JP2020015729A - Phenol liquified resin - Google Patents

Abstract

To provide a biomass phenol liquified resin which does not react phenol that is not subjected to phenolysis reaction with formaldehyde when a biomass phenol liquified resin is produced, has high flowability in molding at low softening point even when being distilled away under reduced pressure, is excellent in moldability, and can also reduce a use amount of a curing agent when a cured product is obtained, and a compound which enhances thermal flowability of the resin and enhances curing reactivity.SOLUTION: An agent contains 4-{2-[2-(1-benzofuran-2-yl)ethyl]-1-benzofuran-3-yl}phenol, and the present compound.SELECTED DRAWING: None

Description

  The present invention belongs to the technical field related to phenolic resins. TECHNICAL FIELD The present invention relates to a phenol liquefied resin used for a casting mold, a molding material, an epoxy curing agent, various binders, and the like. The present invention particularly relates to a biomass phenol liquefied resin obtained from biomass.

Due to the development of petrochemicals from the middle of the twentieth century to the present, various kinds of durable and easy-to-use synthetic resins have been used in large quantities, and human life has become extremely convenient and comfortable. .
On the other hand, environmental problems have become serious such as the concentration of carbon dioxide in the air reaching 400 ppm, and resource problems such as a decrease and depletion of petroleum resources have been recognized. Under such a background, there is a strong worldwide demand for more use of biomass, mainly plants, which is a renewable resource as a material and energy source.

  Plastics using plant-derived raw materials are so-called carbon-neutral materials, and can reduce carbon dioxide emissions by that much as compared to plastics produced from fossil resources such as petroleum. This fact is in line with the shift from an oil-dependent society to a sustainable society.In recent years, new technologies have been used to produce fuels, materials and products using biomass instead of petroleum-derived substances. It is becoming more and more required. For example, tire manufacturers also develop and sell tires that are 100% plant-derived.

  In order to convert such biomass into resin and promote industrial use, research and development of technology for liquefying this biomass has been promoted. As one of them, development of using phenol resin after solvolysis (phenolysis) of a plant body (biomass) in the presence of an acidic catalyst and phenol and then liquefying the same is under way. For example, Patent Document 1 discloses a phenol resin (or urethane resin) obtained by reacting a mixture of phenols (or polyhydric alcohols) and wood flour more quickly and smoothly in the presence of a devised acidic catalyst. Is disclosed. It has been confirmed that the heat resistance and the deflection temperature under load of such a phenol resin are equal to or higher than those of conventional materials. With regard to flame retardancy and fire-extinguishing properties, it has passed the evaluation by FMVSS (Federal Motor Vehicle Safety Standards) No. 302 "Regulation of burning speed of automotive interior materials", which is a standard for flame retardancy of automotive interior materials. It has been reported that the phenol resin is excellent (see Non-Patent Document 1).

  Patent Document 2 discloses that phenol is characterized by reacting fructose, a fructose-containing saccharide with phenol in the presence of an acid catalyst, and containing a compound (compound 1) represented by the following formula (1). Resins are disclosed. Patent Document 2 describes that Compound 1 is a reaction product of a phenol and hydroxymethylfurfural. However, there is no indication as to the basis for determining the chemical structure of Compound 1.

  According to Patent Document 2, fructose for producing hydroxymethylfurfural as an intermediate product, a phenol resin which is a product obtained by heating and reacting phenol containing fructose with phenol at 100 to 150 ° C. under an acid catalyst, No. 1 is described as having a low softening point, high fluidity at the time of molding, excellent moldability, and capable of reducing the amount of a curing agent used in obtaining a cured product. However, carbohydrates that produce hydroxymethylfurfural as an intermediate component in a reaction at 120 to 150 ° C. in the presence of an acid catalyst are not limited to fructose and fructose-containing sugars, and widely exist in glucose, mannose, starch, hemicellulose, and the like. Therefore, it is difficult to say that the description in Patent Document 2 that Compound 1 is produced via hydroxymethylfurfural as a reaction product of a phenol and a phenol in the presence of an acid catalyst is correct.

  In addition, an academic paper similar in content to Patent Document 2 has been published (see Non-Patent Document 2). However, the chemical structure of Compound 1 described above is not shown at all. Simply, the enzyme-treated low-molecular-weight product of starch like isomerized saccharide is heated and reacted with phenol at 100 to 150 ° C under an acid catalyst to obtain a product, and the result of field desorption mass spectrometry (FD-MS) is shown. It has just been done. That is, it is only stated that a mass unit structure having a molecular weight of 200, 306, 412, and 518 common to the phenol formaldehyde resin and a component peak presumed to have a furan skeleton represented by a molecular weight of 372 are observed. There is no description that can be linked to Compound 1 above.

  Although Non-Patent Document 2 describes a product produced without formaldehyde, the product has a molecular weight of 200, 306, 412, 518 common to a general phenol formaldehyde resin obtained by reaction with formaldehyde. It is not clear why the mass unit structure exists.

  Heretofore, in many cases, after obtaining a liquefied product, it is reacted with phenol not participating in the phenolic reaction, and then reacted with formaldehyde to consume it. Patent Document 3 discloses an example of a case where wood powder is liquefied with phenol. By doing so, a biomass phenol resin which has high fluidity during molding at a low softening point, has excellent moldability, and can reduce the amount of a curing agent used in obtaining a cured product has been obtained. . Even in cases other than biomass liquefaction, in the case of a biomass phenol resin utilizing a biomass component such as lignin, there are many cases where formaldehyde is reacted in the conversion of the biomass phenol resin (see Non-Patent Documents 3 to 7). In these cases, it can be used in any form of novolak resin or resol resin.Even if it is a novolak resin, the fluidity of the resin, and thus the moldability, can be increased, and furthermore, a curing agent for obtaining a cured product Can be reduced. However, both of them fall into the category of formaldehyde resins as resins, and do not meet the current situation where non-formalin resins are required.

Japanese Patent Application Laid-Open No. 2007-092008 JP 2010-090297 A Japanese Patent No. 3152421

Tsuneoka, K. et al .: Functional Materials, Vol. 30, no. 11, 22-29 (2010). Akihiro Okubo et al .: Network Polymer, Vol. 32, no. 2, 97-100 (2011). C.G.da Silva et.al .: Industrial Crops and Products 42 (2013) 87-95. Amine Moubarik et.al .: Industrial Crops and Products 45 (2013) 296-302. Wei Zhang et.al .: International J. Adhesion & Adhesives 40 (2013) 11-18. Wei Zhang et.al .: Industrial Crops and Products 43 (2013) 326-333. Elaine C. et.al .: Composites: Part B 43 (2012) 2851-2860.

The objects of the present invention include, for example, the following.
(1) First, a more advanced technology development in which the unresolved points in the above-mentioned Patent Document 2 are solved or inaccurate points are corrected.
(2) On the other hand, as can be seen in the technique of Patent Document 1, liquefaction of biomass such as wood flour has effectively proceeded by improving the catalyst. However, the biomass phenol liquefied resin obtained by the technique of Patent Document 1 has a low softening point and low fluidity at the time of molding, and is not satisfactory in moldability in molding for curing to obtain a final product. There are problems, and we need to find a solution. It is known that this problem can be solved by reacting unreacted phenol, which did not participate in the phenolic reaction in the liquefaction process, with formaldehyde to form a resin. On the other hand, in consideration of the current situation where non-formaldehyde resins are required, a method of distilling off the unreacted phenol under reduced pressure without employing a reaction with formaldehyde was adopted, which caused adverse effects on processability. Solving the problem.

(3) It is also important to solve the problem that the curing reactivity is equal to or higher than that of the conventional phenolic resin and the generation of harmful decomposition gases such as formaldehyde and amine during curing is reduced. This is a problem of reducing the amount of a curing agent such as hexamethylenetetramine used for obtaining a cured product of a phenol resin. Furthermore, at present, the phenolic resin described in Patent Document 1 has a longer curing time under the same curing conditions than conventional products, and there is also a problem to solve it.

  Again, the above problems (2) and (3) are that the phenol which did not participate in the phenolic reaction does not react with formaldehyde, and even if it is distilled off under reduced pressure, it has a low softening point and high fluidity during molding. An object is to strongly demand the development of a biomass phenol liquefied resin which is excellent in moldability and can reduce the amount of a curing agent used in obtaining a cured product.

(4) As described in Patent Literature 1, liquefaction of biomass such as wood flour has effectively proceeded by improving the catalyst. However, an acid catalyzed reaction using a sulfuric acid-based homogeneous catalyst is still used, and there is a problem based thereon. In other words, sulfuric acid is an important catalyst in the chemical industry, but has a large burden on production and environmental protection, such as corrosion of metal equipment, separation of products, and waste acid treatment. Therefore, it is desired to use a solid Bronsted acid catalyst which is easy to handle and has a strong acidity and to establish a process using the same. The performance required for a sulfuric acid replacement catalyst includes high activity, heat resistance, chemical stability, and reaction selectivity. In general terms, the problems caused by the use of a sulfuric acid-based homogeneous catalyst are problems to be solved.

The term "biomass" used herein refers to living organisms, especially plants such as wood, bamboo, and coconut, polysaccharides such as cellulose, starch, and pullulan, small sugars such as dextrin, sucrose, and maltose, and monosaccharides such as fructose and glucose. , Lignin, hemicellulose and other plant components, and further include, for example, woody wastes in the wood and pulp industries, thinning materials, building demolition materials and agricultural wastes such as rice straw, pods, bagasse, etc. It contains lignocellulosics, furthermore, old and used rice, food industry waste, and the like. In this specification, unless otherwise specified, these substances are collectively referred to as biomass. In the present invention, in the presence of an acidic catalyst, it is preferable to apply to biomass that has a high melt viscosity only by liquefaction with phenols and obtains only those having poor curing reactivity. It is preferably applied to woods such as ground pulp, and biomass such as starch, dextrin, sucrose and glucose. The term “biomass phenol liquefied resin” refers to a phenol resin precondensate-like resin obtained by liquefying biomass such as wood with phenols in the presence of an acidic catalyst.

  As a result of this study, a novel biomass phenol liquefied resin containing a compound represented by the following formula (A) (hereinafter, referred to as “the compound of the present invention”) was found, and the above-mentioned problem (1) was solved. Further, they have found that the properties of the biomass phenol resin obtained therefrom satisfy the requirements of the above-mentioned problems (2) and (3), and have completed the present invention. The chemical name of the compound of the present invention is 4- {2- [2- (1-benzofuran-2-yl) ethyl] -1-benzofuran-3-yl} phenol.

  In connection with Task 4, the advantages of solid heterogeneous acid-base catalysts over liquid homogeneous acid-base catalysts are listed first: a) the catalyst does not corrode the reaction vessel or reactor; b) In the liquid phase reaction, it is easy to separate the catalyst from the product after the reaction, c) the catalyst can be used repeatedly, and d) disposal of the used liquid catalyst (such as sulfuric acid) requires high cost. However, in the case of a solid catalyst, the problem is much less, and e) the solid catalyst is often superior in activity and selectivity of the catalyst. All of these advantages lead to practical cost reductions and are also positive for environmental conservation. Then, the present inventors studied using a Bronsted acid solid catalyst. That is, the use of a solid acid catalyst such as activated carbon or amberlyst in which the liquefaction catalyst is sulfonated can effectively reduce the environmental load, and at the same time, solve the above-mentioned problems. These catalysts have been reported to be very stable in hot water or acidic aqueous solutions. Further, some biomass, especially monosaccharides mainly containing fructose, are suspended in phenols at a reaction temperature of 100 to 160 ° C., which is convenient for the reaction. The reaction solution can be continuously circulated through the column filled with the solid acid, and has additional advantages such as application to a continuous reaction using an apparatus.

Examples of the present invention include the following.
[1] A biomass phenol liquefied resin comprising the compound of the present invention.
[2] The biomass phenol liquefied resin according to the above [1], wherein the biomass is fructose or a saccharide containing fructose.
[3] The method for producing a biomass phenol liquefied resin according to the above [1] or [2], comprising a step of reacting a saccharide containing fructose with a phenol containing phenol in the presence of an acidic catalyst.
[4] The method for producing a biomass phenol liquefied resin according to the above [3], wherein the saccharide contains 5% by mass or more of fructose.

[5] The method for producing a biomass phenol liquefied resin according to the above [3] or [4], wherein the acidic catalyst is a solid acid catalyst.
[6] The method for producing a biomass phenol liquefied resin according to the above [5], wherein the solid acid catalyst is sulfonated activated carbon or crosslinked polystyrene.
[7] A method for producing a processed phenol resin product, which is produced using the biomass phenol liquefied resin according to [1] or [2].
[8] The compound of the present invention.

Since the biomass phenol liquefied resin of the present invention (hereinafter referred to as “the liquefied resin of the present invention”) has a low softening point and a high fluidity at the time of molding and is excellent in moldability, it is possible to use the liquefied resin of the present invention. A phenolic resin molded product can be easily manufactured. Further, since natural components are used as raw materials, the amount of carbon dioxide emission can be reduced accordingly. In the production of a phenolic resin molded product, the liquefied resin of the present invention has a high curing reactivity, so that the amount of a curing agent (such as hexamethylenetetramine) that causes formaldehyde generation can be reduced. Furthermore, the liquefied resin of the present invention has an advantage that it can be made into a "non-formaldehyde resin" because it is not necessary to carry out a reaction between phenols and formaldehyde which did not participate in the phenolic reaction in the preparation. Also, the related manufacturing method has been improved in terms of green chemistry.

It is a ¹ H- ¹ H COSY NMR spectrum of the compound of the present invention. ¹ is a ¹ H- ¹³ C HSQC NMR spectrum of a compound of the present invention. It is a GPC chromatogram of a liquefaction product. The horizontal axis represents the retention time (minutes), and the vertical axis represents the differential refractometer detection amount (corresponding to the solute concentration). It is a GPC chromatogram of a liquefaction product. The horizontal axis represents the retention time (minutes), and the vertical axis represents the differential refractometer detection amount (corresponding to the solute concentration).

Hereinafter, the present invention will be described in detail.
1 About the liquefied resin of the present invention The liquefied resin of the present invention is characterized by containing the compound of the present invention. The compound of the present invention is obtained by a reaction (phenolysis) between fructose and phenol in the presence of a homogeneous acidic catalyst such as sulfuric acid, or an acidic catalyst such as a sulfonated activated carbon or a solid acid catalyst such as cross-linked polystyrene (eg, Amberlyst (registered trademark)). Obtainable. Therefore, the compound of the present invention can be arbitrarily mixed with a general biomass phenol liquefied resin to prepare the liquefied resin of the present invention. The liquefied resin of the present invention can be prepared by containing the compound of the present invention.

1.1 In the case where the compound of the present invention is arbitrarily blended with the biomass phenol liquefied resin to obtain the liquefied resin of the present invention, the blending amount of the compound of the present invention in the biomass phenol liquefied resin, ie, the content of the compound of the present invention in the liquefied resin of the present invention When the total amount of the liquefied resin of the present invention is 100 parts by mass, the range of 0.5 to 80 parts by mass is appropriate, the range of 1.5 to 20 parts by mass is preferable, and the range of 2.0 to 15 parts by mass is preferred. Is more preferably within the range of parts. If the content of the compound of the present invention is less than 0.5 part by mass, sufficient fluidity may not be obtained, and if it is more than 80 parts by mass, the amount of the compound may be exceeded.

In the liquefied resin of the present invention, in addition to the compound of the present invention, for example, additives such as a pigment, a release agent, an antioxidant, a silane coupling agent, an ultraviolet absorber, and a lubricant, as long as the effects of the present invention are not impaired. Can be included.
The compound of the present invention can be blended with the biomass phenol liquefied resin by mixing the compound of the present invention itself or a composition containing the compound with the biomass phenol liquefied resin in a conventional manner. Such mixing can be performed manually or by using a suitable mixer.

1.1.1 Preparation of the Compound of the Present Invention The compound of the present invention can be obtained by reacting fructose with phenol in the presence of an acidic catalyst. The compounds of the present invention have not been obtained by the reaction of phenol with glucose other than fructose, maltose, dextrin and the like. Therefore, it can be said that the compound of the present invention can be specifically obtained in the reaction between a fructose-related compound and phenol among saccharides.

Here, "fructose" is most preferably fructose with high purity, but may be saccharides containing fructose (including oligosaccharides and polysaccharides containing fructose as constituent sugars). Such saccharides containing fructose include, for example, isomerized sugar, sucrose, and inulin (fructose polymer).
Further, each isomer may be used.
In the case of fructose-containing saccharides, fructose may be contained in an amount of 5 parts by mass or more, preferably 30 parts by mass or more, preferably 55 parts by mass or more, particularly preferably 95 parts by mass or more, with the whole solid content being 100 parts by mass. More preferred. If the fructose content is less than 5 parts by mass, the compound of the present invention may not be obtained in a sufficient amount.

  The mass ratio of fructose to phenol when obtaining the compound of the present invention is appropriately within the range of 1.5 to 20 times by mass of phenol when fructose is 1 part by mass, and 2 to 6 times by mass. Within the range is preferred. If the amount of phenol is less than 1.5 times the mass of fructose, a sufficient amount of the compound of the present invention may not be obtained.

Examples of the acidic catalyst include mineral acids (eg, hydrochloric acid, sulfuric acid, phosphoric acid, etc.) and organic acids (eg, methyl sulfate, paratoluenesulfonic acid, paraphenolsulfonic acid, oxalic acid, etc.). Of these, methyl sulfate, paratoluenesulfonic acid, and paraphenolsulfonic acid are preferred. In the present invention, in addition, a solid acid catalyst such as sulfonated activated carbon and Amberlyst can also be used. By using such a solid acid catalyst, the environmental load due to the reaction can be reduced, the activity and selectivity of the catalyst can be improved, and a continuous device reaction can be performed by using a column packed with a solid acid catalyst. Can also be easier.
The amount of the acidic catalyst to be used varies depending on the type of the mineral acid and the organic acid, etc., but when the total of fructose and phenol is 100 parts by mass, the range of 0.1 to 50 parts by mass is appropriate. , 0.2 to 10 parts by mass. If the amount of the acidic catalyst used is less than 0.1 part by mass, a sufficient amount of the compound of the present invention may not be produced. If the amount is more than 50 parts by mass, acid decomposition or gelation may be caused. In addition, solid acids are appropriately prepared from their types, types of biomass, and the like.

  The reaction temperature is suitably in the range of 20 to 200 ° C, preferably in the range of 100 to 160 ° C. If the reaction temperature is lower than 20 ° C, the compound of the present invention may not be sufficiently reacted and may not be produced. If the reaction temperature is higher than 200 ° C, excessive decomposition may be caused.

  In the case of a homogeneous mineral acid or organic acid, the reaction time is suitably in the range of 0.5 to 20 hours, preferably in the range of 0.5 to 3 hours. If the reaction time is less than 0.5 hour, the compound of the present invention may not be obtained with a sufficient yield, and if it is longer than 20 hours, the productivity may be reduced. In the case of using a solid acid catalyst, the reaction can be carried out by a batch method in which a solid acid catalyst is charged together with biomass and phenol in a flask, and for convenience, the reaction is also employed in the experiments in this patent. Since the liquid ratio cannot be reduced, the frequency of collision between the solid catalyst, the reaction substrate, and the reactant decreases, and the reaction time has to be long. In the future, the reaction time can be shortened by adopting a reaction method in which the liquid ratio is reduced, such as by filling a column with a solid catalyst and injecting and passing a suspension of a reactant such as phenol as a reaction substrate, and passing the suspension.

  After the reaction between fructose and phenol, the compound of the present invention can be isolated and purified by a conventional method using various liquid chromatography including GPC chromatography, thin-layer chromatography, and the like. Specifically, the amount required for analysis, chemical structure determination, and special characterization can be collected using preparative GPC chromatography / high-performance liquid chromatography or preparative thin-layer chromatography.

1.1.2 Preparation of Biomass Phenol Liquefied Resin Biomass phenol liquefied resin can be produced by a known method described in Patent Document 1 or the like. Specifically, for example, it can be produced by liquefying biomass by reacting biomass with phenols (solvolysis, solvolysis) in the presence of an acidic catalyst.

  Examples of the above-mentioned "phenols" include phenol, cresol, xylenol, propylphenol, butylphenol, butylcresol, phenylphenol, cumylphenol, methoxyphenol, bromophenol, and bisphenol A. Among these, phenol, cresol, xylenol, and bisphenol A are preferable, and phenol is more preferable, in terms of high reactivity and easy availability. These may be used alone or in combination of two or more.

When the biomass is a saccharide, examples of the saccharide include a monosaccharide, a disaccharide, a trisaccharide, an oligosaccharide, and a polysaccharide. Specifically, glucose, fructose, mannose, galactose, arabinose, xylose, maltose, isomaltose, lactose, sucrose, trehalose, raffinose, isomerized sugar, dextrin, oligosaccharide, fructan, fructooligosaccharide, starch, crude starch, amylose, Amylopectin, waste molasses (starch grounds) and the like. These may be used alone or in combination of two or more.
Examples of the acidic catalyst include mineral acids (eg, hydrochloric acid, sulfuric acid, phosphoric acid, etc.) and organic acids (eg, methyl sulfate, paratoluenesulfonic acid, paraphenolsulfonic acid, oxalic acid, etc.). Of these, methyl sulfate, paratoluenesulfonic acid, and paraphenolsulfonic acid are preferred.
When the total amount of the biomass and the phenol is 100 parts by mass, the amount of the acidic catalyst is preferably in the range of 0.1 to 50 parts by mass, and more preferably in the range of 0.2 to 10 parts by mass. . If the amount of the acidic catalyst used is less than 0.1 part by mass, a sufficient amount of the liquefied reaction product may not be generated. If the amount is more than 50 parts by mass, acid decomposition or gelation may be caused.
The same applies to the case where the biomass is a saccharide. The mass ratio between the saccharide and the phenol in obtaining the biomass phenolic liquefied resin is as follows when the saccharide is 1 part by mass. The amount of the phenol is preferably 0.5 to 20 times by mass, and more preferably 1.5 to 6 times by mass.

  The acidic catalyst, the amount used, the reaction temperature, the reaction time, and the like are basically the same as those described in the section of “1.1.1 Preparation of the compound of the present invention”.

  Phenols remaining unreacted can be consumed by conducting a resination reaction by adding a predetermined amount of formalin as necessary, or can be distilled off by distillation under reduced pressure. Is preferred.

1.2 In the process of producing a biomass phenol liquefied resin, the compound of the present invention is automatically contained by the reaction between fructose and phenol, and the liquefied resin of the present invention is used.

  As described above, the biomass phenol liquefied resin can be produced by a known method described in Patent Document 1 or the like. Specifically, for example, it can be produced by liquefying biomass by reacting biomass with phenols (solvolysis, solvolysis) in the presence of an acidic catalyst. In this case, the biomass includes the fructose described above, and the phenols include phenol. Otherwise, the biomass phenol liquefied resin can be produced in the same manner as described in the section “1.1.2 Preparation of biomass phenol liquefied resin”.

  The content of phenol in the phenol in the production of the present biomaphenol liquefied resin is 0.5 to 20 parts by mass based on 1 part by mass of fructose in biomass (or saccharides if biomass is saccharide). The range of mass times is appropriate, and the range of 1.5 to 6 times by mass is preferable. When the phenol content is less than 0.5 mass times the fructose content, the content of the compound of the present invention in the liquefied resin of the present invention is reduced, and a sufficiently low softening point or fluidity may not be obtained.

1.3 Uses of the liquefied resin of the present invention The liquefied resin of the present invention can be used, for example, in casting molds, molding materials, epoxy hardeners, binders for reinforcing paper and paper, paints, resins for grindstones, and the like.

2. Processed phenolic resin The present invention includes a processed phenolic resin produced using the liquefied resin of the present invention. Examples of such processed products include any processed products using phenolic resins such as molded products, adhesives, foams, carbon fibers, binders, and paints. Specifically, for example, automobile parts (various pulleys for air compressors, power steering, tensioners, etc.), electric / electronic / heavy electric parts (as printed wiring boards, switchboard breakers, magnet switches, outlet plugs, etc.), Machinery parts such as gears, sliding linings, bearings, etc., as well as daily necessities (bowls, trays, tea tables, pots / kettles / knobs, knobs, iron handles, ashtrays, etc.), insulation for houses and refrigerated warehouses Foams of panels, swords, etc., adhesives such as plywood adhesives, heat insulating materials for automobile power steering hoses, fibers for fireproof clothing, fibers for heat insulating gloves, activated carbon fibers for harmful gas adsorption, binders for firebricks and shell molds And undercoat paints for automobiles, inner paints for food cans, paints for ships, and corrosion-resistant paints for chemical equipment.

  The above-mentioned phenol resin processed product can be produced by a conventional method except that the liquefied resin of the present invention is used. Specifically, in the case of a molded article, for example, a liquefied resin of the present invention and a curing agent, a curing accelerator, an internal release agent, a filler, and the like are appropriately mixed (eg, a ball mill, a kneading extruder, a twin-screw extruder). It can be manufactured by mixing using a twin-screw kneader such as a roll kneader, filling the mixture into a desired mold, and hot-press molding. In addition, the liquefied resin of the present invention is manufactured by suspending in a suitable solvent (eg, acetone, methanol), kneading it with a curing agent, drying, filling in a desired mold, and hot-press molding. be able to.

  Examples of the curing agent include hexamethylenetetramine, benzylamine, benzoxazine, azomethine, epoxy resin, and melamine formaldehyde resin. Of these, hexamethylenetetramine is preferred.

  Examples of the curing accelerator include calcium hydroxide, magnesium oxide, aluminum halides such as aluminum chloride, benzoic acid, calcium acetate, sulfenamides, thiazoles, benzimidazoles, boron trifluoride monoethylamine complex, Examples thereof include dicarboxylic acids such as malonic acid and fumaric acid. Of these, calcium hydroxide and magnesium oxide are preferred.

  Examples of the internal release agent include zinc stearate, calcium stearate, magnesium stearate, and carnauba wax. Of these, zinc stearate is preferred.

As the filler, for example, wood powder, nut shell powder, cellulose powder, cotton fiber, shredded cloth, polyester fiber, polyamide fiber, polyvinyl alcohol fiber, carbon fiber, aromatic polyamide fiber, glass fiber, graphite, sulfide Molybdenum, calcium carbonate, mica, silica powder, talc, clay, wollastonite can be mentioned. Among them, wood powder and cellulose powder are preferred.

  Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples, and Test Examples, but the present invention is not limited to these Examples.

[Example 1]
A mixed solution of phenol and methylsulfuric acid synthesized in advance was weighed into a 200 mL eggplant flask such that the weight ratio of phenol, methanol and sulfuric acid was 95: 5: 3, and the mixture was stirred in a 45 ° C water bath at 400 rpm for 5 minutes. On the other hand, 9.00 g of β-D-fructose dried at 60 ° C. for 12 hours or more is weighed into an inner cylinder of Teflon (registered trademark, the same applies hereinafter), and the above mixed solution is weighed to a liquid ratio of 3 and added. Was. The Teflon inner cylinder was placed in a stainless steel pressure-resistant reaction tube, immersed in an oil bath set at 130 ° C., and stirred at 400 rpm for 60 minutes to perform a reaction. After the reaction, the pressure-resistant reaction tube was cooled in ice water for 15 minutes to obtain a black (black-green) liquid.
Using a part of the coloring liquid, the amount of unliquefied residue and the amount of unreacted phenol were determined at this stage.

  This black liquid was dissolved in a large excess of methanol, and neutralized by adding a theoretical equivalent of magnesium oxide to remove sulfuric acid. This was filtered through a PTFE membrane filter (T050; kept at 0.5 μm) to remove neutralized salts. After concentrating the filtrate with an evaporator set to 45 ° C. in a water bath, methanol and phenol were distilled off by reducing the pressure in an oil bath at 180 ° C. for 50 minutes to obtain a liquefied product (the liquefied resin of the present invention). The liquefied product was solid at room temperature, and was crushed in a mortar, placed in a 50 mL screw cap bottle, and dried with a vacuum dryer at 40 ° C. for 12 hours or more.

[Examples 2 to 7]
Liquefaction and liquefaction were performed in the same manner as in Example 1 except that the liquefaction temperature was set to 100, 110, 120, 140, 150, or 160 ° C., respectively, to obtain a liquefied product (fructose-derived phenol liquefied resin).

[Comparative Examples 1 to 3]
Instead of β-D-fructose, β-D-glucose, β-D-maltose, or sucrose is used, their drying temperature is 80 ° C., and the liquid ratio with the mixed solution is 3, A liquefied product (glucose-derived phenol liquefied resin, maltose-derived phenol liquefied resin, sucrose-derived phenol liquefied resin) was obtained in the same manner as in Example 1 except that maltose and sucrose were changed to 3.16.

[Test Example 1] Measurement of bending strength For each phenol liquefied product obtained in Example 1 and Comparative Examples 1 to 3, a molding composition (compound) was prepared as described below, and a bending test piece was prepared. And the bending strength were measured.
As a result, as shown below, the molded product from fructose phenol liquefied product shows the same strength as the similar molded product from glucose, maltose, and sucrose of the comparative example, and is molded from petroleum-derived novolak resin. The strength was clearly higher than that of the material.

(1) Preparation of molding composition (compound) and bending test piece A molding composition (compound) was prepared in the following quantitative ratio.

  The liquefied product and the reagent were weighed in a pulverizing container with the above-mentioned composition and mixed using a Planetary Mono Mill “pulverisette 6” manufactured by Fritsch Japan to obtain a uniform powdery compound. The mixing conditions are as shown in Table 2 below.

  Next, 5.8 g of the compound was filled in a mold having a size of 80 × 10 × 4 mm, and hot-pressed at 160 to 170 ° C. and 30 MPa for 5 minutes to prepare a test piece for a bending test. The test piece was conditioned at room temperature of 23 ° C. and a relative humidity of 50% under a constant temperature and humidity condition for 48 hours or more, and then the width and the thickness were measured at each of three places with a vernier caliper.

(2) Bending strength measurement test The bending strength was measured using Shimadzu Autograph AGS-5kNG manufactured by Shimadzu Corporation under the conditions of a load speed of 2.0 mm / min and a fulcrum distance of 64 mm according to Japanese Industrial Standards (JIS) K6911. Was measured. Flexural strength and flexural modulus were determined using the company's soft Shikibu. The bending strength measurement was performed twice for each sample.
The strength of the related sample obtained is shown below in comparison with the strength of a molded product from a commercially available novolak resin.

L indicates that the product is a liquefied product, G, M, S, and F indicate that they are derived from glucose, maltose, sucrose, and fructose, respectively, and 130 indicates that the product was liquefied at 130 ° C. Moldings from commercial novolak resins are labeled Novolac.
No difference in the flexural strength characteristics between the starting materials was observed. In addition, all the liquefied material-derived test specimens exhibited flexural strength and flexural modulus higher than those of commercially available novolak resins.

[Test Example 2] Measurement of molecular weight distribution, thermal fluidity characteristics, and heat of curing reaction The phenol liquefied products obtained in Example 1 and Comparative Example 1 were compared with each other in molecular weight distribution by gel permeation chromatography (GPC) described below. As a result, when the starting sugar was fructose, a peak having the minimum molecular weight was observed at a retention time of about 25.1 minutes. The molecular weight of the polystyrene calibration curve was 353 at a retention time of 25.1 minutes. However, it is difficult to determine an accurate molecular weight by GPC, so the molecular weight was determined using high performance liquid chromatography / mass spectrometry (LC / MS). As a result, the molecular weight was determined to be 354. The peak was clearly observed in all cases where the liquefaction temperature was 100-160 ° C. Slightly reduced clarity, but also observed in the case of sucrose. On the other hand, when glucose and maltose were liquefied, no corresponding peak was observed.

  The presence of a compound giving this peak increases the thermal fluidity of the entire liquefied product and enhances the curing reactivity. This is because the measurement of the thermal fluidity by a flow tester described below and the curing reaction heat by the differential scanning calorimeter (DSC) measurement are performed. From the measurement, it became clear as shown in Table 4.

(1) Examination of molecular weight distribution by gel permeation chromatography (GPC) A solution in which each of the obtained phenol resins was dissolved in tetrahydrofuran (THF) was used as a measurement sample, and the molecular weight distribution was examined under the conditions shown in Table 5 below.

(2) Measurement of Glass Transition Point (Tg) by Differential Scanning Calorimeter (DSC) DSC measurement was performed to examine the glass transition point (Tg) of each liquefied product. For the measurement, DSC6200 / EXSTAR6000 manufactured by Hitachi High-Tech Science was used. Each sample was subjected to a heat history removal process as follows. That is, the temperature was raised from room temperature to 140 ° C. at a rate of 20 ° C./min (first heating), and then rapidly cooled to −50 ° C. Then, the temperature was raised again to 200 ° C. at a rate of 20 ° C./min to obtain a DSC thermogram.

  In addition, Tg was determined using the midpoint method with the midpoint of the baseline shift of the DSC thermogram. Other measurement conditions are as shown in Table 6 below.

(3) Measurement of heat flow characteristics by flow tester The heat flow characteristics of each liquefied material were measured using Shimadzu Flow Tester CFT-500 manufactured by Shimadzu Corporation. The thermohydraulic temperature (Tf) was measured by a temperature rise measurement method, and the melt viscosity (η) was measured by a constant temperature measurement method. The conditions at the time of each measurement are as shown in Table 7 below.

[Test Example 3] Chemical structure identification of compound of the present invention From the liquefied product obtained in Example 1, a substance corresponding to the peak at a retention time of about 25.1 minutes by GPC (the lowest molecular weight classification obtained by molecular weight fractionation by GPC) ) Was collected by a preparative thin-layer chromatography to obtain the compound of the present invention. Then, the compound of the present invention was subjected to two-dimensional nuclear magnetic resonance (NMR) spectrum analysis. The results are shown in FIG. ^{1 (1} H- ¹ H COSY NMR spectrum) and FIG. ^{2 (1} H- 13 C HSQC NMR spectrum).
From the spectrum of the above two-dimensional nuclear magnetic resonance (NMR) spectrum analysis, infrared absorption spectrum (FT-IR) measurement, molecular weight measurement by high performance liquid chromatography / mass spectrometer (LC / MS), elemental analysis, etc., the molecular formula is C ₂₄ H ₁₈ O ₃ , which has three benzene rings in one molecule, has only one phenolic hydroxyl group in one molecule, and has no other hydroxyl group. The structure could be identified. NMR analysis before and after acetylation was also performed to obtain information on hydroxyl groups.

[Examples 8, 9 and Comparative Example 4]
Liquefaction was performed in the same manner as in Example 1 except that the liquefaction time was set to 20 minutes (Example 8), 10 minutes (Example 9), or 5 minutes (Comparative Example 4) to obtain a liquefied product.

[Comparative Examples 5 to 8]
Instead of β-D-fructose, β-D-glucose was used, and the liquefaction time was 60 minutes (Comparative Example 5), 20 minutes (Comparative Example 6), 10 minutes (Comparative Example 7), or 5 minutes (Comparative Example). A liquefied product was obtained according to Example 1, except that Example 8) was used.

[Example 10, Comparative Example 9]
The liquefaction catalyst was a solid acid catalyst (Amberlyst (registered trademark) 36, manufactured by Sigma-Aldrich) instead of methyl sulfate, the liquefaction temperature was 130 ° C., and the liquefaction time was 60 minutes (Comparative Example 9) or 300 minutes (implementation). Liquefied products were obtained in the same manner as in Example 1 except that Example 10) was used.

[Test Example 4] Liquefaction time and molecular weight distribution by GPC FIG. 3 shows a GPC chromatogram obtained by measuring the liquefied product obtained in Example 1, Examples 8, 9 and Comparative Examples 4 to 8 by the above-described method. Is shown in comparison with. FIG. 3A shows liquefied products obtained in Example 1, Examples 8, 9 and Comparative Example 4. In FIG. 3A, the top row shows the GPC chromatogram of the liquefied product of Example 1, and the second to bottom rows show the GPC chromatograms of the liquefied product of Examples 8 and 9 and Comparative Example 4 in order. .
In the liquefied product (Examples 1, 8, and 9) obtained by reacting at 130 ° C. for 10 minutes or more, a low molecular weight compound appearing at a retention time of 25.1 minutes was observed. The chemical structure of this compound has been identified as the compound of the present invention (see Test Example 2 and the like). In a short reaction of 5 minutes at 130 ° C. (Comparative Example 4), the presence of a low molecular weight compound was observed due to a retention time of 25.8 minutes, but it is considered to be a precursor of the compound of the present invention.
FIG. 3 (2) shows, in order from the top, glucose-derived liquefied products obtained in Comparative Examples 5 to 8, but there was no peak at a retention time of 25.1 minutes, and the compound of the present invention was not produced.

[Test Example 5] Effect of solid acid catalyst A GPC chromatogram of the liquefied product obtained in Example 10 and Comparative Example 9 is shown in FIG. In FIG. 4, curve A is a GPC chromatogram of the liquefied product of Example 10, curve B is a GPC chromatogram of the liquefied product of Comparative Example 9, and control is a GPC chromatogram of the liquefied product of Example 1. , Respectively.
As is clear from FIG. 4, when a solid acid catalyst is used, a long reaction time is required to produce the compound of the present invention, and a peak of a retention time of 25.1 minutes is observed in a 5-hour reaction. Became. Such a peak corresponds to the compound of the present invention.

The liquefied resin of the present invention is useful for producing a phenolic resin molded product because it has a low softening point and has high fluidity during molding and excellent moldability.

Claims (3)

A compound represented by the following formula (A).

An agent for enhancing the thermal fluidity of a biomass phenol liquefied resin, comprising the compound (A) according to claim 1. An agent for increasing the curing reactivity of a biomass phenol liquefied resin, comprising the compound (A) according to claim 1.

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