WO2019100571A1 - Procédé de modification hydrophile de surface de caoutchouc de silicium et procédé d'application - Google Patents

Procédé de modification hydrophile de surface de caoutchouc de silicium et procédé d'application Download PDF

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WO2019100571A1
WO2019100571A1 PCT/CN2018/072983 CN2018072983W WO2019100571A1 WO 2019100571 A1 WO2019100571 A1 WO 2019100571A1 CN 2018072983 W CN2018072983 W CN 2018072983W WO 2019100571 A1 WO2019100571 A1 WO 2019100571A1
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silicone rubber
hydrophilic
vinyl
monomer
silicon rubber
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PCT/CN2018/072983
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Chinese (zh)
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姜勇
王小红
夏学可
张威
韩雪莲
陈平
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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
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Priority to KR1020207014193A priority Critical patent/KR20200062341A/ko
Publication of WO2019100571A1 publication Critical patent/WO2019100571A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/507—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials for artificial blood vessels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/04—Macromolecular materials
    • A61L29/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/05—Polysiloxanes containing silicon bound to hydrogen

Definitions

  • 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.
  • Silicone rubber 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.
  • 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.
  • silicone rubber 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.).
  • tubular medical devices such as catheters, cannulas, endoscopes, etc.
  • the bulk modification is mainly to blend some hydrophilic monomers with the silicone rubber system.
  • 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.
  • CN104857571A discloses a method for preparing a hydrophilic lubricating silicone rubber catheter and a hydrophilic lubricating coating thereof.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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 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 is greater than that in the hydrogen polysiloxane.
  • 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.
  • 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.
  • 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.
  • 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.
  • the organic solvent is any one or a combination of two of methanol, ethanol, propanol, butanol, and isopropanol.
  • the present invention 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.
  • 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.
  • ATR total reflection infrared spectroscopy
  • 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.
  • 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.
  • 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 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.
  • 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
  • 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.
  • 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 silicatekind or two combinations.
  • These monomers have certain compatibility with silicone rubber, which can ensure good transmittance of the modified silicone rubber.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Table 2 The test results are shown in Table 2:
  • Example 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.
  • Figure 3 is a silicone rubber substrate with a double bond, a hydrophilic silicone rubber grafted with a hydrophilic monomer, corresponding to Example 1.
  • an absorption peak of an amide bond appeared at 1658 cm -1 .
  • 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.

Abstract

L'invention concerne un procédé de modification hydrophile de surface de caoutchouc de silicium, comprenant : étape 10) préparation d'un substrat de caoutchouc de silicium : mélange rigoureux de vinyl polysiloxane, d'hydroxy polysiloxane et d'un monomère de polyvinyle, puis ajout d'un catalyseur, et formation d'un mélange; injection du mélange dans un moule pour le durcissement thermique, et préparation d'un substrat de caoutchouc de silicium pour lequel une surface contient des doubles liaisons; étape 20) préparation d'une solution contenant un monomère hydrophile : dissolution du monomère hydrophile ayant des doubles liaisons, d'un agent de réticulation et d'un photoinitiateur dans un solvant organique, et obtention d'une solution contenant le monomère hydrophile; étape 30) réalisation d'une modification hydrophile de surface du caoutchouc de silicium : positionnement du substrat de caoutchouc de silicium dans la solution préparée à l'étape 20), positionnement sous lumière ultraviolette, élimination après l'initiation des ultraviolets, lavage à l'eau, et obtention du caoutchouc de silicium à modification hydrophile. Dans le procédé, une couche hydrophile est reliée à un corps principal en caoutchouc de silicium au moyen d'une liaison chimique, ce qui peut réduire de manière significative l'angle de contact du matériau de caoutchouc de silicium, et améliorer son caractère hydrophile ainsi que sa biocompatibilité.
PCT/CN2018/072983 2017-11-21 2018-01-17 Procédé de modification hydrophile de surface de caoutchouc de silicium et procédé d'application WO2019100571A1 (fr)

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109485895A (zh) * 2018-06-28 2019-03-19 浙江清华柔性电子技术研究院 硅橡胶制品
CN109651570B (zh) * 2018-12-07 2021-01-05 湖北派克密封件有限公司 一种甲基丙烯酸羟乙酯改性硅橡胶与氢化丁腈橡胶共混胶及其制备方法
CN109575610A (zh) * 2018-12-20 2019-04-05 海昌隐形眼镜有限公司 表面硅氢功能化硅橡胶材料及制备、亲水处理和应用方法
CN109646716B (zh) * 2018-12-28 2021-04-20 深圳大学 人工角膜光学中心部及其制备方法和人工角膜
CN109793941A (zh) * 2019-01-08 2019-05-24 科塞尔医疗科技（苏州）有限公司 一种医用导管用的亲水涂层溶液及其制备方法与使用方法
CN112280088B (zh) * 2020-10-21 2022-12-02 苏州度博迈医疗科技有限公司 一种长效抗菌硅橡胶及其制备方法
CN112538271A (zh) * 2020-12-09 2021-03-23 山东大学 一种可用作医疗导管的亲水性硅橡胶及其制备方法与应用
CN112752419B (zh) * 2020-12-23 2023-03-10 浙江清华柔性电子技术研究院 植入式柔性电子器件及其制备方法
CN114712568B (zh) * 2022-06-07 2023-01-17 中国人民解放军总医院第一医学中心 一种表面改性硅橡胶胃管及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006283012A (ja) * 2005-03-08 2006-10-19 Adeka Corp ケイ素含有硬化性組成物、及びこれを熱硬化させた硬化物
US20060264583A1 (en) * 2005-05-23 2006-11-23 Shin-Etsu Chemical Co., Ltd. Lens-forming silicone resin composition and silicone lens
CN103224597A (zh) * 2013-03-28 2013-07-31 明基材料有限公司 隐形眼镜材料、隐形眼镜及制造方法
CN105555816A (zh) * 2013-09-30 2016-05-04 诺华股份有限公司 具有相对长的热稳定性的硅酮水凝胶透镜

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332922A (en) * 1980-07-18 1982-06-01 Titmus Eurocon Process for rendering silicone rubber contact lenses hydrophilic
CN105601928A (zh) * 2016-02-27 2016-05-25 北京化工大学 一种亲水性巯基改性硅橡胶及其制备方法
CN106046379A (zh) * 2016-06-25 2016-10-26 北京化工大学 一种亲水性巯基改性硅橡胶及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006283012A (ja) * 2005-03-08 2006-10-19 Adeka Corp ケイ素含有硬化性組成物、及びこれを熱硬化させた硬化物
US20060264583A1 (en) * 2005-05-23 2006-11-23 Shin-Etsu Chemical Co., Ltd. Lens-forming silicone resin composition and silicone lens
CN103224597A (zh) * 2013-03-28 2013-07-31 明基材料有限公司 隐形眼镜材料、隐形眼镜及制造方法
CN105555816A (zh) * 2013-09-30 2016-05-04 诺华股份有限公司 具有相对长的热稳定性的硅酮水凝胶透镜

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