CN112898506B - High oxygen permeability silica hydrogel and corneal contact lens - Google Patents

Abstract

The invention discloses a silicone hydrogel, which comprises the following components, which are prepared by polymerization in parts by mass: 5-60 parts of single-end organosiloxane macromonomer, double end-end organosiloxane 0.5-10 parts of alkane macromer, 0-30 parts of other silicon-containing monomers, 5-70 parts of hydrophilic monomers, initiator and crosslinking agent. The present invention takes single-terminated organosiloxane macromonomer as the main component and compounded double-terminated organosiloxane macromonomer, and the compound use of the two produces obvious synergistic effect, which can better improve Oxygen permeability, mechanical properties and hydrophilic properties of silicone hydrogels. The invention also discloses a corneal contact lens prepared by the silicon hydrogel material, which has high oxygen permeability, good light transmission and strong hydrophilicity, good mechanical properties, comfortable to wear, and does not contain solvents. Conducive to large-scale industrial production.

Description

A high oxygen permeable silicone hydrogel and corneal contact lens

Technical Field

The invention relates to a silicone hydrogel material, in particular to a silicone hydrogel with high oxygen permeability and a corneal contact lens, and belongs to the field of contact lens material preparation.

Background Art

Contact lenses, also known as corneal contact lenses, are used to correct vision, protect the eyeball or increase the beauty of the eyes, and are very popular among people. The field of corneal contact lenses has high requirements for the oxygen permeability of materials. If oxygen cannot be supplied normally during the wearing of contact lenses, the cornea will be hypoxic. Long-term insufficient oxygen supply will cause thinning of the corneal epithelium, dry eyes and other problems. With the development of science and technology, corneal contact lenses have gradually developed from early hard materials to soft materials with better comfort. Soft corneal contact lenses, also known as hydrogel corneal contact lenses, have good chemical stability, biocompatibility, ion permeability, surface wettability, mechanical properties and other characteristics. Traditional hydrogel corneal contact lenses are copolymerized by hydrophilic monomers such as hydroxyethyl methacrylate, N-vinyl pyrrolidone, etc., and generally have low oxygen permeability. Long-term wearing will cause corneal hypoxia, leading to ocular surface problems such as dry eyes, conjunctival congestion, and corneal edema.

Later, people found that silicon-containing polymer materials have advantages such as high oxygen permeability, good mechanical properties and biocompatibility. However, the surface of this material is hydrophobic, and when used in biological tissues, it will adhere to lipids and proteins, which is harmful for long-term use. Combining this material with hydrogel materials can form a silicone hydrogel material with good comprehensive performance: the long chain of siloxane forms a continuous phase of a "honeycomb" structure, providing a good channel for oxygen transmission, and the siloxane part determines the oxygen permeability of the material; the hydrophilic part swells to become a hydrogel, and the hydrogel part can reduce the friction between the material and the tissue, increasing the comfort of the wearer. Due to the unique performance advantages of silicone hydrogel, it has broad application prospects in the field of corneal contact lenses.

However, there are still many problems with silicone hydrogel materials. The hydrophobicity of silicone materials easily adsorbs proteins such as lysozymes in tears, and easily adheres to the eyeball, affecting the free rotation of contact lenses. To solve this problem, one research idea is to directly perform coating modification or surface grafting modification on the material surface to improve the hydrophilicity of the lens, but there are still problems such as the surface hydrophilicity cannot be permanently maintained and the process is relatively complicated.

Another research idea is to improve the hydrophilicity of the material itself. Silicone hydrogel lenses are generally copolymerized with silicone monomers and hydrophilic monomers, and usually contain one or more small molecular weight silicone monomers or larger molecular weight silicone oligomers. Small molecule silicone monomers have good hydrophilicity and good compatibility with hydrophilic monomers, but their effect on improving the oxygen permeability of the material is limited. Large molecular weight silicone oligomers are generally obtained by grafting reactive functional groups onto polydimethylsiloxane (PDMS), and copolymerization with hydrophilic monomers can effectively improve the oxygen permeability of the material. However, due to the high hydrophobicity of PDMS, its compatibility with hydrophilic monomers is poor, and the amount added is limited, which limits the improvement of the oxygen permeability of the material; and the surface of the resulting silicone hydrogel is highly hydrophobic, which affects the wearing comfort of the lens. In order to increase the amount of PDMS added and thus increase the oxygen permeability of the material, a suitable organic solvent is added to the formula as a simple solubilizing agent. The right amount of solvent can indeed improve the solubility, but the addition of solvent also destroys the original network structure of the material, reducing the strength and toughness of the finished lens. At the same time, during the polymerization production process, a large amount of solvent will evaporate into the air, which can easily cause fire and explosion, increasing the danger of production operations.

Therefore, developing a solvent-free silicone hydrogel lens that has high oxygen permeability, strong hydrophilicity, and good mechanical properties is one of the technical problems that technicians in this field need to solve urgently.

Summary of the invention

The purpose of the present invention is to provide a silicone hydrogel material and a corneal contact lens prepared using the silicone hydrogel material, which has high oxygen permeability, good light transmittance and strong hydrophilicity, good mechanical properties, comfortable wearing, and does not contain solvent, which is conducive to large-scale industrial production.

The present invention provides a silicone hydrogel, comprising the following components, calculated by weight, prepared by polymerization reaction:

Initiators and cross-linkers;

Among them, the sum of the mass parts of the single-end organic siloxane macromer, the double-end organic siloxane macromer, other silicon-containing monomers and hydrophilic monomers is 100 parts; the initiator accounts for 0.5-3% of the total weight of the single-end organic siloxane macromer, the double-end organic siloxane macromer, other silicon-containing monomers and hydrophilic monomers; the cross-linking agent accounts for 0.5-3% of the total weight of the single-end organic siloxane macromer, the double-end organic siloxane macromer, other silicon-containing monomers and hydrophilic monomers.

According to a specific but non-limiting embodiment of the present invention, the single-terminated organosiloxane macromer is selected from at least one of the two structures shown in formula (I):

Among them, the structural formula of X is as follows:

or

Wherein, _R1 is a hydrogen atom or a methyl group, _R2 is a _C1 - _C10 alkyl group, m is an integer ranging from 5 to 20, and n is an integer ranging from 5 to 100.

According to a specific but non-limiting embodiment of the present invention, the single-terminated organosiloxane macromonomer represented by formula (I) is prepared by the following method: a hydroxyl-terminated polyether-modified polydimethylsiloxane and (meth)acrylate glycidyl are reacted in the temperature range of 20 to 90° C. in the presence of a catalyst.

According to a specific but non-limiting embodiment of the present invention, the double-terminated organosiloxane macromer is selected from at least one of the two structures shown in formula (II) or formula (III):

or

Among them, the structural formula of Y is as follows:

Among them, the value range of a is an integer from 1 to 14, the value range of b is an integer from 1 to 6, and the value range of c is an integer from 13 to 68.

According to a specific but non-limiting embodiment of the present invention, the di-terminated organosiloxane macromonomer represented by formula (II) is prepared by the following method: di-hydroxy-terminated polydimethylsiloxane and methacrylic acid isocyanate are reacted in the temperature range of 20 to 80° C. under the action of a catalyst;

The double-terminated organosiloxane macromolecular monomer represented by formula (III) is prepared by the following method: double-hydroxy-terminated polydimethylsiloxane and glycidyl methacrylate are reacted in the temperature range of 20 to 80° C. under the action of a catalyst.

According to a specific but non-limiting embodiment of the present invention, the other silicon-containing monomers are small molecule silicon monomers or macromolecular silicon monomers, and the small molecule silicon monomers are selected from one or any combination of methacryloxypropyl tris(trimethylsiloxy)silane, methyl-bis(trimethylsiloxy)-silylpropyl methacrylate, 3-(methacryloxy)propyl trimethoxysilane and methacryloxymethyl tris(trimethylsiloxy)silane.

According to a specific but non-limiting embodiment of the present invention, the hydrophilic monomer is one or a combination of N-vinyl pyrrolidone, hydroxypropyl methacrylate, N,N-dimethylacrylamide, hydroxyethyl methacrylate, methacrylic acid, N-vinyl acetamide, glyceryl methacrylate, glycidyl methacrylate, hydroxybutyl methacrylate and N-vinyl methyl acetamide.

According to a specific but non-limiting embodiment of the present invention, the initiator is a photoinitiator or a thermal initiator; wherein the photoinitiator is at least one of 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one and 2,4,6-trimethylbenzyldiphenylphosphine oxide; the thermal initiator is at least one of azobisisobutyronitrile, benzoyl peroxide, azobisisoheptyl cyanide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate and bis(2-phenylethoxy)peroxydicarbonate;

The crosslinking agent is one or any combination of polyethylene glycol diacrylate, ethylene glycol dimethacrylate, triallyl isocyanurate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, diethylene glycol divinyl ether, vinyl methacrylate, divinyl polyethylene glycol and trimethylolpropane trimethacrylate.

In another aspect, the present invention provides a corneal contact lens made of the silicone hydrogel described above.

At the same time, the present invention also provides a method for preparing the above-mentioned corneal contact lens, comprising: uniformly mixing 5 to 60 parts of a single-end organic siloxane macromolecular monomer, 0.5 to 10 parts of a double-end organic siloxane macromolecular monomer, 0 to 30 parts of other silicon-containing monomers, 5 to 70 parts of a hydrophilic monomer, an initiator and a cross-linking agent, photo-initiating or thermally initiating polymerization and curing, and obtaining a corneal contact lens after hydration; wherein the sum of the mass fractions of the single-end organic siloxane macromolecular monomer, the double-end organic siloxane macromolecular monomer, the other silicon-containing monomers and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5 to 3% of the total weight of the single-end organic siloxane macromolecular monomer, the double-end organic siloxane macromolecular monomer, the other silicon-containing monomers and the hydrophilic monomer; and the cross-linking agent accounts for 0.5 to 3% of the total weight of the single-end organic siloxane macromolecular monomer, the double-end organic siloxane macromolecular monomer, the other silicon-containing monomers and the hydrophilic monomer.

The beneficial effects of the present invention are mainly reflected in:

1. The present invention uses a single-terminated organic siloxane macromer as a main component and adds a double-terminated organic siloxane macromer. When the two are used in combination to prepare silicone hydrogel, an obvious synergistic effect is produced, which is more conducive to the formation of a continuous silicon phase of the hydrogel material and obtains a higher oxygen permeability value; at the same time, the double-terminated organic siloxane macromer contains two polymerization-active double bonds, which can be used as a cross-linking agent in the polymerization system to increase the cross-linking degree of the silicone hydrogel material, thereby improving the mechanical properties of the gel material.

2. No solvent is added to the silicone hydrogel formula of the present invention, which is conducive to large-scale industrial production. It not only reduces production costs and environmental pollution, but more importantly, avoids the large-scale volatilization of solvents during the polymerization of mixed monomers to prepare lenses, thereby reducing health hazards to operators and the risk of causing major accidents such as explosions and combustion.

3. Since the single-end-capped and double-end-capped organosiloxane macromolecular monomers of the present invention both contain a hydrophilic polyether structure and a highly oxygen-permeable polysiloxane structure, the two structures are similar and have good compatibility. Therefore, when the two are used in combination, there is no need to add other silicon-containing monomers for solubilization. They can be well miscible with the hydrophilic monomers to obtain a silicone hydrogel material with good light transmission performance.

4. The silicone hydrogel material of the present invention and the corneal contact lens prepared therefrom have high oxygen permeability, good light transmittance, strong hydrophilicity and good mechanical properties, are comfortable to wear and are beneficial to eye health.

5. The production process of the present invention is simple, does not require secondary production, and is suitable for large-scale industrial production.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is an infrared spectrum of the single-terminated organosiloxane macromonomer (M1-w1) prepared in Example 1.

FIG. 2 is an infrared spectrum of the single-terminated organosiloxane macromonomer (M1-w2) prepared in Example 2.

DETAILED DESCRIPTION

The following provides specific embodiments to further illustrate the present invention, but the present invention is not limited to the following embodiments.

The inventors of the present application found in the process of developing silicone hydrogel corneal contact lenses that when a single-end-capped organic siloxane macromer is used as the main component and a double-end-capped organic siloxane macromer is compounded, the two can produce a significant synergistic effect when used in combination to prepare silicone hydrogels, and can better improve the oxygen permeability, mechanical properties and hydrophilic properties of silicone hydrogels. The reason may be that the use of single-end-capped and double-end-capped organic siloxane macromers is more conducive to the formation of a continuous silicon phase of the hydrogel material, and the formation of a continuous organic silicon phase is one of the key factors for improving the oxygen permeability of the material, and a higher oxygen permeability value can be obtained; at the same time, the double-end-capped organic siloxane macromer contains two polymerization-active double bonds, which can be used as a crosslinking agent in the polymerization system. When used in combination with a single-end-capped organic siloxane macromer, the crosslinking degree of the silicone hydrogel material can be increased, thereby improving the mechanical properties of the gel material. In addition, the present invention does not add solvents to the silicone hydrogel formula, avoiding various disadvantages of solvents in the lens production process, which is conducive to large-scale industrial production, so the beneficial effects are very significant. However, the method of preparing silicone hydrogel by using single-terminated organosiloxane macromer as main component and compounding double-terminated organosiloxane macromer as the present invention has not been reported in the literature so far.

The present invention provides a silicone hydrogel, comprising the following components, calculated by weight, prepared by polymerization reaction:

Initiators and cross-linkers;

Among them, the sum of the mass parts of the single-end organic siloxane macromer, the double-end organic siloxane macromer, other silicon-containing monomers and hydrophilic monomers is 100 parts; the initiator accounts for 0.5-3% of the total weight of the single-end organic siloxane macromer, the double-end organic siloxane macromer, other silicon-containing monomers and hydrophilic monomers; the cross-linking agent accounts for 0.5-3% of the total weight of the single-end organic siloxane macromer, the double-end organic siloxane macromer, other silicon-containing monomers and hydrophilic monomers.

Preferably, the mass fraction of the single-end-capped organosiloxane macromolecular monomer is 29 to 60 parts.

Specifically, the single-terminated organosiloxane macromolecular monomer is selected from at least one of the two structures shown in formula (I):

Among them, the structural formula of X is as follows:

or

Wherein, _R1 is a hydrogen atom or a methyl group, _R2 is a _C1 - _C10 alkyl group, m is an integer ranging from 5 to 20, and n is an integer ranging from 5 to 100. Preferably, m is an integer ranging from 7 to 12, and n is an integer ranging from 12 to 50.

The single-end-capped organosiloxane macromolecular monomer of formula (I) is a block copolymer, wherein the polysiloxane segment (1) can effectively improve the oxygen permeability of the silicone hydrogel material, and the polyether segment (2) and the acrylate end-capping group (3) have good hydrophilicity. The single-end-capped structure has only one end with a double-bond functional group with polymerization reaction activity, which greatly reduces the cross-linking degree of the polymer, so that the formed polymer network structure has a larger mesh and can lock more water. Therefore, the single-end-capped structure has better water content and hydrophilicity than the double-end-capped structure.

Through experiments, we found that the length m of the polyether segment (2) has an important influence on the hydrophilicity of the polymer. Appropriately increasing the length of the polyether segment can significantly increase the hydrophilicity of the single-terminated organic siloxane macromer, thereby greatly increasing its addition amount in the silicone hydrogel and significantly improving the oxygen permeability. When the single-terminated organic siloxane macromer is used alone to prepare silicone hydrogel, when the value of m is too small (m < 5), the single-terminated organic siloxane macromer has poor compatibility with the hydrophilic monomer and is difficult to add to the silicone hydrogel in large proportion, and the obtained silicone hydrogel has a low oxygen permeability; when the value of m is between 5 and 20, the hydrophilicity of the single-terminated organic siloxane macromer is significantly improved, and the oxygen permeability of the obtained silicone hydrogel is greatly improved, reaching more than 100 barrer, and can even reach a high level of 160 barrer; when the value of m exceeds 25, the single-terminated organic siloxane macromer is in a paste state, which affects the light transmittance of the lens, and therefore cannot be used to prepare corneal contact lenses.

The single-terminated organosiloxane macromonomer shown in formula (I) can be prepared by the following method:

Hydroxyl-terminated polyether-modified polydimethylsiloxane (HO-PDMS) and (meth) glycidyl acrylate (GMA) react in the temperature range of 20 to 90° C. under the action of a catalyst to generate a single-terminated organosiloxane macromolecular monomer. The catalyst may be at least one of trifluoromethanesulfonic acid, triethylamine or tetrabutylammonium chloride. HO-PDMS and GMA react in equal proportions.

Wherein, _R1 is a hydrogen atom or a methyl group, _R2 is a _C1 - _C10 alkyl group, m is an integer ranging from 5 to 20, and n is an integer ranging from 5 to 100.

The double-terminated organosiloxane macromolecular monomer is selected from at least one of the two structures shown in formula (II) or formula (III):

or

Among them, the structural formula of Y is as follows:

Among them, the value range of a is an integer from 1 to 14, the value range of b is an integer from 1 to 6, and the value range of c is an integer from 13 to 68.

The double-terminated organosiloxane macromonomer shown in formula (II) can be prepared by the following method:

The polydimethylsiloxane (HO-Y-OH) terminated with dihydroxyl groups and isocyanate methacrylate (IEM) are reacted in the temperature range of 20 to 80° C. under the action of a catalyst. The catalyst is at least one of dibutyltin dilaurate, trifluoromethanesulfonic acid, triethylamine or tetrabutylammonium chloride.

The double-terminated organosiloxane macromonomer shown in formula (III) can be prepared by the following method:

It is produced by the reaction of dihydroxy-terminated polydimethylsiloxane (HO-Y-OH) and glycidyl methacrylate (GMA) in the temperature range of 20 to 80°C under the action of a catalyst. The catalyst is at least one of dibutyltin dilaurate, trifluoromethanesulfonic acid, triethylamine or tetrabutylammonium chloride.

Among them, the structural formula of Y is as follows:

Among them, the value range of a is an integer from 1 to 14, the value range of b is an integer from 1 to 6, and the value range of c is an integer from 13 to 68.

The above-mentioned double-terminated organosiloxane macromolecular monomer has been patented, application number: 201510976917X, invention name: hydrophilic siloxane oligomer, silicone hydrogel, corneal contact lens and preparation method, which is cited in full here.

The above-mentioned single-end-capped and double-end-capped organosiloxane macromolecular monomers all have long dimethylsiloxane chains. Since the long dimethylsiloxane chains have longer siloxane bond lengths, higher siloxane bond energies, and the bond angles of the Si-O-Si bonds can vary in the range of 104°-180°, and due to the repulsive effect between the methyl group and the main chain, the long dimethylsiloxane chains present loose and soft characteristics. This structure provides an excellent channel for oxygen transmission, and can directly transmit oxygen in the air to the eyeball. The linear dimethylsiloxane chain has a loose structure and a large free volume. When the molecular weight is large, the organosilicon forms a continuous microphase region of a "honeycomb" structure, which is conducive to the transmission of oxygen. In addition, the PEG chain is embedded in the double-end-capped organosiloxane macromolecular silicon monomer, which can improve the compatibility of the macromolecular silicon monomer with the hydrophilic monomer.

Experiments have shown that the above-mentioned single-end organic siloxane macromer as the main component and the double-end organic siloxane macromer as the crosslinking agent, the combination of the two has a significant synergistic effect, and can better improve the oxygen permeability, mechanical properties and hydrophilic properties of silicone hydrogel. This may be because the oxygen permeability of silicone hydrogel materials is not only related to the structure and addition amount of silicon-containing monomers, but also to the microphase separation of the material. The formation of a continuous silicone phase is the key to improving the oxygen permeability of the material. When the single-end organic siloxane macromer and the double-end organic siloxane macromer are used in combination, it is more conducive to the formation of a continuous silicone phase of the hydrogel material, and a higher oxygen permeability value can be obtained. At the same time, the double-end organic siloxane macromer contains two polymerization-active double bonds, which can be used as a crosslinking agent in the polymerization system. When used in combination with the single-end organic siloxane macromer, it can increase the crosslinking degree of the silicone hydrogel material, thereby improving the mechanical properties of the gel material.

The other silicon-containing monomers can be small molecule silicon monomers, such as one or any combination of methacryloxypropyl tris(trimethylsiloxy)silane (TRIS), methyl-bis(trimethylsiloxy)-silylpropyl methacrylate (SIGMA), 3-(methacryloxy)propyl trimethoxysilane (KH570) and methacryloxymethyl tris(trimethylsiloxy)silane (MTTS); or macromolecular silicon monomers. Other silicon-containing monomers can be used as solubilizing monomers in silicone hydrogels to increase the compatibility of organic siloxane macromolecular monomers and hydrophilic monomers, and they have a certain effect on improving oxygen permeability.

Since both the single-end-capped organosiloxane macromer and the double-end-capped organosiloxane macromer contain a hydrophilic polyether structure and a highly oxygen-permeable polysiloxane structure, the two structures are similar and therefore have good compatibility. When the two organosiloxane macromers are compounded and used, there is no need to add other silicon-containing monomers for solubilization, and they can be well soluble with the hydrophilic monomers to obtain a silicone hydrogel material with good light transmittance. In fact, other silicon-containing monomers can be added or not as needed in actual production. A more preferred embodiment is to not add other silicon-containing monomers in the formula.

The hydrophilic monomer can be one or a combination of N-vinyl pyrrolidone (NVP), hydroxypropyl methacrylate (HPMA), N,N-dimethylacrylamide (DMA), hydroxyethyl methacrylate (HEMA), methacrylic acid (AA), N-vinyl acetamide (NVA), glyceryl methacrylate, glycidyl methacrylate, hydroxybutyl methacrylate and N-vinyl methyl acetamide. Each hydrophilic monomer has different performance characteristics, and compounding multiple formulas can give full play to the excellent performance of each monomer.

The initiator may be a photoinitiator or a thermal initiator. The photoinitiator may be at least one of 2-hydroxy-2-methylpropiophenone (D1173), 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one and 2, 4, 6-trimethylbenzyldiphenylphosphine oxide; the thermal initiator may be at least one of azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), azobisisoheptyl cyanide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate and bis(2-phenylethoxy) peroxydicarbonate.

The crosslinking agent can be one or any combination of polyethylene glycol diacrylate (PEGDA), ethylene glycol dimethacrylate (EGDMA), triallyl isocyanurate (TAIC), triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, diethylene glycol divinyl ether, vinyl methacrylate, divinyl polyethylene glycol and trimethylolpropane trimethacrylate.

In actual production, other functional monomers may be added to the silicone hydrogel material as needed, such as colored monomers, color-changing monomers, or monomers that block ultraviolet light, blue light, or near-infrared light.

The above-mentioned single-end-capped and double-end-capped organosiloxane macromolecular monomers have excellent hydrophilic properties, especially the single-end-capped structure, which can be well mixed with various hydrophilic monomers without solvent dissolution. Therefore, the present invention does not add solvents in the silicone hydrogel formula, which is a huge advantage for large-scale industrial production. Because in large-scale industrial production, the addition of organic solvents is a very serious constraint factor. The addition of organic solvents not only increases production and recycling costs, but also causes environmental pollution. More importantly, in the process of preparing lenses by polymerization of mixed monomers, whether it is thermal polymerization or photopolymerization, a large amount of solvent will evaporate into the air. When the solvent concentration in the air exceeds a certain value, it will not only affect the health of the operators, but also cause dangers such as explosion and combustion.

On the other hand, since the single-end-capped and double-end-capped organosiloxane macromers are well soluble in the hydrophilic monomers, they can be added to the silicone hydrogel in large proportions, greatly increasing the amount of PDMS added, thereby greatly improving the oxygen permeability of the silicone hydrogel. The amount of the organosiloxane macromer added to the silicone hydrogel of the present invention is 5.5-70% in total, and the organosiloxane macromer accounts for almost 5.5-70% of the total weight of the silicone hydrogel, that is, the present invention can achieve an addition amount of more than 50% of the organosiloxane macromer, while the commercially available products can only achieve an addition of about 20% of the organosiloxane oligomer, which is far lower than the addition level of the present invention.

Experiments show that the silicone hydrogel prepared by the present invention has a water content of 25-60%, an oxygen permeability of more than 200 barrer, and a high elongation at break, all greater than 150%.

The present invention also provides a corneal contact lens made of the above silicone hydrogel material. The corneal contact lens is prepared by the following method:

5-60 parts of single-end organosiloxane macromer, 0.5-10 parts of double-end organosiloxane macromer, 0-30 parts of other silicon-containing monomers, 5-70 parts of hydrophilic monomers, initiator and cross-linking agent are uniformly mixed, injected into a corneal contact lens mold, photo-initiated or thermally initiated polymerization and cured, and hydrated to obtain a silicone hydrogel corneal contact lens; wherein the sum of the mass parts of the single-end organosiloxane macromer, the double-end organosiloxane macromer, other silicon-containing monomers and hydrophilic monomers is 100 parts; the initiator accounts for 0.5-3% of the total weight of the single-end organosiloxane macromer, the double-end organosiloxane macromer, other silicon-containing monomers and hydrophilic monomers; the cross-linking agent accounts for 0.5-3% of the total weight of the single-end organosiloxane macromer, the double-end organosiloxane macromer, other silicon-containing monomers and hydrophilic monomers.

The corneal contact lens of the present invention is made of the above-mentioned silicone hydrogel material. The silicone hydrogel material retains the high hydrophilicity of the hydrogel material, has good anti-lipid precipitation performance and biocompatibility, is comfortable to wear, and has high oxygen permeability, which can reduce the incidence of ophthalmic diseases caused by hypoxia and is beneficial to eye health; the good light transmittance ensures the visual effect and comfort of lens wearing.

The present invention is further described below in conjunction with specific examples, but the present invention is not limited to the following examples. The experimental methods used in the above and following examples are conventional methods unless otherwise specified. The materials, reagents, etc. used in the above and following examples, unless otherwise specified, can be obtained from commercial sources.

Example 1

Preparation of Mono-terminated Organosiloxane Macromonomer

Take 14.1g HO-PDMS (number average molecular weight of about 1500, wherein m is about 7, n is about 16, purchased from Nanjing Fuqun Chemical Co., Ltd.), 1.3g glycidyl methacrylate (GMA), 100μL trifluoromethanesulfonic acid, stir magnetically, reflux at 30°C for 24h, and distill under reduced pressure after the reaction to obtain an organosiloxane macromonomer, denoted as M1-w1. Figure 1 is an infrared spectrum of the single-terminated organosiloxane macromonomer (M1-w1) prepared in Example 1.

Where m is approximately 7 and n is approximately 16 (M1-w1)

Example 2

Preparation of Mono-terminated Organosiloxane Macromonomer

Take 54.3g HO-PDMS (number average molecular weight of about 5500, wherein m is about 11, n is about 50, purchased from Nanjing Fuqun Chemical Co., Ltd.), 1.4g glycidyl methacrylate (GMA), 100μL tetrabutylammonium chloride, magnetic stirring, reflux reaction at 50°C for 5h, and vacuum distillation to obtain an organosiloxane macromer, denoted as M1-w2. Figure 2 is an infrared spectrum of the single-terminated organosiloxane macromer (M1-w2) prepared in Example 2.

Among them, m is about 11 and n is about 50

(M1-w2)

Example 3

Preparation of di-terminated organosiloxane macromonomer

Take 13g of diol (the structural formula is shown in Formula W3 below), 20mL of chloroform, 0.1g of catalyst dibutyltin dilaurate, and 1.2g of methacrylate isocyanate (IEM), mix well, and heat to reflux at 50°C for 10h. After the reaction is completed, wash with petroleum ether, let stand and separate, take the lower layer of liquid and distill under reduced pressure to obtain a transparent double-terminated organosiloxane macromolecular monomer (Formula II), recorded as M2-W3.

Example 4

Preparation of di-terminated organosiloxane macromonomer

Take 13 g of diol (the structural formula is shown in Formula W4 below), 30 mL of tetrahydrofuran, 0.6 g of glycidyl methacrylate (GMA), and 0.5 g of trifluoromethanesulfonic acid, stir magnetically, and reflux at 60°C for 30 min. After the reaction, distill under reduced pressure to obtain a transparent double-terminated organosiloxane macromonomer (Formula III), which is recorded as M2-W4.

Embodiment 5-6

A silicone hydrogel is prepared by polymerization of the following components:

The single-terminated organosiloxane macromonomer is prepared by Example 1, and the double-terminated organosiloxane macromonomer is prepared by Examples 3 and 4, respectively.

Embodiment 7-8

A silicone hydrogel is prepared by polymerization of the following components:

The single-terminated organosiloxane macromonomer is prepared by Example 2, and the double-terminated organosiloxane macromonomer is prepared by Examples 3 and 4, respectively.

Examples 9-16

Contact lens preparation

The mono-terminated organosiloxane macromer and the di-terminated organosiloxane macromer are uniformly mixed with other silicon-containing monomers, hydrophilic monomers, initiators and crosslinking agents, injected into a corneal contact lens mold, and polymerized and cured by light initiation or heat initiation, and hydrated to obtain a silicone hydrogel corneal contact lens. The obtained corneal contact lens has a front surface and a back surface, and the front surface and the back surface are not modified.

Among them, the single-terminated organosiloxane macromonomer is prepared by Example 1 or Example 2; the double-terminated organosiloxane macromonomer is prepared by Example 3 or Example 4; other silicon-containing monomers use methacryloxypropyl tris(trimethylsiloxy)silane (TRIS); the hydrophilic monomer uses N-vinyl pyrrolidone (NVP), hydroxypropyl methacrylate (HPMA), and hydroxyethyl methacrylate (HEMA); the crosslinking agent uses ethylene glycol dimethacrylate (EGDMA); the initiator uses 2-hydroxy-2-methylpropiophenone (D1173) and azobisisobutyronitrile (AIBN). The reaction components and ratios of Examples 9-16 are listed in Table 1.

Comparative Examples 1-4

Based on the formulations of Examples 9, 10, 11, and 12, instead of using a single-terminated organosiloxane macromer (prepared by Example 1 or 2) or a double-terminated organosiloxane macromer (prepared by Example 3 or 4) alone, the other components and the proportions remain unchanged, and Comparative Examples 1-4 are prepared in the same manner. The reaction components and ratios are listed in Table 1.

Embodiment 17

Performance Testing

The oxygen permeability values of the corneal contact lenses of Examples 9-16 and Comparative Examples 1-4 were measured respectively by the coulometric method according to the national standard (GBT 11417.3-2012). The test results are listed in Table 1.

The moisture content of the corneal contact lenses of Examples 9-16 and Comparative Examples 1-4 was measured by weighing method, the weight of the glass slide was Q1, the weight of the lens and the glass slide was Q2, and after drying in an oven at 50°C to constant weight, the gross weight was G3, and the moisture content = (Q2-G3)/(Q2-Q1). The test results are listed in Table 1.

The elongation of the corneal contact lenses of Examples 9 to 16 and Comparative Examples 1 to 4 was tested using an electronic tensile testing machine XLW (PC). Each sample was clamped with a clamp for measurement, and the elongation at break of the corneal contact lens samples was measured. The test results are listed in Table 1.

Table 1 Reaction components and ratios (by mass fraction) and properties of Examples 9-16 and Comparative Examples 1-4

After comparing the performance of Examples 9, 10, 11, and 12 with Comparative Examples 1-4, it was found that the oxygen permeability of the corneal contact lens obtained by combining the single-end-capped organosiloxane macromer with the double-end-capped organosiloxane macromer was significantly higher than that of using either one alone, and the elongation at break was also significantly higher, and the water content was also improved. This shows that the combined use of the single-end-capped and double-end-capped organosiloxane macromers has an obvious synergistic effect, which significantly improves the oxygen permeability and elongation at break of the material.

It can be seen from Table 1 that the oxygen permeability values of the corneal contact lenses of the present invention are all above 200 barrer, and some are even as high as above 260 barrer; at the same time, the elongation at break values are also very high, all greater than 150%, and the performance parameters meet the commercial standards, indicating that the corneal contact lenses prepared by the present invention have good flexibility, durability, and are not easy to break.

The above are only specific application examples of the present invention and do not constitute any limitation on the protection scope of the present invention. Any technical solution formed by equivalent transformation or equivalent replacement shall fall within the protection scope of the present invention.

Claims (9)

1. A silicone hydrogel comprising the following components, calculated by weight, prepared by polymerization:

Wherein, the single-terminated organosiloxane macromolecular monomer is selected from at least one of the two structures shown in formula (I):

Among them, the structural formula of X is as follows:

or

Wherein, R ₁ is a hydrogen atom or a methyl group, R ₂ is a C ₁ -C ₁₀ alkyl group, m is an integer ranging from 5 to 20, and n is an integer ranging from 5 to 100; The double-terminated organosiloxane macromolecular monomer is selected from at least one of the two structures shown in formula (II) or formula (III):

or

Among them, the structural formula of Y is as follows:

Wherein, the value range of a is an integer from 1 to 14, the value range of b is an integer from 1 to 6, and the value range of c is an integer from 13 to 68; The sum of the weight parts of the single-end organic siloxane macromer, the double-end organic siloxane macromer, other silicon-containing monomers and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5-3% of the sum of the weight of the single-end organic siloxane macromer, the double-end organic siloxane macromer, other silicon-containing monomers and the hydrophilic monomer; the crosslinking agent accounts for 0.5-3% of the sum of the weight of the single-end organic siloxane macromer, the double-end organic siloxane macromer, other silicon-containing monomers and the hydrophilic monomer. 2. The silicone hydrogel according to claim 1, wherein the single-terminated organosiloxane macromonomer represented by formula (I) is prepared by the following method: a hydroxyl-terminated polyether-modified polydimethylsiloxane and (meth) glycidyl acrylate are reacted in the temperature range of 20 to 90° C. in the presence of a catalyst. 3. The silicone hydrogel according to claim 1, wherein the double-terminated organosiloxane macromolecular monomer represented by formula (II) is prepared by the following method: a double-hydroxy-terminated polydimethylsiloxane and methacrylate isocyanate are reacted in the temperature range of 20 to 80° C. under the action of a catalyst; The double-terminated organosiloxane macromolecular monomer represented by formula (III) is prepared by the following method: double-hydroxy-terminated polydimethylsiloxane and glycidyl methacrylate are reacted in the temperature range of 20 to 80° C. under the action of a catalyst. 4. The silicone hydrogel according to claim 1, wherein the other silicon-containing monomers are small molecule silicone monomers or macromolecular silicone monomers, and the small molecule silicone monomers are selected from one or any combination of methacryloxypropyl tris(trimethylsiloxy)silane, methyl-bis(trimethylsiloxy)-silylpropyl methacrylate, 3-(methacryloxy)propyl trimethoxysilane and methacryloxymethyl tris(trimethylsiloxy)silane. 5. The silicone hydrogel according to claim 1, wherein the hydrophilic monomer is one or a combination of N-vinyl pyrrolidone, hydroxypropyl methacrylate, N,N-dimethylacrylamide, hydroxyethyl methacrylate, methacrylic acid, N-vinyl acetamide, glyceryl methacrylate, glycidyl methacrylate, hydroxybutyl methacrylate and N-vinyl methyl acetamide. 6. The silicone hydrogel according to claim 1, wherein the initiator is a photoinitiator or a thermal initiator; wherein the photoinitiator is at least one of 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one and 2,4,6-trimethylbenzyldiphenylphosphine oxide; and the thermal initiator is at least one of azobisisobutyronitrile, benzoyl peroxide, azobisisoheptylcyanide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate and bis(2-phenylethoxy) peroxydicarbonate. 7. The silicone hydrogel according to claim 1, wherein the crosslinking agent is one or any combination of polyethylene glycol diacrylate, ethylene glycol dimethacrylate, triallyl isocyanurate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, diethylene glycol divinyl ether, vinyl methacrylate, divinyl polyethylene glycol ester and trimethylolpropane trimethacrylate. 8. A corneal contact lens made of the silicone hydrogel according to any one of claims 1 to 7. 9. A method for preparing a corneal contact lens as claimed in claim 8, comprising: uniformly mixing 41-60 parts of a single-end organic siloxane macromer, 0.5-10 parts of a double-end organic siloxane macromer, 0-30 parts of other silicon-containing monomers, 5-70 parts of a hydrophilic monomer, an initiator and a cross-linking agent, photo-initiating or thermally initiating polymerization and curing, and hydrating to obtain a corneal contact lens; wherein the sum of the mass fractions of the single-end organic siloxane macromer, the double-end organic siloxane macromer, the other silicon-containing monomers and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5-3% of the total weight of the single-end organic siloxane macromer, the double-end organic siloxane macromer, the other silicon-containing monomers and the hydrophilic monomer; and the cross-linking agent accounts for 0.5-3% of the total weight of the single-end organic siloxane macromer, the double-end organic siloxane macromer, the other silicon-containing monomers and the hydrophilic monomer.

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