Silicone hydrogel polymer material for contact lenses and preparation method thereof

Abstract

The invention discloses a silicone hydrogel polymer material for contact lenses and a preparation method thereof, and relates to the field of high polymer materials. Siloxane monomers, hydrophilic monomers and a dynamic cross-linking agent are mixed to obtain a monomer mixed solution; mixing functional nanoparticles, the monomer mixed solution and an initiator to obtain a pre-polymerized solution; according to the silicon hydrogel polymer material for the contact lens, the cyclic siloxane monomer and the linear siloxane are copolymerized to form a hydrophobic micro-area with a controllable size, the oxygen permeability is optimized, a borate bond is introduced as a dynamic crosslinking point, a network is reconstructed when ocular surface inflammation occurs, and the contact lens has the advantages that the contact lens is not prone to inflammation; functional nano-particle loaded anti-inflammatory and antibacterial components are released, and the high-oxygen-permeability, intelligent anti-inflammatory and antibacterial, ultra-durable and comfortable silicon hydrogel polymer material for the contact lenses is obtained.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, and in particular to a silicone hydrogel polymer material for contact lenses and a preparation method thereof. Background Art

[0002] Silicone hydrogel materials, such as those used in contact lenses, require the introduction of siloxane components in order to increase the oxygen permeability of the material. Materials containing siloxane molecular structures are highly hydrophobic, and therefore have a certain adverse effect on the biocompatibility of the material, including the easy adsorption of oils and proteins in tears, as well as microorganisms such as bacteria and viruses, which can cause severe inflammatory reactions. In addition, dry spots can appear on the surface of the lens, making it feel dry when worn and affecting the wearing comfort.

[0003] Contact lenses, in addition to meeting optical effectiveness, must also balance safety and wearing comfort. For safety, the industry is constantly pursuing materials with higher oxygen permeability; for wearing comfort, the industry is continuously improving the wettability of the lens surface and its long-term retention. From a material perspective, these two properties can appear to be in conflict. However, combining the lens base material with surface modification technology can achieve improvements in both areas. The base lens material only needs to have a low water content to maximize oxygen permeability. The lens surface is then modified to form a hydrophilic layer with higher wettability, while minimizing its thickness to minimize negatively impact oxygen permeability. Therefore, the current challenges facing silicone hydrogel materials include maintaining long-term wettability of contact lenses, alleviating the soreness caused by prolonged wear, and improving wearing comfort; and increasing the oxygen permeability of the lens to enhance wearing safety. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a silicone hydrogel polymer material for contact lenses and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A silicone hydrogel polymer material for contact lenses comprises the following components, measured by weight: 40-70 parts of a siloxane monomer, 40-50 parts of a hydrophilic monomer, 1-5 parts of a dynamic crosslinking agent, 3-7 parts of functional nanoparticles, and 0.1-1 part of an initiator. Furthermore, the siloxane monomers are cyclopentasiloxane and methacryloxypropyl tris(trimethylsiloxy)silane.

[0006] Furthermore, the mass ratio of cyclopentasiloxane to methacryloxypropyl tris(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 cross-linking agent is 4-vinylphenylboronic acid.

[0010] Furthermore, the preparation method of the functional nanoparticles is: ε-polylysine and resveratrol are dissolved in phosphate buffer to obtain solution A, and polylactic acid-glycolic acid copolymer is dissolved in dichloromethane to obtain solution B. Solution A and solution B are mixed, ultrasonically emulsified, and then injected with a polyvinyl alcohol solution with a mass fraction of 1-3%. The mixture is homogenized for 1-3 minutes, stirred at 20-30°C for 5-7 hours, and centrifuged to obtain nanoparticles. The nanoparticles are then dispersed in a dopamine solution, stirred in the dark at 30-40°C for 1-3 hours, and washed by centrifugation to obtain functional nanoparticles.

[0011] Furthermore, the usage 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 comprises the following steps: S1. Mixing a siloxane monomer, a hydrophilic monomer, and a dynamic crosslinking agent in parts by weight to obtain a monomer mixture; S2. Ultrasonic dispersion of functional nanoparticles in a monomer mixture according to weight, and adding an initiator to obtain a prepolymer solution; S3. Injecting the prepolymer liquid into the contact lens mold, irradiating it with ultraviolet light, then demoulding it, and soaking it to obtain the silicone hydrogel polymer material for contact lenses.

[0014] Beneficial effects of the present invention: (1) Polylactic acid-glycolic acid copolymer is used as a carrier to encapsulate ε-polylysine (antibacterial) and resveratrol (anti-inflammatory, antioxidant) to achieve a sustained release effect and prevent eye infection and inflammation. Polydopamine-modified nanoparticles bind to corneal mucin through the catechol group, and the retention time is prolonged. In addition, the pH-responsive boronate bond forms a stable covalent bond with the diol group in the siloxane network under normal tear fluid (pH 7.4) conditions to maintain the strength of the material. When the pH rises (greater than 7.8) during inflammation, the boronate bond hydrolyzes, the network locally relaxes, and the functional nanoparticles are released.

[0015] (2) Microcracks are generated in the material when blinking and squeezing occur. The broken borate bonds can be spontaneously reorganized in the tear environment (containing polyols), with a high repair efficiency, which improves the fatigue resistance of the lens and extends its service life. In addition, cyclopentasiloxane regulates hydrophobicity and cooperates with hydrophilic monomers (N, N-dimethylacrylamide, hydroxyethyl methacrylate) to avoid dry eye problems. Its rigid ring structure forms molecular-level pores of uniform size during polymerization, which efficiently transmit oxygen, manifested as an increase in the oxygen permeability coefficient and improved wearing comfort. DETAILED DESCRIPTION

[0016] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts 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 comprises the following steps: S1. Mixing, by weight, 40 parts of a siloxane monomer (cyclopentasiloxane and methacryloyloxypropyl tris(trimethylsiloxy)silane in a mass ratio of 1:2), 40 parts of a hydrophilic monomer (N,N-dimethylacrylamide and hydroxyethyl methacrylate in a mass ratio of 2:2), and 1 part of 4-vinylphenylboronic acid to obtain a monomer mixture; S2. Ultrasonic dispersion of 3 parts by weight of functional nanoparticles in the monomer mixture, and adding 0.1 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide to obtain a prepolymer solution; S3. Inject the prepolymer liquid into the contact lens mold, irradiate with ultraviolet light, and then demold. Immerse the lens in a mixed solution of ethanol and water (the volume ratio of ethanol to water is 7:3) for 48 hours, and then transfer it to physiological saline and soak it at room temperature for 24 hours to obtain a silicone hydrogel polymer material for contact lenses.

[0018] The preparation method of the functional nanoparticles is: 1 mg of ε-polylysine and 1 mg of resveratrol were dissolved in 0.1 mL of phosphate buffer to obtain solution A, and 40 mg of poly(lactic-co-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 injected with 10 mL of 1% polyvinyl alcohol solution. 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 a dopamine solution (10 mg of dopamine was dissolved in 5 mL of Tris buffer), stirred in the dark at 30°C 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 comprises the following steps: S1. Mix, by weight, 70 parts of a siloxane monomer (cyclopentasiloxane and methacryloyloxypropyl tris(trimethylsiloxy)silane in a mass ratio of 3:1), 50 parts of a hydrophilic monomer (N,N-dimethylacrylamide and hydroxyethyl methacrylate in a mass ratio of 4:1), and 5 parts of 4-vinylphenylboronic acid to obtain a monomer mixture; S2. Ultrasonic dispersion of 7 parts by weight of functional nanoparticles in the monomer mixture, and addition of 1 part of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide to obtain a prepolymer solution; S3. Inject the prepolymer liquid into the contact lens mold, irradiate with ultraviolet light, and then demold. Immerse the lens in a mixed solution of ethanol and water (the volume ratio of ethanol to water is 7:3) for 48 hours, and then transfer it to physiological saline and soak it at room temperature for 24 hours to obtain a silicone hydrogel polymer material for contact lenses.

[0020] The preparation method of the functional nanoparticles is: 3 mg of ε-polylysine and 2 mg of resveratrol were dissolved in 0.9 mL of phosphate buffer to obtain solution A, and 60 mg of poly(lactic-co-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 injected with 30 mL of 3% polyvinyl alcohol solution. The mixture was homogenized for 3 minutes, stirred at 30°C for 7 hours, and centrifuged to obtain nanoparticles. The nanoparticles were then dispersed in a dopamine solution (30 mg of dopamine was dissolved in 15 mL of Tris buffer), stirred in the dark at 40°C for 3 hours, and centrifuged and washed to obtain functional nanoparticles.

[0021] Example 3 A method for preparing a silicone hydrogel polymer material for contact lenses comprises the following steps: S1, by weight parts, 55 parts of siloxane monomer (the mass ratio of cyclopentadimethylsiloxane and methyl acryloyl propyl tri (trimethylsiloxy) silane is 2:1.5), 45 parts of hydrophilic monomer (the mass ratio of N, N-dimethyl acrylamide and hydroxyethyl methacrylate is 3:1.5) and 3 parts of 4-vinyl phenyl boronic acid are mixed to obtain a monomer mixture solution; S2, by weight parts, 5 parts of functional nanoparticles are ultrasonically dispersed in the monomer mixture solution, and 0.5 parts of phenyl bis (2, 4, 6-trimethyl benzoyl) phosphine oxide is added to obtain a prepolymer solution; S3, the prepolymer solution is injected into a contact lens mold, ultraviolet light is irradiated, then demolding, the lens is immersed in a mixed solution of ethanol and water (the volume ratio of ethanol and water is 7:3) for 48h, then transferred to physiological saline and soaked at room temperature for 24h, to obtain a silicone hydrogel polymer material for contact lenses.

[0022] The preparation method of the functional nanoparticles is: 2mg of ε-polylysine and 1.5mg of resveratrol are dissolved in 0.5mL of phosphate buffer to obtain solution A, 50mg of polylactic acid-glycolic acid copolymer is dissolved in 2mL of dichloromethane to obtain solution B, solution A and solution B are mixed, ultrasonic emulsification, then injected into 20mL of 2% polyvinyl alcohol solution, homogenized for 2min, stirred at 25℃ for 6h, centrifuged to obtain nanoparticles; then the nanoparticles are dispersed in a dopamine solution (20mg of dopamine is dissolved in 10mL of Tris buffer), stirred at 35℃ in the dark for 2h, centrifuged and washed to obtain functional nanoparticles.

[0023] Example 4 A preparation method of a silicone hydrogel polymer material for contact lenses, comprising the following steps: S1, by weight parts, 55 parts of siloxane monomer (the mass ratio of cyclopentadimethylsiloxane and methyl acryloyl propyl tri (trimethylsiloxy) silane is 2:1.5), 45 parts of hydrophilic monomer (the mass ratio of N, N-dimethyl acrylamide and hydroxyethyl methacrylate is 3:1.5) and 3 parts of 4-vinyl phenyl boronic acid are mixed to obtain a monomer mixture solution; S2, by weight parts, 5 parts of functional nanoparticles are ultrasonically dispersed in the monomer mixture solution, and 0.5 parts of phenyl bis (2, 4, 6-trimethyl benzoyl) phosphine oxide is added to obtain a prepolymer solution; S3, the prepolymer solution is injected into a contact lens mold, ultraviolet light is irradiated, then demolding, the lens is immersed in a mixed solution of ethanol and water (the volume ratio of ethanol and water is 7:3) for 48h, then transferred to physiological saline and soaked at room temperature for 24h, to obtain a silicone hydrogel polymer material for contact lenses.

[0024] The preparation method of the functional nanoparticles is: 2 mg of ε-polylysine and 1 mg of resveratrol were dissolved in 0.5 mL of phosphate buffer to obtain solution A, and 50 mg of poly(lactic-co-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 injected with 20 mL of 2% polyvinyl alcohol solution. 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 a dopamine solution (20 mg of dopamine was dissolved in 10 mL of Tris buffer), stirred in the dark at 37°C 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 comprises the following steps: S1. Mix, by weight, 50 parts of a siloxane monomer (cyclopentasiloxane and methacryloyloxypropyl tris(trimethylsiloxy)silane in a mass ratio of 3:2), 45 parts of a hydrophilic monomer (N,N-dimethylacrylamide and hydroxyethyl methacrylate in a mass ratio of 3.5:1), and 3 parts of 4-vinylphenylboronic acid to obtain a monomer mixture; S2. Ultrasonic dispersion of 5 parts by weight of functional nanoparticles in the monomer mixture, and addition of 0.5 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide to obtain a prepolymer solution; S3. Inject the prepolymer liquid into the contact lens mold, irradiate with ultraviolet light, and then demold. Immerse the lens in a mixed solution of ethanol and water (the volume ratio of ethanol to water is 7:3) for 48 hours, and then transfer it to physiological saline and soak it at room temperature for 24 hours to obtain a silicone hydrogel polymer material for contact lenses.

[0026] The preparation method of the functional nanoparticles is: 2 mg of ε-polylysine and 1 mg of resveratrol were dissolved in 0.5 mL of phosphate buffer to obtain solution A, and 50 mg of poly(lactic-co-glycolic acid) was dissolved in 2 mL of dichloromethane to obtain solution B. Solution A and solution B were mixed, ultrasonically emulsified, and then injected with 20 mL of 2% polyvinyl alcohol solution. 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 comprises the following steps: S1. Mix, by weight, 50 parts of a siloxane monomer (cyclopentasiloxane and methacryloyloxypropyl tris(trimethylsiloxy)silane in a mass ratio of 3:2), 45 parts of a hydrophilic monomer (N,N-dimethylacrylamide and hydroxyethyl methacrylate in a mass ratio of 3.5:1), and 3 parts of ethylene glycol dimethacrylate to obtain a monomer mixture; S2. Ultrasonic dispersion of 5 parts by weight of functional nanoparticles in the monomer mixture, and addition of 0.5 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide to obtain a prepolymer solution; S3. Inject the prepolymer liquid into the contact lens mold, irradiate with ultraviolet light, and then demold. Immerse the lens in a mixed solution of ethanol and water (the volume ratio of ethanol to water is 7:3) for 48 hours, and then transfer it to physiological saline and soak it at room temperature for 24 hours to obtain a silicone hydrogel polymer material for contact lenses.

[0028] The preparation method of the functional nanoparticles is: 2 mg of ε-polylysine and 1 mg of resveratrol were dissolved in 0.5 mL of phosphate buffer to obtain solution A, and 50 mg of poly(lactic-co-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 injected with 20 mL of 2% polyvinyl alcohol solution. 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 a dopamine solution (20 mg of dopamine was dissolved in 10 mL of Tris buffer), stirred in the dark at 37°C 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 comprises the following steps: S1. Mix, by weight, 50 parts of a siloxane monomer (methacryloxypropyl tris(trimethylsiloxy)silane), 45 parts of a hydrophilic monomer (N,N-dimethylacrylamide and hydroxyethyl methacrylate in a mass ratio of 3.5:1), and 3 parts of 4-vinylphenylboronic acid to obtain a monomer mixture; S2. Ultrasonic dispersion of 5 parts by weight of functional nanoparticles in the monomer mixture, and addition of 0.5 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide to obtain a prepolymer solution; S3. Inject the prepolymer liquid into the contact lens mold, irradiate with ultraviolet light, and then demold. Immerse the lens in a mixed solution of ethanol and water (the volume ratio of ethanol to water is 7:3) for 48 hours, and then transfer it to physiological saline and soak it at room temperature for 24 hours to obtain a silicone hydrogel polymer material for contact lenses.

[0030] The preparation method of the functional nanoparticles is: 2 mg of ε-polylysine and 1 mg of resveratrol were dissolved in 0.5 mL of phosphate buffer to obtain solution A, and 50 mg of poly(lactic-co-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 injected with 20 mL of 2% polyvinyl alcohol solution. 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 a dopamine solution (20 mg of dopamine was dissolved in 10 mL of Tris buffer), stirred in the dark at 37°C for 2 h, and centrifuged and washed to obtain functional nanoparticles.

[0031] The samples prepared according to the present invention were further tested for their effectiveness. The oxygen transmission rate (Dk value) was measured using polarography. The samples were immersed in artificial tears (containing lysozyme / albumin) for 7 days, and the protein adsorption (μg / cm²) was measured using the BCA method. The samples were then worn continuously for 14 days to assess the incidence of corneal edema and inflammation score (grade 0-4). The test results are described below.

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

[0033] According to the data in Table 1, it can be seen from the comparison between the examples of the present invention and the comparative examples that the high silicone content of the samples prepared by the present invention makes the oxygen permeability higher, and the natural active ingredients are embedded in the biodegradable polymer, which is safer. The functional nanoparticles can significantly reduce the risk of infection, relieve inflammation after wearing, reduce protein precipitation, and extend the service life.

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

Claims

1. A silicone hydrogel polymer material for contact lenses, characterized in that: The composition comprises the following components in parts 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 part of initiator.

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

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

4. The silicone hydrogel polymer material for contact lenses according to claim 1, wherein: 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 dynamic crosslinking agent is 4-vinylphenylboronic acid.

7. The silicone hydrogel polymer material for contact lenses according to claim 1, characterized in that: The preparation method of the functional nanoparticles is: ε-polylysine and resveratrol were dissolved in phosphate buffer to obtain solution A, poly(lactic acid-co-glycolic acid) copolymer was dissolved in dichloromethane to obtain solution B, solution A and solution B were mixed, ultrasonically emulsified, and then injected with a polyvinyl alcohol solution with a mass fraction of 1-3%, homogenized for 1-3 minutes, stirred at 20-30°C for 5-7 hours, and centrifuged to obtain nanoparticles; The nanoparticles are then dispersed in a dopamine solution, stirred at 30-40° C. in the dark for 1-3 hours, and centrifuged and washed to obtain functional nanoparticles.

8. The silicone hydrogel polymer material for contact lenses according to claim 7, characterized in that: The dosage 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.

9. 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.

10. The method for preparing a silicone hydrogel polymer material for contact lenses according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1. Mixing a siloxane monomer, a hydrophilic monomer, and a dynamic crosslinking agent in parts by weight to obtain a monomer mixture; S2. Ultrasonic dispersion of functional nanoparticles in a monomer mixture according to weight, and adding an initiator to obtain a prepolymer solution; S3. Injecting the prepolymer liquid into the contact lens mold, irradiating it with ultraviolet light, then demoulding it, and soaking it to obtain the silicone hydrogel polymer material for contact lenses.

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