Pour point depressants for high monounsaturated vegetable oils and for high monounsaturated vegetable oils/biodegradable base and fluid mixtures

Claim 2

A composition, comprising; (A) at least one vegetable or synthetic triglyceride oil of the formula ##STR56## wherein R 1 , R 2 and R 3 are aliphatic hydrocarbyl groups having at least 60 percent monounsaturated character and containing from about 6 to about 24 carbon atoms and further wherein an oleic acid moiety:linoleic acid moiety is from about 2 up to about 90 and (B) at least one pour point depressant.

Claim 3

The composition of claim 1 wherein the triglyceride is a vegetable oil triglyceride comprising high oleic safflower oil, high oleic corn oil, high oleic rapeseed oil, high oleic sunflower oil, high oleic soybean oil, high oleic cottonseed oil, high oleic lesquerella oil, high oleic meadowfoam oil and high oleic palm olein.

Claim 4

The composition of claim 2 wherein the vegetable oil triglyceride is an ester of at least one straight chain fatty acid and glycerol wherein the fatty acid contains from about 8 to about 22 carbon atoms.

Claim 5

The composition of claim 3 wherein the triglyceride is at least 70 percent monounsaturated.

Claim 6

The composition of claim 4 wherein the triglyceride is at least 80 percent monounsaturated.

Claim 7

The composition of claim 5 wherein the monounsaturated fatty acid is oleic acid.

Claim 8

The composition of claim 1 wherein the pour point depressant is a mixed ester characterized by low-temperature modifying properties of a carboxy-containing interpolymer, said interpolymer having a reduced specific viscosity of from about 0.05 to about 2 and being derived from at least two monomers, one of said monomers being a low molecular weight aliphatic olefin, styrene or a substituted styrene wherein the substituent is a hydrocarbyl group containing from 1 up to about 18 carbon atoms, and the other of said monomers being an alpha, beta-unsaturated aliphatic acid, anhydride or ester thereof, said ester being substantially free of titratable acidity and being characterized by the presence within its polymeric structure of at least one of each of three pendant polar groups which are derived from the carboxy groups of said ester: (A) a relatively high molecular weight carboxylic ester group, said carboxylic ester group having at least 8 aliphatic carbon atoms in the ester radical, (B) a relatively low molecular weight carboxylic ester group having no more than 7 aliphatic carbon atoms in the ester radical, wherein the molar ratio of (A):(B) is (1-20):1, and optionally (C) a carbonyl-amino group derived from an amino compound having one primary or secondary amino group, wherein the molar ratio of (A):(B):(C) is (50-100):(5-50):(0.1-15).

Claim 9

The composition of claim 7 wherein said mixed ester is characterized by low-temperature modifying properties of a carboxy-containing interpolymer, said interpolymer having a reduced specific viscosity of from about 0.05 to about 2 and being derived from at least two monomers, the one being ethylene, propylene, isobutene, styrene or substituted styrene wherein the substituent is a hydrocarbyl group containing from 1 up to about 18 carbon atoms and the other of said monomers being maleic acid or anhydride, itaconic acid or anhydride or acrylic acid or ester, said ester being substantially free of titratable acidity and being characterized by the presence within its polymeric structure of at least one of each of three pendant polar groups which are derived from the carboxy groups of said ester: (A) a relatively high molecular weight carboxylic ester group, said carboxylic ester group having at least 8 aliphatic carbon atoms in the ester radical, (B) a relatively low molecular weight carboxylic ester group having no more than 7 aliphatic carbon atoms in the ester radical, wherein the molar ratio of (A):(B) is (1-20):1, and optionally (C) a carbonyl-amino group derived from an amino compound having one primary or secondary amino radical, wherein the molar ratio of (A):(B):(C) is (50-100): (5-50):(0.1-15).

Claim 10

The composition of claim 7 wherein the molar ratio of (A):(B) is (1-10):1.

Claim 11

The composition of claim 7 wherein the molar ratio of (A):(B):(C) is (70-85):(15-30):(3-4).

Claim 12

The composition of claim 7 wherein the interpolymer is a styrene-maleic anhydride interpolymer having a reduced specific viscosity of from about 0.1 to about 1.

Claim 13

The composition of claim 7 wherein the relatively high molecular weight carboxylic ester group of (A) has from 8 to 24 aliphatic carbon atoms, the relatively low molecular weight carboxylic ester group of (B) has from 3 to 5 carbon atoms and the carbonyl-amino group of (C) is derived from a primary-aminoalkyl-substituted tertiary amine.

Claim 14

The composition of claim 7 wherein the carboxy-containing interpolymer is a terpolymer of one molar proportion of styrene, one molar proportion of maleic anhydride, and less than about 0.3 molar proportion of a vinyl monomer.

Claim 15

The composition of claim 7 wherein said low molecular weight aliphatic olefin of said nitrogen-containing ester is selected from the group consisting of ethylene, propylene or isobutene.

Claim 16

The composition of claim 1 wherein the pour point depressant is an acrylate polymer of the formula ##STR57## wherein R 4 is hydrogen or a lower alkyl group containing from 1 to about 4 carbon atoms, R 5 is a mixture of alkyl, cycloalkyl or aromatic groups containing from about 4 to about 24 carbon atoms, and x is an integer providing a weight average molecular weight (Mw) to the acrylate polymer of about 5000 to about 1,000,000.

Claim 17

The composition of claim 15 wherein R 4 is a methyl group.

Claim 18

The composition of claim 15 wherein the molecular weight of the polymer is from about 50,000 to about 500,000.

Claim 19

The composition of claim 1 wherein the pour point depressant is a methylene linked aromatic compound that is a mixture of compounds having the general structural formula Ar-(R.sup.6)-[-Ar'(R.sup.7)].sub.n Ar" wherein the Ar, Ar' and Ar" are independently an aromatic moiety containing 1 to 3 aromatic rings and the mixture includes compounds wherein moieties are present with 0 substituents, 1 substituent, 2 substituents and 3 substituents, R 6 and R 7 are independently an alkylene containing about 1 to 100 carbon atoms, and n is 0 to 1000 wherein the methylene linked aromatic compound is produced by a process comprising the steps of; (a) providing aromatic compounds containing 1 to 3 aromatic rings which compounds are substituted with 0.to 3 substituents, the compounds being precursors for aromatic moieties Ar, Ar' and Ar" in a reactor; (b) adding a FRIEDEL-CRAFTS or Lewis Acid catalyst to the reactor; (c) adding a chlorinate hydrocarbon to the reactor; (d) adding an olefin to the reactor and (e) adding CH 2 Cl 2 to the reactor wherein step (e) is carried out prior to or concurrently with at least one step of (a)-(d).

Claim 20

The mixture as claimed in claim 18 wherein compounds are present in the mixture wherein the aromatic moieties are naphthalene, the olefin contains about 16 to 18 carbon atoms and the chlorinated hydrocarbon contains about 20 to 26 carbon atoms.

Claim 21

The mixture as claimed in claim 18 including compounds having a molecular weight ranging from about 300 to about 10,000.

Claim 22

The mixture as claimed in claim 18 including compounds having a molecular weight ranging from about 300 to about 300,000.

Claim 23

The composition of claim 1 wherein the pour point depressant is a nitrogen containing polyacrylate ester prepared by reacting an acrylate ester of the formula ##STR58## wherein R 8 is hydrogen or an alkyl group containing from 1 to about 4 carbon atoms and R 9 is an alkyl, cycloalkyl or aromatic group containing from 4 to about 24 carbon atoms with a nitrogen-containing compound at from 0.001-1.0 moles of the nitrogen containing compound for each mole of the acrylate ester.

Claim 24

The composition of claim 22 wherein the nitrogen-containing compound is selected from the group consisting of 4-vinylpyridine, 2-vinylpyridine, 2-N-morpholinoethyl methacrylate, N,N-dimethylaminoethyl methacrylate and N,N-dimethylaminopropyl methacrylate.

Claim 25

The composition of claim 1 further comprising (C) a performance additive selected from the group consisting of (1) at least one alkyl phenol of the formula ##STR59## wherein R 10 is an alkyl group containing from 1 up to about 24 carbon atoms and a is an integer of from 1 up to 5, and optionally (2) a metal deactivator selected from the group consisting of (a) a benzotriazole of the formula ##STR60## wherein R 11 is hydrogen or an alkyl group of 1 up to about 24 carbon atoms, (b) a phosphatide of the formula ##STR61## wherein R 12 and R 13 are aliphatic hydrocarbyl groups containing from 8 to about 24 carbon atoms, and G is selected from the group consisting of hydrogen, ##STR62## (c) a carbamate of the formula ##STR63## wherein R 14 is an allyl group containing from 1 to about 24 carbon atoms, phenyl or alkyl phenyl wherein the alkyl group contains from 1 to about 18 carbon atoms, R 15 and R 16 are hydrogen or an alkyl group containing from 1 to about 6 carbon atoms, with the proviso that R 15 and R 16 are not both hydrogen, (d) citric acid and derivatives of citric acid of the formula ##STR64## wherein R 17 , R 18 and R 19 are independently hydrogen or aliphatic hydrocarbyl groups containing from 1 to about 12 carbon atoms, with the proviso that at least one of R 17 , R 18 and R 19 is an aliphatic hydrocarbyl group, (e) a coupled phosphorus-containing amide of the formula ##STR65## wherein X 1 , X 2 and X 3 , independently is oxygen or sulfur; wherein R 20 and R 21 , independently is a hydrocarbyl, a hydrocarbyl-based oxy, the hydrocarbyl portions of which contain 6 to about 22 carbon atoms, or a hydrocarbyl-based thio, having from 4 to about 34 carbon atoms; wherein R 22 , R 23 , R 24 and R 25 , independently is hydrogen, or an alkyl having from 1 to about 22 carbon atoms, or an aromatic, an alkyl-substituted aromatic or an aromatic-substituted alkyl having from 6 to about 34 atoms; wherein n is zero or 1; wherein n' is 2 or 3; wherein R 26 is hydrogen; and when n' is 2, R 27 is selected from the group consisting of ##STR66## wherein R is an alkyl moiety, in the form of alkylene or alkylidene containing from 1 to 12 carbon atoms and R' is an alkyl moiety, alkylene, alkylidene or carboxyl containing 1 to 60 carbon atoms and when n' is 3, R 27 is ##STR67## (f) a methylacrylate derivative formed by the reaction of equal molar amounts of a phosphorus acid of the formula ##STR68## with methylacrylate wherein X 1 and X 2 are oxygen or sulfur and R 28 and R 29 are each independently a hydrocarbyl, a hydrocarbyl-based thio or preferably a hydrocarbyl-based oxy group wherein the hydrocarbyl portion contains from 1 to about 30 carbon atoms and remaining acidity is neutralized with 1 mole propylene oxide for each 20-25 moles of phosphorus acid; (3) a metal overbased composition; (4) a carboxylic dispersant composition: (5) a nitrogen-containing organic composition comprising (a) an acylated, nitrogen containing compound having a substituent of at least 10 aliphatic carbon atoms made by reacting a carboxylic acylating agent with at least one amino compound containing at least one --NH group, said acylating agent being linked to said amino compound through an imido, ado, amidine or acyloxy ammonium linkage, and (b) at least one amino phenol of the general formula ##STR69## wherein R 30 is a substantially saturated, hydrocarbon-based substituent of at least 10 aliphatic carbon atoms; a, b and c are each independently an integer of one up to three times the number of aromatic nuclei present in Ar with the proviso that the sum of a, b and c does not exceed the unsaturated valences of Ar; and Ar is an aromatic moiety having 0-3 optional substituents selected from the group consisting of lower alkyl, lower alkoxyl, nitro, halo or combinations of two or more of said substituents, (6) a zinc salt of be formula ##STR70## wherein R 31 and R 32 are independently hydrocarbyl groups containing from about 3 to about 20 carbon atoms, (7) a sulfurized composition wherein the sulfurized composition is a sulfurized olefin prepared by reacting an olefin/sulfur halide complex by contacting the complex with a protic solvent in the presence of metal ions at a temperature in the range of 40° C. to 120° C. and thereby removing halogens from the sulfurized complex and providing a dehalogenated sulfurized olefin; and isolating the sulfurized olefin, or the sulfurized composition comprises the reaction product of sulfur and a Diels-Alder adduct in a molar ratio of sulfur to adduct of from about 1:2 to about 4:1 wherein the adduct comprises at least one dienophile selected from the group consisting of alpha, beta ethylenically unsaturated aliphatic carboxylic acid esters, alpha, beta ethylenically unsaturated aliphatic carboxylic acid amides, and alpha, beta ethylenically unsaturated aliphatic halides with at least one aliphatic conjugated diene corresponding to the formula ##STR71## where R 44 through R 49 are each independently selected from the group consisting of hydrogen, alkyl, halo, alkoxy, alkenyl, alkenyloxy, carboxy, cyano, amino, alkylamino, dialkylamino, phenyl, and phenyl substituted with one to three substituents corresponding to R 44 through R 49 ; (8) at least one viscosity index improver; and (9) at least one aromatic amine of the formula ##STR72## wherein R 33 is ##STR73## and R 34 and R 35 are independently a hydrogen or an alkyl group containing from 1 up to about 24 carbon atoms.

Claim 26

The composition of claim 24 wherein within (C)(1) a is 2 and R 10 contains from 1 up to about 8 carbon atoms.

Claim 27

The composition of claim 25 wherein the alkyl phenol is of the formula ##STR74##

Claim 28

The composition of claim 24 wherein within (C)(2)(a) R 11 is hydrogen or an alkyl group containing from 1 up to about 8 carbon atoms.

Claim 29

The composition of claim 24 wherein within (C)(2)(a) R 11 is a methyl group.

Claim 30

The composition of claim 24 wherein within (C)(2)(f) X 1 and X 2 are sulfur and R 28 and R 29 are hydrocarbyl-based oxy groups wherein the hydrocarbyl group contains from 1 to 12 carbon atoms.

Claim 31

The composition of claim 24 wherein within (C)(3) the metal overbased composition is selected from the group consisting of (a) a metal overbased phenate derived from the reaction of an alkylated phenol wherein the alkyl group has at least 6 aliphatic carbon atoms optionally reacted with formaldehyde or a sulfurization agent or mixtures thereof, (b) a metal overbased sulfonate derived from an alkylated aryl sulfonic acid wherein the alkyl group has at least 15 aliphatic carbon atoms and (c) a metal overbased carboxylate derived from fatty acids having at least 8 aliphatic carbon atoms.

Claim 32

The composition of claim 30 wherein the metal is an alkali or alkaline earth metal.

Claim 33

The composition of claim 31 wherein the alkaline earth metal is calcium or magnesium.

Claim 34

The composition of claim 31 wherein the alkali metal is sodium.

Claim 35

The composition of claim 30 wherein the metal overbased composition is treated with a borating agent.

Claim 36

The composition of claim 24 wherein within (C)(4) the carboxylic dispersant composition comprises the reaction of a hydrocarbon substituted succinic acid-producing compound with at least about one-half equivalent, per equivalent of acid producing compound, of an organic hydroxy compound or an amine containing at least one hydrogen attached to a nitrogen atom, or a mixture of said hydroxy compound and amine.

Claim 37

The composition of claim 35 wherein within (C)(4) the succinic acid-producing compound contains an average of at least about 50 aliphatic carbon atoms in the substituent.

Claim 38

The composition of claim 35 wherein within (C)(4) the succinic acid producing compound is selected from the group consisting of succinic acids, anhydrides, esters and halides.

Claim 39

The composition of claim 35 wherein within (C)(4) the hydrocarbon substituent of the succinic acid producing compound is derived from a polyolefin having an Mn value within the range of from about 700 to about 10,000.

Claim 40

The composition of claim 35 wherein within (C)(4) the amine reacted with the succinic acid producing compound is characterized by the formula R.sup.39 R.sup.40 NH wherein R 39 and R 40 are each independently hydrogen, or hydrocarbon, amino-substituted hydrocarbon, hydroxy-substituted hydrocarbon, alkoxy-substituted hydrocarbon, amino, carbamyl, thiocarbamyl, guanyl, and acylimidoyl groups provided that only one of R 39 and R 40 may be hydrogen.

Claim 41

The composition of claim 35 wherein within (C)(4) the amine reacted with the succinic acid producing compound is a polyamine.

Claim 42

The composition of claim 24 wherein within (C)(5)(a) the amino compound is an alkylene polyamine of the general formula ##STR75## wherein U is an alkylene group of 2 to 10 carbon atoms; each R 41 is independently a hydrogen atom, a lower alkyl group or a lower hydroxy alkyl group, with the proviso that at least one R 41 is a hydrogen atom, and n is 1 to 10.

Claim 43

The composition of claim 41 wherein within (C)(5)(a) the acylating agent is a mono- or polycarboxylic acid, or reactant equivalent thereof, containing an aliphatic hydrocarbyl substituent of at least about 30 carbon atoms.

Claim 44

The composition of claim 42 wherein within (C)(5)(a) the substituent is made from a homo- or interpolymer of a C 2-10 1-monoolefin or mixtures thereof.

Claim 45

The composition of claim 43 wherein within (C)(5)(a) the homo- or interpolymer is of ethylene, propylene, 1-butene, 2-butene, isobutene or mixtures thereof.

Claim 46

The composition of claim 41 wherein within (C)(5)(a) the acylating agent is at least one mono-carboxylic acid, or reactant equivalent thereof, having from 12 to 30 carbon atoms.

Claim 47

The composition of claim 45 wherein within (C)(5)(a) the acylating agent is a mixture of fatty monocarboxylic acids, or reactant equivalent thereof, having straight and branched carbon chains.

Claim 48

The composition of claim 46 wherein within (C)(5)(a) the amino compound is an ethylene, propylene or trimethylene polyamine of at least 2 to about 8 amino groups or mixtures of such polyamines.

Claim 49

The composition of claim 24 wherein within (C)(5)(b) R 30 contains up to about 750 carbon atoms and there are no optional substituents attached to Ar.

Claim 50

The composition of claim 48 wherein within (C)(5)(b) R 30 is an alkyl or alkenyl group.

Claim 51

The composition of claim 24 wherein within (C)(5)(b) R 30 contains about 30 to about 750 aliphatic carbon atoms and is made from a homo- or interpolymer of C 2 -C 10 olefins.

Claim 52

The composition of claim 50 wherein within (C)(5)(b) said olefins are selected from the group consisting of ethylene, propylene, butylene and mixtures thereof.

Claim 53

The composition of claim 24 wherein within (C)(5)(b) a, b and c are each 1, there are zero optional substituents attached to Ar, and Ar is a benzene nucleus.

Claim 54

The composition of claim 52 wherein within (C)(5)(b) R 30 is an alkyl or alkenyl group of at least about 30 carbon atoms and up to about 750 carbon atoms and is derived from a homo or interpolymer of C 2 -C 10 1-monoolefins.

Claim 55

The composition of claim 24 wherein within (C)(5)(b) the amino phenol is of the formula ##STR76## wherein R 42 is a substantially saturated hydrocarbon-based substituent having an average of from about 30 to about 400 aliphatic carbon atoms, R 43 is a member selected from the group consisting of lower alkyl, lower alkoxy, nitro, and halo; and z is zero or one.

Claim 56

The composition of claim 54 wherein within (C)(5)(b) R 42 is a purely hydrocarbyl aliphatic group of at least about 50 carbon atoms and is made from a polymer or interpolymer of an olefin selected from the group consisting of C 2-10 1-monoolefins and mixtures thereof.

Claim 57

The composition of claim 55 wherein within (C)(5)(b) z is zero.

Claim 58

The composition of claim 24 wherein within (C)(7) the olefin is an alkylene compound containing one double bond and 2 to 50 carbon atoms, and the sulfur halide is a sulfur chloride.

Claim 59

The composition of claim 24 wherein within (C)(7) the olefin is a mixture of olefins containing isobutene and the sulfur halide is selected from the group consisting of sulfur monochloride, sulfur dichloride and mixtures thereof; the protic solvent is selected from the group consisting of water, alcohols, carboxylic acids and combination thereof; and the metal ions are sodium sulfide/sodium hydrosulfide mixture derived from hydrocarbon purification process streams and sodium hydroxide.

Claim 60

The composition of claim 24 wherein within (C)(7) the sodium sulfide/sodium hydrosulfide mixture is derived from hydrocarbon purification process streams.

Claim 61

The composition of claim 24 wherein within (C)(7) the olefin contains one double bond and 2 to 50 carbon atoms and the sulfur halide is a sulfur chloride.

Claim 62

The composition of claim 60 wherein within (C)(7) the olefin is isobutene, the sulfur halide is sulfur monochloride, and the protic solvent is a water-isopropyl alcohol mixture.

Claim 63

The composition of claim 24 wherein within (C)(7) the molar ratio of sulfur to adduct is from about 2:1 to about 4:1.

Claim 64

The composition of claim 62 wherein within (C)(7) the diene is further characterized in that R 46 and R 47 are hydrogen and are R 44 , R 45 , R 48 and R 49 are each independently hydrogen, chloro, or lower alkyl.

Claim 65

The composition of claim 63 wherein within (C)(7) the dienophile is further characterized in that it contains at least one but not more than two --C(O)OR.sup.50 where R 50 is the residue of a saturated aliphatic alcohol of up to about 40 carbon atoms.

Claim 66

The composition of claim 64 wherein within (C)(7) the diene is piperylene, isoprene, methylisoprene, chloroprene, or 1,3-butadiene.

Claim 67

The composition of claim 65 wherein within (C)(7) the dienophile is an ester of acrylic acid or methacrylic acid.

Claim 68

The composition of claim 65 wherein within (C)(7) the dienophile is an alkyl ester of acrylic acid or methacrylic acid containing at least 4 carbon atoms in the alkyl group.

Claim 69

The composition of claim 67 wherein within (C)(7) the diene is 1,3-butadiene.

Claim 70

The composition of claim 24 wherein within (C)(9) R 33 is ##STR77## and R 34 and R 35 are alkyl groups containing from 4 to 18 carbon atoms.

Claim 71

The composition of claim 69 wherein within (C)(9) R 34 and R 35 are nonyl groups.

Claim 72

The composition of claim 1 further comprising (D) at least one oil selected from the group consisting of (1) synthetic ester base oil comprising the reaction of a monocarboxylic acid of the formula R.sup.36 COOH or a dicarboxylic acid of the formula ##STR78## with an alcohol of the formula R.sup.38 (OH).sub.n wherein R 36 is a hydrocarbyl group containing from about 4 to about 24 carbon atoms, R 37 is hydrogen or a hydrocarbyl group containing from about 4 to about 50 carbon atoms, R 38 is a hydrocarbyl group containing from 1 to about 24 carbon atoms, m is an integer of from 0 to about 6 and n is an integer of from 1 to about 6; (2) a mineral oil; (3) a polyalphaolefin and (4) a vegetable oil.

Claim 73

The composition of claim 24 further comprising (D) at least one oil selected from the group consisting of (1) synthetic ester base oil comprising the reaction of a monocarboxylic acid of the formula R.sup.36 COOH or a dicarboxylic acid of the formula ##STR79## with an alcohol of the formula R.sup.38 (OH).sub.n wherein R 36 is a hydrocarbyl group containing from about 4 to about 24 carbon atoms, R 37 is hydrogen or a hydrocarbyl group containing from about 4 to about 50 carbon atoms, R 38 is a hydrocarbyl group containing from 1 to about 24 carbon atoms, m is an integer of from 0 to about 6 and n is an integer of from 1 to about 6; (2) a mineral oil; (3) a polyalphaolefin and (4) a vegetable oil.