JPS62243686A - Fluidity improver for fuel oil - Google Patents

Abstract

PURPOSE:A fluidity improver, containing a specific polyester compound and specific polymer as essential components and capable of effectively and finely dividing wax crystals present in a fuel oil and well dispersing the crystals in the oil. CONSTITUTION:A fluidity improver, containing (A) a compound expressed by the formula [R is polyfunctional carboxylic acid (optionally having 1-3 hydroxyl groups); A is 2-4C alkylene; R' is alcohol and at least one of m R' groups is 14-30C straight-chain saturated alcohol; m is >=2; n is 1-99] and (B) a polymer, containing (i) a compound selected from the group consisting of nitrogen-containing derivatives of alkenylsuccinic acids, condensates of chlorinated paraffins with naphthalene, nitrogen-containing derivatives of long-chain alkylenedicarboxylic acids, nitrogen-containing derivatives of tricarboxylic acids and reaction products of diisocyanate compounds with dialkylamines and/or (ii) an acrylate or methacrylate having 8-30C alkyl group as essential constituent monomers and having 3,000-200,000mol.wt. as an essential component.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a fluidity improver for fuel oil, which effectively miniaturizes wax crystals present in fuel oil and improves the flowability of wax in the oil. This invention relates to a fuel oil flow improver that can be dispersed.

[Conventional technology]

When petroleum middle distillate oils, such as diesel oil and heavy oil, are exposed to low temperatures in winter or in cold regions, the wax-like substances contained therein precipitate and clog the filters in the fuel piping system of diesel engines. This causes problems such as impeding engine starting, etc., and the fuel oil itself becoming semi-solid or solid, losing its fluidity and clogging the oil pipe. This problem tends to increase further due to the recent trend toward heavier crude oil or the tighter quantity of kerosene and diesel oil, and appropriate measures to address this problem are desired.

Many studies have been conducted to solve these problems, including ethylene-vinyl acetate copolymer, ethylene-(meth)acrylate copolymer, polyethylene, halogenated polyalkylene, and alkyl (meth)acrylate. Polymers, condensates of chlorinated paraffins and naphthalene, nitrogen-containing derivatives of alkenylsuccinic acids, and aliphatic dicarboxylic acid amides have been reported. These modifiers generally improve the quality of fuel oil at low temperatures by adsorbing on or eutecticizing wax that precipitates when fuel oil is exposed to low temperatures, changing the shape and size of wax crystals. It improves liquidity.

[Problem that the invention seeks to solve]

However, in recent years, there have been changes in the demand for fuel oil, and with regard to diesel oil in particular, during times of strong demand for kerosene, etc., the proportion of low boiling point parts in diesel oil is decreasing, and the boiling point range is becoming narrower. There are situations where it is not possible. For gas oils with such narrow boiling point ranges, even if various fluidity-improving additives are added, including the conventionally used ethylene-vinyl acetate (EVA) copolymer, it is difficult to maintain good low-temperature properties. It is difficult to demonstrate fluidity.

That is, for the above fuel oil with a narrow boiling point range, CFPP
No additive has been found to improve flowability that simultaneously has the ability to effectively lower the pour point (cold filtration plugging point, IP 306) and pour point. Furthermore, it has been desired to develop additives that are effective for a wide range of types of fuel oils having various boiling point ranges.

In addition, when fuel oil to which conventional fluidity improvers are added is slowly cooled in a storage tank or drum pipe, there is a drawback that the precipitated wax does not disperse in the oil and often settles to the bottom. is desired.

[Means for solving problems]

Under these circumstances, the present inventors conducted intensive research and found that it is possible to impart good low-temperature fluidity to a wide range of types of fuel oil, that is, it is possible to lower both CFPP and PP at the same time. The present invention has been completed by discovering an additive that can disperse precipitated wax in oil and reduce sedimentation when slowly cooled.

That is, in the present invention, (al) (the following general formula N) (wherein, R is a polyvalent carboxylic acid residue, and may be a polyvalent carboxylic acid residue having 1 to 3 hydroxyl groups.A is an alkylene group having 2 to 4 carbon atoms, R' is an alcohol residue, and at least one of the m R's is a residue of a linear saturated alcohol having 14 to 30 carbon atoms. m is 2
(b-1) a nitrogen-containing derivative of alkenylsuccinic acid, a condensate of chlorinated paraffin and naphthalene, and a long-chain alkylene dicarboxylic acid. A compound selected from the group consisting of a nitrogen-containing derivative, a nitrogen-containing derivative of tricarboxylic acid, and a reaction product of a diisocyanate compound and a dialkylamine, and/or (b-2) having an alkyl group having 8 to 30 carbon atoms (meth ) A molecule that has acrylate as an essential constituent monomer! 3000
The object of the present invention is to provide a fuel oil river fluidity improver comprising a polymer of 200,000 to 200,000 as an essential component.

Component (a) in the present invention is a compound represented by the general formula (I), which can be produced, for example, as follows.

That is, (a) a polyvalent carboxylic acid having two or more carboxyl groups or/and its acid anhydride; and (b) a polyhydric carboxylic acid having two or more carboxyl groups;
It is obtained by reacting and esterifying a polyoxyalkylene ether of 30 linear saturated alcohols and, if necessary, polyoxyalkylene ethers of other alcohols. Examples of the polyhydric carboxylic acid used in this case include R-(-COO11) or/and R-+C00H)-
* (CO) io (in the formula, ■ is an integer of 2 or more,
R may contain one or more ether oxygen atoms or 1,000 onythyl sulfur atoms. In addition, R represents a hydroxyl group from 1 to
It may contain three. ). As polyhydric carboxylic acids that can be used, compounds having two or more carboxyl groups or two
Any acid anhydride obtained by dehydration from the above carboxyl group may be used. For example, divalent carboxylic acids include oxalic acid, maleic acid, maleic anhydride, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, sebacic acid, dodecanedicarboxylic acid, phthalic anhydride,
malonic acid, itaconic acid, itaconic anhydride, adipic acid,
Succinic acid, succinic anhydride, alkenyl succinic a, water alkenyl succinic acid, polybutenyl succinic anhydride, malic acid, tartaric acid, dimer acid, glutaric acid, etc.
Examples of the trivalent carboxylic acids include citric acid, trimellitic acid, trimellitic anhydride, trimeric acid, and butanetricarboxylic acid, and examples of the tetravalent carboxylic acids include pyromellitic acid and pyromellitic anhydride. Also, synthetic polycarboxylic acids can be used. Among these, preferred are di- to tetravalent polycarboxylic acids, and particularly preferred are maleic acid, maleic anhydride, adipic acid, and citric acid. Two or more of these may be used in combination.

In the general formula (R), at least one of the Ro
Examples of alcohols forming linear saturated alcohol residues having 14 to 30 carbon atoms include myristyl alcohol, palmityl alcohol, stearyl alcohol, eicosyl alcohol, behenyl alcohol, and higher alcohols using the Ziegler method. Among these, particularly preferred are stearyl alcohol and behenyl alcohol. These may be used alone or in combination of two or more. For example, a mixed alcohol obtained by reducing and hydrogenating a fatty acid obtained by hydrolyzing rapeseed fatty acid can also be used as it is.

In the general formula (I), R represents a polyvalent carboxylic acid residue, but this may have a carboxyl group that is not esterified.

In the general formula (I), if none of the m Po contains any linear saturated alcohol residue having 14 to 30 carbon atoms, CFI'P (low temperature filtration clogging point IP3
06), PP (pour point JIS K 2269) lowering effect is small.

As Ro in the general formula (I), branched alcohols and unsaturated alcohol residues can be used in addition to the above-mentioned linear saturated alcohol residues.

8 in the above general formula (I) is an alkylene group having 2 to 4 carbon atoms, that is, ethylene, propylene, butylene (I
, 2-12, 3-11, 3- and 1,4-butylene) groups are used. The form -(-OAh not only means that n pieces of one type of alkylene oxide are connected, but also means that n pieces of alkylene oxides of a plurality of types are connected at random or/and in a block shape.

8 is preferably ethylene or/and propylene, and n is preferably in the range of 1 to 99. Particularly preferred are those in which n is in the range of 1 to 60.

A specific method for producing the compound of the general formula ([) is, for example, by adding an alkylene having 2 to 4 carbon atoms to an alcohol while heating it in the presence of a catalyst such as caustic alkali, using a suitable solvent if necessary. Oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) is added in liquid or gaseous form and reacted. Random addition polymerization in which two or more alkylene oxides are mixed and reacted;
Block addition polymerization may be carried out in which alkylene oxides are sequentially added.

The obtained polyoxyalkylene ether is used as it is,
Alternatively, after removing unreacted substances and catalysts depending on the situation, a catalyst such as para-toluenesulfonic acid is usually added and esterified with a polyhydric carboxylic acid under heating. The progress of the esterification reaction can be confirmed by monitoring oxidation, hydroxyl value, saponification value, etc.

Next, component (b-1) used in the present invention will be explained. Component (b-1) is a nitrogen-containing derivative of alkenylsuccinic acid, a condensate of chlorinated paraffin and naphthalene, a nitrogen-containing derivative of long-chain alkylene dicarboxylic acid, a nitrogen-containing derivative of tricarboxylic acid, and a diisocyanate compound and dialkylamine. It is a compound selected from the group consisting of reactants (urea and/or biuret derivatives), and may be a mixture of two or more types.

As a nitrogen-containing derivative of alkenylsuccinic acid, carbon number 1
Reaction product (amide and/or salt) of alkenylsuccinic acid having 0 to 22 alkenyl groups or its anhydride and mono- or dialkylamine, (poly)alkylene polyamine
Preferred is a reaction product of an alkenylsuccinic acid or anhydride thereof having an alkenyl group having 10 to 22 carbon atoms and a dialkylamine having an alkyl group having 14 to 22 carbon atoms.

Examples of condensates of chlorinated paraffins and naphthalene include condensates of chlorinated paraffins having 8 or more carbon atoms and naphthalene. Its molecular weight is usually 2000-8000
is within the range of

Examples of the nitrogen-containing derivatives of long-chain alkylene dicarboxylic acids include those described in JP-A-56-36588. Specifically, it is a reaction product of a dicarboxylic acid having an unsubstituted or alkyl-substituted alkylene group having a linear alkylene chain having 10 or more carbon atoms and a dialkylamine, preferably a linear alkylene group having 14 to 22 carbon atoms. It is a reaction product of a dicarboxylic acid having 14 to 22 carbon atoms and a dialkylamine having two alkyl groups having 14 to 22 carbon atoms.

As a nitrogen-containing derivative of tricarboxylic acid, JP-A-56-8
Examples include those described in Japanese Patent No. 4795, specifically reaction products of aromatic, aliphatic or alicyclic tricarboxylic acids and dialkylamines, preferably trimellitic acid and alkyl having 14 to 22 carbon atoms. It is a reaction product with a dialkylamine having two groups.

Further, examples of reaction products of diisocyanate compounds and dialkylamine include those described in JP-A-56-93796. Specifically, it is a reaction product of aromatic, aliphatic or alicyclic diisocyanate and dialkylamine, preferably tolylene diisocyanate and carbon number 1.
It is a reaction product of a dialkylamine having two alkyl groups of 4 to 22.

Preferred among components (b-1) are nitrogen-containing derivatives of alkenylsuccinic acid.

The component (b-2) used in the present invention has 8 carbon atoms.
It is a polymer with a molecular fi of 3,000 to 200,000 whose essential constituent monomer is (meth)acrylate having ~30 alkyl groups, and this polymer may contain other monomers as constituent components, but in that case, The (meth)acrylate having an alkyl group having 8 to 30 carbon atoms is preferably contained in an amount of 80% by weight or more in the total monomers. Carbon number 10-2
Particularly preferred are (meth)acrylates having two alkyl groups.

(b-2) Component (meth)acrylates include octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, (meth) having a straight chain alkyl group having 8 to 28 carbon atoms, such as stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, and ophtacosyl (meth)acrylate.
Acrylates and (meth)acrylates having a branched alkyl group such as 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isocetyl (meth)acrylate, and isostearyl (meth)acrylate are mentioned.

These alkyl (meth)acrylates may be used alone or in a mixture.

Further, if necessary, it may be copolymerized with a monomer that can be copolymerized with these alkyl (meth)acrylates. However, it is desirable that the copolymer contains 80% by weight or more of alkyl (meth)acrylate.

Seven polymers that can be copolymerized with alkyl (meth)acrylates
Examples include those having a carbon-carbon double bond such as a vinyl group in the molecule, such as styrene, α-methylstyrene, α-olefin, vinyl acetate, maleic anhydride, maleic acid, acrylic acid, and methacrylic acid. acid, acrylonitrile, vinylpyridine, N-vinylpyrrolidone,
N,N-dimethylaminoethyl (meth)acrylate,
Examples include (meth)acrylamide and ethylene oxide adducts of methacrylic acid. However, this is not limited to the above description.

The copolymer may be produced in the same manner as in the case of copolymerization of general acrylic esters or methacrylic esters. For example, alkyl (meth)acrylate and other monomers, if necessary, are mixed in a hydrocarbon solvent (toluene, xylene, etc.). A small amount of a radical-generating catalyst (organic or inorganic peroxide, organic azo compound, etc.) in the presence or absence of a solvent inert to the reaction system, such as an aromatic hydrocarbon solvent, etc. It can be easily produced by heating normally to 60°C to 140°C in the presence of an inert gas atmosphere.

The number average molecular weight of component (b-2) in the present invention is usually 3
000 to 200000, preferably 100
00 to 100000. Incidentally, the number average molecular weight of component (b-2) of the present invention is determined by gel perminination chromatography.

In the present invention, when (a) and (b-1) or (a) and (b-2) are used together, the usage ratio can be set arbitrarily, but the preferred range is (a) in terms of weight ratio.
: (b-1) = 2 : 98~98 : 2 or (a)? (b-2)=2:98 to 98:2. In addition, when (a), (b-1), and (b-2) are used together, the usage ratio can be set arbitrarily,
Normal weight ratio (a): (b-1): (b-2)
= 1: 0.02~50: 0.02~50
It can be used within the range of (
a) : (b-1) : (b-2) = 1 :
o, i-10: 0.1 to 10.

The fuel oils to which the fuel oil fluidity improver of the present invention is applied are mainly distillate fuel oils and fuel oils in which distillate fuel oils are mixed with residual oils, among which preferred are kerosene, light oil, and A heavy oil. .

When adding the improver of the present invention to fuel oil, the amount added is usually 0.0001 to 0.5% (by weight, the same applies hereinafter), preferably 0.001 to 0.1%.

The fluidity improver of the present invention is a fluidity improver for a copolymer system typified by the ethylene-vinyl acetate copolymer that has been used so far, and a condensation system typified by a chlorinated paraffin-naphthalene condensate. Fuel oils with very narrow boiling point ranges, in which none of the flow improvers, nitrogen-containing derivative flow improvers typified by alkenylsuccinic acid and dialkyl amine reactants, can lower CFPP, and n −
It shows excellent cppp lowering ability and excellent PP lowering ability even at a very low addition amount for fuel oil with high paraffin content, and also for fuel oil with a relatively wide boiling point range where the effect of fluidity improving additives is easily seen. Excellent cppp lowering ability and PP
Indicates descent ability.

Furthermore, the improver of the present invention can effectively disperse wax precipitated at low temperatures in a wide range of types of fuel oils having various boiling point ranges.

As previously developed by the present inventors, the fuel oil river flow improver of the present invention has a very narrow range of CFPP in which none of the conventional fuel oil flow improvers can lower the CFPP even when using the ta) component alone. It shows excellent CFPP lowering ability and PP lowering ability for fuel oils with a boiling point range and fuel oils with high low paraffin content, and also has excellent CFPP lowering ability and pp lowering ability for fuel oils with a wide boiling point range. This shows the ability to effectively disperse wax in fuel oil that precipitates at low temperatures into the oil.

However, as a result of intensive research in order to find a more effective fuel oil fluidity improver, the present inventors found that (al component and
By using component (b-1) and/or component (b-2) in combination, superior CFP can be achieved for fuel oils with very narrow boiling point ranges and fuel oils with high n-paraffin content.
They discovered that it exhibits P lowering ability, pp lowering ability, and wax dispersion ability.

In particular, when the three components (, IIL (b-1), and (b-2) are used together), excellent CFPP lowering ability, PP lowering ability, and wax dispersion ability are exhibited.

The compound represented by the formula (]), which is the ta) component of the present invention, is an ester compound having a polyether bond in the molecule. Conventionally, the compound having a polyether bond in the molecule has the following formula: Diesters of polyoxyalkylene glycols represented by the following formula and polyesters of polyoxyalkylene ethers of alkane polyols represented by the following formula (%) are used as fluidity improvers for fuel oil. However, these compounds
Some degree of CFP for narrow boiling range distillate fuel oils
Although it exhibits P lowering ability, it is inferior in terms of CFPP lowering ability for fuel oils with a wide boiling point range, and it has almost no ability to disperse wax components in fuel oil that precipitate during slow cooling. there were.

[Effect]

The details of why the fuel oil flow improver of the present invention can impart good low-temperature flow properties and good wax dispersibility to a wide range of types of fuel oils are not known, but the following characteristics are known: It is assumed that it originates from.

That is, the ester compound of component (a) according to the present invention has a linear saturated alkyl group that is thought to have a property of adsorbing or eutectic to wax precipitated from fuel oil, and a compound that disperses wax crystals in fuel oil. The structure represented by the general formula 1←OA→-, 1 (in the formula, 8 is an alkylene group, and n represents the number of added moles), which is thought to have a function, is connected by an ether bond, so it is difficult to connect with wax. It is inferred that the eutectic occurs smoothly and the effects of the present invention are achieved.

Furthermore, the compounds of components (b-1) and (b-2) are adsorbed onto the surface of the precipitated wax crystal, thereby changing the shape of the crystal. When these components are used in combination with the (Al) component, a synergistic effect appears, making the precipitated wax crystals finer and dispersing them in the oil. Shows descending ability, pp reducing ability, and wax crystal dispersion ability.

These effects can be well understood by observing the dispersion state of wax crystals precipitated while slowly cooling fuel oil to which the improver of the present invention has been added, and by observing the state of precipitation of wax crystals using a W4M mirror. be done. Furthermore, in fact, if fuel oil to which the improver of the present invention has been added is slowly cooled to precipitate wax crystals, and then filtered through a 44 μ filter, it can be effectively filtered, and the precipitated wax crystals mostly pass through the filter. did.

As described above, since the improver of the present invention exhibits the above-mentioned effects, it is useful as a wide range of fuel oil fluidity improvers.

〔Example〕

The present invention will be specifically explained below with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples.

Note that parts in the examples are based on weight unless otherwise specified.

<Production example of component (a)> Production example 1 11! 322 g (I, 0 mol) of behenyl alcohol having a molecule of 1322 and a hydroxyl value of 174 was placed in an autoclave and dissolved by heating at a temperature of 100°C.

Next, 0.56 g (0.01 mol) of potassium hydroxide was added, and after purging the autoclave with nitrogen, the autoclave was heated at 110°C for 7
It was dehydrated by heating and depressurizing at 0 mm 1 g for 1 hour. After that, 1
React with ethylene oxide at 40-160°C for 3 hours,
I added it. The number of moles of ethylene oxide added was 4.0.

Next, ethylene oxide adduct of behenyl alcohol 49
8 g (I,0 mol), maleic acid 58.0 g (0,
5 mol) and para-toluenesulfonic acid 2.8 g (0.5 mol)
Seiyo%) II! The mixture was placed in a four-bottle flask and heated and stirred at 140 to 160° C. for 3 hours under a nitrogen stream while removing generated water to obtain an esterified product. The acid value of this ester is 3
．． It was 7.

Production Example 2 Production Q From 597.6 g (I, 2 mol) of the ethylene oxide adduct of behenyl alcohol used in Example and 76.9 g (0.4 mol) of citric acid (anhydride), Production Example I
An esterified product was obtained in the second step. The acid value of this ester is 4
．． It was 3.

Production example 3 5 moles of ethylene oxide to 1 mole of behenyl alcohol,
An esterified product was obtained according to Production Example 1 from 3 moles of the product obtained by adding 5 moles of propylene oxide and 1 mole of trimellitic acid. The acid value of this ester was 5.1.

Production Example 4 An esterified product was obtained according to Production Example 1 from 4 moles of a product obtained by adding 6 ethylene oxide molecules to 1 mole of stearyl alcohol and 1 mole of pyromellitic acid. The acid value of this ester was 6.2.

Production Example 5 1 mole of hardened rapeseed alcohol to 10% propylene oxide
An esterified product was obtained according to Production Example 1 from 2 moles of the product obtained by adding moles and 1 mole of adipic acid. The acid value of this ester was 3.7.

Production Example 6 Production from 2 moles of a product obtained by adding 5 moles of ethylene oxide to 1 mole of behenyl alcohol, 1 mole of a product obtained by adding 5 moles of ethylene oxide to 1 mole of oleyl alcohol, and 1 mole of citric acid. An esterified product was obtained according to Example 1. The acid value of this ester was 6.0.

Reference Examples 1 to 6 The esters of alkylene oxide adducts produced in Production Examples 1 to 6 were diluted with aromatic solvents to prepare 50% concentrates, which were used in the following tests.

That is, fluidity improvers containing concentrates of component (a) were blended with light oils or A heavy oils shown in Table 1, and their fluidity and dispersibility were tested.

The results are shown in Table 2.

The fluidity test is a low temperature clogging test (CFPP).

British Standard IF'-309) and pour point test (PP, J
ISK-2269).

In addition, the dispersibility test was carried out by putting 100-ml of the test oil into a graduated cylinder and placing it in a low-temperature bath with a programmable temperature controller, from room temperature to 9 points (CP) of the test oil.

JIS K-2269) was rapidly cooled at a rate of 1°C per minute to a temperature 10°C higher than the 9th point, then slowly cooled at a rate of 1°C per hour to a temperature 5°C lower than the 9th point, and left at that temperature for 2 hours. , observed the condition. Judgment was made based on the ratio of the wax-dispersed layer of the test oil produced by wax precipitation to the transparent layer of the upper supernatant. The dispersibility of wax is better as the ratio of the dispersed layer of wax is higher, and when the ratio is 70% or more, ○, 5
0% or more and less than 70% was Δ, and less than 50% was rated ×.

Comparative Examples 1 to 3 The following three types of conventionally known additives were used, and the fluidity of those blended with the light oil or A heavy oil shown in Table 1 in the same manner as Reference Examples 1 to 6 was measured. and dispersibility were tested. The results are shown in Table 2.

<Type of additive> Comparative example 1: Ethylene-vinyl acetate copolymer (number average molecule ff133
00/vinyl acetate content 32% by weight) 50%'a thick material Comparative example 2: 50% of polyethylene glycol (600) dibehenate
% Concentrate Comparative Example 3: 50% Concentrate 1 of Triester of 12 Molar Adduct of Glycerin with Ethylene Oxide and Hehenic Acid
As is clear from Table 2, the ester compounds of Reference Examples 1 to 6 have superior CFPP lil lowering ability and pp lowering ability than other conventional technologies for both narrow boiling point range light oil and wide boiling point range light oil. and wax dispersion ability. However, when the amount added is as low as 250PPat, it is still not sufficient.

Examples 1 to 8 In addition to the above component (a), (b-1) and/or (b-
2) Fuel oil fluidity improvers 1 to 8 of the present invention having the following compositions obtained by adding the components were prepared.

The obtained improvers 1 to 8 were diluted with an aromatic solvent, and 50
Light oil A, B, C or A shown in Table 1 as % concentrate
Add 250 ppn+ to heavy oil and add C in the same manner as Reference Examples 1 to 6.
FPP, PP and dispersibility were evaluated.

The results are shown in Table 3.

Fuel oil fluidity improver composition> Improver l Compound of Production Example 2 40 parts Improver 2 Compound of Production Example 2 40 parts Improver 3 Compound of Production Example 2 25 parts Improver 4 Compound of Production Example 4 25 parts Improver Agent 5 Compound of Production Example 2 25 parts Modifier 6 Compound of Production Example 2 15 parts Polyalkyl polyacrylate 0) 35 parts Modifier 7 Compound of Production Example 2 20 parts Modifier 8 Compound of Production Example 2 25 parts (Note) f) Those having an alkyl group having 16 to 18 carbon atoms. Product name Firmin D86 (manufactured by Kao Corporation) **) A copolymer of 20% by weight of acrylate with an alkyl group of 12 carbon atoms, 60% by weight of acrylate of 14, 15% by weight of acrylate of 16, and 5% by weight of vinylpyrrolidone. Molecular weight: 80.000 [Effects of the Invention] As is clear from Table 3, the fuel oil fluidity improver of the present invention is effective not only for fuel oils with narrow boiling point ranges but also for fuel oils with narrow boiling point ranges than the conventional inventions. It exhibits excellent CFPP lowering ability and I) P lowering ability even in a wide range of fuel oils at low addition amounts, and furthermore, it can disperse wax that precipitates when the fuel oil is slowly cooled into the fuel oil. be able to. This can prevent clogging of filters in the fuel piping system, clogging of oil pipes, etc.

Claims (1)

[Claims] 1. (a) The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R is a polyhydric carboxylic acid residue, and the hydroxyl group is 1 It may be a polyhydric carboxylic acid residue having ~3 carbon atoms.A is an alkylene group having 2 to 4 carbon atoms, R' is an alcohol residue, and m
At least one of the R's is a residue of a linear saturated alcohol having 14 to 30 carbon atoms. m is an integer of 2 or more, n
is an integer from 1 to 99. ) and (b-1) nitrogen-containing derivatives of alkenylsuccinic acids, condensates of chlorinated paraffins and naphthalene, nitrogen-containing derivatives of long-chain alkylene dicarboxylic acids, nitrogen-containing derivatives of tricarboxylic acids, and diisocyanates. A compound selected from the group consisting of a reaction product of a compound and a dialkylamine, and/or (b-2) a (meth)acrylate having an alkyl group having 8 to 30 carbon atoms as an essential constituent monomer with a molecular weight of 3000 to 200,000 polymer as an essential component. 2. (a) and (b-1) or (a) and (b-2)
2. The fluidity improver for fuel oil according to claim 1, wherein the weight ratio of . 3. The fuel according to claim 1, wherein the weight ratio of (a), (b-1), and (b-2) is 1:0.1 to 10:0.1 to 10. Fluidity improver for oil. 4. The nitrogen-containing derivative of alkenylsuccinic acid has 10 carbon atoms.
The fluidity improver for fuel oil according to claim 1, which is a reaction product of an alkenylsuccinic acid having ~22 alkenyl groups or its anhydride and a dialkylamine whose alkyl group has 14 to 22 carbon atoms. .