A contact lens silicone hydrogel polymer material and method of making the same

Abstract

The application discloses a kind of silicon hydrogel polymer materials for contact lenses and preparation method thereof, it is related to polymer material field, siloxane monomer, hydrophilic monomer and dynamic crosslinking agent are mixed to obtain monomer mixed solution;Functional nanoparticles, monomer mixed solution and initiator are mixed to obtain prepolymer liquid;The prepolymer liquid is injected into mould, and then demoulding is irradiated by ultraviolet light, and immersion is obtained, and the silicon hydrogel polymer material for contact lenses is obtained, the application utilizes cyclic siloxane monomer and linear siloxane copolymerization, forms controllable hydrophobic micro area, optimizes oxygen permeability, introduces borate bond as dynamic crosslinking point, network reconfiguration when ocular inflammation, release functional nanoparticles load's anti-inflammatory antibacterial component, and obtained high oxygen permeability, intelligent anti-inflammatory antibacterial and super durable comfortable silicon hydrogel polymer material for contact lenses.

Description

Technical Field

[0001] This invention relates to the field of polymer materials, specifically to a silicone hydrogel polymer material for contact lenses and its preparation method. Background Technology

[0002] Silicone hydrogel materials, when used in contact lenses, require the introduction of siloxane components to improve oxygen permeability. However, materials containing siloxane molecules have strong hydrophobicity, which can negatively impact biocompatibility. This includes the easy adsorption of oils and proteins from tears, as well as bacteria, viruses, and other microorganisms, potentially triggering severe inflammatory reactions. Additionally, it can cause dry spots on the lens surface, resulting in a dry feeling and affecting wearing comfort.

[0003] For contact lenses, in addition to optical effectiveness, safety and wearing comfort must also be considered. Regarding safety, the industry continuously pursues materials with higher oxygen permeability; regarding wearing comfort, the industry is constantly improving the wettability of the lens surface and its long-lasting retention. From a material perspective, these two properties seem contradictory. However, combining the lens substrate material with surface modification technology can simultaneously improve both aspects. For the lens substrate material, it only needs to have a low water content to maximize oxygen permeability. Then, the lens surface is modified to form a hydrophilic layer with higher wettability, while minimizing its thickness to avoid negatively impacting oxygen permeability. Therefore, the current challenges that silicone hydrogel materials need to address include: maintaining the long-lasting wettability of contact lenses, alleviating the discomfort caused by prolonged wear, and improving wearing comfort; increasing the oxygen permeability of the lens, and enhancing wearing safety. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a silicone hydrogel polymer material for contact lenses and its preparation method.

[0005] The objective of this invention can be achieved through the following technical solutions: A silicone hydrogel polymer material for contact lenses, comprising the following components by weight: 40-70 parts of siloxane monomer, 40-50 parts of hydrophilic monomer, 1-5 parts of dynamic crosslinking agent, 3-7 parts of functional nanoparticles, and 0.1-1 parts of initiator. Furthermore, the siloxane monomer is cyclopentadimethylsiloxane and methacryloxypropyltris(trimethylsiloxy)silane.

[0006] Furthermore, the mass ratio of cyclopentadimethylsiloxane to methacryloxypropyltris(trimethylsiloxy)silane in the siloxane monomer is 1-3:1-2.

[0007] Furthermore, the hydrophilic monomers are N,N-dimethylacrylamide and hydroxyethyl methacrylate.

[0008] Furthermore, the mass ratio of N,N-dimethylacrylamide to hydroxyethyl methacrylate in the hydrophilic monomer is 2-4:1-2.

[0009] Furthermore, the dynamic crosslinking agent is 4-vinylphenylboronic acid.

[0010] Furthermore, the preparation method of the functional nanoparticles is as follows: ε-polylysine and resveratrol were dissolved in phosphate buffer to obtain solution A. Polylactic acid-glycolic acid copolymer was dissolved in dichloromethane to obtain solution B. Solution A and solution B were mixed and ultrasonically emulsified. Then, a 1-3% (w / w) polyvinyl alcohol solution was injected, homogenized for 1-3 min, stirred at 20-30℃ for 5-7 h, and centrifuged to obtain nanoparticles. The nanoparticles were then dispersed in dopamine solution and stirred in the dark at 30-40℃ for 1-3 h. After centrifugation and washing, functional nanoparticles were obtained.

[0011] Furthermore, the ratio of the ε-polylysine, resveratrol, phosphate buffer, polylactic acid-glycolic acid copolymer, dichloromethane, and polyvinyl alcohol solution is 1-3 mg: 1-2 mg: 0.1-0.9 mL: 40-60 mg: 1-3 mL: 10-30 mL; the dopamine solution is prepared by dissolving 10-30 mg of dopamine in 5-15 mL of Tris buffer.

[0012] Furthermore, the initiator is phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0013] A method for preparing a silicone hydrogel polymer material for contact lenses includes the following steps: S1. Mix the siloxane monomer, hydrophilic monomer and dynamic crosslinking agent according to the weight parts to obtain a monomer mixture; S2. By weight, the functional nanoparticles are ultrasonically dispersed in the monomer mixture, and an initiator is added to obtain the prepolymer solution. S3. Inject the prepolymer solution into the contact lens mold, irradiate with ultraviolet light, then demold and soak to obtain the silicone hydrogel polymer material for contact lenses.

[0014] The beneficial effects of this invention are: (1) Using polylactic acid-glycolic acid copolymer as a carrier, ε-polylysine (antibacterial) and resveratrol (anti-inflammatory and antioxidant) are encapsulated to achieve sustained release and prevent eye infections and inflammation. The polydopamine-modified nanoparticles bind to corneal mucin through catechol groups, which prolongs the retention time. In addition, pH-responsive borate ester bonds form stable covalent bonds with diol groups in the siloxane network under normal tear conditions (pH 7.4) to maintain the strength of the material. During inflammation, the pH increases (greater than 7.8), the borate ester bonds hydrolyze, the network relaxes locally, and functional nanoparticles are released.

[0015] (2) When blinking, the material produces microcracks. The broken borate ester bonds can spontaneously recombine in the tear environment (containing polyols), resulting in high repair efficiency, which improves the fatigue resistance of the lens and extends its service life. In addition, cyclopentamethoxysiloxane regulates hydrophobicity and works synergistically with hydrophilic monomers (N,N-dimethylacrylamide, hydroxyethyl methacrylate) to avoid dry eye problems. Its rigid ring structure forms uniform molecular-level pores during polymerization, which efficiently transport oxygen, resulting in an improved oxygen permeability coefficient and enhanced wearing comfort. Detailed Implementation

[0016] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. 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.

[0017] Example 1 A method for preparing a silicone hydrogel polymer material for contact lenses includes the following steps: S1. By weight, 40 parts of siloxane monomer (the mass ratio of cyclopentamethoxypropyltris(trimethylsiloxy)silane is 1:2), 40 parts of hydrophilic monomer (the mass ratio of N,N-dimethylacrylamide and hydroxyethyl methacrylate is 2:2) and 1 part of 4-vinylphenylboronic acid are mixed to obtain a monomer mixture. S2. By weight, 3 parts of functional nanoparticles are ultrasonically dispersed in a monomer mixture, and 0.1 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide are added to obtain a prepolymer solution; S3. Inject the prepolymer solution into the contact lens mold, irradiate with ultraviolet light, then demold, immerse the lens in a mixed solution of ethanol and water (volume ratio of ethanol to water is 7:3) for 48 hours, and then transfer it to physiological saline for soaking at room temperature for 24 hours to obtain silicone hydrogel polymer material for contact lenses.

[0018] The preparation method of the functional nanoparticles is as follows: 1 mg of ε-polylysine and 1 mg of resveratrol were dissolved in 0.1 mL of phosphate buffer to obtain solution A. 40 mg of polylactic acid-glycolic acid copolymer was dissolved in 1 mL of dichloromethane to obtain solution B. Solution A and solution B were mixed, ultrasonically emulsified, and then 10 mL of 1% polyvinyl alcohol solution was injected. The mixture was homogenized for 1 min, stirred at 20 °C for 5 h, and centrifuged to obtain nanoparticles. The nanoparticles were then dispersed in dopamine solution (10 mg of dopamine was dissolved in 5 mL of Tris buffer), stirred at 30 °C in the dark for 1 h, and centrifuged and washed to obtain functional nanoparticles.

[0019] Example 2 A method for preparing a silicone hydrogel polymer material for contact lenses includes the following steps: S1. By weight, 70 parts of siloxane monomer (the mass ratio of cyclopentamethoxypropyltris(trimethylsiloxy)silane is 3:1), 50 parts of hydrophilic monomer (the mass ratio of N,N-dimethylacrylamide and hydroxyethyl methacrylate is 4:1) and 5 parts of 4-vinylphenylboronic acid are mixed to obtain a monomer mixture. S2. By weight, 7 parts of functional nanoparticles are ultrasonically dispersed in a monomer mixture, and 1 part of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide is added to obtain a prepolymer solution; S3. Inject the prepolymer solution into the contact lens mold, irradiate with ultraviolet light, then demold, immerse the lens in a mixed solution of ethanol and water (volume ratio of ethanol to water is 7:3) for 48 hours, and then transfer it to physiological saline for soaking at room temperature for 24 hours to obtain silicone hydrogel polymer material for contact lenses.

[0020] The preparation method of the functional nanoparticles is as follows: 3 mg of ε-polylysine and 2 mg of resveratrol were dissolved in 0.9 mL of phosphate buffer to obtain solution A. 60 mg of polylactic acid-glycolic acid copolymer was dissolved in 3 mL of dichloromethane to obtain solution B. Solution A and solution B were mixed, ultrasonically emulsified, and then 30 mL of 3% polyvinyl alcohol solution was injected. The mixture was homogenized for 3 min, stirred at 30 °C for 7 h, and centrifuged to obtain nanoparticles. The nanoparticles were then dispersed in dopamine solution (30 mg of dopamine was dissolved in 15 mL of Tris buffer), stirred at 40 °C in the dark for 3 h, and centrifuged and washed to obtain functional nanoparticles.

[0021] Example 3 A method for preparing a silicone hydrogel polymer material for contact lenses includes the following steps: S1. By weight, 55 parts of siloxane monomer (the mass ratio of cyclopentamethoxypropyltris(trimethylsiloxy)silane to methacryloxypropyltris(trimethylsiloxy)silane is 2:1.5), 45 parts of hydrophilic monomer (the mass ratio of N,N-dimethylacrylamide to hydroxyethyl methacrylate is 3:1.5) and 3 parts of 4-vinylphenylboronic acid are mixed to obtain a monomer mixture. S2. By weight, 5 parts of functional nanoparticles are ultrasonically dispersed in a monomer mixture, and 0.5 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide are added to obtain a prepolymer solution; S3. Inject the prepolymer solution into the contact lens mold, irradiate with ultraviolet light, then demold, immerse the lens in a mixed solution of ethanol and water (volume ratio of ethanol to water is 7:3) for 48 hours, and then transfer it to physiological saline for soaking at room temperature for 24 hours to obtain silicone hydrogel polymer material for contact lenses.

[0022] The preparation method of the functional nanoparticles is as follows: 2 mg of ε-polylysine and 1.5 mg of resveratrol were dissolved in 0.5 mL of phosphate buffer to obtain solution A. 50 mg of polylactic acid-glycolic acid copolymer was dissolved in 2 mL of dichloromethane to obtain solution B. Solution A and solution B were mixed, ultrasonically emulsified, and then 20 mL of 2% (w / w) polyvinyl alcohol solution was injected. The mixture was homogenized for 2 min, stirred at 25 °C for 6 h, and centrifuged to obtain nanoparticles. The nanoparticles were then dispersed in dopamine solution (20 mg of dopamine was dissolved in 10 mL of Tris buffer), stirred at 35 °C in the dark for 2 h, and centrifuged and washed to obtain functional nanoparticles.

[0023] Example 4 A method for preparing a silicone hydrogel polymer material for contact lenses includes the following steps: S1. By weight, 50 parts of siloxane monomer (the mass ratio of cyclopentamethoxypropyltris(trimethylsiloxy)silane is 3:2), 45 parts of hydrophilic monomer (the mass ratio of N,N-dimethylacrylamide and hydroxyethyl methacrylate is 3.5:1) and 3 parts of 4-vinylphenylboronic acid are mixed to obtain a monomer mixture. S2. By weight, 5 parts of functional nanoparticles are ultrasonically dispersed in a monomer mixture, and 0.5 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide are added to obtain a prepolymer solution; S3. Inject the prepolymer solution into the contact lens mold, irradiate with ultraviolet light, then demold, immerse the lens in a mixed solution of ethanol and water (volume ratio of ethanol to water is 7:3) for 48 hours, and then transfer it to physiological saline for soaking at room temperature for 24 hours to obtain silicone hydrogel polymer material for contact lenses.

[0024] The preparation method of the functional nanoparticles is as follows: 2 mg of ε-polylysine and 1 mg of resveratrol were dissolved in 0.5 mL of phosphate buffer to obtain solution A. 50 mg of polylactic acid-glycolic acid copolymer was dissolved in 2 mL of dichloromethane to obtain solution B. Solution A and solution B were mixed, ultrasonically emulsified, and then 20 mL of 2% polyvinyl alcohol solution was injected. The mixture was homogenized for 1 min, stirred at 25 °C for 6 h, and centrifuged to obtain nanoparticles. The nanoparticles were then dispersed in dopamine solution (20 mg of dopamine was dissolved in 10 mL of Tris buffer), stirred at 37 °C in the dark for 2 h, and centrifuged and washed to obtain functional nanoparticles.

[0025] Comparative Example 1 A method for preparing a silicone hydrogel polymer material for contact lenses includes the following steps: S1. By weight, 50 parts of siloxane monomer (the mass ratio of cyclopentamethoxypropyltris(trimethylsiloxy)silane is 3:2), 45 parts of hydrophilic monomer (the mass ratio of N,N-dimethylacrylamide and hydroxyethyl methacrylate is 3.5:1) and 3 parts of 4-vinylphenylboronic acid are mixed to obtain a monomer mixture. S2. By weight, 5 parts of functional nanoparticles are ultrasonically dispersed in a monomer mixture, and 0.5 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide are added to obtain a prepolymer solution; S3. Inject the prepolymer solution into the contact lens mold, irradiate with ultraviolet light, then demold, immerse the lens in a mixed solution of ethanol and water (volume ratio of ethanol to water is 7:3) for 48 hours, and then transfer it to physiological saline for soaking at room temperature for 24 hours to obtain silicone hydrogel polymer material for contact lenses.

[0026] The preparation method of the functional nanoparticles is as follows: 2 mg of ε-polylysine and 1 mg of resveratrol were dissolved in 0.5 mL of phosphate buffer to obtain solution A. 50 mg of polylactic acid-glycolic acid copolymer was dissolved in 2 mL of dichloromethane to obtain solution B. Solution A and solution B were mixed, ultrasonically emulsified, and then 20 mL of 2% polyvinyl alcohol solution was injected. The mixture was homogenized for 1 min, stirred at 25 °C for 6 h, and centrifuged to obtain functional nanoparticles.

[0027] Comparative Example 2 A method for preparing a silicone hydrogel polymer material for contact lenses includes the following steps: S1. By weight, 50 parts of siloxane monomer (the mass ratio of cyclopentamethoxypropyltris(trimethylsiloxy)silane is 3:2), 45 parts of hydrophilic monomer (the mass ratio of N,N-dimethylacrylamide and hydroxyethyl methacrylate is 3.5:1) and 3 parts of ethylene glycol dimethacrylate are mixed to obtain a monomer mixture. S2. By weight, 5 parts of functional nanoparticles are ultrasonically dispersed in a monomer mixture, and 0.5 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide are added to obtain a prepolymer solution; S3. Inject the prepolymer solution into the contact lens mold, irradiate with ultraviolet light, then demold, immerse the lens in a mixed solution of ethanol and water (volume ratio of ethanol to water is 7:3) for 48 hours, and then transfer it to physiological saline for soaking at room temperature for 24 hours to obtain silicone hydrogel polymer material for contact lenses.

[0028] The preparation method of the functional nanoparticles is as follows: 2 mg of ε-polylysine and 1 mg of resveratrol were dissolved in 0.5 mL of phosphate buffer to obtain solution A. 50 mg of polylactic acid-glycolic acid copolymer was dissolved in 2 mL of dichloromethane to obtain solution B. Solution A and solution B were mixed, ultrasonically emulsified, and then 20 mL of 2% polyvinyl alcohol solution was injected. The mixture was homogenized for 1 min, stirred at 25 °C for 6 h, and centrifuged to obtain nanoparticles. The nanoparticles were then dispersed in dopamine solution (20 mg of dopamine was dissolved in 10 mL of Tris buffer), stirred at 37 °C in the dark for 2 h, and centrifuged and washed to obtain functional nanoparticles.

[0029] Comparative Example 3 A method for preparing a silicone hydrogel polymer material for contact lenses includes the following steps: S1. By weight, 50 parts of siloxane monomer (methacryloyloxypropyltris(trimethylsiloxy)silane), 45 parts of hydrophilic monomer (N,N-dimethylacrylamide and hydroxyethyl methacrylate in a mass ratio of 3.5:1) and 3 parts of 4-vinylphenylboronic acid are mixed to obtain a monomer mixture. S2. By weight, 5 parts of functional nanoparticles are ultrasonically dispersed in a monomer mixture, and 0.5 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide are added to obtain a prepolymer solution; S3. Inject the prepolymer solution into the contact lens mold, irradiate with ultraviolet light, then demold, immerse the lens in a mixed solution of ethanol and water (volume ratio of ethanol to water is 7:3) for 48 hours, and then transfer it to physiological saline for soaking at room temperature for 24 hours to obtain silicone hydrogel polymer material for contact lenses.

[0030] The preparation method of the functional nanoparticles is as follows: 2 mg of ε-polylysine and 1 mg of resveratrol were dissolved in 0.5 mL of phosphate buffer to obtain solution A. 50 mg of polylactic acid-glycolic acid copolymer was dissolved in 2 mL of dichloromethane to obtain solution B. Solution A and solution B were mixed, ultrasonically emulsified, and then 20 mL of 2% polyvinyl alcohol solution was injected. The mixture was homogenized for 1 min, stirred at 25 °C for 6 h, and centrifuged to obtain nanoparticles. The nanoparticles were then dispersed in dopamine solution (20 mg of dopamine was dissolved in 10 mL of Tris buffer), stirred at 37 °C in the dark for 2 h, and centrifuged and washed to obtain functional nanoparticles.

[0031] The following is a further effect test of the samples prepared in this invention. The oxygen permeability (Dk value) was measured by polarography; the samples were soaked in artificial tears (containing lysozyme / albumin) for 7 days, and the protein adsorption amount (μg / cm²) was determined by BCA method. The samples were worn continuously for 14 days to evaluate the incidence of corneal edema and inflammation score (0-4 grade). The test results are as follows.

[0032] The results are recorded in Table 1; Table 1: Test Results

[0033] According to the data in Table 1, a comparison between the embodiments and comparative examples of the present invention shows that the high siloxane content of the sample prepared by the present invention results in higher oxygen permeability. The natural active ingredients are encapsulated by biodegradable polymers, resulting in higher safety. The functional nanoparticles can significantly reduce the risk of infection, alleviate inflammation after wearing, reduce protein deposition, and extend service life.

[0034] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A silicone hydrogel polymer material for contact lenses, characterized in that, By weight, it includes the following components: 40-70 parts of siloxane monomer, 40-50 parts of hydrophilic monomer, 1-5 parts of dynamic crosslinking agent, 3-7 parts of functional nanoparticles, and 0.1-1 parts of initiator. The dynamic crosslinking agent is 4-vinylphenylboronic acid; The preparation method of the functional nanoparticles is as follows: ε-polylysine and resveratrol were dissolved in phosphate buffer to obtain solution A. Polylactic acid-glycolic acid copolymer was dissolved in dichloromethane to obtain solution B. Solution A and solution B were mixed, ultrasonically emulsified, and then a 1-3% (w / w) polyvinyl alcohol solution was injected. The mixture was homogenized for 1-3 min, stirred at 20-30℃ for 5-7 h, and centrifuged to obtain nanoparticles. The nanoparticles were then dispersed in a dopamine solution and stirred in the dark at 30-40°C for 1-3 hours. After centrifugation and washing, functional nanoparticles were obtained.

2. The silicone hydrogel polymer material for contact lenses according to claim 1, characterized in that, The siloxane monomers are cyclopentadimethylsiloxane and methacryloyloxypropyltris(trimethylsiloxy)silane.

3. The silicone hydrogel polymer material for contact lenses according to claim 2, characterized in that, The mass ratio of cyclopentadimethylsiloxane to methacryloyloxypropyltris(trimethylsiloxy)silane in the siloxane monomer is 1-3:1-2.

4. The silicone hydrogel polymer material for contact lenses according to claim 1, characterized in that, The hydrophilic monomers are N,N-dimethylacrylamide and hydroxyethyl methacrylate.

5. The silicone hydrogel polymer material for contact lenses according to claim 4, characterized in that, The mass ratio of N,N-dimethylacrylamide to hydroxyethyl methacrylate in the hydrophilic monomer is 2-4:1-2.

6. The silicone hydrogel polymer material for contact lenses according to claim 1, characterized in that, The ratio of the ε-polylysine, resveratrol, phosphate buffer, polylactic acid-glycolic acid copolymer, dichloromethane, and polyvinyl alcohol solution is 1-3 mg: 1-2 mg: 0.1-0.9 mL: 40-60 mg: 1-3 mL: 10-30 mL; the dopamine solution is prepared by dissolving 10-30 mg of dopamine in 5-15 mL of Tris buffer.

7. The silicone hydrogel polymer material for contact lenses according to claim 1, characterized in that, The initiator is phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

8. A method for preparing a silicone hydrogel polymer material for contact lenses according to any one of claims 1-7, characterized in that, Includes the following steps: S1. Mix the siloxane monomer, hydrophilic monomer and dynamic crosslinking agent according to the weight parts to obtain a monomer mixture; S2. By weight, the functional nanoparticles are ultrasonically dispersed in the monomer mixture, and an initiator is added to obtain the prepolymer solution. S3. Inject the prepolymer solution into the contact lens mold, irradiate with ultraviolet light, then demold and soak to obtain the silicone hydrogel polymer material for contact lenses.

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