JP5634302B2 - Low temperature fluidity improver for fatty acid methyl esters - Google Patents

Description

  The present invention relates to a low-temperature fluidity improver that improves the pour point and low-temperature filtration clogging temperature of a fatty acid methyl ester, and can be used and transported in winter or in a cold region without hindrance.

  Fatty acid methyl esters are known as biodiesel fuels and are produced from various vegetable and animal oils. Among these, since vegetable oil is produced from a plant that has absorbed carbon dioxide in the atmosphere, fatty acid methyl esters derived from vegetable oil are classified as renewable energy and are attracting attention as a measure against global warming.

  For example, Patent Document 1 discloses a biodiesel fuel composition in which an antioxidant is added to biodiesel fuel, and the biodiesel fuel contains 1% or more of oleic acid methyl ester and / or linoleic acid methyl ester, As a main component, it comprises one or more fatty acid methyl esters having C4 to C25 carbon atoms, and the antioxidant comprises a natural component and / or a synthetic component, and is based on the total mass of the fatty acid methyl ester. A biodiesel fuel composition, which is added at a ratio of 0.001% to 5%; a method of using the biodiesel fuel composition, wherein A method of using a biodiesel fuel composition characterized by mixing at a volume ratio of 1 to 100% is disclosed. However, fatty acid methyl ester has a high pour point, and problems such as solidification in a fuel tank in winter and solidification in a container at the time of transportation have occurred, so it was necessary to improve low-temperature fluidity.

（式中、ｎは２以上の整数、Ｘ^１〜Ｘ^８はそれぞれ独立して、水素、直鎖炭化水素又は分岐炭化水素基、もしくは炭素数３以上のシクロ炭化水素基を示す。）

（式中、Ｘ^９、Ｘ^１０のうちいずれか一方は炭素数８乃至２４の直鎖又は分岐の炭化水素基で、もう一方は水素を示し、Ｘ^１１はＮＲ^１Ｒ^２又はＮＨＲ^３、Ｘ^１２はＨ^＋、ＨＮ^＋ＨＲ^４Ｒ^５又はＨＮ^＋Ｈ_２Ｒ^６である。また、Ｒ^１〜Ｒ^６はそれぞれ独立して炭素数８乃至２４の炭化水素基を示す）
が開示されている。 Therefore, various low-temperature fluidity improvers are known for fatty acid methyl esters. For example, Patent Document 2 discloses that a compound A represented by the following general formula (1) and a compound B represented by the following general formula (2) have a mass ratio (compound A) :( compound B) of 1:99. Or low-temperature fluidity improver for fatty acid methyl ester to be contained to be 50:50:

(In the formula, n represents an integer of 2 or more, and X ^{1 to} X ⁸ each independently represent hydrogen, a linear hydrocarbon or a branched hydrocarbon group, or a cyclohydrocarbon group having 3 or more carbon atoms.)

(In the formula, one of X ⁹ and X ¹⁰ is a linear or branched hydrocarbon group having 8 to 24 carbon atoms, the other represents hydrogen, and X ¹¹ represents NR ¹ R ² or NHR ³ , X ¹² is H ⁺ , HN ⁺ HR ⁴ R ⁵ or HN ⁺ H ₂ R ⁶ , and R ^{1 to} R ⁶ each independently represents a hydrocarbon group having 8 to 24 carbon atoms)
Is disclosed.

  Patent Document 3 discloses (A) a fatty acid selected from linear saturated fatty acids having 8 to 28 carbon atoms and linear unsaturated fatty acids having 8 to 28 carbon atoms, and (B) a pour point depressant and Oil improver for low sulfur gas oil containing at least one modifier selected from low temperature fluidity improver and having a sulfur content of 0.05% by mass or less; pour point depressant is chlorinated paraffin and naphthalene The oil improver for low sulfur gas oil, which is at least one selected from condensate, condensate of chlorinated paraffin and phenol, polyalkyl methacrylate, polybutene, polyalkyl styrene, polyvinyl acetate and polyalkyl acrylate; low temperature fluidity The improver is at least one selected from ethylene-vinyl acetate copolymer, ethylene-alkyl acrylate and alkenyl succinic acid amide. Sulfur light oil oiliness improver is disclosed.

  However, sufficient effects cannot be obtained with these low-temperature fluidity improvers, and more effective low-temperature fluidity improvers for fatty acid methyl esters have been desired. Therefore, the present inventors have invented a low-temperature fluidity improver for fatty acid methyl esters having good low-temperature fluidity, and have filed a patent application as Japanese Patent Application No. 2010-047953.

JP 2007-016089 A JP 2005-187581 A JP-A-10-110175

  However, even with fatty acid methyl esters whose pour point has been lowered using a low-temperature fluidity depressant, the filter is clogged when the fuel filter is clogged or when it is transferred to the tank after transporting the fatty acid methyl ester. Has been found to occur. Therefore, in order to use fatty acid methyl ester as fuel, it is necessary to lower the pour point and lower the low temperature filtration clogging temperature (CFPP) so that the filter does not clog. CFPP is the lowest temperature that can be filtered when fatty acid methyl ester is filtered with a filter having a specific roughness, and at a temperature lower than CFPP, crystals and wax components are produced and the filter is clogged.

  Pour point and CFPP are both indicators of the low-temperature properties of a substance. If pour point is lowered, CFPP tends to decrease, but in the case of fatty acid methyl ester, pour point and CFPP are not correlated, and pour point is Even if lowered, CFPP may not fall. That is, when fatty acid methyl ester is used as a fuel in winter or in cold regions, it is necessary to improve both the pour point and CFPP at the same time. Accordingly, an object of the present invention is to provide a low temperature fluidity improver capable of improving the low temperature fluidity of fatty acid methyl esters and improving CFPP as well as existing low temperature fluidity improvers.

  Therefore, the present inventors have intensively studied and found a low-temperature fluidity improver that can simultaneously improve the low-temperature fluidity of fatty acid methyl ester and CFPP, and have reached the present invention. That is, the present invention is a low temperature fluidity improver for fatty acid methyl esters represented by the following general formula (1).

（式中、Ｒ^１及びＲ^２はそれぞれ独立して水素原子又はドデシル基を表し、ｍ及びｎはそれぞれ独立して１〜５０の数を表し、−Ｃ _１６ Ｈ _３３ はヘキサデシル基を表し、ｐは１〜５，０００の数を表す。但し、Ｒ^１及びＲ^２の合計の８０モル％以上はドデシル基、且つｍ／ｎ＝０．４〜４でなければならない。）

(Wherein, R ¹ and R ² each independently represent a hydrogen atom or a dodecyl group , m and n each independently represent a number of 1 to 50, —C ₁₆ H ₃₃ represents a hexadecyl group , p Represents a number of 1 to 5,000, provided that 80 mol% or more of the total of R ¹ and R ² must be a dodecyl group and m / n = 0.4 to 4.

  The effect of the present invention is to provide a low temperature fluidity improver for fatty acid methyl esters that can simultaneously improve the low temperature fluidity of fatty acid methyl esters and CFPP.

  The low temperature fluidity improver for fatty acid methyl esters of the present invention is represented by the following general formula (1).

（式中、Ｒ^１及びＲ^２はそれぞれ独立して水素原子又は炭素数１〜３０の脂肪族炭化水素基を表し、ｍ及びｎはそれぞれ独立して１〜５０の数を表し、ｐは１〜５０００の数を表す。但し、Ｒ^１及びＲ^２の合計の８０モル％以上は炭素数１〜３０の脂肪族炭化水素基、且つｍ／ｎ＝０．４〜４でなければならない。）

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 30 carbon atoms, m and n each independently represent a number of 1 to 50, and p is 1) Represents a number of ˜5000, provided that 80 mol% or more of the total of R ¹ and R ² must be an aliphatic hydrocarbon group having 1 to 30 carbon atoms and m / n = 0.4 to 4).

In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 30 carbon atoms, and examples of the aliphatic hydrocarbon group having 1 to 30 carbon atoms include: Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, secondary pentyl, hexyl, isohexyl, secondary hexyl , Heptyl group, isoheptyl group, secondary heptyl group, octyl group, isooctyl group, secondary octyl group, nonyl group, isononyl group, secondary nonyl group, decyl group, isodecyl group, secondary decyl group, undecyl group, isoundecyl group Secondary undecyl group, dodecyl group, isododecyl group, secondary dodecyl group, tridecyl group, isotridecyl group, secondary tridecyl group, tetradecyl group Group, isotetradecyl group, secondary tetradecyl group, hexadecyl group, isohexadecyl group, secondary hexadecyl group, stearyl group, eicosyl group, docosyl group, tetracosyl group, hexacosyl group, octacosyl group, triacontyl group, 2-butyl Octyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldecyl, 2-octyldecyl, 2-decyltetradecyl, 2-dodecylhexadecyl Group, alkyl group such as monomethyl branched-isostearyl group; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, isopentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group Group, decenyl group, undecenyl group, dode Alkenyl groups such as senyl, tetradecenyl and oleyl groups; cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl And cycloalkyl groups such as a methylcyclohexenyl group and a methylcycloheptenyl group. Among these, since the improvement effect of CFPP is great, an aliphatic hydrocarbon group having 12 to 30 carbon atoms is preferable, an alkyl group having 12 to 18 carbon atoms is more preferable, and an alkyl group having 12 to 16 carbon atoms is more preferable.

Although it can be seen from the general formula (1) that there are n × p R ¹ and R ² , each may be independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 30 carbon atoms. However, 80 mol% or more of the total amount of n × p R ¹ and R ² must be an aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably 90 mol% or more, and 95 mol% or more. More preferred. When the aliphatic hydrocarbon group having 1 to 30 carbon atoms is less than 80 mol%, the low temperature fluidity and the improvement rate of CFPP are significantly reduced. In view of economy, the upper limit is preferably 99.9 mol% or less. In order to make the same value 100 mol%, synthesis takes time, and a great deal of labor may be required.

  In General formula (1), m and n represent the number of 1-50, respectively, and p represents the number of 1-5,000. The molecular weight of the polymer represented by the general formula (1) is determined by a combination of these numbers. The molecular weight of the polymer is not particularly specified, but if the molecular weight is low, the effect as a low temperature fluidity improver will be low, and if the molecular weight is too high, handling may be difficult or it may not dissolve in the fatty acid methyl ester. The weight average molecular weight of the general formula (1) is preferably 1,000 to 600,000, more preferably 3,000 to 250,000, and still more preferably 5,000 to 100,000. For the same reason, m and n are each preferably a number from 1 to 20, and p is preferably a number from 3 to 1,000. The weight average molecular weight can be measured using an instrument such as GPC.

  The ratio of m and n in the general formula (1) represents the copolymerization ratio of units corresponding to m and n, respectively, but m / n (value obtained by dividing m by n) is in the range of 0.4 to 4. It must be 0.5-2, more preferably 0.6-1.2, still more preferably 0.7-1.0. If this value is less than 0.4, the solubility in fatty acid methyl ester may be low, or the effect of improving low-temperature fluidity may be low. If it is greater than 4, the effect of improving CFPP will be extremely low. . The general formula (1) may be any of random polymerization, block polymerization, and random / block polymerization, but is preferably random polymerization because of easy production.

The form of the group represented by —C ₁₆ H ₃₃ described in the structural formula represented by the general formula (1) may be linear or branched as long as it is an aliphatic hydrocarbon group, but improves CFPP. A linear hexadecyl group is preferred because of its high effect.

  The method for producing the low-temperature fluidity improver for fatty acid methyl esters of the present invention is not specified, and any known method may be used. However, since the reaction is easy, the following method is used. It is preferable.

  The whole amount of α-octadecene and maleic anhydride is charged into a reaction vessel, and the polymerization reaction is carried out at 40 to 250 ° C., preferably 80 to 250 ° C. for 2 to 30 hours. A solvent may or may not be used, but since the polymerization reaction proceeds easily, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, an ether solvent such as tetrahydrofuran, or an aromatic solvent such as xylene or toluene is used. It is preferable to do. The amount of the solvent may be 10 to 200% by mass based on the total amount of α-octadecene and maleic anhydride. Although a catalyst may or may not be used, polymerization of azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, etc. is possible because the reaction rate can be increased and the yield can be improved. It is preferred to use an initiator. The amount of the catalyst may be 0.1 to 5% by mass based on the total amount of α-octadecene, maleic anhydride and the like. Α-Octadecene used as a raw material is an aliphatic hydrocarbon having 18 carbon atoms having a double bond at the end of the molecule, which may be linear or branched, but has a high effect of improving low-temperature fluidity and CFPP. A straight chain is preferred. When olefins other than carbon number 18 are used, low temperature fluidity is improved, but CFPP is not improved. A chain transfer agent such as 1-decanethiol or carbon tetrachloride can be used for the purpose of adjusting the molecular weight of the polymer.

  Examples of the α-olefin used here include 2-methyl-1-heptadecene, 2-ethyl-1-hexadecene, 2-butyl-1-tetradecene, 2-hexyl-1-dodecene, and 2-octyl-1- Examples include decene, 3-methyl-1-heptadecene, 3-ethyl-1-hexadecene, 3-butyl-1-tetradecene, 3-hexyl-1-dodecene, and 3-octyl-1-decene.

Next, in the polymer obtained by the above reaction, an aliphatic alcohol having 1 to 30 carbon atoms is added in an amount of 1.6 to 2.0 mol (R ¹ and R) with respect to 1 mol of maleic anhydride used in the above reaction. The amount of 80% or more of the total of ² becomes an aliphatic hydrocarbon group having 1 to 30 carbon atoms) may be esterified, and specific reaction conditions include dehydration at 50 to 250 ° C. for 1 to 60 hours It only has to react.

  Examples of the aliphatic alcohol having 1 to 30 carbon atoms used here include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, isopentanol, secondary pentanol, neo Pentanol, tertiary pentanol, hexanol, secondary hexanol, heptanol, secondary heptanol, octanol, 2-ethylhexanol, secondary octanol, nonanol, secondary nonanol, decanol, secondary decanol, undecanol, secondary undecanol, dodecanol Secondary dodecanol, tridecanol, isotridecanol, secondary tridecanol, tetradecanol, secondary tetradecanol, hexadecanol, secondary hexadecanol, stearyl alcohol , Isostearyl alcohol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, myricyl alcohol, 2-butyloctanol, 2-butyldecanol, 2-hexyloctanol, 2-hexyldecanol, 2-octyldecanol, Examples include 2-hexyl decanol, 2-octyl decanol, 2-decyl tetradecanol, and 2-dodecyl hexadecanol.

  A catalyst may or may not be used, but is preferably used because the reaction proceeds quickly. Examples of the catalyst include strong acids such as sulfuric acid and toluenesulfonic acid; metal halides such as titanium tetrachloride, hafnium chloride, zirconium chloride, aluminum chloride, gallium chloride, indium chloride, iron chloride, tin chloride, boron fluoride; water Sodium oxide, potassium hydroxide, sodium methylate, alkali metal or alkaline earth metal hydroxide such as sodium carbonate, alcoholate, carbonate; metal oxide such as aluminum oxide, calcium oxide, barium oxide, sodium oxide Product; organometallic compound such as tetraisopropyl titanate, dibutyltin dichloride, dibutyltin oxide, dibutyltin bis (2-ethylhexylthioglycolate); soap such as sodium octylate, potassium octylate, sodium laurate, potassium laurate; Activity And solid acids such as activated clay and the like, from 0.01 to 5% by weight, based on the reaction product the total amount the amount used is preferably 0.05 to 2 mass%. In addition, it is preferable to remove the catalyst remaining in the system after completion of the reaction by filtration or adsorption treatment.

  By the above reaction, the low temperature fluidity improver for fatty acid methyl esters of the present invention is obtained. The solvent used in the reaction may or may not be removed, but it is preferable not to remove the solvent because the viscosity of the product decreases and handling becomes easier, and another type of solvent is added after removing the solvent. More preferably. Another type of solvent is not limited as long as the low-temperature fluidity improver of the present invention dissolves, and examples thereof include light oil and known organic solvents, which are excellent in the effect of improving low-temperature fluidity. Aromatic solvents such as toluene, monoethylbenzene, monopropylbenzene, monobutylbenzene, xylene, diethylbenzene, dipropylbenzene, dibutylbenzene, trimethylbenzene, triethylbenzene, tripropylbenzene, tributylbenzene are preferred, and trimethylbenzene, tributylbenzene, Ethylbenzene, tripropylbenzene, tributylbenzene and the like are more preferable, and trimethylbenzene is still more preferable. Although the dilution rate with a solvent is not prescribed | regulated, it is preferable to dilute so that the density | concentration of the low-temperature fluidity improver for fatty acid methyl esters of this invention may be 2-90 mass%, and it may dilute to 10-85 mass%. More preferably, it is more preferably diluted to 30 to 80% by mass.

  Furthermore, the low-temperature fluidity improver for fatty acid methyl ester of the present invention includes an ethylene vinyl acetate copolymer (EVA), a styrene (meth) acrylate copolymer, in addition to the compound represented by the general formula (1), One or two or more kinds of polymers such as a (meth) acrylic acid ester polymer and a vinyl acetate polymer (hereinafter collectively referred to as polymer B) can be used in combination. Any polymer B may be polymerized by a known method, and the low temperature fluidity may be further improved by using it together with the compound represented by the general formula (1).

  The ethylene vinyl acetate copolymer is a copolymer obtained by copolymerization of ethylene and vinyl acetate, and its structure is not particularly specified, but since a combined effect is expected, the weight average molecular weight is 1,000 to 600,000. Preferably, 3,000-100,000 are more preferable. The reaction ratio of ethylene and vinyl acetate is preferably ethylene / vinyl acetate = 1/9 to 9/1 (molar ratio), more preferably 1/4 to 8/2 (molar ratio), and 1/1 to 7 /. 3 (molar ratio) is more preferable. The polymerization form may be either block polymerization or random polymerization, but is preferably random polymerization because it is easy to produce.

  Styrene (meth) acrylic acid ester copolymer is a copolymer obtained by copolymerization of styrene and acrylic acid ester or methacrylic acid ester, and its structure is not particularly specified, but the combined effect is expected. The average molecular weight is preferably 1,000 to 600,000, more preferably 3,000 to 100,000. The reaction ratio of styrene to acrylic acid ester or methacrylic acid ester is preferably styrene / (meth) acrylic acid ester = 1/9 to 9/1 (molar ratio), and preferably 1/4 to 2/1 (molar ratio). More preferred. Further, the (meth) acrylic acid ester is preferably an esterification reaction of (meth) acrylic acid and an alcohol having 1 to 30 carbon atoms, and (meth) acrylic acid and an aliphatic alcohol having 4 to 18 carbon atoms are esterified. Those obtained by the reaction are more preferable. The polymerization form may be either block polymerization or random polymerization, but is preferably random polymerization because it is easy to produce.

  The (meth) acrylic acid ester polymer is a homopolymer of acrylic acid ester or methacrylic acid ester, and its structure is not particularly specified, but since a combined effect is expected, the weight average molecular weight is 1,000 to 600, 000 is preferable, and 7,000 to 300,000 is more preferable. The (meth) acrylic acid ester is preferably an esterification reaction of (meth) acrylic acid and an alcohol having 1 to 30 carbon atoms, and (meth) acrylic acid and an aliphatic alcohol having 4 to 18 carbon atoms are used. What was esterified is more preferable.

  The vinyl acetate polymer is a homopolymer of vinyl acetate and its structure is not particularly specified, but since a combined effect is expected, the weight average molecular weight is preferably 1,000 to 600,000, and preferably 3,000 to 150. 1,000 is more preferable.

  Among these, since a synergistic effect is high, a styrene (meth) acrylic acid ester copolymer and a (meth) acrylic acid ester polymer, which are acrylic polymers, are preferable.

  The low-temperature fluidity improver composition for fatty acid methyl esters of the present invention is a blend of polymer B and a polymer represented by the general formula (1). The blending ratio of the polymer B and the polymer represented by the general formula (1) is not particularly specified, but the polymer represented by the general formula (1) / polymer B = 10/90 to 90/10 (mass ratio). It is preferable that it is 30 / 70-80 / 20 (mass ratio), and 50 / 50-70 / 30 (mass ratio) is still more preferable.

  Any fatty acid methyl ester used in the low-temperature fluidity improver for fatty acid methyl esters of the present invention can be used as long as it is made from natural fats and oils or waste cooking oils obtained from plants and animals. As such natural fats and oils, for example, as plant-derived natural fats and oils, linseed oil, eno oil, jute deer oil, olive oil, cacao butter, kapok oil, white mustard oil, sesame oil, rice bran oil, safflower oil, shea nut oil, cinnakiri oil , Soybean oil, tea seed oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, castor oil, sunflower oil, cottonseed oil, coconut oil, tree wax, peanut oil, Jatropha oil, sand peach oil, flower bud oil and A mixture thereof and the like can be mentioned, and examples of animal-derived natural fats and oils include beef tallow and pork fat. Among these, when used as fuel, plant-derived natural fats and oils are preferable from the viewpoint of renewable energy. The fatty acid methyl ester may be produced by any known method, for example, by heating the above natural oil and methanol under an alkali catalyst such as sodium hydroxide or potassium hydroxide. Examples include a method obtained by transesterification to remove glycerin that is produced as an impurity.

  The fatty acid methyl ester composition of the present invention is obtained by adding the low temperature fluidity improver for fatty acid methyl esters of the present invention or the low temperature fluidity improver composition for fatty acid methyl esters of the present invention to the fatty acid methyl esters. The addition amount is not particularly defined, but in any case, the low-temperature fluidity improver for fatty acid methyl esters of the present invention represented by the general formula (1) is 0.01 to 5 mass based on the total amount of the fatty acid methyl ester composition. % Is preferable, 0.05-3 mass% is more preferable, and 0.1-1 mass% is still more preferable. If it is less than 0.01% by mass, the low temperature fluidity or CFPP of the fatty acid methyl ester may not be improved, and if it exceeds 5% by mass, the effect corresponding to the amount added may not be obtained.

  When fatty acid methyl esters are used as fuels, these fuels are commonly referred to as biodiesel fuels. Biodiesel fuel may be used as a 100% by mass fatty acid methyl ester product or as a mixture of light oil and fatty acid methyl ester. As diesel oil, No. 1 diesel oil or No. 2 standardized in JIS K2204 Any general diesel oil that can be used in diesel engines such as diesel oil and No. 3 diesel oil can be used. When blending light oil and fatty acid methyl ester, it is preferable to blend so that fatty acid methyl ester is 2% by mass or more based on the total amount of biodiesel fuel. If the fatty acid methyl ester is less than 2% by mass, it is insufficient to achieve the original purpose of biodiesel fuel, which is to reduce the amount of fossil fuel used and reduce carbon dioxide emissions. The significance may fade.

  The biodiesel fuel composition of the present invention is a mixture of light oil and the fatty acid methyl ester composition of the present invention. When a 100% by mass fatty acid methyl ester product is used as the fuel, the fatty acid methyl ester composition of the present invention is It becomes the biodiesel fuel composition of the present invention. The concentration of the low-temperature fluidity improver for fatty acid methyl esters of the present invention contained in the biodiesel fuel composition of the present invention is not particularly defined, but considering the concentration contained in the fatty acid methyl ester composition of the present invention, the concentration is 0. 0002-5 mass% is preferable, 0.001-3 mass% is more preferable, 0.002-1 mass% is still more preferable.

  In the biodiesel fuel composition of the present invention, a cetane number improver can be blended as necessary. As the cetane improver, various compounds known as cetane improvers for light oils can be arbitrarily used. For example, 2-chloroethyl nitrate, 2-ethoxyethyl nitrate, isopropyl nitrate, butylnite. Rate, primary amyl nitrate, secondary amyl nitrate, isoamyl nitrate, primary hexyl nitrate, secondary hexyl nitrate, n-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, cyclohexyl night Examples thereof include ethylene glycol dinitrate and the like, and alkyl nitrates having 6 to 8 carbon atoms are particularly preferable. The content of the cetane number improver is 500 to 1,400 ppm by mass, preferably 600 to 1,250 ppm by mass, more preferably 700 to 1,100 ppm by mass, based on the total amount of the biodiesel fuel composition. is there. When the cetane number improver is blended, if the blending amount is less than 500 ppm by mass, a sufficient cetane number improving effect cannot be obtained, and particulate matter (PM), aldehydes in diesel engine exhaust gas, and further This is not preferable because NOx may not be sufficiently reduced. Moreover, even if the compounding quantity of a cetane number improvement agent exceeds 1,400 mass ppm, the effect corresponding to it cannot be expected but it may become economically disadvantageous.

  Moreover, a detergent can be mix | blended with the biodiesel fuel composition of this invention as needed. Examples of the detergent include imide compounds; alkenyl succinimides such as polybutenyl succinimides synthesized from polybutenyl succinic anhydrides and ethylene polyamines; polyhydric alcohols such as pentaerythritol and polybutyls. Succinic acid esters such as polybutenyl succinic acid ester synthesized from tenyl succinic anhydride; copolymer polymers such as dialkylaminoethyl methacrylate, polyethylene glycol methacrylate, vinyl pyrrolidone and alkyl methacrylate copolymers, carboxylic acids and amines Ashless detergents such as reaction products of alkenyl succinic acid imide and reaction products of carboxylic acid and amine are preferred. These detergents can be used alone or in combination of two or more. The blending amount of the detergent is not particularly limited, but in order to bring out the effect of blending the detergent, specifically, the effect of suppressing clogging of the fuel injection nozzle, the blending amount of the detergent is the biodiesel fuel composition. It is in the range of 30 to 300 mass ppm, preferably 60 to 200 mass ppm with respect to the total amount of the object. When the blending amount of the detergent is less than 30 ppm by mass, the above-mentioned effect may not appear, and even if it exceeds 300 ppm by mass, an effect commensurate with it cannot be expected. Conversely, NOx in diesel engine exhaust gas , PM, aldehydes, etc. may be increased.

  Furthermore, other known fuel oil additives can be added to the biodiesel fuel composition of the present invention alone or in combination of several kinds for the purpose of further enhancing the performance. Examples of other additives include alcohols such as methanol, ethanol, propanol, 2-propanol and butanol, amines such as triethanolamine and alkyldiethanolamine, hydrocarbon solvents such as hexane, toluene, trimethylbenzene and mineral oil, Esters such as alkyl methyl esters and polyhydric alcohol esters; antioxidants such as phenols, amines, and vitamins; lubricity improvers such as fatty acids, glycerin esters, alkylamines, and fatty acid amides; metal impurities such as salicylidene derivatives Activating agents; Antifreezing agents such as polyglycol ethers; Corrosion inhibitors such as aliphatic amines and alkenyl succinic acid esters; Antistatic agents such as anionic, cationic and amphoteric surfactants; Colorants such as azo dyes ; Silicon-based Agent; drainage agents. The blending amount of other additives can be arbitrarily determined, but the blending amount of each additive is 0.001 to 0.5% by mass, more preferably 0.001 with respect to the total amount of the biodiesel fuel composition. It is in the range of -0.2% by mass.

Hereinafter, the present invention will be specifically described by way of examples.
To a 2000 ml flask equipped with a nitrogen inlet tube, a reflux tube, a nitrogen blowing tube equipped with a stirrer and a thermometer and a condenser, 0.5 mol (126 g) of 1-octadecene and 0.5 mol (50 g) of maleic anhydride as α-olefin, 700 g of methyl ethyl ketone as a solvent and 0.02 mol (0.6 g) of di-tert-butyl peroxide as a catalyst were charged and heated at 120 ° C. for 5 hours to complete the reaction. The solvent was distilled off from the resulting reaction product under reduced pressure to obtain 102 g of a random copolymer of 1-octadecene and maleic anhydride. Subsequently, 88 g was taken out from the obtained random copolymer, charged into a 300 ml flask equipped with a stirrer, a suction pipe for decompression and a thermometer, and further 0.50 mol (93 g) of 1-dodecanol was charged, and p- After adding 0.5 g of toluenesulfonic acid and stirring at 200 ° C. for 5 hours to proceed with the esterification reaction, the pressure was reduced to 1.4 × 10 ⁴ Pa and the reaction was further carried out at 200 ° C. for 3 hours for esterification. The reaction was completed to obtain 170 g of the low temperature fluidity improver of Example 1 (m = 1, n = 1, p = 30 (average value of general formula (1))).

The low temperature fluidity improvers of Examples 2 to 15 and Comparative Examples 1 to 9 were also synthesized by the same method as in Example 1. The weight average molecular weight of the synthesized polymer was measured by GPC and calculated in terms of styrene. The equipment and conditions used are as follows. The composition and evaluation results of the above polymers are shown in Table 1.
Examples 9 to 15 are reference examples.

Equipment used: GL-7400RI (manufactured by GL Sciences Inc.)
Detector: GL-7454 (manufactured by GL Sciences Inc.)
Detection: RI
Column: KF-404HQ (two), KF-402.5HQ, KF-401HQ (all manufactured by GL Sciences Inc.) connected in series Sample concentration: 1%
Solvent: THF
Injection volume: 5ml
Flow rate: 0.3 ml / min Column temperature: 40 ° C

<Pour point test>
The low-temperature fluidity improver was added to soybean oil-derived fatty acid methyl ester so as to be 0.5% by mass (biodiesel fuel composition), and JIS K2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products” The measurement was performed by the method described in the above. That is, 45 ml of the biodiesel fuel composition prepared above is placed in a test tube and heated to 45 ° C., and then the sample is cooled using a cooling bath. Each time the temperature of the sample drops 2.5 ° C, the test tube is removed from the cooling bath and tilted. The temperature when the sample stops moving for 5 seconds is read, and the value obtained by adding 2.5 ° C to this value is the pour point. It was.

<CFPP test>
It added to soybean oil origin fatty acid methyl ester so that the said low-temperature fluidity improver might be 0.5 mass%, and measured based on the method as described in JISK2288 "light oil and clogging point test method". That is, 45 ml of the biodiesel fuel composition prepared above was placed in a test tube, cooled, and each time the temperature decreased by 1 ° C., the sample was passed through a circular wire mesh filter having a diameter of 45 μm and a diameter of 14 mm under a reduced pressure of 2 kPa. The time required for 20 ml of the sample to pass through the filter with a wire mesh was measured, and the temperature when the filtration passage time of the sample exceeded 60 seconds was read as CFPP (clogging point). The devices used are the following devices.
Equipment used: Automatic pour point / cloud point / clogging point tester RPCF-01ML (manufactured by Rihga Co., Ltd.)

Alpha Olefin * Examples 1-14 are all 1-octadecene, Example 15 is 2-octyl-1-decene * Comparative Example 1: 1-dodecene, Comparative Example 2: 1-hexadecene, Comparative Example 3: 1-icosene Comparative Examples 4 to 8: 1-octadecene * Comparative Example 9 used styrene as a raw material instead of α-olefin.
Alcohol * Examples 1-8: all 1-dodecanol, Example 9: 1-icosanol, Example 10: 1-decanol, Example 11: 1-hexadecanol, Example 13: 2-decyl-1 Tetradecanol, Example 14: 1-octacosanol, Example 15: 1-Dodecanol * Comparative Examples 1-9: 1-dodecanol * Comparative Example 10 is evaluated only with soybean methyl ester oil used in the test * In the compounds in Table 1, the groups corresponding to R ¹ and R ² in the general formula (1) are all the same groups.

<Evaluation with composition>
Sample 1: Ethylene vinyl acetate copolymer Random polymerized product having a vinyl acetate content of 30% by mass and a weight average molecular weight of 33,000 Sample 2: Styrene 2-ethylhexyl acrylate copolymer Styrene / 2-ethylhexyl acrylate = 1/1 ( Mole ratio), random polymer product sample having a weight average molecular weight of 19,000 Sample 3: 2-ethylhexyl acrylate polymer Weight average molecular weight of 28,000
Sample 4: Vinyl acetate polymer Weight average molecular weight 32,000

  Each of Samples 1 to 4 above and the polymer used in Example 3 and the polymer used in Example 13 were mixed at a weight ratio of 1: 1, and soybean oil-derived fatty acid so that the mixture would be 0.5% by mass. It was added to the methyl ester and pour point and CFPP tests were performed. Each formulation is as follows and the results are listed in Table 2.

Example 16: Mixture of Sample 1 and Polymer of Example 3 Example 17: Mixture of Sample 1 and Polymer of Example 13 Example 18: Mixture of Sample 2 and Polymer of Example 3 Example 19: Sample Example 20: Mixture of sample 3 and polymer of Example 3 Example 21: Mixture of sample 3 and polymer of Example 13 Example 22: Sample 4 and Example 3 Example 23: Mixture of Sample 4 with the polymer of Example 13

Claims (6)

The low-temperature fluidity improver for fatty acid methyl esters represented by the following general formula (1).

(Wherein, R ¹ and R ² each independently represent a hydrogen atom or a dodecyl group , m and n each independently represent a number of 1 to 50, —C ₁₆ H ₃₃ represents a hexadecyl group , p Represents a number of 1 to 5,000, provided that 80 mol% or more of the total of R ¹ and R ² must be a dodecyl group and m / n = 0.4 to 4. The low-temperature fluidity improver for fatty acid methyl esters according to claim 1, which is obtained by subjecting α-octadecene and maleic anhydride to a polymerization reaction and esterifying 1-dodecanol to the obtained polymer. The low-temperature fluidity improver for fatty acid methyl esters according to claim 1 or 2, an ethylene vinyl acetate copolymer, a styrene (meth) acrylic acid ester copolymer, a (meth) acrylic acid ester polymer, and a vinyl acetate polymer. A low-temperature fluidity improver composition for fatty acid methyl esters, comprising any one or more selected from the group consisting of: A fatty acid methyl ester composition containing 0.01 to 5% by mass of the low-temperature fluidity improver for fatty acid methyl esters according to claim 1 or 2 . A biodiesel fuel composition containing 0.0002 to 5 mass% of the low-temperature fluidity improver for fatty acid methyl esters according to claim 1 or 2 . The low-temperature fluidity improver for fatty acid methyl esters according to claim 1, wherein α-octadecene and maleic anhydride are subjected to a polymerization reaction and 1-dodecanol is esterified to the obtained polymer. Production method.