GB2089356A - Polymeric reaction products of amines and epoxyhalo compounds for use as hydrocarbon oil additives - Google Patents

Abstract

The polymeric reaction products formed by reacting alkoxyalkylamines of poly(oxyalkylene)amines with epoxyhalo compounds selected from epihalohydrins and 1-halo-3,4- epoxybutanes, 2,3-epoxybutanes, 4,5- epoxypentanes and 3,4- epoxypentanes at temperatures in the range from 40 DEG C to 150 DEG C in the presence of inorganic bases may be used as sedimentation and degradation inhibitors in hydrocarbon oils, antifoulants, carburettor detergents, lubricant additives, and corrosion inhibitors.

Description

SPECIFICATION Poiymeric reaction products of amines and epoxyhalo compounds for use as hydrocarbon oil additives Various types of petroleum-derived hydrocarbon oils undergo deterioration on storage upon exposure to severe conditions. Thus, fuel oils such as gasoline, diesel fuel, jet fuel, other aviation fuel, burner oil, furnace oil, kerosene, and naphtha, for example, as well as other oils such as lubricating oils, cutting oils and slushing oils, undergo deterioration as evidenced by such changes as, for example, formation of sediment and discoloration.

Sediment formation is undesirable for various reasons, The settling of accumulated particles in tanks storing hydrocarbon oils requires periodic draining and cleaning of such storage tanks, leading to temporary unavailability of storage capacity, substantial diversion of manpower, and problems of waste disposal. Sediment formation in burner oil tends to plug devices such as strainers, burner tips and injectors. In diesel fuel such sediment tends to form sludge and varnish in the engine. If the oil is used as a heat-exchange medium, as for example with jet fuel, the sediment tends to plug exchanger coils. In gasoline the sediment may tend to deposit on sensitive parts in an internal combustion engine, such as carburettors, thereby decreasing the efficiency of combustion and causing increased fuel consumption.

It is apparent, therefore, that it is desirable to reduce sediment formation in hydrocarbon oils. One method of effecting such a reduction would be to eliminate, to a substantial degree, those processes which lead to particle formation, such as oxidation. Another method would be to prevent agglomeration and/or settling of the formed particulate matter by effectively maintaining the fine particles in a well dispersed state, because when the particles are well-dispersed the aforementioned difficulties associated with sediment formation either do not occur or are of substantially lessened severity.

Discoloration of hydrocarbon oils is undesirable because it is an indication that degradation has occurred or is occurring. Hence there is a marked customer preference for lighter oils, and there is an economic incentive for minimizing discoloration and degradation of hydrocarbon oils, especially during long-term storage.

We have found polymeric reaction products which may be used to prevent the deterioration of hydrocarbon oils, as evidenced by sediment formation and discoloration, by incorporation into the oil in suitable amounts.

According to the present invention there is provided a polymeric reaction product formed by reacting an alkoxyalkylamine or a poly(oxyalkylenelamine with an epoxyhalo compound which is an epihalohydrin, a 1 -halo-3,4-epoxybutane, a 1 -halo-2,3-epoxybutane, a 1-halo-4,5-epoxypentane or a 1 -halo-3,4-epoxypentane, at a temperature of from 400C to 1 500C in the presence of an inorganic base.

One embodiment of a polymeric reaction product according to the invention is the product of 1 molar proportion of an alkoxyalkylamine, suitably one in which the alkoxy moiety is an aliphatic group of from 1 to 25 carbon atoms, preferably 6 to 20 carbon atoms, the alkyl moiety is an alkylene group of from 2 to 10 carbon atoms, preferably propylene, and the amine is a primary amine which may contain multiple alkylene amino units, preferably NH, or NH(CH,-)3NH2, and from 0.5 to 2 molar proportions of an epihalohydrin, preferably epichlorohydrin.

Another embodiment of a polymeric reaction product according to the invention is the product of 1 molar proportion of a poly(oxyalkylene)amine, preferably tne diamine from polyisopropylene glycol of molecular weight from 200 to 2000, with from 0.5 to 2 molar proportions of an epihalohydrin, preferably epichlorohydrin.

The invention also provides a method of inhibiting sedimentation and discoloration of a hydrocarbon oil comprising dissolving therein an amount of from 0.0001 to 1% by weight of a polymeric reaction product according to the invention.

Hydrocarbon oils are stored and utilized under a diversity of temperatures. Consequently, it is desirable that additives which may be incorporated in said oils should be readily pumpable, even at a low temperature. Among the physical attributes ensuring easy pumping are a relatively low pour point and a suitable viscosity at low temperatures. Another desirable attribute of additives which inhibit sedimentation is that they should exhibit enhanced dispersant capability toward solid particulate matter but minimal dispersant capability toward water, for it is preferable to leave water as a separate phase in hydrocarbon oils. The reaction products of this invention have been found to act as superior sedimentation inhibitors while having low pour points, desirable viscosities. and low dispersability toward water.Additionally, the reaction products of this invention, when used as additives to hydrocarbon oils, effectively retard their discoloration. Because of their structure, other uses for said reaction products include applications as antifoulants, carburettor detergents, lubricant additives, and corrosion inhibitors.

The reaction products proposed according to this invention are polymeric reaction products of an aikoxyalkylamine or a poly(oxyalkylene)amine with an epoxyhalo compound formed at a reaction temperature of from 400C to 1 500C in the presence of an inorganic base. Such reaction products generally have relatively low pour points and viscosities and have a broad range of uses, as is described herein. Such attributes are desirable in ease of handling and utilizing these materials in their perceiveci uses. For example, additives for hydrocarbon oils frequently are metered into the oil by pumping under a wide range of temperatures, and it is desirable that such additives remain liquid and pourable, with not too high a viscosity at low temperatures, to ensure pumpability.

The reaction frequency is conducted in a high-boiling, unreactive solvent to moderate the exothermix reaction and for ease of manipulation, both during the reaction and afterwards. However, the use of a solvent, where such use is undesirable, may be eliminated, although the results will not necessarily be equivalent. Among the solvents which may be used are included toluene, xylene, mesitylene, ethylbanzene, propylbenzene, and other alkylated and polyalkylated aromatics as examples of suitable high-boiling but unreactive materials.

The term "alkoxyalkylamines" as used in the specification encompasses primary amines, including monoamines, diamines, triamines and higher amines. Where monoamines are used the amine can be represented as RORlNH2. The alkoxy moiety, RO, of such monoamines suitably has from 1 to 25 carbon atoms, and preferably from 6 to 20 carbon atoms. Representathe of the carbonaceous portion of the alkoxy moiety are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl and pentacosyl groups. Such groups commonly have their commercial origin in fatty acids and petroleum-derived alcohols, and consequently are often supplied as mixtures.

Therefore it is to be understood that amines containing a combination of the aforementioned groups are within the scope of this invention.

When the carbonaceous portion of the alkoxy moiety is derived from fatty acids the major proportion is an unbranched aliphatic group. When the carbonaceous portion comes from petroleumderived olefins, the major proportion generally is a branched aliphatic group. In each case minor amounts of unsaturated material may be present. Therefore it is to be understood that the carbonaceous portion of the alkoxy group of the alkoxyalkylamines of this invention may be comprised of a major proportion of either unbranched or branched aliphatic groups and may contain minor amounts of unsaturation.

The alky moiety, R1, of the alkoxyalkylamines is suitably an alkylene radical of from 2 to 10 carbon atoms. Examples of alkylene radicals which may be used are ethylene, propylene, butylene, amylene, hexylene, heptylene, octylene, nonylene and decylene. In a preferred embodiment the alkylene radical is propylene. Such alkylene radicals generally are unsubstituted, but branched alkylene groups may be employed, although not necessarily with equilvalent results. Examples of the latter are isopropylene, sec-butylene, iso-butylene, sec-amylene and iso-amylene.

We have found that diamines, triamines, tetramines and higher amines also form polymeric reaction products according to this invention. In the case of diamines the structure may be represented as B-0-B1NHB2NH2, where RO and R' bear the same meanings as set forth above for the monoamines. The group R2 is, like Ra, suitably an alkylene radical of from 2 to 10 carbon atoms, generally unbranched but not necessarily so. R1 and R2 may be the same or may be different.Examples of diamines, cited solely for illustrative purposes, are alkoxyalkyl ethylenediamine, alkoxyalkyl propylenediamine, alkoxyalkyl butyienediamine, alkoxyalkyl amylenediamine and alkoxyalkyl hexylenediamine, alkoxyalkyl isopropylenediamine, alkoxyalkyl isobutylenediamine and alkoxyalkyl secbutylenediamine. In a preferred embodiment both R1 and R2 are prnpylene groups, -CH2CH2CH2-.

In a like manner the triamines can be represented as ROR1NHR2NHR3NH2, the tetramines as ROR'NHR2NHR3NHR4NH2, the pentamines as ROR'NHR2NHR3NHR4NHRsNH2, and so forth, with a general formula of ROR'(NHR2)m~,NH2, where m is the number of amino groups present in the polyamine and is an integer which is usually less than 10. The definitions of RO and R1 in such polyamines conform to that given hereinbefore. Where m is equal to or greater than 2, the group R2 is an alkylene group otherwise conforming to the definition hereinbefore set forth for R1 (individual R2s being identical or different).

Examples of such amines are alkoxyalkyl diethylenetriamine, alkoxyalkyl triethylenetetramine, alkoxyalkyl polyethyleneimine and alkoxyalkyl dipropylenetriamine.

Just as the alkoxy group may contain a mixture of carbonaceous groupings, so may the diamines, triamines, etc. contain a mixture of amino groupings. Therefore it is to be understood that this invention encompasses all mixtures of amines whose major components conform to those definitions set forth above.

The poly(oxyalkylene)amines suitable for use in this invention include monoamines and diamines, Such amines may be regarded as the reaction products of a poly(oxyalkylene)glycol with ammonia, in which either both available hydroxyl groups are aminated to give diamines, or in which one available hydroxyl group is etherified and the other is aminated to give monoamines. Such poly(oxyalkylene)amines may be represented by the structure A~tR10)n~RNH2.

The moiety R of the poly(oxyalkylene)amines used in this invention is suitably an alkylene radical of from 2 to 10 carbon atoms. Such alkylene radicals may be linear or branched alkylene radicals.

Examples of branched alkylene radicals which may be employed in this invention are isopropylene, secbutylene, iso-butylene, sec-amylene and iso-amylene. In one preferred embodiment R is ethylene, whereas in another preferred embodiment R is isopropylene.

The moieties R1 of the poly(oxyalkylene)amines used in this invention are suitably each independently alkylene radicals of from 2 to 10 carbon atoms, either linear or branched, for example those given above for the moiety R. The number of oxyalkylene moieties present, n, may vary from 2 to 50 or more. Each of the groups R1 may be the same or different. In one embodiment, all oxyalkylene groups are the same, i.e. each R' is identical.In another embodiment, a chain of identical oxyalkylene moieties is flanked on one or both sides by one or more other oxyalkylene groups, to afford u partial structure which may be represented as: (R2O)a~-(R'O)b~(R30)C where a + b + c = n, R2 and R3 are moieties of the same class as R1 but where either R2 or R3, or both, are different from R1 and may be different from each other.

Alkylene radicals which are particularly preferred are nthylene and isopropylene radicals.

The moiety A of the poly(oxyalkylene)amines used in this invention may be the amino group, H2N.

in such an instance the poly(oxyalkylene)amine employed in this invention is a diamine which may result from the amination of both hydroxyl groups of a poly(oxyalkylene) glycol.

The moiety A also may be an alkoxy group. The alkoxy group of said moiety A suitably has from 1 to 40 carbon atoms, but preferably has from i to 20 carbon atoms. As mentioned previously, when the carbonaceous portion of the alkoxy group is derived from fatty acids the major portion is an unbranched aliphatic group, but when the carbonaceous portion comes from petroleum-derived olefins, the major portion generally is a branched aliphatic group. In each case minor amounts of unsaturated material may be present. Therefore it is to he understood that the carbonaceous portion of the alkoxy group of the poly(oxyalkylene)amines for use in this invention may be comprised of either a major portion of unbranched or branched aliphatic groups which may contain minor amounts of unsaturation.

The moiety A in the poly(oxyalkylene)amines also may be derived from trimethylolpropane. In such an instance A may be represented as:

where R and R1 conform to the definitions given to them previously, and y and z are integers from 1 to 10. The moiety B may be hydrogen or an alkyl group of from 1 to 10 carbon atoms.

The amine or mixture of amines is reacted with an epoxyhalo compound. Epichlorohydrin is preferred, although other epihalohydrins, epibrnmohydrin and epiiodohydrin, may be used but not necessarily with equivalent results in every case. Other epoxyhalo compounds which may be employed in this invention are 1 -chloro-3,4-epoxybutane, 1 #hlorn-2 ,3-epoxybutane, 1 -chloro-4,5-epoxypentane, 1 -chlorn-3,4-epoxypentane, and the corresponding bromo and iodo compounds. Suitable condensation products may also be obtained when using a mixture of epoxyhalo compounds, where each of the components meets the qualifications set forth above. The amount of epoxyhalo compound used suitably ranges from 0.5 to 2 moles per mole of amine.

The preparation of the polymeric reaction products of this invention is effected by contacting the epoxyhalo compound and the amine, generally in a high boiling aromatic solvent, at a suitable temperature, and removing the inorganichalide which forms with an inorganic base. Generally, the reaction is conducted at a temperature from 400C to 1 5000, a preferred temperature range being from 600C to 12500. Inorganic bases suitable for use in the present invention include the alkali metal hydroxides and carbonates and the alkaline earth oxides, hydroxides and carbonates.Examples of such materials, cited for illustrative purposes only, are the hydroxides and carbonates of lithium, sodium, potassium, rubidium and cesium, magnesium oxide, magnesium hydroxide, magnesium carbonate, calcium oxide, calcium hydroxide, calcium carbonate, barium oxide, barium hydroxide, and barium carbonate. Where the epoxyhalo compound is used in up to equal molar proportions of the amine, then the molar amount of base employed is approximately equal to that of the amine, although an excess of base over amine up to about 50% often may be employed advantageously. Where the epoxyhalo compound is used in greater than molar proportions relative to amine, then the molar amount of base is about equal to that of epihalohydrin although an excess up to 50% may be used.

The mode of preparation of the reaction products (condensation products) of this invention is susceptible to numerous variations on the theme of directly reacting the amine with the epoxyhalo compound under reaction conditions. An example of one general mode is the addition of an epoxyhalo compound to a solution of the amine in a suitable solvent, generally a high-boiling aromatic compound or mixtures thereof. Reaction between the components occurs to a given acidity, or given amount of amine hydrohalide formation, at which time either aqueous or solid inorganic base is added to remove the halide thus formed. The primary reaction product therefrom undergoes further condensation leading to the ultimate reaction product.

An example of another mode of preparation is the concurrent addition of epoxyhalo compound and amine to the solvent employed at a suitable temperature. When reaction has occurred to a desired amount of acidity, aqueous or solid inorganic base is added and the liberated reaction product thereupon undergoes further condensation leading to the ultimate reaction product.

In still another method of preparation, the epoxyhalo compound and amine are added concurrently to the solvent containing a portion of the inorganic base employed. The base may be either in solution or as a solid. After reaction has occurred to a given amount of acidity the remaining portion of solid or aqueous base is added and the primary reaction product thereupon undergoes further condensation leading to the ultimate reaction product.

The chemical structures of the polymeric reaction products of this reaction are unknown. Based upon the chernical properties of the reactants, one can surmise that, using a monoamine RORtNH2 and epichlorohydrin as typical of reactants, a likely primary reaction product is the hydrochloride salt of the structure:

Upon addition of base, the hydrochlonde salts are converted to the free base which can react with additional epichlorohydrin to give materials with the structure:

When a monoamine, XNH2, and epichlorohydrin are used as typical reactants, the primary reaction product may be the hydrochloride salt of the structure::

Upon addition of base, the hydrochloride salts are converted to the free base which can react with additional epichlorohydrin to give materials which may have the structure,

In addition, especially when diamines and other polyamines are used, cyclization and cross-linking may occur to a substantial degree.

The reaction products of this invention have been shown to be good dispersants of solid particulate matter while being poor dispersants of water. This combination of properties is an excellent one for use of these materials as sedimentation inhibitors of hydrocarbon oils, especially fuel oils.

Additionally, the reaction products described herein show substantial inhibition of discoloration in hydrocarbon oils. Thus they are superior additives for preserving quality of hydrocarbon oils upon storage, especially at elevated temperatures or for relatively long periods of time. The polymeric reaction products of tiis invention also have significant potential as corrosion inhibitors, carburettor detergents, antifoulants and lubricant additives.

The following Examples are merely illustrative of this invention.

EXAMPLE I Epichlorohydrin (o3.2 g, 0.09 mol) was added dropwise over about 50 minutes to a stirred, pale yellow solution initially at about 900C, of tridecyloxypropylamine (280.4 g, 1.05 mol), dissolved in 222 9 of Espesol 38C. The latter is the trade name for hioh boiling bottoms from xylene fractionation as supplied by Charter Oil Co. The solution was stirred for about 1.5 hours at 9'1 1 1 1 OOC, after which a solution of 20 wt.% acueous sodium hydroxide containing 0.99 mol of base was added over about 40 minutes while the reaction temperature was maintained at 85-94#C. The mixture was stirred for about 2.5 hours at 8.3~91 OC, and an additional 0.09 mol of base in water was added. The mixture was cooled, the phase layers were separated, and the organic phase was filtered to give a clear, amber solution (544 g) which contained 53.2 wt% active ingredient by the nitrogen jet gum method, ANSI/ASTM D 381-70 modified in that nitrogen is used as the gas.

EXAMPLE II Epichlorohydrin (0.240 mol) was added over 50 minutes to a pale yellow solution of Ntridecyloxtpropyl-1 ,3-propylenediamine (0.26 mol) in 60 g of the aforementionecl solvent at 76-80' C.

The mixture was stirred at 77-830C for about 30 minutes, and 0.26 mol of a 20 wt.'3ó aqueous sodium hydroxide solution was added over 15 minutes. Stirring at 78-830C was continued for about 1.8 hours, an additional 0.024 mol of base was added, and the mixture was stirred for an additional 0.5 hr at 82~83 C. Finally the phase layers were separated, 10 g xylene was added to the organic phase, and water was removed by azeotropic distillation to give 152 g (96%) of a clear yellow solution containing 54 wt.% of active ingredient.

EXAMPLE Ill Tridecyloxypropylamine (0.750 mol) and epichlorohydrin (0.712 mol) were added separately but concurrently to a stirred mixture of Espesol 3BC (160 g) and 22 wt.% aqueous sodium hydroxide containing 0.0712 mol of base at 73-830C over a period of 1.5 hr. After an additional 10 min. at 80tC 22 wt.% aqueous sodium hydroxide containing 0.712 mol of base was added over 13 min. The mixture was stirred at 78-870C for 1 hour, then at 11 00C for 2 hr. Phase layers were separated and the organic phase was filtered to give 387 g (97%) of a solution containing 53.4 wt.% of active ingredient.

EXAMPLE IV N-tridecyloxypropyl-1 3-propylenediamine (0.740 mol) and epichlorohydrin (0.70 mol) were added concurrently over about 40 minutes to a mixture of Espesol 3BC (172 g) and 22 wt.% aqueous sodium hydroxide containing 0.070 mol of base at 75--900C. After 8 minutes an additional 22 wt.% aqueous sodium hydroxide (0.70 mol of base) was added over 15 min. The temperature was increased to 1 1 OCO for 1 hour and the mixture was stirred for 2 additional hours at that temperature. Phase layeis were separated 15 g of xylene was added to the organic phase, and water was removed by azeotropic distillation to give 423 g (97%) of a light amber solution containing 53 wt.% of active ingredient.

EXAMPLE An alkoxypropyl-1,3-propylenediamine mixture rich in C12~C,5 groupings (0.594 mol) and epichlorohydrin (0.56 mol) were added concurrently over a period of 1 hour to a mixture of 137 g.

Espesol 3BC and 22 wt.% aqueous sodium hydroxide (0.056;nol) at 71~91 C. After 5 minutes, 0.56 mol of additional base, as a 22 wt.% aqueous solution, was added with stirring at 83--920C over 13 min. The temperature was raised to 1 080C and the mixture was stirred at 106-1 090C for about hours. Phase layers were separated, 15 g xylene was added to the organic phase and water was removed by azeotropic distillation to give 361 g (96%) of a clear yellow solution containing 54.3 wt.'Xo active ingredient.

EXAMPLE VI The polymeric reaction products of this invention generally have relatively low pour points and viscosities. These properties are desirable to ensure ease of manipulation even at low temperatures where such materials can be anticipated to be used. In Table I are collected several representative reaction products from epichlorohydrin and alkoxyalkylamines whose pour points and viscosity were determined as a 50% solution in Espesol 3BC. For comparison a commercially successful additive sold under the trade name of Polyflo 130 by UOP Inc., and here designated as PFi 30, used to inhibit sedimentation and discoloration is included.The pour point was determined by the method of ANSl/ASTM D97-66; viscosity was determined by using the methods ANSI/ASTM D445-74 and D2161-74.

TABLE 1 Pour Points and Kinematic Viscosities of 50 Weight % Solutions Ratio Viscosity Epichlorohydrin/ Pour Point (Saybolt Universal Amine Amine ( C) Second) PF130 ~ -12 204 Cs#10OC3NH2 19/20 < -40 79.4 C130C3NH2 6/7 < -40 62.3 C10OC3NHC3NH2 9/11 -18 78.9 C,3OC3NHC3NH2 12/13 < -40 53.2 The data of Table 1 shows the dramatic improvement achievable by the reaction products of this invention relative to a product which can be taken as an industry standard. Most of the reaction products show a pour point less than 400 C, with a viscosity one-half to one-fourth of the standard.

EXAMPLE VII The dispersing tendency of the polymeric reaction products of this invention was determined using the method of ANSI/ASTM D1094 72. In this method the condition of the interface and the degree of separation between a phosphate buffer and a hydrocarbon was determined after the ingedients had been shaken together for 2 minutes. The condition of the interface is rated from 1 (best) to 4 (worst), and the separation from 1 (best) to 3 (worst). For these tests isooctane was used as the hydrocarbon containing about 30 ppm of the various reaction products. The first entry is the commercial product described in Example Vl. In all cases the reaction product resulted from the use of epichlorohydrin with the specified amine.

TABLE 2 Shake Test with Isooctane Epichlorohydrin/ Conc.

Amine Amine (ppm) Interface Separation PF130 ~ 12 4 3 c8~10oc3NH2 19/20 30 1 1 C6OC3NH2 19/20 34 1 1 C13OC3NH2 6/7 34 1 1 C,ooC3NHC3NH2 12/13 34 4 1 C13OC3NHC3NH2 12/13 20 1-2 1 These data show that most of the polymeric reaction products of this invention show relatively little dispersability toward water. Phase separation is clean, as evidenced by the condition of the interface, and emulsifying properties are quite low as evidenced by separation. There is marked improvement over the standard, which shows the products of this invention have a quite desirable selectivity as regards dispersability.

EXAMPLE VIII The amine used was methoxy poly(isopropyleneoxy) isopropylene amine, of approximate formula CH3O-(-CH2CH(CH3)O-)9-CH2CH(CH3)NH2.

and supplied by Jefferson Chemical Co., Inc. as Jeffamine M-600. Epichlorohydrin (9.2 g, 0.10 mol) was added dropwise over one minute to a pale yellow solution of amine at 750C in 60 g Espesol 3BC (high boiling bottoms from xylene fractionation as supplied by Charter Oil Co.) and 2-propanol (20 g). The resulting solution was stirred at 75~78.5 C for 1 hour 47 minutes, giving a solution with an acidity of 14% of the theoretical maximum. The temperature was raised to 860C and kept there for 1 hour 5 minutes, giving a solution with an acidity of 28%. Then 17 wt.% aqueous sodium hydroxide solution (25.8 g, 0.110 mol, 10% excess) was added in one portion. The mixture was stirred at 840C for 1 hour 10 minutes. The phase layers were separated.The organic layer was azeotropically distilled with collection of the 2-propanol-water azeotrope. The solution was cooled and suction-filtered, giving a light yellow solution (1 14.6 g, 92%, 52.7 wt.% active ingredient).

EXAMPLE IX The amine used was of the structure HzNCH(CH3)CH2#(OCH(CH3)#CH2)fl(#0CH2CH2#)b(#OCH2CH(CH3))CNH2 of approximate molecular weight 600, where b is 13-14, and a + c is 3-4. Epichlorohydrin (18.5 g, 0.200 mol) was added dropwise over 6 minutes to a stirred light yellow solution of such amine (60.0 g, 0.200 eq, 0.100 mol) in Espesol 3BC (70.0 g) and 2-propanol (25.0 g) at 59-600C.The temperature was kept at 59-6O0C for one hour. The temperature was raised over 10 minutes and held at 78.50C for 2 hours 9 minutes, giving a solution with an acidity 29% of the theoretical maximum. Then 1 7 wt.% aqueous sodium hydroxide (49.4 g, 0.200 mel, 10% excess) was added over 2 minutes to the stirred solution.The temperature was raised from 71 C to 790C over 40 minutes and kept at 79~79.5 C for 30 minutes. The phase layers were separated, giving a light yellow, cloudy organic layer containing water droplets. The resulting solution was dried by azeotropic distillation with 2-propanol (10.0 9). The resulting solution was filtered, giving a clear, light yellow solution (131.3 g, 90%, 54.2 wt.% active ingredient by nitrogenjet gum method, ANSl/ASTM D381--70 modified in that nitrogen is used as the gas).

EXAMPLE X The amine was the diaminated product of poly(isopropyleneoxy) glycol, approximate molecular weight 230, containing 3-4 isopropylene units. Epichlorohydrin (17.6 g, 0.19 mol) was added dropwise over 21 minutes to a stirred, almost colorless solution of the amine (46.8 g, 0.20 mol) in Espesol 3BC (45.0 g) at 75.5-78.50C. The temperature was kept at 78.5-.80.50C for 14 minutes, raised from 80.50C to 860C over 9 minutes, and kept at 86-880C for 39 minutes after which an aliquot had an acidity of 37% of the maximum theoretical.Then 20 wt.% aqueous sodium hydroxide (42.0 g, 0.21 mol, 10% excess) was added to the stirred solution at 84-870C over 38 minutes. The resulting mixture was stirred at 85~90.5 C for 2 hours 7 minutes. then more 20 wt.% aqueous sodium hydroxide (3.8 g, 0.019 mol, total 20% excess) was added to the mixture at 900C. The mixture was stirred at 90-91 C for 31 minutes. The phase layers were separated. The organic layer was dried by azeotropic distillation with 2-propanol and suction-filtered, giving a clear, pale yellow filtrate (87.8 g, 86%, 45.6 wt.% active ingredient by nitrogen-jet gum method).

EXAMPLE Xl The amine was of the same structurai type as used in Example X but with a somewhat higher molecular weight, about 400. Epichlorohydrin (8.3 g, 0.090 rnol) was added dropwise over 8 minutes to a stirred, very pale yellow solution of the amine (41.0 g, 0.200 eq,0.100 mol) in Espesol 3BC (40.0 g) at 75--75.5 C. The resulting solut;on was stirred at 75.5-760C for 56 minutes. The temperature was increased in two steps from 75.5 C to 930C over 56 minutes and kept at 930C for 6 minutes after which an aliquot had an acidity of 32% of the maxirnum theoretical.Then 20 wt.% aqueous sodium hydroxide (19.8 g, 0.099 mol, 10% excess) was added drcpwise over 6 minutes to the stirred solution at 93~88 C. The mixture was stirred at 88--93 C for 17 minutes and at 93-940C for one hour 10 minutes with some white salt settling to the bottom. Then additional 20 wt.% aqueous sodium hydroxide (1.8 g, 0.0090 mol, total excess 20 < /ó) was added. The resulting mixture was stirred at 91 0C for 50 minutes. The phase layers were separated, giving a pale yellow organic layer containing some suspended water. The solution was dried by azeotropic distillation with 2-propanol (20.1 g).The resulting solution was suction-filtered, giving a light yellow solution (65.9 g, 77%, 53.1 wt.% active ingredient by nitrogen-jet gum method).

EXAMPLE XII In this example the amine was a substituted ether of the type

where x + y + z had an average value of about 5.3. Epichlorohydrin (8.7 g, 0.094 mol) was added dropwise over 12 minutes to a stirred, pale yellow solution of said amine (44.1 g, 0.30 eq, 0.10 mol) in Espesol 3BC (47.0 g) at 75~77 C. The resulting solution was stirred at 77-780C for 14 minutes.

The temperature was increased stepwise from 77.50C to 940C over 45 minutes and maintained there for 13 minutes to an acidity of 44% of the maximum theoretical. Then 20 wt.% aqueous sodium hydroxide (21.0 g, 0.105 mel, 10% excess) was added dropwise over 13 minutes to the stirred solution at 94.5~90 C. The mixture was filtered and the phase layers were separated. The organic layer was filtered, giving a clear pale yellow filtrate (87.4 g, 96%. 46.1 wt.% active ingredient by nitrogen-jet gum method).

EXAMPLE Xlil In Table 3 are collected several representative reaction products from epichlorohydrin and poly(oxyalkylene)amines whose pour points and viscosity have been determined as a 50% solution in Espesol 3BC. For comparison the commercially successful additive PF 130, as identified in Example VI is included. The pour point was determined by the method of ANSI/ASTM D97-66. The viscosity was determined using the method of ANSI/ASTM D445--74 and D21 61--74. The reaction products entered in the Table were: entry 2, that of Example VIII; entry 3, that of Example XII; entry 4, that of Example X; entry 1, from H2NCH(CH3)CH2(OCH2CH--(CH3))33NH2 and and 1 molar proportion of epichlorehydrin.

TABLE 3 Pour Points and Kinematic Viscosities of 50 Weight % Solutions Viscosity Saybolt No. Pour Point ( C) Universal Second 1 < -54 122 2 < -54 50.4 3 -29 100 4 -34 -.

PF 130 -12 204 The data of Table 1 shows dramatic improvernent by reaction products according to this invention relative to a product which can be taken as an industry standard. Many reaction products show a pour point less than #400 C, with a viscosity one-half to one-fourth of the standard.

EXAMPLE XIV The dispersing tendency of the polymeric reaction products was determined using the method of ANSI/ASTM D1094--72. In this method the condition of the interface and the degree of separation between a phosphate buffer and a hydrocarbon is determined after being shaken for 2 minutes. The condition of the interface is rated from 1 (best) to 4 (worst), and the separation from 1 (best) to 3 (worst). In this test isooctane was used as the hydrocarbon. The last entry is the commercial product described in Example XIII. In all cases the reaction product resulted from the use of epichlorohycirin.

Entry 1 is the reaction product of Example IX; entry 4 is that of Example VIII; entry 2 is that of H2NCH{CH3)CH2~(OCHi^H3}CH2)a~(OCHZCH2)b~(OCH(CH3)CH2)s~NH2, where b is approximately 21, a -- c approximately 4, with 2 moles epichlorohydrin; entry 3 is the same as entry 1 of Table 3.

TABLE 4 Shake Test With Isooctane No. Conc. (ppm) Interface Separation 1 12 1 2 2 12 1 2 3 24 1b 2 4 24 1b 2 PF130 12 4 3 These data show that most of the polymeric reaction products of this invention show relatively little dispersability toward water. Phase separation is clean, as evidenced by the condition of the Interface, and emuls.fying properties are quite low, as evidenced by the separation. There is marked improvement over the standard, which shows the products of this invention have a quite desirable selectivity as regards dispersability.

EXAMPLE XV In this example are collected data concerning several representative reaction products according to this invention prepared from epichlorohydrin. All the reaction products were used at a concentration of 1 7 ppm in the same fuel oil. Their efficacy in inhibiting sedimentation and discoloration was determined by an accelerated storage stability test conducted as follows: One liter of fuel oil is poured into a flask containing four sandblasted steel strips. Oxygen is blown into the flask for 5 minutes and the flask is stoppered securely, then heated at 1 000C for 16 hours. The flask is cooled for one hour and the oil is filtered through a weighted 0.8 micron millipore filter disc, the color of the filtrate being measured.

The flask and steel strips are washed with a solvent, such as isooctane, the washings are filtered through the same filter disc, and the filter disc and material collected thereon are washed with a separate portion of solvent. The disc is then heated at 950C to remove solvent, after which the disc is cooled and its weight taken to determine the weight of the sediment thereon.

The change in color is determined from the absorbence of the sample before and after heating.

Material which tends to prevent discoloration will show a small change in absorbence than a blank sample, i.e. one in which the fuel oil has no additives. The efficiency of the reaction products of this invention is preventing discoloration was determined, at the same weight-weight concentration, relative to Polyflo 130, a commercial product of UOP Inc., by comparing the difference between the absorbence of the blank Bank, and that containing the reaction products of this invention, A, with that of the standard, A,30, using the formula: Blank - A relative efficiency = Ablank - A130 Values greater than one show the material is superior to the standard in retarding discoloration.

The weight of sediment observed in the presence of various additive materials is a direct measure of their inhibitory tendencies toward sediment formation. A comparison of the efficacy of the materials of this invention with that of the successful commercial product Polyflo 130 is the ratio of weight of sediment formed in the presence of Polyflo to the weight formed in the presence of the materials of this invention at the same weight-weight concentration.

Physical Properties and Inhibitor Efficiency of Additives Relative Efficiency Mole Ratio Epichlorohydrin Sedimentation Amine to Amine Inhibition Discoloration C60(CH2)3NH2 .95 .7 0.8 Cs#i0O(CH2)3NH2 .95 1.0 0.6 C8#10O(CH2)3NH(CH2)3NH2 .95 1.3 1.7 C10O(CH2)3NH(CH2)3NH2 .92 1.2 1.1 C12150(CH2)3NH(CH2)3NH2 1.0 1.0 C13O(CH2)3NH(CH2)3NH2 1.03 1.3 1.3 C13O(CH2)3NH(CH2)3NH2 .95 1.7 1.3 C13O(CH2)3NH(CH2)3NH2 .92 2.5 1.0 C130(CH2)3NH(CH2)3NH2 .94 5.0 1.2 C13O(CH2)3NH(CH2)3NH2 1.03 1.4 1.3 Physical Properties and Inhibitor Efficiency of Additives Mole Ratio Epichlorohydrin Sedimentation Amine to Amine Inhibition Discoloration See Example Xll 0.93 0.8 0.7 See Example 0.90 0.6 0.8 See Example X 0.95 1.1 1.5 As the data on this Table show, the reaction products of this invention are of comparable or superior efficiency relative to a commercial standard in inhibiting sedimentation and discoloration in a typical fuel oil.

Claims (27)

1. A polymeric reaction product formed by reacting an alkoxyalkylamine of a poly(oxyalkylene)amine with an epoxyhalo compound which is an epihalohydrin, 1-halo-3,4epoxybutane, a 1 -halo-2,3-epoxybutane, a 1 -halo-4,5-epoxypentane or a 1 -halo-3,4-expoxypentane, at a temperature of from 400C to 1 500C in the presence of an inorganic base.

2. A polymeric reaction product as claimed in claim 1 wherein an alkoxyalkylamine is used having an alkoxy moiety which is an aliphatic group of from 1 to 25 carbon atoms, an alkyl moiety which is an alkylene radical from 2 to 10 carbon atoms and an amine moiety which has the formula NH2 or (HNB2)rnNH2 where m is an integer from 1 to 10 and R2 is alkylene of from 2 to 10 carbon atoms.

3. A polymeric reaction product as claimed in claim 2 wherein he alkoxy moiety of the alkoxyalkylamine is an aliphatic group of from 6 to 20 carbon atoms.

4. A polymeric reaction product as claimed in claim 2 or 3 wherein the alkoxyalkylamine is an alkoxypropylamine.

5. A polymeric reaction product as claimed in claim 4 wherein the alkoxypropylamine is tridecyloxypropylamine.

6. A polymeric reaction product as claimed in claim 2 or 3 wherein the alkoxyalkylamine is an alkoxypropyl propylenediamine.

7. A polymeric reaction product as claimed in claim 6 wherein the alkoxypropyl propylenediamine is N-tridecyloxypropyl- 1 ,3-propylenediamine.

8. A polymeric reaction product as claimed in any of claims 2 to 7 which has been formed at a temperature of from 60 C to 1250C.

9. A polymeric reaction product as claimed in claim 1 wherein a poly(oxyalkylene)amine is used which has the structure A~(R10)n~RNH2, where (a) R and each R' are independently selected from alkylene radicals of from 2 to 10 carbon atoms; (b) n is an integer from 2 to 50; (c) A is H2N, alkoxy of from 1 to 40 carbon atoms, or

where B is hydrogen or alkyl of from 1 to 10 carbon atoms, R and R' have the above meanings, R2 has the meaning given in claim 2 and y and z are integers from 1 to 10.

10. A polymeric reaction product as claimed in claim 9 wherein R in the formula of the poly(oxyalkylene)amine is ethylene ir isopropylene.

1 A polymeric reaction product as claimed in claim 9 or claim 10 wherein each R1 in the formula Wf the poly(oxyalkylene)amine is independently ethylene or isopropylene.

12. A polymeric reaction product as claimed in any of claims 9 to 1 1 wherein A in the formula of the pely(oxyalklylene)amine is H2N or alkoxy of from 1 to 20 carbon atoms.

13. A polymeric reaction product as claimed in any of claims 9 to 12 which has been formed at a temperature of from 600C to 1 C.

14. A polymeric reaction product as claimed in any of claims 1 to 13 wherein the epoxyhalo compound is epichlorohydrin.

15. A polymeric reaction product as claimed in any of claims 1 to 14 wherein the molar ratio of epoxyhalo compound to alkoxyalkylamine or poly(oxyalkylene)amine is from 0.7:1 to 1.2:1.

1 6. A process for the manufacture of a polymeric reaction product as claimed in any of claims 1 to 8 or 14 which comprise commingling 1 molar proportion of an alkoxyalkylamine with 0.5 to 2.0 molar proportions of an epoxyhalo compound at a temperature from 400C to 1 500C in the presence of an inorganic base, and recovering the reaction product.

17. A process for the manufacture of a polymeric reaction product as claimed in any of claims 9 to 14 which comprises commingling 1 molar proportion of a poly(exyalkylene)amine as defined in any of claims 9 to 12 with from 0.5 to 2.0 molar proportions of an epoxyhalo compound as defined in claim 1 or 14 at a temperature of from 400C to 1 500C in the presence of an inorganic base, and recovering the reaction product.

18. A process as claimed in claim 16 or 17 wherein the inorganic base is a hydroxide or carbonate of lithium, sodium, potassium, rubidium, cesium, calcium, magnesium or barium.

19. A process as claimed in claim 1 6 or 17 carried out substantially as hereinbefore described or exemplified in any of the foregoing Examples I to V or VIII to XII.

20. A polymeric reaction product as claimed in claim 2 when manufactured by a process as claimed in claim 16, 18 or 19.

21. A polymeric reaction product as claimed in claim 9 when manufactured by a process as claimed in any of claims 17 to 19.

22. A composition comprising a major proportion of hydrocarbon oil and containing from 0.0001% O/o to 1% by weight of a polymeric reaction product as claimed in any of claims 9 to 13 or 21.

23. A composition comprising a major proportion of a hydrocarbon oil and containing from 0.001% to 1% by weight of a polymeric reaction product as claimed in any of claims 2 to 8 or 20.

24. A composition as claimed in claim 22 or 23 wherein the hydrocarbon oil is a fuel oil.

25. A composition as claimed in claim 24 wherein the fuel oil is selected from gasoline, diesel fuel, jet fuel, aviation fuel, burner oil, furnace oil, kerosene and naphtha.

26. A composition as claimed in any of claims 22 to 25 whe in the epoxyhalo compound from which the polymeric reaction product is derived is epichlorohydrin.

27. A method of inhibiting sedimentation and discoloration of a hydrocarbon oil comprising dissolving therein a amount of from 0.0001 to 1% by weight of a polymeric reaction product as claimed in any of claims 1 to 15, 20 and 21.