JP2005015798A - Oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a fuel oil composition having improved low-temperature performance, wherein the composition is derived from animal oil or vegetable oil or is their mixture with petroleum-based fuel oil. <P>SOLUTION: This oil composition comprises an oil obtained from a methyl ester of an animal or a vegetable material or or a derivative thereof, or a mixtures thereof with a petroleum-based oil, mixed with an ethylene-vinyl ester copolymer cold flowability improving additive having at least 17 mole% vinyl ester units and containing 5 or more alkyl branches per 100 methylene groups on the main chain. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to the use of wax crystal modifying additives in oils or derivatives thereof derived from animal or plant raw materials or both, or mixtures of these oils and petroleum oils.

  Oils obtained from animal or plant sources are mostly metabolites containing monocarboxylic acids, ie triglycerides of saturated or unsaturated acids containing 10 to 25 carbon atoms.

  In general, oils as described above contain a large number of acid glycerides, and the number and type of acids differ depending on the raw material from which the oil is derived, and may additionally contain phosphoglycerides. These oils can be obtained by methods known in the art.

  Examples of these oil derivatives include alkyl esters such as methyl esters of fatty acids of vegetable oils or animal oils. Such esters can be produced by transesterification.

  Therefore, when referring to oils derived from animal or plant-based raw materials in this specification, both oils obtained from animal or plant-based raw materials or both, or derivatives thereof are included.

FR-A-2,492,402 describes a fuel composition containing one or more fatty acid esters of animal and plant materials represented by the general formula R ¹ —COO—R ² . In the above formula, R ¹ is a substantially linear saturated or unsaturated aliphatic group containing 5 to 23 carbon atoms, and R ² is a linear or branched saturated or unsaturated group containing 1 to 12 carbon atoms. Saturated aliphatic group is shown. This fuel composition is described as being particularly suitable for use in diesel engines and having a range approximately equal to the cetane index of conventional diesel fuels derived from mineral oil.

  However, fatty acid ester compositions have limited utility as diesel fuel due to their low temperature properties. DE-A-4,040,317 discloses that if the temperature falls below -5 ° C, the above fuel may be solidified in the supply line due to insufficient filterability and this low temperature. As a method for improving the filterability, short-chain fatty acid methyl esters and specific polymer materials, that is, polymer esters of acrylic acid and / or methacrylic acid derived from alcohol having 1 to 22 carbon atoms, A process is described which involves adding a mixture of the ester copolymer.

  There is ample record in this field regarding the low temperature properties of crude oils and lubricating oils as well as petroleum oils such as fuel oils such as middle distillate fuel oils, ie mineral oils and their derivatives. Similarly, the use of additives that modify the wax crystal structure of these mineral oils and their derivatives is also known. Examples of such additives and their use are described in U.S. Pat.No. 3,048,479, GB-A-1,263,152, U.S. Pat.No. 3,961,916, U.S. Pat.No. 4,211,534, EP-A-153,176 and EP-A-153,177. Has been.

  In contrast to the mineral oils and their derivatives, the low temperature properties of the oils of the present invention, which are oils derived from animal or plant materials, are mainly governed by the precipitation of fatty acid esters with high molecular weight present as the main component. Such fatty acid esters are often derived from a mixture of saturated and unsaturated fatty acids. By way of example only, the main components of rapeseed oil methyl ester are methyl esters of oleic acid, linoleic acid, linolenic acid and erucic acid.

  In general, the exact ratio of each component in an individual oil may vary depending on the seasonal variation of the fatty acids that make up the raw material, or the specific method used to obtain the fatty acids. The number of unsaturated fatty acid derivatives such as is significantly higher than that of saturated fatty acid derivatives.

  Although this oil has a predominance of ethylenically unsaturated fatty acid ester, its crystallization behavior is different from the behavior of the mineral oil described above. -It is believed to be due to structural differences in the hydrocarbon chains of alkanes and unsaturated fatty acid esters.

  EP0629231B1 describes throughout the use of low temperature fluidity enhancing additives commonly used in petroleum-based fuels for the purpose of improving the low temperature properties of oils derived from animal or vegetable oils. Among the additives described in EP0629231B1, mention is made of an ethylene unsaturated ester copolymer fluidity improver. EP0629231B1 page 11 polymer A contains about 16 mol% vinyl acetate.

  The present invention relates to fuel oils derived from animal oils or vegetable oils and petroleum-based fuels according to a specific limited category having a specific vinyl ester content and a specific degree of branching among ethylene-vinyl ester copolymers. This is based on the finding that the low temperature performance in a mixture with oil is improved.

  The present invention contains a large amount of an oil obtained from animal oils or vegetable oils or both methyl esters thereof, or a derivative thereof, or a mixture thereof with petroleum oils, and further contains an oxyhydrocarbon chain. A small amount of ethylene-vinyl ester copolymer flow improver having a polymethylene main chain divided into segments is mixed, and the vinyl ester content in the polymer is at least 17 mol%, preferably 17-25 mol%, more It is preferably 17 to 19 mol%, and when the number of alkyl moieties relative to 100 methylene moieties of the main chain is determined, the number of short alkyl branched chains is more than 5, preferably 6 to 8. The ester is an ester of a monocarboxylic acid having 2 to 30 carbon atoms, preferably 2 to 10 carbon atoms.

  Preferred copolymers include ethylene-vinyl acetate, ethylene-vinyl propionate, ethylene-vinyl hexanoate, ethylene-2-ethyl hexanoate vinyl, or ethylene-vinyl octanoate copolymer. The number average molecular weight (Mn) of the copolymer is in the range of 1,000 to 10,000, preferably 2,000 to 6,000, more preferably 3,000 to 5,000, as measured by gel permeation chromatography (GPC) based on polystyrene.

  The copolymer may be in the form of a mixture of two copolymers as described in US Pat. No. 3,961,916. If desired, additional comonomers can be added to derive copolymers, such as terpolymers, quaternary copolymers or even multi-component copolymers where the additional comonomer is propylene or isobutylene. Good.

  Copolymers can be made by directly polymerizing comonomers. It can also be obtained by transesterifying a certain ethylenically unsaturated ester copolymer or hydrolyzing or reesterifying it into a different unsaturated ester copolymer. For example, an ethylene-vinyl hexanoate copolymer or an ethylene-2-ethyl hexanoate vinyl copolymer can be prepared from, for example, an ethylene-vinyl acetate copolymer using this method.

The polymers of the present invention can be used with one or more of the following conventional low temperature fluidity enhancing additives.
(A) Another ethylenically unsaturated ester copolymer (b) Comb polymer (c) Polar nitrogen compound (d) Compound containing cyclic structure (e) Hydrocarbon polymer (f) Polyoxyalkylene compound (g) Hydrocarbylation Aromatic pour point depressant (h) alkylphenol formaldehyde condensate

  The features of the present invention will be described in more detail.

Oils:
Examples of oils derived from animal or plant materials include rapeseed oil, cilantro oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, palm kernel oil, coconut oil, mustard oil , Beef tallow and fish oil. In addition, oils derived from corn, jute, sesame, shea butter, subterranean fruit, flaxseed can also be derivatized by methods known in the art. Rapeseed oil is a mixture of partially esterified fatty acids and glycerol, but this rapeseed oil is recommended because it can be used in large quantities and can be obtained in a simple manner by squeezing rapeseed.

  As lower alkyl esters of fatty acids, for example, the following commercially available mixtures may be considered. That is, for example, lauric acid, myristic acid, palmitic acid, palmitooleic acid, stearic acid, oleic acid, elaidic acid, petrothelic acid, ricinoleic acid, eleostearic acid, linoleic acid, linolenic acid, eicosanoic acid, gadoleic acid, These are ethyl esters, propyl esters, butyl esters, especially methyl esters of fatty acids having 12 to 22 carbon atoms such as docosanoic acid or erucic acid, and iodine values of 50 to 150, especially 90 to 125. A mixture having particularly advantageous properties is a mixture containing a methyl ester of a fatty acid having 16 to 22 carbon atoms as a main component (that is, containing at least 20% by mass) and having 1, 2 or 3 double bonds. . Recommended fatty acid lower alkyl esters are methyl esters of oleic acid, linoleic acid, linolenic acid and erucic acid.

  Commercially available mixtures of the type described above can be obtained, for example, by cleavage or esterification by transesterifying animal and vegetable oils with lower aliphatic alcohols. For the production of lower alkyl esters of fatty acids, it is advantageous to start with fats and oils with high iodine value, such as oils such as sunflower oil, rapeseed oil, cilantro oil, castor oil, soybean oil, cottonseed oil, peanut oil or beef fat It is. A lower alkyl ester of a fatty acid based on a new kind of rapeseed oil, the fatty acid component of which is more than 80% by mass and derived from an unsaturated fatty acid having 18 carbon atoms is recommended.

  Particularly preferred are the oils of the present invention that can be used as biofuel. Biofuels, i.e. fuels derived from animal or plant sources, are considered to be less likely to destroy the environment during combustion and are derived from renewable resources. It is reported that the amount of carbon dioxide produced during combustion is less than that produced by an equivalent amount of petroleum distillate fuel (eg, diesel fuel) and little sulfur dioxide is produced. Certain vegetable oil derivatives, such as those obtained by saponification or reesterification with monovalent alkyl alcohols, can be used as an alternative to diesel fuel. Among rapeseed oil esters, for example, rapeseed oil methyl ester (RME) has been used alone or in a mixture with petroleum distillate fuel. That is, biofuel is oil obtained from plant or animal raw materials or both, or derivatives thereof, which can be used as fuel.

  Most of the aforementioned oils can be used as biofuels, but vegetable oils or derivatives thereof are preferred, and among them, particularly preferred biofuels are rapeseed oil, cottonseed oil, soybean oil, sunflower oil, olive oil, palm oil or these. Of these, the rapeseed oil methyl ester is particularly preferred.

The present invention can also be applied to a mixture containing 95 to 5% by mass of the biofuel and 5 to 95% by mass of petroleum-based fuel. Petroleum-based fuel oils can include atmospheric distillate or vacuum distillate, cracked gas oil, or blends of any ratio of direct and pyrolysis and / or catalytic cracking fractions. The most common petroleum distillate fuel oils are kerosene, jet fuel, diesel fuel, heating oil, and heavy oil fuel. These distillate fuel oils usually have a boiling point in the range of 100 to 500 ° C. The heating oil may be a straight-run, normal-pressure distillate, but may contain vacuum gas oil, cracked gas oil, or both. The fuel may contain a large amount or a small amount of a component derived from the Fischer-Tropsch process. Fischer-Tropsch fuels are known as FT fuels, which include what are referred to as gas-to-liquid (GTL) fuels and conventional coal or biomass fuels. In order to produce such a fuel, first, synthesis gas (CO + H ₂ ) is generated and converted into linear paraffin by the Fischer-Tropsch method. In addition, linear paraffins can be modified by catalytic cracking / catalytic reforming or isomerization, hydrocracking, hydroisomerization, and other hydrocarbon compounds such as isoparaffins, cycloparaffins, and aromatic compounds. Become. The resulting FT fuel can be used as is, or can be used with other fuel components and other fuels described herein.

  The concentration of the additive in the oil may be, for example, within a range of 1 to 10,000 ppm of the additive (active ingredient) based on the mass of the fuel, and the active ingredient is 10 to 10 mass based on the mass of the fuel. It is good in the range of 5,000 ppm, for example, 10 to 2,000 ppm.

  Additives can be mixed into the bulk oil by methods known in the art. When two or more kinds of additive components or auxiliary components are used, these components may be mixed together and mixed with oil, or any combination may be used, but they may be mixed separately.

  A concentrate containing an additive dissolved or dispersed in a carrier liquid (eg, a solution) is convenient as a means of mixing the additive. The concentrate of the present invention is convenient as a means for mixing an additive with a bulk oil such as a distillate fuel, and may be mixed by a method known in this field. If necessary, other additives may be added to the concentrate, preferably 3 to 75% by weight, more preferably 3 to 60% by weight, most preferably 10 to 50% by weight of additives, Preferably, it can be made into a solution and contained in oil. Examples of carrier liquids include hydrocarbon solvents such as petroleum fractions such as naphtha, kerosene, diesel oil, and heating oil; for example, aromatic fractions sold under the trade name “SOLVESSO”. And organic solvents including aromatic hydrocarbons such as hexane; and paraffinic hydrocarbons such as hexane and pentane and isoparaffins. As a matter of course, the carrier liquid must be selected in consideration of compatibility with additives and fuels.

  The additive of the present invention may be mixed into the bulk oil by other methods known in the art. When an auxiliary agent is required, it may be mixed simultaneously with the additive of the present invention, or may be separately mixed with bulk oil.

  Conventional low temperature fluidity enhancing additives used with the polymers of the present invention are defined as (A) to (H) below.

(A) Another ethylene-unsaturated ester copolymer having a unit represented by the formula —CR ⁷ R ⁸ —CHR ⁹ — in addition to a unit derived from ethylene is particularly preferred. In the formula, R ⁸ represents hydrogen or a methyl group, R ⁷ represents —OOCR ¹⁰ or COOR ¹⁰ group, and R ¹⁰ represents hydrogen or a linear or branched group having 1 to 28 carbon atoms, preferably 1 to 9 carbon atoms. Represents a chain alkyl group, but when R ⁷ is —COOR ¹⁰ , R ¹⁰ is not hydrogen. R ⁹ represents hydrogen or —COOR ¹⁰ .

  A copolymer of ethylene and an ethylenically unsaturated ester or a derivative thereof may be included. An example is a copolymer of ethylene and an unsaturated carboxylic acid ester. Ethylene-vinyl ester copolymers are preferred, with ethylene-vinyl acetate, ethylene-vinyl propionate, ethylene-vinyl hexanoate, ethylene-2-ethyl hexanoate vinyl or ethylene-vinyl octanoate copolymers being preferred.

  It is preferable that 0.3 to 15 mol%, preferably 3.5 to 15 mol% of vinyl ester is contained in the copolymer.

  These may be in the form of a mixture of two copolymers as described in US Pat. No. 3,961,916. If desired, additional comonomers can be added to derive copolymers, such as terpolymers, quaternary copolymers and even multi-component copolymers where the additional comonomer is propylene or isobutylene. Good.

  Copolymers can be made by directly polymerizing comonomers. It can also be obtained by transesterifying a certain ethylenically unsaturated ester copolymer or hydrolyzing or reesterifying it into a different unsaturated ester copolymer. For example, an ethylene-vinyl hexanoate copolymer or an ethylene-2-ethyl hexanoate vinyl copolymer can be prepared from, for example, an ethylene-vinyl acetate copolymer using this method.

(B) Comb polymer This type of polymer is a polymer in which a branched branch containing a hydrocarbyl group is suspended from the polymer main chain, co-authored by 鼎 omb-Like Polymers. Structure and Properties NA Plate, VP Shibaev, J. Poly. Sci. Macromolecular 8th edition, pages 117-253, described in 1974.

  In general, the comb polymer contains one or more long hydrocarbyl branches, usually 10-30 carbon atoms, such as oxyhydrocarbyl branches, which are pendent from the polymer backbone, The branched chain is directly or indirectly bonded to the main chain. An example of an indirect bond is a case where atoms or groups are bonded via an intervening bond, and this bond includes an ionic bond such as a covalent bond and / or a bond in a salt.

  The comb polymer is a homopolymer having at least 25 mol%, preferably at least 40 mol%, more preferably at least 50 mol% of the total units having side chains containing at least 6 and preferably at least 10 atoms. Advantageously it is a polymer or copolymer.

式中、
Ｄは、Ｒ¹¹、ＣＯＯＲ¹¹、ＯＣＯＲ¹¹、Ｒ¹²ＣＯＯＲ¹¹又はＯＲ¹¹、
Ｅは、水素、ＣＨ₃、Ｄ又はＲ¹²、
Ｇは、水素又はＤ、
Ｊは、水素、Ｒ¹²、Ｒ¹²ＣＯＯＲ¹¹、アリール基又は複素環基、
Ｋは、水素、ＣＯＯＲ¹²、ＯＣＯＲ¹²、ＯＲ¹²又はＣＯＯＨ、
Ｌは、水素、Ｒ¹²、ＣＯＯＲ¹²、ＯＣＯＲ¹²、ＣＯＯＨ又はアリール、
Ｒ¹¹は、炭素数１０個以上のヒドロカルビル、
Ｒ¹²は、炭素数１個以上のヒドロカルビルもしくはヒドロカルビレン、
さらに、ｍ及びｎはモル分率を表し、ｍは有限で好ましくは１．０〜０．４の範囲、ｎは１未満で好ましくは０〜０．６の範囲である。 Examples of recommended comb polymers include polymers represented by the following general formula.

Where
D is R ¹¹ , COOR ¹¹ , OCOR ¹¹ , R ¹² COOR ¹¹ or OR ¹¹ ,
E is hydrogen, CH ₃ , D or R ¹² ,
G is hydrogen or D,
J is hydrogen, R ¹² , R ¹² COOR ¹¹ , an aryl group or a heterocyclic group,
K is hydrogen, COOR ¹² , OCOR ¹² , OR ¹² or COOH,
L is hydrogen, R ¹² , COOR ¹² , OCOR ¹² , COOH or aryl,
R ¹¹ is a hydrocarbyl having 10 or more carbon atoms,
R ¹² is a hydrocarbyl or hydrocarbylene having 1 or more carbon atoms,
Furthermore, m and n represent mole fractions, m is finite and preferably in the range of 1.0 to 0.4, and n is less than 1 and preferably in the range of 0 to 0.6.

Advantageously, R ¹¹ represents a hydrocarbyl group having 10 to 30 carbon atoms, and R ¹² is advantageously a hydrocarbyl or hydrocarbylene group having 1 to 30 carbon atoms.

  The comb polymer may contain units derived from other monomers as desired or required.

  The comb polymer may be a copolymer of maleic anhydride or fumaric acid or itaconic acid and another ethylenically unsaturated monomer such as an α-olefin including styrene or an unsaturated ester such as vinyl acetate. Or a homopolymer of fumaric acid or itaconic acid. The use of an equimolar amount of comonomer is not essential but is recommended, and a molar ratio of 2: 1 to 1: 2 is a suitable range. Examples of olefins that can be used, for example, for copolymerization with maleic anhydride include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene.

  The acid or anhydride group of the comb polymer may be esterified by any suitable method. Although it is preferred that maleic anhydride or fumaric acid be at least 50% esterified, it is not essential. Examples of alcohols that can be used include n-decan-1-ol, n-dodecan-1-ol, n-tetradecan-1-ol, n-hexadecan-1-ol and n-octadecan-1-ol. Is mentioned. Furthermore, the alcohols can contain up to one methyl branch per chain, for example 1-methylpentadecan-1-ol or 2-methyltridecan-1-ol. . The alcohol may be a mixture of normal alcohol and an alcohol having one methyl branch.

Although it is preferred to use pure alcohol rather than commercially available alcohol mixtures, when a mixture is used, the above R ¹² refers to the average number of carbon atoms in the alkyl group. When an alcohol having a branch at the 1- or 2-position is used, R ¹² indicates a linear main chain portion of the alcohol.

  These comb polymers are fumaric acid ester or itaconic acid ester polymers and copolymers such as described in EP-A-153,176, EP-A-153,177, EP-A-225,688 and WO91 / 16407. Particularly preferred.

  Particularly preferred fumaric acid ester comb polymers are copolymers of alkyl fumarate and vinyl acetate, wherein the alkyl group has 12 to 20 carbon atoms, more preferably the alkyl group has 14 carbon atoms. In the production method, for example, an equimolar mixture of fumaric acid and vinyl acetate was obtained by solution copolymerization. The copolymer is reacted with an alcohol or a mixture of alcohols. In this case, the alcohol is preferably a linear alcohol. When a mixture is used, a mixture of 14 and 16 normal alcohols having a mass ratio of 1: 1 is advantageous. Further, a mixture of an ester having 14 carbon atoms and an ester mixture having 14 to 16 carbon atoms can be advantageously used. In this mixture, the mass ratio of the ester of 14 carbon atoms to the ester mixture of 14 and 16 carbon atoms is advantageously 1: 1-4: 1, preferably 2: 1-7: 2, most preferably About 3: 1. When measured by the gas phase osmotic pressure method, those having a number average molecular weight of 1,000 to 100,000, more preferably 1,000 to 30,000 are particularly preferred comb polymers.

  Other suitable comb polymers include alpha-olefin polymers and copolymers, esterified copolymers of styrene and maleic anhydride, and esterified copolymers of styrene and fumaric acid, Mixtures of two or more comb polymers can also be used in the present invention, and such use is advantageous as described above. Examples of comb polymers other than the above include hydrocarbon polymers, such as a copolymer of ethylene and at least one α-olefin, and the α-olefin preferably has 20 carbon atoms at most. For example, n-decene-1 and n-dodecene-1. The number average molecular weight of such a copolymer is preferably at least 30,000 as measured by GPC. The hydrocarbon copolymer can be prepared by a method known in this field, for example, using a Ziegler-based catalyst.

(C) Polar Nitrogen Compounds This type of compound is an oil-soluble polar nitrogen compound having 1 or more, preferably 2 or more substituents represented by the formula> NR ¹³ , wherein R ¹³ represents a hydrocarbyl group having 8 to 40 atoms, and the substituent or one or more substituents may be in the form of a cation derived from the above hydrocarbyl group. Oil-soluble polar nitrogen compounds are usually those that can function as a wax crystal growth inhibitor in fuel and include, for example, one or more of the following compounds.

Substitution of formula> NR ¹³ with an amide formed by reacting an amine salt and / or at least one mole part of a hydrocarbyl-substituted amine with one mole part of a hydrocarbyl acid having 1 to 4 carboxylic acid groups or its anhydride. The group is represented by the formula —NR ¹³ R ¹⁴ , wherein R ¹³ is as defined above, R ¹⁴ represents hydrogen or R ¹³ , and R ¹³ and R ¹⁴ may be the same or different. Often this substituent constitutes part of an amine salt and / or an amide group of the compound.

  Esters / amides having a total of 30 to 300, preferably 50 to 150 carbon atoms may be used. This nitrogen compound is described in US Pat. No. 4,211,534. Suitable amines are primarily primary, secondary, tertiary or quaternary amines having 12 to 40 carbon atoms, or mixtures thereof, but shorter chain amines are also oil-soluble in the final nitrogen compounds. In general, if the total number of carbon atoms is about 30 to 300, it can be used. The nitrogen compound preferably contains at least one linear alkyl segment having 8 to 40 carbon atoms, preferably 14 to 24 carbon atoms.

  Suitable amines include primary, secondary, tertiary or quaternary amines, with secondary amines being preferred. Tertiary and quaternary amines form amine salts. Examples of amines include tetradecylamine, cocoamine, hydrogenated tallow amine. Examples of secondary amines include dioctacedylamine and methylbehenylamine. A mixture of amines is preferably derived from natural raw materials. The recommended amine was derived from hydrogenated beef tallow consisting of approximately 4% alkyl groups with 14 carbon atoms, 31% with 16 carbon atoms and 59% with 18 carbon atoms. Secondary hydrogenated tallow amine.

  Examples of suitable carboxylic acids and anhydrides for preparing the nitrogen compounds include ethylenediaminetetraacetic acid, and cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2 -Carboxylic acids based on cyclic skeletons such as 1,4-dicarboxylic acids including dicarboxylic acids, naphthalenedicarboxylic acids and dialkylspirobislactones. In general, these acids contain approximately 5 to 13 carbon atoms in the cyclic moiety. Acids useful and suitable in the present invention are, for example, benzenedicarboxylic acids such as phthalic acid, isophthalic acid, and tetraphthalic acid. Phthalic acid and its anhydride are particularly preferred. Particularly preferred compounds are amide-amine salts formed by reacting 1 mole part of phthalic anhydride with 2 mole parts of dihydrogenated tallow amine. Diamide formed by dehydrating this amide-amine salt is another recommended compound.

  Other examples include long chain alkyl or alkylene substituted dicarboxylic acid derivatives such as amine salts of monoamides of substituted succinic acids, examples of which are known in the art and are described, for example, in US Pat. No. 4,147,520. ing. Suitable amines include those described above.

  Still another example is a condensate, such as the condensate described in EP-A-327,427.

(D) comprises a ring structure, the following formula on the ring structure: with a compound having at least two substituents represented by -A-NR ¹⁵ R ^16, wherein, A is an aliphatic linear or branched Hydrocarbylene group, optionally, but interrupted by one or more heteroatoms, R ¹⁵ and R ¹⁶ may be the same or different and each independently represents 9-40 atoms. Represents a hydrocarbyl group containing one and optionally may be interrupted by one or more heteroatoms. The substituents may be the same or different, and the compound is optional but may be in the form of a salt. A preferably has 1 to 20 carbon atoms, and is preferably a methylene group or a polymethylene group. Such compounds are described in WO93 / 04148 and WO94 / 07842.

式中、Ｔは水素又はＲ¹⁷で、Ｒ¹⁷は炭素数１〜４０のヒドロカルビルを表し、Ｕは水素、Ｔ又はアリールであり、
ｖ及びｗはモル分率を表し、ｖは１．０〜０．０の範囲内でありｗは０．０〜１．０の範囲内である。 (E) Hydrocarbon polymers Examples of suitable hydrocarbon polymers are those represented by the general formula:

In the formula, T is hydrogen or R ¹⁷ , R ¹⁷ represents a hydrocarbyl having 1 to 40 carbon atoms, U is hydrogen, T or aryl,
v and w represent mole fractions, v is in the range of 1.0 to 0.0 and w is in the range of 0.0 to 1.0.

  Examples of hydrocarbon polymers are disclosed in WO91 / 11488.

  The recommended copolymer is an ethylene-α-olefin copolymer having a number average molecular weight of at least 30,000. The α-olefin preferably has at most 28 carbon atoms. Examples of such olefins include propylene, 1-butene, isobutene, n-octene-1, isooctene-1, n-decene-1, and n-dodecene-1. The copolymer may contain other copolymerizable monomers, for example, olefins other than α-olefins, non-conjugated dienes, and the like, for example, in a small amount of up to 10% by mass. The recommended copolymer is particularly preferably an ethylene-propylene copolymer.

  As described above, the number average molecular weight of the ethylene-α-olefin copolymer is preferably at least 30,000, and advantageously at least 60,000, when measured by gel permeation chromatography (GPC) as a polystyrene standard. , Preferably at least 80,000. Although there is no upper limit in terms of functionality, the preferred molecular weight is in the range of 60,000 and 80,000 to 120,000 because mixing becomes difficult because the viscosity increases when the molecular weight exceeds approximately 150,000.

  Advantageously, the molar content of ethylene in the copolymer is from 50 to 85%. Further, the ethylene content is more advantageously 57 to 80%, preferably 58 to 73%, more preferably 62 to 71%, and most preferably 65 to 70%.

  The recommended ethylene-α-olefin copolymer is an ethylene-propylene copolymer having a molar content of ethylene of 62 to 71% and a number average molecular weight in the range of 60,000 to 120,000. An ethylene-propylene copolymer having a molar content of 62 to 71% and a molecular weight in the range of 80,000 to 100,000.

  The copolymer can be prepared using any method known in the art, for example using a Ziegler catalyst. The polymer may be substantially amorphous because the high crystallinity of the polymer is relatively insoluble in fuel oil at low temperatures.

  Other suitable hydrocarbon polymers include low molecular weight ethylene-α-olefin copolymers, but a number average molecular weight measured by the gas phase osmotic pressure method is advantageously at most 7,500, and more preferably 1,000 to 6,000. Is advantageous, preferably 2,000 to 5,000. Suitable α-olefins are those listed above or styrene, which is also preferably propylene. The ethylene content is advantageously from 60 to 77 mol%, but in the ethylene-propylene copolymer, ethylene can be advantageously used as long as it is up to 86 mol% by mass.

(F) Polyoxyalkylene compounds Examples include polyoxyalkylene esters, ethers, esters / ethers, and mixtures thereof, and in particular, at least one linear alkyl group having 10 to 30 carbon atoms. Preferably, it contains at least 2 and a polyoxyalkylene glycol group having a molecular weight of up to 5,000, preferably 200 to 5,000, and the alkyl group in the polyoxyalkylene glycol contains 1 to 4 carbon atoms. These substances are the subject of EP-A-0061895. Other such additives are described in US Pat. No. 4,491,455.

Recommended esters, ethers or esters / ethers are those represented by the general formula R ¹⁸ —O (D) —O—R ¹⁹ .
In which R ¹⁸ and R ¹⁹ may be the same or different;
(A) n-alkyl-
(B) n-alkyl-CO-
(C) n-alkyl-O—CO (CH ₂ ) _x — or (d) n-alkyl-O—CO (CH ₂ ) _x —CO—
X is 1 to 30, for example, the alkyl group is a linear alkyl group containing 10 to 30 carbon atoms, D represents a polyalkylene moiety of glycol, and the alkylene group has 1 to 4 carbon atoms For example, polyoxymethylene, polyoxyethylene or polyoxytrimethylene moieties which are substantially linear. Although there may be some degree of branching of the lower alkyl side chain (such as in polyoxypropylene glycol), it is preferred that the glycol is substantially linear. D may also contain nitrogen.

  Examples of suitable glycols include substantially linear polyethylene glycols (PEG) and polypropylene glycols (PPG) having a molecular weight of 100 to 5,000, preferably 200 to 2,000. Esters are preferred, but fatty acids with 10-30 carbons are useful in reacting with glycols to form ester additives, and use of fatty acids with 18-24 carbons, especially behenic acid is recommended. The These esters can also be prepared by esterifying a polyethoxylated fatty acid or polyethoxylated alcohol.

  Polyoxyalkylene diesters, diethers, ethers / esters and mixtures thereof are suitable as additives, especially small amounts of monoethers and monoesters (these are often formed during the manufacturing process). Diesters are recommended for use in a narrow range of boiling fractions. Preferably a large amount of dialkyl compound is present. In particular, polyethylene glycol, polypropylene glycol or a stearic acid or behenic acid diester of a polyethylene / polypropylene glycol mixture is preferred.

  Other examples of the polyoxyalkylene compounds include those described in JP-B-2-51477 and JP-B-3-34790, and alkoxyl described in EP-A-117108 and EP-A-326356. An esterified ester of a fluorinated amine is exemplified.

(G) Hydrocarbylated aromatic compound This substance is a condensate having an aromatic moiety and a hydrocarbyl moiety. Conveniently, the aromatic moiety is an aromatic hydrocarbon which may be unsubstituted or substituted, for example with a non-hydrocarbon substituent.

  Such aromatic hydrocarbons preferably contain a maximum number of substituents and / or a maximum of 3 fused rings, with naphthalene being preferred. The hydrocarbyl moiety is a moiety containing hydrogen and carbon and is bonded to the rest of the molecule by a carbon atom. This may be either saturated or unsaturated, may be linear or branched, and may contain one or more heteroatoms provided they do not substantially affect the hydrocarbyl properties of this moiety. . The hydrocarbyl moiety is preferably an alkyl moiety and conveniently contains more than 8 carbon atoms. The molecular weight of such a condensate is, for example, preferably 2,000 to 200,000, more preferably 2,000 to 20,000, and further preferably 2,000 to 8,000.

  Examples of this compound are known in the art primarily as lube oil pour point depressants and dewaxing aids, as described earlier in this specification, for example, halogenated waxes as aromatic hydrocarbon compounds. And can be condensed. More specifically, the halogenated wax has 15 to 60, for example, 16 to 50 carbon atoms, a melting point of about 200 to 400 ° C., and chlorine of 5 to 25 mass%, for example 10 to 18 mass. When the chlorination treatment is carried out so that the concentration becomes%, the above condensation may be Friedel-Crafts condensation. In order to produce the same condensate, it can also be produced from olefins and the above aromatic hydrocarbon compounds.

(H) Alkylphenol formaldehyde condensates Suitable alkylphenol formaldehyde condensates are disclosed in EP0311452 and EP0851776.

The alkylphenol formaldehyde condensate may be obtained by a condensation reaction between the following reactants.
(I) at least one aldehyde or ketone or equivalent to these, and
(Ii) at least one aromatic moiety comprising one or more aromatic moieties having at least one substituent represented by the formula -XR ¹ and at least one other substituent represented by the formula -R ² Wherein X represents oxygen or sulfur, R ¹ represents hydrogen or a moiety having at least one hydrocarbyl group, R ² represents a linear or branched hydrocarbyl group, preferably 4 carbon atoms. Compounds representing hydrocarbyl groups containing -40, more preferably 8-30, most preferably 8-18.

  The alkylphenol formaldehyde condensate may be contained in the fuel oil in an amount of 5 to 5000 ppm, preferably 10 to 1000 ppm, and most preferably 20 to 500 ppm.

  The present invention will be described in detail, but will be described for the purpose of illustration as follows.

(Additive)
The following additives were used.
Polymer 1: ethylene having a vinyl acetate concentration of about 38.1 wt% (16.7 mol%), a number average molecular weight of about 2470, and about 7.6 alkyl branches per 100 methylene units / Vinyl acetate copolymer.
Polymer 2: an ethylene / vinyl acetate copolymer having a vinyl acetate concentration of about 15% by mass (5 mol%), a number average molecular weight of about 6500, and containing about 8 alkyl branches per 100 methylene units .
Polymer 3: The polymer of the present invention. The vinyl acetate concentration is about 40% by weight (17.5 mol%), the number average molecular weight is about 3700, and about 6 alkyl branches per 100 methylene units.
Auxiliary: Comb polymer di-n-dodecyl fumarate / vinyl acetate copolymer.

(test)
Polymers 1, 2, 3 and auxiliaries were dissolved in the same rapeseed oil methyl ester fuel sample and the cold filter clogging point (CFPP) test was measured by the whistle of the Institute of Petroleum Vol. 52, No. 510. June 1966, following procedures detailed on pages 173-185. CFPP is a criterion for filterability. The results are shown in the table below.

注：「ｐｐｍ Ａｉ」とは低温流動性向上添加剤の有効成分を質量によるｐｐｍの単位で表したもので、担体溶媒の量は含まれていない。

Note: “ppm Ai” represents the active ingredient of the low temperature fluidity improving additive in ppm by mass and does not include the amount of carrier solvent.

  Examples of the present invention, in Example A, Example B and Example C, each include polymer 3, which is the polymer of the present invention, resulting in excellent performance in the CFPP test.

Claims (10)

  Oils or derivatives thereof derived from methyl esters of animal and / or plant raw materials, or mixtures of said oils and petroleum oils, and containing at least 17 mol% of vinyl ester units, and methylene in the main chain A composition containing an ethylene-vinyl ester copolymer low-temperature fluidity improver having 5 or more alkyl branches per 100. The composition is
(A) an ethylenically unsaturated ester copolymer different from the copolymer,
(B) comb polymer,
(C) polar nitrogen compounds,
(D) a compound containing a cyclic structure,
(E) a hydrocarbon polymer,
(F) a polyoxyalkylene compound,
The composition of claim 1, further comprising one or more of (g) a hydrocarbylated aromatic pour point depressant, or (h) an alkylphenol formaldehyde condensate.   The composition according to claim 1 or 2, wherein the copolymer contains 17 to 25 mol% of vinyl ester.   The composition according to any one of claims 1 to 3, wherein the vinyl copolymer has 6 to 8 alkyl branches.   The composition according to any one of claims 1 to 4, wherein the vinyl ester is vinyl acetate and contains 17 to 19 mol% of vinyl acetate units.   The composition according to any one of claims 1 to 5, wherein the large amount of oil is a biofuel selected from the group comprising methyl esters of rapeseed oil, cottonseed oil, soybean oil, sunflower oil, olive oil or palm oil. object.   The composition according to any one of claims 1 to 6, wherein the composition contains a low-temperature fluidity improving additive (active ingredient) in an amount of 1 to 10000 ppm, preferably 10 to 5000 ppm, based on the mass of the oil. object.   An additive concentrate for blending with the oil of claim 1, comprising a solution containing 3 to 75% by weight of the copolymer of claim 1.   At least 17 moles of vinyl ester units for the purpose of improving the low temperature properties of oils or derivatives thereof derived from methyl esters of animal or plant materials or both, or mixtures of said oils and petroleum oils. %, And the use of an ethylene-vinyl ester copolymer low temperature fluidity improver containing 5 or more alkyl branches per 100 main chain methylenes.   A method for improving the low temperature properties of oils or derivatives thereof derived from methyl esters of animal or plant materials or both, or mixtures of said oils and petroleum oils, comprising at least 17 mol% vinyl ester units A process comprising adding to the oil an ethylene-vinyl ester copolymer low temperature fluidity improver comprising 5 or more alkyl branches per 100 main chain methylenes.