JPH0639448B2 - Method for producing polyoxyalkylene polyol oleate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a polyoxyalkylene polyol oleate.

[Conventional technology]

Polyoxyalkylene polyol oleate is an emulsifier,
It is used as a dispersant and the like, and is produced by an esterification reaction between a polyoxyalkylene polyol and oleic acid or a transesterification reaction between a polyoxyalkylene polyol and methyl oleate.

However, since the conventional polyoxyalkylene polyol oleate uses oleic acid which has not been sufficiently purified as a raw material, it is colored and has a bad odor. Moreover, the degree of coloring and odor is increased by heating or simply leaving it unsuitable for use in medicine, cosmetics and the like.

To elaborate on conventional oleic acid, conventional oleic acid uses distillation as a purification step.However, by simply distilling, not only impurities in the same boiling range as oleic acid but also impurities having a vapor pressure to some extent are included. Since most of them are entrained in the oleic acid fraction, the effect of separating impurities is insufficient. Further, since the distillation is carried out at a high temperature, degradation of the unsaturated fatty acid due to heat, deterioration of the substrate such as polymerization and isomerization, and a low-boiling point component due to the thermal portion of impurities are mixed in the oleic acid fraction. As a result, the quality of oleic acid deteriorates, and only oleic acid that is colored and has an odor is obtained. Moreover, when the obtained oleic acid was heated, the degree of coloring and odor tended to further increase.

[Problems to be solved by the invention]

Conventional polyoxyalkylene polyol oleate is
Since the above-mentioned oleic acid is used as a raw material and heated during the production of an ester, the obtained product is colored and has an odor. There is a problem in using it in cosmetics and the like, and the development of colorless and odorless polyoxyalkylene polyol oleate has been earnestly desired.

[Means for solving problems]

As a result of diligent studies, the present inventors have found that by esterifying a polyoxyalkylene polyol with oleic acid produced by a specific method, a colorless, odorless, and stable polyoxyalkylene polyol oleate can be obtained. And completed the present invention. That is, the polyoxyalkylene polyol represented by the general formula (1), a fatty acid mixture containing oleic acid and urea are dissolved in an organic solvent and then cooled to separate and remove the precipitated crystals, which are contained in the organic solvent solution. Characterized in that the fatty acid mixture is partially saponified and then recrystallized to separate the crystals, and the obtained crystals are esterified with oleic acid produced by a method of recovering oleic acid by acid decomposition. A method for producing an oxyalkylene polyol oleate.

However, B is a residue of a compound having 3 to 24 hydroxyl groups,
AO is an oxyalkylene group having 2 to 18 carbon atoms, Y is a hydrocarbon group having 1 to 24 carbon atoms, or (AO) _n H, n = 1.
˜100, a = 0 to 23, a + b = 3 to 24.

The method for producing oleic acid used in the present invention will be described in detail.

(A) A fatty acid mixture containing oleic acid and urea are dissolved in an organic solvent, and then cooled to decompose and remove the precipitated crystals. (B) The fatty acid mixture contained in the organic solvent solution is partially saponified and then recrystallized. This is a method for producing oleic acid, in which crystals are separated and the obtained crystals are acid-decomposed.

The step (a) is a step of removing higher saturated fatty acids having 16 or more carbon atoms and monounsaturated fatty acids higher than oleic acid from a fatty acid mixture containing oleic acid, and the resulting organic solvent solution inevitably contains a small amount. Urea remains. When the following step (b) is carried out using this organic solvent solution, the residual urea forms a suitable adduct with the acid salt of oleic acid to form a hard and free-flowing crystal, and therefore the partially saponified fatty acid mixture is mixed. The crystalline state of is improved and filtration of crystals obtained by recrystallization is facilitated, and polyunsaturated fatty acids such as linoleic acid, monounsaturated fatty acids lower than oleic acid, lower saturated fatty acids and other impurities can be efficiently removed. Since it can be performed well, the production of high-purity oleic acid is facilitated.

The fatty acid mixture containing oleic acid used as a raw material can be used if it contains oleic acid, olive oil, sesame oil, rice bran oil, soybean oil, tea seed oil,
Camellia oil, corn oil, rapeseed oil, palm oil, peanut oil,
Fatty acids obtained by hydrolyzing fats and oils such as safflower oil, beef tallow, lard, chicken oil, sheep fat, fish oil and the like can be used, and oleic acid containing commercially available impurities can also be used as a raw material. . As a matter of course, the higher the content of oleic acid, the more efficiently the highly pure oleic acid can be obtained.

As the organic solvent used in the step (a), methanol,
Lower alcohols such as ethanol, n-propanol, and isopropanol, and mixed solvents containing these as the main components are used. The amount of the organic solvent used cannot be unconditionally specified depending on the composition of the raw material fatty acid, the target purity and yield, the setting of the number of crystallizations, etc., but is preferably 0.5 to 10 times the weight of the raw material fatty acid. If it is less than 0.5 times by weight, the separation effect will be lowered, and if it is more than 10 times by weight, the fatty acid concentration will be low and the production efficiency will be lowered, which is disadvantageous.

The amount of urea used depends on the composition of the raw material fatty acid, the target purity and yield, the crystallization temperature, the amount of solvent, etc., but the saturated fatty acid having 16 or more carbon atoms and oleic acid contained in the raw material fatty acid. It is preferably 3 to 50 times by weight of the total amount of the higher monounsaturated fatty acids. If it is less than 3 times by weight, the removal of saturated fatty acids having 16 or more carbon atoms and monounsaturated fatty acids higher than oleic acid will be insufficient, and if it is more than 50 times by weight, the oleic acid yield will decrease.

In the step (a), a fatty acid mixture containing urea and oleic acid is added to an organic solvent and dissolved by heating, and then gradually cooled,
It is usually 30 ° C or lower, preferably 20 to -20 ° C. Saturated fatty acids having 16 or more carbon atoms, monounsaturated fatty acids higher than oleic acid, and the like form adducts with urea and are crystallized. Therefore, these crystals are removed by usual means such as filtration and centrifugation.

Usually, step (a) is sufficient for one operation, but when separation of saturated fatty acids having 16 or more carbon atoms and monounsaturated fatty acids higher than oleic acid is insufficient, this step may be repeated. .

In the step (b), first, a basic compound such as lithium, sodium, potassium hydroxide or carbonate, or a basic compound such as ammonia or the like is added to the organic solvent solution of the fatty acid mixture obtained in the step (b) to partially ken it. Turn into. Oleic acid forms an acid salt by this partial saponification, and when cooled, the acid salt of oleic acid and a small amount of urea remaining in step (a) form an appropriate adduct to form crystals that are easy to filter as a whole, It is easy to separate components to be removed such as polyunsaturated fatty acids. The saponification rate in this case is from 20% of the oleic acid contained to 60% of the total fatty acid mixture, preferably from 30% of the oleic acid to 55% of the total fatty acid mixture. When the saponification rate is less than 20% of oleic acid, the yield of oleic acid obtained is low, and when it exceeds 60% of the total fatty acid mixture, the separation effect is lowered and the crystalline state of the crystallized acid salt of oleic acid is deteriorated. It is difficult to filter and the purity of the obtained oleic acid decreases.

The temperature for cooling to crystallize the acid salt of oleic acid is 10 to -30 ° C, preferably 5 to -20 ° C. 1
If the temperature is higher than 0 ° C, the yield of oleic acid will decrease, and if it is lower than -30 ° C, the purity of oleic acid will decrease.

The produced crystals of the acidic salt of oleic acid can be separated from a solution containing a polyunsaturated fatty acid and the like by a usual method.

The crystal of the acid salt of oleic acid can be further improved in purity by repeating recrystallization.

Solvents used for repeating recrystallization of the acid salt of oleic acid include methanol, ethanol, isopropanol, and n.
-A polar solvent such as butanol, isobutanol, acetone, methyl ethyl ketone, diethyl ether, ethyl acetate, acetonitrile, or a mixed solvent containing these is used. In this case, the concentration of the acid salt of oleic acid is 10 to 10.
50% by weight, and the cooling temperature is preferably 5 to -20 ° C.

The step (c) is a step of adding an acid to an acid salt of oleic acid to cause acid decomposition to obtain oleic acid.

As the acid used for acid decomposition, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, carbonic acid, inorganic acids such as boric acid, acetic acid, oxalic acid, malonic acid, succinic acid, malic acid,
Organic acids such as tartaric acid and citric acid can be used. The amount of the acid used is at least equivalent to the base forming the acid salt of oleic acid, and preferably at least 1.2 times equivalent.

After acid decomposition, the acid remaining in oleic acid is removed by washing with water, and a small amount of polybasic acid such as oxalic acid and citric acid can be added during this washing to prevent emulsification during washing with water, and olein The acid decomposition of the acid salt of the acid is also carried out completely.

In this way, high-purity oleic acid can be obtained, but in order to remove a trace amount of impurities, it is also possible to carry out an adsorbent treatment or distillation which is usually used for refining fatty acids.

As the adsorbent used for the adsorbent treatment, clay, activated clay,
Activated carbon, silica gel, alumina, silica-alumina, ion exchange resins, synthetic adsorbents and the like are available, and they are used alone or as a mixture. Although the amount of the adsorbent used varies depending on the degree of purification of oleic acid and the target quality, it is 0.1 to 5% by weight relative to oleic acid. The temperature of the adsorbent treatment is not less than the melting point of oleic acid, preferably 30 to 80 ° C. The processing time is about 20 minutes to 2 hours.

Distillation is performed under reduced pressure in an atmosphere of an inert gas under the conditions usually used for distillation of oleic acid. A vacuum degree as high as possible and a distillation temperature as low as possible are preferable.

Examples of the oxyalkylene group having 2 to 18 carbon atoms represented by AO include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, dodecene oxide,
It is derived from tetradecene oxide, hexadecene oxide, octadecene oxide, tetrahydrofuran or the like alone or a mixture thereof, and as the hydrocarbon group having 1 to 24 carbon atoms represented by Y, a methyl group, an ethyl group,
Allyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, hexyl group, heptyl group, 2-ethylexyl group, octyl group, nonyl group, decyl group, undecyl group,
Lauryl group, tridecyl group, myristyl group, cetyl group,
Isocetyl group, stearyl group, isostearyl group, olein group, octyldodecyl group, behenyl group, decyltetradecyl group, benzyl group, cresyl group, butylphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group , Dioctylphenyl group, dinonylphenyl group, styrenated phenyl group and the like.

Examples of the compound having 3 to 24 hydroxyl groups include glycerin, diglycerin, polyglycerin, trimethylolethane, trimethylolpropane, 1,3,5 pentanetriol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, sorbitol. And glycerin condensates, polyhydric alcohols such as adonitol, arabitol, xylitol, mannitol, or their partially etherified products, xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, iso. Examples thereof include sugars such as maltose, trehalose, sucrose, raffinose, gentianose, and melezitose, and their partially etherified products.

The esterification reaction is carried out by mixing oleic acid and polyoxyalkylene polyol in the presence or absence of a catalyst such as paratoluenesulfonic acid, sulfuric acid, sodium hydroxide or the like in the range of 90 to 2
At 50 ° C., if necessary, a solvent such as benzene, toluene, xylene may be used, or the reaction may be performed under reduced pressure.

In the present invention, the production method of oleic acid to be used is specified because only the polyoxyalkylene polyol oleate with remarkable coloring and odor can be obtained by using the other production method.

Examples of the present invention will be shown below.

[Example 1] 12.42 kg of urea was added to 40 kg of methanol and dissolved by heating.
Oleic safflower oil distilled fatty acid 1 heated to 50 ℃
0 kg was added and dissolved. Then, the mixture was cooled to 10 ° C. with stirring, and the resulting crystals were centrifugally filtered to obtain 52.12 kg of a filtrate (fatty acid content 6.52 kg, acid value 198.5, urea content 2.32 kg).
415 g of sodium hydroxide was added to this filtrate (containing fatty acid of 45 g).
5.76 kg of an aqueous solution containing (% equivalent weight) was added and dissolved, and the mixture was cooled to −7 ° C. with stirring and filtered to obtain 4.27 kg of acid salt crystals of oleic acid (acid content of 3.7 kg). To this crystal was added 18.56 kg of an aqueous solution containing 930 g of phosphoric acid (1.5 equivalents of acid salt), and the mixture was heated to be acid-decomposed. 0.5% by weight of the obtained oil layer
After sufficiently washing with an aqueous citric acid solution, the product was dehydrated to obtain 3.56 kg of purified oleic acid.

564 g (2 mol) of the obtained purified oleic acid, 1000 g (0.5 mol) of polyoxyethylene (40 mol) sorbitol and 5 g of paratoluenesulfonic acid were mixed and the mixture was heated at 120 ° C.
Heated to. Next, under nitrogen gas flow, 110-130 ℃, 10
The esterification reaction was performed for 8 hours at mmHg or less. After cooling to 70 ° C. and neutralizing with a 10 wt% sodium hydroxide aqueous solution, heating to 100 ° C. and dehydration at 100 to 120 ° C. and 10 mmHg or less for 3 hours, the formed salt was filtered off and 1490 g of polyoxyethylene ( 40 mol) sorbitol tetraoleate was obtained.

The obtained polyoxyalkylene polyol oleate,
In this example, polyoxyethylene (40 mol) sorbitol tetraoleate was subjected to quality evaluation of the following items, and the results are shown in Table 1.

(1) Hydroxyl value, saponification value, peroxide value immediately after production,
Color, smell.

(2) Take 150 g sample in 300 ml beaker, and after heating at 100 ° C. for 24 hours, hydroxyl value, saponification value, peroxide value, color and odor.

(3) After taking 150 g of a sample in a 300 ml sample bottle, sealing it and leaving it in a thermostat at 50 ° C. for 3 months, the hydroxyl value, saponification value, peroxide value, color and odor.

In the following examples and comparative examples, quality evaluation was performed by the same method.

Comparative Example 1 Using commercially available distilled oleic acid as oleic acid, esterification was performed in the same manner as in Example 1 to obtain 1470 g of polyoxyethylene (40 mol) sorbitol tetraoleate.

The obtained polyoxyethylene (40 mol) sorbitol tetraoleate was subjected to the same quality evaluation as in Example 1, and the results are also shown in Table 1.

[Example 2] 282 g (1 mol) of oleic acid and polyoxypropylene (70 mol) pentaerythritol 2100 produced in Example 1
Dissolve 8 g of g (0.5 mol) paratoluene sulfonic acid in 1 of toluene and charge into a 4-necked flask of 5 equipped with a cooling tube and a water separator until about 18 ml of water is separated at 110 to 120 ° C. The reaction was carried out. 10% by weight, cooled to 80 ℃
After neutralizing with a sodium hydroxide solution, water 1 at 80 ° C. was added and the mixture was washed with water and left standing to remove the separated water. After washing with water twice more, 110-120 ℃, 10mmHg
After the volatile components were distilled off over 3 hours, the remaining salt was filtered off to obtain 2280 g of polyoxypropylene (70 mol) pentaerythritol dioleate. The quality was evaluated and the results are shown in Table 2.

[Comparative Example 2] As oleic acid, commercially available distilled oleic acid was used for esterification in the same manner as in Example 2 to obtain 2260 g of polyoxypropylene (70 mol) pentaerythritol dioleate. The quality was evaluated and the results are also shown in Table 2.

[Example 3] 282 g (1 mol) of oleic acid prepared in Example 1 and 500 g (0.33 mol) of polyoxyethylene (30 mol) diglycerin and 2.5 g of paratoluenesulfonic acid prepared in Example 1 were used under the same conditions as in Example 1. Esterification was carried out to obtain 730 g of polyoxyethylene (30 mol) diglycerin trioleate.
The quality of the obtained product was evaluated, and the results are shown in Table 3.

Comparative Example 3 Using commercially available distilled oleic acid as oleic acid, esterification was carried out in the same manner as in Example 3 to obtain 700 g of polyoxyethylene (30 mol) diglycerin trioleate. The quality was evaluated and the results are also shown in Table 3.

[Example 4] 282 g (1 mol) of oleic acid prepared in Example 1, polyoxyethylene (10 mol) and polyoxypropylene (10 mol)
Methyl glycoside (300 g, 0.25 mol) and paratoluenesulfonic acid (2 g) were esterified in the same manner as in Example 1 to give 540 g of polyoxyethylene (10 mol).
Polyoxypropylene (10 mol) methyl glucoside tetraoleate was obtained. The quality of the obtained product was evaluated, and the results are shown in Table 4.

Comparative Example 4 Using commercially available distilled oleic acid as oleic acid, esterification was carried out in the same manner as in Example 4 to obtain 530 g of polyoxyethylene (10 mol) polyoxypropylene (10 mol) methylglucoside tetraoleate. Got ate. The quality was evaluated and the results are also shown in Table 4.

[Effects of the Invention] According to the method of the present invention, a polyoxyalkylene polyol oleate comprising a highly pure oleic acid and a polyoxyalkylene polyol produced by a specific method is colored,
It is a product that has no odor and is stable over time even when heated.

Claims (1)

[Claims] 1. A polyoxyalkylene polyol represented by the following general formula (1) is dissolved in an organic solvent of a fatty acid mixture containing oleic acid and urea, and then cooled to separate and remove precipitated crystals, The fatty acid mixture contained in the organic solvent solution is partially saponified and then recrystallized to separate the crystals, and the obtained crystals are esterified with oleic acid produced by a method of acid-decomposing and recovering oleic acid. A method for producing a polyoxyalkylene polyol oleate, comprising: However, B is a residue of a compound having 3 to 24 hydroxyl groups,
AO is an oxyalkylene group having 2 to 18 carbon atoms, Y is a hydrocarbon group having 1 to 24 carbon atoms, or (AO) _n H, n = 1.
˜100, a = 0 to 23, a + b = 3 to 24.