# US 11,999,917 B2 · Mannich-based quaternary ammonium salt fuel additives

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- Number: US 11,999,917 B2
- Document ID: US11999917B2
- Status: Granted
- Kind: B2
- Application number: 17/445,926
- Filed: 2021-08-25
- Published: 2023-03-16
- Granted: 2024-06-04
- Earliest claimed: 2021-08-25
- Assignees: Afton Chemical Corporation
- Applicants: Afton Chemical Corporation
- Inventors: Scott D. Schwab; Geeta Vadehra; Michel Nuckols
- Web page: https://patentgrep.com/patent/US11999917B2

## CPC

- C10L 1/221: {compounds of uncertain formula; reaction products where mixtures of compounds are obtained}
- C10L 1/2222: {(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates (C10L1/221 takes precedence)}
- C10L 1/14: Organic compounds
- C10L 1/1881: {carboxylic group attached to an aliphatic carbon atom}
- C10L 1/19: Esters {ester radical containing compounds; ester ethers; carbonic acid esters (C10L1/1802, C10L1/1805, C10L1/1808, C10L1/1811, C10L1/1814, C10L1/1817 take precedence)}
- C10L 1/231: {nitro compounds; nitrates; nitrites (C10L1/221 takes precedence)}
- C10L 10/18: use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
- C10L 2200/0259: Nitrogen containing compounds
- C10L 2200/0446: Diesel
- C10L: FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS

## Abstract

The present disclosure provides fuel additives including Mannich-based quaternary ammonium salt additives, fuel compositions including such additives, and Methods of improving performance of fuel injector using such additives.

## Claims

### Claim 1

A quaternary ammonium salt fuel additive comprising the structure of Formula I
wherein
R1 is a hydrocarbyl radical, wherein the number average molecular weight of the hydrocarbyl is about 200 to about 5,000;
R2 is hydrogen or a C1-C6 alkyl group;
R3 is hydrogen or, together with R4, a —C(O)— group or a —CH2— group forming a ring structure with the nitrogen atom closest to the aromatic ring;
R4 is one of hydrogen, C1-C6 alkyl, —(CH2)a—NR5R6, —(CH2)a-Aryl(R1)(R2)(OR3), or together with R3, a —C(O)— group or a —CH2— group forming a ring structure with the nitrogen atom closest to the aromatic ring;
R5 is C1-C6 alkyl or, together with Ye, forms a C1-C6 alkyl substituted —C(O)O⊖;
R6 and R7, independently, are C1-C6 alkyl;
a is an integer from 1 to 10, b is an integer selected from either 0 or 1, and c is an integer from 0 to 10;
X is oxygen or nitrogen; and
Y⊖ is an anionic group having a structure R8C(O)O⊖ wherein R8 is one of (i) together with R5 a C1-C6 alkyl group or (ii) a C1-C6 alkyl, an aryl, a C1-C4 alklylene-C(O)O—R2 or a —C(O)O—R2 group.

### Claim 2 (depends on 1)

The quaternary ammonium salt fuel additive of claim 1, wherein R1 is a hydrocarbyl radical derived from a polyisobutylene polymer or oligomer, the number average molecular weight being about 500 to about 1,500, R2 is hydrogen or a methyl group, R3 and R4 are each hydrogen; a is an integer from 1 to 4, and b and c are each 0.

### Claim 3 (depends on 2)

The quaternary ammonium salt fuel additive of claim 2, wherein R5, R6, and R7 are each C1-C6 alkyl and wherein Y⊖ is the anionic group having the structure R8C(O)O ⊖ with R8 being the C1-C6 alkyl, an aryl, a C1-C4 alklylene-C(O)O—R2 or a —C(O)O—R2 group.

### Claim 4 (depends on 1)

The quaternary ammonium salt fuel additive of claim 1, wherein R1 is a hydrocarbyl radical derived from a polyisobutylene polymer or oligomer; R2 is hydrogen or a methyl group, the number average molecular weight being about 500 to about 1,500, R3 together with R4 is the —C(O)— group or the —CH2— group forming a ring structure with the nitrogen atom closest to the aromatic ring; a is an integer from 1 to 4, b and c are each 0.

### Claim 5 (depends on 4)

The quaternary ammonium salt fuel additive of claim 4, wherein and R5, R6, and R7 are each C1-C6 alkyl and wherein Y⊖ is the anionic group having the structure R8C(O)O⊖ with R8 being the C1-C6 alkyl, an aryl, a C1-C4 alklylene-C(O)O—R2 or a —C(O)O—R2 group.

### Claim 6 (depends on 1)

The quaternary ammonium salt fuel additive of claim 1, wherein R1 is a hydrocarbyl radical derived from a polyisobutylene polymer or oligomer, the number average molecular weight being about 500 to about 1,500, R2 is hydrogen or a methyl group, R3 is hydrogen, R4 is the C1-C6 alkyl group, the —(CH2)a—NR5R6 group, or the —(CH2)a-ArylR1R2OR3 group, a is an integer from 1 to 4, b and c are each 0.

### Claim 7 (depends on 6)

The quaternary ammonium salt fuel additive of claim 6, wherein and R5, R6, and R7 are each C1-C6 alkyl and wherein Y⊖ is the anionic group having the structure R8C(O)O⊖ with R8 being the C1-C6 alkyl, an aryl, a C1-C4 alklylene-C(O)O—R2 or a —C(O)O—R2 group.

### Claim 8 (depends on 1)

The quaternary ammonium salt fuel additive of claim 1, wherein R1 is a hydrocarbyl radical derived from a polyisobutylene polymer or oligomer, the number average molecular weight being about 500 to about 1,500, R2 is hydrogen or a methyl group, R3 and R4 are each hydrogen; a is an integer from 1 to 4, b is 1, c is an integer from 1 to 4, and X is nitrogen or oxygen.

### Claim 9 (depends on 8)

The quaternary ammonium salt fuel additive of claim 8, wherein and R5, R6, and R7 are each C1-C6 alkyl and wherein Y⊖ is the anionic group having the structure R8C(O)O⊖ with R8 being the C1-C6 alkyl, an aryl, a C1-C4 alklylene-C(O)O—R2 or a —C(O)O—R2 group.

### Claim 10 (depends on 1)

The quaternary ammonium salt fuel additive of claim 1, wherein the quaternary ammonium salt fuel additive is derived from (i) a Mannich reaction product or derivative thereof having at least one tertiary amino group and prepared from a hydrocarbyl-substituted phenol, cresol, or derivative thereof, an aldehyde, and a hydrocarbyl polyamine providing the tertiary amino group and reacted with (ii) a quaternizing agent selected from the group consisting of a carboxylic or polycarboxylic acid, ester, amide, or salt thereof or halogen substituted derivative thereof.

### Claim 11 (depends on 10)

The quaternary ammonium salt fuel additive of claim 10, wherein the hydrocarbyl polyamine has the structure R9R10N—[CH2]a—Xb—[CH2]c—NR9R10 wherein R9 and R10 are independently a hydrogen or a C1 to C6 alkyl group with one R9 and R10 pair forming a tertiary amine, X is oxygen or nitrogen, a is an integer from 1 to 10, b is an integer of 0 or 1, and c is an integer from 0 to 10.

### Claim 12 (depends on 10)

The quaternary ammonium salt fuel additive of claim 10, wherein the quaternizing agent is a diester of a polycarboxylic acid.

### Claim 13 (depends on 12)

The quaternary ammonium salt fuel additive of claim 12, wherein the quaternizing agent is a diester of oxalic acid, phthalic acid, maleic acid, or malonic acid, or combinations thereof.

### Claim 14 (depends on 10)

The quaternary ammonium salt fuel additive of claim 10, wherein the quaternizing agent is a halogen substituted derivative of a carboxylic acid.

### Claim 15 (depends on 14)

The quaternary ammonium salt fuel additive of claim 14, wherein the halogen substituted derivative of a carboxylic acid is a mono-, di-, or tri- chloro- bromo-, fluoro-, or iodo-carboxylic acid, ester, amide, or salt thereof selected from the group consisting of halogen-substituted acetic acid, propanoic acid, butanoic acid, isopropanoic acid, isobutanoic acid, tert-butanoic acid, pentanoic acid, heptanoic acid, octanoic acid, halo-methyl benzoic acid, and isomers, esters, amides, and salts thereof.

### Claim 16 (depends on 15)

The quaternary ammonium salt fuel additive of claim 15, wherein the quaternary ammonium salt fuel additive is an internal salt substantially devoid of free anion species.

### Claim 17

A fuel composition comprising a major amount of fuel and a minor amount of a quaternary ammonium salt having the structure of Formula I
wherein
R1 is a hydrocarbyl radical, wherein the number average molecular weight of the hydrocarbyl is about 200 to about 5,000;
R2 is hydrogen or C1-C6 alkyl;
R3 is hydrogen or, together with R4, a —C(O)— group or a —CH2— group forming a ring structure with the nitrogen atom closest to the aromatic ring;
R4 is one of hydrogen, C1-C6 alkyl, —(CH2)a—NR5R6, —(CH2)a-ArylR1R2OR3, or together with R3, a —C(O)— group or a —CH2— group forming a ring structure with the nitrogen atom closest to the aromatic ring;
R5 is C1-C6 alkyl or, together with Y⊖, forms a C1-C6 alkyl substituted —C(O)O⊖;
R6 and R7, independently, are C1-C6 alkyl;
a is an integer from 1 to 10, b is an integer selected from either 0 or 1, and c is an integer from 0 to 10;
X is oxygen or nitrogen; and
Y⊖ is an anionic group having a structure R8C(O)O⊖ wherein R8 is one of (i) together with R5 a C1-C6 alkyl group or (ii) a C1-C6 alkyl, an aryl, a C1-C4 alklylene-C(O)O—R2 or a —C(O)O—R2 group.

### Claim 18 (depends on 17)

The fuel composition of claim 17, wherein R1 is a hydrocarbyl radical derived from a polyisobutylene polymer or oligomer, the number average molecular weight being about 500 to about 1,500, R2 is hydrogen or a methyl group, R3 and R4 are each hydrogen; a is an integer from 1 to 4, and b and c are each 0.

### Claim 19 (depends on 18)

The fuel composition of claim 18, wherein R5, R6, and R7 are each C1-C6 alkyl and wherein Y⊖ is the anionic group having the structure R8C(O)O⊖ with R8 being the C1-C6 alkyl, an aryl, a C1-C4 alklylene-C(O)O—R2 or a —C(O)O—R2 group.

### Claim 20 (depends on 17)

The fuel composition of claim 17, wherein the fuel is diesel and includes about 20 to about 200 ppm of the quaternary ammonium salt or wherein the fuel is gasoline and includes about 5 to about 20 ppm of the quaternary ammonium salt.