Side chain type amphiphilic organosiloxane macromonomer as well as preparation method and application thereof

Abstract

The invention discloses a side-chain type amphiphilic organosiloxane macromonomer and a preparation method and application thereof, the side-chain type amphiphilic organosiloxane macromonomer can be well mixed with various hydrophilic monomers under the condition of no hydrotropy of a solvent, and a silicon hydrogel material with high oxygen permeability and high hydrophilicity can be prepared. The invention also discloses a silicon hydrogel which is prepared from the side chain type amphiphilic organosiloxane macromonomer and the following components through polymerization reaction: 5-45 parts of side chain type organosiloxane macromonomer, 0-30 parts of micromolecular silicon monomer, 25-70 parts of hydrophilic monomer, an initiator and a cross-linking agent. The silicon hydrogel has good hydrophilic performance, high light transmittance and high oxygen permeability. Meanwhile, the invention further discloses a corneal contact lens which is made of the silicone hydrogel material and has the advantages of being good in oxygen permeability, hydrophilicity, light transmission, wearing comfort and the like.

Description

Technical Field

[0001] The present invention relates to a side chain amphiphilic organosiloxane macromolecular monomer and a preparation method and application thereof, in particular to a side chain amphiphilic organosiloxane macromolecular monomer and a preparation method thereof and application of the side chain amphiphilic organosiloxane macromolecular monomer in preparing silicone hydrogel and corneal contact lens, belonging to the field of contact lens material preparation. Background Art

[0002] Corneal contact lenses are lenses that are worn directly on the eyeball to correct vision, also known as contact lenses. The materials used to make corneal contact lenses are not only required to have good light transmittance, biocompatibility, surface hydrophilicity and suitable mechanical properties, but also to have high oxygen permeability.

[0003] Traditional corneal contact lenses are made of hydrogels obtained by copolymerization of hydrophilic monomers such as hydroxyethyl methacrylate and N-vinyl pyrrolidone. They 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. In order to solve the problem of poor oxygen permeability, silicone hydrogels are now commonly used to make corneal contact lenses.

[0004] Silicone hydrogel lenses are generally copolymerized with silicone monomers and hydrophilic monomers, and usually contain one or two or more high molecular weight silicone monomers or low molecular weight silicone monomers. Small molecular weight silicone monomers such as methacryloxypropyl tri(trimethylsiloxy)silane (TRIS), methyl-bis(trimethylsiloxy)-silylpropyl methacrylate (SIGMA), etc., have good hydrophilicity and good compatibility with hydrophilic monomers, but due to their small molecular weight, they have limited effect on improving the oxygen permeability of the material. High molecular weight silicone monomers are generally obtained by grafting hydrophilic functional groups onto polydimethylsiloxane (PDMS). PDMS molecules have a helical three-dimensional structure, small intermolecular forces, low cohesive energy density, and loose structure. Therefore, this material has high air permeability, and the oxygen permeability (Dk) of pure polydimethylsiloxane can reach 600 barrer. Introducing reactive PDMS oligomers into the hydrogel structure can greatly improve the oxygen permeability of silicone hydrogels. However, due to the high hydrophobicity of PDMS and its poor compatibility with hydrophilic monomers, the amount of PDMS added is limited, which restricts the improvement of the oxygen permeability of the lens material. At the same time, the surface of the resulting silicone hydrogel is highly hydrophobic, affecting the wearing comfort of the lens.

[0005] Therefore, developing an organosiloxane macromolecular monomer that can be used to prepare silicone hydrogel lenses that have both high oxygen permeability and high hydrophilicity is one of the technical problems that technical personnel in this field urgently need to solve. Summary of the invention

[0006] Object of the Invention: The first object of the present invention is to provide a side-chain amphiphilic organosiloxane macromonomer. The second object of the present invention is to provide a preparation method of the side-chain amphiphilic organosiloxane macromonomer. The third object of the present invention is to provide the preparation of a silicone hydrogel or a contact lens using the side-chain amphiphilic organosiloxane macromonomer. The fourth object of the present invention is to provide a silicone hydrogel prepared using the side-chain amphiphilic organosiloxane macromonomer. The fifth object of the present invention is to provide a contact lens prepared using the side-chain amphiphilic organosiloxane macromonomer or the silicone hydrogel. The last two objects of the present invention are to provide a preparation method of the contact lens.

[0007] Technical Solution: A side-chain amphiphilic organosiloxane macromonomer described in the present invention, the structural general formula of the side-chain amphiphilic organosiloxane macromonomer is shown as the following formula (I):

[0008]

[0009] Among them, X1 is an alkyl group with C1-C 10 of alkyl,

[0010] X2 is a is an integer between 4 and 20,

[0011] X3 is

[0012] R1 is a hydrogen atom, a phenyl group or an alkyl group with C1-C 10 of alkyl, R2 is a hydrogen atom, a phenyl group or an alkyl group with C1-C 10 of alkyl, m, n, and q are all integers between 5 and 100.

[0013] The preparation method of the side-chain amphiphilic organosiloxane macromonomer described in the present invention includes the following steps:

[0014] (1) Octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane are synthesized into a linear hydrogen-containing polydimethylsiloxane macromolecule under the action of a siloxane end-capping agent and a catalyst;

[0015] (2) Then, an allyl polyether capped with a hydroxyl group and a hydrophilic monomer are added, and a side-chain grafted polydimethylsiloxane macromolecule is synthesized through a hydrosilylation reaction under the action of a catalyst.

[0016] (3) Finally, it reacts with isocyanatoethyl methacrylate under the action of a catalyst to generate a side-chain amphiphilic organosiloxane macromonomer.

[0017] Furthermore, in step (1), the catalyst is nkc-9 cation exchange resin.

[0018] Further, in step (1), the structural general formula of the siloxane end-capping agent is shown as the following formula II:

[0019]

[0020] Among them, R1 is a hydrogen atom, a phenyl group or a C1-C 10 alkyl group.

[0021] Further, in step (1), the molar ratio of octamethylcyclotetrasiloxane to the siloxane end-capping agent is 1:1 to 50:1, and the molar ratio of tetramethylcyclotetrasiloxane to the siloxane end-capping agent is 1:1 to 50:1.

[0022] Further, in step (1), the reaction temperature is 20-90 °C.

[0023] Further, in step (2), the structural general formula of the allyl polyether capped with hydroxyl groups is shown as the following formula III:

[0024]

[0025] Among them, a is an integer between 4 and 20.

[0026] Further, in step (2), the hydrophilic monomer is N,N-dimethylacrylamide, N-methyl-N-vinylacetamide or N-vinylpyrrolidone.

[0027] Further, in step (2), the catalyst is chloroplatinic acid.

[0028] Further, in step (2), the molar ratio of the allyl polyether capped with hydroxyl groups to tetramethylcyclotetrasiloxane is 1:1 to 1:20, and the molar ratio of the hydrophilic monomer to tetramethylcyclotetrasiloxane is 1:1 to 1:20.

[0029] Further, in step (2), the reaction temperature is 10-120 °C.

[0030] Further, in step (3), the catalyst is dibutyltin dilaurate.

[0031] Further, in step (3), the molar ratio of isocyanatoethyl methacrylate to the allyl polyether capped with hydroxyl groups is 1:1.

[0032] Further, in step (3), the reaction temperature is 10-60 °C.

[0033] The present invention also includes using the side-chain amphiphilic organosiloxane macromonomer described above to prepare silicone hydrogels or contact lenses.

[0034] The present invention also includes a silicone hydrogel, which contains the side-chain amphiphilic organosiloxane macromonomer described in the present invention and the following components, and is prepared by a polymerization reaction according to the following parts by mass:

[0035] 5-45 parts of the side-chain amphiphilic organosiloxane macromonomer of formula (I),

[0036] 0-30 parts of a small molecule silicon monomer,

[0037] 25-70 parts of a hydrophilic monomer,

[0038] an initiator and a crosslinking agent;

[0039] wherein, the sum of the parts by mass of the side-chain amphiphilic organosiloxane macromonomer, the small molecule silicon monomer and the hydrophilic monomer of formula (I) is 100 parts; the initiator accounts for 0.5-3% of the total weight of the side-chain amphiphilic organosiloxane macromonomer, the small molecule silicon monomer and the hydrophilic monomer; the crosslinking agent accounts for 0.5-3% of the total weight of the side-chain amphiphilic organosiloxane macromonomer, the small molecule silicon monomer and the hydrophilic monomer.

[0040] Further, the small molecule silicon monomer is one or any combination of methacryloxypropyl tris(trimethylsiloxy)silane, methyl-di(trimethylsiloxy)-silylpropyl methacrylate glycerol ester, 3-(methacryloxy)propyltrimethoxysilane, and methacryloxymethyl tris(trimethylsiloxy)silane.

[0041] Further, the hydrophilic monomer is one or a combination of N-vinylpyrrolidone, hydroxypropyl methacrylate, hydroxyethyl methacrylate, N,N-dimethylacrylamide, methacrylic acid, N-vinylacetamide, glycerol methacrylate, glycidyl methacrylate, hydroxybutyl methacrylate, N-vinyl-N-methylacetamide, acrylic acid, and acrylamide.

[0042] Further, the initiator is a photoinitiator or a thermal initiator; the photoinitiator is at least one of 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2,4,6-trimethylbenzyl diphenylphosphine oxide; the thermal initiator is at least one of azobisisobutyronitrile, benzoyl peroxide, azodiisovaleronitrile, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and bis(2-phenylethoxy) peroxydicarbonate.

[0043] Further, the crosslinking agent is one or any combination of polyethylene glycol diacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triallyl isocyanurate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, diethylene glycol divinyl ether, vinyl methacrylate, divinyl polyethylene glycol ester, and trimethylolpropane trimethacrylate.

[0044] The present invention also includes a contact lens, comprising the side-chain amphiphilic organosiloxane macromonomer described in the present invention or the silicone hydrogel described in the present invention.

[0045] The preparation method of the contact lens described in the present invention includes the following steps:

[0046] Mix the side-chain amphiphilic organosiloxane macromonomer of formula (I), small molecular silicon monomer, hydrophilic monomer, initiator, and crosslinking agent evenly, inject them into a contact lens mold, carry out photoinitiated or thermally initiated polymerization, demold, extract the unpolymerized monomers and oligomers in the lens with deionized water, and immerse them in physiological saline for equilibration to obtain the contact lens.

[0047] Further, 5-45 parts of the side-chain amphiphilic organosiloxane macromonomer of formula (I), 0-30 parts of the small molecular silicon monomer, and 25-70 parts of the hydrophilic monomer, and the sum of the mass parts of the side-chain amphiphilic organosiloxane macromonomer, small molecular silicon monomer, and hydrophilic monomer is 100 parts; the initiator accounts for 0.5-3% of the total weight of the side-chain amphiphilic organosiloxane macromonomer, small molecular silicon monomer, and hydrophilic monomer; the crosslinking agent accounts for 0.5-3% of the total weight of the side-chain amphiphilic organosiloxane macromonomer, small molecular silicon monomer, and hydrophilic monomer.

[0048] The side-chain amphiphilic organosiloxane macromonomer provided by the present invention has excellent miscibility with various hydrophilic monomers without solvent solubilization, and can prepare a silicone hydrogel with high hydrophilicity and high oxygen permeability; at the same time, a contact lens prepared by using it is also provided, which has good oxygen permeability, light transmittance, hydrophilicity, and is comfortable to wear.

[0049] The side-chain type organosiloxane macromonomer structure of the present invention has a higher moisture content and better hydrophilicity than the main-chain type structure. It has good compatibility with small-molecule organosilicon monomers and hydrophilic monomers, and a large proportion of macromolecular organosilicon monomers can be added to the silicone hydrogel, significantly increasing the addition amount of the organosiloxane macromonomer, thereby significantly improving the oxygen permeability of the silicone hydrogel material. The silicone hydrogel prepared from the side-chain type amphiphilic organosiloxane macromonomer has both high oxygen permeability and high hydrophilicity. The contact lens prepared from it has good oxygen permeability, light transmittance, strong hydrophilicity, and is comfortable to wear. Usually, the main-chain type organosiloxane macromonomer can only be miscible with hydrophilic monomers with the participation of a co-solvent. However, the side-chain type amphiphilic organosiloxane macromonomer can be miscible well with various hydrophilic monomers without the need for solvent assistance, and avoiding the use of solvents is beneficial to large-scale industrial production. Therefore, the beneficial effects of the present invention are very significant.

[0050] Advantages: Compared with the prior art, the present invention has the following remarkable advantages:

[0051] (1) The organosiloxane macromonomer provided by the present invention has a side-chain type structure, that is, it contains double bond functional groups with polymerization reaction activity on the side chain. Compared with the main-chain capped organosiloxane macromonomer, the number of hydrophilic groups connected to the side chain has been significantly increased, thereby effectively improving the hydrophilicity of the organosiloxane macromonomer.

[0052] (2) The side-chain type amphiphilic organosiloxane macromonomer of the present invention is a graft copolymer with three different repeating units, which are respectively connected with different alkyl groups and hydrophilic groups, so that the organosiloxane macromonomer has excellent hydrophilicity and lipophilicity at the same time, and has very good miscibility with hydrophilic monomers and small-molecule silicon monomers. It can be added to the silicone hydrogel in a large proportion without adding a co-solvent, so that the prepared silicone hydrogel has high hydrophilicity, high oxygen permeability and light transmittance at the same time.

[0053] (3) The silicone hydrogel material prepared by the present invention has excellent oxygen permeability and light transmittance, and at the same time maintains the hydrophilicity and flexibility of the gel. Solvents do not need to be added to the formula, reducing the production cost and being more conducive to large-scale industrial production.

[0054] (4) The contact lens prepared by the present invention has good oxygen permeability, light transmittance, hydrophilicity, is comfortable to wear, and the high oxygen permeability can reduce the incidence of ophthalmic diseases caused by hypoxia, which is beneficial to eye health. Detailed implementation mode

[0055] The technical solution of the present invention will be further described below.

[0056] The present invention provides a side-chain amphiphilic organosiloxane macromonomer having a structure as shown in formula (I):

[0057]

[0058] Wherein, X1 is an alkyl group of C1-C 10 and

[0059] X2 is

[0060] X3 is one of them,

[0061] R1 and R2 are hydrogen atoms, phenyl groups or alkyl groups of C1-C 10 , m, n, and q are integers between 5 and 100, and a is an integer between 4 and 20.

[0062] The side-chain amphiphilic organosiloxane macromonomer of the above formula (I) is a block copolymer, wherein the polysiloxane segment (1) imparts good oxygen permeability to the material, and the polyether segment (2), isocyanate group (3), amide group (4), (6) and vinylpyrrolidone group (5) have good hydrophilicity. Compared with the main-chain structure, more hydrophilic groups can be connected to one main chain in formula (I), thereby effectively improving the hydrophilicity of the macromolecular silicon monomer, having better compatibility with hydrophilic monomers under the condition of no solvent, and a silicone hydrogel with better hydrophilicity and light transmittance can be prepared.

[0063] The side-chain amphiphilic organosiloxane macromonomer of formula (I) can be prepared by the following method:

[0064] First, octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane are used under the action of a siloxane end-capping agent and a catalyst nkc-9 cation exchange resin to synthesize a linear hydrogen-containing polydimethylsiloxane macromolecule with a side chain at a reaction temperature of 20-90°C; then, a hydroxyl-terminated polyether allyl polyether and a hydrophilic monomer N,N-dimethylacrylamide or N-methyl-N-vinylacetamide or N-vinylpyrrolidone are used under the action of a catalyst chloroplatinic acid to synthesize a side-chain grafted polydimethylsiloxane macromolecule through a hydrosilylation reaction at a reaction temperature of 10-120°C. Finally, it reacts with isocyanatoethyl methacrylate under the action of a catalyst dibutyltin dilaurate at a reaction temperature of 10-60°C to generate a side-chain amphiphilic organosiloxane macromonomer.

[0065]

[0066] 10 and

[0067] X2 is

[0068] X3 is one of

[0069] R1 and R2 are hydrogen atoms, phenyl groups or C1-C 10 alkyl groups, m, n, and q are integers between 5 and 100, and a is an integer between 4 and 20.

[0070] Furthermore, the present invention provides a silicone hydrogel, which contains the following components and is prepared by a polymerization reaction according to mass parts:

[0071] 5-45 parts of the side-chain amphiphilic organosiloxane macromonomer of formula (I),

[0072] 0-30 parts of small molecule silicone monomer,

[0073] 25-70 parts of hydrophilic monomer,

[0074] initiator and crosslinking agent;

[0075] Among them, the sum of the mass parts of the side-chain amphiphilic organosiloxane macromonomer, small molecule silicone monomer and hydrophilic monomer is 100 parts; the initiator accounts for 0.5-3% of the total weight of the side-chain amphiphilic organosiloxane macromonomer, small molecule silicone monomer and hydrophilic monomer; the crosslinking agent accounts for 0.5-3% of the total weight of the side-chain amphiphilic organosiloxane macromonomer, small molecule silicone monomer and hydrophilic monomer.

[0076] Specifically, the side-chain amphiphilic organosiloxane macromonomer of formula (I) is as described above.

[0077] The small molecule silicone monomer can be one or any combination of methacryloxypropyl tris(trimethylsiloxy)silane (TRIS), methyl-bis(trimethylsiloxy)-silylpropyl glycerol methacrylate (SIGMA), 3-(methacryloxy)propyltrimethoxysilane (KH570) and methacryloxymethyl tris(trimethylsiloxy)silane (MTTS). The small molecule silicone monomer acts as a solubilizing monomer in the silicone hydrogel, which can increase the compatibility of the organosiloxane macromonomer and the hydrophilic monomer. At the same time, the small molecule silicone monomer plays a certain role in improving the oxygen permeability.

[0078] The hydrophilic monomer is one or a combination of N-vinylpyrrolidone, hydroxypropyl methacrylate, hydroxyethyl methacrylate, N,N-dimethylacrylamide, methacrylic acid, N-vinylacetamide, glycerol methacrylate, glycidyl methacrylate, hydroxybutyl methacrylate, N-vinyl-N-methylacetamide, acrylic acid, acrylamide. Each hydrophilic monomer has different performance characteristics, and only by compounding multiple formulations can the excellent performance of each monomer be fully exerted.

[0079] The initiator described above can be a photoinitiator or a thermal initiator. Among them, the photoinitiator can be at least one of 2-hydroxy-2-methylpropiophenone (D1173), 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2,4,6-trimethylbenzyl diphenyl phosphine oxide; the thermal initiator can be at least one of azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), azodiisovaleronitrile, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and bis(2-phenylethoxy) peroxydicarbonate.

[0080] 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 ester, and trimethylolpropane trimethacrylate.

[0081] During actual production, other functional monomers can also 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.

[0082] Due to the excellent hydrophilicity of the organosiloxane macromonomer of formula (I), it is miscible with hydrophilic monomers and does not require solvent assistance for dissolution. Therefore, no solvent is added to the silicone hydrogel formulation of the present invention, which is a great advantage for large-scale industrial production. Because in large-scale industrial production, the addition of organic solvents is a very serious limiting factor. Adding organic solvents not only increases production and recovery costs but also causes environmental pollution. More importantly, during the process of polymerizing mixed monomers to prepare lenses, whether it is thermal polymerization or ultraviolet polymerization, the solvent will volatilize into the air in large amounts. When the solvent concentration in the air exceeds a certain value, it will not only affect the health of operators but also pose risks such as explosion and combustion.

[0083] On the other hand, due to the good miscibility of the organosiloxane macromonomer with hydrophilic monomers, it can be added to the silicone hydrogel in a large proportion, thereby significantly improving the oxygen permeability of the silicone hydrogel. The addition amount of the organosiloxane macromonomer of the present invention in the silicone hydrogel is 5-45%, and the organosiloxane macromonomer almost accounts for 5-45% of the total weight of the silicone hydrogel. That is to say, the present invention can achieve an addition amount of the organosiloxane macromonomer above 40%, while commercially available products can only achieve an addition amount of the organosiloxane macromonomer of about 20%, which is much lower than the addition level of the present invention.

[0084] The present invention effectively solves the problem of difficult mutual solubility between macromolecular monomers of organopolysiloxane and hydrophilic monomers, and greatly improves the oxygen permeability of the silicone hydrogel while maintaining a relatively high water content, thereby enabling the silicone hydrogel material to have both high oxygen permeability and high water content. Experiments show that the water content of the silicone hydrogel of the present invention is above 50%, the oxygen permeability reaches above 120 barrer, and can even reach above 160 barrer, and the surface contact angle is below 70°. The comprehensive performance is significantly higher than that of the silicone hydrogel material made of main-chain amphiphilic organosiloxane macromolecular monomers.

[0085] The present invention also provides a contact lens made of the above silicone hydrogel material. The contact lens is prepared by the following method:

[0086] 5-45 parts of the side-chain amphiphilic organosiloxane macromolecular monomer of formula (I), 0-30 parts of the small-molecule silicone monomer, 25-70 parts of the hydrophilic monomer, the initiator and the crosslinking agent are mixed evenly, injected into the contact lens mold, and polymerized by photoinitiation or thermal initiation, then demolded, and the unpolymerized monomers and oligomers in the lens are removed by extraction with deionized water, and immersed in physiological saline for equilibration, thereby obtaining the silicone hydrogel contact lens; wherein, the sum of the mass parts of the side-chain amphiphilic organosiloxane macromolecular monomer, the small-molecule silicone monomer and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5-3% of the total weight of the side-chain amphiphilic organosiloxane macromolecular monomer, the small-molecule silicone monomer and the hydrophilic monomer; the crosslinking agent accounts for 0.5-3% of the total weight of the side-chain amphiphilic organosiloxane macromolecular monomer, the small-molecule silicone monomer and the hydrophilic monomer.

[0087] The contact lens of the present invention is made of the above 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 the high oxygen permeability and light transmittance can reduce the incidence of ophthalmic diseases caused by hypoxia, which is beneficial to eye health.

[0088] The present invention will be further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments.

[0089] The experimental methods used in the above and the following embodiments are all conventional methods unless otherwise specified.

[0090] The materials, reagents, etc. used in the above and the following embodiments can be obtained from commercial sources unless otherwise specified.

[0091] Example 1

[0092] Preparation of the side-chain amphiphilic organosiloxane macromolecular monomer

[0093] First, take 50 g of octamethylcyclotetrasiloxane (D4), 5.4 g of tetramethylcyclotetrasiloxane (D4H), 3.65 g of hexamethyldisiloxane, and 3 g of nkc-9 cation exchange resin and place them in a three-necked flask. React at 65 °C for 7 h to obtain side-chain PDMS (number-average molecular weight of 5000). Then, take 20 g of side-chain PDMS and 0.15 mL of chloroplatinic acid-isopropanol solution. Slowly add 7.1 g of polyethylene glycol (PEG) and 0.78 g of N-vinyl-N-methylacetamide dropwise at 120 °C and react for 5 h. Cool down to 45 °C, add 0.06 g of dibutyltin dilaurate, and slowly add 2.63 g of isocyanatoethyl methacrylate (IEM) dropwise and react for 5 h to obtain a side-chain amphiphilic organosiloxane macromonomer, denoted as M1-w1.

[0094] Perform 1H NMR analysis on the side-chain amphiphilic organosiloxane macromonomer (M1-w1) prepared in this example. The results are as follows:

[0095] For M1-w1 1 1H NMR (600 MHz, CDCl3) δ 0 - 0.09 (s, 384H, Si-CH3), δ 0.46 (t, 16H, Si-CH2), δ 1.19 - 1.53 (m, 12H, C-CH2-C), δ 1.87 (s, 18H, C-CH3), δ 2.29 (t, 6H, O=C-CH3), δ 2.94 (t, 6H, N-CH3), δ 3.32 - 3.60 (m, 156H, O-CH2-C), δ 4.16 (t, 4H, N-CH2), δ 5.22 (t, 6H, N-H), δ 5.52 (s, 12H, C=CH2), δ 6.05 (s, 12H, C=CH2)

[0096] From the above analysis, the structural formula of M1-w1 is shown as follows:

[0097]

[0098] Where m is approximately 60, n is approximately 6, q is approximately 2, and a is approximately 6.

[0099] Example 2

[0100] Preparation of side-chain amphiphilic organosiloxane macromonomer

[0101] First, take 50 g of octamethylcyclotetrasiloxane (D4), 5.4 g of tetramethylcyclotetrasiloxane (D4H), 3.65 g of hexamethyldisiloxane, and 3 g of nkc-9 cation exchange resin and place them in a three-necked flask. React at 65 °C for 7 h to obtain side-chain PDMS (number-average molecular weight of 5000). Then, take 20 g of side-chain PDMS and 0.15 mL of chloroplatinic acid-isopropanol solution. Slowly add 5.9 g of PEG and 1.13 g of N-vinyl-N-methylacetamide dropwise at 120 °C. React for 5 h, cool down to 45 °C, add 0.06 g of dibutyltin dilaurate, and slowly add 2.28 g of IEM dropwise. React for 5 h to obtain a side-chain amphiphilic organosiloxane macromonomer, denoted as M1-w2.

[0102] Perform 1H NMR analysis on the side-chain amphiphilic organosiloxane macromonomer (M1-w2) prepared in this example. The results are as follows:

[0103] For M1-w2 1 1H NMR (600 MHz, CDCl3) δ 0 - 0.09 (s, 384H, Si-CH3), δ 0.46 (t, 16H, Si-CH2), δ 1.19 - 1.53 (m, 10H, C-CH2-C), δ 1.87 (s, 15H, C-CH3), δ 2.29 (t, 9H, O=C-CH3), δ 2.94 (t, 9H, N-CH3), δ 3.32 - 3.60 (m, 130H, O-CH2-C), δ 4.16 (t, 6H, N-CH2), δ 5.22 (t, 5H, N-H), δ 5.52 (s, 10H, C=CH2), δ 6.05 (s, 10H, C=CH2). From the above analysis, the structural formula of M1-w2 is as shown in the following formula:

[0104]

[0105] where m is approximately 60, n is approximately 5, q is approximately 3, and a is approximately 6.

[0106] Example 3

[0107] Preparation of Side-Chain Amphiphilic Organosiloxane Macromonomer

[0108] First, 50 g of octamethylcyclotetrasiloxane (D4), 5.4 g of tetramethylcyclotetrasiloxane (D4H), 3.65 g of hexamethyldisiloxane, and 3 g of nkc-9 cation exchange resin were placed in a three-necked flask and reacted at 65 °C for 7 h to obtain side-chain PDMS (number-average molecular weight of 5000); then, 20 g of side-chain PDMS and 0.15 mL of chloroplatinic acid-isopropanol solution were taken, and 4.73 g of PEG and 1.56 g of N-vinyl-N-methylacetamide were slowly added dropwise at 120 °C, and the reaction was carried out for 5 h. The temperature was lowered to 45 °C, 0.06 g of dibutyltin dilaurate was added, and 1.88 g of IEM was slowly added dropwise, and the reaction was carried out for 5 h to obtain a side-chain amphiphilic organosiloxane macromonomer, denoted as M1-w3.

[0109] 1H NMR analysis was performed on the side-chain amphiphilic organosiloxane macromonomer (M1-w3) prepared in this example, and the results are as follows:

[0110] For M1-w3 1 1H NMR (600 MHz, CDCl3) δ 0 - 0.09 (s, 384H, Si-CH3), δ 0.46 (t, 16H, Si-CH2), δ 1.19 - 1.53 (m, 8H, C-CH2-C), δ 1.87 (s, 12H, C-CH3), δ 2.29 (t, 12H, O=C-CH3), δ 2.94 (t, 12H, N-CH3), δ 3.32 - 3.60 (m, 104H, O-CH2-C), δ 4.16 (t, 8H, N-CH2), δ 5.22 (t, 4H, N-H), δ 5.52 (s, 8H, C=CH2), δ 6.05 (s, 8H, C=CH2)

[0111] From the above analysis, the structural formula of M1-w3 is shown as follows:

[0112]

[0113] Among them, m is about 60, n is about 4, q is about 4, and a is about 6.

[0114] Example 4

[0115] Preparation of side-chain amphiphilic organosiloxane macromonomer

[0116] First, take 50 g of octamethylcyclotetrasiloxane (D4), 5.4 g of tetramethylcyclotetrasiloxane (D4H), 3.65 g of hexamethyldisiloxane, and 3 g of nkc-9 cation exchange resin and place them in a three-necked flask. React at 65 °C for 7 h to obtain side-chain PDMS (number-average molecular weight of 5000). Then, take 20 g of side-chain PDMS and 0.15 mL of chloroplatinic acid-isopropanol solution. Slowly add 5.9 g of PEG and 0.89 g of N-vinylpyrrolidone (NVP) dropwise at 120 °C and react for 5 h. Cool down to 45 °C, add 0.06 g of dibutyltin dilaurate, and slowly add 2.28 g of IEM dropwise and react for 5 h to obtain a side-chain amphiphilic organosiloxane macromonomer, denoted as M2.

[0117] Perform 1H NMR analysis on the side-chain amphiphilic organosiloxane macromonomer (M2) prepared in this example. The results are as follows:

[0118] For M2, 1 1H NMR (600 MHz, CDCl3) δ 0 - 0.09 (s, 384H, Si-CH3), δ 0.46 (t, 16H, Si-CH2), δ 1.19 - 1.53 (m, 10H, C-CH2-C), δ 1.87 (s, 15H, C-CH3), δ 3.32 - 3.60 (m, 130H, O-CH2-C), δ 4.16 (t, 18H, N-CH2), δ 5.22 (t, 5H, N-H), δ 5.52 (s, 10H, C=CH2), δ 6.05 (s, 10H, C=CH2).

[0119] From the above analysis, the structural formula of M2 is shown as follows:

[0120]

[0121] Among them, m is about 60, n is about 5, q is about 3, and a is about 6.

[0122] Example 5

[0123] Preparation of side-chain amphiphilic organosiloxane macromonomer

[0124] First, 50 g of octamethylcyclotetrasiloxane (D4), 5.4 g of tetramethylcyclotetrasiloxane (D4H), 3.65 g of hexamethyldisiloxane, and 3 g of nkc-9 cation exchange resin were placed in a three-necked flask and reacted at 65 °C for 7 h to obtain side-chain PDMS (number-average molecular weight of 5000); then, 20 g of side-chain PDMS and 0.15 mL of chloroplatinic acid-isopropanol solution were taken, and 4.73 g of PEG and 1.56 g of N,N-dimethylacrylamide (DMA) were slowly added dropwise at 120 °C, reacted for 5 h, cooled to 45 °C, 0.06 g of dibutyltin dilaurate was added, and 1.88 g of IEM was slowly added dropwise and reacted for 5 h to obtain a side-chain amphiphilic organosiloxane macromonomer, denoted as M3.

[0125] 1H NMR analysis was performed on the side-chain amphiphilic organosiloxane macromonomer (M3) prepared in this example, and the results are as follows:

[0126] For M3, 1 1H NMR (600 MHz, CDCl3) δ 0 - 0.09 (s, 384H, Si-CH3), δ 0.46 (t, 16H, Si-CH2), δ 1.19 - 1.53 (m, 8H, C-CH2-C), δ 1.87 (s, 12H, C-CH3), δ 2.94 (t, 24H, N-CH3), δ 3.32 - 3.60 (m, 104H, O-CH2-C), δ 5.22 (t, 4H, N-H), δ 5.52 (s, 8H, C=CH2), δ 6.05 (s, 8H, C=CH2).

[0127] From the above analysis, the structural formula of M3 is as shown in the following formula:

[0128]

[0129] Among them, m is about 60, n is about 4, q is about 4, and a is about 6.

[0130] Examples 6 - 10

[0131] A silicone hydrogel was prepared by polymerization from the following components:

[0132]

[0133] Among them, the side-chain amphiphilic organosiloxane macromonomer was prepared respectively in Examples 1 - 5, and the other components and amounts remained unchanged.

[0134] The above monomers, initiator, and crosslinking agent were mixed evenly, injected into a polypropylene mold, polymerized by photoinitiation, then demolded, and hydrated to obtain the silicone hydrogel.

[0135] Examples 11 - 20

[0136] Preparation of Contact Lenses

[0137] Mix the side-chain amphiphilic organosiloxane macromonomer uniformly with small molecule silicon monomer, hydrophilic monomer, initiator and crosslinking agent, inject it into a polypropylene mold, and carry out photoinitiated polymerization (set the voltage to 175V and the light intensity to 15mV / cm 2 , polymerize for 1h), then demold, and obtain a silicone hydrogel contact lens after hydration. The obtained silicone hydrogel contact lens has a front surface and a rear surface.

[0138] Among them, the side-chain amphiphilic organosiloxane macromonomer is prepared by Examples 1-5, the small molecule silicon monomer uses methacryloxypropyltris(trimethylsiloxy)silane (TRIS), the hydrophilic monomer uses N-vinylpyrrolidone (NVP), N,N-dimethylacrylamide (DMA), hydroxypropyl methacrylate (HPMA), acrylic acid (AA), the initiator uses 2-hydroxy-2-methylpropiophenone (D1173), and the crosslinking agent uses ethylene glycol dimethacrylate (EGDMA). The reaction components and their ratio relationships of Examples 11-20 are listed in Table 1.

[0139] Comparative Example 1

[0140] Replace the side-chain amphiphilic organosiloxane macromonomer of the present invention with commercially available main-chain methacryloxybutyl-terminated polydimethylsiloxane (PDMS-25, CAS No.: 70877-62-2), prepare contact lenses according to the methods of Examples 11-20, the reaction components and their ratio relationships used are shown in Table 1, and other reaction conditions remain unchanged.

[0141] Table 1 Reaction Components and Their Ratio of Examples 11-20 and Comparative Example 1 (by mass fraction)

[0142]

[0143]

[0144] Use the polarography method of the national standard (GBT 11417.3-2012 Ophthalmic Optics Contact Lenses Part 3: Soft Contact Lenses) to measure the oxygen permeability values of the contact lenses prepared in Examples 11-20 and Comparative Example 1, and the test results are listed in Table 2.

[0145] Use a contact angle tester to measure the surface contact angles of the contact lenses prepared in Examples 11-20 and Comparative Example 1, and the test results are listed in Table 2.

[0146] The water content of the contact lenses prepared in Examples 11-20 and Comparative Example 1 was measured by the weighing method. The weight of the glass slide was Q1, the weight of the lens and the glass slide was Q2. After drying to a constant weight in an oven at 50 °C, the gross weight was G3. The water content = (Q2 - G3) / (Q2 - Q1). The test results are listed in Table 2.

[0147] Table 2 Test Results

[0148]

[0149] As can be seen from Table 2, the oxygen permeability of the contact lenses in Examples 11-20 is above 120 barrer, and in some examples it is even as high as above 160 barrer, far higher than that of Comparative Example 1; while maintaining high oxygen permeability, the water content of the contact lenses in Examples 11-20 is above 50%, and the surface contact angle is below 70°, which is also significantly better than that of Comparative Example 1. This shows that the contact lenses prepared from the side-chain amphiphilic organosiloxane macromonomer of the present invention have both excellent properties of high oxygen permeability and high hydrophilicity.

[0150] Those skilled in the art should understand that the present invention is not limited by the above specific embodiments. The descriptions in the above specific embodiments and the specification are only to further illustrate the principle of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed. The scope of the present invention claimed is defined by the claims and their equivalents.

Claims

1. A side-chain amphiphilic organosiloxane macromonomer, characterized in that, The structural general formula of the side-chain amphiphilic organosiloxane macromonomer is as shown in the following formula (I): Among them, X1 is an alkyl group having C1-C 10 and X2 is a is an integer between 4 and 20, X3 is R1 is a hydrogen atom, a phenyl group or an alkyl group having C1-C 10 and R2 is a hydrogen atom, a phenyl group or an alkyl group having C1-C 10 , and m, n, and q are all integers between 5 and 100.

2. The preparation method of the side-chain amphiphilic organosiloxane macromonomer according to claim 1, characterized in that, It includes the following steps: (1) Octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane are synthesized into a linear hydrogen-containing polydimethylsiloxane macromolecule under the action of a siloxane capping agent and a catalyst; (2) Then a hydroxyl-terminated polyether allyl polyether and a hydrophilic monomer are added, and a side-chain grafted polydimethylsiloxane macromolecule is synthesized through a hydrosilylation reaction under the action of the catalyst chloroplatinic acid; (3) Finally, it reacts with isocyanatoethyl methacrylate under the action of a catalyst to generate a side-chain amphiphilic organosiloxane macromonomer.

3. The side-chain amphiphilic organosiloxane macromonomer according to claim 1 is used for preparing a silicone hydrogel or a contact lens.

4. A silicone hydrogel, characterized in that, It contains the side-chain amphiphilic organosiloxane macromonomer according to claim 1 and the following components, and is prepared by a polymerization reaction according to the mass parts: The side-chain amphiphilic organosiloxane macromonomer of formula (I) 5 - 45 parts, Small molecule silicon monomer 0 - 30 parts, Hydrophilic monomer 25 - 70 parts, Initiator and crosslinking agent; Among them, the sum of the mass parts of the side-chain amphiphilic organosiloxane macromonomer, small molecule silicon monomer and hydrophilic monomer of formula (I) is 100 parts; the initiator accounts for 0.5 - 3% of the sum of the weights of the side-chain amphiphilic organosiloxane macromonomer, small molecule silicon monomer and hydrophilic monomer; the crosslinking agent accounts for 0.5 - 3% of the sum of the weights of the side-chain amphiphilic organosiloxane macromonomer, small molecule silicon monomer and hydrophilic monomer.

5. The silicone hydrogel according to claim 4, characterized in that, The small molecule silicon monomer is one or any combination of methacryloxypropyl tris(trimethylsiloxy)silane, methyl-di(trimethylsiloxy)-silylpropyl glycerol methacrylate, 3-(methacryloyloxy)propyltrimethoxysilane and methacryloxymethyl tris(trimethylsiloxy)silane.

6. The silicone hydrogel according to claim 4, wherein The hydrophilic monomer is one or a combination of N-vinylpyrrolidone, hydroxypropyl methacrylate, hydroxyethyl methacrylate, N,N-dimethylacrylamide, methacrylic acid, N-vinylacetamide, glycerol methacrylate, glycidyl methacrylate, hydroxybutyl methacrylate, N-vinyl-N-methylacetamide, acrylic acid, acrylamide.

7. The silicone hydrogel according to claim 4, characterized in that, The initiator is a photoinitiator or a thermal initiator; the photoinitiator is at least one of 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2,4,6-trimethylbenzyl diphenyl phosphine oxide; the thermal initiator is at least one of azobisisobutyronitrile, benzoyl peroxide, azodiisooctanenitrile, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate and bis(2-phenylethoxy) peroxydicarbonate.

8. The silicone hydrogel according to claim 4, characterized in that, The crosslinking agent is one or any combination of polyethylene glycol diacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triallyl isocyanurate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, diethylene glycol divinyl ether, vinyl methacrylate, divinyl polyethylene glycol ester and trimethylolpropane trimethacrylate.

9. A contact lens, characterized in that, Comprising a side-chain amphiphilic organosiloxane macromonomer as described in claim 1 or a silicone hydrogel as described in any one of claims 4-8.

10. The method for preparing the contact lens according to claim 9, characterized in that, Comprising the following steps: Mixing a side-chain amphiphilic organosiloxane macromonomer of formula (I), a small molecule silicone monomer, a hydrophilic monomer, an initiator and a crosslinking agent uniformly, injecting the mixture into a contact lens mold, carrying out photoinitiated or thermally initiated polymerization, demolding, extracting unpolymerized monomers and oligomers in the lens with deionized water, and immersing the lens in physiological saline for equilibration to obtain a contact lens.

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