US20070283618A1

US20070283618A1 - Diesel detergents

Info

Publication number: US20070283618A1
Application number: US11/450,040
Authority: US
Inventors: Dennis J. Malfer; Scott D. Schwab; Joshua J. Bennett
Original assignee: Afton Chemical Corp
Current assignee: Afton Chemical Corp
Priority date: 2006-06-09
Filing date: 2006-06-09
Publication date: 2007-12-13
Also published as: BE1017295A3; DE102007004888A1

Abstract

A composition for use in preventing deposits in an engine and/or fouling of injectors is prepared by reacting (a) an alkenyl-substituted succinic acid having a molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention
This invention relates to compositions containing the reaction product of (a) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000. These compositions act as detergents and prevent formation of deposits and/or remove already formed deposits in injectors, such as fuel injectors, and/or in engines, including diesel engines.
2. Background Art
The use of conventional fuels without detergent and corrosion-inhibiting additives promotes the accumulation of deposits in the induction system, in particular at the injectors, which become fouled, or even in the combustion chamber, resulting from the presence of polar aromatic compounds and traces of lubricants.
The accumulation of deposits has a detrimental effect on the quality of evaporation of the fuel, which causes an increase in consumption, an increase in the emission of pollutants and of smoke, which is significantly greater during acceleration, and, finally, an increase in noise.
To overcome this problem of fouling of the engine, it is possible to periodically clean the fouled components and particularly the injectors but, in the long run, this method becomes very expensive.
Another method for reducing fouling by deposits in engines, including the injectors is to utilize detergents that are capable of being absorbed on the metal surfaces to prevent the formation of deposits and/or to remove the deposits already formed by cleaning the injectors. Examples of such detergents are the products resulting from the condensation of polyalkenyl succinic anhydrides with polyamines, such as tetraethylenepentamine (“TEPA”), described in U.S. Pat. No. 3,172,892.

BRIEF SUMMARY OF THE INVENTION

The compositions of the invention may be utilized as detergents to prevent formation of deposits and/or remove already formed deposits in injectors, such as fuel injectors, and/or engines, including diesel engines.
In one aspect, the disclosure herein is directed to novel compositions containing the reaction product of (a) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000.
In another aspect, the disclosure herein is directed to a method of making a novel composition containing the reaction product of (a) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000.
In yet another aspect, the disclosure herein is directed to an additive composition that contains a detergent that is the reaction product of (a) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000.
In still yet another aspect, the disclosure herein is directed to a method of preventing deposits in an engine comprising contacting the engine with the reaction product of (a) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000.
In another aspect, the disclosure herein is directed to a method of preventing injector fouling comprising contacting the injector with the reaction product of (a) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000.
In yet another aspect, the disclosure herein is directed to a use of a composition comprising, or consisting essentially of, the reaction product of (a) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 750 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000.
In still yet another aspect, the disclosure herein is directed to an engine comprising a composition that contains the reaction product of (a) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 750 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000.

DETAILED DESCRIPTION OF THE INVENTION

The present disclosure is directed to novel compositions containing the reaction product of an alkenyl-substituted succinic anhydride and a polyaziridine.
As used herein, the singular forms “a” or “an” or “the” include plural references unless the context clearly dictates otherwise. For example, reference to “an alkenyl-substituted succinic anhydride” includes a composition comprising only one specific alkenyl-substituted succinic anhydride, as well as a composition comprising a mixture of alkenyl-substituted succinic anhydrides.
As used herein, the term “about” encompasses the range of experimental error that occurs in any measurement.

Alkenyl-Substituted Succinic Anhydride

The alkenyl-substituted succinic anhydrides that are reacted with the polyaziridines having an average molecular weight of about 250 to about 5000 to yield the reaction product included in the compositions disclosed herein, generally have an average molecular weight of about 250 to about 3000. In one embodiment, the average molecular weight of the alkenyl-substituted succinic anhydride is about 500 to about 2500. In another embodiment, the average molecular weight of the alkenyl-substituted succinic anhydride is about 600 to about 2000. In yet another embodiment, the average molecular weight of the alkenyl-substituted succinic anhydride is about 750 to about 1500. In still yet another embodiment, the average molecular weight of the alkenyl-substituted succinic anhydride is about 850 to about 1200. In another embodiment, the average molecular weight of the alkenyl-substituted succinic anhydride is about 950. The molecular weight of the alkenyl-substituted succinic anhydride is determined by a Total Number calculation that utilizes an acid/base titration.
In one embodiment, the alkenyl-substituted succinic anhydride includes an alkenyl-substituent group containing an average of at least about 30 carbon atoms. In another embodiment, the alkenyl-substituent group contains an average of at least about 40 carbon atoms. In yet another embodiment, the alkenyl-substituent group has an average of at least about 50 carbon atoms. In still yet another embodiment, the alkenyl-substituent group contains an average of at least about 60 carbon atoms. In another embodiment, the alkenyl-substituent group contains an average of at least about 75 carbon atoms. In yet another embodiment, the alkenyl-substituent group contains an average of at least 100 carbon atoms.
In one embodiment, the alkenyl-substituent group contains an average number of carbon atoms of about 30 to about 150. In another embodiment, the alkenyl-substituent group contains an average number of carbon atoms of about 40 to about 100. In yet another embodiment, the alkenyl-substituent group contains an average number of carbon atoms of about 50 to about 75. In still yet another embodiment, the alkenyl-substituent group contains an average number of about 70 carbon atoms.
In one embodiment, the alkenyl-substituent group has an average molecular weight about 200 to about 2950. In another embodiment, the alkenyl-substituent group has an average molecular weight of about 550 to about 1950. In yet another embodiment, the alkenyl-substituent group has an average molecular weight of about 700 to about 1450. In still yet another embodiment, the alkenyl-substituent group has an average molecular weight of about 850 to about 1150. In another embodiment, the alkenyl-substituent group has an average molecular weight of about 950.
Optionally, the alkenyl-substituent group may include one or more carbon-carbon double bonds.
Non-limiting examples of suitable alkenyl-substituent groups include polyethylene, polypropylene, polybutene, poly(1-hexene), polyisobutene, or poly(1-butene), or mixtures of poly(ethylene/propylene), poly(ethylene/butene), poly(propylene/1-hexene), poly(isobutene), or poly(1-butene). The alkenyl-substituent groups may consist of a mixture of any of these substituent groups and may optionally include molecules of differing numbers of carbon atoms and/or molecular weights. Additionally, the alkenyl-substituent groups may optionally be substituted.
In one embodiment, the alkenyl-substituent group is poly(isobutene). In another embodiment, the alkenyl-substituent group is poly(isobutene) having an average molecular weight of about 200 to about 2950. In yet another embodiment, the alkenyl-substituent group is poly(isobutene) having an average molecular weight of about 450 to about 2450. In still yet another embodiment, the alkenyl-substituent group is poly(isobutene) having an average molecular weight of about 550 to about 1950. In another embodiment, the alkenyl-substituent group is poly(isobutene) having an average molecular weight of about 700 to about 1450. In yet another embodiment, the alkenyl-substituent group is poly(isobutene) having an average molecular weight of about 850 to about 1150. In still yet another embodiment, the alkenyl-substituent group is poly(isobutene) having an average molecular weight of about 950.
A specific example of a suitable alkenyl-substituted succinic anhydride includes, but is not limited to, polyisobutylene succinic anhydride (“PIBSA”). In one embodiment, PIBSA has an average molecular weight of about 250 to about 3000. In another embodiment, PIBSA has an average molecular weight of about 500 to about 2500. In yet another embodiment, PIBSA has an average molecular weight of about 600 to about 2000. In still yet another embodiment, PIBSA has an average molecular weight of about 750 to about 1500. In another embodiment, PIBSA has an average molecular weight of about 900 to about 1200. In yet another embodiment, PIBSA has an average molecular weight of about 1000.
In one embodiment, PIBSA has an alkenyl-substituent group containing an average of at least about 30 carbon atoms. In another embodiment, PIBSA has an alkenyl-substituent group containing an average of at least 40 carbon atoms. In yet another embodiment, PIBSA has an alkenyl-substituent group containing an average of at least about 50 carbon atoms. In still yet another embodiment, PIBSA has an alkenyl-substituent group containing an average of at least about 60 carbon atoms. In another embodiment, PIBSA has an alkenyl-substituent group containing an average of at least about 75 carbon atoms. In yet another embodiment, PIBSA has an alkenyl-substituent group containing an average of at least 100 carbon atoms.
In one embodiment, PIBSA has an alkenyl-substituent group containing an average number of carbon atoms of about 30 to about 150. In another embodiment, PIBSA has an alkenyl-substituent group containing an average number of carbon atoms of about 40 to about 100. In yet another embodiment, PIBSA has an alkenyl-substituent group containing an average number of carbon atoms of about 50 to about 75. In still yet another embodiment, PIBSA has an alkenyl-substituent group containing an average number of carbon atoms of about 70.
Methods of preparing the alkenyl-substituted succinic anhydride are well known to persons of ordinary skill in the art. For example, alkenyl-substituted succinic anhydrides may be prepared using a thermal process known as “ene chemistry” (see, e.g., U.S. Pat. No. 3,361,673) and a chlorination process (see, e.g., U.S. Pat. No. 3,172,892).

Polyaziridine

The polyaziridine is a molecule having a straight or branched chain and is the product of a polymerization reaction of aziridine molecules. See Dick, C. R. and Ham, G. E., “Characterization of Polyethylenimine” J. Macromol. Sci.—Chem. A4:1301-1314 (1970). The polyaziridine will generally be an unbranched chain; however, the polyaziridine may include branching.
In one embodiment, the polyaziridine has an average molecular weight of about 250 to about 5000. In another embodiment, the polyaziridine has an average molecular weight of about 250 to about 3000. In yet another embodiment, the polyaziridine has an average molecular weight of about 250 to about 1000. In still yet another embodiment, the polyaziridine has an average molecular weight of about 250 to about 800. In another embodiment, the polyaziridine has an average molecular weight of about 350 to about 650. In yet another embodiment, the polyaziridine has an average molecular weight of about 400 to about 600. In still yet another embodiment, the polyaziridine has an average molecular weight of about 400. In another embodiment, the polyaziridine has an average molecular weight of about 600.
In one embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 7.0 to about 120.0. In another embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 7.0 to about 100.0. In yet another embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 7.0 to about 75.0. In still yet another embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 7.0 to about 60.0. In another embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 7.0 to about 50.0. In yet another embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 7.0 to about 35.0. In still yet another embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 7.0 to about 25.0. In another embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 7.0 to about 20.0. In yet another embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 7.0 to about 18.0. In still yet another embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 7.5 to about 17.5. In another embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 8.0 to about 16.0. In yet another embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 8.5 to about 15.5. In still yet another embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 9.0 to about 15.0.
In one embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 8.5 to about 9.5. In another embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 9.5 to about 10.5. In yet another embodiment, the average number of nitrogen atoms per molecule of the polyaziridine is about 14.5 to about 15.5.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 8 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 8 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 8 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 8 nitrogen atoms per molecule.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 9 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 9 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 9 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 9 nitrogen atoms per molecule.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 10 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 10 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 10 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 10 nitrogen atoms per molecule.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 11 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 11 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 11 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 11 nitrogen atoms per molecule.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 12 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 12 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 12 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 12 nitrogen atoms per molecule.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 13 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 13 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 12 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 13 nitrogen atoms per molecule.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 14 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 14 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 14 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 14 nitrogen atoms per molecule.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 15 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 15 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 15 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 15 nitrogen atoms per molecule.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 16 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 16 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 16 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 16 nitrogen atoms per molecule.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 20 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 20 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 20 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 20 nitrogen atoms per molecule.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 25 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 25 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 25 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 25 nitrogen atoms per molecule.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 35 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 35 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 35 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 35 nitrogen atoms per molecule.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 50 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 50 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 50 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 50 -p In one embodiment, the polyazirdine contains greater than-about 35%, by weight of total polyaziridine molecules polyaziridine molecules with at least 60 nitroge atoms per molecule. In another embodiment the polyiridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 60 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 60 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 60 nitrogen atoms per molecule.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 75 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 75 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 75 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 75 nitrogen atoms per molecule.
In one embodiment, the polyaziridine contains greater than about 35%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 100 nitrogen atoms per molecule. In another embodiment, the polyaziridine contains greater than about 50%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 100 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine contains greater than about 75%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 100 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine contains greater than about 90%, by weight of total polyaziridine molecules, polyaziridine molecules with at least 100 nitrogen atoms per molecule.
In one embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 7 nitrogen atoms per molecule. In another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 8 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 9 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 10 nitrogen atoms per molecule. In another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 11 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 12 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 13 nitrogen atoms per molecule. In another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 14 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 15 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 16 nitrogen atoms per molecule. In another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 20 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 25 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 35 nitrogen atoms per molecule. In another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 50 nitrogen atoms per molecule. In yet another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 60 nitrogen atoms per molecule. In still yet another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 75 nitrogen atoms per molecule. In another embodiment, the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 100 nitrogen atoms per molecule.
The polyaziridine may be prepared by any method known in the art.
Additionally, the polyaziridine is commercially available. For example, suitable polyaziridines are available from Sigma-Aldrich and BASF (sold under the tradename Lupasol®).

Method of Preparing the Compositions

One embodiment of the invention is directed to a method of preparing a novel composition comprising contacting or reacting (a) the alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 described above with (b) the polyaziridine having an average molecular weight of about 250 to about 5000 described above.
The alkenyl-substituted succinic anhydride and the polyaziridine may be reacted at a molar ratio of about 1.0:1.0 to about 2.5:1.0. In one embodiment, the alkenyl-substituted succinic anhydride and the polyaziridine may be reacted at a molar ratio of about 1.1:1.0 to about 2.3:1.0. In another embodiment, the alkenyl-substituted succinic anhydride and the polyaziridine may be reacted at a molar ratio of about 1.2:1.0 to about 1.9:1.0. In yet another embodiment, the alkenyl-substituted succinic anhydride and the polyaziridine may be reacted at a molar ratio of about 1.4:1.0. In still yet another embodiment, the alkenyl-substituted succinic anhydride and the polyaziridine may be reacted at a molar ratio of about 1.8:1.0.

Compositions

The novel compositions of this invention contain the reaction product of (a) an alkenyl-substituted succinic anhydride with an average molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000. In one embodiment, the reaction product of (a) the alkenyl-substituted succinic anhydride with an average molecular weight of about 250 to about 3000 and (b) the polyaziridine having an average molecular weight of about 250 to about 5000 is included in a fuel composition. In another embodiment, the reaction product of (a) the alkenyl-substituted succinic anhydride with an average molecular weight of about 250 to about 3000 and (b) the polyaziridine having an average molecular weight of about 250 to about 5000 is formulated as an additive, such as a concentrate, and may optionally be added to a fuel composition before the fuel composition is contacted with the engine, such as a diesel engine, and/or an injector, including a fuel injector.
In one embodiment, the reaction product of (a) an alkenyl-substituted succinic anhydride with the average molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 750 is included in a fuel composition, such as a diesel fuel composition.
When formulating a fuel composition of this invention, the reaction product of (a) the alkenyl-substituted succinic anhydride with an average molecular weight of about 250 to about 3000 and (b) the polyaziridine having an average molecular weight of about 250 to about 5000 is employed in an amount sufficient to reduce or inhibit deposit formation in an engine, i.e., compression ignition-internal combustion diesel engine. Thus, the fuel composition will contain a minor amount of the reaction product to control or reduce formation of engine deposits and a major amount of a hydrocarbon. In one embodiment, the hydrocarbon boils in the diesel fuel range.
In another embodiment, the fuel composition will contain, on an active ingredient basis, an amount of the reaction product of about 10 to about 10,000 ppm (parts by weight of the reaction product per million parts by weight of fuel plus reactant product). In yet another embodiment, the fuel composition will contain, on an active ingredient basis, about 50 to about 1000 ppm. In still yet another embodiment, the fuel composition will contain, on an active ingredient basis, about 100 to about 500 ppm.
In another embodiment, the reaction product of (a) the alkenyl-substituted succinic anhydride with an average molecular weight of about 250 to about 3000 and (b) the polyaziridine having an average molecular weight of about 250 to about 5000 is formulated as an additive, such as a concentrate, and may optionally be added to a fuel composition prior to contacting the engine, such as a diesel engine and/or the injector, including a fuel injector. The reaction product of (a) the alkenyl-substituted succinic anhydride with an average molecular weight of about 250 to about 3000 and (b) the polyaziridine having an average molecular weight of about 250 to about 5000 may be formulated in the additive with a carrier. In one embodiment, the carrier is a liquid carrier fluid.
Typically, the additive contains about 30 to about 80 weight percent of the reaction product of (a) the alkenyl-substituted succinic anhydride with an average molecular weight of about 250 to about 3000 and (b) the polyaziridine having an average molecular weight of about 250 to about 5000. In one embodiment, the additive contains about 50 to about 70 weight percent of the reaction product of (a) the alkenyl-substituted succinic anhydride with an average molecular weight of about 250 to about 3000 and (b) the polyaziridine having an average molecular weight of about 250 to about 5000.
In another embodiment, the additive may contain about 20 to about 70 weight percent of the carrier. In yet another embodiment, the additive may contain about 30 to about 50 weight percent of the liquid carrier fluid.
In general, the weight ratio of carrier to the novel composition containing the reaction product of (a) the alkenyl-substituted succinic anhydride with an average molecular weight of about 250 to about 3000 and (b) the polyaziridine having an average molecular weight of about 250 to about 5000, on an active ingredient basis, will usually be about 0.3:1 to about 2:1. In one embodiment, the weight ratio of carrier to the novel composition containing the reaction product of (a) the alkenyl-substituted succinic anhydride with an average molecular weight of about 250 to about 3000 and (b) the polyaziridine having an average molecular weight of about 250 to about 5000, on an average ingredient basis, will usually be about 0.5:1 to about 1:1. The active ingredient basis excludes the weight of (i) the unreacted alkenyl-substituted succinic anhydride or the polyaziridine molecules associated with, and remaining, in the product as produced and used, and (ii) solvent(s), if any, used in the manufacture of the novel composition, either during or after its formation but before addition of the carrier.
The proportion of the carrier used relative to the novel composition containing the reaction product of (a) the alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) the polyaziridine having an average molecular weight of about 250 to about 5000, in the additive packages of this invention, is such that the fuel composition containing the diluted additive, when consumed in an engine, such as a diesel engine, results in improved cleanliness as compared to cleanliness of the same engine operated on the same fuel composition except for being devoid of the carrier with the novel composition.
Alternatively, the proportion of the carrier used relative to the novel composition containing the reaction product of (a) the alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) the polyaziridine having an average molecular weight of about 250 to about 5000, in the additive packages of this invention, is such that the fuel composition containing the diluted additive, when consumed in an injector, such as a fuel injector, results in improved cleanliness as compared to cleanliness of the same injector operated on the same fuel composition except for being devoid of the carrier with the novel composition.
The additives used in formulating the preferred fuels of this invention can be blended into the fuel, such as a diesel fuel, individually or in various sub-combinations. In one embodiment, all of the components are blended concurrently using an additive concentrate as this takes advantage of the mutual compatibility afforded by the combination of ingredients when in the form of an additive concentrate. Also, use of a concentrate reduces blending time and lessens the possibility of blending errors.
In addition to the reaction product of (a) the alkenyl-substituted succinic anhydride and the polyaziridine, the fuel compositions and/or additive concentrates may optionally contain additional components. For example, the fuel compositions and/or additive concentrates may include one or more of cetane improvers, friction modifiers, detergents, dispersants, antioxidants, heat stabilizers, corrosion inhibitors, dehazers, metal deactivators, antifoaming agents, cosolvents, package compatibilisers, lubricity additives, antistatic additives, cold flow additives, demulsifiers, and the like. Similarly, the fuel compositions and/or additive concentrates may contain suitable amounts of conventional fuel blending components such as methanol, ethanol, dialkyl ethers, and the like.
This invention is applicable to the operation of engines (e.g., engines used in electrical power generation installations, in pumping stations, engines used as prime movers in automobiles, trucks, road-grading equipment, military vehicles, etc.). Additionally, the invention is applicable to the operation of injectors, such as fuel injectors. Accordingly, one embodiment of the invention includes a method for reducing the amount of deposits of an engine which comprises contacting the engine with a fuel composition comprising a major amount of a hydrocarbon and a minor portion of a composition containing the reaction product of the reaction between (a) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000. In another embodiment, the invention includes a method for reducing the amount of deposits of a diesel engine which comprises contacting the engine with a fuel composition comprising a major amount of a hydrocarbon that boils in the diesel fuel range and a minor portion of a composition containing the reaction product of the reaction between (a) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000.
Another embodiment of the invention includes a method for preventing injector fouling comprising contacting an injector with a fuel composition comprising a major amount of a hydrocarbon and a minor portion of the composition containing the reaction product of the reaction between (a) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000. In another embodiment, the invention includes a method for preventing injector fouling comprising contacting a fuel injector with a fuel composition comprising a major amount of a hydrocarbon and a minor portion of the composition containing the reaction product of the reaction between (a) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000.
Another embodiment of the invention includes the use of a composition containing the reaction product of (a) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 750 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000. In one embodiment, the use of the composition is as a detergent. In another embodiment, the use of the composition is to reduce the amount of deposits in a diesel engine. In yet another embodiment, the use of the composition is to prevent injector fouling.
In some embodiments, the reaction between (a) the alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) the polyaziridine having an average molecular weight of about 250 to about 750 may occur in the carrier liquid. In other instances, the preformed reactant product is blended with a suitable amount of the carrier liquid. If desired, the reactant product can be formed in a suitable solvent or carrier liquid and then blended with an additional quantity of the same or a different carrier liquid.

EXAMPLES

The following examples are illustrative, but not limiting, of the methods of the present invention. Other suitable modifications and adaptations of the variety of conditions and parameters normally encountered in the field, and which are obvious to those skilled in the art, are within the spirit and scope of the invention.

Example 1

162.96 grams (0.172 equivalents) PIBSA (equivalent weight of 950) was added to a 500 mL flask equipped with a Dean Stark trap and a nitrogen purge. The PIBSA was heated to approximately 150° C. Then, 54.38 grams (0.129 moles) polyaziridine (molecular weight of 423) was added over a 17 minute period. The polyaziridine may be added under a slight vacuum. The ratio of equivalents of PIBSA to moles of polyaziridine in the reaction was 1.3 to 1.
The reaction continued for approximately two hours at 155° C. The reaction may occur under a slight vacuum. During the reaction, the water byproduct was removed by the flow of nitrogen. The resulting product was a brown viscous liquid. An infrared spectrum indicated that the product contained both imide and amide moieties.

Example 2

196.08 grams (0.206 equivalents) PIBSA (equivalent weight of 950) and 64.88 grams toluene were added to a 500 mL flask equipped with a Dean Stark trap and a nitrogen purge. Once the PIBSA and toluene were completely mixed, 52.02 grams (0.123 moles) polyaziridine (molecular weight of 423) was added. The ratio of equivalents of PIBSA to moles of polyaziridine in the reaction was 1.7 to 1.
The reaction mixture was heated to 155-160° C. and held there for approximately3 hours. During the reaction, the water byproduct was removed by azeotropic distillation with toluene. After the reaction was complete, toluene was removed by distillation under a nitrogen purge. The resulting product was a brown viscous liquid. An infrared spectrum indicated that the product contained both imide and amide moieties.

Example 3

172.47 grams (0.182 equivalents) PIBSA (equivalent weight of 950) and 49.35 grams toluene were added to a 500 mL flask equipped with a Dean Stark trap and a nitrogen purge. Once the PIBSA and toluene were completely mixed, 41.90 grams (0.099 moles) polyaziridine (molecular weight of 423) was added. The ratio of equivalents of PIBSA to moles of polyaziridine in the reaction was 1.8 to 1.
The reaction mixture was heated to 155-160° C. and held there for approximately 2.5 hours. During the reaction, the water byproduct was removed by azeotropic distillation with toluene. After the reaction was complete, toluene was removed by distillation under a nitrogen purge. The resulting product was a brown viscous liquid.

Example 4

145.47 grams (0.153 equivalents) PIBSA (equivalent weight of 950) and 74.94 grams toluene were added to a 500 mL flask equipped with a Dean Stark trap and a nitrogen purge. Once the PIBSA and toluene were completely mixed, 70.28 grams (0.117 moles) polyaziridine (molecular weight of 600) was added. The ratio of equivalents of PIBSA to moles of polyaziridine in the reaction was 1.3 to 1.
The reaction mixture was heated to 140-145° C. and held there for approximately 4 hours. During the reaction, the water byproduct was removed by azeotropic distillation with toluene. After the reaction was complete, toluene was removed by distillation under a nitrogen purge. The resulting product was a brown viscous liquid.

Example 5

126.16 grams (0.060 moles) PIBSA (equivalent weight of 2120) and 114.42 grams toluene were added to a 500 mL flask equipped with a Dean Stark trap and a nitrogen purge. Once the PIBSA and toluene were completely mixed, 32.36 grams (0.054 moles) polyaziridine (molecular weight of 600) was added. The ratio of equivalents of PIBSA to moles of polyaziridine in the reaction was 1.1 to 1.
The reaction mixture was heated to 160-165° C. and held there for approximately 5 hours. During the reaction, the water byproduct was removed by azeotropic distillation with toluene. After the reaction was complete, toluene was removed by distillation under a nitrogen purge. The resulting product was a brown viscous liquid.

Example 6

The compositions of Examples 1-5 were compared with compositions containing the reaction product of PIBSA and TEPA in the XUD9 test. The results of the test are shown in Table 1 below.

TABLE 1

Results of XUD9 Test

				Average Flow
	Equivalents			Remaining @
	PIBSA/Mole		Treat Rate	.1 mm Needle
Example	Amine	Additive	(mg/kg)	Lift

Comparative	—	None	—	11.0
Comparative	1.0/1.0	PIBSA(equivalent weight = 950)/TEPA	30	20.2
Comparative	1.0/1.0	PIBSA(equivalent weight = 950)/TEPA	60	39.5
1	1.3/1.0	PIBSA(equivalent weight = 950)/	30	34.7
		Polyaziridine(Mn = 423)
1	1.3/1.0	PIBSA(equivalent weight = 950)/	60	74.8
		Polyaziridine(Mn = 423)
2	1.7/1.0	PIBSA(equivalent weight = 950)/	30	—
		Polyaziridine(Mn = 423)
2	1.7/1.0	PIBSA(equivalent weight = 950)/	60	64.2
		Polyaziridine(Mn = 423)
3	1.8/1.0	PIBSA(equivalent weight = 950)/	30	30.6
		Polyaziridine(Mn = 423)
3	1.8/1.0	PIBSA(equivalent weight = 950)/	60	56.1
		Polyaziridine(Mn = 423)
4	1.3/1.0	PIBSA(equivalent weight = 950)/	30	32.8
		Polyaziridine(Mn = 600)
4	1.3/1.0	PIBSA(equivalent weight = 950)/	60	59.7
		Polyaziridine(Mn = 600)
5	1.1/1.0	PIBSA(equivalent weight = 2120)/	30	28.9
		Polyaziridine(Mn = 600)
5	1.1/1.0	PIBSA(equivalent weight = 2120)/	60	45.7
		Polyaziridine(Mn = 600)

The embodiments of the invention include one or more of the above described aspects. It will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.
All patents and publications cited herein are fully incorporated by reference herein in their entirety.

Claims

1. A composition comprising a reaction product of (a) an alkeny-1-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000.

2. The composition of claim 1, wherein the alkenyl-substituted succinic anhydride has an average molecular weight of about 600 to about 2000.

3. The composition of claim 1, wherein the alkenyl-substituent group contains at least 30 carbon atoms.

4. The composition of claim 1, wherein the alkenyl-substituent group of the alkenyl-substituted succinic anhydride has an average molecular weight of about 200 to about 2950.

5. The composition of claim 1, wherein the alkenyl-substituted succinic anhydride is polyisobutylene succinic anhydride.

6. The composition of claim 5, wherein the polyisobutylene succinic anhydride has an average molecular weight of about 600 to about 2000.

7. The composition of claim 5, wherein the alkenyl-substituent group of the polyisobutylene succinic anhydride contains at least 30 carbon atoms.

8. The composition of claim 5, wherein the alkenyl-substituent group of the polyisobutylene succinic anhydride has an average molecular weight of about 200 to about 2950.

9. The composition of claim 1, wherein the polyaziridine has an average molecular weight of about 250 to about 3000.

10. The composition of claim 1, wherein the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 8 nitrogen atoms per molecule.

11. The composition of claim 1, wherein the average number of nitrogen atoms per molecule of the polyaziridine is about 7.0 to about 120.0.

12. The composition of claim 1, wherein the alkenyl-substituted succinic anhydride and the polyaziridine are reacted at a molar ratio of about 1.0:1.0 to about 2.5:1.0.

13. The composition of claim 12, wherein the alkenyl-substituted succinic anhydride and the polyaziridine are reacted at a molar ratio of about 1.2:1.0 to about 1.9:1.0.

14. A fuel composition comprising the composition of claim 1 in a minor amount and a major amount of a hydrocarbon.

15. The fuel composition of claim 14, wherein the hydrocarbon boils in the diesel fuel range.

16. The fuel composition of claim 14, wherein the composition of claim 1 is present in an amount that is about 10 to about 10,000 parts per million.

17. The fuel composition of claim 14, wherein the fuel composition additionally contains one or more additives selected from the group consisting of cetane improvers, friction modifiers, detergents, dispersants, antioxidants, heat stabilizers, corrosion inhibitors, dehazers, metal deactivators, antifoaming agents, cosolvents, package compatibilisers, lubricity additives, antistatic additives, cold flow additives, and demulsifiers.

18. An engine comprising the composition of claim 1.

19. A method of preventing injector fouling comprising contacting an injector with the composition of claim 1.

20. A method of preventing deposits in an engine comprising contacting the engine with the composition of claim 1.

21. A method of preparing the composition of claim 1, wherein the method comprises contacting (a) the alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 with (b) the polyaziridine having an average molecular weight of about 250 to about 5000.

22. The method of claim 21, wherein the alkenyl-substituted succinic anhydride has an average molecular weight of about 600 to about 2000.

23. The method of claim 21, wherein the alkenyl-substituent group of the alkenyl-substituted succinic anhydride contains at least 30 carbon atoms.

24. The method of claim 21, wherein the alkenyl-substituted succinic anhydride is polyisobutylene succinic anhydride.

25. The method of claim 21, wherein the polyaziridine has an average molecular weight of about 250 to about 3000.

26. The method of claim 21, wherein the polyaziridine is a mixture in which the predominant polyaziridine molecule contains at least about 8 nitrogen atoms per molecule.

27. The method of claim 21, wherein the average number of nitrogen atoms per molecule of the polyaziridine is about 7.0 to about 120.0.

28. The method of claim 21, wherein the alkenyl-substituted succinic anhydride and the polyaziridine are reacted at a molar ratio of about 1.0:1.0 to about 2.5:1.0.

29. The method of claim 28, wherein the alkenyl-substituted succinic anhydride and the polyaziridine are reacted at a molar ratio of about 1.2:1.0 to about 1.9:1.0.

30. Use of a composition comprising a reaction product of (a) an alkenyl-substituted succinic anhydride having an average molecular weight of about 250 to about 3000 and (b) a polyaziridine having an average molecular weight of about 250 to about 5000.