Polycarbonate resin, and preparation method therefor and use thereof

Abstract

Provided in the present application are a polycarbonate resin, and a preparation method therefor and the use thereof. The polycarbonate resin contains a structural unit as represented by formula I. By defining the polycarbonate resin containing the structural unit as presented by formula I, the polycarbonate resin has the advantages of relatively good molecular chain flexibility, a high Abbe number, a high refractive index and a relatively low birefringence. Moreover, since the structure does not contain heteroatoms such as sulfur and nitrogen, the polycarbonate resin has excellent heat resistance, and undesirable phenomena such as yellowing are not prone to occurring during the processing and use processes. In addition, the polycarbonate resin has simple preparation raw materials and a low cost, there is no need to add an acid catalyst during the preparation process, and same is very environmentally friendly, and can be applied to the fields of optical components, electronic products or medical products, etc.

Description

Polycarbonate resin, preparation method and application thereof TECHNICAL FIELD

[0001] The present application relates to the technical field of optical plastics, for example, a polycarbonate resin, a preparation method and application thereof. BACKGROUND

[0002] With the rapid development of smart phones and new energy automobile industry, the demand for optical lens products is rapidly increasing. Polycarbonate is the preferred material for making optical lenses such as mobile phone lenses, vehicle-mounted lenses, and VR / AR glasses due to its good dimensional stability, high light transmittance, high refractive index, and easy molding.

[0003] Currently, polycarbonate resin is usually prepared using bisphenol A, and the obtained bisphenol A polycarbonate has a low refractive index of only 1.58 and a serious birefringence phenomenon, which cannot be applied in the field of high-end optical materials. Therefore, in order to improve the refractive index of polycarbonate resin and reduce its birefringence phenomenon, it is urgent to develop new polycarbonate products to meet the use requirements of different customers.

[0004] CN101490130A reports a kind of low birefringence polycarbonate prepared by reacting isosorbide and bisphenol A as dihydroxy monomer with diphenyl carbonate; however, the refractive index of the polycarbonate is still low, and the heat resistance is poor, which limits its application range.

[0005] CN112961336A reports a kind of dihydroxy monomer with multi-aromatic ring structure, which is reacted with diphenyl carbonate to prepare a kind of polycarbonate with high refractive index and low birefringence; however, the dihydroxy monomer with multi-aromatic ring structure used in the polycarbonate has a very complex structure, which is difficult to synthesize and difficult to realize industrial scale-up.

[0006] CN115725063A reports a kind of dihydroxy monomer with a new structure prepared by reacting anthracene ring and p-benzoquinone, and a kind of polycarbonate with high refractive index and low birefringence prepared by reacting the dihydroxy monomer with diphenyl carbonate; however, a large amount of acidic reagent is used in the synthesis process of the dihydroxy monomer with a new structure, and the solubility is poor, which makes the purification difficult and the product yield low. At the same time, the polycarbonate prepared by using the dihydroxy monomer with a new structure has a small Abbe number due to the presence of a large number of aromatic ring structures in the main chain, which is prone to chromatic aberration, thereby limiting the use of the product.

[0007] Therefore, in view of the above technical problems, it is urgent to develop a kind of polycarbonate resin with high refractive index, high Abbe number, low birefringence and excellent heat resistance. SUMMARY

[0008] The following is a summary of the subject matter described in detail in this document. This summary is not intended to limit the scope of protection of the claims.

[0009] The present application provides a polycarbonate resin, a preparation method and application thereof, the polycarbonate resin has the characteristics of high refractive index, low birefringence, high Abbe number and excellent heat resistance, can meet the current market use demand, and the raw material structure of the polycarbonate resin is simple, synthesis is easy, and industrial amplification is convenient to realize.

[0010] In the first aspect, the present application provides a polycarbonate resin, the polycarbonate resin contains a structural unit shown in formula I:

[0011] In formula I, X is selected from C1-C6(e.g. C1, C2, C3, C4, C5 or C6) linear or branched alkylene;

[0012] R1 and R2 are each independently selected from any one of H, C1-C20(e.g. C1, C3, C5, C9, C11, C13, C15, C17, C19 or C20, etc.) linear or branched alkyl, C1-C20(e.g. C1, C3, C5, C9, C11, C13, C15, C17, C19 or C20, etc.) linear or branched alkoxy, C5-C20(e.g. C5, C9, C11, C13, C15, C17, C19 or C20, etc.) cycloalkyl, C5-C20(e.g. C5, C9, C11, C13, C15, C17, C19 or C20, etc.) cycloalkoxy, C6-C20(e.g. C6, C9, C11, C13, C15, C17, C19 or C20, etc.) aryl, C6-C20(e.g. C6, C9, C11, C13, C15, C17, C19 or C20, etc.) aryloxy;

[0013] R3 and R4 are each independently selected from any one of H, C1-C20(e.g. C1, C3, C5, C9, C11, C13, C15, C17, C19 or C20, etc.) linear or branched alkyl, or are connected into a ring through any one of a single bond, C1-C3(e.g. C1, C2 or C3) alkylene, C1-C3(e.g. C1, C2 or C3) alkylenoxy;

[0014] n is an integer of 0-5(e.g. 0, 1, 2, 3, 4 or 5).

[0015] The polycarbonate resin provided by the application contains a structural unit shown in Formula I; on one hand, due to the long alkyl chain contained in the main chain, the flexibility of the molecular chain is good, and the Abbe number is high; on the other hand, due to the high weight of the structural unit shown in Formula I in a unit volume, the refractive index of the polycarbonate resin can be effectively improved, the balance of the refractive index and the Abbe number is realized, and the birefringence is low; in addition, the structural unit shown in Formula I does not contain heteroatoms such as sulfur and nitrogen, and the obtained polycarbonate resin also has excellent heat resistance, and is not easy to produce yellowing and other adverse phenomena in the processing and application process, and can be applied in the fields of optical components, electronic products, medical products and the like.

[0016] In one embodiment, the X is selected from C1-C2 alkylene.

[0017] In one embodiment, the R1 and R2 are each independently selected from any one of H, C1-C6 linear or branched alkyl, C1-C6 linear or branched alkoxy, C5-C10 cycloalkyl, C5-C10 cycloalkoxy, C6-C12 aryl, and C6-C12 aryloxy.

[0018] In one embodiment, the R3 and R4 are each independently selected from any one of H or methyl, or are connected into a ring through any one of a single bond, C1-C3 alkylene, and C1-C3 alkylenoxy.

[0019] In one embodiment, the n is an integer of 0-1.

[0020] In one embodiment, the structural unit shown in Formula I is at least one of the structural units shown in Formulas A1-A3.

[0021] In one embodiment, the polycarbonate resin further contains a structural unit shown in Formula II as follows:

[0022] In Formula II, Y is selected from C1-C6 (for example, C1, C3, C5 or C6, etc.) linear or branched alkylene;

[0023] R5~R6are each independently selected from any one of H, C1~C20(e.g., C1, C3, C5, C9, C11, C13, C15, C17, C19, or C20, etc.) straight chain or branched alkyl, C1~C20(e.g., C1, C3, C5, C9, C11, C13, C15, C17, C19, or C20, etc.) straight chain or branched alkoxy, C5~C20(e.g., C5, C9, C11, C13, C15, C17, C19, or C20, etc.) cycloalkyl, C5~C20(e.g., C5, C9, C11, C13, C15, C17, C19, or C20, etc.) cycloalkoxy, C6~C20(e.g., C6, C9, C11, C13, C15, C17, C19, or C20, etc.) aryl, C6~C20(e.g., C6, C9, C11, C13, C15, C17, C19, or C20, etc.) aryloxy;

[0024] L is selected from any one of C1~C8(e.g., C1, C3, C5, or C8, etc.) straight chain or branched alkyl, C6~C20(e.g., C6, C9, C11, C13, C15, C17, C19, or C20, etc.) cycloalkyl, C6~C20(e.g., C6, C9, C11, C13, C15, C17, C19, or C20, etc.) arylalkyl, C6~C20(e.g., C6, C9, C11, C13, C15, C17, C19, or C20, etc.) diarylalkyl;

[0025] m is an integer from 0 to 5 (e.g., 0, 1, 2, 3, 4, or 5).

[0026] It is to be noted that the above-mentioned C6~C20(e.g., C6, C9, C11, C13, C15, C17, C19, or C20, etc.) arylalkyl refers to a group formed by substituting at least one H on the alkyl with the above-mentioned listed aryl, including but not limited to phenylalkyl, biphenylalkyl, naphthylalkyl, fluorenyl, etc. In one embodiment, the structural unit represented by Formula II is at least one of the structural units represented by Formula B1~B2:

[0027] In one embodiment, the mole percentage of the structural unit represented by Formula I in the polycarbonate resin is ≥0.5%, such as 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 3%, 5%, 7%, 9%, 11%, 13%, 15%, 17%, 19%, 20%, 40%, 60%, or 80%, etc., and optionally >10%; further limiting the mole percentage of the structural unit represented by Formula I in the polycarbonate resin can make it have the highest refractive index and the highest Abbe number.

[0028] In one embodiment, the polycarbonate resin has a glass transition temperature (Tg) of 130 to 160°C, such as 130°C, 135°C, 140°C, 150°C, or 160°C, etc.

[0029] In a second aspect, the present application provides a method for preparing the polycarbonate resin according to the first aspect, characterized in that the method comprises: subjecting a dihydroxyl compound having a structure shown in Formula III, optionally a dihydroxyl compound having a structure shown in Formula IV, and a carbonic acid diester to a polycondensation reaction to obtain the polycarbonate resin.

[0030] In Formula III, R1-R4 and n each independently have the same defined range as in Formula I.

[0031] In Formula IV, R5-R6, L, and m each independently have the same defined range as in Formula II.

[0032] The method for preparing the polycarbonate resin provided by the present application is carried out by a melt polycondensation method. After subjecting a dihydroxyl compound having a structure shown in Formula III, optionally a dihydroxyl compound having a structure shown in Formula IV, and a carbonic acid diester to an ester exchange reaction under heating and removing by-products, the polycarbonate resin is obtained.

[0033] In one embodiment, the molar ratio of the sum of the dihydroxyl compound having a structure shown in Formula III and the dihydroxyl compound having a structure shown in Formula IV to the carbonic acid diester is 1:(1-1.1), such as 1:1, 1:1.02, 1:1.04, 1:1.06, 1:1.08, or 1:1.1, etc., and can be 1:(1-1.05).

[0034] In one embodiment, the carbonic acid diester comprises any one or a combination of at least two of diphenyl carbonate, ditolyl carbonate, dimethyl carbonate, or diethyl carbonate, and can be diphenyl carbonate.

[0035] In one embodiment, the dihydroxyl compound having a structure shown in Formula III is at least one of compounds C1-C3:

[0036] In one embodiment, the dihydroxyl compound having a structure shown in Formula IV comprises bisphenol A and / or 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene.

[0037] In one embodiment, the polycondensation reaction is carried out in the presence of an alkaline catalyst.

[0038] In one embodiment, the basic catalyst comprises any one or a combination of at least two of lithium hydroxide, sodium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, cesium hydroxide, strontium hydroxide, barium hydroxide, lithium carbonate, sodium bicarbonate, magnesium bicarbonate, sodium carbonate, magnesium carbonate, potassium carbonate, calcium bicarbonate, calcium carbonate, cesium carbonate, strontium carbonate, barium carbonate, lithium acetate, sodium acetate, magnesium acetate, potassium acetate, calcium acetate, strontium acetate, barium acetate, sodium stearate, magnesium stearate, potassium stearate, calcium stearate, lithium benzoate, sodium benzoate, potassium benzoate, calcium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, disodium phenyl phosphate, magnesium phenyl phosphate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, diethylamine, triethylamine, dimethylbenzylamine, triphenylamine, tetramethylboron hydride ammonium, tetrabutylboron hydride ammonium, tetrabutylammonium tetraphenylborate, or tetraphenylammonium tetraphenylborate, optionally any one or a combination of at least two of sodium hydroxide, sodium bicarbonate, or sodium carbonate.

[0039] In one embodiment, the molar ratio of the sum of the dihydroxy compound having the structure of Formula III and the dihydroxy compound having the structure of Formula IV to the basic catalyst is 1:(10 -3 ~ 10 -8 , for example, 1:10 -3 , 1:10 -4 , 1:10 -5 , 1:10 -6 , 1:10 -7 , or 1:10 -8 , etc., optionally 1:(10 -4 ~ 10 -6 .

[0040] In one embodiment, the preparation method specifically comprises the following steps: adding a dihydroxy compound having the structure shown in Formula III, a dihydroxy compound having the structure shown in Formula IV, a carbonic acid diester and a basic catalyst into a reaction kettle, and replacing the air in the reaction kettle with nitrogen for 3-5 times (for example, 3 times, 4 times or 5 times, etc.), keeping the normal pressure in the kettle, first increasing the temperature to 160-190°C (for example, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C or 190°C, etc.), reacting for 5-10 min (for example, 5 min, 6 min, 7 min, 8 min, 9 min or 10 min, etc.), then reducing the pressure in the reaction kettle to 15-35 kPa (for example, 15 kPa, 20 kPa, 25 kPa, 30 kPa or 35 kPa, etc.), reacting for 40-70 min (for example, 40 min, 50 min, 60 min or 70 min, etc.), then increasing the temperature to 190-220°C (for example, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C or 220°C, etc.), then reducing the pressure in the reaction kettle to 5-25 kPa (for example, 5 kPa, 10 kPa, 15 kPa, 20 kPa or 25 kPa, etc.), reacting for 40-70 min (for example, 40 min, 50 min, 60 min or 70 min, etc.), then increasing the temperature to 220-240°C (for example, 220°C, 225°C, 230°C, 235°C or 240°C, etc.), then reducing the pressure in the reaction kettle to 1-5 kPa (for example, 1 kPa, 2 kPa, 3 kPa, 4 kPa or 5 kPa, etc.), reacting for 30-60 min (for example, 30 min, 40 min, 50 min or 60 min, etc.), then increasing the temperature to 240-260°C (for example, 240°C, 245°C, 250°C, 255°C or 260°C, etc.), then reducing the pressure in the reaction kettle to 0.1-1 kPa (for example, 0.1 kPa, 0.3 kPa, 0.5 kPa, 0.7 kPa, 0.9 kPa or 1 kPa, etc.), continuing to react for 40-70 min (for example, 40 min, 50 min, 60 min or 70 min, etc.), after the reaction is completed, nitrogen is introduced, the material is discharged from the reaction kettle, and after water cooling, granulation and drying, the polycarbonate resin is obtained.

[0041] In a third aspect, the present application provides a polycarbonate resin composition, which comprises the polycarbonate resin according to the first aspect and an additive.

[0042] In one embodiment, the mass percentage of the polycarbonate resin in the polycarbonate resin composition is 90-99.9%, for example, 90%, 92%, 94%, 96%, 98%, 99%, 99.2%, 99.4%, 99.6% or 99.9%, etc.

[0043] In one embodiment, the additive includes any one or a combination of at least two of an antioxidant, a dye, a blueing agent, a flame retardant, a mold release agent, a UV absorber, a lubricant, a crystallization nucleating agent, a reinforcing agent, an antistatic agent, or an antibacterial agent.

[0044] In a fourth aspect, the present application provides an optical lens comprising at least one of the polycarbonate resin according to the first aspect or the polycarbonate composition according to the third aspect.

[0045] Compared with the related art, the present application has the following advantages:

[0046] (1) The polycarbonate resin provided by the present application contains structural units shown in Formula I, has the advantages of good molecular chain flexibility, high Abbe number, high refractive index, and low birefringence; at the same time, it does not contain heteroatoms such as sulfur and nitrogen, and is not prone to yellowing and other adverse phenomena during processing and application, and can be applied in the fields of optical components, electronic products, medical products, etc.

[0047] (2) The raw material of the polycarbonate resin provided by the present application is simple to synthesize and low in cost, and no acidic catalyst is needed in the preparation process, which is very friendly to the environment.

[0048] Other aspects can be apparent after reading and understanding the accompanying drawings and detailed description. BRIEF DESCRIPTION OF DRAWINGS

[0049] The accompanying drawings are used to provide a further understanding of the technical solutions of the present application, and constitute a part of the specification, and are used to explain the technical solutions of the present application together with the embodiments of the present application, and do not constitute a limitation on the technical solutions of the present application.

[0050] FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a dihydroxy compound C1 provided by Preparation Example 1;

[0051] FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a dihydroxy compound C2 provided by Preparation Example 2;

[0052] FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of a dihydroxy compound C3 provided by Preparation Example 3. DETAILED DESCRIPTION

[0053] The technical solutions of the present application will be further described by specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application, and should not be regarded as a specific limitation on the present application.

[0054] Preparation Example 1

[0055] A dihydroxy compound C1, the synthesis route of which is as shown below:

[0056] The preparation method comprises the following steps: 20 g of 1,2-dimethylol ethylene is mixed with 20 g of anthracene, and then dissolved in 150 mL of anhydrous toluene, and then reacted at 160 DEG C under reflux for 4 h; after the reaction is completed, the temperature is cooled to room temperature, and then the anhydrous toluene is removed by rotary evaporation after sufficient water washing; and then the obtained crude product is purified by recrystallization to obtain the dihydroxyl compound C1.

[0057] Preparation Example 2

[0058] A dihydroxyl compound C2 has the following structural formula:

[0059] The preparation method is different from that of Preparation Example 1 in that cyclohexene-1,4-diol is used to replace 1,2-dimethylol ethylene, and other substances, the amount and the conditions are referred to Preparation Example 1.

[0060] Preparation Example 3

[0061] A dihydroxyl compound C3 has the following synthesis route:

[0062] The preparation method comprises the following steps: the dihydroxyl compound C1 (Preparation Example 1) is mixed with 2-bromoethyl acetate in a molar ratio of 1:2, and then dissolved in dichloromethane, and then heated and refluxed to react overnight; after the temperature is cooled to room temperature, the dichloromethane is removed to obtain an intermediate product D1; then the intermediate product D1 is reacted with an excess of sodium hydroxide aqueous solution at a reflux temperature for 180 min, and then purified by recrystallization with tetrahydrofuran to obtain the dihydroxyl compound C3.

[0063] Structural characterization:

[0064] (1) The dihydroxyl compounds obtained in Preparation Examples 1-3 are respectively tested by using a nuclear magnetic resonance spectrometer, the nuclear magnetic resonance hydrogen spectrum of the dihydroxyl compound C1 provided in Preparation Example 1 is shown in Fig. 1, the nuclear magnetic resonance hydrogen spectrum of the dihydroxyl compound C2 provided in Preparation Example 2 is shown in Fig. 2, and the nuclear magnetic resonance hydrogen spectrum of the dihydroxyl compound C3 provided in Preparation Example 3 is shown in Fig. 3.

[0065] As can be seen from Figs. 1-3, the dihydroxyl compounds with specific structures are successfully prepared in Preparation Examples 1-3.

[0066] Example 1

[0067] A polycarbonate resin comprises structural units shown in formula A1 and structural units shown in formula B2.

[0068] The preparation method of the polycarbonate resin provided in the example comprises the following steps:

[0069] (1) 1.01 kg (4.20 mol) of diphenyl carbonate, 1.73 kg (3.94 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 5 g (0.02 mol) of dihydroxy compound C1, and 3.17 x 10 -4 g (7.92 x 10 -6 mol) of sodium hydroxide were added to a 5 L reaction kettle, and the inside of the reaction kettle was replaced with nitrogen 5 times to maintain normal pressure inside the kettle;

[0070] (2) The temperature inside the reaction kettle was increased to 190°C in 20 min, and the reaction was continued for 10 min, after which the pressure inside the reaction kettle was decreased to 25 kPa in 5 min, and the reaction was continued for 50 min;

[0071] (3) The temperature inside the reaction kettle was increased to 210°C in 10 min, and the pressure inside the reaction kettle was decreased to 15 kPa, and the reaction was continued for 60 min;

[0072] (4) The temperature inside the reaction kettle was increased to 230°C in 10 min, and the pressure inside the reaction kettle was decreased to 5 kPa, and the reaction was continued for 50 min;

[0073] (5) The temperature inside the reaction kettle was increased to 260°C in 10 min, and the pressure inside the reaction kettle was decreased to 0.1 kPa, and the reaction was continued for 60 min;

[0074] (6) After the reaction was completed, nitrogen was introduced, the material was discharged from the kettle through a lower discharge valve, and was cut into particles after being cooled with water and collected;

[0075] (7) The collected particles were vacuum dried at 80°C for 4 h to obtain the polycarbonate resin.

[0076] Example 2

[0077] A polycarbonate resin containing structural units represented by Formula A1 and structural units represented by Formula B2.

[0078] The preparation method of the polycarbonate resin provided in this example is different from that of Example 1 in that the amount of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene in step (1) is 1.58 kg (3.60 mol), the amount of dihydroxy compound C1 is 0.11 kg (0.4 mol), and the amount of sodium hydroxide is 1.60 x 10 -3 g (4.00 x 10 -5 mol), and the other substances, amounts, and steps are the same as in Example 1.

[0079] Example 3

[0080] A polycarbonate resin containing structural units represented by Formula A1 and structural units represented by Formula B2;

[0081] The preparation method of the polycarbonate resin provided in the embodiment is different from that of Example 1 in that the feeding amount of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene in step (1) is 1.48 kg (3.38 mol), the feeding amount of dihydroxy compound C1 is 0.20 kg (0.69 mol), the feeding amount of sodium hydroxide is 8.16 x 10 -3 g (2.04 x 10 -4 mol), and other substances, amounts and steps are the same as those of Example 1.

[0082] Example 4

[0083] A polycarbonate resin containing structural units represented by Formula A1 and structural units represented by Formula B2;

[0084] The preparation method of the polycarbonate resin provided in the embodiment is different from that of Example 1 in that the feeding amount of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene in step (1) is 0.89 kg (2.04 mol), the feeding amount of dihydroxy compound C1 is 0.58 kg (2.04 mol), the feeding amount of sodium hydroxide is 4.89 x 10 -4 g (1.22 x 10 -5 mol), and other substances, amounts and steps are the same as those of Example 1.

[0085] Example 5

[0086] A polycarbonate resin containing structural units represented by Formula A1 and structural units represented by Formula B2;

[0087] The preparation method of the polycarbonate resin provided in the embodiment is different from that of Example 1 in that the feeding amount of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene in step (1) is 0.36 kg (0.82 mol), the feeding amount of dihydroxy compound C1 is 0.93 kg (3.26 mol), the feeding amount of sodium hydroxide is 3.26 x 10 -3 g (8.16 x 10 -5 mol), and other substances, amounts and steps are the same as those of Example 1.

[0088] Example 6

[0089] A polycarbonate resin containing structural units represented by Formula A1 and structural units represented by Formula B2;

[0090] The preparation method of the polycarbonate resin provided in the embodiment is different from that of Example 1 in that 9 g (0.02 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 1.17 kg (4.10 mol) of dihydroxy compound C1, and 9.88 x 10 -4 g (2.47 x 10 -5 mol) of sodium hydroxide are added in step (1), and other substances, amounts, and steps are the same as in Example 1.

[0091] Example 7

[0092] A polycarbonate resin containing structural units represented by Formula A1 and structural units represented by Formula B1;

[0093] The preparation method of the polycarbonate resin provided in the embodiment is different from that of Example 1 in that 1.01 kg (4.20 mol) of diphenyl carbonate, 0.12 kg (0.55 mol) of bisphenol A, 1.05 kg (3.65 mol) of dihydroxy compound C1, and 6.72 x 10 -4 g (1.68 x 10 -5 mol) of sodium hydroxide are added in a 5L reactor in step (1), and other substances, amounts, and steps are the same as in Example 1.

[0094] Example 8

[0095] A polycarbonate resin containing structural units represented by Formula A2 and structural units represented by Formula B2;

[0096] The preparation method of the polycarbonate resin provided in the embodiment is different from that of Example 1 in that 1.01 kg (4.20 mol) of diphenyl carbonate, 1.71 kg (3.90 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 29 g (0.10 mol) of dihydroxy compound C2, and 1.60 x 10 -4 g (4.00 x 10 -6 mol) of sodium hydroxide are added in a 5L reactor in step (1), and other substances, amounts, and steps are the same as in Example 1.

[0097] Example 9

[0098] A polycarbonate resin containing structural units represented by Formula A3 and structural units represented by Formula B2;

[0099] The preparation method of the polycarbonate resin provided in the embodiment is different from that of Example 1 in that 1.01 kg (4.20 mol) of diphenyl carbonate, 1.67 kg (3.80 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 71 g (0.20 mol) of dihydroxy compound C3, and 1.52 x 10 -4 g (3.80 x 10 -6 mol) of sodium hydroxide are added to the 5L reaction kettle of step (1), and other substances, amounts, and steps are the same as those of Example 1.

[0100] Example 10

[0101] A polycarbonate resin containing only structural units represented by Formula A1;

[0102] The preparation method of the polycarbonate resin provided in the embodiment is different from that of Example 1 in that 1.01 kg (4.20 mol) of diphenyl carbonate, 1.17 kg (4.08 mol) of dihydroxy compound C1, and 1.63 x 10 -3 g (4.08 x 10 -5 mol) of sodium hydroxide are added to the 5L reaction kettle of step (1), and other substances, amounts, and steps are the same as those of Example 1.

[0103] Comparative Example 1

[0104] A polycarbonate resin is different from that of Example 1 in that 1.01 kg (4.20 mol) of diphenyl carbonate, 0.96 kg (4.20 mol) of bisphenol A, and 5.04 x 10 -4 g (1.26 x 10 -5 mol) of sodium hydroxide are added to the 5L reaction kettle of step (1), and other substances, amounts, and steps are the same as those of Example 1.

[0105] Comparative Example 2

[0106] A polycarbonate resin is different from that of Example 1 in that 1.01 kg (4.20 mol) of diphenyl carbonate, 0.51 kg (2.24 mol) of bisphenol A, 0.80 kg (1.83 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 1.63 x 10 -3 g (4.08 x 10 -5 mol) of sodium hydroxide are added to the 5L reaction kettle of step (1), and other substances, amounts, and steps are the same as those of Example 1.

[0107] Comparative Example 3

[0108] A polycarbonate resin, differing from that in Example 1, is prepared by adding 1.01 kg (4.20 mol) diphenyl carbonate, 0.12 kg (0.53 mol) bisphenol A, 1.56 kg (3.55 mol) 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, and 1.63 × 10⁻⁶ ppm of bisphenol A to the 5L reactor in step (1). -3 g(4.08×10 -5 Sodium hydroxide (mol) was used, and the other substances, amounts, and procedures were the same as in Example 1.

[0109] Comparative Example 4

[0110] A polycarbonate resin, differing from that of Example 1, is provided in that: in step (1), the 5L reactor contains 1.01 kg (4.20 mol) of diphenyl carbonate, 1.85 kg (4.20 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, and 1.63 × 10⁻⁶ ppm of fluorene. -3 g(4.08×10 -5 Sodium hydroxide (mol) was used, and the other substances, amounts, and procedures were the same as in Example 1.

[0111] Comparative Example 5

[0112] A polycarbonate resin, which differs from Example 1 in that: in step (1), 1.01 kg (4.20 mol) of diphenyl carbonate, 1.53 kg (4.08 mol) of B2 monomer from patent CN115725063A, and 1.63 × 10⁻⁶ mol of diphenyl carbonate were added to the 5L reactor. -3 g(4.08×10 -5 Sodium hydroxide (mol) was used, and the other substances, amounts, and procedures were the same as in Example 1.

[0113] Application Example 1

[0114] A polycarbonate resin composition comprising 99.9% polycarbonate resin (Example 1) by weight and 0.1% antioxidant 1010 by weight.

[0115] Performance testing:

[0116] (1) Glass transition temperature (Tg): Measured using dynamic differential thermal analysis (DSC) according to the method provided in ASTM E1356.

[0117] (2) Refractive index (n) D ( ): Under the condition of a film thickness of 1.0 mm, the refractive index n of the sample at 25 °C was determined using an Abbe refractometer. D The test wavelength was 589nm.

[0118] (3) Abbe number (v): v = (nD-1) / (nF-nC), wherein nD refers to the refractive index at a wavelength of 589 nm, nC refers to the refractive index at a wavelength of 656 nm, and nF refers to the refractive index at a wavelength of 486 nm.

[0119] (4) Birefringence (Δn): The polymer is molded into a 1 mm thick film, and the birefringence Δn is measured using an ellipsometer.

[0120] The polycarbonate resins provided by Examples 1-10 and Comparative Examples 1-3 and the polycarbonate resin composition provided by Application Example 1 were tested according to the above test methods, and the test results are shown in Table 1:

[0121] Table 1

[0122] According to the data in Table 1, it can be seen that:

[0123] The polycarbonate resins provided by Examples 1-10 and the polycarbonate composition provided by Application Example 1 can maintain a high Abbe number while increasing the refractive index, and the heat resistance is not affected, and the birefringence is low, meeting the dual requirements of light and thin optical lens products and low dispersion performance; the polycarbonate resins provided by Comparative Examples 1-5 cannot simultaneously have high refractive index, high Abbe number and low birefringence.

[0124] The applicant declares that the present application illustrates a polycarbonate resin, its preparation method and application through the above examples, but the present application is not limited to the above examples, that is, it does not mean that the present application must rely on the above examples to be implemented. Those skilled in the art should understand that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific methods, etc. fall within the scope of protection and disclosure of the present application.

Claims

1. A polycarbonate resin, wherein, The polycarbonate resin contains the structural unit shown in Formula I and the structural unit shown in Formula B2: In Formula I, X is selected from C1-C6 straight-chain or branched alkylene groups; R1 and R2 are each independently selected from any one of H, C1-C20 straight-chain or branched alkyl, C1-C20 straight-chain or branched alkoxy, C5-C20 cycloalkyl, C5-C20 cycloalkoxy, C6-C20 aryl, and C6-C20 aryloxy. R3 and R4 are each independently selected from H, C1-C20 straight-chain or branched alkyl groups, or linked into a ring through a single bond, C1-C3 alkylene group, or C1-C3 alkene group; n is an integer from 0 to 5; 2. The polycarbonate resin according to claim 1, wherein, X is selected from C1-C2 alkylene groups; R1 and R2 are each independently selected from any one of H, C1-C6 straight-chain or branched alkyl, C1-C6 straight-chain or branched alkoxy, C5-C10 cycloalkyl, C5-C10 cycloalkoxy, C6-C12 aryl, and C6-C12 aryloxy. R3 and R4 are each independently selected from H or methyl, or are linked together in a ring via a single bond, a C1-C3 alkylene group, or a C1-C3 alkene group.

3. The polycarbonate resin according to claim 1, wherein, The n is an integer from 0 to 1.

4. The polycarbonate resin according to claim 1, wherein, The structural unit shown in Formula I is at least one of the structural units shown in Formulas A1 to A3; 5. The polycarbonate resin according to claim 1, wherein, The polycarbonate resin has a molar percentage content of the structural unit shown in Formula I of ≥0.5%.

6. A method for preparing the polycarbonate resin according to any one of claims 1 to 5, wherein, The preparation method includes: performing a polycondensation reaction on a dihydroxy compound having the structure shown in Formula III, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and a carbonate diester to obtain the polycarbonate resin; In Equation III, R1 to R4 and n each have the same defined range as in Equation I.

7. A polycarbonate resin composition, wherein, The polycarbonate resin composition comprises the polycarbonate resin and additives as described in any one of claims 1 to 5.

8. An optical lens, wherein, The optical lens comprises at least one of the polycarbonate resins as described in any one of claims 1 to 5 or the polycarbonate resin composition as described in claim 7.

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