JPH0649464A - Additive for fuel oil - Google Patents

Abstract

PURPOSE:To provide an additive for fuel oil containing a mixture of a specific polyester derivative and a reaction product of an aromatic dicarboxylic acid and a long-chain alkylamine, etc., capable of remarkably lowering the flow point and the cold clogging temperature and useful for a fluidity improving agent for fuel oil. CONSTITUTION:The additive for fuel oil can be produced by compounding (A) at least one kind of amide-amine salt, diamide, etc., of an aromatic dicarboxylic acid (e.g. phthalic anhydride) and a long-chain alkylamine (e.g. di-hardened beef tallow alkylamine) and (B) a polyester derivative expressed by formula (R<1> and R<2> are 6-29C hydrocarbon group; A<1> and A<2> are 2-4C alkylene; Y is simple bond or bivalent aliphatic or aromatic group; k and m are integer of 1-50; n is integer of 1-10) (e.g. polyoxyethylene behenate). The additive can remarkably lower the flow point and the cold clogging temperature and disperse the precipitated crystals in the form of sufficiently small particles even under practical cooling condition and is suitable as an agent for improving the fluidity of a fuel oil.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel fuel oil additive,
More specifically, it has a good pour point depressing ability and a low temperature clogging temperature depressing ability, and is capable of sufficiently refining and dispersing precipitated crystals even under actual cooling conditions, which is suitable as a fluidity improving agent for fuel oil. The present invention relates to an additive for fuel oil.

[0002]

2. Description of the Related Art When a middle distillate fuel such as diesel fuel or heavy fuel oil A is exposed to a low temperature in winter or in a cold region, wax-like substances contained therein are deposited,
The filter of the fuel piping system of the diesel engine may become clogged, causing troubles such as engine starting, or the fuel oil itself may become semi-solid or solid and lose fluidity.
It causes troubles such as blocking the oil supply pipe. Since such problems tend to further increase due to the recent heavier crude oil and the quantitative tightness of kerosene and light oil, appropriate measures against this problem have been desired.

Conventionally, various additives for preventing such troubles of fuel oil at low temperature have been known, but all of these additives change the size and shape of precipitated wax crystals. Then, by reducing the cohesive force between the crystals and between the wax and the oil, the pour point is lowered so that it can pass through a coarse filter. However, during operation of the diesel engine at low temperatures, the precipitated wax crystals do not become so small that they pass through the vehicle paper fuel filter, which results in the formation of a permeable cake on the filter to pass the liquid fuel.

As such a fluidity improver, for example, polyethylene glycol dibehenate (JP-A-57-1)
77092) or an esterification product of a polyethylene glycol ester of a polycarboxylic acid with a fatty acid (Japanese Patent Laid-Open No. Sho 6-62).
No. 1-123698, No. 62-18493,
No. 62-109892, No. 61-207495, No. 61-213292), an esterified product of an ethylene oxide adduct of ethylenediamine (JP-A-57).
-170993), triethanolamine monostearate (Japanese Patent Publication No. 50-36246), polyester derivatives (Japanese Patent Laid-Open No. 62-18493) and the like are known. Although the plugging temperature drops, the effect on the drop of pour point is insufficient. Further, these may be added with other fluidity improvers such as ethylene-vinyl acetate copolymer (EVA) (Japanese Patent Laid-Open Publication No. Sho 4 (1999) -43,091).
7-10626, 57-170992,
No. 59-207989, No. 61-181892, Japanese Patent Application No. 61-153709), poly (meth) acrylate (JP-A Nos. 51-61509 and 63-23990), ethylene-propylene. Copolymer (JP-A-60-137998, JP-B 2-
No. 138389) and the like, the low temperature clogging temperature and the pour point are lowered, but the precipitated crystals cannot be said to be sufficiently miniaturized under slow cooling conditions, and the wax crystals are dispersed in oil. No, often with the drawback of settling to the bottom.

Further, as a fluidity improver, an amide / amine salt of an aromatic dicarboxylic acid (JP-A-49-53902).
JP-A-62-587) and a combination system thereof with an ethylene-vinyl acetate copolymer or an ethylene-propylene copolymer (JP-A-56-92996, 58-58).
No. 1792 gazette, No. 63-165487 gazette) and the like are known, but these are effective for lowering the low temperature clogging temperature and the pour point, but under the slow cooling conditions, the precipitation crystals become finer. It is not sufficient, and there are drawbacks such as the precipitation of wax crystals.

As described above, in the conventional fluidity improver, the wax crystals deposited are small enough to pass through the paper fuel filter of the vehicle, even though they are effective in lowering the pour point of fuel oil and the low temperature clogging temperature. The problem of clogging there remains unsolved, and the wax crystals precipitated do not disperse in the oil and often accompany the drawbacks of settling to the bottom, so improvements have been desired. .

[0007]

SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of the conventional flowability improvers and can simultaneously lower the pour point and the low temperature clogging temperature, and precipitates even when slowly cooled. The purpose of the present invention is to provide a fuel oil additive capable of sufficiently refining crystals and precipitating wax crystals dispersed in oil to prevent sedimentation.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention are keen to develop an additive which, when added to fuel oil, effectively lowers the pour point, prevents low temperature clogging and suppresses the precipitation of wax crystals. As a result of repeated studies, it was found that the object can be achieved by combining two specific compounds, and the present invention has been completed based on this finding.

That is, the present invention comprises (A) at least one selected from amide amine salts of aromatic dicarboxylic acids and long-chain alkylamines and diamides;

[Chemical 2] (In the formula, R ¹ and R ² are each a hydrocarbon group having 6 to 29 carbon atoms, A ¹ and A ² are each an alkylene group having 2 to 4 carbon atoms, Y is a bond, or a divalent aliphatic or aromatic group. Group residue, k and m are each an integer of 1 to 50, and n is 1 to
An integer of 10) and a mixture with a polyester derivative represented by the formula (10).

In the composition of the present invention, an amide / amine salt or diamide of an aromatic dicarboxylic acid and a long chain alkylamine is used as the component (A). Examples of the aromatic dicarboxylic acid which is one of the raw materials of the component (A) include benzenedicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and phthalic anhydride, 2,3-naphthalenedicarboxylic acid, 1,8- Naphthalene dicarboxylic acid, 1,4
-Naphthalenedicarboxylic acids such as naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid.

The long-chain alkylamine as the other raw material includes, for example, primary or secondary amines having at least one linear or branched, saturated or unsaturated alkyl group having 10 to 30 carbon atoms. To be A secondary amine having a linear saturated alkyl group having 10 to 30 carbon atoms is preferably used.

As the component (A), an amide / amine salt may be used alone, a diamide may be used alone, or a mixture of a diamide and an amide / amine salt may be used. In particular, it is advantageous to use a mixture containing the diamide and the amide amine salt in a weight ratio of 50:50 to 95: 5.

In the additive of the present invention, the polyester derivative represented by the general formula (I) is used as the component (B). R ¹ and R ² in the formula (I) are each a hydrocarbon group having 6 to 29 carbon atoms, preferably an aliphatic hydrocarbon group, and particularly preferably a linear alkyl group.
These may be introduced as a linear fatty acid residue ^{(R 1 CO-, R 2 CO-} ). As the linear fatty acid, a monovalent carboxylic acid having 7 to 30 carbon atoms, for example, n-decanoic acid,
n-dodecanoic acid (lauric acid), n-tetradecanoic acid (myristic acid), n-hexadecanoic acid (palmitic acid), n-octadecanoic acid (stearic acid), n-eicoic acid (arachidic acid), n-docosanoic acid ( Behenic acid),
Examples thereof include n-tetracosanoic acid (lignoceric acid), n-hexaeiicoic acid, n-octaeicoic acid, and n-triacontanoic acid. These may be used alone or in combination of two or more. For example, mixed fatty acids obtained by hydrogenating fatty acids obtained by hydrolyzing natural fats and oils such as beef tallow, rapeseed oil, fish oil, and coconut oil can be used as they are. Preferably, these hydrogenated fatty acids are used.

A ¹ and A ² in the general formula (I) are each an alkylene group having 2 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, a tetramethylene group, and the like. , Propylene oxide, tetrahydrofuran or the like.

Y is a bond or a divalent aliphatic group such as an alkylene group or a divalent aromatic group such as a phenylene group, which is a dicarboxylic acid or a derivative thereof. Can be introduced. Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid,
Examples thereof include pimelic acid, phthalic acid, terephthalic acid, naphthalic acid and their anhydrides.

Further, k and m are the addition mole numbers of the oxyalkylene groups (A ¹ O) and (A ² O), respectively, and are ¹ to 5
It is an integer of 0, preferably 1 to 25, more preferably 1 to 15. For example, (A ¹ O) k can be introduced by adding a single alkylene oxide such as ethylene oxide, or by sequentially adding ethylene oxide and propylene oxide, or by adding a mixed alkylene oxide thereof. It can also be introduced in the form of random addition, etc. n is 1 to 1
It is an integer of 0, preferably 1-5.

The polyester derivative used in the composition of the present invention is obtained, for example, by first adding an alkylene oxide to a fatty acid, then adding a dibasic acid and further adding an alkylene oxide, and if necessary, adding the dibasic acid and the alkylene oxide. It can be produced by repeating the addition step and finally crosslinking the obtained alkylene oxide adduct with a dibasic acid. In addition, a method in which a polyoxyalkylene glycol and a dibasic acid are preliminarily reacted to obtain a polyester polyol having a hydroxyl group at a terminal, and a terminal hydroxyl group is further ester-capped with a fatty acid, or a polyoxyalkylene glycol and a fatty acid are used in advance. Any method such as a method of producing an ester polyether having a hydroxyl group at the terminal and crosslinking this with a dibasic acid can be employed.

The mixing ratio of the component (A) and the component (B) in the additive of the present invention is 50 to 95% by weight of the component (A), 50 to 5% by weight of the component (B), and preferably the component (A). 70 to 95% by weight and (B) component 30 to 5% by weight are selected.

The fuel oil additive of the present invention thus obtained exhibits good pour point depressing ability and low temperature clogging temperature depressing ability, and actual cooling conditions (slow cooling of about 1 ° C./hr). Crystals that precipitate even underneath are sufficiently miniaturized and dispersed,
Sedimentation can be prevented. The reason for this is not necessarily clear, but it is likely that the compound of component (B) used in the additive of the present invention has a linear saturated alkyl group that exhibits the property of being adsorbed or eutecticized by wax precipitated from fuel oil. It is thought that this is because the wax crystal nucleation effect is exerted. Furthermore, the compound of the component (A) has an action of adsorbing to the precipitated wax crystal surface to control the crystal growth and change the crystal shape. (This can be observed under a microscope under slow cooling.) By using the component (A) and the component (B) together, a synergistic effect appears, and the precipitated wax crystals are made finer to form in the oil. It is presumed that it is dispersed in the solution to prevent sedimentation.

Such effects are obtained by observing the dispersed state of the precipitated wax crystals while gradually cooling the fuel oil to which the additive of the present invention has been added, and performing a simple oil permeability test to check the filterability. It is understood by observing with a microscope after filtering out the precipitated crystals. The additive of the present invention is usually added to fuel oil in an amount of 10 to 1000 ppm.

The additives of the present invention include ethylene vinyl acetate copolymer, ethylene / acrylate copolymer,
Polymer-based additives such as ethylene-propylene copolymer, polyalkyl (meth) acrylate, branched polyethylene, chlorinated polyethylene, condensates of chlorinated paraffin and naphthalene, and surfactants such as nitrogen-containing derivatives of alkenylsuccinic acid You can also do it.

[0022]

The fuel oil additive of the present invention has good pour point depressing ability and low temperature clogging temperature depressing ability, and
Even under actual cooling conditions, precipitated crystals can be sufficiently fined and dispersed to prevent sedimentation, and are suitably used as a fluidity improver for fuel oil.

[0023]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. The performance of the fuel oil additive was evaluated by conducting the following various tests.

(1) Measurement of Wax Crystal Size The test oil is placed in a thermostatic bath equipped with a program control and cooled to the cloud point of the test oil + 10 ° C. at a cooling rate of 7.5 ° C./h. From the cloud point of the test oil + 10 ° C to the measurement temperature (-8.5
C.) is gradually cooled at a cooling rate of 1.degree. C./h, and the temperature is maintained for 2 hours. Then, the sample is suction filtered using a glass filter to filter out crystals, and then washed with cold acetone. The crystal thus obtained was observed under a microscope to measure its size.

(2) Simple oil passage test The low temperature filtration characteristics of the test oil were measured as follows. 35
0 ml of the test oil is put into a graduated cylinder and cooled from room temperature to the cloud point of the test oil + 10 ° C. at a cooling rate of 7.5 ° C./h. Then, from the cloud point of the test oil + 10 ° C to the measurement temperature (-8.
(5 ° C.) at a cooling rate of 1 ° C./h and then held at the measurement temperature for 2 hours, after which the plate crystals of the test oil surface layer are removed by suction, forming during cooling the oil / air interface. Avoid being affected by this test by unusually large wax crystals that have a tendency to develop. The wax that has settled in the graduated cylinder is dispersed by gently stirring, and then a CFPP filter unit is inserted. The cock is opened to reduce the pressure to 500 mmHg, and when 200 ml of the test oil passes through the filter and is stored in the calibrated receiver, the cock is closed. Pass if 200 ml of test oil is collected within 30 seconds of passing the filter of the given mesh, pass if the flow rate is too slow, indicating that the filter is blocked. The mesh size of the finally passed filter mesh was recorded.

(3) Low temperature clogging test Clow temperature clogging temperature C was performed according to JIS K-2288.
FPP was determined.

(4) Pour point test Pour point PP was determined by carrying out according to JIS K-2269.

(5) Dispersibility test 100 ml of test oil was put in a 100 ml Epton tube and cooled at room temperature to the cloud point of the test oil + 10 ° C. at 7.5 ° C./h in a thermostat with program temperature control. Quenching at a speed, then from the cloud point + 10 ° C to the measured temperature (-8.5
℃) at a cooling rate of 1 ℃ / h, gradually cooled to 24
After leaving for a while, the state was observed. The judgment was performed by the ratio of the wax dispersion layer of the test oil generated by the wax precipitation and the transparent layer of the upper supernatant. The dispersibility of the wax is better as the proportion of the wax dispersion layer is larger. The proportion is 70% or more as ◯, 50% or more and less than 70% as Δ, and less than 50% as x. In addition, light oil A having the properties shown in Table 1 was used in the test.
And light oil B were used.

[Table 1]

Production of Component (A) Production Example 1 1 mol of phthalic anhydride and 2 mol of di-hardened beef tallow alkylamine were placed in a 2-liter four-necked flask and placed under a nitrogen stream at 115 to 115
After heating with stirring at 125 ° C. for 1 hour, p-toluenesulfonic acid was added, and while further removing the produced water under reduced pressure, heating was performed with stirring at 145 to 155 ° C. for 5 hours. The acid value of this amidated product was 43 and the amine value was 46.

Production Example 2 1 mol of phthalic anhydride and 2 mol of di-cured tallow alkylamine were heated at 110 to 120 ° C. for 2 hours with stirring to obtain an amide amine salt. This product had an acid value of 50 and an amine value of 53.

Production Example 3 In the same manner as in Production Example 1, an amidated product of 1 mol of 2,3-naphthalenedicarboxylic acid anhydride and 2 mol of di-hardened tallow alkylamine was produced.

Production Example 4 In the same manner as in Production Example 1, an amidated product of 1 mol of 1,8-naphthalenedicarboxylic acid anhydride and 2 mol of di-hardened tallow alkylamine was produced.

Production Example 5 In the same manner as in Production Example 2, an amide amine salt of 1 mol of 2,3-naphthalenedicarboxylic acid anhydride and 2 mol of di-hardened tallow alkylamine was produced.

Production of Component (B) Production Example 6 2 mol of behenic acid and 0.5% by weight of potassium acetate were charged into an autoclave, dissolved, replaced with nitrogen and deaerated, and then heated to 150
Reacting 10 moles of ethylene oxide at ~ 190 ° C,
A monoester polyether of polyoxyethylene behenate (average number of moles of ethylene oxide added: 4.5, hydroxyl value: 107, acid value: 2.9) was obtained. To this monoester polyether, 1 mol of adipic acid and 0.5% by weight of p-toluenesulfonic acid were added, and the mixture was heated under reduced pressure at 140 to 160 ° C. for 5 hours while stirring to obtain an esterified product. . The acid value of this ester was 8.5.

Production Examples 7 to 9 Polyester ethers were obtained in the same manner as in Production Example 6 using the raw materials shown in Table 2. The results are shown in Table 2.

[Table 2] Note 1) The abbreviations indicate the following, and the number of moles indicates the average number of moles of alkylene oxide added. EO: ethylene oxide, PO: propylene oxide,
THF: Tetrahydrofuran, EO / PO: Random addition, PO-EO: Block addition 2) Neutralization value 168.6

Production Example 10 1 mol of adipic acid and polyethylene glycol (molecular weight 2
00) 2 mol and 1% by weight of p-toluenesulfonic acid
It was put in a 4-necked flask of 1 l and heated under stirring under reduced pressure at 120 to 130 ° C. for 3 hours while removing generated water to obtain an esterified product. The acid value of this ester was 5.3. Furthermore, 2 mol of behenic acid was added to the esterified product, and the product water was removed under reduced pressure at 140 to 160 ° C.
The mixture was heated with stirring for 5 hours to obtain an esterified product. The acid value of this ester was 10.1.

Production Examples 11 to 13 Polyester ethers were obtained in the same manner as in Production Example 10 using the raw materials shown in Table 3. The results are shown in Table 3.

[Table 3] Note 1) Abbreviations indicate the following. EG: ethylene glycol, PO: propylene oxide, THF: tetrahydrofuran, EO: ethylene oxide, and EG-EO / PO (8/2) is a random adduct of ethylene glycol with a molar ratio of EO and PO of 8/2.

Examples 1 to 16 and Comparative Examples 1 to 6 The fluidity improver having the composition shown in Table 4 was diluted with an aromatic solvent and subjected to the test as a concentrate having a concentration of 50% by weight. Add 3 parts of the concentrate to each of light oil A and light oil B shown in Table 1 above.
The test oil was added at a rate of 00 ppm, and various tests were performed on this test oil to evaluate the performance of the fluidity improver. The results are shown in Table 5.

[Table 4]

[Table 5]

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[Procedure amendment]

[Submission date] May 14, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction content]

[Document name] Statement

Title of the invention Additive for fuel oil

[Claims]

[Chemical 1] (In the formula, R ¹ and R ² are each a hydrocarbon group having 6 to 29 carbon atoms, A ¹ and A ² are each an alkylene group having 2 to 4 carbon atoms, Y is a mere bond, or a divalent aliphatic or aromatic group. Group group, k and m are each an integer of 1 to 50, and n is 1 to
Which is an integer of 10), and a mixture with a polyester derivative represented by the formula (10).

Detailed Description of the Invention

[0001]

The present invention relates to a novel fuel oil additive,
More specifically, it has a good pour point depressing ability and a low temperature clogging temperature depressing ability, and is capable of sufficiently refining and dispersing precipitated crystals even under actual cooling conditions, which is suitable as a fluidity improving agent for fuel oil. The present invention relates to an additive for fuel oil.

[0002]

2. Description of the Related Art When a middle distillate fuel such as diesel fuel or heavy fuel oil A is exposed to a low temperature in winter or in a cold region, wax-like substances contained therein are deposited,
The filter of the fuel piping system of the diesel engine may become clogged, causing troubles such as engine starting, or the fuel oil itself may become semi-solid or solid and lose fluidity.
It causes troubles such as blocking the oil supply pipe. Since such problems tend to further increase due to the recent heavier crude oil and the quantitative tightness of kerosene and light oil, appropriate measures against this problem have been desired.

Conventionally, various additives for preventing such troubles of fuel oil at low temperature have been known, but all of these additives change the size and shape of precipitated wax crystals. Then, by reducing the cohesive force between the crystals and between the wax and the oil, the pour point is lowered so that it can pass through a coarse filter. However, in operating a diesel engine at low temperatures, the precipitated wax crystals do not become so small that they pass through the vehicle paper fuel filter, which results in the formation of a permeable cake on the three filters to pass the liquid fuel. .

As such a fluidity improver, for example, polyethylene glycol dibehenate (JP-A-57-1)
77092) or an esterification product of a polyethylene glycol ester of a polycarboxylic acid with a fatty acid (Japanese Patent Laid-Open No. Sho 6-62).
No. 1-123698, No. 62-18493,
No. 62-109892, No. 61-207495, No. 61-213292), an esterified product of an ethylene oxide adduct of ethylenediamine (JP-A-57).
-170993), triethanolamine monostearate (Japanese Patent Publication No. 50-36246), polyester derivatives (Japanese Patent Laid-Open No. 62-18493) and the like are known. Although the plugging temperature drops, the effect on the drop of pour point is insufficient. In addition, these may be added with other fluidity improvers such as ethylene-vinyl acetate copolymer (EVA) (Japanese Patent Laid-Open Publication No. 4 (1999) -43242).
7-10626, 57-170992,
No. 59-207989, No. 61-181892, Japanese Patent Application No. 61-153709), poly (meth) acrylate (JP-A Nos. 51-61509 and 63-23990), ethylene-propylene. Copolymer (JP-A-60-137998, JP-B 2-
No. 138389) and the like, the low temperature clogging temperature and the pour point are lowered, but the precipitated crystals cannot be said to be sufficiently miniaturized under slow cooling conditions, and the wax crystals are dispersed in oil. No, often with the drawback of settling to the bottom.

Further, as a fluidity improver, an amide / amine salt of an aromatic dicarboxylic acid (JP-A-49-53902).
JP-A-62-587) and a combination system thereof with an ethylene-vinyl acetate copolymer or an ethylene-propylene copolymer (JP-A-56-92996, 58-58).
No. 1792, No. 63-165487, etc.) are known, but they are effective for lowering the low temperature clogging temperature and the pour point, but under the slow cooling condition, the precipitation crystals become finer. It is not sufficient, and there are drawbacks such as the precipitation of wax crystals.

As described above, in the conventional fluidity improver, the wax crystals deposited are small enough to pass through the paper fuel filter of the vehicle, even though they are effective in lowering the pour point of fuel oil and the low temperature clogging temperature. The problem of clogging there remains unsolved, and the precipitated wax crystals do not disperse in the oil and often have the drawback of settling at the bottom, so improvement thereof has been desired. .

[0007]

SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of the conventional flowability improvers and can simultaneously lower the pour point and the low temperature clogging temperature, and precipitates even when slowly cooled. The purpose of the present invention is to provide a fuel oil additive capable of sufficiently refining crystals and precipitating wax crystals dispersed in oil to prevent sedimentation.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention are keen to develop an additive which, when added to fuel oil, effectively lowers the pour point, prevents low temperature clogging and suppresses the precipitation of wax crystals. As a result of repeated studies, it was found that the object can be achieved by combining two specific compounds, and the present invention has been completed based on this finding.

That is, the present invention comprises (A) at least one selected from amide amine salts of aromatic dicarboxylic acids and long-chain alkylamines and diamides;

[Chemical 2] (In the formula, R ¹ and R ² are each a hydrocarbon group having 6 to 29 carbon atoms, A ¹ and A ² are each an alkylene group having 2 to 4 carbon atoms, Y is a mere bond, or a divalent aliphatic or aromatic group. Group residue, k and m are each an integer of 1 to 50, and n is 1.
The fuel oil additive comprises a mixture with a polyester derivative represented by the formula:

In the composition of the present invention, an amide / amine salt or diamide of an aromatic dicarboxylic acid and a long chain alkylamine is used as the component (A). Examples of the aromatic dicarboxylic acid which is one of the raw materials of the component (A) include benzenedicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and phthalic anhydride, 2,3-naphthalenedicarboxylic acid, 1,8- Naphthalene dicarboxylic acid, 1,4
-Naphthalenedicarboxylic acids such as naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid.

The long-chain alkylamine as the other raw material includes, for example, primary or secondary amines having at least one linear or branched, saturated or unsaturated alkyl group having 10 to 30 carbon atoms. To be A secondary amine having a linear saturated alkyl group having 10 to 30 carbon atoms is preferably used.

As the component (A), an amide / amine salt may be used alone, a diamide may be used alone, or a mixture of a diamide and an amide / amine salt may be used. In particular, it is advantageous to use a mixture containing the diamide and the amide amine salt in a weight ratio of 50:50 to 95: 5.

In the additive of the present invention, the polyester derivative represented by the general formula (I) is used as the component (B). R ¹ and R ² in the formula (I) are each a hydrocarbon group having 6 to 29 carbon atoms, preferably an aliphatic hydrocarbon group, and particularly preferably a linear alkyl group.
These may be introduced as a linear fatty acid residue ^{(R 1 CO-, R 2 CO-} ). As the linear fatty acid, a monovalent carboxylic acid having 7 to 30 carbon atoms, for example, n-decanoic acid,
n-dodecanoic acid (lauric acid), n-tetradecanoic acid (myristic acid), n-hexadecanoic acid (palmitic acid), n-octadecanoic acid (stearic acid), n-eicoic acid (arachidic acid), n-docosanoic acid ( Behenic acid),
Examples thereof include n-tetracosanoic acid (lignoceric acid), n-hexaeiicoic acid, n-octaeiicoic acid, and n-triacontanoic acid. These may be used alone or in combination of two or more. For example, mixed fatty acids obtained by hydrogenating fatty acids obtained by hydrolyzing natural fats and oils such as beef tallow, rapeseed oil, fish oil, and coconut oil can be used as they are. Preferably, these hydrogenated fatty acids are used.

A ¹ and A ² in the general formula (I) are each an alkylene group having 2 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, a tetramethylene group, and the like. , Propylene oxide, tetrahydrofuran or the like.

Y is a bond or a divalent aliphatic group such as an alkylene group or a divalent aromatic group such as a phenylene group, which is a dicarboxylic acid or a derivative thereof. Can be introduced. Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid,
Examples thereof include pimelic acid, phthalic acid, terephthalic acid, naphthalic acid and their anhydrides.

Further, k and m are the addition mole numbers of the oxyalkylene groups (A ¹ O) and (A ² O), respectively, and are ¹ to 5
It is an integer of 0, preferably 1 to 25, more preferably 1 to 15. For example, (A ¹ O) k can be introduced by adding a single alkylene oxide such as ethylene oxide, or by sequentially adding ethylene oxide and propylene oxide, or by adding a mixed alkylene oxide thereof to block addition. It can also be introduced in the form of random addition, etc. n is 1 to 1
It is an integer of 0, preferably 1-5.

The polyester derivative used in the composition of the present invention is obtained, for example, by first adding an alkylene oxide to a fatty acid, then adding a dibasic acid and further adding an alkylene oxide, and if necessary, adding the dibasic acid and the alkylene oxide. It can be produced by repeating the addition step and finally crosslinking the obtained alkylene oxide adduct with a dibasic acid. In addition, a method in which a polyoxyalkylene glycol and a dibasic acid are preliminarily reacted to obtain a polyester polyol having a hydroxyl group at a terminal, and a terminal hydroxyl group is further ester-capped with a fatty acid, or a polyoxyalkylene glycol and a fatty acid are used in advance. Any method such as a method of producing an ester polyether having a hydroxyl group at the terminal and crosslinking this with a dibasic acid can be employed.

The mixing ratio of the component (A) and the component (B) in the additive of the present invention is 50 to 95% by weight of the component (A), 50 to 5% by weight of the component (B), and preferably the component (A). 70 to 95% by weight and (B) component 30 to 5% by weight are selected.

The fuel oil additive of the present invention thus obtained exhibits good pour point depressing ability and low temperature clogging temperature depressing ability, and actual cooling conditions (slow cooling of about 1 ° C./hr). Crystals that precipitate even underneath are sufficiently miniaturized and dispersed,
Sedimentation can be prevented. The reason for this is not necessarily clear, but it is likely that the compound of component (B) used in the additive of the present invention has a linear saturated alkyl group that exhibits the property of being adsorbed or eutecticized by wax precipitated from fuel oil. It is thought that this is because the wax crystal nucleation effect is exerted. Furthermore, the compound of the component (A) has an action of adsorbing to the precipitated wax crystal surface to control the crystal growth and change the crystal shape. (This can be observed under a microscope under slow cooling.) By using the component (A) and the component (B) together, a synergistic effect appears, and the precipitated wax crystals are made finer to form in the oil. It is presumed that it is dispersed in the solution to prevent sedimentation.

Such effects are obtained by observing the dispersed state of the precipitated wax crystals while gradually cooling the fuel oil to which the additive of the present invention has been added, and performing a simple oil permeability test to check the filterability. It is understood by observing with a microscope after filtering out the precipitated crystals. The additive of the present invention is usually added to fuel oil in an amount of 10 to 1000 ppm.

The additives of the present invention include ethylene vinyl acetate copolymer, ethylene / acrylate copolymer,
Polymer-based additives such as ethylene-propylene copolymer, polyalkyl (meth) acrylate, branched polyethylene, chlorinated polyethylene, condensates of chlorinated paraffin and naphthalene, and surfactants such as nitrogen-containing derivatives of alkenylsuccinic acid You can also do it.

[0022]

The fuel oil additive of the present invention has good pour point depressing ability and low temperature clogging temperature depressing ability, and
Even under actual cooling conditions, precipitated crystals can be sufficiently fined and dispersed to prevent sedimentation, and are suitably used as a fluidity improver for fuel oil.

[0023]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. The performance of the fuel oil additive was evaluated by conducting the following various tests.

(1) Measurement of Wax Crystal Size The test oil is placed in a thermostatic bath equipped with a program control and cooled to the cloud point of the test oil + 10 ° C. at a cooling rate of 7.5 ° C./h. From the cloud point of the test oil + 10 ° C to the measurement temperature (-8.5
C.) is gradually cooled at a cooling rate of 1.degree. C./h, and the temperature is maintained for 2 hours. Then, the sample is suction filtered using a glass filter to filter out crystals, and then washed with cold acetone. The crystal thus obtained was observed under a microscope to measure its size.

(2) Simple oil passage test The low temperature filtration characteristics of the test oil were measured as follows. 35
0 ml of the test oil is put into a graduated cylinder and cooled from room temperature to the cloud point of the test oil + 10 ° C. at a cooling rate of 7.5 ° C./h. Then, from the cloud point of the test oil + 10 ° C to the measurement temperature (-8.
(5 ° C.) at a cooling rate of 1 ° C./h and then held at the measurement temperature for 2 hours, after which the plate crystals of the test oil surface layer are removed by suction, forming during cooling the oil / air interface. Avoid being affected by this test by unusually large wax crystals that have a tendency to develop. The wax that has settled in the graduated cylinder is dispersed by gently stirring, and then a CFPP filter unit is inserted. The cock is opened to reduce the pressure to 500 mmHg, and when 200 ml of the test oil passes through the filter and is stored in the calibrated receiver, the cock is closed. Pass if 200 ml of test oil is collected within 30 seconds of passing the filter of the given mesh, pass if the flow rate is too slow, indicating that the filter is blocked. The mesh size of the finally passed filter mesh was recorded.

(3) Low temperature clogging test, conducted according to JIS K-2288, low temperature clogging temperature C
FPP was determined.

(4) Pour point test The pour point PP was determined by carrying out according to JIS K-2269.

(5) Dispersibility test 100 ml of test oil was put in a 100 ml Epton tube and cooled at room temperature to the cloud point of the test oil + 10 ° C. at 7.5 ° C./h in a thermostat with program temperature control. Quenching at a speed, then from the cloud point + 10 ° C to the measured temperature (-8.5
℃) at a cooling rate of 1 ℃ / h, gradually cooled to 24
After leaving for a while, the state was observed. The judgment was performed by the ratio of the wax dispersion layer of the test oil generated by the wax precipitation and the transparent layer of the upper supernatant. The dispersibility of the wax is better as the proportion of the wax dispersion layer is larger. The proportion is 70% or more as ◯, 50% or more and less than 70% as Δ, and less than 50% as x. In addition, light oil A having the properties shown in Table 1 was used in the test.
And light oil B were used.

[0029]

[Table 1]

Production of Component (A) Production Example 1 1 mol of phthalic anhydride and 2 mol of di-hardened beef tallow alkylamine were placed in a four-necked flask of 21 and placed under a nitrogen stream at 115-115.
After heating with stirring at 125 ° C. for 1 hour, p-toluenesulfonic acid was added, and the product water was further removed under reduced pressure while heating with stirring at 145 to 155 ° C. for 5 hours. The acid value of this amidated product was 43 and the amine value was 46.

Production Example 2 1 mol of phthalic anhydride and 2 mol of di-hardened tallow alkylamine were heated at 110 to 120 ° C. for 2 hours with stirring to obtain an amide amine salt. This product had an acid value of 50 and an amine value of 53.

Production Example 3 By the same method as in Production Example 1, an amidation product of 1 mol of 2,3-naphthalenedicarboxylic acid anhydride and 2 mol of di-hardened tallow alkylamine was produced.

Production Example 4 In the same manner as in Production Example 1, an amidated product of 1 mol of 1,8-naphthalenedicarboxylic acid anhydride and 2 mol of di-hardened tallow alkylamine was produced.

Production Example 5 By the same method as in Production Example 2, an amide / amine salt of 1 mol of 2,3-naphthalenedicarboxylic acid anhydride and 2 mol of di-hardened tallow alkylamine was produced.

Production of Component (B) Production Example 6 2 mol of behenic acid and 0.5% by weight of potassium acetate were charged into an autoclave, dissolved, replaced with nitrogen, and deaerated, then 150
Reacting 10 moles of ethylene oxide at ~ 190 ° C,
A monoester polyether of polyoxyethylene behenate (average number of moles of ethylene oxide added: 4.5, hydroxyl value: 107, acid value: 2.9) was obtained. To this monoester polyether, 1 mol of adipic acid and 0.5% by weight of p-toluenesulfonic acid were added and heated under reduced pressure at 140 to 160 ° C. for 5 hours while stirring to obtain an esterified product. . The acid value of this ester was 8.5.

Production Examples 7 to 9 Polyester ethers were obtained in the same manner as in Production Example 6 using the raw materials shown in Table 2. The results are shown in Table 2.

[0037]

[Table 2]

Note 1) Abbreviations indicate the following, respectively,
The number of moles indicates the average number of moles of alkylene oxide added. EO: ethylene oxide, PO: propylene oxide,
THF: Tetrahydrofuran, EO / PO: Random addition, PO-EO: Block addition 2) Neutralization value 168.6

Production Example 10 1 mol of adipic acid and polyethylene glycol (molecular weight 2
00) 2 mol and 1% by weight of p-toluenesulfonic acid to 2
The mixture was placed in a 4-necked flask of No. 1 and heated under stirring at 120 to 130 ° C. for 3 hours under reduced pressure while removing generated water to obtain an esterified product. The acid value of this ester was 5.3. Furthermore, 2 mol of behenic acid was added to the esterified product, and the product water was removed under reduced pressure at 140 to 160 ° C.
The mixture was heated with stirring for 5 hours to obtain an esterified product. The acid value of this ester was 10.1.

Production Examples 11 to 13 Polyester ethers were obtained in the same manner as in Production Example 10 using the raw materials shown in Table 3. The results are shown in Table 3.

[0041]

[Table 3]

Note 1) Abbreviations indicate the following, respectively. EG: ethylene glycol, PO: propylene oxide, THF: tetrahydrofuran, EO: ethylene oxide, EG-EO / PO (8/2) is a random adduct of ethylene glycol with a molar ratio of EO and PO of 8/2.

Examples 1 to 16 and Comparative Examples 1 to 6 The fluidity improver having the composition shown in Table 4 was diluted with an aromatic solvent and subjected to a test as a concentrate having a concentration of 50% by weight. Add 3 parts of the concentrate to each of light oil A and light oil B shown in Table 1 above.
The test oil was added at a rate of 00 ppm, and various tests were performed on this test oil to evaluate the performance of the fluidity improver. The results are shown in Table 5.

[0044]

[Table 4]

[0045]

[Table 5]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Noriko Mimura 4-2-3 Nishihara-cho, Fuchu-shi, Tokyo Citiheim im North Isle No. 202

Claims (2)

[Claims] 1. At least one selected from (A) an amide / amine salt of an aromatic dicarboxylic acid and a long-chain alkylamine and a diamide, and (B) a general formula: (In the formula, R ¹ and R ² are each a hydrocarbon group having 6 to 29 carbon atoms, A ¹ and A ² are each an alkylene group having 2 to 4 carbon atoms, Y is a bond, or a divalent aliphatic or aromatic group. Group group, k and m are each an integer of 1 to 50, and n is 1 to 1
An additive for fuel oil, which is a mixture with a polyester derivative represented by the formula: 2. The additive for fuel oil according to claim 1, wherein the component (A) contains diamide and amide / amine salt in a weight ratio of 50:50 to 95: 5.