Mineral oils with improved conductivity and cold flowability
View Patent ↗The invention provides compositions comprising at least one alkylphenol-aldehyde resin (constituent I) and, based on the alkylphenol resin, from 0.005 to 10% by weight of at least one oil-soluble organic ammonium sulfonate (constituent II).
1. A mineral oil distillate having a sulfur content of 350 ppm or less, which comprises from 5 to 500 ppm of at least one alkylphenol-aldehyde resin (constituent I) and from 0.001 to 10 ppm of at least one oil-soluble organic ammonium sulfonate (constituent II), wherein the one alkylphenol-aldehyde resin has a repeating structural unit of the formula
where R 5 is C 1 -C 200 -alkyl or -alkenyl and n is from 2 to 100.
2. The mineral oil distillate of claim 1 , wherein the aldehyde which is condensed to form the at least one alkylphenol-aldehyde resin has from 1 to 12 carbon atoms.
3. The mineral oil distillate of claim 1 , wherein the at least one alkylphenol-aldehyde resin has an alkyl group with from 1 to 200 carbon atoms.
4. The mineral oil distillate of claim 1 , wherein the at least one alkylphenol-aldehyde resin has a molecular weight of from 400 to 20 000 g/mol.
5. The mineral oil distillate of claim 1 , wherein the at least one oil-soluble organic ammonium sulfonate is prepared from an oil soluble sulfonic acid having at least one sulfonic acid group and at least one saturated or unsaturated radical selected from the group consisting of a linear, a branched, a cyclic hydrocarbon radical, and mixtures thereof having from 1 to 40 carbon atoms.
6. The mineral oil distillate of claim 1 , wherein the at least one oil-soluble organic ammonium sulfonate is prepared from an oil-soluble amine of the general formulae
NR 1 R 2 R 3 or NR 1 R 2 —[(CH 2 ) n —NR 2 ] m R 3
or mixtures thereof, where R 1 is an alkyl radical having from 1 to 24 carbon atoms or an alkenyl radical having from 2 to 24 carbon atoms, R 2 and R 3 are each independently H or as defined for R 1 , n is from 2 to 6 and m is from 1 to 6.
7. The mineral oil distillate of claim 1 , further comprising a copolymer comprising as monomers ethylene and from 6 to 21 mol % of a compound selected from the group consisting of a vinyl ester, an acrylic ester, a methacrylic ester, an alkyl vinyl ester, and mixtures thereof, and optionally an alkene.
8. The mineral oil distillate of claim 1 , further comprising a reaction product of a compound of the formula NR 6 R 7 R 8 , where R 6 , R 7 and R 8 may be the same or different and at least one of these groups is C 8 -C 36 -alkyl, C 6 -C 36 -cycloalkyl, C 8 -C 36 -alkenyl, and the remaining groups are either hydrogen, C 1 -C 36 -alkyl, C 2 -C 36 -alkenyl, cyclohexyl, or a group of the formulae -(A-O) x -E or —(CH 2 ) n —NYZ, where A is an ethyl or propyl group, x is from 1 to 50, E=H, C 1 -C 30 -alkyl, C 5 -C 12 -cycloalkyl or C 6 -C 30 -aryl, and n=2, 3 or 4, and Y and Z are each independently H, C 1 -C 30 -alkyl or (A-O) x with compounds which have a functional group of the formula
>C═O.
9. The mineral oil distillate of claim 1 , wherein said distillate further comprises a comb polymer of the formula
where
A is R′, COOR′, OCOR′, R″-COOR′, OR′;
D is H, CH 3 , A or R″;
E is H, A;
G is H, R″, R″-COOR′, an aryl radical or a heterocyclic radical;
M is H, COOR″, OCOR″, OR″, COOH;
N is H, R″, COOR″, OCOR, an aryl radical;
R′ is a hydrocarbon chain having from 8 to 50 carbon atoms;
R″ is a hydrocarbon chain having from 1 to 10 carbon atoms;
m is between 0.4 and 1.0; and
n is between 0 and 0.6.
10. The mineral oil distillate of claim 1 , wherein said distillate further comprises a polyoxyalkylene compound selected from the group consisting of an ester, an ether, an ester/ether, and mixtures thereof, said compound having at least one alkyl radical having from 12 to 30 carbon atoms.
11. The mineral oil distillate of claim 1 , wherein said distillate further comprises a copolymer comprising structural units of ethylene, structural units which derive from α-olefins having from 3 to 24 carbon atoms and having a molecular weight of up to 120 000 g/mol.
12. A method for improving the electrical conductivity of low sulfur middle distillates, said method comprising adding to said middle distillates having a sulfur content of 350 ppm or less a composition comprising at least one alkylphenol-aldehyde resin and from 0.005 to 10% by weight of at least one oil-soluble organic ammonium sulfonate, based on the alkylphenol-aldehyde resin, wherein the at least one alkylphenol-aldehyde resin has a repeating structural unit of the formula
where R 5 is C 1 -C 200 -alkyl or -alkenyl and n is from 2 to 100.
13. The method of claim 12 , wherein the aldehyde which is condensed to form the at least one alkylphenol-aldehyde resin has from 1 to 12 carbon atoms.
14. The method of claim 12 , wherein the at least one alkylphenol-aldehyde resin has an alkyl group with from 1 to 200 carbon atoms.
15. The method of claim 12 , wherein the at least one alkylphenol-aldehyde resin has a molecular weight of from 400 to 20 000 g/mol.
16. The method of claim 12 , wherein the at least one oil-soluble organic ammonium sulfonate is prepared from an oil soluble sulfonic acid having at least one sulfonic acid group and at least one saturated or unsaturated radical selected from the group consisting of a linear, a branched, a cyclic hydrocarbon radical, and mixtures thereof having from 1 to 40 carbon atoms.
17. The method of claim 12 , wherein the at least one oil-soluble organic ammonium sulfonate is prepared from an oil-soluble amine of the general formulae
NR 1 R 2 R 3 or NR 1 R 2 —[(CH2) n -NR 2 ] m R 3
or mixtures thereof, where R 1 is an alkyl radical having from 1 to 24 carbon atoms or an alkenyl radical having from 2 to 24 carbon atoms, R 2 and R 3 are each independently H or as defined for R 1 , n is from 2 to 6 and m is from 1 to 6.
18. The method of claim 12 , wherein the composition further comprises a copolymer comprising as monomers ethylene and from 6 to 21 mol % of a compound selected from the group consisting of a vinyl ester, an acrylic ester, a methacrylic ester, an alkyl vinyl ester, and mixtures thereof, and optionally an alkene.
19. The method of claim 12 , wherein the composition further comprises a reaction product of a compound of the formula NR 6 R 7 R 8 , where R 6 , R 7 and R 8 may be the same or different and at least one of these groups is C 8 -C 36 -alkyl, C 6 -C 36 -cycloalkyl, C 8 -C 36 -alkenyl, and the remaining groups are either hydrogen, C 1 -C 36 -alkyl, C 2 -C 36 -alkenyl, cyclohexyl, or a group of the formulae -(A-O) x -E or —(CH 2 ) n —NYZ, where A is an ethyl or propyl group, x is from 1 to 50, E=H, C 1 -C 30 -alkyl, C 5 -C 12 -cycloalkyl or C 6 -C 30 -aryl, and
n=2, 3 or 4, and Y and Z are each independently H, C 1 -C 30 -alkyl or -(A-O) x with compounds which have a functional group of the formula
>C═O.
20. The method of claim 12 , wherein the composition further comprises a comb polymer of the formula
where
A is R′, COOR′, OCOR′, R″-COOR′, OR∝ 0 ;
D is H, CH 3 , A or R″;
E is H, A;
G is H, R″, R″—COOR′, an aryl radical or a heterocyclic radical;
M is H, COOR″, OCOR″, OR″, COOH;
N is H, R″, COOR″, OCOR, an aryl radical;
R′ is a hydrocarbon chain having from 8 to 50 carbon atoms;
R″ is a hydrocarbon chain having from 1 to 10 carbon atoms;
m is between 0.4 and 1.0; and
n is between 0 and 0.6.
21. The method of claim 12 , wherein the composition further comprises a polyoxyalkylene compound selected from the group consisting of an ester, an ether, an ester/ether, and mixtures thereof, said compound having at least one alkyl radical having from 12 to 30 carbon atoms.
22. The method of claim 12 , wherein the composition further comprises a copolymer comprising structural units of ethylene, structural units which derive from α-olefins having from 3 to 24 carbon atoms and having a molecular weight of up to 120 000 g/mol.
23. A method for improving the cold flowability of low sulfur middle distillates, said method comprising adding to said middle distillates having a sulfur content of 350 ppm or less a composition comprising at least one alkylphenol-aldehyde resin and, based on the alkylphenol-aldehyde resin from 0.005 to 10% by weight of at least one oil-soluble organic ammonium sulfonate wherein the at least one alkylphenol-aldehyde resin has a repeating structural unit of the formula
where R 5 is C 1 -C 200 -alkyl or -alkenyl and n is from 2 to 100.
24. The method of claim 23 , wherein the at least one alkylphenol-aldehyde resin has a molecular weight of from 400 to 20 000 g/mol.
25. The method of claim 23 , wherein the at least one oil-soluble organic ammonium sulfonate is prepared from an oil soluble sulfonic acid having at least one sulfonic acid group and at least one saturated or unsaturated radical selected from the group consisting of a linear, a branched, a cyclic hydrocarbon radical, and mixtures thereof having from 1 to 40 carbon atoms.
26. The method of claim 23 , wherein the at least one oil-soluble organic ammonium sulfonate is prepared from an oil-soluble amine of the general formulae
NR 1 R 2 R 3 or NR 1 R 2 —[(CH2) n -NR 2 ] m R 3
or mixtures thereof, where R 1 is an alkyl radical having from 1 to 24 carbon atoms or an alkenyl radical having from 2 to 24 carbon atoms, R 2 and R 3 are each independently H or as defined for R 1 , n is from 2 to 6 and m is from 1 to 6.
27. The method of claim 23 , wherein the composition further comprises a copolymer comprising as monomers ethylene and from 6 to 21 mol % of a compound selected from the group consisting of a vinyl ester, an acrylic ester, a methacrylic ester, an alkyl vinyl ester, and mixtures thereof, and optionally an alkene.
28. The method of claim 23 , wherein the composition further comprises a reaction product of a compound of the formula NR 6 R 7 R 8 , where R 6 , R 7 and R 8 may be the same or different and at least one of these groups is C 8 -C 36 -alkyl, C 6 -C 36 -cycloalkyl, C 8 -C 36 -alkenyl, and the remaining groups are either hydrogen, C 1 -C 3-6 -alkyl, C 2 -C 36 -alkenyl, cyclohexyl, or a group of the formulae -(A-O) x -E or —(CH 2 ) n —NYZ, where A is an ethyl or propyl group, x is from 1 to 50, E=H, C 1 -C 30 -alkyl, C 5 -C 12 -cycloalkyl or C 6 -C 30 -aryl, and
n=2, 3 or 4, and Y and Z are each independently H, C 1 -C 30 -alkyl or -(A-O) x with compounds which have a functional group of the formula
>C═O.
29. The method of claim 17 , wherein the composition further comprises a comb polymer of the formula
where
A is R′, COOR′, OCOR′, R″—COOR′, OR′;
D is H, CH 3 , A or R″;
E is H, A;
G is H, R″, R″-COOR′, an aryl radical or a heterocyclic radical;
M is H, COOR″, OCOR″, OR″, COOH;
N is H, R″, COOR″, OCOR, an aryl radical;
R′ is a hydrocarbon chain having from 8 to 50 carbon atoms;
R″ is a hydrocarbon chain having from 1 to 10 carbon atoms;
m is between 0.4 and 1.0; and
n is between 0 and 0.6.
30. The method of claim 23 , wherein the composition further comprises a polyoxyalkylene compound selected from the group consisting of an ester, an ether, an ester/ether, and mixtures thereof, said compound having at least one alkyl radical having from 12 to 30 carbon atoms.
31. The method of claim 23 , wherein the composition further comprises a copolymer comprising structural units of ethylene, structural units which derive from α-olefins having from 3 to 24 carbon atoms and having a molecular weight of up to 120 000 g/mol.