|Publication number||US2197835 A|
|Publication date||Apr 23, 1940|
|Filing date||Aug 3, 1938|
|Priority date||Aug 3, 1938|
|Publication number||US 2197835 A, US 2197835A, US-A-2197835, US2197835 A, US2197835A|
|Inventors||Orland M Reiff|
|Original Assignee||Socony Vacuum Oil Co Inc|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (37), Classifications (160)|
|External Links: USPTO, USPTO Assignment, Espacenet|
Patented Apr. 23, 1940- UNITED STATES txamine PATENT OFFICE MINERAL OIL COMPOSITION Orland M. Reifi, Woodbury, N. J., assignor to Socony-Vacuum Oil Company, Incorporated, New York, N. Y., a corporation of New York No Drawing. Application August 3, 1938, Serial No. 222,755
This invention has to do in a general way with mineral oil compositions and is more particularly concerned with the production of a mineral oil fraction of the viscous type having an improving agent incorporated therein.
It is a primary object of this invention to provide a mineral oil composition of the type above referred to which has been improved in several related and unrelated properties by a single improving agent. The invention is predicated upon the discovery of a novel class of improving agents of multifunctional activity, which may be broadly described as oil-miscible metalorganic compounds or compositions characterized by the presence of a wax-substituted aryl nucleus.
I have found that compounds or compositions falling into the above general class, when blended in a minor proportion with a mineral oil fraction of the lubricant type, are eifective to depress the pour point, improve the viscosity index (V. I.) and inhibit oxidation of the oil. By inhibiting oxidation these improving agents act to retard the formation of sludge and acidic products of oxidation. They also have a peptizing action on such sludge as may eventually be formed. Thus the improving agents contemplated herein, may, for example, be used in internal combustion engine lubricants to retard or prevent the sticking of piston rings, the corrosion of bearings (particularly those formed of alloy metals normally susceptible to corrosion)','etc.,-and -at'i'il'fe same time will act to deprgssthepour point and improue the viscosity index of "the "bfilj rfifoiigh the proper'choi'ceof metal substituents (lead, copper, tin, or zinc for example) the load-carrying capacity or lubricity of the oil may also be improved. This so-called extreme pressure (E. P.) value of heavy lubricants may be even further improved by the presence in these metalorganic compounds of other substituents such as sulfur and chlorine.
The use of these improving agents is not confined to lubricating oils, however, but they may be employed in any mineral oil fraction where one or more of the improved properties recited above is desired.
1/ Although I do not wish to be bound by any theory as to the manner in which the improving agents described herein function in a mineral oil fraction, it appears that pour point and V. I. improving properties are derived from the large complex molecular structure obtained fromthe wax or equivalent long chain aliphatic hydrocarbon substituent and the associated aryl nucleus or nuclei and that the antioxidant properties of' long chain aliphatic group or radical derived from some other compound or material in suflicient amount to render the compostion miscible with mineral oil under normal conditions of handling and use and a metal or metallo constituent which may be in the form of a metal atom directly attached to the hydrocarbon radical or group or which may be present as a metallo complex, such as a metal-substituted hydroxy, thiohydroxy,'carboxy, or thiocarboxy group corresponding respec- I.
tively to an oxide, a mercaptide, a metal'carboxylate, or a metal salt of a thio acid such as thiolic or xanthic acid and the like.
Compounds or compositions of the above general character may also be broadly classified into two groups, depending upon whether the metal or metallo complex (metallo-oxy, metal carboxylate, metal, etc.) is directly attached to the aryl nucleus which carries the wax substituent or is directly attached to a hydrocarbon substituent or substituted hydrocarbon substituent in the aryl nucleus.
To facilitate the description and illustration of the general class of compounds or compositions contemplated herein vas oil-improving. a nts, we may represent these compounds or compositions by the following general formula:
in which (Wax) molecular radical or group of a predominantly aliphatic hydrocarbon material characterized by a relatively long chain molecular structure .of at least twenty carbon atoms, such as petroleum wax, ester wax, and the like, which radical or group is present asa substituent attached to an aryl nucleus T; n represents the number of wax is'equal to one or. a whole number correspon ing to the number of valences on the aryl nucleus T which are not indicates the characterizing 5o substituents attached to a single nucleusT. and f' satisfied by residual hym a or othersubstituents T-representsiiramfiatic I hydrocarbon radical such as, for example, one selected from the group comprising monocyclic or polycyclic aryl, alkaryl, hydroxy-aryl, halogenaryl, amino-aryl, nitro-aryl radicals or groupsfdiaryl radicals in which the aryl nuclei are directly connected, diaryl radicals in which the aryl nuclei are connected through an ether, keto, or thio-ether linkage, etc; Z represents nitrogen, oxygen or sulfur or the related elements, selenium and tellurium, or a radical selected from the group consisting of:
|--ORX); io-R- -X- (-X-(i-X so:); (-R;Sa); (cXN- (RGXN-); (CNN); (RCNN); (-N=N- (NHNH-) which will be hereinafter referred to as group A and in which It represents an aryl or an alkyl radical or group and X, X and X represent oxygen or sulfur; 0 represents the number of Z constituents and is equal to zero or a whole number corresponding to valences on T not satisfied with wax, residual hydrogen, or other substituents; M represents at least one hydrogen equivalent of a metal which is either directly attached to the aryl nucleus T or is attached indirectly to the aryl nucleus T through the atom or group represented by Z; 11 represents the number of Ms and is always equal to a whole number which, if c is a whole number, is equal to c, it being understood that when 0 equals zero, d must be a whole number so that the composition or molecule represented by the above Formula I must contain at least one chemically combined hydrogen equivalent of a metal.
In further amplification of the foregoing general Formula I, it will be seen that when 0 is equal to zero, the metallo substituent becomes the hydrogen equivalent of a metal (M) directly attached to the nucleus T, in which event the compound is represented by the formula (wax) n-T-M'; also when 0 is a whole number and Z is oxygen or sulfur, the formula for the composition may be written:
in which X represents oxygen, sulfur, selenium or tellurium and M" represents the hydrogen equivalent of a metal. Instead of including the isolated metal substituent M, the (X"M") substituent, and the substituents of group A all under the one representation (ZcMd) as was done in general Formula I, I may also represent the group of compounds or compositions contemplated herein by the general formula representation:
in which M'k indicates the hydrogen equivalent of a metal directly attached to the nucleus T; M indicates the hydrogen equivalent of a metal indirectly attached to T through oxygen or sulfur (X") and M indicates the hydrogen equivalent of a metal indirectly attached to the nucleus T through Z which may be any one of the radicals listed above in group A. The subscripts I0, 1), and s indicate the number of M, (Z'M) and (X"M) substituents, respectively, and are each equal to zero or a whole number corresponding to the valences on T not satisfied by (wax) 7r, residual hydrogen, or other substituents, at least one of the subscripts k, p, or 3 always being equal to a whole number.
As has been previously pointed out, the wax substituent cooperates with the aryl nucleus to which it is attached in giving pour depressing and V. I. improving properties to the agents contemplated herein. This substituent serves the additional function of solubilizing the compound or composition as a whole. It is important for the uses contemplated herein that these metalorganic compounds be oil-miscible; that is, capable of remaining uniformly dispersed in mineral oil either as a true solution or a colloidal suspension under normal conditions of handling and use. In this regard there appears to be a critical zone or region in the degree of wax-substitution below which the compounds or compositions contemplated herein are not readily soluble in viscous mineral oil fractions. This degree of wax-substitution for an oil-soluble or oil-miscible metalorganic compound of the general type described above may vary over relatively wide limits, depending upon whether the aryl nucleus is monoor poly-cyclic and whether such nucleus carries other substituents, such as hydroxy, alkoxy, aroxy, halogen, nitro, amino radicals or groups, etc. As indicated above, petroleum wax is the preferred source of the wax substituent, but it is to be understood that other equivalent long chain aliphatic hydrocarbon compounds, such as ester waxes, may be employed.
As sources for the aryl nucleus which carries the wax substituent I may employ any one of a multiplicity of monoor polycyclic, substituted or unsubstituted aromatic compounds.
In general it appears that any metal may be used in the compounds contemplated herein to provide compositions which have multifunctional mineral oil-improving properties. Metal substituents which are considered particularly useful in these improving agents may be broadly classified as the metals belonging to the silver, copper, tin, aluminum, iron, alkali and alkaline earth analytical groups, which include: silver, mercury, lead, and thallium; bismuth, copper, and cadmium; arsenic, antimony, and tin; iron, cobalt, nickel, and manganese; barium, calcium, strontium, and magnesium; and sodium, potassium, and lithium, respectively. Other desirable metals include: titanium, cerium, thorium, vanadium, molybdenum, tungsten, uranium, and platinum.
Exemplary types of compounds falling into the general class contemplated by this invention are illustrated in the following table in which the formulae given are for illustrative purposes only and show only the monocyclic nucleus which is unsubstituted except for the wax and a metal or a metallo complex substituent.
Table I 1. Wax-aryl-metallo compounds (a) (wax .M
01. bUlVHUDl IIUND, LAQLHHMU Type compound Illustrative general formula. Type compound Illustrative general formula )n EI (b) (wax),.- -R XM V 10 2. Wax-aryl metal oxides.. (a) (wax)- --0M v A 7. Wax-aryl-ether metal (a) (wax),. X"-RM compounds. A u (b) mm --ROM A V (b) (wax),.- -X"-R-XM 3. Metal salts of wax-nryl (a) (wax),. SM X thio acids. '4 20 V (c) (wax),. -XR-- -XM (b) (wax),. RSM 26 (a) (Wax)n-- -X -XM SH 30 \X n 30 e x R-C-XM wa SM G-XM as (won-Q X,
C-RM 8 Wee); 2311!! 5:150 metal (a) (wax) SH 4o (e) (wax)n 0 WM),.-- C-R-XM H C-XM SM 45 (c) (wax),, C-RCXM 0') )n-- I V 0 XM IB 5 4. Metal] salts of wax-cry] (a) (wax)- C-XM (d) (WflX)'- ac s. 55 2 1 a )n --R-C-XM O l V 9. Wax-aryl-ester metal (a) (wax)n@C-0-RXM 60 or; compounds. I 5. Metal salts of wax-hy- (a) (wax),,-- -C--XM droxy-aromatic acids. (b) (wax)n -CO--RM 65 OM (b) (wax),. -C-XM f 0-0K 70 x (wa 6. Metal salts of wax-hy- (a) (wax) -g,8XM
droxyaromatic aliphatv lc aclds. ("l-KM Type compound Illustrative general formula Type compound Illustrative general formula 10. Metal salts of wax-aryl sullonic acids.
12. Metal salts of win-aryl amides.
In the foregoing exemplary formulae (wax)n has the same significance indicated above in connection with general Formula I: X, X and X represent oxygen, sulfur, or the related elements, selenium and tellurium; R represents an aliphatic or an aromatic group which may or may not be otherwise substituted. R of Formulae 11 and 12 represents hydrogen, alkyl, or aryl radicals, and Mm in Formulae 1(0), 11(a)2, (b)2 and (0)2 represents double compound metal salts formed by addition of inorganic salts to aromatic hydrocarbons and to aromatic amines.
It will be observed from the foregoing illustrative examples that all of the disclosed compounds are metalorganic compounds or compositions which are characterized by the presence of a wax-substituted aryl nucleus. The compounds falling into the groups indicated by the numerals 2 to 12 inclusive may be considered as compounds in which the metal is present in the radical or group WM in which M represents the hydrogen equivalent of a metal and in which W represents nitrogen, oxygen, sulfur, selenium or tellurium, or the radicals --SO3- and in which X and X indicate oxygen or sulfur. In part of these typical compounds the radical WM is directly attached to the aryl nucleus and in other of these compounds the radical WM is attached to adaydrocarbon substituent R which may be either alkyl or aryl in nature.
Compounds of the type represented by groups 2 and 3 may be considered as wax-aryl metalorganic compounds in which the metal is present in the radical XM where X represents oxygen or sulfur or the related elements, selenium and tellurium, and compounds represented in groups 4 to 9 inclusive, which contain either the XM group or the group, may also be considered as compounds containing metal in the radical --XM, since the compounds of these groups which contain the carboxy or thio acid radical will also contain the radical XM discussed above because the radical XM forms part of the metallo-carboxy or metallothio acid radical. Compounds in which the hydrogen of a carboxy or thio acid group is substituted with its equivalent weight of metal may be classified as metalorganic com- 252. UUMPU IHUNS,
fur. It is to be understood that metal attachments to R (where R is aryl) such as M or WM (where W represents nitrogen, oxygen, se-' lenium, tellurium, or (SO3) (CX'X) etc., can also be made on the wax-aryl nucleus, further, where R is aryl in the formulae of Table I, it may,be wax-substituted.
In connection with the illustrative examples given in Table I, it is to be understood that the aryl nucleus may be polycyclic (a nucleus derived from naphthalene, anthracene, diphenyl, etc); also that there may be other substituents in the nucleus than the wax and metal or metallo complex. In this same regard it should be understood that the wax substituent (aliphatic group containing at least twenty carbon atoms) may be polyvalent in nature, in which event each of the polyvalent wax radicals or groups will be attached to a plurality of aryl nuclei, each of which aryl nuclei has at least one metal or metallo complex substituent, and each of which may have attached to it one or more monovalent wax substituents and may, in addition, have other substituents, such as aliphatic hydrocarbon groups containing less than twenty carbon atoms, hydroxy, alkoxy, aroxy, alkaryl, aralkyl, aryl, halogen, cyanogen, nitro, nitroso, amino, keto, ester, aldehyde, amide, thiamide or thiaroxy radicals or groups, etc.
Where nuclear substituents are present containing methylene groups such as alkyl, keto, ether, ester, acid radicals, etc., the same may also carry substituents such as halogen, hydroxy, amino, nitro, cyanogen, etc. Metal compounds containing thiaroxy substituents are an important class. By the reaction of wax-aryl compounds, the metal salts of which are illustrated in Table I, with sulfur dichloride, hydrochloric acid gas is evolved with the formation of the aryl thio ether compound, By reaction with sulfur monochloride the disulfides are formed.
Formula I above illustrates the essential requisites of the compounds or compositions contemplated herein, namely, a wax-substituted aryl nucleus and a metallo complex in chemical combination therewith; and if it is borne in mind that (waxhl may be one or more monovalent or polyvalent aliphatic hydrocarbon groups of at least twenty carbon atoms or a mixture of such groups, that T may be otherwise substituted, and that (ZcMd) represents at least one hydrogen equivalent of a metal or a metallo complex containing one such equivalent of a metal, this formula is a fairly accurate representation of the field of compounds or compositions contemplated herein. To illustrate more completely and more accurately the field of invention, taking into consideration the polyvalent wax type of wax-aryl metalorganic composition and also taking into consideration the possibility of other substituents in the aryl nucleus, I have devised the following general formula:
in which T has the same significance described above under Formula I; (ZcMd) represents at least one metallo atom or one metallo complex of the type described in connection with Formula I; R represents at least one aliphatic or alkyl hydrocarbon (wax) group having at least twenty carbon atoms, such wax group or groups being attached by one valence only to at least one aromatic nucleus T; 12 represents the valence of the wax radical R", which I have found for best results in obtaining oil-miscible products should be one to four; Yb represents a monovalent element or group, such as residual hydrogen, which may be replaced with an aliphatic radical or group containing less than twenty carbon atoms, hydroxy, alkoxy, aroxy alkaryl, aralkyl, aryl, halogen, cyanogen, nitro, nitroso, amino, keto, ester, aldehyde, amide, thiamide or thiaroxy radicals or groups, etc.; 1) represents the number of Ybs and is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied with R or (ZcMd) and e represents a whole number from one to four and indicates the total number of groups (T- (Yb) (ZcMd)) present in the molecule represented by the formula which are attached to the aliphatic group or groups represented by R".
In the foregoing general Formula II it will be seen that the compounds represented thereby include those materials in which all of the .wax substituent (RF) is monovalent (0:1 and e=1) or in which all of the wax substituent is polyvalent (v and e being equal to two, three or four) or since R. is defined as being at least one and may therefore include several such groups, it will be seen that this general Formula II is inclusive of compounds having aliphatic groups or radicals of difierent valences (from one to four) in the same molecule. Also, it will be observed that since e may be any whole number from one to four, the number of aromatic nuclei T in the molecule may likewise vary from one to four. It will be seen, therefore, that the relationship between e and v in Formula II in its broadest aspect is such that when e is equal to one, 12 is equal to one, and when e is greater than one, the valence v of at least one of the R s is equal to e in order to tie the several nuclei or Ts together, the valence of any remaining R s being any whole number equal to or less than c.
The more simple types of compounds coming under general Formula II in which 12 and e is each equal to one and in which there is only one wax substituent R may be illustrated by the following formula showing T for purposes of illustration as a monocyclic nucleus:
there are two such monovalent R" groups, may be represented by the following formula:
H H H 11 HO --C C --OH H H H H in which the chain and substituent characters have the same significance defined above.
Compounds of the type satisfying general Formula II in which R is polyvalent and v and e are more than one and in which there is only one such polyvalent R group may be illustrated by the following formula in which the aryl nucleus T is again indicated for illustration as being monocyclic:
(Z=M.1) (ZMa) (Z=Md) Yr-i- Yr- Yb H \l/ H H0 "o --o --c -CH H H H H H Under this same type of compound indicated by Formula C there may also be more than one R (wax) group (represented by the chain), such compound in which there are, for example, two polyvalent R. groups being illustrated by the following formula in which the characters have the same significance described above under Formula C:
H H H H HC--C "OH I (ZJWJ) (ZBMJ) d) H HG "C "CH have the same significance as in the formulae above.
H H H H 11% -C --C --C -CH /L =Md) I (ZZM.1) I C d) H H Y5 I Y's-p I Y1,- --C- -"CH n H H y I II no --o --o -01! H II II It As to the number of R" (wax") groups going to make up a single molecule, this will vary with the extent to which it is desired to effect substitution of the nucleus with the wax derivatives for obtaining the desired properties in the product aromas and is, 01 course, limited by the number of replaceable hydrogens on the aromatic nucleus which are available for substitution. As will be apparent to those skilled in the art, the maximum number of R groups which can be attached to a single aromatic nucleus will vary as the nucleus is monoor polycyclic and also as the nucleus is otherwise substituted. It will also be apparent that replaceable hydrogens on the nuclei may all be substituted with polyvalent wax substituents.
It will be understood that the oil-improving agents contemplated by this invention may be pure compounds satisfying the general Formula II above with a monoor poly cyclic nucleus as T and with or without one or more of the various Yb substituents. However, in manufacturing the preferred oil-improving products of this invention by procedures in which wax-substitution is eiTected with a chlorinated wax by the Friedel- Crafts reaction, the final oil-improving product is normally or usually a mixture of difierent compounds corresponding to different values of c and v and to different numbers of wax groups R".
Since the wax-aryl metalorganic compounds or compositions described herein are contemplated for use as oil-improving agents, it is important that the wax substituent comprise a sufiicient proportion of the composition as a whole to render the same miscible with mineral oil fractions under normal conditions of handling and use. The amount of wax substituent to accomplish this will, as stated above, vary under different conditions; but, as a general guide, it appears that best results are obtained if the percentage of wax contained in the Wax-aryl constituent calculated as a wax-aromatic compound otherwise unsubstituted is not substantially less than eighty per cent.
Instead of grouping the various possible metal substituents under one radical (ZcMd) as was done in general Formula II, this same type of formula may be employed, indicating the possible metal-bearing substituents with the radicals Mk, (ZM) and (X"M")s, which have the same significance described above in connection with general Formula I. This modification of general Formula II may be written as follows:
Illustrative procedures which may be followed in synthesizing typical compounds or products fallin into the various type compound classifications of Table I will now be described. It is again emphasized that while Table I shows only monocyclic aromatic derivatives, both monoand polycyclic compounds are contemplated herein; and that where the term wax is used, I have reference to any equivalent aliphatic hydrocarbon having at least twenty carbon atoms or organic compositions predominantly comprised of such high molecular weight aliphatic hydrocarbons.
TYPE CoMPoUNn 1 Wax-aryl-metallo compounds illustrated under Example 1, Table I, may be prepared by (a) the Grignard reaction or (b) reaction of wax-aryl compounds with alkali metals in the presence of aliphatic ethers.
The Grignard reaction may be used for the synthesis of various metal compounds other than those of the alkali group. It is well known that aromatic halogen derivatives with the halogen in the nucleus or side chain react in dry ethereal 252. COMPOSITIONS,
or hydrocarbon solution with magnesium metal to form organo magnesium compounds, such as RMgBr and RCHz-MgCl, for example, where R is aryl. These metallo compounds, known as Grignard reagents, can be used in the synthesis of other metal compounds by reaction with a halide of the desired metal whereby double decomposition takes place to form magnesium halide and the desired metallo derivatives.
For the synthesis of Type 1 compounds illustrated as (a) and (b) in Table I, wax benzene is to be first prepared, followed by chlorination at low temperature in the dark to efiect chlorination of the nucleus in synthesis of 1(a) or by chlorination at about 200 F. in the presence of light or carriers such as iodine to produce chlorination of the wax or lower alkyl group in the synthesis of compounds of the 1(b) type.
The formation of the Grignard reagent (waxaryl-magnesium compounds) is to be carried out in the same manner for Type compounds 1(a) and 1(b), followed by reaction with a halide of the desired metal to form the wax-aryl-metallo compound.
Alkali metal compounds of Type 1 Wax naphthalene, for example, is reacted with alkali metal in a proportion of one atomic weight of alkali metal for each mole of wax naphthalene in the presence of an aliphatic ether such as dimethyl ether, the mixture being agitated at a temperature below the boiling point of the ether until solution of the alkali metal takes place.
TYPE COMPOUND 2 Typical compounds or products belonging to representative members of the general class of wax-aryl metalorganic compositions typified by the formulae of group 2 in Table I together with illustrative methods for synthesizing these products will be described in thefollowing examples:
A parafiin wax melting at approximately F. and predominantly comprised of aliphatic hydrocarbon compounds having at least twenty carbon atoms in their molecules was chlorinated by melting the wax and bubbling the chlorine therethrough until it had absorbed about sixteen per cent chlorine, such-product having an average composition between a monochlor wax and a diohlor wax. A uantity of this chlorwax containing three atomic proportions of chlorine was thenreacted with one molecular proportion of phenol (CcHsOI-I) in the presence of aluminum chloride to form a wax-phenol having a phenol content in the neighborhood of about thirteen per cent. After purification to remove all unreacted phenol this wax-phenol was reacted with finely divided metallic sodium at a temperature of 500 F. with rapid stirring and in the presence of a non-oxidizing gas to form a wax-substituted sodium phenate. Wax-substituted potassium phenate may be prepared by following the same procedure, using a temperature of 400 F., the reaction being completed in a one-hour period. Examples of the reacting proportions which may be used in the synthesis are as follows:
Parts by weight (a) Wax-phenol (13.2% c o m b i n e d phenol) 500 Sodium or equivalent amount of potassium 16 (b) Wax-naphthol (15.7% c o m b in e d naphthol) 500 Sodium or equivalent amount of potassium 12% exam m6! Wax-substituted aryl oxides of the alkali or alkaline earth metals and metals from the silver, copper, aluminum, tin, and iron analytical groups can also be prepared by the reaction of the waxhydroxyaromatic compound (wax-phenol) with an alcoholate of the desired metal, the reaction mixture being heated to about 300 F. during a one-hour period. The alcohol is distilled off during the reaction, thereby obtaining a wax-substituted aryl metal oxide as the finished product. Anhydrous methyl and ethyl alcohols are considered preferable for preparing the alcoholates for use in this reaction.
The wax-aryl lead oxide (wax-substituted lead phenate) can be readily prepared by reacting wax-phenol with litharge in the presence of a non-oxidizing gas and heating the mixture with stirring to a temperature of about 500 F. during a one-hour period.
It will be observed that the phenol content of the wax-phenol used in the preparation of wax phenates was given above as being in the neighborhood of thirteen per cent. I have found that as a general proposition where wax-phenols having a phenol content substantially greater than thirteen per cent are employed in the preparation of the wax phenates (wax-substituted aryl metal oxides), products of the desired solubility in viscous mineral oils do not appear to be readily obtained. It may be said, therefore, as a general proposition that the preparation of wax-substituted aryl metal oxides according to the procedures outlined above should be carried out with wax-substituted hydroxyaromatic com pounds in which the ratio of hydroxyaromatic compound to wax-substituted hydroxyaromatic material is not substantially greater than the chemical equivalent of thirteen per cent phenol.
TYPE COMPOUND 3 The type compound represented by Formula 3(a) is to be prepared by the reaction of a waxaromatic compound with sulfur monochloride to form a disulfide, followed by reduction to form the mercaptan.
Naphthalene, for example, is to be reacted with a chlorwax of about sixteen per cent chlorine content in the presence of anhydrous aluminum chloride. By use of the aluminum chloride catalyst in a concentration of about ten per cent by weight in respect to naphthalene, a triwax naphthalene can be prepared by heating the reaction mixture to about 300 F. and holding at this temperature during a one-hour period.
Reaction mixture Grams Chlorwax 200 Naphthalene 45.6 A1C13 4 The reaction product is to be purified by washing with water to remove the aluminum chloride, thereafter separating the water and drying the mixture to obtain the finished wax naphthalene. The. operation of water-washing can be facilitated by the use of diluents such as benzol and using alcohol to break the emulsions. The diluent will also be an aid in drying the product, as
complete removal of water will be effected during the distillation of the diluent.
The wax naphthalene is then to be reacted with sulfur monochloride in the following proportions at about F. to form the disulfide:
V Moles Wax naphthalene; 2
Sulfur monochloride SzClz 1 The disulfide is to be reduced to the mercaptan by treating with reducing agents such as tin or iron in the presence of hydrochloric acid, stirring the mixture vigorously to facilitate the reducing action by improved contacting of the mixture with nascent hydrogen.
The product may then be neutralized with aqueous sodium hydroxide solution to form the sodium mercaptide. The mixture can be dried to give the finished alkali metal salt; or the aqueous mixture can be reacted with aqueous solution of a polyvalent metal salt, stirring the mixture at about 175 F. during a one-hour period to obtain the polyvalent metal mercaptide. The product is to be purified by water-washing to remove reaction salts, followed by separation of the water and drying to give the finished product.
TYPE COMPOUND 4 Example 1 Wax-aromatic acids of type 4(a) wherein X and X represent oxygen are to be prepared from wax-aromatic hydrocarbons by different procedures:
1. By formation of a ketone followed by oxidation of the keto group to a carboxyl radical by reaction with oxidizing agents such as alkali hypochlorites or permanganates.
2. By direct oxidation of, an alkyl group to COOH.
3. By chlorination of the aromatic nucleus of the wax-aromatic hydrocarbon, followed by reaction with sodium and C02.
The preferred procedure consists in formation of a keto product, followed by oxidation. A triwax benzene is to be formed by the Friedel-Crafts reaction described in example of Type compound 3 in formation of wax naphthalene. Without purification of the Friedel-Crafts reaction product, acetyl chloride, for instance, is to be introduced in an amount to form a monoor diketo product, heating the mixture with stirring at about F., using a chlorinated solvent such as ethylene chloride to reduce the viscosity of the mixture.
The ketone may then be purified by washing with water to remove the aluminum chloride, followed by refluxing with sodium hypochlorite for several hours and stirring vigorously to effect the oxidation of the keto group to carboxyl. The use of a hydrocarbon diluent such as benzol will be desirable in this reaction to reduce the viscosity of the mixture. The free acid may then be obtained by neutralizing the mixture with mineral acid. The wax aryl acid thus formed is neutralized with an alcohol solution of sodium hydroxide to form the sodium salt.
The polyvalent metal salts can then be prepared by double decomposition of. the sodium salt with an equivalent amount of the desired polyvalent metal salt in aqueous or non-aqueous medium according to procedures herein outlined.
When the alkali metal salts are to be isolated rather than used as intermediates in the formation of the salts of polyvalent metals, they may be prepared by neutralization of the wax acid with alcoholic solution of alkali hydroxide, distilling the water of reaction and alcohol to give the finished product.
Example 2 Wax-aryl aliphatic acids, the salts of which are illustrated in Type compound 4(1)) of Table I,
wherein X and X represent oxygen, have been prepared by the reaction of a wax-aromatic hydrocarbon with an unsaturated aliphatic acid such as oleic acid; or with a chloraliphatic acid such as chlorstearic acid.
A wax naphthalene, for example, prepared by procedure described under Type compound 3, is condensed with oleic acid, for instance, by use of anhydrous aluminum chloride as a catalyst, using an amount of aluminum chloride sufiicient to neutralize the carboxyl group, and heating the mixture at about 300 F. to bring about the formation of the aluminum salt of the wax-aryl aliphatic acid. The free acid is then obtained by washing the mixture with aqueous hydrochloric acid to decompose completely the aluminum salt.
The polyvalent metal salts are prepared by neutralizing the free acid with aqueous sodium hydroxide solution (20% NaOH) and then reacting with an equivalent of an aqueous solution of a salt of the desired metal, stirring the mixture at about F. during a one-hour period to complete the formation of the polyvalent metal salt. The product is purified by water-washing to remove reaction salts, separating the water and drying to obtain the finished product.
The reaction of double decomposition between the alkali metal salt and the salt of the desired polyvalent metal can also be carried out in nonaqueous medium. In this case the wax-aryl acid is neutralized with alcoholic alkali hydroxide or with a sodium alcoholate (alcoholate prepared preferably from amyl or lower alcohol). The reaction mixture is heated to about 300 F. and held at this temperature about one hour, allowing the alcohol to distil to give the finished alkali metal salt. The mixture is then treated with an alcohol-soluble salt of the desired polyvalent metal in an amount equivalent to the alkali metal salt, thereafter adding about ten per cent by volume of amyl alcohol and refluxing at about 240 F. during a one-hour period to complete the reaction.
The polyvalent metal salt can be purified by filtering, centrifuging or water-washing to remove the reaction salts.
Chlorinated or hydrocarbon solvents such as. tetrachlorethane, Stoddard solvent and toluene may be used during the preparation and purification of the salts to reduce the viscosity of the mixture, in which case the diluent is finally distilled to give the finished product.
Because of emulsions formed in the preparation of alkali salts in aqueous medium, it is preferred to prepare such compounds by the reaction of the wax aryl acids with alkali alcoholates (alcoholates formed preferably from amyl or lower alcohols), heating the reaction mixture to about 300 F. during a one-hour period and allowing the alcohol to distil to obtain the finished salt.
The alcoholate method, as described under the preparation of wax-aryl metal oxides of polyvalent metals (Type compound 2), may also be used in preparing the carboxylates of polyvalent metals of type compounds illustrated in Table 1.
Example 3 Thio acids such as thiolic acid; the salts of which are represented by Type formula 4(a), wherein X represents oxygen and X represents sulfur, are to be prepared by the reaction of wax aryl acid chlorides with sodium sulfide, followed MPUSITIONS,
by neutralization of the alkali salt with mineral TYPE COMPOUND Example 1 A wax-phenol or a wax-substituted hydroxyaromatic compound having a combined phenol content in the neighborhood of from thirteen per cent to sixteen per cent is prepared and converted into the wax-aryl metal oxide or the wax phenate of an alkali metal in the same manner described under Type compound 2 above, after which it is carboxylated according to the Kolbe synthesis (passing CO2 through the compound or a solution thereof at elevated temperature (350 F.) and either atmospheric or superatmospheric pressure) to form the alkali metal salt of the wax-substituted hydroxyaromatic carboxylic acid. This salt constitutes one of the products or improving agents contemplated by this invention and the corresponding salts of other metals may be formed from the alkali metal salt by a process of double decomposition with the alcoholsoluble inorganic or fatty acid salt of the desired metal. Products of this synthesis are typical of the Type compounds 5(a) in Table I.
Example 2 With a wax-substituted hydroxyaromatic carboxylic acid of the type obtained in Example 1 as a starting material the metal salts wherein both the hydroxyl and the carboxyl groups are substituted with metal may be obtained by reacting the hydroxyaromatic salt of Type compound 5(a) with an alcoholate of the desired metal, thereby replacing the hydroxyl hydrogen with such metal. Salts of this last-mentioned type may be obtained in which the metal substituent in the hydroxy group is the same metal as or a different metal from the metal substituent in the carboxy group. Salts of this type, which I may term wax-substituted metaloxyaromatic-metal carboxylate salts, are typical of Type compound 5(b) in Table I.
TYPE COMPOUND 6 Example 1 A wax-phenol having a combined phenol content of about thirteen per cent is reacted withan unsaturated aliphatic acid such as oleic acid in the presence of anhydrous aluminum chloride. By use of an amount of aluminum chloride equivalent to both the hydroxyl group of the phenol examine:
about two parts of benzol and neutralizing with aqueous sodium hydroxide solution (20% NaOH), thereafter forming the polyvalent metal salt by double decomposition with an equivalent amount of the desired metal salt in aqueous solution. The reaction of double decomposition can be completed by stirring the mixture about an hour at 175 F., thereafter water-washing the product to remove completely the reaction salts and distilling the benzol to obtain the finished product.
Products of this example are typical of Type compound 6 (a) in Table I.
Example 2 Type compounds 6(b) of Table I wherein both the hydroxyl and carboxyl group are substituted with metal can be obtained by reacting the metal salt of Example 1 with an alcoholate of the desired metal, whereby the hydroxyl hydrogen is replaced with metal. Salts of this type can be prepared in which the metal substituent of the carboxyl group is unlike the metal substituent in the hydroxyl group. Compounds of this type are termed wax-substituted metaloxyaromaticmetal carboxylate salts of wax-hydroxy-aryl aliphatic acids.
TYPE CoMPoUNn 7 Example 1 Wax-sodium phenate is prepared from waxphenol of about sixteen per cent combined phenol content according to the procedure described in the preparation of Type compound 2. Sodium chloracetate is then prepared by slowly adding to an alcohol solution of chloracetic acid, a standard alcoholic solution of sodium hydroxide, keeping the temperature of the reaction mixture below 100 F. The sodium chloracetate is then added to the wax-sodium phenate, the reaction mixture being held at a temperature of 150 F. during a two-hour period. By diluting the mixture with an appropriate diluent such as Stoddard solvent the mixture can be centrifuged or filtered to remove reaction salts, thereafter removing the diluent by distillation to obtain the sodium salt of a wax-phenyl ether acid as the final product. Corresponding salts of other metals may be prepared by reacting the sodium (or other alkali metal or an alkaline earth metal) salto'f the ether acid with an alcohol-soluble inorganic or fatty acid salt of the desired metal at a temperature of 175 F. over a two-hour period.
It will be understood, of course, that the sodium or other alkali metal salts of other chlororganic acid may be used in the first. step of this procedure to obtain other ether acid salts or oxy-alkyl acid salt substituents on the aryl nucleus.
Products of this example are typical of Type compound 7(a) in Table I.
Example 2 The salts of aryl-xanthic acids illustrated by Type formula 7(a), wherein X" is oxygen and X and X represent sulfur, can be prepared from the reaction product of wax-alkali phenates with carbon disulfide.
A triwax-phenol, for example, formed by the reaction of phenol with chlorwax of nineteen per cent chlorine content, is reacted with sodium ethylate, the mixture being heated to 300 F. and held at this temperature about an hour to form the wax-sodium phenate. By reaction or the phenate with carbon disulfide in a pressure bomb,
heating at about 200 F. during a one-hour period, the wax-aryl sodium xanthate is formed. The product of this reaction is soluble in mineral oil.
Any of the wax-alkali-aryl xanthates can be formed by this reaction by the modification of preparing the wax phenates of the desired alkali metal. The polyvalent metal salts can be prepared by double decomposition of the alkali salt with a salt of the desired polyvalent metal, the reaction being carried out in aqueous or nonaqueous medium.
Example 3 Another example of Type formula 7(d) Wherein X", X and X represent oxygen, is found in the reaction of a wax-alkali phenate with CO2. This product is an intermediate in the formation of the alkali salts of wax-phenolic acids illustrated by Type formula 5(a).
In the reaction of wax-sodium phenate with CO2, the wax phenate is first converted into a product (identified as the intermediate represented by 7(cl)), which is highly resilient when cool but which changes upon further reaction to a more fluid product, the latter being identified as the sodium salt of wax-phenolic acid. The intermediate product is usually designated as an alkali-aryl carbonate, but conducts itself in a manner similar to the aryl ether acids in rearranging to give hydroxyaromatic acids of Type formulae 5(a) and 6(a).
TYPE COMPOUND 8 Example 1 Metal salts of keto acids can be prepared from wax acids formed by the condensation of waxaromatic or wax-substituted mixed aromatic hydrocarbons with anhydrides of dibasic acids, of aliphatic, cycloaliphatic or aromatic type. Examples of mixed aromatic hydrocarbons are phenols, aromatic ethers, and heterocyclic compounds.
Naphthalene, for example, is condensed with chlorwax of about sixteen per cent chlorine content by procedure above outlined and condensed with phthalic anhydride in the presence of aluminum chloride, using the following proportions:
Moles Wax-naphthalene 1 Phthalic anhydride 1 Aluminum chloride 2 The wax-naphthalene and phthalic anhydride are mixed together and dissolved by addition of a chlorinated solvent such as tetrachlorethane, thereafter adding the aluminum chloride in small portions at a time at' room temperature. The reaction temperature is then raised to 200 F. and the mixture stirred for several hours to complete the reaction.
In the formation of the polyvalent metal salts, the reaction mixture is washed with water containing sufficient mineral acid to remove the aluminum and neutralized with aqueous sodium hydroxide solution; an equivalent amount of an aqueous solution of a salt of the desired polyvalent metal is then added, the reaction and purification being carried out by procedures herein outlined.
Example 2 In Example 1, which illustrates a method of preparation of Type compound 8(0), the aromatic nucleus to which the carboxylate radical is attached is not wax-substituted. Type compound 8(d) is an example of a wax-substituted aromatic nucleus to which the carboxylate radical is directly attached. In preparing this latter type of product wax-benzene, for instance, is to be converted to a diketo product by reaction with an acid chloride such as acetyl chloride, as described under preparation of compounds of Type 4 (a). Mixed ketones are to be formed also by use of both aliphatic and aromatic acid chlorides. The diketo product is to be partially oxidized to give the desired keto acid from which the metal salts may be prepared. R of Formula 8 ((1) will be alkyl when an aliphatic acid chloride only is used in formation of the diketo product; R will be aryl when a mixed aliphatic-aromatic diketo product is formed in the synthesis of keto acids.
TYPE COMPOUND 9 Example 1 Wax-aryl ester metal compounds represented by Formula 9 (a, b, c) are to be prepared from the reaction products of wax-aromatic acids with alcohols. Compounds 9 (a, b) are to be prepared from esters formed by the reaction of monobasic wax aryl acids with monoor dihydric alcohols; Compound 9 (c) from acid esters of wax-aryl dibasic acids and monohydric alcohols.
Compound represented by 9 (c), for example, is to be prepared by the reaction of a wax aryldicarboxy acid with sufficient aliphatic or aromatic monohydric alcohol to form the acid ester, thereafter neutralizing with sodium hydroxide solution to form the alkali salt, followed by reaction with a salt of the desired polyvalent metal in aqueous or non-aqueous medium by procedures herein outlined to form the polyvalent metal salt.
Example 2 The wax-aryl ester metal compounds represented by Formula 9 (d, e, 1) have been prepared from the reaction products of wax-phenols and wax phenolic acids with aliphatic or aromatic acid chlorides. Compounds 9 (d, e) are prepared from esters formed by the reaction of wax-monoand polyhydric phenols with monobasic acid chlorides; Compound 9 (I) from acid esters of wax phenolic acids and monobasic acid chlorides.
Compounds represented by 9 (j), for example, may be prepared by the reaction of wax phenolic acid with acetyl chloride, for instance, to form the acid ester. The acid ester is then neutralized with alcoholic alkali hydroxide to form the alkali salt as one product of this invention. The salts of polyvalent metals are then prepared by double decomposition of the alkali salt with a salt of the desired metal in aqueous or non-aqueous medium to form the polyvalent metal salt.
TYPE COMPOUND 10 Metal salts represented by Type formulae 10 (a) and 10 (0), wherein R. is aryl, are to be prepared from the sulfonic acids resulting from the sulfonation of wax-aromatic hydrocarbons, waxphenols or wax-aryl ethers.
Compounds represented by Type formulae 10 (b) and 10(0), wherein R is alkyl, are to be prepared by the halogenation of wax-aromatic compounds whereby the side chain is substituted, followed by reaction with alkali sulfite to form the wax-aryl-aliphatic sulfonates.
The polyvalent metal salts are to be prepared by the reaction of the alkali salt with an in- 2oz. UUIVIPUSI HONS, a lilfll 5 A e e a et od o the fo at on of Metal compounds wherein a valence of a polypollnds of yp 11 Consists in e formation of valent metal is satisfied by a hydroxyl group conmetal salts of aromatic amines resulting from m t basic metal compounds The method of the nitration d following reduction of formation consists in the use of one extra equivaa a yd s, wax-hyd y r at lent of alkali hydroxide in the neutralization of hydrocarbons, and wax-aromatic ethers. Nitrath free ax acid, followed by treating with a 10 tion o e nucleus followed y reduction Will amount of polyvalent metal salt equivalent to the give arylamines; reduction of nitro groups present 1 1i hydroxide d, in side chains will result in the formation of wax- DOUBLE COMPOUNDS FROM WAX-ABOMATIO Coluaryl'ahphatlc ammes' room) WITH BIETAL HALIDE AN METALS 15 Metal compounds of the (a, b, c)1 type can be S 8 D 15 formed from the alkali metals, substituting one It has been previously pointed out that double or both of the hydrogens of the amino group compounds can be formed with metal halides and with metal. aromatic amines (Type compounds 11(CL)2, (1292,
Metal compounds of the (a, b, 0)2 type are and (0)2. Likewise, double compounds can be formed from inorganic salts such as ZnClz, COClz, formed by an addition reaction of wax-aro- 20 HzPtClc, HAuCla, etc., wherein straight addition matic compounds with metallic halides such as to the amino group takes place to form double stannic chloride, aluminum chloride, etc. The compounds. V Grignard reagents above described are examples By the well-known procedure of diazotization, of addition compounds formed by the reaction of the wax-arylamines are to be converted to the aryl halides with metals. Further, the alkali 25 diazo c p n s which may be represented y metals form metal salts with aromatic comthe gro p (N=N) Because of the alkaline pounds by an addition reaction, giving derivatives nature of the diazo compounds, double salts can of the double compound type. It is to be underbe formed by e ion With inorganic metal salts stood, therefore, that the present invention con- (--N=N-MHe). templates waX-aryl metallo compounds of both 30 By reactions w w to the art, the product the addition and substitution type as multiresulting from the reaction of diazotization may functional mi al oil-improving agents. be converted to compounds of the general formula Numerous compounds or compositions falling (N=NA) whe ein A y be within the broad general class contemplated (S B (CX' from Which metal Salts herein have been synthesized and tested in min- 35 can be derived (N=N'SO3 eral oil fractions of the viscous or lubricant type N=N-CXXM). and all of them have been found to be possessed y reduction of the product of diazotizetion of multifunctional oil-improving properties in y diaZonium chloride) in acid medium the that they all have been definitely proved to effect 40 W 37 hydrazines are to be formed, having improvement in at least two of the following 4 (--N'I-INH) as a characteriz ng p- The properties, namely, pour point, viscosity index, ClPaZlneS are known to form Salts of the type of and inhibition of oxidation. All of the composithe eryleminestions which have been tested for all three prop- TYPE COMPOUND 12 erties have been found to be improving agents Wax-aryl amides, the metal salts of which are all h Tllese l p be used in 45 illustrated by Type formulae 12, are to be viscous mineral oil fractlons in varying amounts pared from wax-aryl and wax-aryl ether acids rangmg m oneslxteenth P t E ten per by the general method of formation of the acid cent dependmg upon condltlqn of chlorides followed by treating with ammonia. etc., and Table II below is representative of the The thiamides can be formed from the amides by numer 011s waxaryl-metano compositions which 50 reaction with P2S5 have been prepared and tested to demonstrate the The amides and thiamides are known to be efficacy f the n r l class of compounds nd tautomeric in form, whereby two types of metal compositions contemplated by this invention. salts (a, b, oh and 2 are possible. In one type (a, b, c) 1 the amino hydrogen is substituted with Table II v 55 metal; in the (a, b, (2)2 type the substitution Cuprio Salt of Wax-phenol oarboXyllo eold with metal takes place in the OH or SH group, Aluminum salt of Wax-phenol carboxylic acid leaving the nitrogen valence (R) satisfied with Zino Salt of waX-phenol oalboxyllo fie hydrogen alkyl, or aryl radica1s Chromic salt of wax-phenol carboxyllc acid (30 Amidines f the general formula Ferric salt of wax-phenol carboxylic acid 50 are to be prepared from the amides or thiamides Cobaltous Salt of Wax-Phenol oarboXylio a by replacement of oxygen or sulfur with NH or MangaIlOv-S Salt of Wa -p f y acid NR (R being alkyl, aryl, OH, etc.) using methods Calcium salt of wax-phenol carboxyllc acid familiar to the art. Where hydrogen is substi- Magnesium Salt of WaX-Phenol carboXylio acid G5 tuted with an OH group amidoximes are formed \VPQtaSSlUm salt of Wax-phenol carboxylic acid CNNOH) Salts of the amine type can be Sodium salt of wax-phenol carboxylic acid prepared from the amidines' Cobalt salt of wax-pheno1 carboxylic acid Sodium salt of Wax-beta naphthol carboxylic acid NEUTRAL ACID AND BASIC METAL SALTS OF Sodium salt of wax-alpha naphthol carboxylic ARYL COMPOUNDS acid 70' In the foregoing discussion, methods have been Wax-lead phenate a given for the preparation of neutral metal salts, Wax-stannous phenate but it is to be understood that acid and basic Wax-aluminum phenate metal salts of compounds represented by Type Wax-zinc phenate l5 formulae 2-12 are also contemplated. Wax-calcium phenate 15 organic salt of the desired metal in aqueous solution by procedures above outlined.
TYPE COMPOUND 11 Metal compounds wherein one or more acid groups, such as phenolic OH, mercaptan, SH, carboxy or thiolic groups, etc., remain unsubstituted are considered as acid metal salts.
Wax-potassium phenate nitrogen, sulfur, oxygen, selenium, tellurium, Wax-sodium phenate (SO3), (-CXN), (-CNN), and Wax-sodium beta naphtholate Wax-sodium alpha naphtholate I Wax-sodium phenate-sodium carboxylate salt Wax-cupric phenate-sodium carboxylate salt Wax-Cobaltous phenate-manganous carboxylate salt Wax-cobaltous phenate-cobaltous salt Wax-stannous phenate-stannous carboxylate salt Wax-stannous phenate-cobaltous carboxylate salt Wax-ferric phenateferric carboxylate salt Zinc salt of wax-phenyl-methyl carboxy ether acid Cobaltous salt of wax-phenyl-methyl carboxy ether acid Dicobaltous salt of dicarboxy wax phenolic acid Cobaltous salt of wax-naphthyl-stearic acid Cobaltous salt of wax-hydroxy-phenyl stearic acid Cobaltous salt of wax-naphthoyl benzoic acid Wax-phenyl sodium xanthate All of the products enumerated in the above table can be broadly identified as oil-miscible metalorganic compounds or compositions which are characterized by the presence of a wax-substituted aryl nucleus. In some of these products the metal is present as a metallo-complex directly attached to the aryl nucleus, and in others it is present in a side chain (ether acid, aryl aliphatic acid, etc.) substituent. All of the compounds listed above satisfy and come under general Formulae I, I and II, II. It is to be understood that certain of these compounds or compositions may be preferred for use in certain mineral oil fractions and certain of the compounds or compositions may be preferred to others, depending upon the conditions or properties which are to be improved, but it is, as stated above, a characteristic of all of these products or compositions that they have multifunctional oilimproving properties which may vary in magnitude, etc., with the oil and the constituents of the compounds. Some of the compounds or compositions or sub-groups of compounds or compositions may be preferred to others from the standpoint of cost, ease of synthesis, odor, color, etc., but it is not my intention in the present application to draw any preferential differentiation or distinction between the various subgroups, since they are being made the subject matter of additional applications. It is emphasized, therefore, that the invention is not limited by the specific examples or illustrative procedures described above but includes within its scope such variations and modifications as fairly come within the scope of the appended claims.
1. A mineral oil composition comprising: a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound characterized by the presence carboxylate "of a wax-substituted aryl nucleus.
in which X and X represent oxygen or sulfur.
3. A mineral oil composition comprising a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound characterized by the presence of a wax-substituted aryl nucleus, at least part of the metal in said compound being present in the radical XM in which M represents the hydrogen equivalent of a metal and X represents elements from the group consisting of sulfur and oxygen.
4. A mineral oil composition comprising a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound characterized by the presence of a wax-substituted aryl nucleus, at least part of the metal in said compound being present in the radical in which M represents the hydrogen equivalent of a metal and X and X represent elements from the group consisting of oxygen and sulfur.
5. A mineral oil composition comprising a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound characterized by the presence of a wax-substituted aryl nucleus, at least part of the metal in said compound being present in the radical ZM attached to said wax-substituted aryl nucleus and in which M represents the hydrogen equivalent of a metal and Z represents a radical selected from the group consisting of nitrogen, sulfur, oxygen, selenium, tellurium:
in which R represents a hydrocarbon group and X, X, and X" represent radicals selected from the group consisting of oxygen and sulfur.
6. A mineral oil composition comprising a viscous mineral oil fraction and in admixture therewith an oil-miscible metalorganic compound which is characterized by the presence of a wax-substituted aryl nucleus, said metalorganic compound being present in an amount sufficient to improve the oil in at least two of the following respects: improvement of pour point; improvement of viscosity index; and inhibition of oxidation.
'7. A mineral oil composition comprising a viscous mineral oil fraction and in admixture therewith from about one-sixteenth per cent to about ten per cent of an oil-miscible metalorganic compound which is characterized by the presence of a wax-substituted aryl nucleus.
8. A mineral oil composition comprising a viscous mineral oil fraction and in admixture therewith from about one-sixteenth per cent to about ten per cent of an oil-miscible metalorganic compound which is characterized by the presence of LUL: UUIVIFUOI l IUHO an aryl nucleus having part of its nuclear hydrogen substituted with petroleum wax.
9. A mineral oil composition comprising a mineral oil fraction and in admixture therewith a minor proportion of a metalorganic compound which is characterized by the presence of a waxsubstituted aryl nucleus and in which said wax substituent-comprises a sufiicient proportion of said compound to render same miscible with said oil fraction under normal conditions of handling and use.
10. A mineral oil composition comprising a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound characterized by the presence of a wax-substituted aryl nucleus, at least part of the metal in said compound being present in the radical -WM in which M represents the hydrogen equivalent of a metal and W represents a radical selected from the group consisting of sulfur, oxygen, and the radical x! in which X and X represent element selected from the group consisting of oxygen and sulfur, said radical -WM being a substituent in said aryl nucleus.
11. A mineral oil composition comprising a mineral oil fraction and in admixture therewith a minor proportion of a metalorganic compound having the general formula:
wherein: T represents an aromatic nucleus; (ZcMd) represents a metallo substituent which is attached to said aromatic nucleus and wherein: Z represents a radical selected from the group consisting of nitrogen, sulfur, oxygen, selenium, tellurium, and
in which R. represents a hydrocarbon group and X, X and X" represent elements selected from the group consisting of om'gen and sulfur; M represents the hydrogen equivalent of a metal; 0 is equal to zero or a whole number; and d is a whole number which, when 0 is a whole number, is equal to 0; Yb represents a monovalent radical selected from the group consisting of allphatic hydrocarbon radicals having less than twenty carbon atoms, hydroxy, alkoxy, aroxy, aralkyl, alkaryl, aryl, halogen, cyanogen, nitro, nitroso, amino, keto, ester, aldehyde, amide, thiamide, and thiaroxy radicals; 1) represents the number of Ybs and is equal to zero or a whole number corresponding to the valences on T not satisfied by R or (ZcMd) R, represents at least one aliphatic group of at least twenty carbon atoms having a valence v of one to four and attached by one valence only to at least one nucleus T; and e is a whole number from one-to four.
12. A mineral oil composition comprising a mineral oil fraction and in admixture therewith a minor proportion of a wax-aryl metalorganic compound having the general'formula:
in which T represents an aromatic hydrocarbon radical selected from the group consisting of monocyclic and polycyclic aryl, aralkyl, hydroxyaryl, halogen-aryl, amino-aryl, nitro-aryl, and diaryl radicals; (wax) represents aliphatic hydrocarbons characterizing wax attached to the aryl nucleus T; n represents the number of wax groups and is equal to a whole number corresponding to valences on T not satisfied by residual hydrogen or other substituents; M represents the hydrogen equivalent of a metal directly attached to the nucleus T; (X"'M") represents, a metallo complex directly attached to the nucleus 'I in which M" is the hydrogen equivalent of a metal and X represents an element from the group consisting of oxygen, sulfur; selenium, and tellurium; (ZM)represents a metallo complex attached to the nucleus T and wherein M is the hydrogen equivalent of a metal and Z repre sents a radical selected from the group consisting of:
(-NHNH-), -oNN-), -RoNN- in which R represents a hydrocarbon group, and X, X and X" represent elements selected from the group consisting of oxygen, sulfur, selenium, and tellurium; and k, p, and s are subscripts indicating the number of M, (Z'M) and (X"'M) substituents respectively and each is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied by residual hydrogen or other substituents, at least one of the subscripts lc, p, or s always being equal to a whole number.
ORLAND M. REIEF.
DISCLAIMER -.:5:';;:;" 2,197,835.0rland M. Rez'fi, Woodbury, N. J. MINERAL OIL COMPOSITION. Patent 3 dated April 23, 1940. Disclaimer filed July 16, 1942, by the assignee,
Socony-T acuum Oil Company, Incorporated. Hereby disclaims the following subject matter from each of the claim patent: A mineral oil fraction having in admixture therewith a minor proportion of a metal salt of a wax-substituted aromatic sulfonic acid.
[Oflicial Gazette August 25, 1942.]
n s m sald 1 v CERTIFICATE.OF CORRECTION. Patent No. 2,197,855. April 2;, 191m.
ORLAND M. REIFF.
It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 15 first column, line 25, claim 10, for the words "an element read "elementsand that the said Letters Patent shouldbe read with this correction there-' in that the same may conform to the record of the case in the Patent Office.
Signed and sealed this 18th day of March, A. 1). 191m.
Henry Van Arsdale,
(Seal) Acting Commissioner of Patents.
DlSCLAlMER 2,197 ,835.Orland M Reifl, Woodbury, N. J. MINERAL OIL COMPOSITION. Patent dated April 23, 1940. Disclaimer filed July 16, 1942, by the assignee, Socony-T acuum Oil Company, Incorporated. Hereby disclaims the following subject matter from each of the claims insaid patent:
A mineral oil fraction having in admixture therewith a minor proportlon of a metal salt of a. wax-substituted aromatic sulfonic acid.
[Ofliciql Gazette August 25, 1942.]
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US2421004 *||Aug 3, 1944||May 27, 1947||Socony Vacuum Oil Co Inc||Mineral oil composition|
|US2428340 *||Dec 21, 1944||Sep 30, 1947||Griffin Chemical Company||Composition of matter, its preparation and utilization|
|US2429905 *||Sep 10, 1943||Oct 28, 1947||Sun Oil Co||Lubricant composition|
|US2436051 *||Aug 29, 1944||Feb 17, 1948||Standard Oil Co||Lubricant|
|US2438599 *||Jun 17, 1944||Mar 30, 1948||Monsanto Chemicals||Lubricating oil composition|
|US2442915 *||Jun 22, 1944||Jun 8, 1948||Socony Vacuum Oil Co Inc||Mineral oil composition|
|US2448037 *||Dec 8, 1944||Aug 31, 1948||Lubri Zol Dev Corp||Lubricating compositions|
|US2451037 *||Dec 5, 1942||Oct 12, 1948||Texas Co||Lubricating oil|
|US2503246 *||Sep 28, 1948||Apr 11, 1950||Lubrizol Corp||Asphalt emulsion|
|US2518372 *||Nov 20, 1946||Aug 8, 1950||Socony Vacuum Oil Co Inc||Alkyl substituted thiophene sulfonic acid salts as detergents in mineral oil compositions|
|US2586191 *||Aug 21, 1948||Feb 19, 1952||Harvel Corp||Salts of sulfonated ethers of hydrogenated cardanol as inhibitors for mineral hydrocarbon oils|
|US2652341 *||Mar 25, 1950||Sep 15, 1953||Lubrizol Corp||Asphalt emulsion|
|US2658872 *||Mar 5, 1949||Nov 10, 1953||Standard Oil Dev Co||Modified copolymers and preparation and uses thereof|
|US2659696 *||Jul 17, 1950||Nov 17, 1953||Union Oil Co||Lubricating oil containing a metal salt of a condensation product of an alkyl substituted phenol and an olefin oxide|
|US2665252 *||Sep 25, 1948||Jan 5, 1954||Lubrizol Corp||Lubricants|
|US2677659 *||Mar 21, 1952||May 4, 1954||Socony Vacuum Oil Co Inc||Mineral oil compositions having stabilized low pour points|
|US2816076 *||Aug 7, 1953||Dec 10, 1957||Monsanto Chemicals||Oil-soluble sulfonated hydrocarbons|
|US2984553 *||Oct 24, 1956||May 16, 1961||Socony Mobil Oil Co Inc||Fuel oil composition|
|US2984554 *||Oct 24, 1956||May 16, 1961||Socony Mobil Oil Co Inc||Fuel oil composition|
|US3044960 *||May 26, 1959||Jul 17, 1962||Exxon Research Engineering Co||Lubricating oil containing metal salts derived from hydrogenated bridged phenols andlow molecular weight acids|
|US3044961 *||Apr 1, 1959||Jul 17, 1962||Exxon Research Engineering Co||Metal salts of bridged phenols and low molecular weight acids|
|US3112331 *||Nov 3, 1961||Nov 26, 1963||American Potash & Chem Corp||Silyl, germanyl and stannyl imido phosphoranes, arsanes and stibanes|
|US3252910 *||Jul 1, 1963||May 24, 1966||Socony Mobil Oil Co Inc||Lubricants containing metal compounds of n, n'-substituted dithiooxamides|
|US3268568 *||Jul 14, 1965||Aug 23, 1966||Engelhard Ind Inc||Gold aryl mercaptides|
|US3297586 *||Dec 29, 1964||Jan 10, 1967||Shell Oil Co||Vanadium complexes and polymerization catalyst prepared therefrom|
|US3526661 *||Feb 19, 1968||Sep 1, 1970||Exxon Research Engineering Co||Oil-soluble multifunctional detergent-dispersant comprising an amide of a polyamine and an alkaryl keto acid|
|US4566982 *||Jan 4, 1984||Jan 28, 1986||Exxon Research And Engineering Co.||Metal dithiobenzoates as lubricant additives|
|US4755311 *||Aug 14, 1986||Jul 5, 1988||The Lubrizol Corporation||Phosphorus-, sulfur- and boron-containing compositions, and lubricant and functional fluid compositions containing same|
|US6617287||Oct 22, 2001||Sep 9, 2003||The Lubrizol Corporation||Manual transmission lubricants with improved synchromesh performance|
|US8796192||Oct 29, 2010||Aug 5, 2014||Chevron Oronite Company Llc||Natural gas engine lubricating oil compositions|
|US8841243||Mar 31, 2010||Sep 23, 2014||Chevron Oronite Company Llc||Natural gas engine lubricating oil compositions|
|US8969273||Feb 18, 2009||Mar 3, 2015||Chevron Oronite Company Llc||Lubricating oil compositions|
|US9481841||Dec 8, 2005||Nov 1, 2016||The Lubrizol Corporation||Process of preparation of an additive and its use|
|US20090093384 *||Oct 3, 2007||Apr 9, 2009||The Lubrizol Corporation||Lubricants That Decrease Micropitting for Industrial Gears|
|EP0695798A2||Aug 2, 1995||Feb 7, 1996||The Lubrizol Corporation||Lubricating compositions, concentrates, and greases containing the combination of an organic polysulfide and an overbased composition or a phosphorus or boron compound|
|EP0769546A2||Oct 17, 1996||Apr 23, 1997||The Lubrizol Corporation||Antiwear enhancing composition for lubricants and functional fluids|
|WO2011066059A1||Nov 1, 2010||Jun 3, 2011||The Lubrizol Corporation||Methods of controlling sulfur trioxide levels in internal combustion engines|
|U.S. Classification||508/184, 556/182, 556/148, 556/46, 556/139, 556/52, 556/87, 562/471, 556/63, 556/50, 562/460, 556/69, 556/58, 556/106, 556/51, 556/35, 556/70, 534/13, 556/170, 556/120, 556/112, 508/546, 556/116, 556/110, 562/424, 556/183, 556/77, 556/49, 252/400.1, 556/178, 556/45, 558/270, 556/54, 556/131, 556/64, 556/117, 556/137, 556/119, 556/138, 556/134, 556/107, 562/493, 556/179, 508/551, 556/1, 252/389.1, 252/402, 556/150, 252/391, 562/419, 556/176, 252/403, 556/135, 556/147, 556/177, 556/43, 556/31, 556/85, 556/146, 508/556, 556/184, 556/44, 556/27, 556/136, 556/37, 556/121, 508/541, 534/12, 556/28, 556/108, 508/443, 556/130, 556/42, 556/33, 556/57, 556/76, 252/392, 556/56, 556/78, 508/462, 562/475, 556/34, 556/140, 558/245, 508/501, 562/418, 534/11, 534/15, 556/81, 508/526, 558/248, 556/114, 556/61, 556/80, 508/418, 556/113, 556/40, 556/30, 558/243, 556/105, 556/55, 556/111, 534/16, 556/132|
|Cooperative Classification||C10N2210/01, C10M2211/044, C10M2215/062, C10M2207/286, C10M2219/044, C10M2215/202, C10M159/18, C10N2210/08, C10M2219/082, C10M2227/09, C10M2215/28, C10M2207/121, C10M2215/042, C10M2219/06, C10N2210/07, C10M2207/142, C10M2219/087, C10N2210/03, C10M2207/32, C10N2210/05, C10M2219/085, C10M2207/283, C10M2215/08, C10M2215/18, C10M2215/182, C10M2219/086, C10M2227/081, C10M2207/027, C10M2219/046, C10M2207/285, C10N2210/02, C10N2210/04, C10M2207/028, C10M2219/084, C10M2207/021, C10M2211/042, C10M2207/141, C10M2207/046, C10M2207/282, C10M2207/023, C10M2211/06, C10N2210/06, C10M2215/14, C10M2207/122, C10M2207/284, C10M2215/082, C10M2207/14, C10M2219/062, C10M2215/06, C10M2207/281, C10M2207/124, C10M2207/262, C10M2227/08, C10M2219/089|