High refractive index material having various functional groups and its manufacturing method

Abstract

To provide monomers for optical resins for manufacturing optical resins with a high refractive index that can be used as an alternative to glass.SOLUTION: There is provided a new compound with a high refractive index of 1.7 or more, which has a fluorene and xanthene-based complex cardo structure expressed by the following formula. The compound of this invention can be applied to the manufacture of high refractive index optical resins. The fluorene and xanthene-based complex cardo structure of this compound has a high glass transition temperature (Tg) with the mobility of the molecular chain suppressed to the greatest extent possible. Therefore, it can also be used widely in the manufacture of high-heat-resistant resins that require thermal stability.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention was made under the support of the Ministry of Trade, Industry and Energy of the Republic of Korea under Project ID No. 1415179963 and Project No. 20013223, the research management specialist for this project is the Korea Institute for Industrial Technology Assessment and Management, the research project name is "Materials and Components Technology Development", the research topic name is "Development of thermoplastic optical resin with a refractive index of 1.65 or more and a light-blocking agent with an optical density of 6.5 or more for optical lenses of smart devices", the project execution organization is Kuppo Chemical Co., Ltd., and the research period is from 2024.01.01 to 2024.12.31.

[0002] Furthermore, this invention was made under the support of the Ministry of Trade, Industry and Energy of the Republic of Korea under project specific number 1415178757 and project number 20013794, the research management specialist organization for this project is the Korea Institute for Industrial Technology Assessment and Management, the research project name is "Demonstration Project for Fostering Industrial Technology Hub Centers", the research topic name is "Composite Material Simultaneous Design Industrial Technology Hub Center", the project execution organization name is the Seonggyuk University Industry-Academia Cooperation Foundation, and the research period is from 2024.01.01 to 2024.12.31.

[0003] The present invention claims priority to Korean Patent Application No. 10-2023-0072497, filed on June 5, 2023, the disclosure of which is incorporated herein by reference.

[0004] The present invention relates to a high refractive index material having various functional groups and a method for producing the same. More specifically, the compound has a complex cardo structure of fluorene and xanthene, and relates to a high refractive index monomer that can be used for optical resins that require a refractive index of 1.7 or higher. [Background technology]

[0005] Conventionally, refractive index-enhancing monomers such as those shown below have been used to manufacture optical resins with high refractive indexes that can replace glass. However, most monomers have a refractive index of around 1.3 to 1.6, which limits their applicability to applications requiring a high refractive index.

[0006] [ka]

[0007] Therefore, there is a need to develop new compounds with higher refractive indexes than existing commercially available optical resin monomers. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Korean Patent No. 10-2418855 Summary of the Invention [Problem to be solved by the invention]

[0009] The present inventors have made extensive research efforts to develop high refractive index materials having various functional groups. As a result, they have designed a composite cardo structure of fluorene, which has a high molar refractive index and a low birefringence, and xanthene, which has a high molar refractive index, and by introducing a heteroatom that provides synergy in improving the refractive index, they have developed a novel monomer compound with a higher refractive index than existing commercially available materials. Therefore, an object of the present invention is to provide a compound having the structure of the following chemical formula 1 and a method for preparing the same:

[0010] [ka]

[0011] where X and R 1a , R 1b , R 2a , and R 2b represents a substituent; X is O, S, or SO; k1 and k2 independently represent an integer of 0 to 4; and p1 and p2 independently represent an integer of 0 to 4 (provided that p1+p2 is an integer of 1 to 8). [Means for solving the problem]

[0012] The present inventors have made extensive research efforts to develop high refractive index materials having various functional groups, and as a result, have prepared a compound having the structure of the following Chemical Formula 1, thereby completing the present invention.

[0013] According to one aspect of the present invention, there is provided a compound having the chemical structure of Formula 1:

[0014] [ka]

[0015] where X and R 1a , R 1b , R 2a , and R 2b represents a substituent; X is O, S, or SO; k1 and k2 independently represent an integer of 0 to 4; and p1 and p2 independently represent an integer of 0 to 4 (provided that p1+p2 is an integer of 1 to 8).

[0016] R 2a , and R 2b are independently H, linear or branched C 1-10 Alkyl, linear or branched C 1-10 Alkoxy, C 1-10 Hydroxyalkoxy, C 1-10 Alkoxy (C 1-10 ) Alkoxy, Phenyl, C 1-10 Alkoxyphenyl, halogen, amino, C 1-5 Haloalkyl, C 1-5 Alkylamino, C 1-5 Dialkylamino, arylamino, diarylamine, aryl C 1-5 It represents an alkylamino or cyclic amino group.

[0017] On the other hand, this compound has a complex cardo structure of fluorene and xanthene, and is a high refractive index monomer that can be used for optical resins that require a refractive index of 1.7 or more.

[0018] As used herein, the term "cardo compound" refers to a compound having a molecular backbone with cyclic side groups. Cardo compounds have a structural feature in which bulky lateral groups exist in the polymer backbone, providing significant rotational hindrance to the backbone. This results in exceptionally high heat resistance (high glass transition temperature) and excellent processability.

[0019] In one embodiment of the present invention, R 2a and R 2b The substituent represented by is not particularly limited, but is generally H or an alkyl group in many cases. The alkyl group may be a C1 to C6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a t-butyl group (for example, C 1-4 Examples of the R include alkyl groups, particularly methyl groups. 2a and R 2b may be different or the same. 2a or R 2b The bonding positions (substitution positions) of are not particularly limited. The substitution numbers k1 and k2 are preferably 0 or 1. Furthermore, the substitution numbers k1 and k2 may be different from each other or may be the same.

[0020] In one embodiment of the present invention, the compound represented by the above Chemical Formula 1 may be represented by any one of the following Chemical Formulas 1-1 to 1-4:

[0021] [ka]

[0022] where X and R 1a , R 1b , R2a , and R 2b The conditions related to the above are as in Chemical Formula 1.

[0023] In one embodiment of the present invention, the R 1a and R 1b may each be selected from the substituents represented by the following chemical formulas 2-1 to 2-17:

[0024] [ka] JPEG0007782874000006.jpg249169JPEG0007782874000007.jpg157169

[0025] In one embodiment of the present invention, the substitution numbers p1 and p2 are each independently 0 or 1. In addition, the substitution numbers p1 and p2 may be different or the same.

[0026] In one embodiment of the present invention, the compound of the present invention has a chemical structure selected from the following formulas 3-1 to 3-16:

[0027] [ka] JPEG0007782874000009.jpg231169JPEG0007782874000010.jpg138169

[0028] In other embodiments of the present invention, X may be O.

[0029] In a specific embodiment of the present invention, when X is O, the compounds of the present invention are represented by the following formulas 4-1 to 4-12:

[0030] [ka] JPEG0007782874000012.jpg218169JPEG0007782874000013.jpg79169

[0031] In a specific embodiment of the present invention, when X is O, the compound of the present invention is represented by any one of the following formulas 4-13 to 4-18:

[0032] [ka]

[0033] In other embodiments of the present invention, X may be S.

[0034] In a specific embodiment of the present invention, when X is S, the compound of the present invention is represented by any one of the following formulas 5-1 to 5-9:

[0035] [ka] JPEG0007782874000016.jpg153169

[0036] In a specific embodiment of the present invention, when X is S, the compound of the present invention has a chemical structure represented by any one of the following formulas 5-10 to 5-13:

[0037] [ka]

[0038] In yet another embodiment of the present invention, X may be SO2.

[0039] In a specific embodiment of the present invention, when X is SO2, the compound of the present invention has a chemical structure represented by any one of the following formulas 6-1 to 6-5:

[0040] [ka]

[0041] In another embodiment of the present invention, when X is SO2, the compound of the present invention is represented by the following formula 6-6:

[0042] [ka]

[0043] According to another aspect of the present invention, the xanthene derivative compound of the present invention has four phenyl groups and can improve or enhance various properties, including optical properties. Therefore, the xanthene derivative compound of the present invention may be usefully used as a resin component, an additive, or the like. Furthermore, since the xanthene derivative compound of the present invention has multiple hydroxy groups, when a resin component is formed by adjusting the number of hydroxy groups to one or more and introducing a functional group, the properties of the resin can be efficiently improved.

[0044] In one embodiment of the present invention, the resin component may be (i) a resin containing a xanthene-based compound represented by Chemical Formula 1 of the present invention as a monomer, or (ii) a resin composed of the xanthene-based compound and a resin.

[0045] In one embodiment of the present invention, the resin constituting the resin component (said resin component (i) or (ii)) is not particularly limited, and a conventional thermoplastic resin or thermosetting resin (or photocurable resin) can be used. The resin constituting the resin component can be used alone or in combination of two or more kinds.

[0046] Examples of thermoplastic resins include olefin resins (polyethylene, polypropylene, polymethylpentene, amorphous polyolefin, etc.), halogen-containing vinyl resins (chlorine-containing resins such as polyvinyl chloride, fluorinated resins, etc.), acrylic resins, styrene resins (polystyrene, acrylonitrile-styrene resin, etc.), polycarbonate resins (bisphenol A polycarbonate, etc.), polyester resins (polyalkylene arylate resins such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polyarylate resins, liquid crystal polyesters, etc.), polyacetal resins, polyamide resins (polyamide 6, polyamide 66, polyamide 46, polyamide 6T, etc.), , polyamide MXD, etc.), polyphenylene ether resins (modified polyphenylene ether, etc.), polysulfone resins (polysulfone, polyethersulfone, etc.), polyphenylene sulfide resins (polyphenylene sulfide, etc.), polyimide resins (polyetherimide, polyamideimide, polyaminobismaleimide, bismaleimide triazine resin, etc.), polyetherketone resins (polyetherketone, polyetheretherketone, etc.), thermoplastic elastomers (polyamide elastomers, polyester elastomers, polyurethane elastomers, polystyrene elastomers, polyolefin elastomers, polydiene elastomers, polyvinyl chloride elastomers, fluorine-based thermoplastic elastomers), etc. The thermoplastic resins can be used alone or in combination of two or more.

[0047] Examples of thermosetting resins include phenolic resins, amino resins (such as urea resins and melamine resins), furan resins, unsaturated polyester resins, epoxy resins, thermosetting polyurethane resins, silicone resins, thermosetting polyimide resins, diallyl phthalate resins, and vinyl ester resins (such as resins obtained by reacting epoxy resins with (meth)acrylic acid or derivatives thereof, and resins obtained by reacting polyhydric phenols with glycidyl (meth)acrylate). Thermosetting resins (or photocurable resins) also include polyfunctional (meth)acrylates and vinyl ethers (such as divinyl ethers obtained by reacting diol components with acetylene). Thermosetting resins can be used alone or in combination.

[0048] Furthermore, the thermosetting resin may contain an initiator, a reactive diluent, a curing agent, a curing accelerator, etc. depending on the type of thermosetting resin (or photocurable resin). For example, a resin composition containing an epoxy resin or a urethane resin may contain an amine curing agent, etc., and a resin composition containing an unsaturated polyester resin or a vinyl ester resin may contain an initiator (e.g., peroxide), a polymerizable monomer (a reactive diluent such as (meth)acrylic acid ester or styrene), etc.

[0049] The resin component (i) or resin component (ii) of the present invention can be used alone or in combination of two or more kinds.

[0050] Furthermore, the resin component (i) contained as the constituent (monomer component) may be prepared by using a xanthene derivative compound corresponding to this polymerization component (or monomer component) as a polymerization component or constituent (e.g., a polyol component such as a diol component) of the resin. For example, in resins (such as polyester resins, polyurethane resins, epoxy resins, vinyl ester resins, epoxy resins, polyfunctional (meth)acrylates, (poly)urethane (meth)acrylates, (poly)ester (meth)acrylates, and vinyl ethers) that use a polyol component (particularly a diol component) as a polymerization component or constituent, the xanthene derivative compound may be used in part or all of the polyol component.

[0051] In the resin component (i), the xanthene derivative compounds can be used alone or in combination of two or more as polymerization components (or constituents).

[0052] Resins (or resin components) constituting the preferred resin component include polyester resins, polyurethane resins (thermoplastic or thermosetting polyurethane resins), polycarbonate resins, acrylic resins (including thermosetting or photocurable resins such as polyfunctional (meth)acrylates), epoxy resins, vinyl ethers, etc. Also preferred are resins (thermoplastic resins) containing an aromatic ring (benzene ring), such as aromatic polycarbonate resins (bisphenol A polycarbonate, etc.), polyester resins (polyalkylene arylate resins; polyarylate resins using aromatic dicarboxylic acids (terephthalic acid, etc.) and aromatic diols (biphenol, bisphenol A, xylene glycol, alkylene oxide adducts thereof, etc.) as polymerization components), polysulfone resins (polysulfone, polyethersulfone, etc.), and polyphenylene sulfide resins (polyphenylene sulfide, etc.).

[0053] Below, we will describe in detail a representative resin (or resin component) containing a xanthene derivative compound represented by the above chemical formula 1 as a monomer component (polymerization component, constituent component, copolymerization component) (or resin component (i)).

[0054] (1) Polyester resin A polyester resin containing the xanthene derivative compound as a polymerization component (particularly a polyester resin obtained by polymerizing the xanthene derivative compound (generally, a compound where p1 = p2 = 1) as a monomer component of the resin) can be obtained by reacting at least the xanthene derivative compound with a dicarboxylic acid component, and polyester resins include saturated or unsaturated polyester resins as well as polyarylate resins that use aromatic dicarboxylic acids as polymerization components.

[0055] The polyol component (particularly, the diol component) of the polyester resin can be formed by combining the xanthene derivative compound with other diol components. Examples of such diol components (or diols) include alkylene glycols (e.g., linear or chain C2-12 alkylene glycols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol, hexanediol, neopentyl glycol, octanediol, and decanediol), (poly)oxyalkylene glycols (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, and C2-4 alkylene glycol), alicyclic diols (e.g., 1,4-cyclohexanediol, Examples of suitable diols include 1,4-cyclohexanedimethanol, 2,2-bis(4-hydroxycyclohexyl)propane or its alkylene oxide adducts (e.g., 2,2-bis(4-(2-hydroxyethoxy)cyclohexyl)propane), aromatic diols (e.g., biphenol, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bisphenol AD, bisphenol F or their alkylene oxide (C2-3 alkylene oxide) adducts (e.g., 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane), xylene glycol, etc.). These diols can be used alone or in combination of two or more.

[0056] Preferred diols are linear or chain C2-10 alkylene glycols, particularly C2-6 alkylene glycols (e.g., linear or chain C2-4 alkylene glycols such as ethylene glycol, propylene glycol, and 1,4-butanediol). At least ethylene glycol is often used as the diol. Use of such diols (e.g., ethylene glycol) can improve polymerization reactivity and at the same time impart flexibility to the resin.

[0057] The ratio (molar ratio) of the xanthene derivative compound to the diols (former / latter) may be, for example, about 100 / 0 to 50 / 50, preferably about 100 / 0 to 75 / 25 (e.g., 100 / 0 to 70 / 30), and more preferably about 100 / 0 to 90 / 10 (e.g., 100 / 0 to 80 / 20).

[0058] The diol component may be used in combination with a polyol such as glycerin, trimethylolpropane, trimethylolethane, or pentaerythritol, if necessary.

[0059] Examples of dicarboxylic acid components constituting polyester resins include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and their ester-forming derivatives (e.g., acid anhydrides, acid halides (e.g., acid chlorides), lower alkyl esters (e.g., C1-2 alkyl esters), etc. These dicarboxylic acids can be used alone or in combination of two or more.

[0060] Examples of the aliphatic dicarboxylic acid include saturated C3-20 aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and hexadecanedicarboxylic acid (preferably saturated C3-14 aliphatic dicarboxylic acids); unsaturated C4-20 aliphatic dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and mesaconic acid (preferably unsaturated C4-14 aliphatic dicarboxylic acids); and ester-forming derivatives thereof. In the unsaturated polyester resin, the proportion of the aliphatic unsaturated dicarboxylic acid (maleic acid or its anhydride, etc.) may be, for example, about 10 to 100 mol%, preferably 30 to 100 mol%, and more preferably 50 to 100 mol% (e.g., 75 to 100 mol%) relative to the total dicarboxylic acid components.

[0061] Examples of alicyclic dicarboxylic acids include saturated alicyclic dicarboxylic acids (C3-10 cycloalkane-dicarboxylic acids such as cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and cycloheptanedicarboxylic acid), unsaturated alicyclic dicarboxylic acids (C3-10 cycloalkene-dicarboxylic acids such as 1,2-cyclohexenedicarboxylic acid and 1,3-cyclohexenedicarboxylic acid), polycyclic alkanedicarboxylic acids (di- or tricyclic C7-10 alkane-dicarboxylic acids such as bornanedicarboxylic acid, norbornanedicarboxylic acid, and adamantanedicarboxylic acid), polycyclic alkenedicarboxylic acids (di- or tricyclic C7-10 alkene-dicarboxylic acids such as bornenedicarboxylic acid and norbornenedicarboxylic acid), and ester-forming derivatives thereof.

[0062] Examples of aromatic dicarboxylic acids include aromatic C8-16 dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid (e.g., 2,6-naphthalenedicarboxylic acid), 4,4-diphenyldicarboxylic acid, diphenylether-4,4-dicarboxylic acid, 4,4-diphenylmethanedicarboxylic acid, and 4,4-diphenylketonedicarboxylic acid; and derivatives thereof capable of forming esters.

[0063] The dicarboxylic acid may be used in combination with a polycarboxylic acid such as trimellitic acid or pyromellitic acid, if necessary.

[0064] The dicarboxylic acid component is generally at least one selected from aliphatic dicarboxylic acids and alicyclic dicarboxylic acids, and particularly preferably an aliphatic dicarboxylic acid (a saturated aliphatic dicarboxylic acid or an ester-forming derivative thereof, particularly a saturated C3-14 aliphatic dicarboxylic acid such as adipic acid, suberic acid, or sebacic acid) or an alicyclic dicarboxylic acid (a C5-10 cycloalkanedicarboxylic acid such as cyclohexanedicarboxylic acid).

[0065] The polyarylate resin uses a dicarboxylic acid component containing at least an aromatic dicarboxylic acid, and the aromatic dicarboxylic acid can be used in combination with other dicarboxylic acids (aliphatic dicarboxylic acids and / or alicyclic dicarboxylic acids). The ratio of the aromatic dicarboxylic acid to the other dicarboxylic acid (molar ratio) may be, for example, about 100 / 0 to 10 / 90, preferably 100 / 0 to 30 / 70, and more preferably about 100 / 0 to 50 / 50.

[0066] In polyester resins, the ratio (molar ratio) of the dicarboxylic acid component to the polyol component (diol component, such as the xanthene derivative compound described above) may generally be the former / latter = 1.5 / 1 to 0.7 / 1, preferably 1.2 / 1 to 0.8 / 1 (particularly, 1.1 / 1 to 0.9 / 1).

[0067] The weight average molecular weight Mw (polystyrene equivalent) of the polyester resin is not particularly limited, and may be, for example, 100 to 50 × 10 4 , preferably 500 to 30 × 10 4 (e.g., 1000 to 20 × 10 4 ), more preferably 3000 to 30 × 10 4 In the unsaturated polyester resin, the molecular weight per double bond may be about 300 to 1000, preferably about 350 to 800, and more preferably about 400 to 700. The terminal group of the polyester resin may be a hydroxy group or a carboxyl group, and may be protected with a protecting group as necessary.

[0068] The polyester resin can be produced by a condensation reaction of a polyol component (particularly, a diol component) composed of the xanthene derivative compound with the dicarboxylic acid component by a conventional method, such as a direct polymerization method (direct esterification method) or an ester exchange method.

[0069] (2) Polyurethane resin The polyol component (diol component) constituting the polyurethane-based resin containing the xanthene derivative compound as a polymerization component (monomer component) may be composed solely of the xanthene derivative compound, or may be used in combination with the diols exemplified in the section on polyester-based resins. Also useful as the diol component of the polyurethane-based resin are diol components containing the xanthene derivative compound as a structural unit, such as polyester diols produced by reacting a diol component composed of a xanthene derivative compound in which p1 = p2 = 1 in Chemical Formula 1 above with a dicarboxylic acid component, and polyether diols produced by reacting the diol component with an alkylene oxide. The diol components can be used alone or in combination of two or more. If necessary, the diol component may be used in combination with a polyol component such as a triol.

[0070] The content of the xanthene derivative compound in the polyol component (diol component) may be, for example, about 10 to 100 mol %, preferably about 20 to 80 mol %, and more preferably about 30 to 70 mol %, based on the entire polyol component (diol component).

[0071] Diisocyanate compounds that make up polyurethane resins include aromatic diisocyanates [paraphenylene diisocyanate, tolylene diisocyanate (TDI), xylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), naphthalene diisocyanate (NDI), bis(isocyanatophenyl)methane (MDI), toluidine diisocyanate (TODI), 1,2-bis(isocyanatophenyl)ethane, 1,3-bis(isocyanatophenyl)ethane, Examples of diisocyanate compounds include diisocyanate compounds such as cyclohexane-1,4-diisocyanate, 1,4-bis(isocyanatophenyl)propane, 1,4-bis(isocyanatophenyl)butane, polymeric MDI, alicyclic diisocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, and aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), and lysine diisocyanate (LDI). These diisocyanate compounds can be used alone or in combination of two or more. These diisocyanate compounds can be used in combination with polyisocyanate compounds (e.g., aliphatic triisocyanates such as 1,6,11-undecane triisocyanate methyl octane and 1,3,6-hexamethylene triisocyanate; triisocyanate compounds such as alicyclic triisocyanates such as bicycloheptane triisocyanate), or monoisocyanate compounds (C alkyl isocyanates such as methyl isocyanate; C cycloalkyl isocyanates such as cycloalkyl isocyanates; C aryl isocyanates such as phenyl isocyanate), if necessary. The isocyanate compounds also include derivatives such as polymers or modified products of the polyisocyanate compounds.

[0072] Polyurethane resins can be obtained by a conventional method, for example, by urethane reaction using 0.7 to 2.5 moles, preferably 0.8 to 2.2 moles, and more preferably 0.9 to 2 moles of a diisocyanate component per mole of a polyol component (diol component). Using about 0.7 to 1.1 moles of the diisocyanate component per mole of the diol component can produce a thermoplastic resin, while using an excess mole (for example, about 1.5 to 2.2 moles) of the diisocyanate component can produce a thermosetting resin having a glass-type isocyanate group at the terminal.

[0073] (3) Polycarbonate resin Examples of polycarbonate resins containing the xanthene derivative compound as a polymerization component include polycarbonate resins obtained by a conventional method, for example, by reacting a polyol component (particularly, a diol component) composed of at least the xanthene derivative compound (generally, a compound in which p1 = p2 = 1 in the above Chemical Formula 1) with phosgene (phosgene method), or by reacting a polyol component (diol component) composed of the xanthene derivative compound with a carbonate ester (ester interchange method).

[0074] The polyol component (diol component) may be composed of the xanthene derivative compound alone, or may be composed of the xanthene derivative compound and other diols (diols exemplified in the section on polyester-based resins above, particularly aromatic diols or alicyclic diols). The other diols may be used alone or in combination of two or more. Among the other diols, aromatic diols such as bisphenols such as bisphenol A, AD, and F are particularly preferred. The ratio of the xanthene derivative compound having a hydroxy group to the diols can be selected from the same range as in the case of the polyester-based resins.

[0075] The molecular weight of the polycarbonate resin is not particularly limited, and for example, the weight average molecular weight is 1×10 3 ~100×10 4 (e.g., 1×10 4 , 100×104 ), preferably 5 × 10 3 ~50×10 4 (e.g., 1×10 4 , 50×10 4 ), more preferably 1 × 10 4 , 25×10 4 (e.g., 1×10 4 , 10×10 4 ) may be about the same.

[0076] (4) Epoxy resin The diol or polyol component constituting the epoxy resin may be composed solely of the xanthene derivative compound, or may be composed of a combination of the xanthene derivative compound (generally a compound where p1 = p2 = 1 in the above Chemical Formula 1), the polyester resin, and other diols (particularly, aromatic diols or alicyclic diols). The other diols may be used alone or in combination of two or more. Among the diols, aromatic diols such as bisphenols A, AD, and F are particularly preferred. The ratio of the xanthene derivative compound to the diols may be selected from the same range as in the polyester resin. Furthermore, the bisphenol xanthene compound and, if necessary, other diols may be used in combination with polyols (e.g., phenol novolak).

[0077] The epoxy resin may be obtained by reacting at least the xanthene derivative compound with epichlorohydrin. The weight average molecular weight Mw of the epoxy resin may be, for example, about 300 to 30,000, preferably about 400 to 10,000, and more preferably about 500 to 5,000.

[0078] (5) Vinyl ester resin The vinyl ester resin can be obtained by a conventional method, for example, by reacting the epoxy resin (the epoxy resin containing the xanthene derivative compound) with a polymerizable monomer having at least a carboxyl group (unsaturated monocarboxylic acid). The polymerizable monomer having a carboxyl group may be used in combination with the polyester resin and a dicarboxylic acid (aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, or aromatic dicarboxylic acid (isophthalic acid, terephthalic acid, etc.)) as needed.

[0079] As the polymerizable monomer having a carboxyl group, an unsaturated monocarboxylic acid can be used. As the unsaturated monocarboxylic acid, (meth)acrylic acid can generally be used, and cinnamic acid, crotonic acid, sorbic acid, maleic acid monoalkyl ester (monomethyl maleate, etc.), etc. can also be used. These monomers can be used alone or in combination of two or more.

[0080] The amount of unsaturated monocarboxylic acid used may be about 0.5 to 1.2 mol, preferably about 0.7 to 1.1 mol, and more preferably about 0.8 to 1 mol, per 1 mol of epoxy group in the epoxy resin.

[0081] The vinyl ester resin can also be obtained by reacting the xanthene derivative compound with glycidyl (meth)acrylate. The amount of glycidyl (meth)acrylate used may be, for example, about 1 to 3 moles, preferably about 1 to 2 moles, per mole of the xanthene derivative compound.

[0082] (6) Acrylic resin The acrylic resin monomer can be obtained by reacting the xanthene derivative compound with a polymerizable monomer having a carboxyl group. As the polymerizable monomer having a carboxyl group, generally, an unsaturated monocarboxylic acid, particularly (meth)acrylic acid, can be used. Alternatively, cinnamic acid, crotonic acid, sorbic acid, or a monoalkyl maleate (e.g., monomethyl maleate) can also be used. Furthermore, instead of the unsaturated carboxylic acid, a reactive derivative such as an acid chloride or a C1-2 alkyl ester can also be used. These monomers can be used alone or in combination of two or more.

[0083] The acrylic resin may be a homopolymer or copolymer of the (meth)acrylic monomer having a xanthene skeleton, or a copolymer of the (meth)acrylic monomer having a xanthene skeleton and another copolymerizable monomer. The copolymerizable monomer may be either a monofunctional compound or a polyfunctional compound, or a combination of a monofunctional compound and a polyfunctional compound. Examples of copolymerizable monomers include carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, and maleic anhydride; (meth)acrylic acid esters [e.g., C1-6 alkyl (meth)acrylate esters such as methyl (meth)acrylate]; (meth)acrylic acid hydroxyalkyl esters [e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate]; vinyl cyanides such as (meth)acrylonitrile; aromatic vinyl monomers such as styrene; vinyl carboxylate esters such as vinyl acetate; and α-olefins such as ethylene and propylene.

[0084] These copolymerizable monomers can be used alone or in combination of two or more.

[0085] Furthermore, a monomer having multiple (meth)acryloyl groups obtained by reacting the xanthene derivative compound with a polymerizable monomer having a carboxyl group may be used as an acrylic resin (i.e., a thermosetting acrylic resin, an oligomer (resin precursor)).

[0086] The resin component (ii) can be produced or prepared by mixing the xanthene derivative compound with a resin (and, if necessary, an additive).

[0087] The mixing method is not particularly limited, and for example, a melt-kneading method using a mixer such as a ribbon blender, a tumble mixer, or a Henschel mixer, or a mixing means such as a kneader such as an open roller, a kneader, a Banbury mixer, or an extruder can be used. These mixing methods can be used alone or in combination of two or more.

[0088] The ratio of the xanthene derivative compound in the resin component (ii) may be, for example, about 1 to 80 parts by weight, preferably about 5 to 60 parts by weight, and more preferably about 20 to 60 parts by weight, per 100 parts by weight of the resin.

[0089] The resin component may contain an additive, and since the resin component has a xanthene skeleton derived from the xanthene derivative compound, the dispersibility of the additive can be improved.

[0090] The additives may be liquid or solid (e.g., powder or granular solid) at room temperature (e.g., about 15 to 25°C). Examples of additives include fillers or reinforcing agents, colorants (dyes and pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (antioxidants, UV absorbers, heat stabilizers, etc.), mold release agents (natural waxes, synthetic waxes, straight-chain fatty acids or metal salts thereof, acid amides, esters, paraffins, etc.), antistatic agents, dispersants, flow control agents, leveling agents, antifoaming agents, surface modifiers (e.g., silane coupling agents or titanium-based coupling agents), stress reducers (e.g., silicone oil, silicone rubber, various plastic powders, various high-performance plastic powders), heat resistance improvers (e.g., sulfur compounds, polysilanes), and carbon materials. These additives can be used alone or in combination.

[0091] Among these additives, fillers, colorants (dyes and pigments such as black pigments, red pigments, green pigments, and blue pigments), flame retardants, and carbon materials are preferred. Carbon materials that function as fillers, reinforcing agents, colorants, and conductive agents are also preferred.

[0092] Depending on the form (resin pellets, coating composition, etc.), the resin component can be molded into a molded product by a known molding method, such as injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, or coating method (spin coating, roll coating, curtain coating, dip coating, casting molding, etc.). Examples of the shape of the molded product include two-dimensional structures (films, sheets, coating films (or thin films), plates, etc.) and three-dimensional structures (for example, pipes, rods, tubes, leather, hollow articles, etc.).

[0093] In another aspect of the present invention, there is provided a polyurethane (co)polymer produced from polymerization components including the xanthene derivative compound according to the above-mentioned aspect of the present invention; and a diisocyanate compound.

[0094] In this specification, the term "(co)polymer" refers to both a polymer and a copolymer, where the term "polymer" refers to a homopolymer made of a single repeating unit, and the term "copolymer" refers to a composite polymer having two or more types of repeating units.

[0095] In this specification, the term "(co)polymer" is used to mean a random (co)polymer, a block (co)polymer, a graft (co)polymer, and the like.

[0096] In one embodiment of the present invention, the diisocyanate compound contains an isocyanate group and reacts with the hydroxy group of the xanthene derivative compound or the additional diol compound to form a urethane bond.

[0097] The diisocyanate compound is not particularly limited as long as it can be used in the production of polyurethane.

[0098] In one embodiment of the present invention, the diisocyanate compound may be at least one selected from the group consisting of methylene diphenyl diisocyanate (MDI), p-phenylene diisocyanate (PPDI), tolylene-2,4-diisocyanate (2,4-TDI), tolylene-2,6-diisocyanate (2,6-TDI), xylene diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), 4,4'-methylenedicyclohexyl diisocyanate (H12MDI), 1,4-cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), and 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI).

[0099] In yet another aspect, the present invention provides a polycarbonate (co)polymer produced from polymerization components including the xanthene derivative compound according to the above-mentioned aspect of the present invention; and a polycarbonate precursor.

[0100] In one embodiment of the present invention, the polycarbonate precursor is represented by the following chemical formula:

[0101] [ka]

[0102] In the above chemical formula, Rb1 and Rb2 may be the same or different and each independently represent a halogen group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group, and b1 and b2 each represent 0 or 1.

[0103] The polycarbonate precursor serves to link additional comonomers as needed, and specific examples thereof include phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, mK cresyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, and bishaloformates, and any one or a mixture of two or more of these can be used.

[0104] The polymerization may be carried out by either interfacial polymerization or melt polymerization.

[0105] The solvent that can be used in the polymerization is not particularly limited as long as it is a solvent that is used in the polymerization of polycarbonates in the art, and for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used.

[0106] The polymerization is preferably carried out in the presence of an acid binder, and examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine.

[0107] Furthermore, it is preferable to carry out the polymerization in the presence of a molecular weight regulator to regulate the molecular weight of the polycarbonate during the polymerization. C1-20 alkylphenols can be used as the molecular weight regulator, and specific examples thereof include p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol. The molecular weight regulator can be added before, during, or after the initiation of polymerization.

[0108] In addition, to accelerate the polymerization reaction, a reaction accelerator such as a tertiary amine compound, a quaternary ammonium compound, or a quaternary phosphonium compound, such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, may be used.

[0109] According to yet another aspect of the present invention, there is provided an optical lens comprising a polymer or copolymer according to one aspect of the present invention described above.

[0110] The optical lens can be manufactured in a desired form by extruding the polymer or copolymer described above, and other processing methods besides extrusion are also applicable.

[0111] In one embodiment of the present invention, the polymer or copolymer that can be used to manufacture the optical lens has high transmittance and high heat resistance, making it easier to process than conventional optical lens materials, and enabling mass production of plastic lenses by injection molding. [Effects of the Invention]

[0112] The present invention relates to novel high-refractive-index xanthene monomers with various functional groups, i.e., novel high-refractive-index compounds having a fluorene and xanthene composite cardo structure and a refractive index of 1.7 or higher. The compounds of the present invention are applicable to the production of high-refractive-index optical resins. Furthermore, the fluorene and xanthene composite cardo structure of the compounds minimizes the fluidity of the molecular chains, resulting in a high glass transition temperature (Tg). Therefore, the compounds can be widely used in the production of high-heat-resistant resins, which require high thermal stability. DETAILED DESCRIPTION OF THE INVENTION

[0113] The present invention will be described in more detail below with reference to examples. It will be apparent to those skilled in the art that these examples are merely for the purpose of more specifically illustrating the present invention, and that the scope of the present invention is not limited to these examples according to the gist of the present invention. [Example]

[0114] The method for synthesizing the novel spiro structure compound of the present invention is as follows.

[0115] Production Example 1: Production method for compound 5 (2,2'-(spiro[fluorene-9,9'-thioxanthene]-2,7-diylbis(oxy))diethanol) (FTX) (1) Synthesis of Compound 3 (2,7-dimethoxyspiro[fluorene-9,9'-thioxanthene]) 1) Synthesis of Compound 1 (2,7-dimethoxyfluorenone)

[0116] [ka]

[0117] 2) Synthesis of Compound 2 ((2-Bromophenyl)thiobenzene)

[0118] [ka]

[0119] 3) Synthesis of compound 3 (2,7-dimethoxyspiro[fluorene-9,9'-thioxanthene])

[0120] [ka]

[0121] 7.857g (29.6mmol) of (2-bromophenyl)thiobenzene was placed in a two-neck flask equipped with a thermometer and a stirrer. 15ml of dry THF was added and stirred. After maintaining the temperature at -78°C, 18ml of 1.5M nBuLi was added dropwise. Stirring was continued at the same temperature for 1 hour. 5.2g (21.8mmol) of 2,7-dimethoxyfluorene was placed in another two-neck flask equipped with a stirrer. 70ml of dry THF was added and stirred, and then transferred to the flask maintained at -78°C using a syringe. Stirring was continued at the same temperature for 1 hour, followed by gradually raising the temperature to room temperature and stirring for 3 hours. The reaction solution was reduced in pressure and extracted with chloroform and NaCl. The organic layer was separated and reduced in pressure to obtain solid intermediate 1 (7.69g, 83% yield).

[0122] A two-neck flask equipped with a thermometer, stirrer, and condenser was charged with 17.69 g (18 mmol) of the intermediate. 70 ml of acetic acid and 10 ml of 36% HCl were added, and the mixture was stirred at 80°C for 10 hours. The remaining HCl was neutralized with NaHCO3 and water, and the mixture was filtered. The filtered solid was extracted with chloroform and NaHCO3. The organic layer was purified under reduced pressure to obtain solid compound 3 (7.15 g, 80% yield).

[0123] (2) Synthesis of Compound 4 and Compound 5 (FTX) 1) Compound 4 (spiro[fluorene-9,9'-thioxanthene]-2,7-diol) synthesis

[0124] [ka]

[0125] 3 g (7.34 mmol) of 2,7-dimethoxyspiro[fluorene-9,9'-thioxanthene] was placed in a two-neck flask equipped with a thermometer and a stirrer. 60 ml (0.12 M) of dichloromethane was added and stirred. After the temperature was lowered to 0°C, 22 ml (22.02 mmol) of 1.0 M BBr3 in dichloromethane was slowly added dropwise. The mixture was stirred for 3 hours while gradually warming to room temperature. After the temperature was lowered to 0°C, ice was added to quench the remaining BBr3, followed by extraction with dichloromethane and NaHCO3. The organic layer was separated and purified under reduced pressure to obtain solid compound 4, spiro[fluorene-9,9'-thioxanthene]-2,7-diol (2.7 g, 97% yield, 99.8% purity).

[0126] 2) Compound 5 (2,2'-(spiro[fluorene-9,9'-thioxanthene]-2,7-diylbis(oxy))diethanol) synthesis (FTX synthesis)

[0127] [ka]

[0128] A three-neck flask equipped with a thermometer, stirrer, and condenser was charged with 42.5 g (6.57 mmol) of compound 5. 13 ml of DMF was added and stirred. 1 ml (15.77 mmol) of ethylene carbonate and 0.2 ml (0.2 mmol) of TBAF (Tetra-n-butylammonium fluoride) were added. The mixture was stirred at 150°C for 3 hours. After the reaction was completed, the temperature was lowered to room temperature, and the compound was extracted with chloroform and water. The organic layer was separated and purified under reduced pressure to obtain solid compound 5, FTX (2,2'-(spiro[fluorene-9,9'-thioxanthene]-2,7-diylbis(oxy))diethanol) (2.83 g, 92% yield, 99.6% purity).

[0129] Production Example 2: Method for producing compound 6 (2,7-bis(2-hydroxyethoxy)spiro[fluorene-9,9'-thioxanthene]10',10'-dioxide) (FTXDO)

[0130] [ka]

[0131] Compound 5, 105 mg (0.22 mmol) of FTX (2,2'-(spiro[fluorene-9,9'-thioxanthene]-2,7-diylbis(oxy))diethanol), was placed in a two-neck flask equipped with a thermometer and a stirrer. 7 ml (0.03 M) of dichloromethane was added, and the temperature was lowered to 0°C. At the same temperature, 101 mg (0.44 mmol) of mCPBA (meta-Chloroperoxybenzoic acid) was added. The mixture was gradually warmed to room temperature and stirred for 5 hours.

[0132] After the reaction was complete, the mixture was extracted with dichloromethane and NaHCO3. The organic layer was separated and concentrated. The concentrate was purified by column chromatography (eluent: ethyl acetate-hexane) to obtain solid compound 6, FTXDO (2,7-bis(2-hydroxyethoxy)spiro[fluorene-9,9'-thioxanthene]10',10'-dioxide) (83 mg, yield: 75%, purity: 99.2%).

[0133] Production Example 3: Method for producing compound 10 (2,2'-(spiro[fluorene-9,9'-xanthene]-2,7-diylbis(oxy))diethanol) (FX) (1) Synthesis of Compound 7 (2,7-dibromospiro[fluorene-9,9'-xanthene])

[0134] [ka]

[0135] A two-neck flask equipped with a thermometer and stirrer was charged with 30 g (88.76 mmol) of 2,7-dibromofluorene and 83 g (887.6 mmol) of phenol and stirred. 24 ml (355.04 mmol) of methanesulfonic acid was added and stirred at 150°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature and extracted with chloroform, NaHCO3, and NaCl. The organic layer was separated and purified under reduced pressure to obtain solid compound 7 (33.28 g, 76.5% yield, 99.8% purity).

[0136] (2) Synthesis of compound 8 (2,7-dimethoxyspiro[fluorene-9,9'-xanthene])

[0137] [ka]

[0138] A two-neck flask equipped with a thermometer, stirrer, and condenser was charged with 1 g (2.039 mmol) of compound 7, 1.55 g (8.159 mmol), and 3.3 ml of dry DMF and stirred under a nitrogen atmosphere. 14.7 ml (4.6 M) of NaOMe was added and refluxed at 120°C for 24 hours with stirring. After the reaction was complete, the mixture was diluted with chloroform and extracted with NH4Cl and water. The organic layer was separated and purified under reduced pressure to obtain solid compound 8 (0.7 g, 87% yield, 99.7% purity).

[0139] (3) Compound 9 (2,7-dihydroxyspiro[fluorene-9,9'-xanthene]) synthesis

[0140] [ka]

[0141] A two-neck flask equipped with a thermometer, stirrer, and condenser was charged with 2 g (5.096 mmol) of compound 8 and maintained under a nitrogen atmosphere. 13 ml (0.4 M) of glacial acetic acid and 2.49 ml (45.86 mmol) of 47% HBr were added and refluxed at 120°C for 48 hours with stirring. After the reaction was complete, the mixture was cooled to room temperature and extracted with chloroform and NaHCO3. The organic layer was separated and purified under reduced pressure to obtain solid compound 9 (2,7-dihydroxyspiro[fluorene-9,9'-xanthene]) (1.8 g, 97% yield, 99.5% purity).

[0142] (4) Synthesis of compound 10 (2,2'-(spiro[fluorene-9,9'-xanthene]-2,7-diylbis(oxy))diethanol) (FX synthesis)

[0143] [ka]

[0144] A two-neck flask equipped with a thermometer, stirrer, and condenser was charged with 2 g (5.488 mmol) of compound 9 (2,7-dihydroxyspiro[fluorene-9,9'-xanthene]), 13 mL of dry DMF, 0.887 mL (12.07 mmol) of ethylene carbonate, and 0.1 mL (0.1 mmol) of TBAF, and the mixture was refluxed and stirred at 150 °C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was separated and purified under reduced pressure to obtain solid compound 10 (2.0 g, 83.3% yield, 99.3% purity).

[0145] Production Example 4: Synthesis of FXAR

[0146] [ka]

[0147] A three-neck flask equipped with a thermometer, stirrer, and condenser was charged with 3.36 g (7.4 mmol) of compound 10 (2,2'-(spiro[fluorene-9,9'-xanthene]-2,7-diylbis(oxy))diethanol, 1.4 mL (18.2 mmol) of acrylic acid, 0.37 g (1.95 mmol) of p-toluenesulfonic acid monohydrate, 0.04 g (0.34 mmol) of hydroquinone, and 20 mL of dry toluene, and the mixture was stirred at 120 °C for 7 hours. After cooling to room temperature, the compound was extracted with chloroform and aqueous NaOH. The organic layer was separated, reduced pressure, and purified to obtain 3.66 g of solid compound FXAR (yield 88.0%, purity 99.2%).

[0148] 1 H-NMR (500MHz, CDCl3): δ= 7.52-7.54 (m, 2H), 7.11-7.13 (m, 4H), 6.83-6.84 (d, J = 8.2 Hz, 2H), 6.73 (m, 2H), 6.61 (s, 2H), 6.36-6.37 (d, J = 7.3 Hz, 2H), 6.34 (d, J = 1.5 Hz, 1H), 6.31 (d, J = 1.2 Hz, 1H), 5.99-6.04 (dd, J1= 17.4 Hz, J2= 8.9 Hz, 1H), 5.99-6.04 (dd, J1= 17.4 Hz, J2=11.9 Hz, 1H), 5.73-5.75 (dd, J1= 10.4 Hz, J2= 1.2 Hz, 2H), 4.34-4.35 (t, J = 3.7 Hz, 4H), 4.02 (d, J = 4, 4H).

[0149] Production Example 5: Synthesis of FTXEP

[0150] [ka]

[0151] In a two-neck flask equipped with a thermometer and stirrer, 5.70 g (15.0 mmol) of compound 4 (spiro[fluorene-9,9'-thioxanthene]-2,7-diol) and 35 ml of DMF were mixed, and 792 mg (33.0 mmol) of NaH was slowly added at room temperature, followed by stirring for 20 minutes. 4.17 g (45.0 mmol) of epichlorohydrin was added, and the mixture was stirred at room temperature for 24 hours. Ethyl acetate and water were added to the reaction mixture to extract the compound. The organic layer was separated and purified under reduced pressure to obtain 6.29 g of solid compound FXEP (yield 85.0%, purity 98.8%).

[0152] 1 H-NMR (500MHz, CDCl3): δ= 7.57 (d, J = 8.2 Hz, 4H), 7.39 (d, J=7.6 Hz, 4H), 7.25 (s, 1H), 7.14 (t, J=7.6 *2, 4H), 7.08 (m, 2H), 6.92 (dd, J1=8.5Hz, J2= 2.4 Hz, 4H), 6.88(m, 3H),6.54 (m, 4H), 4.1 (m, 4H), 3.84(dd, = 10.8 Hz, J2= 5.6 Hz, 4H), 3.27(m, 4H), 2.83(m, 4H), 2.68(dd, J1=5Hz, J2=2.6Hz, 4H).

[0153] Production Example 6: Synthesis of FXEP

[0154] [ka]

[0155] In a two-neck flask equipped with a thermometer and stirrer, 3.64 g (10.0 mmol) of compound 9 (2,7-dihydroxyspiro[fluorene-9,9'-xanthene]) and 25 ml of DMF were mixed, and 528 mg (22.0 mmol) of NaH was slowly added at room temperature and stirred for 20 minutes. 2.78 g (30.0 mmol) of epichlorohydrin was added and stirred for 24 hours at room temperature. Ethyl acetate and water were added to the reaction mixture to extract the compound. The organic layer was separated and purified under reduced pressure to obtain 4.10 g of solid compound FXEP (86.0% yield, 98.5% purity).

[0156] 1 H-NMR (500MHz, CDCl3): δ= 7.52 (m, 2H), 7.19 (d, J = 2.1, 3H), 7.13 (m, 4H), 6.83 (dd, J1 = 8.2 Hz, J2 = 2.1 Hz, 2H), 6.72 (m, 2H), 6.36 (d, J = 7.9 Hz, 2H), 4.02 (m, 2H), 3.76 (m, 2H), 3.19 (s, 2H), 2.6 (m, 2H).

[0157] Production Example 7: Synthesis of FTXAL

[0158] [ka]

[0159] A three-neck flask equipped with a thermometer, stirrer, and condenser was charged with 3.80 g (10.0 mmol) of compound 4 (spiro[fluorene-9,9'-thioxanthene]-2,7-diol), 4.42 g (32.0 mmol) of K2CO3, and 30 ml of acetone, and stirred at room temperature for 10 minutes. The temperature was raised to 65°C, and 2.66 g (22 mmol) of allyl bromide was added dropwise over 15 minutes, followed by reflux and stirring for 24 hours. After cooling to room temperature, the acetone was distilled off, and dichloromethane and water were added to extract the compound. The organic layer was separated, reduced pressure, and purified to obtain 4.15 g of solid compound FTXAL (90.0% yield, 99.5% purity).

[0160] 1 H-NMR (500MHz, CDCl3): δ= 7.49(d, J = 8.5 Hz, 2H), 7.32 (dd, J1 = 7.9 Hz, J2 = 1.2 Hz, 2H), 7.19 (s, 1H), 7.06 (m, 3H), 6.83 (m, 3H), 6.5 (dd, J1 = 8.1 Hz, J2 = 1.1 Hz, 2H), 5.9 (m, 2H), 5.27 (m, 2H), 4.35(m, 3H).

[0161] Preparation Example 8: Synthesis of FTXSI

[0162] [ka]

[0163] A two-neck flask equipped with a thermometer and stirrer was charged with 5.0 g (10.9 mmol) of FTXAL compound, 4.7 g (23.9 mmol) of 3-mercaptopropyltrimethoxysilane, and 50 ml of THF, and stirred at room temperature for 30 minutes. 5 mg of photoinitiator 1-hydroxycyclohexylphenyl ketone was added, and the reaction mixture was irradiated with UV light at 53 mW for 120 seconds. The reaction mixture was then stirred for 1 hour. The THF solvent was distilled under reduced pressure, and the compound was extracted by adding EtOAc and water. The organic layer was separated, purified under reduced pressure, and yielded 8.15 g of solid compound FTXSI (88.0% yield, 98.8% purity).

[0164] 1H-NMR (500MHz, CDCl3): δ= 7.57-7.55 (d, J = 8.2 Hz, 2H), 7.4-7.38 (d, J = 7.6 Hz, 2H), 7.15-7.14 (m, 2H), 7.06-7.05 (d, J = 2.4 Hz, 2H), 6.9-6.78 (m, 4H), 6.57-6.55 (d, J = 7.9 Hz, 2H), 3.94-3.92 (m, 4H), 3.75-3.54 (m, 18H), 2.64-2.61 (m, 4H), 2.52-2.49 (m, 4H), 1.99-1.96 (m, 4H), 1.7-1.66 (m, 4H), 0.77-0.71 (m, 4H).

[0165] Production Example 9: Synthesis of FTXAH

[0166] [ka]

[0167] A two-neck flask equipped with a thermometer and stirrer was charged with 3.33 g (15.8 mol) of trimellitic anhydride chloride and 5 mL of dry THF and stirred at 0 °C under an argon atmosphere. A solution of 2.00 g (5.26 mmol) of compound 4 (spiro[fluorene-9,9'-thioxanthene]-2,7-diol) and 1.28 mL of dry pyridine in 10 mL of dry THF was slowly added dropwise and stirred at 0 °C for 3 hours. The mixture was then stirred at room temperature for an additional 24 hours. The salt formed was filtered using hexane, and the filtrate was distilled under reduced pressure to remove the solvent. The concentrated solution was recrystallized with acetic anhydride to obtain 3.26 g of solid compound FTXAH (yield 85.0%, purity 99.6%).

[0168] 1H-NMR (500MHz, CDCl3): δ= 8.76 (d, J = 0.6 Hz, 2H), 8.65-8.67 (dd, J1 = 7.9 Hz, J2 = 1.2 Hz, 2H), 8.13-8.15 (d, J = 7.9 Hz, 2H), 7.86-7.88 (d, J = 8.2 Hz, 2H), 7.49-7.50 (d, J = 2.1 Hz, 2H), 7.42-7.43 (m, J = 7.9 Hz, 2H), 7.35-7.37 (m, 2H), 7.19-7.22 (t, J = 7.5 Hz, 2H), 6.96-6.99 (m, 2H), 6.64-6.66 (m, J = 7.9 Hz, 2H).

[0169] Production Example 10: Synthesis of FXAM

[0170] [ka]

[0171] A three-neck flask equipped with a thermometer, stirrer, and condenser was charged with 1.70 g (3.47 mmol) of compound 7 (2,7-dibromospiro[fluorene-9,9'-xanthene]), 0.90 g (13.88 mmol), sodium azide, 0.52 g (4.51 mmol), CuO, 0.5 g (3.47 mmol), and 5 ml of DMSO. The mixture was stirred at 100 °C under an argon atmosphere for 12 hours. After cooling to room temperature, 1.5 ml of aqueous NH4Cl and 5 ml of EtOAc were added and the mixture was stirred for 1 hour. The solid particles were filtered through Celite using EtOAc. The filtrate was extracted with EtOAc and aqueous NaHCO3. The organic layer was separated and purified under reduced pressure to obtain 1.12 g of solid compound FXAM (89.0% yield, 99.0% purity).

[0172] 1H-NMR (500MHz, DMSO): 7.36-7.37 (d, J = 7.9 Hz, 2H), 7.23-7.24 (m, 4H), 6.87-6.89 (m, 2H), 6.51-6.52 (d, J = 8.2 Hz, 2H), 6.39-6.40 (d, J = 7.6 Hz, 2H), 6.21 (s, 2H), 4.97 (s, 4H).

[0173] Production Example 11: Synthesis of FTXDOAR

[0174] [ka]

[0175] Compound 6, 5.00 g (10.0 mmol) of FTXDO (2,7-bis(2-hydroxyethoxy)spiro[fluorene-9,9'-thioxanthene]10',10'-dioxide), 1.7 mL (24.6 mmol) of acrylic acid, 0.50 g (2.63 mmol) of p-toluenesulfonic acid monohydrate, 0.05 g (0.46 mmol) of hydroquinone, and 30 mL of dry toluene were added to a three-neck flask equipped with a thermometer, stirrer, and condenser, and the mixture was stirred at 120 °C for 7 hours. After cooling to room temperature, the compound was extracted with chloroform and aqueous NaOH. The organic layer was separated, reduced pressure, and purified to obtain 5.17 g of solid compound FTXDOAR (yield 85.0%, purity 99.7%).

[0176] 1H-NMR (500MHz, CDCl3): δ= 8.15-8.17 (dd, J1 = 8.1 Hz, J2 = 1.1 Hz, 2H), 7.56-7.58 (m, 2H), 7.40-7.43 (m, 2H), 7.22 (m, 4H), 6.89-6.91 (dd, J1 = 8.4 Hz, J2 = 2.3 Hz, 2H), 6.82-6.83 (m, 2H), 6.55-6.57 (m, 2H), 6.30-6.33 (d, J = 1.2 Hz, 2H), 5.98-6.04 (m, 2H), 5.72-5.74 (dd, J1 = 10.5 Hz, J2 = 1.4 Hz, 2H), 4.32-4.34 (m, 4H), 3.99-4.00 (m, 4H).

[0177] Production Example 12: Synthesis of 2-hydroxyspiro[fluorene-9,9'-xanthene] (mFXOH)

[0178] [ka]

[0179] 10 g (50.96 mmol) of 2-hydroxy-9-fluorene and 23.9 g (254.8 mmol) of phenol were added to a three-neck flask equipped with a thermometer, stirrer, and condenser. 9.0 mL (142.7 mmol) of methanesulfonic acid was then added, and the reaction mixture was stirred at 150 °C for 3 hours. Upon completion of the reaction, the mixture was cooled to room temperature and the compound was extracted with ethyl acetate and aqueous NaHCO3. The organic layer was separated, purified under reduced pressure, and yielded 13.9 g of the solid compound, 2-hydroxyspiro[fluorene-9,9'-xanthene](FXmOH) (78.3% yield, 99.7% purity).

[0180] 1H-NMR (500MHz, CDCl3): δ= 7.62-7.55 (m, 2H), 7.27-7.23 (m, 1H), 7.14-7.09 (m, 4H), 7.06-7.03 (m, 2H), 6.76-6.74 (dd, J = 8.2 Hz, 1.8 Hz, 1H), 6.71-6.69 (t, 2H), 6.52 (s, 1H), 6.36-6.35 (d, J = 7.6 Hz, 2H), 4.82 (s, 1H). Example 13: Synthesis of mFX

[0181] [ka]

[0182] In a three-neck flask equipped with a thermometer, stirrer, and condenser, 4 g (11.5 mmol) of mFXOH was dissolved in 15 mL of DMF, and 0.836 mL (12.6 mmol) of ethylene carbonate and 0.1 mL (0.1 mmol) of TBAF were added. The mixture was stirred at 150°C for 2 hours. After the reaction was complete, the temperature was lowered to room temperature and the mixture was extracted with ethyl acetate. The organic layer was separated, distilled, and then crystallized with ethyl acetate and hexane to obtain 4.47 g of white solid compound mFX (yield 99.3%, purity 99.7%).

[0183] 1 H-NMR (500MHz, CDCl3): δ= 7.63-7.61 (dd, J = 7.9 Hz, 3.4 Hz, 2H), 7.27-7.23 (m, 1H), 7.15-7.10 (m, 4H), 7.07-7.04 (m, 2H), 6.86-6.84 (dd, J = 8.4 Hz, 2.3 Hz, 1H), 6.72-6.69 (m, 2H), 6.64-6.63 (d, J = 2.4 Hz, 1H), 6.36-6.34 (dd, J = 7.8 Hz, 1.4 Hz, 2H), 3.89-3.88 (m, 2H), 3.78-3.77 (d, J = 4 Hz, 2H).

[0184] Preparation Example 14: Synthesis of mFXAR

[0185] [ka]

[0186] A three-neck flask equipped with a thermometer, stirrer, and condenser was charged with 2 g (5.1 mmol) of mFX, 0.64 mL (7.65 mmol) of m-acrylic acid, and 10 mL of toluene. Next, 0.1 g of p-toluenesulfonic acid monohydrate was added, and the mixture was heated and stirred at 100°C for 4 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with chloroform, and the organic layer was separated and distilled. After that, the organic layer was recrystallized with ethyl acetate and hexane to obtain 1.92 g of the white solid compound mFXAR (yield 82.2%, purity 99.8%).

[0187] 1 H-NMR (500MHz, CDCl3): δ= 7.63-7.61 (dd, J = 7.9 Hz, 2.1 Hz, 2H), 7.28-7.25 (t, 1H), 7.15-7.11 (m, 4H), 7.07-7.04 (m, 2H), 6.87-6.85 (m, 1H), 6.72-6.69 (m, 2H), 6.64-6.63 (m, 1H), 6.36-6.34 (d, J = 7.9 Hz, 2H), 6.01 (s, 1H), 5.46-5.45 (d, J = 1.2 Hz, 1H), 4.33-4.31 (m, 2H), 4.03-4.01 (m, 2H), 2.93 (s, 3H).

[0188] Production Example 15: Synthesis of Compounds 4, 13, and 15

[0189] [ka]

[0190] Synthesis of compounds 4, 13, and 15 In a three-neck flask equipped with a thermometer, stirrer, and condenser, 6 g / 6.18 g / 6.61 g (12.6 mmol) of compounds 3-1 / 3-2 / 3-3, respectively, 1.82 g (25.3 mmol) of acrylic acid, 0.016 g (0.12 mmol) of 4-methoxyphenol, 0.025 g (0.12 mmol) of tetraethylammonium bromide, and 25 g of cyclopentanone were mixed. The mixture was stirred at 120 °C for 5 hours and then cooled to room temperature. Ethyl acetate and water were added to the reaction mixture to extract the compounds. The organic layer was separated and purified under reduced pressure to obtain solid compounds 4 / 13 / 15, 7.19 g / 7.21 g / 7.41 g (yields 92.0% / 90% / 88.0%, purities 98.5% / 98.7% / 98.8%), respectively.

[0191] <Compound 4 NMR> 1 H NMR (500 MHz, CDCl3) δ 7.60 (d, 2H), 7.22-7.17 (m, 4H), 6.90 (dd, 2H), 6.81-6.76 (m, 2H), 6.67 (d, 2H), 6.44-6.39 (m, 4H), 6.15-6.09 (m, 2H), 5.84 (dd, 2H) 4.31-4.27 (m, 4H), 4.20-4.17 (m, 2H), 3.94-3.90 (m, 4H), 3.75 (s, 2H); <Compound 13 NMR> 1 H NMR (500 MHz, CDCl3) δ 7.76 (d, 2H), 7.55 (d, 2H), 7.22-7.17 (m, 2H), 6.90 (dd, 2H), 6.81 (s, 2H), 6.67 (d, 2H), 6.44-6.39 (m, 4H), 6.15-6.09 (m, 2H), 5.84 (dd, 2H) 4.31-4.27 (m, 4H), 4.20-4.17 (m, 2H), 3.94-3.90 (m, 4H), 3.75 (s, 2H); <Compound 15 NMR> 1H NMR (500 MHz, CDCl3) δ 7.76 (d, 2H), 7.62 (d, 2H), 7.33-7.30 (m, 2H), 7.06 (dd, 2H), 6.86 (s, 2H), 6.70 (d, 2H), 6.44-6.39 (m, 4H), 6.15-6.09 (m, 2H), 5.84 (dd, 2H) 4.31-4.27 (m, 4H), 4.20-4.17 (m, 2H), 3.94-3.90 (m, 4H), 3.75 (s, 2H).

[0192] Production Example 16: Synthesis of Compounds 6, 8, 10, and 16

[0193] [ka]

[0194] Synthesis of compounds 6, 8, 10, and 16 A three-neck flask equipped with a thermometer, a stirrer, and a condenser was charged with 6.20 g and 6.68 g (10 mmol) of compound 4 / 15, respectively, PGMEA (propylene glycol monomethyl ether acetate) (amounts such that the ratio of the total mass of compound 4 / 15 and compound 5 / 7 / 9 to the total mass of compound 4 / 15, compound 5 / 7 / 9, and PGMEA was 68%), 3.08 g, 3.76 g, and 2.96 g (20 mmol) of compound 5 / 7 / 9, respectively, 0.001 g (0.032 mmol) of 4-methoxyphenol, and 0.026 g (0.1 mmol) of triphenylphosphine. At this time, the PGMEA was added in an amount such that the mass ratio of (compound 4 + compound 5) / (compound 4 + compound 5 + PGMEA), (compound 4 + compound 7) / (compound 4 + compound 7 + PGMEA), (compound 4 + compound 9) / (compound 4 + compound 9 + PGMEA), or (compound 15 + compound 9) / (compound 15 + compound 9 + PGMEA) was 68%.

[0195] The mixture was stirred at 120°C for 2 hours and then at 70°C for 4 hours. Ethyl acetate and water were added to the reaction mixture to extract the compounds. The organic layer was separated, purified under reduced pressure, and solid compounds 6, 8, 10, and 16 were obtained in amounts of 8.47g, 8.77g, 7.61g, and 8.58g (yields: 85.0%, 88%, 83%, and 90%, respectively; purity: 98.7%, 98.6%, 99.0%, and 99.2%).

[0196] <Compound 6 NMR> 1 H NMR (500 MHz, CDCl3) δ 11.00 (s, 2H), 8.13 (d. 2H), 7.59 (d, 2H), 7.39 (d, 2H), 7.22-7.17 (m, 4H), 6.85-6.81 (m, 2H), 6.81-6.77 (m, 2H), 6.66 (d, 2H), 6.43 (d, 2H), 6.27 (dd, 2H), 6.05 (m, 2H), 5.59 (dd, 2H), 5.06 (m, 2H), 4.70-4.66 (m, 4H), 4.45-4.41 (m, 4H), <Compound 8 NMR> 1 H NMR (500 MHz, CDCl3) δ 11.00 (s, 2H), 7.59 (d, 2H), 7.22-7.17 (m, 4H), 6.91-6.98 (m, 2H), 6.81-6.77 (m, 2H), 6.66 (d, 2H), 6.43 (d, 2H), 6.27 (dd, 2H), 6.05 (m, 2H), 5.59 (dd, 2H), 5.06 (m, 2H), 4.51-4.46 (m, 4H), 4.23-4.18 (m, 4H), 3.54 (s, 8H), <Compound 10 NMR> 1H NMR (500 MHz, CDCl3) δ 11.00 (s, 2H), 8.32-8.28 (m, 4H), 7.92-7.88 (m, 4H), 7.59 (d, 2H), 7.22-7.17 (m, 4H), 6.86-6.81 (m, 2H), 6.81-6.78 (m, 2H), 6.66 (d, 2H), 6.43 (d, 2H), 6.27 (dd, 2H), 6.05 (m, 2H), 5.59 (dd, 2H), 5.06 (m, 2H), 4.70-4.66 (m, 4H), 4.45-4.21 (m, 4H), <Compound 16 NMR> 1 H NMR (500 MHz, CDCl3) δ 11.00 (s, 2H), 8.32-8.28 (m, 4H), 7.90-7.86 (m, 4H), 7.76 (d, 2H), 7.68-7.63 (m, 4H), 7.33-7.28 (m, 2H), 6.81-6.77 (m, 2H), 6.66 (d, 2H), 6.43 (d, 2H), 6.27 (dd, 2H), 6.05 (m, 2H), 5.59 (dd, 2H), 5.06 (m, 2H), 4.70-4.66 (m, 4H), 4.45-4.41 (m, 4H).

[0197] Production Example 17: Synthesis of Compounds 12 and 14 Synthesis of compounds 12,14

[0198]

change

[0199] A three-neck flask equipped with a thermometer, stirrer, and condenser was charged with 6.20 g and 6.36 g (10 mmol) of Compound 4 / 13, respectively, cyclopentanone (amounts such that the ratio of the total mass of Compound 4 / 13 and Compound 11 to the total mass of Compound 4 / 13, Compound 11, and cyclopentanone was 50%), 2.97 g (15 mmol) of Compound 11, 0.001 g (0.032 mmol) of 4-methoxyphenol, and 0.026 g (0.1 mmol) of triphenylphosphine. The cyclopentanone was added in an amount such that the mass ratios of (Compound 4 + Compound 11) / (Compound 4 + Compound 11 + cyclopentanone) and (Compound 13 + Compound 11) / (Compound 13 + Compound 11 + cyclopentanone) were 50%.

[0200] The mixture was stirred at 120°C for 2 hours and then at 70°C for 6 hours. Ethyl acetate and water were added to the reaction mixture to extract the compounds. The organic layer was separated and purified under reduced pressure to obtain solid compounds 12 and 14 (8.54g / 8.88g, yields 84.0% and 86%, purity 98.6% and 99.1%, respectively).

[0201] <Compound 12 NMR> 1 H NMR (500 MHz, CDCl3) δ 11.00 (bs, 2H), 8.83 (s, 2H), 8.75 (s, 2H), 8.17-8.13 (m, 4H), 7.74-7.70 (m, 4H), 7.59 (d, 2H), 7.22-7.17 (m, 4H), 6.91-6.87 (m, 2H), 6.81-6.77 (m, 2H), 6.66 (d, 2H), 6.43 (d, 2H), 6.27 (dd, 2H), 6.05 (m, 2H), 5.59 (dd, 2H), 5.06 (m, 2H), 4.70-4.65 (m, 4H), 4:30-4:24 (m, 4H) <Compound 14 NMR> 1H NMR (500 MHz, CDCl3) δ 11.00 (bs, 2H), 8.83 (s, 2H), 8.75 (s, 2H), 8.17-8.12 (m, 4H), 7.74-7.70 (m, 4H), 7.66 (d, 2H), 7.42-7.38 (m, 4H), 7.03-6.91 (m, 2H), 6.81-6.77 (m, 2H), 6.66 (d, 2H), 6.43 (d, 2H), 6.27 (dd, 2H), 6.05 (m, 2H), 5.59 (dd, 2H), 5.06 (m, 2H), 4.69-4.65 (m, 4H), 4.44-4.40 (m, 4H).

[0202] Production Example 18: Synthesis of Compound FXAH [FXAH manufacturing method]

[0203] [ka]

[0204] A two-neck flask equipped with a thermometer and stirrer was charged with 8.66 g (41.2 mmol) of trimellitic anhydride chloride and 20 mL of dry THF, and the mixture was stirred at 0°C under an argon atmosphere. A solution of 5.0 g (13.7 mmol) of FX, 3.3 mL of dry pyridine, and 22 mL of dry THF was slowly added dropwise, followed by stirring at 0°C for 3 hours. The mixture was then stirred at room temperature for an additional 24 hours. After filtering the salt produced using hexane, the filtrate was distilled under reduced pressure to remove the solvent. The concentrated solution was recrystallized with acetic anhydride to obtain 8.0 g of solid compound FXAH (yield 82.0%, purity 99.0%).

[0205] 1 H NMR (CDC13, 500 MHz, ppm): 8.57 (d, 2H), 8.56 (s, 2H), 8.44 (d, 2H), 7.94 (d, 2H), 7.44 (d, 2H), 7.27 (dd, 2H), 7.22 (dd, 2H), 7.21 (d, 2H), 7.19 (d, 2H), 7.05 (dd, 2H).

[0206] Production Example 19: Synthesis of Compounds FXAHAR and FTXAHAR [FXAHAR / FTXAHAR manufacturing method]

[0207] [ka]

[0208] A three-neck flask equipped with a thermometer, stirrer, and condenser was mixed with 7.1 g / 7.3 g (10.0 mmol) of FXAH / FTXAH, respectively, 2.32 g / 2.60 g (20.0 mmol) of 2-hydroxyethyl acrylate / 2.60 g (20.0 mmol) of 2-hydroxyethyl methacrylate, 0.013 g (0.10 mmol) of 4-methoxyphenol, 0.021 g (0.10 mmol) of tetraethylammonium bromide, and 30 g of cyclopentanone. The mixture was stirred at 120 °C for 6 hours and then cooled to room temperature. Ethyl acetate and water were added to the reaction mixture to extract the compounds. The organic layer was separated and purified under reduced pressure to obtain 8.0 g / 7.9 g of solid compounds FXAHAR / FTXAHAR, respectively (yields: 85.0% / 82%, purity: 98.9% / 99.0%).

[0209] <Compound FXAHAR NMR> 1 H NMR (CDC13, 500 MHz, ppm): 1 H NMR (CDC13, 500 MHz, ppm): 11.00 (s, 2H), 8.45 (s, 2H), 8.41 (d, 2H), 8.34 (d, 2H), 7.94 (d, 2H), 7.44 (s, 2H), 7.27 (d, 2H), 7.22 (dd, 2H), 7.21 (d, 2H), 7.19 (d, 2H), 7.05 (dd, 2H), 6.27 (s, 2H), 6.06 (s, 2H), 5.59 (s, 2H), 4.56 (d, 4H), 4.48 (d, 4H). <Compound FTXAHAR NMR> 11H NMR (CDC13, 500 MHz, ppm): 11.00 (s, 2H), 8.46 (s, 2H), 8.41 (d, 2H), 8.34 (d, 2H), 7.94 (d, 2H), 7.65 (d, 2H), 7.44 (s, 2H), 7.33 (dd, 2H), 7.27 (d, 2H), 7.07 (dd, 2H), 7.03 (d, 2H), 6.48 (s, 2H), 6.40 (s, 2H), 4.56 (d, 4H), 4.48 (d, 4H), 2.01 (s, 6H).

Claims

[Claim 1] A compound represented by the following chemical formula 1: 【Chemistry 1】 In the above formula 1, X, R1a, R1b, R2a, and R2b represent substituents; X is O, S, or SO ２ and k1 and k2 are 0; p1 and p2 each independently represent 0 or 1; i) When X is O, it is represented by any one of the following chemical formulas 4-1 to 4-4, 4-6 to 4-14, 4-17 and 4-18; 【Chemistry 2】 【change】 【change】 ii) When X is S, it is represented by any one of the following chemical formulas 5-1 to 5-13: 【Transformation 3】 【change】 【change】 iii) When X is SO 2 , it is represented by any one of the following chemical formulas 6-1 to 6-6. 【Chemistry 4】

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