Patent GB-532876-A (GB)
Title: Improvements in or relating to mineral oil compositions
IPC: C10M159/18
Filed: 1939-07-25
Abstract: 532.876. Oil compositions. SOCONYVACUUM OIL CO., Inc. July 25, 1939, No. 21647. Convention date, Aug. 3, 1938 [Class 91] Improving agents for addition to mineral oils which have the effect of depressing the pour point, improving the viscosity, having a peptizing action on any sludge which may be formed, and inhibiting the oxidation of the oil comprise a group of oil-miscible metal organic compounds characterized by the presence of a wax-substituted aryl nucleus. The compounds of the invention are included in the general formula where (Wax) indicates the radical of a predominantly aliphatic hydrocarbon compound having a long chain molecular structure of at least 20 carbon atoms such as petroleum wax or ester wax. T represents an aryl nucleus. n represents the number of wax substituents attached to the aryl nucleus T. Z is nitrogen. oxygen, sulphur, selenium, tellurium or a #X<SP>1</SP> ## radical selected from the group (-R-); (-#C-X-); X' X<SP>1</SP> ## ## (-R-X); (-R-#C-X-) ; (-X<SP>11</SP>-R-X) ; (-X<SP>11</SP>-R-#C-X-); #O #O #X<SP>1</SP> #O ## ## ## (-#C-R-X-); (-#C-R-#C-X-); (-#C-O-R-X); #O #X<SP>1</SP> ## ## (-#C-O-R-#C-X-); (-SO 3 -); (-R-SO,-) (-CXN-); (-RCXN-); (-CNN-) ; (RCNN-); (-N=N-); (NH.NH-); which groups are referred to hereinafter as Group A and in which groups R represents an aryl or an alkyl radical, R<SP>1</SP> represents hydrogen or an alkyl or aryl radical and X, X<SP>1</SP> and X<SP>11</SP> represent oxygen or sulphur. c represents the number of Z constituents and is equal to zero or a whole number corresponding to the valences on T not satisfied with wax, residual hydrogen or other constituents, 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 T through the group Z. d represents the number of M units present and is always equal to a whole number, which if c is a whole number is equal to c. The aryl radical T may be one selected from the group comprising monocyclic or polycyclic aryl, alkaryl, hydroxy-aryl, halogen-aryl, amino-aryl, nitro-aryl radicals or groups, diaryl radicals in which the aryl nuclei are connected through an ether, keto, or thioether linkage. Metals mentioned as suitable for use in the compounds of the present invention include silver, mercury, lead, thallium, bismuth, copper, cadmium, arsenic, antimony, tin, iron, cobalt, nickel, manganese, barium, calcium, strontium. magnesium, sodium, potassium, lithium, titanium, cerium, thorium, vanadium, molybdenum, tungsten, uranium and platinum. The aryl nucleus which may be polyvalent as well as monovalent may contain other substituents in the nucleus than the wax and the metal complex. Each aryl nucleus must have at least one and may have more than one wax substituent, and in addition may have other substituents, such as aliphatic hydrocarbon groups containing less than 20 carbon atoms, mercapto, hydroxy, alkoxy, aroxy, alkaryl, aralkyl, aryl, halogen, cyanogen, nitro, nitroso, amino, keto, ester, aldehyde, amide, thiamide, or thiaroxy radicals or groups. When nuclear substituents are present containing methylene groups such as alkyl, keto, ether, ester and acid radicals, these may also carry substituents such as halogen, hydroxy, amino, nitro and cyanogen. Metal compounds containing thiaroxy substituents are stated to be important. The wax substituent may also be polyvalent, in which event each of the polyvalent wax radicals will be attached to a plurality of aryl nuclei, each of which aryl nuclei has at least one metallo complex substituent and each of which again may have attached to it one or more monovalent wax substituents. The aryl nucleus and also the wax substituents may in addition bear any of the substituents referred to above. In consequence of this the simple formula above for the compounds of the invention may be replaced by: which indicates a distribution of the metal complexes into their different sub-divisions. In the formula above Y represents a monovalent aliohatic radical of less than 20 carbon atoms, and hydroxy. mercapto, alkoxy, aroxy, aralkyl, aryl, halogen, cyanogen, nitro, nitroso, amino, keto, ester, aldehyde, amide, thiamide and thiaroxy radicals. b represents the number of Y radicals and is equal to zero or a whole number corresponding to the number of valences on T not satisfied by the wax, metal or metallo group. M<SP>1</SP> 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 sulphur or selenium or tellurium (X<SP>111</SP>). M indicates the hydrogen equivalent of a metal directly attached to the nucleus T through Z<SP>1</SP> which may be one of the radicals listed above as Group A. The subscripts k p and s indicate the number of M<SP>1</SP>, (Z<SP>1</SP>M) and (X<SP>111</SP>M<SP>11</SP>) substituents respectively, and are each equal to zero or a whole number corresponding to the valences on T not satisfied by (wax) n , residual hydrogen or other substituents, at least one of the subscripts always being equal to a whole number. The above formula which is based on a monovalent wax substituent becomes replaced by more complex formulae when the wax residue is polyvalent. Such formulae include in which T has the same significance as in the first formula. (Z c M d ) represents at least one metallo atom or one metallo complex of the type described in the first formula. R<SP>v</SP>, R<SP>v</SP>, R<SP>1v1</SP> and R<SP>11v11</SP> each represent at least one aliphatic or alkyl hydrocarbon (wax) group having at least 20 carbon atoms such wax group or groups being attached by one valence only to at least one aromatic nucleus T. v, v' and v<SP>11</SP> represent the valences of the wax radicals, which should preferably be one to four. (Y b ) has the same significance as in the first formula and e represents a whole number from 1 to 4 equal to v and indicates the total number of groups (TÀ(Y b )À(Z c M d )) present in the molecule represented by the formula which are attached to the aliphatic group or groups. Numerous examples are given of individual sub-groups of compounds which come within the general formulae above. The compounds of the invention may be pure compounds corresponding to one of the formulae above. However as usually prepared by procedures in which wax-substitution is effected with a chlorinated wax by the Friedel-Crafts reaction, the final product is usually a mixture of different compounds corresponding to different values of e and v and to different numbers of wax groups. Exemplary types of compounds within the invention which are referred to, together with their methods of preparation are as follows: Type I. Wax-aryl-metallo compounds of the general formulae: These compounds may be prepared either by the Grignard reaction or by the reaction of wax aryl compounds with alkali metals in the presence of aliphatic ethers. The synthesis of compounds (a) and (b) above is carried out by the preparation of wax benzene by the Friedel-Crafts reaction followed by chlorination at low temperature in the dark to produce compounds of type (a) or by chlorination in the presence of light or carriers at about 200F. to produce compounds of type (b). The formation of the Grignard reagent is carried out by treatment of the chloro compound with magnesium followed by reaction with a halide of the desired metal to form the wax-aryl metallo compound. In the preparation of alkali metal compounds (c) wax naphthalene for example is reacted with alkali metal in the presence of an aliphatic ether such as dimethyl ether. Type II. Wax-aryl metal oxides of the general formulae: An example of the preparation of these compounds is as follows: A paraffin wax is chlorinated and then reacted with phenol in the presence of aluminium chloride to form a wax phenol. Excess phenol is removed and the product is reacted with finely divided metallic sodium at 500F. in the presence of a non- oxidizing gas to form a wax substituted sodium phenate. Wax-substituted aryl oxides of the alkali or alkaline earth metals and metals from the silver, copper, aluminium, tin and iron analytical groups can also be prepared by the reaction of the wax phenol with an alcoholate of the desired metal, the reaction mixture being heated to 300 F. for one hour. Type III. Metal salts of wax-aryl thio acids of the general formulae: Compounds of type III are formed by reacting a wax-aromatic compound with sulphur monochloride to form a disulphide followed by reduction to form the mercaptan. The wax aromatic compound may be prepared for example by reacting naphthalene with a chlorwax in the presence of aluminium chloride. Type IV. Metal salts of wax-aryl acids of the general formulae : The preferred method of making compounds of type IVa consists in forming a ketone followed by oxidation. Thus a triwax benzene formed as described under type III compounds is reacted with acetyl chloride in a chlorinated solvent, and the product oxidized with sodium hypochlorite. The sodium salt is formed by neutralization and the polyvalent metal salts from this by double decomposition. Other methods are the direct oxidation of an alkyl group to COOH, and by chlorination of the aromatic nucleus of the wax-aromatic hydrocarbon followed by reaction with sodium and carbon dioxide. Salts of wax-aryl aliphatic acids of the formula IVb are 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. Polyvalent metal salts are obtained from the sodium salt by double decomposition. Thio acids such as thiolic acid, the salts of which are represented by formula IVa where X<SP>1</SP> represents oxygen and X represents sulphur are prepared by the reaction of wax aryl acid chlorides with sodium sulphide, followed