Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~557Q(~ :
This invention is concerned with a novel,
improved process for solubilizing and/or stably dispersing
salts of the alkali metals in a substantially inert organic
liquid media compound and to the novel dispersions produced
by the process. Also, the invention is concerned with novel
lubricant and fuel compositions comprising the basic alkali
salt dispersions, which are the products of the subject
process.
Solutions and/or substantially stable dispersions
of basic metal-containing compositions are well known in the
art as are various methods for their preparation. They are
used extensively as detergent and corrosion inhibitors in
lubricating compositions and, particularly, as additives for
lubricants used in internal combustion engines. Also, these
dispersions of overbased metals have been found to be
particularly useful as additives for petroleum-distillate
fuels, especially as anti-screen clogging agents and as smoke
suppressants in diesel fuels. ~ -~
;.:., : : -.
Basic metal-containing compositions, methods for
their preparation, and their utilities are described~in the
following representative U.S. patents: 2,616,905; 2,723,234;
:
2,777,874; 2,781,403; 3,03I,284; 3,256,186; 3,312,618;
3,342,733; 3,410,670 and 3~,410,671. German Auslegeschrift
:` `
1,243,915 and UOS. patent 3,437,465 descrlbe the use~of ~ ~;
~basic metal-containing compositlons as smoke suppressants in
diesel fuel~. All of the above are referred to as exempli~
fying the state of the àrt and for their disclosure of;the
utility of such~baslc meta1-conta1ning compositions. ~
~os~
The basic alkali salt-containing dispersions
produced by the process of the present invention are
particularly useful as additives for lubricating compo-
sitions. For example, these products function effectively
as detergents in lubricating oil compositions for internal
combustion engines. Likewise, in petroleum distillate
fuels, such as gasoline, kerosene~ and fuel oils, they
-are useful as anti-screen clogging agents, and in diesel
and jet fuels they are useful as smoke suppressants, i.e.,
they suppress the formation of black exhaust smoke.
More particularly, this invention is concerned
with the preparation of solutions and/or stable dispersions
in a substantially inert organic media of basic lithium -~-
sulfonates, basic sodium sulfonates, and basic potassium
sulfonates, having metai ratios in the range of from about
four (1~) up to about forty (40). Likewise, the invention
is concerned with the preparation of novel lubricant and
fuel compositions comprising the subject basic lithium
sulfonates) basic sodium sulfonates/ and basic potassiurn `
sulfonates. Another aspect of this invention is the
-preparation o~ the subject basic alkali sulfonates ln the -~
~ ~ .
form of clear,-filterable, homogeneous solutions or sub-
stantially stable dispersions in such organic media
including lubricating olls and normally liquid ~uels.
In the prior art, r.qetal salts of acids having
metal ratios in excess of one have been referred to by a
variety of names, such as "basic~salts", "comp1ex salts",
"super-based salts"/ and "overbased salts". The terminol- ;
ogy of "basic salts" is used herein to define alkali-metal
. . .
salts having metal ratlos in excess of one. The process
-2~
?
~(3 5~700
employed for making such salts is referred to as "over-
basing". The exact nature of these baslc salts is not
clearly understood. Some workers in the art have suggested
~ that the basic salts comprise solutions or, more likely,
stable dispersions of the salt formed by contacting the
acidic material with the basically reacting material.
Others regard the basic salts as "polymeric salts" formed
by the reaction of the acidic material, the soluble acid
being overbased, and the basically reacting metal compound
(German Auslegeschri~t 1,243,915). In view of the above,
the subject basic alkali-metal salts are described herein
. .. .
by reference to the process by which they are formed.
As used herein and in the appended claims, the
"basic" alkali sulfonates are characterized by having a
stoichiometric excess of equivalents of the alkali me-tal
component, in relation to the equivalents of the oil
soluble sulfonic acid component. Thus, while a "normal"
.
or "neutral" alkali sulfonate has a ratio of equivalents
of alkali metal to equivalents of sulfonate of l:1, a
"basic" sul~onate or "baslc" salt has a ratio of equiv-
alen~s of alkali to equivalents of sulfonate greater
~ . ~
than 1:1, such as 1.1:1, 2:1, 4:1, 10:1, 30:1, etc. The
term "metal ratio" is used to designate the ratio o~
equivalents of metal to acid in a basic salt to the number
~ ~ o~ equivalents expected to~be present in a normal sul-
fonate based~upon the usual stoichiometry of the compounds
; involved.~ For example, a disperslon of a "normal" lithium
sulfonate containing one equivalent of an oil-soluble ~ -
sul~onic~acid and one equivalent of lithiurn would have a
30~ metal ratio of one A dispersion of a "basic" sodi~n
~3~
iC~55700
sulfonate containing one equivalent of an oil-soluble
sul~onic acid and 20 equivalents of sodium, would have a
metal ratio o~ 20. In a similar manner, a dispersion of
a ~Ibasic~ potassium sulfonate characterized by the pre-
sence of one equivalent of a petrosulfonic acid~ one
equivalent of an alkyl phenyl sulfonic acid and sixteen
equivalents o potassium, would have a metal ratio of -.
eight.
The process of the present invention is -~or the .
preparation of stable oil-soluble dispersions o~ basic :
alkali sulfonates having metal ratios o~ at least about
four, which comprises intimately contacting; (A) acidic
gaseous materials selected from the group consisting of ~.
carbon dioxide, hydrogen sulfide~ sulfur dioxide, or
mixtures thereof, wi~h (B) a reaction mixture compri.sing
(i) one or more oil-soluble sul~onic acids or derivatives . :~
thereof succeptible to overbasing, (ii) one or more alkali
metals or basically reacting alkali metal compounds, (lil) :~
one or more lower aliphatic alcohols, and (iiii) one or ~
more oil-soluble carboxylic acids or derivatives thereo~;
~or~a. period o~ time suf~icient for the acidic gaseous ~.
material and the components of the reaction mixture to
. .
form the desired disper~ions of basic alkali sul~onates
having the desired metal ratio; wherein the ratlo o~
~ equivalents ~of the carboxylic~ acld component (iili) to
equivalents~o~the sulfonic aold component (l) is;in:the~
range of from about 1:1 to~about 1:20; the ratlo of ~ ~:
equlvalents ~of the alkall component (ii) to equivalents
of the sulfon~Lc acid component (i) is at least 4~ and
1(35570~
the ratio Or equivalents of the alcoholic component (iii)
to equivalents of the sulfonic acid component (i) is in
the range of from about 1:1 to nbout 80:1.
The invention also includes the stable oil-
soluble dispersions of basic alkali sulfonates prepared
according to the above process, as well as lubricant or
fuel compositions comprising a ma~or proportion of lubri-
cating oil or a normally liquid fuel and a minor proportion
of the stable dispersion of the basic alkali sulfonates.
The stable dispersions of the basic alkall sul- -
fonates prepared by the process of the present invention
will have a metal ratio in the range of from about four
(4) up to about forty (~0), with the usual product havi.ng `
a range of from about six (6) to thirty (30). Generally -
the range of metal ratios will be from about eight (8) to
about twenty-five (25).
In the initial reaction mixture, the ratio of
equivalents of the carboxylic acid component (iiii) to ~ - -
equivalents of the sulfonic acld component (i) is ln the
range of from about 1:1 to about 1:20, preferably in the
. ~ range of from about 1:2 to about 1:10. The ratio of~
equivalents~of the alkali metal component (ii) to equiv-
alents of the ~ulfonic acld component (i) is in the~range
of from about ~:1 to about 40:1, preferably in the range
~ ~ of from about 6:1 to about 30:1, and more preferably from
about 8:1 to`about 25:1.~ The ratio of equivalents- of
; t:he alcoholic component~ to equlvalents of~the
sulfonic acid component (i) is in the range of from about~
1; to ~ab;~ut~ ~n~ refe-ably f~om ab~ut 2:1 t~o ab~ut ,O l
1(g5570(~ ; "
It will be apparent to those skilled in the art
that the ratio of equivalents of the alkali metal com-
ponent (ii) to equivalents o~ the sulfonic acid component
(i) may exceed about 40:1. However, such an excess
normally will serve no useful purpose, so that in the
interest o~ economy and other practical considerations,
the ratio of about 4:1 -to about ~0:1 will be used.
The alkali metals are regarded herein as having
one equivalent per molecular weight. The oil-soluble
sulfonic acids and oil-soluble carboxylic acids are
regarded as having one equivalent per acidic hydrogen or -
acid group. Accordingly~ mono-carboxylic acids or mono-
sulfonic acids or their equivalent derivatives, such as ~;
esters, metal salts, and ammonium saltsJ have one equiv-
alent: weight per molecular weight of the acid or deriv-
ative. A disul~onic acid or dicarboxylic acid, or
equivalent derivatives, such as esters, and salts, has
. .
two equivalents per molecular weight. The lower aliphatic
alcohols have one equivalent per hydroxy group. Thus,
~ ~ methanol has one equivalent per~molecular weight, whlle
ethylene glycol has two equivalen-ts per molecular weight.
Generally~ the acldlc gaseous material lS con- - -
tacted with the reaction mixture until there is no further
~ reaction between the comp~onents of the reaction~mixture
-~ 25 ~ and~-the acidic materiaIJ or until a reaction between the
gaseous material and the mixture substantially c~eases~
hile~ it is preferred that~the reaction be continued ~mtll~
no~further overbased prod~uct is ~ormed, useful dispersions
within the~sc~ope~of this~invention,~can be prepared when
30;~ contact b~etween the gaseous~materlal and the~reaction~
1~55700 ~;.
mixture is maintained for a period of time sufficient
for about 70% of the total acidic gaseous material to
react with the mixture. The lower limit of about 70~ is
relative to the amount required if the reaction mixture
were permitted to proceed to its completion or "end
point".
The determination of the point at which the
reaction between the acidic gaseous material and the
reaction mixture is completed or substantially ceases,
may be ascertained by any of a number of methods con-
ventional in the art. One such method involves a measure-
ment of the amount of gas being contacted with the mixture
and the amount of gas leaving the mixture, thus~ where
the amount o:~ gas being contacted with the reaction mix-
ture substantially equals, i.e., corresponds froin abbut 90
to about 100~, the gas leaving the mixture. The amount of
gas being contacted with the mixture and leaving~the mix-
ture is readil~ determined by the use of metered inlet
and outlet valves for the gas. ~ ~ -
The temperature at which the acidic gaseous
rnaterial~ls contacted with th-~ components of th~ re~action
mixture is not critical. Thus, the minimum temperature
IS that ternperature at wh~ich the reaction mixture remains
fluid, i.e,, does not solidify. The maximum temperature
25 ~ ~ is dependant upon the decomposition temperature of the
reaction mixture, product,~or gaseous reactants. Thus,
the reàctlon~tempera~ure~will be in the range of from about~
the~solidiflcation tempe~rature of the reactlon~mlxture~up~
to~the decomposition temperature of that component of` ~ ~
0~ the mixture or~product or acidic gaseoùs reactant having ~ -
~5570~
the lowest decomposition temperature. Usually, the
reaction temperature will be in the range of from about
25C. up to about 200C.~ and preferably in the range of
~rom about 50C. to about 150C. The acidic gaseous
material is conveniently contacted with the components of
the reaction mixture at the reflux temperature of the
mixture. This reflux temperature will obviously depend
upon the boiling points of the various components of the
reaction mixture. Thus, when methanol is being used, the
contact temperature will be at about the reflux temperature
o~ methanol.
Normall~, the reaction will be conducted at
atmospheric pressure although super atmospheric pressure
o~ten expedites the reaction and is conducive to optimum
-15 utilization of the acidic gaseous reactant. The process 7^" .'.''
can also be carried out at reduced pressure but, for
obvious practical reasons, this is usually not done.
The process of the present invention is con- ;
ducted in the presence of a substantially inert organic liquld
diluent, which functions as both the dispersing media and
the reaction media. This diluent will comprise at least
about 10~ by weight of the total weight of the inltlal
reaction mixture. Ordinaril~, the amount of diluent used
will not exceed about 80~ by weight of the reaction mix-
::
25 ~ ture. Preferably, the amount of diluent used will be in
thè~range of ~rom about ~O%~up to about 70% of the total`
nitlal we1ght of the reactlon mixture.
Although~a wide variety of diluents ~are useful,
it is p;re~ferre~d to use~a dlluent whlch is soluble in
30 ~ lubrlcating oil or normally liquid fuel, particularly
~5570~ :
when the final reaction product is to be used as an
additive in lubricant or fuel compositions. Accordingly,
the diluent usually comprises a low viscosity lubricating
O11J such as synthetic or natural lubricating oils, or a
normally liquid petroleum distillate fuel, such as kero-
sene or diesel fuel.
Other organic diluents can be employed either
'alone or in combination with each other or in combination
with the above-discussed lubricating oils or liquid fuel
diluents. Particularly preferred diluents include the
aromatic and halo-aromatic hydrocarbons, such as benzene,
toluene, xylene, chlorobenzene; lower boiling petroleum
distillates, such as petroleum ether and the various
naphthas; the normally liquid aliphatic and halo-aliphati.c
hydrocarbons, such as hexane, heptane, hexene, cyclo-
hexene, cyclopentane, cyclohexane, ethylcyclohexane, and
the like. Dialkyl ketones, such as dipropyl ketone, and
ethyl-butyl ketone, and the alkyl aryl ketones, such as
acetophenone are likewise useful as suitable diluents.
Also, ethers3 such as n-propyl ether, n-butyl ether, n-
butyl methyl ether, and isoamyl ether are useful diluents.
These diluents may be used alone or in'.combination with~
mineral oil or other natural or synthetic oils.
When a combination of oil and one or more of
~ another diluent is used, the weight ratio of oil to the
other diluent is generally in the range of from about 1:20
to about 20~ It is usual~ly desirable for a mineral
lubricating oil to c~omprise at least about 50~by weight~
of the weight of dlluent,~especially if the product is ~ -
,
. :
1(3557011:~
to be used as a lubricant additive. The total amount of ;
diluent present is not particularly critical, since the
diluent is inactive. However~ the diluent will ordinarily
comprise from about 10$ to about 80~, and pre~erably about
30~ to about 70% by weight of the reaction mixture based
upon the total weight of material in the reaction mixture.
The process of the present invention may be
conducted in the presence of small amounts of water~
which may be introduced into the reaction mixture through
the use of technical grade reagents, or otherwise.
Generally, water may be present in the initial reaction
mixture in amounts up to about 10~ by weight o~ the total
initial reaction mixture without having harmful effects.
Upon completion of the above treatment with the
acidic gaseous material, any resulting solids are preferably
removed from the reaction mass by filtration, or other
conventional means. Optionally, readily removable diluents,
,
the alcoholic promoters, and/or water formed during the
reaction can be removed by conventional techniques, sUch
. .
as distillation, prior to use. It is usually desirable
to remove substantially all water from the reaction mix-
:: . .
ture since the presence of water o~ten leads to dif~
culties in filtration and may lead to the ~ormation of
undesirable aqueous emulslons in ~uels and lubrlcant
composit~ons. Any water present in the reaction~mass is
: .
read~ly~removed by heating at atmospheric or reduced
pressures or as an azeotrope
When used as an additive, the resulting reaction ;
productJ including the inert diluent, can be added directly
30 ~ to the lubricating oil or fuel composition in which it is
~5~7~
to be employed. As will be apparent to those skilled in
the art, the amount of diluent employed can be increased
or decreased during formulation of the dispersions or
before adding it to the ~uel or lubri.cant, to facilitate
mixing, temperature control, or to meet so~e other parti-
cular requirements related to the ultimate use of the
composition.
The acidic gaseous materials used in the process
of the present invention are either carbon dioxide, h~dro-
gen sul~ide, or sulfur dioxide. Mixtures o~ these gases
are also useful. Carbon dioxide is the particularly
pre~erred gaseous material due to overall considerations
of cost, ease o~ use, availability and perrormance o~ the
resulting product.
- 15 The subject basic alkali sulfonates are prepared
using llthiurn, sodium, or potassium, or their basically
reacting compounds, such as hydroxides, alkoxides derived .:
from alcohols of up to ten carbon atoms3 particularly
lower alkanols o~ up to seven carbon atoms, hydrides, :
.
~ 20 and amides. Thus, useful basically reacting alkali- ~
-~ metal compounds include sodium hydroxide, potassium :
hydroxide, lithium hydroxide~ sodium propoxide, Iithium
methoxide, and potassium ethoxide, sodium butoxide,
-
lithium hydride~ sodium hydride, potassium hydride,
potassium amide, sodium amide, and lithium amide. As the
~pre~erred baslc alkall sulfonate containing dispersions of
this invention are the basic sodium sul~onate containing
dispersions, sodium and its basically reacting compounds,~
especially~ sodium hydroxide and sodium alkoxides, are the
30~ preferred alkali metal reactants.
:~ : . . . .
.
~S~70s~ . ':
The oil-soluble sulfonic acids useful in the
preparation o~ the subject basic alkali metal sulfonates
correspond to the following .~ormulas:
` RX-T-(so3H)~ (I)
R'-(S03H)r (II)
In formula (I), T represents a cyclic nucleus
of the mono- or polynuclear type, includ mg benzene,
naphthalene, anthrasene,1,2,3~4,-tetrahydronaphthalene,
thianthrene, biphenyl and the like. Usually, T is an
arolmatic hydrocarbon nucleus such as benzene or naphthalene.
R represents a hydrocarbon or a substantially hydrocarbon
radical containing at least about eight aliphatic carbon
ato~s per sul~onic acid molecule, and preferably at least
about twelve aliphatic carbon atoms. Thus, R represents, ~ -
15 for example, aliphatic groups such as alkyl, alkenyl,
alkoxy, al~oxy alkyl, carboalkoxy alkyl and aryl alkyl. :
The variables x and y are integers having val.ues of 1,2,
or 3 and their combined average value preferably will be
from two to four.
2~0 ~ More specifically, R represents aliphatic hydro-
ca.rbon~groups such as alkyl or alkenyl radicals, whlch
.
. may contain additional substituènts on the alkyl or
alkenyl radical provided the substantiaI hydrocarbon
character of the radlcal lS retained. Representative;
examples of R include butyl~ lsobutyl, pentyl~ octyl,
nonyl, dodecyl, docosyl, tetracontyl, 5-chlorohexyl,
4-ethoxypentyl, 4-hexenyl, 3-c~yclohexyloctyl, 4-(p-chloro~
phenyl)~-octyl, 2,3,5-trlmethylheptylJ 4-ethyl-5-methyloctyl
and substituents derived~from polymerized olefins~such as
GI~rO~ 0~ ol~ropl ne~ o-
~0~7~0
butylenes, ethylene-propylene copolymers, chlorinated
ole~in polymers, oxidized ethylene-propylene copolymers,
and the like having number average molecular weights in
the range o~ about 150 to about 6,ooo. Representative
of the non-hydrocarbon groups which can be substituted on
the substantially hydrocarbon radical R, include nitro,
amino, chloro~ bromo, lower alkoxy, lower alkyl mercapto,
oxo (=0), thio ~=S), interrupting groups such as the -NH-,
-0-, -S-, and the like,provided the substantial hydrocarbon
character o~ the R radical is retained. For purposes of`
this invention the substantial hydrocarbon character is
retained so long as any non-carbon atoms present in the
R radical does not account ~or more than about 10~ o~ the
~ .
total weight of the R radical. Usually R is an aliphatic
hydrocarbyl group, i.e., alkyl or alkenyl o~ ~rom about
eight to about ~our hundred carhon ato~s and pre~erably
~rom about twelve to about one hundred carbon atoms. Such
- , ..
al~yl or alkenyl groups include those derived ~rolll poly- ~-
merized ole~ins as described above
In Formula (II), R' represents an aliphatic
hydrocarbon radical, aliphatic-substituted cycloaliphatic
: .
; ~ ~ radical, ~or a-substantialLy hydrocarbon radical. Where
R' is an aliphatic radicalJ it should contain at least
about 15 to about 18 carbon atoms, and where R' is an
allphatic~-substltuted cycloallphatic radical, the aliphatic
substituents should contain a total of at least about 12 ~ -
carbon at;oms Representative~examples of R' are~alkyl~
alkenyl, anù alkoxyalkyl radicals, and aliphati~c-sub-
stituted cycloaliphatic radicals wherein the aliphatic~
1~57[)~
substituents are alkoxy, alkoxy aryl, carboalkoxy aryl,
etc. Generally, the cycloaliphatic radical will be a
cycloalkane nucleus or a cycloalkene nucleus such as cyclo-
pentane, cyclohexane~ cyclohexene, cyclopentene, and the
like. Specific representative examples of R' are cetyl-
cyclohexyl, laurylcyclohexylJ cetyloxyethyl, and octa-
decenyl radicals, and radicals derived from petroleum,
saturated and unsaturated paraffin wax, and polymerized
mono- and di-olefins containing up to about eight carbon
atoms per olefin monomer unit. As discussed with regard
to R above, R' can also contain other substituents such
as hydroxy, mercapto, halo, nitro, amino, nitrosoJ carboxy,
lower carbyl alkoxy, and the like as long as the substantial
hydrocarbon character of the group is not destroyed.
Illustrative examples of the sulfonic acids are
mahogany sùlfonic acids, petrolatum sulfonic acids, mono-
; ., .
and polywax-substituted naphthalene sulfonic acids, ;
cetylchlorQbenzene sulfonic acids, cetylphenol sulfonic~
- acids, cetylphenol disulfide sulfonic acids, cetoxycapryl
. . .
benzene sulfonic acids, dicetyl thianthrene sulfonic acids
- dilauryl be~a-naphthyl sulfonic acidsl dicapryl nitro-
: ..
naphthalene sulfonic acids, paraffin wax sulfonic acids,
~- unsaturated paraffin wax sulfonic acidsl hydroxy-substituted
paraffin wax sulfonic acids, tetraisobutylene sulfonic
~; 25 ~ acids, tetramylene sulfonlc aclds, chloro-substituted
paraffin wax sulfonic acidl nitrosyl-substituted paraffin
wax sulfonic acidsl petroleum naphthalene sulfonic acids,~
cetylcyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic
acids, mono-~ and polywax-substituted cyclohexyl sulfonic
~ ~ acldsl and the like.
: :~
.
1OSS7~
As used herein, the terminology "petroleum
sulfonic acids" or "petrosulfonic acids" includes the well~
known class o~ sulfonic acids derived from petroleum pro-
ducts according to conventional processes known in the
art. Such processes are disclosed in the following repre-
sentative U.S. patentsl 2,480,6~8; 2,48~800; 2,717,265;
2,72~,261; 2,794,829; 2,8~2,801; 3,225, o86; ~,337,613;
-and 3,351,655. Other prior U.S. patents discussing the
preparation of sulfonic acids discussed above are 2,616,904;
lo 2,616,905; 2,723,234; 2,723,235; 2,723,236; 2,777~ 874;
and the other U.S. patents referred to in each of these '
patents. Since, from the above, it is apparent that these
oil~soluble sul~onic acids are well known in the art, no
~urther discussion o~ these is required herein ~ '
Of course, mi~tures Or the above-described
sulfonic acids and their derivat'ives succeptible'to over-
basing can be employed in the process of the present
invention. Representative examples of derivatives of the
sulfonic acids succeptible to overbasing include metal
2Q salts, such as the alkaline earth salts (magnesi~
calcium, barium), zinc, lead, etc; ammonium salts;
amine salts, such as ethyl amine~ butyl amine, ethylene
~ ~ polyamine; esters, such as ethyl, butyl, glycerol,; etc; ~ '
;~ - and their anhydrides.
The alcoholic component of the reaction mixture
serves as a promoter and is a lower aliphatic mono- or
dlhydric alcohol. The lower alcohols usef`al in the pro~
cess Or the present invention include alcohols having up
to about eight~carbon atoms. Representative o~ the
examples of ùseful alcohols are methanol, ethanol,
1~557~(~
l-propanol, l-hexanol~ isopropanol, isobutanol, 2-pentanol,
2,2-dimethyl-1-propanol, l-octanol, ethylene glycol,
l,~-propanediol, and l,5-pentanediol. Mixtures of these
alcohols are also useful. A particularly useful alcoholic
component is a member selected from the group consisting
of methanolJ ethanol, and propanol. Methanol is especially
preferred as the alcoholic component.
The oil-soluble carboxylic acid component of the
reaction mixture corresponds to the general formula
R-(COO~I)n, wherein n is a positive whole number having a
value of from 1 to 6, preferably 1 or 2, and R/~represents
a saturated or substantially saturated aliphatic hydro- :
carbon radical having at least eight aliphatic carbon atoms.
Depending upon the value of n, R/will be a mono- to hexa~
valent radical.
In addition to the acid, functional derivatives
of the acid are useful in the process of the present inven-
tion. Thus, the corresponding acid anhydrides, esters,
amides, imides, amidines, metal salts, and mixtures of
these are equally useful.
The hydrocarbon substituent, R may contain inert
polar substituents provided they do not alter substantially
the hydrocarbon character of R~l Preferably the upper lim3t
on the percentage of polar substituents is about 10~ by
weight based upon the t~otal weight of the hydrocarbon sub-
- stituent. Exemplary polar substituents include halo,
carbonyl, oxo(-0-), formyl~ nitro, thio(~S-), etc. Like-
wise, the hydrocarbon substituent (R'/)may contain olefinic
unsaturatian up to a maximum of about 5~ olefinic linkages
~0 ~ based upon the ~otal number of carbon-to-carbon covaIent
: ,
~ -16- ' ~
: :
57~
linkages present in the substituent. Preferably, the
number of olefinic linkages will not exceed two percent
of the total covalent linkages. The number of carbon
atoms in the hydrocarbon substituent (~ will vary from
about eight up to about 700 depending upon the source of R.
As discussed below, a particularly preferred series of
oil-soluble carboxylic acid cornponen-ts LS based upon the
reaction product formed by reacting, according to known
procedures, a polyolefin or halogenated polyolefin with
alpha, beta-unsaturated acids or their anhydrides such as
acrylic, methacrylic, maleic, and fumaric acids, and maleic
anhydride to form the corresponding polyolefin-substituted
acid. The substituents (R~, in these products have a
sufficient number of carbon atoms to provide number
average molecular weights in the range of from about 150
up to about 10,000, with a preferred range of from about
700 to about 5,000.
The oil-soluble monocarboxylic acids useful in
the process of the present invention correspond to the
general formula: R-COOH, wherein R is defined above. ~ ;
Specific illustrative examples of these monocarboxylic ~ "
acids included caprylic acid, capric acid, palmitic acld,
stearic acid, isostearlc acid, linoleic acid, behenic acid -
- and hydrocarbon-substituted propionic acids A parti-
;~ 25 ~ cularly preferred group~of useful monocarboxylic aclds is
.:. :
~ the hydrocarbon-substituted propionic acids, which can
: .
conveniently be prepared by a reaction of` a halogenated
polyolefin, such as chlorinated polyisobutylene, with
acrylic acid or methacrylic acid. The hereinabove dis-
.
cussed derivatives of the acid functions of these illus-
-17-
~ , . ..
~`.,Z,,,..~ ,'".",: ,. ........
7~
trative monocarboxylic acids are also useful.
The oil-soluble dicarboxylic acids useful in
the process of the present invention correspond to the
general formula:
H
R" - C - C02H ~ :
H2C - C02H :.
wherein R" is as defined above. The R" group includes
olefin polymers derived fro~ ethylene, propylene, l-~utene,
isobutene, l-pen~ene, 2-pentene, l-hexene~ 3-hexene~ and
high molecular weight substantially saturated petroleum
fractions. The hereinabove discu~sed derivatives o~ the
acid ~unction are also useful. :
The hydrocarbon-substituted succini~ a~ids and
their derivatives constitute the most preferred class of
oil-soluble carboxylic acids for use in the subject processO
Another particularly use~ul cla~s o~ oil-soluble carboxylic
acids are those based upon the polyolefin-substituted acrylic
acids and the polyole in-substituted methacrylic acids.
These classes of oil-soluble ~arboxylic a~ids and their
~ derivatives are well known in the ar~, and methods ~o~
their preparation, a~ well as representative examples o ~ `
the types useful in the present~invention are des~ 3ed in
detail in the:following U.S. :patents: 3,172,892; 3,216,936:
~ : .. .
~: ; 3,21g,6~6; 3,271,310; 3,272,746; 3,278,5S0; 3,281,428;
3,306,gO~J 3,i316,771; 3,;373,111: 3,381,022; 3,341,542;
3,344,170: 3,~48,048: 3,~54,607: 3,515,669: 3,522,}79:
3,54~,678; 3,542,680; 3,579:,450~3,632,510: 3,632,511r :
:
.
and 3,639,242.: : ::
18 -
: ~ , -
,, . . . . . - , , - . . . .... .... . . .. .. . . . . .. .. .. .. . . ...
1~57C~0
Some of the function derivatives of the above-
discussed polyolefin-substituted acids, useful in the
subject process, are the amides, esters and various salts.
Thus, the reaction product of polyolef`in-substituted
succinic acids and mono- or polyamines, particularly
- polyalkylene polyamines, having up to about ten amino
nitrogens are especially suitable. This reaction product
generally comprises a mixture of amides, imides, and/or
amidines. The reaction products of polyisobutylene-
substituted succinic anhydride and polyethylene polyamine
containing up to about ten amino nitrogens are particularly
usèful. These anhydride-amine products are disclosed and
exemplified in U.S. patents 3,018,250; 3,024,195,
3,172,892; 3,216,936; 3,219,666; and 3,272,746. Included
in this group of functional derivatives are those products
prepared by post-treating the reaction products of the
amine and substituted succinic anhydride with carbon di-
sulfide, a boron compound, an alkyl nitrile, urea, thlourea,
guanidine, alkylene oxides and the like as dlsclosed and
exemplified in U.S. patents 3,200,107; 3,256j 185;
3, o87,936; 3,254,025; 3, 281, 1~28; 3~ 278,550; 3~ 312,619;
and~British Specification l,053,577. The half-amide~and~ -
half-metal salts and half-ester and half-metal salt
derivatives of hydrocarbon-substituted succinic acids are ~ -
also useful. These products are disclosed in U.S. patents
: 3,163,603 and 3,522,179, : ~ :
Also useful are the esters prepared by the
;:: ~ . : : ::: .
reaction o~ the polyolefin-substituted acids or anhydrides
;with a mono- or polyhydroxy~compound~ such as aliphatic ;~
30 ~ alcohols or~phenols. Typical~esters of this type are
"~
1~5570~;D
disclosed in ~ritish Specification 981,850, U.S. patents
3,311,558 and 3,522,179. Preferred esters are the esters
of polyolefin-substituted succinic acids or anhydrides
and polyhydric aliphatic alcohols containin~ two to ten
hydroxy groups and up to about forty aliphatic carbon
atoms. This class of alcohols includes ethylene glycol,
glycerol, sorbitol, pentaerythritol, polyethylene glycol,
diethanol amine, triethanol amine, N,N'-di(hydroxyethyl)-
ethylene diamine, and the like. When the alcoholic
reactant contains reactive amino hydrogens, the reaction
product may comprise products resulting from the reaction
of the acid group with both the hydroxy and amino functions.
Thus, this reaction mixture can include half-esters, half-
amides, esters, amides, and imides, as discussed in U.S.
patent 3,324,033.
Suitable monocarboxylic acid derivatives and
methods for their preparation are disclosed in detail in
British Patent Specification 1,075,121, U.S. patents :
3,272,746; 3,340,281; 3,341,542; and 3,342,733. .
The foregoing U.S. patents and foreign specifi- ~
cations are referred to for their disclosure of (1) the :
requisite acids or acid-produclng compounds such as acid ~:
halides, acid anhydrides, (2) process for pr~paring esters,
amides, imides, and amidines, and (3) actual examples of:
.
suitable esters, amides, etc. which can be satisfactorily ~: -
employed in the process of the present invention.
.
A clear understanding of the new process oE this .:~
r invention, the novel reaction products, and lubricant and
i~ ~fuel compositions containing the novel products, may be
,
2 0
.
': ~ : : `
~:
,~ ~
C i :: :
.
`. `, .. .. ,.. ., . .. . , . . " .. , .. -.. ..... "., , . ,, .. .-. .. ` ., . . , .. . ` ~ - . ... . ,` ,. , . i .
10557~ :
obtained from the examples given below~ which illustrate
the presently preferred best modes for carrying out this
invention.
Example 1
A solution of 790 grams (1 equivalent) of an
alkylated benzene sulfonic acid, 71 grams of a polybutenyl
succinic anhydrideJ (equivalent weight about 560)~ and 176
-grams of mineral oil is prepared in a reactor at room
temperature. Sodium hydroxide (~20 gramsJ 8 e~uivalents)
is added to this solution followed by the addition of 640
grams (20 equivalents) of methanol. The temperature of
the resulting mixture increases to 89C. (reflux) over a
period of 10 minutes due to exotherming of this reaction
mixture. During this periodJ the reaction mixture is
carbonated with carbon dioxide at a rate of ~c~h (cubic
feet/hr.). Carbonation is continued for about ~0 minutes
as the temperature of the reaction mixture gradually~
decreases to 74~C. The methanol and other volatile
materials are stripped from the carbonated mixtUYe by
blowing nitrogen through the mixture at a rate o~ 2cfhJ ~;
while slowly~increasing the temperature to 150~C., over a
period of about 90 minutes. After completlon of the
strippingJ the reaction mixture is held at a temperature
in the range of 155-165~C. for about 30 minutes, and then
filtered to yield an oil solution of the desired basic
...
~ ~ sodiwn sulfonate having a metal ratio of about 7.75. ~ ~
: . :
This solution contains 1~,~4~ oil.
; Example 2
Following~the general procedure of Example~lJ
30 ~ a solution of 780 grams (1 equlvalent)of an alkylated
35S71D0
benzene sulfonic acidJ 119 grams o~ a polybutenyl succinic
anhydride (equivalent weight about 560), and 442 grams of
mineral oil is prepared and mixed with 800 grams (20
equivalents) of sodium hydroxide and 704 grams (22 equiv-
alents) of methanol. This reaction mixture is carbonated
by intimately contacting it with carbon dioxide at a rate
of 7cfh for a period of 11 minutes, as the temperature
slowly increases to 97C. The rate of carbon dioxide flow
is reduced to 6cfh and the temperature of the mixture
decreases slowly to 88C. over a period of about 40 minutes.
The rate of carbon dioxide flow is reduced to 5cfh for a
period of about 35 minutes and the reaction temperature
slowly decreases to 73C. The volatile materials are
stripped by blowing nitrogen through the carbonated mix-
ture at a rate of 2cfh for 105 minutes as the temperature
is slowly increased to l60aC. A:~ter the stripping is
completed, the mixture is held at a temperature of 160C.
for an additional 45 minutes and then filtered to yield
an oil solution of the desired basic sodium sul~onate,
having a metal ratio of about 19.75. This solution con-
tains 18.7% oil.
Example ~
Following the general procedure of Example 1J a
- - solution of 3120 grams (4 equivalents) of an alkylated
benzene sul~onic acid, 284 grams of the polybutenyl
succinic anhydride (equivalent weight about 560), and 704
grams of mineral oil is prepared and mixed with 1280 grams
(32 equivalents) of sodlum hydroxide and 2560 grams (80
equivalentsj of methanol. Thls reaction mixture is car-
~ bonated using carbon dioxide at a rate of lOcfh for a
:
-22-
.;
.: . ,:, -: . , ... . . . :- . , ~.. - .-: , .. .. : ,
~557~6~
total period of about 65 minutes During this time, the
temperature of the reaction mixture increases to 90C.
and then slowly decreases to 70C. The volatile material
is stripped by blowing with nitrogen gas at the rate of 2
cfh for 2 hours as the temperature of the mixture is slowly
increased to 160aC. After the stripping is complete, the
mixture is held at a temperature of 160C. for 0.5 hour~
and then filtered to yield a clear oil solution of the
desired sodium salt, having a metal ratio of 7.75. This
solution has a 12.35~ oil content.
Example
Following the general procedure of Example 1~ a
solution of 3200 grams (4 equivalents) of an alkylated
benzene sulfonic acid~ 284 grams of a polybutenyl succinic
anhydride, and 623 grams of mineral oil is prepared and
mixed with 1280 grams (32 equivalents) o~ sodium hydroxide
and 2560 grams (80 equivalents) of methanol. The reaction
mixture is carbonated using carbon dioxide at a rate of 10 -
cfh for a total period of about 77 minutes. During thLs
time the temperature of the reaction mixture increases
to 92C. and then gradually drops to 73C. The volatile
materials are stripped by blowing with nitrogen gas at a
rate of 2 cfh for a period of about 2 hours as the temper-
ature of the reaction mixture is slowly increased to 160C.
The final tracing of the volatile material is stripped
from the reaction mixture using a vacuum o~ 30mm/Hg and
a temperature of 170C. After the stripping is complete
l . . .. ..
the mixture 1s held at a temperature of 170C. and then
filtered to yield a clear oil solution of the desired
I
sodium salt~ having a metal ratio of about 7.72. This ~
. ~ .
.~ .,.
,~
~ -23-
Z~ :
~ , - . . . . . , , , . . - - , -; .. . , .. ~ .. , . ~ . ... - ... .. .. . . . ... . . . .
i~S~7~
solution has arl oil content of 11,~.
Example rj
Following the general procedure of Example 1, a
solution of 780 grams (1 equivalent) of an alkylated
benzene sulfonic acid, 86 grams of a polybutenyl succinic
anhydride (equivalen-t weight about 560), and 251~ grams of
mineral oil is prepared and mixed with 480 grams (12
equivalents) of sodium hydroxlde and 640 grams (20 equiv-
alents) of methanol. This reaction mixture is carbonated
using carbon dioxide at a rate of 6 cfh for a total period
of about 45 minutes. During this tirne the temperature of
the reaction mixture increases to 95C. and then gradually
cools to 74C. The volatile material is stripped by
blowing with nitrogen gas at a rate of 2cfh for a period
f about one hour as the temperature of the mixture is
increased to 160C. After stripping is complete the mix-
ture is held at a temperature of 160C. for 0.5 hour and
then fil-tered to yield an oil solution of the desired
sodium salt~ having a metal ratio of 11.~3. The oil content
of this solu-tion is 14.7~.
~3xample 6
Following the general procedure of Example 1, a
solution of 3120 grams (4.0 equivalents) of an alkylated
benzene sulfonic acid, ~44 grams of polybutenyl succinic
anhydride (equivalent weight about 560), and 1016 grarns
of mineral oil is prepared and mixed with 1920 grams (48
equivalents) of sodium hydroxide and 2560 grams (80 equiv-
alents) of methanol. This mixture i.s carbonated over a
period of about two hours using carbon dioxide at a rate
of lOcfh. During this period of carbonation the temperature
-
.
~5576~)
of the mixture increases to 96C. and then gradually cools
to 74C. The volatile materials are stripped from ~he
react:ion mixture by nitrogen a~ a ra-te of 2 cfh, for a
period of two hours, as the temperature is increased from
74C. to 160C. by external heating. This stripped mix-
ture is heated for an additional one hour at 160C., and
then filtered. The filtrate is vacuum stripped (30mm/Hg)
at 160C., to remove a small amount of water, and again
filtered to give a solution of the desired sodium salt,
having a metal ratio of about 11.8. The oil content of
this solution is 14.7~.
Example 7
~ollowing the general procedure of Example 1, a
solution of 2800 grams (3.5 equivalents) of an alkylated
benzene sulfonic acid, 302 grarns of polybutenyl succinic
anhydride, and 818 grams of mineral oil is prepared and
mixed with 1680 grams (42 equivalents) of sodium hydroxide
and 2240 grams (70 equivalents) of methanol. This mixture
is carbonated over a period of about 90 minutes using
carbon dioxide at a rate of lOcfh. During this peri.od of
carbonation, the temperature of the mixture increases to
96C. and then slowly cools to 76C. The volatile materials
are stripped from the reaction mixture using nitrogen at a
rate of 2cfh, as the temperature is slowly increased from
76C. to 165C. by external heating. Water is removed
,
from the reaction mixture by stripping under vacuum~ 35mm/
Hg, at 165C. After filtration, a solution of the desired
basic sodiurn salt is obtained. This has a metal ratio of
about 10.8 and the oil content of the solution is 13.6~.
. .
~ ~25-
~C~557C~
Fxample 8
Following the general procedure of Example 1, a
solution of 780 grams (1.0 equivalent) of an al~ylated
benzene sulfonic acid, 103 grams of a polybutenyl succinic
anhydride (equivalent weight about 560), and 350 grams of
mineral oil is prepared and mixed well with 640 grams (16
equivalents) of sodium hydroxide and 640 grams (20 equiv-
alents) of methanol. This mixture is carbonated over a
period of about one hour using carbon dioxide at a rate o:~
6cfh. During this period of carbonation, the temperature
of the mixture increases to 95C. and then gradually cools
to 75C. The volatile material is stripped from the reac- ; -
tion rnixture by nitrogen gas at a rate of 2cfh over a
period of 95 minutes. During this period of stripping,
the temperature of the reaction mixture initially drops to
70aC., over a period of 30 minutes, and then slowly rises
to 78C. over a period of 15 minutes. The mixture is then
heated to 155C. over a period of 80 minutes. The strlpped
- mixture is heated for an additional 30 minute period at a
temperature in the range of 155-160C. J and then filtered.
The filtrate is an oil solution of the desired basic
sodium sulfonate, having a metal ratio of about 15.2. This
solution has an oil content of 17.1~.
Example 9
.
Following the general procedure of Example 1, a
solution of 2400 grams (3.0 equivalents) of an alkylated
~benzene sulfonic acid, 308 grams of a polybutenyl succinic
anhydride, and 991 grams of mineral oil is prepared and
mixed well with 1920 grams (48 equivalents) of sodium
hydroxide and 1920 grams (60 equivalents) of methanol.
: -
: - :
~26--
~' ' ' ' :~ ',:
~5570~
This reaction mixture is carbonated by intimately con-
tacting it with carbon dioxide at a rate of lOcfh for a
total period of 110 minutes. During this period of time,
the temperature of the reaction mixture initially rises to
98C. and then slowly decreases to 76C. over a period of
about 95 minutes. The methanol and water are stripped ~-~
from the reaction mixture by nitrogen gas at a rate of 2cfh,
as the temperature of the reaction mixture slowly increases
to 165C. The last traces of volatile material are stripped
from the reaction mixture using a vacuum of 30mm/Hg at a
temperature of 160C. After vacuum stripping, the mixture
is filtered to yield an oil solution of the desired
sodium sa]t, having a metal ratio of 15.1. The solution
has an oil content of 16.1~.
Exam~e 10 ~ -
Following the general procedure of Example 1, a
solution of 780 grams (1 equivalent) of an alkylated
benzene sulfonic acid, 119 grams of a polybutenyl succinic
anhydride (equivalent weight about 560) and ~2 grams of
mineral oil is prepared and mixed well with 800 grams (20
equivalen-ts) of sodium hydroxide and 640 grams (20 equiv-
alents) of methanol. This mixture is carbonated over a
period of about 55 minutes, using carbon dioxide at a rate -
- flow of 8cfh. During this period of carbonation~ the
temperature of the mixture increases to 95~C. and -then
slowly decreases to 67C. The methanol and water are
strlpped from the reaction mixture by the use of nltrogen
gas at 2cfh for a period of about ~0 minutes~ whlle the
temperature of the reaction mixture is slowIy increased
to 160C. After this strippingJ the temperature of the
'.'~ ' ' ' '
27
'
~5~7~
mixture is maintained for about 30 minutes at a ternperature
in the range of 160-165C. It is then filtered to give a
solution of the corresponding sodium sulfonate, having a
metal ratio of about 16.8. The final solution contains
18.7,~ oil.
Example 11
Following the general procedure of Example 1,
836 grams (1 equivalent) of a sodium petroleum sulfonate
(sodium "PETRONATE") in an oil solution containing ~8~ oil,
and 63 grams of a polybutenyl succinic anhydride (equiv-
- alent weight about 560) is introduced into a reactor and
is heated to 60C. This mixture of acids is treated with
280 grams (7.0 equivalents) of sodium hydroxide and 320
grams (10 equivalents) of methanol. The reaction mixture
is carbonated using carbon dioxide at a rate of 4 cfh :~or
a total period of about 45 minutes. During this time, the
temperature of the reaction mixture increases to 85C.
and then slowly decreases to 74C. The volatile material
is stripped by blowing with nitrogen gas at a rate of 2
cfh) while the temperature of the mixture is gradually
increased to 160C. After the stripping- has been com-
pleted, the mixture is heated an additional 30 minutes at
160C., and then is filtered to yield the corresponding
sodium salt in solution. This has a metal ratio of 8.o,
and the solution has an oil content of 22.2~.
Example 12
Following a general procedure of Example 11,
1256 grams (1.5 equivalents) of the sodium petroleum
sulfonate in an oil solution containing 48~ oil and 95
grams of polybutenyl succinic anhydride is introduced into
',
'
-28-
` ' "
1Ci557~
a reactor and heated to 60C. This solution of acid is
treated with 420 grams (10.5 equi~alents) of sodium
hydroxide and 960 grams (30 equivalents) of methanol.
Carbonation of this mixture is accomplished using carbon
dioxide at the rate of 4cfh for a total period of 60
minutes. During this timeS the te~perature of the mixture
is increased to 90C. and then slowly decreases to 70CC.
The volatile materials are stripped fro~ the carbonated
mixture using nitrogen gas and slowly increasing the
temperature to 160C. After stri.pping the reaction mi~
ture is allowed to stand at 160QC. for appro~imately 30
minutes and then is filtered to yield an oil solution of `~
the sodium sulfonate, having a meta] ratio of about 8.o
The oil content of the solution is 22.2C~.
In the above examples, as well as the specifi-
cation and claims, all percentages are expressed as
percentage by weight, and all parts are expressed as parts -
by weight, unless otherwise noted. Likewise, all tempera- -
tures are expressed in degrees centigrade (~C.). The rate
of flow of the acidic gaseous material was measured in
cubic feet per hour (cfh).
The basic alkali sulfonate dispersions of the
present invention are particularly useful as additives -for lubricants and fuels, and can be emplo~ed in a manner
slmilar to that known in the art ~or other basic salts.
In this regzrd, reference is made to the fol:Lowing U.S
patents; 25585,520; 2,739,124; 2,895,913; 2,889,279i~
3,149, o74; 3,150, o89; and 3, 235, 494.
In lubricant compositions, such as crankcase
lubricating oil, the basic alkali sulfonates function as -
'',
-2 9 - :
~ .", '
~L~5~7~0
detergents to pror.lote engine cleanliness and reduce wear
by neutralizing acidic products, such as those formed by
the oxidation of the oil components or formed during com-
bustion. These acidic contaminants, if not neutralized,
will lead to increased engine wear and the formation of
lacquer on engine parts. The subject sulfonates also
have the property of dispersing insoluble materials formed
in lubricants as a result of fuel combustion or oil oxi-
dation. Accordingly, they reduce sludge formation.
In fuel compositions, such as petroleum dis-
tillate fuel, the basic alkali sulfonates promote engine
cleanliness, particularly to the components of the fuel
system, such as fuel lines, carburetors, injectors, pumps,
and the like. In furnace fuel oil, they serve as anti-
screen clogging agents. In diesel fuels and other fuels
which tend to produce black exhaust smoke upon combustion,
the subject salt dispersions tend to suppress the forrnation
and evolution of these black eY~haust smokes. When used as
crankcase lubricant additives, the basic salts of the
present invention also reduce or eliminate the preignition
tendency in gasoline fuel engines relative to lubricant
compositions containing other basic salts used in the fuel
composition ~-
The additives of the present invention can be
effectively employed in a varlety of lubricating compo-
sitions based upon diverse oils of lubricating viscosity,
such as natural oil or syn-thetic lubricating oil or
suitable miY~tures thereof. The lubricating compositions
contemplated are principally crankcase lubricating oils
for spark-ignited and compression-ignited internal com-
:
.: " '
~ ~3~
~L~557~
bustion enginesJ including automobile and truck engines,
two-cycle engine lubricants, aviation piston engines,
marine and low-load diesel engines, and the like. How-
ever, automatic transmission fluids, trans-a~le lubricants,
gear lubricants, metal-working lubricants, hydraulic fluids~
and other lubricating oil and ~rease compositions can --
benefit from the incorporation of the present additives
therein. Likewise, the additives of the presen~ invention
can be effectively employed in fuel compositions based upon
the normal]y liquid hydrocarbon fuels or petroleum dis-
tillate fuels, such as fuel oils~ diesel fuelJ gasolineJ
aviation gasolineJ aviation jet fuel and -the like.
When used as an additive for lubricating compo-
sitionsJ the basic alkali sulfonate dispersions can be added
directly to the lubricantJ or can be modified prior to its
addition to the lubricant. The amount of the subject
sulfonates used will depend upon the nature of the parti- :
cular lubricant compositionJ and the environment under
which the resulting composition is to be used. In genera],
they will be used in an arnount in the range of from about
0.001% to about 30~ by weight of the total composition. ~ ~
For exarnple~ these basic alkali sulfonate dispersions can ~ ~ :
be successfully employed as detergent-dispersant additives
for lubricating oils when employed in amounts sufficient to
provide a sulfate ash content to the lubricatin~ oil of ~:
from about 0.01~ to about 20~, preferably from about 0.1
to about 10~. If the lubricating oil is to be used as a
crankcase lubricant for gasoline engines, it normally will
contain abou-t 1~ ash. On the other hand, for use in
crankcase lubricants for diesel enginesJ sufficient additive
~'~
~ -31-
:1~5~70~
should be used to provide the l~bricant with an ash con-
tent of from about 0.1% to about 5% ash, while marine
diesel engines may require enough additiv~ to provide an
ash content of 10% or mvre.
When the basic alkali ~;ulfonate dispersions
are added to fuels as anti-screen clogging agents, they
will normally be employed in an amount such that the ash
content o~ the ~uel will be from about 0.0001% to about
0.1%. If the additive is used in a diesel fuel to suppress
the formation of black exhaust smoke upon combustion of
the fuel in a diesel engine, enough additiva should be
added to impart a sulfate ash content to the diesel fuel
of from about 0.001% to about 1%, pre~erably about 0.05%
to about 0.5%.
The basic alkali sulfonate dispersions of the
present invention can be used alone or Ln combination :
with other fuel and lubricant additives known in the prior
art. These additives include, other detergents o~ the
ash-containing type, ashless dispersants, viscosity index
improvers, pour point depressants, anti-foam agents,
extreme pres~ure agents, anti-wear age~ts, rust inhibiting
agents, axidation inhibitors, corrosion inh~bitors, de-
; i~ers, anti-knock agents, and other smoke suppressant~.
These additional additives are well known in the art and
a brief survey of conventional additives ~or lubricating
compositions is contained in the publications LU~RIC~T . ;
ADDITIVES, C.V. Smalheer and R. Kennedy Smith, published
: . . .
by the Lezius-Hilas Co., cleveland, Ohio (1967), and
LUBRICANT ADDITIVESt M.W. Ranney, published by Noyes ~ -
~: Data Corp~, Park Ridge. ~.J. (1973).
70(~
These publications establish the stat~ o~ the art in
regara to identifying general types and specific examples
of other additives which can ~e used in conjunction with
the basic alkali metal sulfonate dispersions of this
invention.
When additional additives are presentt they will
normally be employed in the convention in amounts in
which they are normally employed; that is, the~ will
comprise from about 0.001% to ~bout 25% by weight of the
total cGmpvsition, depending on the nature of the addi~
tive and the particular lubricating composi~ion or fuel
composition in question. For example, ashless dispersants
can be employed in amounts rom about 0.1% to about 10%f
while additional metal-containing detergents will be present
in amounts from about 0.1% to about 20% by weight. As is
apparent, the basic alkali sulonate di~persions may contain
a dispersant, such as an ester or an amide of a hydrocarbon-
substitu~ed succinic acid, ~n addition to the subject salt.
Accordingly, it will be obvious to one sXilled in the axt ;-
that the present dispersion ca~ be sub~tituted in known
lubricating compositions in such a manner that the alkali
sulfonate replares all or a portion of other metal-containi~g
d~tergents in the known composition, w~ile th~ dispersant
repla~es all or a portion o the ashless dispersant Ln the ; :~
i lubricating ~:omposition. Other additives, such as pour
point depressants, extreme pressure additives, viscosity
i~dex Lmproving agents~ anti-oaming agents, a~d the l~ke,
are normally employed in amDuntæ of from about 0.001% to
`~ about 10% by weight of the total composition, depending
upon the nature and purpose o~ the particular additive.
. . .
~ 33 -
1055~
The ash-containing detergents are the well known
neutral and basic alkali or alkaline earth metal salts of
sul~onic acids, carboxylic acids or organo-phosphorus-
containing acids. These phosphorus-containing acids are
characterized by at least one direct carbon-to-phosphorus
linkage, and can be prepared by steam-treating an olefin
polymer, i e., pol~isobutylene, with a phosphorizing agent,
such as phosphorus trichloride, phosphorus heptasul~ide,
phosphorus pentasul~ide, phosphorus trichloride, and sulfur,
white phosphorus and a sulfur halide, or phosphorothioic
chloride. When used as an ash-containing detergcnt, the
most commonly used salts of these acids are the sodium,
potassium5 lithium~ calcium, magnesium, strontium, and
barium salts. The calcium and barium salts are used exten-
sively than the others. The "basic salts" are those metal
salts known in the art wherein the metal is present in a
stoichiometrically larger a~ount than that necessary to -
neutralize the acid. The calciu~-and barium-overbased
petrosulfonic acids are typical exa~ples of such basic
2Q salts.
The extreme pressure agents, corrosion-inhibiting
agents, and oxida-tion-inhibiting agents, are exemplified -
by chlorinated aliphatic hydrocarbons, such as chlorinated
wax; organic sul~ides and polysulfides; such as benzyl
disulfide, bis-(chlorobenzyl)disu].fide, dibutyl tetra-
- sulfide, sulfurized sperm oil, sulfurized methyl ester of
oleic acidj sulfurized alkyl phenolJ sulfurized dipentene, ;
A`- sulfurized terpene, and sulfurized Diels-Alder adducts;
phosphosulfurized hydrocarbons, such as the reaction
product of phosphorus sulfide with turpentine or methyl
: " ':
~3~~
5570~
. .
oleate; phosphorus esters such as the dihydrocarbon and
trihydrocarbon phosphites,i.e., dibutyl phosphite,
diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl
phosphite, dipentylphenyl phosphite, tridecyl phosphite,
:. . .
distearyl phosphite, and po:Lypropylene substituted phenyl
,- phosphite; metal thiocarbamates, such as zinc dioctyl-
dithiocarbamate and barium heptylphenol dithiodicarbonate;
Group II metal salts of phosphorodithioic acids, such as
zinc dicyclohexyl phosphorodithioate, and the zinc salt
of a phosphorodithioic acid.
The ashless detergents or dispersants include
. products obtained by the reaction of hydrocarbon-substituted
succlnic compounds and alkylene polyamines or polyhydric
alcohols, which can be further post-treated with materials
such as boric acid, metal compounds, etc. Such hydrocarbon-
substituted succinic acid derivatives have previously been
discussed above
Pour point depressing agents are illustrated by
the polymers o~ ethylene, propylene, isobutylene, and -
poly(alkyl methacrylates). Anti-foam agents include
polymeric alkyl siloxanes, poly-(alkyl methacryates),;
copolymers of diacetone acrylamide and alkyl acrylates or
; methacrylates, and the condensation products of alkyl
phenol wlth forma-ldehyde and an amine Viscoslty index
, 25 improvers include, polymerized and copolymerized alkyl
`~ - methacrylates and polyisobutylenes.
` ~The dispersions o~the present invention are
s-~ effectively employed ln a variety of lubricating compo-
~ sitions based upon diverse oils of lubricating viscosity.
;~ 30 ~ Thus~ both natural and synthetic base lubrlcating oi:Ls ~
~ ~35- ;
111~557~i~
are contemplated as the base of the lubricating oil and
grease composition of the present invention,
The natural oils include animal and vegetable
oils, such as castor oil and lard oil, as well as, solvent-
rèfined or acid-refined mineral lubricating oils of the
paraffinic, naphthenic, or mixed paraffinic-naphth~-?nic
types. Oils of lubricating viscosity derived from coal or
~ shale are also useful base oils.
t, Synthetic lubricating oils include hydrocarbon ;-
~ 10 oils and halo-substituted hydrocarbon oils such as poly-r, merized and interpolymerized olefins, i.e., polybutylenes,
., ~
propylene, isobutYlene copolymers, chlorinated butylenes,
etc; alkyl benzenes, i.e., dodecyl benzenes, tetradecyl
benzenes, etc; polyphenols, i.e., biphenol, terphenols,
etc.; and the like. Alkylene oxide polymers and inter- -
polymers and derivatives thereof where the terminal
hydroxyl groups have been modified by esteri~ication,
etherification, etc. constitute another class of known
synthetic lubricating oils, These are exemplified by
the oils prepared by polymerization of ethylene oxide or
propylene oxide. The alkyl and aryl ethers of these pol~-
~: oxyalkylene polymers, i.e., methyl polyisopropylene glycol
ether, diphenyl ether of polyethylene glycol, diethyl
ether of polypropylene glycol, or mono- and polycarboxylic
esters thereof, for example, the acetic acid esters, mixed ;~
~ C3-C8 fatty acid esters or the C13 Oxo acid diester of~
r~ tetraethylene glycol. ~ -
,- Another suitable class of synthetic~lubricating `
, ~ oils comprise the esters of dicarboxylic acids, such as
~-~ 3Q phthalic acid, succinic acid, maleic acld, azelaic dcid,
. .
k
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- .
~ 36-
f~
~57~3~
:
suberic acLd, sebacic acid, with a variety of alcohols.
Specific examples of these esters include dibutyl adipate,
di(2-ethylhexyl)sebacate, and the like. Silicon-based
oils such as the polyalkyl-polyaryl-polyalkoxy or poly-
aryloxy-siloxane oils and the silicate oils, i.e.,
tetraethyl silicate, comprise another useful class of
synthetic lubricants. Other synthetic lubricating oils
include liquid esters of phosphorus-containing acids, i.e.,
tricresyl phosphate, polymeric tetrahydrofurans, and the
like.
.
The following lubricant and fuel compositions -
exemplify the incorporation of the basic alkali sulfonate
dispersions of the present invention into these type co~npo-
sitions. Unless otherwise indicated "percent" and "parts"
are used :Ln the specification and claims to mean "percent
by weight" or "parts by weight".
Example A
A composition for use as an automatic trans-
mission fluid is prepared using an ATF base oil plus 12.36~
total additives. These additives are added as a concentrate
which contains 3~ of a conventional comrnercial seal sweller,
3~25~ of a viscosity index improver, derived from mixed
~` esters of a styrene-maleic acid interpolyrner as disclosed
- in U.S. patent 3,702,300, 4~ of an ashless dispersant,
`~ 25 which lS the reaction product (1:1 equivalents) of poly-
.
- isobutenyl succinic anhydride and tetraethylene pentamine~
prepared according to the procedure of U.S. patent
: . . . , . ~ .
3,172,892, 0.71~ of a zinc isobutylamyl phosphorodithioate
`;- oxidation inhibitor, l~ of the product of Example 1, 0.2
` of a conventional friction modifier, based upon Polyoxy-
. ~ .. - :
: `:
: - :
:, ~ - , :
- 37
:
i~s~
ethylene(2)Tallowamine (Ethomeen T/12~), 0.2% mineral oil,
200ppm of a conventional silicone based anti-foaming agent,
and 0.025% of a dye.
Example B
A diesel fuel com~ositi.on is prepared containing
1% of the product of Example 8, and lOO~pm of a conventional
silicone based anti-foaming age~t.
Example C
A.jet aviation fùel composition is prepared
containing 0.25% of the product of Example 1, and lOOppm
of a conventional anti-foaming agent~
Example D . .
A lubricating composition is prepared usLng a S~E 90
base oil, 20% by volume of the product of Example 5, and
5~ppm of a conventional silicone based anti-foaming agent ;
ExamPle E
A lubricating composition is prepared using a SAE 30
base oil, and as additives, 4% by volume of a dispersant
based upon the reaction product of a polyisobutylene sucainic
anhydride, pentaerythritol, a poly(oxyethylene)-(oxypropylene)
glycerol, ~nd polyethylene polyamine as descr~bed in E~ample :~
llB of British Patent 1,306,529, 0.5% by volume of a
commercial demulsifier, 0 1% zinc as zinc isobutyl-p-amyl
phosphorodithioate as an oxidation inh~bitor, and 2.5%
[10 TB~(Total base numher~] of t~e product of Example 8. ~ :
~xample F :
::'
A lubricating composition is prepared using a
SAE 20 base oil, and, as additives, 0.2% of a commercial
* Trade Mark
.~
~ss~
:
acrylate based pour poin-t depressant, l~,5~ by v~lume of a
di~persant as described in Example E, 0.57~ o~ ~he zinc
based oxidation inhibitor described in Example E) 0.5~ :
sul~ate ash as the product o~ Example 1~ and 40ppm o~ a
conventional silicone based anti-foaming agent.
Example G
A lubricating composition is prepared using a
SAE 30 base oil, andJ as additives, 2.45~ by volume o~ the
product of Example 1, 1% by volume of an ashless dispersant
as described in Example A, o. 6% by volume of a zinc based
- oxidation in~libitor as described in Example E, and-30ppm
of a conventional silicone based anti-foaming agent.
Exam~le H
A lubricating composition is prepared using a
SAE 30 base oil, and, as additives, ~ by volume o~ the
dispersant described in Example E, 0.5~ demulsifier as
described in Example E, 0.1~ zinc as zinc isobutyl~p-amyl
phosphorodithioate, and 3,17~ (10 TBN) of the product of
Example 10.
Exam~le I
A lubricating composition is prepared using a ;
SAE lOW-30 base oil, and, as additives, 5.75~ of a com-
bination pour point depressant and viscosity index improver,
; - which was based upon a mixture of a fumaric-vinyl acetate -
ethyl vinyl ether copolymer as described in U.S. patent
3,250,715, and polyacrylate, 4.5~ by volume of the dis
persant described in Example E, 0.57~ of the zinc based
oxidation inhibitor described in Example H~ and 0~5
sulfate ash as the product of Example 10.
- :
. . .
. ~ '.' '
_
~.
- ~¢i 557~0
Example J
A lubricating composition is prepared using a 100N
base oil and a total of 13.36% of additives, these additives
are 3.75% of the viscosity index improver as described in
Example A, 3.5% of a commercial seal-sweller, 4% by volume
of the ashless dispersant desc~bed in E~ample A, 0.71% of
a zinc dioctyl phosphorodithioate ~xidation inh~bitor,
0.2% of the friction modifier described in Example A,
0.2% mineral oil and 1% of the product o Example 3.
Example K :
Three gasoline fuel compositions were prepared
using the product of Example 1 as the additive in concen-
trations of 67.5 pounds, 33.75 pounds, and 1000 pounds per
1000 barrels (42 U.S. gallons per barrel~ of gasoline.
ExamPle L
A lubricating composition is prepared using a
SAE 20 base oil and, as additives, 4~5% of the demulsiier
described in Example E, 0.57% of the zinc based oxidation ~ -
inh~bitor described in Example E, 0.25% sulfate ash as an
overbased magnesium petroleum ~ulfonate, 0.25% sulfate :~
ash as the product of Exa~ple 1, 0.2% of a conventional
commercial pour point depressant (AcrylOid 150*), and 30 ppm
of a conventional silicone based anti-foaming agent.
Example M
A lubricating comp~sition is prepared u~ing a
SAE 10W base oil and, as additives, 12% of a commercial
viscosity index improver, 3.42% of a di~persant ba~ed up~n
the 1:1 mole reaction product o~ a polyisobutenyl succinic
anhydride and pentaerythritol, 1.05% of a dispersant bas~d
* Trade Mark
- 40 -
' ~ :'.
~05~70~ :
upon the reaction product Or a polyisobutenyl succinic
anhydride and the reaction product of adipic acid and
amino-ethyl ethanolamine, 0.12% of a commercial demuls:ifier,
1.73% of the product of Example 2, 1.63~ zinc methylethyl
phosphorodithioate~ and 50ppm of a silicone based anti-
foaming agent.
Example N
A lubricating composition is prepared using a
lOW-50 base oil andJ as additives~ 8.4% of a hydrogenated
butadiene-styrene viscosity index improver, 7.25% of the
product of Example 2, 2% by volume of the dispersant
described in Example E, and 0.1% of a conventional pour
point depressant (PAM-140),
Exam~le 0 .
A lubricating composition is prepared using a
synthetic lubricating oil base consisting essentially of
the diethylether of propylene glycol having an average - :molecular weight of about 1500, and 1% of the product of j :Example l.
- ~, .
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