JP2020169144A - Fluorene compound and method for producing the same - Google Patents

Abstract

To provide a novel fluorene compound that has high heat resistance and is useful as material for polyester resin, and a method for producing the same.SOLUTION: The present invention provides a fluorene compound represented by the formula (1) (where Ar1a, Ar1b, Ar2a, Ar2b each denote an arene ring, R1a, R1b, R2a, R2b each denote a substituent, Z1, Z2 each denote an arene ring, A1, A2 each denote an alkylene group, m1, m2 each denote an integer of 1 or greater, R3a, R3b, R4a, R4b each denote a substituent).SELECTED DRAWING: None

Description

The present invention relates to a novel fluorene compound and a method for producing the same.

The polyester resin (thermoplastic polyester or saturated polyester resin) imparts various properties by combining a dicarboxylic acid component and a diol component, which are polymerization components, according to the intended use. Therefore, polyester resins are used as various products from industrial products such as electric / electronic parts and automobile parts to daily necessities such as clothing and food containers.

Such polyester is lighter and more flexible than inorganic materials such as glass, and its use is also being considered for applications such as optical members such as optical lenses. However, it may not be available for applications such as in-vehicle optical lenses that are expected to be used in a high temperature environment, and a polyester resin (or resin raw material) having higher heat resistance is required.

On the other hand, Japanese Patent No. 5598489 (Patent Document 1) discloses a biphenyl derivative represented by the following formula as a compound useful as a resist underlayer film material.

(In the formula, the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. X and z independently represent 0 or 1, respectively.)

Japanese Patent No. 5598489

Patent Document 1 describes that when a biphenyl derivative represented by the above formula is used as a resist underlayer film material, a resist underlayer film having excellent etching resistance, high heat resistance, high solvent resistance, etc. can be formed. It is described that the biphenyl derivative may be converted into a novolak using formaldehyde or the like and used in the form of a novolak resin.

However, the use of the biphenyl derivative described in Patent Document 1 is specified as a novolak resin as a resist underlayer film material, and cannot be used as a polymerization component of a polyester resin or the like.

Therefore, an object of the present invention is to provide a novel fluorene compound having high heat resistance and useful as a raw material for a polyester resin, and a method for producing the same.

As a result of diligent studies to achieve the above problems, the present inventors have found that a biphenyl derivative having a 9,9-bisarylfluorene skeleton and a compound having an oxyalkylene group have high heat resistance. The present invention has been completed by finding that it can be used as a resin raw material (or a polymerization component) for a polyester resin.

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

(In the formula, Ar ^1a , Ar ^1b , Ar ^2a and Ar ^2b represent an allene ring, R ^1a , R ^1b , R ^2a and R ^2b represent substituents, and p1a, p1b, p2a and p2b are integers of 0 or more. ¹ and Z ² represent an allene ring, A ¹ and A ² represent an alkylene group, m1 and m2 represent an integer of 1 or more, and R ^3a , R ^3b , R ^4a and R ^4b are substituents. , Q1 and q2 indicate integers from 0 to 4, and r1 and r2 indicate integers of 0 or more.)

In the above formula (1), Z ¹ and Z ² may be a C _6-12 arene ring, A ¹ and A ² are C _2-4 alkylene groups, and m 1 and m ² are integers of 1 to 3. There may be.

The present invention also includes a method for producing a compound represented by the above formula (1), in which reaction between a compound represented by the following formula (2) and a compound represented by the following formula (3a). The compound represented by the above formula (1) may be produced by the reaction between the compound represented by the following formula (4) and at least one selected from alkylene oxide, alkylene carbonate and haloalkanol. A compound represented by the formula (1) may be produced.

(In the formula, Z is the same as Z ¹ and Z ² , R ⁴ is the same as R ^4a and R ^4b , A is the same as A ¹ and A ² , and m is the same as m 1 and m 2. Ar ^1a , Ar ^1b , Ar ^2a , Ar ^2b , R ^1a , R ^1b , R ^2a , R ^2b , p1a, p1b, p2a, p2b, Z ¹ , Z ² , A ¹ , A ² , m1, m2. , R ^3a , R ^3b , R ^4a , R ^4b , q1, q2, r1 and r2 are the same as in the above equation (1).

The present invention also includes a polyester resin obtained by reacting a diol component with a dicarboxylic acid component, and the diol component may contain at least the fluorene compound (1).

In the specification of the present application and claims, the number of carbon atoms of the substituent may be indicated by C ₁ , C ₆ , C _10, or 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".

The novel fluorene compound of the present invention has high heat resistance and can be used as a raw material (or a polymerization component) for a polyester resin having high heat resistance.

[Fluorene compound (1) (compound having a fluorene skeleton represented by the formula (1))]
The novel fluorene compound of the present invention (a novel compound having a fluorene skeleton) is represented by the above formula (1).

In the above formula (1), examples of the allene ring (aromatic hydrocarbon ring) represented by Ar ^1a , Ar ^1b , Ar ^2a and Ar ^2b include a monocyclic allene ring such as a benzene ring and a polycyclic allene ring. An example is a ring-set arene ring.

Examples of the polycyclic allene ring include a fused bicyclic alley ring such as a naphthalene ring, and a condensed polycyclic C _10-14 allene ring such as a condensed tricyclic allene ring such as an anthracene ring and a phenanthrene ring, and particularly naphthalene. Rings are preferred.

Examples of the ring-aggregated arene ring include a bi-C _6-12 allene ring such as a biphenyl ring, a binaphthyl ring, and a phenylnaphthalene ring, and a biphenyl ring is particularly preferable.

The types of Ar ^1a , Ar ^1b , Ar ^2a, and Ar ^2b may be the same or different from each other, and are usually the same.

Preferred Ar ^1a , Ar ^1b , Ar ^2a and Ar ^2b are C _6-10 allene rings such as a benzene ring and a naphthalene ring, and more preferably a benzene ring and a naphthalene ring, particularly a benzene ring.

Examples of the substituent represented by R ^1a , R ^1b , R ^2a and R ^2b include a halogen atom; a hydrocarbon group such as an alkyl group and an aryl group, and a cyano group.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the alkyl group include a linear or branched C _1-6 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a t-butyl group. Examples of the aryl group include a C _6-10 aryl group such as a phenyl group. The substituents represented by R ^1a , R ^1b , R ^2a and R ^2b may be the same or different.

Preferred R ^1a , R ^1b , R ^2a and R ^2b are linear or branched C _1-6 alkyl groups, cyano groups, halogen atoms, and more preferably linear or branched chains such as methyl groups and ethyl groups. State C _1-3 alkyl group, particularly C _1-2 alkyl group such as methyl group. The types of R ^1a , R ^1b , R ^2a and R ^2b may be the same or different from each other, and are usually the same. When R ^1a , R ^1b , R ^2a or R ^2b is an aryl group, the ring-aggregated array ring may be formed together with the rings Ar ^1a , Ar ^1b , Ar ^2a and Ar ^2b to be bonded.

The substitution numbers p1a, p1b, p2a and p2b of R ^1a , R ^1b , R ^2a and R ^2b can be selected from integers of 0 or more, for example, integers of 0 to 8, and preferably 0 in the following steps. ~ 4, 0-3, 0-2, 0 or 1, especially 0. The substitution numbers p1a, p1b, p2a or p2b may be the same or different from each other. When the number of substitutions p1a, p1b, p2a or p2b is 2 or more, the types of ² or more R ^1a , R ^1b , R ^2a or R ^2b may be the same or different from each other. The substitution positions of R ^1a , R ^1b , R ^2a and R ^2b are not particularly limited, and in the case of a fluorene ring in which Ar ^1a , Ar ^1b or Ar ^2a , Ar ^2b is a benzene ring, for example, positions 2 to 7 are used. It is preferably in the 2nd, 3rd or 7th place.

In formula (1), the central biphenyl ring (or the biphenyl ring corresponding to formula (2b) described later, or the biphenyl ring formed by two benzene rings substituted by R ^3a and R ^3b ), Ar ^1a and Which position (or positional relationship) is the bond position with the two fluorene rings formed by Ar ^2a and Ar ^1b and Ar ^2b (that is, the fluorene ring corresponding to the fluorenones represented by the formula (2a) described later). It may be. For example, the bond position is, for example, the 4,4'position, the 3,3' position, the 2,2' position, etc. with respect to the biphenyl ring in which two benzene rings are bonded to each other at the 1,1'position. It may be, and usually, it is often in the 4 or 4'position.

In the present specification and claims, the "fluorene skeleton" (or "fluorene ring") is a fluorene skeleton containing a fluorene skeleton such as a benzofluorene skeleton (benzofluorene ring) or a dibenzofluorene skeleton (dibenzofluorene ring). It is also used to mean including.

The substituents represented by R ^3a and R ^3b include halogen atoms; hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups; alkoxy groups; acyl groups; nitro groups; cyano groups; substituted amino groups. And so on.

Examples of the halogen atom, alkyl group, and aryl group include substituents similar to those of R ^1a , R ^1b , R ^2a, and R ^2b , including preferred embodiments. Examples of the cycloalkyl group include a C _5-8 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. Examples of the aralkyl group include a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group. Examples of the alkoxy group include a linear or branched C _1-10 alkoxy group such as a methoxy group. Examples of the acyl group include a C _1-6 acyl group such as an acetyl group. Examples of the substituted amino group include a dialkylamino group and a diacylamino group. The dialkylamino group is a diC _1-4 alkylamino group such as a dimethylamino group, and the diacylamino group is a diC such as a diacetylamino group. Examples thereof include _1-4 acylamino groups. The substituents represented by R ^3a and R ^3b may be the same or different.

Preferred R ^3a and R ^3b are linear or branched C _1-6 alkyl groups, C _5-8 cycloalkyl groups such as cyclohexyl groups, C _6-14 aryl groups, linear or branched such as methoxy groups. It is a chain C _1-4 alkoxy group, more preferably a linear or branched C _1-3 alkyl group such as a methyl group or an ethyl group, and particularly a C _1-2 alkyl group such as a methyl group. The types of R ^3a and R ^3b may be the same or different from each other, and are usually often the same. When R ^3a or R ^3b is an aryl group, R ^3a or R ^3b may form the ring-aggregated array ring together with the benzene ring to be bonded.

The substitution numbers q1 and q2 of R ^3a and R ^3b can be selected from integers of 0 to 4, and are preferably 0 to 3, 0 to 2, 0 or 1, and particularly 0 in the following steps. The substitution numbers q1 and q2 may be the same or different from each other. When the number of substitutions q1 or q2 is 2 or more, the types of 2 or more R ^3a or R ^3b may be the same or different from each other. The replacement positions of R ^3a and R ^3b are not particularly limited.

Examples of the alle ring (aromatic hydrocarbon ring) represented by the ring Z ¹ and the ring Z ² include a monocyclic alle ring such as a benzene ring, a polycyclic alle ring, and a ring-assembled alle ring.

Examples of the polycyclic array ring and the ring assembly array ring include the same array rings as those of Ar ^1a , Ar ^1b , Ar ^2a and Ar ^2b , including preferred embodiments.

The types of ring Z ¹ and ring Z ² may be the same or different from each other, and are usually the same.

Preferred rings Z ¹ and Z ² are C _6-10 allene rings such as a benzene ring and a naphthalene ring, and more preferably a benzene ring or a naphthalene ring, particularly a naphthalene ring.

When Ar ^1a , Ar ^1b , or Ar ^2a , Ar ^2b is a benzene ring, the substitution positions of rings Z ¹ and Z ² bonded to the 9-position of the fluorene ring are not particularly limited, and for example, ring Z ¹ and ring Z ¹ and When the ring Z ² is a naphthalene ring, it may be at either the 1-position or the 2-position, but usually when it is bonded at the 2-position of the naphthalene ring (or in a 2-naphthyl relationship). There are many.

The substituents represented by R ^4a and R ^4b are the same as those of R ^3a and R ^3b , including preferred embodiments. In addition, R ^4a and R ^4b may be the same or different. When R ^4a or R ^4b is an aryl group, R ^4a or R ^4b may form the ring-aggregate array ring together with the ring Z ¹ and the ring Z ² . When the number of substitutions r1 or r2 is 2 or more, the types of two or more R ^4a or R ^4b substituted with the same ring Z ¹ and ring Z ² may be the same or different from each other.

The substitution numbers r1 and r2 of ^R4a and ^R4b can be selected from integers of 0 or more, for example, integers of 0 to 8, and preferably, 0 to ⁴ , 0 to 3, 0 to 2, 0 or 0 or 0 to 3, 0 to 2, 0 or It is 1, especially 0. The substitution numbers r1 and r2 may be the same or different from each other.

Examples of the alkylene group represented by A ¹ and A ² include a linear group such as an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butandyl group, and a tetramethylene group. Examples thereof include a branched C _2-6 alkylene group. The types of A ¹ and A ² may be the same or different from each other, and are usually the same. Preferred A ¹ and A ² are a linear or branched C _2-3 alkylene group, more preferably a linear or branched C _2-3 alkylene group, particularly an ethylene group.

The number of repetitions (number of added moles) m1 and m2 of the oxyalkylene groups OA ¹ and OA ² may be an integer of 1 or more and can be selected from a range of about 1 to 10, preferably 1 to 6 in a stepwise manner. , 1-3, 1-2, especially 1. In the present specification and the scope of patent claims, the "repetition number (additional number of moles)" may be an average value (arithmetic mean value, arithmetic mean value) or an average number of additional moles, and a preferred embodiment is Similar to the preferred range of integers. When m1 and m2 are 2 or more, the 2 or more oxyalkylene groups OA ¹ and OA ² may be the same or different.

In the above formula (1), the substitution positions of the group [−O− (A ¹ O) _m1 −H] and the group [−O− (A ² O) _m2 −H] are not particularly limited, and the ring Z ¹ , It suffices to replace each of them at an appropriate replacement position of ring Z ² . The substitution positions of the group [-O- (A ¹ O) _m1- H] and the group [-O- (A ² O) _m2- H] are the fluorene rings when the ring Z ¹ and the ring Z ² are benzene rings. (Ar ^1a , Ar ^1b , or Ar ^2a , Ar ^2b is a benzene ring) The 2-position, 3-position, or 4-position of the phenyl group bonded to the 9-position, preferably the 3-position or 4-position, particularly the 4-position. It is often replaced with a position. When ring Z ¹ and ring Z ² are naphthalene rings, a naphthyl group bonded at the 1-position or 2-position with respect to the 9-position of the fluorene ring (Ar ^1a , Ar ^1b , or Ar ^2a , Ar ^2b is a benzene ring). In many cases, it is substituted at any of the 5th to 8th positions, and the 1st position of the naphthalene ring or the 9th position of the fluorene ring (Ar ^1a , Ar ^1b , or Ar ^2a , Ar ^2b is a benzene ring). It is preferable that the 2-position is substituted (replaced in the relationship of 1-naphthyl or 2-naphthyl), and the substitution positions are substituted in the relationship of 1, 5-position, 2, 6-position, and 2,6. It is particularly preferable to replace with a place.

Typical compounds represented by the formula (1) are compounds in which Ar ^1a , Ar ^1b , Ar ^2a , Ar ^2a , Z ¹ and Z ² are benzene rings, that is, bis [9- (hydroxy (poly). ) Alkoxyphenyl) Fluorene-9-yl] Biphenyls; compounds in which Ar ^1a , Ar ^1b , Ar ^2a and Ar ^2a are benzene rings and Z ¹ and Z ² are naphthalene rings, ie, bis [9- (hydroxy) (Poly) alkoxynaphthyl) fluorene-9-yl] Biphenyls and the like can be mentioned. In addition, in the present specification and claims, "(poly) alkoxy" is used in the meaning including both an alkoxy group and a polyalkoxy group.

Examples of the bis [9- (hydroxy (poly) alkoxyphenyl) fluoren-9-yl] biphenyls include bis [9- (hydroxy (poly) alkoxyphenyl) fluoren-9-yl] biphenyl and bis [9- Examples thereof include (alkyl-hydroxy (poly) alkoxyphenyl) fluoren-9-yl] biphenyl and bis [9- (aryl-hydroxy (poly) alkoxyphenyl) fluoren-9-yl] biphenyl.

As the bis [9- (hydroxy (poly) alkoxyphenyl) fluoren-9-yl] biphenyl, 4,4'-bis [9- (4- (2-hydroxyethoxy) phenyl) fluoren-9-yl] biphenyl, 4,4'-Bis [9- (4- (2-hydroxypropoxy) phenyl) fluoren-9-yl] biphenyl, 4,4'-Bis [9- (4- (2- (2-hydroxyethoxy) ethoxy) ethoxy ) Phenyl) Fluoren-9-yl] biphenyl, 3,3'-bis [9- (4- (2-hydroxyethoxy) phenyl) fluoren-9-yl] biphenyl, 2,2'-bis [9- (4) Examples thereof include bis [9- (hydroxy (mono or deca) C _2-4 alkoxy-phenyl) fluoren-9-yl] biphenyl such as − (2-hydroxyethoxy) phenyl) fluoren-9-yl] biphenyl.

Biphenyl [9- (alkyl-hydroxy (poly) alkoxyphenyl) fluoren-9-yl] Biphenyl is 4,4'-bis [9- (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene- 9-yl] biphenyl, 4,4'-bis [9-(4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluoren-9-yl] biphenyl, 4,4'-bis [9-( 4- (2- (2-Hydroxyethoxy) ethoxy) -3-methylphenyl) fluoren-9-yl] Biphenyl and other bis [9- (hydroxy (mono or deca) C _2-4 alkoxy-C _1-4 alkyl -Phenyl) Fluoren-9-yl] Biphenyl and the like.

Biphenyl [9- (aryl-hydroxy (poly) alkoxyphenyl) fluoren-9-yl] Biphenyl is 4,4'-bis [9- (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene- 9-Il] biphenyl, 4,4'-bis [9- (4- (2- (2-hydroxyethoxy) ethoxy) -3-phenylphenyl) fluoren-9-yl] Biphenyl and other bis [9- (hydroxy) (Mono or deca) C _2-4 alkoxy-C _6-10 aryl-phenyl) Fluoren-9-yl] Biphenyl and the like can be mentioned.

Examples of the bis [9- (hydroxy (poly) alkoxynaphthyl) fluoren-9-yl] biphenyls include 4,4'-bis [9- (6- (2-hydroxyethoxy) -2-naphthyl) fluorene. -9-yl] biphenyl, 4,4'-bis [9-(6- (2-hydroxypropoxy) -2-naphthyl) fluoren-9-yl] biphenyl, 4,4'-bis [9- (6- (6-) (2- (2-Hydroxyethoxy) ethoxy) -2-naphthyl) fluoren-9-yl] biphenyl, 4,4'-bis [9-(5- (2-hydroxyethoxy) -1-naphthyl) fluoren-9 -Il] biphenyl, 3,3'-bis [9-(6- (2-hydroxyethoxy) -2-naphthyl) fluoren-9-yl] biphenyl, 2,2'-bis [9- (6- (2-) -Hydroxyethoxy) -2-naphthyl) fluoren-9-yl] Biphenyl and other bis [9- (hydroxy (mono or deca) C _2-4 alkoxy-naphthyl) fluoren-9-yl] biphenyl and the like can be mentioned.

Of these compounds, bis [9- (hydroxy (poly) alkoxynaphthyl) fluorene-9-yl] biphenyls are preferable, and 4,4'-bis [9- (6- (2-) "from the viewpoint of heat resistance and the like. -Hydroxyethoxy) -2-naphthyl) fluorene-9-yl] Biphenyl and other 4,4'-bis [9- (hydroxy (mono or penta) C _2-3 alkoxy-naphthyl) fluorene-9-yl] biphenyl More preferred.

(Characteristics of Fluorene Compound (1))
Since the fluorene compound or fluorene derivative (1) of the present invention has two fluorene skeletons in one molecule, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (BPEF), 9 , 9-Bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene (BNEF) has higher heat resistance than compounds having a known 9,9-bisarylfluorene skeleton.

The 5% weight loss temperature of the fluorene compound (1) of the present invention can be selected from the range of about 350 to 500 ° C., preferably 380 to 480 ° C., more preferably 400 to 450 ° C., and particularly 41 to 430 ° C. The 10% weight loss temperature of the fluorene compound (1) of the present invention can be selected from the range of about 380 to 550 ° C, preferably 400 to 500 ° C, more preferably 420 to 480 ° C, and particularly 440 to 460 ° C. is there. The weight loss temperature can be measured using a differential thermogravimetric analyzer, and in detail, can be measured by the method described in Examples.

[Method for producing fluorene compound (1)]
(Method A)
The method for producing the novel fluorene compound (1) of the present invention is not particularly limited, and is represented by, for example, fluorenones represented by the formula (2a) and the formula (2b) according to the following reaction formula (method A). A biphenyl derivative represented by the formula (2) is prepared by the reaction with the organic metal reagent, and the biphenyl derivative represented by the formula (2) and an array having a hydroxyalkoxy group represented by the formula (3a) are prepared. The fluorene compound (1) of the present invention may be prepared by reacting with a ring.

[In the formula, Ar ¹ is the same as Ar ^1a and Ar ^1b including preferred embodiments, Ar ² is the same as Ar ^2a and Ar ^2b including preferred embodiments, and R ¹ is preferred as R ^1a and R ^1b. The same including the embodiments, R ² is the same as R ^2a and R ^2b including the preferred embodiments, p1 is the same as p1a and p1b including the preferred embodiments, and p2 is the preferred embodiments of p2a and p2b. Same including, M represents a lithium atom or group [-MgX] (X represents a halogen atom), Z is the same as Z ¹ and Z ² in a preferred manner, A is A ¹ and It is the same as A ² including the preferred embodiment, m is the same as m1 and m2 including the preferred embodiment, R ⁴ is the same as R ^4a and R ^4b including the preferred embodiment, and r is r1 and r2. Ar ^1a , Ar ^1b , Ar ^2a , Ar ^2b , Z ¹ , Z ² , A ¹ , A ² , R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R. ^3b , R ^4a , R ^4b , m1, m2, p1a, p1b, p2a, p2b, q1, q2, r1, and r2 are the same as described above, including preferred embodiments].

The fluorenones represented by the formula (2a) may be any fluorenones corresponding to the fluorene skeleton formed by Ar ^1a and Ar ^2a and / or Ar ^1b and Ar ^2b in the formula (1), for example, 9 -Fluorenone, benzofluorenone, dibenzofluorenone, etc. can be used.

In the formula (2b), in the group [-MgX] represented by M, the halogen atom represented by X includes a fluorine atom, a chlorine atom, a bromine atom and the like, and is usually a bromine atom in many cases. .. The group M is preferably a group [−MgX]. Further, the types of M to be substituted with different benzene rings may be different from each other, but usually they are often the same. Further, the substitution position of M may be any position, but usually, it is often the 2,2'position, 3,3'position or 4,4'position of the biphenyl ring, and is preferably 4,. It is the 4'position.

As the organometallic reagent represented by the formula (2b), M in the formula (2b) is a Grignard reagent represented by a group [-MgX] (X represents a halogen atom), and M is a lithium atom. Examples thereof include an organolithium reagent which is (Li). Organometallic reagents such as Grignard reagents and organolithium reagents represented by the formula (2b) can be prepared by conventional methods, for example, direct metallization of 4,4'-dihalobiphenyl with metallic magnesium or metallic lithium. It may be prepared by a metal-halogen exchange reaction with an organometallic compound such as C _1-6 alkylmagnesium halide such as isopropylmagnesium bromide and alkyllithium such as methyllithium and butyllithium.

The ratio of fluorenones (2a) can be selected from the range of about 1.2 to 20 mol with respect to 1 mol of the organometallic reagent (2b), and preferably, 1.5 to 10 mol, 1 .8-8 mol, 2-5 mol.

The reaction between the fluorenones (2a) and the organometallic reagent (2b) may be carried out in the presence of a catalyst. The catalyst may be an organic catalyst, but an inorganic catalyst such as a metal compound is usually used. Examples of the metal compound include metal cyanides such as copper (I) cyanide and copper (II) cyanide; and metal halides such as lithium chloride, lithium bromide, lithium iodide, copper (I) chloride and copper (II) chloride. Compounds: Metal halides such as lithium perchlorate. These catalysts can be used alone or in combination of two or more. The amount of the catalyst used is not particularly limited and can be selected from the range of about 0.01 to 5 mol, preferably 0.2 to 2 mol, with respect to 1 mol of the organometallic reagent.

The reaction between the fluorenones (2a) and the organometallic reagent (2b) may be carried out in the presence of a solvent. The solvent is not particularly limited as long as it is a solvent that is inert to the reaction between the fluorenones (2a) and the organometallic reagent (2b), and examples thereof include aprotic solvents such as hydrocarbons, ethers, and amides. Examples of the hydrocarbons include aromatic hydrocarbons such as toluene, xylene and ethylbenzene. Examples of ethers include dialkyl ethers such as diethyl ether and dipropyl ether; and cyclic ethers such as 1,4-dioxane and tetrahydrofuran. Examples of amides include N, N-dimethylformamide and the like. These solvents can be used alone or in combination of two or more.

Moreover, the reaction may be carried out in the air or in an atmosphere of an inert gas. Examples of the inert gas include nitrogen gas and argon gas. The reaction may be carried out under reduced pressure, but is usually carried out under pressurized pressure or normal pressure. The reaction temperature can be selected from the range of about 0 to 150 ° C., preferably 10 to 100 ° C., 20 to 80 ° C., and 30 to 60 ° C. in a stepwise manner. The reaction may be carried out under reflux of the solvent.

Examples of the compound represented by the formula (3a) include the compounds corresponding to the allene ring having a hydroxyalkoxy group in the fluorene compound (1), specifically, alkylene glycol monoaryl ethers and dialkylene glycol monoaryl ethers. And so on.

Examples of the alkylene glycol monoaryl ethers include 2-phenoxyethanol (ethylene glycol monophenyl ether), propylene glycol monophenyl ether, tetramethylene glycol monophenyl ether and the like with _respect to C _2-4 alkylene glycol monophenyl ether (or 1 mol of phenol). C _2-4 alkylene oxide to 1 mole are added adduct) Te, ethylene glycol mono-naphthyl ether, propylene glycol mono-naphthyl ether, C _2-4 alkylene glycol mono-naphthyl ether (or naphthol 1 mole of tetramethylene glycol mononaphthyl ether On the other hand, C _2-4 alkylene glycol mono C _6-10 aryl ether such as C _2-4 alkylene oxide mono-C _6-10 aryl ether and the like (additional substance to which 1 mol of C _2-4 alkylene oxide is added) can be mentioned.

Examples of dialkylene glycol monoaryl ethers include diC _2-4 alkylene glycol monophenyl ethers such as diethylene glycol monophenyl ether and dipropylene glycol monophenyl ether; and di C ₂ such as diethylene glycol mononaphthyl ether and dipropylene glycol mononaphthyl ether. _-4 alkylene glycol mononaphthyl ether and the like.

The compounds represented by these formulas (3a) can be used alone or in combination of two or more. Among the compounds represented by these formulas (3a), preferably C _2-4 alkylene glycol mono C _6-10 aryl ether, more preferably in C _2-4 alkylene glycol mono naphthyl ethers such as ethylene glycol mononaphthyl ether is there.

The ratio of the compound represented by the formula (3a) can be selected from the range of about 1.8 to 20 mol, preferably 2 to 10 mol, more preferably 2.5 mol, with respect to 1 mol of the biphenyl derivative (2). ~ 5 mol.

The reaction between the biphenyl derivative (2) and the compound represented by the formula (3a) may be carried out in the presence of a catalyst, and the catalyst may be either an acid catalyst or a basic catalyst. The acid catalyst may be either an inorganic acid or an organic acid, examples of the inorganic acid include sulfuric acid, hydrogen chloride, hydrochloric acid, phosphoric acid and the like, and examples of the organic acid include sulfonic acid, specifically, Examples thereof include alkane sulfonic acid such as methane sulfonic acid and ethane sulfonic acid, and arene sulfonic acid such as toluene sulfonic acid. Examples of the basic catalyst include tertiary amines such as triethylamine, organic bases such as heterocyclic tertiary amines such as pyridine and morpholin; alkali metals such as sodium hydroxide and calcium hydroxide, or alkaline earth metal hydroxides. Alkaline metals such as sodium carbonate, sodium hydrogencarbonate, magnesium carbonate or alkaline earth metal carbonates, alkali metals such as sodium methoxydo, sodium ethoxyoxide, potassium t-butoxide Linear or branched C _1-6 Examples thereof include inorganic bases such as alkoxides. These catalysts can be used alone or in combination of two or more.

The amount of the catalyst used can be selected according to the type of catalyst, and can be selected from the range of about 0.1 to 100 parts by mass with respect to 100 parts by mass of the biphenyl derivative (2), for example, 1 to 80 parts by mass, preferably. It is 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and particularly 30 to 50 parts by mass.

The reaction between the biphenyl derivative (2) and the compound represented by the formula (3a) may be carried out in the presence of a solvent. The solvent is not particularly limited as long as it is a solvent inert to the reaction, and examples thereof include hydrocarbons, halogen-based solvents, ethers, ketones, nitriles, amides, and sulfoxides. Examples of the hydrocarbons include aromatic hydrocarbons such as toluene, xylene and ethylbenzene. Examples of the halogen-based solvent include halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, and trichloroethane. Examples of ethers include dialkyl ethers such as diethyl ether and dipropyl ether; and cyclic ethers such as 1,4-dioxane and tetrahydrofuran. Examples of the ketones include dialkyl ketones such as acetone, methyl ethyl ketone (ethyl methyl ketone), diisopropyl ketone, and isobutyl methyl ketone. Examples of nitriles include acetonitrile and the like. Examples of the amides include N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc). Examples of sulfoxides include dimethyl sulfoxide (DMSO) and the like. These solvents can be used alone or in combination of two or more.

Moreover, the reaction may be carried out in the air or in an atmosphere of an inert gas. Examples of the inert gas include nitrogen gas and argon gas. The reaction may be carried out under reduced pressure, but is usually carried out under pressurized pressure or normal pressure. The reaction temperature can be selected from the range of about 0 to 150 ° C., preferably 10 to 100 ° C., 20 to 80 ° C., and 30 to 60 ° C. in a stepwise manner. The reaction may be carried out under reflux of the solvent.

After completion of the reaction, the fluorene compound (1) can be separated and purified by a conventional separation method, for example, a separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a separation means combining these.

(Method B)
The method for producing the fluorene compound (1) is not limited to the above method A, and the biphenyl derivative (2) prepared by the method A is reacted with the compound represented by the following formula (3b) to carry out the following formula (4). ) Is prepared, and the compound represented by the formula (4) and the compound corresponding to the alkylene groups A ¹ and A ² (or the oxyalkylene groups OA ¹ and OA ² ) in the formula (1) are used. May be reacted to prepare.

(In the formula, Z, R ⁴ , r, Ar ^1a , Ar ^1b , Ar ^2a , Ar ^2b , Z ¹ , Z ² , R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , R ^4a , ^R4b , p1a, p1b, p2a, p2b, q1, q2, r1, and r2 are the same as described above, including preferred embodiments.)

Examples of the compound represented by formula (3b), in the compounds represented by formula (4), compounds corresponding to the arene ring Z ¹ and Z ² corresponds to a hydroxy group, specifically, phenols, Hydroxy C _6-12 arenes such as naphthols and phenylphenols can be mentioned.

Examples of phenols include phenol; C _1-6 alkyl-phenol such as cresol and ethyl phenol; and di C _1-6 alkyl-phenol such as xylenol. Examples of naphthols include naphthols such as 1-naphthol and 2-naphthol; C _1-6 alkyl-naphthols such as methyl naphthol and ethyl naphthol; and di C _1-6 alkyl-naphthols such as dimethyl naphthol. Examples of phenylphenols include mono- and di-C _1-6 alkyl-phenols such as phenylphenol; methylphenylphenol. The compounds represented by these formulas (3b) can be used alone or in combination of two or more.

The reaction conditions between the biphenyl derivative (2) and the compound represented by the formula (3b) are the same as those of the biphenyl derivative (2) and the compound represented by the formula (3a) in the method A, including preferred embodiments. is there.

Examples of the compound corresponding to the alkylene groups A ¹ and A ² (or the oxyalkylene groups OA ¹ and OA ² ) in the formula (1) include alkylene oxides, alkylene carbonates and haloalkanols. Examples of the alkylene oxide include C _2-4 alkylene oxides such as ethylene oxide and propylene oxide. Examples of the alkylene carbonate include C _2-4 alkylene carbonate such as ethylene carbonate and propylene carbonate. Examples of the halo alkanol include halo C _1-4 alkanols such as 3-chloropropanol. These compounds can be used alone or in combination of two or more.

When the compound represented by the formula (4) is reacted with an alkylene oxide or an alkylene carbonate, the (poly) oxyalkylene unit can be introduced via the hydroxy group of the compound represented by the formula (4). When an alkylene carbonate is used, an oxyalkylene unit (alkoxy unit) is introduced by causing a decarboxylation reaction after the addition of the alkylene carbonate.

The ratio of the compound corresponding to the alkylene groups A ¹ and A ² (or the oxyalkylene groups OA ¹ and OA ² ) can be adjusted according to the number of the oxyalkylene groups OA ¹ and OA ² to be added, and is represented by the formula (4). It can be selected from the range of about 1.5 to 30 mol, preferably 1.8 to 20 mol, and more preferably 2 to 10 mol, based on 1 mol of the hydroxy group of the compound.

The reaction between the compound represented by the formula (4) and the compound corresponding to the alkylene groups A ¹ and A ² (or the oxyalkylene groups OA ¹ and OA ² ) may be carried out in the presence of a catalyst, and the catalyst may be used. , A basic catalyst or an acid catalyst may be used, but a basic catalyst is usually used in many cases. Examples of the basic catalyst include tertiary amines such as triethylamine, amines such as heterocyclic tertiary amines such as pyridine and morpholine, alkali metal acetate such as sodium acetate and calcium acetate, and alkaline earth metal salts. Organic bases: alkali metals such as sodium hydroxide and calcium hydroxide or alkaline earth metal hydroxides, alkali metals such as sodium carbonate and magnesium carbonate, or inorganic bases such as alkaline earth metal carbonates can be mentioned. These catalysts can be used alone or in combination of two or more.

The amount of the catalyst used can be adjusted according to the type of catalyst, and can be selected from the range of about 0.1 to 100 parts by mass with respect to 100 parts by mass of the compound represented by the formula (4), for example, 1 to 80 parts by mass. Parts, preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass.

The reaction between the compound represented by the formula (4) and the compound corresponding to the alkylene groups A ¹ and A ² (or the oxyalkylene groups OA ¹ and OA ² ) may be carried out in the presence of a solvent, and the reaction may be carried out as a solvent. In the method A, the same solvent as the solvent described in the section of the reaction between the biphenyl derivative (2) and the compound represented by the formula (3a) can be mentioned.

Moreover, the reaction may be carried out in the air or in an atmosphere of an inert gas. Examples of the inert gas include nitrogen gas and argon gas. The reaction may be carried out under reduced pressure, but is usually carried out under pressurized pressure or normal pressure. The reaction temperature can be selected from the range of about 0 to 150 ° C., preferably 10 to 100 ° C., 20 to 80 ° C., and 30 to 60 ° C. in a stepwise manner. The reaction may be carried out under reflux of the solvent.

After completion of the reaction, the fluorene compound (1) can be separated and purified by a conventional separation method, for example, a separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a separation means combining these.

[Use of Fluorene Compound (1)]
The fluorene compound (1) of the present invention has an alcoholic hydroxyl group, unlike the compound described in Patent Document 1. Therefore, it can be used as a raw material for a polyester resin, and a polyester resin having heat resistance can be prepared by utilizing the high heat resistance of the fluorene compound (1).

Specifically, since the fluorene compound (1) of the present invention has two hydroxy groups, it can be used as a diol component (polymerization component) of a polyester resin. Therefore, in the preparation of the polyester resin, the diol component may contain at least the fluorene compound (1).

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. The evaluation methods in Examples and Comparative Examples are as follows.

(Heat resistance (weight reduction temperature))
Using a differential thermogravimetric analyzer (manufactured by Hitachi High-Tech Science Corporation, "TG / DTA6200"), the 5% weight loss temperature and the 10% weight loss temperature were measured under the following conditions.

Measurement temperature range: 30-520 ° C
Temperature rise temperature: 10 ° C / min Gas atmosphere: Under nitrogen atmosphere.

(Remaining heating)
The weight loss was measured when the mixture was heated to 180 ° C. and left for 1 minute without any change in weight.

(purity)
Using liquid chromatography (LC, manufactured by Shimadzu Corporation, “LC-2010A”), acetonitrile / water (volume ratio) = 70/30 → 95/5 → 70/30 was measured as an eluate.

(Molecular weight)
Elute acetonitrile / water (volume ratio) = 50/50 → 80/20 → 95/5 → 50/50 using a liquid chromatography mass spectrometer (LCMS, manufactured by Shimadzu Corporation, “Ninetex XB-C18”) Measured as a liquid.

(Refractive index)
Using a refractometer (manufactured by Atago, "DR-M2"), the refractive index was measured at a measurement temperature of 25 ° C. and a wavelength of 589 nm.

[Example 1]
(Synthesis of biphenyl derivative)
160.68 g (0.52 mol) of 4,4'-dibromobiphenyl was dissolved in 1 L of dehydrated THF (tetrahydrofuran) to prepare a biphenyl solution. Under a nitrogen stream, 150 mL of the biphenyl solution and a small amount of dibromoethane were added to a flask containing 25.0 g (1.03 mol) of magnesium and 21.83 g (0.52 mol) of lithium chloride to react. Started. After the reaction was started, 850 mL of the biphenyl solution was added dropwise into the separable flask while maintaining the exotherm. After completion of the dropwise addition, 500 mL of THF was added and the mixture was aged under reflux for 8 hours to prepare a Grignard reagent represented by the following formula (2b-1).

Subsequently, after cooling the temperature in the flask to 55 ° C., 141.33 g (0.78 mol) of 9-fluorenone dissolved in 400 mL of dehydrated THF was added dropwise into the flask over 2 hours. After completion of the dropping, the flask was aged under reflux for 5.5 hours, the flask was cooled in an ice bath, and 1 L of saturated aqueous ammonium chloride solution and 1 L of ion-exchanged water were added to complete the reaction. After completion of the reaction, a white precipitate was formed in the reaction solution to form a suspension. 150 mL of methyl isobutyl ketone (MIBK) is added to the reaction solution, transferred to a separating funnel in a suspension state, the aqueous layer is extracted, and the organic layer is washed with 500 mL of ion-exchanged water. Concentrated under reduced pressure. The organic layer concentrated under reduced pressure was recrystallized from diisopropyl ether, the resulting white crystals were filtered off, and dried to obtain a biphenyl derivative represented by the following formula (2-1).

(Synthesis of NEO adduct of biphenyldifluorene)
10 g (19.4 mmol) of the biphenyl derivative obtained by the above reaction, 10.95 g (58.2 mmol) of NEO (ethylene glycol mononaphthyl ether or ethylene oxide adduct of naphthol), and 75 g of dichloromethane were placed in a 300 mL separable flask. The mixture was stirred at 10 ° C. 4.4 g (45.8 mmol) of methanesulfonic acid was slowly added dropwise with stirring at 10 ° C. or lower. After completion of the dropping, the mixture was stirred at room temperature, further heated to 40 ° C., and reacted under reflux for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction solution was added dropwise to a mixed solution of methanol / distilled water (volume ratio) = 4/1, and the mixture was stirred at room temperature. Then, the crystals formed in the mixed solution are filtered off by a Kiriyama funnel and dried to obtain a NEO adduct (or 4,4'-bis [9) of biphenyldifluorene represented by the following formula (1-1). -(6- (2-Hydroxyethoxy) -2-naphthyl) fluorene-9-yl] biphenyl) 15.3 g (yield 92%) was obtained.

The ¹ H NMR, heating residue, purity, molecular weight and refractive index of the NEO adduct of biphenyldifluorene obtained are shown below.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ (ppm) = 4.00 (4H, d), 4.17 (4H, d), 7.08 (4H, m), 7.09-7.56 (26H) , M), 7.62 (2H, d), 7.80 (4H, d).

Heating residue (180 ° C): 99.4%
Purity: 94%
Weight average molecular weight: 855
Refractive index (589 nm, 25 ° C.): 1.68.

[Comparative Example 1]
The heat resistance of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (BPEF) was evaluated.

[Comparative Example 2]
The heat resistance of 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene (BNEF) was evaluated.

Table 1 shows the heat resistance evaluation results of Example 1 and Comparative Examples 1 and 2.

As is clear from Table 1, the 5% weight loss temperature and the 10% weight loss temperature were higher in Example 1 than in Comparative Examples 1 and 2, and the NEO adduct of biphenyldifluorene obtained in Example 1 was It was confirmed that it has high heat resistance.

In the present invention, the novel fluorene compound is useful as a polymerization component (or resin raw material, monomer), reagent, or the like of a polyester resin. The polyester resin using the compound as a polymerization component has high heat resistance. Therefore, the polyester resin (or its resin composition) is, for example, a paint, an ink, an adhesive, an adhesive, a resin filler, an antistatic agent, a protective film for electronic devices, electric / electronic materials, electric / electronic parts, or It can be suitably used for equipment, mechanical parts or equipment, optical members, and the like. Examples of electrical / electronic materials include charging trays, conductive sheets, carrier transport agents, light emitters, organic photoconductors, heat-sensitive recording materials, hologram recording materials, and examples of electrical / electronic parts or devices include inkjet printers and digital papers. , Organic semiconductor lasers, dye-sensitized solar cells, photochromic materials, organic EL elements, etc. Examples of mechanical parts or devices include automobiles, aerospace materials, sensors, sliding members, etc., and optical members include Examples include optical films (or optical sheets), optical lenses, optical fibers, optical disks, and the like. In particular, polyester resin is excellent in optical properties, and is therefore useful for forming (or forming) a molded product (optical member) for optical use.

Claims (4)

A fluorene compound represented by the following formula (1).

(In the formula, Ar ^1a , Ar ^1b , Ar ^2a and Ar ^2b represent an allene ring, R ^1a , R ^1b , R ^2a and R ^2b represent substituents, and p1a, p1b, p2a and p2b are integers of 0 or more. ¹ and Z ² represent an allene ring, A ¹ and A ² represent an alkylene group, m1 and m2 represent an integer of 1 or more, and R ^3a , R ^3b , R ^4a and R ^4b are substituents. , Q1 and q2 indicate integers from 0 to 4, and r1 and r2 indicate integers of 0 or more.) The fluorene compound according to claim ^1, wherein Z ¹ and Z ² are C _6-12 alle rings. The fluorene compound according to claim 1 or 2, wherein A ¹ and A ² are C _2-4 alkylene groups, and m 1 and m ² are integers of 1 to 3. It is selected from the reaction between the compound represented by the following formula (2) and the compound represented by the following formula (3a), or the compound represented by the following formula (4) and alkylene oxide, alkylene carbonate and haloalkanol. The method for producing a fluorene compound according to any one of claims 1 to 3 by reacting with at least one kind.

(In the formula, Z is the same as Z ¹ and Z ² , R ⁴ is the same as R ^4a and R ^4b , A is the same as A ¹ and A ² , and m is the same as m 1 and m 2. Ar ^1a , Ar ^1b , Ar ^2a , Ar ^2b , R ^1a , R ^1b , R ^2a , R ^2b , p1a, p1b, p2a, p2b, Z ¹ , Z ² , A ¹ , A ² , m1, m2. , R ^3a , R ^3b , R ^4a , R ^4b , q1, q2, r1 and r2 are the same as in the above equation (1).