JPH0552191B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing polyalcohol fatty acid esters, and more particularly to a method for easily producing polyalcohol fatty acid esters with a high synthesis rate using an enzymatic method. [Prior Art] Various methods for chemically producing fatty acid esters of polyalcohols have been proposed, but either esterification or alcoholysis has been put into practical use as an industrial production method. Esterification involves adding an excess of polyalcohol to the fatty acid ester, and alcoholysis involves adding an excess of polyalcohol to the fatty acid ester, and generally heating the mixture to 200-250°C in the presence of a catalyst.
Polyalcohol fatty acid esters are produced. On the other hand, it has been known for a long time about animal and plant lipases that glyceride is synthesized from glycerin and fatty acids by lipases, but in recent years, along with the development of microbial lipases, there have been reports on the production of glycerides by lipases. and patents began to be seen. For example, Tsujisaka et al. reported the production of glycerides using four types of acid lipases: Aspergillus niger, Rhizopus delemar, Geotricum candidum, and Penicillium cyclopium. Reporting [Biochim. Biophys. Acta.,
489, 415 (1979)]. Additionally, they are Biochim.
In Biophys. Acta. 575 , 156 (1979), it was reported that esters were also produced between propylene glycol or diglycerin and oleic acid using the above lipase. In addition, a patent related to an enzymatic production method for monoglycerides uses the four types of acidic lipases used by Tsujisaka et al., and adds water and 0.01% protein to glycerin and fatty acids to produce glycerides including monoglycerides in an emulsion. method (Japanese Patent Publication No. 51-7754), method using lipase produced by Rhizopus chinensis HIS (Japanese Patent Publication No. 57-23535), further using Candida cylindracea etc. as the lipase, There is a method of producing glyceride using an emulsion in which water is added to glycerin and fatty acid methyl (JP-A-59-118094, JP-A-59-118095). However, all of the above methods involve the production of monoglyceride by lipase in an emulsion in which a large molar excess of glycerin relative to the fatty acid is added and water is used as a reaction solvent. [Problems to be solved by the invention] As mentioned above, in the chemical production method of polyalcohol fatty acid ester, the reaction is carried out under high temperature conditions, but it is necessary to increase the reaction temperature in order to proceed with the reaction. On the other hand, heat causes intramolecular dehydration and decomposition of the polyalcohol, causing coloration, polymerization, and even burnt odor, which has an unfavorable effect on the performance of the product as a surfactant and its commercial value. Furthermore, due to the need to minimize the adverse effects of heat, there are certain permissible limits on reaction heat, reaction time, and substrate concentration, and in practice, the monoester concentration that can be produced is limited to 40 to 50%. On the other hand, the enzymatic reaction method using lipase allows the reaction to be carried out under mild conditions of room temperature and pressure, and does not have any adverse effects on polyalcohols or their ester products. Many technical proposals have been made regarding the production of glyceride by lipase, but these proposals have various problems. There are many possible reasons for this, but the biggest reason seems to be the low synthesis attainment rate. In other words, although all of the previously proposed reports involve adding a large excess of glycerin to fatty acids and their lower alcohol esters, there is a large amount of unreacted glycerin in the ester product. Even if the amount of fatty acids and lower alcohols is small, about 30% of the added amount remains. Monoglycerides containing a large amount of unreacted fatty acids and their lower alcohol esters have almost no commercial value, and even if attempts are made to separate and remove these unreacted substances from the monoglyceride mixture that has produced them, unlike separation from triglycerides, , it is very difficult to remove it, and if we dare to remove it, we will lose economic efficiency. Furthermore, in the conventional proposal for a method for producing polyalcohol fatty acid ester using an enzymatic method, water is used as a reaction solvent. This is because fatty acids and polyalcohols are poorly soluble in each other, and they alone cannot provide fluidity. Therefore, lipase is dissolved in water, and an emulsion is formed using water as a medium to widen the interfacial area to facilitate the reaction. However, in this case, the fatty acid and polyalcohol will separate unless a surfactant is added to maintain a stable emulsion or an emulsified state is constantly maintained by vigorous stirring. The reaction cannot proceed. However, there is a natural limit to the expansion of the interfacial area, and lipase is originally known as a typical hydrolytic enzyme along with protease and amylase, and its general function is to convert esters in the presence of water. Not only does this reduce the ability to produce esters, but there is also the risk of causing re-decomposition of the esters that have been produced. In addition, all proposals for water solvent systems have problems, such as the need for strong centrifugal separation in order to separate the ester product obtained by the water emulsion reaction from the emulsion after the reaction. Thus, there has been a desire for a method for easily obtaining polyalcohol fatty acid esters by an enzymatic method without the drawbacks of using an aqueous solvent system and with a high synthesis rate, and the present invention solves this problem. [Means for solving the problem] In view of the above-mentioned circumstances, the present inventors believe that the action of enzymes is indispensable to the presence of water as in the past, and as long as we consider reactions in aqueous systems, the ester synthesis reaction is Based on the idea that the reaction equilibrium law between hydrolysis and synthesis reaction must be followed, and low synthesis rate and re-decomposition cannot be avoided, water is added substantially without being bound by conventional concepts. We conducted intensive research on lipases that enable the production of polyalcohol fatty acid esters in the presence or absence of organic solvents. As a result, lipases such as those produced by microorganisms of the genus Achromobacter (Japanese Patent Publication No. 49-32080), lipases produced by microorganisms of the genus Alcaligenes (Japanese Patent Publication No. 58-36953, Japanese Unexamined Patent Publication 1973-
No. 59093) is dehydrated in the presence or absence of an organic solvent without substantially adding water until the water content of the reaction system reaches 0.1% by weight (hereinafter, % water content is 0.1% by weight). It has been found that there is a surprising phenomenon in which a wide range of fatty acids and polyalcohols produce esters consisting mainly of monoesters at high concentrations when the reaction is carried out in the following manner (indicated by weight percentage). The present invention was completed based on this discovery. That is, the present invention uses a polyalcohol selected from propylene glycol, glycerin, and polyglycerin, and a saturated or unsaturated fatty acid having a carbon number of _C2 to _C22 (where the fatty acid has a hydroxyl group, a carboxyl group, or a phenyl group as a substituent). may have)
Alternatively, a mixture of a C ₁ to _{C 3} lower alcohol and the above-mentioned fatty acid forming an ester is added in the presence or absence of an organic solvent (excluding a primary alcohol solvent) without substantially adding water. This is a method for producing polyalcohol fatty acid ester, which is characterized by allowing microbial alkaline lipase to act on the reaction system while dehydrating it so that the water content of the reaction system becomes 0.1% or less. The object of the present invention is to provide a method for easily obtaining polyalcohol fatty acid esters with a high synthesis rate (esterification rate) that is not possible with enzymatic methods. In the present invention, polyalcohol fatty acid esters include not only esters produced from polyalcohols and fatty acids by the action of lipase, but also polyalcohol fatty acid esters produced between lower alcohol esters of fatty acids and polyalcohols. The present invention will be explained in detail below. The polyalcohols used in the present invention include propylene glycol [CH ₃・CHOH ・CH ₂ OH], glycerin [CH ₂ OH ・CHOH ・CH ₂ OH], and polyglycerin [CH ₂ OH ・CHOH ・CH ₂ -O ( −
CH ₂ −CHOH−CH ₂ −O) _o CH ₂ −CHOH・CH ₂
OH] (however, n = 0 to 28). Generally, polyglycerin is produced by heating glycerin at 150 to 300° C. for about 2 to 20 hours in the presence of an inert gas and a catalyst to cause a dehydration condensation reaction. Therefore, polyglycerin has a wide range of polymerization degrees, and linear polyglycerin with n=0 to 28 can be obtained, but by selecting the above reaction conditions, the desired average degree of polymerization can be achieved. Polyglycerin is produced. Commercially available polyglycerin includes, for example, diglycerin with n=0,
Examples include tetraglycerin with n = 2, hexaglycerin with n = 4, and decaglycerin with n = 8, but these are all products that have an average degree of polymerization calculated from the hydroxyl value, and are not single polymers. Not polyglycerin. Therefore, in the present invention, any polymer of glycerin can be used as polyglycerin. Furthermore, the fatty acid used in the method of the present invention is a saturated or unsaturated fatty acid having a carbon number of _C2 to _C22 (the fatty acid may be substituted with a hydroxyl group, a carboxyl group, or a phenyl group). In the present invention, fatty acid refers not only to acids present in oils and fats, but also includes other organic acids. Examples of unsubstituted _C2 to _C22 fatty acids include acetic acid, propionic acid, acrylic acid,
Butanoic acid, crotonic acid, methacrylic acid, valeric acid, caproic acid, 2-methylvaleric acid, sorbic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid , linoleic acid, eicosanoic acid, docosanoic acid, arachidonic acid, etc. Furthermore, among fatty acids with substituents, those having a hydroxyl group include ricinoleic acid, dihydroxystearic acid, etc., and examples of fatty acids having a carboxyl group include malonic acid, maleic acid, succinic acid, glutaric acid, Adipic acid,
Examples include pimelic acid, suberic acid, azelaic acid, sebacic acid, and tetradecanedioic acid. Examples of those having a phenyl group include phenyl acetic acid, cinnamic acid, and 3-phenylpropionic acid. Furthermore, the above fatty acid may form an ester with a C ₁ to C ₃ lower alcohol, and this C ₁
~ _C3 lower alcohols include methanol, ethanol, propanol, glycerin,
Specific examples of these fatty acid esters include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, ethyl laurate, ethyl palmitate, ethyl stearate, ethyl oleate, and laurin. Examples of glycerides include glycerin tristearate, glycerin trioleate, coconut oil, soybean oil, cottonseed oil, palm oil, beef tallow, lard, and olive oil. . Examples include the fatty acids and lower alcohol esters thereof as described above, but in the present invention, there is no restriction on the selection of the fatty acids and lower alcohol esters. Next, regarding the microbial alkaline lipase used to carry out the present invention, any microbial alkaline lipase can be used, but for example, Meito-AL-865 belonging to the genus Achromobacter (hereinafter referred to as "Lipase-AL") produced by the lipase (Special Publication No. 49-32080) (hereinafter referred to as "Lipase-AL") produced by No. 1213 of the Microtechnical Research Institute, Meito PL-266 (hereinafter referred to as "Lipase-AL") produced by the genus Alcaligenes. Lipase (Special Publication No. 58-36953) (hereinafter referred to as
Lipase No. PL266), Meito No. PL-679 (Feikoken Bacterial Serial No. 3783), which also belongs to the genus Alcaligenes.
Lipase (Japanese Unexamined Patent Publication No. 53-59093) (hereinafter referred to as Lipase-PL679) produced by
In particular, it can be cited as a specific example of an effective lipase with excellent solvent resistance and ester synthesis ability. This point will be explained using an experimental example. Experimental example 1 Stability in solvent Lipase-PL679 (Meito Sangyo), Lipase-
Take 25 mg each of PL266 (Meito Sangyo) and Lipase-AL (Meito Sangyo) powders into a 7 ml centrifuge tube with a stopper, and add various solvents such as tertiary butyl alcohol, acetonitrile, tertiary amyl alcohol, acetone,
Hexane, diacetone alcohol, 2,4-dimethyl-3-pentanol, and 2 ml of water were added, thoroughly stirred, and shaken at 37°C for 24 hours, and the remaining activity was measured by lipase titration. Lipase was measured using the method of Kunio et al. for lipase-PL679 and lipase-PL266 [Agric.Biol.
Chem. 46 (5), p. 1159, 1982], and for lipase-AL, the method of Kunio et al. [Oil Kagaku 23 (2), p. 98,
1974]. The results are shown in Table 1. [Table] Experimental Example 2 Ester synthesis ability of various lipases in solvent Various lipases, namely alkaline lipase Lipase-PL679 (Meito Sangyo), Lipase-PL266
(Meito Sangyo), Lipase-AL (Meito Sangyo), and non-alkaline lipase Lipase-MY (Meito Sangyo), Lipase-MAP4 (Amano Pharmaceutical), Lipase-AP10 (Amano Pharmaceutical), Oripase 2S (Osaka Seiken) ),
Lipase powder 100mg such as Talypase (Tanabe Pharmaceutical)
, various solvents, namely tertiary butyl alcohol,
In the presence of tertiary amyl alcohol, diacetone alcohol, and 5 ml of 2,4-dimethyl-3-pentanol, 0.5 g of the dehydrating agent Molecular Seasieves 3A [sold by Wako Pure Chemical Industries, Ltd.] was added, and polyalcohol was added. Ester synthesis was carried out by reacting 0.163 g of glycerin as a compound and 0.5 g of oleic acid as a fatty acid at 37°C for 48 hours, and the production of ester was determined by the consumption of fatty acids. The results are shown in Table 2. [Table] The above lipase-AL, lipase-PL266, and lipase-PL679 are all alkaline lipases that are composed of high molecular weight proteins and have an optimal pH on the alkaline side. It is presumed that this is somehow related to particularly high stability in solvents and ability to synthesize esters. Therefore, even lipases other than these can maintain their activity stably in the presence or absence of organic solvents (excluding primary alcohol solvents) without substantially adding water. In addition, any microbial alkaline lipase can be used as long as it is a microbial alkaline lipase with a strong ability to synthesize esters between polyalcohols and fatty acids, and is compatible with the practice of the present invention, and there are no restrictions on its origin or type. Further, in the present invention, the microbial alkaline lipase added to the synthesis reaction system may be a purified product or a crude product, and its form may be a powdered or granular enzyme or a dried product of bacterial cells. Furthermore, immobilization carriers such as polypropylene membranes,
It is also possible to use dry immobilized enzymes supported and immobilized on various polymers such as ion exchange resins, or inorganic materials such as celite, glass beads, zeolite, and bentonite. By immobilizing the enzyme on these carriers, it is possible to spread the contact between the substrate and the enzyme, which is more advantageous in proceeding with the reaction than using enzyme powder. In the present invention, the organic solvent used in the reaction in the presence of an organic solvent (excluding primary alcohol solvents) is liquid at the reaction temperature, stably maintains the lipase activity, and is capable of retaining the insoluble state. Any lipase may be used as long as it can generate an ester of polyalcohol and fatty acid, but as long as it satisfies the above conditions, it can also be used with an organic solvent or such an organic solvent that can simultaneously dissolve both polyalcohol and fatty acid substrates. It is desirable to use it in combination with a solvent. Examples of organic solvents used in the present invention include aliphatic hydrocarbons such as n-heptane, pentane, n-hexane, petroleum ether, isooctane, etc.; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloptane, etc. ;benzene,
Aromatic hydrocarbons such as toluene, xylene, phenol, etc. Ketones such as acetone, methyl isobutyl ketone, etc.; Acetonitrile, 2
- nitrogen-containing solvents such as nitropropane, pyridine, quinoline, dimethylformamide, etc.; ethers such as dimethyl ether, diethyl ether, diisopropyl ether, dioxane, etc.; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, etc.; Sulfoxide solvents such as dimethyl sulfoxide; 2,4-
Secondary alcohols such as dimethyl-3-pentanol, 2,6-dimethyl-4-heptanol; tertiary butyl alcohol, tertiary amyl alcohol, diacetone alcohol, 3-methyl-3
- tertiary substances such as pentanol, 3-ethyl-3-pentanol, 2-methyl-2-hexanol;
Examples include alcohols such as alcohols. Particularly preferred among these are aromatic hydrocarbons, fatty acid hydrocarbons, and secondary and tertiary alcohols. Among these, the above-mentioned alcohol solvents dissolve well both polyalcohol and fatty acid or its lower alcohol ester. Therefore, it is preferable from the viewpoint of proceeding with the reaction, and is an extremely effective reaction solvent, especially when the reaction solution is continuously poured into an enzyme-filled tank. Further, although the reaction solvent can be used alone, two or more kinds of solvents can also be used in combination. The manner in which fatty acids and polyalcohols are brought into contact with microbial alkaline lipase in the presence of an organic solvent to generate esters can be selected as appropriate, but it can be carried out under stirring or shaking conditions. Under reaction conditions in which both substrates can be dissolved in an organic solvent, the reaction can be carried out by filling a reaction tower with solid lipase powder or lipase supported and immobilized on bentonite and dehydrated, and circulating the reaction solution inside the tower. . Next, when an organic solvent is not used in the present invention, the fatty acid may be liquefied by heating if necessary, and microbial alkaline lipase may be allowed to act on the polyalcohol and fatty acid as a liquid mixture. In the present invention, the mixing molar ratio of polyalcohol and fatty acid or its lower alcohol ester, the amount of lipase used, the amount of organic solvent used, etc. can be appropriately selected to best promote the reaction and obtain a high yield. , and conditions that are easy to operate the reaction may be adopted. The molar ratio of fatty acid or lower alcohol ester added to 1 mole of polyalcohol may be, for example, 0.01 to 100 moles, preferably 0.1 to 10 moles, and most preferably 0.2 to 5 moles. Furthermore, it is also possible to react by mixing several types of polyalcohols, fatty acids, etc. Next, is there any limit to the amount of microbial alkaline lipase used? For example, the amount used can be 10 to 100,000 units, preferably 500 to 50,000 units per gram of fatty acid or its lower alcohol ester, and the reaction conditions and The amount to be used may be determined taking into account that it depends on the type of microbial alkaline lipase used. When using an enzyme immobilized on a carrier, the higher the specific activity, the more preferable it is, and the
An example is a carrier carrying about 1,000 to 300,000 units of microbial alkaline lipase. In addition, the amount of organic solvent used is as follows:
Although it depends on the type and concentration of the substrate, as a guideline, it is desirable to add an organic solvent to the extent that the organic solvent in which the substrate is dissolved moves freely and comes into contact with the enzyme, promoting the reaction. There are no particular restrictions, but
For example, 1 to 99% (W/W) of the reaction system, preferably
The reaction may be carried out by adding about 10 to 95% (W/W). One feature of the present invention is that the ester production reaction is carried out by microbial alkaline lipase in the presence or absence of an organic solvent (excluding primary alcohol solvents) without substantially adding water. However, this does not mean that the water content in the reaction system is absolutely zero. It is impossible and unnecessary to create such a situation in practice. However, the less water in the reaction system, the higher the production rate of polyalcohol fatty acid ester, and there is no fear of re-decomposition, and the enzyme activity can be maintained stably for a long time, increasing the degree of enzyme reuse. Therefore, in the present invention, the polyalcohol fatty acid ester producing reaction is carried out using solid microbial alkaline lipase while not only adding substantially no water but also removing water produced by the reaction. . However, this does not mean that esters will not be produced by allowing a small amount of water to coexist in the reaction system. In the present invention, "substantially no water is added" means that substrates and enzymes are used as they are without using any water in the reaction.
Alternatively, the reaction is carried out by dissolving or dispersing the substrate in an organic solvent. In other words, all substances involved in the reaction contain a certain amount of water, and the amount is approximately 1 to 5% for polyalcohols, approximately 0.02% for fatty acids or their lower alcohol esters, approximately 4 to 18% for enzymes, and approximately 4 to 18% for enzymes. Even the solvent is about 0.02 to 0.1%, and even if these are used as is, the initial moisture content of the reaction system as a whole is in the range of about 0.2 to 1.0%.
In such cases, virtually no water is added. Further, if water is produced as a by-product due to moisture absorption from the air or ester synthesis during the reaction, the water content will further increase, but in this case as well, substantially no water is added. The water content of the reaction system is determined by the substrate used in the reaction,
When using enzymes, organic solvents, etc. as dry as possible, and when there is water that enters from the air or water that is produced as a by-product from synthetic reactions, drying agents such as zeolite, silica gel, and In addition to removing moisture using plaster, mirabilite, etc., dry air or inert gas can be vented into the reaction tank, stirred, and then exhausted to the outside of the reaction tank, or the exhaust gas can be cooled and condensed to remove moisture. , water in the reaction system can be removed by means such as refluxing the organic solvent. By such means, the water content of the reaction system can be reduced to 0.1%.
For example, when the molar ratio of glycerin and oleic acid is 1:1, the ester synthesis rate can be increased to about 80-98%, and the concentration of monoglyceride in the obtained glyceride can be reduced to It can be increased to 60-90%. Lipase as microbial alkaline lipase
An example of an experiment in which the ester synthesis rate with respect to the water content (%) of the reaction system was investigated using PL679 is as follows. Experimental example 3 oleic acid 5g (17.7 mmol), glycerin
1.63 g (17.7 mmol) or 8.2 g of hexaglycerin (polyglycerin #500 manufactured by Sakamoto Pharmaceutical Co., Ltd.)
(17.7 mmol), 50 ml of tertiary butyl alcohol,
Put 1 g of Lipase-PL679 powder and 5 g of Molecular Sieves 3A (dehydrating agent sold by Wako Pure Chemical Industries, Ltd.) into a 500 ml Erlenmeyer flask, and add water to make it 0 to 20% (% of the entire reaction system). The mixture was reacted by shaking at 40° C. for 48 hours, and the ester synthesis rate was measured as described in Example 2 below. Also, after the reaction,
0.5 g of the reaction solution was taken, and the water content of the reaction solution was examined using a moisture measuring device using a Karl Fischer reagent (manufactured by Mitsubishi Chemical Industries, Ltd.). The results are shown in Table 3. [Table] The ester production reaction in the present invention proceeds even at room temperature, so there is no particular need for heating, but in general, an appropriate temperature should be selected taking into consideration the boiling point of the organic solvent used and the action temperature of the enzyme. It is desirable to conduct the temperature at a temperature of 0 to 90°C, for example, but it is usually 20 to 90°C.
It can be carried out at a temperature of 60°C. In addition, the reaction time can be selected as appropriate,
For example, the reaction time can be specified as 10 minutes to 10 days, preferably 1 to 96 hours. In addition, if necessary, the formation of the desired target product can be confirmed by measuring the reduction rate of fatty acids in the reaction system or by tracking the ester production process using techniques such as TLC (thin layer chromatography). The reaction time may be determined by After the reaction is completed, the polyalcohol fatty acid ester produced in the absence of an organic solvent can be separated using an organic solvent. In addition, the polyalcohol fatty acid ester produced by the reaction in an organic solvent can be separated from the reaction system using alumina silicate, ion exchange resin, gel for molecular sieves, or adsorption chromatography, or the reaction solvent can be removed. After that, it can be separated and purified using the above method, distillation, solvent fractionation, urea addition method, high performance liquid chromatography, etc. [Effects of the Invention] According to the present invention, it is possible to obtain polyalcohol fatty acid esters with a high synthesis rate (esterification rate) that was not possible with conventionally proposed enzymatic methods, and with almost no residual fatty acids added. can. In addition, the present invention does not require a large excess of polyalcohol relative to fatty acids or their lower alcohol esters,
Ester can be obtained at a sufficiently high concentration even at a 1:1 molar ratio, and the substrate concentration can be varied from a few percent to several tens of percent.
can be varied within a wide range up to high concentrations. Furthermore, in the present invention, polyalcohol fatty acid esters with a high monoester concentration, which are difficult to obtain by chemical methods, can be obtained. Furthermore, in the present invention, there is no need to use toxic reaction catalysts used in chemical methods, and the ester is synthesized under extremely mild reaction conditions, so there is no change in the structure of the polyalcohol itself. ,
A polyalcohol fatty acid ester useful as a highly safe surfactant with excellent properties is obtained. Among the polyalcohol fatty acid esters obtained in the present invention, polyalcohol fatty acid esters in which the acid is a monocarboxylic acid can be used in foods, such as margarine, corn syrup, mayonnaise,
It is used to emulsify fatty foods such as peanut butter, solubilize dairy products, juices, fragrances, essential oils, etc., and is also used as an anti-aging agent for bread, cakes, cutlets, noodles, chikuwa, kamaboko, fish sausages, etc.
Oil separation prevention agent for sausages, pressed ham, etc., foaming agent for sponge cake, ice cream, marshmallow, etc., tyokolate, cocoa, chewing gum,
It can be used in many ways, such as as a lubricant for milk powder, a dispersant, etc. In addition, the various polyalcohol fatty acid esters obtained in the present invention can be used as cosmetics, such as basic cosmetics such as creams, milky lotions, and lotions, makeup products such as foundations, white powders, and lipsticks, and hair products such as hair tonics, pomades, and hair liquids. It can be applied to many products such as products, fragrances such as perfumes and colognes, nail polishes such as enamel, cleaning agents such as shampoo and conditioner, and toothpaste. In addition, the polyalcohol fatty acid ester obtained by the present invention can be used as a surfactant, as well as in cosmetics, for emulsification of various ointments, solubilization of fat-soluble vitamins, corticosteroids, etc. , and may be used in pharmaceuticals such as eye drops. Furthermore, in the field of agrochemicals, it can be applied to emulsifying and dispersing many products such as insecticides and spreading agents. Note that some of the polyalcohol fatty acid esters obtained in the present invention also contain weakly acidic surfactants, but most of them are nonionic surfactants that are not biotoxic and do not cause contact allergies. It is expected to be a highly safe surfactant. [Example] Examples of the present invention will be shown below. In the examples, a dehydrating agent molecular sieves (manufactured by Wako Pure Chemical Industries, Ltd.) was used so that the water content of the reaction system was 0.1% or less. Example 1 Oleic acid 0.5 g (1.77 mmol), glycerin
0.163 g (1.77 mmol), 5 ml of tertiary butyl alcohol, 0.1 g of Lipase-PL679 powder, and 0.5 g of Molecular Sieves 3A were placed in a stoppered test tube, mixed well, and then shaken at 37°C for 48 hours. After the reaction, centrifuge and transfer 5μ of the supernatant to a thin layer of silica gel (Merck, Silica Gel 60 TLC Plate No. 5721 20 x 20
cm) and developed using petroleum ether-ether-acetic acid (70:30:1 V/V) as a developing solvent. 50% sulfuric acid or iodine was used to detect spots. When spots were detected using 50% sulfuric acid or iodine, two spots were detected in addition to unreacted oleic acid and glycerin. of this unknown spot
Since the Rf values matched those of commercially available glycerin monooleate (manufactured by Funakoshi Pharmaceutical Co., Ltd.) and glycerin diolate (manufactured by Funakoshi Pharmaceutical Co., Ltd.), these two spots were used as glycerin monooleate and glycerin diolate, which are oleic acid esters of glycerin. . Incidentally, since the spots on TLC of glycerin monooleate were overwhelmingly larger than those of glycerin diolate, it was decided to purify glycerin monooleate. Glycerol monooleate was purified using preparative TLC. Spot 0.5 ml of the reaction solution on the line of a thin layer of silica gel (Silica gel TLC plate No. 13894, 0.5 mm, 20 x 20 cm manufactured by Merck), and add petroleum ether-ether-acetic acid (70:30:1 V/V).
was developed as a developing solvent. After unfolding, both ends are 3cm
It was cut out and detected with 50% sulfuric acid to determine the Rf value of glycerin monooleate. The silica gel corresponding to the determined Rf value was scraped off from the TLC plate, and the silica gel was extracted with 10 ml of chloroform-methanol (2:1 V/V). Filter the extract through No. 5C paper to remove the silica gel, and then add 3 ml of water to remove the silica gel.
The chloroform layer was washed twice and separated. The separated chloroform layer was dried at 30°C under reduced pressure. The yield of the obtained glycerin monooleate was 10 mg, and it was found to be a single product on TLC. IR of glycerin monooleate
The spectrum (infrared absorption spectrum) is from JASCO.
It was measured using a liquid film method using an A202 infrared spectrophotometer. The results are shown in Table 4 (Run No. 1). Further, in place of 0.5 g of oleic acid, 0.5 g of other fatty acids or fatty acid esters shown in Table 4 were used in the same manner as above to obtain a glycerin monoester. The IR spectra are shown in Table 4 (Run Nos. 2 to 25). Next, instead of 0.163g of glycerin, use 0.135g of propylene glycol or 0.294g of diglycerin.
g, or 0.56 g of tetraglycerin (polyglycerin #310 manufactured by Sakamoto Pharmaceutical Co., Ltd.), or 0.82 g of hexaglycerin (polyglycerin #500 as above),
or decaglycerin (same as polyglycerin #
750) and 0.5 g of various fatty acids or fatty acid esters shown in Table 4 were carried out in the same manner as above to obtain esters of propylene glycol, diglycerin, tetraglycerin, hexaglycerin, and decaglycerin. The IR spectra are shown in Table 4 (Run Nos. 26 to 150). [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] From the results in Table 4, absorption of ester bond is seen around 1740 Kaiser and absorption of alcohol is seen around 3400 Kaiser. This indicates that the above product is a polyalcohol fatty acid ester. Example 2 1.63 g (17.7 mmol) of glycerin, 5 g (17.7 mmol) of oleic acid, 50 ml of tertiary butyl alcohol, 1 g of lipase-PL679 powder, and 10 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask and heated at 40°C for 48 hours. Glycerol oleate was prepared by shaking reaction for a period of time. The ester synthesis rate of this reaction solution is 94
It was %. The ester synthesis rate was determined by titrating the amount of fatty acids added to the reaction system consumed for ester synthesis with an alkaline solution, and was expressed as a percentage of the reduction rate of fatty acids relative to the amount of fatty acids before the reaction. After the reaction, the mixture was centrifuged at 10,000 g for 10 minutes to remove insoluble matter and obtain a supernatant. Further, 30 ml of tertiary butyl alcohol was added to the insoluble matter to wash away the insoluble matter, followed by centrifugation to obtain a supernatant. These supernatants were combined and concentrated using an evaporator to remove tertiary butyl alcohol to obtain 6.0 g of glycerin oleate.
The acid value of this glycerin oleate was 9. Note that the acid value was measured based on the standard oil and fat analysis test method. The composition ratio of glycerin oleate is Iatroskyan (Iatroskyan TH10 manufactured by Yatron)
It was calculated using That is, 1μ of a 1% chloroform solution of glycerin oleate was spotted on Chromarot SII (silica gel rod manufactured by Yatron), and hexane-chloroform-acetic acid (50:20:0.5V/
V) was developed as a developing solvent for about 10 cm, and subjected to Iatroscan, and the weight ratio of the components was determined from the peak area ratio. Glycerin oleate component composition ratio: 72% glycerin monooleate, glycerin diolate
24% and 4% oleic acid. And no glycerin triolate was detected. Note that monoolein (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a standard substance. Example 3 Glycerin 1.63 g (17.7 mmol), oleic acid 5 g (17.7 mmol), 2,4-dimethyl-3
-Pentanol 50ml, Lipase-PL679 powder 1
5 g of Molecular Sieves 3A were placed in a 300 ml Erlenmeyer flask and reacted with shaking at 40° C. for 48 hours to prepare glycerol oleate. The ester synthesis rate of this reaction solution was 89%. Thereafter, the same procedure as in Example 2 was carried out to obtain 5.8 g of glycerin oleate. The acid value of this glycerin oleate was 15. The component composition ratio of glycerin oleate determined by Iatroskian was 77% glycerin monooleate, 12% glycerin diolate, and 10% oleic acid. And no glycerin triolate was detected. Example 4 5 g (17.7 mmol) of oleic acid, 50 ml of tertiary butyl alcohol, 1 g of lipase-PL679 powder,
Take 5 g of Molecular Sieves 3A in a 500 ml Erlenmeyer flask, add 1.63 g (17.7 mmol), 3.26 g (35.4 mmol), and 4.89 g (53.1 mmol) of glycerin to the Erlenmeyer flask, and heat at 30°C for 72 hours. Glycerol oleate was prepared by shaking reaction for a period of time. Thereafter, the same procedure as in Example 2 was carried out to determine the ester synthesis rate of the reaction solution, the yield and acid value of glycerin oleate, and the component composition ratio of glycerin oleate determined by Iatroskian. The results are shown in Table 5. [Table] From the results in Table 5, it can be seen that as the glycerin/oleic acid ratio increases, the content of glycerin monooleate increases. Example 5 Glycerin 1.63 g (17.7 mmol), oleic acid 5 g (17.7 mmol), diacetone alcohol
Add 50ml, 1g of Lipase-PL679 powder, and 10g of Molecular Sieves 3A to a 500ml Erlenmeyer flask.
A shaking reaction was performed at 40°C for 72 hours to prepare glycerin oleate. The ester synthesis rate of this reaction solution was 82%. Thereafter, the same procedure as in Example 2 was carried out to obtain 5.9 g of glycerin oleate. The acid value of this glycerin oleate was 27. Example 6 1.63 g (17.7 mmol) of glycerin, 5 g (17.7 mmol) of oleic acid, 50 ml of tertiary butyl alcohol, 3 g of lipase-AL powder, and 10 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask.
A shaking reaction was performed at 40°C for 48 hours to prepare glycerin oleate. The ester synthesis rate of this reaction solution was 88%. Thereafter, the same procedure as in Example 2 was carried out to obtain 6.0 g of glycerin oleate. The acid value of this glycerin oleate was 18. Also, instead of lipase AL powder, lipase
The same procedure as above was carried out using 3 g of PL266 powder. The ester synthesis rate of this reaction solution was 82%. The yield of glycerin oleate was 5.8g.
The acid value was 25. Example 7 1.63 g (17.7 mmol) of glycerin, 5 g (17.7 mmol) of oleic acid, 50 ml of n-hexane, 5 g of molecular sieves 3A, and 1 g of lipase-PL679 powder were placed in a 500 ml Erlenmeyer flask and heated at 30°C.
Glycerol oleate was prepared by shaking reaction for 48 hours. The ester synthesis rate of this reaction solution was 95%. After the reaction, n-hexane was removed under reduced pressure, and 50 ml of tertiary butyl alcohol was added to the residue. From then on,
Proceed as in Example 2 and add 5.8 g of glycerin oleate.
I got it. The acid value of this glycerin oleate was 6. Also, instead of n-hexane, isooctane 20
Glycerin oleate was prepared in the same manner as above using a mixed solvent of 30 ml and 30 ml of tertiary butyl alcohol. The ester synthesis rate of this reaction solution was 94%. And the yield of glycerol oleate obtained is
It weighed 5.7g and had an acid value of 8. Example 8 1.62 g (17.6 mmol) of glycerin, 5 g (17.6 mmol) of stearic acid, 50 ml of tertiary amyl alcohol, 5 g of molecular sieves 4A, and 1 g of lipase-PL679 powder were placed in a 500-volume Erlenmeyer flask.
A shaking reaction was performed at 50°C for 72 hours to prepare glycerin stearate. The ester synthesis rate of this reaction solution is 98
It was %. Thereafter, the same procedure as in Example 2 was carried out to obtain 5.8 g of glycerin stearate. The acid value of this glycerin stearate was 3. The component composition ratio of glycerin stearate determined by Iatroskian was 79% glycerin monostearate, 18% glycerin distearate, and 3% stearic acid. And glycerol tristearate was not detected. Example 9 1.63 g (17.7 mmol) of glycerin, 4.5 g (17.7 mmol) of valmitic acid, 50 ml of tertiary butyl alcohol, 5 g of molecular sieves 5A, and 1 g of lipase-PL679 powder were placed in a 500 ml Erlenmeyer flask and heated at 40°C. Glycerin palmitate was prepared by shaking reaction for 72 hours. The ester synthesis rate of this reaction solution was 98%. Thereafter, the same procedure as in Example 2 was carried out to obtain 5.5 g of glycerin palmitate. The acid value of this glycerin palmitate was 2. The component composition ratio of glycerin palmitate determined by Iatroskian was 62% glycerin monopalmitate, 35% glycerin dipalmitate, 2% palmitic acid, and 1% glycerin tripalmitate. Example 10 1.63 g (17.7 mmol) of glycerin, 3.5 g (17.7 mmol) of lauric acid, 50 ml of tertiary butyl alcohol, 5 g of molecular sieves 3A, and 2 g of lipase PL679 powder were placed in a 500 ml Erlenmeyer flask.
A shaking reaction was performed at 40°C for 48 hours to prepare glycerin laurate. The ester synthesis rate of this reaction solution is 81%
It was hot. Thereafter, the same procedure as in Example 2 was carried out to obtain 4.5 g of glycerin laurate. The acid value of this glycerin laurate was 36. In addition, glycerin ricinoleate was prepared in the same manner as above using 5.3 g (17.7 mmol) of ricinoleic acid instead of 3.5 g of lauric acid. The ester synthesis rate of this reaction solution was 81%. The yield of glycerin ricinoleate obtained was 6.3g.
The acid value was 29. Example 11 1.63 g (17.7 mmol) of glycerin, 2.05 g (17.7 mmol) of caproic acid, 25 ml of tertiary butyl alcohol, 1 g of lipase-PL679 powder, and 5 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask and heated at 40°C for 48 hours. Glycerin capronate was prepared by shaking reaction. The ester synthesis rate of this reaction solution is 72
It was %. Thereafter, the same procedure as in Example 2 was carried out to obtain 3.1 g of glycerin capronate. The acid value of this glycerin capronate was 70. Also, instead of 2.05g of caproic acid, use cinnamic acid.
Glycerin cinnamate was prepared in the same manner as above using 2.6 g (17.7 mmol). The ester synthesis rate of this reaction solution was 30%. Thereafter, the same procedure as in Example 2 was carried out, and 3.7 g of glycerin cinnamate was added.
I got it. Example 12 1.63 g (17.7 mmol) of glycerin, 3.6 g (17.7 mmol) of sebacic acid, 1 g of lipase PL679 powder, 5 g of molecular sieves 3A, and 50 ml of tertiary butyl alcohol were placed in a 500 ml Erlenmeyer flask.
A shaking reaction was performed at 40°C for 48 hours to prepare glycerin sebaccinate. The ester synthesis rate of this reaction solution is 40%
It was hot. Thereafter, the same procedure as in Example 2 was carried out to obtain 4.3 g of glycerin sebaccinate. Example 13 1.63 g (17.7 mmol) of glycerin, 5.2 g (17.7 mmol) of methyl oleate, 50 ml of tertiary butyl alcohol, 1 g of lipase-PL679 powder, and 5 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask and heated at 30°C for 24 hours. Glycerol oleate was prepared by shaking reaction for a period of time. Thereafter, the same procedure as in Example 2 was carried out to obtain 5.8 g of glycerin oleate. The component composition ratio of this glycerin oleate was determined by Iatroskian and was found to be 70% glycerin monooleate, 10% glycerin diolate, 1% oleic acid, and 19% methyl oleate. Example 14 Glycerin 1.63 g (17.7 mmol), Olive oil 7.8 g (8.9 mmol), Lipase-PL679 powder 1
g, 50 ml of tertiary butyl alcohol, and 5 g of molecular sieves 3A in a 500 ml Erlenmeyer flask.
A shaking reaction was performed at 40°C for 24 hours to prepare glycerin olive oil fatty acid ester. Thereafter, the same procedure as in Example 2 was carried out to obtain glycerin olive oil fatty acid ester 8.7
I got g. The acid value of this glycerin olive oil fatty acid ester was 2. When the component composition ratio of this ester was determined by Iatroskian, it was found that glycerin monoester was 65%;
The composition was 30% glycerin diester, 2% fatty acid, and 1% glycerin triester. Further, in place of olive oil, 7.8 g (8.9 mmol) of beef tallow was used to prepare glycerin tallow fatty acid ester in the same manner as above. Thereafter, the same procedure as in Example 2 was carried out to obtain 8.2 g of glycerin tallow fatty acid ester.
I got it. The acid value of this glycerin beef tallow fatty acid ester was 2. The component composition ratio of this ester, determined by Iatroskian, was 60% glycerin monoester, 36% glycerin diester, 2% fatty acid, and 2% glycerin triester. Example 15 1.35 g (17.7 mmol) of propylene glycol,
5 g (17.7 mmol) of oleic acid, 50 ml of tertiary butyl alcohol, 1 g of lipase PL679 powder, and 5 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask and reacted with shaking at 40° C. for 48 hours to prepare propylene glycol oleate. The ester synthesis rate of this reaction solution was 92%. Thereafter, the same procedure as in Example 2 was carried out to obtain 5.6 g of propylene glycol oleate. The acid value of this propylene glycol was 12. The component composition ratio of propylene glycol oleate determined by Iatroskian was 81% propylene glycol monooleate, 12% propylene glycol dioleate, and 7% oleic acid. Note that propylene glycol monooleate (manufactured by Riken Vitamin Co., Ltd.) was used as a standard sample. Further, propylene glycol oleate was prepared in the same manner as above except that 3 g of Lipase-PL266 powder or 3 g of Lipase-AL powder was used instead of 1 g of Lipase-PL679 powder. Lipase-PL266
The ester synthesis rate was 82%, and the yield of propylene glycol oleate was 5.5g.
The acid value was 30. The ester synthesis rate when using Lipase-AL was 80%, the yield of propylene glycol oleate was 5.5 g, and the acid value was 32. Example 16 1.35 g (17.7 mmol) of propylene glycol,
5 g (17.7 mmol) of oleic acid, 30 ml of diacetone alcohol, 1 g of Lipase-PL679 powder, and 10 g of Molecular Sieves 3A were placed in a 500 ml Erlenmeyer flask and reacted with shaking at 40° C. for 48 hours to prepare propylene glycol oleate. The ester synthesis rate of this reaction solution was 80%. Thereafter, the same procedure as in Example 2 was carried out to obtain 5.2 g of propylene glycol oleate. The acid value of this propylene glycol oleate is
It was 30. Also, instead of 30ml of diacetone alcohol,
The same procedure as above was carried out using 50 ml of 2,4-dimethyl-3-pentanol. The ester synthesis rate of this reaction solution was 82%, the yield of propylene glycol oleate was 5.5 g, and the acid value was 29. Example 17 1.35 g (17.7 mmol) of propylene glycol,
5 g (17.7 mmol) of oleic acid, n-pentane
Add 50ml, 1g of Lipase-PL679 powder, and 5g of Molecular Sieves 3A to a 500ml Erlenmeyer flask.
A shaking reaction was performed at 40°C for 48 hours to prepare propylene glycol oleate. The ester synthesis rate of this reaction solution was 97%. Thereafter, the same procedure as in Example 2 was carried out to obtain 5.0 g of propylene glycol oleate. The acid value of this propylene glycol oleate was 4. Further, the same procedure as above was carried out using a mixed solvent of 30 ml of n-hexane and 20 ml of tertiary butyl alcohol instead of 50 ml of n-pentane. The ester synthesis rate of this reaction solution was 97%, the yield of propylene glycol oleate was 5.0 g, and the acid value was 3. Example 18 1.34 g (17.6 mmol) of propylene glycol,
Stearic acid 5g (17.6 mmol), tertiary amyl alcohol 50ml, Lipase-PL679 powder 1g,
10 g of Molecular Sieves 4A was placed in a 500 ml Erlenmeyer flask and reacted with shaking at 50° C. for 48 hours to prepare propylene glycol stearate. The ester synthesis rate of this reaction solution was 96%. Thereafter, the same procedure as in Example 2 was carried out to obtain 5.6 g of propylene glycol stearate. The acid value of this propylene glycol stearate was 7. The component composition ratio of propylene glycol stearate determined by Iatroskian was 83% propylene glycol monostearate, 11% propylene glycol distearate, and 6% stearic acid. Example 19 1.35 g (17.7 mmol) of propylene glycol,
Palmitic acid 4.5g (17.7mmol), tertiary butyl alcohol 500ml, Lipase-PL679 powder 1g,
5 g of Molecular Sieves 5A was placed in a 500 ml Erlenmeyer flask and reacted with shaking at 40° C. for 48 hours to prepare propylene glycol balmitate. The ester synthesis rate of this reaction solution was 95%. Thereafter, the same procedure as in Example 2 was carried out to obtain 5.2 g of propylene glycol palmitate. The acid value of this propylene glycol palmitate was 8. The component ratio of propylene glycol palmitate determined by Iatroskian was 57% propylene glycol monopalmitate, 35% propylene glycol dipalmitate, and 8% palmitic acid. Example 20 1.35 g (17.7 mmol) of propylene glycol,
3.5 g (17.7 mmol) of lauric acid, 50 ml of tertiary butyl alcohol, 2 g of Lipase-PL679 powder, and 10 g of Molecular Sieves 3A were placed in a 500 ml Erlenmeyer flask and reacted with shaking at 40°C for 96 hours to prepare propylene glycol laurate. . The ester synthesis rate of this reaction solution was 80%. Thereafter, the same procedure as in Example 2 was carried out to obtain propylene glycol laurate 4.7
I got g. The acid value of this propylene glycol laurate was 35. Further, propylene glycol ricinoleate was prepared in the same manner as above using 5.3 g (17.7 mmol) of ricinoleic acid instead of 3.5 g of lauric acid. The ester synthesis rate of this reaction solution was 80%, the yield of propylene glycol ricinoleate was 5.1 g, and the acid value was 30. Example 21 1.35 g (17.7 mmol) of propylene glycol,
Sebacic acid 3.6g (17.7mmol), lipase
PL679 powder 1g, Molecular Sieves 3A 5g,
50 ml of tertiary butyl alcohol was placed in a 500 ml Erlenmeyer flask and reacted with shaking at 40° C. for 48 hours to prepare propylene glycol sebaccinate. The ester synthesis rate of this reaction solution was 30%. Thereafter, the same procedure as in Example 2 was carried out to obtain 4.0 g of propylene glycol sebaccinate. Also, instead of 3.6g of sebacic acid, 2.6g of cinnamic acid
Propylene glycol cinnamate was prepared in the same manner as above using g (17.7 mmol). The ester synthesis rate of this reaction solution was 25%, and the yield of propylene glycol cinnamate was 3.3g.
It was hot. Example 22 1.35 g (17.7 mmol) of propylene glycol, 5.3 g (17.7 mmol) of methyl oleate, 50 ml of tertiary butyl alcohol, 2 g of lipase-PL679 powder, and 5 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask and heated at 40°C. Propylene glycol oleate was prepared by shaking reaction for 48 hours. From then on,
The same procedure as in Example 2 was carried out to obtain 6.1 g of propylene glycol oleate. The component ratio of propylene glycol oleate determined by Iatroskian was 60% propylene glycol monooleate and 40% mixture of propylene glycol dioleate and methyl oleate. Example 23 2.94 g (17.7 mmol) of diglycerin, 5 g (17.7 mmol) of oleic acid, 25 ml of tertiary butyl alcohol, 1 g of lipase-PL679 powder, and 5 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask and heated at 30°C for 48 hours. Diglycerol oleate was prepared by shaking reaction for a period of time. The ester synthesis rate of this reaction solution is 93
It was %. Thereafter, the same procedure as in Example 2 was carried out to obtain 7.2 g of diglycerol oleate. The acid value of the obtained diglycerol oleate was 9. Example 24 5.6 g (17.7 mmol) of tetraglycerin, oleic acid (17.7 mmol), 30 ml of tertiary butyl alcohol, 10 ml of n-hexane, 1 g of lipase-PL679 powder, and 5 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask. A shaking reaction was performed at 40°C for 48 hours to prepare tetraglycerol oleate. The ester synthesis rate of this reaction solution was 95%. Thereafter, the same procedure as in Example 2 was carried out, and 9.5 g of tetraglycerol oleate was added.
I got it. The acid value of this tetraglycerol oleate was 4. Example 25 5.5 g (17.6 mmol) of tetraglycerin, 5 g (17.6 mmol) of stearic acid, 50 ml of tertiary butyl alcohol, 1 g of lipase-PL679 powder, and 5 g of molecular sieves 4A were placed in a 500 ml Erlenmeyer flask and heated at 50°C for 48 hours. Tetraglycerol stearate was prepared by shaking reaction for a period of time. The ester synthesis rate of this reaction solution was 97%. Thereafter, the same procedure as in Example 2 was carried out to obtain 9.7 g of tetraglycerol stearate. The acid value of this teila glycerin stearate was 3. Example 26 5.5 g (17.7 mmol) of tetraglycerin, 4.5 g (17.7 mmol) of palmitic acid, 50 ml of tertiary amyl alcohol, 1 g of lipase-PL679 powder, and 5 g of molecular sieves 3A were placed in a 300 ml Erlenmeyer flask and heated at 40°C. Tetraglycerin palmitate was prepared by shaking reaction for 48 hours. The ester synthesis rate of this reaction solution was 98%. Thereafter, the same procedure as in Example 2 was carried out to obtain 9.1 g of tetraglycerin palmitate. The acid value of this tetraglycerin palmitate was 2. Further, tetraglycerol laurate was prepared in the same manner as above using 3.5 g of lauric acid instead of 4.5 g of palmitic acid. The ester synthesis rate of this reaction solution was 90%, the yield of the obtained tetraglycerol laurate was 8.0 g, and the acid value was 10. Example 27 8.2 g (17.7 mmol) of hexaglycerin, 5 g (17.7 mmol) of oleic acid, 50 ml of tertiary butyl alcohol, 1 g of lipase-PL679 powder, and 5 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask and heated at 40°C for 48 hours. Hexaglycerol oleate was prepared by shaking reaction for a period of time. The ester synthesis rate of this reaction solution was 96%. Thereafter, the same procedure as in Example 2 was carried out to obtain 12 g of hexaglycerol oleate. The acid value of this hexaglycerol oleate was 3. Further, decaglycerin oleate was prepared in the same manner as above using 13.4 g (17.7 mmol) of decaglycerin instead of 8.2 g of hexaglycerin. The ester synthesis rate of this reaction solution was 95%, the yield of decaglycerol oleate was 16 g, and the acid value was 2. 1 ml of the 2% chloroform solution of hexaglycerol oleate (sample 1) and decaglycerol oleate (sample 2) prepared as above was spotted on Chromarot SII, and a mixture of benzene-chloroform-methanol-ammonia (80:40:10:
1V/V) as a developing solvent and analyzed with Iatroskian. In addition, as a standard material, SY
Glister MO500 (hexaglycerin monooleate, manufactured by Sakamoto Pharmaceutical Co., Ltd.), SY Glister PO500 (hexaglycerin pentaoleate, manufactured by Sakamoto Pharmaceutical Co., Ltd.), SY Glister MO750 (decaglycerin monooleate, manufactured by Sakamoto Pharmaceutical Co., Ltd.), and SY Glister DAO750 (decaglycerin monooleate, manufactured by Sakamoto Pharmaceutical Co., Ltd.) Glycerin decaolate (manufactured by Sakamoto Pharmaceutical Co., Ltd.) was used. The results are shown in FIG. From Figure 1, it can be seen that the above-mentioned hexaglycerol oleate (sample 1) and decaglycerol oleate (sample 2) are mainly composed of monoesters because their analysis patterns are similar to those of commercially available polyglycerol monooleate. It seems to be. Example 28 8.2 g (17.7 mmol) of hexaglycerin, 5 g (17.7 mmol) of oleic acid, 50 ml of diacetone alcohol, 1 g of lipase-PL679 powder, and 10 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask and shaken at 40°C for 48 hours. The reaction was carried out to prepare hexaglycerol oleate. The ester synthesis rate of this reaction solution was 91%. Thereafter, the same procedure as in Example 2 was carried out to obtain 12.1 g of hexaglycerin oleate. The acid value of this hexaglycerol oleate was 7. Also, instead of 50ml of diacetone alcohol,
Hexaglycerol oleate was prepared in the same manner as above using 50 ml of 2,4-dimethyl-3-pentanol. The ester synthesis rate of this reaction solution is 80%
The yield of hexaglycerol oleate obtained is
It weighed 12g and had an acid value of 15. Furthermore, instead of 50ml of diacetone alcohol,
Hexaglycerol oleate was prepared in the same manner as above using 50 ml of n-heptane. The ester synthesis rate of this reaction solution was 80%, the yield of hexaglycerol oleate was 12 g, and the acid value was 15. Example 29 8.2 g (17.7 mmol) of hexaglycerin, 5 g (17.7 mmol) of oleic acid, 50 ml of tertiary butyl alcohol, 3 g of lipase-PL266 powder, and 10 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask, and the mixture was heated at 40°C at 96°C. Hexaglycerol oleate was prepared by shaking reaction for a period of time. The ester synthesis rate of this reaction solution was 91%. Thereafter, the same procedure as in Example 2 was carried out to obtain 11.5 g of hexaglycerin oleate. The acid value of this hexaglycerol oleate was 7. Further, hexaglycerol oleate was prepared in the same manner as above using 3 g of Lipase-AL powder instead of 3 g of Lipase-PL266 powder. The ester synthesis rate of this reaction solution was 93%, the yield of hexaglycerol oleate was 11.3 g, and the acid value was 6. Example 30 8.2 g (17.7 mmol) of hexaglycerin, 5.1 g (17.7 mmol) of stearic acid, 50 ml of tertiary butyl alcohol, 1 g of lipase-PL679 powder, and 5 g of molecular sieves 5A were placed in a 500 ml Erlenmeyer flask and heated at 40°C. Hexaglycerol stearate was prepared by shaking reaction for 48 hours. The ester synthesis rate of this reaction solution was 98%. Thereafter, the same procedure as in Example 2 was carried out to obtain 11.7 g of hexaglycerol stearate. The acid value of this hexaglycerol stearate was 1. Hexaglycerin palmitate was also prepared in the same manner as above using 4.5 g (17.7 mmol) of palmitic acid instead of 5.1 g of stearic acid. The ester synthesis rate of this reaction solution was 98%, and the yield of hexaglycerin palmitate was 8.5%.
g, and the acid value was 1. Furthermore, hexaglycerol laurate was prepared in the same manner as above using 3.5 g (17.7 mmol) of lauric acid instead of 5.1 g of stearic acid.
The ester synthesis rate of this reaction solution was 90%, the yield of the obtained hexaglycerol laurate was 10.3 g, and the acid value was 9. Example 31 8.2 g (17.7 mmol) of hexaglycerin, 5.3 g (17.7 mmol) of ricinoleic acid, 50 ml of tertiary butyl alcohol, 1 g of lipase-PL679 powder, and 5 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask and heated at 40°C. Hexaglycerol ricinoleate was prepared by shaking reaction for 48 hours. The ester synthesis rate of this reaction solution was 85%. Thereafter, the same procedure as in Example 2 was carried out to obtain 11.5 g of hexaglycerin ricinoleate. The acid value of this hexaglycerol ricinoleate was 10. Further, hexaglycerin capronate was prepared in the same manner as above using 2.05 g (17.7 mmol) of caproic acid instead of 5.3 g of ricinoleic acid. The ester synthesis rate of this reaction solution was 83%, and the yield of hexaglycerol capronate was 8.7%.
g, and the acid value was 14. Furthermore, hexaglycerin cinnamate was prepared in the same manner as above using 2.6 g (17.7 mmol) of cinnamic acid instead of 5.3 g of ricinoleic acid. The ester synthesis rate of this reaction solution was 20%, and the yield of hexaglycerol cinnamate was 9.1%.
It was hot at g. Example 32 8.2 g (17.7 mmol) of hexaglycerin, 3.6 g (17.7 mmol) of sebacic acid, 50 ml of tertiary butyl alcohol, 1 g of lipase-PL679 powder, and 5 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask and heated at 40°C. Hexaglycerin sebaccinate was prepared by shaking reaction for 48 hours. The ester synthesis rate of this reaction solution was 50%. Thereafter, the same procedure as in Example 2 was carried out to obtain 10.7 g of hexaglycerin sebaccinate. Example 33 8.2 g (17.7 mmol) of hexaglycerin, 5.2 g (17.7 mmol) of methyl oleate, 50 ml of tertiary butyl alcohol, 2 g of lipase-PL679 powder, and 5 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask and heated at 40°C. A shaking reaction was performed for 72 hours to prepare hexaglycerol oleate. Thereafter, the same procedure as in Example 2 was carried out to obtain 12.4 g of hexaglycerol oleate. When the component composition ratio of this hexaglycerol oleate was examined by Iatroskian, it was found to be 80% hexaglycerol monooleate and 20% methyl oleate. Example 34 13.4 g (17.7 mmol) of decaglycerin, 5.1 g (17.7 mmol) of stearic acid, 50 ml of tertiary butyl alcohol, 1 g of lipase-PL679 powder, and 5 g of molecular sieves 3A were placed in a 500 ml Erlenmeyer flask and heated at 40°C. Decaglycerin stearate was prepared by shaking reaction for 48 hours. The ester synthesis rate of this reaction solution was 95%. Thereafter, the same procedure as in Example 2 was carried out to obtain 17.5 g of decaglycerin stearate.
The acid value of this decaglycerol stearate was 3. Decaglycerin palmitate was also prepared in the same manner as above using 4.5 g (17.7 mmol) of palmitic acid instead of 5.1 g of stearic acid.
The ester synthesis rate of this reaction solution was 97%, the yield of decaglycerin palmitate was 17 g, and the acid value was 2. Furthermore, decaglycerol laurate was prepared in the same manner as above using 3.5 g (17.7 mmol) of lauric acid instead of 5.1 g of stearic acid. The ester synthesis rate of this reaction solution was 91%, the yield of the obtained decaglycerin laurate was 15.0 g, and the acid value was 7. Example 35 10 g of Lipase-PL679 powder was placed in a 200 ml beaker, 100 ml of water was added to dissolve it, 10 g of bentonite was added, and the mixture was stirred at room temperature for 30 minutes to adsorb Lipase-PL679 onto the bentonite. Bentonite was recovered by centrifugation at 5,000 g for 5 minutes, and 100 ml of acetone was added thereto and stirred to suspend, and bentonite was recovered by centrifugation again. Thereafter, this operation was repeated twice to dehydrate and then dry under reduced pressure to prepare bentonite adsorption-immobilized lipase PL-679. This bentonite adsorption recirculation lipase
PL6791g, glycerin 1.63g (17.7 mmol),
5 g (17.7 mmol) of oleic acid, 50 ml of tertiary butyl alcohol, and 5 g of molecular sieves 3A.
The mixture was placed in a 500 ml Erlenmeyer flask and reacted with shaking at 40°C for 48 hours to prepare glycerol oleate. The ester synthesis rate of this reaction solution was 95%. Thereafter, the same procedure as in Example 2 was carried out to obtain 5.9 g of glycerin oleate. The acid value of this glycerin oleate was 8. Further, propylene glycol oleate was prepared in the same manner as above using 1.35 g (17.7 mmol) of propylene glycol instead of 1.63 g of glycerin. The ester synthesis rate of this reaction solution was 93%, and the yield of propylene glycol oleate was
It weighed 5.7g and had an acid value of 10. Furthermore, hexaglycerol oleate was prepared in the same manner as above using 8.2 g (17.7 mmol) of hexaglycerin instead of 1.63 g of glycerin. The ester synthesis rate of this reaction solution was 96%, and the yield of hexaglycerol oleate was 12.1 g.
The acid value was 3. Example 36 1.63 g (17.7 mmol) of glycerin, 5 g (17.7 mmol) of oleic acid, molecular sieves
5 g of 3A and 1 g of lipase-PL679 powder were placed in a 100 ml Erlenmeyer flask and reacted with shaking at 40° C. for 48 hours to prepare glycerol oleate. The ester synthesis rate of this reaction solution was 95%. After the reaction, 50 ml of tertiary butyl alcohol was added, and the same procedure as in Example 2 was carried out to obtain 5.7 g of glycerin oleate. The acid value of this glycerin oleate was 9. Further, propylene glycol oleate was prepared in the same manner as above using 1.35 g (17.7 mmol) of propylene glycol instead of 1.63 g of glycerin. The ester synthesis rate of this reaction solution was 96%,
The yield of propylene glycol oleate obtained is
It weighed 5.3g and had an acid value of 7. Furthermore, hexaglycerol oleate was prepared in the same manner as above using 8.2 g (17.7 mmol) of hexaglycerin instead of 1.63 g of glycerin. The ester synthesis rate of this reaction solution was 81%, and the yield of hexaglycerol oleate was 12.1 g.
The acid value was 13.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the results of analyzing the product of Example 27 using Iatroskian and comparing it with a standard substance.

Claims (1)

[Claims] 1 Polyalcohol selected from propylene glycol, glycerin, and polyglycerin and the number of carbon atoms
C ₂ - C ₂₂ saturated or unsaturated fatty acids (here fatty acids have hydroxyl groups, carboxyl groups,
may have a phenyl group) or C ₁ - C ₃
A reaction system is added to the mixture of the lower alcohol and the fatty acid forming the ester in the presence or absence of an organic solvent (excluding the primary alcohol solvent) without substantially adding water. A method for producing polyalcohol fatty acid ester, which comprises allowing microbial alkaline lipase to act while dehydrating so that the moisture content of the polyalcohol fatty acid ester is 0.1% by weight or less.