CA1259305A - Sulfur-containing compositions, and additive concentrates, lubricating oils, and metal working lubricants containing same - Google Patents

Abstract

Title: SULFUR-CONTAINING COMPOSITIONS, AND ADDITIVE
CONCENTRATES, LUBRICATING OILS, AND METAL
WORKING LUBRICANTS CONTAINING SANE

Abstract of the Disclosure Sulfur-containing compositions are described which are prepared by sulfurizing (A) at least one fatty acid ester of a polyhydric alcohol, or (B) at least one fatty acid, fatty acid ester of a monohydric alcohol, or a mixture thereof, or (C) at least one other olefin, or (D) mixtures of any two or more of (A), (B) and (C), in the presence of a catalytic amount of (E) at least one salt of at least one dithiocarbamic acid of the formula R1(R2)N-CSSH
wherein R1 and R2 are each independently hydrocarbyl groups, or (F) at least one mercapto benzothiazole, or (G) mixtures of (E) and (F) Preferably, various mixtures of (A), (B) and (C) are sulfurized in accordance with the invention. The incorporation of a catalytic amount of salt of at least one dithiocarbamic acid of Formula I or at least one mercapto benzothiazole (or mixtures thereof) results in the preparation of sulfurized compositions which are characterized by excellent oil solubility and higher sulfur contents, and the compositions generally are lighter in color when compared to sulfurized compositions prepared in the absence of such catalysts. The sulfurized compositions prepared in accordance with the present invention are useful as general purpose antioxidants and friction modifiers for lubricating compositions and automatic transmission fluids and in particular, as additives in metal working lubricants.

Description

3~

Title: SULFUR-CONTAINING COMPOSITIONS, AND ADDITIVE
CONCENTRATES, LUBRICATING OILS, AND METAL WORKING
LUBRICANTS CONTAINING SAM~.

Technical Field of the Invention This invention relates to sulfur-containing compositions which are oil-soluble and which are useful as additives for lubricating oils and for metal working lubricants. More particularly, the invention relates to an improved method of sulfurizing fatty acid esters, fatty acids, other olefin compounds and mixtures thereof utilizing as a catalyst, salts of dithiocarbamic acids, mercapto benzothiazoles, and mixtures thereof.

Background of the Invention Various compositions prepared by the sulfurization of organic compounds and more particularly olefins and olefin-containing compounds are known in the art, as are lubricants containing these products. Typical sulfurized compositions prepared by reacting olefins such as isobutene, diisobutene, and triisobutene with sulfur under various conditions are described in, for example, Chemical R_ ew, 65, 237 (1965). Other references describe the reaction of such olefins with hydrogen sulfide and elemental sulfur to form predominantly mercaptans with sulfides, disulfides and higher polysulfides also being S0069 08/01/85 760186 12-2275 1 101 300.00CH
S0070 08/01/85 760186 12-2275 1 103 490.00CH

~.

~p ~ 25 .

-2-forrled as by-products. ~eference is made to ~
~h~ SQsJ~ 60, 2452 (1938), and U.S. Patents

3,221,056, 3t419.614 and 4,191,659. U.S. Patent 3,419,61~ describes a process for increasing the yield of mercaptan by carrying out the reaction of olefin with hydrogen sulfide and sulfur at a hiqh t~mperature in the presence of various basic n,aterials. U.S.
Patent ~,191,659 describes the preparation o sulfurized compositions by reaction at superatmospheric pressure of olefins with a mixture of sulfur and hydrogen sulfide in the presence of a catalyst followed by treatrllent with an alkali metal sulfide. The use of sulfuriæed natural and synthetic oils as additives in lubricating compositiolls has been suggested in the art such as in, for example, U.S. Patents 2,299,813 antl

4,~60,438.
In the past, sulfurized sperm oil was used - widely as an additive in many lubricant forrnulatiolls such as in gear oil, worm, and spur gears, autor~iatic transmission fluids, waxing lubricants, and as metal-working additives. Sulfurized sperm oil is especially useful for improving extrenle pressure properties while providing excellent "slip" and some degree of rust-inhibition in motor oils, gear lubricants, and rolling oils. However, the sUlfurized sperm oils have been replaced in recent years by other sulfurized compositions as a result of the reduction in availability of sperm oil and increased cost.
Sulfurized olefins such as those described above do not always exhibit the degree of lubricity which is - necessary in many applications.
Sulfuriæed fatty oils such as sulfuriæed lard oil have been described in the alt, but sulfurized lard , . ~ ' ;
.
~ . , .

, - .
.

3(~5 oil generally is not ade~uatcly solubIe in parafinic base oils to be useful. Several patcnts havc issued in the last decade suggesting solutions to the solubility problems exhibited by sulfurized lard oil. A number of the prior art suggestions have involved sulfurizing mixtures of fatty oils such as lard oil and soybean oil I and various olefinic compounds. For example, U.~.
Patents 3,953,347 and 3,926,822 describe compositions of matter useful as lubricant additives which are sulfurized compositions prepared by reacting sulfur with a mixture connprising at least one fatty acid ester, at least one aliphatic olefin containing about 8 to about 36 carbon atoms and optionally, at least one fatty acid. The sulfurized compositions are preparcd by heating such mixtures of fatty acid ester and fatty acid olefin with sulfur at temperatures of fron~ ~5 to about 200C. In addition to the above-described reagent, the reaction mixture may also inc]ude sulfurization pron~oters such as phosphorous-cGntaining reagents such as phosphorous acid csters, and surface-active agcnts such as lecithin. An example of a phosphorous acid ester given in these patents is triphenylphosphite.
U.S. Patent 2rO12~446 describes a method of sulfurizing pine oil which is reported as being useful as an additive for lubricant manufacture.
- U.S. Patent 4,188,300 describes a sulfurized product obtained by sulfurizing an olefin with a prime ~, burning grade lard oil having a very low free acid content. These products are reported to exhibit improved solubility in paraffinic oils as compared to s products obtained when an olefin is co-sulfurized with lard oil having a higher content of free acids such as ' ~ .

1 , ~ ' .
, i '; 1 ~ ., ~ . ' 'lt _ ~ . t~
. _.. . . .
. ' I

~ - `
,;~
~ l ~ ;i9;~0~i , .
inter-strained lard oil or extra win~er-strained lard oil. Co-sulfurized products containing about 5 to 25~
¦ . by weight of sulfur are obtained and are reported as being useful as metal-working oil additives. The preparation of various synthetic sulfurized oil of the reaction of sulfur, lard oil and polyisobutylene oligomers containing at least one pair of maxinlally crowded geminal methyl groups (e.g., tetraisobutylene) ~;, is described in U.S. Patent 4,1Ç6,795. The preparation of synthetic sulfurized oil uceul as the replacement

5! for sulfurized sperm oil also is described in U.s.
Patents 3,843,534; 3,~25,495; 4,166,795; 4,166,796;
1 4,166,797; 4,321,153; 4,456,54û; and 4,4~7,705. ~rhe j l sulfurization generally is carried out using elenlent.ll sulfur, and simultaneous sulfurization and chlorination ¦ may be cffected by reacting with sulfur monochloride.
1, Phosphosulfurization is described in these patellts and ¦ may be carried out by addition of small an~ounts oL a phosphorus sulfide to the sulfurized blend followed by heating.
¦ When preparing sulfurized compositions for use i as lubricant additives, it generally is desirable to obtain products by the most inexpensive procedure ? utilizing inexpensive raw n;aterial. The color of the j ~ sulfurized conlpositions obtained should preferably be ~n 1 ~ - light, and the sulfur contained in the products should 3~ not be active sulfur.
! The present invention also relates to metal working operations and more particularly to lubricants ¦ ~ for use during such operations. In its broadest sense, it comprises a method for lubricating netal during working thereof and metal workpieces having on the ~ surface thereof a film of a lubricant composition.
.-.~

\
. ; '` ' ~1 ~ . .. t' .

1~ 59~05i -Said composition comprises a major an,ount of a lubricating oi] and a minor amount of at least onc sulfurized composition prcpared in accordance with this invention.
Metal working operations, for example, rolling, forging, hot-pressing, blanking, bending, stamping, drawing, cutting, punching, spinning and the like, generally employ a lubricant to facilitate the same. Lubricants greatly improve these operations in that they can reduce the power requircd for the operation, prcvent sticking and decrease wcar of dies, cutting tools and the likc. In addition, they frequently provide rust-inhibiting properties to thc metal being treated.
Many prcsently known metal wor~in(~ lubricants are oil-based lubricants containing a relatively large~
amount of active sulfur present in additivcs thcrein.
(By "active sulfur" as u~ed hercin is meant chemically combined sulfur in a form which causcs stainlllg of copper.) The presence of active sulfur is sometimes detrimental because of its tendency to stain copper, as well as other metals including brass and alun~illunl.
Nevertheless, its presence has frcquently been necessary because of the beneficial extrenle pressure properties of active sulfur-containing compositions, especially for the working of ferrous netals.
~umm~3y of the InY~n~ion f Sulfurized compositions are described which are prepared by reacting at an elevated temperature, a sulfurizing agent with (~) at least one fatty acid ester of a polyhydric alcohol, or (B) at least one fatty acid, a fatty acid ester of a monohydric alcohol, or a mixture thereof, or ~C) at least one other o~efin, .

:. . . -. , ~
~ ..', ~ ~n~ ~

.

-6- ~2~3~.5 or (D) a mixture of any two or more of (A), (B) and (C) in the presence of a catalytic amount of (B) at least one salt of at least one dithiocarbamic acid of the formula R1(R2)N-CSSH (I) wherein R1 and R2 are each independently hydrocarbyl groups, or (F) at least one mercapto benzothiazole, or (G) mixtures of ~E) and (F). More generally, the invention relates to sulfurized compositions prepared by reacting at an elevated temperature, a sulfurizing agent with a mixture of (A) about 100 parts by weight of at least one fatty acid ester of a polyhydric alcohol, (B) from about 0 to about 200 parts by weight of at least one fatty acid, fatty acid ester of a monohydric a].cohol, or a mixture thereof, (C) from about 0 to about 400 parts by weight of at least one other olefin, and a catalytic amount of (E) at least one salt of at least one dithiocarbamic acid of the formula R1(R2)N-CSSH (I) wherein R1 and R2 are each independently hydrocarbyl groups, or (F) at least one mercapto benzothiazole, or (G) mixtures of (E) and (F). The incorporation of the catalyst results in the preparation of sulfurized compositions which are characterized by higher sulfur contents, and the compositions are lighter in color and have less odor when compared to sulfurized compositions prepared in the absence of such catalysts. The sulfurized compositions prepared in ;''~
~....

1~ 5.33~5 _ 7 _ accordancc with thc present invention arc uscful as gcneral purpose antioxidants and friction modificrs for lubricating compositions, and as additivcs in metal working lubricants.
Detailed ~escription of thc Prefcrred Embodimcnts Componcnt (A) which is sulfuri~,ed in accordance with tllc prcsent invention is at least one fatty acid ester of a polyhydric alcohol. The term "fatty acid" as used in the specificntion and claims rcfers to acids which may be obtaincd by the hydrolysis of a naturally occurring vegetable or animal fat or oil. These are usually in Cl6_20 range and include palmitic acid, stearic acid, oleic acid, linolcic acid, etc.
The fatty acid esters which are useful as component (A) are thc fatty acid csters of polyhydric alcohols. Examples of suitable polyhydric alco~ols include ethylene glycol, propylenc glycol, trimetllylenc glycol, neopentyl glyco], glycerol, ctc. Fatty oils which are naturally occurring esters cf glyccrol with the above-noted long chain carboxylic acids, and synthctic esters of similar structure are uscful.
Usually preferrcd fatty acid esters in the process of the present invention are fatty oils derived from unsaturated acids, especially oleic and linoleic acids, including such naturally occurring animal fats and vegetable oils as tall oil, lard oil, peanut oil, cottonseed oil, soybean oil, sunflower oil; corn oil, etc. Specially grown sunflower oils containing high amounts of oleic acid (e.g., ~ 80~ by weight or more of oleic acid) can be sulfuri~ed in accordance with the process of this invention. Such sunflower oils are available commercially under the general trade ' , .' ' :' .

.:.

desi~nation TKISUN from $VO Enterprises Corpor,ltion, WickliLl-c, OlliO.
~ lthough various compositions preparcd in accordance wi~h the method of the invention utilizing only one type of fatty acid ester of a polyhydric alcohol are soluble and uscful as oil additives, thc usc of mixtures of fatty acid esters of po]yhydric aleohols is prcferred. In partieular, mixtures of fatty acid esters of polyhydric alcohols containing at least about 50~ by weight of lard oil, gencrally from about 50'~ to about 80~ by weig}-t of lard oil rcsults in the formation of sulfurized compositions containirlg ~he desirably high amounts of sulfur and arc relativcly inexpensive. Morcover, such sulfurized materia]s preparcd in accordance with the proccss of this invcntioll are characterizcd by a rcdu(:tion in undesirable color ancl odor. Thc examples of mi~turc-;
based on lard oil includc, for examplc, a mixturc of 50 parts by wcight of lard oil and 50 parts by wcic,ht c>f soybean oil, a mixture containing 75 parts of larcl oil and 25 parts of soybcan oil, and a mixturc comprising 60 parts of lard oil and 40 parts of peanut oil.
The compositions which can be sulfurized in aecordance with the method of the present invcntion may be (B) at least one fatty acid or fatty acicl estcr of a monohydrie alcohol, or mixtures thereof. Eatty acids of the type described above ean be utilized, and the fatty aeids generally utilized are unsaturated fatty aeids sueh as oleie aeid or linoleie aeid. ~lixtures of fatty aeids SUCII as obtained from tall oil or by the hydrolysis of peanut oil, soybean oil, sunflower oil, ete., also are useful. Esters of fatty âcids obtained from monohydrie aleohols eontaillirlg up 1~ ~ . - --,:
. :
~ . - -~ l~ f3 P~

. .

. ~

to about 20 carbon atoms can be utilized as component (B)either alone or in combination with fatty acids. Examples of monohydric alcohols useful in preparing the fatty acid esters include methanol, ethanol, n-propanol, isopropanol, the butanols, etc. Specific examples of fatty acid esters of monohydric alcohols useful as component (B) in the process of the invention include methyl oleate, ethyl oleate, lauryl oleate, methyl linoleate, oleyl stearate, cetyl linoleate, etc.
The compositions which can be sulfurized in accordance with this invention may be other olefinic compounds (C) such as, for example; aliphatic arylaliphatic or alicyclic olefinic hydrocarbons containing at least three carbon atoms; Diels-Alder adducts of at least one dienophile with at least one aliphatic conjugated aliphatic diene; and at least one terpene compound. The olefinic compound contain at least one olefinic double bond which is defined as a non-aromatic double bond. That is, the double bond connects two aliphatic carbon atoms.
In one embodiment, the olefin utili~ed as component (C) may be defined by the formula R1R2C=cR3R4 (II) wherein each of R1, R2, R3 and R4 is hydrogen or an organic group, with the proviso that at least one R group must be an organic group. In general, the R values in the above formula may be satisfied by such groups as -R5, -C(R5)3, -CooR5, -CON(R 52~ -COON(R )4, COOM, -CN, -C-R5, -X, -R5X, -YR5, -R5YR5, -R N(R )2 or -Ar, ,f ~, - - ~
~ ~:593~5 wherein cach R is indcpendently hydrogen, alkyl . ! alkcnyl, aryl, alkylaryl, substituted alkyl or substi-I tuted alkenyl, with the proviso that any two R5 groups can be alkylene or substituted alkylene wllereby a ring of up to about 12 carbon atoms is formed;
Ar i9 an aryl or substituted aryl group of up t to about 12 carbon atoms in the substituent;
M is one equivalent of a metal cation tpreferably Group I or II, e.g., sodium, potassium, barium, calcium);
X is halogen (e.~., chloro, bromo, or iodo);
I anc 3 Y is oxygen or divalent sulfur.
Any two of R , R , ~3 and R4 may also , together form any al~ylenc or substituted a1kylene , group; i.e., the olefinic compound mav be alicyc1ic.
The nature of thc substituents in thc substitutcd moieties described above is not normally a ~ eritical aspect of the invention and any such ! substituent is useful so long as it is or can be made eompatible with lubricating environments and does not ,1 interfere under the contemplated reaction conditions.
Thus, substituted eompounds which are so unstable as to ; ~ deleteriously decomposo under the reaction conditions ; employed are not contemplated. However, certain substituents such as keto or aldeliydo ean desirably undergo sulfurization. The sPlection of suitable substituents is within the skil; of the art or may be established through routine testing. Typical of such substituents include any of the above listed moieties as well as hydroxy, carboxy, carbalkoxy, amidine, , ~ ~ amino, sulfonyl! sulfinyl, sulfonate, nitro, phosphate, phosphite, alkali metal mereapto and the like.

, ~ :
~ .

_.,.___ _ . . ~ . . . _~ .. __ ... ___ ... _ .. _ __ \

, ~ . ~
. The olcfinic compound is usually one in which each 1~ group wllich is not hydrogen i9 illdCpClldClltly alkyl or a].kenyl, or (lcss oftcn) a corresponding .~ ~ substituted group. Monoolef.~nic and diolefinic compounds, particularly the former, are prcfcrrcd, and ~ especially terminal monoolofinic hydrocarbons; that is, t those compounds in which R3 and R are hydrogen and and R2 are alky.l (that is, tlle olefin is aliphatic).
' ' Olefinic compounds having at least about 3 carbon atoms, and especially about 3 to about 36 carbon atoms are desirable. Olefins containing from about 8 to 24 ~ I carbon atoms are particularly useful.
.' ~ The olcfinic cornpound also can be an aryl.lli-phatic compound, particularly whercin the ary] group i5 j 1 a phenyl or substitute~ phenyl gronp. .speciic examples include styrenc, alpha-metllyl styrcnc, vin51 I ¦ toluene, 9-ethyl vinyl benzenc, etc.
I , Propylene, isobutcne ancl ~.hcir dim-~ls, ¦ ¦ trimers, tetramcrs and oligomers, and mixturcs thcrc~f ~ ! are ùseful olefinic compounds. ~xamplcs o~ usef~ll olefins include isobutene, l-butenc, l-hexene, l-octene, diisobutene, cyclohexenc, triisobutelle, commercially available higher aliphatic alpha-olefins, especially those in the C12_30 range~ such as 1-hexadecene and 1-octadccene, and conu~ercial mixtures - j thereof such as Cl5_20 alpha-olcfins, C16 alpha-olefins, C15_18 alpha-olefins~ C22_28 P
¦ olefins, etc.
~ Polymers of olefins such as, for example, ., i isobutene also are useful so long as they and their ~: ~ sulfurized derivativcs are ccmpatible witll the othcr : . : . conmponents, and the sulfurized product does not lose ~ : its desirable properties. PGlybutenes having number . -, ., , ~ , ~s~

average molecular weights of up to about 1000 or 1500 are examples of useful polyolefins.
Generally, the olefinic component (B) is at least one aliphatic, aryl aliphatic, or alicyclic olefinic compound containing at least about 3 carbon atoms. Such olefinic compounds containing from about 3 to about 36 carbon atoms and more preferably from about 8 to about 24 carbon atoms are particularly useful. It is common to use mixtures of such olefins as component (C) since these mixtures are available commercially.
The olefinic compound can also be an internal olefin. The internal olefins may be represented by the following general formula CH3(CH2)nCH=cH~(cH2)mcH3 (III) wherein n and m are independently integers from 0 to about 15 and the total number of carbon atoms is at least 8.
Examples of internal olefins useful in this invention include 2-octene, 2-dodecene, 4-dodecene, 9-oc-tadecene,

7-te-tradecene, 7-hexadecene and 11-eicodecene. Mixtures of two or more olefins including mixtures of alpha- and internal olefins are useful. One method for preparing such mixtures of olefins is by the isomerization of commercially avialable alpha-olefins, and the product of the isomerization reaction is a mixture of olefins wherein the double bond is in the 1,2,3,4, etc. position.
Alternatively, the mixtures of olefins may be obtained by fractionation or by blending of olefins of various types and molecular weights. The isomerization of terminal olefins is effected by heating the olefin with mildly acidic catalysts such as Amberlyst 15. Alpha-olefins, and particularly those containing about 10 to about 20 carbon 3~3~
-13~

atoms are preferrred. Mixtures of such olefins are commercially available and are particularly desirable for use in the present invention.
In another embodiment, the olefin (C) is a Diels-Alder adduct. The Diels-Alder adducts are a well-known, art-recognized class of compounds prepared by the diene synthesis or Diels-Alder reaction. A summary of the prior art relating to this class of compounds is found in the Russian monograph, Dienovvi Sintes, Izdatels-two Akademii Nauk SSSR, 1963 by A.S. Onischenko. (Translated into the English language by L. Mandel as A.S. Onischenko, Diene Synthesis, N.Y., Daniel Davey and Co., Inc., 1964.) The preparation of a number of Diels-Alder adducts useful in the present invention is described in U.S. Reissue Patent 27,331.
Basically, the diene synthesis (Diels-Alder reaction) involves the reaction of at least one conjugated diene, >C=C-C~C<, with at least one ethylenically or acetylenically unsaturated compound, >C=C< or -C=C-, these latter compounds being known as dienophiles. The reaction can be represented as follows:

Reaction 1:

/c\
>C=C-C=C< + >C=C< ~ -C C-ll A
--C C--\C/

"~

~2~

Reaction 2:
~ \ /

>C=C--C=C< + --C-C--~ --C C--~I B 11 --C\c /C--The products, A and B are commonly referred to as Diels-Alder adducts. It is these adducts which are used as as starting materials for the prepartion of the sulfurized Diels~Alder adducts utilized in the invention.
Representative examples of such 1,3-dienes include aliphatic conjugated diolefins or dienes of the formula ~ I I /
j i C~_____ 3 C4 \ (III) R R

wherein R through R5 are éach independently selected from the group consisting of alkyl, halo, alkoxy, alkenyl, alkenyloxy, carboxy, cyano, amino, alkylamino, dialkylamino, phenyl, and phenyl-substituted with 1 to 3 substituents corresponding to R through R5 with the proviso that a pair of R's on adjacent carbons do not form an additional double bond in t:he diene. Preferably not more than three oE the R variables are other than hydrogen and at least one is hydrogen. Normally, the total carbon content of the diene will not exceed 20. In one preferred aspect of the invention, adducts are used where R2 and R3 ~!
.; , -15- ~2~3~

are both hydrogen and at least one of the remaining R
variables is also hydrogen. Preferably, the carbon content of these R variables when other than hydrogen is 7 or less.
In this most preferred class, those dienes where R, R1, R4 and R5 are hydrogen, chloro, or lower alkyl are especially useful. Specific examples of the R Variables include the following groups: methyl, ethyl, phenyl, HOOC-, N_C-, CH30-, CH3COO-, CH3CH20-, CH3C(O)-, HC(O)-, Cl, Br, tert-butyl, CF3, tolyl, etc. Piperylene, isoprene, methylisoprene, chloroprene, and 1,3-butadiene are among the preferred dienes for use in preparing the Diels-Alder adducts.
In addition to these linear 1,3-conjugated dienes, cyclic dienes are also useful as reactants in the formation of the Diels-Alder adducts. Examples of these cyclic dienes are the cyclopentadienes, fulvenes, 1,3-cyclohexadienes, 1,3-cycloheptadienes, 1,3,5-cycloheptatrienes, cyclooctatetraene, and 1,3;5-cyclononatrienes. Various substituted derivatives of these compounds enter into the diene synthesis.
The dienophiles suitable for reacting with the above dienes to form the adducts used as reactants can be represented by the formula K ~ / K2 / C C \ (IV) wherein the K variables are the same as the R variables in Formula III above with the proviso that a pair of K's may form an additional carbon-to-carbon bond, i.e., K-C-C-K2, but do not necessarily do so.

`,l,,' -lG-~ preferred class oE dienophiles are those wherein at least one of the K variables is selectcd from the class of electron-accepting groups such as formyl, cyano, nitro, carboxy, carbohyclrocarbyloxy, hydrocarbylcarbonyl, hydrocarbylsulfonyl, carbamyl, acylcarban,yl, N-acyl-N-hydrocarby]carban,yl, M-hydro-carbylcarbamyl, end N,N-dihydrocarbylcarbamyl. ~hose R
variables which are not electron-accepting groups are hydrogen, hydrocarbyl, or substituted-hydrocarbyl groups. Usually the hydrocarbyl and substituted hydrocarbyl groups will not contain more than lO carbon ; ato~l!s e1Ch .
The hydrocarby] groups prcscnt as N-hydro-carbyl substituents are preferably alkyl of ~ to 30 carbons and especially l to lO carbons. Representativc of this class of dienophilcs are the following:
nitroalkenes, e.g., l-nitrobutcnc-l, l-nitropcntene-l, 3-methyl-l-nitrobutene-l, 1-nitroheptene-l, l-nitro-octene-1, 4-ethoxy-1-nitrobutcrle-1; a~pha, beta-ethylenically unsaturated aliphatic carboxylic acicl esters, e.g., alkylacry]ates and a~pha-methyl alkylacrylates (i.e., alkyl methacrylates) such as butylacrylate and butylmethacrylate, decyl acrylate and decylmethacrylate, di-(n-butyl)-maleate, di-(t-butyl-maleate); acrylonitrile, methacrylonitrile, beta-nitrostyrene, methylvinylsulfone, acrolein, acrylic acidS alpha, beta-ethylenically unsaturated aliphatic carboxylic acid amides, e.g., acrylamide, N,N-dibutyl-acrylamide, methacrylamide, N-dodccylmethacrylamide, N-pentyl-crotonamide; crotonaldehyde, crotonic acid, beta, beta-dimethyldivinylketone, metllyl-vinylketone, N-vlnyl pyrrolidone, alkenyl halides, and the like.

.
, . ..
:~
J ..

.

One preferred cluss of clienoplliles are those wherein at least one, but not more than t~o of i;
variables is -C~O)O-Ro where Ro is the resitlue of a saturatcd aliphatic alcohol of up to about ~0 carbon atoms; e.g., for example at least one ~ i5 carbohydro-; carbyloxy such as carboethoxy, carbobutoxy, etc., thc i aliphatic alcohol fron, ~hich -r~O is derived can be a nono or polyhydric alcohol such as alkylene~lycols, I; alkanols, aminoalkanols, alkoxy-substituted al~anols, ! ethanol, ethoxy ethanol, propanol, beta-diethyl-t , aminoeth~nol, clodecyl alcohol, diethy]ene ~Jlycol, ~ I tripropylenc glycol, tetrabuty]ene (~lycol, hexanol, ;; octanol, isooctyl alcohol, and the likc. In tHis ¦ ~ especially preferred class of dicnoijhile-:, not more than two h variables will be -C(O)-O-~O grollps and , , thc rcmailling ~ variables will be hyclrocJen or lo~cr ¦ I alkyl, e.g., mcthyl, ethyl, propyl, isoproE,yl, and the like.
I Specific exa~ples of dienophiles of tl,c type ! discussed above arc t},ose wherein at least one o t},e ii I variables is one o~ the following groups: hydrogell, methyl, ethyl, phenyl, HOOC-, ilC(O)-, Cil2=Cil-, ilC--C-, , ~ CH3C(O)O-, ClCH2-, HOC112-, alpha-pyridyl, -NO2, Cl, Br, propyl, iso-butyl, etc. - ~
In ~ddition to the ethylenically unsaturated ¦ ~ dienophiles, there are ~lany useful acetylel:ically , 1 ~ ~ unsaturated dienophiles such a~; propiolaldehyde, ~, ~ methylethynylketone, propylethynylketone, propenyl-; t ethynylketone, propiolic acid, propiolic acid nitrile, ethylpropiolate, tetrolic acid, proE~argylaldehyde, aeetylenedicarboxylic acid, the dimethyl ester of acetylenedicarboxylic ac3d, dibenzoylacety~ene, and the ~ like.
'.~ , .. . .
~' ~' , ,.

, _ . , , :. .

t,~

~ 5 Cyclic dienophiles incluce cyclopentencdione, coumarin, 3-cyanocoumarin, dimethyl maleic anhydride, 3,6-endomethylene-cyclohexenedicarboxylic acid, etc.
With the exception of the unsaturated dicarboxylic anhydrides derived Lrorn linear dicarboxylic acids ¦ (e.g., maleic anhydride, methylnlaleic anhydride, chloromaleic anhydride), this class of cyclic dienophiles are limited in con,mercial usefulness due to ~- their limited availability and other economic considerations.
~ The reaction products of these dienes and f~ dienophi]es correspond to the general iormulae `~ Rl \ / R

2 _ C / i C /
~~ \ Kl ¦` R3 / K2 C ~ K3 ~4\ R5 .' and (V) ¦ j ¦ K2 . . ~ R4~ \ R5 :
..
~ \~ . .
,~
.

.i !
O~;;

~, ,. I -19-wherein R through R5 and K through R3 are as defined hereinbefore. lf thc dienophile moiety entering into the reaction is acetylenic rather than ethylenic, two of the K variables, one frosn each carbon, form anothe. carbon-to-carbon doublc boncl.
Where the diene and/or the dienopnile is itself cyclic, the adduct cbvlously will be bicyclic, tricyclic, fused, etc., as exemplified below:
B~ is~
.~ O
>C=C-C=C< + CH-C~ O

CH-C~ ~ \ O
~' l\
.
a~lio~ 4:

Normally, the adducts involve the reaction of i , ~ equisnolar amounts of diene and dienophile. However, if the dienophile has more than one ethylenic linka~e, it . ~ ~ i8 possible for additional dies~e to react if preCent in . ~ the reaction mixture.
~ ; The adducts and processes of preparing the ; ~ 1 ~ ~ adducts are further exen;pliEied by the following ~ ~ ~e:amples. Unle:s otherwlse indicated in these e:ampi~es :. ~ ~ , . . '' ~. :

.

~ -2~- ~259305 and in other parts of tl-is specifieation, as well as in the appended clairlc, al] parts and pel-centa(J~s are by wei(Jht .
F.X~MPLE DA-l A mixture comprisin~ 400 parts of toluene and 66.7 parts of aluminum chloride is charged to a \ ; t~lo-liter flask fittcd with a stirrer, nitro~en inlet ~¦ tube, and a solid earbon dioxide-eooled reflux eondenscr. ~ second mixture eonprising 640 parts (5 moles) of butyl aery]ate and 240.8 parts oL toluene is ¦ ~dded to tl,e AlC13 slurry while n,aintajninc~ the t temperature within the rangc of 37-58C over a 0.25-hour period. Thercafter, 313 parts (5.R molcs) of butadiene i5 addcd to tl,e slurry over a 2.75-hour period ~hile naintaining ti~~e tcnpeLature of the ' reaction mass at 50-61~C by means of external cooling.
j! The reaetion mass is blown with nitrogen for abollt 0.33 ¦~ hour and then transferLed to a four-liter separatc)ly !~ funrlel and ~aslled with a solution of 150 part:s of eoneentrated hyclroehlorie aeid in 1100 parts of water.
¦ Thereafter, the produet is subjeeted to two additional / I ~ater washin~s using lOnO parts o watcr for e.,c~
wash. The washed reaetion prodllet is subse~uently - - distilled to ren~ove ~nreaeted butyl aerylate and ~ toluene~ The residue of this first distillation step j ~; ~ is subjeeted to further distillation at a pressure of 9-10 millimeters of mereury whereupon 785 parts of the ~desired produet is eolleeted over the temperature of 105-115C.
EX~.PLE D~-2 - The adduct of isoprene and acryl~nitrile is i ~ - prepared by mixing 136 rarts of isoprene, 106 parts of acrylonitrile, and 0.5 - parts of hyclro~1uinone ". ~ - -.

'-' ~ ' ~L259305 (polymeri~2tion inhibitor) in a rockln~ autoclave and thereafter heatin~ Lor ~6 hours at a ten,perature within the range of 130-1~0C. The autoc1ave is vented and the contents decanted thereby producing 240 parts of a light yellow liquid. This liquid is stripped at a temperature of 90C and a pressure of 10 millimeters of mercury thereby yieldin~ the desired liquid product as the residue.

¦ Usin~ the procedure of Exanple D~-2, 1~6 ~arts I of isoprene, 172 parts of methyl acrylate, and 0.9 part of hyc]roquinone are converteæ to the isoprene-metllyl acry]ate adduct.
iEXP~IPI.E D~-4 Following the procedure of Example DA-2, ]04 parts of liquified butadiene, 166 parts of m-:thyl I acrylate, and 1 part of hydroquinoIle are charged to tl,e ,~ rocking autoclave and heated to 130-135C for 14 ! hours. The product is subseouently c,ecaI)tcd and 1' stripped yielding 237 parts of the adduct.
f EX~PLE D~-5 ,~ One-hundred thirty-nine parts (1 mole) of the adduct of butadiene and methyi acrylate is ^ transesterified with 158 parts (1 niole) of decyl I ,, alcohol. The reactants are added to a reaction flask j ;~ and 3 parts of sodium methoxide are added. Thereafter, ¦¦ ~the reaction mixture is heated at a temperature of I~ 1~0-200C for a period of 7 hours. The reaction mass is washed with a 10~ sodium hydroxide solution and then 250 parts of naphtha is added. The nai,htha sollltion is washed with water. At the completion of t}-,e washin~, 150 parts of toluene are added and the reaction mass i&
` ~ ~tripped at 150C under pressure of 28 parts Oe ~ l~S~
I ~ -22-.
mercury. A dark-brown fluid product (225 parts) i5 recovercd. This product is fraetionated under reduced pressure resul~ing in the recover~ of l7~ ~arts of tl1e product boiling in the range of 130-133DC at a 1ress11re of 0.45 to 0.6 parts of nlercury.
EX~PLr )~-6 The general procedurc of Exa1lp~e n~-l is repeatcd exce~t that only 270 parts (5 mole~) of 4utadiene is included in the reaetion mixture.
[~ ~s mentioned a~ove, the other olefin conE)ound ~ (C) n,ay be at least one terpene cor~;pound.
i ~he tcrDI "terpene eompound" as used in the speeifieation and elains is intended to inelude the various isomerie terpene hydrocarbon~ having the enpirieal iormula Clolll~, sueh as contain~c. in turpentine, pine oi~ and di~entcnc-s, and the various syntlletic a11d natural y occuring oxygen-containincJ
!. derivative~ ture~ of these various con~Jounds 1~ ~3enerally will be utilized, especially who11 natl1ral roducts such as pine oil and turpentine are used.
Pine oil, for ex~mple, which is obtained by destructive distillation of waste pine wood with super-heated steam eonlprises a mixture of terpene derivatives sueh as alpha-terpineol, beta-terpineol, alpha-fenehol, ea~phor, borneol/isoborneol, fenehone, estragole, dihydro ~ alpha-terpineol, anethole, and other mono-terpene~ hydrocarbons. The speeifie ratios and amounts of the various eomponents in a given pine oil ill depend upon the partieular souree and the degree Il of purifieation. A group of pine oil-derived produets t~ are available eommereially from Hereules Ineorporated.
It has been found that the pine oil produets ~enerally known as terpene aleohols available from 11ereules `'', ;:
.
: .. : . ~
;. ~
.

~ .. ~ . . .. .

i2590~

Incorpc)ratec1 are particularly usc!ful in the l~reparation of the sulfurizecl proc.llct6 oi the invention. ~aml,les of such produe~3 include alpha-Terpinc-ol ccJntaining about ~5-97% of alpha-terpineol, a high purity tertiary terpene aleohol mixture typieally eontai~ing 96.3~ oî
tertiary aleohols; Terpineol 318 Prime which is a mixture of isomerie terpineols obtained by c1ehydration of terpene hydrate and eontains about 60-65 ~-eight pereent of alpha-terpineol and 15-20~ beta-tc~rpineol, and 18-20~ of other tertiary terpene aleohols. Otl-er mixtures and grades of useful pine oil proc7uscts also are av~ailahle from l,ereules uncer sueh desi~nations as Yarmor ~ 302, }lereo pine oil, Yar~or 302~;, Yarr~c,l- ~ alld Yarnlor 60.
l'he terpene eompounds whieh ean be utilized in the preparation of the sulfurized co~,~positions of tl,e present invention also may be sulfurizet7 tcrLellc eampounds, sulfurized mixtures of te~penc! eonlpounc7~ Ol mixtures of at least one tclpene eomEIound and at least one sulfurized terpene conpound. Sulfurized ter,~cne eompounds ean be preLJc~red by sulfurizin~ terpene eompounds with sulfur, sulfur halic7es, or mixtures of sulfur or sulfur-dioxide with hydro~Jen sulficle as will be deseribed more fully hereinafter. ~]so, the ~ulfurization of various terpene eompounds has been deseribed in the prior a~t. For eYample, the sulfurization of pine oil is deseribed in U.S. Patent 2,~12,446.
The eompositions whieh can be sulfurized in aeeordanee with this invention nay be ~D) a mixture of two or more of (~), (B) and (C) deseribed above. Thus a mixture of (~) at least one fatty aeid ester and (C) at least one olefin may be sulfurlzed by the proeess of ! --2~-this invcntion. Other combinations inc]ode t},e I following: (A) and (n); (B) and (C); and (A), (~) and ! (C).
! In one prccrrcd en;bodiment, the sulfurized compositions of t:},c in~ell-ion are prcparcd by rcactiny at an elcvated ten,perature a ~ulfurizin~ agent with a mixturc comprisin~ (~) about 100 parts b~ wcigl,t of at least one fatty acid cster of a polyhydric alcohol, (B) : from abollt 0 to about 200 parts by weight of at least one $atty acicl, fatty acid ester of a morlohydric alcohol, or a mixture thereof, (C) $ron, about: 0 to about 400 parts by weight of at ]east onc ot}lcr ole$in in the presence of (E) at least one salt of at lca~t one dithiocarbamic acid of tl,c $ormula 2)~-CSS~I (I) . wherein Rl and R~ arc each ind(l~cndell-~y hydrocarbyl groups, or (F) at least one r.lercai)to '! benzothiazole, or (C) mixtures o$ (E) and (E).
!i Preferably these mixtures will contain at ].cast about two parts of the fatty acid or fatty aci~l estcr (r). A
.1 preferred range is $rom about 2 to about 100 uarts o ~B) per 100 parts of (A). Otller pre$erred nlixtureC
contain at least about 25 parts of the aliphatic olefin . ~ ~ (C). A particu~arly useful range o$ (C) is from about : ~ ~ - 25 to about 100 parts of (C) per 100 parts of (A). In;~ ~ : another preferred embodiment the mixture .which is . sulfurized will contain all three components ~A), (B) ~: ~ I ~ . . and (C).
: . The sulfurization reactions of the present .: ~ : ~ invention are carried out in the presence of a .~ . : catalytic amount of (E) at least one salt of ~t least one dithiocarba~ic acid of the fornlula . ,, , . ~

.

-25 ~

R1(R2)N-CSSH (I) wherein R1 and R2 are each independently hydrocarbyl groupS. The hydrocarbyl groups R1 and R2 may be alkyl groups, cycloalkyl groups, aryl groups, alkaryl groups or aralkyl groups. R1 and R2, taken together, may represent the group consisting of polymethylene and alkyl-substituted polymethylene groups thereby forming a cyclic compound with the nitrogen. Generally, the alkyl group will contain from about 1 to about 20 carbon atoms and more generally from about 2 to about 10 carbon atoms. The salts may be metal, ammonia or amine type salts.
The metal of the metal salt may be a monovalent metal or a polyvalent metal, although polyvalent metals are preferred because they are generally more oil-soluble than alkali metal salts. Suitable polyvalent metals include, for example, the alkaline earth metals, zinc, cadmium, magnesium, tin, molybdenum, iron, copper, nickel, cobalt, chromium, lead, etc. The Group II metals are preferred.
The ammonium and amine salts may be characterized by the general formula R1(R2)NCSS N(H)R5R4R3 (VI) wherein R1 and R2 are as defined in Formula I, and R3, R4, and R5 are each independently hydrogen or hydrocarbyl groups such as R1 and R2. Such salts can be prepared by methods known in the art. For example, the preformed dithiocarbamic acid can be treated with ammonia or a substituted amine R3R4R5N. Specific examples of such salts include ...................................................

~;

-~26-I dimethylacyclohexyl-amnlonium dibutyltl)iocarbamatc and ., piperidinium pentanlethylenedithiocarballlate.
~Iternatively, the sa~ts can be prepared directly from the reaction of an excess of an amine, (e.g., ¦ RlR2NII) with carbon di~ulfide as il~ustrated in the ~ j following reaction.

- ~; 2 ~ 2NI~ + 5~S2~1(R2)N-Css N(H)2(R2) ?
¦ In such instances, the two Rl groups in the salt are identical and the two R2 ~roups in the ~ product also are iclentical.
; Mixtures oE metal salts, amine salts, and metal and amine salts of dithiocarbanlic acids also are ¦ contcniplated as bein~ useful in the present invention.
~uch mixtures can be prepared by first preparing mixturcs of dithiocarbarnic acids and thereafter converting said acid mixtures to salts, or 1 alternatively, the salts of various dithiocarban,ic ! ~ ! acids can be prepared and thereafter mi~cd to give the I desired product. Thus, the mixtures which can be , incorporated in the compositions of the invention may ! be merely the physical mixture of the different : , ~ ~ dithiocarbalric salts or different dithiocarbamate groupings attached to the same polyvalent metal atom.
i ~ Examples of alkyl groups are ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, decyl, dodecyl, j tsidecyl, pentadecyl and hexadecyl groups including isomeric forms thereof. Examples of cycloalkyl groups ln~lude cyclohexyl and cycloheptyl groups, and examples of aralkyl groups include benzyl and phenylethyl.
Examples of polymethylene groups include penta- and hexamethylene groups, and examples of alkyl-substituted . . : ~ .
,, \ ' ' ' .
I ~.
., .. ;. ~, . . . , . .

,: :

,l t ~2~3 . . .
.

polymct}lylcnc groups includc mcthyl pentamcthylene, dimctllyl pentametllylcnc, etc.
Spccific c~amples of tllc mctal dithiocar-bamates useful as componcnt (E~ in tlle compositions of this invention includc bismuth dimethyldithiocarbamatc, calcium dicthyldithiocarbamatc, calcium diamyldithio-carbamate, cadmium dicthyldithiocarbamate, coppcr dilllcthyldithiocarbam(to, zinc diethyldithiocarbamatc, , zinc dibcnzyldithiocarbamatc, zinc dibutylditllio-carbamate, zinc diamyldithiocarbamate, zinc di(~-ethyl-hcxyl)ditlliocarbamate, cadmium dibutyldithiocarbamate, t cadmium dioctyldithiocarbamatc, cadmium octyl-butyl-dithiocarbamate, magnesium dibutyldithiocarbamate, I ma~nesium dioctyldithiocarbamate, cadmium dicctyl-dithiocarbamate, sodium diamyldithiocarbamatc, sodium diisopropyldithiocarbamatc, etc.
, The various metal salts of dithiocarbamic ~, acids utilizcd in thc compositions of tllis invc1ltioll are well known in tlc art and Call be prepared by known 1 techniques.
¦ The catalyst for the sulurization reaction also can be (F) at least one mercapto benzothiazole 1 which may be mercapto benzothiazole itsclf or l! derivatives such as metal salts. Thc mctal of the metal salts may be any of the metals described above with respect to the metal salts of t?-e dithiocarbamic ~ acids (E). The metal salts arc known in the art, and 3 ~ the Group II metal salts are preferred as catalysts in ~ ~ the sulfurization process of this invention.
- Mixtures of the salts of thc dithiocarbamic acids and salts of mercapto benzothiazole can be utilized as the catalysts. It is generally preferred, however, to utilize the dithiocarbamate salts alone.
\ '~ : ~ :
: - -'. ~
~ L
.~

, . ~ .. .
.

The amount of catalyst (E), (F) or (G) used in the reaction is an amount sufficient to cat:aly~c thc sulfurization reaction. Generally amoun~s of flom about 0.0001 to about 5~ by weiyht of the catalyst based on the comhined wcight of (A~, (B) and (C) arc sufficient.
I`he sulfurization reaction generally is effected at an elevated tcmperature of froM about S0 to about 350C, more preforably, at a temperature of from about 50 to about 200C. The reaction is eff~cLed with efficient agitation and usually in an inert atmosphere such as nitrogen. If any of the reagcnts are appreciably volatile at the reaction tempcrature, the reaction vessel m~y be sealed and maintained under pressure. ~lthough generally not necessary, thc reaction may be effected in the presence of an inert solvent such as all alcohol, ether, estcr, aliptlatic hydrocarbon, halogcnat~d aromaLic hydrocarbon, ctc., which is a liquid within the temperature ran(3~ cmplo)~ed for the reaction.
The sulfuri~ing agents useful in thc proccss of the present invention include~ sulfur, a mixture of hydrogen sulfide and sulfur or sulfur dioxide, etc.
Preferably, the sulfurizing agcnt is elemcntal sulfur.
It is frequently advantageous to add the sulfuri4ing agent portionwise to th~ mixture of the other reagents.
When elemental sulfur is utilized as a sul~urizing agent, the reaction is in some instances e~o~hcrmic which can be utilized as a cost-cutting benefit. The amount of sulfur or sulfurizing agent added to the reaction mixture can be varied over a wide range àlthough the amount included in the reaction mixture should be an ~ !~

: ., -~ ~ ~,~ ......
.... .

amount suficient to provide a sulfurized product containing ~I-e desired amount of sulfur which generally i5 at least about 10% by weight.
Following the sulfurization reaction, it is preferred to ren,ove substalltially all low boilin~
materials, typically by venting thc rcaction vessel, by sparging with an inert gas 5uch as nitrogen, by vacuum distillation or stripping, etc. Insoluble by-products may be removed by filtration if necessary, usu.llly at an elevatcd tenlperaturc (about 60-120C).
A further optional step in thc preparation of the sulfurized compositions is the treatmcnt of the sulfurized product obtained a5 described above to reduce any active sulfur which n,ay be present. ~n illustrative method is the trcatment with an alkali metal sulfide. Other optional trc~tnlcnts nlay be employed to improve product cluality such as odor, color, and staining characteristics of the sulfurized compositions.
The following examplcs illustratc the preparation of the sulfurized compositic,n of tl-c present invention. Unless otherwise indIcatcd in t~,e examples and elsewhere in the specification and claims, all parts and percentages are by weight, and temperatures are in degrees centigrade.
EX~MPIE 1 ~ A mixture of 1000 parts of conimercial Cls_l6 alpha-olefins, 137 parts of sulfur and 10 parts of zinc diamyldithiocarbamate is prcpared and heatcd to temperature of 150C. The mixture is maintained at this temperature for a total of about 12 hours and filtered through a filter aid. The filtrate is thc desired sulfurized composition containing 12.69% sulfur (theory, 11.9~).

_ ...... \ ., ~'~
.

3~15 , A mixture of 900 parts of commercial C15 18 alpha-oleEins, 100 parts of pine oil, 141 parts of sulfur and 10 parts of zine diamyldithiocarhamate is preparcd and heated to 130C. ~he mixturc is maintained at this temperature with stirring for a total of about 12 hours ancl filtered through a filter aid. The filtratc is the desired product containing i 12.61~ sulfur (theory, 12.25).
¦ EXAM~I.E 3 ' A mixture of 561 parts of l-octcne, lf.0 parts S of sulfur and lO parts of zinc diamy]dithiocarbamatc is prepared and heated to a tempcrature of about 130C.
; The mixture is maintained at this temperaturc for about S 6 hours and filtered. Thc filtrate is th~ desired product containing 23.2~ sulfur (theory, 22.22).

1 The product of ~xample 3 (500 parts) is I stripped by heating to 100C and thercafter 130C ullder vacuum. The residue (367 part) is the desired product ` eontaining 30.31% sulfur.
; EXAMPLE 5 . I ~ . A mixture of 1052 parts of 1-decene, 360 . ~ ~ ~ parts of sulfur and 15 parts of zinc diamyldithio-carbamate is prepared and heated to a temperature of -~ - 130C. The mixture is maintained at this temperature with stirring for a total Oc g hours and thereafter at a temperature of 150C for 6 hours. The temperature then is lowered to 100C and filtered. The filtrate is - - the desired product containing 25.8~ sulfur (theory, 25.~8).

IA mixture of 1052 parts of isome i~ed 1~ deeene (isomerized by treatment with Amberlyst~15) !
~ ~ 360 ~ ~ parts :
. . . ~ ' .
"~
`'.: ~
~ ~ ~0 C'~

,. . .

.. . - : - - ~ .

12~3~
.

of sulfur and 15 parts of zinc diamyldithiocarbc~ a-e is preparcd and heated to 130C. The mixture i5 maintained at this ter,lperature for 9 hours and thercafter at 150C for 6 hours. The nlixture is cooled to 90C and filtered. The filtrate is the desired product containing 25.6~ sulfur (theory, 25.5).

A mixture of 1000 parts of a conmlercial C16~1~ alpha-olefin, 137 parts of sulfur and 10 parts of zinc diamyldithiocart,anatc is prepared, purged with nitro(~en and heated to 130DC. The mixturc is maintained at 130C for 6 hours, cooled to 100C and filtered. rrhe filtrate is the desired product ContainintJ 11.85~ sulfur ~theo.y, 12.15).
EX~MPI.E 8 A mixture of 700 parts of connlclcial C~
alpha-olefin, 164.7 parts of sulfur and 7 parts of zinc diamyldithiocarbanlate is preparcd, pur(~ed with slitro~ell and heat^d to 13CC. The mixture is naintained at this temperature for about 12 hours and thercafter at a tenlperature of 150C for 6 hours. The nlixture is cooled to 100C and filtered. The filtrate is the desired product containing 18.9% sulfur (theory, 19.08).
_ _ EX~M~LE 9 A mixture of 1000 parts of a comnlercial ~C16_1g alpha-olefin, 235.2 parts of sulfur and 10 parts of zinc diamyldithiocarbamate is prepared, purged with nitrogen and heated to 130C. The mixture is maintained at this ten,perature for about 12 hours, at 150C for 6 hours, and finally at a temperature of ~ ~ 180C for 3 hours. After cooling to 100C, the mixture .~ is filtered, and the iltrate is the desired product containing 17.4% sulfur (theory, 19.08).
, :: :

L~
... .-. .

. ~ . .
.

l, ~ :

~ .

~ mixture of 100 parts of commercial C16_1~
alpha-olefin, 255.4 parts of sulfur and 10 parts of zincs diamyldithiocarbanate is prcpared, pur~ed with nitrc.cen anZ heated to 18CC. The mixture is maintained at this temperaturc for a total of about 12 hours and thereafter at 150C for about 3 hours. ~fter cooling to 100C, tl-e mixture i5 filtered, and the iltrate is the desircd product containing 20.66C
f sulfur (theory, 20.37).

A mixture of 663.8 parts of soybean oil, 301.4 ~; parts of con,nercial C]5-l8 alpha-olein, 34.8 parts ii of oleic acid, 118 L;arts of sulfur and 10 parts of ~inc ~ dialllyldithiOCarbarl~ate i5 prcpared, Lur~Jed with nitro(~en t and heated to 130C. The mixture is naintained at this I ten,perature for a total of about 9 hours and filtered.
I, The filtrate is thc d~sired product containing 10.
~ / sulfur (theory, 10.683.
EXAMPI,E 12 I The procedure of Example 11 is repeated except that 124.2 parts of sulfur is included in the mixture.
The product obtained in this manner contains 18.0 ~ sulfur (theory, 18.26).
~ - EX~MPLE 13 A mixture of 1056 parts of soybean oil, 124.6 ~ ~ parts of sulfur and 10.6 parts of xinc dian,yldithio-- carbanate is prepared, purged with nitrogen and heated ~o 130C. The mixtùre is maintained at this temperaturc f~r about 9 hours, cooled to 100C and filtered. The fi~trate is the desired product containing 10.2~ sulfur (thcory, 10.68).

:- ' .~ . . ' .~ . ~ , .
- ., ~''' "' ' ' ... .

.~

. .
"~ i A mixturc of 1000 parts of sunflower oil, 118 parts of sulfur and 10 parts of æinc diamyldithio-carbamate is prepared, purged with nitrogcn and heated to 130C. The mixture is maintained at this temperature for about 12 hours and at a temperaturc of ¦ 150C for 3 hours. After cooling to about 110C, the mixture is filt~red, and the filtrate is the desired product containing 9.91~ sulfur (theory, 10.68).
EX~MPLE 15 A mixture of 900 grams of the Die1s-~ldcr I ~ adduct of Example DA-6, 149 parts of sulfur and 9 parts ! q of 7inc diamyldithiocarbamate is prcpared, purged withnitrogen and hcated to a tcmperaturc oL about 130C.
I ¦! The mixture is maintained at this tcmperature for about ¦ ~ 6 hours. Aftcr cooling to about 95C, t:hc mixturc isj' filtered. The filtraLe is tlle dcsired product ~' containing 11.81~ sulfur (~heoly, 13,95).
EXA~PLE 16 I The general procedure of Exan~ple 15 is ¦~ repeated except that the mixture contains 320 parts of . ,I sulfur. The product o~taincd in this manner contains 22.6~ sulfur (theory, 26).
EXA~IPLE 17 j I A mixture of 1000 parts of a commercial C16 18 a~pha-olefin, 225.4 parts of sulfur and 14.7 I parts of the amine salt of diamyldithiocarbamic acid . tl I prepared by the reaction of two moles of diamylamine ~ 1~ ~ with one mole of carbon disulfide is prcpared, purgcd I ~ with nitrogen and heated to 130C. The mixture is maintained at this temperature for a total of 12 hours . ~ ~ and at a tempe~ature of 150c for an additional 6 " ~ " : ~ ' ' .
~ ~ ;`;' , , ., , . . - ~ .

!
~25~

hours. After cooling to 100C, the mixture is j filtered, and the filtrate is the desired product containing 20.1~ sulfur (theory, 20.30).

A mixture of 1000 parts of commercial C16_1g alpha-olefin, 255.4 parts of sulfur and B.9 parts of copper (II) dibutyldithiocarbamate is prepared, purged il with nitrogen and heated to 130C. The mixture is ; maintained at this temperature for a total of 12 hours ! ~ and at a temperature of 150C for an adclitional 6 hours. After cooling to about lC0C, the mixture is , filtered, and the filtrate is the desired product ¦ , containing 20.5% sulfur (theory, 20.4;.
EXA~1PL~ 19 , A mixture of 1000 parts of commercial Cls_lg alpha-olefin, 137 parts of sulfur, 10 parts of ~ 2-mercaptobenzothiazole and 10 parts of zinc oxide is I prepared and heated to 130C. The mixture is ¦ : maintained at this temperature for 6 hours, and at a temperature of 150C for an additional 6 hours. After i cooling, the mixture is filtered, and the filtrate is the desired product containing 11.26~ sulfur (theory, 11.94).
The sulfurized compositions of this invention I I ~ can be employed as general purpose antioxidants, i extreme pressure and friction modifiers in a variety of ~1 ~ ~ I ~ Iubricating compositions based on diverse oils of `: ~ 7 ~ : lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. The lubricating compositions contemplated include crank-case lubricating oils for spark-ignited and compression-~; ~~ ~ ~ ignited internal combustion engines including automoblle and truck engines, two-cycle englne : :

~, .

.. .

.

~ 3 [)S
.
.
-35_ lubricants, aviation piston engines, marine and railroad diesel enyines, and the likc. ~lowcver, automatic transmission fluids, transaxle lubricants, gear lubricants, metal-working lubricantc, hydraulic fluids, and other lubricating oil and grease compositions also can bcncfit from the incorporation of the prcsent compositiorls.
The compositions of the invention can be added directly to the lubricant. Preferably, however, they are diluted with a substantially inert, normally liquid organic dilucnt such as mineral oil, naphtha, benzene, toluene or xylene, to form an additive conccntrate.
These concentrates usually contain from about 20% to about 90~ by weight of the sulfurized com~ositions of this invention and may contain, in addition, onc or more other additives known in the art and describcd belo~. The remainder of the conccntratc is the substantially inert normally liquid dilucnt.
The lubricating oil compositions of the present invention comprisc a major amoullt of oil Or lubricating viscosity, including natural and synthetic lubricatinq oils and mixtures thereof.
Natural oils include animal oils and vcgetable oils (e g castor oil, lard oil) as well as mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lùbricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubrieating viscosity derived from eoal or shale are also useful. Synthetic lubricating oils include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, ': ' ~ ' ' ' ' ' 1~ `

: - , 1 ~2~3~5 .

.
chlorinated polybutylenes, etc.); poly(l-hexenes), I poly~l-octenes), poly(l-decenes)~ etc. and mixturcs thel of; alkylbenzenes ~e.g., dodecylben~enes, tetradecylbcnzenes, dinonylbenzenes, di-(2-ethylhexyl)-ben~enes, etc.); polyphenyls (e.g., biphenylsr terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides and the i derivatives, analogs and homologs thereof alld the like.
Alkylene oxide polymers and interpolyDers and derivativcs thereof where the terminal hy~3roxyl groups ' have been modified by esterification, ethcrification, etc., constitute anothcr class of knowl) synthctic ~' I lubricating oils that can bc uscd. These a.e ~' cxenlplified by the oils prepared through polymerization ' of ethylene oxide or propylene oxide, thc alkyl anci aryl ethers of these polyoxyalkyletle polymers ~e.5., methylpolyisopropylene glycol ether having an average molecular weight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of about ' ' 500-1000, diethyl ether of polypropylcne glycol having ~1 a molecular weight of about 1000-1500, etc.) or mono-and polycarboxylic esters thereof, or example, the , acetic acid esters, mixed C3-Cg fatty acid esters, j ~ or the C13Oxo acid diester of tetraethylene glycol.
Another suitable clas.s of synthetic ' ; lubr'ieating oils that can be used comprises the esters of dicarboxylic acids ~e.g., phthalic acid, succinic 1~ ~ acid, alkyl succinic acids, alke:--l succinic acids, ;'~ ~ maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic ~- acid, alkyl malonic acids, alkenyl malonic acids, etc.) ~' I ~ 'with a variety o alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2~ethylhexyl alcohol, :, . ~. .
-,- ~'' I ~---~

.

~-j ~

., ethylene glycol, diethylene glycol monoether, propylene glycol, etc.) Specific examples of these esters include dibutyl adipate, di(2-cthylhexyl) sebacate, _~ di-n-hexyl fumarate, dioctyl sebacate, diisooctyl a~elate, diisodecyl azelate, dioctyl phthalate, didecyl phthnlatc, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex estcr formed by i reactin~J onc mole of scbacic acid with two moles of tetra~thylene glycol and two moles of 2-ethylhexanoic acid ~nd the like.
;ters useful as synthetic oils also include ! those made from Cs to C12 monocarboxylic acids and j polyols and polyol ethers such as ncopentyl glycol, trimethylol propanc, pentaerythritol, dipentacry-thritol, tripentaerytllritol, etc.
Silicon-based oils such as the poly~lkyl-, ; 1 polyaryl-, polyalkoxy-, or polyal~loxy-siloxanc oils and silicate oils comprise another useflll class of - j synthetic lubricants (e.g., tetraethyl silicate, _ ~ tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-hexyl)silicate, tetra-(p-tert-butyl-; ~- phenyl)silicate, hexyl-(4-methyl-2-pentoxy)disiloxane, poly~lethyl)siloxanes, poly(methylphenyl)siloxanes, etc~). Other synthctic lubricating oils include liquid esters of phosphorus-containin~ acids ~e.g., tricresyl phosphate, trioctyi phosphate, diethyl ester of decane phosphonic acid, etc.), polymeric tetrahydrofurans and the like.
- ~ Unrefined, refined and rerefined oils, either natural or synthetic (as well as mixtures of two or more of any of these) of the type disclosed herein-above can be used in the compositions of the present '' T`'; ~ ~ invention. Unrefined oils are those obtained dlrectly ~,., : :~
~"' :

.

.-, ~, .1 - ~2~9301~ i .' .
,,, . -3~-from a natural or synthetic source without further purification treatment. Yor example, a shale oil obtainec directly from retorting operations, a petroleum oil obtained directly rom prinary distillation or ester oil obtained directly from an r ' esterification process and used without further treatment would be an unrefined oil. Refined oils are i similar to the unrefined oils except tlley have been further treated in one or more purification steps to ~i improve one or more properties. Many such purification techniques are known to those skillcd in the art such I as solvent extraction, secondary distillatioll, acid or ~ I base extraction, filtration, percolation, etc.
_ ~! Rercfined oils are obtained by processes similar to (~ those used to obtain refined oils applicd to reilled I oils which have beell already used in servicc. ~uch j rerefined oils are also known as rcclaimed or reprocessed oils and often are additionally proce~sed by techniques dirccted to removal of sFent additives , and oil breakdown products. ;
~ ~11 The sulfurized compositiol7s of the present ;.~ j invention will normally be employed in the lubricating eomposition of the invention in an amount of from about 0.001% to about 20% by weïght o~ the partieular oil in which they are utilized. The optimum amount to be used : ¦ , in a given lubricant obviously would depend on the -- : 7 other contents of the partieular Iubricating eomposition, the operating conditions to which it is to ~; be subjected, and the particular additives employed.
In lubricating eompositions operated under extremely adv~rse eonditions, such as lubricating coopositions ; for marine diesel engines, the eompositions may be i present in the lubrieant in amounts of up to about 30~
' .
`.; ~
.. , ' .' ~ 'l .

L

~IL25~33~5 , -39~
by weight, or more, of the total weight of the _ lubricating composition.
The invention also contemplates the use of other additives in the lubrieant compositions of this invention. Such additives are those normally used in ¦ lubricating oils such as, for example, detergents, dispersants, oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, antiwear s agents, color stabilizers and anti-foam agents.
The ash-producing detergents are exempliLied by oil-soluble neutral and basic salts oE alkali or alkaline earth metals with sulonic acids or carboxylic aeids. The most commonly used salts of cuch acids are those of sodium, potassium, lithium, ealcium, I~ magnesium, strontium and barium.
I; The term "basie salt" is used to designcfte 1~ metal salts wherein the metal is present in ! ~ stoichiometrically larger amounts than the or~anic ~cid ¦ group. The eommonly employed methods for preparing the basie salts involve heating a mineral oil solution of I an acid with a stoichiometric excess of a metal I neutralizing agent such as the metal oxide, hydroxide, ¦ - ~ earbonate, bicarbonate, or sulfise at a temperature of about 50C and filtering the resultin~ mass. The use of a "promoter" in the neutralization step to aid the :. f ~ ineorporation of a large exeess of metal likewise is ¦ ~ known. Examples of eompounds useful as the promoter -~ l inelude p'7enolie substanees such as phenol, naphthol, f ~, ~ alkylphenol, thiophenol, sulfurized alkylphenol, and ... ~ eondensation produets of formaldehyde with a phenolie 1~ ~ substanee; aleohols sueh as methanol, 2-propanol, octyl aleohol, eellosolve, earbitol, ethylene glycol, stearyl , aleohol, and eyelohexyl alcohol; and amines such as ,'~
' ~ .' ' ...... , . .. , , , ., . ... . . .. ... _ ., o~
"~

aniline, phenylen~diamine, phenothiazine, phenyl-beta-naphthylamine, and dodecylamine. ~ particuiarly : eff~ctive method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least ¦ one alcohol promoter, and carbonating the mixture at an elevated ten:perature such as 60-200C.
Ashless detergents and dispersant~ are so called despite the fact that, depending on its ¦ constitution, the dispersant may upon combustion yield a non-volatile material such as boric oxide; however, it does not ordinarily contain metal and therefore does not yield a metal-containing ash on combustion. Many types are known in the art, and any of them are , suitable for use in the lubricant compositions of this , invention. The following are illustrative:
I~ (1) Reaction products of carboxylic acids (or I derivatives thereof) containing at least about 34 and ¦~ preferably at least about 54 carbon atoms with nitrogen I" ! containing compounds such as amine, organic hydroxy i compounds such as phenols and alcohols, andJor basic inorganic materials. Examples of these "carboxylic jJ dispersants" are described in British Patent-1,306,529 ~i ~ ~ .and in many U.S. patents including the following:
~ , ~ ~ 3,1~3,603 3,351,552 3,541,012 `.~ , 3,215,707 3,399,141 3,542,680 ~ ~I 3,271,310 3,433,744 3,574,101 : ~ 3 3,281,3J7 3,448,048 3,630,904 3,311,558 3,451,933 3,632,511 3,340,281 3,467,66/3 3,725,441 . ~ ~ 3,346,493 3,522,179 Re 26,433 (2) Reaction products of relatively high ~molecular weight aliphatic or alicyclic halides with .. .
.
~j ' .' '`.. ..

~:5~3~i amines, preferably polyalkylene polyamines. These may be characterized as "amine dispersants" and examples thereof are described for example, in the following U.S. patents:
3,275,554 3,454,555 3,438,757 3,565,804 (3) Reaction products of alkyl phenols in which the alkyl group contains at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines), which may be characterized as "Mannich dispersants". The materials described in the following U.S. patents are illustrative:
2,459,112 3,442,808 3,591,598 2,984,55G 3,454,497 3,634,515 3,166,516 3,461,172 3,697,574 3,355,270 3,539,633 3,725,480 3,413,347 3,586,629 3,980,569 (4) Products obtained by post-treating the carboxylic, amine or Mannich dispersants with such reagents as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, or the like. Exemplary materials of this type are described in the following U.S. patents:
3,036,003 3,282,955 3,493,520 3,639,242 3,200,107 3,366,569 3,513,093 3,649,659 3,254,025 3,373,111 3.539,633 3,697,574 3,278,550 3,442,808 3,579,450 3/703,536 3,281,428 3,455,832 3,600,372 3,708,422 (5) Interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers 'I

I. .

1~593~5 containing polar substituents, e.g., aminGalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates. These may be characterized as __ "polymeric dispersants" and examples thereof are disclosed in the following U.S. patenLs:
! 3,329,658 3,666,730 3,4~9,250 3,6~7,84g 3,519,565 3,702,300 , The above-noted patents are incorporated by reference herein for their disclosures of ashless dispersants.
Auxiliary extreme pressure agents and corrosion- and oxidation-inhibiting agents which may be include~ in the lubricants of the invention are exemplified by chlorinated aliphatic hydrocarbons such as chlorinatcd wax; organic sulfides and pol~sulfides such as benzyl disulfide, bis(chlorobenzyl)dislllfide, ; dibutyl tetrasulfide, sulfurized methyl es~er of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene. Group II metal phosplloro-dithioates also may be included in some of the lubricant. Examples of useful metal phosphoro-dithioates include zinc dicyclohexylphosphoro-dithioate, zinc dioctylphosphorodithioate, barium di(heptylphenyl)phosphorodithioate, cadmium dinonyl-phosphorodithioate, and the zinc salt of a phosphoro-ithioic acid produced by the reaction of phosphorus j pentasulfide with an equimolar mixture of isopropyI
alcohol and n-hexyl alcohol. When it is desired to formulate lubricating oils containing low amounts of ~1 ; phosphorus, such phosphorodithioiates should be avoided when possible.
Many of the above-mentioned auxiliary extreme pressure agents and corrosion-oxidation inhibitors also , ; . ,.:

serve as antiwear agents. Zinc dialkylphosphorodithioates are well known examples.
Pour point depressants are a particularly useful type of additive often included in the lubricating oils described herein. The use of such pour point depressants in oil-based compositions to improve low temperature properties of oil-based compositions is well known in the art. See, for example, page 8 of "Lubricant Additives" by C.V. Smalheer and R. Kennedy Smith (Lezius-Hiles Co.
publishers, Cleveland, Ohio, 1967).
Examples of useful pour point depressants are polymethacrylates; polyacrylates; polyacrylamides;
condensation products of haloparaffin waxes and aromatic compounds; vinyl carboxylate polymers; and terpolymers of dialkylfumarates, vinyl esters of fatty acids and alkyl vinyl ethers. Pour point depressants useful for the purposes of this invention, techniques for their preparation and their uses are described in U.S. Patents 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498;
2,666,746; 2,721,877; 2,721,878; and 3,250,715.
Anti-foam agents are used to reduce or prevent the formation o stable foam. Typical anti-foam agents include silicones or organic polymers. Additional anti-foam compositions are described in "Foam Control Agents", by Henry T. Kerner (Noyes Data Corporation, 1976), pages 125-162.
The sulfurized compositions of this invention have been found to be particularly effective as additives in metal working lubricants where they impart excellen-t extreme pressure characteristics to the . ~

:

_~4_ ~25~3Q~
lubricant. An ingredient which is often preferably included in the metal working lubricants of this invention (especially for stainless steel) is at least one chlorinatcd wax, especially a chlorinated paraffin _ wax. The chlorinated wax preferably has a molecular weight between about 350 and about 700 and contains about 30~ to about 70% chlorine by weight.
Other additives which may optionally be present in the metal working lubricants for use in this ; ~ invention include:
antioxidants, typically hindered ph~nols;
surfactants, usually nonionic surfactants such as oxyalkylated phenols and the like; and ¦ corrosion, wear and rust-inhibiting agents.
j Friction modifying agents, of which are the following are illustrative: alkyl or alkenyl phosphates or phosphites in which thc alkyl or alkenyl ! group contains from about 10 to about 40 carbon atoms, and metal salts thcreof, especially zinc salts;
10-20 fatty acid amides; C10-2o alkyl amines, I especially tallow amines and ethoxylated derivatives ,I thereof; salts of such amines with acids such as boric ¦ acid or phosphoric acid which have been partially esterified as noted above; C10-2o alkyl-substituted i ~- ¦~ ~ imidazolines and similar itrogen heterocycles.
3 ~ ~ ~ The metal working lubricants whose use is , 1~ ~ contemplated according to this invention will generally I contain from about 0.5~ to about 15~ by weight, ~ ~ preferably from about 1% to about 10~, o~ the _ ;~ i ~l I sulfurized compositions of the invention. Other ingredients such as those described above will be present in amounts sufficient to provide the metal ~orl~g lubl~Fanl wl~h ~he proo~r~es s-c- s ~i : ~ ' '' ~59305 antioxidants, corrosion-inllibition, wear-resistance, rust-inhibition, etc.
The following are illustrative examples of the concentrates ana lubricants of the inventionO All parts and percentages a~e by weight of the total composition unless otherwise indicated. All amounts listed in the examples, except those for mineral oil, are exclusive of oil present as diluent.
.
Pacts by ¦ Mineral oil 50 7 Product of Example 5 50 ¦' ~xn~le~ Qn~S~n~L~5~L
~; Mineral oil 60 ~ j Product of Example 6 40 h TABLE I
. 1~ E~Am4l~s C-G (Luhrican~L C _~_ E F _Ç_ l; .
- 1~ Mineral oil 95 95 96 96 95 . ~ Product of Example 1 5 ` ~ ~ 4 ~ ~~ ~ 4 -~

~ ' ~; '~
`- ~ L
. .. ; . . . . . .

. . ~
.

~' l ~ s l -~6-. ,.

" , ~,~., i .P~l~I~k~is~n~L 11 1 ~ ' ~ Mineral oil tSAE-80) 93.48 93.68 93.995 ~' ¦ Product of Example 6 5.0 -- --n 16 Zinc salt o O,O-di i~ (C12_14 alkyl) phosphorodithioic acid 1.0 0.8 1.5 Poly(alkyl methacrylate) ~ pour point depressant 0.5 0.5 0.5 ;~ Silicone anti-foanl agent 0.02 0.02 0.005 . 1.
. .~ .
T~EL~
E~mples R-L _K~
Mineral oil 95.0 93.0 94.0 I Product of Example 6 2.5 -- 2.0 I; n 16 ; '~ Chlorinated (about ; 42~ chlorine) paraffin wax 2.5 ~ 305 3.0 Triphenyl phosphate ~ 1.0 ~;i ~ Any metal to be worked may be treated j j - ~ according to the method of this invention. Examples - ~ ~ are ferrous metals, aluminum, copper, magnesium, -~ ~ ~ titanium, ~inc and manganese. Alloys thereof, with and ~- ~ ~ without other elements such as silicon, may also be treate~; examples of suitable alloys are brass and various steels (e.g., stainless steel).

` ~ ''\
., , ~

~ .
.
.

~ L2~3(~

The metal working compositions uscd in the method of this iavention can be applicd to the metal workpiece prior to or during the working operation in any suitable manner. They may be applied to the entire surface of the metal, or to any portion of that surface with which contact is desired. For example, the lubricant can be brushed or sprayed on the nnetal, or the metal can be immersed in a bath of the lubricant.
In high speed metal forming operations spraying or immersion are preferred.
In a typical embodiment of the mcthod of this invention, a ferrous metal workpiece is coated with the lubricant prior to the working operation. For example, if the workpiece is to be cut it may be coated with the ' I lubricant beforc contact with the cuttinc~ tool. (The I~ invention is particularly useful in connection with i cutting operations.) It is a]so within the scope of I the invcntion to apply the lubricant to the wolkpiece i as it contacts the cutting tool, or to apply it to the cutting tool itself whereupon it is transferred to the workpiece by contact. Thus, the method of this I invention in a c3eneric sense comprises any metal I working operation wherein the workpiece has on its surface, during said operation, the above-described lubrie~nt~regard1ess Oe how applied.

~: : : :
~, ~ ~ ~
~: ,~:
., :
' v , ' ~_ __ , " . ......... ',.
, _. ... ... . . , .

' ., .. . . - . -: ...

Claims (69)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A sulfurized composition prepared by reacting at an elevated temperature, a sulfurizing agent with (A) at least one fatty acid ester of a polyhydric alcohol, or (B) at least one fatty acid, fatty acid ester of a monohydric alcohol, or a mixture thereof, or (C) at least one other olefin, or (D) mixtures of any two or more of (A), (B) and (C), in the presence of a catalytic amount of (E) at least one salt of at least one dithiocarbamic acid of the formula R1(R2)N-CSSH

wherein R1 and R2 are each independently hydrocarbyl groups, or (F) at least one mercapto benzothi-azole, or (G) mixtures of (E) and (F).

2. The sulfurized composition of claim 1 wherein the salt of dithiocarbamic acid (E) is metal salt.

3. The sulfurized composition of claim 1 wherein the mercapto benzothiazole (F) is a metal salt.

4. The sulfurized composition of claim 2 wherein the metal salt is a Group II metal salt.

5. The sulfurized composition of claim 1 wherein the catalyst is (F) at least one Group II
metal salt of a mercapto benzothiazole.

6. The sulfurized composition of claim 1 wherein the sulfurizing agent is sulfur.

7. The sulfurized composition of claim wherein the reaction is conducted at a temperature of from about 50 to about 350°C.

8. The sulfurized composition according to claim 1 wherein the catalyst is (E) at least one metal salt of at least one dithiocarbamic acid of the formula R1(R2)N-CSSH
wherein R1 and R2 are each independently hydrocarbyl groups.

9. The sulfurized composition of claim 4 wherein R1 and R2 are each independently alkyl groups containing from 1 to about 20 carbon atoms.

10. The sulfurized composition of claim wherein the other olefin (C) is at least one aliphatic, aryl aliphatic or alicyclic olefinic hydrocarbon containing at least 3 carbon atoms.

11. The sulfurized composition of claim wherein the other olefin (C) is an aliphatic olefin which may be propylene, butylene or isobutylene, and dimers, trimers, tetramers and low molecular weight polymers thereof.

12. The sulfurized composition of claim wherein (C) is at least one aliphatic olefin containing from about 8 to about 36 carbon atoms.

13. The sulfurized composition of claim wherein the aliphatic olefin is an aliphatic alpha-olefin.

14. The sulfurized composition of claim 13 wherein the olefin is an isomerized aliphatic alpha olefin.

15. The sulfurized composition of claim 1 wherein the olefin (C) is at least one Diels-Alder adduct of at least one dienophile with at least one aliphatic conjugated diene.

16. The sulfurized composition of claim 1 wherein the other olefin (C) is at least one terpene compound.

17. The sulfurized composition of claim 1 prepared from a mixture comprising (A) about 100 parts by weight of at least one fatty acid ester of a polyhydric alcohol, and (C) from about 0 to about 400 parts by weight of at least one other olefin.

18. The sulfurized composition of claim 17 wherein the olefin is at least one aliphatic olefin containing from about 3 to about 36 carbon atoms.

19. The sulfurized composition of claim 17 wherein the mixture contains from about 25 to 100 parts by weight of olefin (C).

20. A sulfurized composition prepared by reacting at an elevated temperature, a sulfurizing agent with a mixture comprising (A) about 100 parts by weight of at least one fatty acid ester of a polyhydric alcohol, (B) from about 0 to about 200 parts by weight of at least one fatty acid, fatty acid ester of a monohydric alcohol, or a mixture thereof, and (C) from about 0 to about 400 parts by weight of at least one other olefin in the presence of a catalytic amount of (E) at least one salt of at least one dithiocarbamic acid of the formula R1(R2)N-CSSH

wherein R1 and R2 are each independently hydrocarbyl groups containing from 1 to about 20 carbon atoms, or (F) at least one mercapto benzothi-azole, or (G) mixtures of (E) and (F).

21. The sulfurized composition of claim 20 wherein the salt (E) is a metal salt.

22. The sulfurized composition of claim 20 wherein the salt (F) is a metal salt.

23. The sulfurized composition of claim 20 wherein the sulfurizing agent is sulfur.

24. The sulfurized composition according to claim 20 wherein the reaction is conducted at a temperature of from about 50 to about 350°C.

25. The sulfurized composition of claim 20 wherein the reaction is conducted at a temperature of from about 50 to about 200°C.

26. The sulfurized composition of claim 20 wherein the mixture contains from about 2 to about 200 parts of at least one other olefin (C).

27. The sulfurized composition of claim 20 wherein the mixture contains from about 25 to about 100 parts of the olefin (C).

28. The sulfurized composition of claim 20 wherein the other olefin (C) is at least one aliphatic olefin containing from about 3 to about 36 carbon atoms.

29. The sulfurized composition of claim 28 wherein the olefin is an alpha olefin.

30. The sulfurized composition of claim 28 wherein the olefin (C) is an isomerized alpha-olefin.

31. The sulfurized composition of claim 28 wherein the other olefin (C) is at least one terpene compound.

32. The sulfurized composition of claim 20 wherein the mixture contains a catalytic amount of a Group II metal salt of the dithiocarbamic acid.

33. The sulfurized composition of claim 20 wherein the mixture contains a catalytic amount of a Group II metal salt of the mercapto benzothiazole.

34. The sulfurized composition of claim 20 wherein the fatty acid ester (A) is a fatty oil.

35. The sulfurized composition of claim 20 wherein the olefin (C) is an olefin containing from about 10 to about 20 carbon atoms.

36. A sulfurized composition prepared by reacting at an elevated temperature, a sulfurizing agent with a mixture comprising (A) from about 0 to 100 parts by weight of at least one fatty acid ester of a polyhydric alcohol (B) from about 0 to about 200 parts by weight of at least one fatty acid, fatty acid ester of a monohydric alcohol, or a mixture thereof, and (C) about 100 parts by weight of at least one other olefin, in the presence of a catalytic amount of (E) at least one salt of at least one dithiocarbamic acid of the formula R1(R2)N-CSSH

wherein R1 and R2 are each independently hydrocarbyl groups containing from 1 to about 20 carbon atoms, or (F) at least one metal salt of at least one mercapto benzothiazole, or (G) mixtures of (F) and (G).

37. The sulfurized composition of claim 36 wherein the sulfurizing agent is sulfur.

38. The sulfurized composition of claim 36 wherein the reaction is conducted at a temperature of from about 50 to about 350°C.

39. The sulfurized composition of claim 36 wherein the olefin (C) is an aliphatic olefin containing from about 8 to about 36 carbon atoms.

40. The sulfurized composition of claim 36 wherein the olefin (C) is at least one sulfurized Diels-Alder adduct of at least one dienophile with at least one aliphatic conjugated diene.

41. The composition of claim 40 wherein the dienophile comprises an alpha, beta-ethylenically unsaturated aliphatic carboxylic acid ester, carboxylic acid amide, halide, nitrile, aldehyde, ketone, or mixtures thereof.

42. The composition of claim 40 wherein the aliphatic conjugated diene corresponds to the formula wherein R through R5 are each independently selected from the group consisting of hydrogen, alkyl, halo, alkoxy, alkenyl, alkenyloxy, carboxy, cyano, amino, alkylamino, dialkylamino, phenyl, and phenyl substituted with one to three substituents corresponding to R through R5, or R, R2, R3 and R5 are as described and R1 and R4 are alkylene groups joined together to form a cyclic diene.

43. The composition of claim 42 wherein R2 amd R3 are hydrogen, and R, R1, R4 and R5 are each independently hydrogen, halo, or lower alkyl.

44. The composition of claim 36 wherein the dienophile is further characterized in that it contains at least one, but not more than two -C(O)ORO groups wherein RO is residue of a saturated aliphatic alcohol of up to about 40 carbon atoms.

45. The composition according to claim 42 wherein the diene is piperylene, isoprene, methylisoprene, chloroprene, 1,3-butadiene, or mixtures thereof.

46. The composition according to claim 45 wherein the diene is 1,3-butadiene.

47. The composition according to claim 44 wherein said dienophile is an ester of acrylic acid or methacrylic acid.

48. The sulfurized composition of claim 36 wherein the catalyst is a Group II metal salt of the dithiocarbamic acid.

49. The sulfurized composition of claim 36 wherein the catalyst is a Group II metal salt of a mercaptobenzothiazole.

50. The sulfurized composition of claim 36 wherein the fatty acid (B) is tall oil or other fatty acid mixture containing oleic acid.

51. The sulfurized composition of claim 36 wherein the amount of catalyst present is from about 0.0001 to about 5 parts by weight per 100 parts of the combined weight of (A), (B) and (C).

52. An additive concentrate comprising a substantially inert, normally liquid diluent and from about 20 to about 90% by weight of the sulfurized composition of claim 1.

53. An additive concentrate comprising a substantially inert, normally liquid diluent and from about 20 to about 90% by weight of the composition of claim 11.

54. An additive concentrate comprising a substantially inert, normally liquid diluent and from about 20 to about 90% by weight of the composition of claim 14.

55. An additive concentrate comprising a substantially inert, normally liquid diluent and from about 20 to about 90% by weight of the composition of claim 26.

56. A lubricating oil composition comprising a major amount of an oil of lubricating viscosity and a minor, property improving amount of the composition of claim 1.

57. A lubricating oil composition comprising a major amount of an oil of lubricating viscosity and a minor, property improving amount of the composition of claim 17.

58. A lubricating oil composition comprising a major amount of an oil of lubricating viscosity and a minor, property improving amount of the composition of claim 20.

59. A lubricating oil composition comprising A major amount of an oil of lubricating viscosity and a minor, property improving amount of the composition of claim 36.

60. A method for lubricating metal during working thereof which comprises applying to said metal, a composition comprising a major amount of a lubricating oil and a minor amount of the sulfurized composition of claim 1.

61. A method for lubricating metal during working thereof which comprises applying to said metal, a composition comprising a major amount of a lubricating oil and a minor amount of the sulfurized composition of claim 17.

62. A method for lubricating metal during working thereof which comprises applying to said metal, a composition comprising a major amount of a lubricating oil and a minor amount of the sulfurized composition of claim 20.

63. A method for lubricating metal during working thereof which comprises applying to said metal, a composition comprising a major amount of a lubricating oil and a minor amount of the sulfurized composition of claim 36.

64. The method of claim 60 wherein the composition also contains a minor amount of at least one chlorinated wax.

65. The method of claim 62 wherein the composition also contains a minor amount of at least one chlorinated wax.

66. The method of claim 63 wherein the composition also contains a minor amount of at least one chlorinated wax.

67. The sulfurized composition of claim 36 wherein the olefin (C) is an aliphatic alpha-olefin.

68. The sulfurized composition of claim 36 wherein the olefin (C) is an isomerized aliphatic alpha-olefin.

69. The sulfurized composition of claim 36 wherein the olefin (C) is at least one terpene compound.