US2815326A - Additive for mineral oils - Google Patents

Description

2,815,326 Patented Dec. 3, 1957 ADDITIVE FOR MINERAL ()[LS Elmer B. Cypher-s, Cranford, and Walter E. Waddey,

Westfield, N. J., assignors to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Application May 1, 1953, Serial No. 352,578

8 Claims. (Cl. 252) The present invention relates to a new composition of matter having special properties for improving the oxidation resistance of lubricants, and the like, when added thereto in small amounts. More particularly, the present invention is concerned with sulfurized hydrocarbon products, for example, monocyclic terpenes, and the like, having improved and unexpected properties imparted thereto. The products of this invention have the property, when used in small quantities, or inhibiting oxidation in mineral base and other lubricating oils, greases, and the like. When used in somewhat larger quantities, the products also add substantially to the load-bearing characteristics of such oils and greases.

This application is a continuation-in-part of Serial No. 130,758 filed on December 2, 1949 and now abandoned.

The products of this invention, in general, are useful in hydrocarbon or mineral base lubricants broadly, which includes the usual crankcase oils for internal combustion engines, gear oils, greases, and the like, containing major proportions of mineral lubricating oil fractions as the basic lubricant. They are also of utility in synthetic oils and related products, such as the esters of polybasic acids, the polyglycols, and the like, or blends thereof, with mineral oil base lubricants.

The invention also comprises a new method of procedure for preparing the improved products. Finally, the invention embraces a new composition comprising the oils or other lubricants, including such products in eifective proportions.

It is an object of the present invention to provide a simple and effective one-step process for sulfurizing terpenes. The product made by this process is at one and the same time (1) a potent bearing corrosion inhibitor for use in motor oils and (2) a product which is itself non-corrosive to copper in the concentrations normally-used for motor oil formulations.

An additional object of the present invention is to increase the load-bearing capacity of lubricating compositions, and this is accomplished by providing a sulfurized terpene hydrocarbon which not only has useful extreme pressure properties, but is non-corrosive to copper even in comparatively high concentrations. It is believed that none of these objects have been fully achieved in the prior art.

The invention has particular application to the controlled sulfurization of monocyclic terpenes, such as dipentene, but it is applicable to other and related hydrocarbons and the acid and ester derivatives thereof. In general, these materials may be described broadly as terpenes (C H sesqui-terpenes (C H diterpenes (C H and their simple acid, alcohol and lower alkyl ester derivatives.

The monocyclic terpenes having the general formula C H are especially useful, for example, dipentene CHCH CH CH3C CH-C CH2C 2 CH3 and its monocyclic isomers, e. g., terpinolene, which has the closely related structural formula CHCH2 C 8 CHz-C C=C CHz-C 2 C are particularly suitable.

The sulfurization of the terpenes, in general, has been the subject of extensive effort in the prior art. Terpenes are very attractive starting materials for sulfurized products because of their relative abundance and low cost and also because of their ready reactivity with sulfur. However, they are unusually difiicult to sulfurize in a satisfactory manner. One of the difiiculties which arises is that of controlling the sulfurization reaction. For example, if sulfur and a terpene are simply mixed and heated, as in Kobb, U. S. Patent No. 1,844,400, a reaction takes place suddenly when the melting point of sulfur is reached, the mixture often boiling over the top of the reaction vessel. Holt et al., disclose in U. S. Patent No. 2,443,823, that the terpene may be added gradually to molten sulfur and this procedure is helpful in controlling the reaction. Watson, No. 2,445,983, teaches a similar procedure, but in both these disclosures further treatment with alkaline materials is required to obtain a useful product.

The sulfurized terpene products obtained by the Kobb method and by the Holt and Watson methods are all corrosive to metals without further extensive treatment which imposes .severe limits on their usefulness. The products can be subjected to treatment with aqueous sodiumlrydroxide solution, as taught by Powers in U. S. Patent No. 1,926,648, which improves their stability sufficiently for their use in cutting oils, but this treatment apparently does not remedy their corrosiveness toward copper sufficiently to permit the satisfactory use of these prior art products in engine oils. Treating the sulfurized terpene products with aqueous sodium sulfide solution, as taught by Holtin U. S. Patent No. 2,443,823, reduces the corrosiveness toward copper to acceptable limits, but the resulting product thereby appears to lose much of its potency as a bearing corrosion inhibitor in automotive engines.

These points are illustrated by the data in the following table, which shows the results obtained in the standard 36-hour CRCL4 Chevrolet engine test and in the standard copper strip corrosion test (described later under Example I). The Chevrolet tests were run on a V. I. high quality motor oil base stock (containing a viscosity index improver) of SAE 20-10 W grade containing 1.5% of a detergent composition containing barium alkyl phenol sulfide, and 0.2% of sulfurized dipentene treated as shown.

Sulfurized Dipentene Inhibitor CRCL4 0.5% inhibitor in sit-20 motor oil, 3 hrs. at 212 F. Visual rating scale, 0 like new. 10 blackremovable deposit, 7 or less is generally con-- sidered acceptable.

It will be obvious from the data shown above that, in general, the prior art preparations are not satisfactory in situations requiring both copper strip corrosion and bearing corrosion inhibiting properties. It will be apparentthat the production of a successful oxidationinhibitor of the type concerned in this invention presents peculiar problems in that it is exceedingly difiicult to incorporate or to retain just the right amount of sulfur of the correct degree of chemical activity in the terpene molecule.

The diflierences between the sulfurized terpenes of the prior art and the sulfurized and subsequently or simultaneously desulfurized terpenes of the present invention are emphasized by inspection of comparative infra-red absorption spectra. Commercial dipentene sulfurized in the conventional manner (with no catalyst present) shows an absorption band at 10.2 microns but no absorption in the l1.28ll.4 micron range which is typical of type III olefins (CH =CRR"), cyclic olefins and cyclic diolefins including dipentene. Untreated dipentene shows strong absorption in this band. After desulfurization according to the invention, the products absorb in the ll.28-ll.4 micron range, but not at 10.2 microns. This suggests that the terpenic structure is retained in the case where the sulfurization catalyst is used.

The chemical reactions occurring between sulfur and terpenic compounds are complex, which is not surprising in view of the several different types of double bonds in terpenes, the different ways in which sulfur can react, the ease of isomerization of terpenes, and the possibility of disproportionation yielding both benzene and naphthene rings. As a result of the involved nature of the reaction, the mechanism and the chemical nature of all the products have not been completely identified. However, the present inventors have found certain new and advantageous principles and procedures, which if followed will result in the production of sulfurized terpene products having the desirable property of low corrosivity toward metals such as copper, and the property also of inhibition of oil oxidation which leads to hearing corrosion in engines.

According to the present invention, it has been found that a partial desulfurization of the initial sulfur-terpene adduct is an essential step in the manufacture of high quality products. Best results are obtained when the proportion of sulfur employed in the reaction mixture is relatively high, for example, equal to or greater than one atom of sulfur per double bond in the terpene molecule, and when the subsequent desulfurization is extensive. Further, ithas been found that the desulfurization should occur through the elimination of hydrogen sulfide from the sulfur-terpene adduct.

The desulfurization catalysts useful in the present invention may be selected from any of the well known materials known to the art as rubber vulcanization accelerators. Such materials are discussed in Compounding Ingredients for Rubber second edition, 1947, compiled by the editors of India Rubber World. Specific classes of compounds include thiazole derivatives such as mercaptobenzothiazole (Captax); aryl guanidine derivatives such as di-orthotolyl-guanidine, diphenyl guanidine (DPG), tri-phenyl guanidine, and mixtures of aryl guanidines; dithiocarbamate derivatives such as piperidinium pentamethylene diothiocarbamate (Pip-Pip), 2,4- dinitrodimethyl dithiocarbamate, and the zinc, copper, selenium and tellurium salts of dialkyl dithiocarbamates (Zimate etc.); sulfide derivatives of such compounds, such as benzothiazyl disulfide, tetramethylthiuram disulfide (Tuads), tetramethyl thiuram monoand tetrasulfides, dibutyl xanthogen disulfide, 2-benzothiazyl-N,N- diethylthiocarbamyl sulfide (Ethylac); amino-halide condensation products such as those of aniline and formaldehyde, toluene and various aldehydes, and of aniline and acetaldehyde; thiourea derivatives such as symmetrical diphenyl thiourea; nitroso derivatives such as a polymer of p-nitroso benzene; xanthates such as zinc butyl-xanthates, and the like.

Compounds such as those listed above may be used singly or in combination. For example, mixtures of mercaptobenzo thiazole and diphenyl guanidine or of methyl thiuram disulfide and diphenyl guanidine are quite effective.

The amount of catalyst which is employed may vary from about 0.05% to about 5.0% preferably 0.3 to 1.5%, by weight of the reactants. It will be obvious from the data presented in connection with the attached drawing that the catalytic desulfurization reaction can be carried out subsequent to the sulfurization (attached drawing, curve B), or simultaneously therewith (attached drawing, curve C). This is also illustrated by Examples I to IV. Suitable temperatures for both sulfurization and desulfurization are above the melting point of sulfur and not above about 425 F., the preferred range being within the limits of about 300 to 400 F. The proportion of sulfur employed is generally in the range from about 20 to about 35% by weight, based on the total com-' position, from 25 to 33% being preferred.

The invention will be more fully understood by reference to the following specific examples.

EXAMPLE 1.-(METHOD A) 5.5 grams of Captax (mercaptobenzothiazole) and 2.75 grams of DPG (diphenyl guanidine) were added to grams of fiowers of sulfur and the mass was melted and heated to a temperature of 300 F. in a flask equipped with a stirrer and a reflux condenser. To this mixture there was gradually added 400 grams of commercial Dipentene. The approximate composition of the commercial Dipentene is as follows:

On a percentage basis, the amounts employed were 73% Dipentene and 27% sulfur, combined with about 1% Captax and 0.5% DPG. The terpenic material was added over a period of about 20 minutes, during which the temperature of the mix was kept at 300 F. Thereafter, the temperature was raised to about 350 F. and held there for 5 hours. Samples of the reaction product were taken at 3 hours and at 5 hours. At the end of 5. hours, the yield was about 84% of a clear, oily sulfurized product which showed a sulfur analysis of 18.83% by weight. Using SAE grade 20 extracted Mid-Continent lubricating oil, an excellent copper strip rating of 5 was obtained (heated in the presence of clean copper for 3 hours at 212 F.). The entire reaction ran very smoothly.

EXAMPLE 2.-(METHOD B) 2.67 grams of Tuads (tetramethyl thiuram disulfide),

134.0 grams of sulfur and 400 grams of the commercial Dipentene of Example 1, plus one drop of a defoaming solution were stirred in a one-liter, 3-neck flask equipped with a reflux condenser. The temperature was raised to 300 F. in 25 minutes and maintained in this range for 5 hours. The product showed the following characteristics:

Gravity A. P. I 3.3

Neutralization number 3.31 Saponification number 92.51 Sulfur, Wt. percent 23.4

Copper strip test 5 0.5% by weight of this material in an EXAMPLE 3.--(METHOD c) 11.0 grams of Captax (mercaptobenzothiazole), 5.5 grams of DPG (diphenyl guanidine) and 770.0 grams of Dipentene were stirred in a 3-liter, 4-neck flask The data in Table I show (a) that several different methods of carrying out the reaction give satisfactory results, (b) that a variety of compounds of the rubber accelerator type are effective catalysts forthe reaction with reflux condenser and heated to F in 28 5 yielding non-corrosive products, Tuads or a combinaminutes. When the temperature reached 300 F. sulfur of captgxu and DPG P esPecauy useful (6) was added in small portions, maintaining the temperature that the reactwn can be earned E presenge of between 298 F. and 307 F. 330.0 grams of sulfur were catalysts at temperatures as low as 300 and m as added over a period of 57 minutes. The temperature was htfle as hours (d) that as much as 30% sulfur can then raised to 3300 R and held at F. for 5 10 be employed when catalysts are present, and (e) that hours Samples taken after 1 2 3 and 5 hours at as little as 20% sulfur yields a COl'I'OSlVe product when 33023500 F showed the fongwing haracterisficy no catalyst is used, even at a relatively high temperature:

' and long reaction time.

In general, the reaction conditions preferred are a temsulfur copper perature of about 300 to 350 F. and a reaction time of Hours at 330-340 F. Perceni; Strip 1.5 to 12 hours, using 25 to 30% by weight of sulfur and Test 0.3 to 1.5% of catalyst. Broader ranges of 280 or 300 to 425 F., reaction time of 1 to hours, sulfur range #3 from 20 to 35%, or even as high as 40%, based on the 20: 55 7 20 weight of the total reactant mixture, and 0.05 to 5% of 19-33 6 catalyst, may be employed. The reaction conditiones may be varied somewhat, depending upon the proportions of sulfur and desulfurization catalyst employed. Yleld at 5 hourszssq- The monocyclic terpenes are preferred, specifically dipentene and terpinolene, but the invention is applicable EXAMPLE 4.(METHOD D) to the terpenes broadly.

EXAMPLE 6 900.0 grams of sulfur were heated in a 5-l1ter, 4neck flask to 300 F. in 18 minutes. The molten sulfur was A semes of Sulfunzed d1Pente11e Preparations were i d and 2400 gems of i were added made on a pilot plant scale. These reactions, shown in gradually at 298-3l0 F. over a period of 41 i t Table II, show additional conditionsof time and temperaand the reaction continued at 306-322 F. for one hour. time Whleh e) be p y Wlth P D At this point, with a temperature of 310 F., a solution catalyst to Obtam non-corrqslve P one ,P to f 65 grams f dissolved in 59 4 grams f Previ. be observed from the data in Table II 18 that non-corroously sulfurized Dipentene was added gradually over slvlty as by the Copper Str1P test is dependent On a period f 14 i The temperature had dropped a decrease in original or normal sulfur content through to 292 at this point and was gradually raised to 337 evolution of hydrogen sulfide, one of the main contribu- F. over the next 3 hours and to 350 F. in the fourth tions of fhecetalyst being pp y 10 Promote Smooth hour. Heating was continued for an additional 8 hours desulfurlzatlon of unstable p f flddllets- It at 350 F., making a total of 12 hours after addition of 40 Will also be noted from the data in Table II that when the catalyst. The product contained 18.88% sulfur and p y g f Sulfur a temperature of 303 F. gave gave a rating f 6 in the copper Strip test a non-corrosive product in 4 hours (run 52), whereas a temperature of 275 F. did not give a non-corrosive EXAMPLE 5 product even'in 10 hours (run 55). Further, the use 45 of a larger amount of sulfur, 29%, gave an unsatis- A number of preparations were carried out under a factory product at 300 F. (run 53), whereas 30% sulvariety of conditions, reactant proportions and methods, fur gave non-corrosive products at higher temperatures similar to those described in Examples 1 to 4. Details (runs 59, 62, 63, and 66). Thus, the required temof these experiments and the quality of the products as perature and time for a particular proportion of sulfur measured by copper strip corrosion are given in Table I. 50 are simply related.

Table I CATALYTIC SULFURIZATION 0F DIPENTENE Soaking Soaking Sulfur, Percent Copper Run No. Catalyst Temp., Time, Method Yield, Wt. Strip,

F. Hrs. Percent 3 Hrs./

Added Found 212F 1.5% C+D 350 5 A 27 5 0.5% Tuads-.. 300 5 B 25 5 1.5% c+D 340 5 o 30 o 0.2% Toads". 350 11. 5 D 27 6 1.0% 'luads... 300 3 B 27 10 1.0% Toads..- 300 3 B 25 6 1.0% Tuads 300 1. 0 27 5 1.0% Tuads 340 3. 5 B 27 6 1 0% Tuads... 340 8 A 30 6 03 0+ 350 7 A 27 6 0.5% DPG 350 5 A 27 .0 4 1.5% C+D 350 2 A 30 20. 2 6 1.0% Captex 350 10 A 27 noanalysis. 8 10 340 6 A 20 do no analysis 10 340 6 A 27 o o 10 340 5 A 30 do do 10 1 Method ASulfur and catalyst heated to 300 F., dipentene added at 300 F., mixture heated as shown. Method BAll reactants mixnd and heated together. Method C-Catalyst and part of dipentene heated to 300 F. S urry of sulfur in rerrainirvg d per ter e added at 300 F. and heated as shown. Method D-Sulfur heated to 300 F., dipe tene added at 300 F catalyst added as 10% solution in previously sulfurized dlpentene, mixture heated as shown.

2 C+D=67% Captax and 33% DPG (diphenyl guanidine).

7 8 Table II sulfur reduced the bearing weight loss to 0.20-0.25 gm./

SULFURIZED "DIPENTENE" PILOT PLANT DATA bearing, and (3) that 1.0% of samples made with 30% sulfur reduced this value to 0.11-0.13 gm./bearing. All

[Catalyst: 1.0% "Captax"+0.5% DPG."]

of these samples were acceptable in the copper strip all cases, clean engines and low bearing weight losses resulted from using these combinations.

m Q1 wmmw%%um w m fm n b sw oduuauuo n e e 3 hD s r t T m .rLE e w a s "m n v efilh C m L a t m M we a a m s h r e V E W R S 47411943 a m R O N m a m rattattt m n M a w W e 6 N Ms D 3 2972 Wb E 3 m mm 6MW7777 a H mm mm m Rm oooodcuo m .m w s m m m m m n H L h e .u m a ci I O mm m m m s e R 5" n V O t u m m E o m e c w a H mm b m n g T 0 mm mmm w a n 0 o m m h nd u m we 0 6 d m Pm m fih R m m m a m e m C d D S w e w u ab m R c d t m 2 e n 1" U m m w M a o w 0 e I 8 H1 H t w m T v a n n 6 H W w w s 1 n s n as 1 o I .1 o 6 0 V f n t m. o mk 5 5 0 5 w 1 W 2 3 .m fi F 5 09a u 1 O 2 mmm w 2 2 %mmm%m%%.m.u.mmmmmmmnfiwmmflwwfimmm I c uo 000 SFWH NNN. flit ll] fl E. u 3 3 5 5 5 5 3 5 w m a mm a a m a a w a wee T N M 5 .0 5 w W W ww W m m M m w 0 1 1 l l lllfllul ll ll l r H r ll l lll lifl ltll ll n n n u n u u n n u n u u 0 u m m m m m m m m m m n R u n n n n n u 5 9 L 2 3 5 1 Cu Strip Test-{i hrs. at 212 F 0.5% in SAE 0!].

Table IV 36-HOUR ORC-L4 CHEVROLET ENGINE TESTS [Performance at sulfurizcd dipentene in combination with detergents-1 High Grade SAE 3D20W Motor Oil Base.--

. 1 0 053 785 b wl w w WJ Pmofm 80 0 00 0 000 0 m m We Ge B B 5 w 3% meme... 5 a 0 L 2 2L ZLLZQ n vm H m 8 n was manna D o Lu 0 0 0 coded lam RZ g D 4 4 06 09286 E on 6 A 3. m V3 0 0 0 00 000 00 0 299 88292 m m a. a. W 6 R 4 4 l .n. m D. 11 a 8 III 11111 D S m I I d a m T m AU 00003 "M IW M 4 2 23332 S mm 000 00 n n n n u n "1 mm fl n Tm t .c m n "a m 9 n "my mmm m 9 "mm m%=". "0% a r u r n u n "or D .OWOOCWOOOO W m edd eddddye 0 D D H N u n .s N1 -0 n n u e S a e B x H B O n m 0 o m M o w m M w m a W B m E A S e d a r G m. m

egular Grade SAE It will be evident from the foregoing that: (1)1116 effectiveness of the product is not directly related to the In Table III are shown the results of 36-hour CRC-L-4 Chevrolet engine tests on a 95 viscosity index solventextracted Mid-Continent lubricating oil of SAE. 30 7 final sulfur content; (2) the effectiveness is directly r'e-- grade, and the same oil containing several examples lated to the amount of sulfur originally added; (3) a of the sulfurized commercial Dipentene of the present substantial degree of desulfurization is necessary to yield invention. It will be noted (1) that 0.75% of a sample the most desirable product; and (4) the elfectiveness: made with 27% sulfur reduced the copper-lead bearing depends largely on the particular molecular structure weight loss, in the standard test, from 0.87 to 0.49 gm./ which is obtained by the use of the catalysts. It is bebearing, (2) that 1.0% of samples made with 27% lieved that the final molecular or compositional structure obtained in the products of this invention is substantially different from any previously disclosed in the art.

It will be understood that the finished product will he used in proportions of about 0.05% to preferably in the range from 0.1% to 2% by Weight of the lubricant in which it is incorporated. The quanities mentioned are suitable for corrosion and oxidation inhibition. Where load-bearing properties are more important, greater quantities may be used, up to about or 12% by weight. When used in such quantities, the products add materially to the load-bearing properties of the lubricant. The higher concentrates such as oil blends containing up to 50% or more are of use mainly to facilitate handling and blending of the product in various oils and other lubricants.

The products of the present invention may be employed not only in ordinary hydrocarbon lubricating oils, but also in the heavy duty type of lubricating oils compounded with detergent additives such as metal soaps, metal petroleum sulfonates, and metal phenates, alcoholates, alkyl phenol sulfides and polysulfides, organo-phosph-ates and phosphites, thiophosphates and thiophosphites, xanthates and thioxanthates, carbamates, amines, and the like. They may be combined also with other conventional anti-oxidants, corrosion inhibitors, metal deactivators, pour point depressants, viscosity index improvers, and the like. They may be used in greases and in gear oils and other heavy lubricants as well as in crankcase lubricating oils, although their primary use is in the latter.

The compounds of the present invention may also be used as additives for other types of mineral oils such as motor fuels, diesel fuels and kerosene, engine flushing oils, industrial oils, process oils, general machinery oils, rust preventive compositions, and other mineral oil base compositions wherein it is desired to improve the oxidation resistance and other properties of the composition.

What is claimed is:

1. A mineral oil composition consisting essentially of a mineral base lubricant containing in the range of about 0.05 to 12% by Weight, based on the total composition, of a sulfur containing reaction product having an infrared absorption spectra in the 11.28 to 11.4 micron range, obtained by sulfurizing a cyclic non-aromatic unsaturated organic material selected from the class consisting of terpenes, sesqui-terpenes and diterpenes having the general formula (C H where n is an integer of value 2 to 4, with 20 to 35% by weight of sulfur based on the combined reactants and desulfurizing the resultant sulfurized material by heating it in the presence of 0.05 to 5% of a desulfurization catalyst of rubber vulcanization accelerator type selected from the group consisting of thiazole derivatives, aryl guanidine derivatives and dithiocarbamates, said sulfurizing and desulfurizing steps being carried out at a reaction temperature between 300 and 425 F. for a total period of 1 to 20 hours until evolution of H 8 has substantially ceased and the product is substantially non-corrosive to copper.

2. A composition as in claim 1 wherein said mineral oil is a lubricating oil.

3. Composition according to claim 1 prepared by a. process wherein sulfurization precedes desulfurization.

4. Composition according to claim 1 prepared by a process wherein the sulfurization and desulfurization are conducted simultaneously.

5. Composition according to claim 1, wherein the organic material is predominantly a C H monocyclic terpene.

6. Composition according to claim 1, wherein the reaction temperature is between 300 and 350 F.

7. A mineral lubricating oil composition consisting essentially of a lubricant base stock containing about 0.05 to 12% by weight, based on the total composition of the reaction product having an infra-red absorption spectra in the 11.28-11.4 micron range obtained by treating a O l-I monocyclic terpene with 25 to 33% by Weight of sulfur and 0.05 to 5.0% by weight of tetramethyl thiuram disulfide, said treating being carried out at a temperature in the range of about 300425 F. for a total period of 1 to 20 hours until evolution of H 5 has substantially ceased and the product is substantially non-corrosive to copper.

8. A mineral lubricating oil composition consisting essentially of a lubricant base stock containing about 0.05 to 12% by weight, based on the total composition of the reaction product having an infra-red absorption spectra in the 11.28-11.4 micron range obtained by treating a C H monocyclic terpene with 25 to 33% by weight of sulfur and 0.05 to 5.0% by weight of a mixture of benzothiazole and diphenyl guanidine, said treating being carried out at a temperature in the range of about 300- 425 F. for a total period of 1 to 20 hours until evolution of H S has substantially ceased and the product is substantially non-corrosive to copper.

References Cited in the file of this patent UNITED STATES PATENTS 2,206,151 Bennett July 2, 1940 2,338,829 Werntz Jan. 11, 1944 2,417,305 Knowles et a1 Mar. 11, 1947 2,443,823 Holt June 22, 1948 FOREIGN PATENTS 206,848 Great Britain July 10, 1924

Claims (1)

1. A MINERAL OIL COMPOSITION CONSISTING ESSENTIALLY OF A MINERAL BASE LUBRICANT CONTAINING IN THE RANGE OF ABOUT 0.05 TO 12% BY WEIGHT, BASED ON TH E TOTAL COMPOSITION, OF A SULFUR CONTAINING REACTION PRODUCT HAVING AN INFRARED ABSORPTION SPECTRA IN THE 11.28 TO 11.4 MINCRON RANGE, OBTAINED BY SULFURINZING A CYCLIC NON-AROMATIC UNSATURATED ORGANIC MATERIAL SELECTED FROM THE CLASS CONSISTING OF TERPENES, SESQUI-TERPENES AND DITERPENES HAVING THE GEN-NERAL FORMULA (C5HG)N, WHERE N IS AN INTEGER OF VALUE 2 TO 4 WITH 20 TO 35% BY WEIGHT OF SULFUR BASED ON THE COMBINED REACTANTS AND DESULFURIZING THE RESULTANT SULFURIZED MATERIAL BY HEATING IT IN THE PRESENCE OF 0.05 TO 5% OF A DESULFURIZATION CATALYST OF RUBBER VULCANIZATION ACCELERATOR TYPE SELECTED FROM THE GROUP CONSISTING OF THIAZOLE DERIVATIVES, ARYL GUANIDINE DERIVATIVES AND DITHIOCARBAMATES, SAID SULFURIZING AND DESULFURIZING STEPS BEING CARRIED OUT AT A REACTION TEMPERATURE BETWEEN 300* AND 425* F. FOR A TOTAL PERIOD OF 1 TO 20 HOURS UNTIL EVOLUTION OF H3S HAS SUBSTANTIALLY CEASED AND THE PRODUCT IS SUBSTANTIALLY NON-CORROSIVE TO COPPER.