JP2001055359A - Monounsaturated fatty acid specified with its double bond position - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an alkenoic acid having a specific carbon number containing a specific amount of a specific isomer and useful as a raw material of a soap composition or soft finishing agent composition. SOLUTION: This objective monounsaturated fatty acid of a 14-22C alkenoic acid which is an isomer of the formula: CH3(CH2)mCH=CH(CH2)nCOOR [10<=(m+n)<=18] and contains 20-93 wt.% isomer of n=7, 1-10 wt.% isomer of n<=6 and 5-80 wt.% isomer of n>=8, is obtained by hydrogenating a polyunsaturated fatty acids of the formula: CH3(CH2)cCH=CH(CH2)bCH=CH (CH2)a-COOR [8<=(a+b+c)<=16; R is H, a 1-10C alkyl or the like] or the formula: CH3(CH2)dCH=CH(CH2)cCH=CH(CH2)bCH=CH(CH2)a-COOR [6<=(a+b+c)<=14)].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to monounsaturated fatty acids whose double bond position is specified.

[0002]

2. Description of the Related Art It is known that the melting point of a fatty acid having one unsaturated double bond in a molecule decreases as the position of the double bond becomes more internal when the hydrocarbon chain is the same. . For example, in the case of octadecenoic acid having a hydrocarbon chain length of 18, oleic acid, which is cis-9-octadecenoic acid, has the lowest melting point (13 ° C.), and cis-6-octadecenoic acid (petrosenic acid) has a melting point of 30 ° C. In the case of -11-octadecenoic acid, the melting point rises when the position of the double bond is shifted to both sides from the median value of the hydrocarbon chain, such as 15 ° C. Oleate soap has a low melting point, and therefore has poor foaming properties such as bubble power and fineness of foam, and further has a disadvantage that when solidified, the soap becomes too soft. For this reason, Japanese Patent Application Laid-Open No. 3-244699 discloses a high melting point substance, elaidic acid salt (elaidic acid (trans-9).
Attempts have been made to improve the foaming performance by adding (octadecenoic acid) a melting point of 46 ° C.

[0003] On the other hand, when a compound (IV) in which oleic acid is used as a raw material and converted into quaternary ammonium is used as a softening agent for clothing, it has excellent water absorbency due to its hydrophilic property, but has poor flexibility. There was a drawback that it would be inferior. Therefore, as disclosed in Japanese Patent Application Laid-Open No. 2-139480, a quaternary ammonium compound (V) derived from elaidic acid, which is a high-melting substance, is added to improve the flexibility.

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As described above, a raw material such as oleic acid having a double bond position at the median of a hydrocarbon chain and having a cis structure is used as a soap composition or a soft finish composition. Discloses a method for solving the drawback caused by the low melting point by some means.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an alkenoic acid or an ester thereof which compensates for the performance disadvantages of monounsaturated fatty acids caused by having a low melting point.

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the inventors of the present invention have conducted intensive studies and as a result, synthesized using monounsaturated fatty acids having widely distributed double bond positions as raw materials. The present inventors have found that compounds greatly improve quality and properties, and completed the present invention. That is, the present invention is an isomer represented by the following general formula (I), which contains 20 to 93% by weight of n = 7, 1 to 10% by weight of n ≦ 6, and 5 to 80% by weight of n ≧ 8. Having 14 or more carbon atoms
22. Alkenic acid or an ester thereof is provided.

[0007]

Embedded image (Wherein, R represents hydrogen or an alkyl or alkenyl group having 1 to 10 carbon atoms. In addition, m and n represent 10 ≦ m + n ≦ 1
0 or natural number that satisfies 8)

[0008] The monounsaturated fatty acids of the present invention include octadecenoic acid, hexadecenoic acid, tetradecenoic acid, oleic acid, tutuic acid, fiseteric acid, myristoleic acid,
5-myristoleic acid, pentadecenoic acid, zomaric acid, 2-palmitoleic acid, 7-palmitoleic acid, cis-9-palmitoleic acid, trans-9-palmitoleic acid, petroselinic acid, petroseleidic acid, elaidic acid, basenic acid, Ascrepic acid, vaccenic acid,
Gadolinic acid, codoic acid, gondoic acid, trans-
Gondoic acid, cetreic acid, erucic acid, brassic acid and the like. Preferably a fatty acid having one double bond having 10 to 22 carbon atoms, more preferably a fatty acid having one double bond having 14 to 20 carbon atoms, more preferably octadecenoic acid, hexadecenoic acid, Zomaric acid, 2-palmitoleic acid, 7-palmitoleic acid, cis-9-palmitoleic acid, petroselinic acid, petroseleidic acid, elaidic acid, basenic acid, and oleic acid. In addition, methanol, ethanol, propanol, isopropanol with these monounsaturated fatty acids,
Esters with butanol, pentanol, hexanol, cyclohexanol, octanol, decanol, etc.
Preferably, methanol, ethanol, propanol,
Esters with isopropanol are mentioned.

The contents of the isomers represented by the general formula (I) are represented by the positions from the 2-position to the 8-position,
1.0% to 10.0% by weight or less, and 90.0% to 90.0%
3.0% by weight, 10th or higher is 5.0 to 80.0% by weight. Preferably, 3.0% by weight or less in the 2nd to 7th positions,
1.0 to 8.0% by weight, 92.0 to 92.0%
%, 2.5 to 35.0% by weight at 10th position, 1.0 to 29.0% by weight at 11th position, 0.5 to 20.0% by weight at 12th position, 5.0% by weight at 13th position or more % Or less. More preferably, the second to seventh positions are 1.0% by weight or less, and the eighth position is 1.
5 to 6.0% by weight, 94.0th position 24.0 to 91.0% by weight,
3.0 to 30.0% by weight in 10th place, 1.5 to 2 in 11th place
7.0% by weight, 12th rank 0.8-18.0% by weight, 13
Or more is 3.0% by weight or less.

The determination of the above positional isomer is carried out as follows. That is, the monounsaturated fatty acids of the present invention are subjected to a dimethyl disulfide addition GCMS method. The method is described in Fr.
ancis (GW Francis, Chemica)
l and Physicsof Lipids, 2
9, 369 (1981)) and Shibahara et al. (K. Yamamoto, A. Shibahara, C.).
chemical and Physics of Lip
ids, 60, 39 (1991)) as a method for determining the double bond position of unsaturated fatty acids. This method
Dimethyl disulphide and I ₂ as a catalyst utilizes the addition to the double bond portion in monounsaturated fatty acids. When the obtained dimethyl disulfide adduct is analyzed by GCMS, the position of the double bond can be determined from the mass spectrum pattern. For example, taking methyl oleate as an example, peaks are given at 217 and 173, the following structural formula can be estimated, and the ninth position can be determined as a double bond position. The double bond position can be similarly determined for other positional isomers.

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The monounsaturated fatty acids of the present invention include, as saturated fatty acids, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, laurenic acid,
Tridecanoic acid, myristic acid, pentatecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid,
Arachinic acid, heneicosanoic acid, behenic acid, tricosanoic acid and the like, and their esterified products with an alcohol having an alkyl group or an alkenyl group having 1 to 10 carbon atoms may be mixed.

The monounsaturated fatty acids of the present invention can be obtained by hydrogenating a polysaturated fatty acid represented by the general formula (II) or (III) as a raw material. Examples of the polysaturated fatty acids include tetradecadienoic acid, tetradecatrienoic acid, hexadecadienoic acid, hexadecatrienoic acid, octadecadienoic acid, octadecatrienoic acid, icosatrienoic acid, docosadienoic acid, linoleic acid, and linoelaidic acid. , Α-eleostearic acid, β-eleostearic acid, linolenic acid, γ-linolenic acid, linolenic elaidic acid, pseudo eleostearic acid, and the like. It is preferably a fatty acid having two or more double bonds having 16 to 18 carbon atoms, and more preferably linoleic acid or linolenic acid. Methanol with these polyunsaturated fatty acids,
Esters with ethanol, propanol, isopropanol, butanol, pentanol, hexanol, cyclohexanol, octanol, decanol, etc., preferably esters with methanol, ethanol, propanol and isopropanol.

[0013]

Embedded image (In the formula, a, b, and c represent 0 or a natural number satisfying 8 ≦ a + b + c ≦ 16. In addition, R represents hydrogen or a carbon number of 1 to 1.
0 represents an alkyl or alkenyl group)

Embedded image (Where a, b, c, and d represent 0 or a natural number satisfying 6 ≦ a + b + c + d ≦ 14, and R represents hydrogen or an alkyl group or alkenyl group having 1 to 10 carbon atoms)

Hydrogenation (hereinafter also referred to as hydrogenation) is used to gradually prevent deterioration of fats and oils and fatty acids having a large number of unsaturated double bonds in the molecule due to oxidation, and to reduce color tone and odor. BACKGROUND ART In order to improve and further improve various physical properties, it is widely practiced to hydrogenate and reform fats and oils and fatty acids in the presence of a catalyst. Among such hydrogenation reactions, a hydrogenation reaction that leaves a double bond in a molecule may be referred to as a partial hydrogenation reaction, and a hydrogenation reaction that leaves no double bond at all may be referred to as an extreme hydrogenation reaction. In order to obtain the compound of the present invention, a partial hydrogenation reaction is performed. This partial hydrogenation reaction is
Reaction temperature 100 to 250 ° C, preferably 160 to 21
The reaction is performed by stirring the polysaturated fatty acid at 0 ° C. in a hydrogen atmosphere in the presence of a catalyst. At this time, the hydrogen pressure is 0.001 to 3.0M.
Pa · G, preferably 0.01 to 1.0 MPa · G. As the catalyst, a compound containing nickel, cobalt, copper, copper-chromium, platinum, and palladium is used. In particular, reduced nickel, nickel formate , Raney nickel, flake nickel and stabilized nickel mainly composed of nickel as a constituent element and supported on diatomaceous earth are preferably used. The amount used depends on the hydrogenation temperature and time, but is usually 0.01 to 1.0% by weight, preferably 0.05 to 0.1% by weight, based on the raw material polyunsaturated fatty acids.
3% by weight. By this partial hydrogenation, the carbon-carbon double bond in the molecule existing in the polyunsaturated fatty acids is hydrogenated. Here, if the partial hydrogenation reaction proceeds excessively, the reaction will extremely shift to a hydrogenation reaction. Therefore, hydrogen gas is introduced while grasping the amount of hydrogen addition so that one double bond remains in the molecule.

In the present invention, the reaction vessel is preferably a pressure-resistant type equipped with a stirrer, and its shape and size are not particularly limited. Further, the reaction vessel may be a batch-type reaction vessel or a continuous-type reaction vessel.
After the completion of the partial hydrogenation reaction, the reaction vessel is cooled to 50 to 120 ° C. or lower, and the catalyst is filtered to obtain a desired monounsaturated fatty acid.

The monounsaturated fatty acids of the present invention obtained by the above partial hydrogenation reaction have a carboxyl group in the molecule and can be used as various raw materials. For example, sodium hydroxide, alkali metal salts such as potassium hydroxide,
A monounsaturated fatty acid salt obtained by neutralization or hydrolysis with an organic amine such as triethanolamine or diethanolamine can be used as a soap composition to provide a detergent having excellent foam properties. Further, the carboxyl group was esterified with a dialkylene dimethyl ammonium salt or a monounsaturated fatty acid obtained by using a monounsaturated amine obtained by aminating an organic amine such as ammonia with hydrogen and hydrogen and diethanolmethylamine. Ammonium salts that have been quaternized with methylene chloride or the like later provide softener compositions with high flexibility. Furthermore, the monounsaturated aliphatic alcohol obtained by hydrogenating the carboxyl group and the compound obtained by addition-polymerizing the alkylene oxide thereto were used as a nonionic activator, and the monounsaturated aliphatic alcohol was sulfated. The compounds can be used as anionic surfactants.

[0017]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the following examples, “%” is “% by weight”.

Example 1 A 5-L four-necked flask was equipped with a stirrer, a thermometer, and a condenser.
1315 g of dehydrated methanol (manufactured by Kanto Chemical Co., Ltd.)
2000g, p-toluenesulfonic acid (manufactured by Kanto Chemical Co.)
After the addition of 5 g, the mixture was refluxed at 68 ° C. for 8 hours while stirring. Thereafter, methanol and generated water were distilled off under reduced pressure, and 2,000 g of dehydrated methanol and Molecular Sieve 4A (manufactured by Junsei Chemical Co., Ltd.) were added thereto.
For 8 hours. After methanol and water were distilled off from the obtained product under reduced pressure, 1000 g of ether and 1000 g of water in which 2 g of sodium hydrogen carbonate were dissolved were added to extract an esterified product. Subsequently, the ether layer was repeatedly washed with water until the aqueous layer became neutral. 30 g of anhydrous sodium sulfate was added to the obtained ether layer, and the mixture was allowed to stand for one day and night. Then, sodium sulfate was filtered, and ether was distilled off under reduced pressure. The properties of the obtained esterified product (A) were as follows. After 820 g of the esterified product (A) and 0.62 g of flake nickel catalyst SO-550 manufactured by Sakai Chemical Co. were placed in a 1.5 L autoclave, and the atmosphere was replaced with nitrogen while stirring, the reactor was heated to 190 ° C. Subsequently, hydrogen was introduced from the sparger at a rate of 500 mL / min, and the hydrogen supply amount was 60.
When reaching 35 SL, the hydrogen supply was stopped. The pressure gauge at this time indicated 0.2 MPa · G. When the temperature of the reaction solution reached 50 ° C., filtration was performed to remove the nickel catalyst. The properties of the obtained partially hydrogenated esterified product (B) were as follows.

Next, the partially hydrogenated esterified product (B) was prepared by the method of Shibahara et al. (K. Yamamoto, A. Shibahara, C.
chemical and Physics of Li
pids, 60, 39 (1991)).
Dimethyl disulfide was added to the double bond to the monounsaturated fatty acids using ₂ as a catalyst, and the resulting dimethyl disulfide adduct was analyzed by GCMS. The analysis was performed as follows. An extract equivalent to 3 μmol as a partially hydrogenated esterified product is placed in a small test tube with a glass stopper, and 1 ml of dimethicyl disulfide containing 13 mg of iodine is added. After bubbling with nitrogen and sealing, the mixture is shaken in a 35 ° C. incubator at a stroke rate of 40 times / min for 30 minutes. 30% after opening (wt / vo
l) Aqueous NaHSO ₃ solution is added until the color of I ₂ disappears, 1 ml of hexane-ether (1: 1) is added and shaken. The dimethyl disulfide adduct is recovered in the upper layer.
This upper layer is directly injected into the GCMS. GCMS analysis (GC conditions) Column: SP2330 (80% bicyanopropyl 20% cyanopropyphenylpolysoloxane) Column temperature: 200 ° C → 250 ° C 3 ° C / min Inlet temperature: 250 ° C Detector temperature: 250 ° C Carrier gas: He split 100: 1 (MS condition) Inlet and Ion Mode Inlet selection Capillary Run time (min) 30 Ion mode EI + Accel voltage (KV) 10 Time for accelon (min) Table 1 shows the results obtained by analyzing the positional isomer of the compound (B).

[0020]

[Table 1]

Example 2 Pastel M-182 manufactured by Lion Oreo Chemical Co., Ltd.
(Composition analysis (GC analysis): C16F0 = 0.5%, C1
8F0 = 9.0%, C18F1 = 74.0%, C18F
(2 = 16.0%, C20F0 = 0.5%) as a raw material and partially hydrogenated by the method according to Example 1 to obtain a partially hydrogenated esterified product (C). Table 2 shows the results of analyzing the positional isomers of the partially hydrogenated esterified product (C).

[0022]

[Table 2]

Reference Example According to Example 1, Extra Oleic 90 manufactured by NOF Corporation was esterified. The properties of the obtained esterified product (D) were as follows. Table 3 shows the results of analyzing the positional isomers of the esterified product.

[0024]

[Table 3]

Example 3 To each of 1126 g of the partially hydrogenated ester (B), the partially hydrogenated ester (C) and the ester (D),
238 g of methyldiethanolamine, 0.84 g of magnesium oxide, 1.18 g of potassium hydroxide and 3 g of water were charged into a 2 L 4-neck flask equipped with a gas injection tube and a two-stage condenser, and nitrogen gas was injected at a rate of 0.8 L / min. The temperature was raised from room temperature to 200 ° C. while distilling off the by-product methanol, and reacted at 200 ° C. for 10 hours. The concentration of unreacted methyl ester in the reaction was 3-4%. Then, while stirring vigorously at 65 ° C., a solution of a mixed solvent of sulfuric acid having a concentration of 29.8% with an equivalent ratio of 1.05 times the amount of the alkali catalyst (sulfuric acid / ethanol / water = 29.8 / 6).
After adding 3.1 / 7.1), the mixture was aged for 30 minutes. After ripening, centrifugation was performed at 3500 G for 1 minute. In the upper layer, a pale yellow transparent dialkylene ester amine (E, EB, EC, E-
D) 1100 g were obtained. Esteramine (E) 700g
And 61 g of ethanol were charged into an autoclave, and 83 g of methyl chloride was introduced at 90 ° C. over 7 hours to cationize. After completion of the reaction, the mixture was cooled and depressurized, and then 132 g of ethanol was added at 75 ° C. 48 g of water was added to cool the reaction product and adjust the concentration of the cation active ingredient to 68%. Thus, the pale yellow transparent dialkylene diester cation (F, FB, F depending on the esteramine used)
-C, FD) 1000 g of a 68% solution was obtained. Next, 25 g of F was taken as an oil phase, and 75 g of water adjusted to pH = 3 was taken as an aqueous phase, and emulsified at 40 ° C. using an emulsifier. Table 4 shows the viscosity of the obtained emulsion.

[0026]

[Table 4]

As described above, the viscosity of the obtained emulsion tends to show a lower viscosity as the position of the double bond is distributed.
When weighing a certain amount after emulsified product is bottled, FD
It has been found that FB and FC can be weighed quickly as compared with, and this is a great advantage.

Claims (1)

[Claims] 1. An isomer represented by the following general formula (I), wherein n = 7 is 20 to 93% by weight, n ≦ 6 is 1 to 10% by weight, and n ≧ 8 is 5 to 80% by weight. An alkenoic acid having 14 to 22 carbon atoms or an ester thereof. Embedded image (Wherein, R represents hydrogen or an alkyl or alkenyl group having 1 to 10 carbon atoms. In addition, m and n represent 10 ≦ m + n ≦ 1
Indicates 0 or a natural number that satisfies 8. )