United States Patent Office
`
`3,373,198
`Patented Mar. 2, 1968
`
`3,373,108
`METHOD OF PREPARing gWERBASED CAELCUM
`SJLFGNATE OL CONCENTRATES
`Robert A. Woodle, Edward H. Holst, and Robert S.
`Edwards, Nederland, Tex., assigliors to Texaco race
`New York, N.Y., a corporation of Delaware
`No Drawing. Fied Apr. 12, 1966, Ser. No. 541,949
`4 Claims. (C. 252-33)
`
`-wd
`
`ABSTRACT OF THE DISCLOSURE
`A method of producing an overbased calcium Sulfonate
`lube oil concentrate comprising contacting a mixture of
`normal calcium sulfonate, basic calcium inorganic com
`pound, an oxygenated vehicle, a lubricating oil and a thio
`phenol with carbon dioxide and separating residual Water,
`oxygenated vehicle and thiophenol from the final reaction
`mixture leaving said concentrate as residue.
`
`5
`
`0.
`
`-ammed
`
`20
`
`2
`and of sufficient size to produce an unacceptable amount
`of haze in the unfiltered and filtered product.
`We have discovered, and this constitutes our invention,
`a method of producing overbased calcium sulfonate lubri
`cating oil concentrate having a calcium metal ratio of at
`least about 2 and up to 20 and higher, preferably between
`about 10 and 18, a calcium content of at least 2 wt. per
`cent and up to 20 wt. percent and higher, preferably be
`tween about 11 and 18 wt. percent, and a total base
`number (TBN), as defined in ASTM D664, of at least
`about 20 and up to 500 and higher, preferably between
`about 280 and 450, in which the resultant overbased cal
`cium sulfonate particles are in a fine colloidal-like state,
`and therefore, do not have a tendency to precipitate upon
`storage. Further, the formed overbased sulfonate particles
`are of such fineness as to permit the passage of the crude
`concentrate through a standard clarifying means at an
`improved flow rate with reduced loss of overbased cal
`cium sulfonate to produce a product of commercially
`acceptable clarity. More particularly, we have discovered
`a particular combination of ingredients, reaction condi
`tions and reaction steps which accomplishes the foregoing
`result.
`Broadly, our process comprises forming a first reaction
`mixture consisting of (1) normal calcium sulfonate, (2)
`a basic calcium compound selected from the group con
`sisting of calcium hydroxide, a combination of calcium
`oxide and water and mixtures thereof, (3) an oxygenated
`vehicle selected from the group consisting of water, lower
`alkanol, lower alkoxy-ethanols and mixtures thereof, (4)
`a lubricating oil, and (5) a thiophenol compound of the
`formula:
`
`S.E. R. % l R
`
`30
`
`This invention relates to a method for preparing Over
`based calcium sulfonate lubricating oil concentrates of
`improved filterability and clarity containing a high pro
`portion of oil dispersible calcium.
`25
`The overbased calcium sulfonate lube oil concentrates
`are useful as detergent-dispersant additives in lubricating
`oils, e.g., in amounts between about 1 and 10 wt. percent.
`By the term “overbased calcium sulfonate lubricating
`oil concentrate' we mean a product wherein the ratio of
`filterable oil dispersible calcium equivalents to Sulfonic
`acid equivalents in the product is substantially above that
`present in ormal calcium sulfonate, that is, the equivalent
`ratio of calcium moiety to sulfonic acid moiety is Sub
`stantially greater than 1:1. The formula for the normal
`calcium salt of monosulfonic acid can be written as
`(RSO)Ca where R stands for hydrocarbyl radical. It is
`to be noted that the number of hydrogen equivalents of
`calcium and of sulfonic acid filterably dispersed in said
`normal sulfonate are each 2 and therefore the calcium
`metal ratio is 1. In contradistinction, products from our
`process have substantially higher calcium metal ratios,
`e.g., of at least 2 and as high as 20 and higher. By the
`term “calcium metal ratio' we mean the ratio of equiva
`lents of calcium to equivalents of sulfonic acid present
`45
`in the particular concentrate in a stable filterable disper
`SO.
`It is theorized that the overbased calcium Sulfonates
`contemplated herein are a complex mixture of normal
`calcium sulfonates and calcium carbonate in a physical
`50
`and/or chemical relationship with calcium carbonate Sup
`plying the excess, that is, the overbasing calcium. Further
`the overbased calcium sulfonate exists as solid, finely di
`vided particles in the lubricating oil medium of the con
`centrate.
`55
`In the past, much difficulty has been encountered in
`manufacturing overbased calcium sulfonate lube oil con
`centrates in that often substantial portions of the calcium
`values therein would undesirably precipitate during stor
`age and/or the concentrates were very turbid and required
`filtration to gain consumer acceptance. However, upon fil
`tration either an unacceptable amount of calcium values
`was lost and/or the particles of the calcium sulfonate
`calcium carbonate complex were of an undesirably large
`size to substantially block (blind) the filtering mechanism
`
`where R and R' are members, each containing less than
`13 carbon atoms, selected from the group consisting of
`hydrogen, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkoxy,
`acyl, halogen, nitro, and amino. The mole ratio of normal
`calcium sulfonate to basic calcium compound to oxy
`genated vehicle to thiophenol is advantageously between
`about 1:2:40:10 and 1:19:5:40. When the "basic calcium
`compound” reactant is calcium oxide and water, the mole
`ratio of CaO:HO is advantageously between about 1:0.1
`and 1:5. The resultant reaction mixture is heated to a
`temperature of between about 50 and 200 F., preferably
`between 70 and 140 F., under a pressure of between
`about 0.1 and 50 atmospheres, preferably between about
`0.9 and 3 atms., for a period of between about 0.1 and
`12 hours, preferably between about 0.5 and 4 hours. At
`the end of the first reaction period, carbon dioxide is
`passed through the first reaction mixture at a temperature
`between about 50 and 200 F., preferably between about
`70 and 180 F., under a carbon dioxide pressure of be
`tween about 0.1 and 50 atmospheres, preferably between
`about 0.9 and 4 atmospheres, in an amount of between
`about 1 and 40 and higher moles of carbon dioxide per
`mole of basic calcium compound reactant. The carbon
`dioxide reaction period is normally conducted for a pe
`riod between 0.1 and 12 hours, preferably between 2 and
`6 hours. At the end of the carbon dioxide reaction period,
`
`60
`
`65
`
`Page 1 of 5
`
`ORONITE EXHIBIT 1012
`
`

`

`5
`
`10
`
`5
`
`20
`
`25
`
`3,373,108
`4.
`3.
`ent can be a synthetic lubricant such as polyoxyalkylene
`the thiophenol compound, oxygenated vehicle and any
`glycol of a molecular weight between about 200 and 4000,
`other volatilizable diluents or solvents in the carbon di
`polymerized olefin, trioctylphosphate, polymeric tetrahy
`oxide reaction mixture are removed from the carbon di
`drofuran and polyalkyl silicone polymer in a molecular
`oxide treated mixture via standard means Such as frac
`Weight range of 200 to 2000. The concentration of the
`tional distillation, e.g., at a temperature between about 300
`normal calcium sulfonate in the diluted calcium sulfonate
`and 270 F. at atmospheric or reduced pressure of be
`reactant charge material is normally between 10 and 100
`tween about 1 and 50 mm. Hg leaving crude overbased
`wt. percent and more generally between about 30 and
`calcium sulfonate lubricating oil concentrate of the type
`70 wt. percent. The term “water immiscible' denotes solu
`defined. Under the preferred conditions, the crude concen
`bility in water of less than 5 wt. percent at room tem
`trate is filtered utilizing standard filter mechanisms such
`perature.
`as passing the crude product through cloth or blotter
`It is to be noted by the term "normal calcium sul
`paper precoated with a filter aid such as inert diatoma
`fonate' we intend sulfonate reactant in its diluted as well
`ceous amorphous silica The resultant filtrate is the clari
`as its undiluted form.
`-
`fied version of overbased calcium sulfonate lube oil con
`The normal calcium sulfonate reactant is prepared by
`centrate of the invention.
`standard means such as reacting a combination of calcium
`In the foregoing procedure it is theorized the thio
`oxide and water, calcium oxide alone or calcium hy
`phenol compound reacts with the added calcium hydrox
`droxide with sulfonic acid or a double decomposition re
`ide or in situ formed calcium hydroxide to form an in
`action wherein sodium sulfonate is reacted with a calcium
`termediate calcium thiophenolate which is soluble in the
`halide such as as calcium chloride to convert the sodium
`reaction medium and then the intermediate thiophenolate
`Sulfonate to the corresponding normal calcium sulfonate.
`is converted into fine calcium carbonate particles by the
`These reactions normally take place in the aforementioned
`carbon dioxide contact with the normal calcium sulfonate
`water immiscible diluents at a temperature between about
`functioning in complex with the formed calcium carbon
`100 and 200' F. utilizing a mole ratio of inorganic cal
`ate particles to aid in their colloidal-like dispersion
`cium reactant to sulfonic acid or alkali metal sulfonate be
`throughout the final lube oil concentrate. This formation
`tween about 1:2 and 1.1:2. The normal calcium sulfonate
`of calcium carbonate particles through the intermediate
`reactant may be preformed or formed in situ in the
`formation of a reaction mixture of calcium thiophenolate
`method of the invention as a preliminary first step.
`appears to permit the creation of very fine, e.g., less than
`Specific examples of the thiophenol compounds con
`about 0.4 micron normal calcium sulfonate-calcium car
`templated herein are thiophenol, 1,4-dithiophenol; 2
`bonate particles that impart substantially less haze and
`methylthiophenol; 2,6-dimethylthiophenol; 4-cyclohexyl
`substantially more filterability and storage stability to the
`thiophenol; 4-phenylthiophenol; 4-benzylthiophenol; 404'-
`final overbased calcium sulfonate lube oil concentrate
`methylphenyl)thiophenol; 3-nitrothiophenol; 3,5-ninitro
`than if calcium carbonate is formed directly from calcium
`thiophenol; 2-hydroxythiophenol; 4-aminothiophenol; 5
`hydroxide in the reaction in situ.
`ethoxythiophenol; 5-acetylthiophenol; and 2-ethyl-4-hy
`Under most preferred conditions, the first stage reaction
`is conducted under a blanket of inert gas such as nitrogen
`droxythiophenol.
`-
`In regard to the oxygenated vehicle, this vehicle is
`in order to reduce side reactions. Further, also included in
`preferably lower alkanol, that is C to C alkanols and
`the first stage reaction is volatilizable inert liquid hydro
`preferably methanol. It can also include a lower alkoxy
`carbon diluent such as the saturated aliphatic and aro
`ethanol such as 2-methoxyethanol, 2-ethoxyethanol, 2
`matic hydrocarbons. Still further, in the final fractional
`propoxyethanol and 2-butoxyethanol.
`distillation step to remove the thiophenol, oxygenated
`In addition to the oxygenated vehicle, a volatile inert
`derivative and volatilizable diluent a stripping gas is pref
`liquid hydrocarbon diluent is also preferably included
`erably employed, this gas either being carbon dioxide or
`in the first reaction mixture to facilitate contact. Specific
`an inert gas such as nitrogen. The stripping gas rate is
`examples of such medium are liquid aromatic and sat
`normally between about 0.1 and 7 standard cubic feet/
`urated aliphatic hydrocarbon having boiling points be
`hour/gallon (s.c.f.h./gallon) of carbon dioxide treated
`tween about 190 and 290 F. Such as toluene, xylene and
`product.
`heptane. The volatile diluent normally present in the
`In regard to the normal calcium sulfonate reactant, the
`initial reaction mixture is in an amount betwen about 15
`sulfonic acid from which it is derived are any of the oil
`and 40 wt. percent.
`soluble sulfonic acids such as mahogany sulfonic acid,
`The lubricating oil employed in the initial charge can
`alkylated aromatic sulfonic acid, petrolatum sulfonic acid,
`be either mineral lubricating oil or synthetic lubricating
`paraffin wax sulfonic acid, petroleum naphthene sulfonic
`oil, for example, of the type described in connection with
`acid, polyisobutylene Sulfonic acid, mono- and poly-wax
`the Sulfo reactant. Specific examples of suitable lubricat
`or other alkyl substituted benzene sulfonic acid, mono
`ing oils are the solvent dewaxed paraffinic and naphthenic
`and poly-wax or other alkyl substituted naphthalene sul
`petroleum lubricating oils obtained in petroleum refin
`fonic acid, mono- and poly-wax or other substituted
`ing. A particularly preferred lubricating oil is naphthenic
`cyclohexyl sulfonic acid and mixtures thereof. Preferably,
`base oil since it appears to produce the clearest final com
`the sulfonic acid will have been one derived from sulfona
`positions in the concentrate. Advantageously, the lubri
`tion of a petroleum hydrocarbon fraction. The preferred
`cating oil component has an SUS viscosity between about
`sulfonic acids have a molecular weight between about 450
`70 and 900 at 100 F., preferably between about 100
`and 550 but the molecular weight of the sulfonic acid
`and 300. The total lubricating oil content of the initial
`can be as low as 350 or as high as 1500 for making suf
`charge including the lubricating oil associated with the
`ficiently oil soluble normal calcium sulfonate. Particularly
`preferred sulfonic acids are the petroleum hydrocarbon
`Sulfo reactant is advantageously between about 10
`and 50 wt. percent. The function of the lubricating oil
`sulfonic acid of a molecular weight of about 480. By the
`component is not only to facilitate contact of the over
`term "oil soluble' we means soluble in a conventional
`based calcium sulfonate product, but also to facilitate
`lubricating oil fraction to the extent of at least about 5
`introduction of the overbased sulfonate into lubricant
`wt. percent.
`compositions as an additive.
`Ordinarily, the normal calcium sulfonate reactant use
`In order to aid in the dispersion of the formed cal
`ful in the method of the invention is introduced into the
`cium sulfonate particles in a lubicating oil concentrate,
`first reaction stage in a diluted form, the diluent being
`standard dispersants are advantageously incorporated as
`an oil, water immiscible, organic medium which normally
`one of the initial charge materials such as N-octadecyl
`will be a petroleum or synthetic hydrocarbon lubricating
`Sulfo Succinamate, tetrasodium N-(1,2-dicarboxyethyl-n-
`oil, a gas oil fraction or even a lighter cut such as ben
`octadecylsulfo Succinamate, sodium dioctylsulfo succinate,
`Zene or light solvent naphtha. Alternatively, the oil dilu
`
`30
`
`3 5
`
`40
`
`50
`
`60
`
`65
`
`70
`
`Page 2 of 5
`
`

`

`3,373,108
`5
`6
`oleyl primary amine, N-"tallow' 1,3-propane diamine, and
`sulfonate lube oil concentrate as the residue. The residue
`oxylated nonyl phenols of the formula:
`was then filtered through a 2 ft. blotter paper filter uti
`lizing 1 wt. percent finely divided diatomaceous silica
`filter aid in the crude concentrate. The resultant over
`based calcium sulfonate lube oil concentrate filtrate
`weighed 9586 grams and filtered through the filter at a
`rate of 5 gallons/hour/ft. The test data on the over
`based calcium sulfonate filtrate product is reported below
`in Table II:
`
`(OCH2CH)OH
`
`Y-CoE19
`
`Table II
`12.9
`Calcium, wt. percent------------------------
`1.6
`Sulfur ------------------------------------
`335
`TBN-------------------------------------
`Specific gravity 60/60 F. ------------------ 1.1913
`Viscosity, 210 F. cs. ----------------------- 9.30
`Lumetron' -------------------------------
`5.5
`Carbon dioxide, wt. percent ----------------- 10.95
`H2S, wt. percent --------------------------- 0.004
`Sodium, wt. percent ------------------------ 0.05
`25 vol. percent of filtrate in mineral lubricating oil of an
`SUS viscosity at 100° F. of about 845.
`EXAMPLE III
`This example illustrates the preparation of the normal
`calcium sulfonate utilized as a reactant.
`The procedure employed was the same as that utilized
`in Example I except the quantities employed were 210
`lbs. of the sodium petroleum sulfonate oil solution of
`Example I, 163 lbs. of petroleum naphthene lube oil of an
`SUS viscosity of about 100 at 100 F., 18 lbs. calcium
`chloride and 54 lbs. water. The test results on the resultant
`normal calcium sulfonate-lube oil mixture were as follows:
`Table III
`
`0.
`
`20
`
`wherein n is an average integer of from 2 to 9. The
`added dispersant is desirably present in the initial reac
`tion mixture between about 0.1 and 5 wt. percent.
`The following examples further illustrate the inven
`tion, but are not to be construed as limitations thereof:
`EXAMPLE I
`This example illustrates the production of the normal
`calcium sulfonate reactant.
`To a 500 gallon stainless steel reactor there was
`charged 1750 lbs. of a mineral oil solution of sodium
`petroleum sulfonate having a molecular weight of about
`500 giving an analysis of 3 wt. percent Na. about 24
`wt. percent mineral oil, about 4 wt. percent water and
`a kinematic viscosity of about 1200 at 210 F. In addi
`tion, there was also charged 1360 lbs. of naphthenic
`base lubricating oil of an SUS viscosity of 300 at 100
`F. and 154 lbs. of calcium chloride dissolved in 462 lbs.
`of water. The reactor contents were heated to 350 F.
`with nitrogen blowing. The reactor was held at 350 F.
`for 4 hours during which time all water present in the
`reaction mixture was removed. Into the resultant normal
`calcium sulfonate-lube oil reactant mixture there was
`incorporated 1 wt. percent finely divided diatomaceous
`silica as a filter aid and said product was pressure filtered
`through blotter paper.
`The test data results on the resultant filtered normal
`calcium sulfonate reactant mixture are found below in
`Table I:
`-
`
`Table I
`
`Results
`Test:
`Calcium ------------------------------
`1.96
`Sulfur --------------------------------
`2.25
`Sodium, wt. percent -------------------- 0.07
`Specific gravity, 60/60 F. ----------- -
`0.9764
`Viscosity, 210°F, cs. -------------------
`441
`
`25
`
`30
`
`35
`
`40
`
`Results
`Tests:
`Calcium, wt. percent --------------------
`1.81
`Sulfur, wt. percent----------------------
`2.36
`Sodium, wt. percent --------------------
`0.24
`Specific gravity 60/60 F. --------------- 0.9839
`Viscosity, 210 F. CS. ------------------
`150
`EXAMPLE IV
`This example further illustrates the method of the in
`vention.
`To a stainless steel 10-gallon reactor there was charged
`2640 grams of petroleum naphthene oil of an SUS vis
`cosity of about 100 at 100 F., 7250 grams normal calcium
`sulfonate-lube oil mixture prepared as in Example III,
`3870 grams toluene, 3870 grams methanol, 700 grams
`water and 9430 grams thiophenol. The reaction mixture
`was stirred for 10 minutes while purging the reactor with
`nitrogen. The agitation and nitrogen purge were stopped
`and the reactor was charged with 2180 grams calcium ox
`ide. The stirring of the reaction mixture was reinstituted
`and rapid stirring was continued throughout the remainder
`of the run. The reactor was then vented, blown with
`nitrogen at a rate of 16 s.c.f. h. and heated over a half
`hour period in the range of 145-175 F. The nitrogen
`blowing was halted and the reactor contents were then
`refluxed for a 4-hour period at 178 F. At the end of the
`4-hour period the contents were cooled to 146 F. over a
`1.5 hour period. Carbon dioxide was then bubbled through
`the cooled reaction mass at 146 F. for a period of 3.5
`hours at a rate of 43 s.c.f.h. During this 3.5 hour period
`6820 grams of carbon dioxide were introduced. The re
`actor was then vented and the reaction mixture stripped
`at 345 F. with carbon dioxide at 20 s.c.f.h. under a pres
`sure of 20 mm. Hg to remove thiophenol, methanol,
`toluene and water as well as volatilizable by-products leav
`ing a crude overbased calcium sulfonate lube oil concen
`trate as residue. The crude residue to which was added
`finely divided diatomaceous silica in an amount of 1 wt.
`percent was filtered on a 2 ft. pressure blotter filter at
`300 F. There was recovered 11,350 grams of overbased
`
`50
`
`55
`
`60
`
`EXAMPLE
`This example illustrates the method of the invention.
`To a 10 gallon stainless steel reactor there was charged
`7248 grams of filtered calcium sulfonate-lube oil reactant
`mixture of Example i, 2633 grams of naphthenic base oil
`of a viscosity of 100 at 100° F., 3869 grams toluene, 3869
`grams methanol, 21.74 grams calcium oxide, 698 grams
`water and 8571 grams thiophenol. The resultant mixture
`being continuously stirred throughout the entire process,
`was heated to 175 F. for a 1.5 hour period and held at
`175 F. for an additional 2-hour period. The stirred mix
`ture was then cooled from 175 F. over a 0.5 hour period
`and carbon dioxide was bubbled through the stirred reac
`tion mixture at a temperature of 146 F. for a 4-hour
`period utilizing a carbon dioxide rate of 43 s.c.f.h. Dur
`ing the carbon dioxide blowing step the charged carbon
`dioxide was continuously vented from the reactor. The
`amount of carbon dioxide introduced into the system over
`65
`the 4-hour period was 6820 grams. At the end of the 4
`hour period the carbon dioxide blowing was continued
`for an additional 2 hours and during which time vacuum
`stripping by raising the temperature from 146 to 300
`F. and reducing the pressure to 20 mm. Hg was instituted.
`The resultant vacuum stripping was continued for an addi
`tional 2-hour period at a temperature range of 303 to
`350 F. substituting nitrogen for carbon dioxide as the
`stripping gas, thereby stripping out water, methanol, tol
`uene and thiophenol leaving the crude overbased calcium
`
`70
`
`Page 3 of 5
`
`

`

`5
`
`0
`
`5
`
`30
`
`35
`
`40
`
`45
`
`55
`
`60
`
`65
`
`fined.
`
`-
`
`N
`
`Results
`Tests:
`Calcium, wt. percent ------------------------
`12.8
`Sulfur, wt. percent ------------------------
`1.7
`TBN -------------------------------------
`348
`Specific gravity 60/60 F. ------------------- 1.2272
`Kinetic viscosity, 210 F. c.S. ---------------- 194A36
`Lumetron -------------------------------
`9.5
`Carbon dioxide, wt. percent ------------------
`10.8
`H2S, wt. percent --------------------------- 0.0001.
`Sodium, wt. percent ------------------------
`0.17
`125 vol. percent of filtrate in petroleum lubricating oil of an
`SUS viscosity at 100° F. of about 845.
`EXAMPLE V
`This comparative example illustrates the importance of
`employing a thiophenol compound within the scope de
`To a 2-liter stainless steel reactor there was charged 254
`grams of a filtered normal calcium sulfonate-lube oil
`solution giving the following analysis: wt. percent
`Ca=1.58
`wt. percent S=2.5, wt. percent Na=0.20, wt. percent
`HO-0.01, specific gravity 60/60 F.-0.98 le, kinetic vis
`cosity, cs. at 210 F-275. There was also charged 95
`grams methanol, 62 grams calcium oxide, 10 grams water
`and 458 grams pentanethiol. The resultant mixture being
`continuously stirred throughout the entire process, was
`heated to 140 F. for a 2-hour period and held at 140
`F. for an additional 3-hour period. The mixture was held
`between 137 and 140 F. and carbon dioxide was bubbled
`through the stirred reaction mixture at 50 p.s.i.g. for a
`4 hour period utilizing a carbon dioxide rate of 217.5
`grams/hr. During the carbon dioxide blowing step the
`charged carbon dioxide was vented continuously from the
`reactor. At the end of the 4-hour period the mixture was
`transferred to a 3 liter flask. The temperature was raised
`from 80 to 350°. F. and carbon dioxide blowing was con
`tinued for an additional 2 hours at a rate of 56 grams/hr.
`at 350° F. at a pressure of 10 mm. Hg. This vacuum
`stripping resulted in the removal of water, methanol and
`pentanethiol leaving an obviously unfilterable residue.
`We claim:
`4. A method of producing an overbased calcium sul
`fonate lubricating oil concentrate comprising:
`(a) forming a first reaction mixture composed of nor
`mal calcium sulfonate derived from an oil soluble hy
`drocarbyl sulfonic acid, a basic calcium compound
`selected from the group consisting of calcium hy
`droxide and a combination of calcium oxide and wa
`ter and mixtures thereof, an oxygenated vehicle se
`lected from the group consisting of lower alkanol
`and lower alkoxyethanol, a lubricating oil selected
`from the group consisting of mineral lubricating oil
`and synthetic lubricating oil of an SUS viscosity at
`100° F. between about 70 and 900 and a thiophenol
`compound of the formula:
`SHR
`/
`%
`
`3,373,108
`8
`7
`to form carbon dioxide treated second reaction mix
`calcium sulfonate lubricating oil concentrate as filtrate
`having the following properties:
`ture at said temperature,
`-
`- -
`(c) separating residual water, oxygenated vehicle and
`Table IV
`thiophenol from said second reaction mixture leav
`ing said concentrate as residue,
`(d) said normal calcium sulfonate, said basic calcium
`compound, said oxygenated vehicle, said thiophenol
`being present in said first reaction mixture in a mole
`ratio of between about 1:2:40:10 and 1:19:5:40,
`said lubricating oil being present in an amount be
`tween about 10 and 50 wt. percent, and the mole ratio
`of calcium oxide to water in said combination being
`between about 1:0.1 and 1:5.
`2. A method of producing an overbased calcium sul
`fonate lubricating oil concentrate comprising:
`(a) forming a first reaction mixture composed of nor
`mal calcium sulfonate derived from an oil soluble
`hydrocarby sulfonic acid, thiophenol, a basic cal
`cium compound selected from the group consisting of
`calcium hydroxide and a combination of calcium ox
`ide and water and mixtures thereof, an oxygenated
`vehicle selected from the group consisting of lower
`alkanol and lower alkoxyethanol and a lubricating
`oil selected from the group consisting of mineral
`lubricating oil and synthetic lubricating oil of an
`SUS viscosity at 100 F. between about 70 and 900,
`(b) maintaining said first reaction mixture at a tem
`perature between about 50 and 200 F. while con
`tacting said first reaction mixture with carbon dioxide
`to form carbon dioxide treated second reaction mix
`ture at said temperature,
`.
`.
`(c) separating residual water, oxygenated vehicle and
`thiophenol from said second reaction mixture leave
`ing said concentrate as residue,
`(d) said normal calcium sulfonate, said basic calcium
`compound, said oxygenated vehicle, said thiophenol
`being present in said first reaction mixture in a mole.
`ratio of between about 1:2:40:10 and 1:19:5:40,
`said lubricating oil being present in an amount be
`tween about 10 and 50 wt. percent and the mole ratio
`of calcium oxide to water in said combination being
`between about 1:0.1 and 1:5.
`3. A method of preparing an overbased calcium sul
`fonate lubricating oil concentrate comprising:
`(a) forming a first reaction mixture composed of nor
`mal calcium sulfonate derived from an oil soluble
`hydrocarbyl sulfonic acid of a molecular weight of
`between about 350 and 1500, thiophenol, a basic cal
`cium compound selected from the group consisting
`of calcium hydroxide, a combination of calcium ox
`ide and water and mixtures thereof, an oxygenated
`vehicle selected from the group consisting of lower
`alkanol and lower alkoxyethanol, a lubricating oil
`having an SUS viscosity at 100°. F. of between about
`100 and 300, and a volatilizable diluent selected
`from the group consisting of aromatic and saturated
`aliphatic hydrocarbon having a boiling point between
`190 and 300 F.
`-
`(b) heating said first reaction mixture at a temperature
`between about 50 and 200 F., subsequently passing
`carbon dioxide through said first reaction mass at
`a temperature between about 50 and 200 F. in an
`amount of carbon dioxide to basic metal compound
`of at least about one mole carbon dioxide per mole
`basic calcium compound,
`-
`(c) Subsequently stripping said first reaction mass at
`a temperature between about 300 and 370 F. under
`a pressure of between about 1 and 50 mm. Hg to
`remove thiophenol, residual water, volatizable dil
`uent and oxygenated vehicle leaving said overbased
`calcium sulfonate oil concentrate as residue,
`(d) said normal calcium sulfonate, said basic calcium
`compound, said oxygenated vehicle and said thio
`phenol in said first reaction mixture being present in
`a mole ratio between about 1:2:40:10 and 1:19:5:40,
`
`R
`where R and R' are members, each containing less
`than 13 carbon atoms, selected from the group con
`sisting of hydrogen, alkyl, cycloalkyl, aryl, alkaryl,
`aralkyl, alkoxy, acyl, halogen, nitro, and amino,
`(b) maintaining said first reaction mixture at a tem
`perature between about 50 and 200. F. while con
`tacting said first reaction mixture with carbon dioxide
`
`70
`
`Page 4 of 5
`
`

`

`3,373,108
`9
`said lubricating oil being present in an amount be
`ing oil is mineral lubricating oil of an SUS viscosity at
`tween about 10 and 50 wt. percent, the mole ratio
`100 F. between about 100 and 300.
`of calcium oxide to water in said combination being
`between about 10:0.1 and 1:5, and said volatilizable
`References Cited
`diluent being present in an amount of between 15
`UNITED STATES PATENTS
`and 40 wt. percent.
`2,616,924
`11/1952
`Asseff et al. -------- 252-33 X
`4. A method in accordance with claim 3 wherein said
`3,027,325
`3/1962
`McMillen et al. ------ 252-33
`first heating is conducted in an inert gas atmosphere, said
`3,057,896
`10/1962
`Schlicht et al. ------ 252-33 X
`oxygenated vehicle is methanol, said volatilizable diluent
`3,223,630
`12/1965
`Gragson ------------ 252-33
`is toluene, said basic compound is said combination of 10 3,256,186
`6/1966
`Greenwald ---------- 252-33
`calcium oxide and water, said normal calcium sulfonate
`is derived from a petroleum sulfonic acid having a molec
`DANIEL E. WYMAN, Primary Examiner.
`ular weight between about 450 and 550 and said lubricat
`PATRICK. P. GARVIN, Examiner.
`
`Page 5 of 5
`
`