US2255085A - Lubricating composition - Google Patents

Description

to 'form a microscopic ,flim

The halogenated carbon indicated as preferable in surfaces and exert venting subsequent fusing taneo .-may be expressed as follows: ,(;1)v 1 Ro Patented Sept. 9, 1941 4 UNITED STATES PATENT OFFICE .RBSSUED 2,255,085 LUBRICATlNG-COMPOSITION Carl F. Prutton, Cleveland, and Albert K. Smith,

Shaker,Heights,'0hio, assignors to The Lubri- Zol Development Corporation, Cleveland, Ohio,- a corporationofDelaware No Drawing. Application November 21, 1938,

Serial No. 241,606 4 Claims. (Cl. 252-457) October 22,1937,- now Patent No. 2,204,620.

It has been explained that the reason why such'compounds thus improve the extreme pressure characteristics of the lubricant probably is due to thefact that such addition agents chemically react with the bearing surfaces under the conditions imposed by relative movement and extreme pressure between the bearing surfaces t of ametallic halide which prevents'seizing between the bearing surfaces by acting as an anti-fluxing agent.

ring compounds were is taught that the lubricating properties of a (Note: The hydrogen evolved by (2) probably would act to reduce one or more of the organic compounds rather than to appear as free hydrogen.)

The correctness of the foregoing theory is-substantiated by the fact that when a chlorinated said patents dueto the fact that such compounds are relatively "stable, 1'. e.,they do not readily hydrolyze in the presence of moisture which usually occurs in varying quantities in mineral oils. In other words, the halogenated carbon ring compounds are sumciently stable so that decomposition and attack thereof upon the metallic surfaces occurs only in the areas where extreme pressure is enacountered, i. e.', on the bearing surfaces.

One theory of the action of halogen 'compounds; specifically chlorine compounds, in increasing film strength, assumes that, as above indicated, under the stress of the rubbing action of bearing surfaces in motion under load, chlorides of the bearing metals are formed on their at HCl-ROH tact-1ra R x c main: andone of the metals of the aring'surfaces; P

an anti-fluxing effect in p reused without the addition of some other lubri- I larly pointed out in the claims.

, ture and especially of free water is objectionable in a lubricant besides being a highly variable factor in normal service, it is advisable to supply an oil soluble substitute for the same.

It is the principal object of this invention, therefore, to provides. lubricating composition as the type utilizing halogenated organic compounds as the extreme pressure addition agent but so modified as to be effective in the manner defined without being dependent upon the presence in-the lubricating composition of some addition material such as water.

Other objects of our invention the description proceeds. v I

To the accomplishment of theforegoing and related ends, said invention, then consists of the means hereinafter fully described and The following description sets forth d t one approved combination of ingredients em' bodying our invention, suchdisclosed means 'constituting, however, but one of various forms in which the principle of the invention may be used.

Broadly stated, thisvinvention comprises the use as a lubricant of oxygen and halogen bearing organic compounds and more specifically, oxygen and halogen bearing organic ring compounds,

either used alone or incorporated with any suitable oil base.

The oxygen which is included inthe molecule of the addition agent acts to increase the effectiveness of the latter in raising the film strength of a mineral. oil to which the addition agent is added or toimprove the lubricatihg properties of the halogenated compound when then cause an increase in the film will appear particucant. The oxygen probably acts in the same way as water in making possible the formation of hydrochloric acid as an intermediate step in the surface reaction above explained.

By combining in a. single molecule the halogen and the oiwgen atoms, a lubricant is afl'ectedin two ways:

First: The oxygen is always available at the exact point where required; and

Second: The molecule is more strongly ab-- sorbed by metal surfaces than similar halogen compounds which .do not contain oxygen.

The' latter circumstance enhances the efl'ect of equivalent to an increase in concentration of the compound at the bearing surfaces.

We have found that certain. oxygen-containing organic ring compounds which havebeen chlorinated and added to a lubricatingoil are capable of improving the properties of such oil, particularly when employed for thin-film lubricating purposes. The addition of these certainoxygen containing organicring compounds which have been chlorinated and added the lubricating oil have been found to improve the properties M thereof to an even greater extent than certain similar chlorinated hydro-carbons, notably when added in very small amounts.

The halogen and oxygen-containing organic ring compounds added to a suitable oil base .are.

. as above indicated, preferably of the chlorinated species. and particularly the compounds which have been found to produce very satisfactory results, may be classified as follows; viz:

(1) Hydrogenation products of benzene (e. g. cyclohexane, cyclohexene, cyciohexadiene). (2) Hydrogenation products of naphthalene (e. g. decahydronaphcompounds containing both heterogeneous ring .small amounts of such compounds because it is 11'. Indirectly some other atom, i. e'.,- in the form of an structures and carbon ring structures.

. The foregoing compounds may also be classifled according to the nature ofthe attachment of the oxygen to the compound, viz:

I. Directly attached to one or more carbon atoms, as in the case of: (1') Ethers and analogous compounds. (2") Compounds containingthe EG-OH radicle, such as alcohols and other derivatives of carbinol (including phenols, cresols, naphthols etc.) (3) Compounds containing the carbonyl C=O) radicle, such as aldehydes, ketones, organic acids, esters and salts of organic acids, thio-acidsand esters of thio-acids. (4') Compounds in which oxygen forms a .part of the ring structure, e. g.

furan and its derivatives, anthraquinone, etc. attached through the means of inorganic radicle, e.,g.:

- Amide Phosphate Arsenate Phosphite 'Arsenife Sulphate Chlorate Sulphite Chlorite Sulphinic acid Cyanate Sulphone Hydroxylamine" Sulphonic acid Hypochlorite Sulphoxide' Nitrate Thiocyanate Nitrite Isothiocyanate Nitro Thio-sulphate Nitroso 'Ihio-phosphate Perchlorate Isocyanate The halogen and oxygen-bearing organic ring compounds of the ester and salt type include thalene, tetrahydronaphthalene' etc. (3) Naphthenes, naphthenic acid, etc. (0) Of mixed type such as oxygen and halogen-bearing derivatives of indene, hydrindene, hydranthracene, etc. 1 II. "Heterogeneous ring type compounds:

(a) 01' the aromatic or allied type including oxygen and halogen-bearing deucts, or both. They may be formed by halogenarivatives of'pyridine, quinoline, etc. j

e (b) Other types such as oxygen and halo gen-bearing derivatives of furar i and its derivatives vpyrrole etc..

Included in Class II are two principal types of compounds, viz: Compounds in which all of the ring structures are of the heterogeneous type and and of thiophene,

compounds of the aromatic type which may be classified as follows:

1. Esters and salts of an aromatic acid;

2. Esters formed by the combination of a phenol, cresol, naphthol, etc. with an organic acid of either the fatty or aromatic type;

aromatic alcohol (either mono-hydric or poly-hydric) with an organic. acid of either the fatty or aromatic type.

In addition to the substituents containing oxygen, other substituents may also be present with-' out'destroying, and in certain cases, improving the effect on the lubricating qualities of the 011 3..An ester formed .by the combination of an such as other aryl groups, alkyl groups, and

amino and substituted amino groups,'imin o, azo, hydrazo, hydrazine, nitrile, mercapto', sulphide,

polysulphide. Specific examples of compounds of the various classes described above are halogen derivatives I of the compounds listed below. These derivatives may be substitution 'products,'addition prodtion of the compound listed, or of intermediate compounds or by some other method.

Class 'Acetanilide I(a)- -I"(3') Acetophenone I(a)-I(3') Aluminum phenyl mer- I(a)'-I'(3') capto 'stearate I Aluminum phenyl I(a)-'-1'(3'l stearate 1 Amylsallcy'late I( a)I-'(2') and (3) Amino phenol In the following table are given examples of aromatic acids, halogen-bearing derivatives of which may be employed as addition agents in accordance with our invention:

I Benmic acid Benzoic acid. derivatives Azobenzoic acid Mercapto benaoic acid Lauryl benzoic acid Salicylic acid Salicylic acid derivatives Ethyl salicylic acid Carboxylic acid Carboxylic acid derivatives Pyrrole carboxylic acid I Thiophene carboxylic acid Acetic acid "Acetic acid derivatives Class .Cinnamic acid Phenyl ethyl sulphate I(a)-II' P hthalic acid Phenyl ethyl sulphite' I(a)--II' Toluic-acid Phenyl ethyl sulphone 1(a) -II' Mercapto rosolic acid Phenyl ethyl tmosul' m Among the esters and salts, halogen derivatives Phate of which are likewise suitable for use as addi-. Phenyl' hydmxylamme tion agents, are the esters and salts which may Phenyl memapto gear I(a)I be derived irom'the aromatic acids listed imate mediately above and mono and *polyhydric alco- P 5g gg zgg i I(a) I hols, or other hydroxy compounds (including c a phenols). Specific examples of such alcohols and Phenyl naphthe ate 1(5) (3); (3 hydroxy compounds are those specifically identi- Phenyl naphthyl keton fl under on p g 5 Phenyl mmte lf Among the salts of aromatic acids, the halo- Phenyl oleate Ha) (3 gen-bearingderivatives of which may also be em- Phenyl oxydisulphide I(a)'-I (3 loyed as addition agents, arethe salts of the Phenyl Pheml aromatic acids listed above,includin'g the sodi- Phenyl ph gt (3) um, calcium, aluminum, magnesium, zinc and, Phenyl phenyl'naph' Kb) (3)' I'(3 A lead salts, and salts derived from ammonia, subthenatestituted ammonias and other organic bases such Phenyl phenyl-stearate: I(a) I'(3') as qumdune and fl m PP 9-way, Y A very important group of esters, halogenand esters a bearing derivatives of which are particularly i Propyl alcohol suited for use as addition agents, esp cially in Phenyl steam (3 certain types of lubricants, are the esters of alco- Phenyl t acid t 9 2 hols of the benzenoid type. Specific examples of Pyridine steam-t9 11(5)"?! (3 such alcohols are the following: Pyrrol stearate II(b)- I'(3) Sodium phenylmercap- I(a)I'(3') Benz alcohol tosteamte v Phenyl ethyl alcohol Sodium phenylstearate. I(a)I'(3') Benzhydml I Sodium thiobenroate I(a)I'(3')' Phenyl Stearanilid I I(a)I'(3') phenylmropyl alcohol Tertiary amyl phenol 1(a) -(I) (2') Phenyl benzyl a h 'Thiobenzoic acid I(a),I'(3')' a5 mfuryl 4 Toluic acid fI(8.)-I'(3') J Naphmfienzyl Tricresyl phosphate -I(a)- -.II' Cinnarnyl alcohol I p yl flrsenate I(a)II' This class of esters may be derived from alco- Trlp arsenite K n- I hols of thebenzenoid type, such as those listed p e yl Phosphate U 40 above andorganic acids, either aliphatic or aro-' Triphenyl P -W i matic or from such alcohols and inorganic acids. Tri-tertiary amyl 1(a) II' 1 Examples of such organic andsinorganic acids are ph nvl phosphate those listed under (6) (b) on page 5. Zinc benzoate. MF- The class of unsaturated oxygen compounds is Zinc phenylstearate 1(a) I'(3) particularly suited, after halogenation or halogen treatment, for use as addition agents in accordance with our. invention. The following is a clas- .sification or these unsaturated oxygen compounds along with specific examples of the various groups within this sub-class; v

( 1) Unsaturated alcohols, e. g.-

Vinyl ethyl alcohol Allyl alcohol Crotonyl alcohol Oleyl alcohol v Propargyl alcohol.

(2) Unsaturated aldehydes, e.. g.

Acrolein g Crotonaldehyde Hexadienal Octatrienal Citral Propargylic aldehyde (3) Unsaturated ketones, e. g.-

, Allyl acetone Di-allyl ketone Mesityl oxide Phorone Vinyl lauryl ketone Acetylenic ketones (e. g.

R-CEC-CO-R'),

such as: I Allylene methyl ketone' Allylene lauryl ketohe 2,265,086 t 34 ga es... Unsaturated acids, such as those Ketene listed under above. Acetyl ketene Aromatic acids, including: (4) Unsaturated ethers, e. g. Benzoic acid Di-vinyl ether 5 Phgthalic acids Di-allyl ether Salicylic acid 1 Allyl ethyl ether lfl lic acid Vinyl ethyl ether Cinnamic acid Ally1 iso-amyl ether y loliphatic acids, including: Allyl lauryl ether Naphthenic acids I Propargyl ethyl ether x ydrobenzoic acid (5) Unsaturated acids, e, g.- fieterocyclic a ids in ludin Vinyl acetic acid i i d. Vinylac'ryiic acid Pyrrol carboitylic acids Vinyl glycolic acid 5 n a c 8,, n u ne:' Acrylic id Hydro-halogen acids Crotonic acid y-halogen acidsv Oleic acid ulphurous acid Linoleic acid phuric acid Maleic'acid Thiosulphuric acid ,Fumaric acid rbonic acid Linolenic acid Thiocarbonic acids Elaeostearic acid y o en sulphide Propiolic acid Phosphorou a id Stearolic acid D O DhOric acids (6) Unsaturated esters, e. g. phoric acid (a) Esters of unsaturated acids. (e. g. Thiophosnhoric acids 7 those listed under (5) above aswell as cyaaic a id unsaturated aromatic acids such as Thlocyamc acid, cinnamic and coumaric) with mono-' y flcy nic' acid and poly-hydric alcohols, or other rlc acid v hydroxy compounds (including phe-, (7) salts 0f unsaturated, acidsvincluding the-4 nols). Examples of such alcohols Ammonium and Substituted 8 and hydroxy compounds are: m nium Methyl alcohol Sodium Ethyl alcohol Aluminum Propyl alcohols Calcium Butyl alcohols Magnesium Amyl alcohols 40 Zinc Lauryl alcohols Lead Y Cetyl alcohols Salts of unsaturated acids general and B 810011011 more 9 6 101 such acids s those p f yl l h listed under (5)- above and. of unsatu- Tetrahydroiurfuryl alcohol omatic acids.

Ethylene glycol Propylene glycol Di-ethylene glycol Glycerol rythritol Phenol Polyhydroxy-benzenes Alkylated phenols Naphthols Unsaturated alcohols (e.

listed under (1) above) (1)), Esters ofunsaturated alcohols (e. g. those listed under '(1) above) with organic acids, either aliphatic or aromatic, or with inorganic acids.

g. those commercial 'produc Examples of such acids arealiphatic acids, including Saturated acids, such as:

Acetic acid f 'Propionic acids Butyric acids Laurie acids Palmitic' acid Stearic acid Oxalic acid Citric acid Lactic acid Glycoiic acid Malonic' acid (2) Esters, produced by esteri fying the acids In addition to the compounds listed above, tures of unsaturated oxygen-bearing or v 88-1110 compounds may be used as the unsaturated reactant. Examples-oi such materials are 'the'fatty oils of unsaturated character, e. g;: T

Useful Qdditional above fatty oils are, e. g.- (1) Acids, extracted from the oils (by direct hydr'olysis, or by saponiiicatioh and, subsequent hydrolysis, or otherwise.

(1) e. g. to formesters/analogous to any of those listed under (6) in Table No. 2.

r I ,I

ts comprising complex mix unsaturated oxygen 00211 1 pounds which may be derived from of the ('3) Soaps, produced by; saponlryin the oils directly or by neutralizing the acids of (1) with alkalles, e. g. to form salts analogous to those listed under (7) in Table No. 2. The unsaturated oxygen compounds are of particular importance and may, therefore, be I (3) Compounds containing the carbonyl C=O radicle, such as amides, aldehydes, ketones, organic acids, esters and salts of organic acids (including such salts of both inorganic and organic bases) thio-acids and esters and salts of thio-acids' (4) Compounds in which oxygen-forms. a part of the ring structure, e. g. furan and its derivatives, etc.

(55) Compounds with an inorganic radicle where the oxygen is directly attached to a carbon atom, e. g.-

Arsenites' Thiophosphites, Hypochlorites s-hydroxylamines Phosphites Borates Thiophosphatesn'. Indirectly attached through the means. of some other atom, i. e., in the form of an inorganic radicle, e. g.

Arsenate Phosphate Chlorate Sulphate Chlorlte Sulphite Cyanate Sulphinic acid ashydroxylamine Sulphone Nitrate 1 Sulphonic acid Nitrite Sulphoxide Nitro Thiophosphate Nitroso Thiophosphite Oxime T'ilio-sulphate Perchlorate (Note-This class includes salts or organic bases with inorganic oxy-acids.)

In addition to the, unsaturated compounds above-described, certain unsaturated cyclic com pounds are also of use, such as the cyclo-oleflnes (e. g. cyclo-hexene) and derivatives of them.

As a matter of convenience, the halogen and oXygen-contalning-substituted diphenyls, as well as the halogen and'oxygen-containing substituted benzenes where two ormore phenyl'groups are directly linked, may be inclusively referred to as halogen and oxygen-containing substituted polyphenyls.

This invention also contemplates the use of halogen-bearing acids (and salts and esters derived from them) which maybe derived from compounds formed by condensing unsaturated acids. (such as those includedamong the unsaturated oxygen-bearing compounds referred to, above) with an aromatic: compound in the presence of a catalyst such as anhydrous aluminum chloride. Italso contemplates the use of such halogen-bearing salts and. esters as may be derived from compounds formed by similarly condensing unsaturated salts and 'esters (such as those included among theunsaturated oitygeilbearing compounds referred to above) with an aromatic compound.

Examples of other halogen-bearing aromatic ,5 acids, esters and salts of the type contemplated ,hereby (for example those which may be derived from compounds formed by condensing an aromatic acid, ester, or salt, with an unsaturated aliphatic compound) will be found in the com pending application of Carl F. Prutton, Ser. No.

216,153, filed June 27, 1938. v

As previously indicated, the foregoing so-called addition agents may, for most uses, be added in minor amounts to other lubricants such as mineral oil, fish oil, lard oil, castor oil, rape-seed oil, etc., and-in some cases, depending upon the character of use, as well as the character of the selected agents, the latter may be effectively used in their pure state.

The optimum amount of the halogen compound to be employed is usually dependent upon various considerations such as its cost, the'character of the selected compounds, the character of the addition agent to which the same is added and more particularly, the character of the use to which the same is put. For most uses, since the cost of such halogen compounds is usually con- 'siderably greater than lubricants such as mineral oil, optimum results are obtained by using minimum quantities to these halogenated addition agents. For the purpose of lubricating and reducing the friction between relatively moving parts of an internal combustion engine such as crank case bearings, piston and cylinder surfaces,

5 as well as piston rings and valves,a composition according to our invention comprises a major proportion of a suitable 011 base such as mineral oil and concentrations of from one-fourth of 1% to 2% of halogen compounds of the above de- 40 fined type. If the valve structure of the engine is to be lubricated separately from the remainder of the mechanism by means acting inan auxiliary fashion such as by the addition of'the lubricating-composition to the engine fuel, the composition for such purposes will preferably contain a largeramount of such halogen compounds,

i.'e. from about 2% to about 10%.

Whenlubricating bearing surfaces such as gears and the like where extreme temperatures are usually not encountered a composition comprising a major proportion of a suitable oil base and a total of less than about 20% of at least one halogen and oxygen-containing organic compound of the enumerated class will be found very satisfactory. Y When combined with a lubricating oil such as mineral oil, the optimum amount of the'halogen compound to be employed will depend largely upon the halogen content of the particular com pound, its physical characteristics and especially its efl'ecton the viscosity of the oil to which it is added. when addition agents of the above enumeratedclass having very low viscosity are employed, and added to lubricants such as mineral oil, the limit of the amount of such compounds which may be added and which will produceimproved results depends in a large measure upon the reduction in viscosity of the composition caused by the addition of such compounds. When, however, the more viscous compounds are employed, or where the particular use does not require thick film lubrication, the so-called ad tion agents may, as previously indicated, be e ployed in their pure state.

Experiments have shown that when compounds which readily hydrolize, such as chlorinated open chain compounds, are added to the oily base,

hydrolysis will take place to such an extent that the metal parts of any machine being lubricated will be seriously attacked and corroded by the acid generated. 0n the other hand, the addition of chlorinated organic ring compounds of we have listed a large number of classes and specific examples of addition agents, the halogenbearin g derivatives of which are contemplated A i. e., the unhalogenatedmaterials named, as well the above enumerated class does not cause corrosion.

Certain of the halogen and oxygen-bearing open chain or aliphatic compounds, in their pure state, or when added to a suitable basa do result, however, in a lubricant particularly suitable for certain purposes. Examples of the foregoing are halogenated fatty oils such as chlorinated cottonseed oil and chlorinated cocoanut oil. As above indicated, such compounds readily hydrolize and while thus not preferred as a lubricant for use in the crank case of internal combustiontengines, are nevertheless, admirably suited" for use as lubricants in metal working such as drawing; extruding, rolling, etc., where the lubricant is in contact with the metallic surface for only relatively a short length of time and where 'the very slight amount of corrosion which may result is not particularly objectionable. Furthermore, such compounds are admirably suited for use in lubricants in die drawing or similarly workingcertain corrosion resistance materials such as stainless steel and the like.

With regard to the stability of the organic ring compounds contemplated, the most resistant to hydrolysis of the halogen are those in which the halogen is directly attached to an atom which is part of a benzenoid ring structure,- Examples of such ring structures are aryl groups such as the phenyl and naphthyl groups. In any case, for most uses, it is preferred to have the halogen attached to an atom which is part of an organic ring structure and especially a six-member-ed organic ring structure.

The compositionscomprising our invention have certain advantages when used as a lubricant of which the following may be mentioned:'

second-The friction between the bearing surfaces is reduced, especially in the higher pres- --sure range, belowtthat obtained with ordinary lubricants.

.Irrthe. foregoing description of,our invention an aromatic acid.

I as the halogen-free analogs of the halogenated or halogen-bearing materials named, may be employed to advantage in lubricating compositions since many of such possess valuable properties as addition agents.

These unhalogenated materials may be used, as

the sole addition agent to impart improved lubrieating properties to a mineral oil (or other lubricating medium) or may advantageously be used in conjunction with other addition agents, such as organic halogen compounds, organic phosphorus compounds (e. 'g. esters of phosphoric and phosphorous acids), organic sulphur compounds, soaps, oiliness agents, oxidation inhibitors, viscosity index improvers, 'or such other addition agents as may be employed for the same or other purposes.

Other modes of applying the" principle of our invention may be employed instead of the one explained, change being made as regards the materials employed, provided the ingredients stated by anyof the following claims or'the equivalent of such stated ingredients be employed.

- We, therefore, particularly point out and distinctly claim as our invention:

1. A lubricating composition comprising a major proportion of mineral lubricating oil and a minor proportion of a halogen and oxygenbearing compound of the class consisting of halogen-bearing aromatic acids, halogen-bearing esters of aromatic acids and halogen-bearing salts of aromatic acids.

2. A lubricating composition as defined by claim 1 and being further characterized by the fact that the major portion of the halogen present is attached to a benzenoid ring structure.

3. A lubricating composition comprising "a major proportion of mineral lubricating oil and a minor proportion of a halogenbearing ester of CARL F. PRU'ITON.J ALBERT K. SMITH.