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

Method for surface hydrophilic modification of silicon rubber and application method 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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French (fr)
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/en
Publication of WO2019100571A1 publication Critical patent/WO2019100571A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12Chemical modification
    • C08J7/16Chemical modification with polymerisable compounds
    • C08J7/18Chemical modification with polymerisable compounds using wave energy or particle radiation
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14Macromolecular materials
    • A61L27/18Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/507Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials for artificial blood vessels
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/04Macromolecular materials
    • A61L29/06Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions 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
    • C08L83/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00Characterised 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
    • C08J2383/04Polysiloxanes
    • C08J2383/07Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00Characterised 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
    • C08J2483/04Polysiloxanes
    • C08J2483/05Polysiloxanes 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

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

一种硅橡胶表面亲水改性的方法及应用方法Method and application method for hydrophilic modification of silicone rubber surface 技术领域Technical field
本发明属于材料表面改性技术领域,具体来说,涉及一种硅橡胶表面亲水改性的方法及应用方法。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.
背景技术Background technique
硅橡胶(文中简称:PDMS)是指含官能团的聚硅氧烷与交联剂在一定条件下反应形成的具有三维网络结构的弹性体。硅橡胶的优点是无毒、生物相容性好、氧气透过率高、制备方法简单、成本低、柔软而且有一定强度,所以硅橡胶是制造体腔及血管内介入器械(如角膜接触镜、医用导管、内窥镜、腔道内支架等)的最佳材料。但是硅橡胶属于非极性材料,表面能很低,所以将其用于接触式医疗器械时还存在问题。比如,表面很容易粘附非极性物质,细菌通过粘附蛋白质很容易在硅橡胶表面聚集,进而形成菌落,长期留置于人体时易引起感染。同时,硅橡胶用于长期植入式医疗器械时其表面易粘附大量血小板而引起血栓,甚至引起管形医用装置(如导管、套管、内窥镜等)的内腔堵塞。为了使硅橡胶材料具有更广泛的应用,提高其生物相容性,改善其表面亲水性是十分必要的。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.
目前硅橡胶亲水改性的研究主要集中在两个方向上:本体改性和表面改性。本体改性主要是将一些亲水单体与硅橡胶体系共混,虽然能实现硅橡胶表面亲水化,但是本体改性或多或少都会影响硅橡胶的本体结构,对其理化性能的影响要比表面改性大。表面改性的本质就是在生物材料表面引入生物相容性良好的物质,覆盖原有生物相容性差的物质,以“欺骗”被植入的生物体,避免产生过于激烈的排异反应,从而达到改性目的。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公开了一种生物亲和性硅橡胶的制备方法。该专利首先利用等离子体处理室温硫化硅橡胶,在硅橡胶表面产生羟基活性点;再向非极性溶剂中加入等离子体处理过的硅橡胶、有机胺,冰盐浴下搅拌,滴加含有溴化剂和非极性溶剂的混合液,撤去冰盐浴升到室温,继续避光搅拌,得到表面含溴基团的硅橡胶;最后将表面含有溴基团的硅橡胶、丙烯酰胺单体、CuCl/bpy催化剂置 于反应容器中,再用注射器向反应容器中注入经脱气处理的溶剂,将反应容器置于恒温油浴中反应;洗涤、干燥后即得到表面接枝聚丙烯酰胺的亲水性硅橡胶。虽然该方法能将硅橡胶表面接触角从108°降低到16°,但是该方法涉及步骤较多,每一步反应条件都比较苛刻,难以实现。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公开了一种亲水润滑硅橡胶导尿管及其亲水润滑涂层的制备方法。该方法是先将硅橡胶导管置于含有光引发剂的溶液中,然后取出,放入亲水单体溶液中紫外引发接枝,得到亲水涂层。虽然该方法能显著降低接触角,但亲水涂层与本体之间并没有化学键连接,涂层很不稳定。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.
发明内容Summary of the invention
技术问题:本发明所要解决的技术问题是:提供一种硅橡胶表面亲水改性的方法及应用方法,该方法中亲水层与硅橡胶本体通过化学键连接,可显著降低硅橡胶材料的接触角,改善其亲水性,提高其生物相容性,同时具有良好的透光率等性能。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.
技术方案:为了解决上述技术问题,本发明实施例采用如下技术方案:Technical Solution: In order to solve the above technical problem, the embodiment of the present invention adopts the following technical solutions:
一种硅橡胶表面亲水改性的方法,包含以下步骤:A method for hydrophilically modifying a surface of a silicone rubber, comprising the steps of:
步骤10)制备硅橡胶基片:将乙烯基聚硅氧烷、氢基聚硅氧烷和多乙烯基单体混合均匀,然后加入催化剂,并混合均匀,形成混合物;将混合物注入到模具中进行热固化,制成表面含有双键的硅橡胶基片;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;
步骤20)制备含有亲水单体的溶液:将带有双键的亲水性单体、交联剂、光引发剂溶解于有机溶剂中,得到含有亲水单体的溶液;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;
步骤30)进行硅橡胶表面亲水改性:将步骤10)制备的硅橡胶基片放入步骤20)制成的溶液中,置于紫外灯光下,紫外引发后取出,水洗得到亲水改性后的硅橡胶。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.
作为优选例,所述步骤10)中,硅橡胶基片中各组分质量分数如下:As a preferred example, in the step 10), the mass fraction of each component in the silicone rubber substrate is as follows:
乙烯基聚硅氧烷:55~84%;Vinyl polysiloxane: 55 to 84%;
氢基聚硅氧烷:7.2~25%;Hydrogen-based polysiloxane: 7.2 to 25%;
多乙烯基单体:5~24.6%;Polyvinyl monomer: 5 to 24.6%;
催化剂:0.1~0.4%。Catalyst: 0.1 to 0.4%.
作为优选例,所述步骤20)中,各物质质量分数如下:As a preferred example, in the step 20), the mass fraction of each substance is as follows:
亲水单体:5~35%;Hydrophilic monomer: 5 to 35%;
交联剂:1~5%;Crosslinking agent: 1 to 5%;
光引发剂:0.2~1%;Photoinitiator: 0.2 to 1%;
有机溶剂:60~90%。Organic solvent: 60 to 90%.
作为优选例,所述步骤10)中,所述乙烯基聚硅氧烷中的乙烯基摩尔含量和多乙烯基单体中的乙烯基摩尔含量之和,大于氢基聚硅氧烷中的氢基的摩尔含量。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.
作为优选例,所述步骤10)中,多乙烯基单体为甲基丙烯酸烯丙酯、四甲基二乙烯基二硅氧烷、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇四丙烯酸酯、四乙烯硅烷、乙二醇二甲基丙烯酸酯、新戊二醇二丙烯酸酯、1,4-二乙烯基-1,1,4,4-四甲基二甲硅烷基乙烷、硅酸四烯丙酯中的任意一种或两种组合。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.
作为优选例,所述步骤20)中,亲水单体为甲基丙烯酸-2-羟乙酯、N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、乙烯基磺酸钠、2-乙烯基吡咯、4-乙烯基吡咯、丙烯酰胺、聚乙二醇甲醚丙烯酸酯中的任意一种或两种组合。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.
作为优选例,所述步骤20)中,交联剂为N,N-亚甲基双丙烯酰胺、双烯丙酯乙缩醛、1,4-丁二醇二甲基丙烯酸酯、1,5-己二烯、甲基丙烯酰氧基乙烯基酯、甲基丙烯酸烯丙酯、乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇四丙烯酸酯、新戊二醇二丙烯酸酯中的任意一种。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.
作为优选例,所述步骤20)中,光引发剂为安息香、二乙氧基苯乙酮、2-羟基-2-甲基苯丙酮、1-羟基环己基苯基甲酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮、对苯氧基-2,2-二氯苯乙酮、2-二甲氨基-2-苄基-1-[4-(4-吗啉基)苯基]-1-丁酮中的任意一种。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.
作为优选例,所述步骤20)中,有机溶剂为甲醇、乙醇、丙醇、丁醇、异丙醇中的任意一种或两种组合。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.
一种亲水改性后的硅橡胶的应用方法,用于制作角膜接触镜、人工晶状体、医用导管、人工皮肤或者人工血管。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.
有益效果:与现有技术相比,本发明具有以下有益效果:本发明通过一步制成表面带有双键的硅橡胶基片,可接枝亲水单体进行表面亲水改性。本发明亲水涂层与硅橡胶本体通过化学键连接,从而使亲水层更稳定,可显著降低硅橡胶的表面接触角,改善其亲水性,提高其生物相容性,同时具有良好的透过率和机械性能。改性后的硅橡胶可用于角膜接触镜、人工晶状体、医用导管及人工血管领域。另外,本方法中每一步的反应条件都较易实现,原料易得,不需要使用昂贵的设备与试剂。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.
附图说明DRAWINGS
图1为本发明试验中对比例1的硅橡胶样品的全反射红外光谱(ATR)图;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;
图2为本发明试验中实施例1中步骤10)制备的带双键的硅橡胶基片的ATR图;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;
图3为本发明试验中实施例1中步骤30)制备的亲水改性硅橡胶的ATR图;Figure 3 is an ATR diagram of the hydrophilic modified silicone rubber prepared in the step 30) in Example 1 of the present invention;
图4为本发明试验中对比例1硅橡胶样品的接触角图;Figure 4 is a contact angle diagram of a silicone rubber sample of Comparative Example 1 in the test of the present invention;
图5为本发明试验中实施例1改性后亲水硅橡胶样品的接触角图。Figure 5 is a contact angle diagram of a modified hydrophilic silicone rubber sample of Example 1 in the test of the present invention.
具体实施方式Detailed ways
下面结合实施例,对本发明实施例的技术方案进行详细的说明。The technical solutions of the embodiments of the present invention are described in detail below with reference to the embodiments.
本发明实施例的一种硅橡胶表面亲水改性的方法,包含以下步骤:A method for hydrophilically modifying a surface of a silicone rubber according to an embodiment of the invention comprises the following steps:
步骤10)制备硅橡胶基片:将乙烯基聚硅氧烷、氢基聚硅氧烷和多乙烯基单体混合均匀,然后加入催化剂,并混合均匀,形成混合物;将混合物注入到模具中进行热固化,制成表面含有双键的硅橡胶基片。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.
作为优选,所述步骤10)中,硅橡胶基片中各组分质量分数如下:Preferably, in the step 10), the mass fraction of each component in the silicone rubber substrate is as follows:
乙烯基聚硅氧烷:55~84%;Vinyl polysiloxane: 55 to 84%;
氢基聚硅氧烷:7.2~25%;Hydrogen-based polysiloxane: 7.2 to 25%;
多乙烯基单体:5~24.6%;Polyvinyl monomer: 5 to 24.6%;
催化剂:0.1~0.4%。Catalyst: 0.1 to 0.4%.
作为优选,所述步骤10)中,乙烯基聚硅氧烷中的乙烯基摩尔含量和多乙烯基单体中的乙烯基摩尔含量之和,大于氢基聚硅氧烷中的氢基的摩尔含量。乙烯基摩尔含量大于氢基摩尔含量,才能制成表面带有双键的硅橡胶基片。优选的, 乙烯基聚硅氧烷的粘度为100~1000cst,乙烯基的摩尔含量为0.0085~0.035%;氢基聚硅氧烷粘度为10~70cst,氢基的摩尔含量为0.15~0.5%。模具中进行热固化,固化温度可为50~100℃。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.
优选的,多乙烯基单体为甲基丙烯酸烯丙酯、四甲基二乙烯基二硅氧烷、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇四丙烯酸酯、四乙烯硅烷、乙二醇二甲基丙烯酸酯、新戊二醇二丙烯酸酯、1,4-二乙烯基-1,1,4,4-四甲基二甲硅烷基乙烷、硅酸四烯丙酯中的任意一种或两种组合。这些单体与硅橡胶具有一定相容性的,能够保证改性后硅橡胶具有良好透光率。同时,这些单体分子中含有多个乙烯基,单体中部分乙烯基与氢基聚硅氧烷反应,剩余乙烯基和亲水单体反应。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.
步骤20)制备含有亲水单体的溶液:将带有双键的亲水性单体、交联剂、光引发剂溶解于有机溶剂中,得到含有亲水单体的溶液。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.
作为优选,所述步骤20)中,各物质质量分数如下:Preferably, in the step 20), the mass fraction of each substance is as follows:
亲水单体:5~35%;Hydrophilic monomer: 5 to 35%;
交联剂:1~5%;Crosslinking agent: 1 to 5%;
光引发剂:0.2~1%;Photoinitiator: 0.2 to 1%;
有机溶剂:60~90%。Organic solvent: 60 to 90%.
所述步骤20)中,亲水单体为甲基丙烯酸-2-羟乙酯、N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、乙烯基磺酸钠、2-乙烯基吡咯、4-乙烯基吡咯、丙烯酰胺、聚乙二醇甲醚丙烯酸酯中的任意一种或两种组合。这些亲水单体都带有双键,可进行自由基聚合反应。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.
交联剂为N,N-亚甲基双丙烯酰胺、双烯丙酯乙缩醛、1,4-丁二醇二甲基丙烯酸酯、1,5-己二烯、甲基丙烯酰氧基乙烯基酯、甲基丙烯酸烯丙酯、乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇四丙烯酸酯、新戊二醇二丙烯酸酯中的任意一种。交联剂作为自由基聚合的交联剂。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.
光引发剂为安息香、二乙氧基苯乙酮、2-羟基-2-甲基苯丙酮(D-1173)、1-羟基环己基苯基甲酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮、对苯氧基-2,2-二氯苯乙酮、2-二甲氨基-2-苄基-1-[4-(4-吗啉基)苯 基]-1-丁酮中的任意一种。光引发剂作为自由基聚合的引发剂。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.
有机溶剂为甲醇、乙醇、丙醇、丁醇、异丙醇中的任意一种或两种组合。这些有机溶剂能够溶解亲水单体、引发剂和交联剂。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.
步骤30)进行硅橡胶表面亲水改性:将步骤10)制备的硅橡胶基片放入步骤20)制成的溶液中,置于紫外灯光下,紫外引发后取出,水洗得到亲水改性后的硅橡胶。紫外光强为50~220V,光照射时间为5~60min。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.
利用上述方法制备的亲水改性后的硅橡胶,可用于制作角膜接触镜、人工晶状体、医用导管、人工皮肤或者人工血管。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.
上述实施例的方法中,步骤10)中,乙烯基聚硅氧烷和多乙烯基单体在铂催化剂作用下,与氢基聚硅氧烷发生硅氢加成反应,形成硅橡胶基片,因为乙烯基与氢基的摩尔比大于1,所以制成的硅橡胶基片表面带有多余双键。步骤30)中,带有双键的亲水单体,在引发剂、交联剂和紫外光照条件下,与硅橡胶基片表面的双键发生自由基聚合,将亲水单体接枝到硅橡胶表面,实现硅橡胶表面亲水改性。该实施例的方法制备表面亲水改性的硅橡胶,是通过一步制备表面带有双键的硅橡胶基片,可接枝亲水单体。而现有技术是制成硅橡胶后,利用各种手段在表面构造可反应官能团,再接枝亲水单体;或者采用溶剂使硅橡胶溶胀,通过物理或者化学方法将亲水单体嵌入到内部。与现有技术相比,本发明实施例的方法采用简单的共聚方法,直接制备了表面带有可反应性双键的硅橡胶,而不需要利用一些昂贵的设备(如等离子体处理器)或苛刻的反应条件(如真空脱气)在硅橡胶表面构造双键。本发明实施例的方法每一步反应条件都较易实现,原料易得,反应条件可控,并且本发明实施例对硅橡胶的光学性能和机械性能影响较小。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.
本发明实施例的方法,多乙烯基单体与乙烯基聚硅氧烷和氢基聚硅氧烷共聚,制备表面多余双键的基片,亲水单体与硅橡胶表面双键发生聚合,从而使亲水单体以化学键的形式接枝到硅橡胶表面,达到亲水改性的效果。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.
本发明实施例中,亲水涂层与硅橡胶本体通过化学键连接,从而使亲水层更稳定,可显著降低硅橡胶的表面接触角,改善其亲水性,提高其生物相容性,同时具有良好的透过率和机械性能。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.
本发明实施例的方法,首先在硅橡胶体系里加入多乙烯基单体,制备表面具 有可反应性双键的硅橡胶基片,然后将该基片浸泡在含有亲水单体、交联剂和光引发剂的溶液中,在紫外光条件下使硅橡胶表面的双键与亲水单体中的双键在溶液中发生聚合,使疏水的硅橡胶基片与亲水单体通过化学键连接,在硅橡胶表面接上一层亲水层,经处理后的硅橡胶基片具有良好的机械性能、光学性能、亲水性和生物相容性。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.
下面通过实验来验证本发明实施例方法制备的硅橡胶具有良好的性能。The silicone rubber prepared by the method of the embodiment of the present invention was verified by experiments to have good performance.
实施例1Example 1
(1)制备硅橡胶基片:将0.7g粘度750cst的乙烯基聚硅氧烷,0.2g的季戊四醇四丙烯酸酯,0.099g粘度30cst的氢基聚硅氧烷混合均匀,然后加入0.001g的催化剂,并混合均匀,形成混合物;将混合物注入模具中,60℃固化,制成表面含有双键的硅橡胶基片。(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)制备含有亲水单体的溶液:分别将0.15g的N-乙烯基己内酰胺,0.02g的三羟甲基丙烷三甲基丙烯酸酯,0.005g的1-羟基环己基苯基甲酮溶于0.825g的甲醇溶液中。(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)进行硅橡胶表面亲水改性:将步骤(1)所制备的硅橡胶基片放入步骤(2)制成的溶液中,置于紫外灯光下,光强为220V,光照时间5min后取出,去离子水冲洗得到亲水改性后的硅橡胶。(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.
实施例2Example 2
(1)制备硅橡胶基片:将0.648g粘度500cst的乙烯基聚硅氧烷,0.1g的乙二醇二甲基丙烯酸酯,0.25g粘度70cst的氢基聚硅氧烷混合均匀,然后加入0.002g的催化剂,并混合均匀,形成混合物;将混合物注入模具中,70℃固化,制成表面含有双键的硅橡胶基片。(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)制备含有亲水单体的溶液:分别将0.15g的甲基丙烯酸-2-羟乙酯,0.2g的N-乙烯基吡咯烷酮,0.04g的季戊四醇四丙烯酸酯,0.01g的2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮溶于0.6g的异丙醇溶液中。(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)进行硅橡胶表面亲水改性:将步骤(1)所制备的硅橡胶基片放入步骤(2)制成的溶液中,置于紫外灯光下,光强为50V,光照时间60min后取出, 去离子水冲洗得到亲水改性后的硅橡胶。(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.
实施例3Example 3
(1)制备硅橡胶基片:将0.696g粘度650cst的乙烯基聚硅氧烷,0.15g的1,4-二乙烯基-1,1,4,4-四甲基二甲硅烷基乙烷,0.15g粘度65cst的氢基聚硅氧烷混合均匀,然后加入0.004g的催化剂,并混合均匀,形成混合物;将混合物注入模具中,65℃固化,制成表面含有双键的硅橡胶基片。(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)制备含有亲水单体的溶液:分别将0.25g的2-乙烯基吡咯,0.03g的甲基丙烯酰氧基乙烯基酯,0.002g的D-1173溶于0.718g的异丙醇溶液中。(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)进行硅橡胶表面亲水改性:将步骤(1)所制备的硅橡胶基片放入步骤(2)制成的溶液中,置于紫外灯光下,光强为80V,光照时间50min后取出,去离子水冲洗得到亲水改性后的硅橡胶。(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.
实施例4Example 4
(1)制备硅橡胶基片:将0.75g粘度400cst的乙烯基聚硅氧烷,0.05g的甲基丙烯酸烯丙酯,0.1985g粘度40cst的氢基聚硅氧烷混合均匀,然后加入0.0015g的催化剂,并混合均匀,形成混合物;将混合物注入模具中,80℃固化,制成表面含有双键的硅橡胶基片。(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)制备含有亲水单体的溶液:分别将0.1g的N-乙烯基吡咯烷酮,0.015g的乙二醇二甲基丙烯酸酯,0.01g的2,4,6-三甲基苯甲酰基-二苯基氧化膦溶于0.875g的乙醇溶液中。(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)进行硅橡胶表面亲水改性:将步骤(1)所制备的硅橡胶基片放入步骤(2)制成的溶液中,置于紫外灯光下,光强为150V,光照时间10min后取出,去离子水冲洗得到亲水改性后的硅橡胶。(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.
实施例5Example 5
(1)制备硅橡胶基片:将0.725g粘度500cst的乙烯基聚硅氧烷,0.15g的三羟甲基丙烷三甲基丙烯酸酯,0.1225g粘度50cst的氢基聚硅氧烷混合均匀,然后加入0.0025g的催化剂,并混合均匀,形成混合物;将混合物注入模具中, 90℃固化,制成表面含有双键的硅橡胶基片。(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)制备含有亲水单体的溶液:分别将0.05g的乙烯基磺酸钠,0.04g的三乙二醇二甲基丙烯酸酯,0.01g的2-二甲氨基-2-苄基-1-[4-(4-吗啉基)苯基]-1-丁酮溶于0.9g丙醇和异丙醇的混合溶液中。(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)进行硅橡胶表面亲水改性:将步骤(1)所制备的硅橡胶基片放入步骤(2)制成的溶液中,置于紫外灯光下,光强为90V,光照时间45min后取出,去离子水冲洗得到亲水改性后的硅橡胶。(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.
实施例6Example 6
(1)制备硅橡胶基片:将0.84g粘度700cst的乙烯基聚硅氧烷,0.085g的四乙烯硅烷,0.072g粘度55cst的氢基聚硅氧烷混合均匀,然后加入0.003g的催化剂,并混合均匀,形成混合物;将混合物注入模具中,75℃固化,制成表面含有双键的硅橡胶基片。(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)制备含有亲水单体的溶液:分别将0.15g的丙烯酰胺,0.0255g的双烯丙酯乙缩醛,0.0075g的二乙氧基苯乙酮溶于0.817g的乙醇溶液中。(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)进行硅橡胶表面亲水改性:将步骤(1)所制备的硅橡胶基片放入步骤(2)制成的溶液中,置于紫外灯光下,光强为75V,光照时间55min后取出,去离子水冲洗得到亲水改性后的硅橡胶。(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.
实施例7Example 7
(1)制备硅橡胶基片:将0.821g粘度1000cst的乙烯基聚硅氧烷,0.075g的硅酸四烯丙酯,0.1g粘度10cst的氢基聚硅氧烷混合均匀,然后加入0.004g的催化剂,并混合均匀,形成混合物;将混合物注入模具中,55℃固化,制成表面含有双键的硅橡胶基片。(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)制备含有亲水单体的溶液:分别将0.3g的聚乙二醇甲醚丙烯酸酯,0.01g的甲基丙烯酸烯丙酯,0.01g的2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮溶于0.68g的乙醇溶液中。(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)进行硅橡胶表面亲水改性:将步骤(1)所制备的硅橡胶基片放入步骤(2)制成的溶液中,置于紫外灯光下,光强为100,光照时间20min后取出, 去离子水冲洗得到亲水改性后的硅橡胶。(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.
实施例8Example 8
(1)制备硅橡胶基片:将0.55g粘度100cst的乙烯基聚硅氧烷,0.246g的新戊二醇二丙烯酸酯,0.2g粘度35cst的氢基聚硅氧烷混合均匀,然后加入0.004g的催化剂,并混合均匀,形成混合物;将混合物注入模具中,65℃固化,制成表面含有双键的硅橡胶基片。(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)制备含有亲水单体的溶液:分别将0.19g的4-乙烯基吡咯,0.05g的1,4-丁二醇二甲基丙烯酸酯,0.01g的对苯氧基-2,2-二氯苯乙酮溶于0.75g的乙醇溶液中。(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)进行硅橡胶表面亲水改性:将步骤(1)所制备的硅橡胶基片放入步骤(2)制成的溶液中,置于紫外灯光下,光强为110V,光照时间15min后取出,去离子水冲洗得到亲水改性后的硅橡胶。(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.
实施例9Example 9
(1)制备硅橡胶基片:将0.65g粘度400cst的乙烯基聚硅氧烷,0.1875g的四乙烯硅烷,0.16g粘度45cst的氢基聚硅氧烷混合均匀,然后加入0.0025g的催化剂,并混合均匀,形成混合物;将混合物注入模具中,90℃固化,制成表面含有双键的硅橡胶基片。(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)制备含有亲水单体的溶液:分别将0.08g的甲基丙烯酸-2-羟乙酯,0.03g的新戊二醇二丙烯酸酯,0.008g的2-二甲氨基-2-苄基-1-[4-(4-吗啉基)苯基]-1-丁酮溶于0.882g乙醇和异丙醇的混合溶液中。(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.
(3)进行硅橡胶表面亲水改性:将步骤(1)所制备的硅橡胶基片放入步骤(2)制成的溶液中,置于紫外灯光下,光强为90V,光照时间45min后取出,去离子水冲洗得到亲水改性后的硅橡胶。(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.
对比例1Comparative example 1
硅橡胶基片的准备:将0.94g粘度500cst的乙烯基聚硅氧烷,0.056g粘度30cst的氢基聚硅氧烷混合均匀,加入0.004g的催化剂,混合均匀后注入模具 中,80℃固化,得到未改性的基础硅橡胶样品。对比例1是不添加多乙烯基单体的硅橡胶基片,不进行亲水改性。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.
各实施例和对比例中,组分质量分数如表1所示:In each of the examples and comparative examples, the component mass fractions are shown in Table 1:
表1Table 1
Figure PCTCN2018072983-appb-000001
Figure PCTCN2018072983-appb-000001
性能测试:本发明对实施例1~12和对比实施例1进行接触角、相对蛋白吸附率、透光率测试。采用紫外-可见光分光光度计UV-2450测量硅橡胶样品的透光率。采用接触角测量仪CAM200(KSV)测量硅橡胶样品的表面接触角。使用BCA蛋白浓度测定试剂盒检测硅橡胶样品对牛血清白蛋白和溶菌酶的相对吸附率。测试结果如表2所示: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:
表2测试结果Table 2 test results
Figure PCTCN2018072983-appb-000002
Figure PCTCN2018072983-appb-000002
通过表2可以看出:实施例1~9的表面接触角均明显低于对比例1。与对比例1相比,实施例1~9对牛血清白蛋白和溶菌酶的相对吸附率明显减少。实施例1~9的透光率要略低于对比例1。这是因为与不改性硅橡胶相比,改性后硅橡胶表面覆盖了一层亲水层,所以透过率会略有下降,但是总体透光率均在92%以上,满足一般光学器械的基本要求。从以上分析结果可知,采用本发明实施例的亲水改性方法对硅橡胶进行亲水改性后,其表面亲水性显著增强,相对蛋白吸附率明显减少。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.
图1是不添加多乙烯单体的硅橡胶,即对比例1,在1638cm -1左右没有-C=C-吸收峰出现。这说明不添加多乙烯基单体的硅橡胶表面并没有多余双键,不能进行表面亲水改性。 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.
图2是添加多乙烯基单体后的硅橡胶,对应实施例1。从图2中可以看出,1638cm -1左右出现了-C=C-双键的吸收峰。这说明通过添加多乙烯基单体,成功的制备了表面具有双键的硅橡胶基片。 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.
图3是带有双键的硅橡胶基片,接枝亲水单体后的亲水硅橡胶,对应实施例1。从图3中可以看出,在1658cm -1处出现酰胺键的吸收峰。这说明N-乙烯基己内酰胺成功接枝到硅橡胶表面,说明带有双键的亲水单体可以与带有双键的硅橡胶发生反应,从而实现了硅橡胶的表面改性。 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.
图1至图3可知:通过本发明方法,可一步在表面制备带有双键的硅橡胶基片,该基片可与带双键的亲水单体反应,实现硅橡胶表面的亲水改性。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.
图4是对比例1硅橡胶样品的接触角图,接触角为110°。图5是实施例1改性后亲水硅橡胶样品的接触角图,接触角为55°。从图4个图5可知:通过本发明方法,可显著降低硅橡胶的表面接触角。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.
以上描述了本发明的基本原理和优点。本领域的技术人员应该了解,以上实施例仅用于进一步说明本发明,但并非用以限制本发明的范围,任何所属领域一般技术人员都可以轻易达成的修饰和改变均包括在本发明说明书揭示内容和所附权利要求书的范围内。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 (10)

  1. 一种硅橡胶表面亲水改性的方法,其特征在于,包含以下步骤:A method for hydrophilically modifying a surface of a silicone rubber, characterized in that it comprises the following steps:
    步骤10)制备硅橡胶基片:将乙烯基聚硅氧烷、氢基聚硅氧烷和多乙烯基单体混合均匀,然后加入催化剂,并混合均匀,形成混合物;将混合物注入到模具中进行热固化,制成表面含有双键的硅橡胶基片;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;
    步骤20)制备含有亲水单体的溶液:将带有双键的亲水性单体、交联剂、光引发剂溶解于有机溶剂中,得到含有亲水单体的溶液;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;
    步骤30)进行硅橡胶表面亲水改性:将步骤10)制备的硅橡胶基片放入步骤20)制成的溶液中,置于紫外灯光下,紫外引发后取出,水洗得到亲水改性后的硅橡胶。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.
  2. 按照权利要求1所述的硅橡胶表面亲水改性的方法,其特征在于,所述步骤10)中,硅橡胶基片中各组分质量分数如下: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:
    乙烯基聚硅氧烷:55~84%;Vinyl polysiloxane: 55 to 84%;
    氢基聚硅氧烷:7.2~25%;Hydrogen-based polysiloxane: 7.2 to 25%;
    多乙烯基单体:5~24.6%;Polyvinyl monomer: 5 to 24.6%;
    催化剂:0.1~0.4%。Catalyst: 0.1 to 0.4%.
  3. 按照权利要求1所述的硅橡胶表面亲水改性的方法,其特征在于,所述步骤20)中,各物质质量分数如下: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:
    亲水单体:5~35%;Hydrophilic monomer: 5 to 35%;
    交联剂:1~5%;Crosslinking agent: 1 to 5%;
    光引发剂:0.2~1%;Photoinitiator: 0.2 to 1%;
    有机溶剂:60~90%。Organic solvent: 60 to 90%.
  4. 按照权利要求1所述的硅橡胶表面亲水改性的方法,其特征在于,所述步骤10)中,所述乙烯基聚硅氧烷中的乙烯基摩尔含量和多乙烯基单体中的乙烯基摩尔含量之和,大于氢基聚硅氧烷中的氢基的摩尔含量。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.
  5. 按照权利要求1所述的硅橡胶表面亲水改性的方法,其特征在于,所述步骤10)中,多乙烯基单体为甲基丙烯酸烯丙酯、四甲基二乙烯基二硅氧烷、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇四丙烯酸酯、四乙烯硅烷、乙二醇二甲基丙烯酸酯、新戊二醇二丙烯酸酯、1,4-二乙烯基-1,1,4,4-四甲基二甲硅烷基乙 烷、硅酸四烯丙酯中的任意一种或两种组合。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.
  6. 按照权利要求1所述的硅橡胶表面亲水改性的方法,其特征在于,所述步骤20)中,亲水单体为甲基丙烯酸-2-羟乙酯、N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、乙烯基磺酸钠、2-乙烯基吡咯、4-乙烯基吡咯、丙烯酰胺、聚乙二醇甲醚丙烯酸酯中的任意一种或两种组合。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.
  7. 按照权利要求1所述的硅橡胶表面亲水改性的方法,其特征在于,所述步骤20)中,交联剂为N,N-亚甲基双丙烯酰胺、双烯丙酯乙缩醛、1,4-丁二醇二甲基丙烯酸酯、1,5-己二烯、甲基丙烯酰氧基乙烯基酯、甲基丙烯酸烯丙酯、乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇四丙烯酸酯、新戊二醇二丙烯酸酯中的任意一种。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.
  8. 按照权利要求1所述的硅橡胶表面亲水改性的方法,其特征在于,所述步骤20)中,光引发剂为安息香、二乙氧基苯乙酮、2-羟基-2-甲基苯丙酮、1-羟基环己基苯基甲酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮、对苯氧基-2,2-二氯苯乙酮、2-二甲氨基-2-苄基-1-[4-(4-吗啉基)苯基]-1-丁酮中的任意一种。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.
  9. 按照权利要求1所述的硅橡胶表面亲水改性的方法,其特征在于,所述步骤20)中,有机溶剂为甲醇、乙醇、丙醇、丁醇、异丙醇中的任意一种或两种组合。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.
  10. 一种权利要求1所述方法制备的亲水改性后的硅橡胶的应用方法,用于制作角膜接触镜、人工晶状体、医用导管、人工皮肤或者人工血管。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.
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