molar amounts of Water. SO sh-o--R The borated derivatives can be conveniently pro OCH O o duced by the reaction of selected mixtures of the com / (R"-O)-B pounds in accordance herewith with boric acid in a N suitable solvent or solvents at temperatures ranging OCH2 from about 10 C.