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CN-122011478-A - Silicon hydrogel material and preparation method and application thereof

CN122011478ACN 122011478 ACN122011478 ACN 122011478ACN-122011478-A

Abstract

The invention discloses a silicon hydrogel material, a preparation method and application thereof. The preparation method comprises the steps of solidifying and forming 2-hydroxyethyl methacrylate (HEMA), 3- (trimethylsiloxy) propyl methacrylate (TRIS), ethylene Glycol Dimethacrylate (EGDMA), a silane coupling agent and a photoinitiator through photopolymerization reaction to obtain a silicon hydrogel substrate, carrying out oxygen plasma treatment, preparing a PDMS hydrophobic layer, carrying out oxygen plasma treatment, soaking in an organic solution containing a hydrophobic initiator, and forming a hydrophilic polymer layer. The invention realizes the high oxygen permeability, long-acting moisture retention, low friction and protein deposition resistance of the lens by constructing a double-layer functional interface of hydrophobic water locking and hydrophilic lubrication.

Inventors

  • SUN SHUQING
  • An Xulian
  • TENG LULU

Assignees

  • 清华大学深圳国际研究生院

Dates

Publication Date
20260512
Application Date
20260302

Claims (10)

  1. 1. A method for preparing a silicone hydrogel material, comprising the steps of: 1) The preparation method comprises the steps of (1) carrying out photopolymerization curing molding on 2-hydroxyethyl methacrylate (HEMA), 3- (trimethylsiloxy) propyl methacrylate (TRIS), ethylene Glycol Dimethacrylate (EGDMA), a silane coupling agent and a photoinitiator to obtain a silicon hydrogel substrate, or carrying out photopolymerization curing molding on 2-hydroxyethyl methacrylate (HEMA), 3- (trimethylsiloxy) propyl methacrylate (TRIS), ethylene Glycol Dimethacrylate (EGDMA), N-vinyl pyrrolidone (NVP), a silane coupling agent and a photoinitiator to obtain a silicon hydrogel substrate; 2) Performing oxygen plasma treatment on the silicon hydrogel substrate obtained in the step 1); 3) Preparing a hydrophobic layer on the surface of the silicon hydrogel substrate treated in the step 2), wherein the hydrophobic layer is Polydimethylsiloxane (PDMS); 4) Oxygen plasma treatment is carried out on the PDMS layer obtained in the step 3); 5) Immersing the sample subjected to the oxygen plasma treatment in the step 4) in an organic solution containing a hydrophobic initiator; 6) Immersing the sample obtained in the step 5) in an aqueous solution containing a hydrophilic monomer and a water-soluble initiator, and forming a hydrophilic polymer layer by polymerization.
  2. 2. The method according to claim 1, wherein in step 1), the silane coupling agent is methacryloxypropyl trimethoxysilane; preferably, the photoinitiator is selected from any one of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO) and Irgacure-2959; Preferably, the mass ratio of the 2-hydroxyethyl methacrylate (HEMA), the 3- (trimethylsiloxy) propyl methacrylate (TRIS), the Ethylene Glycol Dimethacrylate (EGDMA), the N-vinyl pyrrolidone (NVP), the silane coupling agent and the photoinitiator is 80-95:1-10:1-2:0-20:0.5-5:0.3-0.7, preferably 80-95:1-10:1-2:10-20:0.5-5:0.3-0.7; Preferably, the photopolymerization reaction is carried out under the conditions that the ultraviolet light intensity is 200-500 mW/cm 2 , the reaction time is 30 s-60 min, and the preferable reaction time is 5-30 min; Preferably, the photopolymerization is carried out under oxygen-barrier conditions.
  3. 3. The method according to claim 1, wherein in the step 2), the oxygen plasma treatment power is 30-60W, and the treatment time is 2-5 min.
  4. 4. The method according to claim 1, wherein in the step 3), the step of preparing the hydrophobic layer comprises mixing PDMS with a curing agent, coating the mixture on the surface of the silicon hydrogel substrate treated in the step 2), and forming the hydrophobic layer after curing; Preferably, the coating is spin coating; preferably, the rotating speed of the spin coating is 500-4000 rmp, and the spin coating time is 5-130 s; Preferably, the spin coating is step spin coating, specifically spin coating at a speed of 500-1500 rpm for 5-10 s, and spin coating at a speed of 2000-4000 rmp for 30-120 s; preferably, the curing temperature is 60-100 ℃, and the curing time is 1-4 hours; preferably, the method further comprises the steps of washing and nitrogen blow-drying after the step 3), wherein the washing is isopropanol washing and water washing.
  5. 5. The method according to claim 1, wherein in the step 4), the oxygen plasma treatment power is 30-60W, and the treatment time is 2-5 min.
  6. 6. The preparation method according to claim 1, wherein in the step 5), the hydrophobic initiator is a photoinitiator or a thermal initiator, the photoinitiator is benzophenone, the thermal initiator is benzoyl peroxide, the solvent of the organic solution containing benzophenone is ethanol solution or isopropanol, and the solvent of the organic solution containing benzoyl peroxide is acetone; Preferably, in the organic solution containing the hydrophobic initiator, the concentration of the hydrophobic initiator is 5-15 wt.%; Preferably, the soaking time is 3-5 min.
  7. 7. The method according to claim 1, wherein in the step 6), the hydrophilic monomer is a photoinitiating monomer or a thermally initiating monomer, and the water-soluble initiator is a photoinitiator or a thermal initiator; preferably, the photoinitiating monomer is at least one selected from the group consisting of 2-hydroxyethyl methacrylate (HEMA), acrylamide (AAm), acrylic Acid (AA), N-Vinylpyrrolidone (VP), N-Dimethylacrylamide (DMAA); preferably, the thermally initiated monomer is selected from at least one of acrylamide (AAm), acrylic Acid (AA), N-Dimethylacrylamide (DMAA); Preferably, the photoinitiator is Irgacure-2959; Preferably, the thermal initiator is ammonium persulfate; preferably, in the aqueous solution containing the hydrophilic monomer and the water-soluble initiator, the concentration of the hydrophilic monomer is 15-25 wt%, and the concentration of the water-soluble initiator is 0.1-1 wt%, preferably 0.5-1 wt%; preferably, the thickness of the hydrophilic polymer layer is 10-50 μm.
  8. 8. The preparation method of the polymer composition according to claim 1, wherein in the step 6), the polymerization reaction is photopolymerization or thermal polymerization, the condition of the photopolymerization is ultraviolet irradiation, the reaction is carried out for 40-60 min, and the condition of the thermal polymerization is polymerization at room temperature to 90 ℃ for 70-100 min; Preferably, the step 6) further comprises cleaning and stabilizing treatment, wherein the cleaning is soaking and cleaning in water to remove unreacted monomers, initiators and oligomers, the stabilizing treatment is in a dry and fixed form, the soaking and cleaning time is 20-30 h, water is replaced every 4-6 h, the soaking and cleaning time is preferably 12-24 h, the drying is natural drying or drying, preferably drying is carried out, and the drying temperature is 40-60 ℃.
  9. 9. A silicone hydrogel material obtainable by the method of any one of claims 1 to 8.
  10. 10. Use of the method of any one of claims 1-8 or the silicone hydrogel material of claim 9 in the preparation of a contact lens; Preferably in the preparation of bandage mirrors.

Description

Silicon hydrogel material and preparation method and application thereof Technical Field The invention belongs to the technical field of biomedical polymer materials and ophthalmic medical devices, and particularly relates to a silicon hydrogel material and a preparation method and application thereof. Background Silicon hydrogel materials are widely used in contact lenses, bandaged lenses and biological soft tissue replacement materials due to their high moisture content and excellent oxygen permeability. Existing silicone hydrogel bandages are typically formed by photoinitiated or thermally initiated polymerization using hydroxyethyl methacrylate (HEMA) co-polymerization systems containing a silicone monomer (e.g., 3- (trimethylsiloxy) propyl methacrylate, TRIS), which maintains moderate flexibility while ensuring high oxygen permeability. However, in the actual clinical use process, the traditional silicon hydrogel bandage mirror has the following general problems that firstly, the surface hydrophobicity is high, the tear wettability is poor, the evaporation rate is high, and thus the surface of the mirror is dry and uncomfortable to wear, secondly, the surface friction coefficient is high, the cornea epithelium is easily damaged in the eyelid repeated friction process, thirdly, the hydrophobic interface is easy to adsorb protein and lipid impurities, the light transmittance and the biocompatibility of the mirror are affected, and the long-term use of the mirror in xerophthalmia patients and postoperative protection is limited. To improve the wettability and surface friction characteristics of silicone hydrogel materials, researchers have proposed various modification strategies including co-incorporation of hydrophilic monomers, surface plasma treatment, surface coating of hydrophilic polymers, and hybrid modification with hydrophilic additives (e.g., polyethylene glycol PEG, polyvinylpyrrolidone PVP, etc.). However, these methods generally have the disadvantages that the copolymerization modification reduces the proportion of the silica segment, which leads to a significant reduction in oxygen transmittance, the plasma treatment effect is short, the degradation over time is easy, the adhesion of the surface coating type modified layer is poor, the peeling is easy in the wearing or cleaning process, and the modification of the additive is easy to cause the phase separation of the system, which results in a reduction in mechanical properties and optical uniformity. Therefore, how to achieve both long-term stable moisture retention and low friction properties while maintaining high oxygen permeability is still a key challenge in silicone hydrogel bandaging mirror research. Disclosure of Invention The invention aims to solve the technical problems of poor surface wettability, high friction coefficient, insufficient moisturizing performance, serious protein deposition and the like of a silicon hydrogel bandage mirror in the prior art, and provides a silicon hydrogel material, a preparation method thereof and application thereof in preparing contact lenses. The preparation method provided by the invention has the advantages of simple process and strong controllability, and the prepared silicon hydrogel material has clean surface and high stability, and has super-hydrophilicity and low friction coefficient. The silicon hydrogel material provided by the invention can obviously improve the hydrophilicity and lubricity of the surface of the material on the basis of ensuring high oxygen permeability, thereby realizing comfort and biocompatibility of long-term wearing, and being further applied to cornea repair, xerophthalmia auxiliary treatment and postoperative protection. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: In one aspect, the present invention provides a method of preparing a silicone hydrogel material comprising the steps of: 1) The preparation method comprises the steps of (1) carrying out photopolymerization curing molding on 2-hydroxyethyl methacrylate (HEMA), 3- (trimethylsiloxy) propyl methacrylate (TRIS), ethylene Glycol Dimethacrylate (EGDMA), a silane coupling agent and a photoinitiator to obtain a silicon hydrogel substrate, or carrying out photopolymerization curing molding on 2-hydroxyethyl methacrylate (HEMA), 3- (trimethylsiloxy) propyl methacrylate (TRIS), ethylene Glycol Dimethacrylate (EGDMA), N-vinyl pyrrolidone (NVP), a silane coupling agent and a photoinitiator to obtain a silicon hydrogel substrate; 2) Performing oxygen plasma treatment on the silicon hydrogel substrate obtained in the step 1); 3) Preparing a hydrophobic layer on the surface of the silicon hydrogel substrate treated in the step 2), wherein the hydrophobic layer is Polydimethylsiloxane (PDMS); 4) Oxygen plasma treatment is carried out on the PDMS layer obtained in the step 3); 5) Immersing the sample subjected to the oxygen plasma treatment in the step 4) in an