WO2011090008A1

WO2011090008A1 - Novel compound; method for synthesizing said compound; and antioxidant, release agent, resin composition, and resin mold product containing said compound

Info

Publication number: WO2011090008A1
Application number: PCT/JP2011/050695
Authority: WO
Inventors: 晴生岩沢; 知弘小畑; 彰基伊藤; 光男阿久津
Original assignee: Jsr株式会社
Priority date: 2010-01-19
Filing date: 2011-01-18
Publication date: 2011-07-28

Abstract

Provided are a novel compound exhibiting excellent heat resistance, a method for synthesizing said compound, and an antioxidant, a release agent, a resin composition, and a resin mold product which contain said compound. The compound is represented by general formula (1).

Description

NOVEL COMPOUND, METHOD FOR SYNTHESIZING THE COMPOUND, ANTIOXIDANT, RELEASE AGENT, RESIN COMPOSITION, AND RESIN MOLDED BODY CONTAINING THE COMPOUND

The present invention relates to an antioxidant for a polymer material such as a synthetic resin, a novel compound useful as a mold release agent, a method for synthesizing the compound, an antioxidant comprising the compound, a mold release agent, a resin composition, and It relates to a resin molded body.

Polymer materials such as synthetic resins are packaging materials, building materials, automotive parts, daily goods, agricultural materials, medical equipment, digital camera lenses, mobile phone lenses, because of their excellent mechanical and chemical properties. It is used in a wide range of applications such as optical lenses represented by CDs, Blu-ray pickup lenses, microlenses, substrates such as disks, light guide plates, and prism sheets.

In recent years, in the field of optical components, a molded product made of a transparent thermoplastic resin has been used from the viewpoint of processability and flexibility, and the surface of the molded product has diffusion, light collection, diffraction, reflection, etc. A fine shape for imparting optical properties is imparted. The compacts having these fine shapes can be obtained by injection molding, thermal transfer molding applying melt processing by a press method, or a method of transferring a fine shape previously formed on a metal surface by a known method.

This molded article made of a transparent thermoplastic resin is usually used as an optical element as it is, and an optical element obtained by a method of coating and curing an ultraviolet curable transparent resin on the surface of the molded article as a substrate. Also used as a transparent stamper to form.

However, polymer materials usually show deterioration phenomena such as coloring due to exposure to high temperatures during heat processing, easily lose their original functions, and may not be suitable for practical use. In addition, after a polymer material is used for various purposes, deterioration phenomena such as coloring may be seen over time.

As a method for suppressing this deterioration phenomenon such as coloring, a method of adding various antioxidants to a synthetic resin is known. Antioxidants used here include primary antioxidants such as phenolic antioxidants and amine antioxidants, and secondary antioxidants such as phosphorus antioxidants and thioether antioxidants.

Among these compounds, for example, the compounds shown in Patent Document 1 are known as phenolic antioxidants, and for example, the compounds shown in Patent Document 2 are known as phosphorus antioxidants. . However, these compounds have insufficient heat resistance and have problems such as decomposition when exposed to high temperatures during heat processing.

In addition, when a molded body having the above-mentioned fine shape is formed by injection molding or thermal transfer molding, it is difficult to release from the mold to be used, or the resin remains in the mold even if release is possible. Sometimes. Therefore, as a method for improving the releasability, a method of adding various release agents to the synthetic resin is known. Examples of the release agent used here include a fluorine-based release agent, a silicone-based release agent, and a fatty acid ester-based release agent.

As these release agents, for example, a silicone release agent as shown in Patent Document 3 is known. However, this release agent has insufficient heat resistance, and has a problem that it is decomposed by being exposed to a high temperature during heat processing.

Japanese Patent Laid-Open No. 08-040984 JP 2006-176706 A JP 2002-307523 A

The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a novel compound having high heat resistance, a method for synthesizing the compound, and an antioxidant, a release agent, a resin composition, and a resin molded body containing the compound.

The present inventors diligently studied to solve the above problems. As a result, it has been found that the above problem can be solved by using a compound having the following structure, and the present invention has been completed. That is, the present invention provides the following [1] to [10].

[1] A compound represented by the following formula (1).

In the formula (1), each L is independently a hydrogen atom, a group represented by the following formula (2), a group represented by the following formula (3), or R ⁸ CO— (R ⁸ is a group having 1 to 40 carbon atoms. Or a monovalent halogenated hydrocarbon group having 1 to 40 carbon atoms, and each R ⁴ independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. A hydrocarbon group or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and each R ⁵ independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent hydrocarbon group having 1 to 20 carbon atoms. A is a single bond, a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, -S-, -SO ₂ -, -CO- or -O-, m is an integer of 0 to 10, and n is an integer of 0 to 4. However, not all four Ls are hydrogen atoms.

In the formula (2), each R ¹ is independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and R ² is Each independently represents a single bond or —CO—, and each R ³ independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms. is there.

In the formula (3), each R ⁶ is independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and R ⁷ is These are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms.

[2] The compound according to [1], wherein in the formula (1), L is a group represented by the formula (2).
[3] The compound according to [2], wherein in the formula (2), R ² is a single bond.

[4] In the above formula (1), each L is independently a hydrogen atom or a group represented by the above formula (3), and at least one of the plurality of L is a group represented by the above formula (3). The compound according to [1].

[5] In the above formula (1), each L is independently a hydrogen atom or a group represented by R ⁸ CO—, and at least one of the plurality of L is a group represented by R ⁸ CO—. 1].

[6] An antioxidant containing the compound according to any one of [2] to [4].

[7] A mold release agent containing the compound according to [5].

[8] A resin composition containing the compound according to any one of [1] to [5].

[9] A resin molding containing the compound according to any one of [1] to [5].

[10] A step of reacting a compound represented by the following formula (4) with one compound selected from the group consisting of compounds represented by the following formula (5), the following formula (6) and the following formula (7). A method for synthesizing a compound represented by the following formula (1).

In the formula (4), each R ⁴ is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ is each independently And a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and A is a single bond and a divalent hydrocarbon group having 1 to 20 carbon atoms. , A divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, —S—, —SO ₂ —, —CO— or —O—, m is an integer of 0 to 10, and n is 0 to 4 Is an integer.

In the formula (5), each R ¹ is independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and R ³ is Each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and Y represents a group represented by R ⁹ SO ₃ —, hydroxyl group Group or carboxyl group. R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms.

In the formula (6), each R ⁶ is independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and R ⁷ is Each independently is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and X is a halogen atom.

In the formula (7), each R ⁸ independently represents a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 40 carbon atoms, and Z represents a hydroxy group, Or it is a halogen atom.

In formula (1), L is independently a hydrogen atom, a group represented a group represented by or R ⁸ CO- in group represented by the following formula (2), the following equation (3), R ⁸ is Each independently has the same meaning as R ⁸ in formula (7), and R ⁴ , R ⁵ , A, m and n are each independently R ⁴ , R ⁵ , A, m in formula (4). And n are synonymous. However, not all four Ls are hydrogen atoms.

In Formula (2), R ¹ and R ³ are each independently synonymous with R ¹ and R ^{3 in} Formula (5), and R ² is independently a single bond or —CO—.

In formula (3), R ⁶ and R ⁷ are each independently synonymous with R ⁶ and R ^{7 in} formula (6).

The novel compound of the present invention has high heat resistance. For this reason, this compound can be suitably used as an antioxidant or mold release agent for polymer materials such as synthetic resins.
In addition, it is possible to provide a resin composition and a resin molded body that are less prone to deterioration phenomena such as coloring and have excellent releasability.
Furthermore, the synthesis method according to the present invention can easily synthesize a high-purity novel compound with good yield.

Hereinafter, the novel compound of the present invention, a method for producing the compound, and an antioxidant, a release agent, a resin composition, and a resin molded body containing the compound will be described in detail.

[Compound]
The novel compound of the present invention is a compound represented by the following formula (1). In the following, the compound represented by the following formula (1) is also referred to as “compound (1)”.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ¹ , R ⁴ and R ⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, and a pentyl group. And alkyl groups having 1 to 20 carbon atoms such as hexyl group; cycloalkyl groups having 3 to 20 carbon atoms such as cyclopentyl group and cyclohexyl group; aromatic carbonization having 6 to 20 carbon atoms such as phenyl group, naphthyl group and biphenyl group Examples thereof include a hydrogen group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group and an allyl group.

Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms in R ¹ , R ⁴ and R ⁶ include a halogenated alkyl group having 1 to 20 carbon atoms, a halogenated cycloalkyl group having 3 to 20 carbon atoms, and Examples thereof include a halogenated aromatic hydrocarbon group having 6 to 20 carbon atoms. Examples of the halogenated alkyl group include a trichloromethyl group, a trifluoromethyl group, a tribromomethyl group, a pentachloroethyl group, a pentafluoroethyl group, and a pentabromoethyl group. As the halogenated cycloalkyl group, Examples thereof include a chlorocyclopentyl group and a chlorocyclohexyl group, and examples of the halogenated aromatic hydrocarbon group include a chlorophenyl group and a chloronaphthyl group.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in the above R ³ , R ⁵ , R ⁷ and A include divalent linear or branched hydrocarbon groups having 1 to 20 carbon atoms, And 20 divalent alicyclic hydrocarbon groups and 6 to 20 carbon divalent aromatic hydrocarbon groups.

Examples of the divalent linear or branched hydrocarbon group having 1 to 20 carbon atoms in R ³ , R ⁵ , R ⁷ and A include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, Alkylene groups such as hexamethylene group and heptamethylene group; branched chain alkylidene groups such as propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group and hexylidene group; alkenylene group; Can be mentioned. In these, an alkylene group is preferable.

Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms in R ³ , R ⁵ , R ⁷ and A include cyclopropylene group, cyclobutylene group, cyclopentylene group and cyclohexylene group. Alkylene group; cycloalkenylene groups such as cyclobutenylene group, cyclopentenylene group and cyclohexenylene group. The bonding site of the alicyclic hydrocarbon group may be on any carbon on the alicyclic ring.

Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms in R ³ , R ⁵ , R ⁷ and A include arylene groups such as a phenylene group, a biphenylene group and a naphthylene group.

Examples of the divalent halogenated hydrocarbon group having 1 to 20 carbon atoms in the above R ³ , R ⁵ , R ⁷ and A include at least hydrogen atoms of the divalent hydrocarbon group having 1 to 20 carbon atoms exemplified above. And a group in which one is substituted with a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom).

Examples of the monovalent hydrocarbon group having 1 to 40 carbon atoms in R ⁸ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Alkyl groups having 1 to 40 carbon atoms such as a group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, lauryl group, myristyl group, palmityl group, stearyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, A cycloalkyl group having 3 to 40 carbon atoms such as cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, etc .; phenyl group, toluyl group, xylyl group, naphthyl group, An aromatic hydrocarbon group having 6 to 40 carbon atoms such as benzyl group; vinyl group, allyl group, 1 Propenyl, 1,3-butadienyl group, isopropenyl group, 1-butenyl, 2-butenyl, and the like alkenyl group having 2 to 40 carbon atoms, such as 2-pentenyl group.

Examples of the monovalent halogenated hydrocarbon group having 1 to 40 carbon atoms in R ⁸ include a halogenated alkyl group having 1 to 40 carbon atoms, a halogenated cycloalkyl group having 3 to 40 carbon atoms, and a 6 to 40 carbon atom. And halogenated aromatic hydrocarbon groups. Examples of the halogenated alkyl group include trichloromethyl group, trifluoromethyl group, tribromomethyl group, pentachloroethyl group, pentafluoroethyl group, pentabromoethyl group, heptafluoropropyl group, heptabromopropyl group, nonafluorobutyl. Group, nonabromobutyl group, and the like. Examples of the halogenated cycloalkyl group include chlorocyclopentyl group and chlorocyclohexyl group. Examples of the halogenated aromatic hydrocarbon group include chlorophenyl group and chloronaphthyl group. It is done.

In the above formula (1),
Each A is preferably independently an isopropylidene group, —S—, —SO ₂ —, —CO—, or —O—.
n is preferably 0.

The compound (1) is a compound in which all four Ls are groups represented by the above formula (2) (hereinafter also referred to as “compound (1-1)”). It is preferable from the viewpoint of suppressing the compatibility with the resin and the deterioration phenomenon of the resin.

In compound (1-1),
R ¹ is preferably each independently a hydrogen atom or a monovalent hydrocarbon group having 3 to 20 carbon atoms, and at least one R ¹ bonded to any one aromatic ring has 3 to 20 carbon atoms. It is more preferable that one or two R ¹ adjacent to the —OH group bonded to the aromatic ring is a monovalent hydrocarbon group having 3 to 20 carbon atoms. The monovalent hydrocarbon group having 3 to 20 carbon atoms is particularly preferably a t-butyl group,
R ² is preferably independently a single bond,
R ³ is preferably each independently a divalent linear or branched hydrocarbon group having 1 to 20 carbon atoms, more preferably a methylene group, an ethylene group or a trimethylene group,
m is preferably 0 or 1, and more preferably 0.

In the above formula (2), when R ² is a single bond, the compound has an antioxidant effect, higher heat resistance, and excellent compatibility with the resin.

In addition, when the compound (1-1) is a compound represented by the following formula (1 ′) (hereinafter also referred to as “compound (1 ′)”), this compound is preferably used as an antioxidant. Can do.

Wherein ^{(1 '), R 1 ~} R 5, A, m and n have the same meanings as ^{^{R 1 ~ R 5, A,}} m and n in the formula (1) or (2).

Compound (1) is a compound in which L is independently a hydrogen atom or a group represented by the above formula (3) (provided that at least one of a plurality of L is a group represented by the above formula (3)). In the following, “compound (1-2)” is also preferable from the viewpoint of heat resistance of the compound, compatibility with the resin, and suppression of the deterioration phenomenon of the resin. It is more preferable that the compound be a group represented by

In compound (1-2),
R ⁶ is preferably independently a hydrogen atom or a monovalent hydrocarbon group having 3 to 20 carbon atoms, and at least one R ⁶ bonded to any one aromatic ring has 3 to 20 carbon atoms. More preferably, one or two of R ⁶ bonded to the ortho-position and para-position of the carbon atom on the aromatic ring bonded to the oxygen atom are monovalent having 3 to 20 carbon atoms. R ⁶ bonded to the ortho and para carbon atoms on the aromatic ring bonded to the oxygen atom is more preferably a monovalent hydrocarbon having 3 to 20 carbon atoms. More preferably, the monovalent hydrocarbon group having 3 to 20 carbon atoms is particularly preferably a t-butyl group,
R ⁷ is preferably each independently a divalent linear or branched hydrocarbon group having 1 to 20 carbon atoms, more preferably a methylene group, an ethylene group or a trimethylene group,
m is preferably 0 or 1, and more preferably 1.

Compound (1) is a compound wherein each L is independently a hydrogen atom or a group represented by R ⁸ CO— (provided that at least one of the plurality of L is a group represented by R ⁸ CO—. Compound (1-3) ”) is preferable from the viewpoint of the heat resistance of the compound, the compatibility with the resin, the releasability of the resin composition containing the compound and the resin molding, and the like. More preferably, the compounds are such that all Ls are groups represented by R ⁸ CO—. Incidentally, R ⁸ has the same meaning as R ⁸ in the compound described above (1).

In compound (1-3),
R ⁸ is preferably independently a monovalent hydrocarbon group having 5 to 40 carbon atoms, more preferably a monovalent hydrocarbon group having 10 to 30 carbon atoms,
R ⁵ is preferably each independently a divalent linear or branched hydrocarbon group having 1 to 20 carbon atoms, more preferably a methylene group, an ethylene group or a trimethylene group,
m is preferably 0 or 1, and more preferably 0.

[Method for Synthesizing Compound (1)]
The compound (1) of the present invention includes a compound represented by the following formula (4) (hereinafter also referred to as “compound (4)”) and a compound represented by the following formula (5) (hereinafter “compound (5)”). And a compound represented by the following formula (6) (hereinafter also referred to as “compound (6)”) and a compound represented by the following formula (7) (hereinafter also referred to as “compound (7)”). It can be synthesized by a method including a step of reacting one compound (i) selected from the group consisting of By reacting compound (4) with compound (i), high-purity novel compound (1) can be easily synthesized in good yield.

In the formula (4), R ⁴ , R ⁵ , A, m and n are each independently synonymous with R ⁴ , R ⁵ , A, m and n in the formula (1).

In formula (5), R ¹ and R ³ each independently have the same meaning as R ¹ and R ³ in the formula (2), Y is R ⁹ SO ₃ -, a group represented by a hydroxyl group Or it is a carboxyl group. R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms.

Examples of the hydrocarbon group having 1 to 20 carbon atoms in R ⁹ include the same functional groups as the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ¹ .

In the formula (6), R ⁶ and R ⁷ are independently the same as R ⁶ and R ⁷ in the formula (3), and X is a halogen atom.

In addition, the compound (6) can be obtained from Phosphorus and Sulfur, 1984, Vol. 19, pp. It can be synthesized by the method described in 285-293.

In the formula (7), R ⁸ is a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 40 carbon atoms, and Z is a hydroxy group or a halogen atom. . Incidentally, R ⁸ has the same meaning as R ⁸ in the compound described above (1).

The temperature and time of the above reaction are not particularly limited, but the reaction temperature is usually −30 to 120 ° C., preferably −20 to 90 ° C., particularly preferably −10 to 80 ° C .; the reaction time is usually 0 1 to 48 hours, preferably 0.5 to 24 hours, particularly preferably 1 to 10 hours.

<< Method for Synthesizing Compound (1-1) >>
The method for synthesizing the compound (1-1) is not particularly limited, but preferably includes a step of reacting the compound (4) and the compound (5).

In the reaction of compound (4) and compound (5), the molar ratio of compound (4) to compound (5) (compound (5) / compound (4)) is usually from 4 to 20, preferably 4.05-5.
When the compound (4) and the compound (5) are reacted in such an amount, the high-purity novel compound (1-1) can be easily synthesized with better yield.

<Synthesis Method of Compound (1-1) wherein R ² is —CO—>
In compound (1-1), a compound in which R ² is —CO— can be obtained by reacting compound (4) with a compound in which Y is a carboxyl group in compound (5) (hereinafter “ Also referred to as “Reaction (I)”).

The reaction (I) can be carried out in the presence of carbodiimide and / or a base catalyst. Examples of the carbodiimide include dicyclohexyl carbodiimide and diisopropyl carbodiimide.

The molar ratio of compound (5) to carbodiimide (carbodiimide / compound (5)) is usually 1 to 20, preferably 1.05 to 5.

Examples of the base catalyst include N, N-dimethylaminopyridine, triethylamine, pyridine and sodium carbonate.
The molar ratio of the compound (5) to the base catalyst (base catalyst / compound (5)) is usually 0.01 to 1, preferably 0.05 to 0.5.

In the above reaction (I), an organic solvent such as methylene chloride, chloroform, carbon tetrachloride and / or 1,2-dichloroethane, water or the like may be used as a solvent. The amount of the solvent to be used is generally 0.1-50 ml, preferably 1-20 ml, particularly preferably 2-10 ml, per 1 g of compound (5).

In the reaction (I), the molar ratio between the compound (4) and the compound (5), and the reaction temperature and time are the same as described above.

<Synthesis Method of Compound (1-1) wherein R ² is a Single Bond>
In the compound (1-1), the compound in which R ² is a single bond includes the compound (4) and the group (5) in which Y is a hydroxyl group or a group represented by R ⁹ SO ₃ — ⁹ is a hydrocarbon group having 1 to 20 carbon atoms.) (Hereinafter also referred to as “reaction (II)”).

The reaction (II) can be performed in the presence of a catalyst or the like. Examples of the catalyst include sodium hydride. The molar ratio of the compound (4) to the catalyst (catalyst / compound (4)) is usually 0.01 to 20, preferably 0.1 to 10.

In the reaction (II), an organic solvent such as N, N-dimethylacetamide, methylene chloride, chloroform, carbon tetrachloride and / or 1,2-dichloroethane, water or the like may be used as a solvent. The amount of the solvent to be used is generally 0.1 to 50 ml, preferably 1 to 20 ml, particularly preferably 2 to 10 ml or less per 1 g of compound (5).

In the reaction (II), the molar ratio between the compound (4) and the compound (5), and the reaction temperature and time are the same as described above.

<Synthesis Method of Compound (1 ′)>
In addition, when synthesize | combining a compound (1 '), what is necessary is just to use the compound represented by following formula (5') instead of a compound (5) in the said synthetic method.

In the formula (5 '), R ^1, R ³ and Y have the same meanings as R ^1, R ³ and Y in the formula (5).

<< Method for Synthesizing Compound (1-2) >>
The method for synthesizing the compound (1-2) is not particularly limited, but preferably includes a step of reacting the compound (4) and the compound (6) (hereinafter also referred to as “reaction (III)”).

In the reaction (III), the molar ratio of the compound (4) to the compound (6) (compound (6) / compound (4)) is usually 1 to 20, preferably 4 to 20, and more preferably 4.05. ~ 6.
When the compound (4) and the compound (6) are reacted in such an amount, the high-purity novel compound (1-2) can be easily synthesized with better yield.

In the above reaction (III), the reaction temperature and time are the same as described above.

The reaction (III) can be performed in the presence of a base catalyst or the like. Examples of the base catalyst include N, N-dimethylaminopyridine, triethylamine, pyridine and sodium carbonate.
The molar ratio of the compound (6) to the base catalyst (base catalyst / compound (6)) is usually 0.05 to 5, preferably 0.5 to 2.

In the reaction (III), an organic solvent such as methylene chloride, chloroform, carbon tetrachloride and / or 1,2-dichloroethane, water or the like may be used as a solvent. The amount of the solvent to be used is generally 0.1-50 ml, preferably 1-20 ml, particularly preferably 2-10 ml per 1 g of compound (6).

<< Method of Synthesizing Compound (1-3) >>
The method for synthesizing the compound (1-3) is not particularly limited, but preferably includes a step of reacting the compound (4) and the compound (7) (hereinafter also referred to as “reaction (IV)”).

In the reaction (IV), the molar ratio of the compound (4) to the compound (7) (compound (7) / compound (4)) is usually 1 to 20, preferably 4 to 20, and more preferably 4.05. ~ 5.
When compound (4) and compound (7) are reacted in such an amount, novel compound (1-3) with high purity can be easily synthesized with better yield.

In the above reaction (IV), the reaction temperature and time are the same as described above.

Examples of the compound (7) include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid. Acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, linoglyceric acid, serotic acid, heptacosanoic acid, montanic acid, mellicic acid, laccellic acid, isopropionic acid, isovaleric acid, isobutyric acid, 2-methyl Butyric acid, cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cycloheptanecarboxylic acid, cyclooctanecarboxylic acid, cyclopropylacetic acid, cyclobutylacetic acid, cyclopentylacetic acid, cyclohexylacetic acid, cycloheptylacetic acid Cyclooctylacetic acid, norbornanecarboxylic acid, dinorbornanecarboxylic acid, norbornaneacetic acid, dinorbornaneacetic acid, 4-methylcyclohexanecarboxylic acid, 4-ethylcyclohexanecarboxylic acid, 4-propylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4- Propylcyclohexanecarboxylic acid, 4-methyldicyclohexanecarboxylic acid, 4-ethyldicyclohexanecarboxylic acid, 4-propyldicyclohexanecarboxylic acid, 4-butyldicyclohexanecarboxylic acid, 4-propyldicyclohexanecarboxylic acid, cholestanoic acid, trifluoro Examples include acetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluorovaleric acid, and halides of these acids.

The reaction (IV) can be performed in the presence of carbodiimide and / or a base catalyst. Examples of the carbodiimide include dicyclohexyl carbodiimide and diisopropyl carbodiimide.

The molar ratio of compound (7) to carbodiimide (carbodiimide / compound (7)) is usually 1 to 20, preferably 1.05 to 5.

Examples of the base catalyst include N, N-dimethylaminopyridine, triethylamine, pyridine and sodium carbonate.
The molar ratio of the compound (7) to the base catalyst (base catalyst / compound (7)) is usually 0.01 to 1, preferably 0.03 to 0.5.

In the above reaction, an organic solvent such as methylene chloride, chloroform, carbon tetrachloride and / or 1,2-dichloroethane, water or the like may be used as a solvent. The amount of the solvent to be used is generally 0.1-50 ml, preferably 1-20 ml, more preferably 2-15 ml per g of compound (7).

<Synthesis Method of Compound (4)>
The compound (4) can be obtained by a known method. For example, a compound represented by the following formula (9) by hydrogenating a compound represented by the following formula (8) (hereinafter referred to as the compound ( 9).) Step (i), wherein the compound (9) is oxidized to obtain a compound represented by the following formula (10) (hereinafter also referred to as compound (10)) (ii), compound ( 10) and a compound represented by the following formula (11) (hereinafter also referred to as compound (11)) and a compound (hereinafter referred to as compound (11 ′) obtained in step (iii) and step (iii) And a production method comprising a step (iv) of reacting an alkylene carbonate or a compound represented by the following formula (12) (hereinafter also referred to as compound (12)) in this order. Can do. In the compound (4), when a compound in which m is 0 is synthesized, the above step (iv) is not necessary.

(In Formula (8), A is synonymous with A in Formula (1).)

(In formula (9), A has the same meaning as A in formula (1).)

(In Formula (10), A is synonymous with A in Formula (1).)

(In the formula (11), R ⁴ and n have the same meanings as R ⁴ and n in the formula (1).)

In the compound (11), a compound in which R ⁴ is bonded to the para position of phenol is not preferable.

(In the formula (12), R ⁵ and m are as defined and R ⁵ and m in the formula (1), X 'is a halogen atom.)
A conventionally known method can be applied to the step (i).

In the step (ii), a conventionally known method can be applied. For example, the compound (9) may be reacted in the presence of an oxidizing agent and a solvent.

Examples of the oxidizing agent include hypohalous acids such as hypochlorous acid and hypobromite, salts thereof, and halogens such as chlorine.
The molar ratio of compound (9) to oxidant (oxidant / compound (9)) is preferably 2 to 3, more preferably 2.1 to 2.3.

The solvent is not particularly limited, but is preferably a solvent that does not easily react with the oxidizing agent and has high solubility for the compound (9). For example, methanol, acetic acid, toluene, chlorobenzene, dioxane, and these are used. The mixed solvent containing can be mentioned.
The amount of the solvent to be used is generally 0.1 to 50 ml per 1 g of compound (9).

The conditions for this step (ii) are not particularly limited, but the reaction temperature is usually from 0 ° C. to the boiling point of the solvent, preferably from 10 to 40 ° C .; the reaction time is usually from 0.1 to 10 hours.

The step (iii) can be produced by a conventionally known method. For example, the compound (10) and the compound (11) may be reacted in the presence of an acid catalyst.

The molar ratio of compound (10) to compound (11) (compound (11) / compound (10)) is usually from 4 to 50, preferably from 4 to 10.

Examples of the acid catalyst include inorganic acids such as hydrogen chloride gas, hydrochloric acid, sulfuric acid and phosphoric acid, and organic acids such as P-toluenesulfonic acid, oxalic acid and methanesulfonic acid.
The weight ratio of the compound (10) to the acid catalyst (acid catalyst / compound (10)) is preferably 0.05 to 1, more preferably 0.3 to 0.7.

In the step (iii), an appropriate cocatalyst, for example, an alkyl mercaptan such as methyl mercaptan, ethyl mercaptan, dodecyl mercaptan and / or octyl mercaptan can be added together with the acid catalyst to promote the reaction.
The weight ratio of the compound (10) to the promoter (promoter / compound (10)) is preferably 0.01 to 0.1, more preferably 0.02 to 0.06.

In the step (iii), a solvent may be used as necessary. For example, aromatic compounds such as benzene, toluene and xylene, saturated hydrocarbons such as n-hexane, cyclohexane and n-pentane, methanol and t-butanol Alcohols such as can be used alone or in combination.
The weight ratio of the compound (11) to the solvent (solvent / compound (11)) is preferably 0.01 to 10, more preferably 0.1 to 2.

The conditions for this step (iii) are not particularly limited, but the reaction temperature is usually from 0 ° C. to 60 ° C., preferably from 10 to 40 ° C .; the reaction time is usually from 1 to 10 hours, preferably 1-5 hours.

The step (iv) can be produced by a conventionally known method. For example, the compound (11 ′) (a compound in which m = 0 in the compound (4)) and an alkylene carbonate or the compound (12) May be reacted in the presence of a base catalyst.

The molar ratio of compound (11 ′) to alkylene carbonate (alkylene carbonate / compound (11 ′)) is usually from 4 to 20, preferably from 4 to 10, and the compound (11 ′) and compound (12) The molar ratio (compound (12) / compound (11 ′)) is usually 4 to 20, preferably 4 to 10.

Here, examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, and butylene carbonate.

Examples of the base catalyst include carbonates such as potassium carbonate and sodium carbonate, quaternary ammonium salts such as tetrabutylammonium bromide, tetrabutylammonium chloride, tetramethylammonium bromide and tetramethylammonium chloride.
The weight ratio of the compound (11 ′) to the base catalyst (base catalyst / compound (11 ′)) is preferably 0.01 to 1, more preferably 0.05 to 0.5.

In step (iv), a solvent may be used as necessary. For example, a polar aprotic solvent such as N, N-dimethylformamide, acetonitrile and / or dimethyl sulfoxide, etc. may be used alone or in combination. Can be used.
The weight ratio of the compound (11 ′) to the solvent (solvent / compound (11 ′)) is preferably 0.01 to 10, and more preferably 0.1 to 2.

The conditions for this step (iv) are not particularly limited, but the reaction temperature is usually 0 ° C. to 200 ° C., preferably 30 to 160 ° C .; the reaction time is usually 1 to 10 hours, preferably 1-5 hours.

<Synthesis Method of Compound (5) wherein Y is a Group Represented by R ⁹ SO ₃ —>
In the compound (5), the compound in which Y is a group represented by R ⁹ SO ₃ — (wherein R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms) It can be obtained by reacting a compound in which Y is a hydroxyl group with a compound represented by the following formula (13) (hereinafter also referred to as “compound (13)”) (hereinafter referred to as “reaction (V)”). Say.).

In the formula (13), R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms, and X is a halogen atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms in R ⁹ include the same functional groups as the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ¹ .

In the reaction (V), the molar ratio of the compound (5) to the compound (13) (compound (13) / compound (5)) is usually 1 to 20, preferably 2 to 5.

Reaction (V) can be performed in the presence of a base catalyst. Examples of the base catalyst include N, N-dimethylaminopyridine, triethylamine, pyridine and sodium carbonate. The molar ratio of the compound (13) to the base catalyst (base catalyst / compound (13)) is usually 0.01 to 10, preferably 0.1 to 5.

In the reaction (V), an organic solvent such as N, N-dimethylacetamide, methylene chloride, chloroform, carbon tetrachloride and / or 1,2-dichloroethane, water or the like may be used as a solvent. The amount of the solvent to be used is generally 0.1-50 ml, preferably 1-20 ml, particularly preferably 2-10 ml per g of compound (5).

The conditions for the reaction (V) are not particularly limited, but the reaction temperature is usually −30 to 120 ° C., preferably −20 to 90 ° C., particularly preferably −10 to 80 ° C .; the reaction time is usually 0.1 to 48 hours, preferably 0.5 to 24 hours, particularly preferably 1 to 10 hours.

[Antioxidant]
The antioxidant according to the present invention only needs to contain the compound (1), and preferably consists essentially of the compound (1), and contains the compound (1-1) or the compound (1-2). More preferably.

Since the compound (1-1) and the compound (1-2) are excellent in heat resistance and compatibility with the resin, the resin and the resin that are exposed to a high temperature particularly during processing and molding. It can be suitably used as an antioxidant for molded articles.

[Release agent]
The release agent according to the present invention only needs to contain the compound (1), preferably consists essentially of the compound (1), and more preferably contains the compound (1-3).

Since the compound (1-3) is excellent in heat resistance and compatibility with the resin, it is particularly suitable as a mold release agent for resins and resin moldings that may be exposed to high temperatures during processing and molding. It can be preferably used.

[Resin composition]
The resin composition according to the present invention contains the compound (1). The resin composition of the present invention preferably contains a resin and the compound (1).

Examples of the resin include cyclic olefin polymer, acrylic resin (PMMA), polycarbonate resin (PC), polyarylate resin (PAR), polysulfone resin (PSF), polyethersulfone resin (PES), polyparaphenylene resin ( PPP), polyarylene ether phosphine oxide resin (PEPO), polyimide resin (PPI), polyetherimide resin (PEI), and polyamideimide resin (PAI). Among these resins, a cyclic olefin polymer is preferably used from the viewpoint of compatibility with the compound (1).

In the resin composition, the compound (1) content is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin.

[Resin molding]
The resin molding which concerns on this invention contains the said compound (1). The resin molded body of the present invention is preferably obtained by molding the above resin composition.

Such a resin molded body is not particularly limited, but specifically, packaging materials, building materials, automotive parts, daily goods, agricultural materials, medical instruments, digital camera lenses, mobile phone lenses Examples thereof include resin moldings used in a wide range of applications such as optical lenses represented by CDs, Blu-ray pickup lenses, microlenses, substrates such as disks, light guide plates and prism sheets.

The compound (1-1) and the compound (1-2) are particularly excellent in heat resistance and compatibility with the resin. The resin composition and the resin molded body containing the compounds (1-1) and (1-2) are excellent in storage stability, and particularly, deterioration phenomenon such as coloring does not easily occur even when exposed to high temperature.

The above compound (1-3) is particularly excellent in heat resistance. The resin composition and resin molding containing the compound (1-3) are excellent in releasability, and particularly excellent in work moldability even when exposed to high temperatures.

The present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples.

(Synthesis Example 1)
To a 1 L three-necked flask equipped with a dropping funnel and a thermometer, 3- (3 ′, 5′-di-tert-butyl-4′-hydroxy-phenyl) -propyl alcohol represented by the following formula (3-A) 8 g (0.4 mol) was weighed out and dissolved in 500 ml of methylene chloride under a nitrogen atmosphere, and the flask was cooled in an ice bath. To this solution, 121 g (1.2 mol) of triethylamine was added, and then the solution temperature was kept at 5 ° C. or lower, and 105.4 g (0.92 mol) of methanesulfonyl chloride was added dropwise through a dropping funnel over 90 minutes. Next, the ice bath was removed, the temperature was raised to 20 ° C., the mixture was stirred at 20 ° C. for 1 hour, ice water was added to the reaction solution, and the methylene chloride layer was separated by a liquid separation operation. The methylene chloride layer was further washed with 200 ml of distilled water, dried over magnesium sulfate and filtered, and then the solvent was distilled off to obtain 137 g of a crude product (methanesulfonate).

3. In a 1 L three-necked flask equipped with a dropping funnel and a thermometer, 3.84 g (160 mmol) of sodium hydride purified from a sodium hydride mineral oil suspension was weighed. To this, 100 ml of N, N-dimethylacetamide was added under a nitrogen atmosphere to form a suspension, and then cooled in an ice bath. Next, 18.5 g of 4,4 ′, 4 ″, 4 ′ ″-[(1-methylethylidene) di-4-cyclohexanyl-1-ylidene] tetrakisphenol represented by the following formula (2-A) (32 mmol) was dissolved in 100 ml of N, N-dimethylacetamide and added dropwise to the suspension over 30 minutes. This solution was stirred for 30 minutes under ice-cooling, and then a solution of 54.8 g (160 mmol) of the methanesulfonate synthesized above in 200 ml of N, N-dimethylacetamide was dropped into this solution over 30 minutes. . After 30 minutes, the solution was warmed to room temperature and after another 30 minutes, it was warmed to 70 ° C. After 5 hours, the reaction solution was cooled to room temperature, and ammonium chloride was poured into the reaction solution to complete the reaction. The solution after the reaction was extracted with 300 ml of ethyl acetate three times, and the organic layer was collected and washed with distilled water, and this was distilled off under reduced pressure to obtain a crude product. This crude product was purified by silica gel column chromatography to obtain 35.1 g of a white solid from an ethyl acetate-hexane fraction. Further, 35.1 g of this white solid was recrystallized with a mixed solvent of diethyl ether-hexane to obtain 30.3 g (yield 61%) of the desired product represented by the following formula (1-A).

¹ H-NMR measurement of this compound (AVANCE500 type manufactured by Bruker Co., Ltd.), MS analysis (ACQUITY UPLC ® system manufactured by Nippon Waters Co., Ltd.) and analysis by SYNPT HDMS (High Definition Mass Spectrometry) system and TG-DTA The company made TG8120) and confirmed that the desired compound was obtained. The analysis results were as follows.

¹ H-NMR (solvent: CDCl ₃ ) chemical shift σ: 7.23 ppm (aromatic ring hydrogen, 4H), 7.03 ppm (aromatic ring hydrogen, 4H), 6.99 ppm (aromatic ring hydrogen, 4H), 6.96 ppm (Aromatic ring hydrogen, 4H), 6.83 ppm (aromatic ring hydrogen, 4H), 6.72 ppm (aromatic ring hydrogen, 4H), 5.01 ppm (phenolic hydroxyl group, 4H), 3.95 ppm (aromatic ring —O—) _{C H 2 -, 4H),} 3.89ppm ( aromatic _{-O-C H 2 -, 4H} ), 2.73ppm ~ 2.65ppm (12H), 2.03ppm ( aromatic ring -CH _₂ -C H ₂ - CH _2- , 8H), 1.84 ppm (cyclohexane cyclic hydrogen, 4H), 1.58 ppm to 1.21 ppm (14H), 1.41 ppm (tert-butyl group, 72H), 0.52 ppm (methyl group, 6H) .

LC-MS: [M ⁺ + Na] = 1585.1150 (calc. 1185.1106), [M ⁺ + K] = 1601.1073 (calc. 1601.0846)
TG-DTA: melting point = 170 ° C.]

(Synthesis Example 2)
4,4 ′, 4 ″, 4 ′ ″-[(1-methylethylidene) di-4-cyclohexanyl-1-ylidene] tetrakisphenol 25.9 g (45 mmol) represented by the above formula (2-A) ), And 56.2 g (202.5 mmol) of 3- (3 ′, 5′-di-tert-butyl-4′-hydroxy-phenyl) -propionic acid represented by the following formula (3-B) The solution was weighed into a three-necked flask, dissolved in 800 ml of methylene chloride, and cooled in an ice bath. After cooling, 44.5 g (216 mmol) of dicyclohexylcarbodiimide and 2.7 g (25 mmol) of N, N-dimethylaminopyridine were added to the solution and stirred under a nitrogen atmosphere. After 30 minutes, the reaction solution was warmed to room temperature and stirred at room temperature of 25 ° C. for 4 hours. After 4 hours, the solvent-insoluble matter precipitated in the reaction solution was removed by suction filtration, and the solvent-soluble matter was collected and distilled off under reduced pressure. When the total amount of the residue solution reached about 500 ml, the residue solution was transferred to a separatory funnel, washed with 100 ml of 10% dilute hydrochloric acid, then washed with 100 ml of saturated aqueous sodium hydrogen carbonate solution, and washed twice with 100 ml of distilled water. Then, it was dried with magnesium sulfate. The dried solution was filtered and evaporated under reduced pressure to obtain a white solid as a crude product of the target product. The white solid was recrystallized from n-hexane to obtain 52.6 g (yield 72%) of the target compound represented by the following formula (1-B).

¹ H-NMR measurement (AVANCE500 type manufactured by Bruker Co., Ltd.), MS analysis (ACQUITY UPLC ® system manufactured by Nihon Waters Co., Ltd.) system and SYNAPT HDMS (High Definition Mass Spectrometry) system, analysis by TG-DTA The company made TG8120) and confirmed that the desired compound was obtained. The analysis results were as follows.

¹ H-NMR (solvent: CDCl ₃ ) Chemical shift σ: 7.32 ppm (aromatic ring hydrogen, 4H), 7.12 ppm (aromatic ring hydrogen, 4H), 7.04 ppm (aromatic ring hydrogen, 4H), 7.02 ppm (Aromatic ring hydrogen, 4H), 6.99 ppm (aromatic ring hydrogen, 4H), 6.85 ppm (aromatic ring hydrogen, 4H), 5.08 ppm (phenolic hydroxyl group, 4H), 2.97 ppm (aromatic ring—OCO—) C H _2- , 4H), 2.82 ppm (aromatic ring-OCO-C H _2- , 4H), 2.66 ppm (cyclohexane cyclic hydrogen, 2H), 1.90 ppm to 1.21 ppm (16H), 1.43 ppm (Tert-butyl group, 72H), 0.51 ppm (methyl group, 6H).

LC-MS: [M ⁺ + Na] = 1641.0172 (calc. 1641.0277), [M ⁺ + K] = 1657.240 (calc. 1657.0016)
TG-DTA: Melting point = 181 ° C.

(Synthesis Example 3)
4,4 ′, 4 ″, 4 ′ ″-[(1-methylethylidene) di-4-cyclohexanyl-1-ylidene] tetrakisphenol 100 g (173 mmol) represented by the above formula (2-A), Add 122 g (1384 mmol) of ethylene carbonate, 11.1 g (35 mmol) of tetrabutylammonium bromide and 100 ml of N, N-dimethylformamide to a 500 ml three-necked flask equipped with a Dimroth condenser and a thermometer, and stir at 150 ° C. for 4 hours. I did it. The reaction mixture was cooled, N, N-dimethylformamide was distilled off under reduced pressure, 500 ml of chloroform was added, and the mixture was transferred to a separatory funnel. 100 ml of 5% aqueous potassium hydroxide solution was added thereto, and the organic layer was separated. To this organic layer was further added 100 ml of 5% aqueous potassium hydroxide solution, and the organic layer was separated. Thereafter, this solution was washed twice with 100 ml of distilled water. The chloroform solution obtained here was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystals were recrystallized from ethyl acetate to obtain 111 g (yield 85%) of a compound represented by the following formula (2-B).

It was confirmed that the target compound was obtained by ¹ H-NMR measurement of this compound (AVANCE500 type manufactured by Bruker Co., Ltd.). The analysis results were as follows.

¹ H-NMR (solvent: CDCl ₃ ) chemical shift σ: 7.25 ppm (aromatic ring hydrogen, 4H), 7.05 ppm (aromatic ring hydrogen, 4H), 6.86 ppm (aromatic ring hydrogen, 4H), 6.75 ppm (Aromatic ring hydrogen, 4H), 4.07 ppm (aromatic ring —O—C H ₂ —, 4H), 4.01 ppm (aromatic ring —O—C H ₂ —, 4H), 3.95 ppm (aromatic ring —O _{_{-CH 2 -C H 2 -OH, 4H}} ), 3.90ppm ( aromatic _{_{-O-CH 2 -C H 2 -OH}} , 4H), 2.63ppm ( cyclohexane cyclic hydrogen, 4H), 1.99ppm (hydroxyl Hydrogen, 2H), 1.94 ppm (hydroxyl hydrogen, 2H), 1.84 ppm (cyclohexane cyclic hydrogen, 4H), 1.60 ppm (cyclohexane cyclic hydrogen, 4H), 1.38 ppm (cyclohexane cyclic hydrogen, 2H). 20 pm (cyclohexane cyclic hydrogen, 4H), 0.52ppm (methyl, 6H).

3.07 g (4.09 mmol) of the compound represented by the above formula (2-B) synthesized in the above step and 3- (3 ′, 5′-di-tert-butyl-) represented by the above formula (3-B) 4'-Hydroxy-phenyl) -propionic acid (5.0 g, 18.0 mmol) was weighed into a 100 mL three-necked flask and dissolved in 40 mL of methylene chloride. To this solution, 4.05 g (19.6 mmol) of dicyclohexylcarbodiimide and 0.25 g (2.0 mmol) of N, N-dimethylaminopyridine were added and stirred under a nitrogen atmosphere. After stirring for 4 hours, the solvent-insoluble matter deposited in the reaction solution was removed by suction filtration, and the solvent-soluble matter was collected and distilled off under reduced pressure. The residue solution is dissolved in 100 ml of chloroform, transferred to a separatory funnel, washed with 20 ml of 10% dilute hydrochloric acid, then washed with 20 ml of a saturated aqueous sodium bicarbonate solution, and further washed twice with 20 ml of distilled water, and then with magnesium sulfate. Dried. The solution after drying was filtered and evaporated under reduced pressure to obtain a white solid as a crude product of the target product. This white solid was purified by silica gel column chromatography, and 4.23 g (yield 58%) of the target compound represented by the following formula (1-C) was obtained from the ethyl acetate: n-hexane fraction.

This compound was subjected to ¹ H-NMR measurement (AVANCE500 type, manufactured by Bruker Co., Ltd.) and analyzed by TG-DTA (TG8120, manufactured by Rigaku Corporation), and it was confirmed that the target compound was obtained. The analysis results were as follows.

¹ H-NMR (solvent: CDCl ₃ ) Chemical shift σ: 7.25 ppm (aromatic ring hydrogen, 4H), 7.05 ppm (aromatic ring hydrogen, 4H), 6.98 ppm (aromatic ring hydrogen, 8H), 6.84 ppm (aromatic hydrogen, 4H), 6.73ppm (aromatic hydrogen, 4H), 5.05 ppm (phenolic hydroxyl group, 4H), 4.43ppm (aromatic _{_{-O-CH 2 -C H 2 -OC}} = O, 4H), 4.38ppm (aromatic _{_{-O-CH 2 -C H 2 -OC}} = O), 4.14ppm ( aromatic _{-O-C H 2 -, 4H} ), 4.08ppm ( aromatic -O- _{C H 2 -, 4H),} 2.87ppm ( aromatic ring _{_{-CH 2 -C H 2 -C = O}} , 4H), 2.63ppm ( aromatic ring _{_{-C H 2 -CH 2 -C = O}} , cyclohexane cyclic hydrogen , 12H), 1.84 ppm (cyclohexane cyclic hydrogen, 4H), 1. 60 ppm (cyclohexane cyclic hydrogen, 4H), 1.38 to 1.20 ppm (t-butyl group, cyclohexane cyclic hydrogen, 78H), 0.52 ppm (methyl group, 6H).

(Synthesis Example 4)
4,4 ′, 4 ″, 4 ′ ″-[(1-methylethylidene) di-4-cyclohexanyl-1-ylidene] tetrakisphenol 5.0 g (8) represented by the above formula (2-A) .67 mmol), 5.27 g (2.2 mmol) of potassium carbonate and 75 ml of dimethylacetamide were added to a 500 ml three-necked flask equipped with a Dimroth condenser and a thermometer, and the mixture was heated and stirred at 140 ° C. for 1 hour. Subsequently, the reaction solution was allowed to cool to room temperature, 5.58 g (69.35 mmol) of 2-chloroethanol and 0.28 g (0.87 mmol) of tetrabutylammonium bromide were added, and the mixture was heated and stirred at 140 ° C. for 2 hours. Thereafter, the reaction vessel was cooled to room temperature, 100 ml of distilled water was added, and then the organic layer was extracted with 100 ml of ethyl acetate. After this extraction operation was repeated twice more, the organic layer obtained here was collected and further washed twice with 100 ml of distilled water. After the organic layer was distilled off under reduced pressure, a crude product of the target compound was obtained. The crude product obtained here was purified by silica gel column chromatography, and 5.67 g (yield 87%) of the compound represented by the above formula (2-B) was obtained from the ethyl acetate-n-hexane fraction. .

This compound was subjected to ¹ H-NMR measurement (AVANCE500 type manufactured by Bruker Co., Ltd.) to confirm that the target compound was obtained. The analysis results were as follows.

¹ H-NMR (solvent: CDCl ₃ ) Chemical shift σ: 7.26 ppm (aromatic ring hydrogen, 4H), 7.05 ppm (aromatic ring hydrogen, 4H), 6.86 ppm (aromatic ring hydrogen, 4H), 6.75 ppm (Aromatic ring hydrogen, 4H), 4.07 ppm (aromatic ring —OC H ₂ —CH ₂ —OH, 4H), 4.01 ppm (aromatic ring —OC H ₂ —CH ₂ —OH, 4H), 3.95 ppm ( aromatic ring _{_{-OCH 2 -C H 2 -OH, 4H}} ), 3.90ppm ( aromatic ring _{_{-OCH 2 -C H 2 -OH, 4H}} ), 2.63ppm ( cyclohexyl ring on hydrogen, 4H), 1.98ppm ( aromatic ring _{_{-OCH 2 -CH 2 -O H, 4H}} ), 1.84ppm ( cyclohexyl ring on hydrogen, 4H), 1.59ppm (cyclohexyl ring on hydrogen, 4H), 1.38ppm (cyclohexyl ring on hydrogen, 2H) 1 20 ppm (cyclohexyl ring on hydrogen, 4H), 0.52ppm (methyl, 6H).

1.85 g (2.458 mmol) of the compound represented by the above formula (2-B) synthesized in the above step was weighed into a 100 ml three-necked flask equipped with a dropping funnel and a thermometer, and 15 ml of methylene chloride was added under a nitrogen atmosphere. Dissolved and ice-cooled. To this solution, 1.49 g (14.7 mmol) of triethylamine was added. Next, 5.77 g (11.8 mmol) of 2,4,8,10-tetra-tert-butyl-6-chloro-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin was added to methylene chloride. After dissolving in 40 ml, the dropping funnel was opened and dripped into the reaction solution over 1 hour. 30 minutes after the completion of dropping, the ice container was removed from the reaction container, and the mixture was further stirred at room temperature of 23 ° C. for 4 hours. Next, the reaction vessel was transferred to a separatory funnel, 100 ml of distilled water was added, the organic layer was extracted with 100 ml of chloroform, this extraction operation was repeated three times, the organic layer was collected, and the organic layer was washed with distilled water. The organic layer was dried over magnesium sulfate and then distilled off under reduced pressure to obtain the target crude crystal. The structure of this crude crystal was confirmed by ¹ H-NMR measurement (AVANCE500 type manufactured by Bruker Co., Ltd.) and GPC analysis (HLC-8020 manufactured by Tosoh Corporation). In addition to the compound (1-D), the above formula (2 -B) one to three hydroxyl groups of the compound represented by 2,4,8,10-tetra-tert-butyl-6-chloro-12H-dibenzo [d, g] [1,3,2] dioxa It was confirmed that the compound obtained by reacting with phosphocin was present.

The crude crystal was recrystallized three times with isopropyl alcohol to obtain 4.59 g (yield 73%) of a target white crystal represented by the following formula (1-D).

This compound was analyzed by ¹ H-NMR measurement (AVANCE500 type manufactured by Bruker, Inc.) and ³¹ P-NMR measurement (AVANCE500 type manufactured by Bruker, Inc.), and it was confirmed that the target compound was obtained. The analysis results were as follows.

¹ H-NMR (solvent: CDCl ₃ ) Chemical shift σ: 7.30 ppm (aromatic ring hydrogen, 8H), 7.26 ppm (aromatic ring hydrogen, 12H), 7.08 ppm (aromatic ring hydrogen, 4H), 6.92 ppm (aromatic hydrogen, 4H), 6.81ppm (aromatic hydrogen, 4H), 4.78 ppm (aromatic ring _{_{-OCH 2 -C H 2 -OP, 4H}} ), 4.72ppm ( aromatic ring -OCH ₂ -C H ₂ -OP, 4H), 4.35 ppm (aromatic ring —OC H ₂ —CH ₂ —OP and Ph—C H ₂ —Ph, 8H), 4.29 ppm (aromatic ring —OC H ₂ —CH ₂ —OP, 4H), 3.44 ppm (Ph—C H ₂ —Ph, 4H), 2.66 ppm (hydrogen on the cyclohexyl ring, 4H), 1.87 ppm (hydrogen on the cyclohexyl ring, 4H), 1.60 ppm (hydrogen on the cyclohexyl ring) 4H), 1 45ppm ~ 1.14ppm (tert- butyl group, 144H, cyclohexyl ring on hydrogen, 6H), 0.52ppm (methyl, 6H).

³¹ P-NMR (solvent: CDCl ₃ ) Chemical shift σ: 130.22 ppm, 130.10 ppm (phosphite, CH ₂ —OP (aromatic) ₂ ).

(Evaluation Example 1) Antioxidation Effect 1 kg of a 10% (wt / wt) toluene solution of an ARTON resin (ARTON R5300, manufactured by JSR Corporation) was prepared, and the compound synthesized in Synthesis Example 1, 2 or 4 or Irganox 1010 (manufactured by Nippon Ciba-Geigy Co., Ltd.), which is a typical commercially available phenolic antioxidant, was added in an amount of 0.3 g (0.3% with respect to the ARTON resin) and dissolved. Subsequently, after filtering with a PTFE filter, the toluene solution was distilled off under reduced pressure and concentrated and solidified. The solid was heated at 330 ° C. for 3 hours under an argon atmosphere, then redissolved in toluene, adjusted to a 10% (w / w) toluene solution, and the yellowness was measured. The results are shown in Table 1.

(Evaluation example 2) Thermal analysis (TG-DTA)
Weights of the compounds synthesized in Synthesis Examples 1 to 4 above, Irganox 1010 (manufactured by Ciba Geigy Japan) Irgafos 168 (manufactured by Ciba Geigy Japan) and Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.) at 300 ° C. for 1 hour The decrease rate was measured by TG-DTA (TG8120 manufactured by Rigaku Corporation).
Measurement conditions: In a nitrogen atmosphere, the temperature was raised to 300 ° C. at 40 ° C./min, then held at 300 ° C. for 1 hour, and the weight reduction rate was calculated. The results are shown in Table 2.

For the compounds synthesized in Synthesis Examples 1 to 4, the weight reduction rate is small compared to Irganox 1010, Irgafos 168, and Sumilizer GP, and the compounds synthesized in Synthesis Example 1 and Synthesis Example 4 have a particularly weight reduction rate. I found it small.

(Evaluation Example 3) Storage stability 0.9 g of ARTON resin (ARTON R5300, manufactured by JSR Corporation) and 0.1 g of the compound synthesized in Synthesis Example 1 were mixed, and the mixture was dissolved in 9 g of methylene chloride. A solution having a solid content concentration of 10 wt% was prepared. The solution was applied to a petri dish, dried, and allowed to stand overnight to form a film. Then, after peeling off the obtained film from a petri dish, it dried at 100 degreeC with the vacuum dryer for 24 hours. The obtained film was cut into a test tube and heated at 300 ° C. for 18 hours using a solder bath while flowing nitrogen gas. Each 30 mg of the film before and after heating was dissolved in 5 mL of tetrahydrofuran (THF), and GPC measurement was performed using these solutions. The peak area (polymer part) of the RI detection region was determined, and the gel fraction was calculated from the area before and after heating according to the following formula.

Moreover, it replaced with the compound synthesize | combined in the synthesis example 1, and measured the gel fraction similarly using Irganox1010 (made by Nippon Ciba-Geigy Co., Ltd.). The results are shown in Table 3, respectively.
Gel fraction (%) = (1−peak area of RI detection region of resin after heating / peak area of RI detection region of resin before and after heating) × 100

(Synthesis Example 5)
10.0 g (17) of 4,4 ′, 4 ″, 4 ′ ″-[(1-methylethylidene) di-4-cyclohexanyl-1-ylidene] tetrakisphenol represented by the above formula (2-A) .3 mmol) and 20.2 g (70.9 mmol) of stearic acid were weighed into a 500 mL three-necked flask and 200 ml of methylene chloride was added and dissolved. After this solution was cooled in an ice bath, 15.7 g (76.1 mmol) of dicyclohexylcarbodiimide and 0.42 g (3.5 mmol) of N, N-dimethylaminopyridine were added and stirred under a nitrogen atmosphere. After 30 minutes, the reaction solution was warmed to room temperature and stirred at room temperature of 25 ° C. for 4 hours. In the reaction solution, the precipitated solvent-insoluble matter was removed by suction filtration, and the solvent-soluble matter was collected and distilled off under reduced pressure. When the organic content reaches about 100 ml, the liquid is transferred to a separatory funnel, washed with 50 ml of 10% dilute hydrochloric acid, then washed with 50 ml of saturated aqueous sodium carbonate solution, washed twice with 100 ml of distilled water, and then washed with magnesium sulfate. After drying, filtration with filter paper and distillation under reduced pressure were performed to obtain white crystals as a target crude product. The structure of this crude crystal was confirmed by ¹ H-NMR measurement (AVANCE500 type manufactured by Bruker Co., Ltd.) and GPC analysis (HLC-8020 manufactured by Tosoh Corporation). As a result, in addition to the compound (1-A), the above formula (2 It was confirmed that a compound obtained by reacting one to three phenolic hydroxyl groups of the compound represented by -A) with stearic acid was present.

Next, this white solid was recrystallized from ethyl acetate-n-hexane to obtain 23.6 g (yield 83%) of the target compound represented by the following formula (1-E).

This compound was subjected to ¹ H-NMR measurement (AVANCE500 type manufactured by Bruker Co., Ltd.) and analyzed by TG-DTA (TG8120 manufactured by Rigaku Corporation), and it was confirmed that the target compound was obtained. The analysis results were as follows.

¹ H-NMR (solvent: CDCl ₃ ) Chemical shift σ: 7.32 ppm (aromatic ring hydrogen, 4H), 7.13 ppm (aromatic ring hydrogen, 4H), 7.03 ppm (aromatic ring hydrogen, 4H), 6.89 ppm (Aromatic ring hydrogen, 4H), 2.68 ppm (cyclohexane cyclic hydrogen, 2H), 2.52 ppm (COO—C H ₂ —4H), 1.90 ppm to 1.20 ppm (136H), 0.88 ppm (stearic acid methyl group, 12H), 0.51ppm (CH ₃ groups, 6H).

TG-DTA: Decomposition point = 423 ° C

(Evaluation example 4)
1 kg of 10% (wt / wt) toluene solution of ARTON resin (ARTON R5300, manufactured by JSR Corporation) was prepared, and 0.5 g of the compound synthesized in Synthesis Example 5 (0.5% based on ARTON resin) was prepared there. ) Was added and dissolved. Next, the mixture obtained with a large amount of methanol was solidified and isolated, and then granulated with a twin screw extruder to obtain pellets. The pellets obtained here were injection molded using an inline injection molding machine (clamping 75 ton, cylinder diameter 28 mn).

The injection molding conditions were such that the cylinder temperature was 330 ° C., the injection speed was 200 mm / s, and the mold temperature was raised to 150 ° C. at the measured surface temperature.
After cooling the mold, the molded body was removed from the mold, and as a result of observing it with a microscope with an arbitrary 10 mm × 10 mm area at 10 locations and a magnification of 100 times, peeling (missing) was observed in all areas. It did not occur.

Claims

A compound represented by the following formula (1).

(In the formula (1), each L is independently a hydrogen atom, a group represented by the following formula (2), a group represented by the following formula (3) or R 8 CO— (R 8 is a group having 1 to A monovalent hydrocarbon group having 40 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 40 carbon atoms), and each R 4 independently represents a monovalent hydrocarbon having 1 to 20 carbon atoms. Or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and each R 5 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms or 2 having 1 to 20 carbon atoms. A is a single bond, a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, -S-, -SO 2 -, -. a CO- or -O-, m is an integer from 0 to 10, n is an integer of 0 to 4 However, 4 Not when all the L is a hydrogen atom.)

(In formula (2), R 1 each independently represent a hydrogen atom, a monovalent halogenated hydrocarbon group of monovalent hydrocarbon group having 1 to 20 carbon atoms of 1 to 20 carbon atoms, R 2 Each independently represents a single bond or —CO—, and each R 3 independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms. .)

(In the formula (3), R 6 is, independently, a hydrogen atom, a monovalent halogenated hydrocarbon group of monovalent hydrocarbon group having 1 to 20 carbon atoms of 1 to 20 carbon atoms, R 7 Are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms.)
The compound according to claim 1, wherein in the formula (1), L is a group represented by the formula (2).
The compound of Claim 2 whose R < 2 > is a single bond in the said Formula (2).
In the above formula (1), each L is independently a hydrogen atom or a group represented by the above formula (3), and at least one of the plurality of Ls is a group represented by the above formula (3). 1. The compound according to 1.
In the formula (1), each L is independently a hydrogen atom or a group represented by R 8 CO—, and at least one of the plurality of L is a group represented by R 8 CO—. The described compound.
An antioxidant containing the compound according to any one of claims 2 to 4.
A mold release agent containing the compound according to claim 5.
A resin composition containing the compound according to any one of claims 1 to 5.
A resin molded body containing the compound according to any one of claims 1 to 5.
A step of reacting a compound represented by the following formula (4) with one compound selected from the group consisting of compounds represented by the following formula (5), the following formula (6) and the following formula (7): A method for synthesizing a compound represented by the following formula (1).

(In Formula (4), each R 4 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and R 5 is each represented by Independently, it is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and A is a single bond, a divalent hydrocarbon having 1 to 20 carbon atoms. A divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, —S—, —SO 2 —, —CO— or —O—, m is an integer of 0 to 10, and n is 0 to It is an integer of 4.)

In (formula (5), R 1 each independently represent a hydrogen atom, a monovalent halogenated hydrocarbon group of monovalent hydrocarbon group having 1 to 20 carbon atoms of 1 to 20 carbon atoms, R 3 Are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and Y is a group represented by R 9 SO 3 —, A hydroxyl group or a carboxyl group, wherein R 9 is a hydrocarbon group having 1 to 20 carbon atoms.)

(In the formula (6), R 6 are each independently a hydrogen atom, a monovalent halogenated hydrocarbon group of monovalent hydrocarbon group having 1 to 20 carbon atoms of 1 to 20 carbon atoms, R 7 Are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and X is a halogen atom.)

(In Formula (7), each R 8 independently represents a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 40 carbon atoms, and Z represents a hydroxy group. Or a halogen atom.)

(In formula (1), L is independently a hydrogen atom, a group represented a group represented by or R 8 CO- in group represented by the following formula (2), the following equation (3), R 8 Are each independently synonymous with R 8 in formula (7), and R 4 , R 5 , A, m and n are each independently R 4 , R 5 , A, (It is synonymous with m and n. However, not all four Ls are hydrogen atoms.)

(In Formula (2), R 1 and R 3 are each independently synonymous with R 1 and R 3 in Formula (5), and R 2 is independently a single bond or —CO—. .)

(In formula (3), R 6 and R 7 independently has the same meaning as R 6 and R 7 in the formula (6).)