Use of amines and/or Mannich adducts in fuel and lubricant compositions for direct-injection spark ignition engines

Abstract

The present invention relates to the use of amines and/or Mannich adducts as detergents and/or dispersants in fuel and lubricant compositions for direct-injection gasoline engines. The invention further relates to fuel and lubricant compositions which comprise at least one such Mannich adduct, and also a bisaminoalkylated Mannich adduct.

Claims

1. A process for reducing deposits in a direct-injection gasoline engine, comprising: directly injecting a fuel into a combustion chamber of the direct injection gasoline engine through a nozzle disposed in the combustion chamber; wherein the fuel comprises a Mannich reaction mixture of (i) an reaction product of a phenol of formula HOC.sub.6(H.sub.4.m)(R.sup.9).sub.m and a polyisobutene of formula HR.sup.8, (ii) an aldehyde of formula CHR.sup.10O and (iii) a secondary amine of formula HNR.sup.1R.sup.2, wherein R.sup.9 is a C.sub.1-C.sub.6-alkyl group and m is a number from 0 to (4-n), R.sup.8 is a polyisobutene radical which is derived from a reactive polyisobutene polymer having at least 50 mol % of terminal double bonds based on the total number of polyisobutene macromolecules, and R.sup.10 is H or C.sub.1-C.sub.6-alkyl, R.sup.1 and R.sup.2 are each independently H, C.sub.1-C.sub.20-alkyl or C.sub.3-C.sub.2-cycloalkyl, and two alkyl radicals together with the nitrogen atom to which they are bonded may form a ring and the alkyl and the cycloalkyl radicals may be interrupted by one or more groups selected from O and NR.sub.4 and/or may be substituted by one or more OR.sup.5 or NR.sup.6R.sup.7 groups, where R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are each independently H, C.sub.1-C.sub.20-alkyl or C.sub.3-C.sub.20-cycloalkyl, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are each independently H, C.sub.1-C.sub.20-alkyl or C.sub.3-C.sub.20-cycloalkyl, wherein the Mannich reaction mixture comprises at least one Mannich adduct of the formula I ##STR00007## wherein n is a number from 1 to 3, with the proviso that the sum of the molecular weights of the radicals R1 and R2 is from 120 to 1,000 g/mol.

2. The process as claimed in claim 1, wherein the sum of the molecular weights of the radicals R.sup.1 and R.sup.2 is from 180 to 600 g/mol.

3. The process as claimed in claim 1, wherein the radicals R.sup.1 and R.sup.2 are each independently H, C.sub.6-C.sub.20-alkyl, C.sub.6-C.sub.20-cycloalkyl,
R.sup.11R.sup.12).sub.xNR.sup.4.sub.yCR.sup.13R.sup.14).sub.zNR.sup.6R.sup.7(II),
R.sup.11R.sup.12).sub.xO.sub.yCR.sup.13R.sup.14).sub.zNR.sup.6R.sup.7(III) or
R.sup.11R.sup.12).sub.xNR.sup.4.sub.yCR.sup.13R.sup.14).sub.zOR.sup.5(IV) where R.sup.4, R.sup.5, R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are each independently H or C.sub.1-C.sub.6-alkyl, R.sup.6 and R.sup.7 are each independently H, C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-hydroxyalkyl, x and z are each independently a number from 1 to 20 and y is a number from 0 to 10.

4. The process as claimed in claim 1, wherein R.sup.8 is in the p-position to the OH group in formula I.

5. The process as claimed in claim 1, wherein the fuel comprises the Mannich reaction mixture the form of a concentrate comprising the Mannich reaction mixture in an amount of from 0.1 to 80% by weight.

6. The process as claimed in claim 1, further comprising combusting the fuel in the combustion chamber of the direct injection gasoline engine at a lambda value of from 0.9 to 9.

7. A process as claimed in claim 1, wherein the Mannich reaction mixture comprises at least one Mannich adduct of the formula I.1 ##STR00008## wherein R.sup.8 has a number-average molecular weight of from 300 to 3000, R.sup.1 and R.sup.2 are each independently C.sub.6-C.sub.20-alkyl, C.sub.6-C.sub.20-cycloalkyl,
R.sup.11R.sup.12).sub.xNR.sup.4.sub.yCR.sup.13R.sup.14).sub.zNR.sup.6R.sup.7(II),
R.sup.11R.sup.12).sub.xO.sub.yCR.sup.13R.sup.14).sub.zNR.sup.6R.sup.7(III) or
R.sup.11R.sup.12).sub.xNR.sup.4.sub.yCR.sup.13R.sup.14).sub.zOR.sup.5(IV), R.sup.4, R.sup.5, R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are each independently H or C.sub.1-C.sub.6-alkyl, R.sup.6 and R.sup.7 are each independently H, C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-hydroxyalkyl, R.sup.9 is a C.sub.1-C.sub.6-alkyl group, x and z are each independently a number from 1 to 20 and y is a number from 0 to 10; and m is 0 or 1.

8. The process as claimed in claim 1, further comprising combusting the fuel in the combustion chamber of the direct injection gasoline engine under lean conditions.

9. The process as claimed in claim 1, wherein the Mannich reaction mixture does not comprise water.

10. The process as claimed in claim 1, wherein the Mannich reaction mixture further comprises the phenolic reaction product.

11. The process as claimed in claim 1, wherein the Mannich reaction mixture further comprises the phenolic reaction product in an amount of from 5 to 10 mol % based on the total amount of the Mannich reaction mixture.

12. The process as claimed in claim 1, wherein the phenolic reaction product mixture comprises a 2,4-R.sup.8-substituted phenolic product.

13. The process as claimed in claim 1, wherein the phenolic reaction product mixture comprises a 2,4-R.sup.8-substituted phenolic product in an amount of 5 to 10 mol % based on the total amount of the phenol.

14. A process for reducing deposits in a direct-injection gasoline engine, comprising: directly injecting a fuel into a combustion chamber of the direct injection gasoline engine through a nozzle disposed in the combustion chamber; wherein the fuel comprises a Mannich reaction mixture of (i) an reaction product of a phenol of formula HOC.sub.6H.sub.(4-m)(R.sup.9).sub.m and a polyisobutene of formula HR.sup.8, (ii) an aldehyde of formula CHR.sup.10O and (iii) a secondary amine of formula HNR.sup.1R.sup.2, wherein R.sup.9 is a C.sub.1-C.sub.6-alkyl group and m is a number from 0 to (4-n), R.sup.8 is a polyisobutene radical which is derived from reactive a polyisobutene polymer having at least 50 mol % of terminal double bonds based on the total number of polyisobutene macromolecules, and R.sup.10 is H or C.sub.1-C.sub.6-alkyl, R.sup.1 and R.sup.2 are each independently H, C.sub.1-C.sub.20-alkyl or C.sub.3-C.sub.20-cycloalkyl, and two alkyl radicals together with the nitrogen atom to which they are bonded may form a ring and the alkyl and the cycloalkyl radicals may be interrupted by one or more groups selected from O and NR.sup.4 and/or may be substituted by one or more OR.sup.5 or NR.sup.6R.sup.7 groups, where R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are each independently H, C.sub.1-C.sub.20-alkyl or C.sub.3-C.sub.20-cycloalkyl, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are each independently H, C.sub.1-C.sub.20-alkyl or C.sub.3-C.sub.20-cycloalkyl, wherein the Mannich reaction mixture comprises at least one Mannich adduct of the formula I ##STR00009## wherein n is 2, with the proviso that the sum of the molecular weights of the radicals R.sup.1 and R.sup.2 is from 120 to 1,000 g/mol.

15. The process as claimed in claim 14, wherein the sum of the molecular weights of the radicals R.sup.1 and R.sup.2 is from 180 to 600 g/mol.

16. The process as claimed in claim 14, wherein the radicals R.sup.1 and R.sup.2 are each independently H, C.sub.6-C.sub.20-alkyl, C.sub.6-C.sub.20-cycloalkyl,
R.sup.11R.sup.12).sub.xNR.sup.4.sub.yCR.sup.13R.sup.14).sub.zNR.sup.6R.sup.7(II),
R.sup.11R.sup.12).sub.xO.sub.yCR.sup.13R.sup.14).sub.zNR.sup.6R.sup.7(III) or
R.sup.11R.sup.12).sub.xNR.sup.4.sub.yCR.sup.13R.sup.14).sub.zOR.sup.5(IV) where R.sup.4, R.sup.5, R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are each independently H or C.sub.1-C.sub.6-alkyl, R.sup.6 and R.sup.7 are each independently H, C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-hydroxyalkyl, x and z are each independently a number from 1 to 20 and y is a number from 0 to 10.

17. The process as claimed in claim 14, wherein R.sup.8 is in the p-position to the OH group in formula I.

18. The process as claimed in claim 14, wherein the fuel comprises the Mannich reaction mixture the form of a concentrate comprising the Mannich reaction mixture in an amount of from 0.1 to 80% by weight.

19. The process as claimed in claim 14, further comprising combusting the fuel in the combustion chamber of the direct injection gasoline engine at a lambda value of from 0.9 to 9.

20. A process as claimed in claim 14, wherein the Mannich reaction mixture comprises at least one Mannich adduct of the formula I.1 ##STR00010## wherein R.sup.8 has a number-average molecular weight of from 300 to 3000, R.sup.1 and R.sup.2 are each independently C.sub.6-C.sub.20-alkyl, C.sub.6-C.sub.20-cycloalkyl,
R.sup.11R.sup.12).sub.xNR.sup.4.sub.yCR.sup.13R.sup.14).sub.zNR.sup.6R.sup.7(II),
R.sup.11R.sup.12).sub.xO.sub.yCR.sup.13R.sup.14).sub.zNR.sup.6R.sup.7(III) or
R.sup.11R.sup.12).sub.xNR.sup.4.sub.yCR.sup.13R.sup.14).sub.zOR.sup.5(IV) R.sup.4, R.sup.5, R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are each independently H or C.sub.1-C.sub.6-alkyl, R.sup.6 and R.sup.7 are each independently H, C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-hydroxyalkyl, R.sup.9 is a C.sub.1-C.sub.6-alkyl group, x and z are each independently a number from 1 to 20 and y is a number from 0 to 10; and m is 0 or 1.

21. The process as claimed in claim 14, further comprising combusting the fuel in the combustion chamber of the direct injection gasoline engine under lean conditions.

22. The process as claimed in claim 14, wherein the Mannich reaction mixture does not comprise water.

23. The process as claimed in claim 14, wherein the Mannich reaction mixture further comprises the phenolic reaction product.

24. The process as claimed in claim 14, wherein the Mannich reaction mixture further comprises the phenolic reaction product in an amount of from 5 to 10 mol % based on the total amount of the Mannich reaction mixture.

25. The process as claimed in claim 14, wherein the phenolic reaction product mixture comprises a 2,4-R.sup.8-substituted phenolic product.

26. The process as claimed in claim 14, wherein the phenolic reaction product mixture comprises a 2,4-R.sup.8-substituted phenolic product in an amount of 5 to 10 mol % based on the total amount of the phenol.

Description

EXAMPLES

I. Preparation of 4-polyisobutenylphenol and of 2-methyl-4-polyisobutenylphenol

1.1 Preparation of 4-polyisobutenylphenol

(1) The preparation was effected starting from phenol and Glissopal 20 1000 by a process described in DE-A 19948111.

(2) In a 4 l four-neck flask, 203.9 g of phenol were melted under nitrogen at from 40 to 45 C. 95.5 g of BF.sub.3-diethyl ether adduct were added dropwise and the mixture was cooled to from 20 to 25 C. 998 g of polyisobutene having an M.sub.N of 1000 and a dimethylvinylidene content of 85%, dissolved in 1800 ml of hexane, were added dropwise at from 20 to 25 C. within 3 hours. Stirring was continued overnight. Subsequently, the reaction was ended by adding 500 ml of 25% ammonia solution. The organic phase was removed and subsequently washed 7 times with 500 ml of water and dried over Na.sub.2SO.sub.4, and the solvent was removed under reduced pressure: 1060 g of oil (polyisobutenylphenol).

(3) NMR: 7.2 ppm (doublet, 2H), 6.7 ppm (doublet, 2H), 4.8 ppm 35 (singlet, broad 1H), 1.75 ppm (singlet, 2H), 1.5-0.5 ppm (singlet, 165H).

(4) This corresponds to an M.sub.N of the alkyl radical of 1150. Within the range from 7.1 to 6.75 there are small signals which suggest that, in addition to the main product (p-polyisobutenylphenol), from 5 to 10% of 2,4-substituted phenol have formed which is in agreement with the low molecular weight increase determined.

I.2 Preparation of 2-methyl-4-polyisobutenylphenol

(5) The preparation was effected starting from cresol and Glissopal 1000 by a process described in DE-A 19948111.

(6) In a 4 l four-neck flask, 234.3 g of cresol were melted under nitrogen at from 40 to 45 C. 95.5 g of BF.sub.3-diethyl ether adduct were added dropwise and the mixture was cooled to from 20 to 25 C. 998 g of polyisobutene having an M.sub.N of 1000 and a dimethylvinylidene content of 85%, dissolved in 1800 ml of hexane, were added dropwise at from 20 to 25 C. within 3 hours. Stirring was continued overnight. Subsequently, the reaction was ended by adding 500 ml of 25% ammonia solution. The organic phase was removed and subsequently washed 7 times with 500 ml of water and dried over Na.sub.2SO.sub.4, and the solvent was removed under reduced pressure. 2-Methyl-4-polyisobutenylphenol was obtained in the form of an oil.

II. Conversion of Polyisobutenylphenols to Mannich Adducts I

II.1 Reaction of the polyisobutenylphenol from 1.1 with paraformaldehyde and N,N-bis[3-(N,N-dimethylamino)propyl]amine

(7) A 1 l flask equipped with a water separator was initially charged with 219.8 g of 4-polyisobutenylphenol from I.1 in 1000 ml of xylene. 15.1 g of paraformaldehyde were added and the mixture was heated to 90 C. for 1 h. Subsequently, 93.9 g of N,N-bis[3-(N,N-dimethylamino)propyl]amine were added rapidly, whereupon 8 ml of aqueous phase separated. The solution was concentrated on a rotary evaporator at 145 C. and 5 mbar. A product mixture of 10% of monoaminoalkylated and 90% of bisaminoalkylated polyisobutenylphenol were obtained as a light-colored oil in a yield of 278.4 g. The mono- and bisaminomethylated products were identified by means of the shifting of the benzylic proton (aromatic ring-CH.sub.2NR.sup.5R.sup.6) in the 1H NMR spectrum.

II.2 Reaction of the polyisobutenylphenol from 1.1 with paraformaldehyde and N,N-di(2-ethylhexyl)amine

(8) In a similar manner to II.1, the polyisobutenylphenol from I.1 was reacted with paraformaldehyde and N,N-di(2-ethylhexyl)amine in a molar ratio of 1:1.2:1.2. The reaction resulted in a product mixture of 90% of monoaminoalkylated and 4% of bisaminoalkylated polyisobutenylphenol.

II.3 Reaction of the polyisobutenylphenol from I.1 with paraformaldehyde and N,N-di(2-ethylhexyl)amine

(9) In a similar manner to II.1, the polyisobutenylphenol from I.1 was reacted with paraformaldehyde and N,N-di(2-ethylhexyl)amine in a molar ratio of 1:2.4:2.4. The reaction resulted in a product mixture of 20% of monoaminoalkylated and 80% of bisaminoalkylated polyisobutenylphenol.

II.4 Reaction of the polyisobutenylcresol from 1.2 with paraformaldehyde and N,N-3-(dimethylamino)propylamine

(10) In a similar manner to II.1, N,N-3-(dimethylamino)propylamine was reacted with the polyisobutenylcresol from 1.2 in a cresol to amine to aldehyde ratio of 1:1:1. The monoaminomethylated cresol was obtained in a yield of 80%. No bisaminomethylated cresol was obtained.

III. Engine Tests

(11) Test Engine:

(12) The test engine used was a modern direct-injection gasoline engine whose cylinder geometry is configured in a such a way that 25 uniform fuel distribution takes place. The experiments were carried out in the lean range.

(13) Type: Four-cylinder, four-stroke, 2.0 l

(14) Capacity: 1998 cm.sup.3

(15) Spark plugs/cylinder: 1

(16) Valves/cylinder: 4

(17) Bore: 86 mm

(18) Stroke: 86 mm

(19) Injection system: common Rail high pressure DI

(20) Injection pressure: approx. 100 bar

(21) Temperature of the cooling liquid: 90 C.

(22) Oil temperature: 94 C.

(23) Test cycle: M 102 E (CEC F-05-A-93), 100 h

(24) Fuel: sulfur-free Superplus to DIN EN 228

(25) The fuel was admixed with 5 different additive packages and subjected to the abovementioned test cycle. Subsequently, the appearance in the interior of the injection nozzle was evaluated.

(26) Additive packages: In addition to the additives specified, the solvent contained in all additive packages was a mixture of xylene and C.sub.11-C.sub.14-paraffins. Additive package 1 (comparative)39% by weight of Mannich adduct a* 17% by weight of polypropoxylate-fatty alcohol ether 44% by weight of solvent Additive package 2 (comparative)39% by weight of Mannich adduct b** 17% by weight of polypropoxylate-fatty alcohol ether 44% by weight of solvent Additive package 339% by weight of Mannich adduct c*** 17% by weight of polypropoxylate-fatty alcohol ether 44% by weight of solvent Additive package 49% by weight of tridecylamine 36% by weight of Mannich adduct a* % by weight of polypropoxylate-fatty alcohol ether % by weight of solvent Additive package 59% by weight of ethylhexylamine 36% by weight of Mannich adduct a* % by weight of polypropoxylate-fatty alcohol ether % by weight of solvent
*Mannich adduct a: Mannich adduct of the formula I where
m=0
n=1
R.sup.8=radical derived from reactive polyisobutene
R.sup.10H
R.sup.1, R.sup.2=methyl

(27) The Mannich adduct a is obtainable by reaction of the polyisobutenylphenol from example I.1 with formaldehyde and dimethylamine in approximately equimolar amounts.

(28) **Mannich adduct b: Mannich adduct of the formula I where

(29) m=0

(30) n=1

(31) R.sup.8=radical derived from low-reactivity polyisobutene

(32) R.sup.10H

(33) R.sup.1H

(34) R.sup.2=3-N,N-dimethylaminopropyl

(35) The Mannich adduct b is obtainable by reaction according to WO 01/42399, p. 16.

(36) ***Mannich adduct c: Mannich adduct of the formula I where

(37) m=0

(38) n=2

(39) R.sup.8=radical derived from reactive polyisobutene

(40) R.sup.10H

(41) R.sup.1, R.sup.2=3-N,N-dimethylaminopropyl

(42) The Mannich adduct c is obtainable by reaction according to II.11

(43) TABLE-US-00001 Additive Dosage Appearance in the interior package No. [mg/kg] of the injection nozzles heavy deposits 1 500 heavy deposits 2 500 heavy deposits 3 500 clean 4 550 clean 5 550 slight deposits

(44) As the engine test shows, the components A and B used in accordance with the invention in the additive packages 3 to 5, unlike the prior art additives, substantially prevent the formation of deposits in the engine chamber of direct-injection gasoline engines.