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United States Patent (19) 11 Patent Number: 5,055,626 Ho Et Al

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United States Patent (19) 11 Patent Number: 5,055,626 Ho Et Al United States Patent (19) 11 Patent Number: 5,055,626 Ho et al. 45) Date of Patent: Oct. 8, 1991 (54) NOVEL LUBRICANTS A Class of Thermally Stable and Wide Liquid Range (75) Inventors: Suzzy C. Ho, Plainsboro; Margaret Fluids", Preprints of Division of Petroleum Chemistry, M. Wu, Belle Mead, both of N.J. No. 4; pp. 1053-1058, American Chemical Society, 73) Assignee: Mobil Oil Corporation, Fairfax, Va. Aug. 26-31, 1984. (21) Appl. No.: 471,454 Primary Examiner-Curtis R. Davis (22 Filed: Jan. 29, 1990 Attorney, Agent, or Firm-Alexander J. McKillop; Charles J. Speciale; Malcolm D. Keen 51) Int. Cl. ......................... C07C 15/00; C07C2/52 52 U.S. Cl. ..................................... 585/416; 585/420 (57) ABSTRACT 58) Field of Search ................................ 585/416, 420 Alkylaromatic lubricant products are produced by the (56) References Cited reaction of a long chain alkyne such as octyne, decyne U.S. PATENT DOCUMENTS or dodecyne over a reduced Group VIB metal oxide 2,217,0ll 10/1940 Grosse et al. ....................... 585/420 catalyst, preferably reduced chromium on silica. The 2,781408 2/1957 Witt et al. ....... ... 585/416 products, which are predominantly n-alkyl substituted, 2,819,325 1/1958 Lanning et al. ... 585/46 possess excellent thermal and oxidative stability and 4,827,064 5/1989 Wu ........................................ 585/10 may be used as lubricant base stocks and viscosity in 4,827,073 5/1989 Wu ...................................... 585/.530 provers. OTHER PUBLICATIONS Eapen et al., "Poly-normal-alkylbenzene Compounds: 21 Claims, No Drawings 5,055,626 1. 2 straight or branched chain. Indeed, some of the alkyl NOVEL LUBRICANTS substituents. may be straight chain and others may be branched chain in the same molecule. This invention relates to novel synthetic lubricants. It Reference is here made to an article by K. C. Eapen more particularly refers to synthetic alkyl aromatic et al. Poly-normal-alkylbenzene Compounds. A Class of lubricants and a novel process for producing them. Thermally Stable and Wide Liquid Range Fluids: Pre prints of the Division of Petroleum Chemistry, No. 4, BACKGROUND OF THE INVENTION pages 1053-1058 American Chemical Society, Philadel In recent years there has been a pronounced effort to phia Meeting, Aug. 26–31, 1984. This article reviews produce superior lubricants. Attempts to make such 10 the state of the art relative to making alkyl aromatic superior lubricant materials have revolved around in compounds for use as lubricants, as well as a review of proved refining of natural mineral oil base stocks and the properties of such lubricants as have been made the creation of new synthetic base stocks which have with these base stocks. It is well known, from conven good basic lubricity characteristics. Where new com tional inorganic chemistry, that reactions requiring stoi pounds were synthesized, there were attempts made to 15 chiometric quantities of Grignard reagents as described produce compounds which had known oxidation resis in this reference, are difficult and expensive to run. tant sites, such as quaternary carbon atoms. Addition Further, it is known that this type of reaction is difficult ally, it was attempted to produce long chain hydrocar to control in that the amount of alkylation and the par bon compounds, since it was known from mineral oil ticular position of the alkyl substitution may not always technology, that long chain hydrocarbons had both 20 be exactly where it is most desired that it be. As a result, good lubricity and good smoke points. Although long while the reaction may be generally known, the produc chain aliphatic groups have good lubricating properties, tion of reaction products which are suited to use as they usually also have relatively high freeze and cloud lubricants is in no way shown by this reference, nor is it points. s possible to use this stoichiometric Grignard reagent Thus, many synthetic lubricants are based on decene 25 reaction to produce lubricant quality products. oligomers because these compounds have an excellent In this art, it is to be noted that the lubricant base combination of properties including long aliphatic stock is often the whole reaction product, or at least a chains, which provide good slipperiness, relatively low substantial portion thereof, with a minimum of product freeze and cloud points, and oxidation resistant loci in purification. It is most unusual for a pure compound or the same molecules. 30 compounds to be used as a lubricant base stock because Recently, it has been found, by one of the inventors of the cost of isolation of a pure compound would be so the subject matter hereof, that decenes which have been significant that the product so produced might well be oligomerized over Group VI B metal catalysts, particu priced out of the market almost regardless of the prop larly reduced chromium catalysts, produce unusually erties that it possessed. Thus, the lubricant base stock fine lubricant base stocks. The products of this oligo 35 which is actually used is usually a mixed reaction prod merization tend to have very uniform molecular struc uct which has been refined to the least extent possible ture, low branch ratios and low pour points. Fine syn consistent with obtaining the properties which are de thetic lubricants and viscosity index (V I) improvers sired. have been formulated from these decene oligomers, which are principally trimers. Reference is here made to 40 SUMMARY OF THE INVENTION U.S. Pat. Nos. 4,827,064 and 4,827,073, issued in the Thus, this invention is directed to a novel process for name of one of the inventors hereof, which show the producing lubricant base stocks which are predomi novel production of excellent alpha olefin oligomers nantly n-alkyl aromatic in nature, have high viscosity which find utility in the lubricant field. index, low pour point, good thermal oxidation stability, Alkyl aromatics are very well known organic com 45 and good additive solubility. This process comprises the pounds. They have a wide variety of known uses in reaction of a substituted acetylene, a 1-alkyne, in detergent and lubricant technologies, and they have contact with a transition metal catalyst, preferably acti-. been used as precursors for producing over-based aryl vated metal on a refractory substrate, under conditions sulfonates. conducive to the aromatization of the 1-alkyne, into In general, alkyl aromatics have usually been made 50 alkyl substituted aromatic compounds, in which the by alkylating existing, preformed aromatic compounds, alkyl portions are derived from the alkyl portions of the such as benzene, toluene, xylene, naphthalene, etc., with substituted acetylene, and the cyclic, aromatic portions alpha olefins. There has recently arisen an interest in are derived from the cyclooligomerization of the alkyne finding alkyl aromatics which would be useful in lubri portion of the reactant molecules (the cyclization and cant formulations. Inherently, these materials should 55 aligomerization the reactant). One particularly desirable make good lubricant base stocks because they have long attribute of the process of this invention is the fact that alkyl chains to provide the needed lubricity characteris the catalysts are regenerable and reusable, and do not tics, and aromatic nuclei which should provide good leave the reaction zone as a necessary adjunct to the oxidation resistance and solvency for polar additives, reaction product requiring later separation and purifica such as antiwear additives, antioxidants, etc. Further, tion. their molecular structure is such that these molecules should have relatively low freeze and cloud points. DETAILED DESCRIPTION OF THE Alkyl aromatics are commercially available materi INVENTION als. They are conventionally synthesized by the direct According to one aspect of this invention, a desired addition of olefins, particularly alpha olefins, to aro 65 product mixture comprising alkyl aromatics is pro matic nuclei, particularly benzene. This reaction is duced by contacting substituted acetylenes with a suit known to produce a mixture of mono and multi substi able catalyst under aromatization conditions. The na tuted benzenes in which the alkyl groups may be ture of the product mixture is very much a function of 5,055,626 3 4. the substituted acetylene, or 1-alkyne, which is used as catalyzing the desired aromatization reaction, without the reactant. significant catalysts of the undesired isomerization reac According to this invention, the 1-alkyne reactant tions, are possessed by Cr II on high surface area silica. used herein suitably contains between about 8 and 20 Good conversion can also be achieved by the use of carbon atoms which are preferably in a substantially reduced tungsten and/or molybdenum based catalysts. straight chain configuration. Although straight chain In addition to the silica support, alumina, titania, silica reactant alkynes are preferred, it is within the scope of alumina, magnesia and the like have been found to be this invention to utilize alkyne reactants which have useful as support materials either singly or in various some branching in the molecule. combinations. The existence of branching has little or no effect upon 10 The support material, regardless of its composition, the conversion of the alkyne to the desired alkyl aro should have high surface area, suitably provided by a matic, unless the branching is so close to the alkyne pore system of average pore size of about 40 to 350 (A) group that it offers spatial interference with the aroma angstrons. The high surface area is beneficial in Sup tization reaction. Thus, it is preferred that, if the reac porting large amounts of highly dispersed, active tant alkyne contains branches these branches be some 15 Group VI B metal centers so as to give high efficiency what distant from the alkyne group so as to pose mini of metal catalyst usage. This results in high catalyst mum spatial interference with the aromatization of the activity for the specific reaction desired without unde alkyne group portion of the reactant molecule.
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