JP7232692B2 - Fluorene compound and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to novel fluorene compounds and methods for producing the same.

Polyester resins (thermoplastic polyesters or saturated polyester resins) are provided with various properties by combining dicarboxylic acid components and diol components, which are polymerization components, depending on the application. Therefore, polyester resins are used in a variety of products ranging from industrial products such as electric/electronic parts and automobile parts to daily necessities such as clothing and food containers.

Such polyesters are lighter and more flexible than inorganic materials such as glass, and are being studied for use in applications such as optical members such as optical lenses. However, in some cases, it cannot be used for applications such as optical lenses for vehicles that are expected to be used in a high-temperature environment, and polyester resins (or resin raw materials) with higher heat resistance are desired.

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.

(Wherein, ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. x and z each independently represent 0 or 1.)

Japanese Patent No. 5598489

Patent Document 1 describes that when the 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 novolakated using formaldehyde or the like and used in the form of a novolac resin.

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

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

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

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

(Wherein, Ar ^1a , Ar ^1b , Ar ^2a and Ar ^2b represent arene rings, R ^1a , R ^1b , R ^2a and R ^2b represent substituents, p1a, p1b, p2a and p2b are integers of 0 or more , Z ¹ and Z ² represent an arene ring, A ¹ and A ² represent an alkylene group, m1 and m2 represent an integer of 1 or more, R ^3a , R ^3b , R ^4a and R ^4b are substituents , q1 and q2 are integers of 0 to 4, and r1 and r2 are integers of 0 or more.)

In the above formula (1), Z ¹ and Z ² may be C _6-12 arene rings, A ¹ and A ² are C _2-4 alkylene groups, m1 and m2 are integers of 1 to 3, There may be.

The present invention also includes a method for producing a compound represented by the formula (1), which comprises reacting a compound represented by the following formula (2) with a compound represented by the following formula (3a) The compound represented by the above formula (1) may be produced by the reaction of the compound represented by the following formula (4) with at least one selected from alkylene oxides, alkylene carbonates and haloalkanols to obtain the above Compounds of formula (1) may be produced.

(Wherein, 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 , m is the same as m1 and m2 and 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 formula (1).)

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

In the specification and claims of the present application, the number of carbon atoms in a substituent may be indicated by C ₁ , C ₆ , C ₁₀ or the like. For example, an alkyl group with 1 carbon atom is indicated by "C ₁ alkyl" and an aryl group with 6 to 10 carbon atoms is indicated by "C _6-10 aryl".

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

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

In the formula (1), the arene ring (aromatic hydrocarbon ring) represented by Ar ^1a , Ar ^1b , Ar ^2a and Ar ^2b includes monocyclic arene rings such as benzene ring, polycyclic arene rings, A ring-aggregated arene ring and the like can be mentioned.

Polycyclic arene rings include condensed bicyclic arene rings such as naphthalene ring, condensed polycyclic C _10-14 arene rings such as condensed tricyclic arene rings such as anthracene ring and phenanthrene ring, especially naphthalene. A ring is preferred.

The ring-aggregated arene ring includes biC _6-12 arene rings such as biphenyl ring, binaphthyl ring and phenylnaphthalene ring, with biphenyl ring being particularly preferred.

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

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

Examples of substituents represented by R ^1a , R ^1b , R ^2a and R ^2b include halogen atoms; hydrocarbon groups such as alkyl groups and aryl groups; and cyano groups.

A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and the like. The alkyl group includes linear or branched C _1-6 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group. Aryl groups include C _6-10 aryl groups such as phenyl groups. 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, more preferably methyl groups, ethyl groups and the like. such as C _1-3 alkyl groups, especially C _1-2 alkyl groups such as methyl groups. The types of R ^1a , R ^1b , R ^2a and R ^2b may be the same or different, and are usually the same. When R ^1a , R ^1b , R ^2a or R ^2b is an aryl group, it may form the ring-aggregated arene ring together with the bonding rings Ar ^1a , Ar ^1b , Ar ^2a and Ar ^2b .

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, preferably 0 ~4, 0-3, 0-2, 0 or 1, especially 0. The number of substitutions p1a, p1b, p2a, or p2b may be the same or different. 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. ^The substitution positions of R ^1a , R ^{1b ,} R ^2a and ^{R 2b are} not particularly ^limited . It is preferably at the 2nd, 3rd or 7th position.

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

In the present specification and claims, the term "fluorene skeleton" (or "fluorene ring") refers to a skeleton containing a fluorene skeleton such as a benzofluorene skeleton (benzofluorene ring) and a dibenzofluorene skeleton (dibenzofluorene ring). Also used in the sense of including.

Examples of 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; etc.

The halogen atom, the alkyl group and the aryl group include the same substituents as the aforementioned R ^1a , R ^1b , R ^2a and R ^2b including preferred embodiments. Cycloalkyl groups include C _5-8 cycloalkyl groups such as cyclopentyl and cyclohexyl groups. Aralkyl groups include C _6-10 aryl-C _1-4 alkyl groups such as benzyl group. Alkoxy groups include linear or branched C _1-10 alkoxy groups such as methoxy groups. Acyl groups include C _1-6 acyl groups such as an acetyl group. Examples of substituted amino groups include dialkylamino groups and diacylamino groups. Examples of dialkylamino groups include di-C _1-4 alkylamino groups such as dimethylamino group, and examples of diacylamino groups include di-C alkylamino groups such as diacetylamino group. _{A 1-4} acylamino group and the like can be mentioned. 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, and linear or branched groups 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, especially 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, and are usually the same. When R ^3a or R ^3b is an aryl group, R ^3a or R ^3b may form the ring-assembled arene ring together with the benzene ring to which it is bound.

The substitution numbers q1 and q2 of R ^3a and R ^3b can be selected from integers of 0 to 4, preferably 0 to 3, 0 to 2, 0 or 1, especially 0, stepwise below. Note that the substitution numbers q1 and q2 may be the same or different. When the substitution number q1 or q2 is 2 or more, the types of the 2 or more R ^3a or R ^3b may be the same or different. The substitution positions of R ^3a and R ^3b are not particularly limited.

The arene rings (aromatic hydrocarbon rings) represented by ring Z ¹ and ring Z ² include monocyclic arene rings such as benzene ring, polycyclic arene rings, and ring-assembled arene rings.

The polycyclic arene ring and ring-assembled arene ring include the same arene rings as 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, and are usually the same in many cases.

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

When Ar ^1a , Ar ^1b , Ar ^2a , or Ar ^2b is a benzene ring, the substitution positions of ring Z ¹ and ring Z ² bonded to the 9-position of the fluorene ring are not particularly limited ^. 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 for R ^3a and R ^3b including preferred embodiments. 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-assembled arene ring together with ring Z ¹ and 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 on the same ring Z ¹ or ring Z ² may be the same or different.

The substitution numbers r1 and r2 of R ^4a and R ^4b can be selected from integers of 0 or more, for example, integers of 0 to 8, preferably 0 to 4, 0 to 3, 0 to 2, 0 or 1, especially 0. Note that the substitution numbers r1 and r2 may be the same or different.

Examples of the alkylene group represented by A ¹ and A ² include straight-chain or A branched C _2-6 alkylene group is included. The types of A ¹ and A ² may be the same or different, and are usually the same. Preferred A ¹ , A ² are linear or branched C _2-4 alkylene groups, more preferably linear or branched C _2-3 alkylene groups, especially ethylene groups.

The number of repetitions (number of moles added) 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. , 1-3, 1-2, especially 1. In the present specification and claims, the "repeating number (number of moles added)" may be an average value (arithmetic mean value, arithmetic mean value) or an average number of moles added, and a preferred embodiment is Similar to the preferred integer range. Moreover, when m1 and m2 are 2 or more, two 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. It suffices that they are respectively substituted at appropriate substitution positions of ring Z ² . When the group [-O-(A ¹ O) _m1 -H] and the group [-O-(A ² O) _m2 -H] are substituted on 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) at any of the 2-, 3-, and 4-positions of the phenyl group bonded to the 9-position, preferably at the 3- or 4-position, particularly at the 4-position It is often replaced by the position. When the ring Z ¹ and ring Z ² are naphthalene rings, the naphthyl group bonded to the 9-position of the fluorene ring (Ar ^1a , Ar ^1b or Ar ^2a , Ar ^2b is a benzene ring) at the 1- or 2-position It ^is often substituted at any position of ⁵ to 8 positions, and ^the 1 ^position of the naphthalene ring or 2-position is substituted (substitution in the relationship of 1-naphthyl or 2-naphthyl), and substitution is preferably in the 1,5-position, 2,6-position relationship with respect to this substitution position, and 2,6 Substitution at the position is particularly preferred.

Typical compounds represented by the formula (1) include 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)fluoren-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, i.e. bis[9-(hydroxy (Poly)alkoxynaphthyl)fluoren-9-yl]biphenyls and the like. In the present specification and claims, "(poly)alkoxy" is used to include both alkoxy groups and polyalkoxy groups.

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

Bis[9-(hydroxy(poly)alkoxyphenyl)fluoren-9-yl]biphenyl includes 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) )phenyl)fluoren-9-yl]biphenyl, 3,3′-bis[9-(4-(2-hydroxyethoxy)phenyl)fluoren-9-yl]biphenyl, 2,2′-bis[9-(4 bis[9-(hydroxy(mono- or deca)C _2-4 alkoxy-phenyl)fluoren-9-yl]biphenyl such as -(2-hydroxyethoxy)phenyl)fluoren-9-yl]biphenyl;

Bis[9-(alkyl-hydroxy(poly)alkoxyphenyl)fluoren-9-yl]biphenyl includes 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-( Bis[9-(hydroxy(mono- or deca)C _2-4 alkoxy-C _1-4 alkyl such as 4-(2-(2-hydroxyethoxy)ethoxy)-3-methylphenyl)fluoren-9-yl]biphenyl -phenyl)fluoren-9-yl]biphenyl and the like.

Bis[9-(aryl-hydroxy(poly)alkoxyphenyl)fluoren-9-yl]biphenyl includes 4,4′-bis[9-(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene- 9-yl]biphenyl, bis[9-(hydroxy (mono to deca)C _2-4 alkoxy-C _6-10 aryl-phenyl)fluoren-9-yl]biphenyl and the like.

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- (2-(2-hydroxyethoxy)ethoxy)-2-naphthyl)fluoren-9-yl]biphenyl, 4,4′-bis[9-(5-(2-hydroxyethoxy)-1-naphthyl)fluorene-9 -yl]biphenyl, 3,3′-bis[9-(6-(2-hydroxyethoxy)-2-naphthyl)fluoren-9-yl]biphenyl, 2,2′-bis[9-(6-(2 bis[9-(hydroxy(mono- or deca)C _2-4 alkoxy-naphthyl)fluoren-9-yl]biphenyl such as -hydroxyethoxy)-2-naphthyl)fluoren-9-yl]biphenyl.

Among these compounds, bis[9-(hydroxy(poly)alkoxynaphthyl)fluoren-9-yl]biphenyls are preferred, and from the viewpoint of heat resistance, 4,4′-bis[9-(6-(2 4,4′-bis[9-(hydroxy(mono- or penta)C _2-3 alkoxy-naphthyl)fluoren-9-yl]biphenyl such as -hydroxyethoxy)-2-naphthyl)fluoren-9-yl]biphenyl More preferred.

(Properties 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) and other known compounds having a 9,9-bisarylfluorene skeleton have higher heat resistance.

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, particularly 410 to 430°C. Further, 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, particularly 440 to 460°C. be. The weight loss temperature can be measured using a differential thermogravimetric analyzer, and in detail, it 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. For example, according to the following reaction scheme (Method A), A biphenyl derivative represented by the formula (2) is prepared by reaction with an organometallic reagent, and the biphenyl derivative represented by the formula (2) and the arene having a hydroxyalkoxy group represented by the formula (3a) 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 R ² is the same as R ^2a and R ^2b including preferred embodiments, p1 is the same as p1a and p1b including preferred embodiments, and p2 is the same as p2a and p2b including preferred embodiments. M represents a lithium atom or a group [-MgX] (X represents a halogen atom), Z is the same as Z ¹ and Z ² including preferred embodiments, A is A ¹ and The same as ^A2 including preferred embodiments, m is the same as m1 and m2 including preferred embodiments, ^R4 is the same as ^R4a and ^R4b including preferred embodiments, 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 above, including preferred embodiments]

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

In the group [-MgX] represented by M in formula (2b), 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. . The group M is preferably the group [--MgX]. Further, the types of M substituting different benzene rings may be different from each other, but they are usually the same in many cases. Further, the substitution position of M may be any position, but usually the 2,2'-position, 3,3'-position or 4,4'-position of the biphenyl ring, preferably 4, 4' position.

As the organometallic reagent represented by formula (2b), M in formula (2b) is a Grignard reagent represented by a group [-MgX] (X represents a halogen atom), and M is a lithium atom. (Li) organic lithium reagents, and the like. Organometallic reagents such as Grignard reagents and organolithium reagents represented by formula (2b) can be prepared by conventional methods. or by a metal-halogen exchange reaction with an organometallic compound such as a C _1-6 alkylmagnesium halide such as isopropylmagnesium bromide, or an alkyllithium such as methyllithium or butyllithium.

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

The reaction between fluorenone (2a) and organometallic reagent (2b) may be carried out in the presence of a catalyst. The catalyst may be an organic catalyst, but usually an inorganic catalyst such as a metal compound is used. Metal compounds include metal cyanides such as copper (I) cyanide and copper (II) cyanide; metal halides such as lithium chloride, lithium bromide, lithium iodide, copper (I) chloride and copper (II) chloride; perhalogenate metal salts such as lithium perchlorate; These catalysts can be used alone or in combination of two or more. The amount of the catalyst to be 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, per 1 mol of the organometallic reagent.

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

Also, the reaction may be carried out in air or under an inert gas atmosphere. Examples of inert gas include nitrogen gas and argon gas. Moreover, although the reaction may be carried out under reduced pressure, it is usually carried out under increased pressure or normal pressure in many cases. 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 stages. In addition, you may perform reaction under reflux of a solvent.

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

Alkylene glycol monoaryl ethers include C _2-4 alkylene glycol monophenyl ethers such as 2-phenoxyethanol (ethylene glycol monophenyl ether), propylene glycol monophenyl ether, and tetramethylene glycol monophenyl ether (or per mol of phenol adduct obtained by adding 1 mol of C _2-4 alkylene oxide); C _2-4 alkylene glycol mononaphthyl ether such as ethylene glycol mononaphthyl ether, propylene glycol mononaphthyl ether, tetramethylene glycol mononaphthyl ether (or 1 mol of naphthol C _2-4 alkylene glycol mono C _6-10 aryl ethers such as adducts in which 1 mol of C _2-4 alkylene oxide is added to ).

Dialkylene glycol monoaryl ethers include di _-C2-4 alkylene glycol monophenyl ether such as diethylene glycol monophenyl ether and dipropylene glycol monophenyl ether; di- _C2 such as diethylene glycol mononaphthyl ether and dipropylene glycol mononaphthyl ether. _-4 alkylene glycol mononaphthyl ether and the like.

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

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, per 1 mol of the biphenyl derivative (2). ~5 moles.

The reaction between the biphenyl derivative (2) and the compound represented by 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 inorganic acids include sulfuric acid, hydrogen chloride, hydrochloric acid, and phosphoric acid. Examples of organic acids include sulfonic acid, specifically, Examples include alkanesulfonic acids such as methanesulfonic acid and ethanesulfonic acid, and arenesulfonic acids such as toluenesulfonic acid. Basic catalysts include tertiary amines such as triethylamine, organic bases such as heterocyclic tertiary amines such as pyridine and morpholine; alkali metal or alkaline earth metal hydroxides such as sodium hydroxide and calcium hydroxide; alkali metal or alkaline earth metal carbonates such as sodium carbonate, sodium bicarbonate, magnesium carbonate, alkali metal linear or branched C _1-6 such as sodium methoxide, sodium ethoxide, potassium t-butoxide Examples 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, for example 1 to 80 parts by mass, preferably 100 parts by mass of the biphenyl derivative (2). 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, particularly 30 to 50 parts by mass.

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

Also, the reaction may be carried out in air or under an inert gas atmosphere. Examples of inert gas include nitrogen gas and argon gas. Moreover, although the reaction may be carried out under reduced pressure, it is usually carried out under increased pressure or normal pressure in many cases. 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 stages. In addition, you may perform reaction under reflux of a solvent.

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

(Method B)
The method for producing the fluorene compound (1) is not limited to the method A, and the biphenyl derivative (2) prepared by the method A is reacted with the compound represented by the following formula (3b) to obtain the following formula (4). ), 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) may be prepared by reacting

(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 , R ^4b , p1a, p1b, p2a, p2b, q1, q2, r1, and r2 are the same as above, including preferred embodiments.)

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

Phenols include phenol; C _1-6 alkyl-phenols such as cresol and ethylphenol; and di-C _1-6 alkyl-phenols such as xylenol. Naphthols include naphthols such as 1-naphthol and 2-naphthol; C _1-6 alkyl-naphthols such as methylnaphthol and ethylnaphthol; and di-C _1-6 alkyl-naphthols such as dimethylnaphthol. Phenylphenols include phenylphenol; mono- or di-C _1-6 alkyl-phenols such as methylphenylphenol. These compounds represented by formula (3b) can be used alone or in combination of two or more.

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

Compounds corresponding to the alkylene groups A ¹ and A ² (or the oxyalkylene groups OA ¹ and OA ² ) in formula (1) include alkylene oxides, alkylene carbonates and haloalkanols. Alkylene oxides include C _2-4 alkylene oxides such as ethylene oxide and propylene oxide. Alkylene carbonates include C _2-4 alkylene carbonates such as ethylene carbonate and propylene carbonate. Haloalkanols include haloC _1-4alkanols such as 3-chloropropanol and the like. These compounds can be used individually or in combination of 2 or more types.

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

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

The reaction between the compound represented by 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. , a basic catalyst or an acid catalyst, but usually a basic catalyst is often used. Basic catalysts include tertiary amines such as triethylamine, amines such as heterocyclic tertiary amines such as pyridine and morpholine, and alkali metal or alkaline earth metal salts of acetates such as sodium acetate and calcium acetate. Organic bases; alkali metal or alkaline earth metal hydroxides such as sodium hydroxide and calcium hydroxide; inorganic bases such as alkali metal or alkaline earth metal carbonates such as sodium carbonate and magnesium carbonate; These catalysts can be used alone or in combination of two or more.

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

The reaction between the compound represented by 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. includes the same solvent as the solvent described in the section of the reaction of the biphenyl derivative (2) with the compound represented by the formula (3a) in the method A.

Also, the reaction may be carried out in air or under an inert gas atmosphere. Examples of inert gas include nitrogen gas and argon gas. Moreover, although the reaction may be carried out under reduced pressure, it is usually carried out under increased pressure or normal pressure in many cases. 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 stages. In addition, you may perform reaction under reflux of a solvent.

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

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

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 should contain at least the fluorene compound (1).

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited by these examples. In addition, each evaluation method in an Example and a comparative example is as follows.

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

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

(heating residue)
It was heated to 180° C., and the weight loss was measured when the weight change disappeared and the weight was left for 1 minute.

(purity)
Acetonitrile/water (volume ratio) = 70/30 → 95/5 → 70/30 was used as an eluent for measurement using liquid chromatography (LC, manufactured by Shimadzu Corporation, "LC-2010A").

(molecular weight)
Using a liquid chromatography mass spectrometer (LCMS, manufactured by Shimadzu Corporation, "Ninetex XB-C18"), acetonitrile/water (volume ratio) = 50/50 → 80/20 → 95/5 → 50/50 is eluted. Measured as a liquid.

(refractive index)
Using a refractometer (“DR-M2” manufactured by Atago Co., Ltd.), 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 charged with 25.0 g (1.03 mol) of magnesium and 21.83 g (0.52 mol) of lithium chloride to react. started. After starting the reaction, 850 mL of the biphenyl solution was dropped into the separable flask while maintaining heat generation. After completion of dropping, 500 mL of THF was added and aged under reflux for 8 hours to prepare a Grignard reagent represented by the following formula (2b-1).

Subsequently, after cooling the temperature inside the flask to 55° C., 141.33 g (0.78 mol) of 9-fluorenone dissolved in 400 mL of dehydrated THF was dropped into the flask over 2 hours. After completion of the dropwise addition, the mixture was aged under reflux for 5.5 hours, cooled in an ice bath, and 1 L of saturated ammonium chloride aqueous solution and 1 L of ion-exchanged water were added to terminate the reaction. After completion of the reaction, a white precipitate was formed in the reaction liquid, which turned into a suspension. 150 mL of methyl isobutyl ketone (MIBK) was added to the reaction solution, the suspension was transferred to a separating funnel, the aqueous layer was extracted, and the organic layer was separated and washed with 500 mL of ion-exchanged water. Concentrated under reduced pressure. The organic layer concentrated under reduced pressure was recrystallized with diisopropyl ether, and the resulting white crystals were separated by filtration 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. , and stirred at 10°C. While stirring at 10° C. or less, 4.4 g (45.8 mmol) of methanesulfonic acid was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature, 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 little by little to a mixed solution of methanol/distilled water (volume ratio)=4/1, followed by stirring at room temperature. After that, the crystals generated in the mixed solution are filtered off with a Kiriyama funnel and dried to give a biphenyldifluorene NEO adduct represented by the following formula (1-1) (or 4,4′-bis[9 15.3 g (92% yield) of -(6-(2-hydroxyethoxy)-2-naphthyl)fluoren-9-yl]biphenyl) were obtained.

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

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 are higher in Example 1 than in Comparative Examples 1 and 2, and the NEO adduct of biphenyldifluorene obtained in Example 1 is was confirmed to have high heat resistance.

In the present invention, the novel fluorene compound is useful as a polymerizable component (or resin raw material, monomer) for polyester resins, a reagent, and the like. A polyester resin using the above compound as a polymerization component has high heat resistance. Therefore, polyester resins (or resin compositions thereof) are, for example, paints, inks, adhesives, adhesives, resin fillers, antistatic agents, protective films such as electronic devices, electrical / electronic materials, electrical / electronic parts or It can be suitably used for equipment, mechanical parts or equipment, optical members, and the like. Examples of electric/electronic materials include charging trays, conductive sheets, carrier transport agents, light-emitting bodies, organic photoreceptors, heat-sensitive recording materials, and hologram recording materials. , organic semiconductor lasers, dye-sensitized solar cells, photochromic materials, organic EL elements, etc.; include optical films (or optical sheets), optical lenses, optical fibers, and optical discs. In particular, polyester resins are useful for constructing (or forming) moldings (optical members) for optical applications because of their excellent optical properties.

Claims (3)

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

(wherein Ar ^1a , Ar ^1b , Ar ^2a and Ar ^2b represent a C _6-10 arene ring, R ^1a , R ^1b , R ^2a and R ^2b are linear or branched C _1-3 alkyl groups , p1a, p1b, p2a and p2b are integers from 0 to 2 , Z ¹ and Z ² are C _6-10 arene rings, A ¹ and A ² are linear or branched C _{2- 4} alkylene groups, m1 and m2 are integers of 1 to 3 , R ^3a , R ^3b , R ^4a and R ^4b are linear or branched C _1-3 alkyl groups , q1 and q2 are An integer from 0 to 2 is shown, and r1 and r2 are integers from 0 to 2. ) The fluorene compound according to claim 1, wherein A ¹ and A ² are C _2-3 alkylene groups, and m1 and m2 are integers of 1-2 . Reaction of a compound represented by the following formula (2) with a compound represented by the following formula (3a), or a compound represented by the following formula (4) and selected from alkylene oxide, alkylene carbonate and haloalkanol A method for producing the fluorene compound according to claim 1 or 2 by reacting with at least one.

(Wherein, 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 , m is the same as m1 and m2 and 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 formula (1) described in claim 1. )