JPH0689346B2 - Flow improver polyester for hydrocarbons - Google Patents

Abstract

A polymer or copolymer of weight average molecular weight from 1000 to 200,000 prepared from an ethylenically unsaturated ester and containing from 0.1 to 50% by weight of polyoxyalkylene groups of molecular weight from 100 to 5000 is used to improve the cold flow properties of liquid hydrocarbon especially distillate fuels and has improved interaction with other additives.

Description

DETAILED DESCRIPTION OF THE INVENTION Wax-containing mineral oils have the property of decreasing fluid temperature and decreasing fluidity. This loss of fluidity is generally due to an increase in viscosity and / or increased crystallization of the wax into plate crystals, eventually forming a spongy mass and trapping the oil therein.

It has been known for many years that various compositions act as wax crystal modifiers and pour point depressants when fitted to waxy mineral oils. These compositions modify the size and shape of the wax crystals, reducing the adhesion between the wax and the oil so that the oil is fluid at low temperatures.

Various pour point depressants are described in the literature, some of which are in commercial use. For example, U.S. Pat.No. 3,048,479
The issue, fuel, in particular heating oil, the use of copolymers of ethylene and C ₃ -C ₅ vinyl esters such as vinyl acetate as pour point depressants for diesel and jet fuel is disclosed. Hydrocarbon polymeric pour point depressants based on ethylene and higher alpha olefins such as propylene are also known. U.S. Pat.No. 3,961,916
U.S. Pat. No. 5,837,849 discloses the use of a mixture of copolymers, one of which is a wax crystal nucleator and the other is a growth inhibitor that controls the size of the wax crystals.

Similarly, British Patent 1,263,152 suggests that the size of the wax crystals can be controlled by the use of copolymers with low degree of side chain branching.

Distillation with high final boiling point as a copolymer of di-n-alkyl fumarate and vinyl acetate previously used as pour point depressant for lubricating oils as a co-additive with ethylene / vinyl acetate copolymer The ability to be used in the treatment of oil fuels and to improve their cold flow properties is also described, for example in British Patent No. 1,46.
Proposed in No. 9,016. According to British Patent No. 1,469,016, these polymers are C ₆ -C ₁₈ unsaturated C ₄ -C ₈ dicarboxylic acids.
It can be an alkyl ester, especially lauryl fumarate, lauryl fumarate-hexadecyl. Typically the material used is a mixed ester (Polymer A) having an average of about 12 carbon atoms.

Applicant's European patent applications 85,301,047, 85,301,048
Nos. 85,301,675 and 85,301,676 show that the copolymers contain very specific alkyl groups, for example specific di-n-alkyl fumarate / vinyl acetate copolymers, It is suggested that the efficacy can be improved. For example, the average number of carbon atoms in the alkyl group in the copolymer must be 12 to 14, only 10% by weight of the copolymer in which the alkyl group contains 14 or more carbon atoms, and preferably the alkyl group Polymers which must contain only 20% by weight of a copolymer containing less than 12 carbon atoms are particularly effective for certain fuels, and polymers with specific long alkyl groups are particularly useful for other fuels. Was found to be effective.

Applicant's European Patent Application No. 0,061,895A ₂ contains at least 2
A polyoxyalkylene ester having a C _{10 to} C ₃₀ linear saturated alkyl group and a polyoxyalkylene glycol group having a molecular weight of 100 to 5,000, wherein the alkyl group in the polyoxyalkylene glycol has 1 to 4 carbon atoms, ether,
The use of esters / ethers and mixtures thereof as additives to distillate petroleum fuels is described.

It has also been shown in many cases that the use of a mixture of two additives gives a synergistic improvement in the cold flow properties, especially in distillate petroleum fuels. However, mixing can sometimes cause problems with additive interactions that reduce their effectiveness, which often mixes large amounts of fuel containing different additives for storage from different sources. It can cause serious problems for refiners who may want to, and the purpose of the present invention is to reduce this problem.

This time, it is possible to incorporate polyoxyalkylene glycol groups into unsaturated ester copolymers and use them in heavy fuels, residual fuel oils in crude oils, and as pour point depressants in lubricating oils, although hydrocarbons, especially It has been found that an effective cold flow improver for distillate fuels can be provided.
Unsaturated ester copolymers incorporating polyoxyalkylene groups can be of the type previously proposed as flow improvers for middle distillate fuels. It has also been found that the use of these copolymers in distillate fuels can reduce the problem of adverse interactions with other additives such as ethylene vinyl acetate copolymers.

Accordingly, the present invention provides a method for improving the flow characteristics of petroleum distillate fuels,
0.1 to 50% by weight of 100 to 5,000 polyoxyalkylene groups
Provided is an additive containing a polymer or copolymer of an ethylenically unsaturated ester having a weight average molecular weight of 1,000 to 200,000.

The polymers of the present invention are used as additives to distillate fuels, they are preferably used in amounts of 0.0001 to 5% by weight, based on the weight of distillate petroleum fuel oils, and also in the present invention. Distillate fuels containing various additives are included.

The polymer used in the present invention preferably has a weight average molecular weight in the range of 1,000 to 100,000, preferably 20,000 to 70,000, as measured by gel permeation chromatography calibrated against polystyrene molecular weight standards.

The unsaturated esters of the present invention can be derived from ethylenically unsaturated mono-, di- or polycarboxylic acids or mixtures thereof, the unsaturated esters or mixtures thereof and other ethylenically unsaturated monomers such as ethylene, propylene. Or you can get it with butene. Examples of dicarboxylic acid esters useful in making polymers are of the general formula: Where R ₁ and R ₂ are hydrogen or a C ₁ -C ₄ alkyl group such as methyl, R ₃ is an average C ₈ -C ₁₈ , the preferred average depending on the application to which the polymer is directed. ₃ is used as a lube pour point depressant as well as a mixture of a wide range of alkyl groups as used in GB 1,469,016 or they can not only improve cold flow and filterability but also lower the cloud point of the fuel Applicant's European patent applications 85,301,047, 85,3 used as distillate additive
No. 01,048, No. 85,301,675 and No. 85,301,676, and R ₄ can be represented by COOR ₃ , hydrogen or a C ₁ -C ₄ alkyl group). When these types of unsaturated esters are used as raw materials in the production of the polymers of the present invention, polyoxyalkylene groups can be incorporated into the molecule during the esterification of carboxylic acids to produce the esters. For example, polyethylene glycol can be mixed with the alcohol, R ₃ OH, in a suitable ratio and used, for example, for the esterification of fumaric acid. The esters of the above formula may be homopolymerized or co-polymerized with other ethylenically unsaturated monomers such as short chain unsaturated esters such as vinyl acetate, vinyl propionate and vinyl butyrate, and alkyl acrylates and alkyl methacrylates. It can be polymerized.

Typical copolymers of the above type are obtainable by copolymerization of dicarboxylic acid mono- or di-ester monomers such as dialkyl fumarate with various amounts of other unsaturated esters or olefins, for example 5 to 70 mole%. be able to. The formula for such other esters is: [Wherein R ¹ is hydrogen or a C ₁ -C ₄ alkyl group, and R ″
Is the -COOR 'or -OOCR' (was Isuzu and R 'is C ₁ -C ₅ alkyl group branched branched or unbranched), R
Is R "or hydrogen]. Examples of these short chain esters are methacrylates, acrylates, fumarates, and maleates, with vinyl esters such as vinyl acetate and vinyl propionate being preferred. .
More specific examples include methyl methacrylate, isopropenyl acetate and isobutyl acrylate.

Preferred copolymers of this type according to the invention contain 40 to 60 mol% of fumaric acid esters containing polyoxyalkylene moieties and 60 to 40 mol% of vinyl acetate.

These ester polymers are generally prepared by dissolving the ester monomer in a solution of a hydrocarbon solvent such as heptane, benzene, cyclohexane or white oil, generally at a temperature in the range of 20 to 150 ° C., and an inert gas to eliminate oxygen. For example, it is usually prepared by promoting polymerization under a blanket of nitrogen or carbon dioxide with a peroxide or azo type catalyst such as benzoyl peroxide, azobisisobutyronitrile.

Another method of incorporating a polyoxyalkylene group into the ester copolymer of the present invention is the above ethylenically unsaturated ester and formula: R-COOR ', where R is an ethylenically unsaturated hydrocarbyl group and R'is a poly Is an oxyalkylene group) is copolymerized with an ethylenically unsaturated ester. Examples of such esters include polyethylene glycol mono- or di-oleate, polyethylene glycol mono- or di-cinnamate, polyethylene glycol acrylate and the like. For example, fumaric acid di-
Hexadecyl, vinyl acetate and oleic acid with a molecular weight of 60
The diester of 0 with polyoxyethylene glycol can be copolymerized to provide the copolymer of the present invention.

Alternatively, the polyoxyalkylene group can be incorporated into the ester polymer by preparing a polymer containing free acid groups and then esterifying with a polyoxyalkylene alcohol or glycol. For example, copolymers of maleic anhydride with other unsaturated substances such as vinyl esters, dialkyl fumarate, styrenes or olefins can be esterified with polyoxyalkylene alcohols or glycols. The polyoxyalkylene alcohol used is itself a monoalcohol and the group at the other end can be etherified or esterified so that further desired groups are introduced into the polymer chain. The polyoxyalkylene alcohol or glycol can be mixed with other alcohols, especially linear alkyl alcohols, when the product is used as an additive to distillate fuels.

Examples of polyoxyalkylene alcohols that can be used have the general formula: R-O- (A) -O-H where R is hydrogen, -alkyl, And A is a polyoxyalkylene segment having an alkylene group of 1 to 4 carbon atoms, such as polyoxymethylene, polyoxyethylene or polyoxytrimethylene), an ester, ether or ester / ether. Polyoxyalkylene segment itself is about 100 ~
It preferably has a molecular weight of 5,000.

Examples of suitable alcohols and glycols are about 100, especially when the material is used as an additive to distillate fuels.
Substantially linear polyethylene glycol (PEG) and polypropylene glycol (PPG) having a molecular weight of ˜5,000, preferably about 200 to 2,000. Monoesters of these glycols can be used, esters of fatty acids containing about 1 to 30, preferably 2 to 30 carbon atoms being preferred, C _{18 to} C ₂₄ fatty acids, especially behenic acid or stearic acid and behenic acid. It is preferred to use a mixture of These esters can also be prepared by esterifying polyethoxylated fatty acids or polyethoxylated alcohols, for example monomethyl ether of PEG,
Alternatively, polyethoxylated fatty alcohols such as the commercially available "Brij" material can be used. Particularly preferred compounds for use as distillate fuel flow improvers, especially in distillates with a narrow boiling range, are vinyl acetate, fumaric acid and at least 95 mole% C ₁₂ / C ₁₄ straight chain alcohols and 5 mole%.
Is a copolymer with an equimolar amount of fumaric acid ester produced by esterification with a mixture of polyethylene glycol having a molecular weight of up to 600.

Alternatively, ester polymers or copolymers containing free carboxylic acids or hydroxy groups can be reacted with ethylene oxide or propylene oxide to produce materials of the invention.

The compounds of the present invention can be used as additives to improve the low temperature properties of hydrocarbon fuels such as crude oil, residual fuel oil and distillate fuel, where they reduce the pour point and the wax crystal size. To improve low temperature filterability,
In some cases, the cloud point of the fuel can be lowered. Distillate fuels mean fuels commonly used in diesel vehicles and heating oils which generally boil in the range 120 to 500 ° C., in particular 160 to 400 ° C., in particular household heating oils. In addition, when used in some distillate fuels, they are less prone to adverse interactions with other distillate additives than similar additives containing no polyoxyalkylene groups. The compounds can be used with high potency, but are found to be particularly effective in distillate fuels when used in combination with other additives conventionally conventionally proposed to improve the cold flow properties of distillate fuels. Was given.

The additive of the present invention comprises at least two C _{10 to} C ₃₀ linear saturated alkyl groups and a molecular weight of 100 to 5,000, preferably 200 to 5,0.
It can be used with polyoxyalkylene esters, ethers, esters / ethers and mixtures thereof, including 00 polyoxyalkylene glycols, wherein the alkyl group in the polyoxyalkylene glycol contains 1 to 4 carbon atoms. These substances are European patent publication No.
It constitutes the subject of 0,061,892A2. Examples of suitable co-additives of this type are glycols, generally substantially linear polyethylene glycol (PEG) and polypropylene glycol (PPG) and about 10 to 30, preferably 18 to 24 carbon atoms, especially Is a reaction product of behenic acid or a mixture of stearic acid and behenic acid, which can be prepared by esterification of their esters or polyethoxylated fatty acids or polyethoxylated alcohols. Esters obtained by reacting fatty acids with polyalkoxylated amines or ammonia can also be used.

The polymers or copolymers of the present invention can also be used when used as an additive in fuels, especially distillate fuels, and with ethylenically unsaturated ester copolymer flow enhancers. The unsaturated monomer copolymerizable with ethylene has the general formula: (In the formula, R ₃ is hydrogen or methyl, R ₂ is a —OOCR ₅ group (however, R ₅ is hydrogen or C _{1 to} C ₂₈ , usually C _{1 to} C ₁₇ , preferably C _{1 to} C ₈ ). A straight or branched chain alkyl group), or R ₂ is a —COOR ₅ group (where R ₅ is as defined above but not hydrogen) and R ₄ is hydrogen or defining the unsaturated mono -COOR ₅ in which] - and di - include esters. When R ₂ and R ₄ are hydrogen and R ₂ is —OOCR ₅ , the monomer has C _{1 to} C ₂₉ , usually C _{1 to} C ₁₈ monocarboxylic acid, preferably C ₂
~C include _5-vinyl alcohol esters of monocarboxylic acids. Examples of vinyl esters that can be copolymerized with ethylene include vinyl acetate, vinyl propionate and vinyl isobutyrate, vinyl acetate being the preferred vinyl ester. 20-40% by weight of copolymer, especially 25
It is preferred to include ˜35 wt% vinyl ester. They can also be a mixture of two copolymers as described in US Pat. No. 3,961,916.

It is preferred that these copolymers have a number average molecular weight of 1,000 to 6,000, preferably 1,000 to 4,000, measured by vapor phase permeation pressure (VPO).

The polymers and copolymers of the present invention can also be used in distillate fuels in combination with ionic or nonionic polar compounds having the ability to act in the fuel as wax crystal growth inhibitors. It has been found that polar nitrogen-containing compounds are particularly effective when used in combination with glycol esters, ethers or esters / ethers, and such ternary mixtures are within the scope of this invention. These polar compounds are generally, C ₂₀ -C ₃₀₀ formed by the reaction of one mole proportion of hydrocarbyl acid or their anhydrides with at least 1 molar proportions and 1-4 carboxylic acid groups hydrocarbyl-substituted amine , Preferably C _{20 to} C ₁₀₀ amine salts and / or amides, esters / amides can also be used. These nitrogen compounds are described in US Pat. No. 4,211,534. Suitable amines are usually long chain C ₂₀ -C ₄₀ primary, secondary, and tertiary or quaternary amines or mixtures thereof, but more nitrogen compounds amines short is generated is oil-soluble If you can use it,
It therefore usually contains about 20 to 300 total carbon atoms. Both nitrogen compounds also less having one linear C ₈ -C ₄₀ alkyl segment.

Suitable amines include primary, secondary, tertiary or quaternary, but secondary is preferred. Tertiary and quaternary amines can simply form amine salts.
Examples of amines are tetradecylamine and cocoamine (coco
amine), hydrogenated tallow amine and the like. Examples of secondary amines include dioctadecyl amine, methyl-behenyl amine and the like. Amine mixtures are also suitable, and many amines derived from natural substances are mixtures. A preferred amine is of the formula HNR ₁ R _{2 where} R ₁ and R ₂ are alkyl groups derived from hydrogenated tallow fat consisting of about 4% C ₁₄ , 31% C ₁₆ , 59% C ₁₈ . It is a secondary hydrogenated tallow amine.

Examples of carboxylic acids (and their anhydrides) suitable for the structure of these nitrogenated compounds include cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, cyclopentanedicarboxylic acid, dialpha-naphthylacetic acid, naphthalenedicarboxylic acid and the like. Generally these acids have about 5 to 13 carbon atoms in the cyclic portion. Preferred acids useful in the present invention are benzenedicarboxylic acids such as fumaric acid, terephthalic acid and orthophthalic acid. Orthophthalic acid or its anhydride is a particularly preferred embodiment.

It is preferred that the nitrogen-containing compound have at least one straight chain alkyl segment containing 8 to 40, preferably 8 to 24 carbon atoms extending from the compound. At least 1
It is necessary that an ammonium salt, amine salt or amide bond is present in the molecule. A particularly preferred amine compound is 1 mol part of phthalic anhydride and 2 parts of dihydrogenated tallow amine 2.
It is an amide-amine salt formed by reaction with a molar part. Another preferred embodiment is the diamide formed by dehydration of this amide-amine salt.

Other amine derivatives that can be used as co-additives are oil-soluble amine carboxylates and / or amides such as trioctylamine myristate or behenate. The reaction products of polyamines with fatty carboxylic acids, such as the reaction products of tetraethylenepentamine with stearic acid or behenic acid, can be used as well as the fatty amides themselves.
The copolymers can be used in combination with one or more additives of the type mentioned.

The relative proportion of additives used in the preferred mixture of the present invention is 0.5% ester polymer containing polyoxyalkylene groups.
-20 parts by weight to 1 part of other additives. The total amount of additives used depends on the individual fuel, but generally 0.0001-
5% by weight is used.

The additive system of the present invention may conveniently be supplied as a concentrate in oil which is mixed into a large quantity of fuel. These concentrates may also contain other additives if desired. These concentrates preferably contain from 3 to 75% by weight, more preferably from 3 to 60% by weight and most preferably from 10 to 50% by weight of additives. Such concentrates are also within the scope of this invention.

The present invention is illustrated by the following examples, in which the effectiveness of the additive of the present invention as a pour point depressant and filterability improver in distillate fuels is described in "Journal of the Institute. Of Petroleum (Journal
of the Institute of Petroleum) "52, 510, 19
Compared to other similar additives in the Cold Filter Plugging Point Test (CFPPT) performed by the procedure detailed in 66-7, pp. 173-185. This test is designed to correlate with the cold flow of middle distillate fuels in automatic diesel.

Briefly, a 40 ml sample of the oil to be tested is cooled in a bath maintained at about -34 ° C to provide about 1 ° C / min of non-linear cooling. Regularly (starting at least 2 ° C above cloud point 1 ° C)
The oil, cooled per drop), is tested for its ability to flow through a fine screen during a specified time using a test device which is a pipette with a lower end attached to an inverted funnel located below the surface of the oil to be tested. A 350 mesh screen with an area defined by a diameter of 12 mm is stretched over the funnel mouth. Periodic tests are each started by applying a vacuum to the upper end of the pipette, thereby sucking the oil in the pipette through the screen to the mark indicating 20 ml of oil. Allow oil to return to the CFPP tube immediately after each successful pass. Temperature 1 until oil does not fill the pipette within 60 seconds
Repeat the test for each drop in ° C. This temperature is indicated as the CFPP temperature. The difference between CFPP between the fuel without additive and the same fuel with additive is shown as the CFPP drop due to additive. Effective additive flow enhancers are given at the same concentration of additive as CFPP drop.

Example 1 The fuel used in this example was as follows: The additives used were: Additive 1: Mixture C ₁₂ / C obtained by reacting a 50:50 molar mixture of normal C ₁₂ and C ₁₄ alcohols with fumaric acid.
_{14 A} copolymer obtained by solution copolymerizing fumarate and vinyl acetate at a molar ratio of 1: 1 using azobisisobutyronitrile as a catalyst at 60 ° C.

Additive 2: Dibehenate ester of polyethylene glycol having a molecular weight of 600.

Additive 3: Dibehenate ester of polyethylene glycol having a molecular weight of 400.

Additive 4: Same as Additive 1 except that the C ₁₂ / C ₁₄ alcohol mixture used for the esterification of fumaric acid contained 2.5 moles of polyethylene glycol with an average molecular weight of 600 and the polymerization was carried out at 80 ° C. Met.

Additive 5: Same as Additive 4 except that 2.5 moles of polyethylene glycol, having a molecular weight of 750, was used in place of polyethylene glycol having a molecular weight of 600, 2.5 moles.

The CFPP drop obtained in the fuel when treated with these additives and their mixtures was as follows: In each case a large decrease in CFPP temperature is shown when the polyoxyalkylene segment is present in the molecule.

Example 2 The additive of Example 1 was tested in the following fuel.

Additives required to reach the target CFPP (Additive 1 or 5
The amount of the 2: 1 polymerization mixture of the additive and Additive 3) was also measured with the following results: Example 3 The CFPP drop obtained with a 2: 1 mixture of additives 1, 4 or 5 and 3 was observed as follows: Example 4 Ethylene vinyl acetate (EVA) according to British Patent No. 1,263,152 containing 36% by weight of vinyl acetate in the fuel G containing the additive of the present invention and having a number average molecular weight of 2,000 as measured by the vapor phase osmosis method. ) Used together with the copolymer.

The other additives used were as follows: Additive 1 of Example 1 Additive 6 was the C ₁₂ / C ₁₄ alcohol mixture used for the esterification of fumaric acid in the molecular weight 600 poly-ethylene glycol dioleate. Additive 1 except that 5 mol% was added
Was the same as

Additives 6 except that to obtain a dialkyl fumarate of the following, n-C ₁₂ alcohol 45 moles n-C ₁₄ alcohol 45 moles _{n-C 16 (CH 2 -CH} 2 O) 200 -OH 10 mole mixture of Was the same as additive 1.

Additive 8 was the same as Additive 6 except that 2 mol% polyethylene glycol having a molecular weight of 600 was used.

The CFPP values obtained were as follows: Example 5 The effect of the amount of additive used on the CFPP values of fuels E, F, G and I was measured using the following additive mixture.

Code Mixture X 2: 1 molar ratio of Additive 1 and Additive 3 Y 2: 1 molar ratio of Additive 5 and Additive 3 The results are shown graphically in FIGS.
The figure also includes the results obtained using the same treat rate of EVA copolymer alone used in Example 4.

Example 6 The compounds of this invention were tested as pour point depressants in salt vent neutral lubricating oils. The polymer was added with an equimolar amount of the following: fumaric acid ester prepared from a mixture of C ₁₂ 20 parts C ₁₃ 30 parts C ₁₄ 30 parts C ₁₅ 20 parts alcohol, vinyl acetate (Additive 9) and alcohol mixture. Prepared by the method described above from a similar polymer containing 2.5 mol% of polyethylene glycol having a molecular weight of 750 (Additive 10).

The pour point was measured by the method of ASTM D 97 and the following results were obtained.

Example 7 Additive 9 was the same as Additive 1 except that a mixture of C ₁₂ and C ₁₄ alcohols was replaced with a commercial alcohol mixture sold as Dobanol 25. Dobanol 25 is a mixture of C ₁₂ alcohol 20% by weight C ₁₃ alcohol 30% by weight C ₁₄ alcohol 30% by weight C ₁₅ alcohol 20% by weight, 80% by weight of which is normal alcohol and 20% by weight of which is methyl at the 1 position. Has a branch.

Additive 10 was the same as Additive 9 except that a mixture of 1.975 moles of dovanol 25, and 0.025 moles of polyethylene glycol having a molecular weight of 750 was used.

These additives were added to Fuel D and untreated CFPP at -5 ° C and the following ASTM D-96 distillation values, Initial boiling point 202 ° C 20% 272 90% 329 Final boiling point 344 in Fuel J with additives and additives in Fuel J. Tested as a 4: 1 ratio mixture with 3, the following results were obtained: Example 8 Tested in Fuel K with + 5 ° C cloud point and the following ASTM D-96 distillation values, initial boiling point 203 ° C 20% 261 90% 322 final boiling point 349 ° C, the appearance of the fuel at 1 ° C hourly. After cooling it was recorded at -5 ° C.

The results were as follows using 1,000 ppm of additive as a 4: 1 mixture: Additive Appearance Additive 1: Additive 2 Solid Additive 5: Additive 2 Fluid Additive 1: Additive 3 Solid Body Additive 5: Additive 3 Fluid Example 9 Additive 11 was the same as Additive 1 except that 10 mol% of the C ₁₂ / C ₁₄ alcohol was replaced by monomethyl ether of polyethylene glycol having a molecular weight of 750. It was

Additives were treated with untreated CFPP at -2 ° C and initial boiling point 198 ° C 20% 256 90% 343 final boiling point 367 ASTM D-96 distillation value Fuel D50 wt% and fuel D50
Wt%, 32 wt% vinyl acetate ethylene vinyl acetate copolymer was tested in a blend containing 200 ppm, -9 ° C.
CFPP of was obtained. The amount of additive required to provide -9 ° C CFPP to the blend was determined to be: Additives used 1: 11: 3 1: 3 ratio 1: 1: 1 2: 1 required. The test was repeated using a mixture containing 50 ppm by weight of fuel J and 50% by weight of fuel M containing 200 ppm of ethylene vinyl acetate copolymer as the fuel amount 600> 1200.

Fuel M had an untreated CFPP of -4 ° C and an ASTM D-96 distillation value with an initial boiling point of 186 ° C 20% 254 90% 331 final boiling point 355.

The amounts of additives required to give -9 ° C CFPP were found to be: Additives used 1: 11: 3 1: 3 ratio 1: 1: 1 2: 1 amounts required. 600 1200

[Brief description of drawings]

1 to 4 are graphs showing the influence of the additive treatment rate on the CFPP of the fuel.

Claims (3)

[Claims] 1. Produced from ethylenically unsaturated ester,
An additive for improving the flow characteristics of petroleum distillate fuels, which contains a polymer or copolymer having a weight average molecular weight of 1,000 to 200,000 and containing 0.1 to 50% by weight of a polyoxyalkylene group having a molecular weight of 100 to 5,000. 2. Manufactured from ethylenically unsaturated ester,
A polymer or copolymer having a weight average molecular weight of 1,000 to 200,000 containing 0.1 to 50% by weight of a polyoxyalkylene group having a molecular weight of 100 to 5,000, and optionally other additives, 3 to 75 based on the weight of the concentrated liquid. A concentrated liquid additive for improving the flow characteristics of petroleum distillate fuel, which is contained by weight. 3. Manufactured from an ethylenically unsaturated ester,
Molecular weight 100 to 5,000 Distillation of polymer or copolymer having a weight average molecular weight of 1,000 to 200,000 containing 0.1 to 50% by weight of polyoxyalkylene group 0.0001 based on the weight of petroleum fuel oil
Distillated petroleum fuel containing ~ 5% by weight.