WO2020124828A1

WO2020124828A1 - Surface silicon-hydrogen functionalized silicone rubber material, and preparation, hydrophilic treatment and application method

Info

Publication number: WO2020124828A1
Application number: PCT/CN2019/078617
Authority: WO
Inventors: 姜勇; 史琳; 未英英; 关贵钰; 韩雪莲; 陈平; 陈家华
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: 2018-12-20
Filing date: 2019-03-19
Publication date: 2020-06-25
Also published as: CN109575610A

Abstract

Disclosed are a surface silicon-hydrogen functionalized silicone rubber material, and a preparation, hydrophilic treatment and application method. A silicone rubber material with low lipid absorption can be directly prepared. The surface silicon-hydrogen functionalized silicone rubber material is formed by reacting the following components in parts by weight: 30-60 parts of vinyl silicone oil, 1-20 parts of silicon rubber inhibitor, 0.5-1 part of catalyst, and 30-60 parts of hydrogen-based silicone oil.

Description

Surface silicon hydrogen functionalized silicone rubber material and its preparation, hydrophilic treatment and application method

Technical field

The invention belongs to the technical field of preparation and modification of surface functionalized materials, in particular to a surface silicon-hydrogen functionalized silicone rubber material and its preparation, hydrophilic treatment and application method.

Background technique

Silicone rubber materials have long been widely used in the manufacture of various biomedical materials, such as human implants, catheters, pacemaker seals, and corneal contact lenses. The advantages of silicone rubber materials are: (1) can be obtained by low-temperature polymerization; (2) soft and flexible, easy to remove from the template without damaging itself and the template; (3) high visible light transmittance is suitable for optical inspection ; (4) Biologically inert and non-toxic; (5) Gas permeability is good, which is conducive to supplying oxygen to the closed system for cell culture; (6) It is easy to seal with other materials. However, there are still some problems in using silicone rubber materials for implantable biomedical materials. The surface of the silicone rubber material easily adsorbs proteins. When silicone rubber material is used as an implant, it can cause inflammation around the implant. In addition, there is a big problem of silicone rubber materials is lipid adsorption. The lipid adsorption of silicone rubber is particularly high, and the higher lipid adsorption will affect its hydrophilicity and biocompatibility. When used as a contact lens or an intraocular lens, it is necessary to reduce its lipid adsorption in addition to its biocompatibility. At present, there is no method for directly preparing silicone rubber with lower lipid adsorption, and more is to reduce its lipid adsorption through post-processing.

At present, the hydrophilic modification methods of silicone rubber are mainly divided into two types: surface modification and bulk modification. The bulk modification is mainly divided into two types: the first is to directly add hydrophilic monomers to synthesize block copolymers. This method will destroy the mechanical properties of silicone rubber, reduce the visible light transmittance, and limit its use range; the second Yes: The interpenetrating network method uses organic reagents to dissolve the two polymer networks and then copolymerize at the same time. This method must ensure that there is no chemical reaction between the two networks, or first synthesize the first network, and then use the organic reagent swelling method to dissolve the second Network embedding. This method is very complicated, the reaction conditions are very harsh, and it is difficult to industrialize. Surface hydrophilic modification is to graft hydrophilic monomers onto the surface of silicone rubber through physical or chemical methods. Physical methods include layer-by-layer self-assembly and electrostatic adsorption between each layer of compounds to adsorb hydrophilic monomers on the surface. This method is complex and non-persistent. The chemical method is to functionalize the surface, and the functional methods include plasma treatment method, chemical etching method and the like, which uses functional groups to graft hydrophilic monomers. Plasma treatment requires the necessary equipment, while chemical etching requires strong acids and bases to etch the surface. The chemical etching method requires necessary protective measures to operate, and is not suitable for industrialization.

There are many ways to hydrophilize the surface of silicone rubber, but most of them are difficult to industrialize. If the silicone rubber material is produced at the same time as it is functionalized, it can not only produce a material with excellent performance, but also reduce the difficulty of later surface treatment.

Summary of the invention

The technical problem to be solved by the present invention is to provide a surface silicon-hydrogen functionalized silicon rubber material and its preparation, hydrophilic treatment and application method, which can directly prepare a silicon rubber material with very low lipid adsorption, and then add it through silicon-hydrogen addition The reaction one-step method prepares a surface-hydrophilic silicone rubber material to improve the hydrophilicity and anti-protein adsorption of the silicone rubber material.

To solve the above technical problems, the present invention adopts the following technical solutions:

In a first aspect, an embodiment of the present invention provides a surface silicon-hydrogen functionalized silicone rubber material, which includes the following components reacted by weight:

30-60 parts of vinyl silicone oil;

1-20 parts of silicone rubber inhibitor;

Catalyst 0.5～1;

30～60 parts of hydrogen-based silicone oil.

As a preferred example, the ratio of the parts by weight of the vinyl silicone oil to the parts by weight of the hydrogen-based silicone oil is 0.5 to 2:1.

In a second aspect, an embodiment of the present invention provides a method for preparing a surface silicon-hydrogen functionalized silicone rubber material, which includes the following steps: taking 30 to 60 parts of vinyl silicone oil and 1 to 20 parts of a silicone rubber inhibitor in parts by weight, 0.5 to 1 part of the catalyst, after mixing, add 30 to 60 parts of hydrogen-based silicone oil, mix well to form a prepolymer solution; then pour the prepolymer solution into the mold; place the mold in the oven The polymer solution is cured to prepare a surface-silicon functionalized silicone rubber material.

As a preferred example, the silicone rubber inhibitor is ethynylcyclohexanol, methylbutynol, vinyltriethoxysilane, allyltrimethoxysilane, 3-trimethoxysilane acrylic acrylate, Propargyl alcohol, diallyl maleate, phenylacetylene, (3-acrylamidopropyl) tris(trimethylsiloxy)silane, trimethylolpropane trimethacrylate, tetramethyltetraethylene One or any combination of the base ring tetrasiloxane.

As a preferred example, the catalyst is one of platinum-divinyltetramethylsiloxane, chloroplatinic acid, aluminum isopropoxide, aluminum acetylacetonate, dibutyltin dilaurate, stannous chloride, or random combination.

As a preferred example, the hydrogen-based silicone oil is dimethylmethylhydrogen (siloxane and polysiloxane), poly(methylhydrogensiloxane), hydrogen-terminated dimethyl (siloxane and silicone) (Polysiloxane), trimethyl-terminated methylhydrogenated methyloctadecylsiloxane, hydrogen-terminated polyphenyl-(dimethylsiloxane) siloxane, hydrogen-terminated polyphenyl One or any combination of methyl siloxanes.

As a preferred example, the curing of the prepolymer solution in the mold is carried out by a gradient curing method, which includes: the curing temperature is gradually increased from room temperature to the target temperature, the heating time is 0.5 to 3 hours, and the constant temperature curing time at the target temperature is 3 to 12 hours; the target temperature is 50 to 100°C.

In a third aspect, an embodiment of the present invention provides a method for hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material, including:

Step 10) Preparation of hydrophilic treatment agent: in parts by weight, take 40 to 80 parts of water-soluble polymer, 0.1 to 1 part of catalyst, and 20 to 60 parts of organic solvent, mix evenly to prepare a hydrophilic treatment agent, and add 2 to 8 Store in dark place at ℃;

Preparation of surface silicon-hydrogen functionalized silicone rubber material: in weight parts, take 30 to 60 parts of vinyl silicone oil, 1 to 20 parts of silicone rubber inhibitor, and 0.5 to 1 part of catalyst. After mixing, add 30 to 60 parts of hydrogen-based silicone oil Parts, mix evenly to form a prepolymer solution; then pour the prepolymer solution into the mold; place the mold in an oven, and solidify the prepolymer solution in the mold to prepare the surface silicon hydrogen functionalized silicone rubber material ;

Step 20) The surface-silicon-hydrogenized functional silicone rubber material prepared in step 10) is immersed in the hydrophilic treatment agent prepared in step 10) to perform a hydrosilylation reaction to prepare a hydrophilic modified silicone rubber material.

As a preferred example, the hydrophilic treatment method of the surface silicon hydrogen functionalized silicone rubber material further includes:

Step 30) Prepare a mixed solution of organic solvent and water as a cleaning agent for the hydrophilic silicone rubber material; soak the hydrophilic silicone rubber material prepared in step 20) in the cleaning agent to remove unreacted hydrophilic polymer and solvent; Then rinse with pure water to remove the organic solvent in the cleaning agent to obtain the hydrophilic modified silicone rubber material after cleaning.

As a preferred example, the water-soluble polymer is a hydrophilic monomer containing a double bond.

As a preferred example, the water-soluble polymer is polyvinylpyrrolidone, 2-methacryloyloxyethyl phosphate choline, methoxypolyethylene glycol methacrylate, ethylene glycol dimethacrylate, methyl alcohol One or any combination of acryloyl ethyl sulfobetaine, diallyl polyethylene glycol, polyethylene glycol diacrylate, and hydroxyethyl methacrylate.

As a preferred example, the catalyst is one or any of platinum-divinyltetramethylsiloxane, chloroplatinic acid, aluminum isopropoxide, aluminum acetylacetonate, dibutyltin dilaurate, and stannous chloride. combination.

As a preferred example, the organic solvent is butanediol, ethanol, isopropanol, propylene glycol or isobutanol.

As a preferred example, in the step 20), during the hydrosilylation reaction, the reaction temperature is 30 to 70° C., and the reaction time is 1 to 6 hours.

As a preferred example, in the step 30), the cleaning agent is a butanediol aqueous solution, an ethanol aqueous solution, an isopropyl alcohol aqueous solution, a propylene glycol aqueous solution, or an isobutanol aqueous solution, and the mass concentration of the cleaning agent is 1-25%.

According to a fourth aspect, an embodiment of the present invention provides a surface silicon-hydrogen functionalized silicone rubber material, which is used as a medical catheter, wound dressing, mepitel, corneal contact lens, or human implant.

Compared with the prior art, the present invention has the following beneficial effects: immersing the silicone rubber material functionalized on the surface with silicon hydrogen in a water-soluble polymer solution with double bonds, using the principle of silicon hydrogen addition for chemical grafting, and one-step preparation The hydrophilic silicone rubber material firmly grafts hydrophilic molecules onto the surface of the silicone rubber. Compared with the prior art, the hydrophilic treatment method of the embodiment of the present invention does not require a cumbersome treatment process. In addition, the silicon-hydrogen-functionalized silicone rubber material prepared in the embodiment of the present invention can reduce lipid adsorption by more than 95%; after undergoing surface hydrophilic treatment, lipid adsorption can be further reduced by more than 60%. The hydrophilicity and anti-protein adsorption ability of silicone rubber functionalized with silicon hydrogen have also been significantly improved.

BRIEF DESCRIPTION

1 is a total reflection infrared spectrum ATR spectrum chart of the surface-free functional group silicone rubber material prepared in Comparative Example 1 in the experiment of the present invention;

2 is a total reflection infrared spectroscopy ATR spectrum chart of the surface silicon hydrogen functionalized silicone rubber material prepared in Comparative Example 2 in the experiment of the present invention;

FIG. 3 is an ATR spectrum chart of the hydrophilic modified silicone rubber material prepared in step (3) in Example 1 in the experiment of the present invention;

4 is a contact angle diagram of a surface-free silicone rubber material prepared in Comparative Example 1 in the test of the present invention;

5 is a contact angle diagram of the surface silicon hydrogen functionalized silicone rubber material prepared in Comparative Example 2 in the experiment of the present invention;

Fig. 6 is a contact angle diagram of the silicone rubber material after hydrophilic modification in step (3) of Example 6 in the test of the present invention.

detailed description

In order to make the technical means, creative features, and objectives of the present invention easy to understand and understand, the present invention will be further described in detail with reference to specific embodiments, but the present invention is not limited in any way.

A surface silicon-hydrogen functionalized silicone rubber material according to an embodiment of the present invention is characterized by including the following components by weight:

30-60 parts of vinyl silicone oil;

1-20 parts of silicone rubber inhibitor;

Catalyst 0.5～1;

30～60 parts of hydrogen-based silicone oil.

In the above embodiment, the ratio of the parts by weight of the vinyl silicone oil to the parts by weight of the hydrogen-based silicone oil is 0.5 to 2:1, for example, the ratio of the parts by weight of vinyl silicone oil to the parts by weight of the hydrogen-based silicone oil is 0.5:1 , 1.5:1, 1:1, 2:1. The selected silicone rubber inhibitor in the system is a compound containing one or more double bonds and triple bonds. It can react with the silicon-hydrogen bond in the hydrogen-based silicone oil through the mechanism of the silicon-hydrogen addition reaction. Silicone rubber inhibitors with multiple double bonds have multiple reactive sites, which increase the crosslinking density of the polymer, so that the surface-silicon functionalized silicone rubber material can be crosslinked and shaped. The inhibitors used in the prior art all contain a reactive functional group, have few reactive sites, and have low cross-linking density. It is difficult to reserve unreacted silicon-hydrogen bonds on the surface.

The surface of the silicone rubber material that has not been surface functionalized is rich in Si-CH ₃ bonds. The surface silicon-hydrogen-functionalized silicone rubber surface is rich in Si-H bonds, and the difference in electronegativity between CH bonds is smaller than that of Si-H bonds. The greater the difference in electronegativity, the greater the polarity of the bond and the greater the hydrophilicity. This is because water is a compound containing polar bonds, explained by the principle of similar miscibility: water prefers surfaces with large polar bonds. Similarly, lipids are compounds that are insoluble in water but soluble in fat-soluble solvents and tend to adsorb on the surface of non-polar materials. By functionalizing the surface silicon hydrogen of the silicone rubber material, the polarity of the surface is increased to achieve the purpose of hydrophilicity and oleophobicity, that is, to increase the hydrophilicity and reduce the lipid adsorption. Grafting hydrophilic monomers on the surface of silicone rubber material further improves the surface polarity, and the hydrophilicity and lipid adsorption are also improved. The adsorption of protein is caused by the low surface energy of the material surface. The low surface energy of the material surface will show hydrophobicity. Protein molecules are composed of a hydrophobic end and a hydrophilic end, with the hydrophilic end facing outward for contact with water molecules and the hydrophobic end facing in for contact with the surface of the material. When the surface of the material is hydrophobic, the hydrophobic end of the protein will interact with the surface of the hydrophobic material, resulting in protein adsorption. By hydrophilically modifying the surface of the material, it can play a role in resisting protein adsorption.

By adding a silicone rubber inhibitor containing double bonds to the system, the double bonds on the silicone rubber inhibitor react with the silicon hydrogen to increase the crosslink density. By controlling the ratio of reactants, silicon-hydrogen bonds can be reserved, and the polymer can be cross-linked to form. The extraction of silicon-hydrogen bonds can reduce the lipid adsorption of silicone rubber materials, and can provide functional groups for subsequent hydrophilic modification.

The present invention also provides an embodiment. The preparation method of the above surface silicon hydrogen functionalized silicone rubber material includes the following steps:

In terms of parts by weight, take 30 to 60 parts of vinyl silicone oil, 1 to 20 parts of silicone rubber inhibitor, and 0.5 to 1 part of catalyst. After mixing, add 30 to 60 parts of hydrogen-based silicone oil, mix evenly to form polydimethyl Silicone (hereinafter referred to as PDMS) solution; then pour the PDMS solution into the mold; place the mold in an oven to cure the PDMS solution in the mold to prepare a surface-silicon functionalized silicone rubber material.

In this embodiment, preferably, the silicone rubber inhibitor is ethynylcyclohexanol, methylbutynol, vinyltriethoxysilane, allyltrimethoxysilane, 3-trimethoxysilane Propylene acrylate, propynol, phenylacetylene, diallyl maleate, (3-acrylamidopropyl) tris(trimethylsiloxy) silane, trimethylolpropane trimethacrylate, tetra One or any combination of methyltetravinylcyclotetrasiloxane.

Preferably, the catalyst is one or any of platinum-divinyltetramethylsiloxane, chloroplatinic acid, aluminum isopropoxide, aluminum acetylacetonate, dibutyltin dilaurate, and stannous chloride. combination.

Preferably, the hydrogen-based silicone oil is dimethylmethylhydrogen (siloxane and polysiloxane), poly(methylhydrogensiloxane), hydrogen-terminated dimethyl (siloxane and polysiloxane) Siloxane), trimethyl-terminated methylhydrogenated methyloctadecyl siloxane, hydrogen-terminated polyphenyl-(dimethylsiloxane) siloxane, hydrogen-terminated polyphenyl methyl One or any combination of siloxanes.

Preferably, the curing of the PDMS solution in the mold is performed by a gradient curing method, which includes: the curing temperature is gradually increased from room temperature to the target temperature, the heating time is 0.5 to 3 hours, and the constant temperature curing time at the target temperature is 3 to 12 Hours; the target temperature is 50-100°C. This method can reduce the reaction rate and make the reaction more complete.

The above preparation method has the advantages of easily available reaction conditions, controllable reaction rate, no by-products, and deep curing, which is suitable for industrialization and has a wider range of applications. There are also condensation reactions in the preparation of existing silicone rubber materials, and organic peroxide pendants cause two kinds of cross-linking reactions, which belong to free radical-initiated reactions and the reaction rate is uncontrollable. The reaction of this embodiment is uniformly mixed at room temperature and can be reacted. The reaction rate can be controlled by adding the amount of silicone rubber inhibitor, and the degree of reaction can be controlled by controlling the temperature of the reaction. No by-products will be produced after the reaction is completed.

The present invention also provides a third embodiment, a method for hydrophilic treatment of surface silicon hydrogen functionalized silicone rubber material, including:

Step 10) Preparation of hydrophilic treatment agent: in parts by weight, take 40 to 80 parts of water-soluble polymer, 0.1 to 1 part of catalyst, and 20 to 60 parts of organic solvent, mix evenly to prepare a hydrophilic treatment agent, and add 2 to 8 Store in dark place at ℃.

Preparation of surface silicon-hydrogen functionalized silicone rubber material: in weight parts, take 30 to 60 parts of vinyl silicone oil, 1 to 20 parts of silicone rubber inhibitor, and 0.5 to 1 part of catalyst. After mixing, add 30 to 60 parts of hydrogen-based silicone oil Parts, mix evenly to form a prepolymer solution; then pour the prepolymer solution into a mold; place the mold in an oven to cure the prepolymer solution in the mold to prepare a surface silicone functionalized silicone rubber material. The size of the mold depends on the actual needs. For example, using a mold with a length and width of 1 cm x 1 cm, other sizes can also be used.

Step 20) The surface-silicon-hydrogenized functional silicone rubber material prepared in step 10) is immersed in the hydrophilic treatment agent prepared in step 10) to perform a hydrosilylation reaction to prepare a hydrophilic modified silicone rubber material. Preferably, during the hydrosilylation reaction, the reaction temperature is 30-70°C, and the reaction time is 1-6 hours.

In the hydrophilic treatment method of this embodiment, the silicone rubber material on the surface of silicon hydrogen is grafted with a hydrophilic monomer through a silicon hydrogen addition reaction.

Preferably, the water-soluble polymer is a hydrophilic monomer containing double bonds. For example, the water-soluble polymer is polyvinylpyrrolidone, 2-methacryloyloxyethyl phosphate choline, methoxypolyethylene glycol methacrylate, ethylene glycol dimethacrylate, methacrylic acid One or any combination of acylethylsulfobetaine, diallyl polyethylene glycol, polyethylene glycol diacrylate, and hydroxyethyl methacrylate.

Preferably, the catalyst is one or any combination of platinum-divinyltetramethylsiloxane, chloroplatinic acid, aluminum isopropoxide, aluminum acetylacetonate, dibutyltin dilaurate, stannous chloride .

Preferably, the hydrophilic treatment method of the surface silicon hydrogen functionalized silicone rubber material further includes:

Through step 30) and cleaning the hydrophilic silicone rubber material prepared in step 20), the hydrophilic modified silicone rubber material after cleaning is obtained. Preferably, the organic solvent is butanediol, ethanol, isopropanol, propylene glycol or isobutanol. Select the cleaning agent according to the solvent used in the hydrophilic treatment. Preferably, the cleaning agent is a butylene glycol aqueous solution, an ethanol aqueous solution, an isopropyl alcohol aqueous solution, a propylene glycol aqueous solution or an isobutanol aqueous solution, and the mass concentration of the cleaning agent is 1-25%.

The embodiment of the invention adopts a one-step method to prepare the surface-silicon functionalized silicone rubber material. Compared with the prior art, the method is simple in operation, non-toxic and harmless, and easy to be industrialized. The surface silicon-hydrogen-functionalized silicone rubber material prepared in the embodiment of the present invention has excellent optical properties, and lipid adsorption can be reduced by more than 95% compared with ordinary silicone rubber materials. By hydrosilylation reaction, hydrophilic monomers containing double bonds are grafted to further improve the hydrophilicity and protein adsorption of the material, and lipid adsorption can be further reduced by more than 60%.

The surface silicon-hydrogen functionalized silicone rubber material prepared in the above embodiments can be used as a medical catheter, wound dressing, mepitel, corneal contact lens, or human implant.

The following provides specific examples to verify the excellent performance of the surface silicon hydrogen functional silicone rubber material of the present application.

Example 1

(1) Preparation of surface silicon-hydrogen functionalized silicone rubber material: first mix 30g vinyl silicone oil, 1g diallyl maleate, 0.5g platinum-divinyltetramethylsiloxane for 2 hours, then add 30g Dimethyl methyl hydrogen (silicone and polysiloxane) are mixed evenly to form a prepolymer solution; then the prepolymer solution is poured into a mold and placed in an oven, the temperature is raised from room temperature to 100°C, and the temperature is raised for a long time 3 hours, constant temperature curing at 100°C for 3 hours; after curing, the silicone rubber material is peeled off the mold for use.

(2) Hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material: add 20g of methoxypolyethylene glycol methacrylate and 20g of polyethylene glycol diacrylate to 60g of isopropanol, and add 0.4g of chlorine The platinum acid was mixed uniformly to prepare a hydrophilic treatment agent, and then the prepared silicone rubber material was immersed in the hydrophilic treatment agent and reacted at 50°C for 3.5 hours.

(3) Cleaning of silicone rubber materials: prepare a 1% isopropyl alcohol aqueous solution as a cleaning agent, soak the hydrophilic silicone rubber material in the cleaning agent to remove unreacted hydrophilic polymers and solvents, and then use pure Water repeatedly rinses to remove the organic solvent in the cleaning agent to obtain a hydrophilically modified silicone rubber material.

Example 2

(1) Preparation of surface silicon-hydrogen functionalized silicone rubber material: firstly 45g vinyl silicone oil, 10g ethynyl cyclohexanol, 5g diallyl maleate, 0.2g aluminum isopropoxide, 0.3g chloroplatinic acid, Mix 0.2g of stannous chloride for 2.5 hours, then add 50g of hydrogen-terminated dimethyl (silicone and polysiloxane) and mix well to form a prepolymer solution; then pour the prepolymer solution into the mold and put After entering the oven, the temperature is raised from room temperature to 90°C, the heating time is 2 hours, and the temperature is cured at 90°C for 4 hours; after curing and molding, the silicone rubber is peeled off the mold for use.

(2) Hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material: add 25g polyvinylpyrrolidone and 25g methacryloyl ethyl sulfobetaine to 50g butanediol, add 0.1g platinum-divinyl tetra Methyl siloxane is mixed and uniformly formulated into a hydrophilic treatment agent, and then the prepared silicone rubber material is soaked in the hydrophilic treatment agent and reacted at 30°C for 6 hours.

(3) Cleaning of silicone rubber material: prepare a 5% butanediol aqueous solution as a cleaning agent, soak the hydrophilic-treated silicone rubber material in the cleaning agent to remove unreacted hydrophilic polymer and solvent, and then use pure Water repeatedly rinses to remove the organic solvent in the cleaning agent to obtain a hydrophilically modified silicone rubber material.

Example 3

(1) Preparation of surface silicon hydrogen functionalized silicone rubber material: 30g vinyl silicone oil, 10g vinyl triethoxysilane, 10g (3-acrylamidopropyl) tris (trimethylsiloxy) silane, 0.6 g Aluminium acetylacetonate is mixed for 3 hours, then add 30g of poly(methylhydrogensiloxane), 30g of dimethylmethylhydrogen (siloxane and polysiloxane) and mix well to form a prepolymer solution; then The prepolymer solution was poured into the mold and placed in an oven. The temperature was raised from room temperature to 80°C, the temperature was raised for 2 hours, and the temperature was cured at 80°C for 5 hours. After curing, the silicone rubber was peeled off the mold for use.

(2) Hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material: add 80g of 2-methacryloyloxyethyl phosphate choline to 20g of propylene glycol, add 0.3g of aluminum acetylacetonate, 0.2g of platinum-di Vinyltetramethylsiloxane is mixed uniformly to prepare a hydrophilic treatment agent, and then the prepared silicone rubber material is soaked in the hydrophilic treatment agent and reacted at 35°C for 5 hours.

(3) Cleaning of silicone rubber material: prepare a 10% aqueous solution of propylene glycol as a cleaning agent, soak the hydrophilic silicone rubber material in the cleaning agent to remove unreacted hydrophilic polymer and solvent, and then repeat with pure water The organic solvent in the cleaning agent is removed by rinsing to obtain a hydrophilically modified silicone rubber material.

Example 4

(1) Preparation of surface silicon-hydrogen functionalized silicone rubber material: first mix 60g vinyl silicone oil, 10g tetramethyltetravinylcyclotetrasiloxane, 0.8g chloroplatinic acid for 2 hours, then add 30g trimethyl seal The methylhydrogenated methyloctadecylsiloxane at the end is mixed evenly to form a prepolymer solution; then the prepolymer solution is poured into a mold and placed in an oven. The temperature is raised from room temperature to 50°C, and the heating time is 0.5 hours, 50 Constant temperature curing at ℃ for 12 hours; after curing, the silicone rubber is peeled off the mold for use.

(2) Hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material: 65 ethylene glycol dimethacrylate was added to 35g of ethanol, 0.7g of dibutyltin dilaurate was added and mixed uniformly to prepare a hydrophilic treatment agent, followed by The silicone rubber material was immersed in a hydrophilic treatment agent and reacted at 70°C for 1 hour.

(3) Cleaning of silicone rubber material: prepare 25% ethanol aqueous solution as cleaning agent, soak the hydrophilic silicone rubber material in the cleaning agent to remove unreacted hydrophilic polymer and solvent, and then repeat with pure water The organic solvent in the cleaning agent is removed by rinsing to obtain a hydrophilically modified silicone rubber material.

Example 5

(1) Preparation of surface silicon hydrogen functionalized silicone rubber material: firstly 54g vinyl silicone oil, 12g methylbutynol, 6g trimethylolpropane trimethacrylate, 0.2g dibutyltin dilaurate, 0.3g Chloroplatinic acid was mixed for 3.5 hours, then 36g of hydrogen-terminated polyphenyl-(dimethylsiloxane) siloxane was added to mix well to form a prepolymer solution; then the prepolymer solution was poured into the mold and placed In the oven, the temperature is raised from room temperature to 70°C, the heating time is 1 hour, and the temperature is cured at 70°C for 6 hours. After curing, the silicone rubber is peeled off the mold for use.

(2) Hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material: 37g ethylene glycol dimethacrylate, 23g diallyl polyethylene glycol are added to 40g isobutanol, 0.9g subchlorinated chloride is added Tin is mixed uniformly to make a hydrophilic treatment agent, and then the prepared silicone rubber material is soaked in the hydrophilic treatment agent and reacted at 60°C for 2 hours.

(3) Cleaning of silicone rubber material: prepare a 23% aqueous solution of isobutanol as a cleaning agent, immerse the hydrophilic silicone rubber material in the cleaning agent to remove unreacted hydrophilic polymer and solvent, and then use pure Water repeatedly rinses to remove the organic solvent in the cleaning agent to obtain a hydrophilically modified silicone rubber material.

Example 6

(1) Preparation of surface silicon hydrogen functionalized silicone rubber material: firstly 35g vinyl silicone oil, 4g (3-acrylamidopropyl) tris(trimethylsiloxy) silane, 4g propynol, 0.6g chlorinated Tin is mixed for 1.8 hours, then add 15g of poly(methylhydrogensiloxane) and 20g of hydrogen-terminated polyphenylmethylsiloxane and mix well to form a prepolymer solution; then pour the prepolymer solution into the mold Put it in the oven, the temperature starts to rise from room temperature to 60 ℃, the heating time is 0.8 hours, 60 ℃ constant temperature curing for 8 hours; after curing molding, the silicone rubber is peeled off the mold for use.

(2) Hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material: add 20g of methacryloyl ethyl sulfobetaine and 55g of methoxypolyethylene glycol methacrylate to 25g of isopropanol, add 0.6g of aluminum isopropoxide was mixed and uniformly formulated into a hydrophilic treatment agent, and then the prepared silicone rubber material was soaked in the hydrophilic treatment agent and reacted at 40°C for 4 hours.

(3) Cleaning of silicone rubber material: prepare a 15% isopropyl alcohol aqueous solution as a cleaning agent, soak the silicone rubber material after hydrophilic treatment in the cleaning agent to remove unreacted hydrophilic polymer and solvent to obtain hydrophilic Modified silicone rubber material.

Example 7

(1) Preparation of surface silicon-hydrogen functionalized silicone rubber material: firstly 48g vinyl silicone oil, 8g allyltrimethoxysilane, 4g trimethylolpropane trimethacrylate, 4g phenylacetylene, 0.9g chloroplatin Acid mix for 2.8 hours, then add 25g of hydrogen-terminated dimethyl (siloxane and polysiloxane), 23g of dimethyl methyl hydrogen (siloxane and polysiloxane) and mix well to form a prepolymer Solution; then pour the prepolymer solution into the mold and put it into an oven, the temperature is raised from room temperature to 75 ℃, the temperature is raised for 1 hour, and the temperature is cured at 75 ℃ for 7 hours; after curing, the silicone rubber is peeled off the mold for use.

(2) Hydrophilic treatment of surface silicon hydrogen functionalized silicone rubber material: add 15g hydroxyethyl methacrylate and 25g polyvinylpyrrolidone to 60g propylene glycol, add 1g platinum-divinyltetramethylsiloxane and mix well It is formulated into a hydrophilic treatment agent, and then the prepared silicone rubber material is soaked in the hydrophilic treatment agent, and reacted at 55°C for 3.8 hours.

(3) Cleaning of silicone rubber material: prepare 8% propylene glycol aqueous solution as a cleaning agent, soak the hydrophilic silicone rubber material in the cleaning agent to remove unreacted hydrophilic polymer and solvent, and then repeat with pure water The organic solvent in the cleaning agent is removed by rinsing to obtain a hydrophilically modified silicone rubber material.

Example 8

(1) Preparation of surface silicon-hydrogen functionalized silicone rubber material: firstly 57g vinyl silicone oil, 3g 3-trimethoxysilane acrylic acrylate, 2g trimethylolpropane trimethacrylate, 1g platinum-divinyl Tetramethylsiloxane mixed for 3.5 hours, then added 36g of poly (methylhydrogensiloxane), 21g of trimethyl-terminated methylhydrogenated methyloctadecylsiloxane and mixed well to form a prepolymer solution; Then pour the prepolymer solution into the mold and put it into the oven. The temperature is raised from room temperature to 85°C, the heating time is 2.5 hours, and the temperature is cured at 85°C for 10 hours. After curing, the silicone rubber is peeled off the mold and used.

(2) Hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material: add 80g of ethylene glycol dimethacrylate to 20g of butanediol, add 0.3g of chloroplatinic acid and mix evenly to make a hydrophilic treatment agent, followed by The prepared silicone rubber material was immersed in a hydrophilic treatment agent and reacted at 65°C for 1.5 hours.

(3) Cleaning of silicone rubber material: prepare a 17% butylene glycol aqueous solution as a cleaning agent, soak the hydrophilic silicone rubber material in the cleaning agent to remove unreacted hydrophilic polymer and solvent, and then use pure Water repeatedly rinses to remove the organic solvent in the cleaning agent to obtain a hydrophilically modified silicone rubber material.

Comparative Example 1

Preparation of surface non-functional silicone rubber material: mix 30g vinyl silicone oil, 0.01g maleic anhydride diallyl ester, 0.05g platinum-divinyltetramethylsiloxane for 2 hours, then add 1g poly(methyl (Hydroxysiloxane) Mix evenly. Pour the solution into the mold and put it in an oven. The temperature will be increased from room temperature to 50°C. The heating time is 0.5 hours, and the temperature is cured at 50°C for 12 hours. After curing, the silicone rubber material is peeled off the mold and set aside.

Comparative Example 2

Preparation of surface silicon hydrogen functionalized silicone rubber material: mix 30g vinyl silicone oil, 10g tetramethyltetravinylcyclotetrasiloxane, 0.5g chloroplatinic acid for 2 hours, then add 30g dimethylmethylhydrogen (silicon Oxane and polysiloxane) are mixed evenly. Pour the solution into the mold and put it in the oven. The temperature is raised from room temperature to 50°C. The heating time is 0.5 hours. The temperature is cured at 50°C for 12 hours. After curing, the silicone rubber material is peeled The mold is spared.

Performance tests were conducted on the silicone rubber materials prepared in the above examples and comparative examples.

Performance test 1: The contact angle measuring instrument CAM200 was used to test the water contact angle of Examples 1 to 8 and Comparative Examples 1 and 2.

Performance test 2: BCA protein concentration determination kit was used to detect the adsorption of silicone rubber material to bovine serum albumin and lysozyme. Taking Comparative Example 1 as a control, the relative protein adsorption rates of Comparative Example 2 and Examples 1 to 8 are the relative percentages of the protein adsorption rates of Comparative Example 2 and Examples 1-8 to the protein adsorption rates of Comparative Example 1.

Performance test 3: The iron oxide color reagent met the lipid coloring method to detect the lipid adsorption of Examples 1 to 8 and Comparative Examples 1 and 2, and then use the 7200 spectrophotometer to detect the lipid adsorption amount;

Performance test 4: A UV-2600 ultraviolet-visible light spectrophotometer was used to detect the visible light transmittance of Examples 1 to 8 and Comparative Examples 1 and 2.

The above test results are shown in Table 1:

Table 1

It can be seen from Table 1 that the contact angle (80°) of the silicone rubber material rich in silicon-hydrogen bonds on the surface of Comparative Example 2 is significantly lower than that of the silicone rubber material without functional groups on the surface (109°) of Comparative Example 1. This is because Si-H is more hydrophilic than Si-C. The water contact angles of Examples 1 to 8 are all below 60°, and their relative protein adsorption rate is significantly lower than that of the comparative example. This is because by grafting water-soluble molecules on the surface, a hydrophilic layer is formed on the surface of the silicone rubber material, which reduces the water contact angle and the relative adsorption rate of protein. It can be seen that the lipid adsorption of Comparative Examples 1-8 and Comparative Examples 1 and 2: through the surface silicon-hydrogen functionalization, the lipid adsorption of the silicone rubber material is reduced by more than 95%, and then the surface is prepared by a one-step method of silicon-hydrogen addition reaction The hydrophilic silicone rubber material, its lipid adsorption is further reduced by more than 60%. The visible light transmittance of the hydrophilic silicone rubber materials prepared by the method of the present invention are all above 95%. Therefore, the material can be used in the field of optical instruments.

FIG. 1 is an infrared diffuse reflection diagram of the surface of Comparative Example 1 without functionalized silicone rubber material. There is no stretching vibration peak of silicon hydrogen at 2160cm ^-1 , and there is no characteristic peak of other functional groups in the figure. This shows that the silicone rubber material of Comparative Example 1 has no reactive functional groups on the surface and cannot be subjected to subsequent hydrophilic modification.

2 is an infrared diffuse reflection diagram of the surface silicon hydrogen functionalized silicone rubber material in Comparative Example 2. FIG. By adding an inhibitor containing a double bond and adjusting the ratio of the double bond to the molar amount of silicon-hydrogen, a silicone rubber material functionalized with surface silicon-hydrogen was prepared. It can be seen from Figure 2 that there is a characteristic peak at 2160 cm ^-1 , which belongs to the stretching vibration peak of silicon hydrogen; the peak at 914 cm ^-1 is the bending vibration peak of silicon hydrogen. This shows that the surface of the silicone rubber material of Comparative Example 2 is rich in Si-H bonds and subsequent hydrophilic treatment steps can be performed.

3 is an ATR diagram of the hydrophilic modified silicone rubber material prepared in step (3) in Example 1. FIG. It can be seen from the figure that there is a stretching vibration peak of -CH ₂ -unit at 2875cm ^-1 , and a stretching vibration peak of anti-symmetrical -CH ₂ -CH ₂ -O unit at 1349cm-1, which shows that The CH ₂ -CH ₂ -O repeating unit in the diol derivative appeared on the surface of the silicone rubber; the stretching vibration peak of the silicon hydrogen at 2160 cm ^-1 disappeared, and the bending vibration of the silicon hydrogen at 914 cm ^-1 also disappeared. Ethylene glycol derivatives have been successfully grafted onto the surface functionalized silicone rubber material by hydrosilylation.

4 is a contact angle diagram of the silicone rubber material of Comparative Example 1, and the contact angle is 109°. This shows that the silicone rubber material without functionalization on the surface is hydrophobic.

Fig. 5 is a contact angle diagram of the surface silicon-hydrogen-functionalized silicone rubber material in step (1) of Example 3, and the contact angle is 80°. This shows that the Si-H bond derived from the surface is beneficial to improve the surface energy of the material surface, improve its hydrophilicity and anti-lipid adsorption capacity.

6 is a contact angle diagram of the silicone rubber after hydrophilic modification in step (3) of Example 6, and the contact angle is 51°. Figures 3 and 6 illustrate that the present invention can utilize the mechanism of the silicon-hydrogen addition reaction to react the hydrophilic molecules containing double bonds with the silicon-hydrogen bonds on the surface of the material, so that the silicone rubber is wrapped by the hydrophilic layer, which improves the silicone rubber material. Hydrophilic.

The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above specific embodiments. The above specific embodiments and the descriptions in the specification are only for further illustrating the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention There will be various changes and improvements in the invention, and these changes and improvements fall within the scope of the claimed invention. The scope of protection claimed by the present invention is defined by the claims and their equivalents.

Claims

A surface silicon-hydrogen functionalized silicone rubber material, characterized by comprising the following components by weight:

30-60 parts of vinyl silicone oil;

1-20 parts of silicone rubber inhibitor;

Catalyst 0.5～1;

30～60 parts of hydrogen-based silicone oil.
The surface silicon-hydrogen functionalized silicone rubber material according to claim 1, wherein the ratio of the weight parts of the vinyl silicone oil to the weight parts of the hydrogen-based silicone oil is 0.5 to 2:1.
A preparation method of surface silicon-hydrogen functionalized silicone rubber material, which is characterized by comprising the following steps:

In terms of parts by weight, take 30 to 60 parts of vinyl silicone oil, 1 to 20 parts of silicone rubber inhibitor, and 0.5 to 1 part of catalyst. After mixing, add 30 to 60 parts of hydrogen-based silicone oil, mix evenly to form a prepolymer solution. ; Then pour the prepolymer solution into the mold; put the mold into the oven, and solidify the prepolymer solution in the mold to prepare the surface silicon hydrogen functionalized silicone rubber material.
The method for preparing a surface-silicon-hydrogen functionalized silicone rubber material according to claim 3, wherein the silicone rubber inhibitor is ethynylcyclohexanol, methylbutynol, vinyltriethoxysilane , Allyltrimethoxysilane, 3-trimethoxysilane acrylic acrylate, propynol, diallyl maleate, phenylacetylene, (3-acrylamidopropyl) tris(trimethylsiloxy) ) One or any combination of silane, trimethylolpropane trimethacrylate, and tetramethyltetravinylcyclotetrasiloxane.
The preparation method of surface silicon hydrogen functionalized silicone rubber material according to claim 3, characterized in that the catalyst is platinum-divinyltetramethylsiloxane, chloroplatinic acid, aluminum isopropoxide, acetyl One or any combination of aluminum acetone, dibutyltin dilaurate, and stannous chloride.
The method for preparing a surface-silicon-hydrogen functionalized silicone rubber material according to claim 3, wherein the hydrogen-based silicone oil is dimethyl methyl hydrogen (siloxane and polysiloxane), poly(A Hydrogen siloxane), hydrogen-terminated dimethyl (siloxane and polysiloxane), trimethyl-terminated methyl hydrogenated methyl octaalkyl siloxane, hydrogen-terminated polyphenyl- (Dimethicone) One or any combination of siloxane and hydrogen-terminated polyphenylmethylsiloxane.
The method for preparing a surface silicon-hydrogen functionalized silicone rubber material according to claim 3, wherein the curing of the prepolymer solution in the mold is performed by a gradient curing method, which includes: the curing temperature is gradually increased from room temperature To the target temperature, the heating time is 0.5 to 3 hours, and the constant temperature curing time at the target temperature is 3 to 12 hours; the target temperature is 50 to 100°C.
A method for hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material, characterized in that it includes:

Step 10) Preparation of hydrophilic treatment agent: in parts by weight, take 40 to 80 parts of water-soluble polymer, 0.1 to 1 part of catalyst, and 20 to 60 parts of organic solvent, mix evenly to prepare a hydrophilic treatment agent, and add 2 to 8 Store in dark place at ℃;

Preparation of surface silicon-hydrogen functionalized silicone rubber material: in weight parts, take 30 to 60 parts of vinyl silicone oil, 1 to 20 parts of silicone rubber inhibitor, and 0.5 to 1 part of catalyst. After mixing, add 30 to 60 parts of hydrogen-based silicone oil Parts, mix evenly to form a prepolymer solution; then pour the prepolymer solution into the mold; place the mold in an oven, and solidify the prepolymer solution in the mold to prepare the surface silicon hydrogen functionalized silicone rubber material ;

Step 20) The surface-silicon-hydrogenized functional silicone rubber material prepared in step 10) is immersed in the hydrophilic treatment agent prepared in step 10) to perform a hydrosilylation reaction to prepare a hydrophilic modified silicone rubber material.
The method for hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material according to claim 8, further comprising:

Step 30) Prepare a mixed solution of organic solvent and water as a cleaning agent for the hydrophilic silicone rubber material; soak the hydrophilic silicone rubber material prepared in step 20) in the cleaning agent to remove unreacted hydrophilic polymer and solvent; Then rinse with pure water to remove the organic solvent in the cleaning agent to obtain the hydrophilic modified silicone rubber material after cleaning.
The method for hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material according to claim 8, wherein the water-soluble polymer is a hydrophilic monomer containing a double bond.
The method for hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material according to claim 10, wherein the water-soluble polymer is polyvinylpyrrolidone, 2-methacryloyloxyethyl phosphate choline, methyl alcohol Oxypolyethylene glycol methacrylate, ethylene glycol dimethacrylate, methacryloyl ethyl sulfobetaine, diallyl polyethylene glycol, polyethylene glycol diacrylate, methyl One or any combination of hydroxyethyl acrylates.
The method for hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material according to claim 8, wherein the catalyst is platinum-divinyltetramethylsiloxane, chloroplatinic acid, aluminum isopropoxide, One or any combination of aluminum acetylacetonate, dibutyltin dilaurate, and stannous chloride.
The method for hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material according to claim 8, wherein the organic solvent is butanediol, ethanol, isopropanol, propylene glycol or isobutanol.
The method for hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material according to claim 8, wherein in the step 20), during the silicon-hydrogen addition reaction, the reaction temperature is 30-70°C, and the reaction time is long 1 to 6 hours.
The method for hydrophilic treatment of surface silicon-hydrogen functionalized silicone rubber material according to claim 9, characterized in that in step 30), the cleaning agent is butanediol aqueous solution, ethanol aqueous solution, isopropyl alcohol aqueous solution, propylene glycol An aqueous solution or an isobutanol aqueous solution, and the mass concentration of the cleaning agent is 1-25%.
A surface silicon-hydrogen functionalized silicone rubber material according to claim 1, which is used as a medical catheter, wound dressing, mepitel, corneal contact lens, or human implant.