TWI468370B - Methods for producing esterified compounds - Google Patents

Description

Method for producing esterified compound

The present invention relates to a method for producing an esterified compound, which comprises a compound obtained by bonding at least one of a furanose structure or a pyranose structure of one or more and twelve or less. A method of producing an esterified compound by esterification, which is excellent in phase solubility with an amorphous resin and a crystalline resin, and is useful as a resin modifier, and can suppress coloring due to heating, and The resin modifier is used for improving the moldability, physical properties, flexibility, and impact resistance of the amorphous resin and the crystalline resin.

As a resin modifier, a sucrose benzoate is known, which is a compound obtained by bonding at least one of a furanose structure or a pyranose structure of one or more and 12 or less. An esterified compound (hereinafter referred to as "esterified compound") which is esterified, and a resin modifier is known to improve the formability, physical properties, or crystallinity of the amorphous resin. The softness and the impact resistance of the ester, such as ABS (Acrylonitrile-Butadiene-Styrene, C An acrylonitrile-butadiene-styrene resin, a polyvinyl chloride resin, an epoxy resin, an unsaturated polyester resin, and the like (Patent Documents 1 to 3).

However, when this esterified compound is added as a modifier, there is a problem in the hue of the product consisting of such a resin, or the thermal stability of a hue. That is, the esterified compound is generally produced using an organic solvent, but first, coloring occurs in the heating step of removing the organic solvent in the manufacturing process thereof. When the organic solvent used in the production process is removed, heating of 100 ° C or more, preferably 110 ° C or more is usually required, but under such heating conditions of 100 ° C or more, the coloring of the esterified compound proceeds. Further, even by using a special processing apparatus (for example, a thin film distillation apparatus), efforts are made to shorten the processing time to suppress the thermal history of the esterified compound when the organic solvent is removed, and to suppress the coloring as much as possible. There is a problem in that coloring occurs after the esterification compound is added to the resin due to the heat history during processing and molding of the resin.

Therefore, as a modifier of a resin requiring optical transparency, the prior esterified compound is by no means satisfactory.

[Previous Technical Literature] (Patent Literature)

(Patent Document 1) Japanese Patent Laid-Open No. 52-81362

(Patent Document 2) Japanese Patent Publication No. 62-15582

(Patent Document 3) Japanese Patent Laid-Open No. 6-255274

The present invention provides a method for producing an esterified compound which is excellent in phase solubility with an amorphous resin and a crystalline resin, and which is useful as a resin modifier, and can suppress coloration due to heating, and is thermally stable. The resin modifier is excellent in moldability, physical properties, flexibility, and impact resistance of the amorphous resin and the crystalline resin.

The inventors of the present invention have intensively studied and solved the above problems, and found that in the step of producing an esterified compound, the step of adsorbing the organic solvent solution of the esterified compound can be used to suppress the heat history. The present invention has been completed by repeating the review. That is, the first aspect of the present invention is a method for producing an esterified compound, which is characterized in that a compound obtained by bonding at least one of a furanose structure or a pyranose structure of one or more and twelve or less is esterified. A method for producing an esterified compound which is obtained by bonding at least one of a furanose structure or a pyranose structure of one or more and 12 or less, and an aromatic monocarboxylic acid. The ester, and the method for producing the esterified compound comprises the steps of subjecting the organic solvent solution of the esterified compound to an adsorbent treatment.

The foregoing adsorbent treatment, preferably in the organication of the aforementioned esterified compound The step of filtering the adsorbent after the solvent solution and the adsorbent are mixed and stirred.

The aforementioned adsorbent is preferably a synthetic zeolite.

Preferably, the compound obtained by bonding at least one of a furanose structure or a pyranose structure of one or more and 12 or less is sucrose, and the aromatic monocarboxylic acid is benzoic acid.

The esterified compound obtained by the production method of the present invention preferably has a hue of 50% or less in an APHA (American Public Health Association).

Further, the esterified compound is preferably a color phase of APHA 30 or less in a 50% toluene solution after heating at 110 ° C for 12 hours.

[Best Embodiment of the Invention]

The method for producing an esterified compound of the present invention includes a compound obtained by bonding at least one of a furanose structure or a pyranose structure of one or more and 12 or less, and esterification with an aromatic monocarboxylic acid. reaction.

The furanose structure of the present invention bonded by one or more and less than 12 The compound which is at least one of the pyranose structures is not particularly limited, and specific examples thereof include glucose, galactose, mannose, fructose, and wood. Xylose, or arabinose, lactose, sucrose, nystose, 1F-fructosylnystose, stachyose, maltitol (maltitol), lactitol, lactulose, cellobiose, maltose, cellotriose, maltotriose, raffinose Or cane fructose (kestose) and the like. Further, examples thereof include gentiobiose, gentiotriose, gentiotetraose, xylotriose, galactosylsucrose, and the like. Among these compounds, a compound having both a pyranose structure and a furanose structure is particularly preferred. For example, sucrose, canetriose, canetetraose, 1F-fructose-based canetetraose, stachyose, etc. are preferred, and sucrose is more preferred.

The aromatic monocarboxylic acid of the present invention is not particularly limited, and specific examples thereof include benzoic acid and toluic acid, which are obtained by introducing an alkyl group or an alkoxy group into a benzene ring of benzoic acid. An aromatic monocarboxylic acid having two or more benzene rings, such as aromatic monocarboxylic acid; cinnamic acid; benzilic acid, dibenzoic acid, naphthoic acid or tetrahydronaphthoic acid; Or such derivatives, more specifically, xylic acid, 2,3-dimethylbenzoic acid, 3,5-dimethylbenzoic acid (mesitylenic) Acid), 2,3,4-trimethyl Prehnitylic acid, 2,3,5-trimethylbenzoic acid, 2,4,5-trimethylbenzoic acid, 2,4,6-trimethyl Mesitoic acid, α-isodurylic acid, cuminic acid, α-toluic acid, hydrogen atoporic acid Hydratropic acid), atropic acid, hydrogen cinnamic acid, salicylic acid, o-anisic acid, meta-anisic acid, anisic acid, creosotic acid, neighbor O-homosalicylic acid, meta-salonic acid, ascorbic acid, 2,3-ditobenzoic acid, 2,4-dihydroxybenzoic acid, β-resorcylic acid, Vanillic acid, isovaleric acid, veratric acid, 2,3-dimethoxyic acid, gallic acid , asaronic acid, mandelic acid, anisic acid, levic acid, 3,4-dimethoxybenzoic acid, 2,3-dimethoxyphenylacetic acid (o-homoveratric acid), phthalonic acid, coumarin (P-coumaric acid), but particularly preferred is benzoic acid.

In the present invention, a compound obtained by bonding at least one of a furanose structure or a pyranose structure of one or more and 12 or less, and an aromatic monocarboxylic acid may be subjected to an esterification reaction by a conventional method. The production can be carried out, for example, according to the method for producing sucrose benzoate disclosed in Japanese Laid-Open Patent Publication No. 61-4839 or Japanese Patent Publication No. 40-5688.

That is, by using sucrose as a raw material and chlorine of an aromatic monocarboxylic acid The compound can be produced by performing an esterification reaction in a mixture of a hydrophilic solvent and water in the presence of a basic compound. As the hydrophilic solvent, for example, a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone; an ether solvent such as dioxane or tetrahydrofuran; an ester solvent such as methyl acetate; and an alcohol such as tertiary butanol are preferably used. Either solvent can be used.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonia, trimethylamine, and triethylamine.

The mixing ratio of the hydrophilic solvent to water is preferably such that the water content of the uniform liquid layer composed of the two becomes 7 to 80%. This is because, in such a hydrophilic solvent, although one of the raw materials, that is, the chloride of the aromatic monocarboxylic acid, or the product, that is, the ester, is dissolved therein, the other of the raw materials is sucrose, if alone. The hydrophilic solvent is completely insoluble or can be dissolved in a hydrophilic solvent to a degree that is not practical from the viewpoint of reaction efficiency, but the mixture can be dissolved by mixing a good solvent of sucrose, that is, water. The practical degree of sucrose is the reason. Therefore, by utilizing such a property of the hydrophilic solvent, the reaction rate of the sucrose and the chloride of the aromatic monocarboxylic acid can be controlled, and as a result, the amount of the chloride of the sucrose/aromatic monocarboxylic acid can be determined ( Mohrby), an ester having a low ratio of substitution or an average degree of ester substitution. For example, by increasing the amount of chloride of the aromatic monocarboxylic acid relative to the amount of sucrose fed, an ester having a relatively low proportion of low substituents or a relatively large average degree of ester substitution can be obtained; By reducing the amount of chloride of the aromatic monocarboxylic acid relative to the amount of sucrose fed, an ester having a relatively low proportion of low substituents or a relatively small average degree of ester substitution can be obtained.

As a method of the reaction, in the mixed liquid composed of a hydrophilic solvent and water, the chloride of the sucrose and the aromatic monocarboxylic acid is dissolved or suspended, and the chloride of the aromatic monocarboxylic acid is added dropwise. An equal amount or a plurality of excess of the basic compound; or in the mixture, after dissolving or suspending the sucrose and the basic compound, dropping the chloride of the aromatic monocarboxylic acid; or dissolving or suspending the sucrose in the mixed solution A method of simultaneously or alternately dropping a chloride of an aromatic monocarboxylic acid with a basic compound.

On the other hand, according to the method disclosed in Japanese Patent Publication No. 40-5688, the esterification reaction can be carried out by changing the hydrophilic solvent to another solvent, and the other solvent is selected from aromatic or One or two or more solvents of the substituted aromatic hydrocarbon, chlorinated aliphatic hydrocarbon, and lower aliphatic ether. Here, examples of the aromatic or substituted aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, chlorobenzene, chlorotoluene, etc.; and chlorinated aliphatic hydrocarbons include dichloromethane, chloroform, and carbon tetrachloride. And tetrachloroethylene; and the lower aliphatic ether may, for example, be diethyl ether or diisopropyl ether.

The reaction temperature may be from -15 ° C to 100 ° C, more preferably from -10 ° C to 30 ° C. However, after the entire reaction raw material is dropped, heating can be carried out in a high temperature zone in order to accelerate the completion of the reaction.

The pH in the reaction is preferably kept weakly alkaline. On the other hand, under strong alkali (depending on the reaction temperature, etc., for example, pH of 13 or higher), since the side reaction of hydrolysis of the aromatic monocarboxylic acid is remarkable, it is preferably, for example, at a pH of about 8 to 13 under.

The reaction time is not particularly limited as long as it is such that the reaction between the raw materials can be sufficiently completed. Although the specific time depends on the amount of the raw material compound or various conditions, it is usually sufficient for about one hour.

The method for producing an esterified compound of the present invention includes a compound obtained by bonding at least one of a furanose structure or a pyranose structure of one or more and 12 or less, and an ester with an aromatic monocarboxylic acid. After the reaction, the organic solvent solution of the esterified compound is subjected to an adsorption treatment step.

The adsorption treatment is carried out by separating the oil layer from the aqueous layer from the reaction mixture after completion of the esterification reaction, and bringing the oil layer into contact with the adsorbent. The method of contacting is not particularly limited, and a method of passing the oil layer through a packed column filled with an adsorbent, a method of adding an adsorbent to the oil layer and stirring, and then filtering and separating the adsorbent may be employed. In these methods, since the adsorbed dose used can exhibit efficacy even in a small amount, no special equipment (packing tower) or the like is required, and the adsorbent is preferably used. A method of adding to the oil layer and stirring, and then separating the adsorbent by filtration.

As the adsorbent used for the adsorption treatment, an adsorbent which is a porous solid and is generally used in the industry can be used. Specific examples thereof include cerium oxide, metal cerate, and other inorganic adsorbents. Specific examples of the cerium oxide include cerium gel, diatomaceous earth, and the like. The metal of the metal niobate may, for example, be an alkali metal such as sodium or potassium, an alkaline earth metal such as magnesium or calcium, or aluminum; and specific examples thereof include zeolite and synthetic zeolite. Examples of the other inorganic adsorbent include hydroxyapatite, activated clay, and inorganic synthetic adsorbents which are mainly composed of Mg, Al, Si, or the like, or a combination thereof. : KYOWAAD, Kyowa Chemical Industry Co., Ltd., etc.).

The amount of the adsorbent added is preferably 0.01 parts by mass or more and 1.0 part by mass or less with respect to 100 parts by mass of the solid content in the oil layer. When the amount is less than 0.01 parts by mass, the coloring prevention effect is insufficient, and even if it exceeds 1.0 part by mass, the coloring prevention effect is fixed, which is industrially disadvantageous.

The stirring time is not particularly limited and is 10 minutes or longer and 120 minutes or shorter. The stirring time is appropriately set depending on the amount of the adsorbent added. When the amount of the addition is large, the specific coloring prevention effect can be exhibited with a short stirring time.

In the method for producing the esterified compound of the present invention, the mixture after completion of the esterification reaction may be washed with water. The water washing can be carried out by a conventional method, for example, by adding water to the mixture after completion of the esterification reaction, stirring the mixture in a hot water bath, allowing the aqueous phase to separate, and then removing it. . The hot water bath temperature is preferably from 40 to 60 °C. When the temperature is 40° C. or less, the cleaning tends to be insufficient, and when it is 60° C. or more, the decomposition of the ester tends to occur. The stirring is not particularly limited as long as it is a water-soluble impurity, that is, a halogen ion or the like, which is sufficiently moved to the aqueous phase, and is usually sufficient for about 30 minutes. The number of times of washing differs depending on the raw materials used, the reaction conditions of the esters, and the like, and is usually sufficient from about 5 to 8 times.

The method for producing an esterified compound of the present invention comprises the step of drying an organic solvent solution.

The method of drying the organic solvent solution may be any of the conventional methods, and it is preferred to dry under reduced pressure by bringing it into contact with the heating surface under reduced pressure to distill off the solvent or the like. The conditions for drying under reduced pressure vary depending on various conditions such as the amount of raw materials used, the required drying efficiency, and the type of organic solvent to be used. The pressure is usually preferably 0.01 KPa ‧ abs or more. When the pressure is lower than 0.01 KPa‧abs, there is a tendency that the equipment becomes expensive. On the other hand, the pressure is preferably 15 KPa‧abs or less, more preferably 4 KPa‧abs or less. When the pressure is more than 15 KPa‧abs, the drying efficiency tends to decrease. In addition, the temperature of the heating surface when drying is performed (hereinafter, referred to as "heating temperature"), it is preferably 90 ° C or higher, more preferably 100 ° C or higher. When the heating temperature is lower than 90 ° C, the drying efficiency tends to decrease. On the other hand, the heating temperature is preferably 300 ° C or lower, more preferably 200 ° C or lower, still more preferably 160 ° C or lower. When the heating temperature exceeds 300 ° C, there is a tendency to color.

For the contact of the organic solvent solution of the esterification compound with the heating surface, for example, a vacuum drum dryer, a vacuum belt dryer, a film distillation machine, a flash distillation machine, a vacuum extruder, a stirring tank, or the like can be used. Implementation. These machines may be used alone or in combination of two or more of the same or different machines. When it is used in combination of two or more types, it is preferable to increase the degree of refining by joining, especially by connecting in series. Specific examples of the connection include, for example, a connection between a thin film distillation machine and a thin film distillation machine, a connection between a flash distillation machine and a thin film distillation machine, a connection between a stirring tank and a thin film distillation machine, and a connection between a stirring tank and a vacuum extruder.

The esterification ratio of the ester moiety of the compound obtained by the production method of the present invention, which is bonded to at least one of a furanose structure or a pyranose structure of one or more and 12 or less, is not The specific limitation can be appropriately set depending on the phase solubility with the amorphous resin and the crystalline resin.

For example, in the sucrose aromatic monocarboxylic acid ester, at least one of a furanose structure or a pyranose structure bonded to one or more and 12 or less is bonded. When one of the compounds is sucrose and the aromatic monocarboxylic acid is benzoic acid, it is possible to efficiently produce a sucrose aromatic monocarboxylic acid ester having a low thermal stability and a low esterification ratio. The ratio of the substituents of the 6-substituents or less is preferably, for example, 95% by mass or less, more preferably 85% by weight or less, still more preferably 50% by mass or less, most preferably 10% by mass or less. Here, the term "6-substituent" means that six of the eight hydroxyl groups in the total of sucrose are esterified by an aromatic monocarboxylic acid. For the sake of convenience, in the present specification, a substituent below the 6-substituent is referred to as a low-substituent.

The average value of the esterification ratio of the sucrose aromatic monocarboxylic acid ester, preferably the alcohol portion of sucrose (hereinafter referred to as "average ester substitution degree" or "average degree of substitution") is large, specifically, The average degree of ester substitution is, for example, 5.0 or more, preferably 6.0 or more, and more preferably 7.0 or more.

In the esterified compound obtained by the production method of the present invention, the hue in the 50% toluene solution is preferably APHA 30 or less. Further, in the esterified compound obtained by the production method of the present invention, after heating at 110 ° C for 12 hours, the hue in the 50% toluene solution is preferably 30 or less, more preferably 25 or less, still more preferably 15 or more. the following. When the hue is more than 30, when it is used as a resin modifier, the appearance (hue) and optical transparency of the resin tend to be lowered.

The esterified compound obtained by the production method of the present invention is used for The resin modifier is particularly useful as a modifier for resins requiring optical transparency because it has excellent characteristics for suppressing coloration by heating.

The resin to which the esterification compound is added is a crystalline resin such as a crystalline polyester resin, in addition to an amorphous resin such as an ABS resin, a polyvinyl chloride resin, an epoxy resin or an unsaturated polyester. The resin can be appropriately selected depending on the use thereof. Further, the sucrose aromatic monocarboxylic acid ester of the present invention to be added to the resin can be appropriately selected in a ratio of a low substituent or a degree of ester substitution depending on the kind and use of the resin.

The "ABS resin" is not particularly limited, and examples thereof include those obtained by graft-polymerizing acrylonitrile, styrene, α-methylstyrene, methyl methacrylate or the like with a rubbery polymer. The polymer is composed of polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, chlorinated polyethylene, acrylic rubber (such as methyl acrylate, ethyl acrylate, butyl acrylate, etc.) And a copolymer obtained with acrylonitrile, styrene, acrylic acid, acrylamide, 2-chloroethyl vinyl ether, etc., and, for example, an acrylonitrile-polybutadiene-styrene graft copolymer Wait. The ABS resin may be used alone or in combination of two or more.

The "polyvinyl chloride resin" is not particularly limited, and examples thereof include a vinyl chloride homopolymer resin; a chlorinated vinyl chloride resin; and one or more of all monomers copolymerizable with the vinyl chloride monomer. a vinyl chloride copolymerized resin obtained by random copolymerization or block copolymerization (for example, acetic acid B) An ester-vinyl chloride copolymer, an ethylene-vinyl chloride copolymer, or the like; and a resin obtained by grafting a functional group such as a hydroxyl group to the resin, or reacting such a functional group with a reactive compound to graft a bond The knot is made. The polyvinyl chloride resin may be used alone or in combination of two or more.

The "epoxy resin" is not particularly limited, and examples thereof include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol novolak type epoxy resin, and an alkyl group. An aralkyl type epoxy resin such as a phenol novolak type epoxy resin or a phenol biphenyl aralkyl epoxy resin, a biphenol type epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, or a combination An epoxide of a benzene type epoxy resin, a fluorene type epoxy resin, a condensate of a phenol and an aromatic aldehyde having a phenolic hydroxyl group, a triepoxypropyl isocyanurate, an alicyclic epoxy resin, or the like. The epoxy resins may be used alone or in combination of two or more.

The "unsaturated polyester resin" is not particularly limited, and is, for example, subjected to an addition reaction or a dehydration condensation reaction of an α,β-olefin-based unsaturated dicarboxylic acid or an anhydride thereof and a glycol. Synthesizer. Further, dicyclopentadiene or the like may be used in combination, and it may be reacted with a saturated dicarboxylic acid or an aromatic dicarboxylic acid or an anhydride thereof or a carboxylic acid. Examples of the "α,β-olefin-based unsaturated dicarboxylic acid" include maleic acid, fumaric acid, itaconic acid, citraconic acid, and anhydrides of such dicarboxylic acids. Examples of the "dicarboxylic acid" used in combination with these α,β-olefin-based unsaturated dicarboxylic acids include, for example, adipic acid, sebacic acid, succinic acid, phthalic anhydride, and phthalic acid. , isophthalic acid, p-phthalate Acid, tetrahydrophthalic acid, tetrachlorophthalic acid, and the like. Among these, fumaric acid which is an α,β-olefin-based unsaturated dicarboxylic acid and phthalic acid as a dicarboxylic acid are preferably used in combination. The unsaturated polyester resin may be used alone or in combination of two or more.

The "crystalline polyester resin" is not particularly limited, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, and poly 2,6-naphthalene dicarboxylate. Ester, polycyclohexane dimethanol terephthalate, polydiphenyl-4,4'-dicarboxylic acid 1,4-butane diester, poly-extension ethoxybenzoate, polyterephthalic acid a crystalline polyester such as 1,3-propanediester or polyhexamethylene terephthalate; among these, polyethylene terephthalate or polyterephthalic acid 1 is preferred. 4-butyl diester, polyethylene 2,6-naphthalenedicarboxylate. The crystalline polyester resin may be used alone or in combination of two or more.

According to the production method of the present invention, the phase solubility with the amorphous resin and the crystalline resin is excellent, and the moldability, physical properties, flexibility, impact resistance, and the like can be improved, and both can be suppressed. Excellent characteristics of heating and coloring. Therefore, an esterified compound which can be used as a modifier of a resin requiring optical transparency can be provided. Further, according to the production method of the present invention, since it is possible to easily produce an esterified compound which exhibits such excellent characteristics without using a special processing apparatus (for example, a thin film distillation apparatus), it is industrially related to the production cost and the like. It is beneficial.

"Embodiment"

The present invention will be described in detail based on the embodiments, but the invention is not limited thereto. In this specification, the term "parts" means "parts by mass".

[Materials used]

Sucrose: 99.9%, manufactured by Shin Kong Sugar Co., Ltd.

Benzoyl chloride: >99.5%, manufactured by Kawaguchi Pharmaceutical Co., Ltd.

Adsorbent: Product name Molecular sieve 13X, manufactured by Union Showa Co., Ltd.

[Manufacture of esterified compound] (Example 1)

In a 1 liter five-necked flask equipped with a stirring bar, a thermometer, a cooling condenser, a dropping funnel, and a pH electrode connected to a pH meter, 34.2 parts of sucrose and 70 parts of water were fed, and then cooled to 10 ° C or less in a water bath. 100 parts of cyclohexanone containing 75.0 parts of benzamidine chloride (1) was slowly added. Thereafter, while maintaining the temperature at 20 ° C or lower, 48.5 parts of a 48% aqueous sodium hydroxide solution was added from the dropping funnel at a pH maintained at 10 to 11. After removing the water bath, stirring was continued at room temperature of 20 to 30 ° C for 1 hour to complete the reaction. After the reaction was completed, a certain amount of sodium carbonate was added and heated to convert a residual trace of benzamidine chloride into sodium benzoate. Thereafter, it was allowed to stand for about 30 minutes to separate the aqueous phase and remove it. A molecular sieve 13X 0.07 parts was fed to the oil phase, and stirred at room temperature of 20 to 30 ° C for 0.5 hour. Thereafter, the mixture was filtered under reduced pressure using a 0.2 μm filter paper, and the molecular sieve 13X was separated by filtration to obtain a clear oil phase, and then the temperature was raised to 120 ° C, and the solvent was distilled off under reduced pressure. The target esterified compound is obtained.

(Example 2)

The treatment was carried out in the same manner as in Example 1 except that 82.1 parts of benzamidine chloride and 53.1 parts of a 48% aqueous sodium hydroxide solution were used to obtain a target esterified compound.

(Example 3)

The treatment was carried out in the same manner as in Example 1 except that 93.7 parts of benzamidine chloride and 60.6 parts of a 48% aqueous sodium hydroxide solution were used to obtain a target esterified compound.

(Example 4)

Except that 106.7 parts of benzamidine chloride and 69.0 parts of 48% aqueous sodium hydroxide solution were used, the others were treated in the same manner as in Example 1 to obtain a target esterified compound.

(Example 5)

The treatment was carried out in the same manner as in Example 1 except that 113.9 parts of benzamidine chloride and 73.7 parts of a 48% aqueous sodium hydroxide solution were used to obtain a target esterified compound.

(Comparative Examples 1 to 5)

Except that the treatment was not carried out using an adsorbent, the others were treated in the same manner as in Examples 1 to 5, respectively, to obtain an esterified compound.

[Average degree of substitution and determination of the ratio of each substituent]

The measurement was carried out by the following method. The results of the measurements are shown in Table 1 below.

(average degree of substitution)

It was determined by proton nuclear magnetic resonance ( ¹ H-NMR).

(proportion of each substitute)

Determined by liquid chromatography mass spectrometry (LC-MS).

[assessment]

The evaluation was carried out by the following methods. The results of the measurements are shown in Table 1 below.

(hue)

In the test tube, 5 g of each ester obtained in the above Examples and Comparative Examples was added, and the hue was determined in accordance with the method disclosed in JIS K2421. That is, after diluting each sample to 50% with toluene, the color of the diluted liquid was judged to be the same value of the APHA standard solution (Hazen color number: APHA) when compared with the naked eye.

(hue stability)

5 g of each ester obtained in the above Examples and Comparative Examples was placed in a test tube, and heated in an oil bath at 110 ° C for 12 hours. With respect to each of the samples thus obtained, the hue was determined in the same manner as the method described in the above (hue).

As shown in Table 1, in the case of treatment with an adsorbent, not only In Examples 4 and 5 in which the proportion of the low-substituents which are less likely to be colored was small, even in Examples 1 to 3 in which the proportion of the low-substituents which are easy to be colored was large, the excellent result of the hue of the product was 30 or less, and not only that. After heating at 110 ° C for 12 hours thereafter, the hue of the product did not change and showed high heat stability. On the other hand, in the case where the treatment was not carried out using the adsorbent, the color change before and after the heat treatment was large and the thermal stability was low regardless of the ratio of the low-substance.

[Industrial use possibility]

The esterified compound obtained by the production method of the present invention is excellent in phase solubility with an amorphous resin and a crystalline resin, and can improve such moldability, physical properties, flexibility, and impact resistance. It is possible to suppress the excellent characteristics of coloring by heating, and therefore, it is used as a modifier for a resin, and particularly as a modifier for a resin requiring optical transparency.

The present invention has been described in detail with reference to the specific embodiments thereof, and it is obvious that various modifications and changes can be made without departing from the spirit and scope of the invention.

The present application is based on Japanese Patent Application No. 2012-121804 filed on May 29, 2012, the content of which is hereby incorporated by reference.

Claims (5)

A method for producing an esterified compound, which is a method for producing an esterified compound by esterifying a compound obtained by bonding at least one of a furanose structure or a pyranose structure of one or more and 12 or less. The esterified compound is a compound obtained by bonding at least one of a furanose structure or a pyranose structure of one or more and 12 or less, and an ester of a chloride of an aromatic monocarboxylic acid, and the ester The method for producing a chemical compound comprises the steps of subjecting an organic solvent solution of the esterified compound to an adsorbent treatment. The method for producing an esterified compound according to claim 1, wherein the adsorbent treatment is a step of filtering the adsorbent by stirring and mixing the organic solvent solution of the esterified compound with an adsorbent. The method for producing an esterified compound according to claim 1, wherein the adsorbent is a synthetic zeolite. The method for producing an esterified compound according to claim 2, wherein the adsorbent is a synthetic zeolite. The method for producing an esterified compound according to any one of claims 1 to 4, wherein the method of bonding at least one of a furanose structure or a pyranose structure of one or more and twelve or less is bonded. The compound is sucrose and the aromatic monocarboxylic acid is benzoic acid.