Tetracarboxylic acid dianhydride having a fluorene skeleton, its production method and polyimide using the same

Abstract

To provide a method for producing a fluorene tetracarboxylic acid dianhydride that is suitable for producing a polyimide with a hydroxy group-containing fluorene compound as a starting material.SOLUTION: A method for producing a compound of formula (1) from a compound of formula (2) through a compound of formula (5) (rings Z1, Z2 each denote an arene ring, R1a, R1b each denote an alkylene group, m1, m2, n1, n2 each denote an integer, R2a, R2b, R3, R4a, R4b each denote a substituent, and k, p1, p2 each denote an integer).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a tetracarboxylic acid dianhydride having a 9,9-bisarylfluorene skeleton, which is useful for producing polyimides, a method for producing the same, and polyimides using the same. [Background technology]

[0002] Compounds having a 9,9-bisarylfluorene skeleton have various excellent properties such as optical properties, thermal properties, and mechanical properties, and are therefore used in various fields as raw materials (or monomers) for resins for optical components, additives such as resin modifiers, etc. An example of such a compound having a fluorene skeleton is a tetracarboxylic acid dianhydride having a 9,9-bisarylfluorene skeleton (hereinafter sometimes simply referred to as "fluorenetetracarboxylic acid dianhydride"). This fluorenetetracarboxylic acid dianhydride is reacted with a diamine to produce a polyimide.

[0003] For example, Japanese Patent Laid-Open Publication No. 2007-91701 (Patent Document 1) describes a method for producing a fluorenyl group-containing polyesterimide having a high glass transition temperature, high transparency, high solubility, and high alkaline etching properties. Comparative Example 4, which is a comparative example of this polyesterimide, discloses the structural formula and physical properties such as the glass transition temperature of a polyimide composed of 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride and 4,4'-oxydianiline.

[0004] Furthermore, Japanese Patent Application Laid-Open No. 2020-193325 (Patent Document 2) describes an organic film-forming material capable of forming an organic film that has high heat resistance and good adhesion to a substrate, and the organic film-forming material, which is a polyimide polymer, is prepared using 9,9-bis[6-(3,4-dicarboxyphenoxy)-2-naphthyl]fluorene dianhydride.

[0005] Furthermore, Japanese Patent Laid-Open Publication No. 2005-298625 (Patent Document 3) describes, as an example, a polyimide having an ester group or an amide group and a fluorene skeleton as a polyimide having both excellent heat resistance and a low dielectric constant, and discloses, as a comparative example to the above polyimide, Comparative Compound P-41, a polyimide using 9,9-bis[4-(3,4-dicarboxyphenoxy)-3-phenylphenyl]fluorene dianhydride as the tetracarboxylic acid of the polyimide. This polyimide was prepared according to the manufacturing method described in Example 2 of Japanese Patent Laid-Open Publication No. 11-116675 (Patent Document 4).

[0006] Patent Document 4 describes a method for producing 9,9-bis[4-(3,4-dicarboxyphenoxy)-3-phenylphenyl]fluorene dianhydride as a starting material useful for producing polyimides that combine heat resistance and low dielectric properties. In the examples of this document, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene and N-phenyl-4-nitrophthalimide are reacted to synthesize 9,9-bis[4-(N-phenylphthalimide-4-oxy)-3-phenylphenyl]fluorene in a yield of about 77%. This phthalimide compound is then reacted under reflux in an aqueous sodium hydroxide solution to synthesize 9,9-bis[4-(3,4-dicarboxyphenoxy)-3-phenylphenyl]fluorene in a yield of about 58%. This tetracarboxylic acid compound is then refluxed with acetic anhydride to dehydrate, synthesizing 9,9-bis[4-(3,4-dicarboxyphenoxy)-3-phenylphenyl]fluorene dianhydride in a yield of about 72%. The yield of this entire process is about 32%.

[0007] Japanese Patent Laid-Open Publication No. 2009-73738 (Patent Document 5) describes a method for producing 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene. In the examples of this document, 9,9-bis(4-hydroxyphenyl)fluorene is reacted with 4-nitrophthalonitrile to synthesize 9,9-bis[4-(3,4-dicyanophenoxy)phenyl]fluorene, and this tetranitrile compound is reacted in an aqueous potassium hydroxide solution to synthesize 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene with a total yield of 87%. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-91701 [Patent Document 2] Japanese Patent Publication No. 2020-193325 [Patent Document 3] Japanese Patent Application Laid-Open No. 2005-298625 [Patent Document 4] Japanese Patent Application Publication No. 11-116675 [Patent Document 5] Japanese Patent Application Laid-Open No. 2009-73738 Summary of the Invention [Problem to be solved by the invention]

[0009] Patent Document 1 describes 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, and Patent Document 2 describes 9,9-bis[6-(3,4-dicarboxyphenoxy)-2-naphthyl]fluorene dianhydride, but does not describe a method for producing these fluorenetetracarboxylic dianhydrides.

[0010] Patent Document 3 describes 9,9-bis[4-(3,4-dicarboxyphenoxy)-3-phenylphenyl]fluorene dianhydride, and Patent Document 4 describes a method for producing this compound in which 9,9-bis[4-(3,4-dicarboxyphenoxy)-3-phenylphenyl]fluorene dianhydride is prepared using N-phenyl-4-nitrophthalimide, but the yield is low at about 32%.

[0011] In Patent Document 5, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene is synthesized, but there is no description of tetracarboxylic dianhydride. When the tetracarboxylic acid is reacted with a diamine, amidation tends to occur, and the ring-closing efficiency decreases, making it difficult to efficiently synthesize a polyimide.

[0012] Therefore, an object of the present invention is to provide a method for producing fluorenetetracarboxylic dianhydride suitable for producing polyimides, using a compound having a 9,9-bisarylfluorene skeleton containing a hydroxy group (hereinafter, sometimes simply referred to as a "hydroxy group-containing fluorene compound") as a starting material.

[0013] Another object of the present invention is to provide a fluorenetetracarboxylic dianhydride suitable for producing polyimides.

[0014] A further object of the present invention is to provide a polyimide produced from the fluorenetetracarboxylic dianhydride. [Means for solving the problem]

[0015] As a result of intensive research to achieve the above object, the present inventors have found that fluorenetetracarboxylic acid dianhydride can be obtained by reacting a hydroxy group-containing fluorene compound with a nitrophthalonitrile in the presence of a base catalyst, hydrolyzing the resulting tetracarbonitrile compound having a 9,9-bisarylfluorene skeleton (hereinafter, sometimes simply referred to as "fluorenetetracarbonitrile"), and reacting the resulting tetracarboxylic acid having a 9,9-bisarylfluorene skeleton (hereinafter, sometimes simply referred to as "fluorenetetracarboxylic acid") with a dehydrating agent, thereby completing the present invention.

[0016] That is, the method of the present invention is a method for producing fluorenetetracarboxylic dianhydride (1) represented by the following formula (1), and includes a first step of reacting a hydroxyl group-containing fluorene compound (2) represented by the following formula (2) with a nitrophthalonitrile (3) represented by the following formula (3) in the presence of a base catalyst to obtain fluorenetetracarbonitrile (4) represented by the following formula (4); a second step of hydrolyzing the fluorenetetracarbonitrile (4) obtained in the first step to obtain fluorenetetracarboxylic acid (5) represented by the following formula (5); and a third step of reacting the fluorenetetracarboxylic acid (5) obtained in the second step with a dehydrating agent to obtain the fluorenetetracarboxylic dianhydride (1).

[0017] [ka]

[0018] (In the formula, ring Z 1 and Z 2 are the same or different and represent an arene ring; R 1a and R 1b are the same or different and represent an alkylene group; m1 and m2 are the same or different and represent an integer of 0 or 1 or more; R 2a and R 2b are the same or different and represent a substituent; n1 and n2 are the same or different and represent an integer of 0 or 1 or more; R 3 represents a substituent, k represents 0 or an integer of 1 to 8, and R4a and R 4b are the same or different and represent a substituent, and p1 and p2 are the same or different and represent an integer of 0 or 1 to 3.

[0019] [ka]

[0020] (In the formula, Z 1 , Z 2 , R 1a , R 1b , R 2a , R 2b , R 3 , k, m1, m2, n1 and n2 are the same as in the formula (1).

[0021] [ka]

[0022] (In the formula, R 4 represents a substituent, and p represents 0 or an integer of 1 to 3.

[0023] [ka]

[0024] (In the formula, Z 1 , Z 2 , R 1a , R 1b , R 2a , R 2b , R 3 , R 4a , R 4b , k, m1, m2, n1, n2, p1 and p2 are the same as in the formula (1).

[0025] [ka]

[0026] (In the formula, Z 1 , Z 2 , R1a , R 1b , R 2a , R 2b , R 3 , R 4a , R 4b , k, m1, m2, n1, n2, p1 and p2 are the same as in the formula (1).

[0027] In the formula (1), ring Z 1 and Z 2 are the same or different C 6-12 is an aryl group, and R 1a and R 1b are the same or different and are linear or branched chain C 2-6 an alkylene group, m1 and m2 are the same or different and each represent an integer of 0 or 1 to 10; R 2a and R 2b are the same or different C 1-6 Alkyl group or C 6-10 In the aryl group, n1 and n2 may be the same or different and may be an integer of 0 or 1-2.

[0028] In the first step, the hydroxy group of the compound represented by formula (2) may be an alcoholic hydroxy group.

[0029] The present invention also includes a fluorenetetracarboxylic dianhydride (1a) represented by the following formula (1a).

[0030] [ka]

[0031] (m1 and m2 may be the same or different and represent an integer of 1 or more; Z 1 , Z 2 , R 1a , R 1b , R 3 , R 4a , R 4b , k, p1 and p2 are the same as in equation (1).

[0032] Furthermore, the present invention also encompasses a polyimide having, as polymerization components, a tetracarboxylic dianhydride component including a fluorenetetracarboxylic dianhydride component represented by the following formula (1) and at least one diamine component selected from an aliphatic diamine component, an alicyclic diamine component, and an aromatic diamine component, wherein the aromatic diamine component contains at least a diamine component having an arene ring represented by the following formula (6):

[0033] [ka]

[0034] (In the formula, Z 1 , Z 2 , R 1a , R 1b , R 2a , R 2b , R 3 , R 4a , R 4b , k, m1, m2, n1, n2, p1 and p2 are the same as above).

[0035] [ka]

[0036] (wherein ring Ar represents a monocyclic arene ring or a fused polycyclic arene ring; R 5a and R 5b are the same or different and represent a divalent group; q1 and q2 are the same or different and represent 0 or 1; R 6 represents an alkyl group or an aryl group, and r represents an integer of 0 or 1 or more).

[0037] In the present invention, the hydroxy group-containing fluorene compound may be a compound having an alcoholic hydroxy group.

[0038] In this specification and claims, the number of carbon atoms is represented by C1, C6, C 10For example, an alkyl group with 1 carbon atom is represented as "C1 alkyl," and an aryl group with 6 to 10 carbon atoms is represented as "C 6-10 It is indicated as "aryl".

[0039] Furthermore, in this specification and claims, the term "type" attached to a compound name or the like means that the compound "may have a substituent" and "may have a substituent".

[0040] The compound represented by formula (1), the compound represented by formula (1a), the compound represented by formula (2), the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5) may be simply referred to as compound (1), compound (1a), compound (2), compound (3), compound (4), and compound (5), respectively. [Effects of the Invention]

[0041] In the present invention, a fluorenetetracarboxylic dianhydride suitable for producing polyimides can be easily and efficiently produced using a hydroxy group-containing fluorene compound as a starting material.

[0042] Furthermore, the method can produce fluorenetetracarboxylic dianhydride even when the hydroxyl group-containing fluorene compound has an alcoholic hydroxyl group instead of a phenolic hydroxyl group, and can produce fluorenetetracarboxylic dianhydride that has high solubility in various solvents.

[0043] Furthermore, when a tetracarboxylic dianhydride component containing a fluorenetetracarboxylic dianhydride component and a diamine component are used as polymerization components, a transparent polyimide can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0044] [First step (preparation of fluorenetetracarbonitrile (4)] In the first step of the method of the present invention, compound (4) is obtained by reacting compound (2) with compound (3) in the presence of a base catalyst.

[0045] (Hydroxy group-containing fluorene compound (2)) In the formula (2), ring Z 1 and Z 2 The arene ring (aromatic hydrocarbon ring) represented by the formula (I) may be either a monocyclic arene ring (such as a benzene ring) or a polycyclic arene ring. Polycyclic arene rings include fused polycyclic arene rings and ring-assembled arene rings.

[0046] The fused polycyclic arene ring includes, for example, fused bicyclic to fused tetracyclic arene rings. Examples of the arene as the fused bicyclic arene ring include C 11 arenes such as naphthalene and indene. 10-16 Examples of arenes as fused tricyclic arene rings include anthracene and phenanthrene. Examples of arenes as fused tetracyclic arene rings include pyrene. Examples of fused polycyclic arenes include C arenes such as naphthalene and anthracene among the above-mentioned arenes. 10-16 Arenes are preferred, C 10-14 Arenes are more preferred, and naphthalene is especially preferred.

[0047] Examples of the ring-assembled arene ring include a biarene ring, a triarene (or terarene) ring, etc. Examples of arenes as biarene rings include C phenyl, (1,1'-, 1,2'-)binaphthyl, (1-, 2-)phenylnaphthalene, etc. 12-20 Examples of arenes as triarene rings (or terarene rings) include C terphenyls such as (o-, m-, p-)terphenyls. 18-30 Arene is one example.

[0048] Preferred ring-assembled arene rings include biC 6-10 Examples include an arene ring, and a biphenyl ring is particularly preferred.

[0049] Two Z rings 1 and Z 2The types of rings Z may be the same or different, and are usually the same. 1 and Z 2 Among them, C rings such as benzene ring, naphthalene ring, and biphenyl ring 6-12 arene rings are preferred, and among these, C 6-10 An arene ring is more preferred, and a naphthalene ring is particularly preferred.

[0050] In addition, the ring Z bonded to the 9-position of the fluorene ring 1 and Z 2 The substitution position of ring Z is not particularly limited. 1 and Z 2 When ring Z is a naphthalene ring, it may be at either the 1-position or the 2-position, preferably the 2-position. 1 and Z 2 When is a biphenyl ring, it may be at any one of the 2-, 3- and 4-positions, preferably the 3-position.

[0051] base R 1a and R 1b Examples of the linear or branched alkylene group represented by the formula (I) include linear or branched C alkylene groups such as an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butanediyl group, and a tetramethylene group. 2-6 alkylene groups. Preferred alkylene groups R 1a and R 1b As for the C 2-4 A linear or branched alkylene group, more preferably an ethylene group or a propylene group 2-3 Alkylene groups, especially ethylene groups.

[0052] Oxyalkylene group (R 1a O), (R 1b The repeating numbers (number of moles added) m1 and m2 of O) are each an integer of 0 or more and can be selected, for example, from the range of 0 to 20. Preferred ranges are 0 to 15, 0 to 10, 0 to 8, 0 to 6, 0 to 5, 0 to 4, and 0 to 3, more preferably 0 to 2, and particularly preferably 0 or 1.

[0053] In the present specification and claims, the "repeating numbers (number of moles added) m1 and m2" may be arithmetic average values ​​or average numbers of moles added. Furthermore, in the method of the present invention, even if the hydroxy group of compound (2) is not phenolic but alcoholic, the reaction can be carried out easily or efficiently, so m1 and / or m2 may be 1 or more. For example, they can be selected from the range of 1 to 20. Preferred ranges are, in the following stepwise order, 1 to 15, 1 to 10, 1 to 8, 1 to 6, 1 to 5, 1 to 4, and 1 to 3, more preferably 1 or 2, and particularly preferably 1.

[0054] Furthermore, the two repeat numbers m1 and m2 may be the same or different. When m1 and m2 are 2 or more, two or more oxyalkylene groups (R 1a O), (R 1b The types of rings Z) may be the same or different. 1 and Z 2 The oxyalkylene group (R 1a O), (R 1b The types of O) may be the same or different from each other.

[0055] Group [-O(R 1a O) m1 H], [-O(R 1b O) m2 H] ring Z 1 , Z 2 The substitution position for ring Z 1 and Z 2 The position of the ring Z is not particularly limited as long as it is other than the bonding position of the ring Z to the 9-position of the fluorene ring. 1 and Z 2 When ring Z is a benzene ring, it may be located at any of the 2- to 6-positions relative to the 1-position of the phenyl group bonded to the 9-position of the fluorene ring, preferably at the 3- or 4-position, and more preferably at the 4-position. 1 and Z 2is a naphthalene ring, it is usually substituted at any one of the 5- to 8-positions of a naphthyl group bonded at the 1- or 2-position to the 9-position of the fluorene ring, and the 1- or 2-position of the naphthalene ring is substituted at the 9-position of the fluorene ring (substitution in the form of a 1-naphthyl or 2-naphthyl relationship), and a group [-O(R 1a O) m1 H], [-O(R 1b O) m2 H] is preferably substituted at the 1,5-position or the 2,6-position, and particularly preferably at the 2,6-position. 1 and Z 2 is a biphenyl ring, the group [—O(R 1a O) m1 H], [-O(R 1b O) m2 The substitution position of H] may be any of the 2- to 6-positions and the 2'- to 6'-positions of the biphenyl ring. For example, the 3- or 4-position of the biphenyl ring may be bonded to the 9-position of the fluorene ring. When the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene ring, the group [—O(R 1a O) m1 H], [-O(R 1b O) m2 The substitution position of [—O(R H)] may be any of the 2-, 4-, 5-, 6-, 2′-, 3′-, and 4′-positions of the biphenyl ring, preferably either the 6- or 4′-position, and particularly preferably the 6-position. When the 4-position of the biphenyl ring is bonded to the 9-position of the fluorene ring, the group [—O(R 1a O) m1 H], [-O(R 1b O) m2 The substitution position of [H] may be any of the 2-, 3-, 2'-, 3'-, and 4'-positions of the biphenyl ring, preferably either the 2- or 4'-position, and particularly preferably the 2-position.

[0056] base R 2a and R 2bExamples of the substituent represented by the formula (I) include a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, a mercapto group, an acyl group, a carboxy group, a carbamoyl group, a nitro group, an amino group, a substituted amino group, and groups in which these substituents are bonded to each other.

[0057] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0058] Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0059] Examples of the alkyl group include linear or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups. 1-10 Preferred alkyl groups include linear or branched C 1-6 alkyl group, more preferably a linear or branched C 1-4 It is an alkyl group.

[0060] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Examples include a cycloalkyl group.

[0061] Examples of the aryl group include C phenyl, alkylphenyl, biphenylyl, and naphthyl groups. 6-12 Examples of the alkylphenyl group include a methylphenyl group (tolyl group) and a dimethylphenyl group (xylyl group).

[0062] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples include alkyl groups.

[0063] Examples of the alkoxy group include linear or branched C alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, s-butoxy, and t-butoxy groups. 1-10 Examples include an alkoxy group.

[0064] Examples of the cycloalkyloxy group include C 11 groups such as a cyclohexyloxy group. 5-10 Examples thereof include a cycloalkyloxy group.

[0065] Examples of the aryloxy group include C aryloxy groups such as phenoxy groups. 6-10 Examples thereof include an aryloxy group.

[0066] Examples of the aralkyloxy group include C aryloxy groups such as benzyloxy groups. 6-10 Aryl-C 1-4 Examples thereof include an alkyloxy group.

[0067] Examples of the alkylthio group include a C alkylthio group such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, and a t-butylthio group. 1-10 Examples include an alkylthio group.

[0068] Examples of the cycloalkylthio group include a C cyclohexylthio group. 5-10 Examples include a cycloalkylthio group.

[0069] Examples of the arylthio group include C thiophenoxy group (phenylthio group) and the like. 6-10 Examples include an arylthio group.

[0070] Examples of the aralkylthio group include C aryl groups such as benzylthio groups. 6-10 Aryl-C 1-4 Examples include an alkylthio group.

[0071] Examples of the acyl group include C acetyl groups. 1-6 Examples include an acyl group.

[0072] Examples of the substituted amino group include a dialkylamino group and a bis(alkylcarbonyl)amino group. Examples of the dialkylamino group include a di-C group such as a dimethylamino group. 1-4 Examples of the bis(alkylcarbonyl)amino group include bis(C 1-4 alkyl-carbonyl)amino groups.

[0073] Examples of groups in which these substituents are bonded to each other include C aryl groups such as alkoxyaryl groups, specifically methoxyphenyl groups. 1-6 Alkoxy C 6-10 Examples include an aryl group.

[0074] These groups R 2a and R 2b Among these, representative examples include a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a substituted amino group, etc. When the number of substitutions n1 and n2 is 1 or more, preferred groups R 2a , R 2b Examples of the alkyl group include an alkyl group, an aryl group, and an alkoxy group. The alkyl group may be a straight or branched C 1-6 The alkyl group is preferred, and the aryl group is preferably a C aryl group such as a phenyl group. 6-12 An aryl group is preferred, and the alkoxy group is a straight-chain or branched C 1-4 Among them, an alkyl group and an aryl group are preferred, and a linear or branched C alkyl group such as a methyl group is more preferred. 1-4 C such as alkyl group and phenyl group 6-10 An aryl group is more preferred, and a methyl group or a phenyl group is more preferred, with a methyl group being particularly preferred. 2a and R 2b is an aryl group, ring Z 1 and Z 2 may form a ring assembly arene ring together with

[0075] base R 2a , R 2bThe number of substitutions n1 and n2 in the ring Z 1 and Z 2 can be appropriately selected depending on the type of ring, and may be, for example, an integer of 0 to 8. Preferably, they are 0 to 6, 0 to 4, 0 to 3, and 0 to 2 in the following stepwise order, and among these, 0 or 1 is particularly preferred, with 0 being particularly preferred from the viewpoint of achieving a good balance between a high refractive index and high heat resistance. 1 and Z 2 In the formula, the group R 2a and R 2b The types of substitutions and the numbers n1 and n2 may be the same or different. 1 , Z 2 Two or more groups R 2a , R 2b The types of groups R may be the same or different. 2a , R 2b The substitution position of ring Z is not particularly limited. 1 , Z 2 and the group [-O(R 1a O) m1 H], [-O(R 1b O) m2 H] and at a position other than the bonding position to the 9-position of the fluorene ring.

[0076] base R 3 Examples of the substituent represented by the formula include a hydrocarbon group and a halogen atom.

[0077] Examples of the hydrocarbon group include an alkyl group and an aryl group. Examples of the alkyl group include a linear or branched C alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. 1-6 Examples of the aryl group include C phenyl groups and the like. 6-10 Examples include an aryl group.

[0078] Examples of halogen atoms include fluorine atoms, chlorine atoms, and bromine atoms.

[0079] These groups R3 Among these, alkyl groups and halogen atoms are preferred, and among these, alkyl groups, particularly straight-chain or branched C groups such as methyl groups, are preferred. 1-4 Alkyl groups are preferred.

[0080] base R 3 The number of substitutions k is, for example, 0 to 7, preferably 0 to 6, 0 to 5, 0 to 4, 0 to 3, 0 to 2, more preferably 0 or 1, and particularly preferably 0. When k is 2 or more, in two different benzene rings constituting the fluorene ring, two or more groups R substituted on the same or different benzene rings are 3 The types of groups R may be the same or different, but are preferably the same. 3 The substitution position of is not particularly limited, and may be, for example, the 2- to 7-positions of the fluorene ring, such as the 2-, 3-, or 7-position.

[0081] Representative examples of the hydroxy group-containing fluorene compound (2) include 9,9-bis(hydroxyaryl)fluorenes in which m1 and m2 in the formula (2) are each 0; and 9,9-bis[(hydroxy(poly)alkoxy)aryl]fluorenes in which m1 and m2 are each 1 or more, for example, 1 to 10, preferably 1 to 6, more preferably 1 to 3, and particularly 1. In this specification and claims, unless otherwise specified, the term "(poly)alkoxy" is used to include both an alkoxy group and a polyalkoxy group.

[0082] A preferred hydroxyl group-containing fluorene compound (2) is a compound represented by the formula (2) in which the ring Z 1 and Z 2is a monocyclic arene ring or a fused polycyclic arene ring, and m1 and m2 are 0 to 10, for example, 0 to 6, preferably 0 to 4, more preferably 0 to 3, particularly 0 or 1. Examples of the 9,9-bis(hydroxyaryl)fluorenes include 9,9-bis(hydroxy-monocyclic or fused polycyclic C arene rings) such as 9,9-bis(hydroxyphenyl)fluorene and 9,9-bis(hydroxynaphthyl)fluorene. 6-14 Examples of the 9,9-bis[(hydroxy(poly)alkoxy)aryl]fluorenes include 9,9-bis[hydroxy(poly)alkoxy)phenyl]fluorene and 9,9-bis[(hydroxy(poly)alkoxy)naphthyl]fluorene. 2-6 Alkoxy-monocyclic or fused polycyclic C 6-14 aryl]fluorenes and the like.

[0083] Examples of 9,9-bis(hydroxyphenyl)fluorenes include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, and 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene.

[0084] Examples of 9,9-bis(hydroxynaphthyl)fluorenes include 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 9,9-bis(5-hydroxy-1-naphthyl)fluorene, and 9,9-bis(6-hydroxy-3-methyl-2-naphthyl)fluorene.

[0085] Examples of the 9,9-bis[(hydroxy(poly)alkoxy)phenyl]fluorenes include 9,9-bis[(hydroxy(mono to deca)C] such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, and 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene. 2-6 alkoxy)phenyl]fluorene and the like.

[0086] Examples of the 9,9-bis[(hydroxy(poly)alkoxy)naphthyl]fluorenes include 9,9-bis[(hydroxy(mono to deca)C] such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene, 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene, and 9,9-bis[6-(2-(2-hydroxyethoxy)ethoxy)-2-naphthyl]fluorene. 2-6 alkoxy)naphthyl]fluorene and the like.

[0087] These hydroxyl group-containing fluorene compounds (2) are commercially available products.

[0088] (Nitrophthalonitriles (3)) In the formula (3), R 4 Examples of the substituent represented by the formula (I) include an alkyl group, an aryl group, an alkoxy group, and a halogen atom.

[0089] Examples of the alkyl group include linear or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and t-butyl groups. 1-6 Examples include alkyl groups.

[0090] The aryl group includes, for example, a C phenyl group. 6-10 Examples include an aryl group.

[0091] Examples of the alkoxy group include linear or branched C alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, and t-butoxy groups. 1-6 Examples include an alkoxy group.

[0092] Examples of halogen atoms include fluorine atoms, chlorine atoms, and bromine atoms.

[0093] These groups R 4 Among these, alkyl groups and halogen atoms are preferred, and among these, alkyl groups, particularly straight-chain or branched C groups such as methyl groups, are preferred. 1-4 Alkyl groups are preferred.

[0094] Also, the group R 4 The substitution position of is not particularly limited as long as it is other than the substitution positions of a cyano group and a nitro group, and when a nitro group is substituted at the 3-position of the benzene ring, it may be, for example, the 4-position, 5-position, 6-position, etc., preferably the 6-position. When a nitro group is substituted at the 4-position of the benzene ring, it may be, for example, the 3-position, 5-position, 6-position, etc., preferably the 6-position.

[0095] base R 4 The number of substitutions p is, for example, an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, particularly preferably 0. When p is 2 or more, two or more groups R 4 The types may be the same or different from each other, and are preferably the same.

[0096] The substitution position of the nitro group may be either the 3rd or 4th position relative to the cyano groups bonded to the 1st and 2nd positions of the benzene ring, and preferably the 4th position.

[0097] Representative nitrophthalonitriles (3) include, for example, nitrophthalonitriles such as 3-nitrophthalonitrile and 4-nitrophthalonitrile; C phthalonitriles such as 4-methyl-3-nitrophthalonitrile and 3-methyl-4-nitrophthalonitrile; 1-6 Examples of the compound (3) include alkyl-nitrophthalonitriles and halonitrophthalonitriles such as 4-fluoro-3-nitrophthalonitrile, 3-fluoro-4-nitrophthalonitrile, 4-chloro-3-nitrophthalonitrile, and 3-chloro-4-nitrophthalonitrile. Among these, 3-nitrophthalonitrile and 4-nitrophthalonitrile are preferred, and 4-nitrophthalonitrile is more preferred. Furthermore, commercially available products may be used as the compound (3). These compounds (3) may be used alone or in combination of two or more, but are preferably used alone.

[0098] The proportion of compound (3) can be selected, for example, within a range of about 1.5 to 10 moles per mole of compound (2), and is preferably 2 to 5 moles, more preferably 2 to 3 moles, and particularly preferably 2 to 2.5 moles.

[0099] (base catalyst) The base catalyst is not particularly limited and may be an organic base or an inorganic base. Examples of organic bases include trialkylamines such as triethylamine; heterocyclic tertiary amines such as pyridine and N-methylmorpholine; and the like. Examples of inorganic bases include alkali metal carbonates such as potassium carbonate, sodium carbonate, lithium carbonate, and cesium carbonate; alkali metal bicarbonates such as potassium bicarbonate, sodium bicarbonate, lithium bicarbonate, and cesium bicarbonate; alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide, and cesium hydroxide; and alkali metal hydrides such as sodium hydride, potassium hydride, and lithium hydride.

[0100] The base is preferably an inorganic base, and carbonate is preferred from the viewpoints of cost, ease of handling, etc., and potassium carbonate or sodium carbonate is more preferred. When reacting 9,9-bis[(hydroxy(poly)alkoxy)aryl]fluorenes, sodium hydride or potassium hydride is more preferred from the viewpoints of cost, ease of handling, and the fact that a moderate reaction rate can be obtained at a low temperature.

[0101] The catalytic amount of the base catalyst is, for example, 0.1 to 10 mol, preferably 0.5 to 7 mol, and more preferably 1 to 5 mol, relative to 1 mol of compound (2).

[0102] (solvent) The reaction may usually be carried out in the presence of a solvent inert to the reaction. Examples of the solvent include ketones, ethers, sulfoxides, and amides. Examples of ketones include acetone and methyl ethyl ketone; examples of ethers include chain ethers such as diethyl ether and diisopropyl ether, and cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane; examples of sulfoxides include dimethyl sulfoxide (DMSO); and examples of amides include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP). These solvents can be used alone or in combination as a mixed solvent of two or more.

[0103] As the solvent, amides are preferred, DMF is more preferred, and it is particularly preferred to use DMF alone.

[0104] The amount of the solvent used is not particularly limited, and is, for example, 10 to 2000 parts by mass, preferably 50 to 1500 parts by mass, and more preferably 100 to 1000 parts by mass, relative to 100 parts by mass of the hydroxy group-containing fluorene compound.

[0105] (Reaction conditions) The reaction in the first step may be carried out in air or in an inert gas atmosphere, preferably in an inert gas atmosphere, such as nitrogen or a rare gas, such as argon.

[0106] The reaction temperature is not particularly limited and is 0 to 80° C., for example, 10 to 70° C., and preferably 20 to 60° C. When an alkali metal hydride is used as the base catalyst, the reaction temperature may be lower than the above reaction temperature, and may be about 10 to 30° C. The reaction time is not particularly limited and is, for example, 0.5 to 5 hours, and preferably 1 to 4 hours.

[0107] After the reaction is completed, the group [—O(R 1a O) m1 -], [-O(R 1b O) m2 The substitution position of the -] is the same as the substitution position of the nitro group in the formula (3).

[0108] R 4a and R 4b The substituents represented by the formula (3), the substitution positions, and the numbers of substitutions represented by p1 and p2 are respectively R 4 and p, including preferred embodiments.

[0109] In addition, in the formula (4), Z 1 , Z 2 , R 1a , R 1b , R 2a , R 2b , R 3 , k, m1, m2, n1 and n2 are the same as in the formula (2) above, including preferred embodiments.

[0110] If necessary, the compound (4) may be purified by a conventional separation and purification means such as washing, neutralization, extraction, concentration, filtration, reprecipitation, recrystallization, crystallization, column chromatography, centrifugation, or a combination thereof.

[0111] [Second step (preparation of fluorenetetracarboxylic acid (5)] In the second step of the method of the present invention, the cyano group of the compound (4) obtained in the first step is hydrolyzed and substituted with a carboxy group to obtain a compound (5).

[0112] (base catalyst) The base catalyst is not particularly limited and may be an inorganic base, preferably a metal hydroxide. Examples of the metal hydroxide include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide, and cesium hydroxide. Of these, sodium hydroxide and potassium hydroxide are more preferred.

[0113] The catalytic amount of the base catalyst is, for example, about 0.1 to 100 mol, preferably about 0.5 to 50 mol, and more preferably about 1 to 30 mol, per 1 mol of compound (4).

[0114] (solvent) The reaction solvent may be any solvent inert to the reaction, and examples thereof include water; alcohols such as methanol and ethanol; ethers such as cyclic ethers such as dioxane and tetrahydrofuran (THF) and chain ethers such as diethyl ether; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and benzonitrile; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP); sulfoxides such as dimethyl sulfoxide (DMSO); and hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0115] These solvents can be used alone or in combination of two or more. Among these solvents, a mixed solvent of water and alcohols such as ethanol is preferred.

[0116] The amount of the solvent used is not particularly limited as long as it can solubilize (or disperse) the raw material mixture including compound (4) and the base catalyst and does not impair the reaction, and is, for example, 10 to 2000 parts by mass, preferably 50 to 1500 parts by mass, more preferably 100 to 1000 parts by mass, and particularly preferably 400 to 800 parts by mass relative to 100 parts by mass of compound (4).

[0117] (Reaction conditions) The reaction in the second step may be carried out under the same atmosphere as that shown in the first step.

[0118] The reaction temperature is not particularly limited and is, for example, 40 to 110° C., preferably 50 to 100° C., and more preferably 60 to 90° C. The reaction time is not particularly limited and is, for example, 10 to 80 hours, and preferably 15 to 60 hours.

[0119] After the reaction is completed, the group [—O(R 1a O) m1 -], [-O(R 1b O) m2 -] substitution position and Z 1 , Z 2 , R 1a , R 1b , R 2a , R 2b , R 3 , R 4a , R 4b , k, m1, m2, n1, n2, p1 and p2 are the same as in the formula (4) above, including preferred embodiments.

[0120] If necessary, the compound (5) may be purified by the same method as that shown in the first step.

[0121] [Third Step (Preparation of Fluorenetetracarboxylic Dianhydride (1)] In the third step of the method of the present invention, compound (5) obtained in the second step is reacted with a dehydrating agent to effect ring closure by intramolecular dehydration, thereby obtaining compound (1).

[0122] (dehydrating agent) The dehydrating agent is not particularly limited as long as it can dehydrate and ring-close the carboxy group of compound (5) to form an acid anhydride group, and an acid anhydride may also be used. Examples of acid anhydrides include saturated aliphatic monocarboxylic anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, and ethanoic propionic anhydride; unsaturated aliphatic monocarboxylic anhydrides such as (meth)acrylic anhydride and crotonic anhydride; alicyclic monocarboxylic anhydrides such as cyclohexanecarboxylic anhydride and tetrahydrobenzoic anhydride; aromatic monocarboxylic anhydrides such as benzoic anhydride and 4-methylbenzoic anhydride; saturated aliphatic dicarboxylic anhydrides such as succinic anhydride; unsaturated aliphatic dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride; alicyclic dicarboxylic anhydrides such as 1-cyclohexene-1,2-dicarboxylic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride; dicarboxylic anhydrides such as aromatic dicarboxylic anhydrides such as phthalic anhydride and naphthalic anhydride; and polycarboxylic anhydrides such as trimellitic anhydride and pyromellitic anhydride. These acid anhydrides can be used alone or in combination, with acetic anhydride being preferred.

[0123] The amount of the dehydrating agent used can be selected from the range of, for example, about 1.5 to 100 moles per mole of compound (5), and may be 2 moles or more or an excess amount, preferably 2 to 70 moles, more preferably 2 to 50 moles, and particularly preferably 2 to 30 moles.

[0124] (solvent) The reaction may be carried out in the absence or presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction, and examples include aromatic hydrocarbons such as toluene and xylene; haloalkanes such as dichloromethane and chloroform; ethers such as dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and 1,4-dioxane; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; and nitriles such as acetonitrile. Furthermore, the dehydrating agent, such as acetic anhydride, may be used as the solvent, and preferably as the solvent. These solvents may be used alone or in combination.

[0125] The amount of the solvent used is, for example, 10 to 2000 parts by mass, preferably 50 to 1500 parts by mass, more preferably 100 to 1000 parts by mass, and particularly preferably 400 to 800 parts by mass, relative to 100 parts by mass of compound (5).

[0126] (Reaction conditions) The reaction in the third step may be carried out under the same atmosphere as that shown in the first step, including the preferred embodiment.

[0127] The reaction temperature is not particularly limited and is 80 to 150° C., for example, 90 to 140° C., preferably 100 to 130° C., and more preferably 110 to 130° C. The reaction time is not particularly limited and may be, for example, 5 to 15 hours, and preferably 7 to 12 hours.

[0128] After the reaction is completed, the reaction product may be purified by the same method as that shown in the first step.

[0129] [Fluorenetetracarboxylic dianhydride (1)] The reaction in the third step gives compound (1).

[0130] In the formula (1), the group [—O(R 1a O) m1 -], [-O(R 1b O) m2-] and Z 1 , Z 2 , R 1a , R 1b , R 2a , R 2b , R 3 , R 4a , R 4b , k, m1, m2, n1, n2, p1 and p2 are the same as in the formula (4) including preferred embodiments thereof.

[0131] Representative examples of the fluorenetetracarboxylic dianhydride (1) include 9,9-bis[(dicarboxyphenoxy)aryl]fluorene dianhydrides in which m1 and m2 are each 0 in the formula (1); and 9,9-bis[(dicarboxyphenoxy)(poly)alkoxyaryl]fluorene dianhydrides in which m1 and m2 are each 1 or more, for example, 1 to 10, preferably 1 to 6, more preferably 1 to 3, and particularly 1.

[0132] Examples of the 9,9-bis[(dicarboxyphenoxy)aryl]fluorene dianhydrides include 9,9-bis[(dicarboxyphenoxy)phenyl]fluorene dianhydride, 9,9-bis[(dicarboxyphenoxy)naphthyl]fluorene dianhydride, 9,9-bis[alkyl-(dicarboxyphenoxy)phenyl]fluorene dianhydride, and 9,9-bis[aryl-(dicarboxyphenoxy)phenyl]fluorene dianhydride. 6-14 aryl]fluorene dianhydrides.

[0133] Examples of 9,9-bis[(dicarboxyphenoxy)phenyl]fluorene dianhydride include 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride.

[0134] Examples of 9,9-bis[(dicarboxyphenoxy)naphthyl]fluorene dianhydride include 9,9-bis[6-(3,4-dicarboxyphenoxy)-2-naphthyl]fluorene dianhydride and 9,9-bis[5-(3,4-dicarboxyphenoxy)-1-naphthyl]fluorene dianhydride.

[0135] Examples of the 9,9-bis[alkyl-(dicarboxyphenoxy)phenyl]fluorene dianhydride include 9,9-bis[mono or diC] such as 9,9-bis[3-methyl-4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride and 9,9-bis[3,5-dimethyl-4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride. 1-4 alkyl-(dicarboxyphenoxy)phenyl]fluorene dianhydride and the like.

[0136] Examples of the 9,9-bis[aryl-(dicarboxyphenoxy)phenyl]fluorene dianhydride include 9,9-bis[C 6-10 aryl-(dicarboxyphenoxy)phenyl]fluorene dianhydride.

[0137] Furthermore, examples of the 9,9-bis[(dicarboxyphenoxy)(poly)alkoxyaryl]fluorene dianhydrides include 9,9-bis[(dicarboxyphenoxy)(poly)alkoxyphenyl]fluorene dianhydride, 9,9-bis[(dicarboxyphenoxy)(poly)alkoxynaphthyl]fluorene dianhydride, 9,9-bis[alkyl-(dicarboxyphenoxy)(poly)alkoxyphenyl]fluorene dianhydride, and 9,9-bis[aryl-(dicarboxyphenoxy)(poly)alkoxyphenyl]fluorene dianhydride. 6-14 aryl]fluorene dianhydrides.

[0138] Examples of the 9,9-bis[(dicarboxyphenoxy)(poly)alkoxyphenyl]fluorene dianhydride include 9,9-bis[(dicarboxyphenoxy)(mono to deca)C such as 9,9-bis[4-(2-(3,4-dicarboxyphenoxy)ethoxy)phenyl]fluorene dianhydride, 9,9-bis[4-(2-(3,4-dicarboxyphenoxy)propoxy)phenyl]fluorene dianhydride, and 9,9-bis[4-(2-(2-(3,4-dicarboxyphenoxy)ethoxy)ethoxy)phenyl]fluorene dianhydride. 2-6 alkoxyphenyl]fluorene dianhydride and the like.

[0139] Examples of the 9,9-bis[(dicarboxyphenoxy)(poly)alkoxynaphthyl]fluorene dianhydride include 9,9-bis[6-(2-(3,4-dicarboxyphenoxy)ethoxy)-2-naphthyl]fluorene dianhydride, 9,9-bis[6-(2-(3,4-dicarboxyphenoxy)propoxy)-2-naphthyl]fluorene dianhydride, 9,9-bis[5-(2-(3,4-dicarboxyphenoxy)ethoxy)-1-naphthyl]fluorene dianhydride, and 9,9-bis[6-(2-(2-(3,4-dicarboxyphenoxy)ethoxy)ethoxy)-2-naphthyl]fluorene dianhydride, such as 9,9-bis[(dicarboxyphenoxy)(mono to deca)C 2-6 Alkoxynaphthyl]fluorene dianhydride.

[0140] Examples of the 9,9-bis[alkyl-(dicarboxyphenoxy)(poly)alkoxyphenyl]fluorene dianhydride include 9,9-bis[mono- or di-C] such as 9,9-bis[4-(2-(3,4-dicarboxyphenoxy)ethoxy)-3-methylphenyl]fluorene dianhydride, 9,9-bis[4-(2-(3,4-dicarboxyphenoxy)propoxy)-3-methylphenyl]fluorene dianhydride, 9,9-bis[4-(2-(3,4-dicarboxyphenoxy)ethoxy)-3,5-dimethylphenyl]fluorene dianhydride, and 9,9-bis[4-(2-(2-(3,4-dicarboxyphenoxy)ethoxy)ethoxy)-3-methylphenyl]fluorene dianhydride.1-4 Alkyl-((dicarboxyphenoxy)(mono to deca)C 2-6 alkoxy)phenyl]fluorene dianhydride and the like.

[0141] Examples of the 9,9-bis[aryl-(dicarboxyphenoxy)(poly)alkoxyphenyl]fluorene dianhydride include 9,9-bis[C such as 9,9-bis[4-(2-(3,4-dicarboxyphenoxy)ethoxy)-3-phenylphenyl]fluorene dianhydride, 9,9-bis[4-(2-(3,4-dicarboxyphenoxy)propoxy)-3-phenylphenyl]fluorene dianhydride, and 9,9-bis[4-(2-(2-(3,4-dicarboxyphenoxy)ethoxy)ethoxy)-3-phenylphenyl]fluorene dianhydride. 6-10 Aryl-(dicarboxyphenoxy)(mono to deca)C 2-6 alkoxyphenyl]fluorene dianhydride and the like.

[0142] Among these fluorenetetracarboxylic dianhydrides (1), those having the ring Z in the formula (1) 1 and Z 2 is a fused polycyclic arene ring, and m1 and m2 are 0. 9,9-bis(dicarboxyphenoxy fused polycyclic aryl)fluorene dianhydrides are preferred. 10-14 Among them, 9,9-bis[6-(3,4-dicarboxyphenoxy)-2-naphthyl]fluorene dianhydride is particularly preferred, as it has a high refractive index and high heat resistance in a well-balanced manner.

[0143] Fluorenetetracarboxylic dianhydride (1) has a high refractive index and high heat resistance.

[0144] The refractive index of fluorenetetracarboxylic dianhydride (1) may be, for example, about 1.55 to 2 at a temperature of 25° C. and a wavelength of 589 nm, and preferred ranges are 1.56 to 1.9, 1.57 to 1.8, 1.58 to 1.7, 1.59 to 1.65, and 1.6 to 1.63 in the following stepwise order.

[0145] The melting point of the fluorenetetracarboxylic dianhydride (1) may be, for example, about 100 to 350°C, and preferred ranges are 130 to 320°C, 150 to 300°C, 200 to 290°C, 230 to 285°C, and 250 to 280°C in the following stepwise order.

[0146] The 5% mass reduction temperature of the fluorenetetracarboxylic dianhydride (1) may be, for example, about 150 to 500°C, and preferred ranges are 170 to 490°C, 250 to 480°C, 300 to 470°C, 350 to 460°C, 370 to 450°C, and 390 to 445°C in the following stepwise order.

[0147] The temperature at which fluorenetetracarboxylic dianhydride (1) undergoes a 10% mass reduction may be, for example, about 150 to 550°C, and preferred ranges are 170 to 530°C, 200 to 520°C, 210 to 510°C, 250 to 500°C, 300 to 490°C, 350 to 480°C, and 400 to 475°C in the following stepwise manner.

[0148] In this specification and claims, the refractive index, melting point, 5% mass reduction temperature, and 10% mass reduction temperature of the fluorenetetracarboxylic dianhydride (1) can be measured by the method described in the examples below.

[0149] (Fluorenetetracarboxylic dianhydride (1a)) In the present invention, compound (1a) is a novel compound.

[0150] In the formula (1a), n1 and n2 are 0, and Z 1 , Z 2 , R 1a , R 1b , R 3 , R4a , R 4b , k, p1 and p2 are the same as in the formula (1) above, including preferred embodiments thereof.

[0151] In the formula (1a), the oxyalkylene group (R 1a O), (R 1b The repeating numbers (number of moles added) m1 and m2 of O) can each be 1 or more, for example, selected within the range of 1 to 20. Preferred ranges are 1 to 15, 1 to 10, 1 to 8, 1 to 6, 1 to 5, 1 to 4, and 1 to 3, in the following stepwise order, more preferably 1 or 2, and particularly preferably 1.

[0152] As in the formula (1), the "repeating numbers (number of moles added) m1, m2" may be an arithmetic mean value or an average number of moles added, and m1 and m2 may be the same or different. The same applies to preferred embodiments.

[0153] Compound (1a) has m1 and m2 each being 1 or more, and not only has flexibility but also has ring Z 1 and Z 2 Since the ring is an unsubstituted arene ring, it has high solubility in various solvents and is easy to handle.

[0154] Representative examples of compound (1a) include 9,9-bis[(dicarboxyphenoxy)(poly)alkoxyaryl]fluorene dianhydrides, in which m1 and m2 in the formula (1a) are each 1 or more, for example, 1 to 10, preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1.

[0155] Examples of the 9,9-bis[(dicarboxyphenoxy)(poly)alkoxyaryl]fluorene dianhydrides include 9,9-bis[(dicarboxyphenoxy)(poly)alkoxyphenyl]fluorene dianhydride and 9,9-bis[(dicarboxyphenoxy)(poly)alkoxynaphthyl]fluorene dianhydride, and other 9,9-bis[(dicarboxyphenoxy)(poly)alkoxy C 6-14aryl]fluorene dianhydrides, and the same compounds as those of the above formula (1) can be mentioned.

[0156] Among the compounds (1a), 9,9-bis[(dicarboxyphenoxy)alkoxyaryl]fluorene dianhydrides in which m1 and m2 are 1 in the formula (1a) are preferred, and 9,9-bis[(dicarboxyphenoxy)C 2-6 Alkoxy C 6-14 [aryl]fluorene dianhydrides are more preferred, and among these, 9,9-bis[4-(2-(3,4-dicarboxyphenoxy)ethoxy)phenyl]fluorene dianhydride is particularly preferred.

[0157] [Polyimide] (Tetracarboxylic dianhydride component) The polyimide of the present invention contains, as a polymerization component, a tetracarboxylic dianhydride component containing a fluorenetetracarboxylic dianhydride component represented by the following formula (1).

[0158] [ka]

[0159] (In the formula, Z 1 , Z 2 , R 1a , R 1b , R 2a , R 2b , R 3 , R 4a , R 4b , k, m1, m2, n1, n2, p1 and p2 are the same as above, including preferred embodiments.

[0160] A typical fluorenetetracarboxylic dianhydride component is the same as the above-mentioned fluorenetetracarboxylic dianhydride (1).

[0161] The fluorene tetracarboxylic dianhydride component may be used alone or in combination with other tetracarboxylic dianhydride components, such as aromatic tetracarboxylic dianhydride components other than the fluorene tetracarboxylic dianhydride component, or alicyclic tetracarboxylic dianhydride components.

[0162] Examples of the aromatic tetracarboxylic dianhydride component include arene tetracarboxylic acids, specifically C tetracarboxylic acids such as pyromellitic acid and naphthalene tetracarboxylic acid. 6-20 arene-tetracarboxylic acids, etc.; aryl tetracarboxylic acids, specifically di-C such as 3,3,4,4-biphenyltetracarboxylic acid 6-10 aryltetracarboxylic acids, etc.; bis(dicarboxyaryl)alkanes, specifically bis(dicarboxy C) such as 3,3',4,4'-tetracarboxydiphenylmethane and 2,2'-bis(3,4-dicarboxyphenyl)propane; 6-10 Aryl)C 1-10 Alkanes, etc.; bis(dicarboxyaryl) ethers, specifically bis(dicarboxy C) such as 4,4'-oxydiphthalic acid 6-10 aryl) ethers, etc.; bis(dicarboxyaryl) ketones, specifically bis(dicarboxy C) such as 3,3',4,4'-benzophenonetetracarboxylic acid; 6-10 aryl) ketones, etc.; bis(dicarboxyaryl) sulfones, specifically bis(dicarboxy C) such as 3,3',4,4'-diphenylsulfonetetracarboxylic acid 6-10 Examples of the alicyclic tetracarboxylic acid dianhydride component include hydrogenated products of the dianhydrides of the aromatic tetracarboxylic acids. These tetracarboxylic acid dianhydride components may be used alone or in combination of two or more.

[0163] The proportion of the fluorenetetracarboxylic dianhydride component represented by the formula (1) is, for example, 30 to 100 mol%, preferably 40 to 100 mol%, 50 to 100 mol%, 60 to 100 mol%, 70 to 100 mol%, 75 to 100 mol%, and particularly 80 to 100 mol%, based on the total tetracarboxylic dianhydride component.

[0164] (Diamine component) The polyimide of the present invention may contain at least one diamine component selected from an aliphatic diamine component, an alicyclic diamine component, and an aromatic diamine component as a polymerization component.

[0165] The aliphatic diamine component may be a linear or branched C diamine such as ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, or 1,1,2,2-tetramethylethylenediamine. 2-10 Alkanes; bis(amino)-linear or branched C 2-10 Alkoxy)C 1-4 Alkanes and the like can be mentioned.

[0166] Alicyclic diamine components include C 1,4-cyclohexanediamine 5-10 Cycloalkanediamines; amino (amino C) such as isophoronediamine (or 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane); 1-4 Alkyl)C 5-10 Cycloalkanes: bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, etc. 1-4 Alkyl)C 5-10 Cycloalkanes; bis(amino C) compounds such as bis(4-aminocyclohexyl)methane and bis(4-amino-3-methylcyclohexyl)methane 5-10 Cycloalkyl)C 1-4 Alicyclic diamines such as alkanes are also included.

[0167] The aromatic diamine component is preferably a diamine component having at least an arene ring represented by the following formula (6).

[0168] [ka]

[0169] (wherein ring Ar represents a monocyclic arene ring or a fused polycyclic arene ring; R 5a , R 5b are the same or different and represent a divalent group; q1 and q2 are the same or different and represent 0 or 1; R 6 represents an alkyl group or an aryl group, and r represents an integer of 0 or 1 or more).

[0170] In the formula (6), examples of the arene ring represented by the ring Ar include monocyclic arene rings such as a benzene ring and fused polycyclic arene rings. Preferred arene rings include a benzene ring and fused bicyclic to tricyclic arene rings. 10-16 A fused polycyclic arene ring such as an arene ring, for example, a benzene ring, a naphthalene ring, or an anthracene ring, and particularly a benzene ring in terms of transparency.

[0171] base R 5a , R 5b Examples of the group R include an alkylene group, an oxyalkylene group, a cycloalkylene group, and an oxycycloalkylene group, and the hydrogen atoms of these groups may be substituted with halogen atoms, alkoxy groups, acyl groups, nitro groups, cyano groups, amino groups, etc. 5a and R 5b Examples of the alkylene group include a straight-chain or branched-chain C 1-6 Alkylene group, linear or branched C 1-4 Alkylene groups are more preferred, especially methylene groups. 5a and R 5b The types may be the same or different.

[0172] The group [-(R 5a )q1 -NH2] and [-(R 5b ) q2 For example, when Ar is a benzene ring, it may be substituted at the 1,2-positions, 1,3-positions, or 1,4-positions, preferably at the 1,4-positions. When Ar is a naphthalene ring, it may be substituted at any of the 1- to 8-positions, for example, it may be substituted at the 1- or 2-positions and the 5- to 8-positions, preferably at the 1,5- or 2,6-positions, and particularly preferably at the 2,6-positions.

[0173] base R 5a , R 5b The repeating numbers (number of moles added) q1 and q2 are each 0 or 1, and particularly 0.

[0174] base R 6 The substituent represented by the formula (I) may be an alkyl group or an aryl group, and is preferably an alkyl group, and particularly preferably a linear or branched C 1-4 Alkyl groups are preferred.

[0175] base R 6 The number of substitutions r is, for example, an integer of about 0 to 6, preferably an integer of 0 to 5, an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 1, particularly preferably 0. When r is 2 or more, the number of substitutions r of the two or more groups R substituted on the ring Ar is 2 or more. 6 The types of groups R may be the same or different, but are preferably the same. 6 The substitution position of the group R 5a and R 5b The position may be any position other than the substitution position of

[0176] Examples of the aromatic diamine component represented by the formula (6) include diamino C compounds such as phenylenediamines, such as m-phenylenediamine, p-phenylenediamine, 4-methyl-1,2-phenylenediamine, and 4-methyl-1,3-phenylenediamine, and naphthalenediamines, such as 1,5-naphthalenediamine and 1,8-naphthalenediamine. 6-20arenes; aminobenzylamines such as 4-aminobenzylamine, aminoethylanilines such as 4-(2-aminoethyl)aniline, and the like (amino C 1-4 Alkyl)amino C 6-20 Arenes; bis(amino C) compounds such as xylylenediamines, e.g., m-xylylenediamine 1-4 Alkyl)C 6-20 Arenes are included, among which diamino C 6-20 Arenes are preferred, and phenylenediamines are particularly preferred.

[0177] The aromatic diamine component may contain an aromatic diamine component different from the aromatic diamine component represented by formula (6), and examples thereof include diaminodiaryls, bis(aminoaryl)alkanes, bis(aminoaryl)ethers, bis(aminoaryloxy)aryls, bis[(aminoaryloxy)aryl]alkanes, bis(aminoaryl)ketones, bis(aminoaryl)sulfides, bis(aminoaryl)sulfones, aryl-trialkylindanediamines, and diamines having a 9,9-bisarylfluorene skeleton.

[0178] Examples of diaminodiaryls include diaminodi-C diaminobiphenyls such as 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, and 4,4'-diamino-3,3'-bis(trifluoromethyl)biphenyl. 6-10 Examples thereof include aryls.

[0179] Examples of bis(aminoaryl)alkanes include bis(amino C) compounds such as 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,2-bis(4-aminophenyl)propane, bis(4-amino-3-ethylphenyl)methane, and bis(4-amino-3,5-diethylphenyl)methane. 6-10 Aryl)C 1-4 Alkanes and the like can be mentioned.

[0180] Bis(amino C 6-10 aryl) ethers, such as bis(amino C) 6-10 Examples of bis(aminoaryloxy)aryls include bis(amino C aryls) such as 1,3-bis(3-aminophenoxy)benzene and 1,3-bis(4-aminophenoxy)benzene. 6-10 Aryloxy)C 6-10 Examples of bis[(aminoaryloxy)aryl]alkanes include bis[(amino C aryl)alkanes such as 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. 6-10 Aryloxy)C 6-10 Aryl]C 1-6 Alkanes and the like can be mentioned.

[0181] Bis(aminoaryl)ketones include bis(amino C) compounds such as 3,3'-diaminobenzophenone and 4,4'-diaminobenzophenone. 6-10 Examples of bis(aminoaryl) sulfides include bis(amino C) ketones such as bis(4-aminophenyl) sulfide. 6-10 aryl) sulfides, etc. Bis(amino C) such as bis(3-aminophenyl) sulfone and bis(4-aminophenyl) sulfone. 6-10 aryl) sulfones and the like.

[0182] Examples of aryl-trialkylindanediamines include C 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine and 3-(4-aminophenyl)-1,1,3-trimethylindan-5-amine. 6-10 Aryl-triC 1-4 Examples include alkylindanediamines.

[0183] Diamines having a 9,9-bisarylfluorene skeleton include 9,9-bis(aminoaryl)fluorene and 9,9-bis(aminophenoxy)arylfluorene. Examples of 9,9-bis(aminoaryl)fluorene include 9,9-bis(amino C) such as 9,9-bis(4-aminophenyl)fluorene. 6-20 9,9-bis(aminophenoxy)arylfluorenes include 9,9-bis(amino C) such as 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene, 9,9-bis[4-(4-aminophenoxy)-3-phenylphenyl]fluorene, and 9,9-bis[4-(4-amino-2-trifluoromethylphenoxy)-3-phenylphenyl]fluorene. 6-12 Aryloxy)C 6-20 Arylfluorenes and the like.

[0184] These diamine components can be used alone or in combination of two or more. From the viewpoint of transparency of the polyimide, aromatic diamine components are preferred, and aromatic diamine components represented by formula (6) are more preferred. When the aromatic diamine component represented by formula (6) is contained, the ratio of the aromatic diamine component represented by formula (6) to the total aromatic diamine components is, for example, 20 to 100 mol%, and thereafter stepwise thereafter 30 to 100 mol%, 40 to 100 mol%, 50 to 100 mol%, 60 to 100 mol%, 70 to 100 mol%, 80 to 100 mol%, preferably 90 to 100 mol%, and particularly 100 mol%.

[0185] When the aromatic diamine component represented by the formula (6) is contained, the proportion of this aromatic diamine component is, for example, 20 to 100 mol%, and thereafter stepwise thereafter 30 to 100 mol%, 40 to 100 mol%, 50 to 100 mol%, 60 to 100 mol%, 70 to 100 mol%, and particularly 80 to 100 mol%, based on the total diamine components.

[0186] (Manufacturing method) The polyimide of the present invention can be obtained by reacting the tetracarboxylic dianhydride component with the diamine component using a conventional method, i.e., by reacting the tetracarboxylic dianhydride component with the diamine component (condensation reaction, polymerization reaction) to obtain the corresponding polyamic acid, and then by dehydrating and cyclizing the obtained polyamic acid.

[0187] In the step of obtaining a polyamic acid, the ratio of the tetracarboxylic dianhydride component to the diamine component in the reaction can be appropriately selected. For example, the ratio of the tetracarboxylic dianhydride component is 0.7 to 1.5 mol, preferably 0.9 to 1.1 mol, more preferably 0.95 to 1.05 mol, and particularly preferably about 1 mol, per 1 mol of the diamine component.

[0188] The reaction (condensation reaction, polymerization reaction) may be carried out in the absence or presence of a solvent. The solvent may be any component that is liquid at the reaction temperature. For example, the solvent may be a component that is solid at room temperature or liquid at the reaction temperature. Representative solvents (organic solvents) include ethers such as chain ethers (e.g., diphenyl ether) and cyclic ethers (e.g., tetrahydrofuran); halogenated chain hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride) and halogenated aromatic hydrocarbons (e.g., trichlorobiphenyl); aromatic hydrocarbons (e.g., benzene, toluene, xylene); nitrogen-containing heterocyclic compounds (e.g., N-methyl-2-pyrrolidone); sulfone compounds (e.g., aliphatic sulfones (e.g., sulfolane, dimethyl sulfone), and aromatic sulfones (e.g., diphenyl sulfone). The solvents may be used alone or in combination.

[0189] The reaction (condensation reaction, polymerization reaction) may be carried out in the presence of a catalyst, if necessary. Examples of the catalyst include amine catalysts such as trimethylamine, triethylamine, triethylenediamine, tributylamine, dimethylaniline, pyridine, α-picoline, β-picoline, γ-picoline, isoquinoline, lutidine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,4-diazabicyclo[2.2.2]octane, and 1,8-diazabicyclo[5.4.0]-7-undecene.

[0190] The reaction temperature is, for example, 10 to 200°C, preferably 20 to 150°C, and more preferably 30 to 100°C.

[0191] The reaction may be carried out in air, or in an atmosphere or under a flow of an inert gas such as helium, nitrogen, argon, etc. The reaction may also be carried out under normal pressure, elevated pressure, or reduced pressure.

[0192] This reaction (condensation reaction, polymerization reaction) produces polyamic acid, which is then dehydrated and cyclized to produce transparent polyimide.

[0193] In the dehydration ring-closure step, the method for dehydrating and ring-closing the polyamic acid obtained by the reaction is not particularly limited, and examples thereof include a method using a dehydrating agent which is an acid anhydride such as acetic anhydride, a method of heating at a high temperature, and a method of combining these.

[0194] After the reaction is completed, the product polyimide can be separated and purified by a conventional separation method such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. [Example]

[0195] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Evaluation methods are shown below.

[0196] [Evaluation method] (Nuclear Magnetic Resonance Spectrum) 1 H-NMR: Measurement was performed using a nuclear magnetic resonance spectrometer (BRUKER "ADVANCE III HD"). The measurement solvent was deuterated chloroform or deuterated dimethyl sulfoxide, and the internal standard was tetramethylsilane ( 1 H:0 ppm), deuterated chloroform ( 13 C: 77 ppm), or deuterated dimethyl sulfoxide ( 1 H: 2.5 ppm, 13 C: 40 ppm).

[0197] (Melting Point) Measurements were performed by differential scanning calorimetry (DSC) using a differential scanning calorimeter (SII NanoTechnology Inc., "EXSTAR DSC6200") under a nitrogen stream at a temperature rise rate of 10°C / min in the temperature range of 30 to 300°C.

[0198] (Heat resistance (mass loss temperature)) Using a differential thermogravimetric analyzer ("TG / DTA6200" manufactured by Hitachi High-Tech Science Corporation), the 5% mass loss temperature and the 10% mass loss temperature were measured in a nitrogen atmosphere at a temperature rise rate of 10°C / min in the temperature range of 30 to 520°C.

[0199] (purity) The measurement was carried out using liquid chromatography (LC, manufactured by Shimadzu Corporation, "LC-2010A"), with an eluent of acetonitrile / water (volume ratio) = 80 / 20 → 95 / 5 → 80 / 20.

[0200] (molecular weight) Measurements were performed using a liquid chromatography mass spectrometer (LCMS, Shimadzu Corporation, "Ninetex XB-C18"), with acetonitrile / water (volume ratio) = 50 / 50 → 80 / 20 → 95 / 5 → 50 / 50 as the eluent.

[0201] (refractive index) Measurements were taken using a multi-wavelength Abbe refractometer "DR-M2 / 1550" (manufactured by Atago Co., Ltd.) at a light source wavelength of 589 nm and a measurement temperature of 25°C.

[0202] Example 1 (first step) A separable flask was charged with 17.5 g (50 mmol) of 9,9-bis(4-hydroxyphenyl)fluorene, 18.2 g (110 mmol) of 4-nitrophthalonitrile, and 112 g of N,N-dimethylformamide (DMF), and the resulting mixture was stirred. To this solution, 27.6 g (200 mmol) of potassium carbonate and 37.5 g of DMF were added, followed by stirring at 50 °C for 3 hours. The solvent was removed by heating under reduced pressure, and 100 g of toluene and 150 g of ion-exchanged water were added. The mixture was stirred at 70 °C for 1 hour and then cooled to 20 °C to precipitate crystals. The crystals were filtered and rinsed with 100 g of ion-exchanged water and 50 g of ethanol, yielding 27 g (90% yield) of crude 9,9-bis[4-(3,4-dicyanophenoxy)phenyl]fluorene (BPF-PN). The LC purity of this crude crystal (BPF-PN) was 99%. The chemical structure of the crude crystal is 1 The compound was identified by H-NMR spectroscopy.

[0203] (Second process) 30.1 g (50 mmol) of crude BPF-PN crystals obtained in the previous step was added to a three-neck flask, followed by 47.8 g of ethanol, 47.8 g of dioxane, and 140.3 g (800 mmol) of 24% by weight potassium hydroxide aqueous solution. The mixture was stirred at 80°C under reflux for approximately 18 hours. After the reaction was completed, the mixture was cooled to 30°C and then 85.9 g (820 mmol) of hydrochloric acid was added to neutralize the reaction solution. 28.7 g of DMF was added to the reaction solution, and the mixture was stirred at 75°C to dissolve the solution. The solvent was then distilled off, followed by the addition of 191 g of methyl isobutyl ketone (MIBK). The mixture was then separated and the aqueous layer was removed. This was followed by a total of five acid washes, in which 95 g of 5% by weight hydrochloric acid was added and stirred, to pickle the organic layer. The organic layer was heated and concentrated under reduced pressure to remove the solvent, yielding 34 g (100% yield) of oily 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene (BPF-P). The LC purity of this oily product (BPF-P) was 98%. The chemical structure of the product is 1 The compound was identified by H-NMR spectroscopy.

[0204] (Third step) 42.4 g (50 mmol) of BPF-P obtained in the previous step and 102 g (1 mol) of acetic anhydride were added to a three-neck flask and reacted under reflux at 120°C, and the refluxing components were poured out. After the reaction was completed, the mixture was slowly cooled to room temperature, and then 85 g of acetone was added and stirred at 10°C or below. The crystals were then filtered to obtain 26 g of 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride (BPF-PA) represented by the following formula (7) (80% yield for the entire process). The LC purity of the obtained crystals (BPF-PA) was 99%. The chemical structure of the crystals is: 1 The compound was identified by H-NMR spectroscopy.

[0205] [ka]

[0206] Example 2 (first step) A 2-L four-neck flask was charged with 80 g (178 mmol) of 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 64.6 g (373 mmol) of 4-nitrophthalonitrile, and 532 g of DMF under a nitrogen stream. Then, 98.2 g (711 mmol) of potassium carbonate and 19.5 g of DMF were added, heated to 45-54°C, and stirred for 4 hours. After the reaction was complete, the DMF was concentrated, and 600 g of MIBK and 900 g of ion-exchanged water were added. The mixture was heated to 80°C, dissolved, and separated to extract the organic layer. This organic layer was concentrated to obtain 133 g (100% yield) of yellow crystalline 9,9-bis[6-(3,4-dicyanophenoxy)-2-naphthyl]fluorene (BNF-PN). The LC purity of the resulting crystals (BNF-PN) was 97.6%. The chemical structure of the crystal is: 1 The compound was identified by H-NMR spectroscopy.

[0207] (Second process) In a 2-L four-neck flask, 103 g (147 mmol) of the BNF-PN obtained in the previous step and 290 g of ethanol were added under a nitrogen stream and stirred, and 878 g (4.39 mol) of a 20% by mass aqueous sodium hydroxide solution was added and reacted for 56 hours at 80° C. After the reaction, 392.4 g (3.76 mol) of concentrated hydrochloric acid and 39.2 g of ion-exchanged water were added to adjust the pH to 7, and the solvent was then concentrated and removed. 60.7 g (587 mmol) of concentrated hydrochloric acid and 6.1 g of ion-exchanged water were added to adjust the pH to 1, and 561 g of ethyl acetate and 140 g of MIBK were added, and the mixture was heated to 70° C. and separated to extract the organic layer. An additional 280 g of ion-exchanged water was added and the mixture was washed a total of four times. The organic layer was concentrated to obtain 117 g (100% yield) of orange crystals of 9,9-bis[6-(3,4-dicarboxyphenoxy)-2-naphthyl]fluorene (BNF-P). The LC purity of the obtained crystals (BNF-P) was 94%. The chemical structure of the crystals is as follows: 1 The compound was identified by H-NMR spectroscopy.

[0208] (Third step) In a 1 L four-neck flask, 107 g (137 mmol) of BNF-P obtained in the previous step and 280 g (2.75 mol) of acetic anhydride were added under a nitrogen stream and allowed to react for 8 hours under reflux at 120°C. The organic solvent was then concentrated, 200 g of toluene was added, and the mixture was heated to 50°C for dissolution. 1 kg of heptane was added dropwise to crystallize the target product. The precipitate was collected and dried under reduced pressure at 60-80°C to obtain 76.5 g of 9,9-bis[6-(3,4-dicarboxyphenoxy)-2-naphthyl]fluorene dianhydride (BNF-PA) represented by the following formula (8) (75% yield overall). The LC purity of the obtained crystals (BNF-PA) was 75%. The chemical structure of the crystals is: 1 The compound was identified by H-NMR spectroscopy.

[0209] [ka]

[0210] Example 3 (first step) A 500 mL four-neck flask was charged with 20 g (45.6 mmol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and 160 mL of DMF, and the mixture was cooled to 10°C. 4.03 g (101 mmol) of sodium hydride was added to the solution, followed by 16.6 g (96.0 mmol) of 4-nitrophthalonitrile. The mixture was then heated to room temperature and stirred for 4 hours. 2.0 L of 0.1 M hydrochloric acid was charged to a 5 L four-neck flask, cooled to 15°C, and the reaction solution was slowly added to the hydrochloric acid. After stirring the reaction solution, the precipitated crystals were filtered, washed with 500 mL of distilled water, and dried at 50°C to obtain 77.5 g of crude crystals. The obtained crude crystals were added to 250 mL of heptane, stirred and washed at room temperature for 3 hours, filtered, and dried at 50°C to obtain 29.3 g (yield 92.8%) of pale yellow solid 9,9-bis[4-(2-(3,4-dicyanophenynoxy)ethoxy)phenyl]fluorene (BPEF-PN). The LC purity of the obtained crystals (BPEF-PN) was 82.8%. The chemical structure of the crystals is as follows: 1 The compound was identified by H-NMR spectroscopy.

[0211] (Second process) A 500 mL four-neck flask was charged with 7.31 g (10.6 mmol) of BPEF-PN obtained in the previous step, 80 mL of DMF, and 40 mL of ethanol. The mixture was heated to 77°C, and then 40 mL (160 mmol) of 4 M aqueous sodium hydroxide solution was added. The mixture was stirred at 80°C for 25 hours. After cooling to room temperature, 500 mL of 0.5 M hydrochloric acid was added to the reaction solution. The precipitated solid was filtered, washed with 400 mL of distilled water and 100 mL of heptane, and then dried at 70°C to obtain 6.83 g (84.2% yield) of brown solid 9,9-bis[4-(2-(3,4-dicarboxyphenyloxy)ethoxy)phenyl]fluorene (BPEF-P). The LC purity of the obtained crystals (BPEF-P) was 98%. The chemical structure of the crystals is 1 The compound was identified by H-NMR spectroscopy.

[0212] (Third step) Into a 100 mL four-neck flask, 4.0 g (5.22 mmol) of BPEF-P obtained in the previous step and 20 mL of acetic anhydride were added, and the mixture was stirred at 130°C for 11 hours. The acetic anhydride was distilled off under reduced pressure at 80°C, yielding 3.51 g of crude crystals. The obtained crude crystals were added to 17 mL of heptane, washed with stirring at room temperature, and then filtered to obtain 3.3 g (86.8% yield for the entire process) of 9,9-bis[4-(2-(3,4-dicarboxylic acid phenynoxy)ethoxy)phenyl]fluorene dianhydride (BPEF-PA) represented by the following formula (9) as a brown solid. The LC purity of the obtained crystals (BPEF-PA) was 99%. The chemical structure of the crystals is 1 The compound was identified by H-NMR spectroscopy.

[0213] [ka]

[0214] Example 4 (first step) A separable flask was charged with 18.9 g (50 mmol) of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 18.2 g (110 mmol) of 4-nitrophthalonitrile, and 112 g of DMF, and the mixture was stirred. To this reaction solution, 27.6 g (200 mmol) of potassium carbonate and 37.5 g of DMF were added, and the mixture was stirred at 50 ° C. for 3 hours. The solvent was removed by heating under reduced pressure, and 100 g of toluene and 150 g of ion-exchanged water were added. The mixture was stirred at 70 ° C. for 1 hour, and then cooled to 20 ° C. to precipitate crystals. The crystals were filtered and rinsed with 100 g of ion-exchanged water and 50 g of ethanol, yielding 28.3 g (90% yield) of crude 9,9-bis[4-(3,4-dicyanophenoxy)-3-methylphenyl]fluorene (BCF-PN). The LC purity of the obtained crude crystal (BCF-PN) was 99%. The chemical structure of the crystal was 1 The compound was identified by H-NMR spectroscopy.

[0215] (Second process) 31.5 g (50 mmol) of crude BCF-PN crystals obtained in the previous step were added to a three-neck flask, followed by 47.8 g of ethanol, 47.8 g of dioxane, and 140.3 g (800 mmol) of 24% by weight potassium hydroxide aqueous solution. The mixture was stirred at 80°C reflux for approximately 18 hours. After the reaction was completed, the mixture was cooled to 30°C and then 85.9 g (820 mmol) of hydrochloric acid was added to neutralize the reaction solution. 28.7 g of DMF was added, and the mixture was stirred at 75°C until dissolved. The solvent was then distilled off. 191 g of MIBK was then added, and the aqueous layer was removed by separation. This was followed by an acid wash in which 95 g of 5% hydrochloric acid was added and stirred, repeated five times in total, to acid-wash the organic layer. The organic layer was heated and concentrated under reduced pressure to remove the solvent, yielding 35.3 g (yield 100%) of oily 9,9-bis[4-(3,4-dicarboxyphenoxy)-3-methylphenyl]fluorene (BCF-P). The LC purity of the oily product (BCF-P) obtained was 98%. The chemical structure of the product is as follows: 1 The compound was identified by H-NMR spectroscopy.

[0216] (Third step) 35.3 g (50 mmol) of BCF-P obtained in the previous step and 102 g (1 mol) of acetic anhydride were added to a three-necked flask and reacted under reflux at 120°C, and the refluxing components were poured out. After the reaction was completed, the mixture was slowly cooled to room temperature, 85 g of acetone was added, and the mixture was stirred at 10°C or below. The crystals were then filtered to obtain 33.5 g of 9,9-bis[4-(3,4-dicarboxyphenoxy)-3-methylphenyl]fluorene dianhydride (BCF-PA) represented by the following formula (10) (80% yield for the entire process). The LC purity of the obtained crystals (BCF-PA) was 99%. The chemical structure of the crystals is as follows: 1 The compound was identified by H-NMR spectroscopy.

[0217] [ka]

[0218] (Characteristics of fluorenetetracarboxylic dianhydrides obtained in Examples 1 to 4) The properties of BPF-PA, BNF-PA, BPEF-PA, and BCF-PA obtained in Examples 1 to 4, as well as the properties of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) as Comparative Example 1 and pyromellitic dianhydride (PMDA) as Comparative Example 2, were evaluated and are shown in Table 1.

[0219] [Table 1]

[0220] As is clear from Table 1, compared to Comparative Examples 1 and 2, BPF-PA had higher 5% mass loss temperatures and 10% mass loss temperatures, BNF-PA had higher 10% mass loss temperatures, and BCF-PA had higher 5% mass loss temperatures and 10% mass loss temperatures, confirming that BPF-PA, BNF-PA, and BCF-PA have high heat resistance. In particular, it was confirmed that BNF-PA has a well-balanced high refractive index and high heat resistance. Furthermore, a comparison between Example 1 and Example 4 confirmed that BPF-PA, which does not have a methyl group in the benzene ring bonded to the 9-position of the fluorene, has a higher refractive index and heat resistance than BCF-PA.

[0221] Example 5 10.8 g (0.1 mol) of p-phenylenediamine was dissolved in 380 g of N-methyl-2-pyrrolidone (NMP), and 64.2 g (0.1 mol) of BPF-PA synthesized in Synthesis Example 1 was added to this solution and homogenized under a nitrogen atmosphere. The reaction solution was applied to a glass plate, and after removing the solvent at 130°C, imidization was carried out under vacuum at 300°C for 1 hour to obtain a transparent polyimide film.

[0222] It was confirmed that the polyimide of Example 5 has high transparency and is useful for optical molded articles such as optical films. [Industrial Applicability]

[0223] In the method of the present invention, fluorene tetracarboxylic dianhydride can be produced using a hydroxyl group-containing fluorene compound as a starting material. Such fluorene tetracarboxylic dianhydride has various excellent properties, such as optical properties, heat resistance, water resistance, moisture resistance, chemical resistance, electrical properties, mechanical properties, and dimensional stability. Therefore, the fluorene tetracarboxylic dianhydride can be suitably used as a resin raw material, such as a raw material for polyimide resins.

[0224] In particular, the polyimide of the present invention, which has a tetracarboxylic dianhydride component containing a fluorenetetracarboxylic dianhydride component as a polymerization component, has high heat resistance and can be applied to printed wiring boards, etc., and also has excellent optical properties, so is useful as an optical molded product (optical molded product or optical component). Examples of such optical molded products include optical films (or optical sheets) and optical lenses.

Claims

1. The following formula (1) 【Chemistry 1】 (In the formula, ring Z １ and Z ２ are the same or different and represent a monocyclic arene ring or a fused bicyclic to fused tetracyclic arene ring; R １ａ and R １ｂ are the same or different and represent an alkylene group; m1 and m2 are the same or different and represent an integer of 0 or 1 or more; R ２ａ and R ２ｂ are the same or different and represent a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, a mercapto group, an acyl group, a carboxy group, a carbamoyl group, a nitro group, an amino group, or a substituted amino group; n1 and n2 are the same or different and represent an integer of 0 or 1 or more; R ３ represents a hydrocarbon group or a halogen atom, k represents 0 or an integer of 1 to 8, and R ４ａ and R ４ｂ are the same or different and represent an alkyl group, an aryl group, an alkoxy group, or a halogen atom; p1 and p2 are the same or different and represent 0 or an integer of 1 to 3. and a refractive index of 1.6 to 2, The following formula (2) 【Chemistry 2】 (In the formula, Z １ , Z ２ , R １ａ , R １ｂ , R ２ａ , R ２ｂ , R ３ , k, m1, m2, n1, and n2 are the same as in formula (1). and a compound (2) represented by the following formula (3): 【Transformation 3】 (In the formula, R ４ represents an alkyl group, an aryl group, an alkoxy group or a halogen atom, and p represents 0 or an integer of 1 to 3), in the presence of a base catalyst to obtain a compound represented by the following formula (4): 【Chemistry 4】 (In the formula, Z １ , Z ２ , R １ａ , R １ｂ , R ２ａ , R ２ｂ , R ３ , R ４ａ , R ４ｂ , k, m1, m2, n1, n2, p1, and p2 are the same as in formula (1). The first step is to obtain a tetracarbonitrile (4) represented by the following formula (5): 【Transformation 5】 (In the formula, Z １ , Z ２ , R １ａ , R １ｂ , R ２ａ , R ２ｂ , R ３ , R ４ａ , R ４ｂ , k, m1, m2, n1, n2, p1, and p2 are the same as in formula (1). and a third step of reacting the tetracarboxylic acid (5) obtained in the second step with a dehydrating agent, followed by crystallization using acetone alone, heptane alone, or a combination of toluene and heptane, to obtain a tetracarboxylic acid dianhydride (1) represented by formula (1).

2. In formula (1), ring Z １ and Z ２ are the same or different and C ６－１２ is an arene ring, and R １ａ and R １ｂ are the same or different and are linear or branched chain C ２－６ an alkylene group, m1 and m2 are the same or different and each represent an integer of 0 or 1 to 10; R ２ａ and R ２ｂ are the same or different and C １－６ Alkyl group or C ６－１０ The method of claim 1, wherein the aryl groups, n1 and n2, are the same or different and each is an integer of 0 or 1 to 2.

3. 3. The method according to claim 1, wherein in the first step, the hydroxy group of the compound represented by formula (2) is an alcoholic hydroxy group.

4. The following formula (1a) 【Transformation 6】 (wherein rings Z 1 and Z 2 may be the same or different and represent a fused bicyclic to fused tetracyclic arene ring; m1 and m2 may be the same or different and represent an integer of 1 or more; R 1a, R １ｂ , R ３ , R ４ａ , R ４ｂ , k, p1 and p2 are the same as those in formula (1) of claim 1. and a refractive index of 1.6 to 2.

5. The following formula (1) 【Transformation 7】 (wherein rings Z 1 and Z 2 are the same or different and represent a fused bicyclic to fused tetracyclic arene ring; m1 and m2 are the same or different and represent an integer of 1 or more; R １ａ , R １ｂ , R ２ａ , R ２ｂ , R ３ , R ４ａ , R ４ｂ , k, n1, n2, p1 and p2 are the same as in formula (1) of claim 1. and a diamine component, wherein the diamine component is represented by the following formula (6): 【Transformation 8】 (wherein ring Ar is a monocyclic arene ring or a fused polycyclic arene ring and represents a C 6-20 arene ring; R ５ａ and R ５ｂ are the same or different and represent an alkylene group, an oxyalkylene group, a cycloalkylene group, or an oxycycloalkylene group; q1 and q2 are the same or different and represent 0 or 1; R ６ represents an alkyl group or an aryl group, and r represents an integer of 0 or 1 or more. A polyimide containing at least a diamine component having a C 6-20 arene ring represented by the formula:

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