Thermoplastic resin copolymer, method for producing the same, and use thereof

Abstract

The application discloses a thermoplastic resin copolymer, a manufacturing method and application thereof. The thermoplastic resin copolymer is formed by synergic copolymerization of a high-rigidity monomer with a specific dihydroxy compound to form a structural unit, has high refractive index, low haze, high light transmittance, excellent wear resistance and other advantages, and has low production cost, and can be applied to optical forming bodies.

Description

TECHNICAL FIELD

[0001] The present application relates to a thermoplastic resin, in particular to a thermoplastic resin copolymer, its manufacturing method and application. BACKGROUND

[0002] As the focus of future car companies, the hardware "arms race" of intelligent driving continues to upgrade. The new car released recently has significantly improved the configuration of an average of 5 cameras compared to the previous round of intelligent car models. The demand for environmental perception of autonomous driving requires higher resolution cameras to obtain more information and detect longer distances. With the development trend of lightweight camera equipment, plastic lenses have gradually replaced glass lenses.

[0003] Optical lenses composed of optical resins (such as polycarbonate resin) have the advantage of being able to be mass-produced by injection molding. Patent US4810771A proposes a high-refractive polyester resin material that can be used for optical lenses, which is prepared using 9,9-bis-(4-hydroxyphenyl) fluorene as a monomer, and the refractive index can reach about 1.64. Later, Konica patent JP2001072872A discloses a thermoplastic resin material that can be used for optical lenses and its manufacturing method, mainly using 2,2-bis-(2-hydroxyethoxy)-1,1-naphthalene as a polymerization monomer, which can be used to prepare polyester, polycarbonate, polyurethane, sulfone polymer and other optical resin materials, and the refractive index is higher, which can reach about 1.66.

[0004] However, polycarbonate resin generally has a large friction coefficient (about 0.73), and has poor wear resistance compared to most other engineering plastics, and the large friction coefficient will increase the resistance of PC falling off from the mold during injection molding, causing a certain amount of lens breakage and affecting the yield of finished products. Therefore, it is of great significance to prepare polycarbonate resin with improved wear resistance and demolding property. SUMMARY

[0005] In order to solve the above technical problems, the present application provides a thermoplastic resin copolymer, its manufacturing method and application. The present application develops a new structure of high rigidity monomer, and through the synergistic effect of the monomer and a specific dihydroxy compound, a thermoplastic resin copolymer with high refractive index, light transmittance, high wear resistance and demolding property is unexpectedly prepared, thereby completing the present application.

[0006] To achieve the above object, the technical scheme adopted by the present application is as follows:

[0007] A thermoplastic resin copolymer, comprising a structural unit derived from a compound represented by general formula A, a structural unit derived from a compound represented by general formula B, and a structural unit derived from a compound represented by general formula C;

[0008]

[0009] wherein X represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group; R1to R6independently represent hydrogen, halogen, mercapto, cyano, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an aralkoxy group having 6 to 20 carbon atoms, preferably hydrogen, an alkyl group having 1 to 3 carbon atoms, an aryl group or aralkyl group having 6 to 12 carbon atoms; a and b independently represent an integer not higher than 10, and neither a nor b is 0, preferably a and b independently represent an integer between 1 and 6; m and n independently represent an integer of 2 to 5, for example 2, 3, 4, 5;

[0010] Y represents an alkyl group having 1 to 4 carbon atoms, preferably a methylene group, an ethylene group, a propylene group; R7to R 10 independently represent hydrogen, halogen, cyano, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an aralkoxy group having 6 to 20 carbon atoms, preferably hydrogen, an alkyl group having 1 to 3 carbon atoms, an aryl group or aralkyl group having 6 to 12 carbon atoms; c and d independently represent an integer not higher than 10, and neither c nor d is 0, preferably c and d independently represent an integer between 1 and 6;

[0011] Z represents an alkyl group having 1 to 4 carbon atoms, preferably a methylene group, an ethylene group, a propylene group; R 11 to R 14 independently represent hydrogen, halogen, cyano, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an aralkoxy group having 6 to 20 carbon atoms, preferably hydrogen, an alkyl group having 1 to 3 carbon atoms, an aryl group or aralkyl group having 6 to 12 carbon atoms; e and f independently represent an integer not higher than 10, and neither e nor f is 0, preferably e and f independently represent an integer between 1 and 6.

[0012] The structural unit derived from the compound represented by the general formula A, B, C is not particularly limited in the form in which it is contained in the resin. For example, in the present application, the thermoplastic resin composition can contain a copolymer containing the structural unit derived from the compound represented by the general formula A, B, C, or can be a binary resin composition containing a homopolymer of each structural unit; or can be a blend of a homopolymer containing the structural unit derived from the compound represented by the general formula A with a homopolymer containing the structural unit derived from the compound represented by the general formula B and a homopolymer containing the structural unit derived from the compound represented by the general formula C, or a blend of a homopolymer containing the structural unit derived from the compound represented by the general formula A with a copolymer containing the structural unit derived from the compound represented by the general formula B.

[0013] The thermoplastic resin composition described in the present application can contain any structure of random, block, and alternating copolymer structures.

[0014] As a preferred embodiment of the present application, the molar content of the structural unit derived from the compound represented by the general formula A in the thermoplastic resin copolymer is 5 to 90 mol%;

[0015] The molar content of the structural unit derived from the compound represented by the general formula B in the thermoplastic resin copolymer is 5 to 80 mol%;

[0016] The molar content of the structural unit derived from the compound represented by the general formula C in the thermoplastic resin copolymer is 5 to 70 mol%.

[0017] As a preferred embodiment of the present application, the molar content of the structural unit derived from the compound represented by the general formula A in the thermoplastic resin copolymer is 10 to 80 mol%;

[0018] The molar content of the structural unit derived from the compound represented by the general formula B in the thermoplastic resin copolymer is 10 to 70 mol%;

[0019] The molar content of the structural unit derived from the compound represented by the general formula C in the thermoplastic resin copolymer is 10 to 60 mol%.

[0020] As a preferred embodiment of the present application, the compound represented by the general formula A has the following structure:

[0021]

[0022] Preferably, the compound represented by the general formula B has the following structure:

[0023]

[0024] Preferably, the compound represented by the general formula C has the following structure:

[0025]

[0026] As a preferred embodiment of the present application, the thermoplastic resin copolymer is one or more of polyester, polycarbonate, polyester carbonate, polyphenylene ether, polyurethane, sulfone polymer, sulfide polymer, epoxy resin, phenol resin, polyamide, polyimide, polymethyl methacrylate, preferably one or more of polyester, polycarbonate, polyester carbonate. The thermoplastic resin copolymer can be prepared by using the currently known preparation method.

[0027] Preferably, the thermoplastic resin copolymer is a polycarbonate resin having a refractive index of 1.66-1.75 at 20°C, wavelength 589 nm, an Abbe number not higher than 24, a haze not higher than 1% at 1 mm thickness, a light transmittance > 87%, and a friction coefficient of 0.1-0.5;

[0028] The weight average molecular weight of the polycarbonate resin is 30000-200000, preferably 50000-100000.

[0029] The present application also provides a manufacturing method of a thermoplastic resin copolymer, which is prepared by using dihydroxy compounds containing compounds represented by general formulae A, B, C and other raw materials to react;

[0030] The other raw materials are one or more of carbonic acid diester, dicarboxylic acid, dicarboxylic acid ester;

[0031]

[0032] wherein X represents an alkyl group having 1-10 carbon atoms, preferably an alkyl group having 1-6 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group; R1-R6 independently represent hydrogen, halogen, mercapto, cyano, an alkyl group having 1-20 carbon atoms, an alkoxy group having 1-20 carbon atoms, a cycloalkyl group having 5-20 carbon atoms, a cycloalkoxy group having 5-20 carbon atoms, an aryl group having 6-20 carbon atoms, an aralkyl group having 6-20 carbon atoms, an aralkoxy group having 6-20 carbon atoms, preferably hydrogen, an alkyl group having 1-3 carbon atoms, an aryl group having 6-12 carbon atoms or an aralkyl group; a and b independently represent an integer not higher than 10, and neither a nor b is 0, preferably a and b independently represent an integer between 1 and 6; m and n independently represent an integer of 2-5, for example 2, 3, 4, 5;

[0033] Y represents an alkyl group having 1-4 carbon atoms, preferably a methylene group, an ethylene group, a propylene group; R7-R 10each independently represents hydrogen, halogen, cyano, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, cycloalkyl group having 5 to 20 carbon atoms, cycloalkoxy group having 5 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aralkyl group having 6 to 20 carbon atoms, aralkyloxy group having 6 to 20 carbon atoms, preferably hydrogen, alkyl group having 1 to 3 carbon atoms, aryl group having 6 to 12 carbon atoms or aralkyl group; c and d each independently represent an integer not higher than 10, and c and d are not 0 at the same time, preferably c and d each independently represent an integer between 1 and 6;

[0034] Z represents alkyl group having 1 to 4 carbon atoms, preferably methylene, ethylene, propylene; R 11 ~R 14 each independently represents hydrogen, halogen, cyano, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, cycloalkyl group having 5 to 20 carbon atoms, cycloalkoxy group having 5 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aralkyl group having 6 to 20 carbon atoms, aralkyloxy group having 6 to 20 carbon atoms, preferably hydrogen, alkyl group having 1 to 3 carbon atoms, aryl group having 6 to 12 carbon atoms or aralkyl group; e and f each independently represent an integer not higher than 10, and e and f are not 0 at the same time, preferably e and f each independently represent an integer between 1 and 6.

[0035] In the present application, the dicarboxylic acid is selected from any one or a combination of at least two of terephthalic acid, p-phenylenediacetic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,2-biphenyl dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 2,2'-bis(carboxymethyloxy)-1,1'-binaphthalene, preferably 1,4-cyclohexane dicarboxylic acid and / or 2,6-naphthalene dicarboxylic acid.

[0036] In the present application, the dicarboxylic acid ester is selected from any one or a combination of at least two of dimethyl terephthalate, diethyl terephthalate, dimethyl p-phenylenediacetate, dimethyl 1,4-naphthalene dicarboxylate, dimethyl 2,6-naphthalene dicarboxylate, dimethyl 2,2-biphenyl dicarboxylate, dimethyl 1,4-cyclohexane dicarboxylate, 2,2'-bis(carboxylic acid methyl ester group methoxy)-1,1'-binaphthalene, preferably dimethyl 1,4-cyclohexane dicarboxylate and / or dimethyl 2,6-naphthalene dicarboxylate.

[0037] The molar ratio of the other raw material to the dihydroxy compound is (0.95 to 1.15): 1, preferably (1.0 to 1.1): 1.

[0038] In the production of the thermoplastic resin composition of the present application, an antioxidant, a release agent, an ultraviolet absorber, a flowability improver, a crystallization nucleating agent, a reinforcing agent, a dye, a toner, an antistatic agent, or an antibacterial agent, and the like can be optionally added as an auxiliary agent.

[0039] As a preferred embodiment of the present application, the reaction is prepared by ester exchange polycondensation method by using dihydroxy compounds containing compounds represented by general formulae A, B, C and a carbonic acid diester in the presence of an optional basic compound catalyst, an ester exchange catalyst or a mixed catalyst composed of both;

[0040] Preferably, the carbonic acid diester is one or more of diphenyl carbonate, ditolyl carbonate, diethylphenyl carbonate, diisopropylphenyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc., preferably diphenyl carbonate;

[0041] Preferably, the molar ratio of the carbonic acid diester and the dihydroxy compound is (0.95-1.15):1, preferably (1.0-1.1):1;

[0042] Preferably, the basic compound catalyst is one or more of lithium chloride, sodium chloride, potassium chloride, cesium chloride, lanthanum acetylacetonate, cerium acetylacetonate, tetrabutyl titanate, tetraisopropyl titanate, sodium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, sodium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, cesium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenylphosphate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylamine, dimethylbenzylamine, triphenylamine, diethylamine, tetramethylboron hydride ammonium, tetrabutylboron hydride ammonium, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate, preferably one or more of sodium hydroxide, sodium bicarbonate, cesium carbonate;

[0043] Preferably, the ester exchange catalyst is one or more of zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride, tetraisopropyl titanate, tetrabutyl titanate, tin acetate, cerium acetylacetonate, zirconium acetylacetonate, zirconium acetate, tetrabutoxy zirconium, preferably one or more of lanthanum acetylacetonate, zirconium acetate, zinc acetate;

[0044] Preferably, the amount of the basic compound catalyst, the ester exchange catalyst or the mixed catalyst composed of both is 1x10 -9 ~ 1x10 -3 , preferably 1x10 -6 ~ 5x10 -4 , based on the dihydroxy compound.

[0045] In the present application, the method of performing the ester exchange polycondensation is not particularly limited, and various methods known in the art can be used, such as interfacial polycondensation, solution polycondensation, melt polycondensation, etc. In some preferred embodiments, the ester exchange polycondensation is preferably performed by melt polycondensation.

[0046] As a preferred embodiment of the present invention, the manufacturing method includes the following steps:

[0047] A dihydroxy compound, a diester, optionally an alkaline compound catalyst, an transesterification catalyst, or a mixture thereof are added to the reactor. After the reactor is fully purged with nitrogen, the temperature is raised to melt the material inside the reactor. The melting temperature is 180–210°C, preferably 190–200°C, and the residence time during this stage is 40–100 min, preferably 50–80 min.

[0048] Start stirring, activate pressure control, and raise the temperature to 210–250°C, preferably 220–240°C. During this stage, the system pressure is 10–50 kPaA, preferably 20–30 kPaA, and the residence time is 60–320 min, preferably 150–240 min. Then, continue to reduce the pressure and increase the temperature to start the polycondensation reaction. During this stage, the system pressure is 10–500 PaA, preferably 50–100 PaA, the reaction temperature is 230–280°C, preferably 220–260°C, and the residence time is 10–120 min, preferably 20–60 min. During the reaction, the generated small molecule compounds are immediately removed by distillation, and finally, a thermoplastic resin copolymer is obtained in the reactor.

[0049] The blends described in this invention can be obtained by blending different thermoplastic resin compositions obtained by polymerization in equipment such as extruders, kneaders, and mixers.

[0050] The present invention also provides the application of the thermoplastic resin copolymer as described above or the thermoplastic resin copolymer prepared by the method described above in optical forming bodies.

[0051] As a preferred embodiment of the present invention, the thermoplastic resin copolymer is suitable for preparing optical lenses or optical films.

[0052] The thermoplastic resin copolymer provided by this invention has a high refractive index, low haze, good light transmittance, good high-temperature wear resistance and demolding properties, and is easy to process. It is beneficial to save production costs and improve product yield, and is suitable for the field of optical forming bodies. Detailed Implementation

[0053] The present invention will now be described in conjunction with specific embodiments. It should be noted that the embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-substantial improvements and adjustments made to the present invention based on its content are within the scope of protection of the present invention.

[0054] The main testing methods involved in this invention are as follows:

[0055] 1) Weight average molecular weight (Mw): Using gel permeation chromatography (GPC), tetrahydrofuran as the developing solvent, a standard curve was prepared using a standard polystyrene of known molecular weight (molecular weight distribution = 1). Based on this standard curve, Mw was calculated from the retention time of the GPC.

[0056] 2) Refractive index (nD): The refractive index (nD) of the thermoplastic resin composition of the present application at 23°C, wavelength 589 nm was measured according to the method of JIS-K-7142 using an Abbe refractometer for a 0.1 mm thick film composed of the thermoplastic resin composition prepared in the examples.

[0057] 3) Abbe number: The refractive indices at 23°C, wavelengths 486 nm, 589 nm and 656 nm were measured using an Abbe refractometer for a 0.1 mm thick film composed of the polycarbonate resin prepared in the examples, and further the Abbe number v was calculated using the following formula,

[0058] v = (nD - 1) / (nF - nC)

[0059] wherein nD represents the refractive index at D light (D light - yellow light, 589.3 nm, D line in the sodium light spectrum), nF represents the refractive index at F light (F light - blue light, 486.1 nm, F line in the hydrogen light spectrum), and nC represents the refractive index at C light (C light - red light, 656.3 nm, C line in the hydrogen light spectrum).

[0060] 4) Haze: Measured according to ISO 14782.

[0061] 5) Light transmittance: Measured using the method of JIS-K-7361-1 using a turbidimeter for a 0.1 mm thick film composed of the polycarbonate resin prepared in the examples.

[0062] 6) Wear resistance: The coefficient of friction was measured according to the method of GB / T 10006.

[0063] 7) Yield of finished product (mold release performance): The ratio of the number of lenses that passed the inspection to the total number (including broken lenses) after the injection-molded lenses were removed from 1 kg of resin.

[0064] The sources of some of the reagent raw materials used in the examples and comparative examples of the present application are as follows, and the remaining reagent raw materials, unless otherwise specified, are commercially available products:

[0065] (1) The compound of general formula A can be prepared by two steps: 1) phenol ketone condensation reaction of aryl phenol and its derivatives with anthraquinone and its derivatives; 2) reaction of the dihydroxy compound prepared in step 1) with alkylene oxide (such as ethylene oxide, propylene oxide) or alkylene carbonate (such as ethylene carbonate, propylene carbonate, etc.) to prepare, and the above two reaction types and synthesis methods are well known to those skilled in the art.

[0066]

[0067] The preparation steps of compound A-1 are as follows:

[0068] Take 223.18 g of β-anthracenol [CAS No.: 613-14-9], 104.1 g of anthraquinone in a three-necked flask, add 500 mL of toluene, and stir well until dissolved. Slowly drop the mixture of 1.1315 g of concentrated sulfuric acid and 0.42 g of mercaptopropionic acid into the above solution, heat to 70°C and react for 3 h. After the reaction is completed, cool to room temperature, and add sodium hydroxide solution to neutralize the system to neutral. Add 500 mL of anhydrous methanol, analyze and crush the solid, then filter, wash with methanol and dry to obtain intermediate M-1.

[0069] 1 H-NMR (400 MHz, CDCl3) / δ x 10 -6 : 8.24-8.18 (d, 4H), 7.86-7.85 (m, 4H), 7.7-7.66 (m, 4H), 7.52 (m, 2H), 7.36-7.22 (m, 8H), 7.04 (m, 2H), 5.35 (s, 2H).

[0070] Weigh 200 g of intermediate M-1 and 4.12 g of potassium hydroxide into 500 mL of diethylene glycol dimethyl ether, replace 3 times with 0.5 MPa nitrogen, heat to 120°C, and pass in ethylene oxide gas, keeping the molar ratio of ethylene oxide to intermediate at 2.35:1, and react for 6 h. After the reaction is completed, cool to room temperature, filter, wash with water, and dry to obtain A-1.

[0071] 1 H-NMR (400 MHz, CDCl3) / δ x 10 -6 : 8.25 (s, 4H), 7.85-7.84 (m, 4H), 7.7-7.66 (m, 4H), 7.52-7.11 (m, 12H), 4.41 (m, 4H), 3.79 (m, 4H), 3.65-3.44 (m, 10H).

[0072]

[0073] The preparation procedure of the compound of A-2 is as follows:

[0074] Take 223.18 g of β-anthracenol [CAS No.: 613-14-9], 104.1 g of anthraquinone in a three-necked flask, add 500 mL of toluene, and stir well until dissolved. Slowly drop a mixture of 1.1315 g of concentrated sulfuric acid and 0.42 g of mercaptopropionic acid into the above solution, and heat to 70°C for 3 h. After the reaction is completed, cool to room temperature, and add a sodium hydroxide solution to neutralize the system to neutral. Add 500 mL of anhydrous methanol, and filter the solid after stirring and crushing, wash with methanol, and dry to obtain the intermediate M-1.

[0075] Take 200 g of the intermediate M-1 and 4.29 g of potassium hydroxide into 500 mL of N,N-dimethylformamide, replace three times with 0.5 MPa of nitrogen, and heat to 130°C. Maintain the molar ratio of ethylene oxide to the intermediate at 2.25:1, and react for 4 h. After the reaction is completed, cool to room temperature, and filter, wash with water, and dry to obtain A-2.

[0076] 1 H-NMR (400 MHz, CDC13) / δ x 10 -6 : 8.25 (m, 4H), 7.85-7.84 (m, 4H), 7.70-7.66 (m, 4H), 7.52 (m, 2H), 7.36-7.21 (m, 8H), 7.11 (m, 2H), 4.43 (m, 4H), 3.69-3.65 (m, 6H).

[0077] (2) The compound represented by the general formula B is prepared by referring to the method disclosed in Japanese Patent JP2014227387A.

[0078] The preparation procedure of the compound of B-1 is as follows:

[0079]

[0080] Take 120 g of 1,1'-bi-2-naphthol [CAS No.: 602-09-5], 84.7 g of ethylene carbonate, and 6 g of potassium carbonate in a three-necked flask, add 300 g of toluene, and stir well until dissolved. React at 115°C for 8 h. After the reaction is completed, wash with an aqueous sodium hydroxide solution until neutral. Separate the organic phase, recrystallize by cooling, filter, and dry to obtain B-1.

[0081] 1 H-NMR (400 MHz, CDC13) / δ x 10 -68.48-8.05 (m, 4H), 7.77 (d, 2H), 7.55-7.44 (m, 4H), 7.11 (d, 2H), 4.43 (t, 4H), 3.69-3.65 (m, 6H).

[0082] The preparation procedure of the compound B-2 is as follows:

[0083]

[0084] Weigh 220 g of 6-hydroxy-1-phenylnaphthalene [CAS No.: 156152-21-5], 1 g of copper (I) chloride in a three-necked flask, add 500 g of N,N'-dimethylformamide, and stir thoroughly at 60°C until dissolved. While blowing air into the solution, heat the reaction for about 48 h. After the reaction is completed, add 1.5 L of deionized water to the reaction solution, filter out the insoluble matter, and wash thoroughly with water and methanol, and dry to obtain the intermediate M-2.

[0085] 1 H-NMR (400MHz, CDC13) / δ x 10 -6 8.37-8.31 (m, 4H), 7.99-7.79 (m, 6H), 7.59-7.41 (m, 8H), 7.04 (d, 2H), 5.35 (s, 2H).

[0086] Weigh 109.54 g of the intermediate M-2, 50.75 g of vinylene carbonate, and 3 g of potassium carbonate in a three-necked flask, add 200 g of toluene, and stir thoroughly until dissolved. React at 110°C for 10 h. After the reaction is completed, wash with an aqueous sodium hydroxide solution until neutral. Separate the organic phase, and recrystallize by cooling. After filtration and drying, obtain B-1.

[0087] 1 H-NMR (400MHz, CDC13) / δ x 10 -6 8.44-8.31 (m, 4H), 7.97-7.79 (m, 6H), 7.61-7.41 (m, 8H), 7.11 (d, 2H), 4.43 (t, 4H), 3.69-3.65 (m, 6H).

[0088] (3) Compound C-1

[0089] The compound C-1 is a commercially available product, 9,9-bis[3-phenyl-4-(2-hydroxyethoxy)phenyl]fluorene, CAS No. 156326-38-4, Huanghua Xinnuolixing Co., Ltd.

[0090] Compound C-2 is a commercially available product, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, CAS No. 117344-32-8, Teijin Chemicals Co., Ltd.

[0091]

[0092] Example 1

[0093] Into a 200 ml four-necked flask equipped with a stirrer and a distillation apparatus, 3.77 g (0.005 mol) of A-1, 29.93 g (0.08 mol) of B-1, 8.85 g (0.015 mol) of C-1, 20.35 g (0.095 mol) of diphenyl carbonate, 18.35 mg (1.0 x 10 -4 mol) of zinc acetate were placed, and the inside of the flask was replaced with nitrogen four times. The flask was heated to 180°C under a nitrogen atmosphere of 101 kPa (A), and after 100 minutes from the start of heating, it was confirmed that the starting materials were completely dissolved. Thereafter, the stirring was started, the pressure was adjusted to 10 kPa (A), and the temperature was increased to 210°C at a rate of 30°C / hr. At this time, it was confirmed that phenol, which was a by-product, started to distill. The reaction was maintained at 210°C for 320 minutes, and then the temperature was increased to 230°C at a rate of 60°C / hr. After the temperature reached 230°C, the pressure was gradually decreased to 10 Pa (A) over a period of 1 hour, and the reaction was stirred for 120 minutes under this condition. After the reaction was completed, the inside of the flask was replaced with nitrogen to return to the normal pressure, and the obtained thermoplastic resin composition was taken out. The properties of the composition were evaluated, and the results are shown in Table 1.

[0094] Example 2

[0095] Into a 200 ml four-necked flask equipped with a stirrer and a distillation apparatus, 60.01 g (0.09 mol) of A-2, 2.63 g (0.005 mol) of B-2, 2.19 g (0.005 mol) of C-2, 24.21 g (0.10 mol) of ditolyl carbonate, 32.58 mg (1.0 x 10 -7 mol) of cesium carbonate were placed, and the inside of the flask was replaced with nitrogen four times. The flask was heated to 210°C under a nitrogen atmosphere of 101 kPa (A), and after 40 minutes from the start of heating, it was confirmed that the starting materials were completely dissolved. Thereafter, the stirring was started, the pressure was adjusted to 20 kPa (A), and the temperature was increased to 250°C at a rate of 30°C / hr. At this time, it was confirmed that phenol, which was a by-product, started to distill. The reaction was maintained at 250°C for 60 minutes, and then the temperature was increased to 280°C at a rate of 60°C / hr. After the temperature reached 280°C, the pressure was gradually decreased to 500 Pa (A) over a period of 1 hour, and the reaction was stirred for 10 minutes under this condition. After the reaction was completed, the inside of the flask was replaced with nitrogen to return to the normal pressure, and the obtained thermoplastic resin composition was taken out. The properties of the composition were evaluated, and the results are shown in Table 1.

[0096] Example 3

[0097] Into a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, were placed 6.67g (0.01mol) of A-2, 36.86g (0.07mol) of B-2, 11.81g (0.02mol) of C-1, 29.71g (0.11mol) of diethylphenyl carbonate, 0.044μg (1.0 x 10 -10 mol) of acetylacetone lanthanum. After four nitrogen purges, the temperature was raised to 190°C under a nitrogen atmosphere of 101Kpa (A). After 80 minutes of heating, the starting materials were confirmed to be completely dissolved, and then the stirring was started and the temperature was raised to 220°C at a rate of 30°C / hr. At this time, the phenol, which was a by-product, was confirmed to be distilled off, and the reaction was maintained at 220°C for 240 minutes. Then, the temperature was raised to 260°C at a rate of 60°C / hr, and after the temperature reached 260°C, the pressure was gradually reduced to 50Pa (A) within 1 hour. The reaction was stirred for 60 minutes under these conditions, and then the reaction was terminated. After the termination of the reaction, the nitrogen was introduced into the four-necked flask to return to the normal pressure, and the thermoplastic resin composition was taken out to evaluate the properties. The results are shown in Table 1.

[0098] Example 4

[0099] Into a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, were placed 60.34g (0.08mol) of A-1, 5.27g (0.01mol) of B-2, 4.39g (0.01mol) of C-2, 26.01g (0.115mol) of dicyclohexyl carbonate, 4.2mg (5.0 x 10 -5 mol) of sodium bicarbonate. After four nitrogen purges, the temperature was raised to 200°C under a nitrogen atmosphere of 101Kpa (A). After 50 minutes of heating, the starting materials were confirmed to be completely dissolved, and then the stirring was started and the pressure was adjusted to 50Kpa (A). The temperature was raised to 240°C at a rate of 30°C / hr. At this time, the phenol, which was a by-product, was confirmed to be distilled off, and the reaction was maintained at 240°C for 180 minutes. Then, the temperature was raised to 250°C at a rate of 60°C / hr, and after the temperature reached 250°C, the pressure was gradually reduced to 100Pa (A) within 1 hour. The reaction was stirred for 20 minutes under these conditions, and then the reaction was terminated. After the termination of the reaction, the nitrogen was introduced into the four-necked flask to return to the normal pressure, and the thermoplastic resin composition was taken out to evaluate the properties. The results are shown in Table 1.

[0100] Example 5

[0101] A-1, 9.35 g (0.025 mol) of B-1, 26.31 g (0.06 mol) of C-2, 22.49 g (0.105 mol) of diphenyl carbonate, 16.37 μg (5.0 x 10 -8 mol) of zirconium acetate were put into a 200 ml four-necked flask equipped with a stirrer and a distillation apparatus. After nitrogen substitution was performed four times, heating was performed under a nitrogen atmosphere of 101 Kpa (A) to 195°C. After 75 min from the start of heating, it was confirmed that the raw materials were completely dissolved. Thereafter, stirring was started, the pressure was adjusted to 40 Kpa (A), and heating was performed at a rate of 30°C / hr to 210°C. At this time, it was confirmed that phenol, which was a by-product, started to distill. The reaction was maintained at 210°C for 200 min. Thereafter, heating was performed at a rate of 60°C / hr to 220°C. After the temperature reached 220°C, the pressure was gradually decreased to 260 Pa (A) over a period of 1 hr. The reaction was stirred under these conditions for 80 min, and then terminated. After the termination of the reaction, the four-necked flask was filled with nitrogen to return to normal pressure. The obtained thermoplastic resin composition was taken out, and performance evaluation was performed. The results are shown in Table 1.

[0102]

Example 6

[0103] A-2, 1.87 g (0.005 mol) of B-1, 41.32 g (0.07 mol) of C-1, 25.33 g (0.112 mol) of dicyclohexyl carbonate, 40 μg (1.0 x 10 -6 mol) of sodium hydroxide were put into a 200 ml four-necked flask equipped with a stirrer and a distillation apparatus. After nitrogen substitution was performed four times, heating was performed under a nitrogen atmosphere of 101 Kpa (A) to 205°C. After 45 min from the start of heating, it was confirmed that the raw materials were completely dissolved. Thereafter, stirring was started, the pressure was adjusted to 25 Kpa (A), and heating was performed at a rate of 30°C / hr to 240°C. At this time, it was confirmed that phenol, which was a by-product, started to distill. The reaction was maintained at 240°C for 150 min. Thereafter, the pressure was gradually decreased to 380 Pa (A) over a period of 1 hr. The reaction was stirred under these conditions for 100 min, and then terminated. After the termination of the reaction, the four-necked flask was filled with nitrogen to return to normal pressure. The obtained thermoplastic resin composition was taken out, and performance evaluation was performed. The results are shown in Table 1.

[0104]

Example 7

[0105] A-2, 1.87 g (0.005 mol) of B-1, 41.32 g (0.07 mol) of C-1, 25.33 g (0.112 mol) of dicyclohexyl carbonate, 40 μg (1.0 x 10 -7mol) cesium carbonate was placed in a 200 ml four-necked flask equipped with a stirrer and distillation apparatus, and the same operation as in Example 1 was performed, except that the obtained thermoplastic resin (polyester carbonate) copolymer was subjected to performance evaluation, and the results are shown in Table 1.

[0106] [Comparative Example 1]

[0107] A thermoplastic resin copolymer was prepared in substantially the same manner as in Example 1, except that the raw material monomer A-1 was replaced with BNEA (Chengdu Yuanda Chemical Co., Ltd.) in the same molar amount. The obtained thermoplastic resin copolymer was subjected to performance evaluation, and the results are shown in Table 1.

[0108]

[0109] [Comparative Example 2]

[0110] A thermoplastic resin copolymer was prepared in substantially the same manner as in Example 1, except that the raw material monomer B-1 was not added. The obtained thermoplastic resin copolymer was subjected to performance evaluation, and the results are shown in Table 1.

[0111] [Comparative Example 3]

[0112] A thermoplastic resin copolymer was prepared in substantially the same manner as in Example 1, except that the raw material monomer C-1 was not added. The obtained thermoplastic resin copolymer was subjected to performance evaluation, and the results are shown in Table 1.

[0113] [Comparative Example 4]

[0114] A thermoplastic resin copolymer was prepared in substantially the same manner as in Example 1, except that the raw material monomer C-1 was replaced with hydroquinone dihydroxyethyl ether [CAS No. 104-38-1, Beijing Bailingwei Technology Co., Ltd.] in the same molar amount. The obtained thermoplastic resin copolymer was subjected to performance evaluation, and the results are shown in Table 1.

[0115] Table 1, Performance Evaluation Results

[0116] Molecular weight Refractive index Abbe number Haze / % Transmittance / % Friction coefficient Yield of finished product / % Example 1 96545 1.701 21.3 0.28 89.5 0.36 94 Example 2 198870 1.749 18.9 0.96 87.1 0.11 96 Example 3 87711 1.687 20.7 0.66 89.3 0.41 93 Example 4 142300 1.737 19.6 0.87 88.3 0.19 95 Example 5 51996 1.662 23.7 0.45 89.5 0.36 94 Example 6 32056 1.675 23.1 0.32 89.7 0.49 92 Example 7 90450 1.696 20.5 0.64 89.2 0.28 95 Comparative Example 1 78560 1.719 21.8 0.43 90.2 0.55 88 Comparative Example 2 36653 1.657 23.9 0.37 89.1 0.68 83 Comparative Example 3 85300 1.692 21.6 0.43 88.9 0.70 80 Comparative Example 4 91228 1.694 21.5 0.61 89.0 0.69 82

[0117] The above only describes preferred embodiments of the present application, and it should be noted that those skilled in the art can make several improvements and supplements without departing from the method of the present application, and these improvements and supplements should also be considered within the protection scope of the present application.

Claims

1. A thermoplastic resin copolymer, characterized in that, It includes structural units derived from compounds of general formula A, structural units derived from compounds of general formula B, and structural units derived from compounds of general formula C; Wherein, X represents an alkyl group with 1 to 10 carbon atoms; R1 to R6 independently represent hydrogen, halogen, mercapto, cyano, alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 20 carbon atoms, cycloalkyl group with 5 to 20 carbon atoms, cycloalkoxy group with 5 to 20 carbon atoms, aryl group with 6 to 20 carbon atoms, aralkyl group with 6 to 20 carbon atoms, and aralkoxy group with 6 to 20 carbon atoms; a and b independently represent integers not higher than 10, and neither a nor b is 0; m and n independently represent integers from 2 to 5. Y represents an alkyl group with 1 to 4 carbon atoms; R7 to R 10 Each of the following groups independently represents hydrogen, halogen, cyano, alkyl with 1 to 20 carbon atoms, alkoxy with 1 to 20 carbon atoms, cycloalkyl with 5 to 20 carbon atoms, cycloalkoxy with 5 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, aralkyl with 6 to 20 carbon atoms, and aralkoxy with 6 to 20 carbon atoms; c and d independently represent integers not higher than 10, and neither c nor d is 0; Z represents an alkyl group having 1 to 4 carbon atoms; R 11 ~R 14 Each of the following groups independently represents hydrogen, halogen, cyano, alkyl with 1 to 20 carbon atoms, alkoxy with 1 to 20 carbon atoms, cycloalkyl with 5 to 20 carbon atoms, cycloalkoxy with 5 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, aralkyl with 6 to 20 carbon atoms, and aralkoxy with 6 to 20 carbon atoms; e and f independently represent integers not higher than 10, and neither e nor f is 0.

2. The thermoplastic resin copolymer according to claim 1, characterized in that, In general formula A, X represents an alkyl group having 1 to 6 carbon atoms.

3. The thermoplastic resin copolymer according to claim 2, characterized in that, In general formula A, X represents methylene, ethylene, or propylene.

4. The thermoplastic resin copolymer according to claim 1, characterized in that, In general formula A, R1 to R6 independently represent hydrogen, alkyl with 1 to 3 carbon atoms, aryl or aralkyl with 6 to 12 carbon atoms, respectively.

5. The thermoplastic resin copolymer according to claim 1, characterized in that, In general formula B, Y represents methylene, ethylene, or propylene.

6. The thermoplastic resin copolymer according to claim 1, characterized in that, In general formula B, R7~R 10 Each of the following can be independently represented: hydrogen, alkyl with 1 to 3 carbon atoms, aryl or aralkyl with 6 to 12 carbon atoms.

7. The thermoplastic resin copolymer according to claim 1, characterized in that, In general formula C, Z represents methylene, ethylene, or propylene.

8. The thermoplastic resin copolymer according to claim 1, characterized in that, In general formula C, R 11 ~R 14 Each of the following can be independently represented: hydrogen, alkyl with 1 to 3 carbon atoms, aryl or aralkyl with 6 to 12 carbon atoms.

9. The thermoplastic resin copolymer according to claim 1, characterized in that, The structural units derived from the compound represented by general formula A have a molar content of 5 to 90 mol% in the thermoplastic resin copolymer; The structural units derived from the compound shown in general formula B have a molar content of 5 to 80 mol% in the thermoplastic resin copolymer; The structural units derived from the compound represented by general formula C have a molar content of 5–70 mol% in the thermoplastic resin copolymer.

10. The thermoplastic resin copolymer according to claim 9, characterized in that, The structural units derived from the compound represented by general formula A have a molar content of 10–80 mol% in the thermoplastic resin copolymer; The structural units derived from the compound shown in general formula B have a molar content of 10 to 70 mol% in the thermoplastic resin copolymer; The structural units derived from the compound represented by general formula C have a molar content of 10–60 mol% in the thermoplastic resin copolymer.

11. The thermoplastic resin copolymer according to any one of claims 1 to 10, characterized in that, The compound represented by general formula A has the following structural formula:

12. The thermoplastic resin copolymer according to claim 11, characterized in that, The compound represented by general formula B has the following structural formula:

13. The thermoplastic resin copolymer according to claim 11, characterized in that, The compound represented by general formula C has the following structural formula:

14. The thermoplastic resin copolymer according to any one of claims 1 to 10, characterized in that, The thermoplastic resin copolymer is one or more of polyester, polycarbonate, polyester carbonate, polyphenylene ether, polyurethane, sulfone polymer, thioether polymer, epoxy resin, phenolic resin, polyamide, polyimide, and polymethyl methacrylate. The polycarbonate resin has a weight-average molecular weight of 30,000-200,000.

15. The thermoplastic resin copolymer according to claim 14, characterized in that, The thermoplastic resin copolymer is one or more of polyester, polycarbonate, and polyester carbonate.

16. The thermoplastic resin copolymer according to claim 14, characterized in that, The thermoplastic resin copolymer is a polycarbonate resin with a refractive index of 1.66-1.75 at 20°C and a wavelength of 589nm, an Abbe number not higher than 24, a haze of not higher than 1% at a thickness of 1mm, a light transmittance of >87%, and a coefficient of friction of 0.1-0.

5.

17. The thermoplastic resin copolymer according to claim 14, characterized in that, The weight-average molecular weight of the polycarbonate resin is 50,000-100,000.

18. A method for manufacturing a thermoplastic resin copolymer, characterized in that, It is prepared by reacting a dihydroxy compound containing compounds of general formulas A, B, and C with other starting materials; The other raw materials are one or more of the following: diester, dicarboxylic acid, and dicarboxylic acid ester; Wherein, X represents an alkyl group with 1 to 10 carbon atoms; R1 to R6 independently represent hydrogen, halogen, mercapto, cyano, alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 20 carbon atoms, cycloalkyl group with 5 to 20 carbon atoms, cycloalkoxy group with 5 to 20 carbon atoms, aryl group with 6 to 20 carbon atoms, aralkyl group with 6 to 20 carbon atoms, and aralkoxy group with 6 to 20 carbon atoms; a and b independently represent integers not higher than 10, and neither a nor b is 0; m and n independently represent integers from 2 to 5. Y represents an alkyl group with 1 to 4 carbon atoms; R7 to R 10 Each of the following groups independently represents hydrogen, halogen, cyano, alkyl with 1 to 20 carbon atoms, alkoxy with 1 to 20 carbon atoms, cycloalkyl with 5 to 20 carbon atoms, cycloalkoxy with 5 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, aralkyl with 6 to 20 carbon atoms, and aralkoxy with 6 to 20 carbon atoms; c and d independently represent integers not higher than 10, and neither c nor d is 0; Z represents an alkyl group having 1 to 4 carbon atoms; R 11 ~R 14 Each of the following groups independently represents hydrogen, halogen, cyano, alkyl with 1 to 20 carbon atoms, alkoxy with 1 to 20 carbon atoms, cycloalkyl with 5 to 20 carbon atoms, cycloalkoxy with 5 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, aralkyl with 6 to 20 carbon atoms, and aralkoxy with 6 to 20 carbon atoms; e and f independently represent integers not higher than 10, and neither e nor f is 0.

19. The method for manufacturing the thermoplastic resin copolymer according to claim 18, characterized in that, In general formula A, X represents an alkyl group having 1 to 6 carbon atoms.

20. The method for manufacturing the thermoplastic resin copolymer according to claim 19, characterized in that, In general formula A, X represents methylene, ethylene, or propylene.

21. The method for manufacturing the thermoplastic resin copolymer according to claim 18, characterized in that, In general formula A, R1 to R6 independently represent hydrogen, alkyl with 1 to 3 carbon atoms, aryl or aralkyl with 6 to 12 carbon atoms, respectively.

22. The method for manufacturing the thermoplastic resin copolymer according to claim 18, characterized in that, In general formula B, Y represents methylene, ethylene, or propylene.

23. The method for manufacturing the thermoplastic resin copolymer according to claim 18, characterized in that, In general formula B, R7~R 10 Each of the following can be independently represented: hydrogen, alkyl with 1 to 3 carbon atoms, aryl or aralkyl with 6 to 12 carbon atoms.

24. The method for manufacturing the thermoplastic resin copolymer according to claim 18, characterized in that, In general formula C, Z represents methylene, ethylene, or propylene.

25. The method for manufacturing the thermoplastic resin copolymer according to claim 18, characterized in that, In general formula C, R 11 ~R 14 Each of the following can be independently represented: hydrogen, alkyl with 1 to 3 carbon atoms, aryl or aralkyl with 6 to 12 carbon atoms.

26. The method for manufacturing the thermoplastic resin copolymer according to claim 18, characterized in that, It is prepared by reacting a dihydroxy compound containing compounds of general formulas A, B, and C with a diester of carbonate in the presence of an optional basic catalyst, a transesterification catalyst, or a mixture of both, via transesterification polycondensation.

27. The method for manufacturing the thermoplastic resin copolymer according to claim 26, characterized in that, The carbonate diester is one or more of the following: diphenyl carbonate, dimethyl carbonate, diethylphenyl carbonate, diisopropylphenyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc.

28. The method for manufacturing the thermoplastic resin copolymer according to claim 26, characterized in that, The molar ratio of the carbonate diester to the dihydroxy compound is (0.95–1.15):

1.

29. The method for manufacturing the thermoplastic resin copolymer according to claim 28, characterized in that, The molar ratio of the carbonate diester to the dihydroxy compound is (1.0–1.1):

1.

30. The method for manufacturing the thermoplastic resin copolymer according to claim 26, characterized in that, The alkaline compound catalyst is one or more of the following: lithium chloride, sodium chloride, potassium chloride, cesium chloride, lanthanum acetylacetonate, cerium acetylacetonate, tetrabutyl titanate, tetraisopropyl titanate, sodium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, sodium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, cesium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenyl phosphate, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethylbenzyl ammonium hydroxide, triethylamine, dimethylbenzylamine, triphenylamine, diethylamine, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutyltetraphenylborate, and tetraphenyltetraphenylborate.

31. The method for manufacturing the thermoplastic resin copolymer according to claim 26, characterized in that, The transesterification catalyst is one or more of zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride, tetraisopropyl titanate, tetrabutyl titanate, tin acetate, cerium acetylacetone, zirconium acetylacetone, zirconium acetate, and tetrabutoxyzirconium.

32. The method for manufacturing the thermoplastic resin copolymer according to claim 26, characterized in that, The amount of basic compound catalyst, transesterification catalyst, or a mixture of both, added, based on a molar ratio, is 1 × 10⁻⁶ of the dihydroxy compound. -9 ~1×10 -3 .

33. The method for manufacturing the thermoplastic resin copolymer according to claim 32, characterized in that, The amount of basic compound catalyst, transesterification catalyst, or a mixture of both, added, based on a molar ratio, is 1 × 10⁻⁶ of the dihydroxy compound. -6 ~5×10 -4 .

34. The method for manufacturing the thermoplastic resin copolymer according to claim 7, characterized in that, Includes the following steps: Dihydroxy compound, diester, optionally basic compound catalyst, transesterification catalyst or a mixture of both is added to the reactor. After the reactor is fully purged with nitrogen, the temperature is raised to melt the material in the reactor. The melting temperature is 180-210℃ and the residence time in this stage is 40-100 min. Start stirring, activate pressure reduction control, and raise the temperature to 210–250°C. During this stage, the system pressure is 10–50 kPaA, and the residence time is 60–320 min. Then, continue to reduce the pressure and increase the temperature to start the polycondensation reaction. During this stage, the system pressure is 10–500 PaA, the reaction temperature is 230–280°C, and the residence time is 10–120 min. During the reaction, the generated small molecule compounds are immediately removed by distillation, and finally, a thermoplastic resin copolymer is obtained in the reactor.

35. The method for manufacturing the thermoplastic resin copolymer according to claim 34, characterized in that, The temperature is raised to 190-200℃, and the residence time in this stage is 50-80 minutes.

36. The method for manufacturing the thermoplastic resin copolymer according to claim 34, characterized in that, Start stirring, turn on pressure reduction control, and raise the temperature to 220-240℃. During this stage, the system pressure is 20-30 kPaA, and the residence time is 150-240 min. Then continue to reduce the pressure and increase the temperature to start the polycondensation reaction. During this stage, the system pressure is 50-100 PaA, the reaction temperature is 220-260℃, and the residence time is 20-60 min.

37. The use of a thermoplastic resin copolymer as described in any one of claims 1 to 17 or a thermoplastic resin copolymer prepared by the method described in any one of claims 18 to 36 in an optical forming body.

38. The application according to claim 37, characterized in that, The thermoplastic resin copolymer is suitable for preparing optical lenses or optical films.

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