JP5607393B2 - Fluorene derivative and method for producing the same - Google Patents

Description

  The present invention relates to a novel compound (monofunctional compound) having a fluorene skeleton (9,9-bisphenylfluorene skeleton) and a method for producing the same.

  A compound that can select monomer components or modify resins in order to impart or improve properties such as thermal properties (heat resistance, etc.) and optical properties (high refractive index, etc.) in resins and resin raw materials The method of adding is taken. For example, a compound having a fluorene skeleton (such as a 9,9-bisphenylfluorene skeleton) is known to have an excellent function in terms of refractive index, heat resistance, and the like. As a method for expressing such an excellent function of the fluorene skeleton in a resin, a fluorene compound having a reactive group (hydroxyl group, amino group, etc.), for example, bisphenol fluorene (BPF), biscresol fluorene (BCF), bis A general method is to use phenoxyethanol fluorene (BPEF) or the like as a base component of a resin and introduce a fluorene skeleton into a part of the skeleton structure of the resin. For example, as an example using such a resin having a fluorene skeleton, JP-A No. 2002-284864 (Patent Document 1) discloses a molding material composed of a polyester resin having a 9,9-bisphenylfluorene skeleton. It is disclosed. JP-A-2004-339499 (Patent Document 2) discloses a resin having a fluorene skeleton such as bisphenolfluorene, bisaminophenylfluorene, or bisphenoxyethanolfluorene as a polymerization component (polyester resin, polycarbonate resin, A urethane resin, an acrylic resin, a polyamide resin, a polyimide resin, an epoxy resin, a vinyl ester resin, a phenol resin, an aniline resin, and the like) and an additive are disclosed.

  Thus, polyfunctional (particularly bifunctional) fluorene compounds such as BPF, BCF, and BPEF are known as resin monomers.

  On the other hand, monofunctional fluorene compounds such as 9-fluorenol and 9-fluorenylmethanol are also known. For example, regarding 9-fluorenylmethanol, JP-A-8-268941 (Patent Document 3) reacts a secondary alcohol with fluorene-9-carbaldehyde in the presence of a specific zirconium catalyst. A method for producing 9-fluorenylmethanols is disclosed.

  JP 2009-13096 A (Patent Document 4) discloses that a compound represented by the following formula (1A) and a compound represented by the following formula (1B) are reacted to form the following formula (1). It is described that the compound represented by this can be manufactured.

Wherein ring Z ¹ and ring Z ² are the same or different and are aromatic hydrocarbon rings, E is an oxygen atom, sulfur atom or imino group, R ¹ is a non-reactive substituent, R ² is an alkylene group, R ³ And R ⁴ are the same or different and represent a non-reactive substituent, k is an integer of 0 to 4, and m, n, and p are each an integer of 0 or more.)
However, although the compound of this document is monofunctional, it has two aromatic hydrocarbon groups at the 9-position of fluorene, has a high viscosity, and handling properties may not be sufficient.

  JP-A-2000-26349 (Patent Document 5) reacts 9-fluorenone with alkylphenols (2,5-xylenol, etc.) in the presence of an acid catalyst (hydrogen chloride, etc.) and an alkyl mercaptan. It is disclosed that 9,9-bis (4-hydroxy-2,5-alkylphenyl) fluorene such as 9,9-bis (4-hydroxy-2,5-dimethylphenyl) fluorene can be obtained. .

  Japanese Patent Application Laid-Open No. 2003-221352 (Patent Document 6) discloses a method of producing bisphenol fluorenes by reacting fluorenone with phenols in the presence of thiols and sulfuric acid. In this document, dialkylphenols (2,3-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 2,6-di-tert-butylphenol, etc.) are exemplified as phenols. However, an example using 2,5-dialkylphenol such as 2,5-dimethylphenol is not disclosed.

JP 2002-284864 A (Claims) JP 2004-339499 A (claims, paragraph number [0032]) JP-A-8-268941 (Claims, paragraph number [0001]) JP 2009-13096 A (claims, paragraph number [0001]) JP 2000-26349 A (claims, paragraph [0017], paragraph [0045] (Example 4)) JP2003-221352A (Claims, paragraph [0017], paragraph [0045] (Example 4))

  Accordingly, an object of the present invention is to provide a novel monofunctional fluorene skeleton-containing compound useful as a diluent (or diluent raw material), a resin monomer raw material, and the like, and a method for producing the same.

  Another object of the present invention is to provide a method for efficiently producing the novel monofunctional fluorene skeleton-containing compound as described above.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that in the presence of an acid catalyst (such as sulfuric acid) and a thiol (such as mercaptocarboxylic acid), a fluorenone and a 2,5-dialkylphenol ( For example, when a specific phenol such as 2,5-xylenol is reacted, a compound in which two phenols are substituted at the 9-position of fluorene [for example, 9,9- (4 -Hydroxy-2,5-dialkylphenyl) fluorene etc.], and a specific monofunctional compound in which one 2,5-dialkylphenyl group or the like is substituted at the 9-position of fluorenes, and such a compound Has been found useful as a monomer raw material, a diluent (or a diluent raw material), etc., and has completed the present invention.

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

(In the formula, R ¹ represents a substituent, R ² represents an alkylene group, R ^{3 to} R ⁵ represent a substituent, k represents an integer of 0 to 4, m represents an integer of 0 or more, and n represents 0 to 0. (It is an integer of 2.)
In the above formula (1), R ^{3 to} R ⁵ may be, for example, the same or different and may be a hydrocarbon group (for example, an alkyl group, an aryl group, etc.) or an alkoxy group. In particular, in the formula (1), R ³ and R ⁴ may be an alkyl group (for example, a C _1-4 alkyl group such as a methyl group), and n may be 0.

  Such a fluorene compound is a monofunctional compound having a hydroxyl group, and as a compound derivatized as it is or as necessary (for example, (meth) acrylated, glycidyletherified, etc.) ) Or a diluent. Therefore, the fluorene compound (or its derivative, for example, (meth) acrylate of the fluorene compound, glycidyl ether of the fluorene compound, etc.) may be a compound for use as a resin raw material or a diluent.

  In the present invention, in the presence of an acid catalyst and thiols, the following formula (2)

(In the formula, R ¹ and k are the same as above.)
And a compound represented by the following formula (3)

(Wherein R ^{2 to} R ⁵ , m, and n are the same as described above.)
And a method for producing the compound represented by the formula (1) by reacting with the compound represented by formula (1).

  In particular, in this method, an acid having a dehydrating action (such as sulfuric acid) may be suitably used as the acid catalyst. Typically, sulfuric acid as the acid catalyst is used in an amount of 100 parts by weight of the compound represented by the formula (2). You may use 30 weight part or more with respect to.

  The compound of the present invention is a monofunctional compound having a specific fluorene skeleton, and is useful as a diluent (or a diluent raw material), a monomer raw material, a resin initiator, and the like. Such a monofunctional compound (or a derivative thereof, for example, (meth) acrylate (monofunctional (meth) acrylate), glycidyl ether (monoglycidyl ether), etc.) has a 9-phenylfluorene skeleton. In particular, it is useful as a resin modifier that can impart high heat resistance and excellent optical properties (low birefringence, high refractive index, etc.) or a raw material thereof (particularly a diluent or a diluent raw material). Further, in the present invention, the novel monofunctional fluorene skeleton-containing compound as described above can be efficiently produced with high purity.

[Fluorene compound represented by formula (1)]
The compound of the present invention (fluorene compound) is represented by the following formula (1).

(In the formula, R ¹ represents a substituent, R ² represents an alkylene group, R ^{3 to} R ⁵ represent a substituent, k represents an integer of 0 to 4, m represents an integer of 0 or more, and n represents 0 to 0. (It is an integer of 2.)
In the above formula (1), the substituent represented by the group R ¹ is not particularly limited as long as it is a non-reactive substituent. For example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.) , A hydrocarbon group [for example, an alkyl group, an aryl group (C _6-10 aryl group such as a phenyl group)] and the like, and is often a cyano group or an alkyl group (particularly an alkyl group). Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . In addition, when k is plural (two or more), the groups R ¹ may be different from each other or the same. Further, the groups R ¹ substituted on the two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or different. Further, the bonding position (substitution position) of the group R ¹ with respect to the benzene ring constituting the fluorene is not particularly limited. The preferred substitution number k is 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the number of substitutions k may be the same or different from each other.

In the formula (1), the alkylene group represented by the group R ² is not particularly limited. For example, a C _2-10 alkylene group (for example, ethylene group, trimethylene group, propylene group, butane-1,2- C _2-6 alkylene group such as diyl group and hexylene group) can be exemplified, and C _2-4 alkylene group (particularly, C _2-3 alkylene group such as ethylene group and propylene group) is particularly preferable. R ² may be the same or different alkylene groups (that is, when m is plural, R ² may be the same or different). That is, when m is 2 or more, the polyalkoxy (polyoxyalkylene) group [— (OR ² ) _m —] may be composed of the same oxyalkylene group, and a plurality of oxyalkylene groups (for example, oxy Ethylene group and oxypropylene group).

The number (number of added moles) m of the oxyalkylene group (OR ² ) can be selected, for example, from a range of about 0 to 15, for example, 0 to 10 (for example, 1 to 10), preferably 0 to 8 (for example, 1-8), more preferably 0-6 (eg 1-6), in particular 0-4 (eg 1-4), usually 0-2 (eg 1-2) Also good. In addition, the compound in which m is 1 or more includes a compound corresponding to an oxyalkylene group (OR ² ) other than the method described later, and a compound corresponding to an oxyalkylene group (OR ² ) [eg, alkylene oxide (eg, ethylene oxide, propylene oxide, etc. C _2-4 alkylene oxide), alkylene carbonate (for example, C _2-4 alkylene carbonate such as ethylene carbonate) and the like] can also be obtained.

In the formula (1), examples of the substituents R ³ and R ⁴ include an alkyl group (eg, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, preferably Is a C _1-8 alkyl group, more preferably a C _1-6 alkyl group, etc., a cycloalkyl group (C _5-10 cycloalkyl group such as a cyclohexyl group, preferably a C _5-8 cycloalkyl group, more preferably Is a C _5-6 cycloalkyl group), an aryl group (eg, a C _6-14 aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, preferably a C _6-10 aryl group, more preferably a C _{6 -8} aryl group, etc.), aralkyl groups (C _6-10 aryl-C _1-4 alkyl group such as benzyl group, phenethyl group, etc.) Hydrogen group; alkoxy group (C _1-12 alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, preferably C _1-8 alkoxy group, more preferably C _1-6 alkoxy group, etc.), cycloalkoxy group (C _5-10 cycloalkyloxy group such as cyclohexyloxy group), aryloxy group (C _6-10 aryloxy group such as phenoxy group), aralkyloxy group (for example, C _6-10 such as benzyloxy group) Aryl-C _1-4 alkyloxy group) or the like —OR ⁶ [wherein R ⁶ represents a hydrocarbon group (such as the hydrocarbon group exemplified above). An alkylthio group (a C _1-20 alkylthio group such as a methylthio group, an ethylthio group, a propylthio group or a butylthio group, preferably a C _1-8 alkylthio group, more preferably a C _1-6 alkylthio group), a cycloalkylthio group ( C _5-10 cycloalkylthio group such as cyclohexylthio group), arylthio group (C _6-10 arylthio group such as thiophenoxy group), aralkylthio group (for example, C _6-10 aryl-C ₁ such as benzylthio group) _-4 alkylthio group) or the like -SR ⁶ (wherein R ⁶ is the same as described above); acyl group (C _1-6 acyl group such as acetyl group); alkoxycarbonyl group (C such as methoxycarbonyl group) _C1-4 alkoxy - carbonyl group); a halogen atom (fluorine atom, chlorine atom, bromine atom Nitro group; cyano group; mercapto group; carboxyl group; amino group; carbamoyl group; substituted amino group (for example, dialkylamino group such as dimethylamino group); sulfonyl group; Bonded substituents [eg, alkoxyaryl groups (eg, C _1-4 alkoxy C _6-10 aryl groups such as methoxyphenyl group), alkoxycarbonylaryl groups (eg, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, etc. C _1-4 alkoxy-carbonyl C _6-10 aryl group etc.)] and the like.

Of these, typically, the groups R ³ and R ⁴ are a hydrocarbon group, —OR ⁶ (wherein R ⁶ represents a hydrocarbon group), —SR ⁶ (wherein R ⁴ is the above-mentioned group). As well as an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, or a substituted amino group.

Preferred groups R ³ and R ⁴ include a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, C _6-10 aryl group), aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group etc.), alkoxy group (C _1-4 alkoxy group etc.) and the like. In particular, R ³ represents a hydrocarbon group (especially an alkyl group such as a C _1-4 alkyl group (especially a methyl group)) or an aryl group [eg a C _6-10 aryl group (especially a phenyl group)]. Group).

R ³ and R ⁴ may be the same or different groups.

In the formula (1), as the substituent R ⁵ , the same groups as those exemplified in the above R ³ and R ⁴ (for example, hydrocarbon groups such as alkyl groups, alkoxy groups, halogen atoms, etc.) ). R ⁵ may be the same as or different from R ³ and / or R ^4, and when n is 2, the two R ⁵ may be the same or different groups. n may be 0 to 2, preferably 0 to 1, and more preferably 0. Although the substitution position of the radicals R ⁵ are not particularly limited, when n is 1, may be either 3-position or 6-position of the phenyl group substituted at position 9 of the fluorene.

Representative compounds represented by the formula (1) include, for example, 9- (4-hydroxy-3,5-dialkylphenyl) fluorene [for example, 9- (4-hydroxy-3,5-dimethylphenyl) A compound in which m is 0 in the above formula (1) such as 9- (4-hydroxy-3,5-diC _1-4 alkylphenyl) fluorene] such as fluorene; 9- [4- (hydroxyalkoxy) -3 , 5-dialkyl phenyl] fluorene {e.g., 9- [4- (2-hydroxyethoxy) -3,5-dimethylphenyl)] fluorene such as 9- [4- (hydroxy _{C 2-4} alkoxy) -3,5 In the above formula (1), m is 1 or more, such as —di-C _1-4 alkylphenyl] fluorene}.

(Production method)
Although the compound of this invention is not specifically limited, Usually, in presence of an acid catalyst, following formula (2)

(In the formula, R ¹ and k are the same as above.)
And a fluorenone represented by the following formula (3)

(Wherein R ^{2 to} R ⁵ , m, and n are the same as described above.)
It can manufacture by making the compound represented by these react.

  Conventionally, when a fluorenone is reacted with a phenol (for example, phenol, cresol, 2,6-xylenol, etc.) in the presence of an acid catalyst, a compound in which two phenols are substituted at the 9-position of the fluorenone (9 , 9-bisphenol fluorenes), it is known that in the present invention, among the phenols, the compound represented by the above formula (3) (that is, 2,5-substituted phenol) is particularly selected. It has been found that, when used, a compound in which one phenol is substituted at the 9-position of fluorenones is selectively obtained. The reason why such a compound is obtained is not clear, but in addition to the steric influence by the substituents at the 2- and 5-positions, the catalyst is selectively used depending on the catalyst used in the reaction (such as sulfuric acid), the amount used and the reaction conditions. It appears that a compound of formula (1) is obtained.

  Examples of the compound (fluorenones) represented by the formula (2) used as a raw material include fluorenone. The purity of the fluorenones is not particularly limited, but is usually 95% by weight or more, preferably 98% by weight or more, and more preferably 99% by weight or more.

Examples of the compound represented by the formula (3) used as a raw material (2,5-substituted phenols and the like) include 2,5-dialkylphenol (for example, 2,5 such as 2,5-xylenol). - compounds in which m is 0 in the di _{C 1-4} alkylphenol) the formula, such as (3), alkylene glycol mono (2,5-dialkyl phenyl) ethers {e.g., 2- (2,5-dimethylphenoxy) ethanol, etc. C _2-4 alkylene glycol mono (2,5-diC _1-4 alkylphenyl) ether} and the like. In the formula (3), R ⁵ is not substituted at the 4-position of the group — [O— (RO) _m —H].

  The purity of the compound represented by the formula (3) is not particularly limited, but is usually 95% by weight or more, preferably 98% by weight or more, and more preferably 99% by weight or more.

  In the reaction, the ratio (use ratio) of the compound represented by the formula (3) is not particularly limited, but is, for example, 0.5 to 100 mol with respect to 1 mol of the compound represented by the formula (2). (E.g., 0.7 to 70 mol), and can be selected from, for example, 1 to 50 mol (e.g., 1.2 to 30 mol), preferably 1.5 to 20 mol (e.g., 1.8 to 15). Mol), more preferably about 2 to 10 mol (for example, 2.5 to 8 mol).

Examples of the acid catalyst include inorganic acids {for example, sulfuric acid, hydrogen halide (hydrogen chloride, hydrogen bromide, hydrogen iodide, etc.), hydrohalic acid [for example, hydrochloric acid (for example, 5-36% by weight, preferably 20- About 36% by weight of an aqueous solution of hydrogen chloride, etc.), hydrobromic acid, hydroiodic acid, etc.], phosphoric acid, etc.}, organic acid {e.g., carboxylic acid, sulfonic acid [e.g. C _1-4 alkane sulfonic acid such as acid), arene sulfonic acid (eg C _6-10 arene sulfonic acid such as benzene sulfonic acid, toluene sulfonic acid (p-toluene sulfonic acid etc.)), haloalkane sulfonic acid (eg , Halo C _1-4 alkanesulfonic acid such as trifluoromethanesulfonic acid, etc.)] and the like}. The sulfuric acid includes dilute sulfuric acid (for example, sulfuric acid having a concentration of about 30 to 90% by weight), concentrated sulfuric acid (for example, sulfuric acid having a concentration of 90% by weight or more), fuming sulfuric acid, and the like, and can be converted into sulfuric acid in the reaction system. If present, sulfur trioxide may be used as the sulfuric acid precursor. Usually, as sulfuric acid, 80 to 99% by weight (for example, 85 to 98% by weight), preferably about 90 to 97.5% by weight sulfuric acid (concentrated sulfuric acid) may be used in terms of H ₂ SO ₄ .

Moreover, a solid acid can also be used as an acid catalyst. Examples of the solid acid include inorganic solid acids [metal compounds (SiO ₂ , Al ₂ O ₃ , TiO ₂ , Fe ₂ O ₃ , ZrO ₂ , SnO ₂ , V ₂ O ₅ and other oxides, SiO ₂ —Al ₂ O _3]. , SiO ₂ —TiO ₂ , TiO ₂ —ZrO ₂ , SiO ₂ —ZrO ₂ and other complex oxides, sulfides such as ZnS, CaSO ₄ , Fe ₂ (SO ₄ ) ₃ , CuSO ₄ , NiSO ₄ , Al ₂ ( SO ₄ ) ₃ , MnSO ₄ , BaSO ₄ , CoSO ₄ , ZnSO ₄ and other sulfates, P, Mo, V, W, Si and other polyacids (AlPO ₄ , Ti phosphates, etc.) salt, etc.), _etc.); clay minerals (acid clay, montmorillonite, etc.);; _{(NH 4)} 2 SO ₄ nonmetal sulfates such as zeolite (Y-type having an acidic OH group, X type, a type, ZSM , _Mordenite, VIPI _5, AlPO 4 _-5, including AlPO ₄ -11); kaolin, etc.], can be exemplified an organic solid acid (such as ion-exchange resins). The solid acid may be porous or non-porous depending on the type of solid acid.

The ion exchange resin mainly includes strong acid cation exchange resin [for example, ion exchange resin having sulfonic acid group [sulfonated product of crosslinked polystyrene such as styrene-divinylbenzene copolymer, sulfonic acid group (or —CF ₂ CF _2]. A fluorine-containing resin having a SO ₃ H group (for example, a block copolymer of [2- (2-sulfotetrafluoroethoxy) hexafluoropropoxy] trifluoroethylene and tetrafluoroethylene (Nafion manufactured by DuPont), etc. Fluorine-containing ion exchange resins, etc.], weak acid cation exchange resins [for example, ion exchange resins having a carboxylic acid group (methacrylic acid-divinylbenzene copolymer, etc.), etc.] ), Etc. In addition, heat resistance with bromine introduced into the molecule Can also be used in the ion exchange resin. Among these solid acid cation exchange resin is preferred.

The ion exchange resin may be a gel type ion exchange resin, but usually, from the viewpoint of catalytic activity, a porous ion exchange resin [in addition to micropores, macropores (for example, pores having a pore diameter of about 50 to 1000 mm) are used. Having an ion exchange resin]. Among porous ion exchange resins, for example, an ion exchange resin based on a styrene-divinylbenzene copolymer having a high divinylbenzene ratio (crosslinking degree) is called a high porous resin. The porosity of the porous ion exchange resin is usually about 0.03 to 0.6 cm ³ / g, for example, 0.05 to 0.55 cm ³ / g, preferably 0.1 to 0.5 cm ³ / g. g, more preferably about 0.15 to 0.45 cm ³ / g (particularly 0.2 to 0.4 cm ³ / g). The nitrogen adsorption specific surface area of the ion exchange resin is usually about 10 to 90 m ² / g, for example, 15 to 80 m ² / g, preferably 20 to 70 m ² / g, more preferably 25 to 60 m ² / g ( In particular, it may be about 30 to 50 m ² / g). Commercially available ion exchanges such as “Levacit K2649” manufactured by Bayer; “Amberlist 31”, “Amberlist 131”, “Amberlist 121” manufactured by Organo; “Nafion” manufactured by DuPont, etc. A resin may be used.

  There is no restriction | limiting in particular in the form of a solid acid, Although a film form may be sufficient, Usually, it is granular and fine particle may be sufficient.

  Preferred acid catalysts include sulfuric acid, sulfonic acid, solid acid and the like, and particularly acid having dehydrating action such as sulfuric acid is preferred.

  The acid catalysts may be used alone or in combination of two or more.

  In the present invention, the reason why one compound represented by the formula (3) is substituted at the 9-position of fluorene is not clear, but the type of acid catalyst to be used is also important for the following reason. Conceivable. That is, when fluorenone is reacted with phenols in the presence of an acid catalyst and thiols, one phenol is first substituted (added) to fluorenone, and a hydroxyl group is generated at the 9-position of fluorene. Is protonated by an acid catalyst, and the second phenol is substituted with elimination of water, whereby a compound in which two phenols are substituted at the 9-position of fluorene is obtained. On the other hand, in the present invention, a hydroxyl group formed at the 9-position of fluorene by using a compound represented by the above formula (3) having a relatively large steric hindrance and using an acid (such as sulfuric acid) having a dehydrating action. The elimination (dehydration) of water accompanying the protonation of the group proceeds predominantly, and it seems that the substitution of the second compound represented by the formula (3) does not occur at the 9th position of fluorene. Thus, in order to cause dehydration to occur preferentially, it is also important to select an acid that has a strong dehydrating action, or to use a relatively large amount thereof. Hydrochloric acid has no dehydrating action.

  Although the usage-amount of an acid catalyst (for example, the said inorganic acid or the said organic acid) can be selected according to the kind of acid catalyst, for example with respect to 100 weight part of compounds represented by the said Formula (2), 0. 1 to 1000 parts by weight (for example, 1 to 800 parts by weight), preferably 3 to 700 parts by weight, more preferably 5 to 500 parts by weight, and particularly 10 to 300 parts by weight (for example, 20 to 200 parts by weight). It may be about 30 parts by weight or more (for example, about 30 to 500 parts by weight, preferably 40 to 400 parts by weight, more preferably 50 to 300 parts by weight). As described above, when the amount of the acid catalyst used is relatively large, the compound represented by the formula (1) can be produced more advantageously by combining with the compound represented by the formula (3). Can do.

  Moreover, the usage-amount of an acid catalyst is 0.1-100 mol (for example, 0.3-50 mol) with respect to 1 mol of compounds represented by said Formula (2), Preferably 0.5-30 mol More preferably, it may be about 0.7 to 20 mol (for example, 1 to 10 mol), and may generally be about 0.5 to 5 mol (for example, 1 to 3 mol).

  Furthermore, the usage-amount of an acid catalyst is 0.01-800 weight part (for example, 0 weight part) with respect to 100 weight part of total amounts of the compound represented by the said Formula (2) and the said Formula (3). 0.05 to 500 parts by weight), preferably 0.5 to 300 parts by weight, more preferably 1 to 200 parts by weight, especially 2 to 100 parts by weight (for example, 3 to 80 parts by weight). It may be about 5 to 50 parts by weight.

  In general, the reaction may be carried out in combination with a thiol as a co-catalyst in addition to the acid catalyst. When the acid catalyst and thiols are combined, the reaction can proceed effectively.

Examples of thiols include conventional thiols that function as promoters, such as mercaptocarboxylic acid (thioacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, mercaptobenzoic acid. Etc.), alkyl mercaptans (for example, C _1-20 alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, dodecyl mercaptan, preferably C _1-16 alkyl mercaptan), aralkyl mercaptans ( Benzyl mercaptan etc.).

Of these thiols, mercaptocarboxylic acids [for example, mercaptoalkanoic acids such as mercapto C _2-6 alkanoic acid (for example, β-mercaptopropionic acid)] and alkyl mercaptans (for example, C _1-16 alkyl mercaptan) are preferable. In particular, mercaptocarboxylic acid is preferred. Thiols can be used alone or in combination of two or more.

  When using thiols, the usage-amount of thiols can be selected from the range of about 0.001-1 weight part with respect to 1 weight part of compounds represented by said Formula (2), for example, 0.005 -0.8 weight part, Preferably it is 0.01-0.7 weight part, More preferably, about 0.03-0.5 weight part may be sufficient. Moreover, the usage-amount of thiols is 0.001-0.8 weight part with respect to 100 weight part of total amounts of the compound represented by the compound represented by said Formula (2), and said Formula (3), for example. The amount may preferably be about 0.005 to 0.5 parts by weight, more preferably about 0.01 to 0.3 parts by weight.

  Moreover, the usage-amount of thiols can be selected from the range of about 0.001-30 weight part with respect to 1 weight part of acid catalysts, for example, 0.005-20 weight part, Preferably it is 0.03-8 weight. Part, especially about 0.05 to 5 parts by weight.

  The reaction may be performed in the absence of a solvent or in a solvent. Examples of the solvent include alcohol solvents (for example, alkanols such as methanol, ethanol and isopropanol), ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane), halogen solvents (salt chloride). And halogenated hydrocarbons such as methylene, chloroform and carbon tetrachloride), and organic solvents such as aromatic solvents (aromatic hydrocarbons such as benzene, toluene and xylene, anisole and the like). An excess of the compound represented by the formula (3) may be used as a solvent. The solvents may be used alone or in combination of two or more.

  The amount of the solvent used can be selected from a range of about 1 to 300 parts by weight with respect to 1 part by weight of the total amount of the compound represented by the formula (2) and the compound represented by the formula (3). It may be about 3 to 200 parts by weight, preferably about 5 to 100 parts by weight.

  The reaction temperature can be selected according to the type of the compound represented by the formula (2) to be used, the compound represented by the formula (3), the acid catalyst, the thiols, and the like. Preferably it is carried out at about 10 to 120 ° C, preferably about 20 to 100 ° C. The reaction time can be adjusted according to the type of raw material, the reaction temperature, the concentration in the solvent, etc., for example, 30 minutes to 48 hours, preferably 1 to 36 hours, more preferably about 2 to 24 hours. Also good.

  The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), or may be performed at normal pressure or under pressure. The progress of the reaction can be confirmed (or traced) by high performance liquid chromatography (HPLC), thin layer chromatography (TLC), or the like.

  In the reaction mixture after completion of the reaction, in addition to the generated compound represented by the formula (1), an unreacted compound represented by the formula (2), an unreacted formula (3) Compounds, catalysts (acid catalysts, thiols), side reaction products and the like. Therefore, it can be separated and purified by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.

Examples of the crystallization solvent include hydrocarbons [aliphatic hydrocarbons (hexane, heptane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, etc. ), Etc.], water, alcohols [lower aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol ( _C1-3 alkanols, etc.)], ketones [acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, ethylpropyl Examples include ketones, lower aliphatic ketones (such as C _3-7 dialkyl ketones) such as di-n-propyl ketone and diisopropyl ketone, cyclohexanones, etc., ethers (such as dialkyl ethers such as diethyl ether and diisopropyl ether), and the like. The crystallization solvents may be used alone or in combination of two or more.

  The amount of the crystallization solvent used is not particularly limited, and is 0.5 to 50 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 1 part by weight of the reaction mixture (solid content conversion). It may be about a part. Such a crystallization operation may be performed once or may be repeated a plurality of times.

The compound represented by the formula (1) can be obtained by the steps as described above. In addition, in the said Formula (1), although it is preferable to manufacture the compound whose m is 1 or more by the said method, in order to make it react efficiently, m is a compound represented by the said Formula (3). A compound in which m is 0 in the formula (1) is generated using a compound in which the compound is 0, and then the generated compound (a compound in which m is 0 in the formula (1)) and an alkylene group R ² ( Alternatively, it can also be produced by reacting a compound corresponding to the oxyalkylene group OR ² ).

Examples of the compound corresponding to the alkylene group R ² include alkylene oxide (C _2-4 alkylene oxide such as ethylene oxide, propylene oxide and butylene oxide, particularly C _2-3 alkylene oxide) and alkylene carbonate (ethylene carbonate, propylene carbonate and butylene). C _2-4 alkylene carbonates such as carbonate, especially C _2-3 alkylene carbonates), haloalkanols (for example, halo C _2-6 alkanols such as 3-chloropropanol) and the like. These compounds may be used alone or in combination of two or more. When alkylene oxide or alkylene carbonate is reacted, a (poly) oxyalkylene unit can be introduced via the hydroxyl group of the compound represented by the formula (1) (a compound in which m is 0). When using an alkylene carbonate, an oxyalkylene unit (alkoxy unit) is introduced by decarboxylation after the addition of the alkylene carbonate.

  The fluorene compound of the present invention is a monofunctional fluorene skeleton-containing compound having a hydroxyl group, and can be used for various applications (diluents and the like). In such an application, the fluorene compound of the present invention may be used as it is, or may be used after derivatization. For example, when used as a diluent for a resin (for example, a heat or photocurable resin such as an epoxy resin or a heat (or light) curable (meth) acrylic resin), the compound represented by the formula (1) is used. It may be used as a derivative (for example, (meth) acrylate (monofunctional (meth) acrylate), glycidyl ether, etc.). For this reason, the derivative | guide_body of the fluorene compound represented by the said Formula (1) is also contained in this invention.

[Derivative of fluorene compound represented by formula (1)]
The derivative of the fluorene compound represented by the formula (1) is not particularly limited depending on the application, but representative derivatives include, for example, a polymerizable unsaturated using a compound represented by the formula (1) as a raw material. And a monofunctional compound having a group, a containing compound having a crosslinkable group using a compound represented by the formula (1) as a raw material, and the like.

  As a representative monofunctional compound having a polymerizable unsaturated group, for example, a compound represented by the following formula (1A) ((meth) acrylic group-containing monofunctional compound, that is, the formula (1) (Meth) acrylates of the compounds represented.

(In the formula, R ⁷ represents a hydrogen atom or a methyl group. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , k, m, and n are the same as described above.)
In the compound represented by the above formula (1A), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , k, m, and n are the same as described above, and the preferred embodiments are also the same as described above.

As a typical compound represented by the formula (1A), for example, 9- (4- (meth) acryloyloxy-3,5-dialkylphenyl) fluorene [for example, 9- (4- (meth) acryloyloxy] Compound in which m is 0 in the above formula (1A) such as 9- (4- (meth) acryloyloxy-3,5-diC _1-4 alkylphenyl) fluorene] such as −3,5-dimethylphenyl) fluorene 9- [4-((meth) acryloyloxyalkoxy) -3,5-dialkylphenyl] fluorene {eg 9- [4- (2- (meth) acryloyloxyethoxy) -3,5-dimethylphenyl) fluorene such as 9- [4 - ((meth) acryloyloxy _{C 2-4} alkoxy) _{-3,5-di-C 1-4} alkyl phenyl] fluorene} How the formula (1A) m is included compound is one or more.

  In addition, the compound represented by the formula (1A) is a conventional method, for example, a compound represented by the formula (1), (meth) acrylic acid or a derivative thereof (acid halide, acid anhydride, etc.) Can be made to react.

  Moreover, as a typical monofunctional compound having the crosslinkable group, for example, a compound represented by the following formula (1B) (a glycidyl group-containing monofunctional compound, that is, represented by the formula (1)) Glycidyl ethers of the compounds).

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , k, m, and n are the same as described above.)
In the compound represented by the above formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , k, m, and n are the same as described above, and the preferred embodiments are the same as described above.

As a typical compound represented by the formula (1B), for example, 9- (4-glycidyloxy-3,5-dialkylphenyl) fluorene [for example, 9- (4-glycidyloxy-3,5-dimethyl) A compound in which m is 0 in the formula (1B) such as 9- (4-glycidyloxy-3,5-diC _1-4 alkylphenyl) fluorene] such as phenyl) fluorene; 9- [4- (glycidyloxy) Alkoxy) -3,5-dialkylphenyl] fluorene {e.g. 9- [4- (glycidyloxy C _2-4 alkoxy) such as 9- [4- (2-glycidyloxyethoxy) -3,5-dimethylphenyl) fluorene ) _{-3,5-di-C 1-4} alkyl phenyl] the expression, such as fluorene} in (1B) m is included compound is one or more

  The compound represented by the formula (1B) can be produced by a conventional method, for example, by reacting the compound represented by the formula (1) with epichlorohydroline.

  The compound (or derivative thereof) of the present invention can be used for various applications as described above, and in particular, resin monomers, resin modifiers (diluents, polymerization initiators, endblockers, copolymerizable monomers). (Or a resin modifier) etc.). In particular, by using the above-mentioned compound (or a derivative thereof) as a diluent (or a constituent of the diluent), the heat or photo-curing resin is improved in handling properties, while having high heat resistance and excellent optical properties ( Since low birefringence, high refractive index, etc.) can be imparted to heat or a photocurable resin (or a cured product thereof), it is extremely useful.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

In Examples, ¹ H-NMR spectrum was measured with a JEOL GTX-400 spectrometer using tetramethylsilane as an internal standard and CDCl ₃ as a solvent.

Example 1
In a 1 L separable flask, 9-fluorenone (manufactured by Osaka Gas Chemical Co., Ltd., purity 99.5%) 18 g (0.1 mol), 2,5-xylenol 48.9 g (0.4 mol), 3- After charging 1 g of mercaptopropionic acid and 30 g of dioxane as a solvent, the mixture was heated to 65 ° C. and completely dissolved. Thereafter, 13.5 g of sulfuric acid as a catalyst was added dropwise over 1 hour, and the reaction was continued for 6 hours while stirring at 65 ° C. The component fractionated by HPLC from the obtained reaction solution was analyzed by FD-MS and NMR, and was a compound [9- (4-hydroxy-2,5-dimethylphenyl) fluorene] represented by the following formula. It was confirmed. The molecular weight analyzed by FD-MS was 286.

¹ H-NMR (CDCl ₃ -300 MHz): δ (ppm) = 7.8 (d, 2.3 H), 7.3 (s, 2 H), 7.2 (s, 3.5 H), 6.6 (S, 0.5H,), 6.3 (s, 0.4H), 6.0 (s, 0.4H), 5.3 (s, 0.5H). 4.9 (s, 0.3H), 2.2 (s, 1.3H), 2.0 (s, 0.8H), 1.8 (s, 0.8H)
In addition, the purity of the compound represented by the above formula is 91.6%, and the compound of Example 4 of Patent Document 6 represented by the following formula [ie, 9,9-bis (4- The presence of hydroxy-2,5-dimethylphenyl) fluorene] could not be observed.

(Comparative Example 1)
9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene was reacted in the same manner as in Example 1 except that 2,6-xylenol was used instead of 2,5-xylenol. was gotten.

(Comparative Example 2)
9,9-bis (4-hydroxy-2,6-dimethylphenyl) fluorene was reacted in the same manner as in Example 1 except that 3,5-xylenol was used instead of 2,5-xylenol. Thus, various compounds obtained by substituting two 3,5-xylenols at the 9-position of fluorene were obtained.

  The compound of the present invention (or a derivative thereof) is a monofunctional fluorene skeleton-containing compound (or a derivative thereof) having a hydroxyl group, and is a resin raw material, a polymerization initiator, a terminal blocking agent [or a sealing agent such as a heat It can be suitably used for applications such as end-capping agents for curable resins (such as epoxy resins), end-capping agents for thermoplastic resins (for example, polyester resins), and the like] and diluents. In particular, derivatives of the above compounds ((meth) acrylate, glycidyl ether, etc.) can be suitably used as resin raw materials (monomers) and diluents (reactive diluents). And by using the compound (or which derivative) of this invention for such a use, the fluorene skeleton (9-phenylfluorene skeleton) which has the outstanding characteristics, such as high heat resistance and a high refractive index, can simply be resin ( Or a cured product thereof).

Claims (6)

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

(In the formula, R ¹ represents a substituent, R ² represents an alkylene group, R ^{3 to} R ⁵ represent a substituent, k represents an integer of 0 to 4, m represents an integer of 0 or more, and n represents 0 to 0. (It is an integer of 2.) The fluorene compound according to claim 1, wherein in formula (1), R ^{3 to} R ⁵ are the same or different and each is a hydrocarbon group or an alkoxy group. The fluorene compound according to claim 1 or 2, wherein in formula (1), R ³ and R ⁴ are alkyl groups, and n is 0.   The fluorene compound according to any one of claims 1 to 3, which is a compound for use as a resin raw material or a diluent. In the presence of an acid catalyst and thiols, the following formula (2)

(Wherein R ¹ and k are the same as in claim 1 ).
And a compound represented by the following formula (3)

(Wherein R ^{2 to} R ⁵ , m and n are the same as those in claim 1 ).
The method of manufacturing the compound represented by Formula (1) of Claim 1 by making the compound represented by these react.   The production method according to claim 5, wherein 30 parts by weight or more of sulfuric acid as an acid catalyst is used with respect to 100 parts by weight of the compound represented by the formula (2).