Method for producing phenol composition and phenol composition

Abstract

To provide a method of producing a phenol composition with an enhanced phenol content in the phenol composition.SOLUTION: A method for producing a phenol composition comprises a step A of heating a mixture containing a cured product of a thermosetting resin composition and a zeolite to decompose the cured product of the thermosetting resin composition, wherein the zeolite includes an ion-exchanged zeolite.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing a phenol composition and a phenol composition.

Background Art

[0002] Consideration has been made to produce various components by pyrolyzing resins.

[0003] Patent Document 1 discloses a method for producing benzene, which includes a step of obtaining a reaction product containing benzene by contacting a polyphenylene sulfide resin with a zeolite catalyst and subjecting the polyphenylene sulfide resin to pyrolysis and desulfurization reactions, wherein the zeolite catalyst is a proton-exchanged zeolite and the molar ratio of SiO2 to Al2O3 (SiO2 / Al2O3 ratio) is 5 to 100. Further, Patent Document 1 describes that "a method for producing benzene is provided, which can obtain benzene, a low-molecular hydrocarbon, in a high yield from PPS (polyphenylene sulfide) by pyrolysis and desulfurization reactions".

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Regarding the production of various components by pyrolyzing resins, when producing a phenol composition by pyrolyzing a resin, there is room for improvement in increasing the content of phenols in the phenol composition. The present invention provides a method for producing a phenol composition in which the content of phenols in the phenol composition is increased.

Means for Solving the Problems

[0006] According to the present invention, there are provided a method for producing a phenol composition and a phenol composition as described below.

[0007] 1. A step A of decomposing a cured product of the thermosetting resin composition by heat-treating a mixture containing the cured product of the thermosetting resin composition and zeolite, A method for producing a phenol composition, wherein the zeolite contains ion-exchanged zeolite. 2. The method for producing a phenol composition according to 1., wherein the ion-exchanged zeolite contains one or more selected from the group consisting of beta-type zeolite, ZSM-5 type zeolite, ferrierite type zeolite, mordenite type zeolite, L-type zeolite and Y-type zeolite. 3. The method for producing a phenol composition according to 2., wherein the ion-exchanged zeolite contains one or more selected from the group consisting of ferrierite type zeolite, mordenite type zeolite, L-type zeolite and Y-type zeolite. 4. The method for producing a phenol composition according to any one of 1. to 3., wherein the cation of the ion-exchanged zeolite contains one or more selected from the group consisting of hydrogen ion, ammonium ion, sodium ion and potassium ion. 5. The method for producing a phenol composition according to any one of 1. to 4., wherein the ion-exchanged zeolite contains an alkali metal ion-exchanged type zeolite. 6. The specific surface area of the zeolite measured by the BET method is 50 m 2 / g or more and 1000 m 2 / g or less. The method for producing a phenol composition according to any one of 1. to 5. 7. The method for producing a phenol composition according to any one of 1. to 6., wherein the pore diameter of the zeolite is 0.1 Å or more and 40 Å or less. 8. The method for producing a phenol composition according to any one of 1. to 7., wherein the molar number of SiO2 with respect to 1 mol of Al2O3 in the zeolite is 5 mol or more and 500 mol or less. 9. The method for producing a phenol composition according to any one of 1. to 8., wherein the cured product of the thermosetting resin composition contains the cured product of the phenol resin composition. 10. The method for producing a phenol composition according to any one of 1. to 9., wherein the average particle diameter of the cured product of the thermosetting resin composition is 10 μm or more and 10 mm or less. 11. The method for producing a phenol composition according to any one of 1. to 10., wherein the heating temperature in the step A is 300°C or more and 1200°C or less. 12. A phenol composition obtained by the method for producing a phenol composition according to any one of 1. to 11. 13. The phenol composition according to 12., wherein the content of phenols in the phenol composition is 55% by mass or more.

Effect of the Invention

[0008] According to the present invention, a method for producing a phenol composition with an improved content of phenols in the phenol composition can be provided.

Embodiments for Carrying Out the Invention

[0009] Hereinafter, the present invention will be described based on embodiments.

[0010] [Method for Producing Phenol Composition] Hereinafter, the method for producing the phenol composition of the present embodiment will be described.

[0011] The method for producing a phenol composition of the present embodiment includes a step A of decomposing the cured product of the thermosetting resin composition by heat-treating a mixture containing the cured product of the thermosetting resin composition and zeolite, and the zeolite contains ion-exchanged zeolite.

[0012] The phenol composition in the present embodiment is a composition containing phenols. The phenols in the present embodiment are compounds having one or more hydroxy groups on the benzene ring. Further, the phenols of the present embodiment are monocyclic. The phenols of this embodiment include, for example, one or more selected from the group consisting of isomers of dimethylphenol (dimethylphenol other than 2,6-dimethylphenol and 2,4-dimethylphenol), 2,6-dimethylphenol, 2,4-dimethylphenol, ortho-cresol, para-cresol, and phenol.

[0013] The zeolite in this embodiment is a general term for crystalline aluminosilicates. The ion-exchanged zeolite in this embodiment contains a cation capable of ion exchange in the structure of the zeolite.

[0014] Although the mechanism by which the content of phenols in the phenol composition is improved by the method for producing the phenol composition of this embodiment is not clear, it is presumed that the ion-exchanged zeolite functions as a solid acid catalyst or a solid base catalyst, so that the reaction transition state becomes a state suitable for the production of phenols, thereby improving the content of phenols in the phenol composition.

[0015] From the viewpoint of further improving the content of phenols in the phenol composition, the ion-exchanged zeolite of this embodiment preferably contains one or more selected from the group consisting of beta-type zeolite, ZSM-5 type zeolite, ferrierite type zeolite, mordenite type zeolite, L-type zeolite, and Y-type zeolite, more preferably contains one or more selected from the group consisting of ferrierite type zeolite, mordenite type zeolite, L-type zeolite, and Y-type zeolite, still more preferably contains one or more selected from the group consisting of mordenite type zeolite and Y-type zeolite, and still more preferably contains mordenite type zeolite.

[0016] Examples of commercially available ion-exchange zeolites of the present embodiment include, for example, the HSZ (registered trademark) series manufactured by Tosoh Corporation. The HSZ series includes, for example, the HSZ-900 series which is a beta-type zeolite, the HSZ-800 series which is a ZSM-5 type zeolite, the HSZ-700 series which is a ferrierite type zeolite, the HSZ-600 series which is a mordenite type zeolite, the HSZ-500 series which is an L-type zeolite, and the HSZ-300 series which is a Y-type zeolite.

[0017] From the viewpoint of further improving the content of phenols in the phenol composition, the cation of the ion-exchange zeolite of the present embodiment preferably contains one or more selected from the group consisting of hydrogen ions, ammonium ions, sodium ions, and potassium ions, more preferably contains one or more selected from the group consisting of ammonium ions, sodium ions, and potassium ions, still more preferably contains one or two selected from the group consisting of sodium ions and potassium ions, and still more preferably contains sodium ions.

[0018] From the viewpoint of further improving the content of phenols in the phenol composition, the ion-exchange zeolite of the present embodiment preferably contains an alkali metal ion-exchanged zeolite, more preferably contains one or two selected from the group consisting of sodium ion-exchanged zeolite and potassium ion-exchanged zeolite, and still more preferably contains sodium ion-exchanged zeolite.

[0019] From the viewpoint of further improving the content of phenols in the phenol composition, the specific surface area of the zeolite of the present embodiment measured by the BET method is preferably 50 m 2 / g or more, more preferably 75 m 2 / g or more, still more preferably 100 m 2 / g or more, still more preferably 125 m 2 / g or more, still more preferably 150 m 2 / g or more, and preferably 1000 m 2 / g or less, more preferably 900 m 2 / g or less, still more preferably 800 m 2 / g or less, still more preferably 700 m 2 / g or less, still more preferably 670 m 2 / g or less, and preferably 50 m 2 / g or more and 1000 m 2 / g or less, more preferably 75 m 2 / g or more and 900 m 2 / g or less, still more preferably 100 m 2 / g or more and 800 m 2 / g or less, still more preferably 125 m 2 / g or more and 700 m 2 / g or less, still more preferably 150 m 2 / g or more and 670 m 2 / g or less.

[0020] From the viewpoint of further improving the content of phenols in the phenol composition, the pore diameter of the zeolite of this embodiment is preferably 0.1 Å or more, more preferably 0.5 Å or more, still more preferably 1 Å or more, still more preferably 2 Å or more, still more preferably 4 Å or more, and preferably 40 Å or less, more preferably 25 Å or less, still more preferably 15 Å or less, still more preferably 12 Å or less, still more preferably 10 Å or less, and preferably 0.1 Å or more and 40 Å or less, more preferably 0.5 Å or more and 25 Å or less, still more preferably 1 Å or more and 15 Å or less, still more preferably 2 Å or more and 12 Å or less, still more preferably 4 Å or more and 10 Å or less.

[0021] In the zeolite of the present embodiment, the molar number of SiO2 with respect to 1 mol of Al2O3 is preferably 5 mol or more, more preferably 6 mol or more, from the viewpoint of further improving the content of phenols in the phenol composition, and preferably 500 mol or less, more preferably 200 mol or less, still more preferably 100 mol or less, still more preferably 70 mol or less, still more preferably 40 mol or less, still more preferably 20 mol or less. The molar number of SiO2 with respect to 1 mol of Al2O3 can be measured by, for example, fluorescence X-ray analysis (XRF).

[0022] The shape of the zeolite of the present embodiment is not particularly limited, and may be, for example, powder, pellet, or bead.

[0023] When the shape of the zeolite of the present embodiment is powder or bead, the average particle diameter of the zeolite of the present embodiment is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, still more preferably 2 μm or more, still more preferably 4 μm or more, from the viewpoint of further improving the content of phenols in the phenol composition, and preferably 100 μm or less, more preferably 50 μm or less, still more preferably 30 μm or less. The average particle diameter of the zeolite of the present embodiment is the value of the cumulative particle diameter 50% (D 50 ) by the laser diffraction / scattering particle size distribution measurement method.

[0024] In the method for producing the phenol composition of the present embodiment, the cured product of the thermosetting resin composition of the present embodiment preferably contains the cured product of the phenol resin composition from the viewpoint of further improving the content of phenols in the phenol composition.

[0025] The phenolic resin contained in the phenolic resin composition of this embodiment is not particularly limited, and may include a novolak-type phenolic resin, a resol-type phenolic resin, or a mixture of a novolak-type phenolic resin and a resol-type phenolic resin. For example, it may include Sumilite Resin (registered trademark) PR-217, PR-311, PR-50590B, PR-961A, PR-9480, PR-51283 manufactured by Sumitomo Bakelite Co., Ltd.

[0026] The thermosetting resin composition of this embodiment may contain a thermosetting resin other than the phenolic resin. For example, it may contain one or two selected from the group consisting of epoxy resins, melamine resins, and urea resins.

[0027] The thermosetting resin composition of this embodiment may contain, for example, an uncured or semi-cured resin.

[0028] The cured product of the thermosetting resin composition of this embodiment does not refer to the concept of only containing the cured product of the thermosetting resin composition alone. For example, a molding material or molded product containing an inorganic filler such as silica fine particles and glass fibers, or an organic filler such as wood powder; a laminate containing an inorganic base material such as glass woven fabric and glass non-woven fabric, or an organic base material such as paper and cloth; a metal-clad laminate obtained by laminating a metal foil such as a copper foil on the laminate; and one or two selected from the group consisting of printed circuit boards obtained by processing metal-clad laminates and the like may be included.

[0029] From the viewpoint of improving the efficiency of the decomposition reaction, the cured product of the thermosetting resin composition of this embodiment is preferably made into particles by treatment such as grinding.

[0030] From the viewpoint of reducing the labor required for grinding, the average particle size of the cured product of the thermosetting resin composition of this embodiment is preferably 10 μm or more, and from the viewpoint of further improving the content of phenols in the phenol composition, it is preferably 10 mm or less. The average particle size of the cured product of the thermosetting resin composition of this embodiment is the value of the cumulative particle size 50% (D 50 ) measured by the laser diffraction / scattering particle size distribution measurement method.

[0031] From the perspective of further improving the content of phenols in the phenol composition, the heating temperature in Step A of the method for producing the phenol composition of this embodiment is preferably 300°C or higher, more preferably 400°C or higher, still more preferably 500°C or higher, and even more preferably 550°C or higher. And it is preferably 1200°C or lower, more preferably 1000°C or lower, still more preferably 800°C or lower, and even more preferably 700°C or lower. And it is preferably 300°C or higher and 1200°C or lower, more preferably 400°C or higher and 1000°C or lower, still more preferably 500°C or higher and 800°C or lower, and even more preferably 550°C or higher and 700°C or lower.

[0032] When mixing zeolite and the cured product of the thermosetting resin composition, from the perspective of further improving the content of phenols in the phenol composition, the mass of the zeolite of this embodiment relative to 1 g of the cured product of the thermosetting resin composition of this embodiment in the mixture is preferably 1 g or more, more preferably 5 g or more, and still more preferably 8 g or more. And from the perspective of the balance between reducing the amount of zeolite used and the amount of phenols generated, it is preferably 50 g or less, more preferably 30 g or less, and still more preferably 20 g or less.

[0033] When mixing zeolite and the cured product of the thermosetting resin composition, the mixture may contain components other than the cured product of the thermosetting resin composition and zeolite. For example, it may contain phenols.

[0034] The method for producing the phenol composition of this embodiment may include steps other than Step A. For example, it may include a step of purifying the phenol composition.

[0035] [Phenol Composition] Hereinafter, the phenol composition of this embodiment will be described.

[0036] The phenol composition of this embodiment is obtained by the method for producing the phenol composition of this embodiment.

[0037] The content of phenols in the phenolic composition of this embodiment is preferably 55% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, still more preferably 70% by mass or more, still more preferably 75% by mass or more, still more preferably 80% by mass or more, and, for example, 99% by mass or less.

[0038] The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the scope that can achieve the object of the present invention are included in the present invention.

Examples

[0039] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.

[0040] (Examples 1 to 7) A thermal decomposition test was conducted using an apparatus in which a gas chromatography mass spectrometer (manufactured by Agilent Technologies, gas chromatography model name: 7890B, mass spectrometer model name: 5977B) was connected to a thermal decomposition apparatus (manufactured by FRONTIER LAB, model name: EGA / PY-3030D). The sample for the thermal decomposition test was prepared by the following procedure. PR-217 manufactured by Sumitomo Bakelite Co., Ltd. was cured under the conditions of 200 ° C. for 1 hour to obtain a cured product. The obtained cured product was pulverized and used as the sample. A mixture of 0.2 mg of the obtained sample and 2.0 mg of the zeolite described in Table 1 was set in the above pyrolysis apparatus, heated from 80°C to 600°C at a heating rate of 50°C / min, maintained at 600°C for 2 minutes, and the identification and quantification of phenols contained in the pyrolysis products generated by pyrolysis were performed using the above gas chromatography-mass spectrometry apparatus. In this example, the total content of isomers of dimethylphenol (dimethylphenol other than 2,6-dimethylphenol and 2,4-dimethylphenol), 2,6-dimethylphenol, 2,4-dimethylphenol, orthocresol, paracresol, and phenol was defined as the content of phenols. Note that all of the zeolites described in Table 1 are of the HSZ (registered trademark) series manufactured by Tosoh Corporation.

[0041] (Comparative Example 1) A pyrolysis test was conducted in the same manner as in Examples 1 to 7 except that no zeolite was used. The results are shown in Table 1.

[0042]

Table 1

[0043] According to the production method of the example, a phenol composition (a composition containing phenols) could be produced. Also, according to the production method of the example, the content of phenols in the phenol composition was improved compared to the comparative example. From this, it can be seen that the content of phenols in the phenol composition can be improved by the production method of this embodiment.

Claims

1. A method for producing a phenol composition, comprising a step A of decomposing a cured product of the thermosetting resin composition by heat-treating a mixture containing the cured product of the thermosetting resin composition and zeolite, wherein the zeolite contains ion-exchanged zeolite.

2. The method for producing a phenol composition according to claim 1, wherein the ion-exchanged zeolite contains one or more selected from the group consisting of beta-type zeolite, ZSM-5 type zeolite, ferrierite-type zeolite, mordenite-type zeolite, L-type zeolite and Y-type zeolite.

3. The method for producing a phenol composition according to claim 2, wherein the ion-exchanged zeolite contains one or more selected from the group consisting of ferrierite-type zeolite, mordenite-type zeolite, L-type zeolite and Y-type zeolite.

4. The method for producing a phenol composition according to claim 1 or 2, wherein the cation of the ion-exchanged zeolite contains one or more selected from the group consisting of hydrogen ion, ammonium ion, sodium ion and potassium ion.

5. The method for producing a phenol composition according to claim 1 or 2, wherein the ion-exchanged zeolite contains alkali metal ion-exchanged zeolite.

6. The specific surface area of the zeolite measured by the BET method is 50 m ２ / g or more and 1000 m ２ / g or less, the method for producing a phenol composition according to claim 1 or 2.

7. The method for producing a phenol composition according to claim 1 or 2, wherein the pore diameter of the zeolite is 0.1 Å or more and 40 Å or less.

8. In the zeolite, the number of moles of SiO2 per 1 mole of Al ２ O ３ is 5 moles or more and 500 moles or less, and the method for producing a phenol composition according to claim 1 or 2. ２ ​

9. The method for producing a phenol composition according to claim 1 or 2, wherein the cured product of the thermosetting resin composition contains a cured product of a phenol resin composition.

10. The method for producing a phenol composition according to claim 1 or 2, wherein the average particle diameter of the cured product of the thermosetting resin composition is 10 μm or more and 10 mm or less.

11. The method for producing a phenol composition according to claim 1 or 2, wherein the heating temperature in the step A is 300 ° C or more and 1200 ° C or less.

12. A phenol composition obtained by the method for producing a phenol composition according to claim 1 or 2.

13. The phenol composition according to claim 12, wherein the content of phenols in the phenol composition is 55% by mass or more.

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