A high oxygen permeable silicon hydrogel contact lens and a method for making the same

Abstract

The application discloses a high-oxygen-permeable silicon hydrogel contact lens, which comprises the following raw material components in percentage by mass: macromolecular siloxane I 30-40%, macromolecular siloxane II 5-10%, small-molecule siloxane 10-20%, hydrophilic monomer 20-30%, humectant 2-5%, crosslinking agent 0.5-1.5%, initiator 0.5-1% and functional monomer 2-5%. The macromolecular siloxane I used in the silicon hydrogel contact lens has a narrow molecular weight distribution and good reaction repeatability, and a quaternary ammonium salt functional group is introduced into the macromolecular siloxane I, which is beneficial to the uniformity of the macromolecular siloxane in a PP mold, so that the lens obtains a better hydrophilic surface; meanwhile, the preparation process equipment of the macromolecular siloxane I is simple, raw materials are cheap and easy to obtain, and operation is convenient; and the obtained lens has a high oxygen permeability coefficient, and a lens with good surface hydrophilicity and good wetness can be obtained without surface treatment.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of contact lens preparation, in particular to a high oxygen permeable silicone hydrogel contact lens and a preparation method thereof. BACKGROUND

[0002] Silicone hydrogel contact lenses have been used more than traditional hydrogel contact lenses, because the high oxygen permeability of silicone hydrogel makes the wearer have a longer comfortable wearing time. The introduction of fluorine in silicone hydrogel contact lenses can further improve the oxygen permeability of the contact lenses, and the lenses can also have better processing performance and better improve the disadvantage of protein adsorption resistance of silicone hydrogel lenses. However, polydimethylsiloxane makes the lens surface not hydrophilic, and low wettability can cause discomfort to the wearer, which requires the introduction of hydrophilic groups from the molecular structure.

[0003] Patent CN 101163991A discloses a preparation method of macromolecular organosilicon containing allyl polyethylene glycol ether similar to fluorosiloxane, but a modified PP mold (increasing the polarity of the mold) is still needed to prepare the silicone hydrogel lens, because the small surface polarity of the conventional PP mold causes the enrichment of the silicon component in the polymerization liquid to the PP mold surface, thereby resulting in insufficient lens surface wettability. CN101589091A discloses the preparation of macromolecular siloxane containing quaternary ammonium salt, but the preparation method still needs to be optimized. More methods to improve the wettability of the lens surface are: lens surface treatment (such as: CN 104837612A; CN 107532083A), addition of PVP and other moisturizers. SUMMARY

[0004] The present application aims at the deficiencies in the prior art, and provides a high oxygen permeable silicone hydrogel contact lens and a preparation method thereof. By optimizing the reaction conditions of macromolecular siloxane I and removing low molecular weight polymers through more optimal post-treatment conditions, the molecular weight distribution coefficient of the macromolecular siloxane I is ensured to be less than 1.8. At the same time, the introduction of quaternary ammonium salt functional groups in the molecule is beneficial to the uniformity of the macromolecular siloxane in the PP mold, so that the lens has a better hydrophilic surface, greatly improves the initial wearing feeling of the prepared lens, and the bacteriostatic property of the quaternary ammonium salt better protects the eye health of the wearer. In addition, the lens has high oxygen permeability, excellent high wettability surface, protein adsorption resistance, and does not need surface treatment.

[0005] In order to solve the above technical problems, the first aspect of the present application provides a high oxygen permeable silicone hydrogel contact lens, which comprises the following raw material components: macromolecular siloxane I, macromolecular siloxane II, small molecule siloxane, hydrophilic monomer, moisturizer, crosslinking agent, initiator and functional monomer.

[0006] The molecular weight of the macromolecular siloxane I is 10000-15000, the molecular weight distribution coefficient is less than 1.8, and the structural formula is:

[0007]

[0008] wherein a:b:c=(0.1-0.2):0.1:(0.7-0.8); b / (a+c)=1 / 9, d is 7-8 or 23-30;

[0009] The structural formula of the macromolecular siloxane II is:

[0010]

[0011] wherein R1 is H or CH3, R2 is one of C3-C6 alkyl, and n is a natural number between 9-24;

[0012] The structural formula of the moisturizing agent is:

[0013]

[0014] wherein R is one of H, OH, and polyhydroxy compound; X and Y are independently one of O, S, and N, and the anion can also be bromine, iodine, or other organic acid group.

[0015] Further, the preparation method of the macromolecular siloxane I includes the following steps:

[0016] S1, 1,3-bis(3-chloropropyl)tetramethyldisilane, D3F, D3, D3H, phosphonium alcohol salt are added to an organic solvent, triflic acid is added under low temperature conditions, stirring for 2h, then slowly warming up and reacting for 22-24h, and then post-processing to obtain intermediate I;

[0017] S2, the intermediate I and allyl polyethylene glycol ether are subjected to addition reaction in an organic solvent, and post-processing to obtain intermediate II;

[0018] wherein Karstedt catalyst or speier catalyst is added before the addition reaction, and the addition reaction temperature is 25-50℃;

[0019] S3, the intermediate II and N-(3-dimethylaminopropyl) methacrylamide are subjected to heating reflux reaction in an organic solvent, post-processing, and freeze-drying to obtain the macromolecular siloxane I;

[0020] The structural formula of the D3F, D3, D3H, phosphonium alcohol salt, intermediate I, and intermediate II is respectively:

[0021]

[0022]

[0023] Wherein, a:b:c=(0.1-0.2):0.1:(0.7-0.8); b / (a+c)=1 / 9, d is 7 or 8.

[0024] In S1, three raw materials D3F, D3, D3H for ring-opening reaction are all six-membered rings containing three silicon, so as to obtain close ring-opening reaction rate.

[0025] Further, in S1, the organic solvent is one or a mixture of two of toluene, dichloromethane, chloroform, tetrahydrofuran.

[0026] Further, in S2, the organic solvent is one or a mixture of two of isopropyl alcohol, methanol, ethanol, acetonitrile, toluene.

[0027] Further, in S3, the organic solvent is one or a mixture of two of isopropyl alcohol, methanol, ethanol, acetonitrile.

[0028] Further, in S1, the temperature for adding trifluoromethanesulfonic acid is 0°C, and the reaction temperature is 10°C, and a lower reaction temperature is to better control the molecular weight distribution, and the ring-opening of D3 can be well performed at low temperature;

[0029] The organic solvent accounts for 80% of the total reaction volume, and a low reaction concentration can better inhibit the generation of super-molecular polymerization products;

[0030] The post-treatment specifically includes: using a mixed solvent of methanol and nitromethane with a volume ratio of 5:1 to extract the oligomers and a small amount of unopened raw materials and other cyclic body by-products generated in the reaction.

[0031] Further, in S2, the post-treatment specifically includes: dissolving the intermediate II crude product in a mixed solvent of methyl tert-butyl ether and ethyl acetate with a volume ratio of 1:5, and then extracting the remaining raw material allyl polyethylene glycol ether with purified water.

[0032] Further, in S3, the post-treatment specifically includes: dissolving the macromolecular siloxane I crude product in purified water, and then extracting the remaining raw material N-(3-dimethylaminopropyl) methacrylamide with a mixed solvent of dichloromethane and ethyl acetate with a volume ratio of 1:1.

[0033] Further, in S3, the water content in the product after freeze-drying is less than 0.15wt%.

[0034] Further, the mass percentage includes the following components: macromolecular siloxane I 30-40%, macromolecular siloxane II 5-10%, small molecular siloxane 10-20%, hydrophilic monomer 20-30%, humectant 2-5%, crosslinking agent 0.5-1.5%, initiator 0.5%-1%, functional monomer 2-5%.

[0035] Further, the small molecule siloxane is methacryloxypropyl tris(trimethylsiloxy)silane and / or (3-methacryloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methyl;

[0036] Further, the hydrophilic monomer is one or more of N-vinylpyrrolidone, N,N-dimethylacrylamide, N-methyl-N-vinylacetamide, N-vinylacetamide;

[0037] Further, the crosslinking agent is ethylene glycol dimethacrylate and / or tetraethylene glycol dimethacrylate;

[0038] Further, the initiator is azobisisobutyronitrile (AIBN);

[0039] Further, the functional monomer comprises one or more of ultraviolet absorber, molecular weight regulator, lens morphology improver, demolding promoter, reactive dye.

[0040] Further, the ultraviolet absorber is one or more of UV416, UV090, UV725; the molecular weight regulator is allyl hydroxyethyl ether; the lens morphology improver is one or more of 2-hydroxyethyl methacrylate, glycidyl methacrylate, isobornyl methacrylate, methyl methacrylate; the demolding promoter is sodium salt of bis(2-ethylhexyl)sulfosuccinate; the reactive dye is RB246 and / or RB247.

[0041] The second aspect of the present application provides a preparation method of the high-oxygen-permeable silicone hydrogel contact lens of the first aspect, characterized in that: raw material components are mixed and dissolved in an organic solvent to obtain a polymerization solution; the polymerization solution is placed in a mold and subjected to heat treatment under a protective atmosphere of nitrogen; after natural cooling to room temperature, the lens is demolded and extracted to obtain the high-oxygen-permeable silicone hydrogel contact lens.

[0042] Further, the heat treatment is specifically: incubation at 60°C for 60-100 min, followed by uniform heating to 110-120°C for 4 h, and incubation for 1 h.

[0043] Further, the demolding and extraction are specifically: placing the mold after heat treatment in an aqueous ethanol solution with a concentration of 20wt%-80wt% for hydration, so as to demold the lens and extract a small amount of residual monomers and oligomers in the lens.

[0044] The present application has the following beneficial effects:

[0045] The macromolecular siloxane I used in the present application has narrow molecular weight distribution, good reaction repeatability, and the introduction of quaternary ammonium salt functional groups is beneficial to the uniformity of the macromolecular siloxane in the PP mold, so that the lens obtains a better hydrophilic surface; at the same time, the preparation process of the macromolecular siloxane I is simple, the raw materials are cheap and easy to obtain, and the operation is convenient.

[0046] The lens has high oxygen permeability coefficient and excellent protein adsorption resistance, and at the same time, no solvent needs to be introduced into the polymerization liquid, and the lens with good surface wetness can be obtained without surface treatment. BRIEF DESCRIPTION OF DRAWINGS

[0047] In order to more clearly illustrate the technical solutions of the present application, the drawings needed in the embodiments will be briefly introduced below, and obviously, the drawings in the following description are only embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to these drawings without creative labor.

[0048] Figure 1 It is the macromolecular siloxane I nuclear magnetic spectrum prepared by example 1 of the present application. DETAILED DESCRIPTION

[0049] The technical solutions of the present application will be described below in combination with specific embodiments of the present application, and obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0050] Example 1

[0051] This embodiment relates to a preparation method of macromolecular siloxane I, comprising the following steps:

[0052] S1, 5000 mL of chloroform (water content less than 100 ppm) was added to a 10 L jacketed reactor, then 40 g of 1,3-bis(3-chloropropyl)tetramethyldisilane, 550 g of D3, 116 g of D3F, 55 g of D3H, 1.5 g of phosphonium salt was added. Start stirring, under nitrogen protection, the reaction liquid was reduced to 0°C, 0.3 g of triflic acid was added with a syringe, and stirring was maintained at 0°C for 2 hours. Open the high and low temperature cycle device, maintain the liquid temperature at 10°C, and continue to incubate for 22 hours. Add 2 g of powdered sodium bicarbonate, continue to stir for 3 h, neutralize the triflic acid, and quench the reaction. Filter, concentrate the filtrate to remove the solvent, and obtain 0.77 kg of crude product. Add 230 ml of mixed solvent (methanol: nitromethane = 5:1) for washing, and separate the layers after standing. The lower layer is a slightly milky white liquid, which is the product phase, and the upper layer is a clear liquid (containing small molecule oligomers), which is repeated three times. The lower target phase is removed from the light component to obtain the product intermediate I 500 g, which is a colorless clear liquid. The designed molecular weight is about 5300, 1 HNMR shows that the actual molecular weight is 6300. GPC detection was performed on intermediate I, with the following conditions: (1) Equipment: LC-20ADXR pump; RID-20A differential refractive detector; LabSulutions chromatography workstation; CTO-20A chromatographic column thermostat; SIL-20AXR automatic sampler. (2) Method: Standard: PEG / PEO (molecular weight 3140-250000); mobile phase: acetonitrile: water = 75:25; chromatographic column: SB-804HQ 300*8.0mm 10um; flow rate: 0.8 ml / min.; column temperature: 40°C; detector temperature: 40°C; time: 20 min. GPC detection results show that the distribution coefficient is 1.4.

[0053] S2, 1.2 L of isopropyl alcohol was added to a 5 L reaction bottle, then 500 g of intermediate I was added, followed by 338 g of allyl polyethylene glycol ether (molecular weight 400-450). Start stirring, maintain the reaction liquid at 25°C under nitrogen protection, add 0.8 g of Karstedt catalyst (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution, platinum 2%) with a syringe, and maintain 25 degree stirring for 12 hours. During the reaction, the system changes from a slightly milky white turbid liquid to a light yellow clear transparent liquid. After removing the solvent under reduced pressure, a viscous nearly solid liquid is obtained, 1600 ml of mixed solvent methyl tert-butyl ether: ethyl acetate = 1:5 is added, stirred and dissolved, then 300 ml of purified water is added for washing, and the layers are separated after standing. The upper layer is a slightly yellow transparent liquid, which is the target phase, and the lower layer is the water phase. The organic phase is washed with water for 3 times to remove excess raw material allyl polyethylene glycol ether and other impurities. The organic phase is concentrated to remove the solvent to obtain the target product intermediate II, a slightly yellow transparent liquid 780 g, 1HNMR shows the molecular weight is about 9300.

[0054] S3, 1.0 L of ethanol was added to a 5 L reaction flask, then 780 g of intermediate II and 31 g of N-(3-dimethylaminopropyl) methacrylamide were added. The reaction was heated to 80°C for 12 h, 50 g of activated carbon was added (for decolorization), and after heating for another half hour, the mixture was filtered while hot. After the ethanol was removed from the filtrate by concentration, 2 L of purified water was added to the residue, which was stirred and dissolved, then washed with 160 ml of mixed solvent (dichloromethane: ethyl acetate = 1:1) three times until the excess N-(3-dimethylaminopropyl) methacrylamide raw material was completely washed out. The water phase containing the product was filtered again through a G6 sand core funnel, and the product was obtained by freeze-drying, which was a yellowish viscous liquid product 675 g. The nuclear magnetic resonance (solvent: deuterated chloroform) of the product is shown in Figure 1 The molecular weight is about 10000.

[0055] Example 2

[0056] This example relates to a method for preparing a macromolecular siloxane I, comprising the following steps:

[0057] S1, 13000 mL of toluene (water content less than 100 ppm) was added to a 20 L jacketed reaction kettle, then 60 g of 1,3-bis(3-chloropropyl)tetramethyldisilane, 1100 g of D3, 420 g of D3F, 118 g of D3H, and 2.1 g of phosphonium alcohol salt were added. The stirring was started, and the reaction solution was cooled to 0°C under nitrogen protection. 0.9 g of trifluoromethanesulfonic acid was added with a syringe, and the stirring was continued at 0°C for 2 hours. The high-low temperature circulation device was started, and the liquid temperature was maintained at 10°C. The reaction was continued for 22 hours. 4 g of powdered sodium bicarbonate was added, and the stirring was continued for 3 h to neutralize the trifluoromethanesulfonic acid and quench the reaction. The mixture was filtered, and the filtrate was concentrated to remove the solvent to obtain 1.69 kg of crude product. The crude product was washed with 500 ml of mixed solvent (methanol: nitromethane = 5:1), and the mixture was allowed to stand to separate into two layers. The lower layer was a slightly milky liquid, which was the product phase, and the upper layer was a clear liquid (containing small molecule oligomers), which was washed three times. The target phase in the lower layer was subjected to light component removal to obtain the product intermediate I 1080 g, which was a colorless clear liquid. The designed molecular weight is about 8200, 1 HNMR shows that the actual molecular weight is 9800. GPC detection (conditions same as in Example 1) shows that the molecular weight distribution coefficient is 1.38.

[0058] S2, 3.0L acetonitrile was added into a 5L reaction flask, then intermediate I 1080g, allyl polyethylene glycol ether (molecular weight 1000) 670g were added in sequence, heated. The stirring was started, after the allyl polyethylene glycol ether was dissolved, 2.5g speier catalyst (chloroplatinic acid isopropanol solution, 1g chloroplatinic acid was dissolved in 50ml isopropanol) was added by syringe under nitrogen protection, the reaction was kept at 50°C for 16 hours. During the reaction, the system changed from milky white turbid liquid to light yellow-brown clear transparent liquid. After the solvent was removed by concentration under reduced pressure, a viscous liquid was obtained, which was nearly solid. 6000ml mixed solvent methyl tert-butyl ether: ethyl acetate = 1:5 was added, after stirring and dissolving, 500ml purified water was added for washing, and the upper layer was the target phase, which was a light yellow transparent liquid. The lower layer was the water phase. The organic phase was washed with water for 3 times (the separation was particularly slow and required a long time to stand). The excess raw material allyl polyethylene glycol ether was washed out. The organic phase was concentrated to remove the solvent, and the target product intermediate II was obtained, which was a light yellow waxy solid: 1465g, 1 HNMR showed that the molecular weight was about 12700, and GPC detection results (the conditions were the same as above) showed that the molecular weight distribution coefficient was 1.52.

[0059] S3, 2.5L acetonitrile was added into a 5L reaction flask, then intermediate II 1465g, N-(3-dimethylaminopropyl) methacrylamide 45g were added. The temperature was heated to 80°C for 12 hours, 50g activated carbon was added (for decolorization), and the heating was continued for half an hour. Then the mixture was filtered while hot. After the acetonitrile was removed by concentration of the filtrate, 3L purified water was added to the residue. After stirring and dissolving, 300ml (dichloromethane: ethyl acetate = 1:1) was added for washing 3 times, until the excess N-(3-dimethylaminopropyl) methacrylamide raw material was completely washed out. The water phase containing the product was filtered again through a G6 sand core funnel, and the product was obtained by freeze-drying, which was a light yellow solid: 1322g, 1 HNMR showed that the molecular weight was about 13100. GPC detection results (the conditions were the same as above) showed that the molecular weight distribution coefficient was 1.46.

[0060] Examples 3-9

[0061] This example relates to a method for preparing a silicone hydrogel contact lens, which specifically comprises the following steps:

[0062] The following compounds were optionally added into a 5000ml single-mouth flask with stirring (replaced by A, B, C, …, W), and there was no special requirement for the order of addition. The raw material components added in each example were shown in Table 1.

[0063] A: Siloxane I (alpha, omega-bis(methacryloxypropyl)-poly(dimethylsiloxane)- poly(trifluoropropyl-methylsiloxane)-poly(omega-methoxy-poly(ethylene glycol) propylmethylsiloxane)) from Example 1, molecular weight: 10000.

[0064] B: Siloxane I from Example 2, molecular weight: 13100.

[0065] C: Macromolecular siloxane II: [Methacryloxy(3-dimethylsilyl)propyl] terminated n-propyl terminated poly(methyl-trifluoropropyl-siloxane) (CAS: 1072465-05-3).

[0066] D: Hydrophilic monomer 1: N-vinylacetamide (CAS: 5202-78-8).

[0067] E: Hydrophilic monomer 2: N-vinylpyrrolidone (CAS: 88-12-0).

[0068] F: Hydrophilic monomer 3: N,N-dimethylacrylamide (CAS: 2680-03-7).

[0069] G: Hydrophilic monomer 4: N-methyl-N-vinylacetamide (CAS: 3195-78-6).

[0070] H: Small molecule siloxane 1: Methacryloxypropyltris(trimethylsiloxy)silane (CAS: 17096-07-0).

[0071] I: Small molecule siloxane 2: (3-methacryloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methyl (CAS: 69861-02-5)

[0072] J: Humectant 1 structure: where R = OH, X, Y are oxygen.

[0073] K: Humectant 2 structure same as Humectant 1, where R = H, X, Y are nitrogen.

[0074] L: Crosslinker 1: Ethylene glycol dimethacrylate (CAS: 97-90-5).

[0075] M: Crosslinker 2: Tetraethylene glycol dimethacrylate (CAS: 45103-58-0).

[0076] N: UV absorber 1: 2-acrylic acid 2-(4-benzoyl-3-hydroxyphenoxy)ethyl ester (UV 416, CAS: 16432-81-8).

[0077] O: UV absorber 2: 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl] ethyl 2- methylacrylate (UV090, CAS: 96478-09-0).

[0078] P: 2-Hydroxyethyl methacrylate (CAS: 868-77-9).

[0079] Q: Glycidyl methacrylate (CAS: 106-91-2).

[0080] R: Methyl methacrylate (CAS: 7534-94-3).

[0081] S: Isobornyl methacrylate (CAS: 106-91-2).

[0082] T: Sodium salt of bis(2-ethylhexyl)sulfosuccinate (CAS: 577-11-7).

[0083] U: Reactive dye 1: RB246 (CAS: 121888-69-5).

[0084] V: Reactive dye 2: RB247 (CAS: 109561-07-1).

[0085] W: Allyl hydroxyethyl ether (CAS: 111-45-5).

[0086] In addition to the above-mentioned substances, isopropyl alcohol is additionally added in a total mass of 10%, and the material is fully dissolved by stirring at 20-25°C, and the mixture is uniformly mixed for 1 h. The obtained mixed solution is filtered through a pressure filter with a pore size of 0.2 microns to obtain a formula polymerization solution. The formula polymerization solution is added into a full mold (material: PP for the female mold and PP for the male mold, and the PP material does not need to be modified to enhance polarity) through an automatic liquid injection machine, and is placed in an oven for curing. The temperature rising program is as follows: from room temperature to 60 degrees for 60 minutes, then uniformly heated to 110 degrees at a speed of 4 h, kept for 1 h, then uniformly cooled to 40 degrees at a speed of 4 h, and removed from the oven to obtain a lens to be demolded.

[0087] The female mold is separated by a mold separating machine, and the dry piece is directly sucked. The dry piece is first swelled with 20% ethanol aqueous solution. Then, 80% ethanol aqueous solution is used to replace the 20% ethanol aqueous solution for immersion for 1 h, and the amount of the lens to the solvent is 2 ml of 80% ethanol aqueous solution for 1 piece of lens. After the extraction is completed, pure water is added for balance three times (0.5 h each time), 3 ml of pure water for 1 piece of lens, and finally physiological saline is used for balance for 1 h to obtain the lens after sterilization. The sterilization condition is high-pressure steam sterilization at a temperature of 120 degrees for 25 minutes.

[0088]

[0089]

[0090] The lenses obtained in Examples 3-9 were tested:

[0091] ADk test:

[0092] The 201T oxygen permeability instrument (Creathch / Rehder-Dev Co, USA) was used to measure the Dk value according to the national standard GBT 11417.7-2012 by using the polarographic method. The results are shown in Table 2. The unit of Dk described herein is: 10 -11 (cm 2 / s)[mLO2 / (mL.hPa)].

[0093] B UV transmittance test:

[0094] The SP-1920 UV spectrophotometer (Shanghai Spectrum) was used to test the transmittance, and the transmittance of the lenses was scanned according to GBT 11417.5-2012. In this case, the T% value is the average value of the transmittance in this waveband.

[0095] C Water content test: The water content was tested according to GBT 11417.7-2012, method 4.5.

[0096] D Surface hydrophilicity / wettability: The surface hydrophilicity of the contact lenses was evaluated by the water film break uptime (WBUT). Operation: The contact lenses were immersed in standard saline overnight, and one side edge of the lens was lifted out of the water surface with tweezers. The time from lifting out of the water surface to the disappearance of the water film on the surface of the lens (water film retention time) was measured. The disappearance of the water film was determined by the naked eye. The test was performed 3 times, and the average value was calculated.

[0097] E Contact angle test: The water contact angle (WCA) on the contact lenses is a general measure of the surface wettability of the contact lenses. The dynamic floating bubble contact angle of the contact lenses was measured using the instrument device from FDS Future Digital Science Company. The FDS device can measure the advancing contact angle. The finished lenses after sterilization were tested at room temperature.

[0098] The test results of the lenses obtained in Examples 3-9 are shown in Table 2.

[0099]

[0100] As can be seen from Table 1, the lenses obtained in Examples 4-9 of the present application have excellent performance without improving the surface of the mold, and have high oxygen permeability, high wettability surface and other properties. The wettability of the lenses obtained in Example 3 without using the macromolecular siloxane I of the present application is poor, and the contact angle is large, which indicates that the macromolecular siloxane I can significantly improve the hydrophilicity of the surface of the lenses.

[0101] The present application has been described in detail by reference to particular embodiments and illustrative examples, but these are not intended to limit the present application to the details described herein. Various modifications and equivalents can occur to one skilled in the art without departing from the spirit and scope of the present application, and it is understood that the present application is intended to cover what falls within the scope of the appended claims.

Claims

1. A high oxygen permeable silicone hydrogel contact lens characterized in that, The raw material components include: macromolecular siloxane I, macromolecular siloxane II, small molecular siloxane, hydrophilic monomer, moisturizing agent, crosslinking agent, initiator and functional monomer; The macromolecular siloxane I has a molecular weight of 10000-15000, a molecular weight distribution coefficient less than 1.8 and a structural formula of: Wherein, a:b:c=(0.1-0.2):0.1:(0.7-0.8); b / (a+c)=1 / 9, d is 7-8 or 23-30; The macromolecular siloxane II has a structural formula of: Wherein, R1 is H or CH3, R2 is one of C3-C6 alkyl, and n is a natural number between 9-24; The moisturizing agent has a structural formula of: Wherein, R is one of H and OH; X and Y are independently one of O, S and N; M is one of chlorine, bromine and iodine; The small molecular siloxane is methacryloyloxypropyl tris(trimethylsiloxy)silane and / or (3-methacryloyloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methyl; The functional monomer includes one or more of ultraviolet absorber, molecular weight regulator, lens shape improver, demolding promoter and active dye. The lens shape improver is one or more of 2-hydroxyethyl methacrylate, glycidyl methacrylate, isobornyl methacrylate and methyl methacrylate; and the demolding promoter is sodium salt of bis(2-ethylhexyl)sulfosuccinate.

2. The high oxygen permeable silicone hydrogel contact lens of claim 1, wherein, The preparation method of the macromolecular siloxane I includes the following steps: S1, 1,3-bis(3-chloropropyl)tetramethyldisilane, D3F, D3, D3H and phosphonium alcohol salt are added into an organic solvent, trifluoromethanesulfonic acid is added under low temperature conditions for reaction, and an intermediate I is obtained after post-processing; S2, the intermediate I and allyl polyethylene glycol ether are added into an organic solvent for addition reaction, and an intermediate II is obtained after post-processing; S3, the intermediate II and N-(3-dimethylaminopropyl) methacrylamide are reacted in an organic solvent, and the macromolecular siloxane I is obtained after post-processing and freeze-drying; The structural formulas of the D3F, D3, D3H, phosphonium alcohol salt, intermediate I and intermediate II are respectively as follows: wherein a:b:c = (0.1-0.2):0.1:(0.7-0.8); b / (a+c) = 1 / 9, and d is 7 or 8.

3. The high oxygen permeable silicone hydrogel contact lens of claim 2, wherein, In S1, the temperature for adding trifluoromethanesulfonic acid is 0℃, and the reaction temperature is 10℃; And / or, the post-processing specifically refers to that a mixed solvent of methanol and nitromethane with a volume ratio of 5:1 is used to extract oligomers, a small amount of unopened raw materials and other cyclic body by-products generated in the reaction.

4. The high oxygen permeable silicone hydrogel contact lens of claim 2, wherein, In S2, the post-processing specifically refers to that the intermediate II crude product is dissolved in a mixed solvent of methyl tert-butyl ether and ethyl acetate with a volume ratio of 1:5, and then pure water is used to extract the remaining raw material allyl polyethylene glycol ether.

5. The high oxygen permeable silicone hydrogel contact lens of claim 2, wherein, In S3, the post-processing specifically refers to that the macromolecular siloxane I crude product is dissolved in pure water, and then a mixed solvent of dichloromethane and ethyl acetate with a volume ratio of 1:1 is used to extract and remove excess raw materials and other fat-soluble impurities.

6. The high oxygen permeable silicone hydrogel contact lens of claim 1, wherein, The raw material components include, by mass percentage, 30-40% of macromolecular siloxane I, 5-10% of macromolecular siloxane II, 10-20% of small molecular siloxane, 20-30% of hydrophilic monomer, 2-5% of humectant, 0.5-1.5% of crosslinking agent, 0.5-1% of initiator, and 2-5% of functional monomer.

7. The high oxygen permeable silicone hydrogel contact lens of claim 1 wherein, The hydrophilic monomer is one or more of N-vinyl pyrrolidone, N,N-dimethyl acrylamide, N-methyl-N-vinyl acetamide, and N-vinyl acetamide. The crosslinking agent is ethylene glycol dimethacrylate and / or tetraethylene glycol dimethacrylate. The initiator is azobisisobutyronitrile.

8. The method of making a high oxygen permeable, silicone hydrogel contact lens of any one of claims 1-7, wherein, The raw material components are mixed and dissolved in an organic solvent to obtain a polymerization solution, the polymerization solution is placed in a mold and subjected to heat treatment under a protective atmosphere, and then the mold is demolded and extracted after natural cooling, to obtain the high-oxygen-permeable silicone hydrogel contact lens.

9. The method of making a high oxygen permeable, silicone hydrogel contact lens of claim 8, wherein, The heat treatment specifically comprises: keeping at 60℃ for 60-100 min, and then uniformly heating to 110-120℃ at a speed of 4h, and keeping at 110-120℃ for 1h.

10. The method of making a high oxygen permeable, silicone hydrogel contact lens of claim 8, wherein, The demolding and extraction specifically comprise: placing the mold after heat treatment in a 20wt%-80wt% ethanol aqueous solution for hydration, so as to demold the lens and extract a small amount of residual monomer and oligomer in the lens.

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