MXPA99003924A - Monoamines and a method of making the same - Google Patents

Abstract

The present invention provides a novel oligomeric olefin monoamine for use as an additive in fuel and related products and a method of producing the same. The oligomeric olefin monoamine is free of any undesirable halogens. The method of making the oligomeric olefin includes the steps of forming an oligomeric olefin epoxide, converting the epoxide to an alcohol and then converting the alcohol through the use of ammonia to an oligomeric olefin monoamine.

Description

ONOAMINS AND A METHOD TO PREPARE THEM FIELD OF THE INVENTION The present invention relates to novel oligomeric olefinic monoamines and methods for making them. More particularly, the present invention relates to novel oligomeric olefinic monoamines without halogens which, when added to fuels, can be used to control or limit the formation of undesirable deposits in various components of combustion engines.

BACKGROUND OF THE INVENTION Fuel additives for deposit control are well known in the field of the prior art. These additives are useful in limiting the formation of undesirable deposits in engine intake systems (eg, carburetors, manifolds, valves, fuel injectors, combustion chambers, etc.). A fuel additive for significant control of deposits that is generally used in current fuels is produced by the chlorination of polybutene followed by the amination of chlorinated polybutene to give polybutene amine. Polybute amines typically contain between about 0.25 and 1.0 percent residual chlorine. From the point of view of the current interest with respect to the halogenated compounds, it is desirable to decrease or eliminate the presence of chlorine or other halogens in the fuel additives. The present invention satisfies this need as it provides a process and a material that is free of any halogen.

SUMMARY OF THE INVENTION The present invention provides a novel non-halogen additive that includes oligomeric olefin monoamines having the formula: The additive may also include an oligomeric olefinic monoamine having the formula: The invention may also include an oligomeric olefin monoamine having the following structure: The oligomeric olefinic monoamine is first produced by epoxidizing a specific class of oligomeric olefins to give epoxidized oligomeric olefins, converting the epoxidized oligomeric olefin to an alcohol and then admixing the alcohol to the oligomeric olefinic monoamine. The oligomeric olefin which can be used in the production of the oligomeric olefinic monoamine is any oligomeric olefin with unsaturation in the terminal monomer unit. The oligomeric olefinic monoamine of the present invention is useful as an additive in fuels and lubricating oils. The aforementioned and other features of the invention are fully described below and in particular are pointed out in the claims and the following description sets forth in detail certain illustrative embodiments of the invention, these, however, are indicative of some of the ways in which that the principles of the present invention can be employed.

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an oligomeric olefinic monoamine which is essentially free of halogen. The oligomeric olefinic monoamine has the following formula or structure: The invention can also provide oligomeric olefinic monoamines having the following structures: The oligomeric olefinic monoamine of the present invention is useful as an additive for use in fuels and oils. Fuels include, for example, gasoline or motor fuel, aviation fuel, marine fuels and diesel fuels. The oils include, for example, crankcase oils, transmission oils and gear oils. In general, the oligomeric olefinic monoamine of the present invention is produced by epoxidizing an oligomeric olefin to an epoxidized oligomeric olefin, converting the epoxidized oligomeric olefin to an alcohol, and then admixing the alcohol to an oligomeric olefinic monoamine. The oligomeric olefin used to produce the monoamine of the present invention can be derived from several sources These include polyisobutylenes and polybutenes. The key to making the oligomeric olefin useful in the practice of the present invention is that the oligomeric olefin must have unsaturation in the terminal monomer unit. Polybutene is the trade name for oligomers manufactured from C4 olefinic refining fractions from the processes of catalytic decomposition or vapor breakdown of petroleum. The olefinic portion of these C4 fractions consists mainly of isobutylene, but also contains other C4 olefins. Products that consist entirely of polyisobutylene are also available in the market. The commercial polyisobutylene provides a material having the following chemical structure in its terminal monomer unit: Structures with additional end groups that may also be present in commercial polyisobutylenes and polyisobutenes are as follows: These oligomeric olefins will also produce oligomeric olefinic monoamines using the process of the present invention. At least two of the structures above can be found in commercially available polybutene products (although the proportion of these structures in general is different depending on the nature of the catalysts used to produce the polybutenes and polyisobutylenes). The average molecular weight of the commercial polybutenes and the commercial polyisobutylenes of interest is generally greater than about 400, preferably between about 400 and 3,000, more preferably between about 600 and 2,200 and preferably superlative between about 800 and 1,600. However, the aforementioned ranges, it is understood that the practice of the present invention is possible with any of the commercially available polybutene or polyisobutylene oligomers having any average molecular weight between about 400 and 3000 and having unsaturation in the terminal unit. Typical, useful polyisobutylenes and polybutenes that are currently commercially available include, for example, Indopol® H300 (Mn 1300) from Amoco; Parapol® 950 (Mn 950) or Parapol® 1300 (Mn 1300) both from Exxon; Napvis® 30 (Mn 1300) or Ultravis® 10 (Mn 950) or Ultravis® 30 (Mn 1300) all from British Petroleum and Glissopal® ES 3250 (Mn 1000) from BASF. The initial step of preparing the compositions of the present invention is the epoxidation of the unsaturation in the oligomeric olefin. Preferably, the epoxidation reaction occurs upon reaction of the oligomeric alefin with hydrogen peroxide in the presence of an organic carboxylic acid. Due to the high viscosity of the initial oligomeric olefins, the epoxidation reaction is convenient to carry out in a hydrocarbon solvent. The amount of hydrogen peroxide is generally between about 0.5 and 2.5 and preferably between about 1.5 and 2.0 moles per mole of olefin based on the average molecular weight of the olefin. The organic carboxylic acid is in general a monocarboxylic acid having a total of carbon atoms between 2 and 4 with acetic acid being preferred. The amount of organic carboxylic acid is generally between about 0.15 and 0.5 moles, and preferably between about 0.25 and 0.40 moles per mole of olefin based on the average molecular weight of the olefin. further 52/63 of this organic carboxylic acid, an acid catalyst is also required. The acid catalyst may be one or more of the organic acids or one or more of the inorganic acids or combinations thereof which are used to effect the epoxidation reaction. This reaction is described in Organic Peroxides, Vol. 1, Wiley Interscience, New York, 1970, Daniel Swern, pages 340-369, which is considered part of the present reference. Examples of specific acid catalysts include methanesulfonic acid, toluenesulfonic acid, sulfuric acid, phosphoric acid and the like and are used in small amounts for example between about 0.0025 and 0.030 moles per mole of the olefin based on the numerical average molecular weight thereof . The hydrocarbon solvent used in the epoxidation reaction can generally be an inert organic solvent, i.e. a solvent that does not react with any of the reactants. These solvents include aromatic solvents having a total of carbon atoms between about 6 and 9, specific examples include xylene, toluene, C9 aromatics and the like, an aliphatic solvent having between about 6 and 10 carbon atoms with specific examples that include isooctane, heptane, cyclohexane and the like or various substituted aromatic compounds 52/53 with aliphatic groups and the like, as well as combinations thereof. The temperature of the epoxidation reaction will depend on the organic acid that is used and is a function of the stability of the intermediate peracid and the reaction rate thereof. For acetic acid, the reaction temperature in general is between about 60 ° C and 85 ° C, conveniently between about 75 ° C and 85 ° C, and preferably between about 78 ° C and 82 ° C. Suitable reaction temperatures for other organic carboxylic acids used as reagents will vary according to the stability of the intermediate peracid and its reactivity. Some acids can work at temperatures as low as 20 ° C. Since the reaction is exothermic, it is generally necessary to cool the reaction after the temperature has begun to stay within the above ranges. In general, the reaction is carried out at atmospheric pressure, preferably in an inert atmosphere such as nitrogen. The epoxide is a viscous liquid, between colorless and light yellow that can be isolated by the elimination of the solvent by a variety of conventional techniques such as vacuum extraction, film drying by evaporation and the like. In general, the degree of 52/63 epoxidation or conversion is approximately 90 percent. The resulting intermediate is used without further purification in the subsequent reduction step. It will be understood that the epoxidation can be achieved by any of the methods employed in the conversion of olefins to epoxides and the present invention is not limited to the technique described above. It will also be understood that various reagents can be used to effect the epoxidation, including, for example, t-butyl hydroperoxide, peracetic acid and m-chloroperbenzoic acid. The epoxidation steps provide materials with the following structures in the terminal groups: • CH3 52/63 In a subsequent step of the process, the epoxide is converted to an alcohol by catalytic reaction with hydrogen. This hydrogenation is carried out at elevated temperatures and pressures in the presence of a metal catalyst. Examples of suitable metal catalysts include Raney nickel systems, nickel on diatomaceous earth, copper chromite, platinum on carbon, Raney cobalt and palladium on carbon. Raney nickel is a metal catalyst that is preferred. This hydrogenation step is also carried out using hydrogen gas at a pressure of at least 400 psi. The hydrogenation can be carried out at any temperature. However, to have speeds consistent with commercial practice, a temperature of about 125 ° C or higher is preferred. Preferably, the temperature of the reaction does not exceed about 250 ° C. During pressurization and heating, the hydrogenation vessel is preferably stirred. Organic solvents such as methylcyclohexane, xylene, toluene, aromatic C9 solvents and hydrocarbons such as isooctane, heptane, cyclohexane and various aromatic compounds substituted with aliphatic groups or mixtures of those mentioned above can be added to the container to lower the viscosity. However, the selection of the solvent should be done carefully 52/53 to avoid reducing the solvent during hydrogenation. The alcohol prepared by hydrogenation is predominantly the product anti-Mar ovnicov. This product is also the preferred product of amination. Other methods used to produce the anti-Markovnicov product employ lithium aluminum hydride with aluminum chloride, a metal reduction mixture of lithium solution in ethyl amine and butanol and mixtures of diborane and sodium borohydride. Other methods for the reduction of an epoxide to an alcohol are described in the series "Compendium of Organic Synthetic Methods," Wiley Interscience, New York, 1971, Ian T. Harrison and Shuyen Harrison or "Advanced Organic Chemistry," John Wiley and Sons, New York, 1992, Jerry March, pages 443 and 444. These references are considered part of this as a reference for the expositions relating to the hydrogenation The alcohol can be removed from the container and then the amination carried out as a completely separate step. However, it will be understood that the amination step can also be performed in the same container. If desired, the alcohol solution can be separated from the catalyst using conventional techniques such as filtration or decantation. 52/63 The alcohol formation step provides materials with the following structures: -CH2OH -CH2CT 'CH, , CH, -CH • CH OH CH3 The next step in the process is the amination of alcohol. The amination is carried out using liquid ammonia (NH3) at elevated pressure and temperature in the presence of a metal catalyst. Examples of suitable metal catalysts are discussed above, again being the Raney nickel catalyst a metal catalyst that is preferred. The amination is carried out using ammonia gas at a pressure of at least about 1000 psi and a temperature of at least 150 ° C. Preferably, the amination is not carried out using a temperature exceeding about 260 ° C. Between about 2 and 200 of NH3 are used per 52/63 each mole of alcohol to be converted. In addition to NH3, the hydrogen gas is preferably charged into the vessel to increase the pressure thereof between 100 and about 500 psi beyond the level created by the NH3 gas. During the amination, preferably the container is maintained with agitation. Organic solvents such as those listed above, in relation to the hydrogenation step, can be added to the vessel to promote agitation. Also, preferably, the amination is carried out by adding a suppressor of side reactions which serves to suppress the formation of undesirable secondary amines. Examples of these side reaction suppressors include, for example, carboxylic acids such as acetic acid. In addition, it is believed that the addition of materials such as glyme (glyme-abbreviation of glycol dimethyl ether) or polyethers can be used during amination to increase the solubility of ammonia whereby it helps to suppress the formation of undesirable secondary amines. After the amination, the amine is separated from the catalyst (for example, by filtration) and recovered by solvent extraction. Ambering provides materials with the following terminal group structures: 52/63 The oligomeric olefinic monoamine which as a final product is generated by the process can be diluted with solvent (s), for example, C9 aromatic solvent or toluene, to the desired percentage of basic nitrogen as is well known in the art. The dilution facilitates the mixing of the final product with the oil or fuel to which it will be added. The final product can also be added to a vehicle to facilitate its use. The vehicle can have a synergistic effect on the properties of the final product. Suitable carriers include conventional products such as mineral oils and poly (oxyalkylene) derivatives. The final product of the present invention will generally be employed in a 52/63 hydrocarbon distillate fuel with a boiling point in the range of gasoline or diesel, but the use of the final product in other fuels such as aviation and marine fuels is also contemplated. In general, a dilution between about 50 ppm and 2000 ppm of additive in the fuel is convenient. To demonstrate the practice of the present invention, the following illustrative examples are given. The specific embodiments described below are intended to illustrate, but not limit the present invention.

Ej «ampio I Polyolefin Epoxidation A 1.0 L flask was charged with 300g of Ultravis (Polybutene Brithish Petroleum) and 150g of heptane. The material was stirred until the solution was complete. The reactor was then charged with 7.94g of glacial acetic acid, 0.97g of 85% phosphoric acid and 0.7g of 50% sulfuric acid. The mixture was then heated to 80 ° C. A constant feed addition funnel was charged with 42.9 g of 70% hydrogen peroxide. The peroxide was added dropwise to the reaction mixture over a period of one hour. The reaction was then stirred at 80 ° C for 6 more hours. ++++ The reaction was then cooled to 52/63 room temperature. The aqueous phase was separated and discarded. The organic phase was then washed twice with 300 ml of water. After the organic phase was washed to remove the acids from the product it was dried and the solvent was removed to provide 303g of epoxidized polybutene and an oxirane value of 1.27.

Example II Hydrogenation of Polybutene in Epoxide Several batches of polybutene epoxide were prepared using the procedure described in Example I to produce a large amount of epoxide. A 1.8 L Parr reactor was charged with 500 polybutene epoxide. The epoxide was diluted with 250 ml of methylcyclohexane and 25g of Raney nickel catalyst was added. The reactor was purged with nitrogen and then evacuated in such a way that no oxygen remained in the reactor. The reactor was pressurized with hydrogen gas at 650 psi. The agitator was operated and the reactor was heated to 160 ° C. When the reaction reached 160 ° C, the pressure was adjusted to 900 psi by the addition of hydrogen. The reactor was kept stirred at 160 ° C for three hours. At the end of three hours, the pressure in the reactor had dropped to 780 psi. The pressure in the reactor was increased again up to 900 psi by the addition of hydrogen and the reaction was 52/63 stirred for an additional hour at 160 ° C. The reactor was then cooled to room temperature and the pressure in it was relieved until the pressure in the reactor equaled the atmospheric pressure. The product was removed from the reactor and the catalyst was removed from the product by filtration. The solvent was removed from the product by distillation to provide 400g of the polybutene alcohol. The NMR analysis indicated that the epoxide became 82% to the terminal alcohol.

Example III Amination of Polybutene Alcohol A Parr reactor of 1.0 L was charged with 140.78 g of polybutene alcohol prepared as described in Example II. The reactor was then charged with 17.52 g of Raney nickel, 120.77 g of xylene and 25.09 g of water. The reactor was sealed, purged with nitrogen and charged with 151.7 g of liquid anhydrous ammonia. A hydrogen cylinder was connected to the reactor and the reactor pressure was increased by 150 psi with hydrogen. The agitator was operated and the reactor was heated to 230 ° C. The reaction pressure when the reactor reached 230 ° C was 3100 psig. The reaction was stirred for 16 hours at 230 ° C. The reaction was then cooled to room temperature and the reactor pressure was vented in a purification system 52/63 to retain the unreacted ammonia. The product solution was then removed from the reactor and then the catalyst was removed by filtration. To remove some unreacted ammonia from the product, the product solution was then washed twice with 150 ml of water.The washings were separated and discarded.The product solution was dried and the solvent was removed. analysis of the product to determine the% of basic nitrogen revealed that this reaction provided a product with 0.35% basic nitrogen that represents 34% conversion based on the available hydroxyl groups.

Example IV Amination of Polybutene Alcohol A Parr reactor of 1.0 L was charged with 129.4 g of polybutene alcohol was prepared as described in Example II. The reactor was then charged with 26.5 g of Raney nickel and 138.7 g of xylene. The reactor was sealed and purged with nitrogen. The reactor was then charged with 250 g of liquid anhydrous ammonia. A hydrogen cylinder was connected to the reactor and the reactor pressure was increased by 100 psi with hydrogen. The agitator was operated and the reactor was heated to 220 ° C. The reaction pressure when the reactor reached 220 ° C was adjusted to 3000 psig 52/53 venting excess pressure. The reaction was stirred for 16 hours at 220 ° C. The reaction was then cooled to room temperature and the reactor pressure was vented in a scrubbing system to retain the unreacted ammonia. The solution The product was then removed from the reactor and the catalyst was removed from the product solution by filtration. The product solution was washed twice with 150 ml of water to remove some amount of unreacted ammonia. The washing waters were separated and discarded. The product solution was then dried and the solvent was removed. The analysis of the product for the% of basic nitrogen revealed that this reaction provided a product with 0.39% of basic nitrogen which represents 38% conversion based on the available hydroxyl groups.

Example V Amination of Alcohol with Acetic Acid A Parr reactor of 1.0 L was charged with 166.82g of Ultravis 10 alcohol prepared as described above in the Example II The reactor was then charged with 18. Og of Raney nickel and 166.08g of xylenes and llg of glacial acetic acid. The reactor was sealed and purged with nitrogen. The reactor was charged with 150. lg of anhydrous, anhydrous ammonia. A hydrogen cylinder was then connected to the reactor and 52/63 the reactor pressure was increased by 250 psi with hydrogen. The agitator was operated and the reactor was heated to 220 ° C. The reaction pressure when the reactor reached 220 ° C was adjusted to 2200 psig. The reaction was stirred for 16 hours at 220 ° C. The reaction was then cooled to room temperature and the reactor pressure was vented in a scrubbing system to retain the unreacted ammonia. The product solution was then removed from the reactor and the catalyst was removed from the product solution by filtration. The product solution was washed with 150 ml of water to remove some amount of unreacted ammonia. The washing waters were separated and discarded. The product was then dried and the solvent was removed. The analysis of the product for the percentage of basic nitrogen revealed that this reaction provided a product with 0.63% of basic nitrogen that represents a 63% conversion based on the available alcohol. It is understood that the practice of the present invention is not limited to the specific described herein, the examples have been provided simply to enable those skilled in the art to have elements by which the present invention is evaluated. Accordingly, it is well for the scope of that invention to vary the reaction conditions 52/63 set forth herein to the extent that it may be necessary to adapt the selected reagents. The steps that are not critical in the recovery of the product can be varied depending on the equipment used as well as the preferences of the operator. Based on the foregoing discussion, it will now be evident that the process of the present invention will realize the objectives set forth above. Therefore, it is understood that any apparent variations fall within the scope of the claimed invention and in this way, the selection of the specific reagents, as well as the process conditions, can be determined without deviating from the spirit of the invention disclosed and described. here. In particular, the additives for the control of deposits, according to the present invention, are not necessarily limited to those having the polyolefins exemplified herein or the molar proportions employed. On the other hand, as noted above, other reaction temperatures can replace those discussed herein. Thus, the scope of the invention will include all modifications and variations that may fall within the scope of the following claims. 52/63

Claims (21)

1. CLAIMS: 1. A halogen-free additive composition for use in fuels and oils that includes an oligomeric olefin monoamine having the formula:
2. 2. A non-halogen additive according to claim 1, further comprising an oligomeric olefinic monoamine having at least one of the following formulas:
3. 3. A non-halogen additive composition according to claim 1, wherein the molecular weight of the oligomeric olefinic monoamine is between about 400 and 3,000.
4. 4. A non-halogen additive composition according to claim 1, wherein the oligomeric olefin comprises polyisobutylene.
5. 5. A method for making a non-halogen oligomeric olefinic monoamine composition for use as an additive comprising the steps of: A) providing an oligomeric olefin; B) epoxidizing the oligomeric olefin to give an epoxidized oligomeric olefin; C) converting the epoxidized oligomeric olefin to an alcohol; and D) admixing the alcohol product from step C to give the oligomeric olefinic monoamine.
6. 6. A method according to claim 5, wherein the oligomeric olefin comprises an oligomeric olefin showing unsaturation in the terminal monomer unit of the oligomeric olefin.
7. 7. A method according to claim 5, wherein the oligomeric olefin comprises polyisobutylene or polybutene.
8. 8. A method according to claim 5, wherein the oligomeric olefin includes materials having the following structure in the terminal group: -
9. 9. A method according to claim 5, wherein the epoxidation step B provides a product having the following structure in the terminal group:
10. 10. A method according to claim 5, wherein during step C the epoxidized oligomeric olefin is converted to an alcohol by catalytic reaction with hydrogen at elevated temperature and pressure.
11. 11. A method according to claim 5, wherein during step D the alcohol is aminated using ammonia at elevated temperature and pressure in the presence of a metal catalyst and a side reaction suppressor.
12. 12. A fuel composition comprising an additive, the additive that includes an olefinic monoamine 52/63 oligomeric that has the formula:
13. 13. A fuel composition according to claim 12, wherein the additive includes an oligomeric olefin monoamine having at least one of the following formulas:
14. 14. A fuel composition according to claim 12, comprising a material selected from the group consisting of aviation fuel, gasoline, marine fuel and diesel fuel.
15. 15. A method for producing an oligomeric olefinic monoamine to be used as an additive comprising the steps of: I. providing a source of oligomeric olefin; II. epoxidizing the oligomeric olefin by reacting the oligomeric olefin with hydrogen peroxide in the presence of an organic acid and an acid catalyst to give an epoxidized oligomeric olefin; III. converting the epoxidized oligomeric olefin to an alcohol by catalytic reaction with hydrogen; and IV. converting the alcohol to an oligomeric olefin monoamine using ammonia at elevated pressure and temperature in the presence of a metal catalyst.
16. 16. A method according to claim 15, wherein the organic acid of Step II comprises a carboxylic acid.
17. 17. A method according to claim 15, wherein the hydrogenation reaction of Step III is carried out in the presence of a metal catalyst.
18. 18. A method according to claim 17, wherein the metal catalyst comprises a material selected from the group consisting of Raney nickel, copper chromite, platinum and palladium. 52/63
19. 19. A method according to claim 15, wherein Step IV is carried out in the presence of a side reaction suppressor.
20. 20. A method according to claim 19, wherein the side reaction suppressor comprises a material selected from the group consisting of a carboxylic acid, glyme (glycol dimethyl ether) and a polyether.
21. 21. A method according to claim 15, wherein during step IV hydrogen gas is used together with the ammonia at elevated pressure. 52/63