US3773787A

US3773787A - Imido polyphenyl oxides

Info

Publication number: US3773787A
Application number: US00112396A
Authority: US
Inventors: J Dickert; I Heilweil
Original assignee: Mobil Oil Corp
Current assignee: ExxonMobil Oil Corp
Priority date: 1969-09-12
Filing date: 1971-02-03
Publication date: 1973-11-20
Anticipated expiration: 1990-11-20
Also published as: FR2061187A5; GB1296425A; DE2045095A1; US3622514A

Abstract

THIS INVENTION PROVIDES COMPOUNDS HAVING A DIPHENYL ETHER OR A POLYPHENYL ETHER MOIETY BETWEEN TERMINAL IMIDE STRUCTURES, AS WELL AS LUBRICANT COMPOSITIONS CONTAINING SAME. THE NEW COMPOUNDS IMPART EXTREME PRESSURE, DETERGENCY, AND ANTIOXIDANT PROPERTIES TO THE LUBRICANT.

Description

Y Patented Nov. 20, 1973 US. Cl. 260-326 N 9 Claims ABSTRACT OF THE DISCLOSURE This invention provides compounds having a diphenyl ether or a polyphenyl ether moiety between terminal imide structures, as well as lubricant compositions containing same. The new compounds impart extreme pres sure, detergency, and antioxidant properties to the lubricant.

CROSS-REFERENCE TO RELATED APPLICATIONS This is a division of application Ser. No. 857,591, filed Sept. 12, 1969, now US. Pat. No. 3,622,514.

BACKGROUND. OF THE INVENTION Field of the invention The invention relates to a new class of compounds and to the use thereof in lubricant compositions to impart extreme pressure, detergency and antioxidant properties thereto. More particularly, the new class of compounds have a diphenyl ether or a polyphenyl ether moiety between terminal imido structures.

Summary of the prior art It is known that sliding or rubbing metal or other solid surfaces arev subject to wear under conditions of extreme pressure. Wearing is particularly acute in modern engines in which high temperatures and contact pressures are prevalent. Under such conditions, severe errosion of metal surfaces can take place, even with lubricants of ever-increasing sophistication, in the absence of load carrying additives. As a consequence, much effort has been expended in discovering additives useful in preventing such wear.

With certainmetals, and under certain conditions, particularly high temperature conditions, many of the conventional additives can cause chemical corrosion. It is contemplated that the compounds of the present invention will cause little, if any such corrosion.

,SUMMARY OF THE INVENTION In accordance with the invention, there are provided compounds of the formula United States Patent wherein:

R is selected from the group consisting of ethylene, propylene, cycloalkylene of from about 3 to about 6 carbon atoms, the alkyl-substituted derivatives thereof, wherein the substituent contains from 2 to about 200 carbon atoms, arylene having from 6 to about 10 carbon atoms, and substituted arylene, wherein the substituent is selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, halo (e.g., chlorine, bromine, iodine, fluorine), hydroxy and mercapto and wherein the said substituents have from 6 to about 30 carbon atoms;

R is selected from the group consisting of hydrocarbylene of from 1 to about 10 carbon atoms and the substituted members thereof, wherein the substituent is selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, halo, hydroxy and mercapto and wherein the said substituents have from 6 to about 30 carbon atoms;

n is an integer of from 0 to about 10;

q is an integer of from 0 to about 50; and

M is selected from the group consisting of oxygen, sulfur,

selenium and tellurium.

It will be understood with respect to R above, that hydrocarbylene is meant to include CH groups, cycloalkylene groups of from 3 to about 6 carbon atoms and arylene groups.

There are also provided lubricant compositions comprising a major amount of a lubricating oil and a minor amount sufi'icient to provide extreme pressure properties thereto of a compound as described above.

PREPARATION OF THE COMPOUNDS AND SCOPE In general, the compounds may be prepared by any known means. For example, the diphenyl oxide derivatives may be prepared from anhydrides and the appropriate diaminodiphenyl oxide in accordance with the reaction.

ZH-N R In the above, as has already been stated, the R group may have substituted thereon an alkyl group of from 2 to about 200 carbon atoms. Preferably the hydrocarboyl will contain from about 16 to about 175 carbons. Such alkyl groups may be placed in the molecule by any appropriate means. In the case of maleic anhydride, this can be done by reacting an olefin therewith. These olefins may be derived from monomers, i.e., ethylene, propylene, butylene, octene, dodecene, hexadecene, or the like. They may also be derived from polyolefins, such as polypropylene, polybutylene, and the like.

Useful anhydrides include those derived from dibasic acids such as succinic and glutaric acids. Also included are the dibasic acid anhydrides having a phenyl, naphthyl or anthryl nucleus in the molecule, as well as the substituted members of such aromatic diacids.

As has already been indicated, the scope of the phenyl portion is not limited to diphenyl oxide derivatives. The portion may, of course, be derived from diphenyl oxide, diphenyl selenide, or the like, but the compounds of the invention include in their scope also those having a plurality of units therein.

The lubricants which are improved by the new compounds of this invention include hydrocarbon mineral oil, either paraflinic or naphthenic, or one of the synthetic lubricating fluids. Such synthetic fluids include polyolefins, polyalkylene oxides, silicone polymers, polyarylethers, polyacetals, and organic esters. This latter class includes diesters, such as those obtained from dicarboxylic acids and monohydric alcohols, triesters, such as those prepared from trimethylolpropane and monocarboxylic acids, and tetraesters obtained form pentaerythritol and monocarboxylic acids, the acids having from 1 to about 30 carbon atoms, or mixtures of such acids. In addition solid lubricants, i.e., greases, capable of being compounded may also be used as the base media in this invention.

The following illustrative examples are intended to describe the invention more fully, and are not to be construed as limitations thereon. All parts, weights and percentages are by weight unless otherwise noted.

EXAMPLE 1 paration of 4,4-di-C-n-hexadecylsuccinimidodiphenyl oxide ethanol-water solution, then from methanolnAfter further purification of the product, the melting point was 76.5 79 C.

Analysis.Calculated from C H N O (percent): C, 76.80; H, 9.92; N, 3.44. Found (percent): C, 74.03; H, 9.62; N, 3.81.

EXAMPLE 2 Preparation of 4,4-di-C-polypropylsuccinimidodiphenyl oxide l RUE-4) N O R-36 carbon atoms CH2?l I About 60 parts (0.1 mole) of polypropylsuccinic'anhydride, about 10 parts (0.05 mole) of- 4,4-diaminodiphenyl oxide and about 250 milliliters of N,N-dime"thy'1- formamide were placed in a reaction flask, stirred and heated to reflux temperature (about 143 C.) for about 6 hours, then allowed to cool to room temperature. -The mixture was warmed in a steam bath, transferred to a beaker and mixed with 800 milliliters of distilled water. Two layers formed, the top layer being a dark brown gel. After stirring at room temperature for about 1 hour, the gel became a solid resin-like material. This material was separated and washed with water.

The product was stirred with warm water and the water decanted, three times, then stirred with warm ethanol, which was also decanted, three times. Benzene wasthen added to the product and the mixture stirred and heated on a steam bath in a flask equipped with a Dean-Stark trap to remove traces of water and ethanol. The benzene was substantially removed by distillation at steam bath temperature and complete removal was accomplished under reduced pressure. This procedure yielded 50 parts of a product containing 79.81% C, 11.42% H, 2.02% N and 5.99% 0.

EXAMPLE 3 Preparation of 4,4-diphthalimidomethyldiphenyl oxide ll 2 A. mixture of about 29.4 parts (0.02 mole) ofphthalirnide, about 15.2 parts (0.11 mole) of anhydrous potassium carbonate, about 27.6 parts (0.1 mole) of 4,4'-dichloromethyldiphenyl oxide and about 200 milliliters of N,N-dimethylformamide was placed in a 'reactidnfflask, stirred and heated at reflux temperature (about 148 C.) for about 6 hours. The product was washed once N,N-dimethylform'amide, twice with water. The damp solid (38 parts) was placed in a vacuum oven'at 55 The mixture was allowed to cool to room temperature, chilled in an ice bath, and the solvent layer decanted 01f aviscous insoluble lower layer (product).. About 400 milliliters of benzene wasadded to this product, stirred and warmed on asteam bath to effect solution andfil- 60 C. for about 30 hours, at which time the melting point tered. The benzene was removed by vacuum distillation was 251-256 C. This sample was digested in hot benon a steam bath. The product was stirred two times'with zene, cooled and recovered by vacuum filtration and reethanol, decanting the ethanol each time, and two times crystallized from N,N-dimethylformamide to give the with water, also decanting the water each time. The prodproduct melting at 269.5 270 C. The analysis is shown not was then dissolved in benzene and the solution washed below. by shaking with water. The final traces of water were re- Calculated (for C H N O (percent): C, 73.76; H, moved by azeotropic distillation with the benzene. The 4.13; N, 5.73. Found (percent): C, 73.37; H, 4.38; N, benzene was finally removed by vacuum distillation. 5.98. Analysis.Found (percent): C, 80.08; H, 11.00; N,

' EXAMPLE 4 0.87. Preparation of 4,4'-disuccinimidomethyldiphenyl oxide EXAMPLE 6 Preparation of 4,4-di-C-polybutenylsuccinimidomethyldiphenyl oxide II CHz-C RCH-C N or1.- o N-on,- 0 R-CmH|n CHr-C om-o A mixture of about 27.5 parts (about 0.05 mole) of a polybutenylsuccinimide (molecular weight about 2550), A mix of about parts mole) of succinabout 6.7 parts 0.025 mole) of dichloromethyldiphenyl imide, Parts mole) Potassium carbonate, oxide, about 8.3 parts (0.06 mole) of potassium carbon- Parts mole) of 4,4-dichlolomethyldiphenyl Oxide 3 ate, and 300 milliliters of N,N-dimethylformamide was and 200 milliliters of N,N-dime hylf rm was Stirred stirred and heated at reflux temperature (about 148 C.) and heated to reflux temperature (about for about 3 hours. The mixture was cooled and the dark about 6 hours. The Solut o was cooled to room p supernatant liquid was decanted off the sludge (a viscous was filtered, and the filtrate was diluted with about insoluble liquid) in the bottom of the reaction flask. The 500 milliliters of water. This solution was extracted three Sludge was dissolved i 250-300 1, of benzene and fil. times, each time about 200 milliliters Of benzene. te -a1 The benzene was removed by distillation at 90.- The benzene solution was filtered and dried over anhy- 100 C. giving 122 grams of product havingthe f ll drous sodium sulfate. The drying agent was removed by i analysis; filtration and the solvent was removed by vacuum distilla- F nd (percent): C, 79.85; H, 12.92; N, 2.30; O, 2.92. tion on a steam bath. 30.9 parts of brown liquid product EXAMPLE 7 was obtained having the following analysis:

Analysis.-Found (percent): C, 71.60; H, 5.99; N, 5.77. m-Bis[p-(C-n-hexadecylsuccinimido)phenoxy] benzene 0 010E330 H-(U} (IL-C H C "Ha 3, C-CH| o (i EXAMPLE 5 This product was prepared substantially as described in Preparation of 4,4'-di-C-polypropylsuccinimidomethyl- Example except that t flp- P yl benzene diphenyl oxide was used lnstead of 4,4'-d1am1nod1phenyl oxide. The melt- 0 ing point of the product after recrystallization from eth- RCH ll anol-acetone was 98101 C. The product had the follow- 1 mg ana ysrs. 0 Calculated (for C I-1 N 0 (percent): C, 76.95; H, 9.35; N, 3.09. Found (percent): C, 76.86; H, 9.31; N, 3.02. o 2 About 120 parts (0.2 mole) of polypropylsuccinic an- EVALUATION OF PRODUCTS hydride (molecular weight of about 600) was mixed with 11 w Test about 1 liter of reagent grade toluene. The mixture was a stirred and warmed on a steam bath to effect solution. In this test, three steel balls of 52100 steel are held While stirring continued, the mixture was cooled (icein a ball cup. A fourth ball positioned on a rotatable axis water bath) to about 3 C. Anhydrous ammonia was is brought into contact with the three balls and is rotated passed over the surface of the cooled, stirred mixture until aga st th T e rce with which t ata all i no more heat was evolved (about 3 hours). The toluene held against the three stationary balls may be varied acwas removed by distillation and the mixture was heated cording to the desired load. The test lubricant is added to under vacuum at 280-300 C. for about 4 hours. 114 the ball cup and acts as a lubricant for the rotation. At parts of product was obtained having 80.92% C, 12.34% the end of the test, the steel balls are investigated for wear H, 1.06% N and 5.39% O. scar; the extent of scaring represents the effectiveness of About 60 parts of the above product, about 13.4 parts the lubricant as an anti-wear agent. The results shown in of chloromethyldiphenyl oxide, about 16.6 parts of re- Table II were obtained using 2.4% by weight of the comagent grade potassium carbonate and about 300 millipound. The tests were carried out at 200 F. for 30 liters of N,N-dimethylformamide were stirred and heated minutes, under a load of 40 kg. and at a rotational speed at reflux temperature (about C.) for about 4 hours.

of 600 r.p.m.

7 Pin-on-Disk Wear Test ,diskconcentric with the axis thereof. Both pin and disk are submergedin a. vessel holding the test lubricant so that the point of contact between the pin and the rotating disk is lubricated at all times. The force of the disk against the pin may be changed by varying a load outside of the lubricant vessel. The pin and disk used in the following tests were AISI 1018 steel and AISI 1020 steel, respectively. The results shown in Table I were obtained at a load of 8 kg. and a sliding velocity of cm./sec. The tests were carried out at 200 F. over a 5-hour period.

The evaluation for the wear rate is reported in units of cc./cm., that is, volume of metal worn away from the pin per distance traveled by the pin.

The lubricants used in the above tests are identified as follows.

Designation: Fluid A n-Hexadecane. B polyphenyl ether. C Decene trirner.

A mixed isomeric five ring polyphenyl ether having an estimated boiling point of 982 F. at 706 mm. Hg and a kinematic viscosity of 3-63 cs, at 100 F. (13.1 cs. at 210 F.).

A hydrogenated decene-l trimer having a kinematic viscosity of 16.68 cs. at 100 F. (3.71 cs. at 210 F.) and a pour point below --35 F.

Friction.

Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departmg from the spirit and scope of this invention, as those skilled in the art will readily understand. Variations such as structures in which an imido group is attached to only one end ofa polyphenyl ether or in which the imido groups are in a chain'or incorporated into a polymer structure are examples. i I

We claim: 1. A compound of the formula wherein R is ethylene, alkyl-substituted ethylene, the alkyl containing (from 2 to '200carbon atoms, or phenylene, n is zero or 1 and q is zero or 1.

2. The compound of claim 1 wherein q is zero. 3. The compound of claim 2 wherein R is CitHaCH- and n is 0.

4. The compound of claim 2 whereinR is CuHn-CH- and n is 0.

5. The compound of claim 2 having the formula- 0 Gila-"J1 i CH|C/ ll 2 6. The compound of claim 2 wherein R is CuHn-CH- and n is 1. 7. The compound of claim 2 wherein R is 11eHm H (BI-Ir and n is 1.

8. The compound of claim 2 wherein R is and n is 1.

9. The compound of claim 1 wherein R is CuHu-CH n is zero and q is 1.

References Cited UNITED STATES PATENTS 3,154,560 I 10/ 1964 Osuch 260-3263 JOSEPH A. NARCAVAGE, Primary Examiner mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No- 3,773,7 7 Dated November 973 Inventor(s) JOSEPH JOHN DICKERT, JR. and ISRAEL -JOEL HEILWEIL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

. v I a i Column 6, line 26, "27.5" should be 127.5

Signed and sealed this lth' da or April: l9 7l (SEAL) Attest: v v

EDWARD M.FLETCHER,JR. C. MARSHALL DANN Atte sting Officer Commissioner of Patents