Novel phenol compound

Abstract

To provide a novel phenolic compound.SOLUTION: The present invention discloses, for example, a compound of the structural formula illustrated below.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a novel phenolic compound.

Background Art

[0002] Phenolic compounds are widely used as monomers in the synthesis of phenolic resins, resol resins, polyphenylene ether resins, etc. For example, phenolic resins and resol resins are obtained by polymerizing a phenolic compound and formaldehyde under an acid or base catalyst, and polyphenylene ether is obtained by an oxidative polymerization method using 2,6-xylenol as a raw material.

[0003] Phenolic resins have been used for a long time as thermosetting resins having excellent heat resistance and flame retardancy, and polyphenylene ether has attracted attention in the fields of communication equipment, etc. as a material having low dielectric characteristics. Conventionally, in such resins and polymers, in accordance with the usage method and application, studies have been advanced on introducing a functional functional group into a part of the molecular structure.

[0004] For example, Patent Document 1 discloses a polyphenylene ether in which a reactive group is introduced into the side chain using a phenolic compound having an allyl group as a raw material, and Patent Document 2 discloses that a polyphenylene ether useful as a compatibilizer for a polymer alloy can be obtained by producing and using a phenol substituent having an alcoholic hydroxyl group.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, the methods of use and required properties of phenolic resins, polyphenylene ethers, etc. are diverse. In addition to the patent documents described above, a method for more simply introducing a desired functional group is demanded.

[0007] Therefore, an object of the present invention is to provide a novel phenolic compound useful for the synthesis of polymers containing phenols as monomers, for example.

Means for Solving the Problems

[0008] As a result of intensive studies, the present inventors have found a novel phenolic compound having a specific structure and completed the present invention. That is, the present invention is as follows.

[0009] The present invention is a compound represented by the following formula 1. (Formula 1) JPEG0007695811000001.jpg3464(In the formula, R 1 ~R 4 independently of each other, represent H or an alkyl group having 3 or less carbon atoms, R 5 represents -(CH2) n -S-R A n represents an integer of 2 or more and 4 or less, R A represents any one of the structure of the following formula 2, an alkyl group having 1 to 3 carbon atoms substituted with a carboxyl group, an alkyl group having 2 to 4 carbon atoms substituted with two hydroxyl groups, or an alkyl group having 6 to 10 carbon atoms.) (Formula 2) JPEG0007695811000002.jpg12115(In the formula, m represents an integer of 1 or more and 4 or less, R x 、R y 、R z independently of each other, represent an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.)

Effects of the Invention

[0010] According to the present invention, there is provided a novel phenol compound useful for the synthesis of polymers containing, for example, phenols as monomers.

Mode for Carrying Out the Invention

[0011] Hereinafter, the structure, production method, uses, etc. of the phenol compound according to the present invention will be described, but these are examples of the present invention, and the present invention is not limited thereto at all.

[0012] In addition, when isomers exist in the described compounds, unless otherwise specified, the present invention includes all possible isomers.

[0013] Also, in the present invention, hydrocarbon groups such as alkyl groups may be linear or branched.

[0014] <<<Structure of Phenol Compound>>> The phenol compound according to the present invention has a structure represented by the following formula (1). (Formula 1) JPEG0007695811000003.jpg3464

[0015] In Formula 1, R 1 ~R 4 independently of each other, represent H or an alkyl group having 3 or fewer carbon atoms, R 5 represents -(CH2) n -S-R A n represents an integer of 2 or more and 4 or less (preferably 3 or more and 4 or less), R A represents any one of the following structures: an alkyl group having 1 to 3 carbon atoms (preferably 2 carbon atoms) substituted with a carboxyl group; an alkyl group having 2 to 4 carbon atoms (preferably 3 carbon atoms) substituted with two hydroxyl groups; an alkyl group having 6 to 10 carbon atoms (preferably 7 to 9 carbon atoms, more preferably 8 carbon atoms).

[0016] (Formula 2) JPEG0007695811000004.jpg12115

[0017] In Formula 2, m represents an integer of 1 or more and 4 or less (preferably 3 or more and 4 or less), R x , R y , R z independently of each other, represents an alkyl group having 1 to 3 carbon atoms (preferably 1 to 2 carbon atoms) or an alkoxy group having 1 to 3 carbon atoms (preferably 1 to 2 carbon atoms).

[0018] In Formula 1, R 1 is preferably hydrogen or a methyl group, and R 2 to R 4 are preferably hydrogen.

[0019] In Formula 2, R x , R y , R z are preferably such that at least one of them is an alkoxy group having 1 to 3 carbon atoms, and preferably two or more of them are alkoxy groups having 1 to 3 carbon atoms.

[0020] When the alkyl group is substituted with a carboxyl group, any position of the alkyl group may be substituted with a carboxyl group. Similarly, when the alkyl group is substituted with a hydroxyl group, any position of the alkyl group may be substituted with a hydroxyl group.

[0021] Thus, the phenolic compound according to the present invention has a structure in which various organic groups having a sulfide bond are bonded to phenols (compounds having at least a hydroxy group as an aromatic substituent).

[0022] <<Specific Examples of Phenolic Compounds>> <Phenolic Compound A> Phenolic Compound A is a compound in which, in Formula 1, R A is represented by the structure of Formula 2.

[0023] Phenolic compound A is preferably a compound represented by formula A.

[0024] (Formula A) JPEG0007695811000005.jpg2264

[0025] In formula A, R 1 is H or a methyl group, n is an integer of 3 or 4, m is an integer of 3 or 4, R x 、R y 、R z independently of one another represent an alkyl group having 1 to 2 carbon atoms or an alkoxy group having 1 to 2 carbon atoms.

[0026] In formula A, R 1 is preferably H.

[0027] In formula A, n is preferably 3.

[0028] In formula A, m is preferably 3.

[0029] In formula A, R x 、R y 、R z One or more of them are preferably an alkoxy group having 1 to 2 carbon atoms, and two or more of them are preferably an alkoxy group having 1 to 2 carbon atoms.

[0030] Specific examples of phenolic compound A include the compounds represented by the following formulas A1 - A3.

[0031] (Formula A1) JPEG0007695811000006.jpg3364

[0032] (Formula A2) JPEG0007695811000007.jpg3764

[0033] (Formula A3) JPEG0007695811000008.jpg3864

[0034] <Phenolic compound B> In the above formula 1, phenolic compound B is a compound in which R A is an alkyl group having 1 to 3 carbon atoms substituted with a carboxyl group. Phenolic compound B is preferably a compound represented by formula B.

[0035] (Formula B) JPEG0007695811000009.jpg2764

[0036] In formula B, R 1 is H or a methyl group, n is an integer of 3 or 4, R A represents an alkyl group having 2 carbon atoms substituted with a carboxyl group.

[0037] In formula B, R 1 is preferably H.

[0038] In formula B, n is preferably 3.

[0039] Specific examples of phenolic compound B include the compounds shown in the following formulas B1 - B2.

[0040] (Formula B1) JPEG0007695811000010.jpg2864

[0041] (Formula B2) JPEG0007695811000011.jpg3164

[0042] <Phenolic compound C> In the above formula 1, phenolic compound C is a compound in which R A is an alkyl group having 2 to 4 carbon atoms substituted with two hydroxyl groups.

[0043] Phenol compound C is preferably a compound represented by formula C.

[0044] (Formula C) JPEG0007695811000012.jpg2964

[0045] In formula C, R 1 is H or a methyl group, n is an integer of 3 or 4, R A represents an alkyl group having 3 carbon atoms substituted with two hydroxyl groups.

[0046] In formula C, R 1 is preferably H.

[0047] In formula C, n is preferably 3.

[0048] Specific examples of phenol compound C include the compounds shown in the following formula C1.

[0049] (Formula C1) JPEG0007695811000013.jpg2864

[0050] <Phenol compound D> Phenol compound D has a structure in which, in the above formula 1, R A is an alkyl group having 6 to 10 carbon atoms.

[0051] Phenol compound D is preferably a compound represented by formula D.

[0052] (Formula D) JPEG0007695811000014.jpg2964

[0053] In formula D, R 1 is H or a methyl group, n is an integer of 3 or 4, R Arepresents an alkyl group having 7 to 9 carbon atoms.

[0054] In formula D, R 1 is preferably H.

[0055] In formula D, n is preferably 3.

[0056] In formula D, R A is preferably an alkyl group having 8 carbon atoms.

[0057] Specific examples of the phenolic compound D include the compounds represented by the following formula D1.

[0058] (Formula D1) JPEG0007695811000015.jpg3264

[0059] <<<Production method of phenolic compound>>> The phenolic compound according to the present invention can usually be synthesized by subjecting a phenol having an alkenyl group and a compound having a terminal thiol group and a desired organic group (thiol compound) to an enethiol reaction.

[0060] The phenolic compound according to the present invention can be produced, for example, as follows.

[0061] <<Synthesis>> Subject an alkenyl group-containing phenol and a thiol compound to an enethiol reaction.

[0062] In the enethiol reaction, a carbon-carbon double bond and a thiol group are subjected to an addition reaction in a 1:1 ratio. More specifically, in the enethiol reaction, a thioyl radical is generated by adding a thermal radical generator to the thiol and heating it, or by irradiating it with an energy ray, and a reaction occurs in which the thiol group is added to the ethylenic double bond by the radical. Since the thioyl radical reacts chainwise in the enethiol reaction, the phenolic compound according to the present invention can be synthesized with high efficiency.

[0063] The blending ratio (molar ratio) of phenols having an alkenyl group and a thiol compound may be an equal amount, or either one may be blended in excess.

[0064] The conditions for energy ray irradiation, the type and amount of the initiator to be blended, the solvent to be used, the concentration of each compound in the solvent, the reaction conditions (reaction temperature, reaction time, stirring conditions, atmosphere), etc. may be appropriately set according to the raw materials to be used and are not limited.

[0065] <<Raw materials>> <Phenols having an alkenyl group> As the phenols having an alkenyl group, the compounds represented by the following formula i can be used.

[0066] (Formula i) JPEG0007695811000016.jpg3264

[0067] In formula i, R 1 ~R 4 each independently represents H or an alkyl group having 3 or fewer carbon atoms, p represents an integer of 0 or more and 2 or less.

[0068] <Thiol compound> As the thiol compound, the compounds represented by the following formula ii can be used.

[0069] (Formula ii) JPEG0007695811000017.jpg964

[0070] In formula ii, R A represents any one of the structure of the following formula 2, an alkyl group having 2 to 4 carbon atoms substituted with two hydroxyl groups, an alkyl group having 1 to 3 carbon atoms substituted with a carboxyl group, or an alkyl group having 6 to 10 carbon atoms.

[0071] (Formula 2) JPEG0007695811000018.jpg12115

[0072] In Formula 2, m represents an integer of 1 or more and 4 or less, R x 、R y 、R z independently of one another, represent an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.

[0073] Here, the phenolic compound according to the present invention can also be synthesized by subjecting phenols having a terminal thiol group and a compound having an alkenyl group and a desired organic group to an enethiol reaction.

[0074] <<<Use of phenolic compound>>> The phenolic compound according to the present invention can be used as a substitute for part or all of ordinary phenols, and can be contained, for example, as a monomer when synthesizing a phenolic resin, a resol resin or a polyphenylene ether resin. According to such a usage method, effects such as adjusting the fluidity (viscosity) of the obtained resin, improving the affinity between the resin component and an inorganic filler such as silica, and improving the adhesion to a conductor material such as a metal plating when using the resin as an insulating material or the like can be expected. In addition, since the phenolic compound according to the present invention has reactivity with an epoxy group, an isocyanate group or the like, it can also be used as an additive for modifying and imparting functions to a composition containing a compound having these functional groups.

Example

[0075] <<Example 1>> 2-Allylphenol was used as the alkenylphenol, and (3-mercaptopropyl)trimethoxysilane was used as the thiol compound, and these were subjected to an enethiol reaction. Specifically, it is as follows.

[0076] 2.0 g (1.5×10 -2 mol) of 2-allylphenol and 3.9 g (2.0×10-2 (1 mol) was added to 8.9 g of toluene so that the total monomer concentration became 40 wt%. After stirring under a nitrogen atmosphere and heating to 60°C, 0.057 g of AIBN (azo polymerization initiator) was added so as to be 1 mol% with respect to the total molar amount of the monomers, and the mixture was stirred at 60°C under a nitrogen atmosphere for 10 hours to obtain Reaction Product I. With respect to the obtained reaction composition I, it was isolated with a mixed solvent of ethyl acetate / hexane by column chromatography, and the solvent was distilled off with an evaporator to obtain a compound represented by the following Formula I in a yield of 90% as a light brown liquid.

[0077] 1 1H-NMR (400 MHz, Acetone-d6), 0.771 (t, 2H, J = 6.0 Hz, -CH2-Si-), 1.70 (quin, 2H, J = 6.0 Hz, -CH2-CH2-Si-), 1.90 (quin, 2H, J = 6.0 Hz, -S-CH2-CH2-CH2-Ar), 2.52 (t, 2H, J = 6.0 Hz, -S-CH2-), 2.53 (t, 2H, J = 6.0 Hz, -S-CH2-), 2.72 (t, 2H, J = 6.0 Hz, Ar-CH2-), 3.50 (s, 9H, -CH3), 6.77 (t, 1H, J = 6.0 Hz, Ar-H), 6.83 (d, 1H, J = 6.0 Hz, Ar-H), 7.06 (d, 1H, J = 6.0 Hz, Ar-H), 7.07 (t, 1H, J = 6.0 Hz, Ar-H), 8.05 (s, 1H, Ar-OH)

[0078] (Formula I) JPEG0007695811000019.jpg3364

[0079] <<Example 2>> 2-Allylphenol was used as the alkenyl group phenols, and (3-mercaptopropyl)triethoxysilane was used as the thiol compound, and these were subjected to an enethiol reaction. Specifically, it is as follows.

[0080] Reaction Product II was obtained in the same manner as in Example 1 except that the thiol compound was changed. The obtained Reaction Composition II was isolated by column chromatography with an ethyl acetate / hexane mixed solvent, and the solvent was distilled off with an evaporator to obtain the compound represented by the following Formula II as a pale brown liquid in a yield of 90%.

[0081] 1 H-NMR (400MHZ, Acetone-d6), 0.717 (t, 2H, J = 6.0 Hz, -CH2-Si-), 1.19 (t, 9H, J = 6.0 Hz, -CH2-CH3), 1.67 (quin, 2H, J = 6.0 Hz, -CH2-CH2-Si-), 1.89 (quin, 2H, J = 6.0 Hz, -S-CH2-CH2-CH2-Ar), 2.53 (t, 2H, J = 6.0 Hz, -S-CH2-), 2.54 (t, 2H, J = 6.0 Hz, -S-CH2-), 2.79 (t, 2H, J = 6.0 Hz, Ar-CH2-) 3.80 (q, 1H, J = 6.0 Hz, -O-CH2-), 7.10 (t, 1H, J = 6.0 Hz, Ar-H), 7.17 (d, 1H, J = 6.0 Hz, Ar-H), 7.23 (d, 1H, J = 6.0 Hz, Ar-H), 7.24 (t, 1H, J = 6.0 Hz, Ar-H), 8.12 (s, 1H, Ar-OH)

[0082] (Formula II) JPEG0007695811000020.jpg4164

[0083] <<Example 3>> 2-Allylphenol was used as the alkenyl group phenols, and 3-mercaptopropyl(dimethoxy)methylsilane was used as the thiol compound, and these were subjected to an enethiol reaction. Specifically, it is as follows.

[0084] The reaction product III was obtained in the same manner as in Example 1 except that the thiol compound was changed. With respect to the obtained reaction composition III, it was isolated with a mixed solvent of ethyl acetate / hexane by column chromatography, the solvent was distilled off with an evaporator, and the compound represented by the following formula III was obtained as a pale brown liquid with a yield of 90%.

[0085] 1 H-NMR (400MHZ, Acetone-d6), 0.0622 (s, 6H, J = 6.0 Hz, -CH3), 0.715 (t, 2H, J = 6.0 Hz, -CH2-Si-), 1.62 (quin, 2H, J = 6.0 Hz, -CH2-CH2-Si-), 1.89 (quin, 2H, J = 6.0 Hz, -S-CH2-CH2-CH2-Ar), 2.50 (t, 2H, J = 6.0 Hz, -S-CH2-), 2.53 (t, 2H, J = 6.0 Hz, -S-CH2-), 2.71 (t, 2H, J = 6.0 Hz, Ar-CH2-), 3.45 (s, 6H, -O-CH3), 7.09 (t, 1H, J = 6.0 Hz, Ar-H), 7.15 (d, 1H, J = 6.0 Hz, Ar-H), 7.21 (d, 1H, J = 6.0 Hz, Ar-H), 7.25 (t, 1H, J = 6.0 Hz, Ar-H), 8.12 (s, 1H, Ar-OH)

[0086] (Formula III) JPEG0007695811000021.jpg3564

[0087] <<Example 4>> 2-Allylphenol was used as the alkenyl group phenols, and thioacetic acid was used as the thiol compound, and these were subjected to an enethiol reaction. Specifically, it is as follows.

[0088] A reaction product IV was obtained in the same manner as in Example 1 except that the thiol compound was changed. With respect to the obtained reaction composition IV, it was isolated with a mixed solvent of ethyl acetate / hexane by column chromatography, and the solvent was distilled off with an evaporator to obtain a compound represented by the following formula IV in a yield of 90% as a light brown liquid.

[0089] 1 H-NMR (400MHZ, Acetone-d6), 1.39 (d, 3H, J = 6.0 Hz, -CH3), 1.90 (quin, 2H, J = 6.0 Hz, -CH2-CH2-CH2-), 2.71 (t, 2H, J = 6.0 Hz, Ar-CH2-), 2.73 (t, 2H, J = 6.0 Hz, -S-CH2-), 3.44 (q, 1H, J = 6.0 Hz, -CH-), 6.75 (t, 1H, J = 6.0 Hz, Ar-H), 6.81 (d, 1H, J = 6.0 Hz, Ar-H), 7.01 (t, 1H, J = 6.0 Hz, Ar-H), 7.09 (d, 1H, J = 6.0 Hz, Ar-H), 8.13 (s, 1H, Ar-OH), 10.2 (s, 1H, -COOH)

[0090] (Formula IV) JPEG0007695811000022.jpg3064

[0091] <<Example 5>> 2-Allylphenol was used as the alkenyl group phenols, and 3-mercaptopropionic acid was used as the thiol compound, and these were subjected to an enethiol reaction. Specifically, it is as follows.

[0092] A reaction product V was obtained in the same manner as in Example 1 except that the thiol compound was changed. With respect to the obtained reaction composition V, it was isolated with a mixed solvent of ethyl acetate / hexane by column chromatography, and the solvent was distilled off with an evaporator to obtain a compound represented by the following formula V in a yield of 90% as a light brown liquid.

[0093] 1H-NMR (400 MHz, Acetone-d6), 1.90 (quin, 2H, J = 6.0 Hz, -CH2-CH2-CH2-), 2.58 (t, 2H, J = 6.0 Hz, -CH2-), 2.60 (t, 2H, J = 6.0 Hz, -CH2-), 2.73 (t, 2H, J = 6.0 Hz, -CH2-), 2.75 (t, 2H, J = 6.0 Hz, -CH2-), 6.71 (t, 1H, J = 6.0 Hz, Ar-H), 6.86 (d, 1H, J = 6.0 Hz, Ar-H), 7.14 (t, 1H, J = 6.0 Hz, Ar-H), 7.28 (d, 1H, J = 6.0 Hz, Ar-H), 8.13 (s, 1H, Ar-OH), 10.2 (s, 1H, -COOH)

[0094] (Formula V) JPEG0007695811000023.jpg3564

[0095] [[Example 6]] 2-Allylphenol was used as the alkenyl group phenols and α-thioglycerol was used as the thiol compound, and they were subjected to an enethiol reaction. Specifically, it was as follows.

[0096] Reaction product VI was obtained in the same manner as in Example 1 except that the thiol compound was changed. For the obtained reaction composition VI, it was isolated by column chromatography with an ethyl acetate / hexane mixed solvent, and the solvent was distilled off with an evaporator to obtain a compound represented by the following formula VI in a yield of 90% as a light brown liquid.

[0097] 1H-NMR (400 MHz, Acetone-d6), 1.85 (quin, 2H, J = 6.0 Hz, -CH2-CH2-CH2-), 2.5 - 2.6 (m, 6H, Ar-CH2-, -S-CH2-CH2-, -CH2-OH), 3.51 (sext, 1H, J = 6.0 Hz, -CH-), 3.55 (d, 2H, J = 6.0 Hz, -S-CH2-CH2-), 3.70 (t, 1H, J = 6.0 Hz, -CH2-OH), 3.79 (s, 1H, J = 6.0 Hz, -CH-OH), 6.72 (t, 1H, J = 6.0 Hz, Ar-H), 6.80 (d, 1H, J = 6.0 Hz, Ar-H), 6.98 (t, 1H, J = 6.0 Hz, Ar-H), 7.06 (d, 1H, J = 6.0 Hz, Ar-H), 8.13 (s, 1H, Ar-OH)

[0098] (Formula VI) JPEG0007695811000024.jpg3064

[0099] [[Example 7]] 2-Allylphenol was used as the alkenyl group phenols and 2-ethyl-1-hexanethiol was used as the thiol compound, and they were subjected to an enethiol reaction. Specifically, it is as follows.

[0100] Reaction product VII was obtained in the same manner as in Example 1 except that the thiol compound was changed. For the obtained reaction composition VII, it was isolated with a mixed solvent of ethyl acetate / hexane by column chromatography, and the solvent was distilled off with an evaporator to obtain a compound represented by the following formula VII in a yield of 90% as a light brown liquid.

[0101] 1H-NMR (400 MHz, Acetone-d6), 0.864 (t, 3H, J = 6.0 Hz, -CH3), 0.892 (t, 3H, J = 6.0 Hz, -CH3), 1.3 - 1.4 (m, 9H, -CH-CH2-CH2-CH2-CH3, -CH2-CH3), 1.88 (quin, 2H, J = 6.0 Hz, -S-CH2-CH2-), 2.50 (d, 2H, J = 6.0 Hz, -S-CH2-CH-), 2.53 (t, 2H, J = 6.0 Hz, -S-CH2-), 2.71, (t, 2H, J = 6.0 Hz, Ar-CH2-), 6.71 (t, 1H, J = 6.0 Hz, Ar-H), 6.84 (d, 1H, J = 6.0 Hz, Ar-H), 7.00 (t, 1H, J = 6.0 Hz, Ar-H), 7.07 (d, 1H, J = 6.0 Hz, Ar-H), 8.15 (s, 1H, Ar-OH)

[0102] (Formula VII) JPEG0007695811000025.jpg3264

Claims

【Claim 1】 A compound represented by the following formula 1. (Formula 1) (In the formula, R １ ~R ４ independently represent H or an alkyl group having 3 or fewer carbon atoms, R ５ is -(CH ２ ) ｎ -S-R Ａ represents, n represents an integer of 2 or more and 4 or less, R Ａ represents the structure of the following formula 2.) (Formula 2) (In the formula, m represents an integer of 1 or more and 4 or less, R ｘ , R ｙ , R ｚ independently represent an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.)

Images