SYNTHETIC LUBRICITY ADDITIVES FOR HYDROCARBON FUELS

Abstract

Lubricity additives for fuels compositions are provided which are hydrocarbyl-containing oxygenated polyamines according to Formula I:

##STR00001##

wherein one or more of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is a carbon- and oxygen-containing group including a hydrophobic hydrocarbyl portion.

Claims

1. A method for improving the lubricity of a fuel composition comprising: adding a composition comprising a compound of Formula I: ##STR00018## to a fuel composition, wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are independently selected from H, OH, alkyl, aryl, alkyl aryl, and aryl alkyl, optionally substituted, (CH.sub.2).sub.xNR.sup.5R.sup.6, and a carbon- and oxygen-containing group including one or more oxygen atoms in the form of (i) a hydroxyl group, (ii) an ether group, (iii) an ester group, or more than one of (i)-(iii), wherein at least one of R.sup.1-R.sup.4 is the carbon- and oxygen-containing group, wherein x is an integer in the range of 1-4, wherein y is an integer in the range of 1-11, 1-10 or 1-9, and wherein R.sup.5 and R.sup.6 have the same meaning as any one of R.sup.1-R.sup.4, optionally wherein the compound has a number of carbon atoms that is three times or greater than a number of nitrogen atoms in the compound, wherein the compound improves lubricity of the fuel composition.

2. The method of claim 1, wherein the number of carbon atoms is three, four, five, six, seven, eight, nine, or ten times greater than the number of nitrogen atoms, or the nitrogen atom to carbon atom ratio is in the range of 1:4 to 1:30, 1:5 to 1:25, or 1:6 to 1:20.

3. The method of claim 2, wherein the number of carbon atoms is four, five, six, seven, eight, nine, or ten times of greater than a number of oxygen atoms in the compound, or the oxygen atom to carbon atom ratio is in the range of 1:5 to 1:25 or 1:6 to 1:20.

4. The method of claim 1, wherein the compound has a nitrogen atom to oxygen atom ratio in the range of 1:5 to 5:1, 3:10 to 10:3, or 1:4 to 4:1.

5. The method of claim 1, wherein the compound has a molecular weight in the range of about 100 Da to about 2000 Da, about 150 Da to about 1800 Da, about 200 Da to about 1600 Da, or about 250 Da to about 1500 Da.

6. The method of claim 1 wherein the R.sup.1-R.sup.4 group(s) that are not either the carbon- and oxygen-containing group(s) or (CH.sub.2).sub.xNR.sup.5R.sup.6 are H.

7. The method of claim 1 wherein the compound is of Formula II: ##STR00019## wherein R.sup.1-R.sup.4 are independently selected from H, OH, alkyl, aryl, alkyl aryl, and aryl alkyl, and the carbon- and oxygen-containing group, wherein y is an integer in the range of 1-8, and wherein at least one of R.sup.1-R.sup.4 is the carbon- and oxygen-containing group.

8. The method of claim 1 wherein two, three, or four of R.sup.1-R.sup.4 are the carbon- and oxygen-containing groups.

9. The method of claim 8, wherein the carbon- and oxygen-containing groups are different based on (i) number of carbons, (ii) number of oxygens, or both (i) and (ii).

10. The method of claim 1 wherein the carbon- and oxygen-containing group(s) has an amount of carbon atoms in the range of 6-30, 8-24, 10-22, or 12-20.

11. The method of claim 1 wherein any of R.sup.1-R.sup.4 has the Formula (CR.sup.7.sub.2).sub.q(CHOH)R.sup.8, wherein R.sup.7 is independently selected from H and alkyl, wherein q is 0 (a covalent bond), or an integer in the range of 1-4, and R.sup.8 is selected from the group consisting of C6-C28 linear, branched, cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl.

12. The method of claim 11, wherein R.sup.7 is H; q is 2; and R.sup.8 is selected from the group consisting of C10-C22 linear, branched, cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl.

13. The method of claim 1 wherein any of R.sup.1-R.sup.4 has the Formula (CR.sup.9.sub.2).sub.q(CHOH)(R.sup.10O)R.sup.11, wherein R.sup.9 is independently selected from H and alkyl, q is 0 (a covalent bond) or an integer in the range of 1-4, preferably, 1 or 2, R.sup.10 is (CH.sub.2).sub.w, wherein w is 1, 2, or 3, and R.sup.11 is selected from the group consisting of C6-C28 linear, branched, cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl, optionally wherein R.sup.9 is H; q is 2; w is 1, and R.sup.11 is selected from the group consisting of C10-C22 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl.

14. The method of claim 1, wherein the compound of Formula I has an acid value of less than about 1.5, less than about 1.25, less than about 1, or less than about 0.75.

15. The method of claim 1 wherein the composition comprises a mixture of two or more different compounds of Formula I, wherein the compounds are different based on at least the number of nitrogen atoms in the compounds.

16. The method of claim 1, wherein the compound of Formula I is added to the fuel composition at a concentration in the range of about 30 ppm to about 1000 ppm, about 50 ppm to about 500 ppm, or about 75 ppm to about 300 ppm.

17. The method of claim 1, wherein the fuel composition comprises diesel fuel.

18. A fuel composition comprising a compound of Formula I: ##STR00020## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are independently selected from H, OH, alkyl, aryl, alkyl aryl, and aryl alkyl, optionally substituted, (CH.sub.2).sub.xNR.sup.5R.sup.6, and a carbon- and oxygen-containing group including one or more oxygen atoms in the form of (i) a hydroxyl group, (ii) an ether group, (iii) an ester group, or more than one of (i)-(iii), wherein at least one of R.sup.1-R.sup.4 is the carbon- and oxygen-containing group, wherein x is an integer in the range of 1-4, wherein y is an integer in the range of 1-11, 1-10 or 1-9, and wherein R.sup.5 and R.sup.6 have the same meaning as any one of R.sup.1-R.sup.4, optionally wherein the compound has a number of carbon atoms that is three times or greater than a number of nitrogen atoms in the compound.

19. A method for making an oxygenated polyamine fuel lubricity additive comprising: reacting a polyamine of Formula III: ##STR00021## wherein R.sup.12, R.sup.13, R.sup.14, and R.sup.15, are independently selected from H, OH, alkyl, aryl, alkyl aryl, and aryl alkyl, optionally substituted, wherein at least one of R.sup.12-R.sup.15 is H, wherein x is an integer in the range of 1-4, wherein y is an integer in the range of 1-11, 1-10, or 1-9, with an epoxide-containing compound having a number of carbons in the range of 6-30, 8-24, 10-22, or 12-20, to provide the oxygenated polyamine, optionally wherein the polyamine and the epoxide-containing compound are present in a molar ratio in the range of 1:1 to 1:6, optionally wherein the epoxide-containing compound has a single epoxide group or the epoxide-containing compound is a glycidyl ether compound, optionally wherein the epoxide-containing compound is of Formula IV: ##STR00022## wherein R.sup.16 is (CH.sub.2) or (CH.sub.2CH.sub.2), wherein R.sup.17 is a hydrocarbyl group, wherein R.sup.17 optionally has a number of carbons in the range of 6-28, 8-24, or 10-22 optionally wherein the epoxide-containing compound is of Formula V: ##STR00023## wherein R.sup.18 is (CH.sub.2) or (CH.sub.2CH.sub.2), wherein R.sup.19 is (CH.sub.2).sub.w, wherein w is an integer in the range of 1-3, optionally wherein R.sup.20 is a linear or branched alkyl group of having a number of carbons in the range of 6-24, 8-22, or 10-20.

20. A lubricity additive composition comprising the compound of Formula I of claim 1.

Description

DETAILED DESCRIPTION

[0020] Additional embodiments of the compounds, compositions, methods of the present disclosure are described below. The preceding summary of the present disclosure is not intended to describe each embodiment of the present invention. The details of one or more embodiments of the invention are also set forth in the description below. Other features, objects, and advantages of the invention will be apparent from the description and from the claims.

[0021] In particular, hydrocarbyl-containing oxygenated polyamines are described, such as those of Formula I and Formula II, which have a polyamine core and include one or more chemical groups which include an oxygen atom and carbon-containing hydrophobic group.

[0022] The hydrocarbyl-containing oxygenated polyamines can be used as lubricity compounds, can be present in additive compositions, and can be used in methods for improving lubricity in a fuel composition. In particular, the hydrocarbyl-containing oxygenated polyamines can be used as a diesel fuel lubricity additive composition, and in methods for improving the lubricity of a diesel fuel, such as ultra-low sulfur diesel (ULSD).

[0023] The terms comprising and including and the like are intended to be open-ended and non-limiting, and therefore do not exclude other features (e.g., another component(s), or another step(s) of a method) that are not specifically recited. For example, a fuel composition that comprises or includes the hydrocarbyl group-containing oxygenated polyamine and components of a hydrotreated fractional distillation of petroleum oil (e.g., petroleum diesel, like ULSD) may have one or more other component(s) in the fuel composition, such as other additives. Examples of other optional additives include dispersants, antioxidants, viscosity index modifiers, corrosion inhibitors, and the like.

[0024] Likewise, a method for forming a lubricated fuel composition can comprise or include a step of adding the hydrocarbyl group-containing oxygenated polyamines to petroleum diesel, like ULSD, and may also include one or more other steps that a performed before, during, after, the addition of the lubricity additive. Such additional steps can include the addition of one or more other components to the fuel, or performing one or more other treatment or refining steps to the fuel.

[0025] Compositions of the disclosure can include those recited compounds and optionally can include other components in the composition but in very small amounts (e.g., described in terms of a composition consisting essentially of the recited components). For example, a composition that consist essentially of a hydrocarbyl group-containing oxygenated polyamine may include one or more other additional component(s), but not in an amount that is greater than about 1% (wt), greater than about 0.5% (wt), greater than about 0.1% (wt), or greater than about 0.01% (wt), of the total composition. A composition that consists essentially of the hydrocarbyl group-containing oxygenated polyamine lubricity additive that is dissolved in a solvent, aside from the polyamine and solvent, can optionally include one or more other (e.g., solid) component(s) but in an amount less than about 1% (wt) of the total composition weight. In a composition consisting of the recited components there is no other measurable amount of component other than the recited component.

[0026] As used herein, the terms substantially and consisting essentially of modifying, for example, the type or quantity of an ingredient in a composition, a property, a measurable quantity, a method, a position, a value, or a range, employed in describing the embodiments of the disclosure, refers to a variation that does not affect the overall recited composition, property, quantity, method, position, value, or range thereof in a manner that negates an intended composition, property, quantity, method, position, value, or range. Examples of intended properties include, solely by way of nonlimiting examples thereof, dispersibility, stability, rate, solubility, and the like; intended values include weight of a component added, concentration of components added, and the like. The effect on methods that are modified include the effects caused by variations in type or amount of materials used in a process, variability in machine settings, the effects of ambient conditions on a process, and the like wherein the manner or degree of the effect does not negate one or more intended properties or results; and like proximate considerations. Where modified by the term substantially or consisting essentially of, the claims appended hereto include equivalents to these types and amounts of materials.

[0027] Optionally, compositions of the disclosure may be described as omitting certain components that are not relevant to the polyamine lubricity additive, or fuel compositions including the polyamine, such as omitting compounds that have no practical use or that provide no benefit for a fuel composition, or that would be detrimental if present in a fuel composition.

[0028] As used herein, the term about modifying, for example, the quantity of an ingredient in a composition, concentration, volume, process temperature, process time, yield, flow rate, pressure, and like values, and ranges thereof, employed in describing the embodiments of the disclosure, refers to variation in the numerical quantity that can occur, for example, through typical measuring and handling procedures used for making compounds, compositions, concentrates, or use formulations; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of starting materials or ingredients used to carry out the methods, and like proximate considerations. The term about also encompasses amounts that differ due to aging of a formulation with a particular initial concentration or mixture, and amounts that differ due to mixing or processing a formulation with a particular initial concentration or mixture. Where modified by the term about the claims appended hereto include equivalents to these quantities. Further, where about is employed to describe any range of values, for example about 1 to 5 the recitation means 1 to 5 and about 1 to about 5 and 1 to about 5 and about 1 to 5 unless specifically limited by context.

[0029] As used herein, the term optional or optionally means that the subsequently described object (e.g., compound), event (e.g., processing step), or circumstance may, but need not occur, and that the description includes instances where the object, event, or circumstance occurs and instances in which it does not.

[0030] The current description and appended claims may include identifiers, such as numerical, alphabetical, or alphanumeric identifiers to facilitate an understanding of claim features, such as steps within a process claim, components in a composition claim, or combinations thereof. For example, a claim may include features preceded by (a), (b), (c), etc., or (i), (ii), (iii), etc., but unless otherwise noted the alphabetical or numerical order does not imply that a particular step (e.g., (b)) occurs after another particular step (e.g., (a)) in the claimed process, or that a particular component in a composition (e.g., (ii)) is present in an amount greater than another particular component (e.g., (i)) in the claimed composition. Further, a process that comprises multiple steps (a), (b), (c), may include further steps (e.g., (d), (e), etc.) that are performed before, between, after, or any combination thereof, of any of the claimed steps. Where appropriate, a process having multiple steps may be described with the steps occurring in a particular order as dictated by the alphabetical or numerical order, or a composition having multiple components may be described with the components being present in amounts as dictated by the alphabetical or numerical order.

[0031] As used herein, the articles a, an and the refer to one or more of the object of the article.

[0032] Described herein include hydrocarbyl-containing oxygenated polyamines that are compounds of Formula I:

##STR00005##

[0033] In Formula I, at least one of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 includes a hydrocarbyl group and one or more oxygen atoms. The term hydrocarbyl group and hydrocarbyl are used to described carbon-containing chemical groups, as well-known to those skilled in the art. A hydrocarbyl group refers to a univalent chemical group formed by removing a hydrogen from a hydrocarbon. One or more of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 can include a hydrocarbyl group that is, for example, linear, branched, or cyclic, which can be saturated, partially saturated, or fully saturated. For example, hydrocarbyl groups can include linear alkyl, branched alkyl, or cyclic alkyl, aryl, aralkyl, and the like. Hydrocarbyl groups can include aliphatic groups such as substituted or unsubstituted alkyl or alkenyl, alicyclic groups, cycloalkyl and cycloalkenyl, aromatic groups, and aliphatic-, and alicyclic-substituted aromatic groups.

[0034] Substituted hydrocarbyl groups can optionally be used. As described herein, at least one of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 includes a hydrocarbyl group and one or more oxygen atoms, and the oxygen can be a part of one or more chemical group(s) that is substituted on the hydrocarbyl group, such as hydroxyl, which does not have another heteroatom. However, the hydrocarbyl groups can optionally be substituted with a group other than an oxygen-containing group like hydroxyl. If the hydrocarbyl group is substituted with a group other than an oxygen-containing group, the chemical nature of the non-oxygen substitutions (non-oxygen substituents) do not, or do not substantially, alter the hydrocarbon properties of the hydrocarbyl group. Exemplary substituents that are not hydrogen, carbon, or an oxygen-containing group include halo substituents, such as chloro and fluoro; mercapto, and alkylmercapto, as well as oxygen-containing groups that also include a non-oxygen heteroatom, like nitro, nitroso, and sulfoxy. Mixtures of different substituent groups can be used. In embodiments, a hydrocarbyl group can include three substituent groups, two substituent groups, or one substituent group. Preferably, the hydrocarbyl group has no substituent groups, or one substituent groups.

[0035] In the at least one of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 that includes a hydrocarbyl group and one or more oxygen atoms, the oxygen is in the form of a hydroxyl, ether, or ester group, or more than one of these types of groups. Preferably, at least one of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 includes one or more hydroxyl groups attached to one or more carbons of the hydrocarbyl group.

[0036] In the at least one of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 that includes a hydrocarbyl group and one or more oxygen atoms, the oxygen atom can be separated from the most proximal nitrogen of the polyamine portion to which it is attached to by a desired number of carbon atoms. For example, in embodiments, the oxygen atom is separated from the polyamine nitrogen by one carbon, by two carbons, by three carbons, by four carbons, or by five carbons. Preferably, the oxygen atom is separated from the most proximal nitrogen of the polyamine portion by one or two carbon atoms.

[0037] Also, in Formula I, x is an integer in the range of 1-4. As such, the hydrocarbyl-containing oxygenated polyamine can be one based on a polyamine such as polyethylene amine, polypropylene amine, or polybutylene amine. A polyamine used to form the compounds of Formula I can optionally be one derived from two or more different alkyleneamines, such as a mixture of two or more of ethyleneamine, propyleneamine, and butyleneamine.

[0038] Also, in Formula I, y is an integer in the range of 1-11, 1-10 or 1-9. Accordingly, a polyamine used to form the compounds of Formula I can be derived from a compound such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethyleneamine, hexaethyleneamine, heptaethyleneamine, octaethyleneamine, nonaethyleneamine, or decaethyleneamine; dipropyleneamine, tripropyleneamine, tetrapropyleneamine, pentapropyleneamine, hexapropyleneamine, heptapropyleneamine, octapropyleneamine, nonapropyleneamine, or decapropyleneamine; or dibutyleneamine, tributyleneamine, tetrabutyleneamine, pentabutyleneamine, hexabutyleneamine, heptabutyleneamine, octabutyleneamine, nonabutyleneamine, or decabutyleneamine. Optionally, such polyamines can be referred to as alkyleneamine oligomers.

[0039] Compositions including compounds of Formula I can be prepared using as staring materials a mixture of two or more different alkyleneamines, such as two or more alkylamines that are of different y integers (lengths), or two or more alkylamines having different chemistries (such as a mixture of polyethyleneamine and polypropyleneamine).

[0040] In Formula I, R.sup.5 and R.sup.6 have the same meaning as R.sup.1-R.sup.4. Also compounds of Formula I may have a number of carbon atoms that is three times or greater than a number of nitrogen atoms in the compound. For example, if tetraethylenepentamine (C.sub.8H.sub.23N.sub.5) is used as the starting polyamine, the chemical modification to provide R groups adds at least seven (7) carbon atoms, in one or more R groups (C=8+7?N=5?3).

[0041] In embodiments the number of carbon atoms is four, five, six, seven, eight, nine, or ten times greater than the number of nitrogen atoms. For example, if tetraethylenepentamine (C.sub.8H.sub.23N.sub.5) is used as the starting polyamine, the chemical modification to provide R groups adds at least 12, 17, 22, 27, 32, 37, or 42 carbon atoms in one or more R groups. In embodiments the number of carbon atoms is in the range of 3-10, 4-9, or 5-8 times greater than the number of nitrogen atoms in the compound.

[0042] Optionally, compounds of Formula I can be described with regards to the ratio between nitrogen atoms and carbon atoms. In embodiments, the nitrogen atom to carbon atom ratio is in the range of 1:4 to 1:30, 1:5 to 1:25, or 1:6 to 1:20.

[0043] Optionally, compounds of Formula I can be described with regards to the ratio of carbon atoms to oxygen atoms. In some embodiments, the number of carbon atoms is five, six, seven, eight, nine, or ten times or greater than a number of oxygen atoms in the compound. In some embodiments, the oxygen atom to carbon atom ratio is in the range of 1:5 to 1:25, or 1:6 to 1:20.

[0044] Optionally, compounds of Formula I can be described with regards to the ratio of nitrogen atoms to oxygen atoms. In some embodiments, the compound has a nitrogen atom to oxygen atom ratio in the range of 1:5 to 5:1, 3:10 to 10:3, or 1:4 to 4:1.

[0045] Optionally, compounds of Formula I can be described with regards to their molecular weight. In some embodiments, compounds of Formula I have a molecular weight of at least about 100 Da, of at least about 150 Da, of at least about 200 Da, of at least about 250 Da, or of at least about 400 Da, such as in the range of about 100 Da to 2000 Da, about 150 Da to about 1800 Da, about 200 Da to about 1600 Da, or about 250 Da to about 1500 Da.

[0046] As noted herein, in Formula I, at least one of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 includes a hydrocarbyl group and one or more oxygen atoms. In embodiments, two, three, four, or five of R.sup.1-R.sup.4 are the carbon- and oxygen-containing groups. If the compound of Formula I includes two or more of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 being carbon- and oxygen-containing groups, then these two or more groups can be the same, or these two or more can be different. If two or more of R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are different, then the difference can be with regards to the carbon content, the chemical structure, or the oxygen content in these groups.

[0047] As noted herein, in Formula I, at least one of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 includes a hydrocarbyl group and one or more oxygen atoms, and in embodiments an amount of carbon atoms in the range of 6-30, 8-24, 10-22, or 12-20.

[0048] In embodiments, any one or more of R.sup.1-R.sup.4 has the Formula (CR.sup.7.sub.2).sub.q(CHOH)R.sup.8, wherein R.sup.7 is independently selected from H and alkyl, wherein q is 0 (a covalent bond), or an integer in the range of 1-4, and R.sup.8 is selected from the group consisting of C6-C28 saturated, partially saturated, or unsaturated, linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl, optionally substituted with a group including a non-oxygen atom. In some more specific embodiments, R.sup.7 is H; q is 2; and R.sup.8 is selected from the group consisting of C10-C22 linear, branched, cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl.

[0049] In embodiments, one or more of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are selected from:

##STR00006##

[0050] In other embodiments any one or more of R.sup.1-R.sup.4 has the Formula (CR.sup.9.sub.2).sub.q(CHOH)(R.sup.10O)R.sup.11, wherein R.sup.9 is independently selected from H and alkyl, q is 0 (a covalent bond) or an integer in the range of 1-4, preferably, 1 or 2, R.sup.10 is (CH.sub.2).sub.w, wherein w is 1, 2, or 3, and R.sup.11 is selected from the group consisting of C6-C28 saturated, partially saturated, or unsaturated, linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl, optionally substituted with a group including a non-oxygen atom. In some more specific embodiments, R.sup.9 is H; q is 2; w is 1, and R.sup.11 is selected from the group consisting of C10-C22 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl.

[0051] In embodiments, one or more of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are selected from:

##STR00007##

[0052] For compounds of Formula I, in embodiments, any one or more of the R.sup.1-R.sup.4 group(s) that are not groups having the hydrocarbyl group and one or more oxygen atoms, or (CH.sub.2).sub.xNR.sup.5R.sup.6, can be H.

[0053] Formula I also encompasses hydrocarbyl-containing oxygenated polyamines of Formula II, which are based on a polyethyleneamine, as follows:

##STR00008##

[0054] In Formula II, R.sup.1-R.sup.4 are independently selected from H, OH, alkyl, aryl, alkyl aryl, and aryl alkyl, and the hydrocarbyl- and oxygen-containing group, wherein y is an integer in the range of 1-10, and wherein at least one of R.sup.1-R.sup.4 is the hydrocarbyl- and oxygen-containing group. In more specific aspects of Formula II, the integer y and the R.sup.1-R.sup.4 groups as described with reference to Formula I herein can be applied to Formula II.

[0055] In some embodiments the disclosure provides a composition comprising a mixture of two or more compounds of Formula I or Formula II. For example, a composition can include a mixture of two or more hydrocarbyl-containing oxygenated polyamines which are different based on at least the number of nitrogen atoms in the compounds. For example, the hydrocarbyl-containing oxygenated polyamines can be prepared from a starting composition with a mixture of polyamines of different lengths, such as a mixture of polyamines having two of more polyamines that have 5, 6, 7, 8, or 9 nitrogen atoms.

[0056] For example, a composition such as ETHYLENEAMINE E-100? (Huntsman) which is a mixture of tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), hexaethyleneheptamine (HEHA), and higher molecular weight products, and includes various linear, cyclic, and branched products with a number-average molecular weight of 250-300 g/mole, can be used to prepare hydrocarbyl-containing oxygenated polyamines of the disclosure. The resulting product will include a mixture of compounds with different polyamine lengths and therefore different molecular weights.

[0057] Beneficially, hydrocarbyl-containing oxygenated polyamines of the disclosure show a low acid value (acid number). Low acid values are desirable in a fuel composition such as diesel because it reduces the likelihood of additive breakdown, and therefore fuel Formulations with additives, including those lubricity additives of the disclosure, can maintain desirable properties over longer periods of storage. In embodiments, hydrocarbyl-containing oxygenated polyamines of the disclosure have an acid value of less than about 1.5, less than about 1.25, less than about 1, or less than about 0.75. Exemplary acid values are in the range of about 0.25 to about 1.5, about 0.4 to about 1.4, or about 0.5 to about 1.25.

[0058] In other aspects, the disclosure provides a method for making a hydrocarbyl-containing oxygenated polyamine fuel lubricity additive. As a general matter, the method involves reactive a polyamine, or polyamine derivative, with an epoxide-containing compound that includes a hydrocarbyl group. For example, in one mode of practice, the method includes a step of reacting a polyamine of Formula III:

##STR00009##

wherein R.sup.12, R.sup.13, R.sup.14, and R.sup.15, are independently selected from H, OH, alkyl, aryl, alkyl aryl, and aryl alkyl, optionally including substitution, wherein at least one of R.sup.12-R.sup.15 is H, wherein x is an integer in the range of 1-4, wherein y is an integer in the range of 1-10 or 1-9, with an epoxide-containing compound that includes a hydrocarbyl group to provide the hydrocarbyl-containing oxygenated polyamine product. The hydrocarbyl group can have a number of carbons in the range of 6-30, 8-24, 10-22, or 12-20. In aspects, the epoxide-containing compound has a single epoxide group or the epoxide-containing compound is a glycidyl ether compound.

[0059] Polyamine reactants include linear or branched polyethyleneamine, polypropyleneamine, and polybutyleneamine, including polyamines species such as ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), propylenediamine, dipropylenetriamine, tripropylenetetramine, N-3-aminopropyl ethylenediamine (Am3), N,N-bis(3-aminopropyl)ethylenediamine (Am4), N,N,N-tris(3-aminopropyl)ethylene-diamine (Am5); N-3-aminopropyl-1,3-diaminopropane, N,N-bis(3-aminopropyl)-1,3-diaminopropane, N,N,N-tris(3-aminopropyl)-1,3-diaminopropane, putrescine (butane-1,4-diamine), cadaverine (Pentane-1,5-diamine), spermidine (N.sup.1-(3-Aminopropyl)butane-1,4-diamine), spermine (N,N-bis(3-aminopropyl)butane-1,4-diamine), thermospermine (N-[3-(3-aminopropylamino)propyl]butane-1,4-diamine), caldopentamine (N-[3-[3-(3-aminopropylamino)propylamino]propyl]propane-1,3-diamine), and caldohexamine (N-[3-[3-[3-(3-aminopropylamino)propylamino]propyl-amino]propyl]propane-1,3-diamine), tris(3-aminopropyl)amine.

[0060] Epoxide-containing reactants include oxirane- and oxitane-containing reactants, such as those according to Formula IV:

##STR00010##

wherein R.sup.16 is (CH.sub.2) or (CH.sub.2CH.sub.2), wherein R.sup.17 is a hydrocarbyl group. In embodiments R.sup.17 is a linear or branched alkyl group of having a number of carbons in the range of 6-28, 8-24, or 10-22. Exemplary reactive compounds are 1,2-epoxyalkanes such as the species of 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, and 1,2-epoxyoctadecane.

[0061] In some modes of practice, the oxirane-containing reactant is of Formula V:

##STR00011##

wherein R.sup.18 is (CH.sub.2) or (CH.sub.2CH.sub.2), wherein R.sup.19 is (CH.sub.2).sub.w, wherein w is an integer in the range of 1-3, and wherein R.sup.20 is a linear or branched alkyl group of having a number of carbons in the range of 6-24, 8-22, or 10-20. Exemplary reactive compounds are C8-C10 alkyl glycidyl ethers and C12-C14 alkyl glycidyl ethers.

[0062] In some cases, the polyamine reactant includes hydrogen atoms on all of the R.sup.12-R.sup.15 groups. These active hydrogen groups are reactive with the epoxide group of the hydrocarbyl-containing reactant. A total number of active hydrogens can be determined on the polyamine reactant. Next, a molar ratio of the epoxide- and hydrocarbyl-containing reactant to the polyamine reactant can be chosen to provide a desired number of R.sup.12-R.sup.15 groups that become derivatized to form a compound of Formula I that includes R groups containing oxygen, such as in the form of a hydroxyl group, and the hydrocarbyl group.

[0063] In some embodiments, the reaction uses a molar ratio of about 1:1 polyamine reactant to epoxide- and hydrocarbyl-containing reactant, to provide a hydrocarbyl-containing oxygenated polyamines product with a single R group. In some embodiments, the reaction uses a molar ratio of about 1:2, uses a molar ratio of about 1:3, uses a molar ratio of about 1:4, or uses a molar ratio of about 1:5 polyamine reactant to epoxide- and hydrocarbyl-containing reactant, to provide a hydrocarbyl-containing oxygenated polyamines product with two, three, four, or five R groups, respectively. In embodiments of the below formula wherein k is 10, the maximum number of substituted R groups can be 14, meaning up to a 1:14 ratio of polyamine reactant to epoxide- and hydrocarbyl-containing reactant can be used for forming compounds of the disclosure (e.g., in Formula I herein R.sup.3 can be repeated up to 11 times, and therefore up to 14 of groups R.sup.1-R.sup.4 can be carbon- and oxygen-containing groups, such as described herein).

[0064] An exemplary reaction scheme (Scheme 1) is shown below:

##STR00012##

Wherein

[0065] R=H and/or

##STR00013## [0066] k=Integer of 1-10 [0067] X is (CH.sub.2O).sub.nR1, n=0,1 [0068] R1 is linear or branched C8-C30 alkylene group

[0069] Exemplary compounds can be formed having the structures as shown in Table 1 below:

TABLE-US-00001 TABLE 1 Structure [00014] 1,2-Epoxyhexadecane-PEHA (1:3 adduct) [00015] 1,2-Epoxydodecane-PEHA (1:2 adduct) [00016] 1,2-Epoxytetradecane-TEPA (1:3 adduct) [00017] 1,2-Epoxyhexadecane-PEHA (1:4 adduct)

[0070] As shown, for many hydrocarbyl-containing oxygenated polyamine products formed only a portion of the active hydrogens of the polyamine are replaced by R groups. Generally, about 7.5% or greater, 10% or greater, 12.5% or greater, 15% or greater, 17.5% or greater, 20% or greater, 22.5% or greater, or 25% or greater of the active hydrogens are replaced by R groups, and generally less than 75%, less than 65%, less than 55%, and less than 50% of the active hydrogens are replaced by R groups, or an amount of active hydrogens are replaced in a range according to any of the % values herein described (e.g., 7.5%-75%, 7.5%-65%, 7.5%-55%, 10%-75%, 10%-65%, 10%-55%, etc.).

[0071] In some cases, the polyamine reactant includes an alkyl, aryl, alkyl aryl, and aryl alkyl group, optionally substituted, on one or more, but not all of R.sup.12-R.sup.15. For these types of polyamine reactants, there is at least one alkyl, etc., group and at least one active hydrogen, and preferably multiple active hydrogens, or more active hydrogens than alkyl, etc, groups. Exemplary reactants of this type include alkylated polyamines such as described in US2009/0029175, which are formed by reacting a polyamine reactant, such as described herein, with an C1-C10 alkylated aldehyde or ketone, or an alkyl halide.

[0072] Reaction can be carried out for a time and temperature sufficient to prepare the hydrocarbyl-containing oxygenated polyamine product. For example, reaction times and temperatures and times may be in the range of about 100? C. to about 160? C., or about 120? C. to about 140? C., and for about 1 to 6 hours, or for about 2 to 4 hours.

[0073] Reactions can be carried out either in bulk (no solvent, i.e., neat) or in a suitable solvent, such as heavy aromatic naphtha (HAN). Other types of solvents such as low molecular weight organic liquids like halogenated organic solvents, such as methylchloroform, 1,1,2-trichloro-1,2,2-trifluoroethane, trichloroethylene, and trifluorotoluene; aromatic solvents, such as benzene, toluene, and xylene; aliphatic and alicyclic hydrocarbons, such as hexane, heptane, and cyclohexane; ethers, such as diethyl ether, diisopropyl ether, and tetrahydrofuran; esters, such as ethyl acetate and butyl acetate; alcohols, such as ethanol and isopropyl alcohol; ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; sulfoxides, such as dimethyl sulfoxide; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, can be used.

[0074] The hydrocarbyl-containing oxygenated polyamines can be in form of a stock or concentrate composition for addition to a fuel composition, such as USDL. The stock composition can be in neat form with essentially no, or no measureable other component (e.g., no solvent). Alternatively, the polyamine product can be in the form of a concentrate, such as where the hydrocarbyl-containing oxygenated polyamine is the predominant (i.e., >50% by weight) component in the stock composition, with the other component(s) being a solvent or solvent mixture compatible with the hydrocarbyl-containing oxygenated polyamine. Accordingly, the disclosure also provides a lubricity additive composition including the compound of Formula I, or a compound prepared according to the method of as described herein, and a fuel-compatible diluent.

[0075] If the hydrocarbyl-containing oxygenated polyamine is in a gel or solid form at room temperature in the absence of solvent, typically a solvent will be added to solubilize the compound. Small volumes of solvent may be used in these cases, such as less than 25%, less than 20%, less than 15%, or less than 10% by weight, and wherein the concentrate is stable during prolonged storage at temperatures below room temperature.

[0076] In addition to the hydrocarbyl-containing oxygenated polyamine, compositions of the disclosure (e.g., stock compositions, diluted compositions, fuel compositions, such as diesel fuel) may optionally include one or more additional components. Such optional additional compounds can include corrosion inhibitors, solvents, de-emulsifiers, amine stabilizers, dispersants, antioxidants, combustion improvers, cold flow improvers, pour point depressants, heat stabilizers, cetane improvers, conductivity improvers, metal deactivators, marker dyes, organic nitrate ignition accelerators, and other components useful for fuel compositions. In addition to the hydrocarbyl-containing oxygenated polyamine lubricity improver, the other optional additive(s) can be present in the fuel composition in amounts sufficient to provide effective additive properties.

[0077] In some embodiments, the hydrocarbyl-containing oxygenated polyamine lubricity enhancer is added to a petroleum product that is or derived from a crude oil, a reduced crude oil, a heavy oil, a bitumen, a coker charge, a hydrotreater influent, a hydrotreater effluent, a flashed crude, a light cycle oil, or a diesel or naphtha refinery stream. The hydrocarbyl-containing oxygenated polyamine lubricity enhancer can be added to naphtha products, such as diesel fuel, more specifically described herein. A diesel fuel Formulation can be one that has particular specifications and that complies with diesel fuel standards, such as for example EN 590 (Europe) or ASTM D975 (USA).

[0078] The hydrocarbyl-containing oxygenated polyamine lubricity enhancer can be present in a fuel composition in an amount suitable to provide lubricity to the fuel composition. For example, the polyamine can be present at a concentration of 30 ppm (parts per million by weight) or greater, 50 ppm or greater, 75 ppm or greater, 100 ppm or greater, 125 ppm or greater, or 150 ppm or greater. The polyamine can be present at a concentration of up to 1000 ppm, up to 900 ppm, up to 800 ppm, up to 700 ppm, up to 600 ppm, up to 500 ppm, up to 400 ppm, or up to 300 ppm. The polyamine can be present in an amount of in a range according to any of the ppm values herein described (e.g., 50 ppm to 1000 ppm, 50 ppm to 800 ppm, 50 ppm to 500 ppm, 75 ppm to 1000 ppm, 75 ppm to 800 ppm, 75 ppm to 500 ppm, etc.).

[0079] An additives composition including the hydrocarbyl-containing oxygenated polyamine lubricity enhancer described herein, and optional components used in Formulating the fuels, can be blended into a base diesel fuel individually, or in various sub-combinations. In some embodiments, additive components including the hydrocarbyl-containing oxygenated polyamine lubricity enhancer can be blended into the diesel fuel using a package composition, wherein the components therein are mutually compatible, and therefore provide a convenient way of including additives to the fuel. In some embodiments, the additive is prepared, packaged, and sold separately from diesel fuel, such as would be the case for when the additive is in a concentrated form. An additive composition, e.g., a concentrate including the hydrocarbyl-containing oxygenated polyamine lubricity enhancer, can be blended into the diesel fuel by a user. In other cases, the additive composition can be added to diesel fuel at a terminal location, such as where large quantities of fuel from a pipeline distribution system are stored.

[0080] In embodiments, the hydrocarbyl-containing oxygenated polyamines can be used in a wide variety of diesel fuel applications. For example, the polyamine lubricants of the disclosure can be used for diesel fuels for vehicles such as automobiles, trucks, construction equipment, military vehicles and equipment, aircraft including planes and helicopters, etc. (e.g., ambulatory diesel engines). The polyamine lubricants of the disclosure can also be used for stationary diesel engines, such as those used in pumping stations and engines for electrical power generation installations.

[0081] Lubricity is a measure of a substance's ability to reduce the friction and wear between surfaces which are in relative motion. The lubricity of a fuel formulation can be assessed by any suitable method, such as one that allows assessment of wear scar produced on an oscillating ball from contact with a stationary plate while immersed in the formulation that includes the lubricity enhancer to be tested. More specifically, the ability of a compound to provide lubricity to a fuel composition can be measured by wear scar diameter (WSD) analysis, using standard test method, such as ASTM D 6079, or the standard test method ISO 12156 measuring HFRR (high friction reciprocating rig) wear scar. In such tests measuring the extent of wearing, the test substance undergoes wearing because of friction. WSD is thus a measure of the fluid lubricity, and the lower the WSD value, the better lubricity the compound provides. The formulation may have a lubricity such that it gives a HFRR (high friction reciprocating rig) wear scar result, according to the standard test method ISO 12156, of 550 um or less, preferably 500 um or less, or more preferably 460 um or less.

[0082] Improved or enhanced lubricity of a formulation with the hydrocarbyl-containing oxygenated polyamine lubricity enhancer may be understood by a lower degree of wear scar, or of other friction-induced damage, in two relatively-moving components which are exposed to the compound. The inventive hydrocarbyl-containing oxygenated polyamines of the disclosure may be used to achieve any degree of improvement in the lubricity of a fuel formulation, and/or for the purpose of achieving a desired target lubricity, for example a target set by an applicable current standard such as EN 590. With regards to lubricity and reducing wear, the hydrocarbyl-containing oxygenated polyamine can show an improvement as expressed by a certain percentage of improvement as calculated by subtracting the wear number from a composition with hydrocarbyl-containing oxygenated polyamine from the wear number from a composition with no lubricity enhancer, and then dividing the result by the wear number from a composition with no enhancer (e.g., 558?408=150, 150/558=26.9% improvement in lubricity). In embodiments, addition of the hydrocarbyl-containing oxygenated polyamines provides an improvement in lubricity of greater than 5%, greater than 10%, greater than 15%, greater than 20%, greater than 25%, or greater than 30%, such as up to 35%, for example in the range of 5%-35%, or 10%-35%, as compared to a composition with no lubricity enhancer.

[0083] Unless otherwise noted, all reagents were obtained or are available from Aldrich Chemical Co., Milwaukee, WI, (Aldrich) or may be synthesized by known methods. All parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, unless noted otherwise. The terms weight %, % by weight, and wt % are used interchangeably.

[0084] Various modifications and alterations of this disclosure will become apparent to those skilled in the art without departing from the scope and principles of this disclosure, and it should be understood that this disclosure is not to be unduly limited to the illustrative embodiments set forth hereinabove. Objects and advantages of this disclosure are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure.

EXAMPLES

[0085] Polyamine-hydrophobic epoxide adducts were synthesized as lubricity improvers for ULSD. The generic synthesis reaction for preparation of such amine-epoxide adduct chemistries is shown in Scheme 1.

[0086] The amine-epoxide adducts (III) were conveniently prepared by reacting a polyamine (I) with a hydrophobic epoxide (II) at 120-140? C. for 2-4 h. Reactions were carried out either in bulk (no solvent) or heavy aromatic naphtha (HAN) as solvent.

[0087] Lubricity Performance Data (HFRR: High Frequency Reciprocating Rig, ISO 12156, ASTM D6079): The results are given in the Table 2 below. The data show that some of the amine-epoxide adduct chemistries show at least equivalent or better performance compared to the incumbent chemistry (EC5725A, wear scar=397 um).

TABLE-US-00002 TABLE 2 Wear Scar S. No Sample ID Amine Epoxide Amine:Epoxide (um) 8606-24 Diethylenetriamine 1,2-Epoxyhexadecane 1:3 moles 413 1. 8275-80 Diethylenetriamine C8-C10 alkyl glycidyl ether 1:5 moles 390 2. 8606-02 Diethylenetriamine C12-C14 alkyl glycidyl ether 1:3 moles 408 8606-33 Tetraethylenepentamine 1,2-Epoxytetradecane 1:3 moles 440 8606-34 Tetraethylenepentamine 1,2-Epoxytetradecane 1:4 moles 418 3. 8606-41 Tetraethylenepentamine 1,2-Epoxyhexadecane 1:3 moles 401 8606-40 Tetraethylenepentamine 1,2-Epoxyhexadecane 1:4 moles 442 4. 8606-99 Tetraethylenepentamine C12-C14 alkyl glycidyl ether 1:4 moles 514 5. 8606-100 Tetraethylenepentamine C12-C14 alkyl glycidyl ether 1:5 moles 457 6. 8511-35 Ethyleneamine E-100 C12-C14 alkyl glycidyl ether 1:1 mole 490 7. 8511-42 Pentaethylenehexamine C12-C14 alkyl glycidyl ether 1:1 mole 524 8. 8511-41 Pentaethylenehexamine C12-C14 alkyl glycidyl ether 1:2 moles 530 9. 8511-94 Pentaethylenehexamine C12-C14 alkyl glycidyl ether 1:3 moles 414 10. 8511-95 Pentaethylenehexamine C12-C14 alkyl glycidyl ether 1:4 moles 401 11. 8606-22 Pentaethylenehexamine 1,2-Epoxydodecane 1:2 moles 414 12. 8606-42 Pentaethylenehexamine 1,2-Epoxytetradecane 1:2 moles 389 8606-46 Pentaethylenehexamine 1,2-Epoxyhexadecane 1:2 moles 417 8606-47 Pentaethylenehexamine 1,2-Epoxyhexadecane 1:3 moles 370 13. 8606-48 Pentaethylenehexamine 1,2-Epoxyhexadecane 1:4 moles 415 14. EC5725A 397 Blank 558

[0088] Acid Number Data (Selected): The results are given in the Table 3 below. The data show that amine-epoxide adduct chemistries show low acid number values.

TABLE-US-00003 TABLE 3 Acid Number S. No Sample ID Amine Epoxide Amine:Epoxide (mg KOH/g) 1. 8275-80 Diethylenetriamine C8-C10 alkyl glycidyl ether 1:5 moles 1.30 2 8511-42 Pentaethylenehexamine C12-C14 alkyl glycidyl ether 1:1 mole 0.67 3. 8511-41 Pentaethylenehexamine C12-C14 alkyl glycidyl ether 1:2 moles 0.64 4. 8511-95 Pentaethylenehexamine C12-C14 alkyl glycidyl ether 1:4 moles 0.59 5. 8606-22 Pentaethylenehexamine 1,2-Epoxydodecane 1:2 moles 1.20