Note: Descriptions are shown in the official language in which they were submitted.
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2729R/B
TITLE: STYRENE-DIENE POLYMER VISCOSITY MODIFIERS
FOR ENVIRONMENTALLY FRIENDLY FLUIDS
FIELD OF THE INVENTION
The present invention relates to natural oils or synthetic triglycerides that
contain a styrene-diene viscosity modifier. The styrene-diene viscosity modifier is
15 soluble in the natural oil and the synthetic triglyceride. Natural oils and synthetic
triglycerides that contain the styrene-diene viscosity modifiers have utility inenvironmentally friendly farm tractor lubricants and chain bar lubricants and
hydraulic fluids.
BACKGROUND OF THE INVENTION
Successful use of vegetable oils and other biodegradable oils as
environmentally friendly base fluids in industrial applications is contingent onimproving their viscometries and low temperature flow properties. For example,
25 a sunflower oil cont~ining an oleic acid content of 80 percent has a pour point of
-12C and turns solid in the Brookfield viscosity measurement. Many of the
industrial applications require a pour point of less than -25C and a Brookfieldviscosity of 7500 to 150,00 centipoises (cP) at -25~C.
A key to lltili7ing a polymer for the thickening of a base oil is that the
30 polymer be soluble in the base oil. This solubility problem is not present for
polymers in mineral oil. Natural oils and synthetic triglycerides is another matter.
In fact, it is very ~ llt in finding hydrocarbon polymers that are soluble in
natural oils and synthetic triglycerides. Hydrocarbon polymers insoluble in
natural oils and synthetic triglycerides are olefin copolymers (OCP), ethylene-
35 propylene diene monomer (EPDM~, high molecular weight polybutylene (PBU)
2 1 78039
5 and butyl rubbers. The present invention relates to hydrogenated random blockstyrene/diene polymers that are soluble in natural oils and synthetic triglycerides.
U.S. Patent No. 2,336,195 (Sparks et al, December 7, 1943) relates to
improving viscosity char~cteri~tics of hydrocarbon oils by the addition of normal
mono-olefin polymers. A normal mono-olefin polymer is converted to a high
10 molecular weight polymer by compressing an olefin, such as ethylene or
propylene, to a high superatomspheric ples~u.e in excess of 500 atmospheres.
U.S. Patent No. 3,554,911 (Schiff et al, January 12, 1971) relates to
improved lubricating oils, particularly mineral lubricating oils, and processes of
pl~a hlg the same. In another aspect, ~is reference relates to the addition of a15 small amount of a hydrogenated random b~lt~ n~-styrene copolymer to
lubrication oils to produce formulations that are shear stable and have a high
viscosity index (V.I.). Accordingly, this reference relates to hydrogenated
random bllt~lien~-styrene copolymers having defined arnounts of butadiene and
styrene which are blended with suitable mineral oils to increase the viscosity and
20 improve the viscosity index.
U.S. Patent No. 3,772,169 (Small et al, November 13, 1973) provides an
oil composition which comprises:
1. a lubricating oil,
2. a random copolymer of butadiene and styrene cont~ining 3044
25 percent weight of units derived from butadiene and 56 - 70 percent weight of units
derived from styrene, which copolymer has been hydrogenated until at least 95
percent of the olefinic double bonds and at most 5 percent of the aromatic
ullsaLuldtion has been saturated, and
3. an oil - soluble polyester which comprises molecular unit derived
30 from an alkyl ester of an (x - olefinically unsaturated carboxylic acid in which the
alkyl chain or chains contain(s) at least 7 carbon atoms.
U.S. Patent No. 3,772,196 (St. Clair et al, November 13, 1973)
provides for lubricating oil compositions for internal combustion engines tha~ have
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unexpectedly wide temperature operating characteristics. This composition
contains a combination of a 2-block copolymer comprising a first polymer block of
an alkenyl arene, e.g., styrene and a second essentially completely hydrogenatedpolymer block of isoprene and certain pour point depressants in a lubricant basestock having a viscosity index of at least 85
SUMMARY OF THE INVENTION
A composition is disclosed which comprises
(A) a major amount of at least one natural oil or synthetic triglyceride of the
formula
CH2--O--CR
CH--O~R2
CH2--O--~R3
wherein Rl, R2 and R3 are aliphatic groups that contain from about 7 to about 23carbon atoms, and
(B) a minor amount of a composition comprising a hydrogenated
h~tiC conjugated diene/mono-vinyl alo~ ic random block copolymer.
DE~TAILED DESCRIPTION OF T~F INVENTION
(A) The Natural Oil Or Synthetic Trigl~ceride
In practicing this invention, a synthetic triglyceride or a natural oil is
employed of the formula
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-
CH2--OC--
CH--O~--R2
CH2--O~,--R3
wherein Rl, R2 and R3 are aliphatic hydrocarbyl groups that contain from about 7
to about 23 carbon atoms and preferably from about 11 to about 21 carbon atoms.
The term "hydrocarbyl group" as used herein denotes a radical having a carbon
atom directly ~tt~h~A to the r~orn~in-1Pr of the molecule. The aliphatic
10 hydrocarbyl groups include the following:
(1) Aliphatic hydrocarbon groups; that is, aLkyl groups such as heptyl,
nonyl, undecyl, tridecyl, heptadecyl; alkenyl groups cont~inin a single double
bond such as heptenyl, nonenyl, undecenyl, tridecenyl, heptadecenyl,
heneicosenyl; aL~enyl groups cont~inin,, 2 or 3 double bonds such as 8,11-
hept~clçc~ienyl and 8,11,14-hept~(lec~trienyl. All isomers of these are included,
but straight chain groups are preferred.
(2) Substituted aliphatic hydrocarbon groups; that is groups cont~inin~
non-hydrocarbon substituents which, in the context of this invention, do not alter
the predomin~ntly hydrocarbon character of the group. Those skilled in the art
20 will be aware of suitable substituents; examples are hydroxy, carbalkoxy,
(especially lower carbalkoxy) and aL~coxy (especially lower alkoxy), the terrn,
"lower" denoting groups cont~ining not more than 7 carbon atoms.
(3) Hetero atom groups; that is, groups which, while having
predomin~ntly aliphatic hydrocarbon character within the context of this invention,
25 contain atoms other than carbon present in a chain or ring otherwise composed of
aliphatic carbon atoms. Suitable hetero atoms will be apparent to those skilled in
the art and include, for example, oxygen, nitrogen and sulfur.
Naturally occurring oils are vegetable oil triglycerides. The synthetic
triglycerides are those formed by the reaction of one mole of glycerol with three
21 78039
moles of a fatty acid or ~ Lul`e of fatty acids. Preferred are vegetable oil
triglycerides. The p-efelled vegetable oils are soybean oil, corn oil, lesquerella
oil, rapeseed oil, sunflower oil, canola oil, coconut oil, peanut oil, safflower oil,
castor oil and palm olein.
In a pler~lled embodiment, the aliphatic hydrocarbyl groups are such that
the triglyceride has a monounsaturated character of at least 60 percent, preferably
at least 70 percent and most preferably at least 80 percent. Naturally occurringtriglycerides having utility in this invention are exemplified by vegetable oils that
are g~ont-ti~lly modified such that they contain a higher than normal oleic acidcontent. Normal sunflower oil has an oleic acid content of 25-30 percent. By
genetically modifying the seeds of sunflowers, a sunflower oil can be obtained
wherein the oleic content is from about 60 percent up to about 90 percent. That
is, the Rl, R2 and R3 groups are hept~ecçnyl groups and the RlCOO-, R2COO-
and R3Coo-to the 1,2,3-propanetriyl group -CH2CHCH2- are the residue of an
oleic acid molecule. U.S. Patent No. 4,627,192 and 4,743,402 are herein
incorporated by ler~lellce for their disclosure to ~e ~,ep~l~tion of high oleic
sunflower oil.
For example, a triglyceride comprised exclusively of an oleic acid moiety
has an oleic acid content of 100% and consequently a monounsaturated content of
100%. Where the triglyceride is made up of acid moieties that are 70% oleic
acid, 10% stearic acid, 13% palmitic acid, and 7% linoleic acid, the
monounsalulaled content is 70%. The plere"ed triglyceride oils are high oleic (at
least 60 percent) acid triglyceride oils. Typical high oleic vegetable oils employed
within the instant invention are high oleic safflower oil, high oleic canola oil, high
oleic peanut oil, high oleic corn oil, high oleic rapeseed oil, high oleic sunflower
oil, high oleic soybean oil, high oleic cottonseed oil, and high oleic palm olein.
Canola oil is a variety of rapeseed oil cont~ining less than 1 percent eruic acid. A
plefelled high oleic vegetable oil is high oleic sunflower oil obtained from
Helianthus sp. This product is available from SVO Enterprises F~stl~ke, Ohio as
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Sunyl~ high oleic sunflower oil. Sunyl 80 oil is a high oleic triglyceride wherein
the acid moieties comprise 80 percent oleic acid. Another preferred high oleic
vegetable oil is high oleic rapeseed oil obtained from Brassica cam~estris or
Brassica napus, also available from SVO Enterprises as RS high oleic rapeseed
oil. RS80 oil ~ignifit?c a rapeseed oil wherein the acid moieties comprise 80
percent oleic acid.
It is further to be noted that genP.ti~lly modified vegetable oils have high
oleic acid contents at the expense of the di-and tri- unsaturated acids. A normal
sunflower oil has from 2040 percent oleic acid moieties and from 50-70 percent
linoleic acid moieties. This gives a 90 peroent content of mono- and di- unsaturated
acid moieties (20+70) or (40+50). Ge~Pti~lly modifying vegetable oils gel~ldl~ alow di- or tri- ullsaLulal~d moiety vegetable oil. The gçn~ti~lly modified oils of this
invention have an oleic acid moiety:linoleic acid moiety ratio of from about 2 up to
about 90. A 60 percent oleic acid moiety content and 30 percent linoleic acid
moiety content of a triglyceride oil gives a ratio of 2. A triglyceride oil made up of
an 80 percent oleic acid moiety and 10 percent linoleic acid moiety gives a ratio of
8. A triglyceride oil made up of a 90 percent oleic acid moiety and 1 percent
linoleic acid moiety gives a ratio of 90. The ratio for normal sunflower oil is 0.5
(30 percent oleic acid moiety and 60 percent linoleic acid moiety).
(B) The Random Block Copolymer
The random block copolymers of this invention comprise the product
copol~l.leli~a~ion of two monomers. The first monomer is a conjugated diene and
the second monomer is a mono-vinyl aromatic. The random block copolymer
formed is then hydrogenated to remove substantially all of the unsaturation.
Examples of vinyl substituted aromatics include styrene, alphamethyls~rene,
ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, para-tertiary-
butylstyrene, with styrene being ~l~rell~d. Examples of conjugated dienes include
piperylene, 2,3-dimethyl-1,3-but~ n.o, chloroprene, isoprene and 1,3-butadiene
` - 2 1 78039
5 with isoprene and 1,3-but~ n~ being particularly piertlled. Mixtures of such
conjng,~teA dienes are useful.
The vinyl ~ulJ~liLuLed aromatic monomer content of these random block
copolymers is in the range of from about 20 percent to about 70 percent by weight
and preferably from about 40 percent to about 60 percent by weight. Thus, the
10 aliphatic conjugated diene monomer content of these copolymers is in the range of
from about 30 pel~;ellL to about 80 percent by weight and preferably from about 40
percent to about 60 percent by weight.
What follows is a ~ cmsion on the different types of random block
copolymers.
In general, it is prer~llcd that these block copolymers, for reasons of
oxidative stability, contain no more than about 5 percent and preferably no morethan about 0.5 percent residual olefinic unsaturation on the basis of the total number
of carbon-to-carbon covalent linkages within the average molecule. Such
unsa~uldtion can be measured by a number of means well known to those of skill in
the art, such as infrared, NMR, etc. Most preferably, these copolymers contain no
discernible ll-lsalu,alion as determined by the aforementioned analytical techniques.
The random block copolymers of this invention typically have a number
average molecular weight in the range of about 5,000 to about 1,000,000; preferably
about 30,000 to about 300,000. The weight average molecular weight for these
copolymers is generally in the range of about 50,000 to about 500,000; preferably
about 30,000 to about 300,000.
I. Random Copolymers: Those in which the comonomers are randomly, or
nearly randomly, arranged in the polymer chain, with no ~ignificant degree of
blocking homopolymer segments of either monomer. The general polymer structure
of a random copolymer can be lep~csell~cd by:
--S-D-D-S-D-S-S-D-S-D-S-S-D-S-S-D-D-S-D-D-S-D--
21 78039
..
5 wlælei~ S denotes a vinyl aromatic monomer such as styrene, and D denotes a
conjugated diene monomer such as 1,3-bllt~llirnr- or isoprene. Such random
copolymers, may easily be made by free radical copolyl~ ~tion.
While the diene monomer introduces an olefinic ~uls~ ion of some sort,
either in the main backbone of the polymer, or l)elld~ll on it, it is to be understood
10 that the olefinic sites may be ~IJb~ ;Ally removed by hydrogenation.
II. Regular Linear Block Copolymers: Those in which a small llu~lll)er of
relatively long chains of homopolymer of one type of monomer are ~ltrrn~tely
jointed to a small number of relatively long chains of homopolymer of another type
of lllollollæl. Normal, or regular, block copolymers usually have from 1 to about 3,
15 preferably only from 1 to 2 relatively large homopolymer blocks of each monomer.
Thus, a linear regular diblock copolymer of styrene or other vinyl aromatic
monomer S and conjugated diene D would have a general structure replesellL~d by a
large block of homopolymer S ~tt~rh--sl to a large block of homopolymer D:
SSSSSSSSSSSSS--DDDDDDDDDDDDDDDDDDDD
20 The blocks of monomer S and monomer D are not nrcess~rily of the same size ormolecular weight. As before, it is understood that the initial olefinic unsaLul~Lion
introduced into the copolymer by diene monomer D has been subst~nti~lly removed
by hydrogenation. Linear diblock copolymers colll~lisillg hydrogenated poly-
(styrene-b-isoprene) are sold under the trade names "Shellvis 40, 50 and 90" by
25 Shell Ch~mir~l Col~ly.
In like ll~ er, regular triblock copolymers are understood as having three
relatively large major blocks, or segments of homopolymer composed of either twomonomers; i.e., as in:
SSSSSSSSSSSS-DDDDDDDDDDDD-SSSSSSSSSSSSSS
30 and,
DDDDDDDDDDD-SSSSSSSSSSSSSSS-DDDDDDDDDDDDD
A third monomer A may also be incorporated in these linear, regular block
copolymers. In this in~t~nre, several configurations are possible, depending on how
2 1 78039
S the homopolymer se~m~nt~ are incorporated with respect to each other. For
example, a linear triblock copolymer of monomers S, D and A could be representedby several dir~c~l configurations:
DDDDDDDDDDD-AAA~SSSSSSSSSSSSSSS,
DDDDDDDDDDD-SSSSSSSSSS~SSSSS-AAAA AAAAA~,
or,
AAAA~-DDDDDDDDDDDDDD-SSSSSSSSSSSSSSS .
m. Linear Random Block Copolymers: Those in which a relatively large
l,u..lbel of relatively short segm.ont~ of homopolymer of one type of monomer
1~ alternate with a relatively large .-ul-.bt;. of short segments of homopolymer of
another monomer type.
Random block polymers of this invention may be linear, or they may be
partially, or highly branched. The relative a~ ge..lent of homopolymer segments
in a linear random block polymer, which is the most ~.eft;l-ed block polymer of this
20 invention, may be represented by:
--DDDD-AAAAA-DDD-AA-DDDDD-AAA-DD-AAAAAA-DDD--
wherein D represents a conjugated diene monomer, and A represents a vinyl
aromatic monomer. The arrangement of the individual homopolymer segm~nt~ of
each type of monomer in a linear random block polymer is al~e.l~l~.
IV. Linear Tapered Random Block Copolymers:
A special type of configuration in linear random block copolymers is the
linear tapered random block structure. In this all~.g~ ent, a major portion of ~e
polymer backbone is of the random block type, with larger blocks of one type of
homopolymer situated at one end of the molecule. The synthesis of this type of
polymer is usually carried out by ~ a~ g a linear random block copolymer, ~en
adding more of one of the monomer types near the end of the polymerization, so that
the additional polymer forms a series of ever larger homopolymer blocks at the end
of the growing linear polymer chain. The vinyl substituted aromatic monomer is
2 1 78039
5 generally chosen to provide the larger, tapered homopolymer blocks, ~lthollgh other
types of monomers may be used for ~is purpose.
SSSSSSSSSSSSSSSSSS-DD-SSSSS-DDD-SSS-DDD-SS-DDDD
Linear tapered random block copolymers may have si,,nifi-~ntly dirre.cllL
solubilities in diluents normally used in lubricant formulations, as well as superior
10 thickening power at high tel~ ure, better high temperature viscosity under
conditions of high shear, and hll~lovcd low temperature viscometrics, col.l~aled to
simple random block copolymers of similar molecular weight, made from the same
monomers.
The styrene/diene block polymers considered in this invention are usually
15 made by anionic polymerization, using a variety of techniques, and altering reaction
conditions to produce the most desirable microstructural features in the resulting
polymer.
In an anionic polym~ri7~tion, the initiator may be either an organom~t~llic
such as an alkyl lithillm, or the anion formed by electron ~ Ç~l from a Group IA20 metal to an aromatic such as lla~~ lPn~-. The most efficacious organomPt~ is
usually an alkyl lithium such as sec-butyl lithium, and the polymerization is initi~t~d
by butyl anion addition to either the diene monomer, or to styrene. With sec-butyl
lithium initiator, propagation occurs in only one direction, and the growing polymer
is anionically charged on one end, the negative charge being associated with a
25 positively-charged lithium gegenion.
Using an alkyl lithium initiator, a homopolymer of one monomer, e.g.,
styrene, may be grown selectively, with each polymer molecule having an anionic
L~lll~illllS, and lithium gegenion:
Bu Li + mS (monomer) ~ Bu (-S-)m . Li
30 Since all the anionic sites are ~c~ ed to have equal reactivity toward monomer
molecules, polymer growth at each site is essentially the same, and the res-lltin~
polymers will, when monomer is completely depleted, all be of similar molecular
weight and composition. Thus, polymers made by anionic polymerization are said
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to be nearly monodisperse; i.e., the ratio of weight average molecular weight to
~ulllbel average molecular weight is very nearly 1Ø In practice, the polydispersity
factor for properly syntht~si7~A styrene-diene anionic block polymers is usually about
1.05- 1.10.
As long as nothing is introduced into the poly,.æ.,~alion ll~i~lule that would
act to tellllil~lc the activity of the growing anionic end of a styrene homopolymer
segment, the composition con~titllte~ a "living" polymer that m~int~in~ its activity,
and can grow further by interaction with monomers that are also capable of anionic
polymerization. These monomers may be additional styrene or similar vinyl
aromatic monomers, or they may comprise a dirrclcllL chemical type, such as 1,3-dienes (e.g., 1,3-but~ nP- or isoprene). Addition of 1,3-b~lt~ n~ or isoprene tothe homopolystyrene-lithium living polymer produces a second segment which
grows from the anion site to produce a living di-block polymer having an anionicterminus, with lithium gegenion.
Bu-(-S-)m- Li ~ nD (monomer) ~ Bu-(-S-)m-(-D-)n- Li
Again, the size of this "D" block, i.e., the degree of polylllcli~Lion (DP"),
will be .l~ l plhlcipally by the amount of diene monomer added, and the
u~lber of active anionic sites available. As in the case of the first (polystyrene)
segm~nt, the molecular weight of the new (polydiene ) segments will all be about the
same, and the polydispersity factor of the new poly S-block-poly-D living polymer
25 will remain about 1Ø Similarly, the l~, ,,,ill~ of the new S-D diblock polymer will
be anionic with a lithium gegenion, and the diblock will be living" in the sense that
the anionic site will remain active toward further polymerization when exposed to
additional anionically-polymerizable monomers. Introduction of additional styrene
could produce a new poly S-block-poly D-block-poly S, or S-D-S triblock polymer;higher orders of block polymers could theoretically be made by consecutive stepwise
additions of different monomers in dir~lclll sequences.
A common practice in m~n lf~ re of S-D-S type triblock polymers is to
couple a living diblock polymer by exposure to an agent such as
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dialkyldichlorosilane. When the carbanionic "heads" of two S-D diblock living
polymers are coupled using such an agent, precipitation of LiCI occurs to give an S-
D-S triblock polymer of somewhat dirrt;,elll structure than that obtained by thesequential monomer addition method described above, wherein the size of the
central D block is double that of the D block in t'ne starting living (anionic) diblock
int~rm.oAi~te:
2(-S-)m (-D-~n- . +Li + Me2SiCk ~ (-S-),~(-D-)2n (-S)m +2 LiCI
The polyl,~ i~lion to form block polymers may also be approached in a
slightly different manner. In cases where metal n~rhth~ is used to initiate
polymerization, single electron-transfer to monomer (S) ge~ ~s a radical-anion
which may dimerize to yield a di-anionic nuceophile which is capable of initi~ting
polymerization in two directions sim-llt~nPously. Thus,
Naph ~i + S (monomer) ~ Naph + .S Li
+ + -- -- +
2 S Li ~ Li S--S Li (dianion)
Li S--S Li + (monomer) ~ Li (-S-)m+2 Li
The polyS segment is a living dianionic species that can continue to initiate
poly"leli~ation in two directions. Exposure to a second monomer (D) results in
formation of a polyDblock-PolyS-block-PolyD, or a D-S-D triblock polymeric
dianion.:
~-S-)m+2 + nD (monomer) ~ Li+ ~)n/2-(S)m+2-(D)nl2 ~1+
Again, the dianion is living, in the sense that it may continue to interact withadditional anionically-polymerizable monomers of the same, or dirr~ çh~
type, in the formation of higher order block polymers.
The effect of solvents in anionic polymerization is considerable, and can
de~l"~ e in large measure the nature of the copolymer that is llltim~t~ly formed.
Polymerization is frequently carried out in what is considered to be a non-polarsolvent such as hexane, heptane or an aromatic such as benzene or toluene. Non-
polar palarr~l~ic solvents tend to inhibit charge separation at the growing anion, and
21 78039
.
5 ~liminish the basicity of the active organolithium head. These L,alarrll~ic solvents
also tend to slow down the rates of initiation and elllyh~size the dirrelellces in
relative rate of poly~ li~tion between various anionically-poly~ i~ble
mono,ll~ls. Thus, when two dirr~lclll monomer types are available, the one whichinitiates faster takes precedenr~.
Usually, the same monomer will also polymerize faster, building a segment
that is richer in that monomer, and co,-~.",--~ted by occasional incorporation of the
other monomer. In some cases, this can be used beneficially to build a type of
polymer referred to as a random block polymer", or "tapered block polymer".
When a lllix~ of two dirrelel~ monomers is anionically polymerized~in a non-
15 polar paraffinic solvent, one will initiate selectively, and usually polylllc~ e to
produce a relatively short segment of homopolymer. Incorporation of the second
monomer is inevitable, and this produces a short segment of dir~ele-ll structure.
Incorporation of the first monomer type then produces another short segment of that
homopolymer, and the process continnes, to give a more or less "random"
20 ~lt~rn~ting di~Llibulion of relatively short segments of homopolymers, of dirr~lc
lengths. At some point, one monomer will be considerably depleted over the other,
favoring incorporation of the first, more or less on the basis of the principle of mass
action. The result of enrichm~-nt of one monomer over the other in the latter stages
of polymerization produces even longer blocks of homopolyrner derived from the
25 monomer in higher collcellkalion. The result is a ~tapered block copolymer",
having a mlllti~ 1e of shorter homopolymer segm~ntc, usually diads (2 monomers) to
pentads (5-monomers), and a "tail" enriched in longer segm~nt~ of the less reactive
monomer.
An alternative way of preparing random or tapered block copolymers
30 involves initiation of styrene, and interrupting with periodic, or step, additions of
diene monomer. The additions are programmed according to the relative reactivityratios and rate Coll~ of the styrene and particular diene monomer.
13
21 78039
Promoters" are electron-rich molecules that tend to enh~nre the basic nature
of the organolithium active site by coor~in~ting with the positively-charged lithium
cation, polarizing the charged species to effect greater charge separation at the active
site where interaction with virgin monomer occurs. Promoters include
tetrahydrofuran, tetrahydro~ , linear and crown ethers, N,N-dimethylform~mide,
tetramethyl ethylenedi~minP, and other non-protic agents that have non-bonding
electron pairs available for coordination. Promoters tend to facilitate anionic
initiation and poly~ l~Lion rates in general, while lesse~ing the relative dirr~ ces
in rates between various mo,l~ el.,. Promoters may be added in small amounts to
polymerization I~ ules co..~ i"g mixed monomers in non-polar paraffinic or
15 aromatic solvents in order to speed the reaction, and to effect the nature of the size
and distribution of blocks in the final copolymer.
Promoters also inflllPrlre the way in which diene monomers are incorporated
into the block polymer. A diene monomer can polymerize by 1,2- or 1,4-addition
(see following reaction scheme), and the 1,4-addition can (theoretically) be either in
20 a trans- or cis- configuration. Studies using 1,3-bllt~ nP/s~rrene monomers with
sec-butyl lithium initiator, have shown that in non-polar paraffinic solvents, the
diene monomer incorporates pre~c"..i,.~ ly (86-95%) by cis-1,4-addition. Addition
of small amounts of tetrahydroru.all promoter cause 1,3-but~AiPnP to increasingly
favor 1,2-polymerization over the normal 1,4-cis-polymerization.
Hydrogenation of the ullsa~ulated block polymers obtained initially as
polymerization products produces polymers that are more oxidatively and thermally
stable. Reduction is typically carried out at part of the polymerization process,
using finely divided, or supported, nickel catalyst. Other transition metals may also
be used to effect tl~lsrorl.lation. Hydrogenation is normally carried out to theextent of reducing approximately 94-96% of the olefinic lln~ r~tion in the initial
polymer. This means that the manner in which ~e diene monomer incorporates
becomes an important pararneter affecting the final physical and solution properties
of the hydrogenated polymers at ambient and low temperatures. The figure below
14
21 78039
.
5 shows diene incorporated both in a 1,4-cis and 1,2-manner. Hydrogenation of a
1,4-cis configuration produces linear polyethylene segments in the polymer,
reducing solubility in general, and introducing highly crystalline sites that tend to
associate at low leln~elalulc~s, and introduce potentially undesirable melt-associated
thermal transitions.
&H=C~
-(-CH2 CH2-)X- ~-(cH2cH2cH2cH2)
cis-l,~
CH2=CH-CH=CH2
1,3-L - -
-(-CH2-CH-)x~ ~-(CH2CH2)x-
~H=CH2 CH2CH3-
1,2-
In contrast, hydrogenation of diene introduced by 1,2-polymerization results in a
pendant alkyl group t_at enh~n~s solubility, decreases crystallinity in the diene
segments, and substantially reduces the tendency toward association. The ability to
control the balance of 1,4- and 1,2-modes of diene monomer incorporation, in order
25 to optimize overall properties of the hydrogenated block polymer, for use as a
viscosity modifier in lubricating oil compositions.
Isoprene incorporates into block polymers in a similar manner to that of 1,3-
bllt~1içn~, i.e., either by 1,4-cis or 3,4-polymerization. As with 1~3-bllt~ enp-
~predominalllly cis-1,4-incorporation is usual in non-polar p~rr~ic solvents, but
30 promoters, such as tetrahydrofuran, favor 3,4-polymerization. Again, a balance of
properties may be achieved by using small amounts of electron-rich promoters to
speed initiation and polylll~ ion, and to influence the nature and properties of the
final, hydrogenated polymer. With isoprene, there will be no possibility of
formation of crystalline polyethylene segments on the hydrogenation, because there
35 will always be aliphatic substituents in the polyisoprene blocks.
2 1 78039
CH3
/CH=C\ CH3
-(-CH2 CH2 )X- ~ -(cH2cH2cH2cH2)
ICH3 cis-1,4
CH2=C-CH=CH2
isoprene
-(-CH2--CH-)x~ ~ -(CH2 CH2)x-
CH=CH2 H2-CH3
3,4 CH3
It can be seen, then that the physical and solution properties of block
copolymers are dependent on both the monomers used, and the method of
preparation. The morphological characteristics of polymer solutions are similarly
dependent on polymer micro~lu~lulc. Morphology refers to the actual
col~,lllation of polymers under a defined set of conditions, and is dependent onstructure, polymer concentration, t~ ela~ulc, and additional influences of solvents
and other agents. Many types of block polymers show a good deal of intermolecular
associative behavior, wherein blocks, or segments, of like homopolymer may
agglollleldt~. In this sense, the block polymers demonstrate a kind of surface-active
nature,wherein they form micelles, similar to those formed by cl~si~l surfactants.
Su~lLing this plo~l~y are studies which have shown that block polymers have the
ability to stabilize colloidal dispersions. An exarnple of surfactant ~o~l~ies can be
shown by the ability of poly~lylelle-block copolymers to stabilize
dimethylform~micle-hexane emulsions.
Associative polymers can agglolllcla~e in several ways, to produce discreetly
dirr~ structures, d~ellding on the nature and arrangement of their blocks.
Morphological slructures range from spherical and core-shell, to cylindrical andlamellar. In a spherical or core-shell association, the center of the sphere is usually
formed by the more highly associative or crystalline segments, surloullded by a
(usually more diffuse) rnantle or shell which is enriched in the second type of
segment, which is frequently swollen by solvent or diluent. The cylindrical form is
similar to a spherical form, except that the core extends from one end to the other,
16
21 78039
S in an elongated shape, rather than a sphere. The lamellar form comprises an
arrangement of parallel planes of associated blocks, allelllatillg by type of segment.
The morphology of copolymers having highly crystalline segments are usually
controlled by the temperature at which such cryst~lli7~tion occurs, since this
effectively ~free~es" the entire structure. Thus, segments having signifi-~nt
10 crystallinity can effectively impose their morphology on the rçm~in-l~r of the
copolymer.
Intermolecular association of oil-soluble block copolymers used as viscosity
m~ifi~rs for l~lica,l~ can pose significant problems, in terms of handleability of
concen~ s. The polymer content of a polymeric viscosity improver concentrate
15 ranges typically from about 540% by weight, in a mineral oil, synthetic
hydrocarbon, or ester diluent. With non-associative polymers, such as OCP,
EPDM, but~l polymer or polymethacrylates, concentrates can be prepared at
relatively high polymer concentrations, without experiencing unduly highly bulk
viscosities. The styrene-diene block copolymers, however, are highly associative20 through the mutual affinity of their polystyrene segments, so that the amount of
polymer that can be dissolved before the concentrate viscosity become too great to
pour, is relatively low. The association problem is exacerbated by the use of non-
polar mineral oils or synthetic hydrocarbon diluents that are relatively poor solvents
for the poly~ylel1e segTn~ntc in the block copolymers. In these diluents, the degree
25 of association is relatively high, and the combined effective molecular weight of the
aggregates, astronomical. The effective thickening power of the copolymer
aggregates renders the concentrate a gel, and the collce~ dl~ becomes unpourable at
alllres as high as 100C.
In general, polystyrene-block-polyisoprene hydrogenated diblock copolymers
30 have two relatively large segments associated to a much greater degree than do
random block polymers of similar composition and molecular weight that have a
much larger number of relatively short polystyrene segments. Typically, the diblock
` 2178039
5 copolymer concentrate can contain no more than about 6% by weight, and the
random block copolymer no more than about 8% to be pourable at 100C.
In general, it is ~lefell~d that these block copolymers, for reasons of
oxidative stability, contain no more than about 5 percent and preferably no morethan ahout 0.5 percent residual olefinic ul~lu-~tion on the basis of the total number
10 of carbon-to carbon covalent linkages within the average molecule. Such
u.lsathlation can be ll.~s~d by a number of means well known to those of skill in
the art, such as infrared NMR, etc. Most preferably, these copolymers contain nodiscernible unsaturation as ~ . ., .i "~ by the aforementioned analytical techniques.
Examples of commercially available random block copolymers include the
15 varioius Glissoviscal block copolymers m~mlf~rtllred by BASF. Two especially
0 0
er~lled copolymers are Glissoviscal SGH and Glissoviscal CE-5260.
In addition to components (A) and (13), the compositions of this invention
may also contain (C) at least one oxidation inhibitor, (D) at least one extreme
pressurelanti-wear additive or mixtures thereof.
(C) The Oxidation Inhibitor
The oxidation inhibitor comprises
(1) an aLkyl phenol,
(2) an aromatic amine, or
(3) aheterocyclic amine.
(C1) The Alkyl Phenol
Component (C)(1) is an aLkyl phenol of the formula
(OH)z
~3(R4)a
30 wherein R4 is an alkyl group cont~ining from 1 up to about 24 carbon atoms, a is
an integer of from 1 up to 3 and z is 1 or 2. Preferably R4 contains from 1 to 12
18
21 78039
5 carbon atoms and most preferably from 4 to 12 carbon atoms. R4 may be either
straight chained or branched ch~in-od and branched chain is l~refel~ed. The
preferred value for a is 2 and the preferred value for z is 1.
Mixtures of alkyl phenols may be employed. Preferably the phenol is a
butyl substituted phenol cont~inin~ two t-butyl groups. When a is 2, the t-butyl10 groups occupy the 2,6-position, that is the phenol is sterically hindered:
(OH)
~.
When a is 3, the t-butyl groups occupy the 2,4,6- positions.
(C2) The Aromatic Amine
Component (C)(2) is an aromatic amine of the formula
RC
~(NHRs)b
wherein b is 1 or 2 and when b is 1, R~ is ~ or ~R7
and R6 and R7 are independently a hydrogen or an alkyl group cont~ining from 1
up to about 24 carbon atoms, and when b is 2, R5 and R6 are independently
20 hydrogen, an ar~l group or an alkyl group con~ining from 1 up to about 18
~ SR7
carbon atoms. Preferably b is 1, R5 is \_J and R6 and R7 are both nonyl
groups. When b is 2, R5 preferably is ~ and R6 and R7 are both
hydrogen.
19
21 78039
-
5 (C3) The Heterocyclic Amine
Component (C3) is a heterocyclic amine of formulae (a) or (b)
Z Z
'~' or (~
(a) (b)
wherein R8 is indep~nr~ently a hydrogen or an aLkyl group co..~ from 1 up to
about 4 carbon atoms, Z is hydrogen or O and X is hydrogen, -NR14R15 or
10 -oRI5 wherein Rl4 and Rl5 are independently hydrogen or aLkyl groups co
from 1 up to about 18 carbon atoms.
Within formula (C3a) and (C3b) R8 is preferably methyl. Compounds
having utility in this invention within formula (C3a) are 2,2,6,6-
t~Ll~l~Lhylpiperidine where X and Z are both hydrogen; 2,2,6,6-tetramethyl-1-
piperidinol where X is -oRl5 and Rl5 and Z are both hydrogen; and 2,2,6,6-
tetramethyl-l-piperidinyloxy free radical where Z is ~ O and X is hydrogen.
A compound having utility in this invention within formula (C3b) is 2,2,6,6-
tetramethyl~piperidone where Z is hydrogen.
20 (D) The Extreme Ples~ule/Allliwear Additive
The extreme pressure/allLiwear additive comprises
(1) a metal sulfur/phosphorus salt,
(2) a metal sulfur/nitrogen salt,
(3) a benzotriazole,
(4) a sulfurized composition, and
(S) a deliv~tiv~ of a dimerca~Lo~ ole.
(Dl) The Metal Sulfur/Phosphorus Salt
Component (Dl) is a metal sulfur/phosphorus salt of the formula
21 78039
~
~R \ p"S S~
~Rloo/ ~x
wherein R9 and Rl are independently hydrocarbyl groups cont~ining from 3 up to
about 20 carbon atoms, Ml is a metal selected from the group consisting of
lithillm, sodium, calcium, barium, copper, zinc, antimony, tin, cerium and othermembers of the l~nth~ni~le series, and x is the valence of Ml.
Component (D1) is readily obtainable by the reaction of phosphorus
pe~t~c~llfi-l~ (P2S5) and an alcohol or phenol. The reaction involves mixing at a
temperature of about 20C to about 200C. four moles of an alcohol or phenol
with one mole of phosphorus pent~c~llfi~e. Hydrogen sulfide is liberated in thisreaction.
The R9 and R10 groups are independently hydrocarbyl groups that are
preferably free from acetylenic and usually also from ethylenic unsaturation andhave from 3 to about 20 carbon atoms, preferably 3 to about 16 carbon atoms and
most preferably 3 to about 12 carbon atoms.
Preferred metals acting as M1 are copper, zinc, tin and cerium.
The following examples outline how component (D1) is l"epaled.
F,Y~mrle (Dl)-l
A reaction vessel is charged with 804 parts of a mixture of 6.5 moles of
isobutyl alcohol and 3.5 moles of mixed ~ laly amyl alcohols (65% w n-amyl
and 35% w 2-methyl-1-butanol). Phosphorus pentasulfide (555 parts, 2.5 moles)
is added to the vessel while m~int~ining the reaction temperature between about
104-107C. After all of the phosphorus pentasulfide is added, the mixture is
heated for an additional period to insure completion of the reaction and filtered.
The filtrate is the desired phosphorodithioic acid which contains about 11.2%
phosphorus and 22.0% sulfur.
A reaction vessel is charged with 448 parts of zinc oxide (11 equivalents)
and 467 parts of the above alcohol mixture. The above phosphorodithioic acid
; 2 1 78039
(3030 parts, 10.5 equivalents) is added at a rate to ,,.~i,.l~i,~ the reaction
t~ dlule at about 45 -50C . The addition is completed in 3 .5 hours
whereupon the temperature of the ll~Ll~lule is raised to 75C for 45 "~ill..les. After
cooling to about 50C, an additional 61 parts of zinc oxide (1.5 equivalents) are
added, and this ll~i~lule is heated to 75C for 2.5 hours. After cooling to ambient
t~ln~el~lùle, the mixture is stripped to 124C at mm. pressure. The residue is
filtered twice through diatomaceous earth, and the filtrate is the desired zinc salt
cont~inin~ 22.2% sulfur (theory, 22.0), 10.4% phosphorus (theory, 10.6) and
10.6% zinc (theory, 11.1).
F,Y~mrle (D1)-2
The procedure of Example (Dl)-l is essçnti~lly followed except that 2-
methylpentyl alcohol is used in place of the isobutyl alcohol and amyl alcohols.The product obtained has 8.5% phosphorus, 17.6% sulfur and 9.25% zinc.
(D2) The Metal Sulfur/Nitrogen Salt
Component (D2) is a metal sulfur/nitrogen salt of the formula
/Rll S \
N--C--S M2
\ Rl~ /
wherein R~l and Rl2 are independently hydrocarbyl groups cont~inin~ from 1 up toabout 24 carbon atoms, M2 is a metal moiety selected from the group consisting of
copper, zinc, antimony, tin, cerium and other members of the l~nth~ni~le series
25 and a molybdenum cation selected from the group consisting of -Mo=O and
O=Mo=O), and y is the valence of M2.
Preferably Rll and Rl2 are aliphatic groups cont~ining from 3 up to about
12 carbon atoms and M2 is preferably copper, antimony or zinc.
An example of a metal sulfur/nitrogen salt is an antimony
30 dialkyldithiocarbamate obtained from the R.T. Vanderbilt Company and known as
2 1 78039
S Vanlube 73. From laboratory analysis Vanlube 73 is believed to consist of
antimony dipentyldithioc~l,a,llate.
(D3) The Benzotriazole
Component (D3) is a benzotriazole of the formula
R16
RL~N
wherein Rl3 is hydrogen or an alkyl group cont~ining from 1 up to about 12
carbon atoms, Rl6 is hydrogen or -CH2SRl; where Rl7 is an alkyl group
cont~ining from 1 up to about 18 carbon atoms.
Preferably Rl3 is a methyl group and Rl6 is hydrogen which results in (D3)
15 being tolyltriazole of the forrnula
~H
H3C~N
Tolyltriazole is available under the trade name Cobratec TT-100 from Sherwin-
Williams Chemical.
(D4) The Sulfuriæd Composition
Within the purview of this invention, three dirrelellL sulfurized
compositions (D4a), (D4b) and (D4c) are envisaged and have utility. The first
sulfurized composition (D4a), is a sulfurized olefinic hydrocarbon prepared in
25 esse-nti~lly a two-step process that involves: 1) reacting an olefin with a sulfur
halide to form a sulfochlorinated adduct, and 2) contacting the sulfochlorinatedadduct with sodium sulfide or sodium polysulfide in a protic solvent. The proticsolvent may be water and an alcohol of 4 carbon atoms or less. Preferably, the
alcohol is isopropyl alcohol. The sodium polysulfide solution is best pl~yared by
23
2 1 78039
5 dissolving sulfur into an aqueouss Na7S or NaSH/Na2S solution. Water and
aqueous NaOH are added as n~cess~ry to adjust the basic sulfide concentration toa range of 18-21 percent Na2S and 2-5 percent NaOH.
Additions of sulfur dichloride (SCl2) or sulfur monochloride (S2Cl2) to an
olefin produces sulfochloride interm~ tes having sulfide and disulfide groups in10 the adducts. Contact of the sulfochloride intermediates withi the sodium sulfide or
sodium polysulfide solutions described results in nucleophilic displacement of
active chlorine as sodium chloride, and produces additional sulfide or polysulflde
groups within the product molecule. The product is a sllbst~nti~lly chlorine-free
sulfurized compound that can be used as a lubricant additive.
A wide variety of olefins may be charged to the initial sulfochlorination
reaction including hydrocarbon olefins having a single double bond with ~e~ inalor internal double bonds and cont~inin~ from about 2 to 50 or more, preferably 2to 8 carbon atoms per molecule in either straight, branched chain or cyclic
compounds, and these may be exemplified by ethylene, propylene, butene-l, cis-
and trans- butene-2, isobutylene, diisobutylene, triisobutylene, pentenes,
cyclopentelle, cyclohexene, the octenes, decene-1, etc. In general C3 6 olefins or
ules thereof are desirable for plep~illg sulfurized products for use as extreme
pressure additives. The combined sulfur content of the product decreases with
increasing olefin carbon number, while miscibility with oil increases.
The molar ratio of olefin to sulfur halide will vary depending on the
amount of sulfurization desired in the end product and the amount of olefinic
unsaturation. The molar ratio of sulfur halide to olefin could vary from 1:(1-20).
When the olefin to be sulfurized contains a single double bond, one mole of the
olefin can be reacted with 0.5 moles or less of S2Cl2 (sulfur monochloride). Theolefin is generally added in excess with respect to the amount of the sulfur being
added so that all of the sulfur halide will be reacted and any unreacted olefin can
remain as unreacted diluent oil or can be removed and recycled.
21 78039
After the sulfurization-dechlorination reaction, the reaction mixture is
allowed to stand and separate into an aqueous layer and another liquid layer
cont~ining the desired organic sulfide product. The product is usually dried by
heating at moderately elevated temperatures under sllb~tm~spheric pressure, and
its clarity may often be improved by filtering the dried product through a bed of
bauxite, clay or ~ tl~m~reous earth particles.
The following examplé is provided so as to provide those of ordinary skill
in the art with a complete disclosure and description of how to make the first
sulfurized composition.
F~mrle (D4a)-1 ~
Added to a three-liter, four-necked flask are 1100 grarns (8.15 moles) of
sulfur monochloride. While stirring at room temperature 952 grarns (17 moles) ofisobutylene are added below the surface. The reaction is exothermic and the
addition rate of isobutylene controls the reaction temperature. The temperature is
allowed to reach a maximum of 50C and obtained is a sulfochlorination reaction
product.
A blend of 1800 grams of 18% Na2S solution is obtained from process
streams. To this blend is added 238 grams 50% aqueous NaOH, 525 grams water
and 415 grams isopropyl alcohol to prepare a reagent for use in the sulruliGation-
dechlorination reaction. To this reagent is added 1000 grams of the sulfo-
chlorination reaction product in about 1.5 hours. One hour after the addition iscompleted, the contents are permitted to settle and the liquid layer is drawn off
and discarded. The organic layer is stripped to 120C and 100 mm Hg to remove
any volatiles. Analyses: % sulfur 43 .5, ~ chlorine 0.2.
Table I outlines other olefins and sulfur chlorides that can be utilized in
p~ aling the first sulfurized composition. The procedure is essentially the sameas in Example (D4a)-1. In all the examples, the metal ion reagent is prepared
according to Example (D4a)-1.
21 78039
Table I
xa~ le ~Ole~ ur Chlorid:e~le~tio~ e~:SC~
(D4a)-2 n-butene SCl~ 2.3:1
(D4a)-3 propene S2Cl2 2.5:1
(D4a)4 n-pentene S2C12 2.2:1
(D4a)-5n-butene/isobutylene S~cl2 2.5:1
1:1 weight
(D4a)-6isobutylenel2-pentene S~cl2 2.2:1
1: 1 weight
~D4a)-7isobutylene/2-pentene S2cl2 2.2:1
3:2 weight
(D4a)-8isobutylene/propene S2Cl2 - 2.3:1
6:1 weight
(D4a)-9n-pentene/2-pentene S~Cl2 2.2:1
1: 1 weight
(D4a)-102-pentene/propene S~Cl2 2.2:1
3:2 weight
The second sulfurized composition (D4b). is also a sulfurized olefinic
hydrocarbon that comprises the reaction product of sulfur and a Diels-Alder
10 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, Dienovyi Sintes, Izdatelstwo ~k~dernii Nauk SSSR, 1963 by A.S.
Onischenko. (Tr~n~l~tecl into the Fnali~h language by L. Mandel as A.S.
15 Onischenko, Diene Synthesis, N.Y., Daniel Davey and Co., Inc., 1964). This
monograph and references cited therein are incorporated by reference into the
present specification.
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
20 or acetylenically unsaturated compound, > C=C <, these latter compounds being known as dienophiles. The reaction can be represented as follows:
26
2 1 78039
-
Reaction 1:
\ /
/c~
_ C
>C=C-C=C~ + >C=C< ¦ A ¦
C
/c/
Reaction 2:
\ /
/c\
>C=C-C=C~ +-C-C ~ ¦ B ¦
C
/ \
The products, A and B are commonly referred to as Diels-Alder adducts.
It is these adducts which are used as starting materials for the plep~lion of the
15 second sulfurized composition.
Representative examples of such 1,3-dienes include aliphatic conjugated
diolefins or dienes of the formula
R~ R~l
Rl9~ 1 1 ,R~2
18 C=c--C=c 23
wherein Rl8 through R23 are each independently selected from the group consisting
20 of halogen, alkyl, halo, alkoxy, alkenyl, alkenyloxy, carboxy, cyano, amino,
alkylamino, dialkylamino, phenyl, and phenyl-substituted with 1 to 3 substituents
corresponding to Rl8 through R23 with the proviso that a pair of R's on adjacentcarbons do not form an additional double bond in the diene. Preferably not more
2 1 78039
5 than three of 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
lled aspect of the invention, adducts are used where R20 and R2l are both
hydrogen and at least one of the rem~ining R variables is also hydrogen.
Preferably, the carbon content of these R variables when other than hydrogen is 7
10 or less. In this most plerelled class, those dienes where R~, Rl9, R22 and R23 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-,
CH3COO-, CH3CH2O-, CH3C(O)-, HC(O), -C1, -Br, tert-butyl, CF3, tolyl, etc.
Piperylene, isoprene, methylisoprene, chloroprel1e, and 1,3-butadiene are among
15 the plefelled dienes for use in ~l~h~g the Diels-Alder adducts.
The dienophiles suitable for reacting with the above dienes to form the
adducts used as re~ct~nt~ can be represented by the formula
K1 ~3
2 ~ 4
wheleill the K variables are the same as the R variables in the diene formula
20 above.
A plefelled class of dienophiles are those wherein at least one of the K
variables is selected from the class of electron-accepting groups such as formyl,
cyano, nitro, carboxy, carbohydrocarbyloxy, hydrocarbylcarbonyl,
hydrocarbylsulfonyl, calballlyl, acylacarbanyl, N-acyl-N-hydrocarbylc~l,anlyl, N-
25 hydrocarbykall,;llllyl, and N,N-dihydrocarbylcalb~lyl. Those K 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 10 atoms each.
The hydrocarbyl groups present as N-hydrocarbyl sllbsth-~ents are
30 preferably alkyl of 1 to 30 carbon atoms and especially 1 to 10 carbon atoms.Repres~ ive of this class of dienophiles are the following: maleic anhydride,
nitroalkenes, e.g., 1-nitrobutene-1, 1-nitropentene-1, 3-methyl-1-nitro-butene-1, 1-
28
2 1 78039
5 nitroheptene-1, l-nitrooctene-1, 4-ethoxy-1-nitrobutene-1; alpha, beta-ethylenically
unsaturated aliphatic carboxylic acid esters, e.g., alkylacrylates and alpha-methyl
alkylacrylates (i.e., alkyl m-~th~rylates) such as butylacrylate and
butylm~th~-rylate, decyl acrylate and decylmPth~crylate, di-(n-butyl)-maleate, di-
~t-butyl-maleate); acrylonitrile, methacrylonitrile. beta-nitrostyrene, methylvinyl-
10 sulfone, acrolein, acrylic acid; alpha, beta-ethylenically unsaturated aliphatic
carboxylic acid amides, e.g., acrylamide, N,N-dibutylacrylamide,
mPth~crylamide, N-dodecylm---th~crylamide, N-penyl-crotonamide;
crotonaldehyde, crotonic acid, beta, beta-dimethyldivinylketone, methyl-vinyl-
ketone, N-vinyl pyrrolidone, alkenyl halides, and the like.
One plefelled class of dienophiles are those wherein at least one, but not
more than two of K variables is -C(O)O-R where R is the residue of a saturatedaliphatic alcohol of up to about 40 carbon atoms; e.g., for example at least one K
is carbohydrocarbyloxy such as carboethoxy, carbobutoxy, etc., the aliphatic
alcohol from which -R is derived can be a mono- or polyhydric alcohol such as
alkyleneglycols, alkanols, aminoalkanols, alkoxy-substituted alkanols, ethanol,
ethoxy ethanol, propanol, beta~iethylaminoethanol, dodecyl alcohol, diethylene
glycol, Llipl~ylene glycol, tetrabutylene glycol, hexanol, octanol, isooctyl
alcohol, and the like. In this especially ~lefelled class of dienophiles, not more
than two K variables will be -C(O)-O-R groups and the rem~ining K variables
will be hydrogen or lower alkyl, e.g., methyl, ethyl, propyl, isopropyl, and thelike.
Specific exarnples of dienophiles of the type discussed above are those
wherein at least one of the K variables is one of the following groups: hydrogen,
methyl, ethyl, phenyl, HOOC-, HC(O)-, CH2=CH-, HC-C-, CH3C(O)-,
C1CH2-, HOCH2-, alpha-pyridyl, -NO2, -C1, -Br, propyl, iso-butyl, etc.
In addition to the ethylenically unsacurated dienophiles, there are many
useful acety}enically unsaturated dienophiles such as propiolaldehyde,
methylethynylketone, propylethynylketone, propenylethynylketone, propiolic acid,
2~
21 78039
5 propiolic acid nitrile, ethylpropiolate, tetrolic acid, propargylaldehyde,
acetylenedicarboxylic acid, the dimethyl ester of acetylenedicarboxylic acid,
dibenzoylacetylene, and the like.
The second sulfurized compositions are readily l,repa[ed by heating a
ure of sulfur and at least one of the Diels-Alder adducts of the types discussed10 hereinabove at a temperature within the range of from about 100C to about
200C will normally be used. This reaction results in a n~ u~e of products, someof which have been identified. In the compounds of know structure, the sulfur
reacts with the substituted ullsaluldl~d cycloaliphatic react~nt~ at a double bond in
the nucleus of the unsaturated reactant.
The molar ratio of sulfur to Diels-Alder adduct used in the ~,~a.dlion of
this sulfur-cont~ining composition is from about 1:2 up to about 4:1. Generally,the molar ratio of sulfur to Diels-Alder adduct will be from about 1:1 to about 4:1
and preferably about 2:1 to about 4:1.
The reaction can be contlllcted in the presence of suitable inert organic
solvents such as mineral oils, alkanes of 7 to 18 carbons, etc., although no solvent
is generally n~cess~ry After completion of the reaction, the reaction mass can be
filtered and/or subjected to other conventional purification techniques. There is no
need to separate the various sulfur-co~ ,i"~ products as they can be employed inthe form of a reaction mixture comprising the compounds of known and unknown
structure.
As hydrogen sulfide is an undesirable co,~ A,,I7 it is advantageous to
employ standard procedures for ~sisring in the removal of the H2S from the
products. Blowing with steam, alcohols, air, or nitrogen gas assists in the
removal of H2S as does heating at reduced pressures with or without the blowing.It is sometimes advantageous to incorporate materials useful as
sulfurization catalysts in the reaction mixture. These materials may be acidic,
basic or neutral. Useful neutral and acidic materials include acidified clays such
as "Super Filtrol", p-toluenesulfonic acid, diallylphosphoro~ithioic acids,
2 1 78039
.
phosphorus sulfides such as phosphorus pe-nt~slllfide and phosphites such as triaryl
phosphites (e.g., triphenyl phosphite).
The basic materials may be inorganic oxides and salts such as sodium
hydroxide, calcium oxide and sodium sulfide. The most desirable basic catalysts,however, are nitrogen bases including ammonia and amines. The amines include
~ llal y, secondary and tertiary hydrocarbyl amines wherein the hydrocarbyl
radicals are aL~yl, aryl, aralkyl, alkaryl or the like and contain about 1-20 carbon
atoms. Suitable amines include aniline, benzylamine, dibenzylamine,
dodecylamine, naphthylamine, tallow amines, N-ethyl~ipropylamine, N-
phenylbenzylamine, N,N-diethylbutylamine, m-toluidine and 2,3-xylidine. Also
useful are heterocyclic amines such as prrolidine, N-methylpyrrolidine, piperidine,
pyridine and quinoline.
The ple~lled basic catalysts include ammonia and primary, secondary or
tertiary alkyl~min~s having about 1-8 carbon atoms in the alkyl radicals.
Representing amines of this type are methylamine, dimethylamine,
trimethylamine, ethylamine, diethylamine, triethylamine, di-n-butylamine, tri-n-butylamine, tri-sec-hexylamine and tri-n-octylamine. Mixtures of these amines
can be used, as well as ~ L~l~es of ammonia and amines.
When a catalyst is used, the amount is generally about 0.05-2.0% of the
weight of the adduct.
The following example illustrates the pLepalalion of the second sulfurized
composition. Unless otherwise in~ te l in these examples and in other parts of
this specification, as well as in the appended claims, all parts and percentages are
by weight.
FY~mple (1)4b)-1
A mixture comprising 400 parts of toluene and 66.7 parts of allminum
chloride is charged to a two-liter flask fitted with a stirrer, nitrogen inlet tube, and
a solid carbon dioxide-cooled reflux condenser. A second mixture comprising 640
parts (5 moles) of butyl acrylate and 240 8 parts of toluene is added to the AlC13
- 2178039
slurry while m~int~inin~ the temperature within the range of 37-58C over a 0.25-
hour period. Thereafter, 270 parts (5 moles) of butadiene is added to the slurryover a 2.75-hour period while m~int~inin~ the temperature of the reaction mass at
50-61C by means of external cooling. The reaction mass is blown with nitrogen
for about 0.33 hour and then transferred to a four-liter separatory funnel and
washed with a solution of 150 parts of concentrated hydrochloric acid in 1100
parts of water. Thereafter, the product is subjected to two additional water
washings using 1000 parts of water for each wash. The washed reaction product
is subsequently distilled to remove unreacted butyl acrylate and toluene. The
residue of this first tii~till~tion step is subjected to further ~1istill~tion at a pressure
of 9-10 millimetPrs of mercury whereupon 785 parts of the desired product is
collected over the temperature of 105-115C.
A mixture of 728 parts (4.0 moles) of the above material, 218 parts (6.8
moles) of sulfur, and 7 parts of triphenyl phosphite is pLepaled and heated withstirring to a temperature of about 181C over a period of 1.3 hours. The mixtureis m~int~in-~l under a nitrogen purge at a temperature of 181-187C for 3 hours.After allowing the material to cool to about 85C over a period of 1.4 hours, the
e is filtered using a filter aid, and the filtrate is the desired second
sulfurized composition co"~ g 23.1 % sulfur.
The third sulfurized composition (D4c) is prepared by sulfurizing a mixture
comprising three essential reagents. This first reagent is a fatty oil; that is, at
least one naturally occurring ester of glycerol and a fatty acid, or a synthetic ester
of similar structure. Such fatty oils are animal or vegetable oil tryiglycerides of
the formula
2 1 78039
CH2-OC~I
o
CH-OC-IR2
CH2{)C ~3
wherein R~, R2 and R3 are ~liph~tic groups co,.l~;";,~g from about 7 to about 23carbon atoms. A non-exhaustive list of triglycerides include peanut oil, collonseed
oil, soyl~ oil, sunflower oil and corn oil. These triglycerides are the same as
colll~ollelll (A) disclosed above.
The second reagent is at least one aL~enyl carboxylic acid of the formula
R25CooH Wll~leill R25 contains about 7 to about 29 carbon atoms. The carboxylic
acids are ol~i~ily free from acetylenic unsaLulaLion. Suitable acids include
(preferably) oleic acid, linoleic acid, linolenic acid, 14-hydroxy~ eicosenoic acid
and ricinoleic acid. In particular, the carboxylic acid may be an ul~lulal~d fatty
acid such as oleic or linoleic acid, and may be a ll~i~lule of acids such as is obtained
from tall oil or by the hydrolysis of peanut oil, soybean oil or the l~ke. The amount
of carboxylic acid used is about 2-50 parts by weight per 100 parts of triglyceride;
about 2-8 parts by weight is ~lefell~d.
The third reagent is at least one ~ul~L~ lly aliphatic monoolefin co"l~i"i"g
from about 4 to about 36 carbon atoms, and is present in the amount of about 25400
parts by weight per 1000 parts of triglyceride. Suitable olefins include the octenes,
~lecen. s, do~e~en~s, eicosenes and triacontenes, as well as analogous compoundscolll;1i"i"g aromatic or non-hydrocarbon substitl-~nt~ which are subst~nti~lly inert in
the context of this invention. (As used in the specification and appended claims, the
term "~ub~L~tially inert when used to refer to solvents, ~ nt~, substih-~nt~ and
the like is int~ntl~d to mean that the solvent, diluent, substituent, etc. is inert to
ch~mi~l or physical change under the conditions which it is used so as not to
inl~lr~le materially in an adverse manner with the pl~dlion, storage, blending
2 1 7803q
5 and/or functioning of the composition, additive, co~ d, etc. in the context of its
intPn-lP~ use). For example, small amounts of a solvent, diluent, substih~Pnt etc.
can undergo minim~l reaction or degradation without plevell~illg the making and
using of this component as described herein. In other words, such reaction or
degradation, while technir~lly ~licc~. .,;ble, would not be sllffiripnt to deter a worker
10 of ollli~u.~ skill in the art from making and using this component for its intPn~PA
purposes. "S~lbst~nti~lly inert" as used herein is, thus, readily understood anda~lecial~d by those of oldi~uy skill in the art. Terminal olefins, or a - olefins, are
eÇ.,lled, especially those co..l;.;..;..~ from about 12 to about 20 carbon atoms.
Especially ~leÇ~ d are straight chain a olefins. Mixtures of these olefins are
collllller~_ially available and such ll~lules are contemplated for use in this invention.
This sulfurized composition is prepared by r~cli-~g a ll~i~ e comprising a
triglyceride, a fatty acid and an aliphatic monoolefin with a sulfurizing agent at a
temperature between about 100C and about 250C, usually between about 150 and
about 210C. The sulruliz,l~g reagent may be, for example, sulfur, a sulfur halide
such as sulfur monochloride or sulfur dichloride, a ll~i~lule of hydrogen sulfide and
sulfur dioxide, or the like. FlPmPnt~l sulfur is often pl~r.,lled and the invention
especially contemplates the use of sulfurized composition pl~ared by reacting sulfur
with the arolesaid ll~lul~. The weight ratio of the cc,lllbi.~lion of ~Liglycelide,
fatty acid and aliphatic monoolefin to sulfur is between about 5:1 and about 15:1,
generally between about 5:1 and about 10:1.
In addition to the above described reagents, the reaction ll~i~e may contain
other materials. These may include, for example, sulfurization promoters, typically
phosphorus-co~ g reagents such as phosphorous acid esters such as lecithin.
The sulfurization reaction is effected by merely heating the reagents at the
temperature inflir~tPA above, usually with efficient agitation and in an inert
atmosphere (e.g., nitrogen). If any of the reagents, especially the aliphatic
monoolefin, are appreciably volatile at the reaction temperature, the reaction vessel
may be m~int~inPA under pressure. It is frequently advantageous to add sulfur
34
21 78039
5 portionwise to the ~ ule of the other reagents. While it is usually ~r~rell~,d of the
reagent previously described, the reaction may also be effected in the presence of a
substantially inert organic diluent (e.g., an alcohol, ether, ester, aliphatic
hydrocarbon, halogenated aromatic hydl~l,on or the like) which is liquid within
the temperature range employed. When the reaction ~ c~d~ule is relatively high,
10 e.g., about 200C, there may be some evolution of sulfur from the product which is
avoided if a lower reaction lelu~eldlule (e.g., from about 150 to about 170C) is
used. However, the reaction som~tim~s requires a longer time at lower
t~lll~la~ules and an adeql~t~ sulfur content is usually obtained when the
~lll~elalule is at the high end of the recited range.
Following the reaction, volatile materials may be removed by blowing with
air or nitrogen and insoluble by products by filtration, usually at an elevated
temperature (from about 80 to about 120C). The filtrate is the desired sulfur
product.
U.S. Patent Nos. 3,926,8æ and 3,953,347 are incol~ola~d by lefelellce
20 herein for their disclosures of a suitable sulfurized ll~Ll~lule of triglyceride,
carboxylic acid and aliphatic monoolefin. Several specific sulfurized compositions
are described in examples 10-18 of 3,926,822 and 10-19 of 3,953,347. The
following example illustrates the pl~dldlion of one such composition. (In the
specification and claims, all parts and percentages are by weight unless otherwise
25 in~ t~l )
Ex~nple (D4c)-1
A mi~lule of 100 parts of soybean oil, 5.25 parts of tall oil acid and 44.8
30 parts of commercial Cl5 l8 straight chain - olefins is heated to 167C under
nitrogen, and 17.4 parts of sulfur is added. The temperature of the ll~xlule rises to
208C. Nitrogen is blown over the surface at 165-200C for 6 hours and the
2 ~ 78039
S ~ Lule iS then cooled to 90C and filtered. The filtrate is the desired product and
cont~in~ 10.6% sulfur.
(D5) The Derivative Of A Dimercaptothi~ 7.01e
The dimercaptothi~ 701e derivatives which can be utilized as component
10 (DS) in the composition of the present invention contain the dil,lelca~othi~ 7.Qle
nucleus have the following structural formulae and names:
2,5-dimercapto-1,3,4-thi~ 7.ole
N N
Il 11
HS C~S~C SH
3,5-dimercapto-1,2,4-thi~ 701e
S N
11
HS C~N~C SH
3,4-dimercapto-1,2,5-thi~ 701e
HS--C C--SH
Il 11
S
4,5-dimercapto-1,2,3-thi~ 7.ole
N C--SH
N C--SH
~S~
Of these the most readily available, and the one plcL~lled for the purpose of this
invention, is 2,5-dimercapto-1,3,4-thi~ 7.ole. This compound will somP.tim~os be
36
2 1 78039
S referred to hereinafter as DMTD. However, it is to be understood that any of the
other dimer~a~ 7Qles rnay be substituted for all or a portion of the DMTD.
DMTD is conveniently prepared by the reaction of one mole of hydrazine, or
a hydrazine salt, with two moles of carbon ~lisl.lfi~ in an ~lk~lin~ medium, followed
by ~riflifi~tion
Derivatives of DMTD have been described in the art, and any such
colll~oullds can be included in the compositions of the present invention. The
preparation of some derivatives of DMTD is described in E.K. Fields "Tn~llctri~land F.ngin~ring Chemistry", 49, p. 13614 (September 1957). For the prepal~lion
of the oil-soluble derivatives of DMTD, it is possible to utilize already prepared
15 DMTD or to prepare ~e DMTD in situ and subsequently adding the material to be reacted with DMTD.
U.S. Patents 2,719,125; 2,719,126; and 3,087,937 describe the ~lepa.alion
of various 2,5-bis-(hydrocarbon dithio)-1,3,4-thi~ 701es. The hydrocarbon group
may be
20 aliphatic or aromatic, including cyclic, alicyclic, aralkyl, aryl and alkaryl. Such
compositions are effective corrosion-illl~ibhuls for silver, silver alloys and similar
metals. Such polysulfides which can be represented by the following general
formula
N-- N
Il 11
R--(S),~ S--C~ ,C--S--(S),,~--R'
25 wherein R and R' may be the same or dirrelelll hydrocarbon groups, and x and y
be integers from 0 to about 8, and the sum of x and y being at least 1. A process
for plcpalillg such derivatives is described in U.S. Patent 2,191,125 as complisillg
the reaction of DMTD with a suitable sulfenyl chloride or by reacting the
dimercapto ~ thi~701e with chlorine and reacting the resulting disulfenyl chloride
30 with a plilllaly or tertiary melcaptall. Suitable sulfenyl chlorides useful in the first
procedure can be obtained by chlorinating a melcaL,~n (RSH or R'SH) with chlorine
2 1 78039
5 in carbon tetrachloride. In a second procedure, DMTD is chlorinated to form the
desired bissulfenyl chloride which is then reacted with at least one mel~_a~L~ll (RSH
and/or R'SH). The disclosures of U.S. Patents 2,719,125; 2,719,126; and
3,087,937 are hereby incorporated by reference for their description of derivatives
of DMTD useful in the compositions of the invention.
U.S. Patent 3,087,932 describes a one-step process for preparing 2,5-bis
(hydrocarbyldithio)-1,3,4-thi~ 7Ole. The procedure involves the reaction of either
DMTD or its alkali metal or ammonium salt and a ,llerc~ in the presence of
hydrogen peroxide and a solvent. Oil-soluble or oil-dispersible reaction products of
DMTD can be prepared also by the reaction of the DMTD with a lll~lca~ and
forrnic acid. Compositions pl~aled in this manner are described in U.S. Patent
2,749,311. Any lllelcaptal1 can be employed in the reaction although aliphatic and
aromatic mono- or poly-merca~ cont~inin~ from 1 to 30 carbon atoms are
plefelled. The disclosures of U.S. Patents 3,087,932 and 2,749,311 are hereby
incorporated by reference for their description of DMTD derivatives which can beutilized as a metal passivator.
Carboxylic esters of DMTD having the general formula
N N
Il 11
R--C(O)--S--C~ ~C--S--C(O~R
wherein R and R' are hydrocarbon groups such as aliphatic, aryl and alkaryl groups
co~ i"g from about 2 to about 30 or more carbon atoms are described in U.S.
Patent 2,760,933. These esters are prepared by reacting DMTD with an organic
acid halide (chloride) and a molar ratio of 1:2 at a l~,llL,elaLule of from about 25 to
about 130C. Suitable solvents such as benzene or dioxane can be utilized to
facilitate the reaction. The reaction product is washed with dilute aqueous allcali to
remove hydrogen chloride and any unreacted carboxylic acid. The disclosure of
U.S. Patent 2,760,933 is hereby incorporated by reference for its description ofvarious DMTD derivatives which can be utilized in the compositions of the present
invention.
38
2 1 78039
5Con-l~r~ tion products of alpha-halogenated ~liph~tir monocarboxylic acids
having at least 10 carbon atoms with DMTD are described in U.S. Patent
2,836,564. These con-1en~tion products generally are characterized by the
following formula
N N
Il 11
HOOC--CH(R)--S--C~ ,C--S--CH(R~COOH
10 wl~eleill R is an alkyl group of at least 10 carbon atoms. Examples of alpha-halogenated aliphatic fatty acids which can be used include alpha-bromo-lauric acid,
~lph~hloro-lauric acid, alpha-chloro-stearic acid, etc. The disclosure of U.S. Patent
2,836,564 is hereby incorporated by reference for its disclosure of derivatives of
DMTD which can be utilized in ~e compositions of the present invention.
15Oil-soluble reaction products of unsaturated cyclic hydrocarbons and
unsaturated ketones are described in U.S. Patents 2,764,547 and 2,799,652,
respectively, and a disclosure of these references also are hereby incorporated by
~cç~le~lce for their description of materials which are useful as a DMTD derivative
in the present invention. Examples of unsaturated cyclic hydrocarbons described in
20 the '547 patent include styrene, alpha-methyl styrene, pinene, di~enLelle,
cyclopent~ n~, etc. The ullsaLuldL~d ketones described in U.S. Patent 2,799,652
include aliphatic, aromatic or heterocyclic unsaturated ketones cont~inin~ from about
4 to 40 carbon atoms and from 1 to 6 double bonds. Examples include mesityl
oxide, phorone, isophorone, benzal acetophenone, furfural acetone, difurfuryl
25 acetone, etc.
U.S. Patent 2,765,289 describes products obtained by reacting DMTD with
an aldehyde and a diaryl arnine in molar proportions of from about 1:1:1 to about
1:4:4. The res-lltin~ products are suggested as having the general formula
N N
Il 11
R2N--CH(R")--S--C~ ~C-S--CH(R")--NR'2
39
2 1 7803~
5 wllelei~l R and R' are the same or different aromatic groups, and R" is hydrogen,
and alkyl group, or an aromatic group. The aldehydes useful in the preparation of
such products as represented by Formula X include aliphatic or aromatic aldehydes
cont~inin~ from 1 to 24 carbon atoms, and specific examples of such aldehydes
include forn~ yde, a~et~ yde, benzaldehyde, 2-ethylehexyl aldehyde, etc.
10 The disclosure of this patent also is hereby incorporated by refierence for its
ntific~tion of various materials which can be utilized in the compositions of this
invention.
Amine salts of DMTD such as those having the following formula
N
Y--S--C C S N~
\ / H
S
15 in which Y is hydrogen or the amino group
/R
N~
H
in which R is an aliphatic, aromatic or heterocyclic group, cont~ining from about 6
to about 60 carbon atorns also have utility as component (D5). The amine used inthe pl~al~Lion of the amine salts can be aliphatic or aromatic mono- or polyamines,
20 and the amines may be prirnary, secondary or tertiary amines. Specific examples of
suitable amines include hexylamine, dibutylamine, dodecylamine, ethylen~ min~,
propylen~li~minP, tetraethylenepent~min~, and mixtures thereof. The disclosure of
U.S. Patent 2,910,439 is hereby incorporated by leî~lel.ce for its listing of suitable
amine salts.
2 1 78039
.
S Dithiocalbal~; derivatives of DMTD are described in U.S. Patents
2,690,999 and 2,719,æ7. Such compositions can be ~cplcsell~d by the following
for nulae
N N
Il 11
~2N--C(S)--S--C~S,C-S--C(S)--NR2
and
N N
Il 11
R2N--C(S)--S--C~s~C-SH
whelei~l the R groups are straight-chain or branch-chain saturated or uns~Lulated
hydrocarbon groups selected from the group COllsiSlillg of alkyl, aralkyl and aL~caryl
groups. The disclosures of these two patents also are hereby incorporated by
lerelellce for the identification of various thi~ 7yl dithiocall,a llal~s which are
useful in the compositions of the present invention.
U.S. Patent 2,850,453 describes products which are obtained by reacting
DMTD, an aldehyde and an alcohol or an aromatic hydroxy compound in a molar
ratio of from 1:2:1 to 1:6:5. The aldehyde employed can be an aliphatic aldehydeco~t~ining from 1 to 20 carbon atoms or an aromatic or heterocyclic aldehyde
COI,l1i.lil~ from about 5 to about 30 carbon atoms. Exarnples of suitable aldehydes
include formaldehyde, acet~ltlellyde, ben7~1~yde. The reaction can be con~-lcte~in the presence or absence of suitable solvents by (a) mixing all of the re~rt~nt~
together and heating, (b) by first reacting an aldehyde with the alcohol or the
aromatic 2-hydroxy compound, and then reacting the res~llt~nt ;~ te with the
thi~ 7O1e, or ~c) by reacting the aldehyde with thi~ 7O1e first and the resulting
interrnto~ te with the hydroxy compound. The disclosure of U.S. Patent 2,850,453is hereby incorporated by lefelellce for its identification of various materials which
can be utili_ed in the compositions of the present invention.
U.S. Patent 2,703,784 describes products obtained by reacting DMTD with
an aldehyde and a mercaptan. The aldehydes are similar to those disclosed in U.S.
41
21 78039
Patent 2,850,453, and the melca~tans may be aliphatic or aromatic mono- or poly-elcaptans cont~ining from about 1 to 30 carbon atoms. Examples of suitable
IllelcaL1~ls include ethyl melcd~all, butyl mercaptan, octyl me.ca~Lall, thiophenol,
etc. The disclosure of this patent also is incorporated by reference.
The preparation of:
2-hydrocarbyldithio-5-mercapto-1,3,4-thi~ 7.oles having the formula
N N
Il 11
R'--S--S--C~ ,C-SH
wllerein R' is a hydrocarbyl substituent is described in U.S. Patent 3,663 j561. The
compositions are prepared by the oxidative coupling of equimolecular portions of a
hydrocarbyl merca~ and DMTD or its alkali metal mercaptide. The compositions
are reported to be excellent sulfur scavengers and are useful in preventing copper
corrosion by active sulfur. The mono-melca~ans used in the preparation of the
compounds are represented by the formula
R'SH
wherein R' is a hydrocarbyl group cont~inin,, from 1 to about 280 carbon atoms. A
peroxy compound, hypohalide or air, or mixtures thereof can be utilized to promote
the oxidative coupling. Specific exarnples of the monomercaptan include methyl
Illel~,d~l, isopropyl lllelca~ , hexyl me~ an, decyl melcd~ , and long chain
alkyl mel~;a~ls, for exarnple mercaptans derived from propene polymers and
isobutylene polymers especially polyisobutylenes. having 3 to about 70 propene or
isobutylene units per molecule. The disclosure of U.S. Patent 3,663,561 is hereby
incorporated by reference for its identification of DMTD derivative which are useful
as in the compositions of this invention.
Another material useful as component (D5) in the compositions of the
present invention is obtained by reacting a thi~ 7O1e, preferably DMTD with an
oil-soluble dispersant, preferably a substantially neutral or acidic carboxylic
dispersant in a diluent by heating the mixture above about 100(:. This procedure,
and the derivatives produced thereby are described in U.S Patent 4,136,043, the
42
21 78039
5 disclosure of which is hereby incorporated by reference. The oil-soluble di~e~which are utilized in the reaction with the ~hi~ 7O1es are often identified as "ashless
dis~~ ". Various types of suitable ashless di~ useful in the reaction are
described in '043 patent.
Another material useful as component (D5) in the compositions of the
10 invention is obtained by reacting a thi~ 7ole, preferably DMTD, with a peroxide,
preferably hydrogen peroxide. The rçsllltin~ nitrogen- and sulfur-cont~inin~
composition is then reacted with a polysulfide, melca~ or arnino compound
(especially oil-soluble, nitrogen-co,-l~i"i"~ dispersants). This procedure and the
derivatives produced thereby are described in U.S. Patent 4,246,126, the~disclosure
15 of which is incorporated herein by lefelellce.
U.S. Patent 4,140,643 describes nitrogen and sulfur-col,l~;"i"~ compositions
which are oil-soluble and which are prepared by reacting a carboxylic acid or
anhydride cont~inin~ up to about 10 carbon atoms and having at least one olefinic
bond with compositions of the type described in U.S. Patent 4,136,043. The pre-
20 ferred carboxylic acid or anhydride is maleic anhydride. The disclosures of U.S.Patents 4,136,043 and 4,140,643 are hereby incorporated by rt:r~leilce for their
disclosures of materials useful as component (DS) in the compositions of the present
invention.
U.S. Patent 4,097,387 describes DMTD derivatives prepared by reacting a
25 sulfur halide with an olefin to form an intermediate which is then reacted with an
aL~ali metal salt of DMTD. More recently, U.S. Patent 4,487,706 describes a
DMTD derivative prepared by reacting an olefin, sulfur dichloride and DMTD in a
one-step reaction. The olefins generally contain from about 6 to 30 carbon atorns.
The disclosures of U.S. Patents 4,097,387 and 4,487,706 are hereby incorporated
30 by reference for their descriptions of oil-soluble DMTD derivatives which are useful
as component (D5) in the compositions of this invention.
The compositions of the present invention comprising components (A) and
(B) or (A) and (B) with (C) or (D) or with (C) and (D) are useful as viscosity
43
2 1 78039
S modifled environm~ont~lly friendly farm tractor lubricants and chain bar lubricants
and hydraulic fluids.
When the composition comprises components (A) and (B), the following
states the ranges of these components in parts by weight:
Component Generally Preferred Most Preferred
(A) 80 - g9.5 90 - 99.5 96 - 99
(B) 0.5 - 20 0.5 -10 1- 4
When the composition comprises components (A), (B) and (C); or (A), (B)
and (D), the following states the range of these components in parts by weight:
Component Generally Preferred Most ~efelled
(A) 80 - 99.5 90 - 99.5 93 - 98.5
(B) 0.5 -12 0.5 - 6 1- 4
(C)or(D) 0.5-8 0.5-4 0.5-3
When the composition comprises components (A), (B), (C) and (D), the following
states the range of these components in parts by weight:
Component Generally Pl~fell~dMost Preferred
(A) 80 - 99 90 - 99 91 - 98
(B) 0.5-10 0.5-6 1-5
(C) 0.25 - 5 0.25 - 2 0.5 - 2
(D) 0.25 - 5 0.25 - 2 0.5 - 2
It is understood that other components besides (A), (B), (C) and (D) may
be present within the composition of this invention.
The components of this invention are blended together according to the
above ranges to effect solution. Ther following Table II outlines examples so as20 to provide those of ordinary skill in the art with a complete disclosure and
description on how to make the compositions of this invention and is not intended
21 78039
5 to limit the scope of what the inventor regards as the invention. All parts are by
weight.
While the invention has been explained in relation to its preferred
embodiments, it is to be understood that various modifications thereof will become
apparent to those skilled in the art upon reading the specification. Therefole, it is
10 to be understood that the invention disclosed herein is intended to cover such
modifications as fallwithin the scope of the appended claims.
2 t 78039
.
Table II
:~C parts Sunyl ( o 39.52 .65
2 99 parts Sunyl 80 oil1 part Glissoviscal SGH 63.57 13.16
3 98 parts Sunyl 80 oil2 parts Glissoviscal SGH 117.97 20.11
4 97 parts Sunyl 80 oil3 parts Glissoviseal SGH 268.85 30.70
96 parts Sunyl 80 oil4 parts Glissoviscal SGH 705.67 46.21
6 95 parts Sunyl 80 oil5 parts Glissoviseal SGH 1915.2 70.43
7 94 parts Sunyl 80 oil6 parts Glissoviseal SGH 5007.4113.37
8 92 parts Sunyl 80 oil8 parts Glissoviseal SGH 10,000 344.4
9 90 parts Sunyl 80 oil10 parts Glissoviseal SGH 88,6001181.0
99 parts Sunyl 80 oil1 part Glissoviseal CE-5260 61.56 12.50
11 98 parts Sunyl 80 oil2 parts Glissoviseal CE-5260 98.70 18.74
12 97 parts Sunyl 80 oil3 parts Glissoviscal CE-5260 152.56 25.72
13 96 parts Sunyl 80 oil4 parts Glissoviscal CE-5260 242.05 36.65
14 95 parts Sunyl 80 oil5 parts Glissoviscal CE-5260 392.20 49.23
94 parts Sunyl 80 oil6 parts Glissoviseal CE-5260 694.21 72.17
16 92 parts Sunyl 80 oil8 parts Glissoviscal CE-5260 2487.9140.09
17 90 parts Sunyl 80 oil10 parts Glissoviscal CE-5260 9919.0265.88
46
