Novel bisphenol-fluorene-like high-refraction compound

Abstract

The invention discloses a novel bisphenol-fluorene-like high-refraction compound which has a chemical structure shown as a formula (I) or a formula (II), wherein # imgabs0 # R is a hydrogen atom or methyl, and X is an oxygen atom or a sulfur atom. The invention also discloses an application of the novel bisphenol fluorene-like high-refraction compound. The invention also discloses a synthesis method of the novel bisphenol fluorene-like high-refraction compound. The sulfur element is introduced into the structure, so that the refractive index of the material can be effectively improved. Therefore, the structure of the bisphenol fluorene is improved, the sulfur element is introduced, and the cargo structure of the bisphenol fluorene is retained, so that the refractive index of the material can be improved, and other characteristics of the bisphenol fluorene structure can be retained.

Description

Technical Field

[0001] The invention relates to the field of high refraction, in particular to a novel bisphenol fluorene-like high refraction compound. Background Art

[0002] Optical resins are becoming more and more popular due to their light weight, impact resistance, easy processing and molding, dyeability and excellent optical properties. They are gradually replacing inorganic optical materials and are widely used in the manufacturing fields of optical fiber communication materials, LED packaging, resin lenses, precision lenses and functional coatings. Bisphenol fluorene structural compounds are widely used because of their high refractive index. In addition to the large volume of benzene ring side groups that give the bisphenol fluorene structure a high refractive index, its unique cargo structure has the following advantages: on the one hand, the four benzene rings are distributed in different planes, which can reduce the directional arrangement of the molecular chain and thus reduce the birefringence value; on the other hand, bisphenol fluorene has a large volume of benzene ring side groups, and the polarizability of the side chain is greater than that of the main chain, showing negative birefringence characteristics, so that the material has a very low birefringence.

[0003] Unfortunately, although the refractive index of bisphenol fluorene compounds is higher than that of other compounds (such as bisphenol A, biphenyl, etc.), its refractive index is still relatively low. For example, the refractive index of 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, which is widely used in the field of photocuring, is only 1.59. Now many application scenarios require the refractive index of the material to be higher than 1.6, which limits its application to a certain extent. Summary of the invention

[0004] The purpose of the present invention is to provide a novel bisphenol fluorene-like high-refractive compound.

[0005] The innovation of the present invention is that the introduction of sulfur into the structure can effectively improve the refractive index of the material. In view of this, the structure of bisphenol fluorene is improved, sulfur is introduced, and its cargo structure is retained, so that the refractive index of the material can be improved and other characteristics of the bisphenol fluorene structure (such as low birefringence, good heat resistance, etc.) can be retained.

[0006] In order to achieve the above-mentioned object of the invention, the technical solution of the present invention is:

[0007] A novel bisphenol fluorene-like high-refractive compound having a chemical structure of the following formula (I) or formula (II):

[0008]

[0009] R is a hydrogen atom or a methyl group, and X is an oxygen or sulfur atom.

[0010] Furthermore, the formula (I) is

[0011]

[0012] Further, the formula (II) is

[0013]

[0014] A novel application of a bisphenol fluorene-like high-refractive compound, formula (I) or formula (II) as a photocurable optical film optical device, is applied to the fields of optical fiber communication materials, LED packaging, resin lenses, precision lenses and functional coating manufacturing.

[0015] A method for synthesizing a novel bisphenol fluorene-like high-refractive compound comprises the following steps:

[0016]

[0017] 1) using anisole as solvent, carrying out Friedel-Crafts reaction with 9-thioxanthone, and then removing the methyl group to obtain intermediate III;

[0018] 2) Intermediate III reacts with Tf2O, and then undergoes metal-catalyzed thiolation reaction and deprotection to obtain intermediate VI.

[0019] 3) Intermediate III reacts with epichlorohydrin to obtain a cation-curable compound

[0020]

[0021] Reaction with ethylene oxide, followed by esterification with acryloyl chloride or methacryloyl chloride, can produce free radical polymerizable compounds

[0022]

[0023] 4) Intermediate VI reacts with epichlorohydrin to obtain a cation-curable compound Reaction with ethylene oxide, followed by esterification with acryloyl chloride or methacryloyl chloride, can produce free radical polymerizable compounds

[0024] The beneficial effects of the present invention are:

[0025] 1. The introduction of sulfur into the structure of the present invention can effectively improve the refractive index of the material. In view of this, the structure of bisphenol fluorene is improved, sulfur is introduced, and its cargo structure is retained, so that the refractive index of the material can be improved and other properties of the bisphenol fluorene structure (such as low birefringence, good heat resistance, etc.) can be retained. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present invention will be described clearly and completely below.

[0027] Embodiment 1: A novel bisphenol fluorene-like high refractive compound having the chemical structure of the following formula (I) or formula (II):

[0028]

[0029] R is a hydrogen atom or a methyl group, and X is an oxygen or sulfur atom.

[0030] The formula (I) is

[0031]

[0032] Formula (II) is

[0033]

[0034] Embodiment 2: A method for synthesizing a novel bisphenol fluorene-like high-refractive compound, comprising the following steps:

[0035] 1) using anisole as solvent, carrying out Friedel-Crafts reaction with 9-thioxanthone, and then removing the methyl group to obtain intermediate III;

[0036] 2) Intermediate III reacts with Tf2O, and then undergoes metal-catalyzed thiolation reaction and deprotection to obtain intermediate VI.

[0037] 3) Intermediate III reacts with epichlorohydrin to obtain a cation-curable compound

[0038]

[0039] Reaction with ethylene oxide, followed by esterification with acryloyl chloride or methacryloyl chloride, can produce free radical polymerizable compounds

[0040]

[0041] 4) Intermediate VI reacts with epichlorohydrin to obtain a cation-curable compound Reaction with ethylene oxide, followed by esterification with acryloyl chloride or methacryloyl chloride, can produce free radical polymerizable compounds

[0042] Example 3: The synthetic routes of intermediate compounds III and VI are as follows:

[0043]

[0044] (1) The synthesis process of compound II is as follows:

[0045] At room temperature, sulfuric acid (98%, 5g, 50mmol) was added to glacial acetic acid (5.3g, 85mmol) under vigorous stirring to obtain a mixture. After the mixture was cooled to 15°C, thioglycolic acid (230mg, 2.5mmol) was added, and then anisole (19mL, 0.125mol) and 9-thioxanthone (5.3g, 25mmol) were added dropwise at this temperature. After the addition was completed, the reaction was heated to 150°C and maintained for 5h to obtain a reaction solution No. 1. After the reaction was completed, the reaction solution No. 1 was quenched into water and extracted with dichloromethane to obtain an organic phase No. 1. After the organic phase No. 1 was combined, the organic phase No. 1 was washed with sodium bicarbonate aqueous solution, washed with saturated brine, dried with anhydrous sodium sulfate and rotary evaporated to obtain an orange-yellow oily crude product. Recrystallization from ethanol gave compound II (3g, yield 60%, purity 98%).

[0046] (2) The synthesis process of compound III is as follows:

[0047] Compound II (3 g, 7.3 mmol) was dissolved in anhydrous dichloromethane (30 ml), and boron tribromide (1 M, 2.8 mL, 28 mmol) was slowly added dropwise at 0°C to obtain reaction solution No. 2. After the addition, reaction solution No. 2 was allowed to naturally warm to room temperature and continued to stir for 16 h. After the reaction was completed, reaction solution No. 2 was quenched into a saturated sodium bicarbonate aqueous solution, extracted with ethyl acetate, and the organic phase No. 2 was combined and washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure to remove the organic solvent, and separated by column chromatography to obtain compound III (2.23 g, purity 98%, yield 80%).

[0048] The chemical structure of compound III was tested, and the NMR characterization results are as follows: 1 H NMR(400MHz,DMSO-d)δ7.41-7.29(d,2H),7.28-7.19(d,2H),7.15-7.03(m,4H),6.91–6.85(d,4H),6.67–6.61(d,4H)

[0049] (3) The synthesis process of compound IV is as follows:

[0050] Compound III (38.2 g, 0.1 mol) and pyridine (23.8 g, 0.3 mol) were dissolved in dichloromethane (200 mL) to obtain a mixed solution No. 3. Trifluoromethanesulfonic anhydride (70.5 g, 0.25 mol) was slowly added dropwise to the mixed solution No. 3 at 0°C. After the addition, stirring was continued for 2 hours to obtain a reaction solution No. 3. After the reaction was completed, the reaction solution No. 3 was quenched into a saturated sodium bicarbonate aqueous solution and extracted with ethyl acetate to obtain an organic phase No. 3. The combined organic phase No. 3 was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was separated by chromatography to obtain compound IV (51.7 g, purity 97%, yield 80%)

[0051] (4) The synthesis process of compound V is as follows:

[0052] Compound IV (51.7 g, 80 mmol), p-methoxybenzyl alcohol (27.2 g, 176 mmol), potassium carbonate (33.2 g, 240 mmol) were dispersed in anhydrous dioxane (500 mL), and Pd2(dBa)3 (3.7 g, 4 mmol) and Binap (5 g, 8 mmol) were added to the mixture under nitrogen atmosphere. After the addition, the mixture was heated to 120°C and kept under reflux for 5 h to obtain reaction solution No. 4. After the reaction was completed, the reaction solution No. 4 was filtered to remove the solid potassium carbonate, and the filtrate was concentrated and separated by column chromatography to obtain compound V (41.6 g, yield 80%, purity 95%)

[0053] (5) The synthesis process of compound VI is as follows

[0054] Compound V (41.6 g, 64 mmol) was slowly added to trifluoroacetic acid (200 mL) at room temperature, stirred evenly, and then slowly heated to 80°C and maintained for 5 h to obtain reaction solution No. 5. After the reaction was completed, reaction solution No. 5 was concentrated to remove most of the trifluoroacetic acid. The residue was quenched into a saturated sodium bicarbonate aqueous solution (300 mL), filtered, and the solid was washed 3 times with petroleum ether. After drying in a vacuum oven, compound VI (23.7 g, purity 96%, yield 90%) was obtained.

[0055] The chemical structure of the test compound VI and the NMR characterization results are as follows: 1 H NMR(400MHz,DMSO-d)δ7.15–7.11(d,2H),7.09-7.07(d,4H),7.04-7.01(d ,2H),6.95-6.91(m,2H),6.89–6.85(m,2H),6.80-6.77(m,4H),3.3(s,2H).

[0056] Example 4: Compound 1 is: The synthetic route of compound 1 is as follows:

[0057]

[0058] (1) The synthesis process of compound 1a is as follows:

[0059] In an autoclave, compound III (40 g, 0.104 mol) and ethylene oxide (460 g, 10.5 mol) were added to the autoclave in sequence at a controlled temperature of 0°C. After the addition was completed, the temperature of the autoclave was raised to 50°C, the pressure was 1 MPa, and the reaction was maintained for 5 hours to obtain reaction solution No. 6. After the reaction was completed, the reaction vessel was cooled to room temperature, and after the pressure was released, the crude compound 1a (49 g, HPLC purity 96%, yield 99%) concentrated from the reaction solution No. 6 was directly used in the next step.

[0060] (2) The synthesis process of compound 1 is as follows:

[0061] Compound 1a (49 g, 0.104 mol), triethylamine (31.6 g, 0.312 mol) and anhydrous ethyl acetate (300 ml) were added to a three-necked flask equipped with a magnetic stirrer, a constant pressure dropping funnel and a nitrogen protection device, and slowly dissolved in an ice-water bath. After the system temperature dropped to 0°C, acryloyl chloride (20.7 g, 0.23 mol) was slowly added dropwise. After the addition was completed, stirring was continued at room temperature for 16 h. The ammonium salt was removed by vacuum filtration, and the filtrate was extracted with water 3 times to remove the unreacted acryloyl chloride. The obtained organic layer solution was dried with anhydrous sodium sulfate, concentrated and filtered, and separated by column chromatography to obtain a colorless oily liquid compound 1 (48 g, yield 80%, purity 98%).

[0062] The chemical structure of test compound 1 and the NMR characterization results are as follows: 1 H NMR(400MHz,DMSO-d)δ7.43-7.34(d,2H),7.29-7.20(d,2H),7.17-7.06(m,4H),6. 93–6.87(d,4H),6.69–6.63(d,4H),6.44–6.35(m,2H)6.21–6.15(m,2H),5.85–5.75

[0063] (m,2H),4.11–4.05(t,4H),3.83–3.78(t,4H)

[0064] Example 5: Compound 2 The synthesis process is similar to that of compound 1, and compound 2 can be prepared by reacting methacryloyl chloride instead of acryloyl chloride with compound 1a.

[0065] Example 6: Compound 3 is

[0066] The synthetic route of compound 3 is the same as that of compound 1, as shown in the figure below:

[0067]

[0068] The chemical structure of test compound 3 and the NMR characterization results are as follows:

[0069] 1 H NMR(400MHz,DMSO-d)δ7.47-7.33(m,6H),7.29-7.17(m,

[0070] 6H),7.17-7.06(m,4H),),6.44–6.35(m,2H),6.21–6.15

[0071] (m,2H),5.85–5.75(m,2H),4.11–4.05(t,4H),3.83–3.78

[0072] (t,4H)

[0073] Example 7: Compound 4 The synthesis process is similar to that of compound 3, and compound 4 can be prepared by reacting methacryloyl chloride instead of acryloyl chloride with compound 2a.

[0074] Example 8: Compound 5 is

[0075] The synthetic route of compound 5 is as follows:

[0076]

[0077] (1) Compound III (40 g, 0.104 mol) was dissolved in epichlorohydrin (300 mL), and potassium hydroxide (16.8 g, 0.3 mol) was added at room temperature. After the addition was completed, the mixture was stirred at room temperature for 16 h to obtain reaction solution No. 7. After the reaction was completed, the reaction solution No. 7 was quenched into a saturated aqueous solution of ammonium chloride and extracted with ethyl acetate three times to obtain an organic phase No. 7. The combined organic phase No. 7 was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to column chromatography to obtain compound 5 (36 g, purity 98%, yield 70%)

[0078] The chemical structure of test compound 5 and the NMR characterization results are as follows: 1H NMR(400MHz,DMSO-d)δ7.41-7.33(d,2H),7.28-7.21(d,2H),7.17-7.05(m,4H),6.93–6.88(d,4H),6.69–6.63(d,4H ), 4.25–4.23(d,2H),3.78–3.75(d,2H),3.29–3.27(m,2H),2.81–2.78(m,2H),2.68–2.66(m,2H),1.60–1.59(m,2H)

[0079] Example 9: Compound 6 uses compound VI as raw material, and the synthesis method is the same as that of compound 5.

[0080] Example 10: The synthesis method is the same as above (same as Example 8), compound III and compound VI are reacted with 2-(chloromethyl)-2-methyloxirane to obtain compound 7 and compound 8 The chemical structure of test compound 8 and the NMR characterization results are as follows: 1 H NMR(400MHz,DMSO-d)δ7.53-7.44(d,2H),7.39-7.34(d,2H),7.27-7.21(m,6H),7.15–7.06(m,6H),3.61(s,4H),2.78(s,4H),1.39(s,6H)

[0081] The refractive index and properties of some products in the present invention are as follows:

[0082]

[0083]

[0084] Application in optical film Comparative Example 1

[0085] Taking the compound of comparative example 1 as an example, light-initiated free radical polymerization is adopted, and the specific operation is as follows: 2 parts by weight of photoinitiator (1173) is evenly mixed with 50 parts by weight of the compound of comparative example 1 and 50 parts by weight of OPPEA (a high-refractive compound diluent), and then evenly applied on a glass slide. The optical film of comparative example 1 is obtained by irradiating with a high-pressure mercury lamp (lamp distance 5 cm, light intensity I365 = 1 mW / cm2). The refractive index of the film is measured to be 1.60, and the cured film is colorless.

[0086] Application of optical film Embodiment 1 of the present invention

[0087] The photopolymerization of the above product compounds 1-4 containing (meth)acrylate groups is suitable for photoinitiated free radical polymerization. Taking compound 1 as an example, it is compounded with photoinitiator 1173 and high-refractive compound diluent OPPEA, and the formula ratio is the same as that of the above-mentioned comparative example 1. The optical film obtained after curing is colorless and transparent, and the refractive index is 1.645, which is significantly higher than that of comparative example 1.

[0088] Application in optical film Comparative Example 2

[0089] Taking the compound of comparative example 2 as an example, photo-initiated cationic polymerization is adopted, and the specific operation is as follows: 2 parts by weight of cationic photoinitiator (6976) is evenly mixed with 50 parts by weight of the compound of comparative example 2 and 50 parts by weight of bisphenol A epoxy (CAS: 1675-54-3, refractive index 1.57), and then evenly smeared on a glass slide. The optical film of cationic polymerization of comparative example 2 is obtained by irradiation with a high-pressure mercury lamp (lamp distance 5 cm, light intensity I365 = 1 mW / cm2). The refractive index of the film is measured to be 1.635, and the cured film is colorless.

[0090] Application of optical film Embodiment 2 of the present invention

[0091] Compounds 5 and 6 in the present invention are suitable for photoinitiated cationic polymerization. Taking compound 6 as an example, it is compounded with cationic photoinitiator 6976 and bisphenol A epoxy, and the formula ratio is the same as that of the above-mentioned comparative example 2. The optical film obtained after curing is colorless and transparent, and the refractive index is 1.695, which is significantly higher than that of comparative example 2.

[0092] The described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

Claims

1. A novel bisphenol fluorene-like high refractive compound, characterized in that: It has the chemical structure of the following formula (I) or formula (II): R is a hydrogen atom or a methyl group, and X is an oxygen or sulfur atom.

2. The novel bisphenol fluorene-like high refractive compound according to claim 1, characterized in that: The formula (I) is 3. The novel bisphenol fluorene-like high refractive compound according to claim 1, characterized in that: The formula (II) is 4. Application of a novel bisphenol fluorene-like high refractive compound, characterized in that: Formula (I) or (II) is used as a photocurable optical film optical device and is applied to the fields of optical fiber communication materials, LED packaging, resin lenses, precision lenses and functional coating manufacturing.

5. A method for synthesizing a novel bisphenol fluorene-like high-refractive compound, characterized in that: The following steps are involved: 1) using anisole as solvent, carrying out Friedel-Crafts reaction with 9-thioxanthone, and then removing the methyl group to obtain intermediate III; 2) Intermediate III reacts with Tf2O, and then undergoes metal-catalyzed thiolation reaction and deprotection to obtain intermediate VI. 3) Intermediate III reacts with epichlorohydrin to obtain a cation-curable compound Reaction with ethylene oxide, followed by esterification with acryloyl chloride or methacryloyl chloride, can produce free radical polymerizable compounds Intermediate VI reacts with epichlorohydrin to obtain a cationically curable compound. Reaction with ethylene oxide, followed by esterification with acryloyl chloride or methacryloyl chloride, can produce free radical polymerizable compounds

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