Diol derivative crystal of 2,7-bis(phenylethynyl)fluorene and preparation method thereof

Abstract

The present invention discloses a diol derivative crystal of 2,7-bis(phenylethynyl)fluorene having the general formula (I), wherein R represents phenyl, biphenyl or naphthyl; the preparation method of the crystal comprises the following steps: (1) reacting 2,7-dibromo-9-fluorenone with phenoxyethanol, o-phenylphenoxyethanol or 2-naphthyloxyethanol to obtain the corresponding dibromo compound; (2) reacting the dibromo compound with phenylacetylene in a molar ratio of 1:2 to 4, under alkaline conditions, using a palladium complex and cuprous halide as catalysts, in an organic solvent, at 60 to 120 °C, for a reaction time of 2 to 24 hours, and then performing recrystallization to obtain the crystal; the refractive index of the crystal is 1.67 to 1.69, which is used for the preparation of optical resin materials, can improve the refractive index of the materials, and the crystal is a non-inclusion body, which is beneficial to the manufacture of high-quality optical resin materials; the preparation method is simple and easy to industrialize.

Description

Technical Field

[0001] The present invention relates to an optical material, and particularly to a diol derivative crystal of 2,7-bis(phenylethynyl)fluorene and a preparation method thereof. Background Art

[0002] Resin materials such as polycarbonate, polyester, polyacrylate, polyurethane, and epoxy resin using diol with a fluorene skeleton as a raw material monomer have attracted attention in recent years as new optical materials such as optical lenses and optical films due to their excellent optical properties and heat resistance.

[0003] The refractive index of traditional bisphenol A polycarbonate is only 1.58. Compared with traditional bisphenol A polycarbonate, the refractive index of the diol monomer with a fluorene skeleton and its polycarbonate has been greatly improved. Japanese Patent 2016074644 discloses that the refractive index of 9,9-(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF) monomer is 1.62, and International Patent WO2007142149 discloses that the refractive index of the polycarbonate obtained by copolymerizing BPEF is 1.62 - 1.64. Due to the rapid development of information technology, especially the development of optical lenses towards thinner, lighter, and more miniature directions, there is an urgent need to further improve the refractive index of optical resin materials. Summary of the Invention

[0004] Object of the Invention: The first object of the present invention is to provide a diol derivative crystal of 2,7-bis(phenylethynyl)fluorene with a high refractive index; another object of the present invention is to provide a preparation method of the crystal.

[0005] Technical Solution: The diol derivative crystal of 2,7-bis(phenylethynyl)fluorene of the present invention is characterized in that the structural formula is:

[0006]

[0007] Wherein, the aryl group Ar is phenyl, biphenyl, or naphthyl.

[0008] The crystal is a non-inclusion body of solvent-free complexation or inclusion. It is a well-known fact that fluorene derivatives are extremely prone to inclusion complexation with organic solvents to form inclusion bodies. Such solvent inclusion bodies have serious adverse effects on the subsequent polymerization reaction to produce polycarbonate. On the one hand, during the polymerization reaction process, the release of the solvent seriously affects the quality of the polycarbonate, and on the other hand, the release of the solvent has an adverse impact on the environment.

[0009] When the aryl group Ar is a phenyl group, the crystal is 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))diethanol (hereinafter referred to as Compound 1) (English name 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))diethanol), and its structural formula is:

[0010]

[0011] In the X-ray powder diffraction pattern of the crystal, characteristic diffraction peaks appear at diffraction angle 2θ values of 7.7±0.20, 8.0±0.20, 17.6±0.20, 18.2±0.20, 19.1±0.20, 20.1±0.20, 20.5±0.20, 21.2±0.20, 21.9±0.20; and it has an endothermic peak measured by a differential scanning calorimeter in the temperature range of 240-260 °C.

[0012] The crystallization solvent of the crystal is a mixture of toluene and anisole.

[0013] When the aryl group Ar is a biphenyl group, the crystal is 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-diyl)bis([1,1'-biphenyl]-5,2-diyl))bis(oxy))diethanol (hereinafter referred to as Compound 2) (English name 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-diyl)bis([1,1'-biphenyl]-5,2-diyl))bis(oxy))diethanol), and its structural formula is:

[0014]

[0015] In the X-ray powder diffraction pattern of the crystal, characteristic diffraction peaks appear at diffraction angle 2θ values of 4.6±0.20, 8.0±0.20, 9.3±0.20, 14.2±0.20, 16.3±0.20, 20.5±0.20, 27.5±0.20; and it has an endothermic peak measured by a differential scanning calorimeter in the temperature range of 180-200 °C.

[0016] When the aryl group Ar is a biphenyl group, the crystallization solvent of the crystal is a mixture of toluene and methanol.

[0017] When the aryl Ar is naphthyl, the crystal is 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-diyl)bis(naphthalene-6,2-diyl))bis(oxy))diethanol (hereinafter referred to as Compound 3) (English name 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-diyl)bis(naphthalene-6,2-diyl))bis(oxy))diethanol), and its structural formula is:

[0018]

[0019] The crystal is Type A crystal or Type B crystal.

[0020] For the Type A crystal, in the X-ray powder diffraction pattern, characteristic diffraction peaks appear at diffraction angle 2θ values = 5.4±0.20, 7.3±0.20, 9.9±0.20, 16.2±0.20, 18.2±0.20, 18.5±0.20, 19.6±0.20, 21.0±0.20, 23.3±0.20, 24.1±0.20, 26.1±0.20; it has an endothermic peak measured by a differential scanning calorimeter in the temperature range of 230-250°C.

[0021] The crystallization solvent for the Type A crystal is toluene.

[0022] For the Type B crystal, in the X-ray powder diffraction pattern, diffraction angle 2θ values = 5.7±0.20, 7.1±0.20, 10.8±0.20, 11.4±0.20, 12.0±0.20, 14.6±0.20, 17.4±0.20, 17.8±0.20, 19.1±0.20, 19.5±0.20, 20.2±0.20, 20.9±0.21, 21.6±0.20, 23.0±0.20, 23.4±0.20, 25.1±0.20, 25.5±0.20; it has an endothermic peak measured by a differential scanning calorimeter in the temperature range of 180-210°C.

[0023] The crystallization solvent for the Type B crystal is a mixture of toluene and acetonitrile.

[0024] The preparation method of the diol derivative crystal of 2,7-bis(phenylethynyl)fluorene group of the present invention: Using a dibromo compound and phenylacetylene as raw materials, with a molar ratio of 1:2-4, under alkaline conditions, using a palladium complex and cuprous halide as catalysts, in an organic solvent, at 60-120°C, and reacting for 2-24 hours to obtain.

[0025] Under alkaline conditions, in the presence of a palladium complex and cuprous halide as co-catalysts, a dibromo compound and phenylacetylene undergo a Sonogashira coupling reaction to obtain a diol derivative crystal of 2,7-bis(phenylethynyl)fluorene. The reaction route is as follows:

[0026]

[0027] The aryl group Ar is phenyl, biphenyl or naphthyl.

[0028] Preferably, the palladium complex is tetrakis(triphenylphosphine)palladium Pd(PPh3)4, dichloro[bis(triphenylphosphine)]palladium Pd(PPh3)2Cl2, dichloro[bis(tricyclohexylphosphine)]palladium Pd(PCy3)2Cl2, palladium chloride / triphenylphosphine PdCl2 / PPh3 or palladium acetate / triphenylphosphine Pd(OAc )2 / PPh3.

[0029] Preferably, the cuprous halide is cuprous chloride, cuprous bromide or cuprous iodide.

[0030] Preferably, the alkaline condition is an alkali metal compound or an organic base; the alkali metal compound is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, sodium isopropoxide, potassium isopropoxide, potassium tert-butoxide, sodium tert-butoxide. The organic base is at least one of triethylamine, tripropylamine, triisopropylamine, N-ethyldiisopropylamine, pyridine, piperidine, pyrrolidine.

[0031] Preferably, the organic solvent is an aromatic solvent such as toluene, xylene or ethylbenzene; a ketone solvent such as acetone, butanone or methyl isobutyl ketone; an ether solvent such as tetrahydrofuran, methyl tert-butyl ether, anisole, ethylene glycol dimethyl (ethyl) ether or diethylene glycol dimethyl (ethyl) ether; an alcohol solvent such as methanol, ethanol, propanol, isopropanol, n-butanol or isobutanol; a polar aprotic solvent such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.

[0032] The synthesis method of the dibromo compound is as follows: In a 500 ml four-necked flask, add 33.8 g of 2,7-dibromo-9-fluorenone and 48 g of phenoxyethanol (48 g of phenoxyethanol can be replaced by 70 g of o-phenylphenoxyethanol or 70 g of 2-naphthyloxyethanol), 50 g of toluene, 0.5 g of 3-mercaptopropionic acid, stir, and dropwise add 30 g of 98% sulfuric acid by mass. After the addition is complete, control the temperature at 60 °C and react for 9 h. Monitor the end of the reaction by HPLC. Add 30% NaOH for neutralization, wash with water until neutral, cool down to crystallize, filter by suction, wash with toluene, and dry in vacuo at 100 °C for 8 h to obtain the dibromo compound.

[0033] Mechanism of the invention: According to the optical refraction theory in physics (Lorentz-Lorenz formula), increasing the molecular polarizability can effectively increase the refractive index. Ethynylphenyl is a group that can be highly polarized. In this invention, ethynylphenyl conjugated with the fluorene ring is introduced into the fluorene diol monomer molecule through the Sonogashira reaction, and a diol derivative monomer with a high refractive index of 2,7-bis(phenylethynyl) is synthesized.

[0034] Advantages: Compared with the prior art, the present invention has the following remarkable advantages: (1) The crystal of the diol derivative of 2,7-bis(phenylethynyl)fluorene is a novel compound with a refractive index of 1.67 - 1.69, which can be used in the preparation of optical resin materials to increase the refractive index of the materials; (2) This crystal is a non-inclusion body with a purity greater than 98%, which is beneficial to the manufacture of high-quality optical resin materials; (3) The preparation method is simple and easy for industrial production. Description of the drawings

[0035] Figure 1 It is the general formula of the structural formula of the crystal of the diol derivative of 2,7-bis(phenylethynyl)fluorene of the present invention;

[0036] Figure 2 It is the 1H NMR spectrum of Compound 1 prepared in Example 1;

[0037] Figure 3 It is the DSC spectrum of the thermal analysis of Compound 1 prepared in Example 1;

[0038] Figure 4 It is the TGA spectrum of the thermal analysis of Compound 1 prepared in Example 1;

[0039] Figure 5 It is the XRD spectrum of Compound 1 prepared in Example 1;

[0040] Figure 6 It is the 1H NMR spectrum of Compound 2 prepared in Example 2;

[0041] Figure 7 It is the DSC spectrum of the thermal analysis of Compound 2 prepared in Example 2;

[0042] Figure 8 It is the TGA spectrum of the thermal analysis of Compound 2 prepared in Example 2;

[0043] Figure 9 It is the XRD spectrum of Compound 2 prepared in Example 2;

[0044] Figure 10 It is the 1H NMR spectrum of Compound 3 prepared in Example 3;

[0045] Figure 11 It is the DSC spectrum of the thermal analysis of Crystal Form A of Compound 3 prepared in Example 3;

[0046] Figure 12 Thermogravimetric analysis (TGA) spectrum of Compound 3 polymorph A prepared in Example 3;

[0047] Figure 13 XRD spectrum of Compound 3 polymorph A prepared in Example 3;

[0048] Figure 14 Differential scanning calorimetry (DSC) spectrum of Compound 3 polymorph B prepared in Example 4;

[0049] Figure 15 Thermogravimetric analysis (TGA) spectrum of Compound 3 polymorph B prepared in Example 4;

[0050] Figure 16 XRD spectrum of Compound 3 polymorph B prepared in Example 4;

[0051] Figure 17 XRD spectrum of the compound prepared in Comparative Example 1;

[0052] Figure 18 Differential scanning calorimetry (DSC) spectrum of the compound prepared in Comparative Example 2;

[0053] Figure 19 Thermogravimetric analysis (TGA) spectrum of the compound prepared in Comparative Example 2;

[0054] Figure 20 XRD spectrum of the compound prepared in Comparative Example 2;

[0055] Figure 21 XRD spectrum of the compound prepared in Comparative Example 3. Detailed implementation manners

[0056] The technical solutions of the present invention will be further described below in conjunction with examples.

[0057] The analysis methods adopted in the present invention are as follows:

[0058] 1. Purity determination method (HPLC): Instrument: LC-15C (Shimadzu); Column type: Kromasil100-5 C18 150×4.6mm; Mobile phase: acetonitrile / water; Flow rate: 1 mL / min; Detection wavelength: 260 nm; Injection volume: 2 μL; Pump mode: binary high-pressure gradient.

[0059] 2. Thermal analysis method: Measured by Pyris1 thermal analyzer (Perkin Elemer), DSC heating range 45 - 300 °C, 10 °C / min; TGA heating range 25 - 500 °C, 10 °C / min.

[0060] 3. Chromaticity analysis: It was detected with a Transmission color meter TZ6000 (Nippon Denshoku Industries Co., Ltd., Japan). 10 g of the sample was added to 20 g of DMF, and after stirring until dissolved and clear, the detection was carried out.

[0061] 4. The X-ray powder diffraction spectrum was measured with an X'TRA X-ray diffractometer (ARL Company, Switzerland), using a copper target and a continuous scanning mode. The scanning range (2θ) was 2° to 40°, the scanning step was 0.02°, and the scanning speed was 2.5° / min.

[0062] 5. Refractive index (nD): The refractive index at 25 °C was measured using a DR-M2 Abbe refractometer manufactured by ATAGO, with a wavelength of 589 nm.

[0063] 6. Drying loss meter: PRECISA / XM60 was used to measure the drying at 150 °C for half an hour.

[0064] 7. Nuclear magnetic resonance spectrometer: Bruker AV 300 nuclear magnetic resonance spectrometer (using DMSO-d6 as the solvent and TMS as the internal standard).

[0065] Example 1

[0066] The diol derivative crystal of 2,7-bis(phenylethynyl)fluorenyl of the present invention is specifically 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-ylidene)bis(4,1-phenylene))bis(oxy))diethanol crystal (Compound 1), and its preparation method includes the following steps:

[0067] (1) Preparation of dibromo compound 9,9-bis(6-(2-hydroxyethoxy)phenyl)-2,7-dibromofluorene

[0068] In a 500 ml four-necked flask, 33.8 g of 2,7-dibromo-9-fluorenone, 48 g of phenoxyethanol, 50 g of toluene and 0.5 g of 3-mercaptopropionic acid were added, stirred, and 30 g of 98% sulfuric acid by mass fraction was added dropwise. After the dropwise addition, the temperature was controlled at 60 °C, and after reacting for 9 h, the reaction was monitored by HPLC until it ended. 30% NaOH aqueous solution was added for neutralization, washed with water until neutral, cooled for crystallization, filtered by suction, washed with toluene, and dried under vacuum at 100 °C for 8 hours to obtain 50 g of the intermediate 9,9-bis(6-(2-hydroxyethoxy)phenyl)-2,7-dibromofluorene; the yield was 85%, and the purity (HPLC): 99.0%.

[0069] (2) Preparation of 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-ylidene)bis(4,1-phenylene))bis(oxy))diethanol crystal (Compound 1)

[0070] In a 500 ml four-necked flask, under nitrogen protection, 30 g of 9,9-bis(6-(2-hydroxyethoxy)phenyl)-2,7-dibromofluorene, 20 g of phenylacetylene and 100 g of Et3N were successively added, then 0.5 g of Pd(PPh3)4 and 0.1 g of CuI were added. The mixture was heated at 80 °C for 6 hours, and the reaction was monitored by HPLC until completion. The solvent was removed by distillation under reduced pressure, then 100 g of toluene was added, and the mixture was heated to dissolve. 1 M hydrochloric acid was added dropwise to neutralize, and the mixture was washed with water until neutral. The layers were separated, 50 g of anisole was added, the temperature was lowered to 50 °C, crystallization occurred, and the product was filtered by suction, washed with toluene, and dried in vacuo at 100 °C for 10 h to obtain 26 g of 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))diethanol (Compound 1), with a yield of 80% and a purity (HPLC) of 99.0%.

[0071] 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))diethanol (Compound 1) 1 H NMR (300 MHz, DMSO-d6) δ: 8.03 (d, 2H, Ar-H), 7.61 (d, 2H, Ar-H), 7.54–7.57 (m, 6H, Ar-H), 7.41–7.43 (m, 6H, Ar-H), 7.06 (d, 4H, Ar-H), 6.86 (d, 4H, Ar-H), 4.84 (t, 2H, OH), 3.93 (t, 4H, CH2), 3.68 (t, 4H, CH2)( Figure 2 ).

[0072] The maximum melting endothermic peak measured by differential scanning calorimetry was 251.55 °C, as shown in Figure 3 .

[0073] TGA detection showed no weight loss at 250 °C, indicating a non-inclusion complex without solvent complexation or inclusion, as shown in Figure 4 .

[0074] The chromaticity of the crystal of Compound 1 was 10 APHA, and the refractive index was 1.67 (25 °C, 589 nm).

[0075] Figure 5 The X-ray diffraction pattern of the crystal is shown in Table 1. Characteristic diffraction peaks appeared at diffraction angles 2θ values of 7.7 ± 0.20, 8.0 ± 0.20, 17.6 ± 0.20, 18.2 ± 0.20, 19.1 ± 0.20, 20.1 ± 0.20, 20.5 ± 0.20, 21.2 ± 0.20, 21.9 ± 0.20.

[0076] Table 1

[0077]

[0078]

[0079] Example 2

[0080] The diol derivative crystal of 2,7-bis(phenylethynyl)fluorene of the present invention, specifically 2,2'-(((2,7-bis(phenylethynyl)-9H-fluoren-9,9-ylidene)bis([1,1'-biphenyl]-5,2-ylidene))bis(oxy))diethanol crystal (Compound 2), and its preparation method includes the following steps:

[0081] (1) Preparation of dibromo compound 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-2,7-dibromofluorene

[0082] In a 500 ml four-necked flask, add 33.8 g of 2,7-dibromo-9-fluorenone, 70 g of o-phenylphenoxyethanol, 200 g of toluene, and 0.5 g of 3-mercaptopropionic acid, stir, and dropwise add 30 g of concentrated sulfuric acid with a mass fraction of 98%. After the addition is complete, control the temperature at 60 °C, react for 9 hours, and monitor the end of the reaction by HPLC. Add 30% NaOH for neutralization, wash with water until neutral, then cool down to crystallize, filter by suction, wash with toluene, and dry in vacuo at 100 °C for 8 h to obtain 67 g of intermediate 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-2,7-dibromofluorene; the yield is 90%, and the purity (HPLC): 99.0%.

[0083] (2) Preparation of 2,2'-(((2,7-bis(phenylethynyl)-9H-fluoren-9,9-ylidene)bis([1,1'-biphenyl]-5,2-ylidene))bis(oxy))diethanol crystal (Compound 2)

[0084] In a 500 ml four-necked flask, under nitrogen protection, sequentially add 36 g of 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-2,7-dibromofluorene, 20 g of phenylacetylene, and 100 g of Et3N, then add 0.5 g of Pd(PPh3)4 and 0.1 g of CuI, heat and react at 80 °C for 6 hours, and monitor the end of the reaction by HPLC. Evaporate the solvent under reduced pressure, add 100 g of toluene, heat to dissolve, dropwise add 1M hydrochloric acid for neutralization, wash with water until neutral, separate the water layer, add 50 g of methanol, cool down to 50 °C, crystallize, filter by suction, wash with toluene, and dry in vacuo at 100 °C for 10 hours to obtain 32 g of 2,2'-(((2,7-bis(phenylethynyl)-9H-fluoren-9,9-ylidene)bis([1,1'-biphenyl]-5,2-ylidene))bis(oxy))diethanol (Compound 2), the yield is 85%, and the purity (HPLC) is 98.5%.

[0085] 2,2'-(((2,7-Bis(phenylethynyl)-9H-fluoren-9,9-ylidene)bis([1,1'-biphenyl]-5,2-ylidene))bis(oxy))diethanol 1 H NMR(300MHz,DMSO-d6)δ:8.07(d,2H,Ar-H),7.62(d,4H,Ar-H),7.54(d,4H,Ar-H),7.40–7.44(m,14H,Ar-H),7.34(d,2H,Ar-H),7.24(d,2H,Ar-H),7.10(d,4H,Ar-H),4.78(t,2H,OH),4.01(t,4H,CH2),3.65(t,4H,CH2)( Figure 6 )。

[0086] The maximum melting endothermic peak measured by differential scanning calorimeter is 192.97 °C, see Figure 7 。

[0087] There is no weight loss at 250 °C detected by TGA, which is a non-inclusion body without solvent complexation or inclusion, see Figure 8 。

[0088] The chromaticity of the crystal of Compound 2 is 10 APHA, and the refractive index is 1.68 (25 °C, 589 nm).

[0089] Figure 9 The X-ray diffraction pattern of the crystal is shown in Table 2. Characteristic diffraction peaks appear at diffraction angles 2θ values of 4.6 ± 0.20, 8.0 ± 0.20, 9.3 ± 0.20, 14.2 ± 0.20, 16.3 ± 0.20, 20.5 ± 0.20, 27.5 ± 0.20.

[0090] Table 2

[0091]

[0092]

[0093] Example 3

[0094] The crystal of the diol derivative of 2,7-bis(phenylethynyl)fluorene group of the present invention is specifically 2,2'-(((2,7-bis(phenylethynyl)-9H-fluoren-9,9-ylidene)bis(naphthalen-6,2-ylidene))bis(oxy))diethanol (Crystal Form A of Compound 3), and its preparation method includes the following steps:

[0095] (1) Dibromo compound 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-dibromofluorene

[0096] In a 500 ml four-necked flask, 33.8 g of 2,7-dibromo-9-fluorenone, 70 g of 2-naphthoxyethanol, 200 g of toluene and 0.5 g of 3-mercaptopropionic acid were added. The mixture was stirred, and 30 g of concentrated sulfuric acid with a mass fraction of 98% was added dropwise. After the addition was completed, the temperature was controlled at 60 °C. After reacting for 9 h, the reaction was monitored by HPLC until it ended. 30% NaOH was added for neutralization, washed with water until neutral, cooled to crystallize, filtered by suction, washed with toluene, and dried in vacuo at 100 °C for 8 h to obtain 56 g of the intermediate 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-dibromofluorene; the yield was 80%, and the purity (HPLC): 99.0%.

[0097] (2) Synthesis of 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-diyl)bis(naphthalene-6,2-diyl))bis(oxy))diethanol (Compound 3 Crystal Form A)

[0098] In a 500 ml four-necked flask, under nitrogen protection, 35 g of 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-dibromofluorene, 20 g of phenylacetylene and 100 g of Et3N were added in sequence. Then 0.5 g of Pd(PPh3)4 and 0.1 g of CuI were added. The mixture was heated and reacted at 80 °C for 6 hours, and the reaction was monitored by HPLC until it ended. The solvent was removed by distillation under reduced pressure, 100 g of toluene was added and heated to dissolve, 1M hydrochloric acid was added dropwise for neutralization, washed with water until neutral, the water was separated, crystallized at 70 °C, filtered by suction, washed with toluene, and dried in vacuo at 100 °C for 10 h to obtain 32 g of 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-diyl)bis(naphthalene-6,2-diyl))bis(oxy))diethanol (Compound 3 Crystal Form A), with a yield of 86% and a purity (HPLC) of 98.5%.

[0099] 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-diyl)bis(naphthalene-6,2-diyl))bis(oxy))diethyl 1 HNMR(300MHz,DMSO-d6)δ:8.13(d,2H,Ar-H),7.66–7.79(m,8H,Ar-H),7.53–7.57(m,6H,Ar-H),7.37–7.41(m,8H,Ar-H),7.30(d,2H,Ar-H),7.10(d,2H,Ar-H),4.94(t,2H,OH),4.08(t,4H,CH2),3.77(t,4H,CH2)( Figure 10 )

[0100] The maximum melting endothermic peak of DSC measured by a differential scanning calorimeter was 243.43 °C, see Figure 11 。

[0101] The TGA test shows no weight loss at 250 °C, indicating a non-inclusion complex without solvent complexation or inclusion. See Figure 12 。

[0102] The chromaticity of crystal (A) of Compound 3 is 10 APHA, and the refractive index is 1.69 (25 °C, 589 nm).

[0103] Figure 13 The X-ray diffraction pattern of the crystal is as shown in Table 3. Characteristic diffraction peaks appear at diffraction angles 2θ values of 5.4 ± 0.20, 7.3 ± 0.20, 8.5 ± 0.20, 9.9 ± 0.20, 10.4 ± 0.20, 11.3 ± 0.20, 12.1 ± 0.20, 14.4 ± 0.20, 16.2 ± 0.20, 16.5 ± 0.20, 17.2 ± 0.20, 17.7 ± 0.20, 18.2 ± 0.20, 18.5 ± 0.20, 19.6 ± 0.20, 20.4 ± 0.20, 21.0 ± 0.20, 22.0 ± 0.20, 22.6 ± 0.20, 23.3 ± 0.20, 24.1 ± 0.20, 24.5 ± 0.20, 25.3 ± 0.20, 26.1 ± 0.20, 27.6 ± 0.20, 28.0 ± 0.20, 28.9 ± 0.20, 29.8 ± 0.20, 31.3 ± 0.20.

[0104] Table 3

[0105]

[0106] Example 4

[0107] The crystal of the diol derivative of 2,7-bis(phenylethynyl)fluorene of the present invention is specifically 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-ylidene)bis(naphthalene-6,2-ylidene))bis(oxy))diethanol (Crystal Form B of Compound 3), and its preparation method includes the following steps:

[0108] (1) The synthesis of the dibromo compound 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-dibromofluorene is the same as that in Example 3.

[0109] (2) Synthesis of 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-ylidene)bis(naphthalene-6,2-ylidene))bis(oxy))diethanol (Crystal Form B of Compound 3)

[0110] In a 500 ml four-necked flask, under nitrogen protection, 35 g of 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-dibromofluorene, 20 g of phenylacetylene and 100 g of Et3N were successively added, then 0.5 g of Pd(PPh3)4 and 0.1 g of CuI were added. The mixture was heated and reacted at 80 °C for 6 hours, and the reaction was monitored by HPLC until completion. The solvent was removed by distillation under reduced pressure, 100 g of toluene was added and heated to dissolve, 1 M hydrochloric acid was added dropwise for neutralization, washed with water until neutral, the water layer was separated, 50 g of acetonitrile was added, the temperature was lowered to below 10 °C for crystallization, filtered by suction, washed with toluene, and dried in vacuo at 100 °C for 10 hours to obtain 32 g of 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-ylidene)bis(naphthyl-6,2-ylidene))bis(oxy))diethanol (Compound 3 Crystal Form B), with a yield of 86% and a purity (HPLC) of 98.0%. The 1H NMR spectrum was the same as that in Example 3.

[0111] The maximum melting endothermic peak measured by differential scanning calorimetry was 196.31 °C, as shown in Figure 14 .

[0112] The TGA test showed no weight loss at 250 °C, indicating a non-inclusion complex without solvent complexation or inclusion, as shown in Figure 15 .

[0113] The chromaticity of Compound 4 Crystal (B) was 10 APHA, and the refractive index was 1.69 (25 °C, 589 nm).

[0114] Figure 16 The X-ray diffraction pattern of the crystal is as follows. Characteristic diffraction peaks appeared at diffraction angles 2θ values of 5.7±0.20, 7.1±0.20, 8.6±0.20, 9.4±0.20, 10.8±0.20, 11.4±0.20, 12.0±0.20, 13.2±0.20, 14.6±0.20, 15.7±0.20, 17.4±0.20, 17.8±0.20, 19.1±0.20, 19.5±0.20, 20.2±0.20, 20.9±0.21, 21.6±0.20, 23.0±0.20, 23.4±0.20, 25.1±0.20, 25.5±0.20, 27.2±0.20, 28.5±0.20, as shown in Table 4.

[0115] Table 4

[0116]

[0117] Comparative Example 1

[0118] The intermediate 9,9-bis(6-(2-hydroxyethoxy)phenyl)-2,7-dibromofluorene was synthesized as in Example 1;

[0119] In a 500 ml four-necked flask, under nitrogen protection, 30 g of 9,9-bis(6-(2-hydroxyethoxy)phenyl)-2,7-dibromofluorene, 20 g of phenylacetylene and 100 g of Et3N were successively added. Then, 0.5 g of Pd(PPh3)4 and 0.1 g of CuI were added. The mixture was heated at 80 °C for 6 hours, and the reaction was monitored by HPLC until completion. After cooling to room temperature, the solid was filtered off, washed with dilute hydrochloric acid until neutral, and then dissolved by heating with 50 g of N,N-dimethylformamide and 50 g of water. After cooling to room temperature, a precipitate was formed, filtered off, washed with toluene, and dried in vacuo at 100 °C for 10 h to obtain 27 g of 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-ylidene)bis(4,1-phenylene))bis(oxy))diethanol (Compound 1) with a yield of 85%. The purity (HPLC) was 97%. The 1H NMR spectrum was the same as that in Example 1.

[0120] The melting range was determined to be 180 - 240 °C using a capillary melting point apparatus, and the weight loss on drying was determined to be 6% using a drying loss instrument. It was an inclusion compound. The X-ray diffraction pattern of the crystal is shown in Figure 17 . As shown in Table 5, characteristic diffraction peaks appeared at diffraction angles 2θ of 4.9 ± 0.20, 7.2 ± 0.20, 9.9 ± 0.20, 15.3 ± 0.20, 19.2 ± 0.20, 20.5 ± 0.20, and 28.3 ± 0.20.

[0121] Table 5

[0122]

[0123] Comparative Example 2

[0124] The intermediate 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-2,7-dibromofluorene was synthesized as in Example 2; in a 500 ml four-necked flask, under nitrogen protection, 36 g of 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-2,7-dibromofluorene, 20 g of phenylacetylene and 100 g of Et3N were successively added. Then, 0.5 g of Pd(PPh3)4 and 0.1 g of CuI were added. The mixture was heated at 80 °C for 6 hours, and the reaction was monitored by HPLC until completion. The solvent was removed by distillation under reduced pressure, 100 g of toluene was added, and the mixture was heated to dissolve. 1 M hydrochloric acid was added dropwise for neutralization, washed with water until neutral, the layers were separated, cooled to 30 °C, crystallized, filtered off, washed with toluene, and dried in vacuo at 100 °C for 10 h to obtain 30 g of 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-ylidene)bis([1,1'-biphenyl]-5,2-ylidene))bis(oxy))diethanol (Compound 2) with a yield of 75%. The 1H NMR spectrum was the same as that in Example 2, and the purity (HPLC) was 98%.

[0125] The maximum melting endothermic peak of DSC measured by differential scanning calorimeter is 130.42 °C, see Figure 18 .

[0126] The residual toluene detected by TGA is 2.023%, which is an inclusion compound, see Figure 19 .

[0127] The X-ray diffraction pattern of the crystal, see Figure 20 , as shown in Table 6, characteristic diffraction peaks appear at diffraction angles 2θ values of 5.22 ± 0.20, 8.26 ± 0.20, 8.56 ± 0.20, 9.26 ± 0.20, 10.00 ± 0.20, 10.44 ± 0.20, 14.50 ± 0.20, 15.60 ± 0.20, 16.30 ± 0.20, 17.20 ± 0.20, 17.70 ± 0.20, 17.96 ± 0.20, 18.88 ± 0.20, 19.36 ± 0.20, 20.14 ± 0.20, 20.50 ± 0.21, 20.98 ± 0.20, 21.44 ± 0.20, 22.38 ± 0.20, 22.88 ± 0.20, 24.40 ± 0.20.

[0128] Table 6

[0129]

[0130]

[0131] Comparative Example 3

[0132] Synthesize the intermediate 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-dibromofluorene as in Example 3; in a 500 ml four-necked flask, under nitrogen protection, add 35 g of 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-dibromofluorene, 20 g of phenylacetylene and 100 g of Et3N in sequence, then add 0.5 g of Pd(PPh3)4 and 0.1 g of CuI, heat and react at 80 °C for 6 hours, and monitor the reaction by HPLC until it ends. Cool to room temperature, filter out the solid by suction, wash it with 1M dilute hydrochloric acid until neutral, filter, add 50 g of N,N-dimethylformamide and 50 g of water, heat and dissolve, cool to room temperature to precipitate, filter by suction, wash with toluene, and dry in vacuum at 100 °C for 10 hours to obtain 32 g of 2,2'-(((2,7-bis(phenylethynyl)-9H-fluorene-9,9-ylidene)bis(naphthyl-6,2-ylidene))bis(oxy))diethanol (Compound 3), with a yield of 86% and a purity (HPLC) of 97%. The 1H NMR spectrum is the same as that of Example 3.

[0133] The melting range measured by a capillary melting point apparatus is 210 - 230 °C, and the drying loss measured by a drying loss instrument is 5%, which is an inclusion compound.

[0134] The X-ray diffraction pattern of the crystal is shown in Figure 21 , and characteristic diffraction peaks appear at a diffraction angle 2θ value of 19.34 ± 0.20 as shown in Table 7.

[0135] Table 7

[0136]

Claims

1. A diol derivative crystal of 2,7-bis(phenylethynyl)fluorene, characterized in that, The structural formula is as follows: ； Among them, the aryl group Ar is phenyl, biphenyl or naphthyl.

2. The diol derivative crystal of 2,7-bis(phenylethynyl)fluorene according to claim 1, characterized in that, When the aryl group Ar is phenyl, in the X-ray powder diffraction pattern of the crystal, characteristic diffraction peaks appear at diffraction angle 2θ values of 7.7±0.20, 8.0±0.20, 17.6±0.20, 18.2±0.20, 19.1±0.20, 20.1±0.20, 20.5±0.20, 21.2±0.20, 21.9±0.

20.

3. The diol derivative crystal of 2,7-bis(phenylethynyl)fluorene according to claim 1, characterized in that, When the aryl group Ar is phenyl, the crystal has an endothermic peak measured by a differential scanning calorimeter in the temperature range of 240~260 °C.

4. The diol derivative crystal of 2,7-bis(phenylethynyl)fluorene according to claim 1, characterized in that, When the aryl group Ar is phenyl, the crystal crystallization solvent is a mixture of toluene and anisole.

5. The diol derivative crystal of 2,7-bis(phenylethynyl)fluorene according to claim 1, characterized in that, When the aryl group Ar is biphenyl, in the X-ray powder diffraction pattern of the crystal, characteristic diffraction peaks appear at diffraction angle 2θ values of 4.6±0.20, 8.0±0.20, 9.3±0.20, 14.2±0.20, 16.3±0.20, 20.5±0.20, 27.5±0.

20.

6. The diol derivative crystal of 2,7-bis(phenylethynyl)fluorene according to claim 1, characterized in that, When the aryl group Ar is biphenyl, the crystal has an endothermic peak measured by a differential scanning calorimeter in the temperature range of 180~200 °C.

7. The diol derivative crystal of 2,7-bis(phenylethynyl)fluorene according to claim 1, characterized in that, When the aryl group Ar is biphenyl, the crystal crystallization solvent is a mixture of toluene and methanol.

8. The diol derivative crystal of 2,7-bis(phenylethynyl)fluorene according to claim 1, characterized in that, When the aryl group Ar is naphthyl, the crystal is type A crystal or type B crystal; in the X-ray powder diffraction pattern of the type A crystal, characteristic diffraction peaks appear at diffraction angle 2θ values of 5.4±0.20, 7.3±0.20, 9.9±0.20, 16.2±0.20, 18.2±0.20, 18.5±0.20, 19.6±0.20, 21.0±0.20, 23.3±0.20, 24.1±0.20, 26.1±0.20; in the X-ray powder diffraction pattern of the type B crystal, characteristic diffraction peaks appear at diffraction angle 2θ values of 5.7±0.20, 7.1±0.20, 10.8±0.20, 11.4±0.20, 12.0±0.20, 14.6±0.20, 17.4±0.20, 17.8±0.20, 19.1±0.20, 19.5±0.20, 20.2±0.20, 20.9±0.21, 21.6±0.20, 23.0±0.20, 23.4±0.20, 25.1±0.20, 25.5±0.

20.

9. The diol derivative crystal of 2,7-bis(phenylethynyl)fluorene according to claim 8, characterized in that, The type A crystal has an endothermic peak measured by a differential scanning calorimeter in the temperature range of 230~250 °C.

10. The diol derivative crystal of 2,7-bis(phenylethynyl)fluorenyl according to claim 8, characterized in that, The crystal crystallization solvent of the type A crystal is toluene.

11. The diol derivative crystal of 2,7-bis(phenylethynyl)fluorene according to claim 8, characterized in that, The type B crystal has an endothermic peak measured by a differential scanning calorimeter in the temperature range of 180~210 °C.

12. The diol derivative crystal of 2,7-bis(phenylethynyl)fluorene according to claim 8, characterized in that, The crystal crystallization solvent of the type B crystal is a mixture of toluene and acetonitrile.

13. The diol derivative crystal of 2,7-bis(phenylethynyl)fluorene according to any one of claims 1 to 12, characterized in that, The crystal is a non-inclusion body without solvent complexation or inclusion.

14. A method for preparing the crystal according to claim 1, characterized in that, Using a dibromo compound and phenylacetylene as raw materials, with a molar ratio of 1:2 to 4, under alkaline conditions, using a palladium complex and cuprous halide as catalysts, in an organic solvent, at 60 to 120 °C, with a reaction time of 2 to 24 hours, and then performing recrystallization to obtain crystals.

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