JP2020142997A - Fluorene compound and manufacturing method thereof - Google Patents

Abstract

To provide a monofunctional fluorene compound capable of forming a resin having a high refractive index even if it is monofunctional (or even if two aryl groups are not substituted at the 9 position of the fluorene skeleton).SOLUTION: The compound of the present invention is represented by the following formula (1) (wherein, Z represents an aromatic hydrocarbon ring; R1 and R3 each represents a non-reactive group; R2 represents a hydrocarbon group; R4 represents a hydrogen atom or a methyl group; A represents an alkylene group; k represents an integer of 0 to 8; m represents an integer of 0 or 1; n represents an integer of 0 or more; and p represents an integer of 1 or more).SELECTED DRAWING: None

Description

The present invention relates to a monofunctional fluorene compound having a substituent such as an aryl group at the 9-position and a method for producing the same.

A compound having a fluorene skeleton has optical properties such as a high refractive index and excellent properties such as heat resistance, and is therefore used as a resin raw material or a resin additive. Typically, a resin or monomer having a 9,9-bisarylfluorene skeleton, for example, a polyfunctional (meth) acrylic system such as 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. Resins and the like are known, but such polyfunctional (meth) acrylic resins often have high viscosity and low handleability. Therefore, the development of a monofunctional fluorene compound that can be used as a reactive diluent or the like is underway.

Patent Document 1 describes compounds represented by the following formula (2).

(In the formula, ring Z ¹ and ring Z ² are aromatic hydrocarbon rings, E is an oxygen atom, a sulfur atom or an imino group, R ¹ is a cyano group or an alkyl group, R ² is an alkylene group, and R ³ and R ⁴ are. R ⁵ is a hydrogen atom or a methyl group, k is an integer of 0 to 4, and m, n and p are integers of 0 or more, respectively), such as a hydrocarbon group.

Further, Patent Document 2 describes a monofunctional (meth) acrylate represented by the following formula (1).

(In the formula, R ¹ is a cyano group, a halogen atom or an alkyl group, R ² is a hydrogen atom or a methyl group, R ³ is an alkylene group, R ⁴ is a direct bond, an alkylidene group or an alkylene group, R ⁵ is a substituent, k. Is an integer of 0 to 4, m is an integer of 0 or more, and n is 0 or 1).

JP-A-2009-13096 JP-A-2009-79013

In the examples of Patent Document 1, 9- [4- (2-acryloyloxyethoxy) phenyl] -9-phenylfluorene, 9- [4- (2-methacryloyloxyethoxy) phenyl] -9-phenylfluorene and the like are prepared. Has been done. However, these compounds tend to have a high melting point and are difficult to handle. In addition, since the synthesis of the raw material 9-phenylfluorenol requires an expensive metal containing palladium or a ligand, the cost is high and it is difficult to completely remove the metal catalyst in the purification process. ..

Further, in the examples of Patent Document 2, 9-[(meth) acryloyloxymethyl] fluorene, 9-methacryloyloxyfluorene and the like are prepared. However, these compounds are colored yellow and have a low refractive index.

Therefore, it is an object of the present invention to be able to form a polymer (or cured product) having a high refractive index even if it is monofunctional (or even if two aryl groups are not substituted at the 9-position of the fluorene skeleton). It is an object of the present invention to provide a novel monofunctional fluorene compound and a method for producing the same.

Another object of the present invention is to provide a monofunctional fluorene compound having an fluorene skeleton but having excellent handleability and a method for producing the same.

Still another object of the present invention is to provide a monofunctional fluorene compound in which coloration is suppressed and a method for producing the same.

Another object of the present invention is to provide a monofunctional fluorene compound having a reduced content of metal impurities, and a method for efficiently or easily producing the fluorene compound with high productivity.

As a result of diligent studies to achieve the above problems, the present inventors have found that a (meth) acryloyloxy (poly) alkoxy group is bonded to an aryl group substituted at the 9-position of the fluorene skeleton via a carbonyl group. We have found that the monofunctional (meth) acrylate compound has a surprisingly high refractive index and suppresses coloring, and completed the present invention.

That is, the novel compound of the present invention is represented by the following formula (1).

(In the formula, Z represents an aromatic hydrocarbon ring, R ¹ and R ³ each independently represent a non-reactive group, R ² represents a hydrocarbon group, and R ⁴ represents a hydrogen atom or a methyl group. , A represents a linear or branched alkylene group, k independently represents an integer of 0 to 8, m represents 0 or 1, n represents an integer of 0 or more, and p represents 1 or more. Indicates an integer of).

In the above formula (1), Z may be a C _6-12 allene ring, R ¹ may be a hydrocarbon group, a cyano group or a halogen atom, and R ³ may be a halogen atom or a hydrocarbon group [-. ^Ra ], group [-OR ^a ] (in the formula, ^Ra represents the hydrocarbon group), group [-SR ^a ] (in the formula, ^Ra represents the hydrocarbon group), acyl group, nitro It may be a group, a cyano group, or a mono or di-substituted amino group, A may be a linear or branched C _2-6 alkylene group, and n may be an integer of 0-4. Often, p may be an integer of 1-10.

In the above formula (1), Z may be a benzene ring or a naphthalene ring, R ¹ may be a linear or branched alkyl group, and R ² may be a linear or branched alkyl group. Alternatively, it may be a cycloalkyl group, R ³ may be a linear or branched alkyl group or an aryl group, and A may be a linear or branched C _2-4 alkylene group. Often, k may be an integer of 0 to 2, m may be 1, n may be an integer of 0 to 2, and p may be an integer of 1 to 5.

The present invention also includes a method for producing a compound represented by the formula (1) by reacting a compound represented by the following formula (2b) with a compound represented by the following formula (3). To do.

(In the formula, X ² represents a hydroxyl group, an alkoxy group or a halogen atom, and Z, R ¹ , R ² , R ³ , k, m and n are the same as in the above formula (1)).

^{(Wherein, R} 4, A and p are as defined above formula (1)).

The present invention includes a polymerizable composition (or curable composition) containing the compound represented by the formula (1), and a polymer (or cured product) obtained by polymerizing the polymerizable composition, that is, A polymer containing the compound represented by the formula (1) as a polymerization component (or monomer component) is also included.

In addition, in this specification and claims, the number of carbon atoms of a substituent may be indicated by C ₁ , C ₆ , C _{10, and the} like. For example, an alkyl group having 1 carbon atom is indicated by "C ₁ alkyl", and an aryl group having 6 to 10 carbon atoms is indicated by "C _6-10 aryl".

Since the novel monofunctional compound of the present invention has a predetermined chemical structure, it has a surprisingly high refractive index even if it is monofunctional (even if two aryl groups are not substituted at the 9-position of the fluorene skeleton). A resin having the above can be formed. In addition, despite having a fluorene skeleton with high heat resistance, the melting point is not too high, so that the fluidity can be easily improved or adjusted without heating to an excessively high temperature, and coloring by heating (coloring by heating ( Or yellowing) can be suppressed, and since it can take a solid form at room temperature, it is easy to measure at the time of use and is excellent in handleability. Further, the monofunctional compound is suppressed in coloring. Moreover, the content of metal impurities is also reduced. In the present invention, such a monofunctional compound can be produced efficiently or easily with high productivity.

[Monofunctional fluorene compound represented by the formula (1) and its properties]

(In the formula, Z represents an aromatic hydrocarbon ring, R ¹ and R ³ each independently represent a non-reactive group, R ² represents a hydrocarbon group, and R ⁴ represents a hydrogen atom or a methyl group. , A represents a linear or branched alkylene group, k independently represents an integer of 0 to 8, m represents 0 or 1, n represents an integer of 0 or more, and p represents 1 or more. Indicates an integer of).

In the above formula (1), examples of the substituent (non-reactive group or non-radical polymerizable group) represented by R ¹ include a hydrocarbon group, specifically, an alkyl group, an aryl group and the like; a cyano group. ; Halogen atom, specifically, a fluorine atom, a chlorine atom, a bromine atom and the like can be mentioned.

Examples of the alkyl group include linear or branched C _1-6 such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group and t-butyl group. Alkyl groups can be mentioned.

Examples of the aryl group include a C _6-10 aryl group such as a phenyl group.

If k is 1 or more, of these radicals R ^1, an alkyl group, a cyano group or a halogen atom, more preferably an alkyl group, among others, straight-chain or branched-chain C _1-4 alkyl group, In particular, a linear or branched C _1-3 alkyl group such as a methyl group is preferable.

The substitution number k of the radicals ^{R 1} are, for example, 0-7 about integers, the preferable range, the following stages, an integer of 0 to 6, an integer of 0 to 5, an integer of 0 to 4, 0 to 3 It is an integer, an integer of 0 to 2, more preferably 0 or 1, especially 0. If k is 2 or more, two or more kinds of groups R ¹ may be the same or different from each other. The substitution position of the group R ¹ is not particularly limited. For example, when k is 2 or more, the group R ¹ may be substituted with at least one benzene ring forming a fluorene ring, and both benzene rings may be substituted. It may be replaced with. The substitution position of a representative group R ^1, for example, may be any position 2-position to 7-position of the fluorene ring, specifically, 2-position, like the 3-position and / or 7 There may be. The number of substitutions, the substitution positions, and the types of substituents in the two benzene rings forming the fluorene ring may be the same or different from each other.

Examples of the hydrocarbon group represented by R ² include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

Examples of the alkyl group include linear or branched C _1-10 alkyl such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group and t-butyl group. Examples thereof include a linear or branched C _1-6 alkyl group, and more preferably a linear or branched C _1-4 alkyl group.

Examples of the cycloalkyl group include C _5-10 cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group.

Examples of the aryl group include a C _6-12 aryl group such as a phenyl group, an alkylphenyl group, a biphenylyl group and a naphthyl group. Examples of the alkylphenyl group include mono to tri-C _1-4 alkyl-phenyl groups such as a methylphenyl group (tolyl group) and a dimethylphenyl group (xysilyl group).

Examples of the aralkyl group include C _6-10 aryl-C _1-4 alkyl groups such as a benzyl group and a phenethyl group.

The number of substitutions m may be either 0 or 1, but is preferably 1 from the viewpoint of suppressing side reactions and coloring. When m is 1, R ² may be an aryl group such as an alkyl group or a phenyl group, or an aralkyl group such as a benzyl group or a phenethyl group, and the alkyl group may be used because it is easy to prepare and productivity can be improved. preferable. Among them, a hydrocarbon group having a small number of carbon atoms is preferable, for example, a linear or branched C _1-6 alkyl group, and more preferably, a linear or branched C _{1-4 in a} stepwise manner. Alkyl group, linear or branched C _1-3 alkyl group, C _1-2 alkyl group, and methyl group is particularly preferable. Further, from the viewpoint that the melting point can be reduced and the handleability can be improved while maintaining a high refractive index, R ² is preferably an aliphatic hydrocarbon group such as an alkyl group or a cycloalkyl group, and more preferably linear. Alternatively, it is a branched C _1-6 alkyl group or a C _5-10 cycloalkyl group. Of these, alkyl groups such as linear or branched C _1-4 alkyl groups are preferable, and among them, linear or branched C _1-3 alkyl groups are preferable, and C _1-2 is particularly preferable. It is an alkyl group, most preferably a methyl group. In the present invention, even if R ² is not a group having an aromatic hydrocarbon ring skeleton such as an aryl group whose refractive index can be easily improved, the refractive index is unexpectedly high, so that a high refractive index and handleability are well balanced. It is compatible.

Examples of the arene ring (aromatic hydrocarbon ring) represented by Z include a monocyclic arene ring such as a benzene ring and a polycyclic arene ring (polycyclic aromatic hydrocarbon ring). Examples of the polycyclic arene ring include a fused polycyclic arene ring (condensed polycyclic aromatic hydrocarbon ring), a ring-assembled arene ring (ring-assembled aromatic hydrocarbon ring), and the like.

Examples of the fused polycyclic arene ring include a fused bicyclic arene ring, specifically, a fused bicyclic _C10-16 arene ring such as a naphthalene ring; and a fused tricyclic arene ring, specifically. , Anthracene ring, phenanthrene ring and other fused bicyclic arene rings and the like. Preferred fused polycyclic arene rings include fused polycyclic C _10-16 arene rings such as naphthalene ring and anthracene ring, and more preferably fused polycyclic C _10-14 arene ring, in particular. A naphthalene ring is preferred.

The ring-aggregated arene ring includes, for example, a bearene ring, specifically, a bi-C _6-12 arene ring such as a biphenyl ring, a binaphthyl ring, or a phenylnaphthalene ring; An example is the Tel C _6-12 arene ring. Examples of the phenylnaphthalene ring include a 1-phenylnaphthalene ring and a 2-phenylnaphthalene ring. Preferred ring-assembled arene rings include biC _6-10 arene rings such as a biphenyl ring, a binaphthyl ring, and a phenylnaphthalene ring, and a biphenyl ring is particularly preferable.

In the present specification and claims, a ring-set arene ring containing a fused polycyclic arene ring frame such as a naphthalene ring frame is classified as a ring-set arene ring.

Among the rings Z, a C _6-12 arene ring such as a benzene ring, a naphthalene ring, and a biphenyl ring is preferable, and a C _6-10 arene ring such as a benzene ring and a naphthalene ring is more preferable, which is excellent in productivity and can be colored. A benzene ring is particularly preferable from the viewpoint of excellent balance between high refractive index and handleability while suppressing the ring.

As a substitution position of the ring Z bonded to the 9-position of the fluorene ring, for example, when the ring Z is a benzene ring, the (meth) acryloyl group-containing group in the ring Z (that is, the group [-C (= O)) is usually used. -(OA) _p -OC (= O) -CR ⁴ = CH ₂ ])) is preferably at the o-position or the p-position, and more preferably at the p-position.

As the substituent represented by R ³ (non-reactive group or a non-radical polymerizable group) is, for example, a hydrocarbon group or a group [-R ^a], specifically, an alkyl group, a cycloalkyl group, an aryl group, Aralkyl group, etc .; group [-OR ^a ] (in the formula, ^Ra represents the above hydrocarbon group), specifically, alkoxy group, cycloalkyloxy group, aryloxy group, aralkyloxy group, etc .; group [- SR ^a ] (in the formula, ^Ra represents the above hydrocarbon group), specifically, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, etc .; an acyl group, specifically, an acetyl group, etc. C _1-6 alkyl-carbonyl group and the like; nitro group; cyano group; mono or di-substituted amino group, specifically, dialkylamino group, bis (alkylcarbonyl) amino group and the like.

Examples of the alkyl group represented by ^Ra include linear or branched groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group and t-butyl group. _Examples thereof include a chain C _1-10 alkyl group, preferably a linear or branched C _1-6 alkyl group, and more preferably a linear or branched C _1-4 alkyl group. Examples of the cycloalkyl group represented by ^Ra include C _5-10 cycloalkyl groups such as cyclopentyl group and cyclohexyl group. Examples of the aryl group represented by ^Ra include a C _6-12 aryl group such as a phenyl group, an alkylphenyl group, a biphenylyl group and a naphthyl group. Examples of the alkylphenyl group include mono to tri-C _1-4 alkyl-phenyl groups such as a methylphenyl group (tolyl group) and a dimethylphenyl group (xysilyl group). Examples of the aralkyl group represented by ^Ra include C _6-10 aryl-C _1-4 alkyl groups such as a benzyl group and a phenethyl group.

Specifically, as the group [-OR ^a], it includes groups corresponding to the example of the hydrocarbon group R ^a. Examples of the alkoxy group include a linear or branched C _1-10 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group and a t-butoxy group. Examples of the cycloalkyloxy group include a C _5-10 cycloalkyloxy group such as a cyclohexyloxy group. Examples of the aryloxy group include a _C6-10 aryloxy group such as a phenoxy group. Examples of the aralkyloxy group include a C _6-10 aryl-C _1-4 alkyloxy group such as a benzyloxy group.

Specifically, as the group [-SR ^a], it includes groups corresponding to the example of the hydrocarbon group R ^a. Examples of the alkylthio group include C _1-10 alkylthio groups such as methylthio group, ethylthio group, propylthio group, n-butylthio group and t-butylthio group. Examples of the cycloalkylthio group include a C _5-10 cycloalkylthio group such as a cyclohexylthio group. The arylthio group, for example, C _6-10 arylthio groups such as thiophenoxy group (or phenylthio group). Examples of the aralkylthio group include a C _6-10 aryl-C _1-4 alkylthio group such as a benzylthio group.

In the mono or di-substituted amino group, examples of the dialkylamino group include a diC _1-4 alkylamino group such as a dimethylamino group. Examples of the bis (alkylcarbonyl) amino group include a bis (C _1-4 alkyl-carbonyl) amino group such as a diacetylamino group.

Among these groups R ^3, typically alkyl group, a cycloalkyl group, an aryl group, a hydrocarbon group such as an aralkyl group, an alkoxy group, an acyl group, a nitro group, a cyano group, and a substituted amino group .. When n is 1 or more, the preferred group R ³ is an alkyl group, specifically, a linear or branched C _1-6 alkyl group such as a methyl group; an aryl group, specifically, phenyl. C _6-14 aryl groups such as groups; alkoxy groups, specifically, linear or branched C _1-4 alkoxy groups such as methoxy groups, and among them, alkyl groups and aryl groups are preferable. In particular, linear or branched C _1-4 alkyl groups such as methyl groups and C _6-10 aryl groups such as phenyl groups are preferable. When the group R ³ is an aryl group, the group R ³ may form the ring-aggregated arene ring together with the ring Z. When the substitution number n is 2 or more, two or more kinds of the radicals R ³ to be substituted with the ring Z may be the same or different from each other.

The substitution number n of the group R ³ can be appropriately selected depending on the type of the ring Z, and may be, for example, an integer of about 0 to 8, preferably an integer of 0 to 4, 0 to 3, stepwise. It is an integer, an integer of 0 to 2, more preferably 0 or 1, especially 0. The substitution position of the radicals R ³ is not particularly limited, binding position of the 9-position of the ring Z and a fluorene ring, and ring Z and (meth) acryloyl group-containing group (i.e., group [-C (= O) - ( OA) It may be replaced with a position other than the coupling position with _p -OC (= O) -CR ⁴ = CH ₂ ]).

The (meth) acryloyl group-containing group can be substituted at an appropriate position on the ring Z, and when the ring Z is a benzene ring, it is preferably at the 2- or 4-position, and more preferably at the 4-position.

Examples of the linear alkylene group represented by A include a linear C _2-6 alkylene group such as an ethylene group, a trimethylene group and a tetramethylene group, and a linear C _2-4 alkylene group is preferable. More preferably, it is a linear C _2-3 alkylene group, particularly an ethylene group, and examples of the branched alkylene group include a branched chain such as a propylene group, a 1,2-butandyl group and a 1,3-butanjiyl group. Examples thereof include a C _3-6 alkylene group, preferably a branched C _3-4 alkylene group, and a propylene group is particularly preferable. Of these alkylene groups A, preferably linear or branched C _2-6 alkylene groups, linear or branched C _2-4 alkylene groups, linear or branched chains, in a stepwise manner. It is a _C2-3 alkylene group, of which an ethylene group and a propylene group are preferable, and an ethylene group is particularly preferable. When the number of repetitions p is 2 or more, the types of the 2 or more groups A forming the polyoxyalkylene group may be different from each other, but are often the same.

The number of repetitions p of the oxyalkylene group (-OA-) may be selected from, for example, an integer in the range of about 1 to 20, and the preferable range is preferably 1 to 15, 1 to 10, 1 to 1 in stages. It is 8, 1-5, 1-3, 1-2, and in particular, it is often 1. The number of repetitions p may be an average value (or an arithmetic mean value or an arithmetic mean value), that is, an average number of added moles, and the range thereof is the same as the range of the integers including the preferred embodiment. If the value of the number of repetitions p is too large, characteristics such as high refractive index and high heat resistance may deteriorate.

The number of repetitions p can be measured by a conventional method. For example, when a predetermined alkylene oxide (alkylene carbonate or haloalkanol) is reacted with a raw material hydroxy compound to form a (poly) alkyleneoxy group. , A method of calculating as an arithmetic mean or arithmetic mean value from the ratio of the amount of the hydroxy compound (or hydroxyl value) to the amount of alkylene oxide (alkylene carbonate or haloalkanol) consumed in the reaction, for example, Japanese Patent Application Laid-Open No. It can be measured by the method described in Japanese Patent Application Laid-Open No. 2013-53310.

R ⁴ may be either a hydrogen atom or a methyl group, but is usually a hydrogen atom because it is easy to improve the refractive index and curability.

Representative compounds represented by the formula (1) include, for example, 9-[(meth) acryloyloxy (poly) alkoxycarbonylaryl] -9-alkylfluorenes, 9-[(meth) acryloyloxy (poly). Alkoxy) carbonylaryl] -9-cycloalkylfluorenes, 9-[(meth) acryloyloxy (poly) alkoxy) carbonylaryl] -9-arylfluorenes, 9-[(meth) acryloyloxy (poly) alkoxy) carbonyl Aryl] -9-alkoxyfluorenes and the like.

In addition, in this specification and claims, "(poly) alkoxy" is used in the meaning which includes both an alkoxy group and a polyalkoxy group.

Examples of 9-[(meth) acryloyloxy (poly) alkoxycarbonylaryl] -9-alkylfluorenes include 9- [4- (2- (meth) acryloyloxyethoxy) carbonylphenyl] -9-methylfluorene, 9- [4- (2- (meth) acryloyloxypropoxy) carbonylphenyl] -9-methylfluorene, 9- [4- (4- (meth) acryloyloxybutoxy) carbonylphenyl] -9-methylfluorene, 9- [4- (2- (2- (meth) acryloyloxyethoxy) ethoxy) carbonylphenyl] -9- [(meth) acryloyloxy (mono to deca) C _2-6 alkoxy) carbonyl C ₆ such as -9-methylfluorene _-10aryl ] -9-C _1-6 alkyl-fluorene and the like.

9-[(meth) acryloyloxy (poly) alkoxy) carbonylaryl] -9-cycloalkylfluorenes include, for example, 9- [4- (2- (meth) acryloyloxyethoxy) carbonylphenyl] -9-cyclohexyl. Examples thereof include 9-[(meth) acryloyloxy (mono to deca) C _2-6 alkoxy) carbonyl C _6-10 aryl] -9-C _5-10 cycloalkyl-fluorene such as fluorene.

9-[(meth) acryloyloxy (poly) alkoxy) carbonylaryl] -9-arylfluorenes include, for example, 9- [4- (2- (meth) acryloyloxyethoxy) carbonylphenyl] -9-phenylfluorene. 9-[(Meta) acryloyloxy (mono to deca) C _2-6 alkoxy) carbonyl C _6-10 aryl] -9-C _6-12 aryl-fluorene and the like.

9-[(meth) acryloyloxy (poly) alkoxy) carbonylaryl] -9-aralkylfluorenes include, for example, 9- [4- (2- (meth) acryloyloxyethoxy) carbonylphenyl] -9-benzylfluorene. 9-[(meth) acryloyloxy (mono to deca) C _2-6 alkoxy) carbonyl C _6-10 aryl] -9-C _6-12 aryl C _1-6 alkyl-fluorene and the like.

Preferred compounds represented by the formula (1) include 9-[(meth) acryloyloxy (poly) alkoxycarbonylaryl] -9-alkylfluorenes and 9-[(meth) acryloyloxy (poly) alkoxy) carbonylaryl. ] -9-Cycloalkylfluorenes, among which 9-[(meth) acryloyloxy (mono to) such as 9- [4- (2- (meth) acryloyloxyethoxy) carbonylphenyl] -9-methylfluorene. Hexa) C _2-4 alkoxy) carbonylphenyl] -9-C _1-4 alkyl-fluorene.

The monofunctional (meth) acrylate represented by the formula (1) has a high refractive index even if it is monofunctional (or even if two aryl groups are not substituted at the 9-position of the fluorene skeleton). And coloring is suppressed.

The melting point of the monofunctional (meth) acrylate represented by the formula (1) may be, for example, 30 to 100 ° C., and the preferred range is 40 to 90 ° C., 50 to 50 to 90 ° C. in the following steps. The temperature is 80 ° C., 55 to 75 ° C., 60 to 70 ° C., 62 to 67 ° C., and more preferably 64 to 65 ° C. If the melting point is too high, sufficient fluidity may not be obtained with a small amount of heating, and handleability or moldability may deteriorate, and heating to a high temperature to ensure fluidity may cause coloring (or yellowing). There is also. On the other hand, if the melting point is too low, it becomes a liquid or a viscous liquid at room temperature, which makes it difficult to measure during use and may reduce handleability.

[Method for producing monofunctional fluorene compound represented by formula (1)]
The method for producing the compound represented by the formula (1) is not particularly limited, but can be typically prepared according to the following reaction process formula or the like.

(In the formula, X ¹ represents a halogen atom, X ² represents a hydroxyl group, an alkoxy group or a halogen atom, and Z, R ¹ , R ² , R ³ , R ⁴ , A, k, m, n and p are preferred embodiments. Is the same as above).

(Preparation of compound represented by formula (2b))
The compound represented by the formula (2b) is represented by the formula (2a) obtained by reacting, for example, the compound represented by the formula (i) (4) with the compound represented by the formula (5a). The compound to be hydrolyzed may be prepared by a method of reacting the compound represented by the formula (ii) (4) with the compound represented by the formula (5b).

In the compound represented by the formula (4) to be subjected to the reaction with the compound represented by the formula (5a) or (5b), the substitution number m of R ² may be 1, but the reactivity is easily improved. From the point, it is usually 0 in many cases. Typical examples of the compound represented by the formula (4) include 9H-fluorene, 9-methylfluorene, 9-phenylfluorene and the like, and 9H-fluorene is preferable.

In the compounds of the formula (5a) or (5b), the halogen atom represented by X ^1, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, usually bromine atom or iodine atom A bromine atom is preferable because it is often present and it is easy to selectively prepare a monosubstituted product.

In the compounds of the formula (5b), the alkoxy group represented by X ^2, for example, a lower alkoxy group, specifically, a methoxy group, an ethoxy group, t-linear or branched butoxy group Examples thereof include a chain C _1-4 alkoxy group, which is usually a t-butoxy group.

Further, examples of the halogen atom represented by X ² include a chlorine atom, a bromine atom, an iodine atom and the like, and usually, it is often a chlorine atom or a bromine atom. Among the compounds represented by the formula (5b), X ² is preferably an alkoxy group from the viewpoint that the compound represented by the formula (2b) can be easily prepared.

In the compounds of the formula (5a) or (5b), the substitution position of X ¹ in ring Z is the same, including the preferred embodiments and the coupling position of the 9-position of fluorene in the ring Z in the formula (1) Yes, the substitution positions of the cyano group or the group [-C (= O) -X ² ] in the ring Z are the bonding positions with the (meth) acryloyl group-containing group in the ring Z of the above formula (1) and preferred embodiments, respectively. the same, including the substitution position of R ³ in the ring Z is the same as in the formula, including the preferred embodiments (1).

Typical examples of the compound represented by the formula (5a) include halo-cyanoC _6-10 arene such as p-bromobenzonitrile and p-iodobenzonitrile.

The compound represented by formula (5b), typically, compound ^{X 2} is an alkoxy group, e.g., p- bromo benzoate, t-p-bromobenzoic acid butyl, p- iodobenzoic acid t- Examples thereof include halo- (C _1-4 alkoxy-carbonyl) C _6-10 arenes such as butyl.

The ratio of the compound represented by the formula (5a) or (5b) to be used may be, for example, about 1 to 10 mol with respect to 1 mol of the compound represented by the formula (4), and is preferably in the range of 1 to 10 mol. , 1.3-8 mol, 1.5-6 mol, 1.8-5 mol, 2-4.5 mol, 2.3-4 mol, more preferably 2.5-. It is 3.5 mol.

The reaction between the compound represented by the formula (4) and the compound represented by the formula (5a) or (5b) may usually be carried out in the presence of a base. Examples of the base include organic bases such as amines, quaternary ammonium metal alkoxides, organic lithium compounds, organic magnesium compounds (Grignard reagents), and organic acid salts; metal carbonates or hydrogen carbonates, metal hydroxides, metals. Examples include inorganic bases such as hydrides.

Examples of the amines include aliphatic amines, aromatic amines, and heterocyclic amines. Aliphatic amines include, for example, triethylamine, diisopropylethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, dicyclohexylethylamine, N, N, N', N'-tetramethylethylenediamine and the like. Examples include tertiary amines. Examples of the aromatic amine include aromatic tertiary amines such as N, N-dimethylaniline. Examples of the heterocyclic amine include pyridine, lutidine, colisine, 4- (dimethylamino) pyridine, 4-pyrrolidinopyridine, 1-methylpiperidine, 1-ethylpiperidine, 1,2,2', 6,6'. -Pentamethylpiperidin, 1-methylpyrrolidine, imidazole, 2,6-dimethylpiperazine, 4-methylmorpholin, 1,5-diazabicyclo [4.3.0] -5-nonen, 1,8-diazabicyclo [5.4] .0] -7-Undesen, etc.) and the like.

Examples of the quaternary ammonium hydroxide include tetraalkylammonium hydroxide such as tetramethylammonium hydroxide and trimethylbenzylammonium hydroxide.

Examples of the metal alkoxide include alkali metal C _1-6 alkoxides such as potassium t-butoxide.

Examples of the organic lithium compound include alkyllithium such as methyllithium, n-butyllithium, s-butyllithium and t-butyllithium; aryllithium such as phenyllithium; lithium diisopropylamide (LDA) and lithium 2,2. Examples thereof include lithium amides such as 6,6-tetramethylpiperazide (LiTMP) and lithium hexamethyldisilazide (LHMDS).

Examples of the organic magnesium compound (Grignard reagent) include alkylmagnesium halides such as methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium bromide, isopropylmagnesium bromide, n-butylmagnesium bromide, and t-butylmagnesium bromide. Cycloalkylmagnesium halides such as cyclopropylmagnesium bromide and cyclopentylmagnesium bromide; arylmagnesium halides such as phenylmagnesium bromide and phenylmagnesium iodide; and aralkylmagnesium halides such as benzylmagnesium bromide.

Examples of the organic acid salt include organic acid metal salts such as sodium acetate.

Examples of the metal carbonate or hydrogen carbonate include alkali metal or alkaline earth metal carbonates or hydrogen carbonates such as potassium carbonate, sodium carbonate, potassium hydrogen carbonate, and sodium hydrogen carbonate.

Examples of the metal hydroxide include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, or alkali earth metals.

Examples of the metal hydride include hydrides of alkali metals such as sodium hydride or alkaline earth metals.

These bases may be used alone or in combination of two or more. Of these bases, metal alkoxides, especially alkali metal alkoxides such as potassium t-butoxide, are preferred.

The ratio of the base used may be, for example, about 0.1 to 20 mol with respect to 1 mol of the compound represented by the formula (4), and the preferable range is 0.5 to 0.5 to 2 in stages. It is 15 mol, 1 to 10 mol, 1.5 to 8 mol, 2 to 8 mol, 3 to 7 mol, 4 to 6 mol, and more preferably 4.5 to 5.5 mol. The proportion of the base used is, for example, 10 to 1000 parts by mass, 50 to 800 parts by mass, 100 to 600 parts by mass, 150 to 530 parts by mass with respect to 100 parts by mass of the compound represented by the formula (4). It is 200 to 480 parts by mass, 250 to 430 parts by mass, 300 to 380 parts by mass, and more preferably 330 to 350 parts by mass. If the proportion of bases is too small, the reaction may not proceed sufficiently, and if the proportion of bases is too large, when m is 0, the formula (5a) is for one compound represented by the formula (4). ) Or (5b), the amount of by-products such as disubstituted products in which a plurality of compounds are reacted increases, and the yield of the target mono-substituted product (compound represented by the formula (2a) or (2b)) is increased. The rate may decrease.

Further, the reaction between the compound represented by the formula (4) and the compound represented by the formula (5a) or (5b) is usually carried out in order to selectively improve the yield of the monosubstituted product of the target product. , In the presence of a catalyst. Examples of the catalyst include divalent zinc compounds such as zinc halide and dialkyl zinc, and the reaction is usually carried out in the presence of at least one zinc compound selected from these divalent zinc compounds. There are many. Among them, zinc halide is less soluble in the organic layer than metal catalysts containing palladium and ligands and can be easily removed by washing after the reaction is completed. Therefore, the content of metal impurities from the target fluorene compound can be effectively adjusted. Can be reduced.

Examples of zinc halide include zinc fluoride, zinc chloride, zinc bromide, zinc iodide and the like. Examples of the dialkyl zinc include diC _1-6 alkyl zinc such as dimethylzinc and diethylzinc. These catalysts can be used alone or in combination of two or more.

Among these zinc compounds, zinc halide is preferable, zinc chloride, zinc bromide, and zinc iodide are preferable, and zinc chloride is particularly preferable.

The ratio of the catalyst used may be, for example, about 0.5 to 10 mol, more specifically about 0.55 to 9 mol, with respect to 1 mol of the compound represented by the formula (4), which is preferable. The range is as follows, in stages, 0.6 to 8 mol, 0.65 to 7 mol, 0.7 to 6 mol, 0.75 to 5.5 mol, 0.8 to 5 mol, 0.85 to 4.5 mol, 0.9-4 mol, 0.95-3.5 mol, 1-3 mol, 1.1-2.5 mol, 1.2-2 mol, 1.3-1.8 mol It is more preferably 1.4 to 1.6 mol. If the proportion of the catalyst is too small, the yield of the monosubstituted product of the target product may decrease. When the divalent zinc compound is zinc halide and the ratio of use thereof is 1 mol or more with respect to 1 mol of the compound represented by the formula (1), the mono-substituted product of the target substance is more selectively selected ( It seems easy to obtain (efficiently).

The ratio of the divalent zinc compound to the base may be, for example, the former / the latter (molar ratio) = 1 / 0.5 to 1/20, and the preferable range is as follows, step by step. 1 / 1-1 / 10, 1 / 1.5-1 / 8, 1/2-1 / 7, 1 / 2.3-1 / 6.5, 1 / 2.5-1 / 6, 1 / It is 2.6 to 1 / 5.8, 1 / 2.8 to 1 / 5.5, and more preferably 1/3 to 1 / 5.3. If the proportion of base is too small with respect to the catalyst, the reaction may not proceed sufficiently. If the ratio of the base is too large with respect to the catalyst, side reactions may easily occur, and particularly when m is 0, by-products such as disubstituted products may increase.

The reaction between the compound represented by the formula (4) and the compound represented by the formula (5a) or (5b) may be carried out in the absence of a solvent, but is usually carried out in a solvent. .. Examples of the solvent include aprotonic polar solvents such as ethers, ketones, esters, carbonates, amides, ureas, nitriles, nitrated hydrocarbons, phosphoramides, sulfones, sulfoxides and the like. Be done.

Examples of the ethers include chain ethers and cyclic ethers. Examples of chain ethers include diC _1-6 alkyl ethers such as diethyl ether, diisopropyl ether, and dibutyl ether; ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene. Examples thereof include (mono to hexa) C _2-4 alkylene glycol di C _1-6 alkyl ethers such as glycol dimethyl ether. Examples of the cyclic ethers include tetrahydrofuran (THF), tetrahydropyran, 1,4-dioxane, 1,3-dioxane, 1,3-dioxolane and the like.

Examples of the ketones include chain ketones and cyclic ketones. Examples of chain ketones include diC _1-6 alkyl-ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of cyclic ketones include C _5-10 cycloalkanone such as cyclohexanone.

Examples of the esters include chain esters and cyclic esters (or lactones). Examples of the chain esters include C _2-6 alkanoic acid C _1-6 alkyl esters such as methyl acetate, ethyl acetate and butyl acetate. Examples of the lactones include 5- to 7-membered ring lactones such as γ-butyrolactone, γ-valerolactone, and γ-caprolactone (or γ-hexanolactone).

Examples of the carbonates include chain carbonates and cyclic carbonates. Examples of the chain carbonates include diC _1-6 alkyl-carbonate such as dimethyl carbonate (or dimethyl carbonate), ethyl methyl carbonate, and diethyl carbonate (or diethyl carbonate). Examples of the cyclic carbonates include di-tetramethylene carbonates such as ethylene carbonate (or ethylene carbonate) and propylene carbonate (or propylene carbonate).

Examples of the amides include chain amides, cyclic amides (or lactams) and the like. Examples of chain amides include N, N-diC _1-6 alkyl-C ₁ such as N, N-dimethylformamide (DMF), N, N-diethylformamide, and N, N-dimethylacetamide (DMAc). _-6 Alkaneamide and the like can be mentioned. Examples of the cyclic amides include 5- to 7-membered ring lactams such as N-methyl-2-pyrrolidone.

Examples of the ureas (or ureas) include chain ureas and cyclic ureas. Examples of chain ureas include tetra C _1-6 alkyl-urea such as tetramethylurea, tetraethylurea and tetraisopropylurea. Examples of cyclic ureas include 1,3-dimethyl-2-imidazolidinone (DMI or N, N'-dimethylethylene urea), N, N'-dimethyl-N, N'-trimethylene urea (or N, N, N'-di C _1-6 alkyl-N, N'-di to tetramethylene urea and the like such as N'-propylene urea) can be mentioned.

Examples of the nitriles include cyanide hydrocarbons, specifically, cyanide C _1-6 alkanes such as acetonitrile and propiononitrile, and cyanide arenes such as benzonitrile.

Examples of the nitrated hydrocarbons include nitro C _1-6 alkane such as nitromethane, nitroethane, 1-nitropropane and 2-nitropropane, and nitroarene such as nitrobenzene.

Examples of the phosphoramides include hexa-C _1-6 alkylphosphoramides such as hexamethylphosphoramides.

Examples of the sulfones include chain sulfones and cyclic sulfones. Examples of chain sulfones include di-C _1-6 alkyl sulfones such as ethyl methyl sulfone and isopropyl ethyl sulfone. Examples of the cyclic sulfones include tri-hexamethylene sulfones such as sulfolane (or tetramethylene sulfone or tetrahydrothiophene-1,1-dioxide).

Examples of the sulfoxides include diC _1-6 alkyl sulfoxides such as dimethyl sulfoxide (DMSO).

These solvents can also be used alone or in combination of two or more. Among these solvents, amides such as DMF, sulfoxides such as DMSO, and among them, amides such as DMF are often used. The amount of the solvent used is not particularly limited as long as the reaction system can be uniformly dispersed and the reaction can be carried out efficiently. For example, 100 to 10,000 with respect to 100 parts by mass of the compound represented by the formula (4). It is about a mass part, preferably 1000 to 5000 parts by mass, and more preferably 2000 to 4000 parts by mass.

The reaction between the compound represented by the formula (4) and the compound represented by the formula (5a) or (5b) may usually be carried out in an inert atmosphere such as nitrogen gas or a rare gas, and may be carried out under normal pressure or It may be carried out under pressure. Further, the reaction may be carried out with stirring. The reaction temperature can be selected from, for example, a range of about 0 to 200 ° C., and the preferred range is, in stages, 20 to 150 ° C., 50 to 120 ° C., 60 to 100 ° C., 70 to 90 ° C., 75 to 85 ° C. ℃. If the reaction temperature is too high, side reactions may easily occur, and particularly when m is 0, the proportion of by-products such as disubstituted products may increase. Even if the reaction temperature is relatively low, the reaction seems to proceed efficiently. The reaction time is not particularly limited and can be selected from, for example, a range of about 30 minutes to 48 hours. The preferred range is 1 to 24 hours, 2 to 12 hours, and 2.5 to 6 in the following steps. It's time.

After completion of the reaction, the reaction mixture (reaction solution or reaction mixture) is prepared by conventional purification or separation means such as filtration, concentration, extraction, neutralization, washing, drying, crystallization, recrystallization, column chromatography and the like. , These may be purified by a combination of means.

(Hydrolyzed compound represented by formula (2a))
When the compound represented by the formula (2a) is synthesized by the method (i), the compound is further hydrolyzed by a conventional method, for example, by hydrolyzing in the presence of an acid or a base. In 2b), a compound in which X ² is a hydroxyl group can be prepared.

Examples of the acid include an inorganic acid; an organic acid; a Lewis acid such as boron trifluoride etherate and tin tetrachloride; and a solid acid catalyst such as a cation exchange resin. Examples of the inorganic acid include strong acids, specifically sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and the like; homo- or heteropolyacids, specifically, tonguestric acid, molybdrine acid, tonguestofic acid, molybdose silicic acid and the like. Be done. Examples of the organic acid include sulfonic acid, specifically, alkane sulfonic acid such as methane sulfonic acid and ethane sulfonic acid, fluorinated alkane sulfonic acid such as trifluoromethane sulfonic acid, and allene sulfone such as p-toluene sulfonic acid. Examples include acid. These acid catalysts may be used alone or in combination of two or more.

Examples of the base include the bases exemplified in the reaction between the compound represented by the formula (4) and the compound represented by the formula (5a) or (5b), and these bases can be used alone or. Two or more types can be used in combination.

Of these, bases, such as alkali metal hydroxides such as sodium hydroxide, are commonly used. The ratio of the acid or base may be, for example, about 1 to 100 mol, preferably 10 to 70 mol, more preferably 30 to 30 to 1 mol of the cyano group of the compound represented by the formula (2a). It is 50 mol.

The ratio of water may be 2 mol or more with respect to 1 mol of the cyano group of the compound represented by the formula (2a), and 100 parts by mass of the compound represented by the formula (2a). It may be about 5000 parts by mass. Usually, water is often added to the reaction system in the form of an aqueous solution of acid or base.

The hydrolysis reaction may be carried out in the presence of a phase transfer catalyst. Examples of the interphase transfer catalyst include organic ammonium compounds (or quaternary ammonium compounds), specifically, organic ammonium halides such as tetraalkylammonium halide and trialkylammonium halide; tetraalkylammonium hydroxide and trialkylaralkyl. Examples thereof include organic ammonium hydroxide such as ammonium hydroxide.

Examples of the tetraalkylammonium halide include tetra C _1-8 alkylammonium halides such as tetramethylammonium bromide and tetrabutylammonium bromide. Examples of the trialkylaralkylammonium halide include tri-C _1-8 alkyl-C _6-10 aryl C _1-4 alkylammonium halide such as triethylbenzylammonium chloride.

Examples of the tetraalkylammonium hydroxide include tetra C _1-8 alkylammonium halides such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Examples of the trialkyl aralkylammonium hydroxide include tri-C _1-8 alkyl-C _6-10 aryl C _1-4 alkyl ammonium hydroxide such as trimethylbenzylammonium hydroxide.

These phase transfer catalysts can also be used alone or in combination of two or more. Of these phase transfer catalysts, organic ammonium halides, specifically trialkylaralkylammonium halides such as triethylbenzylammonium chloride, are often used.

The ratio of the phase transfer catalyst may be, for example, about 0.001 to 1 mol, preferably 0.1 to 0.5, based on 1 mol of the cyano group of the compound represented by the formula (2a). It is about 0.2 to 0.4 mol, more preferably 0.2 to 0.4 mol.

The hydrolysis reaction may be carried out in the absence of a solvent, but is usually carried out in a solvent. Examples of the solvent include alcohols, specifically, C _1-4 alcohols such as methanol and ethanol. The amount of the solvent used is not particularly limited as long as the reaction proceeds efficiently.

The hydrolysis reaction is usually carried out in an inert atmosphere such as nitrogen gas or a rare gas, or may be carried out under normal pressure or pressure. Further, the reaction may be carried out with stirring. The reaction temperature can be selected from, for example, a range of about 10 to 100 ° C., and the preferred range is, in stages, 20 to 100 ° C., 50 to 99 ° C., 70 to 97 ° C., 75 to 95 ° C., 80 to 90 ° C. ℃. The reaction may be carried out at the reflux temperature. The reaction time is not particularly limited and can be selected from, for example, a range of about 1 to 48 hours, and the preferred range is 12 to 36 hours and 18 to 24 hours in a stepwise manner.

After completion of the hydrolysis reaction, the reaction mixture (reaction solution or reaction mixture) is prepared by conventional purification or separation means, for example, filtration, concentration, extraction, neutralization, washing, drying, crystallization, recrystallization, column chromatography and the like. Purification may be performed by means or a means combining these.

(Preparation of compound represented by formula (1))
The compound represented by the formula (1) may be prepared by a method of reacting the compound represented by the formula (2b) with the compound represented by the formula (3).

In the compound represented by the formula (2b), m is preferably 1 from the viewpoint of suppressing side reactions and coloring. Incidentally, when m in the formula (2a) or (2b) is zero, as described later, the compounds wherein m is 0 in the formula (2a) or (2b), halogen corresponding to hydrocarbon group ^{R 2} R ² may be introduced by reacting with a hydrocarbon.

Further, in the compound represented by the formula (2b), X ² is often a hydroxyl group or an alkoxy group. In addition, X ² in the formula (2b) may be the same group as X ² derived from the raw material such as the formula (5b), and may be used as a raw material by a conventional chemical reaction such as a hydrolysis reaction or an esterification reaction. May have been converted to different groups.

Examples of the compound represented by the representative formula (2b) include compounds corresponding to the compound represented by the above-exemplified representative formula (1), and examples thereof include 9- (4-carboxyphenyl) -9. 9- (carboxyaryl) -9-alkylfluorene such as −methylfluorene, 9- (alkoxycarbonylaryl) -9-alkylfluorene such as 9- (4-t-butoxycarbonylphenyl) -9-methylfluorene, etc. Be done.

Typical compounds represented by the formula (3) include hydroxy C _2-6 such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Examples thereof include alkyl (meth) acrylates or C _2-6 alkylene oxides (or corresponding alkylene carbonates or haloalkanols) adducts thereof. The compound represented by the preferred formula (3) is a compound having p of 1, and among them, a hydroxy C _2-4 alkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate.

The ratio of the compound represented by the formula (3) to be used may be, for example, about 1 to 2 mol with respect to 1 mol of the compound represented by the formula (2b), and the preferable range is as follows in stages. , 1-1.5 mol, 1-1.2 mol, 1-1.1 mol.

In the formula (2b), when X ² is a hydroxyl group or an alkoxy group, the reaction may use a conventional esterification catalyst. Examples of the catalyst include acid catalysts; base catalysts; titanium (IV) alkoxides such as titanium (IV) tetraisopropoxide. Examples of the acid catalyst include the acids exemplified in the section of hydrolysis. Of these catalysts, a base catalyst can be preferably used.

Examples of the base catalyst include bases exemplified in the reaction between the compound represented by the formula (4) and the compound represented by the formula (5a) or (5b). These base catalysts can also be used alone or in combination of two or more. Of these base catalysts, amines such as N, N-dimethylaminopyridine are often used.

The ratio of the catalyst used may be, for example, about 0.01 to 1 mol with respect to 1 mol of the compound represented by the formula (2b), and the preferable range is 0.05 to 0 in the following steps. It is .5 mol, 0.1-0.4 mol, 0.15-0.3 mol.

The reaction may be carried out in the presence of a condensing agent. Examples of the condensing agent include conventional condensing agents such as carbodiimides. Examples of carbodiimides include diisopropylcarbodiimide (DIC), di-t-butylcarbodiimide, dicyclohexylcarbodiimide (DCC), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide (WSC or EDC), 1- (3). -Dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (WSC · HCl or EDC · HCl), 1,3-bis (2,2-dimethyl-1,3-dioxolan-4-ylmethyl) carbodiimide (BDDC), 1 -Cyclohexyl-3- (2-morpholinoethyl) -carbodiimide meth-p-toluenesulfonate (CMC), polymer-supported carbodiimide and the like.

These condensing agents may be used alone or in combination of two or more. Among these condensing agents, DCC, WSC, WSC / HCl and the like are often used. The proportion of the condensing agent used may be, for example, about 1 to 3 mol with respect to 1 mol of the compound represented by the formula (2b), and the preferable range is 1.1 to 2 mol in the following steps. , 1.2 to 1.8 mol, 1.3 to 1.5 mol.

The hydrolysis reaction may be carried out in the absence of a solvent, but is usually carried out in a solvent. Examples of the solvent include alcohols, specifically, C _1-4 alcohols such as methanol and ethanol. The amount of the solvent used is not particularly limited as long as the reaction proceeds efficiently.

The reaction may be carried out in the presence or absence of the thermal polymerization inhibitor, and if necessary, the thermal polymerization inhibitor may be added after the reaction is completed. Examples of the thermal polymerization inhibitor include benzoquinone; hydroquinone, hydroquinone monomethyl ether (MEHQ), hydroquinones such as t-butylhydroquinone and p-benzoquinone; catechols such as pt-butylcatechol and 2-methoxyphenol; N. , N-diethylhydroxylamine and other amines; 1,1-diphenyl-2-picrylhydrazyl; tri-p-nitrophenylmethyl; phenothiazine and the like. The thermal polymerization inhibitor may be used alone or in combination of two or more. Of these thermal polymerization inhibitors, catechols such as 2-methoxyphenol are often used.

The ratio of the thermal polymerization inhibitor may be, for example, about 0.001 to 10 parts by mass with respect to 100 parts by mass of the compound represented by the above formula (3), and the above formula (1) obtained by the reaction. For example, it may be about 0.0001 to 0.1 parts by mass with respect to 100 parts by mass of the compound represented by.

The reaction may be carried out in the presence of a solvent. Solvents include, for example, hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, and the like; halogenation. Hydrocarbons, specifically methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, etc .; ethers, specifically, dialkyl ethers such as diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, etc. Cyclic ethers, etc .; Ketones, specifically acetone, methyl ethyl ketone, etc .; Sulfoxides, specifically dimethyl sulfoxide, etc .; Amidos, specifically N, N-dimethylformamide, N, N- Dimethyl acetamide, N-methyl-2-pyrrolidone and the like; nitriles such as acetonitrile and the like can be mentioned. The solvent may be used alone or in combination of two or more. Of these solvents, ethers such as THF are often used. The ratio of the solvent is not particularly limited, and is, for example, about 100 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the compound represented by the formula (2b) and the compound represented by the formula (3). It is also good, usually 400 to 600 parts by mass.

The reaction can be carried out in air or in an inert atmosphere such as nitrogen gas or rare gas with stirring, and may be carried out under normal pressure, pressurization or reduced pressure. Further, in order to effectively prevent unexpected polymerization during the reaction, air may be blown into the reaction solution.

The reaction temperature and reaction time can be appropriately selected according to the type of raw material used, and when X ² is a halogen atom in the above formula (2b), the reaction temperature is, for example, −10 ° C. to 30 ° C., preferably 0. ~ 20 ° C, more preferably 2-10 ° C. When X ² is a hydroxyl group or an alkoxy group in the above formula (2b), the reaction temperature may be, for example, 50 to 150 ° C., preferably 80 to 130 ° C., more preferably 100 to 120 ° C., and condensation When the agent is used, it is, for example, 10 to 70 ° C, preferably 20 to 60 ° C, and more preferably 30 to 50 ° C. The reaction may be carried out at the reflux temperature. The reaction time is not particularly limited, and is, for example, about 1 to 48 hours, preferably 12 to 36 hours.

After completion of the reaction, the produced compound represented by the formula (1) is prepared by a conventional method, for example, neutralization, washing, dehydration, filtration, adsorption, concentration, drying, extraction, crystallization, recrystallization, reprecipitation, Separation and purification may be performed by a separation and purification means such as centrifugation and column chromatography, or a means combining these.

Substituents such as R ¹ , R ² , and R ³ in the formula (1) are represented by the formulas (4), (5a) and / or (5b) which are raw materials as described in the reaction process formula. The compound may be contained, and may be introduced by a chemical reaction at any stage until the compound represented by the formula (1) is prepared. For example, in the case of R ² , in the formula (2a) or (2b), the compound in which m is 0 and the formula (6) R ^2- X ³ (in the formula, R ² is a hydrocarbon group and X ³ is a halogen atom). represented by reacting the halogenated hydrocarbons in the illustrated) may be introduced a hydrocarbon group R ^2. As described above, when the compound in which m is 0 in the formula (4) is used and R ² is introduced later, the reactivity with the compound represented by the formula (5a) or (5b) due to the steric hindrance of R ² is reduced. It is preferable in that it can be prevented.

In the formula (6), examples of the halogen atom represented by X ^3, a chlorine atom, a bromine atom, an iodine atom and the like, are often iodine atom. Examples of the compound represented by the representative formula (6), include halogenated hydrocarbons corresponding to the specific hydrocarbon radicals R ² exemplified in terms of the formula (1), for example, halogenated alkyl, halogen Cycloalkyl halides, aryl halides, aralkyl halides and the like. Of these, alkyl halides such as methyl iodide are often used.

The proportion of the halogenated hydrocarbon represented by the formula (6) may be, for example, about 1 to 20 mol, which is preferable with respect to 1 mol of the compound represented by the formula (2a) or (2b). The range is 1.5 to 10 mol, 2 to 5 mol, 2.5 to 3.5 mol, and usually 5 to 7 mol in a stepwise manner.

The reaction between the compound represented by the formula (2a) or (2b) and the compound represented by the formula (6) may be carried out in the presence of a base. Examples of the base include the base exemplified in the reaction between the compound represented by the formula (4) and the compound represented by the formula (5a) or (5b). These bases can also be used alone or in combination of two or more. Of these bases, alkali metal alkoxides such as potassium t-butoxide are often used.

The ratio of the base used may be, for example, about 1 to 10 mol with respect to 1 mol of the compound represented by the formula (2a) or (2b), and the preferable range is 1.5 in the following steps. ~ 8 mol, 2-6 mol, 2.5-5.5 mol, 3-5 mol, 3.5-4.5 mol.

When represented by the formula (2a) or (2b), the reaction with the compound represented by the formula (6) may be carried out in a solvent. Examples of the solvent include aprotic polar solvents exemplified in the reaction between the compound represented by the formula (4) and the compound represented by the formula (5a) or (5b). These solvents can also be used alone or in combination of two or more. Of these solvents, amides such as DMF are often used. The ratio of the solvent used is not particularly limited, and may be, for example, about 100 to 3000 parts by mass, preferably 500 parts by mass, based on 100 parts by mass of the compound represented by the formula (2a) or (2b). ~ 2000 parts by mass.

When represented by the formula (2a) or (2b), the reaction with the compound represented by the formula (6) can usually be carried out in an inert atmosphere such as nitrogen gas or a rare gas with stirring. It may be carried out under normal pressure, pressurization or reduced pressure. The reaction temperature is, for example, 0 to 100 ° C, preferably 10 to 50 ° C, and more preferably 20 to 35 ° C. The reaction time is not particularly limited, and is, for example, about 1 to 48 hours, preferably 12 to 36 hours. After completion of the reaction, the reaction product is separated by conventional methods such as neutralization, washing, dehydration, filtration, adsorption, concentration, drying, extraction, crystallization, recrystallization, reprecipitation, centrifugation, column chromatography and the like. Separation and purification may be carried out by a purification means or a means in which these are combined.

[Composition containing a compound represented by the formula (1) and a polymer thereof]
Since the monofunctional fluorene compound represented by the formula (1) has an appropriately low melting point, it can take a solid form at room temperature and can easily improve its fluidity with a little heating. It can also be used in a solvent-free system as a polymerization component or a reactive diluent. Therefore, the present invention also includes a polymerizable composition (or curable composition) containing the monofunctional fluorene compound represented by the above formula (1) and a polymer (or cured product) thereof.

(Polymerizable composition)
The polymerizable composition may contain at least the compound represented by the formula (1), and may not contain other polymerization components (or copolymerization components), and may contain, if necessary. You may. The copolymerization component may be a monofunctional polymerization component or a polyfunctional polymerization component.

The monofunctional polymerization component (or reactive diluent) is not particularly limited, and is a polymerizable group (or polymerizable unsaturated bond), for example, an alkenyl group such as a vinyl group or an allyl group, or (meth) acryloyl. Any compound having one group or the like may be used, and specific examples thereof include a monofunctional vinyl-based monomer; a monofunctional (meth) acrylic-based monomer and the like. Examples of the monofunctional vinyl-based monomer include α-olefin-based monomers such as ethylene and propylene; styrene-based monomers such as styrene, α-methylstyrene and vinyltoluene; vinyl ester-based monomers such as vinyl acetate; N-vinylpyrrolidone. And so on. Examples of the monofunctional (meth) acrylic monomer include (meth) acrylic acid; (meth) acrylamide; N-substituted (meth) acrylamide such as N-methylol (meth) acrylamide and N, N-dimethyl (meth) acrylamide; (Meta) acrylonitrile; examples include monofunctional (meth) acrylate.

These monofunctional polymerization components can be used alone or in combination of two or more. Among these monofunctional polymerization components, monofunctional (meth) acrylic monomers, especially monofunctional (meth) acrylates, are often used.

Examples of the monofunctional (meth) acrylate include an aliphatic monofunctional (meth) acrylate; an alicyclic monofunctional (meth) acrylate; an aromatic monofunctional (meth) acrylate; and a monofunctional containing a sulfur atom. Sexual (meth) acrylates can be mentioned. These monofunctional (meth) acrylates can also be used alone or in combination of two or more.

Examples of the aliphatic monofunctional (meth) acrylate include C _1-20 alkyl (meth) acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

Examples of the alicyclic monofunctional (meth) acrylate include a bridge such as C _5-10 cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate. Cyclic (meth) acrylates can be mentioned.

Examples of the aromatic monofunctional (meth) acrylate include aryl (meth) acrylate such as phenyl (meth) acrylate; aralkyl (meth) acrylate such as benzyl (meth) acrylate; and aryloxyalkyl (meth) acrylate. C _6-12 aryloxy C _2-4 such as 2-phenoxyethyl (meth) acrylate, 2- (2-naphthoxy) ethyl (meth) acrylate, 2- (o-phenylphenoxy) ethyl (meth) acrylate. Alkyl (meth) acrylates and the like; mono (meth) acrylates of bisphenols or biphenols (or their alkylene oxide adducts) such as mono (meth) acrylates of ethylene oxide adducts of bisphenol A; 9- (meth) acryloyloxymethylfluorene. Examples thereof include (meth) acrylate having a fluorene skeleton such as.

Examples of the monofunctional (meth) acrylate containing a sulfur atom include alkylthio (meth) acrylate, arylthio (meth) acrylate, aralkylthio (meth) acrylate, and arylthioalkyl (meth) acrylate. Examples of the alkylthio (meth) acrylate include C _1-6 alkylthio (meth) acrylate such as methylthio (meth) acrylate. Examples of the arylthio (meth) acrylate include C _6-10 arylthio (meth) acrylate such as phenylthio (meth) acrylate. Examples of the aralkylthio (meth) acrylate include C _6-10 aryl C _1-6 alkylthio (meth) acrylate such as benzylthio (meth) acrylate. Examples of the arylthioalkyl (meth) acrylate include C _6-10 arylthio C _2-4 alkyl (meth) acrylate such as phenylthioethyl (meth) acrylate.

The polyfunctional polymerization component is not particularly limited, and usually, a polyfunctional (meth) acrylate having a plurality of (two or more) (meth) acryloyl groups is often used. The number of (meth) acryloyl groups per molecule is, for example, 2-10, preferably 2-6, more preferably 2-4, especially 2-3, especially 2.

Examples of the polyfunctional (meth) acrylate include epoxys such as aliphatic epoxy (meth) acrylate, alicyclic epoxy (meth) acrylate, aromatic epoxy (meth) acrylate, and poly (meth) acrylate of novolak type epoxy resin. (Meta) acrylate (vinyl ester resin); urethane (meth) acrylate; polyester (meth) acrylate (poly (meth) acrylate of polyester polyol having two or more hydroxyl groups); alkylene glycol di (meth) acrylate; polyalkylene glycol Di (meth) acrylate; Di (meth) acrylate of alicyclic diol; Di (meth) acrylate of biphenols or bisphenols or their alkylene oxide (alkylene carbonate or haloalkanol) adduct; about 3 to 6 hydroxyls Examples thereof include a low molecular weight polyol compound having a group or a poly (meth) acrylate of an alkylene oxide (alkylene carbonate or haloalkanol) adduct thereof. These polyfunctional (meth) acrylates may be used alone or in combination of two or more. Commercially available products may be used as these polyfunctional (meth) acrylates.

Examples of the aliphatic epoxy (meth) acrylate include (poly) alkylene glycol diglycidyl ether such as di (meth) acrylate of 1,6-hexanediol diglycidyl ether and di (meth) acrylate of polypropylene glycol diglycidyl ether. Di (meth) acrylate can be mentioned.

Examples of the alicyclic epoxy (meth) acrylate include cyclohexanediol, cyclohexanedimethanol, dicyclopentadienedimethanol, norbornanediol, norbornenedimethanol, adamantandiol, adamantandimethanol, tricyclodecanediol, and tricyclodecandi. Di (meth) acrylate of epoxy compound (diglycidyl ether) corresponding to a diol having a C _5-15 aliphatic hydrocarbon ring such as methanol; Di (meth) acrylate of hydrogenated bisphenol A diglycidyl ether, which will be described later. Examples thereof include the di (meth) acrylate of the diglycidyl ether of the hydrogenated product of the bisphenols or biphenols described in the group epoxy (meth) acrylates or their alkylene oxide (alkylene carbonate or haloalkanol) adducts.

Examples of the aromatic epoxy (meth) acrylate include diglycidyl ethers of bisphenols or biphenols such as di (meth) acrylates of bisphenol A diglycidyl ether or alkylene oxide (alkylene carbonate or haloalkanol) adducts thereof. Di (meth) acrylate can be mentioned. Examples of bisphenols include bisphenol A, bisphenol F, bisphenol AD, and bisphenol S. Examples of biphenols include p, p'-biphenol, m, m'-biphenol, o, o'-biphenol.

Examples of the alkylene glycol di (meth) acrylate include C _2-10 alkylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate and butanediol di (meth) acrylate.

Examples of the polyalkylene glycol di (meth) acrylate include di-hexa C _2-10 alkylene glycol di (meth) acrylate such as diethylene glycol di (meth) acrylate.

Examples of the di (meth) acrylate of the alicyclic diol include cyclohexanediol, cyclohexanedimethanol, dicyclopentadienedimethanol, norbornandiol, norbornenedimethanol, adamantandiol, adamantandimethanol, tricyclodecanediol, and tricyclo. The bisphenol according to the aromatic epoxy (meth) acrylate such as the di (meth) acrylate of hydrogenated bisphenol A; the di (meth) acrylate corresponding to the diol having a C _5-15 aliphatic hydrocarbon ring such as decandimethanol. Diols or biphenols or di (meth) acrylates of hydrogenators of their alkylene oxide (alkylene carbonate or haloalkanol) adducts.

Examples of the poly (meth) acrylate of the low molecular weight polyol compound having about 3 to 6 hydroxyl groups or an alkylene oxide (alkylene carbonate or haloalkanol) adduct thereof include glycerin tri (meth) acrylate and diglycerin tetra ( Meta) acrylate, trimethylolethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, sorbitol tri to hexa (meth) acrylate can be mentioned.

(Components other than polymerization components)
The curable composition may further contain a polymerization initiator, a solvent, an additive and the like, if necessary, in addition to the polymerization component (or monomer component).

The polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photoradical generator).

Examples of the thermal polymerization initiator include organic peroxides and azo compounds. Examples of the organic peroxide include dialkyl peroxides such as di-t-butyl peroxide; diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; t-butyl hydroperoxide, cumene hydroperoxide, and peracetic acid. Peracids (or peracid esters) such as t-butyl acetate; ketone peroxides; peroxycarbonates; peroxyketals. Examples of the azo compound include azonitrile compounds such as 2,2'-azobis (isobutyronitrile), azoamide compounds, and azoamidine compounds. These thermal polymerization initiators can be used alone or in combination of two or more.

Examples of the photopolymerization initiator include benzoins, specifically benzoin alkyl ethers such as benzoin and benzoin ethyl ether; acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like. Acetophenones; Aminoacetophenones such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone-1; Anthracinones such as anthraquinone and 2-methylanthraquinone; 2,4-dimethylthioxanthone, Thioxanthones such as 2,4-diethylthioxanthone and 2-chlorothioxanthone; quettals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; xanthones and the like. These photopolymerization initiators may be used alone or in combination of two or more.

The ratio of the polymerization initiator (heat and / or photopolymerization initiator) is 0.1 to 15 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 1 part by mass with respect to 100 parts by mass of the total amount of the polymerization components. It is 8 parts by mass, more preferably 2 to 5 parts by mass.

Further, the photopolymerization initiator may be combined with a photosensitizer. Typical photosensitizers are tertiary amines such as trialkylamines; trialkanolamines such as triethanolamine; dialkylaminobenzoic acid alkyl esters, specifically p- (dimethylamino) benzoic acid. Ethyl N, N-dimethylaminobenzoate such as ethyl ester, N, N-dimethylaminobenzoate amyl such as p- (dimethylamino) benzoate; bis such as 4,4-bis (diethylamino) benzophenone ( Dialkylamino) benzophenone; conventional photosensitizers such as dialkylaminobenzophenone such as 4- (dimethylamino) benzophenone can be mentioned. These photosensitizers may be used alone or in combination of two or more.

The ratio of the photosensitizer is 1 to 200 parts by mass, preferably 5 to 150 parts by mass, and more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the polymerization initiator.

The curable composition does not have to contain a solvent, but may contain a solvent, if necessary, in order to adjust the handleability. The solvent is not particularly limited, and for example, hydrocarbons, specifically, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene and xylene. Such as; halogenated hydrocarbons, specifically, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, etc .; ethers, specifically, chain ethers such as diethyl ether, tetrahydrofuran, 1,4, etc. -Cyclic ethers such as dioxane; ketones, specifically dialkyl ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclic ketones such as cyclohexanone; esters, specifically methyl acetate, acetate, etc. Acetate esters such as ethyl and butyl acetate; glycol ether acetates, specifically (poly) alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether acetate; sulfoxides, specific Examples include dimethylsulfoxide and the like; amides, specifically dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and the like; nitriles, specifically acetonitrile and the like. These solvents can also be used alone or as a mixed solvent in combination of two or more.

The ratio of the solvent is not particularly limited, and the solid content (components other than the solvent) may be contained so as to be, for example, about 0.1 to 50% by mass with respect to the entire curable composition.

The curable composition may contain conventional additives such as colorants, stabilizers, fillers, antistatic agents, flame retardants, surfactants, plasticizers, hardeners, polymerization inhibitors and the like. Examples of the stabilizer include a heat stabilizer, an antioxidant, an ultraviolet absorber and the like. These additives can be used alone or in combination of two or more.

The ratio of the additive is, for example, 30% by mass or less, preferably 20% by mass or less, 10% by mass or less, and 5% by mass or less in a stepwise manner with respect to the entire curable composition. The ratio may be 0.001 to 15% by mass, specifically, 0.01 to 3% by mass.

(Polymer)
The polymer (or cured product) of the present invention may contain at least a structural unit represented by the following formula (1A).

(In the formula, Z, R ¹ , R ² , R ³ , R ⁴ , A, k, m, n and p are the same as in the above formula (1) including the preferred embodiment).

The polymer may be a homopolymer or a copolymer. In the polymer, the proportion of the structural unit represented by the formula (1A) may be, for example, about 10 mol% or more, specifically about 30 to 90 mol%, based on the total components. The preferred range is, in stages, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, and usually 100 mol% (single weight). (Union) in many cases.

Further, the polymer may be a polymer having a substantially linear molecular structure (or a thermoplastic resin), or a polymer having a three-dimensional network structure (curable resin). Usually, it is often a polymer having a linear molecular structure.

The polymer (or cured product) can be easily cured and produced by applying active energy (or active energy rays) to the polymerizable composition (or curable composition). As the active energy, thermal energy and / or light energy such as ultraviolet rays and X-rays are useful.

When heat treatment is performed using thermal energy, the heating temperature is, for example, 50 to 200 ° C., preferably 60 to 150 ° C., and more preferably 70 to 120 ° C.

When light is irradiated using light energy (for example, ultraviolet rays), the amount of light irradiation energy can be appropriately selected depending on the application, for example, 50 to 10000 mJ / cm ² , preferably 70 to 8000 mJ / cm ^2. , more preferably 100~5000mJ / cm ^2, particularly 500~3000mJ / cm ^2.

The shape of the cured product is not particularly limited, and may be a cured product having a three-dimensional structure such as a lens shape or a tubular shape, or a cured product (or a cured film) having a two-dimensional structure such as a film shape, a sheet shape, or a plate shape. It may be a cured product having a one-dimensional structure such as linear, fibrous, or rod-shaped.

The method for producing the cured product is not particularly limited, and for example, the curable composition is molded or cast (injected) into a predetermined mold according to the shape of the cured product, and then cured (heated and / or). It may be manufactured by light irradiation). Further, in the case of a cured product having a two-dimensional structure, for example, the curable composition is used as a base material or a substrate, for example, a metal such as aluminum; an inorganic material or ceramics such as titanium oxide, glass or quartz; a cyclic olefin resin or polycarbonate. It may be produced by applying it to an organic material such as a based resin or plastic; a porous body such as wood to form a film-like coating film (or thin film), and then subjecting it to a curing treatment.

Since the cured product of the present invention contains a structural unit represented by the above formula (1A), it exhibits a high refractive index. The refractive index (refractive index after curing) nD at a temperature of 25 ° C. and a wavelength of 589 nm of the cured product may be, for example, about 1.55 to 1.7, and the preferred range is 1.56 in the following steps. ~ 1.68, 1.57 to 1.67, 1.58 to 1.66, 1.59 to 1.65, 1.6 to 1.64, 1.605 to 1.635, 1.61 to 1. It is .63, more preferably 1.615 to 1.625.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. The details of the evaluation items and raw materials are shown below.

[Evaluation method]
(HPLC)
Using "LCMS-2020" manufactured by Shimadzu Corporation as an HPLC (high performance or high performance liquid chromatograph) apparatus and "KINTEX XB-C18" manufactured by Shimadzu Corporation as a column, mobile phase: acetonitrile / water. (Volume ratio) was changed from 50/50 to 95/5 over 10 minutes, and then measured at 95/5 under the condition of holding for 5 minutes to calculate HPLC purity [area%].

(Refractive index nD)
A cured film (polymer or polymer) is prepared using the obtained compound, and then refracted at a temperature of 25 ° C. and a wavelength of 589 nm using a reflection spectroscopic film thickness meter (“FE-3000” manufactured by Otsuka Electronics Co., Ltd.). The rate was measured.

The cured film (polymer or polymer) was prepared as follows. A polymerizable composition obtained by adding a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) at a ratio of 3 parts by mass to 100 parts by mass of the obtained compound and mixing at a temperature of 65 ° C. The prepared and obtained polymerizable composition was applied onto quartz glass to form a coating film having a thickness of about 100 μm. The obtained coating film was irradiated with ultraviolet rays under the condition of 500 mJ / cm ² using an ultraviolet irradiator (H015-L31: manufactured by Eye Graphics Co., Ltd.) to obtain a cured film.

(Melting point)
The melting point of the obtained compound was measured using "Melting point M-565" manufactured by BUCHI.

( ^{1 1} H-NMR)
¹ H-NMR spectrum was measured using "ULTRA SHIELD (registered trademark) 300" manufactured by BRUKER, using deuterated chloroform (CDCl ₃ ) as a solvent and tetramethylsilane (TMS) as a standard substance.

[Example 1]
(Synthesis of 9- (4-cyanophenyl) fluorene)
In a reactor equipped with a magnetic stir bar and a three-way cock, 9H-fluorene (7.61 g, 45.8 mmol), p-bromobenzonitrile (25.0 g, 137 mmol), potassium t-butoxide (t-BuOK; 25. 7 g, 229 mmol) and zinc chloride (ZnCl ₂ ; 9.36 g, 68.7 mmol) were charged and replaced with nitrogen, and then N, N-dimethylformamide (DMF; 230 mL) was added and stirred for 30 minutes to disperse. .. Then, after stirring at 80 ° C. for 3 hours, the mixture was cooled to room temperature. The completion of the reaction was confirmed by thin layer chromatography (TLC) analysis. After neutralization with an aqueous solution of ammonium chloride, an extraction operation was carried out using ethyl acetate, and the obtained organic layer was dried to obtain a brown solid substance. The solid material was analyzed by HPLC, and 90 area% of the target product (single-substituted product) in which one 4-cyanophenyl group was substituted at the 9-position of 9H-fluorene and two of the groups were substituted at the 9- and 9-positions. It was confirmed that the 9,9-2 substituted product contained in 3 area% and the disubstituted product different from the 9,9-2 substituted product contained in 2 area%.

The reaction mixture was heated to 75 ° C. under reduced pressure by an oil rotary pump to distill off DMF, purified water (1200 mL) and ethyl acetate (800 mL) were added, and the mixture was stirred for 30 minutes and then separated. The aqueous layer was extracted with ethyl acetate (3 x 200 mL), the organic layers were collected, washed with purified water (3 x 400 mL) and dried over sodium sulfate. Silica gel (“Silica gel 60N spherical neutral” manufactured by Kanto Chemical Co., Ltd .; 45 g) is added to the obtained filtrate (organic layer), stirred at room temperature for 5 minutes, and then concentrated under reduced pressure (oil rotary pump) at 50 ° C. The mixture was dried to obtain crude-adsorbed silica gel (52.2 g). Silica gel (“Silica gel 60N spherical neutral” manufactured by Kanto Chemical Co., Ltd .; 244 g), the obtained crude adsorbed silica gel (52.2 g) and sodium sulfate (10 g) were charged in this order on the column, and hexane / ethyl acetate was added. Chromatography with (volume ratio) = 85/15 as the mobile phase gave 9- (4-cyanophenyl) fluorene (1 substituent; 5.14 g, yield 42.0%).

(Synthesis of 9- (4-cyanophenyl) -9-methylfluorene)
A reactor equipped with a magnetic stirrer and a three-way cock was charged with 9- (4-cyanophenyl) fluorene (4.33 g, 16.2 mmol) and replaced with nitrogen, and then DMF (60 mL) was added to dissolve the reactor. Then nitrogen was blown in for 30 minutes. Under water cooling, potassium t-butoxide (7.44 g, 66.3 mmol) was added to dissolve and disperse for 30 minutes, then methyl iodide (14.4 g, 101 mmol) was added dropwise over 5 minutes under water cooling. The mixture was stirred at room temperature for 23 hours. Purified water (120 mL) was added to the reaction solution for stirring and dispersion, and the pH of the reaction solution was adjusted to about 3 with hydrochloric acid, then chloroform (120 mL) was added and the mixture was stirred for 15 minutes. The liquid was separated and the aqueous layer was extracted with chloroform (3 × 20 mL), the organic layers were combined, washed with purified water (3 × 200 mL), and dried over sodium sulfate. Sodium sulfate is filtered off, silica gel (7.0 g) is added, and the mixture is stirred at 60 ° C. for 5 minutes, and then concentrated to dryness at 60 ° C. under reduced pressure (oil rotary pump). 11.6 g) was obtained. Chromatography in which silica gel (62.0 g), crude-adsorbed silica gel (11.6 g) and sodium sulfate (10 g) are charged in this order on a column, and hexane / ethyl acetate (volume ratio) = 80/20 is used as a mobile phase. As a result, 9- (4-cyanophenyl) -9-methylfluorene (3.22 g, yield 70.6%) in the form of a slightly yellowish brown solid was obtained.

(Synthesis of 9- (4-carboxyphenyl) -9-methylfluorene)
In a reactor equipped with a magnetic stir bar and a three-way cock, 9- (4-cyanophenyl) -9-methylfluorene (3.22 g, 11.4 mmol), triethylbenzylammonium chloride (0.870 g, 3.82 mmol), After charging ethanol (93 mL) and a 5N aqueous sodium hydroxide solution to replace the space with nitrogen (purging with nitrogen gas), the mixture was stirred and refluxed at 85 ° C. for 19 hours and cooled to room temperature. After adjusting the pH to about 2 by adding hydrochloric acid to the reaction solution, ethanol was distilled off at 50 ° C. under reduced pressure (diaphragm pump), and then methyl t-butyl ether (150 mL) was added to separate the solutions. The aqueous layer was extracted with methyl t-butyl ether (3 x 150 mL), the organic layers were combined, washed with purified water (3 x 200 mL) and dried over sodium sulfate. Sodium sulfate is filtered off and concentrated to dryness at 60 ° C. under reduced pressure (oil rotary pump) to give a slightly brown solid 9- (4-carboxyphenyl) -9-methylfluorene (3.38 g, yield 98). .3%) was obtained.

(Synthesis of 9- [4- (2-acryloyloxyethoxy) carbonylphenyl] -9-methylfluorene)
In a reactor equipped with a magnetic stirrer, 9- (4-carboxyphenyl) -9-methylfluorene (4.36 g, 14.5 mmol) and tetrahydrofuran (THF; 35 mL) were charged and dissolved by stirring, and then 2-hydroxy. Ethyl acrylate (1.73 g, 14.9 mmol) and N, N-dimethylaminopyridine (0.386 g, 3.16 mmol) were added and dissolved by stirring, followed by 1- (3-dimethylaminopropyl) -3-. Ethylcarbodiimide hydrochloride (3.86 g, 20.2 mmol) was added, the mixture was stirred at 40 ° C. for 22 hours, and cooled to room temperature. After distilling off THF at 50 ° C. under reduced pressure (diaphragm pump), purified water (800 mL) and chloroform (200 mL) were added, and the mixture was stirred for 30 minutes. After separation, the aqueous layer was extracted with chloroform (3 x 200 mL), the organic layers were combined and washed with purified water (3 x 500 mL) and then dried over sodium sulfate. After filtering sodium sulfate, silica gel (10.1 g) is added, stirred at 45 ° C. for 5 minutes, and dried under reduced pressure (oil rotary pump) at 45 ° C. to adsorb crude silica gel (15). .1 g) was obtained. Silica gel (100 g), crude adsorbed silica gel (15.1 g) and sodium sulfate (10 g) are charged in this order on a column, and purified by chromatography with hexane / ethyl acetate (volume ratio) = 80/20 as the mobile phase. A slightly yellow viscous liquid was obtained. When the obtained viscous liquid was allowed to stand at room temperature for 1 week, a white solid 9- [4- (2-acryloyloxyethoxy) carbonylphenyl] -9-methylfluorene (3.22 g, yield 70.6) was allowed to stand. %; A compound represented by the following formula (1-1)) was obtained. The melting point of the obtained compound was 64 to 65 ° C. The measurement results of ¹ H-NMR are shown below.

^{1 1} H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 7.88 (2H, d), 7.73 (2H, d), 7.37 (2H, m), 7.22 (6H, m) ), 6.42 (1H, d), 6.13 (1H, m), 5.84 (1H, d), 4.48 (4H, m), 1.90 (3H, s).

The refractive index (refractive index after curing) nD of the cured film (polymer or polymer) obtained by using the compound represented by the above formula (1-1) is 1.62, which is 9,9-bis. Although it does not have an arylfluorene skeleton, it showed a surprisingly high refractive index.

The compound of the present invention has a relatively low melting point, can be stably stored at room temperature, has excellent handleability, and can easily impart fluidity with a little heating, and thus is suitably used for applications such as reactive diluents. it can. A fluorene skeleton having excellent properties such as a high refractive index can be easily introduced into a resin. Further, the obtained resin can be suitably used as an optical material, and examples of the shape of such an optical material include a film or sheet shape, a plate shape, a lens shape, and a tubular shape.

Typically, the (meth) acrylate or cured product thereof of the present invention is a graphite precursor; a gas separation film such as a CO ₂ gas separation film; a film for a fuel cell; a light emitting material such as a light emitting material for an organic EL; an organic substance. Semiconductors; adhesives or adhesives such as optical adhesives and optical adhesives; coating agents (coating agents), specifically, optical overcoating agents or hardware such as coating agents for LED (light emitting diode) elements Coating agents, ink materials, etc .; lenses, specifically, pickup lenses such as pickup lenses for DVDs (digital versatile discs), microlenses such as microlenses for liquid crystal projectors, eyeglass lenses, etc .; films or sheets, especially Optical film or optical sheet, specifically, a polarizing film such as a polarizing film for a liquid crystal display, an antireflection film (or an antireflection film) such as an antireflection film for a display device, a film for a touch panel, a film for a flexible substrate, and a display. Films, specifically PDPs (plasma displays), LCDs (liquid crystal displays), VFDs (vacuum fluorescent displays), SEDs (surface conductive electron emitting element displays), FEDs (electric field emitting displays), NEDs (nano-emissive displays) ), CRT, electronic paper and other displays, especially filters and protective films in thin displays, prism sheets, etc .; optical fibers; optical waveguides; holograms and the like.

Claims (5)

The following formula (1)

(In the formula, Z represents an aromatic hydrocarbon ring, R ¹ and R ³ each independently represent a non-reactive group, R ² represents a hydrocarbon group, and R ⁴ represents a hydrogen atom or a methyl group. , A represents a linear or branched alkylene group, k independently represents an integer of 0 to 8, m represents 0 or 1, n represents an integer of 0 or more, and p represents 1 or more. Indicates an integer of)
The compound represented by. In the formula (1), Z is a C _6-12 allene ring, R ¹ is a hydrocarbon group, a cyano group or a halogen atom, and R ³ is a halogen atom, a hydrocarbon group [-R ^a ], a group [ -OR ^a ] (in the formula, ^Ra represents the hydrocarbon group), group [-SR ^a ] (in the formula, ^Ra represents the hydrocarbon group), acyl group, nitro group, cyano group, or Claim 1 is a mono or di-substituted amino group, where A is a linear or branched C _2-6 alkylene group, n is an integer of 0-4, and p is an integer of 1-10. The compound described. In the formula (1), Z is a benzene ring or a naphthalene ring, R ¹ is a linear or branched alkyl group, and R ² is a linear or branched alkyl group or a cycloalkyl group. , R ³ is a linear or branched alkyl group or aryl group, A is a linear or branched C _2-4 alkylene group, k is an integer of 0 to 2, and m is 1. The compound according to claim 1 or 2, wherein n is an integer of 0 to 2 and p is an integer of 1 to 5. The following formula (2b)

(In the formula, X ² represents a hydroxyl group, an alkoxy group or a halogen atom, and Z, R ¹ , R ² , R ³ , k, m and n are the same as in the above formula (1)).
The compound represented by and the following formula (3)

^{(Wherein, R} 4, A and p are as defined above formula (1))
The method for producing the compound according to any one of claims 1 to 3 by reacting with the compound represented by. A polymer containing the compound according to any one of claims 1 to 3 as a polymerization component.