JP2009286743A - Diol compound, method for producing the same and resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new plastic material by using 5-hydroxymethylfurfural obtained as a byproduct from a biomass resource and glycerol as raw materials. <P>SOLUTION: This diol compound obtained from 5-hydroxymethylfurfural with pentaerythritol is a diol compound having two polymerizable functional groups in one molecule, and a resin produced by using the above diol compound as a raw material is the plastic material obtained from the biomass resource. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a diol compound and a resin.

  In recent years, with increasing interest in environmental and energy resource issues, plastic materials are also made from raw materials obtained from biomass resources such as plants from plastic materials derived from fossil fuel resources such as petroleum, which are currently widely used as general-purpose products. Conversion to plastic materials that had been used is being attempted.

The saccharification reaction that hydrolyzes cellulose with an acid to produce sugar has been studied for some time, and in recent years, many attempts have been made to further ferment the obtained sugar to ethanol and use it as energy. It is being considered. In these saccharification reactions, it is known that furfurals are produced as by-products (Non-patent Documents 1 and 2), and an example thereof is 5-hydroxymethylfurfural. 5-hydroxymethylfurfural is a compound having a hydroxyl group and an aldehyde group in one molecule, and 2,5-furandicarboxylic acid obtained by oxidizing 5-hydroxymethylfurfural can be used as a substitute for terephthalic acid, As in Non-Patent Document 3, reduction / hydrocracking of 5-hydroxymethylfurfural into 2,5-dimethylfuran and use as biofuel (Non-Patent Document 3) has been studied. . Furthermore, a new synthesis method for obtaining 5-hydroxymethylfurfural with a high yield of 70% using chromium chloride as a catalyst in an ionic liquid has been reported (Non-Patent Document 4). Interest was growing.
Yuri Roman-Leshko et al., Science, 2006, 312, p. 1933-1937. "New Process Makes Diesel Fuel, Industrial Chemicals from diesel fuel, industrial chemicals from simple sugar", University of Wiscon-Madison, June 29, 2006. Yuri Roman-Leshkov et al., Nature, 2007, 447, p. 982-985. Haibo Zhao et al., Science, 2007, 316, p. 1597-1600.

  The present invention provides a novel plastic material and a raw material compound thereof using 5-hydroxymethylfurfural obtained as a by-product from biomass resources as a raw material.

  The inventors of the present invention have made extensive studies to solve the above problems, and the diol compound obtained from 5-hydroxymethylfurfural and pentaerythritol is a compound having two polymerizable functional groups in one molecule. It was found that the resin produced from the compound as a raw material is a plastic material obtained from biomass resources.

That is, the present invention
[1] A diol compound represented by the following formula (1).

[2] A method for producing a diol compound according to [1], wherein the diol compound is produced by an acetalization reaction using 5-hydroxymethylfurfural and pentaerythritol as raw materials.
[3] A resin containing a diol residue represented by the following formula (2).

Consists of.

  Since the present invention can provide a new plastic material manufactured from biomass resources, it can greatly contribute to the construction of a sustainable social structure by the effect of reducing the environmental load.

  Hereinafter, the diol compound of the present invention, its production method, and the resin will be specifically described.

  The diol compound of the present invention is a compound represented by the above formula (1). An example of a method for obtaining the diol compound of the present invention includes a method of acetalizing 5-hydroxymethylfurfural and pentaerythritol, and the reaction can be advanced only by using an acid catalyst. From the viewpoint of reaction yield and the like, it is preferable to obtain the diol compound by the acetalization reaction, but in the present invention, the diol compound can be obtained by any method other than the acetalization reaction.

  The acetalization reaction is a reaction in which an alcohol is condensed with a ketone or an aldehyde under an acid catalyst. The acid catalyst used in the acetalization reaction of the present invention includes sulfuric acid, paratoluenesulfonic acid, and the like, and the eliminated protons coordinate with the oxygen atom of the aldehyde group to increase the electrophilicity of the carbon atom of the aldehyde group, There is no particular limitation as long as it makes it easy to add the oxygen atom of the group to the carbon atom, and an acid catalyst used in a normal acetalization reaction can be used. Moreover, the addition amount of the acid catalyst should just contain only the quantity which can advance this acetalization reaction, Usually, it is about 0.1-5 mol% with respect to the compound which has an aldehyde group used as a raw material. is there. If the amount of the catalyst is too large, it is not preferable because it is difficult to isolate the target compound from the produced crude product, or the raw material or the target compound may be modified such as oxidation.

  The above-mentioned 5-hydroxymethylfurfural is not particularly limited as long as it can obtain the diol compound of the present invention, even if it is obtained by any method such as those usually obtained as a reagent, but for the purposes of the present invention. From the viewpoint of providing a new plastic material produced from a certain biomass resource, it is preferable to use biomass-derived 5-hydroxymethylfurfural. As a method for obtaining 5-hydroxymethylfurfural from biomass, any known method may be used, but a method obtained by saccharification reaction of cellulose is preferable from the viewpoint of abundant raw materials and reaction efficiency. As a method for obtaining the 5-hydroxymethylfurfural by saccharification reaction of cellulose, for example, the methods described in Non-Patent Documents 1 and 2 described in the background art can be used.

  The pentaerythritol described above is not particularly limited as long as it can obtain the diol compound of the present invention, even if it is obtained by any method such as those usually obtained as a reagent.

  In the acetalization reaction described above, when 5-hydroxymethylfurfural and pentaerythritol are reacted with each other, either of them may be reacted in a solvent, or both may be mixed and reacted without using a solvent. Can be used. When no solvent is used, there is a merit that the step of adding or distilling off the solvent can be omitted, but the reaction operation may be difficult. Conversely, when the reaction is carried out using an appropriate solvent, there is a merit that the reaction operation becomes easy, but there is a problem that a step of adding or evaporating the solvent is required. Therefore, it suffices to determine which method to select together with other reaction conditions such as the manufacturing environment, reaction temperature, and catalyst concentration.

  In addition, regarding the reaction temperature in the acetalization reaction described above, when the reaction is performed at a relatively low temperature such as room temperature, there is a merit that the progress of the side reaction can be suppressed, but the progress rate of the target reaction is low. In contrast, when the reaction is performed at a relatively high temperature, such as refluxing the solvent, the progress rate of the target reaction can be increased, but the side reaction is likely to proceed, making it difficult to isolate the target product. There is a problem. Therefore, an optimal reaction temperature may be determined together with other reaction conditions such as the production environment and catalyst concentration.

  In addition, since the acetalization reaction described above is a reversible reaction, increasing the degree of progress of the acetalization reaction can be achieved by setting reaction conditions that move the equilibrium in the reaction to the product side. . For example, since the acetalization reaction is a dehydration condensation reaction, it is considered that the reaction yield can be increased by removing generated water from the reaction system. Examples of a method for removing water from the reaction system include a method in which a reaction is performed with a dehydrating agent such as molecular sieves or calcium chloride. Further, the equilibrium can be moved to the production side by charging a large amount of either 5-hydroxymethylfurfural or pentaerythritol as a reaction raw material. In this case, the reaction conditions may be determined by comprehensively judging the amount of raw material supplied and the yield of the target product.

  As a method for isolating the diol compound of the present invention from the reaction crude obtained by the acetalization reaction described above, various known methods such as distillation, recrystallization, and chromatography can be used. However, because the physical and chemical properties of the raw materials and products are similar, it is difficult to isolate the target product by distillation or recrystallization methods. It is preferable to separate using

  The above-mentioned chromatographic method uses the difference in the size, adsorption power, hydrophobicity, etc. of each substance to be separated, and separates the substances into components in the process of moving the moving layer through or inside the solid layer. In the present invention, any known method can be used as long as it is a method capable of isolating a target compound from a reaction crude product, such as column chromatography or adsorption chromatography. Is preferable from the viewpoint of easy operation. Moreover, as a moving bed used in this case, a general mixed solvent system such as a hexane / ethyl acetate system or a chloroform / methanol system can be used.

  The diol compound of the present invention can be converted to other compounds by further substitution with a functional group. As for the introduction of the substituent, 5-hydroxymethylfurfural or pentaerythritol may be substituted in advance, and then the acetalization reaction may be performed to obtain the substituted target product, or the substitution may be performed after obtaining the diol compound of the present invention. A group may be introduced. For example, an alkyl group can be introduced onto the furan ring of the diol compound. As the introduction method, as shown by the following general formula (3), 2-hydroxymethylfurfural is converted to 2 equivalents of methanol under an acid catalyst. And acetalization reaction to form a dimethyl acetal form, then reacting 2 equivalents of butyl lithium in tetrahydrofuran at minus 78 ° C., one with lithium methoxide and the other with lithium substitution on the adjacent furan ring, Convert lithium on the furan ring into an alkyl group by reacting with 1 equivalent of alkyl halide, and finally react with water with an acid catalyst to convert lithium methoxide back to hydroxyl group, and simultaneously convert dimethylacetal group back to aldehyde group. 4-alkyl-5-hydroxymethylfurf having an alkyl group introduced on the furan ring Newsletter Lumpur, then subjected to acetalization reaction of pentaerythritol, a method can be cited to give a compound obtained by introducing an alkyl group on the furan ring of the diol compound of the present invention.

  The resin of the present invention is a resin containing a diol residue represented by the above formula (2). As a method for obtaining the resin, the diol compound of the present invention represented by the formula (1) is synthesized, and further polymerized with a compound having two or more polymerizable functional groups in the molecule such as dicarboxylic acid or diisocyanate. Examples thereof include a method for obtaining a polymer compound containing a diol residue represented by the formula (2). From the viewpoint of providing a new plastic material produced from a biomass resource, which is the object of the present invention, using a compound obtained from a biomass resource for a compound having two or more polymerizable functional groups in the molecule. preferable.

  Examples of the compound having two or more polymerizable functional groups in the molecule described above include dicarboxylic acid and diisocyanate. In these cases, resins produced in combination with the diol compound of the present invention are polyester resin and polyurethane resin, respectively. It becomes.

  Examples of dicarboxylic acids that can be used in the production of the resin of the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenic acid, 4,4′-dicarboxydiphenyl ether, bis (p- Carboxyphenyl) alkane, 4,4′-dicarboxyphenylsulfone, oxalic acid, malonic acid, succinic acid, aliphatic dicarboxylic acid such as adipic acid and the like can be mentioned, and these can be used alone or in combination.

  Examples of diisocyanates that can be used in the production of the resin of the present invention include tolylene diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, water. Added tolylene diisocyanate, and these may be used alone or in combination.

  In order to obtain the resin of the present invention, a polycondensation of a diol compound and a dicarboxylic acid includes a thermal polymerization method in which a raw material is heated at a high temperature to perform polymerization, and dicarboxylic acid as a highly reactive acid chloride such as chloroform or dichloromethane. In the interfacial polycondensation method in which the diol compound is dissolved in an aqueous alkali solution and condensed in an interface layer with a chloroform solution, N, N-dimethylformamide or N-, together with the diol compound as an acid chloride, Examples thereof include a low temperature solution condensation method in which condensation is performed in a solution of methyl-2-pyrrolidinone or the like, and any known method may be used to produce the resin of the present invention.

  In addition, in order to obtain the resin of the present invention, the diol compound and the diisocyanate are reacted with each other in addition to the usual method of mixing and reacting the diol compound and the diisocyanate, and also using a functional group such as a carboxyl group or an amino group. The foamed polyurethane can also be produced by adding a foaming agent and polymerizing it.

  In addition, when manufacturing the resin of this invention, it is preferable to use the diol compound of this invention, but it is also possible to use together with other polyols as needed as a copolymer resin. Examples of polyols that can be used in this case include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. These may be used alone or in combination of two or more.

  A filler can be added to the resin of the present invention as long as the effects of the present invention are not impaired. As the filler, known ones generally used as fillers for resins are used, and the strength, rigidity, heat resistance, dimensional stability and the like of the resin of the present invention can be improved. For example, glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone koji fiber, metal fiber, wollastonite, zeolite, sericite, kaolin, Mica, talc, clay, pyrophyllite, bentonite, montmorillonite, asbestos, aluminosilicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, Examples thereof include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide, and silica. These may be hollow, and two or more of these fillers may be used. These fillers may be used after being treated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound. As for montmorillonite, organic montmorillonite obtained by cation exchange of interlayer ions with an organic ammonium salt may be used. In order to reinforce the resin, glass fiber and carbon fiber are particularly preferable among the fillers.

  Further, the resin of the present invention includes various additives such as an antioxidant, a heat stabilizer, a weathering agent, a release agent and a lubricant, a pigment, a dye, a plasticizer, and an antistatic agent as long as the effects of the present invention are not impaired. The flame retardant can be added at any time.

  The resin of the present invention can be molded into a desired shape by any molding method such as injection molding, extrusion molding, blow molding, vacuum molding, melt spinning, film molding, and the like, fibers, films, containers, electric and electronic parts, automobiles It can be used as various products such as parts.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited by these examples. In the examples, the following various solvents and chromatographic carriers were used unless otherwise specified.
5-hydroxymethylfurfural: Tokyo Chemical Industry Co., Ltd., first grade pentaerythritol: Tokyo Chemical Industry Co., Ltd. Toluene: Nacalai Tesque Co., Ltd., special grade sulfuric acid: Wako Pure Chemical Industries, Ltd., special grade n-hexane: Nacalai Tesque Co., Ltd., special grade acetic acid Ethyl: Nacalai Tesque Co., Ltd., special grade N-methyl-2-pyrrolidinone: Wako Pure Chemical Industries, Ltd., Special grade terephthalic acid chloride: Tokyo Chemical Industry Co., Ltd., Primary dichloromethane: Nacalai Tesque Co., Ltd. Co., Ltd., first grade silica gel: manufactured by Merck, silica gel 60, particle size 0.063-0.200 mm
Example 1
In a 2 L reaction vessel equipped with a stirrer, reflux condenser and Dean-Stark trap, 50.0 g (0.396 mol) of 5-hydroxymethylfurfural, 27.0 g (0.198 mol) of pentaerythritol, 500 ml of toluene and sulfuric acid 0.117 g (1.19 mmol) was added, and the mixture was heated and stirred in nitrogen for 4 hours while toluene was refluxed in an oil bath. After completion of the reaction, the solvent was distilled off, and the resulting crude reaction product was subjected to silica gel column chromatography (silica gel: 2.3 kg, moving layer: n-hexane / ethyl acetate = 1/1 (v / v), n-hexane. / Ethyl acetate = 1/4 (v / v), ethyl acetate), and the solvent was distilled off to obtain 9.39 g (yield 13.5%) of the diol compound of the present invention.

(Example 2)
A 200 ml reaction vessel equipped with a stirrer and a dropping funnel was charged with 8.81 g (25.0 mmol) of the diol compound obtained in Example 1 and 50 ml of N-methyl-2-pyrrolidinone, and completely dissolved. In a nitrogen atmosphere in an ice bath, a solution prepared by dissolving 5.07 g (25.0 mmol) of terephthalic acid chloride in 20 ml of dichloromethane was added dropwise over 1 hour with stirring, and stirring was continued for 2 hours. Next, the obtained reaction solution was filtered, and then poured into 1 L of distilled water to reprecipitate, filtered and dried to obtain 8.66 g of resin powder (yield 71.8%).

(Example 3)
Into a 50 ml reaction vessel equipped with a stirrer was charged 8.81 g (25.0 mmol) of the diol compound obtained in Example 1 and 4.21 g (25.0 mmol) of hexamethylene diisocyanate, and a nitrogen atmosphere at room temperature for 3 hours. Stirring was performed to obtain 12.3 g (yield 94.3%) of a solid resin.

  The diol compound and resin obtained from the present invention can provide a new plastic material produced from biomass resources. The plastic material can be suitably used for fibers, films, containers, and various products such as electric and electronic parts and automobile parts.

Claims (3)

A diol compound represented by the following formula (1).

  The method for producing a diol compound according to claim 1, wherein the diol compound is produced by an acetalization reaction using 5-hydroxymethylfurfural and pentaerythritol as raw materials. A resin containing a diol residue represented by the following formula (2).