Monomeric compound, polymer and optical lens

Abstract

The invention discloses a monomeric compound, a polymer and an optical lens, and relates to the technical field of optical materials, the structural formula of the monomeric compound is as shown in formula (I), in the formula, A is hydrogen or methyl; r1 comprises at least one of hydrogen, fluorine, chlorine, bromine, iodine, a cyano group, a nitro group, a phenyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkyl substituted phenyl group and a C1-C6 alkoxy substituted phenyl group; n = 1, 2, 3, 4 or 5; b comprises a C1-C6 alkyl group, a C1-C6 alkoxy group or does not exist; d comprises a conjugated cyclic group or a substituted conjugated cyclic group. The novel monomeric compound provided by the invention can be used for preparing a polymer with high refractive index, and the polymer has good light transmission and mechanical properties at the same time.

Description

Technical Field

[0001] This invention relates to the field of optical materials technology, and in particular to a monomer compound, a polymer, and an optical lens. Background Technology

[0002] As a special type of optical material, optometry materials must meet at least the following core performance indicators: 1) high light transmittance; 2) good mechanical strength; and 3) adaptability to conventional molding and processing techniques. When optometry materials are used in intraocular implants, low-refractive-index materials often require a greater surface curvature to achieve optical correction while maintaining the same refractive power. However, a greater surface curvature leads to an increase in the overall thickness of the product, and such a bulky product design has significant clinical limitations in ophthalmic implant surgery applications.

[0003] Therefore, developing optometry materials that simultaneously meet the requirements of lightweight and thin design, excellent mechanical properties, and good adaptability to processing technology remains an important technological challenge in this field. Summary of the Invention

[0004] The main objective of this invention is to propose a monomer compound, a polymer, and an optical lens, aiming to solve the problem of insufficient refractive index of polymer materials used in optical materials in the prior art.

[0005] To achieve the above objectives, the present invention proposes a monomeric compound, the structural formula of which is shown in formula (I):

[0006] (I); Where A is hydrogen or methyl; R1 includes at least one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, phenyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl-substituted phenyl, and C1-C6 alkoxy-substituted phenyl; n = 1, 2, 3, 4 or 5; B includes C1-C6 alkyl, C1-C6 alkoxy, or is absent; D includes conjugated cyclic groups or substituted conjugated cyclic groups.

[0007] In one embodiment, D comprises a phenyl or substituted phenyl group, and the monomer compound has the structural formula shown in formula (II):

[0008] (II); Wherein, R2 is at least one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, phenyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl-substituted phenyl and C1-C6 alkoxy-substituted phenyl; i = 1, 2, 3, 4 or 5.

[0009] In one embodiment, the monomeric compound comprises at least one of A1 to A5: .

[0010] In one embodiment, D comprises a thickened aromatic hydrocarbon, the monomer compound having the structural formula shown in formula (III), formula (IV), or formula (V):

[0011] (III)

[0012] (Ⅳ)

[0013] (V); R2, R3, R4, R5, R6, R7, R8, and R9 are selected from at least one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, phenyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl-substituted phenyl, and C1-C6 alkoxy-substituted phenyl. i1 = 1, 2 or 3, j1 = 1, 2, 3 or 4; i2 = 1, 2 or 3, j2 = 1 or 2, k = 1, 2, 3 or 4; i3 = 1, 2, 3 or 4, j3 = 1, 2, 3 or 4.

[0014] In one embodiment, the monomeric compound comprises at least one of A6 to A10: .

[0015] The present invention also provides a polymer obtained by polymerization of a crosslinking agent and the aforementioned monomer compound.

[0016] In one embodiment, the polymer is obtained by polymerization of a crosslinking agent and the aforementioned monomer compound, the polymer has a refractive index of 1.54 to 1.58, a visible light transmittance of ≥85%, and a non-blue light transmittance of ≥89%.

[0017] In one embodiment, the polymer is obtained by polymerization of a crosslinking agent and the aforementioned monomer compound, wherein the polymer has a refractive index ≥1.59, a visible light transmittance ≥68%, and a non-blue visible light transmittance ≥83%.

[0018] The present invention also provides an optical lens comprising the aforementioned polymer.

[0019] In one embodiment, at 100mm -1 At spatial frequencies, the modulation transfer function value of the optical lens is >0.5; and / or, The cylindrical lens of the optical lens is <0.14D; and / or, The absolute value of the spherical aberration of the optical lens is <0.30 μm.

[0020] The present invention provides a novel monomeric compound with two important molecular structural features: First, it has a discontinuously distributed diester bond structure. This design helps to hinder the molecular chain crystallization behavior during the polymerization of the monomeric compound into a polymer, constructing an amorphous polymer and thus ensuring good transparency of the polymer material. Second, it has two conjugated cyclic group positions with a reasonable chemical bond spacing between them, avoiding the influence of steric hindrance, reducing the difficulty of polymerizing the monomeric compound into a polymer, and ensuring that the polymer material has good mechanical strength and refractive index. Therefore, the polymer formed by the polymerization of the novel monomeric compound provided by the present invention has good light transmittance, mechanical strength, and high refractive index, making it suitable as an ophthalmic lens material such as intraocular lenses, orthokeratology lenses, and corneal implants. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0022] Figure 1 The spectral transmittance curves of polymers B1 to B9 of the present invention are shown. Figure 2 The spectral transmittance curves of polymers B10 to B14 of this invention are shown. Figure 3 The stress-strain curves of polymers B1~B10 and B12~B14 of the present invention are shown. Figure 4The images show physical representations of the five optical lenses used in this invention (from left to right, they correspond to polymer materials B2, B8, B9, B10, and B12, respectively). Figure 5 This is a magnified image of the font produced by the optical lens made of polymer material B2 according to the present invention. Figure 6 Power-Distance curve of the optical lens prepared from polymer material B2 of the present invention; Figure 7 Power-Distance curve of the optical lens prepared from polymer material B8 of the present invention; Figure 8 Power-Distance curve of the optical lens prepared from polymer material B9 of the present invention; Figure 9 Power-Distance curve of the optical lens made of polymer material B10 of the present invention; Figure 10 Power-Distance curve of the optical lens made of polymer material B12 of the present invention.

[0023] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially. Furthermore, the meaning of "and / or" throughout the text includes three parallel solutions; for example, "A and / or B" includes solution A, or solution B, or a solution where both A and B are satisfied simultaneously. In addition, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] This invention provides a monomeric compound, the structural formula of which is shown in formula (I):

[0026] (I); Wherein, A is hydrogen or methyl; R1 includes at least one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, phenyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl-substituted phenyl, and C1-C6 alkoxy-substituted phenyl; n = 1, 2, 3, 4, or 5; B includes C1-C6 alkyl, C1-C6 alkoxy, or is absent; D includes a conjugated cyclic group or a substituted conjugated cyclic group.

[0027] The present invention provides a novel monomeric compound having at least the following molecular structural features: First, it has a discontinuously distributed diester bond structure. This design helps to hinder the molecular chain crystallization behavior during the polymerization of the monomeric compound into a polymer, constructing an amorphous polymer and thus ensuring good light transmittance of the polymer material. Second, it has two conjugated cyclic group positions with a reasonable chemical bond spacing between the two positions, avoiding the influence of steric hindrance, reducing the difficulty of polymerizing the monomeric compound into a polymer, and ensuring that the polymer material has good mechanical strength and refractive index. Therefore, the polymer formed by the polymerization of the novel monomeric compound provided by the present invention has good light transmittance, mechanical strength, and high refractive index, making it suitable as an ophthalmic lens material such as intraocular lenses, orthokeratology lenses, and corneal implants.

[0028] It is understood that the branched benzene ring between the diester bonds may have one R1 substituent, which may be any one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, phenyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl-substituted phenyl, or C1-C6 alkoxy-substituted phenyl. The branched benzene ring between the diester bonds may also have two, three, four, or five R1 substituents. The R1 substituents may be the same or different. When they are different, they may be two or more of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, phenyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl-substituted phenyl, or C1-C6 alkoxy-substituted phenyl, all of which are within the scope of protection of this invention. C1-C6 alkyl refers to a straight-chain or branched saturated aliphatic hydrocarbon group containing 1 to 6 carbon atoms. That is, the substituent can be a saturated aliphatic hydrocarbon group containing one carbon atom, two carbon atoms, three carbon atoms, four carbon atoms, five carbon atoms, or six carbon atoms. C1-C6 alkyl-substituted phenyl refers to a group formed by replacing one or more hydrogen atoms on a phenyl (-C6H5) ring with a C1-C6 alkyl group. In other words, the substituted position is a benzene ring derivative with two carbon-carbon bonds, and at least one of the substituted positions on this benzene ring derivative is replaced by a C1, C2, C3, C4, C5, or C6 alkyl group. Similarly, the definitions of C1-C6 alkoxy and C1-C6 alkoxy-substituted phenyl are similar to those of C1-C6 alkyl and C1-C6 alkyl-substituted phenyl.

[0029] It should be noted that the conjugated cyclic structures (which can be conjugated cyclic groups or substituted conjugated cyclic groups) in the conjugated cyclic group positions of the novel monomer compound provided by this invention exhibit significant polarization, which is the basis for improving the polymer's refractive index. However, an unreasonable arrangement of multiple sterically hindered conjugated groups in the molecule can affect the polymerization effect of the compound, and poor polymerization can negatively impact the mechanical properties of the material. Therefore, setting chemical bonds to stagger the positions of the two conjugated cyclic groups can reduce the polymerization steric hindrance during the self-polymerization of this novel monomer compound, allowing the polymer molecular chains to grow longer. Longer molecular chains result in greater mechanical strength in the material. This is an optimization method for the novel monomer compound of this invention to improve the refractive index while maintaining good mechanical strength.

[0030] It should be noted that B may or may not be present. When B is present, it can be a C1-C6 alkyl or C1-C6 alkoxy group, with D connected to the oxygen element in B or to the carbon element in B. When B is absent, D is connected to an ester group. D can be a conjugated cyclic group or a substituted conjugated cyclic group. A conjugated cyclic group refers to a cyclic structure composed of three or more atoms, with alternating single and double (or triple) bonds within the ring or between the ring and side groups, forming a π-electron delocalization (i.e., a conjugated system). A substituted conjugated cyclic group refers to a group formed when one or more hydrogen atoms of a conjugated cyclic group are replaced by other substituents. As can be seen from formula (I), in the novel monomer compound provided by the present invention, both ester groups are located on the main chain where the C-C double bond (used for polymerization reaction) is located, and D is also located on the main chain. The other benzene ring is located on the alkyl group between the diester bonds. That is, the present invention sets two ester bonds and two conjugated cyclic groups. The two conjugated cyclic groups can effectively improve the refractive index of the polymer material, and the two ester bonds can hinder the crystallization of the polymer molecular chain, thereby improving the transparency of the polymer material and thus improving the light transmittance of the material. Furthermore, the first conjugated cyclic group position is set between the first ester bond and the second ester bond, and the second conjugated cyclic group position is set on the other side of the second diester bond. This design can ensure that the polymer material has good refractive index, light transmittance, and mechanical strength.

[0031] In some embodiments, D comprises a phenyl or substituted phenyl group, and the monomeric compound has the structural formula shown in formula (II):

[0032] (II); Wherein, R2 is at least one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, phenyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl-substituted phenyl and C1-C6 alkoxy-substituted phenyl; i = 1, 2, 3, 4 or 5.

[0033] In the technical solution of this invention, D includes a conjugated cyclic group or a substituted conjugated cyclic group, wherein D is preferably phenyl or a substituted phenyl group, as phenyl or a substituted phenyl group can better improve the refractive index of the polymer material. Furthermore, depending on the differences between A, B, and D, the structural formula of the monomer compound is preferably at least one of A1 to A5: .

[0034] Compared to A1, A4 contains a B group, but the refractive index and hardness of the homopolymer prepared from A4 are lower than those from A1, although their visible light transmittance is not significantly different. Similarly, the performance comparison of the homopolymers prepared from A2 and A5 yields similar results. Generally, the chemical separation between the benzene ring and the ester group makes the polymer chains of A3, A4, and A5 more flexible than those corresponding to A1 and A2. However, A3 contains a meta-nitro group; the polarity and steric hindrance of the nitro group can restrict the movement of molecular segments to some extent, thus increasing the glass transition temperature of the material. Additionally, A3 has shorter alkene chemical bonds, which causes the difference between the polymers corresponding to A3 and those corresponding to A4 and A5. Therefore, the following is reasonable: at room temperature, polymers prepared from A1, A2, and A3 are glassy polymers, while polymers prepared from A4 and A5 are rubbery polymers. The tensile strength of the glassy polymers corresponding to A1, A2, and A3 is higher than that of the rubbery polymers corresponding to A4 and A5.

[0035] Preferably, in some embodiments, D comprises a thickened aromatic hydrocarbon, the monomer compound having the structural formula shown in formula (III), formula (IV), or formula (V):

[0036] (III)

[0037] (Ⅳ)

[0038] (V); Wherein, R2, R3, R4, R5, R6, R7, R8, and R9 are selected from at least one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, phenyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl-substituted phenyl, and C1-C6 alkoxy-substituted phenyl; i1 = 1, 2, or 3, j1 = 1, 2, 3, or 4; i2 = 1, 2, or 3, j2 = 1, 2, k = 1, 2, 3, or 4; i3 = 1, 2, 3, or 4, j3 = 1, 2, 3, or 4. It is understood that when D is a thickened aromatic hydrocarbon, the polymer formed by the polymerization of the monomer compound has a better refractive index. More preferably, the monomer compound includes at least one of A6 to A10: .

[0039] Among A6 and A7, when A is hydrogen, the polymer formed by the monomer compound has a higher refractive index, as well as better light transmittance and hardness. This is because the polarization ability of the functional groups is ranked as follows: aromatic ring > methylene > methyl; the greater the polarization ability, the higher the refractive index. The polymer with high polarization ability has a larger proportion of highly polarized groups than that with A6. Compared to A9, A7 has a higher refractive index because A9 has an additional methylene group that contributes less to the refractive index. Furthermore, compared to A2, replacing a single benzene ring with a fused ring structure formed by two benzene rings sharing a single side results in a higher refractive index for the polymer formed in A7.

[0040] The monomeric compounds in this invention are prepared by a two-step organic reaction. Specifically: the first step involves an addition reaction between an aromatic epoxide or its derivative analogue and an aromatic substituted carboxylic acid. The addition reaction is catalyzed under basic or acidic conditions, using aprotic solvents such as alkanes, haloalkanes, tetrahydrofuran, dioxane, N,N-dimethylformamide, dimethyl sulfoxide, ethyl acetate, and butyl acetate. Catalysts include boron trifluoride, tetrabutylammonium bromide, tetrabutylammonium chloride, berberine trifluorosulfonate, zinc chloride, sodium hydroxide, and hydrogen chloride. After the addition reaction, the intermediate product is obtained by column chromatography. The second step involves the condensation of the intermediate product with an alkenyl carboxylic acid or alkenyl acyl chloride to obtain the monomeric compound. The condensation reaction is carried out under the action of a catalyst, removing a small molecule and forming an ester-containing compound. The synthetic methods for all monomeric compounds provided in this invention are similar.

[0041] The present invention also provides a polymer obtained by polymerization of a crosslinking agent and the aforementioned monomer compounds. Therefore, it possesses all the beneficial effects of the aforementioned monomer compounds, which will not be elaborated further here. Preferably, the polymer is obtained by polymerization of a crosslinking agent and monomer compounds of formula (I) or A1~A5, the polymer has a refractive index of 1.54~1.58, a visible light transmittance ≥85%, and a non-blue light transmittance ≥89%. More preferably, the polymer is obtained by polymerization of a crosslinking agent and monomer compounds of formula (III), (IV), or (V), or A6~A10. The polymer has a refractive index ≥1.59, a visible light transmittance ≥68%, and a non-blue light visible light transmittance ≥83%. The refractive index of the polymer is significantly improved. At the same time, the polymer obtained by polymerization of monomer compounds of formula (III), (IV), or (V), or A6~A10 has blue light absorption and can be used in the field of digital device protection. Moreover, its non-blue light visible light transmittance is basically at the level of the polymer obtained by polymerization of monomer compounds of formula (I) or A1~A5, thus expanding the application field of the polymer.

[0042] It should be noted that the content of crosslinking agent in the polymer provided by the present invention is no more than 10%, and it ultimately exists in the polymer in the form of specific compound segments.

[0043] The present invention also provides an optical lens comprising the aforementioned polymer. Therefore, it possesses all the beneficial effects of the aforementioned polymer, which will not be elaborated further here. Preferably, at 100mm... -1 At spatial frequencies, the modulation transfer function value of the optical lens is >0.5; and / or, the cylindrical lens diameter of the optical lens is <0.14D; and / or, the absolute value of the spherical aberration of the optical lens is <0.30μm. Wherein, at 100mm... -1 At spatial frequency, a modulation transfer function value > 0.5 indicates that the optical lens has excellent imaging quality, and the absolute value of spherical aberration is relatively small compared to that of a cylindrical lens, making it suitable for manufacturing precision optical devices and meeting the requirements of optometry devices.

[0044] The technical solution of the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings. It should be understood that the following embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0045] Example 1 A monomeric compound A1 is prepared by the following steps: (1) Synthesis of 2-hydroxy-2-phenylethylbenzoate: Take a single-necked flask, weigh out 5.00 g of benzoic acid and 5.41 g of styrene oxide, add 0.20 g of tetrabutylammonium bromide catalyst, dissolve in 100 mL of N,N-dimethylformamide, stir magnetically, set the temperature to 80 °C, and react for 16 hours. Then raise the temperature to 100 °C and continue the reaction for 5 hours. After the reaction is complete, allow it to return to room temperature, remove the solvent by rotary evaporation, dissolve the remaining substance in ethyl acetate, and wash three times with saturated sodium bicarbonate and water, respectively. Take the organic phase, add anhydrous magnesium sulfate and dry, after drying for 4 hours, filter to obtain the filtrate, remove the solvent by rotary evaporation to obtain a viscous crude product. Purify the crude product by column chromatography (ethyl acetate / petroleum ether = 1 / 10) to obtain 8.87 g of purified 2-hydroxy-2-phenylethylbenzoate, which is a clear liquid. 1 HNMR confirmed the chemical structure of the purified product in this step. 1 H NMR (400 MHz, CDCl3) δ 8.07 – 8.02 (m,2H), 7.61 – 7.54 (m, 1H), 7.40 (dddd, J = 17.3, 11.3, 3.5, 2.0 Hz, 7H), 5.11(dd, J = 8.1, 3.5 Hz, 1H), 4.53 (dd,J = 11.6, 3.5 Hz, 1H), 4.43 (dd, J = 11.6, 8.1Hz, 1H).

[0046] (2) Synthesis of A1 from 2-hydroxy-2-phenylethylbenzoate: Take a single-necked flask, weigh 1.51 g of the purified product from the previous step, 2-hydroxy-2-phenylethylbenzoate, and 0.95 g of triethylamine. Add 0.15 g of 4-dimethylaminopyridine and dissolve it in 100 mL of tetrahydrofuran. Stir magnetically in an ice bath. Then weigh 0.98 g of methacryloyl chloride, dilute it with 20 mL of tetrahydrofuran, and slowly add it dropwise using a constant pressure dropping funnel. A large amount of white turbidity is produced in the flask. After the addition is complete, continue stirring at room temperature for 5 hours to obtain a mixture. Filter the mixture to remove the white precipitate, collect the filtrate, and remove the solvent by rotary evaporation. Dissolve the residue in dichloromethane and wash three times with saturated sodium bicarbonate and water, respectively. Take the organic phase, add anhydrous magnesium sulfate and dry for 4 hours. Filter to obtain the filtrate, remove the solvent by rotary evaporation to obtain the crude product. The crude product was purified by column chromatography (ethyl acetate / petroleum ether = 1 / 10) to obtain 0.28 g of purified product, which was a clear viscous liquid. 1 HNMR confirmed the chemical structure of the purified product in this step. 1 H NMR (400 MHz, CDCl3) δ 8.06 – 7.97 (m, 2H), 7.60 – 7.50 (m, 1H), 7.47 – 7.35 (m, 7H), 6.24(dd, J = 7.9, 3.9 Hz, 1H), 6.21 (s, 1H), 5.60 (dd, J = 5.5, 4.0 Hz, 1H), 4.68 –4.61 (m, 1H), 4.58 (dd, J = 11.8, 4.0 Hz, 1H), 1.96 (s, 3H).

[0047] Example 2 A monomeric compound A2 is prepared in a manner similar to that in Example 1, except that: In the second step reaction (2), methacryloyl chloride in Example 1 was replaced with an equimolar amount of acryloyl chloride, and the rest of the operation was completely consistent with Example 1.

[0048] final product 1 HNMR characterization is as follows: 1H NMR (400 MHz, CDCl3) δ 8.12 – 7.97 (m, 2H), 7.59 – 7.52 (m, 1H), 7.50 – 7.31 (m, 7H), 6.43 (ddd, J = 29.7, 17.3, 1.0 Hz,1H), 6.28 (ddd, J = 18.0, 11.4, 7.0 Hz, 1H), 6.21 – 6.05 (m, 1H), 5.85 (ddd, J =18.0, 10.4, 1.0 Hz, 1H), 4.66 – 4.60 (m, 1H), 4.58 (dd, J = 8.3, 3.6 Hz, 1H).

[0049] Example 3 A monomeric compound A3 is prepared in a manner similar to that in Example 1, except that: In the first step reaction (1), benzoic acid in Example 1 was replaced with an equimolar amount of m-nitrophenylpropionic acid, and the rest of the feeding and operation were completely the same.

[0050] product 1 HNMR characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ 8.13 – 7.97 (m, 2H), 7.53– 7.40 (m, 2H), 7.34 (dt, J = 11.6, 5.9 Hz, 5H), 6.22 – 6.13 (m, 1H), 6.09 –6.02 (m, 1H), 5.58 (d, J = 23.2 Hz, 1H), 4.44 – 4.31 (m, 2H), 3.13 – 2.94 (m,2H), 2.81 – 2.60 (m, 2H), 1.92 (d, J = 23.2 Hz, 3H).

[0051] Example 4 A monomeric compound A4 is prepared in a manner similar to that in Example 1, except that: In the first step reaction (1), benzoic acid in Example 1 was replaced with phenylbutyric acid in equal molar amounts, and the rest of the operation was completely consistent with Example 1.

[0052] product 1 HNMR characterization is as follows: 1H NMR (400 MHz, CDCl3) δ 7.41 – 7.27 (m, 7H), 7.16(dd, J = 11.7, 7.4 Hz, 3H), 6.19 (s, 1H), 6.08 (dd, J = 8.0, 3.9 Hz, 1H), 5.60(s, 1H), 4.49 – 4.37 (m, 1H), 4.37 – 4.30 (m, 1H), 2.61 (t, J = 7.5 Hz, 2H), 2.32 (t, J = 7.4 Hz, 2H), 1.95 (s, 3H), 1.93 – 1.89 (m, 2H).

[0053] Example 5 A monomeric compound A5 is prepared in a manner similar to that in Example 1, except that: In the first step reaction (1), benzoic acid in Example 1 was replaced with phenylbutyric acid in an equal molar amount; In the second step reaction (2), methacryloyl chloride in Example 1 was replaced with an equimolar amount of acryloyl chloride, and the rest of the operation was completely consistent with Example 1.

[0054] product 1 HNMR characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ 7.41 – 7.24 (m, 7H), 7.22– 7.12 (m, 3H), 6.42 (ddd, J = 21.8, 17.3, 1.4 Hz, 1H), 6.23 – 6.13 (m, 1H), 6.09 (ddd, J = 10.6, 6.1, 3.1 Hz, 1H), 5.85 (td, J = 10.8, 1.4 Hz, 1H), 4.43 –4.38 (m, 1H), 4.37 – 4.32 (m, 1H), 2.62 (dd, J = 14.0, 6.6 Hz, 2H), 2.44 – 2.26(m, 2H), 1.94 (dp, J = 15.0, 7.5 Hz, 2H).

[0055] Example 6 A monomeric compound A6 is prepared in a manner similar to that in Example 1, except that: In the first step reaction (1), benzoic acid in the example was replaced with an equimolar amount of 2-naphthoic acid, and the rest of the operation was completely consistent with Example 1.

[0056] product 1 HNMR characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ 8.62 (dd, J = 37.6, 10.4 Hz,1H), 8.05 – 7.91 (m, 2H), 7.91 – 7.86 (m, 2H), 7.61 – 7.53 (m, 2H), 7.45 –7.31 (m, 5H), 6.35 – 6.26 (m, 1H), 6.24 – 6.05 (m, 1H), 5.64 – 5.51 (m, 1H), 4.74 – 4.66 (m, 1H), 4.64 – 4.51 (m, 1H), 2.02 – 1.92 (m, 3H).

[0057] Example 7 A monomeric compound A7 is prepared in a manner similar to that in Example 1, except that: In the first step reaction (1), benzoic acid in Example 1 was replaced with an equimolar amount of 2-naphthoic acid; In the second step reaction (2), methacryloyl chloride in Example 1 was replaced with an equimolar amount of acryloyl chloride, and the rest of the operation was completely consistent with Example 1.

[0058] product 1 HNMR characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ 8.56 (s, 1H), 8.01 (dd, J =8.6, 1.6 Hz, 1H), 7.93 (t, J = 8.6 Hz, 1H), 7.88 (t, J = 8.0 Hz, 2H), 7.63 – 7.53(m, 2H), 7.50 – 7.35 (m, 5H), 6.52 – 6.45 (m, 1H), 6.33 (dt, J = 7.9, 3.8 Hz,1H), 6.26 – 6.16 (m, 1H), 5.87 (dd, J = 10.4, 1.2 Hz, 1H), 4.70 (dd, J= 11.8,8.0 Hz, 1H), 4.66 – 4.61 (m, 1H).

[0059] Example 8 A monomeric compound A8 is prepared in a manner similar to that in Example 1, except that: In the first step reaction (1), benzoic acid in the example was replaced with an equimolar amount of 1-naphthaleneacetic acid, and the rest of the operation was completely consistent with Example 1.

[0060] product 1 HNMR characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ 7.99 – 7.74 (m, 5H), 7.52 – 7.35 (m, 7H), 6.15 – 6.05 (m, 1H), 6.02 (s, 1H), 5.50 (s, 1H), 4.47 – 4.39(m, 1H), 4.39 – 4.35 (m, 1H), 4.10 – 4.01 (m, 2H), 1.90 – 1.82 (m, 3H).

[0061] Example 9 A monomeric compound A9 is prepared in a manner similar to that in Example 1, except that: In the first step reaction (1), benzoic acid in Example 1 was replaced with an equimolar amount of 1-naphthaleneacetic acid. In the second step reaction (2), methacryloyl chloride in Example 1 was replaced with an equimolar amount of acryloyl chloride. The remaining operations were completely consistent with those in Example 1.

[0062] product 1 HNMR characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ 7.98 – 7.76 (m, 5H), 7.53– 7.33 (m, 7H), 6.33 (dd, J = 17.3, 1.4 Hz, 1H), 6.09 – 6.04 (m, 1H), 6.02 (dd, J = 8.1, 5.8 Hz, 1H), 5.79 (dd, J = 10.4, 1.4 Hz, 1H), 4.38 (s, 1H), 4.36 (d, J =5.9 Hz, 1H), 4.06 (s, 2H).

[0063] Example 10 A monomeric compound A10 is prepared in a manner similar to that in Example 1, except that: In the first step reaction (1), benzoic acid in Example 1 was replaced with an equimolar amount of 9-anthracarboxylic acid; In the second step reaction (2), methacryloyl chloride in Example 1 was replaced with an equimolar amount of acryloyl chloride, and the rest of the operation was completely consistent with Example 1.

[0064] product 1 HNMR characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ 8.54 (d, J = 4.1 Hz, 1H),8.07 – 7.87 (m, 4H), 7.62 – 7.31 (m, 9H), 6.60 – 6.43 (m, 1H), 6.35 – 6.28(m, 1H), 6.23 (dd, J = 17.6, 10.4 Hz, 1H), 5.93 (dd, J = 28.2, 10.4 Hz, 1H), 5.02(dd, J = 11.8, 7.9 Hz, 1H), 4.86 (dd, J = 11.9, 3.8 Hz, 1H).

[0065] Performance testing I. Properties of Monomer Compounds Table 1 summarizes the monomeric compounds and their physical states provided in Examples 1-10.

[0066] Table 1 Monomer compounds and their states

[0067] The monomer compounds listed in Table 1 are used as raw materials for polymer material preparation. Their apparent state at room temperature and pressure significantly impacts their operability, particularly during bulk polymerization. All the monomer compounds listed are liquids or viscous substances, which facilitates bulk polymerization. It is worth noting that monomers containing fused-ring aromatic groups, such as A6 to A10, have higher viscosity at room temperature and pressure. These raw materials require longer mixing and dissolution times or slight heating to promote uniform dissolution, and ultrasonic vibration to ensure a homogeneous, bubble-free mixture; otherwise, the transparency and mechanical strength of the material will be affected. It should be noted that A10 has excessive viscosity, exhibiting a difficult-to-flow state at room temperature, and cannot dissolve the other added reactants. Therefore, it cannot be directly used for bulk polymerization and must be blended and copolymerized with other non-viscous monomers to prepare the polymer.

[0068] II. Polymer Preparation and Characterization 1. Nine single monomer compounds, A1 to A9, were used to prepare polymers B1 to B9. The specific preparation steps were as follows: the total amount of monomer compounds was 94.8 wt%, the amount of crosslinking agent ethylene glycol dimethacrylate was 3.8 wt%, and the amount of initiator 2,5-dimethyl-2,5-bis(2-ethylhexanoic acid peroxide)hexane was 1.4 wt%. The above materials were weighed and mixed, and then ultrasonically vibrated for 5 minutes to completely dissolve them into a transparent state. The dissolved mixture was filtered through a 0.22 μm polytetrafluoroethylene filter membrane and transferred to a curing mold. It was then placed in an inert atmosphere oven for curing. The curing conditions were: 50℃ for 2 hours, then increased to 70℃ for 3 hours, and then increased to 85℃ for 16 hours. After curing, the obtained polymers were removed from the mold and placed in a 60℃ vacuum oven to dry overnight to obtain nine homopolymers.

[0069] 2. Two or more monomer compounds selected from A2, A4, A5, A8, A9, and A10 are used together to prepare five groups of copolymers B10 to B14 using the preparation method described in step 1. It is worth noting that during the mixing solution stage, because some of the monomers are relatively viscous, the fluidity of the mixed solution can be increased by appropriately raising the temperature to achieve a more uniform mixing state.

[0070] The performance of the nine homopolymers and five copolymers prepared above was tested, and the specific tests are shown below: (1) Glass transition temperature: The glass transition temperature of the material was measured using a Shimadzu differential scanning calorimeter, model DSC-60Plus, at a temperature rate of 20℃ / min. (2) Determination of refractive index and Abbe number: The refractive index and Abbe number of the material were determined using an Aituo Abbe refractometer, model DR-M2. The Abbe number Vd = (nD-1) / (nF-nC), where nD, nF, and nC are the refractive indices at 589nm, 486nm, and 656nm, respectively. (3) Measurement of spectral transmittance: The spectral transmittance of the materials in the wavelength range of 300~1100nm was measured using a Shimadzu visible-ultraviolet spectrophotometer, model UV-1900i; among them, the spectral transmittance curves of polymers B1~B9 are shown in the figure. Figure 1 As shown in the figure, the spectral transmittance curves of polymers B10~B14 are as follows. Figure 2 As shown; (4) Determination of mechanical parameters: The elastic modulus, tensile strength, and elongation at break were determined by a universal testing machine (model WBE-9010B) at room temperature under constant-rate tensile testing; the Shore hardness was determined by a Shore A hardness tester (model LX-A) from Shanghai Yizong Precision Instruments Co., Ltd., at room temperature; the stress-strain curves of polymers B1~B10 and B12~B14 are shown in the figure. Figure 3 As shown in Table 2, the test results for the homopolymer are shown in Table 3, and the test results for the copolymer are shown in Table 4.

[0071] Table 2 shows the performance characterization results of the homopolymers corresponding to Examples 1-9.

[0072] Table 3 Performance characterization results of the copolymer

[0073] From Table 2, Table 3 and Figure 1 , Figure 2 and Figure 3 It can be seen that (1) polymers B1~B14 have refractive indices of 1.54~1.62, but the refractive indices of B1~B5 are lower than those of B6~B9. This may be because the molecules of B6~B9 have more aromatic ring structures, indicating that the larger refractive index is affected by the large number of aromatic ring structures in the molecular structure. (2) From Figure 3 The stress-strain curves show that the mechanical differences of the polymer materials are relatively large, which may be due to the different side group steric hindrances of the polymers formed by the polymerization of monomer compounds. (3) In this invention, the spectral transmittance of the visible light region (400~780nm) is divided into the blue light transmittance region of 400~500nm and the non-blue light transmittance region of 500~780nm. Table 1 shows the average transmittance of visible light (average transmittance of spectral transmittance of 400~780nm, hereinafter referred to as T1) and the average transmittance of visible light after deducting the blue light region (average transmittance of spectral transmittance of spectral transmittance of 500~780nm, hereinafter referred to as T2) to distinguish the influence of blue light absorption on the overall visible light transmittance: From Tables 2~4 and Figures 1-2 It is known that the T2 of all polymer materials is around 90%, while the T1 shows some differences. This difference is reflected in the light transmittance in the blue light region. Specifically, the T1 of some polymer materials is lower than their T2, and these materials appear pale yellow or yellow because they have significant blue light absorption characteristics. The remaining materials have T1 and T2 that are closer, with no blue light absorption, and therefore appear colorless and transparent. The root cause of this difference may be the electron-withdrawing side groups of the aromatic rings in the molecular structure and the oxidation of the aromatic rings. According to the test results, high-refractive-index materials exhibit good optical performance and good mechanical adjustability.

[0074] Specifically, comparing A1 and A4, A4 contains a B group, but the refractive index and hardness of the homopolymer B4 prepared from A4 are lower than those of the homopolymer B1 prepared from A1, although their visible light transmittance is not significantly different. Similarly, the performance comparison results for the homopolymers prepared from A2 and A5 are similar. Comparing A6 and A7, when the A group is hydrogen, the polymer B7 formed from the monomer compound has a higher refractive index and better transmittance and hardness in the visible light region. Comparing A7 and A9, the copolymer B7 formed from A7 has a higher refractive index because A9 contains one more methylene group than A7, and the contribution of the methylene group to the material's refractive index is relatively small compared to the rest of the molecule. Furthermore, compared to A2 and A7, replacing a single benzene ring with a fused ring structure formed by two benzene rings sharing a single side results in a polymer with a higher refractive index in A7.

[0075] It should be noted that the homopolymers prepared by the monomers in Example 7 have the same average spectral transmittance in the blue light transmission region of 400-500 nm and the non-blue light transmission region of 500-780 nm. The blue light absorption is due to the yellowing of the polymer. The A7 polymerization process may have avoided oxidation and did not result in yellowing, so no blue light absorption occurred.

[0076] III. Fabrication and Characterization of Optical Lenses Using a polypropylene mold (a combination mold of a female mold and a male mold, both with optical surfaces designed on their inner surfaces), lens samples were prepared by casting according to the proportions of five polymers (B2, B8, B9, B10, and B12). The specific steps were as follows: the raw materials were weighed, mixed, and dissolved evenly, then dropped onto the female mold, the male mold was closed, and the samples were placed in an oven for curing. The curing temperature program was consistent with that used for the second polymer preparation. The resulting five sets of lens samples all contained biconvex optical surfaces, consisting of two regions: a central biconvex lens region with focusing capabilities and a planar region with no optical power at the edge. Subsequently, the optical imaging quality of the five sets of lens samples was evaluated using a LAMBDA-X optical analyzer (model NIMO TR0815) with a 3mm aperture, measuring various optical parameters, including optical power, in physiological saline solution at 100mm. -1 MTF at spatial frequency 100 The data for cylindrical lens and spherical aberration are shown in Table 5. The external images of the five optical lenses are shown below. Figure 4 As shown; the visual magnification effect of lens B2 on the font is shown in the image below. Figure 5 As shown; Figure 6 , Figure 7 , Figure 8 , Figure 9 , Figure 10 The graphs show the changes in optical power within a radius of 1.5 mm from the center of each of the five optical lenses.

[0077] Table 5 Optical parameters of different optical lenses

[0078] Depend on Figure 4 It can be seen that the optical surfaces of the five sets of optical lenses are in good condition. Figure 5 It can be seen that lens B2 produces a clear image. (Based on Table 5 and...) Figures 6 to 10 It can be seen that the optical power values ​​of the five lens groups fluctuate relatively little, indicating good uniformity in optical power; the MTF of all lenses... 100 A value >0.5 indicates excellent imaging quality. Furthermore, the absolute value of spherical aberration and cylindrical lens strength are both relatively small. This demonstrates that the monomeric compound of this invention is well-suited for casting processes, and the resulting optical lenses meet the requirements for manufacturing precision optical devices and can adapt to the needs of complex optical designs, making it an excellent optical material.

[0079] In summary, this invention has prepared a class of monomeric compounds with typical structural characteristics and their high refractive polymers using chemical methods. The good usability of these compounds has been verified through lens fabrication, demonstrating that this invention yields an excellent optical material with practical value, which can be used in the development of high-quality thin lenses.

[0080] The above are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the patent protection scope of the present invention.

Claims

1. A monomeric compound, characterized in that, The structural formula of the monomer compound is shown in formula (Ⅰ): （Ⅰ）； Where A is hydrogen or methyl; R1 includes at least one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, phenyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl-substituted phenyl, and C1-C6 alkoxy-substituted phenyl; n = 1, 2, 3, 4 or 5; B includes C1-C6 alkyl, C1-C6 alkoxy, or is absent; D includes conjugated cyclic groups or substituted conjugated cyclic groups.

2. The monomeric compound according to claim 1, characterized in that, D includes phenyl or substituted phenyl compounds, and the structural formula of the monomeric compound is shown in formula (II): （Ⅱ）； Wherein, R2 is at least one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, phenyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl-substituted phenyl and C1-C6 alkoxy-substituted phenyl; i = 1, 2, 3, 4 or 5.

3. The monomeric compound according to claim 2, characterized in that, The monomeric compound includes at least one of A1 to A5: 。 4. The monomeric compound according to claim 1, characterized in that, D includes thickened aromatic hydrocarbons, the structural formula of which is shown in formula (III), formula (IV), or formula (V): （Ⅲ）、 （Ⅳ）、 （Ⅴ）； R2, R3, R4, R5, R6, R7, R8, and R9 are selected from at least one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, phenyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl-substituted phenyl, and C1-C6 alkoxy-substituted phenyl. i1 = 1, 2 or 3, j1 = 1, 2, 3 or 4; i2 = 1, 2 or 3, j2 = 1 or 2, k = 1, 2, 3 or 4; i3 = 1, 2, 3 or 4, j3 = 1, 2, 3 or 4.

5. The monomeric compound according to claim 4, characterized in that, The monomeric compound includes at least one of A6 to A10: 。 6. A polymer, characterized in that, The polymer is obtained by polymerization of a crosslinking agent and a monomer compound as described in any one of claims 1 to 5.

7. The polymer according to claim 6, characterized in that, The polymer is obtained by polymerization of a crosslinking agent and a monomer compound as described in claim 2 or 3. The polymer has a refractive index of 1.54 to 1.58, a visible light transmittance of ≥85%, and a non-blue visible light transmittance of ≥89%.

8. The polymer as claimed in claim 6, characterized in that, The polymer is obtained by polymerization of a crosslinking agent and a monomer compound as described in claim 4 or 5, wherein the polymer has a refractive index ≥ 1.59, a visible light transmittance ≥ 68%, and a non-blue visible light transmittance ≥ 83%.

9. An optical lens, characterized in that, The optical lens comprises the polymer as described in any one of claims 6 to 8.

10. The optical lens as claimed in claim 9, characterized in that, At 100mm -1 At spatial frequencies, the modulation transfer function value of the optical lens is >0.5; and / or, The cylindrical lens of the optical lens is <0.14D; and / or, The absolute value of the spherical aberration of the optical lens is <0.30 μm.

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