Synthetic lubricity additives for hydrocarbon fuels
Lubricity additives for fuels compositions are provided which are hydrocarbyl-containing oxygenated polyamines according to Formula I: wherein one or more of —R 1 , —R 2 , —R 3 , and —R 4 is a carbon- and oxygen-containing group including a hydrophobic hydrocarbyl portion.
1. A method for improving the lubricity of a fuel composition comprising:
adding a composition comprising a compound of Formula I:
to a fuel composition,
wherein —R 1 , —R 2 , —R 3 , and —R 4 , are independently selected from—H, —OH, alkyl, aryl, alkyl aryl, and aryl alkyl, optionally substituted, —(CH 2 ) x NR 5 R 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 1 -R 4 is the carbon- and oxygen-containing group, and the carbon- and oxygen-containing group has a C6-C30 linear, branched, cyclic alkyl, aryl, alkyl-aryl, or aryl-alkyl terminal portion, wherein x is an integer in the range of 1-4, wherein y is an integer in the range of 1-11, and wherein R 5 and R 6 have the same meaning as any one of R 1 -R 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 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.
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.
4. The method of claim 1 , wherein the compound has a number of nitrogen atoms in the range of 3-12, and a nitrogen atom to oxygen atom ratio in the range of 1:5 to 5:1.
5. The method of claim 1 , wherein the compound has a molecular weight in the range of about 100 Da to about 2000 Da.
6. The method of claim 1 wherein the R 1 -R 4 group(s) that are not either the carbon- and oxygen-containing group(s) or —(CH 2 ) x NR 5 R 6 are —H.
7. The method of claim 1 wherein the compound is of Formula II:
wherein R 1 -R 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 1 -R 4 is the carbon- and oxygen-containing group.
8. The method of claim 1 wherein two, three, or four of R 1 -R 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.
11. The method of claim 1 wherein any of R 1 -R 4 has the Formula-(CR 7 2 ) q (CHOH)R 8 , wherein R 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 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 7 is —H; q is 2; and R 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 1 -R 4 has the Formula —(CR 9 2 ) q (CHOH)(R 10 O)R 11 , wherein R 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 10 is (CH 2 ) w —, wherein w is 1, 2, or 3, and R 11 is selected from the group consisting of C6-C28 linear, branched, cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl, optionally wherein R 9 is —H; q is 2; w is 1, and R 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.
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.
17. The method of claim 1 , wherein the fuel composition comprises diesel fuel.
18. A fuel composition comprising a compound of Formula I:
wherein —R 1 , —R 2 , and —R 3 are independently selected from —H, —OH, alkyl, aryl, alkyl aryl, and aryl alkyl, optionally substituted, —(CH 2 ) x NR 5 R 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), and the carbon- and oxygen-containing group has a C6-C30 linear, branched, cyclic alkyl, aryl, alkyl-aryl, or aryl-alkyl terminal portion, wherein at least one of R 1 -R 4 is the carbon- and oxygen-containing group, and wherein —R 4 is —(CH 2 ) x NR 5 R 6 , wherein x is an integer in the range of 1-4, wherein y is an integer in the range of 1-11, and wherein R 5 and R 6 have the same meaning as any one of R 1 -R 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:
wherein —R 12 , —R 13 , —R 14 , and —R 15 , are independently selected from —H, —OH, alkyl, aryl, alkyl aryl, and aryl alkyl, optionally substituted, wherein at least one of R 12 -R 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, with
an epoxide-containing compound having a number of carbons in the range of 6-30,
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:
wherein R 16 is —(CH 2 )— or —(CH 2 CH 2 )—, wherein R 17 is a hydrocarbyl group, wherein R 17 optionally has a number of carbons in the range of 6-28,
optionally wherein the epoxide-containing compound is of Formula V:
wherein R 18 is —(CH 2 )— or —(CH 2 CH 2 )—, wherein R 19 is —(CH 2 ) w —, wherein w is an integer in the range of 1-3, optionally wherein R 20 is a linear or branched alkyl group of having a number of carbons in the range of 6-24.
20. A lubricity additive composition comprising the compound of Formula I of claim 1 .