Thermoplastic resin composition, manufacturing method thereof, and optical lens

Abstract

A thermoplastic resin composition contains a structural unit derived from a compound represented by the general formula (A) and a structural unit derived from a compound represented by the general formula (B). In the differential molecular weight distribution curve obtained by measuring the thermoplastic resin by gel permeation chromatography based on polystyrene conversion, with the logarithm of the molecular weight M, log(M), on the horizontal axis and dw / dlog(M), which is obtained by differentiating the concentration fraction w with respect to the logarithm of the molecular weight log(M), on the vertical axis, the following conditions are satisfied: (1) the value of dw / dlog(M) reaches a maximum in the range of 4.5 ≤ log(M) ≤ 5.2, and (2) in the differential molecular weight distribution curve, the value obtained by integrating the value of dw / dlog(M) in the range of 4.0 ≤ log(M) ≤ 4.3 is 20% or less relative to the value obtained by integrating the value of dw / dlog(M) over the entire range of log(M).

Description

Technical Field

[0001] The present invention relates to the field of optical resins, and particularly to a thermoplastic resin composition, a manufacturing method thereof, and an optical lens. Background Art

[0002] The process of glass lenses is complex, with good light transmittance and stability, and is commonly used in professional equipment such as single-lens reflex cameras and high-end scanners. On the premise of ensuring product performance and stability, the cost of glass-plastic hybrid lenses is reduced, and various indicators are between those of plastic lenses and glass lenses. Security and automotive lenses use a combination of glass-plastic hybrid lenses. The outermost lens is still a glass lens because plastic lenses cannot withstand harsh outdoor or driving environmental conditions; the inner lenses are replaced with plastic lenses, which can reduce the weight of the lens, improve production efficiency, and reduce costs at the same time. In the mobile phone field, since it does not involve high-temperature and high-humidity application scenarios, plastic lenses are completely used.

[0003] Currently, optical polycarbonate has the advantages of high refractive index, easy molding, and high production efficiency. Patent US4810771 proposed a high-refractive polyester resin material for optical lenses, which was prepared using 9,9-bis-(4-hydroxyphenyl)fluorene as a monomer, and the refractive index could reach about 1.64. Later, Konica Patent JP2001072872 disclosed a thermoplastic resin material for optical lenses and its manufacturing method, mainly using 2,2-bis-(2-hydroxyethoxy)-1,1-binaphthalene as a polymerization monomer, which can be used to prepare optical resin materials such as polyester, polycarbonate, polyurethane, and sulfone polymer, and has a higher refractive index, reaching about 1.66. However, due to the presence of a conjugated benzene ring structure in these polymerization monomers and the defect of low degree of polymerization in the synthesis process, the color of optical polycarbonate turns yellow, thus affecting the light transmittance of plastic lenses at short-wave wavelengths (320 - 400 nm).

[0004] To solve this problem, the inventors of the present invention found that by controlling the molecular weight distribution of polycarbonate, the chain segment length and oligomer content of the polymer can be effectively controlled, thereby improving the high-temperature resistance, yellowing resistance, high transparency and other properties of polymer molecules. Summary of the Invention

[0005] The purpose of the present invention is to provide a thermoplastic resin composition, a manufacturing method thereof, and its application in the field of optical lenses. This thermoplastic resin has a high refractive index, and is characterized by high-temperature resistance, yellowing resistance, and high transparency, and can meet the usage requirements of optical lenses.

[0006] To solve the above problems, the present invention provides a thermoplastic resin composition. In the differential molecular weight distribution curve obtained by measuring the thermoplastic resin composition using gel permeation chromatography based on polystyrene, with the logarithm of the molecular weight M, log(M), on the horizontal axis and dw / dlog(M), where w is the concentration fraction differentiated with respect to log(M), on the vertical axis, the following conditions are satisfied:

[0007] (1) The value of dw / dlog(M) reaches a maximum in the range of 4.5 ≤ log(M) ≤ 5.2, preferably in the range of 4.6 ≤ log(M) ≤ 5.0;

[0008] (2) In the differential molecular weight distribution curve, the value obtained by integrating the value of dw / dlog(M) in the range of 4.0 ≤ log(M) ≤ 4.3 is 20% or less, preferably 10% or less, relative to the value obtained by integrating the value of dw / dlog(M) over the entire range of log(M).

[0009] The composition contains structural units derived from a compound represented by the general formula (A) and structural units derived from a compound represented by the general formula (B), where

[0010]

[0011] In the general formula (A), Z1 and Z2 represent aryl groups having 6 to 14 carbon atoms, preferably a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring; X1 and X2 each represent an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, more preferably a methylene group, an ethylene group, or a propylene group; R1 to R4 each independently represent a hydrogen atom, a halogen atom, a cyano group, 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, or an aryloxy group having 6 to 20 carbon atoms; the value of m can independently be 0 to 10; the value of n can independently be 0 to 4;

[0012]

[0013] In general formula (B), Y1 and Y2 each represent an alkylene group having 1 to 10 carbon atoms, or a linking group having 1 to 6 carbon atoms and having 1 to 2 carbon atoms on the main chain substituted by a sulfur atom; R5 to R8 each independently represent a hydrogen atom, a halogen atom, a cyano group, 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 or an aryloxy group having 6 to 20 carbon atoms; W represents a direct bond, -O-, -S-, -NH-, a sulfone group or a sulfoxide group, an alkylene group having 1 to 6 carbon atoms, a sub-cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms; the value of q is independently 0, 1, 2, 3;

[0014] Wherein, the molar ratio of the structural unit derived from the compound represented by general formula (A) to the structural unit derived from the compound represented by general formula (B) is 1 / 99 to 99 / 1, preferably 10 / 90 to 80 / 20;

[0015] There is no particular limitation on the form in which the structural units derived from the compounds represented by general formula (A) and general formula (B) according to the present invention are contained in the resin. For example, in the present invention, the thermoplastic resin composition may contain a copolymer containing the structural units derived from the compounds represented by general formula (A) and general formula (B), or may be a binary resin composition containing homopolymers composed of the respective structural units; or it may also be a blend obtained by blending a homopolymer containing the structural unit derived from the compound represented by general formula (A) with a homopolymer containing the structural unit derived from the compound represented by general formula (B), or a blend obtained by blending a homopolymer containing the structural unit derived from general formula (A) with a copolymer containing the structural unit derived from the compound represented by general formula (B).

[0016] The thermoplastic resin composition according to the present invention may include any structure of random, block and alternating copolymerization structures.

[0017] For the optical thermoplastic resin composition according to the present invention, the weight average molecular weight Mw of the thermoplastic resin is 10,000 to 200,000, preferably 20,000 to 90,000;

[0018] For the thermoplastic resin composition according to the present invention, the refractive index nD at 20 °C and a wavelength of 589 nm is 1.63 to 1.75, the Abbe number is not higher than 24, and the orientation birefringence Δn is 2.0×10 -3 Hereinafter, the glass transition temperature Tg is 130 to 180 °C;

[0019] The thermoplastic resin composition has 10 cm when measured at 260 °C under a load of 2.16 kg according to ISO 1133 3 / 10 minutes to 60 cm3 / Melt volume rate of 10 minutes;

[0020] The b value of the yellowness index measured for the thermoplastic resin composition at a thickness of 1 mm is not higher than 4.0, and the b value of the yellowness index measured at a thickness of 3 mm is not higher than 8.0;

[0021] For the thermoplastic resin composition at a thickness of 1 mm, the average transmittance at wavelengths from 780 nm to 1000 nm is 85% or more.

[0022] In the thermoplastic resin composition of the present invention, additives such as a release agent, an ultraviolet absorber, a fluidity improver, a crystal nucleating agent, a reinforcing agent, a dye, an antistatic agent, or an antibacterial agent can be added.

[0023] The thermoplastic resin composition of the present invention can be prepared by reacting a dihydroxy compound represented by general formula (A) and general formula (B) with a dicarbonate and / or a dicarboxylic acid and / or a dicarboxylic acid ester;

[0024] Preferably, the dihydroxy compound reacts with the dicarbonate and / or the dicarboxylic acid and / or the dicarboxylic acid ester in the presence of an alkaline compound catalyst, a transesterification catalyst, or a mixed catalyst composed of both, or under a catalyst-free condition, by melt transesterification polycondensation;

[0025] Preferably, the dihydroxy compound represented by general formula (A) is at least one of the following structures:

[0026]

[0027]

[0028] Preferably, the dihydroxy compound represented by general formula (B) is at least one of the following structures:

[0029]

[0030] In the present invention, the dicarbonate is one or more of diphenyl carbonate, dimethylxylene carbonate, diethylbenzene carbonate, diisopropylbenzene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc., preferably diphenyl carbonate;

[0031] The dicarboxylic acid is any one or a combination of at least two of terephthalic acid, terephthalic diacetic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2-biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,2'-bis(carboxymethoxy)-1,1'-binaphthalene, preferably terephthalic acid and / or 2,6-naphthalenedicarboxylic acid;

[0032] The dicarboxylic acid ester is any one or a combination of at least two of dimethyl terephthalate, diethyl terephthalate, dimethyl terephthalate diacetate, dimethyl 1,4-naphthalenedicarboxylate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl 2,2-biphenyldicarboxylate, dimethyl 1,4-cyclohexanedicarboxylate, and dimethyl 2,2'-bis(carboxymethoxymethyl)-1,1'-binaphthalene, preferably dimethyl terephthalate and / or dimethyl 2,6-naphthalenedicarboxylate;

[0033] The molar ratio of the sum of the carbonic acid diester and / or dicarboxylic acid and / or dicarboxylic acid ester to the sum of the dihydroxy compounds of the general formulas (A) and (B) added is 0.90 to 1.20:1, preferably 0.94 to 1.1:1;

[0034] The basic compound catalyst described in the present invention is one or several of lithium chloride, sodium chloride, potassium chloride, cesium chloride, lanthanum acetylacetonate, cerium acetylacetonate, 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, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenyl phosphate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylamine, dimethylbenzylamine, triphenylamine, diethylamine, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutyltetraphenylborate ammonium, and tetraphenyltetraphenylborate ammonium, etc., preferably one or several of sodium hydroxide, sodium bicarbonate, and cesium carbonate;

[0035] The transesterification catalyst described in the present invention can be one or several of zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride, tin acetate, cerium acetylacetonate, zirconium acetylacetonate, zirconium acetate, and tetrabutoxy zirconium, etc., preferably one or several of lanthanum acetylacetonate, zirconium acetate, and zinc acetate;

[0036] The molar ratio of the sum of the basic compound catalyst and / or transesterification catalyst added in the present invention to the sum of the dihydroxy compounds is 1×10 -7 ~1×10 -2 , preferably the ratio is 1×10 -6 ~5×10 -4 .

[0037] During the experiment, the inventors found that the polymerization activity of the dihydroxy compound represented by the general formula (B) is higher than that of the dihydroxy compound represented by the general formula (A). During the experiment, only the dihydroxy compound represented by the general formula (B) can be first put into the reaction kettle for prepolymerization to obtain a macromolecular prepolymer; then the dihydroxy compound represented by the general formula (A) is put into the reaction kettle for transesterification polycondensation, so as to increase the chain segment length of the polymer, reduce the generation of oligomers, and achieve the purpose of controlling the molecular weight distribution of the polymer.

[0038] In some preferred embodiments of the present invention, the preparation method of the thermoplastic resin composition includes: adding the dihydroxy compound represented by the general formula (B), carbonic acid diester and / or dicarboxylic acid and / or dicarboxylic acid ester, catalyst, and optional additives into the reactor, replacing the air in the reactor with nitrogen 3 to 5 times sufficiently, and then heating up to make the materials in the reactor molten, the melting temperature is 180 - 240 °C, preferably 190 - 220 °C, and the residence time at this stage is 40 - 100 min, preferably 50 - 80 min. After the materials are molten, start stirring, turn on the decompression or pressure control, and heat up to the transesterification reaction temperature, the transesterification reaction temperature is 210 - 250 °C, preferably 220 - 240 °C, and the residence time at this stage is 60 - 240 min, preferably 100 - 180 min. Then add the dihydroxy compound represented by the general formula (A) into the reactor and continue to react for 20 - 150 min, preferably 40 - 100 min. Then, continue to reduce the pressure and increase the temperature to start the polycondensation reaction. The system pressure at this stage is 10 - 500 Pa(A), preferably 50 - 100 Pa(A), the reaction temperature is 230 - 270 °C, preferably 230 - 255 °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 high molecular weight thermoplastic resin composition is obtained in the reactor.

[0039] The blend of the present invention can be obtained by blending different thermoplastic resin compositions obtained by polymerization in equipment such as an extruder, kneader, and mixer.

[0040] The present invention also relates to the application of the thermoplastic resin composition in the field of optical lenses.

[0041] The beneficial effects of the present invention are as follows:

[0042] The thermoplastic resin composition of the present invention has a high refractive index, good fluidity, is easy to process, high temperature resistant, yellowing resistant, and highly transparent, and can be used in the field of optical lenses. The optical lens using the thermoplastic resin composition of the present invention can make the lens thinner and lighter, reduce the number of lenses, thereby reducing costs, and has a wide application prospect. Description of the Drawings

[0043] Figure 1 It is the differential molecular weight distribution curve of the product of Example 1. Detailed implementation manners

[0044] The present invention will be described below in conjunction with the detailed implementation manners. It should be noted here that the examples are only used to further illustrate the present invention, and cannot be understood as limiting the protection scope of the present invention. Any non-substantive improvement and adjustment made according to the content of the present invention fall within the scope of protection of the present invention.

[0045] 1) Weight-average molecular weight (Mw): Using gel permeation chromatography (GPC), tetrahydrofuran was used as the eluent solvent, and a standard curve was made using standard polystyrene with a known molecular weight (molecular weight distribution = 1). Based on this standard curve, Mw was calculated from the retention time of GPC.

[0046] 2) Refractive index (nD): For a 1 mm thick film composed of the thermoplastic resin composition obtained in the examples, using an Abbe refractometer, the refractive index (nD) of the thermoplastic resin composition of the present invention at 20 °C and a wavelength of 589 nm was measured according to the method of JIS-K-7142.

[0047] 3) Abbe number: For a 0.1 mm thick film composed of the polycarbonate resin obtained in the examples, the refractive indices at wavelengths of 486 nm (F light), 589 nm (D light), and 656 nm (C light) at 20 °C were measured using an Abbe refractometer, and the Abbe number ν was further calculated using the following formula:

[0048] ν = (nD - 1) / (nF - nC).

[0049] 4) Orientation birefringence (Δn): After cutting a 0.1 mm thick cast film into a 5.0 cm square, the two ends of the film were inserted into chucks (3.0 cm between the chucks) and stretched to 1.5 times at Tg + 5 °C of the polycarbonate resin. The phase difference (Re) at 589 nm was measured using an ellipsometer, and the orientation birefringence (Δn) was calculated from the following formula:

[0050] Δn = Re / d

[0051] Δn: Orientation birefringence; Re: Phase difference; d: Thickness.

[0052] 5) Melt index: Measured according to ISO 1133 at 260 °C under a load of 2.16 kg.

[0053] 6) Light transmittance: For a 1 mm thick film composed of the polycarbonate resin obtained in the examples, the light transmittance at wavelengths from 780 nm to 1000 nm was measured using a turbidimeter according to the method of JIS-K-7361-1.

[0054] 7) b value: After drying the prepared polycarbonate resin in vacuum at 120 °C for 4 hours, an injection molding machine was used to perform injection molding at a barrel temperature of 270 °C and a mold temperature of Tg - 10 °C to obtain a disc-shaped test sheet with a diameter of 50 mm and a thickness of 1 mm. Using this sheet, the b value was measured in accordance with JIS K7105.

[0055] The sources of some of the reagent raw materials used in the examples and comparative examples of the present invention are as follows. For the remaining reagent raw materials, unless otherwise specified, they are all commercially available products:

[0056] A-1 was prepared according to the following method:

[0057] Weigh 194.3 g of β-anthrol and 68.6 g of 9-fluorenone into a three-necked flask, add 500 mL of toluene, and stir well until dissolved. A mixed solution of 0.99 g of concentrated sulfuric acid and 0.25 g of mercaptopropionic acid was slowly added dropwise to the above solution, and the mixture was heated to 65 °C and reacted for 3 h. After the reaction was completed, it was cooled to room temperature, and the system was neutralized to neutral with sodium hydroxide solution. 600 mL of anhydrous methanol was added, and the solid was fully precipitated, crushed, filtered, washed with methanol, and dried to obtain the bisphenol compound intermediate A.

[0058] Weigh 200 g of intermediate A and 4.56 g of potassium hydroxide and add them to 600 mL of N,N-dimethylformamide. Nitrogen was charged three times at 0.5 MPa, and the temperature was raised to 125 °C. Ethylene oxide gas was introduced, and the molar ratio of ethylene oxide to intermediate A was maintained at 2.45:1, and the reaction was carried out for 5 h. After the reaction was completed, it was cooled to room temperature, filtered, washed with water, and dried to obtain A-1. The NMR results of the target product are as follows: 1H-NMR(400 MHz, CDCl3) / δ×10 -6 : 8.25(s, 4H), 7.87 - 7.84(m, 6H), 7.7(s, 2H), 7.25(m, 2H), 7.38 - 7.11(m, 10H), 4.43(t, 4H), 3.69 - 3.65(m, 6H).

[0059] 2,2-bis(2-hydroxyethoxy)-6,6-diphenyl-1,1-binaphthalene (B-1) was prepared according to the following method:

[0060] Compound B-1 can be prepared with reference to the methods disclosed in Japanese Patent Laid-Open No. 2014-227387, Japanese Patent Laid-Open No. 2014-227388, and Japanese Patent Laid-Open No. 2015-168658, including (1) a method of reacting 1,1-binaphthol with ethylene glycol monotosylate, (2) a method of reacting binaphthol compounds with haloalkanol or alkylene carbonate, (3) a method of reacting 1,1-binaphthol with ethylene carbonate or propylene carbonate, etc. Among them, in the present invention, compound B-1 is prepared by a method of reacting binaphthol compounds with alkylene carbonate. The NMR results of the target product are as follows: 1H-NMR (400 MHz, CDCl3) δ / ×10 -6 : 8.07 (d, 2H), 7.95 - 7.77 (m, 6H), 7.52 - 7.41 (m, 10H), 7.11 (d, 2H), 4.43 (m, 4H), 3.69 - 3.65 (m, 6H).

[0061] Compound B-2 can be prepared with reference to the method disclosed in Chinese Patent CN112175178A, and compound B-3 can be prepared with reference to the method disclosed in Patent RO105571B1. The NMR results of compound B-2 are as follows: 1H-NMR (400 MHz, CDCl3) δ / ×10 -6 : 8.05 - 8.01 (m, 4H), 7.55 (m, 4H), 7.44 (m, 2H), 6.85 (d, 2H), 4.43 (t, 4H), 3.69 (m, 4H), 3.65 (m, 2H). The NMR results of compound B-3 are as follows: 1H-NMR (400 MHz, CDCl3) δ / ×10 -6 : 8.11 - 8.02 (m, 4H), 7.65 (m, 2H), 7.54 - 7.41 (m, 4H), 6.92 (m, 2H), 4.84 (s, 2H), 4.43 (t, 4H), 3.69 - 3.65 (m, 6H).

[0062] Example 1

[0063] 26.31 g (0.05 mol) of B1, 23.14 g (0.108 mol) of diphenyl carbonate, 84.01 μg (1.0×10 -6Put 16.8 g (0.2 mol) of sodium bicarbonate into a 200 ml four-necked flask equipped with a stirrer and a distillation device. Replace the air with nitrogen four times. Heat it to 200 °C under a nitrogen atmosphere of 101 Kpa(A). After heating for 60 min, confirm that the raw materials are completely dissolved. Then start stirring and adjust the pressure to 20 Kpa(A). At the same time, increase the temperature to 230 °C at a rate of 30 °C / hr. At this time, confirm that phenol, which is a by-product, starts to distill out. Maintain the reaction at 230 °C for 150 min. Then add 29.51 g (0.05 mol) of A2 to the flask and continue the reaction for 80 min. Then increase the temperature to 250 °C at a rate of 60 °C / hr. After the temperature reaches 250 °C, gradually reduce the pressure to 50 Pa(A) within 1 hour. Stir and react under this condition for 40 min to end the reaction. After the reaction is completed, fill the four-necked flask with nitrogen to return to normal pressure. Take out the resulting thermoplastic resin composition and conduct performance evaluation. The results are listed in Table 1.

[0064] Example 2

[0065] Put 15.79 g (0.03 mol) of B1, 12.18 g (0.03 mol) of B2, 22.06 g (0.103 mol) of diphenyl carbonate, and 3.274 mg (1.0×10 -5 mol) of zirconium acetate into a 200 ml four-necked flask equipped with a stirrer and a distillation device. Except for this, perform the same operations as in Example 1. Then add 23.61 g (0.04 mol) of A2 to the flask and continue to perform the same operations as in Example 1. Take the resulting thermoplastic resin composition and conduct performance evaluation. The results are listed in Table 1.

[0066] Example 3

[0067] Put 11.65 g (0.03 mol) of B3, 23.56 g (0.11 mol) of diphenyl carbonate, and 1.835 mg (1.0×10 -5 mol) of zinc acetate into a 200 ml four-necked flask equipped with a stirrer and a distillation device. Except for this, perform the same operations as in Example 1. Then add 11.81 g (0.02 mol) of A2 and 21.93 g (0.05 mol) of A3 to the flask and continue to perform the same operations as in Example 1. Take the resulting thermoplastic resin composition and conduct performance evaluation. The results are listed in Table 1.

[0068] Example 4

[0069] Put 40.21 g (0.099 mol) of B2, 19.28 g (0.09 mol) of diphenyl carbonate, and 4 μg (1.0×10 -7Put 0.4 g (0.01 mol) of sodium hydroxide into a 200 ml four-necked flask equipped with a stirrer and a distillation device. Otherwise, perform the same operations as in Example 1. Then add 0.64 g (0.001 mol) of A1 to the flask and continue to perform the same operations as in Example 1. The obtained thermoplastic resin composition was subjected to performance evaluation, and the results are listed in Table 1.

[0070] Example 5

[0071] Put 0.3882 g (0.001 mol) of B3, 25.71 g (0.12 mol) of diphenyl carbonate, and 84 mg (1.0×10 -3 mol) of sodium bicarbonate into a 200 ml four-necked flask equipped with a stirrer and a distillation device. Otherwise, perform the same operations as in Example 1. Then add 31.27 g (0.049 mol) of A1 and 29.51 g (0.05 mol) of A2 to the flask and continue to perform the same operations as in Example 1. The obtained thermoplastic resin composition was subjected to performance evaluation, and the results are listed in Table 1.

[0072] Example 6

[0073] Put 26.31 g (0.05 mol) of B1, 15.53 g (0.04 mol) of B3, 20.14 g (0.094 mol) of diphenyl carbonate, and 436.23 μg (1.0×10 -6 mol) of lanthanum acetylacetonate into a 200 ml four-necked flask equipped with a stirrer and a distillation device. Otherwise, perform the same operations as in Example 1. Then add 4.39 g (0.01 mol) of A3 to the flask and continue to perform the same operations as in Example 1. The obtained thermoplastic resin composition was subjected to performance evaluation, and the results are listed in Table 1.

[0074] Example 7

[0075] Put 8.12 g (0.02 mol) of B2, 22.49 g (0.105 mol) of diphenyl carbonate, and 162.9 mg (5.0×10 -4 mol) of cesium carbonate into a 200 ml four-necked flask equipped with a stirrer and a distillation device. Otherwise, perform the same operations as in Example 1. Then add 19.15 g (0.03 mol) of A1 and 29.51 g (0.05 mol) of A2 to the flask and continue to perform the same operations as in Example 1. The obtained thermoplastic resin composition was subjected to performance evaluation, and the results are listed in Table 1.

[0076] Comparative Example 1

[0077] Put 29.51 g (0.05 mol) of A2, 26.31 g (0.05 mol) of B1, 23.14 g (0.108 mol) of diphenyl carbonate, and 84.01 μg (1.0×10 -6 mol) of sodium bicarbonate into a 200 ml four-necked flask equipped with a stirrer and a distillation device. Otherwise, perform the same operations as in Example 1. For the obtained thermoplastic resin composition, conduct performance evaluation, and the results are listed in Table 1.

[0078] Table 1

[0079]

Claims

1. A thermoplastic resin composition, characterized in that, In the differential molecular weight distribution curve obtained by measuring the thermoplastic resin using gel permeation chromatography based on polystyrene, with the logarithm of the molecular weight log(M) on the horizontal axis and dw / dlog(M), where w is the concentration fraction differentiated with respect to log(M), on the vertical axis, the following conditions are satisfied: (1) The value of dw / dlog(M) reaches a maximum in the range of 4.5 ≤ log(M) ≤ 5.

2. (2) In the differential molecular weight distribution curve, the value obtained by integrating the value of dw / dlog(M) in the range of 4.0 ≤ log(M) ≤ 4.3 is 20% or less of the value obtained by integrating the value of dw / dlog(M) over the entire range of log(M). The thermoplastic resin composition contains structural units derived from a compound represented by the general formula (A) and structural units derived from a compound represented by the general formula (B), where In the general formula (A), Z1 and Z2 represent aryl groups having 6 to 14 carbon atoms; X1 and X2 each represent an alkylene group having 1 to 10 carbon atoms; R1 to R4 each independently represent a hydrogen atom, a halogen atom, a cyano group, 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, or an aryloxy group having 6 to 20 carbon atoms; the value of m is independently 0 to 10; the value of n is independently 0 to 4. In the general formula (B), Y1 and Y2 each represent an alkylene group having 1 to 10 carbon atoms, or a linking group having 1 to 6 carbon atoms with 1 to 2 carbon atoms on the main chain replaced by a sulfur atom; R5 to R8 each independently represent a hydrogen atom, a halogen atom, a cyano group, 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, or an aryloxy group having 6 to 20 carbon atoms; W represents a direct bond, -O-, -S-, -NH-, a sulfone group or a sulfoxide group, an alkylene group having 1 to 6 carbon atoms, a sub-cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms; the value of q is independently 0, 1, 2, 3.

2. The thermoplastic resin composition according to claim 1, wherein In the general formula (A), Z1 and Z2 represent a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring; X1 and X2 each represent an alkylene group having 1 to 6 carbon atoms.

3. The thermoplastic resin composition according to claim 2, wherein, In the general formula (A), X1 and X2 each represent a methylene group, an ethylene group, a propylene group.

4. The thermoplastic resin composition according to claim 1 or 2, characterized in that, The value of dw / dlog(M) reaches a maximum in the range of 4.6 ≤ log(M) ≤ 5.

0.

5. The thermoplastic resin composition according to any one of claims 1 to 3, characterized in that, In the differential molecular weight distribution curve, the value obtained by integrating the value of dw / dlog(M) in the range of 4.0 ≤ log(M) ≤ 4.3 is 10% or less of the value obtained by integrating the value of dw / dlog(M) over the entire range of log(M).

6. The thermoplastic resin composition according to claim 1, wherein The thermoplastic resin composition described above contains structural units derived from the compound represented by the general formula (A) and structural units derived from the compound represented by the general formula (B), wherein the molar ratio of the structural units derived from the compound represented by the general formula (A) to the structural units derived from the compound represented by the general formula (B) is 1 / 99 to 99 / 1.

7. The thermoplastic resin composition according to claim 6, characterized in that, The molar ratio of the structural units derived from the compound represented by the general formula (A) to the structural units derived from the compound represented by the general formula (B) is 10 / 90 to 80 / 20.

8. The thermoplastic resin composition according to any one of claims 1 to 3 and 6 to 7, characterized in that, The weight average molecular weight Mw of the thermoplastic resin is 10,000 to 200,000; and / or The thermoplastic resin composition has a refractive index nD of 1.63 to 1.75 at 20 °C and a wavelength of 589 nm, an Abbe number of not more than 24, and an orientation birefringence Δn of 2.0×10 -3 Hereinafter, the glass transition temperature Tg is 130 to 180 °C; and / or The thermoplastic resin composition has a melt volume rate of 10 cm 3 / 10 minutes to 60 cm 3 / 10 minutes as measured according to ISO 1133 at 260 °C under a load of 2.16 kg; and / or The yellowness index b value measured for the thermoplastic resin composition at a thickness of 1 mm is not higher than 4.0, and the yellowness index b value measured at a thickness of 3 mm is not higher than 8.0; and / or For the thermoplastic resin composition at a thickness of 1 mm, the average transmittance at wavelengths of 780 nm to 1000 nm is 85% or more.

9. The thermoplastic resin composition according to claim 8, wherein, The weight average molecular weight Mw of the thermoplastic resin is 20,000 to 90,000.

10. The method for preparing a thermoplastic resin composition according to any one of claims 1 to 9, characterized in that, The transesterification polycondensation or esterification polycondensation of the dihydroxy compounds represented by the structural general formula (A) and the structural general formula (B) with a carbonic acid diester and / or a dicarboxylic acid and / or a dicarboxylic acid ester is carried out; Wherein, In the general formula (A), Z1 and Z2 represent aryl groups having 6 to 14 carbon atoms; X1 and X2 each represent an alkylene group having 1 to 10 carbon atoms; R1 to R4 each independently represent a hydrogen atom, a halogen atom, a cyano group, 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 or an aryloxy group having 6 to 20 carbon atoms; the value of m is independently 0 to 10; the value of n is independently 0 to 4; In the general formula (B), Y1 and Y2 each represent an alkylene group having 1 to 10 carbon atoms, or a linking group having 1 to 6 carbon atoms and having 1 to 2 carbon atoms on the main chain substituted by a sulfur atom; R5 to R8 each independently represent a hydrogen atom, a halogen atom, a cyano group, 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 or an aryloxy group having 6 to 20 carbon atoms; W represents a direct bond, -O-, -S-, -NH-, a sulfone group or a sulfoxide group, an alkylene group having 1 to 6 carbon atoms, a sub-cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms; the value of q is independently 0, 1, 2, 3.

11. The method for preparing the thermoplastic resin composition according to claim 10, characterized in that, In the general formula (A), Z1 and Z2 represent a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring; X1 and X2 each represent an alkylene group having 1 to 6 carbon atoms.

12. The method for preparing the thermoplastic resin composition according to claim 11, wherein In the general formula (A), X1 and X2 each represent a methylene group, an ethylene group, a propylene group.

13. The method for preparing the thermoplastic resin composition according to claim 10, wherein Including: The dihydroxy compound represented by the general formula (B), a carbonic acid diester and / or a dicarboxylic acid and / or a dicarboxylic acid ester, a catalyst, and optionally an auxiliary agent are added to a reactor, and the temperature is raised to melt the materials in the reactor, and the melting temperature is 180 to 240 °C, and the residence time at this stage is 40 to 100 min; After the material is melted, the temperature is raised to the transesterification reaction temperature, which is 210 - 250°C. The residence time at this stage is 60 - 240 min. Then, the dihydroxy compound shown by the general formula (A) is added to the reactor and the reaction continues for 20 - 150 min. Then, the pressure is further reduced and the temperature is raised to start the polycondensation reaction. The system pressure at this stage is 10 - 500 Pa, the reaction temperature is 230 - 270°C, and the residence time is 10 - 120 min.

14. The method for preparing a thermoplastic resin composition according to any one of claims 10 to 13, characterized in that, The molar ratio of the dicarbonate and / or dicarboxylic acid and / or dicarboxylic acid ester to the total of the added dihydroxy compounds of the general formulas (A) and (B) is 0.90 - 1.20:

1.

15. The method for preparing a thermoplastic resin composition according to claim 14, characterized in that, The molar ratio of the dicarbonate and / or dicarboxylic acid and / or dicarboxylic acid ester to the total of the added dihydroxy compounds of the general formulas (A) and (B) is 0.94 - 1.1:

1.

16. Use of the thermoplastic resin composition according to any one of claims 1 - 9 or the thermoplastic resin composition prepared by the preparation method according to any one of claims 10 - 15, wherein the thermoplastic resin composition is used for an optical lens.

Images