High-refraction polymer and application thereof

Abstract

The invention belongs to the technical field of high-refraction polymers, and particularly relates to a high-refraction polymer and application thereof in the field of optical lenses. The high refractive polymer includes: (1) a repeating structural unit derived from a silicon-containing monomer compound; the silicon-containing monomer compound is shown as a general formula (X1n) or a general formula (X2n); (2) one or more of a repeating structural unit derived from a compound represented by general formula (A) and a repeating structural unit derived from a compound represented by general formula (B); the high-refraction polymer is suitable for preparing optical lenses or optical films, the impact strength and the flaking rate of the high-refraction polymer are remarkably improved, and meanwhile the water absorption rate is obviously reduced. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of high-refractive polymers, and in particular relates to a high-refractive polymer and an application thereof in the field of optical lenses. Background Art

[0002] Optical glass and optical resin are the two main materials for cameras. Among them, optical resin has gradually become the mainstream of the market due to its advantages such as easy molding, high production efficiency and low cost.

[0003] The mainstream optical resins on the market currently include: high-refractive PC (polycarbonate), high-refractive polyester, cycloolefin polymer COC and COP. Among them, high-refractive PC is an indispensable material in optical lenses because of its high refractive index.

[0004] Patent document CN201310062561.X discloses a polycarbonate containing 9,9-bis-(4-(2-hydroxyethoxy)phenyl)fluorene and its derivatives. The resin can be used to produce an optical lens with high refractive index, low Abbe number, low birefringence, high transparency and high glass transition temperature (heat resistance).

[0005] Patent document CN104769007A discloses a polycarbonate containing 2,2-bis-(2-hydroxyethoxy)-1,1-binaphthyl and its derivatives; the polycarbonate resin exhibits physical properties such as high refractive index, low Abbe number, high transparency, a glass transition temperature suitable for injection molding, and low birefringence; in addition, by using the resin, an excellent optical lens with substantially no optical deformation can be obtained.

[0006] Patent document CN110741030A discloses a polycarbonate containing 9,9-bis(4-(2-hydroxyethoxy)phenyl)dinaphthylfluorene structural units; the thermoplastic resin has a high refractive index, can reduce birefringence and achieve a balance between heat resistance and formability.

[0007] However, the products disclosed in the above patent documents are prone to stress cracking and poor impact performance at low temperatures due to the large number of macrocyclic structures contained in the materials themselves, which limits the application of polycarbonate resin materials in low-temperature places. In addition, there are also defects such as relatively poor resistance to wet and hot aging, easy water absorption and degradation during processing, causing the lens to turn white after injection molding, affecting the performance of the material.

[0008] The introduction of polysiloxane into polycarbonate resin materials can significantly improve the flame retardancy, low temperature resistance, hydrolysis resistance and other properties of the materials. Therefore, the performance of polysiloxane during polymerization will significantly affect the properties of the copolymer and its resin material after polymerization.

[0009] In view of this, continuing to research and develop polycarbonate resins that introduce polysiloxane into their molecular structures becomes a direction worth exploring. Summary of the invention

[0010] In view of the problems existing in the prior art, the purpose of the present invention is to provide a high-refractive polymer and its application. By constructing the molecular structure and introducing a special siloxane structure into the structural system, the low-temperature resistance, hydrolysis resistance, scratch resistance and other properties of the resin material can be improved; the high-refractive polymer of the present invention is suitable for preparing optical lenses or optical films, and its impact strength and film formation rate are significantly improved, while the water absorption rate is significantly reduced.

[0011] In order to achieve the above object, the present invention provides the following technical solutions:

[0012] In a first aspect, a high refractive polymer is provided, comprising the following structural units:

[0013] (1) A repeating structural unit derived from a silicon-containing monomer compound; the silicon-containing monomer compound is represented by the general formula (X1n) or the general formula (X2n); wherein,

[0014] The general formula (X1n) is as follows:

[0015]

[0016] The general formula (X2n) is as follows:

[0017]

[0018] In the general formula (X1n) and the general formula (X2n), n is each independently 1-10 (e.g., 2, 3, 4, 5, 6, 7, 8, 9), preferably 2-7;

[0019] (2) any one or more of the repeating structural units derived from the compound represented by the general formula (A) and the repeating structural units derived from the compound represented by the general formula (B); wherein,

[0020] The general formula (A) is as follows:

[0021]

[0022] In the general formula (A), R 1 , R 2 Each of them is independently a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C5-C20 cycloalkyl group, a C5-C20 cycloalkoxy group, a C6-C20 aryl group, or a C6-C20 aryloxy group, preferably a hydrogen atom, a C1-C3 alkyl group, or a C6-C12 aryl group;

[0023] The general formula (B) is as follows:

[0024]

[0025] In the general formula (B), R 3 , R 4 Each of them is independently a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C5-C20 cycloalkyl group, a C5-C20 cycloalkoxy group, a C6-C20 aryl group, or a C6-C20 aryloxy group, and is preferably a hydrogen atom, a C1-C3 alkyl group, or a C6-C12 aryl group.

[0026] In some embodiments, the high refractive polymer comprises the following structural units:

[0027] (1) A repeating structural unit derived from a silicon-containing monomer compound;

[0028] (2) Repeating structural units derived from the compound represented by general formula (A).

[0029] In some embodiments, the high refractive polymer comprises the following structural units:

[0030] (1) A repeating structural unit derived from a silicon-containing monomer compound;

[0031] (2) Repeating structural units derived from the compound represented by general formula (B).

[0032] In some embodiments, the high refractive polymer comprises the following structural units:

[0033] (1) A repeating structural unit derived from a silicon-containing monomer compound;

[0034] (2) Repeating structural units derived from the compound represented by the general formula (A) and repeating structural units derived from the compound represented by the general formula (B).

[0035] In some embodiments, the structural formula of the high refractive polymer may be a compound shown in the following formula I or formula II:

[0036]

[0037] In Formula I and Formula II, R 1 , R 2 are independently a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C5-C20 cycloalkyl group, a C5-C20 cycloalkoxy group, a C6-C20 aryl group, or a C6-C20 aryloxy group, preferably a hydrogen atom, a C1-C3 alkyl group, or a C6-C12 aryl group; R 3 , R 4They are independently hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, C5-C20 cycloalkyl, C5-C20 cycloalkoxy, C6-C20 aryl, C6-C20 aryloxy, preferably hydrogen atom, C1-C3 alkyl, C6-C12 aryl; n appearing in each repeating structural unit can be independently 1-10.

[0038] In Formula I and Formula II, the values ​​of L, M, and N can be determined based on the (molar or mass) proportions of the repeating structural units derived from the compound represented by the general formula (A), the repeating structural units derived from the compound represented by the general formula (B), and the repeating structural units derived from the silicon-containing monomer compound contained in the high-refractive polymer.

[0039] In the text, C1-C20 alkyl groups may be, for example, methyl, ethyl, n-propyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, C12 alkyl, C16 alkyl, etc. C1-C20 alkoxy groups may be, for example, methoxy, ethoxy, propoxy, C12 alkoxy, C16 alkoxy, etc. C5-C20 cycloalkyl groups may be, for example, C6 cycloalkyl, C10 cycloalkyl, C12 cycloalkyl, etc. C6-C20 aryl groups may be, for example, phenyl, naphthyl, etc.

[0040] In some embodiments, in the high refractive polymer, the ratio of each repeating structural unit is as follows:

[0041] The molar ratio of the repeating structural unit derived from the compound represented by the general formula (A) to the repeating structural unit derived from the silicon-containing monomer compound is (0 to 99):1 (for example, 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 8:1, 10:1, 12:1, 15:1, 18:1, 20:1, 40:1, 50:1, 60:1, 85:1, 90:1, 95:1), preferably (1 to 20:1);

[0042] The molar ratio of the repeating structural unit derived from the compound represented by general formula (B) to the repeating structural unit derived from the silicon-containing monomer compound is (0 to 99):1 (for example, 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 8:1, 10:1, 12:1, 15:1, 18:1, 20:1, 40:1, 50:1, 60:1, 85:1, 90:1, 95:1), preferably (1 to 20:1);

[0043] Furthermore, the contents of the repeating structural unit derived from the compound represented by the general formula (A) and the repeating structural unit derived from the compound represented by the general formula (B) are not 0 at the same time.

[0044] In the high refractive polymer of this invention, the terminal hydroxyl group mainly comes from the silicon-containing monomer compound, the compound represented by the general formula (A), and the compound represented by the general formula (B).

[0045] In some embodiments, in the high refractive polymer, the terminal hydroxyl content is less than or equal to 1000 ppm (e.g., 950 ppm, 900 ppm, 800 ppm, 600 ppm, 400 ppm, 250 ppm, 200 ppm, 150 ppm, 100 ppm, 50 ppm), preferably 300-500 ppm.

[0046] In the high refractive polymer herein, the small molecule byproducts may include phenol, which is mainly derived from carbonic acid diester.

[0047] In some embodiments, the content of small molecule by-products in the high refractive polymer is less than or equal to 500 ppm (e.g., 450 ppm, 400 ppm, 350 ppm, 280 ppm, 250 ppm, 220 ppm, 200 ppm, 180 ppm, 150 ppm, 80 ppm, 50 ppm, 20 ppm), preferably 100-300 ppm.

[0048] In some embodiments, the compound represented by the general formula (A) is selected from at least one of the compound BPEF (9,9-bis[(4-hydroxyethoxy)phenyl]fluorene) and the compound BPPF (9,9-bis[4-(1-pyrenyl)phenyl]fluorene); wherein,

[0049] The compound BPEF is shown in the following structural formula:

[0050]

[0051] The compound BPPF is shown in the following structural formula:

[0052]

[0053] In some embodiments, the compound represented by the general formula (B) is selected from at least one of the compound BHEBN (2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl) and the compound BHEBBN (2,2'-bis(2-hydroxyethoxy)-5,5'-diphenyl-1,1'-binaphthyl); wherein,

[0054] The compound BHEBN is shown in the following structural formula:

[0055]

[0056] The compound BHEBBN is shown in the following structural formula:

[0057]

[0058] In the present invention, there is no particular requirement for the source of the silicon-containing monomer compound, which can be directly purchased or made by oneself. For example, in some embodiments, those skilled in the art can prepare it by any feasible method based on the preparation method disclosed in the prior art and as needed, and the present invention does not particularly limit the specific preparation process.

[0059] In some embodiments, the silicon-containing monomer compound is a product prepared by the following method:

[0060] (1) contacting o-allylphenol or p-allylphenol with siloxane and performing an esterification reaction to prepare an intermediate C;

[0061] (2) contacting ethylene oxide with the intermediate C obtained in step (1) and performing a polymerization reaction to prepare the silicon-containing monomer compound.

[0062] In the method for preparing the silicon-containing monomer compound recorded in the text, the operation process described in step (1) is a process disclosed in the prior art, and the present invention does not make special restrictions and requirements. For example, it can be implemented with reference to the content recorded on page 6 of the document "Master's Thesis Synthesis and Performance Research of Siloxane Bisphenol / Para-Substituted Aniline Benzoxazine, Hebei University, Wang Rongrong", Chapter 2 Synthesis and Characterization of Siloxane Bisphenol / Para-Substituted Aniline Benzoxazine". The operation process described in step (2) is a process disclosed in the prior art, and the present invention does not make special restrictions and requirements. For example, it can be prepared with reference to the content disclosed in the document: "Synthesis Research of High Refractive Index Optical Resin Monomer Phenyl Diether Fluorene, Contemporary Chemical Research, 2022, 24, 180-182".

[0063] In order to obtain the silicon-containing monomer compound, the method for preparing the silicon-containing monomer compound of the present invention may include the following process conditions:

[0064] In some embodiments, in step (1), the general structural formula of the siloxane is as shown below:

[0065] In the formula, n=1-10 (e.g., 2, 3, 4, 5, 6, 7, 8, 9), preferably n=2-7.

[0066] In some embodiments, in step (1), the molar ratio of o-allylphenol or p-allylphenol to siloxane is 1:(0.5-0.75), for example, 1:0.54, 1:0.56, 1:0.58, 1:0.6, 1:0.62, 1:0.63, 1:0.64, preferably 1:(0.55-0.65).

[0067] In some embodiments, in step (1), the conditions of the esterification reaction include: the reaction temperature is 50-100°C (for example, 55°C, 65°C, 70°C, 80°C, 85°C, 95°C), preferably 60-90°C; the reaction time is 1-12h (for example, 1.5h, 3h, 5h, 8h, 10h), preferably 2-6h.

[0068] In some embodiments, in step (1), the esterification reaction is carried out in the presence of catalyst-I, which is a Castel catalyst; the molar amount of catalyst-I is 0.1-1 mol% of the molar amount of Si-H, for example, 0.2 mol%, 0.4 mol%, 0.5 mol%, 0.6 mol%, 0.8 mol%, 0.9 mol%.

[0069] In some embodiments, in step (2), the molar ratio of ethylene oxide to the intermediate C obtained in step (1) is 1:(0.4-0.5), for example, 1:0.42, 1:0.44, 1:0.45, 1:0.48, 1:0.49, preferably 1:(0.43-0.47).

[0070] In some embodiments, in step (2), the conditions of the polymerization reaction include: the reaction temperature is 60-90°C (for example, 62°C, 70°C, 75°C, 80°C, 88°C), preferably 65-85°C; the reaction time is 3-8h (for example, 3.5h, 4.5h, 5h, 6.5h, 7h), preferably 4-6h.

[0071] In some embodiments, in step (2), the polymerization reaction is carried out under the action of catalyst-II, and the catalyst-II is sodium hydroxide; the molar ratio of catalyst-II to ethylene oxide is 0.05:(0.1-1), for example, 0.05:0.15, 0.05:0.2, 0.05:0.4, 0.05:0.5, 0.05:0.6, 0.05:0.8.

[0072] In the present invention, the preparation process of the high refractive polymer may not be particularly limited. For example, it may be implemented with reference to the existing preparation methods disclosed in the art; for example, it may refer to the contents recorded in patent document CN 114957954 A.

[0073] In some embodiments, the high refractive polymer is a product obtained by contacting and polymerizing a compound represented by the general formula (A) and / or a compound represented by the general formula (B), a silicon-containing monomer compound, and a carbonic acid diester.

[0074] In some examples, in order to obtain the high refractive polymer, the preparation method used in the present invention includes the following process conditions:

[0075] In some embodiments, the molar ratio of the total amount of the compound represented by the general formula (A), the compound represented by the general formula (B), and the silicon-containing monomer compound to the amount of the carbonate diester is (0.9-1):1, for example, 0.92:1, 0.94:1, 0.95:1, 0.96:1, 0.98:1, and preferably (0.93-1):1.

[0076] In some embodiments, the molar fraction of the silicon-containing monomer compound used in the total amount of the compound represented by the general formula (A), the compound represented by the general formula (B), and the silicon-containing monomer compound is 1 mol%-10 mol%, for example, 1.5 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 8 mol%, 9 mol%.

[0077] In some embodiments, the carbonic acid diester is selected from at least one of diphenyl carbonate, ditolyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate, preferably selected from at least one of diphenyl carbonate and ditolyl carbonate.

[0078] In some embodiments, the high refractive polymer is prepared by melt transesterification polycondensation in the presence or absence of a polymerization catalyst.

[0079] In some embodiments, the polymerization catalyst is selected from at least one of sodium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylamine, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride, tin acetate, cerium acetylacetonate, zirconium acetylacetonate, zirconium acetate and tetrabutoxyzirconium, preferably selected from at least one of sodium hydroxide, sodium bicarbonate, cesium carbonate, cerium acetylacetonate, zirconium acetate and zinc acetate.

[0080] In some embodiments, the molar ratio of the polymerization catalyst to the carbonic acid diester is 1×10 -8 ~1×10 -3 , for example, 2×10 -8 , 5×10 -8 , 1×10 -7 , 5×10 -7 , 2×10 -6 , 5×10 -6 , 1×10 -5 ,,2×10 -5 , 5×10 -5 , 5×10 -4 , preferably 1×10 -6 ~1×10 -4 .

[0081] In the method for preparing the high-refractive polymer as described above, the polymerization reaction specifically includes: a material melting stage, an ester exchange stage, and a polycondensation stage; wherein:

[0082] The conditions of the melting stage include: a melting temperature of 100 to 250°C (e.g., 120°C, 150°C, 180°C, 240°C), preferably 140 to 200°C, a residence time of 20 to 50 min (e.g., 25 min, 35 min, 45 min), preferably 30 to 40 min;

[0083] The conditions of the transesterification stage include: a pressure of 20 to 80 KPa (e.g., 25 KPa, 30 KPa, 40 KPa, 50 KPa, 60 KPa, 70 KPa), a reaction temperature of 140 to 280° C. (e.g., 150° C., 180° C., 200° C., 260° C.), preferably 170 to 250° C., a reaction time of 30 to 180 min (e.g., 35 min, 40 min, 50 min, 80 min, 100 min, 120 min, 150 min), preferably 60 to 90 min;

[0084] The conditions of the polycondensation stage include: a pressure of 5 to 1000 Pa (A) (e.g., 6 Pa (A), 10 Pa (A), 20 Pa (A), 40 Pa (A), 60 Pa (A), 80 Pa (A), 100 Pa (A), 200 Pa (A), 500 Pa (A), 800 Pa (A)), preferably 50 to 150 Pa (A), a temperature of 200 to 350° C. (e.g., 220° C., 240° C., 260° C., 320° C., 340° C.), preferably 250 to 300° C., and a time of 5 to 90 min (e.g., 6 min, 10 min, 18 min, 20 min, 30 min, 40 min, 50 min, 80 min), preferably 15 to 60 min. During the reaction, the generated small molecule compounds are immediately removed by distillation.

[0085] The high refractive polymer of the present invention is particularly suitable for preparing optical lenses or optical films.

[0086] In some embodiments, the weight average molecular weight of the high refractive polymer is 10,000 to 150,000 (e.g., 15,000, 40,000, 50,000, 80,000, 100,000, 120,000, 140,000), preferably 20,000 to 130,000, and more preferably 30,000 to 120,000; the molecular weight distribution is 1.5-3.0, for example, 1.6, 1.8, 2.0, 2.2, 2.4, 2.5, 2.8, 2.9.

[0087] In some embodiments, the refractive index of the high refractive polymer at 23° C. and a wavelength of 589 nm is 1.625 to 1.685, for example, 1.628, 1.630, 1.635, 1.64, 1.65, 1.66, or 1.68.

[0088] In some embodiments, the Abbe number of the high refractive polymer is no greater than 24, for example, 23, 22, 20, 18, 16, 15, 14, 12, 10, 9, 8, 6, 5, 4, 2, or 1.

[0089] In some embodiments, the transmittance of the high refractive polymer is greater than or equal to 88% (e.g., 90%, 92%, 94%, 95%, 96%, 98%), the haze is less than or equal to 0.7% (e.g., 0.5%, 0.4%, 0.3%, 0.2%, 0.15%, 0.1%), and the b value is less than or equal to 2 (e.g., 1.8, 1.6, 1.5, 1.2, 1.0, 0.8, 0.5).

[0090] In a second aspect, a use of the high refractive polymer as described above in an optical lens is provided.

[0091] In the present invention, the method for applying the high-refractive polymer in the field of optical lenses can be achieved through conventional operations in the art, which will not be described in detail.

[0092] In the art, high-refractive polyesters contain a large number of rigid rings (such as naphthalene rings) in their structures, which limit the internal rotation of the molecular chain segments. In addition, the strong polar carbonate bonds they contain also provide a large intermolecular force, which binds the molecular chains to each other, further increasing the rigidity of the polymer materials, thereby increasing the difficulty of processing these polymer materials. In addition, the large number of carbonate bonds in the material are highly hygroscopic and sensitive to moisture, and are prone to degradation; conventional high-refractive PC products have poor scratch resistance, and yellowing is obvious when exposed to ultraviolet rays for a long time, which affects the user experience of end users.

[0093] The present invention can significantly improve the above problems by introducing special silicon-containing monomer compounds into the polymer structure; the introduction of the selected organic silicon group into the polymer molecular chain can increase the length of the structural unit and increase the flexibility of the molecular chain, thereby improving the processability of the product, especially significantly improving the impact strength and the film forming rate; at the same time, the "-Si-O-Si-" in the organic siloxane is a hydrophobic group, which can effectively change the surface properties of the material and reduce the water absorption rate of the material, which not only greatly improves the hydrolysis resistance of the polycarbonate product, but also improves the dimensional stability of the material; and the introduction of silicon increases the hardness and oxidation resistance of the material, thereby improving the wear resistance and yellowing resistance of the material.

[0094] Compared with the prior art, the technical solution of the present invention has at least the following beneficial effects:

[0095] The present invention can improve the processability of the product by introducing a special silicon-containing monomer compound into the polymer structure, especially significantly improving the impact strength and the film-forming rate; the obtained polymer material has the characteristics of good wear resistance, low water absorption, easy processing, etc., and is particularly suitable for the application of aspherical small-sized products such as optical lenses, and the film-forming rate is significantly improved; at the same time, the obtained polymer material also has a stable high light transmittance, which greatly improves the yellowing, degradation and other phenomena that occur during the product reprocessing process, and can meet the use requirements of multi-lens lenses. DETAILED DESCRIPTION

[0096] In order to understand the technical features and contents of the present invention in detail, the preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described in the embodiments, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described here.

[0097] Unless otherwise specified, the experimental procedures used in the following examples are all conventional methods.

[0098] The raw materials, reagents, etc. used in the following examples can all be obtained from commercial sources; the specific information of some raw materials is as follows:

[0099] Diphenyl carbonate: purchased from Shanghai Titan;

[0100] The compound represented by general formula (A), BPEF, was purchased from Jiangsu Yongxing;

[0101] The compound represented by general formula (A), BPPF, was purchased from Jiangsu Yongxing;

[0102] The compound represented by general formula (B), BHEBN, was purchased from Jiangsu Yongxing;

[0103] The compound represented by the general formula (B), 2,2-bis(2-hydroxyethoxy)-5,5-diphenyl-1,1-binaphthyl (BHEBBN): prepared by referring to the method described in paragraph

[0080] of patent document CN 114957954 A;

[0104] The silicon-containing monomer compound (compound represented by the general formula X1n and X2n) is prepared by the following steps:

[0105] (1) o-allylphenol or p-allylphenol is mixed with siloxane for esterification reaction to prepare intermediate C (compounds represented by general formula C1n and general formula C2n). The specific operation process and process conditions can be in accordance with the literature "Master's thesis Synthesis and performance study of siloxane bisphenol / para-substituted aniline type benzoxazine, Hebei University, Wang Rongrong", Chapter 2 Synthesis and characterization of siloxane bisphenol / para-substituted aniline type benzoxazine", page 6;

[0106]

[0107] In the general formulas C1n and C2n, n=1-10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9;

[0108] (2) Ethylene oxide is polymerized with the intermediate C prepared in step (1) to prepare silicon-containing monomer compounds represented by general formula (X1n) and general formula (X2n). The specific operation process and process conditions can refer to the content recorded in the document "Synthesis Research of High Refractive Index Optical Resin Monomer Phenyl Diether Fluorene, Contemporary Chemical Research, 2022, 24, 180-182".

[0109]

[0110] In the general formula (X1n) and the general formula (X2n), n=1-10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9.

[0111] The performance testing methods of the polymers obtained in each embodiment and comparative example are as follows:

[0112] 1) Weight average molecular weight (Mw) and molecular weight distribution (PDI): A gel permeation chromatograph (GPC) was used with dichloromethane as the developing solvent and a standard polystyrene with a known molecular weight (molecular weight distribution = 1) was used to prepare a standard curve; based on the standard curve, the Mw and PDI of the polymer sample to be tested were calculated from the retention time of GPC.

[0113] 2) Water absorption rate: The polymer sample to be tested is immersed in 23°C distilled water, the weight change before and after is measured with a balance, and then the water absorption rate is calculated.

[0114] 3) Test of polymer terminal hydroxyl content and small molecule by-product (such as phenol, alcohol, etc.) content: After the polymer sample to be tested is dissolved in dichloromethane, it is derivatized by trifluoroacetic anhydride, and then the derivatized product is tested for nuclear magnetic resonance 19F spectrum, and fluorobenzene is used as internal standard for quantification; during the test, if the small molecule by-product includes phenol, the derivatized sample will have a peak at -74.7ppm in the spectrum, from which its content can be calculated; the derivatized sample will have a peak at -74.8ppm in the spectrum, from which the content of primary hydroxyl can be calculated, and the derivatized sample will have a peak at -75.3ppm in the spectrum, from which the content of secondary hydroxyl can be calculated;

[0115] Instrument used: Bruker AVANCE NEO 600M spectrometer; Test probe: 5mm BBO probe; Test solvent: CDCl 3 ; Test temperature: 25℃.

[0116] 4) Refractive index (nD): The refractive index of the polymer sample to be tested was measured at 23° C. and a wavelength of 589 nm using an Abbe refractometer according to the method of GB / T 7962.4-2010.

[0117] 5) Abbe number: Use an Abbe refractometer to measure the refractive index of the polymer sample at wavelengths of 486 nm, 589 nm and 656 nm at 23°C, and further calculate the Abbe number ν using the following formula:

[0118] ν=(nD-1) / (nF-nC); where:

[0119] nD represents the refractive index at a wavelength of 589 nm at 23°C;

[0120] nF represents the refractive index at a wavelength of 486 nm at 23°C;

[0121] nC represents the refractive index at a wavelength of 656 nm at 23°C;

[0122] The refractive index at a wavelength of 486 nm at 23° C. and the refractive index at a wavelength of 656 nm at 23° C. can also be obtained by the refractive index testing method given above.

[0123] 6) Transmittance and haze: The polymer sample to be tested was measured using a turbidity meter according to the method of JIS-K-7361-1.

[0124] 7) b value: Use an injection molding machine to perform injection molding on the polymer sample at a barrel temperature of 270°C and a mold temperature of Tg-10°C to obtain a disc-shaped test plate piece with a diameter of 50 mm and a thickness of 3 mm; use the plate piece and determine its b value according to the JIS K7105 method.

[0125] 8) Impact test: The notched cantilever beam impact strength is tested on the polymer sample in an environment of 25° C. and 50% relative humidity according to ASTM D256. The testing machine model is Instron CEAST 9050.

[0126] 9) Spherical lens processing: The polymer sample to be tested is vacuum dried at 120°C for 8 hours and then injection molded; wherein, the molding temperature is Tg+110°C, the mold temperature is Tg-10°C, and the polymer sample to be tested is injected into a lens sample with a thickness of 0.2mm, a convex curvature radius of 5mm, a concave curvature radius of 4mm, and a diameter of 5mm using a SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd.

[0127] Example 1

[0128] The preparation process of the silicon-containing monomer compound represented by formula X21 is as follows:

[0129] (1) In the presence of a Custer catalyst, p-allyl phenol and siloxane are mixed for esterification reaction at a temperature of 60° C. for 6 hours; wherein the molar amount of the Custer catalyst is 0.2 mol% of Si—H, and the molar ratio of p-allyl phenol to siloxane is 1:0.55; and finally an intermediate represented by formula C21 is obtained;

[0130] Wherein, the structural formula of the siloxane is:

[0131]

[0132] (2) In the presence of sodium hydroxide as a catalyst, ethylene oxide is mixed with the intermediate represented by formula C21 obtained in step (1) for polymerization reaction, and the reaction is carried out at 65° C. for 6 hours; wherein the molar ratio of ethylene oxide to the intermediate represented by formula C21 is 1:0.43, and the molar ratio of the amount of catalyst sodium hydroxide to ethylene oxide is 0.05:1, and finally a silicon-containing monomer compound represented by formula X21 is obtained.

[0133] The preparation steps of high refractive polymer are:

[0134] 0.036 mol BPEF, 0.057 mol BHEBN, 0.005 mol silicon-containing monomer compound of formula X21 prepared above, 0.1 mol diphenyl carbonate, and 5.0×10 -71 mol sodium hydroxide was added into a reaction kettle equipped with a stirrer and a distillation device; nitrogen was introduced for replacement 3 times, and the mixture was heated to 132°C at normal pressure and kept for 30 min. After the raw materials were completely melted, stirring was started, and the system pressure was adjusted to 40 KPa(A), and the temperature was raised to 235°C. By-products began to distill out, and the reaction was maintained for 80 min under this condition; then the system was heated to 250°C, and the pressure was reduced by program, and the system pressure was gradually reduced to 80 Pa(A) within 1 hour. The reaction was continued for 30 min under this condition to terminate the reaction.

[0135] The generated high-refractive polymer was taken out and the performance was evaluated. The physical properties of the obtained high-refractive polymer were as follows:

[0136] The hydroxyl content at the polymer end was 889 ppm, and the free small molecule byproduct content was 230 ppm;

[0137] The molecular weight of the polymer is 120120, PDI is 1.9, the refractive index at 23°C and wavelength of 589nm is 1.641, the Abbe number is 21.2, the transmittance is 89.9%, the haze is 0.35%, the b value is 1.32, and the Tg is 135°C;

[0138] The polymer has an Izod notched impact strength of 52 J / m 2 , water absorption rate is 0.08%;

[0139] The polymer was processed into spherical lenses with a film forming rate of 99.8%. The molecular weight after processing into films was 119500 and the PDI was 2.0.

[0140] Comparative Example 1

[0141] The preparation steps of the polymer refer to Example 1, except that the silicon-containing monomer compound represented by formula X21 is replaced by an equal molar amount of BPEF, and other operations and conditions remain unchanged to obtain the polymer.

[0142] The generated high-refractive polymer was taken out and the performance was evaluated. The physical properties of the obtained high-refractive polymer were as follows:

[0143] The hydroxyl content at the polymer end was 733 ppm, and the free small molecule byproduct content was 210 ppm;

[0144] The molecular weight of the polymer is 118710, the PDI is 1.8, the refractive index at 23°C and a wavelength of 589nm is 1.643, the Abbe number is 22.1, the transmittance is 88.8%, the haze is 0.39%, the b value is 1.39, and the Tg is 142°C;

[0145] The polymer has an Izod notched impact strength of 31 J / m 2 , water absorption rate is 0.15%;

[0146] The polymer was processed into spherical lenses with a film formation rate of 85.2%. The molecular weight after processing into films was 107230 and the PDI was 2.4.

[0147] Example 2

[0148] The preparation process of the silicon-containing monomer compound represented by formula X12 is as follows:

[0149] (1) In the presence of a Custer catalyst, o-allyl phenol and siloxane are mixed for esterification reaction at a temperature of 70° C. for 8 hours; wherein the molar amount of the Custer catalyst is 0.4 mol% of Si-H, and the molar ratio of o-allyl phenol to siloxane is 1:0.6; and finally an intermediate represented by formula C12 is obtained;

[0150] Wherein, the structural formula of the siloxane is:

[0151]

[0152] (2) In the presence of sodium hydroxide as a catalyst, ethylene oxide is mixed with the intermediate represented by formula C12 obtained in step (1) for polymerization reaction, and the reaction is carried out at 75° C. for 5 hours; wherein the molar ratio of ethylene oxide to the intermediate represented by formula C12 is 1:0.45, and the molar ratio of the amount of catalyst sodium hydroxide to ethylene oxide is 0.07:1, and finally a silicon-containing monomer compound represented by formula X12 is obtained.

[0153] The preparation steps of high refractive polymer are:

[0154] 0.02 mol BPEF, 0.07 mol BHEBBN, 0.009 mol silicon-containing monomer compound of formula X12 prepared above, 0.1 mol diphenyl carbonate, 4.0×10 -7 1 mol tetrabutylammonium hydroxide was added into a reaction kettle equipped with a stirrer and a distillation device, and nitrogen was introduced for replacement 3 times. The mixture was heated to 180°C at normal pressure and kept for 30 min. After the raw materials were completely melted, stirring was started. The system pressure was adjusted to 60 KPa (A), and the temperature was raised to 220°C. By-products (phenol and butanol) began to distill out. The reaction was maintained for 60 min under this condition. Then the system was heated to 240°C, and the pressure was reduced by program. The system pressure was gradually reduced to 100 Pa (A) within 1 hour. The reaction was continued for 45 min under this condition to terminate the reaction.

[0155] The generated high-refractive polymer was taken out and the performance was evaluated. The physical properties of the obtained high-refractive polymer were as follows:

[0156] The hydroxyl content at the polymer end was 721 ppm, and the free small molecule byproduct content was 152 ppm;

[0157] The polymer has a molecular weight of 73830, a PDI of 1.81, a refractive index of 1.663 at 23°C and a wavelength of 589nm, an Abbe number of 23.2, a transmittance of 89.6%, a haze of 0.33%, a b value of 1.52, and a Tg of 132°C;

[0158] The polymer has an Izod notched impact strength of 55 J / m 2 , water absorption rate is 0.06%;

[0159] The polymer was processed into spherical lenses with a film formation rate of 99.3%. The molecular weight after processing into films was 69835 and the PDI was 1.92.

[0160] Comparative Example 2

[0161] The preparation steps of the polymer refer to Example 2, except that the silicon-containing monomer compound represented by formula X12 is replaced by an equal molar amount of BPEF, and other operations and conditions remain unchanged to obtain the polymer.

[0162] The generated high-refractive polymer was taken out and the performance was evaluated. The physical properties of the obtained high-refractive polymer were as follows:

[0163] The hydroxyl content at the polymer terminal was 690 ppm, and the content of free small molecule by-products was 139 ppm.

[0164] The polymer has a molecular weight of 63455, a PDI of 1.82, a refractive index of 1.661 at 23°C and a wavelength of 589nm, an Abbe number of 23.1, a transmittance of 88.7%, a haze of 0.41%, a b value of 1.57, and a Tg of 133°C;

[0165] The polymer has an Izod notched impact strength of 26 J / m 2 , water absorption rate is 0.16%;

[0166] The polymer was processed into spherical lenses with a film formation rate of 86.2%. The molecular weight after processing into films was 49801 and the PDI was 3.51.

[0167] Example 3

[0168] The preparation process of the silicon-containing monomer compound represented by formula X23 is as follows:

[0169] (1) In the presence of a Custer catalyst, p-allyl phenol and siloxane are mixed for esterification reaction at a temperature of 80° C. for 4 hours; wherein the molar amount of the Custer catalyst is 0.6 mol% of Si—H, and the molar ratio of p-allyl phenol to siloxane is 1:0.65, and finally an intermediate represented by formula C23 is obtained;

[0170] Wherein, the structural formula of the siloxane is:

[0171]

[0172] (2) In the presence of sodium hydroxide as a catalyst, ethylene oxide is mixed with the intermediate represented by formula C23 obtained in step (1) for polymerization reaction, and the reaction is carried out at 85° C. for 3 hours; wherein the molar ratio of ethylene oxide to the intermediate represented by formula C23 is 1:0.47, and the molar ratio of the amount of catalyst sodium hydroxide to ethylene oxide is 0.08:1, and finally a silicon-containing monomer compound represented by formula X23 is obtained.

[0173] The preparation steps of high refractive polymer are:

[0174] 0.09 mol BPPF, 0.004 mol BHEBN, 0.004 mol silicon-containing monomer compound of formula X23 prepared above, 0.1 mol diphenyl carbonate, 5.0×10 -6 1 mol tin acetate was added into a reaction kettle equipped with a stirrer and a distillation device, and nitrogen was introduced for replacement 3 times. The mixture was heated to 160°C at normal pressure and kept for 30 min. After the raw materials were completely melted, stirring was started. The system pressure was adjusted to 30 Kpa (A), and the temperature was raised to 250°C. By-products (phenol and octanol) began to distill out. The reaction was maintained for 80 min under this condition. The system was then heated to 300°C, and the pressure was reduced by program. The system pressure was gradually reduced to 100 Pa (A) within 1 hour. The reaction was continued for 15 min under this condition to terminate the reaction.

[0175] The generated high-refractive polymer was taken out and the performance was evaluated. The physical properties of the obtained high-refractive polymer were as follows:

[0176] The hydroxyl content at the polymer end was 421 ppm, and the free small molecule byproduct content was 134 ppm;

[0177] The polymer has a molecular weight of 82350, a PDI of 1.97, a refractive index of 1.672 at 23°C and a wavelength of 589nm, an Abbe number of 21.7, a transmittance of 89.3%, a haze of 0.33%, a b value of 1.43, and a Tg of 143°C;

[0178] The polymer has an Izod notched impact strength of 47 J / m 2 , water absorption rate is 0.13%;

[0179] The polymer was processed into spherical lenses with a film formation rate of 98.2%. The molecular weight after processing into films was 81030 and the PDI was 2.10.

[0180] Comparative Example 3

[0181] The preparation steps of the polymer refer to Example 3, except that the silicon-containing monomer compound represented by Formula X23 is replaced by an equal molar amount of BPPF, and other operations and conditions remain unchanged to obtain the polymer.

[0182] The generated high-refractive polymer was taken out and the performance was evaluated. The physical properties of the obtained high-refractive polymer were as follows:

[0183] The hydroxyl content at the polymer end was 355 ppm, and the free small molecule byproduct content was 163 ppm;

[0184] The polymer has a molecular weight of 75430, a PDI of 1.92, a refractive index of 1.669 at 23°C and a wavelength of 589nm, an Abbe number of 22.2, a transmittance of 89.1%, a haze of 0.33%, a b value of 1.45, and a Tg of 139°C;

[0185] The polymer has an Izod notched impact strength of 20 J / m 2 , water absorption rate is 0.21%;

[0186] The polymer was processed into spherical lenses with a film formation rate of 70.3%. The molecular weight after processing into films was 61230 and the PDI was 2.03.

[0187] Example 4

[0188] The preparation process of the silicon-containing monomer compound represented by formula X25 is as follows:

[0189] (1) In the presence of a Custer catalyst, p-allyl phenol and siloxane are mixed for esterification reaction at a temperature of 90° C. for 2 hours; wherein the molar amount of the Custer catalyst is 1 mol% of Si—H, and the molar ratio of p-allyl phenol to siloxane is 1:0.6, and finally an intermediate represented by formula C25 is obtained;

[0190] Wherein, the structural formula of the siloxane is:

[0191]

[0192] (2) In the presence of sodium hydroxide as a catalyst, ethylene oxide is mixed with the intermediate represented by formula C25 obtained in step (1) for polymerization reaction, and the reaction is carried out at 85° C. for 3 hours; wherein the molar ratio of ethylene oxide to the intermediate represented by formula C25 is 1:0.43, and the molar ratio of the amount of catalyst sodium hydroxide to ethylene oxide is 0.1:1, and finally a silicon-containing monomer compound represented by formula X25 is obtained.

[0193] The preparation steps of high refractive polymer are:

[0194] 0.07 mol BPPF, 0.02 mol BHEBBN, 0.005 mol silicon-containing monomer compound represented by formula X25 prepared as above, 0.1 mol diphenyl carbonate, 1.0×10 -6 1 mol tin acetate was added into a reaction kettle equipped with a stirrer and a distillation device, and nitrogen was introduced for replacement 3 times. The mixture was heated to 200°C at normal pressure and kept for 20 minutes. After the raw materials were completely melted, stirring was started, and the system pressure was adjusted to 70Kpa(A). The temperature was raised to 260°C, and by-products (phenol and octanol) began to distill out. The reaction was maintained for 90 minutes under this condition. Then the system was heated to 265°C, and the pressure was reduced by program. The system pressure was gradually reduced to 80Pa(A) within 1 hour, and the reaction was continued for 25 minutes under this condition to terminate the reaction.

[0195] The generated high-refractive polymer was taken out and the performance was evaluated. The physical properties of the obtained high-refractive polymer were as follows:

[0196] The hydroxyl content at the polymer end was 421 ppm, and the free small molecule byproduct content was 188 ppm;

[0197] The polymer has a molecular weight of 52340, a PDI of 1.71, a refractive index of 1.681 at 23°C and a wavelength of 589nm, an Abbe number of 21.3, a transmittance of 89.1%, a haze of 0.32%, a b value of 1.51, and a Tg of 135°C;

[0198] The polymer has an Izod notched impact strength of 45 J / m 2 , water absorption rate is 0.11%;

[0199] The polymer was processed into spherical lenses with a film formation rate of 98.2%. The molecular weight after processing into films was 49450 and the PDI was 1.98.

[0200] Comparative Example 4

[0201] The preparation steps of the polymer are similar to those of Example 4, except that the silicon-containing monomer compound represented by Formula X25 is replaced by an equal molar amount of BHEBBN, and other operations and conditions remain unchanged to obtain the polymer.

[0202] The generated high-refractive polymer was taken out and the performance was evaluated. The physical properties of the obtained high-refractive polymer were as follows:

[0203] The hydroxyl content at the polymer end was 392 ppm, and the free small molecule byproduct content was 192 ppm;

[0204] The polymer has a molecular weight of 51340, a PDI of 1.89, a refractive index of 1.688 at 23°C and a wavelength of 589nm, an Abbe number of 21.7, a transmittance of 86.2%, a haze of 0.34%, a b value of 1.62, and a Tg of 134°C;

[0205] The polymer has an Izod notched impact strength of 24 J / m 2 , water absorption rate is 0.21%;

[0206] The polymer was processed into spherical lenses with a flake rate of 73.2%. The molecular weight after flake processing was 47905 and the PDI was 2.37.

[0207] Embodiment 5:

[0208] The preparation process of the silicon-containing monomer compound represented by formula X21 is the same as that of Example 1.

[0209] The preparation steps of the high refractive polymer refer to Example 1, with the only difference being that the amount of the silicon-containing monomer compound represented by Formula X21 is replaced by 0.001 mol (i.e., the molar fraction of the silicon-containing monomer compound to the total amount of BPEF, BHEBN and the silicon-containing monomer compound is 1.06%); other operations and conditions remain unchanged to obtain the polymer.

[0210] The generated high-refractive polymer was taken out and the performance was evaluated. The physical properties of the obtained high-refractive polymer were as follows:

[0211] The hydroxyl content at the polymer end was 699 ppm, and the free small molecule byproduct content was 198 ppm;

[0212] The molecular weight of the polymer is 104320, PDI is 1.87, the refractive index at 23°C and wavelength 589nm is 1.642, the Abbe number is 21.6, the transmittance is 90.1%, the haze is 0.32%, the b value is 1,23, and the Tg is 136°C;

[0213] The polymer has an Izod notched impact strength of 48 J / m 2 , water absorption rate is 0.1%;

[0214] The polymer was processed into spherical lenses with a film formation rate of 98.1%. The molecular weight after processing into films was 97650 and the PDI was 1.92.

[0215] Comparative Example 5

[0216] The preparation process of the silicon-containing monomer compound represented by formula X21 is the same as that of Example 1.

[0217] The preparation steps of the high refractive polymer refer to Example 1, with the only difference being that the amount of the silicon-containing monomer compound represented by Formula X21 is 0.0003 mol (i.e., the molar fraction of the silicon-containing monomer compound in the total amount of BPEF, BHEBN and the silicon-containing monomer compound is less than 1%); other operations and conditions remain unchanged to obtain the polymer.

[0218] The generated high-refractive polymer was taken out and the performance was evaluated. The physical properties of the obtained high-refractive polymer were as follows:

[0219] The hydroxyl content at the polymer end was 743 ppm, and the free small molecule byproduct content was 167 ppm;

[0220] The polymer has a molecular weight of 109650, a PDI of 1.88, a refractive index of 1.640 at 23°C and a wavelength of 589 nm, an Abbe number of 21.2, a transmittance of 90.2%, a haze of 0.33%, a b value of 1.29, and a Tg of 136°C;

[0221] The polymer has an Izod notched impact strength of 36 J / m 2 , water absorption rate is 0.19%;

[0222] The polymer was processed into spherical lenses with a film formation rate of 82.1%. The molecular weight after processing into films was 89230 and the PDI was 2.01.

[0223] It can be seen from the experimental results of various embodiments and comparative examples that, compared with the comparative examples, the polymer molecular chains of various embodiments of the present invention have increased flexibility of the molecular chains and improved processability of the products, thereby significantly improving impact strength and sheeting rate due to the introduction of the selected special organosilicon groups and controlling their content within a suitable range; at the same time, the "-Si-O-Si-" in the organosiloxane effectively changes the surface properties of the material, reduces the water absorption rate of the material, greatly improves the hydrolysis resistance of the polycarbonate product, and enhances the dimensional stability of the material.

[0224] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the spirit of the present invention.

Claims

1. A highly refractive polymer, It is characterized in that It includes the following structural units: (1) A repeating structural unit derived from a silicon-containing monomer compound; the silicon-containing monomer compound is represented by the general formula (X1n) or the general formula (X2n); wherein, The general formula (X1n) is as follows: The general formula (X2n) is as follows: In the general formula (X1n) and the general formula (X2n), n is each independently 1-10, preferably 2-7; (2) any one or more of the repeating structural units derived from the compound represented by the general formula (A) and the repeating structural units derived from the compound represented by the general formula (B); wherein, The general formula (A) is as follows: In the general formula (A), R 1 , R 2 Each of them is independently a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C5-C20 cycloalkyl group, a C5-C20 cycloalkoxy group, a C6-C20 aryl group, or a C6-C20 aryloxy group, preferably a hydrogen atom, a C1-C3 alkyl group, or a C6-C12 aryl group; The general formula (B) is as follows: In the general formula (B), R 3 , R 4 Each of them is independently a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C5-C20 cycloalkyl group, a C5-C20 cycloalkoxy group, a C6-C20 aryl group, or a C6-C20 aryloxy group, and is preferably a hydrogen atom, a C1-C3 alkyl group, or a C6-C12 aryl group.

2. The high refractive polymer according to claim 1, It is characterized in that In the high refractive polymer, the ratio of each repeating structural unit is as follows: The molar ratio of the repeating structural unit derived from the compound represented by the general formula (A) to the repeating structural unit derived from the silicon-containing monomer compound is (0 to 99):1, preferably (1 to 20):1; The molar ratio of the repeating structural unit derived from the compound represented by the general formula (B) to the repeating structural unit derived from the silicon-containing monomer compound is (0 to 99):1, preferably (1 to 20):1; Furthermore, the contents of the repeating structural unit derived from the compound represented by the general formula (A) and the repeating structural unit derived from the compound represented by the general formula (B) are not 0 at the same time.

3. The high refractive polymer according to claim 1 or 2, It is characterized in that In the high refractive polymer, the terminal hydroxyl content is less than or equal to 1000ppm, preferably 300-500ppm; In the high-refractive polymer, the content of small molecular by-products is less than or equal to 500 ppm, preferably 100-300 ppm.

4. The high refractive polymer according to any one of claims 1 to 3, It is characterized in that The compound represented by the general formula (A) is selected from at least one of the compound BPEF and the compound BPPF; wherein, The compound BPEF is shown in the following structural formula: The compound BPPF is shown in the following structural formula:

5. The high refractive polymer according to any one of claims 1 to 4, It is characterized in that The compound represented by the general formula (B) is selected from at least one of the compound BHEBN and the compound BHEBBN; wherein, The compound BHEBN is shown in the following structural formula: The compound BHEBBN is shown in the following structural formula:

6. The high refractive polymer according to any one of claims 1 to 5, It is characterized in that The silicon-containing monomer compound is a product prepared by the following method: (1) contacting o-allylphenol or p-allylphenol with siloxane and performing an esterification reaction to prepare an intermediate C; (2) contacting ethylene oxide with the intermediate C obtained in step (1) and performing a polymerization reaction to prepare the silicon-containing monomer compound.

7. The high refractive polymer according to claim 6, It is characterized in that In step (1), the general structural formula of the siloxane is as follows: Wherein, n=1-10, preferably n=2-7; Preferably, in step (1), the molar ratio of o-allylphenol or p-allylphenol to siloxane is 1:(0.5-0.75), more preferably 1:(0.55-0.65); Preferably, in step (1), the conditions of the esterification reaction include: a reaction temperature of 50 to 100° C., more preferably 60 to 90° C.; a reaction time of 1 to 12 h, more preferably 2 to 6 h; Preferably, in step (1), the esterification reaction is carried out in the presence of catalyst-I, wherein the catalyst-I is a Custer catalyst; and the molar amount of the catalyst-I is 0.1-1 mol% of the molar amount of Si-H.

8. The high refractive polymer according to claim 6, It is characterized in that In step (2), the molar ratio of ethylene oxide to the intermediate C obtained in step (1) is 1:(0.4-0.5), preferably 1:(0.43-0.47); and / or In step (2), the polymerization reaction conditions include: reaction temperature of 60 to 90° C., preferably 65 to 85° C.; reaction time of 3 to 8 hours, preferably 4 to 6 hours; and / or In step (2), the polymerization reaction is carried out under the action of catalyst-II, and the catalyst-II is sodium hydroxide; the molar ratio of catalyst-II to ethylene oxide is 0.05:(0.1-1).

9. The high refractive polymer according to any one of claims 1 to 8, It is characterized in that The high refractive polymer is a product obtained by contacting and polymerizing a compound represented by the general formula (A) and / or a compound represented by the general formula (B), a silicon-containing monomer compound and a carbonic acid diester; Preferably, the molar ratio of the total amount of the compound represented by the general formula (A), the compound represented by the general formula (B), the silicon-containing monomer compound and the amount of the carbonic acid diester is (0.9-1):1, more preferably (0.93-1):1; Preferably, the molar fraction of the amount of the silicon-containing monomer compound used in the total amount of the compound represented by the general formula (A), the compound represented by the general formula (B), and the silicon-containing monomer compound is 1 mol% to 10 mol%; Preferably, the carbonic acid diester is at least one selected from diphenyl carbonate, ditolyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate, more preferably at least one selected from diphenyl carbonate and ditolyl carbonate.

10. The high refractive polymer according to claim 9, It is characterized in that The high refractive polymer is prepared by melt transesterification polycondensation method in the presence or absence of a polymerization catalyst; Preferably, the polymerization catalyst is selected from at least one of sodium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylamine, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride, tin acetate, cerium acetylacetonate, zirconium acetylacetonate, zirconium acetate and tetrabutoxyzirconium, more preferably selected from at least one of sodium hydroxide, sodium bicarbonate, cesium carbonate, cerium acetylacetonate, zirconium acetate and zinc acetate; Preferably, the molar ratio of the polymerization catalyst to the carbonic acid diester is 1×10 -8 ~1×10 -3 , more preferably 1×10 -6 ~1×10 -4 .

11. The high refractive polymer according to any one of claims 1 to 10, It is characterized in that The weight average molecular weight of the high refractive polymer is 10,000 to 150,000, preferably 20,000 to 130,000, more preferably 30,000 to 120,000; and / or The refractive index of the high refractive polymer at 23° C. and a wavelength of 589 nm is 1.625 to 1.685; and / or The Abbe number of the high refractive polymer is not higher than 24; and / or The high-refractive polymer has a light transmittance greater than or equal to 88%, a haze less than or equal to 0.7%, and a b value less than or equal to 2.

12. Use of the high refractive polymer according to any one of claims 1 to 11 in an optical lens.

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