ALKOXYLATED AMINES AS FUEL ADDITIVES

Abstract

The present invention describes alkoxylated amines as fuel additives for reducing injector deposits in direct injection gasoline engines.

Claims

1-13. (canceled)

14. A fuel additive concentrate comprising (A), (B1), (B2) and (B3): (A) at least one compound of formula (I) or (II) ##STR00005## wherein R is a divalent organic radical, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are each independently hydrogen or a monovalent organic radical or a [X.sub.i].sub.nH radical or R.sup.1 and R.sup.2 together with the nitrogen atom form a five- to seven-membered ring, w is a positive integer, x, y and z are each independently zero or a positive integer, n is a positive integer, and each X.sub.i for i=1 to n is independently selected from the group consisting of CH.sub.2CH.sub.2O, CH.sub.2CH(CH.sub.3)O, CH(CH.sub.3)CH.sub.2O, CH.sub.2C(CH.sub.3).sub.2O, C(CH.sub.3).sub.2CH.sub.2O, CH.sub.2CH(C.sub.2H.sub.5)O, CH(C.sub.2H.sub.5)CH.sub.2O and CH(CH.sub.3)CH(CH.sub.3)O, with the provisos that: the sum total of x, y and z is non-zero, at least one of the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 radicals is not hydrogen, and at least one of the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 radicals represents a [X.sub.i].sub.nH radical, (B1) at least one compound (B1a) which is a polyisobuteneamine obtainable by hydroformylation and subsequent reductive amination of polyisobutene with Mn=300 to 5000, (B2) at least one carrier oil selected from the group consisting of polyolefins, (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started polyetheramines and carboxylic esters of long-chain alkanols, and (B3) at least one corrosion inhibitor selected from the group consisting of mono-, di- and polycarboxylic acids having at least 12 carbon atoms, ammonium salts of organic carboxylic acids and heterocyclic aromatics.

15. A fuel composition comprising (A), (B1), (B2), (B3), (C) and optionally (D): (A) at least one compound of formula (I) or (II) ##STR00006## wherein R is a divalent organic radical, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are each independently hydrogen or a monovalent organic radical or a [X.sub.i].sub.nH radical or R.sup.1 and R.sup.2 together with the nitrogen atom form a five- to seven-membered ring, w is a positive integer, x, y and z are each independently zero or a positive integer, n is a positive integer, and each X.sub.i for i=1 to n is independently selected from the group consisting of CH.sub.2CH.sub.2O, CH.sub.2CH(CH.sub.2)O, CH(CH.sub.3)CH.sub.2O, CH.sub.2C(CH.sub.3).sub.2O, C(CH.sub.3).sub.2CH.sub.2O, CH.sub.2CH(C.sub.2H.sub.5)O, CH(C.sub.2H.sub.5)CH.sub.2O and CH(CH.sub.3)CH(CH.sub.3)O, with the provisos that: the sum total of x, y and z is non-zero, at least one of the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 radicals is not hydrogen, and at least one of the R, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 radicals represents a [X.sub.i].sub.nH radical, (B1) at least one compound having detergent action, (B2) at least one carrier oil selected from the group consisting of polyolefins, (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started polyetheramines and carboxylic esters of long-chain alkanols, (B3) at least one corrosion inhibitor selected from the group consisting of mono-, di- and polycarboxylic acids having at least 12 carbon atoms, ammonium salts of organic carboxylic acids and heterocyclic aromatics, (C) at least one gasoline fuel, and (D) optionally an alcohol.

16. The fuel additive concentrate of claim 14, wherein the R radical is selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,8-octylene and 1,10-decylene.

17. The fuel additive concentrate of claim 14, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6, if they do not represent a [X.sub.i].sub.nH radical, are independently selected from the group consisting of hydrogen and an alkyl radical having 1 to 12 carbon atoms.

18. The fuel additive concentrate of claim 17, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6, if they do not represent a [X.sub.i].sub.nH radical, are independently selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl and tert-butyl.

19. The fuel additive concentrate of claim 14, wherein the compound is a compound of the formula (I).

20. The fuel additive concentrate of claim 19, wherein x=1 or 2 and R is 1,2-ethylene, 1,2-propylene or 1,3-propylene.

21. The fuel additive concentrate of claim 19, wherein R.sup.1 and R.sup.2 are each independently C.sub.1- to C.sub.4-alkyl and R.sup.3 and R.sup.4 are each independently a [X.sub.i].sub.nH radical.

22. The fuel additive concentrate of claim 21, wherein each X.sub.i for i=1 to n is independently selected from the group consisting of CH.sub.2CH(CH.sub.3)O, CH(CH.sub.3)CH.sub.2O, CH.sub.2C(CH.sub.3).sub.2O, C(CH.sub.3).sub.2CH.sub.2O, CH.sub.2CH(C.sub.2H.sub.5)O and CH(C.sub.2H.sub.5)CH.sub.2O.

23. The fuel additive concentrate of claim 14, wherein the compound (A) satisfies the formula (III) ##STR00007## wherein R.sup.1, R.sup.2 and X.sub.i are as defined in claim 14, and p and q are each independently a positive integer.

24. The fuel additive concentrate of claim 14, wherein the sum total of p and q is from 2 to 50.

25. The fuel additive concentrate of claim 14, wherein the radicals in formula (I) are defined as follows: (Ia) R is 1,2-ethylene, w=1, R.sup.1 to R.sup.3 are methyl and R.sup.4 is a [X.sub.i].sub.nH chain; (Ib) R is 1,2-ethylene, w=1, R.sup.1 and R.sup.2 are methyl and R.sup.3 and R.sup.4 are each independently a [X.sub.i].sub.nH chain; (Ic) R is 1,2-propylene, w=1, R.sup.1 and R.sup.2 are methyl and R.sup.3 and R.sup.4 are each independently a [X.sub.i].sub.nH chain; (Id) R is 1,3-propylene, w=1, R.sup.1 and R.sup.2 are methyl and R.sup.3 and R.sup.4 are each independently a [X.sub.i].sub.nH chain; (Ie) R is 1,3-propylene, w=1, R.sup.1 and R.sup.2 are ethyl and R.sup.3 and R.sup.4 are each independently a [X.sub.i]H chain; (It) R is 1,3-propylene, w=1, R.sup.1 and R.sup.2 are n-butyl and R.sup.3 and R.sup.4 are each independently a [X.sub.i].sub.nH chain; or (Ig) R is 1,2-ethylene, w=1, R.sup.1 to R.sup.4 are a [X.sub.i].sub.nH chain.

26. The fuel additive concentrate of claim 14, wherein the radicals in formula (II) are defined as follows: (IIa) R is 1,2-ethylene, x and y are 1, z=0 and R.sup.1 to R.sup.4 and R.sup.6 are each independently a [X.sub.i].sub.nH chain; (IIb) R is 1,2-propylene, x and y are 1, z=0 and R.sup.1 to R.sup.4 and R.sup.6 are each independently a [X.sub.i].sub.nH chain; or (IIc) R is 1,3-propylene, x and y are 1, z=0 and R.sup.1 to R.sup.4 are each independently a [X.sub.i].sub.nH chain, and R.sup.6 is C.sub.1- to C.sub.20-alkyl.

27. The fuel additive concentrate of claim 23, wherein the radicals in formula (III) are defined as follows: (IIIa) R is 1,2-ethylene and R.sup.1 and R.sup.2 are methyl; (IIIb) R is 1,2-ethylene and R.sup.1 and R.sup.2 are ethyl; (IIIc) R is 1,2-ethylene and R.sup.1 and R.sup.2 are n-butyl; (IIId) R is 1,2-ethylene and R.sup.1 and R.sup.2 are collectively a 1,4-butylene chain; (IIIe) R is 1,2-ethylene and R.sup.1 and R.sup.2 are collectively a 1,5-pentylene chain; (IIIf) R is 1,2-ethylene and R.sup.1 and R.sup.2 are collectively a 3-oxa-1,5-pentylene chain; (IIIg) R is 1,2-propylene and R.sup.1 and R.sup.2 are methyl; (IIIh) R is 1,2-propylene and R.sup.1 and R.sup.2 are ethyl; (IIIi) R is 1,2-propylene and R.sup.1 and R.sup.2 are n-butyl; (IIIj) R is 1,2-propylene and R.sup.1 and R.sup.2 are collectively a 1,4-butylene chain; (IIIk) R is 1,2-propylene and R.sup.1 and R.sup.2 are collectively a 1,5-pentylene chain; (IIIl) R is 1,2-propylene and R.sup.1 and R.sup.2 are collectively a 3-oxa-1,5-pentylene chain; (IIIm) R is 1,3-propylene and R.sup.1 and R.sup.2 are methyl; (IIIn) R is 1,3-propylene and R.sup.1 and R.sup.2 are ethyl; (IIIo) R is 1,3-propylene and R.sup.1 and R.sup.2 are n-butyl; (IIIp) R is 1,3-propylene and R.sup.1 and R.sup.2 are collectively a 1,4-butylene chain; (IIIq) R is 1,3-propylene and R.sup.1 and R.sup.2 are collectively a 1,5-pentylene chain; or (IIIm) R is 1,3-propylene and R.sup.1 and R.sup.2 are collectively a 3-oxa-1,5-pentylene chain.

Description

EXAMPLES

[0101] Abbreviations, analysis and chemicals used

OHN: hydroxyl number, determined to DIN 53240-1
Total amine value: determined to DIN EN 13716:2001
M.sub.n: number-average molecular weight to DIN 55672-1
M.sub.w: mass-average molecular weight to DIN 55672-1
D: polydispersity to DIN 55672-1
Potassium contents: determined by ICP-OES
DMAPA: 3-(dimethylamino)propylamine (CAS 109-55-7) from BASF SE
PO: propylene oxide (CAS 75-56-9) from BASF SE
BuO: 1,2-butylene oxide (CAS 106-88-7) from BASF SE
Quadrol L from BASF SE: ethylenediamine4PO
N,N,N,N-tetrakis(2-hydroxypropyl)ethylenediamine, CAS 102-60-3
DETA: diethylenetriamine from BASF SE, CAS 111-40-0
Isotridecanol N from BASF SE, CAS 27458-92-0
Ambosol: hydrated magnesium silicate from PQ Corporation.
Viscosities and densities were determined with a Stabinger viscometer to ASTM D7042.

SYNTHESIS EXAMPLES

Synthesis Example 1: DMAPA2PO

[0102] A 3.5 L pressure autoclave with pitched blade stirrer was initially charged with DMAPA (408.8 g; 4.0 mol) and water (4.1 g, demineralized) and the stirrer was switched on. The reactor was inertized with nitrogen, then heated to 130 C., and nitrogen was used to establish a pressure of 2.0 bar absolute. Propylene oxide (465 g; 8.0 mol) was metered in over a period of 6 h. The mixture was left to react at 130 C. for 6 h and cooled down to 50 C., the reactor was purged with nitrogen and the product was discharged. Then the product was freed of low boilers on a rotary evaporator (90 C./10 mbar/2 h).

[0103] .sup.1H NMR analysis in CDCl.sub.3 confirmed the structure.

Synthesis Example 2: DMAPA25PO

[0104] A 3.5 L pressure autoclave with pitched blade stirrer was initially charged with the product from synthesis example 1 (339 g; 1.55 mol) and 50% aqueous KOH solution (14.5 g) and the stirrer was switched on. This was followed by evacuation to a pressure of 10 mbar and heating to 105 C. for 2 h in order to distill off the water present in the starter mixture. The reactor was inertized with nitrogen, then heated to 130 C., and nitrogen was used to establish a pressure of 2.0 bar absolute. Propylene oxide (2075 g; 35.7 mol) was metered in over a period of 7 h. The mixture was left to react at 130 C. for 10 h and cooled down to 80 C., the reactor was purged with nitrogen and the product was discharged. The product was freed of low boilers on a rotary evaporator (90 C./10 mbar/2 h). Subsequently, 73 g of Ambosol were added to the product, and the mixture was stirred at 80 C. for 2 h and filtered with the aid of a pressure suction filter (filter medium: Seitz K 150 depth filter). This gave 2412 g of the product (99.9% of theory) in the form of a yellow oil.

[0105] OHN 76.3 mg KOH/g, total amine value 67.9 mg KOH/g, DMAPA content by liquid chromatography <0.005%, potassium content <10 ppm, M.sub.n 1658 g/mol, M.sub.w 1891 g/mol, D 1.14, kin. viscosity at 40 C. 113.4 mm.sup.2/s.

Synthesis Example 3: DMAPA15 PO

[0106] DMAPA15 PO was obtained in an analogous manner to synthesis example 2.

[0107] OHN 99.9 mg KOH/g, M.sub.n 1026, M.sub.w 1185 g/mol, D 1.15, potassium content <10 ppm.

Synthesis Example 4: Ethylenediamine25 PO

[0108] In an analogous manner to synthesis example 2, ethylenediamine25 PO was obtained by reacting Quadrol L (ethylenediamine4PO) with 21 equivalents of PO.

[0109] OHN 121.3 mg KOH/g, total amine value 72.2 mg KOH/g, M.sub.n 1804 g/mol, M.sub.w 1902 g/mol, D 1.05, potassium content <10 ppm, dyn. viscosity at 40 C. 198.4 mPas.

Synthesis Example 5: DETA5 PO

[0110] DETA5 PO was obtained in an analogous manner to synthesis example 1 by propoxylation of DETA.

Synthesis Example 6: DETA25 PO

[0111] DETA25 PO was obtained in an analogous manner to synthesis example 2 by propoxylation of DETA5 PO (synthesis example 5).

Synthesis Example 7: DMAPA2BuO

[0112] A 3.5 L pressure autoclave with pitched blade stirrer was initially charged with DMAPA (408.8 g; 4.0 mol) and the stirrer was switched on. The reactor was inertized with nitrogen, then heated to 120 C., and nitrogen was used to establish a pressure of 2.0 bar absolute. 1,2-Butylene oxide (577 g; 8.0 mol) was metered in over a period of 15 h. The mixture was left to react at 120 C. for 6 h and cooled down to 50 C., the reactor was purged with nitrogen and the product was discharged. Then the product was freed of low boilers on a rotary evaporator (90 C./10 mbar/2 h).

[0113] .sup.1H NMR analysis in CDCl.sub.3 confirmed the structure.

Synthesis Example 8: DMAPA25BuO

[0114] A 2 L pressure autoclave with pitched blade stirrer was initially charged with the product from synthesis example 7 (130 g; 0.528 mol) and 50% aqueous KOH solution (6.0 g) and the stirrer was switched on. This was followed by evacuation to a pressure of 10 mbar and heating to 95 C. for 2 h in order to distill off the water present in the starter mixture. The reactor was inertized with nitrogen, then heated to 140 C., and nitrogen was used to establish a pressure of 2.5 bar absolute. 1,2-Butylene oxide (875 g; 12.1 mol) was metered in over a period of 14 h. The mixture was left to react at 140 C. for 4 h and cooled down to 80 C., the reactor was purged with nitrogen and the product was discharged. The product was freed of low boilers on a rotary evaporator (90 C./10 mbar/2 h). Subsequently, 30 g of Ambosol were added to the product, and the mixture was stirred at 80 C./100 mbar for 2 h and filtered with the aid of a pressure suction filter (filter medium: Seitz K 900 depth filter). The product was obtained in the form of a yellow oil.

[0115] OHN 63.7 mg KOH/g, total amine value 49.7 mg KOH/g, M.sub.n 2374 g/mol, M.sub.w 2550 g/mol, D 1.07.

USE EXAMPLES

[0116] The following additive package formulations were produced:

TABLE-US-00001 Carrier Coaddi- Synthesis Synthesis PIBA* oil** tives*** example 2 example 3 [%] [%] [%] [%] [%] Formulation 1 44.22 26.61 29.17 Formulation 2 44.22 18.36 29.17 8.25 Formulation 3 44.22 18.36 29.17 8.25 Formulation 4 47.24 9.73 27.03 16.00

[0117] The formulations were monophasic and did not show any phase separation or precipitation on storage at 10 C. over 6 weeks or on storage over 5 C. over 3 months.

TABLE-US-00002 Carrier Synthesis Synthesis PIBA* oil**** example 8 example 2 [%] [%] [%] [%] Formulation 5 64.52 35.48 Formulation 6 64.52 18.06 17.42 Formulation 7 64.52 18.06 17.42

TABLE-US-00003 Carrier Solvent, Synthesis Synthesis PIBA* oil** corrosion example 2 example 3 [%] [%] inhibitor [%] [%] Formulation 8 30.86 18.57 50.57 Formulation 9 30.01 18.06 49.15 2.78 Formulation 10 30.01 18.06 49.15 2.78 *detergent additive obtainable by hydroformylation and amination with polyisobutene having an Mn of 1000 **PO/BuO-based carrier oil *** friction modifier, solvent and corrosion inhibitor ****PO-based carrier oil

Engine Tests

Use as Carrier Oil:

Valve Sticking Test in the VW Wasserboxer Engine (CEC F-016-96) at 18 C.:

[0118] The testing of the valve sticking performance was undertaken by tests in the VW Wasserboxer test to CEC F-16-T-96. The base fuel used was a Eurosuper fuel to EN 228. The criteria of the test method were used to test for a pass (no valve sticking in three successive test runs) or a fail (valve sticking in the first, second or third of the successive test runs). Valve sticking becomes noticeable here by virtue of the engine starting only with a delay, if at all. In order to enable a differentiation, testing was deliberately effected in the boundary range of expected valve sticking. The doses of the particular additives specified in ppm by weight (reported as pure substance content, without solvent) are based in each case on the total amount of gasoline fuel formulation used.

Fuel: MIRO 95 OKTAN E10

[0119] Formulation 4 at 1000 mg/kg: 3pass
Formulations 5-7 at 2325 mg/kg: 3pass

Reduction of Injector Deposits

[0120] The engine test was conducted as described in WO 2014/023853, page 22 line 20 to page 23 line 5.

[0121] For this purpose, by an in-house method, a commercially available, turbocharged four-cylinder gasoline engine (capacity 1.6 L) with direct injection was with an E0 gasoline comprising 7% by volume of oxygen-containing compounds.

[0122] The fuel was admixed with 80 ppm by weight of the products specified from the synthesis examples or formulations and the FR value was determined over the run time. The FR value is a parameter which is established by the engine control system and corresponds to the injection time of the fuel into the combustion space. When the FR value increases in the course of the test run, this indicates deposits at the injection nozzle; the greater the increase, the more deposits have formed. If the FR value, by contrast, remains constant or even falls in the course of a test run, the injection nozzle remains free of deposits.

[0123] At the same time, the combustion space deposits are determined (deposits at the top end of the piston: PTD, deposits in the cylinder head: CHD).

Test Run 1: Base Value without Additive

[0124] Starting at 0, the FR value falls at first and then reaches 0 again after about 30 hours and reaches a final value of +2.60 after a run time of 50 hours.

Test Run 2: Addition of 80 ppm by Weight of the Compound from Synthesis Example 2 to the Fuel

[0125] Starting at 0, the FR value falls constantly and reaches a final value of 2.00 after a run time of 50 hours.

Test Run 3: Addition of 80 ppm by Weight of the Compound from Synthesis Example 3 to the Fuel

[0126] Starting at 0, the FR value falls constantly andultimately rising again slightlyreaches a final value of 1.58 after a run time of 50 hours.

Test Run 4: Comparison to EP 700985

[0127] Starting at 0 with an unadditized fuel the FR value reaches a value of 7.0 (dirty-up) after 80 h. Thereafter, 65 ppm of PIBA and 55 ppm of polyetheramine according to preparation example B of EP700985 (iso-C.sub.13H.sub.27O (CH.sub.2CHEtO).sub.21(CH.sub.2CHEt)-NH.sub.2) are added to the fuel. After a further 20 h of run time, an FR value of 4.1 is attained (clean-up). The relative clean-up is thus 41%.

Test Run 5: Addition of Synthesis Example 2

[0128] Starting at 0 with an unadditized fuel the FR value rises and reaches a value of 6.8 (dirty-up) after 60 h. Thereafter, 65 ppm of PIBA, 55 ppm of carrier oil and 55 ppm of synthesis example 2 are added to the fuel. After a further 20 h of run time, an FR value of 2.0 is attained (clean-up). The relative clean-up is thus 71%.

Reduction of Combustion Space Deposits in an M111 (PFI) Engine:

[0129] MIRO E10 fuel, 95 octane; test to CEC F-020-98

TABLE-US-00004 Dosage [mg/kg] PTD.sup.1) CHD.sup.2) Formulation 1 365 2819 1609 Formulation 2 365 2036 1071 Formulation 3 365 2244 1051 .sup.1)Piston top deposit; .sup.2)cylinder head deposit

Reduction of Combustion Space Deposits in an M111 (PFI) Engine:

[0130] MIRO E10 fuel, 95 octane; test to CEO F-020-98

TABLE-US-00005 Dosage [mg/kg] PTD.sup.1) CHD.sup.2) Formulation 8 1400 4912 1152 Formulation 9 1440 4720 940 Formulation 10 1440 4768 1007 .sup.1)Piston top deposit; .sup.2)cylinder head deposit