CN113248719B - Single-end-capped organic siloxane oligomer, silicon hydrogel, corneal contact lens and preparation method - Google Patents

Abstract

The invention discloses a single-end-capped organosiloxane oligomer, which is well mixed with various hydrophilic monomers under the condition of no solvent-assisted solubilization, and overcomes the problem of organosiloxane oligomer and hydrophilic The problem of insoluble monomers is difficult to dissolve each other, and silicon hydrogel materials with high oxygen permeability and high hydrophilicity can be prepared. At the same time, the present invention also provides a silicone hydrogel, which is formed by the polymerization of the single-terminated organosiloxane oligomer and a hydrophilic monomer. No solvent is added to the formula of the silicone hydrogel, which is beneficial to large Large-scale industrial production; and the proportion of organosiloxane oligomer added in the silicone hydrogel is large, so that the silicone hydrogel has high oxygen permeability, while maintaining the high hydrophilicity and flexibility of the gel . The present invention also provides a corneal contact lens, which is made of the silicon hydrogel material and has the advantages of high oxygen permeability, strong hydrophilicity, good light transmission, less lipid deposition, good flexibility, and comfortable wearing. advantage.

Description

Single-terminated organosiloxane oligomer, silicone hydrogel, contact lens and preparation method

technical field

The invention relates to a single-end capped organosiloxane oligomer, a silicon hydrogel, a corneal contact lens and a preparation method, and belongs to the field of material preparation of contact lens lenses.

Background technique

Contact lenses, also known as contact lenses, are lenses that are worn directly on the eyeball to correct vision. Compared with ordinary glasses, contact lenses are convenient, beautiful and comfortable. Contact lenses can be divided into hard contact lenses and soft contact lenses. Rigid contact lenses, due to their hard material and poor wettability, can easily cause discomfort to the eyeball when wearing them. Soft contact lenses have good chemical stability, light transmittance, biocompatibility, ion permeability and mechanical properties, and are more comfortable to wear.

In the history of the development of the soft contact lens industry, hydrogel materials made of acrylic acid first appeared. In the 1970s, poly(2-hydroxyethyl methacrylate) (HEMA) and other Hydrophilic polymer-based hydrogels were introduced as materials to meet the requirements for gas transport and mechanical operability of contact lenses. However, these polymers are not inherently oxygen permeable, and can only transmit oxygen through the water molecules swollen in them, resulting in lower oxygen permeability.

The field of contact lenses has high requirements on the oxygen permeability of materials. If oxygen cannot be supplied normally during the wearing of contact lenses, the cornea will be hypoxic. Long-term insufficient oxygen supply will cause thinning of the corneal epithelium and dry eyes. In order to solve the problem of oxygen supply, in the early stage, people tried to improve the oxygen permeability of hydrogels by increasing the water content. However, without changing the composition of conventional hydrogels, simply increasing the water content, the maximum oxygen permeability value can only reach 40 barrer. Although it can meet the needs of some biomedical fields, the oxygen permeability requirements for contact lenses are relatively high. product, its application still has limitations.

With the deepening of research, people have discovered many materials with high oxygen permeability. Among them, silicon-containing polymer materials have the advantages of extremely high oxygen permeability, good mechanical properties, biocompatibility, safety and environmental protection. Hydrophobic, it will adhere to lipids and proteins when applied to biological tissues, and it is harmful for long-term use. The properties of this material and hydrogel materials are complementary, so researchers have tried to change the composition of the hydrogel and combine it with materials with high oxygen permeability to improve its oxygen permeability. Based on the good air permeability and biocompatibility of silicon-containing polymers, the combination of the two forms a silicone hydrogel with good comprehensive properties. The siloxane part determines the oxygen permeability of the material, and the hydrogel part can reduce the material Wear with tissue for added comfort. Based on the unique performance advantages of silicone hydrogels, it has broad application prospects in the field of contact lenses.

Silicone hydrogel lenses are generally copolymerized by silicone monomers and hydrophilic monomers, and usually contain one or two or more small molecular weight silicone monomers or larger molecular weight silicone oligomers. Small molecule silicone monomers such as methacryloyloxypropyl tris(trimethylsiloxane) silane (TRIS), 3-(3-methacryloyloxy-2-hydroxypropyl)propyl bis (Trimethylsiloxane) methylsilane (SIGMA), etc., have good hydrophilicity and good compatibility with hydrophilic monomers, but have a limited effect on improving the oxygen permeability of the material. Organosilicon oligomers with larger molecular weight are generally obtained by grafting reactive functional groups with polydimethylsiloxane (PDMS), and can be copolymerized with hydrophilic monomers, which can effectively improve the oxygen permeability value of the material. However, due to the high hydrophobicity of PDMS, the compatibility with hydrophilic monomers is poor, and the addition amount is limited, which limits the improvement of the oxygen permeability value of the material; and the surface of the obtained silicone hydrogel has strong hydrophobicity, which affects the performance of the lens. Wearing comfort.

In addition, due to the low surface energy and hydrophobicity of PDMS, after the polymerization of silicone monomers and hydrophilic monomers, the silicon-containing groups easily migrate to the surface of the silica hydrogel, resulting in higher lipid adsorption. Excessive lipid adsorption of the lens can easily cause blurred vision, reduce wearing comfort, and cause inflammation after long-term wearing.

Therefore, it is urgent for those skilled in the art to develop an effective organosiloxane oligomer for preparing silicone hydrogel lenses with high oxygen permeability, high hydrophilicity and anti-lipid precipitation properties. one of the technical problems.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a single-terminated organosiloxane oligomer, which has good mutual solubility with various hydrophilic monomers in the absence of solvent-assisted solubilization, and can prepare high oxygen permeability and high hydrophilicity. Silicon hydrogel lenses with high permeability and low lipid adsorption rate; at the same time, a silicone hydrogel material and a corneal contact lens are also provided, which have good oxygen permeability, light transmittance and anti-lipid precipitation performance, and strong hydrophilicity. , good flexibility, comfortable to wear.

The present invention provides a single-terminated organosiloxane oligomer having the structure shown in formula (I):

Wherein, the value range of m is an integer between 4-20, the value range of n is an integer between 5-100, and R is a C ₁ -C ₁₀ alkyl group.

The present invention also provides a method for preparing the single-terminated organosiloxane oligomer, which comprises: under the action of a catalyst, in the temperature range of 20-90° C., the single-hydroxyl-terminated polyether-modified polydimethyl The siloxane is first reacted with isophorone diisocyanate, and then hydroxyethyl methacrylate is added to continue the reaction to obtain the single-terminated organosiloxane oligomer of formula (I).

The single-terminated organosiloxane oligomers are used to prepare silicone hydrogels and contact lenses.

On the other hand, the present invention also provides a silicone hydrogel, comprising the single-terminated organosiloxane oligomer and the following components, which are prepared by a polymerization reaction in parts by mass:

5 to 55 parts of the mono-terminated organosiloxane oligomer of formula (I),

Small molecule silicon monomer 0～30 parts,

15-70 parts of hydrophilic monomers,

Initiators and crosslinkers;

Among them, the sum of the mass fractions of single-terminated organosiloxane oligomer, small molecular silicon monomer and hydrophilic monomer is 100 parts; 0.5-3% of the weight of the silicon monomer and the hydrophilic monomer; the cross-linking agent accounts for 0.5-3% of the weight of the mono-terminated organosiloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer .

According to a specific but non-limiting embodiment of the present invention, the mass fraction of the mono-terminated organosiloxane oligomer of formula (I) is 30-55 parts.

According to a specific but non-limiting embodiment of the present invention, the small molecular silicon monomer is methacryloyloxymethyltris(trimethylsiloxy)silane, methacryloyloxypropyltris (Trimethylsiloxane)silane, γ-aminopropyltriethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, and 3-(3-methacryloyloxy- One or any combination of 2-hydroxypropyl)propylbis(trimethylsiloxane)methylsilane.

According to a specific but non-limiting embodiment of the present invention, the hydrophilic monomer is N-vinylpyrrolidone, vinylcyclohexanamide, polyether methacrylate, methacrylic acid, hydroxyl methacrylate Ethyl Esters, Hydroxypropyl Methacrylate, Hydroxybutyl Methacrylate, Glyceryl Methacrylate, Glycidyl Methacrylate, N,N-Dimethacrylamide, N-Vinylacetamide and N-Ethylene One or a combination of several methyl acetamides.

According to a specific but non-limiting embodiment of the present invention, the initiator is a photoinitiator or a thermal initiator; the photoinitiator is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2- At least one of methyl propiophenone and 2,4,6-trimethylbenzyldiphenylphosphine oxide, and the thermal initiator is azobisisobutyronitrile, azobisisoheptanenitrile and peroxide at least one of benzoyl;

The crosslinking agent is triallyl isocyanurate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetraethylene glycol dimethyl acrylate. At least one of acrylate, divinyl polyethylene glycol ether, and trimethylolpropane trimethacrylate.

The present invention also provides a corneal contact lens, which is made of the silicon hydrogel.

At the same time, the present invention also provides a method for preparing the corneal contact lens, comprising: adding 5-55 parts of the mono-terminated organosiloxane oligomer of formula (I), 0-30 parts of a small molecular silicon monomer, a hydrophilic 15-70 parts of sexual monomers, initiator and cross-linking agent are mixed evenly, injected into the contact lens mold, photo-induced or thermally induced to polymerize and cure, and hydrated to obtain contact lenses; The sum of parts by mass of polymer, small molecular silicon monomer and hydrophilic monomer is 100 parts; the initiator accounts for the weight of single-terminated organosiloxane oligomer, small molecular silicon monomer and hydrophilic monomer The cross-linking agent accounts for 0.5-3% of the total weight of the mono-terminated organosiloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer.

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

1. The single-terminated organosiloxane oligomer of the present invention has excellent hydrophilicity and good mutual solubility with hydrophilic monomers, which effectively solves the problem that the organosiloxane oligomers and hydrophilic monomers are difficult to dissolve in each other. The problem is that it can be added to the silicone hydrogel in a large proportion without the need for a co-solvent, which greatly increases the addition amount of the organosiloxane oligomer and significantly improves the oxygen permeability of the silicone hydrogel, so that the The prepared silicone hydrogel material has high hydrophilicity, high oxygen permeability and good light transmittance at the same time.

2. There is no solvent added to the silicone hydrogel formulation of the present invention, which is beneficial to large-scale industrial production, not only reduces production costs, reduces environmental pollution, but more importantly, avoids the use of solvents in the process of preparing lenses by polymerizing mixed monomers. A large amount of volatilization reduces the health hazards to operators and the risk of major accidents such as explosion and combustion.

3. The silicon hydrogel material prepared by the present invention has good oxygen permeability and light transmittance, while maintaining the high hydrophilicity and flexibility of the gel, and has good anti-lipid precipitation performance.

4. The corneal contact lens prepared by the present invention has properties such as high oxygen permeability, high water content and good anti-lipid deposition, comfortable to wear, good flexibility, and high oxygen permeability can reduce ophthalmic diseases caused by hypoxia The incidence is beneficial to eye health.

Description of drawings

FIG. 1 is the nuclear magnetic spectrum of the single-terminated organosiloxane oligomer prepared in Example 1. FIG.

Detailed ways

Specific embodiments are provided below to further illustrate the present invention, but the present invention is not limited to the following embodiments.

The inventors of the present application have found through experiments that when the polyether segment is connected to the long polysiloxane chain, the synthesized organosiloxane oligomer has better hydrophilicity and good mutual solubility with hydrophilic monomers, and can A large proportion of organosiloxane oligomer is added to the silicone hydrogel, which greatly increases the addition amount of the organosiloxane oligomer, thereby significantly improving the oxygen permeability of the silicone hydrogel material. Usually, the organosiloxane oligomer needs to be well miscible with the hydrophilic monomer under the participation of co-solvent. Once dissolved, it can be well mixed with various hydrophilic monomers, so no solvent is added to the silicone hydrogel formulation of the present invention, and avoiding the use of solvents is beneficial to large-scale industrial production, so the present invention has very significant beneficial effects. However, the structure of the single-terminated organosiloxane oligomer provided by the present invention and the silicon hydrogel prepared therefrom have not been reported in the literature.

The present invention provides a single-terminated organosiloxane oligomer having the structure shown in formula (I):

Wherein, the value range of m is an integer between 4-20, the value range of n is an integer between 5-100, and R is a C ₁ -C ₁₀ alkyl group. Preferably, the value range of m is an integer between 8 and 15, and the value range of n is an integer between 20 and 60.

The single-terminated organosiloxane oligomer of the above formula (I) is a block copolymer, wherein the polysiloxane long chain (1) gives the material good oxygen permeability, the polyether segment (2) and the end group The grafted amide and methacrylate groups (3) provide good hydrophilicity. We found through experiments that when the polyether segment (2) is connected to the polysiloxane long chain (1), the synthesized polymer has better hydrophilicity and good mutual solubility with hydrophilic monomers, which solves the problem of organosiloxane oxygen. Alkane oligomers and hydrophilic monomers are difficult to dissolve in each other. A large proportion of organosiloxane oligomers can be added to silicone hydrogels without the need for co-solvents, which greatly improves the efficiency of organosiloxane oligomers. The added amount of oligomer significantly improves the oxygen permeability and light transmittance of the silicone hydrogel material. Moreover, the connection between the polyether segment (2) and the polysiloxane long chain (1) is also beneficial to improve the anti-lipid precipitation performance of the silicone hydrogel material. The lipid adsorption of gel lenses is lower.

Mono-terminated organosiloxane oligomers of formula (I) can be prepared by the following methods:

Under the action of a catalyst, the monohydroxy-terminated polyether-modified polydimethylsiloxane (HO-PDMS) first reacts with isophorone diisocyanate (IPDI) in the temperature range of 20 to 90 °C to generate IPDI The end-capped intermediate product is then added with hydroxyethyl methacrylate (HEMA) to continue the reaction to obtain a single-end capped organosiloxane oligomer. Wherein, the catalyst is dibutyltin dilaurate. HO-PDMS was reacted with IPDI and HEMA in equal proportions.

Wherein, the value range of m is an integer between 4-20, the value range of n is an integer between 5-100, and R is a C ₁ -C ₁₀ alkyl group.

Further, the present invention provides a silicone hydrogel, comprising the following components, in parts by mass, prepared by a polymerization reaction:

5 to 55 parts of the mono-terminated organosiloxane oligomer of formula (I),

Small molecule silicon monomer 0～30 parts,

15-70 parts of hydrophilic monomers,

Initiators and crosslinkers;

Among them, the sum of the mass fractions of single-terminated organosiloxane oligomer, small molecular silicon monomer and hydrophilic monomer is 100 parts; 0.5-3% of the weight of the silicon monomer and the hydrophilic monomer; the cross-linking agent accounts for 0.5-3% of the weight of the mono-terminated organosiloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer .

Preferably, the mass fraction of the mono-terminated organosiloxane oligomer of formula (I) is 30-55 parts, and the mass fraction of other components is unchanged.

Specifically, the mono-terminated organosiloxane oligomers of formula (I) are as described above.

The small molecular silicon monomer can be methacryloyloxymethyl tris(trimethylsiloxy) silane (MTTS), methacryloyloxypropyl tris(trimethylsiloxane) silane (TRIS), γ-aminopropyltriethoxysilane (KH-550), 3-(methacryloyloxy)propyltrimethoxysilane (KH-570), and 3-(3-methacryloyl One or any combination of oxy-2-hydroxypropyl)propylbis(trimethylsiloxane)methylsilane (SIGMA). As a solubilizing monomer in silicone hydrogels, small molecular silicon monomers can increase the compatibility of siloxane macromonomers and hydrophilic monomers. At the same time, small molecular silicon monomers have a certain effect on the improvement of oxygen permeability. effect.

The hydrophilic monomer can be N-vinylpyrrolidone (NVP), vinylcyclohexanamide (NVCA), polyether methacrylate, methacrylic acid (MAA), hydroxyethyl methacrylate (HEMA) ), hydroxypropyl methacrylate (HPMA), hydroxybutyl methacrylate, glycerol methacrylate, glycidyl methacrylate, N,N-dimethylacrylamide (DMA), N-vinylethyl One or a combination of N-vinylmethylacetamide (NVA) and N-vinylmethylacetamide. 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 is a photoinitiator or a thermal initiator. The photoinitiator is at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl propiophenone (D1173) and 2,4,6-trimethylbenzyldiphenylphosphine oxide. The thermal initiator is at least one of azobisisobutyronitrile (AIBN), azobisisoheptanenitrile and benzoyl peroxide (BPO).

The crosslinking agent can be triallyl isocyanurate (TAIC), ethylene glycol dimethacrylate (EGDMA), triethylene glycol dimethacrylate, polyethylene glycol diacrylate ( PEGDA), at least one of tetraethylene glycol dimethacrylate, divinyl polyethylene glycol ether, and trimethylolpropane trimethacrylate.

In actual production, other functional monomers can also be added to the silicone hydrogel material as required, such as a colored monomer, a color-changing monomer, or a monomer that blocks ultraviolet light, blue light, and near-infrared light.

Since the single-terminated organosiloxane oligomer of formula (I) has excellent hydrophilicity, it has good compatibility with hydrophilic monomers, and does not require solvent to assist solubilization, so in the silicone hydrogel formulation of the present invention No solvent is added, 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.

At the same time, since the single-terminated organosiloxane oligomer of formula (I) has good mutual solubility with hydrophilic monomers, it can be added to the silicone hydrogel in a large proportion, which greatly improves the addition of organosiloxane oligomers. Therefore, the oxygen permeability of the silicone hydrogel was significantly improved. The added amount of the single-terminated organosiloxane oligomer of the present invention in the silicone hydrogel is 5-55%, and the organosiloxane oligomer almost accounts for 5-55% of the total weight of the silicone hydrogel. That is to say, the present invention can achieve the addition amount of the organosiloxane oligomer to reach more than 40%, while the commercially available mono-terminated organosiloxane oligomer can only add about 20%, which is far lower than the present invention. Add level.

The invention effectively solves the problem that the organosiloxane oligomer and the hydrophilic monomer are difficult to dissolve each other, and greatly improves the oxygen permeability of the silicon hydrogel on the premise of maintaining a high water content, thereby realizing the silicon hydrogel The material has the goals of high oxygen permeability and high water content, which greatly improves the performance of silicone hydrogel materials. Experiments show that the water content of the silicon hydrogel prepared by the present invention is 30-60%, and the oxygen permeability can reach more than 150 barrer, even more than 180 barrer, which is significantly higher than that of commercially available silicon hydrogel corneal contact lenses; The adsorption is very low, less than 0.0030mg/piece, indicating that the lens prepared by the present invention has excellent lipid adsorption resistance; meanwhile, the elongation at break reaches more than 160%, indicating that the contact lens prepared by the present invention has good flexibility.

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:

Mix 5-55 parts of single-terminated organosiloxane oligomer of formula (I), 0-30 parts of small molecular silicon monomer, 15-70 parts of hydrophilic monomer, initiator and cross-linking agent evenly, Injected into a contact lens mold, photo-induced or thermally induced polymerization and curing, and hydrated to obtain a silicone hydrogel contact lens; wherein, single-terminated organosiloxane oligomer, small molecular silicon monomer and hydrophilic mono The sum of the mass parts of the body is 100 parts; the initiator accounts for 0.5-3% of the weight of the single-terminated organosiloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer; 0.5-3% of the weight sum of terminal organosiloxane oligomer, small molecular silicon monomer and hydrophilic monomer.

The corneal contact lens of the present invention is made of the above-mentioned silicon hydrogel material. The silicon hydrogel material has good oxygen permeability and light transmittance, while maintaining the high hydrophilicity and flexibility of the gel, and has good anti-lipid precipitation properties. The corneal contact lens prepared with this silicone hydrogel is comfortable to wear, has good flexibility and high oxygen permeability, can reduce the incidence of ophthalmic diseases caused by hypoxia, and is beneficial to eye health; good light transmission performance ensures The visual effect and comfort of wearing.

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

Example 1

Preparation of Mono-terminated Organosiloxane Oligomers

Take 50g of monohydroxy-terminated polyether-modified polydimethylsiloxane (HO-PDMS, the number average molecular weight is about 1500, the structural formula is as shown above, wherein m is about 8, n is about 15, purchased from Nanjing Fu Group Chemical Co., Ltd.), dropwise add 0.3g dibutyltin dilaurate, stir evenly, gradually add IPDI 7.41g, turn on the constant temperature water bath heating device at the same time, adjust the temperature to 70°C, start timing after the dropwise addition, and react for 4h. The temperature was lowered to 50° C., 4.34 g of HEMA monomer was added dropwise, and the mixture was stirred for 24 h to obtain a product, which was recorded as M1 (the structural formula is shown in the above formula (I), where m is about 8 and n is about 15), which is sealed and stored. FIG. 1 is the nuclear magnetic spectrum of the single-terminated organosiloxane oligomer prepared in Example 1. FIG.

Example 2

Preparation of Mono-terminated Organosiloxane Oligomers

Take 50g of monohydroxy-terminated polyether-modified polydimethylsiloxane (HO-PDMS, the number average molecular weight is about 3000, the structural formula is as shown above, wherein m is about 10, n is about 35, purchased from Nanjing Fu Group Chemical Co., Ltd.), dropwise add 0.2g dibutyltin dilaurate, stir evenly, gradually add IPDI 3.71g, turn on the constant temperature water bath heating device at the same time, adjust the temperature to 70°C, start timing after the dropwise addition, and react for 4h. The temperature was lowered to 50° C., 2.17 g of HEMA monomer was added dropwise, and the mixture was stirred for 24 h to obtain a product, which was recorded as M2 (the structural formula is shown in formula (I) above, where m is about 10 and n is about 35), which is sealed and stored.

Example 3

Preparation of Mono-terminated Organosiloxane Oligomers

Take 50g of monohydroxy-terminated polyether-modified polydimethylsiloxane (HO-PDMS, the number average molecular weight is about 4000, the structural formula is as shown above, wherein m is about 12, n is about 45, purchased from Nanjing Fu Group Chemical Co., Ltd.), dropwise add 0.2g dibutyltin dilaurate, stir evenly, gradually add IPDI 2.78g, turn on the constant temperature water bath heating device at the same time, adjust the temperature to 70°C, start timing after the dropwise addition, and react for 4h. The temperature was lowered to 50°C, 1.63 g of HEMA monomer was added dropwise, and the mixture was stirred for 24 h to obtain a product, which was recorded as M3 (the structural formula is shown in formula (I) above, where m is about 12 and n is about 45), which is sealed and stored.

Example 4

Preparation of Mono-terminated Organosiloxane Oligomers

Take 50g of monohydroxy-terminated polyether-modified polydimethylsiloxane (HO-PDMS, the number average molecular weight is about 6000, the structural formula is as shown above, wherein m is about 15, n is about 70, purchased from Nanjing Fu Group Chemical Co., Ltd.), add 0.15g of dibutyltin dilaurate dropwise, stir evenly, gradually add 1.85g of IPDI, turn on the constant temperature water bath heating device at the same time, adjust the temperature to 70°C, start timing after the dropwise addition is complete, and react for 4h. The temperature was lowered to 50°C, 1.08 g of HEMA monomer was added dropwise, and the mixture was stirred for 24 h to obtain a product, which was recorded as M4 (the structural formula is shown in the above formula (I), where m is about 15 and n is about 70), which is sealed and stored.

Examples 5-8

A silicone hydrogel prepared by polymerization of the following components:

In Examples 5-8, the single-terminated organosiloxane oligomers were prepared from Examples 1-4, respectively, and other components and parts were unchanged.

Examples 9-16

Preparation of Contact Lenses

The mono-terminated organosiloxane oligomer, small molecular silicon monomer, hydrophilic monomer, initiator and crosslinking agent are mixed uniformly, injected into the contact lens mold, thermally induced to polymerize, then demolded, and made after hydration. Silicone hydrogel contact lenses were obtained. The resulting contact lens has an anterior surface and a posterior surface.

Among them, the single-terminated organosiloxane oligomers were prepared from Examples 1-4 respectively; the small molecular silicon monomer was methacryloyloxypropyl tris(trimethylsiloxane) silane (TRIS); The water monomer adopts N-vinylpyrrolidone (NVP), vinylcyclohexanamide (NVCA), hydroxypropyl methacrylate (HPMA); the initiator adopts azobisisobutyronitrile (AIBN); Ethylene glycol methacrylate (EGDMA). The contact lenses of Examples 9-16 were all prepared according to the above-mentioned process, and their respective reaction components and proportioning relationships (in parts by mass) are listed in Table 1.

Comparative example 1-2

The monoblock of the present invention was replaced with a commercially available mono-terminated macrosilicon monomer (7-9% methacryloyloxypropyl-methylsiloxane)-dimethylsiloxane copolymer (RMS-083). For the end-capped organosiloxane oligomer, contact lenses were prepared according to the methods of Examples 9-16. The reaction components and the proportioning relationship used are shown in Table 1, and other reaction conditions remain unchanged.

The reaction components and proportions (in parts by mass) of Table 1 Examples 9-16 and Comparative Examples 1-2

Example 17

The elongation rates of the contact lenses prepared in Examples 9-16 were respectively tested using an electronic tensile tester XLW (PC). Each sample was clamped with a splint for measurement, and the tensile elongation at break of the contact lens sample was measured. The test results are listed in Table 2.

The oxygen permeability values of the contact lenses prepared in Examples 9-16 were measured by the national standard (GBT 11417.3-2012) coulometric method, and the test results are listed in Table 2.

The moisture content of the contact lenses prepared in Examples 9-16 were measured by weighing method, the weight of the glass slide Q1, the weight of the lens and the glass slide Q2, after drying in a 50°C oven to constant weight, the gross weight G3, the water content = (Q2-G3)/(Q2-Q1), the test results are shown in Table 2.

The lipid adsorption of Examples 9-16 was detected by the chromogenic method of jarosite chromogenic reagent and lipid, and then the amount of lipid adsorption was detected by evolution 220 spectrophotometer.

Various performance tests were carried out with Examples 1-2 and Examples 9-16, and the test results are listed in Table 2.

Table 2 Performance test results

As can be seen from Table 2, the oxygen permeability of the contact lenses of the present invention is all above 150 barrer, and some examples are even as high as 180 barrer or more, which is significantly higher than the comparative example; and the water content of the contact lenses of the present invention is also significantly higher than The lipid adsorption of the corneal contact lens of the present invention is very low, which is lower than that of the comparative example to a greater extent, and is reduced by more than 40% compared with the comparative example; this shows that the cornea prepared from the single-terminated organosiloxane oligomer of the present invention Contact lenses have excellent properties such as high oxygen permeability, high water content and anti-lipid adsorption. Meanwhile, the corneal contact lens of the present invention has a high elongation at break, indicating that the corneal contact lens prepared by the present invention has good flexibility, durability and is not easy to break.

It should be understood by those skilled in the art that the present invention is not limited by the above-mentioned specific embodiments, and the descriptions in the above-mentioned 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 Various changes and modifications of the invention are also possible, all of which fall within the scope of the claimed invention. The claimed scope of the present invention is defined by the claims and their equivalents.

Claims (10)

1. A mono-end-capped organosiloxane oligomer having the structure of 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).

2. A method of preparing the mono-end-capped organosiloxane oligomer of claim 1 comprising: 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 use of the mono-end-capped organosiloxane oligomer of claim 1 in the preparation of silicone hydrogels and corneal contact lenses.

4. The silicone hydrogel is characterized by comprising the following components in parts by mass and prepared through polymerization reaction:

5 to 55 portions of single-end-capped organic siloxane oligomer,

0 to 30 parts of micromolecular silicon monomer,

15 to 70 parts of hydrophilic monomer,

an initiator and a crosslinking agent;

wherein 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 sum of the mass parts of the single-end-capped organic siloxane oligomer, the micromolecular 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 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-capping organosiloxane oligomer, the weight of the micromolecule silicon monomer and the weight of the hydrophilic monomer.

5. The silicone hydrogel of claim 4, wherein the mass fraction of the mono-end-capped organosiloxane oligomer of formula (I) is from 30 to 55 parts.

6. The silicone hydrogel of claim 4 or 5, wherein the small molecule silicon monomer is one or any combination of methacryloxymethyltris (trimethylsiloxy) silane, methacryloxypropyltri (trimethylsiloxy) silane, γ -aminopropyltriethoxysilane, 3- (methacryloxy) propyltrimethoxysilane, and 3- (3-methacryloxy-2-hydroxypropyl) propylbis (trimethylsiloxane) methylsilane.

7. The silicone hydrogel of claim 4 or 5, wherein said hydrophilic monomer is one or a combination of N-vinyl pyrrolidone, vinyl cyclohexanamide, polyether methacrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, glycerol methacrylate, glycidyl methacrylate, N-dimethylacrylamide, N-vinylacetamide and N-vinylmethylacetamide.

8. The silicone hydrogel of claim 4 or 5, 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;

the cross-linking agent is at least one of triallyl isocyanurate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetraethylene glycol dimethacrylate, divinyl polyethylene glycol ether and trimethylolpropane trimethacrylate.

9. A corneal contact lens made from the silicone hydrogel of any one of claims 4 to 8.

10. A method of making a corneal contact lens as in claim 9, comprising: uniformly mixing 5-55 parts of single-end-capped organic siloxane oligomer shown in the formula (I), 0-30 parts of micromolecule silicon monomer, 15-70 parts of hydrophilic monomer, initiator and cross-linking agent, injecting into a corneal contact lens mould, carrying out polymerization and curing under photo-initiation or thermal initiation, and hydrating to obtain the corneal contact lens; wherein the sum of the mass parts of the single-end-capped organic siloxane oligomer, the micromolecular 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 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-capping organosiloxane oligomer, the weight of the micromolecule silicon monomer and the weight of the hydrophilic monomer.

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