(12) United States Patent
`Abraham et al.
`
`USOO6777378B2
`(10) Patent No.:
`US 6,777,378 B2
`(45) Date of Patent:
`Aug. 17, 2004
`
`(54) MOLYBDENUM, SULFUR AND BORON
`CONTAINING LUBRICATING OL
`COMPOSITION
`
`(75) Inventors: William D. Abraham, South Euclid,
`OH (US); Jack C. Kelley, Chagrin
`Falls, OH (US); Jonathan S. Vilardo,
`Willoughby, OH (US)
`-
`-
`-
`-
`(73) Assignee: The Lubrizol Corporation, Wickliffe,
`OH (US)
`
`(*) Notice:
`
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 171 days.
`
`(21) Appl. No.: 10/077,416
`(22) Filed:
`Feb. 15, 2002
`(65)
`Prior Publication Data
`US 2003/0166477 A1 Sep. 4, 2003
`(51) Int. Cl." ............................................. C10M 141/12
`(52) U.S. Cl. ....................... 508,185; 508/230; 508/363;
`508/364; 508/365; 508/371; 508/375
`(58) Field of Search ................................. 508/198, 199,
`508/362,363, 364, 365, 185
`
`(56)
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`3,405,064 A 10/1968 Miller - - - - - - - - - - - - - - - - - - - - - - - 252/51.5
`
`3,541,014 A 11/1970 Le Suer ..................... 252/49.7
`4,178.258 A 12/1979 Papay et al. ............ 252/32.7 E
`4,234,435 A 11/1980 Meinhardt et al. ......... 252/51.5
`4.258,822 A 3/1981 de Vries et al. ........... 252/46.4
`4,265,773 A 5/1981 deVries et al. ...... ... 252/46.4
`4,315,826 A 2/1982 Schlicht et al. ............ 252/46.4
`4,370.248 A * 1/1983 Horodysky et al. ......... 508/199
`4,507,216 A
`3/1985 Braid et al. ................. 508/199
`
`
`
`4.584,115 A 4/1986 Davis ........................ 252/49.6
`4,692.257 A * 9/1987 Horodysky
`... 508/199
`5.240,624 A 8/1993 Koch ...............
`... 252/49.6
`5,281,347 A
`1/1994 Igarashi et al. ...
`... 252/42.7
`5,595.964 A
`1/1997 Bardasz ...........
`... 508/423
`5,605,880 A 2/1997 Arai et al. ........
`... 508/379
`5629272 A * 5
`Y/1 - 2
`f1997 Nakazato et al. .
`... 508/185
`5,631,213 A * 5/1997 Tanaka et al. ........
`... 508/363
`5,698,499 A * 12/1997 Baranski et al. ............ 508/198
`5,759,965 A * 6/1998 Sumiejski ............
`... 508/186
`5,916,851 A * 6/1999 Hosonuma et al. ......... 508/363
`6,103,672 A 8/2000 Dunn et al. ...........
`... 508/185
`6,103,674. A
`8/2000 Nalesnik et al. ............ 508/334
`6,165.235 A 12/2000 Kolp et al. ................... 44/331
`6.228.818 B1 * 5/2001 Schwind et al. ..
`... 508/187
`6,500,786 B1 12/2002 Hartley et al. .............. 508/365
`FOREIGN PATENT DOCUMENTS
`
`2/1982
`7/1996
`
`O 609 623
`EP
`96/06904
`WO
`* cited by examiner
`Primary Examiner Ellen M. McAvoy
`(74) Attorney, Agent, or Firm-David M. Shold; Michael F.
`Esposito; Neil Duchez
`(57)
`ABSTRACT
`This invention relates to a lubricating oil composition,
`comprising:
`(A) a base oil;
`(b) a. lying and R E. otein
`erTVed Irom a basic nitrogen containing compound, a
`
`molybdenum compound and carbon disulfide;
`
`d; and
`taini
`(C) b
`a Doron-containing compound; an
`(D) optionally a phosphorus containing compound, pro
`vided the phosphorus content of the lubricating oil
`composition does not exceed about 0.10% by weight.
`
`18 Claims, No Drawings
`
`ORONITE EXHIBIT 1005
`
`Page 1 of 11
`
`

`

`US 6,777,378 B2
`
`1
`MOLYBDENUM, SULFUR AND BORON
`CONTAINING LUBRICATING OIL
`COMPOSITION
`
`TECHNICAL FIELD
`
`This invention relates to molybdenum, Sulfur and boron
`containing lubricating oil compositions. More particularly,
`this invention relates to a lubricating oil composition con
`taining a molybdenum and Sulfur containing composition, a
`boron-containing compound, and optionally a phosphorus
`containing compound provided the amount of phosphorus
`does not exceed about 0.10% by weight.
`
`BACKGROUND OF THE INVENTION
`
`For more than 40 years, Zinc dialkyl dithiophosphates
`(ZDDP) have been used as antiwear and antioxidant addi
`tives in engine lubricating oil compositions. During this
`period typical concentrations of phosphorus contributed to
`the lubricating oil compositions by these compounds
`exceeded 0.10% by weight. However, ILSAC GF-3 require
`ments limit the amount of phosphorus that can be used in a
`lubricating oil composition to a maximum concentration of
`0.10% by weight, and it is believed that GF-4 may limit the
`amount of phosphorus to a maximum concentration of
`0.05% by weight. The problem therefore is to provide for a
`reduction in the amount of phosphorus-containing additives
`used in these lubricating oil compositions and yet provide
`the lubricating oil with required antiwear and antioxidant
`properties.
`The use of molybdenum and Sulfur containing composi
`tions in lubricating oil compositions as antiwear agents and
`antioxidants is known. U.S. Pat. No. 4,285,822 discloses
`lubricating oil compositions containing a molybdenum and
`Sulfur containing composition prepared by (1) combining a
`polar Solvent, an acidic molybdenum compound and an
`oil-soluble basic nitrogen compound to form a
`molybdenum-containing complex and (2) contacting the
`complex with carbon disulfide to form the molybdenum and
`Sulfur containing composition.
`The replacement of part of the ZDDP in a lubricating oil
`composition with a molybdenum and Sulfur containing
`composition of the type described in the above-mentioned
`patent provides the advantage of restoring antiwear and
`antioxidant properties lost with the reduction in ZDDP.
`However, a problem with these compositions is that they fail
`to pass the required GF-3/GF-4 Sequence VIII Bearing
`Corrosion Engine Test. This problem has been overcome
`with the present invention.
`
`SUMMARY OF THE INVENTION
`
`This invention relates to a lubricating oil composition,
`comprising:
`(A) a base oil;
`(B) a molybdenum and Sulfur containing composition
`derived from a basic nitrogen containing compound, a
`molybdenum compound and carbon disulfide;
`(C) a boron-containing compound Selected from the group
`consisting of:
`(C-I) aborated ester represented by one or more of the
`formulae
`
`15
`
`25
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`2
`
`RO
`V
`RO-B O
`/
`RO
`
`OR
`RO
`/
`V
`RO-B-O-B-OR or
`
`s B ry
`
`RO "N,1 B OR
`
`(C-I-1)
`
`(C-I-2)
`
`(C-1-3)
`
`wherein in formulae (C-I-1), (C-I-2) and (C-I-3),
`each R is independently a hydrocarbon group and
`any two adjacent R groups may together form a
`cyclic group;
`(C-II) at least one borated epoxide comprising the
`product made by reacting a boron reactant with one
`or more epoxides represented by the formula
`
`R
`
`R
`
`R-C
`C-R
`No1
`
`(C-II-1)
`
`wherein in formula (C-II-1) each R is independently
`hydrogen or a hydrocarbon group and any two
`adjacent R groups may together form a cyclic group,
`with the proviso that when a single epoxide is used
`the total number of carbon atoms in the R groups
`does not exceed about 12, and when a mixture of
`epoxides is used the average on a mole basis for the
`total number of carbon atoms in the R groups for the
`mixture does not exceed about 12, and
`(C-III) mixture of (C-I) and (C-II); and
`(D) optionally a phosphorus containing compound pro
`vided the phosphorus content of the lubricating oil
`composition does not exceed about 0.10% by weight.
`DETAILED DESCRIPTION OF THE
`INVENTION
`The terms “hydrocarbon” and “hydrocarbyl” when refer
`ring to a group having a carbon atom directly attached to the
`remainder of a molecule denote a group having a hydrocar
`bon or predominantly hydrocarbon character within the
`context of this invention. These groups include the follow
`Ing:
`(1) Purely hydrocarbon groups; that is, aliphatic, (e.g.,
`alkyl or alkenyl), alicyclic (e.g., cycloalkyl or
`cycloalkenyl), aromatic, aliphatic- and alicyclic
`Substituted aromatic, aromatic-Substituted aliphatic and
`alicyclic groups, and the like, as well as cyclic groups
`wherein the ring is completed through another portion
`of the molecule (that is, any two indicated Substituents
`may together form an alicyclic group). Examples
`include methyl, ethyl, octyl, cyclohexyl, phenyl, etc.
`(2) Substituted hydrocarbon groups; that is, groups con
`taining non-hydrocarbon Substituents which do not
`alter the predominantly hydrocarbon character of the
`group. Examples include hydroxy, nitro, cyano, alkoxy,
`acyl, etc.
`(3) Hetero groups; that is, groups which, while predomi
`nantly hydrocarbon in character, contain atoms other
`
`Page 2 of 11
`
`

`

`3
`than carbon in a chain or ring otherwise composed of
`carbon atoms. Suitable hetero atoms include, for
`example, nitrogen, oxygen and Sulfur.
`In general, no more than about three Substituents or hetero
`atoms, and in one embodiment no more than one, will be
`present for each 10 carbon atoms in the hydrocarbyl group.
`The term “lower” as used herein in conjunction with
`terms Such as hydrocarbyl, alkyl, alkenyl, alkoxy, and the
`like, is intended to describe Such groups which contain a
`total of up to 7 carbon atoms.
`The term “oil-soluble” refers to a material that is soluble
`in mineral oil to the extent of at least about one gram per liter
`at 25° C.
`The term “TBN' refers to total base number. This is the
`amount of acid (perchloric) needed to neutralize a materials
`basicity, expressed as milligrams of KOH per gram of
`Sample.
`The term “TAN' refers to total acid number. This is the
`amount of base (potassium hydroxide orSodium hydroxide)
`needed to neutralize a materials acidity, expressed as mil
`ligrams of KOH per gram of Sample.
`The Lubricating Oil Composition.
`The inventive lubricating oil composition may be com
`prised of a major amount of base oil. The base oil may be
`present in an amount greater than about 50% by weight, and
`in one embodiment greater than about 60%, and in one
`embodiment greater than about 70%.
`The inventive lubricating oil composition may have a
`viscosity of up to about 17 cSt at 10 C., and in one
`embodiment about 5 to about 17 cSt at 10 C., and in one
`embodiment about 6 to about 13 cSt at 100° C.
`The inventive lubricating oil composition may have an
`SAE Viscosity Grade of OW, OW-20, OW-30, OW-40, OW-50,
`OW-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W,
`1OW-20, 10W-30, 10W-40, 10W-50, 10W-60, 15W-30,
`15W-40, 15W-50, 20W, 20W-50, or 30W.
`The inventive lubricating oil composition may have a
`molybdenum content of about 25 to about 800 parts per
`million (ppm), and in one embodiment about 50 to about 700
`ppm, and in one embodiment about 100 to about 600 ppm.
`The inventive lubricating oil composition may have a
`sulfur content of about 0.02 to about 1.3% by weight, and in
`one embodiment about 0.07 to about 0.8% by weight, and in
`one embodiment about 0.1 to about 0.5% by weight.
`The inventive lubricating oil composition may have a
`boron content of about 30 to about 600 ppm, and in one
`embodiment about 35 to about 400 ppm, and in one embodi
`ment about 40 to about 200 ppm.
`The inventive lubricating oil composition may have a
`phosphorus content of up to about 0.10% by weight, and in
`one embodiment up to about 0.09% by weight, and in one
`embodiment up to about 0.08% by weight, and in one
`embodiment up to about 0.075% by weight, and in one
`embodiment up to about 0.07% by weight, and in one
`embodiment up to about 0.06% by weight, and in one
`embodiment up to about 0.05%.
`The ash content of the inventive lubricating oil compo
`sition as determined by the procedures in ASTM D-874-96
`may be in the range up to about 1.2% by weight, and in one
`embodiment up to about 1.1% by weight, and in one
`embodiment from about 0.3 to about 1.2% by weight, and in
`one embodiment about 0.3 to about 1.1% by weight, and in
`one embodiment about 0.3 to about 1.0% by weight, and in
`one embodiment about 0.5 to about 1.0% by weight.
`The inventive lubricating oil composition may have a
`chlorine content of up to about 100 ppm, and in one
`embodiment up to about 80 ppm, and in one embodiment up
`
`4
`to about 50 ppm, and in one embodiment up to about 30
`ppm, and in one embodiment up to about 10 ppm.
`The inventive lubricating oil composition may be used as
`a lubricating oil composition for internal combustion
`engines Such as gasoline powered engines and diesel
`engines, including passenger car engines and heavy duty
`diesel engines. In one embodiment, the inventive lubricating
`oil composition exhibits enhanced GF-4 Sequence VIII
`Bearing Corrosion Engine Test results.
`(A) The Base Oil
`The base oil used in the inventive lubricating oil compo
`Sition may be Selected from any of the base oils in Groups
`I-V as specified in the American Petroleum Institute (API)
`Base Oil Interchangeability Guidelines. The five base oil
`groups are as follows:
`
`Base Oil
`Category
`
`Group I
`Group II
`Group III
`Group IV
`Group V
`
`Sulfur (%)
`
`Saturates (%)
`
`&90
`andfor
`>O.O3
`290
`and
`sO.O3
`290
`and
`sO.O3
`All polyalphaolefins (PAOs)
`All others not included in
`Groups I, II, III or IV
`
`Viscosity
`Index
`
`80 to 120
`80 to 120
`2120
`
`Groups I, II and III are mineral oil base stocks.
`The base oil may be a natural oil, Synthetic oil or mixture
`thereof. The natural oils that are useful include animal oils
`and vegetable oils (e.g., castor oil, lard oil) as well as
`mineral lubricating oils. Such as liquid petroleum oils and
`solvent treated or acid-treated mineral lubricating oils of the
`paraffinic, naphthenic or mixed paraffinic-naphthenic
`types. Oils derived from coal or shale are useful.
`Synthetic lubricating oils include hydrocarbon oils. Such
`as polymerized and interpolymerized olefins (e.g.,
`polybutylenes, polypropylenes, propylene isobutylene
`copolymers, etc.); poly(1-hexenes), poly-(1-octenes), poly
`(1-decenes), etc. and mixtures thereof, alkylbenzenes (e.g.,
`dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di
`(2-ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls,
`terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl
`ethers and alkylated diphenyl Sulfides and the derivatives,
`analogs and homologs thereof and the like.
`Alkylene oxide polymers and interpolymers and deriva
`tives thereof where the terminal hydroxyl groups have been
`modified by esterification, etherification, etc., constitute
`another class of known Synthetic lubricating oils that can be
`used.
`Another Suitable class of Synthetic lubricating oils that
`can be used comprises the esters of dicarboxylic acids (e.g.,
`phthalic acid, Succinic acid, alkyl Succinic acids, alkenyl
`Succinic acids, maleic acid, azelaic acid, Suberic acid, Seba
`cic acid, fumaric acid, adipic acid, linoleic acid dimer,
`malonic acid, alkyl malonic acids, alkenyl malonic acids,
`etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl
`alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene
`glycol, diethylene glycol monoether, propylene glycol, etc.)
`Esters useful as Synthetic oils also include those made
`from Cs to C monocarboxylic acids and polyols and polyol
`etherS Such as neopentyl glycol, trimethylol propane,
`pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
`The synthetic base oil may be a poly-alpha-olefin (PAO).
`Typically, the poly-alpha-olefins are derived from mono
`mers having from about 4 to about 30 carbon atoms.
`The synthetic base oil may be an oil derived from Fischer
`Tropsch synthesized hydrocarbons. Fischer-Tropsch synthe
`
`US 6,777,378 B2
`
`15
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`50
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`Page 3 of 11
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`

`

`US 6,777,378 B2
`
`S
`sized hydrocarbons are made from Synthesis gas containing
`H and CO using a Fischer-Tropsch catalyst. These hydro
`carbons may require further processing in order to be useful
`as the base oil. For example, the hydrocarbons may be
`hydroisomerized, hydrocracked or dewaxed using known
`techniques.
`Unrefined, refined and rerefined oils, either natural or
`Synthetic (as well as mixtures of two or more of any of these)
`of the type disclosed hereinabove can be used as the base oil.
`Unrefined oils are those obtained directly from a natural or
`Synthetic Source without further purification treatment.
`Refined oils are similar to the unrefined oils except they have
`been further treated in one or more purification Steps to
`improve one or more properties. Rerefined oils are obtained
`by processes Similar to those used to obtain refined oils
`applied to refined oils which have been already used in
`Service. Rerefined oils are also known as reclaimed or
`reprocessed oils and often are additionally processed by
`techniques directed to removal of spent additives and oil
`breakdown products.
`(B) The Molybdenum and Sulfur Containing Composition.
`The molybdenum and Sulfur containing composition may
`be derived from a basic nitrogen containing compound, a
`molybdenum compound and carbon disulfide. In one
`embodiment, the basic nitrogen containing compound may
`be reacted initially with the molybdenum compound to form
`a molybdenum containing intermediate, and then the molyb
`denum containing intermediate is reacted with the carbon
`disulfide to form the desired molybdenum and sulfur con
`taining composition. Alternatively, the basic nitrogen con
`taining compound may be reacted initially with the carbon
`disulfide to form a sulfur containing intermediate, and then
`the Sulfur containing intermediate may be reacted with the
`molybdenum compound to form the desired molybdenum
`and Sulfur containing composition. In one embodiment, the
`molybdenum and Sulfur containing composition is a molyb
`denum dithiocarbamate.
`The basic nitrogen containing compound may be a nitro
`gen containing compound having a TBN of at least about 30,
`and in one embodiment at least about 50, and in one
`embodiment at least about 80. The basic nitrogen containing
`compound may be: the product made by the reaction of a
`carboxylic acid or reactive equivalent thereof with an alky
`lene polyamine; a hydrocarbyl amine; or a mixture thereof.
`In one embodiment, the carboxylic acid or reactive
`equivalent thereof used to make the basic nitrogen contain
`ing compound may have about 8 to about 34 carbon atoms
`per molecule, and in one embodiment about 12 to about 24
`carbon atoms. The acids may be monobasic acids or poly
`basic acids. The reactive equivalents include acid halides,
`anhydrides, and esters, including partial esters. The acids
`include fatty acids. Examples include lauric acid, myristic
`acid, palmitic acid, Stearic acid, isotearic acid, oleic acid,
`linoleic acid, linolenic acid, arachidic acid, behenic acid,
`erucic acid, lignoceric acid, and the like. Tall oil fatty acids
`and coconut oil fatty acids may be used. Dimers and trimers
`of fatty acids may be used. The polybasic acids may be
`hydrocarbon Substituted dicarboxylic acids, although tricar
`boxylic or tetracarboxylic acids may be used.
`These include hydrocarbon Substituted Succinic acids or
`anhydrides. The hydrocarbon Substituents on these polyba
`sic acids may have about 6 to about 30 carbon atoms, and in
`one embodiment about 12 to about 24 carbon atoms, and in
`one embodiment about 12 to about 18 carbon atoms.
`In one embodiment, the carboxylic acid or reactive
`equivalent thereof is a hydrocarbon Substituted carboxylic
`acid or reactive equivalent made by reacting one or more
`
`5
`
`15
`
`25
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`6
`alpha, beta olefinically unsaturated carboxylic acid reagents
`containing 2 to about 20 carbon atoms, exclusive of the
`carboxyl groups, with one or more olefin polymers. The
`olefin polymer may contain about 30 to about 500 carbon
`atoms, and in one embodiment 50 to about 500 carbon
`atoms, and in one embodiment about 50 to about 250 carbon
`atoms. In one embodiment, the olefin polymer has a number
`average molecular weight of about 750 to about 3000, and
`in one embodiment about 900 to about 2300.
`The alpha-beta olefinically unsaturated carboxylic acid
`reagents may be either monobasic or polybasic in nature.
`Exemplary of the monobasic alpha-beta olefinically unsat
`urated carboxylic acid reagents include the carboxylic acids
`corresponding to the formula
`R-CH=-cool
`
`wherein R is hydrogen, or a Saturated aliphatic or alicyclic,
`aryl, alkylaryl or heterocyclic group, and R is hydrogen or
`a lower alkyl group. R may be a lower alkyl group. The total
`number of carbon atoms in R and R' typically does not
`exceed about 18 carbon atoms. Specific examples of useful
`monobasic alpha-beta olefinically unsaturated carboxylic
`acids include acrylic acid; methacrylic acid, cinnamic acid;
`crotonic acid; 3-phenyl propenoic acid; alpha, and beta
`decenoic acid. The polybasic acid reagents may be
`dicarboxylic, although tri- and tetracarboxylic acids can be
`used. Exemplary polybasic acids include maleic acid,
`fumaric acid, meSaconic acid, itaconic acid and citraconic
`acid. Reactive equivalents of the alpha-beta olefinically
`unsaturated carboxylic acid reagents include the anhydride,
`ester or amide functional derivatives of the foregoing acids.
`A useful reactive equivalent is maleic anhydride.
`The olefin monomers from which the olefin polymers may
`be derived are polymerizable olefin monomers characterized
`by having one or more ethylenic unsaturated groups. They
`can be monoolefinic monomerS Such as ethylene, propylene,
`butene-1, isobutene and octene-1 or polyolefinic monomers
`(usually di-olefinic monomerS Such as butadiene-1,3 and
`isoprene). Usually these monomers are terminal olefins, that
`is, olefins characterized by the presence of the
`group>C=CH2. However, certain internal olefins can also
`Serve as monomers (these are Sometimes referred to as
`medial olefins). When such medial olefin monomers are
`used, they may be employed in combination with terminal
`olefins to produce olefin polymers that are interpolymers.
`Generally the olefin polymers are homo- or interpolymers
`of terminal hydrocarbon olefins of about 2 to about 30
`carbon atoms, and in one embodiment about 2 to about 16
`carbon atoms. Typically, the olefin polymers are homo- and
`interpolymers of terminal olefins of 2 to about 6 carbon
`atoms, and in one embodiment 2 to about 4 carbon atoms.
`In one embodiment, the olefin polymer is a polyisobutene
`(or polyisobutylene) obtained by the polymerization of a C
`refinery stream having abutene content of about 35 to about
`75% by weight and an isobutene content of about 30 to about
`60% by weight in the presence of a Lewis acid catalyst Such
`as aluminum chloride or boron trifluoride. These poly
`isobutenes may contain predominantly (that is, greater than
`about 50 percent of the total repeat units) isobutene repeat
`units.
`The olefin polymer may be a polyisobutene having a high
`methylvinylidene isomer content, that is, at least about 50%
`by weight, and in one embodiment at least about 70% by
`weight methylvinylidenes. Suitable high methylvinylidene
`polyisobutenes include those prepared using a boron trif
`
`Page 4 of 11
`
`

`

`7
`luoride catalyst. These are described in U.S. Pat. Nos.
`4,152,499 and 4,605,808, which are incorporated herein by
`reference.
`The carboxylic acid or reactive equivalent thereof may be
`a hydrocarbon-Substituted Succinic acid or anhydride
`wherein the hydrocarbon substituent has about 30 to about
`500 carbon atoms, and in one embodiment from about 50 to
`about 500, and in one embodiment from about 50 to about
`250 carbon atoms. In one embodiment, the hydrocarbon
`Substituent is a polyisobutene group. The hydrocarbon Sub
`Stituent may have a number average molecular weight of
`about 750 to about 3000, and in one embodiment about 900
`to about 2300.
`In one embodiment, the hydrocarbon-Substituted Succinic
`acids or anhydrides are characterized by the presence within
`their structure of an average of at least about 1.3 Succinic
`groups, and in one embodiment from about 1.5 to about 2.5,
`and in one embodiment form about 1.7 to about 2.1 Succinic
`groups for each equivalent weight of the hydrocarbon Sub
`Stituent. The ratio of Succinic groups to equivalent of Sub
`Stituent groupS present in the hydrocarbon-Substituted Suc
`cinic acylating agent (also called the “Succination ratio’) can
`be determined by one skilled in the art using conventional
`techniques (Such as from Saponification or acid numbers).
`This is described in U.S. Pat. No. 4,234,435, which is
`incorporated herein by reference.
`The conditions, i.e., temperature, agitation, Solvents, and
`the like, for reacting an alpha, beta olefinically unsaturated
`carboxylic acid reagent with an olefin polymer, are known to
`those in the art. Examples of patents describing various
`procedures for preparing these compounds include U.S. Pat.
`Nos. 3,215,707; 3,219,666; 3,231,587; 3,912,764; 4,110,
`349; 4,234,435; and 6,165,235 and U.K. Patent 1,440,219.
`The disclosures of these patents are incorporated herein by
`reference.
`The alkylene polyamines include those compounds rep
`resented by the formula
`
`R
`
`R
`
`wherein n is from 1 to about 14; each R is independently a
`hydrogen atom, a hydrocarbyl group or a hydroxy
`Substituted or amine-Substituted hydrocarbyl group having
`up to about 30 atoms, or two R groups on different nitrogen
`atoms can be joined together to form a R' group, with the
`proviso that at least one R group is a hydrogen atom, and R'
`is an alkylene group of 1 to about 10 carbon atoms, and in
`one embodiment about 2 to about 10 carbon atoms. R' may
`be ethylene or propylene. Alkylene polyamines where each
`R is hydrogen or an amino-Substituted hydrocarbyl group
`with the ethylene polyamines and mixtures of ethylene
`polyamines are useful n may have an average value of from
`1 to about 10, and in one embodiment about 2 to about 10,
`and in one embodiment about 2 to about 7, and in one
`embodiment about 4 to about 6. The alkylene polyamines
`include methylene polyamine, ethylene polyamines, propy
`lene polyamines, butylene polyamines, pentylene
`polyamines, heXylene polyamines, heptylene polyamines,
`etc. The higher homologs of Such amines and related amino
`alkyl-Substituted piperazines are also included.
`Alkylene polyamines that are useful include ethylene
`diamine, diethylene triamine, triethylene tetramine, tetraeth
`ylene pentamine, pentaethylene hexamine, propylene
`diamine, trimethylene diamine, hexamethylene diamine,
`decamethylene diamine, octamethylene diamine,
`
`US 6,777,378 B2
`
`8
`di(heptamethylene) triamine, tripropylene tetramine, trim
`ethylene diamine, di(trimethylene) triamine, N-(2-
`aminoethyl)piperazine, 1,4-bis(2-aminoethyl)piperazine,
`and the like. Higher homologs as are obtained by condensing
`two or more of the above-illustrated alkylene amines are
`useful, as are mixtures of two or more of any of the
`afore-described polyamines.
`Alkylene polyamines are described in detail under the
`heading “Diamines and Higher Amines” in The Encyclope
`dia of Chemical Technology, Second Edition, Kirk and
`Othmer, Volume 7, pages 27–39, Interscience Publishers,
`Division of John Wiley and Sons, 1965, which is hereby
`incorporated by reference for the disclosure of useful
`polyamines. These compounds may be prepared by the
`reaction of an alkylene chloride with ammonia or by reac
`tion of an ethylene imine with a ring-opening reagent Such
`as ammonia, etc. These reactions often result in the produc
`tion of Somewhat complex mixtures of alkylene polyamines,
`including cyclic condensation products Such as piperazines.
`The alkylene polyamines may be those resulting from the
`Stripping of the above-described alkylene polyamine mix
`tures. In this instance, lower molecular weight alkylene
`polyamines and Volatile contaminants are removed from an
`alkylene polyamine mixture to leave as residue what is often
`termed “alkylene polyamine bottoms'. In general, alkylene
`polyamine bottoms can be characterized as having less than
`about 2% by weight, and in one embodiment less than about
`1% by weight material boiling below about 200 C. In one
`embodiment, the alkylene polyamine bottoms are ethylene
`polyamine bottoms. These may contain less than about 2%
`by weight total diethylene triamine (DETA) or triethylene
`tetramine (TETA). A sample of an ethylene polyamine
`bottoms obtained from the Dow Chemical Company of
`Freeport, Tex. designated “E-100” shows a specific gravity
`at 15.6°C. of 1.0168, a percent nitrogen by weight of 33.15
`and a viscosity at 40 C. of 121 centistokes. Gas chroma
`tography analysis indicates that this Sample contains about
`0.93% “Light Ends" (most probably DETA), 0.72% TETA,
`21.74% tetraethylene pentamine and 76.61% pentaethylene
`hexamine and higher (by weight). The alkylene polyamine
`bottoms may include cyclic condensation products Such as
`piperazine and higher analogs of diethylenetriamine,
`triethylenetetramine, and the like. The Stripped alkylene
`polyamines disclosed in U.S. Pat. No. 5,792,730 may be
`used; this patent is incorporated herein by reference.
`The reaction between the carboxylic acid or reactive
`equivalent thereof and the alkylene polyamine may be
`carried out under conditions that provide for the formation
`of the desired product which may be an amide, an imide, a
`Salt, or a mixture thereof. Typically, the reaction is carried
`out at a temperature in the range from about 50 C. to about
`250 C., and in one embodiment from about 80 C. to about
`220 C.; optionally in the presence of a substantially inert
`organic liquid Solvent/diluent, until the desired product has
`formed. In one embodiment, the carboxylic acid or reactive
`equivalent and the alkylene polyamine are reacted in
`amounts sufficient to provide from about 0.3 to about 3
`equivalents of carboxylic acid or reactive equivalent thereof
`per equivalent of alkylene polyamine. In one embodiment,
`this ratio is from about 0.5:1 to about 2:1, and in one
`embodiment about 0.5:1 to about 1:1.
`The number of equivalents of the carboxylic acid or
`reactive equivalent thereof depends on the total number of
`carboxylic functions present which are capable of reacting
`with the alkylene polyamine. For example, there would be
`two equivalents in an anhydride derived from one mole of
`olefin polymer and one mole of maleic anhydride.
`
`15
`
`25
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`Page 5 of 11
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`

`

`15
`
`25
`
`35
`
`40
`
`The weight of an equivalent of an alkylene polyamine is
`the molecular weight of the alkylene polyamine divided by
`the total number of nitrogens present in the molecule. The
`weight of an equivalent of a commercially available mixture
`of alkylene polyamines can be determined by dividing the
`atomic weight of nitrogen (14) times 100, that is 1400, by
`the % N contained in the alkylene polyamine; thus, an
`alkylene polyamine mixture having a % N of 34 would have
`an equivalent weight of 41.2.
`The hydrocarbyl amines which are useful as the basic
`nitrogen containing compound may be hydrocarbyl amines
`having about 6 to about 30 carbon atoms, and in one
`embodiment about 8 to about 22 carbon atoms. These
`include fatty amines. These compounds may be Saturated or
`unsaturated. They may be primary, Secondary or tertiary
`amines. These hydrocarbyl amines may be prepared by
`reacting a fatty acid with ammonia to form a fatty acid
`amide, converting the amide to a nitrile, and then reducing
`the nitrile to the amine. Any of the fatty acids described
`above may be used. Examples of useful hydrocarbyl amines
`include oleyl amine, coconut amine, tallow amine, lauryl
`amine, caprylamine, isoStearyl amine, Stearyl amine, palm
`itic amine, and the like, and mixtures of two or more thereof.
`The hydrocarbyl amines may be hydrocarbon Substituted
`polyamines having a number average molecular weight in
`the range of about 100 to about 5000, and in one embodi
`ment about 300 to about 4000. These may be prepared by
`reacting a halogen-containing hydrocarbon (e.g., chlorinated
`olefin polymer) with an alkylene polyamine using known
`techniques. Any of the olefin polymers and alkylene
`polyamines discussed above may be used. Examples of
`useful hydrocarbon Substituted polyamines include poly
`isobutene (Mn=500–3000) substituted alkylene polyamines
`Such as polyisobutene Substituted ethylene diamine. Hydro
`carbon Substituted polyamines that may be used are
`described in U.S. Pat. Nos. 3,275,554; 3,454,555; 3,565,
`804; and 3,574,576, which are incorporated herein by ref
`CCCC.
`The molybdenum compound may be any acidic molyb
`denum compound.
`The term “acidic' is used to refer to any molybdenum
`compound that reacts with the basic nitrogen containing
`compound. Typically these molybdenum compounds are
`hexavalent and may be represented by the following: molyb
`dic acid, ammonium molybdate, Sodium molybdate, potas
`sium molybdate and other alkaline metal molybdates and
`other molybdenum Salts. Such as hydrogen Salts, e.g., hydro
`gen sodium molybdate, MoC)C1, MoC).Br., Mo.OCl,
`molybdenum trioxide or Similar acidic molybdenum com
`pounds.
`The carbon disulfide may be derived from any sour