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  • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
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Definitions

• Detergent range alkyl trimethyl ammonium chlorides of limited hydrocarbon solubility are especially useful as antihaze and/or antimicrobial agents for heating oils.
• the water solubility of the new oil additives unexpectedly facilitates their bactericidal effectiveness.
• antihaze activity of these additives is uniquely unaffected by polar oligomeric additives such as cold flow improvers and detergents also present in the oil products.
• This invention relates to liquid hydrocarbons containing minor amounts of surface active, higher alkyl trimethyl ammonium salts.
• this invention relates to hydrocarbon, oils, i.e., fuels, containing higher alkyl trimethyl ammonium salt additives.
• this invention relates to middle distillate fuels having higher alkyl trimethyl ammonium chlorides together with polar oligomeric additives.
• One useful aspect of the invention relates to the suppression of water-in-oil emulsion forming tendencies of liquid hydrocarbons by the use of minor amounts of said additives.
• the inhibition of haze formation in heating oils containing cold flow improver additives is of particular interest.
• Another useful aspect of the invention is the inhibition of microbiological deterioration, particularly of bacterial attack, of hydrocarbons.
• the higher dialkyl dimethyl ammonium salts are known oil soluble surfactants and microbiocides.
• U.S. Pat. Nos. 3,008,813 and 3,265,474 to .l. R. Siege] and U.S. Pat. 3,346,353 to B. R. Strickland and I... Berkowitz all describe hydrocarbon oils which contain higher dialkyl dimethyl ammonium salts, especially chlorides to improve their water tolerance.
• Other inventions involving similar compositions containing oil soluble quaternary ammonium salts are described in U.S. Pat. Nos. 3,033,665, 3,158,647 and 3,397,970.
• liquid hydrocarbon compositions containing higher monoalkyl trimethyl ammonium salts have highly unexpected useful properties. Although most of these monoalkyl salts such as the chlorides have a limited oil solubility, this does not adversely affect their usefulness. Surprisingly, oils containing these salts have properties which are absent in similar compositions containing the oil soluble salts of the prior art.
• monoalkyl trimethyl ammonium salts is particularly unique in hydrocarbons containing high molecular weight polar organic compounds.
• Such polymers in general facilitate the formation of water in oil emulsions, stabilize such emulsions and counteract the effect of antihaze agents.
• the additives of the present invention in contrast to quaternary ammonium salts having two or three higher alkyl groups, are effective in the presence of polar oligomers such as a low molecular weight ethylenevinyl acetate copolymer.
• This effectiveness of the salts of the present invention in the presence of such polymers is very important since such polymers are increasingly used, for example, to improve the cold flow properties of oils and to provide detergency to hydrocarbon systems.
• known antihaze agents often stabilize rather than break water in oil emulsions.
• emulsion stabilization results in water pickup from tank and ship bottoms.
• the hazy oil so obtained has an adverse appeal to the customer when contrasted with the clear oil he expects.
• the microbiocidal effect of monoalkyl trimethyl ammonium salts of low oil solubility in the present hydrocarbon compositions is surprisingly advantageous. This effect is associated with the preferential water solubility of such salts.
• Water solubility is important since the microbial degradation of oil, which is primarily due to bacterial activity, occurs at the water-oil interface. Since the amount of water, petroleum products are exposed to, is relatively small, preferential water solubility of our oil bactericides means concentration at their site of action rather than complete loss through selective extraction.
• liquid hydrocarbons containing minor amounts of surface active, C higher alkyl trimethyl ammonium salts have a surprising resistance to forming water in oil emulsions and to microbial degradation.
• the compositions of the present invention were distinguished over known hydrocarbon oil compositions containing higher dialkyl dimethyl ammonium salts by comparative evaluations of their antihaze and antibacterial properties.
• the present compositions were found to be particularly unique in retaining their haze resistance even in the presence of polar oligomeric additives, such as ethylene-vinyl acetate copolymers.
• the essential minor higher alkyl trimethyl ammonium salt components of the present compositions are characterized as follows: [R N (CI'I3)a] Q, wherein R is a C to C open chain aliphatic hydrocarbon group such as alkyl, alkenyl and alkynyl.
• the alkyl group may be interrupted by arylene groups such as phenylene, by amino, sulfide and oxide groups. As such the alkyl group may be branched or straight chain. A straight chain structure is preferred. Branching is preferably limited to methyl groups.
• the open chain alkyl group may have a saturated cyclic component such as cyclohexylene and cyclopentylene.
• the number of carbon atoms in the aliphatic group is preferably between Cg and C more preferably between C and C Salt mixtures having components with aliphatic groups of different carbon atoms are surprisingly advantageous.
• the aliphatic group is preferably saturated, i.e., an open chain alkyl radical such as shown by the formula [C H N (CH Cl".
• Preferred alkyl radicals have a completely non-branched straight chain structure or an alphamethyl substituted normal alkyl structure as shown by the following salt formula:
• n, m and l are numbers in accord with the number of carbons in the aliphatic group. These three formulae are of course related to the more general earlier formula.
• the R group of the earlier formula equals the C I-I Cl-I (Cl-l and the CH (CI-I ),,,CH(CI-I of the present formula. Accordingly, the preferable number ranges are 8 to 40 for n, 7 to 39 for m and 6 to 38 for l. In the case of unsubstituted normal alkyl groups, the most preferred number of carbon atoms is 14. However, it is surprisingly advantageously to employ a mixture of n-alkyl compounds derived from coconut oil. Similarly, the a-methyl branched product is preferably derived from a mixture of detergent range olefins.
• the higher alkyl group of the present salts is the hydrophobic part of a surfactant molecule.
• it is an oil soluble group; nevertheless its size, i.e., carbon number, is limited by a limited water solubility requirement for the overall molecule.
• this group must be large enough to assure some oil solubility.
• the water versus oil solubility ratios, i.e., coefficients, are very important in determining the demulsifying and bactericidal properties of the salts in hydrocarbon systems. The optimum properties for a practical use will, of course, also depend on the hydrocarbon, e.g. on its paraffinic versus aromatic character.
• the Q anion of the salts of the present invention includes negatively charged, nonradical species inorganic and organic in character.
• Inorganic anions include halides such as chloride, bromide, fluoride; phosphates such as polyphosphates; phosphite; sulfate and nitrite.
• Organic anions include carboxylates, having 1 to 30, preferably 1 to 18, carbon atoms, such as acetate, neotridecanoate, ethylenediamine tetraacetate; organic phosphate and phosphine anions such as C to C dialkyl dithiophosphate, phosphate, phosphite and phosphonate; C to C hydrocarbon sulfonate such as methanesulfonate, benzenesulfonate, tetrapropylenesulfonate; C to C alkyl sulfate such as methylsulfate.
• carboxylates having 1 to 30, preferably 1 to 18, carbon atoms, such as acetate, neotridecanoate, ethylenediamine tetraacetate
• organic phosphate and phosphine anions such as C to C dialkyl dithiophosphate, phosphate, phosphite and phosphonate
• Chloride anions are most preferred because of the ease of preparation of the chloride salts and their high effectiveness.
• the Q anion may be a complex anion formed by combining one of the simple anions such as the chloride with a metal salt or an acid such as boron fluoride or acetic acid. In general, monovalent anions are preferred.
• the ammonium salt component is usually present in the liquid hydrocarbon at a concentration of 0.0001 to 1 percent, preferably 0.0005 to 0.1 percent, most preferably, 0.00l to 0.004 percent.
• concentration of the salt is somewhat dependent on the major hydrocarbon component used and the properties desired. The above preferred concentrations are mainly recommended for heating oils resistant to water haze. Another important property of similar oil compositions is resistance to microbiological degradation. Other properties include reduced corrosivity, detergent action, etc.
• ammonium salts especially the higher n-alkyl trimethy] ammonium chlorides, are commercially available. Salts containing a mixture of alkyl groups are especially widely used because they can be manufactured from readily available agricultural products, such as coconut oil, tallow oil, soya oil. The preparation of such chlorides, their compositions and suppliers are described in the monograph on Cationic Surfactants cited hereinabove.
• the major hydrocarbon components of the present compositions are preferably hydrocarbon oils of natural origin such as crude petroleum and distillate fuels.
• the petroleum distillates have preferable boiling ranges between and 900F.
• Such products include gasolines, jet fuels, diesel fuels, heating oils, lubricating oil, transformer oils. Distillate fuels boiling in the range between about 250 and 750F. are particularly preferred.
• Heating oil and diesel fuel are specific choice hydrocarbons. They are described in ASTM Specifications D-396-48T and D-975-53-T. Most specifically, Grades 1 and 2 heating oils are used. Jet fuels are other specific examples. Typical aviation turbojet fuels are described by US. Military Specifications and referred to as JP-4, .IP-5, JP-6, etc.
• the polar oligomeric additives of the present compositions are optional minor components. Such additives are described in detail in US Pat. Nos. 3,008,813; 3,265,474; 3,346,353 and 3,397,970 which were referred to earlier. These additives preferably contain a major proportion of nonpolar hydrocarbon groups such as alkyl, alkylene, phenyl, naphthyl, and a major proportion of polar atoms such as oxygen and chlorine. The oxygen is preferably present in est'er groups.
• a preferred polar oligomer is the copolymer of ethylene and vinyl-acetate described by M. J. Wisotsky, A. E. Kober and I. A.
• Such polymers have a preferable molecular weight range of 400 to 20,000. Increasingly more preferred molecular weight ranges are from 500 to 10,000, from 500 to 5,000, from 1,000 to 3,000.
• polymeric additives are preferably employed in concentrations ranging from about 0.00l-to 2 percent, more preferably 0.001 to 0.15 percent, most preferably 0.005 to 0.05 percent.
• these polymers are mainly employed to secure the desired degree of fluidity at low tempertures.
• such additives have a polymethylene chain interrupted by aliphatic groups having substituents containing oxygen, chlorine and aromatic radicals.
• Such polymers can be preparedby copolymerizing a major amount of .etylene with minor amounts of an ethylenic monomer having substituents containing the above radicals.
• substituted ethylenes are vinyl esters of C -C monocarboxylic acids, acrylate, maleate and fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones.
• the copolymerization is usually catalyzed by free radical type chemical or irradiation initiators.
• compositions have a unique resistance to water haze formation and microbial degradation due to the presence of the higher alkyl trimethylammonium salt component.
• the haze behavior is usually determined in the Waring Blender Test, In this, five milliliters of water and.
• the rate of the breakup of the emulsion is measured spectrophotometrically.
• the amount of light transmitted through a sample from the top of the mixture is indirectly related to haze.
• the microbial degradation of hydrocarbons is mainly due to bacterial attack by gram negative organisms at water-oil interfaces. Certain bacteria readily metabolize straight chain hydrocarbons. These hydrocarbons are present in petroleum and hydrocarbon fuels. The higher the percentage of paraffinic hydrocarbons, the faster the microbial degradation. Fast microbial degradation is concurrent with a rapid increase of the number of bacteria in the water phase.
• the inhibition of microbial degradation is indirectly measured by determining the concentration of additives which will inhibit the multiplication of bacteria or kill the microorganisms. Usually, serial dilution tests are carried out using different additive concentrations. A known concentration of a bacterial culture is an aqueous nutrient medium which is overlayered with oil. Bacterial counts are made at various intervals after the inoculation.
• the abovedescribed higher alkyl trimethylammonium salts are surprisingly useful as demulsifiers for water in hydrocarbon systems particularly as antihaze agents for hydrocarbon fuels and petroleum crudes.
• such salts are useful antihaze agents in middle distillate fuels such as heating oil and diesel fuel.
• the said higher alkyl trimethyl ammonium salts are unexpectedly useful to prevent the microbial degradation of liquid hydrocarbons when in Contact with water.
• These salts are particularly effective bacteriostatic and bactericidal agents for petroleum and products derived therefrom such as distillate fuels. They are specifically useful as heating oil, diesel fuel, jet fuel and crude oil bactericides.
• the present invention provides methods for preventing and breaking water in oil emulsions especially haze in the systems described. It also provides a method for similarly preventing and inhibiting microbial, particularly bacterial, attack and deterioration.
• the present aliphatic hydrocarbyl trimethyl ammonium salts may be added to the liquid hydrocarbon as such or in the form of a concentrate solution in polar organic solvents.
• exemplary solvents are alcohols such as isopropanol, ethylene glycol; kettones such as methyl isobutyl ketone; esters such as ethyl acetate, tricresyl phosphate, etc.
• These salts may also be used in composite multipurpose formulations with other oil additives such as flow improvers, antioxidants, etc.
• EXAMPLES A. Effectiveness of Surface Active Quaternary Ammonium Compounds as Demulsifiers in the Waring Blender Test The antihaze effectiveness of various quaternary ammonium chlorides in oil was tested in a Waring Blender Test. In this test the oil was mixed with one percent water and a certain amount of the ammonium chloride in the blender at 10,000 rpm for 2 minutes to produce the test emulsions. The stability of the emulsions was then determined by a periodical measurement of their light transmittance. The light transmittance is directly related to the clarity of the resulting oil.
• the oil was a heating oil containing percent alkyl, 10 percent aryl and essentially no olefinic hydrogens by proton magnetic resonance (pmr) spectroscopy.
• the flow improver composition consisted of about 52 percent ethylene vinyl acetate copolymer and 48 percent light mineral oil.
• the copolymer had a number average molecular weight of about 2,605 by vapor phase osmometry. Its pmr spectrum showed a ratio of about 6.8 for the ethylene versus vinyl acetate derived structural units. For every one hundred methylene atoms in the backbone of the copolymer there were about 10-12 methyl branches.
• This copolymer was prepared by copolymerizing ethylene and vinyl acetate using an ethylene pressure of 950 psig at a temperature of about with di-tertiary butyl peroxide initiator.
• the C -a1kyl derivative is more effective than the C compound although the latter is more surface active.
• the higher dialkyl derivative in Group II, dicoco dimethyl ammonium chloride is an outstandingly effective demulsifier in the absence of the copolymer but an emulsion stabilizer in its presence.
• the compound of the third group i.e., the higher trialkyl methyl derivative has no significant beneficial action in the absence of the polar copolymer and an adverse effect in its presence.
• EXAMPLE 2 Effectiveness of Various Monoalkyl Trimethyl Ammonium Chlorides in thePresence and in the Absence of a Slightly Branched Ethylene Vinyl Acetate Copolymer
• a polar oligomer again an ethylene-vinyl acetate copolymer was used. This copolymer again had a molecular weight range in the 2,000s. Also, this copolymer had a high ethylene-vinyl acetate ratio, i.e., about 8. How ever, this polymer had only about 4 methyl branches per 100 methylene groups.
• this copolymer has more crystalline character and lower solubility. As such it is dissolved in a naphthenic solvent and employed as a concentrate.
• the other significant difference is the absence of crosslinking in this copolymer as opposed to the minor amount of gel in the cosequent to the mixing this control is almost completely clear just like most of the oils containing the test compounds.
• the demulsifying effect of the test compounds in this case is best observed shortly after mixing. The one hour data show that at the higher concentration all these quatemaries acted as effective demulsifiers (No.
• the sect-alkyl groups have the following composition: I)? Cu; 187: C l7'7r C I67: C r; I67: Cm; 14% Cm; I394 C 5% C polymer of the previous example. These differences are largely due to the lower temperature of polymerization of the present product, i.e., about C.
• the test data on compositions containing no quaternary additive show that, in contrast to the highly branched copolymer of Example 1 (No. 3), the slightly branched copolymer of Example 2 (No. 2) has no adverse effect on the emulsification tendency of the base oil (No. l).
• the transparency data of the first seven hours after the mixing show that the addition of the monoalkyl ammonium compounds helps to demulsify in the presence of both copolymers (Nos. 49).
• the dialkyl compound shows no beneficial effect in the presence of either of the copolymers (Nos. 1 1 and 12) although it is effective in their absence (No. In general, the effects are more pronounced and the differences are more significant in the presence of the highly branched copolymer.
• Oxidant Oxidant" Polymer ppm 0 l 5 7 24 l 3 17 29 73 2 2O 24 68 94 92 94 98 3 21 ll 59 67 74 79 89 4 21 9 48 71 74 79 87 5 21 20 20 63 95 96 97 I00 6 21 l5 6 30 39 43 41 61 7 21 15 20 24 62 81 84 92 88 8 21 15 7 34 69 61 57 77 9 21 I5 20 I2 45 64 7O 71 74 Used as a isopmpanol Solution Composed of light cracked oil and 25% virgin gas oil A mixture of methyl cyclohexyl amines Dieyclohexyl amine A multipurpose additive consisting of an acrylate copolymer which is described in Table V EXAMPLE Effectiveness of Monococo Trimethyl Ammonium Chloride as a Dehazing Agent in Various Heating Oils in the Presence of an Acrylate Copolymer As a hydrocarbon phase for
• monium chloride is further illustrated in various heat- As the water phase a P basal salt medium was used. ing oils. These oils also contained antioxidants and an Thi medium was similar to the one reported by E. .I. acrylate copolymer as a multipurpose additive.
• Table V. Iowa entitled Effect of Hydrocarbon Structure on The light transmittance data show that in each case Mechanisms of Microbial Alkane Metabolism, pubthe addition of the quaternary compound increased the lished by University Microfilms, Inc. as No. 66-7218 in transmittance, i.e., reduced haze. The difference in the Ann Arbor, Michigan.
• test compound was added as a 0.1 verse effect, however, is overcome by the addition of ml solution. Onto the top of the final water solution, the higher monoalkyl quaternary compound. 100 ml of the oil was layered.
• a multipurpose additive consisting of a 71 diluent solution of a copolymer of 52.671 di-C oxo alkyl fumarate, 26.8% di-C -alkyl fumarate 17.2% vinyl acetate,
• test bottles were closed with rubber stoppers and vented through a No. 18 gauge hypodermic needle. They were incubated for 7 days under stationary conditions on a laboratory bench at about 24C. Thereafter, 1 ml was withdrawn from the interface region of each bottle, using a 1 ml tuberculine syringe fitted with a No. 18 gauge needle. A 0.1 ml sample of each of 10' 10' and 10" dilutions were spread over a nutrient agar plate, which was subsequently incubated for 72 hours. Thereafter, the number of viable cells was determined and tabulated as shown in Table VI.
• the sharp reduction of viable cells by the application of the experimental and control compounds showed a generally high effectiveness.
• the lower cell count in the mixture containing 500 ppm monococo trimethyl ammonium chloride (No. 1) than in the similar mixture containing the dicoco compound (No. 2) indicates that the higher monoalkyl salts are surprisingly more effective than the higher dialkyl derivatives.
• the higher monoalkyl compound having a branched alkyl chain is more effective than the known oil bactericide control.
• the bacteria were from the Borregas Field, Kingsville, Texas.
• the test system was a 3.5 percent NaCl sulfate reducing broth bacteria culture containing 100,000 bacteria per milliliter. Different concentrations of the ammonium chlorides were added to vials containing the broth medium. The media were then inoculated. The vials were incubated at C. and observed at intervals for evidence of bacterial growth. The results are shown by Table VII.
• EXAMPLE 8 Effectiveness of Quaternary Higher Monoalkyl Versus Dialkyl Ammonium Chlorides as Crude Oil Bactericides against Aerobic Bacteria
• the comparative effectiveness of a pair of ammonium chlorides was determined against aerobic bacteria from Block 73, Louisiana.
• the test system was a 3.5 percent NaCl aerobic broth bacteria culture containing 100,000 bacteria per milliliter.
• the test procedure was the same as in the previous example. The results are shown by Table VIII.
• EXAMPLE 9 Effect of Higher n-Alkyl Trimethyl Ammonium Chlorides as Middle Distillate Bactericides
• the comparative bactericidal effectiveness of tri- 10 methyl ammonium chloridies having higher n-alkyl groups'of different chain length was investigated in a P basal salt medium overlayered with diesel fuel.
• test organisms two gram negative strains isolated from tank bottoms of a home oil heater were used (Nos. 1 and 2). l
• EXAMPLE 10 Effect of Straight Chain and Branched Higher Alkyl Trimethyl Ammonium Chloride as Middle Distillate Bactericides
• the comparative effectiveness of several higher 1- alkyl and 2-alkyl trimethyl ammonium chlorides was investigated using the test procedure described in the previous example. However, in this test only one gram negative bacterial strain was used. This strain was isolated from the heating oil tank bottoms of a home. The test mixtures were sampled after 24 and 48 hours. The results are shown in Table X.
• EXAMPLE 1 Effect of n-Dodecyl Trimethyl Ammonium Chloride as a Jet Fuel Bactericide The effect of various concentrations of n-dodecyl trimethyl ammonium chloride on the growth of various bacterial strains utilizing jet fuel was studied.
• the five bacterial isolates were routinely maintained on nutrient agar slants by weekly transfers.
• the above five cultures 24 hr. old slant cultures) were inoculated into culture tubes containing 7 ml of sterile nutrient broth and incubated at 30C. under stationary conditions for 24 hours. At the end of the incubation period, contents from each tube were transferred under sterile conditions into sterilized centrifuge tubes.
• the cells were harvested by centrifugation of 10,000 RPM for 15 minutes. The cells were washed by resuspending the pellet in 10 ml sterile P basal salts medium and recentrifuged. The washed cells were resuspended again in l ml of sterile medium.
• composition of claim 1 wherein the liquid hydrocarbon is crude petroleum or a petroleum distillate and the higher alkyl trimethyl ammonium salt is present at concentrations between abot 0.001 percent and 1 percent.
• composition of claim 2 wherein said higher alkyl trimethyl ammonium salt is a chloride in a concentration ranging from 0.00l to 0.004 percent by weight.
• composition of claim 3 wherein said ammonium chloride is present in a petroleum crude.
• composition of claim 5 wherein said petroleum distillate is a distillate fuel boiling in the range between about 250 and 750F.
• composition of claim 7 wherein said salt has an aliphatic R group of the formula C l-[ wherein n is 8 to 40.
• composition of claim 8 wherein the structure of the group C,,H is Cl-l (Ch and CH (CH CH(CH wherein m is 7 to 39 and l is 6 to 38.
• composition of claim 7 wherein said salt has the group Q, selected from the group consisting of halide, phosphate, phosphite, sulfate, nitrite, carboxylate, sulfonate and phosphonate.
• composition of claim 10 wherein the group O is selected from the group of nonradical anions consisting of halide, phosphate, phosphite, sulfate, nitrite, carboxylate, sulfonate, phosphonate.
• composition of claim 7 wherein the liquid hydrocarbon is crude petroleum or a petroleum distillate.
• composition of claim 13 wherein the petroleum distillate also contains a minor polar ethylene copolymer additive having a molecular weight range of about 400 to 20,000 said additive being derived using comonomers selected from the group consisting of vinyl esters of C -C monocarboxylic acids, acrylate esters of C to C alcohols, maleate esters of C, to C alcohols, fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones in amounts sufficient to secure fluidity at low temperatures.
• a minor polar ethylene copolymer additive having a molecular weight range of about 400 to 20,000 said additive being derived using comonomers selected from the group consisting of vinyl esters of C -C monocarboxylic acids, acrylate esters of C to C alcohols, maleate esters of C, to C alcohols, fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones in amounts sufficient to secure fluidity at low temperatures.
• a petroleum distillate composition boiling in the range between about 250 and 750F. having increased resistance to emulsion formation and microbial degradation containing from about 0.001 to 0.1 percent of a salt of the formula wherein n is 8 to 25, and from about 0.001 to 2 percent of a polar polymer additive having a molecular weight range of about 400 to 20,000 said additive being derived using comonomers selected from the group consisting of vinyl esters of C C monocarboxylic acids, acrylate esters of C to C alcohols, maleate esters of C to C alcohols, fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones, in amounts sufficient to secure fluidity at low temperatures.
• composition of claim 7 wherein said salt is monococo trimethyl ammonium chloride.
• a crude petroleum or petroleum distillate composition containing as a minor component a surface active, water soluble, saturated, open chain higher alkyl trimethyl ammonium salt, said alkyl group containing a minimum of eight carbon atoms and a minor polar polymeric additive having a molecular weight range of about 400 to 20,000 and prepared by the copolymerization of ethylene and vinyl acetate, in amounts sufficient to increase its resistance to emulsion formation.
• composition of claim 2 wherein said petroleum also contains a minor polar ethylene copolymer additive having a molecular weight range of 400 to 20,000, said additive being derived using comonomers selected from the group consisting of vinyl esters of C -C monocarboxylic acids, acrylate esters of C to C alcohols, maleate esters of C 1 to C alcohols, fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones in amounts sufficient to secure fluidity at low temperatures.
• a minor polar ethylene copolymer additive having a molecular weight range of 400 to 20,000, said additive being derived using comonomers selected from the group consisting of vinyl esters of C -C monocarboxylic acids, acrylate esters of C to C alcohols, maleate esters of C 1 to C alcohols, fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones in amounts sufficient to secure fluidity at low temperatures.

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