Oxygen-permeable silica hydrogel material for contact lenses and preparation method of oxygen-permeable silica hydrogel material

Abstract

The invention relates to the technical field of hydrogel materials, and discloses an oxygen-permeable silicon hydrogel material for contact lenses and a preparation method thereof.The preparation method comprises the steps that ethylene glycol diglycidyl ether and bis (2-chloroethyl) amine hydrochloride are subjected to a ring-opening reaction, and an intermediate product 1, 2-propylene glycol is obtained; carrying out substitution and hydrolysis reaction on the polyalkenyl quaternary ammonium salt and diethyl iminodiacetate to obtain an intermediate product 2, and carrying out quaternization reaction on the intermediate product 2 and chloropropene by utilizing a tertiary amine structure contained in the intermediate product 2 to obtain the polyalkenyl quaternary ammonium salt. And finally, carrying out polymerization reaction on the silicon hydrogel, hydroxyethyl methylacrylate, gamma-(methacryloyloxy) propyltrimethoxysilane and vinyl-terminated dimethyl polysiloxane, putting the obtained product into a contact lens half mold for reaction, and demolding to obtain the oxygen-permeable silicon hydrogel material. The hydrogel material prepared in the invention has good hydrophilic effect and oxygen permeation effect, and can be widely applied to contact lenses.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogel materials, and specifically to an oxygen-permeable silicone hydrogel material for contact lenses and a preparation method thereof. Background Art

[0002] Contact lenses are ophthalmic medical devices worn on the cornea of the eyeball to protect the eyes and correct vision. With the rapid development of the economy and society, people's requirements for the performance of contact lenses are also getting higher and higher. At present, soft contact lenses prepared from hydrogel polymers are more acceptable to the public in the market, and their oxygen permeability is proportional to the water content.

[0003] Among the materials for preparing contact lenses, silicone hydrogels are the most popular because they not only have the softness and comfort of hydrogels but also have the high oxygen permeability of siloxanes. However, hydrophobic siloxane groups tend to accumulate on the material surface, affecting surface wettability. Therefore, it is necessary to perform hydrophilic treatment on the surface of silicone hydrogels to meet the requirements of adapting to the eye environment as contact lenses. However, when the water content is relatively high, the mechanical properties of the material will also be reduced.

[0004] For example, the patent with the authorization announcement number CN 118638279 B discloses a high-oxygen-permeable silicone hydrogel material, its preparation method and application. A silicone hydrogel prepared by this invention has good antibacterial properties and biocompatibility, and has certain potential in contact lenses. Summary of the Invention

[0005] (1) Technical Problems to be Solved

[0006] Aiming at the deficiencies of the prior art, the present invention provides an oxygen-permeable silicone hydrogel material for contact lenses and a preparation method thereof. The prepared silicone hydrogel material has good hydrophilic effect and oxygen permeability.

[0007] (2) Technical Solutions

[0008] An oxygen-permeable silicone hydrogel material for contact lenses, the oxygen-permeable silicone hydrogel material is composed of the following components in parts by weight: 10-20 parts of N-vinylpyrrolidone, 100 parts of 2-hydroxyethyl methacrylate, 10-25 parts of γ-(methacryloyloxy)propyltrimethoxysilane, 10-20 parts of vinyl-terminated dimethylpolysiloxane, 10-25 parts of polyene-based quaternary ammonium salt;

[0009] The preparation method of the oxygen-permeable silicone hydrogel material is as follows:

[0010] Add the initiator and cross-linking agent to N-vinyl pyrrolidone, stir to dissolve, then add hydroxyethyl methacrylate, γ-(methacryloyloxy)propyltrimethoxysilane, vinyl-terminated dimethylpolysiloxane and polyenyl quaternary ammonium salt, stir to mix evenly, add to the contact lens half mold, place in a constant temperature water bath, control the temperature at 70-80°C, react for 15-20 hours, and after the reaction is completed, demold to obtain an oxygen-permeable silicone hydrogel material.

[0011] Preferably, the initiator is azobisisobutyronitrile, and its mass dosage is 0.1-0.4% of the total mass of N-vinyl pyrrolidone, hydroxyethyl methacrylate, γ-(methacryloyloxy)propyltrimethoxysilane, vinyl-terminated dimethylpolysiloxane, and polyenyl quaternary ammonium salt.

[0012] Preferably, the crosslinking agent is N,N'-methylenebisacrylamide, and its mass dosage is 0.5-2% of the total mass of N-vinyl pyrrolidone, hydroxyethyl methacrylate, γ-(methacryloyloxy)propyltrimethoxysilane, vinyl-terminated dimethylpolysiloxane, and polyenyl quaternary ammonium salt.

[0013] Preferably, the preparation method of the polyalkenyl quaternary ammonium salt is:

[0014] (1) Add ethylene glycol diglycidyl ether and bis(2-chloroethyl)amine hydrochloride into a flask, stir and mix evenly, control the temperature to 70-85° C., react for 5-8 hours, and after the reaction is completed, wash with ethanol and dry to obtain an intermediate product 1;

[0015] (2) The intermediate product 1 and triethylamine are added to a tetrahydrofuran solvent, and under a nitrogen atmosphere, diethyl iminodiacetate is added thereto at -10 to 0°C, the mixture is stirred and mixed evenly, the temperature is raised to room temperature, the reaction is carried out for 20-28 hours, the mixture is filtered, the mixture is rotary evaporated, the mixture is dissolved in a dichloromethane solvent, the mixture is extracted and washed with deionized water, the organic phase is dehydrated with anhydrous calcium chloride, filtered, hydrochloric acid is added thereto, the mixture is stirred at room temperature for 20-25 hours, the mixture is distilled under reduced pressure until a large amount of precipitates are precipitated, the mixture is filtered, and the mixture is dried to obtain an intermediate product 2;

[0016] (3) Under nitrogen protection, the intermediate product 2 is added to an ethanol solvent, and then allyl chloride is added thereto, the temperature is controlled at 40-55° C., and the reaction is carried out for 24-30 hours. After the reaction is completed, the reaction is performed by rotary evaporation, washed with acetone, and dried to obtain a polyenyl quaternary ammonium salt.

[0017] More preferably, in (1), the molar ratio of ethylene glycol diglycidyl ether to bis(2-chloroethyl)amine hydrochloride is 1:2-2.5.

[0018] Further preferably, in (2), the molar ratio of intermediate 1, triethylamine, and diethyl iminodiacetate is 1:4 - 4.5:4.2 - 4.5.

[0019] Further preferably, in (3), the molar ratio of intermediate 2 and allyl chloride is 1:6.5 - 8.

[0020] (III) Beneficial technical effects:

[0021] In the present invention, ethylene glycol diglycidyl ether and bis(2-chloroethyl)amine hydrochloride undergo a ring-opening reaction to obtain intermediate 1. Intermediate 1 is subjected to a substitution and hydrolysis reaction with diethyl iminodiacetate to obtain intermediate 2. Utilizing the tertiary amine structure contained therein, a quaternization reaction is carried out with allyl chloride to obtain a polyenyl quaternary ammonium salt. Finally, it is subjected to a polymerization reaction with 2-hydroxyethyl methacrylate, γ-(methacryloyloxy)propyltrimethoxysilane, and vinyl-terminated dimethyl polysiloxane, and then reacted in a contact lens half mold, demolded, to obtain an oxygen-permeable silicone hydrogel material.

[0022] The oxygen-permeable silicone hydrogel material prepared in the present invention contains a relatively large number of hydrophilic groups such as hydroxyl groups and carboxyl groups, which can form hydrogen bonds with water molecules, increasing the water content of the hydrogel material. Moreover, in the polyenyl quaternary ammonium salt prepared in the present invention, due to the presence of a relatively large number of alkenyl groups, when it is polymerized with other raw materials, a relatively large number of crosslinking sites can be generated, making the spatial structure between the polymer networks larger, and further increasing the water content of the hydrogel material. The contained trimethoxysilyl group, due to its relatively long Si-O bond, occupies a relatively large three-dimensional space in the polymer molecule, can effectively reduce the intermolecular force of the polymer, increasing the oxygen solubility coefficient, which is beneficial to the increase of the oxygen permeability of the hydrogel material. In addition, the hydrogel material prepared in the present invention contains a relatively large number of quaternary ammonium salt antibacterial structures, which can kill eye microorganisms when contact lenses are used for a long time, achieving a good antibacterial effect. Description of the Drawings

[0023] Figure 1 is the reaction route of the polyenyl quaternary ammonium salt. Detailed Embodiments

[0024] To better illustrate the present invention and facilitate understanding of its technical solutions, the present invention is further described in detail below. However, the following embodiments are only simple examples of the present invention and do not represent or limit the scope of the claimed protection of the present invention. The scope of protection of the present invention is subject to the claims. In the detailed embodiments, vinyl-terminated dimethyl polysiloxane, CAS No. 68083-19-2, is purchased from Bashi Fu (Shanghai) Biomedical Technology Co., Ltd.

[0025] Example 1

[0026] (1) 0.4 mol of ethylene glycol diglycidyl ether and 0.8 mol of bis(2-chloroethyl)amine hydrochloride were added to a flask, stirred and mixed evenly. The reaction temperature was controlled at 85 °C and the reaction was carried out for 6 h. After the reaction, it was washed with ethanol and dried to obtain intermediate 1.

[0027] (2) 0.1 mol of intermediate 1 and 0.45 mol of triethylamine were added to 400 mL of tetrahydrofuran solvent. Under a nitrogen atmosphere, at -10 °C, 0.45 mol of diethyl iminodiacetate was added thereto, stirred and mixed evenly, then heated to room temperature and reacted for 24 h. It was filtered by suction and rotary evaporated, then dissolved in 200 mL of dichloromethane solvent, extracted and washed with deionized water. The organic phase was dehydrated using anhydrous calcium chloride, filtered, 300 mL of hydrochloric acid with a mass fraction of 30% was added thereto, and stirred at room temperature for 25 h. It was distilled under reduced pressure until a large amount of precipitate was separated out, filtered and dried to obtain intermediate 2.

[0028] (3) Under nitrogen protection, 0.1 mol of intermediate 2 was added to 200 mL of ethanol solvent, and then 0.65 mol of allyl chloride was added thereto. The temperature was controlled at 55 °C and the reaction was carried out for 26 h. After the reaction, it was rotary evaporated, washed with acetone and dried to obtain a polyene quaternary ammonium salt.

[0029] (4) 0.13 g of azobisisobutyronitrile initiator and 1 g of N,N'-methylenebisacrylamide crosslinking agent were added to 5 g of N-vinylpyrrolidone, stirred and dissolved. Then 50 g of 2-hydroxyethyl methacrylate, 5 g of γ-(methacryloyloxy)propyltrimethoxysilane, 5 g of vinyl-terminated dimethyl polysiloxane and 5 g of polyene quaternary ammonium salt were added thereto, stirred and mixed evenly. Then it was added to a contact lens half mold, placed in a constant temperature water bath, and the temperature was controlled at 70 °C and the reaction was carried out for 16 h. After the reaction, it was demolded to obtain an oxygen-permeable silicone hydrogel material.

[0030] Example 2

[0031] (1) 0.4 mol of ethylene glycol diglycidyl ether and 1 mol of bis(2-chloroethyl)amine hydrochloride were added to a flask, stirred and mixed evenly. The temperature was controlled at 75 °C and the reaction was carried out for 8 h. After the reaction, it was washed with ethanol and dried to obtain intermediate 1.

[0032] (2) Add 0.1 mol of intermediate 1 and 0.4 mol of triethylamine to 400 mL of tetrahydrofuran solvent. Under a nitrogen atmosphere, at 0 °C, add 0.4 mol of diethyl iminodiacetate to it, stir and mix evenly, warm up to room temperature, react for 20 h, filter by suction, rotary evaporate, dissolve it in 200 mL of dichloromethane solvent, extract and wash with deionized water, dehydrate the organic phase with anhydrous calcium chloride, filter, add 300 mL of hydrochloric acid with a mass fraction of 30% to it, stir and react at room temperature for 24 h, distill under reduced pressure until a large amount of precipitate is separated out, filter, and dry to obtain intermediate 2.

[0033] (3) Under nitrogen protection, add 0.1 mol of intermediate 2 to 200 mL of ethanol solvent, then add 0.65 mol of allyl chloride to it, control the temperature at 55 °C, react for 26 h. After the reaction is completed, rotary evaporate, wash with acetone, and dry to obtain a polyenyl quaternary ammonium salt.

[0034] (4) Add 0.07 g of azobisisobutyronitrile initiator and 1.4 g of N,N'-methylenebisacrylamide crosslinking agent to 6 g of N-vinylpyrrolidone, stir to dissolve, then add 50 g of 2-hydroxyethyl methacrylate, 7.5 g of γ-(methacryloyloxy)propyltrimethoxysilane, 7.5 g of vinyl-terminated dimethyl polysiloxane, and 7.5 g of polyenyl quaternary ammonium salt, stir and mix evenly, then add it to a contact lens half mold, place it in a constant temperature water bath, control the temperature at 80 °C, react for 15 h. After the reaction is completed, demold to obtain an oxygen-permeable silicone hydrogel material.

[0035] Example 3

[0036] (1) Add 0.4 mol of ethylene glycol diglycidyl ether and 0.9 mol of bis(2-chloroethyl)amine hydrochloride to a flask, stir and mix evenly, control the temperature at 70 °C, react for 5 h. After the reaction is completed, wash with ethanol and dry to obtain intermediate 1.

[0037] (2) Add 0.1 mol of intermediate 1 and 0.45 mol of triethylamine to 400 mL of tetrahydrofuran solvent. Under a nitrogen atmosphere, at -5 °C, add 0.42 mol of diethyl iminodiacetate to it, stir and mix evenly, warm up to room temperature, react for 28 h, filter by suction, rotary evaporate, dissolve it in 200 mL of dichloromethane solvent, extract and wash with deionized water, dehydrate the organic phase with anhydrous calcium chloride, filter, add 300 mL of hydrochloric acid with a mass fraction of 30% to it, stir and react at room temperature for 20 h, distill under reduced pressure until a large amount of precipitate is separated out, filter, and dry to obtain intermediate 2.

[0038] (3) Under nitrogen protection, 0.1 mol of the intermediate product 2 was added to 200 mL of ethanol solvent, and then 0.8 mol of allyl chloride was added thereto. The temperature was controlled at 40°C and the reaction was carried out for 30 hours. After the reaction was completed, the mixture was rotary evaporated, washed with acetone, and dried to obtain a polyene quaternary ammonium salt.

[0039] (4) Add 0.3 g of azobisisobutyronitrile initiator and 0.8 g of N,N'-methylenebisacrylamide crosslinker to 8 g of N-vinylpyrrolidone and stir to dissolve. Then add 50 g of hydroxyethyl methacrylate, 10 g of γ-(methacryloyloxy)propyltrimethoxysilane, 10 g of vinyl-terminated dimethylpolysiloxane and 10 g of polyolefin quaternary ammonium salt and stir to mix evenly. Then add the mixture to the contact lens half mold and place it in a constant temperature water bath at 75°C for 20 h. After the reaction is completed, demold and obtain an oxygen-permeable silicone hydrogel material.

[0040] Example 4

[0041] (1) 0.4 mol of ethylene glycol diglycidyl ether and 0.8 mol of bis(2-chloroethyl)amine hydrochloride were added to a flask, stirred and mixed evenly, and the temperature was controlled at 85° C. The reaction was carried out for 6 h. After the reaction was completed, the product was washed with ethanol and dried to obtain an intermediate product 1.

[0042] (2) 0.1 mol of intermediate 1 and 0.4 mol of triethylamine were added to 400 mL of tetrahydrofuran solvent. Under a nitrogen atmosphere, 0.42 mol of diethyl iminodiacetate was added thereto at 0°C, the mixture was stirred and mixed evenly, the temperature was raised to room temperature, the reaction was carried out for 26 h, suction filtered, rotary evaporated, dissolved in 200 mL of dichloromethane solvent, extracted and washed with deionized water, the organic phase was dehydrated with anhydrous calcium chloride, filtered, 300 mL of 30% hydrochloric acid was added thereto, the reaction was stirred at room temperature for 24 h, and the mixture was distilled under reduced pressure until a large amount of precipitate was precipitated, filtered, and dried to obtain intermediate 2.

[0043] (3) Under nitrogen protection, 0.1 mol of the intermediate product 2 was added to 200 mL of ethanol solvent, and then 0.65 mol of allyl chloride was added thereto. The temperature was controlled at 40°C and the reaction was carried out for 24 hours. After the reaction was completed, the mixture was rotary evaporated, washed with acetone, and dried to obtain a polyene quaternary ammonium salt.

[0044] (4) 0.25 g of azobisisobutyronitrile initiator and 1.7 g of N,N'-methylenebisacrylamide crosslinking agent were added to 10 g of N-vinylpyrrolidone, stirred and dissolved. Then, 50 g of 2-hydroxyethyl methacrylate, 12.5 g of γ-(methacryloyloxy)propyltrimethoxysilane, and 12.5 g of polyalkenyl quaternary ammonium salt were added thereto, stirred and mixed evenly. Then, the mixture was added to a contact lens half mold, placed in a constant temperature water bath, the temperature was controlled at 75 °C, and the reaction was carried out for 18 h. After the reaction was completed, demolding was carried out to obtain an oxygen-permeable silicone hydrogel material.

[0045] Comparative Example 1

[0046] The difference between this comparative example and Example 1 is that: in step (4), γ-(methacryloyloxy)propyltrimethoxysilane and vinyl-terminated dimethylpolysiloxane are not contained.

[0047] Comparative Example 2

[0048] The difference between this comparative example and Example 1 is that: in step (4), polyalkenyl quaternary ammonium salt is not contained.

[0049] An oxygen permeability tester was used to test the oxygen permeability. The hydrogel was immersed in physiological saline for 48 h, and according to the test method of GB / T 11417.3-2012, the oxygen permeability performance was tested at 37 °C and a relative humidity of 90%, and the oxygen permeability coefficient was tested.

[0050] Table 1 Oxygen Permeability Coefficient Test

[0051] <![CDATA[Oxygen permeability coefficient (10 -11 cm 2 ·mLO 2 / s·mL·mmHg)]]> Example 1 100.8 Example 2 106.0 Example 3 109.2 Example 4 108.4 Comparative Example 1 69.4 Comparative Example 2 83.2

[0052] As can be seen from the table, the hydrogel material prepared by the present invention has good oxygen permeability performance.

[0053] The oxygen-permeable silicone hydrogel was added to a 0.9% sodium chloride aqueous solution, immersed at room temperature for 24 h, fully swollen, the water on the surface of the material was blotted dry with filter paper, and the wet weight W of the lens was weighed with an electronic balance 1 , and then the material was placed at 70 °C and dried for 5 h, and the dry weight W 2 was measured. The water content (%) = (W 1 - W 2 / W 1 ) × 100%.

[0054] Table 2 Water Content Test

[0055] Water content (%) Example 1 38.9 Example 2 43.8 Example 3 45.2 Example 4 47.5 Comparative Example 1 49.4 Comparative Example 2 32.0

[0056] As can be seen from the table, the water content of Comparative Example 1 containing polyene quaternary ammonium salt is higher than that of Comparative Example 2 without polyene quaternary ammonium salt. This is because Comparative Example 1 contains more hydrophilic groups, which can form hydrogen bonds with water molecules. Moreover, Comparative Example 1 contains more alkenyl groups, which can form a larger spatial network structure, increasing the water content. The water content of Comparative Example 1 is higher than that of Example 1 because γ-(methacryloyloxy)propyltrimethoxysilane and vinyl-terminated dimethylpolysiloxane are hydrophobic monomers, which will weaken the hydrogen bond interaction of the material with water molecules and reduce the water content. As can be seen from Examples 1-5, as the dosage of polyene quaternary ammonium salt increases, the water content increases.

[0057] For the material that remains moist, bend it back and forth at 90° repeatedly with your fingers. When bending, it feels soft and elastic, and the material does not deform. Reach the specified number of 500 times and check if it deforms.

[0058] Table 3 Deformation Resistance Test

[0059]

[0060]

[0061] As can be seen from the table, the silicone hydrogel material prepared by the present invention has good fatigue strength.

[0062] The present invention uses the above examples to illustrate the detailed products and methods of the present invention, but the present invention is not limited to the above detailed products and methods, that is, it does not mean that the present invention must rely on the above detailed products and methods to be implemented. Those skilled in the art should understand that any improvement to the present invention, equivalent replacement of the products of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An oxygen-permeable silicone hydrogel material for contact lenses, characterized in that: The oxygen-permeable silicone hydrogel material is composed of the following components in parts by weight: 10-20 parts by weight of N-vinyl pyrrolidone, 100 parts of hydroxyethyl methacrylate, 10-25 parts of γ-(methacryloyloxy)propyltrimethoxysilane, 10-20 parts of vinyl-terminated dimethyl polysiloxane, and 10-25 parts of polyenyl quaternary ammonium salt; The preparation method of the oxygen-permeable silicone hydrogel material is: Add the initiator and cross-linking agent to N-vinyl pyrrolidone, stir to dissolve, then add hydroxyethyl methacrylate, γ-(methacryloyloxy)propyltrimethoxysilane, vinyl-terminated dimethylpolysiloxane and polyenyl quaternary ammonium salt, stir to mix evenly, add to the contact lens half mold, place in a constant temperature water bath, control the temperature at 70-80°C, react for 15-20 hours, and after the reaction is completed, demold to obtain an oxygen-permeable silicone hydrogel material.

2. The oxygen-permeable silicone hydrogel material for contact lenses according to claim 1, characterized in that: The initiator is azobisisobutyronitrile, and its mass dosage is 0.1-0.4% of the total mass of N-vinyl pyrrolidone, hydroxyethyl methacrylate, γ-(methacryloyloxy)propyltrimethoxysilane, vinyl-terminated dimethylpolysiloxane and polyenyl quaternary ammonium salt.

3. The oxygen-permeable silicone hydrogel material for contact lenses according to claim 1, characterized in that: The crosslinking agent is N,N'-methylenebisacrylamide, and its mass dosage is 0.5-2% of the total mass of N-vinyl pyrrolidone, hydroxyethyl methacrylate, γ-(methacryloyloxy)propyltrimethoxysilane, vinyl-terminated dimethylpolysiloxane and polyenyl quaternary ammonium salt.

4. The oxygen-permeable silicone hydrogel material for contact lenses according to claim 1, characterized in that: The preparation method of the polyalkenyl quaternary ammonium salt is: (1) Add ethylene glycol diglycidyl ether and bis(2-chloroethyl)amine hydrochloride into a flask, stir and mix evenly, control the temperature to 70-85° C., react for 5-8 hours, and after the reaction is completed, wash with ethanol and dry to obtain an intermediate product 1; (2) The intermediate product 1 and triethylamine are added to a tetrahydrofuran solvent, and under a nitrogen atmosphere, diethyl iminodiacetate is added thereto at -10 to 0°C, the mixture is stirred and mixed evenly, the temperature is raised to room temperature, the reaction is carried out for 20-28 hours, the mixture is filtered, the mixture is rotary evaporated, the mixture is dissolved in a dichloromethane solvent, the mixture is extracted and washed with deionized water, the organic phase is dehydrated with anhydrous calcium chloride, filtered, hydrochloric acid is added thereto, the mixture is stirred at room temperature for 20-25 hours, the mixture is distilled under reduced pressure until a precipitate is precipitated, the mixture is filtered, and the mixture is dried to obtain an intermediate product 2; (3) Under nitrogen protection, the intermediate product 2 is added to an ethanol solvent, and then allyl chloride is added thereto to carry out a reaction. After the reaction is completed, the mixture is rotary evaporated, washed with acetone, and dried to obtain a polyenyl quaternary ammonium salt.

5. The oxygen-permeable silicone hydrogel material for contact lenses according to claim 4, characterized in that: In the above (1), the molar ratio of ethylene glycol diglycidyl ether to bis(2-chloroethyl)amine hydrochloride is 1:2-2.

5.

6. The oxygen-permeable silicone hydrogel material for contact lenses according to claim 4, characterized in that: In the above (2), the molar ratio of the intermediate product 1, triethylamine and diethyl iminodiacetate is 1:4-4.5:4.2-4.

5.

7. The oxygen-permeable silicone hydrogel material for contact lenses according to claim 4, characterized in that: In the above (3), the molar ratio of the intermediate product 2 to allyl chloride is 1:6.5-8.

8. The oxygen-permeable silicone hydrogel material for contact lenses according to claim 4, characterized in that: In the step (3), the reaction temperature is 40-55°C and the reaction time is 24-30h.

Images