TWM521076U - A silicone hydrogel contact lens containing crossed silicone monomers - Google Patents

Description

Hydrophobic lens containing cross-shaped bismuth monomer

The present invention relates to a contact lens and a substrate thereof, and more particularly to a hydrophobic glue made of a hydrophobic polymer containing a polymerizable functional group and a hydrophilic group. lens.

Since Silicone hydrogel has good oxygen permeability, wettability and biocompatibility, it is widely used in the manufacture of contact lenses. Today, tantalum monomers used in contact lens manufacturing can be classified into linear type. Oxyalkane and cross-type alkane, as disclosed in Taiwan Patent Publication No. TWI434865, discloses a linear polyoxyalkylene having a hydrophilic side chain such as a guanamine functional group or a phosphorylcholine functional group, or as disclosed in the U.S. Patent Publication. No. 4,463,149 discloses a structure of a small molecular cross-type oxirane.

Although linear linear decane can be modified to have good hydrophilicity, linear siloxane is a one-dimensional structure, and its oxygen permeability is often lower than that of a two-dimensional structure of a cross-type siloxane. Although cross-type oxane has a good oxygen permeability, due to its hydrophobic nature, it also causes a decrease in water content.

Therefore, how to synthesize a hydrophobic plastic lens with high oxygen permeability and high water content is the technical problem to be solved in this case.

The present invention provides a hydrophobic plastic lens comprising a lens body having an inner surface and an outer surface, the lens body being composed of a central optical zone and an edge zone, the central optical zone having a diameter of 5 to 10 mm, the central optical The thickness of the region is between 0.04 and 0.15 mm, and the thickness of the edge region is 0.22 mm. The lens system is made of a hydrophobic gel prepolymer containing a polymerizable functional group and a hydrophilic group of a cross-type alkane polymer.

In the above preferred embodiment, the cross-type alkane polymer containing a polymerizable functional group and a hydrophilic group has the chemical structure of the formula (I):

In the formula (I), R ₂ is a chemical structure represented by the following formula,

In R ₂ , the m value is between 5 and 1000, the n value is between 0 and 150, and the hydrophilic group R ₄ is a hydrophilic structure represented by the following formula.

In R ₄ , the y value is between 0 and 100, the z value is between 0 and 50, and R ₃ is any one of a hydroxyl group and a methyl group.

In the above preferred embodiments, at least three of the R ₂ have a hydrophilic group R ₄ .

In the above preferred embodiment, wherein the hydrophilic group R ₄ is selected from the group consisting of 3-allyloxy-1,2, propylene glycol, 2-allyloxyethanol, trimethylolpropane allyl ether At least one of them.

In the above preferred embodiment, the hydrophobic gel lens further comprises: tris-[tris(trimethyldecyloxy)]propyl methacrylate decane, N-vinylpyrrolidone, 2-hydroxy methacrylate At least one of the ethyl esters.

In the above preferred embodiment, the central optical zone diameter is further between 6.5 and 9 mm.

In the above preferred embodiment, the central optical zone thickness is further between 0.06 and 0.1 mm.

S11~S14‧‧‧Steps

1‧‧‧ lens body

11‧‧‧Central Optical Zone

12‧‧‧Edge area

13‧‧‧ outer surface

14‧‧‧ inner surface

D1‧‧‧Center optical zone diameter

Fig. 1 is a schematic flow chart showing the steps of the synthesis of a cross-type alkane polymer containing a polymerizable functional group and a hydrophilic group provided in the present invention.

Fig. 2 is a plan view (A) of the hydrophobic rubber lens of the third embodiment of the present invention.

Fig. 3 is a side view (B) of the hydrophobic rubber lens of the third embodiment of the present invention.

Since the creation method of the hydrophobic gel lens disclosed in the present invention, the ring opening polymerization and the hydrogenation reaction (Hydrosilation) used in the present invention have been known to those skilled in the related art, and therefore, The description will not be fully described.

The present invention provides a water-repellent gel lens made of a hydrophobic polymer containing a polymerizable functional group and a hydrophilic group of a cross-type alkane siloxane monomer, and the preparation method comprises the following steps: first hydrogenation reaction, ring-opening polymerization reaction And a second hydrogenation reaction.

Referring to FIG. 1 , firstly, a cross-type oxime having a hydrogen group at the end is provided (step S11), and the cross-type oxirane having a hydrogen group at the end is represented by the following formula.

Wherein R ₀ is a chemical structure represented by the following formula,

In R ₀ , the d value is between 0 and 20.

The cross-type oxime having a hydrogen group at the end, for example, in the case of d = 0, is Tetrakis (dimethylsilyl) orthosilicate.

The first hydrogenation reaction is carried out with tetrakis(dimethylmethoxyoxy)decane (step S12) as shown in the following chemical reaction formula (a):

Step S12 is to add allyl methacrylate (2) to tetrakis(dimethylmethoxyoxy)decane at a temperature of 85 to 90 ° C to contain a platinum catalyst (Pt/C). Catalyzing the first hydrogenation reaction to obtain a cross-type alkane small molecule (3) containing a polymerizable functional group R having the chemical structure shown below:

Wherein, the polymerizable functional group has a structural formula of Si—O—Si.

Subsequently, a ring-opening polymerization reaction (step S13) is carried out as shown in the following chemical reaction formula (b):

Step S13 is to add a strong acid (6) to a mixture of cyclodecane (4), cyclohydrooxane (5) and a small cross-type alkane small molecule (3) containing a polymerizable functional group R, Wherein, the molar number of the strong acid (6) is the total number of moles of the mixture of the cyclopentane (4), the cyclohydrooxane (5) and the cross-type alkane small molecule (3) containing the polymerizable functional group R 1~10%. The ring-opening polymerization reaction is carried out at room temperature (about 35 ° C) to form a crucible-containing polyaluminoxane polymer (7) containing a hydrogen group. The R _{1 of the} polymer (7) has the chemical structure shown below:

Among them, the m value is between 5 and 1000, and the value of n representing the hydrogen group (Si-H) is between 0 and 150.

In the ring-opening polymerization reaction (step S13), the cyclodecoxy alkane (4) may be at least one of Octamethylcyclotetrasiloxane and Hexamethylcyclotrisiloxane; The hydroquinone (5) may be 2,4,6,8 tetramethylcyclotetrasiloxane; the strong acid (6) is represented by the chemical reaction formula (b). In addition to trifluoromethane sulfonic acid, sulfuric acid (Sulfuric acid) may be used instead.

Thereafter, a second hydrogenation reaction is carried out (step S14), as shown in the chemical reaction formula (c):

Step S14 is: adding a hydrophilic compound (8) to a crucible-containing polyaluminoxane polymer (7), and catalyzing with a platinum-containing catalyst (Pt/C) at a temperature of 85 to 90 ° C. a second hydrogenation reaction to obtain a cross-type alkane polymer (9) containing a polymerizable functional group and a hydrophilic group, the cross-type azide polymer containing a polymerizable functional group and a hydrophilic group (9) R ₂ has the chemical structure shown below:

Wherein, the m value is between 5 and 1000, the n value is between 0 and 150, and the hydrophilic group R ₄ is a hydrophilic structure represented by the following:

In the above hydrophilic compound (8) and hydrophilic group R ₄ , y value is from 0 to 100, z value is from 0 to 50, and R ₃ is any one of hydroxyl group (OH) and methyl group (CH ₃ ). By. And the hydrophilic compound (8) may be 3-Allyloxy-1,2-propanediol, 2-Allyloxyethanol, trimethylol At least one of Trimethylolpropane allyl ether.

Among the four R ₂ of the above-mentioned cross-type aramid polymer (9) having a polymerizable functional group and a hydrophilic group, at least three R ₂ have a hydrophilic group R ₄ .

Example 1

The first hydrogenation reaction: synthesis of a small molecule of a cross-type alkane having a polymerizable functional group.

Allyl methacrylate (10.52g, 83.39mmol), stabilizer: 4-methoxyphenol (9mg) and platinum-containing catalyst (Pt/C) (5% on carbon, 0.6g Place in a 250mL double-necked flask; install a reflux tube and a serum plug on the 250mL double-necked flask, vacuum and then inject nitrogen three times, then take the solvent: anhydrous toluene (60mL) and use a glass syringe Inject it into a 250 mL double neck bottle. Then, tetrakis(dimethylamyloxy)decane (6 g, 18.25 mmol) was taken and poured into a 250 mL double-necked flask with a syringe. The 250 mL double-necked flask was placed in an oil bath and heated to 85-90 ° C for reaction. After 23 hours, the liquid was collected by suction filtration (4-6 times), and the collected liquid was subjected to gravity filtration. (Gravity filtration 1 time).

The organic solvent was removed under reduced pressure. Then, ethyl acetate (ethyl acetate) (100 mL) and saturated brine (150 mL) were used to extract the product which was concentrated under reduced pressure (repeated extraction 5 times), and the organic layer was collected. The mixture was concentrated under reduced pressure using a reduced pressure concentrating apparatus, and the product collected from the organic layer was concentrated by heating in a water bath (about 50 ° C) and vacuum (about 3 hours) to remove an organic solvent. The cross-type alkane small molecule containing a polymerizable functional group was collected by flow column chromatography (EA/Hexane = 1/20) in a yield of about 37%.

The results of hydrogen nuclear magnetic resonance spectroscopy of a small molecule of a cross-type alkane having a polymerizable functional group are as follows: ¹ H NMR (CDCl ₃ , 400 MHz): δ 6.09 (s, 4 H), 5.54 (s, 4H), 4.10 ( t,8 H), 1.93 (m, 12H), 1.63-1.79 (m, 8H), 0.55-0.64 (m, 8H), 0.04-0.20 (m, 24H), where δ 6.09 (s, 4 H) 5.54 (s, 4H), 4.10 (t, 8 H) and 1.93 (m, 12H) These values represent the formation of small cross-type alkane-containing molecules containing polymerizable functional groups.

Ring-opening polymerization: synthesis of a crucible-containing polyaluminoxane polymer containing a hydrogen group (n = 8, m = 43).

Octamethylcyclotetraoxane (15g, 50.57mmol), 2,4,6,8 tetramethylcyclotetraoxane (3g, 12.47mmol), polymerizable functional group produced by hydrogenation of the first hydrazine A small cross-type alkane small molecule (2.4 g, 2.88 mmol) and a solvent: Chloroform (14 mL) were placed in a 250 mL two-necked flask; a serum plug and a check valve were placed on the 250 mL double-necked flask. Nitrogen gas was introduced from the one-way valve port, and trifluoromethanesulfonic acid (0.1 mL) was taken and injected into the 250 mL double-necked flask with a syringe, and reacted under nitrogen atmosphere and room temperature (about 35 ° C) for 24 hours, and then the device was opened. The serum plug on a 250 mL double-necked flask was added with a saturated aqueous solution of sodium carbonate (0.5 mL) to terminate the ring-opening polymerization.

The organic solvent was removed by a rotary concentrator, followed by an extraction step, and the above-mentioned product after rotary concentration was extracted with ethyl acetate (200 mL) and saturated brine (150 mL) (repeated extraction 5 times), and the upper organic layer was collected. Reuse decompression The reduction machine was concentrated under reduced pressure and the organic solvent was removed. The product obtained by concentration under reduced pressure was dissolved in acetone (6 mL), and then re-precipitated by dropping into methanol (Methanol) (27 mL); then, gravity filtration was carried out with filter paper, and the upper layer of the filter paper was washed with methanol (250 mL). Sticky substance. The upper layer of the dope was collected and the organic solvent was removed by a rotary concentrator; the second reprecipitation step was repeated. The upper layer of the filter paper was collected to obtain 10.9 g of a colorless viscous hydrazine-containing cross-type polyaluminoxane polymer (yield about 53%).

The results of hydrogen nuclear magnetic resonance spectroscopy of a cross-type polyaluminoxane polymer containing a hydrogen group are as follows: ¹ H NMR (CDCl ₃ , 400 MHz): δ 6.1 (s, 4H), 5.56 (s, 4H), 4.70 (m) , 32H), 4.10 (t, 8H), 1.95 (s, 12H), 1.65-1.75 (m, 8H), 0.50-0.65 (m, 8H), 0.04-0.20 (m, Si-CH3), of which 4.70 ( m, 32H) This value represents the formation of a hydrazine group.

The second hydrogenation reaction: synthesis of a cross-type alkane polymer containing a polymerizable functional group and a hydrophilic group (n = 8, m = 50).

3-Allyloxy-1,2,propanediol (4.69 g, 35.49 mmol) and a platinum-containing catalyst (Pt/C) (5% on carbon, 0.95 g) were placed in a 250 mL double-necked flask; The 250 mL double-necked flask was equipped with a reflux tube and a dropping tube, vacuumed and filled with nitrogen three times; solvent: anhydrous toluene (35 mL) was injected into the 250 mL double-necked flask with a syringe, and a 250 mL double-necked flask was placed. Oil bath and heat to 85~90 °C.

The rhodium-containing hydrogen-containing cross-type polyaluminoxane polymer obtained by ring-opening polymerization (n=8, m=43, molecular weight estimated to be about 15500 by NMR) (10 g, 0.645 mmol) was placed in another 100 mL double neck. In the bottle, a serum plug and a check valve were placed on the 100 mL double-necked flask, followed by evacuation and nitrogen gas three times, and anhydrous toluene (25 mL) and stabilizer: 4-methoxyphenol (6 mg/20 mL in toluene, 4mL) and inject it into a 100mL double-necked flask, and then extract the hydrogen-containing hydrogen-containing cross-type polyaluminoxane polymer solution dissolved in anhydrous toluene from a 100mL double-necked flask with a syringe; then, inject it The tube was placed on a 250 mL double-necked flask and dropped into a 250 mL double-necked flask (dropping time not exceeding 4 minutes). If there is still residue in the 100mL double-necked flask, the residue in the 100mL double-necked flask can be washed with anhydrous toluene (15mL) from the syringe, and the washed residue can be injected into the dropping tube, and then dropped into the 250mL double-necked bottle. in.

The 250 mL double-necked flask placed in the oil bath was continuously heated and maintained at 85-90 ° C, and subjected to a second hydrogenation reaction under a nitrogen atmosphere; after 24 hours of reaction, the liquid was collected by suction filtration ( 4~6 times), gravity filtration (2 times), using a rotary concentrator to remove the organic solvent, and then dissolving the product after rotary concentration in acetone (15 mL), and adding the product dissolved in acetone to the purified water (76 mL). Reprecipitation was carried out, gravity filtration was carried out using a filter paper, the product of the upper layer of the filter paper was washed with pure water (about 250 mL), the upper layer product was collected, and the organic solvent was removed by a rotary concentrator, and the above-mentioned reprecipitation step was repeated. The thick layer of the upper layer of the filter paper was collected to obtain about 8.12 g of a yellow and clear viscous polymer of a cross-type alkane having a polymerizable functional group and a hydrophilic group (8.12 g, yield 63%).

The results of hydrogen nuclear magnetic resonance spectroscopy of a polymer of a cross-type alkane having a polymerizable functional group and a hydrophilic group are as follows: ¹ H NMR (CDCl ₃ , 400 MHz): δ 6.1 (s, 4H), 5.54 (s, 4H), 4.10(t,8H), 3.40-3.90(m,288H), 1.94(s,12H),1.55-1.85(m,72H),0.47-0.60(m,72H),0.04-0.20(m,Si-CH3 ), wherein 3.40 - 3.90 (m, 288H) represents the formation of a hydrophilic structure in the polymer.

Example 2

A cross-type alkane polymer containing a polymerizable functional group and a hydrophilic group (n=8, m=50), a linear alkane (n=32, m=200) and a US patent respectively synthesized by the present invention A small molecule cross-type oxime disclosed in US Pat. No. 4,463, 149 discloses a hydrophobic gel lens, the formulation of which is shown in the following table: TRIS: 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate)

NVP: N-Vinyl-2-pyrrolidone

HEMA: 2-hydroxyethyl methacrylate (Hydroxyethyl Methacrylate)

Example 3

The hydrophobic gel prepolymer formed by mixing the respective formulas in Example 2 was poured into a mold to prepare a hydrophobic rubber lens, as shown in Fig. 2, and Fig. 2 is a plan view of the hydrophobic gel lens of the present invention. The manufactured hydrophobic lens has a lens body 1 composed of a central optical zone 11 located at the center of the lens body 1 and an edge zone 12 located at the outer edge of the lens body 1, as shown in Fig. 3, the third A side view of the water-repellent lens of the present invention, the lens body 1 has an outer surface 13 and an inner surface 14, and the central optical zone 11 and the edge region 12 are connected to each other to form a semi-arc lens structure, wherein The central optical zone diameter D1 is between 5 and 10 mm. In a preferred embodiment, the central optical zone diameter D1 is between 6.5 and 9 mm. In addition, the thickness of the central optical zone is between 0.04 and 0.15 mm. In another preferred embodiment, the thickness of the central optical zone is between 0.06 and 0.1 mm, and the thickness of the edge zone is 0.22 mm.

The oxygen permeability and water content of the above three water-repellent lenses made of different bismuth monomer formulations were tested separately. The test results are shown in the following table:

It can be seen from the above table that, in the case where the values of n and m are the same, the water-permeable gel lens containing the cross-type alkoxysilane polymer oxime monomer synthesized by the present invention has higher oxygen permeability than that of the linear type siloxane. Water gel lens. The hydrophobic gel lens containing a small molecule cross-type azide is a small molecule polymer, and the relatively hydrophilic structure thereof is (O=CO), so the oxygen permeability and water content are higher than the above two. low.

In addition, the cross-type azide polymer containing a polymerizable functional group and a hydrophilic group synthesized by the present method can be used as a hydrophobic rubber lens in addition to a hydrophobic rubber lens, and can be applied to other materials. Water-repellent materials for medical or health care products.

In summary, the present invention provides a hydrophobic gel lens made of a hydrophobic polymer containing a polymerizable functional group and a hydrophilic group, which has a high oxygen permeability and a high water content. The characteristics of the rate; therefore, this creation is a very industrial value.

This creation has been modified by those skilled in the art, and is not intended to be protected as intended.

1‧‧‧ lens body

11‧‧‧Central Optical Zone

12‧‧‧Edge area

13‧‧‧ outer surface

14‧‧‧ inner surface

Claims (7)

A hydrophobic gel lens comprising a lens body having an inner surface and an outer surface, the lens body being composed of a central optical zone and an edge zone, the central optical zone connecting the edge zone to form a semi-arc lens structure, The central optical zone has a diameter of 5 to 10 mm, the central optical zone has a thickness of 0.04 to 0.15 mm, and the edge zone has a thickness of 0.22 mm, wherein the lens system comprises a cross-type oxygen containing a polymerizable functional group and a hydrophilic group. It is made of a hydrophobic polymer prepolymer of an alkane polymer. The hydrophobic gel lens according to claim 1, wherein the cross-type alkane polymer containing a polymerizable functional group and a hydrophilic group has the chemical structure of the formula (I): In the formula (I), R ₂ is a chemical structure represented by the following formula, In R ₂ , the m value is between 5 and 1000, the n value is between 0 and 150, and the hydrophilic group R ₄ is a hydrophilic structure represented by the following formula. In R ₄ , the y value is between 0 and 100, the z value is between 0 and 50, and R ₃ is any one of a hydroxyl group and a methyl group. The hydrophobic gel lens of claim 2, wherein at least three of the R ₂ have a hydrophilic group R ₄ . The hydrophobic gel lens of claim 2, wherein the hydrophilic group R ₄ is selected from the group consisting of: 3-allyloxy-1,2, propylene glycol, 2-allyloxyethanol, trimethyl At least one of an alcohol propane allyl ether. The hydrophobic gel lens of claim 1, wherein the hydrophobic gel lens further comprises: tris-[tris(trimethyldecyloxy)]propyl methacrylate decane, N-vinylpyrrolidone, At least one of 2-hydroxyethyl methacrylate. The hydrophobic gel lens of claim 1, wherein the central optical zone diameter is further between 6.5 and 9 mm. The hydrophobic gel lens of claim 1, wherein the central optical zone thickness is further between 0.06 and 0.1 mm.