Saccharide derivative, molding and method for producing the same

Abstract

To provide a saccharide derivative in which a processing temperature of a saccharide derivative can be moved from a high-temperature range to a low-temperature range.SOLUTION: In a saccharide derivative of the embodiment, its saccharide is selected from any one of monosaccharide, disaccharide, amylose having a molecular weight (Mw) of 20000 or less, and xylan having a molecular weight (Mw) of 20000 or less. In the saccharide derivative, hydrogen of hydroxyl group of the monosaccharide is substituted for a structure having an aliphatic hydrocarbon chain such as palmityl or stearyl, and an aromatic ring such as benzyl or tolyl.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a saccharide derivative that is easy to manufacture as a biomass material and whose processing temperature can be controlled. In particular, the present invention relates to a saccharide derivative that can be processed at a lower temperature, a molded article using the saccharide derivative, and a method for producing the saccharide derivative.

Background Art

[0002] In recent years, saccharides have attracted attention as raw materials with a low environmental impact. Patent Document 1 proposes an aromatic aliphatic mixed cellulose ester in which both the degree of substitution of an aromatic acyl group and the degree of substitution of a saturated aliphatic acyl group are 0.1 or more and 2.9 or less, for the purpose of providing an electrode for a non-aqueous electrolyte secondary battery. Further, Patent Document 2 proposes synthesizing a cellulose ester selectively substituted using trifluoroacetic anhydride and cellulose together with various acyl donors or acyl donor precursors. Patent Document 3 proposes a poly-α-1,3-glucan ester derivative substituted with an acetyl group and a benzoyl group. Furthermore, Patent Document 4 proposes a polysaccharide ether ester for the purpose of obtaining a polysaccharide derivative having both thermoplasticity and biodegradability using a standard solvent.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0004] In the industrial production of saccharide derivatives, the ease of obtaining raw sugars and the simplicity of synthesis are important. In this regard, the inventions of Patent Document 1 and Patent Document 2 have the problem that cellulose used as a raw material is hardly soluble in various solvents, and the reaction must be carried out after protecting the hydroxyl groups of cellulose with a protecting group such as an acetyl group. The invention of Patent Document 3 has the problem that poly α-1,3-glucan is a compound obtained by chemical synthesis or biosynthesis of fungi and bacteria, so it is difficult to obtain and not suitable for mass production. The invention of Patent Document 4 has the problem that the synthesis of the substituent itself is multi-step and the control of the reaction is difficult, so the synthesis yield decreases. In addition, the saccharide derivative has the problem that the processing temperature is in a high temperature range.

[0005] In order to solve these problems, the present inventors provide a technique that enables a significant shift in the processing temperature to the low temperature region.

Means for Solving the Problems

[0006] In order to solve these problems, the present inventors developed saccharide derivatives using monosaccharides, disaccharides, amylose with a molecular weight (Mw) of 20,000 or less, and xylan with a molecular weight (Mw) of 20,000 or less. These saccharides are easily available as natural product-derived products, highly soluble in various general solvents such as water, pyridine, DMSO, and DMF, and can be easily subjected to operations from synthesis to purification, and derivatives can be obtained in high yields.

[0007] Furthermore, in the derivatives using these saccharides, by coexisting a structure having an aliphatic hydrocarbon chain and an aromatic ring in the molecule, compared with saccharide derivatives substituted with only one of the structures having an aliphatic hydrocarbon chain or an aromatic ring, the movement of thermal properties such as melting point and loss elastic modulus to the low temperature region was enabled. In addition, it was found that the processing temperature can be controlled by the composition ratio.

[0008] The saccharide derivative of the present embodiment is such that the saccharide is at least one selected from monosaccharides, disaccharides, amylose having a molecular weight (Mw) of 20,000 or less, and xylan having a molecular weight (Mw) of 20,000 or less, and the substituent contains the structures of both the following (Formula 1) and the following (Formula 2). [Chemical formula] (Formula 1) [Chemical formula] (Formula 2) In Formula 1, R1 is an aliphatic hydrocarbon chain, which may be linear, branched, saturated or unsaturated, and may be an ester bond or an ether bond. In Formula 2, R2 is a structure having an aromatic ring, and may be an ester bond or an ether bond.

[0009] It is preferable that the hydrogen of the hydroxyl group of the saccharide is completely substituted by the substituents of (Formula 1) and (Formula 2), and the aliphatic substitution ratio, which is the ratio of the substituent of (Formula 1) to all substituents, is 10% or more and 90% or less.

[0010] In (Formula 1), it is preferable that R1 is palmitoyl or stearyl. In (Formula 2), it is preferable that R2 is phenyl, benzyl or tolyl. The saccharide used as a raw material for the saccharide derivative is preferably glucose, sucrose, amylose having a molecular weight (Mw) of 8,000 to 12,000, or xylan having a molecular weight (Mw) of 300 to 1,500. The saccharide derivative of the present embodiment can be formed into a molded article.

[0011] The method for producing the saccharide derivative of the present embodiment is to react at least one saccharide selected from monosaccharides, disaccharides, amylose having a molecular weight (Mw) of 20,000 or less, and xylan having a molecular weight (Mw) of 20,000 or less with the substituents of both the above (Formula 1) and the above (Formula 2). (a) A dissolving step of dissolving the saccharide in its good solvent, (b) A first reaction step of esterifying or etherifying some of the hydroxyl groups of the saccharide; (c) A second reaction step of esterifying or etherifying the remaining hydroxyl groups of the saccharide after the first reaction; (d) A purification step of purifying the reaction product from the reaction solution after the second reaction.

Advantages of the Invention

[0012] The saccharide derivative of the present invention is easily industrially producible as a biomass material, and the processing temperature can be controlled, particularly at low temperatures.

Embodiments for Carrying Out the Invention

[0013] <<Saccharides>> The saccharide used in the saccharide derivative of this embodiment is at least one saccharide selected from monosaccharides, disaccharides, amylose with a molecular weight (Mw) of 20,000 or less, and xylan with a molecular weight (Mw) of 20,000 or less. The saccharides of this embodiment have high solubility in various reaction solvents such as water, pyridine, DMSO, and DMF, and can easily perform the steps from synthesis to purification, and derivatives can be obtained in high yields. When the molecular weight (Mw) of amylose or xylan is greater than 20,000, the solubility in the reaction solvent decreases, the reaction system is restricted, and the synthesis of the target saccharide derivative becomes difficult. Among them, considering that it is easily obtained by simple treatment when extracted from natural products, for amylose, the molecular weight (Mw) is preferably 8,000 to 12,000, and for xylan, the molecular weight (Mw) is preferably 300 to 1,500.

[0014] <Monosaccharide> The monosaccharides of this embodiment are saccharides that cannot be hydrolyzed further. Specifically, examples include heptose, hexose, pentose, tetrose, triose, or rare sugars. Heptose includes sedoheptulose, coliosse, etc., and hexose includes glucose, mannose, galactose, fructose, glucuronic acid, galacturonic acid, etc. In addition, pentose includes xylose, arabinose, ribose, lyxose, ribulose, xylulose, deoxyribose, etc., and tetrose includes erythrose, threose, erythrulose, etc. Triose includes glyceraldehyde, dihydroxyacetone, etc., and rare sugars include xylitol, erythritol, psicose, allose, sorbose, tagatose, talose, idose. These are merely examples and are not limited thereto. Among monosaccharides, xylose and glucose, which are easy to extract, decompose, and purify from biomass-derived raw materials, are desirable, and in particular, glucose, which has a large number of hydroxyl groups and allows for a wide range of substitution ratios, is more desirable.

[0015] <Disaccharide> The disaccharides of this embodiment refer to sugars in which two monosaccharide molecules are dehydrated and condensed to form a glycosidic bond to become one molecule. The bonding mode between monosaccharides can be any of [1→1], [1→2], [1→3], [1→4], [1→6], and can be either an α-glycosidic bond or a β-glycosidic bond. Specific examples of disaccharides include lactose in which galactose and glucose are bonded, sucrose in which glucose and fructose are bonded, and in addition, maltose, cellobiose, xylobiose, arabinobiose, gentiobiose, mannobiose, trehalose, lactulose, melibiose (planteobiose), melibulose, rutinose, rutinosulose, primeverose, vicianose, nigerose, laminaribiose, turanose, kojibiose, sophorose, etc. These are merely examples and are not limited thereto. Among disaccharides, sucrose, which is easy to extract, decompose, and purify from biomass-derived raw materials, is desirable.

[0016] <Amylose> The amylose of this embodiment has a molecular weight (Mw) of 20,000 or less and includes a polysaccharide in which glucose is arranged linearly by α-[1→4] bonds and a polysaccharide having a branched chain by α-[1→6] bonds in a part thereof. Further, the amylose of this embodiment has a molecular weight (Mw) of 20,000 or less and may include a mixture of amylose and amylopectin. Such amylose may have a part of the hydroxyl groups of the raw material substituted, and can be obtained by hydrolyzing starch obtained from plants by an ordinary method with an acid or an enzyme treatment or the like to reduce the molecular weight.

[0017] <Xylan> The xylan of this embodiment has a molecular weight (Mw) of 20,000 or less and is a multimer of xylose. In its bonding mode, it may be either [1→3] or [1→4], and may be either an α-glycosidic bond or a β-glycosidic bond. Such xylan is a natural product-derived one obtained by extracting hemicellulose constituting the plant cell wall and hydrolyzing it with an acid or an enzyme treatment or the like to reduce the molecular weight. Xylan may have a branched chain and may have a part of the hydroxyl groups of the raw material substituted. The monosaccharides constituting the xylan of this embodiment may include a small amount of glucose, mannose, galactose, and arabinose.

[0018] <<Saccharide derivative>> The saccharide derivative of this embodiment is partially or entirely substituted with substituents. The substituents of the derivative include the structures of both (Formula 1) and (Formula 2).

[0019] [Chemical formula] (Formula 1)

[0020] [Chemical formula] (Formula 2)

[0021] In the substituent of the saccharide derivative (Formula 1), the structure of R1 is an aliphatic hydrocarbon chain, which may be linear, branched, saturated or unsaturated. Examples of the linear saturated hydrocarbon chain include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, palmityl, margaryl, stearyl, nonadecyl, arachidyl, heneicosyl, behenyl, tricosyl, tetracosyl, etc. Examples of the branched saturated hydrocarbon chain include, but are not limited to, isopropyl, sec-butyl, isobutyl, tert-butyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, tert-pentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isolauryl, isomyristyl, isopentadecyl, isopalmitoyl, isomargaroyl, isostearyl, isononadecyl, isoarachidyl, isoheneicosyl, isobehenyl, isotricosyl, isotetracosyl, etc.

[0022] Examples of the unsaturated hydrocarbon chain include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, etc. having a double bond, and ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, icosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, etc. having a triple bond.

[0023] These hydrocarbon chains may be used alone or in combination of two or more. The main raw materials of these hydrocarbon chains may be those directly isolated from natural products, those semi-synthesized using the isolated ones as starting materials, or synthetic products. From the perspective of reducing environmental impact, those derived from natural products are preferred over synthetic products, and palmitoyl and stearyl, which can be easily obtained as vegetable fatty acids, are more preferred.

[0024] In the substituent of the saccharide derivative (Formula 2), R2 has a structure with an aromatic ring. Examples of the structure with an aromatic ring include phenyl, benzyl, tolyl, xylyl, mesityl, as-pseudocumyl, v-pseudocumyl, s-pseudocumyl, duryl, methoxyphenyl, hydroxyphenyl, acetylphenyl, cinnamyl, etc. Further, examples of the structure with an aromatic ring also include those having the aromatic ring structure of polycyclic aromatic compounds such as naphthalene and anthracene, heterocyclic aromatic compounds such as furan and pyrrole, and non-benzene aromatic compounds such as azulene, but are not limited thereto.

[0025] These structures with an aromatic ring may be used alone or in combination of two or more. The main raw materials of these aromatic rings may be those directly isolated from natural products, those semi-synthesized using the isolated ones as starting materials, or synthetic products. From the perspective of reducing environmental impact, those derived from natural products are preferred over synthetic products, and phenyl, benzyl or tolyl derived from plants, which are easily available, are preferred, and phenyl is more preferred.

[0026] The saccharide derivative of this embodiment can control the processing temperature to the low temperature side by including the structures of both (Formula 1) and (Formula 2) in its substituent, and can provide a saccharide derivative that can be processed at low temperature. Compared with the case where the substituent is (Formula 1) or (Formula 2) alone, the saccharide derivative containing the structures of both (Formula 1) and (Formula 2) can shift the processing temperature to the low temperature side by 5 °C or more, preferably 10 °C or more, more preferably 20 °C or more, and even more preferably 30 °C or more in terms of temperature characteristics.

[0027] The temperature characteristics in this case refer to the melting point or the loss modulus G” as shown in the examples being 103 Refers to the temperature T1000 that becomes below Pa. Note that, as will be described in detail in the examples, T1000 is an index of the fluidization temperature. In this embodiment, by grasping such a tendency, it is possible to design a saccharide derivative having temperature characteristics suitable for processing temperatures that have been difficult in the past.

[0028] By derivatizing saccharides with both aliphatic and aromatic substituents, it is considered that the intermolecular interactions between aliphatic hydrocarbon chains, the intermolecular interactions between structures having aromatic rings, and π-π stacking can be inhibited respectively, and the intramolecular and intermolecular interactions of the saccharide derivative can be weakened. As a result, it is considered that the temperature characteristics of the saccharide derivative were able to be lowered because the mobility of the substituents at lower temperatures was improved and the mobility of the sugar backbone was improved chainwise.

[0029] The substituent of the saccharide derivative of this embodiment may be an ester bond (when having a C=O bond in () in the substituent (Formula 1) (Formula 2)) or an ether bond (when not having a C=O bond in () in the substituent (Formula 1) (Formula 2)) in its bonding mode. Also, the substituent of the saccharide derivative may be in a single bonding mode of only an ether bond or only an ester bond, or both may be mixed. From the simplicity of synthesis, an ester bond is preferred.

[0030] Some of the hydroxyl groups derived from unsubstituted saccharides may remain, but by making it a fully substituted product, the hydrophilicity decreases and the yield improves during simple purification using water. Also, by making it a fully substituted product, the fluidity improves at a lower temperature. This change in thermal properties is considered to be due to the disappearance of hydrogen bonds and the improvement of molecular mobility. The fully substituted product referred to here means one in which 95% or more of the hydroxyl groups of the saccharide are substituted, preferably 99% or more, and more preferably 100%.

[0031] When the hydrogen of the hydroxyl group of the saccharide is completely substituted, the aliphatic substitution ratio, which is the ratio of the substituents of (Formula 1) to all substituents, is preferably 10% or more and 90% or less. By controlling the processing temperature, especially when the substituent is (Formula 1) or (Formula 2) alone, the temperature characteristics can be significantly shifted to the lower temperature side. From this perspective, the lower limit of the aliphatic substitution ratio described above is more preferably 20% or more, even more preferably 30% or more, and the upper limit is more preferably 80% or less, even more preferably 70% or less.

[0032] <Method for Producing Saccharide Derivative> The method for producing a saccharide derivative reacts both the substituents of (Formula 1) and (Formula 2) with a saccharide selected from at least one saccharide of a monosaccharide, a disaccharide, amylose having a molecular weight (Mw) of 20,000 or less, and xylan having a molecular weight (Mw) of 20,000 or less. The method for producing a saccharide derivative (a) A dissolution step of dissolving the saccharide in its good solvent; (b) A first reaction step of esterifying or etherifying some of the hydroxyl groups of the saccharide; (c) A second reaction step of esterifying or etherifying the remaining hydroxyl groups of the saccharide after the first reaction; (d) A purification step of purifying the reaction product from the reaction solution after the second reaction.

[0033] By having these steps, the target saccharide derivative can be obtained in a very simple method with a homogeneous reaction system and sequential input of reaction raw materials. The saccharide may be any one of a monosaccharide, a disaccharide, amylose, and xylan, or a mixture of two or more saccharides.

[0034] The good solvent in step (a) is a solvent capable of almost completely dissolving the raw material saccharide. Examples of such good solvents include, but are not limited to, water, pyridine, DMF, DMSO, and mixtures thereof. Methods of dissolving in the solvent include stirring, shaking, ultrasonic waves, heating, etc.

[0035] By undergoing step (b) and step (c), both substituents of formula (1) and formula (2) are reacted with the saccharide. Thus, it is substituted with the substituent of formula (1) in step (b) and subsequently substituted with the substituent of formula (2) in step (c), or substituted with the substituent of formula (2) in step (b) and subsequently substituted with the substituent of formula (1) in step (c). At this time, as a result of step (c), the hydroxyl group of the saccharide may or may not remain. Also, it is preferable from the viewpoint of reaction control to substitute a substituent with a desired small equivalent amount in step (b).

[0036] When the reactions of step (b) and step (c) are esterification, usually, an acid halide, acid anhydride, carboxylic acid, ester, ketone, aldehyde, alcohol, etc. are reacted with the hydroxyl group of the saccharide. Among these, acid halides, acid anhydrides, and carboxylic acid esters are preferable, and acid halides are more preferable, and acid chlorides are even more preferable, from the viewpoints of easy availability of raw materials, synthesis of raw materials, and ease of derivatization reaction. As methods of esterification, the Schotten–Baumann reaction, Fischer ester synthesis, transesterification reaction, Mitsunobu reaction, synthesis via an active species using pyridine or DMAP (N,N-dimethyl-4-aminopyridine), etc. are known. When using an acid halide, it is preferable to use the Schotten–Baumann reaction or a reaction in pyridine, from the viewpoints of the yield during synthesis and easy availability of reagents.

[0037] When the reactions of step (b) and step (c) are etherification, usually, an alkyl halide, alkyl tosylate, dialkyl sulfate, alcohol, etc. are reacted with the hydroxyl group of the saccharide. Among these, alkyl halides or alcohols are preferable, and alkyl halides are more preferable, and alkyl chlorides are even more preferable, from the viewpoints of easy availability of raw materials, synthesis of raw materials, and ease of reaction during derivatization. As methods of etherification, Williamson ether synthesis, Mitsunobu reaction, dehydration condensation using an acid catalyst, etc. can be mentioned. When using an alkyl halide, it is desirable to use Williamson ether synthesis, from the viewpoints of the yield during synthesis and easy availability of reagents.

[0038] In the above esterification or etherification reaction, an organic acid, an organic base, an inorganic acid, an inorganic base, a metal catalyst, etc. can be added to the reaction system for the purpose of starting the reaction or promoting the reaction.

[0039] The purification process in step (d) is carried out by, for example, combining liquid-liquid separation purification using two liquids, removal of the solvent by drying under reduced pressure, recrystallization using a saturated solvent, reprecipitation using a poor solvent, etc., but is not limited thereto. The appropriate purification method varies depending on the melting point of the compound to be synthesized. For a compound that is liquid at room temperature, a combination of liquid-liquid separation purification and removal of the solvent by drying under reduced pressure is effective, and for a compound that is solid at room temperature, it is effective to repeatedly perform reprecipitation using a poor solvent while changing the poor solvent.

[0040] <Method for manufacturing a molded article> The saccharide derivative of the present embodiment is preferably made into a molded article that contains all or part of it. The resin composition containing at least part of the saccharide derivative of the present embodiment can be processed into a molded article of a desired shape by heating to melt, fluidize, or soften it and then charging it into a mold and compressing it, or extruding it into a rod shape, a fiber shape, a hollow shape, or a sheet shape.

[0041] The plastic resin combined with the saccharide derivative as the molded article may be a non-degradable plastic material or a biodegradable plastic material. Examples of non-degradable plastic materials include general-purpose plastics such as PP (polypropylene), PE (polyester), PET (polyethylene terephthalate), PC (polycarbonate), PMMA (polymethyl methacrylate), PS (polystyrene), COP (cycloolefin polymer), and COC (cycloolefin copolymer).

[0042] Biodegradable plastic materials include PLA (polylactic acid), PBS (polybutylene succinate), PBAT (polybutylene adipate terephthalate), PHA (polyhydroxyalkanoic acid), PHB (polyhydroxybutyric acid), PHBH (copolyester composed of R-3-hydroxybutanoic acid (3HB) and R-3-hydroxyhexanoic acid (3HH)), cellulose or its derivative materials, hemicellulose or its derivative materials, and the like. Neither biodegradable plastic materials nor non-biodegradable plastic materials are limited to these.

[0043] Examples of the molding method of the molded product include, for example, injection molding, extrusion molding, casting, calender molding, slush molding, blow molding, vacuum molding, powder molding, foam molding, extrusion lamination molding, T-die molding, air-cooled inflation molding, water-cooled inflation molding, microwave molding which is a type of optical molding that heats the mold with radiation, and the like. Further, it may be formed into a molded product by deforming (molding) using its own weight without using a mold, 3D printing, or applying an external force using tools.

[0044] The molded product can be molded into various shapes such as, for example, films, thin plates, thick plates, corrugated boards, threads, filaments, rods, pipes, columns, shaped objects, artworks, and the like.

[0045] <Industrial Applicability> The saccharide derivative obtained according to this embodiment can be applied in fields such as the chemical industry, food industry, petroleum industry, civil engineering and construction industry, textile industry, pulp and paper industry, paint and ink industry, metal industry, machinery industry, ceramics industry, or pharmaceutical industry. It is particularly suitable in the chemical industry field, and it is possible to provide a saccharide derivative suitable as a viscosity reducer, plasticizer, fluidizing agent, thickener, lubricant, binder, and emulsion stabilizer.

Examples

[0046] <Measurement and Evaluation Methods> (1) Measurement of Melting Point A differential scanning calorimeter (DSC) (DSC3100 manufactured by Netzsch Japan Co., Ltd.) was used. The measurement conditions were as follows: heating rate: 10 °C / min, measurement temperature range: -80 °C to 200 °C, and the measurement was carried out under an air atmosphere. "ND" indicates non-detection. (2) Measurement of loss elastic modulus G" A dynamic viscoelasticity measuring device (ARES-G2 rheometer manufactured by TA Instruments Japan Co., Ltd.) was used. The measurement temperature was measured under a temperature decreasing condition of 1 °C / min starting from the temperature at which the fluidity was sufficiently high until the temperature at which the fluidity was not shown. The measurement system was carried out under the conditions of a stainless-steel parallel plate with a diameter of 25 mm, a frequency of 1 Hz, and an air atmosphere. As an example, the results obtained in Example 6 below are shown in Table A.

[0047]

Table A

[0048] The loss elastic modulus G" is a value correlated with viscosity, and the lower the G", the higher the fluidity. In this example, the temperature decreasing measurement was started from 60 °C at which the fluidity was sufficiently high and measured until -10 °C at which the fluidity disappeared. The region where the fluidity changes is between 30 °C and 40 °C, and it can be seen that it can be easily processed at temperatures above this. The temperature at which the value of the loss elastic modulus G" becomes 10 3 Pa is effective as a typical index, and this is denoted as T1000. The T1000 of Example 6 in Table A is 34 °C. "ND" of T1000 shown in Table 1 indicates that denaturation and carbonization occurred during the temperature increasing process before the start of the measurement, and the temperature at which the value of G" becomes 10 3 Pa could not be found.

[0049] (3) Measurement of the molecular weight (Mw) of amylose and xylan Gel permeation chromatography (GPC) (main body: Waters ACQUITY Arc, detector: RI, column: Shodex OHpak SB-803 HQ, OHpak SB-802 HQ) was used to determine the weight average molecular weight Mw. The measurement conditions were as follows: the solvent was only water, the sample concentration was 0.1%, the injection volume was 10 μL, the flow rate was 0.5 mL / min, and the column temperature was 40 °C. (4) Measurement of the ratio of substituents The hydroxyl value of the purified sample, if necessary, was measured by back titration. The degree of substitution of each substituent was calculated from the amount of residual hydroxyl groups in the raw material and the products of each step. (5) MFR (melt flow rate) measurement Using a measuring device compliant with JIS K7210―1:2014, MFR was measured under the following conditions. Temperature: 200 °C Load: 5.0 Kgf Charge amount: 4.5 g Measuring machine: Melt Indexer LMFI 5500 manufactured by Nippon Dynisco

[0050] <Reagents used> The reagents used in the examples and comparative examples are as follows. Pyridine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.5+% (mass / mass) (C5H5N) (GC)), Benzoyl chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.0+% (Titration)), Palmityl chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 97.0+% (Titration)), Ethyl acetate (manufactured by Junsei Chemical Co., Ltd., purity 99.5+% (mass / mass)), Methanol (manufactured by Sigma-Aldrich, 99.8+% (GC)).

[0051] <Examples 1-4, Comparative Examples 1-2: The saccharide is amylose> The saccharide derivatives of Examples 1-4 and the saccharide derivatives of Comparative Examples 1-2 were prepared by stirring and dissolving 60 g of amylose derived from corn extract (glucose component 95%, molecular weight Mw of about 10,000) in 600 mL of pyridine (dissolution step).

[0052] In Example 1, after amylose was completely dissolved in pyridine, the solution was ice-cooled using an ice bath, and 81 g of benzoyl chloride was added dropwise with stirring (the first reaction step). Subsequently, 200 g of palmitoyl chloride was added dropwise (the second reaction step). After the addition was completed, the reaction solution was removed from the ice bath and stirred for a total of 12 hours. Thereafter, the reaction solution was added to 2 L of water, stirred, and the water was removed by filtration. The precipitate was dissolved in 300 mL of ethyl acetate, stirred while flowing it little by little into 3 L of methanol, and finally the precipitated product was filtered and dried to obtain 218 g of amylose palmitate benzoate derived from corn extract (purification step). The substitution ratio of the saccharide derivative synthesized in Example 1 was 50% for the aliphatic hydrocarbon chain and 50% for the structure having an aromatic ring.

[0053] In Example 2, the reactant added dropwise in the first reaction step was changed to 18 g of benzoyl chloride, and the reactant added dropwise in the second reaction step was changed to 300 g of palmitoyl chloride. Otherwise, it was produced in the same manner as in Example 1. In Example 2, 260 g of amylose palmitate benzoate derived from corn extract was obtained. The substitution ratio of the saccharide derivative synthesized in Example 2 was 90% for the aliphatic hydrocarbon chain and 10% for the structure having an aromatic ring.

[0054] In Example 3, the reactant added dropwise in the first reaction step was changed to 34 g of palmitoyl chloride, and the reactant added dropwise in the second reaction step was changed to 158 g of benzoyl chloride. The dropping order of palmitoyl chloride and benzoyl chloride was reversed from that in Example 1. Otherwise, it was produced in the same manner as in Example 1. In Example 3, 171 g of amylose palmitate benzoate derived from corn extract was obtained. The substitution ratio of the saccharide derivative synthesized in Example 3 was 10% for the aliphatic hydrocarbon chain and 90% for the structure having an aromatic ring.

[0055] In Example 4, the reactant dropped in the first reaction step was changed to 68 g of palmitoyl chloride, and the reactant dropped in the second reaction step was changed to 138 g of benzoyl chloride. The dropping order of palmitoyl chloride and benzoyl chloride was reversed compared to Example 1. Other than that, it was produced in the same manner as in Example 1. In Example 4, 180 g of amylose palmitate benzoate derived from corn extract was obtained. The substitution ratio of the saccharide derivative synthesized in Example 4 was 20% for the aliphatic hydrocarbon chain and 80% for the structure having an aromatic ring.

[0056] In Comparative Example 1, the reactant dropped in the first reaction step was 340 g of palmitoyl chloride, and the second reaction step was not carried out. Other than that, it was produced in the same manner as in Example 1. In Comparative Example 1, 291 g of amylose palmitate derived from corn extract was obtained. The saccharide derivative synthesized in Comparative Example 1 had 100% aliphatic hydrocarbon chain.

[0057] In Comparative Example 2, the reactant dropped in the first reaction step was 166 g of benzoyl chloride, and the second reaction step was not carried out. Other than that, it was produced in the same manner as in Example 1. In Comparative Example 2, 150 g of amylose benzoate derived from corn extract was obtained. The saccharide derivative synthesized in Comparative Example 2 had 100% aromatic hydrocarbon chain.

[0058] <Example 5, Comparative Examples 3 - 4: The saccharide is glucose> For the saccharide derivative of Example 5 and the saccharide derivatives of Comparative Examples 3 - 4, 30 g of plant-derived glucose was stirred and dissolved in 400 mL of pyridine (dissolution step).

[0059] In Example 5, after the glucose was completely dissolved in pyridine, the solution was ice-cooled using an ice bath, and 28 g of benzoyl chloride was added dropwise with stirring (the first reaction step). Subsequently, 210 g of palmitoyl chloride was added dropwise (the second reaction step). After the addition was completed, the reaction solution was removed from the ice bath and stirred for a total of 12 hours. Thereafter, the reaction solution was added to 1 L of water and stirred, and the water was removed by filtration. The precipitate was dissolved in 150 mL of ethyl acetate, stirred while flowing it little by little into 2 L of methanol, and finally the precipitated product was filtered and dried to obtain 193 g of plant-derived glucose palmitate benzoate (purification step). In the saccharide derivative synthesized in Example 5, the substitution ratio was 80% for the aliphatic hydrocarbon chain and 20% for the structure having an aromatic ring.

[0060] In Comparative Example 3, the reactant added dropwise in the first reaction step was 280 g of palmitoyl chloride, and the second reaction step was not performed. It was produced in the same manner as in Example 5 except for this, and in Comparative Example 3, 204 g of plant-derived glucose palmitate was obtained. The saccharide derivative synthesized in Comparative Example 3 has 100% aliphatic hydrocarbon chain.

[0061] In Comparative Example 4, the reactant added dropwise in the first reaction step was 140 g of benzoyl chloride, and the second reaction step was not performed. It was produced in the same manner as in Example 5 except for this, and in Comparative Example 4, 108 g of plant-derived glucose benzoate was obtained. The saccharide derivative synthesized in Comparative Example 4 has 100% aromatic hydrocarbon chain.

[0062] <Example 6, Comparative Examples 5-6: The saccharide is sucrose> For the saccharide derivative of Example 6 and the saccharide derivatives of Comparative Examples 5-6, 30 g of plant-derived sucrose was stirred and dissolved in 400 mL of pyridine (dissolution step).

[0063] In Example 6, after the sucrose was completely dissolved in pyridine, the solution was ice-cooled using an ice bath, and 35 g of benzoyl chloride was added dropwise with stirring (the first reaction step). Subsequently, 170 g of palmitoyl chloride was added dropwise (the second reaction step). After the addition was completed, the reaction solution was removed from the ice bath and stirred for a total of 12 hours. Thereafter, the reaction solution was added to 1 L of water, stirred, and the water was removed by filtration. The precipitate was dissolved in 150 mL of ethyl acetate, poured little by little into 2 L of methanol while stirring, and finally the precipitated product was filtered and dried to obtain 148 g of plant-derived sucrose palmitate benzoate (purification step). In the saccharide derivative synthesized in Example 6, the substitution ratio was 70% for the aliphatic hydrocarbon chain and 30% for the structure having an aromatic ring.

[0064] In Comparative Example 5, the reactant added dropwise in the first reaction step was 230 g of palmitoyl chloride, and the second reaction step was not carried out. Otherwise, it was produced in the same manner as in Example 6. In Comparative Example 5, 167 g of plant-derived sucrose palmitate was obtained. The saccharide derivative synthesized in Comparative Example 5 has 100% aliphatic hydrocarbon chain.

[0065] In Comparative Example 6, the reactant added dropwise in the first reaction step was 120 g of benzoyl chloride, and the second reaction step was not carried out. Otherwise, it was produced in the same manner as in Example 6. In Comparative Example 6, 90 g of plant-derived sucrose benzoate was obtained. The saccharide derivative synthesized in Comparative Example 6 has 100% aromatic hydrocarbon chain.

[0066] <Example 7, Comparative Examples 7-8: The saccharide is xylan> For the saccharide derivative of Example 7 and the saccharide derivatives of Comparative Examples 7-8, 60 g of xylan derived from corn extract (xylose component 95%, molecular weight Mw about 450) was stirred and dissolved in 600 mL of pyridine (dissolution step).

[0067] In Example 7, after the xylan was completely dissolved in pyridine, the solution was ice-cooled using an ice bath, and 38 g of benzoyl chloride was added dropwise with stirring (the first reaction step). Subsequently, 290 g of palmitoyl chloride was added dropwise (the second reaction step). After the addition was completed, the reaction solution was removed from the ice bath and stirred for a total of 12 hours. Then, the reaction solution was added to 2 L of water, stirred, and the water was removed by filtration. The precipitate was dissolved in 300 mL of ethyl acetate, stirred while being slowly poured into 3 L of methanol little by little, and finally, the precipitated product was filtered and dried to obtain 258 g of xylan palmitate benzoate derived from corn extract (purification step). In the saccharide derivative synthesized in Example 7, the substitution ratio was 80% for the aliphatic hydrocarbon chain and 20% for the structure having an aromatic ring.

[0068] In Comparative Example 7, the reactant added dropwise in the first reaction step was 370 g of palmitoyl chloride, and the second reaction step was not performed. Otherwise, it was produced in the same manner as in Example 7. In Comparative Example 7, 300 g of xylan palmitate derived from corn extract was obtained. The saccharide derivative synthesized in Comparative Example 7 has 100% aliphatic hydrocarbon chain.

[0069] In Comparative Example 8, the reactant added dropwise in the first reaction step was 190 g of benzoyl chloride, and the second reaction step was not performed. Otherwise, it was produced in the same manner as in Example 7. In Comparative Example 8, 159 g of xylan benzoate derived from corn extract was obtained. The saccharide derivative synthesized in Comparative Example 8 has 100% aromatic hydrocarbon chain.

[0070] The melting points and T1000 of Examples 1 - 7, Comparative Examples 1 - 8, and the raw material sugars (Reference Examples 1 - 4) are summarized in Table 1. In the process of measuring T1000 for each example and comparative example, no denaturation or carbonization occurred as in the raw material sugars (Reference Examples 1 - 4). Regarding "ND" in the melting point and T1000, refer to the measurement and evaluation methods.

Table 1

[0071] <When the saccharide is amylose> Compared with unsubstituted saccharides such as the raw material sugar (Reference Example 1), in Comparative Examples 1 and 2, by being substituted only with an aliphatic group or an aromatic group, the melting point and the value of T1000 were measured, and fluidity was exhibited.

[0072] When both aliphatic and aromatic substituents were introduced as in Example 1, the melting point decreased by 53 °C and 64 °C respectively compared with Comparative Examples 1 and 2, and T1000 decreased by 41 °C and 71 °C. Also, in Example 2 with a high aliphatic substitution ratio, the melting point and T1000 decreased by approximately 30 °C to 40 °C compared with Comparative Example 1 substituted only with an aliphatic group. Examples 3 and 4 with a high aromatic substitution ratio also showed a decrease of 6 °C or more compared with Comparative Example 2 substituted only with an aromatic group. Looking at Examples 1 to 4, it can be seen that the aliphatic substitution ratios are in the order of 50, 90, 20, 10%, and the effect of lowering the temperature is high. It is understood that the higher the effect, the closer the both substitution ratios are. Also, when one of the substitution ratios is high, it is understood that the higher the aliphatic substitution ratio, the slightly higher the effect.

[0073] <When the saccharide is glucose> Compared with unsubstituted saccharides such as the raw material sugar (Reference Example 2), in Comparative Example 3 substituted only with an aliphatic group, the melting point decreased by 70 °C, and the value of T1000 was measured and fluidity was exhibited. Also, in Comparative Example 4 substituted only with an aromatic group, the melting point increased by 4 °C, and the value of T1000 was measured and fluidity was exhibited. When both aliphatic and aromatic substituents were introduced as in Example 5, the melting point decreased by 22 °C and 96 °C respectively compared with Comparative Examples 3 and 4, and T1000 decreased by 13 °C and 116 °C.

[0074] <When the saccharide is sucrose> Compared with unsubstituted saccharides such as the raw material sugar (Reference Example 3), in Comparative Example 5 substituted only with an aliphatic group, the melting point decreased by 112 °C, and the value of T1000 was measured and fluidity was exhibited. Also, in Comparative Example 6 substituted only with an aromatic group, the melting point decreased by 31 °C, and the value of T1000 was measured and fluidity was exhibited. When both aliphatic and aromatic substituents were introduced as in Example 6, the melting point decreased by 31 °C and 122 °C respectively compared to Comparative Examples 5 and 6, and T1000 decreased by 44 °C and 154 °C.

[0075] <The saccharide is xylan> Compared with unsubstituted saccharides such as the raw material sugar (Reference Example 4), Comparative Example 7 substituted only with an aliphatic group had a melting point decrease of 48 °C, and the value of T1000 was measured and fluidity was exhibited. Also, Comparative Example 8 substituted only with an aromatic group had a melting point decrease of 16 °C, and the value of T1000 was measured and fluidity was exhibited. When both aliphatic and aromatic substituents were introduced as in Example 7, the melting point decreased by 47 °C and 79 °C respectively compared to Comparative Examples 7 and 8, and T1000 decreased by 48 °C and 90 °C.

[0076] <Example 8: Molding processability> In Example 8, the melt flow rate (MFR) of a resin mixture of 5 wt% of the saccharide derivative of Example 6 (sucrose substituted with both aliphatic 70% and aromatic 30% substituents) and 95 wt% of a styrene resin (PSJ - polystyrene GPPS (grade name: HF77) manufactured by PS Japan) was measured.

[0077] Compared with the MFR of 2.1 g / 10 min for 100 wt% of the styrene resin, the MFR of the resin mixture of Example 8 increased up to 4.1 g / 10 min. Since T1000 is at a low temperature in Examples 1 - 5 and Example 7 as in Example 6, it can be estimated that similar results can be obtained even if the saccharide of the saccharide derivative is amylose, glucose or xylan. Also, it can be estimated that the plastic resin combined with the saccharide derivative is applicable to general - purpose plastics and biodegradable plastic materials.

[0078] Using the resin mixture of Example 8, a flat plate of 40 mm × 40 mm × 1 mm and a dumbbell of 5A size were molded. It was confirmed that the moldability was improved as compared with the styrene resin (100% by weight). In addition, it was also possible to mold the flat plate and the dumbbell only with the saccharide derivative (100% by weight) of Example 2 (amylose substituted with both aliphatic 90% and aromatic 10% substituents).

Claims

1. A saccharide derivative in which at least a part of the hydrogen of the hydroxyl group of the saccharide is substituted with a substituent, wherein the saccharide is at least one saccharide selected from monosaccharides, disaccharides, amylose having a molecular weight (Mw) of 20,000 or less, and xylan having a molecular weight (Mw) of 20,000 or less, and the substituent is a saccharide derivative containing the structures of both the following (Formula 1) and the following (Formula 2). 【Chemical 1】 (Formula 1) In Formula 1, R1 is an aliphatic hydrocarbon chain, which may be linear, branched, saturated or unsaturated, and may not contain the C=O bond in ( ). 【Chemical Formula 2】 (Formula 2) In Formula 2, R2 is a structure having an aromatic ring, and may not contain the C=O bond in ( ).

2. The saccharide derivative according to Claim 1, wherein the hydrogen of the hydroxyl group of the saccharide is completely substituted with the substituents of (Formula 1) and (Formula 2), and the aliphatic substitution ratio, which is the ratio of the substituent of (Formula 1) to all the substituents, is 10% or more and 90% or less.

3. The saccharide derivative according to Claim 1 or Claim 2, wherein in (Formula 1), R1 is palmitoyl or stearyl.

4. The saccharide derivative according to Claim 1 or Claim 2, wherein in (Formula 2), R2 is phenyl, benzyl or tolyl.

5. The saccharide derivative according to any one of Claims 1 to 4, wherein the saccharide serving as a raw material for the saccharide derivative is glucose or sucrose.

6. The saccharide derivative according to any one of Claims 1 to 4, wherein the saccharide serving as a raw material for the saccharide derivative is amylose having a molecular weight (Mw) of 8,000 to 12,000.

7. The saccharide derivative according to any one of Claims 1 to 4, wherein the saccharide serving as a raw material for the saccharide derivative is xylan having a molecular weight (Mw) of 300 to 1,500.

8. A molded article containing the saccharide derivative according to any one of Claims 1 to 7.

9. A method for producing a saccharide derivative, in which at least one saccharide selected from monosaccharides, disaccharides, amylose having a molecular weight (Mw) of 20,000 or less, and xylan having a molecular weight (Mw) of 20,000 or less is reacted with substituents of both the following (Formula 1) and the following (Formula 2), 【Chemical Formula 3】 (Formula 1) 【Chemical Formula 4】 (Formula 2) (a)A dissolution step of dissolving the saccharide in its good solvent; (b)A first reaction step of esterifying or etherifying some of the hydroxyl groups of the saccharide; (c)A second reaction step of esterifying or etherifying the remaining hydroxyl groups of the saccharide after the first reaction; (d)A purification step of purifying the reaction product from the reaction solution after the second reaction. A method for producing a saccharide derivative having

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