United States Patent (19) 11 Patent Number: 4,594,171 Horodysky et al. (45) Date of Patent: Jun, 10, 1986 54 FRCTION REDUCING ADDITIVES AND 56) References Cited COMPOSITIONS THEREOF U.S. PATENT DOCUMENTS 75 Inventors: Andrew G. Horodysky, Cherry Hill; 4,273,665 6/1981 Braid et al. ........................ 252/49.6 Joan M. Kaminski, Mullica Hill, both 4,406,802 9/1983 Horodysky et al................ 252/49.6 of N.J. 4,478,732 10/1984 Horodysky et al. ............... 252/49.6 Assignee: 73 Mobil Oil Corporation, New York, Primary Examiner-Jacqueline V. Howard N.Y. Attorney, Agent, or Firm-Alexander J. McKillop; 21 Appl. No.: 624,563 Michael G. Gilman; Howard M. Flournoy 22) Filed: Jun. 26, 1984 57 ABSTRACT Related U.S. Application Data Certain borated additive compounds, such as borated mixed ethoxylated amines and ethoxylated amides or 62 Division of Ser. No. 265,301, May 20, 1981, Pat. No. hydroxyalkyl imidazolines and hydroxyesters or hydro 4,478,732. lyzed hydroxyalkyl imidazolines and ethoxylated am 51 nt. Cl. ................ C10M 133/46; C10M 141/06; COM 141/12 ides and combinations thereof, provide highly effective (52) U.S. C. .............................. 252/49.6; 252/51.5 R; multifunctional characteristics for various lubricating 252/389 R; 252/400R media into which they are incorporated. 58 Field of Search ............. 252/49.6, 51.5 R, 400 R, 252/389 R 12 Claims, No Drawings 4,594,171 1. 2 yalkenyl hydrocarby imidazolines in various combina FRCTION REDUCING ADDITIVES AND tions. In addition to these novel compounds, the inven COMPOSITIONS THEREOF tion is also directed to lubricant compositions having significant multifunctional characteristics, such as for This is a division of copending application Ser. No. 5 example, reduced friction and increased oxidative and 265,301, filed May 20, 1981 and now U.S. Pat. No. thermal stability and to a method of reducing fuel con 4,478,732. sumption in internal combustion engines by treating the BACKGROUND OF THE INVENTION moving surfaces thereof with said compositions. 1. Field of the Invention O DESCRIPTION OF SPECIFIC EMBODIMENTS This invention relates to lubricant additives and com The generalized structure of the hydroxyalkyl or positions thereof and, more particularly, to lubricant hydroxyalkenyl hydrocarbyl amides useful herein be compositions having multifunctional capabilities com fore boration, is: prising oils of lubricating viscosity or greases prepared therefrom containing a minor amount of said multifunc 15 tional additive which is derived from various borated O / (CH2CH2O).H22 mixtures of hydroxyesters, ethoxylated hydrocarbyl Re-CN amines, ethoxylated hydrocarbyl amides, hydroxyalkyl N or hydroxyalkenyl hydrocarbyl imidazolines, or hydro (CH2CH2O).H lyzed hydroxyalkly or hydroxyalkenyl hydrocarbyl 20 where R usually will contain from about 10 to 30 car imidazolines. bon atoms and is an alkyl or substituted alkyl group 2. Description of the Prior Art which may be primary, secondary or tertiary, straight Currently there is a serious effort on the part of the chain, branched, or cyclic and may contain one or more automotive industry and the oil industry to provide double bonds, halogen or one or more sulfur atoms or means for prolonging engine life and reducing the 25 an aromatic ring. x and y may be the same or different amount of fuel consumed by internal combustion en and each is from 1 to about 10, however, the sum of x gines. Many solutions have been tried; some strictly and y must always be 2 or greater. Propoxylated amides mechanical, some have been done with lubricating oils can also be used. A few examples of the above described and some have been done by adding friction reducing amide structure include bis(2-hydroxyethyl)oleamide, additives thereto. It has now been found that certain 30 bis(2-hydroxyethyl)cocamide, bis(2-hydroxyethyl)- borated mixed hydroxy esters and hydrolyzed hydroxy soyamide, bis(2-hydroxyethyl)octadecylamide, poly alkyl or hydroxyalkenyl hydrocarbyl imidazolines; bo oxyethylene (5) oleamide, polyoxyethylene (4) cocoa rated mixed hydrolyzed hydroxyalkyl or hydroxyalke mide, polyoxyethylene (5) soyamide, etc. nyl hydrocarbyl imidazolines and hydroxyalkyl or hy The generalized structure of the hydroxyalkyl or droxyalkenyl hydrocarby imidazolines; borated mixed 35 ethoxylated hydrocarbyl amides and hydrolyzed hy hydroxyalkenyl hydrocarbyl amines, in accordance droxyalkyl or hydroxyalkenyl hydrocarbyl imidazo herewith before boration, is: lines; borated mixed ethoxylated hydrocarbyl amines and hydrolyzed hydroxyalkyl or hydroxyalkenyl hy drocarbyl imidazolines; borated mixed ethoxylated hy drocarbyl amines and hydroxyesters; borated mixed ethoxylated hydrocarbyl amides and hydroxyesters; (CH2CH2OH borated mixed hydroxyalkyl or hydroxyalkenyl hydro and as stated hereinabove x and y may be the same or carbyl imidazoline and hydroxyesters; borated mixed different and each is from 1 to about 10, with the pro ethoxylated hydrocarbyl amines and ethoxylated hy 45 viso that the sum of x and y must be 2 or greater. A drocarbyl amides; borated mixed ethoxylated hydro non-exhaustive list of examples include bis(2-hydroxye carbyl amides and hydroxyalkyl or hydroxyalkenyl thyl)oleylamine, bis(2-hydroxyethyl)soyamine, bis(2- hydrocarby imidazolines; borated mixed ethoxylated hydroxyethyl)cocoamine, bis(2-hydroxyethyl)oc hydrocarbyl amines and hydroxyalkyl or hydroxyalke tadecylamine, polyoxyethylene (5) oleylamine, poly nyl hydrocarby imidazolines, and borated mixtures of 50 various such combinations provide multifunctional oxyethylene (5) soyaamine, polyoxyethylene (4) cocoa characteristics that are not obtainable with the individ mine, etc. ual borated materials or physical mixtures of such bo The generalized structure of the hydroxyesters, use rated materials. The borated derivatives disclosed ful herein before boration, is exemplified by the follow 1ng: herein provide improved oxidative and thermal stabil 55 ity, volatility, bearing corrosion inhibiting properties and friction reduction relative to the individual borated materials. These borated mixtures are to the best of applicants' knowledge novel and unknown heretofore and thus accordingly have not been previously used in 60 the lubricating art. SUMMARY OF THE INVENTION where This invention is directed to novel, additive com R"=CH2OH, CH3 or H pounds, that is, borates of mixed hydroxy esters, ethox 65 R's CH2OH, H, or CR2'OCOR ylated hydrocarbyl amines, ethoxylated hydrocarbyl y = 1 to 5 amides, hydroxyl alkyl or hydroxyalkenyl hydrocarbyl The hydroxy esters must contain at least one free imidazolines, and hydrolyzed hydroxyalkyl or hydrox hydroxyl group but may contain two or more. The 4,594, 171 3 4. hydroxy esters may also contain one ester group (as is sion inhibiting properties not generally found in the glycerol monooleate) or more (as is glycerol dioleate). non-borated material and are superior to equivalent The esters can be used in pure form, or preferably in physical mixtures of the individual borated materials. mixtures such as mixtures of glycerol mono- and diole The higher molecular weight borated mixtures also ate. R is a hydrocarbyl group having from about 10 to 5 appear to be relatively resistant to hydrolysis and retain about 30 carbon atoms and said hydrocarby moiety their multifunctional characteristics even after being in may be alkyl, straight or branched, cyclic or substi the presence of water at elevated temperatures. tuted; and may contain one or more double bonds, halo Exemplary mixed borates so prepared are mixed hy gen or one or more sulfur atoms or aromatic rings and droxyalkyl or hydroxyalkenyl hydrocarbyl imidazo y is 1 to about 5. The hydroxy esters may be made by 10 the reaction of polyhydroxy alcohols with organic acids line-ethoxylated hydrocarbyl amine borates such as: where glycerol and oleic acid are used in the prepara tion of glycerol monooleate. Thioglycerol hydroxyes CH2CH2 (OCH2CH2) ters can also be used. N Y -UH2uriu-CHCHO b^ Nam-Ra Sorbitan hydroxyesters and hydroxyesters prepared 15 N1 N / from trimethylolpropane and pentaerythritol are also (OCH2CH2) useful, e.g., sorbitan monooleate, trimethylolpropane R monooleate, trimethylolpropane dioleate, pentaerythri tol dioleate monolaurate and the like. The mixed hydrolyzed hydroxyalkyl or hydroxyalke Also useful are hydroxyalkyl or hydroxyalkenyl alkyl 20 nyl hydrocarbyl inidazoline-ethoxylated hydrocarby or alkenylimidazolines and/or hydrolysis products of amide borates included in the present invention are such the imidazoline. The general structure of such com 2S pounds can be as described below: CH2CH2 (OCH2CH2) O N 25 N? Y re CHCHO2Uhiu- b^ YN re-C-R,R etc. / Yeh, N1 N / Re-C H2 (OCH2CH2) R N/N 30 R is defined above. (CH2CH2O).H A generalized structure of useful mixed ethoxylated hydrocarbyl amine-ethoxylated hydrocarbyl amide bo where R is about 10-30 carbon atoms and may be alkyl rates is as follows: or alkenyl, arylalkyl, alkyl aryl etc. and x is 1 to 5. Their resepctive ring-opened hydrolysis products are made 35 O (CH2CH2O). by treatment of the above-described imidazolines with / at least molar amounts of water and result in structures RCN B-(OCH2CH2). N / such as: (CH2CH2O) N-R (HOCH2CH2) Various similar or related ring-opened borate struc tures, where R, x, and y are as previously defined O above, are also included with all of the mixed borates O (CH2CH2O).H. 45 disclosed hereinabove. / RCN Mixed hydroxyester-ethoxylated hydrocarbyl amine borates such as: CH2CH2NH2 CH2CH2O where R and x are defined as above. 50 The borated derivatives are conveniently produced RN B-O-CH2 by the reaction of the selected mixture of compounds N / with, for example, boric acid, in the presence of a suit CH2CH2O (HOH). able solvent or solvents at temperatures ranging from CH:or about 110° C. to about 280 C. Specific reactin condi- 55 O tions and molar equivalents vary with the various reac tants and can be readily determined by one of ordinary skill in the art. Besides direct treatment with boric acid other boration procedures several of which are well CH2CH2OH RN OCH2 known in the art can be used, for example, transesterifi- 60 N / cation with a trialkyl borate such as tributyl borate.