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

Patent metadata

Field	Value
Publication number	US-9938479-B2
Application number	US-201615062799-A
Country	US
Kind code	B2
Filing date	Mar 7, 2016
Priority date	Dec 2, 2002
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

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.

First claim

The invention claimed is:

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 6 (H 4.m )(R 9 ) m and a polyisobutene of formula HR 8 , (ii) an aldehyde of formula CHR 10 O and (iii) a secondary amine of formula HNR 1 R 2 ,
wherein R 9 is a C 1 -C 6 -alkyl group and m is a number from 0 to (4-n),
R 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 10 is H or C 1 -C 6 -alkyl,
R 1 and R 2 are each independently H, C 1 -C 20 -alkyl or C 3 -C 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 4 and/or may be substituted by one or more OR 5 or NR 6 R 7 groups, where R 4 , R 5 , R 6 and R 7 are each independently H, C 1 -C 20 -alkyl or C 3 -C 20 -cycloalkyl,
R 4 , R 5 , R 6 and R 7 are each independently H, C 1 -C 20 -alkyl or C 3 -C 20 -cycloalkyl, wherein the Mannich reaction mixture comprises at least one Mannich adduct of the formula I

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 1 and R 2 is from 180 to 600 g/mol.

3. The process as claimed in claim 1 , wherein the radicals R 1 and R 2 are each independently H, C 6 -C 20 -alkyl, C 6 -C 20 -cycloalkyl,
R 11 R 12 ) x —NR 4 y CR 13 R 14 ) z —NR 6 R 7   (II),

R 11 R 12 ) x —O y CR 13 R 14 ) z —NR 6 R 7   (III) or

R 11 R 12 ) x —NR 4 y CR 13 R 14 ) z —OR 5   (IV)

where R 4 , R 5 , R 11 , R 12 , R 13 and R 14 are each independently H or C 1 -C 6 -alkyl,
R 6 and R 7 are each independently H, C 1 -C 6 -alkyl or C 1 -C 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 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

wherein R 8 has a number-average molecular weight of from 300 to 3000,
R 1 and R 2 are each independently C 6 -C 20 -alkyl, C 6 -C 20 -cycloalkyl,
R 11 R 12 ) x —NR 4 y CR 13 R 14 ) z —NR 6 R 7   (II),

R 11 R 12 ) x —O y CR 13 R 14 ) z —NR 6 R 7   (III) or

R 11 R 12 ) x —NR 4 y CR 13 R 14 ) z —OR 5   (IV),

R 4 , R 5 , R 11 , R 12 , R 13 and R 14 are each independently H or C 1 -C 6 -alkyl,
R 6 and R 7 are each independently H, C 1 -C 6 -alkyl or C 1 -C 6 -hydroxyalkyl,
R 9 is a C 1 -C 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 8 -substituted phenolic product.

13. The process as claimed in claim 1 , wherein the phenolic reaction product mixture comprises a 2,4-R 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 6 H (4-m) (R 9 ) m and a polyisobutene of formula HR 8 , (ii) an aldehyde of formula CHR 10 O and (iii) a secondary amine of formula HNR 1 R 2 ,
wherein R 9 is a C 1 -C 6 -alkyl group and m is a number from 0 to (4-n),
R 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 10 is H or C 1 -C 6 -alkyl,
R 1 and R 2 are each independently H, C 1 -C 20 -alkyl or C 3 -C 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 4 and/or may be substituted by one or more OR 5 or NR 6 R 7 groups, where R 4 , R 5 , R 6 and R 7 are each independently H, C 1 -C 20 -alkyl or C 3 -C 20 -cycloalkyl,
R 4 , R 5 , R 6 and R 7 are each independently H, C 1 -C 20 -alkyl or C 3 -C 20 -cycloalkyl,
wherein the Mannich reaction mixture comprises at least one Mannich adduct of the formula I

wherein n is 2,
with the proviso that the sum of the molecular weights of the radicals R 1 and R 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 1 and R 2 is from 180 to 600 g/mol.

16. The process as claimed in claim 14 , wherein the radicals R 1 and R 2 are each independently H, C 6 -C 20 -alkyl, C 6 -C 20 -cycloalkyl,
R 11 R 12 ) x —NR 4 y CR 13 R 14 ) z —NR 6 R 7   (II),

R 11 R 12 ) x —O y CR 13 R 14 ) z —NR 6 R 7   (III) or

R 11 R 12 ) x —NR 4 y CR 13 R 14 ) z —OR 5   (IV)

where R 4 , R 5 , R 11 , R 12 , R 13 and R 14 are each independently H or C 1 -C 6 -alkyl,
R 6 and R 7 are each independently H, C 1 -C 6 -alkyl or C 1 -C 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 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 mixtu

Assignees

• Basf Se

Inventors

• Lange Arno
• Rath Hans Peter
• Walter Marc
• Bergemann Marco
• Schmidt Helmut

Classifications

• C10M133/08

  containing hydroxy groups · CPC title

• C10L1/1616

  fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine · CPC title

• C10L1/1608

  Well defined compounds, e.g. hexane, benzene · CPC title

• C10M2215/044

  having cycloaliphatic groups · CPC title

• C10L1/221

  compounds of uncertain formula; reaction products where mixtures of compounds are obtained · CPC title