NZ231731A

NZ231731A - Additive for fuels of internal combustion engines comprising a polyalkylene succinimide

Info

Publication number: NZ231731A
Application number: NZ23173189A
Authority: NZ
Inventors: Guy Paul Abramo; Jeffrey Charles Trewella
Original assignee: Mobil Oil Corp
Priority date: 1988-12-30
Filing date: 1989-12-12
Publication date: 1991-03-26
Also published as: JPH02276892A; AU4732789A; EP0376578A1

Description

New Zealand Paient Spedficaiion for Paient Number £31 731 2317 3 1 Priority Date(s): .. .CvA: J Complete Specification Fifed: ^ ^9 c'clss: S.IQ. UW&lGGZtigfe, P.O. Journal. No* ■ •■Aci.sK.......

NEW ZEALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION POLYALKYLENE SUCCINIMIDE DEPOSIT CONTROL ADDITIVES AND FUEL COMPOSITIONS CoHTAlNiNG S4M£ H^We, MOBIL OIL CORPORATION, a corporation organised under the laws of the State of New York, United States of America, of 150 East 42nd Street, New York, State of New York, United States of America, hereby declare the invention for whichC^-/ we pray that a patent may be granted to<jpe/us, and the method by which it is to be performed, to be particularly described in and by the following statement:- (followed by page la) V/( Y, ' W"v'' • ■" " F- '>4- 23 17 3 1 POLYALKYLENE SUCCINIMIDE DEPOSIT CONTROL ADDITIVES AND FUEL COMPOSITIONS CONTAINING SAME This invention relates to additives for controlling or preventing engine deposits and to fuel compositions containing these additives.

Hydrocarbyl succinimides, such as those derived from 5 poly-alkylene polyamines, are known materials which have been widely used as fuel detergents. For example. U.S. Patent No. 4,240,803 describes the use of alkenyl succinimides in gasoline to reduce engine deposits. U.S. Patent No. 4,482,357 discloses additive mixtures for diesel fuels which include a hydrocarbyl 10 succinimide or succinamide and the reduction of coke deposition by the use of these additive mixtures.

This invention provides an additive composition for reducing carbon deposits in internal combustion engines comprising: (a) a polyalkylene succinimide prepared by reacting a polyalkylenesuccinic acid or anhydride, wherein the polyalkylene is derived from a C2, C-j, or Cj olefin or mixture thereof, with a polyalkylene polyamine of the formula NH2 (RNH)-R NH2 in which R is an alkylene radical having from 1 to 5 carbon atoms and n is from 0 to 10, (b) a polyalkylene, and (c) a mineral oil. 2317 31 F-SW4 — 2 - This invention also provides a liquid fuel composition comprising a major amount of a liquid fuel and a minor amount of an additive composition for reducing carbon deposits in internal combustion engines comprising: (a) a polyalkylene succinimide prepared by reacting a polyalklyenesuccinic acid or anhydride, wherein the polyalkylene is derived from a C2, Cj, or C4 olefin or mixture thereof with a polyalkylene polyamine of the formula NH, (RNH)n—R NH2 in which R is an alkylene radical having from 1 to 5 carbon atoms and n is from 0 to 10, (b) a polyalkylene, and (c) a mineral oil.

V This invention further provides a method for cleaning a gasoline internal combustion engine with fuel injectors having deposits from fuel decomposition which noticeably affect performance comprising running the engine for a period of time 20 sufficient to improve performance with a fuel containing greater than 80 pounds per thousand barrels of an additive composition for reducing carbon deposits in internal combustion engines comprising from 22 to 28 parts of a polyalkylene succinimide, between 40 to 50 parts of a polyalkylene, and 25 between about 27 to 33 parts of a mineral oil.

The polyalkylenesuccinimide utilized to make the additive composition of this invention is prepared by reacting a polyalkylenesuccinic acid or anhydride, wherein the polyalkylene is derived from a C2, or olefin, or 2317 r 5 o F-5444 -- 3 -• mixtures thereof, with a polyalkylene polyamine of the formula NH, ■(RNH) — R NH2 in which R is an alkylene radical having from 1 to 5 carbon atoms and "n" is from 0 to 10.

The polyalkylenesuccinic anhydride can be made in accordance with a prior art process involving the thermal condensation of a polyalkylene or polyalkylene mixture with maleic anhydride. This is conveniently carried out at from 1S0°C to 2S0°C, preferably 175°C to Z25°C.

Particularly preferred is the succinic acid or anhydride derived from a polyalkylene such as isobutylene.

Suitable polyamines include methylene diamine, ethylene diamine, diethylene triamine, dipropylene triamine, triethylene tetramine, tetraethylene pentamine, pentamethylene hexamine, hexaethylene heptamine and undecaethylene dodecamine.

One series of reactions, showing one possible product, is as follows: 0 II R'H + CH—C \ 0, / CH—C S CH —C «■ \ 0 / <*2-0 m2—(RMi)f{-H r— ch—1 ch2-c I 0 \ / N—(RNH)jj-H "J'tf.J-* I0,T1. 2317 31 -F-5144- -- 4 -- In the formula above, R1 is polyalkylene containing 12 to 500 carbons, R is alkylene containing 1 to 5 carbon atoms and n is from 0 to 10.

The reaction mixture may contain from 1 mole of the anhydride per mole of the amine, or it may have an amount of anhydride equivalent to the total NH functions in the amine, i.e., up to 14 moles of anhydride per mole of amine.

The polyalkylene component of the additive composition preferably is a liquid polyalkylene where the average number of carbon atoms per molecule is between 12 and 500. Preferably, the polyalkylene is a polymer of ethylene or propylene and, even more preferably, is polyisobutylene wherein the average number of carbon atoms per molecule is between 12 and 500.

The mineral oil can be characterized as one having a viscosity from 100 to 800 SUS at 100°F, and a minimum viscosity index of 90, more typically 91.

The three-component additive composition is formulated by mixing the components in the following broad and preferred proportions: Polyalkylene succinimide Polyalkylene Mineral Oil (100 SUS) Parts by Weight Range Preferred Range to 30 22 to 28 to 55 40 to 50 24 to 36 27 to 33 or Mineral Oil (700 SUS) 32 to 42 35 to 39 In general, the invention contemplates the use of the additive in a fuel composition in a concentration of from 80 lbs. to 400 lbs. per 1,000 barrels of fuel, and most preferably, from 120 lbs. to 250 lbs. per 1,000 barrels, the base gasoline containing F-5164 less than 0.1 weight percent sulfur. Since sulfur and olefins are believed to contribute to gum formation, their reduction is advantageous in obtaining good cleanliness performance. The gasoline can also contain conventional additives such as antioxidants, metal deactivators, lead alkyls, lead scavengers, and corrosion inhibitors.

EXAMPLE 1 Premium unleaded gasoline containing various quantities of a polyisobutylene succinimide, polyalkylene, and a mineral oil mixed in the ratios shown below were evaluated in a single cylinder CLR engine using a 10W-30 mineral oil lubricant. After 40 hours of operation at 1100 rpm and 10 to 12 inches manifold vacuum, the intake valve was removed, its combustion chamber side cleaned and the gross weight determined. Deposits were then removed mechanically and the valve's tare weight was measured in order to calculate the net weight of deposits.

The table below presents the results for several runs with premium unleaded gasoline containing various additive package components alone and in specific combinations. As indicated, use of polyisobutylenesuccinimide alone at 50 pounds per 1000 barrels (Run B) increased ITV deposits 171% compared to Run A in which no additives were present in the fuel. The use of 60 pounds of mineral oil per 1000 barrels (Run D) also increased ITV deposits, but only slightly. Polyalkylene alone at 100 pounds per thousand barrels (Run C) did reduce intake valve deposits to 37% of Run A. However, significant further reductions in deposits were obtained when packages of the type described herein were used (Runs E and -F-StW 2317 3 1 Table 1 CLR Intake Valve Cleanliness Test Results Concentration Pounds Per 1000 Barrels of Fuel Polyal- Pkg. PIB-Succinimide kylene 100 SUS Mineral Oil 700 SUS Mineral Oil Intake Valve Deposits Weight, Mgs. Percent of Base A - - - B 50 - - - 511 171 C - 109 37 D - 351 117 E 50 90 60 - 54 18 F 56 133 _ Ill 3 1 Average of 8 runs Premium unleaded gasoline, for example, Phillips J alone and 15 containing additive packages C and E were evaluated in the standard CRC carburetor cleanliness test. After 20 hours of operation with the standard cycle, the tared carburetor sleeve was removed and weighed to determine the weight of deposits thereon. Table II below presents the results of several runs. ( 20 Use of a polyalkylene package C provided no carburetor keep-clean performance. The package E embodying this invention provided significant improvements in carburetor cleanliness. 2317 31 F-5144- -- 7 -- Table II Carburetor Cleanliness Test Results Concentration Pounds Per 1000 Barrels of Fuel Light Polyal- Mineral Carburetor Sleeve Deposits Pkg. PIB-Succinimide kylene Oil Weight, Mgs. Percent of Base A 24 C - 100 - 23 96 E 50 90 60 2 8 231731 — 8 — \

Claims

WHAT WE CLAIM IS: 10

An additive composition for reducing carbon deposits in internal combustion engines comprising: (a) a polyalkylene succinimide prepared by reacting a polyalkylenesuccinic acid or anhydride, wherein the polyalkylene is derived from a C2, C^, or olefin or mixture thereof, with a polyalkylene polyamine of the formula NH. '(RNH)-R NH2 in which R is an alkylene radical having from 1 to 5 carbon atoms and n is from 0 to 10, (b) a polyalkylene, and (c) a mineral oil. L
2. The additive composition of claim 1 wher polyalkylene succinic acid or anhydride is derived from isobutylene.
3. The additive composition of claim 1 or 2 wherein the polyalkylene succinimide is prepared from a polyamine selected from methylene diamine, ethylene diamine, diethylene triamine, dipropylene triamine, triethylene tetrajnine, tetraethylene pentamine, pentamethylene hexamine, hexaethylene heptamine, and undecaethylene dodecamine.
4. The additive composition of any one of claims l to 3 wherein the polyalkylene is a liquid polyalkylene wherein the average number of carbon atoms per molecule is between 12 and 500. 2317 3 1 FHH-64-* -- 9 --
5. The additive composition of claim 1 wherein the polyalkylene is preponderantly polyethylene or polypropylene or polyisobutylene.
6. The additive composition of any one of claims 1 to 5 wherein the mineral oil has a viscosity of from 100 SUS to 800 SUS at 100°F, and a minimum viscosity index of 90.
7. The additive composition of claim 6 wherein the mineral oil has a viscosity of from 105 to 115 SUS at 100°F, and a minimum viscosity index of 95.
8. The additive composition of any one of claims 1 to 6 wherein the mineral oil has a minimum viscosity index of 91. C
9. The additive composition of any one of claims 1 to 8 comprising from 20 to 30 parts by weight of a polyalkylene succinimide, from 35 to 55 parts of a polyalkylene, and from 24 to 36 parts of a mineral oil.
10. The additive composition of claim 9 comprising from 22 to 28 parts by weight of a polyalkylene succinimide, from 40 to 50 parts of a polyalkylene, and from 27 to 33 parts of a mineral oil.
11. A. liquid fuel composition comprising a major amount of a liquid fuel and a minor amount of an additive composition for reducing carbon deposits in internal combustion engines comprising: (a) a polyalkylene succinimide prepared by reacting a polyalkylenesuccinic acid or anhydride, wherein the polyalkylene is derived from a C2, C^, or olefin or mixture thereof with a polyalkylene polyamine of the formula '»# ' ' " - v- r NH2 (RNH)n—R NH2 in which R is an alkylene radical having from 1 to 5 carbon atoms and n is from 0 to 10, (b) a polyalkylene, and (c) a mineral oil.
12. The liquid fuel composition of claim 11 wherein the polyalkylene succinic acid or anhydride is derived from isobutylene.
13. The liquid fuel composition of claim 11 wherein the polyalkylene succinimide is prepared from a polyamine selected from methylene diamine, ethylene diamine, diethylene triamine, dipropylene triamine, triethylene tetramine, tetraethylene pentamine, pentamethylene hexamine, hexaethylene heptamine, and undecaethylene dodecamine.
14. The liquid fuel composition of claim 11 wherein the polyalkylene is a liquid polyalkylene wherein the average number of carbon atoms per molecule is between 12 and 500.
15. The liquid fuel composition of claim 11 wherein the polyalkylene is preponderantly polyethylene or polypropylene or polyisobutylene.
16. The liquid fuel composition of any one of claims" 11 to 15 wherein the mineral oil has a viscosity of from 100 to 800 SUS at 100°F, and a minimum viscosity index of 90. 2 31 7 3 1 -- ii --
17. The liquid fuel composition of claim 11 wherein said mineral oil has a viscosity of from 105 to 115 SUS at 100°F, and a minimum viscosity index of 95.
18. The liquid fuel composition of any one of claims 11 to 16 wherein the mineral oil has a minimum viscosity index of 91.
19. The liquid fuel composition of any one of claims 11 to 18 wherein the additive comprises from 20 to 30 parts by weight of a polyalkylene succinimide, from 35 to 55 parts of a polyalkylene, and from 24 to 36 parts of a mineral oil.
20. The liquid fuel composition of claim 19 wherein the additive comprises from 22 to 28 parts by weight of a polyalkylene succinimide, from 40 to 50 parts of polyalkylene, and from 27 to 33 parts of a mineral oil.
21. The liquid fuel composition of any one of claims 11 to 20 wherein the liquid fuel component is gasoline or diesel fuel.
22. The liquid fuel composition of claim 11/i/herein the additive comprises from 22 to 28 parts by weight of a polybutylene succinimide, from 40 to 50 parts of polybutylene, and from 27 to 33 parts of a mineral oil having a viscosity of from 100 SUS to 800 SUS at 100°F, and a minimum viscosity index of 90 and the liquid fuel component is gasoline
23. A method for cleaning a gasoline internal combustion engine with fuel injectors having deposits from fuel decomposition which noticeably affect performance comprising running the engine for a period of time sufficient to improve performance with a fuel containing greater than 80 pounds per ?31731 — 12 - thousand barrels of an additive composition for reducing carbon deposits in internal combustion engines comprising from 22 to 28 parts of a polyalkylene succinimide between 40 to 50 parts of a polyalkylene, and between 27 to 33 parts of a mineral oil.
24. The method of claim 23 wherein the additive comprises from 22 to 28 parts by weight of a polybutylene succinimide, from 40 to 50 parts of polybutylene, and from 27 to 33 parts of a mineral oil having a viscosity of from 100 SUS to 800 SUS at 100°F, and a minimum viscosity index of 90 and the liquid fuel component is gasoline.
25. An additive composition according to any one of claims 1 to 10, substantially as herein described with reference to the examples.
26. A liquid fuel composition according to any one of claims 11 to 22, substantially as herein described with reference to the examples.
27. A method for cleaning a gasoline internal combustion engine according to claim 23 or 24, substantially as herein described with reference to the examples. ).Vr. P.\ Sr.. By authorised Agents., A. J. PARK. & SON. /4/UA^(jU.