Патент USA US2387286код для вставки
Patented‘ Oct. 23, 1945 ‘ . 2,387,286 UNITED STATE 5 PATENT "OFFICE ' 2,387,286 . - SULPHURIZED CARDANOL ETHERS , Ferdinand r. Otto, Woodbury, N. J., assignor to Socony-Vacuum Oil Company, Incorporated, a corporation of New York ' ‘ No Drawing. Application November 25, 1943. Serial No. 511,703 ' ' ' __8-Claims.' (credo-1'25). .' This invention has to do with new chemical compounds or reaction products which may be generally designated as sulphurized cardanol eth ers or as sulphur-containing reaction products of cardanol ethers and elementary sulphur. ( Making use of this term. the following ‘structural The present invention is predicated upon the discovery that the compounds or reaction prod uctsFcontempIated herein when blended with a viscous mineral oil fraction such as a hydrocarbon formula represents cardansl ethyl ether '4 0 CH5 lubricating ,oil, will improve various properties of I 1 i‘ ' . the oil.‘ For example, these compounds or reac-" 0101121 tion products will inhibit oxidation of the oil, thereby retarding the formation of sludge and acidic products. They also'retard changes in vis co'sity,‘in the oil, with temperature change during It is to be understood that all cardanol others are contemplated herein for reaction with ele mentary sulphur and'that all organic radicals may replace the ethyl (,—CaHs) radical. shown ‘It is to be understood, however, that the pres ent invention is not concerned with mineraloil compositions, such compositions forming the sub ject matter of my copending application Serial No. 424,127, ?led December 23, 1941, ofwhich the , above. '~ In this resarchthe orsaniclradical may be alkyl such as methyl; propyl, butyl, decyl, etcyl,v " 20 , representedby methyl phenyl and methyl naph present application is a continuation~in-part and thyl, etc.; cycloalkyl as represented by cyclo p to which reference is made for further details in the composition of these compounds or reaction products. . octadecyi, etc.; aralhl such as benzyl, etc; aryl as typi?ed by phenyl, naphthyl, etc.;~ allsaryl as phenyl; etc. - While ‘the. mechanism of the reaction of car-a danol ethers‘ with elementary sulphur is, as yet. 25 - It is also to be understood that the‘ use of the compounds or reaction products contemplated notwhoily understood, it is most probable that herein is not confined to the improvement of ' sulphur reacts with‘ the carbon atoms of the un mineral oils. For example, they may be used as saturated bond of the cutting oils, rubber accelerators, 'etc., and as in 30 following manner, termediates in the production of other chemical 1 group —CnH§a-:, in the - compositions. ‘Numerous other uses and applica- ‘ tions of these compounds or reaction products will be readih'r apparent to those skilled in the art 1 from the description of their composition and as. typical methods for preparing them, as provided hereinafter. ' wherein R is an organic radical. = As aforesaid, the compounds or reaction prod- - dots of the present invention are obtained by re action of cardanol ethers and elementary sulphur. The term “cardariol? as described in U. 5.‘ Patent , 2,181,119, denotes a phenol ha an empirical _ formula oi Gaol-Iss0, and probable structural for mula of I-ImGmCaHrQOI-I with one unsaturated bond in the HarzCm-radical, which is meta to the -OH radical. The ethers of cardanol, or» car danol ethers, contemplated herein are those in which the hydrogen of the —OI-l radical has been replaced by an organic radical, as, for example, an 50 aromatic or an aliphatic radical, with preference given to the cardan'yl alkyl ethers. The term “cardanyl" as used herein describes ‘ - not in any way to be construed so as to limit the ‘ scope of this invention, for the ‘sulphurized car danol others herein descrimd are contemplated . broadly as the reaction products of elementary sulphur and cardanol others. , The reactlonproducts contemplated herein are illustrated by those shown in the following typical examples. > EXPLE 1 Rrmcrron Pnonucr 0am... ' ARY SULPHUR as ‘ I ' The foregoing suggested expltion oi the re ' .action mechanism is merely speculation and is CARDANYL Ems Emma ' One hundred, and sixty- grams of cardanyl ' that group or radical which remains on the re ethyl ether and 16.2'era'ms of elementary, sulphur. moval of the —OH group from cardanol, as were heated in the presence of .a non-oxidizing ' 1 ' ‘2,887,286 reaction temperatures used therein may be varied gas‘, such as nitrogen, at approximately 175°, C. p for a period of 24 hours. considerably. For example, temperatures in the During the reaction, practically no hydrogen sulphide was evolved, an neighborhood of from about 110° C. to about 200° ' indication that the major portion of the sulphur C. are satisfactory, but preference-is given to re action temperatures of the orderoi about 150° C. reacts withthe unsaturated group of the alkyl side chain of the cardanyl ethyl ether. A copper to about 175° C. . '.- j . ' Simila?t, it is preferred to react from about 0.5 to about 2.0 atomic proportions‘ of sulphur with strip test on a 1 per cent blend of the reaction product in a mineral oil, heated for ,3 hours at 150° C. gave no appreciable discoloration of the one mol of cardanyl ether in order to prepare the copper strip, therefore indicating that all of the 10 reaction products of this invention._ Particularly preferred products, however, are prepared by re sulphur had been chemically combined. The acting one atomic proportion of sulphur with one product may be improved in color by contacting it for approximately 1/2 hour with 10 per cent to , mol of a cardanyl ether under the foregoing re action conditions. , 20 per cent of superé?ltrol clay, followed by ?l It is to be further ‘understood that although I _ tration through more clay to obtain the ?nished 15 product, which is a light brown oil and contains . have described certain preferred procedures for preparing the reaction products contemplated ' about 9 per cent sulphur. herein and have shown illustrative reaction prod ucts, the invention is not limited to the particular Rnaorron Pnonucr or Erasmus“ Super-run m 20 procedures or products, but includes within its EXAMPLE 2 CARDANYL Ocranrcrr. Erma _ scope such changes and modi?cations as fairly (a) Preparation of cardanyl octadecyl ether come within the spirit of the appended claims. I claim: reaction mixture - Cardanol _ '72 n-Octadecyl chloride _________ __'__- _______ __ I 1.- As a new composition of matter, an oily, sul 25 phur-containing reaction product obtained by re action of a cardanol ether and elementary sul Grams 72 phur. Sodium dissolved in 150 cc. of butanoi _____ __ 5.8 ‘ ' 2. As a new composition of matter, an oily, sul phur-containing reaction product obtained by re The cardanol was added to the stirred solution 30 acting a cardanol ether and elementary sulphur at a temperature between about 110° C. and about of sodium butylate to. form the corresponding so , Procedure - . 200° C. dium cardanolate. Octadecyl chloride was then _ 3. As a newcomposition of matter, an oily, sul i added and the mixture was heated for 14 hours phur-containing reaction product obtained by re at 120° C. in an atmosphere of nitrogen. The butanol was then allowed to distill from the mix 35 action of from about 0.5 to about 2.0 atomic pro .‘portions of elementary sulphur and about 1.0 mol ture and the temperature was gradually raised to of a cardanol ether at a temperature between 200° C. After heating for 5 hours at this tem about 110° 0. and about 200° C. perature the product was cooled, diluted with 4. As a new composition of matter, an oily, sul benzol, acidi?ed with dilute hydrochloric acid. and water washed until neutral. The mixture 40 phu‘r-containing reaction product obtained by re acting a cardanyl alkyl ether and elementary was then topped under diminished pressure to sulphur at a temperature between about 110° C. 340°~ C. to remove unreacted cardanol vand octa decyl chloride. and about 200° C. The residue, representing the sulphur reaction mixture portions of elementary sulphur and about 1.0 mol .Grams of a cardanyl alkyl ether at a-temperature be tween about 110° C. and about 200° C. 50 _6. As a new composition of matter, an oily, sul Cardanyl octadecyl ether_________________ __ 50 ' ' ' 3 ' phur-containing reaction product obtained by re Procedure The cardanyl, octadecyl ether (prepared in (a)) and sulphur were heated, with stirring, for a period of 3 hours at 170° C. in the presence 0! a non-oxidizing gas such as nitrogen. action of cardanyl ethyl ether and elementary ' sulphur at a temperature between aboutv 150° C. and about 175° C. so The re action mixture .was then ?ltered to obtain the ?nished compound. 'A polished copper strip, im mersed in a one per‘ cent blend of the productin '‘ mineral oil, showed no discoloration after heating for 24 hours at 100° 0.. thereby indicating that all the sulphur was chemically combined. The ’ _ , The preparation of typical reaction products shown above is but illustrative inasmuch as the ‘ , > '1. As a new composition of matter, an oily, sul phur-containing reaction product obtained by re action of one mol of cardanyl ethyl ether and one atomic proportion of elementary sulphur at about 175° C. ' ' . - 8. As a new composition or matter, an oily, sul sulphurized cardanyl octadecyl ether is a viscous brown 011 containing 5.9% sulphur. ‘ 45 phur-containing reaction product obtained by re- ‘ action of from about 0.5 to about 2.0 atomic pro (b) Reaction product of (a) and elementary Sulphur ' 5. As a new composition of matter, an oily, sul cardanyl octadecyl ether, was a ?uid brown oil. phur-containing reaction product obtained by re. action of one mol of cardanyl octadecyl ether and one atomic proportion oi‘ elementary sulphur at about 170° C. 4 FERDINAND P. UI'TO. '