WO2022141794A1 - 单封端两亲性有机硅氧烷大分子单体、硅水凝胶、角膜接触镜及制备方法 - Google Patents

单封端两亲性有机硅氧烷大分子单体、硅水凝胶、角膜接触镜及制备方法 Download PDF

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WO2022141794A1
WO2022141794A1 PCT/CN2021/079427 CN2021079427W WO2022141794A1 WO 2022141794 A1 WO2022141794 A1 WO 2022141794A1 CN 2021079427 W CN2021079427 W CN 2021079427W WO 2022141794 A1 WO2022141794 A1 WO 2022141794A1
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organosiloxane
amphiphilic
capped
monomers
macromonomer
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PCT/CN2021/079427
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English (en)
French (fr)
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张雪勤
吴姝
陈平
韩雪莲
王玉东
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江苏海伦隐形眼镜有限公司
东南大学
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Publication of WO2022141794A1 publication Critical patent/WO2022141794A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04—Contact lenses for the eyes
    • G02C7/049—Contact lenses having special fitting or structural features achieved by special materials or material structures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the invention relates to a single-end-capped amphiphilic organosiloxane macromonomer, a silicon hydrogel, a corneal contact lens and a preparation method, and belongs to the field of material preparation of contact lens lenses.
  • hydrogel contact lenses are copolymerized with hydrophilic monomers such as hydroxyethyl methacrylate, N-vinylpyrrolidone, etc.
  • hydrophilic monomers such as hydroxyethyl methacrylate, N-vinylpyrrolidone, etc.
  • corneal hypoxia There is a general low oxygen permeability, and long-term wearing will cause corneal hypoxia. , resulting in ocular surface problems such as dry eyes, conjunctival hyperemia, and corneal edema.
  • Silicon hydrogel is a new type of material obtained by introducing silicone structural units into hydrogels. It combines the high oxygen permeability of silicone and the softness of hydrogels, and has higher oxygen permeability than hydrogels. ability, which has been used as one of the materials for contact lenses in recent years. For those who wear contact lenses for a long time and those who are prone to dry eyes, silicone hydrogel contact lenses have huge advantages. In recent years, the contact lens market has rapidly changed from hydrogel to silicone hydrogel. Currently, more than half of the contact lenses in the global market are silicone hydrogel lenses.
  • Silicone hydrogel lenses are generally copolymerized by silicone monomers and hydrophilic monomers, and usually contain one or more of low molecular weight silicone monomers or larger molecular weight silicone oligomers.
  • Small molecule silicone monomers such as methacryloxypropyl tris(trimethylsiloxane) silane (TRIS), methyl-bis(trimethylsiloxane)-silylpropylmethyl Glyceryl acrylate (SIGMA), etc., have good hydrophilicity and good compatibility with hydrophilic monomers, but their effect on improving the oxygen permeability of the material is limited.
  • Organosilicon oligomers with larger molecular weight are generally obtained by grafting reactive functional groups to polydimethylsiloxane (PDMS).
  • PDMS molecules have a helical three-dimensional structure, with small intermolecular forces and low cohesive energy density. , the structure is loose, so this material has high air permeability.
  • the introduction of reactive PDMS oligomers into the hydrogel structure can greatly improve the oxygen permeability of silicon hydrogels.
  • the amount of PDMS added is limited, which limits the improvement of the oxygen permeability value of the lens material, and the obtained silicone hydrogel surface has strong hydrophobicity , affecting the wearing comfort of the lens.
  • the object of the present invention is to provide a single-end-capped amphiphilic organosiloxane macromonomer, which is excellent in mutual miscibility with various hydrophilic monomers without solvent-assisted solubilization, and can prepare high hydrophilicity and high oxygen permeability silicon hydrogel; at the same time, a silicon hydrogel material and a corneal contact lens are also provided, which have good oxygen permeability, light transmittance, strong hydrophilicity, and are comfortable to wear.
  • the present invention provides a single-end-capped amphiphilic organosiloxane macromonomer, which has the structure shown in formula (I):
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a C 1 -C 10 alkyl group
  • the value of m is an integer in the range of 5-20
  • the value of n is an integer in the range of 5-100 .
  • the present invention provides a method for preparing the single-terminated amphiphilic organosiloxane macromonomer, comprising: polyether-modified polydimethylsiloxane and (meth)acrylic isocyanate terminated by hydroxyl groups, Under the action of the catalyst, the reaction is formed in the temperature range of 20 to 80 °C.
  • the single-end-capped amphiphilic organosiloxane macromonomer is used to prepare silicone hydrogels and contact lenses.
  • the present invention also provides a silicone hydrogel, comprising the single-end-capped amphiphilic organosiloxane macromonomer and the following components, which are prepared by polymerization in parts by mass:
  • the single-end-capped amphiphilic organosiloxane macromonomer is one or a combination of the two structures shown in formula (I);
  • the sum of the mass fractions of bulk, small molecular silicon monomers and hydrophilic monomers is 100; 0.5-3% of the weight of the sum of the monomers;
  • the cross-linking agent accounts for 0.5-3% of the weight of the single-end amphiphilic organosiloxane macromonomer, the small-molecule silicon monomer and the hydrophilic monomer.
  • the small-molecule silicon monomer is methacryloyloxypropyl tris(trimethylsiloxane) silane, methyl-bis(tri(trimethylsiloxane) silane) Methylsiloxane)-silylpropyl glycerol methacrylate, 3-(methacryloyloxy)propyltrimethoxysilane and methacryloxymethyltris(trimethylsiloxane) base) one or any combination of silanes.
  • the hydrophilic monomer is N-vinylpyrrolidone, hydroxypropyl methacrylate, N,N-dimethylacrylamide, methyl methacrylate
  • the hydrophilic monomer is N-vinylpyrrolidone, hydroxypropyl methacrylate, N,N-dimethylacrylamide, methyl methacrylate
  • the initiator is a photoinitiator or a thermal initiator
  • the photoinitiator is 2-hydroxy-2-methylpropiophenone, 1- At least one of hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2,4,6-trimethylbenzyldiphenylphosphine oxide
  • the thermal initiators described are azobisisobutyronitrile, benzoyl peroxide, azobisisoheptyl cyanide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate and bis( at least one of 2-phenylethoxy) esters.
  • the crosslinking agent is polyethylene glycol diacrylate, ethylene glycol dimethacrylate, triallyl isocyanurate, dimethacrylate Triethylene Glycol Methacrylate, Tetraethylene Glycol Dimethacrylate, Diethylene Glycol Divinyl Ether, Vinyl Methacrylate, Divinyl Polyethylene Glycol, and Trimethylolpropane Trimethyl One or any combination of base acrylates.
  • the present invention also provides a corneal contact lens, which is made of the above-mentioned silicone hydrogel.
  • the present invention also provides a preparation method of the corneal contact lens, comprising: mixing 5-60 parts of the single-end-capped amphiphilic organosiloxane macromonomer of formula (I) and 0 parts of a small molecular silicon monomer.
  • hydrophilic monomer ⁇ 30 parts, 10-70 parts of hydrophilic monomer, initiator and cross-linking agent are mixed evenly, injected into contact lens mold, photo-induced or thermally-induced polymerization and curing, and hydrated to obtain contact lens;
  • the sum of the parts by mass of the amphiphilic organosiloxane macromonomer, the small molecular silicon monomer and the hydrophilic monomer is 100 parts;
  • the initiator accounts for the single end-capped amphiphilic organosiloxane macromonomer 0.5 to 3% of the weight of the sum of , small molecular silicon monomers and hydrophilic monomers;
  • the cross-linking agent accounts for the single end-capped amphiphilic organosiloxane macromonomers, small molecular silicon monomers and hydrophilic monomers 0.5 to 3% of the total weight.
  • the organosiloxane macromonomer provided by the present invention has a single-end capped structure, that is, only one end contains a double bond functional group with polymerization activity. Compared with organosiloxane macromonomers containing two or more double bonds, the crosslinking degree of the polymer is significantly reduced, thereby effectively improving the hydrophilicity and water content of organosiloxane macromonomers .
  • the single-end amphiphilic organosiloxane macromonomer of the present invention is a block copolymer with a longer polyether segment, so that the organosiloxane macromonomer has excellent hydrophilicity It has good mutual solubility with hydrophilic monomers, and can be added to silicon hydrogels in a large proportion without adding co-solvents, effectively solving the mutual miscibility of organosiloxane macromonomers and hydrophilic monomers. Therefore, the prepared silicone hydrogel has high hydrophilicity, high oxygen permeability and good light transmittance at the same time.
  • the silicon hydrogel material prepared by the present invention has excellent oxygen permeability and light transmittance, while maintaining the hydrophilicity and flexibility of the gel.
  • the corneal contact lens prepared by the present invention 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.
  • FIG. 1 is the nuclear magnetic spectrum of the single-end-capped amphiphilic organosiloxane macromonomer (M1-w1) prepared in Example 1.
  • FIG. 1 is the nuclear magnetic spectrum of the single-end-capped amphiphilic organosiloxane macromonomer (M1-w1) prepared in Example 1.
  • FIG. 2 is the nuclear magnetic spectrum of the single-end-capped amphiphilic organosiloxane macromonomer (M1-w2) prepared in Example 2.
  • FIG. 2 is the nuclear magnetic spectrum of the single-end-capped amphiphilic organosiloxane macromonomer (M1-w2) prepared in Example 2.
  • the inventors of the present invention have found through long-term research that the single-terminated organosiloxane macromonomer structure has higher water content and better hydrophilicity than the double-terminated structure; in addition, increasing the length of the polyether segment can The hydrophilicity of the organosiloxane macromonomer is obviously improved, so that the addition amount of the organosiloxane macromonomer in the silicone hydrogel can be increased in a large proportion.
  • the silicone hydrogel prepared from the single-terminated organosiloxane macromonomer has both high oxygen permeability and high hydrophilicity, and the corneal contact lens prepared from it has high oxygen permeability, good light transmittance, and hydrophilicity. Strong and comfortable to wear.
  • the double-terminated organosiloxane macromonomer needs the participation of a co-solvent to achieve good mutual solubility with the hydrophilic monomer.
  • the inventors of the present invention found that the single-terminated organosiloxane macromonomer is in the It can be well mixed with various hydrophilic monomers under the condition that no solvent is needed for co-dissolution, avoids the use of solvents, and is beneficial to large-scale industrial production, so the beneficial effect of the present invention is very significant.
  • the structure of the single-terminated organosiloxane macromonomer provided by the present invention and the silicon hydrogel prepared therefrom have not been reported in the literature.
  • the present invention provides a single-end-capped amphiphilic organosiloxane macromonomer, which has the structure shown in formula (I):
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a C 1 -C 10 alkyl group
  • the value of m is an integer in the range of 5-20
  • the value of n is an integer in the range of 5-100 .
  • the value range of m is an integer between 7-12
  • the value range of n is an integer between 12-50.
  • the single-ended amphiphilic organosiloxane macromonomer of the above formula (I) is a block copolymer, wherein the polysiloxane segment (1) can effectively improve the oxygen permeability of the silicone hydrogel material, and the polysiloxane segment (1) can effectively improve the oxygen permeability of the silicone hydrogel material.
  • the ether segment (2) and the acrylate-based end capping group (3) have good hydrophilicity.
  • only one end of the formula (I) has a double-bond functional group with polymerization activity, which greatly reduces the cross-linking degree of the polymer and makes the formed polymer network structure have a larger mesh. Therefore, It locks in more water, thereby increasing the water content and hydrophilicity of the polymer.
  • the length m of the polyether segment (2) has an important influence on the hydrophilicity of the polymer. If the value of m is too small (m ⁇ 5), the compatibility between the organosiloxane macromonomer and the hydrophilic monomer is poor, and it is difficult to add a large proportion to the silicone hydrogel, and the prepared silicone hydrogel is oxygen permeable.
  • the hydrophilicity of the organosiloxane macromonomer is obviously improved, and the oxygen permeability of the prepared silicone hydrogel is greatly improved, reaching more than 100 barrer, or even It can reach more than 160barrer, which shows that appropriately increasing the length of the polyether segment can significantly improve the hydrophilicity of the polymer, so that the organosiloxane macromonomer and the hydrophilic monomer are mutually miscible, and can be added to the silicon water in a large proportion.
  • the organosiloxane macromonomer is paste-like, which affects the light transmission performance of the lens, so it cannot be used to prepare contact lenses.
  • Mono-capped amphiphilic organosiloxane macromonomers of formula (I) can be prepared by the following methods:
  • HO-PDMS Hydroxyl-terminated polyether-modified polydimethylsiloxane
  • IEM (meth)acrylic isocyanate
  • the catalyst may be at least one of dibutyltin dilaurate, trifluoromethanesulfonic acid, triethylamine or tetrabutylammonium chloride.
  • HO-PDMS and IEM were reacted in equal proportions.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a C 1 -C 10 alkyl group
  • the value of m is an integer in the range of 5-20
  • the value of n is an integer in the range of 5-100 .
  • the present invention provides a silicone hydrogel, comprising the following components, in parts by mass, prepared by a polymerization reaction:
  • the sum of the mass fractions of single-terminated amphiphilic organosiloxane macromonomers, small molecular silicon monomers and hydrophilic monomers is 100 parts; 0.5-3% of the total weight of alkyl macromonomers, small molecular silicon monomers and hydrophilic monomers; 0.5 to 3% of the total weight of hydrophilic monomers.
  • the mass fraction of the single-terminated amphiphilic organosiloxane macromonomer is 29-60 parts.
  • the mono-terminated amphiphilic organosiloxane macromonomers of formula (I) are as described above.
  • the mono-terminated amphiphilic organosiloxane macromonomer is one or a combination of the two structures represented by formula (I).
  • the small molecular silicon monomer can be methacryloyloxypropyl tris(trimethylsiloxane) silane (TRIS), methyl-bis(trimethylsiloxane)-silyl propylene glyceryl methacrylate (SIGMA), 3-(methacryloyloxy)propyltrimethoxysilane (KH570) and methacryloxymethyltris(trimethylsiloxy)silane (MTTS) one or any combination.
  • TIS methacryloyloxypropyl tris(trimethylsiloxane) silane
  • SIGMA methyl-bis(trimethylsiloxane)-silyl propylene glyceryl methacrylate
  • KH570 3-(methacryloyloxy)propyltrimethoxysilane
  • MTTS methacryloxymethyltris(trimethylsiloxy)silane
  • the hydrophilic monomer can be N-vinylpyrrolidone (NVP), hydroxypropyl methacrylate (HPMA), N,N-dimethylacrylamide (DMA), hydroxyethyl methacrylate (HEMA) ), methacrylic acid (AA), N-vinylacetamide (NVA), one of glycerol methacrylate, glycidyl methacrylate, hydroxybutyl methacrylate, N-vinylmethylacetamide one or a combination of several.
  • NVP N-vinylpyrrolidone
  • HPMA hydroxypropyl methacrylate
  • DMA N,N-dimethylacrylamide
  • HEMA hydroxyethyl methacrylate
  • AA methacrylic acid
  • N-vinylacetamide N-vinylacetamide
  • the performance characteristics of each hydrophilic monomer are different, and the composite use of multiple monomers can give full play to the excellent performance of each monomer.
  • the initiator can be a photoinitiator or a thermal initiator.
  • the photoinitiator can be 2-hydroxy-2-methylpropiophenone (D1173), 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and At least one of 2,4,6-trimethylbenzyldiphenylphosphine oxide;
  • the thermal initiator can be azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), At least one of diisoheptyl peroxydicarbonate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and bis(2-phenylethoxy) peroxydicarbonate.
  • the crosslinking agent can be polyethylene glycol diacrylate (PEGDA), ethylene glycol dimethacrylate (EGDMA), triallyl isocyanurate (TAIC), triethylene dimethacrylate
  • PEGDA polyethylene glycol diacrylate
  • EGDMA ethylene glycol dimethacrylate
  • TAIC triallyl isocyanurate
  • triethylene dimethacrylate One of alcohol ester, tetraethylene glycol dimethacrylate, diethylene glycol divinyl ether, vinyl methacrylate, divinyl polyethylene glycol ester and trimethylolpropane trimethacrylate species or any combination.
  • silicone hydrogel material in actual production, other functional monomers can also be added to the silicone hydrogel material as required, such as containing colored monomers, color-changing monomers or monomers that block ultraviolet light, blue light, and near-infrared light.
  • the organosiloxane macromonomer of formula (I) has excellent hydrophilicity, it has good compatibility with hydrophilic monomers, and does not require solvent to help dissolve, so no solvent is added to the silicone hydrogel formulation of the present invention. , 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. Adding organic solvents not only increases production and recovery costs, but also causes environmental pollution. More importantly, in the process of preparing lenses through the polymerization of mixed monomers, whether it is thermal polymerization or photopolymerization, a large amount of solvent will be volatilized into the air. When the solvent concentration in the air exceeds a certain value, it will not only affect the health of operators, but also There is a danger of explosion, burning, etc.
  • organosiloxane macromonomers and hydrophilic monomers have good mutual solubility, they can be added to the silicone hydrogel in a large proportion, thereby greatly improving the oxygen permeability of the silicone hydrogel.
  • the added amount of the organosiloxane macromonomer in the silicone hydrogel of the present invention is 5-60%, and the organosiloxane macromonomer accounts for almost 5-60% of the total weight of the silicone hydrogel, that is to say , the present invention can achieve the addition of the organosiloxane macromonomer to more than 40%, while the commercially available products can only add about 20% of the organosiloxane macromonomer, which is far lower than the addition of the present invention. Level.
  • the invention effectively solves the problem that the organopolysiloxane macromonomer and the hydrophilic monomer are difficult to dissolve in each other, and greatly improves the oxygen permeability of the silicon hydrogel on the premise of maintaining a relatively high water content, thereby realizing the Hydrogel materials have the goals of high oxygen permeability and high water content, which greatly improves the performance of silicone hydrogel materials.
  • the water content of the silicone hydrogel of the present invention is 30-50%, and the oxygen permeability can reach more than 100 barrer, even more than 160 barrer, which is significantly higher than that of the silicone hydrogel made of double-terminated organopolysiloxane macromonomers. Silicone hydrogel material.
  • the present invention also provides a corneal contact lens made of the above-mentioned silicon hydrogel material.
  • the contact lens is prepared by the following method:
  • the corneal contact lens of the present invention is made of the above-mentioned silicon hydrogel material.
  • the silicon hydrogel material retains the high hydrophilicity of the hydrogel material, and has good anti-lipid deposition performance and biocompatibility. Comfortable; high oxygen permeability can reduce the incidence of ophthalmic diseases caused by hypoxia, which is beneficial to eye health; good light transmission performance ensures the visual effect and comfort of wearing.
  • HO-PDMS number average molecular weight is about 1500, where m is about 7 and n is about 16, purchased from Nanjing Fuqun Chemical Co., Ltd.
  • CH 2 Cl 2 dichloromethane
  • dilaurel 0.1 g of dilaurel
  • FIG. 1 is the nuclear magnetic spectrum of the single-end-capped amphiphilic organosiloxane macromonomer (M1-w1) prepared in Example 1.
  • FIG. 1 is the nuclear magnetic spectrum of the single-end-capped amphiphilic organosiloxane macromonomer (M1-w1) prepared in Example 1.
  • HO-PDMS number average molecular weight is about 5500, wherein m is about 11, n is about 50, purchased from Nanjing Fuqun Chemical Co., Ltd.
  • 80 mL CH 2 Cl 2 and 0.2 g dibutyltin dilaurate stir well mixed. Then weigh the corresponding proportion of IEM and CH 2 Cl 2 and mix, add the constant pressure dropping funnel, and add the mixture of IEM and CH 2 Cl 2 dropwise to the reaction.
  • the constant temperature water bath heating device was turned on, the temperature was adjusted to 55°C, and the reaction was carried out for 10 hours.
  • FIG. 2 is the nuclear magnetic spectrum of the single-end-capped amphiphilic organosiloxane macromonomer (M1-w2) prepared in Example 2.
  • a silicone hydrogel prepared by polymerization of the following components:
  • the single-end-capped amphiphilic organosiloxane macromonomer was prepared from Example 1 and Example 2, respectively.
  • the single-end-capped amphiphilic organosiloxane macromonomer, together with the small molecular silicon monomer, hydrophilic monomer, initiator and cross-linking agent are mixed uniformly, injected into the contact lens mold, and the polymerization is initiated by light or heat. , and then demolded, and the silicone hydrogel contact lens was prepared after hydration.
  • the resulting contact lens has an anterior surface and a posterior surface.
  • the single-end-capped amphiphilic organosiloxane macromonomer was prepared from Example 1 or Example 2, and the small molecular silicon monomer was methyl-bis(trimethylsiloxane)-silylpropane glycerol methacrylate (SIGMA), the hydrophilic monomer is hydroxyethyl methacrylate (HEMA), N-vinylacetamide (NVA), hydroxypropyl methacrylate (HPMA), and the initiator is 2- Hydroxy-2-methylpropiophenone (D1173), and ethylene glycol dimethacrylate (EGDMA) as the cross-linking agent.
  • SIGMA small molecular silicon monomer
  • HEMA hydroxyethyl methacrylate
  • NVA N-vinylacetamide
  • HPMA hydroxypropyl methacrylate
  • the initiator is 2- Hydroxy-2-methylpropiophenone
  • EGDMA ethylene glycol dimethacrylate
  • a contact lens was prepared according to the method of Example 5-12, and the reaction The components and proportions are shown in Table 1, and other reaction conditions remain unchanged.
  • the molecular formula of the double-terminated organosiloxane macromonomer M2-w1 is as follows:
  • the oxygen permeability values of the contact lenses prepared in Examples 5-12 and Comparative Example 1 were measured by the national standard (GBT 11417.3-2012) coulometric method, and the test results are listed in Table 2.
  • the oxygen permeability of the contact lenses of the present invention are all above 100 barrer, and some are even as high as 160 barrer or more, which is significantly higher than that of Comparative Example 1; at the same time, the moisture content of the contact lenses of the present invention is also significantly higher than that of Comparative Example 1. This shows that the corneal contact lens prepared from the single-terminated organosiloxane macromonomer has the excellent properties of high oxygen permeability and high water content.

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Abstract

一种单封端两亲性有机硅氧烷大分子单体，在无溶剂助溶的情况下它和各种亲水性单体互混优良，能够制备高透氧性、高亲水性的硅水凝胶材料。还提供了一种硅水凝胶，包含该单封端两亲性有机硅氧烷大分子单体和下列组分通过聚合反应制成：单封端两亲性有机硅氧烷大分子单体5～60份，小分子硅单体0～30份，亲水性单体10～70份，引发剂和交联剂；该硅水凝胶具有良好的亲水性能、高透光性能和高透氧性能。还提供一种角膜接触镜，由该硅水凝胶材料制成，具有良好的透氧性、透光性、强亲水性和配戴舒适性等优点。

Description

单封端两亲性有机硅氧烷大分子单体、硅水凝胶、角膜接触镜及制备方法 技术领域
本发明涉及一种单封端两亲性有机硅氧烷大分子单体、硅水凝胶、角膜接触镜及制备方法，属于隐形眼镜镜片的材料制备领域。
背景技术
传统水凝胶角膜接触镜是由亲水性单体如甲基丙烯酸羟基乙酯，N-乙烯基吡咯烷酮等共聚而成的，普遍存在着透氧率较低，长期配戴会造成角膜缺氧，从而导致眼干、结膜充血、角膜水肿等眼表问题。
硅水凝胶是将有机硅结构单元引入到水凝胶中得到的新型材料，结合了有机硅的高透氧性和水凝胶的柔软性特点，拥有比水凝胶更高的氧气透过能力，近些年来用作角膜接触镜的材料之一。对于长时间配戴角膜接触镜者及容易眼干者，硅水凝胶角膜接触镜有着巨大的优势。近几年角膜接触镜市场快速从水凝胶向硅水凝胶转变，目前全球市场大约半数以上的角膜接触镜为硅水凝胶镜片。
硅水凝胶镜片一般是由有机硅单体和亲水性单体共聚而成，通常含有一种或两种以上的小分子量有机硅单体或分子量较大的有机硅齐聚物。小分子有机硅单体例如甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷(TRIS)、甲基-二(三甲基硅氧烷基)-甲硅烷基丙基甲基丙烯酸甘油酯(SIGMA)等，亲水性较好，与亲水性单体具有良好的相溶性，但是它们对材料透氧值的提升作用有限。分子量较大的有机硅齐聚物一般是由聚二甲基硅氧烷(PDMS)接枝反应性官能团得到的，PDMS分子呈螺旋状立体结构，分子间的作用力小，内聚能密度低，结构疏松，因此这种材料具有较高的透气性。将具有反应活性的PDMS齐聚物引入到水凝胶结构中，可以大大提高硅水凝胶的透氧率。但是，由于PDMS具有高疏水性，与亲水性单体的相溶性较差，因而PDMS的加入量有限，限制了镜片材料透氧值的提高，同时得到的硅水凝胶表面疏水性较强，影响了镜片的配戴舒适性。
因此，开发一种有效的两亲性有机硅氧烷大分子单体，能够用于制备兼具高透氧性和高亲水性的硅水凝胶镜片，是本领域技术人员亟待解决的技术问题之一。
发明内容
本发明的目的是提供一种单封端两亲性有机硅氧烷大分子单体，在无溶剂助溶的情况下它和各种亲水性单体互混优良，能够制备高亲水性和高透氧性的硅水凝胶；同时还提供一种硅水凝胶材料以及角膜接触镜，具有良好的透氧性、透光性、强亲水性，配戴舒适。
本发明提供一种单封端两亲性有机硅氧烷大分子单体，具有如式(I)所示的结构：
Figure PCTCN2021079427-appb-000001
其中，X结构为
Figure PCTCN2021079427-appb-000002
或者为
Figure PCTCN2021079427-appb-000003
其中，R 1为氢原子或甲基，R 2为C 1-C 10的烷基，m的取值范围为5-20之间的整数，n的取值范围为5-100之间的整数。
本发明提供一种所述单封端两亲性有机硅氧烷大分子单体的制备方法，包括：由羟基封端的聚醚改性聚二甲基硅氧烷和(甲基)丙烯酸异氰酸酯，在催化剂的作用下，在20～80℃区间温度内反应生成。
所述的单封端两亲性有机硅氧烷大分子单体用于制备硅水凝胶和角膜接触镜。
本发明还提供一种硅水凝胶，包含所述的单封端两亲性有机硅氧烷大分子单体和下列组分，按照质量份数计，通过聚合反应制成：
式(I)的单封端两亲性有机硅氧烷大分子单体  5～60份，
小分子硅单体                             0～30份，
亲水性单体                               10～70份，
引发剂和交联剂；
其中，单封端两亲性有机硅氧烷大分子单体为式(I)所示的两种结构中的 一种或两种的组合；单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体的质量份数之和为100份；引发剂占单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体重量和的0.5～3％；交联剂占单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体重量和的0.5～3％。
根据本发明的一个具体但非限制性的实施方案，其中，所述的小分子硅单体是甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷、甲基-二(三甲基硅氧烷基)-甲硅烷基丙基甲基丙烯酸甘油酯、3-(甲基丙烯酰氧)丙基三甲氧基硅烷和甲基丙烯酰氧基甲基三(三甲基硅氧基)硅烷中的一种或任意组合。
根据本发明的一个具体但非限制性的实施方案，其中，所述的亲水性单体是N-乙烯基吡咯烷酮、甲基丙烯酸羟丙酯、N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸、N-乙烯基乙酰胺、甲基丙烯酸甘油酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸羟丁酯和N-乙烯基甲基乙酰胺中的一种或几种的组合。
根据本发明的一个具体但非限制性的实施方案，其中，所述的引发剂是光引发剂或热引发剂；所述的光引发剂是2-羟基-2-甲基苯丙酮、1-羟基环己基苯基酮、2-羟基-2-甲基-1-苯基-丙烷-1-酮和2，4，6-三甲基苄基二苯基氧化膦中的至少一种；所述的热引发剂是偶氮二异丁腈、过氧化苯甲酰、偶氮二异庚氰、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯和过氧化二碳酸双(2-苯基乙氧基)酯中的至少一种。
根据本发明的一个具体但非限制性的实施方案，其中，所述的交联剂是聚乙二醇二丙烯酸酯、二甲基丙烯酸乙二醇酯、异氰脲酸三烯丙酯、二甲基丙烯酸三乙二醇酯、二甲基丙烯酸四乙二醇酯、二乙二醇二乙烯基醚、甲基丙烯酸乙烯酯、二乙烯基聚乙二醇酯和三羟甲基丙烷三甲基丙烯酸酯中的一种或任意组合。
另一方面，本发明还提供一种角膜接触镜，由以上所述的硅水凝胶制成。
同时，本发明还提供一种所述角膜接触镜的制备方法，包括：将式(I)的单封端两亲性有机硅氧烷大分子单体5～60份、小分子硅单体0～30份、亲水单体10～70份、引发剂和交联剂混合均匀，注入角膜接触镜模具中，光引发或热引发聚合固化，水合后制得角膜接触镜；其中，单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体的质量份数之和为100份；引发剂占单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体重量和的0.5～3％；交联剂占单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体重量和的0.5～3％。
本发明的有益效果主要体现在：
1.本发明提供的有机硅氧烷大分子单体为单封端结构，即只有一端含有具有聚合反应活性的双键官能团。与含有两个或多个双键的有机硅氧烷大分子单 体相比，明显降低了聚合物的交联度，从而有效提高了有机硅氧烷大分子单体的亲水性和含水率。
2.本发明的单封端两亲性有机硅氧烷大分子单体为嵌段共聚物，具有较长的聚醚链段，从而使有机硅氧烷大分子单体具有优异的亲水性，与亲水性单体互溶性良好，在不需要添加助溶溶剂的条件下可以大比例添加到硅水凝胶中，有效解决了有机硅氧烷大分子单体和亲水性单体互溶难的问题，从而使制得的硅水凝胶同时具备高亲水性、高透氧性和良好的透光性。
3.本发明制备的硅水凝胶材料具有优异的透氧性和透光性，同时保持了凝胶的亲水性和柔韧性。
4.本发明制备的角膜接触镜，配戴舒适，高透氧性能可以减少因缺氧导致的眼科疾病的发病率，有利于眼睛健康。
附图说明
图1是实施例1制备的单封端两亲性有机硅氧烷大分子单体(M1-w1)的核磁谱图。
图2是实施例2制备的单封端两亲性有机硅氧烷大分子单体(M1-w2)的核磁谱图。
具体实施方式
下文提供了具体的实施方式进一步说明本发明，但本发明不仅仅限于以下的实施方式。
本发明的发明人经长期研究发现，单封端的有机硅氧烷大分子单体结构比双封端结构具有更高的含水率和更好的亲水性；另外增加聚醚链段的长度可以明显提高有机硅氧烷大分子单体的亲水性，从而可以大比例提高有机硅氧烷大分子单体在硅水凝胶中的添加量。由单封端有机硅氧烷大分子单体制备的硅水凝胶兼具高透氧性和高亲水性，由它制备的角膜接触镜透氧性高、透光性好，亲水性强，配戴舒适。通常双封端有机硅氧烷大分子单体需要在助溶剂的参与下才能与亲水性单体实现良好互溶，然而本发明的发明人发现，单封端有机硅氧烷大分子单体在不需要溶剂助溶的条件下就可以与各种亲水性单体互混优良，避免使用溶剂，有利于大规模工业化生产，因此本发明有益效果十分显著。而本发明提供的单封端有机硅氧烷大分子单体结构以及由其制备的硅水凝胶目前未见文献报道。
本发明提供一种单封端两亲性有机硅氧烷大分子单体，具有如式(I)所示的结构：
Figure PCTCN2021079427-appb-000004
其中，X的结构式如下：
Figure PCTCN2021079427-appb-000005
或者为
Figure PCTCN2021079427-appb-000006
其中，R 1为氢原子或甲基，R 2为C 1-C 10的烷基，m的取值范围为5-20之间的整数，n的取值范围为5-100之间的整数。优选地，m的取值范围为7-12之间的整数，n的取值范围为12-50的之间整数。
上述式(I)的单封端两亲性有机硅氧烷大分子单体为嵌段共聚物，其中聚硅氧烷链段(1)可以有效提高硅水凝胶材料的透氧性，聚醚链段(2)和丙烯酸酯基封端基(3)具有很好的亲水性。与双封端结构相比，式(I)仅一端有一个具有聚合反应活性的双键官能团，大大降低了聚合物的交联度，使形成的聚合物网状结构具有更大的网眼，因此能锁住更多水分，从而提高聚合物的含水率和亲水性。
我们通过实验发现，聚醚链段(2)的长度m值对聚合物的亲水性有重要影响。m取值过小时(m<5)，有机硅氧烷大分子单体与亲水性单体相溶性较差，难以大比例添加到硅水凝胶中，制得的硅水凝胶透氧率较低；m取值范围在5-20之间时，有机硅氧烷大分子单体的亲水性明显趋好，制得的硅水凝胶透氧率大幅提升，达到100barrer以上，甚至能达到160barrer以上，这说明适当增加聚醚链段的长度能显著改善聚合物的亲水性，使有机硅氧烷大分子单体与亲水性单体互溶良好，可以大比例添加到硅水凝胶中，从而大幅提升了透氧率；当m取值超过25时，有机硅氧烷大分子单体呈膏状，影响镜片透光性能，因此无法用 于制备角膜接触镜。
式(I)的单封端两亲性有机硅氧烷大分子单体可以通过以下方法制备：
由羟基封端的聚醚改性聚二甲基硅氧烷(HO-PDMS)和(甲基)丙烯酸异氰酸酯(IEM)，在催化剂的作用下，在20～80℃区间温度内反应生成式(I)的有机硅氧烷大分子单体。其中，催化剂可以是二月桂酸二丁基锡、三氟甲磺酸、三乙胺或者四丁基氯化铵中的至少一种。HO-PDMS与IEM按等比例反应。
Figure PCTCN2021079427-appb-000007
其中，X结构为
Figure PCTCN2021079427-appb-000008
其中，R 1为氢原子或甲基，R 2为C 1-C 10的烷基，m的取值范围为5-20之间的整数，n的取值范围为5-100之间的整数。
进一步地，本发明提供一种硅水凝胶，包含下列组分，按照质量份数计，通过聚合反应制成：
式(I)的单封端两亲性有机硅氧烷大分子单体    5～60份，
小分子硅单体                               0～30份，
亲水性单体                                 10～70份，
引发剂和交联剂；
其中，单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体的质量份数之和为100份；引发剂占单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体重量和的0.5～3％；交联剂占单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体重量和的0.5～3％。
优选地，所述单封端两亲性有机硅氧烷大分子单体的质量份数为29～60份。
具体地，式(I)的单封端两亲性有机硅氧烷大分子单体如上所述。单封端两亲性有机硅氧烷大分子单体为式(I)所示的两种结构中的一种或两种的组合。
所述的小分子硅单体可以是甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷(TRIS)、甲基-二(三甲基硅氧烷基)-甲硅烷基丙基甲基丙烯酸甘油酯(SIGMA)、3-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH570)和甲基丙烯酰氧基甲基三(三甲基硅氧基)硅烷(MTTS)中的一种或任意组合。小分子硅单体在硅水凝胶中作为增溶单体，可以增加有机硅氧烷大分子单体和亲水性单体的相溶性，同时小分子硅单体对透氧性能的提高有一定的作用。
所述的亲水性单体可以是N-乙烯基吡咯烷酮(NVP)、甲基丙烯酸羟丙酯(HPMA)、N,N-二甲基丙烯酰胺(DMA)、甲基丙烯酸羟乙酯(HEMA)、甲基丙烯酸(AA)、N-乙烯基乙酰胺(NVA)、甲基丙烯酸甘油酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸羟丁酯、N-乙烯基甲基乙酰胺中的一种或几种的组合。每种亲水单体的性能特点不同，将多种单体复合使用可以充分发挥每种单体的优良性能。
所述的引发剂可以是光引发剂或热引发剂。其中，光引发剂可以是2-羟基-2-甲基苯丙酮(D1173)、1-羟基环己基苯基酮、2-羟基-2-甲基-1-苯基-丙烷-1-酮和2，4，6-三甲基苄基二苯基氧化膦中的至少一种；所述的热引发剂可以是偶氮二异丁腈(AIBN)、过氧化苯甲酰(BPO)、偶氮二异庚氰、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯和过氧化二碳酸双(2-苯基乙氧基)酯中的至少一种。
所述的交联剂可以是聚乙二醇二丙烯酸酯(PEGDA)、二甲基丙烯酸乙二醇酯(EGDMA)、异氰脲酸三烯丙酯(TAIC)、二甲基丙烯酸三乙二醇酯、二甲基丙烯酸四乙二醇酯、二乙二醇二乙烯基醚、甲基丙烯酸乙烯酯、二乙烯基聚乙二醇酯和三羟甲基丙烷三甲基丙烯酸酯中的一种或任意组合。
在实际生产时，硅水凝胶材料还可以根据需要添加其它功能性单体，例如包含有色单体、变色单体或阻隔紫外光、蓝光、近红外光单体。
由于式(I)的有机硅氧烷大分子单体具有优异的亲水性，它与亲水单体相溶性良好，不需要溶剂助溶，故本发明的硅水凝胶配方中没有添加溶剂，这对于大规模工业化生产来说是一巨大优势。因为在大规模工业生产中，添加有机溶剂是一个非常严重的制约因素，添加有机溶剂不但增加生产和回收成本，还会造成环境污染。更重要的是，在混合单体聚合制备镜片的过程中，无论是热聚合还是光聚合，溶剂都会大量挥发到空气中，当空气中溶剂浓度超过一定值后，不但会影响操作人员健康，还会有爆炸、燃烧等危险。
另一方面，由于有机硅氧烷大分子单体与亲水性单体互溶良好，可以大比例添加到硅水凝胶中，从而大幅提升了硅水凝胶的透氧率。本发明有机硅氧烷大分子单体在硅水凝胶中的添加量为5-60％，有机硅氧烷大分子单体几乎占硅水凝胶总重量的5-60％，也就是说，本发明可以做到有机硅氧烷大分子单体的添加量达到40％以上，而市售产品只能做到有机硅氧烷大分子单体添加20％左右， 远低于本发明的添加水平。
本发明有效解决了有机聚硅氧烷大分子单体和亲水性单体互溶难的问题，在保持较高含水率的前提下大幅提高了硅水凝胶的透氧率，从而实现了硅水凝胶材料兼具高透氧性和高含水率的目标，极大提高了硅水凝胶材料的性能。实验表明，本发明的硅水凝胶含水率在30-50％，透氧率达到100barrer以上，甚至能达到160barrer以上，显著高于由双封端有机聚硅氧烷大分子单体制成的硅水凝胶材料。
本发明还提供一种由上述硅水凝胶材料制成的角膜接触镜。该角膜接触镜通过以下方法制备：
将式(I)的单封端两亲性有机硅氧烷大分子单体5～60份、小分子硅单体0～30份、亲水单体10～70份、引发剂和交联剂混合均匀，注入角膜接触镜模具中，光引发或热引发聚合固化，水合后制得硅水凝胶角膜接触镜；其中，单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体的质量份数之和为100份；引发剂占单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体重量和的0.5～3％；交联剂占单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体重量和的0.5～3％。
本发明的角膜接触镜采用上述硅水凝胶材料制成，硅水凝胶材料保留了水凝胶材料的高亲水性，有很好的抗脂质沉淀性能和生物相容性，配戴舒适；高透氧性可以减少因缺氧导致的眼科疾病的发病率，有利于眼睛健康；良好的透光性能保证了配戴的视觉效果和舒适度。
下面结合具体实施例对本发明作进一步阐述，但本发明并不限于以下实施例。
上文及下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
上文及下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1
单封端两亲性有机硅氧烷大分子单体的制备
取HO-PDMS(数均分子量约为1500，其中m约为7，n约为16，购自南京福群化工有限公司)30g，加入50mL二氯甲烷(CH 2Cl 2)和0.1g二月桂酸二丁基锡，搅拌混合均匀。再称取对应比例的IEM与CH 2Cl 2混合，加入恒压滴液漏斗，向反应液滴加IEM与CH 2Cl 2混合液。同时打开恒温水浴加热装置，调节温度到55℃，反应10h。反应结束后，50℃旋蒸30min，得到有机硅氧烷大分子单体，记为M1-w1。图1是实施例1制备的单封端两亲性有机硅氧烷大分子单体(M1-w1)的核磁谱图。
Figure PCTCN2021079427-appb-000009
其中，m约为7，n约为16
(M1-w1)
实施例2
单封端两亲性有机硅氧烷大分子单体的制备
取HO-PDMS(数均分子量约为5500，其中m约为11，n约为50，购自南京福群化工有限公司)50g，加入80mL CH 2Cl 2和0.2g二月桂酸二丁基锡，搅拌混合均匀。再称取对应比例的IEM与CH 2Cl 2混合，加入恒压滴液漏斗，向反应液滴加IEM与CH 2Cl 2混合液。同时打开恒温水浴加热装置，调节温度55℃，反应10h，反应结束后50℃旋蒸30min，得到有机硅氧烷大分子单体，记为M1-w2。图2是实施例2制备的单封端两亲性有机硅氧烷大分子单体(M1-w2)的核磁谱图。
Figure PCTCN2021079427-appb-000010
其中，m约为11，n约为50
(M1-w2)
实施例3-4
一种硅水凝胶，由下列组分通过聚合反应制备：
Figure PCTCN2021079427-appb-000011
其中，单封端两亲性有机硅氧烷大分子单体分别由实施例1和实施例2制备。
实施例5-12
角膜接触镜的制备
将单封端两亲性有机硅氧烷大分子单体，连同小分子硅单体、亲水单体、引发剂和交联剂混合均匀，注入角膜接触镜模具中，光引发或热引发聚合，然后脱模，水合后制得硅水凝胶角膜接触镜。制得的角膜接触镜具有前表面和后表面。
其中，单封端两亲性有机硅氧烷大分子单体由实施例1或实施例2制备，小分子硅单体采用甲基-二(三甲基硅氧烷基)-甲硅烷基丙基甲基丙烯酸甘油酯(SIGMA)，亲水单体采用甲基丙烯酸羟乙酯(HEMA)，N-乙烯基乙酰胺(NVA)，甲基丙烯酸羟丙酯(HPMA)，引发剂采用2-羟基-2-甲基苯丙酮(D1173)，交联剂采用二甲基丙烯酸乙二醇酯(EGDMA)。实施例5-12的反应组分和配比关系列于表1中。
表1 实施例5-12和对比例1的反应组分和配比(按质量份数计)
Figure PCTCN2021079427-appb-000012
Figure PCTCN2021079427-appb-000013
对比例1
用双封端有机硅氧烷大分子单体(M2-w1)替代本发明的单封端两亲性有机硅氧烷大分子单体，按照实施例5-12的方法制备角膜接触镜，反应组分和配比关系见表1，其它反应条件不变。双封端有机硅氧烷大分子单体M2-w1分子式如下：
Figure PCTCN2021079427-appb-000014
其中，m约为7，n约为16
(M2-w1)
实施例13
采用国标(GBT 11417.3-2012)库仑法分别测实施例5-12和对比例1制备的角膜接触镜的透氧值，测试结果列于表2中。
采用称重法测实施例5-12和对比例1制备的角膜接触镜的含水率，载玻片重量Q1，镜片与载玻片重量Q2，50℃烘箱内干燥至恒重后，毛重G3，含水率＝(Q2-G3)/(Q2-Q1)，测试结果列于表2中。
表2 测试结果
Figure PCTCN2021079427-appb-000015
从表2可以看出，本发明的角膜接触镜透氧率都在100barrer以上，有的甚至高达160barrer以上，显著高于对比例1；同时本发明的角膜接触镜含水率也明显高于对比例1。这说明本发明由单封端有机硅氧烷大分子单体制备的角膜接触镜具有高透氧、高含水率的优良性能。
本领域的技术人员应该了解，本发明不受上述具体实施例的限制，上述具体实施例和说明书中的描述只是为了进一步说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护的范围由权利要求书及其等效物界定。

Claims (10)

  1. 一种单封端两亲性有机硅氧烷大分子单体，其特征在于，具有如式(I)所示的结构：
    Figure PCTCN2021079427-appb-100001
    其中，X的结构式如下：
    Figure PCTCN2021079427-appb-100002
    或者为
    Figure PCTCN2021079427-appb-100003
    其中，R 1为氢原子或甲基，R 2为C 1-C 10的烷基，m的取值范围为5-20之间的整数，n的取值范围为5-100之间的整数。
  2. 一种如权利要求1所述的单封端两亲性有机硅氧烷大分子单体的制备方法，其特征在于，包括：由羟基封端的聚醚改性聚二甲基硅氧烷和(甲基)丙烯酸异氰酸酯，在催化剂的作用下，在20～80℃区间温度内反应生成。
  3. 权利要求1所述的单封端两亲性有机硅氧烷大分子单体用于制备硅水凝胶和角膜接触镜。
  4. 一种硅水凝胶，其特征在于，包含权利要求1所述的单封端两亲性有机硅氧烷大分子单体和下列组分，按照质量份数计，通过聚合反应制成：
    式(I)的单封端两亲性有机硅氧烷大分子单体  5～60份，
    小分子硅单体                            0～30份，
    亲水性单体                             10～70份，
    引发剂和交联剂；
    其中，单封端两亲性有机硅氧烷大分子单体为式(I)所示的两种结构中的一种或两种的组合；单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体的质量份数之和为100份；引发剂占单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体重量和的0.5～3％；交联剂占单封端两亲性有 机硅氧烷大分子单体、小分子硅单体和亲水性单体重量和的0.5～3％。
  5. 根据权利要求4的硅水凝胶，其特征在于，所述的小分子硅单体是甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷、甲基-二(三甲基硅氧烷基)-甲硅烷基丙基甲基丙烯酸甘油酯、3-(甲基丙烯酰氧)丙基三甲氧基硅烷和甲基丙烯酰氧基甲基三(三甲基硅氧基)硅烷中的一种或任意组合。
  6. 根据权利要求4的硅水凝胶，其特征在于，所述的亲水性单体是N-乙烯基吡咯烷酮、甲基丙烯酸羟丙酯、N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸、N-乙烯基乙酰胺、甲基丙烯酸甘油酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸羟丁酯和N-乙烯基甲基乙酰胺中的一种或几种的组合。
  7. 根据权利要求4的硅水凝胶，其特征在于，所述的引发剂是光引发剂或热引发剂；所述的光引发剂是2-羟基-2-甲基苯丙酮、1-羟基环己基苯基酮、2-羟基-2-甲基-1-苯基-丙烷-1-酮和2，4，6-三甲基苄基二苯基氧化膦中的至少一种；所述的热引发剂是偶氮二异丁腈、过氧化苯甲酰、偶氮二异庚氰、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯和过氧化二碳酸双(2-苯基乙氧基)酯中的至少一种。
  8. 根据权利要求4的硅水凝胶，其特征在于，所述的交联剂是聚乙二醇二丙烯酸酯、二甲基丙烯酸乙二醇酯、异氰脲酸三烯丙酯、二甲基丙烯酸三乙二醇酯、二甲基丙烯酸四乙二醇酯、二乙二醇二乙烯基醚、甲基丙烯酸乙烯酯、二乙烯基聚乙二醇酯和三羟甲基丙烷三甲基丙烯酸酯中的一种或任意组合。
  9. 一种角膜接触镜，其特征在于，由权利要求4-8中任一所述的硅水凝胶制成。
  10. 一种如权利要求9所述的角膜接触镜的制备方法，其特征在于，包括：将式(I)的单封端两亲性有机硅氧烷大分子单体5～60份、小分子硅单体0～30份、亲水单体10～70份、引发剂和交联剂混合均匀，注入角膜接触镜模具中，光引发或热引发聚合固化，水合后制得角膜接触镜；其中，单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体的质量份数之和为100份；引发剂占单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体重量和的0.5～3％；交联剂占单封端两亲性有机硅氧烷大分子单体、小分子硅单体和亲水性单体重量和的0.5～3％。
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