Thermoplastic resin, method for producing same, optical resin composition, and optical device

Abstract

The invention relates to a thermoplastic resin and a preparation method thereof, an optical resin composition and an optical device. The thermoplastic resin is formed by polymerizing a first monomer and a second monomer, and the first monomer comprises one or more of dibasic ester and dicarboxylic acid; the second monomer comprises a monomer A, a monomer B and a monomer C. The thermoplastic resin has excellent ultraviolet (UV) aging resistance while maintaining high Abbe number, refractive index and light transmittance. (A) (B) (C)

Description

Technical Field

[0001] This application relates to the field of optical resin technology, and in particular to a thermoplastic resin and its preparation method, an optical resin composition, and an optical device. Background Technology

[0002] With the rapid development of optical technology, the demand for high-performance optical materials is increasing. Optical resins, due to their significant advantages such as light weight, ease of processing and molding, and high design flexibility, are gradually replacing traditional glass. Furthermore, as people's living standards improve, more and more people are enthusiastic about outdoor activities, leading to increasingly higher requirements for the UV resistance of optical resins. UV light triggers photo-oxidative degradation reactions in resins, resulting in surface powdering, cracking, yellowing, embrittlement, and severe deterioration of core optical properties (such as light transmittance).

[0003] Polycarbonate, a lightweight and highly impact-resistant engineering plastic, is widely used in eyeglass lenses, optical lenses, and electronic display panels. However, ordinary polycarbonate has a low Abbe number and significant dispersion, leading to chromatic aberration in imaging and affecting visual clarity, making it difficult to meet the requirements of high-end optical devices. Methods exist to copolymerize diesters / carboxylic acids with dihydroxy compounds of specific structures to prepare thermoplastic resins with high Abbe numbers, refractive indices, and light transmittance as optical resins. However, for outdoor applications (UV protection), these modification methods are insufficient. Summary of the Invention

[0004] Based on this, this application provides thermoplastic resins and their preparation methods, optical resin compositions, and optical devices. The thermoplastic resins, while maintaining high Abbe numbers, refractive indices, and light transmittance, exhibit excellent resistance to ultraviolet (UV) aging.

[0005] A first aspect of this application provides a thermoplastic resin formed by polymerization of a first monomer and a second monomer, wherein the first monomer comprises one or more of a diester and a dicarboxylic acid;

[0006] The second monomer includes monomer A, monomer B, and monomer C;

[0007] The monomer A has the structural features shown in the following formula (A):

[0008] (A),

[0009] Wherein, each X is an alkylene group from C1 to C4;

[0010] R1 and R2 are each independently H, halogen, or C1~C4 alkyl;

[0011] Z1 ring is a C5~C10 cycloalkyl group;

[0012] The monomer B has the structural features shown in the following formula (B):

[0013] (B)

[0014] In each of these, Y is an independent C1~C4 alkylene group;

[0015] R3, R4, R5 and R6 are each independently H, halogen, C1~C6 alkyl, C1~C6 alkoxy, C5~C10 cycloalkyl, C5~C10 heterocyclic, C6~C14 aryl or C6~C14 heteroaryl;

[0016] Each of the Z2 rings is independently a C6~C14 aryl group;

[0017] m and n are each independent integers from 1 to 4;

[0018] The monomer C has the structural features shown in the following formula (C):

[0019] (C),

[0020] R7 and R8 are each independently H, halogen, C1~C6 alkyl, C1~C6 alkoxy, C5~C10 cycloalkyl, C5~C10 heterocyclic, C6~C14 aryl or C6~C14 heteroaryl.

[0021] In some of these embodiments, formula (A) has one or more of the following features:

[0022] (1) Each of X is an alkylene group of C1 to C2;

[0023] (2) R1 and R2 are each independently H;

[0024] (3) Ring Z1 is or ;

[0025] Optionally, monomer A comprises one or more of the following compounds:

[0026] (A-1) and (A-2).

[0027] In some of these embodiments, formula (B) has one or more of the following features:

[0028] (1) Each Y is an independent C2~C3 alkylene group;

[0029] (2) R3, R4, R5 and R6 are each independently H, phenyl or naphthyl, and can be H or phenyl;

[0030] (3) Each of the Z2 rings is independently phenyl, naphthyl, anthraceneyl or phenanthrene, and may be phenyl;

[0031] Optionally, monomer B comprises one or more of the following compounds:

[0032] (B-1) and (B-2).

[0033] In some implementations, R7 and R8 in equation (C) are each independently H.

[0034] In some embodiments, the first monomer:

[0035] The diester includes one or more of diesters and dicarboxylic acid esters;

[0036] Optionally, the carbonate diester includes one or more of diphenyl carbonate, dimethyl carbonate, diethylphenyl carbonate, diisopropylphenyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate, and may further include diphenyl carbonate.

[0037] Optionally, the dicarboxylic acid ester includes one or more of dimethyl terephthalate, diethyl terephthalate, dimethyl terephthalate, dimethyl 1,4-naphthalenedicarboxylate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl 2,2-biphenyl dicarboxylate, dimethyl 1,4-cyclohexanedicarboxylate, and 2,2'-bis(carboxymethyl methoxy)-1,1'-binaphthyl, and may further include one or both of dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate;

[0038] The dicarboxylic acid includes one or more of terephthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2-biphenyl dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, and may further include one or both of terephthalic acid and 2,6-naphthalenedicarboxylic acid.

[0039] In some embodiments, in the second monomer, monomer A is 10% to 50%, monomer B is 5% to 80%, and monomer C is 2% to 75% by molar percentage.

[0040] In some embodiments, the molar ratio of the first monomer to the second monomer is (1~1.1):1, and can be (1.03~1.07):1.

[0041] A second aspect of this application provides a method for preparing the thermoplastic resin described in the first aspect, comprising the following steps:

[0042] The first monomer and the second monomer are mixed to carry out a polymerization reaction;

[0043] Optionally, the polymerization reaction is carried out in the presence of a catalyst;

[0044] Further, optionally, the catalyst comprises a basic compound catalyst and / or an transesterification catalyst;

[0045] Optionally, the polymerization reaction is a melt transesterification polycondensation method.

[0046] A third aspect of this application provides an optical resin composition comprising the thermoplastic resin described in the first aspect and functional additives.

[0047] Optionally, the functional additives include one or more of the following: release agents, ultraviolet absorbers, flow improvers, crystal nucleating agents, reinforcing agents, dyes, antistatic agents, and antibacterial agents.

[0048] A fourth aspect of this application provides an optical device comprising the thermoplastic resin described in the first aspect or the optical resin composition described in the third aspect.

[0049] The above-mentioned thermoplastic resins, by using suitable monomers for polymerization, can form thermoplastic resins that maintain high Abbe number, refractive index and light transmittance while having excellent resistance to ultraviolet (UV) aging, making them suitable for outdoor optical devices. Detailed Implementation

[0050] The following detailed description, in conjunction with specific embodiments, illustrates the thermoplastic resin and its preparation method, the optical resin composition, and the optical device of this application. This application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0051] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0052] As used herein, the terms “and / or,” “or / and,” and “and / or” may include any one of two or more of the related listed items, as well as any and all combinations of the related listed items, including any two related listed items, any more related listed items, or a combination of all the related listed items.

[0053] In this article, "one or more" refers to any one, two or more of the listed items.

[0054] In this application, terms such as "first aspect," "second aspect," "third aspect," and "fourth aspect" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, terms such as "first," "second," "third," and "fourth" serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0055] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0056] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0057] Unless otherwise specified, the percentage content mentioned in this application refers to mass percentage for solid-liquid mixtures and solid-phase-solid mixtures, and volume percentage for liquid-phase-liquid mixtures.

[0058] Unless otherwise specified, all percentage concentrations mentioned in this application refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of that component.

[0059] Unless otherwise specified, the temperature parameters in this application may be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows for temperature fluctuations within the precision range controlled by the instrument.

[0060] In this application, room temperature generally refers to 4℃~30℃, and preferably 20±5℃.

[0061] In this document, the term "alkyl" refers to a monovalent residue formed by the loss of a hydrogen atom from a saturated hydrocarbon containing a primary (normal) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof. Phrases containing this term, such as "C1-C4 alkyl," refer to alkyl groups containing 1 to 4 carbon atoms, and each occurrence can be independently referred to as C1 alkyl, C2 alkyl, C3 alkyl, and C4 alkyl. Suitable examples include, but are not limited to: methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(CH3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3). "C1~C6 alkyl" refers to alkyl groups containing 1 to 6 carbon atoms. Each occurrence can be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl, which will not be elaborated further here. Correspondingly, "alkylene" refers to a divalent residue formed by losing a hydrogen atom from an alkyl group.

[0062] "Halogen" refers to F, Cl, Br or I.

[0063] "Alkoxy" refers to a group with the structure -O-alkyl, i.e., an alkyl group as defined above connected to an adjacent group via an oxygen atom. Phrases containing this term, such as "C1~C6 alkoxy," refer to alkyl moieties containing 1 to 6 carbon atoms, and each occurrence can be independently C1 alkoxy, C2 alkoxy, C3 alkoxy, C4 alkoxy, C5 alkoxy, or C6 alkoxy. Suitable examples include, but are not limited to: methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt), and tert-butoxy (-OC(CH3)3 or -OtBu).

[0064] "Cycloalkyl" refers to a non-aromatic hydrocarbon containing a ring of carbon atoms, which can be monocycloalkyl, spirocycloalkyl, or bridged cycloalkyl. Phrases containing this term, such as "C5-C10 cycloalkyl," refer to cycloalkyl compounds containing 5 to 10 carbon atoms, and each occurrence can independently be C5-cycloalkyl, C6-cycloalkyl, C7-cycloalkyl, C8-cycloalkyl, C9-cycloalkyl, or C10-cycloalkyl. Suitable examples include, but are not limited to, cyclopentyl, cyclohexyl, and cycloheptyl.

[0065] "Heterocyclic group" refers to a cycloalkyl group in which at least one carbon atom is replaced by a non-carbon atom. The non-carbon atom can be an N atom, O atom, S atom, etc., and can be a saturated ring or a partially unsaturated ring. Phrases containing this term, such as "C5-C10 heterocyclic group," refer to heterocyclic groups containing 5 to 10 carbon atoms, and each occurrence can independently be a C5 heteroalkyl, C6 heteroalkyl, C7 heteroalkyl, C8 heteroalkyl, C9 heteroalkyl, or C10 heteroalkyl. Suitable examples include, but are not limited to: dihydropyridyl, tetrahydropyridyl (piperidinyl), tetrahydrothiophenyl, sulfur-oxidized tetrahydrothiophenyl, tetrahydrofuranyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and dihydroindolyl.

[0066] "Aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing one hydrogen atom. It can be a monocyclic aryl, fused-ring aryl, or polycyclic aryl. For polycyclic compounds, at least one ring must be an aromatic ring system. For example, "C6-C14 aryl" refers to an aryl group containing 5 to 10 carbon atoms, and each occurrence can be independently C6, C7, C8, C9, C10, C11, C12, C13, or C14 aryl. Suitable examples include, but are not limited to: benzene, biphenyl, naphthalene, anthracene, phenanthrene, dinaphthalene, triphenylene, and their derivatives.

[0067] In this document, the term "heteroaryl" refers to an aryl group in which at least one carbon atom is replaced by a non-carbon atom, which can be an N atom, O atom, S atom, etc. For example, "C6~C14 heteroaryl" refers to a heteroaryl group containing 6 to 14 carbon atoms, and each occurrence can be independently C6 heteroaryl, C7 heteroaryl, C8 heteroaryl, C9 heteroaryl, C10 heteroaryl, C11 heteroaryl, C12 heteroaryl, C13 heteroaryl, and C14 heteroaryl. Suitable examples include, but are not limited to: benzofuranyl, benzothiopheneyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiopheneyl, furanopyrrolyl, furanofuranyl, thienofuranyl, benzoisoxazolyl, benzoisothiazolyl, and benzoimidazolyl.

[0068] Some embodiments of this application provide a thermoplastic resin formed by polymerization of a first monomer and a second monomer, wherein the first monomer comprises one or more of a diester and a dicarboxylic acid;

[0069] The second monomer includes monomer A, monomer B, and monomer C;

[0070] The monomer A has the structural features shown in the following formula (A):

[0071] (A),

[0072] Wherein, each X is an alkylene group from C1 to C4;

[0073] R1 and R2 are each independently H, halogen, or C1~C4 alkyl;

[0074] Z1 ring is a C5~C10 cycloalkyl group;

[0075] Understandably, ring With ring Dense connections between them;

[0076] The monomer B has the structural features shown in the following formula (B):

[0077] (B)

[0078] In each of these, Y is an independent C1~C4 alkylene group;

[0079] R3, R4, R5 and R6 are each independently H, halogen, C1~C6 alkyl, C1~C6 alkoxy, C5~C10 cycloalkyl, C5~C10 heterocyclic, C6~C14 aryl or C6~C14 heteroaryl;

[0080] Each of the Z2 rings is independently a C6~C14 aryl group;

[0081] m and n are each independent integers from 1 to 4;

[0082] The monomer C has the structural features shown in the following formula (C):

[0083] (C),

[0084] R7 and R8 are each independently H, halogen, C1~C6 alkyl, C1~C6 alkoxy, C5~C10 cycloalkyl, C5~C10 heterocyclic, C6~C14 aryl or C6~C14 heteroaryl.

[0085] Without limitation, the polymerization method can be transesterification polycondensation and / or esterification polycondensation, and the resulting thermoplastic resin can be one or more of polyester, polycarbonate, and polyester carbonate, and can be a copolymer containing corresponding structural units of each monomer. It can contain any structure including random, block, and alternating copolymer structures.

[0086] Specifically, in formula (A):

[0087] In some embodiments, X is each independently a C1-C2 alkylene group, for example a methylene group.

[0088] In some implementations, R1 and R2 are each independently H.

[0089] In some implementations, the Z1 ring is... or .

[0090] Without limitation, monomer A comprises one or more of the following compounds:

[0091] (A-1) and (A-2).

[0092] Specifically, in formula (B):

[0093] In some embodiments, Y is independently a C2-C3 alkylene group, for example, an ethyl group.

[0094] In some embodiments, R3, R4, R5, and R6 are each independently H, phenyl, or naphthyl. Further, R3, R4, R5, and R6 are each independently H or phenyl.

[0095] In some embodiments, each of the Z2 rings is independently phenyl, naphthyl, anthraceneyl, or phenanthryl. Further, each of the Z2 rings is independently phenyl.

[0096] Without limitation, monomer B comprises one or more of the following compounds:

[0097] (B-1) and (B-2).

[0098] Specifically, in equation (C):

[0099] In some embodiments, R7 and R8 are each independently H. Accordingly, the monomer C comprises:

[0100] (C-1).

[0101] In some embodiments, the first monomer includes one or more of a diester and a dicarboxylic acid ester.

[0102] Without limitation, the diester includes one or more of diphenyl carbonate, dimethyl carbonate, diethylphenyl carbonate, diisopropylphenyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. In some embodiments, the diester includes diphenyl carbonate.

[0103] Without limitation, the dicarboxylic acid ester includes one or more of dimethyl terephthalate, diethyl terephthalate, dimethyl terephthalate, dimethyl 1,4-naphthalenedicarboxylate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl 2,2-biphenyl dicarboxylate, dimethyl 1,4-cyclohexanedicarboxylate, and 2,2'-bis(carboxymethyl methoxy)-1,1'-binaphthalate. In some embodiments, the dicarboxylic acid ester includes one or both of dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate.

[0104] In some embodiments, the dicarboxylic acid in the first monomer comprises one or more of terephthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2-biphenyl dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl. In some embodiments, the dicarboxylic acid comprises one or both of terephthalic acid and 2,6-naphthalenedicarboxylic acid.

[0105] In some embodiments, the second monomer comprises, by molar percentage, 10% to 50% monomer A, 5% to 80% monomer B, and 2% to 75% monomer C. Specifically, the molar percentage of monomer A includes, but is not limited to: 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or any two of the foregoing; the molar percentage of monomer B includes, but is not limited to: 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 48%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, or any two of the foregoing; and the molar percentage of monomer C includes, but is not limited to: 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or any two of the foregoing.

[0106] In some embodiments, the molar ratio of the first monomer to the second monomer is (1~1.1):1. Specifically, the molar ratio of the first monomer to the second monomer includes, but is not limited to: 1:1, 1.03:1, 1.05:1, 1.07:1, 1.1:1, or any range between the foregoing. The molar ratio of the first monomer to the second monomer is (1.03~1.07):1.

[0107] In some embodiments, the thermoplastic resin has the following characteristics:

[0108] (1) The refractive index nD at 20℃ and wavelength 589nm is 1.52~1.63;

[0109] (2) The Abbe number is 25-50;

[0110] (3) Orientation birefringence Δn is 1×10 -3 the following;

[0111] (4) The average transmittance is above 89% when the wavelength is 780nm~1000nm;

[0112] (5) The yellowness change value Δb≤3 of the 3mm specimen after 14 days of QUV aging test (ASTM G154), the average transmittance of the specimen under wavelength of 780nm~1000nm is above 89%, and the tensile strength (refer to ISO-527 standard injection molding tensile specimen) is above 80MPa.

[0113] Some embodiments of this application provide a method for preparing the thermoplastic resin as described above, comprising the following steps:

[0114] The first monomer and the second monomer are mixed and subjected to a polymerization reaction.

[0115] Without limitation, the polymerization reaction can be carried out in the presence of a catalyst, or it can be carried out using melt transesterification polycondensation. Understandably, when using melt transesterification polycondensation, a catalyst may not be required.

[0116] In some embodiments, the polymerization reaction can be carried out in the presence of a catalyst, including basic compound catalysts and / or transesterification catalysts.

[0117] Without limitation, the alkaline compound catalyst comprises one or more 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, tetramethylborohydride, tetrabutylammonium borohydride, tetrabutyltetraphenylborate, and tetraphenyltetraphenylborate. In some embodiments, the alkaline compound catalyst comprises one or more of sodium hydroxide, sodium bicarbonate, and cesium carbonate.

[0118] Without limitation, the transesterification catalyst includes one or more of zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride, tin acetate, cerium acetylacetone, zirconium acetylacetone, zirconium acetate, and tetrabutoxyzirconium. In some embodiments, the transesterification catalyst includes one or more of lanthanum acetylacetone, zirconium acetate, and zinc acetate.

[0119] Without limitation, the molar ratio of the catalyst to the second monomer can be 5 × 10⁻⁶. -7 ~2×10 -2 Specifically, this molar ratio includes, but is not limited to: 5 × 10⁻⁶ -7 1.0×10 -5 mol, 5.0 × 10 -4 mol, 2×10 -2 In some embodiments, the molar ratio of the catalyst to the second monomer is 1 × 10⁻⁶. -5 ~5×10 -4 .

[0120] Without limitation, the method for preparing the thermoplastic resin includes the following steps:

[0121] The first monomer, the second monomer, and the catalyst are added to the reactor. The air in the reactor is fully replaced with nitrogen 3 to 5 times. Then the temperature is raised to melt the material in the reactor. The melting temperature is 180℃ to 210℃, or 190℃ to 200℃. The residence time in this stage is 40 min to 100 min, or 50 min to 80 min.

[0122] After the materials melt, start stirring and activate pressure control (either depressurization or pressurization) to raise the temperature to the first temperature, which is 210℃~250℃, optionally 220℃~240℃. The residence time in this stage is 60min~320min, optionally 150min~240min, and this stage mainly involves reactions such as transesterification. Then, continue to reduce the pressure and increase the temperature to initiate the polycondensation reaction. The system pressure in this stage is 10Pa~500Pa(A), preferably 50Pa~100Pa(A), the reaction temperature is 230℃~270℃, optionally 230℃~255℃, and the residence time is 10min~120min, optionally 20min~60min. Understandably, small molecule compounds generated during the reaction are immediately removed by distillation.

[0123] Other embodiments of this application provide optical resin compositions comprising the thermoplastic resin as described above and functional additives. Without limitation, the functional additives include one or more of the following: release agents, ultraviolet absorbers, flow improvers, nucleating agents, reinforcing agents, dyes, antistatic agents, and antibacterial agents, which may be added according to application and process requirements. It is understood that the functional additives may be blended after the thermoplastic resin is prepared, or they may be added simultaneously during the polymerization reaction of the first and second monomers.

[0124] Other embodiments of this application provide optical devices, including the thermoplastic resin described above or the optical resin composition described above. Without limitation, the optical devices may include, for example, optical molded bodies, optical lenses, and optical films.

[0125] For experimental parameters not specified in the following specific embodiments, please refer to the guidelines given in this application document first, or refer to experimental manuals or other experimental methods known in the art, or refer to the experimental conditions recommended by the manufacturer.

[0126] The raw materials and reagents involved in the following specific embodiments can be obtained commercially or prepared by those skilled in the art using known methods.

[0127] Monomer A can be converted into a polycyclic diene via the Diels-Aldell reaction, and then into a polycyclic diol via hydroformylation. The Diels-Aldell reaction and hydroformylation are well-known techniques.

[0128] Monomer B can be prepared by reacting 9-fluorenone with phenoxyethanol under the combined action of a strong acid catalyst and a mercapto compound as an auxiliary catalyst. This technique is well known.

[0129] Monomer C can be prepared by direct dehydration cyclization of sorbitol under an acidic catalyst, a well-known technique.

[0130] Example 1

[0131] This embodiment provides a thermoplastic resin, and the preparation method is as follows:

[0132] 1.96 g (0.01 mol) of A-1, 47.22 g (0.08 mol) of B-1, 1.46 g (0.01 mol) of C-1, 21.42 g (0.10 mol) of diphenyl carbonate, and 1.63 μg (5.0 × 10⁻⁶) of [unclear - possibly a specific compound or ingredient]. -8Cesium carbonate (mol) was placed in a 200 mL four-necked flask equipped with a stirrer and distillation apparatus. The flask was purged with nitrogen four times and heated to 120 °C under a nitrogen atmosphere of 101 kPa (A). After heating for 60 min to confirm complete dissolution of the raw materials, stirring was started, and the pressure was adjusted to 25 kPa (A). Simultaneously, the temperature was increased to 210 °C at a rate of 30 °C / hr. At this point, phenol, a byproduct, began to distill off. The reaction was maintained at 210 °C for 180 min, then increased to 230 °C at a rate of 60 °C / hr. Once the temperature reached 230 °C, the pressure was gradually reduced to 50 Pa (A) over one hour, and the reaction was continued under stirring for 60 min. The reaction was then terminated. After the reaction, nitrogen was introduced into the four-necked flask to restore atmospheric pressure. The flask was then removed, pelletized, and molded to obtain the thermoplastic resin.

[0133] Example 2

[0134] This embodiment provides a thermoplastic resin, prepared in the same way as in Embodiment 1, but with the main difference being the amount and type of raw materials.

[0135] Specifically: 11.11g (0.05mol) A-2, 21.03g (0.048mol) B-2, 0.29g (0.002mol) C-1, 23.56g (0.11mol) diphenyl carbonate, and 43.6μg (1.0×10⁻⁶) were added. -6 Lanthanum acetylacetone (mol) was placed in a 200 mL four-necked flask equipped with a stirrer and distillation apparatus, and otherwise the same procedure as in Example 1 was performed.

[0136] Example 3

[0137] This embodiment provides a thermoplastic resin, prepared in the same way as in Embodiment 1, but with the main difference being the amount and type of raw materials.

[0138] Specifically: 3.92g (0.02mol) A-1, 2.19g (0.005mol) B-2, 10.95g (0.075mol) C-1, 22.06g (0.103mol) diphenyl carbonate, and 917.5μg (5.0×10⁻⁶) were added. -5 1 mol) of zinc acetate was placed in a 200 mL four-necked flask equipped with a stirrer and distillation apparatus, and the same procedure as in Example 1 was performed.

[0139] Example 4

[0140] This embodiment provides a thermoplastic resin, prepared in the same way as in Embodiment 1, but with the main difference being the amount and type of raw materials.

[0141] Specifically: 3.33g (0.015mol) A-1, 17.71g (0.03mol) B-1, 8.03g (0.055mol) C-1, 22.92g (0.107mol) diphenyl carbonate, and 16.80mg (2.0×10) -3 Sodium bicarbonate (mol) was placed in a 200 ml four-necked flask equipped with a stirrer and distillation apparatus, and otherwise the same operation as in Example 1 was performed.

[0142] Comparative Example 1

[0143] This comparative example provides a thermoplastic resin, prepared in the same way as in Example 1, except that monomer C-1 is not used.

[0144] Specifically: 0.02 mol A-1, 0.08 mol B-1, 0.1 mol diphenyl carbonate, 5.0 × 10 -8 1 mol of cesium carbonate was placed in a 200 mL four-necked flask equipped with a stirrer and distillation apparatus, and otherwise the same operation as in Example 1 was performed.

[0145] Comparative Example 2

[0146] This comparative example provides a thermoplastic resin, prepared in the same way as in Example 1, except that monomer B-1 is not used.

[0147] Specifically: 0.01 mol A-1, 0.09 mol C-1, 0.1 mol diphenyl carbonate, 5.0 × 10 -8 1 mol of cesium carbonate was placed in a 200 mL four-necked flask equipped with a stirrer and distillation apparatus, and otherwise the same operation as in Example 1 was performed.

[0148] Comparative Example 3

[0149] This comparative example provides a thermoplastic resin, prepared in the same way as in Example 1, except that monomer A-1 is not used.

[0150] Specifically: 0.09 mol B1, 0.01 mol C1, 0.1 mol diphenyl carbonate, and 5.0 × 10⁻⁶ mol of methyl methacrylate (MCP) were added. -8 1 mol of cesium carbonate was placed in a 200 mL four-necked flask equipped with a stirrer and distillation apparatus, and otherwise the same operation as in Example 1 was performed.

[0151] Test example:

[0152] 1) Weight-average molecular weight (Mw): Using gel permeation chromatography (GPC), a standard curve was prepared using tetrahydrofuran as the developing solvent and 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.

[0153] 2) Refractive index (nD): The prepared thermoplastic resin composition was made into a film with a thickness of 1 mm. The refractive index (nD) of the material at 20 °C and wavelength of 589 nm was determined using an Abbe refractometer according to the method of JIS-K-7142.

[0154] 3) Abbe number: The prepared thermoplastic resin composition was made into a film with a thickness of 0.1 mm. The refractive index at wavelengths of 486 nm, 589 nm, and 656 nm at 23 °C was measured using an Abbe refractometer. The Abbe number ν was then calculated using the following formula:

[0155] ν=(nD-1) / (nF-nC)

[0156] nD: The refractive index of the material at a wavelength of 589 nm;

[0157] nF: The refractive index of the material at a wavelength of 486 nm;

[0158] nC: The refractive index of the material at a wavelength of 656 nm.

[0159] 4) Orientation birefringence (Δn): After cutting a 0.1 mm thick cast film into 5.0 cm squares, insert both ends of the film into chucks (3.0 cm apart) and stretch it to 1.5 times its original strength at Tg+5℃ of polycarbonate resin. Use an ellipsometer to measure the phase difference (Re) at 589 nm, and calculate the orientation birefringence (Δn) using the following formula.

[0160] Δn=Re / d

[0161] Re: phase difference; d: thickness.

[0162] 5) Light transmittance: The prepared thermoplastic resin composition was made into a film with a thickness of 1 mm, and the average light transmittance at wavelengths of 780 nm to 1000 nm was measured using a turbidimeter according to the method of JIS-K-7361-1.

[0163] 6) Tensile strength: The resin granules were injection molded at 245℃ with reference to the ISO-527 standard to test the tensile strength of the specimen.

[0164] 7) Anti-UV aging:

[0165] 7.1 Yellowing change value Δb: The resin granules were injection molded into a 3mm thick sample at 245℃. After 14 days of QUV aging test (ASTM G154), the yellowing change value Δb of the sample before and after aging was measured.

[0166] 7.2 Tensile strength after aging: Tensile strength was tested again after 14 days of QUV aging test (ASTM G154).

[0167] 7.3 Transmittance after aging: After 14 days of QUV aging test (ASTM G154), the transmittance was repeated.

[0168] The test results are shown in Table 1 below:

[0169] Table 1

[0170]

[0171] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0172] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A thermoplastic resin, characterized in that, Formed by polymerization of a first monomer and a second monomer, wherein the first monomer comprises one or more of a diester and a dicarboxylic acid; The second monomer includes monomer A, monomer B, and monomer C; The monomer A has the structural features shown in equation (A): （A）， Wherein, each X is an alkylene group from C1 to C4; R1 and R2 are each independently H, halogen, or C1~C4 alkyl; Z1 ring is a C5~C10 cycloalkyl group; The monomer B has the structural features shown in the following formula (B): （B）， In each of these, Y is an independent C1~C4 alkylene group; R3, R4, R5 and R6 are each independently H, halogen, C1~C6 alkyl, C1~C6 alkoxy, C5~C10 cycloalkyl, C5~C10 heterocyclic, C6~C14 aryl or C6~C14 heteroaryl; Each of the Z2 rings is independently a C6~C14 aryl group; m and n are each independent integers from 1 to 4; The monomer C has the structural features shown in the following formula (C): （C）， R7 and R8 are each independently H, halogen, C1~C6 alkyl, C1~C6 alkoxy, C5~C10 cycloalkyl, C5~C10 heterocyclic, C6~C14 aryl or C6~C14 heteroaryl.

2. The thermoplastic resin according to claim 1, characterized in that, Equation (A) has one or more of the following characteristics: (1) Each of X is an alkylene group of C1 to C2; (2) R1 and R2 are each independently H; (3) Ring Z1 is or ; Optionally, monomer A comprises one or more of the following compounds: (A-1) Sum (A-2).

3. The thermoplastic resin according to claim 1, characterized in that, Equation (B) has one or more of the following characteristics: (1) Each Y is an independent C2~C3 alkylene group; (2) R3, R4, R5 and R6 are each independently H, phenyl or naphthyl, and can be H or phenyl; (3) Each of the Z2 rings is independently phenyl, naphthyl, anthraceneyl or phenanthrene, and may be phenyl; Optionally, monomer B comprises one or more of the following compounds: (B-1) and (B-2).

4. The thermoplastic resin according to claim 1, characterized in that, In equation (C), R7 and R8 are each independently represented by H.

5. The thermoplastic resin according to claim 1, characterized in that, In the first monomer: The diester includes one or more of diesters and dicarboxylic acid esters; Optionally, the carbonate diester includes one or more of diphenyl carbonate, dimethyl carbonate, diethylphenyl carbonate, diisopropylphenyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate, and may further include diphenyl carbonate. Optionally, the dicarboxylic acid ester includes one or more of dimethyl terephthalate, diethyl terephthalate, dimethyl terephthalate, dimethyl 1,4-naphthalenedicarboxylate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl 2,2-biphenyl dicarboxylate, dimethyl 1,4-cyclohexanedicarboxylate, and 2,2'-bis(carboxymethyl methoxy)-1,1'-binaphthyl, and may further include one or both of dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate; The dicarboxylic acid includes one or more of terephthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2-biphenyl dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, and may further include one or both of terephthalic acid and 2,6-naphthalenedicarboxylic acid.

6. The thermoplastic resin according to claim 1, characterized in that, In the second monomer, monomer A is 10%~50%, monomer B is 5%~80%, and monomer C is 2%~75% by molar percentage.

7. The thermoplastic resin according to any one of claims 1 to 6, characterized in that, The molar ratio of the first monomer to the second monomer is (1~1.1):1, and can be selected as (1.03~1.07):

1.

8. A method for preparing the thermoplastic resin according to any one of claims 1 to 7, characterized in that, Includes the following steps: The first monomer and the second monomer are mixed to carry out a polymerization reaction; Optionally, the polymerization reaction is carried out in the presence of a catalyst; Further, optionally, the catalyst comprises a basic compound catalyst and / or an transesterification catalyst; Optionally, the polymerization reaction is a melt transesterification polycondensation method.

9. An optical resin composition, characterized in that, Includes the thermoplastic resin as described in any one of claims 1 to 7 and the functional additives; Optionally, the functional additives include one or more of the following: release agents, ultraviolet absorbers, flow improvers, crystal nucleating agents, reinforcing agents, dyes, antistatic agents, and antibacterial agents.

10. An optical device, characterized in that, It includes the thermoplastic resin according to any one of claims 1 to 7 or the optical resin composition according to claim 9.

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