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United States Patent (19) 11 Patent Number: 4,910,263 Brois Et Al

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United States Patent (19) 11 Patent Number: 4,910,263 Brois Et Al United States Patent (19) 11 Patent Number: 4,910,263 Brois et al. (45) Date of Patent: Mar. 20, 1990 (54) OIL ADDITIVES CONTAINING A 3,382,215 5/1968 Baum ................. 525/351 X 3,647,849 3/1972 Venerable et al. 260/454 THIOCARBAMYL MOIETY 3,749,747 7/1973 Fancher .............................. 260/454 75) Inventors: Stanley J. Brois, Spring, Tex.; 3,867,360 2/1975 Jones ............................... 525/351 X Antonio Gutierrez, Mercerville, N.J. FOREIGN PATENT DOCUMENTS 73 Assignee: Exxon Research & Engineering Company, Florham Park, N.J. 514052 10/1939 United Kingdom .................. 252/47 (21) Appl. No.: 252,942 OTHER PUBLICATIONS E. Reid, "Organic Chemistry of Bivalent Sulfur', vol. (22 Filed: Oct. 3, 1988 VI, 1966, pp. 62-65 and 220-221. R. G. Guy et al., “Pseudohalogen Chemistry”, J. Chem. Related U.S. Application Data Soc. 1973, pp. 281-284. 60 Division of Ser. No. 89,449, Aug. 20, 1987, Pat. No. R. G. R. Bacon, Chapter 27, "Thiocyanates, Thi 4,794,146, which is a continuation of Ser. No. 908,786, ocyanogen, and Related Compounds,’ Organic Sulfur Sep. 18, 1986, Pat. No. 4,717,754, which is a continua tion of Ser. No. 776,019, Sep. 13, 1985, abandoned, Compounds, edited by N. Kharasch, vol. 1, Pergamon which is a continuation of Ser. No. 320,574, Nov. 21, Press, 1961, NY, Symposium Publications Division, pp. 1981, abandoned, which is a continuation of Ser. No. 306-325. 109,778, Jan. 7, 1980, abandoned. R. G. Guy, "Thiocyanogen Halides,", Mechanisms of 5ll Int. Cl." ................................................ C08F 8/32 Reactions of Sulfur Compounds, vol. 3, pp. 57-61 (1968). 52 U.S. Cl. .............................. 525/331.7; 525/331.8; A. B. Angus and R. G. R. Bacon, "Thiocyanogen Chlo 525/332.8; 525/333.1; 525/333.7; 525/374; ride, Part I", J. Chem. Soc., pp. 774-778 (1958). 525/375; 525/379; 525/380 Primary Examiner-Joseph L. Schofer 58) Field of Search ............... 525/331.7, 331.8, 332.8, Assistant Examiner-Bernard Lipman 525/333.1, 333.9, 528/481,503 Attorney, Agent, or Firm-J. B. Murray, Jr. (56) References Cited 57 ABSTRACT U.S. PATENT DOCUMENTS An oil-soluble additive for lubricating oil applications is 2,168,674 8/1930 Loane et al. .............................. 87/9 provided by the formation of an adduct of thiocyano 2,169,700 8/1939 Loane et al. .............................. 87/9 gen halide and polyalkene, removal of the hydrogen 2,218,918 10/940 Loane et al. .... ... 252/47 halide from said adduct and thermal rearrangement of 2,619,464. 1 1/1952 Otto ............w ... 252/47 the product to provide a polyalkenyl isothiocyanate 2,680,759 6/1954 Otto ..................................... 260/454 which can be subsequently derivitized to provide a 2,689,255 9/1954 Craig et al. ..... ... 260/454 2,954,393 9/1960 Haimsohn et al. .................. 260/454 thiocarbamyl moiety containing product having excel 3,149,141 9/1964 Venerable et al. .................. 260/454 lent sludge dispersement properties. 3,318,936 5/1967 Sakai et al. .......................... 260/454 3,330,763 7/1967 Damrath ..... ... 252/47.5 4 Claims, No Drawings 4,910,263 1. 2 to both fuels and lubricating oils. For example, in U.S. OLADDTIVES CONTAINING A Pat. No. 2,168,674 to Loane et al., mineral oils contain THOCARBAMYL MOETY ing fatty acid thiocyanates, such as lauroyl thiocyanate and stearoylthiocyanate, have been suggested as oxida This is a division of application Ser. No. 89,449, filed 5 tion inhibitors for lubricating oils; in No. 2,169,700, the Aug. 20, 1987, now U.S. Pat. No. 4,794,146 which was same inventors have disclosed mineral oils containing a continuation of Ser. No. 908,786, filed Sept. 18, 1986, polyethiocyanates having the formula, R(SCN)n, now U.S. Pat. No. 4,717,754, which in turn was a con wherein R is an aliphatic radical or an aromatic radical, tinuation of Ser. No. 776,019, filed Sept. 13, 1985, now and n is an integer greater than one; and, in 2,619,464 abandoned, which was a continuation of Ser. No. O and 2,680,759 it is reported that mineral lubricating oils 320,574, filed Nov. 21, 1981, now abandoned, which containing small amounts of high molecular weight was a continuation of Ser. No. 109,778, filed Jan. 7, alkyl monothiocyanates, preferably C21-C34 monothi 1980, now abandoned. ocyanates as paraffin wax monothicyanates, are resis tant to oxidation and have a reduced tendency to cor BACKGROUND OF THE INVENTION 15 rode hard metal alloy bearings (the polythiocyanates 1. Field of the Invention are noted as ineffective due to their substantial insolubil This invention relates to sulfur- and nitrogen-contain ity in mineral lubricating oils). The referenced latter ing compositions and in a more particular sense it relates compositions are produced by the reaction of an alkyl to those compounds having a thiocarbamyl moiety chloride with an inorganic salt of thiocyanic acid, e.g. adapted for use as additives in hydrocarbon oils. This 20 ammonium thiocyanate, at a temperature of at least 100 invention relates also to hydrocarbon oils, especially C. lubricating oil compositions containing said sulfur- and U.S. Pat. No. 3,330,763 discloses the use of hydrocar nitrogen-containing compositions. bylamine salts of thiocyanic acid as load-carrying addi 2. General Background tives in lubricating oils. The problem of deterioration of hydrocarbon oils has 25 been the cause of principal concern in the formulation Further, the isomerization of allylic thiocyanates has of hydrocarbon oil compositions such as fuels and lubri been attributed to the occurrence of a cyclic intramo cating compositions. Deterioration of hydrocarbon oils lecular transition state (Organic Sulfur Compounds results in the formation of products which are corrosive edited by N. Kharasch, Vol. 1, pg. 312, 1961, Pergamon to the metal surfaces with which the oils come into 30 Press, NY). contact. It results also in the formation of products It is, accordingly, an object of this invention to pro which have a tendency to agglomerate to form sludge vide novel compositions of matter. and varnish-like deposits. It is also an object of this invention to provide com In recent years it has been a common practice to positions adapted for use as multifunctional additives in incorporate into hydrocarbon oils chemical additives 35 hydrocarbons, particularly for fuels and oils. which are capable of inhibiting the deterioration of oil It is also an object of this invention to provide com and the formation of these harmful deposits. Such addi positions useful as corrosion, oxidatin inhibitors and/or tives have generally been classified into three principal dispersants in hydrocarbon lubricating oils. groups according to the manner in which they function SUMMARY OF THE INVENTION to improve hydrocarbon oil. One group of such addi tives are the oxidation inhibitors which function to In U.S. patent application Ser. No. 74,821 filed Sept. stabilize the oil against oxidative degradation. Another 12, 1979 now abandoned of common assignee, it has group of such additives are the corrosion inhibitors been reported than an allylic thiocyanate resulting from which counteract the corrosiveness of the products of the reaction of an alkenyl halide with potassium thiocy oil degradation or passivate the metal surfaces against 45 anate is, after isomerization to an isothiocyanate, sus the corrosive action of such products. Still another ceptible to derivatization with protic reactants, particu group of such additives are the detergents or dispersing larly upon reaction with: amines, preferably alkylene agents which function to maintain products of oil degra polyamines: alcohols, preferably polyols; thiols; and, dation in dispersion in the oil phase and to prevent the mixtures thereof to yield thiocarbamyl derivatives hav deposition of sludge and varnish. 50 ing activity in hydrocarbons, particularly fuels and Two or more such additives are often needed in a lubricating oils. hydrocarbon oil to stabilize the oil against formation of It has now been discovered that a thiocyanogen hai harmful degradation products. The incorporation in an ide, preferably ClSCN, can be readily added to a polyal oil, however, of several different types of additives not kene to produce alkenyl isothiocyanates in high yield only is costly, but is also dependent upon the compati 55 and purity. This had made possible the synthesis of: bility of the additives with one another. Thus, it is haloalkenyl isothiocyanates e.g. chloropolyisobutenyl known that additives which are effective separately isothiocyanate; alkenyl isothiocyano succinic anhy may not be used in combination because of their incom dride, e.g. polyisobutenyl isothiocyano succinic anhy patibility. A great deal of effort has recently been de dride; and poly(ethylene-C3 to Cs a-olefin-C4 to C30 voted to the development of so-called "multi-func 60 diene) isothiocyanates and polyisothiocyanates. tional" additive, i.e., an additive which, by itself, is The reaction of the invention comprises an equimolar capable of imparting several desirable properties to an reaction of a polyalkene e.g. an olefin such as polyisobu oil. It will be readily appreciated that the use of such tylene with a thiocyanogen halide, e.g. thiocyanogen additive is highly advantageous from the standpoint of chloride to yield allylically unsaturated hydrocarbyl both economy and convenience. 65 isothiocyanate which is susceptible to derivatization 3. Prior Art Publications with protic reactants, particularly upon reaction with: Sulfur- and nitrogen-containing compositions are amines, preferably alkylene polyamines: alcohols, pref stated to provide such desirable multifunctional activity erably polyols; thiols; and, mixtures thereof to yield 4,910,263 3 4. thiocarbamyl derivatives having activity in hydrocar tetrahydrofuran (THF) and methanol. Usually the mix bons, particularly fuels and lubricating oils.
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