FUNCTIONALIZED POLYMERS
This invention relates to functionalized polymers derived from functionalized monomers. The functionalized polymer may be reacted with an enophilic reagent (e.g., maleic anhydride) to form an enophilic reagent modified functionalized polymer. The functionalized polymer may be further reacted with one or more additional reagents, e.g., an oxygen-containing reagent (e.g., alcohol, polyol), a nitrogen-containing reagent (e.g., amine, polyamine, aminoalcohol), a metal, a metal compound, or a mixture of two or more thereof. The invention relates to lubricants, functional fluids, fuels, dispersants, detergents and polymer compositions.
1 . A composition, comprising:
a functionalized polymer derived from a functionalized monomer,
the functionalized monomer comprising a hydrocarbyl group with one or more carbon-carbon double bonds and one or more functional groups attached to the hydrocarbyl group, the hydrocarbyl group containing at least about 5 carbon atoms, the functional group comprising a carboxylic acid group or a derivative thereof, a hydroxyl group, an amino group, a carbonyl group, a cyano group, or a mixture of two or more thereof;
wherein when the functionalized polymer is derived from methyl 9-decenoate and an alpha-olefin, the alpha-olefin contains at least about 8 carbon atoms.
2 . The composition of claim 1 wherein the functionalized monomer is reacted with an enophilic reagent to form an enophilic reagent modified functionalized monomer, the functionalized polymer being derived from the enophilic reagent modified functionalized monomer, the enophilic reagent comprising an oxidizing agent, a sulfurizing agent, a sulfur oxidizing agent, an enophilic acid, anhydride and/or ester reagent, an aromatic compound, a hydroxylating agent, a halogenating agent, or a mixture of two or more thereof, the enophilic reagent being reactive towards one or more of the carbon-carbon double bonds in the hydrocarbyl group and/or the functional group.
3 . The composition of claim 1 wherein the functionalized monomer comprises an unsaturated carboxylic acid, anhydride, ester, amide, imide, alcohol, amine, aldehyde, ketone, nitrile, salt, ester salt, amide salt, or a mixture of two or more thereof.
4 . The composition of claim 1 wherein the functionalized polymer comprises one or more carbon-carbon double bonds and is reacted with an enophilic reagent to form an enophilic reagent modified functionalized polymer, the enophilic reagent comprising an oxidizing agent, a sulfurizing agent, a sulfur oxidizing agent, an enophilic acid, anhydride and/or ester reagent, an aromatic compound, a hydroxylating agent, a halogenating agent, or a mixture of two or more thereof, the enophilic reagent being reactive towards one or more of the carbon-carbon double bonds in the functionalized polymer and/or the functional group.
5 . The composition of claim 1 wherein the functionalized polymer comprises a homopolymer, copolymer, oligomer, co-oligomer, or a mixture of two or more thereof.
6 . The composition of claim 1 wherein the functionalized polymer comprises repeating units derived from two or more of the functionalized monomers.
7 . The composition of claim 1 wherein the functionalized polymer comprises from about 5 to about 99 mole percent repeating units derived from the functionalized monomer.
8 . The composition of claim 1 wherein the functionalized polymer is derived from the functionalized monomer and a comonomer, the comonomer comprising an olefin, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, unsaturated nitrile, vinyl ester, vinyl ether, halogenated monomer, unsaturated polycarboxylic acid or derivative thereof, polyhydric alcohol, polyamine, polyalkylene polyamine, monoisocyanate, diisocyanate, alkenyl-substituted aromatic compound, akenyl-substituted heterocyclic compound, organosilane, or a mixture of two or more thereof.
9 . The composition of claim 8 wherein the comonomer comprises an olefin containing from 2 to about 30 carbon atoms per molecule.
10 . The composition of claim 1 wherein the hydrocarbyl group contains one, two, three or four carbon-carbon double bonds.
11 . The composition claim 8 wherein the comonomer contains one, two, three or four carbon-carbon double bonds.
12 . The composition of claim 1 wherein the functionalized polymer has a number average molecular weight in the range from about 100 to about 50,000.
13 . The composition of claim 1 wherein the functionalized monomer contains a carbon-carbon double bond in the terminal position of the hydrocarbyl group.
14 . The composition of claim 1 wherein the functionalized polymer is derived from the functionalized monomer and a comonomer, the comonomer comprising an olefin chain with a carbon-carbon double bond in the terminal position of the olefin chain.
15 . The composition of claim 1 wherein the functional group is attached to a terminal carbon atom on the hydrocarbyl group.
16 . The composition of claim 1 wherein the functional group is attached to an internal carbon atom in the hydrocarbyl group.
17 . The composition of claim 1 wherein the functionalized polymer is derived from methyl 9-decenoate.
18 . The composition of claim 1 wherein the functionalized polymer is derived from methyl 9-decenoate and 1-decene.
19 . The composition of claim 2 wherein the oxidizing agent comprises a compound containing an oxygen-oxygen single bond.
20 . The composition of claim 2 wherein the oxidizing agent comprises a compound containing a peroxide group or a peroxide ion.
21 . The composition of claim 2 wherein the oxidizing agent comprises hydrogen peroxide, an organic peroxide, an inorganic peroxide, or a mixture of two or more thereof.
22 . The composition of claim 2 wherein the sulfurizing agent comprises elemental sulfur, sulfur halide, a combination of sulfur or sulfur oxide with hydrogen sulfide, phosphorus sulfide, aromatic sulfide, alkyl sulfide, sulfurized olefin, sulfurized oil, sulfurized fatty ester, diester sulfide, or a mixture of two or more thereof.
23 . The composition of claim 2 wherein the sulfur oxidizing agent comprises a sulfonating agent, sulfinating agent, sulfenating agent, or a mixture of two or more thereof.
24 . The composition of claim 23 or wherein the sulfur oxidizing agent comprises sulfur trioxide, oleum, chlorosulfonic acid, sodium bisulfite, or a mixture of two or more thereof.
25 . The composition of claim 2 wherein the enophilic acid, anhydride and/or ester reagent comprises one or more olefinically unsaturated carboxylic acids and/or derivatives thereof.
26 . The composition of claim 2 wherein the enophilic acid, anhydride and/or ester reagent comprises one or more compounds represented by the formula
wherein R 1 and R 2 are independently hydrogen or hydrocarbyl groups.
27 . The composition of claim 2 wherein the enophilic acid, anhydride and/or ester reagent comprises one or more unsaturated dicarboxylic acids and/or derivatives thereof.
28 . The composition of claim 2 wherein the enophilic acid reagent comprises acrylic acid; methacrylic acid; cinnamic acid; crotonic acid; 3-phenyl propenoic acid; maleic acid; fumaric acid; mesconic acid; itaconic acid; citraconic acid; or a mixture of two or more thereof.
29 . The composition of claim 2 wherein the enophilic acid, anhydride and/or ester reagent comprises maleic anhydride.
30 . The composition of claim 2 wherein the aromatic compound comprises an aromatic compound, aliphatic-substituted aromatic compound, or aromatic-substituted aliphatic compound.
31 . The composition of claim 2 wherein the aromatic compound comprises a substituted aromatic compound containing one or more substituent groups selected from hydroxy, halo, nitro, amino, cyano, alkoxy, acyl, epoxy, acryloxy, mercapto, or a mixture of two or more thereof.
32 . The composition of claim 2 wherein the aromatic compound contains from 6 to about 40 carbon atoms.
33 . The composition of claim 2 wherein the aromatic compound comprises benzene, toluene, ethylbenzene, styrene, alpha-methyl styrene, propylbenzene, xylene, mesitylene, methylethylbenzene, naphthalene, anthracene, phenanthrene, methynaphthalene, dimethylnaphthalene, tetralin, phenol, mono-substituted alkyl phenol, di-substituted alkyl phenol, tri-substituted alkyl phenol, dihydroxybenzene, naphthol, dihydroxynaphthalene, aromatic amine, pyridine, aniline, toluidine, phenylenediamine, toluenediamine, diphenylamine, alkyldiphenylamine, phenothiazine, or a mixture of two or more thereof.
34 . The composition of claim 2 wherein the aromatic compound comprises o-, m- and/or p-xylene, toluene, tolylaldehyde, aminotoluene, o-, m- and/or p-cresol, benzaldehyde, or a mixture of two or more thereof.
35 . The composition of claim 2 wherein the hydroxylating agent comprises water, hydrogen peroxide, or a mixture thereof.
36 . The composition of claim 2 wherein the halogenating agent comprises fluorine, chlorine, bromine, iodine, hydrogen chloride, hydrogen bromide, hydrogen fluoride, iodine monochloride, antimony pentafluoride, molybdenum pentachloride, nitrogen fluoride oxide, antimony pentachloride, tungsten hexafluoride, tellurium hexafluoride, sulfur tetrafluoride, sulfur monochloride, silicon tetrafluoride, phosphorus pentafluoride, or a mixture of two or more thereof.
37 . A dispersant composition derived from a nitrogen-containing reagent and/or an oxygen-containing reagent, the functionalized polymer of claim 1 , and an enophilic reagent, wherein the enophilic reagent comprises an enophilic acid, anhydride and/or ester.
38 . The dispersant composition of claim 37 wherein the functionalized polymer is derived from the functionalized monomer and a comonomer, the comonomer comprising an olefin containing from 2 to about 30 carbon atoms.
39 . The dispersant composition of claim 37 wherein the functionalized polymer is derived from methyl 9-decenoate, or methyl 9-decenoate and 1-decene.
40 . The dispersant composition of claim 37 wherein the enophilic acid, anhydride and/or ester reagent comprises one or more compounds represented by the formula
wherein R 1 and R 2 are independently hydrogen or hydrocarbyl groups.
41 . The dispersant composition of claim 37 wherein the enophilic acid, anhydride and/or ester reagent comprises one or more unsaturated dicarboxylic acids and/or derivatives thereof.
42 . The dispersant composition of claim 37 wherein the enophilic acid, anhydride and/or ester reagent comprises acrylic acid; methacrylic acid; cinnamic acid; crotonic acid; 3-phenyl propenoic acid; maleic acid; fumaric acid; mesconic acid; itaconic acid; citraconic acid; maleic anhydride; or a mixture of two or more thereof.
43 . The dispersant composition of claim 37 wherein the enophilic acid, anhydride and/or ester reagent comprises maleic anhydride.
44 . The dispersant composition of claim 37 wherein the functionalized polymer contains from about 5 to about 99 mole percent of repeating units derived from the functionalized monomer.
45 . The dispersant composition of claim 37 wherein the nitrogen-containing reagent comprises ammonia, an amine containing one or more primary and/or secondary amino groups, a mono-substituted amine, di-substituted amine, an amino-alcohol, an amine terminated poly (oxyalkylene), or a mixture of two or more thereof.
46 . The dispersant composition of claim 37 wherein the nitrogen-containing reagent comprises methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, methanolamine, dimethanolamine, ethanolamine, diethanolamine, propanolamine, dipropanolamine, butanolamine, dibutanolamine, pentanolamine, dipentanolamine, hexanolamine, dihexanolamine, heptanolamine, diheptanolamine, octanolamine, dioctanolamine, aniline,
ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,3-bis(aminomethyl)cyclohexane, meta-xylenediamine, 1,8-naphthalenediamine, p-phenylenediamine, N-(2-aminoethyl)-1,3-propanediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, dipentylenetriamine, dihexylenetriamine, diheptylenetriamine, dioctylenetriamine, spermidine, melamine, triethylenetetramine, tripropylenetetramine, tributylenetetramine, tripentylenetetramine, trihexylenetetramine, triheptylenetetramine, trioctylenetetramine, hexamine, an imidazole, aminopropylimidazole, oxazolidine, or a mixture of two or more thereof.
47 . The dispersant composition of claim 37 wherein the nitrogen-containing reagent comprises a polyamine represented by the formula
wherein each R is independently hydrogen, a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group containing up to about 30 carbon atoms, or up to about 10 carbon atoms, with the proviso that at least one R is hydrogen, n is a number in the range from 1 to about 10, or from about 2 to about 8, and R 1 is an alkyene group containing 1 to about 18 carbon atoms, or 1 to about 10 carbon atoms, or from about 2 to about 6 carbon atoms.
48 . The dispersant composition of claim 37 wherein the polyamine comprises methylene polyamine, ethylene polyamine, propylene polyamine, butylenes polyamine, pentylene polyamine, hexylene polyamine, heptylene polyamine, ethylene diamine, triethylene tetramine, tris(2-aminoethyl)amine, propylene diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(trimethylene) triamine, 2-heptyl-3-(2-aminopropyl)imidazoline, 1,3-bis(2-amino-ethyl)piperazine, 1,4-bis(2-aminoethyl)piperazine, 2-methyl-1-(2-aminobutyl)piperazine, or a mixture of two or more thereof.
49 . The dispersant composition of claim 37 wherein the oxygen-containing reagent comprises methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, isopropanol, isobutanol, sec-butanol, tert-butanol, isopentanol, amyl alcohol, isoamyl alcohol, tert-pentanol, cyclopentanol, neopentyl alcohol, cyclohexanol, 2-ethylhexanol, allyl alcohol, crotyl alcohol, methylvinyl carbinol, benzyl alcohol, alpha-phenylethyl alcohol, beta-phenylethyl alcohol, diphenylcarbinol, triphenylcarbinol, cinnamyl alcohol, or a mixture of two or more thereof.
50 . The dispersant composition of claim 37 wherein the oxygen-containing reagent comprises one or more polyols containing from 2 to about 10 carbon atoms, and from 2 to about 6 hydroxyl groups.
51 . The dispersant composition of claim 37 wherein the oxygen-containing reagent comprises ethylene glycol, glycerol, trimethylolpropane, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-ethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, pentaerythritol, sorbitol, or a mixture of two or more thereof.
52 . The dispersant composition of claim 37 wherein the dispersant is derived from an oxygen-containing reagent and a nitrogen-containing reagent, the dispersant being formed by the reaction of the functionalized polymer (i) and/or reaction product (ii) with the oxygen-containing reagent to form an intermediate product, the intermediate product being reacted with the nitrogen-containing reagent.
53 . The dispersant of claim 37 wherein the functionalized polymer and an alkenyl succinic anhydride are reacted with the nitrogen-containing reagent and/or oxygen-containing reagent.
54 . The dispersant composition of claim 53 wherein the alkenyl succinic anhydride comprises a polyisobutenyl succinic anhydride.
55 . The dispersant composition of claim 37 , wherein the dispersant is mixed with a succinimide.
56 . The dispersant composition of claim 55 wherein the succinimide is a polyisobutenyl succinimide.
57 . A detergent composition comprising a neutral or overbased detergent derived from a metal or metal compound, the functionalized polymer of claim 1 , and an enophilic reagent, wherein the enophilic reagent comprises an enophilic acid, anhydride and/or ester, and/or a sulfur oxidizing agent.
58 . The detergent composition of claim 57 wherein the detergent is an overbased detergent.
59 . The detergent composition of claim 57 wherein the functionalized polymer is derived from the functionalized monomer and a comonomer, the comonomer comprising an olefin containing from 2 to about 30 carbon atoms, or from about 6 to about 24 carbon atoms.
60 . The detergent composition of claim 57 wherein the functionalized polymer is derived from methyl 9-decenoate, or methyl 9-decenoate and 1-decene.
61 . The detergent composition of claim 57 wherein the enophilic acid, anhydride and/or ester reagent comprises acrylic acid; methacrylic acid; cinnamic acid; crotonic acid; 3-phenyl propenoic acid; maleic acid; fumaric acid; mesconic acid; itaconic acid; citraconic acid; or a mixture of two or more thereof.
62 . The detergent composition of claim 57 wherein the enophilic acid, anhydride and/or ester reagent comprises maleic anhydride.
63 . The detergent composition of claim 57 wherein the functionalized polymer contains from about 5 to about 99 mole percent of repeating units derived from the functionalized monomer.
64 . The detergent composition of claim 57 wherein the metal comprises an alkali metal, alkaline earth metal, titanium, zirconium, molybdenum, iron, copper, aluminum, zinc, or a mixture of two or more thereof.
65 . The detergent composition of claim 57 wherein one or more alkarylsulfonic acids are mixed with the functionalized polymer.
66 . The detergent composition of claim 57 wherein the detergent is derived from (1) the functionalized polymer, enophilic reagent and, optionally, in combination with an alkaryl sulfonic acid, and (2) a reaction medium, (3) a stoichiometric excess of at least one metal base, (4) a promoter, and (5) an acidic material.
67 . The detergent composition of claim 57 wherein the detergent comprises a boron-containing overbased detergent.
68 . A concentrate composition comprising from about 0.1% to about 99% by weight of the composition of claim 1 , and a normally liquid diluent.
69 . A lubricant or functional fluid composition comprising the composition of claim 1 .
70 . The lubricant or functional fluid composition of claim 69 wherein the composition further comprises an API Group I, Group II, Group III, Group IV, Group V base oil, a natural oil, an estolide, or a mixture of two or more thereof.
71 . The lubricant or functional fluid composition of claim 69 wherein the lubricant or functional fluid composition further comprises a supplemental detergent, supplemental dispersant, corrosion inhibitor, oxidation inhibitor, antiwear agent, friction modifier, pour point depressant, anti-foam agent, metal deactivator, viscosity modifier, extreme pressure agent, demulsifier, seal swelling agent, or a mixture of two or more thereof.
72 . The lubricant or functional fluid composition of claim 69 wherein the lubricant or functional fluid composition comprises a grease composition, the grease composition comprising lithium hydroxide, lithium hydroxide monohydrate, or a mixture thereof.
73 . A fuel composition comprising the composition of claim 1 .
74 . The fuel composition of claim 73 wherein the composition further comprises a normally liquid fuel.
75 . The fuel composition of claim 74 wherein the normally liquid fuel is derived from petroleum, crude oil, a Fischer-Tropsch process, coal, natural gas, oil shale, biomass, or a mixture of two or more thereof.
76 . The fuel composition of claim 74 wherein the normally liquid fuel comprises a synthetic fuel.
77 . The fuel composition of claim 73 wherein the fuel composition comprises gasoline or a middle distillate fuel.
78 . The fuel composition of claim 73 wherein the fuel composition comprises kerosene, jet fuel, diesel fuel, fuel oil, heating oil, naphtha, or a mixture of two or more thereof.
79 . The fuel composition of claim 73 wherein the fuel composition further comprises: one or more functional additives, the one or more functional additives, comprising a cold flow improver additive for increasing horsepower; additive for improving fuel economy; additive for lubricating and reducing wear of engine components; additive for cleaning and preventing deposit buildup; additive for reducing smoke and particulate emissions; additive for removing water; additive for reducing rust and corrosion; additive for upgrading and stabilizing the fuel; additive for improving storage and combustion capabilities; antioxidant; antistatic agent; corrosion inhibitor; fuel system icing inhibitor; cold flow improver; biocide; metal deactivator; additive for reducing fuel line and filter clogging; additive for improving fuel atomization; additive for reducing deposits on burner nozzles; additive for enhancing flame stabilization; additive for improving combustion; additive for reducing soot formation; additive for neutralizing vanadium and sodium; additive for improving heat transfer; additive for reducing the formation of sulfur trioxide; additive for reducing stack temperatures; additive for reducing carbon monoxide, oxygen and/or unburnt hydrocarbon in stack gases; additive for reducing fuel consumption; polar compound for dispersing paraffins; oil-soluble amphiphile; pour point depressant; dewaxing additive; sludge inhibitor; dehazer; additive for reducing cloud point; or a mixtures of two or more thereof.
80 . A composition comprising the composition of claim 1 , and further comprising water, solvent, thixotropic additive, pseudoplastic additive, rheology modifier, anti-settling agent, leveling agent, defoamer, pigment, dye, plasticizer, viscosity stabilizer, biocide, viricide, fungicide, crosslinker, humectant, surfactant, detergent, soap, fragrance, sweetener, alcohol, food product, food additive, or a mixture of two or more thereof.
81 . The composition of claim 81 wherein the composition is in the form of a liquid, a solid, or a mixture thereof.
82 . The composition of claim 1 wherein the functionalized monomer comprises a natural oil derived unsaturated fatty acid, unsaturated fatty ester, polyunsaturated fatty acid, polyunsaturated fatty ester, or a mixture of two or more thereof.
83 . The composition of claim 1 wherein the functionalized monomer comprises a natural oil derived unsaturated monoglyceride, unsaturated diglyceride, unsaturated triglyceride, or a mixture of two or more thereof.
84 . The composition of claim 1 wherein the functionalized monomer comprises a terminal functional group and an alkene chain, the alkene chain being: an alkene chain of about 10 to about 30 carbon atoms and a carbon-carbon double bond between the C 9 and C 10 carbon atoms in the alkene chain; or an alkene chain of about 8 to about 30 carbon atoms and a carbon-carbon double bond between the C 6 and C 7 carbon atoms in the alkene chain; or an alkene chain of about 12 to about 30 carbon atoms and a carbon-carbon double bond between the C 11 and C 12 carbon atoms in the alkene chain; or an alkene chain of about 14 to about 30 carbon atoms and a carbon-carbon double bond between the C 13 and C 14 carbon atoms in the alkene chain; or an alkene chain of about 14 to about 30 carbon atoms and carbon-carbon double bonds between the C 9 and C 10 carbon atoms and between the C 12 and C 13 carbon atoms in the alkene chain; or an alkene chain of about 16 to about 30 carbon atoms and carbon-carbon double bonds between the C 9 and C 10 carbon atoms, between the C 12 and C 13 carbon atoms, and between C 15 and C 16 carbon atoms in the alkene chain; or an alkene chain of about 16 to about 30 carbon atoms and carbon-carbon double bonds between the C 6 and C 7 carbon atoms, between the C 9 and C 10 carbon atoms, between the C 12 and C 13 carbon atoms, and between the C 15 and C 16 carbon atoms in the alkene chain.
85 . The composition of claim 1 wherein the functionalized monomer is derived from vegetable oil, algae oil, fungus oil, animal oil, animal fat, tall oil, sucrose, lactose, glucose, fructose, or a mixture of two or more thereof.
86 . The composition of claim 1 wherein the functionalized monomer is derived from canola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower seed oil, linseed oil, palm kernel oil, tung oil, jatropha oil, mustard oil, camellina oil, pennycress oil, castor oil, coriander oil, almond oil, wheat germ oil, bone oil, lard, tallow, poultry fat, algal oil, yellow grease, fish oil, sugar cane, sugar beet, corn syrup, or a mixture of two or more thereof.
87 . The composition of claim 1 wherein the functionalized monomer is derived from a natural oil, the natural oil comprising refined, bleached and/or deodorized natural oil.
88 . The composition of claim 87 wherein the refined, bleached and/or deodorized natural oil comprises refined, bleached and/or deodorized soybean oil.
89 . The composition of claim 1 wherein the functionalized monomer comprises an estolide.
90 . The composition of claim 1 wherein the functionalized monomer is derived from an estolide.
91 . The composition of claim 1 wherein the functionalized monomer is derived from a metathesized natural oil, the metathesized natural oil comprising the product of a self-metathesis process or a cross-metathesis process.
92 . The composition of claim 91 wherein the metathesized natural oil is made by reacting one or more natural oils and/or natural oil derived unsaturated carboxylic acids and/or esters in the presence of a metathesis catalyst to form the metathesized natural oil.
93 . The composition of claim 91 wherein the metathesized natural oil is made by reacting (a) one or more natural oils and/or natural oil derived unsaturated carboxylic acids and/or esters with (b) another olefinic compound in the presence of a metathesis catalyst.
94 . The composition of claim 91 wherein the metathesized natural oil is made by reacting a natural oil and/or natural oil derived unsaturated carboxylic acid and/or ester in the presence of a metathesis catalyst to form a first metathesized natural oil; and then reacting the first metathesized natural oil in a self-metathesis reaction to form another metathesized natural oil, or reacting the first metathesized natural oil in a cross-metathesis reaction with a natural oil and/or natural oil derived unsaturated carboxylic acid and/or ester to form another metathesized natural oil.
95 . The composition of claim 91 wherein the metathesized natural oil is formed in the presence of a metathesis catalyst, the metathesis catalyst comprising a metal carbene catalyst based upon ruthenium, molybdenum, osmium, chromium, rhenium, and/or tungsten.
96 . The composition of claim 91 wherein the metathesized natural oil is formed in the presence of a metathesis catalyst, the metathesis catalyst being represented by the following formula (I)
wherein:
M is ruthenium, molybdenum, osmium, chromium, rhenium, and/or tungsten;
L 1 , L 2 and L 3 are neutral electron donor ligands;
n is 0 or 1, such that L 3 may or may not be present;
m is 0, 1, or 2;
X 1 and X 2 are anionic ligands; and
R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups,
wherein any two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 can be taken together to form a cyclic group, and further wherein any one or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 may be attached to a support.
97 . The composition of claim 96 wherein M is Ru, W and/or Mo.
98 . The composition of claim 91 wherein the metathesized natural oil is formed in the presence of a metathesis catalyst, the metathesis catalyst being represented by the formula
wherein:
M is a Group 8 transition metal;
L 1 , L 2 and L 3 are neutral electron donor ligands;
n is 0 or 1, such that L 3 may or may not be present;
m is 0, 1, or 2;
X 1 and X 2 are anionic ligands; and
R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups,
wherein any two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 can be taken together to form a cyclic group, and further wherein any one or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 may be attached to a support;
X and Y are independently N, O, S, or P; p is zero when X is O or S; q is zero when Y is O or S; p is 1 when X is N or P; q is 1 when Y is N or P; and
Q 1 , Q 2 , Q 3 and Q 4 are independently linkers, and w, x, y and z are independently zero or 1.
99 . The composition of claim 91 wherein the metathesized natural oil is formed in the presence of a metathesis catalyst, the metathesis catalyst being represented by one or more of the following formulae
wherein:
L 1 is a neutral electron donor ligand;
X 1 and X 2 are independently anionic ligands; and
M is a Group 8 transition metal.
100 . The composition of claim 91 wherein the metathesized natural oil is formed in the presence of a metathesis catalyst, the metathesis catalyst being represented by one or more of the following formulae (VII), (VIII), (IX) or (X):
wherein:
M is a Group 8 transition metal;
L 1 , L 2 and L 3 are neutral electron donor ligands;
r and s are independently zero or 1;
t is an integer in the range from zero to 5;
X 1 and X 2 are anionic ligands; and
R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups,
wherein any two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 can be taken together to form a cyclic group, and further wherein any one or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 may be attached to a support;
Y is a non-coordinating anion; Z 1 and Z 2 are independently selected from —O—, —S—, —NR 2 —, —PR 2 —, —P(═O)R 2 —, —P(OR 2 )—, —P(═O)(OR 2 )—, —C(═O)—, —C(═O)O—, —OC(═O)—, —OC(═O)O—, —S(═O)—, and —S(═O) 2 —; and Z 3 is a cationic moiety.
101 . The composition of claim 91 wherein the metathesized natural oil is formed in the presence of a metathesis catalyst, the metathesis catalyst being represented by the formula
wherein:
X 1 and X 2 are anionic ligands;
L 1 is a neutral electron donor ligand;
R 1 is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups;
Y is a positively charged Group 15 or Group 16 element substituted with hydrogen, C 1 -C 12 hydrocarbyl, substituted C 1 -C 12 hydrocarbyl; heteroatom-containing C 1 -C 12 hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; and
Z − is a negatively charged counterion.
102 . The composition of claim 91 wherein the metathesized natural oil is formed in the presence of a metathesis catalyst, the metathesis catalyst being ruthenium (II) dichloro (3-methyl-1,2-butenylidene) bis(tricyclopentylphosphine); ruthenium (II) dichloro (3-methyl-1,2-butenylidene)bis(tricyclohexylphosphine); ruthenium (II) dichloro (phenylmethylene)bis(tricyclohexylphosphine); ruthenium (II) [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene) dichloro (phenylmethylene) (triphenylphosphine); ruthenium (II) dichloro (vinyl phenylmethylene)bis(tricyclohexylphosphine); ruthenium (II) dichloro (tricyclohexylphosphine) (o-isopropoxyphenylmethylene); and/or ruthenium (II) (1,3-bis-(2, 4, 6,-trimethylphenyl)-2-imidazolidinylidene) dichloro (phenylmethylene) (bis 3-bromopyridine).
103 . The composition of claim 91 wherein the metathesized natural oil is formed in the presence of a metathesis catalyst, the metathesis catalyst being represented by structures 12, 14 or 16, where Ph is phenyl, Mes is mesityl, and Cy is cyclohexyl:
104 . The composition of claim 91 wherein the metathesized natural oil is formed in the presence of a metathesis catalyst, the metathesis catalyst being represented by structures 18, 20, 22, 24, 26 or 28 where Ph is phenyl, Mes is mesityl, py is pyridyl, Cp is cyclopentyl and Cy is cyclohexyl:
105 . The composition of claim 91 wherein the metathesized natural oil is formed in the presence of a metathesis catalyst, the metathesis catalyst being represented by one or more of the following structures
wherein Ph represents phenyl, Cy represents cyclohexane, Me represents methyl, nBu represents n-butyl, i-Pr represents isopropyl, py represents pyridine (coordinated through the N atom), and Mes represents mesityl (i.e., 2,4,6-trimethylphenyl).
106 . The composition of claim 92 wherein the natural oil or natural oil derived unsaturated carboxylic acid and/or ester is partially hydrogenated prior to the reaction in the presence of the metathesis catalyst.
107 . The composition of claim 91 wherein the metathesized natural oil comprises from 1 to about 100 metathesis repeating groups.
108 . The composition of claim 91 wherein the metathesized natural oil comprises a metathesis dimer, metathesis trimer, metathesis tetramer, metathesis pentamer, metathesis hexamer, metathesis heptamer, metathesis octamer, metathesis nonamer, metathesis decamer, or a mixture of two or more thereof.
109 . The composition of claim 2 wherein the enophilic reagent reacts on the hydrocarbyl group.
110 . The composition of claim 4 wherein the enophilic reagent reacts on the backbone of the functionalized polymer.
111 . The composition of claim 2 wherein the enophilic reagent reacts in an ene reaction with one or more carbon-carbon double bonds in the hydrocarbyl group.
112 . The composition of claim 4 wherein the enophilic reagent reacts in an ene reaction with one or more carbon-carbon double bonds in the functionalized polymer.
113 . The composition of claim 2 wherein the enophilic reagent reacts with the carbon atoms of one or more carbon-carbon double bonds in the hydrocarbyl group.
114 . The composition of claim 4 wherein the enophilic reagent reacts with the carbon atoms of one or more carbon-carbon double bonds in the functionalized polymer.
115 . The composition of claim 2 wherein the enophilic reagent reacts with the functional group in the hydrocarbyl group.
116 . The composition of claim 4 wherein the enophilic reagent reacts with the functional group in the functionalized polymer.