A high-refractive polymer and its preparation method and application

Abstract

The present invention provides a high-refractive polymer, a preparation method, and applications thereof. The high-refractive polymer comprises a structural unit #imgabs0# derived from a bio-based monomer represented by general formula (Y), and further comprises one or both of a structural unit #imgabs1# derived from a compound represented by general formula (A) and a structural unit #imgabs2# derived from a compound represented by general formula (B). The high-refractive polymer of the present invention is suitable for use in the preparation of optical lenses.

Description

Technical Field

[0001] The present invention relates to the field of bio-based polymers, and in particular to a high-refractive polymer, a preparation method thereof, and applications in the field of optical lenses. Background Art

[0002] Cameras are key components in areas such as mobile smart terminals, intelligent vehicles, and security surveillance. The main materials used for cameras are optical glass and optical resin. Optical glass, however, is expensive, difficult to shape, and technically challenging, making it difficult to meet the demands of daily use. Optical resin, however, is becoming the mainstream in the market due to its advantages of easy molding, high production efficiency, and low cost.

[0003] The mainstream optical resins currently on the market include high-refractive PC, high-refractive polyester, cycloolefin polymer COC and COP. Among them, high-refractive PC is an indispensable material in optical lenses due to its high refractive index. The monomers involved in the high-refractive PC currently reported in the market and patents are bisphenol or diether compounds derived from fluorene rings and naphthalene rings. High-refractive PC patent manufacturers mainly protect monomers and monomer ratios. In Mitsubishi's patents, the core monomers are mainly dinaphthol and bisphenol fluorene compounds. In Teijin's patents, the core monomers are diether fluorene, methyl bisphenol fluorene, dinaphthol, and bisphenol anthrone compounds.

[0004] Patent document CN201310062561.X proposes a polycarbonate containing 9,9-bis-(4-(2-hydroxyethoxy)phenyl)fluorene and its derivatives, patent document CN104769007A discloses a polycarbonate containing 2,2-bis-(2-hydroxyethoxy)-1,1-binaphthyl and its derivatives; patent document CN110741030A discloses a polycarbonate containing 9,9-bis(4-(2-hydroxyethoxy)phenyl)dinaphthylfluorene structural units.

[0005] The monomers mentioned above all come from coal tar, which has complex composition and high boiling point, and purification requires high energy consumption. On the other hand, these monomers are non-biobased and non-degradable. Bio-based polymer materials have many advantages such as sustainable development, low environmental pollution, good biocompatibility and easy degradation. They have received more and more attention in recent years and have triggered a research boom in many fields such as substitutes for petroleum-based polymer materials. Bio-based high-refractive PC has also become the focus of people's attention. Summary of the Invention

[0006] To address the aforementioned issues in the prior art, the present invention provides a high-refractive polymer and a method for preparing the same. Through structural construction, the system incorporates bio-based monomers, offering numerous advantages, including the excellent biocompatibility of bio-based materials. Furthermore, during the reaction, the system generates alcohol as a byproduct, facilitating the separation and collection of phenol, reducing energy consumption for industrial production and the risk of pipeline blockage. The high-refractive polymer of the present invention is suitable for use in the preparation of optical lenses or optical films, with significantly improved impact strength and film formation rate.

[0007] To achieve the above object, the present invention adopts the following technical solutions:

[0008] The present invention provides a high-refractive polymer, comprising:

[0009] Structural units derived from bio-based monomers represented by general formula (Y),

[0010]

[0011] In the general formula (Y), R1 each independently represents a hydrogen atom or a methyl group; R2 each independently represents a C2-C15 alkyl group or a C5-C15 cycloalkyl group, preferably a C4-C8 alkyl group or a C6-C10 cycloalkyl group, more preferably an n-butyl group, an n-hexyl group, an n-octyl group, or a cyclohexyl group; R3 represents a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C5-C20 cycloalkyl group, a C5-C20 cycloalkyloxy group, a C6-C20 aryl group, or a C6-C20 aryloxy group, preferably a C6-C12 cycloalkyl group or a C6-C20 alkyl group, more preferably a hexyl group, an octyl group, or a cyclohexyl group;

[0012] A structural unit derived from a compound represented by general formula (A),

[0013]

[0014] In the general formula (A), R4 and R5 each independently represent 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;

[0015] A structural unit derived from a compound represented by general formula (B),

[0016]

[0017] In the general formula (B), R6 and R7 each independently represent a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C5-C20 cycloalkyl group, a C1-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;

[0018] wherein the structural unit derived from the compound represented by general formula (A) and the structural unit derived from the compound represented by general formula (B) are selected from one or both;

[0019] The high-refractive polymer has a terminal hydroxyl content of less than 1000 ppm, preferably 300-500 ppm.

[0020] In the present invention, the compound represented by the general formula (A) is selected from at least one of the following structural compounds BPEF, BPPF, and BAAPEF:

[0021]

[0022] The compound represented by the general formula (B) is selected from at least one of the following structural compounds BHEBN, BHEBBN

[0023]

[0024] In the present invention, the high refractive index polymer is terminated with a benzene ring, has a terminal hydroxyl content of less than 1000 ppm, preferably 300-500 ppm, and is mainly derived from monomers of general formula (A) and / or general formula (B).

[0025] In the present invention, the content of small molecule byproducts in the high-refractive polymer is less than 500 ppm, preferably 100-300 ppm; the small molecule byproducts include phenol and C4-C8 alcohols, such as butanol, hexanol, and octanol. The small molecule byproducts in the composition of the present invention are primarily derived from carbonic acid diesters and / or monomers of formula (Y), primarily phenol.

[0026] The polymer of the present invention has a low content of terminal hydroxyl groups and small molecule byproducts. The reduction of the content of terminal hydroxyl groups and small molecule byproducts in the system reduces the hydrolyzable groups in the system, improves the stability of the polymer, and helps to avoid degradation during product processing. On the other hand, the reduction of hydroxyl groups weakens the hydrogen bonding effect of the high-refractive polyester product. In addition, the Y monomer has a flexible long-chain structure, which reduces the rigidity of the product, lowers the Tg, and improves the processability of the product, especially significantly improving the impact strength and the sheeting rate. The present invention greatly reduces the yellowing and degradation phenomena that occur during product reprocessing by limiting the terminal hydroxyl groups and small molecule byproducts in the system.

[0027] In the present invention, the high refractive polymer has a weight average molecular weight of 10,000 to 150,000, preferably 20,000 to 130,000, and more preferably 30,000 to 120,000.

[0028] In the present invention, the refractive index of the high-refractive polymer is 1.625 to 1.685 at 23° C. and a wavelength of 589 nm;

[0029] In the present invention, the Abbe number of the high-refractive polymer is not higher than 24, the light transmittance of the high-refractive polymer is greater than 88%, the haze is less than 0.7%, and the b value is less than 2.

[0030] In addition, the high-refractive polymer of the present invention also has stable high light transmittance, excellent dimensional stability, good product flexibility, strong plasticity, low rigidity and Tg, and improves the processing performance of the product.

[0031] In the present invention, the high-refractive polymer comprises a structural unit derived from a bio-based monomer represented by general formula (Y), and any one or two of a structural unit derived from a compound represented by general formula (A) and a structural unit derived from a compound represented by general formula (B), wherein the molar ratio of the structural unit derived from the bio-based monomer represented by general formula (Y) to the structural unit derived from the compound represented by general formula (A) and the structural unit derived from the compound represented by general formula (B) is 1:0~20:0~20, preferably 1:0.1~15:0.1~15, and the structural unit derived from the compound represented by general formula (A) and the structural unit derived from the compound represented by general formula (B) are not both 0.

[0032] In the present invention, the bio-based monomer represented by general formula (Y) has no particular requirements on its source and can be directly purchased or prepared by oneself. Technicians can prepare it by any feasible method based on existing technology as needed, and the present invention does not particularly limit its specific preparation process. In some examples, the method for preparing the bio-based monomer represented by general formula (Y) comprises the following steps:

[0033] (1) preparing intermediate C by esterification reaction of vanillic acid or syringic acid with alcohol;

[0034] (2) The dibromoalkane is polymerized with the intermediate C prepared in step (1) to prepare a bio-based monomer represented by the general formula (Y).

[0035] In step (1) of the preparation method of the present invention, an esterification reaction is carried out in the presence of a catalyst. The scheme used is a process disclosed in the prior art and is not specifically required by the present invention. For example, the preparation can be made with reference to the method disclosed in the document Partially bio-based poly(amide imide)s by polycondensation of aromatic diacylhydrazides based on lignin-derived phenolic acids and aromatic dianhydrides: Synthesis, characterization, and computational studies. Journal of Polymer Science Part A: Polymer Chemistry. 2017; 55: 3636-3645.

[0036] In some examples, in step (1), the alcohol is selected from at least one of butanol, hexanol, octanol, and cyclohexanol;

[0037] The molar ratio of the vanillic acid or syringic acid to the alcohol is 1:1-4, preferably 1:1.5-2.5;

[0038] The esterification reaction temperature is 100-150°C, preferably 120-140°C; the time is 1-12 hours, preferably 2-6 hours;

[0039] The esterification reaction is carried out under the action of a catalyst, and the catalyst is preferably sulfuric acid;

[0040] Preferably, the amount of the catalyst is 0.5-3 wt% of the alcohol mass.

[0041] The intermediate obtained in step (1) of the preparation method of the present invention has a structure shown in general formula (C):

[0042]

[0043] In formula (C), R1 and R2 are the same as R1 and R2 in general formula (Y).

[0044] In step (2) of the preparation method of the present invention, a polymerization reaction is carried out in the presence of a catalyst. The scheme used is a process disclosed in the prior art, and the present invention does not make specific requirements. For example, the preparation can be made with reference to the method disclosed in the document Partially bio-based poly(amide imide)s by polycondensation of aromatic diacylhydrazides based onlignin-derived phenolic acids and aromatic dianhydrides: Synthesis, characterization, and computational studies. Journal of Polymer Science Part A: Polymer Chemistry. 2017; 55: 3636-3645.

[0045] In some examples, in step (2), the dibromoalkane is selected from at least one of dibromohexane, dibromooctane, and 1,4-dibromocyclohexane;

[0046] The molar ratio of the dibromoalkane to the intermediate C prepared in step (1) is 1:0.4-0.8, preferably 1:0.5-0.6;

[0047] The reaction temperature is 80-140°C, preferably 100-120°C; the time is 8-20, preferably 12-16;

[0048] The polymerization reaction is carried out under the action of a catalyst, and the catalyst is preferably potassium carbonate;

[0049] Preferably, the molar ratio of the catalyst to the dibromoalkane is 1:0.5-1.

[0050] The present invention also provides a method for preparing the high-refractive polymer, which can be prepared by polymerization reaction of a compound represented by general formula (A) and / or general formula (B) with a bio-based monomer represented by general formula (Y), and an optional carbonic acid diester. This method is a process disclosed in the prior art. In some examples, the preferred conditions used in the present invention are as follows:

[0051] In the preparation method of the present invention, the molar ratio of the sum of the bio-based monomer represented by general formula (Y) and the carbonic acid diester to the sum of the compounds represented by general formula (A) and general formula (B) is 1 to 0.9:1, preferably 1 to 0.93:1.

[0052] In the preparation method of the present invention, 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 at least one of diphenyl carbonate and ditolyl carbonate.

[0053] The preparation method of the present invention can be prepared by melt transesterification polycondensation in the presence of a catalyst or in the absence of a catalyst;

[0054] The 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 at least one of sodium hydroxide, sodium bicarbonate, cesium carbonate, cerium acetylacetonate, zirconium acetate, and zinc acetate;

[0055] The molar ratio of the amount of the catalyst to the sum of the bio-based monomer and the carbonate diester represented by the general formula (Y) is 1×10 -8 ~1×10 -3 , preferably 1×10 -6 ~1×10 -4 .

[0056] The preparation method of the present invention, the polymerization reaction specifically includes a material melting stage, an ester exchange stage, and a condensation stage; wherein the melting stage has a melting temperature of 100-250°C, preferably 140-200°C, and a residence time of 20-50 minutes, preferably 30-40 minutes; the ester exchange stage has a pressure of 20-80 kPa, a reaction temperature of 140-280°C, preferably 170-250°C, and a reaction time of 30-180 minutes, preferably 60-90 minutes; the condensation stage has a pressure of 5-1000 Pa(A), preferably 50-150 Pa(A), a temperature of 200-350°C, preferably 250-300°C, and a reaction time of 5-90 minutes, preferably 15-60 minutes. During the reaction, the generated small molecule compounds are immediately removed by distillation.

[0057] The high-refractive polymer of the present invention is suitable for preparing optical lenses or optical films.

[0058] Traditional high-refractive polyesters contain a large amount of rigid rings (such as naphthalene rings) in their structure, resulting in strong molecular chain rigidity. This causes the product to become whitish and have poor transparency, while the toughness of the product is insufficient and brittle. The present invention solves the above problems by introducing a bio-based monomer shown in the general formula (Y) and optional general formula (A) and general formula (B) compounds, wherein the formula A and formula B compounds ensure that the polymer product has a high refractive index, and the bio-based monomer Y has a flexible long-chain structure, which reduces the rigidity of the product. The synergistic effect of the two types of monomers improves the performance of the material. In addition, the high-refractive polyester product of the present invention is fully or partially terminated with a benzene ring, and the terminal hydroxyl content is less than 1000ppm. The content of small molecule by-products such as phenol in the system is less than 500ppm. The reduction of hydroxyl content in the system reduces the hydrolyzable group in the system on the one hand, improves the stability of the polymer, and is conducive to avoiding degradation in the product processing process. On the other hand, the reduction of hydroxyl weakens the hydrogen bond influence of the high-refractive polymer product, and Y has a flexible long-chain structure, which reduces the rigidity of the product, reduces Tg, improves the processability of the product, and especially improves impact strength and flake rate. The limitation of terminal hydroxyl groups and small molecule by-products in the system greatly improves the yellowing and degradation phenomena that occur during product reprocessing.

[0059] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0060] This invention uses bio-based monomers made from vanillic acid / syringic acid and alcohol to produce a high-refractive polymer. This polymer exhibits excellent dimensional stability, flexibility, and plasticity, making it particularly suitable for small-sized, aspherical products such as optical lenses. It also offers stable high light transmittance, significantly reducing yellowing and degradation during reprocessing, meeting the requirements of multi-element lenses.

[0061] The polymer system of the present invention contains bio-based monomers, is sustainable, has little environmental pollution, and complies with current policies and regulations. DETAILED DESCRIPTION

[0062] The present invention is now described below in conjunction with specific embodiments. It should be noted that the embodiments are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Any non-substantial improvements and adjustments made based on the contents of the present invention are also protected by the present invention.

[0063] The main performance testing methods used for the polymer of the present invention are as follows:

[0064] 1) Weight-average molecular weight (Mw) and molecular weight distribution (PDI): Gel permeation chromatography (GPC) was used with dichloromethane as the developing solvent. A calibration curve was prepared using standard polystyrenes of known molecular weight (molecular weight distribution = 1). Based on this calibration curve, Mw and PDI were calculated from the GPC retention times.

[0065] 2) Glass transition temperature (Tg) was measured using a DSC-60A at a heating rate of 20°C / min.

[0066] 3) Polymer terminal hydroxyl group and small molecule byproduct (phenol) content testing: Samples were dissolved in dichloromethane and derivatized with trifluoroacetic anhydride. After derivatization, the 19F nuclear magnetic resonance spectrum was analyzed using fluorobenzene as the internal standard for quantification. Phenol derivatization peaked at -74.7 ppm, primary hydroxyl peaked at -74.8 ppm, and secondary hydroxyl peaked at -75.3 ppm.

[0067] Instrument: Bruker AVANCE NEO 600M spectrometer; test probe: 5 mm BBO probe; test solvent: CDCl3; test temperature: 25°C.

[0068] 4) Refractive Index (nD): The refractive index (nD) of the high refractive polymer of the present invention at 23°C and a wavelength of 589 nm, and the refractive index (nD) in the range of -10 to 50°C and a wavelength of 589 nm were measured using an Abbe refractometer according to the method of GB / T 7962.4-2010.

[0069] 5) Abbe number: The refractive index at wavelengths of 486 nm, 589 nm, and 656 nm at 23° C. was measured using an Abbe refractometer, and the Abbe number ν was calculated using the following formula:

[0070] ν=(nD-1) / (nF-nC).

[0071] 6) Light transmittance and haze: Measured using a turbidity meter according to the method of JIS-K-7361-1.

[0072] 7) b value: Injection molding was performed using an injection molding machine at a cylinder temperature of 270°C and a mold temperature of Tg-10°C to produce a disc-shaped test plate with a diameter of 50 mm and a thickness of 3 mm. The b value was measured using this plate in accordance with JIS K7105.

[0073] 8) Impact test: The notched Izod impact strength test was conducted in accordance with ASTM D256 in an environment of 25° C. and 50% relative humidity using an Instron CEAST 9050 testing machine.

[0074] 9) Spherical lens processing: After vacuum drying at 120°C for 8 hours, the molding temperature was set to Tg+110°C, the mold temperature was set to Tg-10°C, and a lens with a thickness of 0.2mm, a convex curvature radius of 5mm, a concave curvature radius of 4mm, and a diameter of 5mm was injection molded using a SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd.

[0075] In the examples and comparative examples of the present invention, the sources of the main raw materials are as follows. Unless otherwise specified, other raw materials and reagents were purchased from common commercial sources:

[0076] Diphenyl carbonate: Shanghai Titan;

[0077] BPEF: Jiangsu Yongxing;

[0078] BPPF:Jiangsu Yongxing

[0079] BHEBN: Jiangsu Yongxing;

[0080] 2,2-bis(2-hydroxyethoxy)-5,5-diphenyl-1,1-binaphthyl (BHEBBN): prepared according to the method disclosed in patent CN114957954A;

[0081] Preparation of bio-based monomer represented by general formula (Y) (Y-1 compound)

[0082] (1) Vanillic acid butyl ester was prepared from vanillic acid and butanol according to the literature [Partially bio-based poly(amide imide)s by polycondensation of aromatic diacylhydrazides based on lignin-derived phenolic acids and aromatic dianhydrides: Synthesis, characterization, and computational studies. Journal of Polymer Science Part A: Polymer Chemistry. 2017; 55: 3636-3645].

[0083] (2) Using butyl vanillate and dibromohexane as raw materials, according to the literature Vanillin-based polyschiffvitrimers: reprocessability and chemical recyclability (J) ACSS Sustain. Chem. Eng., 2018, 6: 15463-15470, compound Y-1 was prepared, in which R1 is hydrogen, R2 is butyl, and R3 is hexyl.

[0084] Preparation of the bio-based monomer (Y-2 compound) represented by the general formula (Y): The preparation method refers to the method for compound Y-1, except that: step (1) uses syringic acid and butanol as raw materials to prepare butyl syringate, and step (2) uses butyl syringate and dibromooctane as raw materials to prepare compound Y-2, in which R1 is methoxy, R2 is butyl, and R3 is octyl.

[0085] Preparation of the bio-based monomer (Y-3 compound) represented by the general formula (Y): The preparation method refers to the method for compound Y-1, except that: step (1) uses syringic acid and octanol as raw materials to prepare octyl syringate, and step (2) uses octyl syringate and 1,4-dibromocyclohexane as raw materials to prepare compound Y-3, in which R1 is methoxy, R2 is octyl, and R3 is cyclohexyl.

[0086] Preparation of the bio-based monomer (Y-4 compound) represented by the general formula (Y): The preparation method refers to the method for compound Y-1, except that: step (1) uses syringic acid and hexanol as raw materials to prepare hexyl syringate, and step (2) uses hexyl syringate and 1,4-dibromocyclohexane as raw materials to prepare compound Y-4, in which R1 is methoxy, R2 is hexyl, and R3 is cyclohexyl.

[0087] Example 1

[0088] The steps for preparing a high refractive index polymer are as follows:

[0089] 0.036 mol BPEF, 0.06 mol BHEBN, 0.041 mol Y-1 compound, 0.059 mol diphenyl carbonate, 5.0×10 -7 1 mol of sodium hydroxide was added to a reactor equipped with a stirrer and a distillation apparatus. The atmosphere was replaced with nitrogen three times, and the mixture was heated to 140°C at normal pressure and held for 30 minutes. Once the raw materials were completely melted, stirring was started, the pressure was adjusted to 40 kPa(A), and the temperature was raised to 240°C. Byproducts began to distill off, and the reaction was maintained for 90 minutes. The temperature was then raised to 250°C and the pressure was programmed to be reduced to 100 Pa(A) over 1 hour. The reaction was continued for 30 minutes, and the reaction was terminated.

[0090] The generated high-refractive polymer was taken out and performance evaluation was performed. The measured physical properties of the obtained high-refractive polymer are shown below: the hydroxyl content at the end of the polymer was 723 ppm, and the content of free small molecule by-products was 210 ppm.

[0091] Molecular weight 119340, PDI 1.9, refractive index 1.647, Abbe number 22.2, transmittance 88.9%, haze 0.32%, b value 1.34, Tg 135℃, Izod notched impact strength 48 J / m 2 .

[0092] Processed into spherical lenses, the film yield is 99.8%, the molecular weight after processing is 118300, and the PDI is 2.0.

[0093] Comparative Example 1

[0094] The polymer was prepared by referring to the method of Example 1, except that the compound Y-1 was replaced by an equimolar amount of diphenyl carbonate, and the other operations and conditions remained unchanged to obtain the polymer.

[0095] The generated high-refractive polymer was taken out and the performance was evaluated. The measured physical properties of the obtained high-refractive polymer are shown below: the hydroxyl content at the end of the polymer was 703 ppm, and the content of free small molecule by-products was 235 ppm;

[0096] Molecular weight 117820, PDI 1.8, refractive index 1.642, Abbe number 22.1, transmittance 88.2%, haze 0.39%, b value 1.39, Tg 142°C, Izod notched impact strength 33 J / m 2 .

[0097] The spherical lens was processed into a sheet with a yield of 87.2%. The molecular weight after processing was 117230 and the PDI was 2.4.

[0098] Example 2

[0099] 0.029 mol BPEF, 0.07 mol BHEBBN, 0.1 mol Y-2 compound, and 4.0×10-7 mol tetrabutylammonium hydroxide were added to a reactor equipped with a stirrer and a distillation apparatus. The atmosphere was replaced with nitrogen three times, and the mixture was heated to 180°C at normal pressure and allowed to stand for 30 min. After the raw materials were completely melted, stirring was started, the pressure was adjusted to 60 kPa(A), and the temperature was raised to 230°C. By-products (phenol and butanol) began to distill off, and the reaction was maintained for 60 min. The temperature was then raised to 250°C, and the pressure was reduced by a program. The pressure was gradually reduced to 100 Pa(A) within 1 hour, and the reaction was terminated after 45 min.

[0100] The generated high-refractive polymer was taken out and performance evaluation was performed. The measured physical properties of the obtained high-refractive polymer are shown below: the hydroxyl content at the end of the polymer was 621 ppm, and the content of free small molecule by-products was 182 ppm.

[0101] Molecular weight 62830, PDI 1.81, refractive index 1.663, Abbe number 23.2, transmittance 89.6%, haze 0.33%, b value 1.52, Tg 132°C, Izod notched impact strength 38 J / m 2 .

[0102] Processed into spherical lenses, the film yield is 99.6%, the molecular weight after processing is 61235, and the PDI is 1.92.

[0103] Comparative Example 2

[0104] The same reaction conditions as above were followed, except that the amount of BPEF used was increased from 0.029 mol to 0.035 mol, and other operations and conditions remained unchanged, to obtain a polymer.

[0105] The generated high-refractive polymer was taken out and performance evaluation was performed. The measured physical properties of the obtained high-refractive polymer are shown below, wherein the terminal hydroxyl content of the product is 3690 ppm, and the content of free small molecule by-products is 1139 ppm.

[0106] Molecular weight 63455, PDI 1.82, refractive index 1.661, Abbe number 23.1, transmittance 88.7%, haze 0.41%, b value 1.57, Tg 133℃, Izod notched impact strength 29 J / m 2 .

[0107] The spherical lens was processed into a sheet with a yield of 76.2%. The molecular weight after processing was 39801 and the PDI was 3.51.

[0108] Example 3

[0109] 0.094 mol BPPF, 0.004 mol BHEBN, 0.04 mol Y-3 compound, 0.06 mol diphenyl carbonate, and 5.0×10-6 mol tin acetate were added to a reactor equipped with a stirrer and a distillation apparatus. The mixture was replaced with nitrogen three times and heated to 160°C at normal pressure. The mixture was kept for 30 min. After the raw materials were completely melted, stirring was started and the pressure was adjusted to 30 kPa(A). The temperature was raised to 250°C. By-products (phenol and octanol) began to distill off. The reaction was maintained for 80 min. The temperature was then raised to 300°C. The pressure was reduced by a program and gradually reduced to 100 Pa(A) within 1 hour. The reaction was continued for 15 min. The reaction was terminated.

[0110] The generated high-refractive polymer was taken out and subjected to performance evaluation. The measured physical properties of the obtained high-refractive polymer are shown below: the hydroxyl content at the polymer terminal was 321 ppm, and the content of free small molecule by-products was 154 ppm.

[0111] Molecular weight 92350, PDI 1.87, refractive index 1.672, Abbe number 21.2, transmittance 90.3%, haze 0.29%, b value 1.41, Tg 141°C, Izod notched impact strength 38 J / m 2 .

[0112] The spherical lens was processed to a film yield of 98.9%, and the molecular weight after processing was 91,000 and the PDI was 2.11.

[0113] Comparative Example 3

[0114] The polymer was prepared by referring to the method of Example 3, except that the reaction was carried out under the same conditions as above, except that the Y-3 compound was replaced with an equimolar amount of dimethyl terephthalate, and the other operations and conditions remained unchanged to obtain the polymer.

[0115] The generated high-refractive polymer was taken out and performance evaluation was performed. The measured physical properties of the obtained high-refractive polymer are shown below. The terminal hydroxyl content of the product was 355 ppm, and the content of free small molecule by-products was 182 ppm.

[0116] Molecular weight 95430, PDI 1.92, refractive index 1.669, Abbe number 22.5, transmittance 89.3%, haze 0.33%, b value 1.45, Tg 139℃, Izod notched impact strength 21J / m 2 .

[0117] The spherical lens was processed into a film with a film yield of 60.1%. The molecular weight after processing into films was 91230 and the PDI was 2.03.

[0118] Example 4

[0119] 0.075 mol BPPF, 0.02 mol BHEBBN, 0.012 mol Y-4 compound, 0.088 mol diphenyl carbonate, and 1.0×10⁻⁶ mol tin acetate were added to a reactor equipped with a stirrer and a distillation apparatus. The atmosphere was purged with nitrogen three times and heated to 2000°C at atmospheric pressure for 20 minutes. Once the raw materials were completely melted, stirring was initiated and the pressure was adjusted to 80 kPa(A). The temperature was raised to 250°C, at which point byproducts (phenol and octanol) began to distill. The reaction was maintained for 90 minutes, then the temperature was raised to 270°C and the pressure was gradually reduced to 100 Pa(A) over 1 hour. The reaction was continued for 30 minutes before termination. The resulting high-refractive polymer was removed and evaluated for performance. The measured physical properties of the resulting high-refractive polymer are shown below: the terminal hydroxyl content of the product was 391 ppm, and the content of free small molecule byproducts was 114 ppm.

[0120] 51350, PDI 1.72, refractive index 1.681, Abbe number 21.8, transmittance 89.8%, haze 0.33%, b value 1.41, Tg 133℃, Izod notched impact strength 35J / m 2 .

[0121] The spherical lens was processed into a sheet with a yield of 98.2%. The molecular weight after processing into sheets was 49,000 and the PDI was 1.98.

[0122] Comparative Example 4

[0123] The polymer was prepared by referring to the method of Example 4, except that the Y-4 compound was replaced with an equal molar amount of dimethyl naphthalene dicarboxylate. Other operations and conditions remained unchanged to obtain the polymer.

[0124] The generated high-refractive polymer was taken out and performance evaluation was performed. The measured physical properties of the obtained high-refractive polymer are shown below, wherein the terminal hydroxyl content of the product is 402 ppm, and the content of free small molecule by-products is 134 ppm.

[0125] Molecular weight 53420, PDI 1.82, refractive index 1.678, Abbe number 20.7, transmittance 88.3%, haze 0.34%, b value 1.52, Tg 129℃, Izod notched impact strength 24J / m 2 .

[0126] The spherical lens was processed into a sheet with a yield of 73.2%. The molecular weight after processing was 51905 and the PDI was 1.97.

Claims

1. A high refractive polymer, characterized in that The structural units of the polymer are selected from: Structural units derived from bio-based monomers represented by general formula (Y), In the general formula (Y), R1 each independently represents a hydrogen atom or a methoxy group; R2 each independently represents a C2-C15 alkyl group or a C5-C15 cycloalkyl group; R3 represents a C6-C12 cycloalkyl group or a C6-C20 alkyl group; A structural unit derived from a compound represented by general formula (A), In the general formula (A), R4 and R5 each independently represent 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; A structural unit derived from a compound represented by general formula (B), In the general formula (B), R6 and R7 each independently represent a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C5-C20 cycloalkyl group, a C20 cycloalkoxy group, a C6-C20 aryl group, or a C6-C20 aryloxy group; Wherein, the structural unit derived from the compound represented by general formula (A) and the structural unit derived from the compound represented by general formula (B) are optionally one or both; The high refractive index polymer has a terminal hydroxyl content of less than 1000 ppm; The polymer is prepared by polymerizing a compound represented by general formula (A) and / or general formula (B) with a bio-based monomer represented by general formula (Y) and an optional carbonic acid diester; the carbonic acid diester is selected from at least one of diphenyl carbonate and ditolyl carbonate.

2. The high refractive index polymer according to claim 1, wherein In the general formula (Y), the R2s each independently represent a C4-C8 alkyl group or a C6-C10 cycloalkyl group; and R3 represents a hexyl group, an octyl group or a cyclohexyl group.

3. The high refractive index polymer according to claim 2, wherein The R2s each independently represent n-butyl, n-hexyl, n-octyl, or cyclohexyl.

4. The high refractive index polymer according to claim 1, wherein In the general formula (A), R4 and R5 each independently represent a hydrogen atom, a C1-C3 alkyl group, or a C6-C12 aryl group.

5. The high refractive index polymer according to claim 1, wherein In the general formula (B), R6 and R7 each independently represent a hydrogen atom, a C1-C3 alkyl group, or a C6-C12 aryl group.

6. The high refractive index polymer according to claim 1, wherein The high-refractive polymer has a terminal hydroxyl content of 300-500 ppm.

7. The high refractive polymer according to claim 1, wherein The compound represented by the general formula (A) is selected from at least one of the following structural compounds BPEF and BPPF The compound represented by the general formula (B) is selected from at least one of the following structural compounds BHEBN, BHEBBN 8. The high refractive index polymer according to claim 1, wherein The content of small molecule by-products in the high refractive index polymer is less than 500 ppm; the small molecule by-products include phenol and C4-C8 alcohols; The high refractive polymer has a weight average molecular weight of 10,000 to 150,000; The refractive index of the high-refractive polymer is 1.625 to 1.685 at 23° C. and a wavelength of 589 nm; The Abbe number of the high refractive index polymer is not higher than 24; The high-refractive polymer has a light transmittance greater than 88%, a haze less than 0.7%, and a b value less than 2.

9. The high-refractive polymer according to claim 8, wherein The content of small molecular by-products in the high-refractive polymer is 100-300 ppm.

10. The high refractive index polymer according to claim 8, wherein The C4-C8 alcohols are butanol, hexanol and octanol.

11. The high refractive index polymer according to claim 8, wherein The high-refractive polymer has a weight-average molecular weight of 20,000 to 130,000.

12. The high refractive index polymer according to claim 8, wherein The high-refractive polymer has a weight-average molecular weight of 30,000 to 120,000.

13. The high refractive index polymer according to claim 1, wherein The high-refractive polymer comprises a structural unit derived from a bio-based monomer represented by general formula (Y), and any one or two of a structural unit derived from a compound represented by general formula (A) and a structural unit derived from a compound represented by general formula (B), wherein the molar ratio of the structural unit derived from the bio-based monomer represented by general formula (Y) to the structural unit derived from the compound represented by general formula (A) and the structural unit derived from the compound represented by general formula (B) is 1:0-20:0-20, and the structural unit derived from the compound represented by general formula (A) and the structural unit derived from the compound represented by general formula (B) are not both 0.

14. The high refractive polymer according to claim 13, wherein The molar ratio of the structural unit derived from the bio-based monomer represented by general formula (Y), the structural unit derived from the compound represented by general formula (A), and the structural unit derived from the compound represented by general formula (B) is 1:0.1-15:0.1-15.

15. The high refractive index polymer according to claim 1, wherein The method for preparing a bio-based monomer represented by general formula (Y) comprises the following steps: (1) preparing intermediate C by esterification reaction of vanillic acid or syringic acid with alcohol; (2) The dibromoalkane is polymerized with the intermediate C prepared in step (1) to prepare a bio-based monomer represented by the general formula (Y).

16. The high refractive index polymer according to claim 15, wherein In step (1), the alcohol is selected from at least one of butanol, octanol, and cyclohexanol; The molar ratio of the vanillic acid or syringic acid to the alcohol is 1:1 to 4; The esterification reaction is carried out under the action of a catalyst, which is sulfuric acid; In step (2), the dibromoalkane is selected from at least one of dibromohexane, dibromooctane, and 1,4-dibromocyclohexane; The molar ratio of the dibromoalkane to the intermediate C prepared in step (1) is 1:0.4-0.8; The reaction temperature is 80-140°C; The polymerization reaction is carried out under the action of a catalyst, which is potassium carbonate.

17. The high refractive polymer according to claim 16, wherein In step (1), the molar ratio of the vanillic acid or syringic acid to the alcohol is 1:1.5-2.

5.

18. The high refractive index polymer according to claim 16, wherein In step (1), the amount of the catalyst is 0.5-3 wt% of the alcohol mass.

19. The high refractive index polymer according to claim 16, wherein In step (2), the molar ratio of the dibromoalkane to the intermediate C prepared in step (1) is 1:0.5-0.

6.

20. The high refractive index polymer according to claim 16, wherein In step (2), the reaction temperature is 100-120°C.

21. The high refractive index polymer according to claim 16, wherein In step (2), the molar ratio of the catalyst to the dibromoalkane is 1:0.5-1.

22. A method for preparing the high refractive index polymer according to any one of claims 1 to 21, characterized in that: Prepared by polymerizing a compound represented by general formula (A) and / or general formula (B), a bio-based monomer represented by general formula (Y), and an optional carbonic acid diester; The carbonic acid diester is selected from at least one of diphenyl carbonate and ditolyl carbonate.

23. The preparation method according to claim 22, characterized in that The molar ratio of the sum of the bio-based monomer represented by the general formula (Y) and the carbonic acid diester to the sum of the compounds represented by the general formula (A) and the general formula (B) is 1 to 0.9:

1.

24. The preparation method according to claim 23, characterized in that The molar ratio of the sum of the bio-based monomer represented by the general formula (Y) and the carbonic acid diester to the sum of the compounds represented by the general formula (A) and the general formula (B) is 1 to 0.93:

1.

25. The preparation method according to claim 22, characterized in that The preparation is carried out by a melt transesterification polycondensation method in the presence of a catalyst or in the absence of a catalyst; The 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; The molar ratio of the catalyst to the sum of the bio-based monomer and the carbonate diester represented by the general formula (Y) is 1×10 -8 ~1×10 -3 .

26. The preparation method according to claim 25, characterized in that The molar ratio of the catalyst to the sum of the bio-based monomer and the carbonate diester represented by the general formula (Y) is 1×10 -6 ~1×10 -4 .

27. Use of the high-refractive polymer according to any one of claims 1 to 21 or the high-refractive polymer prepared by the preparation method according to any one of claims 22 to 26 in the field of optical lenses or optical films.

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