JP2011219465A - Fluorene polynuclear compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel compound having a 9,9-bis(aryl)fluorene skeleton with high carbon density.SOLUTION: A fluorene polynuclear compound represented by formula is obtained by reacting fluorenones with 9,9-bis(hydroxyaryl)fluorenes in the presence of an acid catalyst. In formula, a ring Z is an aromatic hydrocarbon ring; Ris a substituent; k is an integer of 0-4; n is an integer of 1-4; Ris a substituent; p is an integer of 0-4; and q is an integer of 0 or more.

Description

  The present invention relates to a novel compound having a fluorene skeleton (9,9-bisarylfluorene 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-bisarylfluorene 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), etc. A method of introducing a fluorene skeleton into a part of the skeleton structure of the resin is generally used as a base component of the resin. For example, as an example using such a resin having a fluorene skeleton, Japanese Patent Application Laid-Open No. 2004-339499 (Patent Document 1) includes compounds having a fluorene skeleton such as bisphenol fluorene, bisaminophenyl fluorene, and bisphenoxyethanol fluorene. Addition of resin (polyester resin, polycarbonate resin, urethane resin, acrylic resin, polyamide resin, polyimide resin, epoxy resin, vinyl ester resin, phenol resin, aniline resin, etc.) as a polymerization component A composition containing an agent is disclosed.

  In recent years, a compound having a 9,9-bisnaphthylfluorene skeleton has been developed as a new fluorene compound. For example, Japanese Patent Application Laid-Open No. 2007-99741 (Patent Document 2) discloses that 9,9-bis (hydroxynaphthyl) fluorene or the like can be applied to a thermosetting resin (such as an epoxy resin). Japanese Unexamined Patent Publication No. 2008-274250 (Patent Document 3) discloses a phenol resin using 9,9-bis (hydroxynaphthyl) fluorene as a phenol component. This document describes that the obtained phenolic resin (or its cured product) is excellent in heat resistance and etching resistance.

  As described above, various fluorene compounds have been developed. In the fluorene compounds, further improvement in characteristics such as heat resistance is desired.

JP 2004-339499 A (claims, paragraph number [0032]) JP 2007-99741 A (Claims) JP 2008-274250 A (Claims)

  Therefore, an object of the present invention is to provide a novel fluorene skeleton-containing compound (fluorene polynuclear compound) having many reaction points (or crosslinking points) and a method for producing the same.

  Another object of the present invention is to provide a novel fluorene skeleton-containing compound having a high carbon density and excellent heat resistance, and a method for producing the same.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that when a fluorenone is reacted with a specific fluorene compound having a 9,9-bisarylfluorene skeleton in the presence of an acid catalyst, a plurality of fluorenes are reacted. A novel polynuclear compound in which the compound is linked via a fluorene group (9-fluorenylidene group) derived from a fluorenone is obtained, and such a polynuclear compound has many hydroxyl groups and carbon. The present invention was completed by discovering that it is useful as a raw material having high density and high heat resistance (for example, phenol resin raw material).

That is, the fluorene compound of the present invention has the following formula (1):
Following formula (1)

[Wherein, ring Z is an aromatic hydrocarbon ring, R ¹ is a substituent, k is an integer of 0 to 4, X is a group — [O— (R ² O) _m —H] (wherein R ² is An alkylene group, m represents an integer of 0 or more), n represents an integer of 1 to 4, R ³ represents a substituent, p represents an integer of 0 to 4, and q represents an integer of 0 or more. ]
It is represented by

In the formula (1), the ring Z may be a benzene ring or a naphthalene ring, R ² may be a C _2-4 alkylene group, m may be about 0 to 4, and n is 1 About 3 may be sufficient and q may be about 0-10. Typically, in Formula (1), ring Z may be a naphthalene ring, R ² may be a C _2-4 alkylene group, m may be 0 to 2, n may be 1, and q may be 0 to 4.

  In particular, in the formula (1), m may be 0. Such a compound which is a compound in which m is 0 has 4 or more phenolic hydroxyl groups and is suitable as a phenol component. Therefore, in particular, the fluorene compound of the present invention is a fluorene compound [particularly a phenol resin (such as a novolak phenol resin) raw material] used in the phenol component of the thermosetting resin, in which m is 0 in the formula (1). May be.

  The fluorene compound of the present invention is represented, for example, by the following formula (2) in the presence of an acid catalyst.

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

[Wherein X is a group — [O— (R ² O) _m —H] (wherein R ² and m are as defined above), and Z, R ¹ , k, n, R ³ and p are Same as above. ]
It can manufacture by making the compound represented by these react.

  In this method, the ratio of the compound represented by the formula (3) may be, for example, 5 mol or more with respect to 1 mol of the compound represented by the formula (2). Moreover, in the said method, the usage-amount of an acid catalyst may be 30 weight part or more with respect to 1 weight part of compounds represented by the said Formula (2). Moreover, in the said method, in addition to an acid catalyst, you may make it react in presence of thiols.

  Since the novel fluorene compound (fluorene polynuclear compound) of the present invention has a structure in which a plurality of fluorene compounds such as 9,9-bis (hydroxyaryl) fluorenes are linked via a fluorene group, the reaction point There are many (or cross-linking points). In addition, the carbon density is high and the heat resistance is excellent. Therefore, when the polynuclear compound of the present invention is used as a resin raw material (for example, a phenol resin raw material), a high heat resistance resin having a high carbon density and a high crosslinking density can be obtained.

(Fluorene compound)
The fluorene compound of the present invention (sometimes referred to as a fluorene polynuclear compound, a polynuclear compound, a polynuclear compound, etc.) is represented by the following formula (1).

[Wherein, ring Z is an aromatic hydrocarbon ring, R ¹ is a substituent, k is an integer of 0 to 4, X is a group — [O— (R ² O) _m —H] (wherein R ² is An alkylene group, m represents an integer of 0 or more), n represents an integer of 1 to 4, R ³ represents a substituent, p represents an integer of 0 to 4, and q represents an integer of 0 or more. ]
In the above formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, naphthalene, etc. C _8-20 condensed bicyclic hydrocarbon rings, preferably C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (eg anthracene, phenanthrene, etc.) Tetracyclic aromatic hydrocarbon ring] and the like. Ring Z is preferably a benzene ring or a naphthalene ring. In addition, the substitution position of the ring Z substituted by 9-position of fluorene is not specifically limited. For example, when the ring Z is a naphthalene ring, the group corresponding to the ring Z substituted at the 9-position of fluorene may be a 1-naphthyl group, a 2-naphthyl group, or the like. Further, the plurality of rings Z may be the same or different, and usually may be the same.

  Preferred ring Z is a benzene ring or a naphthalene ring, particularly a naphthalene ring from the viewpoint of improving the carbon density. In the formula (1), the compound in which the ring Z is a naphthalene ring may be, for example, a compound represented by the following formula (1A).

[Wherein X is a group — [O— (R ² O) _m —H] (wherein R ² and m are as defined above), and R ¹ , k, n, R ³ , p and q are Same as above. ]
In the formula (1), the substituent represented by the group R ¹ is usually a non-reactive substituent such as a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydrocarbon. It may be a group [for example, alkyl group, aryl group (C _6-10 aryl group such as 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 group X of the formula (1), the alkylene group represented by the group R ² is not particularly limited, and examples thereof include a C _2-10 alkylene group (for example, ethylene group, trimethylene group, propylene group, butane-1). , 2-diyl group, C _2-6 alkylene group such as hexylene group) and the like, and C _2-4 alkylene group (particularly, C _2-3 alkylene group such as ethylene group and propylene group) is 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 (eg, 1 to 10), preferably 0 to 8 (eg, 1 to 8), more preferably 0 to 6 (for example, 1 to 6), particularly 0 to 4 (1 to 4), and usually 0 to 2 (for example, 1 to 2). . In particular, n may be 0 depending on the application (for example, when a phenolic hydroxyl group is required, such as when used as a phenol resin raw material).

In the formula (1), the number n of the group — [O— (R ² O) _m —H] is, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1. There may be. In the same ring Z or different rings Z, n may be the same or different numbers. In the formula (1), the total number of groups — [O— (R ² O) _m —H] (for example, phenolic hydroxyl group) may be 4 or more, for example, 4 to 50, preferably May be 4 to 30, more preferably 4 to 20, and particularly 4 to 12 (for example, 4 to 10).

The substitution position of the group — [O— (R ² O) _m —H] is not particularly limited, but when the ring Z is a condensed polycyclic aromatic hydrocarbon ring, a hydrocarbon ring bonded to the 9-position of fluorene. It is often substituted with another hydrocarbon ring. For example, when the ring Z is a naphthalene ring, the substitution position of the group — [O— (R ² O) _m —H] is often the 5th to 8th positions.

In the formula (1), the substituent R ³ is usually a group other than the group — [O— (R ² O) _m —H] (wherein R ² and m are the same as above), For example, an alkyl group (for example, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, preferably a C _1-8 alkyl group, more preferably a C _1-6 alkyl group) Cycloalkyl group (C _5-10 cycloalkyl group such as cyclohexyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group etc.), aryl group (for example, phenyl group, tolyl group, xylyl group, _{C 6-14} aryl group such as a naphthyl group, preferably a _{C 6-10} aryl group, more preferably such _{C 6-8} aryl group), an aralkyl group (benzyl group, Enechiru such _{C 6-10} aryl _{-C 1-4} alkyl group such group) hydrocarbon group such as; alkoxy group (methoxy group, an ethoxy group, a propoxy group, _{C 1-12} alkoxy group such as butoxy, preferably C _1-8 alkoxy group, more preferably C _1-6 alkoxy group etc.), cycloalkoxy group (C _5-10 cycloalkoxy group such as cyclohexyloxy group), aryloxy group (C _6-10 such as phenoxy group) An aryloxy group), an aralkyloxy group (for example, a C _6-10 aryl-C _1-4 alkyloxy group such as a benzyloxy group) or the like —OR ⁴ [wherein R ⁴ is a hydrocarbon group (explained above) Hydrocarbon group). 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 ⁴ (wherein R ⁴ is the same as 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 group R ³ is a hydrocarbon group, —OR ⁴ (wherein R ⁴ represents a hydrocarbon group), —SR ⁴ (wherein R ⁴ is the same as defined above). ), An acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a substituted amino group, and the like.

Preferred group R ³ includes 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 and the like), alkoxy group (C _1-4 alkoxy group and the like) 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).

In the same ring Z or different rings Z, R ³ may be the same or different groups.

In the formula (1), the number p of the group R ³ can be selected according to the type of the ring Z, and may be, for example, 0 to 4, preferably 0 to 3, and more preferably 0 to 2. Note that p may be the same or different numbers in the same ring Z or different rings Z.

  Moreover, in the said Formula (1), q should just be 0 or more, can be selected from the range of about 0-30 (for example, 0-20), for example, 0-10, Preferably it is 0-5, More preferably It may be 0-4, especially 0-2.

  Since the fluorene polynuclear compound of the present invention has four or more hydroxyl groups (for example, phenolic hydroxyl groups), there are many reaction points or crosslinking points. The polynuclear compound of the present invention has a structure in which a plurality of fluorene skeletons are linked, and has a high carbon density. Therefore, the polynuclear compound of the present invention is a resin raw material {eg, a polyol component of a thermosetting resin (eg, a polyfunctional (meth) acrylate, a polyfunctional epoxy resin, etc.), a phenol component of a thermosetting resin, etc.} It can be applied in various uses such as additives for resins and curing agents (or crosslinking agents).

  In particular, the fluorene polynuclear compound in which m is 0 in the formula (1) is suitable as a compound for use in the phenol component of the thermosetting resin. Examples of the thermosetting resin include a phenol resin (such as a novolac resin) and a phenoxy resin. In particular, a phenol resin raw material may be used.

(Production method)
Although the fluorene polynuclear compound of the present invention is not particularly limited, for example, in the presence of an acid catalyst, 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 X is a group — [O— (R ² O) _m —H] (wherein R ² and m are as defined above), and Z, R ¹ , k, n, R ³ and p are Same as above. ]
And a compound represented by the formula (a compound having a 9,9-bisarylfluorene skeleton).

  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.

In the formula (3), Z, R ¹ , k, R ² , m, n, R ³ , and p are the same as described above, and preferred embodiments are also the same as described above. Exemplary compounds represented by the formula (3) include compounds in which m is 0 in the formula (3), compounds in which m is 1 or more, and the like.

Examples of the compound in which m is 0 in the formula (3) include 9,9-bis (hydroxyphenyl) fluorene [for example, 9,9-bis (4-hydroxyphenyl) fluorene], 9,9-bis. 9,9 such as (alkyl-hydroxyphenyl) fluorene [for example, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene - bis _{(C 1-4} alkyl - hydroxyphenyl) fluorene], 9,9-bis (aryl - hydroxyphenyl) fluorene [e.g., 9,9-bis 9, such as (4-hydroxy-3-phenylphenyl) fluorene, 9- bis _{(C 6-10} aryl - hydroxyphenyl) fluorene], 9,9-bis (di or trihydroxy A compound in which the ring Z is a benzene ring, such as 9,9-bis (3,4-dihydroxyphenyl) fluorene, etc .; A compound in which a benzene ring is substituted with a naphthalene ring), for example, 9,9-bis (hydroxynaphthyl) fluorene [for example, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 9,9-bis ( 5-hydroxy-1-naphthyl) fluorene and the like].

The compound in which m is 1 or more in the formula (3) (for example, 1 to 10, preferably 1 to 4, more preferably 1 to 2) corresponds to the compound in which m is 0 in the formula (3). A compound (a compound in which m is substituted from 0 to 1 or more), such as 9,9-bis (hydroxyalkoxyphenyl) fluorene {for example, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 9,9-bis (hydroxy _{C 2-4} alkoxyphenyl) fluorene}, 9,9-bis (alkyl - hydroxyalkoxy phenyl) fluorene {e.g., 9,9-bis [4- (2-hydroxyethoxy) -3- 9,9-bis such as methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene (C _1-4 alkyl-hydroxy C _2-4 phenyl) fluorene}, 9,9-bis (di or trihydroxyalkoxyphenyl) fluorene {eg, 9,9-bis [3,4-di (2-hydroxyethoxy) 9,9-bis (di or trihydroxy C _2-4 alkoxyphenyl) fluorene}, 9,9-bis (hydroxyalkoxynaphthyl) fluorene {e.g., 9,9-bis [6- (2 - hydroxyethoxy) -2-naphthyl] compounds m is 1, such as 9,9-bis fluorene (hydroxy _{C 2-4} alkoxy naphthyl) fluorene}; corresponding to, compounds m is 2 or more, For example, 9,9-bis (hydroxypolyalkoxyphenyl) fluorene {for example, 9,9-bis {4-2-2-[(2- Hydroxyethoxy) ethoxy] phenyl} 9,9-bis fluorene [(hydroxy _{C 2-4 alkoxy) C 2-4} alkoxyphenyl] fluorene}, 9,9-bis (hydroxy polyalkoxy naphthyl) fluorene {e.g., 9,9-bis [(hydroxyC _2-4 alkoxy) C _2-4 alkoxynaphthyl] fluorene}, such as 9,9-bis {6- [2- (2-hydroxyethoxy) ethoxy] -2-naphthyl} fluorene} Etc.

  The compound represented by the formula (3) may be a commercially available product, and a conventional method [for example, phenols corresponding to fluorenone in the presence of an acid catalyst and thiols (phenol, cresol, naphthol, etc. ) And the like (such as the method described in JP-A-2007-99741) and the like] may be used.

  In the reaction, the ratio (use ratio) of the compound represented by the formula (3) is, for example, 1 to 1000 mol (for example, 2 to 1 mol) with respect to 1 mol of the compound represented by the formula (2). 800 mol), preferably 3 to 500 mol (for example, 5 to 300 mol), more preferably about 5 to 200 mol (for example, 8 to 100 mol), and usually 5 mol or more (for example, 5 to 5 mol). 500 mol, preferably 6 to 300 mol, more preferably 7 to 200 mol, particularly about 8 to 100 mol).

The reaction may usually be performed in the presence of an acid catalyst. Examples of the acid catalyst include inorganic acids {eg, sulfuric acid, hydrogen halide (hydrogen chloride, hydrogen bromide, hydrogen iodide, etc.), hydrohalic acid [eg, hydrochloric acid (eg, 5 to 36% by weight, preferably About 20 to 36% by weight of an aqueous solution of hydrogen chloride, hydrobromic acid, hydroiodic acid, etc.], phosphoric acid, etc.}, organic acid {eg, carboxylic acid, sulfonic acid [eg, alkane sulfonic acid (eg, C _1-4 alkane sulfonic acid such as methane sulfonic acid), arene sulfonic acid (for example, C _6-10 arene sulfonic acid such as benzene sulfonic acid, toluene sulfonic acid (p-toluene sulfonic acid)), haloalkane sulfonic acid (For example, halo C _1-4 alkane sulfonic acid such as trifluoromethane sulfonic acid etc.) and the like] 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 sulfuric acid is particularly preferred.

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

  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 1 weight part of compounds represented by the said Formula (2), 0. 5 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).

  Moreover, the usage-amount of an acid catalyst is 0.5-1000 mol (for example, 1-800 mol) with respect to 1 mol of compounds represented by the said Formula (2), Preferably it is 3-700 mol, More preferably It may be about 5 to 500 mol (for example, 10 to 400 mol), and is usually about 10 to 1000 mol (for example, 20 to 700 mol, preferably 30 to 500 mol, more preferably 50 to 300 mol). May be.

  Furthermore, the usage-amount of an acid catalyst is 0.05-200 mol (for example, 0.1 mol) with respect to 1 mol of total amounts of the compound represented by the said Formula (2), and the compound represented by the said Formula (3). To 100 mol), preferably 0.5 to 80 mol, more preferably 1 to 50 mol, particularly about 1.5 to 30 mol (for example, 2 to 20 mol), and usually 1 to 15 mol ( For example, it may be about 1.5 to 10 mol, preferably 2 to 7 mol).

  The reaction may be performed in combination with a thiol as a co-catalyst in addition to the acid catalyst. When an acid catalyst and thiols are combined, the reaction can proceed efficiently.

Examples of thiols include conventional thiols that function as promoters, such as mercaptocarboxylic acids (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 0.01-30 weight part with respect to 1 weight part of compounds represented by said Formula (2), for example, 0.05 -20 parts by weight, preferably 0.1-15 parts by weight, more preferably about 0.5-10 parts by weight. 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, and more preferably about 0.007 to 0.3 parts by weight.

  Moreover, the usage-amount of thiols can be selected from the range of about 0.001-20 weight part with respect to 1 weight part of acid catalysts, for example, 0.002-10 weight part, Preferably it is 0.003-5 weight. Part, more preferably 0.005 to 1 part by weight, especially about 0.007 to 0.5 part by weight.

  The reaction may be performed 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). 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 0.1 to 100 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). For example, it may be about 0.3 to 50 parts by weight, preferably 0.5 to 30 parts by weight, and more preferably about 1 to 10 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, more preferably about 20 to 100 ° C. Moreover, reaction time can be adjusted according to the kind of raw material, reaction temperature, the density | concentration in a solvent, etc., for example, for 30 minutes-120 hours, Preferably it is 1 to 96 hours (for example, 2 to 72 hours), More preferably May be about 3 to 48 hours (for example, 5 to 36 hours).

  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. 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, 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.

  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, the compound represented by the formula (1) is separated and purified by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a separation means combining these. May be.

  In addition, in the said Formula (1), although the terminal (both ends) of a polynuclear compound is a compound represented by the said Formula (3), the compound represented by the said Formula (3) used for reaction Depending on the ratio of use, etc., a compound in which a group derived from the compound represented by the formula (2) (fluorene, 9-fluorenol, etc.) is located at the terminal may be obtained. Therefore, in the polynuclear compound of the present invention, the compound represented by the formula (2) is further added to the end of the compound represented by the formula (1) (one end or both ends, particularly one end). A compound substituted with a group derived from [for example, a compound represented by the formula (2) located at a terminal in the formula (1) (or a group corresponding to the compound represented by the formula (2)) Also included are compounds substituted with hydrogen atoms or hydroxy groups (compounds represented by the following formula (1 ′) or the following formula (1 ″)).

[Wherein, E is a hydrogen atom or a hydroxyl group, X is a group — [O— (R ² O) _m —H] (wherein R ² and m are the same as described above), and Z, R ¹ , k , N, R ³ , p, q are the same as above. ]
In the above formulas (1 ′) and (1 ″), q is the same as described above, but q may be 1 or more from the viewpoint of increasing the carbon density.

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

  In the examples, the thermal weight loss (%) was measured as follows.

(Reduction in thermal weight at 500 ° C (%))
Using a differential scanning calorimeter (DSC 6220, manufactured by 5SII), the weight reduction rate (%) was measured when the temperature was lowered to 500 ° C. after raising the temperature to 520 ° C. in an N ₂ atmosphere. ).

(Example 1)
To a 1 L separable flask, 9-fluorenone (Osaka Gas Chemical Co., Ltd., purity 99.5%) 0.36 g (0.002 mol), 9,9-bis (6-hydroxy-2-naphthyl) fluorene (BNF, synthesized according to the method described in JP-A-2007-099741) 45.1 g (0.1 mol), 3-mercaptopropionic acid 0.5 g and dioxane 70 g as a solvent were added and heated to 60 ° C. And dissolved. Thereafter, 28 g of sulfuric acid as a catalyst was dropped over 1 hour, and the reaction was continued for 24 hours while maintaining at 60 ° C. When the reaction liquid was analyzed by FD-MS and NMR, it was confirmed that a compound represented by the following formula was formed. The molecular weights analyzed by FD-MS were 756 (a dinuclear compound in which q is 0 in the following formula), 1062 (a trinuclear compound in which q is 1 in the following formula), 1368 (in the following formula). The yield on the basis of BNF calculated by HPLC was 38%. In addition, the production | generation ratio of each compound computed from FD-MS was 60% for 2 nuclei, 20% for 3 nuclei, and 10% for 4 nuclei with respect to BNF.

  Caustic soda was added to the obtained reaction solution to neutralize it, and toluene was further added, and the mixture was washed three times with water and cooled. As a result, crystals were deposited. When the crystal was isolated by filtration, 5.1 g of a solid was obtained. The weight loss of the obtained solid at 500 ° C. was 36.6%.

(Example 2)
Synthesis was performed in the same manner as in Example 1 except that 9-fluorenone was changed from 0.36 g to 1.8 g (0.01 mol) in Example 1, and the target product (polynuclear compound) was obtained in a yield of 21.0. %. The formation of the binuclear compound (yield 13%), trinuclear compound (yield 6%), and tetranuclear compound (yield 2%) similar to Example 1 was confirmed by FD-MS and NMR. did. Further, the weight loss of the obtained solid at 500 ° C. was 51.1%.

(Comparative Example 1)
The weight loss of 9,9-bis (6-hydroxy-2-naphthyl) fluorene obtained in Example 1 is 88.4%, and the heat resistance of the compounds obtained in Examples 1 and 2 is BNF. It was found that it was much improved compared to.

  Since the polynuclear compound of the present invention has four or more hydroxyl groups (for example, phenolic hydroxyl groups), there are many reaction points or crosslinking points. Moreover, it has a structure in which a plurality of fluorene skeletons are linked, and has a high carbon density. Therefore, the polynuclear compound of the present invention is a resin raw material {for example, a polyol component of a thermosetting resin (for example, polyfunctional (meth) acrylate, polyfunctional epoxy resin, etc.), a thermosetting resin [for example, a phenol resin] (Novolak resin, etc.), phenolic component, etc. of phenoxy resin, etc.], resin additives, curing agents (or crosslinking agents), etc., and can be applied in various applications such as high carbon density, high heat resistance, A material excellent in plasma resistance (or etching resistance) or the like can be obtained.

In particular, the polynuclear compound of the present invention is suitable as a phenol component of a thermosetting resin because it has a large number of crosslinking points with respect to a crosslinking agent such as an aldehyde, easily forms a network-like resin, and has a high carbon density. Such thermosetting resins (such as phenolic resins) include, for example, curing agents [for example, curing agents for epoxy resins (such as curing agents for epoxy resins for semiconductor encapsulation)], adhesives, paints (such as undercoat coatings) , Rubber compounding agents, binders (binders for grindstones, abrasive papers, friction materials, etc.), laminated materials (or laminated products such as copper-clad laminates, laminated tubes, laminated bars, etc.), heat-sensitive materials (heat-sensitive materials) Paper materials, etc.), carbon materials, insulating materials, foams, pressure sensitive materials (pressure sensitive paper materials, etc.), shell molds, various resin materials (raw materials for novolac epoxy resins, resin binders, etc.) Moldings for electronic parts, thin films, etc., circuit forming materials (resist for semiconductor manufacturing, printed wiring boards, etc.), image forming materials (printing plate materials, relief images, etc.), and underlayer films of resist (resist for semiconductor manufacturing, etc.) Her Mask) it can be applied to various applications such as. Among these, in particular, a lower layer film (such as a lower layer film for resist) is an application that requires a high carbon density, and the polynuclear compound of the present invention (a compound in which m is 0 in the formula (1)) It is suitable as a phenol resin (novolak phenol resin) raw material for forming the lower layer film.

Claims (10)

Following formula (1)

[Wherein, ring Z is an aromatic hydrocarbon ring, R ¹ is a substituent, k is an integer of 0 to 4, X is a group — [O— (R ² O) _m —H] (wherein R ² is An alkylene group, m represents an integer of 0 or more), n represents an integer of 1 to 4, R ³ represents a substituent, p represents an integer of 0 to 4, and q represents an integer of 0 or more. ]
A fluorene compound represented by: The fluorene compound according to claim 1, wherein the ring Z is a benzene ring or a naphthalene ring, R ² is a C _2-4 alkylene group, m is 0 to 4, n is 1 to 3, and q is 0 to 10. The fluorene compound according to claim 1, wherein ring Z is a naphthalene ring, R ² is a C _2-4 alkylene group, m is 0 to 2, n is 1, and q is 0 to 4.   The fluorene compound according to any one of claims 1 to 3, wherein m is 0.   m is 0, The fluorene compound in any one of Claims 1-4 used for the phenol component of a thermosetting resin.   m is 0 and it is a phenol resin raw material, The fluorene compound in any one of Claims 1-5. In the presence of an acid catalyst, 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 X is a group — [O— (R ² O) _m —H] (wherein R ² and m are as defined above), and Z, R ¹ , k, n, R ³ and p are Same as above. ]
The method to manufacture the fluorene compound in any one of Claims 1-6 by making the compound represented by these react.   The production method according to claim 7, wherein the ratio of the compound represented by the formula (3) is 5 mol or more with respect to 1 mol of the compound represented by the formula (2).   The production method according to claim 7 or 8, wherein the amount of the acid catalyst used is 30 parts by weight or more with respect to 1 part by weight of the compound represented by the formula (2).   Furthermore, the manufacturing method in any one of Claims 7-9 made to react in presence of thiols.