Note: Descriptions are shown in the official language in which they were submitted.
3~
L-2228RB
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
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~p
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.
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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
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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
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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.
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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,
.
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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
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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
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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
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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,
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5 - 10 -
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.
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. 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
. -,
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-12-
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/
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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
R1 R2 R3 R4
~ 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
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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)
K1 K3
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,,'
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~ 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.
.
, . ..
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-17-
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
-18-
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
-21-
(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.
EXAMPLE DA-3
¦ 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~
-23-
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
05
! --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
. . .
.
- 27 -
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
.~
,
. ~ .. .
.
-28-
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
~ !~
: .,
-~ ~ ~,~ ......
.... .
1259305
-29-
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
,
-30-
EXAMPLE 2
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).
EXAMPLE 9
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).
EXAMPLE 6
IA mixture of 1052 parts of isome i~ed
1~ deeene (isomerized by treatment with Amberlyst~15) !
~ ~ 360 ~ ~ parts
:
. . . ~ ' .
"~
`'.: ~
~ ~ ~0 C'~
,. . .
.. . - : - - ~ .
12~3~
.
-31-
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).
EXAMPLE 7
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,
~ :
-32-
~ .
EXAMPLE 10
~ 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).
1 FXAMPLI 11
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).
:- '
.~ . . '
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- .,
~''' "' ' ' ... .
.~
. .
"~ i
-33-
EXAMPLE 14
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~
-34-
hours. After cooling to 100C, the mixture is
j filtered, and the filtrate is the desired product
containing 20.1~ sulfur (theory, 20.30).
EXAMPLE 18
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
.
-36-
.
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
~
-37-
.,
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
~,., : :~
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.
.-, ~, .1
- ~2~9301~ i
.' .
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. -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~
'
.
`.; ~
.. , '
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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~
"~
-40-
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
-41-
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
-42-
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
,
; . ,.:
-43-
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
-45-
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
. .. ; . . . . . .
. . ~
.
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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(~
-47-
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.
~: : : :
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