JP6602349B2 - Fluidity improver and fuel oil composition - Google Patents

Description

  The present invention relates to a fluidity improver and a fuel oil composition containing the fluidity improver.

  Petroleum middle distillates, such as diesel fuel oil and A heavy oil, when exposed to low temperatures (eg, 0 ° C. to −30 ° C.) in winter or in cold regions, the wax contained therein precipitates, and the piping system Problems occur due to clogging of the filter or solidification in the piping system. In order to solve these problems related to fluidity at low temperatures, many methods for adding an ethylene-unsaturated carboxylic acid vinyl ester copolymer to a base oil have been proposed (for example, Patent Documents 1 to 3). reference). Moreover, as what improves these low-temperature fluidity | liquidity, the ethylene / vinyl acetate / 2-ethylhexanoic acid vinyl copolymer (for example, patent documents 4-6) etc. is proposed. On the other hand, in recent years, from the viewpoint of reducing environmental burden and suppressing flue corrosion, the reduction of sulfur in residual oil that is a heavy oil base material has been studied, and a heavy oil composition using such a low sulfur base material. Things are being sought. However, in what is proposed in the above patent document, fuel oil (light oil) with a high wax content and low sulfur content, residual carbon content, atmospheric residue oil, vacuum residue oil, catalytic cracking residue oil, pyrolysis residue For heavy fuel oils (A heavy oil) containing heavy base materials such as oil and desulfurized heavy oil, the amount of addition required to improve low-temperature fluidity is significantly increased. There was a problem that oiliness deteriorated.

Japanese Patent Laid-Open No. 39-200692 Japanese Patent Publication No. 48-23165 JP 59-136391 A Japanese National Patent Publication No. 10-506134 JP-T-2001-512780 JP-T-2001-512781

  The present invention provides a fluidity improver capable of greatly improving low-temperature fluidity with a small amount of addition to not only low sulfur fuel oil but also heavy fuel oil containing residual carbon and heavy base material, and It aims at providing the low fuel oil composition containing a fluidity improver.

As a result of intensive studies, the present inventor has reached the present invention. That is, the present invention is a fluidity improver shown below; a fuel oil composition comprising 10 to 1000 ppm of the fluidity improver based on the weight of the fuel oil.
A fluidity improver comprising a copolymer (A1), a copolymer (A2) and a copolymer (B), wherein (A1) and (A2) are ethylene (a1) and an aliphatic saturated carboxylic acid. It is a copolymer having an aliphatic saturated carboxylic acid vinyl ester (a2) having 2 to 24 carbon atoms as an essential constituent monomer, and (A1) is a copolymer satisfying all of the following (I) to (III). (A2) is a copolymer satisfying all of the following (IV) to (VI), and (B) is an aromatic hydrocarbon monomer (b1) and a nitrogen atom-containing monomer (b2). ) Is an essential constituent monomer, and (B) is a copolymer satisfying all of the following (VII) to (IX).
(I) The weight average molecular weight is 3,000 to 100,000.
(II) Solubility parameter is 8.5 to 10.0 (cal / cm ³ ) ^1/2
(III) Crystallization start temperature by differential operation calorimeter is 60 ° C. or higher and 80 ° C. or lower (IV) Weight average molecular weight is 3,000 to 100,000
(V) Solubility parameter is 8.5 to 10.0 (cal / cm ³ ) ^1/2
(VI) Crystallization start temperature by differential operation calorimeter is 30 ° C. or higher and lower than 60 ° C. (VII) Weight average molecular weight is 10,000 to 300,000
(VIII) Solubility parameter is 8.5 to 10.0 (cal / cm ³ ) ^1/2
(IX) Crystallization start temperature by differential operation calorimeter is -20 ° C or higher and lower than 30 ° C

  The fluidity improver of the present invention is superior to conventional low-sulfur fuel oils and heavy fuel oils in improving the low-temperature fluidity, and CFPP (cold filter clogging point) and PP (pour point) can be added in a small amount. Can be lowered. In particular, the conventional fluidity improver is effective for light oil having a low wax content with a high wax content and A heavy oil, for which it was difficult to improve low temperature fluidity.

  In the present invention, the copolymer (A1) and the copolymer (A2) are each an aliphatic saturated carboxylic acid vinyl ester (a2) having 2 to 24 carbon atoms of ethylene (a1) and an aliphatic saturated carboxylic acid. Are essential constituent units.

As the aliphatic saturated carboxylic acid vinyl ester (a2) having 2 to 24 carbon atoms of the aliphatic saturated carboxylic acid in the copolymer (A1), a primary aliphatic saturated carboxylic acid [linear aliphatic saturated carboxylic acid ( Acetic acid, n-propionic acid, n-hexanoic acid, n-decanoic acid, n-dodecanoic acid, palmitic acid, stearic acid, behenic acid, etc.)], branched secondary aliphatic saturated carboxylic acid (2-ethylhexanoic acid, etc.) And vinyl esters of branched tertiary aliphatic saturated carboxylic acids (neononanoic acid, neodecanoic acid, neododecanoic acid, etc.).
Specific examples of (a2) include vinyl acetate, vinyl propionate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl neodecanoate, vinyl decanoate, vinyl dodecanoate, vinyl palmitate and vinyl stearate. .
Of (a2), from the viewpoints of solubility of the copolymer (A1) in fuel oil and low-temperature fluidity, aliphatic saturation in which vinyl acetate and aliphatic saturated carboxylic acid have 3 to 20 carbon atoms is preferred. The vinyl acetate is used in combination, and the proportion of vinyl acetate in the combined use is 50 mol% or more, preferably 80 mol% or more of the whole (a2).

(A1) is a constituent monomer, and further, an unsaturated dicarboxylic acid ester (a3) and / or a linear or branched alkyl group having 4 to 22 carbon atoms of the alkyl group in that the low temperature fluidity is improved. It is preferable to contain the alkyl (meth) acrylate (a4) whose carbon number is 1-32.
Examples of (a3) include maleic acid mono- or dialkyl esters and fumaric acid mono- or dialkyl esters having an alkyl group having 4 to 24 carbon atoms in the alkyl group. Of these, from the viewpoint of easy adjustment of the crystallization temperature of the polymer, the alkyl group preferably has an alkyl group having 4 to 18 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms. It is a maleic acid dialkyl ester or a fumaric acid dialkyl ester having a group.
Examples of (a4) include methyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, and dodecyl (meth). Acrylate, isododecyl (meth) acrylate, tridecyl (meth) acrylate, isotridecyl (meth) acrylate, tetradecyl (meth) acrylate, isotetradecyl (meth) acrylate, pentadecyl (meth) acrylate, isopentadecyl (meth) acrylate, hexadecyl ( (Meth) acrylate, 2-octyldecyl (meth) acrylate, octadecyl (meth) acrylate, 2-octyldodecyl (meth) acrylate, 2-decyltetradecyl (meta) Acrylate, 2-hexadecyl octadecyl (meth) acrylate and 2-tetradecyl-octadecyl (meth) acrylate. Among these, from the viewpoint of easy adjustment of the crystallization temperature of the polymer, the linear or branched alkyl (meth) acrylate having a linear or branched alkyl group having 4 to 28 carbon atoms is preferable, and more preferably straight. It is a linear or branched alkyl (meth) acrylate in which the chain or branched alkyl group has 8 to 24 carbon atoms.

(A1) may further contain a radical polymerizable monomer (a5) other than (a1) to (a4) as a constituent monomer.
Examples of (a5) include the following monomers.
Aliphatic vinyl hydrocarbons such as propylene, butene, isobutylene, pentene, 4-methylpentene-1, hexene, octene, decene, dodecene and tetradecene; alicyclic vinyl hydrocarbons such as cyclohexene and (di) cyclopentadiene; And hydroxyl group-containing vinyl monomers such as hydroxystyrene, N-methylol (meth) acrylamide and hydroxyethyl (meth) acrylate; and vinyl monomers having a polyalkylene glycol chain.

  The mol% of ethylene (a1) in the monomer constituting (A1) is preferably 80 to 90 mol%, more preferably 82 to 89 mol based on the total number of moles of the monomer constituting (A1). %, Particularly preferably 83 to 88 mol%, most preferably 84 to 87 mol%. If it is 80 mol% or more, the low temperature fluidity is good, and if it is 90 mol% or less, the low temperature fluidity and oil permeability are good. The mol% of (a2) is preferably 3 to 20 mol%, more preferably 4 to 18 mol%, most preferably 5 to 15 mol% based on the total number of moles of the monomers constituting (A1). is there. The total mol% of (a3) and (a4) is preferably 15 mol% or less, more preferably 1 to 13 mol%, still more preferably 3 based on the total number of moles of the monomers constituting (A1). ~ 11 mol%. The mol% of (a5) is preferably 5 mol% or less, more preferably 3 mol% or less.

  From the viewpoint of adjusting the crystallization start temperature of (A1) to the following predetermined range and from the viewpoint of solubility in fuel oil, (A1) may contain (a3) or (a4) as its constituent monomer. preferable.

  Specific examples of (A1) include ethylene / vinyl acetate / di-n-butyl maleate (molar ratio 85/6/9) copolymer, ethylene / vinyl acetate / 2-ethyl hexanoate / dibutyl maleate (mol). Ratio 84/6/10) copolymer, ethylene / vinyl acetate / vinyl neodecanoate / di-2-ethylhexyl fumarate (molar ratio 85/5/1/9) copolymer, ethylene / vinyl acetate / n-dodecylmeta Examples include acrylate (molar ratio 88/7/5) copolymer and ethylene / vinyl acetate / n-tetradecyl methacrylate copolymer (molar ratio 88/7/5).

The weight average molecular weight (hereinafter abbreviated as Mw) of (A1) is 3,000 to 100,000, preferably 4,000 to 50,000, more preferably 5,000 to 30,000. If it is less than 3,000, the low-temperature fluidity of the fuel oil is lowered, and if it exceeds 100,000, the solubility in the fuel oil is deteriorated and cannot be used for the fuel oil.
In addition, Mw and Mn of (A1), the copolymer (A2), the copolymer (B), and the oil-soluble phenol resin (C) described later are measured by gel permeation chromatography under the following conditions.
<Measurement conditions of molecular weight of (A)>
Apparatus: “HLC-802A” [manufactured by Tosoh Corporation]
Column: 2 “TSK gel GMH6” Measurement temperature: 40 ° C.
Sample solution: 0.5 wt% tetrahydrofuran solution Solution injection amount: 200 μl
Detector: Refractive index detector Standard: Polystyrene

The solubility parameter (hereinafter abbreviated as SP value) of (A1) is 8.5 to 10.0 (cal / cm ³ ) ^1/2 from the viewpoint of solubility in fuel, preferably 8.7 to 9.5 (cal / cm ³ ) ^1/2 . If it is less than 8.5 or more than 10.0, the solubility in fuel oil becomes poor and it cannot be used for fuel oil.
In the present invention, the SP values of the copolymer (A1), the copolymer (A2) and the copolymer (B) described later are the monomers constituting the respective copolymers (hereinafter referred to as “constituent monomer”). SP value of the homopolymer for each (denoted as a body) was calculated by the method described in the Fedors method (Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154). It is the total value of the values obtained by multiplying the SP value of the homopolymer of the constituent monomer by the mole fraction of the constituent monomer in each copolymer.
The SP value of (A1), the copolymer (A2) and the copolymer (B) to be described later is in a desired range by appropriately adjusting the SP value and the molar fraction of the homopolymer of the monomer used. Can be.

The crystallization start temperature measured by the differential scanning calorimeter of (A1) is 60 ° C. or higher and 80 ° C. or lower, preferably 62 ° C. or higher and 77 ° C. or lower, more preferably 65 ° C. or higher and 75 ° C. or lower.
When the temperature is lower than 60 ° C., the low temperature fluidity with respect to the heavy fuel oil is deteriorated, and when it is higher than 80 ° C., the solubility in the heavy fuel oil is deteriorated.
In the present invention, the crystallization start temperature of (A1), the copolymer (A2) and the copolymer (B) described later is a differential scanning calorimeter “UNIX (registered trademark) DSC7” (manufactured by PERKIN-ELMER). The crystallization onset temperature observed when 5 mg of sample is used and cooled from 100 ° C. to −60 ° C. at a constant rate of 10 ° C./min.

  The copolymer (A2) is a copolymer having ethylene (a1) and the above-mentioned (a2) as essential constituent monomers, and (A2) is a constituent monomer other than (a1) and (a2). The aforementioned monomers (a3) to (a5) may be included.

  The content of ethylene (a1) in the monomer constituting (A2) is preferably lower than the content of ethylene (a1) in the monomer constituting (A1). The total content of monomers (a2) to (a5) other than ethylene (a1) in the constituting monomer is the monomer (a2) other than ethylene (a1) in the monomer constituting (A1). It is preferable to make it larger than the total content of (a5). Thereby, the crystallization start temperature of (A2) can be adjusted to a crystallization start temperature lower than (A1).

The degree of branching of (A2) calculated by ¹ H-NMR measurement of the following method is preferably 0.3 to 6.0%, more preferably 0.3 to 5.0%, and particularly preferably 0.4. -3.0%.
If it is 0.3% or more, the solubility in the fuel oil is further improved, so that the oil permeability is easily improved, and if it is 6.0% or less, the low-temperature fluidity can be further improved.

The degree of branching of (A2) can be adjusted by the temperature and pressure during polymerization, the amount of polymerization initiator, and the like.
In order to adjust the degree of branching of (A2) to 0.3 to 6.0%, the polymerization temperature during polymerization is 110 to 160 ° C., the pressure is 100 to 300 MPa, and the amount of polymerization initiator is based on the total amount of monomers. And preferably 0.01 to 0.1% by weight.

The degree of branching is a numerical value representing the number of branch points per 100 methylene. A methylene having no branching point has a branching degree of 0%, and a methylene having all branching points has a branching degree of 100%. The branch in the present invention is a structure obtained by adding ethylene among the structures of (A2), and a part of hydrogen atoms of the ethylene structure is a methyl group (hereinafter, branched methyl). It is a structure formed by chain transfer that occurs during the polymerization reaction of (A2).
The degree of branching in the present invention can be determined by ¹ H-NMR. For example, in the case of a copolymer of ethylene and vinyl acetate, an integrated value [1] of peak shift of 0.8 to 0.9 ppm (derived from a branched methyl group) and an integrated value of peak shift of 1.0 to 1.9 ppm [2] (derived from vinyl methine of ethylene and vinyl acetate), integrated value of peak shift around 2.0 ppm [3] (derived from acetylmethyl group of vinyl acetate) and integrated value of peak shift from 4.7 to 5.0 ppm It can be calculated by the following formula from [4] (derived from vinyl methine of vinyl acetate).
Branching degree (%) = [1] / 3 ÷ {([2] − [1] / 3) / 2 + [1] / 3 + [4]} × 100
When fatty acid vinyl other than vinyl acetate is contained, the peak derived from the fatty acid group may overlap with [1] and [2]. In that case, the intensity [5] (2.0 to 2.3 ppm) of the peak of the proton bonded to the carbon adjacent to the carbonyl group of the fatty acid group and the integrated value [4 of the peak shift of 4.7 to 5.0 ppm] ] (Derived from vinyl methine of fatty acid vinyl), the content of fatty acid vinyl can be obtained, and the absorption of fatty acid groups overlapping [1] and [2] can be calculated from the molar ratio. When 1-olefin other than ethylene is contained, since ¹ H-NMR makes it difficult to distinguish between branched and 1-olefin, the copolymerization ratio of 1-olefin is calculated from the charged amount and the reaction rate during polymerization, It can be calculated by subtracting the absorption of the 1-olefin side chain overlapping with [1] and [2] from the molar ratio.

  In (A2), the mol% of ethylene (a1) with respect to the total number of moles of the monomers constituting (A2) is preferably 80 to 88 mol%, more preferably 81 to 87 mol%, and particularly preferably 82 to 87 mol%, most preferably 82-86 mol%. If it is less than 80 mol%, the low temperature fluidity to fuel oil will deteriorate, and if it exceeds 88 mol%, the low temperature fluidity to fuel oil will deteriorate and oil permeability will also fall. The mol% of (a2) is preferably 12 to 20 mol%, more preferably 10 to 18 mol%, particularly preferably 12 to 17 mol%, based on the total number of moles of the monomers constituting (A2). is there. When the mol% of (a2) is 12 to 20 mol%, the low temperature fluidity and oil permeability to the fuel oil are good, which is preferable. The total mole% of (a3), (a4) and (a5) is 10 mole% or less, preferably 5 mole% or less, more preferably 3 moles based on the total mole number of the monomers constituting (A2). % Or less.

  From the viewpoint of adjusting the crystallization start temperature of (A2) to the following predetermined range and from the viewpoint of solubility in fuel oil, (A2) is (a1) and two or more (a2) as constituent monomers. It is preferable to contain.

  Specific examples of (A2) include ethylene / vinyl acetate (molar ratio 85/15) copolymer, ethylene / vinyl acetate / vinyl neodecanoate (molar ratio 82/3/15) copolymer, ethylene / vinyl acetate / Vinyl neodecanoate (molar ratio 84/15/1) copolymer, ethylene / vinyl acetate / 2-ethylhexanoic acid vinyl (molar ratio 83/15/2) copolymer and ethylene / vinyl acetate / 4-methylpentene 1 copolymer (molar ratio 82/16/2) and the like.

  Mw of (A2) is preferably 3,000 to 100,000, more preferably 4,000 to 50,000, and particularly preferably 5,000 to 30,000. By setting it to 3,000 or more, the low-temperature fluidity is further improved, and by setting it to 50,000 or less, the solubility in the base oil is further improved.

The SP value of the copolymer (A2) is preferably 8.5 to 10.0 (cal / cm ³ ) ^1/2 , more preferably 8.7 to 9.5, from the viewpoint of solubility in fuel. (Cal / cm ³ ) ^1/2 .
The SP value of (A2) is calculated based on the SP value of each monomer constituting (A2) by the above method, and the SP value of each monomer is based on the mole fraction of the constituent monomer units. The average value.
The SP value of (A2) can be adjusted to a desired range by appropriately adjusting the SP value and the mole fraction of the monomer used.

(A2) has a crystallization start temperature measured by a differential scanning calorimeter of 30 ° C. or higher and lower than 60 ° C., preferably 35 ° C. or higher and 57 ° C. or lower, more preferably 40 ° C. or higher and 54 ° C. or lower.
When the crystallization start temperature is 30 ° C. or more and less than 60 ° C., the low-temperature fluidity with respect to the low sulfur fuel oil is good, which is preferable from the viewpoint of solubility in the low sulfur fuel oil.

The copolymer (B) is a copolymer having the aromatic hydrocarbon-containing monomer (b1) and the nitrogen atom-containing monomer (b2) as essential constituent monomers.
(B1) includes styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, 4-ethylstyrene, 4-isopropylstyrene, 4-butylstyrene, 4-phenylstyrene, 4-cyclohexylstyrene, 4- Examples include benzylstyrene, 4-crotylbenzene, indene, 2-vinylnaphthalene, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like.
Among these, styrene, α-methylstyrene, benzyl (meth) acrylate, and phenoxyethyl (meth) acrylate are preferable from the viewpoint of easy adjustment of the SP value and the crystallization temperature of the copolymer (B).

  Examples of the nitrogen atom-containing monomer (b2) include the following monomers (b21) to (b24).

Amide group-containing monomer (b21):
(Meth) acrylamide, monoalkyl (meth) acrylamide [one having an alkyl group having 1 to 4 carbon atoms bonded to a nitrogen atom; for example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (Meth) acrylamide and Nn- or isobutyl (meth) acrylamide etc.], N- (N′-monoalkylaminoalkyl) (meth) acrylamide [one alkyl group having 1 to 4 carbon atoms bound to the nitrogen atom. Those having an aminoalkyl group (2 to 6 carbon atoms); for example, N- (N′-methylaminoethyl) (meth) acrylamide, N- (N′-ethylaminoethyl) (meth) acrylamide, N- (N ′ -Isopropylamino-n-butyl) (meth) acrylamide and N- (N'-n- or isobutylamino-n-butyl) ) (Meth) acrylamide etc.], dialkyl (meth) acrylamide [nitrogen atom having two C1-C4 alkyl groups bonded; for example, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meta ) Acrylamide, N, N-diisopropyl (meth) acrylamide and N, N-di-n-butyl (meth) acrylamide etc.], N- (N ′, N′-dialkylaminoalkyl) (meth) acrylamide [aminoalkyl group Having an aminoalkyl group (2 to 6 carbon atoms) in which two alkyl groups having 1 to 4 carbon atoms are bonded to the nitrogen atom of, for example, N- (N ′, N′-dimethylaminoethyl) (meth) acrylamide, N- (N ′, N′-diethylaminoethyl) (meth) acrylamide, N- (N ′, N′-dimethylaminopropyl) (meth) acrylic And N- (N ′, N′-di-n-butylaminobutyl) (meth) acrylamide etc.]; N-vinylcarboxylic acid amide [N-vinylformamide, N-vinylacetamide, N-vinyl-n- or Isopropionic acid amide, N-vinylhydroxyacetamide and the like] and the like.

Nitro group-containing monomer (b22):
4-nitrostyrene etc. are mentioned.

Primary to tertiary amino group-containing monomer (b23):
Primary amino group-containing monomer {C3-C6 alkenylamine [(meth) allylamine, crotylamine, etc.], Aminoalkyl (C2-C6) (meth) acrylate [Aminoethyl (meth) acrylate, etc.}} Secondary amino group-containing monomer {monoalkylaminoalkyl (meth) acrylate [having an aminoalkyl group (2 to 6 carbon atoms) in which one alkyl group having 1 to 6 carbon atoms is bonded to a nitrogen atom; Nt-butylaminoethyl (meth) acrylate and N-methylaminoethyl (meth) acrylate, etc.], C6-C12 dialkenylamine [di (meth) allylamine, etc.]}; tertiary amino group-containing single amount Body {dialkylaminoalkyl (meth) acrylate [an aminoalkyl group in which two alkyl groups having 1 to 6 carbon atoms are bonded to a nitrogen atom (carbon Having 2 to 6); for example, N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate, etc.], alicyclic (meth) acrylate having a nitrogen atom [morpholinoethyl ( Meth) acrylates, etc.], aromatic monomers [N- (N ′, N′-diphenylaminoethyl) (meth) acrylamide, N, N-dimethylaminostyrene, 4-vinylpyridine, 2-vinylpyridine, N -Vinyl pyrrole, N-vinyl pyrrolidone, N-vinyl thiopyrrolidone, etc.]} and their hydrochlorides, sulfates, phosphates or lower alkyl (C1-8) monocarboxylic acids (such as acetic acid and propionic acid) Examples include salts.

Nitrile group-containing monomer (b24):
Examples include (meth) acrylonitrile.

  Of (b2), (b21) and (b23) are preferred, and N- (N ′, N′-diphenylaminoethyl) (meth) acrylamide and N- (N ′, N′-dimethyl) are more preferred. Aminoethyl) (meth) acrylamide, N- (N ′, N′-diethylaminoethyl) (meth) acrylamide, N- (N ′, N′-dimethylaminopropyl) (meth) acrylamide, N, N-dimethylaminoethyl (Meth) acrylate and N, N-diethylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate and N-vinylpyrrolidone.

(B) may further contain the aforementioned monomers (a3) to (a5) other than (a1) and (a2) as constituent monomers.
When (B) further contains monomers (a3) to (a5) as constituent monomers, among (a3) to (a5), it is preferable from the viewpoint of easy adjustment of the crystallization temperature of the polymer. Is (a4), more preferably a linear or branched chain having 4 to 28 carbon atoms, particularly preferably a linear or branched alkyl (meth) acrylate having 8 to 24 carbon atoms.

The content of (b1) based on the total weight of the monomers constituting (B) is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, and the content of (b2) is preferably Is from 1 to 30% by weight, more preferably from 2 to 20% by weight. The total content of (a3) to (a5) is preferably based on the total weight of the monomers constituting (B). Is 30 to 94% by weight, more preferably 50 to 88% by weight.
Satisfying all of the above contents is preferable from the viewpoint of easily forming a co-crystal with a crystalline substance or residual carbon in the fuel oil and improving the low-temperature fluidity of the fuel oil.

  Specific examples of (B) include styrene / N, N-dimethylaminomethyl methacrylate / linear or branched alkyl methacrylate (molar ratio 14/3/83) copolymer having 12 to 24 carbon atoms, styrene / N, N. -Dimethylaminoethyl methacrylate / C12-24 linear or branched alkyl methacrylate (molar ratio 10/5/85) copolymer, styrene / N- (N ', N'-dimethylaminoethyl) methacrylamide / carbon A linear or branched alkyl methacrylate having a number of 12 to 24 (molar ratio 5/10/85) copolymer, a styrene / morpholinoethyl methacrylate / a linear or branched alkyl methacrylate having a carbon number of 12 to 24 (molar ratio 10/2/88) ) Copolymer and styrene / N-vinylpyrrolidone / C12-24 linear or branched al Like methacrylate (molar ratio 10/3/87).

  The Mw of (B) is preferably 10,000 to 300,000, more preferably 20,000 to 200,000, and particularly preferably 30,000 to 150,000. Satisfying the above range is preferable from the viewpoints of solubility in fuel oil, easy formation of co-crystals with crystalline substances and residual carbon in the fuel oil, and improvement in low-temperature fluidity of the fuel oil.

The SP value of the copolymer (B) is preferably 8.5 to 10.0 (cal / cm ³ ) ^1/2 and more preferably 8.7 to 9.5 from the viewpoint of solubility in fuel. (Cal / cm ³ ) ^1/2 .
The SP value of (B) is calculated based on the SP value of each monomer constituting (B) by the above method, and the SP value of each monomer is based on the mole fraction of the constituent monomer units. The average value.
The SP value of (B) can be adjusted to a desired range by appropriately adjusting the SP value and the mole fraction of the monomer used.

In (B), the crystallization start temperature measured by a differential scanning calorimeter is -20 ° C or higher and lower than 30 ° C, preferably -15 ° C or higher and 25 ° C or lower, more preferably -10 ° C or higher and 20 ° C or lower.
A crystallization start temperature of −20 ° C. or higher and lower than 30 ° C. is preferable from the viewpoint of improving low-temperature fluidity with respect to fuel oil containing residual carbon.

  The crystallization start temperature of (B) is such that the Mw of (B) is in the range of 10,000 to 300,000, and the mol% of (b1) and (b2) in (B) and (a3) to (a5) By adjusting the mol% of the monomer containing an alkyl group (preferably adjusted to the above preferable range), the predetermined range can be obtained.

The copolymers (A1), (A2) and (B) of the present invention can be obtained by a known method. For example, it can be obtained by radical polymerization of the vinyl monomers in a solvent or without a solvent. In this case, as the polymerization initiator, azo initiators (for example, azobisisobutyronitrile, azobisvaleronitrile, etc.) and peroxide initiators (for example, diisopropyl percarbonate, benzoyl peroxide, cumyl peroxide) Lauryl peroxide, di-t-butyl peroxide, etc.) can be used. Solvents include aliphatic hydrocarbons (hexane, heptane, octane, cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, ethylbenzene, C9 aromatic mixed solvents (mixtures of trimethylbenzene, ethyltoluene, etc.), carbon -10 to 11 aromatic mixed solvents etc.], ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) and the like. These polymerization solvents can be distilled off after completion of the polymerization, but the polymers (A1), (A2) and (B) can also be used as solutions. In order to reduce the degree of branching of (A2), it is effective to lower the polymerization temperature (30 to 200 ° C., preferably 30 to 160 ° C.) and use a chain transfer agent in combination. As chain transfer agents, known mercaptans (such as butyl mercaptan and lauryl mercaptan), secondary alcohols (such as isopropyl alcohol and sec-butanol), aromatic compounds (such as toluene, xylene, cumene) and aldehydes (such as propionaldehyde) Etc. can be used.
In the present invention, (A1) and (A2) do not necessarily need to copolymerize the monomers themselves, but polymerize monomers that can be derived into the desired copolymers (A1) and (A2). Then, it can be induced to the target (A1) and (A2) by further reaction. For example, after ethylene and vinyl acetate are polymerized by the above-mentioned known method, this is hydrolyzed and further reacted with a branched aliphatic carboxylic acid having 5 to 24 carbon atoms, an acid halide or an acid anhydride thereof, and the desired ethylene. You may derive | lead to the copolymer which consists of a vinyl ester of C5-C24 branched aliphatic carboxylic acid. Further, after butadiene is copolymerized, it may be hydrogenated to form ethylene units, or after vinyl acetate is copolymerized, it may be derived into a branched aliphatic vinyl carboxylate unit by a transesterification reaction.

The fluidity improver of the present invention may further contain one or more selected from the group consisting of an oil-soluble phenol resin (C), a wax dispersant (D), and a hydrocarbon solvent (E) as necessary.
Examples of the oil-soluble phenol resin (C) include a condensate of an alkylphenol with an aldehyde or an alkylated product of a condensate with a phenol aldehyde.
Examples of the aldehyde used herein include aliphatic aldehydes having 1 to 4 carbon atoms, such as formaldehyde, acetaldehyde, butyraldehyde, and preferably formaldehyde.
Alkylphenols in the case of condensation of alkylphenols with aldehydes are, for example, n-, sec- and tert-butylphenol, n- and isopentylphenol, n- and isohexylphenol, n- and isooctylphenol, n- and isononylphenol, Examples include n- and isodecylphenol, and n- and isododecylphenol, preferably n- and nonylphenol and n- and isodecylphenol.
In the case of condensation of alkylphenol with aldehyde, the molar amount of aldehyde charged per mole of alkylphenol is preferably 0.5 to 2 moles, more preferably 0.7 to 1.3 moles, and particularly preferably 1 mole.
The number average molecular weight (Mn) of (C) is preferably 400 to 10,000, more preferably 400 to 5,000.

The wax dispersant (D) is an oil-soluble compound having a nitrogen atom in the molecule.
The Mw of (D) is not particularly limited, and may be a single compound or a so-called polymer compound. Preferably it is 200-200,000, More preferably, it is 500-30,000.
(D) includes amine compounds, amide compounds, carboxylic acid amine salts, monoalkylamines, dialkylamine or trialkylamine salts of carboxylic acids having 6 to 36 carbon atoms, carboxylic acid imides, and quaternary ammonium carboxyls. Examples include acid salts, amino acids, and low molecular weight urethane compounds.
Of these, amine-based compounds, amide-based compounds and amines are preferred from the viewpoint that oil-solubility is easily obtained and fluidity-improving effects are easily exhibited in combination with (A1), (A2) and (B). It is salt. In the present invention, “oil-soluble” means that 1% by weight or more is dissolved transparently in a 25 ° C. light oil hydrocarbon solvent.

  Preferable (D) includes the following oil-soluble nitrogen-containing low molecular compound (D1) having an Mw of 1,000 or less and the following oil-soluble nitrogen-containing polymer compound (D2) having an Mw of 1,000 or more.

(D1) oil-soluble nitrogen-containing low molecular weight compound (D11) amine compound;
Mono-, di- and trialkylamines having 1 to 36 carbon atoms, mono-, di- and trialkanolamines having 2 to 36 carbon atoms and the like.
(D12) an amide compound;
C6-C36 carboxylic acid amide, N-monoalkyl carboxylic acid amide, N, N-dialkyl carboxylic acid amide, etc.
(D13) Carboxylic acid amine salt Monoalkylamine, dialkylamine or trialkylamine salt of a carboxylic acid having 6 to 36 carbon atoms in total.
In addition, carboxylic acid imides, quaternary ammonium carboxylates, amino acids, low molecular weight urethane compounds and the like can be mentioned.

(D2) oil-soluble nitrogen-containing polymer compound (D21) amino group-containing polymer compound;
A polymer having a vinyl monomer having an amino group as an essential constituent monomer, and examples of the vinyl monomer having an amino group include the amino group-containing vinyl monomers mentioned in the above (b2), and other monomers. And a copolymer thereof.
(D22) an amide group-containing polymer compound;
A polymer having a vinyl monomer having an amide group as an essential constituent monomer, and the vinyl monomer having an amide group includes, in addition to the amide group-containing vinyl monomers mentioned in the above (b2), a maleic acid diester. (N, N-dialkyl) amide and the like are exemplified, and may be a copolymer with another monomer.
The amide group-containing polymer compound is obtained by amidating a polymer having a carboxyl group-containing monomer such as (meth) acrylic acid, (anhydrous) maleic acid and fumaric acid as an essential constituent monomer with an alkylamine. A high molecular compound may be sufficient.
(D23) an amine base-containing polymer compound;
A polymer having a vinyl monomer having an amine base as an essential constituent monomer, and the vinyl monomer having an amine base contains carboxyl groups such as the above-mentioned (meth) acrylic acid, (anhydrous) maleic acid and fumaric acid An amine salt of a monomer (mono, di or trialkylamine etc. is exemplified as an amine salt), and a copolymer with another monomer may be used.
Further, the amine base-containing polymer compound may be a polymer compound obtained by subjecting a polymer having the above-mentioned carboxyl group-containing monomer as an essential constituent monomer to amine conversion with a mono-, di- or trialkylamine. .

  Of the above (D1) and (D2), the group represented by the general formula (1) or the general group is preferable from the viewpoint of the effect of improving fluidity when used in combination with (A1), (A2) and (B). It is a compound which has at least 1 sort (s) of the counter ion shown by Formula (2).

Here, R < ¹ > and R < ² > show a C8-24 saturated aliphatic hydrocarbon group.
However, R ¹ and R ² may be the same or different. When R ¹ and / or R ² has 8 or more carbon atoms, oil solubility is easily exhibited and sludge is hardly generated. Moreover, since R ¹ or R ² is not unsaturated but a saturated hydrocarbon group, the oxidation stability is good.
R ¹ and R ² are preferably straight-chain from the viewpoint of fluidity improving effect, and at least one of them preferably has 14 to 24 carbon atoms.

Examples of the compound having the group represented by the general formula (1) include di- and trialkylamines in the above (D11), dialkylaminoalkyl (meth) acrylate or dialkylaminoalkyl (meth) acrylamide in (D21). And a polymer compound having an N, N-dialkylcarboxylic acid amide in (D12) and a polymer compound having an N, N-dialkylamide group in (D22). It is done.
As the compound having a counter ion represented by the general formula (2), the dialkylamine salt in (D13) above, and the dialkylamine salt of the carboxyl group-containing vinyl monomer in (D23) are essential constituent monomers. And a polymer compound obtained by subjecting a polymer having a carboxyl group-containing monomer as an essential constituent monomer to amine conversion with a dialkylamine.

  In addition, as the compound having the group represented by the general formula (1) and the counter ion represented by the general formula (2), a mixture of each group or a compound having a counter ion and each group and counter ion in one molecule. The polymer compound having

  Preferred dialkylamines used for introducing the group represented by the general formula (1) or the counter ion represented by the general formula (2) include, for example, dioctadecylamine, dipalmitylamine, dicoconut fatty amine, Examples include behenylamine and ditallow fatty amine.

Among the compounds (D), a polymer compound having an N, N-dialkylamide group, represented by the general formula (2), is preferred from the viewpoint of improving fluidity in combination with (A1), (A2) and (B). And a polymer compound having an N, N-dialkylamide group and a counter ion represented by the general formula (2) in one molecule.
Among these, a polymer compound obtained by reacting a copolymer having an unsaturated carboxylic acid as an essential constituent monomer with a dialkylamine having 8 to 24 carbon atoms in the alkyl group is particularly preferable.

  Preferable specific examples of (D) include an amidated product of a (meth) acrylic acid copolymer with a dialkylamine and an amide / amine chloride of a maleic anhydride copolymer with a dialkylamine.

As the hydrocarbon solvent (E) in the present invention, an aromatic hydrocarbon solvent (E1); toluene, xylene, ethylbenzene, C9 (meaning an aromatic hydrocarbon having 9 carbon atoms, the same shall apply hereinafter) is used as a main component. Aromatic hydrocarbons (trimethylbenzene, isopropylbenzene, “Ipsol 100” manufactured by Idemitsu Kosan Co., Ltd., “Swazole 1000” manufactured by Maruzen Petrochemical Co., Ltd.), etc., and aromatic hydrocarbons mainly composed of C10 (diethylbenzene, dimethylethylbenzene) , Tetramethylbenzene, "Ipsol 150" manufactured by Idemitsu Kosan Co., Ltd., "Swazole 1500" manufactured by Maruzen Petrochemical Co., Ltd.), tetralin, etc., aliphatic hydrocarbon solvent (E2): n-hexane, n-heptane, n- Octane, n-decane, etc., or alicyclic hydrocarbon solvent (E3); cyclopentane, cyclo Hexane, cyclooctane, and the like.
From the viewpoint of the solubility of (A1), (A2) and (B) and the flash point of the fluidity improver, the aromatic hydrocarbon solvent (E1) is preferred, and the aromatic containing C9 as a main component is more preferred. And aromatic hydrocarbons mainly composed of C10 and C10.

The fluidity improver of the present invention only needs to contain the copolymer (A1), the copolymer (A2) and the copolymer (B), and the copolymer (A1) relative to the weight of the fluidity improver. The weight percentage is preferably 3.0 to 35.0% by weight, more preferably 5.0 to 30.0% by weight, still more preferably 10 from the viewpoint of the efficiency of adding the fluidity improver to the heavy fuel. 0.0-25.0% by weight.
The weight percentage of the copolymer (A2) with respect to the weight of the fluidity improver is preferably 20.0 to 60.0% by weight, more preferably 25.0 to 55.55% from the viewpoint of the low temperature fluidity of the fuel oil. It is 0% by weight, more preferably 30.0-50.0% by weight.
The weight percentage of the copolymer (B) with respect to the weight of the fluidity improver is preferably 1.0 to 10.0% by weight, more preferably from the viewpoint of low temperature fluidity of the fuel oil and oil permeability at room temperature. It is 1.5 to 8.0% by weight, more preferably 2.0 to 6.0% by weight. In addition, when the total of the weight percentages of the copolymer (A1), the copolymer (A2), and the copolymer (B) with respect to the weight of the fluidity improver is less than 100%, the oil-soluble phenol is further added. It shall contain at least 1 sort (s) among resin (C), wax dispersing agent (D), and hydrocarbon solvent (E).

  The ratio of the total weight of the copolymer (A1), the copolymer (A2) and the copolymer (B) in the fluidity improver of the present invention is the efficiency of adding the fluidity improver to the fuel oil. From the viewpoint of oil permeability at room temperature and the like, it is preferably 40 to 80% by weight, more preferably 45 to 75% by weight, still more preferably 50 to 70% by weight based on the total weight of the fluidity improver. is there.

  The weight ratio [(A1) / (A2)] of the copolymer (A1) and the copolymer (A2) is preferably 5/95 to 40 from the viewpoint of the addition efficiency of the fluidity improver to the heavy fuel. / 60, more preferably 10/90 to 40/60, and still more preferably 20/80 to 40/60.

  The ratio {[(A1) + (A2)] / (B)} between the total weight of the copolymer (A1) and the copolymer (A2) and the weight of the copolymer (B) is low in the fuel oil. From the viewpoint of fluidity and oil permeability at normal temperature, it is preferably 85/15 to 98/2, more preferably 89/11 to 97/3, and further preferably 89/11 to 96/4.

  The weight percentage of (C) with respect to the weight of the fluidity improver is preferably 0.5 to 20.0% by weight, more preferably 1.0 to 15.0% by weight from the viewpoint of the low-temperature fluidity of the fuel oil. Particularly preferably, it is 1.0 to 10.0% by weight.

  The weight percentage of (D) with respect to the weight of the fluidity improver is preferably 0.5 to 20.0% by weight, more preferably 1.0 to 15.0% by weight from the viewpoint of the low temperature fluidity of the fuel oil. Particularly preferably, it is 1.0 to 10.0% by weight.

  The weight percentage of (E) with respect to the weight of the fluidity improver is preferably 10 to 50% by weight, more preferably 20 to 40% by weight, from the viewpoint of handling the fluidity improver.

In the fluidity improver of the present invention, other additives may be added in a proportion of 5% by weight or less based on the weight of the fluidity improver.
Other additives include, for example, lubricity improvers (oleic acid, linoleic acid, linolenic acid, and glycerin esters thereof), rust inhibitors (aliphatic amines and salts thereof, organic phosphates, organic sulfonates, etc.) ), Antioxidants (hindered phenols, salicylidene derivatives, etc.), cetane number improvers (alkyl nitrate esters, amyl nitrate, isopropyl nitrate, etc.), detergent dispersants, combustibility improvers, conductivity enhancers, And other fluidity improvers [known ethylene / vinyl acetate copolymers, ethylene / vinyl acetate / α-olefin copolymers, ethylene / vinyl acetate / vinyl neodecanoate copolymers, polyalkyl (meth) acrylate copolymers Polymers (however, different from (A1), (A2) and (B)), polyol fatty acid esters, etc. ], And the like.

The fuel oil composition of the present invention contains the above fluidity improver and fuel oil.
The method for producing a fuel oil composition of the present invention comprises mixing the above fluidity improver and fuel oil, mixing other additives as necessary, and mixing the above fluidity improver composition and fuel oil. Any method such as a method of mixing other additives as necessary may be used.

The target fuel oil is at least one fuel oil selected from the group consisting of vegetable oils, animal oils, fish oils, middle distillate fuel oils, and hydrotreated oils obtained by hydrotreating them.
Examples of vegetable oils include palm oil, coconut oil, rapeseed oil, soybean oil, sunflower oil, corn oil, sesame oil, tall oil, and peanut oil.
Animal oils include beef tallow, bone oil and whale oil.
Fish oil includes fatty oils collected from sardines and saury.
Middle distillate fuel oil includes JIS No. 1 diesel oil, JIS No. 2 diesel oil, JIS No. 3 diesel oil, JIS No. 3 diesel oil and A heavy oil obtained by distillation of low-sulfur crude oil (for example, Minas crude oil, etc.) Desulfurized diesel oil and A heavy oil produced through hydrodesulfurization treatment process from JIS No. 1 diesel oil produced from a light oil fraction obtained by blending the desulfurized diesel oil and straight run diesel oil (light oil before hydrodesulfurization process), JIS2 No. diesel oil, JIS No. 3 diesel oil, JIS No. 3 diesel oil, A heavy oil and the like.
Examples of the hydrotreated oil include the above-mentioned vegetable oil, animal oil, fish oil, middle distillate fuel oil, hydrotreated oil composed of hydrocarbons obtained by direct hydrocracking, and unsaturated bonds obtained by decarboxylation by catalytic cracking. And hydrotreated oil composed of hydrocarbons obtained by hydrotreating hydrocarbons having the following.
Of these, JIS No. 2 diesel oil blended with 10-30% hydrotreated oil obtained by hydrotreating rapeseed oil and soybean oil, and 50% by weight or more of desulfurized diesel oil produced through hydrodesulfurization treatment process Thus, the fluidity improver of the present invention is useful in JIS No. 2 diesel oil and A heavy oil, and particularly in JIS No. 2 diesel oil and A heavy oil.

  The cloud point of the fuel oil in the present invention has a lower limit of −25 ° C., preferably −8 ° C., more preferably −6 ° C., and an upper limit of + 10 ° C., preferably + 5 ° C., more preferably 0 ° C. When a fuel oil having a cloud point in the above range is used, the fuel oil composition of the present invention is particularly excellent from the viewpoint of low-temperature fluidity.

  The fuel oil composition of the present invention is a fuel oil composition in which the sulfur content of the fuel oil is 0.001% by weight or less based on the weight of the fuel oil, and from the viewpoint of low temperature fluidity, the sulfur content is 0.001% by weight. % Of low sulfur gas oil is preferred.

In the case of a fuel oil composition containing a heavy fraction, the fuel oil composition has a 10% residual carbon content of the fuel oil of 0.2 wt% to 0.5 wt%, and prevents filter clogging by sludge. From the viewpoint, it is preferable that the A heavy oil has a 10% residual carbon content of 0.2 wt% to 0.4 wt%.
The value of 10% residual carbon content means a value measured according to JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.

The content of the fluidity improver of the present invention in the fuel oil composition of the present invention is preferably 10 to 1,000 ppm, more preferably 20 to 800 ppm, particularly preferably 50 to 500 ppm based on the weight of the fuel oil. .
If it is 10 ppm or more, low-temperature fluidity is easily exhibited, and if it is 1000 ppm or less, the addition efficiency is good and the economy is excellent.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

<Production Example 1>
An ethylene / vinyl acetate copolymer (92.5 / 7.5 mol%, branching degree 3.5, Mw 6,500) 600 is placed in a glass reaction vessel equipped with a thermometer, a heating device, a stirring device, and a nitrogen blowing tube. And 400 parts of di-n-butyl maleate were added, and the temperature was raised to 150 ° C. under a nitrogen atmosphere. To this, 20 parts of ditertiary butyl peroxide and 1.5 parts of lauryl mercaptan were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further reacted at 150 ° C. for 2 hours to obtain a copolymer (A1-1).

<Production Example 2>
In a glass reaction vessel equipped with a thermometer, a heating device, a stirring device and a nitrogen blowing tube, 500 parts of ethylene / vinyl acetate copolymer (95/5 mol%, branching degree 4.5, Mw 6,500) and fumaric acid 500 parts of di-2-ethylhexyl was added, and the temperature was raised to 150 ° C. under a nitrogen atmosphere. To this, 20 parts of ditertiary butyl peroxide and 1.5 parts of lauryl mercaptan were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further reacted at 150 ° C. for 2 hours to obtain a copolymer (A1-2).

<Production Example 3>
In a glass reaction vessel equipped with a thermometer, a heating device, a stirrer, and a nitrogen blowing tube, an ethylene / 2-ethylhexanoic acid vinyl copolymer (93.4 / 6.6 mol%, branching degree 3.5, Mw6). , 500) 600 parts and 400 parts of n-dibutyl maleate were added, and the temperature was raised to 150 ° C. under a nitrogen atmosphere. To this, 20 parts of ditertiary butyl peroxide and 1.5 parts of lauryl mercaptan were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further reacted at 150 ° C. for 2 hours to obtain a copolymer (A1-3).

<Production Example 4>
In a glass reaction vessel equipped with a thermometer, a heating device, a stirring device, and a nitrogen blowing tube, an ethylene / vinyl acetate / vinyl neodecanoate copolymer (93.5 / 5.7 / 0.8 mol%, branching degree 3) 0.5, Mw 6,500) and 500 parts of di-2-ethylhexyl fumarate were added, and the temperature was raised to 150 ° C. under a nitrogen atmosphere. To this, 20 parts of ditertiary butyl peroxide and 1.5 parts of lauryl mercaptan were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further reacted at 150 ° C. for 2 hours to obtain a copolymer (A1-4).

<Production Example 5>
An ethylene / vinyl acetate copolymer (92.5 / 7.5 mol%, branching degree 3.5, Mw 6,500) 700 was added to a glass reaction vessel equipped with a thermometer, a heating device, a stirring device and a nitrogen blowing tube. The temperature was raised to 150 ° C. under a nitrogen atmosphere. To this, 300 parts of n-dodecyl methacrylate, 20 parts of ditertiary butyl peroxide and 1.5 parts of lauryl mercaptan were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further reacted at 150 ° C. for 2 hours to obtain a copolymer (A1-5).

<Production Example 6>
An ethylene / vinyl acetate copolymer (92.5 / 7.5 mol%, branching degree 3.5, Mw 6,500) 700 was added to a glass reaction vessel equipped with a thermometer, a heating device, a stirring device and a nitrogen blowing tube. The temperature was raised to 150 ° C. under a nitrogen atmosphere. To this, 300 parts of n-tetradecyl methacrylate, 20 parts of ditertiary butyl peroxide and 1.5 parts of lauryl mercaptan were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further reacted at 150 ° C. for 2 hours to obtain a copolymer (A1-6).

<Comparative Production Example 1>
In a glass reaction vessel equipped with a thermometer, a heating device, a stirring device and a nitrogen blowing tube, an ethylene / vinyl acetate copolymer (96.1 / 3.9 mol%, branching degree 4.5, Mn2,500, Mw6) , 500) 750 parts and 250 parts of di-2-ethylhexyl fumarate were added, and the temperature was raised to 150 ° C. under a nitrogen atmosphere. To this, 20 parts of ditertiary butyl peroxide and 1.5 parts of lauryl mercaptan were added dropwise over 2 hours. After completion of dropping, the reaction was further continued at 150 ° C. for 2 hours to obtain a comparative copolymer (HA1-1).

Table 1 shows analytical values and the like of the copolymers (A1-1) to (A1-6) obtained above and the comparative copolymer (HA1-1).
Note that (a1), (a2-1) to (a2-3), (a3-1), (a3-2), (a4-1), and (a4-2) described in Table 1 and Table 2 The composition is as described below. In addition, the SP value of the homopolymer by each monomer was described after each monomer name. Copolymers (A1-1) to (A1-6), (HA1-1), and (A2-1) to (A) calculated from the SP value and the molar fraction calculated from the number of parts described in each Example. The SP values of A2 to 4) are shown in Tables 1 and 2.
(A1): Ethylene, 8.56
(A2-1): Vinyl acetate, 10.56
(A2-2): 2-ethylhexanoic acid vinyl, 9.28
(A2-3): Vinyl neodecanoate, 9.04
(A3-1): di-n-butyl maleate, 9.34
(A3-2): di-2-ethylhexyl fumarate, 8.95
(A4-1): n-dodecyl methacrylate, 9.02
(A4-2): n-tetradecyl methacrylate, 8.97

<Production Examples 7 to 10>
A pressure-resistant tubular reactor was supplied with a mixture of 1000 parts of the monomers listed in Table 2, 40 parts of 1-propanol and 0.5 parts of diisopropyl percarbonate, under conditions of 120 ° C., 110 MPa, residence time of 3 minutes. Polymerized. After completion of the polymerization, unreacted monomers were removed at 120 ° C. under reduced pressure (0.027 to 0.040 MPa) to obtain copolymers (A2-1) to (A2-4).

  Table 2 shows analytical values and the like of the copolymers (A2-1) to (A2-4) obtained above.

<Production Examples 11-15, Comparative Production Example 2>
25 parts by weight of isopropyl alcohol was charged into a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a dropping funnel, a nitrogen introduction tube, and a decompression device, and the system was heated to 83 ° C. with a nitrogen atmosphere. While stirring the isopropyl alcohol in the reactor, in another glass beaker, 100 parts by weight of the monomer composition shown in Table 1, 18 parts by weight of isopropyl alcohol, and 2,2-azobis (2,4-dimethylvalero). Nitrile) 0.1 part by weight, 2,2-azobis (2-methylbutyronitrile) 0.4 part by weight, and a solution in which dodecyl mercaptan of the amount shown in Table 1 was dissolved were respectively added to a reactor from a separate dropping funnel. The whole amount was charged at a constant rate over 2 hours, and a polymerization reaction was carried out at 83 ° C. for 3 hours after completion of the charging. After completion of the reaction, isopropyl alcohol was removed while raising the temperature from 83 ° C. to 120 ° C. to obtain copolymers (B1) to (B5) and a comparative copolymer (HB1).

  Table 3 shows analytical values and the like of the copolymers (B1) to (B5) and (HB1) obtained above.

The compositions of (b1), (b2-1), (b2-2), and (a4-1) to (a4-6) described in Table 3 are as described below. In addition, the SP value of the homopolymer by each monomer was described after each monomer name. Table 3 shows SP values of the copolymers (B1) to (B5) calculated from this SP value and the molar fraction calculated from the number of parts described in each Example.
(B1): Styrene, 10.55
(B2-1): Dimethylaminoethyl methacrylate, 9.52
(B2-2): diethylaminoethyl methacrylate, 9.35
(B2-3): Morpholinoethyl methacrylate, 10.16
(A4-1): Methyl methacrylate, 9.93
(A4-2): dodecyl methacrylate / tridecyl methacrylate = 60/40 (wt%) (linear ratio = 74%), 8.99
(A4-3): tetradecyl methacrylate / pentadecyl methacrylate = 50/50 (wt%) (linear ratio = 80%), 8.94
(A4-4): Hexadecyl methacrylate, 8.93
(A4-5): Octadecyl methacrylate, 8.90
(A4-6): 2-decyltetradecyl methacrylate, 8.77

<Oil-soluble phenolic resin (C)>
The following compounds were used as (C).
(C-1): Nonylphenol-formaldehyde polycondensate (Mn = 3,500, Mw =
5,500)

<Wax dispersant (D)>
The following compounds were used as (D).
(D-1): Amide amine salt composed of 1 mol of phthalic anhydride and 2 mol of dihydrogenated tallow amine.
(D-2): a copolymer (molar ratio 24/24/50/2) having hexadecaene, octadecaene and maleic anhydride as constituent monomers, and 2 moles of dihydrogenated tallow amine per mole of maleic anhydride. Reaction product of (Mn = 7,500, Mw = 12,500)

<Hydrocarbon solvent (E)>
The following compounds were used as (E).
(E): “Swazol 1500” manufactured by Maruzen Petrochemical Co., Ltd.

<Preparation of fluidity improver>
Examples 1-8 and Comparative Examples 1-4
In a glass container equipped with a stirrer, a heating device and a thermometer, the components described in Table 4 below were charged in the number of parts described and uniformly dissolved at 90 ° C., and Examples 1 to 8 and Comparative Examples 1 to 4 A fluidity improver was obtained.

<Adjustment of fuel oil composition-1>
Examples 9-18, Comparative Examples 5-8
The flow rate improver shown in Table 6 is added to the fuel oil 1 having the properties shown in Table 5 and mixed uniformly. CFPP [Cryogenic filter clogging point (° C.): JIS K2288 ] And PP [pour point (° C): JIS K2269] were measured to evaluate low temperature fluidity. The results are shown in Table 6.
The flow rate improver shown in Table 7 is added to the fuel oil 2 having the properties shown in Table 5 and mixed uniformly, and CFPP [Cryogenic Filter Clogging Point (° C): JIS K2288] ] And PP [pour point (° C): JIS K2269] were measured to evaluate low temperature fluidity. The results are shown in Table 7.

  As is clear from this, the fluidity improver of the present invention gives very low temperature fluidity to any diesel oil.

<Adjustment of fuel oil composition-2>
Examples 19-24, Comparative Examples 9-12
The flowability improver shown in Table 8 is added to the fuel oil 3 having the properties shown in Table 5 and mixed uniformly. CFPP [Cryogenic filter clogging point (° C.): JIS K2288 ], Modified method CFPP [low temperature filter clogging point correcting method No. 4 (° C.): Method described in the 1993 Activity Report by the Japan Oil Society's Fuel Oil Subcommittee Fluidity Committee. ] And PP [pour point (° C): JIS K2269] were measured to evaluate low temperature fluidity. The results are shown in Table 8.
The flowability improver shown in Table 9 is added to the fuel oil 4 having the properties shown in Table 5 and mixed uniformly to obtain CFPP [Cryogenic filter clogging point (° C.): JIS K2288. ], Modified method CFPP [low temperature filter clogging point correcting method No. 4 (° C.): Method described in the 1993 Activity Report by the Japan Oil Society's Fuel Oil Subcommittee Fluidity Committee. ] And PP [pour point (° C): JIS K2269] were measured to evaluate low temperature fluidity. The results are shown in Table 9.

  As is clear from this, the fluidity improver of the present invention gives very low temperature fluidity to any A heavy oil.

The fuel oil composition containing the fluidity improver of the present invention and a low sulfur fuel oil having a sulfur content of 0.001% by weight or less has a sulfur content of 0.001% by weight or less used for diesel engines, boilers, and the like. It is suitable for fuel oil (light oil), jet oil for aircraft and the like.
Moreover, the fuel oil composition containing the fluidity improver of the present invention and a fuel oil having 10% residual carbon content of 0.2% by weight to 0.5% by weight is a residual used in boilers and marine engines. Suitable for heavy oil A having a carbon content of 0.2 wt% to 1.0 wt% or less.

Claims (11)

A fluidity improver comprising a copolymer (A1), a copolymer (A2) and a copolymer (B), wherein (A1) and (A2) are ethylene (a1) and an aliphatic saturated carboxylic acid. It is a copolymer having an aliphatic saturated carboxylic acid vinyl ester (a2) having 2 to 24 carbon atoms as an essential constituent monomer, and (A1) is a copolymer satisfying all of the following (I) to (III). (A2) is a copolymer satisfying all of the following (IV) to (VI), and (B) is an aromatic hydrocarbon monomer (b1) and a nitrogen atom-containing monomer (b2). ) Is an essential constituent monomer, and (B) is a copolymer satisfying all of the following (VII) to (IX).
(I) The weight average molecular weight is 3,000 to 100,000.
(II) Solubility parameter is 8.5 to 10.0 (cal / cm ³ ) ^1/2
(III) Crystallization start temperature by differential operation calorimeter is 60 ° C. or higher and 80 ° C. or lower (IV) Weight average molecular weight is 3,000 to 100,000
(V) Solubility parameter is 8.5 to 10.0 (cal / cm ³ ) ^1/2
(VI) Crystallization start temperature by differential operation calorimeter is 30 ° C. or higher and lower than 60 ° C. (VII) Weight average molecular weight is 10,000 to 300,000
(VIII) Solubility parameter is 8.5 to 10.0 (cal / cm ³ ) ^1/2
(IX) Crystallization start temperature by differential operation calorimeter is -20 ° C or higher and lower than 30 ° C   The copolymer (A1) is further an unsaturated dicarboxylic acid alkyl ester (a3) in which the alkyl group has 4 to 22 carbon atoms and / or a linear or branched alkyl group having 1 to 32 carbon atoms. The fluidity improver according to claim 1, which is a copolymer having a branched alkyl (meth) acrylate (a4) as an essential constituent monomer. The fluidity improver according to claim 1 or 2, wherein the copolymer (A2) is a copolymer having a degree of branching of 0.3 to 6.0% as measured by ¹ H-NMR.   The copolymer (B) is a copolymer further comprising a linear or branched alkyl (meth) acrylate (a4) having 1 to 32 carbon atoms of a linear or branched alkyl group as an essential constituent monomer. Item 4. The fluidity improver according to any one of Items 1 to 3.   The fluidity improver according to any one of claims 1 to 4, wherein the weight ratio [(A1) / (A2)] of the copolymer (A1) and the copolymer (A2) is 5/95 to 40/60. .   The ratio {[(A1) + (A2)] / (B)} of the total weight of the copolymer (A1) and the copolymer (A2) to the weight of the copolymer (B) is 85/15 to 98 The fluidity improver according to any one of claims 1 to 5, which is / 2.   The fluidity improvement according to any one of claims 1 to 6, further comprising at least one selected from the group consisting of an oil-soluble phenol resin (C), a wax dispersant (D), and a hydrocarbon solvent (E). Agent.   A fuel oil composition comprising the fluidity improver according to any one of claims 1 to 7 and a fuel oil, the fuel comprising 10 to 1000 ppm of the fluidity improver based on the weight of the fuel oil. Oil composition.   The fuel oil composition according to claim 8, wherein the sulfur content of the fuel oil is 0.001 wt% or less based on the weight of the fuel oil.   The fuel oil has a 10% residual carbon content (value measured according to JIS K 2270 "Crude oil and petroleum products-residual carbon content" test method) of 0.2 wt% to 0.5 wt%. The fuel oil composition as described.   The fuel oil composition according to any one of claims 8 to 10, wherein the fuel oil is at least one fuel oil selected from the group consisting of vegetable oils, animal oils, fish oils, middle distillate fuel oils, and hydrotreated oils thereof.