Fluorene-containing organic compound, preparation method thereof and resin

Abstract

According to the fluorene-containing organic compound, the preparation method thereof and the resin, the fluorene-containing organic compound has the advantages of being good in dissolution, easy to process, excellent in film forming performance and the like, and the refractive index and the thermal stability of the resin can be improved. According to the preparation method of the fluorene-containing organic compound, mixed acid containing acetic acid is adopted as a solvent of a nucleophilic addition reaction system and also serves as an acid catalyst, the conversion rate of the multi-aromatic-ring phenol intermediate can be increased, then the multi-aromatic-ring phenol intermediate and ethylene carbonate or 2, 3-dihalopropanol are subjected to an etherification substitution reaction, and the fluorene-containing organic compound is obtained. The fluorene-containing organic compound synthesized by the method can be used for preparing polycarbonate resin with high refractive index, and the whole synthesis process has good universality, high reaction activity, high conversion rate and easiness in purification.

Description

Technical Field

[0001] The present application relates to the technical field of organic compound synthesis, and in particular to a fluorene-containing organic compound and a preparation method and resin thereof. Background Art

[0002] Polycarbonate (PC) has the advantages of easy processing and molding, impact resistance, light weight, and easy processing and molding. It is a good type of optical resin material and is widely used in the manufacture of precision optical products, such as optical lenses, optical disc substrates, optical fibers, etc. The refractive index in polycarbonate materials mainly depends on the diol / diphenol optical monomers. The refractive index of traditional bisphenol A polycarbonate is only 1.58. Due to the rapid development of information technology, especially the emergence of 5G and 6G high-frequency communication technologies, optoelectronic devices are developing towards lighter, thinner, smaller and higher heat-resistant requirements. Therefore, optical resins require higher refractive index and higher thermal stability. How to further improve the refractive index and thermal stability of polycarbonate materials is a key technical problem that needs to be solved urgently. Summary of the Invention

[0003] This application proposes a fluorene-containing organic compound, its preparation method, and resin. The fluorene-containing organic compound has advantages such as good solubility, easy processing, and excellent film-forming properties. It can also increase the refractive index and thermal stability of the resin. The preparation method of the fluorene-containing organic compound provided in this application can improve synthesis efficiency and conversion rate.

[0004] In a first aspect, the present application provides a fluorene-containing organic compound, wherein the molecular structure of the fluorene-containing organic compound is shown in Formula I or Formula II:

[0005]

[0006] In Formula I and Formula II, R1, R2, and R3 are each independently selected from a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C1-C50 ether group, a hydrogen atom, a deuterium atom, a disubstituted amino group, -F, -Cl, -Br, -I, -CF3, -NO2, and -CN.

[0007] In some embodiments, in the fluorene-containing organic compound, the substituted or unsubstituted C6-C50 aryl group is an all-carbon aryl group;

[0008] In some embodiments, in the fluorene-containing organic compound, the substituted or unsubstituted C6-C50 aromatic group is a heteroaromatic group, and the heteroatom in the heteroaromatic group includes at least one of an oxygen atom, a nitrogen atom, a sulfur atom, and a selenium atom.

[0009] In some embodiments, in the fluorene-containing organic compound, the substituted or unsubstituted C1-C50 alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl and n-octyl.

[0010] In some embodiments, in the fluorene-containing organic compound, when any one of R1, R2, or R3 is substituted, the substituent is selected from a deuterium atom, a halogen atom, a trifluoromethyl group, and a C1-C8 alkyl group.

[0011] In some embodiments, the fluorene-containing organic compound includes any one of the following compounds:

[0012]

[0013]

[0014] In a second aspect, the present application provides a method for preparing a fluorene-containing organic compound, the method comprising:

[0015] The compound represented by formula (a) and the dinaphthol represented by formula (b) are dissolved in a mixed acid containing acetic acid, and the dinaphthol and 9-fluorenone undergo a nucleophilic addition reaction under acid catalysis. The reaction product is recrystallized after removing the acid solution, and is filtered and dried to obtain a polyaromatic phenol intermediate represented by the corresponding formula (c) or formula (d);

[0016] The polyaromatic ring phenol intermediate represented by formula (c) and ethylene carbonate are dissolved in an organic solvent, and an etherification substitution reaction is carried out under the action of a basic catalyst to obtain a fluorene-containing organic compound represented by formula (I); or

[0017] The polyaromatic ring phenol intermediate represented by formula (d) and 2,3-dihalopropanol are dissolved in an organic solvent, and an etherification substitution reaction occurs under the action of a basic catalyst to obtain a fluorene-containing organic compound represented by formula (II);

[0018]

[0019] Wherein, R1, R2, and R3 are each independently selected from a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C1-C50 ether group, a hydrogen atom, a deuterium atom, a disubstituted amino group, -F, -Cl, -Br, -I, -CF3, -NO2, and -CN.

[0020] In some embodiments, the substituted or unsubstituted C6-C50 aryl group is an all-carbon aryl group.

[0021] In some embodiments, the substituted or unsubstituted C6-C50 aryl group is a heteroaryl group, and the heteroatom in the heteroaryl group includes at least one of an oxygen atom, a nitrogen atom, a sulfur atom, and a selenium atom.

[0022] In some embodiments, the substituted or unsubstituted C1-C50 alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl and n-octyl.

[0023] In some embodiments, when any one of R1, R2, or R3 is substituted, the substituent is selected from a deuterium atom, a halogen atom, a trifluoromethyl group, or a C1-C8 alkyl group.

[0024] In some embodiments, the upper limit of the molar ratio of the compound represented by formula (a) to the dinaphthol is 1:10.

[0025] In some embodiments, the mixed acid further comprises other acids, and the other acids comprise one or more of methanesulfonic acid, trifluoroacetic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, and sulfuric acid.

[0026] In some embodiments, the mixed acid further comprises other acids, and the volume ratio of the other acids to the acetic acid is 1:(1-100).

[0027] In some embodiments, the temperature of the nucleophilic addition reaction is 80° C. to 140° C., and the reaction time is 0.5 h to 36 h.

[0028] In some embodiments, the method of removing the acid from the reaction product is precipitation or extraction.

[0029] In some embodiments, the solvent used in the recrystallization includes one or more of acetone, methanol, ethanol, tetrahydrofuran, ethyl acetate, dichloromethane, acetonitrile, methyl tert-butyl ether, toluene, and petroleum ether.

[0030] In some embodiments, the molar ratio of the polyaromatic ring phenol intermediate to the ethylene carbonate is 1:(2-10).

[0031] In some embodiments, the molar ratio of the polyaromatic ring phenol intermediate to the 2,3-dihalopropanol is 1:(2-10).

[0032] In some embodiments, the organic solvent is one or more of dimethyl sulfoxide, N,N-dimethylformamide, diethylene glycol dimethyl ether, N-methylpyrrolidone, toluene, xylene, and trimethylbenzene.

[0033] In some embodiments, the basic catalyst includes one or more of sodium tert-butoxide, potassium tert-butoxide, potassium phosphate, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, and sodium hydride.

[0034] In some embodiments, the temperature of the etherification substitution reaction is 100°C to 150°C.

[0035] In some embodiments, the etherification substitution reaction time is 0.5 h to 36 h.

[0036] In a third aspect, the present application provides a resin, wherein the raw materials for preparing the resin include any one of the above-mentioned fluorene-containing organic compounds.

[0037] In some embodiments, the raw materials for preparing the resin further include other raw materials, and the other raw materials include at least one of carbonic acid diester, dicarboxylic acid, and dicarboxylic acid ester; the molar ratio of the other raw materials to the fluorene-containing organic compound is (0.95-1.15):1.

[0038] In a fourth aspect, the present application provides an optical film, wherein the raw materials for preparing the optical film include the above-mentioned resin.

[0039] In a fifth aspect, the present application provides an electronic device comprising the above-mentioned optical film.

[0040] Compared with the prior art, this application uses a mixed acid containing acetic acid as the solvent for the nucleophilic addition reaction system, which also serves as an acidic catalyst. This can increase the conversion rate of polyaromatic phenol intermediates, and then the polyaromatic phenol intermediates are subjected to an etherification substitution reaction with ethylene carbonate or 2,3-dihalopropanol to obtain fluorene-containing organic compounds. The fluorene-containing organic compounds synthesized in this application are naphthyloxyspirocyclic diol monomers or aromatic cyclic ether diol monomers. Both types of monomers can be used to prepare high-refractive index polycarbonate resins. The entire synthesis process has good universality, high reactivity, high conversion rate, and easy purification. DETAILED DESCRIPTION

[0041] The technical solutions provided by the present invention are further described below in conjunction with specific examples and comparative examples, but the present application is not limited to the following examples.

[0042] In order to better understand the technical solution of the present application, the embodiments of the present application are described in detail below.

[0043] It should be clear that the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0044] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be understood to indicate or imply relative importance or to implicitly indicate the quantity of the technical features indicated. Thus, a feature specified as "first" or "second" may explicitly or implicitly include one or more of the features.

[0045] At present, the main method used to synthesize spirofluorene monomers is the sulfuric acid / mercaptopropionic acid catalysis method. However, this method has disadvantages such as low reaction rate, low conversion rate, and many side reactions for monomers with spirofluorene cyclic ether structures, which brings great difficulties to the purification of subsequent products. It is also not suitable for the synthesis of some spirofluorene-containing naphthalene polyhydroxy intermediates. Therefore, it is necessary to develop new synthetic methods to expand the synthetic path of polyfluorene monomers and efficiently synthesize this type of organic compounds containing spirofluorene structures as reactive monomers for optical resins.

[0046] The present application provides a method for preparing a fluorene-containing organic compound, the method comprising:

[0047] Step S10, dissolving the compound represented by formula (a) and the dinaphthol represented by formula (b) in a mixed acid containing acetic acid, and subjecting the dinaphthol to a nucleophilic addition reaction with 9-fluorenone under acid catalysis. The reaction product is recrystallized after removing the acid solution, filtered, and dried to obtain a polyaromatic phenol intermediate represented by the corresponding formula (c) or formula (d);

[0048] Step S21, dissolving the polyaromatic ring phenol intermediate represented by formula (c) and ethylene carbonate in an organic solvent, and causing an etherification substitution reaction under the action of a basic catalyst to obtain a fluorene-containing organic compound represented by formula (I); or

[0049] Step S22, dissolving the polyaromatic phenol intermediate represented by formula (d) and 2,3-dihalopropanol in an organic solvent, and subjecting them to an etherification substitution reaction under the action of a basic catalyst to obtain a fluorene-containing organic compound represented by formula (II);

[0050]

[0051] Wherein, R1, R2, and R3 are each independently selected from a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C1-C50 ether group, a hydrogen atom, a deuterium atom, a disubstituted amino group, -F, -Cl, -Br, -I, -CF3, -NO2, and -CN.

[0052] In the preparation method provided in the present application, a mixed acid containing acetic acid is used as a solvent for the nucleophilic addition reaction system, and is also an acidic catalyst, which can improve the conversion rate of polyaromatic ring phenol intermediates. The polyaromatic ring phenol intermediates are then subjected to an etherification substitution reaction with ethylene carbonate or 2,3-dihalopropanol to obtain a fluorene-containing organic compound. The fluorene-containing organic compound synthesized in the present application is a naphthyloxyspirocyclic diol monomer or an aromatic cyclic ether diol monomer. Both types of monomers can be used to prepare high-refractive index polycarbonate resins. The entire synthesis process has good universality, high reaction activity, high conversion rate, and is easy to purify.

[0053] In some embodiments, the sulfuric acid / β-mercaptopropionic acid method can be used to synthesize spirofluorene monomers. Sulfuric acid / β-mercaptopropionic acid provides acidic conditions, dihydroxynaphthalene and fluorenone undergo nucleophilic addition, and finally the water molecules are removed to obtain the target compound. However, due to its poor overall reactivity, slow reaction rate, low conversion rate, and oligomerization of dihydroxynaphthalene and fluorenone will occur during the reaction to obtain oligomeric compounds, and it is difficult to suppress the occurrence of side reactions in the reaction, making the reaction system very complicated and causing great difficulties for the subsequent separation and purification of the compounds.

[0054] In the present application, a mixed acid containing acetic acid is used as a solvent for the nucleophilic addition reaction system. Since the mixed acid containing acetic acid is a mixed solution of multiple inorganic acids, it is an acidic catalyst while serving as a solvent for the reaction system. It can accelerate the reaction rate and improve the conversion rate of polyaromatic ring phenol intermediates. Compared with the sulfuric acid / β-mercaptopropionic acid method for synthesizing spirofluorene monomers, dinaphthol and 9-fluorenone undergo nucleophilic addition reaction under acid catalysis, which can reduce the occurrence of side reactions and improve the conversion rate of spirofluorene monomers (i.e., fluorene-containing organic compounds). And due to the mixed acid reaction system, the subsequent separation and purification of the compound is simpler and easier, and the entire preparation method has good universality and is easy to purify. The preparation method provided in the present application can achieve high yield and high purity preparation of polyaromatic ring cyclic ether structure-containing fluorene organic compounds, so that the fluorene-containing organic compounds have both high refractive index, and the post-processing purification method is efficient and concise.

[0055] The molecular structure of the fluorene-containing organic compound prepared according to the above preparation method is shown in Formula I or Formula II:

[0056]

[0057] In formula (a), formula (b), formula (c), formula (d), formula I and formula II, R1, R2, and R3 are each independently selected from a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C1-C50 ether group, a hydrogen atom, a deuterium atom, a disubstituted amino group, -F, -Cl, -Br, -I, -CF3, -NO2, and -CN.

[0058] In some embodiments, the substituted or unsubstituted C6-C50 aryl group in the fluorene-containing organic compound is an all-carbon aryl group. Alternatively, the C6-C50 aryl group may be a phenyl group, a phenylalkyl group, a biphenyl group, or a condensed-ring aromatic hydrocarbon group (e.g., a naphthyl group, anthracenyl group, or a phenanthrenyl group). The biphenyl group and the condensed-ring aromatic hydrocarbon group may be further substituted with an alkyl group or an alkenyl group. Examples of C6-C50 aryl groups include phenyl, benzyl, biphenyl, p-tolyl, o-tolyl, m-tolyl, and naphthyl.

[0059] In some embodiments, in the fluorene-containing organic compound, the substituted or unsubstituted C6-C50 aryl group is a heteroaryl group, and the heteroatom in the heteroaryl group includes at least one of an oxygen atom, a nitrogen atom, a sulfur atom, and a selenium atom.

[0060] In some embodiments, the substituted or unsubstituted C1-C50 alkyl group in the fluorene-containing organic compound may be a chain alkyl group or a cyclic alkyl group. The chain alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group. The hydrogen atoms on the ring of the cyclic alkyl group may be further substituted by an alkyl group. The preferred lower limit of the number of carbon atoms in the C1-C50 alkyl group is 1, 2, 3, 4, or 5, and the preferred upper limit is 6, 7, 8, or 10. Examples of C1-C50 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, and n-octyl.

[0061] When the aforementioned C1-C50 alkyl group contains an oxygen atom, it may be a C1-C50 alkoxy group. Preferably, a C1-C10 alkoxy group is selected; more preferably, a C1-C6 alkoxy group is selected. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, cyclopentoxy, and cyclohexyloxy.

[0062] In some embodiments, the portion of the substituted or unsubstituted C1-C50 ether group connected to the oxygen atom is a substituted or unsubstituted C1-C50 alkyl group or a trifluoromethyl group. Examples of ether groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, and n-octyl.

[0063] In some embodiments, in the fluorene-containing organic compound, when any one of R1, R2, or R3 is substituted, the substituent is selected from a deuterium atom, a halogen atom, a trifluoromethyl group, and a C1-C8 alkyl group.

[0064] The following is a detailed introduction to this scheme in combination with the synthesis process:

[0065] In step S10, the compound represented by formula (a) and the dinaphthol represented by formula (b) are dissolved in a mixed acid containing acetic acid. Under acid catalysis, the dinaphthol and 9-fluorenone undergo a nucleophilic addition reaction. The reaction product is recrystallized after removing the acid solution, filtered and dried to obtain the corresponding polyaromatic phenol intermediate represented by formula (c) or formula (d). The reaction mechanism is as follows:

[0066]

[0067] In some embodiments, the upper limit of the molar ratio of the compound represented by formula (a) to dinaphthol (formula (b)) is 1:10. Specifically, it can be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, etc., and of course it can also be other values ​​within the above range, which are not limited here. Preferably, the lower limit of the molar ratio of the compound represented by formula (a) to dinaphthol (formula (b)) is 1:2. Controlling the molar ratio of the compound represented by formula (a) to dinaphthol is conducive to the full progress of the reaction and reduces the occurrence of side reactions.

[0068] In the actual addition process, the compound represented by formula (a) and dinaphthol can be added all at once or in small amounts over multiple times to dissolve them in the reaction solvent, and then the mixed acid is gradually added dropwise.

[0069] In some embodiments, the mixed acid further comprises other acids, and the other acids comprise one or more of methanesulfonic acid, trifluoroacetic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, and sulfuric acid.

[0070] In some embodiments, the mixed acid further comprises other acids, and the volume ratio of the other acids to acetic acid is 1:(1-100). Specifically, it can be 1:1, 1:2, 1:3, 1:5, 1:10, 1:20, 1:40, 1:50, 1:60, 1:80 or 1:100, etc., and of course, it can also be other values ​​within the above range, which are not limited here. After a large number of experiments, it was found that mildly acidic acetic acid can act as a solvent in the reaction system and then cooperate with other acids to catalyze the reaction. Preferably, the volume ratio of the other acids to acetic acid is 1:(1-2).

[0071] In some embodiments, the temperature of the nucleophilic addition reaction is 80°C to 140°C. The temperature of the nucleophilic addition reaction can be 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C, etc. Of course, it can also be other values ​​within the above range, which is not limited here. Controlling the temperature of the nucleophilic addition reaction is beneficial to improving the reaction efficiency and conversion rate. Preferably, the temperature of the nucleophilic addition reaction is 120°C to 140°C.

[0072] In some embodiments, the nucleophilic addition reaction time is 0.5 h to 36 h. The etherification substitution reaction time can be 0.5 h, 1 h, 2 h, 5 h, 10 h, 12 h, 15 h, 18 h, 24 h, 32 h, or 36 h, and other values ​​within the above range are also possible. Preferably, the nucleophilic addition reaction time is 24 h to 36 h.

[0073] In some embodiments, the method for removing the acid solution from the reaction product is precipitation or extraction. By using the above-mentioned method for removing the acid solution, the acid solution in the reaction product can be removed quickly and efficiently, and the removal process is simple and convenient.

[0074] In some embodiments, the solvent used for recrystallization includes one or more of acetone, methanol, ethanol, tetrahydrofuran, ethyl acetate, dichloromethane, acetonitrile, methyl tert-butyl ether, toluene, and petroleum ether.

[0075] In step S21, the polyaromatic ring phenol intermediate represented by formula (c) and ethylene carbonate are dissolved in an organic solvent, and an etherification substitution reaction is carried out under the action of an alkaline catalyst. The mixture is extracted, recrystallized, filtered and dried to obtain a fluorene-containing organic compound represented by formula (I).

[0076]

[0077] Among them, R1, R2, and R3 are as described above and will not be repeated here.

[0078] In some embodiments, the molar ratio of the polyaromatic phenol intermediate to ethylene carbonate is 1:(2-10), specifically 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, etc., and of course it can also be other values ​​within the above range, which is not limited here.

[0079] In some embodiments, the organic solvent is one or more of dimethyl sulfoxide, N,N-dimethylformamide, diethylene glycol dimethyl ether, N-methylpyrrolidone, toluene, xylene, and trimethylbenzene. Preferably, the organic solvent is N,N-dimethylformamide or toluene.

[0080] In some embodiments, the alkaline catalyst comprises one or more of sodium tert-butoxide, potassium tert-butoxide, potassium phosphate, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, and sodium hydride. Preferably, the alkaline catalyst is potassium carbonate or potassium phosphate.

[0081] In some embodiments, the temperature of the etherification substitution reaction is 100°C to 150°C. The temperature of the etherification substitution reaction can specifically be 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C, etc., and can also be other values ​​within the above range, which is not limited here. Preferably, the temperature of the etherification substitution reaction is 130°C to 150°C.

[0082] In some embodiments, the etherification substitution reaction time is 0.5 h to 36 h. The etherification substitution reaction time can specifically be 0.5 h, 1 h, 2 h, 5 h, 10 h, 12 h, 15 h, 18 h, 24 h, 32 h, or 36 h, etc., and of course other values ​​within the above range are also possible, and are not limited here. Preferably, the etherification substitution reaction time is 5 h to 24 h.

[0083] In some embodiments, the recrystallization solvent is selected from one or more of acetone, methanol, ethanol, tetrahydrofuran, ethyl acetate, dichloromethane, acetonitrile, methyl tert-butyl ether, toluene, and petroleum ether.

[0084] In step S22, the polyaromatic ring phenol intermediate represented by formula (d) and 2,3-dihalopropanol are dissolved in an organic solvent, and an etherification substitution reaction is carried out under the action of an alkaline catalyst. The mixture is extracted, recrystallized, filtered and dried to obtain a fluorene-containing organic compound represented by formula (II).

[0085]

[0086] Wherein, R1, R2, and R3 are as described above and will not be repeated here, and X is selected from halogen, specifically Cl, Br, and I.

[0087] In some embodiments, the molar ratio of the polyaromatic phenol intermediate to 2,3-dihalopropanol is 1:(2-10), specifically 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10, and other values ​​within the above range are also possible, and are not limited here.

[0088] In some embodiments, the organic solvent is one or more of dimethyl sulfoxide, N,N-dimethylformamide, diethylene glycol dimethyl ether, N-methylpyrrolidone, toluene, xylene, and trimethylbenzene. Preferably, the organic solvent is N,N-dimethylformamide or dimethyl sulfoxide.

[0089] In some embodiments, the alkaline catalyst comprises one or more of sodium tert-butoxide, potassium tert-butoxide, potassium phosphate, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, and sodium hydride. Preferably, the alkaline catalyst is potassium phosphate.

[0090] In some embodiments, the temperature of the etherification substitution reaction is 100°C to 150°C. The temperature of the etherification substitution reaction can specifically be 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C, and can of course be other values ​​within the above range, which is not limited here. Preferably, the temperature of the etherification substitution reaction is 140°C to 150°C.

[0091] In some embodiments, the etherification substitution reaction time is 0.5 h to 36 h. The etherification substitution reaction time can specifically be 0.5 h, 1 h, 2 h, 5 h, 10 h, 12 h, 15 h, 18 h, 24 h, 32 h, or 36 h, and of course other values ​​within the above range are also possible, and are not limited here. Preferably, the etherification substitution reaction time is 24 h.

[0092] In some embodiments, the recrystallization solvent is selected from one or more of acetone, methanol, ethanol, tetrahydrofuran, ethyl acetate, dichloromethane, acetonitrile, methyl tert-butyl ether, toluene, and petroleum ether. Preferably, the recrystallization solvent is toluene.

[0093] In some embodiments, the drying temperature in steps S21 and S22 is 80°C to 120°C, specifically 80°C, 90°C, 100°C, 110°C, or 120°C, and may be other values ​​within the above range. The purpose of drying is primarily to remove residual solvent and water from the product.

[0094] In some embodiments, the fluorene-containing organic compound includes any one of the following compounds:

[0095]

[0096] The present application also provides a resin, the raw materials for preparing the resin including the aforementioned fluorene-containing organic compound. Specifically, the resin can be one or more of polyester, polycarbonate, polyester carbonate, polyphenylene ether, polyurethane, sulfone polymer, thioether polymer, epoxy resin, phenolic resin, polyamide, polyimide, and polymethyl methacrylate. Preferably, the resin includes at least one of polyester, polycarbonate, and polyester carbonate. The resin can be prepared using currently known methods, for example, by an ester exchange polycondensation reaction.

[0097] In some embodiments, the weight average molecular weight of the resin is 5*10 3 ~5*10 5 , specifically it can be 5*10 3 、5.5*10 3 、5.9*10 3 、6.5*10 3 , 7*10 3 ,7.5*103 、8*10 3 , 1*10 4 , 5*10 4 、8*10 4 , 1*10 5 、3*10 5 , 5*10 5 Of course, it can also be other values ​​within the above range, which is not limited here.

[0098] In some embodiments, the resin can be obtained by reacting the fluorene-containing organic compound with other raw materials, wherein the other raw materials include at least one of a carbonic acid diester, a dicarboxylic acid, and a dicarboxylic acid ester.

[0099] In some embodiments, the carbonic acid diester can be selected from one or more of diphenyl carbonate, ditolyl carbonate, diethylphenyl carbonate, diisopropylphenyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc., preferably diphenyl carbonate.

[0100] In some embodiments, the dicarboxylic acid may be selected from any one of terephthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,2-biphenyl dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, and 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, or a combination of at least two thereof.

[0101] In some embodiments, the dicarboxylic acid ester is selected from any one or a combination of at least two of dimethyl terephthalate, diethyl terephthalate, dimethyl terephthalate, dimethyl 1,4-naphthalene dicarboxylate, dimethyl 2,6-naphthalene dicarboxylate, dimethyl 2,2-biphenyl dicarboxylate, dimethyl 1,4-cyclohexane dicarboxylate, and 2,2'-bis(carboxymethyl methoxy)-1,1'-binaphthyl. Preferably, dimethyl 1,4-cyclohexane dicarboxylate and / or dimethyl 2,6-naphthalene dicarboxylate are used.

[0102] In some embodiments, the molar ratio of other raw materials to the fluorene-containing organic compound is (0.95-1.15):1, specifically 0.95:1, 0.98:1, 0.99:1, 1.0:1, 1.05:1, 1.08:1, 1.1:1 or 1.05:1, etc. Of course, it can also be other values ​​within the above range, which is not limited here.

[0103] In some embodiments, the reaction raw materials further include a catalyst, and the catalyst is selected from lithium chloride, sodium chloride, potassium chloride, cesium chloride, lanthanum acetylacetonate, cerium acetylacetonate, tetrabutyl titanate, tetraisopropyl titanate, sodium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, sodium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, cesium carbonate, magnesium acetate, acetic acid, One or more of calcium stearate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenyl phosphate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylamine, dimethylbenzylamine, triphenylamine, diethylamine, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate, preferably one or more of sodium hydroxide, sodium bicarbonate, and cesium carbonate.

[0104] In order to improve the efficiency and yield of resin preparation, antioxidants, release agents, ultraviolet absorbers, fluidity improvers, crystallization nucleating agents, reinforcing agents, dyes, color powders, antistatic agents or antibacterial agents and other additives may be added during the preparation of the resin of the present application, without limitation here.

[0105] In the optional technical solution of this application, the above resin can be used to synthesize high-refractive-index polycarbonate materials, and further used to prepare optical materials such as optical lenses and optical films. In the field of smart terminals, a large amount of optical polycarbonate materials are used in cameras and display polarizers. In addition to synthesizing optical monomers for use in the field of polycarbonate materials, various epoxy resin monomers containing fluorene structures can also be synthesized, and are expected to be used in adhesives, coatings, laminates, molding materials, casting materials and other fields.

[0106] The present application also provides an optical film, the raw materials for preparing the optical film include the above-mentioned resin.

[0107] The present application also provides an electronic device, which includes the above-mentioned optical film. The electronic device can be an optical module, a camera, a mobile phone, a wearable device, etc., which is not limited here.

[0108] The following further describes the embodiments of the present invention in multiple embodiments. The embodiments of the present invention are not limited to the following specific embodiments. Within the scope of the unchanged main rights, appropriate changes can be made to the implementation.

[0109] Example 1 (Benzoxanthene Spirofluorene Diol Monomer 1)

[0110] 1) Under nitrogen, 19.2 g (120 mmol) of 1,5-dihydroxynaphthalene, 7.2 g (40 mmol) of fluorenone, 40 mL of hydrobromic acid, and 40 mL of glacial acetic acid were added to a three-necked flask. The mixture was heated to 120°C, stirred, and dissolved. The entire solution was allowed to react for 18 h. After the reaction was returned to room temperature, water was added to the system to precipitate the reaction product, which was then filtered. The filter cake was retained, dried, slurried in acetone, and filtered. Finally, the mixture was recrystallized from methanol / acetone and dried under vacuum at 100°C for 12 h to obtain 14.8 g of an off-white intermediate (yield: 80%).

[0111]

[0112] 2) Under nitrogen, 14.5 g (31.2 mmol) of the intermediate prepared in step 1), 6.9 g (78.1 mmol) of ethylene carbonate, 886 mg (6.2 mmol) of anhydrous potassium carbonate, and 140 mL of N,N-dimethylformamide (DMF) were added to a two-necked flask and refluxed at 130°C for 3.5 h. After completion of the reaction, the DMF was removed under reduced pressure, and the mixture was extracted 2-3 times with ethyl acetate and saturated brine. The organic phase was dried, cooled, crystallized, filtered, and dried under vacuum at 100°C to obtain 10.3 g of white crystalline particles (yield: 60%), i.e., benzoxanthene spirofluorene diol monomer 1.

[0113]

[0114] Example 2 (Benzoxanthene Spirofluorene Diol Monomer 2)

[0115] 1) Under nitrogen, add 10 g (62.4 mmol) of 1,4-naphthalene diol, 4.5 g (25 mmol) of fluorenone, 40 mL of hydrobromic acid, and 50 mL of glacial acetic acid to a three-necked flask. Heat to 120°C, stir to dissolve, and allow the entire solution to react for 18 hours. After the reaction is returned to room temperature, water is added to the system to precipitate the reaction product, which is then filtered. The filter cake is retained, dried, slurried in acetonitrile, and filtered. Finally, recrystallize from acetonitrile / acetone and dry in a vacuum at 100°C for 12 hours to obtain 9.9 g of an off-white intermediate (yield: 85%).

[0116]

[0117] 2) Under nitrogen, 7 g (15.1 mmol) of the intermediate prepared in step 1), 3.32 g (37.75 mmol) of ethylene carbonate, 416 mg (3 mmol) of anhydrous potassium carbonate, and 70 mL of N,N-dimethylformamide (DMF) were added to a two-necked flask and refluxed at 130°C for 3 h. After completion of the reaction, the DMF was removed under reduced pressure, and the mixture was extracted 2-3 times with ethyl acetate and saturated brine. The organic phase was dried, cooled, crystallized, filtered, and dried under vacuum at 100°C to obtain 5.7 g of white crystalline particles (yield: 68%), i.e., benzoxanthene spirofluorene diol monomer 2.

[0118]

[0119] Example 3 (Benzoxanthene Spirofluorene Diol Monomer 3)

[0120] 1) Under nitrogen, add 24 g (150 mmol) of 1,6-naphthalene diol, 9 g (50 mmol) of fluorenone, 100 mL of hydrobromic acid, and 100 mL of glacial acetic acid to a three-necked flask. Heat to 120°C, stir to dissolve, and allow the entire solution to react for 18 hours. After the reaction is returned to room temperature, water is added to the system to precipitate the reaction product, which is then filtered. The filter cake is retained, dried, slurried in acetone, and filtered. Finally, the mixture is recrystallized from methanol / acetone and dried under vacuum at 100°C for 12 hours to obtain 17.4 g of an off-white intermediate (yield: 75%).

[0121]

[0122] 2) Under nitrogen, 10 g (21.5 mmol) of the intermediate prepared in step 1), 4.74 g (53.8 mmol) of ethylene carbonate, 593 mg (4.3 mmol) of anhydrous potassium carbonate, and 100 mL of N,N-dimethylformamide (DMF) were added to a two-necked flask and refluxed at 130°C for 4 h. After completion of the reaction, the DMF was removed under reduced pressure, and the mixture was extracted 2-3 times with ethyl acetate and saturated brine. The organic phase was dried, recrystallized from tetrahydrofuran and ethyl acetate, and dried under vacuum at 100°C for 12 h to obtain 8 g (yield: 58%) of white crystalline granules, i.e., benzoxanthene spirofluorene diol monomer 3.

[0123]

[0124] Example 4 (Benzoxanthene Spirofluorene Diol Monomer 4)

[0125] 1) Under nitrogen, 7.4 g (46.2 mmol) of 1,7-naphthalene diol, 3.47 g (19.3 mmol) of fluorenone, 50 mL of hydrobromic acid, and 50 mL of glacial acetic acid were added to a three-necked flask. The mixture was heated to 120°C, stirred, and dissolved. The reaction mixture was allowed to react for 18 h. After the reaction was returned to room temperature, water was added to the system to precipitate the reaction product, which was then filtered. The filter cake was retained, dried, slurried in acetone, and filtered. Finally, the mixture was recrystallized from methanol / acetone and dried under vacuum at 100°C for 12 h to obtain 6.5 g of an off-white intermediate (yield: 73%).

[0126]

[0127] 2) Under nitrogen, 6.5 g (14 mmol) of the intermediate prepared in step 1), 3.08 g (35 mmol) of ethylene carbonate, 386 mg (2.8 mmol) of anhydrous potassium carbonate, and 60 mL of N,N-dimethylformamide (DMF) were added to a two-necked flask and refluxed at 130°C for 5 h. After completion of the reaction, the DMF was removed under reduced pressure, and the mixture was extracted 2-3 times with ethyl acetate and saturated brine. The organic phase was dried, cooled, crystallized, filtered, and dried under vacuum at 100°C for 12 h to obtain 4.3 g (yield: 56%) of white crystalline granules, i.e., benzoxanthene spirofluorene diol monomer 4.

[0128]

[0129] Example 5 (Benzoxanthene Spirofluorene Diol Monomer 5)

[0130] 1) Under nitrogen, 4 g (25 mmol) of 1,8-dihydroxynaphthalene, 2.14 g (11.9 mmol) of fluorenone, 424 mL of hydrobromic acid, and 24 mL of glacial acetic acid were added to a three-necked flask. The mixture was heated to 120°C, stirred, and dissolved. The entire solution was allowed to react for 24 h. After the reaction was returned to room temperature, the mixture was extracted three times with ethyl acetate and water. The organic phase was dried, petroleum ether was added, cooled, crystallized, filtered, and dried under vacuum at 100°C for 12 h to obtain 5 g of an off-white intermediate (yield: 92%).

[0131]

[0132] 2) Under nitrogen, 3.77 g (8.1 mmol) of the intermediate prepared in step 1), 2.9 g (32.9 mmol) of ethylene carbonate, 339 mg (1.6 mmol) of anhydrous potassium phosphonate, and 80 mL of N,N-dimethylformamide (DMF) were added to a two-necked flask and refluxed at 130°C for 24 h. After completion of the reaction, the DMF was removed under reduced pressure, and the mixture was extracted 2-3 times with ethyl acetate and saturated brine. The organic phase was dried, cooled, crystallized, filtered, and dried under vacuum at 100°C for 12 h to obtain 3.04 g (yield: 68%) of white crystalline granules, i.e., benzoxanthene spirofluorene diol monomer 5.

[0133]

[0134] Example 6 (Benzoxanthene Spirofluorene Diol Monomer 6)

[0135] 1) Under nitrogen, 24 g (150 mmol) of 2,3-dihydroxynaphthalene, 9 g (50 mmol) of fluorenone, 50 mL of hydrobromic acid, and 50 mL of glacial acetic acid were added to a three-necked flask. The mixture was heated to 120°C, stirred, and dissolved. The entire solution was allowed to react for 24 h. After the reaction was returned to room temperature, the mixture was extracted three times with ethyl acetate and water. The organic phase was dried, concentrated, cooled, and then added to tetrahydrofuran for crystallization. The mixture was then dried under vacuum at 100°C for 12 h to obtain 8.4 g of an off-white intermediate (yield: 35%).

[0136]

[0137] 2) Under nitrogen, 10 g (20.7 mmol) of the intermediate prepared in step 1), 6.7 g (51.75 mmol) of 2,3-dichloropropanol, 26.4 g (124.2 mmol) of anhydrous potassium phosphonate, and 100 mL of N,N-dimethylformamide (DMF) were added to a two-necked flask and heated under reflux at 150°C for 24 h. After completion of the reaction, the DMF was removed under reduced pressure, and the mixture was extracted 2-3 times with ethyl acetate and water. The organic phase was dried and filtered. After removing the ethyl acetate under reduced pressure, 100 mL of toluene was added. The product was cooled at 0°C to precipitate, and then dried under vacuum at 100°C for 12 h to obtain 6 g (yield: 47%) of white crystalline granules, i.e., benzoxanthene spirofluorene diol monomer 6.

[0138]

[0139] Application Example 1

[0140] Synthesis of polycarbonate materials:

[0141] Under nitrogen atmosphere, 0.1 mol of benzoxanthene spirofluorene diol monomer 1 and 0.102 mol of diphenyl carbonate (benzoxanthene spirofluorene diol monomer 1: diphenyl carbonate = 1:1.02, molar ratio) were added to a 250 mL four-necked glass flask equipped with a mechanical stirrer, heated to 200 ° C, and 1×10 -4 mol of 1,5,7-triazidobicyclo(4.4.0)dec-5-ene (relative to the amount of benzoxanthene spirofluorene diol monomer 1) was subjected to an ester exchange reaction at normal pressure for 30 minutes to synthesize a prepolymer; then the reaction temperature was slowly increased to 220°C, the vacuum degree was slowly increased to 10 kPa, and the reaction was continued for 30 minutes; finally, the reaction temperature was slowly increased to 250°C, the vacuum degree was slowly increased to 100 Pa, and the reaction was continued for 20 minutes to finally obtain polycarbonate.

[0142] The obtained polycarbonate had a refractive index nd of 1.6877, an Abbe number v of 17.5, a weight average molecular weight Mw of 15,000, a dispersion index PDI of 2.24, a Tg of 218.2°C, and a T d-5％ It is 360℃.

[0143] Application Example 2

[0144] Synthesis of polycarbonate materials:

[0145] Under nitrogen atmosphere, 0.1 mol of benzoxanthene spirofluorene diol monomer 2 and 0.102 mol of diphenyl carbonate (benzoxanthene spirofluorene diol monomer 2: diphenyl carbonate = 1:1.02, molar ratio) were added to a 250 mL four-necked glass flask equipped with a mechanical stirrer, heated to 180 ° C, and 1×10 -4 mol of 1,5,7-triazidobicyclo(4.4.0)dec-5-ene (relative to the amount of benzoxanthene spirofluorene diol monomer 2) was subjected to an ester exchange reaction at normal pressure for 30 minutes to synthesize a prepolymer; then the reaction temperature was slowly increased to 220°C, the vacuum degree was slowly increased to 10 kPa, and the reaction was continued for 30 minutes; finally, the reaction temperature was slowly increased to 240°C, the vacuum degree was slowly increased to 100 Pa, and the reaction was continued for 20 minutes to finally obtain polycarbonate.

[0146] The obtained polycarbonate had a refractive index nd of 1.6842, an Abbe number v of 17.8, a weight average molecular weight Mw of 24300, a dispersion index PDI of 2.16, a Tg of 206.8°C, and a T d-5％ It is 355℃.

[0147] Application Example 3

[0148] Synthesis of polycarbonate materials:

[0149] Under nitrogen atmosphere, 0.1 mol of benzoxanthene spirofluorene diol monomer 3 and 0.102 mol of diphenyl carbonate (benzoxanthene spirofluorene diol monomer 3: diphenyl carbonate = 1:1.02, molar ratio) were added to a 250 mL four-necked glass flask equipped with a mechanical stirrer, heated to 200 ° C, and 1×10 -4 mol of 1,5,7-triazidobicyclo(4.4.0)dec-5-ene (relative to the amount of benzoxanthene spirofluorene diol monomer 3) was subjected to an ester exchange reaction at normal pressure for 30 minutes to synthesize a prepolymer; then the reaction temperature was slowly increased to 220°C, the vacuum degree was slowly increased to 10 kPa, and the reaction was continued for 30 minutes; finally, the reaction temperature was slowly increased to 250°C, the vacuum degree was slowly increased to 100 Pa, and the reaction was continued for 20 minutes to finally obtain polycarbonate.

[0150] The obtained polycarbonate had a refractive index nd of 1.6866, an Abbe number v of 17.4, a weight average molecular weight Mw of 19600, a dispersion index PDI of 2.27, a Tg of 216.8°C, and a T d-5％ It is 360℃.

[0151] Application Example 4

[0152] Synthesis of polycarbonate materials:

[0153] Under nitrogen atmosphere, 0.1 mol of benzoxanthene spirofluorene diol monomer 4 and 0.102 mol of diphenyl carbonate (benzoxanthene spirofluorene diol monomer 4: diphenyl carbonate = 1:1.02, molar ratio) were added to a 250 mL four-necked glass flask equipped with a mechanical stirrer, heated to 190 ° C, and 1×10 -4 mol of 1,5,7-triazidobicyclo(4.4.0)dec-5-ene (relative to the amount of benzoxanthene spirofluorene diol monomer 4) was subjected to an ester exchange reaction at normal pressure for 30 minutes to synthesize a prepolymer; then the reaction temperature was slowly increased to 210°C, the vacuum degree was slowly increased to 10 kPa, and the reaction was continued for 30 minutes; finally, the reaction temperature was slowly increased to 240°C, the vacuum degree was slowly increased to 100 Pa, and the reaction was continued for 20 minutes to finally obtain polycarbonate.

[0154] The obtained polycarbonate had a refractive index nd of 1.6852, an Abbe number v of 17.5, a weight average molecular weight Mw of 20200, a dispersion index PDI of 2.11, a Tg of 214.4°C, and a T d-5％ It is 358℃.

[0155] Application Example 5

[0156] Synthesis of polycarbonate materials:

[0157] Under nitrogen atmosphere, 0.1 mol of benzoxanthene spirofluorene diol monomer 5 and 0.102 mol of diphenyl carbonate (benzoxanthene spirofluorene diol monomer 5: diphenyl carbonate = 1:1.02, molar ratio) were added to a 250 mL four-necked glass flask equipped with a mechanical stirrer, heated to 180 ° C, and 1×10 -4 mol of 1,5,7-triazidobicyclo(4.4.0)dec-5-ene (relative to the amount of benzoxanthene spirofluorene diol monomer 5) was subjected to an ester exchange reaction at normal pressure for 30 minutes to synthesize a prepolymer; then the reaction temperature was slowly increased to 210°C, the vacuum degree was slowly increased to 10 kPa, and the reaction was continued for 30 minutes; finally, the reaction temperature was slowly increased to 240°C, the vacuum degree was slowly increased to 100 Pa, and the reaction was continued for 20 minutes to finally obtain polycarbonate.

[0158] The obtained polycarbonate had a refractive index nd of 1.6886, an Abbe number v of 17.4, a weight average molecular weight Mw of 19200, a dispersion index PDI of 2.27, a Tg of 219.4°C, and a T d-5％ It is 362℃.

[0159] Application Example 6

[0160] Synthesis of polycarbonate materials:

[0161] Under nitrogen atmosphere, 0.1 mol of benzoxanthene spirofluorene diol monomer 6 and 0.102 mol of diphenyl carbonate (benzoxanthene spirofluorene diol monomer 6: diphenyl carbonate = 1:1.02, molar ratio) were added to a 250 mL four-necked glass flask equipped with a mechanical stirrer, heated to 180 ° C, and 1×10 -4 mol of 1,5,7-triazidobicyclo(4.4.0)dec-5-ene (relative to the amount of 6 mol of benzoxanthene spirofluorene diol monomer) was subjected to an ester exchange reaction at normal pressure for 30 minutes to synthesize a prepolymer; then the reaction temperature was slowly increased to 210°C, the vacuum degree was slowly increased to 10 kPa, and the reaction was continued for 30 minutes; finally, the reaction temperature was slowly increased to 240°C, the vacuum degree was slowly increased to 100 Pa, and the reaction was continued for 20 minutes to finally obtain polycarbonate.

[0162] The obtained polycarbonate had a refractive index nd of 1.6855, an Abbe number v of 17.6, a weight average molecular weight Mw of 24800, a dispersion index PDI of 2.15, a Tg of 212.4°C, and a T d-5％ It is 348℃.

[0163] Comparative Example 1

[0164] Under nitrogen atmosphere, 0.1 mol of 9,9-bis(2-hydroxyethoxy)phenyl)fluorene (abbreviated as BPEF) and 0.102 mol of diphenyl carbonate (dihydroxy compound: diphenyl carbonate = 1:1.02, molar ratio) were added to a 250 mL three-necked glass flask equipped with a mechanical stirrer, heated to 160 °C, and 1×10 -4 mol of 1,5,7-triazidobicyclo(4.4.0)dec-5-ene (relative to the amount of the dihydroxy compound) was subjected to an ester exchange reaction at normal pressure for 20 minutes to synthesize a prepolymer; then the reaction temperature was slowly increased to 250°C, the vacuum degree was slowly increased to 100 Pa, and the reaction was continued for 30 minutes to finally obtain polycarbonate.

[0165] The obtained polycarbonate had a refractive index of 1.6381, an Abbe number of 23.3, a weight average molecular weight of 28,000, a dispersion index of 1.99, a Tg of 149.2°C, and a T d-5％ is 350℃.

[0166] Comparative Example 2

[0167] Under nitrogen atmosphere, 0.1 mol of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BHEBN) and 0.102 mol of diphenyl carbonate (dihydroxy compound: diphenyl carbonate = 1:1.02, molar ratio) were added to a 250 mL three-necked glass flask equipped with a mechanical stirrer, heated to 160 °C, and 1×10 -4 mol of 1,5,7-triazidobicyclo(4.4.0)dec-5-ene (relative to the amount of the dihydroxy compound) was subjected to an ester exchange reaction at normal pressure for 20 minutes to synthesize a prepolymer; then the reaction temperature was slowly increased to 250°C, the vacuum degree was slowly increased to 100 Pa, and the reaction was continued for 30 minutes to finally obtain polycarbonate.

[0168] The obtained polycarbonate had a refractive index of 1.6670, an Abbe number of 19.0, a weight average molecular weight of 24,000, a dispersion index of 1.83, a Tg of 112.2°C, and a T d-5％ It is 334℃.

[0169] Performance testing:

[0170] 1) Weight average molecular weight of resin:

[0171] Gel permeation chromatography (GPC) was used with tetrahydrofuran as the developing solvent and a calibration curve was prepared using standard polystyrenes of known molecular weight (molecular weight distribution = 1). Based on this calibration curve, the weight average molecular weight was calculated from the GPC retention time.

[0172] 2) Optical parameter test of resin:

[0173] Refractive index: can be measured according to ASTM D542 test standard. Specifically, the refractive index of the polymer is measured by Abbe refractometer, model ATAGO DR-M4, and the test wavelength is D light (wavelength 589.3nm).

[0174] Abbe number v: The refractive index of the polymer is measured at different wavelengths (D light, wavelength is 589.3 nm; F light, wavelength is 486.1 nm, C light, wavelength is 656.3), and then calculated by vd = (nD-1) / (nF-nC).

[0175] Weight average molecular weight Mw: tested by gel permeation chromatography (TOSOH HLC-8420GPC), with tetrahydrofuran (THF) solution as the mobile phase, a mobile phase flow rate of 0.35 mL / min, and polystyrene (PS) as the standard sample.

[0176] Glass transition temperature (Tg): The test was conducted using a DSC measuring instrument (NETZSCH DSC 3500) in the temperature range of room temperature to 230°C at a rate of 10°C / min, and the inflection point was selected as the glass transition temperature (Tg) of the polymer.

[0177] Decomposition temperature T d-5％ : In this application, the 5% decomposition temperature (T d-5％ ) was tested by TGA measuring instrument (model NETZSCH TG 209F3) in N2 atmosphere at a temperature range of 25 to 800°C at a rate of 10°C / min.

[0178] 3) Light transmittance:

[0179] The 0.1 mm thick film made of the polycarbonate resin obtained in the example was measured using a turbidity meter according to the method of JIS-K-7361-1. The test structure is shown in Table 1:

[0180] Table 1. Resin components and performance parameters

[0181]

[0182] During the preparation process of the fluorene-containing organic compound provided in the embodiments of the present application, a mixed acid containing acetic acid is used as a solvent for the nucleophilic addition reaction system. Since the mixed acid containing acetic acid is a mixture of multiple inorganic acids, it serves as an acidic catalyst while serving as a solvent for the reaction system. This can increase the conversion rate of polyaromatic ring phenol intermediates and the conversion rate of the fluorene-containing organic compound (monomer).

[0183] The polycarbonate resin prepared from the fluorene-containing organic compound (monomer) of the present application is derived from a fluorene-containing organic compound having a structural unit as shown in Formula I or II. The naphthyloxy spiro ring or aryl cyclic ether structure connected to the fluorene structure can increase the electron density of the fluorene-containing organic compound, resulting in a resin prepared from the monomer having a high refractive index and light transmittance, suitable for various optical film applications. The entire synthesis process has good universality, high reactivity, high conversion rate, and easy purification, which can effectively reduce the production cost of the resin.

[0184] Comparative Example 1 uses bisetherfluorene and diphenyl carbonate to prepare resin, and Comparative Example 2 uses 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl and diphenyl carbonate to prepare resin. The refractive index and thermal stability of the prepared resin are significantly lower than the resin prepared in the application example of this application.

[0185] Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the claims. Any person skilled in the art may make several possible changes and modifications without departing from the concept of the present application. Therefore, the scope of protection of the present application shall be based on the scope defined by the claims of the present application.

Claims

1. A fluorene-containing organic compound, characterized in that: The molecular structure of the fluorene-containing organic compound is shown in Formula I or Formula II: In Formula I and Formula II, R1, R2, and R3 are each independently selected from a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C1-C50 ether group, a hydrogen atom, a deuterium atom, a disubstituted amino group, -F, -Cl, -Br, -I, -CF3, -NO2, and -CN.

2. The fluorene-containing organic compound according to claim 1, characterized in that The fluorene-containing organic compound includes at least one of the following characteristics: 1) The substituted or unsubstituted C6-C50 aryl group is a full-carbon aryl group; 2) The substituted or unsubstituted C6-C50 aryl group is a heteroaryl group, and the heteroatom in the heteroaryl group includes at least one of an oxygen atom, a nitrogen atom, a sulfur atom, and a selenium atom; 3) The substituted or unsubstituted C1-C50 alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl and n-octyl; 4) When any one of R1, R2 or R3 is substituted, the substituent is selected from a deuterium atom, a halogen atom, a trifluoromethyl group, or a C1-C8 alkyl group.

3. The fluorene-containing organic compound according to claim 1, characterized in that The fluorene-containing organic compound includes any one of the following compounds:

4. A method for preparing a fluorene-containing organic compound according to any one of claims 1 to 3, characterized in that: The method comprises: The compound represented by formula (a) and the dinaphthol represented by formula (b) are dissolved in a mixed acid containing acetic acid, and the dinaphthol and 9-fluorenone undergo a nucleophilic addition reaction under acid catalysis. The reaction product is recrystallized after removing the acid solution, and is filtered and dried to obtain a polyaromatic phenol intermediate represented by the corresponding formula (c) or formula (d); The polyaromatic ring phenol intermediate represented by formula (c) and ethylene carbonate are dissolved in an organic solvent, and an etherification substitution reaction is carried out under the action of a basic catalyst to obtain a fluorene-containing organic compound represented by formula (I); or The polyaromatic ring phenol intermediate represented by formula (d) and 2,3-dihalopropanol are dissolved in an organic solvent, and an etherification substitution reaction occurs under the action of a basic catalyst to obtain a fluorene-containing organic compound represented by formula (II); Wherein, R1, R2, and R3 are each independently selected from a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C1-C50 ether group, a hydrogen atom, a deuterium atom, a disubstituted amino group, -F, -Cl, -Br, -I, -CF3, -NO2, and -CN.

5. The preparation method according to claim 4, characterized in that The method satisfies at least one of the following characteristics: 1) The substituted or unsubstituted C6-C50 aryl group is a full-carbon aryl group; 2) The substituted or unsubstituted C6-C50 aryl group is a heteroaryl group, and the heteroatom in the heteroaryl group includes at least one of an oxygen atom, a nitrogen atom, a sulfur atom, and a selenium atom; 3) The substituted or unsubstituted C1-C50 alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl and n-octyl; 4) When any one of R1, R2 or R3 is substituted, the substituent is selected from a deuterium atom, a halogen atom, a trifluoromethyl group, or a C1-C8 alkyl group.

6. The preparation method according to claim 4, characterized in that The upper limit of the molar ratio of the compound represented by formula (a) to the dinaphthol is 1:

10.

7. The preparation method according to claim 4, characterized in that The mixed acid further includes other acids, and the other acids include one or more of methanesulfonic acid, trifluoroacetic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, and sulfuric acid; and / or, the mixed acid further includes other acids, and the volume ratio of the other acids to the acetic acid is 1:(1-100).

8. The preparation method according to claim 4, characterized in that The temperature of the nucleophilic addition reaction is 80° C. to 140° C., and the reaction time is 0.5 h to 36 h.

9. The preparation method according to claim 4, characterized in that The solvent used in the recrystallization includes one or more of acetone, methanol, ethanol, tetrahydrofuran, ethyl acetate, dichloromethane, acetonitrile, methyl tert-butyl ether, toluene, and petroleum ether.

10. The preparation method according to claim 4, characterized in that The molar ratio of the polyaromatic ring phenol intermediate to the ethylene carbonate is 1:(2-10); or the molar ratio of the polyaromatic ring phenol intermediate to the 2,3-dihalopropanol is 1:(2-10).

11. The preparation method according to claim 10, characterized in that: The method satisfies any one of the following characteristics: 5) The organic solvent is one or more of dimethyl sulfoxide, N,N-dimethylformamide, diethylene glycol dimethyl ether, N-methylpyrrolidone, toluene, xylene, and trimethylbenzene; 6) The alkaline catalyst includes one or more of sodium tert-butoxide, potassium tert-butoxide, potassium phosphate, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, and sodium hydride; 7) The temperature of the etherification substitution reaction is 100° C. to 150° C.; 8) The etherification substitution reaction time is 0.5h to 36h.

12. A resin, characterized in that The raw materials for preparing the resin include the fluorene-containing organic compound according to any one of claims 1 to 3.

13. The resin according to claim 12, characterized in that The raw materials for preparing the resin also include other raw materials, and the other raw materials include at least one of carbonic acid diester, dicarboxylic acid, and dicarboxylic acid ester; the molar ratio of the other raw materials to the fluorene-containing organic compound is (0.95-1.15):

1.

14. An optical film, characterized in that: The raw material for preparing the optical film includes the resin according to any one of claims 12 or 13.

15. An electronic device, characterized in that: The electronic device includes the optical film according to claim 14.

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