JP2009286728A - 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 as a byproduct and glycerol as raw materials. <P>SOLUTION: This compound synthesized by performing the acetalization reaction and hydrogenation reaction of the 5-hydroxymethylfurfural with glycerol 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 generated 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 to 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.

On the other hand, since the end of the 19th century, research on removing glycerin from biological oils such as peanut oil by transesterification to obtain fatty acid methyl esters (biodiesel) has been conducted. Again, the technological development has become active. However, while biodiesel is increasingly in the limelight, glycerin, a by-product, is said to be difficult to sell and dispose of because it is currently oversupplied.
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 and glycerin obtained as by-products from biomass resources as raw materials.

  The inventors of the present invention have made extensive studies to solve the above problems, and a compound synthesized by subjecting 5-hydroxymethylfurfural and glycerin to an acetalization reaction and a hydrogenation reaction has a polymerizable functional group in one molecule. It has been found that a resin that is a diol compound having two and is produced from the diol 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 subjecting 5-hydroxymethylfurfural and glycerin as raw materials to an acetalization reaction and a hydrogenation reaction. .
[3] The method for producing a diol compound according to [2], wherein the acetalization reaction is allowed to react in the absence of a solvent.
[4] 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). As an example of the method for obtaining the diol compound of the present invention, there is a method in which 5-hydroxymethylfurfural and glycerol are subjected to an acetalization reaction and a hydrogenation reaction.

  Here, the order of the acetalization reaction and the hydrogenation reaction is not particularly limited, and 5-hydroxymethylfurfural and glycerin are first acetalized to obtain 5-hydroxymethylfurfurylideneglycerol, and further hydrogenated. The target diol compound may be obtained, or 5-hydroxymethylfurfural may be first hydrogenated and then acetalized with glycerin to obtain the target diol compound.

  Hereinafter, a case where the acetalization reaction is performed followed by the hydrogenation reaction will be described. In the present invention, in order to obtain the diol compound, there is no particular problem in obtaining the diol compound by any method other than the acetalization reaction and the hydrogenation reaction. This is a preferable method from the viewpoint of simplicity of reaction, reaction yield, and the like, such as allowing the reaction to proceed under normal temperature and pressure conditions simply by using a catalyst.

  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 above-mentioned glycerin 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 it is a biomass resource that is the object of the present invention. From the viewpoint of providing a new plastic material to be manufactured more, it is preferable to use biomass-derived glycerin. As a method for obtaining the glycerin from biomass, any known method may be used. However, a method obtained by, for example, transesterification from a biological oil or fat is preferable from the viewpoint of abundant raw materials and reaction efficiency. As the bio-derived fats and oils, various fats and oils such as vegetable oils such as peanut oil, rapeseed oil, palm oil, olive oil, sunflower oil, soybean oil and rice oil, and tallow such as fish oil and beef tallow can be used. In addition, as a method for obtaining glycerin from the biological oil or fat, for example, a method in which methanol and a catalyst are added to the biological oil or fat to cause a transesterification reaction, and an acid is added to obtain glycerin together with a fatty acid methyl ester can be used.

  In the acetalization reaction described above, for example, when 5-hydroxymethylfurfural and glycerin are reacted, even if both are reacted in a solvent, both are mixed and reacted without solvent, that is, without using a solvent. However, it does not matter which method is used, but using the method in which the reaction is carried out in the absence of a solvent can eliminate the trouble of adding and evaporating the solvent, and further increase the reaction yield. Therefore, it is preferable.

  Further, the reaction temperature in the acetalization reaction described above is not particularly limited, but it is preferable to carry out the reaction at 50 ° C. or lower because it has advantages such as that the labor for raising the temperature can be omitted and the reaction yield is increased. More preferably, the reaction is carried out at room temperature. When the reaction is performed at 50 ° C. or higher, various side reactions such as hydroxyl group in 5-hydroxymethylfurfural are oxidized and denatured to carboxylic acid, so that isolation becomes difficult and coloring occurs. Or a reduction in the reaction yield is likely to occur. The lower limit of the reaction temperature is not particularly specified, but there is no particular problem if the reaction is carried out at 0 ° C. or higher from the viewpoint of omitting the cooling effort.

  The reaction time of the acetalization reaction described above is not particularly limited as long as the yield of the target 5-hydroxymethylfurfurylideneglycerol is sufficiently high, but other reactions such as reaction temperature and catalyst concentration are acceptable. The optimal time should be determined along with the conditions. For example, when the reaction temperature is 20 ° C. and the catalyst concentration is 3 mol%, the reaction time is suitably in the range of 30 minutes to 2 hours. If the reaction time is too short, the acetalization reaction does not proceed sufficiently, and there is a concern that the target product cannot be sufficiently obtained because the reaction yield is low. Conversely, if the reaction time is too long, the acetalization reaction There is a problem that side reactions other than that proceed, which is not preferable.

  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, for example, the equilibrium can be moved to the production side by charging a large amount of either 5-hydroxymethylfurfural or glycerin 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.

  Regarding the method for isolating the intermediate product for obtaining the diol compound of the present invention from the reaction crude product obtained by the acetalization reaction described above, various known methods such as distillation, recrystallization, chromatography, etc. However, the reaction crude product obtained by the acetalization reaction can be separated and isolated by a direct chromatographic method without undergoing other operations such as dissolution in a solvent. From the viewpoint of obtaining the target compound at a high rate. For example, 4-hydroxymethylfurfurylideneglycerol produced when 5-hydroxymethylfurfural and glycerin are acetalized can be considered to have four structural isomers represented by the following formulas (3) to (6). As envisaged, the four structural isomers have similar physical and chemical properties, so that the following formula, which is an intermediate product for obtaining the diol compound of the present invention in methods such as distillation and recrystallization, is used. It becomes very difficult to isolate (5) and (6). Usually, after the acetalization reaction is completed, an extraction operation is performed using a suitable solvent in order to separate the target product from the raw material glycerin, etc., but the 5-hydroxymethylfurfurylideneglycerol is separated from glycerin. Since the solubility in an incompatible low-polarity solvent is low, the yield of the target compound is reduced if the extraction is performed from the reaction crude product followed by separation by chromatography. For these reasons, the reaction crude product is separated by a direct chromatographic method without undergoing other operations, and the following formulas (5) and (6), which are intermediate products for obtaining the diol compound of the present invention, are simply expressed. Separation is a preferred method.

  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.

  For the hydrogenation reaction described above, the furan ring on 5-hydroxymethylfurfural or 5-hydroxymethylfurfurylideneglycerol may be reduced by tetrahydrolysis by any known method. For example, Wei-Lin Wei et al., Reactive & Functional Polymers (2004), 59, 33-39. The hydrogenation reaction can be carried out using the method described in 1), specifically, a furan compound and hydrogen gas are reacted at room temperature and normal pressure using a silica-alginic acid-amino acid-platinum complex prepared in advance as a catalyst. Thus, the hydrogenated target compound can be obtained.

  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, 5-hydroxymethylfurfurylideneglycerol represented by the above formulas (5) and (6) is synthesized and subjected to hydrogenation reaction, and then a polymerizable functional group in a molecule such as dicarboxylic acid or diisocyanate. Examples thereof include a method of obtaining a polymer compound containing a diol residue represented by the above formula (2) by polymerizing with a compound having two or more groups. 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 Examples, unless otherwise specified, the following various solvents and silica gel were used, and for identification of compounds, a nuclear magnetic resonance apparatus “superconducting FT-NMR EX-270 (270 MHz)” manufactured by JEOL Ltd. was used. Proton nuclear magnetic resonance ( ¹ H-NMR) spectrum was measured at 23 ° C. In this case, tetramethylsilane was used as the internal standard substance.
Sodium alginate: Wako Pure Chemical Industries, Ltd., first grade L-glutamic acid: Wako Pure Chemical Industries, special grade 1M hydrochloric acid: Wako Pure Chemical Industries, Ltd., hexachloroplatinum (IV) hexahydrate for volumetric analysis: Wako Pure Chemical Industries Co., Ltd., special grade ethanol: Nacalai Tesque Co., Ltd., special grade 5-hydroxymethylfurfural: Tokyo Chemical Industry Co., Ltd., first grade glycerin: Wako Pure Chemical Industries, Ltd., special grade sulfuric acid: Wako Pure Chemical Industries, Ltd. Tesque Co., Ltd., special grade ethyl acetate: Nacalai Tesque Co., Ltd. 99.9% (containing 0.05 v / v% TMS)
N-methyl-2-pyrrolidinone: Wako Pure Chemical Industries, Ltd., special grade terephthalic acid chloride: Tokyo Chemical Industry Co., Ltd., special grade dichloromethane: Nacalai Tesque Ltd., special grade hexamethylene diisocyanate: Tokyo Chemical Industry Co., Ltd., special grade silica gel: Merck Ltd. Manufactured, silica gel 60, particle size 0.063-0.200mm
(Reference Example 1)
20.0 g of sodium alginate was dissolved in 200 ml of distilled water, and 10.0 g of L-glutamic acid was dissolved in 100 ml of distilled water in a separate container. After mixing both, 30.0 g of silica gel was added, followed by 60 ml of 1M hydrochloric acid to form a precipitate. The precipitate was heated and pulverized, washed with distilled water until the pH reached 7, and then dried to obtain 58.0 g of a silica-alginate-glutamate ligand in the form of a white powder.

(Reference Example 2)
In a reaction vessel equipped with a stirrer and a reflux condenser, 10.0 g of the silica-alginate-glutamate ligand obtained in Reference Example 1, 1.04 g of hexachloroplatinum (IV) hexahydrate, and 100 ml of ethanol were added. The mixture was heated to reflux for 24 hours with stirring in a nitrogen atmosphere. After completion of the reaction, the reaction product was separated by filtration and dried to obtain 10.0 g of a gray powdery silica-alginate-glutamic acid-platinum complex.

Example 1
In a 500 ml reaction vessel equipped with a stirrer, 50.0 g (0.396 mol) of 5-hydroxymethylfurfural, 73.0 g (0.792 mol) of glycerin and 1.17 g (11.9 mmol) of sulfuric acid were added, and nitrogen was added. Stirring was performed at room temperature for 2 hours under an atmosphere. About the obtained reaction crude product, silica gel column chromatography (silica gel: 3.7 kg, moving layer: n-hexane / ethyl acetate = 1/1 (v / v), n-hexane / ethyl acetate = 1/4 (v / V) and ethyl acetate), followed by concentration, followed by concentration, elution fraction 1 (34.30 g) of a brown liquid, elution fraction 2 (5.65 g) of a white crystalline solid, An elution fraction 3 (9.50 g) and a light yellow liquid elution fraction 4 (5.60 g) were obtained. About each elution fraction, ¹ H-NMR spectrum was measured using DMSO-d6 as a measurement solvent.

  For elution fraction 1, from the high magnetic field side, 4.49 (2H, d), 5.23 (1 H, t), 6.60 (1 H, d), 7.48 (1 H, d), 9. Since a peak was detected in the vicinity of each ppm of 59 (1H, s), the compound was identified as 5-hydroxymethylfurfural.

  For Elution Fraction 2, from the high magnetic field side, 3.43 (2H, t), 3.68 (1H, m), 4.07 (2H, q), 4.34 (2H, d), 5. 21 (1H, d), 5.23 (1H, t), 5.44 (1H, s), 6.22 (1H, d), 6.33 (1H, d), peaks detected in the vicinity of ppm. Therefore, the compound was identified as the diol of the above formula (6).

  For elution fraction 3, from the high magnetic field side, 3.4-4.2 (10H, m), 4.35 (4H, d), 4.91 (2H, t), 5.22 (2H, t ), 5.78 (1H, s), 5.89 (1H, s), 6.23 (2H, d), 6.43 (1H, d), 6.46 (1H, d) The compound was identified as a mixture of the diol of formula (3) and the diol of formula (4).

  For elution fraction 4, from the high magnetic field side, 3.70 (1H, m), 3.85-4.00 (4H, q), 4.35 (2H, d), 4.96 (1H, d) ) 5.21 (1H, t), 5.55 (1H, s), 6.23 (1H, d), and 6.33 (1H, d). Was identified as a diol of formula (5) above.

  Subsequently, 5.00 g of the silica-alginate-glutamate-platinum complex obtained in Reference Example 2 was obtained in a 5 L reaction vessel equipped with a stirrer and connected with a hydrogen injection tube with a cylinder scale. 4.50 g (22.5 mmol) of the diol compound 2 and 4.50 g (22.5 mmol) of the diol compound of the elution fraction 4 and 500 ml of ethanol were added. Degassing and injection were repeated 100 times alternately. After completion of the reaction, the complex was removed by filtration to obtain 5.57 g (27.5 mmol) of the hydrogenated diol compound of the present invention in a yield of 61.2%.

(Example 2)
Into a 200 ml reaction vessel equipped with a stirrer and a dropping funnel is charged 5.05 g (25.0 mmol) of the hydrogenated diol compound obtained in Example 1 and 50 ml of N-methyl-2-pyrrolidinone and completely dissolved. Then, a solution prepared by dissolving 5.07 g (25.0 mmol) of terephthalic acid chloride prepared in 20 ml of dichloromethane in an ice bath in a nitrogen atmosphere was added dropwise over 1 hour with stirring, and then stirred for 2 hours. Continued. Next, the obtained reaction solution was filtered, and then poured into 1 L of distilled water to reprecipitate, filtered and dried to obtain 6.01 g of resin powder (yield 71.9%).

(Example 3)
In a 50 ml reaction vessel equipped with a stirrer, 5.05 g (25.0 mmol) of the hydrogenated diol compound obtained in Example 1 obtained in Example 1 and 4.21 g (25.0 mmol) of hexamethylene diisocyanate were added. Then, the mixture was stirred at room temperature for 3 hours in a nitrogen atmosphere to obtain 9.03 g of solid resin (yield 97.4%).

  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 (4)

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

  A method for producing a diol compound according to claim 1, wherein the diol compound is produced by acetalization reaction and hydrogenation reaction using 5-hydroxymethylfurfural and glycerin as raw materials.   The method for producing a diol compound according to claim 2, wherein the acetalization reaction is allowed to react in the absence of a solvent. A resin containing a diol residue represented by the following formula (2).