A new type of bisphenol fluorene-like high refractive compound

Abstract

The present invention discloses a novel bisphenol fluorene-like high-refractive compound having a 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. The present invention also discloses an application of the novel bisphenol fluorene-like high-refractive compound. The present invention also discloses a method for synthesizing the novel bisphenol fluorene-like high-refractive compound. The present invention introduces sulfur into the structure to effectively increase the refractive index of the material. In view of this, the structure of bisphenol fluorene is improved to introduce sulfur while retaining its cargo structure. This improves the refractive index of the material while retaining other properties of the bisphenol fluorene structure.

Description

Technical Field

[0001] The present 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 gaining increasing popularity due to their lightweight, impact resistance, ease of processing, dyeability, and excellent optical properties. They are gradually replacing inorganic optical materials and are widely used in the manufacturing of fiber optic communication materials, LED packaging, resin lenses, precision lenses, and functional coatings. Bisphenol fluorene compounds are widely used due to their high refractive index. In addition to the high refractive index imparted by the bulky benzene ring side groups, their unique cargo structure offers the following advantages: Firstly, the four benzene rings are distributed in different planes, reducing the directional alignment of the molecular chain and thus lowering the birefringence value; secondly, the large benzene ring side groups in bisphenol fluorene result in a side chain polarizability greater than that of the main chain, resulting in negative birefringence and ultimately, 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 and biphenyl), its refractive index is still relatively low. For example, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, which is widely used in the field of photocuring, has a refractive index of only 1.59. Many current applications require materials with a refractive index higher than 1.6, which to some extent limits its application. 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 this invention lies in the fact that the introduction of sulfur into the structure can effectively increase the refractive index of the material. In view of this, the structure of bisphenol fluorene is improved by introducing sulfur while retaining its cargo structure. This improves the refractive index of the material while retaining other properties of the bisphenol fluorene structure (such as low birefringence and good heat resistance).

[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 the 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] Furthermore, 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 in 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, performing a 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 and deprotection to obtain intermediate VI.

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

[0020]

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

[0022]

[0023] 4) 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 polymer compounds.

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

[0025] 1. Introducing sulfur into the structure of the present invention can effectively increase the refractive index of the material. In view of this, the structure of bisphenol fluorene is improved by introducing sulfur while retaining its cargo structure. This can increase the refractive index of the material while retaining other properties of the bisphenol fluorene structure (such as low birefringence and good heat resistance). DETAILED DESCRIPTION

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

[0027] Example 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] Formula (I) is

[0031]

[0032] Formula (II) is

[0033]

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

[0035] 1) using anisole as solvent, performing a 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 and deprotection to obtain intermediate VI.

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

[0038]

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

[0040]

[0041] 4) 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 polymer 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%, 5 g, 50 mmol) was added to glacial acetic acid (5.3 g, 85 mmol) with vigorous stirring to obtain a mixture. After the mixture was cooled to 15°C, thioglycolic acid (230 mg, 2.5 mmol) was added, followed by dropwise addition of anisole (19 mL, 0.125 mol) and 9-thioxanthone (5.3 g, 25 mmol) at the same temperature. After the addition was complete, the reaction was heated to 150°C and maintained for 5 hours to obtain reaction solution No. 1. After the reaction was completed, reaction solution No. 1 was quenched into water and extracted with dichloromethane to obtain organic phase No. 1. After the organic phases No. 1 were combined, washed with aqueous sodium bicarbonate solution and saturated brine, dried over anhydrous sodium sulfate, and rotary evaporated to obtain a crude orange-yellow oil. Compound II (3 g, 60% yield, 98% purity) was recrystallized from ethanol.

[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). Boron tribromide (1 M, 2.8 mL, 28 mmol) was slowly added dropwise at 0°C to obtain Reaction Solution II. After the addition, Reaction Solution II was allowed to warm to room temperature and stirred for 16 hours. After the reaction, Reaction Solution II was quenched into saturated sodium bicarbonate aqueous solution and extracted with ethyl acetate. The combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to remove the organic solvent. Compound III (2.23 g, 98% purity, 80% yield) was then isolated by column chromatography.

[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 was complete, 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), and potassium carbonate (33.2 g, 240 mmol) were dispersed in anhydrous dioxane (500 mL). Pd2(dBa)3 (3.7 g, 4 mmol) and Binap (5 g, 8 mmol) were added to the mixture under a nitrogen atmosphere. After addition, the mixture was heated to 120°C and refluxed for 5 h to obtain reaction solution No. 4. After the reaction, reaction solution No. 4 was filtered to remove solid potassium carbonate. 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. After stirring, the mixture was slowly heated to 80°C and maintained for 5 hours to obtain Reaction Solution 5. After completion of the reaction, Reaction Solution 5 was concentrated to remove most of the trifluoroacetic acid. The residue was quenched into saturated aqueous sodium bicarbonate (300 mL), filtered, and the solid washed three times with petroleum ether. After drying in a vacuum oven, Compound VI (23.7 g, 96% purity, 90% yield) was obtained.

[0055] The chemical structure of compound VI was tested, 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 sequentially at 0°C. After the additions were complete, the autoclave temperature was raised to 50°C and the pressure was 1 MPa. The reaction was maintained for 5 hours to yield Reaction Solution 6. After the reaction was completed, the autoclave was cooled to room temperature and the pressure was released. The crude product, Compound 1a (49 g, HPLC purity 96%, yield 99%), obtained by concentration of Reaction Solution 6 was used directly 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. The mixture was 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 hours. The ammonium salt was removed by filtration under reduced pressure. The filtrate was extracted three times with water to remove unreacted acryloyl chloride. The resulting organic layer solution was dried over anhydrous sodium sulfate, concentrated, filtered, and separated by column chromatography to obtain compound 1 (48 g, yield 80%, purity 98%) as a colorless oily liquid.

[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 ammonium chloride solution 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 compound 5 was tested, 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 was synthesized using compound VI as the raw material using the same method as compound 5.

[0080] Example 10: The synthesis method is the same as above (same as Example 8), and 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 this invention are as follows:

[0082]

[0083]

[0084] Comparative Example 1 of Application in Optical Film

[0085] Taking the compound of Comparative Example 1 as an example, light-initiated free radical polymerization was carried out, and the specific operation was as follows: 2 parts by weight of photoinitiator (1173) was 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 was 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 was measured to be 1.60, and the cured film was colorless.

[0086] Application of Optical Films in Example 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] Comparative Example 2 of Application in Optical Film

[0089] Taking the compound of Comparative Example 2 as an example, photoinitiator cationic polymerization was used, and the specific operation was as follows: 2 parts by weight of cationic photoinitiator (6976) was mixed evenly 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 applied on a glass slide. The optical film of cationic polymerization of Comparative Example 2 was 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 was measured to be 1.635, and the cured film was colorless.

[0090] Application of Optical Films in Example 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 formulation 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 embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

Claims

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

2. A use of the bisphenol fluorene-like compound according to claim 1, characterized in that: Formula (II) is a photocurable optical film optical device, which is used in the fields of optical fiber communication materials, LED packaging, resin lenses, precision lenses and functional coating manufacturing.

3. A method for synthesizing a bisphenol fluorene-like compound according to claim 1, characterized in that: The following steps are involved: ， 1) Using anisole as solvent, a Friedel-Crafts reaction was carried out with 9-thioxanthone, followed by removal of the methyl group to obtain intermediate III; 2) Intermediate III reacts with Tf2O, followed by metal-catalyzed thiolation and deprotection to obtain intermediate VI; 3) Intermediate III reacts with epichlorohydrin to obtain a cationically curable compound , and ; 4) Intermediate VI reacts with epichlorohydrin to obtain a cationic curable compound and .

Images