JP2008050266A - Phenol derivative and core crosslinking type star polysulfide obtained from the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a core crosslinking type star polysulfide having a high refractive index and to provide a method for producing the same. <P>SOLUTION: The phenol derivative is represented by formula (1) (R<SB>1</SB>is a substituted or nonsubstituted 1-20C monofunctional aromatic group; R<SB>2</SB>is a 1-20C bifunctional organic group; R<SB>3</SB>is a substituted or nonsubstituted 1-20C monofunctional aromatic group). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a phenol derivative and a core cross-linked star polysulfide obtained therefrom.

  Plastic optical materials are superior in mechanical properties to inorganic materials and can control optical properties. Further, in addition to these advantages, the molding process is easy, and mass production is possible at low cost. Therefore, it is applied to various fields such as lenses, spectacle lenses, contact lenses, optical disks, optical fibers and the like.

  One of the important properties of optical resins is the refractive index. Precise control of the refractive index is indispensable when applied to optical lenses, optical waveguides, and the like. In order to control the refractive index, a technique of introducing various substituents into the resin is widely used. The refractive index is mainly governed by molecular refraction, that is, polarizability.

  Chlorine and iodine, which are halogen groups other than fluorine, increase both the molecular refraction and the molecular volume, so that the refractive index becomes high. However, although these compounds have a high refractive index, the Abbe number tends to decrease, resulting in a problem of chromatic aberration. For this reason, there is a method of introducing sulfur atoms as means for increasing the refractive index without greatly reducing the Abbe number.

  On the other hand, in recent years, shape-specific polymers such as star polymers, hyperbranched polymers, and cyclic polymers have been synthesized, and their properties have been gradually revealed. Since star polymers have the most basic structure among shape-specific polymers, they have been studied for a long time as a model of branched polymers. The star polymer has a structure in which a chain polymer is bonded to the center (core), and has been actively studied as a model of a branched polymer for a long time, and many synthetic methods have been reported so far.

  There are roughly two types of star polymer synthesis methods. One is a core-first method, which has drawbacks such as difficulty in synthesizing a core multifunctional initiator. The other is an arm-first method, in which a chain polymer that becomes an arm molecule is polymerized and then reacted with a reagent that becomes a core. Even in this synthesis method, since the synthesis is performed by a polymer reaction between the core reagent and the arm molecule, it is difficult to synthesize a star polymer having the desired number of arms.

  Thus, it has been difficult to synthesize star polymers having many arms by conventional synthesis methods. However, recently, a method for synthesizing a star polymer having a cross-linked structure in a core by adding a divinyl compound after synthesizing an arm molecule by living radical or living cation polymerization has been reported. According to this synthesis method, it is possible to synthesize a star polymer having a large number of arms whose arm length can be easily controlled (Non-patent Document 1). In addition, the basic primary structures of these star polymers have been reported to have excellent fluidity because they have less entanglement between polymer chains than the same linear polymer. However, despite many reports on the thermal properties and flow characteristics of star polymers, there have been few reports on their optical properties.

Previously, the present inventors synthesized various star polysulfides having a calixarene skeleton in the core by the core-first method, and examined the refractive index characteristics. As a result, it was found that the refractive index was higher than that of the corresponding chain polymer due to the increased sulfur content and the high density due to the specific structure of the star polymer (Patent Document 1, Patent). Reference 2).
JP 2005-225799 A JP 2006-16342 A S. Kanaoka, J.A. Ueda, M .; Sawamoto, T .; Higashimura, Macromolecules, 26, 254 (1993)

The objective of this invention is providing a novel phenol derivative and its manufacturing method.
An object of the present invention is to provide a core cross-linked star polysulfide having a high refractive index and a method for producing the same.

（式（１）中、Ｒ_１は置換又は無置換の炭素数１〜２０の１価の芳香族基を示し、Ｒ_２は炭素数１〜２０の２価の有機基を示し、Ｒ_３は置換又は無置換の炭素数１〜２０の１価の芳香族基を示す。）
２．下記式（２）で表されるフェノール誘導体。

（式（２）中、ｎは１〜１０００の整数を表し、Ｒ_１は置換又は無置換の炭素数１〜２０の１価の芳香族基を示し、Ｒ_２は炭素数１〜２０の２価の有機基を示し、Ｒ_３は置換又は無置換の炭素数１〜２０の１価の芳香族基を示し、Ｒ_４及びＲ_５はそれぞれ水素又は炭素数１〜２０の１価の有機基を示し、またＲ_４とＲ_５は結合してもよい。）
３．下記式（３）で表されるフェノール誘導体。

（式（３）中、ｎは１〜１０００の整数を表し、ｍは１〜１０００の整数を表し、Ｒ_１は置換又は無置換の炭素数１〜２０の１価の芳香族基を示し、Ｒ_２は炭素数１〜２０の２価の有機基を示し、Ｒ_３は置換又は無置換の炭素数１〜２０の１価の芳香族基を示し、Ｒ_４及びＲ_５はそれぞれ水素又は炭素数１〜２０の１価の有機基を示し、またＲ_４とＲ_５は結合してもよく、Ｘは酸素又は硫黄を示し、Ｒ_６及びＲ_７はそれぞれ水素又は炭素数１〜２０の１価の有機基を示し、またＲ_６とＲ_７は結合してもよい。）
４．２又は３記載のフェノール誘導体に下記式（４）で表される化合物を反応させることで得られるコア架橋型スターポリスルフィド。

（式（４）中、Ｒ_８は−Ｏ−、−Ｓ−、−ＣＨ_２−、−ＮＨ−、―ＳＯ_２−、―Ｃ（ＣＨ_３）_２−、―ＣＨ（ＣＨ_３）−、又は−Ｃ（ＣＦ_３）_２−であり、Ｒ_９はそれぞれ水素原子、ハロゲン原子又は炭素数１〜６のアルキル基を示す。Ｘ及びＹはそれぞれ硫黄原子又は酸素原子を示す。）
５．１記載のフェノール誘導体に、下記式（５）で表されるチイラン化合物を反応させる２記載のフェノール誘導体の製造方法。

（式中、Ｒ_４及びＲ_５は式（２）と同じである。）
６．１記載のフェノール誘導体に、下記式（５）で表されるチイラン化合物と、下記式（６）で表されるエポキシ化合物又はチイラン化合物を反応させる３記載のフェノール誘導体の製造方法。

（式中、Ｒ_６、Ｒ_７及びＸは式（３）と同じである。）
７．２又は３記載のフェノール誘導体に下記式（４）で表される化合物を反応させるコア架橋型スターポリスルフィドの製造方法。

（式（４）中、Ｒ_８は−Ｏ−、−Ｓ−、−ＣＨ_２−、−ＮＨ−、―ＳＯ_２−、―Ｃ（ＣＨ_３）_２−、―ＣＨ（ＣＨ_３）−、又は−Ｃ（ＣＦ_３）_２−であり、Ｒ_９はそれぞれ水素原子、ハロゲン原子又は炭素数１〜６のアルキル基を示す。Ｘ及びＹはそれぞれ硫黄原子又は酸素原子を示す。）
８．重合性基を有する２又は３記載のフェノール誘導体。
９．８記載のフェノール誘導体に加熱又は活性エネルギー線照射して得られる３次元硬化物。
１０．８記載のフェノール誘導体に加熱又は活性エネルギー線照射する１０記載の３次元硬化物の製造方法。 The present inventors discovered a high refractive index star polymer by reacting with a core compound after synthesizing a macroinitiator by extending a polythioether chain using a phenol derivative as a starting material. Furthermore, the macroinitiator which has a polymeric group was synthesize | combined and the high refractive index photocurable resin was discovered by the photocrosslinking reaction.
According to the present invention, the following phenol derivatives, core cross-linked star polysulfides and the like are provided.
1. A phenol derivative represented by the following formula (1).

(In Formula (1), R ₁ represents a substituted or unsubstituted monovalent aromatic group having 1 to 20 carbon atoms, R ₂ represents a divalent organic group having 1 to 20 carbon atoms, and R ₃ represents A substituted or unsubstituted monovalent aromatic group having 1 to 20 carbon atoms is shown.)
2. A phenol derivative represented by the following formula (2).

(In formula (2), n represents an integer of 1 to 1000, R ₁ represents a substituted or unsubstituted monovalent aromatic group having 1 to 20 carbon atoms, and R ₂ represents ₂ having 1 to 20 carbon atoms. R ₃ represents a substituted or unsubstituted monovalent aromatic group having 1 to 20 carbon atoms, R ₄ and R ₅ represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms, respectively. And R ₄ and R ₅ may be bonded.)
3. A phenol derivative represented by the following formula (3).

(In formula (3), n represents an integer of 1 to 1000, m represents an integer of 1 to 1000, R ₁ represents a substituted or unsubstituted monovalent aromatic group having 1 to 20 carbon atoms, R ₂ represents a divalent organic group having 1 to 20 carbon atoms, R ₃ represents a substituted or unsubstituted monovalent aromatic group having 1 to 20 carbon atoms, and R ₄ and R ₅ represent hydrogen or carbon, respectively. R 1 represents a monovalent organic group having 1 to 20; R ₄ and R ₅ may be bonded; X represents oxygen or sulfur; R ₆ and R ₇ are each hydrogen or 1 having 1 to 20 carbon atoms; A valent organic group, and R ₆ and R ₇ may be bonded.)
The core bridge | crosslinking type star polysulfide obtained by making the compound represented by following formula (4) react with the phenol derivative of 4.2 or 3.

(In Formula (4), R ₈ represents —O—, —S—, —CH ₂ —, —NH—, —SO ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, or -C _{(CF 3) 2} - a and, _{R 9} are each a hydrogen atom, .X and Y represents a halogen atom or an alkyl group having 1 to 6 carbon atoms denotes a sulfur atom or an oxygen atom).
The manufacturing method of the phenol derivative of 2 with which the thiirane compound represented by following formula (5) is made to react with the phenol derivative of 5.1.

(In the formula, R ₄ and R ₅ are the same as in formula (2).)
The method for producing a phenol derivative according to 3, wherein the phenol derivative according to 6.1 is reacted with a thiirane compound represented by the following formula (5) and an epoxy compound or a thiirane compound represented by the following formula (6).

(In the formula, R ₆ , R ₇ and X are the same as in formula (3).)
A method for producing a core cross-linked star polysulfide, comprising reacting the phenol derivative according to 7.2 or 3 with a compound represented by the following formula (4):

(In Formula (4), R ₈ represents —O—, —S—, —CH ₂ —, —NH—, —SO ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, or -C _{(CF 3) 2} - a and, _{R 9} are each a hydrogen atom, .X and Y represents a halogen atom or an alkyl group having 1 to 6 carbon atoms denotes a sulfur atom or an oxygen atom).
8). 4. The phenol derivative according to 2 or 3 having a polymerizable group.
A three-dimensional cured product obtained by heating or irradiating active energy rays to the phenol derivative described in 9.8.
10. The method for producing a three-dimensional cured product according to 10, wherein the phenol derivative according to 10.8 is heated or irradiated with active energy rays.

ADVANTAGE OF THE INVENTION According to this invention, a novel phenol derivative and its manufacturing method can be provided.
According to the present invention, a core-crosslinked star polysulfide having a high refractive index suitable as an optical material can be provided from a novel phenol derivative.

  The star polymer of this invention can manufacture the phenol derivative represented by Formula (1)-(3) as an intermediate body.

R ₁ in the formulas (1) to (3) is a substituted or unsubstituted monovalent aromatic group having 1 to 20 carbon atoms. Examples of the aromatic group include a phenyl group and a naphthyl group. Groups are preferred. Examples of the substituent substituted on the aromatic group include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, t-butyl groups, and other alkyl groups, vinyl groups, Alkenyl groups such as allyl groups, saturated or unsaturated cyclic aliphatic hydrocarbon groups such as cyclohexyl groups and norbornene groups, aromatic groups such as phenyl groups and naphthyl groups, ethers, esters, aminos, and the like Is a substituted organic group. Preferably it is a C1-C6 alkyl group.

R ₂ in the formulas (1) to (3) is a divalent organic group having 1 to 20 carbon atoms, for example, an alkylene group such as a methylene group or an ethylene group, an aromatic group such as a phenylene group, and these are substituted. The organic group is preferably an electron-withdrawing group such as an alkylene group having 1 to 4 carbon atoms or a dinitro-substituted phenylene group from the viewpoint of the reactivity of the chlorine group.

R ₃ in the formulas (1) to (3) is a substituted or unsubstituted monovalent aromatic group having 1 to 20 carbon atoms. Examples of the aromatic group include a phenyl group and a naphthyl group. Groups are preferred. Examples of the substituent substituted on the aromatic group include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, t-butyl groups, and other alkyl groups, vinyl groups, Alkenyl groups such as allyl groups, saturated or unsaturated cyclic aliphatic hydrocarbon groups such as cyclohexyl groups and norbornene groups, aromatic groups such as phenyl groups and naphthyl groups, ethers, esters, aminos, and the like A substituted organic group. Preferably, it is a phenyl group substituted or unsubstituted by a C1-C4 alkyl group, or a naphthyl group.

R ₄ and R _{5 in the} formulas (2) and (3) are each hydrogen or a monovalent organic group having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, or an n-propyl group independently of each other. , Isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl and other alkyl groups, vinyl, allyl and other alkenyl groups, cyclohexyl, norbornene and other saturated or unsaturated cyclic groups An aliphatic hydrocarbon group, an aromatic group such as a phenyl group or a naphthyl group, an ether, an ester, an amino, or an organic group in which these are substituted, and R ₄ and R ₅ are bonded to each other. For example, a ring such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, norbornane ring may be formed. Preferably, R ₄ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₅ is a phenoxyalkyl (preferably having 1 to 4 carbon atoms) group substituted or unsubstituted by an alkyl group having 1 to 4 carbon atoms. It is.

N in Formula (2) and Formula (3) is an integer of 1-1000, Preferably it is 1-100.
The number average molecular weight of the formula (2) is preferably 1000 to 50000.

R ₆ and R ₇ in the formula (3) are each hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and for example, independently of each other, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n Alkyl groups such as butyl group, isobutyl group, sec-butyl group and t-butyl group, alkenyl groups such as vinyl group, allyl group, acrylolyl group, methacryloyl group, styryl group, p-vinylaryl group and vinyloxy group Saturated or aliphatic hydrocarbon groups such as cyclohexyl group, norbornene group, crotonyl group, alkoxy group and phenoxy group, aromatic groups such as phenyl group and naphthyl group, ethers, esters, and these are substituted. An organic group, and R ₆ and R ₇ are bonded to form, for example, cyclobutane, cyclopentane, cyclohexane, cycloheptane, norbornane, etc. A ring may be formed. Preferably, R ₆ is hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably R ₆ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₇ is a (meth) acryloxyalkyl (preferably A group having 1 to 4 carbon atoms.

M in Formula (3) is an integer of 1-1000, Preferably it is 1-100.
The number average molecular weight of the formula (3) is preferably 1000 to 50000.

（式中、Ｒ_４及びＲ_５は式（２）と同じである。） The phenol derivative represented by the formula (2) can be obtained by reacting the compound represented by the formula (1) with a corresponding thiirane compound represented by the following formula. The reaction is preferably carried out in the presence of a salt catalyst.

(In the formula, R ₄ and R ₅ are the same as in formula (2).)

  As the salt catalyst, quaternary ammonium salts such as tetrabutylammonium bromide and tetraethylammonium chloride, and metal salts such as lithium chloride and lithium bromide can be used. The addition amount of the catalyst is preferably equal to the functional group amount of the compound represented by the formula (1).

  Solvents used in the reaction include ethers, halogen solvents, hydrocarbon solvents, aprotic polar solvents such as N, N-dimethylformamide and 1-methyl-2-pyrrolidone, and ketones such as acetone and cyclohexanone. Solvents and esters such as ethyl acetate can be used. Moreover, it can be made to react even without solvent.

Although reaction temperature is normally performed between 0-150 degreeC, Preferably it is 20 to 100 degreeC, More preferably, it is 50 to 100 degreeC. If the reaction temperature is less than 0 ° C, the reaction time may be prolonged, and if the reaction temperature exceeds 150 ° C, side reactions may occur.
The reaction is desirably performed in a state where moisture can be removed, such as an ampoule sealed tube.

（式中、Ｒ_６、Ｒ_７及びＸは式（３）と同じである。） The phenol derivative represented by the formula (3) can be obtained by reacting the compound represented by the formula (1) with the thiirane compound (5) and the corresponding thiirane compound or epoxy compound represented by the formula (6). it can. The phenol derivative represented by the formula (3) can be obtained by reacting the compound represented by the formula (2) with the thiirane compound or epoxy compound represented by the formula (6). The reaction is preferably carried out in the presence of a salt catalyst.

(In the formula, R ₆ , R ₇ and X are the same as in formula (3).)

  As the salt catalyst, quaternary ammonium salts such as tetrabutylammonium bromide and tetraethylammonium chloride, and metal salts such as lithium chloride and lithium bromide can be used. The addition amount of the catalyst is preferably equal to the functional group amount of the compound represented by the formula (1) or (2) of the starting material.

  Solvents used in the reaction include ethers, halogen solvents, hydrocarbon solvents, aprotic polar solvents such as N, N-dimethylformamide and 1-methyl-2-pyrrolidone, and ketone solvents such as acetone and cyclohexanone. Esters such as ethyl acetate can be used. Moreover, it can be made to react even without solvent.

Although reaction temperature is normally performed between 0-150 degreeC, Preferably it is 20-100 degreeC, More preferably, it is 50-100 degreeC. If the reaction temperature is less than 0 ° C, the reaction time may be prolonged, and if the reaction temperature exceeds 150 ° C, side reactions may occur.
The reaction is desirably performed in a state where moisture can be removed, such as an ampoule sealed tube.

（式（４）中、Ｒ_８は−Ｏ−、−Ｓ−、−ＣＨ_２−、−ＮＨ−、―ＳＯ_２−、―Ｃ（ＣＨ_３）_２−、―ＣＨ（ＣＨ_３）−、又は−Ｃ（ＣＦ_３）_２−であり、Ｒ_９はそれぞれ水素原子、ハロゲン原子又は炭素数１〜６のアルキル基を示す。Ｘ及びＹはそれぞれ硫黄原子、又は酸素原子を示す。） A core-crosslinked star polysulfide is obtained by reacting the compound represented by the following formula (4) with the compound of the formula (2) or the formula (3). Preferably, the reaction is performed in the presence of a salt catalyst.

(In Formula (4), R ₈ represents —O—, —S—, —CH ₂ —, —NH—, —SO ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, or -C _{(CF 3) 2} - a and, _{R 9} are each a hydrogen atom, .X and Y are each sulfur atom a halogen atom or an alkyl group having 1 to 6 carbon atoms, or an oxygen atom).

Y in formula (4) is substituted at the ortho, meta, or para position of the benzene ring, preferably at the para position. R ₉ is substituted one by one in addition to the portion where Y is substituted.

  As the salt catalyst, quaternary ammonium salts such as tetrabutylammonium bromide and tetraethylammonium chloride, and metal salts such as lithium chloride and lithium bromide can be used. The addition amount of the catalyst is preferably equal to the functional group amount of the compound represented by the formula (2).

  Solvents used in the reaction include ethers, halogen solvents, hydrocarbon solvents, aprotic polar solvents such as N, N-dimethylformamide and 1-methyl-2-pyrrolidone, and ketone solvents such as acetone and cyclohexanone. Esters such as ethyl acetate can be used. Moreover, it can be made to react even without solvent.

Although reaction temperature is normally performed between 0-150 degreeC, Preferably it is 20-100 degreeC, More preferably, it is 50-100 degreeC. If the reaction temperature is less than 0 ° C, the reaction time may be prolonged, and if the reaction temperature exceeds 150 ° C, side reactions may occur.
The reaction is desirably performed in a state where moisture can be removed, such as an ampoule sealed tube.

The compounds represented by the formulas (2) and (3) are unsaturated hydrocarbon groups having double bonds or triple bonds, and high strain hydrocarbon groups such as acrylic groups, methacryl groups, cyclopropane groups, and cyclobutane groups. Polymeric groups such as radical polymerizable, cationic, and anionic polymerizable groups such as vinyl ether groups, vinyl ester groups, cyclic ether groups such as epoxy groups and oxetane groups, and the like can be included. For example, at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ can contain a polymerizable group.

  When the compounds of formulas (2) and (3) contain a polymerizable group, a three-dimensional cured product can be obtained by adding a corresponding polymerization catalyst and irradiating active energy rays such as heating or light.

  At this time, the compound represented by the formulas (2) and (3) may be mixed with another substance and cured together. Various polymers such as epoxy resin, acrylic resin, polystyrene, polyamide, polyimide, polyamideimide, polyolefin, and siloxane polymer may be blended at an arbitrary ratio.

  Furthermore, for the purpose of enhancing the properties of the three-dimensional cured product, an inorganic filler such as silica or titanium oxide or an organic filler may be added at an arbitrary ratio.

  The thermal radical polymerization initiator is not particularly limited and known ones can be used. Typical examples are peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, lauroyl peroxide, t-butyl peroxydicarbonate, and azo compounds such as azoisobutyronitrile. The amount of thermal radical polymerization initiator used varies depending on the polymerization conditions, the type of initiator, the type and composition of the polymerizable monomer, and cannot be unconditionally limited, but is in the range of 0.01 to 10 equivalent% with respect to the polymerizable group. It is preferred to use. The polymerization temperature and polymerization time are not limited because they vary greatly depending on the type and amount of polymerization initiator and the type of polymerizable monomer, but it is preferable to select conditions so that the polymerization is completed in 2 to 40 hours.

  The initiator for radical polymerization using active energy rays such as ultraviolet rays, visible light, or radiation is not particularly limited, and known ones can be used. Representative examples include benzoyl methyl ether, benzophenone, acetophenone, benzyl methyl ketal, 2-isopropylthioxanthone and the like. These polymerization initiators are generally used in the range of 0.001 to 5 equivalent% with respect to the polymerizable group.

  The thermal cationic polymerization initiator is not particularly limited, and known ones can be used. As a typical example, aluminum chloride, tin chloride, titanium tetrachloride and the like are used. The amount of the thermal cationic polymerization initiator used varies depending on the polymerization conditions, the type of the initiator, the type and composition of the polymerizable monomer, and cannot be unconditionally limited, but is in the range of 0.01 to 10 equivalent% with respect to the polymerizable group. It is preferred to use. The polymerization temperature and polymerization time are not limited because they vary greatly depending on the type and amount of polymerization initiator and the type of polymerizable monomer, but it is preferable to select conditions so that the polymerization is completed in 2 to 40 hours.

  The initiator for cationic polymerization using active energy rays such as ultraviolet rays, visible light, or radiation is not particularly limited, and known ones can be used. Typical examples include sulfonium salts and iodonium salts. These polymerization initiators are generally used in the range of 0.001 to 5 equivalent% with respect to the polymerizable group.

  The anionic polymerization initiator is not particularly limited, and known ones can be used. As typical examples, potassium hydroxide, sodium hydroxide, metallic lithium and the like are used.

  Various sensitizers and promoters may be added to the above catalyst. In order to control the physical properties of the three-dimensional cured product, various additives such as an antioxidant, a metal deactivator, an ultraviolet absorber, a flame retardant, a stabilizer, and a leveling agent may be added.

５００ｍｌ三口フラスコに、ｐ−ｔｅｒｔ−ブチルフェノール３．０ｇ（０．０２ｍｏｌ）、ピリジン３．１６ｍｌ（０．０４ｍｏｌ）、ＴＨＦ２０ｍｌに溶解させた後、ハミルトンシリンジでクロロアセチルクロリド４．５ｍｌ（０．０４ｍｏｌ）を０℃に保ちながら、窒素雰囲気下でゆっくり滴下し、３時間攪拌した。反応終了後、反応溶液を酢酸エチルで希釈し５ｍｏｌ％の炭酸水素ナトリウム水溶液をゆっくり加えて３回洗浄を行った。その後、蒸留水で３回洗浄を行い有機層が中性になったのを確認し、有機層を無水硫酸マグネシウムで乾燥させた。乾燥剤をろ過後、酢酸エチルを減圧留去し、褐色粘性液体を得た。
５０ｍｌ三口フラスコに得られた褐色粘性液体とチオ安息香酸カリウム３．０ｇ（０．０４ｍｍｏｌ）、さらに触媒としてテトラブチルアンモニウムブロミド０．０７ｇ（５ｍｏｌ％）を加え、１−メチル−２−ピロリドン１０ｍｌに溶解させた後、室温で５時間攪拌した。反応終了後、反応溶液を酢酸エチルで希釈し、蒸留水で三回洗浄して、酢酸エチル層を無水硫酸マグネシウムで乾燥した。無水硫酸マグネシウムをろ過後、酢酸エチルを減圧留去し、展開溶媒としてクロロホルムを用いてカラムにて単離精製を行った。クロロホルムを減圧留去し、（７）を褐色粘性液体として４．３０ｇ（６５％）得た。得られた化合物のＩＲ、^１Ｈ−ＮＭＲの結果を以下に示す。
ＩＲ：２９６２、１７５８、１６６０、１５９６、１４８０、１１２８、７５５
^１Ｈ−ＮＭＲ（６００ＭＨｚ、ＤＭＳＯ−ｄ_６）：１．２５（ｓ、９Ｈ）、４．２５（ｓ、４Ｈ）、７．０７（ｄ、２．０Ｈ）、７．４１（ｄ、２．０Ｈ）、７．５６（ｔ、２Ｈ）、７．７０（ｔ、１Ｈ）、７．９７（ｄ、２Ｈ） EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
Example 1
A compound represented by the following formula (7) (hereinafter abbreviated as (7)) was synthesized by the following method.

In a 500 ml three-necked flask, 3.0 g (0.02 mol) of p-tert-butylphenol, 3.16 ml (0.04 mol) of pyridine and 20 ml of THF were dissolved, and then 4.5 ml (0.04 mol) of chloroacetyl chloride with a Hamilton syringe. Was kept dropwise at 0 ° C. under a nitrogen atmosphere and stirred for 3 hours. After completion of the reaction, the reaction solution was diluted with ethyl acetate, and 5 mol% aqueous sodium hydrogen carbonate solution was slowly added to perform washing three times. Thereafter, it was washed with distilled water three times to confirm that the organic layer became neutral, and the organic layer was dried over anhydrous magnesium sulfate. After filtering the desiccant, ethyl acetate was distilled off under reduced pressure to obtain a brown viscous liquid.
The brown viscous liquid obtained in a 50 ml three-necked flask, 3.0 g (0.04 mmol) of potassium thiobenzoate and 0.07 g (5 mol%) of tetrabutylammonium bromide as a catalyst were added, and 10 ml of 1-methyl-2-pyrrolidone was added. After dissolving, the mixture was stirred at room temperature for 5 hours. After completion of the reaction, the reaction solution was diluted with ethyl acetate, washed three times with distilled water, and the ethyl acetate layer was dried over anhydrous magnesium sulfate. After filtering anhydrous magnesium sulfate, ethyl acetate was distilled off under reduced pressure, and isolation and purification were carried out on a column using chloroform as a developing solvent. Chloroform was distilled off under reduced pressure to obtain 4.30 g (65%) of (7) as a brown viscous liquid. The results of IR and ¹ H-NMR of the obtained compound are shown below.
IR: 2962, 1758, 1660, 1596, 1480, 1128, 755
¹ H-NMR (600 MHz, DMSO-d ₆ ): 1.25 (s, 9H), 4.25 (s, 4H), 7.07 (d, 2.0H), 7.41 (d, 2. 0H), 7.56 (t, 2H), 7.70 (t, 1H), 7.97 (d, 2H)

湿度１０％以下のドライバック中において、アンプル管にテトラブチルアンモニウムクロリドを０．００３ｇ（０．１６ｍｍｏｌ）秤り取り、攪拌しながら４０℃で５時間減圧乾燥を行った。その後、（７）０．０５２５ｇ（０．１６ｍｍｏｌ）とスルフィドＡ １．０６４ｇ（６．４ｍｏｌ）をアンプル管に加え、１−メチル−２−ピロリドンに溶解させた。次に、液体窒素を用いて３回凍結脱気を行い、減圧状態でアンプル管を封管した。試料が凍結したのを確認して、９０℃、２４時間の条件で反応を行った。反応終了後、メタノールで２回再沈精製を行い、ｎ＝４０の（８）を１．０１８ｇ（収率９１％）得た。構造確認は、ＩＲ、^１Ｈ−ＮＭＲにより行った。
得られたポリスルフィドの分子量をサイズ排除クロマトグラフィー（ＳＥＣ）で測定したところ、数平均分子量７．１０×１０^３、分散度１．６０であった。
ＩＲ：２９６４、１７３５、１６６２、１５９８、１４９６、７５４
^１Ｈ−ＮＭＲ（５００ＭＨｚ、ＤＭＳＯ−ｄ_６）：１．０５（ｂｒｏａｄｓ ｓ、９Ｈ）、３．００〜３．２２（ｍ、１１９．９Ｈ）、４．０６〜４．１２（ｍ、１１９．９Ｈ）、６．８３〜７．８９（ｍ、２０７．４Ｈ）
スルフィドＡの量を変えて同様に反応を行い評価した結果を次の表に示す。 Example 2
A compound represented by the following formula (8) (hereinafter abbreviated as (8)) was synthesized by the following method.

In a dry pack with a humidity of 10% or less, 0.003 g (0.16 mmol) of tetrabutylammonium chloride was weighed in an ampule tube and dried under reduced pressure at 40 ° C. for 5 hours while stirring. Thereafter, 0.057 g (0.16 mmol) of (7) and 1.064 g (6.4 mol) of sulfide A were added to the ampule tube and dissolved in 1-methyl-2-pyrrolidone. Next, freeze deaeration was performed three times using liquid nitrogen, and the ampoule tube was sealed under reduced pressure. After confirming that the sample was frozen, the reaction was performed at 90 ° C. for 24 hours. After completion of the reaction, reprecipitation purification was performed twice with methanol to obtain 1.018 g (yield 91%) of n = 40 (8). The structure was confirmed by IR and ¹ H-NMR.
When the molecular weight of the obtained polysulfide was measured by size exclusion chromatography (SEC), the number average molecular weight was 7.10 × 10 ³ and the degree of dispersion was 1.60.
IR: 2964, 1735, 1662, 1598, 1496, 754
¹ H-NMR (500 MHz, DMSO-d ₆ ): 1.05 (roads s, 9H), 3.00 to 3.22 (m, 119.9H), 4.06 to 4.12 (m, 119. 9H), 6.83 to 7.89 (m, 207.4H)
The following table shows the results of a similar reaction conducted with varying amounts of sulfide A.

Example 3
The core cross-linked star polysulfide was synthesized by the following method.

In a dry box kept at a humidity of 10% or less, 0.058 g (0.2 mmol) of tetrabutylammonium chloride was weighed into an ampule tube and dried under reduced pressure at 40 ° C. for 5 hours with stirring. Then, 0.066 g (0.2 mmol) of compound (7) (hereinafter abbreviated as (7)), 0.377 g (2.0 mmol) of 3-phenoxypropylene sulfide (hereinafter referred to as sulfide A), 1-methyl-2-pyrrolidone 1 ml was added and sealed. After stirring the ampule tube at 90 ° C. for 24 hours, the reaction solution was purified by reprecipitation twice with methanol to obtain 0.30 g (62%) of Compound (8) (hereinafter abbreviated as (8)). The polymerization degree n of the obtained (8) was calculated by ¹ H-NMR (500 MHz, DMSO-d ₆ ).

  The reaction of the obtained (8) and 0.078 g (0.2 mmol) of compound (9) (hereinafter abbreviated as (9)) in 1-methyl-2-pyrrolidone (NMP) at 90 ° C. for 48 hours. I went there. After completion of the reaction, reprecipitation purification was performed twice in methanol to obtain 0.30 g (62%) of the core cross-linked star polysulfide as a yellow solid.

In addition, (9) can be manufactured by the following method.
To a 100 ml three-necked flask, 5.48 g (0.07 mol) of thiourea and 10 l of water were added, suspended by stirring, and 3.53 g (0.035 mol) of concentrated sulfuric acid was added dropwise. When it became a homogeneous solution, 10.76 g (0.035 mol) of bis (4- (2,3-epoxypropylthio) phenyl) sulfide (manufactured by Sumitomo Seika Co., Ltd.) was added dropwise while maintaining the temperature at 0 ° C. with an ice bath. And added. The mixture was stirred at room temperature for 20 hours, and the resulting white precipitate was collected and washed with ether. Thereafter, it was dried under reduced pressure to obtain 14.0 g (yield 96%) of bis (4- (2,3-epoxypropylthio) phenyl) sulfide-thiouronium hydrochloride as a white solid.
The IR results of the obtained compound are shown below.
IR (cm ⁻¹ ): 3371, 3100, 2925, 1658, 1596, 1493, 995

Into a 100 ml three-necked flask, 14.0 g (0.03 mol) of the obtained bis (4- (2,3-epoxypropylthio) phenyl) sulfide thiouronium hydrochloride and 50 l of water were added and suspended by stirring. . An aqueous sodium carbonate solution (0.03 mol) was added, and the mixture was reacted by stirring at 60 ° C. for 2 hours. The lower layer of the reaction solution was extracted with chloroform, dried over magnesium sulfate, filtered, and chloroform was distilled off under reduced pressure to obtain a white solid. The white solid was recrystallized with chloroform: n-hexane = 1: 3 to obtain 11.2 g (yield 80%) of (9) as colorless transparent needle crystals.
The analysis results of the obtained compound are shown below.
IR (cm ⁻¹ ): 3100, 2983, 995, 811
¹ H-NMR (500 MHz, CDCl ₃ )
δ (ppm) 2.13 (dd, 2H), 2.49 (dd, 2H), 2.81 (dd, 2H), 3.41 (dd, 2H), 3.07 to 3.12 (m, 2H), 7.25-7.36 (m, 2H)
Elemental analysis _{(C 18 H 18 S 5)} : C: 54.7%, H: 4.48%

When the molecular weight of the obtained core cross-linked star polysulfide was measured by a size exclusion chromatography (SEC) method, it had a number average molecular weight of 1.35 × 10 ⁴ and a dispersity of 2.14. The measurement conditions of the SEC method were as follows.
(A) Size exclusion chromatography (SEC): manufactured by Tosoh Corporation, gel permeation chromatography (SEC) HLC-8020 type (b) column: TSKgel G1000H (made by Tosoh Corporation)
(C) Developing solvent: Tetrahydrofuran (d) Standard material: polystyrene The IR results of the obtained compound are shown below.
IR (cm ⁻¹ ): 3100, 2964, 1735, 1662, 1598, 1496, 754

The refractive index of the obtained core cross-linked star polysulfide was measured and found to be 1.651.
Refractive index measurement method: 20 mg of polymer was dissolved in 2 ml of tetrahydrofuran, 0.2 ml of this solution was dropped on a silicon wafer, and applied with a spin coater (manufactured by Asanuma Seisakusho Co., Ltd.). Next, the silicon wafer coated with this solution was dried under reduced pressure at room temperature for 24 hours, and then the refractive index measurement at a wavelength of 632.8 nm was performed 5 times with an ellipsometer (manufactured by Gardner, Inc., model 115B) to remove the maximum and minimum values. The average of three measurements was taken as the refractive index.

Further, Tg of the obtained core cross-linked star polysulfide was measured by the following method. Tg was 30.7 ° C.
Tg measurement method: About 5 mg of polymer was weighed in an aluminum pan, the pan was sealed, and then the temperature was increased at a rate of 10 ° C./min in a nitrogen atmosphere using a differential scanning calorimeter (Seiko Instruments EXSTAR 6000 / TG / DTA6200). The measurement was performed at a temperature setting of -50 ° C to 50 ° C.

  As shown in Table 2, the reaction was performed under the same conditions while changing the amounts of sulfide A and (7), and the obtained core-crosslinked star polysulfide was evaluated. The results are shown in Table 2.

  The refractive index of the obtained core cross-linked star polysulfide was not affected by the degree of polymerization of sulfide A, and was about 1.650 in all cases. This is probably because the density is almost constant.

  (7) The product obtained by reacting 0.4 mmol and 2.0 mmol of sulfide A was insoluble in the organic solvent. Moreover, since the GPC measurement result of the soluble part showed bimodality, it is considered that the cross-linking reaction between the molecules is proceeding between the core-crosslinked star polysulfides in the soluble part.

Example 4
A compound represented by the following formula (10) (hereinafter abbreviated as (10)) was synthesized by the following method.

  Tetrabutylammonium chloride 0.0056 g (0.02 mmol), sulfide A 0.1690 g (1.0 mmol), 3-methacryloyloxypropylene sulfide (hereinafter referred to as sulfide B) in an ampoule tube in a dry box kept at a humidity of 10% or less ) 0.0312 g (0.2 mmol), (7) 0.0065 g (0.02 mmol), and 1 ml of 1-methyl-2-pyrrolidone were added and sealed. After stirring the reaction solution at 70 ° C. for 24 hours, the reaction solution was purified by reprecipitation twice with methanol to obtain 0.0497 g (yield 91%) of (10) as a colorless transparent solid.

When the molecular weight of the obtained compound was measured by the SEC method, the number average molecular weight was 2.0 × 10 ³ and the degree of dispersion was 1.40. The degree of polymerization (m, n) was calculated by ¹ H-NMR (500 MHz, DMSO-d ₆ ). As a result, m = 7 and n = 50. Tg was −4 ° C.

  As shown in Table 3, the reaction was conducted in the same manner while changing the amounts of sulfide A and sulfide B, and evaluation was performed. The results are shown in Table 3.

Example 5
A three-dimensional cured product was synthesized by the following method.
(10) 0.1 g was dissolved in 1 ml of tetrahydrofuran, and Irgacure 907 (manufactured by Ciba Specialty Chemicals, 0.003 g) and 0.001 g of 2-ethylanthraquinone were added. The solution was applied on a potassium bromide plate to form a film. Thereafter, light irradiation was performed for 15 minutes using a 250 W ultra-high pressure mercury lamp as a light source to obtain a three-dimensional cured product.

  For (10) synthesized with varying amounts of sulfide A and sulfide B, the photocuring reaction was performed in the same manner, and the Tg of the resulting cured product was measured. The results are shown in Table 3.

  It was found that Tg after light irradiation increased. Since the product was insoluble in various solvents, it was clarified that a side chain methacryloyl group reacted with light irradiation to obtain a three-dimensional cured product.

The core cross-linked star polysulfide of the present invention is a resin having high heat resistance, adjustable refractive index, and higher refractive index. This resin can be used for an optical lens, an optical film, a liquid crystal display device using the optical film, and the like.
The cured product of the present invention can be used for an optical lens, an optical film, a liquid crystal display device using the optical film, and the like.

Claims (10)

A phenol derivative represented by the following formula (1).

(In Formula (1), R ₁ represents a substituted or unsubstituted monovalent aromatic group having 1 to 20 carbon atoms, R ₂ represents a divalent organic group having 1 to 20 carbon atoms, and R ₃ represents A substituted or unsubstituted monovalent aromatic group having 1 to 20 carbon atoms is shown.) A phenol derivative represented by the following formula (2).

(In formula (2), n represents an integer of 1 to 1000, R ₁ represents a substituted or unsubstituted monovalent aromatic group having 1 to 20 carbon atoms, and R ₂ represents ₂ having 1 to 20 carbon atoms. R ₃ represents a substituted or unsubstituted monovalent aromatic group having 1 to 20 carbon atoms, R ₄ and R ₅ represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms, respectively. And R ₄ and R ₅ may be bonded.) A phenol derivative represented by the following formula (3).

(In formula (3), n represents an integer of 1 to 1000, m represents an integer of 1 to 1000, R ₁ represents a substituted or unsubstituted monovalent aromatic group having 1 to 20 carbon atoms, R ₂ represents a divalent organic group having 1 to 20 carbon atoms, R ₃ represents a substituted or unsubstituted monovalent aromatic group having 1 to 20 carbon atoms, and R ₄ and R ₅ represent hydrogen or carbon, respectively. R 1 represents a monovalent organic group having 1 to 20; R ₄ and R ₅ may be bonded; X represents oxygen or sulfur; R ₆ and R ₇ are each hydrogen or 1 having 1 to 20 carbon atoms; A valent organic group, and R ₆ and R ₇ may be bonded.) A core cross-linked star polysulfide obtained by reacting the phenol derivative according to claim 2 or 3 with a compound represented by the following formula (4).

(In Formula (4), R ₈ represents —O—, —S—, —CH ₂ —, —NH—, —SO ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, or -C _{(CF 3) 2} - a and, _{R 9} are each a hydrogen atom, .X and Y represents a halogen atom or an alkyl group having 1 to 6 carbon atoms denotes a sulfur atom or an oxygen atom). The method for producing a phenol derivative according to claim 2, wherein the phenol derivative according to claim 1 is reacted with a thiirane compound represented by the following formula (5).

(In the formula, R ₄ and R ₅ are the same as in formula (2).) The method for producing a phenol derivative according to claim 3, wherein the phenol derivative according to claim 1 is reacted with a thiirane compound represented by the following formula (5) and an epoxy compound or a thiirane compound represented by the following formula (6).

(In the formula, R ₆ , R ₇ and X are the same as in formula (3).) The manufacturing method of the core bridge | crosslinking type star polysulfide which makes the compound represented by following formula (4) react with the phenol derivative of Claim 2 or 3.

(In Formula (4), R ₈ represents —O—, —S—, —CH ₂ —, —NH—, —SO ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, or -C _{(CF 3) 2} - a and, _{R 9} are each a hydrogen atom, .X and Y represents a halogen atom or an alkyl group having 1 to 6 carbon atoms denotes a sulfur atom or an oxygen atom).   The phenol derivative according to claim 2 or 3, which has a polymerizable group.   A three-dimensional cured product obtained by heating or irradiating active energy rays to the phenol derivative according to claim 8. The method for producing a three-dimensional cured product according to claim 10, wherein the phenol derivative according to claim 8 is heated or irradiated with active energy rays.