WO2019100571A1

WO2019100571A1 - Method for surface hydrophilic modification of silicon rubber and application method

Info

Publication number: WO2019100571A1
Application number: PCT/CN2018/072983
Authority: WO
Inventors: 姜勇; 王小红; 夏学可; 张威; 韩雪莲; 陈平
Original assignee: 海昌隐形眼镜有限公司; 东南大学; 江苏海伦隐形眼镜有限公司
Priority date: 2017-11-21
Filing date: 2018-01-17
Publication date: 2019-05-31
Also published as: CN107759820A; KR20200062341A

Abstract

A method for the surface hydrophilic modification of silicon rubber, comprising: step 10) preparing a silicon rubber substrate: mixing vinyl polysiloxane, hydroxy polysiloxane and a polyvinyl monomer well, then adding a catalyst, and forming a mixture; injecting the mixture into a mold for thermal curing, and preparing a silicon rubber substrate for which a surface contains double bonds; step 20) preparing a solution containing a hydrophilic monomer: dissolving the hydrophilic monomer having double bonds, a cross-linking agent and a photoinitiator into an organic solvent, and obtaining a solution containing the hydrophilic monomer; step 30) performing surface hydrophilic modification of the silicon rubber: placing the silicon rubber substrate into the solution prepared in step 20), placing under ultraviolet light, removing after ultraviolet initiation, washing with water, and obtaining hydrophilically modified silicon rubber. In the method, a hydrophilic layer is connected to a silicon rubber main body by means of a chemical bond, which may significantly reduce the contact angle of the silicon rubber material, and improve the hydrophilicity thereof and improve the biocompatibility thereof.

Description

Method and application method for hydrophilic modification of silicone rubber surface

Technical field

The invention belongs to the technical field of material surface modification, and in particular relates to a method and a method for hydrophilic modification of a surface of a silicone rubber.

Background technique

Silicone rubber (abbreviated as: PDMS) refers to an elastomer having a three-dimensional network structure formed by reacting a functional group-containing polysiloxane with a crosslinking agent under certain conditions. Silicone rubber has the advantages of non-toxicity, good biocompatibility, high oxygen transmission rate, simple preparation method, low cost, softness and certain strength. Therefore, silicone rubber is used to manufacture body cavity and intravascular interventional instruments (such as contact lenses, The best material for medical catheters, endoscopes, intraluminal stents, etc. However, silicone rubber is a non-polar material with a low surface energy, so there are still problems when it is used in contact medical devices. For example, the surface is easy to adhere to non-polar substances, bacteria can easily accumulate on the surface of the silicone rubber by adhering proteins, thereby forming colonies, which may cause infection when left in the human body for a long time. At the same time, when silicone rubber is used in long-term implantable medical devices, its surface tends to adhere to a large number of platelets, causing blood clots, and even causing blockage of the lumen of tubular medical devices (such as catheters, cannulas, endoscopes, etc.). In order to make silicone rubber materials have a wider range of applications, it is necessary to improve their biocompatibility and improve the surface hydrophilicity.

At present, the research on hydrophilic modification of silicone rubber mainly focuses on two directions: bulk modification and surface modification. The bulk modification is mainly to blend some hydrophilic monomers with the silicone rubber system. Although the surface of the silicone rubber can be hydrophilized, the bulk modification will affect the bulk structure of the silicone rubber and its effect on physical and chemical properties. It is larger than the surface modification. The essence of surface modification is to introduce a biocompatible material on the surface of the biomaterial, covering the original biocompatible material to "cheat" the implanted organism to avoid excessively intense rejection. To achieve the purpose of modification.

CN104194025A discloses a process for the preparation of a biocompatible silicone rubber. The patent firstly treats room temperature vulcanized silicone rubber by plasma, and generates hydroxyl active sites on the surface of the silicone rubber; then adds plasma-treated silicone rubber, organic amine to a non-polar solvent, stirs in an ice salt bath, and drops bromine Mixture of chemical agent and non-polar solvent, remove the ice salt bath and raise to room temperature, continue to avoid light and stir to obtain silicone rubber with bromine group on the surface; finally, silicone rubber and acrylamide monomer with bromo group on the surface, The CuCl/bpy catalyst is placed in a reaction vessel, and the degassed solvent is injected into the reaction vessel by a syringe, and the reaction vessel is placed in a constant temperature oil bath for reaction; after washing and drying, a surface grafted polyacrylamide is obtained. Waterborne silicone rubber. Although the method can reduce the surface contact angle of the silicone rubber from 108° to 16°, the method involves many steps, and the reaction conditions in each step are relatively harsh and difficult to achieve.

CN104857571A discloses a method for preparing a hydrophilic lubricating silicone rubber catheter and a hydrophilic lubricating coating thereof. In the method, a silicone rubber catheter is first placed in a solution containing a photoinitiator, and then taken out, and placed in a hydrophilic monomer solution to initiate polymerization by ultraviolet irradiation to obtain a hydrophilic coating. Although the method can significantly reduce the contact angle, there is no chemical bond between the hydrophilic coating and the body, and the coating is unstable.

Summary of the invention

Technical Problem: The technical problem to be solved by the present invention is to provide a method and a method for hydrophilic modification of a surface of a silicone rubber, wherein the hydrophilic layer and the silicone rubber body are chemically bonded to each other, which can significantly reduce the contact of the silicone rubber material. Angle, improve its hydrophilicity, improve its biocompatibility, and have good light transmittance and other properties.

Technical Solution: In order to solve the above technical problem, the embodiment of the present invention adopts the following technical solutions:

A method for hydrophilically modifying a surface of a silicone rubber, comprising the steps of:

Step 10) preparing a silicone rubber substrate: mixing a vinyl polysiloxane, a hydrogen polysiloxane, and a polyvinyl monomer uniformly, then adding a catalyst, and uniformly mixing to form a mixture; injecting the mixture into a mold Heat curing to form a silicone rubber substrate having a double bond on the surface;

Step 20) preparing a solution containing a hydrophilic monomer: dissolving a hydrophilic monomer having a double bond, a crosslinking agent, and a photoinitiator in an organic solvent to obtain a solution containing a hydrophilic monomer;

Step 30) performing hydrophilic modification on the surface of the silicone rubber: the silicone rubber substrate prepared in the step 10) is placed in the solution prepared in the step 20), placed under ultraviolet light, taken out after ultraviolet initiation, and washed with water to obtain hydrophilic modification. After the silicone rubber.

As a preferred example, in the step 10), the mass fraction of each component in the silicone rubber substrate is as follows:

Vinyl polysiloxane: 55 to 84%;

Hydrogen-based polysiloxane: 7.2 to 25%;

Polyvinyl monomer: 5 to 24.6%;

Catalyst: 0.1 to 0.4%.

As a preferred example, in the step 20), the mass fraction of each substance is as follows:

Hydrophilic monomer: 5 to 35%;

Crosslinking agent: 1 to 5%;

Photoinitiator: 0.2 to 1%;

Organic solvent: 60 to 90%.

As a preferred example, in the step 10), the sum of the molar content of the vinyl group in the vinyl polysiloxane and the molar content of the vinyl group in the vinyl monomer is greater than that in the hydrogen polysiloxane. The molar content of the base.

As a preferred example, in the step 10), the polyvinyl monomer is allyl methacrylate, tetramethyldivinyldisiloxane, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate. , tetravinylsilane, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, 1,4-divinyl-1,1,4,4-tetramethylsilylethane, silicic acid Any one or two of tetraallyl ester combinations.

As a preferred example, in the step 20), the hydrophilic monomer is 2-hydroxyethyl methacrylate, N-vinyl pyrrolidone, N-vinyl caprolactam, sodium vinyl sulfonate, 2-vinyl pyrrole, Any one or a combination of 4-vinylpyrrole, acrylamide, polyethylene glycol methyl ether acrylate.

As a preferred example, in the step 20), the crosslinking agent is N,N-methylenebisacrylamide, diallyl acetal, 1,4-butanediol dimethacrylate, 1,5 -hexadiene, methacryloxy vinyl ester, allyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylic acid Any one of an ester, pentaerythritol tetraacrylate, and neopentyl glycol diacrylate.

As a preferred example, in the step 20), the photoinitiator is benzoin, diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2-hydroxy-2-methyl- 1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, p-phenoxy-2,2-dichloroacetophenone, 2-dimethylamino-2-benzyl-1-[ Any one of 4-(4-morpholino)phenyl]-1-butanone.

As a preferred example, in the step 20), the organic solvent is any one or a combination of two of methanol, ethanol, propanol, butanol, and isopropanol.

A method for applying hydrophilically modified silicone rubber for making a contact lens, an intraocular lens, a medical catheter, an artificial skin or an artificial blood vessel.

Advantageous Effects: Compared with the prior art, the present invention has the following advantageous effects: the present invention can form a silicone rubber substrate having a double bond on the surface by one step, and can graft a hydrophilic monomer to perform surface hydrophilic modification. The hydrophilic coating of the invention is chemically bonded to the body of the silicone rubber, thereby making the hydrophilic layer more stable, can significantly reduce the surface contact angle of the silicone rubber, improve the hydrophilicity, improve the biocompatibility, and have a good penetration. Overshoot and mechanical properties. The modified silicone rubber can be used in the fields of contact lenses, intraocular lenses, medical catheters and artificial blood vessels. In addition, the reaction conditions of each step in the method are relatively easy to realize, the raw materials are readily available, and expensive equipment and reagents are not required.

DRAWINGS

1 is a total reflection infrared spectroscopy (ATR) chart of a silicone rubber sample of Comparative Example 1 in the test of the present invention;

Figure 2 is an ATR diagram of a double-bonded silicone rubber substrate prepared in the step 10) of Example 1 of the present invention;

Figure 3 is an ATR diagram of the hydrophilic modified silicone rubber prepared in the step 30) in Example 1 of the present invention;

Figure 4 is a contact angle diagram of a silicone rubber sample of Comparative Example 1 in the test of the present invention;

Figure 5 is a contact angle diagram of a modified hydrophilic silicone rubber sample of Example 1 in the test of the present invention.

Detailed ways

The technical solutions of the embodiments of the present invention are described in detail below with reference to the embodiments.

A method for hydrophilically modifying a surface of a silicone rubber according to an embodiment of the invention comprises the following steps:

Step 10) preparing a silicone rubber substrate: mixing a vinyl polysiloxane, a hydrogen polysiloxane, and a polyvinyl monomer uniformly, then adding a catalyst, and uniformly mixing to form a mixture; injecting the mixture into a mold It is thermally cured to form a silicone rubber substrate having a double bond on its surface.

Preferably, in the step 10), the mass fraction of each component in the silicone rubber substrate is as follows:

Vinyl polysiloxane: 55 to 84%;

Hydrogen-based polysiloxane: 7.2 to 25%;

Polyvinyl monomer: 5 to 24.6%;

Catalyst: 0.1 to 0.4%.

Preferably, in the step 10), the sum of the molar content of the vinyl group in the vinyl polysiloxane and the molar content of the vinyl group in the vinyl monomer is greater than the molar ratio of the hydrogen group in the hydrogen polysiloxane. content. A vinyl rubber substrate having a double bond on the surface can be produced by a vinyl molar content greater than the molar content of the hydrogen radical. Preferably, the vinyl polysiloxane has a viscosity of from 100 to 1000 cSt, a vinyl group has a molar content of from 0.0085 to 0.035%, a hydrogen-based polysiloxane has a viscosity of from 10 to 70 cSt, and a hydrogen group has a molar content of from 0.15 to 0.5%. The mold is thermally cured at a curing temperature of 50 to 100 °C.

Preferably, the polyvinyl monomer is allyl methacrylate, tetramethyldivinyldisiloxane, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, tetravinylsilane, ethylene glycol Any one of dimethacrylate, neopentyl glycol diacrylate, 1,4-divinyl-1,1,4,4-tetramethylsilylethane, tetraallyl silicate Kind or two combinations. These monomers have certain compatibility with silicone rubber, which can ensure good transmittance of the modified silicone rubber. At the same time, these monomer molecules contain a plurality of vinyl groups, and a part of the vinyl groups in the monomers react with the hydrogen-based polysiloxane, and the remaining vinyl groups react with the hydrophilic monomers.

Step 20) Preparation of a solution containing a hydrophilic monomer: a hydrophilic monomer having a double bond, a crosslinking agent, and a photoinitiator are dissolved in an organic solvent to obtain a solution containing a hydrophilic monomer.

Preferably, in the step 20), the mass fraction of each substance is as follows:

Hydrophilic monomer: 5 to 35%;

Crosslinking agent: 1 to 5%;

Photoinitiator: 0.2 to 1%;

Organic solvent: 60 to 90%.

In the step 20), the hydrophilic monomer is 2-hydroxyethyl methacrylate, N-vinylpyrrolidone, N-vinylcaprolactam, sodium vinyl sulfonate, 2-vinylpyrrole, 4-vinyl group Any one or a combination of pyrrole, acrylamide, polyethylene glycol methyl ether acrylate. These hydrophilic monomers all carry a double bond and are capable of undergoing free radical polymerization.

The crosslinking agent is N,N-methylenebisacrylamide, diallyl acetal, 1,4-butanediol dimethacrylate, 1,5-hexadiene, methacryloyloxy Vinyl ester, allyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, neopentyl glycol Any one of diacrylates. The crosslinking agent acts as a crosslinking agent for radical polymerization.

The photoinitiator is benzoin, diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone (D-1173), 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzene Formyl-diphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2-hydroxy-2-methyl-1-[4-( 2-hydroxyethoxy)phenyl]-1-propanone, p-phenoxy-2,2-dichloroacetophenone, 2-dimethylamino-2-benzyl-1-[4-(4-? Any one of phenyl)phenyl]-1-butanone. The photoinitiator acts as an initiator for the free radical polymerization.

The organic solvent is any one or a combination of two of methanol, ethanol, propanol, butanol, and isopropanol. These organic solvents are capable of dissolving hydrophilic monomers, initiators, and crosslinkers.

Step 30) performing hydrophilic modification on the surface of the silicone rubber: the silicone rubber substrate prepared in the step 10) is placed in the solution prepared in the step 20), placed under ultraviolet light, taken out after ultraviolet initiation, and washed with water to obtain hydrophilic modification. After the silicone rubber. The ultraviolet light intensity is 50-220V, and the light irradiation time is 5-60 minutes.

The hydrophilically modified silicone rubber prepared by the above method can be used for making a contact lens, an intraocular lens, a medical catheter, an artificial skin or an artificial blood vessel.

In the method of the above embodiment, in step 10), the vinyl polysiloxane and the polyvinyl monomer undergo a hydrosilylation reaction with the hydrogen-based polysiloxane under the action of a platinum catalyst to form a silicone rubber substrate. Since the molar ratio of the vinyl group to the hydrogen group is more than 1, the surface of the resulting silicone rubber substrate has excess double bonds. In step 30), the hydrophilic monomer having a double bond is subjected to radical polymerization with a double bond on the surface of the silicone rubber substrate under an initiator, a crosslinking agent and ultraviolet light, and the hydrophilic monomer is grafted to the hydrophilic monomer. Silicone rubber surface to achieve hydrophilic modification of silicone rubber surface. The method of this example prepares a surface hydrophilically modified silicone rubber by preparing a silicone rubber substrate having a double bond on the surface in one step, and grafting a hydrophilic monomer. However, in the prior art, after the silicone rubber is made, various functional means are used to construct a reactive functional group on the surface, and then the hydrophilic monomer is grafted; or the solvent is used to swell the silicone rubber, and the hydrophilic monomer is physically or chemically embedded. internal. Compared with the prior art, the method of the embodiment of the present invention directly prepares a silicone rubber having a reactive double bond on the surface by a simple copolymerization method, without using some expensive equipment (such as a plasma processor) or Harsh reaction conditions (such as vacuum degassing) construct double bonds on the surface of the silicone rubber. The method of the embodiment of the invention is easy to realize in each step, the raw materials are easy to obtain, the reaction conditions are controllable, and the embodiment of the invention has little influence on the optical properties and mechanical properties of the silicone rubber.

In the method of the embodiment of the invention, the polyvinyl monomer is copolymerized with the vinyl polysiloxane and the hydrogen polysiloxane to prepare a substrate with excess double bonds on the surface, and the hydrophilic monomer and the double bond on the surface of the silicone rubber are polymerized. Thereby, the hydrophilic monomer is grafted to the surface of the silicone rubber in the form of a chemical bond to achieve the effect of hydrophilic modification.

In the embodiment of the invention, the hydrophilic coating and the silicone rubber body are chemically bonded to each other, thereby making the hydrophilic layer more stable, can significantly reduce the surface contact angle of the silicone rubber, improve the hydrophilicity, and improve the biocompatibility thereof. Has good transmittance and mechanical properties.

In the method of the embodiment of the present invention, a vinyl rubber substrate having a reactive double bond on the surface is prepared by first adding a vinyl monomer to a silicone rubber system, and then immersing the substrate in a hydrophilic monomer and a crosslinking agent. And a solution of the photoinitiator, the double bond on the surface of the silicone rubber and the double bond in the hydrophilic monomer are polymerized in the solution under ultraviolet light, so that the hydrophobic silicone rubber substrate and the hydrophilic monomer are chemically bonded. A hydrophilic layer is attached to the surface of the silicone rubber, and the treated silicone rubber substrate has good mechanical properties, optical properties, hydrophilicity and biocompatibility.

The silicone rubber prepared by the method of the embodiment of the present invention was verified by experiments to have good performance.

Example 1

(1) Preparation of a silicone rubber substrate: 0.7 g of a vinyl siloxane having a viscosity of 750 cst, 0.2 g of pentaerythritol tetraacrylate, and 0.099 g of a hydrogen-based polysiloxane having a viscosity of 30 cst were uniformly mixed, and then 0.001 g of a catalyst was added. And uniformly mixed to form a mixture; the mixture was poured into a mold and cured at 60 ° C to prepare a silicone rubber substrate having a double bond on the surface.

(2) Preparation of a solution containing a hydrophilic monomer: 0.15 g of N-vinylcaprolactam, 0.02 g of trimethylolpropane trimethacrylate, and 0.005 g of 1-hydroxycyclohexyl phenyl ketone were respectively dissolved. In 0.825 g of methanol solution.

(3) performing hydrophilic modification on the surface of the silicone rubber: the silicone rubber substrate prepared in the step (1) is placed in the solution prepared in the step (2), placed under ultraviolet light, the light intensity is 220 V, and the illumination time is 5 min. After removal, it was rinsed with deionized water to obtain a hydrophilically modified silicone rubber.

Example 2

(1) Preparation of a silicone rubber substrate: 0.648 g of a vinyl polysiloxane having a viscosity of 500 cst, 0.1 g of ethylene glycol dimethacrylate, 0.25 g of a hydrogen-based polysiloxane having a viscosity of 70 cst was uniformly mixed, and then added. 0.002 g of the catalyst was uniformly mixed to form a mixture; the mixture was poured into a mold and solidified at 70 ° C to prepare a silicone rubber substrate having a double bond on the surface.

(2) Preparation of a solution containing a hydrophilic monomer: 0.15 g of 2-hydroxyethyl methacrylate, 0.2 g of N-vinylpyrrolidone, 0.04 g of pentaerythritol tetraacrylate, and 0.01 g of 2-hydroxyl group, respectively 2-Methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone was dissolved in 0.6 g of a solution of isopropanol.

(3) Performing hydrophilic modification on the surface of the silicone rubber: the silicone rubber substrate prepared in the step (1) is placed in the solution prepared in the step (2), placed under ultraviolet light, the light intensity is 50 V, and the illumination time is 60 min. After removal, rinse with deionized water to obtain a hydrophilically modified silicone rubber.

Example 3

(1) Preparation of a silicone rubber substrate: 0.696 g of a 650 cst vinylpolysiloxane, 0.15 g of 1,4-divinyl-1,1,4,4-tetramethylsilylethane 0.15g of a hydrogen-based polysiloxane having a viscosity of 65 cst was uniformly mixed, and then 0.004 g of a catalyst was added and uniformly mixed to form a mixture; the mixture was poured into a mold and solidified at 65 ° C to prepare a silicone rubber substrate having a double bond on the surface thereof. .

(2) Preparation of a solution containing a hydrophilic monomer: 0.25 g of 2-vinylpyrrole, 0.03 g of methacryloxyvinyl ester, and 0.002 g of D-1173 were dissolved in 0.718 g of isopropanol, respectively. In solution.

(3) Performing hydrophilic modification on the surface of the silicone rubber: the silicone rubber substrate prepared in the step (1) is placed in the solution prepared in the step (2), placed under ultraviolet light, the light intensity is 80 V, and the illumination time is 50 min. After removal, it was rinsed with deionized water to obtain a hydrophilically modified silicone rubber.

Example 4

(1) Preparation of a silicone rubber substrate: 0.75 g of a vinyl polysiloxane having a viscosity of 400 cst, 0.05 g of allyl methacrylate, 0.1985 g of a hydrogen-based polysiloxane having a viscosity of 40 cst was uniformly mixed, and then 0.0015 g was added. The catalyst was uniformly mixed to form a mixture; the mixture was poured into a mold and cured at 80 ° C to prepare a silicone rubber substrate having a double bond on the surface.

(2) Preparation of a solution containing a hydrophilic monomer: 0.1 g of N-vinylpyrrolidone, 0.015 g of ethylene glycol dimethacrylate, and 0.01 g of 2,4,6-trimethylbenzoyl group, respectively - Diphenylphosphine oxide was dissolved in 0.875 g of ethanol solution.

(3) Performing hydrophilic modification on the surface of the silicone rubber: the silicone rubber substrate prepared in the step (1) is placed in the solution prepared in the step (2), placed under ultraviolet light, the light intensity is 150 V, and the illumination time is 10 min. After removal, it was rinsed with deionized water to obtain a hydrophilically modified silicone rubber.

Example 5

(1) Preparation of a silicone rubber substrate: 0.725 g of a vinyl polysiloxane having a viscosity of 500 cst, 0.15 g of trimethylolpropane trimethacrylate, and 0.1225 g of a hydrogen-based polysiloxane having a viscosity of 50 cst were uniformly mixed. Then, 0.0025 g of a catalyst was added and uniformly mixed to form a mixture; the mixture was poured into a mold and cured at 90 ° C to prepare a silicone rubber substrate having a double bond on the surface.

(2) Preparation of a solution containing a hydrophilic monomer: 0.05 g of sodium vinyl sulfonate, 0.04 g of triethylene glycol dimethacrylate, and 0.01 g of 2-dimethylamino-2-benzyl group, respectively - 1-[4-(4-Morpholinyl)phenyl]-1-butanone was dissolved in 0.9 g of a mixed solution of propanol and isopropanol.

(3) Performing hydrophilic modification on the surface of the silicone rubber: the silicone rubber substrate prepared in the step (1) is placed in the solution prepared in the step (2), placed under ultraviolet light, the light intensity is 90 V, and the illumination time is 45 min. After removal, it was rinsed with deionized water to obtain a hydrophilically modified silicone rubber.

Example 6

(1) Preparation of a silicone rubber substrate: 0.84 g of a vinyl polysiloxane having a viscosity of 700 cst, 0.085 g of tetravinylsilane, 0.072 g of a hydrogen-based polysiloxane having a viscosity of 55 cst was uniformly mixed, and then 0.003 g of a catalyst was added. The mixture was uniformly mixed to form a mixture; the mixture was poured into a mold and cured at 75 ° C to prepare a silicone rubber substrate having a double bond on the surface.

(2) Preparation of a solution containing a hydrophilic monomer: 0.15 g of acrylamide, 0.0255 g of diallyl ester acetal, and 0.0075 g of diethoxyacetophenone were respectively dissolved in 0.817 g of an ethanol solution.

(3) Performing hydrophilic modification on the surface of the silicone rubber: the silicone rubber substrate prepared in the step (1) is placed in the solution prepared in the step (2), placed under ultraviolet light, the light intensity is 75 V, and the illumination time is 55 min. After removal, it was rinsed with deionized water to obtain a hydrophilically modified silicone rubber.

Example 7

(1) Preparation of silicone rubber substrate: 0.821 g of a vinyl polysiloxane having a viscosity of 1000 cst, 0.075 g of tetraallyl silicate, 0.1 g of a hydrogen-based polysiloxane having a viscosity of 10 cst was uniformly mixed, and then 0.004 g was added. The catalyst was uniformly mixed to form a mixture; the mixture was poured into a mold and solidified at 55 ° C to prepare a silicone rubber substrate having a double bond on the surface.

(2) Preparation of a solution containing a hydrophilic monomer: 0.3 g of polyethylene glycol methyl ether acrylate, 0.01 g of allyl methacrylate, and 0.01 g of 2-methyl-1-(4-methyl Thiophenyl)-2-morpholine-1-propanone was dissolved in 0.68 g of ethanol solution.

(3) Performing hydrophilic modification on the surface of the silicone rubber: the silicone rubber substrate prepared in the step (1) is placed in the solution prepared in the step (2), placed under ultraviolet light, the light intensity is 100, and the illumination time is 20 min. After removal, rinse with deionized water to obtain a hydrophilically modified silicone rubber.

Example 8

(1) Preparation of silicone rubber substrate: 0.55 g of a vinyl polysiloxane having a viscosity of 100 cst, 0.246 g of neopentyl glycol diacrylate, and 0.2 g of a hydrogen-based polysiloxane having a viscosity of 35 cst were uniformly mixed, and then 0.004 was added. The catalyst of g was uniformly mixed to form a mixture; the mixture was poured into a mold and solidified at 65 ° C to prepare a silicone rubber substrate having a double bond on the surface.

(2) Preparation of a solution containing a hydrophilic monomer: 0.19 g of 4-vinylpyrrole, 0.05 g of 1,4-butanediol dimethacrylate, and 0.01 g of p-phenoxy-2,2, respectively Dichloroacetophenone was dissolved in 0.75 g of ethanol solution.

(3) Performing hydrophilic modification on the surface of the silicone rubber: the silicone rubber substrate prepared in the step (1) is placed in the solution prepared in the step (2), placed under ultraviolet light, the light intensity is 110 V, and the illumination time is 15 min. After removal, it was rinsed with deionized water to obtain a hydrophilically modified silicone rubber.

Example 9

(1) Preparation of a silicone rubber substrate: 0.65 g of a vinyl polysiloxane having a viscosity of 400 cst, 0.1875 g of tetravinylsilane, 0.16 g of a hydrogen-based polysiloxane having a viscosity of 45 cst was uniformly mixed, and then 0.0025 g of a catalyst was added. The mixture was uniformly mixed to form a mixture; the mixture was poured into a mold and solidified at 90 ° C to prepare a silicone rubber substrate having a double bond on the surface.

(2) Preparation of a solution containing a hydrophilic monomer: 0.08 g of 2-hydroxyethyl methacrylate, 0.03 g of neopentyl glycol diacrylate, and 0.008 g of 2-dimethylamino-2-benzyl, respectively. The base-1-[4-(4-morpholinyl)phenyl]-1-butanone was dissolved in a mixed solution of 0.882 g of ethanol and isopropanol.

Comparative example 1

Preparation of silicone rubber substrate: 0.94g of vinyl polysiloxane with viscosity of 500cst, 0.056g of hydrogen-based polysiloxane with viscosity of 30cst was uniformly mixed, 0.004g of catalyst was added, mixed uniformly, and then injected into the mold, curing at 80 ° C , an unmodified base silicone rubber sample was obtained. Comparative Example 1 is a silicone rubber substrate to which no polyvinyl monomer was added, and was not subjected to hydrophilic modification.

In each of the examples and comparative examples, the component mass fractions are shown in Table 1:

Table 1

Performance Test: The present invention tested the contact angle, relative protein adsorption rate, and light transmittance of Examples 1 to 12 and Comparative Example 1. The transmittance of the silicone rubber sample was measured using an ultraviolet-visible spectrophotometer UV-2450. The surface contact angle of the silicone rubber sample was measured using a contact angle measuring instrument CAM200 (KSV). The relative adsorption rate of bovine serum albumin and lysozyme in the silicone rubber sample was measured using a BCA protein concentration assay kit. The test results are shown in Table 2:

Table 2 test results

As can be seen from Table 2, the surface contact angles of Examples 1 to 9 were significantly lower than Comparative Example 1. Compared with Comparative Example 1, the relative adsorption rates of bovine serum albumin and lysozyme were significantly reduced in Examples 1 to 9. The light transmittances of Examples 1 to 9 were slightly lower than Comparative Example 1. This is because the surface of the modified silicone rubber is covered with a hydrophilic layer compared with the unmodified silicone rubber, so the transmittance will be slightly decreased, but the overall light transmittance is above 92%, which satisfies the general optical device. Basic requirements. It can be seen from the above analysis results that after the hydrophilic modification of the silicone rubber by the hydrophilic modification method of the embodiment of the invention, the hydrophilicity of the surface is remarkably enhanced, and the relative protein adsorption rate is significantly reduced.

Fig. 1 is a silicone rubber to which no polyethylene monomer was added, i.e., Comparative Example 1, and no -C=C-absorption peak appeared at around 1638 cm ^-1 . This indicates that the surface of the silicone rubber to which no polyvinyl monomer is added does not have excess double bonds, and surface hydrophilic modification cannot be performed.

2 is a silicone rubber obtained by adding a polyvinyl monomer, corresponding to Example 1. As can be seen from Fig. 2, an absorption peak of -C=C-double bond appeared around 1638 cm ^-1 . This shows that a silicone rubber substrate having a double bond on the surface was successfully prepared by adding a polyvinyl monomer.

Figure 3 is a silicone rubber substrate with a double bond, a hydrophilic silicone rubber grafted with a hydrophilic monomer, corresponding to Example 1. As can be seen from Fig. 3, an absorption peak of an amide bond appeared at 1658 cm ^-1 . This indicates that N-vinylcaprolactam was successfully grafted onto the surface of the silicone rubber, indicating that the hydrophilic monomer with double bond can react with the silicone rubber with double bond, thereby realizing the surface modification of the silicone rubber.

1 to 3, it can be seen that by the method of the invention, a silicone rubber substrate with double bonds can be prepared on the surface in one step, and the substrate can react with a hydrophilic monomer having a double bond to realize hydrophilic modification of the surface of the silicone rubber. Sex.

Figure 4 is a contact angle diagram of a silicone rubber sample of Comparative Example 1, with a contact angle of 110°. Figure 5 is a contact angle diagram of the modified hydrophilic silicone rubber sample of Example 1, with a contact angle of 55°. As can be seen from Fig. 4 of Fig. 4, the surface contact angle of the silicone rubber can be remarkably reduced by the method of the present invention.

The basic principles and advantages of the present invention have been described above. It should be understood by those skilled in the art that the present invention is not intended to limit the scope of the present invention, and any modifications and changes that can be easily made by those skilled in the art are included in the description of the present invention. It is within the scope of the following claims.

Claims

A method for hydrophilically modifying a surface of a silicone rubber, characterized in that it comprises the following steps:

Step 10) preparing a silicone rubber substrate: mixing a vinyl polysiloxane, a hydrogen polysiloxane, and a polyvinyl monomer uniformly, then adding a catalyst, and uniformly mixing to form a mixture; injecting the mixture into a mold Heat curing to form a silicone rubber substrate having a double bond on the surface;

Step 20) preparing a solution containing a hydrophilic monomer: dissolving a hydrophilic monomer having a double bond, a crosslinking agent, and a photoinitiator in an organic solvent to obtain a solution containing a hydrophilic monomer;

Step 30) performing hydrophilic modification on the surface of the silicone rubber: the silicone rubber substrate prepared in the step 10) is placed in the solution prepared in the step 20), placed under ultraviolet light, taken out after ultraviolet initiation, and washed with water to obtain hydrophilic modification. After the silicone rubber.
The method for hydrophilically modifying a surface of a silicone rubber according to claim 1, wherein in the step 10), the mass fraction of each component in the silicone rubber substrate is as follows:

Vinyl polysiloxane: 55 to 84%;

Hydrogen-based polysiloxane: 7.2 to 25%;

Polyvinyl monomer: 5 to 24.6%;

Catalyst: 0.1 to 0.4%.
The method for hydrophilically modifying a surface of a silicone rubber according to claim 1, wherein in the step 20), the mass fraction of each substance is as follows:

Hydrophilic monomer: 5 to 35%;

Crosslinking agent: 1 to 5%;

Photoinitiator: 0.2 to 1%;

Organic solvent: 60 to 90%.
The method for hydrophilically modifying a surface of a silicone rubber according to claim 1, wherein in the step 10), the molar content of the vinyl group in the vinyl polysiloxane and the polyvinyl monomer The sum of the molar contents of the vinyl groups is greater than the molar content of the hydrogen groups in the hydrogen-based polysiloxane.
The method for hydrophilically modifying a surface of a silicone rubber according to claim 1, wherein in the step 10), the polyvinyl monomer is allyl methacrylate or tetramethyldivinyldisiloxane. Alkane, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, tetravinylsilane, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, 1,4-divinyl-1,1 Any one or a combination of 4,4-tetramethyldisilazaneethane and tetraallyl silicate.
The method for hydrophilically modifying a surface of a silicone rubber according to claim 1, wherein in the step 20), the hydrophilic monomer is 2-hydroxyethyl methacrylate, N-vinylpyrrolidone, N - any one or a combination of two of vinyl caprolactam, sodium vinyl sulfonate, 2-vinyl pyrrole, 4-vinyl pyrrole, acrylamide, polyethylene glycol methyl ether acrylate.
The method for hydrophilically modifying a surface of a silicone rubber according to claim 1, wherein in the step 20), the crosslinking agent is N,N-methylenebisacrylamide or diallyl acetal. , 1,4-butanediol dimethacrylate, 1,5-hexadiene, methacryloxy vinyl ester, allyl methacrylate, ethylene glycol dimethacrylate, triethyl Any one of diol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, and neopentyl glycol diacrylate.
The method for hydrophilically modifying a surface of a silicone rubber according to claim 1, wherein in the step 20), the photoinitiator is benzoin, diethoxyacetophenone, 2-hydroxy-2-methyl Propiophenone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2 -morpholin-1-propanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, p-phenoxy-2,2-dichlorobenzene Any one of ethyl ketone and 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone.
The method for hydrophilically modifying a surface of a silicone rubber according to claim 1, wherein in the step 20), the organic solvent is any one of methanol, ethanol, propanol, butanol, and isopropanol. Two combinations.
A method for applying a hydrophilically modified silicone rubber prepared by the method of claim 1 for making a contact lens, an intraocular lens, a medical catheter, an artificial skin or an artificial blood vessel.