DE2426504A1 - ADDITIONAL COMBINATION FOR MINERAL OILS - Google Patents

Description

LAW 9 /? R RH Λ

DR. JUR. DSfL-CHi = M. WALTER BEIT Z ^ Z O O U H-

AlFRRO i- '. ^ R-pr. ¹ :.?

dr. J ·;:,. · ..;., - ■ * ■ · λ. ; · -. '. wolff

FRAK.;. * I.-v7 .- ,. 'Λ /.Vjli-ijOCHSf

Our number 19 304

Esso Eesearch, and Engineering Company, Linden, U.J., Y.St.A.

Additional combination for mineral oils

Heating oils and other middle distillate mineral oils, e.g. diesel oils, contain normal paraffin hydrocarbon oils, which "at low temperatures tend to precipitate in crystals so large that a gel structure is formed which leads to it leads that the oil loses its flowability, whereby Difficulties arise in transporting the oils through pipes and pumps. The wax crystals precipitated from the solution clog pipes, sieves and filters. This problem has been known for a long time and so far there have been various additives used as a pour point depressant through which the door of the Crystals precipitating from the oil should be changed, which in turn leads to a reduction in the tendency of the wax crystals, solidifying to form a gel leads. Not only should

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Oils with low pour points, but also oils are obtained in which only small v / achskri stalle "form, so that the fluidity of the oils at low operating temperatures is not hindered by setting them in the filters _{or the like}

It has now been found that the flowability of middle distillate mineral oils at low temperatures can be improved if they are mixed with an additional combination consisting of a polymer containing halogenated polymethylene segments or substituting aliphatic hydrocarbon radicals with nitrogen. Succinic acid monoamide or derivative thereof and a small amount of a microcrystalline wax which contains considerable amounts of normal paraffinic hydrocarbons. More specifically, a waxy middle distillate mineral oil will contain about 0.05 to about 2.5% by weight of a microcrystalline wax and about 0.005 to about 0.5% by weight of a mineral oil-soluble additive component of the type mentioned above added, which consists either of a halogenated ethylene-containing polymer with a halogen content of about 1 to 40 wt .- ^ or a hydrocarbon-substituted succinic acid monoamide (hydrocarbyl succinamic acid). The nature of the latter two materials is explained in detail below.

Distillate oils that can be improved with the help of the present invention are those that have boiling points between 121 and 371 ⁰ C (250 and 70 ⁰ F) at atmospheric pressure. act cracked gas oils or mixtures in any proportions of directly distilled and thermally and / or catalytically cracked distillates,

The most common middle distillate mineral oils are kerosene, diesel oils, jet fuels and heating oils. The flowability

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The problem "at low temperatures is most common" with diesel oils and heating oils. A typical specification for heating oils calls for a 10 ^ distillation point not above about 227 ⁰ O (440 ⁰ P), a 50 $ distillation point not above about 271 ⁰ C (52O ⁰ E) and a 90 $ distillation point of at least 282 ⁰ C (540 ⁰ I ¹ ) and no higher than about 338 to 343 ° C (640 to 650 1), with some specifications even setting the 90 ^ distillation point at 375 ⁰ C (675 ⁰ I ¹ ). Heating oils preferably consist of mixtures of Yirgin distillates such as gas oils, naphtha etc. and cracked distillates, for example catalytic reflux oils. The invention is also applicable to diesels with great advantage, have that very fine at low temperatures udder happen, "A typical specification for diesels calls for a minimum Elammpunkt of 38 ⁰ C (100 ⁰ E) and a 90 ^ distillation point 282-338 C (540 and 640 ⁰ E); see ASTM regulations D-396 and D-975).

The microcrystalline yi axes which are used in accordance with the invention are obtained from residual oils. Such microcrystalline waxes are characterized by very small crystal forms, crystal forms, which are considerably finer and smaller comprise than that of paraffin wax, and a melting point in the range of about 63 to about 88 ⁰ C (145 to 19O ⁰ E), that is melting points collected lent higher than the melting points of ordinary paraffin waxes. The average molecular weights of microcrystalline waxes are generally between about 490 and about 800, in contrast to the molecular weights of paraffin waxes, which are between about 350 and 420. Microcrystalline waxes generally contain small amounts, for example 1 to 4% by weight of oil, because it is much more difficult to de-oil microcrystalline waxes than paraffin waxes. Microcrystalline waxes can also be in the form of Pfctrolatum, which contains larger amounts, for example 5 to 30 dollars, of oil

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The oil-soluble polymer with halogenated polymethylene segments, which is used as an additive according to the invention is an oil-soluble, halogenated one, made predominantly of hydrocarbons existing material with an average molecular weight from about 200 "to 500,000, preferably from 500 to 50,000, and more preferably from 500 to 10,000. The average molecular weights the polymers can be determined in a simple manner by the ebullioscopic method or with the aid of an osmometer will.

The halogenated polymers used according to the invention are polymers of ethylene or copolymers of Ethylene with other monoolefins with 3 to 6 carbon atoms, higher olefins in the copolymers not excluded are. Preferably the polymer or copolymer contains from 5 to about 100 weight percent ethylene.

The halogenated polymers used according to the invention are preferably chlorinated polymers. Through the Chlorination creates chlorine substituents on the polymer chain. The chlorination can be carried out using any method, allowing the chlorination to proceed until the desired chlorine content is reached. The optimal chlorine content depends somewhat on the type of polymer to be chlorinated. Generally the chlorinated materials contain about 0.2 up to about 40% by weight, preferably 1 to 35% by weight and more better 1.5 to about 25 wt .- ^ chlorine ,,

In one of the methods of chlorinating the polymer, chlorine is bubbled through the molten polymer at a temperature between about 66-204 ° C (150 to 400 ⁰ I ¹ ). In a second process, the chlorine is passed through a suspension of the polymer in an inert solvent such as carbon tetrachloride or other chlorinated methanes, chlorinated ethanes, etc., at a temperature of at least

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24 ⁰ C (75 ⁰ F). The rate of reaction can be increased by irradiating with visible light ". In a third method, the chlorine is bubbled through an aqueous suspension of the polymer. The first two methods are preferably used because it is believed that this is the way to bubble the chlorine comes into contact with a larger part of the inner polymer chain. The chlorination can also be carried out using known chlorinating agents such as sulfuryl chloride, oxalyl chloride, phosgene and others.

In the context of the present invention, preference is given to using the polymers and the chlorination methods which correspond to those correspond to those described in U.S. Patent 3,337,313 are. A major difference compared to the statements in the patent mentioned is that even after Polymers produced by the Ziegler process for use in the Additional combinations according to the invention are suitable. The polymerization processes, which are carried out with the help of catalysts of the Ziegler type and the polymers that can be obtained with them, which can be used for the purposes of the invention are described in many places in the relevant literature, for example in U.S. Patents 3,389,087 and 3,474,157.

The succinic acid monoamides (hydrocarbyl succinamic acids) substituted on the nitrogen by aliphatic hydrocarbon radicals and their derivatives can for the most part by the formula

R-CH- COX

- COX ¹

being represented; in this formula, R denotes a straight-chain aliphatic hydrocarbon group with either none or one olefinic unsaturation (alkyl or alkenyl) bonded to a secondary carbon atom of the succinyl-G group,

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which have at least 14 carbon atoms, generally Contains 15 to 40 carbon atoms and more preferably 15 to 30 carbon atoms. One of the substituents X and X is Represents hydroxyl and the other means

-HIT ¹

where Ή is the symbol for nitrogen and Y and Γ are aliphatic ^ hydrocarbon groups having 14 to 40, preferably 15 to 30 carbon atoms, the total number of carbon atoms of Y plus Y about 30 to 5 £, usually 32 to 48 and preferably 32 to 40 matters. Particularly suitable is a hydrocarbyl succinamic acid in which the -NYY group is derived from a dihydrogenated tallow amine (iö-ig-C-jg) and / or a di (behenyl-arachidyl) amine (Cp2 "" ^G 24 ^.

Y and Y can be aliphatically saturated or aliphatically unsaturated and are generally free from acetylenic shear Unsaturation; d "h. they mean either alkyl or alkenyl. It can contain one to two sites of olefinic unsaturation. Y and Y can be identical or different, straight-chain or be branched; they are preferably straight-chain. In the normal case of JÜ, the branches are no more than a carbon atom, i.e. it is methyl. The linkage to the nitrogen atom can be via a terminal or an inner carbon atom.

As is apparent from the above formula, _s, it is not important what position has the alkyl or alkenyl group with respect to the carboxamide or carboxyl group. As a result of the size of the amine, the main product in the usual process for production via succinic anhydride is a compound in which the alkenyl group is in the β-position to the carboxamide group.

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Of the derivatives, the most readily available "is preferred. Apart from that, toymen after" both isomers and mixtures of isomers can be used with equal success. In general, both individual compounds and mixtures of compounds can be used. Mixtures of. Homologues and isomers with various C and / or U substituents are often used when the individual precursors of the succinamic acid derivative are not readily available. Examples of succinamic acids are: Ν, ϊϋ-Dihexadeeylhexadecylsuccinaininsäure, B-hexadecyl-Hi-octadecyl-octadeeylsuc- cinamic acid, ΪΓ, ΙΙ-DihexadecenyT-CL ^ ₂ -alkenylsuecinamic acid, N-succadecenyl- lT-octadecosenyl-octadecosenyl Dioctadecenyl-0 ₁ g_ ₁ g-alkenylsucoinamic acid.

As mentioned earlier, suecinamic acid can can be used in the form of their amine salt, preferably as a mixture of acid and amine salt. The acid or the amine salt or mixtures of these two can be represented by the following lörmel:

R-GH- GOX ²

CH ₂ - COX ⁵

in this formula, R has the one already given above

p 3

Meaning and one of the two substituents X and X represents -HTT, where T and Y have the meaning already given above. The other of the two substituents

judge the IOn

-OH (UHY ² Y ⁵ ) h

2 3
ten X and X correspond to the formula

in which Y and Y ^v hydrogen, an aliphatic hydrocarbon radical with 1 to 30 carbon atoms or an oxaliphatic hydrocarbon radical with 3 to 30 carbon atoms

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atoms mean, with an Xether oxygen atom in the nitrogen bonded radical at least in ß-position to the nitrogen atom

2 "5
is available. Y and Y together can optionally form a heterocyclic 5 to 7-membered ring in which nitrogen and oxygen are represented as the only heteroatoms. The value of η can vary between 0 and 1, preferably between 0.1 and 0.9; this means that 10 to 90 mol # of suocinic minic acid are present in the form of the salt.

The aliphatic hydrocarbon groups are preferably saturated; if they are unsaturated, no more than Ethylenic unsaturation is present in two places. The total number the carbon atoms in HHY Y is 0 to 60, generally T to 40.

The groups that have been named for Y and Y also apply to ΊΓ and Ί? “ If, as will be discussed in more detail below, a different 1min is used for salt formation than for the production of succinamic acid a mixture of salts. Both the additional amine and the secondary amine that was used to make the sucoinamic acid participate in the salt formation. Primary amines as well as secondary amines can be used for salt formation. Examples of amines which can be used for salt formation are di-sec-butylamine, heptyP.aiain, dodecylamine, octadecylamine ,. tert-butylamine, morpholine, diethylamine, methoxybutylamine, methoxyhexylamine etc.

The hydrocarbyl-suceinamic acids according to the invention can be prepared easily and simply if an alkyl or alkenyl succinic anhydride is either directly ider ^{with the desired secondary amine at a temperature between about 66 and 121 0} O (150 to 250 ^{0 F) in approximately equimolecular amounts} in one

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inert solvents. The reaction time is in generally between 15 minutes and an hour. This implementation has been known for a long time and therefore does not need any further details to be discussed.

In the case of the alkyl or alkenyl amber used for the reaction one acid anhydride can be a single compound or a mixture of compounds; i.e., various Alkyl or alkenyl groups with different numbers Carbon atoms or different positions to the succinic anhydride group can be used. On the other hand, it is also possible to use a specific single isomer. However, since mixtures are generally more readily available, these are preferred. Often mixtures of aliphatic use substituted succinic anhydrides in which no single homologue in an amount greater than 25 mol $, each However, homolog is present in an amount of at least 5 moles.

Different secondary amines, both those with the same aliphatic hydrocarbon groups and those with different aliphatic hydrocarbon groups can be used for Production of sucoinamic acid can be used. It can either alkyl or alkenyl substituents are present on the nitrogen atom each of which has at least 14 carbon atoms. The difference between the two aliphatic hydrocarbon groups attached to the nitrogen atom is not essential, but is generally less than 8 carbon atoms, more preferably 6 carbon atoms. In most Cases the aliphatic ^ hydrocarbon group is straight-chain, i.e. normal, with the amino nitrogen being either internal or terminal hydrocarbon atoms is bonded.

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It has been found that using a molar ratio of amine to heat. Succinic anhydride of about 1: T, depending on the reaction conditions, a considerable amount of the amine remains in unreacted IOrm and can take part in the salt formation of the succinamic acid formed. Stay babbling in some up to 30 <fo the amine in unreacted IORM back) so as to form a substantial Henge salt. Generally, the salt is present in an amount from 10 to 30% of the total amount of succinamic acid.

In those cases where larger amounts of water are used during the implementation are present, the water can react with the succinic anhydride to form succinic acid If the temperature is not high enough for succinic anhydride to regress, the succinic acid will in most cases Waste left unreacted or with the existing, unreacted amine form an amine salt. The mixtures of the amic acid salts can therefore simply by using a 1: t "molar ratio of amine to succinic anhydride can be obtained without trying to complete the reaction respectively; the amine can also be used in excess of up to one mole,

The amine salts can be easily manufactured so that either directly or in an inert solvent to the Sucoineminsäure are ₀ by gentle heating, the reaction may be facilitated the amine.

According to the invention, together with the sucoinamic acid component an olefin polymer or a mixture of several olefin polymers is used, in particular ethylene-olefin copolymers having a molecular weight from about 1000 to TOO 000, even better about. 11500 to 20,000 at which the molar ratio of ethylene to be a Comonomer is between about 6: 1 and about 1i2:: 1i «

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The polymers used for the purposes of the invention should contain polyethylene segments whose chain length is about of the wax is approximated. That is, the polyethylene segments should average about 6 "to 30 monomers.

The main task of the "other monomer" is to act as "Divider" "to act between the polyethylene segments. For this reason, different monomers can be used, which can be found in easy way to copolymerize with ethylene. These olefins include "hydrocarbon only" terminal ones Olefins and mixtures of such olefins with about 3 "to 30 | usually about 10 "to 30 carbon atoms as well as various, heteroatom-containing, addition polymerization accessible, Terminal olefins such as acrylates, methacrylates, vinyl ethers, vinyl ketones, vinyl esters, dicarboxylic acids and their esters, etc.

The olefins which can be used in the copolymers correspond the formula

in which W is hydrogen or methyl and Z is a hydrocarbon group with 1 "to 30 carbon atoms, usually alkyl, where Z is free from aliphatic saturation.

An olefin containing heteroatoms generally corresponds to the formula _w t

0H _e ,

in which W is hydrogen or alkyl with 1 to 3 carbon

1 1

atoms or Z denotes and Z in turn denotes a carbon hydrogen oxyarbonyl group

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«12 -

I!

(QOC-

represents, in which Q has 1 to 20 carbon atoms and is an aliphatic saturated hydrocarbon, hydrocarbyloxy, acyloxy (Q00 _o ) or hydrocarbon carbonyl radical.

Z is free from aliphatic unsaturation »

Preferably, Z should mean acyloxy or hydrocarbyloxycarbonyl. The heteroatom-containing monomer should generally have 4 to 24 carbon atoms, more preferably 4 to 20 carbon atoms and have 1 to 2 oxygen atoms as heteroatoms and are only olefinically unsaturated at one point.

The type of preparation of the polymer or copolymer used according to the invention together with the succinamic acid component is not critical. Any method of making clay polymers of the desired molecular weight can be used will. In the preparation of the hydrocarbon copolymers, non-stereospecific catalysts are usually used. Examples of such catalysts are triethylaluminum with vanadium oxychloride or titanium tetrachloride. These catalysts belong to the Ziegler-type catalysts. It is also possible to use high pressure free radical polymerizations Perform catalysts.

The ratio of the alkenylsuceinamic acid component to the other polymers should generally be about 0.25 to 1Ό parts, more preferably about 2 to 8 parts and preferably 3 to 6 parts of acid per 1 part of polymer.

Mineral oils treated according to the invention generally contain from about 0.01 to about 2.5% by weight of microcrystalline wax and about 0.005 to about 0.5% by weight of the other additional component, i.e.

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of the halogenated, ethylene-containing polymer or the hydrocarbyl succinamic acid or the amine salt thereof or a combination of the hydrocarbyl succinamic acid component with an olefin polymer or copolymer of the type described above. The weight ratio of the two components in the combination can be between about 20: 1 and 1:20 generally about 10: Λ. to T: 10 and preferably about 5: 1 to 1: 5. Although it is possible to add the individual components directly to the oil by simply mixing them, it is often more advantageous to first prepare a concentrate by adding each component in a separate Solvent or both components dissolve in a common solvent. For this purpose, for example, heavy naphtha (heavy solvent naphtha) or a similar solvent with an aromatic character can be used. The concentrates generally contain 5 to 60 wt .- ^, total additive.

Example 1.

Were prepared oil mixtures by providing a middle distillate oil, which ^ 75 vol cracking distillates having a final boiling point of 352 ⁰ C. (665 ⁰ I) and 25 volume ^ "Straight Run Heavy Virgin laphtha" was, started one; the mineral oil had a cloud point of -11.1: ° C (+12 ⁰ P) and an API density of 30.degree. at 15.6 ^° C (60 ^° I). For the separation, parts of this oil were mixed with a microcrystalline Y / ax in various percentage concentrations and other parts with an alkenylsuccinamic acid derivative or a halogenated essentially ethylene-containing polymer also in different percentage concentrations either with the alkenyl succinamic acid derivative or the halogenated ethylene-containing polymer.

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«I4 -

The mixtures described in the above "used microcrystalline wax had a molecular weight of 634, a melting point of 75 ° G (167 ⁰ I ¹⁾ and a content of normal paraffin from 22.6 to io. In the halogenated polymer was around a substantially only äthylenhaltigen polymer having an average molecular weight of 2500 and a chlorine content of 21 wt -... ° / o It was in the form of a 50 wt .- ^ strength concentrate in a hydrocarbon oil before the succinamic was a Alkenylsuccinaminsäure consisting dihydrierteni Ealgamin and alkenyl sue c insäureanhydrid, derived from C ₁ , - p _O -cfc-01efinen had been prepared according to the method of the example of US Pat. No. 3,444,082; it was in the form of a about 70 wt .- ^ igen concentrate in a hydrocarbon oil.

All mineral oil mixtures as well as samples of the mineral oil without additives were subjected to pourability tests at low temperatures, namely the well-known low temperature sieve test ;; In this test, 2:00 ml cooled a sample of the oil at a controlled rate of 2.2 C ⁰ (4 P) per hour until a temperature of -23.3 C (-10 ⁰ P) reaches? this is the temperature at which the pourability test is carried out. The oil is allowed to flow from an upper compartment of the test device to a lower compartment of the test device at the test temperature, the entire apparatus being kept at the same test temperature. According to the law of gravity, the oil passes through a 30 mesh test sieve with a diameter of 1 cnu for 25 seconds. The percentage of oil that has passed the sieve at the end of the specified time is measured. Have more than 90 YoI. - $> if the oil passes the sieve at the end of the 25-second period, the oil has passed the test.

The composition of the various fuel oil mixtures that are being investigated and the values obtained in the low-temperature fluidity test are summarized in Table I below.

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posed. The percentages by weight of the added materials are in each case based on the total composition based. The specified amount of the second addition "relates In each case, refer to the concentrate of this additive and not the active ingredient.

Table I.

Added additives Amount of oil in $ that

no second additive no at 3uc c inamic acid polymer -23.3 0 "(- 1 (TE.) Wt .- $ no the halogenated Suecinamic acid Sieve pass *. microcrystalline s
wax Gew _o- $ no 0 no halogenated 0 0.2 no $ 0.025 0 0.4 Wt .- $ £ 0.05 polymer 40 Wt .- $ $ 0.015 45 $ 0.025 100 0.2 100 0.2

The data in the table above show that the additive the alkenyl succinamic acid and the halogenated ethylene-containing polymer each have the low temperature properties of heating oil Improved to some extent, while microcrystalline wax alone does not improve low temperature flowability he brings; on the other hand, the combinations of microcrystalline wax with either of the other two additives were in improvement the low-temperature hot properties of fuel oil extremely effective.

Example 2

The additional combinations according to the invention (additive combinations) were tested in a diesel oil for which the requirements

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are much stricter than with heating oil, because diesel oils have to pass much finer sieves or filters. Mixtures were made in a diesel oil that consisted of $ 45 catalytically cracked and $ 55 virgin distillates. The Diesel oil had a boiling range at atmospheric pressure from 202 to 341 ⁰ C (396-646 ° !.), a cloud point of - 16.7 ° ö (+2 ⁰ F.) and an API gravity of 34.2: 15 , 6 ⁰ C (60 ⁰ F.). The diesel oil and the mixtures containing the additives according to the invention were then tested for their low-temperature filterability. For this purpose, 200 ml of the oil were ^{cooled at a rate of 2.2 °} C. (4 ^° E ₀ ) per hour until a temperature of either -20, 6 C, (-5 ⁰ F.) 'Or -23.3 C (-1.0 ⁰ F.) was reached. At these temperatures the flowability and filterability was tested. The cold diesel oil had to pass through a 325 mesh sieve with a diameter of 1 cm, with a vacuum of 10, 16 cm of mercury being applied; the percentage of oil which passed the sieve in 25 seconds was determined.

The composition of the diesel oil blends to be tested and the test results are shown in Table II below. The microcrystalline Wax (referred to as microwax for short) was the same as in Example 1.

Table II Diesel oil quantity in $, which in 25 sec. additions a 325 mesh screen happened at ⁰ C -20.6 at ⁰ C -23.3 0 - no 0 - $ 0.25 microwax 0 - $ 0.5 microwax - 30th 20th $ 0.15 halogenated polymer 35 25th $ 0.20 halogenated polymer 55 0 $ 0.10 succinamic acid

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! Continuation of Table II

$ 0.20 _{micro wax plus 1nn 1no}

0.05 $ succinamic ^{acid ιυυ ιυυ}

$ 0.20 microwax plus

0.15 $ Suceinamic Acid 100 65

It can be seen that the suecinamic acid additives improve the low-temperature pouring properties slightly improved at -20.6 C, but not "at -23.3 G; the microcrystalline wax improved the low tempera No fluidity at all, but the combination of succinamic acid and microwax gave a 10% yield of oil both at -20.6 ° 0 and at -23.3 ° C. The combination of 0.1. Chlorinated ethylene polymer and 0.2 microcrystalline Wax gave a slightly greater improvement than 1. 1/2 times Amount of chlorinated polymer alone could be achieved.

Comparative examples

In the same way as in Example 2, mixtures with diesel oil as the base were prepared. A combination of the microwax with a copolymer was used in a mixture; the copolymer had an average molecular weight of about 2200 and containing about 60 weight percent ethylene and 40 weight percent isobutyl acrylate; It is abbreviated as EBAcr in the following. The second mixture contained a combination of the microcrystalline wax and an ethylene-vinyl acetate copolymer and a third mixture contained a combination of the micro-wax and another ethylene-vinyl acetate polymer ! and vinyl acetate, which repaid is called EVA-1 in, contained about 65 wt .- $ ethylene and 35 percent, - fo vinyl acetate and had an average molecular weight of from about 2400 to _o Preparation of the description of this copolymer is found in the United States - Patent 3 600 057, column 5, lines 22 - 45 _o The second copolymer of ethylene and vinyl acetate,

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hereinafter referred to as EVA-2 ", exhibited an average Molecular weight of about 1900 and a molar ratio of ethylene to vinyl acetate of about 4.2: 1. The description of the manufacture this copolymer is found in Example 1 of US Pat. No. 3,790,359. A fundamental difference between the copolymers EVA-1 and EVA-2 is that the latter has about 3 side chains terminating with methyl groups on the Polyethylene backbone per 1100 methylene groups in the backbone whereas in the copolymer EVA-1 there are about 12 side chains per 100 methylene groups in the backbone. All three above described copolymer materials have already been used as pour point depressants for heating oils and are commercially available available. The three additives were each in the form of a concentrate used in a hydrocarbon oil, the content

of active ingredient was about 50% by weight. The microwax it was the same as in example 1.

The. mixtures obtained in this manner the low-temperature liltrierbarkeitstest described in Example 2 were subjected to, and at a temperature of -2-0,6 ⁰ C ₀ The composition of the mixtures tested and the results of the investigations are summarized in the following Table III.

Table III

Additives 0.2 i 0.3 i 0.3 i $ 0.3 0.2 i
0.15 0.2 0
0.15 I microwax ι Mcr ί EVA-1 ί EVA-2 ι micro wax plus
<? o EBAcr '< Micro wax plus
1o EVA-1.

Diesel oil quantity in 20.6 ⁰ C in 25 sec _o sieve passed

at a 325 mesh

0 0

5 22

0 10

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Table III continued

0.2 io micro wax plus ' ο

$ 0.15 EvA-2. ^ö

It can be seen that in contrast to the combinations of microcrystalline wax and pour point depressant according to the invention No satisfactory flow properties of diesel oil "at low temperature through a fine filter could be achieved when combinations of microcrystalline wax and pour point depressants were used that were not fall within the scope of the present invention.

The combinations of microcrystalline wax and pour point depressants of the type "described and" claimed here be the only additives in mineral oils; you can after too in conjunction with other additives that are commonly used in mineral oil distillates are used, for example along with Eostinhi "bitoren, antioxidants, sludge formation "Preventing agents, demulsifying agents, dyes, opacifying agents, etc ·.

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Claims (1)

Claims 1.) Additional combination to improve the low-temperature filterability Clay mineral oils, consisting of a) a microcrystalline paraffin wax and b) an oil-soluble component, namely either I) a halogenated, ethylene-containing polymer with a halogen content of 1 to 40 percent by weight or II) a hydrocarbyl succinamic acid derivative of the formula R-CH- COX, C. CH ₂ - COX ₅ in which R is a straight-chain aliphatic hydrocarbon radical with 0 to 1 digits of ethylenic unsaturation and 14 to 40 carbon atoms, which is bonded to a secondary carbon atom of the succinyl group, 2 3 1 one of the two groups X and Tr the remainder -NYY represents, where Y and Y are aliphatic hydrocarbon radicals having 14 to 40 carbon atoms, 2 3 and the other of the two groups X and X is a radical of the formula -OH (UHY ² Y ⁵ ) n represents in which η varies between 0 and 1 2 3 and Y and Y ^ Y carbon, aliphatic hydrocarbon radicals with 1 to 30 carbon atoms or oxaliphatic hydrocarbon radicals with 1 to 2 are 3 carbon atoms, where Y and Y together with the nitrogen atom to which they are attached, 409881/0893 a 5 "to 7-membered heterocyclic Can form wherein the weight ratio of component (a) to component (b) is between 20: 1 and about 1:20. 2.) additional combination according to claim 1, characterized in that the component (To) consists of a chlorinated homopolymer of ethylene. 3.) additional combination according to claim 1, characterized in that component (b) consists of a chlorinated copolymer of ethylene with a C ~ - Cg - MonccLelin. 4 °) additional combination according to claim 1, characterized in that component (b) consists of a hydrocarbyl succinamic acid derivative in which the R substituent is derived from mixed cracked G - .., - - Gp ₀ wax olefins. 5o) additional combination according to claim 1, characterized in that di (
group that the -NYT group is derived from amines _s that of the (a) Dihydrogenated tallowamine ('0 - Jg-OUo) »(b £ Di (behenyl-arachidyl) -amine (Opp" ⁰ ^^) » (c) Mixtures of (a) and (b) belong. 6.) Additional concentrate, consisting of about 5 to about 60 % by weight of the additional combination according to claims 1-5 in an aromatic hydrocarbon solvent. Distilled mineral oils with improved low-temperature flow properties, characterized in that the same 409881/0893 contain the additional communication according to claims 1-5 in such amounts that a content of component (a) of 0.01 to 2.5 wt .- $ and of component (t>) of 0.005 "to 0, 5% by weight. 8.) Mineral oils according to claim. 7, characterized in that the oil is a diesel oil. Esso Research and Engineering Company, LindeA, U.J., V.St.A. Dr.H «J.Wolff Lawyer 409881/0893