阅读说明：本技术 一种复合的硅水凝胶角膜接触镜材料及其制备方法 (Composite silicon hydrogel corneal contact lens material and preparation method thereof ) 是由 王玉东 蔡瑞钦 陈平 石婉 于 2020-11-20 设计创作，主要内容包括：一种复合的硅水凝胶角膜接触镜材料及其制备方法,按重量份数计,包括以下组分聚合而成：甲基丙烯酸酯封端聚硅氧烷单体10-40份、双亲性甲基丙烯酸酯双封端聚硅氧烷单体0.1-20份、乙烯基亲水性单体30-60份、甲基丙烯酸酯类单体0-20份、引发剂0.1-3份和交联剂0.1-3份；本发明制备的隐形眼镜采用一步聚合法,使得有机硅单体,疏水性单体聚合时沉积在中心区,制备出中心较硬的材质,而边缘部分则聚集着大量的乙烯基亲水性单体制备出较软的材质,可使所得镜片具备中心区材质较硬,边缘材质较软的复合的特征,其在矫正视力清晰,矫正散光的效果上优势很明显,边缘材质较软,佩戴舒适性强,无需太多的适应时间。(A composite silicon hydrogel contact lens material and a preparation method thereof are disclosed, which comprises the following components by weight: 10-40 parts of methacrylate terminated polysiloxane monomer, 0.1-20 parts of amphiphilic methacrylate double terminated polysiloxane monomer, 30-60 parts of vinyl hydrophilic monomer, 0-20 parts of methacrylate monomer, 0.1-3 parts of initiator and 0.1-3 parts of cross-linking agent; the contact lens prepared by the invention adopts a one-step polymerization method, so that the organosilicon monomer and the hydrophobic monomer are deposited in the central area when polymerized to prepare a material with a harder central area, and a great amount of vinyl hydrophilic monomer is gathered at the edge part to prepare a softer material, so that the obtained lens has the composite characteristics of harder central area material and softer edge material, has clear vision correction and obvious astigmatism correction effect, and has softer edge material, strong wearing comfort and no need of too much adaptation time.)

1. The composite silicon hydrogel contact lens material is characterized by comprising the following components in parts by weight:

2. the composite silicone hydrogel contact lens material of claim 1, wherein the amphiphilic methacrylate double-ended polysiloxane monomer comprises the following two monomers, each having the following structural formula:

wherein, the structural formula of X is as follows:

wherein a is an integer of 0 to 30, b is an integer of 0 to 10, and c is an integer of 5 to 100.

3. The composite silicone hydrogel contact lens material of claim 1, wherein the methacrylate-terminated polysiloxane monomer comprises monomethacryloyloxypropyl polydimethylsiloxane monomer or monomethacryloyloxyethylaminoyloxyethylpropylpolydimethylsiloxane monomer of the respective formulae:

wherein n is an integer of 7 to 11;

and

wherein n is an integer of 6 to 15.

4. The composite silicone hydrogel corneal contact lens material of claim 1, wherein said hydrophilic vinyl monomer is any one of N-vinyl-N-methylacetamide, N-dimethylacrylamide, and N-vinylpyrrolidone.

5. The composite silicone hydrogel contact lens material of claim 1, wherein the methacrylate is any one of methyl methacrylate, ethyl methacrylate, and propyl methacrylate.

6. The composite silicone hydrogel corneal contact lens material of claim 1, wherein said cross-linking agent comprises one or any combination of triethylene glycol dimethacrylate, triethylene glycol divinyl ester, divinyl glycol isocyanurate, vinyl methacrylate, polyethylene glycol dimethacrylate, divinyl polyethylene glycol ester, and polyethylene glycol vinyl methacrylate.

7. The composite silicone hydrogel contact lens material of claim 1, wherein the initiator is one or any combination of azobisisobutyronitrile, benzoyl peroxide, azobisisoheptonitrile, or 2-hydroxy-2-methyl-1-phenyl-1-propanone.

8. A preparation method of a composite silicon hydrogel contact lens material is characterized by comprising the following steps: weighing the components in parts by weight, uniformly mixing, injecting into a corneal contact lens mold, carrying out photoinitiation or thermal initiation polymerization, demolding after the polymerization is finished, sequentially soaking in an organic solvent and deionized water, extracting to remove unpolymerized monomers and oligomers in the lens, soaking in physiological saline for balancing, and preparing the corneal contact lens;

wherein the amphiphilic methacrylate double-end-capped siloxane monomer is prepared by the following method: under the action of catalyst, the hydroxyl-terminated polydimethylsiloxane and glycidyl methacrylate or isocyano ethyl methacrylate react at 20-80 ℃ to generate the amphiphilic methacrylate double-terminated siloxane monomer.

9. The method of claim 8, wherein the contact lens mold is a non-polar mold made of polyethylene, polypropylene and polystyrene or a polar mold made of polyvinyl alcohol.

Technical Field

The invention relates to the technical field of contact lenses, in particular to a composite silicon hydrogel contact lens material and a preparation method thereof.

Background

Contact lenses, also known as contact lenses, are lenses that are attached directly to the tear layer on the surface of the cornea to correct myopia, hyperopia, astigmatism, and to treat certain eye disorders by altering the refractive power of the eye. Conventional contact lenses are largely classified into hard contact lenses and soft contact lenses. The hard corneal contact lens comprises a common hard corneal contact lens prepared from methyl methacrylate and an air-permeable hard corneal contact lens containing silicon-fluorine polymer, and has obvious advantages in the effects of correcting clear vision and astigmatism; soft contact lenses are mainly hydrogel taking hydroxyethyl methacrylate (HEMA) as a main material and contact lenses taking polysiloxane as a main material, are soft and comfortable to wear, and have lower foreign body feeling when worn compared with hard lenses.

However, the two corneal contact lenses also have obvious defects, the hard corneal contact lens has strong wearing foreign body sensation, the wearer needs a long time to adapt, and the soft corneal contact lens is difficult to correct irregular astigmatism, keratoconus and other complex refractive conditions.

Patent US10841726 describes a soft and hard composite silicone hydrogel contact lens that is formed with a substantially rigid central portion; then treating the substantially rigid central portion to form a coating on a periphery of the substantially rigid portion; a substantially flexible outer portion surrounding the substantially rigid central portion and chemically bonding the substantially flexible portion to the substantially rigid portion. The method needs three steps to prepare the corneal contact lens, and the preparation process is complex; patent CN200580032359.6 discloses a method for preparing a soft and hard composite silicone hydrogel contact lens, which comprises adding soft material into a polymerization container, polymerizing, cutting into tapered holes by a cutting method, and adding prepolymer solution of a central hard part for secondary polymerization. This method requires two additions of raw materials, two polymerizations, and the soft and hard mirrors are not bound by covalent bonds, which may present a risk of instability.

Disclosure of Invention

The invention aims to overcome the defects in the prior art, and provides a composite silicon hydrogel contact lens material which is prepared by polymerizing the following components in parts by weight:

wherein the amphiphilic methacrylate double-ended polysiloxane monomer does not comprise a polysiloxane monomer having a hydrophilic group pendant to the siloxane segment.

Preferably, the amphiphilic methacrylate double-end-capped polysiloxane monomer comprises the following two monomers, and the structural formulas are respectively as follows:

wherein, the structural formula of X is as follows:

wherein a is an integer of 0 to 30, b is an integer of 0 to 10, and c is an integer of 5 to 100.

Preferably, the methacrylate-terminated polysiloxane monomer comprises monomethacryloyloxypropyl polydimethylsiloxane monomer or monomethacryloyloxyethylaminoyloxyethylpropylpolydimethylsiloxane monomer, each having the following structural formula:

wherein n is an integer of 7 to 11;

and

wherein n is an integer of 6 to 15.

Preferably, the hydrophilic vinyl monomer is any one of N-vinyl-N-methylacetamide (VMA), N-Dimethylacrylamide (DMA) and N-vinyl pyrrolidone (NVP).

Preferably, the methacrylate is any one of Methyl Methacrylate (MMA), Ethyl Methacrylate (EMA), and propyl methacrylate (PPMA).

Preferably, the crosslinking agent comprises one or any combination of triethylene glycol dimethacrylate (TEGDMA), triethylene glycol divinyl ester (TEGDVE), divinyl glycol ester (EGDVE), triallyl isocyanurate (TAIC), Vinyl Methacrylate (VMAA), polyethylene glycol dimethacrylate (PEGDMA), divinyl polyethylene glycol ester (PEGDVE), and polyethylene glycol methacrylate (PVMAA).

Preferably, the initiator is one or any combination of Azobisisobutyronitrile (AIBN), Benzoyl Peroxide (BPO), Azobisisoheptonitrile (ABVN) or 2-hydroxy-2-methyl-1-phenyl-1-propanone (D1173).

A preparation method of a composite silicon hydrogel contact lens material specifically comprises the following steps: weighing the components in parts by weight, uniformly mixing, injecting into a corneal contact lens mold, carrying out photoinitiation or thermal initiation polymerization, demolding after the polymerization is finished, sequentially soaking in an organic solvent and deionized water, extracting to remove unpolymerized monomers and oligomers in the lens, soaking in physiological saline for balancing, and preparing the corneal contact lens;

wherein the amphiphilic methacrylate double-end-capped siloxane monomer is prepared by the following method: under the action of catalyst, the hydroxyl-terminated polydimethylsiloxane and glycidyl methacrylate react at 20-80 ℃ to generate the amphiphilic methacrylate double-terminated siloxane monomer.

Preferably, the corneal contact lens mold can be a nonpolar mold made of polyethylene, polypropylene, polystyrene or a polar mold made of polyvinyl alcohol.

Compared with the prior art, the invention has the beneficial effects that: the lens prepared by the invention has the composite characteristics of hard material of the central area and soft material of the edge, has obvious advantages in vision correction and astigmatism correction effects, soft material of the edge, strong wearing comfort and no need of too much adaptation time.

If the methacrylate terminated polysiloxane monomer is polymerized with the vinyl hydrophilic monomer, the methacrylate terminated polysiloxane monomer is a lipophilic monomer, the vinyl monomer is a hydrophilic monomer, and the methacrylate terminated polysiloxane monomer and the vinyl monomer cannot be dissolved with each other, so that only the fog-shaped lens can be prepared; if the amphiphilic methacrylate ester double-terminated polysiloxane monomer and the vinyl hydrophilic monomer are polymerized, the two monomers can be effectively dissolved, the amphiphilic methacrylate ester double-terminated polysiloxane monomer is used as a cross-linking agent, the prepared lens is a uniform lens, and the material hardness of the central area and the material hardness of the edge have no obvious difference.

Therefore, the contact lens prepared by the invention adopts a one-step polymerization method, wherein the methacrylate terminated monomer comprises methacrylate terminated polysiloxane monomer, amphiphilic methacrylate double terminated polysiloxane monomer and methacrylate terminated hydrophobic monomer, the polymerization speed of the monomers is higher, a small amount of vinyl monomer can be carried in the polymerization process to be preferentially polymerized, the volume of the material is contracted because the amphiphilic methacrylate double terminated polysiloxane monomer has the crosslinking function, so that the material can be deposited in the central area of the lens to be polymerized, the methacrylate and methacrylate terminated polysiloxane monomer can effectively improve the modulus of the central area, the residual unpolymerized vinyl hydrophilic monomer and a small amount of methacrylate terminated monomer are mainly polymerized at the edge part of the lens in the later period, after the hydration process, because the material formed in the central area and the edge in the polymerization process is different, the central area is mainly polymerized by hydrophobic monomers such as methacrylate terminated polysiloxane monomer, amphiphilic methacrylate double terminated polysiloxane monomer, methacrylate monomer and the like, the methacrylate terminated polysiloxane monomer and the methacrylate monomer do not have hydroxyl, hydrophilic groups such as polyether and the like, and the siloxane side chain of the monomer does not have hydrophilic monomers, so that the swelling rate is low in the hydration process, and the edge of the lens is mainly hydrophilic vinyl monomer mainly containing a large amount of amide groups, the polymer of the lens is softer and has higher expansion rate when meeting water, so that the hydrated lens has the composite characteristics of harder material in the central area and softer material at the edge, and a proper amount of solvent can be added in the process of preparing the lens raw material to increase the solubility of the raw material.

Drawings

FIG. 1 shows the chemical reaction equation for an amphiphilic methacrylate double-ended siloxane monomer;

FIG. 2 is a flow chart of a method of making a silicone hydrogel contact lens material.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

A composite silicon hydrogel contact lens material is polymerized from the following components in parts by weight:

in the technical scheme, the amphiphilic methacrylate double-terminated siloxane monomer is prepared by the following method: under the action of a catalyst, hydroxyl-terminated polydimethylsiloxane and glycidyl methacrylate or isocyano ethyl methacrylate react at a temperature range of 20-80 ℃ to generate an amphiphilic methacrylate double-terminated siloxane monomer, and a specific chemical reaction formula is shown in figure 1.

In the two preparation methods, the catalyst is dibutyltin dilaurate, trifluoromethanesulfonic acid, triethylamine or tetrabutylammonium chloride.

The amphiphilic methacrylate double-end-capped siloxane monomer comprises the following two monomers (respectively marked as M1 and M2), and the structural formulas are respectively as follows:

wherein, the structural formula of X is as follows:

wherein a is an integer of 0 to 30, b is an integer of 0 to 10, and c is an integer of 5 to 100.

In the technical scheme, the methacrylate end-capped polysiloxane monomer comprises a monomethacryloyloxypropyl polydimethylsiloxane monomer (marked as Si-1) or a monomethacryloyloxyethylaminoyloxyethylpropylpolydimethylsiloxane monomer (marked as Si-2), and the structural formulas are respectively as follows:

wherein n is an integer of 7 to 11;

and

wherein n is an integer of 6 to 15.

In the technical scheme, the vinyl hydrophilic monomer is any one of N-vinyl-N-methylacetamide, N-dimethylacrylamide and N-vinyl pyrrolidone.

In the technical scheme, the methacrylate is any one of methyl methacrylate, ethyl methacrylate and propyl methacrylate; the methacrylate monomer has a faster reaction speed relative to the vinyl monomer, and the hydrophilic group of the amphiphilic methacrylate double-end polysiloxane monomer in the invention is not grafted on the side chain of polysiloxane on the main chain segment, has a crosslinking effect, can provide higher hardness when copolymerized with other monomers, and particularly improves the hardness of the central area of the lens.

In the above technical solution, the cross-linking agent includes one or any combination of triethylene glycol dimethacrylate, triethylene glycol divinyl ester, divinyl glycol ester, triallyl isocyanurate, vinyl methacrylate, polyethylene glycol dimethacrylate, divinyl polyethylene glycol ester, and polyethylene glycol vinyl methacrylate.

In the technical scheme, the initiator is one or any combination of azobisisobutyronitrile, benzoyl peroxide, azobisisoheptonitrile or 2-hydroxy-2-methyl-1-phenyl-1-acetone.

A preparation method of a composite silicon hydrogel contact lens material specifically comprises the following steps: weighing the components in parts by weight, uniformly mixing, injecting into a corneal contact lens mold, carrying out photoinitiation or thermal initiation polymerization, demolding after the polymerization is finished, sequentially soaking in an organic solvent and deionized water, extracting to remove unpolymerized monomers and oligomers in the lens, soaking in physiological saline for balancing, and preparing the corneal contact lens;

preferably, the corneal contact lens mold can be a nonpolar mold made of polyethylene, polypropylene, polystyrene or a polar mold made of polyvinyl alcohol.

Next, as shown in the reaction scheme of FIG. 2, 10 specific examples are listed; the specific structures of M1-a, M1-b, M2-a and M2-b in examples 1-10 are as follows:

example 1

Adding 15 parts of silicon monomer M1-a, 135 parts of Si, 39 parts of N-vinyl-N-methylacetamide, 10 parts of methyl methacrylate, 0.25 part of polyethylene glycol dimethacrylate, 0.25 part of ethylene glycol dimethacrylate and 0.5 part of benzoyl peroxide into a glass beaker in sequence, mixing uniformly, injecting into a polypropylene mould, and carrying out thermal initiation polymerization at 50 ℃ for 12 hours; naturally cooling to room temperature, demoulding, soaking the dried slices in 50% ethanol solution for 1h, soaking in pure water for 3h, and then placing in physiological saline for balancing for more than 2h to obtain the corneal contact lens.

Example 2

Adding 15 parts of silicon monomer M1-a, 15 parts of Si-125 parts, 44 parts of N-vinyl-N-methylacetamide, 15 parts of methyl methacrylate, 0.5 part of ethylene glycol dimethacrylate and 0.5 part of azodiisobutyronitrile into a glass beaker in sequence, mixing uniformly, injecting into a polypropylene mould, and carrying out thermal initiation polymerization for 15 hours at 70 ℃; naturally cooling to room temperature, demoulding, soaking the dried slices in 50% ethanol solution for 1h, soaking in pure water for 3h, and then placing in physiological saline for balancing for more than 2h to obtain the corneal contact lens.

Example 3

Adding 15 parts of silicon monomer M2-a, 135 parts of Si-1, 20 parts of N-vinyl pyrrolidone, 29 parts of N, N-dimethylacrylamide, 10 parts of methyl methacrylate, 0.5 part of triallyl isocyanurate and 0.5 part of azodiisoheptacyane into a glass beaker in sequence, mixing uniformly, injecting into a polypropylene mould, and carrying out thermal initiation polymerization at 80 ℃ for 15 hours; naturally cooling to room temperature, demoulding, soaking the dried slices in 25% ethanol solution for 2h, soaking in pure water for 5h, and then placing in physiological saline for balancing for more than 2h to obtain the corneal contact lens.

Example 4

Sequentially adding 10 parts of silicon monomer M2-a, 130 parts of Si, 20 parts of N-vinyl pyrrolidone, 19 parts of N, N-dimethylacrylamide, 10 parts of methyl methacrylate, 0.5 part of ethylene glycol dimethacrylate and 0.5 part of azodiisoheptacyanic into a glass beaker, uniformly mixing, injecting into a polypropylene mould, and thermally initiating polymerization for 15 hours at 80 ℃; naturally cooling to room temperature, demoulding, soaking the dried slices in 25% ethanol solution for 2h, soaking in pure water for 5h, and then placing in physiological saline for balancing for more than 2h to obtain the corneal contact lens.

Example 5

Sequentially adding 5 parts of silicon monomer M1-b, 130 parts of Si, 29 parts of N-vinyl-N-methylacetamide, 19 parts of N-vinyl pyrrolidone, 15 parts of ethyl methacrylate, 0.5 part of polyethylene glycol dimethacrylate and 0.5 part of azodiisoheptacyanic into a glass beaker, uniformly mixing, injecting into a polypropylene mould, and thermally initiating polymerization for 10 hours at 80 ℃; naturally cooling to room temperature, demoulding, soaking the dried slices in 25% ethanol solution for 2h, soaking in pure water for 5h, and then placing in physiological saline for balancing for more than 2h to obtain the corneal contact lens.

Example 6

Sequentially adding 10 parts of silicon monomer M1-b, 230 parts of Si, 39 parts of N-vinyl-N-methylacetamide, 10 parts of N, N-dimethylacrylamide, 10 parts of ethyl methacrylate, 0.5 part of polyethylene glycol dimethacrylate and 0.5 part of azodiisoheptacyanic into a glass beaker, uniformly mixing, injecting into a polypropylene mould, and thermally initiating polymerization for 15 hours at 80 ℃; naturally cooling to room temperature, demoulding, soaking the dried slices in 25% ethanol solution for 2h, soaking in pure water for 5h, and then placing in physiological saline for balancing for more than 2h to obtain the corneal contact lens.

Example 7

Sequentially adding 10 parts of silicon monomer M1-b, 240 parts of Si, 39 parts of N-vinyl-N-methylacetamide, 10 parts of N, N-dimethylacrylamide, 10 parts of ethyl methacrylate, 0.5 part of triethylene glycol divinyl ester and 0.5 part of azodiisoheptacyanic into a glass beaker, uniformly mixing, injecting into a polypropylene mould, and thermally initiating polymerization for 15 hours at 80 ℃; naturally cooling to room temperature, demoulding, soaking the dried slices in 25% ethanol solution for 2h, soaking in pure water for 5h, and then placing in physiological saline for balancing for more than 2h to obtain the corneal contact lens.

Example 8

Sequentially adding 10 parts of silicon monomer M1-b, 230 parts of Si, 39 parts of N-vinyl-N-methylacetamide, 10 parts of N, N-dimethylacrylamide, 10 parts of ethyl methacrylate, 0.5 part of divinyl polyethylene glycol ester and 0.5 part of azodiisoheptacyane into a glass beaker, uniformly mixing, injecting into a polypropylene mould, and thermally initiating polymerization for 15 hours at 80 ℃; naturally cooling to room temperature, demoulding, soaking the dried slices in 25% ethanol solution for 2h, soaking in pure water for 5h, and then placing in physiological saline for balancing for more than 2h to obtain the corneal contact lens.

Example 9

Sequentially adding 5 parts of silicon monomer M1-a, 5 parts of Si-235 parts, 44 parts of N-vinyl-N-methylacetamide, 5 parts of N, N-dimethylacrylamide, 10 parts of ethyl methacrylate, 0.5 part of polyethylene glycol dimethacrylate and 0.5 part of azodiisobutyronitrile into a glass beaker, uniformly mixing, injecting into a polypropylene mould, and thermally initiating polymerization for 10 hours at 80 ℃; naturally cooling to room temperature, demoulding, soaking the dried slices in 25% ethanol solution for 2h, soaking in pure water for 5h, and then placing in physiological saline for balancing for more than 2h to obtain the corneal contact lens.

Example 10

Sequentially adding 10 parts of silicon monomer M1-a, 130 parts of Si, 34 parts of N-vinyl-N-methylacetamide, 10 parts of N-vinyl pyrrolidone, 15 parts of propyl methacrylate, 0.5 part of polyethylene glycol dimethacrylate and 0.5 part of azodiisoheptacyanic into a glass beaker, uniformly mixing, injecting into a polypropylene mould, and thermally initiating polymerization for 15 hours at 80 ℃; naturally cooling to room temperature, demoulding, soaking the dried slices in 25% ethanol solution for 2h, soaking in pure water for 5h, and then placing in physiological saline for balancing for more than 2h to obtain the corneal contact lens.

The performance test data for examples 1-10 are shown in table 1,

although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.