Preparation method and application of silicone hydrogel

Abstract

The invention discloses a preparation method and application of silicone hydrogel. The invention relates to the technical field of silicon hydrogel, which specifically comprises the following preparation steps: step 1, pouring lauryl sodium sulfate into a sodium chloride solution, and carrying out ultrasonic treatment for 15-25 minutes at room temperature; step 2, adding an organic silicon macromonomer, heating to 35-50 DEG C, and stirring to react for 1.5-2 hours; and 3, adding N-vinyl pyrrolidone, hydroxyethyl methylacrylate, octadecyl acrylate and ethylene glycol dimethacrylate, and uniformly stirring and mixing at room temperature. According to the preparation method and the application process of the silicon hydrogel, the crosslinking density of the silicon hydrogel can be better controlled by adopting the organic silicon macromonomer, and the pore size and distribution of the silicon hydrogel can be accurately changed by adjusting the structure and the dosage of the organic silicon macromonomer in the polymerization process, so that the oxygen permeability of the silicon hydrogel is optimized.

Description

Technical Field

[0001] The present invention relates to the technical field of silicone hydrogels, and specifically provides a preparation method and application of a silicone hydrogel. Background Art

[0002] Referring to a Chinese patent for a hydrophilic silicone hydrogel (Publication No.: CN104927002A), the silicone hydrogel is composed of the following components by weight percentage: silicone-containing monomer: 30 - 55%; hydrophilic monomer: 41 - 68%; polyethylene glycol diacrylate: 1 - 3%; free radical initiator: 0.1 - 1%. This silicone hydrogel material has properties such as high mechanical properties, good surface wettability, and good anti-protein deposition performance; at the same time, a preparation method of this silicone hydrogel is provided. In this preparation process, no small molecule cross-linking agent is required. The long chain of polyethylene glycol diacrylate not only plays a role in reducing the cross-linking density but also can improve the surface wettability; an application method of this silicone hydrogel is also provided. This silicone hydrogel is used to prepare contact lenses, and the wearer feels more comfortable. However, the mechanical properties and oxygen permeability of the silicone hydrogel prepared by the above prior art need to be further improved; for this reason, the present invention proposes a preparation method and application of a silicone hydrogel to solve the problems mentioned above. Summary of the Invention

[0003] (I) Technical Problems to be Solved

[0004] In view of the deficiencies of the prior art, the present invention provides a preparation method and application of a silicone hydrogel, solving the problems mentioned in the above background art.

[0005] (II) Technical Solutions

[0006] To achieve the above objectives, the present invention is realized through the following technical solutions: A preparation method of a silicone hydrogel specifically includes the following preparation steps:

[0007] Step 1: Pour sodium dodecyl sulfate into a sodium chloride solution, and under room temperature conditions, perform ultrasonic treatment for 15 - 25 min;

[0008] Step 2: Add a silicone macromonomer, heat to 35 - 50 °C, and stir and react for 1.5 - 2 h;

[0009] Step 3: Add N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, octadecyl acrylate, and ethylene glycol dimethacrylate, and stir and mix evenly under room temperature conditions;

[0010] Step 4: Pour it into a mold and irradiate it with an ultraviolet lamp to cure it into a film;

[0011] Step 5: Immerse the film prepared in Step 4 in ethanol, perform ultrasonic treatment for 10 - 15 min, and then place it in a drying oven at 100 - 110 °C to dry to a constant weight, thus obtaining the silicone hydrogel.

[0012] Preferably, the preparation method of the silicone hydrogel further includes:

[0013] After plasma treatment of the dried film, immerse it in 2-methacryloyloxyethyl phosphorylcholine, then add FeSO4(NH4)2SO4·6H2O, raise the temperature of the water bath to 70 - 80 °C, react for 20 - 24 h, and then soak it in deionized water and perform ultrasonic treatment for 15 - 30 min.

[0014] Preferably, the weight parts of each component added in the silicone hydrogel are as follows: sodium dodecyl sulfate 0.3 - 0.5 parts, sodium chloride solution 7 - 12 parts, organosilicon macromolecular monomer 0.25 - 0.6 parts, N-vinylpyrrolidone 1.5 - 2 parts, 2-hydroxyethyl methacrylate 2.5 - 4.5 parts, octadecyl acrylate 0.8 - 1.6 parts, ethylene glycol dimethacrylate 2 - 4 parts, 2-methacryloyloxyethyl phosphorylcholine 12 - 20 parts, FeSO4(NH4)2SO4·6H2O 0.12 - 0.18 parts.

[0015] Preferably, in Step 1, the concentration of the sodium chloride solution is 0.08 - 0.15 mol / L.

[0016] Preferably, in Step 2, the preparation method of the organosilicon macromolecular monomer is as follows:

[0017] S1: Add 5 - 10 mL of dichloromethane and 1.5 - 3 g of dibutyltin dilaurate to 4.5 - 7 g of organosilicon raw materials, and stir until evenly mixed to obtain a first mixed solution;

[0018] S2: Mix 3.5 - 5 g of isocyanatoethyl methacrylate with 7 - 12 mL of dichloromethane evenly to obtain a second mixed solution;

[0019] S3: Slowly drop the second mixed solution into the first mixed solution, raise the temperature to 30 - 40 °C, stop heating after the reaction ends, and cool to room temperature, and then perform rotary evaporation at a temperature of 35 - 45 °C to obtain the organosilicon macromolecular monomer.

[0020] Preferably, in Step 4, the irradiation wavelength of the ultraviolet lamp is 365 - 380 nm, and the irradiation time is 40 - 50 min.

[0021] Preferably, in Step 5, the mass fraction of ethanol is 75% - 80%.

[0022] An application of a silicone hydrogel in the preparation of an optical device.

[0023] Preferably, a sutureless soft contact lens prepared from a silicone hydrogel is used in vitreous surgery;

[0024] 2n tension-reducing incisions are evenly arranged circumferentially along the sutureless soft contact lens, where n is a positive integer; the tension-reducing incisions are used to provide a contraction margin for the edge contraction tension of the sutureless soft contact lens without affecting the front fitting of the sutureless soft contact lens.

[0025] Preferably, when the cross-section of the sutureless soft contact lens is circular when viewed from above, the outer diameter size range of the sutureless soft contact lens is: 8-20 mm; the central thickness size range of the sutureless soft contact lens is 0.01-0.20 mm; the base curve range of the sutureless soft contact lens body is: 7.2-9.2 mm.

[0026] (III) Beneficial effects

[0027] The present invention provides a preparation method and application of a silicone hydrogel. Compared with the prior art, it has the following beneficial effects:

[0028] (1) The preparation method and application of the silicone hydrogel can better control the crosslinking density of the silicone hydrogel by using organosilicon macromonomers. During the polymerization process, by adjusting the structure and dosage of the organosilicon macromonomers, the pore size and distribution of the silicone hydrogel can be precisely changed, thereby optimizing its gas permeability; and the functional groups in the organosilicon macromonomers can enhance the mechanical properties of the silicone hydrogel, making the silicone hydrogel more tough and durable; and the organosilicon macromonomers are easy to copolymerize with other monomers, so that the prepared silicone hydrogel can carry more functional groups, thereby improving the hydrophilicity of the silicone hydrogel and improving its surface wettability.

[0029] (2) The preparation method and application of the silicone hydrogel remove impurities and pollutants on its surface by plasma treatment of the silicone hydrogel, and at the same time activate it to generate active sites such as free radicals, making it easier for 2-methacryloyloxyethyl phosphorylcholine to undergo grafting reactions or physical adsorption, significantly improving its biocompatibility. When applied to contact lenses, it can reduce protein adsorption, reduce irritation to the eyes, and make wearing more comfortable; at the same time, FeSO4(NH4)2SO4·6H2O is added and ultrasonic treatment is carried out to uniformly disperse the iron salt in the silicone hydrogel system, thereby enhancing the physical properties of the silicone hydrogel and improving its mechanical strength. Description of the drawings

[0030] Figure 1 It is the SEM diagram of the silicone hydrogel of Example 1 and Comparative Example 2 provided for the preparation method and application of a silicone hydrogel of the present invention.

[0031] Figure 2 Schematic structural diagram of a sutureless soft contact lens with a tension-reducing incision added according to the present invention.

[0032] Reference numerals: 1. Sutureless soft contact lens; 2. Tension-reducing incision. Detailed implementation manners

[0033] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention. Silicone raw material: PEG-PDMS-PEG, Nanjing Fuqun Company.

[0034] Example 1

[0035] A preparation method of a silicone hydrogel specifically includes the following preparation steps:

[0036] Step 1: Pour 0.3 g of sodium dodecyl sulfate into 7 g of sodium chloride solution with a concentration of 0.08 mol / L, and perform ultrasonic treatment for 15 min at room temperature;

[0037] Step 2: Add 0.25 g of silicone macromonomer, heat up to 35 °C, and stir and react for 1.5 h; wherein, the preparation method of the silicone macromonomer is: add 5 mL of dichloromethane and 1.5 g of dibutyltin dilaurate to 4.5 g of silicone raw material, stir until evenly mixed to obtain a mixed solution 1; mix 3.5 g of isocyanatoethyl methacrylate with 7 mL of dichloromethane evenly to obtain a mixed solution 2; slowly drop the mixed solution 2 into the mixed solution 1, heat up to 30 °C, stop heating after the reaction ends, and cool to room temperature, and then perform rotary evaporation at a temperature of 35 °C to obtain the silicone macromonomer;

[0038] Step 3: Add 1.5 g of N-vinylpyrrolidone, 2.5 g of 2-hydroxyethyl methacrylate, 0.8 g of octadecyl acrylate, and 2 g of ethylene glycol dimethacrylate, and stir and mix evenly at room temperature;

[0039] Step 4: Pour it into a mold, and irradiate it with a UV lamp with an irradiation wavelength of 365 nm for 40 min to cure it into a film;

[0040] Step 5: Immerse the film prepared in Step 4 in ethanol with a mass fraction of 75%, perform ultrasonic treatment for 10 min, and then place it in a drying oven at 100 °C to dry to a constant weight;

[0041] Step 6: After plasma treatment of the dried film, immerse it in 12 g of 2-methacryloyloxyethyl phosphorylcholine, then add 0.12 g of FeSO4(NH4)2SO4·6H2O, raise the temperature in a water bath to 70 °C, react for 20 h, and then soak it in deionized water and perform ultrasonic treatment for 15 min to obtain the silicone hydrogel.

[0042] Example 2

[0043] A preparation method of a silicone hydrogel specifically includes the following preparation steps:

[0044] Step 1: Pour 0.4 g of sodium dodecyl sulfate into 9 g of sodium chloride solution with a concentration of 0.12 mol / L, and perform ultrasonic treatment for 20 min at room temperature;

[0045] Step 2: Add 0.45 g of organosilicon macromonomer, raise the temperature to 45 °C, and stir and react for 1.8 h; among them, the preparation method of the organosilicon macromonomer is: add 8 mL of dichloromethane and 2.2 g of dibutyltin dilaurate to 5.5 g of organosilicon raw material, stir until evenly mixed to obtain a mixed solution 1; mix 4.2 g of isocyanatoethyl methacrylate with 9.5 mL of dichloromethane evenly to obtain a mixed solution 2; slowly drop the mixed solution 2 into the mixed solution 1, raise the temperature to 35 °C, stop heating after the reaction ends, and cool to room temperature, and then perform rotary evaporation at a temperature of 40 °C to obtain the organosilicon macromonomer;

[0046] Step 3: Add 1.6 g of N-vinylpyrrolidone, 3.5 g of 2-hydroxyethyl methacrylate, 1.2 g of octadecyl acrylate, and 3 g of ethylene glycol dimethacrylate, and stir and mix evenly at room temperature;

[0047] Step 4: Pour it into a mold and irradiate it with a UV lamp with an irradiation wavelength of 370 nm for 45 min to cure it into a film;

[0048] Step 5: Immerse the film prepared in Step 4 in ethanol with a mass fraction of 78%, perform ultrasonic treatment for 12 min, and then place it in a drying oven at 105 °C and dry it to a constant weight;

[0049] Step 6: After plasma treatment of the dried film, immerse it in 16 g of 2-methacryloyloxyethyl phosphorylcholine, then add 0.15 g of FeSO4(NH4)2SO4·6H2O, raise the temperature in a water bath to 75 °C, react for 22 h, and then soak it in deionized water and perform ultrasonic treatment for 25 min to obtain the silicone hydrogel.

[0050] Example 3

[0051] A preparation method of a silicone hydrogel specifically includes the following preparation steps:

[0052] Step 1: Pour 0.5 g of sodium dodecyl sulfate into 12 g of sodium chloride solution with a concentration of 0.15 mol / L, and under room temperature conditions, perform ultrasonic treatment for 25 min;

[0053] Step 2: Add 0.6 g of organosilicon macromonomer, heat up to 50 °C, and stir and react for 2 h; among them, the preparation method of the organosilicon macromonomer is as follows: Add 10 mL of dichloromethane and 3 g of dibutyltin dilaurate to 7 g of organosilicon raw material, stir until evenly mixed to obtain a mixed solution I; Mix 5 g of isocyanatoethyl methacrylate with 12 mL of dichloromethane evenly to obtain a mixed solution II; Slowly drop the mixed solution II into the mixed solution I, heat up to 40 °C, stop heating after the reaction ends, and cool to room temperature, and then perform rotary evaporation at a temperature of 45 °C to obtain the organosilicon macromonomer;

[0054] Step 3: Add 2 g of N-vinylpyrrolidone, 4.5 g of 2-hydroxyethyl methacrylate, 1.6 g of octadecyl acrylate, and 4 g of ethylene glycol dimethacrylate, and stir and mix evenly at room temperature;

[0055] Step 4: Pour it into a mold, and irradiate it with a UV lamp with an irradiation wavelength of 380 nm for 50 min to cure it into a film;

[0056] Step 5: Immerse the film prepared in Step 4 in ethanol with a mass fraction of 80%, perform ultrasonic treatment for 15 min, and then place it in a drying oven at 110 °C to dry to a constant weight;

[0057] Step 6: After performing plasma treatment on the dried film, immerse it in 20 g of 2-methacryloyloxyethyl phosphorylcholine, then add 0.18 g of FeSO4(NH4)2SO4·6H2O, heat up to 80 °C in a water bath, react for 24 h, and then soak it in deionized water and perform ultrasonic treatment for 30 min to obtain the silicone hydrogel.

[0058] Comparative Example 1

[0059] Compared with Example 1, the difference is that the organosilicon macromonomer in Example 1 is replaced with polydimethylsiloxane; the rest remains unchanged. Comparative Example 2

[0060] Compared with Example 1, the difference is that Step 6 in Example 1 is deleted; the rest remains unchanged. Oxygen permeability test: Use a coulomb oxygen permeation meter for testing. Cover the specimen with an aluminum foil mask, leaving an uncovered circular area, and circulate pure oxygen on one side of the film and nitrogen on the other side. Input nitrogen into the coulomb sensor, and when reaching a steady state, obtain the value of DK / t (t is the film thickness); the results are shown in Table 1.

[0061] Water retention rate test: First, soak the specimen in PBS solution for 24 h to stabilize it, then wipe off the water on the surface of the specimen with a spectacle cloth moistened with PBS solution, and measure its initial weight as W t0 ; Place the specimen in a room temperature environment of 22 °C for 1 h, and record its weight at 10 min, 30 min, and 60 min respectively, denoted as W t1 ; Finally, dry the specimen completely and weigh its dry weight, denoted as W t2 ;

[0062] The calculation formula for the water retention rate is as follows: The results are shown in Table 1.

[0063] Table 1

[0064]

[0065] Mechanical property test: Tensile and compression property tests are carried out on the specimen on an electronic universal material testing machine.

[0066] The temperature condition is normal temperature; the results are shown in Table 2.

[0067] Table 2

[0068] Tensile strength / MPa Compressive strength / MPa Example 1 5.32 4.65 Example 2 5.08 4.33 Example 3 4.92 3.98 Comparative example 1 3.59 2.88 Comparative example 2 3.22 2.14

[0069] In the present invention, the silicone hydrogel is used for sutureless soft contact lenses. Specifically, a sutureless soft contact lens with predetermined parameters is applied in eye surgeries, where the eye surgeries include any one of various complex cataract surgeries, glaucoma surgeries, vitreoretinal surgeries, etc. that require surgical operations inside the eyeball; and when the cross-section of the soft contact lens is circular when viewed from above, the outer diameter size range of the soft contact lens is 8 - 20 mm, and the central thickness size range of the soft contact lens is 0.01 - 0.20 mm; the base curve range of the soft contact lens body is 7.2 - 9.2 mm; a mark for distinguishing the front and back of the soft contact lens body is provided on the soft contact lens; the mark is engraved or marked on the front and / or back and / or inside of the soft contact lens for distinguishing and identifying the front and back of the soft contact lens.

[0070] Preferably, the sutureless soft contact lens prepared from the silicone hydrogel is applied in vitreous surgeries;

[0071] As Figure 2 shown: n tension-reducing incisions are evenly arranged along the circumferential direction of the sutureless soft contact lens, where n is a positive integer; the tension-reducing incisions are used to provide a contraction margin for the edge contraction tension of the sutureless soft contact lens without affecting the fitting of the sutureless soft contact lens to the corneal surface.

[0072] It is understandable that a symmetric tension-reducing incision 2 for reducing the shrinkage tension at the edge of the soft contact lens is also provided to facilitate good fitting with the cornea. In this way, after the sutureless soft contact lens is applied to the patient's cornea, if the fitting position is inaccurate and the edge curls, the above-mentioned tension-reducing incision 2 can be used to provide a curling margin for the edge of the sutureless soft contact lens, avoiding poor fitting at the position where the edge of the sutureless soft contact lens contacts the cornea, thereby affecting the clarity of the surgical field.

[0073] When the top-down cross-section of the sutureless soft contact lens is circular, the outer diameter size range of the sutureless soft contact lens is: 8 - 20 mm; the central thickness size range of the sutureless soft contact lens is 0.01 - 0.20 mm; the base curve range of the soft contact lens body is: 7.2 - 9.2 mm.

[0074] The sutureless soft contact lens with predetermined parameters is applied to eye surgeries, where the eye surgeries include any one of various complex cataract surgeries, glaucoma surgeries, vitreoretinal surgeries, etc. that require surgical operations inside the eyeball.

[0075] Meanwhile, the content not described in detail in this specification belongs to the prior art well-known to those skilled in the art.

[0076] It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or further includes elements inherent to such process, method, article or device.

[0077] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a silicone hydrogel, characterized in that: The specific preparation steps include: Step 1: Pour sodium dodecyl sulfate into sodium chloride solution and perform ultrasonic treatment for 15-25 minutes at room temperature; Step 2: Add the organosilicon macromolecular monomer, raise the temperature to 35-50°C, and stir to react for 1.5-2h; Step 3, adding N-vinyl pyrrolidone, hydroxyethyl methacrylate, octadecyl acrylate and ethylene glycol dimethacrylate, and stirring and mixing at room temperature; Step 4: Pour the mixture into a mold and irradiate it with an ultraviolet lamp to solidify it into a film; Step 5: Immerse the film obtained in step 4 in ethanol, perform ultrasonic treatment for 10-15 minutes, and then place it in a drying oven at 100-110° C. to dry to constant weight to obtain a silicone hydrogel.

2. The method for preparing a silicone hydrogel according to claim 1, characterized in that: The preparation method of the silicone hydrogel also includes: After the dried film is treated with plasma, it is immersed in 2-methacryloyloxyethyl phosphorylcholine, and then FeSO4(NH4)2SO4·6H2O is added. The water bath is heated to 70-80°C, reacted for 20-24 hours, and then immersed in deionized water for ultrasonic treatment for 15-30 minutes.

3. The method for preparing a silicone hydrogel according to claim 2, characterized in that: The weight proportions of the components added in the silicone hydrogel are: 0.3-0.5 parts of sodium dodecyl sulfate, 7-12 parts of sodium chloride solution, 0.25-0.6 parts of organic silicon macromolecular monomer, 1.5-2 parts of N-vinyl pyrrolidone, 2.5-4.5 parts of hydroxyethyl methacrylate, 0.8-1.6 parts of octadecyl acrylate, 2-4 parts of ethylene glycol dimethacrylate, 12-20 parts of 2-methacryloyloxyethyl phosphorylcholine, and 0.12-0.18 parts of FeSO4(NH4)2SO4·6H2O.

4. The method for preparing a silicone hydrogel according to claim 1, characterized in that: In the step 1, the concentration of the sodium chloride solution is 0.08-0.15 mol / L.

5. The method for preparing a silicone hydrogel according to claim 1, characterized in that: In the step 2, the preparation method of the organosilicon macromolecular monomer is: S1. Add 5-10 mL of dichloromethane and 1.5-3 g of dibutyltin dilaurate to 4.5-7 g of the organosilicon raw material, and stir until the mixture is uniform to obtain a mixed solution 1; S2, 3.5-5 g of isocyanoethyl methacrylate and 7-12 mL of dichloromethane were mixed evenly to obtain a mixed solution 2; S3. Slowly drop the mixed solution 2 into the mixed solution 1, raise the temperature to 30-40°C, stop heating after the reaction is completed, cool to room temperature, and then perform rotary evaporation at a temperature of 35-45°C to obtain the organosilicon macromolecular monomer.

6. The method for preparing a silicone hydrogel according to claim 1, characterized in that: In the step 4, the irradiation wavelength of the ultraviolet lamp is 365-380nm, and the irradiation time is 40-50min.

7. The method for preparing a silicone hydrogel according to claim 1, characterized in that: In the step 5, the mass fraction of ethanol is 75%-80%.

8. Application of silicone hydrogel in suture-free soft contact lenses.

9. The use of the silicone hydrogel in suture-free soft contact lenses according to claim 8, characterized in that: Silicone hydrogels are used to make suture-free soft contact lenses for use in vitreous surgery; 2n tension-reducing cuts are evenly opened along the circumference of the sutureless soft contact lens, wherein n is a positive integer; the tension-reducing cuts are used to provide a shrinkage margin for the shrinkage tension of the edge of the sutureless soft contact lens without affecting the front fitting of the sutureless soft contact lens.

10. The use of the silicone hydrogel in suture-free soft contact lenses according to claim 9, characterized in that: When the cross-section of the suture-free soft contact lens is viewed from above and is circular, the outer diameter of the suture-free soft contact lens is in the range of 8-20 mm; the central thickness of the suture-free soft contact lens is in the range of 0.01-0.20 mm; and the base curve of the suture-free soft contact lens body is in the range of 7.2-9.2 mm.

Images