Патент USA US2109772код для вставки
hummer-1,1938 _ 4- - 0 2,109,7'l’2 UNITED STATES PATENT OFFICE THIOKENED LUBRICATING OIL . Per 1:. Frolich, Roselle, N. 1., escignor to stand; ard-Oil Development Company, a corporation ' V of Delaware " , .No Drawing.‘ Application October 21, 19:3, _ _ Serial No. 694,616 _ 5 Claims. - (01. 196-151) _ 'Ihis invention relates to improved lubricating from unsaturated hydrocarbons. Many such compositions comprising" solutions of synthetic‘ products are insoluble in practically all solvents ' resinous bodies in lubricating oils and relates and are obviously unsuited for the ‘present in ,more particularly to the improvement of the ventlon. The polymerization and condensation 5 viscosity and viscosity indexof inferior quality products intended for use in this invention are- 5 lubricating oils by addition thereto of resins pre- those resins and resinous products of relatively pared by polymerization and/or condensation high molecular weight, say above 800 to 1000, of oleilnes and diole?nes or mixtures thereof such and including the range to 2,000, 5,000, 10,000 ‘as are found in cracked naphthas. and even higher. which are soluble in benzol, and 10 A class of hydrocarbon resins of varying melt- which preferably are brittle and readily friable 10 r in: point, friability and color, and which are solids which'become. plastic on‘ heating. Such soluble in benzol and gasoline and are insoluble products are designated. by th'e term resin as in ethyl alcohol and acetone is obtained by the used in the claims. polymerization -and condensation of cracked 15 naphthas or of the unsaturated components thereof by the application of heat and pressure or by action of suitable polymerizing agents such as the active halides, for example aluminum chlo-ride, zinc chloride, boron ?uoride, and the like. go It has now been found that these resins are soluble in lubricating oils; particularly those derived from asphaltic or naphthenic base crudes, and that the resulting solutions have a materially higher viscosity and _ viscosity index than the ‘ - It is recognized that the presence of a relatives ly smaller proportion of impurities, such as heavy 15 oils, ‘which may have been present in the initial materials or may be formed during the polymer ization and condensation reaction, may so affect the physical properties of [the crude product that it may be semi-solid, tacky, so toughened as not 20' to be brittle or pulverizalile. or otherwise modi lied. The crude product Containing the resin may also be used for the purpose of this inven tion, provided the impurities are not present in . 25 original lubricating oil. ,It is an object of this invention to increase the viscosity and to im- sumcieht' quantities to offset the advantageous g5 effect of the resin. However. it'is generally pref .prove the lubricating and other qualities ‘of such inferior lubricating oils by addition thereto of such resins. ‘ 3o Resins suitable for this invention may be prepared in a great varietyof ways; for example rel- erable to use resins that are su?iciently pure to be brittle and pulverizable solids at room tem perature. The resin may be puri?ed by distll1a-< tion of vaporlzable oils, preferably in high vac- 3o um and may be separated from Oils and 55 atively pure oleilnes or mixtures of oleiines and diole?nes, such as amylene and isoprene, may be condensed to resins by addition of aluminum 35 chloride or other suitable halide polymerizing, phallic matter by Suitable Selective Solvents, Such as lique?ed hydrocarbon eases. petroleum ether. naphthas. a mixture of benzol and acetone. and the like. 35 agent‘, as described in German Patent 278,4;86 to . Schering. Cracked naphthas such as the condensates or oil ‘gas drips boiling below 200° 1?. obtained in the gasiiication of gas oil may ,be 40 treatedwithasmallamountofalmninumchlw ride as described in U. S. Patent 811,563'to Ihart. .The mixture is ?ltered and a resin ob- tained from the ?ltrate as a residue by distilla- tion vor evaporation oi volatile constituents. As 45 another example a resin may be prepared by contacting a cracked naphtha boiling from 60 to 15.0“ C. with ‘zinc chloride as described in British Patent 3572 of 1914. By still another method the liquid fraction obtained in cracking 5o petroleum oil in vapor phase at 650° C.,may be polymerized to a hard resin by the application of heat without a catalyst as described in U. 8. ' 1,703,950. _ - . ' Itisrecognized that many types of polymerlza55 tlon and condensation products can be obtained The above resins may be used to thicken and . to improve the viscosity index and other lubri veating characteristics of lubricating oils. This is illustrated in the following examples: sample 1 _ 49 A petroleum naphtha obtained by cracking gas ‘ oil in vapor phase, 'at high temperature and lbw pressure, is carefullyfractionated bydistlllation. The fraction boiling below about-180° C. is agi- 45 tated with about 20% by weight of anhydrous aluminum chloride which is added in smallquan titles during continuous and vigorous agitation and cooling to'maintain the‘ reagents at about room temperature and preferably below about 50 40° 0., as described by Thomas and Carmody, J. Ind. 8: Eng. Chem. 24 (1932) p. 1125, and in U. 8. Patent 1,836,629. The reaction mixture is then hydrolyzed. the sludge withdrawn and the resin obtained as a residue on distillationof the so _ 2 2,109,772 oil layer. A solution of 51% by weight of this resin is prepared with a Coastal lubricating oil. The characteristics of the original lubricating oil and the resulting blend are as follows: Coastal oil Blend Saybolt viscosity: Seconds at 100° F___________ __> 360 Seconds at 210° F__________ _Viscosity index. _____________ __.._ 10 50 38 543 58.5 55 lubricating composition will depend upon the solubility of the resin in the oil used and on the extent of improvement desired. Generally, with oils having a viscosity index of 0 to 50, improved lubricants are prepared with about 2 to 10% of the resin in the composition, although lower or higher concentrations such as 1/2% or 1% to 15% or 25% or moremay be used, and will be found suitable with oils of unusually high or low vis cosity and viscosity index. The color, purity, solubility in petroleum sol 10 A fraction boiling _in the gasoline range, con vents, and other qualities of these resins may be taining ole?n and diole?n, and probably aromatic - “modi?ed" or improved by various methods, and and substituted aromatic hydrocarbons, and pro the improved resins may also be used to prepare 15 duced by vapor phase cracking of a petroleum gas blends with lubricating oils as described above. 15 oil fraction at high temperatures and low pres The resins may be puri?ed and improved by suit- . sures by the “Gyro” process, is cooled to —70" F. able‘re?ning methods such as clay treating, sul Boron ?uoride is bubbled through this fraction - furic acid treating, hydrogenation, and the like. for about one hour, with addition of carbon di The solubility of the resins in petroleum oils, 20 oxide snow to maintain the temperature con especially in paraffin base oils, may be improved 20 tinuously at about —'70° F. (It is desirable when by alkylation with suitable alkyl radicals such as ' ' EmampleZ usingboron ?uoride to work at low temperatures, 30 45 50 60 methyl, ethyl, etc. to octyl, decyl and higher in such as 0° F. to —90° F.) A noticeable thicken cluding the alkyl groupsof fatty acids and alco ing of the mixture occurs. The mixture is then ' hols, and the liquid ole?nes obtained by cracking allowed to warm up to room temperature. Any para?in wax. , 25 boron ?uoride present is hydrolyzed, and the gaso The resin may be used in oil blends together line hydrocarbons are removed by distillation. with pour point depressing agents, oxidation There is thus obtained a residue consisting of inhibitors, load bearing or “extreme pressure lu about equal portions of a resin and an oil, the bricant” agents, lead soaps, sulphur compounds, total residue corresponding to 30% of the original’ sulfurized oils, dyes and the like as will be under 30 gasoline. The oil is removed by distillation under stood. a vacuum of about 5 mm. of mercury to a tem This inventlon is not to be limited to any spe-_ perature of about 450° F., the resin being obtained ci?c examples which have been presented herein as the residue. A 10% blend of this resin in the‘ solely for purpose of illustration, but only by the Coastal oil described in Example 1 gives the fol following claims in which it is desired to claim 35 lowing inspection: all novelty insofar as the prior art permits. I claim: Saybolt viscosity: 1. Lubricant comprising a mineral oil and a Seconds at 100° F ____________________ __ 655 normally solid thickener produced by the con Seconds at 210° F ____________________ __ 62.2 densation of ole?n and diole?n hydrocarbons. 40 V. I __________________________________ __ 52 2. Lubricant comprising a mineral oil and a Similar blends may be prepared with resins pre normally solid thickener produced by the con pared by other methods as described above and densation of ole?n and diole?n hydrocarbons in with other types of lubricating oils. . It has been the presence of boron ?uoride at a low temperaf found that these resins are soluble only with ture. 45 diiiiculty in high grade lubricating oils such as 3. Method for improving the lubricating char those of the Pennsylvania type. This invention - acteristics of- lubricating oils of petroleum origin is accordingly particularly suited for the improve: having a viscosity index below 50, which comprises ment of inferior quality lubricating oils such as dissolving therein about 1/2 to 25% of a resin pre lubricating oils having a viscosity index from pared by treating a cracked naphtha with an about 50 to 0, or lower. Such lubricating oils are active halide polymerizing agent under conditions obtained from asphaltic, naphthem'c and aro adapted to produce condensation products of matic base crudes such as Coastal and California, ~ ole?ne and di-ole?ne hydrocarbons present in and may also be obtained from othermineral said cracked naphtha. . I » carbonaceous materials, as by the liquefaction or 4.'Method according to claim 3 in which the 55 destructive distillation of coal, shale, and the like. cracked naphtha boils below 180° C. ' Similar hydrocarbon oils may be prepared syn 5. Method according to claim 3 in which the thetically or by polymerization and condensation resin is prepared by treating a cracked naphtha of lower molecular weight hydrocarbons. Of I boiling below 180° C. with anhydrous aluminum course, with resins of suitable solubility, blends chloride at a temperature below about 40° C. and 60 of exceptionally high viscosity index may be pre separating the resin from the resulting mixture. pared with high grade Pennsylvania type oils. The amount of the resin used in any particular PER K. EROLICH.