Hydrophilic silicone hydrogel as well as preparation method and application thereof
The silicon hydrogel prepared by sol-gel method and comonomer impregnation method solves the problems of poor hydrophilicity and insufficient adhesion of biological materials in existing silicon hydrogels, achieves high hydrophilicity and protein resistance, and improves the wear comfort of corneal contact lenses.
Patent Information
- Application Number
- CN202411815240.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-11
- Publication Date
- 2025-03-18
AI Technical Summary
The existing silicon hydrogel materials have poor hydrophilicity, resulting in insufficient adhesion of biomaterials, affecting the wear comfort and biometric properties of corneal contact lenses.
The semi-interpenetrating grid material of polydimethylsiloxane and polyvinyl alcohol was prepared by the sol-gel method, and a silicon hydrogel with excellent hydrophilic properties and anti-protein adhesion resistance was formed by impregnating comonomers such as betaine sulfonate, betaine methacrylate, beta-hydroxyethyl methacrylic acid, and methacrylic acid.
It improves the hydrophilic properties and protein adhesion of silicon hydrogels, enhances the moisture content of the material, improves the wear comfort of corneal contact lenses, and reduces the water diffusion rate and avoids corneal dehydration.
Smart Images
Figure BDA0005181582380000071
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of silicone hydrogels, and in particular to a hydrophilic silicone hydrogel and a preparation method and application thereof. Background Art
[0002] Corneal contact lenses, also known as "contact lenses", are lenses worn on the cornea of the eyeball to correct vision or protect the eyes. According to the hardness of the material, it includes three types: hard, semi-hard, and soft. Contact lenses not only greatly improve the appearance and convenience of patients with refractive errors such as myopia, hyperopia, and astigmatism, but also provide a wide field of vision and realistic vision. In addition, they also play a special role in controlling the development of myopia and astigmatism in adolescents and treating special eye diseases.
[0003] In the 1960s, hydrogel soft contact lenses invented by chemists not only improved the comfort of wearing, but also made the lenses have a certain oxygen permeability. They were subsequently widely used. However, the oxygen permeability of this hydrogel material is seriously dependent on the water content in the material. Long-term wearing will also cause various diseases caused by corneal hypoxia, thus limiting its scope of application. In order to improve the oxygen permeability of the material, two other silicone acrylate monomers and fluorine-containing acrylate monomers were successively applied to the structure of hard contact lens materials to develop fluorosilicone acrylate hard breathable materials. Subsequently, polysiloxane acrylate monomers were also applied to hydrogel materials to develop soft silicone hydrogel materials. The oxygen permeability of these new materials has been greatly improved, and they can completely get rid of the dependence on water content. On the contrary, the lower the water content in the material, the higher the oxygen permeability of the material.
[0004] Although silicone hydrogel materials need to have a certain water content to provide ideal softness, a higher water content is beneficial to the wearing comfort and biocompatibility of contact lenses; however, a higher water content will reduce the mechanical strength and rigidity of contact lens materials and reduce the oxygen permeability coefficient. In particular, contact lenses with high water content may accelerate the consumption of tears, and insufficient tear supply will cause a series of discomforts such as dry eyes. The higher the water content of the material, the faster the diffusion rate of water from the back surface of the lens to the front surface. After the water on the front surface is lost, the back surface will quickly replenish water to the front surface. The water on the back surface mainly comes from the tear film between the lens and the corneal epithelium. When the water loss of the tear film is too fast, the water in the cornea will also be "sucked" out, causing corneal dehydration.
[0005] However, the hydrophobic nature of silicon-containing monomers means that contact lenses made from them are difficult to wet.The suitability of a material for use in biomedical devices depends on the material's wettability and its tendency to adhere to or react with biological materials such as proteins and lipids. Summary of the invention
[0006] The purpose of the present invention is to provide a hydrophilic silicone hydrogel and a preparation method and application thereof, so as to solve the problems of poor hydrophilicity and adhesion of biomaterials in existing silicone hydrogels.
[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
[0008] A method for preparing a hydrophilic silicone hydrogel comprises the following steps:
[0009] Mixing polydimethylsiloxane, tetraethyl orthosilicate, stannous octoate and a first organic solvent, and adding a polyvinyl alcohol solution to carry out a first reaction after the mixing is completed to obtain a first product;
[0010] Mixing sulfobetaine methacrylate, β-hydroxyethyl methacrylate, methacrylic acid, azobisisobutyronitrile, N,N-dimethylbisacrylamide and a second organic solvent to obtain a second mixed solution;
[0011] The first product is immersed in the second mixed solution, and after reaching swelling equilibrium, a second reaction is carried out to obtain a hydrophilic silicone hydrogel.
[0012] Preferably, in the above method for preparing a hydrophilic silicone hydrogel, the mass ratio of polydimethylsiloxane, tetraethyl orthosilicate and stannous octoate is 80-100:5-30:0.4-3;
[0013] The usage ratio of the polydimethylsiloxane and the first organic solvent is 80-100 g:150-250 mL.
[0014] Preferably, in the above method for preparing a hydrophilic silicone hydrogel, the first organic solvent and the second organic solvent are independently toluene.
[0015] Preferably, in the above method for preparing a hydrophilic silicone hydrogel, the concentration of the polyvinyl alcohol solution is 0.05 to 0.1 g / mL;
[0016] The usage ratio of the polydimethylsiloxane to the polyvinyl alcohol solution is 80-100 g:150-300 mL.
[0017] Preferably, in the above method for preparing a hydrophilic silicone hydrogel, the temperature of the first reaction is 20 to 40° C., and the time of the first reaction is 24 to 48 hours.
[0018] Preferably, in the above method for preparing a hydrophilic silicone hydrogel, the mass ratio of sulfobetaine methacrylate, β-hydroxyethyl methacrylate, and methacrylic acid is 50-80:100-200:5-20;
[0019] The usage ratio of β-hydroxyethyl methacrylate, azobisisobutyronitrile, N,N-dimethylbisacrylamide and the second organic solvent is 100-200 g: 20-40 g: 33-50 g: 100-300 mL.
[0020] Preferably, in the above method for preparing a hydrophilic silicone hydrogel, the immersion temperature is 20-30°C.
[0021] Preferably, in the above method for preparing a hydrophilic silicone hydrogel, the temperature of the second reaction is 60 to 80° C., and the time of the second reaction is 10 to 20 hours.
[0022] The invention also provides a hydrophilic silicone hydrogel prepared by a method for preparing the hydrophilic silicone hydrogel.
[0023] The invention also provides an application of the hydrophilic silicone hydrogel in contact lenses.
[0024] It can be seen from the above technical solution that compared with the prior art, the present invention has the following beneficial effects:
[0025] (1) The present invention successfully prepares a semi-interpenetrating mesh material of polydimethylsiloxane and polyvinyl alcohol by a sol-gel method, wherein polydimethylsiloxane is cross-linked under the action of tetraethyl orthosilicate to form a mesh, and the addition of hydrophilic polyvinyl alcohol reacts with the mesh formed by cross-linking polydimethylsiloxane to form a semi-interpenetrating mesh material; using sulfobetaine methacrylate, methacrylate-β-hydroxyethyl ester, and methacrylic acid as comonomers, the semi-interpenetrating mesh material of polydimethylsiloxane and polyvinyl alcohol is immersed in a mixed solution of the comonomers, and an interpenetrating mesh composite system of polydimethylsiloxane and sulfobetaine methacrylate, methacrylate-β-hydroxyethyl ester, and methacrylic acid as comonomer hydrogel is prepared by a monomer impregnation method. The interpenetrating mesh composite system has excellent hydrophilicity and anti-protein adhesion, and at the same time has a high water content, thereby improving wearing comfort.
[0026] (2) The present invention uses β-hydroxyethyl methacrylate and methacrylic acid as hydrogel comonomers to improve its hydrophilicity and light transmittance. At the same time, sulfobetaine methacrylate, which can produce excellent anti-adhesion properties, is introduced as a comonomer to improve the material's anti-protein adhesion.
[0027] (3) The preparation process of the present invention is simple, easy to operate, and has good repeatability; the raw material price is low, and it can be promoted and used. DETAILED DESCRIPTION
[0028] A method for preparing a hydrophilic silicone hydrogel comprises the following steps:
[0029] Mixing polydimethylsiloxane, tetraethyl orthosilicate, stannous octoate and a first organic solvent, and adding a polyvinyl alcohol solution to carry out a first reaction after the mixing is completed to obtain a first product;
[0030] Mixing sulfobetaine methacrylate, β-hydroxyethyl methacrylate, methacrylic acid, azobisisobutyronitrile, N,N-dimethylbisacrylamide and a second organic solvent to obtain a second mixed solution;
[0031] The first product is immersed in the second mixed solution, and after reaching swelling equilibrium, a second reaction is carried out to obtain a hydrophilic silicone hydrogel.
[0032] In the present invention, the mass ratio of the polydimethylsiloxane, tetraethyl orthosilicate and stannous octoate is preferably 80-100:5-30:0.4-3, more preferably 82-95:7-23:0.9-2.5, and more preferably 87-92:12-20:1.2-2.
[0033] In the present invention, the usage ratio of the polydimethylsiloxane to the first organic solvent is preferably 80-100 g:150-250 mL, more preferably 83-97 g:165-220 mL, and more preferably 85-93 g:180-200 mL.
[0034] In the present invention, the first organic solvent and the second organic solvent are independently preferably toluene.
[0035] In the present invention, the concentration of the polyvinyl alcohol solution is preferably 0.05 to 0.1 g / mL, more preferably 0.06 to 0.09 g / mL, and even more preferably 0.07 to 0.08 g / mL.
[0036] In the present invention, the usage ratio of the polydimethylsiloxane to the polyvinyl alcohol solution is preferably 80-100 g:150-300 mL, more preferably 83-97 g:180-260 mL, and more preferably 85-93 g:200-250 mL.
[0037] In the present invention, the temperature of the first reaction is preferably 20-40°C, more preferably 23-35°C, more preferably 25-30°C; the time of the first reaction is preferably 24-48h, more preferably 25-40h, more preferably 30-35h.
[0038] In the present invention, after the first reaction is completed, the method further comprises:
[0039] The obtained product is washed with water, and then dried after washing;
[0040] The drying temperature is preferably 50 to 80° C., more preferably 55 to 75° C., and more preferably 60 to 70° C.; the drying time is preferably 24 to 48 hours, more preferably 30 to 40 hours, and more preferably 32 to 36 hours.
[0041] In the present invention, the mass ratio of sulfobetaine methacrylate, β-hydroxyethyl methacrylate and methacrylic acid is preferably 50-80:100-200:5-20, more preferably 53-75:130-180:7-18, and more preferably 55-60:140-160:10-15.
[0042] In the present invention, the usage ratio of β-hydroxyethyl methacrylate, azobisisobutyronitrile, N,N-dimethylbisacrylamide and the second organic solvent is preferably 100-200 g: 20-40 g: 33-50 g: 100-300 mL, more preferably 110-180 g: 22-38 g: 35-45 g: 120-280 mL, and more preferably 130-150 g: 25-30 g: 38-40 g: 150-200 mL.
[0043] In the present invention, the immersion temperature is preferably 20 to 30°C, more preferably 22 to 28°C, and even more preferably 25 to 26°C.
[0044] In the present invention, the temperature of the second reaction is preferably 60-80°C, more preferably 65-78°C, and more preferably 68-73°C; the time of the second reaction is preferably 10-20h, more preferably 12-18h, and more preferably 14-16h.
[0045] In the present invention, the second reaction is preferably carried out under vacuum conditions.
[0046] The invention also provides a hydrophilic silicone hydrogel prepared by a method for preparing the hydrophilic silicone hydrogel.
[0047] The invention also provides an application of the hydrophilic silicone hydrogel in contact lenses.
[0048] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0049] Example 1
[0050] 80 g of polydimethylsiloxane, 25 g of tetraethyl orthosilicate, 0.5 g of stannous octoate and 200 mL of toluene were mixed to obtain a first mixed solution; the first mixed solution was dropped into 200 mL of a 0.08 g / mL polyvinyl alcohol solution under stirring, and the mixture was reacted at 25° C. for 24 h. After the reaction, the obtained product was washed with deionized water, and dried at 60° C. for 36 h to obtain a first product;
[0051] 60 g of sulfobetaine methacrylate, 160 g of β-hydroxyethyl methacrylate, 15 g of methacrylic acid, 20 g of azobisisobutyronitrile, 35 g of N,N-dimethylbisacrylamide and 300 mL of toluene were mixed to obtain a second mixed solution;
[0052] The first product was immersed in the second mixed solution at 25° C., and after reaching swelling equilibrium, the mixture was reacted at 70° C. for 15 hours under vacuum conditions to obtain a hydrophilic silicone hydrogel.
[0053] Example 2
[0054] 85 g of polydimethylsiloxane, 25 g of tetraethyl orthosilicate, 2.5 g of stannous octoate and 150 mL of toluene were mixed to obtain a first mixed solution; the first mixed solution was dropped into 200 mL of a 0.06 g / mL polyvinyl alcohol solution under stirring, and the mixture was reacted at 25° C. for 24 h. After the reaction, the obtained product was washed with deionized water, and dried at 60° C. for 36 h to obtain a first product;
[0055] 55 g of sulfobetaine methacrylate, 120 g of β-hydroxyethyl methacrylate, 20 g of methacrylic acid, 25 g of azobisisobutyronitrile, 40 g of N,N-dimethylbisacrylamide and 300 mL of toluene were mixed to obtain a second mixed solution;
[0056] The first product was immersed in the second mixed solution at 25° C., and after reaching swelling equilibrium, the mixture was reacted at 70° C. for 15 hours under vacuum conditions to obtain a hydrophilic silicone hydrogel.
[0057] Example 3
[0058] 88 g of polydimethylsiloxane, 15 g of tetraethyl orthosilicate, 2 g of stannous octoate and 200 mL of toluene were mixed to obtain a first mixed solution; the first mixed solution was dropped into 200 mL of a 0.05 g / mL polyvinyl alcohol solution under stirring, and the mixture was reacted at 25° C. for 24 h. After the reaction, the obtained product was washed with deionized water, and dried at 60° C. for 36 h to obtain a first product;
[0059] 70 g of sulfobetaine methacrylate, 140 g of β-hydroxyethyl methacrylate, 15 g of methacrylic acid, 25 g of azobisisobutyronitrile, 45 g of N,N-dimethylbisacrylamide and 300 mL of toluene were mixed to obtain a second mixed solution;
[0060] The first product was immersed in the second mixed solution at 25° C., and after reaching swelling equilibrium, the mixture was reacted at 60° C. under vacuum conditions for 20 hours to obtain a hydrophilic silicone hydrogel.
[0061] Example 4
[0062] 90 g of polydimethylsiloxane, 25 g of tetraethyl orthosilicate, 1.8 g of stannous octoate and 250 mL of toluene were mixed to obtain a first mixed solution; the first mixed solution was dropped into 200 mL of a 0.1 g / mL polyvinyl alcohol solution under stirring, and the mixture was reacted at 25° C. for 24 h. After the reaction, the obtained product was washed with deionized water, and dried at 60° C. for 36 h to obtain a first product;
[0063] 50 g of sulfobetaine methacrylate, 150 g of β-hydroxyethyl methacrylate, 10 g of methacrylic acid, 22 g of azobisisobutyronitrile, 40 g of N,N-dimethylbisacrylamide and 300 mL of toluene were mixed to obtain a second mixed solution;
[0064] The first product was immersed in the second mixed solution at 25° C., and after reaching swelling equilibrium, the mixture was reacted at 65° C. under vacuum conditions for 15 hours to obtain a hydrophilic silicone hydrogel.
[0065] Example 5
[0066] 93 g of polydimethylsiloxane, 25 g of tetraethyl orthosilicate, 3 g of stannous octoate and 200 mL of toluene were mixed to obtain a first mixed solution; the first mixed solution was dropped into 200 mL of a 0.1 g / mL polyvinyl alcohol solution under stirring, and the mixture was reacted at 25° C. for 24 h. After the reaction, the obtained product was washed with deionized water, and dried at 60° C. for 36 h to obtain a first product;
[0067] 70 g of sulfobetaine methacrylate, 110 g of β-hydroxyethyl methacrylate, 10 g of methacrylic acid, 20 g of azobisisobutyronitrile, 40 g of N,N-dimethylbisacrylamide and 200 mL of toluene were mixed to obtain a second mixed solution;
[0068] The first product was immersed in the second mixed solution at 25° C., and after reaching swelling equilibrium, the mixture was reacted at 60° C. under vacuum conditions for 18 hours to obtain a hydrophilic silicone hydrogel.
[0069] Performance Testing
[0070] The polarographic method in accordance with the national standard GB / T 11417.7-2012 was used to test the oxygen permeability of the hydrophilic silicone hydrogels prepared in Examples 1 to 5. The test results are shown in Table 1.
[0071] The water content of the hydrophilic silicone hydrogels prepared in Examples 1 to 5 was tested by weighing method. The test results are shown in Table 1.
[0072] The contact angles of the hydrophilic silicone hydrogels prepared in Examples 1 to 5 were measured using the drop method in accordance with the national standard GB / T 11417.7-2012. The test results are shown in Table 1.
[0073] Using bovine serum albumin (BSA) as a model protein, the protein adsorption amount on the surface of the hydrophilic silicone hydrogel prepared in Examples 1 to 5 was measured by the bicinchoninic acid method. The test results are shown in Table 1.
[0074] Table 1 Performance test results of hydrophilic silicone hydrogel surfaces in Examples 1 to 5
[0075]
[0076] As shown in Table 1, the oxygen permeability of the hydrophilic silicone hydrogel prepared in the present invention is between 30 and 50 × 10 -11 (cm 2 / s)(mLO 2 / mL·mmHg), indicating that the oxygen permeability of the hydrophilic silicone hydrogel provided by the present invention is well improved; the water content is between 70% and 80%, indicating that the water content of the hydrophilic silicone hydrogel provided by the present invention is relatively high, and the comfort of lens wearing can be effectively improved; the contact angle is between 10° and 15°, indicating that the surface hydrophilicity of the hydrophilic silicone hydrogel provided by the present invention is very good; the protein adsorption amount is between 0.4 and 0.7, indicating that the hydrophilic silicone hydrogel provided by the present invention has excellent anti-protein pollution performance.
[0077] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. A method for preparing a hydrophilic silicone hydrogel, characterized in that: The following steps are involved: Mixing polydimethylsiloxane, tetraethyl orthosilicate, stannous octoate and a first organic solvent, and adding a polyvinyl alcohol solution to carry out a first reaction after the mixing is completed to obtain a first product; Mixing sulfobetaine methacrylate, β-hydroxyethyl methacrylate, methacrylic acid, azobisisobutyronitrile, N,N-dimethylbisacrylamide and a second organic solvent to obtain a second mixed solution; The first product is immersed in the second mixed solution, and after reaching swelling equilibrium, a second reaction is carried out to obtain a hydrophilic silicone hydrogel.
2. The method for preparing the hydrophilic silicone hydrogel according to claim 1, characterized in that: The mass ratio of the polydimethylsiloxane, tetraethyl orthosilicate and stannous octoate is 80-100:5-30:0.4-3; The usage ratio of the polydimethylsiloxane and the first organic solvent is 80-100 g:150-250 mL.
3. The method for preparing the hydrophilic silicone hydrogel according to claim 2, characterized in that: The first organic solvent and the second organic solvent are independently toluene.
4. The method for preparing the hydrophilic silicone hydrogel according to claim 3, characterized in that: The concentration of the polyvinyl alcohol solution is 0.05-0.1 g / mL; The usage ratio of the polydimethylsiloxane to the polyvinyl alcohol solution is 80-100 g:150-300 mL.
5. The method for preparing the hydrophilic silicone hydrogel according to claim 4, characterized in that: The temperature of the first reaction is 20-40° C., and the time of the first reaction is 24-48 hours.
6. The method for preparing the hydrophilic silicone hydrogel according to claim 4 or 5, characterized in that: The mass ratio of the sulfobetaine methacrylate, β-hydroxyethyl methacrylate, and methacrylic acid is 50-80:100-200:5-20; The usage ratio of β-hydroxyethyl methacrylate, azobisisobutyronitrile, N,N-dimethylbisacrylamide and the second organic solvent is 100-200 g: 20-40 g: 33-50 g: 100-300 mL.
7. The method for preparing the hydrophilic silicone hydrogel according to claim 6, characterized in that: The immersion temperature is 20-30°C.
8. The method for preparing the hydrophilic silicone hydrogel according to claim 7, characterized in that: The temperature of the second reaction is 60-80° C., and the time of the second reaction is 10-20 hours.
9. The hydrophilic silicone hydrogel obtained by the method for preparing the hydrophilic silicone hydrogel according to any one of claims 1 to 8.
10. Use of the hydrophilic silicone hydrogel according to claim 9 in contact lenses.