EP0747467B1 - Agents modificateurs de viscosité à base de copolymère de styrène et de diène pour fluides non polluants - Google Patents

Agents modificateurs de viscosité à base de copolymère de styrène et de diène pour fluides non polluants Download PDF

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Publication number
EP0747467B1
EP0747467B1 EP96304157A EP96304157A EP0747467B1 EP 0747467 B1 EP0747467 B1 EP 0747467B1 EP 96304157 A EP96304157 A EP 96304157A EP 96304157 A EP96304157 A EP 96304157A EP 0747467 B1 EP0747467 B1 EP 0747467B1
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Prior art keywords
oil
composition
carbon atoms
hydrogen
sulfur
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EP96304157A
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German (de)
English (en)
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EP0747467A1 (fr
Inventor
Richard Michael Lange
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Lubrizol Corp
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Lubrizol Corp
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Definitions

  • the present invention relates to natural oils or synthetic triglycerides that contain a styrene-diene viscosity modifier.
  • the styrene-diene viscosity modifier is soluble in the natural oil and the synthetic triglyceride.
  • Natural oils and synthetic triglycerides that contain the styrene-diene viscosity modifiers have utility in environmentally friendly farm tractor lubricants and chain bar lubricants and hydraulic fluids.
  • a sunflower oil containing an oleic acid content of 80 percent has a pour point of -12°C and turns solid in the Brookfield viscosity measurement.
  • Many of the industrial applications require a pour point of less than -25°C and a Brookfield viscosity of 7500 to 150,00 centipoises (cP) at -25°C.
  • a key to utilizing a polymer for the thickening of a base oil is that the polymer be soluble in the base oil. This solubility problem is not present for polymers in mineral oil.
  • Natural oils and synthetic triglycerides is another matter. In fact, it is very difficult in finding hydrocarbon polymers that are soluble in natural oils and synthetic triglycerides.
  • Hydrocarbon polymers insoluble in natural oils and synthetic triglycerides are olefin copolymers (OCP), ethylene-propylene diene monomer (EPDM), high molecular weight polybutylene (PBU) and butyl rubbers.
  • OCP olefin copolymers
  • EPDM ethylene-propylene diene monomer
  • PBU high molecular weight polybutylene
  • the present invention relates to hydrogenated random block styrene/diene polymers that are soluble in natural oils and synthetic triglycerides.
  • U.S. Patent No. 2,336,195 (Sparks et al, December 7, 1943) relates to improving viscosity characteristics of hydrocarbon oils by the addition of normal mono-olefin polymers.
  • a normal mono-olefin polymer is converted to a high molecular weight polymer by compressing an olefin, such as ethylene or propylene, to a high superatomspheric pressure in excess of 500 atmospheres.
  • U.S. Patent No. 3,554,911 (Schiff et al, January 12, 1971) relates to improved lubricating oils, particularly mineral lubricating oils, and processes of preparing the same.
  • this reference relates to the addition of a small amount of a hydrogenated random butadiene-styrene copolymer to lubrication oils to produce formulations that are shear stable and have a high viscosity index (V.I.).
  • this reference relates to hydrogenated random butadiene-styrene copolymers having defined amounts of butadiene and styrene which are blended with suitable mineral oils to increase the viscosity and improve the viscosity index.
  • U.S. Patent No. 3,772,196 (St. Clair et al, November 13, 1973) provides for lubricating oil compositions for internal combustion engines that have unexpectedly wide temperature operating characteristics.
  • This composition contains a combination of a 2-block copolymer comprising a first polymer block of an alkenyl arene, e.g., styrene and a second essentially completely hydrogenated polymer block of isoprene and certain pour point depressants in a lubricant base stock having a viscosity index of at least 85
  • composition which comprises
  • a synthetic triglyceride or a natural oil is employed of the formula wherein R 1 , R 2 and R 3 are aliphatic hydrocarbyl groups that contain from 7 to 23 carbon atoms and preferably from 11 to 21 carbon atoms.
  • the term "hydrocarbyl group” as used herein denotes a radical having a carbon atom directly attached to the remainder of the molecule.
  • the aliphatic hydrocarbyl groups include the following:
  • Naturally occurring oils are vegetable oil triglycerides.
  • the synthetic triglycerides are those formed by the reaction of one mole of glycerol with three moles of a fatty acid or mixture of fatty acids.
  • Preferred are vegetable oil triglycerides.
  • the preferred vegetable oils are soybean oil, corn oil, lesquerella oil, rapeseed oil, sunflower oil, canola oil, coconut oil, peanut oil, safflower oil, castor oil and palm olein.
  • the aliphatic hydrocarbyl groups are such that the triglyceride has a monounsaturated character of at least 60 percent, preferably at least 70 percent and most preferably at least 80 percent.
  • Naturally occurring triglycerides having utility in this invention are exemplified by vegetable oils that are genetically modified such that they contain a higher than normal oleic acid content. Normal sunflower oil has an oleic acid content of 25-30 percent. By genetically modifying the seeds of sunflowers, a sunflower oil can be obtained wherein the oleic content is from about 60 percent up to about 90 percent.
  • R 1 , R 2 and R 3 groups are heptadecenyl groups and the R 1 COO-, R 2 COO-and R 3 COO-to the 1,2,3-propanetriyl group -CH 2 CHCH 2 - are the residue of an oleic acid molecule.
  • U.S. Patent No. 4,627,192 and 4,743,402 are herein incorporated by reference for their disclose to the preparation of high oleic sunflower oil.
  • a triglyceride comprised exclusively of an oleic acid moiety has an oleic acid content of 100% and consequently a monounsaturated content of 100%.
  • the triglyceride is made up of acid moieties that are 70% oleic acid, 10% stearic acid, 13% palmitic acid, and 7% linoleic acid, the monounsaturated content is 70%.
  • the preferred triglyceride oils are high oleic (at least 60 percent) acid triglyceride oils.
  • Typical high oleic vegetable oils employed within the instant invention are high oleic safflower oil, high oleic canola oil, high oleic peanut oil, high oleic corn oil, high oleic rapeseed oil, high oleic sunflower oil, high oleic soybean oil, high oleic cottonseed oil, and high oleic palm olein.
  • Canola oil is a variety of rapeseed oil containing less than 1 percent eruic acid.
  • a preferred high oleic vegetable oil is high oleic sunflower oil obtained from Helianthus sp. This product is available from SVO Enterprises Eastlake, Ohio as Sunyl® high oleic sunflower oil.
  • Sunyl 80 oil is a high oleic triglyceride wherein the acid moieties comprise 80 percent oleic acid.
  • Another preferred high oleic vegetable oil is high oleic rapeseed oil obtained from Brassica campestris or Brassica napus, also available from SVO Enterprises as RS high oleic rapeseed oil.
  • RS80 oil signifies a rapeseed oil wherein the acid moieties comprise 80 percent oleic acid.
  • genetically modified vegetable oils have high oleic acid contents at the expense of the di-and tri- unsaturated acids.
  • a normal sunflower oil has from 20-40 percent oleic acid moieties and from 50-70 percent linoleic acid moieties. This gives a 90 percent content of mono- and di- unsaturated acid moieties (20+70) or (40+50).
  • Genetically modifying vegetable oils generate a low di- or tri- unsaturated moiety vegetable oil.
  • the genetically modified oils of this invention have an oleic acid moiety:linoleic acid moiety ratio of from about 2 up to about 90.
  • a 60 percent oleic acid moiety content and 30 percent linoleic acid moiety content of a triglyceride oil gives a ratio of 2.
  • a triglyceride oil made up of an 80 percent oleic acid moiety and 10 percent linoleic acid moiety gives a ratio of 8.
  • a triglyceride oil made up of a 90 percent oleic acid moiety and 1 percent linoleic acid moiety gives a ratio of 90.
  • the ratio for normal sunflower oil is 0.5 (30 percent oleic acid moiety and 60 percent linoleic acid moiety).
  • the random block copolymers of this invention comprise the product copolymerization of two monomers.
  • the first monomer is an aliphatic conjugated diene and the second monomer is a mono-vinyl aromatic.
  • the random block copolymer formed is then hydrogenated to remove substantially all of the unsaturation.
  • Examples of vinyl substituted aromatics include styrene, alphamethylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, para-tertiary-butylstyrene, with styrene being preferred.
  • Examples of conjugated dienes include piperylene, 2,3-dimethyl-1,3-butadiene. chloroprene, isoprene and 1,3-butadiene with isoprene and 1,3-butadiene being particularly preferred. Mixtures of such conjugated dienes are useful.
  • the vinyl substituted aromatic monomer content of these random block copolymers is in the range of from 20 percent to 70 percent by weight and preferably from 40 percent to 60 percent by weight.
  • the aliphatic conjugated diene monomer content of these copolymers is in the range of from 30 percent to 80 percent by weight and preferably from 40 percent to 60 percent by weight.
  • these block copolymers for reasons of oxidative stability, contain no more than 5 percent and preferably no more than 0.5 percent residual olefinic unsaturation on the basis of the total number of carbon-to-carbon covalent linkages within the average molecule. Such unsaturation can be measured by a number of means well known to those of skill in the art, such as infrared, NMR, etc. Most preferably, these copolymers contain no discernible unsaturation as determined by the aforementioned analytical techniques.
  • the random block copolymers of this invention typically have a number average molecular weight in the range of 30,000 to 300,000.
  • the weight average molecular weight for these copolymers is generally in the range of 50,000 to 500,000; preferably 30,000 to 300,000.
  • Linear Random Block Copolymers Those in which a relatively large number of relatively short segments of homopolymer of one type of monomer alternate with a relatively large number of short segments of homopolymer of another monomer type.
  • Random block polymers of this invention may be linear, or they may be partially, or highly branched.
  • the relative arrangement of homopolymer segments in a linear random block polymer which is the most preferred block polymer of this invention, may be represented by: -DDDD-AAAAA-DDD-AA-DDDDD-AAA-DD-AAAAAA-DDD- wherein D represents a conjugated diene monomer, and A represents a vinyl aromatic monomer.
  • D represents a conjugated diene monomer
  • A represents a vinyl aromatic monomer.
  • the arrangement of the individual homopolymer segments of each type of monomer in a linear random block polymer is alternating.
  • a special type of configuration in linear random block copolymers is the linear tapered random block structure.
  • a major portion of the polymer backbone is of the random block type, with larger blocks of one type of homopolymer situated at one end of the molecule.
  • the synthesis of this type of polymer is usually carried out by preparing a linear random block copolymer, then adding more of one of the monomer types near the end of the polymerization, so that the additional polymer forms a series of ever larger homopolymer blocks at the end of the growing linear polymer chain.
  • the vinyl substituted aromatic monomer is generally chosen to provide the larger, tapered homopolymer blocks, although other types of monomers may be used for this purpose.
  • Linear tapered random block copolymers may have significantly different solubilities in diluents normally used in lubricant formulations, as well as superior thickening power at high temperature, better high temperature viscosity under conditions of high shear, and improved low temperature viscometrics, compared to simple random block copolymers of similar molecular weight, made from the same monomers.
  • the styrene/diene block polymers considered in this invention are usually made by anionic polymerization, using a variety of techniques, and altering reaction conditions to produce the most desirable microstructural features in the resulting polymer.
  • the initiator may be either an organometallic such as an alkyl lithium, or the anion formed by electron transfer from a Group IA metal to an aromatic such as naphthalene.
  • organometallic such as sec -butyl lithium
  • the most efficacious organometallic is usually an alkyl lithium such as sec -butyl lithium, and the polymerization is initiated by butyl anion addition to either the diene monomer, or to styrene.
  • sec-butyl lithium initiator propagation occurs in only one direction, and the growing polymer is anionically charged on one end, the negative charge being associated with a positively-charged lithium gegenion.
  • a homopolymer of one monomer e.g., styrene
  • each polymer molecule having an anionic terminus, and lithium gegenion: Bu - • + Li + mS (monomer) ⁇ Bu (-S-) m - • + Li Since all the anionic sites are presumed to have equal reactivity toward monomer molecules, polymer growth at each site is essentially the same, and the resulting polymers will, when monomer is completely depleted, all be of similar molecular weight and composition.
  • polymers made by anionic polymerization are said to be nearly “monodisperse”; i.e., the ratio of weight average molecular weight to number average molecular weight is very nearly 1.0.
  • the polydispersity factor for properly synthesized styrene-diene anionic block polymers is usually about 1.05- 1.10.
  • the composition constitutes a "living" polymer that maintains its activity, and can grow further by interaction with monomers that are also capable of anionic polymerization.
  • monomers may be additional styrene or similar vinyl aromatic monomers, or they may comprise a different chemical type, such as 1,3-dienes (e.g., 1,3-butadiene or isoprene).
  • the size of this "D” block i.e., the degree of polymerization ("DP"), will be determined principally by the amount of diene monomer added, and the number of active anionic sites available.
  • the molecular weight of the new (polydiene ) segments will all be about the same, and the polydispersity factor of the new poly S-block-poly-D living polymer will remain about 1.0.
  • the terminus of the new S-D diblock polymer will be anionic with a lithium gegenion, and the diblock will be "living" in the sense that the anionic site will remain active toward further polymerization when exposed to additional anionically-polymerizable monomers.
  • a common practice in manufacture of S-D-S type triblock polymers is to couple a living diblock polymer by exposure to an agent such as dialkyldichlorosilane.
  • an agent such as dialkyldichlorosilane.
  • precipitation of LiCl occurs to give an S-D-S tri bl ock po ly mer of somewhat different - structure than that ob tained by the sequential monomer addition method described above, wherein the size of the central D block is double that of the D block in the starting living (anionic) diblock intermediate: 2(-S-) m (-D-) n - • + Li + Me 2 SiCl 2 ⁇ (-S-) m (-D-)2 n- (-S)m + 2 LiCl
  • the polymerization to form block polymers may also be approached in a slightly different manner.
  • single electron-transfer to monomer (S) generates a radical-anion which may dimerize to yield a di-anionic nuceophile which is capable of initiating polymerization in two directions simultaneously.
  • Non-polar paraffinic solvents tend to inhibit charge separation at the growing anion, and diminish the basicity of the active organolithium head. These paraffinic solvents also tend to slow down the rates of initiation and emphasize the differences in relative rate of polymerization between various anionically-polymerizable monomers. Thus, when two different monomer types are available, the one which initiates faster takes precedence.
  • the same monomer will also polymerize faster, building a segment that is richer in that monomer, and contaminated by occasional incorporation of the other monomer. In some cases, this can be used beneficially to build a type of polymer referred to as a "random block polymer", or "tapered block polymer".
  • a random block polymer or "tapered block polymer”.
  • a mixture of two different monomers is anionically polymerized in a non-polar paraffinic solvent, one will initiate selectively, and usually polymerize to produce a relatively short segment of homopolymer. Incorporation of the second monomer is inevitable, and this produces a short segment of different structure.
  • An alternative way of preparing random or tapered block copolymers involves initiation of styrene, and interrupting with periodic, or step, additions of diene monomer.
  • the additions are programmed according to the relative reactivity ratios and rate constants of the styrene and particular diene monomer.
  • Promoters are electron-rich molecules that tend to enhance the basic nature of the organolithium active site by coordinating with the positively-charged lithium cation, polarizing the charged species to effect greater charge separation at the active site where interaction with virgin monomer occurs. Promoters include tetrahydrofuran, tetrahydropyran, linear and crown ethers, N,N-dimethylformamide, tetramethyl ethylenediamine, and other non-protic agents that have non-bonding electron pairs available for coordination. Promoters tend to facilitate anionic initiation and polymerization rates in general, while lessening the relative differences in rates between various monomers. Promoters may be added in small amounts to polymerization mixtures containing mixed monomers in non-polar paraffinic or aromatic solvents in order to speed the reaction, and to effect the nature of the size and distribution of blocks in the final copolymer.
  • a diene monomer can polymerize by 1,2- or 1,4-addition (see following reaction scheme), and the 1,4-addition can (theoretically) be either in a trans- or cis- configuration.
  • 1,3-butadiene/styrene monomers with sec-butyl lithium initiator have shown that in non-polar paraffinic solvents, the diene monomer incorporates predominantly (86-95%) by cis-1,4-addition. Addition of small amounts of tetrahydrofuran promoter cause 1,3-butadiene to increasingly favor 1,2-polymerization over the normal 1,4-cis-polymerization.
  • Hydrogenation of the unsaturated block polymers obtained initially as polymerization products produces polymers that are more oxidatively and thermally stable. Reduction is typically carried out at part of the polymerization process, using finely divided, or supported, nickel catalyst. Other transition metals may also be used to effect transformation. Hydrogenation is normally carried out to the extent of reducing approximately 94-96% of the olefinic unsaturation in the initial polymer. This means that the manner in which the diene monomer incorporates becomes an important parameter affecting the final physical and solution properties of the hydrogenated polymers at ambient and low temperatures. The figure below shows diene incorporated both in a 1,4-cis and 1,2-manner.
  • Hydrogenation of a 1,4-cis configuration produces linear polyethylene segments in the polymer, reducing solubility in general, and introducing highly crystalline sites that tend to associate at low temperatures, and introduce potentially undesirable melt-associated thermal transitions.
  • hydrogenation of diene introduced by 1,2-polymerization results in a pendant alkyl group that enhances solubility, decreases crystallinity in the diene segments, and substantially reduces the tendency toward association.
  • Isoprene incorporates into block polymers in a similar manner to that of 1,3-butadiene, i.e., either by 1,4-cis or 3,4-polymerization.
  • 1,3-butadiene predominantly cis-1,4-incorporation is usual in non-polar paraffinic solvents, but promoters, such as tetrahydrofuran, favor 3,4-polymerization.
  • promoters such as tetrahydrofuran
  • a balance of properties may be achieved by using small amounts of electron-rich promoters to speed initiation and polymerization, and to influence the nature and properties of the final, hydrogenated polymer.
  • isoprene there will be no possibility of formation of crystalline polyethylene segments on the hydrogenation, because there will always be aliphatic substituents in the polyisoprene blocks.
  • block copolymers are dependent on both the monomers used, and the method of preparation.
  • the morphological characteristics of polymer solutions are similarly dependent on polymer microstructure. Morphology refers to the actual conformation of polymers under a defined set of conditions, and is dependent on structure, polymer concentration, temperature, and additional influences of solvents and other agents.
  • Many types of block polymers show a good deal of intermolecular associative behavior, wherein blocks, or segments, of like homopolymer may agglomerate. In this sense, the block polymers demonstrate a kind of surface-active nature,wherein they form micelles, similar to those formed by classical surfactants.
  • block polymers have the ability to stabilize colloidal dispersions.
  • An example of surfactant properties can be shown by the ability of polystyrene-block copolymers to stabilize dimethylformamide-hexane emulsions.
  • Associative polymers can agglomerate in several ways, to produce discreetly different structures, depending on the nature and arrangement of their blocks.
  • Morphological structures range from spherical and core-shell, to cylindrical and lamellar.
  • the center of the sphere is usually formed by the more highly associative or crystalline segments, surrounded by a (usually more diffuse) mantle or shell which is enriched in the second type of segment, which is frequently swollen by solvent or diluent.
  • the cylindrical form is similar to a spherical form, except that the core extends from one end to the other, in an elongated shape, rather than a sphere.
  • the lamellar form comprises an arrangement of parallel planes of associated blocks, alternating by type of segment.
  • the morphology of copolymers having highly crystalline segments are usually controlled by the temperature at which such crystallization occurs, since this effectively "freezes" the entire structure. Thus, segments having significant crystallinity can effectively impose their morphology on the remainder of the copolymer.
  • the polymer content of a polymeric viscosity improver concentrate ranges typically from 5-40% by weight, in a mineral oil, synthetic hydrocarbon, or ester diluent.
  • non-associative polymers such as OCP, EPDM, butyl polymer or polymethacrylates, concentrates can be prepared at relatively high polymer concentrations, without experiencing unduly highly bulk viscosities.
  • the styrene-diene block copolymers are highly associative through the mutual affinity of their polystyrene segments, so that the amount of polymer that can be dissolved before the concentrate viscosity become too great to pour, is relatively low.
  • the association problem is exacerbated by the use of non-polar mineral oils or synthetic hydrocarbon diluents that are relatively poor solvents for the polystyrene segments in the block copolymers. In these diluents, the degree of association is relatively high, and the combined effective molecular weight of the aggregates, astronomical.
  • the effective thickening power of the copolymer aggregates renders the concentrate a gel, and the concentrate becomes unpourable at temperatures as high as 100°C.
  • polystyrene-block-polyisoprene hydrogenated diblock copolymers have two relatively large segments associated to a much greater degree than do random block polymers of similar composition and molecular weight that have a much larger number of relatively short polystyrene segments.
  • the diblock copolymer concentrate can contain no more than 6% by weight, and the random block copolymer no more than 8% to be pourable at 100°C.
  • these block copolymers for reasons of oxidative stability, contain no more than about 5 percent and preferably no more than 0.5 percent residual olefinic unsaturation on the basis of the total number of carbon-to-carbon covalent linkages within the average molecule. Such unsaturation can be measured by a number of means well known to those of skill in the art, such as infrared NMR, etc. Most preferably, these copolymers contain no discernible unsaturation as determined by the aforementioned analytical techniques.
  • Examples of commercially available random block copolymers include the various Glissoviscal block copolymers manufactured by BASF. Two especially preferred copolymers are Glissoviscal® SGH and Glissoviscal® CE-5260.
  • compositions of this invention may also contain (C) at least one oxidation inhibitor, (D) at least one extreme pressure/anti-wear additive or mixtures thereof.
  • the oxidation inhibitor comprises
  • Component (C)(1) is an alkyl phenol of the formula wherein R 4 is an alkyl group containing from 1 up to 24 carbon atoms, a is an integer of from 1 up to 3 and z is 1 or 2.
  • R 4 contains from 1 to 12 carbon atoms and most preferably from 4 to 12 carbon atoms.
  • R 4 may be either straight chained or branched chained and branched chain is preferred.
  • the preferred value for a is 2 and the preferred value for z is 1.
  • the phenol is a butyl substituted phenol containing two t-butyl groups.
  • a 2, the t-butyl groups occupy the 2,6-position, that is the phenol is sterically hindered:
  • a 3 the t-butyl groups occupy the 2,4,6- positions.
  • Component (C)(2) is an aromatic amine of the formula wherein b is 1 or 2 and when b is 1, R 5 is and R 6 and R 7 are independently a hydrogen or an alkyl group containing from 1 up to 24 carbon atoms, and when b is 2, R 5 and R 6 are independently hydrogen, an aryl group or an alkyl group containing from 1 up to 18 carbon atoms.
  • R 5 is and R 6 and R 7 are both nonyl groups.
  • R 5 preferably is and R 6 and R 7 are both hydrogen.
  • Component (C3) is a heterocyclic amine of formulae (a) or (b) wherein R 8 is independently a hydrogen or an alkyl group containing from 1 up to 4 carbon atoms, Z is hydrogen or ⁇ O ⁇ and X is hydrogen, -NR 14 R 15 or -OR 15 wherein R 14 and R 15 are independently hydrogen or alkyl groups containing from 1 up to 18 carbon atoms.
  • R 8 is preferably methyl.
  • Compounds having utility in this invention within formula (C3a) are 2,2,6,6-tetramethylpiperidine where X and Z are both hydrogen; 2,2,6,6-tetramethyl-1-piperidinol where X is -OR 15 and R 15 and Z are both hydrogen; and 2,2,6,6-tetramethyl-1-piperidinyloxy free radical where Z is ⁇ O ⁇ and X is hydrogen.
  • a compound having utility in this invention within formula (C3b) is 2,2,6,6-tetramethyl-4-piperidone where Z is hydrogen.
  • the extreme pressure/antiwear additive comprises
  • Component (D1) is a metal sulfur/phosphorus salt of the formula wherein R 9 and R 10 are independently hydrocarbyl groups containing from 3 up to 20 carbon atoms, M 1 is a metal selected from lithium, sodium, calcium, barium, copper, zinc, antimony, tin, cerium and other members of the lanthanide series, and x is the valence of M 1 .
  • Component (D1) is readily obtainable by the reaction of phosphorus pentasulfide (P 2 S 5 ) and an alcohol or phenol.
  • the reaction involves mixing at a temperature of 20°C to 200°C. four moles of an alcohol or phenol with one mole of phosphorus pentasulfide. Hydrogen sulfide is liberated in this reaction.
  • the R 9 and R 10 groups are independently hydrocarbyl groups that are preferably free from acetylenic and usually also from ethylenic unsaturation and have from 3 to 20 carbon atoms, preferably 3 to 16 carbon atoms and most preferably 3 to 12 carbon atoms.
  • Preferred metals acting as M 1 are copper, zinc, tin and cerium.
  • a reaction vessel is charged with 804 parts of a mixture of 6.5 moles of isobutyl alcohol and 3.5 moles of mixed primary amyl alcohols (65% w n-amyl and 35% w 2-methyl-1-butanol).
  • Phosphorus pentasulfide (555 parts, 2.5 moles) is added to the vessel while maintaining the reaction temperature between about 104°-107°C. After all of the phosphorus pentasulfide is added, the mixture is heated for an additional period to insure completion of the reaction and filtered. The filtrate is the desired phosphorodithioic acid which contains about 11.2% phosphorus and 22.0% sulfur.
  • a reaction vessel is charged with 448 parts of zinc oxide (11 equivalents) and 467 parts of the above alcohol mixture.
  • the above phosphorodithioic acid (3030 parts, 10.5 equivalents) is added at a rate to maintain the reaction temperature at about 45°-50°C.
  • the addition is completed in 3.5 hours whereupon the temperature of the mixture is raised to 75°C for 45 minutes.
  • an additional 61 parts of zinc oxide (1.5 equivalents) are added, and this mixture is heated to 75°C for 2.5 hours.
  • the mixture is stripped to 124°C at mm. pressure.
  • the residue is filtered twice through diatomaceous earth, and the filtrate is the desired zinc salt containing 22.2% sulfur (theory, 22.0), 10.4% phosphorus (theory, 10.6) and 10.6% zinc (theory, 11.1).
  • Example (D1)-1 The procedure of Example (D1)-1 is essentially followed except that 2-methylpentyl alcohol is used in place of the isobutyl alcohol and amyl alcohols.
  • the product obtained has 8.5% phosphorus, 17.6% sulfur and 9.25% zinc.
  • R 11 and R 12 are aliphatic groups containing from 3 up to 12 carbon atoms and M 2 is preferably copper, antimony or zinc.
  • Vanlube 73 An example of a metal sulfur/nitrogen salt is an antimony dialkyldithiocarbamate obtained from the R.T. Vanderbilt Company and known as Vanlube 73. From laboratory analysis Vanlube 73 is believed to consist of antimony dipentyldithiocarbamate.
  • Component (D3) is a benzotriazole of the formula wherein R 13 is hydrogen or an alkyl group containing from 1 up to 12 carbon atoms, R 16 is hydrogen or -CH 2 SR 17 where R 17 is an alkyl group containing from 1 up to about 18 carbon atoms.
  • R 13 is a methyl group and R 16 is hydrogen which results in (D3) being tolyltriazole of the formula Tolyltriazole is available under the trade name Cobratec® TT-100 from Sherwin-Williams Chemical.
  • the first sulfurized composition (D4a) is a sulfurized olefinic hydrocarbon prepared in essentially a two-step process that involves: 1) reacting an olefin with a sulfur halide to form a sulfochlorinated adduct, and 2) contacting the sulfochlorinated adduct with sodium sulfide or sodium polysulfide in a protic solvent.
  • the protic solvent may be water and an alcohol of 4 carbon atoms or less.
  • the alcohol is isopropyl alcohol.
  • the sodium polysulfide solution is best prepared by dissolving sulfur into an aqueouss Na 2 S or NaSH/Na 2 S solution. Water and aqueous NaOH are added as necessary to adjust the basic sulfide concentration to a range of 18-21 percent Na 2 S and 2-5 percent NaOH.
  • olefins may be charged to the initial sulfochlorination reaction including hydrocarbon olefins having a single double bond with terminal or internal double bonds and containing from 2 to 50 or more, preferably 2 to 8 carbon atoms per molecule in either straight, branched chain or cyclic compounds, and these may be exemplified by ethylene, propylene, butene-1, cis-and trans- butene-2, isobutylene, diisobutylene, triisobutylene, pentenes, cyclopentene, cyclohexene, the octenes, decene-1, etc.
  • C 3-6 olefins or mixtures thereof are desirable for preparing sulfurized products for use as extreme pressure additives. The combined sulfur content of the product decreases with increasing olefin carbon number, while miscibility with oil increases.
  • the molar ratio of olefin to sulfur halide will vary depending on the amount of sulfurization desired in the end product and the amount of olefinic unsaturation.
  • the molar ratio of sulfur halide to olefin could vary from 1:(1-20).
  • the olefin to be sulfurized contains a single double bond, one mole of the olefin can be reacted with 0.5 moles or less of S 2 Cl 2 (sulfur monochloride).
  • S 2 Cl 2 sulfur monochloride
  • the olefin is generally added in excess with respect to the amount of the sulfur being added so that all of the sulfur halide will be reacted and any unreacted olefin can remain as unreacted diluent oil or can be removed and recycled.
  • the reaction mixture is allowed to stand and separate into an aqueous layer and another liquid layer containing the desired organic sulfide product.
  • the product is usually dried by heating at moderately elevated temperatures under subatmospheric pressure, and its clarity may often be improved by filtering the dried product through a bed of bauxite, clay or diatomaceous earth particles.
  • a blend of 1800 grams of 18% Na 2 S solution is obtained from process streams. To this blend is added 238 grams 50% aqueous NaOH, 525 grams water and 415 grams isopropyl alcohol to prepare a reagent for use in the sulfurization-dechlorination dechlorination reaction. To this reagent is added 1000 grams of the reaction product in about 1.5 hours. One hour after the addition is completed, the contents are permitted to settle and the liquid layer is drawn off and discarded. The organic layer is stripped to 120°C and 100 mm Hg to remove any volatiles. Analyses: % sulfur 43.5, % chlorine 0.2.
  • Example (D4a)-1 Table I outlines other olefins and sulfur chlorides that can be utilized in preparing the first sulfurized composition. The procedure is essentially the same as in Example (D4a)-1. In all the examples, the metal ion reagent is prepared according to Example (D4a)-1.
  • the second sulfurized composition (D4b), is also a sulfurized olefinic hydrocarbon that comprises the reaction product of sulfur and a Diels-Alder adduct.
  • the Diels-Alder adducts are a well known, art-recognized class of compounds prepared by the diene synthesis or Diels-Alder reaction.
  • a summary of the prior art relating to this class of compounds is found in the Russian monograph, Dienovyi Sintes , Izdatelstwo Akademii Nauk SSSR, 1963 by A.S. Onischenko. (Translated into the English language by L. Mandel as A.S. Onischenko, Diene Synthesis , N.Y., Daniel Davey and Co., Inc., 1964).
  • the reaction can be represented as follows:
  • the products, A and B are commonly referred to as Diels-Alder adducts. It is these adducts which are used as starting materials for the preparation of the second sulfurized composition.
  • 1,3-dienes include aliphatic conjugated diolefins or dienes of the formula wherein R 18 through R 23 are each independently selected from halogen, alkyl, halo, alkoxy, alkenyl, alkenyloxy, carboxy, cyano, amino, alkylamino, dialkylamino, phenyl, and phenyl-substituted with 1 to 3 substituents corresponding to R 18 through R 23 with the proviso that a pair of R's on adjacent carbons do not form an additional double bond in the diene.
  • R 18 through R 23 are each independently selected from halogen, alkyl, halo, alkoxy, alkenyl, alkenyloxy, carboxy, cyano, amino, alkylamino, dialkylamino, phenyl, and phenyl-substituted with 1 to 3 substituents corresponding to R 18 through R 23 with the proviso that a pair of R's on adjacent carbons do
  • adducts are used where R 20 and R 21 are both hydrogen and at least one of the remaining R variables is also hydrogen.
  • the carbon content of these R variables when other than hydrogen is 7 or less.
  • those dienes where R 18 , R 19 , R 22 and R 23 are hydrogen, chloro, or lower alkyl are especially useful.
  • Specific examples of the R variables include the following groups: methyl, ethyl, phenyl, HOOC-, N ⁇ C-, CH 3 COO-, CH 3 CH 2 O-, CH 3 C(O)-, HC(O), -C1, -Br, tert-butyl, CF 3 , tolyl, etc.
  • Piperylene, isoprene, methylisoprene, chloroprene, and 1,3-butadiene are among the preferred dienes for use in preparing the Diels-Alder adducts.
  • the dienophiles suitable for reacting with the above dienes to form the adducts used as reactants can be represented by the formula wherein the K variables are the same as the R variables in the diene formula above.
  • a preferred class of dienophiles are those wherein at least one of the K variables is selected from the class of electron-accepting groups such as formyl, cyano, nitro, carboxy, carbohydrocarbyloxy, hydrocarbylcarbonyl, hydrocarbylsulfonyl, carbamyl, acylacarbanyl, N-acyl-N-hydrocarbylcarbamyl, N-hydrocarbylcarbamyl, and N,N-dihydrocarbylcarbamyl.
  • K variables which are not electron-accepting groups are hydrogen, hydrocarbyl, or substituted-hydrocarbyl groups. Usually the hydrocarbyl and substituted hydrocarbyl groups will not contain more than 10 atoms each.
  • the hydrocarbyl groups present as N-hydrocarbyl substituents are preferably alkyl of 1 to 30 carbon atoms and especially 1 to 10 carbon atoms.
  • Representative of this class of dienophiles are the following: maleic anhydride, nitroalkenes, e.g., 1-nitrobutene-1, 1-nitropentene-1, 3-methyl-1-nitro-butene-1, 1-nitroheptene-1, 1-nitrooctene-1, 4-ethoxy-1-nitrobutene-1; alpha, beta-ethylenically unsaturated aliphatic carboxylic acid esters, e.g., alkylacrylates and alpha-methyl alkylacrylates (i.e., alkyl methacrylates) such as butylacrylate and butylmethacrylate, decyl acrylate and decylmethacrylate, di-(n-butyl)-maleate, di-(t-butyl-maleate); acrylonitrile,
  • One preferred class of dienophiles are those wherein at least one, but not more than two of K variables is -C(O)O-R° where R° is the residue of a saturated aliphatic alcohol of up to about 40 carbon atoms; e.g., for example at least one K is carbohydrocarbyloxy such as carboethoxy, carbobutoxy, etc.
  • the aliphatic alcohol from which -R° is derived can be a mono- or polyhydric alcohol such as alkyleneglycols, alkanols, aminoalkanols, alkoxy-substituted alkanols, ethanol, ethoxy ethanol, propanol, beta-diethylaminoethanol, dodecyl alcohol, diethylene glycol, tripropylene glycol, tetrabutylene glycol, hexanol, octanol, isooctyl alcohol, and the like.
  • K variables will be -C(O)-O-R° groups and the remaining K variables will be hydrogen or lower alkyl, e.g., methyl, ethyl, propyl, isopropyl, and the like.
  • acetylenically unsaturated dienophiles such as propiolaldehyde, methylethynylketone, propylethynylketone, propenylethynylketone, propiolic acid, propiolic acid nitrile, ethylpropiolate, tetrolic acid, propargylaldehyde, acetylenedicarboxylic acid, the dimethyl ester of acetylenedicarboxylic acid, dibenzoylacetylene, and the like.
  • the second sulfurized compositions are readily prepared by heating a mixture of sulfur and at least one of the Diels-Alder adducts of the types discussed hereinabove at a temperature within the range of from 100°C to 200°C will normally be used. This reaction results in a mixture of products, some of which have been identified.
  • the sulfur reacts with the substituted unsaturated cycloaliphatic reactants at a double bond in the nucleus of the unsaturated reactant.
  • the molar ratio of sulfur to Diels-Alder adduct used in the preparation of this sulfur-containing composition is from 1:2 up to 4:1.
  • the molar ratio of sulfur to Diels-Alder adduct will be from 1:1 to 4:1 and preferably 2:1 to 4:1.
  • the reaction can be conducted in the presence of suitable inert organic solvents such as mineral oils, alkanes of 7 to 18 carbons, etc., although no solvent is generally necessary.
  • suitable inert organic solvents such as mineral oils, alkanes of 7 to 18 carbons, etc.
  • the reaction mass can be filtered and/or subjected to other conventional purification techniques. There is no need to separate the various sulfur-containing products as they can be employed in the form of a reaction mixture comprising the compounds of known and unknown structure.
  • H 2 S As hydrogen sulfide is an undesirable contaminant, it is advantageous to employ standard procedures for assisting in the removal of the H 2 S from the products. Blowing with steam, alcohols, air, or nitrogen gas assists in the removal of H 2 S as does heating at reduced pressures with or without the blowing.
  • materials useful as sulfurization catalysts may be acidic, basic or neutral.
  • Useful neutral and acidic materials include acidified clays such as "Super Filtrol", p-toluenesulfonic acid, dialkylphosphoro-dithioic acids, phosphorus sulfides such as phosphorus pentasulfide and phosphites such as triaryl phosphites (e.g., triphenyl phosphite).
  • the basic materials may be inorganic oxides and salts such as sodium hydroxide, calcium oxide and sodium sulfide.
  • the most desirable basic catalysts are nitrogen bases including ammonia and amines.
  • the amines include primary, secondary and tertiary hydrocarbyl amines wherein the hydrocarbyl radicals are alkyl, aryl, aralkyl, alkaryl or the like and contain 1-20 carbon atoms.
  • Suitable amines include aniline, benzylamine, dibenzylamine, dodecylamine, naphthylamine, tallow amines, N-ethyl-dipropylamine, N-phenylbenzylamine, N,N-diethylbutylamine, m-toluidine and 2,3-xylidine. Also useful are heterocyclic amines such as prrolidine, N-methylpyrrolidine, piperidine, pyridine and quinoline.
  • the preferred basic catalysts include ammonia and primary, secondary or tertiary alkylamines having 1-8 carbon atoms in the alkyl radicals. Representing amines of this type are methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, di-n-butylamine, tri-n-butylamine, tri-sec-hexylamine and tri-n-octylamine. Mixtures of these amines can be used, as well as mixtures of ammonia and amines.
  • the amount is generally 0.05-2.0% of the weight of the adduct.
  • a mixture comprising 400 parts of toluene and 66.7 parts of aluminum chloride is charged to a two-liter flask fitted with a stirrer, nitrogen inlet tube, and a solid carbon dioxide-cooled reflux condenser.
  • a second mixture comprising 640 parts (5 moles) of butyl acrylate and 240.8 parts of toluene is added to the AlCl 3 slurry while maintaining the temperature within the range of 37-58°C over a 0.25-hour period. Thereafter, 270 parts (5 moles) of butadiene is added to the slurry over a 2.75-hour period while maintaining the temperature of the reaction mass at 50-61°C by means of external cooling.
  • reaction mass is blown with nitrogen for about 0.33 hour and then transferred to a four-liter separatory funnel and washed with a solution of 150 parts of concentrated hydrochloric acid in 1100 parts of water. Thereafter, the product is subjected to two additional water washings using 1000 parts of water for each wash. The washed reaction product is subsequently distilled to remove unreacted butyl acrylate and toluene. The residue of this first distillation step is subjected to further distillation at a pressure of 9-10 millimeters of mercury whereupon 785 parts of the desired product is collected over the temperature of 105-115°C.
  • a mixture of 728 parts (4.0 moles) of the above material, 218 parts (6.8 moles) of sulfur, and 7 parts of triphenyl phosphite is prepared and heated with stirring to a temperature of about 181 °C over a period of 1.3 hours.
  • the mixture is maintained under a nitrogen purge at a temperature of 181-187°C for 3 hours.
  • the mixture is filtered using a filter aid, and the filtrate is the desired second sulfurized composition containing 23.1 % sulfur.
  • the third sulfurized composition (D4c) is prepared by sulfurizing a mixture comprising three essential reagents.
  • This first reagent is a fatty oil; that is, at least one naturally occurring ester of glycerol and a fatty acid, or a synthetic ester of similar structure.
  • fatty oils are animal or vegetable oil tryiglycerides of the formula wherein R 1 , R 2 and R 3 are aliphatic groups containing from 7 to 23 carbon atoms.
  • R 1 , R 2 and R 3 are animal or vegetable oil tryiglycerides of the formula wherein R 1 , R 2 and R 3 are aliphatic groups containing from 7 to 23 carbon atoms.
  • a non-exhaustive list of triglycerides include peanut oil, cottonseed oil, soybean oil, sunflower oil and corn oil. These triglycerides are the same as component (A) disclosed above.
  • the second reagent is at least one alkenyl carboxylic acid of the formula R 25 COOH wherein R 25 contains 7 to 29 carbon atoms.
  • the carboxylic acids are ordinarily free from acetylenic unsaturation. Suitable acids include (preferably) oleic acid, linoleic acid, linolenic acid, 14-hydroxy-11-eicosenoic acid and ricinoleic acid.
  • the carboxylic acid may be an unsaturated fatty acid such as oleic or linoleic acid, and may be a mixture of acids such as is obtained from tall oil or by the hydrolysis of peanut oil, soybean oil or the like.
  • the amount of carboxylic acid used is 2-50 parts by weight per 100 parts of triglyceride; 2-8 parts by weight is preferred.
  • the third reagent is at least one substantially aliphatic monoolefin containing from 4 to 36 carbon atoms, and is present in the amount of 25-400 parts by weight per 1000 parts of triglyceride.
  • Suitable olefins include the octenes, decenes, dodecenes, eicosenes and triacontenes, as well as analogous compounds containing aromatic or non-hydrocarbon substituents which are substantially inert in the context of this invention.
  • substantially inert when used to refer to solvents, diluents, substituents and the like is intended to mean that the solvent, diluent, substituent, etc.
  • Terminal olefins or ⁇ - olefins, are preferred, especially those containing from 12 to 20 carbon atoms. Especially preferred are straight chain ⁇ olefins. Mixtures of these olefins are commercially available and such mixtures are contemplated for use in this invention.
  • This sulfurized composition is prepared by reacting a mixture comprising a triglyceride, a fatty acid and an aliphatic monoolefin with a sulfurizing agent at a temperature between 100°C and 250°C, usually between 150° and 210°C.
  • the sulfurizing reagent may be, for example, sulfur, a sulfur halide such as sulfur monochloride or sulfur dichloride, a mixture of hydrogen sulfide and sulfur dioxide, or the like. Elemental sulfur is often preferred and the invention especially contemplates the use of sulfurized composition prepared by reacting sulfur with the aforesaid mixture.
  • the weight ratio of the combination of triglyceride, fatty acid and aliphatic monoolefin to sulfur is between 5:1 and 15:1, generally between 5:1 and 10:1.
  • reaction mixture may contain other materials. These may include, for example, sulfurization promoters, typically phosphorus-containing reagents such as phosphorous acid esters such as lecithin.
  • the sulfurization reaction is effected by merely heating the reagents at the temperature indicated above, usually with efficient agitation and in an inert atmosphere (e.g., nitrogen). If any of the reagents, especially the aliphatic monoolefin, are appreciably volatile at the reaction temperature, the reaction vessel may be maintained under pressure. It is frequently advantageous to add sulfur portionwise to the mixture of the other reagents. While it is usually preferred of the reagent previously described, the reaction may also be effected in the presence of a substantially inert organic diluent (e.g., an alcohol, ether, ester, aliphatic hydrocarbon, halogenated aromatic hydrocarbon or the like) which is liquid within the temperature range employed.
  • a substantially inert organic diluent e.g., an alcohol, ether, ester, aliphatic hydrocarbon, halogenated aromatic hydrocarbon or the like
  • reaction temperature is relatively high, e.g., about 200°C
  • a lower reaction temperature e.g., from about 150° to about 170°C
  • the reaction sometimes requires a longer time at lower temperatures and an adequate sulfur content is usually obtained when the temperature is at the high end of the recited range.
  • volatile materials may be removed by blowing with air or nitrogen and insoluble by products by filtration, usually at an elevated temperature (from about 80° to about 120°C).
  • the filtrate is the desired sulfur product.
  • a mixture of 100 parts of soybean oil, 5.25 parts of tall oil acid and 44.8 parts of commercial C 15-18 straight chain ⁇ - olefins is heated to 167°C under nitrogen, and 17.4 parts of sulfur is added. The temperature of the mixture rises to 208°C. Nitrogen is blown over the surface at 165°-200°C for 6 hours and the mixture is then cooled to 90°C and filtered. The filtrate is the desired product and contains 10.6% sulfur.
  • dimercaptothiadiazole derivatives which can be utilized as component (D5) in the composition of the present invention contain the dimercaptothiadiazole nucleus have the following structural formulae and names:
  • DMTD is conveniently prepared by the reaction of one mole of hydrazine, or a hydrazine salt, with two moles of carbon disulfide in an alkaline medium, followed by acidification.
  • DMTD Derivatives of DMTD have been described in the art, and any such compounds can be included in the compositions of the present invention.
  • the preparation of some derivatives of DMTD is described in E.K. Fields "Industrial and Engineering Chemistry", 49 , p. 1361-4 (September 1957).
  • For the preparation of the oil-soluble derivatives of DMTD it is possible to utilize already prepared DMTD or to prepare the DMTD in situ and subsequently adding the material to be reacted with DMTD.
  • U.S. Patents 2,719,125; 2,719,126; and 3,087,937 describe the preparation of various 2,5-bis-(hydrocarbon dithio)-1,3,4-thiadiazoles.
  • the hydrocarbon group may be aliphatic or aromatic, including cyclic, alicyclic, aralkyl, aryl and alkaryl.
  • Such compositions are effective corrosion-inhibitors for silver, silver alloys and similar metals.
  • Such polysulfides which can be represented by the following general formula wherein R and R' may be the same or different hydrocarbon groups, and x* and y* be integers from 0 to 8, and the sum of x* and y* being at least 1.
  • a process for preparing such derivatives is described in U.S.
  • Patent 2,191,125 as comprising the reaction of DMTD with a suitable sulfenyl chloride or by reacting the dimercapto diathiazole with chlorine and reacting the resulting disulfenyl chloride with a primary or tertiary mercaptan.
  • Suitable sulfenyl chlorides useful in the first procedure can be obtained by chlorinating a mercaptan (RSH or R'SH) with chlorine in carbon tetrachloride.
  • DMTD is chlorinated to form the desired bissulfenyl chloride which is then reacted with at least one mercaptan (RSH and/or R'SH).
  • RSH mercaptan
  • U.S. Patents 2,719,125; 2,719,126; and 3,087,937 describe derivatives of DMTD useful in the compositions of the invention.
  • U.S. Patent 3,087,932 describes a one-step process for preparing 2,5-bis (hydrocarbyldithio)-1,3,4-thiadiazole.
  • the procedure involves the reaction of either DMTD or its alkali metal or ammonium salt and a mercaptan in the presence of hydrogen peroxide and a solvent.
  • Oil-soluble or oil-dispersible reaction products of DMTD can be prepared also by the reaction of the DMTD with a mercaptan and formic acid. Compositions prepared in this manner are described in U.S. Patent 2,749,311. Any mercaptan can be employed in the reaction although aliphatic and aromatic mono- or poly-mercaptan containing from 1 to 30 carbon atoms are preferred.
  • U.S. Patents 3,087,932 and 2,749,311 describe DMTD derivatives which can be utilized as a metal passivator.
  • Carboxylic esters of DMTD having the general formula wherein R and R' are hydrocarbon groups such as aliphatic, aryl and alkaryl groups containing from 2 to 30 or more carbon atoms are described in U.S. Patent 2,760,933. These esters are prepared by reacting DMTD with an organic acid halide (chloride) and a molar ratio of 1:2 at a temperature of from 25 to 130°C. Suitable solvents such as benzene or dioxane can be utilized to facilitate the reaction. The reaction product is washed with dilute aqueous alkali to remove hydrogen chloride and any unreacted carboxylic acid.
  • U.S. Patent 2,760,933 discloses various DMTD derivatives which can be utilized in the compositions of the present invention.
  • Condensation products of alpha-halogenated aliphatic monocarboxylic acids having at least 10 carbon atoms with DMTD are described in U.S. Patent 2,836,564. These condensation products generally are characterized by the following formula wherein R is an alkyl group of at least 10 carbon atoms.
  • alpha-halogenated aliphatic fatty acids which can be used include alpha-bromo-lauric acid, alphachloro-lauric acid, alpha-chloro-stearic acid, etc.
  • the disclosure of U.S. Patent 2,836,564 is hereby incorporated by reference for its discloses of derivatives of DMTD which can be utilized in the compositions of the present invention.
  • Oil-soluble reaction products of unsaturated cyclic hydrocarbons and unsaturated ketones are described in U.S. Patents 2,764,547 and 2,799,652, respectively, and a disclosure of these references also are hereby incorporated by reference for their describe of materials which are useful as a DMTD derivative in present invention.
  • unsaturated cyclic hydrocarbons described in the the '547 patent include styrene, alpha-methyl styrene, pinene, dipentene, cyclopentadiene, etc.
  • the unsaturated ketones described in U.S. Patent 2,799,652 include aliphatic, aromatic or heterocyclic unsaturated ketones containing from about 4 to 40 carbon atoms and from 1 to 6 double bonds. Examples include mesityl oxide, phorone, isophorone, benzal acetophenone, furfural acetone, difurfuryl acetone, etc.
  • U.S. Patent 2,765,289 describes products obtained by reacting DMTD with an aldehyde and a diaryl amine in molar proportions of from about 1:1:1 to about 1:4:4.
  • the resulting products are suggested as having the general formula wherein R and R' are the same or different aromatic groups, and R" is hydrogen, and alkyl group, or an aromatic group.
  • the aldehydes useful in the preparation of such products as represented by Formula X include aliphatic or aromatic aldehydes containing from 1 to 24 carbon atoms, and specific examples of such aldehydes include formaldehyde, acetaldehyde, benzaldehyde, 2-ethylehexyl aldehyde, etc.
  • Amine salts of DMTD such as those having the following formula in which Y is hydrogen or the amino group in which R is an aliphatic, aromatic or heterocyclic group, containing from 6 to 60 carbon atoms also have utility as component (D5).
  • the amine used in the preparation of the amine salts can be aliphatic or aromatic mono- or polyamines. and the amines may be primary, secondary or tertiary amines. Specific examples of suitable amines include hexylamine, dibutylamine, dodecylamine, ethylenediamine, propylenediamine, tetraethylenepentamine, and mixtures thereof.
  • U.S. Patent 2,910,439 contains a listing of suitable amine salts.
  • Dithiocarbamate derivatives of DMTD are described in U.S. Patents 2,690,999 and 2,719,827.
  • Such compositions can be represented by the following formulae and wherein the R groups are straight-chain or branch-chain saturated or unsaturated hydrocarbon groups selected from the group consisting of alkyl, aralkyl and alkaryl groups.
  • U.S. Patent 2,850,453 describes products which are obtained by reacting DMTD, an aldehyde and an alcohol or an aromatic hydroxy compound in a molar ratio of from 1:2:1 to 1:6:5.
  • the aldehyde employed can be an aliphatic aldehyde containing from 1 to 20 carbon atoms or an aromatic or heterocyclic aldehyde containing from 5 to 30 carbon atoms.
  • suitable aldehydes include formaldehyde, acetaldehyde, benzaldehyde.
  • the reaction can be conducted in the presence or absence of suitable solvents by (a) mixing all of the reactants together and heating, (b) by first reacting an aldehyde with the alcohol or the aromatic 2-hydroxy compound, and then reacting the resultant intermediate with the thiadiazole, or (c) by reacting the aldehyde with thiadiazole first and the resulting intermediate with the hydroxy compound.
  • U.S. Patent 2,850,453 discloses various materials which can be utilized in the compositions of the present invention.
  • U.S. Patent 2,703,784 describes products obtained by reacting DMTD with an aldehyde and a mercaptan.
  • the aldehydes are similar to those disclosed in U.S. Patent 2,850,453, and the mercaptans may be aliphatic or aromatic mono- or poly-mercaptans containing from about 1 to 30 carbon atoms.
  • suitable mercaptans include ethyl mercaptan, butyl mercaptan, octyl mercaptan, thiophenol, etc.
  • the disclosure of this patent also is incorporated by reference.
  • a peroxy compound, hypohalide or air, or mixtures thereof can be utilized to promote the oxidative coupling.
  • the monomercaptan include methyl mercaptan, isopropyl mercaptan, hexyl mercaptan, decyl mercaptan, and long chain alkyl mercaptans, for example mercaptans derived from propene polymers and isobutylene polymers especially polyisobutylenes, having 3 to about 70 propene or isobutylene units per molecule.
  • the disclosure of U.S. Patent 3,663,561 is hereby incorporated by reference for its identification of DMTD derivative which are useful as in the compositions of this invention.
  • Another material useful as component (D5) in the compositions of the present invention is obtained by reacting a thiadiazole, preferably DMTD with an oil-soluble dispersant, preferably a substantially neutral or acidic carboxylic dispersant in a diluent by heating the mixture above about 100°C.
  • a thiadiazole preferably DMTD
  • an oil-soluble dispersant preferably a substantially neutral or acidic carboxylic dispersant in a diluent
  • Another material useful as component (D5) in the compositions of the invention is obtained by reacting a thiadiazole, preferably DMTD, with a peroxide, preferably hydrogen peroxide.
  • a peroxide preferably hydrogen peroxide.
  • the resulting nitrogen- and sulfur-containing composition is then reacted with a polysulfide, mercaptan or amino compound (especially oil-soluble, nitrogen-containing dispersants). This procedure and the derivatives produced thereby are described in U.S. Patent 4,246,126.
  • U.S. Patent 4,140,643 describes nitrogen and sulfur-containing compositions which are oil-soluble and which are prepared by reacting a carboxylic acid or anhydride containing up to 10 carbon atoms and having at least one olefinic bond with compositions of the type described in U.S. Patent 4,136,043.
  • the preferred carboxylic acid or anhydride is maleic anhydride.
  • U.S. Patent 4,097,387 describes DMTD derivatives prepared by reacting a sulfur halide with an olefin to form an intermediate which is then reacted with an alkali metal salt of DMTD. More recently, U.S. Patent 4,487,706 describes a DMTD derivative prepared by reacting an olefin, sulfur dichloride and DMTD in a one-step reaction.
  • the olefins generally contain from 6 to 30 carbon atoms.
  • compositions of the present invention comprising components (A) and (B) or (A) and (B) with (C) or (D) or with (C) and (D) are useful as viscosity modified environmentally friendly farm tractor lubricants and chain bar lubricants and hydraulic fluids.
  • composition comprises components (A) and (B), the following states the ranges of these components in parts by weight: Component Generally Preferred Most Preferred (A) 80 - 99.5 90 - 99.5 96 - 99 (B) 0.5 - 20 0.5 - 10 1 - 4
  • composition comprises components (A), (B) and (C); or (A), (B) and (D); the following states the range of these components in parts by weight: Component Generally Preferred Most Preferred (A) 80 - 99.5 90 - 99.5 93 - 98.5 (B) 0.5 - 12 0.5 - 6 1 - 4 (C) or (D) 0.5 - 8 0.5 - 4 0.5 - 3
  • the composition comprises components (A), (B), (C) and (D)

Claims (23)

  1. Une composition comportant :
    (A) une quantité prépondérante d'au moins un triglycéride d'huile naturelle ou synthétique de la formule
    Figure 00600001
    dans laquelle R1, R2 et R3 sont des groupes aliphatiques, qui renferment de 7 à 23 atomes de carbone, et
    (B) une quantité plus faible d'une composition comportant un copolymère séquencé statistique de composés aromatiques mono-vinyliques/diène conjugué aliphatique hydrogéné ayant un poids moléculaire moyen en nombre du copolymère séquencé statistique dans la gamme de 30 000 à 300 000, et dans lequel le copolymère séquencé statistique a de 30 à 80 % en poids de diènes conjugués aliphatiques et de 20 à 70 % en poids de monomères monovinyl aromatiques, et dans laquelle ladite composition ne renferme pas d'agent abaissant le point d'écoulement.
  2. La composition de la revendication 1, dans laquelle l'huile naturelle est une huile végétale qui comprend l'huile de tournesol, l'huile de carthame, l'huile de maïs, l'huile de soja, l'huile de colza, l'huile de coco, l'huile de lesquerella, l'huile de ricin, l'huile de canola et l'huile d'arachide.
  3. La composition de la revendication 1, dans laquelle le triglycéride synthétique est un ester d'au moins un acide gras à chaíne droite et du glycérol, l'acide gras renfermant d'environ 8 à environ 22 atomes de carbone.
  4. La composition de la revendication 1, dans laquelle l'huile naturelle est une huile végétale modifiée, où R1, R2, R3 sont des groupes aliphatiques qui sont au moins mono-insaturés à 60 %, dans laquelle l'huile végétale génétiquement modifiée comprend de l'huile de tournesol génétiquement modifiée, de l'huile de maïs génétiquement modifiée, de l'huile de soja génétiquement modifiée, de l'huile de colza génétiquement modifiée, de l'huile de canola génétiquement modifiée, de l'huile de carthame génétiquement modifiée ou de l'huile d'arachide génétiquement modifiée.
  5. La composition de la revendication 4, dans laquelle le caractère mono-insaturé est dû à un résidu d'acide oléique, le rapport partie acide oléique:partie acide linoléique est de 2 à 90.
  6. La composition de l'une des revendications précédentes, dans laquelle ledit diène aliphatique conjugué est de l'isoprène ou du butadiène, ledit monomère aromatique à substitution mono-vinyle est du styrène ou un styrène à substitution alkyle, où le groupe alkyle renferme de 1 à 4 atomes de carbone et dans laquelle l'hydrogénation du copolymère séquencé statistique élimine au moins 94 % de l'insaturation oléfinique d'origine.
  7. La composition de l'une des revendications précédentes, comportant en outre (C) au moins un inhibiteur d'oxydation, l'inhibiteur d'oxydation (C) comportant :
    (1) un alkyl phénol de la formule :
    Figure 00610001
    dans laquelle R4 est un groupe alkyle renfermant de 1 à 24 atomes de carbone, a est un nombre entier de 1 à 3 et z est 1 ou 2 ;
    (2) une amine aromatique de la formule :
    Figure 00620001
    dans laquelle b est 1 ou 2 et dans laquelle b est 1, R5 est
    Figure 00620002
    et R6 et R7 représentent indépendamment un hydrogène ou un groupe alkyle renfermant de 1 à 24 atomes de carbone et, lorsque b est 2, R5 ou R6 représentent indépendamment de l'hydrogène, un groupe aryle ou un groupe alkyle renfermant de 1 à 18 atomes de carbone ; ou
    (3) une amine hétérocyclique de la formule (a) ou (b)
    Figure 00620003
    dans lesquelles R8 est indépendamment un hydrogène ou un groupe alkyle renfermant de 1 à 4 atomes de carbone, Z est de l'hydrogène ou →O et X est de l'hydrogène, -NR14R15 ou OR15, où R14 et R15 représentent indépendamment de l'hydrogène ou des groupes alkyle renfermant de 1 à 18 atomes de carbone ;
    (D) au moins un additif de pression extrême/anti-usure, l'additif de pression extrême/anti-usure (D) comporte :
    (1) un sel de phosphore/sulfure métallique de la formule
    Figure 00630001
    dans laquelle R9 et R10 sont indépendamment des groupes hydrocarbyle renfermant de 3 à 20 atmes de carbone, M1 est un métal choisi parmi le lithium, le sodium, le calcium, le baryum, le cuivre, le zinc, l'antimoine, l'étain, le cérium et d'autres éléments de la famille des lanthanides, et x représente la valence de M1 ;
    (2) un sel d'azote/sulfure métallique de la formule
    Figure 00630002
    dans laquelle R11 et R12 représentent indépendamment des groupes hydrocarbyle renfermant de 1 à 24 atomes de carbone, M2 est une partie métallique choisie parmi le cuivre, le zinc, l'antimoine, l'étain, le cérium et d'autres éléments de la famille des lanthanides et un cation molybdène choisi parmi -Mo=O et O=Mo=O, et y est la valence de M2 ;
    (3) un benzotriale de la formule
    Figure 00640001
    dans laquelle R13 est de l'hydrogène ou un groupe alkyle renfermant de 1 à 12 atomes de carbone, R16 est de l'hydrogène ou -CH2SR17, où R17 est un groupe alkyle renfermant de 1 à 18 atomes de carbone ; et
    (4) une composition sulfurée, et
    (5) un dérivé de dimercaptothiadiazole, ou des mélanges de (C) et (D).
  8. La composition de la revendication 7, dans laquelle à l'intérieur de l'alkyl phénol, z est 1, R4 est du t-butyle et a est 2.
  9. La composition de la revendication 7 ou de la revendication 8, dans laquelle à l'intérieur de l'amine aromatique, lorsque b est 1, R5 est
    Figure 00640002
    et R6 et R7 représentent tous les deux des groupes nonyle.
  10. La composition de la revendication 7 ou de la revendication 8, dans laquelle, dans l'amine aromatique, lorsque b est 2, R5 est
    Figure 00640003
    et R6 et R7 sont tous les deux de l'hydrogène.
  11. La composition de l'une quelconque des revendications 7 à 10, dans laquelle, dans l'amine hétérocyclique de la formule (C3a), R8 est du méthyle, Z est →O· et X est de l'hydrogène.
  12. La composition de l'une quelconque des revendications 7 à 11, dans laquelle, l'amine hétérocyclique de la formule (C3a), R8 est du méthyle et X et Z sont tous les deux de l'hydrogène.
  13. La composition de l'une quelconque des revendications 7 à 10, dans laquelle, dans l'amine hétérocyclique de la formule (C3a), R8 est du méthyle, X est -OR15 et R15 et Z sont tous les deux de l'hydrogène.
  14. La composition de l'une quelconque des revendicatons 7 à 10, dans laquelle, dans l'amine hétérocyclique de la formule (C3a), R8 est du méthyle et Z est de l'hydrogène ou →O·.
  15. La composition de l'une quelconque des revendications 7 à 14, dans laquelle dans le benzotriazole, R13 est du méthyle et R16 est de l'hydrogène.
  16. La composition de l'une quelconque des revendications 7 à 15, dans laquelle la composition sulfurée (4) comprend un hydrocarbure oléfinique sulfuré, l'hydrocarbure oléfinique sulfuré (a) est préparé en faisant réagir un adduct d'oléfine/halogénure de soufre en mettant en contact l'adduct d'oléfine/halogénure de soufre avec du sulfure de sodium ou du polysulfure de sodium dans un solvant protique sous des conditions basiques à une température dans la gamme d'au moins 40 °C à 120 °C, en éliminant les halogènes de l'adduct d'oléfine sulfurée/halogénure de soufre et en obtenant un produit complexe à base de polysulfure, ou
    (b) la composition sulfurée comporte le produit de réaction du soufre et d'un adduct de Diels-Alder selon un rapport molaire du soufre à l'adduct de Diels-Alder de 1:2 à 4:1, l'adduct de Diels-Alder comportant au moins un composé diénophile choisi parmi des esters d'acides aliphatiques carboxyliques à insaturation éthylénique, alpha, béta, des amides d'acides aliphatiques carboxyliques à insaturation éthylénique alpha, béta, des halogénures aliphatiques à insaturation éthylénique alpha, béta, des acrylates d'alkyle et des α-méthylacrylates d'alkyle, dans lesquels le groupe alkyle renferme de 1 à 10 atomes de carbone avec au moins un diène aliphatique conjugué correspondant à la formule :
    Figure 00660001
    dans laquelle R18 à R23 sont chacun choisis de façon indépendante parmi l'hydrogène, les groupes alkyle, alcoxy, alcényle, carboxy, cyano, phényle, et phényle substitué par de un à trois substituants correspondant à R18 à R23; ou
    (c) un mélange sulfuré d'un triglycéride dans lequel le triglycéride est un triglycéride d'huile végétale, comprenant l'huile d'arachide, l'huile de coton, l'huile de soja, l'huile de maïs, l'huile de carthame, l'huile de canola, l'huile de tournesol et l'huile de colza, de la formule
    Figure 00660002
    dans laquelle R1, R2 et R3 sont des groupes aliphatiques renfermant de 7 à 23 atomes de carbone, un acide carboxylique dans lequel l'acide carboxylique est un acide alcényle carboxylique de la formule R25 COOH, où R25 renferme de 7 à 29 atomes de carbone, et une oléfine dans laquelle l'oléfine est une monooléfine aliphatique qui renferme de 4 à 36 atomes de carbone.
  17. La composition de la revendication 16, dans laquelle à l'intérieur de (D4a), l'oléfine est un composé de type alkylène renfermant une double liaison de 2 à 50 atomes de carbone, et l'halogénure de soufre est un chlorure de soufre.
  18. La composition de la revendication 16, dans laquelle à l'intérieur de (D4a), l'oléfine est un mélange d'oléfines, qui renferme de l'isobutène et l'halogénure de soufre est choisi parmi le monochlorure de soufre, le dichlorure de soufre et des mélanges de ceux-ci ; le solvant protique est choisi parmi l'eau, des alcools, des acides carboxyliques et des combinaisons de ceux-ci tandis que le mélange de sulfure de sodium/ polysulfure de sodium est dérivé de fractions d'un procédé de purification d'hydrocarbures.
  19. La composition de l'une quelconque des revendications 16 à 18, dans laquelle dans (D4b), le rapport molaire du soufre à l'adduct est de 2:1 à 4:1.
  20. La composition de la revendication 19, dans laquelle, dans (D4b), le diène est en outre caractérisé en ce que R20 et R21 sont de l'hydrogène tandis que R18, R19, R22 et R23 représentent chacun indépendamment de l'hydrogène, du chlore ou un alkyle inférieur.
  21. La composition de la revendication 20, dans laquelle dans (D4b), le diène est du pipérylène, de l'isoprène, du méthylisoprène, du chloroprène ou du 1,3-butadiène tandis que le diénophile est un ester d'acide acrylique ou d'acide méthacrylique.
  22. La composition de la revendication 20 dans laquelle le diénophile est de l'acrylate de butyle ou du méthacrylate de butyle tandis que le diène est du 1,3-butadiène.
  23. La composition de l'une 'quelconque des revendications 16 à 22, dans laquelle le rapport pondéral de la combinaison de triglycéride, d'acide carboxylique et d'oléfine au soufre est de 5-15:1.
EP96304157A 1995-06-07 1996-06-05 Agents modificateurs de viscosité à base de copolymère de styrène et de diène pour fluides non polluants Expired - Lifetime EP0747467B1 (fr)

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