Note: Descriptions are shown in the official language in which they were submitted.
WO g3/23~0~ P~/U~9~/0~71
J ;
Title: LUBRICATING COMPOSITIONS AND CONCENTE~Al~
This appllcation is a continustion-ln-part of pending U.S. Serial No.
07/688,195, filed April 19, 19911 and pending IJ.S. Serial No. 07/69û,1791 filcdApril 199 1991. The disclosures of said prior applicatlons are incorporated here~n
~n their entirety.
Ficld of the Invention
This invention relates to lubricating oil compositions and
concentrates, and more particularly, to lubricating oil co~npositions containingalkali metal overbased salts of hydrocarbyl-substituted c~rboxylic acids~
As engines, specifically, spark-ignited and diesel engines have
increased power outpu~ and complexity, the performance requirements of
lubricating oils have been increased to require lubricating oils that exhibi~ a
reduced tendency: to deteriorate under conditions of use and thereby to reduce
wear, rust, corosion and the formatio~ of such undesirable deposits as varnish,
sludge, carbanaceous materials and resinous:materials which tend to adhere to
various engine parts and reduce the efficiency of engines. Various materials
1" 1 ! ` ` i , ~ ,
have been included in the lubricating oil compositions to enable the oil
composi~ions to meet the various performance requirements, and these include
:
dispe~an~s, detergents, friction modifiers, corrosion inhibitors, antioxidants,
viscosity modifiers, etc. ~ ~
Dispersants ~ are emplo~ed in lubricants to maintain impurities,
~5 partieularly those formed during operatlon of an internal combustion engine, in
W093/~3504 æ~,~3y~'`J',~' PCr/US~/0~718
--2--
suspension ra~her than allowing ~hem to deposit as sludge. Dispersant additives
for lubricants cQmprising the reaction products of hydroxy compounds or amines
with substituted succinic acids or their derivatives have been described in ~he
prior art, and typical dispersions of this type are disclosed in, for example, ll.S.
Paten~ 3,272,746; 3,522,179; 3,219,666; and 4,~34,435. When incorporated into
lubricating oils, the compos~tions described ln the '435 patent function primarily
as dispersants/detergents and ~rlscosity-index improvers.
Alk~11ne earth metal desergents have been lncluded in lubricating
oil compositions to suspend degradativn products of a motor oil and to neutralize
acid products withln the oil In the engines. 1`he alkaline earth metals may be
calcium, magnesium, bariurn or strontium, and mixtures of such met~ls can be
used. The alkaline earth metal detergents generall3~ are basic. Alkali metal
detergents also ha~e been used In lubrlcsting oll compositions to provide
improved detergency.
Alkali metal sal~s, including basic salts, have been described in the
general literaturc ~nd in patents. For example, Canadian Patent t,055,700
describes basic alkali metal sulfcnate dispersions and processes. More particular-
ly, the patent describes solutions and/or stable dispersions of basic lithiurn
sulfonates, basic sodium sulfonat2s and basic potassium sulfonates having metal
ratios ln the range of from sbout 4 to abou~ 40. In the procedure utllized for the
preparation of these overbased sulfonates, the reaction mixture which is
contacted with an acidic gaseous material such as carbon dloxide comprises in
addition to one or more oil-soluble sulfonic acids or deriYatives thereof, one or
more alkali metals or metal compounds, one or morei lower aliphatic mono- or
dihydric alcohols, and one or more oil-soluble carboxylic acids or deri~atives
thereof. These carboxylic acids include mono- and polycarboxylic acids.
U.S. Patent 3,271,310 (LeSuer) describes metal salts of an alkenyl
succinic acid having at least about 50 aliphatic carbon atoms in the alkenyl
substituent. The salts include acidic salts, neutral salts or basic salts, and the
metals are selected from the class consisting of Group I metals, Group 11 metals,
WO 93J23504 PCI/US92~1)871~
aluminurn, lead, tin, cobalt and nickel. Th~i metal salts of the alkenyl succinic
acids are reported to be useful as lubricating additives and rnay be included inlubricating oils in amounts of from abuut 0.1% to about 20% by weight. Other
additives which may be included in the lubricating oils include, for example,
other detergents and dispersants, oxidation-inhibiting agents, corroslon-inhlblting
agents, extreme pressure agents, etc.
U.S. Patent 3,312,618 ~LeSuer~ describes a process for preparing an
oil-soluble highly basiic metal s81t of an orgarlic acid utllizing anhydrous
conditions and certain promoters. The organic ~cids may be sulfonic acids,
phosphorus acids, carboxylic acids or mix~ures thereof. The carboxylic acids
include fatty acids contairling at least lZ carbon atoms such as palmi~ic acid, or
cyclic acids such as those containing a benzenoid structure~ fsr example,
benzene, an oil-soluble group or groups having a total of at least about 15 carbon
atoms and preferably from about 15 to about 200 carbon atoms. The metal
compounds utilized to form the metsl salts include alkali and alkaline esrth
metals.
U.S. Patent 4,283,294 (Clarke) describes lubricating oll composi-
tions useful in mari~e diesel engines, and the compositions comprise in additionto oil, a mixt~Lre of ~ Group la metal o~rerbased detergent, a Group lla metal
overbased detergent, and an antloxidant provided that the weight ratio of the
overbased detergent mixture to the antioxidant is between 7.5:1 ~nd 50:1. The
Group la and lla detergent additives include metal salts of phenols, phenol
sulfides, phosphosulfurized palyolefins, organic sulfonates and carboxylic acids.
The carboxylic acids sre long chain, mono- or dicarboxylic acids such as those
wherein the acid radical contains at least 50 carbon atoms per molecule. Thus,
the metal salts include salts of long chain succinic acids such as those having
molecular weights of 850 to 1~200. The antioxidants described in this patent
include alkylated hindered phenols, organic amines, organic sulfur compounds,
metal thlophosphates, etc. Optlonal additives in the lubricating oil compositions
:
WO 93/23504 PCr/US92/0~718 . .
2~ ?~ 'JJ
are dispersants such as polyisobutenyl succinic anhydride-tetraethylene
pentamine reaction products.
Lubricating oil compositions containing basic alkali metal salts of
sulfonic or carboxylic acids, and carboxyllc derivative compositions obtained byreacting substituted succinlc acylating agents wlth at least one amine compound
are described in U.S. Patents 4,904,401; 4,93~,881; and 4,952,238. The c~rboxylic
sclds rnay be either monocarboxylic acilds or polycarboxylic acids including
dicarboxylic acids such as substituted succinic acid~. Sui~able carboxylic scidsfrom which useful alkali metal salts can be prepared include aliphatic~
cycloaliphatic and arnmatic mono- and polycarboxylic acids including naphthenic
acidls, alkenyl-substituted aromatic a~ids, and allcenyl succinic acids. The
aliphatic acids genel ally contain from about 8 to ~bout 50, and preferably fromabout 12 to about 25 carbon at~ms. These patents also describe basic alkali
metal salts, mixtures of sulfonic scids and carboxylic acids wherein the ratio of
equivalents of the carboxyllc acid when present to the organic sulfonlc acid in
the mixture generally is from about 1:1 to about 1:20 and preferably from abnut
1:2 to about 1:10. The amount of the alkali metal overbased sulfonate or
carboxylate included in these oil compositions may range from about 0~01 to
about 2% by weight. .The oil composition~ may contain other desirable additives
such ss metal salts of dihydrocarbylphosphorodithioic acids, antioxidants, friction
modifiers, neutral and basic salts of phenol sulfides, sulfur-containing compounds
useful in improving antiwear? extreme pressure antioxidant properties, and
neutral or basic alkaline ea~ th me~al salt detergents.
U~K. Patent Application 2,062,672 (Zalar) describes additive
!~ ' 25 ~ compositions ~or lubricating oils which comprise sulfurized alkyl phenol and high
molecular weight dispersants. The dispersants are oil-soluble carboxylic
dispersants containing a hydrocarbon-based radical having a number average
molecular weight of a~ least 1300 attached to a polar group such as succinic acid
or derivative tbereof. Generally, the carboxylic dispersants are reaction
products of carboxylic acids or derivativ~s thereof with ~a) nitrogen-containing
.. . , . . ... ,".. , .. ,~ .. . .. , i
WO 93/~351)4 PCI/US92/08718
f j ~ ~ ,' ,' j ,;, ,_ !
_S_
compounds having at least one ~NH group, (b) organic hydroxy compounds such
as phenols and alcohols, and/or (c) reactive metals or metal-reactive compounds.The carboxylic dispersants may be post-~rested wlth various reagents including
sulfur and sulfur compoundis, urea, thiourea~ aldehydes, ketones, carboxylic acids,
epoxides, boron compounds, phosphorus compounds, etc. The carboxylic acid
which is utilized in the preparation of the dispersanl:s are referred to as acylating
agents. The acyla~ing agent may be prepsred by the alkylat{on of an acid such
as maleic acid or anhydride. The alkylating sgent ma~ be a polymer containing
at least one olefinic bond or a halogen. Thc nwnber a~erage mole~ular weight
of the polymer is at least 1300 and usually is in the range of about 1500 to about
5000. The ratio of Mw to Mn may be from about 1.5 to about 6 ~nd is usually
from 1.5 to about 4. I~epending upon tbe ~nount of the reactants utilized to
form the substituted succinic aclds~ and depending upon the type of dispersant
desired, the mole ratio of the polyrner to the malcic acid or anhydride in the
reaction mixture may be equal to, greater than or less than 1, In some
applications, the dispersant is produced containing an a~rerage of at least 1.3
succinic moieties per polymer moiety. Among the reactivë metal compounds
which may be used to produce the dispersants are alkali metal compounds su,ch
as alkali metal hydroxides, carb~nates, alkoxides, oxides, etc. The patentees
indicate that the lubri~ating oil compositions may also contain other additives
încluding auxiliary detergents and dispersants, corrosion and oxidation-inhibiting
agents, pour point depressing agen~s, extreme pressure agents, etc.
Sum~of the Invention
A lubricating oll~ composition is described which comprises a major
amount of an oil of lubricsting viscosity and
(A) ~ at least about 1% by weight of at Icast one carboxylic
derivati-re composition produced by reacting
(A- I ) at least one substituted succinic acylating agent
containin~ at leas~ about 50 carbon atoms in the substituent with
WO 93/23504 PCr/~S92~871X~
2 ~ Q ~ ~ -6-
(A-2) from abnut 0.5 equivalent up to about 2 moles, per
equivalent of acylating a~ent (A-l), of at least one arnine compound character-
ized by the presence within its structure of at least one HN~ group; and
(B) at least one alkali metal overbased salt of a hydrocarbyl-
subs~ituted carboxylic acid or a mixtwre of a hydrocarbyl carboxylic acld and a
hydrocarbyl-substituted sulfonic acld havlng a me~al ratio of greater than 2 in
an amount sufficient to provide at least about 0.002 equivalent of alkall metal
per 100 grams of the lubricating oil composi~ion wher~in the hydrocarbyl
substituent of ~he carboxylic acid cunt~ns a~ least about 50 carbon atoms,
provided that when the alkali metal salt comprises a mixture of overbased alkalimetal salts of a hydrocarbyl-subs~ituted carboxylic acid and a hydrocarbyl-
subs~ituted sulfonic: acid, then the carboxylic acid coTnprise~ more than 50% ofthe AICid equivslents of the mixture, and provided further that when the
substituted succinic acylating agent (A-1) consist of substitu~nt groups and
succinic groups and said scylating agent is characterized by the presence witbinits structure of an average of at least 1.3 succinic gro1Jps for e~ch equivalentweight of substituent groups tbe metal ratio of the alkali metal overbased salt
(B) is greater than 1.
DescriDtion of the eferred Embodiments
T~roughout this specification and claims, references to percentages
by weight of the various components are on a chemicallbasis unless otherwise
indicated. For example, when the oll compositions of the invention are describedas cont~ining at least 2% by weight of (A), the oil composition comprises at least
2% by weigh~ of ~A) on a chemical basis. Thus, if component (A) is available as
~ a 50% by weight oil solution, at least 4% by wéight of the oil solution would be
included in the lubricant composition.:
The nwnber of equivalents of the acylating agent depends on the
total number of carboxylic functions present. In determining ~he number of
equivalents for the acylating agents, those carboxyl functions which are not
capable of reacting as a carboxylic acid acylating agent are excluded. In
WV 93/23504 P~/US92/08718
general, however, there is one equivalent of acylating agent for each carboxy
group in these acylating agents. For example, there are two equivalents in an
anhydride derived from the reaction of one mole ofolefin polymerand one mole
of maleic anhydride. Conventional technlques are readlly av~ilable for determin-ing the numb~r of carboxyl functions (e.g., acld number, saponiflcation nurnber)and, thus, the number of equivalents of the acylating agent can be readily deter-
mined by one skilled in the art.
An equivalent weight of an amlne or a polyarnine is the molecular
weight of the amine or polyamine divided by the total number of nitrogens
present in the molecule. Thus, ethylene dlamine has an equivalen~ weight equal
to one-half of its molecular weight; diethylene triamine has an equivalent weight
equal to one-third its molecular welght. The equivalent welght of a commer-
cially available mixture of polyalkylene polyamlne can be determined by dividingthe a~omic weight of nitrogen (14) by the %N c~ntalned in the polyamine and
multiplyi~g by 1009 thus, a polyamine mixture containing 34~ nitrogen would
have an equivalent weight of 41.2. An equivalent weight of ammonia or a
monoamine is the molecular w~ight.
An equivalent weight of a hydroxyl-substituted amine to be react~d
with the acyla~ing agents to form the carboxylic derivative (A) is its molecularweight divided by the total number of nitrogen groups present in the molecule.
For the purpose of this invention in preparing component (~, the hydroxyl groupsare ig~lored when calculating equivalent weight. Thus, ethanolamine would have
an equivalent weight equal to its molecular weight, and diethanolamine has an
equivalent weight (based on nitrogen) equal to its molecular weight.
The terms "substituent", "acylating agent" and "substituted succinic
acylating agent" are to be given their norrnal meanings. For example, a
substituent is an a~om or group of atoms that has replaced another atom or groupin a molecule as a result of a reaction. The terrns acylating agent or substituted
succinic acylating agent refer to the compound per se and does not include
WO 93/23504 PCI /US92/0~718
d~s,
unreacted reactarlts used to forrn the acylating agent or substituted succirlic
acylating agent.
The term "hydrocarbyl" includes hydrocarbon, as well as substan-
tially hydrocarbon, groups~ Substantlall~f hydrocarbon describes groups which
contain non-hydrucarbon substituents which do not alter the predominately
hydrocarbon nature of the group.
Ex~mples of hydrocarbyl groups Include the followlng:
~1) hydrocarbun subst~tuentsJ ~hat is, aliphatlc (e.g.t alkyl or
alkenyl), al~cyclic ~e.g., ~ycloalkyl, cycloalkenyl) substituents, aromatic-,
aliphatic- and alicyclic-substituted arom~tic subst~tuents and the like as well as
cyclic substltuents wherein the ring is completed through ~nother portion of ~hemolecule (that is, for example, any two indicated substituents may together formar. alicyclic radical);
(2) substituted hydrocarbon substituents, that is, those
substituents containing non-hydrocarbon groups which, in ~he context of thls
invention, do not alter the predominantly hydrocarbon substituent; those skillled
in the art will be aware of such groups ~e.g., halo (especially chloro and fluoro),
hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.);
~3) hetero substituents9 that is, substituents which will, while
having a predominantly hydrocarborll character within the context of this
invention, contain other than carbon present in a ring or chain otherwise
composed of carbon atoms. Suitable heteroatoms will be apparent to those of
ordinary skill in the art and include, for exsrnple, sulfllr, vxygen, nitrogen and
such substituents as, e.g., pyridyl, furyl, thienyl, imidazolyl, etc. In general, no
more than about 2, preferably oo more than one, non-hydrocarbon substituent
will be present for every 10 carbon atoms in the hydrocarbyl group. Often, therewill be no such non-hydrocarborl subssituents in the hydrocarbyl group and the
hydrocarbyl group is purely hydrocarbon.
WO 93/23504 PCT/US~2/08718
~ ~ s3
Oil of Lubricatin~ Viscosit~
The o~l which is utilized in the preparation of the lubricants of the
invention may be based on natural oils, synthetic oils, or mixtures thereof.
Natural oils include animal oll~ and vegetablc olls (e.g., castor oil,
lard oil) as well as mineral lubricating oils such as li~uid petrcleum oils and sol-
~rent treated or acid treated mineral lubricating oils of the paraffinic, naphthenic
or mixed paraffinic-naphthenic t~pes. C)ils of lubrlcating viscoslty derived from
coal or shale are also useful. Synthetic lubricating uils include hydrocarbon oils
and halo-substituted hydrocarbon oils ~uch as polymerized and ~nterpolyrnerized
olefins ~e.g., polybutylenes, polyprowlenes, propylelle-isobutylene copolymers,
chlorinated polybutylenes, etc.); poly(l-hexenes), poly(1-octenes), poly(l-dec-
enes), etc. and mixtures thereof; alkylbenzenes (e.g., dodecylbenzenes,
tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benæenes, etc.);
polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated
diphenyl ethers and alkyl~ted diphenyl sulfides and the derivatives, analogs andhomologs thereof and th~ llke.
Alkylene oxide polymers and interpolymers and derivatives thereof
where the terminal hydroxyl groups have been modified by esterification,
etherification, etc., constitute another class Or known syn~hetic lubricating oils
that can be used. These are exemplified by the oils prepared through polymer-
ization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of thesepolyoxyalkylene polymers ~e.g.9 methylpoiyisopropylene ~Iycol ether having an
average molecular weight of about 10009 diphenyl ether of polyethylene glycol
ha~ving a molecular weight of about 500-1000, diethyl ether of polypropylene
` 25 glycol having a molecular weight of about 1000-1500, etc.) ~r mono- and polycar-
boxylic ~esters thereof, for example, the acetic acid ~;sters, mixed C3-Cg fattyacid esters, or the C13 Oxo acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils that can be used
comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl
succinic acids, alkenyl succinic acids, maleic acid, a~elaic acid, suberic acid,
WO 93/2351M PCI'/lJS92J0871g~r.~
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sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl
malonic acids, alkenyl malonic ~cids, etc.) with a variety of slcohols (e.g., butyl
alcohol, hexyl alcohol, dodecyl alco~s)l, 2-ethylhexyl alcohol, etlhylene glycol,
diethylene glycol m~noether, propylene glycol, etc.) Specifîc examples of these
esters include dibu~yl ~dipate, di(2-ethylhexyl) sebacate, di-n-hexyl furnarate,dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, dide~fl
phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linolelc acid dimer, the
complex ester formed by reacting one mole oî ~baclc acid with ~wo moles of
te~raethylene glycol and two moles of 2-ethylhexanoic acid antl the likc.
Esters useful as syn~hetlc oils also include those made from Cs to
C12monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol,
trimethylol propane, pen~aerythritol, dipentaerythritol, tripen~aerythritol, etc.
Sllicor~-based oils such ~s the polyalkyl-, polyaryl-7 polyalkoxy-, or
polyaryloxy-siloxane oils and silicate oils cumprise another useful class of
15 synthetic lubricants (e.g., tetraethyl silic~te, tetraisoprowl silicate, tetra-(2-
ethylhexyl)silicate, tetra-(4-methylhexyl)silicate, tetra-~p~tert-butylphenyl)sili-
cate, hexyl-(4-methyl-2-pentoxy)disiloxane, poly~methyl)siloxanes, poly-
(methylphenyl)siloxanes, etc.). Other synthetic lubricating oils include liquid
esters of phosphor~ containing acids ~e.g., tricresyl phosphate, trioctyl phos-
20 phate, diethyl ester of decane phosphonic acid, etc.), polymeric tetrahydrofurans
and the iike.
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
hereinabove can be used in the concentrates of the present invention. Unrefined
25 oils are those obtained directly from a natural or synthetic source without
fur~her purification treatment. For example9 a shale oil obtained directly from
retorting operat~onst a petrvleum oil obtained directly from primary distillation
or es~er oil obtained directly from an esterification process and used without
further treatment would be an unrefined oll. Refined oils are similar tO the
30 unrefined oils except they have been further treated in one or more purification
WO 93t23504 PCr/l~S92~8718
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-1 1-
steps to improve one or more properties. Many such purification techni~ues are
known to those skilled in the art such as solvent extraction, hydrotreating,
~econdary distillation, acid or base ex~raction, filtration, percolation, etc.
Rerefilled oils are ob~ained by processes similar to tho~se used to obtain refined
oils applied to refined oils which have been already used in service. Such
rerefined oils are also known as reclaimed, recycled or reprocessed oils and often
are additionally processed by techniques directed to r~noval of spent addltives,oil contaminants such ~s water and fuel, and oil breakdown products.
(A) Carbox~ c D~rivatives.
Compvnent (A) which is utilized in the lubricatlng oils of the
present invention is at least one carboxylic derivative composition produced by
reacting ~A-1! at least one substitu~ed succinic acylating agent containing at
least about 50 carbon atoms in the substituent with (A-2) at least one amine
compound containing at least one HN~ group~ Generally ~he reaction involves
about 0.5 equlvalent up to about 2 moles of the amine compourld per equivalent
of acylating sgent. In one preferred embodiment, the acylating agent (A-1)
consists of substitue~ groups and succinic groups wherein the substituent groupsare derived from a polyaikene characterized by an Mn Yalue of about 1300 ,to
about 5000 and an Mw/Mn ratio of about 1.5 to about 4.5, and said acylating
agents are further~ ch~racterized by the presence within their structure of an
average of at least about 1.3 succinic groups for each equivalent weight of
substituent groups.
The carboxylic derivatives (A) are included in the oil compositions
to improve dispersancy and Vl properties of the oil compositions. In general from
about 1% andmore often from about 1.5% or 2~ to about 10 or 15% by weight
of component (A) can be included in the oil compositions, although the oil
compositions preferably will contain at least 2.5% and often at least 3% by
weight of component (A)~
The substituted succinic acylating agent (A- 1 ) utilized in the
preparation of the carboxylic derivatlve (A) can be characterized by the presence
.
WO 93~23504 PC~/US92/087
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within its structure of two groups or moieties. The first group or moiety is
referred to hereinafter, for convenience, as the "substituent group(s)" and is
derived from a polyalkene. The poly~lkene from which the substltuted groups are
derived is characterized in onei embodiment as containing at least about 50
carbon atoms and by ~n Mn ~number sverage molecular welght) v~lue of from
about 900 to ab~ut 5000 or even 10,000 ar hlgher. In one preferred embodiment
the Mn is from abuut 1300 to about 5000, and an Mw/Mn value of at least about
1.5 or at least 2.0 up to about 4.0 or 4.5. The abbreviation Mw Is the conYen-
tional symbol representing the weight average molecular we~ght. Gel permeation
chromatography ~GPC) is a method which provides both weight average and
nurnber aYerage molecular weights as well as the entire molecular weight dis-
~ribution of the polymers. For purpcse of this lnvention a serie~s af fract~onated
polymer~s of isobutene, polyisobutene, is used as the calibration s~andard in the
GPC.
The techniques for determining Mn and Mw values of polymers ~re
well known and are described in numerous books and articles. ~or exarnple,
methods îar the determination of Mn and molecular weight distribution of poly-
mers is described in W.W. Yan, J.J. Kirkland and D.D. Bly~ "Modern Size
Exclusion Liquid Chromatographs", J.Wiley & Sons, Inc., 1979.
The second group cr moiety in the acylating agent is refelTed to
herein as the "succinic group(s)".~ The succlnic groups ~re those groups
characterized by the structure
;
O O
1 ! X C C C C
wherein X and X' are the same or different provided at least one oî X and X' is
such that the substituted succinic acylating agent can function as carboxylic
acylating agent. That is, at least one of X and X' must be such that the
substituted acylating agent ~can form amides or amine salts with amino
WO 93/2350q PCI'/USg2/1)8718
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-13-
compounds, and otherwise functivn as a conventional carboxylic acid acylating
agent. Transesterificstion and transamidation reactions are considered, Por
purposes of this invention, as conventional ~cylating reactions.
Thus, ~C and/or X' is usually -OH, -O-hy~rocarbyl, -O-M~ where 1~+
represents one equivalen~ of a metal, amrnonium or amine ca~ian, -NH2, -Cl~ -Br,and together, X and X' can be ~O- so as to form the anhydrlde. The specific
identity of any X or X' group whlch is not one of the above is not critical so long
as its presence does not prevent the remalning group froJn entering into acylation
reactions. Prefersbly, however, ~C and X' are each such that both carboxyl
functions of the succinic group ~i.e., both ~C~)X ~nd -C(O)X' can enter into
scylation reactions.
One of the unsatisfied ~alences in the grouping
I , I
-C-C-
of Formula I forms a carbon bond wi~h a carbon atom in the substituent group.
While other such unsatisfied ~slence may be satisfied by a similar bond with thesame or different substituent group, all but ~he said one such valence is usually
satisfied by hydrogen; i.e., -H.
In one embodiment, the substituted succinic acylating ~gents are
characterized by the presence within their structure of at least one succinic
group (that is, groups corresponding to Formula 1) for each equivalent weight ofsubstituent groups. In a preferred embodiment the substituted succinic acylatingagents are characterized by the presence of an average of at least 1.3 succinic
groups for each ~quivalent weight of substituent groups. For pur;poses of this
invention, the equivalent weight of substltuent groups is deemed to be the
number obtained by dividing the Mn value of the polyalkene from which the
substituent is derived into the total weight of the substituent groups present in
the substituted succinic acylating agents. Thus, if a substituted succinic
acylating agent is characterized by a total weight of substituent group of 5000
WO 93/2350q pcr/us92/o871x
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and the Mn value for the polyalkene from which the substituent groups are
derived is 2aoo, then that substituted succinic acylating agent is characterizedby a total 4f 2O5 (5000/2000=2.5) equivalent weights of substituent groups.
Therefore, that particular succinic acylating ~gent wlll be characterized by thepresence within i~s structure of at le~st 3.25 succinic groups to meet one of the
requlrements of the succinic acylating agents used in this imention.
Another requirement for ~e substltuted succinic acylating agents
in a preferred embodiment is that the subs~ituent groups mus~ have been derived
from a polyalkene characterîzed by an Mw/Mn value of at least about 1.5 or 2~0.
-
The upper limit of Mw/Mn will generally be about 4.0 or 4.5. Values of from 1.5
to sbout 4.5 are useful, and a ratio of 2 to about 4.5 i5 particularly useful.
Polyalkenes having the Mrl and Mw values discussed above are
known in the art and c~n be prepared according to conven~ional procedures. For
example, some of these polyalkenes are described and cxemplified in U.S. Paten~
4,234,435, and the disclosure of this patent relati~e to such polyalkenes is hereby
incorporated by reference. Several such polyalkenes, especially polybutenes, arecommerclally available.
In one preferred embodiment, the succinic groups will normally
correspond to the formula
-
-CH--C~O)R
CH2- C(O)R' (Il)
wherein R ~nd R' are each independently selected from the group consisting of
-OH, -Cl, -O-lower alkyl, and when taken together, R and R' are -O-. In the
latter casel the succinic group is a succinic anhydride group. All the succinic
~5 groups in a par~icular sucl inic acylating agent need not be the same, but they
can be the same. Preferably, the succinic groups will correspond to
WO 93/23504 P~r/US~2~08718
~ J ~. ',Y 1~ J j 5~ ~
-CH--C~OH -CH~ C ~
CH2- C~OH or ¦ / O (III)
O CH2- C~
~0
(A~ (B)
and mixtures of (Ill(A)) snd (111(B)). ProYlding substituted succinic acylat ag
agents whereln the succlnic groups are ~e same or differe~t ls wlthin the
ordinarg skill of the art and can be accompllshed through conrentiunal
procedures such 8S treating the substltuted succinic ~cylating agents themselves(for ex~nple, hydrolyzlng the anhydride ~o the free ~cid or converting the free
acid to an acid chloride with thionyl chloride) ~nd/or ~electing the appropriatemaleic ~r fuTnaric react~nts.
As prev~ously mentionsd, the rninimwn number of æuccinic groups
for each equivalent weight of substltuent group is at least 1 ~nd preferably 1.3.
The maximum number generally will not exceed 4.5. In another preferred
embodim¢nt~ the mlnlmlun wlll be abollt 1.4 succinic groups for each equivalent
weight of substituent group. A rarlge based on this minimum is at least 1.4 to
about 3.S~ and more :specificslly about 1.4 to about 2.5 succinic groups per
equivalent weight of substituent groups~
In addition to preferled substituted succlnic groups where the
preference depends on the number snd identity of succinic groups for each
..
equivalent weight of substituent groups, still further preferences are based on
the identity and characterization of the polyalkenes from which the substituent
':
25 ~ ~ groups are derived. ~
With respect to the value of Mn for example~ a minimum of about
00 and a maximurn ~of about~5000 are preferred with an Mn value in the range
of from about 1500 to about 5000~also be:ng preferred. A more preferred Mn
: ~
WO 93/23s04 pcr/uss2/o8718
--16--
value is orle in ~he range of from about 1500 to about 2800. A most preferred
,
range of Mn values is from about 1500 to about 2400.
Before proceeding to a further discussion of the polyalkenes from
which the substituent groups ~re derived, lt should be pointed out that these
preferred characteristics of the succinic ac~latlng agents ~e intended to be
understood as belng bothindep~ndent and dependent. They arQ in~ended to be
independen~in the s~nse that, for example1 a preference for a minlmum of 1.4
or 1.5 succinic groups per equivalent weight of substituent groups is not tied to
a more preferred value of Mn or Mw/Mn. They a~e Intended to be dependent in
the sense that, for ex~nple, whea a preferen~e for a minimum of 1.4 or 1.5
succinic groups is combined with more preferred values of Mn and/or Mw/Mn, the
combination of preferences does in fact descrlbe 5tili further more preferred
embodiments of the invention. Tbus, the various parame~ers are ~ntended to
stand alone with respect to the particular parameter being discu~sed but can also
be combined with other parameters to iden~ify fuu ther preferences. This ssrne
concept ls intended to appl~lr throughout the specification with respec~ to the
description of preferred values, ranges, ratios, reactants, and the like unJess a
contrary intent is clearly demonstrated or apparent.
In one embodiment, when the Mn of a polyalkene is at the lower
end of the range, e~g., about 1300,~the ratio of succinlc groups to substituent
groups derived from said polyalkene in the acylating agent is preferably higher
than the ratio when the Mn is, for example, 1500. ConYersely when the Mn of
the polyalkene is higher, e.g.9 2000, the ratio may be lower than when the Mrl of
~he polyalkene is, e.g., 1~00.
' 25 The polyalkenes from which the substituent groups are derived are
homopolymers and interpolyrners of pol~nerizable olefin monomers of 2 to about
16 carbon atoms, ususlly 2 to about 6 carbon atoms. The interpolymers are those
in which two or more olefin monomers; are interpolymerized according to well-
known conYentional procedures to forrn polyalkenes having units within their
structure derived from each of said two ~ or more olefin monomers. Thus,
.
WO 93/23504 PCI/US92/0~718
" .. I,; . ~, . ..
. i _7~ J i.~'
7-
"in~erpol~ner(s)" as used herein is inclusive of copolymers, terpol~nners,
tetrapolyrners, and the like. As will be apparent to those of ordinary skill in the
art, the polyalkenes from which the substituent groups are derived are often
conventionalty referred to as "polynlefin~s)".
The olefln monomers frorn which the polyalkenes ~re derived are
polymerizable olefln monomer~ characterlzed by ~he pre~ence of one or more
ethylenicaliy unsa~urated g20ups ~i.e., ~C=Cs); tbat ls, they are monoolefinic
monomers such as ethylene, propylene, butene-1, Isobuterle? ssld octene-1 or
polyolefinic monomers (ususlly dioleflnlc nnonomers) such as butadlene-1,3 ~nd
isoprene.
These olç:fin monomers are usually polyrnerizable teIminal olefins;
that is,, olefins characterized by the presence in ~heir structure of the group
~C=CH2. However, polymerizable intemal olefin monomers (sometimes referred
to in the literature as medial olefins) characterizRd by the presence within their
sl:ructure of the group
-C-C=C-C-
can slso be used to form the polyalkenes. when internal olefin monomers are
employed, they normally will be employed with t~ninal olefins to produce
-
polyalkenes which are irlterpolymers. For purposes of this invention, when a
particular pol~nerized olefin mo~omer can be classified as both a tem~inal olefin
and an in~ernal olefin3 it will be deemed to be a terminal olefin. Thus, 1,3-penta-
diene (i.e., piperylene) is deemed to be 8 terminal olefin for pw~po5es of this
invention.
Some of the substituted succinic acylating agents (A-1) useful in
preparing the carboxylic derivatives ~A) are known in the art and are described
in, for example, U.S. Paten~s 3,087,936 (LeSuer), 3,219,666 (Norrnan) and
4,234,435 (Meinhardt), the disclosures of which are hereby incorporated by
reference. The acylating agents described in the '435 patent are characterized
WO 93/23504 PCl/US92~0X71X
2~ 2~,r~
18
as containing substituent groups derived from polyalkenes having an Mn value of
about 1300 ~o about 5000, and an MwlMn value of about 1.5 to about 4.
There i5 a general preference for aliphatic, hydrocarbon polyalk
enes free from aroma~ic and cycloaliphatic groups. Wlthin this general
preference, there is a further preference for polyalkenes which are derived fromthe group consisting ot homopolymers an~ interpolyrners of ~erminal hydrocarbon
olefins of 2 to about lfi carbon atoms. Th~s further preference is quallfied by the
proviso that, while interpolymers of terminal olefins are usually preferred,
interpolymers optionslly csntaining up to about 40% of polymer unlts derived
from tnternal olefins of up to about 16 carbon atoms are also within a preferredgroup. A more preferred class of polyalkenes are those selected from the group
consisting of homopolymers and interpolymers of terminal olefins of 2 to about
6 carbon atoms, more preferably 2 to 4 carbon atoms. However, another
preferred class of polyalkenes are the lat~er more preferred polyalkenes
optionally containing up to about 25% of polyrner units derived from internal
olefins of up to about 6 carbon atoms.
Vbviously, preparing polyalkenes as described above which meet the
various criteria for Mn and Mw/Mn is within the skill of the art and does no,t
comprise part of the present invention. Techniques readily apparent to those in
the art include contrclling polymerization temperatures, regulating the amount
and type of polymerization initiator and/or catalyst, employing chain terrninating
groups in the polymerization procedure, and the like. Other conventional
techniques such as stripping ~including ~acuum str}pping) a very light end and/or
oxidatively or mechanically degrading high rnolecular weight polyalkene to
i ` 25 produce lower molecular weight polyalkenes can also be used.
In preparing the substituted succinic acylating agents of this
invention9 one or more of the above-described polyalkenes (or halogenated
deravatives thereof) is reacted with one or more acidic reactants selected from
the group eonsistislg of maleiF or fumarlc reactants of the general formula
WO ~3/23504 Pclr/USg2/0871~
, . . , , . ~ ; ,
-19-
X(O)C-CH=CH-C(O)X' (IV)
wherein X and X' are as defined hereinbefore in Formula 1. Freferably th~
malei~ and fumallc re~ctat~ts will be one or more compottnds correspondlng to
the formula
RC(O)-CH~CH-C~O)R' (V)
wherein R and R' are a~ prev~ously defined In Formula 11 herein. Ordinarily, themaleic or fwn~rlc reactan~, wlll be maleic acid, fumaric acid, maleic anhydride,or a mlxture oî ~wo or more of these. The maleic reactan~s are usually
preferred over the fumaric reac~ants because the former are more readily
available and are, in general, more readily reacted with the polyalkenes (or
de~ivatives thereof) to prepare the substituted succinic acylating agents of thepresent invention. The especially preferred reac~an~, are maleie acid, maleic
anhydride, and mixtures of these. Due to availability and ea~e of reaction,
malei~ anhydride will usually ~ empioyed.
Examples of patents describlng various procedlLres for prepariqg
useful acyla~ing agents include U.S. Patents 39215,707 ~Rense3; 3,219,666
(Norman et al); 3,231,587 (Rerlse); 3,912,764 (Palmer3; 4,110,349 (Cohen); and
4,234,435 ~Meinhardt et 81), and U.IC. 1,440,219, The disclosu~es of these patents
are hereby Incorporated by reference.
The relative amount ~of the polyalkene and maleic reactant used in
preparing the hydrocarbyl-substituted succinic acids will var~r according to theproportion of the succmic acid groups de3ired in the product. Thus, for each
mole of the polynner employed, one or more moles of maleic reactant may be
used depending upon whether one or more succinic acld ~roups are to be
incorporated in each polymer molecule. In general, the higher the m olecular
weight ofthe polymer,the greater the proportion of nnaleic reactant which may
be used. On the other hand,if a molar excess of the polymer reactantis used,
WV 93/~3504 PCI/US92/0871X ~
2 i ~ a I J
-20-
the excess polymer will simply remain in the product as diiuent without adverse
effect.
For convenience and brevity, the terrn "rnaleic reactant" is often
used hereinafter~ When used, it should be understood that the term is generic toacidic reactants selected from maleic and fumaric reactants corresponding to
Formulae (IV~ and (V) ~bove including a mlxture oî such reactants.
The acylating reagents described above are intermedintes in
processes for preparing the carboxyli~ deriv~tive compositions (A) comprising
reacting (A-1) one or more acyl~ting reagents wi~h (A-~) at least nne amino
compound characterized by the presence within Its structure o~ at least one HN~
group.
The amino compound (A-2~ characterized by the pre~cence within
its structure of at least one HN< group can be a monoamlne or polyamine
compour~d. Mixtures of two or more amino compounds can be used in the
reaction with one or more acylating reagents of thls invention. Preferably, the
amino compound con~ains at least one primary amino group (i.e., -NH2) and more
preferably the amine is a polyamine, especlally a ~olyamine containing at least
~wo -NH- groups, either or both o~ which are primary or secondary amines. The
amines may be aliphatic, cycloaliphatic. aromatic or heterocyclic amines. The
polyamines not only result in carbo~ylic acid derivative compositions which are
usually more effective as dispersant/detergent additives, relative to derivativecompositions derlYed from monoamines, but these preferred polyamines result
in carboxylic derivative compositions which exhibit more pronounced Vl
improving propertiesO
~nong the preferred amines are the alkylene polyarnines, including
the polyalkylene polyamlnes. The alkylene polyamines include those conforming
to the forrnula
` ~ ~
R3N-~U-NI )n~R3 (Vl)
`
. :
WO ~3/23504 Pcr/US92/~871~
t ~ , . ". ., . ~ ,
-21-
wherein n is from 1 to ~out 10; each R3 is independently a hydrogen atom, a
hydrocar~yl group or a hydroxy-substituted or amine-subs~ituted hydrocarbyl
group having up to ab~ut 30 atosrls, sr two R3 graups un different ni~;rogen atoms
can be joined together to form a U group, with the proviso that at least one R3
group is a hydrogeo atom and U is an alkylene group of about 2 to about 10
carbon atoms. Preferably U i5 ethylene or propylene. Especlally preferred are
the alkylene polyamines where each ~3 is hydrogen or an amino-substituted
hydrocarbyl group with the ethylene polyamine~s and mixtures of ethylene
poly~mines being the most preferred. Usually n will have an aver~ge value of
from about 2 to about 7. Such alkylene polyamines include methylene polyamille,
ethylene polyamines, butylene polyamines~ propylene polyamines, pentylene
poly~nines, hexylene polyamines, heptylene poly~nines, et~. The higher homo-
logs of such amines and related amino alkyl-substituted piperazines are also
included.
lS Alkylene polyamines useful in preparing th¢ csrboxylic derivative
compositions (A) include ethylene dl~nlne, triethylene tetramine, propylene
diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamineJ
hexamethylene diamine, dec~rnethylene diamine, octamethylene diamine,
di(heptametbylene) triamine, tripropylene tetrarnine, tetraethylene pentamine,
trimethylene diamine, pentaethylene hexamine, di(trimethylene)triamine,
N-(2~ oethyl)piperazine,~ 1 ~4-bis(2-sminoethyl)piperazin¢, and the like. Higherhomologs as are obtained by condensing two or more of the above-illustrated
alkylene amines are useful, as are mixtures of two or more of any of ~he
afore-described polyamines.
Ethylene polyamines, such as those mentioned above, are especially
useful for reasons of cost and effectiveness. Such polyamines are described in
detail under the heading !'Diamines and Hig31er Amines" in The Encyclapedia of
Chemical Technology, Second Edition, Kirk and Othmer, Volurne 7, pages 27-39,
Interscience Publishers, Dlvision of John Wilcy and Sons, 196~, which is hereby
incorporatcd by referFnce for the disciosure of useful polyamines. Such
: ~ :
WO 93/23504 PCr/~JS92/~871~ .
3,/.~ h
-22-
compounds are prepared most conveniently by the reaction of an alkylene
chloride with arnmonia or by reaction of an ethylene imine with a ring-opening
reagent such as ammsnia, etc. These reac~ions result in the production of the
sornewhat complex mixtures of alkylene polyamines, including cyclic conden-
sation products such as piperazines. The mixtures are particularly useful in
preparing carboxylic derl~ra~i~re (A) useful In this inventlon. On the other hand,
quite satisfactory products can also be obtained by the use of pure alkylene
polyamines.
Other useful types of poly~nine mixtures ~e those resulting frorn
stripping of the above-de~cribed polyamine mixtures. In this instance, lower
molecular weight polyaTnines and volatile contaminan~s are removed from an
alkylene polyamine mixture to leave as resldue what ts of ~en termcd "polyamine
bottoms". In general, ~lkylene polysmine botton~ can be characterized as having
less than two, ~sually less than 196 (by weight) material boiling below about
200C. In the instance of ethylene polyamine ~ottoms, which are readlly
available and found to be quite useful, the bottoms contain less tb~n about 2%
(by weight) total diethylene triamine ~DEIA) or triethylene tetramine (TEIA).
A typical sample of such ethylene polyamine bot~oms obtained from the Dow
Chemical Company Qf ~reeport, Texas designated "E-}00l' showed a spPcific
gravity at 15.6C of 1.0168, a percent nitrogen by weight of 33.15 and a viscosity
at 40C of 121 ~centistokes. Gas chroma~ography analysis of such a sample
showed It to contain about 0.93h "Light Ends" (most probably DETA), 0.72%
TEI`A, 21.74% tetraethylene pentamine and 76.61% pentaethylene hexamine and
higher ~by weight~. These alkylene polyamine bottoms include cyclic condensa-
tion products such as piperazine arld hi~her analogs of diethylenetriamine~
triethylenetetramine and the like.
These alkylene polyamine bottoms can be reacted solely with the
acylating agent, in which case the amino reactant consists essentially of alkylene
polyamine bottoms, or they can be used with other amines and polyamines, or
WO 93/23504 P~/US92/08718
~ t. 'J '.~1 ', J ~ :.J
23-
alcohols or mixtures thereof. In these latter csses at least one amino reactant
comprises alkylene polyamine bottoms.
Other p~lyamines which can be reacted wlth the acylating agents
(A 1) in sccordance with this invention arè descrlbed in, for example, U.S.
Patents 3,219,666 and 4,234,435, and these paten~s are hereby incorporated by
referenc~ for their disclosures of amines whlch can be reacted wi~h the acylatlng
agents described above to form the carboxyllc derivatives (B) of thls invention.In anu~h~r embodiment, the amine may be a bydroxyamine.
Typ~cslly, the hydr~xya~mines are primary, secondary or tertlary alkanol amines
or mixtures ~hereof. Such amines can be represented by the formulae:
H2N-R'-OH~ (Vll)
and
R'lN~H)-R'-OH (VIII)
wherein each R'l is independently a hydrocsrbyl group of one to about eight
carbon atoms or hydroxyhydrocsrbyl group of two to about ~ight carbon atoms,
preferably one to about four, and R' is a divalent hydrocarby} group of about t~o
to about 18 carbon atoms, preferably two to sbout four. The group -R'-OH in
such formulae represents the hydroxyhydrocarbyl group. R' can be an acyclic,
alicyclic or aromatic group. Typically, R' is an acyclic straight or branched
~0 alkylene group such as an ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadeeyl-
ene, etc. group. Where two R'l groups are present in the same molecule they
can be joined by a direct carbon-to-carbon bond or through a heteroatom (e.g.,
oxygen, nitrogen or sulfur) to form a 5-j 6-, 7- or 8-membered ring structure.
Examples of such heterocyclic amines include N-(hydroxyl lower al-
kyl)-morpholines, -thiomorpholines, -piperidines, -oxazolidines, -thiazolidines and
the like. Typically, however, each R'l is independently a methyl3 ethyl, propyl,butyl1 pentyl or hexyl group.
~YO ~3/2350~ PCJI~/US92/0871~ -~
2; ~S ~
-2~-
Examples of these alkanolamines include mono-, di-, and triethanol
amine, diethylethanolamine, ethylethanolamine, butyldie~hanolamine, etc.
The hydroxyamines can also be an e~her N-(hydroxyhydrocarbyl)-
~nine. These are hydroxypoJy(hydrocarbyloxy) analogs of the above-described
hydroxy amines ~these analogs alsv include h~droxyl-substltuted oxyalkylene
analogs). Such N-~hydroxyhydrocar~yl) amines can be conveniently prepared by
reactlon of epoxides with afore-clescribed amines and can be represented by the
formulae:
H2N~ O)x-~ (IX)
and
R'lN~H)-~R'O)XH (X)
wherein x is a number from about 2 to about 15 and Rl and E~' are a~ described
above. R'l may also be a hydroxypoly(hydrocarbyloxy) group.
The carboxylic derivative compositions (A) produced from the
lS acylating reagents ~A-l) and the aminn compounds (A-2) described hereinbefore
comprise acylated amines which include ~nine salts, amides, imides, amidines,
amidic acids~ amidic salts and imidaxolines as well as mixtures thereof. To
prepare the carboxylic acid derivatives from the acylating reagents and the
amino compounds, one or more acylat~ng reagents and one or more amino
compounds are heated, optionally in the presence of a norrnally liquid, substan-tially inert organic li~uid solvent/diluent, at temperatures in the range of about
80C up to the decomposition point of either the reactants or the carboxylic
derivative but normally at temperatures in the range of about ~00C up to about
300C provided 300C does not exceed the decompositlon point. Temperatures
of abou~ 125C to about 250C are normally used. The acylating reagent and the
amino c~mpound are reacted in amounts sufficient to provide from about
one-half equivalent up to about 2~moles of amino compound per e~uivalent of
acylating reagent.
.
WO 93/23504 P~r/~S92/Og7~
J .~ !J , ~,~
-25-
Because the acylating reagen~s ~A- 1 ) can be reac~ed with the amine
compounds (A-~) in the same manner as the hlgh molecular welght acylating
agents of the prior art are reacted with amines, V.S. Patents 3,172,892;
3,219,666; 3,272,746; and 4,234,435 are expressly incorporated herein by
refelence for their disclosures wlth respect to ~he procedures applicable to
resctlng the aQlating reagents wl~b the amino compaunds as descrlbed above.
ln order to produce carboxyllc deriv~ive compositio~s exhiblting
viscosity index improvlng capabilit~es, lt has been found generally necessary toreact the acylating reagents wlt:h polyfunctional ~znlne reactants. For exarnple,
polyamines having two or more primary ~nd/or secondary amino groups are
preferred. Obviously, however, it is not necessary that all of the amino com-
polmd reacted with the acylating reagents bP polyfunctional. Thus, combinations
of mono and polyfunctional amino compounds be used.
The acylating agent i5 reacted with fram about 0.5 eqtlivalent up
to about 2 moles of the arnine compound per equivalent of acylating agent. In
another e~nbodiment, the amount of ~ine may range from 0.7 up to about1.5
equivalents per equ~valent of acylating agent.
In another embodiment, the acylating agent is reacted with from
aboutO.5 and more often 0.7 equivalent up toless than 1 equivalent (e.g., about
0.95 equivalent) of amine compound, per equi~alent of acylating agent. The
lower limit on the equi~alents of amine compound may be 0.75 or even 0.80 up
to about 0.90 or 0.9$ equivalent, per equivalent of acylating agent. Thus
narrower ranges of equivalents of acylating agents (A-l) to amine compounds
(A-2~ may be from about 0.70 to about 0.90 or about 0.75 to about 0.90 or about
I
` 25 0.75 to about 0.85. It appears, at least in some situations, that when the
equivalent of amine compound is about 0.75 or less, per equivalent of acylating
agent, the effectiveness of the carboxylic derivative as a dispersant is redueed.
In yet another embodiment, the acylating agen~ is reac~ed with
from about 1.0 equivalent up to 2 moles of amine per equivalent of acylating
WO ~3/235(~4 P~/US92/0~71g,~
2 J ~ J ~-J
-26-
agent. More often the acylating agent is reacted with from ~bout 1.0 or 1.1 up
tO l.S equivalents of amine per equivalent of acylating agent.
The amount of' amine compound (A~-2) within the above ranges that
is reacted with the acylating agent ~-1) msy also depend in part on the number
and type of n~trogen atoms present. For exsmple, 1 smaller amount of a
polysarnine containing one or mvre -NH2 groups is required to react with a givenacylating agent than a polyamlne ha~ing the s~rne number of nl~rogen atoms and
fewer or no -NH2 groups. One -NH2 group can react wi~h two -COOH groups to
form an ~rnide. If only secondary nitrogens are pre~ent in the amine compound,
ea- h ~NH group can react with only one -COOH group. Accardlngly, the arnount
of polyamine within the above ranges to be reacted with the acylating agent to
form the carboxylic derivat~ves of the Inventlon can be read~ly determined from
a consideration of the number and types of nltrogen atoms in the polyamine (i.e.,
-I~IH2, ~NH, and >N-).
lS In addition to the relative amoun~s of acylatlng agent and amine
compound used to fo~n the c~boxylic derivat}ve composition (A), o~her features
of the carboxylic derivatiYe compositlons used in this invention are the Mn and
the Mw/Mn values of the polyalkene as well as the presence within the acylating
agents of an average of at least 1 and preferably at least 1.3 succinic groups for
each equivalent weight of substitllent groups. When all of these features are
present in the carboxylic derivative compos~tions (A), the lubricating oi1
cornpositions of the present invention are characterized by imprvved perfor-
mance in combustion engines.
The ratio of succinic groups to the e4uivalent weight of substituent
group present in the scylating agent can be determined from the saponification
nwnber of the reacted mixture c~rrected to account for unreacted polyalkene
present in the reaction mixture at the end of the reaction (generally referred to
as filtrate or residue in the following examples). Saponification number is
deterrnined using the ASTM D-94 procedure. The formula for calculating the
ratio from the saponification nwnber is as follows:
WO 93/23504 PCr/US92/0871 X
,~ ~3 ~
Ra~io = (Mn~(SaD No..co~Tected)_
112,2ûO-gB(Sap No.,corrected)
The corrected saponlfic~tion nwnber is obtained b~r dividing the
s~ponification ntunber by the percent of the polyalkerle ~hat has reacted. For
exarnple, if 10% o~ ~he polyalkene dld no~ reac~ and the saponificatlon number
of the filtrate or res~due Is 95, the corrected saponification number is 95 disrlded
by 0.90 or 105.5.
The preparation nf the acy}atlng agents is ~llus~rated in the
following Examples l-ff and the preparatioll o~ the carboxylic acid derivative
compositlons (A) ls illustrated by ~he following Examples A 1 to A-29. In the
following examples, ~nd elsewhere in the specifica~ion ~nd claims, all percentag-
es and parts are by welght, temperatures are ~n degre~s centlgrade and pressuresare a~nospheric unless otherwise clearly indicated. The desired acylating agentsare sometimes referred to ln the examples as ~Iresidue1~ without speclflc
determination or mention of other mate~ials present or the amoun~s thereof.
A~YIatin~ A~ents
Example 1
A mixture of 510 p~rts (0~28 mvle) of polyisobutene (Mn=1845;
Mw-5325) and 59 parts (0.59 mole) of rnaleic anhydride is heated to 110C~ This
mi~ture is heated to 1 90C in 7 hours during which 43 parts ~0.6 mole) of gaseous
chlorine is added beneath the surface. A~ 190-192C an addisional 11 parts (0.16mole) of chlorine is added over 3.5 bours. The reaction mixture is stripped by
heaeing at 190-1~3~C: with nitrogen blowing for 10 hours. The residue is the
desired polyisobutene-substituted succinic acylating agent having a saponification
equivalent numbeF of 87 as determined by ASTM procedLIre D-94.
Example 2
~ mixture of 1000 parts (0.495 mole~ of polyisobutene ~Mn=2020;
Mw=6049~ and 115 parts (1.17 moles) of maleic anhydride is heated to 110C.
This mixture is heated tO 184C in 6 hours during which 85 parts (1.2 moles) of
WO 93/23~ PCr/US92/V8718 ~
2 ~
-28-
gaseous chlorine is added beneath the surface. At 184-189C an additional 59
parts ~0.83 mole) of chlorine ~s added over 4 hours. The reaction mixture is
stripped by heating at 186-190C wlth nltrogen blowing for 26 hours. The re~sidue
is the de.sired polyisobutene-substltuted succlnic acylating agent having a
saponification equivalent number of 87 as determltled by A5TM procedure D-94.
Example 3
A mixture of 3251 parts of polylsobutene chloride, prepared by the
addltion of 251 parts of gaseous chlorlne to 3000 part~ of polyisobutene
(Mn-1696; Mw=6594) at ~0C in ~.66 hours, snd 345 parts of maleic anhydride is
heated to 200"C in 0.5 h4ur. The reactlon mlxture is held at Z00-224C for 6.33
hourst str~pped at 210C under vacuulTl and flltered. The filtrate is the desired
polyisobutene-substituted succinic acylsting agent ha~ring a saponification
equivalent number of 94 as determined by ASTM procedure D-94.
Exarnple 4
A polyisobutenyl succinic anhydride is prepared by the reaction of
1 mole of a chlorinated polyisobutylene with 1 mole of maleic anhydrlde at
200C. The polylsobutenyl group has an average molecular weight of 85~, and
the resulting substituted succinic anhydride is found to have an acid nurnber of113 (corresponding to,an equivalent weight of 500~.
Example 5
A polyisobutenyl succinic anhydride havi~g an acid number of laS
and an equivalent weight of 540 is prepared by the reaction of 1 mole of a
chlorinated polyisobutylene (having an Mn of about 1050 and a chlorine content
of 4.3~) and 1 mole of maleic anhydride zt a temperature of about 200C.
1 Example 6
~ substituted succinic anhydride is prepared by reacting 1 mole of
maleic anhydride with 1 mole of a chlorinated copolymer of isobutylene and
styrene. The copolymer consists of 94 psrts by weight of isobutylene units and
6 parts by weight of styrene units, has an Mn of about 1200, and is chlorinated
WO 93/23~04 P(~/US92/U8718
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to a chlorine content of 2.8% by weight. The resulting substituted succinic
anhydride has an acid number of 40.
CarboxYlic Derivati~e Com~osi~i~ns ~A
Example A-l
A mL~c~ure is prepared by the addltlorl of 10.2 parts 10.25 equiva-
lent) of a commerc:ial mixture of ethylene polyamines having from about 3 to
about 10 rli~rogen atsms per molecule to 113 p~rts of mineral oil ~nd 161 parts
~0.25 equivalent) Df the substttuted succinic acylating ~gent prepared In Ex~nple
1 at 138C. The reaction mixture is he~ed to 1$0C In ~ ht~urs and stripped by
blowing with nitrogen. The reaction mixture is filtered to yield the filtrate asan oil solution of the desired produet.
Example A-2
A mixture is prepared by the addltion of ~7 parts ~1.38 e~uivalents)
of a commercial mixture of ethylene polyamines having from about 3 to 10
nitrogen atoms per molecule to 10~7 parts of mineral oil arld 893 parts ~1.3~
equivalents) of ~he substituted succinie a~,rlating sgent prepared in Example 2
at 140-145C. The reaction mixture is heated to 155C in 3 hours and stripped
by blowing with nitrogen. The reaction mixture is filtered to yield the fil~ra~eas an oil solution of t~e desired product.
E:xarnple A-3
A mL~cture of 1132 parts of mineral oil arld 709 parts (1.2 equi-/a-
letlts) of a subst~tuted succinic acylating agent prepared as in Example 1 is
prepared, and a solution of 56.8 parts of piperazine (1.32 equivalents) in 200 parts
Qf water is added slowly from a dropping funnel to the abo~e mixture at
130-140C over approximately 4 hours. Heating is continued to 160C as water
is removed. The mixture is maintained at 160-165C for one hour and cooled
overrJight. After reheating the mixture to 160C, the mixture is maintained as
this temperature for 4 hours. Mineral oil (27CI parts) is added, and the mixtureis filtered at 150C through a fil~er aid. The filtratP is an oil solution of the
desired product ~65% oil) containing 0.65% nitrogen (theory, 0.~6%).
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Example A-4
A mix~ure of 1968 parts of mineral oil and 1508 parts ~2.5
equi~ralents) a substituted succinic soylating agent prepared as in Example 1 isheated to 145C whereupon 125.6 parts (3.0 equivalents) of a commercial mixture
of ethylene polyamines as used in Ex~ple A-1 are added oYer a period of 2
hours while malntslning the re~c~ion teanperature at 145-150C. The reactlon
mixture is stirred for 5.S hours at 150-152C while blowing with nitrogen~ The
mixture is filtered at 150C wlth a fllter ald. The fil~rate ls an oil solution of
the desired product (559~ oll) contnitling 1.2û~ nltrogen ~theory, 1.17).
Exarnple A-~
A mlxture of 4082 par~s of mineral oil and 250.8 parts (6.24
equivalents) of a commercial mixture of ethylene polyamlne of the type utilized
in Example A-1 is heated to 110C whereupon 3136 parts (5.2 equivalents) o~ a
substituted succlnic acylating agent prepared as in E:xarnple 1 are added over a: 15 period of 2 hours. During the addition, the temperature is maintained at
110-120~C while blowing wlth nitrogen. When all of the amine has been added,
the mixture is heated to 160C and maintained at this temperature for about 6.5
hours while removing water. The mixture is filtered at 140C with a filter aid"
:~ and the filtrate is aD oil solution of the desired product (55% oil) containing
ZO 1.17% nitrogen (theory, 1.18).
Exarnple A-6
A mixture of 4158 parts of mineral oil and 3136 parts (5.2
equivalents) of a substituted suc~inic ~cylating sgent prepared as in Example 1
is heated to 140(:~ whereupon 312 parts ~7.26 equivalents) of a corr~nercial
mixture of ethylene polyamines as used in Exarnple A-l are added over a period
of one hour as the temperature increases to 140-1 50C. The mixture is
maintained at 150C for 2 hours while blowing with nitrogen and at 160C for 3
hours. The mixture is filtered at 140C with a filter aid. The filtrate is an oil
solution of the desired product (55% oil) containing 1.44~ nitrogen (theory, 1.34).
::
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Example A-7
A mixture of 4053 parts of mineral oil and 287 parts (7.14
equivalents) of a coznrnercial mLlcture of ethylene poly~nines as used in Exaznple
A-l is heated to llû~C whereupon 307S p~ s (5.1 equlv~lents) of ~ substituted
succlnic s~lating ~gent prep~red as in ~cample 1 are added over ~ perlod of one
hour whlle maintainlng the tempera~ure at about llO~C, The mixture is heated
to 160C over a perlod of 2 hours and held at thls temper~ture for an addition~l4 hours. The reactlon m~xture then is filtered at 150C wlth fllter ald, and theflltra~e is an oil solution o~ the desired product; ~55% ~il) contalnlng 1.339
nitrogen (theory, 1~36).
Example A-8
A mixture of 1503 parts of mlneral oll ~nd 1220 parts ~2 equiva-
lents) of a substltuted su~cinic ac~ ing ~gent prepared as In Example 1 is
heated to 110C whereupon 120 parts (3 equlvalen~s) of a comrnerclal mixture
of ethylene polyalTIines of ~he type used in Ex~nple A-l are added over a periodof about 50 minutes. The reactlon m~xture ~s stirred an additional 30 minutes at110C, and the ternperature is then raised to and maintained at about 151C for
4 hours~ A filter aid is added and the mixture is flltered. The filtrate is an oil
solution of the desired product ~53.2~ oil) containing 1.44% nitrogen (theory,
~0 1.49).
Ex~mple A~9
~ A mixture of 3111 parts of mineral oil and 844 par~s (21 equiva-
lents) of a commercial mixture of ethylene polyamine as used in Example A-1 is
heated to 140C whereupon 3885 parts (7.0 equivalents) of a substituted succinic
,
acylating agent prepared as in E~ample 1 are added over a period of about 1.75
hours as the temperature increases to about l SDC. While blowing with nitrogen,the mixture is maintained at 150-15~C for a period of about 6 hours and
thereafter filtered with a filter aid at 13~C. The filtrate is an oil solution of
the desired produc~ (40% oil) containlng 3.5% nitrogeD (theory, 3.78).
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Example A-10
A mixture is prepared by the addition of 18.2 parts (0.433
equivalent) of a commercial mixture ~f ethylene polyamin~s having from about
3 to 10 nitrogen atoms per molecule tD 392 parts of mineral oil and 348 parts
(V.52 equ~valent~ uf ~he substltuted succlnic acyl~tIng agent prepared in ~cample
2 at 1~ûC. The reaction mlxture is he~ted to 150C ln 1.8 hours and stripped
by blowing with nit~ogen. The re~ction mixture is flltered to yleld the fil~rateas an oil solution (55% oil) of the deslred product.
Example A-11
An nppropriate size flask fi~ted wlth a stirrer, nitrogen inlet tube,
addition fun~lel snd Dean-S~ark trap/condenser is charged wlth a mixture of 24B3parts acylatlng agent (4.2 equivalents~ as described In Ex~Tnple 3, and 1104 par~s
oil. This mixt~e is heated to 210C whlle nil:rogen was slowly bubbled through
the mixture. Ethylene polyamine bottoms (134 parts, 3.14 equivalents) ~re slowlyadded over about one hour zt this temper~ture. The temperature is maintained
at about 210C for 3 hours and then 3688 p~rts oil is ~dded to decrease the
temperature to 125C. After stora~e at 13~C for 17.5 hours, the mixture is
filtered through diatomaceous earth to provide a 65% oil solution of the desir~d~cylated arnine bottoms.
Example A-12
A mix~ure of 3ff60 parts (6 equivalents) of a substituted succinic
acylating agent prepared as in Example 1 in 4664 parts of diluent oil is prepared
and heated at about l l O~C whereupon nitrogen is blow:n through the mixture. Tothis mixture there are then added 210 parts t5.25 equivalents) of a commercial
mixture of ethylene polyamines containing from about 3 to about 10 nitrogen
atoms per molecule over a period of one ho~ and the mixture is rnaintained at
110C for an additional 0.5 hour. After heating for 6 hours at 155C while
removing water, a filtrate is added and the reaction mixture is filtered at about
lSOC. The filtrate is the oil solution of the desired product.
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Example A-13
The ~eneral procedure of Example A-12 is repeated with the
exception that 0.8 equivalent of a substituted suc:cinlc acylating agent as
prepared in Example 1 i~ reacted wl~h 0.67 equlvalent of ~he colr~nercial mlxture
of ethylene polyaminesl The product obtained in this marmer is an oil solution
of the product containing 55% diluent oll.
Example A~14
The general procedure of Ex~nple A-12 is repeated except that the
polysmine used in this example Is ~n equivalerlt amount of an alkylene polyaminemixture comprising 80% of ethylene polyamine bottum~ from 1)niorl Carb}de and
20% of a commer~ial mixture of ethylene polyamines corresponding In empirical
for~ula to dlethyleDe triamine. Tb1s polyamine mixture is characterized as
having an equiYalent weight of about 43.3.
Example A-15
The general procedure of Example A-12 is repeated except that the
polyamine u~ilized in this example comprises a mixture of 80 parts by weight of
ethylene polyamine bottoms svailable from Dow and 20 parts by weight of
diethylenetriarnine. This mixture of amines has an equivalent weight of abo~lt
41.3.
Example A-16
A mixture of 444 parts (0.7 equivalent) of a substituted succinic
acylating agent prepared as in Example 1 and 563 parts of mineral oil is prepared
and heated to 140C whereupon ~22.2 parts of an ethylene polyamine mixture
corresponding in empirical formu1a to triethylerle tetramine (0.58 equivalent) are
added over a period of one hour as the temperature is maintained at 140C. The
mixture is blown with nitrogen as ~t is heated to 150C and maintained at this
temperature for 4 hours while removing water. The mixture ~hen is filtered
through a filter aid at about 135C, and the fi1trate is an oil solution of the
desired product comprising abou~ 55%~oi mincral oil.
:
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Example A-17
A mixture of 422 parts ~0.7 equivalent) of a substituted succinic
acylatlng agent prepared as in Example 1 and 18B parts of mineral oil is prepared
and heated to 210C whereupon 22~1 parts (0.53 equivalent) of a cornmercial
5 mlx~ure of ethylene polyamine bottoms from Dow ~re added over a perlod of one
hour blowing with n~trogen. The temperature then i5 increased to about
210-216~C ~nd maintained at this temperature for 3 hours. Mlneral oil (625
parts) is added and ~he mlx~ure is maintained a~ }35C for abou~ 17 hours
whereupon the mixture Is filtered and the filtrate Is an oil solu~ion of the desired
product ~659~ oll).
Example A-18
The general procedure of Ex~mple A-17 is repeated except that the
polyamine used in this ex~ple is a commercial mixture of ethylene polyamines
ha~ring from about 3 to 10 nitrogen atonu per molecu}e (equivalent weight of 42).
lS Exampl~ ~-19
A mixture is prepared of 414 parts (0.71 equivalent) of a substitut~
ed succinic acylsting agent prepared as in Example 1 and 183 parts of mineral
oil. This mixture Is heated to 210C whereupon 20.5 parts ~0.4g equivalent) of
a cornmer~ial ~ ture of ethylene polyamines having from about 3 to 10 nitrogen
atoms per molecule are added over a period of about one hour as the tempera-
ture is increased to 210-217C. The reaction mixture is maintained at this
temperature for 3 hours while blowing with nitrogen, and 61~ parts of mineral
oil a~e added.: The mixture is msintained at 145-135C for about one hour, and
at 135C for 17~hours. The mixture Is filtered while hot, and the filtrate is anoil solution of the desired product (65~ cil).
Example A-2û
A mixture of 414~parts (0.71 equivalent) of a substituted succinic
acylating agent prepared as in Example 1 and 184 parts of mineral oil is prepared
and heated to about 80C whereupon 22.4 parts (0.534 equivalent) of melamine
are added. The mixture is heated to 160C over a period of about 2 hours and
~: :
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maintained at this temperatu~e for 5 hours. After cooling overnight, the mixtureIs heated to 170C over 2.5 hours and to 215C over a period of 1.5 hours. The
mixture is maintained at about 215C for about 4 hours arld at about 220C for
6 hours. After cooling o~Jernlght, ~he reac~lon mlxture is filtered at 150C
through a filter aid. The filtrate Is an oil solut~on of the de~ired product (30%
mlneral oll).
Example A-21
A mLxture of 414 parts ~0.71 ~qu~valent) of a substi~uted acy~ating
agent prepared ~s ln Example 1 and 18~ par~s of mineral oil Is heated to 210C
1~ whereupon 21 parts ~0.53 equivalent~ of a commercial mlxture of ethylene
polysrnlne corresponding in empirical formuls ~o tet~sethylene pentamin~ are
added over a period of 0.5 hour as the temperature i5 maintained at about
210-217C. lJpon completion of the ~dditlon of the pvlyamine, the mixture is
maintained at ~17C for 3 hours while blowing with nltrogen. Mineral oil is
added ~613 parts) and the mixture is maintained at sbout 135C for 17 hours and
filtered. The filtrate ~s an oil solution of ~he desire~ product (65% mineral oil).
ample A-22
A mixture of 414 parts (0.71 equivalent) of a substituted a~ylati~g
agent prepared as in Example 1 and 183 parts of mineral oil is prepared and
heated to 210C whereupon 18.3 par~s (0.44 equivalent) of ethylene amine
bottoms ~Dow) are adde~ over~a period of one hour while blowing wlth nitrogen.
The mixture is heated to about 210-217C in about 15 minutes and maintained
at this temperature for 3 ho~s. An additional 608 parts of mineral oil are addedand the mixture is maintained at about 135~C for 17 hours. The mixture is
filtered at 135C through a filter aid, and the filtrate is an oil solution of the
desired product (65% oil~
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Ex~nple A-23
The general procedure of Example A-22 is repeated except that the
ethylene amine bottoms are replaced by an equi~slent amoUIIt of a comrnercial
m~xture of ethylene poly~mines haYing from ~bout 3 to 10 nitrogen atoms pe
molecule.
Exa~nple A-24
A mlxture of 422 pa~s ~0.70 equi~lent~ of a subs~ituted acylatlng
agent prepared ~s }IJ Ex~nple 1 at~d 190 p~cs of mlneral oil Is hsated to 210C
whereupon 26.75 parts (0.636 equiYalent) of ethylene amine battoms ~Dow) are
added over one hour while bl~wing with nl~rogen. After all of ~he ethylene
amine is added, the mixture is malntalned ~t 210-~15C for about 4 hours, and
632 parts of mlneral oil are added wit~a stirrlng. This mixture is maintained for
17 hours at 135C alld filtered through a filter aid. The filtrate is an oil soluti~n
of the desired product (6596 oll).
a5 . Example ~-25
A mixture of 468 parts (0.8 equivalent) of a substituted succlnic
ac:yla~ing agent prepsred as in Example 1 and 908.1 parts uf mineral oil is beated
to 142C whereupon 28.63 parts (007 equivalent) of ethylene asnine bottoms (Dow)are added over a period of 1.~2 hours. The mixture was stirred an additional 4
;~ 20 hours at about 142C and filtered. The filtrate is an oil solution of the desired
:: product ~65% oil).
EX~T1PIe A-26
A mixture of 2G53 parts of a substituted acylating agent prepared
. ~
as in ExaTnple 1 and 1186 parts of mineral oll is heated to 210C whereupon 154
2~ parts of e~hylene amine bottoms (Dow)~sre added over a period of 1.5 hours as
:~ :; the temperature is maintained~between 210-215C. The mixture is maintained
~ ` :
at 215-220C for a:period of about 6 hours. Mineral oil ~3953 parts) is added at
210C~ and the mixture is stilTed for l7 hours with nitrogen blowing at 135-128C.
: ~ The mixture is filtered hot through a filter aid~ and the filtrate is an oil solution
of the desired product (65% oil). ~ ~
W093/23504 r ~ 3 1 ' ' PCl/US92/0871~3
Example A-27
To a mix~ure of 500 psr~s (1 equivalent) of the polyisobutenyl
succinic anhydrlde prepared in Example 4, and to 160 parts of ~oluene, there areadded at room temperature, 35 parts (1 equIvalent) of diethyl0ne triam}ne. The
addlt{on i5 made portionwise through a period of 15 minu~es, and an Initial
exothermic reaction causes 1:he temperature to rise to about 50C. The mixture
is heated and a water-toluene azeotrope ~ dlstllled from the mlxture. When no
addltional water dlstills, the mlxture 15 heated to 1$0C: at reduced pressure to
remove the toluene. The residue i~ diluted wlth 300 psrts of mineral oll, and this
solution is found to have a nitrogen content of 1.
Example A~28
To a mixture of 300 parts by welgh~ of the polyisobutenyl succlnlc
anhydride prepared in Example 5, and 16û psrts by welght of mineral oil, there
is added at 6~95C, an equivalent amount ~25 parts by weight) of Poly~rlirIe H
which is an ethylene~nlne mixture having atl average composltion corresponding
to that of tetraethylene pentamine. The mixture is then heated to 150C to
distlll water formed ~n the reaction. Nitrogen is bubbled thrQugh the mixture atthis temperatur~ to insure removal of the last traces of water. The residue,is
diluted with 79 par~s by weight of miaeral oil, and this oil solution is found ~o
have a nitrogen content of 1.6%.
Example A-29
To 710 parts (0.51 equivalent) of the substituted succ}nic anhydride
:~ prepared in Example 6, and 500 parts of toluene there are added portionwise 22
parts (0.51 equivalent~ of Polyarnine H. The mixture is heated at reflux
temperature for 3 hotars to remo~e water formed during the reaction by
.
azeotropic distillation. The mixture then is heated to 1 50C/20 mm. to remove
the tuluene. The residue contains 1.1% by weight of nitrogen.
:
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(B) Alkali Metal Overbased Salts of HYdrocarbYI-Substituted CarboxYlic Acids.
The lubrica~ing oil composi~ions of the present invention also
contain (B) an alkall metal overbased salt of a hydrocarbyl-subs~ituted
carboxyllc acid or a mixture of a hydrocArbyl-sub~titu~ed carboxylic acid and a
hydrocarbyl-substltuted sulfonlc acld provlded ~hat ~e carboxylic acld In the
mixture comprises more than 50~ of the ~cld eqllivalents of ~he mixture~ The
hydrocarbyl subs~ituent of the carboxylic acld generally will contain at least 50
carbon atoms.
The amount of the alkall metal overba~ed salt of the hydrocarbyl-
substituted carboxylic acid or mixture of carboxylic acid and sulfonic acid
încluded in the lubricating oil composltions of the present ~nvention ls an amount
sufflcient to provlde at least about û.002 eguivalent of allcali metal per ï00
grams of lubricating oll composlt~Dn~ In other embodiments, sufficient alkali
metal overbased salt is included in the lubricating oil cornposi~ion to provide at
least about 0.003 ~nd even at least about 0.005 equivalen~ of alkali metal per l0
~rams oP ~he lubricating oil composition.
The alkali metal oYerbased salts (E~) are characterized by a metal
content in excess of that which would be present according to the stoichiometry
of the metal and the parti~ular hydrocarbyl-substituted carboxylic acid reacted
with the metal~ The amount of excess metal is common)y expressed in terms of
metal ratio which is the ratio of the total equivalents of the metal to the
equivalents nf the ~cidic orgsnic compol1nd. For example, a salt having 4.5 times
as much metal as present ~n a normal salt is characterized as having a metal
ratio of 4~5. ln the present invention, the alkali metal overbased salts have a
metal ratio o~ greater than l, preferably at least about 1.5 or at least about 2or 3 up to about 30 or even up to about 40. In yet another embodiment the me~al
ratio is at least about 6.5.
In one em~odiment of the present invention, the metal ratio of the
alkali metal overbased salts (B) used in the lubricating oil compositions of thepresent invention is related to the ratio of the succinic groups per equivalent
:
.
WO 93/235(14 ' Pcr/VS92/087 18
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weight of the substituent groups in the acylating agents (A-l). For example,
when the acylating agents contain an average of at least 1 up to less tban 1.3
succinic groups for each equivalent weight of substituent groups, the metal ratio
of the alkali metal overbased salts used in lubrlcating oil compositions containing
carboxylic deri~atives (A) prepared frorn ~uch ac~lating agents i~ at least 2 or3, and in a preferred embodiment is at least about 6.5. When the carboxyl{c
derivati7~e (A) is derived from acylating agents charactcrized by the presence
within their struc~ure of an average of at least 1.3 succlnic groups1 the metal
ratio of the slkali me~al overb~sed salts ~B) used in sombination with such
aa,rlating agents is greater than 1, preferably at least abs~t 1.5.
The alkali metal overbased compositions are prepared by reacting
an acidic material which is typically carbon dioxide with a mixture comprising
the carbo~ylic acid or mixture of carboxylic and sulfoni~; aclds, an alkali metal
compound, typically a metal oxide or hy~roxlde, a promoter and at least one
inert organic diluent for the carhoxylic acid compound.
The hydrocarbyl groups of the hydrocarbyl-substituted carboxylic
acids are deri~ed from polyalkenes which may be characterized as containing at
least about 50 ~arbon atoms up to about 300 or 400 carbon atoms~ In one
embodiment, the polyalkene is characterized by ~n Mn value of at least about
900 or 1000 up to about 2500 or e~en up to about 5000~ The hydrocarbyl groups
of the hydrocarbyl sulfonic acids contain at least about 8 carbon atoms and in
another embodimçnt at least about 20 or eYen 50 carbon atom~.
The polyalkenes from which the hydrocarbyl substituent of the acid
is derived include homopolymers and~interpol~rners of polymerizable olefin
~5 monomers of from 2 to about 16 carbon atoms, usually from 2 to about 6 carbon
atoms, and prefer~bly from 2 to about 4 carbon atoms. The olefins may be
monoolefins such as ethylene, propylene, I-butene, isobutene and l-octene or a
polyolefinic monomer, preferably diolefinlc monomer such as 1,3-butadiene and
isoprene. The polyalkenes are prepared by~conventional procedures. Addi~ional
examples of polyalkenes from which the hydrocarbyl substituent of the succinic
WC) 93/23504 PCr/US92/08718
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and sulfonic acids can be derlved include any of the polyalkenes described abovewith regsrd to the prepar~tiorl of ~he acylating agent ~A- 1), and that portion of
the specification descrlbing such polyalkenes ls herein incorpora~ed by reference.
When preparing the hydrocarbyl-substituted carboxylic acids useful
in preparing the alksll metal salts utilized irl the present inYention, one or more
of the above-describcd polyalkenes i5 reac~ed with one or more a, ~-unsaturated
mono- or dlcarboxylic ~cld reagents by technlques known in the art. For
example, a halogenated hydrocarbon such as can be obtalned from polyisobutene
and a halogenating ~gent can be reacted wlth an a"B-unsaturated carboxylic acid
reagent by mixi~g the reactants a~ a suitable temperature such as 80C or
higher. The reac~lon can be carried out in the presence of an inert solvent or
diluen~.
The a,~-unsaturated monocarboxylic aci~ reagent may be the acid,
ester, amide, ~nide, ~nmonium salt9 or halide. It preferably contains less than
about 12 carbon atoms. Examples of such rnonocarboxylic acids include, for
example, acrylic acid, methacrylic acid (i.e., ~-methylacrylic acid), crotonic
acid, cinnamic acid, a-cthylacrylic acid, a-phenylacrylic acid, a-octylacrylic
acid, ~-propylacrylic acid, ~-octyl~crylic acidt ~-cyclohexylacrylic acid, a-
cyclopentylscrylic acid, ~-decylac~lic aeid, a-methyl-~-pentylacrylic acid, a-
propyl-~-phenylacrylic acid, a-chloroacrylic acid, a-bromoacrylic acid, ,B
chloroacrylic acid, a-chlorocrotonic acld, isocrotonic acld, a-methylcrotonic
acid, a-me~hylisocrotonic acid, p,~-dichloroacrylic acid, etc.
Esters of such a,~-unsaturated carboxylic acids especially those in
which the ester group is derived from a lower alkanol ~i.e., having less than about
8 carbon ato ms) likewise are useful in the invention. Specific examples of suchesters include m ethyl acrylate, m ethyl methacrylate, ethyl acrylate, cyclohexyl
acrylate9 cyclopentyl m ethacrylate, neopentyl a-phenyloacrylate, hexyl a-propyl-
~-propylacrylate, octyl ~-decylacrylate and the like. Other esters such as thosederived from other alcohols (e.g., decyl alcohol, epichlorohydrin, ~-chloroethanol,
dodecyl alcohol, and 4-bromo-1-decanol) are also contemplated. Still other
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WO 93/23504 PCl /US9~/087 18
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esters which are useful in ~he invention are exemplified by those derived from
phenol{c compounds including phenol, naphthol, cresol, o-butylphenol, m-
heptylphenol, p~tertiary bu~ylphenol, o,p-dilsoprapylphenol, a-decyl-,B-rlaphthol,
p-dodecylphenol, and other alkyl phenols and alkyl naphthols In which the ~Ikyl
substituent preferably h~s l~s than about 12 carbon atoms.
The halides of the a,~-unsaturated monocarboxyllc acids are
principally the chlorides ~nd bromides. They are lllustrated by acrylyl chlorlde,
methacrylyl bromide, a-phenylacrylyl chloride, ~-decylacrylyl chloride as well
as the chlorides and bromides of ths above-illustrated ~cids. The arnides and the
arnmonia salts of a, ~-unsaturated monocarboxylic acids include principally those
derived from ammonia or a monoam~ne suc:h as an aliphatic arnlne or an aryl
arnine. Such arnines may be mono-, di~ or trialkyl or aryl amin~s such as
methylamine, dimethylamine, trimethylamine, diethylamine, aniline, toluidine,
cyclohexylamine, dicyclohexylamihe, ~rlethylamine, melamine, piperazine,
pyridine, N-methyloctylamine, N,~-die~hylcyclohexylamine, v-butylanilinet p-
decylaniline, e~c. Again the unsaturated acids from which the amldes and
ammonlum salts of the above amines may be those i11ustrated preYiously. Imldes
of such acids derived from aIIunonia or a primary amine likewise 2re useful ~n
the invention and the imides sre formed by the replacement of 2 hydrogen atoms
of ammonia or a primary amirle with the carboxy radicals of the a,p-unsaturated
monocarboxylic acid. Likewise useful are the anhydrides of sucb monocarboxylic
acids such as are formed by molecular dehydration of the acid. It should be
noted that the above-noted acids and derivatives are capable of yielding the a,~-
! . ,1 unsaturated monocarboxylic acid and, for the~ sake of convenience, they are
described by the generic exp~esslons "a,~-unsaturated monocarboxylic acid
reagent" or "a,~-unsaturated monocarboxyllc acid-producing compound".
Procedures for preparing hydrocarbon-substituted monocarboxylic
acid reagents useful in preparing the alkali metal overbased salts (B) are
described in, for example, U.S. Patent 3,454,607 tLeSuer et al), and the
::
WO 93/23504 PCr/US92~0871~ .
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description of such procedures and additional examples of such reagents are
hereby incorpor~ted by reference.
The following examples lllus~rate such procedures and reagents.
Example 7
A chlorinated polyisobu~e~le having u molecular weight of 1~00 and
a chlorine content of 4.5% (6300 gramst 8 equl~r~lents of chlorine) is mixed with
acrylic acid (940 grams, 13 equivalents) ~nd the mixture is heated to 235C while
hydrogen chloride is evoled. It is then heated at 130~18~C/6 mm. and then
filtered. The filtrate is an ac~d haYing a chlorine cunterlt of 0~62~b and an ~cid
number of 63.
E~arnple B
A mixture of ~crylic acid (72û grams, 10 equivalents) and a
chlorinated polyisobutene having a molecular weight of 1000 and a chlorine
conten~ of 4.3% (6536 grams, 8.equivalents of chlorine~ {s heated at 170-225C
for 12 hours and then at 200C/10 n~. The residue is filtered at 140C and the
filtrate is the desired acid having a chlorine content of 0.36% and an acid
number of 60.
Example 9
The pro,cedure of Example 7 is repeated except that the chlorinated
is~butene i~ replaced on a halogen equivalent bas~s wlth ~ brominated copolymer
of isobutene (98% by weight) and Isoprene (2% by weight) having a molecular
weight of 500Q and a bromine content of 2.5 and that the acr~lic acid used is
replaced on a chemical equivalent basis with phenyl acrylate.
Example 10
' I ` 25 b mixture of crotonic acid (2 equivalents) and a chlorinated
polypropene having;a molecular weight of 2500 and a chlorine content of 5% ~0.5
equivalent of chlorine) is heated at 180-220C for 5 hours and then at 200C/1
mm. The residue is filtered and the filtrate is the desired acid.
WO 93/23504PCI'/USg2/0871~
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Example 1 1
A methyl ester of 8 hlgh molec:ular weight monocarboxylic acid is
prepared by heating an equimolar mixture of a chlorinated polyisobu~ene havng
a molecular weight of 1000 and a chl~rine content of 4.7% by weight and
methylmethacrylate at 140-22~C.
When preparlng the hydrocarbyl-substltu~ed dicarboxyllc acids
useful in preparing the alkali metal salts used in the present invention, one ormore of the above polyalkenes ~or halogenated polyalkene~) is reacted wi~h one
or more acidic reagents selected from the group conslsting of m~leic or fumaric
reactants of the general formula
X(O)C-CH_CH-C(O)X' ~XII~
wherein X an~ X' are the same or dlfferent provided that at least one of X and
X' are esch independently OH, I)-lower hydrocarbyl, O-M, C~l, Br or together, X
and X' can be -O- so as to form the anhydride. C)rdinarily, the maleic or fumaric
reactants will be maleic acid, fumaric acid, maleic anhydride, or a mixture oF
two or more of ~hese. The maleic reactants are usually preferred over ~he
fumaric reactants because the former are more readily available and are, in
general, more readily reaceed with the polyalkenes to prepare the desired
hydrocarbyl-substituted succinic acids.
The hydrocarbyl-substituted succinic acid reagents used to prepa~e
the alkali meeal overbased salts ~B) are similar to the hydrocarbyl-substituted
succinic acids used as the acylating agents (A l) described above where the
`~ ` hydrocarbyl-substituted succinic acids contaln at least about one succinic group
for each equivalent weight of substituent group. Thus, in one embodimen~ the
hydrocarbyl-subs~ituted succinic acids are prepared by reacting about one mole
~or 1 equivalent) of a polyalkene with one mole (or 2 equivalents~ of the maleioor fumaric acid reactant.
WO 93/23504 PCI/US92/OX718
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Procedures for preparing hydrocarbyl-substituted dicarboxylic acid
reagents useful in preparing the alkali metal overbased salts are described in, for
example, UAS. Patents 3,087,936 (LeSuer) ar~d 3,219,6~6 ~Norman), the disclosures
of which are hereby incorporated by reference. Examples of hydrocarbyl-
substltuted succinic acid re~gents useful ln preparing the alkall metal salts ~B)
include the succinic acylating ~gerlts exempllfled aboYe In E7ca~nples 1-6.
In ane embodiment~ the c~rboxylic acid~ are aromatlc carboxylic
acids. A group ~f useful aromatic c~rboxylic ~clds ~re those of the formula
11
~(C-XH)b
(R1 )a Ar\
~XH)C
wherein R1 is an aliphatic hydrocarbyl group preferably derived from the above~
15 described polyalkenes, a is a number in the range of 1 to about 4, usually 1 or 2,
Ar is an aromatic group, each X is independently sulfur or oxygen, preferably
oxygen, b is a number in the range of from 1 to about 4, usually ~ or 2, c is a
number {n the range of zero to about 4, usually 1 to 2~ with the proviso that the
sum of a, b and c does not exceed the number of valences of Ar. E:xamples of
20 aroma~ic carboxylic acids include substltuted benzoic, phthalic and salicylic acids.
The Rl group is a hydrocarbyl group that is directly bonded to the
aromatic group Ar. Examples of Rl groups include substituents derived from
polymerized olefins such as polyethylenes, polypropylenes, polybutylenes, ethyl-25 ene-propylene copolymers, chlorinated olefin polymers and oxidized ethylene-pro-
pylene copolymers.
l`he aromatic group Ar may have the same structure as any of the
aromatic groups Ar dlscussed below. Exampies of the aromatic groups that are
WO 93/23504 PCI/lJSg2/08718
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useful herein include the polyvalent aromatic groups derived from benzene, naph-thalene, anthracene, etc., preferably benzene. Specific examples of Ar groups
include phenylenes and naphthylene, e.g., methylphenylenes, ethoxyphenylerles,
lsopropylphenylenes, hydroxyphenylenes, dlpropoxynapht~lenes, etc.
Within this group o~ aromatlc aclds, a us~ful class of carboxylic
acids ~re those of the formula
(COOH)b
(Rl )a~
~/\
(OH)C
wherein Rl is defined above, a is a nusnber in the range of from 1 to about 4,
preferably 1 to about 3; b is a number in the range of 1 to ~bout 4, preferably
1 to about 2, c is a number in the range of zero to about 4, preferably 1 to about
2, and more preferably 1; with the provlso that the surn of a, b and c does not
:: exceed 6. Preferably, b and c are each one and the carboxyllc acid is a salicylic
1 ~ acid.
Overbased salts prepared from salicylic acids wherein the aliphatic
hydrocarbon substi~uents ~Rl ) are derived from the above-described polyalkenes,particlllarly polymerized lower l-mono-olefins such as polyethylene, polypro-
pylene, polyisobutylene, ethylene/propylene copol~rrners and the like and havingaverage carbon contents of about 50 to about 400 carbon atoms are par~icularly
useful. ~ : `
The above ;aromatic carboxylic acids are well known or can be
prepared ~according to proceduresknowninthe art. Carboxylic acidsof the type
illustrated by these fo~nulae and proc~ses for preparing their neutral and basicmetal salts are well known and disclosed, for example, in U.S. Patents 2,197~832;
:- 2,197,835; 2,2S2,662; 2,252,6fi4; 2,714,092; 3,410,798; and 3,595,791. These
:
:
WO 93/23504 pcr/us92/ox718
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references are incorporated by reference for disclos~e of carboxylic acid, theirbasic sal~ and processes of making the same.
As noted previouslyt the alkali metal overbased hydrocarbyl-
su~stituted carboxyllc acid may be derived from a mixture of hydrocarbyl-
substituted carboxylic acld and hydrocarbyl-substltuted sulfonic scid. The
hydrocarbyl-substituted carboxylic acld in the mlxl;ure generally will contain at
least about 50 carbon a~oms in the hydrocarbyl substltuent, and the hydrocarbyl
subs~ituent may also be characterized as having a number average molecular
weight of at least about 900. The sulfonlc acids useful in the mixtures include
the sulfonic and thiosulfonic acids. Generally they are salts of sulfonic acids.The sulfonic acid$ include the mono- or polynuclear aromatlc or cycloaliphatic
compourlds. The oil-solubls sulfontc acids can be represented for the most part
by one of the following formulae: R2-T-~SC)3)a~ a~d R3-~S~3)bH, where1n T is
a cyclic nucleus such as, for example, benzene, naphthalene, anthracene,
diphenylene oxide, diphenylene sulfide, petroleurn naphthenes, etc. R~ and R3
are generally a hydrocarbon an essentially hydrocarbon group, preferably fre~ ofacetyloenic unsaturation, and contairling about ~ to about 60 or more aliphatic
carbon stoms, preferably an aliphatlc hydrocarbon group swch as alkyl or alkenyl.
When R3 is aliphatlc it usually contains at least about 15 carbons; when it is an
aliphatic-substituted cycloallphatic group, the aliphatic substituents usualloy
contain a total of at least about 12 carbon atoms. Specific examples of R2 and
R3 are groups derived from petrolatum, saturated and unsaturated paraffin wax,
and the above described polyslkenes. The gl'9UpS T, R~, and R3 in the above
formulae can also ~ontain other inorganic or organic substituents in addition to~' 25 those enusnerated above such as, for exarnple, hydroxy, mercapto, halogen, nitro,
amino, nitroso, sulfide, disulfide, etc. In the above Formulae, a and b are at
least }.
~: : Specific examples of such sulfonic acids include mahogany sulfonic
acids, bright stock sulfonic acids, petrolatum sulfonic acids, mono- and polywax-
substituted naphthalene sulfonic~ aciis, cetylchloroben~ene sulfonic acids,
:
WO 93/23504 ~ ~ f~ " .~; PC~/U$92/08718
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cetylphenol sulfonic acids, cetylphenol disulfide sulfonio acids, cetoxycapryl
benzene sulfonic acids, dicetyl thian~hrene sulfonic acids, dllauryl beta-naphthol
sulfunic aclds, di~apryl nitronaphthalene sulfonic acids, saturated paraffin waxsulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-substiltuted
paraffin w ax sulfonic aclds, tetraisobutylene sulfonic ~cids, tetraamylene
sulfonic ac~ds, chlortne substituted psraffin W3LX sulfonle aclds, nltroso
substituted paraffin wax sulfon~c ac~ds, petroleurn naphthene slllfonic aclds,
cetylcyclopentyl sulfonic acids, lauryl cyclohexyl sulfonlc acidls~ m ono- and
polywax substituted cy~lohexyl sulfonlc acids, dodecylbenzene sulfonlc acids,
"dimer alkylate" sulfonic acids, and the like~
Alkyl-substituted benzene sulfollic acids wherein the alkyl group
contains at least 8 carbon atoms includlng dodecyl henzene l'bottoms" sulfonic
acids are p~rticularly useful. The latter sre acids derived from benzene which
has been alkylated with propylene tetramers or isobutene trimers to introduce
1, 2, 3, or more branched-chaîn C12~ubstituents on the benzene ring. Dodecyl
benzene bottoms, principally mlxtures of mono- and di-dodecyl ~enzenes, are
available as by products from the manufacture of household detergents. Similar
products obtained from slkylation bottoms formed during manufacture of linear
alkyl sulfonates (LAS) are also useful in making the sulfanates used in this
invention.
In another embodimen~, the substituted sulfonic acids also may
contain at least 50 carbon atoms. Illustrati~/e examples of th*se sulfonic acidsinclude polybutene or polypropylene substituted naphthalene sulfonic scids,
sulfonic acids derived by the treatment of polybutenes having a number average
I` ' I .
molecular weight (Mn) in ~he range of 700 to 5000, preferably 700 to 1200, more
preferably about 1500 with chlorosulfonic acids, paraffin wax sulfonic acids,
polyethylene (Mn equals about 900-2000, preferably about 900-l500, more
prefera`bly 900-1200 or 1300) sulfonic aclds, etc. Preferred sulfonic acids are
mono-, di-, and tri-alkylated benzene ~including hydrogenated forms thereof)
sulfonic acids.
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The promoters, that is, ~he materials which facilitate the
incorporation of excess metal into the overbased material lmprove contact
between the acidic material and the carboxyllc acid or mixture of carboxylic
acid and sulfonic acid ~over~asing substrate). Generally, ~he promoter is a
materlal which is sligh~ly acldic ~nd able to form a sal~ wlth the basic metal
compound. The promoter must ~Iso be an acid weak enough to be dlsplaced by
the acidic msterjal, usually carbon dioxlde. Generally, the promo~er has a pKa
in the range from about 7 to about 10. A parlticularly compreherlsive discus~ionof suitable promoters is found in UIlS. P~tents 2,777,874, 2,595,910, 2,616,904,3,384,586 and 3,492,231. These paten~s are incsrporated by reference for their
disclosure of promoters. Promoters may include phenolic substances such as
phenols and naphthols; amines such as ~niline, phenylenediamine, dodecylamine;
etc. In one embodiment, the prefe~red prom oters sre the phenolic promoters.
Phenolic promoters include a varlety of hydroxy-substituted benzenes and
naphthalenes. A particularly useful class of phenols are the alkylated phenols of
the type listed in U.S. Patent 2,777,874, e.g., heptylphenols, octylphenols, nonyl-
phenols, and tetrapropenyl-substitu~ed phenols~ Mixtures of variouls promo~ers
are sometimes used.
The inorganic or lower carboxylic acidic materials, which are
reacted with the mixtur~ of promoter9 basic metal compound, reaction medium
and the hydrocarbyl-substituted carbo7~1ic acid are disclosed in the above citedpatents, for example, U.S. Patent 296169904. Included within the lcnown group
of useful ucidic materials are lower carboxylic acids, having from 1 to about 8,preferably 1 to about 4 carbon atoms. ~Examples of these 8cids include formic
acid, acetic acid, propanoic acid, etc., prefersbly acetic acid. Useful inorganic
acidic compounds include HCI, S02, SO3, C02, H2S, N2C)3, etc., are ordinarily
employed as the acidic ma~erials. Preferred acidic materials are carbon dioxide
and acetic acid, more preferably carbon dioxide.
The alkali metals present in ~the alkali metal overbased salts include
principally lithiurn, sodium and potassium, with sodium being preferred. The
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overbased metal salts are prepared using a basic alkali met~l compound. Illus-
trative of basic alkali metal cornpounds are hydroxides, oxides, alkoxides
(typically those in which the alkoxy group contains up to 10 and preferably up ~o
7 carbon atoms), hydrides and amides of alkali metals. Thus, useful basic alkaliB metal compounds include sodium oxide, potassi~ oxide, }ithiurn oxide, sodium
hydroxide, potassiurn hydroxide, lithium hydroxide, sodlurn propoxide, lithium
methoxide, potassium ethoxide, sodiurn butoxide, lithiwn hydride, sodium hydride,
potassium hydrlde, llthiurn amide, sodium amide and pot~ium Dlde. Especially
preferred ~re sodium hydroxlde and the sodium lower allcoxldes (i.e., those
containlng up to 7 carbon atoms).
The alkali metal overbased materials useful in the present invention
may be prepared by methods known to lthose in the art. The methods generally
in~olve add~ng acidic material to a reaotion mixture cornprising the hydrocarbyl-
substituted carboxylic acid or mixture of carboxylic acid and sulfonic acid, thepromoter and a basic alkali metal compound. 1hese processes are described in
the following U.S. Patent Nos.: 2,616,90~; 2,616,gO5; 2,616,9û6; 3,242,080;
3,250,710; 3,256,186; 3,274,135; 3,492,231; and 4,230,586. These patents are
incorporated herein by reference for ~hese disclosures.
In the present invention, the preferred hy~ocarbyl-substituted
carboxylic acids have relatively high molecular weights. Higher temperatures
are generally used to promote contact between the acidic material, the succinic
acid and the basic alkali metal compound. The higher temperatures al50 promote
forrnation of the salt of the weakly acidic prornoter by removal of at leas~ some
of the water4 In preparing the overbased metal salts useful in the present imen-f~ ~5 tion, water must be removed from the reaction.
The reaction generally proceeds at tempera~ures from about 100C
up to the decomposition temperature of the reaction mixture or the individual
components of the reaction. The reaction may proceed at temperatures lower
than IOQ~C, such as 60C or abo~-e, if a vacuum is applied. Generally, the
reaction occurs at a temperature from about 110C to about 200C, preferably
WO 93/23504 pcr/lJs92/o871~
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120C to about 175C and more preferably ~bout 130C to about 150C.
Preferably, the reaction is performed in the presence of a reaction mediurn
which includes naphtha, mineral oll, xylenes, toluenes and the like. In the
present inventlon water may be removed by spply~ng a vacuwn, by blowing the
reactlon mlxture wlth a gas such as ni~rogen or by removing water as an
azeo~rope, such as 8 xylene-water szeotrope. Generally, in the present in~ren-
tlon, the ac~dic m~terlsl is provided as a g~$, usually c~rbon dioxlde. The carbon
dioxlde, whlle participatlng In the overba~ing process, also removes water if the
carbon dloxide is added a~ a r~te which exceeds the rate carbon dioxide is
cons~ned in the reaction.
The alkali metal overbased metal salts used in the present invention
may be prepared incrementally ~batch) or by continuous processes. One
incremental process irlvolves ~he Iollowing steps: (A) adding a basic alkali metal
compound to a resction mixture comprlslng the hydrocarbyl-substituted
carboxylic acid ~or mlxture of carboxylic and sulfonic acids) and promoter7 and
removing free wster from the reaction mixture to form an alkali metal salt of
~he acidic organic compound; (B) adding more basic alkali metal compound to the
reaction mixture and removing free water from the reaction mix~ure; and (Ç)
introducing ~le acidic materlal to the reaction mixture while removing water.
Steps (B~ and (C) ~re repeated until a product of the desired metal ratio is
obtained.
Another me~hod of preparing the alkali metal overbased salts is a
semi-continuous process for preparing the alkali metal overbased salts. The
process invohes (A) adding at least one basic alkali metal compound to a
reaction mixture comprising an alkali metal salt of hydrocarbyl-substituted
carboxylic acid ~or mixture of carboxylic acid and sulfoni~ acid) and removing
free water from the reaction mixture; ~and ~B) concurrently thereafter, ( 1 ) adding
basic alkali metal compound to the reaction mixture; (2~ adding an inorganic or
lower carboxylic acidic material to the reaction mixture; and (3) removing waterfrom the reaction m~xture. The addition of basic alkali me.tal compounds
WO 93/235~4 PCT/US92/~871~
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r , ,~ , , J
-51-
together with the inorganic or lower carboxyli:: acidic material where the
addi~ion is done continuously along with the removal of water results in a
shortened processiDg time for the reaction.
The ~crlTI 'tfree water" refers to the ~nount of water readily
removed from che reaction mixture. This water is typlcally removed by
azeotropic distlllatlon. The wat~r which remains In the reaction mixture is
belle~red to be coordinsted, assoclated, or solvated. The water may be iD the
fo~n of water of hydration. Some basic alksli metal compou~ds may be
delivered to the reaction mixture as aqueou~ solutions. The excess water added,
10 or free water, with the basic alkali metal compound is usually thell remoYed by
azeotropic distlllation, or V8CU1JIIl stripping.
Any water generated during the overbasing process is desirably
removed as ~t is fo~ned ~o minimize or eliminate formation of oll-insoluble
met~l carbonates. During the overbasing proce~ss above, the amount of water
15 present prior to addition of the inorganic or lower csrboxylic sc~dlc material
(steps ~B~ and (~1) above) is less than sbout 30~ by weight of the reaction
mixture, preferabJy less than 20%, more preferably less thin 10%. Generally,
the amount of water present after addition of the inorganic or lower carboxylic
acidic material is u~ to ~bout 4% by weight of the reaction mixture, more
20 preiferably up to about 2%.
In another embodiment, the alkali metal overbased salts are
bora~ed alkali metal overbased salts. Borated overbased metal salts are preparedby reacting a boron compound with the basic alkali metal salt. Boron compounds
includei boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, boron
25 tribromide, boron trichloride, ~boron acid such as boronic acid, boric acid,
tetraboric acid and metaboric acid, boron hydrides, boron amides and various
esters of boron acids. The boron esters are preferably lower alkyl (1-7 carbon
atoms) esters of boric acid. Preferably, the boron compounds are boric acid.
Generally, the overbased metal salt is reacted with a boron compound at about
50C to about 250C, preferably 100C to about 200C. The reaction may be
WO 93/23504 PC~/US92/08718
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accomplished in the presence of a solvent such as r~ineral oil, naphtha, kerosene,
toluene or xylene. The overbased metal salt is reacted with a boron compound
in amounts to provide at least about 0.5%, preferably about 1~ up to about 5%,
preferably about i%, more preferably about 39~ by weight boron to the
composltiorl.
The following examples illsustrate the alkali metal overbased ~alts
(B~ useful in thf~ present invention and methods of making the same.
Example B-1
A reaction vessel is charged with 1122 grsms ~2 equivalen~s) of a
polybutenyl-subs~ituted succinic anhydride derived from a poly~utene (Mn=1000,
1:1 ratio of polybutene to maleic acid), 105 grams (0.4 equivalent) of tetrapro
penyl phenol, 1122 grams of xylene and 1000 grams of 100 neutral mineral oil.
The mixture is stirred and h~ted to 80C under nitrogen, and 580 grams of a
SOg~ aqueous solution of sodium hydroxide are added to the vessel over 10
minutes. The mix,ture is heated from 80C to 120~C over 1.3 hours. Water is
removed by azeotropic ref~ c and the temperature rises to l50~C over 6 hours
while 300 grams of water is collected. (1) The reaction mixture is cooled to
about 80C whereupon 540 grams of a 50q~ aqueous solution of sodium hydroxide
are added to the vessel. (2) The reaction mixture is heated to 140C over 1.7
hours and water is removed at reflux conditions. ~3) The reaction mixture is
carbonated at 1 standard cubic foot per hour (scfb~ while removing water for 5
hours. Steps (1)-(3) are repeated using 560 grams of an aqueous sodium hydroxidesolution. Steps (1)-(3) are repeated using 640 grams of an aqueous sodium
hydroxide solution. Steps ~1~-(3) are then repeated with arlother 640 grams of a50% aqueous sodium hydroxide solution. The reaction mixture is cooled and lOOû
grams of 100 neu~ral mineral oil are~added to the reaction mixture. The reaetionmixture is vacuum stripped to 115C at about 30 millimeters of mercury, The
residue is fiitered through diatomaceous earth. The filtrate has a total base
number of 361, 43.4% sulfated ash, 16.0h sodium, 39.4% oil, a specific gravity
of l.11, and the overbased metal salt has a metal ratio of about 13.
W(~ 93/~3504 PCr/US92/08718
-53-
Exalmple ~2
The overbased salt obtained in Example B-1 ls diluted wi~h mineral
oil to provide a composition containing 13.75 sodi~n, a total base number of
about 320, and 459~ oil.
E~xample ~3
A reaction vessel is charged wlth 700 grams of a 100 neut~al
mineral oil, 700 grams ~1.25 equiYalents) of the ~uccinic anhydride of Ex~mple
~1 and 200 grams (~.5 e~uivalellts) of a 50% a~ueous solution of sodium
hydroxlde. The reactlon mixture is stirred and heated to 80C whereupon 66
grams (0.25 equivalent) of tetr~propenyl phenol ar~ fldded to the reacti~n vessel.
The rea~tion mixture is heated from 80C to 140C over 2~5 hours while blowing
of nitrogen and removing 40 grams of water. Carbon dioxide (28 grams, 1.25
equivalents) is added over 2.25 hours at a temperature from 140-1~5C. The
reaction mixture is blown wlth nitrogen at ~ standard cubic foot per haur (scfh)and a total of 112 grams of water is removed. The reaction temperature is
decreased to lL15C and the resctlorl mlxture is flltered through diatomaceous
earth. The filtrate has 4.06% sodium, a total base number of 89, a specific
gravity of 0.948, 44.$% oil, and the overbased salt has a metal ratio of about ~.
Example B-4
A reaction vessel is charged with 281 grams (0.5 equiYalent) of the
succinic anhydride of Example ~1, 281 grams of x~rlene, 2~ grams of tetrapro-
penyl substituted phenol and 250 grarns of 100 neutral mineral oil. The mixture
is heated to 80C and 272 grams (3.4 equivalents) of an aqueous sodium hydroxidesolution are added to ~he reaction mixture~ The mixture is blown with nitrogen
at 1 scfh, and ~he reaction temperature is increased to 148C. The reaction
mixture is then blown with carbon dioxlde at 1 scfh for one hour and 25 minutes
whlle 150 grams of water are collected. The reaction mixture is cooled to 80C
whereupon 272 grams (3.4 equivalents) of the above sodium hydroxide solution
are added to the reaction mixture, and the mixture is blown with nitrogen at 1
scfh. The reaction temperature is increased tO 140C whereupon the reaction
:
WV 93/23504 PCr/US92/0~718
5~-
mixture is blown with carbon dioxide a~ 1 scfh for 1 hour and 25 minutes while
150 grams of water are collected. The reaction ternperature is decreased tO
100C, and 272 grams (3.4 equivalents) of tbe above sodium hydroxide solution
are added wh~le blowing ~he mixture with nitrogen as 1 scfh. The reaction
temperature is increased to 148C, and the reaction mlxture ~s blown wlth carbondioxide at 1 scfh for 1 hour and 40 minutes whlle 160 grams of water are collect-
ed. The reaction mixture ls cooled to 90C and 250 grams of 100 neutral mineral
oil are added to the reactlon mlxture. The reactlon mixture i5 vacuurn stripped
at 70C and the residue is flltered through diatomaceous earth. The filsrate
c~tains S0.0% sodium sulfate ash by ASrM D-874, total bsse number of 408, a
speclfic gravity of 1.1~, 37.1% oil, and the salt has a metaî rs~io of about 15.8.
Example B-5
A reaction ve~sel is charged with 700 grams of the product of
Example ~4. The reaction mlxture is heated to 75C whereupon 340 grams (5.5
equivalents) of boric acid are added over 30 minutes. The reaction mixture is
heated to 110C over 45 minutes, and the reaction temperature is maintained for
2 hours. A 100 neutral mineral oll (80 grasns) is added to the reaction mixture.The reaction mixture is blown with nitrogen at 1 scfh at 160C for 30 minutes
while 95 grams of water are collected. Xylene ~200 grams) is added to the
reaction mixture and the reaction semperasure is maintained at 130-140C for
3 hours. The reaction mixture is vacuum stripped at 150C and 20 millimeters
of mercury. The residue is ~iltered through diatomaceous earth. The filtrate
contains ~.849~ boron and 33.1% oil. The residue has a total base number of 309. Example B-6
` 25 ~i reaction vessel is charged with 224 grams (0.4 equivalents) of the
suc cinic anhydride o- Example B-~l, 21 grams (0.08 equivalent~ of a tetrapropenyl
phenol, 224 grams of xylene and 224 grams of lO0 neutral mineral oil. The
mixture is heated, and 212 grams (2.65 equivalents) of a 50% aqueous sodium
hydroxide solution are added to the reaction vessel. The reaction temperature
increases to 130C and 41 grams of water are removed by nitrogen blowing at 1
WO 93/23504 P~/US92/0871~
2 ~ 2 ~ !
-55-
scfh. The r¢action mixture is then blown with carbon dioxide at 1 scfh for 1.25
hours. Addi~ional sodîum hydroxide solution (432 grams, $.4 equivalen~s) is added
over four hours while blowing with carbon dioxide at 0.5 scfh at 130C. During
the ~dditicn, 3û1 grams of water are removed from the reaction vessel. The
reaction temperature is incressed to 150C and the rate of carbon dloxide
blowing i8 increased ~o 1.5 scfh and maintained for 1 hour a-ld 15 minutes. The
reaction mixture is cooled to 150C and blown with nitrogen at 1 scfh while 176
grams of oil are added to the reaction mixture. Ths reaction mixture is blown
with nitrogen at 1.8 scfh for 2.5 bours, and the mlxture is then flltered through
diatomaceous earth. The fll~rate contains 15.7~ sodium and 39% oil. The
filtrate has a total base number of 380, and a rnetsl ratio of about 14.5.
Exarnple ~7
A reaction vessel ls charged with ~61 grams ~1 equivalent) of the
succinic anhydride of Example ~1, 52.5 grams (0~2 equivalent) of a te~rapro-
penylphenol, 561 grams xylene and 500 grams of a 100 neutral mineral oil. The
mixture is heated to 50C under nitrogen, and 373.8 grams (6.8 equivalents) of
potassium hydroxide and 299 grams of water are added to the mixture:. The
reaction mixture is hested to 135C while 145 grams of water are rernoved. T~e
azeotropic distillate is clear. Carbon dioxide is added to the reaction mixture
at 1 scfh for two bours while 195 grams of water arc removed azeotropically.
The reaction mixture is cooled to 75C whereupon a second portion of 373.8
grams of potassium~ hydroxide and 150 grams of water are added to the reaction
vessel. The reaction mixture is heated to 150C with azeotropic removal of 70
grams of water. Carbon dioxide (1 scfh) is added for 2.5 hours while 115 grarns
`~ of water is removed azeotropically. The reaction is cooled to 100C where a
~ ~ ~ third portion of 373.8 grams of potassiurn hydroxide and 150 grams of water is
`~ added to the vessel. The reaction mixture is heated to 1 50C while 70 grsms of
water are removed. The reaction mixture is blown with carbcn dioxide at 1 scfh
for one hour while 30 grams of water are removed. The reaction temperature
is decreased to 70C. The reaction mixture is reheated to 1 50C under nitrogen.
WO 93/23504 PCI/US92/0871X
~ ~ @~ ~, f ~J
-56-
At 150~C the reaction mixture is blown with carbon dioxide at 1 scfh for two
hours while 80 grams of water are removed. Tbe carbon dioxide is replaced with
a nitrogen purge, and 60 grams of water is removed. The reaction is ~hen blown
with carbon dioxide at 1 scfh for three hours wlth removal of 64 grams of water.The reac~ion mixture is cooled to 75C where 500 grams of 100 neutral mineral
are sdded to the reaction mixture. The reaction is vacuum s~ripped to 11 5C and25 mllllmeters of mercury, The residue ls flltered through dia~omaceous earth.
The filtrate contains 35% oll~ has a base number of about 322, and a metal ratioof about 13.6.
E:xarnple B-8
An overbased sodi~n sulfona~e/succlnate mi~ture is prepared by
the process described in Example B-l using 562 grams (1 equivalent) of the
succinic anhydride of Exalnple B-1 arld 720 grarns (0.8 equivalent) of a pol~rbut-
enyl-substituted sulfonic acid derived from a polybutene ~Mn=800) and 1632
grams (20.4 equivalents) of a 50~ aqueous solution of sodium hydroxide.
Example B-9
A sodium overbased monocarboxylic acid salt~ is prepared by the
general process of Example B-1 by reacting 1 equivalent of ~he high molecular
weight monocarboxylic acid of Example 8 with a total ~f 15 equivalents of
sodium hydroxide.
The lubricating oil compositions of the present invention contain
a major amount of an oil of lubricating viscosity, at least 1% by weight of the
carboxylic derivative compositions (A) described above, and an amount of at
least one alkali metal overbased salt (B~ of a carboxylic acid or mixture of
carboxylic and sulfonic acids as described above. More often, the lubricating
compositiorls of this invention will contain at least 70% or 80% of oil. The
amount of carboxylic derivative (A) Included in the lubricating oil compositionsof the invention may vary over a wide range provided that the oil composition
con~ains at least about 1% by weight (on a chemical, oil-free basis) of the
carboxylic derivative composition (Al. ln other embodiments, the oil composi-
WO g3/23~04 P(:~/US9~/~871~
tions of the present invention may contain at least about 29~ or 2.5% by weight
or even at least about 3% by weight of the carboxylic derivative composition (~).
The carboxylic derivative composition ~A.) provldes the lubricating oil composi-tions of the present invention with deslrable Vl ~nd disper~ant properties.
As no~ed above, the lubricating oil composltions of the present
inventlon ~Iso contain at least about 0.002 equivalent of alkali metal per lO0
grams of lubricating oil composition. In other embodiments, the lubrlcating oil
composi~ions will con~aln at least about a.oo3 or at least about 0.005 equi~alent
of alkall metal per 100 grams of lubricating oil compositlon. T~e maximum
amount of alkali metal present in the lubricating oil composltions may Yary overa wide range depending upon the nature of the other compo~ents of the
lubricating oil composition and the in~ended use of the lubricating oil composi-tion. Generally, however, the lubricating oil compositions of the pr~sent
invention will contain up to about 0.008 or even 0.01 equivalent of alkall metallS per 100 grams of lubricatlng oil composition.
(C) Metal DihYdrocarbYI DithioPhosPhate.
In addi~ion to the carboxylic dispersant (A) and the alkali metal
overbased metal salt (B), the lubricating oil compositions of the present inventio,n
may contain and generally do contain other additive components including
antiwear agents such as metal salts of dihydrocarbyl dithiophosphates.
The metal dihydrocarbyl dithiophosphate which may be included in
the oil compositions are characterized by the formula
.;, R10 ~ ~
( R2O/ - (Xlll)
wherein Rl and R2 are each independentIy hydrocarbyl groups containing from
3 to about 13 carbon atoms, M is a metal, and n is an integer equal to ~he
valence of M.
WO 93/23504 PCr/US92/0~71B
2 ~ t'i ~
-58-
Generally, the oil composi~ions of the present invention will contain
varying amounts of one or more of the above-identified metal dithiophosphates
such as from about 0.01 up to about 2% or to 5% by weiight, and more generally
from a~out 0.01 to about 1% by weight based on the weight of the total oi{l
composition. The metal dithiophosphates are added to the lubricating oil
composltions of the irmentlon to impro~e the anti-wear and antioxidant
properties of the oll compositions.
The hydrocarbyl groups ~1 and R2 in the dithiophosphate may be
alkyl, cycloalkyl, aralkyl or alkaryl groups, or a ~ubstantially hydrocarbon group
of similar structure. By "substantially hydrocarbon'~ is meant hydrocarbons which
contsin substituent groups such ~s ether, ester, nitro, or halogen whlch do not
msterially affect the hydrocarbon char~cter of the group.
Illustrative alkyl grnups include isopropyl, isobutyl, n-butyl,
sec-butyl, the varlous amyl groups, n-hexyl, methylisobutyl carbirlyl, heptyl,
2-ethylhexyl, diisobutyl, isooctyl, nonyl, behenyl~ decyl, dodecyl, ~rldecyl, etc~
Illustrati~re lower alkylphenyl graups include butylphenyl, amylphenyl, heptylphen~
yl, etc. Cycloalkyl groups likewise are useful and these include chiefly cyclohexyl
and the lower alky!-cyclohexyl radicals. Many substituted hydracarbon groups
may also be used,~ e.g~., chloropentyl, dichloropherlyl, and dlchlcrodecyl.
In another embodiment, at least one af R1 and R2 in Formula XIII
is an isopropyl or secondary butyl group. In yet anather embodiment, both
and R2 are secondary alkyl groups.
The~ phosphorodithioic acids from which the metal salts useful in
this invention are prepared are well known. Examples of dihydracarbyl
j
2S phosphorodithioic acids and metal salts, and processes for preparing such acids
and salts are found in, for example, U.S. Patents 4,263,150; 4,289,635; 4,30~,154;
and 4,417,990. These patents are hereby incorporated by reference for such
disclosures.
The phosphorodithioic acids are prepared by the reaction of
phosphorus pentasulfide With an alcohol or phenol or mixtures of alcohols. The
WV 93/23~)4 P~/~JS92/0871X
S~ r,~
-59-
reaction involves four moles of the alcohol or phenol per mole of phosphorus
pentasulfide, and ma~r be carried out wi~hin the temperature range from about
50C to about 200C~ Thus the preparation of O,Q-di-n-hexyl phosphorodithioic
acid involYes the reaction c~f phosphorus pentasulfide with four moles of n-hexyl
alcohol at about 100C for abou~ two hours. 13ydrogen sulfide is liberated and
thc residue is the de~ined acid. The prep~ration of the m~tal sa}t of this acid
may be ef~ected by reaction wi~h metal oxide. Simply mixing and heating these
two reactants is sufficient to cause ~he reaction to take place and the resultlng
product is sufficiently pure for ~he purpose~ of this illventian.
The metal salts of dihydrocarbyl dithiophosphates which are useful
in this invention include those salts containing Group I metals, Group Il metals,
alurninum, lead, tin, molybdenum, manganese, coba}t, and nickel. The Group 11
metals, aluminum, tin9 iron, cobalt, lead, molybdenum, marlganese, nickel and
copper are among the preferred metals. Zinc and copper are especially useful
metals. In one embodiment, the lubricant compositions of the invention contain
examples of metal compounds which may be reacted with the acid include
lithiurn oxide, lithium hydlroxide, sodium hydroxide, sodiurn carbonate, potassium
hydroxide, potassitLm carbonate, silver oxide, magnesium oxide, magnesi~m
hydroxide, calcium oxide, zinc hydroxide, strontium hydroxidel cadmium oxide,
cadmium hydroxide, barium oxide, alurninwn oxide, iron carbonate, copper
hydroxide, lead hydroxide, tin butylate~ cobalt hydroxide, nickel hydroxide, nickel
carbonate, etc.
In some instances, the incorporation of certain ingredients such as
small amounts of the metal acetate or acetic acid in conjunction with the metal
reactant will facilitate the reaction and result in an improved product. For
example, the use of up to about 5% of zinc acetate in combination with the
required amount of zlnc oxide facilitates the formation of a zinc phosphorodi-
thioate.
WV g3/23504 PCr/US9~/08718,...
~60-
ln one preferred ernbodiment, the alkyl groups Rl and R2 are
derived frorn secondary alcohols such as isopropyl alcohol, secondary butyl
alcohol, 2-pentanol, 2-methyl-4-pentanol, 2-hexanol, 3-hexanol, etc.
Especially useful metal phosphorodithioates can be prepared from
phosphorodithioic acids which in turn are prepared by the reaction of phosphoruspentasulflde with mlxtures of alcohols. In addlt10n, the use of such mixtures
enables the utlllzation of cheaper alcohols which in them~elves may not yield
oil-soluble phosphorodithioic acids.
Useful mixtures of met~l salts of dihydrocarbyl dithiophosphoric
acid are obtained by reacting phoxphorus pentasulfide with a mixture of (a)
isopropyl or secondary butylo alcohol, and ~b) an ~Icohol containin~ at ~least 5carbon atoms wherein at 'east tO mole percent, preferably 20 or 25 mole
percent, of the alcohol in the mixture isopropyl ~Icohol, secondary butyl alcohol
or a mixture thereof.
Thus a mixture of isopropyl and hexyl alcoh~ls can be used to
produce a very effective, oil-soluble metsl phosphorodithioate. For the same
; ~ reason mixtures of phosphorodithioic acids can be reacted wlth the metal
compounds to form less expensive, oil-soluble salts.
The mixtures of alcohols may be mixtures of different primary
alcohols, mixtures of different secondary alcohols or mixtures of primary and
secondary alcohols. E:xamples of useful mixtures include: n-butano; and n-oc-
tanol; n-pentanol and 2-ethyl-1-hexanol; isobutanol and n-hexanol; isobutanol and
isoamyl alcohol; Isopropanoi and 2-methyl-4-pentanol; isopropanol and sec-butyl
slcohol; isopropanol and isooctyl alcohol; etc. Particularly useful alcohol
mixtures are mix~ures of secondary alcohols containing at least about 20 mole
percen~ of isopropyl alcohol, and in a preferred embodiment, at least 40 mole
percent of isopropyl alcohol.
The following examples illustrate the preparation of metal
phosphorodithioates prepared from mixtures of alcohols.
. . . .
WO 93/23504 s~ PCr/
-61 -
Example C-l
A phosphorodithioic acid is prepared by reacting a mixture of
alcohols comprising 6 moles of 4-methyl-2-pentanol and 4 mole~s of isopropyl
alcohol wlth phosphorus pen~asulf~de. The phosphorod~thioic acid then is reactedwlth an oil slurry of zinc oxide. The a~nount of z~nc oxide In the slurry is about
1.08 tlmes the theoretical amount required to compl~tely neutrallze the phos-
phorodithioic acld. The oil solution of the zinc phosphorodl~hio~te obtained in
this manner ~10~6 oil) contains 9.5% phospho~us, 20.0% sulfllr and 10.5% zinc.
E:xample C-2
A phosphorodithloic acid is prepared by re~cting finely powdered
phosphorus pent~sulfide with an alcohol mixture cantaining 11.53 moles (692
parts by weight) of isopropyl alcohol and 7.69 moles ~1000 parts by weight~ of
isooctanol. The phosphorodithioic acid o~tained ~n this manner has an acid
number of about 178-186 and contains 10.0% phosphorus and 21.0% sulfur. This
phosphorodithioic acid is then reacted with an oil slulTy uf zinc oxide. The
quantity of zinc oxide included in the oil slurry is 1.10 times the theoretical
equivalent of the acid number of the phosphorodithioic acid. The oil solution ofthe zinc salt prepared In this manner contains 12~ oil, 8.6% phosphorus, X8.~%
sulf~ and 9.5% zinc.
Example C-3
A phosphorodithioic acid is prepared by reacting a mixture of 1560
parts ~12 mcles) of isooctyl alcohol and 180 parts ~3 moles) of isopropyl alcohol
with 756 parts (3.4 moles) of phosphorus pentasulfide. The reaction is conducted; by heating~ the alcohol mixture to: about 55C and thereafter adding the
phosphorus pentasulfide over a period of 1.5 hours while maintaining the reaction
temperature at about 60-75C. After all of the phosphorus pentasulfide is added,the mixture is heated and stirred for an additional hour at 70-75`C,and there-
after filtered ~hrough a filter aid.
Zinc oxide (282 parts, 6.87 moles) is charged to a reactor with 278
3û par~s of mineral oil. The above-prepared pnospho~ odithiuic acid (2305 parts, 6.28
.
WO 93~23504 pcr/us92/ox718 .
J ~ ~ I~ J .~ ~ ~
-62-
moles) is charged to the zinc oxide slurry over a perlod of 30 minutes with an
exotherm to 60C. The mixture then is hea~ed to 80C and main~ained at this
temperature for 3 bours. After stripping to 100~3C and ff mm.Hg., the mixture
is filtered twice through a filter aid, and the flltrate is the desired oll solutlon
5 of the zinc salt contalning 10~ o~l, 7.97% zinc (theory 7.40); 7.2196 phosphorus
(theory 7.0B); arld 15.64% sulfur ~theory 14.57).
Exasnple C-4
Isopropyl slsohol 1396 part~3, 6.ff moles) and 1287 parts (9.g moles)
of isooctyl alcohol are charged to a reactor ~nd heated wlth stirrillg to 59C.
Phosphorus pentasulfide (833 parts, 3.75 molesl Is then add~d under a nitrogen
sweep. The addition of the phosphorus pentasulfide is comple~ed in about 2 hoursat a reaction temperature between 59-63C. The mixture therl is stirred at
45-63C for about 1,45 hours and filtered~ The filtrate is the desired phosphorodi-
thioic acid.
A reactor is charged wlth 312 parts ~7.7 equivalents~ of zinc oxide
and 58Q parts of mineral oil. While stirring at room temperature, the above-pre-pared phosphorodithioic acid (2287 p~rts, 6.97 e~uivalents) is added over a period
of about 1.26 hours with an exotherm to 54C. The mixture is heated to 78C
and maintalned at 78-85C for 3 hours. The reaction mixture is lracuum stripped
to 100C at 19 mm.Hg. The residue is filtered through a filter aid, and the
filtrate is an oil solution (19c2% oil) of the desired zinc salt containing 7.86%
zinc, 7.76% phosphorus and 14.8% sulfur.
Example C-5
The general procedure of Example C-4 is repeated except that the
,
mole ratio of isopropyl alcohol to isooctyl alcohol is 1:1. The product obtainedin this manner is an oil solution (10% oil) of the zinc phosphorodithioate
containing 8.96% zinc, 8.49%~ phosphorus and 18.05% sulfur.
WO 93/23504 PCI /US92/û871X
-63-
Example C-6
A phosphvrodithioic acid is prepared in accordance with the general
procedure of Example C-4 utilizing an alcohol mixture containing 520 parts (4
moles) of isooc~yl alcohol and 360 parts (6 moles) of isopropyl alcohol with 504S parts (2.27 moles) of phosphorus pentasulfide. The zinc salt is prepared by
reacting an oil slu~Ty of 116.3 part~ of mineral oll arad 141.5 par~s (3.44 moles)
of zinc oxide with 950.8 parts ~3.20 mole~) of the above-prepared phosphorodl-
thioic acid. The product prepared in thls manner is an oll solution ~10% mineraloil) of th¢ desired zinc saltl and the oil solutiorJ contains 9.36% zinc, 8.81%
phosphorus and 18.65% sulfur.
Example (:-7
A mlxture of 520 parts ~4 moles) of isooctyl alcuhol and 559.8 parts
~9.33 moles) of isopropyl alcohol is prepared and heated to 60C at which tlme
672.5 parts (3.03 moles) of phosphorus pentasulfide are added in portions while
stirring. The reaction the~ is maintained at 60-65C for about one hour and
filtered. The filtrate is the dcsired phosphorodithioic acid.
An oil slurry of 188.6 parts ~4 moles) of zinc oxide and 144.2 parts
of mineral oil is prepared, and 1145 parts of the above-prepared phosphorod~
thioic acid are added in portions while maintaining the mixture at about 70C.
2Q After all of the acid is charged, the mixture is heated at 80C for 3 hours. The
reaction mixture then is stripped of water to 110C. The residue is filtered
through a filter aid, and the filtrate is an oil solution (10% mineral oil) of the
desired produc~ containing 9.99% zinc, 19.55% sulfur and 9.33% phosphorus.
Example C-B
A phosphorodithioic acid is prepared by the general procedure of
Example C-4 utilizing 260 parts (2 moles) of isooctyl alcohol, 480 parts (8 moles)
~` of isopropyl alcohol, and 504 parts (2.27 moles) of phosphorus pentasulfide. The
phosphorodithioic acid (1094 parts, 3.84 moles) is added to an oil slurry
containing 181 parts (4.41 moles) of zinc oxide and 135 parts of mineral oil over
a period nf 30 minutes. The mixture is heated to 80C and maintained at this
WO 93/23504 P~/US9~/087l~ .
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-64~
temperature for 3 hours, After stripping to lOO~C and 19 nLm.Hg., the mixture
is filtered twice through a filter aid, and the filtrate is an oil solution (10%mineral oil) of the zinc salt containing 10.06% zinc, 9.04% phosphorus, and 19.2%
sulfur.
Additional specifio examples bf metal phosphorodlth~oates useful
as component (C) in the lubrlcatlng oils of the present In~ention are listed in the
following table. Examples C-9 to C-14 are prepared from s{ngle alcohols, and
Examples C-15 to C-l9 are prepared from alcohol mixtures following the general
procedure of Example C-1.
.. . . .. ., .. ~ .. ~ . .
WO 93/23504 PCr/lJS92)t~87~X
, " ,", ", ,~ ,, ,"
1 .~ ... , . i i, .. ....
-~5-
TABLE
Component C: Metal Phosphorodithioates
PSS ~ M
.Z M n
-
C:-9 n-nonyl n-nonyl Ba 2
C-10 cyclohexyl cyclohexyl Zn 2
Gl 1 isobutyl isobutyl Zn 2
C-12 hexyl hexyl Ca 2
C-13 n-dec~rl n-decyl Zn 2
C-14 4-methyl-2-pentyl 4-methyl-2-pentyl Cu 2
C-15 ~n butyl + dodecyl) (l:l)w Zn
C-16 (isopropyl ~ isooctyl) ~l l)w Ba 2
C-17 (isopropyl ~ 4-methyl-2 pentyl~ (40:60)m Cu 2
`: C-18 (isobutyl I isoamyl)~65:35~rrl Zn ~.
C-l9 (isopropyl~sec-butyl) (40:6~)m Zn 2
Another class of the phosphorodithioate additives contemplated for
use in the lubricating composition o~ this invention comprises the adducts of the
O ~ metal phosphorodithioates descrlbed above with an epoxide. The metal
phosphorodithioates useful in preparing such adducts are for the most part the
zinc phosphorodithioates. The epoxides may be alkylene oxides or arylalkylene
oxides. The a~la!kylene oxides are exemplified by styrene axide, p-ethylstyrene
oxide, alpha-methylstyrene oxide, 3-beta~naphthyl- 1,1 ,3-butylene oxide9 m-~ode-
cylstyrene oxide, and p-chlorostyrene oxide. The alkylene oxides include
principally the lower alkylene oxides irl which the alkylene radical contains 8 or
less carbon atoms. Examples of such lower alkylene oxides are ethylene oxide,
.
W~ 93/23~04 PCr/l)S92/0~71~
2 ~ J ~J ' 11
66
propylene oxide, 1,2-butene oxide, tr~nethylene oxide, tetramethylene oxide,
butadiene monoepoxide, 1,2-hexene oxide, and eplchlorohydrin. Other epoxides
useful herein include, for exarnple, butyl 9,10-epoxy stearate, epoxidized soya
bean oil, epoxidized tung oil, and epoxldized copolym~r of styrene with
butadiene.
The adduct may be obtaiQed by slmply ml~ing ~he metal phosphoro-
dithioate snd the epoxlde. The reaction is usually exothermic and snay be carried
ou~: wlthln wide temperat1lre llmits from sbout 0UC to about 300C. Because the
reaction is exotherrnic, it ts best car~led out by addIng on reactant, usually the
epoxide, in small incremen~s to the other reactant in order to obtain convenientcontrol of the temperature of the reactiorl. The reaction may be carried out in
a solvent such as benzene, mlneral oll, naph~ha, or n-hexene.
The chemical structure of the ~dduct is not known. For the
purpose of this invent~on adducts obtained by the reactlon of one mole of the
phosphorodithioate with from ~bout 0.25 mole to 5 moles, usually up to about
0.75 mole or about 0.5 mole of a lower alkylene oxide, particularly ethylene
oxide and propylenc oxide, have been found to be especially useful and thereforeare preferred.
The preparation of su¢h adducts is more specifically illustrated by
the following example.
Example C-20
A reactor is charged with 2365 parts (3.33 moles) of the zinc
phosphorodithioate prepared in Exarnple C-2, and while stirring at room
temperature, 38.6 parts (0.67 mole) of propylene oxide are added with an
` 2~ exotherm of from 24-31C. The mixture is ma~intained at 80-90C for 3 hours
and then vacuum stripped to 101~C at 7 msn. Hg. The residue is filtered using
a filter aid, and the filtrate is an oil solution (11.8% oil) of the desired salt
containing 17.1% sulfur, 8.17% zinc and 7.44% phosphorus.
In one embodiment, the metal dihydrocarbyl dithiophosphates whîch
are utilized as component (C) in the lubrica~ing oil compositions of the present
WO 93/23504 pcr/uss2/o8718
... ~ ~ ,, ~,,, i
-67-
i~vention will be characterized as having at least one of the hydrocarbyl groups(Rl or R2) attached to the oxygen atoms through a secondary carbon atom. In
one preferred embodiment, both of the hydrocarbyl groups Rl and R2 are
~ttached to the oxygen atoms of the dithlophosphate through seconda~ carbon
atoms. In a further embodiment, the dlhydrocarbyl dithiophosphorlc acid~s used
in the prepara~ion of the metal salts are obtalned by reactlng phosphorus
pentasulfide with a mixture of aliphatic alcohols wherein at least 20 mole
pcrcen~ of the mixture is Isopropyl alcohol. More generally, such mixtures wlll
contain at least 40 mole percent of isopropyl alcohcl. The other alcohols ln themixtures may be elther pr~nary or seccndary alcohols. In som~ ~pplications,
such as in passenger car crankcase oils, metals phosphorod}thioates derived froma mixture of isopropyl and another secondas y ~lcohol (e.g., 2-meth~1-4-pentanol)
appear ~o provlde improved results. For oils designed for use in both compression
and spark-ignited engines, i nproved results nften are obtained when the
phosphorodithioic acid is prepared from a mixture of isoprspyl alcohol and a
:~ primary alcohol such as isooctyl alcohol.
Another class of the phosphorodithioate additives (C) contemplated
as useful in the lubricating compositions ~f the invention comprises mixed met~lsalts of (a) at least oné pbosphorodithioic acid as defined and exemp}ified above,
2Q and (b) at least one aliphatic or alicyclic carboxylic acid. The carboxylic acid
may be a monocarboxylic or polycarboxylic a~id, usually containing from 1 to
abou~ 3 carboxy groups and preferably only 1. It may contain from about 2 to
about 40~ preferably from about 2 to about 20 carbon atoms, and advantageously
a~out 5 to about 20 carbon atorns. The preferred carboxylic acids are those
having the formula R3COOH,~wherein R3 is an aliphatic or alicyclic hydrocar-
bon-based radical preferably free from acetylenic unsaturation. Suitable acids
include the butanoic, pentanoic, hexanoic, oc~anoic, nonanoic, decanoic,
:~: dodecanoic, octadecanoic and eicosanoic acids, as well as olefinic acids such as
oleic, linoleic, and linolenic aclds and linoleic acid dimer. For the most part, R3
is a saturated aliphatic grbup and especially a branched alkyl group such as the
.
WO 93/23~0q PCMJS92/08718.~"
(" ~, S ',~ ~.J ( j 'j ~'J
-68-
isopropyl or 3-heptyl group. Illustra~ive polycarboxylic acids are suecinic, alkyl-
and alkenylsuccinic, adipic, sebacic and citric acids.
The mixed ~netal salts may be prepared by merely blending a metal
salt of a phosphorodithiolc acid with a metal salt of a carboxylic acid in the
desired ratio. The ratio of equivalenl;s of phospholodi~hioic to carboxylic acidsalts is between ~bout 0.5:1 to about 400:1. Preferably, the ratio ls between
about 0.5:1 and sbout 200:1~ ~dYantageously, the r~tio can }~e from about 0~5:1
to about 100:1, preferably f~om ~out ~.5:1 to about 50:1, and more preferably
from about 0.5:1 to about 20:1. Further, ~he ratio can be ~rom about 0.5:1 to
about 4.5:1, preferably about 2.5:1 to about 4.25:1. For this purpose, ~he
equi~alent weight of a phosphorodithioic acid is its molecular weight divided bythe number of -PSSH groups ~herein, and that of a carboxrlic acid ls its
molecular weight dlvided by the nwnber of carboxy groups therein.
A second and preferred method for preparing the mixed metal salt~
useful in this invention is to prepare a mlxture of the acids ln the desired ratlo
and to react the acid mixture with a suitable metal base. When this method of
preparation is used, it i5 frequently possible to prepare a salt contalning an
excess of me~al witb respect to the number of equivalents of acid present; thus
mixed metal salts containing as m~ny as 2 equi~alents and especially up to about1.5 equivalents of metal per equivalent of acid may be prepared. The equivalent
of a metal for this purpose is its atomic weight divided by its valence.
Varian~s of the above-described methods may also be used to
prepare the mixed metal salts useful in this invention. For example, a metal salt
of either aeid may be blended with an acid of the other, and the resulting blend
1 ' ~ ~ I ,
reacted with additional metal base.
Suitable metal bases for the preparation of the mixed metal salts
include the free metals previously enuznerated and their oxides, hydroxides, .
alkoxides and basic salts. Examples; are sodium hydroxide, potassiurn hydroxide,rnagnesiwn oxide, calcium hydroxide, zinc oxide, lead oxide, nickel oxide and the
like.
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The temperature at which the mixed me~al sal~s are prepared is
genersl1y between about 30~ and about 150C, preferably up to about 125CC.
If the mixed salts aré prepared by neutralization of a mlxture of acids with a
metal base, lt is preferred to employ temper~tures abo~e about S0C and
especlally above about 75C~ It is frequently advantageous ~o conduc~ the
reaction in the presence of a ~ubstantially Inert, normally liquid orgallic diluent
such as naphtha, benzene, xylene, m~neral oil or the llke. If the diluent is
mineral oll or is physically and ~hemically simllar to minersl oil, it frequently
need not be removed before using the mlxed metal salt as an ~dditive for
lubrica~lts or functional f~uids.
U.5~ Paten~s 4,308,154 and 4,417,g70 descrlbe proced~res for
preparing these mixed metal sallts and disclose a rlumber ~f examples of such
mixed salts. Such dlsclosures of these patznts are hereby incorporated by
reference.
The preparation of the mixed salts is illustrated by the following
example.
Example C-ZI
A mixture of 67 parts (1.63 equivalents) of zinc oxide and 48 par~s
of mineral oil is ~tirred at room temperature and a mixture of 401 parts (1
equi~alent) of di-(2-ethylhexyl) phosphorodlthioic acid and 36 parts (0.25
equiYalent) of 2-ethylhexanoic acid is added o~er 10 minutes. The temperature
increases to 40C durmg the addition. When sddition is complete, the tempera-
ture is increased to 80C for 3 hours. The mixture is then vacuum stripped at
lG0C to yield Ithe desired mixed metal salt as a 91% solution in mineral oil.
(D) Antioxidant. ~ ~
The lubricating oil compositions of the preserlt invention also may
include an antioxidant (D), with the proviso that (D) the antioxidant and (C) the
metal dithiophosphate are not the same. For instance, (C) and (D) may both be
metal dithiophosphat~s provided that the metal of (C) is not the same as the
metal of (D). In one embodiment, the antioxidants are selected from the group
WO ~3/23~0q 1'~T/US92/~718 ~
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consisting of: sulfur-containing composltions, alkylated aromatic amines, phe-
nols, and oil-soluble transition metal containing compounds. When present, the
lubricating oil co~npositions may contaln from about 0.01 to about 2% or even 5%of at least one antioxidant.
The antioxidant may be one or more sulfur-containing compositicns.
Materials which may be sulfurized to form the sulfurized organic compositions
of the present inventlon include oils, fatty aclds or esters, olefirls or polyoleflns
made thereof or Dlels-Alder adducts.
Olls which may be sulfurlzed are natural or synthetlc oils including
10 mineral oils, lard oil, carboxylic ~cid esters derived from aliphatic alcohols and
fat~y acids vr aliphatic carboxylic acids ~e.g., myrlstyl oleate and oleyl; oleate~
sperm wbale oil, synthetic sperm whale oil subs~itutes and syrlthetic unsaturated
esters or glycerides.
Fatty acids generally contaln from about 8 to about 30 car~on
15 atoms. The unsaturated fatty acids generally contained ln the naturally
occurring vegetable or animal fats and such acids include palmi~oleic acid, oleic
acid, linoleic acid, linolenic acid, and el~cic acid. The fatty acids may comprise
mixtures of acids, such as those obtained frorn naturally occurring animal ar~d
vegetable oils, including beef tallow, depot fat, îard oil, tall oil, peanut o}l, corn
20 oil, safflower oil, sesame oil, poppy-seed oil, soybean oil, cottonseed oiî,
sunflower seed oil, or wheat germ oil. Tall oil is a mixture oî rosin acids, mainly
abietic acid, and unsaturated fatty acids1 mainly o1eic and linoleic acids. Talloil is a by-product of the sulfate process for the manufaGture of wood pulp.
The fatty acid esters also may be prepared from aliphatic olefinic
25 acids of the type described above by reaction with any of the above-descri~edalcohols and polyols. Examples of aliphatic alcohols include monohydrjc alcoholssuch as methanol, ethanol; n- or isopropanol; n-, iso, sec-, or tertbutanol, etc.;
and polyhydric alcohols including ethylene glycol, propylene gîycol, trimethylene
glycol, neopentyl glycol, glycerol, etc.
WO 93/23504 P~/US92/0871X
~; ,, ;'' ''.,: J ,., s'J
The olefinic compounds which may be sulfurized are diverse in
nature. They contain at least one olefinic double bond1 which is defined as a
non-aromatic double bond; that is, one connec~ g two aliphatic carbon atoms.
In lts bro~dest sense, ~he olefln may b13 ~ef~ned by the fonnula R*1R*~C=CR~3-
R 4, whereln each of R*1, R*2, R~3 and R~4 ~s hydrogen or an organic group. In
genernl, the R groups in the aboYe f~rmula which are not hydrogcn may be
s~isfied by such groups as -C~K 5)3,-CooR~5,-CoN~R 5)2,-CooN~R 5)4,
-COOM, -CN, ~X, -YR 5 or -Ar, wherein:
each R 5is independently hydro~en, ~Ikyl, ~lkenyl, azyl, substitu~ed
alkyl, substituted alkenyl or substituted s~rl, witb the proYlso that any two R 5
groups can be alkylene or substituted alkylene whereby a ring of up to about 12
c~rbon atorns is formed;
M is one equlvalent of a metal cation ~preferably Group I or 11, e.g.,
sodium, potassium, bariurn, c~lcium);
X is halogen (e~g., chloro9 bromo, or iodo);
Y is oxygen or divalent sulfur;
Ar is an aryl or substituted aryl group of up to about 12 carbon
atoms.
Any two of R 1, R 2, R 3 and R 4 may also together form an
alkylene OF substituted alkylene ~roup; i.e., the olefinic compound may be
alicyclic.
The olefinic compound is u~ually one in which each R group which
i5 not hydrogen is independently alkyl, alkenyl or aryl group. Monoolefinic and
diole~inic compounds, particularly the fo~ner, are preferred, and especially
terminal monool&finic hydrocarbons, that is, those compvunds in which R 3 and
R 4 are hydrogen and R 1 and R 2 are alkyl or aryl, especially alkyl (that is, the
olefin is aliphatic) having 1 tO about 30, preferably I to about 16, more
preferably 1 to about 8, and more preferably 1 to about 4 carbon atoms. Olefiniccompounds having about 3 to 30 and especially about 3 to 16 (most often less
than 9) carbon atoms are partlcularly desirable.
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lsobutene, propylene and the~r dlrners, trimers and tetramers, and
mixtures thereaf are especially preferred olefinic con~pounds. Of these
compowlds, Isobutylene and diisobutylene are partlcularly des~rable because of
their svailability and th~ p~;l~ularly high sulfur containing compositlons whlchcan be prepared therefrom.
In another embodiment, the sulfurized organic c:ornpound is
sulfurl~ed terpene cozIlpound. The term "terpene compound" as used in the
specification and claims is intended tc~ Include the various isorneric terpene
hydrocarbons having tbe empirlcal formula CloHl6, such as contained In
turpen~ine, pine oil and dipentenes, ~nd the ~arious synthe~lc and naturally
occurring oxygen-ccntaining derlvat1ves. Mixtures of these various sompounds
generally will be utillzed, especially when natural produc~s such as pine oil and
turpsntine are used~ Pine oil, for e~ple, comprises a mlxture of alpha-
terpineol, beta-terpineol, alpha-fenchol, camphor, borneol/isoborneol, fenchone,tS estragole, dilhydro alpha-terpineol, anethole, and other mono-terpene hydrocar-
bons. The specific ratios and amounts of the various components in a given plne
oil will depend upon the p~rticular source and the degree of purification. A
group of pine oil-derived products are available comsnerclally from Hercules
lncorporated. It has been found that the pine oil products genera11y knowrl as
terpene alcohols avallable from Hercules Incorporated are particularly useful inthe preparation of the sulfurized products of the in~ention~ Pine oil products are
available from Hercules under such designations as alpha-Terpineol, Telpineol
318 Prime, Yarmor 3027 Hcrco pine oil, Yarrnor 302W, Yarmor F and Yarrnor 60.
In another embodiment, ttle sulfurized organic composition is at
lea~t one sulfur-containing material which comprises the reaction product of a
sulfur source and at least one Diels-Alder ~dduct. Generally, the molar ratio ofsulfur source to Diels-Alder adduct is in a range of from about 0.75 to about 4.0,
preferably about I to about 3.0, more preferably about I to about 2.5.
The Dlels-Alder adducts are a well-krlown, art-recognized class of
compounds prepared by the diene synthesis or Diels-Alder reaction. A summary
WO 93/23504 rc~/us92/()87lx
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of the prior art relating to this class of campounds is found in the Russian
rnonogr~ph, Dienowl Sintes, Izdatelstwo Akade~ lauk SSSR, 19~3 by A.S.
Onlschenko. (Translated in~:o the Engllsh language by L. Mandel as A.S.
Onischenlco, Piene Synthesis, I~.Y., I:)ani~l D~vey a~d Co., Inc., 1964.) Thls
monograph and references cited thzrein are incorporated by referencc into the
present specification.
Basically, ~he dlene synthesis (l~lels-Alder reaction) involves the
reaction of at least one conjugated dlene with at least one ethylenically or
acetylenlcally unsaturated compound, thes~ latter compounds being known as
dienophiles. Piperylene, isoprene, methylisoprene, chloroprene, and 1 ,3-butadiene
are among the preferred dienes for us~ in preparing the Diels-Alder adducts.
Examples of cycl~c dienes are the cyclopentadienes, fulvenes, 1,3-cyclohexa-
dienes, 1 ,3-cycloheptadienes, 1 ,3,5-cycloeptatrienes, cyclooctatetraene, ~nd
1 ,3,5-cyclononatrienes.
A preferred class of dienophiles are those having at least one
electron-accepting groups selected from groups such as forrnyl, cy~no, n~tro,
carboxy, carbohydrocarbyloxy, etc. Usually the hydrocarbyl and substituted
hydrocarbyl groups, if not present, will not contain more than 10 carbon atoms
each.
One preferred class o f disnophiles are those wherein at ~east one
carboxylic es~er group represented by -C(O)O-Ro where Ro is the residue of a
saturated aliphatic alcohol of up to about 40 carbon atoms, the aliphatic alcohol
from which -Ro is derived can be any of the above-described mono or polyhydric
alcohols. Preferably the alcohol as a lower aliphatic alcohol, more preferably
methanol, ethanol, propanol, or butanol.
In addition to the ethylenically unsaturated dienophiles, there are
rnany useful ac~tylenically unsaturated dienophi}es such as propiolaldehyde,
methyl-ethynylketone, propylethynylketone, ~ propenylethynylketone, propiolic
acid, propiolic acid nitrile, ethyl~propiolate, tetrolic acid, propargylaldehyde,
WO 93/23504 PCr/US92/~7871X
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acetylene-dicarboxylic acid, the dimethyl ester of acetylenedicarboxylic acid,
dibenzoylacetylene, and the like
l~orrnally, the adduc~i invol~e the reactlon of equirnolar amounts
of dlene and dlen~phile. HoweYer, ~f the dienophile has more than one e~hylenic
link~ge, it is posslble for addltional diene to react if present in 1;he reaction
mlxture.
It is frequently ad~antageous to incorporate materlals uscful as
sulfurization promoters in the reac~ion mix~ure~ These materlals may be acidicl
basic or neutral. Useful neutral and acidic materlals include acidified clays such
as "Super Filtrol'l (sulfurlc acid treated diatomaceous earth), p-toluenesulfonic
a~id, phosphorus-containing resgents such as phosphorus acids (e.g., dialkyl~phos-
phorodithioic acids, phosphorus acid esters ~e.g., trlphenyl phosphate), phosphorus
sulfides such as phosphorus pentasulfide and su~rface acti~re agents such as
lecithin.
The preferred prvmoters are basic materials~ These may be
inorganic oxides and salts such as sodium hydroxide, calciuzn oxide and sodium
sulflde. The most desirable basic promoters, however, are nitro~en bases
including ammonla and ~nines.
The amount of promoter material used is generally a~out 0.0005-
2û 2.0% of ~he combined weight of the teI~ene and olefinic compounds. In the case
of the preferred ammonia and amine catalysts, about 0.0005-0.5 mole per mole
of the combined weight is preferred, and about 0.001-0.1 is especially desirable.
Water is also present in the reaction mixture either as a promoter
orl as a diluent for one or more of the promoters recited hereinabove. The
amount of water, when present, is usually about 1-25% ~y weight of the olefinic
compound. The presence of water ls, however, not essential and when certain
types of reaction equlpment are used it may be advantageous to conduct the
reaction under substantially anhydraus conditions.
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When promoters are incorparated into the reaction mixture as
described hereinabove, lt is generally observed ;hat the reaction can be
conducted at lower temperatures, and the product generally is lighter in color.
The sulfur source or reagent used for preparing any of the
sulfur-containing materials of this inverl~iQrl m3y be, for exarnple, sulfur, a sulfur
halide such as sulfur monochlorlde or sulfur dichloride, a mixture of hydrogen
sulfide and sulfur ar sulfur dioxidef or the like. Sulfur, or mlxtures of sulfur and
hydrogen sulfide often are preferred. However, it will be understuod that other
sulfurization rsagents may, when appropriate, be substituted therefor.
~0 Comnlercial sources of all the sulfurlzing re~gents are normally used for ~he
p~ose of thi~ invention, asld ir~purities normslly associated with these comrner-
cial products may be present without adverse results.
When the sulfurlzation reactlon is effected by the use of sulfur
alone, the reaction is effected by merely heatlng the reagents with the sulfur at
temperatures of from about 50 to 250C, usually, from about 150 to abou~ 2I0C.
The weigh~ r~tio of the materials to be sulfurized t~ sulfur is between about 5:1
and about 15:1, generally between about 5:1 and a~out 10:1. The sulfurization
reaction is conducted with efficient agitation and generally in an inert
atmosphere (e.g.~ ni~rogen~. If any of the compos~ents or reagents ~re apprecia-bly volatile at ~he reactiosl temperature, the reaction Yessel may be sealed andmaintained under pressure. It is frequently advantageous to add the sulfur
portionwise to the mixture of the other components.
When mlxtures of sulfur and hydrogen sulfide are utilized in the
, ~ process of thei invention, the amounts of sulfur and hydrogen sulfide per mole of
component(s) eo be sulfurized nre5~respectively~ usually about 0.3 to about 3
gram-atoms and about 0.1 to about~l.5 moles. A preferredrange is from about
0.5 to about 2.0 gram-atoms and about 0.4 to about 1.25 moles, respectively, andthe most desirable ranges are about 0.8 to about 1.8 gram-atoms, and about 0.4
to about 0.8 mole, respectively. In reaction mixture operations, the components
are introduced at levels to provide these ranges. In semi-continuous operations,
.
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they may be admixed at any ratio, but on a mass balance basis, they are present
so as to be consumed in amoun~s within ~hese r~tlos. Thus, for example, if the
re~ction vessel ls initially charged with sulfur alone, the terpene and/or olefinic
compound and hydrogen sulflde sre added incrementally at a rste such that the
desired ratio is ob~ained.
When mixtures of sulfur and hydrogen sulfide are utilized in the
sulfurlzation reactioo, the temperature range of the sulfurization reaction is
generally from about 50 to about 350C. The pref~rred range is about 100 to
about 200C with about 120 ~o ~bout 180~ being e~peclally su~able. The
reaction often is conducted under super atmospheric pressure which may be ~nd
usually is sutogenous pressure ~i.e., pressure whlch ~aturally developed during ~he
course of 1:he reaction), but may also be exter~ally applied pressure. The exactpressure developed during the reaction is dependent upon such factors as design
and operation of th¢ system~ the resction temperature, snd the vapor pressure
of the reactants and products, and it may vary during the course of the reaction.
While }t is preferred generally that th~ reaction mixture conslsts
entireb of ~ the components and reagents described aboYe, the reaction also may
be effected in the presence of an inert solvent (e.g., an alcohol, ether, este~,
:
aliphatic hydrocarbon, halogenated aromatic hydrccarbon, etc.) which is liquid
within the temperature range employed. ~ When the reacti3n temperature is
relatively high, for example, st about 200C, there may be some evolution of
; ~ sulfur from the product which is avoided is a lower reaction temperature such
as from about 15U-170C is used.
In some~ instances, it may be d~sirable to treat the sulfurized
product obtained in accordance with the procedures described herein to reduce
ac:tive~sulfur. The terrn "active sulfur" includes sulfur in a form which can cause
staining of copper~ and similar materials, and~standard tests are available to
determine~sulfur activity. As an alternatlve to the treatment to reduce active
sulfur, metal deactivators can be used with the lubricants containing sulfurizedcompositions.
.
.
WO 93/23504 PCl/US92/08718
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The fol}owing examples relate to sulfurized compositiolls usieful in
the present invention.
Exiample D-l
A reaction ~e~sel is charged with 780 parts isopropyl alcohol, 752
p~rts water, 35 parts of a 50% by weight aqueous solu~ion of sodlum hydroxlde,
60 parts of sulfuric acid treated diatomaceous ear~h (Super Filtrol a~railable from
Engelhard ~orporatlon, Menlo P~rk, New Je~sey) snd 239 parts of sodiwn sulfide.
The mixture is stirred ~nd heated to 77-R0C. The reaction temperature i5 main-
tained for ~wo hours. Themixt~e is cooled to 71C whcreupon 1000 part~ of the
sulfurized olefin prepared by reactlng 337 parts of sulfur monochlorlde with 1000
parts of a mixture of 733 parts of l-dodecene and 100~ pa~ts af Neodene 1618,
a C16_18 olefin mixture ava~lable fro~n Shell Chemical, are added to the mixture.
The re~ction mixture 1~ heated to 77-80C and the temperature Is maintained
until the chlorine content is a mal~imuun of 0.5. The reactiorl mixture is vacuum
stripped to 80C and 20 mlllimeters of mercury. The residue is filtered through
diatomaceous earth. The filtrate has 19~0% sulfur and a specific gravity of 0.95.
Example D-2
A mkture of 100 parts of soybean oil and 50 parts of commerci~l
C16 -olefins is heated to 175C. under nitrogen and 17.4 parts ~f sulfur are
added gradually, whereupon an exothermic reaction causes the temperature to
rise to 205C. The mixturc is h~ated at 188-200C. for 5 hours, allowed to coolgradually to 90C. arld filtered to yield the desired product contaîning 10.13%
sulfur. ~ ~
Ex~nple D-3
2S A mixture~ of lOO parts of so~besn oil, 3.7 parts of tall oil acid and
46.3 par~s of commercial Cls ~8 a-olefins is heated to 165C. under nitrogen and17.4 parts of sulfur are added~ The temperature of the mixture rises to 191C.
It is maintained at 165-200C. for 7 hours and is then cooled to 90C. and
filtered. The product contains 10.l39~ sulfur.
WO 93/23504 pcr/us92/o8718
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Example D-4
A mixture of 93 parts (0.5 equivalent) of pine oil and 48 parts (1.5
equivalents) of sulfur is charged to ~ reactlon vessel equipped with condenser,
thermometer and stirrer. The mlx~ure i5 heated to about 140C wlth nitrogen
blowing and malnt~ined at this temperature ~or ~bout 28 hours. After cooling,
111 p~cs of a C16 alpha-olefin ~vallable from Culf Oil Chemlcals Cornpany
under the general trade name Gulfterle 16) ~re added through an addltion funnel,and after addition is cotnplete, th~ addltion funnel Is replaced with a nitrogentube. The reaction mixture is he~ted to 170C with nitrogen blowing and
1() maintained at the temperature for about 5 hours. The mixture is cooled and
filtered through a fllter ald. The flltra~e Is the desired product having a sulfur
content of 19.01~6 ~theory 19.04%).
Example D-5
(a) A mixture comprising 400 grams of toluene and 66.7 grams
of alumimlrn chloride is charged to a two- liter flask fltted with a stirrer,
nitrogen inlet tube, and a solid carbon dioxide-cooled reflux condenser. A second
m~xture comprising 640 grams (5 moles~ of butylacrylate and 240.8 grams of
toluene is added to the AtC13 slu~Ty over a 0.25-hour period while maintaining
the temperature within the range of 37-58C. Thereafter, 313 grams (5.8 moles)
of butadiene ~re added to the slurry over a 2.75-hour period while maintaining
the temperature of the reaction mass at 60-61C b~ means of external cooling.
The reaction mass is blown with nitrogen for about 0.33-hour and then trans-
ferred to a four-liter separatory funnel and washed wlth a solution of 150 grarns
of concentrated hydr~chloric acid in 1100 gr~ns of water. Thereafter, the
product is subjected to two additional water washings using 1000 ml of water foreach wash. The washed reaction product is subsequently distilled to remove
unreacted butylacrylate and toluene. The residue of this first distillation step is
subje~ted to further distillation at a pressure of 9-10 millimeters of mercury
whereupon 785 grams of ~he desired adduct are collected over the t~mperature
of 105-115C.
.
WC)93/23504 f; y ~ ?~ PCl/US92/nX71
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(b) The above-prepared butadiene-butylacrylate Diels-Alder
adduct (4~50 grams, 25 moles) and 1600 grarns (50 moles) of sulfur flowers are
charged to a 12 liter flask, fit~ed with stirrer, reflwY condenser, and nitrogeninlet tube. I he reaction mixture is heated at a temperature within the range of150-155C for 7 ho~us while p~ssing nI~rogen therethrough at ~ rate of about 0.5cubic feet p~r hour. After heatlng~ ~e mass is perml~ted to cool to room
temperature and filtered, the sulfur-containing product being the flltrate.
The antioxidant (D) may also be ~n alkylated aromatic amine.
Alkylated aromatic ~nines include compounds repre~ented by the formula
R6
Ar3-h-Ar4
wherein Ar3 and Ar4 ~re independently mononuclear or polynuclear, substituted
or unsubstituted aromatic groups; and R6 ls hydlrogen, halogen, OH, NH2, SH~
N02 or a hydrocarbyl group of from 1 to about 50 carbon atoms. Ar3 and Ar4
may be any of the above-described aromatic groups. When Ar3 and/or Ar4 are
substituted aromatic groups, the number of substltuents on Ar3 and/or Ar4 range
independently up to the nwnber of positions ~vailable on Ar3 an~/or Ar4 for
substitution. T~ese substi~uents ~re independently selected from the group
consisting of halogen (e.g., chlorine, bromine, etc.), OH, NH2, SH, N02 or
hydrocarbyl groups of from 1 to about 50 ~arbon atoms.
In a preferred embodiment, antîoxidant ~D~ is represented by the
formula
R8
H
~ f _ N---~\( (XIV)
~7 ~_
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wherein R7 and R~ are independently hydrogen or hydrocarbyl groups of from 1
to about 50 carbon atoms, preferably hydrocarbyl graups af from about 4 to
about 20 carbon atoms. Examples of sroms~ic amines include p,p'-dioctyldi-
phenylamine;octylphenyl-beta-naphthylamlne;octylphenyl-alpha-naphthylamine,
phenyl-alpha~rlaphthylamine; phenyl-beta-naphthylamine; p-octylphenyl-alpha-
naphthylamine and 4-octylphenyl-1-octyl-beta~naphthyliamine and di(nonyl-
phenyl~amine, with di~nonylphenyl)amine preferred.
V.S. Patents 2~558,285; 3,601,632; 3~3~B,975; and 3,S05,225 disclose
diaryl~nines within ~he scope of component (J:)~. These patents are incorporatedherein by reference.
The antioxidants (D) used in the present invention may be one or
more of several ~ of phenolic compounds which may be metal-free phenolic
compounds.
In one embodiment, the antioxid~nt of the present imention
includes at least one metal-free hindered phenol. Alkylene coup}ed derivatives
of said hindered phenols also can be used. Hindered phenols are defined (in the
specification and claims) as those containing a sterically hindered hydroxyl group,
and these ~nclude those deriYatives of dihydroxy aryl compounds wherein tl5e
hydroxyl groups are in the o- or p-position to each other.
The snetal-~ree hindered phenols ma~ be represented by the
following Formulae XY, XVI and XVII.
OH
R9 ~ (XV~
_, ~
R10
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OH OH
R9~ R9 ~XVI)
R10 R10
OH OH
R9 ~ C(R12)~ R~ (XVII)
~ O ~?,10
whereln eac:h R9 is independently an alkyl group cantaining from 3 to about 9
carbon atoms, each R10 is hydrogen or an alkyl group, Rll ls hydrogen or an
slkyl group containi~;g from 1 to about 9 carbon atoms, and ~ach Rl~ is
independently hydrogen or ~ methyl group. In the preferred embodiment, R10 is
an alkyl group conts~ning from about 3 ~o about 50 carbon atoms, preferably
ahout 6 to about 20, more prefer~bly from about 6 to about 12. Exarnples of
such groups include hexyl, heptyl, octyl, decyl, dodecyl, tripropenyl~ tetrapropen-
yl, etc. E:xamples of I?9, R10 and Rll ~groups include propyl, isopropyl, but~l,secondaly butyl, tertiary butyl, heptyl, octyl, and nonyl. Preferablyf each R9 and
Rll are tertiary groups such as tertiar~ butyl, tertiary amyl, etc. The phenoli~compounds of ~the type represented by ~ormula XV may be prepared by various
tech~iques, ansd in one~ embodiment~ such phenols are prepared in stepwise
~: manner by first preparing the para-substituted ~Ikyl phenol, and thereafter
~ alkylating the j para-substituted phenol ~ in the 2- and/or 6-position as desired.
When it is desired to prepare coupled phenols of the type represented by
~: Fonnulae ~CVI and XVII, the second step alkylation is conducted under conditions
which result in the: alkylation of only one of the positions ortho to the hydroxyl
group. ~
Examplès of useful phenolic materials of the type represented by
~ormula XV inciude: 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol;
WO 93/~3504 PCl/US9~iO871~s
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2-t-butyl-4-dodecyl phenol; 2,6-di-~butyl-4-butylphenol; ~,6-dl-t-butyl-4-heptylphenol; 2,6-di t-butyl-4-dodecyl phenol; 2-methyl-6-dl-t-butyl-4-heptyl phenol;
2,4-dimethyl-6-t-butyl phenol; 2,6-t-butyl-~-ethyl phenol; 4-t-butyl catechol; 2,4-
di-t-butyl-p-cresol; 2,6-di-t-butyl-4-methyl phenol; and 2-methyl-6-di-t-
S butyl~4-dodec~rl phenol.
Examples of the ortho coupled phenols of the type represented by
Forrnula ~CVI include: 2,2'-bis(6-~-butyl-4-heptyl phenol); 2,2'-bis(6-t-butyl-4-
octyl phenol); 2,6-bis-~lt-methylcyclohexyl~-4-methyl phenol; and 2l2'-bls(6-
t-butyl-4-dodecyl phenol).
Alkylene-coupled phenolic compounds of the type represented by
Formula XVII can be prepared from ~he phenols represented by Formula XV
wherein R1 1 is hydrogen by reaction of the l~henolic cornpound with an ~ldehydesuch as forrnaldehyde, acetaldehyde, etc. or a ketone such as acetone.
Procedures for coupling of phenolic compounds with aldehydes and ketones are
lS well knGwn in the art, and the procedures do not need to be described in d~tail
herein. To illustrate the process, a phenolic compound cf the type represented
by Forrnula XY wherein R1 1 is hydrogen is heated with a base or an acid, such
as sulfuric acid, in a diluent such as toluene or xylene, and this mixture is then
contacted with an aldehyde or ketone while heating the mixture tp reflux ~nd
removing water as the reaction progresses.
Exarnples of phenolic compounds of the type represented by
Formula XVII include 2,2'-methylene-bis~6-t-butyl 4-heptyl phenol3; 2,2'-methyl-ene-bis(~t-butyl~octyl phenol); 292'-methylene-bis-(4-dode~yl-6-t-butyl phenol);2,2'-methylene-bis-(4-octyl-6-t-butyl phenol); 2,2'-methylene-bis-(4-octyl phenol);
2,2'-methylene-bis-(4-dodecylphenol); 2,2'-me~hylene-bis-(4-heptyl phenol); 2,2'methylene-bisl6-t-butyl-4-dodecyl phenol~; 2,2'-rnethylene-bis(6-t-bu~yl-4-
tetrapropenyl phenol), and 2,2'methylene-bis(6-t-butyl-4-butyl phenol).
The alkylene-coupled phenols may be obtained by reacting a phenol
~2 equivalents) with 1 equivalent of an aldehyde cr ketone. Lower molecular
weight aldehydes are preferred and particularly preferred examples of useful
W0 g3/2351)4 P(~/US92/0~71~s
(, i , ,.; .~ . ,,
-83-
aldehydes include formaldehyde, a reversible polyrner thereof such as paraform-
aldehyde, trioxane, acetaldehyde, etc. AS used In this specification and claims,the word "formaldehyde" shall be deem~d to include such reversible polyrners.
The alkylene-coupled phensls can be derived from phenol or substituted alkyl
phenols, and substituted slkyl phenols are preferred. The phenol must have an
ortho or para pusitiorl ava~lable for reaction with the aldehyde~
In une embod~ment, the phenol w~ll contain one or more alkyl
groups which may or may not resul~ ln a sterically hindered hydroxyl group.
Examples of hindered phenols which can be used in the formation of the alkylene-coupledphenols include: 2,4-dimethylphenol; 2,4-di-t-butyl phenol, 2,6-di-t-butyl
phenol; 4-octyl-6-t-butyl phenol; etc.
In one preferred mbodiment, the phenol from which the alkylen~-
coupled phenols are prepared are phenols substltuted in the para posi~ion with
aliphatic groups containing at least 6 carbon atoms as described above
Generally, the alkyl groups contain from 6 to 12 carbon atoms. Pr~ferred alkyl
groups are derived from polymers of ethylene, propylene, 1-butene and isobutene7preferably propylene tetramer or trlmer.
The reaction between the phenol and the aldehyde, polymer there~f
or ketone is usually carried out between room temperature and about 150C,
2û preferably about 50-125C. Th~ reaction preferably is carried out in ~he
presence of an acidlc or basic material such as hydrochloric acid, acetic acid,
sulfuric acid, amrnonium hydroxide, sodil hydroxide or potassiwn hydroxide.
The relative amounts of the reagents used are not critical, but it is generaJly
convenient ~o juse about 0.3 to about 2.0 moles of phenol per equivalent df
formaldehyde or other aldehyde.
The following exarnples illustrate the preparation of phenolic
compounds of the type represented by Formulae XV and XVII.
Example D-6
A reaction vessel is charged with 3192 parts (12 moles) of a 4-
tetrapropenyl phenol. The phenol is heated to 800e in 30 minutes and 21 parts
WO 93/23504 Pcr/Us92/08718
2 ~ ~s~
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(0.2 mole) of a g3% sulfuric acid solution are added to the vessel. The mixture
is heated to 85C and 1344 parts (24 moles) of lsobutylene are added over 6
hours. The temperature is maintained between 85~91C. Af~er introduction of
the Isobutylene, the reaction Is blown with nltrogen at 2 standard cubic feet per
hour for 30 minutes at 85C. Calcium hydroxlde (6 parts, 0.2 mole) along with
12 p~rts of water are added to the re~ctlon ~vessel. The mlxture is heated to
130C under nitrogen for 1.5 hours. The reaction is vacuum stripped at 130C
and 20 millimeters of mer~ury for 30 minutes. The residue is cooled to gaoc and
the residue is filtered through diatomaceous earth to give the desired product.
The desired product filtrat~ has a specific gra~ity of 0.901 and a percent
hydroxyl (Grignard) equals 4.25 (theoretical 4.49).
Example D-7
A reaction vessel ls charged with 798 parts (3 moles) of 4-
tetrapropenyl phenol. The phenol ~s heated to 95-100C whereupon 5 parts oF a
93% solution of sulfuric acid are added to the vessel. Isobutylene (168 parts, 3moles) is added to the vessel over 1.7 hours at 100C. After introduction of theisobutylene ~he reaction is blown with nitrogen at 2 standard cubic feet per hour
for one-half hour at 100C. An additional 890 parts of the above-describ~d
phenol (2.9~ moles) are added to a reaetion vessel and heated to 34-40~C. A 37%
aqueous formaldehyde solution ~137 grams, 1.7 moles) is added to the vessel. Themixture is heated to 135C with removal of water. Nitrogen blowing at 1.5 scfh
begins at 105-110C. The reac~ion mixture is held at 120C for 3 hours under
nitrogen and cooled to 83C whereupon 4 parts (0.05 mole) of a 50% aqueous
sodium hydroxide solution are added to the vessel. The reaction mixture is
heated to 135C under nitrogen. The reacsion mixture is vacuum stripped to
135C and 20 millimeters of mercury for 10 minutes, cooled to 95C, and the
residue is filtered through diatom~ceous earth. The product has a percent
hydroxyl (Grignard) of 5.47 (~heoretical 5.5) and a molecular weight (vapor phase
osmometry) of 682 (theoretical 667~.
WO g3/Z35~)~ PCr/US92/~8718
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Example 1)-8
The general procedure of Example D-6 is repeated except that the
4-heptyl pherol is replaced by ~n equivalent ~nount of tri-prop~rlene phenol. The
substltuted phenol obtained in this mamler ccntairls S.94% hydroxyl.
Example D-9
The general procedure of Example D-7 is repeated except that the
phenol of Example D-6 is replaced by the phenol of l~cample D 8. The methylene
coupled phenol prepared in this manner contaills 5.74% hydroxyl.
In another embodlment, the lubricànt connpositlons of the present
invention may contain a metal-free ~or ashless) ~Ikyl phenol sulfide. The alkyl
phenols from which the sulfides are prepared also may comprise phenols of the
type discussed above and represented by Formula XV wherein R1 1 is hydrogen.
For example, ~he alkyl phenols which can be converted to allcyl phenol sulfides
include: 2-t~but3rl-4-heptyl phenol; 2-t-butyl-4-octyl phenol; and 2-t-butyl-4-do-
decyl phenol.
The term "alkylphenol sulfides" is meant ~o include s~i-(alkylphenol)-
monosulfides, disulfides, polysulfides, and other products obtained by the reaction
of the alkylphenol with su}fur monochloride, sulfur dichloride or elernental sulfw'.
One mole of phenol is reacted with about 0.5-1.5 moles, or higher, or sulfur
compound. For example, thé alkyl phenol sulfides are readily ~btained by rnixing,
one rnole of an alkylphenol and 0.5-1.0 mole af sulfur dichloride. The reaction
mixture is usually maintained at about 150-160F for about 2-5 hours, after
which time the resulting sulfide is drled and filtered. When elemental sulfur isusçd, one mole of alkyl phenol is reacted with 0.5 to 2.0 moles of elemental
sulfur, and temperatures of about 150-250C or higher are typically used It is
also desirable tha~ the drying operation be conducted under nitrogen or a similar
inert gas.
Suitable basic alkyl phenol sulfides are disclosed, for example, in
U.S Patents 3,372,116; 3,411),798; and 4,021,419, which are hereby incorporated
by reference
WO 93/23504 PCI/US92/08718
- 8 6 -
These sulfur~containing phenolic compositions described in U.S.
Patent 4,021,419 are obtained by sulfurizing a substituted phen~l with sulfur ora sulfur halide and thereafter reac~ing the sulfurized phenol with formaldehyde
or a reversible polymer thereof. Alternatively the substituted phenol can be first
reacted with formaldehyde and thereafter reacted with sulfur or a sulfur halide
to produce the desired alkyl phenol sulflde. The disclosure of U.S. Patent
4,021,419 is hereby incorporated by reference for its disclosure of such
compounds~ and methods for preparlng such compuunds. A synthetic oil of the
type described below is used in place of any mineral or natural oils used in ~hepreparation of the salts for use in this invention.
In another embodiment, the antioxidant (D) may be phenothiazine,
substituted phenothiazines, or derivatives such as represented by ~ormula XVIII
R 1 3S(o)aR 14
~ N ~ (XYIII)
(1?15)b~ ~(R15)b
wherein R14 is selected from the group consis~ing of higher alkyl groups, or an
alkenyl, aryl, alkaryl or aralkyl group and mixtures thereof; R13 is an alkylene,
alkenylene or an aralkylene group, or mixtures tbereof; each R1 5 is independently
alkyl, alkenyl, aryl, alkaryl, aryialkyl, halogen, hydroxyl, alkoxy, alkylthio,
arylthio, or fused aromatic rings, or mixtures thereof; a and b are each
independently 0 or greater.
In another embodiment, the phenothiazine derivatives may be
represented by Formula XIX
WO 93/23504 ~ ~ fr~ ~ ~; . Pcr/uss2~os
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15)b ~ R15)b
~ 13
S(~a ~XIX)
R13
(R15)~ ~ (R )b
S()a~'
wherein R13, R14, R15, a and b are as defined with respect to Fo~nula XVIII.
The above-described phenothiazine derivatit~es, and methods for
their preparation ~re described in U.S. Patent 4,785,095, and the disclosure of
this patent is hereby incorporated by reference for its teachings of such methods
and compounds. In one embodiment, a diallcyldiphenylamine is treated with
sulfur at an elevated temperature such as in ~he range of 145C to 205C for a
suffi~ient time to complete the reaction. A catalyst such as iodine may be
utilized to establish tbe sulfur bridge.
Phenothiazine and its varîous derivatives can be converted to
compounds of Formula ~CVIII by contacting the phenothiazine compound
20 ~ containing the free NH group wlth a thio alcohol of the formula R14SR13OH
where R14 and R13 are defined with respect to Formula XVIII. The thio alcohol
; may be obtained by the reaction of a mercaptan R14SH with an alkyJene oxide
under basic conditions. ~lternatively, the thio alcohol may be obtained by
reacting a terminal olefin with mercaptoethanol under free r~dical conditions.
: ~ 25 The reaction between the thio alcohol and the phenothiazine compound generally
: is conducted in the presence of an inert solvent such as toluene, benzene, etc.
A strong acid catalyst such as sulfuric acid or para-toluene sulfonic acid at about
1 part to about 50 parts of catalyst per 1000 parts of phenothiazine is preferred.
~ ,
WO 93/23504 PCltUS92/1)871~ ~ ~
2 ~ "v ~
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The reaction is conducted generally at reflw~ temperature with removal of water
as It is formed. Conveniently, the reaction temperature may be maintained
between 80C and 170C.
When it is desired to prepare compounds of the type represented
by Formulae XYIII and XIX wherein x is 1 or 2, i.e., sulfones or sulfoxides, thederivatlves ~rep~red by the reactian wl~h the ~hio alcohols descrlbed above are
oxidized with an oxidizing ~gent such as hydrogen peroxide in a solYent such as
gl~cial acetic acid or ethanol under an inert gas blanket. The partial oxida~iontakes place conveniently at from about 20QC to about 150C. The following
examples illustrate the preparation of phenothiazlnes which may be utilized as
the non-phenolic an~ioxidant (D) In the lubricants of the present invention.
Ex~rnple ~-10
One mole of phenothiazine is placed In a one- liter, rsund bottom
flask with 300 ml. of ~oluene. A nltrogen blanket ls maintained in the reactor.
To the mixture of phenothiazine and toluene is added 0.05 mole of sulfuric acid
catalyst. The mixture is then beated to reflux temperature and 1.1 moles of
n-dodecylthioethanol is added ~ropwise over a period of approximately 90
minutes. Water is continuously removed as it is fo~Tled in the reaction process!The reactlon mixture is continuously stirred under ~eflux until
substantially no further wa~er is eYolved. The reaction mixture is then allowed
to cool to 90C. The sulfuric acid catalyst is neutralized with sodium hydroxide.
The solvent is then removed under 8 vacuum of 2 KPa at 110C. The residue is
filtered giving a 95% yield of the desired product.
In another embodiment, the antioxidant (D~ is a transition metal-
containing compos~tion. The transition metal-containing antioxidant is oil-
soluble. The compositions generally contain at least one transition metal
selected from titanium, manganese, cobalt, nickel, copper, and zinc, preferably
manganese, copper, and zinc, more preferably cop~er. The metals may be in the
form of nitrates, nitrites, halides, oxyhalides, carboxylates, borates, phosphates,
phosphites, sulfates, sulfites, carbonates and oxides. The transition metal-
WO 93/23504 ~ 2 ~ .;'~ !" 1 PCI /lJS92/0871 X
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containing composltion is generally in the form of a me~al-organic compound
ccmplex. The organ~c compounds include carboxylic acids and esters, mono- and
dlthlophosphsric acids, dlthiocarbamic acids and dispersants. Gerlerally, the
trarsition metal- ::ontaining compositions contain at least about 5 carbon atomsto render the compositlons oll-soluble.
In one embodiment, the organic compound is a carboxylic acld. The
carboxylic acid may be n mono- or pnlycarboxylic acid contalning frcm 1 to
about 10 carboxylic ~roups and 2 to about 75 carbon atorns, preferably 2 to about
30, more preferably 2 to about 24. Examples of monocarboxylic acids include 2-
ethylhexanoic acid, octanoic scid, decanoic acid, oleic acid, linoleic acid, stearic
acid and gluconic acid. Examples of polycarboxyl~c acids include succinic,
malonic, citraconic aclds as well as substltuted versions of these acids. The
carboxylic acid may be one of the above-described hydrocarbyl-subs~ituted
carbQxylic acylat~ng agents.
In another embodim~nt, the organlc compound is a mono- or
dithiophosphoric acid. The dithiophosphoric acids may be any of the above-
described phosphoric acids ~see dihydrocarbyl dithio~hosphate). A monothiophos-
phoric acid is prepared by treating a dithioph~sphoric acid with steam or water.In another embodiment, the organic compound is a mono- or
dithiocarbamic acid. Mono- or dithiocarbamic acids are prepared by reacting
carbon disulfide or car~on oxysulfide with ~ primary or secondary amine. The
amines may be any of the amines described above.
In another embodiment, the organic compound may be any of the
phenols, aroma~ic amines, or dispersants described above. In a préferred
embodiment, the transition metal~ontaining composition is a lower carboxylic
acid-transition metal-dispersant complex. The lower alkyl carboxylic acids
contain from 1 to about 7 carbon atoms and include fo~nic acid, acetic,
propionic, butanoict 2-ethylhexanoic, benzoic acid, and salicylic acld. The
dispersant may be any of the dispersants described above, preferably the
dispersant is a nitrogen-containing carboxylic dispersant~ The transition metal
W(~ 93/23~04 PCr/US92/0~71~ ~
2 1 'i~
so-
complex is prepared by blending a lower carboxylic acid sal~ of a t:ransi~ion metal
with a dispersant at a temperature frozn about 25C up to the decomposition
temperature of the reaction mixture, usually frorn about 25C up to about 100C.A solvent such a xylene, toluene, naphtha or mineral oll may be used.
E:xaznple D-11
The metal complex is obtained by heating at 160~C for 32 hours 50
par~s of copper diacetate monohydrate, 283 par~ Q'~ 11)0 neu~ral rnineral oll, 2S0
milliliters of xylen~ and 507 par~s of ~n acylated nitr()gen in~ermediate prepared
by reacting 4,392 parts of a polybutene-substl~uted succinic anhydride (prepared10 by the reaction of a chlorinated polybutene having a number average molecularweight of 1000 and a chlorlne content of 4 39~ and Z0% molar excess of maleic
anhydride) with 540 parts of an alkylene amine polyæmine mixture of 3 parts ~y
weight of triethylene tetramine snd 1 part by we1ght of diethylene tri~mineJ and3240 parts of 100 neutral mineral oi1 at 130C-2~0C for 3.5 hours. The reaction15 is vacuum stripped to 110C and 5 millimeters of mercury. The reaction is
filtered chrough diatomaceous earth to yield a filtrate which has 59% by weight
4il, 0~3% by weight colpper snd 1.2% by weight nltrogen.
Example D-12
(a) A mixture of 420 parts [7 moles) of isopropyl alcohol and 518
20 parts (7 moles) of n-butyl alcohol ~s prepared and heated to 60C under a
nitrogen atmosphere. Phosphorus pentasulfide (647 parts, 2.91 moles) is added
over a period of one hour while snaintaining the temperature at 65-~7C~ The
mixture is stirred an additional hour while cooling. The material is filtered
through a filter aid, and the filtrate is the desired phosphorodithioic acid.
(h) A mixture of 69 parts (0.97 èquivalent) of cuprous oxide and
38 parts of mineral oil is prepared, and 239 parts (0.88 equivalent) of the
phosphorordithioic acid prepared in (a) are added over a period of about 2 hours.
The r~action is slightly exothermic during the addition, the mixture is thereafter
stirred for an additional 3 hours; while maintaining the temperature at about
:
WO 93/2350~3 Pcr/us92/08718
t.J ~ ;'J ~
-91- :,
70C. The mixture is stripped to 105C/10 srlrn.Hg. and filtered. The fil~rate is
a dark green liquid containing 17.3~ copper.
Example D-13
A ~nixture of 285 parts of 100 neutral mineral oil and 260 parts ~1.8
equivalents) of copp~r (1) oxide is prepared and heated to 93C. Isopropyl,
me1:hylamyldithiophosphoric acid ~1000 parts, 3.3 equivalen~), prepared frorn
phosphorus pentasulflde and a ~0:40 molar mixture of methylarnyl alcohol and
Isopropyl alcohol, is added over 3 hours to the mixture, while the temperature
is maintained at 95-95C. The reaction mLxture is steam blown a~ 105-110C for
3 hours. The reaction m~xture is then nitrogen blowrl at 82-88C for one hour.
The res3idue is filtered through diatomaceous earth. The filtrate is the desiredproduct and contains 20~ oil and 15~35% copper.
(E) Neutral and Basic ~lkaline Earth M tal Sal~.
The lubricating oil compositiuns of the present invention also may
1~ contain at least one neutral or basi~ alkaline earth metal salt of at least one
acidic orgarlic compound. Such salt cornpounds generally are referred to as
ash-containing detergents. The acidic organic compound may be at least one
sulfur acid, carboxylic acid, phosphorus acid, or phenol, or mixtures thereof.,
Calch~n~ magnesium, bariwn and strontiurn are the preferred
alkaline ~earth metals with magnesium preferred in some lubricating oil
compositions. Salt~ containing a mixture of ions of two or more of these alkaline
earth metals can be used.
l`he salts which are useful as component (E3 can be neutral or basic.
The neutral sal~s contain an amount of alkaline earth metal which is jUst
` 25 sufficient t~ neu~ralize the acidic groups present in the salt anion, and the basic
salts contain an cxcess of the alkaline earth metal cation. Generally, the basicor overbased salts are preferred. The basic or overbased sal~s w~ll have metal
ratios ~MR) of up to about 40 and more particularly from about 2 to about 30 or
40. ~ ~
` ~ :
WO g3t235û4 PCI /IJS9Z/OX7J 8
" ~ 2 (:, ~ d
-92-
ide, carbonate, bicarbonate, sulfide, etc., at temperatures above abou~ 50C. Inaddition, various promoters may be used in the neutralizing process to aid in the
incor~oration of the large excess of metal. These promoters include such
compounds as the phenolic substances, e.g., phenol and naphthol; alcobols such
S as m~thanol, 2-propanol, octyl alcohol and Cellosolve carbitol, amines such as
aniline, phenylenediamine, and dodecyl amine, etc. A particularly effective
process for preparing ~he basic barlum salts comprises mixing the acid with an
excess of bariwn in the presence of the phenolic promoter and a small amount
of water and carbonatlng the mixture at an elevated temperature, e.g., ~0C to
about 200C.
As mentioned above, the ~cidic organic compound from which the
salt of component (E) is derived may be at least one sulfur acid, carboxylic acid,
phosphorus acid, or phenol or mixtures thereof. The sulfur acids include sulfonic
acids, tbiosulfonic, sulfinic, sulfenic, partial ester sulfuric, sulfurous and thiosul-
furic acids.
The sulfonic ac~ds which are useful in preparlng component (E)
include those represented by the formulae
RxT~S03H)y , (XX)
and
~ R'(S03H)r ~XXI)
In these formulae, R' is an aliphatic or aliphatic-substituted cycloallphatic
hydrocarbon or essentially hydrocarbon group free frorn acetylenic unsaturation
and containing up to about 60 carbon atoms. When R' is aliphatic, it usually
contains at least about 15 carbon atoms; when it is an aliphatic-substituted
cycloaliphatic group, the aliphatic substituents usually contain a total of at least
about 12 carbon atoms. Examples of R' are alkyl, alkenyl and alkoxyalkyl
WO 93/23~4 P~r/lJs92/0871
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contains at least about 15 carbon atoms; when it is an aliphatic-substituted
cycloaliphatic group, the atiphatic substltuents usually contain a total of at least
about 12 ?arbon atoms. Examples of R' are alkyl1 alkenyl and alkoxyalkyl
radicals, and allphatic-substituted cyclcialiphatic groups wherein the aliphaticsubstituents are slkylt alkenyl, alkoxy, alkoxyalkyl, carboxy~lky1 and the like.Generally, the s~ycloaliphatic nucleus is derlved from a cycloalkane or a
cycloalkene such as cyclopen~ane, cyclohex~ne, cyclohexene or cyclopentene.
Speciflc example~ of R' are cetylcyclohexyl, lau~ yclohexyl, cetyloxyethyl,
octadecenyl~ and groups derived from pe~roleurxl~ saturated and unsaturated
lQ paraffin wax, and olefin polymers including polymerized monoolefins containing
about 2-8 carbon atoms per olefinic monomer unit and diolefins containing 4 to
8 carbon atoms per monomer unit. R' can also contaln other substituents such
as phenyl, cycloalkyl, hydroxy, mercapto, halo, n~tro, ~nino, nitroso, lower
alkoxy, lower alkylmercapto, carboxy, carbalkoxy, oxo or thio, or interrupting
groups such as -NH-, -O~ or -S-, as long as the essentially hydrocarbon character
is not destroyed.
R in Forrnula XX is generally a hydrocarbon or essentially
hydrocarbon group, preferably free from acetylenic unsaturation, and containing
from about 4 to about ff0 allphatic carbon atoms, preferably an alipha~ic
hydrocarbon group such as alkyl or a!kenyl. It may also, however, contain
substituents or interrupting groups such as those enumerated above provided the
essentially hydrocarbon character thereof is retained. In general, any non-carbon
atoms present in R' or R do not accoun~ for more than 10% of the total weight
thereof.
2s T is a cyclic nucIeus whicb may be derived from an arornatie
hydrocarbon such as~ benzene, naphthalene, anthracene or biphenyl, or from a
` heterocyclic compound~such as pyridine, indole or isoindole. Ordinarily, T is an
aroma~ic hydrocarbon nucleus, espec~ially benzene or naphthalene nucleus.
W{~ ~33/235~4 Pcr/US92/0871
~" ,5~ J ( ) ' ' -94-
The subscript x is at least 1 and is generally 1-3. The subscripts
r and y have an average value of sbout 1-2 per molecule and are generally also
1. ~
The sulfonic acids are generally petrsleurn sulfonic acids or
synthetically prep~red alkaryl sulfonlc acids. Among the petroleurn sulfonic
acids, ~he most useful products ~re those prep~red by the sulfonatlon of sultable
petroleum fractio~ls wlth a subsequent removal of ~cld sludge, and purifica~ion.Synthetic alkaryl sulfonic acids are prepared ususlly from alkylated ben%enes
such ~s the Friedel~ rafts reaction products of benzene and polymers such as
tetrapropylene. The following are specific examples of sulfonic acids useful in
preparing the salts (E:). It is to be understood that such examples se~ve also to
illustrate the salts of such sulfonic acids useful ~s component ~E). In o~her
words, for every sulfonic acid enwnera~ed, it ls intended that the c~rrespondingbasic alkali metal salts thereof are also understood to be illustrated. (The sarne
applies to the lists of other acid material~ listed below.) Such sulfonic acids
include mahogsny sulfonic acids, bright stock sulfonic acids, petrolatum sulfonic
acids, mono- and polywax-substituted naphthalene sulfonic ~cids, cetylchloro-
benzene sulfonic acids, cetylphenol sulfonic acids, cetylphenol disulfide sulfonic
acids, cetoxycap~yl benzene sulfonic acids, dicetyl thianthrene sulfonic acids,
dilauryl beta~naphthol sulfonic acids, dicapryl nitronaphthalene sulfonic acids,saturated paraffin wax:sulforlic aclds, unsaturated paraffin wax sulfonic acids,hydroxy-substituted paraffin wax sulfonic acids, tetraisobutylene sulfonic ~cids,
tetraamylene s~lfonic :acids, chiorine substltuted paraffin wax sulfonic acids,
nitroso substituted paraffin wax sulfonic acids, petroleum naphthene sulfonic
~5 ~ acids, cetylcyclopentyl si~lfonic acids, lauryl cycinhexyl sulfonic acids, mono- and
poJywax substituted cyclohexyl sulfonic acids, dodecylbenzene sulfonic acids,
"dimer alkylate" sulfonic acids, and the like.
Alkyl-substituted benzene sulfonic acids wherein the alkyl group
contains at least ~ carbon atoms including dodeGyl benzene "bottoms" sulfonic
3û acids are particularly useful. The latter are acids derived from benzene which
WO 93/23504 PCr/US92/08718
-95-
has be~n alkylated w~th propylene tetramers or isobutene trimers to introduce
1, 2, 3, or more branched-chain C12 subs~ituents on the benzene ring. Dodecyl
benzene bottoms, principally mixtures of mon~ and di-dodecyl benzenes, are
available as by produc~s from the manufacture of household detergents. Slmilar
products obtalned from slkylation bottoms formed during manufacture of linear
alkyl sulfonates (LAS) are also useful in making the sulf~nates used in this
invention.
The production of sulfonates from detergent mamlf~cture
by-products by reactlon with, e g.? SO3, ls well known to those skilled in the art.
See, for exa~nple, the article "Sulfonstes" in Kirk-Othmer '1Encyclopedia of
Chemical Technology", Second Edition, Vol. 19, pp. ~91 et seq~ published by JohnWiley & Sons, N.Y. (1969).
Other de~criptions of basic sulfonate salts which can be inco~porat
ed in~o the lubricating oil compositions of this inventivn as component (E), andtechnique~ for making them can be found in the following U.S. Patents:
2,174,110; 2,202,781; 2,239,974; 29319,121; 2,337,552; 3,488,284; 3,595,790; and3,798,012. These are hereby incorporated by reference for their disclosures in
this regard.
Suitable carboxylic acids from which useful alkaline earth metal
salts (E) can be prepared include aliphatic, cycloaliphatic and aromatic mono-
and polybasic caxboxylic acids including naphthenic acids, alkyl- or alkenyl-sub-
stituted cyclopentanoic acids, alkyl- or alkenyl-substituted cyclohexanoic acids,
and alkyl- or alkenyl-substituted aromatic carboxylic acids. The aliphatic acidsgenerally contain from about 8 to about 50, and preferably from about 12 to
2 5 about 25 carbon atoms. The cycloaliphatic and aliphatic carboxylic acids are
preferred, and they can be ssturated or unsaturated. Specific examples include
2-ethylhexanoic acid, linolenic acid, propylene tetramer-substituted maleic acid,
behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid,
linoleic acid, lauric acid, oleic acid, ricinoleic acid, undecyclic acid, dioctyl-
cyclopentanecarboxylic acid, myristic acid, dilauryldecahydronaphthalene-carbox-
WO 93/2351~4 PCr/US92/0871
r~ 96--
ylic acid, stearyl-octahydrolndenecarboxylic acld, palmltic acid, alkyl- and
alkenylsuccinic acids, acids forrned by oxidation of petrolaturn or of hydrucarbon
waxes, and comrnercially available mixtures of two or more carboxylic acids suchas tall oil acids, rosin acids~ and the llke.
The equiv~lent weight of the acidic organic compound is its
molecular weight dlvlded by the number of acidic groups [i.e., sulfonic acid or
carboxy groups) pr~sen~ per molecule.
The pentavalent phosphorus acids usefu} in the preparation of
component ~E:) may be an organophosphoric, phosphonic or phosphinic acid, or a
thio analog of any of these.
Component ~E) may also be prep~red frorn phenols; tbat is,
compounds containing a hydroxy group bound dlrectly ~o an ~romatic ring. The
term "phenol" as used herein lncludes compounds having more than one hydrvxy
group bound to an aromatic ring, such as catechol9 resorcinol and hydroquino~e~
It also includes alkylphenols such as the cresols and ethy;phenols, and alkenyl-phenols. Preferred are phenols contai~aing at least one alkyl substituent
containing about 3-100 and especially about 6-50 carbon atoms, such as
heptylphenol, octylphenol, dodecylphenol, tetrapropene-allsylated phenol,
octadecylphenol and polybutenylphenols. Phenols containing more than one alkyl
substituent may also be used, but the monoalkylphenols are preferred because of
their avallability and ease of production.
Also useful ~re condensation products of the above-described
phenols with at least one lower aldehyde or kctone, the term "lower" deno~ing
aldehydes and ketones containing not more than 7 carbon atoms. Suitable
:` 25 al~ehydes include formaldehyde, acetaldehyde, propionaldehyde~ etc.The e~ui~ralent weight of the acidic organic compound .is its
molecular weight divided by the number of acidic groups (i.e., sulfonic acid or
carboxy groups) present per molecule. ~ ~
The amount of component (E) included in the lubricants of the
present invention also may be varied over a wide range, and useful amounts in
.. ... , .. . ~ .~ .. , .. .. , .. , j= ~
WO93/235û~ PCl/US9~/0~718
~k j 3 .,
-97
inv~ntion may ~ary from about 0% or abou~ 0.01~6 up to about 5% or more.
Generally, component (E) is present in an amount of from about 0.1 to about 2%.
The following examples illustrate the preparation of neu~ral and
ba~ic alkaline earth metal salts useful as component ~E).
Example E-1
A mixture of 9û6 grarns of an oil solu~ion of arl alkyl phenyl
sulfonic acid (having an average molecular weight of 450, vapor phase nsmome-
try), 564 grams mineral oll, 600 grams tolwene, ~.7 grams magnesiurn oxide and
120 grams water is blown wlth c~rbon dioxide at a tempera~ure of 78-85C for
7 hours at a rate of about 3 cubic feet of carbon diuxide per hour. The reactionmixture is constantly agitated throughout the carbonation. After carbonation,
the reaction mixture is stripped to 165CC/20 torr and the residue flltered. The
filtrate is an oil solution (34% oil) of the desired overbased magn~sium sulfonate
ha~ring a metal ratio of about 3.
Example E-2
A polyisobutenyl succin~c anhydride is prepared by reacting a mole
of chlorinated poly~isobutene) (haYing an avera~e chlorine content of 4.3% and
an average of 82 carbon atoms) with a rnole of maleic anhydride at ~bout 200C;
The resulting polyisobutenyl succinic anhydride has a saponification number of
90. To a mixture of 1246 grams of this succinic anhydride and 1000 grams of
toluene there is added at 25C, 76.6 ~rarns of bariu~sl oxide. The mixture is
heated ~o 115C and 125 grams of water is added drop-wise over a period of one
hour. The mixture is then allowed to reflux at 1 50C: until all the barium oxide
is reacted. Stripping and filtration provides a filtrate containing the desired
p~bduc~.
Example E-3
A mixture of 160 grams of blend oil, 111 grams of polyisobutenyl
(number average Mw=950) succinic anhydride, 52 grams of n-butyl alcohol, 11
grams of water, 1.98 grams of Peladow (a product of Dow Chemical identified
as containing 94-97% CaC12) and 90 grams of hydrated lime are mixed together.
WO 93/23504 PC}`/lJSg2/0~71X
" r!,
-98-
Additional hydrated lime is added to neu~ralize the subsequently added sulfonic
acid, ~he amount of said additional lime being dependent upon the acid nurnber
of the sulfonic acid. An oil solu~ion (1078 grams, 58~ by weight of oil) of a
straight chain dlalkyl benzene sulfonic acid (Mw=430) is added with the
temperature of the reaction mix~ure not exceeding 79C. The temperature is
adjusted to 60C. The reaction prs~duct of heptyl phenol, lime and formaldehyde
(64.5 grams), and 217 grarns of methyl alcohol are added. The reactlon mlxture
is blown with carbon dioxide to a base number ~bromophenol blue) of 20-30.
Hydra~ed lime (112 grams) ls added to the reaction mixture, and the mixture is
blown with carbon dioxide to a base number ~bromophenol blue~ of 45-60, while
maintaining the temperature of the reaction mixture a~ 46-52C. The la~ter step
of hydrated lime addition followed by carbon dioxide blowing is repeated three
more times with the exception with the last repetition the reaction mixture Is
carbonated to a base mlrnber (bromophenol hlue) of 45-55. The reaction mixture
is flasll dried at 93-104C, kettle dried at 143-160C, filtered and adjusted with
oil to a 12.0% Ca level. The product is an overbased calcium sulfonate having
a base nurnber (bromophenol blue) of 300, a metal content ot 12.0~ by weight,
a metal ratio of 129 a sulfate ash content of 40.7% by weight, and a sulfur
content of 1.5% by wçight. The oil content is 53% by weight.
2Q Example E-4
A reaction mixture comprising 135 grams mineral oil, 330 grams
xylene, ~00 grams (n.235 equivalent) of a mineral oil solution of an alkylphenyl-
sulfonic acid (average molecular weight 425), 19 grams (0.068 equivalent) of tall
oil acids, 60 grams (about 2~75~equivalents) of magnesium oxide, 83 grams
,
methanol, and 62 grams water is carbonated at a rate of 15 grams of carbon
dioxide per hour for about two hours at the ~methanol reflux temperature. ~he
carbon dioxide inlet rate is then reduced to about 7 grams per hour, and the
methanol is removed by raising the temperature to about 98C over a three hour
period. Wa~er (47 grams) is added and carbonation is continued for an additional3.5 hours at a temperature of about 95C. The carbonated mixture is then
WO 93/23504 PC-r/US92/0871~
f ~
99
stripped by heating to a temperature of 140-145C over a 2.5 hour period. This
results in an oil solution of a basic magnesiu n salt characterized by a metal
ratio of about 10.
The carbonated mixture Is cooled to about 60-65~C, and 208 grarns
S xylene, 60 grams magnesium oxide, B3 gr~ns methanol and 62 grams water are
added thereto. Carbonation is resumed at a rate of 1~ grams per hour for two
hours at the methanol reflux ternperature. l`he carbon dioxide addition rate is
reduced to 7 grams per hour and the me~hanol is removed by raising the
temperature to about 95C over a three hour perlcd. An ~dditional 41.5 grams
of water are added and carbonation is coDtinued at 7 grams per hour at a
temperature of about 90-95C for 3.5 hours. The carbonated mass is then
heated to about 150~160C over a 3.5 hour period and then further stripped by
reducing the pressure to 20 mm. (Hg.) at this temperature. The ~arbonated
reaction product is filtered, and the filtr~te is an oil-solution of the desired basic
magnesium salt characterized by a metal ratio of 20.
Example E-5
A mixture of 835 grams of 100 neutral minerai oil, 118 grams of
a polybutenyl (Mw,950)-substituted succ~nic anhydride, 140 grams of a 65:3~
molar mixture of isobutyl alcohol and arnyl alcohol, 43.2 grams of a 15% calciumchloride aqueous solution and 86.4 grams of lime is prepared. YVhile m~intainingthe temperature below 80C, 1000 grams of an 85% solution of a primary bright
stock mono-alkyl benzenle sulfonate, having a molecular weight of about 480, a
neutralization acid number of 110, and 15% by weight of an organic diluen~ is
added to the mixture. The mixture is dried at 150C to about 0.79~ water. The
2~ mixture is cooled to 46-52C where 127 grams of the isobutyl-amyl alcohol
mixture described above, 277 grams of methanol and 87.6 grams of a 31%
solution of calcium overbased, formaldehyde-coup!~d? heptylphenol having a
metal ratio of 8 and 2~2h calcium are added to the mixture. Three increments
of 171 grams of lime are added separately and carbonated to a neutrali7ation
base number in the range ol 50-60. ~ A fourth lime increment of 171 grams is
WO 93/2350~ pcr/us92/o871~
t,f ~ , ~ f " 7, '~J
~ - -100-
added and carbonated to a neutralization base nurnber of 45-55. Approximately
331 grams of carbon dioxide are used. The mixture is dried at 150C to
approximately 0.5% water. The reaction mixture is filtered and the filtrate is
the desired product. The product contain~s 41% oil, 12% calcium and has a metal
ratio of 11.
(F) Friction Modiflers.
The lubricating oil composltlons of the present inYention also may
contain friction modlfiers which provide the lubricating oil wlth additisnal
desirable frictional characteristics~ Generally from about 0.01 to about 2 or 3%10 by weight of the friction modifiers is sufficient to provide improved perfor-mance. Various amides and amines, partlcularly tertlary arni~es sre effective
friction modifiers. Examples Df tertiary arnine frlction modifiers include N-fatty
alkyl-N,N-~,iethanol amines, N-fatty alkyl-N,N-diethoxy ethanol amines, etc.
Such tertiary amines can be prepared by reactin~ a fatty alkyl amine wlth an
15 appropriate number of moles of ethylene oxide. Tert~ary amines derived from
naturally occurring substances such as coconut oil and oleoamine are available
from A~nour Chemical Company under the trade designation "Ethomeen".
Particular examples are the Et~lomeen-C and the Ethomeen-O series. Amides
include fatty acid amides wherein the fatty acid contains from 8 to 22 carbon
20 atoms. Examples include oleylsmides, stearylamides~ laurylamides, etc.
Par~ial fatty acid ~ters of polyhydric alcohols also are useful as
friction modifiers. The fatty acids generally contain from about 8 to about 22
carbon atoms, and the esters may be obtained by reaction with dihydric or
polyhydric alcohols containing 2 to about 8 or 10 hydroxyl groups. Suitable fatty
25 acid esters include sorbitan monooleate, sorbitan dioleate, glycerol monooleate,
glycerol dioleate, and mixtures thereof including commercial mixtures such as
Emerest 2421 (Emery Industries Inc.), etc. Other examples of partial fatty acid
esters of polyhydric alcohols may be found in IC.S. Markley, Ed., "Fatty Acids",second edition, par~s I and V, Interscience Publishers (1968).
W093/7,35~4 'f ~ f~ ?~ PC~/IJS9?~/~8718
-101-
Sulfur containing compounds such as sulfurized C12_24 fats, alkyl
sulfides and polysulfides wherein the alkyl groups contain from 1 to 8 carbsn
atoms, and sulfurlzed polyolefins also may function as friction modifieirs in the
lubrica~ing oil compositions of ~he invention.
The lubricating compositions of the present invention may include
other additives such as supplemer~tary dispersants, antiwear agents, extreme
pressure agents, emulsifiers, demulslfiers, ~ntlrust agents, corrosion inhibitorsj~
viscosity improvers, pour point depressantst dyes, and foam inhibitors. These
additives may be present in ~arious amounts depending on the needs of the final
product.
The supplementary dispersants may be selected from the group
consisting of: (a) amine disperssnts other than the carboxylic derivatives (A)
de~cribed above, (b) ester dlspersants, (c) Mallnich dispersants, (d) dlspersantviscosity improvers and (e) mixtures thereof. In one embodiment, the dispersantsmay be post-trested with such reagen~s as urea, thiourea, carbon disulfide, alde-
hydest ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrldes, ni-
triles, epoxides, boron compounds, phosphorus compounds, etc.
Amine dispersants are hydrocarbyl-substituted amines. The~e
hydrocarbyl-substituted amines are well known to those skilled in the art. Theseamines are disclosed In U.S. patents 3,275,554; 3,438,757; 3,454,555; 3,565,804;3,755,433; and 3,822,289. Thes~i patents are hereby incorporated by reference
for their disclosure of hydrocarbyl amines and methods of making the same.
Typical!y, amine dispersants are prepared by reacting olefins and
~ oleifin polymers (polyalkenes) with amines (mono ~ or polyamines~. The polyalkene
may be any of the polyalkenes described above. The amines may be any of the
amines described above. Examples of amine dispersants include poly(propyl-
ene~amine; N,N-dimethyl-N-poly(ethylene/propylene)amine, (50:50 mole ratio of
monomers); polybutene amine; N,N-di~hydroxyethyl)-N-polybutene amine; N-(2-
hydroxypropyl)-N-polybuteneamine;N-polybutene-aniline;N-polybutenemorphol-
ine; N-poly(butene)ethylenediamine; N-poly(propylene)trimethylenediamine; N-
:
WO ~3/23504 Pcr/usg2/o871X
2 1 v . ~, i
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poly(butene)diethylenetriamine;N',N'-poly(butene)tetraethylenepentamine;N,N-
dirnethyl-N1-poly(propylene)-1,3-propylenediaIrline and the like.
In another embodiment, the supplementary dispersant may be an
ester dispersant. The ester dispers~nt is prepared by reacting at lesst one of the
hydrocarbyl~substituted carboxyllc acylat~ng agents descrlbed abov~ as ~A-1~ wlth
at least one organic hydroxy compound and optlonally an amlne. In another
embodiment, the ester dispersant Is prepared by reacting the a~rla~ing agent
w~th at least one of the above-described hydroxy amine.
The organic hydroxy compound includes compounds of the general
formula R1'~OH)m wherein ~" is a monovalent or polyvalent organic group 30ined
to the -OH groups through a carbon bond, ~nd m is anlnteger of from 1 to about
10 wherein the hydrocarbyl group contains at least about 8 allphatic carbon
atoms. The hydroxy compounds may be aliphatic compounds such as monohydric
and polyhydric alcohols, or aromatic compounds such as phenols and naphthols.
The aromatic hydrcxy compounds from which ~he esters may be deri-ved are
illustrated by the following specific examples: phenol, beta-naphthol, alpha-
naphthol, cresol9 resorcinol, catechol, p,p'-dihydroxybiphenyl, ~-chlorophenol,
2,4-dibu~ylphenol, etc.
The alcohols frorn which the esters may be derived preferably
contain up to about 40 aliphatic carbon atoms, preferably from 2 to about 30,
more preferably 2 to about IO. They may be monohydric alcohols such as
methanol, ethanol, isooctanol, dodecanol, cyclohexanol, etc. In one embodiment,
the hydroxy compounds are polyhydric alcohols, such as alkylene polyols.
Preferably, the polyhydric alc~hols contain from 2 to about 40 carbon atoms,
more preferably 2 to about 20; and preferably from 2 to about IO hydroxyl
groups, more preferably 2 to about 6.~ Polyhydric alcohols include ethylene
glycols, including di-, tri- and tetraethylene ~Iycols; propylene glycols, including
di-, tri- and tetrapropylene glycols; glycerol; bu~ane diol; he~cane diol; sorbitol;
arabieol; mannitol; sucrose; fructose; glucose; cyclohexane diol; erythritol; and
pentaerythritols, including: dl- and tripentaerythritol; preferably, diethylene
WO 93/23504 ;~ 2 .3 .i~ r.J PCrtUS92/08718
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glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol and dipentaeryth-
ritol.
The polyhydric alcohols may be esterifled with monocarboxylic
acids haYiDg from 2 to about 30 c~rbon atoms, preferably about 8 to about 18,
proYided that at least one hydroxyl group remains unesterifled. Exa~nples of
monocarboxylic acids include acetic, propionic, bu~yric and fatty carboxylic
acids. The fat~y monocarboxylic acids Ihave from ab~ut 8 ~o about 30 carbon
atoms and include octanoic9 oleic~ stearic, llnoleic, dodec~noic and tall oi~ acids.
SpecUic examples of these esterified polyhydric alcohols irlclude sorbitol oleate,
including mono- and dioleate, sorbltol stearatet including mono- and distearate,glycerol oleate, including glyc~rol mono-, dl- snd trioleate ~nd erythritol octano-
ate.
The carboxylic ester dispersants may be prep~red by any of seYeral
known methods. The method which is preferred because of conYenience and the
superior properties of the esters it produces, involves the reaction of a the
carboxylic acylating agents described above with one or more alcohols or pheno}sin ratios of from about 0.5 equivalent to about 4 equivàlents of hydroxy
compound per equivalent of acylating agent. The esterification is usually carried
out at a tempera~ure above about 100C, preferably between 150C and 300C.
The water formed as a by-product is removed by distillation as the esterification
proceeds~ The preparation of useful carboxylic ester dispersant is described in
U.S. Pa~ents 3,522,17~ and 4,234,435.
The carboxylic ester dispersants may be further reacted with at
ieast one of the abave described amines and ~referably at least one of the abo~e~5 described polyamines The amine is added in aD amount sufficient to neu~ra}ize
any nones~erifed carboxyl groups. In one preferred embodiment, the nitrogen-
containing carboxylic ester di~persants are prepared by reacting about 1.0 to 2.0
equivalents, preferably about l.0 to 1.8 equivalents of hydroxy compounds, and
up to about 0.3 equivalent, preferably about 0.0'2 to about 0.25 equivalent of
~0 polyamine per equivalent of acyla~lng agent.
WO 93/23S04 PCr/US92~8718
1 04
In another embodirnent, the carboxylic acid acylating agent may
be reacted simultaneously with both the alcohol and the amine. There is
generally at least about 0.01 equivalent of the alcohol and at least 0.01
equivalent of the amine although the to~al ~nount of equivalents of the
comblnation should be at least about O.S equivalent per equivalent vf acylatlng
agent. These ni~rogen-containing carboxylic ester dlspersant compositions are
known ln the art, and the prepar~tion of a number of these deriYatives is
described in, for example, U.S. Patents 3,957,854 and 4,234,43$ which have been
incorporated by reference previously.
The carboxylic ester dispersan~s and methods of making the same
are known in ~he art and are disclosed In O~S. Patents 3,219,6G6; 3,381,022;
3,522,179; and 4t234,435 which are hereby incorporated by reference for their
disclosures of the preparation of carboxylic ester dispersants.
The following examples {llustrate the ester dispersants and the
processes for preparing such esters.
Example SD-l
A subs~antially hydrocarbon-substituted succirlic anhydride is
prepared ~y chlorinating a polybutene having a number average molecular weight
of lQ00 to a chlorine content of 4.5% and then heating the chlorinated poly-
butene wlth 1.2 molar proportions of maleic anhydride at a temperature of
150-220C. A mixture of 874 gr~ns (1 mole) of the succinic anhydride and 104
grams (1 mole) of neopentyl glycol is maintained at 240-250C/30 mrn for 12
hours. The residue is a mixture of the esters resulting from the esterification
of one and both hydroxy groups of the glycol.
Exarnple SD--2
A mixture of 3225 parts (5.0 equivalents) of the polybutene-substi-
tu~ed succinic acylating agent prepared in Example 11, 289 parts (8.5 equivalents)
of pentaerythritol and 5204 parts of mineral oil is heated at 224-235~C for 5.5
hours. Ttle reaction mixture is filtered at 130C to yield an oil solution of ~he
d~sired product.
WO 93/23504 ~ ? f~ ~ 7~ 9 PCI`/ US92/087 1
- 1 05-
The: carboxylic ester derivati~es which are described above
resulting from the reaction of an acylating agent with a hydroxy-containing
compound such as an alcohol or a phenol may be further reacted with any oif the
above-described amines, and particularly polyarnines in the manner descrîbed
S previously for the ni~rogen-containing dispersants.
In another embodiment, the carboxylic acid acylating agent may
be reacted simultaneously with both the alcohol and the amine. There i5
generally at least about 0.01 equi~alent of the alcohol and at least 0.01
equivalen~ of the ~nine although the total arnount of equi1ralents of the
combination should be at least about 0.5 equivalent per equivalent of acyla~ing
agent. These carboxylic ester derivative compositions are known in the art, and
the preparation of a number of these derivatives is described in, for example,
U.S. Patents 3,957,854 and 4,234,435 which are hereby incorporated by reference.The following specific example illustrates the preparation of the esters whereinboth an alcohol and an amine are reacted with the acylating agent.
f~carnple SD-3
A mixture of 1000 parts of polybutene having a number average
molecular weight Gf about 1000 and 108 parts (1.1 moles) of maleic anhydride is
heated to about l9DC and 100 parts (1.43 mole~s) of chlorine ar~ added beneath
the surface over a period of about 4 hours while maintaining the temperature at
about 185-190Co The~ mixture then is blown with nitrogen at this temperature
for several hours, and the residue is the desired polybutenyl-substituted succinic
acylating agent.
A solution of 1000 parts of the above-pr~p~red acylating agent ill
857 parts of mineral oil is heated to about 150C with stirring, and 109 parts (3~2
equivalents) of pentaerythritol are added wlth stirring. The mixture ~s blown
with nitrogen and heated ~o about 200C over a period of about 14 hours to form
an oil solution of the desired carboxylic ester intermediate. To the intermediate,
there are added 19.25 parts (.46 equivalent) of a commercial rrlixture of ethylene
polyamines having an average of abaut 3 to about 10 nitrogen a~oms per
.
WO 93/23504 Pcr/US92/0~718
-
~J ','~1, C~ ?. '(, ~
-106-
molecule. The reaction mixture is stripped by heating at 205C with nitrogen
blowing for 3 hours and filtered. The filtrate is an oil solution (45% 100 neutral
min~ral oil~ of the desired amine-modified carboxylic ester which contains 0.35%nitrogen.
The supplementary dlspersant may al~o be a Mannich dispersant.
Mannicb dispersants are generally formed by the re~ction of at least one
aldehyde, at least one of the above described ~nine and at least one alkyl
substituted hydroxyaromatic compound. The reaction may occur from room
temperature to ~25C, usually from 50 to about 200C (75C-15û~C most
preferred), with the arnounts of the reagents being such that the molar ratio ofhydroxyaromatic compound to formaldebyde to ~mine is in the range from about
(1:1:~1) to about (1:3:3).
The first reagent is an alkyl substituted hydr~xyaromatic
c~mpaund. This term includes phenols (which are preferred), carbon-, oxygen-,
sulfur- and nitrogen-bridged phenols and the like as well as phenols directly
linked through covalent bonds (e.g. 4,4'-bis~hydroxy)biphenyl), hydroxy compounds
deri~ed from fused-ring hydrocarbon (e.g., naphthols and the like); and
polyhydroxy compounds such as catecho!, resorcinol and hydroquinone. Mixtures
of one or more hydroxyaromatic compounds can be used as the firs~ reagent.
The hydroxyaromatic compounds are those substituted with at least
one, and preferably not more than two, aliphatic or alicyclic groups having at
least about 6 (usually at least about 30, more preferably at least 50) carbon
atoms and up to about 400 carbon atoms~ preferably 300, more preferably 200.
These groups may be derived from the above described polyalkenes. In one
;~ 25 embodiment, the hydro~y aromatic compound is a phénol substituted with an
aliphatic or alicyclic hydrocarbon-based group having an Mn of about 420 to
:. .
about 10,000. ~ ~
The second reagent is a hydrocarbon-based aldehyde, preferably a
~` lower aliphatic aldehyde. Suitable aldehydes include formaldehyde, benzalde-
hyde, acetaidehyde, the butyraldehydes, hydroxybutyraldehydes and heptanals,
WO 93/2350~ PC~/VS92/0871X
-107-
as well as aldehyde precursors which react as aldehydes under the conditions of
the reaction such as paraformaldehyde, paraldehyde, formalin and methal.
Formaldehyde and its precursors ~e.g., paraforrnaldehyde, trioxane) are preferred.
Mixtures of aldehydes may be used as the second reagent.
The third reagent is any amine descrlbed abuve. Preferably the
amine ls a polyamine ~s described above.
Mannnich dispersants are descrlbed in the following patents: tJ.S.
Patent 37980,569; U.S. Patent 3,877,899; and U.S. Patent ~,~54,059 ~herein
incorporated by reference for their disclosure to Mannich d~spcrsants).
The supplementary dispessant may also be a dispersant-viscosity
improver. The dispersan~-viscosity improvers include polymer backbones which
are functionalized by reacting with an a~nine source. A true or norrnal blcck
copolymer or a random block copolymel, or combinations of both are utilizcd.
They ~re hydrogenated before use in this invention to remove Yirtually all of
their olefinl~ double bonds. Techniques for accomplishillg this hydrogenation are
well known to those of skill in ~he art. Brlefly, hydrogenation is accomplished
by contscting the copolymers vrith hydrogen at superatmospheric pressures in thepresence of a metal catalyst ~uch as colloidal nickel, palladium supported on
charcoal, etc.
In general, it is preferred that these block copolyrners, for reasons
of oxidative stability, contain no more than about S percent and preferably no
more tha~ about Q.5 percent resi~ual olefinic unsaturation on the b~sis of the
total n~nber of carbon-to-carbon coralent linkages within the average molecule.
Such unsaturation can be measured by a number of means well known to those
` 2~ of skill in the art, such; as infrared, NMR, etc. Most preferably, these copoly-
mers contain no discernible unsaturatlon, as determined by the aforementioned
analytical techniques.
The block copolymers typically have number average molecular
weigh~s (Mn) in the range of about 10,000 to about 500,000 preferably about
30tO00 to about 200,000. The weigh~ average molecular weight (Mw) for these
WO 93/23504 PCI /US92/0871 8
-108-
copolymers is generally in ~he range of about 50,000 to abollt 500,0~0, preferably
about 30,000 to abou~ 300,000.
The amine source may be an unsaturated amine compound or an
unsaturated carboxylic reagent which is capable of reacting with an amine. The
unsaturated carboxylic reagents and ~nines are described above.
E7camples oP saturated amine compounds ~nclude N-(3,6-dioxahep-
tyl)maleimide, N-~3-dimethyl~minopropyl)-maleimide, and N-~2~me~hoxyet.hoxy-
ethyl)maleimide~ Preferred amines ~re ~nmonia and primary amine containing
compounds. Exempla2y of such primary arnine-contairling compounds include
arr~nonia, N,N-dimethylhydrazine, me~hy}amine, ethylamine, butylaminf~, 2-meth-
oxyethylamine, N,l~l-dimethyl-1,3-propanediamine, N-ethyl-N-methyl-1,3-pro-
panediamine, N-methyl-1,3-propanediamine, N-~3~aminopropyl)morpholine,
3-methoxypropylamine, 3-isobutyoxypropylamine and 4,7-di4xyoc~ylamine,
N-(3-aminopropyl~-N-l-methylpiper~zine,N~(2-aminoethyl)piperazine,(2-amino-
ethyl)pyridines, aIIIinopyridines, 2-aminoethylpyridines, 2-aminomethylfursrl,
~amin~2~xotetrahy~rofuran, N-~2-arninoethyl)pyrolidine, 2-aminome~hylpyrrol-
idine, 1-me~hyl-2-arninomethylpyITolidine, 1-amino-pyrrolidine, 1-(3-amino-
propyl)-2-methylpiperidine, 4-aminomethylpiperidine, N-(2-aminoethyl)morpho-
line, l-ethyl-3-aminopiperidine, l-aminopiperidine, N-aminomorpholine, and the
like. Of these compounds, N-(3-aminopropyl)morpholine and N-ethyl-N-methyll ,-
3-propanediamine are preferred with N,I~J-dimethyl-1,3-propanediamine being
highly preferred.
Another group of primary ~nine-containing compounds are the
various amine terminated polyethers. The amine terminated polyethers are
available cornmiercially from Texaco hemical Cornpany under the general trade
designation "Jeffamine~'. Specific examples of these materials include
Jeffamine~ M-600; M-1000; M-2005; and M-2070 amines.
Examples of dispersant-viscosity improvers are given in, for
example, EP 171,167; 3,687,849; 3,756,954; and 4,320,01g, which are herein
incorporated by reference for their disclosure to dispersant-viscosity improvers.
WV~3t23504 2~ $~ PCr/US92/0871~
-10~-
1he above dispersants may be post-treated with one or more
post-treating reagents selected from the group consisting of boron compounds
(discussed above), ciarbon disulfide, hydrogen sulfide, sulfur, sulfur chlorides,
alkenyl cyanides, carboxylic acid acylating agen~, aldehydes, ketones, urea, thi-
ourea, guanidine, dicyanodiiamide, hydrocarbyl phosphates, hydrocarbyl
phosphites, hydrocarbyl thiophosph~tes, hydrociarbyl thiophnsphites, phosphorus
sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates,
hydrocarbyl isocyanates, hydrocarbyl isothiocyanates, epoxides, ¢pisulfides,
forrnaldehyde or formaldehyde-producing compounds wlth pherlols, and sulfur
with phenols.
The following U.S. Patents are expressly incorporated herein by
reference for their disclosure of post-treating processes and post-treating
reagents applicable to the carboxylic derivative compositions of this invention:U.S. PatentNos. 3,087,936; 3,254,025; 3,256,185; 3,278,550; 3,282,955; 3~284,410;
3,338,832; 3,533,94~; 3,639,242; 3,708,522; 3,~59?318, 3,865,~13; 4,234,435; ~c.U.~C. Patent Nos. 1,085,903 and 1,162,436 also describe such processes.
In one embodiment, the dispersants are post-trèated with at least
one boron compound. The reaction of the dispersant with the boron compound~
can be effected simply by mixing the reactants at the desired temperature.
Ordinarily it is preferably between about 50C and about 250C. In some
instances it may be 25C or even lower. The upper limit of the temperature is
the decomposition point of the particular reaction mixture and/or product.
The arnount of boron compound reacted with the dispersant
generally is sufficient to ~rovide from about 0.1 to about 10 atomic proportionsof boron for each mole of dispersant, i.e., the atomic proportion of nitrogen orhydroxyl group contained~ in the dispersant. The preferred amounts of reac~nts
are such as to provide Erom about 0.5 to about 2 atomic proportions of boron foreach mole of dispersant To illustrate, the amount of a boron compound having
one boron a~om per molecule to be ased with one mole of an arnine dispersant
WO 93/23504 PCr/VS92/0871~
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having five nitrogen atoms per molecule is within the range from about 0.1 mole
to about 50 moles, preferably frnm about 0~5 mole to about 10 moles.
~orrosion inhibitors, extrerne pressure and antiwear agents include
but are not limited to metal saltsi of a phosphorus acid, chlorinated aliphatic
hydrociarbons; phosphos usi esters including dlhydrociarbyl and trihydrocarbyl
phosphites; boron-containing compound~ including borate esters; dimercaptothia-
diazole derivatives; benzotriazole derivatives; amino-mercaptothiadiazole
derivatives; and molybdenum cornpounds.
Viscosity impr~vers include l~ut are not lirnited to polyisobutenes,
polymethyacrylate acid ~sters, polyacrylate acid es~ers, diene polymers,
polyalkyl styrenes, alkenyl aryl conjug~ted diene copvlymers ~preferably styrene-
maleic anyhydride copolymer esters), polyolefins and multifunctional viscosity
improvers.
Pour poin~ depressants are a particularly usieful type of additive
often included in the lubricating oils described herein. See for example, page 8of "Lubricant Additives" by C.V. Smalheer and R. Kennedy Smith (Lesius-Hiles
Company Publishers, Cleveland, Ohio, 1967).
Anti-foam agents used to reduce or prevent the formation of stable
foam include silicones or orgarlic polymers. Examples of these and additional
anti-foam compositions are described in "Foam Corltrol Agents", by Henry T.
Kerner (Noyesi Data Corporation, 1976), pages 125-162.
These and other additives are desicribed in greater detail in U.S.
Patent 4,582,618 (Col. 14, line S2 through Col. 17, line 1~, inclusive), herein
- incorporated by reference for its disclosure of other additives that may be used
2~ inicombination~with the present invention.
The lubricating compositions of the present invention may be
prepared by blending components ~A~ and (B) as described above with or without
addltional optional additives such as components (C)-(F) and others described
above in an oil of lubricating vlscosity. More often, one or more of the chemical
components of the present invention are diluted with a substantially inert,
wo 93/2350q 2 ~, i~ s'.b PCr/US92/08718
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normally liquid organic diluent/solvent such as mineral oil, to form an additiv
concentrate. These concentrates usually comprise frorn about 20-90%,
preferably 10-50% of connponent (A), 20 to 80%, preferably 0.1 to 20~6 of
component (B) and optionally one or more of the components ~C) through (F).
Chemical concentrations such a~ 15~, 2096, 30~ or 50~ or higher may be
employed. For example, concentrates may contain on a chemical basis, from
about 10 to about 50% by ~eight of the carboxylic derivative composition ~A) andfrom 0.1 to about 10% of ~E~). The concen~rates may also contain about 0.001 to
about 15% of ~C), ~.V01 to about 15% of ~D) and/or about 1 ~o about 20% of (E).
Blending is accomplished by mixing (usually by stirring) the
ingredients from room temperature up ~o the decomposition temperature of the
mixture or individual components. General}y, the ingredients are blended at a
temperature from sbout 25C up to abol~t 250C, preferably up to about 200C,
more preferably up to about 150C, still more preferably up to about 100C.
The following examples illustrate the concentrates and lubricants
of the present invention. "Bal.i' or "remainder" in the table represents that the
balance or remainder of the composition is oil. Unless otherwise indicated, the
amount of each component in the examples is in percent by volume and reflects
the amount of the oil-containing products used in the lubricants.
WO 93/~3504 PCr/lJS92/t~871~s
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Concentrate Examples
Concentrate I
Product of Example A-l 3 45
Product of Example ~1 12
Mineral Oil ~3
Concentrate II
Product of Example ~-2B40
Product of E:xamp}e B-115
Mineral Oil 45
1 û Concentrate III
Product of Example A-2160
Product of Example ~2 15
Prnduct of Example C-1 5
Mineral Oil 20
Concent ate 1~
Product of Example A-2140
Product of Example B-2 10
Product of Example C-2 5
Product of Example D-5 5
Mineral Oil 40
Concenuate V
Product of Example A-2140
Product of Example B-2 10
Product of Example C-2 5
: 25 hoduct of Example D-7 5
Product of Ex~mple E-l 5
Mineral Oil 35
wc) g3/235n4 ~,~, '?~ J; 2 PCI'/US9~/0871X
~1 13-
Lubricant Examples
Lubricant A
Product of Example A-13 6.0
Product of Exarnple ~2 1.2
100 Neutral Paraffinic Oi} Remainder
Lubricant B
Product of Example A-13 6.2
Product of F,xample B-2 1.2
Product of Example C-l 0.5
100 Neutral Paraffinic (:)il Remainder
Lubricant C
Product of Example A-21 5.8
Product of Example B-l 1.0
Product of Exarnple C-2 0.5
Product of Example D-5 0.5
100 Neutral P~raffinic Oil Remainder
Lubricant D
Product of Example A-20 5.0
Product of E:xample ~1 0.8
Product of Example C-2 0.4
Product oî Example D-5 0.5
Product of Example E-l û.4
100 Neutral Paraffinic Oil Remainder
,~ . ,
WO 93/23504 PCI /US92/~71
,J -1 1 4-
TABl E I
Product of Lubricant (% bv volurne)
Example E F G 5
A-1 6.3 6.3 6.0 ---
A-13 ~ _ 5,5
~1 0.~2 0.8~ 0.75 0.80
C-1 0.~S ~.85 l.l 0.~0
D-6 ~~~ ~'37
D-7 0.32 --- ~- ---
D-13 ~ 0.13 0.13 --- 0.10
Di~nonylphenyl)a~nine ~ -- 0.5 ---
Oleyl amide 0.01 0.ûl 0.01 0.01
89~ Hydrogenated styrene-
butadiene copolymer in
100 neutral mineral oil 8.5 6~5 6.5 6.5
Silicone antifoam agent 80 ppm 80 ppm 80 pprn 80 ppm
Oil Bal. Bal. Bal. Bal.
: :
WO 93/23504 ~ 2 ~ PC~/US92/0871
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oils also can be formulated in accordance with this invention which result in
improved fuel economy when used in the crankcase of a passenger automobile.
While the invention has been explained in rela~ion to its prefe~Ted
embodiments, it is to be understood that various modifications thereof will
5become apparent to those skilled in the art upon reading the specificatlon.
Therefore, it is ta be understood that ~he invention dlsclosed hereln is intended
to co~er such modlfications as fall withln the scope of the appended clain~.
,
, .: i I ~ ,:
