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Publication numberUS3686315 A
Publication typeGrant
Publication dateAug 22, 1972
Filing dateFeb 24, 1969
Priority dateFeb 24, 1969
Publication numberUS 3686315 A, US 3686315A, US-A-3686315, US3686315 A, US3686315A
InventorsRosenwald Robert H
Original AssigneeUniversal Oil Prod Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Reaction product of epichlorohydrin compound and beta-alkylamine
US 3686315 A
Abstract
Reaction product of a epichlorohydrin compound and a beta-alkylamine. The latter is defined as an alkylamine in which the alkyl group is attached to the nitrogen atom at its beta carbon atom. The reaction product is particularly useful as an additive to retard deterioration of hydrocarbon oils.
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United States atent Rosenwald 1 Aug. 22, 1972 [54] REACTION PRODUCT OF [56] References Cited EPICHLOROHYDRIN CONIPOUND AND BETA ALKYLAMINE UNITED STATES PATENTS 72 Inventor; Robert Rosenwald, western 3,497,556 2/1970 Lanner et a1 ..260/584 R Springs, ]11 3,189,652 6/1965 Pollitzer ..260/584 R [73] Assignee: gnivlgil'sal 031 Products Company, Primary Examiner joseph Rebold es ames Assistant Examiner-Richard L. Raymond [22] Filed: Feb. 24, 1969 Attorney-James R. Hoatson, Jr. and Bernard L. 21 App1.No.: 801,853 Kramer Related us. Application Data [57] ABSTRACT [63] Continuation-in-part of Ser. No. 463,901, June Reaction product of a epichlorohydrin compound and 14, 1965, Pat. No. 3,457,053. a beta-alkylamine. The latter is defined as an alkylamine in which the alkyl group is attached to the --260/584 R 72, 260/583 R, nitrogen atom at its beta carbon atom. The reaction 260/583 P product is particularly useful as an additive to retard [51] Int. Cl. ..C07c 91/02, C07c 91/ 10 deterioration f hydrocarbon i [58] Field of Search .260/584 R, 585R, 583 R 3 Claims, N0 Drawings REACTION PRODUCT OF EPICI-ILOROHYDRIN COMPOUND AND BETA-ALKYLAMINE CROSS REFERENCE TO RELATES APPLICATIONS DESCRIPTION OF THE INVENTION The novel compound of the present invention is the reaction product formed by the reaction of a particular type of amine with an epihalohydrin compound. The particular type of amine for use in forming the reaction product is critical and is a beta-alkyl amine, herein referred to as beta-amine, and is one in which the alkyl group is attached to the nitrogen atom at the beta or second carbon atom of the alkyl group. It now has been found that the use of the beta-amine in preparing the reaction product of the present invention offers unexpected advantages over reaction products prepared when using alpha-alkyl amines, herein referred to as alpha-amines, in which the alkyl group is attached to the nitrogen atom at the terminal carbon atom of the alkyl group.

Very effective additives for hydrocarbon oils, particularly hydrocarbon oils higher boiling than gasoline, have been prepared by the reaction of alpha-amines with epihalohydrin compounds. While these additives are very effective, they do have the disadvantage of high pour point and are high cloud point. In other words the reaction product tends to gel and solidify at ambient temperature, especially during the colder seasons of the year. When this occurs, it is objectionable because the user of the additive either must handle a product which is part liquid and part solid or the user must go through the added time and expense of heating the compound in order to form a liquid product. As can be well appreciated, this added requirement interferes with the ready use of theadditive and, in some cases, may mean the difference between a decision to use the additive commercially or not to so use it.

As will be illustrated by the data in the examples appended to the present specifications, the reaction product prepared from the beta-amine is of considerably lower pour point and lower cloud point. Any suitable beta-amine is used as a reactant in preparing the novel additive of the present invention. In one embodiment the beta-amine is a monoamine and, while it may contain from four to about 50 carbon atoms, it preferably contains from about six to about carbon atoms. Illustrative preferred beta-amines include lmethylpentylamine, l-methylhexylamine, l-methylheptylamine, l-methyloctylamine, l-methylnonylamine, l-methyldecylamine, l-methylundecylamine, l-methyldodecylamine, l-methyltridecylamine, l-methyltetradecylamine, l-methylpentadecylamine, l-methylhexadecylamine, l-methylheptadecylamine, l-methyloctadecylamine, l-rnethylnonadecylamine, etc. It is understood that the long alkyl chain may be straight chain or may contain branching in the chain other than any additional carbon attachment to the beta carbon atom.

In another embodiment the beta-amine is a polyarnine containing at least one beta-amine configuo propylenediamine,

ration. Illustrative preferred beta-diamines include N- 1 -methylpentylpropylenediamine, N- 1 -methylhexylpropylenediamine, N- l -methylheptylpropylenediamine, N- l-methyloctylpropylenediamine, N-l-methylnonylpropylenediamine, N- l -methyldecylpropylenediarnine, N- l -methylundecyl-propylenediamine, N- 1 -methyldodecyl-propylenediamine, N-l-methyltridecyl- N- 1 -methyltetradecylpropylenediamine, N-l-methylpentadecylpropylenediamine, N-l-rnethylhexadecylpropylenediamine, N-l-methylheptadecylpropylenediamine, N- l-methyloctadecylpropylenediamine, N-l-methylnonadecylpropylenediamine, etc., similarly substituted ethylenediamines, butylenediamines, pentylenediamines, hexylenediamines, heptylenediarnines, etc., as well as dialkylenetriamines, trialkylenetetramines, tetralkylenepentamines, etc., containing at least one beta-amine configuration. Here again, it is understood that the long alkyl chain may be straight chain or may contain branching along the chain other than additional carbon linkage on the beta carbon atom.

While the preferred beta-amines for use in accordance with the present invention are beta-alkyl amines, it is understood that the corresponding beta-alkylene amines may be used but not necessarily with equivalent results. The beta-alkylene amines, both monoamines and polyamines, will contain unsaturation in the long alkyl chain. Such beta-amines may result when they are prepared from unsaturated fatty acids.

The beta-amines are prepared in any suitable manner. In most methods of preparation a mixture of beta-amines may be formed and such mixture of betaarnines may be used for reaction with the epihalohydrin compound in accordance with the present invention.

As hereinbefore set forth the beta-amine is reacted with an epihalohydrin compound. Epichlorohydrin is preferred. Other epichlorohydrin compounds include 1,2-epoxy-4-chlorobutane, 2,3-epoxy-4-chlorobutane, 1,2-epoxy-5-chloropentane, 2,3-epoxy-5-chloropentane, etc'. In general the chloro derivatives are preferred, although it is understood that the corresponding bromo and iodo compounds may be employed. In some cases epidihalohydrin compounds may be utilized. It is understood that the different epihalohydrin compounds are not necessarily equivalent and that, as hereinbefore set forth,

epichlorohydrin is preferred.

The beta-amine is reacted with the. epihalohydrin compound in a mole ratio of from l to 2 mole proportions of beta-amine to 1 to 1.5 mole proportions of epihalohydrin compound. In a particularly preferred embodiment of the invention, the beta-monoamine is reacted with epichlorohydrin in equal mole proportions, although an excess of one of the reactants may be used when desired. A preferred reaction product is a polymeric product prepared by reacting equal mole proportions of the amine and epichlorohydrin and containsfrom about 2 to 20 or more recurring units and preferably from about 2 to about 10 recurring units.

The desired quantity of beta-amine and epihalohydrin compound may be supplied to the reaction zone and therein reacted, although generally it is preferred to supply one reactant to the reaction zone and then introduce the other reactant step-wise. Thus, usually it is preferred to supply the epichlorohydrin to the reaction zone and to add the beta-amine stepwise, with stirring. Preferably the reaction of epichlorohydrin with the second or later portions of beta-amine is effected at a higher temperature than with the first portion of the beta-amine. The reaction preferably is effected in the presence of a solvent which may comprise a hydrocarbon and particularly an aromatic hydrocarbon including benzene, toluene, xylene, ethylbenzene, cumene, etc., or an alcohol including ethanol, propanol, butanol, etc. In another embodiment the solvent may comprise a glycol including ethylene glycol, propylene glycol, glycerol, etc., or a saturated aliphatic hydrocarbon including hexane, heptane, octane, etc.

The reaction of the beta-amine and epihalohydrin is effected at any suitable temperature which generally will be within the range of from about 50 to about 200C. and preferably within the range of from about 60 to about 150C. Conveniently, this reaction is effected by heating a solution of epichlorohydrin in aromatic solvent, with stirring, gradually adding the betaamine thereto, and continuing the heating, preferably at a higher temperature until the reaction is completed, or the reverse order of adding the reactants may be used. In the preparation of the polymeric reaction product, the reaction mixture, following completion of the reaction of the beta-amine and epihalohydrin, is treated with an inorganic base in order to convert the organic halide salt of the reaction mixture to an inorganic halide salt and to thereby liberate the free amine for further reaction to form the desired polymeric product. This may be effected in any suitable manner and generally is accomplished by reacting the primary reaction product with a strong inorganic base such as sodium hydroxide, potassium hydroxide, etc., to form the corresponding metal halide. The reaction to form the metal halide is effected at a temperature within the range of from about 60 to about 200C. and preferably from about 75 to about 150C. The inorganic base may be added in at least two steps with intervening heating and reacting so that organic halide formed after the first addition of inorganic base is in turn reacted to liberate the free amine.

in one embodiment the product at this stage of manufacture may be withdrawn from the reaction zone and filtered or otherwise treated to remove the inorganic halide. Generally, however, it is preferred to perform the next step in the same reaction zone without removing the inorganic halide. At the conditions used in forming the polymeric reaction product, the inorganic halide is inert and, therefore, its presence is not objectionable. Regardless of whether or not the inorganic halide is removed, the primary reaction product of the amine compound and epihalohydrin compound is now further heated and reacted in order to form the desired linear polymeric reaction product. This further heating and reacting is at a temperature of from about 75 to about 200C. and preferably from about 80 to about 15 C.

After formation of the desired polymeric reaction product or before this step as mentioned above, the inorganic halide salt is removed in any suitable manner,

including filtering, centrifugal separation, etc. in some cases, it may be of advantage to effect the filtration at an elevated temperature which may range from about 35 to about C. or more. When desired, water or other aqueous solvent may be added to the reaction mixture to dissolve and facilitate removal of the inorganic halide salt.

The reaction product prepared in the above manner is a new composition of matter and accordingly is being so claimed in the present application. The reaction product is recovered as a viscous liquid which, as hereinbefore set forth, has a low pour point and low cloud point. Generally, it will range from a light through amber color, although, in some cases, it may be of a dark color. For most uses, the reaction product may be dissolved in a suitable solvent, particularly a hydrocarbon and, more particularly, an aromatic hydrocarbon. Accordingly, a convenient method is to allow the reaction product to be recovered in the solvent used during the manufacture thereof and, when necessary, to add additional solvent to form a final composition of the desired concentration of active ingredients. However, when desired, the solvent used during the reaction may be removed by vacuum distillation.

While the reaction product may be used for the stabilization of gasoline, naphtha, or other relatively low boiling hydrocarbon oils, it is particularly applicable to the stabilization of higher boiling hydrocarbon oils including fuel oil, diesel oil, jet fuel, etc. The fuel oils are marketed under various names including burner oil, furnace oil and, of course, various grades of fuel oil. During storage and/or use, these oils undergo deterioration, with the formation of sediment, undesired discoloration, etc. The formation of sediment is objectionable because the sediment tends to plug strainers, burner tips, injectors, etc., and, when used as diesel fuel, tends to form varnish and sludge in the diesel engine. Discoloration of the oil is objectionable for various reasons, particularly the customers preference for light colored oils.

Deterioration of the jet fuel and burner oil at high temperature also is a serious problem. For example, jet fuel is used as a'heat exchange medium for hot exhaust gases and deterioration of the jet fuel results in plugging of the exchanger coils. This problem of deposit formation in heat exchangers also occurs during the processing of hydrocarbon oils in which the hydrocarbon oil charge at a lower temperature is passed into indirect heat exchange with hot reaction products of the process. This serves the economic ad vantage of partially heating the charge to the process and of partially cooling the reaction products of the process. Here again, it is important that deposit forma tion be. avoided or at least reduced to a minimum in order to permit satisfactory and continuous operation of the heat exchange system. Otherwise plugging of the tubes and/or shell of the heat exchanger will decrease heat transfer and eventually will require shutdown of the plant in order to clean the heat exchanger and, if necessary, to replace all or a portion of the heat exchange equipment.

The above difficulties are avoided by incorporating the novel additive of the present invention into the hydrocarbon oil. The additive serves to retard and/or prevent degradation of the hydrocarbon oil in storage and/or in use, as well as during processing as hereinbefore described.

The additive will be used in hydrocarbon oil in a stabilizing concentration which will be below about 1 percent by weight and within the range of from about 0.0001 percent to about 1 percent and generally from about 0.001 percent to about 0.5 percent by weight. In another embodiment the reaction product of the present invention is used in admixture with certain metal deactivators which appear to increase the potency of the additive beyond that which normally would be expected and thus, results in a synergistic effect. A particularly preferred metal deactivator is disalicylaldiarninopropane. Other metal deactivators include ohydroxybenzalaminophenol, o-hydroxybenzalanthranilic acid, alkylenepolyamine-tetracarboxylic acids and particularly ethylenediaminetetracetic acid, or alkali metal salts thereof. The metal deactivator is used in a minor amount and, accordingly, in a concentration of below about 0.5 percent by weight and within the range of from about 0.00001 percent to about 0.5 percent and generally from about 0.0001 percent to about 0.05 percent by weight.

When desired the additive of the present invention also may be used in conjunction with other antioxidants, cetane improvers, rust inhibitors, etc. Generally, these additives are employed as solutions in suitable solvents and, when desired, the additive of the present invention may be prepared as a mixture with one or more other additives, preferably as a solution in a suitable solvent, and the same marketed and used as a single commodity of multiple purpose.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

EXAMPLE I The reaction product of this example was prepared by the reaction of equal mole proportions of a betamonoamine mixture and epichlorohydrin. The mixed beta-monoamines used in this example are available commercially as Armeen lJ-7 and comprise a mixture of beta-monoarnines containing from aboutseven to about 1 1 carbon atoms per molecule. The mixture of beta-amines has an average molecular weight of 145, an average number of carbon atoms per molecule of 9 and a basic nitrogen equivalent weight of 136 grams.

The reaction was effected by first forming a solution of 93 g. (one mole) of epichlorohydrin in 70 g. of xylene solvent and heating the mixture to a pot temperature of 80C. A separate solution of 136 g. of the mixed beta-monoamines in 70 g. of xylene solvent was prepared. One-half of the latter solution (0.5 mole of amines) was added to the solution of epichlorohydrin with stirring and heating to a pot temperature of 8085 C. for about 1 hour, after which time the remaining solution of beta-monoamine (0.5 mole) was added to the reaction mixture, followed by 60 grams of additional xylene solvent. The reaction mixture was stirred and heated to a pot temperature of about 110C. for about 4 hours. At this time 80 g. of 50 percent sodium hydroxide solution (one mole) was added and the reaction mixture was heated and stirred at a. pot temperature of about 110C. for 3% hours. Following completion of the reaction, 106 g. of water was added and the mixture was allowed to settle into two phases. Ready separation of phases occurred, the water phase containing the sodium chloride. The reaction product was shaken with 8 grams of adsorbent silica gel at 80 C. in order to clear up anyhaze and the mixture'then was filtered and the reaction product was recovered as a light yellow clear liquid.

A portion of the reaction product prepared in the above manner was subjected to vacuum distillation to remove the xylene solvent, and the product was recovered as a light yellow clear liquid having an average molecular weight of 515 g., a basic nitrogen equivalent weight of 4.61, a tertiary basic nitrogen equivalent weight of 3.0 and an acidity of 0.242 meg/g. The reaction product had an average of 2.6 recurring units.

EXAMPLE n The reaction product of this example was prepared in substantially the same manner as described in Example 1 except that the beta-monoarnine used in this example was a mixture available commercially as Armeen L9 and comprises a mixture of betamonoamines containing from about 9 to about 13 carbon atoms per molecule. This mixture of amines has an average molecular weight of 167 g., an average number of carbon atoms per molecule of 11 and a basic nitrogen equivalent weight of 164 g.

The reaction was effected by first forming a solution of 93 g. (one mole) of epichlorohydrin in 93 g. of xylene solvent and forming a separate solution of 164 g. (one mole) of the amines in 82 g. of xylene solvent. As in the preparation of Example 1, the epichlorohydrin solution was heated and the amine solution was added thereto in two separate portions. The reaction vessel was heated initially to a pot temperature of C. for about 1.5 hours and later to a pot temperature up to about 125C. for about 8 hours. Following completion of the reaction, g. of water was added and the mixture was separated in the same manner as described in Example 1, after which the reaction product was shaken with 4 grams of silica adsorbent and filtered. 'A portion of the reaction product was subjected to vacuum distillation to remove the xylene solvent, to leave the reaction product as a clear amber liquid having a total basic nitrogen equivalent weight of 4.24, a tertiary basic nitrogen equivalent weight of 3.61 and an acidity of 0.196 meq/g.

The reaction product of this example was prepared in substantially the same manner as described in Example 1, except that the beta-monoamine used in this example was a mixture available commercially as Armeen L-l 1 and comprises a mixture of betamonoamines containing from about 1 1 to about 15 carbon atoms per molecule. This mixture of amines has an average molecular weight of 204 g., an average number of carbon atoms per molecule of 13 and a basic nitrogen equivalent weight of 204 g.

A solution of 74.5 g. (0.8 mole) of epichlorohydrin in 75 g. of xylene solvent was prepared. A separate solution of 162.8 g. (0.8 mole) of the amines in 81 g. of xylene solvent was separately prepared. The

epichlorohydrin solution was heated to a pot temperature of 96C., with stirring, and one-half of the amine solution was-added thereto, with stirring and heating at about 100C. for about 1 hour, after which the remaining portion of the amine solution was added with stirring and heating to a pot temperature of about 133C. for about 6 hours. Then 64 g. of 50% sodium hydroxide solution was added with continuous stirring and heating to about 112C. As in the previous preparations water, in this case 80 grams, was added to the reaction mixture, followed by settling and separation of layers and then shaking with 8 grams of silica adsorbent and filtering to produce a light yellowish clear product. A portion of the reaction product was subjected to vacuum distillation to remove the xylene solvent and to leave a clear yellowish liquid having an average molecular weight of 774 g., a basic nitrogen equivalent weight of 3.87, a tertiary basic nitrogen equivalent weight of 2.59 and an acidity of 0.096 meq/gThe reaction product had an average of 2.98 recurring units.

EXAMPLE IV The reaction product of this example was prepared in substantially the same manner as described in the previous examples except that the beta-monoamine used in this example was a mixture available commercially as Armeen L-lS and comprises a mixture of beta-monoamines containing from about to about 22 carbon atoms per molecule. This mixture of amines has an average molecular weight of 270 g., an average number of carbon atoms per molecule of and a basic nitrogen equivalent weight of 292 grams.

A solution of 56 g. (0.6 mole) of epichlorohydrin in 70 g. of xylene solvent was prepared. A separate solution of 174 g. of the beta-monoamine mixture in 87 g. of xylene solvent was prepared. The epichlorohydrin solution was heated to a pot temperature of 105C. with stirring and one-half of the amine solution was added and the mixture stirred and heated to a pot temperature of 110C. Thereafter the remaining portion of the amine solution was added and the mixture was stirred and heated to a maximum pot temperature of about 145C. for about 7 hours. Then 48 g. of 50 percent sodium hydroxide solution was added and the stirring and heating to a pot temperature starting at 145C. and dropping to 116C. over a period of about 3% hours. Here again, water was added, the phases separated and the reaction product shaken with 8 grams of adsorbent silica gel and filtered. The reaction product was recovered as a clear light brown liquid.

A portion of the above reaction product was subjected to vacuum distillation to remove the xylene solvent and to leave the reaction product as an amber clear liquid having an average molecular weight of 659, a total basic nitrogen equivalent weight of 2.76, a tertiary basic nitrogen equivalent weight of 1.69 and an acidity of 0.076 meq/g. The reaction product had an average of 1.9 recurring units.

EXAMPLE v The reaction product of this example is prepared by reacting equal mole proportions of N-l-methylheptylamine with epichlorohydrin. The epichlorohydrin is formed as a solution in toluene solvent and the N-lmethylheptylamine is formed as a separate solution in toluene solvent. The epichlorohydrin solution is stirred and heated to a temperature of 100C. and one-half portion of the N-l-methylheptylamine solution is added thereto with stirring and heating to 100C. then the remaining N-l-methylheptylamine solution is added and the mixture is stirred and heated to 120C. An equal mole proportion of 25 percent by weight sodium hydroxide solution is added in increment portions with continued stirring and heating to a temperature of 125C. Following completion of the reaction, the sodium chloride formed during the reaction is removed by filtering and the product is recovered as a solution in toluene solvent. Additional toluene solvent is added to form a final solution containing the active ingredient in a 50 percent by weight concentration.

EXAMPLE V1 The reaction product of this example is prepared by reacting one mole proportion of N-l-methyldecyl propylene-diamine with one mole proportion of epichlorohydrin. Here again, the epichlorohydrin and the amine are formed as separate solutions in xylene solvent. The epichlorohydrin solution is stirred and heated to a temperature of C. and one-half of the amine solution is added thereto with stirring and continued heating at 80C., after which the remaining portion of the amine solution is added with stirring and heating to a temperature of about C. Following reaction of the epichlorohydrin and amine, an equal mole proportion of 35 percent by weight sodium hydroxide solution is added and the mixture is stirred and heated at C. Following completion of the reaction, the reaction mixture is withdrawn and filtered hot to remove the sodium chloride formed during the reaction. The reaction product is recovered and subjected to vacuum distillation to remove the xylene solvent and to recover the reaction product as a clear liquid.

EXAMPLE VII Another reaction product is prepared in substantially the same manner as described in Example VI except that the beta-diamine used is a mixture of betadiamines marketed under the trade name of Duomeen L-ll. This mixture contains beta-diamines having from 14 to about 17 carbon atoms per molecule. The reaction is effected by forming separate solutions of epichlorohydrin in toluene solvent and the betadiamines in toluene solvent. The beta-diamines are added in increment portions to the heated and stirred mixture of epichlorohydrin solution. Potassium hydroxide is added to form potassium chloride and to release the available amines for further reaction to form a polymeric reactionproduct. Following completion of the reaction, the reaction mixture is filtered to remove the potassium chloride and then is subjected to vacuum distillation to recover the reaction product as a clear liquid.

EXAMPLE V111 As hereinbefore set forth, an unexpected and important advantage of the reaction products of the present invention prepared from the beta-amines is the low pourpoint, as well as the low cloud point. The pour point and cloud point of the reaction products of Examples I, II, and III, prepared as solutions containing 50 percent by weight of active ingredients, are reported in the following table. For comparative purposes, the pour point and cloud point of the reaction product prepared from epichlorohydrin and alpha-amine (hydrogenated tallowamine) are also reported in the table. The reaction product prepared from the alphaamine was made in substantially the same manner as described in Examples I through III except that the amine was an alpha-amine instead of a beta-amine.

TABLE I Reaction Product Pour Point Cloud Point Example I -1 F. l 10F. Example II -l 10F. -l10fF. Example III -l 10F. -l 10F. Prepared from hydrogenated tallowamine +60F. +62F.

From the data in the above table, it will be seen that the reaction products prepared from the beta-amines had pour and cloud points of less than minus 110F. Accordingly, no problem of solidification will occur during storage or use of these solutions of reaction products. In contrast, the reaction product prepared from the alpha-amine (hydrogenated tallowamine) in 50 percent solution had pour points and cloud points of about 60F. and solidification problems are encountered when the temperature of storage and/or'use is below this temperature.

EXAMPLE IX As hereinbefore set forth, the additives of the present invention are particularly applicable for use in fuel oil. These were evaluated in various methods. In a one-day fuel stability test, 500 ml. of commercial No. 2 fuel oil are placed in a sealed bottle, into which three iron strips are also placed, and the system is purged with oxygen and sealed. The bottle then is heated at 212F. for 16 hours, after which the fuel oil is allowed to cool, filtered and the deposit formation is determined by weighing.

When evaluating in the above manner, a control or blank sample of the fuel oil, without additive, developed 15.4 mg. of deposit per 100 cc. of fuel oil. The following table reports these data and the results obtained when other samples of the fuel oil containing the additive of the present invention were evaluated in the same manner. The additives of the present invention comprised 50 percent weight solutions in xylene solvent and were used in a concentration of 60 parts per million of the solution (30 parts per million of active ingredients).

As hereinbefore set forth, the additives of the present invention advantageously are used in admixture with a copper deactivator. The following table also reports results of evaluations made with samples of the fuel oil containing 60 parts per million of the additive solution (30 parts per million of active ingredients) and 2 parts per million of salicylal diaminopropane copper deactivator.

TABLE n Deposit Formation Additive mg. of deposit per cc. of oil None 15.4 60 ppm of Example l solution 60 ppm of Example ll solution 60 ppm of Example I]! solution From the data in the above table it will be seen that the control sample, without additive, developed 15 .4 mg. of deposit per 100 cc. of fuel oil. In contrast, the samples containing 60 parts per million of the additive solutions of the present invention reduced these deposits to less than about 4 mg. per 100 cc. of fuel oil.

The table also shows the synergistic effect obtained by using the additive solution in admixture with the copper deactivator. This combination reduced the deposit formation to less than about 0.4 mg. of deposit per 100 cc. of oil.

For comparative purposes, a sample of the fuel oil containing 60 parts per million of a 50 percent by weight reaction product solution prepared in substantially the same manner but using alpha-amine (hydrogenated tallowamine), when evaluated in the same manner, developed 4.8 mg. of deposit per 100 cc. of oil. Another sample containing 60 parts per million of this reaction product and 2 parts per million of salicylal diaminopropane developed 2.0 mg. of deposit per 100 cc. of oil. It will be noted that in this case the combination of reaction product and copper deactivator did not exhibit the high synergistic action was experienced in the case of the mixture of copper deactivator and reaction products prepared from betaamines.

EXAWLE X The additives of the present invention also were evaluated in a 3-month fuel oil stability test in which samples of the fuel oil, with and without additives, were stored in pyrex Erlenmeyer flasks in the dark for 3 months at F., after which time the fuel oil was allowed to cool, then filtered and the deposit weighed. The fuel oil used in this series of tests was a commercial No. 2 fuel oil having a specific gravity of 0.8628 and a boiling range of from 399 to 628%. The results of these evaluations are reported in the following table.

TABLE III Deposit Formation 32 ppm of additive solution of Example ll 0.2 32 ppm of additive solution of Example Ill 32 ppm of additive solution of Example [V 0.5

Here again, it will be noted that the additive solutions of the present invention were very efiective in retarding deposit formation of the fuel oil during storage.

EXAIVIPLE XI A 50 percent by weight solution in xylene solvent of the reaction product, prepared as described in Example I, is used as an additive to prevent heat exchanger deposits in a gasoline reforming unit in which the gasoline is heated to a temperature of 890F. and passed, together with hydrogen, through a reaction chamber containing a bed of catalyst comprising alumina-platinum combined halogen. A series of three heaters and reaction chambers are used. The reaction products from the last reaction chamber are-passed in indirect heat exchange with the gasoline charge to the process. This serves to partially cool the hot reaction products and to partially heat the incoming gasoline charge. Difficulty is experienced because of deposit formation in the heat exchanger tubes. In order to minimize such deposit formation and to considerably extend the operatability of the heat exchanger, 8 parts per million of the additive solution of Example I are incorporated in the hot reaction products leaving the reaction chamber prior to entering the heat exchanger.

I claim as my invention:

1. The reaction product formed by the reaction, at. a temperature of from about 50 to about 200C, of (1) from 1 to 1.5 mole proportions of an epihaiohydrin compound selected from the group consisting of epichlorohydrin, l,2-epoxy-4-chlorobutane, 2,3- epoxy-4-chlorobutane, l ,2-epoxy-5-chloropentane, 2,3-epoxy-5-chloropentane and corresponding bromo and iodo compounds with (2) from 1 to 2 mole proportions of a beta-amine containing from about 4 to about 50 carbon atoms, said beta-amine having an alkyl group attached to a nitrogen atom at its beta carbon atom, thereafter reacting with an inorganic base selected from the group consisting of sodium hydroxide and potassium hydroxide at a temperature of from about 60 to about 200C. to liberate the free amine and to form an inorganic halide salt.

2. The reaction product of claim 1 being a polymeric reaction product formed by the reaction of epichlorohydn'n with the beta-amine, and said polymeric reaction product is formed by-further reacting at a temperature of from about to about 200C.

3. The reaction product of claim 2 being a polymeric reaction product in which the first reaction is at a temperature of from about 60 to about 150C., said inorganic base is sodium hydroxide which is reacted at a temperature of from about 75 to about 150C. to liberate the free amine, and thereafter reacting at a temperature of from about to C. to form the polymeric reaction product.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3189652 *Dec 14, 1960Jun 15, 1965Universal Oil Prod CoPolymeric reaction products of amines and epihalohydrins
US3497556 *Jun 13, 1966Feb 24, 1970Procter & GambleReaction products of primary alkyl amines and epichlorohydrin
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3929655 *Nov 7, 1974Dec 30, 1975Universal Oil Prod CoAdditives for hydrocarbonaceous materials
US3930810 *Jul 31, 1974Jan 6, 1976Universal Oil Products CompanyPolymeric reaction products of epihalohydrin-n-alkyl polyamine, epihalohydrin-alkyl amine, alcohol and ethylene oxide-propylene oxide copolymer
US4239497 *Nov 8, 1979Dec 16, 1980Uop Inc.Inhibiting sedimentation and discoloration using the reaction product of a polyoxyalkylene amine and an epihalohydrin
Classifications
U.S. Classification564/503, 564/476, 44/332, 564/506
International ClassificationC10L1/22, C08G65/00, C08G65/26, C10L1/10
Cooperative ClassificationC08G65/2624, C10L1/221
European ClassificationC08G65/26F1L, C10L1/22W
Legal Events
DateCodeEventDescription
Apr 27, 1989ASAssignment
Owner name: UOP, A GENERAL PARTNERSHIP OF NY, ILLINOIS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:UOP INC.;REEL/FRAME:005077/0005
Effective date: 19880822
Sep 21, 1988ASAssignment
Owner name: UOP, DES PLAINES, IL, A NY GENERAL PARTNERSHIP
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:KATALISTIKS INTERNATIONAL, INC., A CORP. OF MD;REEL/FRAME:005006/0782
Effective date: 19880916