Phosphorus-containing high-refractive-index optical polyarylester and preparation method thereof

Abstract

The invention discloses phosphorus-containing high-refractive-index optical polyarylester and a preparation method, the polyarylester has a structure shown in a formula I: # imgabs0 #, in the formula I, R is selected from at least one of H, halogen, methyl and methoxyl; x is selected from at least one of O and S; and n is in a range of 1 to 1000. The high-refractive-index optical polyester is prepared in a mode of copolymerization of phosphorus-containing DOPO series derivatives and phosphoryl chloride / phosphorosulfuryl chloride, the refractive index (nd) at 589nm can reach 1.64-1.68, the glass-transition temperature can reach 200-300 DEG C, the visible light transmittance is high and is larger than 88%, and the high-refractive-index optical polyester has high potential application value in the aspect of high-refractive-index optical resin.

Description

Technical Field

[0001] The present application relates to a phosphorus-containing high-refractive-index optical polyarylate and a preparation method thereof, and belongs to the field of polymer materials. Background Art

[0002] With the development of electronic science and the Internet, the application fields of optical lenses are becoming increasingly extensive. Resin lenses are popular due to their low manufacturing difficulty, high mass production capacity, low cost and light weight, and are also a hot spot in the field of lens design at this stage.

[0003] The functions of high refractive index optical resin are mainly as follows: 1. The refractive index of the lens is increased, which is convenient for aberration correction and can effectively improve the performance of the lens. 2. The high refractive index can reduce the height of the optical system and achieve a low total length of the lens (TTL), effectively realizing the miniaturization and lightweight of the lens.

[0004] The preparation of thermoplastic high refractive index optical resin mainly adopts the following three aspects in terms of structural design: 1. condensed ring structure, 2. sulfur-containing structure, 3. phosphorus-containing structure. CN 201580023583.2 discloses a polycarbonate resin composition, a polycarbonate composition, but the birefringence of polycarbonate is relatively high. In addition, the requirements of factors such as Abbe number and high temperature fluidity must be combined. The condensed ring structure is relatively rigid, resulting in a high melt index of the material, which is not conducive to high temperature injection molding, and the sulfur-containing structure is usually yellowish in color. This patent adopts a sulfur-containing structure to prepare a high-performance optical resin by reacting a series of DOPO monomer derivatives with phosphorus / phosphorus thiochloride. The material has the advantages of good high temperature fluidity and high refractive index. The refractive index (nd) at 589nm can reach 1.64-1.68, the glass transition temperature can reach 200-300℃, and it has a high visible light transmittance of >88%, which has a high potential application value in high refractive index optical resins. Summary of the invention

[0005] According to one aspect of the present application, a phosphorus-containing high-refractive-index optical polyarylate is provided, wherein the polyarylate has a structure of Formula I:

[0006]

[0007] In Formula I, R is selected from at least one of H, halogen, methyl, and methoxy;

[0008] The X is selected from at least one of O and S;

[0009] The n is 1-1000.

[0010] According to the second aspect of the present application, a method for preparing a phosphorus-containing high-refractive-index optical polyarylate is provided, the preparation method comprising the following steps:

[0011] The preparation method comprises the following steps:

[0012] The phosphorus-containing bisphenol monomer and the phosphorus oxychloride monomer are mixed and reacted under the action of a catalyst to obtain the phosphorus-containing polyarylate.

[0013] The phosphorus-containing bisphenol monomer has a structure of formula II;

[0014]

[0015] Optionally, phosphorus-containing aromatic monophenol, phosphorus-free aromatic monophenol and aromatic aldehyde are mixed, and reacted under the action of catalyst I to obtain phosphorus-containing bisphenol monomer;

[0016] Optionally, the phosphorus-containing aromatic monophenol is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;

[0017] The phosphorus-free aromatic monophenol is selected from at least one of bromophenol, o-cresol and phenol;

[0018] The aromatic aldehyde is selected from at least one of p-hydroxybenzaldehyde, 3-methoxy-4-hydroxybenzaldehyde, and 3-bromo-4-hydroxybenzaldehyde;

[0019] The catalyst I is selected from p-toluenesulfonic acid.

[0020] Optionally, the mass ratio of the phosphorus-containing aromatic monophenol, the phosphorus-free aromatic monophenol, and the aromatic aldehyde is 10-11:9-10:22-35.

[0021] Optionally, the mass ratio of the catalyst I to the phosphorus aromatic monophenol is 0.04:1 to 1:1.

[0022] Optionally, in step I, the reaction conditions of reaction I are as follows:

[0023] The temperature of the reaction I is 130-180°C;

[0024] The reaction time of the reaction I is 20 to 48 hours.

[0025] Optionally, the phosphorus oxychloride-containing monomer is selected from at least one of phosphorus oxychloride, phenyl phosphorus oxychloride, and phenyl phosphorothioyl chloride;

[0026] The catalyst is selected from at least one of triethylamine, nitrogen-methylimidazole, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, and potassium bicarbonate.

[0027] Optionally, the molar ratio of the phosphorus-containing bisphenol monomer to the phosphorus-containing chloride monomer is 0.9:1 to 1.1:1.

[0028] Optionally, the mass ratio of the catalyst to the phosphorus-containing bisphenol monomer is 0.04:1 to 1:1.

[0029] Optionally, the reaction conditions of the reaction are as follows:

[0030] The reaction temperature is 25-260°C;

[0031] The reaction time is 2 to 6 hours.

[0032] This application is prepared by homopolymerizing or copolymerizing DOPO bisphenol structure with phosphoryl chloride / phosphorus thiochloride. The specific structure is as follows:

[0033] DOPO derivatives are as follows:

[0034]

[0035] Wherein R can be H, halogen, methyl, methoxy.

[0036] The structures of phosphorus oxychloride and phosphorus thiochloride are as follows:

[0037]

[0038] 1 The polymerization method can be low temperature solution, high temperature solution, interfacial polymerization, melt polycondensation.

[0039] 2. The bisphenol monomer in the polymer structure can be one or more of the R-substituted monomers. One or two of the acyl chloride monomers in the polymer.

[0040] 3 The catalyst selected in the polymerization process can be one or more of triethylamine, nitrogen-methylimidazole, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, and potassium bicarbonate.

[0041] The preparation process is as follows:

[0042] 1 The polymerization method can be a low-temperature solution, a high-temperature solution, or an interfacial polymerization method. Bisphenol is excessive, and trans-cinnamic acid chloride is added in the late stage of the polymerization reaction for end-capping.

[0043] 2 The bisphenol monomer in the polymer structure can be one or more of the R substitutions.

[0044] 3 The catalyst selected in the polymerization process can be one or more of triethylamine, nitrogen-methylimidazole, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, and potassium bicarbonate.

[0045] 4. The molar ratio of the phosphorus oxychloride monomer to the DOPO diphenol monomer in the preparation method is 0.9:1 to 1.1:1.

[0046] 5. Reaction conditions of the preparation method, such as temperature 0°C to 200°C, solid content 5% to 30%, etc.

[0047] In the present application, "DOPO" refers to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which has a phosphaphenanthrene ring structure and is usually used in the flame retardant field. Here, its application is expanded to be used in optical resin polymers.

[0048] The beneficial effects of this application include:

[0049] The phosphorus-containing polyarylate provided in the present application has a high refractive index, good high temperature fluidity, and light transmittance. The refractive index at 589nm (n d ) can reach 1.64-1.68, the glass transition temperature can reach 200-300°C, and it has a high visible light transmittance of >88%. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 This is a reaction diagram of the phosphorus-containing bisphenol monomer and the acyl chloride monomer of the present application;

[0051] Figure 2 is a differential scanning calorimetry curve of the phosphorus-containing polyarylate prepared in Example 1 of the present application;

[0052] Figure 3 This is a gel permeation chromatogram of the phosphorus-containing polyarylate prepared in Example 2 of the present application;

[0053] Figure 4 This is a gel permeation chromatogram of the phosphorus-containing polyarylate prepared in Example 3 of the present application;

[0054] Figure 5 This is a gel permeation chromatogram of the phosphorus-containing polyarylate prepared in Example 4 of the present application;

[0055] Figure 6 This is a thermogravimetric analysis diagram of the phosphorus-containing polyarylate prepared in Example 5 of the present application;

[0056] Figure 7 This is the H NMR spectrum of the phosphorus-containing polyarylate prepared in Example 1 of the present application;

[0057] Figure 8 This is the H NMR spectrum of the phosphorus-containing polyarylate prepared in Example 3 of the present application;

[0058] Fig. 9 This is the H NMR spectrum of the phosphorus-containing polyarylate prepared in Example 6 of the present application;

[0059] Fig.10 This is the H NMR spectrum of the phosphorus-containing bisphenol monomer synthesized in Example 2 of the present application;

[0060] Fig.11 This is the H NMR spectrum of the phosphorus-containing bisphenol monomer synthesized in Example 6 of the present application;

[0061] Fig.12This is the H NMR spectrum of the phosphorus-containing bisphenol monomer synthesized in Example 4 of the present application;

[0062] Fig.13 This is the H-NMR spectrum of the phosphorus-containing bisphenol monomer synthesized in Example 1 of the present application. DETAILED DESCRIPTION

[0063] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0064] Unless otherwise specified, the raw materials and catalysts in the examples and comparative examples of the present application were purchased through commercial channels.

[0065] The analysis methods in the examples and comparative examples of the present application are as follows:

[0066] The molecular structures of the phosphorus-containing bisphenol monomers and phosphorus-containing polyarylate synthesized in the examples were analyzed using ECZ Luminous (JNM-ECZL series, 400 MHz) nuclear magnetic resonance (NMR) instrument;

[0067] The thermal properties of the phosphorus-containing polyarylate synthesized in the example were analyzed using a TADSC25 Differential Scanning Calorimeter (DSC) instrument;

[0068] The molecular weight and molecular weight distribution of the phosphorus-containing polyarylate synthesized in the example were analyzed using a 2414HPLC gel permeation chromatography (GPC) instrument;

[0069] The thermal stability of the synthesized samples was analyzed using a TA Discovery TGA55 Thermogravimetric Analyzer (TGA).

[0070] Example 1

[0071] (1) Preparation of phosphorus-containing bisphenol monomers

[0072] 10.80g DOPO, 10.25g 3-bromo-4-hydroxybenzaldehyde, 34.6g bromophenol, 432mg p-toluenesulfonic acid were added to a 250mL three-necked flask with mechanical stirring, condensation reflux and nitrogen inlet, and the temperature was raised to 130°C and the reaction was continued for 20h. After the reaction was completed, the reaction product was precipitated in 200mL anhydrous ethanol, the precipitate was filtered, and the precipitate was washed with anhydrous ethanol for three times. Drying in a vacuum oven at 110°C for 10h obtained a white solid, i.e., a phosphorus-containing bisphenol monomer, the nuclear magnetic hydrogen spectrum of which is as follows: Fig.13As shown, the bisphenol at the lowest field position is the proton peak of the phenolic hydroxyl group, the peaks at 6.8-8.4ppm belong to the proton peaks on the phenanthrene ring and the benzene ring connected to it, and the double peak at 4.67ppm belongs to the single proton on the central carbon of the monomer. In addition, from the integrated area of ​​the hydrogen spectrum peak, each group of proton peaks corresponds to the proton on the polymer, indicating the successful synthesis of the phosphorus-containing bisphenol monomer.

[0073] (2) Preparation of phosphorus-containing polyarylate

[0074] 5.72 g of the phosphorus-containing bisphenol monomer obtained above, 1.2 g of sodium hydroxide, 80 mL of deionized water and 2.1 g of benzyltriethylammonium chloride were added into a 500 mL three-necked flask equipped with mechanical stirring, condensation reflux and nitrogen inlet, and stirred until the system was clear. 1.99 g of phenylphosphoryl chloride was dissolved in 60 mL of dichloromethane solution, and slowly added dropwise to the rapidly stirred alkaline solution of the bisphenol monomer, and reacted at 100°C for 2 h. It was sunk into a hydrochloric acid / methanol (volume ratio: 1 / 50) solution, and the filtered solid was washed with deionized water for 3 to 5 times, and dried to obtain polyarylate. The differential scanning calorimetry curve and nuclear magnetic hydrogen spectrum of the polyarylate were shown as follows: Figure 2 , Figure 7 . Such as nuclear magnetic hydrogen spectrum ( Figure 7 ), the double peak near 4.5ppm belongs to the proton peak on the central carbon of the phosphorus-containing bisphenol monomer in the polymer, which is a double peak due to the strong coupling effect of P; 7.5-8.0ppm is the proton peak on the phenanthrene ring in the DOPO structure. In addition, from the integrated area of ​​the hydrogen spectrum peak, each group of proton peaks corresponds to the proton on the polymer, which proves that the polyarylate was successfully synthesized.

[0075] Example 2

[0076] (1) Preparation of phosphorus-containing bisphenol monomers

[0077] 10.80g DOPO, 9.13g vanillin, 24.8g guaiacol, and 432mg p-toluenesulfonic acid were added to a 250mL three-necked flask with mechanical stirring, condensation reflux, and nitrogen inlet, and the temperature was raised to 130°C and the reaction was continued for 20h. After the reaction, the reaction product was precipitated into 200mL anhydrous ethanol, the precipitate was filtered, and the precipitate was washed with anhydrous ethanol for three times. Drying in a vacuum oven at 110°C for 10h gave a white solid, i.e., a phosphorus-containing bisphenol monomer, and the nuclear magnetic hydrogen spectrum of the phosphorus-containing bisphenol monomer was as follows: Fig.10 As shown, first, the double peak between 8.8-9.0ppm is the proton on the phenolic hydroxyl group, and secondly, the double peak at 4.67ppm belongs to the single proton on the central carbon of the monomer, which is attributed to the methoxy group substituted on the benzene ring compared to the peak at 3.65ppm of the bisphenol monomer in other examples. In addition, from the integrated area of ​​the hydrogen spectrum peak, each group of proton peaks corresponds to the proton on the polymer, indicating the successful preparation of the phosphorus-containing bisphenol monomer.

[0078] (2) Preparation of phosphorus-containing polyarylate

[0079] 4.74 g of the phosphorus-containing bisphenol monomer obtained above, 1.2 g of sodium hydroxide, 80 mL of deionized water and a small amount of benzyltriethylammonium chloride were added to a 500 mL three-necked flask equipped with mechanical stirring, condensation reflux and nitrogen inlet, and stirred until the system was clear. 1.99 g of phenylphosphoryl chloride was dissolved in 60 mL of dichloromethane solution, and slowly added dropwise to the rapidly stirred alkaline solution of the bisphenol monomer, and reacted at 10°C for 2 hours. It was sunk into a hydrochloric acid / methanol solution (volume ratio: 1 / 50), and the filtered solid was washed with deionized water for 3 to 5 times, and dried to obtain polyarylate. The gel permeation chromatography of the polyarylate showed Figure 3 , and the number average molecular weight is 17.8 kg / mol, indicating the successful preparation of the polyarylate.

[0080] Example 3

[0081] (1) Preparation of phosphorus-containing bisphenol monomers

[0082] 10.80g DOPO, 9.13g vanillin, 24.8g guaiacol, 432mg p-toluenesulfonic acid were added to a 250mL three-necked flask with mechanical stirring, condensation reflux and nitrogen inlet, and the temperature was raised to 130°C and the reaction was continued for 20h. After the reaction, the reaction product was precipitated into 200mL anhydrous ethanol, the precipitate was filtered, and the precipitate was washed with anhydrous ethanol three times. Drying in a vacuum oven at 110°C for 10h to obtain a white solid, the obtained white solid was dissolved in a NaOH water / ethanol solution, and the solution was filtered to remove insoluble matter. The filtrate was slowly added dropwise to a water / ethanol solution of HCl, the precipitated solid was filtered, and washed with deionized water until neutral. Drying obtained a phosphorus-containing bisphenol monomer with high purity.

[0083] (2) Preparation of phosphorus-containing polyarylate

[0084] 4.47 g of the above-obtained high-purity phosphorus-containing bisphenol monomer and 2.11 g of phenylphosphothioyl chloride were added to a 100 mL three-necked flask, and the temperature was raised to 260° C. under nitrogen flow conditions. The reaction was performed for 4 h to obtain a yellow solid to obtain polyarylate. The gel permeation chromatography and nuclear magnetic hydrogen spectrum of the polyarylate were shown as follows: Figure 4 , Figure 8 . Such as nuclear magnetic hydrogen spectrum ( Figure 8 ), the double peak near 4.5ppm belongs to the proton peak on the central carbon of the phosphorus-containing bisphenol monomer in the polymer, the single peak near 3.8ppm is the proton peak of the methyl ether on the side chain of the polymer; 7.5-8.0ppm is the proton peak on the phenanthrene ring in the DOPO structure. In addition, from the integrated area of ​​the hydrogen spectrum peak, each group of proton peaks corresponds to the proton on the polymer, which proves that the polyarylate was successfully synthesized.

[0085] Example 4

[0086] (1) Preparation of phosphorus-containing bisphenol monomers

[0087] 10.80g DOPO, 6.11g p-hydroxybenzaldehyde, 18.82g phenol, 432mg p-toluenesulfonic acid were added to a 250mL three-necked flask with mechanical stirring, condensation reflux and nitrogen inlet, and the temperature was raised to 130°C and the reaction was continued for 20h. After the reaction, the reaction product was precipitated into 200mL anhydrous ethanol, the precipitate was filtered, and the precipitate was washed with anhydrous ethanol for three times. Drying in a vacuum oven at 110°C for 10h gave a white solid, i.e., a phosphorus-containing bisphenol monomer, and the nuclear magnetic hydrogen spectrum of the phosphorus-containing bisphenol monomer was as follows Fig.12 As shown, the bisphenol at the lowest field position is the proton peak of the phenolic hydroxyl group, the peaks at 6.8-8.4ppm belong to the proton peaks on the phenanthrene ring and the benzene ring connected to it, and the double peak at 4.67ppm belongs to the single proton on the central carbon of the monomer. In addition, from the integrated area of ​​the hydrogen spectrum peak, each group of proton peaks corresponds to the proton on the polymer, indicating the successful synthesis of the phosphorus-containing bisphenol monomer.

[0088] (2) Preparation of phosphorus-containing polyarylate

[0089] 4.14 g of the phosphorus-containing bisphenol monomer obtained above, 3 mL of nitrogen methyl imidazole and 40 mL of dichloromethane were added to a 250 mL three-necked flask with mechanical stirring, condensation reflux and nitrogen inlet, and stirred for 3 hours. Then 1.99 g of phosphoryl chloride was dissolved in 40 mL of dichloromethane solution and added to the reaction flask, and the reaction was continued at 10°C for 3 hours. The reaction solution was sunk into anhydrous methanol, and the precipitate was washed once with anhydrous methanol, filtered and dried to obtain polyarylate. The gel permeation chromatography of the polyarylate showed Figure 4 , and the number average molecular weight was 22.5 kg / mol, indicating the successful preparation of polyarylate.

[0090] Example 5

[0091] (1) Preparation of phosphorus-containing bisphenol monomers

[0092] 10.80g DOPO, 9.13g vanillin, 21.6g o-cresol, 432mg p-toluenesulfonic acid were added to a 250mL three-necked flask with mechanical stirring, condensation reflux and nitrogen inlet, and the temperature was raised to 130°C and the reaction was continued for 20h. After the reaction was completed, the reaction product was precipitated in 200mL anhydrous ethanol, the precipitate was filtered, and the precipitate was washed with anhydrous ethanol for three times. Dry in a vacuum oven at 110°C for 10h to obtain a white solid, i.e., phosphorus-containing bisphenol monomer.

[0093] (2) Preparation of phosphorus-containing polyarylate

[0094] 4.74 g of the phosphorus-containing bisphenol monomer obtained above, 3 mL of triethylamine and 40 mL of dichloromethane were added to a 250 mL three-necked flask with mechanical stirring, condensation reflux and nitrogen inlet, and stirred for 3 hours. Then 2.11 g of phenylphosphothioyl chloride was dissolved in 40 mL of dichloromethane solution and added to the reaction flask, and the reaction was continued at 10°C for 3 hours. The reaction solution was sunk into anhydrous methanol, and the precipitate was washed once with anhydrous methanol, filtered and dried to obtain polyarylate. The thermogravimetric analysis of the polyarylate is shown in Figure 6 As can be seen from the figure, the polyarylate material does not decompose before 400°C, and the 5% thermal decomposition temperature is greater than 400°C, indicating that the thermal stability of the polyarylate is relatively excellent.

[0095] Example 6

[0096] (1) Preparation of phosphorus-containing bisphenol monomers

[0097] 10.80g DOPO, 6.94g 4-hydroxy-3-methylbenzaldehyde, 21.6g o-cresol, 432mg p-toluenesulfonic acid were added to a 250mL three-necked flask with mechanical stirring, condensation reflux and nitrogen inlet, and the temperature was raised to 130°C and the reaction was continued for 20h. After the reaction, the reaction product was precipitated into 200mL anhydrous ethanol, the precipitate was filtered, and the precipitate was washed with anhydrous ethanol three times. Dry in a vacuum oven at 110°C for 10h to obtain a white solid, and the obtained white solid was dissolved in a NaOH water / ethanol solution, and the solution was filtered to remove insoluble matter. The filtrate was slowly added dropwise to a water / ethanol solution of HCl, the precipitated solid was filtered, and washed with deionized water until neutral. Drying gave a phosphorus-containing bisphenol monomer with higher purity, and the nuclear magnetic hydrogen spectrum of the phosphorus-containing bisphenol monomer was as shown Fig.11 As shown in the figure, first, the double peak between 8.8-9.0ppm is the proton on the phenolic hydroxyl group, and secondly, the double peak at 4.67ppm belongs to the single proton on the central carbon of the monomer, which is attributed to the methyl substituted on the benzene ring compared to the peak at 2.03ppm of the bisphenol monomer in other examples. In addition, from the integrated area of ​​the hydrogen spectrum peak, each group of proton peaks corresponds to the proton on the polymer, indicating the successful synthesis of the phosphorus-containing bisphenol monomer.

[0098] (2) Preparation of phosphorus-containing polyester

[0099] 4.14 g of the above-obtained high-purity phosphorus-containing bisphenol monomer, 1.2 g of potassium carbonate, 80 mL of deionized water and a small amount of benzyltriethylammonium chloride were added into a 500 mL three-necked flask equipped with mechanical stirring, condensation reflux and nitrogen inlet, and stirred until the system was clarified. 2.11 g of phenylphosphothioyl chloride was dissolved in 60 mL of dichloromethane solution, and slowly added dropwise to the rapidly stirred alkaline solution of bisphenol monomer, and reacted at 10°C for 2 hours. It was sunk into a hydrochloric acid / methanol (volume ratio: 1 / 50) solution, and the filtered solid was washed with deionized water for 3 to 5 times, and dried to obtain polyarylate. The hydrogen nuclear magnetic spectrum of the polyarylate was shown in Fig. 9 . Such as nuclear magnetic hydrogen spectrum ( Fig. 9 ), the double peak near 4.5ppm belongs to the proton peak on the central carbon of the phosphorus-containing bisphenol monomer in the polymer, 7.5-8.0ppm is the proton peak on the phenanthrene ring in the DOPO structure, and the double peak near 2ppm is attributed to the proton on the methyl group in the phosphorus-containing monomer unit in the polyarylate. In addition, from the integrated area of ​​the hydrogen spectrum peak, each group of proton peaks corresponds to the proton on the polymer, thus proving that the polyarylate was successfully synthesized.

[0100] Comparative Example 1

[0101] Polyester was prepared by low-temperature solution polymerization using bisphenol fluorene and terephthaloyl chloride as raw materials. The preparation process is as follows: bisphenol fluorene (3.42 g, 10.5 mmol) and triethylamine (3 mL) were added to 70 mL of dichloromethane in a three-necked flask equipped with a mechanical stirrer, and stirred at 10°C for about 40 minutes. 60 mL of dichloromethane solution containing terephthaloyl chloride (1.99 g, 10 mmol) was slowly added dropwise to the above mixture, and the viscosity gradually increased. The addition was completed in about 30 minutes, and the reaction was continued at 10°C for 5 hours. The reaction product was precipitated in methanol.

[0102] Table 1 Visible light transmittance, glass transition temperature, and refractive index of phosphorus-containing polyarylate

[0103]

[0104] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A phosphorus-containing high refractive index optical polyarylate, It is characterized in that The polyarylate has the structure of Formula I: In Formula I, R is selected from at least one of H, halogen, methyl, and methoxy; The X is selected from at least one of O and S; The n is 1-1000.

2. The method for preparing the phosphorus-containing high-refractive-index optical polyarylate according to claim 1, It is characterized in that The preparation method comprises the following steps: The phosphorus-containing bisphenol monomer and the phosphorus oxychloride monomer are mixed and reacted under the action of a catalyst to obtain the phosphorus-containing polyarylate. The phosphorus-containing bisphenol monomer has a structure of formula II; 3. The preparation method according to claim 2, It is characterized in that Phosphorus-containing aromatic monophenol, phosphorus-free aromatic monophenol and aromatic aldehyde are mixed, and reacted under the action of catalyst I to obtain the phosphorus-containing bisphenol monomer.

4. The preparation method according to claim 3, It is characterized in that The phosphorus-containing aromatic monophenol is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; The phosphorus-free aromatic monophenol is selected from at least one of bromophenol, o-cresol and phenol; The aromatic aldehyde is selected from at least one of p-hydroxybenzaldehyde, 3-methoxy-4-hydroxybenzaldehyde, and 3-bromo-4-hydroxybenzaldehyde; The catalyst I is selected from p-toluenesulfonic acid.

5. The preparation method according to claim 3, It is characterized in that The mass ratio of the phosphorus-containing aromatic monophenol, the phosphorus-free aromatic monophenol and the aromatic aldehyde is 1-1.1:0.9-1:2.2-3.

5.

6. The preparation method according to claim 3, It is characterized in that The mass ratio of the catalyst I to the phosphorus aromatic monophenol is 0.04:1 to 1:

1.

7. The preparation method according to claim 2, Features ,, the reaction conditions of the reaction I are as follows: The temperature of the reaction I is 130-180°C; The reaction time of the reaction I is 20 to 48 hours.

8. The preparation method according to claim 2, It is characterized in that The phosphorus oxychloride-containing monomer is selected from at least one of phosphorus oxychloride, phenyl phosphorus oxychloride, and phenyl phosphorothioyl chloride; The catalyst is selected from at least one of triethylamine, nitrogen-methylimidazole, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, and potassium bicarbonate.

9. The preparation method according to claim 2, It is characterized in that The molar ratio of the phosphorus-containing bisphenol monomer to the phosphorus-containing chloride monomer is 0.9:1 to 1.1:1; The mass ratio of the catalyst to the phosphorus-containing bisphenol monomer is 0.04:1 to 1:

1.

10. The preparation method according to claim 2, It is characterized in that The reaction conditions of the reaction are as follows: The reaction temperature is 25-260°C; The reaction time is 2 to 6 hours.

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