CN113201102B - Silicon hydrogel, corneal contact lens and preparation method thereof - Google Patents
Silicon hydrogel, corneal contact lens and preparation method thereof Download PDFInfo
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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Abstract
The invention discloses a silicon hydrogel which comprises a single-end-capped organic siloxane oligomer and a double-end-capped organic siloxane oligomer, and is prepared by polymerization reaction of the single-end-capped organic siloxane oligomer and a hydrophilic monomer. The single-end-capped and double-end-capped organic siloxane oligomers used in the invention have good hydrophilic performance and are well soluble with hydrophilic monomers, and especially the composite use of the two can generate obvious synergistic interaction effect, so that the oxygen permeability, the hydrophilic performance, the lipid precipitation resistance and other performances of the silicon hydrogel can be better improved. The silicone hydrogel formulation does not contain a solvent, and is beneficial to large-scale industrial production. The silicon hydrogel material and the corneal contact lens prepared by the invention have high oxygen permeability, good light transmission, high water content, good flexibility and lipid precipitation resistance, and are comfortable to wear. The high oxygen permeability and good lipid precipitation resistance of the lens can reduce the incidence of ophthalmic diseases and is beneficial to eye health.
Description
Technical Field
The invention relates to a silicon hydrogel material, in particular to a silicon hydrogel, a corneal contact lens and a preparation method thereof, belonging to the field of preparation of contact lens materials.
Background
Contact lenses, also known as contact lenses, are worn directly on the eye of a person to correct vision. Compared with the common glasses, the contact lenses are convenient, beautiful and comfortable. The material for the corneal contact lens is required to have not only good light transmission, biocompatibility, surface hydrophilicity, appropriate mechanical properties and the like, but also high oxygen permeability. This is because there is no blood vessel supplying oxygen in the cornea, and oxygen and water in the air are absorbed to promote metabolism, so as to maintain its own nutrition. If oxygen is not normally supplied during the wearing process of the corneal contact lens, the long-term insufficient oxygen supply and oxygen deficiency of the cornea can cause inflammation, and the problems of corneal edema, dry eyes and the like are caused.
Contact lenses can be generally classified into hard contact lenses and soft contact lenses. Hard contact lenses have disadvantages such as being hard in material and poor in wettability, and therefore tend to cause discomfort to the eyeball when worn. The soft contact lens has good chemical stability, light transmission, biocompatibility, ion permeability and mechanical property, is more comfortable to wear, and is the mainstream product of the contact lens at present.
In the development history of the soft contact lens industry, a hydrogel material is firstly formed by polymerizing hydrophilic monomers such as hydroxyethyl methacrylate (HEMA), N-vinyl pyrrolidone (NVP), N-Dimethylacrylamide (DMA) and the like so as to meet the requirements of gas transmission and mechanical operability of the contact lens. However, these polymer networks have poor oxygen-dissolving and diffusing capacity, hardly transmit oxygen, and essentially have no oxygen permeability, and can transmit oxygen only through water molecules swollen therein, thereby obtaining low oxygen permeability. The oxygen permeability coefficient of the hydrogel lens can be improved only by improving the water content of the hydrogel lens, however, the improvement of the oxygen permeability of the hydrogel lens by improving the water content is limited, and the oxygen permeability coefficient of pure water is only 40 barrers, which is the theoretical upper limit of the oxygen permeability of the hydrogel lens. In addition, too high water content may result in poor mechanical performance of the lens, too fast surface water loss, etc.
In order to improve the oxygen permeability of conventional hydrogel materials, attempts have been made to combine a silicon-containing polymer segment having high oxygen permeability with a hydrogel material to prepare a novel hydrogel. After the two are combined, the oxygen permeability of the material is determined by the siloxane part, and the abrasion between the material and tissues can be reduced by the hydrogel part, so that the comfort is improved. The silicone hydrogel lens has high oxygen permeability and excellent comprehensive performance, becomes a latest generation of soft corneal contact lens, and has wide application prospect in the field of corneal contact lenses.
Silicone hydrogel lenses are generally made by copolymerizing silicone monomers and hydrophilic monomers, and usually contain one or more than two small molecular weight silicone monomers or silicone oligomers with larger molecular weights, with the siloxane moiety determining the oxygen permeability of the material. Although the small molecular silicon monomer has good compatibility with the hydrophilic monomer, the improvement effect on the oxygen permeability of the material is limited. The macromolecular silicon monomer is an oligomer with a large number of Si atoms in a molecular structure, is generally obtained by grafting a reactive functional group from Polydimethylsiloxane (PDMS), and is copolymerized with a hydrophilic monomer to effectively improve the oxygen permeability of the material. However, since PDMS has high hydrophobicity and poor compatibility with hydrophilic monomers, the amount of PDMS added is limited, which limits the improvement of oxygen permeability of the material. In order to increase the addition of PDMS and further increase the oxygen permeability of the material, a suitable organic solvent is added to the formulation to improve the compatibility, but the solvent will destroy the original network structure of the material and reduce the strength and toughness of the finished lens, and more seriously, the solvent will volatilize into the air in a large amount during the polymerization production process, which is easy to cause fire and explosion and increases the danger of production operation. In addition, the PDMS has low surface energy and is hydrophobic, and after the organosilicon monomer and the hydrophilic monomer are polymerized, silicon-containing groups are easy to migrate to the surface of the silicon hydrogel, so that high lipid adsorption is caused, the lens is easy to cause visual blurring due to high lipid adsorption, the wearing comfort is reduced, and inflammation is caused after long-term wearing.
Therefore, it is one of the technical problems to be solved by those skilled in the art to develop a silicone hydrogel lens that contains no solvent and has high oxygen permeability, high hydrophilicity and anti-lipid precipitation properties.
Disclosure of Invention
The invention aims to provide a silicon hydrogel material and a corneal contact lens prepared from the silicon hydrogel material, which have the advantages of good oxygen permeability, light transmission, good lipid precipitation resistance, strong hydrophilicity, good flexibility, comfortable wearing, no solvent and contribution to large-scale industrial production.
The invention provides a silicone hydrogel which is characterized by comprising the following components in parts by mass and prepared through polymerization reaction:
an initiator and a crosslinking agent;
wherein the sum of the mass parts of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer; the cross-linking agent accounts for 0.5 to 3 percent of the weight sum of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the micromolecular silicon monomer and the hydrophilic monomer.
According to a particular but non-limiting embodiment of the invention, the mono-end-capped organosiloxane oligomer has the structure according to formula (I):
wherein m is an integer ranging from 4 to 20, n is an integer ranging from 5 to 100, and R is C 1 -C 10 Alkyl group of (1).
According to a particular but non-limiting embodiment of the invention, the mono-end-capped organosiloxane oligomer of formula (I) is prepared by: under the action of a catalyst, in the temperature range of 20-90 ℃, the monohydroxy terminated polyether modified polydimethylsiloxane firstly reacts with isophorone diisocyanate, and then hydroxyethyl methacrylate is added for continuous reaction to obtain the mono-terminated organic siloxane oligomer shown in the formula (I).
According to a particular but non-limiting embodiment of the invention, the double-end-capped organosiloxane oligomer has the structure shown in formula (II):
wherein, the value range of a is an integer between 4 and 20, and the value range of b is an integer between 5 and 100.
According to a particular but non-limiting embodiment of the invention, the double-capped organosiloxane oligomer of formula (II) is prepared by: under the action of a catalyst, in the temperature range of 20-90 ℃, the dihydroxy terminated polyether modified polydimethylsiloxane firstly reacts with isophorone diisocyanate, and then hydroxyethyl methacrylate is added for continuous reaction to obtain the dihydroxy terminated organic siloxane oligomer shown in the formula (II).
According to a specific but non-limiting embodiment of the present invention, the small molecule silicon monomer is one or any combination of methacryloxymethyltris (trimethylsiloxy) silane, methacryloxypropyltris (trimethylsiloxy) silane, gamma-aminopropyltriethoxysilane, 3- (methacryloxy) propyltrimethoxysilane, and 3- (3-methacryloxy-2-hydroxypropyl) propylbis (trimethylsiloxane) methylsilane.
According to a specific but non-limiting embodiment of the invention, the hydrophilic monomer is one or a combination of N-vinyl pyrrolidone, vinylcyclohexamide, polyether methacrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, glycerol methacrylate, glycidyl methacrylate, N-dimethylacrylamide, N-vinylacetamide and N-vinylmethylacetamide.
According to a particular but non-limiting embodiment of the invention, the initiator is a photoinitiator or a thermal initiator; the photoinitiator is at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl propiophenone and 2,4, 6-trimethylbenzyl diphenyl phosphine oxide, and the thermal initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile and benzoyl peroxide;
the cross-linking agent is at least one of triallyl isocyanurate (TAIC), vinyl methacrylate, ethylene Glycol Dimethacrylate (EGDMA), triethylene glycol dimethacrylate, polyethylene glycol diacrylate (PEGDA), tetraethylene glycol dimethacrylate, polyethylene glycol divinyl ether and trimethylolpropane trimethacrylate.
In another aspect, the invention provides a corneal contact lens made from the silicone hydrogel.
Meanwhile, the invention also provides a preparation method of the corneal contact lens, which comprises the following steps: uniformly mixing 20-60 parts of single-end-capped organic siloxane oligomer of formula (I), 10-50 parts of double-end-capped organic siloxane oligomer of formula (II), 0-30 parts of small molecular silicon monomer, 5-70 parts of hydrophilic monomer, initiator and cross-linking agent, injecting into a corneal contact lens mould, carrying out photo-initiated or thermal-initiated polymerization curing, and hydrating to obtain a silicon hydrogel corneal contact lens; wherein the sum of the mass parts of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer; the cross-linking agent accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer.
The invention has the following beneficial effects:
1. the single-end-capped and double-end-capped organic siloxane oligomer used for preparing the silicon hydrogel has good hydrophilic performance and good intersolubility with hydrophilic monomers, and the composite use effect of the two is better than that of single use, so that the obvious synergistic effect can be generated, the formation of a continuous silicon phase of a hydrogel material is facilitated, and a higher oxygen permeation value is obtained; meanwhile, because the single-end and double-end structures are similar and the intermiscibility is good, the invention can be well dissolved with hydrophilic monomers without adding micromolecular silicon monomers for solubilization.
2. The silicon hydrogel formula disclosed by the invention is not added with a solvent, so that the silicon hydrogel is beneficial to large-scale industrial production, the production cost is reduced, the environmental pollution is reduced, more importantly, the solvent is prevented from being volatilized in a large amount in the process of preparing the lens by polymerizing the mixed monomer, and the health hazard to operators and the risks of serious accidents such as explosion, combustion and the like are reduced.
3. The silicon hydrogel material and the corneal contact lens prepared by the invention have high oxygen permeability, good light transmittance, high water content, good flexibility and lipid precipitation resistance, are comfortable to wear, can reduce the incidence of ophthalmic diseases due to the high oxygen permeability and the good lipid precipitation resistance, and are beneficial to eye health.
4. The invention has simple production process, does not need secondary production and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a single end-capped organosiloxane oligomer prepared in example 1.
FIG. 2 is a nuclear magnetic spectrum of a double-capped organosiloxane oligomer prepared in example 3.
Detailed Description
The following specific embodiments are provided to further illustrate the present invention, but the present invention is not limited to only the following embodiments.
The inventor of the application finds through experiments that when the polyether chain segment is connected with the polysiloxane long chain, the synthesized single-end-capped or double-end-capped organic siloxane oligomer has good hydrophilicity and good intersolubility with hydrophilic monomers, can be added into the silicone hydrogel in a large proportion, improves the addition amount of the organic siloxane oligomer to a large extent, and can remarkably improve the oxygen permeability of the silicone hydrogel. Especially, when the two are used in a composite way to prepare the silicon hydrogel, the effect is better than that of single use, obvious synergistic interaction can be generated, and the oxygen permeability, the hydrophilic performance, the lipid precipitation resistance and other performances of the silicon hydrogel are further improved. The reason for this is probably that the single-end-capped and double-end-capped organic siloxane oligomer used in the invention has similar structure and is dissolved similarly and mutually, the composite use of the two is more favorable for the formation of the continuous silicon phase of the hydrogel material, and the formation of the continuous organic silicon phase is one of the key factors for improving the oxygen permeability of the material. In addition, no solvent is added in the formula of the silicon hydrogel, so that various defects of the solvent in the production process of the lens are avoided, large-scale industrial production is facilitated, and the beneficial effect is very obvious.
The invention provides a silicon hydrogel which comprises the following components in parts by mass and is prepared through a polymerization reaction:
an initiator and a crosslinking agent;
wherein the sum of the mass parts of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer; the cross-linking agent accounts for 0.5 to 3 percent of the weight sum of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the micromolecular silicon monomer and the hydrophilic monomer.
Specifically, the single-end-capped organic siloxane oligomer has a structure shown in a formula (I):
wherein m is an integer ranging from 4 to 20, n is an integer ranging from 5 to 100, and R is C 1 -C 10 Alkyl group of (1).
The above-described mono-end-capped organosiloxane oligomers of formula (I) are block copolymers in which the long polysiloxane chains (1) give the material good oxygen permeability and the polyether segments (2) and the end-grafted amide and methacrylate groups (3) provide good hydrophilicity. Experiments show that when the polyether chain segment (2) is connected with the polysiloxane long chain (1), the synthesized polymer has better hydrophilicity and good mutual solubility with hydrophilic monomers, the problem that organic siloxane oligomers and hydrophilic monomers are difficult to mutually dissolve is solved, the organic siloxane oligomers can be added into the silicone hydrogel in a large proportion under the condition of no need of a dissolving assisting solvent, the addition amount of the organic siloxane oligomers is greatly increased, and the oxygen permeability and the light transmittance of the silicone hydrogel material are remarkably improved. In addition, the connection of the polyether chain segment (2) and the polysiloxane long chain (1) is also beneficial to improving the lipid precipitation resistance of the silicone hydrogel material, and experiments show that the lipid adsorption rate of the silicone hydrogel lens prepared by connecting the polyether chain segment and the polysiloxane long chain is lower.
The mono-end-blocked organosiloxane oligomers of the formula (I) can be prepared by the following process:
under the action of a catalyst, in a temperature range of 20-90 ℃, monohydroxy terminated polyether modified polydimethylsiloxane (HO-PDMS) firstly reacts with isophorone diisocyanate (IPDI) to generate an IPDI terminated intermediate product, and then hydroxyethyl methacrylate (HEMA) is added for continuous reaction to obtain the mono-terminated organic siloxane oligomer. Wherein the catalyst is dibutyltin dilaurate. HO-PDMS reacts with IPDI and HEMA in equal proportion.
Wherein m is an integer ranging from 4 to 20, n is an integer ranging from 5 to 100, and R is C 1 -C 10 The alkyl group of (1).
The double-end-capped organic siloxane oligomer has a structure shown in a formula (II):
wherein, the value range of a is an integer between 4 and 20, and the value range of b is an integer between 5 and 100.
The double-end-capped organosiloxane oligomer of the formula (II) above is a block copolymer in which the long polysiloxane chains (4) give the material good oxygen permeability and the polyether segments (5) and the end-grafted amide groups and methacrylate groups (6) provide good hydrophilicity. Experiments show that when the polyether chain segment (5) is connected with the polysiloxane long chain (4), the synthesized polymer has better hydrophilicity and is well dissolved with hydrophilic monomers, the problem that organic siloxane oligomer and hydrophilic monomers are difficult to dissolve in each other is solved, the organic siloxane oligomer can be added into the silicone hydrogel in a large proportion under the condition of not needing a cosolvent, the addition of the organic siloxane oligomer is greatly improved, and the oxygen permeability and the light transmittance of the silicone hydrogel material are obviously improved. In addition, the connection of the polyether chain segment (5) and the polysiloxane long chain (4) is also beneficial to improving the lipid precipitation resistance of the silicone hydrogel material, and experiments show that the silicone hydrogel lens prepared by connecting the polyether chain segment and the polysiloxane long chain has lower lipid adsorption rate.
The double-end-capped organosiloxane oligomer of the formula (II) can be prepared by:
under the action of a catalyst, in a temperature range of 20-90 ℃, dihydroxy-terminated polyether modified polydimethylsiloxane (HO-PDMS-OH) firstly reacts with isophorone diisocyanate (IPDI) to generate an IPDI-terminated intermediate product, and then hydroxyethyl methacrylate (HEMA) is added for continuous reaction to obtain the double-terminated organic siloxane oligomer. Wherein the catalyst is dibutyltin dilaurate.
Wherein, the value range of a is an integer between 4 and 20, and the value range of b is an integer between 5 and 100.
Experiments prove that the single-end-capped and double-end-capped organic siloxane oligomer has better effect when used in a composite way than any one of the single-end-capped and double-end-capped organic siloxane oligomers when used alone, has obvious synergistic effect, and further improves the oxygen permeability, the hydrophilic performance, the lipid precipitation resistance and other performances of the silicon hydrogel. The oxygen permeability of the silicon hydrogel material is related to the structure and the addition of the silicon-containing monomer and the microphase separation of the material, the formation of the continuous organic silicon phase is the key for improving the oxygen permeability of the material, and when the single-end-capped organic siloxane oligomer and the double-end-capped organic siloxane oligomer are compounded for use, the structures of the organic silicon phase and the double-end-capped organic silicon oligomer are similar and compatible, so that the formation of the continuous silicon phase of the hydrogel material is facilitated, and a higher oxygen permeability value can be obtained.
The micromolecular silicon monomer is one or any combination of methacryloxy methyl tri (trimethylsiloxy) silane (MTTS), methacryloxypropyl tri (trimethylsiloxy alkyl) silane (TRIS), gamma-aminopropyltriethoxysilane (KH-550), 3- (methacryloxy) propyltrimethoxysilane (KH-570) and 3- (3-methacryloxy-2-hydroxypropyl) propylbis (trimethylsiloxane) methylsilane (SIGMA). The micromolecule silicon monomer is used as a solubilizing monomer in the silicon hydrogel, so that the intermiscibility of the siloxane macromonomer and the hydrophilic monomer can be increased, and meanwhile, the micromolecule silicon monomer has a certain effect on improving the oxygen permeability.
Because the single-end-capped and double-end-capped organic siloxane oligomers used in the invention both contain hydrophilic polyether structures and highly oxygen-permeable polysiloxane structures, the structures of the two are similar, and the intermiscibility is good, and the single-end-capped and double-end-capped organic siloxane oligomers can be well mutually dissolved with hydrophilic monomers without adding micromolecular silicon monomers for solubilization when the single-end-capped and double-end-capped organic siloxane oligomers are compounded for use, so that the silicon hydrogel material with good light transmittance is obtained. In fact, the small molecule silicon monomer can be added or not added according to the requirement in the actual production. In a more preferred embodiment, no small molecule silicon monomer is added to the formulation.
The hydrophilic monomer is one or a combination of more of N-vinyl pyrrolidone (NVP), vinyl cyclohexane amide (NVCA), polyether methacrylate, methacrylic acid (MAA), hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA), hydroxybutyl methacrylate, glycerol methacrylate, glycidyl methacrylate, N-Dimethylacrylamide (DMA), N-vinyl acetamide (NVA) and N-vinyl methylacetamide. The performance characteristics of each hydrophilic monomer are different, and the excellent performance of each monomer can be fully exerted by using a plurality of monomers in a composite way.
The initiator is a photoinitiator or a thermal initiator. The photoinitiator is at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl phenyl acetone (D1173) and 2,4, 6-trimethylbenzyl diphenyl phosphine oxide, and the thermal initiator is at least one of Azobisisobutyronitrile (AIBN), azobisisoheptonitrile (AIBN) and Benzoyl Peroxide (BPO).
The cross-linking agent is at least one of triallyl isocyanurate (TAIC), vinyl methacrylate, ethylene Glycol Dimethacrylate (EGDMA), triethylene glycol dimethacrylate, polyethylene glycol diacrylate (PEGDA), tetraethylene glycol dimethacrylate, polyethylene glycol divinyl ether and trimethylolpropane trimethacrylate.
In actual production, other functional monomers can be added to the silicone hydrogel material according to needs, such as monomers containing colored monomers, color-changing monomers or monomers for blocking ultraviolet light, blue light and near infrared light.
The single-end-capped and double-end-capped organic siloxane oligomer has excellent hydrophilic performance and can be mixed with various hydrophilic monomers well without solvent for assisting dissolution, so the silicon hydrogel of the invention has no solvent added in the formula, which is a great advantage for large-scale industrial production.
On the other hand, the single-end-capped and double-end-capped organic siloxane oligomer and the hydrophilic monomer are well dissolved mutually, so that the single-end-capped and double-end-capped organic siloxane oligomer and the hydrophilic monomer can be added into the silicon hydrogel in a large proportion, the addition of PDMS is greatly increased, and the oxygen permeability of the silicon hydrogel is greatly improved. The addition total amount of the single-end-capped and double-end-capped organic siloxane oligomer in the silicon hydrogel is at least more than 30 percent, the organic siloxane oligomer at least accounts for 30 percent of the total weight of the silicon hydrogel, and the organic siloxane oligomer of the commercial products can be added by about 20 percent generally and is far lower than the addition level of the invention.
The invention effectively solves the problem that organic siloxane oligomer and hydrophilic monomer are difficult to dissolve mutually, and greatly improves the oxygen permeability of the silicon hydrogel on the premise of keeping high water content, thereby realizing the aim that the silicon hydrogel material has high oxygen permeability and high water content and greatly improving the performance of the silicon hydrogel material. Experiments show that the water content of the silica hydrogel prepared by the invention is 30-45%; the oxygen permeability reaches more than 190barrer, even reaches more than 240barrer, and is obviously higher than that of a silicon hydrogel contact lens sold in the market; moreover, the lipid adsorption is very low and is lower than 0.0029 mg/tablet, which shows that the lens prepared by the invention has excellent lipid adsorption resistance; meanwhile, the elongation at break reaches more than 190%, which shows that the lens prepared by the invention has good flexibility.
The invention also provides a corneal contact lens made of the silicon hydrogel material. The corneal contact lens is prepared by the following method:
uniformly mixing 20-60 parts of single-end-capped organic siloxane oligomer of formula (I), 10-50 parts of double-end-capped organic siloxane oligomer of formula (II), 0-30 parts of small molecular silicon monomer, 5-70 parts of hydrophilic monomer, initiator and cross-linking agent, injecting into a corneal contact lens mold, carrying out photo-initiated or thermal-initiated polymerization curing, and hydrating to obtain the silicon hydrogel corneal contact lens; wherein the sum of the mass parts of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer; the cross-linking agent accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer.
The cornea contact lens is made of the silicon hydrogel material, and the silicon hydrogel material has good oxygen permeability and light transmittance, keeps high hydrophilicity and flexibility of gel, and has good lipid precipitation resistance. The corneal contact lens prepared by the silicon hydrogel is comfortable to wear, good in flexibility and high in oxygen permeability, can reduce the incidence of ophthalmic diseases caused by oxygen deficiency, and is beneficial to eye health; the good light transmission performance ensures the visual effect and comfort of wearing.
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
The experimental procedures used above and in the examples below are conventional unless otherwise specified.
The materials, reagents and the like used above and in the following examples are commercially available unless otherwise specified.
Example 1
Preparation of single-end-capped organosiloxane oligomer
50g of monohydroxy-terminated polyether modified polydimethylsiloxane (HO-PDMS, number average molecular weight of about 1500, structural formula shown above, wherein m is about 8, n is about 15, and purchased from Nanjing Fugu chemical Co., ltd.) is taken, 0.3g of dibutyltin dilaurate is added dropwise, the mixture is stirred uniformly, 7.41g of IPDI is gradually added, a constant temperature water bath heating device is opened at the same time, the temperature is adjusted to be 70 ℃, timing is started after the dropwise addition is completed, and the reaction is carried out for 4 hours. Cooling to 50 deg.C, adding HEMA monomer 4.34g, stirring for 24 hr to obtain product M1 (formula is shown as formula (I), wherein M is about 8, n is about 15), and sealing for storage. FIG. 1 is a nuclear magnetic spectrum of a single end-capped organosiloxane oligomer prepared in example 1.
Example 2
Preparation of mono-end-capped organosiloxane oligomers
50g of monohydroxy-terminated polyether modified polydimethylsiloxane (HO-PDMS, number average molecular weight of about 3000, structural formula shown above, wherein m is about 10, n is about 35, and purchased from Nanjing Fugu chemical Co., ltd.) is taken, 0.2g of dibutyltin dilaurate is added dropwise, the mixture is stirred uniformly, 3.71g of IPDI is gradually added, a constant temperature water bath heating device is opened at the same time, the temperature is adjusted to be 70 ℃, timing is started after the dropwise addition is completed, and the reaction is carried out for 4 hours. Cooling to 50 deg.C, adding 2.17g HEMA monomer dropwise, stirring for 24h to obtain product M2 (formula is shown as formula (I), wherein M is about 10, n is about 35), and sealing for storage.
Example 3
Preparation of double-end-capped organic siloxane oligomer
Taking 50g of dihydroxy-terminated polyether modified polydimethylsiloxane (HO-PDMS-OH, the number average molecular weight is 5500, the structural formula is shown as the above, wherein a is about 11, b is about 50, and the structural formula is purchased from Nanjing Fuqun chemical Co., ltd.), dropwise adding 0.2g of dibutyltin dilaurate, stirring uniformly, gradually adding IPDI 4.042g, simultaneously opening a constant-temperature water bath heating device, adjusting the temperature to 85 ℃, starting timing after the dropwise addition is completed, and reacting for 4h. Cooling to 50 deg.C, adding 2.366g HEMA monomer, stirring for 24 hr to obtain product M3 (formula is shown as formula (II), wherein a is about 11, b is about 50), sealing, and storing. FIG. 2 is a nuclear magnetic spectrum of a double-end-capped organosiloxane oligomer prepared in example 3.
Example 4
Preparation of double-end-capped organic siloxane oligomer
30g of dihydroxy-terminated polyether modified polydimethylsiloxane (HO-PDMS-OH, the number average molecular weight is about 8000, the structural formula is shown as the above, wherein a is about 15, b is about 90 and is purchased from Nanjing Fuqu chemical Co., ltd.), 0.15g of dibutyltin dilaurate is added dropwise, the mixture is stirred uniformly, 1.67g of IPDI is gradually added, a constant temperature water bath heating device is opened at the same time, the temperature is adjusted to 90 ℃, timing is started after the dropwise addition is completed, and the reaction is carried out for 4 hours. Cooling to 50 deg.C, adding 0.97g HEMA monomer dropwise, stirring for 24h to obtain product M4 (formula shown in formula (II), wherein a is about 15 and b is about 90), and sealing for storage.
Examples 5 to 8
A silicone hydrogel prepared by polymerization of:
in examples 5-8, the single end-capped organosiloxane oligomers were prepared from examples 1 or 2, respectively, and the double end-capped organosiloxane oligomers were prepared from examples 3 or 4, respectively, with the other components and parts unchanged.
Examples 9 to 16
Preparation of corneal contact lenses
Uniformly mixing the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer, the hydrophilic monomer, the initiator and the cross-linking agent, injecting the mixture into a corneal contact lens mold, carrying out thermal initiation polymerization, then demolding, and hydrating to obtain the silicon hydrogel corneal contact lens. The contact lens is made to have an anterior surface and a posterior surface.
Wherein the single-end-capped organosiloxane oligomers were prepared in examples 1 and 2, respectively, and the double-end-capped organosiloxane oligomers were prepared in examples 3 and 4, respectively; the small molecular silicon monomer adopts 3- (3-methacryloxy-2-hydroxypropyl) propyl bis (trimethyl siloxane) methyl Silane (SIGMA); the hydrophilic monomer adopts N-vinyl pyrrolidone (NVP), vinyl cyclohexane amide (NVCA) and hydroxypropyl methacrylate (HPMA); the initiator adopts Azobisisobutyronitrile (AIBN); the cross-linking agent is Ethylene Glycol Dimethacrylate (EGDMA). The contact lenses of examples 9-16 were prepared according to the above procedure, and their respective reaction components and formulation relationships (in parts by mass) are shown in table 1.
Comparative examples 1 to 4
Comparative examples 1-4 were prepared according to the methods of examples 9-16, based on the formulations of examples 9, 10, 11, 12, with the reaction components and ratios listed in Table 1, by replacing the single-ended organosiloxane oligomer (prepared from example 1 or 2) or the double-ended organosiloxane oligomer (prepared from example 3 or 4) with the other components and parts.
Example 17
The corneal contact lenses prepared in examples 9 to 16 and comparative examples 1 to 4 were tested for elongation using an electronic tensile tester XLW (PC), respectively. The samples were held by respective holding plates and measured for elongation at break, and the results are shown in Table 1.
The oxygen permeability of the corneal contact lenses prepared in examples 9 to 16 and comparative examples 1 to 4 was measured by national standard (GBT 11417.3 to 2012) coulometry, and the results are shown in Table 1.
The moisture content of the contact lenses prepared in examples 9 to 16 and comparative examples 1 to 4, the weight of the glass slide Q1, the weight of the lens and the glass slide Q2, and the gross weight G3 and the moisture content = (Q2-G3)/(Q2-Q1) after drying in an oven at 50 ℃ to constant weight were measured by a weighing method, respectively, and the test results are shown in table 1.
The lipid adsorption of examples 9-16 and comparative examples 1-4 was examined by the ferric alum chromogenic method in the presence of lipid, and then the amount of lipid adsorption was examined by an evolution220 spectrophotometer.
TABLE 1 reaction Components and ratios (in parts by mass) and Properties of examples 9-16 and comparative examples 1-4
The performance comparison of examples 9, 10, 11 and 12 with comparative examples 1 to 4 respectively shows that the single-end-capped and double-end-capped organosiloxane oligomers are used in a composite manner, compared with the single-end-capped and double-end-capped organosiloxane oligomers, the obtained corneal contact lens has obviously higher oxygen permeability, obviously higher elongation at break, improved water content and obviously lower lipid adsorption value, which shows that the single-end-capped and double-end-capped organosiloxane oligomers have obvious synergistic interaction, the oxygen permeability and elongation at break of the material are obviously improved, and the lipid adsorption value is obviously reduced.
The oxygen permeability of the corneal contact lenses prepared in the embodiments 9 to 16 of the invention is over 190barrer, and some of the oxygen permeability is even over 240 barrer; meanwhile, the lipid adsorption of the corneal contact lens is very low and is lower than 0.0029 mg/lens, which shows that the lens prepared by the invention has excellent lipid adsorption resistance; the elongation at break reaches more than 190%, which shows that the lens prepared by the invention has good flexibility, is durable and is not easy to break.
It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are intended to further illustrate the principles of the invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention, which is also intended to be covered by the appended claims. The scope of the invention is defined by the claims and their equivalents.
Claims (9)
1. The silicone hydrogel is characterized by comprising the following components in parts by mass and prepared through polymerization reaction:
an initiator and a crosslinking agent;
wherein the sum of the mass parts of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer; the cross-linking agent accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer;
the single-end-capped organic siloxane oligomer has a structure shown in a formula (I):
wherein m is an integer ranging from 4 to 20, n is an integer ranging from 5 to 100, and R is C 1 -C 10 Alkyl groups of (a);
the double-end-capped organic siloxane oligomer has a structure shown in a formula (II):
wherein, the value range of a is an integer between 4 and 20, and the value range of b is an integer between 5 and 100.
2. The silicone hydrogel of claim 1, wherein the one-end-capped organosiloxane oligomer of formula (I) is prepared by: under the action of a catalyst, in the temperature range of 20-90 ℃, the monohydroxy terminated polyether modified polydimethylsiloxane firstly reacts with isophorone diisocyanate, and then hydroxyethyl methacrylate is added for continuous reaction to obtain the mono-terminated organic siloxane oligomer shown in the formula (I).
3. The silicone hydrogel of claim 1, wherein the double-capped organosiloxane oligomer of formula (II) is prepared by: under the action of a catalyst, in the temperature range of 20-90 ℃, the dihydroxy terminated polyether modified polydimethylsiloxane firstly reacts with isophorone diisocyanate, and then hydroxyethyl methacrylate is added for continuous reaction to obtain the dihydroxy terminated organic siloxane oligomer shown in the formula (II).
4. The silicone hydrogel of any one of claims 1-3, wherein the small molecule silicon monomer is one or any combination of methacryloxymethyltris (trimethylsiloxy) silane, methacryloxypropyltris (trimethylsiloxy) silane, γ -aminopropyltriethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, and 3- (3-methacryloxy-2-hydroxypropyl) propylbis (trimethylsiloxane) methylsilane.
5. The silicone hydrogel of any one of claims 1-3, wherein the hydrophilic monomer is one or a combination of N-vinylpyrrolidone, vinylcyclohexamide, polyether methacrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, glycerol methacrylate, glycidyl methacrylate, N-dimethylacrylamide, N-vinylacetamide and N-vinylmethylacetamide.
6. The silicone hydrogel of any one of claims 1-3, wherein said initiator is a photoinitiator or a thermal initiator; the photoinitiator is at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl propiophenone and 2,4, 6-trimethylbenzyl diphenyl phosphine oxide, and the thermal initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile and benzoyl peroxide.
7. The silicone hydrogel of any of claims 1-3, wherein said cross-linking agent is at least one of triallylisocyanurate, vinyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol divinyl ether, and trimethylolpropane trimethacrylate.
8. A corneal contact lens made from the silicone hydrogel of any one of claims 1 to 7.
9. A method of making a corneal contact lens as claimed in claim 8, comprising: uniformly mixing 20-60 parts of single-end-capped organic siloxane oligomer of formula (I), 10-50 parts of double-end-capped organic siloxane oligomer of formula (II), 0-30 parts of small molecular silicon monomer, 5-70 parts of hydrophilic monomer, initiator and cross-linking agent, injecting into a corneal contact lens mold, carrying out photo-initiated or thermal-initiated polymerization curing, and hydrating to obtain the silicon hydrogel corneal contact lens; wherein the sum of the mass parts of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer; the cross-linking agent accounts for 0.5 to 3 percent of the weight sum of the single-end-capped organic siloxane oligomer, the double-end-capped organic siloxane oligomer, the micromolecular silicon monomer and the hydrophilic monomer.
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