KR20230171510A - Novel diamine, polyamic acid and polyimide comprising the same - Google Patents

Abstract

The present invention provides a novel fluorene-based diamine, polyamic acid and polyimide polymer manufactured using the diamine, and low dielectric and low dielectric loss polymer coating materials and films for electronic devices using the same.

Description

New diamine, polyamic acid and polyimide polymer containing the same {NOVEL DIAMINE, POLYAMIC ACID AND POLYIMIDE COMPRISING THE SAME}

The present invention relates to a novel fluorene-based diamine, polyamic acid and polyimide polymer manufactured using the diamine, and films and polymer coating materials for electronic devices using the same.

Polyimide resin (polyimide, PI) refers to a highly heat-resistant resin produced by solution polymerizing aromatic dianhydride and aromatic diamine or aromatic diisocyanate to produce a polyamic acid derivative, followed by high temperature and chemical ring-closure dehydration to imidize. . Because these polyimide resins have excellent mechanical, heat resistance, and electrical insulation properties, they are used in a wide range of electronic materials, such as semiconductor insulating films and display printed wiring circuit boards.

In general, polyimide films are made by applying a polyamic acid composition to a substrate and then going through a two-stage heat curing process of pre-curing and main-curing. This pre-curing is a process for volatilizing the solvent in a temperature range of 100 to 150°C, and main-curing is a process for polymerizing polyamic acid into polyimide through ring-closure dehydration reaction in a temperature range of 300 to 550°C. In other words, the above two-step process involves forming a film in a relatively unstable polyamic acid state due to the insoluble and infusible characteristics of polyimide itself, resulting in problems such as complexity of the manufacturing process, increased manufacturing costs, and reduced mass production. It is brought about.

Accordingly, there is a demand for the development of polyamic acid and polyimide materials that exhibit excellent mechanical properties, low dielectric constant and low dielectric loss factor, while improving solubility and processability.

The present invention was devised to solve the above-mentioned problems, and its technical task is to provide a new diamine containing a functional moiety while having a fluorene-based basic skeleton in the molecule.

In addition, the present invention provides a polymer film containing polyamic acid and polyimide polymer that can secure excellent solubility and processability while maintaining an appropriate level of mechanical properties, low dielectric constant and low dielectric loss rate using the novel diamine described above. This is another technical task.

Other objects and advantages of the present invention can be more clearly explained by the following detailed description and claims.

In order to achieve the above technical problem, the present invention provides a compound represented by the following formula (1), specifically a fluorene-based diamine monomer.

In the above equation,

X and Y are the same or different from each other, and are each independently a single bond or an alkyl group of C ₁ to C ₁₀ ,

Z is selected from the group consisting of O, S and NR ₃ ,

m and n are each independently 0 or 1, but if m+n ≤1, Z is not included,

R ₁ to R ₃ are the same or different from each other, and are each independently hydrogen, halogen, nitro group, C ₁ to C ₁₀ alkyl group, C ₂ to C ₂₀ alkenyl group, C ₁ to C ₂₀ alkyloxy group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ C ₂₀ aryloxy group, heterocyclic group with 5 to 20 nuclear atoms, heterocyclic oxy group with 5 to 20 nuclear atoms, alkylsulfanyl group with C ₁ ~ C ₂₀ , C ₆ ~ C ₂₀ arylsulfanyl group, and C ₁ ~ C ₂₀ acyl group, provided that at least one of the plurality of R ₁ and R ₂ is an alkyloxy group, an aryloxy group, and a heterocyclic oxy group. Contains any one of

a and b are each independently integers from 1 to 4,

The alkyl group, alkenyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, and acyl group of R ₁ to R ₃ are each independently hydrogen, deuterium, or halogen. , nitro group, epoxy group, cyano group, C ₁ to C ₁₀ alkyl group, C ₂ to C ₁₀ alkenyl group, C ₂ to C ₁₀ alkynyl group, C ₃ to C ₁₀ cycloalkyl group, nuclear atoms 3 to 10 It may be substituted with one or more substituents selected from the group consisting of a heterocycloalkyl group, a C ₆ to C ₁₀ aryl group, a heteroaryl group with 5 to 10 nuclear atoms, and a C ₁ to C ₁₀ alkyloxy group, At this time, when the substituents are plural, they may be the same or different from each other.

In addition, the present invention provides a diamine containing the compound of formula (1) described above; And it provides a composition for producing polyamic acid containing an acid dianhydride.

In addition, the present invention provides a polyamic acid formed from the above-described composition for producing polyamic acid and a polyimide polymer formed by imidizing the polyamic acid.

According to one embodiment of the present invention, by using a diamine monomer containing a functional moiety in a fluorene-based core such as fluorene, spirofluorene, or xanthene, Compared to conventional diamines, it can exhibit improved processability and solubility characteristics.

In addition, polyamic acid and/or polyimide polymer obtained using the above-mentioned diamine not only exhibits low moisture absorption and low dielectric constant characteristics, but can also exhibit high heat resistance and excellent mechanical properties at the same time. Accordingly, the polyimide film of the present invention is not only useful as a substrate for electronic devices and a coating material for electrical and electronic components, but can also be applied to various other fields.

The effects according to the present invention are not limited to the contents exemplified above, and more diverse effects are included in the present specification.

Hereinafter, the present invention will be described in detail.

All terms (including technical and scientific terms) used in this specification, unless otherwise defined, may be used with meanings that can be commonly understood by those skilled in the art to which the present invention pertains. Additionally, terms defined in commonly used dictionaries are not to be interpreted ideally or excessively unless clearly specifically defined.

In addition, throughout this specification, when a part is said to "include" a certain component, unless specifically stated to the contrary, this is an open term that implies the possibility of further including other components rather than excluding other components. It should be understood as (open-ended terms). In addition, throughout the specification, “above” or “on” means not only the case where it is located above or below the object part, but also the case where there is another part in the middle, and it must be in the direction of gravity. It does not mean that it is located above the standard.

As used herein, “preferred” and “preferably” refer to embodiments of the invention that may provide certain advantages under certain circumstances. However, under the same or different circumstances, other embodiments may also be preferred. Additionally, mention of one or more preferred embodiments does not mean that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

In addition, in this specification, “monomer” and “monomer” have the same meaning. Monomers in the present invention are distinguished from oligomers and polymers, and refer to compounds with a weight average molecular weight (Mw) of 1,000 g/mol or less. The term polymer also includes homopolymers, copolymers, and resins.

<Diamine monomer>

One embodiment of the present invention is a diamine monomer for producing polyamic acid and/or polyimide polymer. These diamine monomers are differentiated from conventional diamines in that they have a structure containing a functional moiety in a fluorene-derived basic skeleton.

For one specific example, the diamine monomer may be represented by the following formula (1).

[Formula 1]

In the above equation,

R ₁ to R ₃ are the same or different from each other, and are each independently hydrogen, halogen, nitro group, C ₁ to C ₁₀ alkyl group, C ₂ to C ₂₀ alkenyl group, C ₁ to C ₂₀ alkyloxy group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ C ₂₀ aryloxy group, heterocyclic group with 5 to 20 nuclear atoms, heterocyclic oxy group with 5 to 20 nuclear atoms, alkylsulfanyl group with C ₁ ~ C ₂₀ , C ₆ ~ C ₂₀ arylsulfanyl group, and C ₁ ~ C ₂₀ acyl group, provided that at least one of the plurality of R ₁ and R ₂ is an alkyloxy group, an aryloxy group, and a heterocyclic oxy group. Contains any one of

a and b are each independently integers from 1 to 4,

The alkyl group, alkenyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, and acyl group of R ₁ to R ₃ are each independently hydrogen, deuterium, or halogen. , nitro group, epoxy group, cyano group, C ₁ to C ₁₀ alkyl group, C ₂ to C ₁₀ alkenyl group, C ₂ to C ₁₀ alkynyl group, C ₃ to C ₁₀ cycloalkyl group, nuclear atoms 3 to 10 It may be substituted with one or more substituents selected from the group consisting of a heterocycloalkyl group, a C ₆ to C ₁₀ aryl group, a heteroaryl group with 5 to 10 nuclear atoms, and a C ₁ to C ₁₀ alkyloxy group, At this time, when the substituents are plural, they may be the same or different from each other.

For one specific example of Formula 1, X and Y are each independently a single bond; Or, _{one of} can do. In other words, m and n can each independently be 0 or 1, but if m+n ≤1, Z is not included.

The heteroatom (e.g., Z) included in the condensed ring may be any conventional heteroatom known in the art without limitation. For example, Z may be selected from the group consisting of O, S, and NR ₃ . Specifically, Z is preferably O or S, and more preferably O.

In addition, even if a plurality of R ₁ and a plurality of R ₂ are expressed as the same, they may be the same or different from each other, and each independently represents hydrogen, a C ₁ to C ₂₀ alkyloxy group, a C ₆ to C ₂₀ aryloxy group, and heterocyclic oxy groups having 5 to 20 nuclear atoms. And, R ₃ is hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₁ to C ₂₀ alkyloxy group, a C ₆ to C ₂₀ aryloxy group, and a heterocyclic oxy group having 5 to 20 nuclear atoms. is selected, and a and b are each independently integers of 1 or 2.

The above-described alkyloxy group, aryloxy group, and heterocyclic oxy group of R ₁ to R ₃ are each independently halogen, CF ₃ , nitro group, cyano group, C ₁ to C ₁₀ alkyl group, and C ₂ to C ₁₀ alkenyl group. , C ₃ to C ₁₀ cycloalkyl group, C ₆ to C ₁₀ aryl group, and heteroaryl group having 5 to 10 nuclear atoms.

The compound represented by Formula 1 contains fluorene in the molecule, and has a fluorene-derived basic skeleton in which an aryl group, spiro group, aliphatic ring, heteroaliphatic ring group, etc. are bonded to the 9th position of the fluorene as a core ( core), and has a structure in which diamine is connected to phenyl rings on both sides of fluorene in the core. When these diamine compounds are used as polyamic acid and/or polyimide materials, they can exhibit appropriate mechanical properties and low dielectric constant properties due to fluorene.

In addition, various functional moieties, such as polar groups (e.g., alkyloxy group, aryloxy group, heterocyclic oxy group) are introduced into the aryl group, spiro group, aliphatic ring, heteroaliphatic ring group, etc. bonded to the fluorene-derived core. By controlling the number of these, solubility, processability, and heat resistance can be improved compared to conventional diamines, and dielectric loss rate can be minimized.

As a preferred example, the compound represented by Formula 1 may be further specified as one of the following Formulas 2 to 7 depending on the types of X, Y, and Z and their bonding positions. However, it is not limited to this.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In the above equation,

R ₁ , R ₂ , R ₃ , a and b are each as defined in Formula 1.

As a more preferable example, the compounds represented by Formulas 2 to 7 can be further specified as any one of Formulas 2A to 7A exemplified below depending on the bonding positions of R ₁ and R ₂ introduced into the fluorene-based basic skeleton. there is. However, it is not limited to this.

[Formula 2A]

[Formula 2B]

[Formula 3A]

[Formula 4A]

[Formula 5A]

[Formula 6A]

[Formula 7A]

In the above equation,

R ₁ to R ₃ are each as defined in Formula 1.

The compound represented by Formula 1 of the present invention described above may be further specified as the compounds exemplified below. However, the compound represented by Formula 1 of the present invention is not limited to those exemplified below.

The method for producing the diamine compound represented by Formula 1 according to the present invention is not particularly limited, and may be produced according to conventional methods known in the art.

An example of the above production method includes synthesizing a dinitro compound containing dinitrofluorene, dinitro spirofluorenxanthene, and a hydroxyl group; Introducing a functional group into a hydroxyl group; and reducing the nitro group.

At this time, the step of reducing the nitro group is not particularly limited, and common methods known in the art can be used. For example, this may include injecting hydrogen gas into a solvent using palladium/carbon, platinum, nickel, etc. as a catalyst, or reacting metals such as iron and tin with hydrogen chloride.

The term “alkyl group” used herein refers to a monovalent substituent derived from a straight-chain or branched saturated hydrocarbon having 1 to 20 carbon atoms (specifically, 1 to 10 carbon atoms). In one embodiment, the alkyl may be selected from the group consisting of methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, etc., but is not limited thereto.

The term “alkenyl group” as used herein refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 20 carbon atoms (specifically, 2 to 10 carbon atoms) having one or more carbon-carbon double bonds. . In one embodiment, the alkenyl may be selected from the group consisting of vinyl, allyl, isopropenyl, 2-butenyl, etc., but is not limited thereto.

As used herein, the term “aryl group” refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 20 carbon atoms (specifically, 6 to 10 carbon atoms) consisting of a single ring or a combination of two or more rings. In addition, forms in which two or more rings are simply attached or condensed to each other may also be included. In one embodiment, the aryl may be selected from the group consisting of phenyl, naphthyl, phenanthryl, anthryl, etc., but is not limited thereto.

As used herein, the term “heterocyclic group” refers to a cyclic monovalent substituent having one or more heteroatoms selected from the group consisting of N, O, S, and Se, and the remainder consisting of C atom(s). At this time, the 'heterocyclic group' may be a single ring or a multiple ring. If the heterocyclic group is an aromatic ring, it is called a heteroaryl group, and if the heterocyclic group is an alicyclic ring, it is called a heterocycloalkyl group. The heterocyclic group may be a cyclic group containing a 4-membered, 5-membered, 6-membered, 7-membered or 8-membered ring, wherein the ring contains one or more ring atoms selected from the group consisting of N, O, Se and S, It has C as the remaining ring atom. In one embodiment, the heterocyclic group is pyrrolidinyl group, piperidinyl group, piperazinyl group, morpholino group, thiomorpholino group, homopiperidinyl group, chromanyl group, isochromanyl group, chromenyl group, and pyrrolyl group. , furanyl group, thienyl group, pyrazolyl group, imidazolyl group, furazanyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, Pyrazinyl group, pyranyl group, indolyl group, isoindolyl group, indazolyl group, purinyl group, indolizinyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, pteridinyl group, quinolizinyl group, It may be selected from the group consisting of benzoxazinyl group, carbazolyl group, phenazinyl group, phenothiazinyl group, and phenanthridinyl group, but is not limited thereto.

The term "alkyloxy group" used herein refers to a monovalent substituent represented by R'O-, where R' refers to alkyl having 1 to 20 carbon atoms (specifically, 1 to 10 carbon atoms), and is a straight chain or branched group. Alternatively, it may include a cyclic structure. In one embodiment, the alkyloxy may be selected from the group consisting of methoxy, ethoxy, n-propoxy, 1-propoxy, t -butoxy, n-butoxy, pentoxy, etc., but is not limited thereto. No.

The term “aryloxy group” used herein refers to a monovalent substituent represented by RO-, where R refers to aryl having 5 to 20 carbon atoms (specifically, 6 to 10 carbon atoms). In one embodiment, the aryloxy may be selected from the group consisting of phenyloxy, naphthyloxy, diphenyloxy, etc., but is not limited thereto.

<Composition for producing polyamic acid>

Another embodiment of the present invention is a composition for producing polyamic acid containing the above-described novel diamine compound, which corresponds to a precursor solution for forming polyamic acid and/or polyimide (co)polymer.

Specifically, the composition for producing polyamic acid includes at least one type of diamine compound and at least one type of acid dianhydride, and the diamine compound includes a compound represented by the above-mentioned formula (1). If necessary, at least one latent hardener and/or conventional additives known in the art may be further included.

Hereinafter, the composition of the composition for producing polyamic acid will be examined in detail as follows.

diamine

The composition for producing polyamic acid according to the present invention includes the compound represented by the above-mentioned formula (1).

Here, the diamine compound represented by Formula 1 is the same as described above, so separate description is omitted.

In the composition for producing polyamic acid according to the present invention, the content of the compound of Formula 1 is not particularly limited and can be appropriately adjusted within the content range known in the art. For example, the compound of Formula 1 may be included in the range of 1 to 100 mol%, specifically 10 to 100 mol%, based on 100 mol% of the total diamine.

The present invention may further include common diamine compounds known in the art.

These diamine compounds can be used without particular limitations as long as they are non-fluorene diamine compounds different from the above-mentioned Chemical Formula 1, and examples include aromatic, alicyclic, or aliphatic compounds having a diamine structure. Specifically, the diamine compound includes non-fluorinated aromatic diamines, fluorinated aromatic diamines with fluorine substituents introduced, sulfone diamines, hydroxy diamines, ether diamines, and alicyclic diamines known in the art, respectively, either alone or in combination of two or more. can do.

Non-limiting examples of diamine compounds that can be used include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenyl Lendiamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5 -Diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3 '-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-dia Minobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4' -diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether , 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldi. Aniline, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodianiline , 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diamino Diphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl (3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'- Diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diamino Benzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene , 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4) -aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5) -diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl) Benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1, 4-phenylenebis(methylene)]dianiline, 4,4'-[1,3-phenylenebis(methylene)]dianiline, 3,4'-[1,4-phenylenebis(methylene)]di Aniline, 3,4'-[1,3-phenylenebis(methylene)]dianiline, 3,3'-[1,4-phenylenebis(methylene)]dianiline, 3,3'-[1, 3-phenylenebis(methylene)]dianiline, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1, 3-phenylenebis[(4-aminophenyl)methanone], 1,3-phenylenebis[(3-aminophenyl)methanone], 1,4-phenylenebis(4-aminobenzoate), 1 , 4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl ) Terephthalate, bis(3-aminophenyl) terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4) -Aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)terephthalate Amide, N,N'-bis(4-aminophenyl)isophthalamide, N,N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4 '-bis(4-aminophenoxy)diphenylsulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3- Amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino- 4-methylphenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1, 4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy) Si)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis (4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane , 1,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxy) Si) undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-(3-aminophenoxy)dodecane. Bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminoctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1 , 12-diaminododecane, and one or more compounds selected from the group consisting of diamine compounds having as the diamine side chain an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocycle, and a cyclic substituent consisting of these. You can. The above-described diamines may be used individually or two or more of them may be used in a mixed form.

Specifically, the fluorinated diamine may be 2,2'-bis(trifluoro methyl)-4,4'-diaminobiphenyl (2,2'-TFDB), which can induce linear polymerization. . In addition, the sulfone diamine may be bis(4-aminophenyl)sulfone (4,4'-DDS), and the hydroxy diamine may be 2,2-bis(3-amino-4-methylphenyl)-hexafluoro. Propane (2,2-Bis (3-amino-4-methylphenyl)-hexafluoropropane, BIS-AT-AF) can be used. Additionally, the ether diamine may be 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether (6-FODA) or oxydianiline (ODA).

acid dianhydride

The composition for producing polyamic acid according to the present invention includes at least one acid dianhydride compound known in the art.

The acid dianhydride monomer may be any compound known in the art having an intramolecular dianhydride structure without limitation. Specifically, common fluorinated aromatic dianhydrides, cycloaliphatic secondary acid dianhydrides, and non-fluorinated aromatic tertiary acid dianhydrides known in the art may be used alone or in combination of two or more types.

The fluorinated aromatic first acid dianhydride monomer is not particularly limited as long as it is an aromatic dianhydride into which a fluorine substituent is introduced. Examples of fluorinated aromatic primary acid dianhydrides that can be used include 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 6-FDA), 4-(trifluoromethyl)pyromellitic dianhydride (4-(trifluoromethyl)pyromellitic dianhydride, 4-TFPMDA), etc. These may be used alone or in combination of two or more types.

Additionally, the alicyclic second acid dianhydride is not particularly limited as long as it is a compound that has an alicyclic ring rather than an aromatic ring in the compound and has a dianhydride structure. Examples of usable alicyclic secondary acid dianhydrides include cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,3,4-cyclopentane tetracarboxylic dianhydride (CPDA), and bicyclo[ 2,2,2]-7-octene-2,3,5,6-tetracarboxylic acid dianhydride (BCDA), etc., but is not particularly limited thereto. The above-described dianhydrides can be used individually or in a mixture of two or more types.

Additionally, the non-fluorinated aromatic third acid dianhydride monomer is not particularly limited as long as it is a non-fluorinated aromatic dianhydride in which a fluorine substituent is not introduced. Non-limiting examples of non-fluorinated aromatic tertiary acid dianhydride monomers that can be used include Pyromellitic Dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (3) ,3′,4,4′-Biphenyl tetracarboxylic acid dianhydride (BPDA), benzophenone tetracarboxylic dianhydride (BTDA), and oxydiphthalic dianhydride (ODPA). These may be used alone, or two or more types thereof may be mixed.

Non-limiting examples of usable acid dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,5,6-anthracenetetracarboxylic dianhydride, 3, 3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether, 3,3 ',4,4'-benzophenone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4- Dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethylsilane , bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3 ＇,4,4＇-Diphenylsulfone tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,3-diphenyl-1,2,3,4-cyclo Butane tetracarboxylic dianhydride, oxydiphthalate tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride Water, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 -Dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4 -Cycloheptane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxylic acid Cyclopentylacetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo[3,3,0]octane-2,4,6,8- Tetracarboxylic dianhydride, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,7, 9-Tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic dianhydride, tricyclo[6.3.0.0＜2,6＞]undecan- 3,5,9,11-tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1 ,2,3,4-Tetrahydrinaphthalene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]octo-7-ene-2,3,5,6-tetracarboxylic acid Dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid dianhydride, tetracyclo[6,2,1,1,0, 2,7]dodeca-4,5,9,10-tetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2:3, 5:6 dicarboxylic acid dianhydride, and 1 , 2,4,5-cyclohexanetetracarboxylic acid dianhydride may be one or more compounds selected from the group, but is not limited thereto. In a preferred embodiment, the acid dianhydride is pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (OPDA), and 4,4'-hexafluoroisopropyldenediphthalic dianhydride (6FDA). , cyclohexane 1,2,4,5-tetracarboxylic dianhydride (HPMDA), 2'-[bicyclo [2.2.1] heptane-2,1'-cyclopentane-3', 2"bicyclo [ 2.2.1] Heptane] -5,6, 5'6"-tetracarboxylic dianhydride (CpODA), and cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA). It may be one or more compounds selected. The above-mentioned acid dianhydrides can be used individually or in a mixture of two or more types.

In the composition for producing polyamic acid of the present invention, the ratio (a/b) of the number of moles of the diamine (a) and the number of moles of the dianhydride component (b) may be 0.7 to 1.3, preferably 0.8 to 1.2. , more preferably in the range of 0.9 to 1.1. However, it is not particularly limited thereto.

menstruum

The composition for producing polyamic acid of the present invention is a solvent for the solution polymerization reaction of the above-described diamine monomer and acid dianhydride monomer, and organic solvents known in the art can be used without limitation.

Non-limiting examples of usable organic solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethyl Urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl Isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, ethylene glycol monoacetate, diethylene glycol dimethyl ether, dimethyl ether Propylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl -3-methoxybutylacetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butylbutyrate, butyl ether, di Isobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, Methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy At least one organic solvent selected from the group consisting of propionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, and 4-hydroxy-4-methyl-2-pentanone. You can. However, it is not limited thereto and may include any organic solvent in which the polymer of the polymerization reaction is dissolved. Preferred examples include m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethylacetate, and One or more polar solvents selected from dimethyl phthalate (DMP) may be used. In addition, a low boiling point solution such as tetrahydrofuran (THF), chloroform, or a solvent such as γ-butyrolactone can be used. The content of the solvent is not particularly limited as long as it is the remaining amount so that the total amount of the composition is 100 parts by weight. In order to obtain an appropriate molecular weight and viscosity of the polyamic acid solution, it may be 50 to 95 parts by weight, specifically 70 to 90 parts by weight, based on the total weight of the composition for producing polyamic acid.

additive

In addition to the above-described components, the composition for producing polyamic acid of the present invention may include at least one common additive known in the art within the range that does not impair the effect of the invention.

Examples of additives that can be used include hardeners, latent hardeners, plasticizers, antioxidants, flame retardants, dispersants, viscosity regulators, leveling agents, inorganic fillers, and curing accelerators. These can be used alone or two or more types can be used together. The content of the additive is not particularly limited and can be appropriately adjusted within the usage range known in the art. For example, the at least one additive may be included in an amount of 0.01 to 10 parts by weight, specifically 0.1 to 5 parts by weight, based on the total weight of the composition for producing polyamic acid.

The composition for producing polyamic acid according to the present invention can be prepared according to a common method known in the art, and can be obtained, for example, by adding a diamine represented by Chemical Formula 1 and an acid dianhydride to a solvent and then reacting. Specifically, it contains a diamine containing the compound of Formula 1, at least one type of dianhydride, a solvent, and, if necessary, conventional additives, preferably with an equivalent ratio of diamine (a) to dianhydride (b) of approximately 1: 1, a composition for producing polyamic acid can be formed.

The composition of the composition for producing polyamic acid is not particularly limited, and for example, based on 100 parts by weight of the total weight of the composition for producing polyamic acid, 2.5 to 25.0 parts by weight of acid dianhydride, 2.5 to 25.0 parts by weight of diamine, and 100 parts by weight of the composition. It may include a residual amount of solvent.

<Polyamic acid>

Another embodiment of the present invention is a polyamic acid formed using the composition for producing polyamic acid described above, and is a polyimide precursor (poly(amic acid), PAA) polymer for producing a polyimide polymer.

For one specific example, the polyamic acid includes a repeating unit represented by any one of the following formulas 8 to 10.

[Formula 8]

[Formula 9]

[Formula 10]

In the above equation,

B of Formula 8; At least one of B ₁ and B ₂ of Formula 9; At least one of B ₁ to B ₃ of Formula 10 includes a group derived from the compound of Formula 1.

The A is a group derived from acid dianhydride,

In Formula 9, x and y are rational numbers that satisfy x+y=1,

In Formula 10, x, y, and z are rational numbers that satisfy x + y + z = 1, 0 < y + z ≤ 0.7, and 0.3 ≤ x + y < 1.

In Formulas 9 and 10, B ₁ to B ₃ may include a group derived from another diamine that is different from the diamine of Formula 1 described above. Since this diamine is the same as the additional diamine component described in the composition for producing polyamic acid described above, separate details are omitted. In addition, in Chemical Formulas 8 to 10, A is a group derived from acid dianhydride, and the component of this acid dianhydride is the same as the specific acid dianhydride component described in the composition for producing polyamic acid, and therefore, further details are omitted. And in Formula 10, B ₁ to B ₃ may be the same as or different from each other, and specifically, B ₂ or B ₃ may be the same as or different from B ₁ .

<Polyimide polymer and film>

In addition, another embodiment of the present invention is a polyimide polymer formed by imidizing the above-described polyamic acid. Specifically, the polyimide polymer is a polyimide resin obtained by dehydrating and ring-closing a polyamic acid-containing solution (eg, polyamic acid solution) formed by solution polymerizing the composition for producing polyamic acid described above.

The polyimide polymer may be a conventional polymer or copolymer, and is not particularly limited. For example, it may be in the form of a common random copolymer or block copolymer known in the art.

For one specific example, the polyimide polymer includes a repeating unit represented by any one of Formulas 11 to 13 below.

[Formula 11]

[Formula 12]

[Formula 13]

In the above equation,

B of Formula 11 above; At least one of B ₁ and B ₂ of Formula 12; At least one of B ₁ to B ₃ of Formula 13 is a group derived from the compound of Formula 1,

The A is a group derived from acid dianhydride,

In Formula 12, x and y are rational numbers that satisfy x+y=1,

In Formula 13, x, y, and z are rational numbers that satisfy x + y + z = 1, 0 < y + z ≤ 0.7, and 0.3 ≤ x + y < 1.

In Formulas 12 and 13, B ₁ to B ₃ may include a group derived from another diamine that is different from the diamine of Formula 1 described above. Since this diamine is the same as the additional diamine component described in the composition for producing polyamic acid described above, separate details are omitted. In addition, in the above formulas 11 to 13, A is a group derived from acid dianhydride, and since the components of this acid dianhydride are the same as the specific acid dianhydride components described in the composition for producing polyamic acid described above, further details are omitted. And in Formula 13, B ₁ to B ₃ may be the same as or different from each other, and specifically, B ₂ or B ₃ may be the same as or different from B ₁ .

The polyimide polymer according to the present invention can be produced according to conventional methods known in the art. For example, preparing a polyamic acid by reacting a diamine containing a compound represented by Formula 1 and an acid dianhydride or a derivative thereof; and dehydrating and ring-closing the polyamic acid to obtain a polyimide polymer.

The step of preparing the polyamic acid may include a polymerization reaction of an acid dianhydride or a derivative thereof, and a diamine compound, and an organic solvent may be used in the polymerization reaction. Since this organic solvent is the same as the specific organic solvent component described in the composition for producing polyamic acid described above, further details are omitted.

In addition, the step of producing a polyamic acid by reacting an acid dihydride or a derivative thereof and a diamine compound in an organic solvent involves stirring a solution in which the diamine compound is dispersed or dissolved in an organic solvent, and the acid dianhydride is added as is or dispersed or dissolved in an organic solvent. It can be performed by a method selected from the group consisting of a method of adding by dissolving, a method of adding a diamine compound to a solution in which the acid dianhydride is dispersed or dissolved in an organic solvent, and a method of alternately adding the acid dianhydride and the diamine compound. there is. In addition, when the acid dianhydride or diamine compound consists of multiple types of compounds, a method of reacting in a premixed state, a method of reacting individually sequentially, and a method of mixing individually reacted low molecular weight substances, etc. This may be performed in any manner selected.

The temperature of the polymerization reaction is not particularly limited and may be, for example, -20°C to 150°C, and preferably -5°C to 100°C.

In addition, the polymerization reaction can be carried out at any concentration of the acid dianhydride and diamine compound, but if the concentration is too low, it may be difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high, making uniform stirring difficult. It could get into trouble. Accordingly, the concentration of the acid dianhydride and the diamine compound in the reaction solution of the acid dianhydride and the diamine may be 1 to 50 mass%, preferably 5 to 30 mass%.

The step of obtaining a polyimide polymer by dehydrating and ring-closing the polyamic acid includes imidizing the polyamic acid. In one embodiment, the polyamic acid may be thermally imidized. Thermal imidization may be performed at 100°C to 400°C, preferably 120°C to 250°C. At this time, the thermal imidization process is preferably performed while removing water generated by the imidization reaction.

In another example, the polyamic acid may be catalytically imidized. Specifically, catalyst imidization can be performed by adding a basic catalyst and an acid anhydride to a solution of polyamic acid and stirring at -20°C to 250°C, preferably 0°C to 180°C.

At this time, the amount of the basic catalyst may be 0.5 to 30 mole times the amic acid group, preferably 2 to 20 mole times. Additionally, the amount of the acid anhydride may be 1 to 50 mole times the amount of the amic acid group, and preferably 3 to 30 mole times the amount of the amic acid group. For example, usable basic catalysts may be selected from the group consisting of pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, and among them, pyridine is preferred because it has an appropriate basicity to proceed with the reaction. do. Examples of usable acid anhydrides may be selected from the group consisting of acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Acetic anhydride is preferred considering ease of purification after completion of the reaction. The imidization rate by catalyst imidization can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

The imidization ratio of the polyimide that has undergone the imidization process may be 1 to 100%, and may be arbitrarily adjusted depending on the use or purpose of the polyimide.

Polyamic acid or polyimide polymer can be recovered by adding a reaction solution of polyamic acid or polyimide to a poor solvent and causing it to precipitate. At this time, the poor solvent may be selected from the group consisting of methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, etc. Additionally, the precipitate precipitated by adding it to the poor solvent may be dried under normal or reduced pressure, at room temperature, or under heating conditions.

The molecular weight of the polyamic acid and polyimide polymer prepared as described above is not particularly limited and can be appropriately adjusted within the usual range known in the art. For example, when measured by gel permeation chromatography, the weight average molecular weight (Mw) may be 5,000 to 1,000,000 g/mol, preferably 10,000 to 150,000 g/mol.

The polyamic acid and polyimide polymer of the present invention are manufactured by including a new diamine containing a functional moiety while having a fluorene-based basic skeleton in the molecule, thereby maintaining an appropriate level of mechanical properties and low dielectric constant while maintaining excellent solubility and processability. and heat resistance can be secured.

For example, the polyimide polymer may satisfy at least two of the following physical properties (i) to (iii), and preferably all of them. (i) the 5 wt% loss temperature (T _d , 5%) measured by thermogravimetric analysis (TGA) exceeds 170°C, (ii) the dielectric constant (Dk) at a frequency of 1 GHz is less than 2.7, and the dielectric loss ( Df) is less than 0.005, and (iii) moisture absorption is less than 0.8%.

The polyimide polymer of the present invention having the above-described physical properties can be applied to all fields where conventional polyimide is used, and may be, for example, films, compositions, and/or polymer coating materials for electronic devices. At this time, there is no particular limitation on the components constituting the composition, content, composition, and/or its use.

Specifically, the present invention provides a polyimide film containing the above-described polyimide polymer.

Such polyimide films can be manufactured according to common methods known in the art, and can be obtained, for example, by applying a composition containing a polyimide polymer onto a substrate and then curing it.

The application method can be used without limitation, conventional methods known in the art, such as spin coating, bar coating, dip coating, solvent casting, and slot die coating. coating) and spray coating. The polyimide layer may be coated with the polyamic acid composition at least once so that the thickness of the polyimide layer ranges from hundreds of nm to tens of μm.

Meanwhile, due to the insoluble and infusible characteristics of polyimide, existing polyimide films are manufactured by applying a relatively unstable polyamic acid composition to a substrate and then going through a two-stage heat curing process of pre-curing and main-curing. At this time, pre-curing is a process for volatilizing the solvent in a temperature range of 100 to 150°C, and main-curing is a process for polymerizing polyamic acid into polyimide through ring-closure dehydration reaction in a temperature range of 300 to 550°C. In contrast, the polyimide film according to the present invention uses a composition containing a polyimide polymer with excellent solubility and processability, and may have a difference in that the polyimide film is manufactured by applying it directly on a substrate.

The thickness of the polyimide film of the present invention formed in this way is not particularly limited and can be appropriately adjusted depending on the field to which it is applied. For example, it may be in the range of 10 to 150㎛, preferably in the range of 10 to 80㎛.

The polyimide film according to the present invention can be applied to various fields, and specifically, can be usefully applied to various technical fields that require heat resistance, excellent mechanical properties, low dielectric constant, etc. For example, flexible display substrates such as displays for organic EL devices (OLED), displays for liquid crystal devices, TFT substrates, flexible printed circuit boards, flexible OLED surface lighting substrates, and substrate materials for electronic paper, and/ Alternatively, it can be used as a protective shield. However, it is not limited to this.

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are merely examples to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

[Synthesis example: Synthesis of diamine monomer]

Synthesis Example 1. 4,4'-(2,7-dinitro- 9H -Synthesis of fluorene-9,9-diyl)diphenol

2,7-dinitro-9-fluorenone (140g, 0.52mol), phenol (500g, 5.3 mol), and sulfuric acid (26g, 0.27mol) were added to a 2L 3neck flask and stirred with a mechanical stirrer at 90°C under nitrogen. . 3-Mercaptopropionic acid (3.0 g, 0.03 mol) was added dropwise at the same temperature and stirred at the same temperature for 12 hours. After the reaction was completed, the compound was added to 3L of methanol/water (7/3) with stirring. The resulting crystals were filtered and washed 2-3 times with methanol/water. The obtained yellow crystals were recrystallized with methanol to obtain yellow crystals. The resulting crystals were filtered, washed twice with a small amount of ethanol, and vacuum dried at 70°C for 24 hours. The yield rate was 55%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 9.51 (2H, s, -OH), 8.38 (4H, m, Ar-H), 8.17 (2H, s, Ar-H), 6.98 (4H, d, Ar-H), 6.69 (4H, d, Ar-H).

Synthesis Example 2. Synthesis of 9,9-bis(4-(hexyloxy)phenyl)-9H-fluorene-2,7-diamine (DABPF1)

2-1: 9,9-bis(4-(hexyloxy)phenyl)-2,7-dinitro- 9H -Synthesis of fluorene

Add 4,4'-(2,7-dinitro- 9H -fluorene-9,9-diyl)diphenol (25.0g, 0.06mol) and potassium carbonate (24g, 0.17mol) to a 1L flask, then add dimethylform. After adding 300ml of amide, it was stirred at room temperature for 1 hour. 1-Bromohexane (21 g, 0.13 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 83%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.38 (4H, m, Ar-H), 8.18 (2H, s, Ar-H), 7.06 (4H, d, Ar-H), 6.82 (4H, d, Ar-H), 3.87 (4H, t, -CH ₂ -), 1.64 (4H, m, -CH ₂ -), 1.24-1.34 (12H, m, -CH ₂ -), 0.88 (6H, t, -CH ₃ ).

2-2: 9,9-bis(4-(hexyloxy)phenyl)- 9H -Synthesis of fluorene-2,7-diamine

9,9-bis(4-(hexyloxy)phenyl)-2,7-dinitro- 9H -fluorene (28g, 0.05mol), 5% palladium/carbon (3.2g, 1mmol) in a 500 mL round flask. After adding 300ml of 2-methoxyethanol, the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 87%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.27 (2H, t, Ar-H), 6.96 (4H, d, Ar-H), 6.79 (4H, d, Ar-H), 6.47 (4H, m, Ar-H), 4.97 (4H, -NH ₂ ), 3.89 (4H, t, -CH ₂ -), 1.67 (4H, m, -CH ₂ -), 1.29 (12H, m, -CH ₂ -), 0.81 (6H, t, -CH ₃ ).

Synthesis Example 3. 9,9-bis(4-(cyclohexylmethoxy)phenyl)- 9H -Synthesis of fluorene-2,7-diamine (DABPF2)

3-1: 9,9-bis(4-(cyclohexylmethoxy)phenyl)-2,7-dinitro- 9H -Synthesis of fluorene

Add 4,4'-(2,7-dinitro- 9H -fluorene-9,9-diyl)diphenol (25.0g, 0.06mol) and potassium carbonate (29g, 0.21mol) to a 1L flask, then add dimethylform. After adding 300ml of amide, it was stirred at room temperature for 1 hour. (Bromomethyl)cyclohexane (29 g, 0.14 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 75%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.37-8.43 (4H, m, Ar-H), 8.18 (2H, s, Ar-H), 7.07 (4H, d, Ar-H) ), 6.86 (4H, d, Ar-H), 3.79 (4H, d, -CH ₂ -), 1.62-1.77 (12H, m, -CH ₂ -) _, 1.01-1.24 (10H, m, -CH _{2 -} ) -).

3-2: 9,9-bis(4-(cyclohexylmethoxy)phenyl)- 9H -Synthesis of fluorene-2,7-diamine

9,9-bis(4-(cyclohexylmethoxy)phenyl)-2,7-dinitro- 9H -fluorene in a 500 mL round flask. (34g, 0.05mol) and 5% palladium/carbon (3.9g, 1mmol) were added, then 300ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 81%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.27 (2H, t, Ar-H), 6.96 (4H, d, Ar-H), 6.79 (4H, d, Ar-H), 6.43 (4H, m, Ar-H), 4.96 (4H, -NH ₂ ), 3.70 (4H, d, -CH ₂ -), 1.63-1.80 (12H, m, -CH ₂ -), 0.97-1.29 ( 10H, m, -CH ₂ -).

Synthesis Example 4. 9,9-bis(4-(hex-5-en-1-yloxy)phenyl)-9 H -Synthesis of fluorene-2,7-diamine (DABPF3)

3-1: 9,9-bis(4-(hex-5-en-1-yloxy)phenyl)-2,7-dinitro-9 H -Synthesis of fluorene

Add 4,4'-(2,7-dinitro- 9H -fluorene-9,9-diyl)diphenol (25.0g, 0.06mol) and potassium carbonate (24g, 0.17mol) to a 1L flask, then add dimethyl After adding 300ml of formamide, it was stirred at room temperature for 1 hour. 6-Bromo-1-hexene (20.5 g, 0.13 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 72%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.48 (2H, s, Ar-H), 8.31 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 7.18 (4H, d, Ar-H), 6.85 (4H, d, Ar-H), 5.82 (2H, m, -CH=), 5.13 (1H, d, =CH ₂ ), 4.88 (1H, d, =CH ₂ ), 4.10 (4H, t, -CH ₂ -), 1.80-2.13 (8H, m, -CH ₂ -) _, 1.57 (4H, m, -CH ₂ -).

3-2: 9,9-bis(4-(hex-5-en-1-yloxy)phenyl)-9 H -Synthesis of fluorene-2,7-diamine

99,9-bis(4-(hex-5-en-1-yloxy)phenyl)-2,7-dinitro- 9H -fluorene (34g, 0.05mol), 5% palladium in a 500 mL round flask. /After adding carbon (3.2g, 1mmol), 300ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 84%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.75 (2H, d, Ar-H), 7.18 (4H, d, Ar-H), 6.95 (2H, s, Ar-H), 6.78-6.85 (6H, m, Ar-H), 5.81 (2H, m, -CH=), 5.28 (4H, s, -NH ₂ ) 5.12 (1H, d, =CH ₂ ), 4.85 (1H, d , =CH ₂ ), 4.11 (4H, t, -CH ₂ -), 1.80-2.14 (8H, m, -CH ₂ -) _, 1.56 (4H, m, -CH ₂ -).

Synthesis Example 5. 9,9-bis(4-((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)phenyl)-9 H -Synthesis of fluorene-2,7-diamine (DABPF4)

5-1: 2,7-dinitro-9,9-bis(4-((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)phenyl)-9 H -Synthesis of fluorene

Add 4,4'-(2,7-dinitro- 9H -fluorene-9,9-diyl)diphenol (25.0g, 0.06mol) and potassium carbonate (24g, 0.17mol) to a 1L flask, then add dimethyl After adding 300ml of formamide, it was stirred at room temperature for 1 hour. 1,1,1,2,2,3,3,4,4-nonafluoro-6-iodohexane (46.6 g, 0.13 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 68%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.18 (2H, s, Ar-H), 8.31 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 7.18 (4H, d, Ar-H), 6.86 (4H, d, Ar-H), 4.05 (4H, t, -CH ₂ -), 1.92-2.05 (4H, m, -CH ₂ -) _.

5-2: 9,9-bis(4-((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)phenyl)-9 H -Synthesis of fluorene-2,7-diamine

In a 500 mL round flask, 2,7-dinitro-9,9-bis(4-((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)phenyl)- 9 H -Fluorene (20g, 0.02mol) and 5% palladium/carbon (3.2g, 1mmol) were added, then 300ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 72%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.75 (2H, d, Ar-H), 7.18 (4H, d, Ar-H), 6.96 (2H, s, Ar-H), 6.78-6.95 (6H, m, Ar-H), 5.28 (4H, s, -NH ₂ ), 4.03 (4H, t, -CH ₂ -), 1.92-2.05 (4H, m, -CH ₂ -) _.

Synthesis Example 6. 9,9-bis(4-((4-(trifluoromethyl)benzyl)oxy)phenyl)-9 H -Synthesis of fluorene-2,7-diamine (DABPF5)

6-1: 2,7-dinitro-9,9-bis(4-((4-(trifluoromethyl)benzyl)oxy)phenyl)-9 H -Synthesis of fluorene

Add 4,4'-(2,7-dinitro- 9H -fluorene-9,9-diyl)diphenol (25.0g, 0.06mol) and potassium carbonate (24g, 0.17mol) to a 1L flask, then add dimethyl After adding 300ml of formamide, it was stirred at room temperature for 1 hour. 4-(Trifluoromethyl)benzyl bromide (29.9 g, 0.13 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 74%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.48 (2H, s, Ar-H), 8.30 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 7.54 (4H, d, Ar-H), 7.10-7.18 (8H, m, Ar-H), 6.85 (4H, d, Ar-H), 5.14 (4H, s, -CH ₂ -).

6-2: 9,9-bis(4-((4-(trifluoromethyl)benzyl)oxy)phenyl)-9 H -Synthesis of fluorene-2,7-diamine

In a 500 mL round flask, 2,7-dinitro-9,9-bis(4-((4-(trifluoromethyl)benzyl)oxy)phenyl) -9H -fluorene (25g, 0.03mol), 5 After adding % palladium/carbon (3.0g, 1mmol), 300ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 72%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.75 (2H, s, Ar-H), 7.54 (4H, d, Ar-H), 7.10-7.18 (8H, m, Ar-H) ), 6.97 (2H, s, Ar-H), 6.78-6.85 (6H, m, Ar-H), 5.28 (4H, s, -NH ₂ ), 5.13 (4H, s, -CH ₂ -).

Synthesis Example 7. 9,9-bis(4-((4-(tert-butyl)benzyll)oxy)phenyl)-9 H -Synthesis of fluorene-2,7-diamine (DABPF6)

7-1: 9,9-bis(4-((4-(tert-butyl)benzyl)oxy)phenyl)-2,7-dinitro-9 H -Synthesis of fluorene

Add 4,4'-(2,7-dinitro- 9H -fluorene-9,9-diyl)diphenol (25.0g, 0.06mol) and potassium carbonate (24g, 0.17mol) to a 1L flask, then add dimethyl After adding 300ml of formamide, it was stirred at room temperature for 1 hour. 4-tert-butylbenzyl bromide (28.4 g, 0.13 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 74%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.17 (2H, s, Ar-H), 8.30 (2H, d, Ar-H), 8.15 (2H, d, Ar-H) 7.37 (4H, d, Ar-H), 7.17 (4H, d, Ar-H), 7.10 (4H, d, Ar-H), 6.85 (4H, d, Ar-H), 5.14 (4H, s, - CH ₂ -) _, 1.33 (18H, s, -CH ₃ ).

7-2: 9,9-bis(4-((4-(tert-butyl)benzyl)oxy)phenyl)-9 H -Synthesis of fluorene-2,7-diamine

In a 500 mL round flask, 9,9-bis(4-((4-(tert-butyl)benzyl)oxy)phenyl)-2,7-dinitro-9 H -fluorene (25 g, 0.03 mol), 5% After adding palladium/carbon (2.9g, 1mmol), 300ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 84%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.75 (2H, d, Ar-H), 7.38 (4H, d, Ar-H), 7.18 (4H, d, Ar-H), 7.11 (4H, d, Ar-H), 6.97 (2H, s, Ar-H), 6.85 (4H, d, Ar-H), 6.78 (2H, d, Ar-H), 5.27 (4H, s, -NH ₂ ) _, 5.14 (4H, s, -CH ₂ -) _, 1.32 (18H, s, -CH ₃ ).

Synthesis Example 8. 9,9-bis(4-((perfluorophenyl)methoxy)phenyl)-9 H -Synthesis of fluorene-2,7-diamine (DABPF7)

8-1: 2,7-dinitro-9,9-bis(4-((perfluorophenyl)methoxy)phenyl)-9 H -Synthesis of fluorene

Add 4,4'-(2,7-dinitro- 9H -fluorene-9,9-diyl)diphenol (25.0g, 0.06mol) and potassium carbonate (24g, 0.17mol) to a 1L flask, then add dimethyl After adding 300ml of formamide, it was stirred at room temperature for 1 hour. 2,3,4,5,6-pentafluorobenzyl bromide (32.6 g, 0.13 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 74%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.47 (2H, s, Ar-H), 8.31 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 7.18 (4H, d, Ar-H), 6.45 (4H, d, Ar-H), 5.16 (4H, s, -CH ₂ -).

8-2: 9,9-bis(4-((perfluorophenyl)methoxy)phenyl)-9 H -Synthesis of fluorene-2,7-diamine

2,7-dinitro-9,9-bis(4-((perfluorophenyl)methoxy)phenyl) -9H -fluorene (20g, 0.03mol), 5% palladium/carbon in a 500 mL round flask. After adding (1.7g, 1mmol), 300ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 84%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.75 (2H, d, Ar-H), 7.18 (4H, d, Ar-H), 6.95 (2H, s, Ar-H), 6.78-6.85 (6H, m, Ar-H), 5.26 (4H, s, -NH ₂ ), 5.15 (4H, s, -CH ₂ -).

Synthesis Example 9. 9,9-bis(4-((3,5-dimethylbenzyl)oxy)phenyl)-9 H -Synthesis of fluorene-2,7-diamine (DABPF8)

9-1: 9,9-bis(4-((3,5-dimethylbenzyl)oxy)phenyl)-2,7-dinitro-9 H -Synthesis of fluorene

Add 4,4'-(2,7-dinitro-9 H -fluorene-9,9-diyl)diphenol (30.0g, 0.07mol) and potassium carbonate (28.2g, 0.20mol) to a 1L flask. After adding 300ml of dimethylformamide, it was stirred at room temperature for 1 hour. 3,5-dimethylbenzyl bromide (33.9 g, 0.17 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 68%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.48 (2H, s, Ar-H), 8.31 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 7.31 (2H, s, Ar-H), 7.18 (4H, d, Ar-H), 7.09 (4H, s, Ar-H), 6.85 (4H, d, Ar-H), 5.16 (4H, s, -CH ₂ -), 2.18 (12H, s, -CH ₃ ).

9-2: 9,9-bis(4-((3,5-dimethylbenzyl)oxy)phenyl)-9 H -Synthesis of fluorene-2,7-diamine

9,9-bis(4-((3,5-dimethylbenzyl)oxy)phenyl)-2,7-dinitro-9 H -fluorene (30g, 0.04mol), 5% palladium in a 500 mL round flask. /After adding carbon (3.2g, 1mmol), 300ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 76%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.75 (2H, d, Ar-H), 7.31 (2H, s, Ar-H), 7.18 (4H, d, Ar-H), 7.09 (4H, s, Ar-H), 6.95 (2H, s, Ar-H), 6.85 (4H, d, Ar-H), 6.78 (2H, d, Ar-H), 5.28 (4H, s, -NH ₂ ), 5.16 (4H, s, -CH ₂ -), 2.18 (12H, s, -CH ₃ ).

Synthesis Example 10. 9,9-bis(4-((3,5-di-tert-butylbenzyl)oxy)phenyl)-9 H -Synthesis of fluorene-2,7-diamine (DABPF9)

10-1: 9,9-bis(4-((3,5-di-tert-butylbenzyl)oxy)phenyl)-2,7-dinitro-9 H -Synthesis of fluorene

Add 4,4'-(2,7-dinitro-9 H -fluorene-9,9-diyl)diphenol (25.0g, 0.06mol) and potassium carbonate (23.5g, 0.17mol) into a 1L flask. After adding 300ml of dimethylformamide, it was stirred at room temperature for 1 hour. 3,5-di-tert-butylbenzyl bromide (34.0 g, 0.12 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 82%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.48 (2H, s, Ar-H), 8.31 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 7.42 (2H, s, Ar-H), 7.14-7.18 (8H, m, Ar-H), 6.85 (4H, d, Ar-H), 5.16 (4H, s, -CH ₂ -), 1.31 (36H , s, -CH ₃ ).

10-2: Synthesis of 9,9-bis(4-((3,5-di-tert-butylbenzyl)oxy)phenyl)-9H-fluorene-2,7-diamine

In a 500 mL round flask, 2,7-dinitro-9,9-bis(4-((perfluorophenyl)methoxy)phenyl)-9 H -fluorene (25 g, 0.03 mol), 5% palladium/carbon. After adding (1.5 g, 1 mmol), 300 ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 64%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.75 (2H, d, Ar-H), 7.42 (2H, s, Ar-H), 7.14-7.18 (8H, m, Ar-H) ), 6.95 (2H, s, Ar-H), 6.85 (4H, d, Ar-H), 6.78 (2H, d, Ar-H), 5.28 (4H, s, -NH ₂ ), 5.16 (4H, s, -CH ₂ -), 1.31 (36H, s, -CH ₃ ).

Synthesis Example 11. Synthesis of 2,7-dinitrospiro[fluorene-9,9'-xanthene]-3',6'-diol

Add 2,7-dinitro-9-fluorenone (30g, 0.11mol), resorcinol (73.4g, 0.67 mol), and p-toluenesulfonic acid (2.0g, 0.01mol) to 200ml of toluene in a 500ml 3-neck flask. The mixture was refluxed and stirred under nitrogen for 12 hours. When the reaction was completed, it was filtered and the filtrate was washed 2-3 times with methanol. The obtained yellow crystals were recrystallized with methanol to obtain yellow crystals. The resulting crystals were filtered, washed twice with a small amount of methanol, and vacuum dried at 70°C for 24 hours. The yield rate was 49%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 9.89 (2H, s, -OH), 8.48 (2H, s, Ar-H), 8.31 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 6.97 (2H, d, Ar-H), 6.39-6.45 (4H, m, Ar-H).

Synthesis Example 12. Synthesis of 3',6'-bis(hexyloxy) spiro[fluorene-9,9'-xanthene]-2,7-diamine (DASFX1)

12-1: Synthesis of 3',6'-bis(hexyloxy)-2,7-dinitrospiro[fluorene-9,9'-xanthene]

Add 2,7-dinitrospiro[fluorene-9,9'-xanthene]-3',6'-diol (25.0g, 0.06mol) and potassium carbonate (22.8g, 0.17mol) in a 1L flask. After adding 300ml of dimethylformamide, it was stirred at room temperature for 1 hour. 1-Bromohexane (20.0 g, 0.12 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 72%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.48 (2H, s, Ar-H), 8.31 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 7.14 (2H, d, Ar-H), 6.57-6.60 (4H, m, Ar-H), 4.06 (4H, t, -CH ₂ -), 1.80 (4H, m, -CH ₂ -), 1.37- 1.47 (12H, m, -CH ₂ -), 0.88 (6H, t, -CH ₃ ).

12-2: Synthesis of 3',6'-bis(hexyloxy) spiro[fluorene-9,9'-xanthene]-2,7-diamine

In a 500 mL round flask, 3',6'-bis(hexyloxy)-2,7-dinitrospiro[fluorene-9,9'-xanthene] (25g, 0.04mol), 5% palladium/carbon ( After adding 3.1g, 1mmol), 300ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 72%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.74 (2H, d, Ar-H), 7.15 (2H, d, Ar-H), 6.94 (2H, s, Ar-H), 6.78 (2H, d, Ar-H), 6.56-6.61 (6H, m, Ar-H), 5.28 (4H, s, -NH ₂ ), 1.80 (4H, m, -CH ₂ -), 1.37-1.47 (12H, m, -CH ₂ -), 0.88 (6H, t, -CH ₃ ).

Synthesis Example 13. Synthesis of 3',6'-bis(cyclohexylmethoxy)spiro[fluorene-9,9'-xanthene]-2,7-diamine (DASFX2)

13-1: Synthesis of 3',6'-bis(cyclohexylmethoxy)-2,7-dinitrospiro[fluorene-9,9'-xanthene]

Add 2,7-dinitrospiro[fluorene-9,9'-xanthene]-3',6'-diol (25.0g, 0.06mol) and potassium carbonate (22.8g, 0.17mol) in a 1L flask. After adding 300ml of dimethylformamide, it was stirred at room temperature for 1 hour. (Bromomethyl)cyclohexane (21.4 g, 0.12 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 81%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.47 (2H, s, Ar-H), 8.30 (2H, d, Ar-H), 8.15 (2H, d, Ar-H), 7.13 (2H, d, Ar-H), 6.55-6.61 (4H, m, Ar-H), 3.86 (4H, d, -CH ₂ -), 1.94 (2H, m, -CH-), 1.37-1.61 (20H, m, -CH ₂ -).

13-2: Synthesis of 3',6'-bis(cyclohexylmethoxy)spiro[fluorene-9,9'-xanthene]-2,7-diamine

3',6'-bis(cyclohexylmethoxy)-2,7-dinitrospiro[fluorene-9,9'-xanthene] in a 500 mL round flask. (25g, 0.04mol) and 5% palladium/carbon (3.0g, 1mmol) were added, then 300ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 87%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.76 (2H, d, Ar-H), 7.14 (2H, d, Ar-H), 6.96 (2H, s, Ar-H), 6.78 (2H, d, Ar-H), 6.57-6.61 (6H, m, Ar-H), 5.27 (4H, -NH ₂ ), 3.86 (4H, m, -CH ₂ -), 1.94 (2H, m , -CH-), 1.38-1.63 (20H, m, -CH ₃ -).

Synthesis Example 14. Synthesis of 3',6'-bis(hex-5-en-1-yloxy)spiro[fluorene-9,9'-xanthene]-2,7-diamine (DASFX3)

14-1: Synthesis of 3',6'-bis(hex-5-en-1-yloxy)-2,7-dinitrospiro[fluorene-9,9'-xanthene]

Add 2,7-dinitrospiro[fluorene-9,9'-xanthene]-3',6'-diol (25.0g, 0.06mol) and potassium carbonate (22.8g, 0.17mol) in a 1L flask. After adding 300ml of dimethylformamide, it was stirred at room temperature for 1 hour. 6-Bromo-1-hexene (19.7 g, 0.12 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 64%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.48 (2H, s, Ar-H), 8.32 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 7.15 (2H, d, Ar-H), 6.57-6.60 (4H, m, Ar-H), 5.82 (2H, m, -=CH ₂ -), 5.13 (1H, d, =CH ₂ ), 4.88 ( 1H, m, =CH ₂ ), 4.10 (4H, t, -CH ₂ -), 2.13 (4H, m, -CH ₂ -), 1.80 (4H, m, -CH ₂ -), 1.57 (4H, m , -CH ₂ -).

14-2: Synthesis of 3',6'-bis(hex-5-en-1-yloxy)spiro[fluorene-9,9'-xanthene]-2,7-diamine

3',6'-bis(hex-5-en-1-yloxy)-2,7-dinitrospiro[fluorene-9,9'-xanthene] (30g, 0.05mol) in a 500 mL round flask. , 5% palladium/carbon (3.2g, 1mmol) was added, then 300ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 81%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.75 (2H, d, Ar-H), 7.14 (2H, d, Ar-H), 6.94 (2H, s, Ar-H), 6.78 (2H, d, Ar-H), 6.57-6.61 (4H, m, Ar-H), 5.82 (2H, m, -=CH ₂ -), 5.27 (4H, s, -NH ₂ ), 5.12 ( 1H, d, =CH ₂ ), 4.86 (1H, m, =CH ₂ ), 4.11 (4H, t, -CH ₂ -), 2.12 (4H, m, -CH ₂ -), 1.82 (4H, m, -CH ₂ -), 1.56 (4H, m, -CH ₂ -).

Synthesis Example 15. 3',6'-bis((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)spiro[fluorene-9,9'-xanthene ]-2,7-diamine synthesis (DASFX4)

15-1: 2,7-dinitro-3',6'-bis((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)spiro[fluorene Synthesis of -9,9'-xanthene]

Add 2,7-dinitrospiro[fluorene-9,9'-xanthene]-3',6'-diol (25.0g, 0.06mol) and potassium carbonate (24g, 0.17mol) to a 1L flask, then add dimethyl After adding 300ml of formamide, it was stirred at room temperature for 1 hour. 1,1,1,2,2,3,3,4,4-nonafluoro-6-iodohexane (45.3 g, 0.12 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 63%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.47 (2H, s, Ar-H), 8.32 (2H, d, Ar-H), 8.15 (2H, d, Ar-H), 7.15 (2H, d, Ar-H), 6.57-6.60 (4H, m, Ar-H), 4.05 (4H, t, -CH ₂ -), 2.01 (4H, m, -CH ₂ -).

15-2: 3',6'-bis((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)spiro[fluorene-9,9'-xanthene ]-2,7-diamine

2,7-dinitro-3',6'-bis((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)spiro[fluorene] in a 500 mL round flask. -9,9'-xanthene] (25g, 0.02mol) and 5% palladium/carbon (1.7g, 1mmol) were added, then 300ml of 2-methoxyethanol was added, and the reactor was replaced with hydrogen using a hydrogen balloon. did. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 86%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.73 (2H, d, Ar-H), 7.13 (2H, d, Ar-H), 6.96 (2H, s, Ar-H), 6.77 (2H, d, Ar-H), 6.56-6.60 (4H, m, Ar-H), 5.29 (4H, s, -NH ₂ ), 4.05 (4H, t, -CH ₂ -), 2.01 (4H , m, -CH ₂ -).

Synthesis Example 16. Synthesis of 3',6'-bis((4-(trifluoromethyl)benzyl)oxy)spiro[fluorene-9,9'-xanthene]-2,7-diamine (DASFX5)

16-1: Synthesis of 2,7-dinitro-3',6'-bis((4-(trifluoromethyl)benzyl)oxy)spiro[fluorene-9,9'-xanthene]

Add 2,7-dinitrospiro[fluorene-9,9'-xanthene]-3',6'-diol (25.0g, 0.06mol) and potassium carbonate (22.8g, 0.17mol) in a 1L flask. After adding 300ml of dimethylformamide, it was stirred at room temperature for 1 hour. 4-(Trifluoromethyl)benzyl bromide (28.9, 0.12 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 81%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.48 (2H, s, Ar-H), 8.32 (2H, d, Ar-H), 8.15 (2H, d, Ar-H), 7.54 (4H, d, Ar-H), 7.11-7.14 (6H, m, Ar-H), 6.57-6.60 (4H, m, Ar-H), 5.14 (4H, s, -CH ₂ -).

16-2: Synthesis of 3',6'-bis((4-(trifluoromethyl)benzyl)oxy)spiro[fluorene-9,9'-xanthene]-2,7-diamine

In a 500 mL round flask, 2,7-dinitro-3',6'-bis((4-(trifluoromethyl)benzyl)oxy)spiro[fluorene-9,9'-xanthene] (25g, 0.03 mol), 5% palladium/carbon (2.9g, 1mmol) was added, 300ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 78%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.75 (2H, d, Ar-H), 7.54 (4H, d, Ar-H), 7.11-7.14 (6H, m, Ar-H) ), 6.94 (2H, s, Ar-H), 6.77 (2H, d, Ar-H), 6.56-6.61 (4H, m, Ar-H), 5.27 (4H, s, -NH ₂ ), 5.14 ( 4H, s, -CH ₂ -).

Synthesis Example 17. Synthesis of 3',6'-bis((4-(tert-butyl)benzyl)oxy)spiro[fluorene-9,9'-xanthene]-2,7-diamine (DASFX6)

17-1: Synthesis of 3',6'-bis((4-(tert-butyl)benzyl)oxy)-2,7-dinitrospiro[fluorene-9,9'-xanthene]

Add 2,7-dinitrospiro[fluorene-9,9'-xanthene]-3',6'-diol (30.0g, 0.07mol) and potassium carbonate (27.4g, 0.2mol) in a 1L flask. After adding 300ml of dimethylformamide, it was stirred at room temperature for 1 hour. 4-tert-butylbenzyl bromide (33.0, 0.15 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 75%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.48 (2H, s, Ar-H), 8.31 (2H, d, Ar-H), 8.15 (2H, d, Ar-H), 7.37 (4H, d, Ar-H), 7.10-7.14 (6H, m, Ar-H), 6.57-6.61 (4H, m, Ar-H), 5.14 (4H, s, -CH ₂ -), 1.33 (18H, s, -CH ₃ ).

17-2: Synthesis of 3',6'-bis((4-(tert-butyl)benzyl)oxy)spiro[fluorene-9,9'-xanthene]-2,7-diamine

3',6'-bis((4-(tert-butyl)benzyl)oxy)-2,7-dinitrospiro[fluorene-9,9'-xanthene] (25g, 0.04mol) in a 500 mL round flask. ), 5% palladium/carbon (3.0g, 1mmol) was added, 300ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 74%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.75 (2H, d, Ar-H), 7.37 (4H, d, Ar-H), 7.10-7.14 (6H, m, Ar-H) ), 6.94 (2H, s, Ar-H), 6.76 (2H, d, Ar-H), 6.54-6.60 (4H, m, Ar-H), 5.28 (4H, s, -NH ₂ ), 5.14 ( 4H, s, -CH ₂ -), 1.32 (18H, s, -CH ₃ ).

Synthesis Example 18. Synthesis of 3',6'-bis((perfluorophenyl)methoxy)spiro[fluorene-9,9'-xanthene]-2,7-diamine (DASFX7)

18-1: Synthesis of 2,7-dinitro-3',6'-bis((perfluorophenyl)methoxy)spiro[fluorene-9,9'-xanthene]

Add 2,7-dinitrospiro[fluorene-9,9'-xanthene]-3',6'-diol (25.0g, 0.06mol) and potassium carbonate (22.8g, 0.17mol) in a 1L flask. After adding 300ml of dimethylformamide, it was stirred at room temperature for 1 hour. 2,3,4,5,6-pentafluorobenzyl bromide (31.6 g, 0.12 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 69%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.46 (2H, s, Ar-H), 8.30 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 7.14 (2H, d, Ar-H), 6.56-6.61 (4H, m, Ar-H), 5.16 (4H, s, -CH ₂ -).

18-2: Synthesis of 3',6'-bis((perfluorophenyl)methoxy)spiro[fluorene-9,9'-xanthene]-2,7-diamine

In a 500 mL round flask, 2,7-dinitro-3',6'-bis((perfluorophenyl)methoxy)spiro[fluorene-9,9'-xanthene] (20g, 0.03mol), 5 After adding % palladium/carbon (1.6g, 1mmol), 300ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 82%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.76 (2H, d, Ar-H), 7.36 (2H, d, Ar-H), 6.95 (2H, s, Ar-H), 6.78 (2H, d, Ar-H), 6.57-6.61 (4H, m, Ar-H), 5.27 (4H, s, -NH ₂ ), 5.15 (4H, s, -CH ₂ -).

Synthesis Example 19. Synthesis of 3',6'-bis((3,5-dimethylbenzyl)oxy)spiro[fluorene-9,9'-xanthene]-2,7-diamine (DASFX8)

19-1: Synthesis of 3',6'-bis((3,5-dimethylbenzyl)oxy)-2,7-dinitrospiro[fluorene-9,9'-xanthene]

Add 2,7-dinitrospiro[fluorene-9,9'-xanthene]-3',6'-diol (30.0g, 0.07mol) and potassium carbonate (27.64g, 0.20mol) in a 1L flask. After adding 300ml of dimethylformamide, it was stirred at room temperature for 1 hour. 3,5-dimethylbenzyl bromide (27.6 g, 0.14 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 72%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.48 (2H, s, Ar-H), 8.31 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 7.31 (2H, s, Ar-H), 7.14 (2H, d, Ar-H), 7.09 (4H, s, Ar-H), 6.57-6.60 (4H, m, Ar-H), 5.16 (4H, s, -CH ₂ -), 2.18 (12H, s, -CH ₃ ).

19-2: Synthesis of 3',6'-bis((3,5-dimethylbenzyl)oxy)spiro[fluorene-9,9'-xanthene]-2,7-diamine

In a 500 mL round flask, 2,7-dinitro-3',6'-bis((perfluorophenyl)methoxy)spiro[fluorene-9,9'-xanthene] (30g, 0.04mol), 5 After adding % palladium/carbon (3.6g, 1mmol), 300ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 75%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.75 (2H, d, Ar-H), 7.31 (2H, s, Ar-H), 6.94-7.09 (6H, m, Ar-H) ), 6.95 (2H, s, Ar-H), 6.78 (2H, d, Ar-H), 6.57-6.60 (4H, m, Ar-H), 5.28 (4H, s, -NH ₂ ), 5.16 ( 4H, s, -CH ₂ -), 2.18 (12H, s, -CH ₃ ).

Synthesis Example 20. Synthesis of 3',6'-bis((3,5-di-tert-butylbenzyl)oxy)spiro[fluorene-9,9'-xanthene]-2,7-diamine (DASFX9)

20-1: 3',6'- Synthesis of bis((3,5-di-tert-butylbenzyl)oxy)-2,7-dinitrospiro[fluorene-9,9'-xanthene]

Add 2,7-dinitrospiro[fluorene-9,9'-xanthene]-3',6'-diol (30.0g, 0.07mol) and potassium carbonate (27.4g, 0.20mol) in a 1L flask. After adding 300ml of dimethylformamide, it was stirred at room temperature for 1 hour. 3,5-di-tert-butylbenzyl bromide (41.0 g, 0.14 mol) was added dropwise, the temperature was raised to 80°C, and the mixture was stirred for 12 hours. When the reaction is completed, the solid is removed by filtration, neutralized with 3N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed 2-3 times with distilled water, concentrated under reduced pressure, and dried under vacuum at 70°C for 24 hours. The yield rate was 84%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.48 (2H, s, Ar-H), 8.31 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 7.42 (2H, s, Ar-H), 7.14 (6H, m, Ar-H), 6.57-6.60 4, m, Ar-H), 5.16 (4H, s, -CH ₂ -), 1.31 (36H, s, -CH ₃ ).

20-2: Synthesis of 3',6'-bis((3,5-di-tert-butylbenzyl)oxy)spiro[fluorene-9,9'-xanthene]-2,7-diamine

In a 500 mL round flask, 2,7-dinitro-3',6'-bis((perfluorophenyl)methoxy)spiro[fluorene-9,9'-xanthene] (25g, 0.03mol), 5 After adding % palladium/carbon (2.5 g, 1 mmol), 300 ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 67%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.75 (2H, d, Ar-H), 7.42 (2H, s, Ar-H), 7.14 (6H, m, Ar-H), 6.95 (2H, s, Ar-H), 6.78 (2H, d, Ar-H), 6.57-6.60 (4H, m, Ar-H), 5.28 (4H, s, -NH ₂ ), 5.16 (4H, s, -CH ₂ -), 1.31 (36H, s, -CH ₃ ).

Synthesis Example 21. Synthesis of 9,9-diphenyl-9H-fluorene-2,7-diamine (Comparative Example 2)

21-1: Synthesis of 4,4'-(2,7-dinitro-9H-fluorene-9,9-diyl)dianiline

2,7-dinitro-9-fluorenone (30 g, 0.11 mol), anilinium chloride (43.0 g, 0.33 mol), and 300 ml of aniline were added to a 1 L flask and stirred at 150°C under nitrogen for 4 hours. After cooling to room temperature, it was added to 50 ml of 10 wt% sodium hydroxide aqueous solution and stirred, and the resulting crystals were recrystallized in ethanol. The yield rate was 54%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.48 (2H, s, Ar-H), 8.31 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 6.73 (4H, d, Ar-H), 6.44 (4H, d, Ar-H), 4.91 (4H, s, -NH ₂ ).

21-2: 2,7-dinitro-9,9-diphenyl-9 H -Synthesis of fluorene

In a 100ml flask, add 4'-(2,7-dinitro-9H-fluorene-9,9-diyl)dianiline (30.0g, 0.07mol) and 300mL dichloromethane and raise the temperature to 40°C under nitrogen. Nitrous acid Amyl (32.0g, 0.27mol) was slowly added dropwise, stirred at the same temperature for 2 hours, and then cooled. The undissolved solid is filtered out, and the filtrate is washed with 1M hydrochloric acid aqueous solution and 10wt% sodium hydroxide aqueous solution in a separatory flask. The organic layer is concentrated, dried, and recrystallized from dichloromethane/petronium. The yield rate is 24%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 8.48 (2H, s, Ar-H), 8.31 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 7.26 (4H, d, Ar-H), 7.18 (2H, t, Ar-H), 7.10 (4H, d, Ar-H).

21-3: Synthesis of 9,9-diphenyl-9H-fluorene-2,7-diamine

In a 500 mL round flask: Add 2,7-dinitro-9,9-diphenyl-9H-fluorene (25g, 0.07mol), 5% palladium/carbon (3.2g, 1mmol), and then add 2-methoxyethanol. 300 ml was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. The stirring speed of the mechanical stirrer was set to 500 rpm, and if the volume of the hydrogen balloon did not decrease after 12 hours of reaction, the catalyst was removed through silica/celite filtration, concentrated under reduced pressure, and purified by silica column with ethyl acetate/hexane. The yield rate was 84%.

¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 7.75 (2H, d, Ar-H), 7.26 (4H, d, Ar-H), 7.18 (2H, t, Ar-H), 7.10 (4H, d, Ar-H), 6.95 (2H, s, Ar-H), 6.78 (2H, d, Ar-H), 5.28 (4H, s, -NH ₂ ).

[Example 1: Preparation of polyamic acid composition and polyimide]

A polyamic acid composition and a polyimide film were prepared using the diamine monomer DABPF1 synthesized in Synthesis Example 2.

Specifically, 8.00 mmol of diamine monomer (DABPF 1), 2.50 g (8.00 mmol) of ODPA, and 3.75 g of isoquinoline were dissolved in 70 g of meta-cresol and then incubated at 70°C for 2 hours and 150°C for 3 hours under a nitrogen atmosphere. It was stirred for a while. After the reaction was completed, the temperature was cooled to room temperature and a polyamic acid composition in the form of a viscous solution was obtained. This solution was precipitated in methanol, filtered, and the precipitate was washed several times with water and methanol. Afterwards, it was dried under reduced pressure at a temperature of 80°C to obtain a polyamic acid polymer.

Some of the synthesized polyamic acid polymers were made into a 10% by weight DMAc solution and applied to a glass plate. The solvent was removed under vacuum conditions and a temperature of 200°C, and an imide ring closure reaction (Imidization) was performed to produce the polyimide film of Example 1. was manufactured.

[Examples 2 to 17]

The polyamic acid composition and polyimide film of Examples 2 to 20 were prepared in the same manner as Example 1, except that the diamine monomers listed in Table 1 below were used instead of the diamine monomer (DABPF1) prepared in Synthesis Example 2. Manufactured. At this time, the mole percentage in Table 1 below represents the mole ratio of each monomer constituting diamine and acid dianhydride.

[Comparative Example 1]

The polyamic acid composition and polyimide film of Comparative Example 1 were prepared in the same manner as Example 1, except that 4,4'-ODA was used instead of the diamine monomer (DABPF1) prepared in Synthesis Example 2.

Specifically, 8.00 mmol of 4,4′-Oxydianiline, 2.50 g (8.00 mmol) of ODPA, and 3.75 g of isoquinoline were dissolved in 70 g of meta-cresol and stirred at 70°C for 2 hours and 150°C for 3 hours in a nitrogen atmosphere. . After the reaction was completed, the temperature was cooled to room temperature and a viscous solution-type polyamic acid composition was obtained. This solution was precipitated in methanol, filtered, and the precipitate was washed several times with water and methanol. Afterwards, it was dried under reduced pressure at a temperature of 80°C to obtain a polyamic acid polymer.

Some of the synthesized polyamic acid polymers were made into a 10% by weight DMAc solution and applied to a glass plate. The solvent was removed under vacuum conditions and a temperature of 200°C, and an imide ring closure reaction (Imidization) was performed to produce the polyimide film of Comparative Example 1. was manufactured.

[Comparative Example 2]

The above comparison, except that 9,9-diphenyl-9 H -fluorene-2,7-diamine prepared in Synthesis Example 21 was used instead of the diamine monomer (4,4'-ODA) used in Comparative Example 1. The polyamic acid composition and polyimide film of Comparative Example 2 were prepared in the same manner as in Example 1.

[Experimental example. Physical property evaluation]

The physical properties of the polyimide films prepared in Examples 1 to 17 and Comparative Examples 1 to 2 were evaluated in the following manner, and the results are shown in Table 1 below.

The specific measurement method for each physical property is as follows, and the judgment criteria are as shown in Table 2 below.

For the film obtained in Example 2, the film forming characteristics and the thickness of the final film obtained were measured, and mechanical properties, thermal properties, and dielectric constant were evaluated, and the results are shown in Table 1 below. The specific measurement method is as follows.

(1) Solubility (polyimide)

While maintaining the temperature at 20°C, small amounts of the sample were added dropwise to 100 g of the solvent being stirred until it no longer dissolved and left for 23 hours. Solubility was measured according to Equation 1 below.

[Equation 1]

Solubility (%) = dissolved sample amount (g)/solvent (100g) ×100

(2) Film thickness

The thickness of the film was measured using a thickness measuring device (KG601B Electric Micro meter (Anritsu)).

(3) Heat resistance

It was measured using a thermogravimetric analyzer (TGA) under a nitrogen atmosphere. At this time, the heat resistance measurement range was 25 to 700°C, and the temperature increase rate was 10°C/min. To remove moisture absorbed from the atmosphere, the weight was calculated as 100% after constant temperature at 105°C for 30 minutes, and the temperature at which 5% weight loss occurs (T _{d, 5%} ) was measured.

(4) Dielectric constant

The size of the specimen was 5 × 5 cm or more, and the thickness of the specimen was 80㎛. Each specimen was placed into the resonator and measured at room temperature/pressure.

(5) Dielectric loss

The size of the specimen was 5 × 5 cm or more, and the thickness of the specimen was 80㎛. Each specimen was placed in the resonator and measured at room temperature/pressure.

(6) Moisture absorption rate

The prepared polyimide film was made into a specimen with a size of 10 x 10 mm, and the initial weight (W1) was measured. Next, each specimen was left in a purified water bath for 24 hours under the conditions of temperature 25 ± 2℃ and relative humidity 30% to absorb moisture. Then, the specimen was taken out, wiped with a cloth, and the weight (W2) was measured after moisture absorption treatment. The moisture absorption rate was calculated by substituting the measured values into Equation 2 below.

[Equation 2]

Moisture absorption rate (%) = [(W2-W1)/W1] ×100

Composition (mol%) thickness

(μm) Properties diamine acid dianhydride Td _5% (℃) Dielectric constant (@1GHz) moisture absorption rate
(%) solubility powder film permittivity
(Dk) oil field loss
(Df) Example 1 DABPF1 ODPA 80 ++ ++ ++ + ++ ++ Example 2 DABPF2 ODPA 80 ++ ++ ++ + ++ ++ Example 3 DABPF3 ODPA 80 + + ++ ++ ++ ++ Example 4 DABPF4 ODPA 80 + + ++ ++ ++ ++ Example 5 DABPF5 ODPA 80 ++ ++ ++ ++ ++ ++ Example 6 DABPF6 ODPA 80 ++ ++ ++ + ++ + Example 7 DABPF7 ODPA 80 ++ ++ ++ ++ ++ ++ Example 8 DABPF8 ODPA 80 ++ ++ ++ ++ ++ + Example 8 DABPF9 ODPA 80 ++ ++ ++ ++ ++ + Example 9 DASFX1 ODPA 80 + + ++ + ++ ++ Example 10 DASFX2 ODPA 80 ++ ++ ++ + ++ ++ Example 11 DASFX3 ODPA 80 + + ++ ++ ++ ++ Example 12 DASFX4 ODPA 80 + + ++ ++ ++ ++ Example 13 DASFX5 ODPA 80 ++ ++ ++ ++ ++ ++ Example 14 DASFX6 ODPA 80 ++ ++ ++ + ++ + Example 15 DASFX7 ODPA 80 ++ ++ ++ ++ ++ ++ Example 16 DASFX8 ODPA 80 ++ ++ ++ ++ ++ + Example 17 DASFX9 ODPA 80 ++ ++ ++ ++ ++ + Comparative Example 1 O.D.A. ODPA 80 + + + ++ ++ ++ Comparative example 2 Synthesis Example 21 ODPA 80 ++ ++ ++ + + +

Properties Judgment criteria Heat resistance (Td _5%) powder + (>150℃), ++ (>170℃) Film (@150 μm) + (> 300℃), ++ (> 400℃) permittivity permittivity + (< 3.5), ++ (< 2.7) oil field loss + (< 0.005), ++ (< 0.004) moisture absorption rate + (<1.0), ++ (<0.8) solubility + NMP, DMF, THF / ++ MC, CHCl ₃ , AcOH

As shown in Table 1, it was found that the polyimide film containing the novel diamine monomer according to the present invention exhibits low dielectric constant and low moisture absorption, making it possible to produce a film with excellent processability and heat resistance.

In the above, preferred embodiments of the present invention have been exemplified, but the present invention is not limited to the specific preferred embodiments described above, and is within the scope of common knowledge in the technical field to which the invention pertains without departing from the gist of the present invention as claimed in the claims. Any person who has a can make various modifications, and such modifications are within the scope of the claims.

Claims (16)

Compound represented by Formula 1:
[Formula 1]

In the above equation,
X and Y are the same or different from each other, and are each independently a single bond or an alkyl group of C ₁ to C ₁₀ ,
Z is selected from the group consisting of O, S and NR ₃ ,
m and n are each independently 0 or 1, provided that if m+n ≤1, Z is not included,
R ₁ to R ₃ are the same or different from each other, and are each independently hydrogen, halogen, nitro group, C ₁ to C ₁₀ alkyl group, C ₂ to C ₂₀ alkenyl group, C ₁ to C ₂₀ alkyloxy group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ C ₂₀ aryloxy group, heterocyclic group with 5 to 20 nuclear atoms, heterocyclic oxy group with 5 to 20 nuclear atoms, alkylsulfanyl group with C ₁ ~ C ₂₀ , C ₆ ~ C ₂₀ arylsulfanyl group, and C ₁ ~ C ₂₀ acyl group, provided that at least one of the plurality of R ₁ and R ₂ is an alkyloxy group, an aryloxy group, and a heterocyclic oxy group. Contains any one of
a and b are each independently integers from 1 to 4,
The alkyl group, alkenyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, and acyl group of R ₁ to R ₃ are each independently hydrogen, deuterium, or halogen. , nitro group, epoxy group, cyano group, C ₁ to C ₁₀ alkyl group, C ₂ to C ₁₀ alkenyl group, C ₂ to C ₁₀ alkynyl group, C ₃ to C ₁₀ cycloalkyl group, nuclear atoms 3 to 10 It may be substituted with one or more substituents selected from the group consisting of a heterocycloalkyl group, a C ₆ to C ₁₀ aryl group, a heteroaryl group with 5 to 10 nuclear atoms, and a C ₁ to C ₁₀ alkyloxy group, At this time, when the substituents are plural, they may be the same or different from each other. According to paragraph 1,
The compound of Formula 1 is a compound represented by any one of the following Formulas 2 to 7:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In the above equation,
R ₁ , R ₂ , R ₃ , a and b are each as defined in clause 1. According to paragraph 1,
The compound represented by Formula 1 is a compound represented by any one of the following Formulas 2A to 7A:
[Formula 2A]

[Formula 2B]

[Formula 3A]

[Formula 4A]

[Formula 5A]

[Formula 6A]

[Formula 7A]

In the above equation,
R ₁ to R ₃ are each as defined in claim 1. According to paragraph 1,
R ₁ and R ₂ are the same as or different from each other, and each independently represents hydrogen, an alkyloxy group of C ₁ to C ₂₀ , an aryloxy group of C ₆ to C ₂₀ , and a heterocyclic oxy group of 5 to 20 nuclear atoms. is selected from a group consisting of
a and b are each independently 1 or 2,
The alkyloxy group, aryloxy group and heterocyclic oxy group are each independently halogen, CF ₃ , nitro group, cyano group, C ₁ to C ₁₀ alkyl group, C ₂ to C ₁₀ alkenyl group, C ₃ to C ₁₀ A compound substituted or unsubstituted with one or more substituents selected from the group consisting of a cycloalkyl group, a C ₆ to C ₁₀ aryl group, and a heteroaryl group having 5 to 10 nuclear atoms. According to paragraph 1,
The compound represented by Formula 1 is a compound selected from the group of compounds represented by the following formula.

A diamine containing the compound of formula (1) according to any one of claims 1 to 5; and
acid dianhydride;
A composition for producing polyamic acid containing. According to clause 6,
A composition for producing polyamic acid, wherein the compound of Formula 1 is contained in the range of 1 to 100 mol% based on 100 mol% of total diamine. According to clause 6,
The diamine is different from the compound of Formula 1 and includes fluorinated primary diamine; A composition for producing a polyamic acid further comprising at least one member selected from the group consisting of sulfone-based secondary diamine, hydroxy-based tertiary diamine, ether-based quaternary diamine, and cycloaliphatic fifth diamine. According to clause 6,
A composition for producing a polyamic acid, wherein the acid dianhydride includes at least one selected from the group consisting of fluorinated aromatic primary acid dianhydride, cycloaliphatic secondary acid dianhydride, and non-fluorinated aromatic tertiary acid dianhydride. According to clause 6,
The acid dianhydride includes tetracarboxylic dianhydride, pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (OPDA), and 4,4'-hexafluoroisopropyldenediphthalic dianhydride ( 6FDA), cyclohexane 1,2,4,5-tetracarboxylic dianhydride (HPMDA), 2'-[bicyclo [2.2.1] heptane-2,1'-cyclopentane-3', 2"bi At least one of cyclo [2.2.1] heptane]-5,6, 5'6"-tetracarboxylic dianhydride (CpODA), and cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA) A composition for producing polyamic acid containing at least one. A polyamic acid formed from the composition for producing polyamic acid of claim 6. According to clause 11,
The polyamic acid is a polyamic acid containing a repeating unit represented by any one of the following formulas 8 to 10:
[Formula 8]

[Formula 9]

[Formula 10]

In the above equation,
B of Formula 8; At least one of B ₁ and B ₂ of Formula 9; At least one of B ₁ to B ₃ of Formula 10 is a group derived from the compound of Formula 1,
The A is a group derived from acid dianhydride,
In Formula 9, x and y are rational numbers that satisfy x+y=1,
In Formula 10, x, y, and z are rational numbers that satisfy x + y + z = 1, 0 < y + z ≤ 0.7, and 0.3 ≤ x + y < 1. A polyimide polymer formed by imidizing the polyamic acid of claim 11. According to clause 13,
The polyimide polymer includes a repeating unit represented by any one of the following formulas 11 to 13.
[Formula 11]

[Formula 12]

[Formula 13]

In the above equation,
B of Formula 11 above; At least one of B ₁ and B ₂ of Formula 12; At least one of B ₁ to B ₃ of Formula 13 is a group derived from the compound of Formula 1,
The A is a group derived from acid dianhydride,
In Formula 12, x and y are rational numbers that satisfy x+y=1,
In Formula 13, x, y, and z are rational numbers that satisfy x + y + z = 1, 0 < y + z ≤ 0.7, and 0.3 ≤ x + y < 1. According to clause 13,
A polyimide polymer satisfying at least two of the following physical properties (i) to (iii):
(i) the 5% weight loss temperature (T _d , 5%) measured by thermogravimetric analysis (TGA) exceeds 170°C;
(ii) at a frequency of 1 GHz, the dielectric constant (Dk) is less than 2.7 and the dielectric loss (Df) is less than 0.005;
(iii) Moisture absorption rate is less than 0.8%. A polyimide film comprising the polyimide polymer of claim 13.