WO1997030103A2

WO1997030103A2 - Preparation of polyetheramines and polyetheramine derivatives

Info

Publication number: WO1997030103A2
Application number: PCT/US1997/002135
Authority: WO
Inventors: Dane Chang; David A. Wilson
Original assignee: The Dow Chemical Company
Priority date: 1996-02-15
Filing date: 1997-02-10
Publication date: 1997-08-21
Also published as: TW341580B; WO1997030103A3

Abstract

Processes for preparing polyetheramines, polyetherpolyamines and their derivatives from ammonia capped polyethers are disclosed. Polyetheramines, polyetherpolyamines and their derivatives are prepared by reacting an ammonia capped polyether with an aldehyde or ketone to form an imine or reaction of an ammonia capped polyether with cyanide compound to form a nitrile intermediate, followed by subsequent hydrogenation of the intermediates to form the final polyetheramine products. A process for producing polyetheramine products by reaction of an ammonia capped polyether with an alkylene oxide followed by amination to produce a polyetheramine is also disclosed.

Description

PREPARATION OF POLYETHERAMINES AND POLYETHERAMINE

DERIVATIVES

This application claims the benefit of U.S. Provisional Application No. 60/011,738, filed February 15, 1996.

This invention relates to production of polyetheramines and their derivatives.

Reductive amination is known in the art and is catalytic amination of aliphatic alkane derivatives such as mono- and poly-hydric alcohols, alcoholamines, and compounds from which these alcohols are derived, including epoxides, ketones and alkyleneimines under reducing conditions, preferably in the presence of hydrogen.

The more desirable amine products are those products in which an amine group replaces the non-amine functional group or groups in the starting material. Heavier, more highly substituted amines and heterocyclic nitrogen compounds can be further synthesized from the preferred polyetheramines .

Rath et al. have disclosed in U.S. Patent 5,112,364, which is incorporated herein by reference in its entirety, reductive aminations of certain polyether alcohols with ammonia and certain primary amines. The process is not applied to secondary and tertiary amines. Ammonia was used to reductively aminate a polypropylene glycol in the teachings of Boettger et al U.S. Patent 4,014,933 with a cobalt, nickel and copper catalyst. Other cobalt, nickel and copper catalysts were used to aminate certain polyoxyalkylene polyols with aromatic amines in the teachings of Gurgiolo U.S. Patent 4,588,840. The use of cobalt, nickel and copper catalysts do not offer the art recognized advantages of nickel/rhenium catalysts which have been developed for improved reductive amination processes.

Polyetheramines produced in accordance with the present invention have many uses. In addition to their use as intermediates for synthesizing other chemical materials, they are utilized, for example, in fungicides, insecticides, other biocides, fuels, detergents, lube (lubrication) oils, dispersants, chelants, defoamers, corrosion inhibitors and others.

Because of the many applications in which polyetheramines can be used, it would be advantageous to have a more efficient process for producing polyetheramines.

SUMMARY OF THE INVENTION

The present invention includes a process for producing polyetheramine products comprising contacting an ammonia capped polyether with an aldehyde or ketone to form an intermediate imine and reduction of the imine under hydrogenation conditions to form the polyetheramine or polyetherpolyamine product.

Another feature of the present invention are imine compounds of the formula

Formula 1 wherein p is 1, 2, or 3;

Ri is (a) a linear or branched polyether chain having from 2 to 100 alkylene oxide units in the chain wherein the polyether chain is obtained from an alkylene oxide of 2 to 8 carbon atoms, or a mixture of such alkylene oxides; (b) a polyether radical of the general formula

-R⁸-Ar-(R⁵) (R^β) (R⁷)

Formula 2

or (c) an alicyclic polyether or alkylalicyclic polyether of the general formula

-R⁸-Cy-(R⁵) (R⁶) (R⁷)

Formula 3 where Ar is an aromatic moiety; Cy represents a cyclic structure of at least about 4 atoms;

R5, R6 and R⁷ may be identical or different and are each independently hydrogen, hydroxyl, or a hydrocarbon radical of 1 to 30 carbon atoms which may be substituted with aldehyde, ketone, or hydroxyl moieties; R⁸ is a polyether chain wherein the chain has from 2 to

100 alkylene oxide units obtained from alkylene oxides of 2 to 8 carbon atoms or a mixture of such alkylene oxides; R2 and R^ are each independently hydrogen, an unsubstituted or inertly substituted alkyl, aryl, arylalkyl, or alkylaryl; with the proviso that when R-- is a moiety of Formula 2 or Formula 3, then p is 1.

The polyetheramine products can be prepared by reaction of an ammonia capped polyether with ethyleneimine (El) or a substituted El.

In another aspect the present invention is a process for producing polyetheramine products comprising contacting an ammonia capped polyether with a cyanide compound to form an intermediate nitrile and reduction of the nitrile under hydrogenation conditions to form the polyetheramine product.

The present invention also includes intermediate nitrile compounds made by the above process of the formula

Formula4

wherein R¹ and p are as previously defined; R^ and R^^υ are each independently hydrogen, or

N

Formula4a

where X and Y are independently hydrogen, an unsubstituted or inertly substituted alkyl, aryl, alkylaryl, or arylalkyl; s is an integer from 1 to 6; with the proviso that at least one of R^ or R10 is

Another feature of the invention includes hydroxyl containing species of an ammonia capped polyether of the formula

Formula5

wherein p is as previously defined and R^ is a linear or branched polyether chain having from 2 to 100 alkylene oxide units in the chain wherein the polyether chain is obtained from an alkylene oxide of 2 to 8 carbon atoms, or a mixture of such alkylene oxides; R-- -- and R^2 _are each independently hydrogen or

Formula5a

where X and Y are as previously defined; n is an integer from 0 to 6; with the proviso that at least one of R^- or R12 i_{s 0}f the Formula 5a.

In yet another aspect, the present invention is a polyetheramine of the formula

Formula6

wherein R^ and p are as previously defined; R2 and R^ are each independently hydrogen, an unsubstituted or inertly substituted alkyl, aryl, arylalkyl, or alkylaryl.

In yet another aspect, the present invention is a process for producing polyetheramine products comprising contacting an ammonia capped polyether with an alkylene oxide to form a hydroxyl containing species of the ammonia capped polyether followed by amination of the hydroxyl containing species to produce the polyetheramine.

The present invention is also to polyetheramines of the formula

Formula 7

wherein R^ and p are as previously defined; R¹^ _ancι R14 _{are eacrι} independently hydrogen,

Formula 7a

Formula 7b

Formula7c

where s, X, and Y are as previously defined; n is an integer from 0 to 6;

R! and R " are each independently hydrogen or a moiety of

Formula 7a, 7b, or 4a; with the proviso that at least one of Rl3 _or R14 J__{S a} moiety of Formula 7c.

When one of R--^ or R14 of Formula 7 is a hydroxyl moiety, the other of R---^ or R~-^ is an amine moiety, s equals 1, n equals zero, and at least one of R-~ and R--6 is hydrogen, than R!3 _anc} R14 _may combine to form a cyclic structure. A polyether amine which can form under these conditions is represented by

Formula8

where R-- and p are as previously defined, with the proviso that when R-- is a moiety of Formula 2 or Formula 3, then p equals 1.

The invention also includes a fuel containing a polyetheramine of any one of Formula 1, 4, 5, 6, 7, 8, or a combination thereof. Preferably the fuel is a hydrocarbon fuel, more preferably diesel fuel, aviation fuel or gasoline or a combination thereof. In general, the fuel will contain per kg of fuel, at least about 1 mg of polyetheramine or derivatives thereof, preferably, from 1 to 2000 mg of such polyetheramines or polyetheramine derivatives of Formula 1, 4, 5, 6, 7, 8, or mixtures thereof. Also included are the same amounts of compounds of any one of Formula 1, 4, 5, 6, 7, 8, or mixtures thereof, in lubricating compositions, corrosion inhibitors, defoammg compositions, dispersants, biocides, defoamers, detergents chelants and combination thereof.

The processes for producing polyetheramines and derivatives thereof disclosed herein provide for intermediate lmines and nitrile capped polyetheramines which have not been previously prepared. The processes disclosed herein also result in the formation of new polyetheramine and poyetherpolyamme compounds.

DETAILED DESCRIPTION OF THE INVENTION

The ammonia capped polyethers used in the present invention can be derived from amination of polyether alcohols and substituted alcohols. In general, reductive amination of alcohols involves a reaction between ammonia and/or amines and alcohols in the presence of hydrogen gas. The amination process consists of a series of hydrogenation and dehydrogenation catalytic reactions. The mechanism of the hydrogenation and dehydrogenation steps are discussed in the prior art literature. The first step in the amination process is believed to be a reversible dehydrogenation of the alcohol to give an intermediate carbonyl, commonly an aldehyde. The aldehyde is then converted to an aminoalcohol by reaction with ammonia or an amine present in the reaction mixture. The aminoalcohol then loses water to form the imine . The imine is then hydrogenated to the amine. When the intermediate aldehyde or the imine reacts with amines in the reaction mixture, substituted and heavier amines are formed.

The polyether derivatives which can be aminated in the practice of the present invention include polyether derivatives having one or more functional groups replaceable by an amine group. Preferred polyether derivatives include those containing from 6 to 500 carbon atoms, more preferably from 10 to 100 carbon atoms.

Preferred arylpolyether derivatives include those having from 5 to 500, more preferably from 10 to 100 carbon atoms. The functional groups present are suitably on primary, secondary or tertiary carbon atoms, preferably on secondary carbon atoms. At least one of the functional groups present is capable of being replaced by an amine group (e.g. H2 from ammonia) in the catalytic amination process of the present invention. The preferred replaceable functional groups include hydroxyl, aldehyde, ketone or imino groups and combinations of said groups. Illustrative examples of preferred polyether starting materials include polyalkylene glycols, polyalkylene glycol derivatives and/or other derivatives of polyoxyalkylene alcohols. Polyalkylene glycol derivatives include those initiated with imidazolidone, glycerin, ethylene glycol, phenol, pyrrolidine, other aromatic amines or derivatives of such initiators.

Preferably, at least one of the functional groups in the polyether starting material is a hydroxy group, ketone, aldehyde, or imino group. When more than one functional group is replaceable, for example, hydroxy, then if such groups are of similar reactivity, they will be replaced to a roughly equal extent. If, however, they have different reactivities replacement can be selective for the more reactive site or that site can be blocked by means within the skill in the art to control position of the amine group. While amination processes are applicable to compounds of various sizes and molecular weights, the process of the invention is particularly useful for compounds having a molecular weight in excess of about 50, preferably in excess of about 200. The starting material, however, is advantageously of insufficient molecular weight to interfere with subsequent reaction or use. Preferably the starting material, has a molecular weight less than about 10,000, more preferably less than about 5,000, and most preferably less than about 2,000. These molecular weights are those designated in the case of molecules having a distribution of molecular weights. Functional groups which are not commonly replaceable during amination are optionally present in the polyether starting material in combination with or in addition to the replaceable functional groups.

Starting materials include polyether alcohols of the formula

R⁸(OH)_P

Formula9

HO-R^b-Ar- ( R- (R^b) (R

Formula 10

or

HO-R⁸-Cy- (R⁵) (R⁶) (R⁷

Formula 11

where Cy, Ar, R^, R^, R⁷, R⁸, and p have the meanings as previously defined. The aromatic moiety (Ar) has at least one ring structure and preferably contains from 5 to 20 carbon atoms. More preferably the Ar moiety contains from 5 to 12 carbon atoms. Most preferred are Ar moieties which contain from 5 to 7 carbon atoms. The Ar moiety may optionally contain at least one heteroatom, preferably nitrogen or oxygen, and more preferably nitrogen. Example of heteroatoms containing Ar moieties are 1, 3-dιazoles, pyrazoles, pyrazines, pyrimidmes, pyndazines, punnes, pteridmes, thiophenes, oxazones, pyridmes, dihydroquinolmes, benzoquinolines, diazaanthracenes, naphthalenes, phenyl groups (benzene rings), and the like, and combinations thereof. Preferably the Ar moiety contains a phenyl group in which case the preferred structure is

Examples of compounds containing an Ar moiety are isobutylphenol, dusododecylphenol, isobutylcresol, isododecylphenol, dusobutylphenol, dusononylphenol, dusobutylcresol, dusoctylphenol, tert-buytlphenol, isooctylphenol, tert-butylcresol, di-tert-butylphenol, di- tert-butylcresol, and mixtures of these.

The cyclic moiety (Cy) contains at least one ring structure and has from 4 to 20 atoms. More preferably the Cy moiety contains from 4 to 12 atoms. A Cy moiety containing 4 to 7 atoms is preferred. The Cy moiety is generally made of carbon atoms and optionally may contain heteroatoms, preferably nitrogen or oxygen. Preferably Cy is a cyclic structure of at least about 5 atoms, primarily carbon. The Cy structure is exemplified by such moieties as cyclohexane, furan, tetrahydrofuran, dioxolane, pyran, tetrahydropyran, dioxepin, azetidine, dihydropyroles, pyrrolidine, pyrroline, pyrrolidinone, cyclic lactams of from 5 to 7 cyclic atoms (preferably from 4 to 6 carbon atoms and one nitrogen atom in the ring) and combinations thereof. Preferably Cy is cyclohexane in which case the molecule conforms to the general formula

where R~", R6, R⁷ and R⁸ are as previously defined.

The starting polyether alcohols are generally synthesized in several stages. For example, in the first step, a phenolpolyether or alkylphenol polyether of the general formula

or a cyclohexanol or an alkylcyclohexanol of the general Formula

where R^, R^, and R⁷ are as previously defined, is oxyalkylated with an alkylene oxide of 2 to 8 carbon atoms or a mixture of such alkylene oxides. The oxyalkylation is carried out in the presence or absence of an alkali, such as potassium hydroxide solution, sodium hydroxide solution or sodium methylate, advantageously at elevated temperatures, for example at from 80°C to 140°C, preferably from 100°C to 120°C.

The selection of a ketone or aldehyde to react with an ammonia capped poyether will depend upon the particular polyetheramine to be produced. In general, an aldehyde for use in the present invention will be formaldehyde or an aldehyde of the general formula Rl⁷-CH=0 and a ketone of the formula R¹⁷R¹⁸C=0 where R¹⁷ and R¹⁸ are each independently an unsubstituted or inertly substituted alkyl, aryl, arylalkyl, or alkylaryl where each alkyl contains 1 to 12 carbon atoms and each aryl, arylalkyl, or alkylaryl contains 5 to 20 carbons atoms. Preferably each alkyl contains 1 to 8 carbon atoms and more preferably from 1 to 4 carbon atoms. Each aryl, arylalkyl, or alkylaryl preferably contains from 5 to 15 carbon atoms and more preferably from 6 to 12 carbon atoms. By inertly substituted, it is meant the substituted groups do not undesirable interfere with the activity of the polyetheramine. As used herein, alkyl is a linear or branched alkyl.

Examples of aldehydes and ketones for use in the present invention include, acetone, propionaldehyde, acetaldehyde, glycoaldehyde, butyraldehyde, benzaldehyde, cyclohexanone, 2-butanone, 3-pentanone, acetophenone, benzophenone. In a preferred embodiment, the ketone or aldehyde is selected from acetone, propionaldehyde, benzaldehyde and cyclohexanone.

Conditions for contacting an ammonia or amino capped polyether with an aldehyde or ketone are generally selected such that the resulting imine can be formed in an economical manner. The reaction condition will also depend on the properties of the ketone or aldehyde used. For example, a reaction with an amino capped polyether and acetone can be done at ambient temperatures and ambient pressure. When the ketone or aldehyde are less compatible, for example, less soluble than acetone, with the amino capped polyether, reaction parameters such as temperature, pressure, and concentration may need to be increased to obtain an acceptable reaction rate. The molar concentration of aldehyde or ketone to the amine capped polyether is generally 1:1 to 10:1. Changes in standard parameters such as temperature, pressure, reactant concentrations and the like, can be varied to determine optimal yield, reaction times.

The nitrile compounds for use as reactants in the present inventions are of the general formula

where x, y, and s, are as previously designed and q is from 0 to 4. Examples of preferred nitrile compounds are glycolonitrile, acrylonitrile, and lactonitrile.

The conditions under which the cyanide compound and ammonia or amine capped polyether are contacted with one another to form a nitrile is dependent upon the individual cyanide and polyether compound. For example, lactonitrile will readily react with an amine capped polyether under ambient conditions. When acrylonitrile is used, an increased temperature and pressure may be needed as disclosed in the working Examples herein. Optimal reaction parameters can be determined by standard procedures in the art. Any alkylene oxide may be reacted with an ammonia or amine capped polyether for use in the present invention. The type of alkylene oxide used will of course, be limited to an alkyl chain length which doesn't inhibit the reaction due to factors such as solubility, steric hindrance, and other reaction parameters known in the art. In general, preferred alkylene oxides are of the general formula

R19-C-C O where R-- 9 _s hydrogen or a C^ - C3 alkyl. Examples of preferred alkylene oxides include ethylene oxide, propylene oxide and butylene oxide. With ethylene oxide and propylene oxide as the most preferred.

The reaction between the alkylene oxide and ammonia capped polyether is generally done where the mixture is subjected to temperatures and pressures above ambient. For example, the pressure is generally from 100 to 5,000 psi. Preferably the mixture is subject to a pressure of 500 to 2,000 psig. The temperature of the mixture for reaction is generally from 50°C to 500°C and more preferably from 100°C to 200°C. Procedures to adjust reaction parameters to increase the rate of reaction or yield of final product, are well known to those skilled in the art .

Other conditions for determining the conditions of contacting an ammonia capped polyether with an aldehyde, ketone, nitrile compound or alkylene oxide, such as the molar ratios of starting materials to be used can be readily determined by those skilled in the art based upon the working examples herein. Hydrogenation of the intermediate materials to produce the final polyetheramine products of the present invention is done under conditions and with catalysts commonly employed in the art for hydrogenation reactions.

Catalysts for amination are well known in the art. Preferred catalysts for amination are those comprising rhenium (atomic number 75) and nickel, and preferably at least one of cobalt, boron and copper and/or ruthenium impregnated on a support material wherein, preferably, the weight ratio of the nickel to the rhenium is in the range of from 1 to 30; the weight ratio of the nickel to the cobalt is from 1 to 20; the weight ratio of the nickel to the boron is from 1 to 20; the weight ratio of the nickel to the copper and/or ruthenium is from 1 to 20; and the total nickel, rhenium, cobalt, boron plus copper and/or ruthenium metal present is preferably in the range of from 5 to 90 percent by weight of the total (support and metal) .

Advantageously, the catalysts are solid catalysts, preferably supported catalysts with the active species provided on the surface of the support through, for example, coating or impregnation. Support materials are preferably not themselves sufficiently catalytically active to produce high yields of product in a reasonable time. Useful supports are advantageously porous and have surface areas preferably of from 10 to 500, more preferably from 100 to 300 square meters per gram.

The catalyst is suitably any convenient size or shape, for instance in the form of powders, spherical or conical pellets, extruded strips. The shape of the support usually depends on the shape suited for a particular apparatus used to perform the reaction.

Impregnated spherical pellets for example, ranging in diameter from 1/32 inch to 3/16 inch and extruded strips of a cylindrical-type shape for example, ranging from 1/32 inch to 1/2 inch in length are among those useful as supports .

While any support material which results in an active amination catalyst is suitably used in the practice of the invention, support materials are not equivalent in their ability to form active Ni-Re catalysts. For example, carbon supported and silica-magnesia supported Ni-Re catalysts using CXC carbon from National Carbon Company even with large surface areas, have reduced catalytic activity in amination reactions . Preferred supports include those based on silicon, aluminum, and/or titanium, preferably based on silica or alumina, particularly alpha -alumina, silica, silica-alumina, kieselguhrs or diatomaceous earths and silica-titania, most preferably silica-based support.

Even the alpha-alumina, silica, silica-alumina, kieselguhrs or diatomaceous earths and silica-titania support materials are not equivalent. Those supports which form more active catalysts are those which yield optimum amination conversions at less severe reaction conditions, for example, lower reaction temperatures.

Therefore, although the catalyst of the invention on most of these supports shows catalytic activity in the amination reaction, some supports are more preferred because they result in a more active catalyst, that are capable of withstanding more extreme reaction conditions, such as higher reaction temperatures and/or exhibit better selectivity for the desired product.

The actual effectiveness of a material as a support in a catalyst is not predictable in advance, but determining effectiveness is within the skill in the art, for instance by methods disclosed in reductive amination catalyst patents such as U.S. Patent 4,123,462 which is hereby incorporated herein by reference in its entirety. Among the types of preferred supports, there appears to be some relationship between catalytic activity and the amount of surface area of the particular support materials . The relationship is believed to be attributable to reactions which occur on the catalyst surface and are, therefore, affected by adsorption- desorption equilibria of the reaction materials. The activity of a catalyst is, therefore, affected, within certain limits, by varying surface area of the supports and other surface properties including support shape, pore size, and pore volume. In general, greater dispersion of the metals on higher surface area active supports produce more active catalysts.

The catalysts include catalysts which contain various other metals in admixture with the nickel and rhenium which do not detrimentally affect catalytic properties. These additional metals, in certain amination processes are optionally used to improve selectivity and activity of the catalyst or extend the activity life and other physical properties of the catalyst. Examples of additional metal components include cobalt, copper, boron, ruthenium, calcium, magnesium, lithium, sodium, potassium, chromium, molybdenum, rubidium, cesium, cerium, iron, silver, zinc, barium, tungsten, uranium, strontium, palladium, titanium, manganese, rhodium and combinations thereof, preferably cobalt, boron, copper, and/or ruthenium.

The catalyst is activated by any procedure wherein the impregnated metal is converted into a catalytically active form. This activation optionally includes alloy formation, proper phase orientation of the metals and/or an adjustment in the oxidation level of the metals. An activation step optionally includes a reduction process within the skill in the art. Often the catalyst is first reduced before effecting the reaction, and then continuously reduced during the course of the reaction to keep the catalyst active and functioning. Insufficient reduction results in depletion of hydrogen at the catalyst surface and resulting decreased reaction.

A preferred activation procedure includes use of a hydrogen atmosphere in contact with the catalyst. The hydrogen is advantageously fed over the catalyst at an elevated temperature, preferably on the order of at least about 150°C, more preferably about 350°C and preferably less than about 600°C, more preferably less than about 500° C for periods of from about 30 minutes to about 8 hours, more preferably from about 3 hours to less than about 6 hours. Specific conditions for reduction depend on the particular catalyst composition being activated.

Before or during an activation step, the catalyst is optionally calcined. In a preferred calcining step, the catalyst is heated to temperatures of from about 200°C to about 500°C for about 45 minutes to about 3 hours or more if convenient. It is preferred that the calcining be carried out in air.

The drying step previously discussed is optionally replaced by a calcining step or activating step. Alternatively, in such cases drying is considered to take place simultaneously with a calcining and/or activating step.

Nickel-rhenium catalysts suitable for use in the practice of the invention are known in the art and include those disclosed by Best, et al . in U.S. Patent 4,111,840. Preferred catalysts are those disclosed by Burgess et al in U.S. Patent 5,196,588 and those disclosed by Chang et al. in U.S. Patent Application Serial Number 08/459,892 filed June 2, 1995, most preferably those disclosed by Chang et al .

The amount of catalyst preferred for use in the practice of the invention depends on many variables including the relative proportions of the reactants, reaction conditions and the degree of conversion and selectivity desired. Moreover, the amount of catalyst also depends on the catalyst itself, for example, its metal loading, activity and age. Overall, the amount of catalyst used in the process is an amount sufficient to result in the desired reaction.

The amination reaction is run under elevated pressure, advantageously sufficient pressure to maintain desired reaction rate at a desired temperature. Conveniently the pressure is at least about 10 atmospheres (1013 kPa) , preferably at least about 200 psig (1378 kPa) , more preferably at least about 500 psig (3,448 kPa), most preferably at least about 1000 psig (6,896 kPa) . Preferably the pressure is lower than a pressure which requires unduly heavy equipment or danger, conveniently less than about 400 atmospheres (40,530 pKa) .

Preferred temperatures for the amination reaction depend on the particular starting material, ratios of reactants, and most importantly, the activity of the catalyst used. Temperatures are advantageously at least sufficient to result in supercritical phase and insufficient to result in undesirably increased by¬ products. Overall, such temperatures are advantageously at least about 120°C, preferably at least about 150°C, more preferably at least about 160°C, most preferably at least about 170°C. Also, to avoid increased by-products, the temperatures are preferably less than about 250°C, more preferably less than about 225°C, most preferably less than about 200°C.

Reactants are optionally fed as a feed stream which is optionally liquid, supercritical fluid or gaseous. Reaction product stream(s) taken from the reaction zone are also optionally liquid, supercritical fluid or gaseous. It is not necessary that the feed stream and the reaction product stream be in the same physical state. For example, a reactant stream is optionally gaseous and a reaction product stream liquid, or vice versa. Feed reactants are suitably supplied in any amount which results in product; conveniently a liquid hourly space velocity (LHSV) (total feed volume divided by volume of reactor containing catalyst per hour) is at least about 0.05 reciprocal hours, advantageously from 0.05 to 2, preferably from 0.1 to 1.5, more preferably from 0.25 to 1.25, most preferably from 0.5 to 1.0 reciprocal hours.

To maintain a given conversion rate, as a reactant polyether derivative feed rate is increased, one or more other process variables are changed; for instance catalytic activity or temperature is increased. Most commonly, a given conversion rate is maintained by an increase in temperature with an increase in for example, polyether derivatives feed rate. Higher temperatures, however, lead to increased by-products; therefore, the LHSV is balanced with the temperature to achieve the optimum result in each situation.

A feed stream to the amination reaction zone comprises reactant polyether derivative, ammonia and hydrogen. Stoichiometrically, one molecular unit of ammonia is required per molecular unit of functional group, for example, hydroxyl, to be replaced. However, the amination reaction is favored by the presence of excess ammonia. Thus, the molar ratio of ammonia to total polyether derivative is advantageously from at least about 1:1 to 100:1, preferably from 5:1 to 70:1, more preferably from 10:1 to 50:1, and most preferably 10:1 to 40:1.

Ammonia employed in the reaction is optionally anhydrous or contains small amounts of water.

Hydrogen is also provided to the amination reaction zone. The amount of hydrogen gas present in the amination process of the present invention is not critical. Advantageously, hydrogen is added in an amount sufficient to maintain the catalyst in an active state. Lower amounts of hydrogen, however, are preferred for maintaining a supercritical state. A preferred amination process is carried out where the hydrogen is present in an amount wherein the hydrogen to ammonia and/or amine molar ratio is greater than 0.01 and preferably less than the ratio 1.0. More preferably, hydrogen is provided in an amount of at least about 0.5 mole percent based on the total moles of ammonia and/or amine, most preferably this percentage is between 1.0 and 10 percent.

Processes of the invention are preferably conducted in a continuous manner more preferably with a reactor feed being passed through a bed of particulate catalyst. The reactor is optionally an up-flow or down-flow reactor and optionally has a fluidized bed or, more commonly, a fixed bed. The catalyst bed optionally contains inert particles which are, for instance, interspersed throughout the bed and/or form discrete layers, for example, at an end or intermediary to the bed. Preferably, flow through a catalyst bed is substantially plug flow. The reductive amination process of the invention is suitably carried out in any equipment having heating means. The process is optionally carried out continuously or in batch. In continuous equipment no agitating means is required because the nature of the continuous process causes the reactants to continually flow in intimate contact with the catalyst material. Agitating means is, however, advantageous in batch processes.

The polyetheramine product compositions from practice of the invention are optionally subjected to separation techniques within the skill in the art for recovering individual components or fractions of the compositions. Illustrative techniques are disclosed in U.S. Patent 5,196,588 (Burgess et al . ) , U.S. Patent 4,400,539 (Gibson, et al.) , U.S. Patent 4,404,405 (Winters), and U.S. Patent 3,151,115 (Moss, et al.) .

Polyetheramine derivatives conveniently produced by the process of the invention are useful in polyurethanes, epoxy resins, fuel and lubrication additives applications, in detergent applications and the like.

The polyetheramines are particularly useful as fuel and lubricant additives because of their solubility therein and the advantageous cleaning effects on fuel injectors. Thus, they are particularly useful in gasoline and other fuels for engines having fuel injectors.

Preferred among these compounds are those represented by Formulas 1, 4, 5, 6, 7, and 8. These compounds are preferred for use as fuel additives because of their surprising solubility when dissolved in fuels. They have other surprising properties of thermal stability and advantageous cleaning effects on fuel systems . The following examples are to illustrate this invention and not limit it. Ratios, parts, and percentages are by weight unless otherwise stated.

EXAMPLE A: AMINATION CATALYST

Preparation of Catalyst - A hot solution containing 118 gm Ni (N0₃) ₂-6H₂0, 10.2 gm NH₄Re0₄, 29.5 gm H3BO3 and 34.5 g. Co(N0₃)₂.6H₂0, and 25.6 gm of Cu (N0₃) ₂ •2.5H₂0 in 400 ml of distilled water was prepared. Fifty g s of predried catalyst support (an alumina support commercially available from U.O.P. under the trade designation SAB-17™) was placed in a 500 ml round bottom flask under vacuum. Then 200 ml of the catalyst solution was added to the support.^" After thorough mixing, the impregnated support was re-dried at 120 C for 2 hour and impregnated as described above with a second batch of the 200 ml catalyst solution. The completely impregnated support was dried again at 120 C for 2 hour, calcined at 300 C in a furnace for 3 hours.

The resulting catalyst contains a Ni/Co/Cu/Re/B metal weight ratio of 48/14/14/14/10 and the Ni/Co and Ni/Cu weight ratios were 3.4.

Activation of Catalyst - The catalyst was loaded into a tubular activation chamber with a stream of pure H2 flow (40 ml/min) evenly through the entire catalyst bed. Temperature inside the chamber was gently heated and held o at 320 ±15 C for 3 hours. Then the heat was turned off and the catalyst was allowed to cool under continuous hydrogen flow. The activated catalyst (total metal loading= 50 wt . percent) was then stored in a nitrogen filled dry box until use. EXAMPLE B: Plug-Flow Reactor

Loading of the catalyst (44 g/75 ml) into a plug-flow having dimensions of 1 inch (25.4 mm) inside diameter and 100 mL capacity, commercially available from Autoclave Engineer rated at 9500 psi (65500 kPa)/5500°F (260°C) reactor, was performed inside a 2 filled drybox (O2 less than 10 ppm) to prevent deactivation of the catalyst. Ceramic beads packing (1/8") was used above and below the catalyst so the catalyst bed was positioned in the constant temperature zone of the reactor.

Example 1 - Amination of a polyoxybutylene alcohol with ammonia

A polyoxybutylene alcohol (M.wt.= 1600) was aminated with ammonia in a conventional plug-flow reactor (75 ml of a 50 wt. percent Ni/Co/Cu/Re/B catalyst on SAB-17® alumina support from UOP) described in Example B under the following conditions: temperature: 200°C; Pressure: 1200 psig; Feed Rates: 1.0 l/min for polyether (LHSV=0.8), 1.0 ml/min for ammonia (NH3/OH molar ratio= 56), 100 seem (11 mole percent) for hydrogen. After removing NH3, the product solution was titrated with 0.2N HCl indicating that 100 percent amination (displacement of the OH group with the NH₂ group) was obtained. l^c NMR spectroscopy was performed for confirmation of the C-N bond.

Example 2

Five hundred grams of the NH3 capped polyether (0.313 moles) from Example 1 and 230 ml of acetone (3.132 moles) were added into a 1-liter container and mixed under ambient conditions for 16 hours. l^C NMR indicated that the conversion of the C-N group to C-N=C(CH3)2 imine group was about 95 percent complete. After removing the excess acetone, the imine was reduced in a conventional plug-flow reactor described in Example B under the following conditions: temperature: 130°C; pressure: 1400 psig; feed rate: 0.5 ml/min for imine compound, 192 seem for H2 • -^C NMR confirms that the final product was about 90 percent isopropylamine capped polyether.

Example 3

Five hundred grams of the NH3 capped polyether (0.313 moles) from Example 1 and 18.2 grams (0.313 moles) of the propionaldehyde were added into a 1-liter container and mixed under ambient conditions for 4 hours. l^C NMR indicated that the conversion of the C-N group to the C- N=CH(C2H5) imine group was about 95 percent complete. The imine compound was reduced in a conventional plug-flow reactor described in Example B under the following conditions: temperature: 120°C; pressure: 1200 psig; feed rates: 0.5 ml/min for imine compound, 195 seem for H2. l^C NMR indicates that the final product solution contains about 80 percent of propylamine capped polyether.

Example 4

Five hundred grams of the NH3 capped polyether (0.313 moles) from Example 1 and 49.2 grams (0.345 moles) of an aqueous 40 wt . percent glycolonitrile solution were added into a 1-liter container and mixed under ambient conditions for 16 hours. ---^C NMR indicated that the conversion of the C-N group to the C-N-CH2-CN cyanide group was about 75 percent complete. Additional stirring for 24 hours yields about 90 percent conversion. The cyanide group was reduced in a conventional plug-flow reactor described in Example B under the following conditions: temperature: 120°C; pressure: 1400 psig; feed rates: 0.5 ml/min for cyanide compound, 200 seem for H2. 13c NMR indicates that the final product solution contains about 75 percent ethylenediamine capped polyether.

Example 5

Five hundred grams of the NH3 capped polyether (0.313 moles) from Example 1 and 22.3 grams (0.313 moles) of lactonitrile were added into a 1-liter container and mixed under ambient conditions for 16 hours. --^C NMR indicated that the conversion of the C-N group to the

C-N-CHCH3CN cyanide group was about 95 percent complete. The cyanide group was reduced in a conventional plug-flow reactor as described in Example B under the following conditions: temperature 110°C, pressure: 1350 psig, feed rates: 0.5 ml/min for cyanide compound, 200 seem for H2. 3c NMR indicates that the final product solution contains about 30 percent 1-methyl ethylenediamine capped polyether.

Example 6

Five hundred grams of the NH3 capped polyether (0.313 moles) from Example 1 and 16.61 grams (0.313 moles) of acrylonitrile were added into a 1-liter container and mixed at 150°C and 1500 psig for 16 hours. ¹³C NMR indicated that the conversion of the C-N group to the C-N-CH2CH2CN cyanide group was about 35 percent. Additional mixing for 60 hours resulted in about 90 percent conversion. The cyanide group was reduced in a conventional plug-flow reactor described in Example B under the following conditions: temperature: 125°C, pressure: 1250 psig, feed rates: 0.45 ml/min for cyanide component, 200 seem for H2. -~^ NMR indicated that the final product solution contained about 60 percent propylenediamine capped polyether. Example 7

Five hundred grams of the NH3 capped polyether (0.313 moles) from Example 1 and 13.8 grams (0.313 moles) of ethylene oxide were added into a 600-ml Parr stir reactor and mixed at 150°C and 1500 psig for 16 hours. The resulting polyether was aminated in a conventional plug- flow reactor described in Example B at the following conditions: temperature: 180°C, pressure: 1200 psig, feed rates: 0.3 ml/min for polyether, 0.5 ml/min for NH3, 100 seem for H2 • -~ ~^ NMR indicated that the final product solution contained about 35 percent ethylenediamine capped polyether, and about an equal amount of a piperazine capped polyether.

Example 8

Five hundred grams of the NH3 capped polyether (0.313 moles) from Example 1 and 27.6 grams (0.626 moles) of ethylene oxide were added into a 600-ml Parr stir reactor and mixed at 150°C, and 1000 psig for 40 hours. The resulting polyol was aminated with NH3 in a conventional plug-flow reactor described in Example B at the following conditions: temperature: 200°C, pressure: 1350 psig, feed rates: 1.0 ml/min for polyether, 1.0 ml/min for NH3, 190 seem for H2 • ¹³C NMR indicated the final product solution contained about 40 percent piperazine capped polyether and 25 percent ethylenediamine capped polyether.

Claims

WHAT IS CLAIMED IS:

1. A process for producing polyetheramine products comprising contacting an ammonia capped polyether with an aldehyde or ketone under conditions to form an

intermediate imine and reduction of the imine under hydrogenation conditions to form the polyetheramine product.

2. The process of Claim 1 wherein the ammonia capped polyalkylene polyether contains from 6 to 500 carbon atoms.

3. The process of Claim 2 wherein the ammonia capped polyalkylene polyether is of the formula:

wherein p is 1, 2, or 3;

R¹ is (a) a linear or branched polyether chain having from

2 to 100 alkylene oxide units in the chain wherein the polyether chain is obtained from an alkylene oxide of 2 to

8 carbon atoms, or a mixture of such alkylene oxides;

(b) a polyether radical of the general formula

-R⁸-Ar-(R⁵) (R⁶)(R⁷)

Formula 2 or (c) an alicyclic polyether or alkylalicyclic polyether of the general formula

-R⁸-Cy-(R⁵) (R⁶)(R⁷) Formula 3 where Ar is an aromatic moiety;

Cy represents a cyclic structure of at least about 4 atoms;

R⁵, R⁶ and R⁷ may be identical or different and are each independently hydrogen, hydroxyl, or a hydrocarbon radical of 1 to 30 carbon atoms which may be substituted with aldehyde, ketone, or hydroxyl moieties;

R⁸ is a polyether chain wherein the chain has from 2 to 100 alkylene oxide units obtained from alkylene oxides of 2 to 8 carbon atoms or a mixture of such alkylene oxides; with the proviso that when R¹ is a moiety of Formula 2 or Formula 3, then p is 1.

4. The process of Claim 3 wherein R¹ is a polyether radical of Formula 2.

5. The process of Claim 4 wherein Ar is selected from 1,3-diazoles, pyrazoles, pyrazines, pyrimidines,

pyridazines, purines, pteridines, thiophenes, oxazones, pyridines, dihydroquinolines, benzoquinolines,

diazaanthracenes, naphthalenes, phenyl groups, and combinations thereof.

6. The process of Claim 3 wherein R¹ is an alicyclic polyether or alkylalicyclic polyether of Formula 3.

7. The process of Claim 6 wherein Cy is selected from cyclohexane, furan, tetrahydrofuran, dioxolane, pyran, tetrahydropyran, dioxepin, azetidine, dihydropyroles, pyrrolidine, pyrroline, pyrrolidinone, cyclic lactams of from 5 to 7 cyclic atoms, and combinations thereof.

8. The process of Claim 1 wherein the ketone is of the formula R¹⁷R¹⁸C=O wherein R¹⁷ and R¹⁸ are each

independently an unsubstituted or inertly substituted alkyl, aryl, arylalkyl, or alkylaryl where each alkyl contains 1 to 12 carbon atoms and each aryl, arylalkyl, or alkylaryl contains 5 to 20 carbons atoms.

9. The process of Claim 1 wherein the aldehyde is formaldehyde or an aldehyde of the formula R¹⁷-CH=O wherein R¹⁷ an unsubstituted or inertly substituted alkyl, aryl, arylalkyl, or alkylaryl where each alkyl contains 1 to 12 carbon atoms and each aryl, arylalkyl, or alkylaryl contains 5 to 20 carbons atoms.

10. The process of Claim 1 wherein the intermediate imine is of the formula

wherein p is 1, 2, or 3;

R¹ is (a) a linear or branched polyether chain having from 2 to 100 alkylene oxide units in the chain wherein the polyether chain is obtained from an alkylene oxide of 2 to 8 carbon atoms, or a mixture of such alkylene oxides;

(b) a polyether radical of the general formula

-R⁸-Ar-(R⁵) (R⁶) (R⁷)

-R⁸-Cy-(R⁵) (R⁶) (R⁷)

Formula 3

where Ar is an aromatic moiety;

Cy represents a cyclic structure of at least about 4 atoms; R⁵, R⁶ and R⁷ may be identical or different and are each independently hydrogen, hydroxyl, or a hydrocarbon radical of 1 to 30 carbon atoms which may be substituted with aldehyde, ketone, or hydroxyl moieties;

R⁸ is a polyether chain wherein the chain has from 2 to 100 alkylene oxide units obtained from alkylene oxides of 2 to 8 carbon atoms or a mixture of such alkylene oxides; R² and R³ are each independently hydrogen, an

unsubstituted or inertly substituted alkyl, aryl,

arylalkyl, or alkylaryl;

with the proviso that when R¹ is a moiety of Formula 2 or Formula 3, then p is 1.

11. The process of Claim 10 wherein each alkyl contains 1 to 12 carbon atoms and each aryl, arylalkyl, or alkylaryl contains 5 to 20 carbon atoms.

12. A process for producing polyetheramine products comprising contacting an ammonia capped polyalkylene polyether with a cyanide compound under conditions to form an intermediate nitrile and reduction of the nitrile under hydrogenation conditions to form the polyetherpolyamine product.

13. The process of Claim 12 wherein the ammonia capped polyalkylene polyether contains from 6 to 500 carbon atoms.

14. The process of Claim 13 wherein the ammonia capped polyalkylene polyether is of the formula:

wherein p is 1, 2, or 3;

R¹ is (a) a linear or branched polyether chain having from

8 carbon atoms, or a mixture of such alkylene oxides;

(b) a polyether radical of the general formula

-R⁸-Ar-(R⁵) (R⁶) (R⁷)

-R⁸-Cy-(R⁵) (R⁶) (R⁷)

Formula 3

wherein Ar is an aromatic moiety;

Cy represents a cyclic structure of at least about 4 atoms;

R⁸ is a polyether chain wherein the chain has from 2 to

100 alkylene oxide units obtained from alkylene oxides of 2 to 8 carbon atoms or a mixture of such alkylene oxides; with the proviso that when R¹ is a moiety of Formula 2 or

Formula 3, then p is 1

15. The process of Claim 14 wherein R¹ is polyether radical of Formula 2.

16. The process of Claim 15 wherein Ar is selected from 1,3-dιazoles, pyrazoles, pyrazines, pyrimidines,

pyridazines, purines, pteridines, thiophenes, oxazones, pyridines, dihydroquinolines, benzoquinolines, diazaanthracenes, naphthalenes, phenyl groups, and

combinations thereof.

17. The process of Claim 14 wherein R¹ is an alicyclic polyether or alkylalicyclic polyether of Formula 3.

18. The process of Claim 17 wherein Cy is selected from cyclohexane, furan, tetrahydrofuran, dioxolane, pyran, tetrahydropyran, dioxepin, azetidine, dihydropyroles, pyrrolidine, pyrroline, pyrrolidinone, cyclic lactams of from 5 to 7 cyclic atoms, and combinations thereof.

19. The process of Claim 12 wherein the intermediate nitrile is of the formula

wherein

p is 1, 2, or 3;

(b) a polyether radical of the general formula

-R⁸-Ar-(R⁵) (R⁶) (R⁷)

-R⁸-Cy-(R⁵) (R⁶) (R⁷)

Formula 3 wherein Ar is an aromatic moiety;

Cy represents a cyclic structure of at least about 4 atoms;

R⁸ is a polyether chain wherein the chain has from 2 to

100 alkylene oxide units obtained from alkylene oxides of

2 to 8 carbon atoms or a mixture of such alkylene oxides; with the proviso that when R¹ is a moiety of Formula 2 or

Formula 3, then p is 1;

R⁹ and R¹⁰ are each independently hydrogen, or

where X and Y are independently hydrogen, an unsubstituted or inertly substituted alkyl, aryl, alkylaryl, or

arylalkyl;

s is an integer from 1 to 6;

with the proviso that at least one of R⁹ or R¹⁰ is

20. The process of Claim 19 wherein each alkyl contains 1 to 12 carbon atoms and each aryl, arylalkyl, or alkylaryl contains 5 to 20 carbon atoms.

21. A process for producing polyetheramine products comprising contacting an ammonia capped polyalkylene polyether with an alkylene oxide under conditions to form a hydroxyl containing species of the ammonia capped polyalkylene polyether followed by amination of the hydroxyl containing species to produce the

polyetherpolyamine.

22. The process of Claim 21 wherein the capped

polyalkylene polyether contains from 6 to 500 carbon atoms.

23. The process of Claim 21 wherein the ammonia capped polyalkylene polyether is of the formula:

wherein p is 1, 2, or 3

(b) a polyether radical of the general formula

-R⁸-Ar-(R⁵) (R⁶) (R⁷)

-R⁸-Cy-(R⁵) (R⁶) (R⁷)

Formula 3 wherein Ar is an aromatic moiety;

Cy represents a cyclic structure of at least about 4 atoms;

24. The process of Claim 23 wherein R¹ is a polyether radical of Formula 2.

25. The process of Claim 24 wherein Ar is selected from 1,3-diazoles, pyrazoles, pyrazines, pyrimidines,

diazaanthracenes, naphthalenes, phenyl groups, and

combinations thereof.

26. The process of Claim 23 wherein R¹ is alicyclic polyether or alkylalicyclic polyether of Formula 3.

27. The process of Claim 26 wherein Cy is selected from cyclohexane, furan, tetrahydrofuran, dioxolane, pyran, tetrahydropyran, dioxepin, azetidine, dihydropyroles, pyrrolidine, pyrroline, pyrrolidinone, cyclic lactams of from 5 to 7 cyclic atoms, and combinations thereof.

28. The process of Claim 21 wherein the hydroxyl

containing species of the ammonia capped polyalkylene polyether is of the formula

wherein

p is 1, 2, or 3;

R¹ is (a) a linear or branched polyether chain having from 2 to 100 alkylene oxide units in the chain wherein the polyether chain is obtained from an alkylene oxide of 2 to

8 carbon atoms, or a mixture of such alkylene oxides;

(b) a polyether radical of the general formula -R⁸-Ar-(R⁵) (R⁶)(R⁷)

-R⁸-Cy-(R⁵)(R⁶)(R⁷)

Formula 3

where Ar is an aromatic moiety;

Cy represents a cyclic structure of at least about 4 atoms;

R⁸ is a polyether chain wherein the chain has from 2 to

100 alkylene oxide units obtained from alkylene oxides of

Formula 3, then p is 1

R¹¹ and R¹² are each independently hydrogen or

arylalkyl;

n is an integer from 0 to 6;

with the proviso that at least one of R¹¹ or R¹² is of the Formula 5a.

29. The process of Claim 28 wherein each alkyl contains 1 to 12 carbon atoms and each aryl, arylalkyl, or alkylaryl contains 5 to 20 carbon atoms.

30, A compound of the Formula

wherein

p is 1, 2, or 3;

R⁴ is a linear or branched polyether chain having from 2 to 100 alkylene oxide units in the chain wherein the polyether chain is obtained from an alkylene oxide of 2 to

8 carbon atoms, or a mixture of such alkylene oxides; and

R² and R³ are each independently hydrogen, an

unsubstituted or inertly substituted alkyl, aryl,

arylalkyl, or alkylaryl.

31. The compound of Claim 30 wherein each alkyl contains 1 to 12 carbon atoms and each aryl, arylalkyl, or

alkylaryl contains 5 to 20 carbon atoms.

32. A compound of the formula

wherein

p is 1 , 2 , or 3 ;

(b) a polyether radical of the general formula

-R⁸-Ar-(R⁵) (R⁶) (R⁷)

-R⁸-Cy-(R⁵) (R ⁶ ) (R⁷)

Formula 3 wherein Ar is an aromatic moiety;

Cy represents a cyclic structure of at least about 4 atoms;

R⁸ is a polyether chain wherein the chain has from 2 to

Formula 3, then p is 1;

R¹³ and R¹⁴ are each independently hydrogen,

or

wherein s is an integer from 1 to 6;

X and Y are independently hydrogen, an unsubstituted or inertly substituted alkyl, aryl, alkylaryl, or arylalkyl; n is an integer from 0 to 6;

R¹⁵ and R¹⁶ are each independently hydrogen or a moiety of

Formula 7a, 7b, or 4a;

with the proviso that at least one of R¹³ or R¹⁴ is a moiety of Formula 7c.

33. The compound of Claim 32 wherein each alkyl contains 1 to 12 carbon atoms and each aryl, arylalkyl, or

alkylaryl contains 5 to 20 carbon atoms.

34. A compound of the formula

wherein p is 1, 2, or 3;

(b) a polyether radical of the general formula -R⁸-Ar-(R⁵) (R⁶)(R⁷)

-R⁸-Cy-(R⁵) (R⁶)(R⁷)

Formula 3

wherein Ar is an aromatic moiety;

Cy represents a cyclic structure of at least about 4 atoms;

R⁸ is a polyether chain wherein the chain has from 2 to

100 alkylene oxide units obtained from alkylene oxides of

2 to 8 carbon atoms or a mixture of such alkylene oxides; R² and R³ are each independently hydrogen, an unsubstituted or inertly substituted alkyl, aryl,

arylalkyl, or alkylaryl;

35. The compound of Claim 34 wherein each alkyl contains 1 to 12 carbon atoms and each aryl, arylalkyl, or

alkylaryl contains 5 to 20 carbon atoms.

36. A compound of the formula

wherein

p is 1 , 2, or 3;

(b) a polyether radical of the general formula

-R⁸-Ar-(R⁵) (R⁶)(R⁷)

-R⁸-Cy-(R⁵) (R⁶)(R⁷)

Formula 3

where Ar is an aromatic moiety;

Cy represents a cyclic structure of at least about 4 atoms;

R⁸ is a polyether chain wherein the chain has from 2 to

100 alkylene oxide units obtained from alkylene oxides of

Formula 3, then p is 1;

R⁹ and R¹⁰ are each independently hydrogen or

arylalkyl;

s is an integer from 1 to 6;

with the proviso that at least one of R⁹ or R¹⁰ is

37. The compound of Claim 36 wherein each alkyl contains 1 to 12 carbon atoms and each aryl, arylakyl, or alkylaryl contains 5 to 20 carbon atoms.

38. A compound of the formula

wherein

p is 1, 2, or 3;

(b) a polyether radical of the general formula -R⁸-Ar-(R⁵) (R⁶) (R⁷)

-R⁸-Cy-(R⁵) (R⁶) (R⁷)

Formula 3

wherein Ar is an aromatic moiety;

Cy represents a cyclic structure of at least about 4 atoms;

R⁸ is a polyether chain wherein the chain has from 2 to

100 alkylene oxide units obtained from alkylene oxides of

2 to 8 carbon atoms or a mixture of such alkylene oxides;

R² and R³ are each independently hydrogen, an

unsubstituted or inertly substituted alkyl, aryl,

arylalkyl, or alkylaryl;

with the proviso that when R¹ is a moiety of Formula 2 or

Formula 3, then p is 1.

39. A compound of the formula

wherein p is 1, 2 or 3;

R⁴ is a linear or branched polyether chain having from 2 to 100 alkylene oxide units in the chain wherein the polyether chain is obtained from an alkylene oxide of 2 to 8 carbon atoms, or a mixture of such alkylene oxides;

R¹¹ and R¹² are each independently hydrogen or

arylalkyl;

n is an integer from 0 to 6;

with the proviso that at least one of R¹¹ or R¹² is of the

Formula 5a.

40. A composition comprising at least about 1 mg per kilogram of fuel of a compound of Claim 30.

41. A composition comprising at least about 1 mg per kilogram of fuel of a compound of Claim 32.

42. A composition comprising at least about 1 mg per kilogram of fuel of a compound of Claim 34.

43. A composition comprising at least about 1 mg per kilogram of fuel of a compound of Claim 36.

44. A composition comprising at least about 1 mg per kilogram of fuel of a compound of Claim 38.

45. A composition comprising at least about 1 mg per kilogram of fuel of a compound of Claim 39.

46. The use of a compound of Claim 30, 32, 34, 36, 38 or 39 as a lubrication additive.

47. The use of a compound of Claim 30 32, 34, 36, 38 or 39 as a corrosion inhibitor.

48. The use of a compound of Claim 30 32, 34, 36, 38 or 39 as a biocide additive.

49. The use of a compound of Claim 30 32, 34, 36, 38 or 39 as a dispersion additive.

50. The use of a compound of Claim 30 32, 34, 36, 38 or 39 as a defoamer additive.

51. A process for producing a polyetheramine product comprising contacting an ammonia capped polyether with an ethyleneimine or substituted ethyleneimine under

conditions to form a polyether amine.