US2308622A

US2308622A - Lubricating oil

Info

Publication number: US2308622A
Application number: US260810A
Authority: US
Inventors: Bert H Lincoln; Gordon D Byrkit
Original assignee: Lubrizol Development Corp
Current assignee: Lubrizol Development Corp
Priority date: 1939-03-09
Filing date: 1939-03-09
Publication date: 1943-01-19
Anticipated expiration: 1960-01-19
Also published as: GB666558A

Description

Patented Jan. 19, 1943 LUBRICATING OIL Bert E. Lincoln and Gordon D. Byrkit, Ponca City,

Okla., assignors, by mesne assignments, to The Lubri-Zol Development Corporation, Cleveland,

Ohio, a corporation of Delaware Np Drawing. Application March 9, 1939, Serial No. 2s0,s10

21 Claims. (Cl. 252-58) invention relates to lubricating oil and specifically to a composition of matter having many desirablecharacteristics for practical lubrication.

This application is a continuation in part of our co-pending application Serial No. 16,410, filed April 15, 1935, now issued as Patent No. 2,150,177 of March 14, 1939. x

In the manufacture of lubricating oil designed for use in modern automotive equipment, the demands on the lubricants have increased markedly in recent years. While the low speed engines designed with Babbitt bearings operating with comparatively large clearances between the journals and bearings and between pistons and cylinders required no exceptional properties in the lubricating oil, the modern high speed engines using harder journals and bearings and operating at much smaller clearances require that the lubricating oil possess a variety of unusual l characteristics in order to lubricate this type of engine satisfactorily. Among these characteristics are increased stability toward heat and oxidation, reduced tendency to develop sludge and acidity in use, and most important of ali, the ability to carry high loads without permitting metal-to-metal contact. The necessity of these properties, particularly that of high film strength in lubricating oils, is emphasized in all the lit-. erature treating of lubrication of modern automotive equipment. Thus, forexample, in the National Petroleum News, vol. 2'7, #5, page 25 (January 30, 1935), numerous recommendations for the use of extreme pressure lubricants in -modem automobiles are cited. The use of such addition agents may affect either favorably or adversely such other properties of the hydrocarbon oil as stability toward heat and oxidation, corrosiveness after'use', cold test, and other important properties. In the design of the addition agent, such other effects must be considered, since the hard alloy bearings are very suscep tible to corrosion, for example, by acids derived from both the addition agent and the hydrocarbon base. Unless very soluble addition agents are used, the cloud-point and cold test oi. the blended oil may be raised. This is a distinct disadvantage, particularly in winter grade oils.

Some addition agents may accelerate oxidation or the oil, while others may be without effect or even decrease the susceptibility to oxidation during use. All of the eflects of the'addition agent on the blend must, therefore, be considered in designing a material for the, improvement of the load-cam ability of the oil. It is also an object of this invention to provide a lubricating composition suitable for use in aviation and Diesel engines.

In the previous art of preparing addition agents for the improvement of the film strength of'lubricating oils, little cognizance has been taken of the relation between the molecular structure of the organic molecule and its effect on the properties of the oil with which it is blended. We have discovered that the presence of particular functional groups and their position in the organic molecule have a profound efiect upon the ability of the material to raise the loadcarrying efliciency of the mineral oil with which it is blended. I

We have discovered that the introduction of negative radicals, and more particularly of aryl groups such as the phenyl or substittued phenyl group, into the molecule of a halogenated organic compound serves to activate the halogen in such a Way that the arylated compound is many times more efiective as an extreme pressure compound than the unarylated compound. This In view of this, we have used the terms.aryl

and substituted aryl" to include halogenated improvement which arylation effects in extreme pressure character is not attended by any deleterious change in any other properties of the addition agent,'but the introduction of the aryl group often improves the other properties of the essence so that the blended oil may have better stability with respect to heat and oxidation, better cold test, better color after use, and other desirable characteristics. The presence of halogen in an aryl radical will increase its negativity.

radicals. The total halogen in the molecule may be on an aliphatic carbon or carbons or on an aryl carbon or carbons or locatedon both kinds of carbon atoms. When conditions of use 're quire that the addition agent be of a highly stable character, 1. e., relatively chemically inactive except under conditions of extreme pressure or temperature, it is often desirable that the halo-' gen be attached to a benzenoid ring structure.

We have further ascertained that in a halogenated, arylated' aliphatic compound designed to be used as an addition agen forlubricating oils and where the halogen is on an aliphatic carbon atom, to obtain the most satisfactory addition agent, it is generally desirable to. have at least one aryl nucleus to each aliphatic carbon atom.

Broadly stated, our invention comprises a new lubricating composition containing at least 90% by weight of a mineral lubricating oil or its equivalent and from an efiective amount to of a halogenated polyarylated aliphatic compound.

While our emphasis is on the use of chlorine compounds because of their ready availability and cheapness, we do not wish to be limited to this one halogen, since the other halogens are suited to our purpose. Bromine and iodine are more costly than chlorine, while fluorine is very active chemically.

The halogenated, arylated aliphatic compounds which we contemplated using may be prepared by any of the methods known to the art, such as the Friedel-Crafts reaction or other condensation reactions. They may be purified by distillation, crystallization or other suitable process. It is important, however, that these essences be free from any traces of hydrochloric or other acids, so that such corrosive substances will not be inadvertently introduced into the blend. These may be removed by washing the essence with dilute caustic, soda ash solutions or the like.

In order to compare various addition agents, we

of the hydrogen atoms of the alkyl halide have been substituted by aryl groups. It is particularly advantageous in these arylated or more particularly, phenylated, alkyl halides to have the phenyl group or groups attached either to the carbon atom which bears the halogen or to the next carbon atom. This proximity is desirable in order that the activating influence of the negative phenyl group be efi'ective. I! the latter be further removed, its influence decreases rapidly with the increase in the number of carbon atoms intervening between the phenyl group and the halogen have made blends consisting of one-half percent or one percent of the added material and 99.5 percent or 99 percent of a well refined mineral or hydrocarbon lubricant of the viscosity of S. A. E. 30. In prac icing our invention, however, the hydrocarbon lubricant of the blend may be any material included in that class named, be it natural or synthetic in character, and including hydrogenated and voltolized'oils. These hydrocarbon oils may be of any classification since the invention is not limited to oils of the S. A. E. classification.

For the sake of comparison we have used 0.5% and 1% concentrations of addition agents in our exemplifying blends. However, it is to be understood that in practicing our invention any suitable concentration of addition agent from 0.2% to 5 or as much as 10% may be used in order to obtain effects of the desired magnitude.

These blends were then tested by recommended methods on the machine manufactured for the purpose by the Timken Roller Bearing Company and hereafter referred to as the Timken machine. Its construction and operation are fully described in the literature of the art.

In order to examine the efiect of introducing various substituents into organic molecules so as to increase the film strength of their blends, we have found it helpful to express the eificiency of the halogens, for example, in the-case of a halogenated addition agent, as a ratio of the Timken film strength in pounds per square inch to the percent of chlorine present in the addition agent.

Efficiency index: Increase in Percent of chlorine in the addition product This ratio, which we have chosen to call the "efliciency index, does not constitute an essential part of our invention. but does serve to make more obvious the effect of diiierences in molecular structure which will make our invention clear to those skilled in the art.

' The advantages of our invention become apparent upon examining the effect of introducing phenyl or other substituted or unsubstituted aromatic radicals of negative character into various organic molecules. Thus alkyl halides of low molecular weight have a much smaller effect on the film strength of blends with mineral oil compared with similar compounds in which part or all film strength (pounds per sq. in.)

atoms.

Aryl groups other than the phenyl group are, of course, entirely satisfactory and among them may be included the following:

Benzyl Anthracyl Tolyl Phenanthryl Xylyl Xenyl Naphthyl The specific examples given herein serve to show how we practice our invention, and are not to be considered as limitations on its scope.

1 Note, ethylene chloride and ethylene dichloride are identical.

It is apparent irom this comparison that while the introduction of the four phenyl groups in the ethylene dichloride increases the effectiveness of the latter in improving the film strength, it also reduces the percentage chlorine content of the molecule so much that in order to make a fair comparison of the two compounds when employing them in equal amounts it is necessary to take this into account. The eiilciency index indicates that such halogen as is contained in the phenylated compound is more than nine times as effective in improving the load carrying characteristics in the blend.

The blend of tetraphenyi ethylene chloride (dichloride) was as stable toward oxidation as the hydrocarbon oil from which it was prepared and a satisfactory cold test was obtained.

The effect 01' phenylation is shown here. both in the Timken test and in the efilciency index, but more strikingly in the latter. While hexyl chloride makes but relatively poor use oi its halogen, beta-phenyl ethyl chloride produces five times the film strength in spite of its lower chlorine content. This is shown in the efliciency index which is about thirty greater in the cas of the more efiiclent compound.

The high value shown for the blend of triphenyl methyl chloride illustrates the advantage *Diphenyl dichior methane of having one or moreof the aryl groups attached to the same carbon bearing the halogen.

This compound is three times as efllcient as betaphenyl ethyl chloride, but beta-phenyl ethyl chloride is much mor efficient than either of the alkyl halides.

All of these blends were satisfactory in other respects, such as cold test, stability, color, noncorrosiveness, and other properties.

Inasmuch as the compositions of our invention are designed to be employed where gumming and.

sludge formation would be highly undesirable, as

in the crankcases of internal combustion engines, the lubricant should be substantially free of compounds havingsuch tendencies suchas unsaturated aliphatic compounds and the like which readily oxidize and/or polymerize to form objectionable materials.

Example III T099 parts of S. A. E. 30 universal oil of high quality, one part'by weight of benzophenone di- "chloride was'added and the two components thoroughly blended together. A load of 59,000

'pounds per square inch was carried satisfactorily by this blend on the Timken machine,

such composition affecting its use as a lubricant improved by incorporating therein from about 0.2% to about 5% of a halogenated polyarylated aliphatic compound having at least a portion of the halogen on such aliphatic group.

' gen on such aliphatic group.

while the unblended oilcarried 6,000 to 7,000 1 pounds per square inch pressure. The efliciency index of this addition agent is 1966.7. 'All other properties of this blend were satisfactory.

Among the groups contemplated by this in;- vention and illustrated by the preceding examples are the following structural groups in which A represents an'aryl group:

A typical compound containing a group such as that of Group 0 is l-chloro, 2, 3 diphenyl propane.

Other'modes of applying the principle of our invention maybe employed instead of the one explained, change being made as regards thecomposition and method herein disclosed, provided the ingredients or steps stated by any of the following claims or the equivalent of such stated ingredients or steps be employed.

W therefore particularly point out and distinctly "claim as our invention:

1. A lubricating composition containing as a principal lubricating constituent at least 90% mineral lubricating oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein a minor amount of a halogenated polyarylated aliphatic compound having at least a portion of the halogen on such aliphatic group. i

2. A lubricating composition containing'as a principal lubricating constituent at least 90% mineral lubricating oilv with the properties of such composition afiectingits use as a lubricant improved by incorporating therein from about 0.2% to about 10% of a halogenated polyarylated aliphatic compound having at least a portion of the halogen on such aliphatic group.

3. A lubricating compositioncontaining as a principal lubricating constituent at least 90% mineral lubricating oil with the properties of 5. A lubricating composition containing as a principal lubricating constituent at least 90% mineral lubricating oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein from about 0.2% toabout 10% ofa chlorinated polyarylated aliphatic compound having at least a portion of the halogen on such aliphatic group.

6. A lubricating composition containing as a principal lubricating constituent at least 90% mineral lubricating 'oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein from about 0.2% to about 5% of a chlorinated poiyarylated aliphatic compound having at least a portion of the halogen on such aliphatic group.

7. A lubricating composition containing as a principal lubricating constituent at least 90% v mineral lubricating oil with theproperties of such composition affecting its use as a lubricant improved by incorporating therein a minor amount of a halogenated polyarylated aliphatic compound in which at least a. portion of the halogen is attached to a benzenoid ring structure.

8. A lubricating. composition containing as a principal lubricating constituent at least mineral lubricating oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein a minor 'amount of a'halogenated polyarylated aliphatic compound in which the halogen is attached to the aliphatic nucleus adjacent to an aryl group.

9. A lubricating composition containing as a principal lubricating constituent at least 90% mineral lubricating oil with the properties of such composition aflecting its use as a lubricant improved by incorporating therein from about 0.2% to about 10% of a chlorinated polyphenylated aliphatic compound.

10. A lubricating oil-comprising in combination a major'amount of hydrocarbon oil'and a minor amount of an oil soluble, arylated, chlorinated aliphatic hydrocarbon containing the following structure:

in which A represents an aryl group. I

11. A lubricating oil comprising in combination a magioramount of hydrocarbon oil and a minor amount of an oil soluble, arylated, chlorinated, aliphatic hydrocarbon containing the following structure: i

in which A represents an aryl group.

genated aliphatic hydrocarbon containing the following structure:

l l ...C C. i t,

in which A represents an aryl group.

13. A lubricating oil comprising in combination a major amount of hydrocarbon oil and'a minor amount of an oil soluble, arylated, halogenated aliphatic hydrocarbon containing the following structure:

in which A represents an aryl group.

14. A lubricating composition containing as a principal lubricating constituent at least 90% mineral lubricating oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein a minor amount of a halogenated polyarylated aliphatic hydrocarbon having at least a portion of the halogen on such aliphatic group.

15. A lubricating composition containing as a principal lubricating constituent at least 90% mineral lubricating oil with the properties of such composition aflecting its use as a lubricant improved by incorporating therein from about 0.2% to about 10% of a halogenated polyarylated aliphatic hydrocarbon having at least a portion of the halogen on such. aliphatic group.

16. A lubricating composition containing as a principal lubricating constituent at least 90% mineral lubricating oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein a minor amount of diphenyl dichlor methane.

17. A lubricating composition comprising a mineral lubricating oil and a small amount of a halogenated polyarylalkyl in which halogen is attached to the alkyl group. v

18. A lubricating composition comprising a mineral lubricating oil and a small amount of a chlorinated polyarylalkyl in which halogen is attached to the alkyl group.