US3576898A - Synthetic hydrocarbons - Google Patents

Abstract

COMPOUNDS OF THE CLASS WHICH EXHIBIT WIDE LIQUID RANGE AND HIGH BOILING POINTS HAVING FROM 24 TO ABOUT 96 CARBON ATOMS AND WHICH HAVE THE CHEMICAL STRUCTURE

(R)2-CH-CH2-(C(-R)2-CH2)A-C(-R)2-CH3

WHEREIN EACH R IS ALKYL AND A IS A WHOLE NUMBER HAVING A VALUE OF FROM 0 TO 1. THE COMPOUNDS ARE PARTICULARLY USEFUL AS JET ENGINE LUBRICANTS.

Description

United States Patent ()ffice 3,576,898 Patented Apr. 27, 1971 3,576,898 SYNTHETIC HYDROCARBONS Edward S. Blake, Kettering, Ohio, and Morris R. Ort, Kirkwood, Mo., assignors to Monsanto Company, St. Louis, M0.

N Drawing. Continuation-impart of application Ser. No.

636,245, May 2, 1967, which is a continuation of application Ser. No. 128,986, Aug. 3, 1961. This application Dec. 6, 1967, Ser. No. 688,379

Int. Cl. C07c 9/16 US. Cl. 260-676 8 Claims ABSTRACT OF THE DISCLOSURE Compounds of the class which exhibit wide liquid range and high boiling points having from 24 to about 96 carbon atoms and which have the chemical structure wherein each R is alkyl and a is a whole number having a value of from O to 1. The compounds are particularly useful as jet engine lubricants.

This application is a continuation-in-part of application Ser. No. 636,245, filed May 2, 1967, now abandoned, which application in turn is a continuation of application Ser. No. 128,986, filed Aug. 3, 1961, now abandoned.

This invention relates to synthetic aliphatic hydrocarbons which exhibit a wide liquid range and high boiling points.

Many different types of materials have been utilized as functional fluids and functional fluids are used in many different types of applications. Such fluids have been used as electronic coolants, diffusion pump fluids, synthetic lubricants, damping fluids, bases for greases, force transmission fluids (hydraulic fluids), heat transfer fluids, die casting release agents in metal extrusion processes and as filter mediums for air conditioning systems. Because of the wide variety of applications and the varied conditions under which functional fluids are utilized, the properties desired in a good functional fluid necessarily vary with the particular application in which it is to be utilized with each individual application requiring a functional fluid having a specific class of properties.

Of the foregoing the use of functional fluids as lubricants, particularly gas turbine or jet engine lubricants, has posed what is probably the most difficult area of application. As the operating temperatures for lubricants have increased it has become exceedingly diflicult to find lubricants which properly function at engine temperatures for any satisfactory length of time. Thus, the requirements of a jet engine lubricant are as follows: The fluid should possess high and low temperature stability, foam resistance, good storage stability and be non-corrosive and nondamaging to metal mechanical members which are in contact with the fluid. Such fluids should, in addition, possess adequate temperature-viscosity properties and satisfactory lubricity, that is, the lubricants must not become too thin at the very high temperatures to which they are subjected nor must they become too thick at lower temperatures and must at the same time be able to provide lubricity over such range of temperatures. In addition, such lubricants should not form deposits which interfere with the proper operation of a jet engine.

As the speed and altitude of operation of jet enginecontaining vehicles increase, lubrication problems also increase because of increased operating temperatures and higher bearing pressures and temperatures resulting from the increased thrust needed to obtain high speeds and altitudes.

More particularly, lubricants which are used to lubricate jet engines can experience bulk oil temperatures of about 400 F., bearing temperatures of 500-550 F. and for certain short periods of time temperatures up to 600 F. This high temperature jet engine environment presents the diflicult problem of obtaining a lubricant which will function under these conditions. In addition, the high temperature jet engine environment is made additionally severe since the seals which are utilized to prevent leakage of the lubricant require a flow of air through the seals. In general, eight seals in a jet engine are utilized with air flow rates through the seals of approximately onehalf cubic foot per minute. Another feature of a jet engine is the use of a breather tube for evacuating air that enters the system through the seals and in addition for evacuating any volatile decomposition products of the lubricant which may accompany the use of the lubricant.

As is seen from the foregoing environmental characteristics of a jet engine, a lubricant can experience temperature ranges of from 400 F. to 600 F. Of particular importance is the bearing temperatures of 500550 F. The lubrication of a bearing in a jet engine is of critical importance since if lubrication fails the hearing will fail, thereby bringing about engine failure. In order to properly lubricate a bearing, the lubricant must not volatilize at the temperatures which result from contact with the bearing. A lubricant which is boiling or in the vapor form cannot lubricate since metal surfaces would not be covered with a lubricating film of the lubricant.

Another important environment characteristic of a jet engine which has been illustrated above is the use of leakage of air through the seals to prevent fluid leakage. Thus, a lubricant which is exposed to this particular environment must not be at or near its boiling point since the passing of air through a liquid will tremendously enhance the volatilization of a lubricant.

Thus, a fluid subject to the environmental temperature conditions of a jet engine which is at or near its boiling point would be lost in but a short period of time as it volatilizes from the bulk oil reservoir through the breather tube. In addition, one of the criteria for use in a jet engine of a lubricant is that it must pass an evaporation loss test which comprises passing air through a lubricant at a given temperature for a certain period of time.

Another problem that arises through the loss of a fluid by volatilization is brought about by the fact that the breather tube can become closed through vapor phase coking of a fluid. A fluid with a high rate of volatilization is very susceptible as it passes through the breather tube to decompose thereby forming carbonaceous deposits in the breather tube, which over a period of time can completely close the breather tube. When this condition occurs, the use of air leakage as a means of preventing fluid leakage is not accomplished. Thus, fluids which are volatilized readily under the influence of air passing through the fluid can reduce or nullify the sealant effect of air.

As is set forth above, a fluid has to have a high boiling point in order to (1) properly lubricate a jet engine bearing at bearing temperatures and (2) prevent fluid volatilization from jet engines.

It has now been found that lubrication of a jet engine and other applications as set forth herein can be accomplished utilizing new synthetic hydrocarbons having a wide liquid range and high boiling points Which are represented by the structural formula wherein R, R and R are each alkyl having from 2 to 16 carbon atoms, R R and R are each alkyl having from 1 to 16 carbon atoms provided that only one of the alkyl groups represented by R R and R can contain 1 carbon atom and further provided that the total number of carbon atoms present in the compound is from at least 24 carbon atoms to about 96 carbon atoms and a is a Whole number having a value of to 1.

The compounds as illustrated above have outstanding liquid properties and high boiling points. The preferred compounds Within the formula set forth above can be defined by the number of carbon atoms in the compound and by the total number of carbon atoms present in certain classes of the radicals represented by R, R R R R and R More particularly when a is 0, it is preferred that the total number of carbon atoms in the compound be from 24 to about 60 and when a is 1, it is preferred that the total number of carbon atoms be from 30 to about 90. In addition, when a has a value of 0, it is preferred that the sum of the carbon atoms present in R and R be from 6 to 28 and more preferably from 8 to 24 and the sum of the number of carbon atoms in R and R be from 8 to 32 carbon atoms and more preferably from 12 to 24 carbon atoms. When a has a value of 1, it is preferred that the sum of the carbon atoms in R R and R, be from 8 to 42 carbon atoms and more preferably from 12 to 36 carbon atoms and the sum of the number of carbon atoms in R, R and R be from 12 to 48 carbon atoms and more preferably from 18 to 42 carbon atoms.

The above ranges of carbon atoms are preferred since the compounds of this invention within the preferred limits as set forth above exhibit wider liquid ranges, whereas all of the compounds within this invention have sufliciently high boiling points to perform as jet engine lubricants.

Typical examples of alkyl groups, alkyl herein defined to include straight-chain alkyl as Well as branched-chain alkyl are methyl ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, isoamyl, 2-methylbutyl, 2,2-dimethyl propyl, l-methyl butyl, diethyl methyl, 1,2-dimethyl propyl, tert-amyl, n-hexyl, l-methylamyl, lethyl butyl, 1,2,2-trimethyl propyl, 3,3-dimethyl butyl,

1,1,2-trimethyl propyl, 2-methyl amyl, 1,1-dimethyl butyl, l-ethyl Z-methyl propyl, 1,3-dimethyl butyl, isohexyl, 3-methyla-myl, 1,2-dimethyl butyl, l-methyl l-ethyl propyl, 2-ethyl butyl, n-heptyl, 1,l,2,3-tetramethyl propyl, 1,2-dimethyl l-ethyl propyl, 1,1,2-trimethyl butyl, l-isopropyl Z-methyl propyl, l-methyl Z-ethyl butyl, 1,1-diethyl propyl, 2-methyl hexyl, 1,1-dimethyl amyl, l-isopropyl butyl, l-ethyl 3-methy1 butyl, 1,4-dimethyl amyl, isoheptyl, l-methyl l-ethyl butyl, l-ethyl Z-methyl butyl, l-methyl hexyl, l-propyl butyl, noctyl, l-methyl heptyl, 1,1-diethyl Z-methyl propyl, 1,1,3,3-tetramethyl butyl, 1,1-diethyl butyl, 1,1-dimethyl hexyl, l-methyl l-ethyl amyl, l-methyl l-propyl butyl, 2-ethyl hexyl, 6-methyl heptyl (iso-octyl), n-nonyl, l-methyl octyl, l-ethyl heptyl, 1,1-dimethyl heptyl, l-ethyl l-propyl butyl, 1,l-diethyl 3- methyl butyl, diisobutyl methyl, 3,5,5-trimethyl hexyl, 3,5- dimethyl heptyl, n-decyl, l-propyl heptyl, 1,1-diethyl hexyl, 1,1-dipropyl butyl, 2-isopropyl S-methyl hexyl, n-undecyl, 3-propyloctyl, 4-butylheptyl, 4-pentylhexyl, 3-ethylnonyl, n-lauryl, 3-ethyl decyl, 3-butyloctyl, 4-pentylheptyl, tridecyl, Z-ethylundecyl, 4-butylnonyl, n-tetradecyl, 4-

butyldecyl, 3-pentylnonyl, n-pentyldecyl, 3-propyldodecyl,

3-butylundecyl, 4-pentyldecyl, n-hexadecyl, Z-ethyltetradecyl, 3-butyldodecyl, S-pentylundecyl, n-heptadecyl, 2- heptyldecyl, 3-propyltetradecyl, n-octadecyl, 2-ethylhexadecyl, 3-propylpentadecyl, 3-butyltetradecyl, 3-pentyltridecyl, n-nonadecyl, 3-propylhexadecyl, 3-pentyltetradecyl,

3-heptyldodecyl, n-eicosyl, 2-ethyloctadecy1, 3-propylheptadecyl, 4-butylhexadecyl and 4-pentylpentadecyl.

The preferred method of producing the compounds of this invention are by the steps of (1) dimerizing an alpha-olefin containing from 3 to 20 carbon atoms, for example, in the presence of a trialkyl aluminum catalyst, to produce a dimer compound or a mixture of dimerized compounds if two dissimilar alpha-olefins are used, followed by (2) dimerizing or trimerizing the dimer compound or mixture of dimer compounds prepared in step (1) using a complexed Friedel-Crafts catalyst to prepare the dimerized compound or a strong Friedel-Crafts catalyst for preparation of trimerized compounds, followed by (3) hydrogenation of a dimerized compound or compounds or a trimerized compound or compounds prepared as in step (2).

In carrying out step (1) of the process, an alpha-olefin, such as alpha-olefins containing from 3 to 20 carbon atoms therein examples of which are propylene, butene-l, pentene-l, 3-methylbutene-1, hexene-l, heptene-l, 3-methylhexene-l, octene-l, 3-methylheptene-1, nonene-l, 4-ethylnonene-l, decene-l, undecene-l, 3-ethylnonene-1, dodecene-l, tridecene-l, 4-propyldecene-l, tetradecene-l, 4-butyldecene-l, pentadecene-l, 3-hexylnonene-1, hexadecene-l, octadecene-l, 3-hexyldodecene-1, eicosene-l and 3-ethyloctadecene-1, is dimerized by heating such olefin at a temperature of from about to about 350 C., preferably from about C. to about 250 C. in the presence of from about 0.1 to about 20 and preferably from about .5 to about 5 weight percent, based on the olefin, of a catalytic compound defined by the formula M(Z) wherein M is a metal selected from the group consisting of aluminum, gallium, indium and beryllium, x is a number corresponding to the valence of the M and each Z independently can be hydrogen, a monovalent saturated aliphatic radical, and a monovalent aromatic radical. It is preferred that the radicals do not contain more than 18 carbon atoms.

Typical examples of suitable catalysts represented by are AlH3, Hal (CH s)2 -2 5)2 4 Q)2 s 5)2 and the like. The aforesaid class of catalysts can also be employed in the form of their complexes with ethers, thioethers, alkaline metal hydrides and alkyls or aryl derivatives thereof, such as, LiAlH LiAl(C H NaAl(C H NaBe(C H and the like. Additionally the aforesaid process can be carried out at atmospheric or superatmospheric pressures for example in a closed vessel at pressures up to 500 atmospheres or higher. The reaction product may be treated with an alcohol and hydrochloric acid to decompose the catalyst and dissolve the salt formed therefrom. The dimerized product of step (1) can be washed several times with water, filtered, dried and fractionally distilled to recover the desired dimerized product.

After the olefin is dimerized in process step (1), the dimer product is treated with a Eriedel-Crafts catalyst such as aluminum chloride, aluminum bromide, ferric chloride, ferric bromide, zinc chloride, stannic chloride, zirconium chloride, titanium tetrachloride, boron trifluoride and complexes thereof, and the like, preferably an aluminum halide, and other acid catalysts, e.g., sulfuric acid, hydrofluoric acid and the like, in an amount of from about .001 to about 20, and preferably from about 0.1 to

about 8 weight percent, based on the weight of the dimer product of process step (1). In order to dimerize the dimer product of process step (1), a Friedel-Crafts catalyst complex with, for example, nitrohydrocarbons is used whereas in order to effect trimerization of the dimer product of process step (1) a noncomplex Friedel-Crafts catalyst is utilized. In general, the concentrations as set forth above apply equally to producing the dimerized and trimerized products of process step (2) utilizing the dimer products of process step (1). The second process step utilized to dimerize the dimer from process step 1) is preferably carried out in the presence of a modifier compound for the Friedel-Crafts catalyst, for example, the nitrohydrocarbons such as the nitroalkanes, e.g., nitromethane, nitroethane, l-nitropropane, 2-nitropropane and the like, and nitrobenzenoid compounds, e.g., nitrobenzene, nitrotoluene and the like. Preferably, the molecular weight of the nitrohydrocarbon should be less than about 150 and the primary nitroalkanes containing up to 3 carbon atoms are the specifically preferred attenuators for the Friedel-Crafts catalyst. It is known that the nitrohydrocarbon forms an addition complex with the Friedel- Crafts catalyst, e.g., AlCl -ZNO wherein Z is the hydrocarbyl group of the nitrohydrocarbon. The nitrohydrocarbon can be employed in an amount of from about 0.1 to about 15 moles or more thereof per mole of the Friedel-Crafts catalyst, since the addition complexes retain their activity even with a large excess of the nitrohydrocarbon solvent. Other attenuators can also be employed for the aforesaid nitrohydrocarbons, for example, various halogenated compounds, such as carbon tetrachloride, tetrachloroethylene, chloroform and the halobenzenes, e.g., chlorobenzene, bromobenzene and higher halogenated benzenes, and aromatic ethers such as diphenyl ether. The Friedel-Crafts catalyst is employed at a temperature of from about 25 C. to about 80 C., and preferably from about to about 35 C. After a reaction period, preferably from about 0.5 to about 3 hours or more the reaction mixture is poured into water and the water and nitrohydrocarbon layers or other attenuator compound separated from the reaction mixture. The reaction mixture can then be diluted with hydrocarbon solvent such as benzene or hexane and the organic phase washed several times with water, dried, filtered and the solvent stripped therefrom by distillation at reduced pressure. The process conditions which are illustrated above for producing the dimerized products of process step (2) can be utilized to prepare the trimerized products of process step (2) utilizing a noncomplexed strong Friedel-Crafts catalyst.

The dimerized and trimerized compounds of process step (2) are then hydrogenated in the presence of a suitable hydrogen system, such as hydrogen in the presence of a suitably hydrogenation catalyst, e.g., a Raney nickel catalyst, to prepare the compounds of this invention. More particularly, the dimerized and trimerized compounds of process step (2) can be hydrogenated utilizing hydrogen and a Raney nickel catalyst at a catalyst concentration of from 5 to 25% by weight based on the weight of the di merized or trimerized product of process step (2) at a temperature of from 100 C. to 250 0., preferably 180 C. to 220 C. for a period of from about 4 to 12 hours, preferably from 6 to 10 hours. In carrying out the hydrogenation step, that is, process step (3), a hydrogen pressure is generally maintained in an autoclave of from approximately 1200 to 2300 p.s.i.g., preferably from 1500 to 2100 p.s.i.g. The compounds of this invention can then be fractionally distilled to separate the compounds of this invention from any unreacted dimerized or trimerized products of process step (2) and/or from any solvent which is utilized to carry out the hydrogenation step. As has been stated above with respect to the 3 preferred process steps that are utilized in preparing compounds of this invention, dissimilar olefins can be utilized in process step (1) which give rise initially to the preparation of a mixture of dimerized compounds of process step (1). The mixture of dimerized compounds of process step (1) can be utilized directly in process step (2) or the compounds which comprise the dimerized compounds of step (1) can be separated and used individually in process step (2). In addition to preparing mixtures of dimerized compounds in process step (1) for utilizing in process step (2), two different dimerized compounds of process step (1) can be made separately in separate process steps and combined in process step (2) to produce a mixture of dimerized and trimerized compounds of process step (2). When two dissimilar dimerized compounds are utilized in process step (2), mixtures of compounds are prepared which can be hydrogenated directly utilizing process step (3) or the mixtures of dimerized and trimerized compounds in process step (2) can be separated by, for example, fractional distillation and individually hydrogenated using process step 3). If, for example, the mixtures of dimerized and trimerized compounds of process step (2) are not separated, mixtures of compounds of this invention are prepared after hydrogenation using process step (3). Again mixtures of compounds of this invention produced in process step (3) can be separated and the individual compounds utilized separately in the uses as set forth or mixtures of compounds can be utilized in the uses as set forth. The compounds of this invention that are present in mixtures of compounds of this invention can be separated by vapor-phase chromatography using a chromatographic column. A chromatographic column that can be utilized is, for example, a column which is 8 feet by inch packed with 18% polyethylene glycol having an ASTM code number of 244 (ASTM system published as ASTM Special Technical Publication No. 343 entitled Compilation of Gas Chromatographic Data) and 1% silver nitrate on 35 to 48 mesh flux calcinated diatomite having a surface area of 1 to 3.5 m. g. The identification of the particular isomers is obtained utilizing a thermal conductivity instrument operating, for example, isothermally at 150 C. A typical instrument is an F and M instrument, Model 770. In

' addition, mixtures of compounds of this invention can be separated by fractional distillation, especially where the compounds of this invention differ with respect to the number of carbon atoms present in the compounds and in addition with respect to boiling points. Confirmation of the structure of a compound of this invention can be accomplished utilizing one or more of the following methods: mass spectroscopy, gas liquid chromatography, molecular weight determination by for example vapor phase osmometer, and nuclear magnetic resonance.

The thermal decomposition points reported herein were determined by the isoteniscopic method, wherein the decomposition point is the temperature at which the rate of decomposition is a half-filled glass vessel and oxygenfree atmosphere is suificient to cause an isothermal rate of pressure rise of 0.014 mm. of mercury per second as measured in an isoteniscopic apparatus of the type described by Smith and Menzies, J. Amer. Chem. Soc. 32, 897, 907, 1412 (1910), as modified and described by Blake et al., J. Chem. and Eng. Data 6, 88-89 (January 1961).

The following examples illustrate the preparation of the dimerized product of process step (1).

EXAMPLE 1 A 1504.8 g. portion (10.72 moles) of decene-l is charged to a 3-liter, stainless steel, rocker bomb. After the addition of the decene-l to the bomb, the bomb is closed and purged with purified nitrogen for a period of about 15 minutes, during which time 30 ml. of triisobutyl aluminum catalyst is introduced. The bomb is then sealed and heated to a maximum temperature of about 225 C. After a period of about 7.5 hours the rocker is shut off and the bomb allowed to cool. The bomb is then vented, ml. of ethanol added to the reaction mixture and the bomb resealed and allowed to rock for about minutes. The bomb is then opened and the reaction mixture transferred to a flask. The reaction mixture is treated with 750 ml. of distilled Water to decompose the aluminum ethoxide and subsequently 200 ml. of concentrated hydrochloric acid is added thereto to solubilize the aluminum salts. The reaction mixture is then Washed With four 500-m. portions of water and the organic phase separated, dried, filtered and fractionally distilled. Approximately 952 g. of the product 2-octyldodecene-1 is obtained at 132 to 135 C./0.25 to 0.15 mm. Hg (11 1.4462) for a yield of about 63.3 percent.

EXAMPLE 2 A mixture of 1053.2 g. (9.42 moles) of octene-l and 50 ml. of diisobutyl aluminum hydride is charged to a 3-liter, stainless steel, rocker bomb in similar manner to the procedure set out in Example 1. The bomb is heated to a maximum temperature of about 200 C. over a period of about 26 hours, then allowed to cool, vented, opened, 200 ml. of ethanol added to the reaction mixture and the bomb rescaled and allowed to rock for about 10 minutes. The bomb is then opened, the reaction mixture transferred to a flask, the bomb washed with 200 ml. of ethanol, the combined reaction mixture and bomb washings poured into 750 ml. of water and well shaken to effect the decomposition of the aluminum catalyst. Then 75 ml. of concentrated hydrochloric acid is mixed therein and the aqueous phase removed. The organic phase is again washed with 500 ml. of water in combination with 25 ml. of concentrated hydrochloric acid, the aqueous phase removed, followed by another wash with 500 ml. of water, after which the organic phase is dried, filtered and fractionated through a Vigreux column. The cut boiling at 139 to 137 C./10 to 8 mm. Hg is recovered and consisted of 634.8 g. of 2-hexyldecene-l, a 60.2% yield.

The relatively long reaction period of the above preparation is not essential as substantially similar yields are obtained in shorter reaction times of the order of from about 6 to 12 hours.

EXAMPLE 3 A mixture of 588 g. (7 moles) of hexene-l and 25 ml. of diisobutyl aluminum hydride is charged to a 3-liter stainless steel, rocker bomb in similar manner to the procedure set out in Example 1. The reaction mixture is heated to a maximum temperature of about 235 C. over a period of about 9.5 hours, then allowed to cool, the

The organic phase is further washed with two 400 ml. portions of water, dried, filtered and fractionated through a Vigreux column. The cut boiling at 205 to 207 C./76O mm. Hg is recovered and consisted of 363.2 g. of 2-buty1- octene-l, a 61.8% yield.

EXAMPLE 4 A mixture of 680.7 g. (4.03 moles) of dodecene-l and 15 ml. of diisobutyl aluminum hydride is charged to a 3-liter, stainless steel, rocker bomb in similar manner to the procedure set out in Example 1. The reaction mixture is heated to a maximum temperature of about 210 C. over a period of about 8 hours, then allowed to cool, the bomb vented, opened, 100 ml. of ethanol introduced into the reaction mixture and the bomb rescaled and allowed to rock for about 10 minutes. The reaction mixture is then removed from the bomb, washed with 500 ml. of water to decompose the aluminum catalyst, 50 ml. of concentrated hydrochloric acid added and the aqueous phase removed. The organic phase is further washed with two 500 ml. portions of water and after the aqueous phase is removed the organic phase is dried, filtered and fractionated through a Vigreux column. The cut boiling at 168 to 170 C./ 0.25 to 0.15 mm. Hg is recovered and consists of 395 g. of 2- decyltetradecene'l, a 58% yield.

EXAMPLE 5 A mixture of 420 g. (3.0 moles) decene-l, 504 g. (3.0 moles) dodecene-l and ml. of diisobutyl aluminum hydride is charged to a 3-liter, stainless steel, rocker bomb in similar manner to the procedure set out in Example 1. The bomb is heated to a maximum temperature of about 200 C. over a period of about 10.3 hours, then allowed to cool, vented, opened, 200 ml. of ethanol added to the reaction mixture, the bomb rescaled and allowed to rock for about 10 minutes. The bomb is then opened, the reaction mixture transferred to a flask, 750 ml. of water and ml. of concentrated hydrochloric acid added thereto and well mixed therein by shaking several times, the aqueous and organic phases allowed to separate and the aqueous phase removed therefrom. The organic phase is washed with two 500 ml. portions of water, dried, filtered and fractionated through a Vigreux column. The codimer mixed product out boiling at 135 to 170 C./0.15 mm. Hg (549.7 g.) is recovered.

Following the procedure of Example 3, the following dimerized products as set forth in Table I were produced using process step (1).

TABLE I Ex. No. Product 6 2-dodecyl-1-hexadecene 4.0,1-tetradecene 2.38, l-dodccene; 2.38, l-tetradeceno 5.0, l-octene; 18.0, propylene... 9 2-mcthyl-1-dodecene and 2-propyl-1-decene 4.0, l-decene; 14.4, propyiene Z-methyl-l-tetradecene and 2-propyl-Ldodecene... 2.0, l-dodecene; 3.52, propyien 2-methyl'1-tetradeceuo and 2-propyl-1-d0decene 2-propyl1-hexadeccne 4.0, l-octene; 11.75, l-butene zethyl-l-dodecene and 2butyl-1-decene 3.64, l-decene; 10.8, 1-butene 2ethyl-1-tetradecene and Z-butyl-l-dodecene 4.0, l-dodecene; 12.0, l-butene Z-ethyl-l-hcxadeeene and 2-butyl-1-tetradecene. 3.0, l-tetradeeeue; 12.5, i-butene 2-ethyl-1-octadecene and 2-butyl-l-hoxadecene. 3.0, l-hexadecene; 10.3, 1-butene 10.0, l-pentene 4.0, l-dodecene; 8.3, 1-pcntene 4.05, l-tetradecene; 10.0, l-pentene. Z-(ZethylhexyD-Gethyi decenc-l 4-ethyl octene-l 22 2-(2-cthyloctyD-6-ethyldecene-1 4-ethy1 decene-l Codimer of l-dodecene and 1-tetradecene 8 Z-methyl-l-decene and 2-pr0py1-1-0ctene..

2ethyl-1-decene and Zbutyl-l-octene 2-propy1-1-heptene 2-propyl-1-tetradeeene and 2-pentyl-l-dodecene propyl-l-hexadeecne and Z-pentyl-l-tetradecen bomb vented, opened, 100 ml. of ethanol introduced into the reaction mixture and the bomb rescaled, heated to 125 C., cooled, vented, the reaction mixture removed from the bomb, the bomb Washed with ethanol and the combined reaction mixture and washings poured into 500 m1. of water to decompose the aluminum catalyst, the mixture well shaken, 25 ml. of concentrated hydrochloric acid added thereto and the aqueous phase removed.

Starting olctins in moles 4.0, l-dodecene; 12.0, propylene 3.04, l-hexadecene; 14.9, propylene.

ML, diisobutyl aluminum Reaction Reaction hydride temp, 0. time, hrs. g. olefin The following compounds of this invention are prepared utilizing the dimerized compounds as set forth in Examples 1 through 22 prepared utilizing process step (1).

EXAMPLE 23 A four-necked, 500 ml. flask is equipped with a stirrer, a thermometer, an addition funnel and a reflux condenser fitted with a Drierite tube to prevent moisture from getting into the system. A solution of 100 ml. of nitromethane and 13.3 g. (0.1 mole) of anhydrous aluminum chlo ride is prepared in the flask while the said flask is held in an ice-water bath to maintain said solution at a temperature of about C. Then 280 g. (1.0 mole) of 2-octyldodecene-l from Example 1 is added slowly to said solution through the dropping funnel over a period of about 30 minutes, during which time the temperature of the mixture varied from about 5 to 8 C. This mixture is then stirred for an additional time of about 3.5 hours, during which time the temperature varied from about 8 to 25 C. The reaction mixture is then poured into 500 ml. of water, 100 ml. of hexane added thereto and the aqueous phase separated from the reaction mixture. The organic phase is then respectively washed with 500 ml. of water, 500 ml. of 10% hydrochloric acid solution, 500 ml. of dilute sodium hydroxide solution and 500 ml. of water. the organic phase filtered, the hexane stripped therefrom by distillation under reduced pressure and the reaction mixture stripped of all lower boiling components including unreacted 2-octyldodecene-1.

The crude 2-octyldodecene-l dimer (157 g.) is charged to a 1-liter, stainless steel, rocking bomb and 30 g. of W-4 Raney nickel (in hexane) added thereto. The bomb is sealed, flushed twice with hydrogen and pressured to 1800 p.s.i.g. with hydrogen at 21 C. After the reaction period of about 8 hours, at 200 C., the bomb is allowed to cool, then vented, opened, the reaction mixture removed, the bomb washed with hexane, the reaction mixture and washings filtered to remove the catalyst, the hexane stripped therefrom by distillation under reduced pressure and the remaining reaction product distilled through a Vigreux column. The product (134.4 g.) boiling at 227 to 228 C./0.05 mm. Hg and having a refractive index of 11 1.4573 is recovered, corresponding to a yield of 85.5%, based on crude dimer. The product was identified as 11,13-di-n-octyl-13-methyltricosane.

Calcd for C H (percent): C, 85.4; H, 14.6. Found (percent): C, 85.41; H, 14.76.

This product is a colorless liquid having a density of 0.826, a pour point of -70 F. and a viscosity in centistokes at temperatures of F., 100 F., 210 F. and 400 F., respectively, of 4085, 35.78, 6.28 and 1.51. The thermal decomposition point of 11,13-di-n-octyl-13-methyltricosane is found to be 615 F., and this compound has a normal boiling point of about 990 F.

The product 11,13-di-n-octyl-l3-methyltricosane is also prepared in a similar manner to the experimental procedure disclosed above, but wherein the 2-octyldodecene-1 is dimerized with ferric chloride and hydrogen chloride.

EXAMPLE 24 The 2-hexyldecene-1 from Example 2 is dimerized in the presence of anhydrous aluminum chloride attenuated with nitromethane in a similar manner to that shown in Example 23. A 500 ml. flask is equipped with a stirrer, thermometer, dropping funnel and reflux condenser fitted with a Drierite tube. Nitromethane (100 ml.) is charged to the flask and cooled to 5 C. by holding said flask in an ice water bath. Then 13.3 g. (0.1 mole) of anhydrous aluminum chloride is added thereto in small increments and dissolved in the nitromethane. Thereafter 224 g. (1.0 mole) of 2-hexyldecene-1 is added to the catalyst solution through the dropping funnel over a period of about minutes, during which time the mixture in the flask is maintained at from 5 to 10 C. by cooling in an ice water bath. Then the reaction mixture is stirred for an additional time of 2 hours at a temperature of from 5 to 15 C., after which time it is poured into 500 m1. of water. The aqueous phase is separated and the organic phase diluted with about 100 ml. of benzene. The organic phase is then washed three times with 500 ml. portions of water, the organic phase recovered and the benzene stripped therefrom by distillation under reduced pressure. The reaction mixture is fractionated through a Vigreux column 10 and a portion of the 2-hexyldecene-1 recovered together with 121.6 g. of the crude 2-l1exyldecene-1 dimer.

The crude dimer is charged to a 1-liter, stainless steel, rocking bomb and 25 g. of Raney nickel catalyst added thereto. The bomb is sealed, flushed twice with hydrogen and then pressured to 1800 p.s.i.g. at 30 C. with hydrogen. The reaction mixture is heated at about 172 C. over a period of about 8.5 hours, and then the bomb is allowed to cool, vented, the contents transferred to a flask and the bomb rinsed with benzene. The combined reaction mixture and rinse is filtered and the filtrate stripped free from benzene by distillation under reduced pressure. The reaction mixture is then refractionated through a Vigreux column and 108.2 g. of the fraction obtained at 179183 C./0.05 mm. Hg having a refractive index of n 1.4543 recovered. This fraction is redistilled and 102.3 g. of the fraction obtained at 181 to 183 .C./ 0.05 mm. Hg having a refractive index of n 1.4543

recovered. The product is identified as 9,11-di-n-hexyl-11- methylnonadecane and has a normal boiling point of 880 F.

Calcd for C H (percent): C, 85.3; H, 14.67. Found (percent): C, 85.42; H, 14.70.

This product is a colorless liquid having a pour point below 80 F. and a viscosity in centistokes at temperatures of F., 50 F., 30 F., 100 F. and 210 F., respectively, of 27016, 8573, 2659, 23.68 and 4.88.

EXAMPLE 25 The 2-but loctene-1 from Example 3 is dimerized in the presence of anhydrous aluminum chloride attenuated with nitromethane in a similar manner to that shown in Example 24. The 168 g. portion (1.0 mole) of 2-buty1- octene-l is added to the catalyst solution in the reaction vessel through the dropping funnel over a period of 55 minutes while the temperature of the reaction mixture is maintained at 8 to 10 C. by cooling the flask in an ice water bath. Then the reaction mixture is stirred for an additional time of 2 hours at a temperature of 5 C. to 10 C., and then poured into 500 ml. of water. The aqueous phase is separated and the organic phase diluted with about 100 ml. of benzene, then washed 3 times with 500 ml. portions of water, the organic phase recovered and the benzene stripped therefrom by distillation under reduced pressure.

The crude 2-butyloctene-1 dimer product together with 30 g. of Raney nickel are charged to a 1-liter, stainless steel, rocking bomb, which is sealed, flushed twice with hydrogen and pressured to 2000 p.s.i.g. at 35 C. with hydrogen. The mixture is reacted for about 8 hours at a temperature of 175 C., then the bomb is cooled, vented, the reaction mixture transferred to a flask, the bomb Washed with benzene, the combined reaction mixture and bomb washings filtered and the benzene stripped therefrom by distillation under reduced pressure. The reaction mixture is fractionated through a Vigreux column and the fraction obtained at 128 to 129 C./0.05 mm. Hg having a refractive index of 11 1.4488 recovered. The product is identified as 7,9-di-n-butyl-9-methylpentadecane. This product is a colorless liquid having a pour point below F. and a viscosity in centistokes at temperatures of 65 F., 30 F., F. and 210 F., respectively, of 16874, 1576, 14.09 and 2.69 and a normal boiling point of 740 F.

EXAMPLE 26 A reaction mixture of 181.1 g. (0.54 mole) of 2-decyltetradecene-l from Example 4, 13.3 g. (0.1 mole) of anhydrous aluminum chloride and 100 ml. of nitromethane are reacted in a 500 m1. flask as described in Example 23 and in a generally similanmanner. The 2-decyltetradecene-1 is added to the catalyst solution over a period of about 15 minutes while the reaction mixture is maintained at a temperature of from about 4 to 10 C. by cooling the flask in an ice water bath. The reaction mixture is stirred for an additional 12-hour period, during which time the temperature is allowed to rise to room temperature. Then the reaction mixture is poured into 500 ml. of water, diluted with about 100 ml. of benzene and the aqueous phase and nitromethane layers separated. The organic phase is washed three times with 500 ml. portions of water, the benzene stripped from the organic phase by fractional distillation under reduced pressure and the unreacted Z-decyltetradecene-l recovered by fractional distillation leaving a product fraction of 76.4 g. (11 '1.4618).

The 76.4 g. 2-decyltetradecene-1 dimer fraction is combined with 38 g. of a similar fraction prepared in like manner to that described hereinabove and introduced into a 1-liter, stainless steel, rocking bomb together with 22 g. of Raney nickel. The bomb is sealed, flushed twice with hydrogen and pressured to 1900 p.s.i.g. at 20 C. with hydrogen. The mixture is heated to about 200 C. and held at about this temperature for a time of about 9.5 hours. Then the bomb is cooled, vented, the contents transferred to a flask, the bomb rinsed with benzene, the combined product filtered, the filtrate stripped of benzene by distillation under reduced pressure and the reaction product fractionated through a Vigreux column. A 96.0 g. fraction was obtained (n 1.4632) and redistilled at 250 to 255 C./0.05 mm. Hg. The product is identified as 13,1S-di-n-decyl-S-methylheptacosane. This product is a colorless liquid having a pour point of 15 F., a refractive index of 11 1.4632, a viscosity in centistokes at temperatures of 100 F. and 210 F., respectively, of 45.06 and 7.74 and a normal boiling point of 1060 F.

EXAMPLE 27 The codimer mixed product from the dimerization of decene-'1 and dodecene-l, i.e., a mixture of 2-octy1dodecene-l, 2-decyldodecene-l, 2-octyltetradecene-1 and 2-decyltetradecene-l from Example 5, in an amount of 308 g. (about 1.0 mole average) together with 6.2 g. (0.5 mole) anhydrous aluminum chloride and 50 ml. of nitromethane are reacted in a 500 ml. flask as described in Example 23. The codimer mixed product is first saturated with hydrogen chloride prior to addition to the reaction flask via the dropping funnel over a period of about 25 minutes, while the contents of the flask are held at a temperature of from about 4 to 8 by cooling in an ice water bath. Then the reaction mixture is stirred for an additional time of about 2.5 hours at a temperature of about to C., after which time it is poured into 500 ml. of water. The aqueous phase is separated and the organic phase diluted with about 200 ml. of hexane, then washed twice with 500 ml. portions of water followed by a wash with 500 ml. of a dilute sodium bicarbonate solution. The hexane is stripped therefrom by distillation under reduced pressure and 136.4 g. of the crude dimer of the original codimer mixed product recovered.

This recovered mixed product is charged to a l-liter, bottom-stirred autoclave together with g. of Raney nickel, the bomb sealed, flushed twice with hydrogen and then pressured to 1900 p.s.i.g. at C. with hydrogen. After a reaction time of about nine hours, during which time the temperature is raised to 196 C., the bomb was allowed to cool, vented, the reaction mixture transferred to a flask and the bomb rinsed with hexane. The combined reaction mixture and rinse is filtered, the filtrate stripped of hexane by distillation under reduced pressure, the reaction mixture fractioned through a Vigreux column and the fraction obtained at 231 to 250 C./0.05 mm. Hg recovered. This reaction mixture consists of saturated hydrocarbon compounds ranging from C H to C H This mixture is a colorless liquid having a pour point of 40 F. having a normal boiling point range of from 990 F. to 1060 F. The compounds after utilizing both fractional distillation and vapor phase chromatography are 11,13-diocty1-l3-methyl tricosane, 11-octyl-13-decyl- 13-1nethyl tricosane, 11,13-di0ctyl-13-methyl pentacosane,

1 2 11-octyl-13-decyl-13-methyl pentacosane, 11,13-didecyl- 13-methyltricosane, 1l-decyl-13-octyl-13-methylpentacosane, 11,13-didecyl-13-methyl pentacosane, 33,15-dioctyl- 15-methyl heptacosane, 13-octyl-15-decyl-15-methyl heptacosane and 13,15-didecyl-15-methyl heptacosane.

EXAMPLE 28 Utilizing a reactor as set forth in Example 23, 280 grams (1 mole) of 2-octyl-1-dodecene is charged to the flask. The temperature is reduced to 0 C. and the reaction flask purged with hydrogen chloride gas. To the reaction flask is then added 3.1 grams (0.023 mole) aluminum chloride over a period of about 5 minutes. The temperature is maintained in the range of -3 to 4 C. for a period of 2% hours. After this time ml. of Water is added to the reaction mixture to decompose the aluminum chloride. To the crude trimer is added hexane and the hexane crude trimer is washed with hydrochloric acid and an aqueous 10% sodium hydroxide solution followed by two water washes. The product is filtered and the hexane is removed by distillation.

Utilizing a hydrogenation reactor as is set forth in Example 23, the crude trimer is charged to the reactor together with 50 g. of Raney nickel. The temperature is increased to 200 C. at a hydrogen pressure of about 2700 p.s.i.g. for a period of 17 hours. The product is distilled at a temperature of 300 C. at 0.05 mm. The compound 11,13,15 trioctyl-l3-decyl-15-methyl pentacosane has a pour point of -30 F. and a viscosity at 210 F. of 18.018.

EXAMPLE 29 Utilizing the procedure as is set forth in Example 28, Z-decyl dodecene-l is trimerized in the presence of aluminum chloride and HCl gas. The crude trimer is hydrogenated for a period of 16 hours utilizing hydrogen and a Raney nickel catalyst at a temperature of about 200 C. The compound is identified as 11,13,13,15-tetradecyl- 15-methyl pentacosane having a boiling point greater than 950 F.

EXAMPLE 30 Utilizing the same equipment as is set forth in Example 28, 2-hexyldecene-1 is trimerized in the presence of aluminum chloride catalyst and gaseous HCl. The crude trimer after distillation is charged into an autoclave together with a Raney nickel catalyst and the hydrogen pressure increased to about 1800 p.s.i.g. A temperature of C. is maintained for a period of 16 hours. After fractional distillation, the compound 9,11,13-hexy1-11- octyl-l3-methyl heneicosane is obtained having a boiling point greater than 860 F.

EXAMPLE 31 To a reactor as described in Example 28 2-dodecyltetradecene is charged together with aluminum chloride and gaseous HCl. The crude trimer is obtained after distillation which is hydrogenated utilizing a Raney nickel catalyst and hydrogen at pressures of from 1600 p.s.i.g. to 1950 p.s.i.g. at a temperature of from 180 C. to C. After fractional distillation the compound 13,l5,15,l7- tetradodecyl-17-methyl nonacosane is obtained having a normal boiling point greater than 1000 F.

The following additional examples of compounds of this invention are prepared as set forth in Table II utilizing the dimerized olefins of process step (1) as is set forth in Table I. The catalyst system that was utilized was an aluminum chloride moderated nitromethane system. In Examples 33 and 36 as set forth in Table II the mixture of compounds was obtained by fractional distillation by separation from the dimethyl derivatives which are also produced in the dimerization reaction in process step (2). The hydrogenation system that is used is hydrogen plus a Raney nickel catalyst.

TABLE II Starting dimer from Mole Example N0. process Step 1 Source ratio Compound 9.1l,dipropyl-11-methyl nonadecene. 32 (a) ff g 1 1 {11,13-dioctyl-lZi-methyltricosane. (b) 2-oc y o ecenexamp 6 SJ-propyl-ll-octyl-ll-methyl heneieosane. 33 (a) Z-methyl decene-1. Example 9 g9-methyl-11-0ctyl-ll-methylheneicosane.

(b) 2-octyl dodecene-l Example 1 lliPdigfityl l-lllil-metlslhyl tricogane.

1e -me nona ecene. 34 (a) g' decene'l gw q 3"} 7,9-dibutgl-9-methyf pentadecene.

(b) damp e 7-butyl-9-ethyl-9-methyl heptadecene.

(b) Z-butyl decene-l Example 14....

1l.l3-diethyl l3-methyl tricosane. g-ethyl dodecene'l-u Example .{9,11-dibutyl-1l-methyl nonadecene.

El-butybll-ethyl-ll-methyl heneicosane. $11,13-dioctyl-13-methyl tricosane. t6-propyl-8-octyl-8-methyl octadecene.

The compounds of this invention are particularly suitable for use in jet engines since the boiling points of the compounds are far in excess of those temperatures encountered in a jet engine. Thus, for example, a compound having a boiling point of about 400 or 450 F. is not suitable for operation in a jet engine at temperatures as set forth above since a compound having this boiling point would be readily volatilized from the jet engine and would not be capable of lubricating critical parts in a jet engine. As has been set forth above, the lubricant of a jet engine must have certain properties and one of the necessary properties of such a lubricant is a relatively high boiling point. As is seen from the foregoing examples, boiling points of over 700 F. and in many cases over 1000 F. are readily obtainable by the compounds of this invention.

As a result of the excellent properties of the compounds of this invention lubrication of gas turbine engines is obtained. Thus this invention relates to a novel method of lubricating gas turbine engines which comprises applying on the bearings a lubricating amount of a compound or mixture of compounds of this invention. In general, a functional fluid should contain at least about 20% by weight of a compound or mixture of compounds of this invention in order to obtain the excellent lubricating properties of these compounds. In addition, the compounds of this invention can be utilized in hydraulic pressure devices which comprise in combination a fluid chamber and an actuating fluid composition in said chamber, said fluid composition comprising one or more compounds of this invention in a concentration of at least about 20% by weight. In such a system, the parts which are so lubricated include the frictional surfaces of the source of power, namely, the pump, valves, operating pistons and cylinders, fluid motors, and in some cases, for machine tools, the ways, tables and slides. The hydraulic system may be of either the constant-volume or the variable-volume type of system.

The pumps may be of various types, including centrifugal pumps, jet pumps, turbine vane, liquid piston gas compressors, piston-type pump, more particularly the variable-stroke piston pump, the variable-discharge or variable displacement piston pump, radial-piston pump, axialpiston pump, in which a pivoted cylinder block is adjusted at various angles with the piston assembly, for example, the Vickers Axial-Piston Pump, or in which the mechanism which drives the pistons is set at an angle adjustable with the cylinder block; gear-type pump, which may be spur, helical or herringbone gears, variations of internal gears, or a screw pump; or vane pumps. The valves may be stop valves, reversing valves, pilot valves, throttling valves, sequence valves, relief valves, servo valves, non-return valves, poppet valves or unloading valves. Fluid motors are usually constantor variabledischarge piston pumps caused to rotate by the pressure of the hydraulic fluid of the system with the power supplied by the pump power source. Such a hydraulic motor may be used in connection with a variabledischarge pump to form a variable-speed transmission.

The compounds of this invention when utilized as a functional fluid can also contain dyes, pour point depressants, metal deactivator, acid scavengers antioxidants, de-

foamers in concentration suflicient to impart antifoam properties, such as from about 10 to about 100 parts per million, viscosity index improvers such as polyalkylacrylates, polyalkylmethacrylates, polycyclic polymers, polyurethanes, polyalkylene oxides, polyalkylene polymers, polyphenylene oxides, polyesters, lubricity agents and the like.

It is also contemplated within the scope of this invention that the compounds of this invention as aforedescribed can be utilized singly or as a fluid composition containing two or more compounds of this invention in varying proportions. The compounds of this invention can also contain in concentrations of from about 20 to about weight percent other fluids which include, in addition to the compounds described above, fluids derived from coal products and synthetic oils, e.g., alkylene polymers (such as polymers of propylene, butylene, etc., and mixtures thereof), alkylene oxide-type polymers (e.g., propylene oxide polymers) and derivatives, including alkylene oxide polymers prepared by polymerizing the alkylene oxide in the presence of water or alcohols, e.g., ethyl alcohol, alkylbenzenes, (e.g., monoalkylbenzene such as dodecylbenzene, tetradecylbenzene, etc.), and dialkylbenzenes (e.g., n-nonyl Z-ethyIheXyIbenZ/ene); polyphenyls (e.g., biphenyls and terphenyls), polyphenyl ethers, polyphenyl thioethers, mixed polyphenyl ether-thioethers wherein the number of aromatic rings in the above compounds varies from about 3 to about 6, halogenated benzene, halogenated lower alkylbenzene, .halogenated biphenyl, monohalogenated diphenyl ethers, trialkyl phosphates, triaryl phosphates, mixed arylalkyl phosphates, U ialkyl, phosphine oxides, diarylalkyl phosphonates, trialkyl phosphonates, aryldialkyl phosphonates, triaryl phosphonates, diand tri-carboxylic acid esters, such as di-2-ethylhexyl adipate, di-2-ethylhexyl sebacate, polyesters, such as trimethylolpropane, pentaerythritol, dipentaerythritol esterified with acids such as butyric, propionic, caproic and 2-ethylhexanoic and complex esters such as are obtained by esterifying a dicarboxylic acid with a glycol and a monocarboxylic acid, and mixtures thereof.

While this invention has been described with respect to various specific examples and embodiments, it is to be understood that the invention is not limited thereto and that it can be variously practiced within the scope of the following claims.

What is claimed is:

1. A compound represented by the structural formula wherein R, R R and R are each normal linear alkyl groups having an even number of carbon atoms and from 2 to 16 carbon atoms, provided that the total number of carbon atoms present in the compound is from at least 24 carbon atoms to about 60 carbon atoms.

2. A compound of claim 1 wherein the number of carbon atoms present in the compound is from at least 24 to about 48.

3. A compound of claim 2 wherein the sum of the 15 carbon atoms present in R and R is from 6 to about 28 and the sum of the carbon atoms present in R and R is from 8 to about 32.

4. A compound of claim 3 wherein the sum of the carbon atoms present in R and R is from 8 to 24 and the sum of the carbon atoms present in R and R is from 12 to 24.

5. A compound of claim 1 which is 9,11-di-n-hexy1-11- methylnonadecane.

6. A compound of claim 1 which is 11,13-di-n-octyl- 1 3-methyltricosane.

7. A compound of claim 1 which is 7,9-di-n-butyl-9- methylpentadecane.

8. A compound of claim 1 which is 13,15-di-n-decyl- IS-methylheptacosane.

1 6 References Cited UNITED STATES PATENTS 2,830,106 4/1958 Good et a1 260683.15 3,156,736 11/1964 Southern et a1. 26'0683.15

OTHER REFERENCES Ferris: Handbook of Hydrocarbons, pub. by Academic Press Inc., New York (1955), pp. 258-269 relied PAUL M. COUGHLAN, JR.,Primary Examiner U.S. Cl. X.R.