An aromatic thioether, polycarbonates made from the thioether, and uses thereof

Abstract

The present application relates to an aromatic sulfide, polycarbonate prepared from the sulfide and application thereof, the aromatic sulfide has the following structure, wherein E1 is -CH(CH3)CH2- or -CH2CH2CH2-; n is 8-20. The aromatic sulfide of one embodiment of the present application can be used for preparing polycarbonate, and the prepared polycarbonate material has better refractive index and higher impact strength.

Description

Technical Field

[0001] This invention relates to polycarbonate, and more particularly to a polycarbonate prepared using aromatic sulfides and its applications. Background Technology

[0002] High-refractive-index polycarbonate (PC) is a special type of optical lens polycarbonate prepared by melt transesterification polymerization using fluorene and naphthalene dihydroxy compounds from the downstream coal tar deep processing industry chain as polymerizing monomers. Its refractive index is typically greater than 1.60. Compared to other optical materials, high-refractive-index PC has a higher refractive index, lower birefringence, and good hydrothermal stability, making it suitable for high-end optical lens applications, including mobile phone lenses, automotive lenses, security lenses, AR / VR glasses, drones, and smart home cameras.

[0003] The monomers used in the preparation of existing high-refractive PC are mainly fluorene and naphthalene dihydroxy compounds. On the one hand, the improvement of the refractive index of the material is limited, and on the other hand, while the refractive index is improved, the Abbe number is significantly reduced. At the same time, the material itself contains a large number of macrocyclic structures, which are prone to stress cracking, and the impact performance at low temperature is poor, which limits its application in low-temperature environments.

[0004] Furthermore, as end-customers increasingly demand higher performance from polycarbonate optical materials, existing products cannot meet their needs. Increasing the refractive index requires adding more rigid rings to the material structure, which further strengthens the rigidity of the rings. These additional rigid rings further reduce the Abbe number, impacting the user experience. In addition, the strong polar carbonate bonds provide significant intermolecular forces, binding the molecular chains together and further increasing the material's rigidity, thus increasing processing difficulty. Summary of the Invention

[0005] To overcome at least one of the defects of the prior art, in a first aspect, one embodiment of the present invention provides an aromatic sulfide having the following structure:

[0006]

[0007] Where E1 is -CH(CH3)CH2- or -CH2CH2CH2-; n is 8 to 20.

[0008] Secondly, one embodiment of the present invention provides a polycarbonate comprising a structural unit X derived from the aforementioned aromatic sulfide, and structural unit A and / or structural unit B; wherein the structures of structural unit X, structural unit A, and structural unit B are as follows:

[0009] Structural unit X:

[0010] Structural Unit A:

[0011] Structural Unit B:

[0012] Among them, R1, R2, R3, and R4 are each independently selected from hydrogen atoms, C1 to C2 atoms. 20 Alkyl groups, C1-C 20 alkoxy groups, C5-C 20 cycloalkyl, C5-C 20 Cycloalkoxy groups, C6-C 20 aryl, C6-C 20 aryloxy groups.

[0013] Thirdly, one embodiment of the present invention provides a method for preparing the above-mentioned polycarbonate, comprising reacting a hydroxyl-containing compound with a diester to perform a polymerization reaction to obtain the polycarbonate; wherein the hydroxyl-containing compound includes the above-mentioned aromatic sulfide and compound A and / or compound B; the structures of compound A and compound B are as follows:

[0014] Compound A:

[0015] Compound B:

[0016] Among them, R1, R2, R3, and R4 are each independently selected from hydrogen atoms, C1 to C2 atoms. 20 Alkyl groups, C1-C 20 alkoxy groups, C5-C 20 cycloalkyl, C5-C 20 Cycloalkoxy groups, C6-C 20 aryl, C6-C 20 aryloxy groups.

[0017] Fourthly, one embodiment of the present invention provides a polycarbonate material comprising the polycarbonate described above or the polycarbonate prepared by the above preparation method.

[0018] Fifthly, one embodiment of the present invention provides an optical device comprising the polycarbonate described above or the polycarbonate prepared by the above-described preparation method.

[0019] In a sixth aspect, one embodiment of the present invention provides the application of the above-described polycarbonate or the polycarbonate prepared by the above-described preparation method as an optical material.

[0020] An aromatic sulfide according to one embodiment of the present invention can be used to prepare polycarbonate, and the resulting polycarbonate material has a better refractive index and higher impact strength. Detailed Implementation

[0021] Typical embodiments embodying the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present invention can have various variations in different embodiments without departing from the scope of the present invention, and the description herein is for illustrative purposes only and not intended to limit the present invention.

[0022] One embodiment of the present invention provides an aromatic sulfide having the following structure:

[0023]

[0024] Where E1 is -CH(CH3)CH2- or -CH2CH2CH2-; n is 8 to 20.

[0025] In one embodiment, n in the aromatic sulfide structure can be 8 to 20, further can be 8 to 16, and even further can be 10 to 16. For example, n can be 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0026] In one embodiment, E1 in the aromatic sulfide structure is attached to the ortho or para position of the 2-hydroxyethoxy group on the benzene ring.

[0027] In one embodiment, the aromatic sulfide is selected from the following structures:

[0028]

[0029] One embodiment of the present invention provides a method for preparing the above-mentioned aromatic sulfide, comprising the following steps:

[0030] (1) A phenolic compound containing a double bond is reacted with sulfur to give an intermediate compound; and

[0031] (2) React the intermediate compound with ethylene oxide to prepare aromatic sulfides;

[0032] Among them, phenolic compounds containing double bonds have the following structures:

[0033]

[0034] E2 is allyl (-CH2CH=CH2) or isopropenyl (-C(CH3)=CH2).

[0035] In one embodiment, in a phenolic compound containing a double bond, E2 is located at the ortho or para position of the hydroxyl group on the benzene ring.

[0036] In one embodiment, the phenolic compound containing a double bond includes one or more of o-allylphenol, p-allylphenol, o-isopropenylphenol, and p-isopropenylphenol.

[0037] In one embodiment, the preparation reaction of the aromatic sulfide can be a prior art. For example, the reaction in step (1) can be carried out according to the method disclosed in the literature "The use of elemental sulfur as an alternative feedstock for polymeric materials. Nat. Chem., 2013, 5, 518-524"; the reaction in step (2) can be carried out according to the method disclosed in the literature "Synthesis Study of High Refractive Index Optical Resin Monomer Phenyl Diether Fluorene, Contemporary Chemical Research, 2022, 24, 180-182".

[0038] In one embodiment, in step (1), the mass ratio of the double-bonded phenol compound to sulfur can be 1:(0.5-8), or more specifically 1:(1-4), for example 1:0.8, 1:0.9, 1:1, 1:1.2, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:5, 1:6, or 1:7.

[0039] In one embodiment, the reaction temperature in step (1) can be 175-195°C, or more specifically 180-190°C, for example 185°C.

[0040] In one embodiment, the reaction time of step (1) can be 1 to 12 hours, and more specifically 2 to 10 hours, for example 2.5 hours, 5 hours, 7.5 hours, or 9 hours.

[0041] In one embodiment, in step (2), the molar ratio of ethylene oxide to the intermediate compound can be 1:(0.4 to 0.5), or more specifically 1:(0.43 to 0.47), for example 1:0.45.

[0042] In one embodiment, the reaction temperature in step (2) can be 60-90°C, or more specifically 65-85°C, such as 70°C, 75°C, or 80°C.

[0043] In one embodiment, the reaction time of step (2) can be 3 to 8 hours, and more specifically 4 to 6 hours, for example 4.5 hours, 5 hours, 5.5 hours, or 7 hours.

[0044] In one embodiment, the reaction in step (2) is carried out in the presence of a catalyst, which may be sodium hydroxide.

[0045] In one embodiment, the molar ratio of the catalyst to ethylene oxide in step (2) is 0.05:(0.1 to 1), for example, 0.05:0.2, 0.05:0.3, 0.05:0.5, or 0.05:0.8.

[0046] One embodiment of the present invention provides the application of the above-mentioned aromatic sulfides in the preparation of polycarbonate.

[0047] One embodiment of the present invention provides a polycarbonate comprising structural unit X derived from the above-mentioned aromatic sulfide, and structural unit A and / or structural unit B; wherein the structures of structural unit X, structural unit A, and structural unit B are as follows:

[0048] Structural unit X:

[0049] Structural Unit A:

[0050] Structural Unit B:

[0051] Among them, R1, R2, R3, and R4 are each independently selected from hydrogen atoms, C1 to C2 atoms. 20 Alkyl groups, C1-C 20 alkoxy groups, C5-C 20 cycloalkyl, C5-C 20 Cycloalkoxy groups, C6-C 20 aryl, C6-C 20 aryloxy groups.

[0052] In one embodiment, the number of carbon atoms contained in the alkyl or alkoxy group of R1, R2, R3 or R4 can be 1 to 20, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0053] In one embodiment, the number of carbon atoms contained in the cycloalkyl or cycloalkoxy group of R1, R2, R3 or R4 can be 5 to 20, for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0054] In one embodiment, the number of carbon atoms contained in the aryl or aryloxy group of R1, R2, R3 or R4 can be 6 to 20, for example 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0055] In one embodiment, R1, R2, R3, and R4 are each independently selected from hydrogen atoms, C1-C3 alkyl groups, and C6-C4 alkyl groups. 12 Aryl groups.

[0056] In one embodiment, in structural unit A, R1 and R2 are both hydrogen atoms, or R1 and R2 are both phenyl atoms.

[0057] In one embodiment, in structural unit B, R3 and R4 are both hydrogen atoms, or R3 and R4 are both phenyl atoms.

[0058] In one embodiment, the polycarbonate includes structural unit X and structural unit A.

[0059] In one embodiment, the polycarbonate includes structural unit X and structural unit B.

[0060] In one embodiment, the polycarbonate includes structural unit X, structural unit A, and structural unit B.

[0061] In one embodiment, in polycarbonate, the molar ratio of structural unit X to structural unit A and structural unit B can be 1:0 to 99:0 to 99, and the molar number of structural unit A and structural unit B is not simultaneously 0; further, the molar ratio of structural unit X to structural unit A and structural unit B can be 1:10 to 80:10 to 80.

[0062] In one embodiment, the molar ratio of structural unit A to structural unit B can be 1 to 18:1 to 4, for example 1:1.7, 1:1.8, 1:2, 1:3, 1:3.5, 1.8:1, 2:1, 5:1, 10:1, 15:1.

[0063] In one embodiment, the molar content of structural unit X in the polycarbonate structural unit can be 4% to 10%, for example, 4.5%, 4.7%, 4.8%, 5%, 5.5%, 6%, 7%, 8%, or 9%. The above molar content is based on the sum of the molar numbers of structural unit X, structural unit A, and structural unit B.

[0064] In one embodiment, the weight-average molecular weight of the polycarbonate can be 10,000 to 150,000, further 20,000 to 130,000, and even further 30,000 to 120,000, for example 11,000, 12,000, 30,000, 50,000, 60,000, 67,000, 68,000, 70,000, 90,000, 91,000, 95,000, 97,000, 98,000, and 100,000.

[0065] In one embodiment, the molecular weight distribution (PDI) of the polycarbonate can be 1.8 to 2.0, for example 1.83, 1.88, or 1.98.

[0066] In one embodiment, the hydroxyl content (or terminal hydroxyl content) of the polycarbonate is less than 1000 ppm, and more particularly, it can be 300–500 ppm. The hydroxyl groups primarily originate from the monomers corresponding to structural unit X, structural unit A, and / or structural unit B.

[0067] In one embodiment, the content of small molecule byproducts in the polycarbonate product is less than 500 ppm, and more specifically 100 to 300 ppm.

[0068] One embodiment of the present invention provides a method for preparing the above-mentioned polycarbonate, comprising polymerizing a hydroxyl-containing compound with a diester to obtain polycarbonate; wherein the hydroxyl-containing compound includes the above-mentioned aromatic sulfide and compound A and / or compound B; the structures of compound A and compound B are as follows:

[0069] Compound A:

[0070] Compound B:

[0071] Among them, R1, R2, R3, and R4 are each independently selected from hydrogen atoms, C1 to C2 atoms. 20 Alkyl groups, C1-C 20 alkoxy groups, C5-C 20 cycloalkyl, C5-C 20 Cycloalkoxy groups, C6-C 20 aryl, C6-C 20 aryloxy groups.

[0072] In one embodiment, the polymerization reaction of the hydroxyl-containing compound with the diester can be carried out using existing processes.

[0073] In one implementation, R1, R2, R3, and R4 are subject to the foregoing limitations.

[0074] In one embodiment, compound A is selected from one or two of the following compounds:

[0075]

[0076] In one embodiment, compound B is selected from one or two of the following compounds:

[0077]

[0078] In one embodiment, the molar ratio of aromatic sulfide to compound A and compound B can be 1:0 to 99:0 to 99, and the molar number of compound A and compound B is not simultaneously 0; further, the molar ratio of aromatic sulfide to compound A and compound B can be 1:10 to 80:10 to 80.

[0079] In one embodiment, the molar ratio of compound A to compound B can be 1 to 18:1 to 4, for example 1:1.7, 1:1.8, 1:2, 1:3, 1:3.5, 1.8:1, 2:1, 5:1, 10:1, 15:1.

[0080] In one embodiment, the hydroxyl-containing compound includes 4 to 10 mol% of an aromatic sulfide. Further, the molar content of the aromatic sulfide in the hydroxyl-containing compound can be, for example, 4.5%, 4.7%, 4.8%, 5%, 5.5%, 6%, 7%, 8%, or 9%. The above molar contents are based on the number of moles of the hydroxyl-containing compound.

[0081] In one embodiment, the molar ratio of the diester to the hydroxyl-containing compound can be (1-1.1):1, and more preferably (1-1.05):1.

[0082] In one embodiment, the diester includes one or more of diphenyl carbonate, xylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Further, the diester may be diphenyl carbonate and / or xylene carbonate.

[0083] In one embodiment, the diester and the hydroxyl-containing compound can be reacted by melt transesterification polycondensation in the presence or without a catalyst.

[0084] In one embodiment, the catalyst for the reaction system of the diester and the hydroxyl-containing compound may be selected from one or more of sodium hydroxide, sodium bicarbonate, magnesium hydroxide, cesium carbonate, calcium hydroxide, strontium hydroxide, barium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylamine, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride, tin acetate, cerium acetylacetone, zirconium acetylacetone, zirconium acetate, and tetrabutoxyzirconium. Further, the catalyst may be selected from one or more of sodium hydroxide, sodium bicarbonate, cesium carbonate, cerium acetylacetone, zirconium acetate, and zinc acetate.

[0085] In one embodiment, the molar ratio of catalyst to diester carbonate can be 1 × 10⁻⁶. -8 ~1×10 -3 It can be further increased to 1×10 -6 ~1×10 -4 .

[0086] In one embodiment, the polymerization reaction of the carbonate diester with the hydroxyl-containing compound includes a material melting stage, a transesterification stage, and a polycondensation stage. Furthermore, small molecule compounds generated during the reaction can be removed in real time by distillation.

[0087] In one embodiment, the temperature of the reaction system during the melting stage can be 100–250°C, more specifically 140–200°C, for example 130°C, 135°C, 150°C, 160°C, or 180°C; the holding time can be 20–50 min, more specifically 30–40 min.

[0088] In one embodiment, the pressure of the reaction system during the transesterification stage can be 20–80 kPa(A), for example 30 kPa, 40 kPa, 60 kPa, or 70 kPa; the reaction temperature can be 140–280 °C, and more specifically 170–250 °C, for example 200 °C, 220 °C, 230 °C, 235 °C, 240 °C, or 260 °C; and the reaction time can be 30–180 min, and more specifically 60–90 min, for example 70 min or 80 min.

[0089] In one embodiment, the pressure of the reaction system during the polycondensation stage can be 5–1000 Pa(A), more specifically 50–150 Pa(A), such as 60 Pa, 80 Pa, 100 Pa, or 120 Pa; the temperature can be 200–350 °C, more specifically 250–300 °C, such as 240 °C, 260 °C, 265 °C, 270 °C, or 280 °C; and the reaction time can be 5–90 min, more specifically 15–60 min, such as 25 min, 30 min, or 45 min.

[0090] One embodiment of the present invention provides a polycarbonate material comprising the above-described polycarbonate.

[0091] In one embodiment, the polycarbonate material (e.g., a film or sheet) has a refractive index of 1.70 to 1.75 at 23°C and a wavelength of 589 nm, for example, 1.71, 1.72, 1.73, or 1.74.

[0092] In one embodiment, the polycarbonate material has an Abbe number of 15 to 20, for example 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5.

[0093] In one embodiment, the impact strength of the polycarbonate material is 50–65 J / m. 2 For example, 51J / m 2 54J / m 2 56J / m 2 62J / m 2 .

[0094] In one embodiment, the light transmittance of the polycarbonate material is above 88%, and can further be 88-90%, for example 88.5% or 88.9%.

[0095] In one embodiment, the haze of the polycarbonate material is below 0.7%, more specifically 0.3% to 0.7%, for example 0.33%, 0.35%, 0.4%, 0.45%, 0.6%, 0.65%, or 0.67%.

[0096] One embodiment of the present invention provides an optical device comprising the polycarbonate described above.

[0097] In one embodiment, the optical device may be an optical lens or an optical film.

[0098] In one embodiment, the optical components can be used in devices or equipment such as mobile phone lenses, automotive lenses, security lenses, AR / VR glasses, drones, and smart home cameras.

[0099] One embodiment of the present invention provides the application of the above-described polycarbonate as an optical material.

[0100] One embodiment of the present invention provides the application of the above-described polycarbonate in the fabrication of optical devices.

[0101] The polycarbonate or its material according to one embodiment of the present invention has an aromatic sulfide structure that gives the material high refractive index and high Abbe number, while also increasing the toughness of the material and improving its processing characteristics, thereby significantly improving the impact strength and yield of the manufactured device.

[0102] The polycarbonate or its material according to one embodiment of the present invention contains an aromatic sulfide structure containing multiple sulfur atoms. Compared with the monosulfide / disulfide structure, the presence of the aromatic sulfide structure increases the flexibility of the polymer, prevents brittle cracking, and improves the processing performance of the material, thereby significantly improving the impact strength and sheet yield of the material, and increasing the refractive index of the material without sacrificing the Abbe number; in addition, the aromatic sulfide structure can reduce the birefringence of the material and improve the overall optical performance of the material.

[0103] The polycarbonate or its material according to one embodiment of the present invention has the characteristics of high refractive index, high Abbe number, and low birefringence, making it particularly suitable for applications in small-sized aspherical products such as optical lenses. Furthermore, due to the flexible sulfide structure of polycarbonate, it can greatly improve phenomena such as chipping that occur during product reprocessing, meeting the needs of multi-lens lenses.

[0104] The preparation of polycarbonate according to one embodiment of the present invention will be further described below with reference to examples. The raw materials and testing methods involved in each example and comparative example are as follows.

[0105] raw material

[0106] Diphenyl carbonate: Shanghai Titan;

[0107] BPEF: Jiangsu Yongxing;

[0108] BPPF: Jiangsu Yongxing

[0109] BHEBN: Jiangsu Yongxing;

[0110] 2,2-Di(2-hydroxyethoxy)-5,5-diphenyl-1,1-binaphthyl (BHEBBN): Prepared according to the method disclosed in patent CN 114957954A.

[0111] Test methods

[0112] 1. Testing of weight-average molecular weight (Mw) and molecular weight distribution (PDI)

[0113] Gel permeation chromatography (GPC) was used with dichloromethane as the developing solvent to prepare a standard curve using standard polystyrene with a known molecular weight (molecular weight distribution = 1). Based on this standard curve, Mw and PDI were calculated from the retention times of GPC.

[0114] 2. Refractive index (nD) test

[0115] The resins prepared in each embodiment or comparative example were made into plates with a thickness of 1 mm, and the refractive index (nD) of the resin plates at 23°C and a wavelength of 589 nm was measured using an Abbe refractometer according to the method of JIS-K-7142.

[0116] 3. Abbe number test

[0117] The refractive indices nF(486), nD(589), and nC(656) at wavelengths of 486 nm, 589 nm, and 656 nm were measured using an Abbe refractometer at 23 °C. The Abbe number ν was then calculated using the following formula:

[0118] ν=(nD-1) / (nF-nC).

[0119] 4. Tests for light transmittance and haze

[0120] Transmittance and haze were determined using a turbidimeter according to the method in JIS-K-7361-1.

[0121] 5. Impact test

[0122] The notched impact strength of the cantilever beam was tested according to ASTM D256 standard in an environment with a temperature of 25°C and a relative humidity of 50% using an Instron CEAST 9050 testing machine.

[0123] 6. Orientation Birefringence (Δn): A 0.1 mm thick polycarbonate casting film is prepared and cut into 5.0 cm squares. The two ends of the film are then inserted into chucks (3.0 cm apart) and stretched to 1.5 times its original strength at Tg + 5°C. The phase difference (Re) at 589 nm is measured using an ellipsometer, and the orientation birefringence (Δn) is calculated using the following formula.

[0124] Δn=Re / d

[0125] Δn: Orientation birefringence; Re: Phase difference; d: Thickness.

[0126] Preparation Example 1

[0127] An intermediate compound was prepared by reacting p-isopropenylphenol with sulfur (mass ratio 1:1) at 195℃ for 4 h. The intermediate compound (molar ratio 1:0.45) was then reacted with ethylene oxide at 70℃ for 5.5 h under sodium hydroxide catalysis (catalyst to ethylene oxide molar ratio 1:4) to obtain compound X1, with the structural formula shown below, where n is 8, abbreviated as "X1-8 compound". Elemental analysis showed that the sulfur content of compound X1-8 was 40.9%.

[0128]

[0129] Preparation Example 2

[0130] An intermediate compound was prepared by reacting o-isopropenylphenol with sulfur (mass ratio 1:4) at 175℃ for 6 h. The intermediate compound (molar ratio 1:0.43) was then reacted with ethylene oxide at 60℃ for 7 h under sodium hydroxide catalysis (catalyst to ethylene oxide molar ratio 1:10) to obtain compound X2, with the structural formula shown below, where n is 12, abbreviated as "X2-12 compound". Elemental analysis showed that the sulfur content of compound X2-12 was 52.1%.

[0131]

[0132] Preparation Example 3

[0133] A propenylphenol was reacted with sulfur (mass ratio 1:8) at 195℃ for 4 h to prepare an intermediate compound. Ethylene oxide was then reacted with the intermediate compound (molar ratio 1:0.47) at 70℃ for 4 h under sodium hydroxide catalysis (catalyst to ethylene oxide molar ratio 1:10) to prepare compound X3, with the structural formula shown below, where n is 16, abbreviated as "X3-16 compound". Elemental analysis showed that the sulfur content of compound X3-16 was 58.9%.

[0134]

[0135] Preparation Example 4

[0136] An intermediate compound was prepared by reacting o-propenylphenol with sulfur (mass ratio 1:2) at 175℃ for 5 h. The intermediate compound (molar ratio 1:0.5) was then reacted with ethylene oxide at 70℃ for 3 h under sodium hydroxide catalysis (catalyst to ethylene oxide molar ratio 1:10) to obtain compound X4, with the structural formula shown below, where n is 10, abbreviated as "X4-10 compound". Elemental analysis showed that the sulfur content of compound X4-10 was 47.2%.

[0137]

[0138] Comparative Preparation Example 1

[0139] (1) Phenol was reacted with disulfur dichloride to prepare the following intermediate compound: the molar ratio of phenol to disulfur dichloride was 2.1:1. The reaction was carried out at 140°C for 6 hours in the presence of alkali metal hydroxide to prepare the following intermediate compound.

[0140]

[0141] (2) Reaction of ethylene oxide with the intermediate compound obtained in step (1): The molar ratio of ethylene oxide to the intermediate compound is 1:0.5, and the reaction is carried out at 80°C for 6 hours to obtain the following disulfide compound.

[0142]

[0143] Example 1

[0144] 0.033 mol BPEF, 0.059 mol BHEBN, 0.005 mol X1-8 compound, 0.1 mol diphenyl carbonate, 5.0 × 10 -7mol of sodium hydroxide was added to the reactor. Nitrogen was purged three times, and the mixture was heated to 132°C under normal pressure and held for 30 minutes until the raw materials were completely melted. Stirring was then started. The pressure was adjusted to 40 kPa(A), and the temperature was raised to 235°C. Byproducts began to distill out, and the reaction was maintained for 80 minutes. Then the temperature was raised to 250°C, and the pressure was gradually reduced to 80 Pa(A) over 1 hour. The reaction was continued for 30 minutes, and then the reaction was terminated.

[0145] The obtained polycarbonate was taken out and its performance was tested according to the aforementioned method. The results are shown in Table 1.

[0146] After vacuum drying the polycarbonate at 120°C for 8 hours, it was injection molded using a Sumitomo Heavy Industries SE30DU injection molding machine at a molding temperature of Tg+110°C and a mold temperature of Tg-10°C. This yielded a spherical lens with a thickness of 0.2 mm, a convex surface curvature radius of 5 mm, a concave surface curvature radius of 4 mm, and a diameter of 5 mm, with a sheet yield of 97.3%.

[0147] Example 2

[0148] 0.021 mol BPEF, 0.069 mol BHEBBN, 0.009 mol X2-12 compound, 0.1 mol diphenyl carbonate, 4.0 × 10 -7 1 mol of tetrabutylammonium hydroxide was added to the reactor. Nitrogen was purged three times, and the mixture was heated to 180°C under normal pressure and held for 30 minutes until the raw materials were completely melted. Stirring was then started. The pressure was adjusted to 60 kPa(A), and the temperature was raised to 220°C. By-products began to distill off, and the reaction was maintained for 60 minutes. Then the temperature was raised to 240°C, and the pressure was gradually reduced to 100 Pa(A) over 1 hour. The reaction was continued for 45 minutes, and then the reaction was terminated.

[0149] The obtained polycarbonate was taken out and its performance was tested according to the aforementioned method. The results are shown in Table 1.

[0150] Polycarbonate was used to fabricate spherical lenses using the same method as in Example 1, with a success rate of 97.3%.

[0151] Example 3

[0152] 0.09 mol BPPF, 0.005 mol BHEBN, 0.004 mol X3-16 compound, 0.1 mol diphenyl carbonate, 5.0 × 10 -61 mol of tin acetate was added to the reactor. Nitrogen was purged three times, and the mixture was heated to 160°C under normal pressure and held for 30 minutes until the raw materials were completely melted. Stirring was then started. The pressure was adjusted to 30 kPa(A), and the temperature was raised to 250°C. By-products began to distill off, and the reaction was maintained for 80 minutes. Then the temperature was raised to 300°C, and the pressure was gradually reduced to 100 Pa(A) over 1 hour. The reaction was allowed to continue for 15 minutes, and then the reaction was stopped.

[0153] The obtained polycarbonate was taken out and its performance was tested according to the aforementioned method. The results are shown in Table 1.

[0154] Polycarbonate was used to fabricate spherical lenses using the same method as in Example 1, with a success rate of 98.3%.

[0155] Example 4

[0156] Add 0.06 mol BPPF, 0.03 mol BHEBBN, 0.005 mol X4-10 compound, 0.1 mol diphenyl carbonate, and 1.0 × 10 -6 1 mol of tin acetate was added to the reactor. Nitrogen was purged three times, and the mixture was heated to 200°C under normal pressure and held for 20 minutes until the raw materials were completely melted. Stirring was then started. The pressure was adjusted to 70 kPa(A), and the temperature was raised to 260°C. By-products began to distill off, and the reaction was maintained for 90 minutes. Then the temperature was raised to 265°C, and the pressure was gradually reduced to 80 Pa(A) over 1 hour. The reaction was continued for 25 minutes, and then the reaction was terminated.

[0157] The obtained polycarbonate was taken out and its performance was tested according to the aforementioned method. The results are shown in Table 1.

[0158] Polycarbonate was used to fabricate spherical lenses using the same method as in Example 1, with a success rate of 96.3%.

[0159] Comparative Example 1

[0160] This example uses essentially the same raw materials and processes as Example 1 to prepare polycarbonate, the only difference being that BPEF is used in place of compound X1-8 in an equal molar amount.

[0161] The obtained polycarbonate was taken out and its performance was tested according to the aforementioned method. The results are shown in Table 1.

[0162] Polycarbonate was used to fabricate spherical lenses using the same method as in Example 1, with a success rate of 87.3%.

[0163] Comparative Example 2

[0164] This example uses essentially the same raw materials and processes as Example 2 to prepare polycarbonate, the only difference being that BPEF is used to replace compound X2-12 in equal molar amounts.

[0165] The obtained polycarbonate was taken out and its performance was tested according to the aforementioned method. The results are shown in Table 1.

[0166] Polycarbonate was used to fabricate spherical lenses using the same method as in Example 1, with a success rate of 73.3%.

[0167] Comparative Example 3

[0168] This example uses essentially the same raw materials and processes as Example 3 to prepare polycarbonate, the only difference being that BPPF is used instead of compound X3-16 in an equimolar amount.

[0169] The obtained polycarbonate was taken out and its performance was tested according to the aforementioned method. The results are shown in Table 1.

[0170] Polycarbonate was used to fabricate spherical lenses using the same method as in Example 1, with a success rate of 79.3%.

[0171] Comparative Example 4-1

[0172] This example uses essentially the same raw materials and processes as Example 4 to prepare polycarbonate, the only difference being that BHEBBN is used instead of compound X4-10 in an equimolar amount.

[0173] The obtained polycarbonate was taken out and its performance was tested according to the aforementioned method. The results are shown in Table 1.

[0174] Polycarbonate was used to fabricate spherical lenses using the same method as in Example 1, with a success rate of 77.7%.

[0175] Comparative Example 4-2

[0176] This example uses essentially the same raw materials and processes as Example 4 to prepare polycarbonate, the only difference being that the disulfide compound in the comparative preparation example 1 is used instead of the X4-10 compound in equimolar amounts.

[0177] The obtained polycarbonate was taken out and its performance was tested according to the aforementioned method. The results are shown in Table 1.

[0178] Polycarbonate was used to fabricate spherical lenses using the same method as in Example 1, with a success rate of 82.7%.

[0179] Table 1

[0180]

[0181] As described in the examples and comparative examples, the differences between Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 3 and Comparative Example 3, and Example 4 and Comparative Example 4-1 are as follows: Comparative Examples 1, 2, 3, and 4-1 did not use aromatic sulfides to prepare polycarbonate. Referring to the results in Table 1, it can be seen that compared to Comparative Examples 1, 2, 3, and 4-1, the polycarbonate materials prepared in Examples 1, 2, 3, and 4 have higher refractive indices, impact strength, and lower birefringence, and the yield of spherical lenses is also higher. Therefore, introducing an aromatic sulfide structure into polycarbonate helps to improve the above-mentioned properties of the material.

[0182] Furthermore, the difference between Example 4 and Comparative Example 4-2 is that the disulfide compound used in Comparative Example 4-2 contains only two sulfur atoms, while the X4-10 compound used in Example 4 contains ten sulfur atoms. As shown in Table 1, the polycarbonate material prepared in Example 4 has better refractive index, impact strength, and yield compared to Comparative Example 4-2. Therefore, compared to aromatic compounds containing two sulfur atoms, using aromatic sulfides containing multiple sulfur atoms to prepare polycarbonate can further improve the refractive index, impact strength, and yield of spherical lenses.

[0183] Unless otherwise specified, the terms used in this invention have the meanings commonly understood by those skilled in the art.

[0184] The embodiments described in this invention are for illustrative purposes only and are not intended to limit the scope of protection of this invention. Those skilled in the art can make various other substitutions, changes and improvements within the scope of this invention. Therefore, this invention is not limited to the above embodiments, but is only defined by the claims.

Claims

1. An aromatic sulfide having the following structure: in, E1 is -CH(CH3)CH2- or -CH2CH2CH2-; n is 8 to 20.

2. The aromatic sulfide according to claim 1, wherein the sulfide is selected from the following structures: And / or, n is 8 to 16.

3. A polycarbonate comprising structural unit X derived from the aromatic sulfide of claim 1 or 2, and structural unit A and / or structural unit B; wherein, The structures of structural unit X, structural unit A, and structural unit B are as follows: Structural unit X: Structural Unit A: Structural Unit B: Among them, R1, R2, R3, and R4 are each independently selected from hydrogen atoms, C1 to C2 atoms. 20 Alkyl groups, C1-C 20 alkoxy groups, C5-C 20 cycloalkyl, C5-C 20 Cycloalkoxy groups, C6-C 20 aryl, C6-C 20 aryloxy groups.

4. The polycarbonate according to claim 3, wherein, R1, R2, R3, and R4 are each independently selected from hydrogen atoms, C1-C3 alkyl groups, and C6-C4 alkyl groups. 12 aryl; and / or, The molar ratio of structural unit X to structural unit A and structural unit B is 1:0~99:0~99, and the number of moles of structural unit A and structural unit B is not simultaneously 0; or, Based on the sum of the molar numbers of structural unit X, structural unit A, and structural unit B, the molar content of structural unit X is 4-10%; and / or, The polycarbonate has a weight-average molecular weight of 10,000 to 150,000; and / or, The polycarbonate has a terminal hydroxyl content of less than 1000 ppm.

5. The polycarbonate according to claim 3, wherein, R1, R2, R3, and R4 are each independently selected from hydrogen atoms, phenyl groups; and / or, The molar ratio of structural unit X to structural unit A and structural unit B is 1:10~80:10~80; and / or, The polycarbonate has a weight-average molecular weight of 20,000 to 130,000; and / or, The polycarbonate has a terminal hydroxyl content of 300–500 ppm.

6. The method for preparing the polycarbonate according to claim 3, comprising reacting a hydroxyl-containing compound with a diester of carbonate to perform a polymerization reaction, thereby obtaining the polycarbonate; wherein, The hydroxyl-containing compound includes the aromatic sulfide according to claim 1 or 2, as well as compound A and / or compound B; the structures of compound A and compound B are as follows: Compound A: Compound B: Among them, R1, R2, R3, and R4 are each independently selected from hydrogen atoms, C1 to C2 atoms. 20 Alkyl groups, C1-C 20 alkoxy groups, C5-C 20 cycloalkyl, C5-C 20 Cycloalkoxy groups, C6-C 20 aryl, C6-C 20 aryloxy groups.

7. The preparation method according to claim 6, wherein, R1, R2, R3, and R4 are each independently selected from hydrogen atoms, C1-C3 alkyl groups, and C6-C4 alkyl groups. 12 aryl; and / or, The molar ratio of structural unit X to structural unit A and structural unit B is 1:0~99:0~99, and the number of moles of structural unit A and structural unit B is not simultaneously 0; or, Based on the sum of the molar numbers of structural unit X, structural unit A, and structural unit B, the molar content of structural unit X is 4-10%; and / or, The polycarbonate has a weight-average molecular weight of 10,000 to 150,000; and / or, The polycarbonate has a terminal hydroxyl content of less than 1000 ppm.

8. The preparation method according to claim 6, wherein, R1, R2, R3, and R4 are each independently selected from hydrogen atoms, phenyl groups; and / or, The molar ratio of structural unit X to structural unit A and structural unit B is 1:10~80:10~80; and / or, The polycarbonate has a weight-average molecular weight of 20,000 to 130,000; and / or, The polycarbonate has a terminal hydroxyl content of 300–500 ppm.

9. The preparation method according to claim 6, wherein, Compound A is selected from one or two of the following compounds: Compound B is selected from one or two of the following compounds: And / or, The carbonate diester includes one or more of diphenyl carbonate, dimethyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate; and / or, The hydroxyl-containing compound includes 4 to 10 mol% of the aromatic sulfide.

10. A polycarbonate material comprising the polycarbonate of any one of claims 3 to 5 or the polycarbonate prepared by any one of claims 6 to 9.

11. An optical device comprising the polycarbonate of any one of claims 3 to 5 or the polycarbonate prepared by any one of claims 6 to 9.

12. The use of the polycarbonate according to any one of claims 3 to 5 or the polycarbonate prepared by any one of claims 6 to 9 as an optical material.

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